KR101730610B1 - Adhesion promoter for photo-resist, and photo-sensitive resin composition comprising the same - Google Patents

Abstract

(상기 화학식 1에서, X는 O- 또는 N(Z²)-이며; Y는 직접결합, 치환 또는 비치환된 C6~C20의 아릴렌기, 또는 치환 또는 비치환된 C6~C20의 사이클로알킬렌기이며; Z¹ 및 Z²는 서로 독립적으로 -H, 치환 또는 비치환된 C1~C6의 알킬기, 치환 또는 비치환된 C6~C20의 아릴기, 치환 또는 비치환된 C6~C20의 사이클로알킬기 또는 R²²Si(R³³)(R⁴⁴)(R⁵⁵)이며; R¹은 C16~C30의 알킬기이며; R² 및 R²²는 서로 독립적으로 C1~C6의 알킬렌기이며; R³, R⁴, R⁵, R³³, R⁴⁴ 및 R⁵⁵는 서로 독립적으로 C1~C6의 알콕시기이다.)The present invention relates to an adhesion promoting agent for photoresists comprising a silane compound satisfying the following formula (1).
[Chemical Formula 1]

(Wherein X is O- or N (Z ² ) -, Y is a direct bond, a substituted or unsubstituted C6-C20 arylene group, or a substituted or unsubstituted C6-C20 cycloalkylene group ; Z ¹ and Z ² are independently -H, a substituted or unsubstituted cycloalkyl group of the aryl group of C1 ~ C6 alkyl group, a substituted or unsubstituted C6 ~ C20 of a substituted or unsubstituted C6 ~ C20, or R ²² together ^{Si (R 33) (R 44} ) (R 55) a; R ¹ is an alkyl group of C16 ~ C30; R ² and R ²² are independently an alkylene group of C1 ~ C6 from each ^{other; R 3, R 4, R} 5 , R ³³ , R ⁴⁴ and R ⁵⁵ are each independently a C 1 to C 6 alkoxy group.)

Description

[0001] The present invention relates to an adhesion promoting agent for photoresists and a photosensitive resin composition containing the same,

The present invention relates to an adhesion promoting agent for photoresists 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 .

In the photosensitive resin composition, improvement in developability such as shortening the development time or improving the sensitivity is a particularly important problem in improvement of production efficiency and the like. Conventionally, a method of improving developability by increasing the proportion of an acid group monomer in the binder resin has been used. However, since the binder resin having a high acid value has a low solubility in a solvent which is usually used in the introduction of a photopolymerizable functional group, precipitation occurs during polymerization and a desired molecular weight can not be obtained. There is a problem that the ratio of the monomer to be imparted is relatively lowered and other properties are deteriorated.

Thus, there is a need for research to improve the developability without compromising the properties of the photosensitive resin composition, and it is also desired to provide a photosensitive resin composition which is superior in adhesion strength to a silane coupling agent that improves the substrate adhesion of the photosensitive resin composition, It is necessary to study the silane compounds.

Korean Patent Registration No. 10-1384457 is disclosed as a similar prior art document.

Korean Patent Registration No. 10-1384457 (April 4, 2014).

In order to solve the above-mentioned problems, it is an object of the present invention to provide an adhesion promoting agent for photoresists having improved developing properties by improving the adhesion of a substrate and a photosensitive resin composition containing the same.

In order to accomplish the above object, the present invention relates to an adhesion promoting agent for photoresists comprising a silane compound satisfying the following formula (1).

[Chemical Formula 1]

In Formula 1, X is -O- or -N (Z ² ) -; Y is a direct bond, a substituted or unsubstituted C6 to C20 arylene group, or a substituted or unsubstituted C6 to C20 cycloalkylene group; Z ¹ and Z ² are each independently -H, a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C6-C20 cycloalkyl group or -R ²² Si ( ^R33 ) ( ^R44 ) ( ^R55 ); R < ¹ > is a C16-C30 alkyl group; R ² and R ²² are each independently a C 1 to C 6 alkylene group; R ³ , R ⁴ , R ⁵ , R ³³ , R ⁴⁴ and R ⁵⁵ are each independently a C 1 to C 6 alkoxy group.

