KR101587778B1 - High-branched dendritic alkali-soluble binder resin, and manufacturing method thereof, and photosensitive resin composition comprising the same - Google Patents

Abstract

The present invention relates to a highly-branched dendritic alkali-soluble binder resin having excellent developability and high substrate adhesion, to a manufacturing method thereof, and to a photosensitive resin composition comprising the highly-branched dendritic alkali-soluble binder resin.

Description

[0001] The present invention relates to a high-branched dendritic alkali-soluble binder resin, a process for producing the same, and a photosensitive resin composition containing the same,

The present invention relates to a highly branched dendritic alkali-soluble binder resin, a process for producing the same, and a photosensitive resin composition containing the same.

The photosensitive resin composition is used in a photosensitive material for various purposes such as a color filter for LCD, a black matrix, an overcoat, and a column spacer. Such a composition is usually used in an alkali-soluble binder resin, a polymerizable compound having an ethylenic unsaturated bond, a photopolymerization initiator, .

Such a photosensitive resin composition is applied on a substrate in a process step to form a coating film. After exposure to light is performed on a specific portion of the coating film using a photomask, the non-visible portion is developed and removed to form a pattern .

Therefore, the alkali-soluble binder resin to be used at this time has adhesion to the substrate and must be able to be coated. It should include photochemistry by exposure and developability by an alkaline developer, and it should be possible to form a fine pattern. Various characteristics such as substrate adhesiveness, sensitivity, developability, chemical resistance, heat resistance, and the like are required in the process step since it has to have a strength to prevent damage in the post-treatment process.

Especially, in the recent LCD market, researches for developing products having higher contrast and brightness than the conventional ones have been continued, and at the same time, a photosensitive material of excellent quality satisfying all the various basic characteristics required in the photosensitive resin composition is required Trend.

A similar prior art document is disclosed in Korean Patent Laid-Open Publication No. 10-2013-0118450 (October 30, 2013).

Korean Patent Publication No. 10-2013-0118450 (Oct. 30, 2013)

An object of the present invention is to provide a high molecular weight dendritic alkali-soluble binder resin having excellent developability and high substrate adhesion, a process for producing the same, and a photosensitive resin composition containing the same.

The present invention relates to a high molecular weight dendritic alkali-soluble binder resin satisfying the following formula (1) and a photosensitive resin composition containing the same.

[Chemical Formula 1]

Wherein L ₁ , L ₂ , L ₃ and L ₄ independently represent a substituted or unsubstituted C1-C10 alkylene group, a substituted or unsubstituted C1-C10 alkyl ester group and a substituted or unsubstituted C1- A ₁ , A ₂ , A ₃ and A ₄ are each independently selected from a substituted or unsubstituted C1-C4 alkyl group, a hydrogen atom, a substituted or unsubstituted C1-C10 alkyl group, An unsubstituted C1-C10 alkyl group and a substituted or unsubstituted C6-C20 aryl group, and contains -SP and contains at least three substituted or unsubstituted C1-C4 alkyl groups; At this time, P has a structure represented by the following formula (2)

(2)

A, b, 0 to 80 mol%, c is 0 to 80 mol%, and d is 10 to 90 mol%, wherein a, b, c and d are mole ratios of repeating units, , Wherein a + b + c + d is 100 mole%; R ₁ and R ₂ are each independently selected from the group consisting of hydrogen, a C1-C3 alkyl group, a C1-C3 alkoxy group and a C1-C3 hydroxyalkyl group; R ₃ and R ₄ are each independently hydrogen or a substituted or unsubstituted C 1 -C 4 alkyl group; X is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkyl ester group, a substituted or unsubstituted C1 to C10 alkyl ether group, a substituted or unsubstituted C1 to C10 alkoxypoly An alkylene glycol ester group, and a substituted or unsubstituted C6 to C20 aryl group; Y is a C1-C10 alkylene group containing or not containing at least one of -COO- and -O-; Z is selected from a C1-C5 alkylene group, a substituted or unsubstituted C6-C20 arylene group, a substituted or unsubstituted C3-C20 cycloalkylene group, and a substituted or unsubstituted C3-C20 cycloalkenylene group . With the proviso that X may be linked to R ₁ or R ₂ to form a ring of carboxylic acid anhydride or imide structure.

Another embodiment of the present invention is a method for preparing a polymer comprising the steps of: a) polymerizing a mixture comprising a first monomer satisfying the following formula (3), a second monomer satisfying the following formula (4), and a thiol compound satisfying the following formula Producing; b) reacting the prepared first polymer with a compound satisfying the following formula (6) to prepare a second polymer; And c) adding a cyclic anhydride to the second polymer so as to introduce an acid group. The present invention also relates to a method for producing a highly dendritic alkali-soluble binder resin.

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

Wherein R ₁ and R ₂ are independently selected from the group consisting of hydrogen, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having ₁ to 3 carbon atoms and a hydroxyalkyl group having ₁ to 3 carbon atoms; R ₃ and R ₄ is independently hydrogen or a substituted or unsubstituted C1-C4 alkyl group; X is a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C1-C10 alkyl ester group, a substituted or unsubstituted C1- A substituted or unsubstituted C1 to C10 alkoxypolyalkylene glycol ester group, and a substituted or unsubstituted C6 to C20 aryl group; Y is -COO- And -O-; L ₁ , L ₂ , L ₃ and L ₄ independently represent a substituted or unsubstituted C1-C10 alkylene group, a substituted or unsubstituted C1-C10 alkylene group, A substituted or unsubstituted C1 to C10 alkyl ester group and a substituted or unsubstituted C1 to C10 alkyl ether group Which is standing in a selected _{one; B 1, B 2, B} 3 and B ₄ are independently from each other and containing a -SH group of a substituted or unsubstituted C1 ~ C10, hydrogen, substituted or unsubstituted alkyl group-substituted C1 ~ C10 And a substituted or unsubstituted C6-C20 aryl group, and contains -SH and contains at least three substituted or unsubstituted C1-C10 alkyl groups, with the proviso that X is R ₁ or R ₂ to form a ring of carboxylic acid anhydride or imide structure.)

The high molecular weight dendritic alkali-soluble binder resin according to the present invention has a dendritic structure of a high molecular weight type and an external acid group, so that the development speed can be appropriately controlled, It is possible to have a very good developing property such as being able to facilitate the development.

