KR20180014539A - Photosensitive Resin Composition,CuredFilmPrepared therefrom, and Electronic Device Incorporating Cured Film - Google Patents

Abstract

The present invention relates to a photosensitive resin composition, a cured film formed from the same, and an electronic device having the cured film. According to an embodiment of the present invention, the photosensitive resin composition comprises: polysiloxane resin; cadmium binder resin; a reactive unsaturated compound; a photopolymerization initiator; and an epoxy ring opening reaction initiator. The photosensitive resin composition, the cured film formed from the same, and the electronic device having the cured film of the present invention can improve a UV transmission coefficient and developability.

Description

[0001] The present invention relates to a photosensitive resin composition, a cured film formed therefrom, and an electronic device having the cured film (Photosensitive Resin Composition, Cured Film Development, and Electronic Device Incorporating Cured Film)

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

In order to form a column spacer, a barrier rib, an overcoat, and a color resist, as well as a passivation insulating film, a gate insulating film, and a planarizing film for insulating between wirings disposed between the wirings in the TFT type liquid crystal display element or the integrated circuit element A negative photosensitive resin composition is mainly used.

The conventional negative photosensitive resin composition is composed of components such as a binder, a reactive unsaturated compound, a photopolymerization initiator, and a solvent, and the binder mainly contains an olefinically unsaturated compound.

However, conventional olefinic unsaturated compounds can not be cured at low temperatures and thus can not be applied to a flexible display manufacturing process. Therefore, there is a demand for the development of a binder and a curing system which can be easily synthesized while having a curing property at a low temperature which is considerably lower than that of the existing organic film and is easy to supply and demand, and researches on this have been continued.

One embodiment of the present invention is to provide a photosensitive resin composition excellent in performance such as chemical resistance, insulation, sensitivity and the like, and particularly excellent in residual film ratio, UV transmittance, developability and the like while being capable of curing at low temperature.

Another embodiment is to provide a cured film produced using the photosensitive resin composition.

Another embodiment is to provide an electronic device comprising the cured film.

One embodiment is a photosensitive resin composition comprising (A) a polysiloxane resin represented by the following formula (1), (B) a carcass binder resin, (C) a reactive unsaturated compound, (D) a photopolymerization initiator, and Lt; / RTI >

[Chemical Formula 1]

(R ¹ R ² R ³ SiO _1/2 ) _M1 (R ⁴ R ⁵ SiO _2/2 ) _D (R ⁶ R ⁷ SiO _1/2 -Y ₁ -SiO _1/2 R ⁸ R ⁹ ) _{M 2} (R ¹⁰ SiO _3/2 ) _{T 1} (SiO _{3/ 2-} Y ₂ -SiO _3/2 ) _{T 2} (SiO _4/2 ) _Q

In Formula 1,

R ¹ to R ¹⁰ each independently represent 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 C1 to C30 A substituted or unsubstituted C2 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C2 to C30 alkoxy group, a substituted or unsubstituted C2 to C30 alkoxy group, a substituted or unsubstituted C2 to C30 alkoxy group, C = O) -, wherein R is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group,

At least one of R ¹ to R ¹⁰ contains an epoxy group,

Y ₁ represents 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 alkenylene group, a substituted or unsubstituted C2 to C30 alkenylene group, C30 alkynylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, or a combination thereof,

Y ₂ represents 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 alkenylene group, a substituted or unsubstituted C2 to C30 alkynylene group, A substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, or a combination thereof,

0 < M1 < 1, 0 <

M1 + M2 + D + T1 + T2 + Q = 1,

The structural units represented by M1, M2, D, T1, T2, and Q may each include one or more different structural units.

M1, M2, D and Q are 0, and 0.8 < T1 < 1 and 0 <

M1, M2, D and Q are each 0 and 0.9 <T1 <1, 0 <T2 <0.1.

The epoxy group equivalent contained in the polysiloxane resin represented by the formula (1) may be from 50 g / eq to 260 g / eq.

The number average molecular weight of the polysiloxane resin represented by Formula 1 may be 100 g / mole to 100,000 g / mole.

Wherein at least ^{one of} R ¹ to R ¹⁰ is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkoxy group, or a combination thereof, wherein at least one of R ¹ to R ¹⁰ is an epoxy group &Lt; / RTI &gt;

The monovalent organic group substituted with an epoxy group may be a C1 to C10 alkyl group substituted with an epoxy group, a C3 to C10 cycloalkyl group substituted with an epoxy group, a C1 to C10 alkoxy group substituted with an epoxy group, a C1 to C10 ether group substituted with an epoxy group, . &Lt; / RTI &gt;

The monovalent organic group substituted with an epoxy group may be an epoxy cycloalkyl group, an oxiranyl alkyl group, an oxetane alkyl group, or a glycidoxyalkyl group.

The cadmium binder resin may include a structural unit represented by the following formula (2).

(2)

In Formula 2,

R ¹¹ and R ¹² are each independently a hydrogen atom or a substituted or unsubstituted (meth) acryloyloxyalkyl group,

R ¹⁵ is a hydrogen atom or a substituted or unsubstituted (meth) acrylate group,

Z ¹ is any one of the linking groups represented by the following formulas (2-1) to (2-3)

Z ² is an acid anhydride residue,

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

In the above Formulas 2-1 to 2-3,

R ¹³ and R ¹⁴ are each independently a hydrogen atom, a halogen atom, or a substituted or unsubstituted C1 to C20 alkyl group,

m1 and m2 are each independently an integer of 0 to 4;

Z ¹ is a linking group represented by Formula 2-3, and Z ² is a residue of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride.

The cationic binder resin may have a weight average molecular weight of 1,000 to 20,000.

The epoxy ring opening reaction initiator may include a sulfonium-based cation and a borate-based anion.

The epoxy ring opening reaction initiator may be a photosensitive resin composition represented by the following formula (6).

[Chemical Formula 6]

In Formula 6,

R ²¹ to R ²⁴ each independently represent a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 aryl group or a substituted or unsubstituted C2 to C20 heteroaryl group,

X ^- is a borate anion.

The borate anion may be represented by the following general formula (7).

(7)

In Formula 7,

R ²⁶ to R ³⁰ are each independently F, Cl, Br or I.

The photosensitive resin composition may further comprise (F) a solvent.