Another aspect of the present invention relates to a photosensitive resin composition comprising an adhesion promoting agent for photoresists and a photosensitive material prepared using the same.

The adhesion promoter for photoresists according to the present invention can prevent the disappearance of the fine pattern due to the hydrophobic property of the long alkyl chain in the development process by using the long silane compound having an alkyl chain, It can have developability. In addition, when a urethane group or a urea group is contained relative to a silane-based compound containing an amine group, stability is more excellent when it is used as a constituent component of the photosensitive resin composition.

Hereinafter, the adhesion promoting agent for photoresists of the present invention will be described in detail. Here, unless otherwise defined, technical terms and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs. In the following description, the gist of the present invention is unnecessarily blurred And a description of the known function and configuration will be omitted.

The present invention relates to an adhesion promoting agent for photoresists comprising a silane compound. The adhesion enhancer for photoresists according to the present invention improves adhesion with a substrate by using a long silane compound having an alkyl chain (Alkyl chain) And thus it can be advantageous to form a very fine and dense fine pattern.

The adhesion promoting agent for photoresists according to an example of the present invention may include a silane compound satisfying the following formula (1).

[Chemical Formula 1]

In Formula 1, X is -O- or -N (Z ² ) -; Y is a direct bond, a substituted or unsubstituted C6 to C20 arylene group, or a substituted or unsubstituted C6 to C20 cycloalkylene group; Z ¹ and Z ² are each independently -H, a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C6-C20 cycloalkyl group, or -R ²² Si ( ^R33 ) ( ^R44 ) ( ^R55 ); R < ¹ > is a C16-C30 alkyl group; R ² and R ²² are each independently a C 1 to C 6 alkylene group; R ³ , R ⁴ , R ⁵ , R ³³ , R ⁴⁴ and R ⁵⁵ may independently be a C 1 to C 6 alkoxy group.

Such an adhesion promoter for photoresists containing a long alkyl chain having a carbon number of 16 or more can prevent the disappearance of fine patterns due to the hydrophobic property of the long alkyl chain during the development process, Lt; / RTI > In addition, in the case of a silane-based adhesion promoter compound containing an amine group, there is a problem that the stability of the silane-based adhesion promoter compound due to the active hydrogen of the amine group is low due to the active hydrogen of the amine group. However, urea bond or urethane bond, thereby improving the stability.

More preferably, the adhesion promoter for photoresists is a silane compound satisfying the above formula (1), X is -O- or -NH-; Y is a direct bond, a phenylene group, a naphthalene group or a cyclohexylene group; Z ¹ is H, a propyl group, a butyl group, a phenyl group, a naphthyl group, a cyclohexyl group or -R ²² Si (R ³³ ) (R ⁴⁴ ) (R ⁵⁵ ); R < ¹ > is a C16-C30 alkyl group; R ² and R ²² are each independently a C 1 to C 6 alkylene group; R ³ , R ⁴ , R ⁵ , R ³³ , R ⁴⁴ and R ⁵⁵ independently of one another may be a methoxy group or an ethoxy group. By using the silane-based compound satisfying this requirement, it is possible to more effectively prevent the disappearance of the fine pattern and further improve the adhesion with the substrate, thereby achieving excellent developability. In addition, this can be advantageous in forming a very fine and dense fine pattern.

In one embodiment, the silane-based compound may be any one or two or more selected from the following formulas (2) to (8).

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

In the above Chemical Formulas 2 to 8, a is a real number of 14 to 28; R may be a methyl group or an ethyl group.

The term "substituted" or "substituted" as used herein refers to a group in which at least one hydrogen atom in the functional group is a halogen atom (F, Cl, Br, I), a C1- A halogenated alkyl group of C1 to C6, a cycloalkyl group of C6 to C20, a cycloalkenyl group of C6 to C20, an allyl group of C6 to C20, a hydroxyl group, an amine group, a carboxylic acid group and an aldehyde group Or may be substituted with at least one substituent selected. In addition, 'direct bond' means that X and R ¹ are directly connected without any other linking group.