Also, by having such a structural property, it can have a high substrate adhesion force and have a lower viscosity than a linear binder resin having a molecular weight in a similar range, so that a smooth surface can be obtained at the time of coating, Lt; RTI ID = 0.0 > of < / RTI >

1 is a schematic view of a highly branched dendritic alkali-soluble binder resin according to an example of the present invention.

The present invention relates to a high-branched dendritic alkali-soluble binder resin, which has a dendritic dendritic structure and is connected to a side branch rather than a main branch. And has an acid group (an external acid group).

In the case of the conventional binder resin, since the development speed is too slow due to the position of the acid group on the well of the linear polymer, There is a problem in that a residual portion is formed due to a long period of time or the pattern is not cleaned neatly according to a pattern. On the contrary, since the linear polymer has an external acid group, the development speed becomes too fast, There has been a disadvantage in that the lower part of the bonded pattern is scraped off by the developer and the taper of the pattern is lengthened after the postbake process. In addition, there has been a problem in that, if the acid value is reduced in order to slow down the developing rate, the phenomenon can not be performed properly.

However, in the case of the binder resin according to the present invention, the development speed can be appropriately controlled by having a dendritic structure of a high molecular weight type and an external acid group, and it is possible to perform a neat development without undeveloped portions, It is possible to have a very good developing property. In addition, by having such a dendritic dendritic structure, a high substrate adhesion force can be obtained, and coating properties can be improved.

Specifically, the highly branched dendritic alkali-soluble binder resin according to the present invention may satisfy the following formula (1). Herein, the term "substituted" or "substituted" as used herein means an alkyl group having at least one hydrogen atom in a functional group, a halogen atom (F, Cl, Br, I), a C1- A C1 to C10 halogenated alkyl group, a C3 to C20 cycloalkyl group, a C3 to C20 cycloalkenyl group, a C6 to C30 allyl group, a hydroxyl group, an amine group, a carboxylic acid group and an aldehyde group Or may be substituted with at least one substituent selected.

[Chemical Formula 1]

In Formula 1,

L ₁ , L ₂ , L ₃ and L ₄ independently represent a substituted or unsubstituted C1-C10 alkylene group, a substituted or unsubstituted C1-C10 alkyl ester group and a substituted or unsubstituted C1-C10 alkyl An ether group;

A ₁ , A ₂ , A ₃ and A ₄ independently represent a substituted or unsubstituted C1-C4 alkyl group, hydrogen, a substituted or unsubstituted C1-C10 alkyl group and a substituted or unsubstituted C6 An aryl group of 1 to 20 carbon atoms, and contains at least three substituted or unsubstituted C1 to C4 alkyl groups containing -SP;

At this time, P has a structure represented by the following formula (2)

(2)

A, b, 0 to 80 mol%, c is 0 to 80 mol%, and d is 10 to 90 mol%, wherein a, b, c and d are mole ratios of repeating units, , Wherein a + b + c + d is 100 mole%;

R ₁ and R ₂ are each independently selected from the group consisting of hydrogen, a C1-C3 alkyl group, a C1-C3 alkoxy group and a C1-C3 hydroxyalkyl group;

R ₃ and R ₄ are each independently hydrogen or a substituted or unsubstituted C 1 -C 4 alkyl group;

X is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkyl ester group, a substituted or unsubstituted C1 to C10 alkyl ether group, a substituted or unsubstituted C1 to C10 alkoxypoly An alkylene glycol ester group, and a substituted or unsubstituted C6 to C20 aryl group;

Y is a C1-C10 alkylene group containing or not containing at least one of -COO- and -O-;

Z is selected from a C1-C5 alkylene group, a substituted or unsubstituted C6-C20 arylene group, a substituted or unsubstituted C3-C20 cycloalkylene group, and a substituted or unsubstituted C3-C20 cycloalkenylene group .

With the proviso that X may be linked to R ₁ or R ₂ to form a ring of carboxylic acid anhydride or imide structure.

More preferably, in formula (1), L ₁ , L ₂ , L ₃ and L ₄ independently represent a substituted or unsubstituted C1-C3 alkylene group, a substituted or unsubstituted C1-C5 alkyl ester group, And A ₁ , A ₂ , A ₃ and A ₄ are independently selected from the group consisting of a substituted or unsubstituted C1-C4 alkyl group, a substituted or unsubstituted C1-C5 alkyl group, Or an unsubstituted C1-C3 alkyl group and a substituted or unsubstituted phenyl group, and may contain at least three substituted or unsubstituted C1-C4 alkyl groups containing -SP; In the formula (2), a, b, c and d are the molar ratios of the respective repeating units, a is 20 to 80 mol%, b is 0 to 50 mol%, c is 0 to 60 mol% and d is 20 to 80 mol% Wherein a + b + c + d is 100 mole%, R ₁ and R ₂ are independently hydrogen or a C ₁ -C ₃ alkyl group, R ₃ and R ₄ are independently hydrogen or a C 1 -C 3 alkyl group , X is a substituted or unsubstituted C1 to C3 alkyl group, a substituted or unsubstituted C1 to C3 alkyl ester group, a substituted or unsubstituted C1 to C3 alkyl ether group, and a substituted or unsubstituted C6 to C20 An aryl group, X may be connected to R ₁ or R ₂ to form a carboxylic acid anhydride or a ring of imide structure, Y is an alkylene group of C1 to C3, and Z is a C1 to C5 alkyl A phenylene group, a cyclohexylene group, and a cyclohexenylene group.

More preferably, in formula (1), L ₁ , L ₂ , L ₃ and L ₄ are each independently a C 1 to C 5 alkyl ester group, and A ₁ , A ₂ , A ₃ and A ₄ independently represent -SP Lt; RTI ID = 0.0 > Cl-C3 < / RTI > In the formula (2), a, b, c and d are the molar ratios of the respective repeating units, a is 30 to 70 mol%, b is 0 to 10 mol%, c is 0 to 40 mol% and d is 30 to 70 mol% Wherein R ₁ and R ₂ are independently hydrogen or a methyl group, R ₃ and R ₄ are each independently hydrogen or a methyl group, X is a C 1 to C 3 alkyl group , A C1 to C3 alkyl ester group substituted with a C6 to C20 aryl group, a C1 to C3 alkyl ester group substituted with a C6 to C20 cycloalkyl group, and a C6 to C20 aryl group, X is R ₁ or R ₂ and N-phenylmaleimide, succinimide or succinic anhydride, Y may be a methylene group, Z may be an ethylene group, a butylene group, a phenylene group, a cyclohexylene group , And a cyclohexenylene group.

