TW201346445A - Photosensitive polymer resin for thick layer and resin composition including the same - Google Patents

Abstract

There are provided a photosensitive polymer resin for a thick layer and a resin composition including the same, and more particularly, a photosensitive polymer resin for a thick layer and a resin composition including the same, in which the photosensitive polymer resin is appropriate for photofabrication, such as bump formation, wiring formation, and processing and manufacturing of a interlayer-insulation layer, a circuit protective film, and precision parts, which are performed in processes for manufacturing circuits boards and for mounting semiconductors or electronic parts on circuits boards. The photosensitive polymer resin is a polymer resin including a divalent fluorene derivative and a tetravalent organic group at a main chain thereof, and has a specific acetal protecting group. The polymer resin may be used as a positive photosensitive resin composition by being mixed with a photoacid generator and a photo active compound or as a negative resin composition by being mixed with a photopolymerization initiator.

Description

Photosensitive polymer for thick layer and composition containing the same

The present invention relates to a thick layer of photosensitive polymer resin and a resin composition comprising the same, and more particularly to a photosensitive polymer resin for a thick layer and a resin comprising the same a resin composition, wherein the photosensitive polymer resin is suitable for photofabrication, such as bump formation, wiring formation, and an interlayer insulating layer, a circuit protection film, and manufacturing and processing of precision parts, Such manufacturing processes are performed in the manufacture of circuit boards and in the installation of semiconductor or electronic components on a circuit board.

The current mainstream etch processing of microfabrication technology is a technical general term for manufacturing a variety of precision components, such as semiconductor packages, by applying a photosensitive resin composition to a The surface of the article to be processed is formed by forming a film, patterning the film via photolithography, and using the film as a mask to electroform the film by etching, electrolytic etching, and electroplating.

In recent years, with the miniaturization of electronic devices, the high-density mounting technology of semiconductor packaging technology has progressed remarkably. Therefore, there is a need for a packaged multi-pin thin film mounting, and miniaturized package size, bare wafer mounting by a flip chip method, and the like are attracting attention. In this high-density mounting technique, for example, a connection terminal, a projection electrode protruding from the package, such as a bump, or a redistribution for mounting and extending from a peripheral point on the wafer A metal post connected between the ends of the wiring of the redistributed wiring is arranged on a substrate at a fixed density.

The desired item for forming a photosensitive resin composition such as a bump is as follows: the photosensitive resin composition should be used to form a film having a thickness of at least 20 μm; the patterned film pair A substrate should have adhesiveness; when plating is formed to form a bump, it should have plating resistance and good wetting property to a plating solution; or, after performing plating, by using one The detaching solution should easily stratify the membrane. Furthermore, in order to meet the fine pitch of the bumps associated with high densification, the material used to form the bumps should have high resolution and improved patterning, wherein The sidewalls of the resist pattern are almost vertical. In addition, the patterned film is required to have no cracks caused by cleaning and drying during plating or after plating. When cracks appear on the film during plating, the precipitate is plated on the undesired parts to cause a short circuit. When cracks appear on the film after plating and plating is performed again due to insufficient plating thickness, plating may precipitate in the crack portion. Therefore, a suitable shape cannot be formed.

As a photoresist for a thick layer, Japanese Patent Application Laid-Open No. 2002-258479, U.S. Patent No. 3,634, 082, and Japanese Patent Application Laid-Open No. 71-16049 disclose a positive for forming bumps or wiring. A photosensitive resin composition having a compound comprising a quinonediazide group. However, the photosensitive resin composition composed of a compound including a novolac resin and a naphthoquinone diazide group and other additives is not satisfactory, especially regarding the generation of cracks. . In other words, it is disadvantageous in that the film of the photosensitive resin composition is weak, so that cracks are easily formed in the film, and the adhesiveness is insufficient, so that the film is delaminated from a substrate.

Further, in the plating, the surface of the pattern formed by the photosensitive resin composition should have sufficient wetting properties for a plating solution. However, this property cannot be obtained from a general composition of a novolak resin, so an additional descum procedure is usually applied to the pattern via ion plasma treatment prior to plating to hydrophilicize the surface. Therefore, the production yield is therefore reduced by an additional procedure.

