WO2016204346A1 - Highly branched dendritic alkali-soluble binder resin, preparation method therefor, and photosensitive resin composition containing same - Google Patents

Abstract

The present invention relates to: a highly branched dendritic alkali-soluble binder resin having an excellent development property and high substrate-adhesiveness; a preparation method therefor; and a photosensitive resin composition containing the same.

Description

Highly branched dendritic alkali-soluble binder resin, preparation method thereof, and photosensitive resin composition comprising the same

The present invention relates to a highly branched dendritic alkali-soluble binder resin, a preparation method thereof and a photosensitive resin composition comprising the same.

Photosensitive resin compositions are used in photoresists for a variety of applications, such as color filters for LCDs, black matrices, overcoats, column spacers, and the like. Such compositions generally include alkali-soluble binder resins, polymerizable compounds having ethylenically unsaturated bonds, photopolymerization initiators, and solvents. It is included.

Such a photosensitive resin composition is applied onto a substrate in the process step to form a coating film, and after exposure by light irradiation using a photomask to a specific portion of the coating film, a pattern is formed by developing and removing the non-exposed part. It is used in such a way.

Therefore, the alkali-soluble binder resin used at this time should be coated with an adhesive force with the substrate, should include photocrosslinkability by exposure and developability by alkaline developer, and should be capable of forming a fine pattern. In order to prevent damage during the post-treatment process, it has to play a role of having strength, and various characteristics such as substrate adhesion, sensitivity, developability, chemical resistance, and heat resistance are required in the process step.

In particular, in the LCD market, research into developing products with higher contrast and brightness than ever before has been ongoing, and at the same time, there is a need for a high-quality photosensitive material that satisfies all the various basic properties required in the photosensitive resin composition. It is a trend.

As a similar prior document, Korean Patent Publication No. 10-2013-0118450 (2013.10.30) is presented.

It is an object of the present invention to provide a highly branched dendritic alkali-soluble binder resin having excellent developability and high substrate adhesion, a method for preparing the same, and a photosensitive resin composition comprising the same.

The present invention relates to a highly branched dendritic alkali-soluble binder resin satisfying the general formula (1) and a photosensitive resin composition comprising the same.

[Formula 1]

(In Formula 1, L ₁ , L ₂ , L ₃ and L ₄ are independently substituted or unsubstituted C1 ~ C10 alkylene group, substituted or unsubstituted C1 ~ C10 alkyl ester group and substituted or unsubstituted A ₁ , A ₂ , A ₃ and A ₄ independently represent -SP and each substituted or unsubstituted C 1 -C 4 alkyl group, hydrogen, substituted or Any one selected from an unsubstituted C1-C10 alkyl group and a substituted or unsubstituted C6-C20 aryl group, which contains -SP and contains at least three substituted or unsubstituted C1-C4 alkyl groups; In this case, P has a structure of Formula 2,

[Formula 2]

In Formula 2, a, b, c and d are 10 to 90 mol%, b is 0 to 80 mol%, c is 0 to 80 mol% and d is 10 to 90 mol% as the molar ratio of each repeating unit. Wherein a + b + c + d is 100 mol%; R ₁ and R ₂ are each independently selected from hydrogen, an alkyl group of C1-C3, an alkoxy group of C1-C3, and a hydroxyalkyl group of C1-C3; R ₃ and R ₄ are each independently hydrogen or a substituted or unsubstituted C1-C4 alkyl group; X is substituted or unsubstituted C1-C10 alkyl group, substituted or unsubstituted C1-C10 alkyl ester group, substituted or unsubstituted C1-C10 alkyl ether group, substituted or unsubstituted C1-C10 alkoxy poly An alkylene glycol ester group and a substituted or unsubstituted C6 to C20 aryl group; Y is a C1-C10 alkylene group containing or without at least one of -COO- and -O-; Z is selected from a C1 to C5 alkylene group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, and a substituted or unsubstituted C3 to C20 cycloalkenylene group Which is either. Provided that X may be linked to R ₁ or R ₂ to form a carboxylic anhydride or an imide structure ring.)

In still another aspect of the present invention, a) a first polymer is polymerized by mixing a mixture comprising a first monomer satisfying Formula 3, a second monomer satisfying Formula 4, and a thiol compound satisfying Formula 5 below. Manufacturing step; b) preparing a second polymer by reacting the prepared first polymer with a compound satisfying the following Formula 6; And c) adding an acid group by adding a cyclic anhydride to the prepared second polymer. 2. The present invention relates to a method for producing a highly branched dendritic alkali-soluble binder resin.

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

(In Formulas 3 to 6, R ₁ and R ₂ are independently selected from hydrogen, an alkyl group of C1-C3, an alkoxy group of C1-C3, and a hydroxyalkyl group of C1-C3; R ₃ and R ₄ independently of each other, 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 Any one selected from a substituted C1-C10 alkyl ether group, a substituted or unsubstituted C1-C10 alkoxy polyalkylene glycol ester group, and a substituted or unsubstituted C6-C20 aryl group; Y is -COO- And C1-C10 alkylene group containing or not including at least one or more of -O-, L ₁ , L ₂ , L ₃ and L ₄ are independently substituted or unsubstituted C 1 -C 10 alkylene group, Substituted or unsubstituted C1 to C10 Alkyl ester group and 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 to C20 aryl group, which contains -SH and contains at least three substituted or unsubstituted C1 to C10 alkyl groups, provided that X is R ₁ or R _{May be} linked to ₂ to form a carboxylic anhydride or imide structure ring.)

