KR20040035345A - Photopolymerizable Resin Composition For Sandblast Resist and photosensitive film laminate comprising the same - Google Patents

Abstract

The present invention relates to a photosensitive resin composition for sandblast resist, which is an alkali-soluble binder polymer, wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ or R ₆ is H, , Cellulose derivatives represented by the formula (1); R ₁ , R ₂ , R ₃ , R ₄ , R ₅ or R ₆ are H, , Cellulose derivatives represented by the formula (1); R ₁ , R ₂ , R ₃ , R ₄ , R ₅ or R ₆ are H, (m is an integer of 3 to 10), Cellulose derivatives represented by the formula (1); And R ₁ , R ₂ , R ₃ , R ₄ , R ₅ or R ₆ are H, (l is an integer from 2 to 10), , When using a cellulose derivative selected from the cellulose derivatives represented by the formula (1), the dry film resist including the same having excellent reactivity, resolution, adhesion, and sandblasting resistance is used for the sandblast resist used in the manufacture of the PDP lower plate. As the adhesion between the sandblast resist and the partition material can be strengthened, and the adhesion between the partition material is remarkably improved, it is possible to obtain an excellent effect of improving adhesion to the white lip material as well as the black lip material.

In the above formula, the total molecular weight of the entire molecule is 30,000 to 100,000.

Description

Photopolymerizable Resin Composition For Sandblast Resist and photosensitive film laminate comprising the same

The present invention relates to a photosensitive resin composition for sandblast resist and a photosensitive film comprising the same, and more particularly, by using a specific cellulose derivative as a binder polymer, a photosensitive resin composition having excellent reactivity, resolution, adhesion, and resistance to sandblasting. And a photosensitive film obtained by using the same.

Dry film resists are widely used as a basic material for circuit patterning in printed circuit board manufacturing, and their application ranges are being expanded in recent years. Efforts are underway to convert many of the areas previously used in liquid resists to dry film resists, especially in IC packaging, lead frame or ball grid alley (BGA) processes. ought. Recently, dry film resists have been used in patterning and partition wall formation processes of indium tin oxide (ITO), which are transparent electrodes, in the production of plasma display panels (PDPs).

Looking at the process of forming the partition wall of the PDP (Plasma Display Panel) lower plate using the dry film resist, the dry film resist is laminated using a heating roller on the PDP (Plasma Display Panel) material on which the partition material is printed. In this process, the photoresist layer of the dry film resist is laminated on the partition material while the protective film of the dry film resist is peeled off using a laminator. In general, lamination proceeds at a speed of 0.5 to 3.5 m / min, a temperature of 100 to 130 ° C., and a heating roll pressure of 10 to 90 psi.

After the lamination process, the glass substrate is left for at least 15 minutes to stabilize the substrate, and then exposed to the photoresist of the dry film resist using a photomask having a desired circuit pattern. In this process, when ultraviolet rays are irradiated to the photomask, the photoresist irradiated with ultraviolet rays is initiated by the photoinitiator contained in the irradiated portion. Initially, oxygen in the photoresist is consumed, and then the activated monomer is polymerized to cause a crosslinking reaction, and then a large amount of monomer is consumed to proceed with the polymerization reaction. On the other hand, the unexposed portion is present in a state where the crosslinking reaction does not proceed.

Next, a developing process of removing unexposed portions of the photoresist is performed. In the case of an alkaline developable dry film resist, 0.2 to 1.2 wt% of potassium carbonate and sodium carbonate aqueous solution is used as a developer. In this process, the photoresist of the unexposed portion is washed away by the saponification reaction between the carboxylic acid of the binder polymer and the developer in the developer, and the cured photoresist remains on the partition wall surface.

As described above, the glass substrate on which the dry film is patterned forms a partition pattern by a sandblasting process. The dry film pattern formed on the partition wall material in the sandblasting process serves as a protective film to prevent the partition material beneath the cutting material.

Thereafter, the partition formation is completed by performing a peeling step of removing the pattern of the dry film resist and a baking step of curing the partition material.