(A) 5 to 25% by weight of the polysiloxane resin represented by the formula (1), 10 to 20% by weight of the cyanide binder resin (B) based on the total weight of the photosensitive resin composition, , (C) 1 to 20% by weight of a reactive unsaturated compound, (D) 0.1 to 10% by weight of a photopolymerization initiator, (E) 0.1 to 10% by weight of an epoxy ring opening initiator, ) &Lt; / RTI &gt; solvent balance.

The photosensitive resin composition may be a negative type photosensitive resin composition.

The photosensitive resin composition may be curable at a temperature of 85 캜 or lower.

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

Another embodiment provides an electronic device comprising the cured film.

The photosensitive resin composition according to one embodiment exhibits not only excellent performance such as chemical resistance, insulation and sensitivity, but also an improved residual film ratio, UV transmittance, developability and the like, which can be cured at low temperature in particular.

In addition, the cured film prepared by curing the photosensitive resin composition according to one embodiment is excellent in low-temperature curing property, chemical resistance, and durability, and is suitable for use as an interlayer insulating film such as a flexible display.

Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

Unless otherwise specified herein, "alkyl group" means a C1 to C20 alkyl group, "alkenyl group" means a C2 to C20 alkenyl group, "cycloalkenyl group" means a C3 to C20 cycloalkenyl group Quot; means a C3 to C20 heterocycloalkenyl group, "an aryl group" means a C6 to C20 aryl group, an "arylalkyl group" means a C6 to C20 arylalkyl group, Refers to a C 1 to C 20 alkylene group, "arylene group" refers to a C6 to C20 arylene group, "alkylarylene group" refers to a C6 to C20 alkylarylene group, "heteroarylene group" refers to a C3 to C20 hetero Quot; means an arylene group, and the "alkoxysilylene group" means a C1 to C20 alkoxysilylene group.

Unless otherwise specified herein, "substituted" means that at least one hydrogen atom is replaced by a halogen atom (F, Cl, Br, I), a hydroxy group, a C1 to C20 alkoxy group, a nitro group, a cyano group, A thio group, an ester group, an ether group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, an amidino group, a hydrazino group, a hydrazino group, a carbonyl group, a carbamyl group, A C3 to C20 cycloalkenyl group, a C3 to C20 cycloalkynyl group, a C2 to C20 alkynyl group, a C6 to C20 aryl group, a C3 to C20 cycloalkyl group, a C3 to C20 cycloalkenyl group, Substituted with a substituent of a C2 to C20 heterocycloalkyl group, a C2 to C20 heterocycloalkenyl group, a C2 to C20 heterocycloalkynyl group, a C3 to C20 heteroaryl group, or a combination thereof.

Also, unless otherwise specified herein, "hetero" means that at least one heteroatom of N, O, S, and P is included in the formula.

&Quot; (Meth) acrylic acid "refers to both" acrylic acid "and" methacrylic acid " "It means both are possible.

"Combination" as used herein, unless otherwise specified, means mixing or copolymerization.

Unless otherwise defined in the chemical formulas in this specification, when a chemical bond is not connected to a position to which a chemical bond is to be connected, it means that a hydrogen atom is bonded at the above position.

In the present specification, the cadmium resin means a resin in which at least one linking group selected from the group consisting of the following formulas (2-1) to (2-3) is included in the main backbone of the resin.

Also, unless otherwise specified herein, "*" means the same or different atom or moiety connected to the formula.

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

The photosensitive resin composition according to one embodiment comprises (A) a polysiloxane resin represented by the following formula (1), (B) a cadmium-based binder resin, (C) a reactive unsaturated compound, (D) a photopolymerization initiator, and Lt; / RTI &gt;

[Chemical Formula 1]

(R ¹ R ² R ³ SiO _1/2 ) _M1 (R ⁴ R ⁵ SiO _2/2 ) _D (R ⁶ R ⁷ SiO _1/2 -Y ₁ -SiO _1/2 R ⁸ R ⁹ ) _{M 2} (R ¹⁰ SiO _3/2 ) _{T 1} (SiO _{3/ 2-} Y ₂ -SiO _3/2 ) _{T 2} (SiO _4/2 ) _Q

In Formula 1,

R ¹ to R ¹⁰ each independently represent 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 C1 to C30 A substituted or unsubstituted C2 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C2 to C30 alkoxy group, a substituted or unsubstituted C2 to C30 alkoxy group, a substituted or unsubstituted C2 to C30 alkoxy group, C = O) -, wherein R is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group,

At least one of R ¹ to R ¹⁰ contains an epoxy group,

Y ₁ represents 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 alkenylene group, a substituted or unsubstituted C2 to C30 alkenylene group, C30 alkynylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, or a combination thereof,

Y ₂ represents 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 alkenylene group, a substituted or unsubstituted C2 to C30 alkynylene group, A substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, or a combination thereof,

0 < M1 < 1, 0 <

M1 + M2 + D + T1 + T2 + Q = 1,

The structural units represented by M1, M2, D, T1, T2, and Q may each include one or more different structural units.

The interlayer insulating film applied to the flexible display is important for low temperature curability, chemical resistance, and etching resistance. In particular, if curing is not performed at a low temperature, panel problems may occur due to generation of haze or outgas in the CVD (chemical vapor deposition) process of the upper film and decrease in etching resistance of the subsequent process.

Conventionally, in order to solve such a problem, attempts have been made to introduce an epoxy group into the acrylic copolymer itself or to realize low-temperature curing properties with the epoxy silicone composition itself, but it is difficult to secure desired hardness at low temperatures in the acrylic copolymer itself , It was difficult to secure pattern characteristics with the epoxy silicone composition.

However, the photosensitive resin composition according to one embodiment contains the polysiloxane resin represented by the above formula (1), that is, a siloxane compound containing an epoxy group together with an epoxy ring opening reaction initiator to induce the ring opening reaction of the epoxy group at a low temperature, Thereby providing a photosensitive resin composition which is curable at a lower temperature and in which a pattern characteristic is realized.

Further, by applying a cadmium-based binder resin capable of mixing with the polysiloxane resin containing the epoxy group, the performance such as transmittance, insulation, chemical resistance, outgassing and the like are remarkably improved, Provided is a photosensitive resin composition capable of securing reliability in use as an interlayer insulating film or the like and capable of shortening a processing time.

Hereinafter, each component of the photosensitive resin composition according to one embodiment will be described in detail.

(A) Polysiloxane  Suzy

The polysiloxane resin may be represented by the following formula (1).