The high-branched dendritic alkali-soluble binder resin according to the present invention has a high-branched dendritic structure and an external acid group, so that the development speed can be adjusted appropriately, and the micro pattern is possible without neat development. It can have a very good developability, such as to facilitate the.

In addition, by having such structural characteristics, it can have a high substrate adhesion, and has a low viscosity compared to the linear binder resin having a molecular weight of a similar range can obtain a smooth surface when coating, can be coated with a desired thickness, etc. It can have an improved coating property of.

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

The present invention relates to a high-branched dendritic alkali-soluble binder resin, which is connected to a side branch rather than a main branch with a high-branched dendritic structure. It is characterized by having an acid group (external acid group).

In the case of the conventional binder resin, the development speed is too slow because the acid groups are located in the well-known linear polymer, and the development time is too long. It took a long time, or there was a problem that residues occurred because it was not developed neatly according to the pattern. On the contrary, as the linear polymer has an external acid group, the development speed was too high, so that part of the pattern to be undeveloped was lost by the developer, or The lower part of the adhered pattern is scraped off by the developer, and after the postbake process, the taper of the pattern becomes long. In addition, there was a problem that the phenomenon is not properly when reducing the acid to slow the development speed.

However, in the case of the binder resin according to the present invention, the development speed can be appropriately adjusted according to the high branched dendritic structure and external acid group, and a neat phenomenon is possible without an undeveloped portion to facilitate a fine pattern. It can have very excellent developability, such as it can. In addition, due to the high-branched dendritic structure, it may have a high substrate adhesion, and thus the coating property may be improved.

Specifically, the highly branched dendritic alkali-soluble binder resin according to the present invention may satisfy the following formula (1). In this case, the term 'substituted' or 'substituted' described below means one or more hydrogen atoms in the functional group, unless otherwise specified in the present specification, a halogen atom (F, Cl, Br, I), an alkyl group of C1 to C10, C1 to C10 In the group consisting of an alkoxy group, a C1-C10 halogenated alkyl group, a C3-C20 cycloalkyl group, a C3-C20 cycloalkenyl group, a C6-C30 allyl group, a hydroxyl group, an amine group, a carboxylic acid group and an aldehyde group It may mean that substituted with one or more substituents selected.

[Formula 1]

In Chemical Formula 1,

L ₁ , L ₂ , L ₃ and L ₄ are each independently 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 Any one selected from ether groups;

A ₁ , A ₂ , A ₃ and A ₄ independently of each other contain -SP, a substituted or unsubstituted C1-C4 alkyl group, hydrogen, a substituted or unsubstituted C1-C10 alkyl group, and a substituted or unsubstituted C6 Any one selected from an aryl group of -C20, which contains -SP and contains at least three substituted or unsubstituted C1-C4 alkyl groups;

In this case, P has a structure of Formula 2,

[Formula 2]

In Formula 2, a, b, c and d are 10 to 90 mol%, b is 0 to 80 mol%, c is 0 to 80 mol% and d is 10 to 90 mol% as the molar ratio of each repeating unit. Wherein a + b + c + d is 100 mol%;

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

R ₃ and R ₄ are each independently hydrogen or a substituted or unsubstituted C1-C4 alkyl group;

X is substituted or unsubstituted C1-C10 alkyl group, substituted or unsubstituted C1-C10 alkyl ester group, substituted or unsubstituted C1-C10 alkyl ether group, substituted or unsubstituted C1-C10 alkoxy poly It may be any one or two or more selected from an alkylene glycol ester group, and a substituted or unsubstituted C6 ~ C20 aryl group;

Y is a C1-C10 alkylene group containing or without at least one of -COO- and -O-;

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

However, X may be linked to R ₁ or R ₂ to form a ring of carboxylic anhydride or imide structure.