Recently, the selection of barrier materials with good luminous efficiency has emerged as a major issue in the manufacture of PDP. In order to satisfy this problem, a white rib material is used in the black rib material in selecting the barrier material. A lot of methods are used. In general, in the PDP lower plate manufacturing method using a dry film as a sand blast mask, in the case of using a white lip material, a lot of diffused reflection of UV occurs in the process of exposing the dry film, and the edge of the dry film pattern after exposure and development of the dry film. The edges are rough. In particular, when the white lip material is used, the adhesion between the dry film and the white lip material is remarkably lower than the adhesion between the black lip material and the dry film, and a lot of lip open defects occur after the sandblasting process. Therefore, when the white lip, which is a partition material having good luminous efficiency, is selected as the PDP partition material, the adhesion between the partition material and the dry film becomes a very important factor in terms of improving PDP manufacturing yield.

As such, the recent trend of changing the partition material from the black lip material to the white lip material in the selection of the partition material for the production of high-brightness PDP, but in general, the adhesion between the sand blast resist and the white lip partition material is different from that of the black lip material. As a result of the significant drop in the adhesion force, the partial delamination of the sandblast resist occurs in the bulkhead forming process, resulting in a large amount of partial lip open failure, resulting in a decrease in yield. Therefore, it is very important to improve the adhesion of the sandblast resist.

Therefore, a lot of efforts are being made to increase the adhesion by changing the composition of the sandblast resist. For example, US Patent No. 5,924,912 discloses a composition in which cellulose acetate phthalate is applied as a binder polymer, and US Patent No. 6,200,733 is disclosed. Compositions in which hydroxypropylmethyl cellulose phthalate and hydroxypropylmethyl cellulose acetate phthalate are applied as binder polymers are disclosed, and US Pat. No. 6,322,947 discloses compositions in which hydroxymethyl cellulose acetate phthalate is applied as binder polymer.

However, in the case of a dry film photoresist using a known carboxyl group-containing cellulose compound, that is, cellulose acetate phthalate (CAP), hydroxypropylmethyl cellulose phthalate (HPMCP), and hydroxypropylmethyl cellulose acetate phthalate (HPMCAP) as a binder polymer, Good adhesion was observed, but the white lip material showed a sharp drop in adhesion.

Therefore, in the present invention, by introducing a new binder polymer, which is a skeletal material of dry film, in order to improve the adhesion of PDP (Plasma Display Panel), the elasticity and flexibility of the sandblast resist are as good as originally required, and The object of this invention is to provide the photosensitive resin composition for sandblast resists which can provide the resist layer patterned by photolithography which is excellent in adhesiveness, and is excellent in alkali developability and peelability.

The photosensitive resin composition for sand blast resist of the present invention for achieving the above object includes an cellulose derivative as an alkali-soluble binder polymer, and includes a reactive oligomer, a photopolymerization initiator, a plasticizer and other additives, wherein the binder polymer is R ₁ , R ₂ , R ₃ , R ₄ , R ₅ or R ₆ are H, , Cellulose derivatives represented by the formula (1); R ₁ , R ₂ , R ₃ , R ₄ , R ₅ or R ₆ are H, , Cellulose derivatives represented by the formula (1); R ₁ , R ₂ , R ₃ , R ₄ , R ₅ or R ₆ are H, (m is an integer of 3 to 10), Cellulose derivatives represented by the formula (1); And R ₁ , R ₂ , R ₃ , R ₄ , R ₅ or R ₆ are H, (l is an integer from 2 to 10), , It is characterized in that it is selected from the cellulose derivative represented by the formula (1).

Formula 1

The total molecular weight of all molecules is 30,000 to 100,000.

The present invention will be described in more detail as follows.

The present invention relates to a photosensitive resin composition having excellent alkali developability, and more particularly to a resin composition having excellent reactivity, resolution, adhesion and resistance to sandblasting.