[Chemical Formula 1]

(R ¹ R ² R ³ SiO _1/2 ) _M1 (R ⁴ R ⁵ SiO _2/2 ) _D (R ⁶ R ⁷ SiO _1/2 -Y ₁ -SiO _1/2 R ⁸ R ⁹ ) _{M 2} (R ¹⁰ SiO _3/2 ) _{T 1} (SiO _{3/ 2-} Y ₂ -SiO _3/2 ) _{T 2} (SiO _4/2 ) _Q

In Formula 1,

R ¹ to R ¹⁰ each independently represent 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 C1 to C30 A substituted or unsubstituted C2 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C2 to C30 alkoxy group, a substituted or unsubstituted C2 to C30 alkoxy group, a substituted or unsubstituted C2 to C30 alkoxy group, C = O) -, wherein R is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group,

At least one of R ¹ to R ¹⁰ contains an epoxy group,

Y ₁ represents 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 alkenylene group, a substituted or unsubstituted C2 to C30 alkenylene group, C30 alkynylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, or a combination thereof,

Y ₂ represents 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 alkenylene group, a substituted or unsubstituted C2 to C30 alkynylene group, A substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, or a combination thereof,

0 < M1 < 1, 0 <

M1 + M2 + D + T1 + T2 + Q = 1,

The structural units represented by M1, M2, D, T1, T2, and Q may each include one or more different structural units.

In Formula 1, Y ₂ may be a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, or a substituted or unsubstituted C6 to C30 arylene group, or a combination thereof , In one embodiment, Y ₂ can be a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C3 to C10 cycloalkylene group, or a substituted or unsubstituted C6 to C20 arylene group, or combinations thereof have.

In formula _{1, (R 6 R 7 SiO} 1/2 -Y 1 -SiO 1/2 R 8 R 9) , or _{(SiO 3/2 -Y 2 -SiO} 3/2) structural unit represented by, in particular, ( SiO _3/2 -Y ₂ -SiO structural unit represented by the _3/2) is the cross-linking agent role. Therefore, the photosensitive resin composition containing the structural units forms a dense structure through crosslinking at the time of curing, so that the cured film produced therefrom has high mechanical strength, for example, high hardness, And at the same time, the penetration of the organic solvent is also effectively blocked, thereby solving the problem of the residual film ratio that the film thickness after development is reduced to fail to form a flat film, and the organic insulating film having excellent chemical resistance, Can be realized.

In one embodiment, the structural unit represented by the T2, _{i.e., (SiO 3/2 -Y 2} -SiO 3/2) molar ratio is 1 mole of the polysiloxane resin of 0 <T2 <0.2, for example, represented by the general formula (I) of the For example, 0 <T2? 0.17, for example 0 <T2? 0.15, for example 0 <T2? 0.13, For example, 0 <T2? 0.09, e.g., 0 <T2? 0.08, such as 0 <T2? 0.07, For example, 0 <T2? 0.04, for example, 0 <T2? 0.03.

By including the structural unit represented by the above T2 within the above range, the photosensitive resin composition has a high surface hardness, a high crack resistance, a low dielectric constant, a high chemical resistance and an etching resistance after curing, Lt; / RTI &gt;

The structural unit represented by T1 in the polysiloxane resin represented by the general formula (1) is 0.8? T1 <1, for example, 0.85? T1 <1, 1, for example, 0.95? T1 <1.

When including a structural unit represented by the structural unit represented by the polysiloxane resin in T1 represented by the following formula (1), i.e., (R ₁₀ SiO _3/2) in the above range, a photosensitive resin comprising a polysiloxane resin represented by the general formula (1) The composition has high storage stability, high permeability after curing, high hardness, high residual film ratio, high resolution, and excellent sensitivity to light.

In one embodiment, M1, M2, D, and Q in Formula 1 are each 0, and 0.8 <T1 <1, 0 <T2 <0.2.

In one embodiment, M1, M2, D, and Q in Formula 1 are each 0 and 0.9 <T1 <1, 0 <T2 <0.1.

In one embodiment, M1, M2, D, and Q in formula (1) are each 0, and 0.95? T1 <1, 0 <T2? 0.05.

At least one of R ¹ to R ¹⁰ in the polysiloxane resin represented by Formula 1 is a monovalent organic group containing an epoxy group. For example, the monovalent organic group comprising an epoxy group may be an epoxy-substituted monovalent aliphatic organic group, an epoxy-substituted monovalent cycloaliphatic group group, or an epoxy-substituted monovalent aromatic organic group.

Examples of the monovalent organic group substituted with an epoxy group include a C1 to C10 alkyl group substituted with an epoxy group, a C3 to C10 cycloalkyl group substituted with an epoxy group, a C1 to C10 alkoxy group substituted with an epoxy group, a C1 to C10 ether group substituted with an epoxy group , Or a combination thereof.

Specific examples of the monovalent organic group substituted with an epoxy group include an epoxycycloalkyl group, an oxiranylalkyl group, an oxetanealkyl group, and a glycidoxyalkyl group. Examples of the monovalent organic group include an epoxycyclohexyl group, an oxetanyl group, Propyl group, and the like, but are not limited thereto.

The equivalent amount of the epoxy group contained in the compound represented by the general formula (1) is 50 g / eq to 260 g / eq. For example, the equivalent of the epoxy group contained in the polysiloxane resin represented by Formula 1 may be, for example, 100 g / eq to 250 g / eq, such as 150 g / eq to 200 g / eq, such as 170 g / g / eq. When the equivalent of the epoxy group is in the above range, the cured film obtained by curing the composition can have high surface hardness and high transmittance, low haze, and excellent folding characteristics. If the epoxy equivalent is less than 50 g / eq, there may be a problem that the epoxy ring opening reaction does not proceed sufficiently within the range of the appropriate initiator. If the epoxy equivalent is more than 260 g / eq, the crosslinking effect due to the epoxy ring-

The polysiloxane resin represented by the formula (1) has a number average molecular weight (g / mole) of 100 to 100,000, for example, a number average molecular weight of 150 to 50,000, for example, a number average molecular weight of 1,000 to 40,000, And may have a number average molecular weight of from 2,000 to 10,000.