More preferably, in Formula 1, L ₁ , L ₂ , L _3, and L ₄ are each independently a substituted or unsubstituted C 1 to C 3 alkylene group, a substituted or unsubstituted C 1 to C 5 alkyl ester group, and a substituted or unsubstituted group. Any one selected from a substituted C1-C5 alkyl ether group, A ₁ , A ₂ , A ₃ and A ₄ independently represent -SP and each substituted or unsubstituted C 1 -C 4 alkyl, hydrogen, substituted Or any one selected from an unsubstituted C1-C3 alkyl group and a substituted or unsubstituted phenyl group, which may contain -SP and may contain at least three or more substituted or unsubstituted C1-C4 alkyl groups; A, b, c and d in the formula (2) is a molar ratio of each repeating unit 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 mol%, R ₁ and R ₂ are each independently hydrogen or an alkyl group of C 1 to C _3, and R ₃ and R ₄ are independently hydrogen or an alkyl group of C 1 to C 3 , X represents a substituted or unsubstituted C1-C3 alkyl group, a substituted or unsubstituted C1-C3 alkyl ester group, a substituted or unsubstituted C1-C3 alkyl ether group, and a substituted or unsubstituted C6-C20 Any one selected from an aryl group, X may be connected to R ₁ or R ₂ to form a ring of a carboxylic anhydride or imide structure, Y is a C1-C3 alkylene group, Z is a C1-C5 alkyl It may be any one selected from a ethylene group, 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 independently of each other an alkyl ester group of C 1 to C 5, and A ₁ , A ₂ , A ₃ and A ₄ independently of each other contain -SP. It may be an alkyl group of C1 ~ C3; A, b, c and d in the formula (2) is a molar ratio of each repeating unit 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%, In this case, a + b + c + d is 100 mol%, R ₁ and R ₂ are each independently hydrogen or methyl group, R ₃ and R ₄ are independently hydrogen or methyl group, X is an alkyl group of C1 ~ C3 , C1 ~ C3 alkyl ester group substituted with C6 ~ C20 aryl group, C1 ~ C3 alkyl ester group substituted with C6 ~ C20 cycloalkyl group, and C6 ~ C20 aryl group, X is R ₁ or R ₂ and N-phenyl maleimide, succinimide or succinic anhydride can be formed, Y is a methylene group, Z is a C1-C5 ethylene group, butylene group, phenylene group, cyclohexylene group , And cyclohexenylene group may be any one selected.

As such, the highly branched dendritic alkali-soluble binder resin that satisfies the formula (1) has a branched branched link to the main branch of the branched branch, and has an acid group linked to the branched branch to have a branched structure than a general branched polymer. Can be. As described above, by having a highly branched dendritic structure and an external acid group, it may have excellent developability and high substrate adhesion.

More specifically, when explaining the structure of the binder resin according to an embodiment of the present invention, it can be displayed as shown in Figure 1, which is to simplify the structure of the high-branched dendritic binder resin in order to help the understanding of the present invention, The present invention is not limited thereto.

As shown in FIG. 1, the binder resin according to one embodiment may be composed mainly of branches, branches and twigs, and has a structure in which twigs (external acid groups) exist in the binder resin at an appropriate ratio to improve developability. Can be. For example, the binder resin may satisfy the following relational formula 1.

[Relationship 1]

0.05 ≤ N ₂ / N ₁ ≤ 0.9

In this case, N ₁ is the number of side branches connected to the main branch of the compound satisfying the formula (1), N ₂ is the number of twigs connected to the side branch of the compound satisfying the formula (1). For example, N ₁ may be 10 to 500.

More preferably, the relation 2 may be satisfied, wherein N ₁ may be 20 to 250. More preferably, the relation 3 may be satisfied, and N ₁ may be 50 to 150.

[Relationship 2]

0.1 ≤ N ₂ / N ₁ ≤ 0.5

[Relationship 3]

0.15 ≤ N ₂ / N ₁ ≤ 0.3

The binder resin according to an embodiment of the present invention may have a weight average molecular weight of 3,000 ~ 100,000 g / mol and a viscosity of 20 ~ 150 cps. As such, by having a low viscosity as compared with the linear binder resin having a molecular weight in a similar range, it is possible to obtain a smooth surface when coating and to have an improved coating property such as coating to a desired thickness. It may more preferably have a weight average molecular weight of 5,000 to 50,000 g / mol and a viscosity of 30 to 120 cps, and more preferably may have a weight average molecular weight of 10,000 to 30,000 g / mol and a viscosity of 50 to 100 cps.

In addition, the binder resin according to an embodiment of the present invention may have an acid value of 30 to 200 mg KOH / g. The development is excellent in this range, the development is neat, it may be easy to form a fine pattern. More preferably, the acid value may be 50 to 150 mg KOH / g, and even more preferably 70 to 130 mg KOH / g.

Method for producing a highly branched dendritic alkali-soluble binder resin, a) a first monomer satisfying the formula (3), a second monomer satisfying the formula (4) and a thiol compound satisfying the formula (5) Preparing a first polymer by polymerizing a mixture including the first polymer; b) preparing a second polymer by reacting the prepared first polymer with a compound satisfying the following Formula 6; And c) introducing an acid group by adding a cyclic anhydride to the prepared second polymer. However, the first monomer satisfies Formula 3, but may be used by mixing two or more different compounds.

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

In Chemical Formulas 3 to 6,

R ₁ and R ₂ are each independently selected from hydrogen, an alkyl group of C1-C3, an alkoxy group of C1-C3, and a hydroxyalkyl group of C1-C3; R ₃ and R ₄ are each independently hydrogen or a substituted or unsubstituted C1-C4 alkyl group;

X is substituted or unsubstituted C1-C10 alkyl group, substituted or unsubstituted C1-C10 alkyl ester group, substituted or unsubstituted C1-C10 alkyl ether group, substituted or unsubstituted C1-C10 alkoxy poly It may be any one or two or more selected from an alkylene glycol ester group, and a substituted or unsubstituted C6 ~ C20 aryl group; Y is a C1-C10 alkylene group containing or without at least one of -COO- and -O-;

L ₁ , L ₂ , L ₃ and L ₄ are each independently 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 Any one selected from ether groups;

B ₁ , B ₂ , B ₃ and B ₄ independently of each other contain -SH, a substituted or unsubstituted C1-C10 alkyl group, hydrogen, a substituted or unsubstituted C1-C10 alkyl group, and a substituted or unsubstituted C6 Any one selected from the aryl group of ~ C20, containing -SH and may contain at least three or more substituted or unsubstituted C1 ~ C10 alkyl group.