The present invention intends to introduce a new one as a binder polymer in manufacturing a photosensitive resin composition for sand blast resist, and compared with CAP (cellulose acetate phthalate), HPMCP It was observed that hydroxypropyl methyl cellulose phthalate (HPMCAP) and hydroxypropyl methyl cellulose acetate phthalate (HPMCAP) showed somewhat good adhesion in black lip material and white lip material. In the case of CAP, the hydroxy group is directly attached to the rigid hexagonal ring structure which can show strong interaction with the bulkhead material, while in the case of HPMCP or HPMCAP, the hydroxy group is relatively far from the hexagonal ring structure. Therefore, the effect of steric hindrance is small, so it is considered to show relatively good adhesion with the bulkhead material. Therefore, the present invention intends to increase adhesion by designing a longer distance between the hydroxy group and the skeleton structure of the binder polymer in the structure of the cellulose derivative used as the binder polymer, and also dehydrated instead of the hydroxyl group of HPMCP and HPMCAP. By introducing the oxypropyl group, a method of increasing the adhesion with the partition material is studied. In addition, an effort to increase the adhesion by increasing the number of carboxyl groups having a strong hydrophilicity, improved adhesion was obtained.

In the present invention, the photosensitive resin composition refers to a photoresist layer disposed between a polyethylene terephthalate (PET) base film and a polyethylene (PE) film in a dry film resist, wherein the photoresist layer is a photoinitiator, (b) A) alkali developable binder polymer, (c) photopolymerizable oligomer and (d) various additives. In particular, the photosensitive resin composition should have good adhesion to the substrate during the sandblasting process, and excellent elasticity and flexibility are required to have the mechanical impact resistance of the sandblasting process.

The binder polymer of the photosensitive resin composition of the present invention for this has a structure as shown in Formula 1, specifically, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ or R ₆ is H, , Cellulose derivatives represented by the formula (1) (hereinafter referred to as BP-1); R ₁ , R ₂ , R ₃ , R ₄ , R ₅ or R ₆ are H, , Cellulose derivatives represented by the formula (1) (hereinafter referred to as BP-2); R ₁ , R ₂ , R ₃ , R ₄ , R ₅ or R ₆ are H, (m is an integer of 3 to 10), Cellulose derivatives represented by the formula (1) (hereinafter referred to as BP-3); And R ₁ , R ₂ , R ₃ , R ₄ , R ₅ or R ₆ are H, (l is an integer from 2 to 10), , It is selected from cellulose derivatives represented by the formula (1) (hereinafter referred to as BP-4).

A method for preparing such a binder polymer is known. For example, in the case of BP-1, cellulose acetate trimellitate is obtained by adding Aldrich's reagent as an additional form of a carboxyl group which can have a strong binding force with the partition material. Experiment.

BP-2 can be synthesized from the reaction of dihydroxypropyl cellulose and phthalic anhydride obtained in the reaction of alkali cellulose with 3-chloro-1,2-propane-diol. Dihydroxypropyl cellulose can be synthesized from the methods described in US Pat. Nos. 1,502,379 and 1,722,927, and the method of introducing phthalate groups thereto can be synthesized using the method of US Pat. No. 2,759,925.

In the case of BP-3 and BP-4, after the etherification reaction between cellulose and various chloride compounds in NaOH atmosphere, the intermediate obtained therein is introduced with phthalate group to the cellulose according to the aforementioned method, that is, the method of US Pat. No. 2,759,925. It can be obtained by. The etherification of BP-3 and BP-4 is according to the methods of US Pat. Nos. 1,502,379 and 1,722,927. Examples of the chloride compound that can be used in the synthesis of BP-3 and BP-4 include 6-chloro-1-hexanol (Cl-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -OH), 3-chloro- 1-propanol (Cl-CH ₂ CH ₂ CH ₂ OH), 2- (2-chloroethoxy) ethanol (Cl-CH ₂ CH ₂ OCH ₂ CH ₂ OH), and 2- [2- (2-chloro Methoxy) ethoxy] ethanol (Cl-CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OH); these reagents can be purchased from Aldrich. However, it is not necessarily limited to the compound.

The acid value of such cellulose derivatives is preferably 50 to 250 mg / KOH.