[Patent Document]

Patent Document 1: Japanese Patent Application Early Disclosure No. 2002-258479

Patent Document 2: US Patent No. 3364082

Patent Document 3: Japanese Patent Application Publication No. 71-16049

In order to solve the above problems in the prior art, it is an object of the present invention to provide a photosensitive polymer resin and a resin composition comprising the same, wherein, particularly for a thick layer, the photosensitive polymer resin is The substrate has excellent adhesion and excellent resolution, and when the photosensitive polymer resin is used, cracks are not generated and a process of removing the residue is not required.

Furthermore, another object of the present invention is to provide a photosensitive polymer resin and a resin composition comprising the resin, wherein the photosensitive polymer resin can be used as a substitution ratio by controlling an acetal protecting group of the resin A negative resin composition can also be used as a positive resin composition.

In order to achieve the above object, an exemplary embodiment of the present invention provides a photosensitive resin comprising a repeating unit represented by the following Chemical Formula 1:

In the above Chemical Formula 1, n is an integer of 1 to 30, m is an integer of 1 to 50, and R ₁ is , ,or (wherein R ₂ and R ₃ are each an alkyl group, an allyl group, an aryl group, an arylalkyl group, or a cycloalkyl group having 1 to 30 carbon atoms, and preferably, a one Methyl or monoethyl), and further, in the above Chemical Formula 1, X is a fluorene derivative compound and Y is a tetravalent organic group.

Further, in the above Chemical Formula 1, X is preferably represented by the following Chemical Formula 2 or Chemical Formula 3:

In the above Chemical Formulas 2 and 3, R ₄ is a hetero element such as O, F, N, or S.

Further, in the above Chemical Formula 1, Y is a tetravalent organic group having 1 to 30 carbon atoms, and is preferably a system , , , ,or .

According to the present invention, the polymer resin preferably has an average molecular weight of 2,000 to 50,000 and a degree of dispersion of preferably 1.0 to 5.0.

Furthermore, the present invention provides a negative photosensitive resin composition comprising the polymer resin. Preferably, the photosensitive resin composition further comprises an ethylenically unsaturated bond compound and a photopolymerization initiator.

Further, the present invention provides a device comprising a resin cured pattern formed of the resin composition. The photosensitive polymer resin composition can be applied to manufacture of a semiconductor device, a device for an LCD, a device for an OLED, a device for a solar cell, a device for a flexible display, and the like. A device for a touch screen or a device for nanoimprint lithography.

Further, the present invention provides a positive photosensitive resin composition comprising the polymer resin. Preferably, the photosensitive resin composition further comprises a photoacid generator and a photoactive material.

Further, the present invention provides a device comprising a resin cured pattern formed of the resin composition. The photosensitive polymer resin composition can be applied to manufacture of a semiconductor device, a device for an LCD, and an OLED device. A device for a solar cell, a device for a flexible display, a device for a touch screen, or a device for nanoimprint technology.

The photosensitive resin composition according to the present invention has high resolution, excellent adhesion to a substrate, and prevention of cracks on the film. Further, by using the photosensitive polymer resin according to the present invention, the defects of the connection projection formed in the plating process are prevented from being pushed by a pattern shape, and thus the size of the critical dimension deviation (CD bias) is small. Moreover, the process of removing the residue on the surface of the hydrophilized film during the drying process after development is not necessary, so the process is simple. Meanwhile, the photosensitive polymer resin according to the present invention can be used for a negative photosensitive resin composition and a positive photosensitive resin composition via a method of controlling a conversion ratio of an acetal protecting group.

1 is a representative GPC spectrum of a polymer resin according to the present invention; FIG. 2 is a photograph showing a thick layer hole pattern obtained from the negative composition of Example 1-1; A photograph of a thick layer pattern obtained from the composition of Comparative Example 1; Fig. 4 is a photograph showing a thick layer pattern obtained from the positive composition of Example 2-1; A thick layer of pores obtained from the composition of Comparative Example 2 is shown Photograph of the pattern; and Fig. 6 is a photograph showing the plating of gold (Au) on the thick hole pattern obtained from the negative composition of Example 1-1.

[Best way]

The present invention relates to a photosensitive polymer resin, and a photosensitive polymer resin composition for forming a thick layer, wherein the composition includes the photosensitive polymer resin. The photosensitive polymer resin is a polymer resin comprising a divalent anthracene derivative in its main chain and comprising a specific acetal protecting group. The polymer resin can be used as a positive photosensitive resin composition by mixing with a photoacid generator or a photoactive material, or can be used as a negative photosensitive resin by mixing with a photopolymerization initiator. The composition is used.

Hereinafter, the present invention will be described in detail.