However, X may be linked to R ₁ or R ₂ to form a ring of carboxylic anhydride or imide structure.

More preferably, in the first monomer satisfying Formula 3, R ₁ and R ₂ are independently of each other hydrogen or an alkyl group of C 1 to C 3, and X is a substituted or unsubstituted C 1 to C 3 alkyl group, a substituted or unsubstituted C 1 It may be any one or two or more selected from an alkyl ester group of ~ C3, a substituted or unsubstituted C1 ~ C3 alkyl ether group, and a substituted or unsubstituted C6 ~ C20 aryl group, X is R ₁ or R ₂ Can be linked to form a ring of carboxylic anhydride or imide structure; In the second monomer satisfying Formula 4, R ₃ is hydrogen or an alkyl group of C 1 to C 3, and Y is an alkylene group of C 1 to C 3; In the thiol-based compound satisfying Formula 5, L ₁ , L ₂ , L _3, and L ₄ are each independently a substituted or unsubstituted C1-C3 alkylene group, a substituted or unsubstituted C1-C5 alkyl ester group, and a substitution. Or any one selected from an unsubstituted C1-C5 alkyl ether group; B ₁ , B ₂ , B ₃ and B ₄ independently of each other contain -SH, a substituted or unsubstituted C1-C4 alkyl group, hydrogen, a substituted or unsubstituted C1-C3 alkyl group, and a substituted or unsubstituted phenyl group Any one selected from-may contain -SH, and may contain at least three or more substituted or unsubstituted C1-C4 alkyl groups.

More preferably, in the first monomer satisfying Formula 3, R ₁ and R ₂ are each independently hydrogen or a methyl group, X is an alkyl ester group of C 1 to C 3 substituted with an alkyl group of C 1 to C 3, an aryl group of C 6 to C 20 It may be any one or two or more selected from C1 ~ C3 alkyl ester group substituted with a C6 ~ C20 cycloalkyl group, and C6 ~ C20 aryl group, X is R ₁ or R ₂ and N-phenyl maleimide, Succinimide or succinic anhydride and the like; In a second monomer satisfying Formula 4, R ₃ is hydrogen or a methyl group, and Y is a methylene group; The thiol-based compound satisfying Formula 5 may be pentaerythritol tetrakis thioglycolate or Pentaerythritol tetrakis 3-mercaptobutylate, and satisfies Formula 6 The compound to be may be acrylic acid or methacrylic acid.

The method for producing a binder resin according to the present invention does not proceed with polymerization in one step, and by sequentially introducing necessary functional groups through several steps, the advantage of polymerizing a binder resin having a desired structure and physical properties as planned. There is an advantage, as the introduction of acid groups in the last step, the acid value is easy to adjust, and because the acid groups are located on the side branches rather than the main one, there is an advantage that the developability can be improved.

Specifically, for each step, first step a) is a first polymer by polymerizing a mixture comprising a first monomer satisfying Formula 3, a second monomer satisfying Formula 4 and a thiol-based compound satisfying Formula 5 In the preparing step, a polymer having a branched main structure is polymerized.

Mixture according to an embodiment of the present invention can be mixed in varying amounts as planned, specifically, for example, 20 to 70 mol% of the first monomer, 20 to 70 mol% of the second monomer and thiol in the total mixture It can be mixed with 1 to 10 mol% of the system compound.

Next, step b) is a step of preparing a second polymer by reacting the first polymer prepared in step a) with a compound that satisfies the formula (6), which can react with a cyclic anhydride to introduce an external acid group. This step is to form a hydroxyl group (-OH). In this case, the compound that satisfies the formula (6) of step b) may be added in a 1 ~ 1.2 times based on the total mole number of the second monomer.

Next, step c) is a step of introducing an acid group by adding a cyclic anhydride to the second polymer prepared in step b), wherein the hydroxyl group formed in step b) reacts with the cyclic anhydride to enable development. Is formed, thereby forming an external acid group into which an acid group is introduced, and a highly branched binder resin can be obtained.

At this time, the cyclic anhydride of step c) may be added in 0.3 ~ 1.1 times based on the total moles of the hydroxyl group formed in step b). The acid value of the highly branched dendritic alkali-soluble binder resin finally obtained can be adjusted to 30-200 mg KOH / g by using the addition amount of cyclic anhydride within the said range.