In the photosensitive resin composition, at least one reactive oligomer is at least one (meth) acrylate at the molecular end obtained from a polyether or polyester compound having a hydroxy group at the molecular end, a diisocyanate compound, and a (meth) acrylate compound having a hydroxy group. The urethane compound having a group preferably has a molecular weight in the range of 1,000 to 30,000.

It is preferable that the weight ratio of a binder polymer and a reactive oligomer is 70: 30-5: 95.

As photopolymerization initiators, as in conventional dry film resist compositions, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, benzoin phenyl ether, benzyl diphenyl disulfide, benzyl dimethyl ketal, anthraquinone And naphthoquinone, benzophenone, pivalon ethyl ether, dichloro acetophenone, dimer of hexaaryl-imidazole, tribromophenyl sulfone, tribromomethylphenyl sulfone and the like.

Plasticizers include dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, diallyl phthalate in the form of phthalic esters; Triethylene glycol diacetate in the form of glycol esters, tetraethylene glycol diacetate, p-toluenesulfonamide in the form of acid amides, benzenesulfonamide, Nn-butylbenzenesulfonamide, and triphenyl phosphate may be used. Can be. However, it is not limited to the examples mentioned above.

Reactive oligomers, photopolymerization initiators, plasticizers and other additives in the photosensitive resin composition of the present invention are in accordance with conventional dry film resist compositions and are not limited in part.

Such a photosensitive resin composition layer preferably has a thickness in the range of 10 to 100 µm in a dry film resist laminated structure.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by the Examples.

In the following experiments, the photopolymerization initiator, the photopolymerizable monomer and the oligomer were tested by fixing with a substance disclosed in the following to observe the nutrition of the binder polymer on the adhesion of the sandblast resist to the PDP partition material.

From the experimental results, it was confirmed that the result of modifying the binder polymer, which is a skeletal material of the dry film, significantly increased the adhesion, and showed sufficient adhesion even in the white lip material, thereby making it possible to manufacture a sandblast resist dry film capable of producing a high resolution PDP. It was.

Synthesis Example

BP-1 was purchased from Aldrich and used Aldrich Catalog No. 43,522-8.

BP-2 was synthesized in two steps according to the following synthesis method:

(Step 1) As an Etherification Reaction, Chloride Derivatives with Cellulose (using methods known from US Patent Nos. 1,502,379 and 1,722,927)

Cellulose was sufficiently impregnated in 50% aqueous solution of caustic soda (cellulose C₆H₁₀O₅In about 4 times the equivalent of 50% aqueous NaOH solution). Cellulose at 0 ° C. Cellulose C₆H₁₀O₅2 to 3 molar equivalents of 3-chloro-1,2-propanediol (Cl-CH) per equivalent₂CH (OH) CH₂OH) and mixed for about 1 hour (knead). The cellulose mass was mixed with 6 equivalents of caustic soda in powder form at 0 ° C., followed by about 3 molar equivalents of 3-chloro-1,2-propanediol (Cl-CH₂CH (OH) CH₂OH) Mixed for about 1 hour and won. And it heated up to room temperature. In order to control the degree of substitution, the reaction time was appropriately adjusted. After the reaction was completed, the reactant of cellulose was sufficiently washed with water and then dried sufficiently using a vacuum oven (the intermediate compound produced by the etherification was called modified cellulose-2).

(Step 2) reacting the material obtained in the etherification with phthalic anhydride to produce cellulose phthalate (synthesized according to the method of US Pat. No. 2,759,925)

The reaction product (modified cellulose-2) produced in step 1 was placed in a reactor, acetic acid was used as a solvent, and a certain amount of pyridine was added thereto to convert acetic acid into pyridine acetate. The content of the chemical used in the reactor is as follows and the reaction time and the reaction temperature was made at about 100 ℃ for 6 hours.

Reactant Molar equivalent Denatured Cellulose-2 One Phthalic anhydride 1.2 Acetic acid 2.4 Pyridine 0.1

Synthesis of BP-3-1: 3-chloro-1,2-propanediol (Cl-CH ₂ CH (OH) CH ₂ OH used in the same manner as the synthesis of BP-2 and used in step 1 of BP-2) The procedure was the same except that 3-chloro-1-propanol (Cl-CH ₂ CH ₂ CH ₂ OH) was used as a raw material for etherification.