Photosensitive polymer resin

The photosensitive polymer resin includes a repeating unit represented by the following Chemical Formula 1. The polymer resin comprises a divalent europium derivative in the main chain. (xanthene) a polymer resin having a structure, a tetravalent organic group, and an acid decomposable acetal protecting group.

In the above Chemical Formula 1, R ₁ is an acid-decomposable acetal protecting group, and is preferably a system , ,or (wherein R ₂ and R ₃ are each an alkyl group, an allyl group, an aryl group, an arylalkyl group, or a cycloalkyl group having 1 to 30 carbon atoms, and preferably a monomethyl group Or monoethyl; R ₂ and R ₃ may be the same or different from each other).

In the above Chemical Formula 1, n is an integer of 1 to 30 and m is an integer of 1 to 50. Preferably, the values of n and m are selected from the above range such that the average molecular weight of the polymer resin is from 2,000 to 50,000 and preferably from 2,000 to 25,000. When the molecular weight of the polymer resin is less than 2,000, since the developing speed is fast, there is an unfavorable situation in which it is difficult to form a pattern and it is difficult to obtain a desired remaining rate. Meanwhile, when the average molecular weight exceeds 50,000, it may be difficult to obtain development by a developing solution. It is preferred that the polymer resin has a dispersity of from 1.0 to 5.0. When the degree of dispersion exceeds 5.0, there may be an unfavorable situation in which the resolution is lowered.

In the above Chemical Formula 1, X is preferably a divalent anthracene derivative represented by the following Chemical Formula 2 or Chemical Formula 3 structure. However, the invention is not limited thereto.

[Chemical Formula 3]

In the above Chemical Formula 2 and Chemical Formula 3, R ₄ is a hetero element such as O, F, S, or N, and is preferably an oxygen atom.

In the above Chemical Formula 1, Y is a tetravalent organic group having 1 to 30 carbon atoms, and is preferably selected from the group consisting of: , , , ,or . However, the invention is not limited thereto.

In the conventional photosensitive resin composition using a resin containing a novolac resin or a naphthoquinonediazide group, since the film system is weak, there is a disadvantage that it is easily broken and the adhesiveness is insufficient. In another aspect, the photosensitive polymer resin according to the present invention comprises an excellent chemical property (e.g., photosensitivity and heat resistance) in the main chain. The structure thus forms a thick layer with excellent adhesion and minimal cracking. Further, since the surface of the pattern formed using the photosensitive polymer resin according to the present invention exhibits a sufficient wet property, it is not necessary to carry out a degreasing process like a novolac resin, thereby improving process efficiency.

2. Negative photosensitive resin composition

The present invention provides a negative photosensitive resin composition comprising the polymer resin. The resin composition further includes, in addition to the polymer resin, a photopolymerization initiator, a compound having an ethylenically unsaturated bond, an additive, and an organic solvent.

The photopolymerization initiator acts on the polymerization of the starting crosslinking monomer by a wavelength such as visible light, ultraviolet light, or far ultraviolet light. Examples of the photopolymerization initiator include acetophenones such as acetophenone, 2,2-diethoxyacetophenone, p-dimethylphenylethyl P-dimethylacetophenone, p-dimethyl aminopropiophenone, dichloroacetophenone, trichloroacetophenone, and tert-butyl acetophenone ( P-tert-butylacetophenone), benzophenones such as benzophenone, 2-chlorobenzophenone, and p,p'-bisdimethylamino Phenyl ketone (p,p'-bisdimethylaminobenzophenone), benzoin ethers such as benzyl, benzoin, benzoin methylether, benzoin Benzoin isopropylether, benzoin isobutylether, sulfur compounds such as benzyldimethyl ketal, sulfur (thioxanthene), 2-chlorosulfur (2-chlorothioxanthene), 2,4-diethyl sulphide (2,4-diethylthioxanthene), 2-methylsulfur (2-methylthioxanthene), with 2-isopropylthio (2-isopropyl thioxanthene), anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone And 2,3-diphenyl anthraquinone, organic peroxides such as azobisisobutyronitrile, benzoyl peroxide, With cumene oxide, thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzoxazole 2-mercaptobenzothiazole, an imidazolyl compound such as 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)-imidazolyl dimer (2-(o-chlorophenyl) )-4,5-di(m-methoxyphenyl)-imidazolyl dimer), three Triazine compounds such as p-methoxy III (p-methoxytriazine) having three halo-methyl groups Compounds such as 2,4,6-parade (trichloromethyl)-symmetric three (2,4,6-tris(trichloromethyl)-s-triazine), 2-methyl-4,6-bis(trichloromethyl)-symmetric three (2-methy1-4,6-bis(trichloromethyl)-s-triazine), 2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl) - Symmetrical three (2-[2-(5-methylfurane-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine), 2-[2-(furan-2-yl)vinyl]-4, 6-bis(trichloromethyl)-symmetric three (2-[2-(furane-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine), 2-[2-(4-diethylamino-2-methylphenyl) Vinyl]-4,6-bis(trichloromethyl)-symmetric three (2-[2-(4-diethylamino-2-methylphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine), 2-[2-(3,4-dimethoxyphenyl)vinyl -4,6-bis(trichloromethyl)-symmetric three (2-[2-(3,4-dimethoxyphenol)ethenyl]-4,6-bis(trichloromethyl)-s-triazine), 2-(4-methoxyphenyl)4,6-bis(trichloromethyl) )-symmetric three (2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine), 2-(4-ethoxystyryl) 4,6-bis(trichloromethyl)-symmetric three (2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine), with 2-(4-n-butoxyphenyl) 4,6-bis(trichloromethyl)-symmetric three (2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine), and aminoketone compounds such as 2-benzyl-2-dimethylamino-1-(4- 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butane-1-one.