Further, the present invention may be related to a photosensitive resin composition containing an adhesion promoting agent for photoresists, and more particularly, to a photosensitive resin composition containing a silane-based compound adhesion promoting agent for photoresists.

The adhesion promoting agent for photoresists according to one example may be contained in an amount of 0.01 to 5% by weight, more preferably 0.05 to 2% by weight, based on the total weight of the composition. In this range, it is possible to improve the adhesion with the substrate without deteriorating the other physical properties of the composition and to have excellent developability, and thus, fine patterns can be neatly formed without undeveloped or lost portions.

In addition, the photosensitive resin composition preferably contains 1 to 20% by weight of an 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% 35 to 95% by weight of a solvent.

The alkali-soluble binder resin according to an exemplary embodiment is not particularly limited as long as it is commonly used in the art, and may be a copolymer of a monomer imparting mechanical strength and a monomer imparting alkali solubility in detail. In one embodiment, the monomer imparting mechanical strength is selected from the group consisting of benzyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, dimethylaminoethyl Butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, ethylhexyl- Hydroxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (Meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, , Ethoxydiethylene glycol (meth) Acrylate, methoxytriethylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, poly (ethylene glycol) methyl ether (meth) acrylate, phenoxy diethylene glycol (Meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, p-nonylphenoxypolypropylene glycol (meth) acrylate, glycidyl (meth) acrylate, tetrafluoropropyl (Meth) acrylate, 3,3,3-hexafluoroisopropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, tribromophenyl Dicyclopentenyl methacrylate, dicyclopentenyloxyethyl acrylate, isobornyl methacrylate, adamantyl methacrylate, methyl [alpha] -hydroxymethyl-acrylate Acrylate, ethyl α- hydroxymethyl acrylate, propyl α- hydroxy methyl acrylate, and butyl α- hydroxymethyl-unsaturated carboxylic acid ester at least one selected from the group consisting of acrylates; At least one aromatic compound selected from the group consisting of styrene,? -Methylstyrene, (o, m, p) -vinyltoluene, (o, m, p) -methoxystyrene, and (o, m, p) Vinyl; One or more unsaturated ethers selected from the group consisting of vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether; At least one unsaturated imide selected from the group consisting of N-phenylmaleimide, N- (4-chlorophenyl) maleimide, N- (4-hydroxyphenyl) maleimide and N-cyclohexylmaleimide; Maleic anhydride, and maleic anhydride such as maleic anhydride and methylmaleic anhydride, but is not limited thereto. Monomers which impart alkali solubility include (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monomethyl maleic acid, 5-norbornene-2-carboxylic acid, mono-2- ((meth) acryloyloxy) ethyl phthalate , Mono-2 - ((meth) acryloyloxy) ethyl succinate, and? -Carboxylic polycaprolactone mono (meth) acrylate. It is not.

The polymerizable compound having an ethylenically unsaturated bond according to an example is not particularly limited as long as it is commonly used in the art. Specific examples thereof include ethylene glycol di (meth) acrylate, (Meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra Propylene glycol di (meth) acrylate having a number of groups of 2 to 14, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, or a mixture thereof, but is not limited thereto .

The coloring agent according to an example is not particularly limited 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) Black (CI 21090), lino 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.

Examples of the photoinitiator include 2,4-trichloromethyl- (4'-methoxyphenyl) -6-triazine, 2 (2'- , 4-trichloromethyl- (4'-methoxystyryl) -6-triazine, 2,4-trichloromethyl- (phenylonyl) -6-triazine, 2,4-trichloromethyl- Tri (4-methoxyphenyl) -6-triazine and 3- {4- [2,4-bis (trichloromethyl) Azine compounds; 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 according to an example is not particularly limited as long as it is commonly used in the art, and specific examples thereof include methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol di Propylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, 2-ethoxypropanol, 2-methoxypropanol, 3-methoxy Butanol, cyclohexanone, 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 glycol monomethyl ether or their mixture It is water, but is not limited to this.

In addition, additives such as a dispersing agent, a dispersion stabilizer, an antioxidant, a surfactant and / or a thermal polymerization inhibitor may be further added as needed within the range not impairing the physical properties of the photosensitive resin composition.