As described above, the highly branched dendritic alkali-soluble binder resin satisfying the formula (1) has a branched structure connected to the branched homopolymers and having a branching structure more branched than a general branched polymer having an acid group connected thereto and having twigs . As described above, by having a dendritic structure having a high molecular weight and an external acid group, excellent developability and high substrate adhesion can be obtained as described above.

More specifically, the structure of the binder resin according to one embodiment of the present invention will now be described with reference to FIG. 1, but the structure of the high molecular weight dendritic binder resin is simplified in order to facilitate understanding of the present invention. The present invention is not limited thereto.

As shown in FIG. 1, the binder resin according to an embodiment of the present invention can be largely composed of known, side, and twin branches and has a structure in which twigs (external acid groups) are present in an appropriate ratio in the binder resin, . For example, the binder resin may satisfy the following relational expression (1).

[Relation 1]

0.05? N ₂ / N ₁ ? 0.9

Wherein N ₁ is the number of side branches connected to the main chain among the compounds satisfying the formula (1), and N ₂ is the number of twigs connected to the side chain among the compounds satisfying the formula (1). For example, N ₁ can be from 10 to 500.

More preferably, formula 2 may be satisfied, where N ₁ may be from 20 to 250. More preferably, R 3 can be satisfied, and N ₁ can be 50 to 150.

[Relation 2]

0.1? N ₂ / N ₁ ? 0.5

[Relation 3]

_{0.15 ≤ N 2 / N 1 ≤} 0.3

The binder resin according to an exemplary embodiment of the present invention may have a weight average molecular weight of 3,000 to 100,000 g / mol and a viscosity of 20 to 150 cps. By having a viscosity lower than that of the linear binder resin having a molecular weight in the similar range, it is possible to obtain a smooth surface at the time of coating and to have an improved coating property such as coating with a desired thickness. More preferably from 5,000 to 50,000 g / mol and a viscosity of from 30 to 120 cps, more preferably from 10,000 to 30,000 g / mol, and a viscosity of from 50 to 100 cps.

In addition, the binder resin according to an exemplary embodiment of the present invention may have an acid value of 30 to 200 mg KOH / g. In such a range, the developing property is excellent and the development is neat, and fine pattern formation can be facilitated. Even more preferably, the acid value may be 50 to 150 mg KOH / g, and more preferably 70 to 130 mg KOH / g.

A method for producing such a highly branched dendritic alkali-soluble binder resin comprises the steps of: a) mixing a first monomer satisfying the following formula (3), a second monomer satisfying the following formula (4), and a thiol compound satisfying the following formula Polymerizing the mixture to produce a first polymer; b) reacting the prepared first polymer with a compound satisfying the following formula (6) to prepare a second polymer; And c) adding a cyclic anhydride to the second polymer to introduce an acid group. However, the first monomer may be a mixture of two or more different compounds which satisfy the formula (3).

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

In the above formulas 3 to 6,

R ₁ and R ₂ are each independently selected from the group consisting of hydrogen, a C1-C3 alkyl group, a C1-C3 alkoxy group and a C1-C3 hydroxyalkyl group; R ₃ and R ₄ are each independently hydrogen or a substituted or unsubstituted C 1 -C 4 alkyl group;

X is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkyl ester group, a substituted or unsubstituted C1 to C10 alkyl ether group, a substituted or unsubstituted C1 to C10 alkoxypoly An alkylene glycol ester group, and a substituted or unsubstituted C6 to C20 aryl group; Y is a C1-C10 alkylene group containing or not containing at least one of -COO- and -O-;

L ₁ , L ₂ , L ₃ and L ₄ independently represent a substituted or unsubstituted C1-C10 alkylene group, a substituted or unsubstituted C1-C10 alkyl ester group and a substituted or unsubstituted C1-C10 alkyl An ether group;

B ₁ , B ₂ , B ₃ and B ₄ each independently represent a substituted or unsubstituted C1-C10 alkyl group, a hydrogen, a substituted or unsubstituted C1-C10 alkyl group and a substituted or unsubstituted C6 C20 aryl group, and may contain at least three or more substituted or unsubstituted C1-C10 alkyl groups containing -SH.

With the proviso that X may be linked to R ₁ or R ₂ to form a ring of carboxylic acid anhydride or imide structure.

More preferably, in the first monomer satisfying the formula (3), R ₁ and R ₂ are independently hydrogen or a C1 to C3 alkyl group, X is a substituted or unsubstituted C1 to C3 alkyl group, a substituted or unsubstituted C1 A substituted or unsubstituted C1 to C3 alkyl ether group, and a substituted or unsubstituted C6 to C20 aryl group, provided that X is R ₁ or R ₂ To form a ring of carboxylic acid anhydride or imide structure; In the second monomer satisfying the general formula (4), R ₃ is hydrogen or a C1 to C3 alkyl group, Y is an alkylene group of C1 to C3; In the thiol compound satisfying the formula (5), L ₁ , L ₂ , L ₃ and L ₄ independently represent a substituted or unsubstituted C1 to C3 alkylene group, a substituted or unsubstituted C1 to C5 alkyl ester group and a substituted Or an unsubstituted C1-C5 alkyl ether group; B ₁ , B ₂ , B ₃ and B ₄ independently represent a substituted or unsubstituted C1-C4 alkyl group, hydrogen, a substituted or unsubstituted C1-C3 alkyl group and a substituted or unsubstituted phenyl group , And may contain at least three substituted or unsubstituted C1-C4 alkyl groups containing -SH.

More preferably, in the first monomer satisfying the general formula (3), R ₁ and R ₂ are independently hydrogen or a methyl group, X is a C1 to C3 alkyl group, a C1 to C3 alkyl ester group substituted with a C6 to C20 aryl group , A C1 to C3 alkyl ester group substituted with a C6 to C20 cycloalkyl group, and an C6 to C20 aryl group, X may be any one or two or more selected from R ₁ or R ₂ and N-phenyl maleimide, Succinimide or succinic anhydride and the like; In the second monomer satisfying the formula (4), R ₃ is hydrogen or a methyl group, and Y is a methylene group; The thiol compound satisfying the formula (5) may be pentaerythritol tetrakis thioglycolate or pentaerythritol tetrakis (3-mercapto butylate), and the thiol compound satisfying the formula May be acrylic acid or methacrylic acid.