The cyclic anhydride can be used without particular limitation as long as it can react with a hydroxyl group to form an acid group (-COOH). Specifically, for example, succinic anhydride, adipic anhydride, phthalic anhydride, hexahydrophthalic anhydride, One, two or more selected from 1,2,3,6-tetrahydro phthalic anhydride and cis-5-norbornene-endo-2,3-dicarboxylic acid anhydride may be used, but is not limited thereto.

In addition, the present invention can obtain a photosensitive resin composition comprising a highly branched dendritic alkali-soluble binder resin, the photosensitive resin composition is a polymerizable compound having an ethylenically unsaturated bond, a colorant, a photoinitiator, a solvent and the like. This can be included more.

The photosensitive resin composition according to one embodiment is 1 to 20% by weight of the highly branched dendritic alkali-soluble binder resin, 1 to 10% by weight of the polymerizable compound having an ethylenically unsaturated bond, 1 to 30% by weight of the colorant, 0.1 to 5% by weight of the initiator % And the solvent 35 to 95% by weight.

The polymerizable compound having an ethylenically unsaturated bond can be used without particular limitation as long as it is commonly used in the art. Specifically, for example, ethylene glycol di (meth) acrylate and polyethylene glycol having 2 to 14 ethylene groups. Di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, number of propylene groups Propylene glycol di (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, or a mixture thereof, which is ˜14, may be used, but is not limited thereto.

Colorants may also be used without particular limitation as long as they are commonly used in the art. Specifically, for example, carmine 6B (CI12490), phthalocyanine green (CI 74260), phthalocyanine blue (CI 74160), and perylene black (BASF K0084). K0086), Cyanine Black, Linol Yellow (CI21090), Linol 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, 202, 214, 215, 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, etc. may be used, but is not limited thereto.

The photoinitiator may also be used without particular limitation as long as it is commonly used in the art, and for example, 2,4-trichloromethyl- (4'-methoxyphenyl) -6-triazine, 2,4-trichloro Rhomethyl- (4'-methoxystyryl) -6-triazine, 2,4-trichloromethyl- (piflonil) -6-triazine, 2,4-trichloromethyl- (3 ', 4 Triazine compounds such as' -dimethoxyphenyl) -6-triazine and 3- {4- [2,4-bis (trichloromethyl) -s-triazin-6-yl] phenylthio} propanoic acid; 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl biimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4', 5 Biimidazole compounds such as 5′-tetraphenylbiimidazole; 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxy Methoxy) -phenyl (2-hydroxy) propyl ketone, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-2-phenyl acetophenone, 2-methyl- (4-methylthiophenyl) -2-mol Acetophenone-based compounds (Irgacure- such as polyno-1-propane-1-one (Irgacure-907) and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one) 369); O-acyl oxime compounds such as Irgacure OXE 01 and Irgacure OXE 02 by CibaGeigy, benzophenone compounds such as 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone ; Thioxanthone-based compounds such as 2,4-diethyl thioxanthone, 2-chloro thioxanthone, isopropyl thioxanthone and diisopropyl thioxanthone; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl phosphine oxide, bis (2,6-dichlorobenzoyl) propyl phosphine oxide Phosphine oxide compounds such as these; 3,3'-carbonylvinyl-7- (diethylamino) coumarin, 3- (2-benzothiazolyl) -7- (diethylamino) coumarin, 3-benzoyl-7- (diethylamino) coumarin, 3-benzoyl-7-methoxy-coumarin, 10,10'-carbonylbis [1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H, 5H, 11H-Cl] It may be a coumarin-based compound such as -benzopyrano [6,7,8-ij] -quinolizine-11-one or a mixture thereof, but is not limited thereto.

The solvent may also be used without particular limitation as long as it is commonly used in the art. Specifically, for example, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene Glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, 2-ethoxy propanol, 2-methoxy propanol, 3-methoxy butanol, cyclohexa Paddy, cyclopentanone, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, 3-methoxybutyl acetate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, methyl cellosolve acetate, butyl acetate, dipropylene May be glycol monomethyl ether or mixtures thereof But, not limited to this.

In addition, additives, such as a dispersing agent, a dispersion stabilizer, an adhesion promoter, and surfactant, can be further added as needed in the range which does not impair the physical property of the photosensitive resin composition.

Such a photosensitive resin composition may 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 the photosensitive resin composition. Specifically, the 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 photolithography process to form a resist film.

The coating method of step a) may be used without any particular limitation as long as it is a commonly used method, and specifically, for example, a photosensitive layer may be formed using spin coating or slit coating. .

After forming the photosensitive layer, a process of vacuuming and / or pre-baking may be further performed. Vacuum treatment according to an example may be carried out for 20 to 60 seconds at a pressure of 0.3 ~ 1 torr, electrothermal treatment may be performed for 60 to 120 seconds at a temperature of 70 ~ 120 ℃.

Next, a photoresist layer may be patterned through a photolithography process to form a resist film, and the photolithography process may use a method commonly used in the art. For example, a patterned resist film may be formed by exposing and developing using a mask having a predetermined pattern formed thereon. More specifically, for example, it may be exposed at an intensity of 30 to 150 mJ / cm 2, and a pattern may be formed by removing a portion not photopolymerized using an aqueous alkali solution of 10 to 12 and washing with water.