The present invention also provides a photosensitive material produced using the photosensitive resin composition. For example, the photosensitive material may be used for a photosensitive material for a color filter, a photosensitive material for a black matrix, a photosensitive material for an overcoat, a photosensitive material for a column spacer, or a photosensitive material for an insulating material.

Hereinafter, the production method according to the present invention will be described in more detail with reference to examples. 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. In addition, the terms used in the description herein are intended only to describe effective embodiments of the invention and are not intended to limit the invention.

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.

[Synthesis Example 1]

11.3 g of 3-aminopropyltrimethoxysilane and 18.4 g of octadecyl isocyanate were mixed with 30 g of a propylene glycol monomethyl ether acetate solvent, and the mixture was stirred at 80 ° C for 10 hours. ≪ / RTI >

_{^{1 H NMR (500MHz, CDCl 3}} , ppm): 3.55 (9H, s, OCH 3), 3.16 (4H, t, NCH 2), 1.6 (2H, m, CH 2), 1.55 (2H, m, CH 2 ), 1.29 (30H, m, CH 2), 0.96 (3H, t, CH 3), 0.58 (2H, t, SiCH 2)

[Synthesis Example 2]

13.3 g of N- [3- (trimethoxysilyl) propyl] butylamine and 16.7 g of octadecyl isocyanate were mixed with 30 g of a propylene glycol monomethyl ether acetate solvent, and the mixture was stirred at 80 DEG C for 10 hours After stirring, the compound of Synthesis Example 2 was obtained.

_{^{1 H NMR (500MHz, CDCl 3}} , ppm): 3.55 (9H, s, OCH 3), 3.16 (6H, t, NCH 2), 1.6 (2H, m, CH 2), 1.59 (2H, m, CH 2 ), 1.55 (2H, m, CH 2), 1.29 (30H, m, CH 2), 0.96 (6H, t, CH 3), 0.58 (2H, t, SiCH 2)

[Synthesis Example 3]

13.9 g of N- [3- (trimethoxysilyl) propyl] aniline and 16.1 g of octadecyl isocyanate were mixed with 30 g of a propylene glycol monomethyl ether acetate solvent, and the mixture was stirred at 80 DEG C for 10 hours To give the compound of Synthesis Example 3.

_{^{1 H NMR (500MHz, CDCl 3}} , ppm): 7.64 (2H, d, ArH), 7.24 (2H, t, ArH), 7.00 (1H, t, ArH), 3.55 (9H, s, OCH 3), 3.16 _{(4H, t, NCH 2)} , 1.6 (2H, m, CH 2), 1.55 (2H, m, CH 2), 1.29 (30H, m, CH 2), 0.96 (3H, t, CH 3), 0.58 (2H, t, SiCH ₂₎

[Synthesis Example 4]

16.1 g of bis [3- (trimethoxysilyl) propyl] amine and 13.9 g of octadecyl isocyanate were mixed with 30 g of a propylene glycol monomethyl ether acetate solvent, and the mixture was stirred at 80 DEG C for 10 hours , The compound of Synthesis Example 4 was obtained.

_{^{1 H NMR (500MHz, CDCl 3}} , ppm): 3.55 (18H, s, OCH 3), 3.16 (6H, t, NCH 2), 1.6 (4H, m, CH 2), 1.55 (2H, m, CH 2 ), 1.29 (30H, m, CH 2), 0.96 (3H, t, CH 3), 0.58 (4H, t, SiCH 2)

[Synthesis Example 5]

17 g of 1-octadecanol and 13 g of 3-isocyanatopropyltrimethoxysilane were mixed with 30 g of a propylene glycol monomethyl ether acetate solvent, and the mixture was stirred at 80 ° C for 10 hours, The compound of Example 5 was obtained.