The method of producing a binder resin according to the present invention is advantageous in that it can polymerize a binder resin having a desired structure and physical properties as planned by sequentially introducing necessary functional groups through various steps without proceeding with polymerization in one step And the acidity can be easily adjusted by introducing the acid group in the last stage, and the acidity can be improved because the acid group is located in the side branch which is not the main body.

Specifically, each step will be described. In step a), a mixture comprising a first monomer satisfying the formula (3), a second monomer satisfying the formula (4), and a thiol compound satisfying the formula (5) is polymerized to form a first polymer A step of polymerizing a polymer having a branched homopolymer structure.

The mixture according to an exemplary embodiment of the present invention may be mixed in different amounts depending on the design. Specifically, for example, 20 to 70 mol% of the first monomer, 20 to 70 mol% of the second monomer, 1 to 10 mol% based on the total weight of the composition.

Next, step b) is a step of reacting the first polymer prepared in step a) with a compound satisfying the formula (6) to prepare a second polymer, and the step of reacting the first polymer with the compound capable of reacting with the cyclic anhydride Forming a lock time (-OH). At this time, the compound satisfying the formula (6) in the step (b) may be added in an amount of 1 to 1.2 times based on the total number of moles of the second monomer.

In step c), a cyclic anhydride is added to the second polymer prepared in step b) to introduce an acid group. In step c), an acid group capable of reacting with the cyclic anhydride with the hydroxy group formed in step b) Whereby an external acid group into which an acid group is introduced into the side chain can be formed, and a binder resin of a high molecular weight type can be obtained.

In this case, the cyclic anhydride in the step c) may be added in an amount of 0.3 to 1.1 times based on the total number of moles of the hydroxyl group formed in the step b). By using the amount of the cyclic anhydride within the above range, the acid value of the finally obtained highly branched dendritic alkali-soluble binder resin can be controlled to 30 to 200 mg KOH / g.

The cyclic anhydride is not particularly limited as long as it can react with a hydroxyl group to form an acid group (-COOH). Specific examples thereof include succinic anhydride, adipic anhydride, phthalic anhydride, hexahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride and cis-5-norbornene-endo-2,3-dicarboxylic acid anhydride, and the like, but not limited thereto.

Further, the present invention can provide a photosensitive resin composition comprising a highly branched dendritic alkali-soluble binder resin, wherein the photosensitive resin composition comprises a polymerizable compound having an ethylenic unsaturated bond, a colorant, a photoinitiator, May be included.

The photosensitive resin composition according to an example includes 1 to 20% by weight of a highly branched dendritic alkali soluble binder resin, 1 to 10% by weight of a polymerizable compound having an ethylenically unsaturated bond, 1 to 30% by weight of a colorant, 0.1 to 5% % Of a solvent and 35 to 95% by weight of a solvent.

The polymerizable compound having an ethylenically unsaturated bond is not particularly limited as long as it is ordinarily used in the art, and specific examples thereof include ethylene glycol di (meth) acrylate, polyethylene glycol having 2 to 14 ethylene groups (Meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra Diethylene glycol di (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and mixtures thereof, but are not limited thereto.

The colorant may also be used without any particular limitation as long as it is commonly used in the art. Specific examples thereof include carmine 6B (CI12490), phthalocyanine green (CI 74260), phthalocyanine blue (CI 74160), perylene black , Cyanine Black (CI21090), Lynol Yellow GRO (CI 21090), Benzidine Yellow 4T-564D, Victoria Pure Blue (CI42595), CI PIGMENT RED 3, 23, 97, 108, 122, 139, 140, 141, 142, 143, 144, 149, 166, 168, 175, 177, 180, 185, 189, 190, 192, 220, 221, 224, 230, 235, 242, 254, 255, 260, 262, 264, 272; C.I. PIGMENT GREEN 7, 36; C.I. PIGMENT blue 15: 1, 15: 3, 15: 4, 15: 6, 16, 22, 28, 36, 60, 64; C.I. PIGMENT yellow 13, 14, 35, 53, 83, 93, 95, 110, 120, 138, 139, 150, 151, 154, 175, 180, 181, 185, 194, 213; C.I. PIGMENT VIOLET 15, 19, 23, 29, 32, 37 and the like can be used, but the present invention is not limited thereto.

The photoinitiator is not particularly limited as long as it is ordinarily used in the art. Specific examples thereof include 2,4-trichloromethyl- (4'-methoxyphenyl) -6-triazine, 2,4- (3 ', 4'-methoxystyryl) -6-triazine, 2,4-trichloromethyl- (triphenyl) Triazine compounds such as 3- {4- [2,4-bis (trichloromethyl) -s-triazin-6-yl] phenylthio} propanoic acid; Bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- , 5'-tetraphenylbiimidazole; 2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy- (4-methylthiophenyl) -2-morpholinocyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, (Irgacure-907), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) 369); O-acyloxime compounds such as Irgacure OXE 01 and Irgacure OXE 02 from Ciba Geigy, benzophenone compounds such as 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) ; Thioxanthone compounds such as 2,4-diethylthioxanthone, 2-chlorothioxanthone, isopropylthioxanthone and diisopropylthioxanthone; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,6-dichlorobenzoyl) propylphosphine oxide Phosphine oxide-based compounds; (Diethylamino) coumarin, 3- (2-benzothiazolyl) -7- (diethylamino) coumarin, 3-benzoyl- Benzoyl-7-methoxy-coumarin, 10,10'-carbonylbis [1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H, 5H, 11H- -Benzopyrano [6,7,8-ij] -quinolizine-11-one, or a mixture thereof, but is not limited thereto.

The solvent is not particularly limited as long as it is commonly used in the art. Specific examples thereof include methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene Propylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, 2-ethoxypropanol, 2-methoxypropanol, 3-methoxybutanol, cyclohexane Propylene glycol methyl ether acetate, 3-methoxybutyl acetate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, methyl cellosolve acetate, butyl acetate, dipropylene glycol monomethyl ether acetate, Glycol monomethyl ether or mixtures thereof. But, not limited to this.