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

Hereinafter, the highly branched dendritic alkali-soluble binder resin according to the present invention, a method for preparing the same, and a photosensitive resin composition will be described in more detail with reference to the following examples. However, the following examples are only one reference for describing the present invention in detail, and the present invention is not limited thereto and may be implemented in various forms.

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

In addition, the following drawings are provided as examples to fully convey the spirit of the present invention to those skilled in the art. Therefore, the present invention is not limited to the drawings presented below and may be embodied in other forms, and the drawings presented below may be exaggerated to clarify the spirit of the present invention.

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

In addition, the unit of the additive which is not specifically described in the specification may be wt%.

The physical properties of the highly branched dendritic alkali-soluble binder resin and 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-phenyl maleimide, 8 g of styrene, 32 g of glycidyl methacrylate, 3 g of pentaerythritol tetrakis thioglycolate are mixed with 300 g of propylene glycol monomethyl ether acetate and the temperature of the reactor under nitrogen atmosphere. When the mixture was heated to 60 ° C. and the temperature of the mixture reached 60 ° C., 4 g of azodiisobutyronitrile (AIBN), a thermal polymerization initiator, was added thereto, followed by stirring 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 monomethyl ether hydroquinone (MEHQ), a thermal polymerization inhibitor, were added to the first polymer solution, stirred at 80 ° C. for 30 minutes, 16.5 g of acrylic acid was added thereto, and 120 ° C. was maintained while maintaining an air atmosphere. Stirred for 24 h. After 24 hours, a second polymer resin binder solution having a molecular weight of 19,000 g / mol was obtained.

As a final synthesis step, 18 g of tetrahydro phthalic anhydride was added to the 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 tetrakis thioglycolate were mixed with 300 g of propylene glycol monomethyl ether acetate and the reactor temperature was maintained at 60 ° C. under a nitrogen atmosphere. When the mixture was heated to 60 ° C., 4 g of AIBN, a thermal polymerization initiator, was added thereto, followed by stirring 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, a thermal polymerization inhibitor, were added to the first polymer solution and stirred at 80 ° C. for 30 minutes. Then, 16.5 g of acrylic acid was added thereto and stirred at 120 ° C. for 24 hours. After 24 hours, a second polymer resin binder solution having a molecular weight of 18,500 g / mol was obtained.

As a final synthesis step, 18 g of tetrahydro phthalic anhydride was added to the second polymer solution and stirred at 90 ° 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 benzyl methacrylate, 10 g of N-phenyl maleimide, 8 g of styrene, 32 g of glycidyl methacrylate, 3 g of pentaerythritol tetrakis 3-mercaptobutylate were mixed with 300 g of propylene glycol monomethyl ether acetate and under nitrogen atmosphere. When the temperature of the reactor was increased to 60 degrees and the temperature of the mixture reached 60 ° C., 4 g of AIBN, which is a thermal polymerization initiator, was added thereto, followed by stirring 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, a thermal polymerization inhibitor, were added to the first polymer solution and stirred at 80 ° C. for 30 minutes. Then, 16.5 g of acrylic acid was added thereto and stirred at 120 ° C. for 24 hours. After 24 hours, a second polymer resin binder solution having a molecular weight of 18,000 g / mol was obtained.

As a final synthesis step, 18 g of tetrahydro phthalic anhydride was added to the second polymer solution and stirred at 90 ° 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, 3 g of pentaerythritol tetrakis 3-mercaptobutylate were mixed with 300 g of propylene glycol monomethyl ether acetate and the temperature of the reactor under nitrogen atmosphere. When the mixture was raised to 60 ° C. and the temperature of the mixture reached 60 ° C., 4 g of AIBN, which is a thermal polymerization initiator, was added thereto, followed by stirring 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.

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

As a final synthesis step, 18 g of tetrahydro phthalic 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 100.

 Comparative Example 1

36 g of benzyl methacrylate, 12 g of N-phenyl maleimide, 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, and the temperature of the reactor was raised to 60 DEG C under a nitrogen atmosphere and the mixture was When the temperature of 60 ℃ was added 4g of AIBN which is a thermal polymerization initiator 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, a thermal polymerization inhibitor, were added to the polymer solution and stirred at 80 ° C. for 30 minutes. Then, 15 g of glycidyl methacrylate was added and stirred at 110 ° C. for 15 hours while maintaining an air atmosphere. It was. 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 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, and the temperature of the reactor was raised to 60 ° C. under a nitrogen atmosphere, and the temperature of the mixture was When the temperature reached 60 ° C., 4 g of AIBN, a thermal polymerization initiator, was added thereto, followed by stirring 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, a thermal polymerization inhibitor, were added to the polymer solution and stirred at 80 ° C. for 30 minutes. Then, 15 g of glycidyl methacrylate was added and stirred at 110 ° C. for 15 hours while maintaining an air atmosphere. It was. 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 Example 3

30 g of benzyl methacrylate, 10 g of N-phenyl maleimide, 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 under nitrogen atmosphere was 60 When it was raised to ℃ and the mixture temperature was 60 ℃, 4g of AIBN, 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.