When the number average molecular weight of the polysiloxane resin represented by the general formula (1) is within the above range, it is possible to reduce the hardness characteristics and the surface wrinkles and stickiness. When the number average molecular weight is less than 100 g / mole, there may be a problem of stability such as increase in molecular weight upon stirring, because of high reactivity. When the number average molecular weight exceeds 100,000 g / mole, Lt; / RTI &gt;

Assuming that the number average molecular weight (M _n) is, for example, the molecules of a molecular weight M _i N _i dog present in the unit volume, to be calculated with equation (2).

&Quot; (2) &quot;

Number average molecular weight (M _n ) = ΣM _i N _i / ΣN _i

The polysiloxane resin represented by the general formula (1) may be contained in an amount of 5 to 25% by weight, for example, 5 to 15% by weight based on the total amount of the photosensitive resin composition. When the polysiloxane resin is contained within the above range, excellent patternability and low-temperature hardening chemical resistance can be realized.

The polysiloxane resin represented by the general formula (1) is, for example, a monomer represented by 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 R ⁷ SiZ ₄ -Y ₁ -SiZ ₅ R ⁸ R ⁹ , a monomer represented by R ¹⁰ SiZ ₆ Z ₇ Z ₈ , a monomer represented by SiZ ₉ Z ₁₀ Z ₁₁ -Y ₂ -SiZ ₁₂ Z ₁₃ Z ₁₄ , and a monomer represented by SiZ ₁₅ Z ₁₆ Z ₁₇ &lt; / RTI &gt;&lt; RTI ID = 0.0 &gt; _18. &Lt; / RTI &gt; Here, the definitions of R ¹ to R ¹⁰ are as defined above, and Z ₁ to Z ₁₈ are each independently a C ₁ to C 6 alkoxy group, a hydroxy group, a halogen group, a carboxyl group, or a combination thereof.

The hydrolysis and polycondensation reaction for preparing the polysiloxane resin represented by the general 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 to 150 ° C, for example, 90 to 130 ° C for 0.5 to 50 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 the same solvent as the solvent that can be contained in the low-temperature curing composition according to the above embodiment including the compound of formula (1) may be used.

The amount of the solvent to be added may be 10 to 1,000 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 4.5 mol per 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 0.001 to 10 parts by weight based on 100 parts by weight of the total weight of the monomers.

(B) Carometer  Binder resin

The cadmium binder resin may include a structural unit represented by the following formula (2).

(2)

In Formula 2,

R ¹¹ and R ¹² are each independently a hydrogen atom or a substituted or unsubstituted (meth) acryloyloxyalkyl group,

R ¹⁵ is a hydrogen atom or a substituted or unsubstituted (meth) acrylate group,

Z ¹ is any one of the linking groups represented by the following formulas (2-1) to (2-3)

Z ² is a residue derived from an acid anhydride:

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

In the above Formulas 2-1 to 2-3,

R ¹³ and R ¹⁴ are each independently a hydrogen atom, a halogen atom, or a substituted or unsubstituted C1 to C20 alkyl group,

m1 and m2 are each independently an integer of 0 to 4;

In one embodiment, Z ¹ may be a linking group represented by Formula 2-3, and Z ² may be a residue of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride.

The cadmium binder resin may have a weight average molecular weight of 1,000 to 20,000, for example, a weight average molecular weight of 3,000 to 8,000. When the cationic binder resin has a weight average molecular weight in the above range, the pattern formation is good without residue, and there is no loss of film thickness during development, and a good pattern can be obtained.

The weight average molecular weight (M _w ) can be calculated, for example, by the following equation (1), assuming that there are N _i molecules of molecular weight M _i in the unit volume.

[Equation 1]

Weight average molecular weight (M _w ) = ΣM _i ² N _i / ΣM _i N _i

For example, the cationic binder resin may be any one selected from the group consisting of the following Formulas (2-1a), (2-2a) and (2-3a), the following Formula (B '), ) In a molar ratio of 1 mol: 2 to 4 mol: 2 to 8 mol, respectively. (A ': B': C 'molar ratio = 1: 2 to 4: 2 to 8)

[Formula 2-1a]

[Formula 2-2a]

[Chemical Formula 2-3a]

(3)

[Chemical Formula 4]

In the above formulas (3) and (4)

L ¹ represents a single bond, a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C2 to C10 alkenylene group, a substituted or unsubstituted C6 to C20 arylene group, -O-, a substituted or unsubstituted C1 To C10 alkyl ether groups or combinations thereof,

X is a halogen atom such as F, Cl, Br or I,

R ^a is a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C1 to C10 alkoxy group, .

The cadmium-based binder resin may include a functional group represented by the following formula (5) in at least one of the two terminals.

[Chemical Formula 5]

In Formula 5,

Z ³ can be represented by the following formulas (5-1) to (5-7).

[Formula 5-1]

(Wherein R ^b and R ^c are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, an ester group or an ether group)

[Formula 5-2]

[Formula 5-3]

[Formula 5-4]

[Formula 5-5]

Wherein R ^d is O, S, NH, a substituted or unsubstituted C1 to C20 alkylene group, a C1 to C20 alkylamine group, or a C2 to C20 alkenylamine group.

[Formula 5-6]

[Formula 5-7]

Examples of the cationic binder resin include fluorene-containing compounds such as 9,9-bis (4-oxiranylmethoxyphenyl) fluorene; Benzene tetracarboxylic dianhydride, benzene tetracarboxylic acid dianhydride, naphthalene tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride, cyclobutanetetracarboxylic dianhydride, Anhydride compounds such as lyrenetetracarboxylic acid dianhydride, tetrahydrofuran tetracarboxylic acid dianhydride, and tetrahydrophthalic anhydride; Glycol compounds such as ethylene glycol, propylene glycol, and polyethylene glycol; Alcohol compounds such as methanol, ethanol, propanol, n-butanol, cyclohexanol and benzyl alcohol; Propylene glycol methyl ethyl acetate, and N-methyl pyrrolidone; Phosphorus compounds such as triphenylphosphine; And an amine or an ammonium salt compound such as tetramethylammonium chloride, tetraethylammonium bromide, benzyldiethylamine, triethylamine, tributylamine, benzyltriethylammonium chloride, and the like.

When the photosensitive resin composition according to one embodiment contains a cadmium-based binder resin as the binder resin, the sensitivity of the photosensitive resin composition upon photo-curing is good and the fine patterning property is excellent and the chemical resistance is improved.

The cadmium binder resin may be contained in an amount of 10% by weight to 20% by weight, for example, 12% by weight to 18% by weight based on the total amount of the photosensitive resin composition. When the cadmium binder resin is contained within the above range, excellent sensitivity, resolution and chemical resistance can be obtained.