The photopolymerization initiator is contained in an amount of from 1 part by weight to 30 parts by weight, and preferably from 5 parts by weight to 20 parts by weight, per 100 parts by weight of the polymer resin.

The compound having an ethylenically unsaturated bond may generally be a crosslinking monomer having at least two ethylenic double bonds, and may include a multifunctional (meth)acrylic-based monomer and Oligomer such as ethylene glycol dipropylene Ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate Ester, tetraethylene glycol dimethacrylate, butylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, trimethylolpropane triacrylate, Trimethylolpropane trimethacrylate, tetramethylolpropane tetraacrylate, tetramethylolpropane tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, Neopentyl alcohol tetraacrylate, neopentyl alcohol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dioxane Tetraol hexamethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, and cardoepoxy diacrylate; polyester (methyl Acrylate A polyester prepolymer obtained by a condensation reaction of a polyvalent alcohol with a unit acid or a polybasic acid and (meth)acrylic acid, and a urethane (meth) acrylate by having two isocyanate groups a compound obtained by reacting a compound with a polyol group and then reacting with (meth)acrylic acid; and an epoxy (meth)acrylic acid obtained by reacting (meth)acrylic acid with an epoxy resin At least one of the ester resins, such as a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a phenol or a cresol novolak type ring Oxygen resin, resol-type epoxy resin, triphenolmethane-type epoxy resin, polycarboxylic acid polyglycidyl ester, diversified An alcohol polyglycidyl ester, an aliphatic or cycloaliphatic epoxy resin, an amine-based epoxy resin, and a dihydroxybenzene type epoxy resin. Further, in view of exposure sensitivity and the like, a polyfunctional (meth)acrylic monomer is preferably used.

The content of the compound having an ethylenically unsaturated bond is preferably from 10 parts by weight to 200 parts by weight, and more preferably from 30 parts by weight to 150 parts by weight, per 100 parts by weight of the polymer resin. When the content is less than 30 parts by weight, there is a disadvantage that it is difficult to realize a pattern due to a low degree of curing with the photosensitive resin. On the other hand, when the content exceeds 150 parts by weight, there may be an unfavorable situation in which the hardness and resolution of the formed pattern are lowered.

Any organic solvent may be used as long as the polymer can be dissolved in the organic solvent, such as an acetate type, an ether type, a glycol type, a ketone type, an alcohol type, and a carbonate type used in a typical photopolymerization composition. Solvent. Examples of the organic solvent are at least one selected from the group consisting of ethyl cellosolve, butyl sirlo, ethyl carbitol, butyl carbitol, and ethyl carbene. Alcohol acetate, butyl carbitol acetate, ethylene glycol, cyclohexanone, cyclopentanone, 3-ethoxypropionic acid, N,N-dimethylacetamide, N-methylpyrrolidone (N-methylpyrrolidone), N-methylcaprolactame, and the like.

The solvent is included in an amount of from 20 parts by weight to 95 parts by weight, and preferably from 30 parts by weight to 90 parts by weight, per 100 parts by weight of the total composition. When the content of the solvent is less than 20 parts by weight, it is difficult to form a film by using a conventional coating method, and when the content of the solvent exceeds 95 parts by weight, it may not be obtained after coating. A film having a desired thickness is obtained.