In addition, additives such as a dispersant, a dispersion stabilizer, an adhesion promoter, and a surfactant can be further added as needed within the range not impairing the physical properties of the photosensitive resin composition.

Such a photosensitive resin composition can be used for a color filter photosensitive material, an overcoat photosensitive material, a column spacer, an insulating material, and the like.

The present invention also provides a method of forming a patterned resist film using a photosensitive resin composition. Specifically, a method of forming a patterned resist film according to the present invention comprises the steps of: a) coating a photosensitive resin composition on a substrate to form a photosensitive layer; And b) patterning the photosensitive layer through a photolithographic process to form a resist film.

The coating method in the step a) is not particularly limited as long as it is a commonly used method. Specifically, the photosensitive layer can be formed using, for example, spin coating or slit coating. .

After the formation of the photosensitive layer, a vacuum process and / or a pre-baking process may be further performed. The vacuum treatment according to an exemplary embodiment may be performed at a pressure of 0.3 to 1 torr for 20 to 60 seconds, and the heat treatment may be performed at a temperature of 70 to 120 ° C for 60 to 120 seconds.

Next, the resist layer can be formed by patterning the photosensitive layer through a photolithography process, and the photolithography process can be performed by a method commonly used in the art. For example, a patterned resist film can be formed by exposure and development using a mask having a predetermined pattern formed thereon. More specifically, for example, the resist can be exposed at an intensity of 30 to 150 mJ / cm 2, and a pattern can be formed by removing an unpolymerized portion using an aqueous alkali solution of 10 to 12 and washing with water.

Thereafter, a post-baking process may be further performed at a temperature of 200 to 240 ° C for 10 to 40 minutes.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings. It should be understood, however, that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the invention.

Unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

In addition, the following drawings are provided by way of example so that those skilled in the art can fully understand the spirit of the present invention. Therefore, the present invention is not limited to the following drawings, but may be embodied in other forms. The following drawings may be exaggerated in order to clarify the spirit of the present invention.

Also, the singular forms as used in the specification and the appended claims are intended to include the plural forms as well, unless the context clearly indicates otherwise.

In addition, the unit of the additives not specifically described in the specification may be% by weight.

The physical properties of the highly branched dendritic alkali-soluble binder resin and the photosensitive resin composition prepared through the following examples and comparative examples were measured as follows.

[Synthesis Example 1]

30 g of benzyl methacrylate, 10 g of N-phenylmaleimide, 8 g of styrene, 32 g of glycidyl methacrylate and 3 g of pentaerythritol tetrakisthioglycolate were mixed with 300 g of propylene glycol monomethyl ether acetate, Was raised to 60 占 폚, and when the temperature of the mixture reached 60 占 폚, 4 g of azodiisobutyronitrile (AIBN) as a thermal polymerization initiator was added and stirred for 12 hours. After 12 hours, a first polymer resin binder solution having a polymerization yield of 98% and a molecular weight of 16,000 g / mol was obtained.

0.5 g of tetrabutylammonium bromide and 0.1 g of monomethylether hydroquinone (MEHQ) as a thermal polymerization inhibitor were added to the first polymer solution and stirred at 80 DEG C for 30 minutes. Then, 16.5 g of acrylic acid was added, and 120 DEG C Lt; / RTI > for 24 hours. After 24 hours, a second polymer resin binder solution having a molecular weight of 19,000 g / mol was obtained.

In the final synthesis step, 18 g of tetrahydrophthalic anhydride was added to this second polymer solution and stirred at 90 ° C for 15 hours to obtain an alkali-soluble resin solution having a molecular weight of 23,500 g / mol and an acid value of 105.

[Synthesis Example 2]

30 g of cyclohexyl methacrylate, 18 g of methyl methacrylate, 32 g of glycidyl methacrylate and 3 g of pentaerythritol tetrakisthioglycolate were mixed with 300 g of propylene glycol monomethyl ether acetate, and the temperature of the reactor was adjusted to 60 DEG C And when the temperature of the mixture reached 60 占 폚, 4 g of AIBN as a thermal polymerization initiator was added thereto and stirred for 12 hours. After 12 hours, a first polymer resin binder solution having a polymerization yield of 98% and a molecular weight of 15,000 g / mol was obtained.

0.5 g of tetrabutylammonium bromide and 0.1 g of MEHQ as a thermal polymerization inhibitor were added to the first polymer solution and stirred at 80 DEG C for 30 minutes. Then, 16.5 g of acrylic acid was added and stirred at 120 DEG C for 24 hours while maintaining the air atmosphere. After 24 hours, a second polymer resin binder solution having a molecular weight of 18,500 g / mol was obtained.

In the final synthesis step, 18 g of tetrahydrophthalic anhydride was added to this second polymer solution and stirred at 90 DEG C for 15 hours to obtain an alkali-soluble resin solution having a molecular weight of 23,000 g / mol and an acid value of 100.

[Synthesis Example 3]

30 g of benzylmethacrylate, 10 g of N-phenylmaleimide, 8 g of styrene, 32 g of glycidyl methacrylate and 3 g of pentaerythritol tetrakis 3-mercaptobutyrate were mixed with 300 g of propylene glycol monomethyl ether acetate, When the temperature of the reactor was raised to 60 DEG C and the temperature of the mixture reached 60 DEG C, 4 g of AIBN as a thermal polymerization initiator was added and stirred for 12 hours. After 12 hours, a first polymer resin binder solution having a polymerization yield of 98% and a molecular weight of 15,000 g / mol was obtained.

0.5 g of tetrabutylammonium bromide and 0.1 g of MEHQ as a thermal polymerization inhibitor were added to the first polymer solution and stirred at 80 DEG C for 30 minutes. Then, 16.5 g of acrylic acid was added and stirred at 120 DEG C for 24 hours while maintaining the air atmosphere. After 24 hours, a second polymer resin binder solution having a molecular weight of 18,000 g / mol was obtained.

In the final synthesis step, 18 g of tetrahydrophthalic anhydride was added to this second polymer solution and stirred at 90 DEG C for 15 hours to obtain an alkali-soluble resin solution having a molecular weight of 23,000 g / mol and an acid value of 100.