(C) a reactive unsaturated compound

As the reactive unsaturated compound, monomers or oligomers commonly used in photosensitive resin compositions, monofunctional or polyfunctional esters of (meth) acrylic acid having at least one ethylenically unsaturated double bond can be used.

Examples of commercially available monofunctional (meth) acrylates include Aronix M-101, M-111, M-114 (manufactured by Toagosei Chemical Industry Co., Ltd.), AKAYARAD TC-110S, (Manufactured by Nihon Kayaku Co., Ltd.), V-158 and V-2311 (manufactured by Osaka Yuki Kagaku Kogyo Co., Ltd.). As the bifunctional (meth) acrylate, commercially available products such as Aronix M-210, Dong M-240, Dong M-6200 (manufactured by Toagosei Chemical Industry Co., Ltd.), KAYARAD HDDA, Dong HX- R-604 (manufactured by Nihon Kayaku Co., Ltd.), V260, V312, and V335 HP (manufactured by Osaka Yukigagaku Kogyo Co., Ltd.). Examples of the (meth) acrylate having three or more functional groups include trimethylol propane triacrylate, pentaerythritol triacrylate, trisacryloyloxyethyl phosphate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, And M-8060, M-8060, M-8060, M-8030, M-8060, (Manufactured by Toagosei Chemical Industry Co., Ltd.), KAYARAD TMPTA, copper DPCA-20, copper-30, copper-60, copper-120 (manufactured by Nihon Kayaku Co., Ltd.) -360, copper-GPT, copper-3PA, and copper-400 (manufactured by Osaka Yukigaya Chemical Co., Ltd.). These compounds may be used singly or in combination of two or more.

The content of the reactive unsaturated compound is 1 wt% to 20 wt%, for example, 3 wt% to 15 wt%, for example, 3 wt% to 10 wt% based on the total amount of the photosensitive resin composition. When the content of the reactive unsaturated compound is less than 1% by weight, the sensitivity tends to lower in the presence of oxygen and pattern formation is difficult. When the content of the reactive unsaturated compound exceeds 20% by weight, compatibility with the cadmium binder resin tends to be lowered. Can be rough.

(D) Light curing Initiator

As the photopolymerization initiator, an acetophenone-based compound, a benzophenone-based compound, a thioxanthone-based compound, a benzoin-based compound, a triazine-based compound or an oxime-based compound can be used as an initiator generally used in a photosensitive resin composition.

Examples of the acetophenone-based compound include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, dichloro-4-phenoxyacetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropanone, p-butyldichloroacetophenone, 1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one.

Examples of the benzophenone compound include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis (dimethylamino) benzophenone, '-Bis (diethylamino) benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, and 3,3'-dimethyl-2-methoxybenzophenone.

Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2- Chlorothioxanthone and the like.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal.

Examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -Dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) (Trichloromethyl) -6-styryl-s-triazine, 2- (naphtho-1-yl) - 4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthol-1-yl) -Bis (trichloromethyl) -6- (4-methoxystyryl) -s-triazine, and the like. .

Examples of the oxime compounds include O-acyloxime compounds, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, O-ethoxycarbonyl-a-oxyamino-1-phenylpropan- Can be used. Specific examples of the O-acyloxime-based compound include 1,2-octanedione, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin- 2-oxime-O-benzoate, 1- (4-phenylsulfanylphenyl) -octane-1,2-dione -1-one oxime-O-acetate and 1- (4-phenylsulfanylphenyl) -butan-1-one oxime- O-acetate and the like can be used.

The photopolymerization initiator may be a carbazole compound, a diketone compound, a sulfonium borate compound, a diazo compound, an imidazole compound, or a nonimidazole compound in addition to the above compounds.

The photopolymerization initiator may be used in combination with a photosensitizer that generates a chemical reaction by absorbing light to be in an excited state and transferring its energy.

Examples of the photosensitizer include tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol tetrakis-3-mercaptopropionate and the like .

The photopolymerization initiator may be included in an amount of 0.1 wt% to 10 wt%, for example, 0.5 wt% to 2 wt% with respect to the total amount of the photosensitive resin composition. If the content of the photopolymerization initiator is less than 0.1% by weight, the sensitivity of the radicals is likely to be lowered by oxygen, and if the content is more than 10% by weight, the color density of the solution may be increased or precipitated.

(E) Epoxy Ring opening reaction Initiator

The epoxy ring opening reaction initiator may include a boron anion and a sulfur cation. For example, the epoxy ring opening reaction initiator may include a borate-based anion compound (a borate-based anion) and a sulfonyl-based cationic compound (a sulfonium-based cation).

For example, the sulfonyl-based cationic compound (sulfonium-based cation) may mean a cationic compound formed by bonding three hydrocarbon groups to a sulfur atom, and the borate-based anion compound (borate-based anion) May refer to an anionic compound formed by bonding a hydrocarbon group.

For example, the epoxy ring opening reaction initiator may be represented by the following formula (6).

[Chemical Formula 6]

In Formula 6,

R ²¹ to R ²⁴ each independently represent a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 aryl group or a substituted or unsubstituted C2 to C20 heteroaryl group,

X ^- is a borate anion.

The borate anion may be represented by the following general formula (7).

(7)

In Formula 7,

R ²⁶ to R ³⁰ each independently may be F, Cl, Br or I.

For example, the epoxy ring opening reaction initiator may include (4-acetoxyphenyl) methyl (phenylmethyl) sulfonium cation and tetrakis (2,3,4,5,6-pentafluorophenyl) borate anion in a molar ratio of 1: 1.

For example, the epoxy ring opening reaction initiator may be represented by the following general formula (8).

[Chemical Formula 8]

The epoxy ring-opening reaction initiator can initiate an epoxy ring-opening reaction at a temperature of 100 ° C or lower, for example, at a temperature of 75 ° C or more and 90 ° C or lower, whereby the photosensitive resin composition according to an embodiment containing the epoxy ring- May be capable of curing at a temperature less than or equal to 85 &lt; 0 &gt; C.

The epoxy ring opening reaction initiator is contained in an amount of 0.1 to 10% by weight, for example, 0.1 to 5% by weight, such as 0.1 to 2% by weight, for example, 0.1 to 1% by weight based on the total amount of the photosensitive resin composition . When the epoxy ring opening reaction initiator is contained within the above range, the developing adhesive force and the low temperature curing chemical resistance according to the lower film, especially the chemical resistance in the etchant, are excellent.