In the present invention, an additive may be used if necessary. Examples of the additive may include a heat stabilizer, a thermal crosslinking agent, a photocurable accelerator, a surfactant, a base quencher, an antioxidant, an adhesive preparation. (adhesion preparation) an adhesion promoter, a light stabilizer, an antifoaming agent, and the like. The above additives may be used singly or in combination as needed.

As a representative additive of the above additives, the adhesion promoter is a component having a function of improving the adhesion strength to a substrate, and an example of the adhesion promoter preferably includes a decane coupling having a reactive functional group. The reactive functional group is a carboxyl group, a methacryl group, a vinyl group, an isocyanate group, and an epoxy group. Specific examples of the adhesion promoter may include one or more selected from the group consisting of: trimethoxysilyl benzoate, γ-methylpropenylpropyltrimethoxydecane (γ-) Methacryloylpropyltrimethoxy silane), vinyltriacetoxy silane, vinyl trimethoxy decane, γ-isocyanate propyltriethoxy silane, γ-glycidoxypropyl Γ-glycidoxypropyltrimethoxy silane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxy silane. The content of the adhesion promoter is preferably from 0.01 part by weight to 10 parts by weight per 100 parts by weight of the polymer resin.

The surfactant has an improved coating property and applicability of the substrate. A component of quality, uniformity, and stain removal function. Examples of the surfactant may include one selected from the group consisting of one or a combination of two or more: a monofluorosurfactant, a monooxane surfactant, and a nonionic surfactant. The surfactant is preferably contained in an amount of from 0.01 part by weight to 10 parts by weight per 100 parts by weight of the polymer resin.

Since the negative photosensitive resin composition has excellent properties such as adhesive strength, heat resistance, insulation, smoothness, and chemical resistance, the negative photosensitive resin composition according to the present invention is suitable for use in photosensitive etching processing, such as Bump formation, wiring formation, and interlayer insulation, a circuit protection film, and fabrication and processing of precision components are performed in a process for manufacturing a circuit board and mounting a semiconductor or electronic component on a circuit board.

3. Positive photosensitive resin composition

The present invention provides a positive photosensitive resin composition comprising the polymer resin. The resin composition further comprises, in addition to the polymer resin, a photoacid generator or a photoactive compound, an additive, and an organic solvent.

The photoacid generator is a compound which generates an acid by irradiation with actinic light or radiation. The photoacid generator has a suitable degree of light absorption at a wavelength of from 250 nm to 400 nm. Any kind of photoacid generator can be used as long as it does not adversely affect the formation of the film. Examples of the photoacid generator may include one selected from the group consisting of two or more of the following: a diazonium salt system, an onium salt system, a phosphonium salt system, a phosphonium salt system, and a quinone imine-sulfonate. System, sulfonium-sulfonate, diazo-diguanide, diterpenoid, n-benzyl sulfonate, and a compound. It is preferably selected from the group consisting of compounds represented by the following Chemical Formula 4 and Chemical Formula 5:

The photoacid generator is preferably contained in an amount of from 0.1 part by weight to 15 parts by weight, and more preferably from 1 part by weight to 10 parts by weight, per 100 parts by weight of the polymer resin. When the content of the photoacid generator is 0.1 part by weight or less, it is difficult to generate an acid, and when the content of the photoacid generator exceeds 15 parts by weight, precipitation may occur due to a decrease in solubility in the composition.

Further, the positive photosensitive resin composition according to the present invention further contains an organic solvent and an additive as needed. The content thereof is the same as that of the negative photosensitive resin composition in the above item 2.

4. Method of forming a thick film

A thick layer of photoresist can be formed using the negative or positive resin composition according to the present invention. Methods of forming the thick layer can include, but are not limited to, methods known in the related art. Examples of the method may include a coating method such as spin coating, dip coating, roll coating, screen coating, flow coating, screen printing, or drop casting. Thereafter, borrowed in a pre-baking program The solvent is volatilized by applying vacuum, infrared rays, or heat. Next, as a selective lithography process, it is subjected to a quasi-molecular laser, far ultraviolet light, ultraviolet light, visible light, electron beam, X-ray, g-ray (wavelength of 436 nm), i- The radiation (wavelength of 365 nm), h-ray (wavelength of 405 nm) or the aforementioned mixed radiation. The exposure can be carried out using an exposure method such as contact, proximity, or projection.