[Synthesis Example 4]

30 g of cyclohexyl methacrylate, 18 g of methyl methacrylate, 32 g of glycidyl methacrylate and 3 g of pentaerythritol tetrakis 3-mercaptobutyrate were mixed with 300 g of propylene glycol monomethyl ether acetate, and the temperature of the reactor Was raised to 60 DEG C, and when the temperature of the mixture reached 60 DEG C, 4 g of AIBN as a thermal polymerization initiator was added and stirred for 12 hours. After 12 hours, a polymer resin binder solution having a polymerization yield of 98% and a molecular weight of 14,000 g / mol was obtained.

To this polymer solution, 0.5 g of tetrabutylammonium bromide and 0.1 g of MEHQ as a thermal polymerization inhibitor were added and stirred at 80 ° C for 30 minutes. Then, 16.5 g of acrylic acid was added and stirred at 120 ° C for 24 hours while maintaining the air atmosphere. After 24 hours, a polymer resin binder solution having a molecular weight of 17,500 g / mol was obtained.

In the final synthesis step, 18 g of tetrahydrophthalic anhydride was added to the polymer solution and stirred at 90 DEG C for 15 hours to obtain an alkali-soluble resin solution having a molecular weight of 22,000 g / mol and an acid value of 100.

 [Comparative Synthesis Example 1]

36 g of benzylmethacrylate, 12 g of N-phenylmaleimide, 10 g of styrene, 20 g of methacrylic acid and 3 g of 1-dodecanethiol were mixed with 300 g of propylene glycol monomethyl ether acetate, the temperature of the reactor was raised to 60 DEG C under a nitrogen atmosphere, The temperature of the solution reached 60 占 폚, 4 g of AIBN as a thermal polymerization initiator was added, and the mixture was stirred for 12 hours. After 12 hours, a polymer resin binder solution having a polymerization yield of 98% and a molecular weight of 18,000 g / mol was obtained.

0.5 g of tetrabutylammonium bromide and 0.1 g of MEHQ as a thermal polymerization inhibitor were added to the polymer solution and stirred at 80 DEG C for 30 minutes. Then, 15 g of glycidyl methacrylate was added and stirred at 110 DEG C for 15 hours while maintaining the air atmosphere Respectively. After 15 hours, an alkali-soluble resin solution having a molecular weight of 20,000 g / mol and an acid value of 90 was obtained.

[Comparative Synthesis Example 2]

30 g of cyclohexyl methacrylate, 18 g of methyl methacrylate, 20 g of methacrylic acid and 3 g of 1-dodecanethiol were mixed with 300 g of propylene glycol monomethyl ether acetate, the temperature of the reactor was raised to 60 DEG C under a nitrogen atmosphere, When the temperature reached 60 占 폚, 4 g of AIBN as a thermal polymerization initiator was added and stirred for 12 hours. After 12 hours, a polymer resin binder solution having a polymerization yield of 98% and a molecular weight of 17,000 g / mol was obtained.

0.5 g of tetrabutylammonium bromide and 0.1 g of MEHQ as a thermal polymerization inhibitor were added to the polymer solution and stirred at 80 DEG C for 30 minutes. Then, 15 g of glycidyl methacrylate was added and stirred at 110 DEG C for 15 hours while maintaining the air atmosphere Respectively. After 15 hours, an alkali-soluble resin solution having a molecular weight of 19,000 g / mol and an acid value of 92 was obtained.

[Comparative Synthesis Example 3]

30 g of benzyl methacrylate, 10 g of N-phenylmaleimide, 8 g of styrene, 32 g of glycidyl methacrylate and 3 g of 1-dodecanethiol were mixed with 300 g of propylene glycol monomethyl ether acetate and the temperature of the reactor was adjusted to 60 When the temperature of the mixture reached 60 占 폚, 4 g of AIBN as a thermal polymerization initiator was added and stirred for 12 hours. After 12 hours, a polymer resin binder solution having a polymerization yield of 98% and a molecular weight of 14,500 g / mol was obtained.

To this polymer solution, 0.5 g of tetrabutylammonium bromide and 0.1 g of MEHQ as a thermal polymerization inhibitor were added and stirred at 80 ° C for 30 minutes. Then, 16.5 g of acrylic acid was added and stirred at 120 ° C for 24 hours while maintaining the air atmosphere. After 24 hours, a polymer resin binder solution having a molecular weight of 18,000 g / mol was obtained.

In the final synthesis step, 18 g of tetrahydrophthalic anhydride was added to the polymer solution and stirred at 90 ° C for 15 hours to obtain an alkali-soluble resin solution having a molecular weight of 22,000 g / mol and an acid value of 98.

[Comparative Synthesis Example 4]

30 g of cyclohexyl methacrylate, 18 g of methyl methacrylate, 32 g of glycidyl methacrylate and 3 g of 1-dodecanethiol were mixed with 300 g of propylene glycol monomethyl ether acetate, the temperature of the reactor was raised to 60 DEG C When the temperature of the mixture reached 60 占 폚, 4 g of AIBN as a thermal polymerization initiator was added and stirred for 12 hours. After 12 hours, a polymer resin binder solution having a polymerization yield of 98% and a molecular weight of 14,000 g / mol was obtained.

To this polymer solution, 0.5 g of tetrabutylammonium bromide and 0.1 g of MEHQ as a thermal polymerization inhibitor were added and stirred at 80 ° C for 30 minutes. Then, 16.5 g of acrylic acid was added and stirred at 120 ° C for 24 hours while maintaining the air atmosphere. After 24 hours, a polymer resin binder solution having a molecular weight of 18,000 g / mol was obtained.

In the final synthesis step, 18 g of tetrahydrophthalic anhydride was added to the polymer solution and stirred at 90 DEG C for 15 hours to obtain an alkali-soluble resin solution having a molecular weight of 22,500 g / mol and an acid value of 100.

 [Comparative Synthesis Example 5]

36 g of benzylmethacrylate, 12 g of N-phenylmaleimide, 10 g of styrene, 20 g of methacrylic acid and 3 g of pentaerythritol tetrakis 3-mercaptobutyrate were mixed with 300 g of propylene glycol monomethyl ether acetate, and the temperature of the reactor When the temperature of the mixture reached 60 占 폚, 4 g of AIBN as a thermal polymerization initiator was added thereto and stirred for 12 hours. After 12 hours, a polymer resin binder solution having a polymerization yield of 98% and a molecular weight of 18,500 g / mol was obtained.