(F) Solvent

The photosensitive resin composition according to one embodiment may further include a solvent. The solvent may be a material which has compatibility with the polysiloxane resin, the cationic binder resin, the reactive unsaturated compound, the photopolymerization initiator and the epoxy ring opening reaction initiator but does not react.

Examples of the solvent include alcohols such as methanol and ethanol; Ethers such as dichloroethyl ether, n-butyl ether, diisobutyl ether, methylphenyl ether and tetrahydrofuran; Glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and diethylene glycol dimethyl ether; Cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate and diethyl cellosolve acetate; Carbitols such as methylethylcarbitol, diethylcarbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether and diethylene glycol diethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl- ; Saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate and isobutyl acetate; Lactic acid esters such as methyl lactate and ethyl lactate; Oxyacetic acid alkyl esters such as methyl oxyacetate, ethyl oxyacetate and butyl oxyacetate; Alkoxyacetic acid alkyl esters such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, and ethyl ethoxyacetate; 3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate and methyl 3-ethoxypropionate; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate and propyl 2-oxypropionate; 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate and methyl 2-ethoxypropionate; 2-methylpropionic acid esters such as methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy- Monooximonocarboxylic acid alkyl esters of 2-alkoxy-2-methylpropionic acid alkyls such as ethyl methyl propionate; Esters such as ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate and methyl 2-hydroxy-3-methylbutanoate; Ketone acid esters such as ethyl pyruvate, and the like, and also include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide , N-methylpyrrolidone, dimethylsulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, And high boiling solvents such as ethyl acetate, diethyl oxalate, diethyl maleate,? -Butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate.

Among them, glycol ethers such as ethylene glycol monoethyl ether and diethylene glycol dimethyl ether are preferable in view of compatibility and reactivity; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; Esters such as ethyl 2-hydroxypropionate; Carbitols such as diethylene glycol monomethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate can be used.

The solvent may be contained in an amount of 50 to 90% by weight based on the total amount of the photosensitive resin composition. When the solvent is contained within the above range, the uniform coating property and the solubility of the internal composition are improved.

(G) Other additives

The photosensitive resin composition according to one embodiment includes malonic acid; 3-amino-1,2-propanediol; A silane-based coupling agent comprising a vinyl group or (meth) acryloxy group; Leveling agents; Fluorine surfactants; Or a combination thereof.

For example, the photosensitive resin composition may further include a silane-based coupling agent having a reactive substituent such as a vinyl group, a carboxyl group, a methacryloxy group, an isocyanate group or an epoxy group in order to improve adhesion with a substrate or the like.

Examples of the silane-based coupling agent include trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanate propyltriethoxysilane,? -Glycine (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. These may be used singly or in combination of two or more.

The silane coupling agent may be included in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the silane coupling agent is contained within the above range, the adhesion and storage stability are excellent.

The above-mentioned photosensitive resin composition may further contain a surfactant such as a fluorine-based surfactant for the purpose of improving coatability and preventing defect formation, if necessary.

The fluorine is a surfactant, the ^{BM Chemie社BM-1000 ®,} BM-1100 ® , and the like; Mechacup F 142D ^® , copper F 172 ^® , copper F 173 ^® , copper F 183 ^® and the like manufactured by Dainippon Ink & Chemicals Incorporated; Sumitomo M. (Note)社Pro rod FC-135 ^®, the same FC-170C ^®, copper FC-430 ^®, the same FC-431 ^®, and the like; Asahi Grass Co., Saffron S-112 ^® of社, such S-113 ^®, the same S-131 ^®, the same S-141 ^®, the same S-145 ^®, and the like; Toray Silicone ^® (Note)社SH-28PA, the same -190 ^®, may be used a fluorine-containing surfactants commercially available under the name such as copper ^{-193 ®, SZ-6032 ®,} SF-8428 ®.

The surfactant may be used in an amount of 0.001 part by weight to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the surfactant is contained within the above range, uniformity of coating is ensured, no staining occurs, and wetting of the glass substrate is excellent.

In addition, a certain amount of other additives such as antioxidants and stabilizers may be added to the photosensitive resin composition within a range that does not impair the physical properties.

The photosensitive resin composition may be a negative type photosensitive resin composition.

The photosensitive resin composition can be cured at a low temperature of 90 占 폚 or lower, such as 85 占 폚 or lower, such as 75 占 폚 or higher and 85 占 폚 or lower.

Another embodiment provides a cured film produced using the above-described photosensitive resin composition. The cured film may be an insulating film. The method of manufacturing the insulating film is as follows.

(1) Coating and Film Formation Step

The above-mentioned photosensitive resin composition is coated on a predetermined pretreated substrate to a desired thickness, for example, a thickness of 1.2 탆 to 3.5 탆 by a method such as spin or slit coat method, roll coating method, screen printing method or applicator method After coating, the coating is formed by removing the solvent by heating at a temperature of 70 ° C to 90 ° C for 1 minute to 10 minutes.

(2) Exposure step

In order to form a pattern necessary for the obtained coating film, a mask of a predetermined type is interposed therebetween and then an active line of 200 to 500 nm is irradiated. As the light source used for the irradiation, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, an argon gas laser, or the like can be used.

The exposure intensity may be, for example, 10 mW / cm ³ to 50 mW / cm ³ (depending on the 365 nm sensor), and the irradiation time may be 5 Second to one minute, but is not limited thereto.

(3) Development step

Following the above exposure step, an unnecessary portion is dissolved and removed by using an alkaline aqueous solution as a developing solution, so that only the exposed portion is left to form an image pattern.

(4) Post-treatment step

The image pattern obtained by the above-described development can be cured by heating again or by active ray irradiation or the like in order to obtain a pattern excellent in terms of heat resistance, light resistance, adhesion, crack resistance, chemical resistance, high strength and storage stability.

By using the above-described photosensitive resin composition, excellent heat resistance and chemical resistance can be obtained even in a low temperature process.

Hereinafter, preferred embodiments of the present invention will be described. However, the following examples are only a preferred embodiment of the present invention, and the present invention is not limited by the following examples.