The composition may use an aqueous alkaline solution as a developing solution. The alkaline developing solution may comprise aqueous ammonia or an aqueous solution of a fourth-grade ammonium hydroxide such as tetramethylammonium hydroxide, and tetraethylammonium hydroxide, or an aqueous amine solution such as ammonia, ethylamine, diethylamine, and Ethylamine. Preferably, an aqueous solution of tetramethylammonium hydroxide (TMAH) is used.

The invention will be described in more detail with reference to the following specific examples. The following examples are merely illustrative of the invention and are not intended to limit the scope of the invention.

Example 1. Synthesis of polymer resin [Synthesis Example 1]

Use the following method to synthesize one (In the above chemical formula 1, the X system Y system A polymer resin of an acetal protecting group of R ₂ -based methyl group and R ₃ -ethyl group).

200 g of propylene glycol monoethylacetate was added as a solvent to a flask equipped with a stirrer, a thermometer, an air bubble device, and a reflux condenser; thereafter, 90 g was added (spiral ring connection [茀- 9,9'- -3',6'-diylbis(oxy)) bis(2-hydroperoxypropane-3,1-diyl) diacrylate ((spiro[fluorene-9,9'-xanthene]- 3',6'-diylbis(oxy))bis(2-hydroperoxypropane-3,1-diyl)diacrylate) and 0.09 g of tetrabutylammonium chloride; the temperature of the flask was increased to 110 °C. Add 47 grams of [5,5'-bi-isobenzofuran]-1,1',3,3'-tetraketone ([5,5'-biisobenzofuran]-1,1',3,3'-tetraone ) to the above solution. The reaction solution was reacted at 110 ° C for 12 hours.

After the temperature of the reaction solution was cooled to room temperature (25 ° C), 0.4 g of a parasulfonic acid pyridinium salt was further added. 6.84 g of ethyl vinyl ether diluted with 15 g of the solvent was slowly dropped into the reaction solution at room temperature. The reaction solution was reacted at room temperature for 8 hours, and thereafter a PGC was used to confirm that the ethyl vinyl ether had been completely consumed (Fig. 1). Based on polystyrene as a standard material, the compound has a weight average molecular weight of 11,000.

[Synthesis Example 2]

A polymer resin was synthesized in the same manner as in Synthesis Example 1, except that the application amount of ethyl vinyl ether as an acetal protecting group was changed to 3.42 g. Its weight average molecular weight is 11,500.

[Synthesis Example 3]

A polymer tree was synthesized in the same manner as in Synthesis Example 1. The amount of the lipid, but [5,5'-biisbenzofuran]-1,1',3,3'-tetraone was changed to 23.5 g. Its weight average molecular weight is 7,800.

[Synthesis Example 4]

A polymer resin was synthesized in the same manner as in Synthesis Example 2 except that the application amount of [5,5'-biisbenzofuran-1,1',3,3'-tetraone was changed to 23.5 g. Its weight average molecular weight is 8,200.

[Synthesis Example 5]

A polymer resin was synthesized in the same manner as in Synthesis Example 1, except that it was used. As an acetal protecting group. Its weight average molecular weight is 12,300.

[Synthesis Example 6]

A polymer resin was synthesized in the same manner as in Synthesis Example 2 except that it was used. As an acetal protecting group. Its weight average molecular weight is 12,600.

[Synthesis Example 7]

A polymer resin was synthesized in the same manner as in Synthesis Example 3 except that it was used. As an acetal protecting group. Its weight average molecular weight is 8,600.

[Synthesis Example 8]

A polymer resin was synthesized in the same manner as in Synthesis Example 4 except that it was used. As an acetal protecting group. Its weight average molecular weight is 8,700.

The structural series of the synthesized polymer resins are shown in Table 1 below.

2. Preparation of negative resin composition [Example 1]

The negative-type compositions of Examples 1-1 to 1-6 were each obtained by using the polymer resins prepared in Synthesis Examples 2 to 4 and 6 to 8. 50 parts by weight of the polymer resin synthesized in Synthesis Examples 1 to 6 and 15 parts of M500 (Miwon Specialty Chemical Co., Ltd.) were added as an ethylenic unsaturation at room temperature. The key compound, 7 parts of Irgarcure TPO (BASF) as a photopolymerization initiator, 3-ethoxypropionic acid ethyl ester as an organic solvent, and 3 parts KBM 403 (SHINETSU) was used as an adhesion promoter, stirred for 6 hours, filtered through a 5.0 micron filter, and then vacuum degassed to prepare a negative composition. The composition had a solids content of 50%. The series of components used in Examples 1-1 to 1-6 are listed in Table 3 below.