0.5 g of tetrabutylammonium bromide and 0.1 g of MEHQ as a thermal polymerization inhibitor were added to the polymer solution and stirred at 80 DEG C for 30 minutes. Then, 15 g of glycidyl methacrylate was added and stirred at 110 DEG C for 15 hours while maintaining the air atmosphere Respectively. After 15 hours, an alkali-soluble resin solution having a molecular weight of 20,000 g / mol and an acid value of 90 was obtained.

[Comparative Synthesis Example 6]

30 g of cyclohexyl methacrylate, 18 g of methyl methacrylate, 20 g of methacrylic acid and 3 g of pentaerythritol tetrakis 3-mercaptobutyrate were mixed with 300 g of propylene glycol monomethyl ether acetate, and the temperature of the reactor was adjusted to 60 DEG C When the temperature of the mixture reached 60 占 폚, 4 g of AIBN as a thermal polymerization initiator was added and stirred for 12 hours. After 12 hours, a polymer resin binder solution having a polymerization yield of 98% and a molecular weight of 18,000 g / mol was obtained.

0.5 g of tetrabutylammonium bromide and 0.1 g of MEHQ as a thermal polymerization inhibitor were added to the polymer solution and stirred at 80 DEG C for 30 minutes. Then, 15 g of glycidyl methacrylate was added and stirred at 110 DEG C for 15 hours while maintaining the air atmosphere Respectively. After 15 hours, an alkali-soluble resin solution having a molecular weight of 20,500 g / mol and an acid value of 90 was obtained.

[Example 1]

5 g of the alkali-soluble resin synthesized in Synthesis Example 1 was added to 35 g of the pigment dispersion liquid, 0.5 g of photoinitiator CGI-242, 5 g of dipentaerythritol hexaacrylate, 0.1 g of 2-methacryloxypropyltrimethoxysilane, 0.1 g of propylene glycol monomethyl ether Acetate were mixed and stirred for about 3 hours to prepare a photosensitive resin composition.

[Example 2]

Except that 5 g of the alkali-soluble resin synthesized in Synthesis Example 2 was used instead of the alkali-soluble resin synthesized in Synthesis Example 1, and the mixture was stirred for about 3 hours to prepare a photosensitive resin composition Respectively.

[Example 3]

Except that 5 g of the alkali-soluble resin synthesized in Synthesis Example 3 was used instead of the alkali-soluble resin synthesized in Synthesis Example 1, and the mixture was stirred for about 3 hours to prepare a photosensitive resin composition Respectively.

[Example 4]

Except that 5 g of the alkali-soluble resin synthesized in Synthesis Example 4 was used instead of the alkali-soluble resin synthesized in Synthesis Example 1, and the mixture was stirred for about 3 hours to prepare a photosensitive resin composition Respectively.

[Comparative Example 1]

Except that 5 g of the alkali-soluble resin synthesized in Comparative Synthesis Example 1 was used instead of the alkali-soluble resin synthesized in Synthesis Example 1, and the mixture was stirred for about 3 hours to prepare a photosensitive resin composition Prepared.

[Comparative Example 2]

Except that 5 g of the alkali-soluble resin synthesized in Comparative Synthesis Example 2 was used in place of the alkali-soluble resin synthesized in Synthesis Example 1, and the mixture was stirred for about 3 hours to prepare a photosensitive resin composition Prepared.

[Comparative Example 3]

Except that 5 g of the alkali-soluble resin synthesized in Comparative Synthesis Example 3 was used instead of the alkali-soluble resin synthesized in Synthesis Example 1, and the mixture was stirred for about 3 hours to prepare a photosensitive resin composition Prepared.

[Comparative Example 4]

Except that 5 g of the alkali-soluble resin synthesized in Comparative Synthesis Example 4 was used instead of the alkali-soluble resin synthesized in Synthesis Example 1, and the mixture was stirred for about 3 hours to prepare a photosensitive resin composition Prepared.

 [Comparative Example 5]

Except that 5 g of the alkali-soluble resin synthesized in Comparative Synthesis Example 5 was used in place of the alkali-soluble resin synthesized in Synthesis Example 1, and the mixture was stirred for about 3 hours to prepare a photosensitive resin composition Prepared.

[Comparative Example 6]

Except that 5 g of the alkali-soluble resin synthesized in Comparative Synthesis Example 6 was used instead of the alkali-soluble resin synthesized in Synthesis Example 1, and the mixture was stirred for about 3 hours to prepare a photosensitive resin composition Prepared.

[Experimental Example 1 - Development Evaluation]

Each of the photosensitive resin composition solutions prepared in Examples 1 to 4 and Comparative Examples 1 to 6 was spin coated on a glass substrate and heat treated at 90 캜 for 100 seconds to form a film film. The exposed substrate was exposed to energy of 100 mJ / cm 2 using a high-pressure mercury lamp while maintaining the exposure gap of 200 탆 by using a photomask, and the exposed substrate was developed with a 0.04 wt% KOH aqueous solution for 60 sec. Respectively.

The following Table 1 shows evaluation of developability according to the developing time of each of the examples and comparative examples. When all development up to the edge of the substrate was clearly developed, the result was "? & △, and when the phenomenon was not completed yet, X was recorded.

Development time 20 seconds 30 seconds 50 seconds Example 1 △ ○ ○ Example 2 ○ ○ ○ Example 3 ○ ○ ○ Example 4 ○ ○ ○ Comparative Example 1 X △ ○ Comparative Example 2 X △ ○ Comparative Example 3 △ △ ○ Comparative Example 4 △ △ ○ Comparative Example 5 X △ ○ Comparative Example 6 X △ ○

[Experimental Example 2 - Evaluation of Sensitivity and Substrate Adhesion]

Each of the photosensitive resin composition solutions prepared in Examples 1 to 4 and Comparative Examples 1 to 6 was spin coated on a glass substrate and heat treated at 90 캜 for 100 seconds to form a film film. The exposed substrate was exposed to energy of 50, 80, and 100 mJ / cm 2 using a high pressure mercury lamp while maintaining an exposure gap of 200 탆 by using a photomask, and then the exposed substrate was developed with a 0.04 wt% KOH aqueous solution for 60 seconds. After developing, after washing and drying, heat treatment was conducted in a convection oven at 230 ° C for 25 minutes, and then the state of the pattern was observed.