Example

Synthetic example  One: Polysiloxane  Resin Manufacturing

1 kg of a mixed solvent of water and toluene in a weight ratio of 5: 5 was introduced into a three-necked flask, and 450 g of glycidoxypropyltrimethoxysilane was added to hexaethoxydisilylethane ((EtO) ₃ SiCH ₂ CH ₂ Si (OEt) ₃ ) were mixed and stirred for 2 hours. After completion of the stirring, condensation polymerization was carried out while heating at 90 DEG C for 3 hours. After cooling to room temperature, the water layer was removed to prepare a polymer solution dissolved in toluene.

The resulting polymer solution was washed with water to remove reaction by-products. The polymer solution was distilled under reduced pressure to remove toluene to obtain a siloxane compound represented by the following formula with a number average molecular weight of 2,974 g / mole and an epoxy equivalent of 174 g / eq. The number average molecular weight was measured with an RI detector from Empower GPC, Waters.

(OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ SiO _3/2 ) _0.95 (SiO _3/2 CH ₂ CH ₂ SiO _3/2 ) _0.05

 (Number average molecular weight: 2,974 g / mole)

Example  1 to Example  3, Comparative Example  1 and Comparative Example  2: Preparation of photosensitive resin composition

The polysiloxane resin prepared in Synthesis Example 1 and the components described below were each mixed in the composition shown in Table 1, and dissolved in diethylene glycol dimethyl ether so that the solid concentration became 30 wt%, respectively. Thereafter, the mixture was filtered through a 0.2 μm Millipore filter Followed by filtration to prepare photosensitive resin compositions according to Examples 1 to 3, Comparative Example 1, and Comparative Example 2, respectively.

(A) Polysiloxane  Suzy

The polysiloxane resin containing the epoxy group of Synthesis Example 1

(B) Photosensitive Cardinal resin

Cathode binder resin represented by the following formula (NSCC, V259ME):

In the above formula, R ₃ is a methacrylic group, Z is a residue derived from 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, and the cation resin has a weight average molecular weight Lt; / RTI &gt;

(C) a reactive unsaturated compound

Dipentaerythritol hexaacrylate (DPHA, Japan)

(D) Light curing Initiator

CGI-242 (Ciba-Geigy)

(E) Epoxy Ring opening reaction Initiator

SI-B3A (Sanshin chemical)

(F) Solvent

Diethylene glycol dimethyl ether

(Unit: wt%) Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 (A) a polysiloxane resin 6.3 9.8 13.1 - 29.5 (B) Cathode binder resin 18.0 15.0 12.0 23.0 - (C) a reactive unsaturated compound 4.2 3.7 3.4 5.8 - (D) a photopolymerization initiator 1.0 1.0 1.0 1.2 - (E) Epoxy ring opening reaction initiator 0.5 0.5 0.5 - 0.5 (F) Solvent 70.0 70.0 70.0 70.0 70.0

Cured film  Manufacturing and Evaluation

(1) Sensitivity evaluation

The photosensitive resin compositions prepared in Examples 1 to 3 and Comparative Examples 1 and 2 were each coated on a glass substrate to a thickness of 3 탆 using a spin coater (Mikasa, Opticoat MS-A150) baked at 85 ° C for 120 seconds using a hot-plate to form a film. Then, the film was formed into a pattern having a line width of 11 μm of 10 μm using a predetermined pattern mask The sensitivity was measured while irradiating ultraviolet rays having an intensity of 25.0 mW / cm &lt; ³ &gt; at 365 nm with an exposure apparatus (UX-1200SM-AKS02, USHIO) while measuring ultraviolet irradiation time. Subsequently, it was developed in an aqueous solution of 2.38% by weight of tetramethylammonium hydroxide at 25 DEG C for 60 seconds, washed with ultrapure water for 60 seconds, and then blow-dried with compressed air. Thereafter, the dried film was heated in an oven at 85 캜 for 60 minutes to be cured to obtain a photoresist film. Sensitivity measurement results are shown in Table 2 below.

(2) Residual film ratio  evaluation

The photosensitive resin compositions prepared in Examples 1 to 3 and Comparative Examples 1 and 2 were each coated on a glass substrate to a thickness of 3 탆 using a spin coater (Mikasa, Opticoat MS-A150) The thickness of the film was measured (Alpha-step, Surface Profiler KLA Tencor) after soft-baking at 85 ° C for 120 seconds using a hot-plate. Ultraviolet rays having an intensity of 25.0 mW / cm ³ at 365 nm, having a line width of 11 μm of 10 μm pattern, were irradiated with ultraviolet rays using a pattern mask (UX-1200SM-AKS02, USHIO) And irradiated for 8.0 seconds.

Thereafter, it was developed in an aqueous solution of 2.38% by weight of tetramethylammonium hydroxide at 25 DEG C for 60 seconds, washed with ultrapure water for 60 seconds, and then blow-dried with compressed air. Then, the dried film was heated in an oven at 85 ° C for 60 minutes to cure the photoresist film, and the thickness of the photoresist film was measured (Alpha-step, Surface Profiler KLA Tencor). The thickness of the film immediately after the soft-baking was compared with the thickness of the photoresist film, and the film thickness reduction ratio was measured to determine the residual film ratio. The results are shown in Table 2 below.

(3) Chemical resistance evaluation

The photosensitive resin compositions prepared in Examples 1 to 3 and Comparative Examples 1 and 2 were each coated on a glass substrate to a thickness of 3 탆 using a spin coater (Mikasa, Opticoat MS-A150) The thickness of the film was measured (Alpha-step, Surface Profiler KLA Tencor) after soft-baking at 85 ° C for 120 seconds using a hot-plate. Ultraviolet rays having an intensity of 25.0 mW / cm ³ at 365 nm, having a line width of 11 μm of 10 μm pattern, were irradiated with ultraviolet rays using a pattern mask (UX-1200SM-AKS02, USHIO) And irradiated for 8.0 seconds.