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

As a final synthesis step, 18 g of tetrahydro phthalic 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 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 and the temperature of the reactor was raised to 60 ° C. under nitrogen atmosphere. When the temperature of the mixture reached 60 ℃, 4g of AIBN, 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.

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

As a final synthesis step, 18 g of tetrahydro phthalic 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 22,500 g / mol and an acid value of 100.

 Comparative Example 5

36 g of benzyl methacrylate, 12 g of N-phenyl maleimide, 10 g of styrene, 20 g of methacrylic acid, and 3 g of pentaerythritol tetrakis 3-mercaptobutylate were mixed with 300 g of propylene glycol monomethyl ether acetate and the temperature of the reactor was changed under nitrogen atmosphere. When the temperature was increased to 60 ° C. and the temperature of the mixture reached 60 ° C., 4 g of AIBN, a thermal polymerization initiator, was added thereto, followed by stirring 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, a thermal polymerization inhibitor, were added to the polymer solution and stirred at 80 ° C. for 30 minutes. Then, 15 g of glycidyl methacrylate was added and stirred at 110 ° C. for 15 hours while maintaining an air atmosphere. It was. 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 Example 6

30 g of cyclohexyl methacrylate, 18 g of methyl methacrylate, 20 g of methacrylic acid, and 3 g of pentaerythritol tetrakis 3-mercaptobutylate were mixed with 300 g of propylene glycol monomethyl ether acetate and the temperature of the reactor was changed to 60 ° C. under a nitrogen atmosphere. When the mixture was heated to 60 ° C., 4 g of AIBN, a thermal polymerization initiator, was added thereto, followed by stirring 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, a thermal polymerization inhibitor, were added to the polymer solution and stirred at 80 ° C. for 30 minutes. Then, 15 g of glycidyl methacrylate was added and stirred at 110 ° C. for 15 hours while maintaining an air atmosphere. It was. 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

35 g of green pigment dispersion liquid 5 g of alkali-soluble resin synthesized in Synthesis Example 1, 0.5 g of photoinitiator CGI-242, 5 g of dipentaerythritol hexaacrylate, 0.1 g of 2-methacryloxypropyl trimethoxysilane, propylene glycol monomethyl ether 60 g of acetate was mixed and stirred for about 3 hours to prepare a photosensitive resin composition.

Example 2

A photosensitive resin composition was prepared by mixing in the same composition as in Example 1 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, followed by stirring for about 3 hours. It was.

Example 3

A photosensitive resin composition was prepared by mixing in the same composition as in Example 1 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, followed by stirring for about 3 hours. It was.

Example 4

A photosensitive resin composition was prepared by mixing with the same composition as in Example 1, 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, followed by stirring for about 3 hours. It was.

Comparative Example 1

A photosensitive resin composition was prepared by mixing in the same composition as in 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, followed by stirring for about 3 hours. Ready.

Comparative Example 2

A photosensitive resin composition was prepared by mixing in the same composition as in Example 1 except that 5 g of the alkali-soluble resin synthesized in Comparative Synthesis Example 2 was used instead of the alkali-soluble resin synthesized in Synthesis Example 1, followed by stirring for about 3 hours. Ready.

Comparative Example 3

A photosensitive resin composition was prepared by mixing in the same composition as in Example 1, 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, followed by stirring for about 3 hours. Ready.

Comparative Example 4

A photosensitive resin composition was prepared by mixing in the same composition as in Example 1, 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. Ready.

 Comparative Example 5

A photosensitive resin composition was prepared by mixing in the same composition as in Example 1, except that 5 g of the alkali-soluble resin synthesized in Comparative Synthesis Example 5 was used instead of the alkali-soluble resin synthesized in Synthesis Example 1. Ready.

Comparative Example 6

A photosensitive resin composition was prepared by mixing in the same composition as in Example 1, 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. Ready.

Experimental Example 1-Developability 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 then subjected to an electrothermal treatment at 90 ° C. for 100 seconds to form a film film. This was exposed to energy of 100 mJ / cm 2 using a high pressure mercury lamp while maintaining an exposure gap of 200 μm using a photomask, and then the exposed substrate was developed with 0.04 wt% KOH aqueous solution for up to 60 seconds to observe the development process. It was.

Table 1 shows the evaluation results of the development time according to the development time of each of the Examples and Comparative Examples, when the development of all the edges of the substrate to a clean development ○, almost developed but still less developed The time when this was seen as △ and the time when the development was not good overall as X was recorded.

Developing 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 Adhesive Force

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 then subjected to an electrothermal treatment at 90 ° C. for 100 seconds to form a film film. This was exposed to an energy of 50, 80 and 100 mJ / cm 2 using a high pressure mercury lamp while maintaining an exposure gap of 200 μm using a photomask, and then the exposed substrate was developed for 60 seconds with a 0.04 wt% KOH aqueous solution. After development, after heat treatment for 25 minutes in a 230 ℃ convection oven through a washing and drying process, the state of the pattern was observed.