Table 2 below shows the measurement and display of the size (탆) of the minimum pattern according to the exposure energy of each of the examples and the comparative examples with an optical microscope. The smaller the size of the minimum pattern, .

Exposure dose 50 mJ / cm 2 80 mJ / cm 2 100 mJ / cm 2 Example 1 12 10 10 Example 2 12 10 10 Example 3 14 12 10 Example 4 12 12 10 Comparative Example 1 18 16 16 Comparative Example 2 16 14 14 Comparative Example 3 16 14 12 Comparative Example 4 16 14 12 Comparative Example 5 16 14 14 Comparative Example 6 16 16 14

Claims (10)

1. A high molecular weight dendritic alkali-soluble binder resin satisfying the following formula (1).
[Chemical Formula 1]

(In the formula 1,
L ₁ , L ₂ , L ₃ and L ₄ independently represent a substituted or unsubstituted C1-C10 alkylene group, a substituted or unsubstituted C1-C10 alkyl ester group and a substituted or unsubstituted C1-C10 alkyl An ether group;
A ₁ , A ₂ , A ₃ and A ₄ independently represent a substituted or unsubstituted C1-C4 alkyl group, hydrogen, a substituted or unsubstituted C1-C10 alkyl group and a substituted or unsubstituted C6 An aryl group of 1 to 20 carbon atoms, and contains at least three substituted or unsubstituted C1 to C4 alkyl groups containing -SP;
At this time, P has a polymer structure of the following Chemical Formula 2,
(2)

A, b, 0 to 80 mol%, c is 0 to 80 mol%, and d is 10 to 90 mol%, wherein a, b, c and d are mole ratios of repeating units, , Wherein a + b + c + d is 100 mole%;
R ₁ and R ₂ are each independently selected from the group consisting of hydrogen, a C1-C3 alkyl group, a C1-C3 alkoxy group and a C1-C3 hydroxyalkyl group;
R ₃ and R ₄ are each independently hydrogen or a substituted or unsubstituted C 1 -C 4 alkyl group;
X is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkyl ester group, a substituted or unsubstituted C1 to C10 alkyl ether group, a substituted or unsubstituted C1 to C10 alkoxypoly An alkylene glycol ester group, and a substituted or unsubstituted C6 to C20 aryl group;
Y is a C1-C10 alkylene group containing or not containing at least one of -COO- and -O-;
Z is selected from a C1-C5 alkylene group, a substituted or unsubstituted C6-C20 arylene group, a substituted or unsubstituted C3-C20 cycloalkylene group, and a substituted or unsubstituted C3-C20 cycloalkenylene group .
With the proviso that X may be linked to R ₁ or R ₂ to form a ring of carboxylic acid anhydride or imide structure.
The method according to claim 1,
Wherein the binder resin has a weight average molecular weight of 3,000 to 100,000 g / mol and a viscosity of 20 to 150 cps.
The method according to claim 1,
Wherein the binder resin has an acid value of 30 to 200 mg KOH / g.
a) preparing a first polymer by polymerizing a mixture comprising a first monomer satisfying the following formula (3), a second monomer satisfying the following formula (4), and a thiol compound satisfying the following formula (5)
b) reacting the prepared first polymer with a compound satisfying the following formula (6) to prepare a second polymer; And
c) adding an acid group by adding a cyclic anhydride to the second polymer;
Soluble dendritic alkali-soluble binder resin.
(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(In the above formulas 3 to 6,
R ₁ and R ₂ are each independently selected from the group consisting of hydrogen, a C1-C3 alkyl group, a C1-C3 alkoxy group and a C1-C3 hydroxyalkyl group; R ₃ and R ₄ are each independently hydrogen or a substituted or unsubstituted C 1 -C 4 alkyl group;
X is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkyl ester group, a substituted or unsubstituted C1 to C10 alkyl ether group, a substituted or unsubstituted C1 to C10 alkoxypoly An alkylene glycol ester group, and a substituted or unsubstituted C6 to C20 aryl group; Y is a C1-C10 alkylene group containing or not containing at least one of -COO- and -O-;
L ₁ , L ₂ , L ₃ and L ₄ independently represent a substituted or unsubstituted C1-C10 alkylene group, a substituted or unsubstituted C1-C10 alkyl ester group and a substituted or unsubstituted C1-C10 alkyl An ether group;
B ₁ , B ₂ , B ₃ and B ₄ each independently represent a substituted or unsubstituted C1-C10 alkyl group, a hydrogen, a substituted or unsubstituted C1-C10 alkyl group and a substituted or unsubstituted C6 To C20 aryl group, and contains at least three or more substituted or unsubstituted C1-C10 alkyl groups containing -SH.
With the proviso that X may be linked to R ₁ or R ₂ to form a ring of carboxylic acid anhydride or imide structure.
5. The method of claim 4,
The mixture of step a) is mixed with 20 to 70 mol% of the first monomer, 20 to 70 mol% of the second monomer, and 1 to 10 mol% of the thiol compound in the whole mixture, and the preparation of the dendritic dendritic alkali- Way.
5. The method of claim 4,
Wherein the compound satisfying the formula (6) in the step (b) is added in an amount of 1 to 1.2 times the total molar amount of the second monomer.
5. The method of claim 4,
Wherein the cyclic anhydride in step c) is added in an amount of 0.3 to 1.1 times based on the total number of moles of the hydroxyl group formed in step b).
8. The method of claim 7,
The cyclic anhydride may be selected from the group consisting of succinic anhydride, adipic anhydride, phthalic anhydride, hexahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, and cis-5-norbornene-endo-2,3-dicar Wherein the binder resin is one or more selected from the group consisting of alicyclic dicarboxylic acid anhydrides and unsaturated dicarboxylic anhydrides.
A photosensitive resin composition comprising a high-molecular weight dendritic alkali-soluble binder resin selected from the group consisting of the compounds represented by any one of claims 1 to 3. a) coating the photosensitive resin composition according to claim 9 onto a substrate to form a photosensitive layer; And
b) patterning the photosensitive layer through a photolithographic process to form a resist film;
≪ / RTI >

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