3. Preparation of positive resin composition [Embodiment 2]

The positive type compositions of Examples 2-1 to 2-8 were each obtained by using the polymer resins prepared in Synthesis Examples 1 to 8. 50 parts by weight of the polymer resin synthesized in Synthesis Examples 1 to 8 and 5 parts by weight of 1,3-di- oxy-1H-benzo[de]isoquinoline-2 (3H) were added at room temperature. )--trifluoromethanesulfonate (1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl trifluoro Methanesulfonate) as a photoacid generator, ethyl 3-ethoxypropionate as an organic solvent, and 3 parts of KBM 403 (Shin-Etsu) as an adhesion promoter, stirred for 6 hours, filtered with a 5.0 micron filter Then, it was vacuum degassed to prepare a positive composition. The composition had a solids content of 50%. The composition table series used in Examples 2-1 to 2-8 are shown in Table 4 below.

[Comparative Example 1]

A negative photosensitive resin composition was prepared using the same composition as in Example 1, except that a propylene-based polymer resin having a weight average molecular weight of 13,000 was used instead of the polymer resin of Synthesis Example 1, which was a propylene-based polymer resin. By Prepared in a solvent of ethyl 3-ethoxypropionate at a solid content of 50%, 30 parts by weight of benzyl methacrylate, 10 parts by weight of methyl methacrylate, and 10 parts by weight of methacrylic acid. And got it.

[Comparative Example 2]

By using 50 parts by weight of a novolac resin having a weight average molecular weight of 40,000 as a novolak resin and 20 parts by weight of PAC (photoactive compound) including a naphthoquinonediazide group and using 3-ethoxy group Ethyl propionate was used as a solvent to prepare a composition having a solid content of 50%.

4. Formation of thick layers

The photosensitive resin compositions obtained in Examples 1 and 2 and Comparative Examples 1 and 2 were applied to a tantalum wafer using a spin coater at 1300 to 1800 rpm for 35 seconds, followed by heating The plate was dried at 90 ° C for 360 seconds. Using an ultrahigh pressure mercury lamp as a light source, the dried photosensitive resin composition is exposed at 1,000 mJ through a predetermined mask; and rotated and developed in a TMAH 2.38% developing solution at 300 ° C for 300 seconds; Then clean. After washing and drying, the composition was baked at 150 ° C for 300 seconds to obtain a pattern. The following test was carried out using the obtained pattern.

5. Evaluation of nature

The properties of the thick layer obtained thereby were evaluated.

(1) Resolution

In the above procedure, the initial film thickness of the substrate formed by a patterning process after coating is 25 micrometers, and the resolution of the substrate is observed by an electron microscope. degree.

The resolutions shown as ◎, ○, △, and × have the following meanings:

◎: A hole pattern of 30 μm was analyzed.

○: A hole pattern of 40 μm was analyzed.

△: A hole pattern of 50 μm was not resolved, but a hole pattern of 80 μm was resolved.

×: A hole pattern of 80 μm was not resolved.

(2) Crack resistance

The patterned substrate obtained by the same method as the resolution test was immersed in a cyan gold plating solution at 46 ° C for 1200 seconds, washed with purified water, and then dried in a rotary dryer. After the substrate was dried for 80 hours, the pattern of the substrate was accurately observed using an electron microscope, and then it was confirmed whether or not cracks occurred.

The crack resistance lines shown as ○, △, and × have the following meanings:

○: No cracks.

△: There are a few cracks.

×: Cracks throughout the pattern were observed.

(3) Critical size deviation

A photoresist pattern having a predetermined film thickness formed on the wafer having a gold sputtered surface in the same manner as the resolution test, followed by the gold plating treatment in a cyanide fund plating solution at 46 ° C It was carried out at 0.6 amps per square metre for 1200 seconds. The plated substrate is subjected to water washing followed by spin drying to obtain a substrate having a plated portion between the composition patterns. Observing the electron using an electron microscope A pattern image of the substrate, followed by a shape of a gold bump.

The shape of the gold bumps shown as ○, △, and × has the following meanings:

○: There was no change in shrinkage from the film pattern of the composition, and the size of the gold bump was the same as the hole size of the resolution test.