_{^{1 H NMR (500MHz, CDCl 3}} , ppm): 4.08 (2H, t, OCH 3), 3.55 (9H, s, OCH 3), 2.96 (2H, t, NCH 2), 1.6 (2H, m, CH 2 ), 1.57 (2H, m, CH 2), 1.29 (30H, m, CH 2), 0.96 (3H, t, CH 3), 0.58 (2H, t, SiCH 2)

[Comparative Synthesis Example 1]

16.9 g of N- [3- (trimethoxysilyl) propyl] butylamine and 13.1 g of decylisocyanate were mixed with 30 g of a propylene glycol monomethyl ether acetate solvent, and the mixture was stirred at 80 DEG C for 10 hours , To obtain the compound of Comparative Synthesis Example 1.

_{^{1 H NMR (500MHz, CDCl 3}} , ppm): 3.55 (9H, s, OCH 3), 3.16 (6H, t, NCH 2), 1.6 (2H, m, CH 2), 1.59 (2H, m, CH 2 ), 1.55 (2H, m, CH 2), 1.33 (2H, t, CH 2), 1.29 (12H, m, CH 2), 0.96 (6H, t, CH 3), 0.58 (2H, t, SiCH 2 )

[Comparative Synthesis Example 2]

13.1 g of 1-decanol and 16.9 g of 3-isocyanatopropyltrimethoxysilane were mixed with 30 g of a propylene glycol monomethyl ether acetate solvent, and the mixture was stirred at 80 DEG C for 10 hours, To obtain the compound of Comparative Synthesis Example 2.

_{^{1 H NMR (500MHz, CDCl 3}} , ppm): 4.08 (2H, t, OCH 2), 3.55 (9H, s, OCH 3), 2.96 (2H, t, NCH 2), 1.6 (2H, m, CH 2 ), 1.57 (2H, m, CH 2), 1.33 (2H, m, CH 2), 1.29 (12H, m, CH 2), 0.96 (3H, t, CH 3), 0.58 (2H, t, SiCH 2 )

[Example 1]

5 g of an alkali-soluble binder resin as a copolymer of benzyl methacrylate / methacrylic acid (molar ratio 70/30, molecular weight 20,000 g / mol, acid value 100 KOH mg / g), green pigment dispersion (CI Pigment Green 7, 20 wt% in PGMEA glycol methyl ether acetate), 0.6 g of photoinitiator OXE-02, 5 g of dipentaerythritol hexaacrylate, 0.2 g of the silane compound synthesized in Synthesis Example 1 and 54.2 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 0.2 g of the silane compound synthesized in Synthesis Example 2 was used instead of the silane compound synthesized in Synthesis Example 1, and the mixture was stirred for about 3 hours to prepare a photosensitive resin composition .

[Example 3]

Except that 0.2 g of the silane compound synthesized in Synthesis Example 3 was used instead of the silane compound synthesized in Synthesis Example 1, and the mixture was stirred for about 3 hours to prepare a photosensitive resin composition .

[Example 4]

Except that 0.2 g of the silane compound synthesized in Synthesis Example 4 was used instead of the silane compound synthesized in Synthesis Example 1, and the mixture was stirred for about 3 hours to prepare a photosensitive resin composition .

[Example 5]

Except that 0.2 g of the silane compound synthesized in Synthesis Example 5 was used instead of the silane compound synthesized in Synthesis Example 1, and the mixture was stirred for about 3 hours to prepare a photosensitive resin composition .

[Comparative Example 1]

Except that 0.2 g of the silane compound synthesized in Comparative Synthesis Example 1 was used in place of the silane compound synthesized in Synthesis Example 1, and the mixture was stirred for about 3 hours to prepare a photosensitive resin composition Respectively.

[Comparative Example 2]

Except that 0.2 g of the silane compound synthesized in Comparative Synthesis Example 2 was used instead of the silane compound synthesized in Synthesis Example 1, and the mixture was stirred for about 3 hours to prepare a photosensitive resin composition Respectively.

[Evaluation of substrate adhesion force]

Each of the photosensitive resin composition solutions prepared in Examples 1 to 5 and Comparative Examples 1 and 2 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 40, 60, and 80 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 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.

The following Table 1 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 value of the remaining minimum pattern is, Which means that the adhesive strength of the substrate is excellent.