Thereafter, it was developed in an aqueous solution of 2.38% by weight of tetramethylammonium hydroxide at 25 DEG C for 60 seconds, washed with ultrapure water for 60 seconds, and then blow-dried with compressed air. The dried film was heated in an oven at 85 캜 for 60 minutes to be cured to obtain a photoresist film. After the initial thickness of the photoresist film was measured, it was allowed to stand at 60 DEG C for 3 minutes in NMP solvent, followed by cleaning with ultrapure water for 30 seconds, followed by blowing with compressed air to dryness. Then, the thickness was re-measured (Alpha-step, Surface profiler, KLA Tencor), and the chemical resistance was confirmed through the ratio of the thickness of the film. The results are shown in Table 2 below.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Sensitivity
(mJ) 35 25 15 50 - Residual film ratio
(%) 96 92 89 95 - Chemical Resistance (%) 91 95 100 78 100

Referring to Table 2, the coating film formed of the photosensitive resin compositions of Examples 1 to 3 according to one embodiment had sensitivity and saturation at a curing temperature lower than that of the coating film formed of the photosensitive resin composition of Comparative Example 1 and Comparative Example 2, And chemical resistance are all excellent. That is, it can be seen that the photosensitive resin composition according to one embodiment has excellent sensitivity to low-temperature curing, residual film ratio, chemical resistance, and the like, and thus an organic insulating film applicable to a flexible display can be manufactured.

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 present invention as defined by the following claims. As will be understood by those skilled in the art. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

Claims (20)

(A) a polysiloxane resin represented by the following formula (1)
(B) a cadmium-based binder resin,
(C) a reactive unsaturated compound,
(D) a photopolymerization initiator, and
(E) Epoxy ring opening reaction initiator
: &Lt; EMI ID =
[Chemical Formula 1]
(R ¹ R ² R ³ SiO _1/2 ) _M1 (R ⁴ R ⁵ SiO _2/2 ) _D (R ⁶ R ⁷ SiO _1/2 -Y ₁ -SiO _1/2 R ⁸ R ⁹ ) _{M 2} (R ¹⁰ SiO _3/2 ) _{T 1} (SiO _{3/ 2-} Y ₂ -SiO _3/2 ) _{T 2} (SiO _4/2 ) _Q
In Formula 1,
R ¹ to R ¹⁰ each independently represent 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 C1 to C30 A substituted or unsubstituted C2 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C2 to C30 alkoxy group, a substituted or unsubstituted C2 to C30 alkoxy group, a substituted or unsubstituted C2 to C30 alkoxy group, C = O) -, wherein R is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group,
At least one of R ¹ to R ¹⁰ contains an epoxy group,
Y ₁ represents 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 alkenylene group, a substituted or unsubstituted C2 to C30 alkenylene group, C30 alkynylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, or a combination thereof,
Y ₂ represents 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 alkenylene group, a substituted or unsubstituted C2 to C30 alkynylene group, A substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, or a combination thereof,
0 < M1 < 1, 0 <
M1 + M2 + D + T1 + T2 + Q = 1,
The structural units represented by M1, M2, D, T1, T2, and Q may each include one or more different structural units. The method of claim 1,
Wherein M1, M2, D and Q are 0, and 0.8 < T1 < 1 and 0 < The method of claim 1,
M1, M2, D and Q are 0, and 0.9 < T1 < 1 and 0 < The method of claim 1,
Wherein the equivalent of the epoxy group contained in the polysiloxane resin represented by the formula (1) is 50 g / eq to 260 g / eq. The method of claim 1,
The number average molecular weight of the polysiloxane resin represented by Formula 1 is 100 g / mole to 100,000 g / mole. The method of claim 1,
Each of R ¹ to R ¹⁰ independently represents a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkoxy group, or a combination thereof,
Wherein at least one of R ¹ to R ¹⁰ is a monovalent organic group substituted with an epoxy group. The method of claim 6,
The monovalent organic group substituted with an epoxy group may be a C1 to C10 alkyl group substituted with an epoxy group, a C3 to C10 cycloalkyl group substituted with an epoxy group, a C1 to C10 alkoxy group substituted with an epoxy group, a C1 to C10 ether group substituted with an epoxy group, Of the photosensitive resin composition. 8. The method of claim 7,
Wherein the monovalent organic group substituted with an epoxy group is an epoxy cycloalkyl group, an oxiranyl alkyl group, an oxetane alkyl group, or a glycidoxyalkyl group. The method of claim 1,
Wherein the cationic binder resin comprises a structural unit represented by the following formula (2): &lt; EMI ID =
(2)

In Formula 2,
R ¹¹ and R ¹² are each independently a hydrogen atom or a substituted or unsubstituted (meth) acryloyloxyalkyl group,
R ¹⁵ is a hydrogen atom or a substituted or unsubstituted (meth) acrylate group,
Z ¹ is any one of the linking groups represented by the following formulas (2-1) to (2-3)
Z ² is an acid anhydride residue,
[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

In the above Formulas 2-1 to 2-3,
R ¹³ and R ¹⁴ are each independently a hydrogen atom, a halogen atom or a substituted or unsubstituted C1 to C20 alkyl group,
m1 and m2 are each independently an integer of 0 to 4; The method of claim 9,
Z ¹ is a linking group represented by the formula (2-3)
And Z &lt; ² &gt; is a residue of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride. The method of claim 1,
Wherein the cationic binder resin has a weight average molecular weight of 1,000 to 20,000. The method of claim 1,
Wherein the epoxy ring opening reaction initiator comprises a sulfonium-based cation and a borate-based anion. The method of claim 12,
Wherein the epoxy ring opening reaction initiator is represented by the following formula (6):
[Chemical Formula 6]

In Formula 6,
R ²¹ to R ²⁴ each independently represent a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 aryl group or a substituted or unsubstituted C2 to C20 heteroaryl group,
X ^- is a borate anion. The method of claim 12,
Wherein said borate anion is represented by the following general formula (7): &lt; EMI ID =
(7)

In Formula 7,
R ²⁶ to R ³⁰ are each independently F, Cl, Br or I. The method of claim 1,
Wherein the photosensitive resin composition further comprises (F) a solvent. 16. The method of claim 15,
The photosensitive resin composition may contain, based on the total weight of the photosensitive resin composition,
(A) 5 to 25% by weight of the polysiloxane resin represented by the general formula (1)
(B) 10% to 20% by weight of a cadmium-based binder resin,
1 to 20% by weight of the reactive unsaturated compound (C)
0.1 to 10% by weight of the photopolymerization initiator (D)
0.1 to 10% by weight of the epoxy ring opening reaction initiator (E), and
The amount of the solvent (F)
. The method of claim 1,
Wherein the photosensitive resin composition is a negative type photosensitive resin composition. The method of claim 1,
Wherein the photosensitive resin composition is curable at a temperature of 85 캜 or less. A cured film produced by curing the photosensitive resin composition of any one of claims 1 to 18. An electronic device comprising the cured film of claim 19.