Table 2 below shows the size (μm) of the smallest remaining pattern according to the exposure energy of each of the Examples and Comparative Examples, measured and marked with an optical microscope, and the smaller the minimum size of the remaining pattern is, the more sensitive and substrate adhesion is. This means excellence.

Exposure	50 mJ / ㎠	80 mJ / ㎠	100 mJ / ㎠
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. Highly branched dendritic alkali-soluble binder resin satisfying the formula (1).

   [Formula 1]

   

   (In Formula 1,

   L ₁ , L ₂ , L ₃ and L ₄ are each independently 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 Any one selected from ether groups;

   A ₁ , A ₂ , A ₃ and A ₄ independently of each other contain -SP, a substituted or unsubstituted C1-C4 alkyl group, hydrogen, a substituted or unsubstituted C1-C10 alkyl group, and a substituted or unsubstituted C6 Any one selected from an aryl group of -C20, which contains -SP and contains at least three substituted or unsubstituted C1-C4 alkyl groups;

   In this case, P has a structure of Formula 2,

   [Formula 2]

   

   In Formula 2, a, b, c and d are 10 to 90 mol%, b is 0 to 80 mol%, c is 0 to 80 mol% and d is 10 to 90 mol% as the molar ratio of each repeating unit. Wherein a + b + c + d is 100 mol%;

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

   R ₃ and R ₄ are each independently hydrogen or a substituted or unsubstituted C1-C4 alkyl group;

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

   Y is a C1-C10 alkylene group containing or without at least one of -COO- and -O-;

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

   Provided that X may be linked to R ₁ or R ₂ to form a carboxylic anhydride or an imide structure ring.)
2. The method of claim 1,

   The binder resin is a high-branched dendritic alkali-soluble binder resin having a weight average molecular weight of 3,000 ~ 100,000 g / mol and a viscosity of 20 ~ 150 cps.
3. The method of claim 1,

   The binder resin is a high branched dendritic alkali-soluble binder resin having an acid value of 30 ~ 200 mg KOH / g.
4. a) preparing a first polymer by polymerizing a mixture including a first monomer satisfying Formula 3, a second monomer satisfying Formula 4, and a thiol compound satisfying Formula 5;

   b) preparing a second polymer by reacting the prepared first polymer with a compound satisfying the following Formula 6; And

   c) introducing an acid group by adding a cyclic anhydride to the prepared second polymer;

   Method for producing a highly branched dendritic alkali-soluble binder resin comprising a.

   [Formula 3]

   

   [Formula 4]

   

   [Formula 5]

   

   [Formula 6]

   

   (In Chemical Formulas 3 to 6,

   R ₁ and R ₂ are each independently selected from hydrogen, an alkyl group of C1-C3, an alkoxy group of C1-C3, and a hydroxyalkyl group of C1-C3; R ₃ and R ₄ are each independently hydrogen or a substituted or unsubstituted C1-C4 alkyl group;

   X is substituted or unsubstituted C1-C10 alkyl group, substituted or unsubstituted C1-C10 alkyl ester group, substituted or unsubstituted C1-C10 alkyl ether group, substituted or unsubstituted C1-C10 alkoxy poly An alkylene glycol ester group and a substituted or unsubstituted C6 to C20 aryl group; Y is a C1-C10 alkylene group containing or without at least one of -COO- and -O-;

   L ₁ , L ₂ , L ₃ and L ₄ are each independently 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 Any one selected from ether groups;

   B ₁ , B ₂ , B ₃ and B ₄ independently of each other contain -SH, a substituted or unsubstituted C1-C10 alkyl group, hydrogen, a substituted or unsubstituted C1-C10 alkyl group, and a substituted or unsubstituted C6 Any one selected from an aryl group of ~ C20, containing -SH and at least three substituted or unsubstituted C1 ~ C10 alkyl group.

   Provided that X may be linked to R ₁ or R ₂ to form a carboxylic anhydride or an imide structure ring.)
5. The method of claim 4, wherein

   Preparation of the highly branched dendritic alkali-soluble binder resin is a 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 total mixture Way.
6. The method of claim 4, wherein

   The compound satisfying the formula (6) of step b) is a method for producing a highly branched dendritic alkali-soluble binder resin is added 1 to 1.2 times based on the total moles of the second monomer.
7. The method of claim 4, wherein

   The cyclic anhydride of step c) is added to 0.3 to 1.1 times based on the total number of moles of the hydroxy group formed in step b) method of producing a high branched dendritic alkali-soluble binder resin.
8. The method of claim 7, wherein

   The cyclic anhydrides include succinic anhydride, adipic anhydride, phthalic anhydride, hexahydrophthalic anhydride, 1,2,3,6-tetrahydro phthalic anhydride, and cis-5-norbornene-endo-2,3-dicar A process for producing a highly branched dendritic alkali soluble binder resin, which is any one or two or more selected from acid anhydrides.
9. The photosensitive resin composition containing the highly branched dendritic alkali-soluble binder resin of any one of Claims 1-3.
10. a) coating the photosensitive resin composition according to claim 9 on a substrate to form a photosensitive layer; And

    b) patterning the photosensitive layer through a photolithography process to form a resist film;

    Method of forming a patterned resist film comprising a.

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