Exposure dose 40 mJ / cm 2 60 mJ / cm 2 80 mJ / cm 2 Example 1 10 10 8 Example 2 10 10 8 Example 3 12 10 8 Example 4 12 10 8 Example 5 12 10 8 Comparative Example 1 14 14 12 Comparative Example 2 16 14 12

[Developability evaluation]

Each of the photosensitive resin composition solutions prepared in Examples 1 to 5 and Comparative Examples 1 and 2 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 80 mJ / cm 2 using a high-pressure mercury lamp while maintaining the exposure gap of 200 탆 using a photomask, and then the exposed substrate was developed with a 0.04% by weight KOH aqueous solution for a maximum of 60 seconds Respectively.

The following Table 2 shows evaluation of developability according to the developing time of each of the examples and the comparative examples. When all development to the edge of the substrate was clearly developed, the result was rated "? & △, and when the phenomenon has not yet been completed, X is recorded.

Development time 30 seconds 40 seconds 60 seconds Example 1 ○ ○ ○ Example 2 ○ ○ ○ Example 3 △ ○ ○ Example 4 △ ○ ○ Example 5 ○ ○ ○ Comparative Example 1 X △ ○ Comparative Example 2 X △ ○

As can be seen from the above, the silane compounds of Examples 1 to 5 had an octadecyl group (carbon number of 18) as compared with the silane compounds of Comparative Examples 1 and 2 having a decyl group (carbon number of 10) It can be seen that a fine pattern can be easily formed, and that the pattern is neatly developed without an undeveloped portion at the time of development.

Claims (7)

1. A photoresist adhesion promoter comprising a silane compound satisfying the following formula (1).
[Chemical Formula 1]

(In Formula 1, X is -O- or -N (Z ²⁾ -, and; Y is a direct bond, a substituted or unsubstituted arylene group unsubstituted C6 ~ C20, or a substituted or unsubstituted cycloalkyl ring of the C6 ~ C20 Z ¹ is a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C6-C20 cycloalkyl group or -R ²² Si (R ³³ ) R ⁴⁴ ) (R ⁵⁵ ), Z ² is -H, a substituted or unsubstituted C 1 -C 6 alkyl group, a substituted or unsubstituted C 6 -C 20 aryl group, a substituted or unsubstituted C 6 -C 20 cycloalkyl group, ^{-R 22 Si (R 33) (} R 44) (R 55) a; R ¹ is an alkyl group of C16 ~ C30; R ² and R ²² are independently an alkylene group of C1 ~ C6 from each other; R ^3, R ⁴ , R ⁵ , R ³³ , R ⁴⁴ and R ⁵⁵ are each independently a C 1 to C 6 alkoxy group.)
The method according to claim 1,
In the silane-based compound satisfying the above formula (1), X is -O- or -NH-; Y is a direct bond, a phenylene group, a naphthalene group or a cyclohexylene group; Z ¹ is a propyl group, a butyl group, a phenyl group, a naphthyl group, a cyclohexyl group or -R ²² Si (R ³³ ) (R ⁴⁴ ) (R ⁵⁵ ); R < ¹ > is a C16-C30 alkyl group; R ² and R ²² are each independently a C 1 to C 6 alkylene group; R ³ , R ⁴ , R ⁵ , R ³³ , R ⁴⁴ and R ⁵⁵ independently represent a methoxy group or an ethoxy group.
3. The method of claim 2,
Wherein the silane compound is any one or two or more selected from the following formulas (3) to (5).
(3)

[Chemical Formula 4]

[Chemical Formula 5]

(In the above formulas 3 to 5, a is a real number of 14 to 28, and R is a methyl group or an ethyl group.)
A photosensitive resin composition comprising the adhesion promoting agent for a photoresist according to any one of claims 1 to 3.
5. The method of claim 4,
The photoresist adhesion promoter is contained in an amount of 0.01 to 5% by weight based on the total weight of the composition.
5. The method of claim 4,
The photosensitive resin composition preferably contains 1 to 20% by weight of an 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% by weight % Of a photoinitiator and 35 to 95% by weight of a solvent.
A photosensitive material produced by using the photosensitive resin composition of claim 4.