△: There was shrinkage of the film pattern of the composition, and the size of the gold bump was changed within 1 micrometer as compared with the standard.

X: There is shrinkage of the film pattern of the composition, and the shape size of the gold bump is at least 1 μm larger than the standard.

(4) PR separationability.

The patterned substrate obtained by the same method as the resolution test was immersed in a mixed solution of 50%/50% dimethyl hydrazine and N,N'-dimethylformamide at room temperature. The composition film was separated by 5 minutes. Observe its shape.

The separation results shown as ○, △, and × have the following meanings:

○: There is no residual pattern or residual film on the surface of the substrate.

△: There is no residual pattern on the surface of the substrate, but there is a residual film.

×: There is a residual pattern on the surface of the substrate.

Among the above results, the results regarding sensitivity, residual ratio, and adhesion are listed in Tables 5 and 6 below.

[Table 5] Results of evaluating the properties of negative compositions

From the results of the above Tables 5 and 6, it can be confirmed that the polymer resin according to the present invention can control the resolution depending on its use as a negative or positive type. For example, as in the synthesis of the compounds of Examples 1 and 5, in the case of a high content of ethyl vinyl ether-based acetal protecting group, when applied to a negative composition, the resolution is lowered, and thus It is preferably applied to a positive composition.

Fig. 2 is a photograph showing a pattern of a hole layer obtained by a negative composition according to Example 1-1, and it can be confirmed that the composition according to Comparative Example 1 shown in Fig. 3 The hole pattern of the thick layer has excellent resolution when compared to the hole pattern of the thick layer obtained. Further, Fig. 4 is a photograph showing a pattern of a hole layer obtained by a positive composition according to Example 2-1, and it can be confirmed that when it is thick layer obtained from the composition according to Comparative Example 2 The hole pattern of the thick layer has excellent resolution when compared to the hole pattern.

At the same time, the resin composition according to the present invention has excellent crack resistance, so that a stable bump can be formed. In addition, the film has excellent strength, so that after plating, the numerical stability of the bump can be ensured. After pattern development, the surface of the film is modified to improve the spreadability of the plating solution in a thermal drying process, thereby forming a stable bump. Figure 6 is a view showing a thick layer of pores obtained from the negative composition according to Example 1-1. A photo of the gold plating on the pattern, and it can be confirmed that a solid bump has been formed.

Claims (13)

A photosensitive polymer resin comprising a repeating unit represented by the following Chemical Formula 1: Wherein n is an integer from 1 to 30, m is an integer from 1 to 50, and R ₁ is , ,or (wherein R ₂ and R ₃ are each an alkyl group, an allyl group, an aryl group, an arylalkyl group, or a cycloalkyl group having 1 to 30 carbon atoms), and the X system is a divalent fluorene. a fluorene derivative compound, and a Y-systemic tetravalent organic group. The polymer resin of claim 1, wherein the X system is represented by the following Chemical Formula 2 or Chemical Formula 3: [Chemical Formula 2] Wherein R ₄ is O, F, N or S. The polymer resin of claim 1, wherein the Y system , , ,or . The polymer resin of claim 1, wherein the polymer resin has an average molecular weight of from 2,000 to 50,000. The resin composition of claim 1, wherein the polymer resin has a degree of dispersion of from 1.0 to 5.0. A negative-type photosensitive resin composition comprising the polymer resin according to any one of claims 1 to 5. The photosensitive resin composition of claim 6, wherein the photosensitive resin composition further comprises an ethylenically unsaturated bond compound and a photopolymerization initiator. An organic device comprising a resin curing pattern formed from the photosensitive resin composition of claim 6. The organic device of claim 8, wherein the organic device is a semiconductor device, a device for a liquid crystal display (LCD), a device for an organic light emitting diode (OLED), a device for a solar cell, A device for a flexible display, a device for manufacturing a touch screen, or a device for nanoimprint lithography manufacturing. A positive-type photosensitive resin composition comprising the polymer resin according to any one of claims 1 to 5. The photosensitive resin composition of claim 8, wherein the photosensitive resin composition further comprises a photoacid generator. An organic device comprising a resin cured pattern formed of the photosensitive resin composition of claim 10. The organic device of claim 12, wherein the organic device is a semiconductor device, a device for an LCD, a device for an OLED, a device for a solar cell, a device for a flexible display, and a device A device for manufacturing a touch screen or a device for manufacturing nano imprint technology.