Synthesis of BP-3-2: 3-chloro-1,2-propanediol (Cl-CH ₂ CH (OH) CH ₂ OH used in the same manner as the synthesis of BP-2 and used in step 1 of BP-2) The procedure was the same except that 6-chloro-1-hexanol (Cl-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -OH) was used as a raw material for etherification.

Synthesis of BP-4-1: 3-chloro-1,2-propanediol (Cl-CH ₂ CH (OH) CH ₂ OH used in the same manner as the synthesis of BP-2 and used in step 1 of BP-2) The procedure was the same except that 2- (2-chloroethoxy) ethanol (Cl-CH ₂ CH ₂ OCH ₂ CH ₂ OH) was used as a raw material for etherification.

Synthesis of BP-4-2: 3-chloro-1,2-propanediol (Cl-CH ₂ CH (OH) CH ₂ OH used in the same manner as the synthesis of BP-2 and used in step 1 of BP-2) The procedure was the same except that 2- [2- (2-chloroethoxy) ethoxy] ethanol (Cl-CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OH) was used as a raw material for etherification. .

Finally, the material synthesized according to the above method has a structure represented by Chemical Formula 1, and the carboxybenzoyl group and the contents of the substituents introduced by the etherification reaction are as follows. In general, it is not easy to identify the position of each substituent in the cellulose derivative, but the degree of substitution can be predicted as the content of each substituent.

Chloride derivatives Content of substituents in the final product (%) Molecular Weight Acid value (mg / KOH) Content of substituents introduced from chloride derivatives Content of Carboxybenzoyl Group BP-2 Cl-CH ₂ CH (OH) CH ₂ OH 10-20 30-35 53,000 120 BP-3-1 Cl-CH ₂ CH ₂ CH ₂ OH 10-20 30-35 48,000 125 BP-3-2 Cl-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -OH 10-20 30-35 60,000 125 BP-4-1 Cl-CH ₂ CH ₂ OCH ₂ CH ₂ OH 10-20 30-35 55,000 120 BP-4-2 Cl-CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OH 10-20 30-35 65,000 115

Examples 1-6 and Comparative Examples 1-2

Next, the photosensitive resin composition was prepared according to a conventional method with the composition as shown in Tables 2 to 9 below.

Example 1 Furtherance Content (parts by weight) Remarks Binder polymer BP-1 160.0 25wt% in MEK Photoinitiator Benzophenone 4,4 '-(bisdiethylmamino) benzophenone luke crystal violet toluene sulfonic acid monohydrate diamond green GH 2.03.03.00.50.5 Photopolymerizable monomer 50ADET-1800 (Keeping in Japan) PU-280 (Miwon Co., Ltd.) PU-210 (Miwon Co., Ltd.) 10.020.010.0 Plasticizer Triethylene glycol diacetate (Aldrich) 3.0 menstruum Methyl ethyl ketone 13.0

Example 2 Furtherance Content (parts by weight) Remarks Binder polymer BP-2 160.0 25wt% in MEK Photoinitiator Benzophenone 4,4 '-(bisdiethylmamino) benzophenone luke crystal violet toluene sulfonic acid monohydrate diamond green GH 2.03.03.00.50.5 Photopolymerizable monomer 50ADET-1800 (Keeping in Japan) PU-280 (Miwon Co., Ltd.) PU-210 (Miwon Co., Ltd.) 10.020.010.0 Plasticizer Triethylene glycol diacetate (Aldrich) 3.0 menstruum Methyl ethyl ketone 13.0

Example 3 Furtherance Content (parts by weight) Remarks Binder polymer BP-3 (m = 3) 160.0 25wt% in MEK Photoinitiator Benzophenone 4,4 '-(bisdiethylmamino) benzophenone luke crystal violet toluene sulfonic acid monohydrate diamond green GH 2.03.03.00.50.5 Photopolymerizable monomer 50ADET-1800 (Keeping in Japan) PU-280 (Miwon Co., Ltd.) PU-210 (Miwon Co., Ltd.) 10.020.010.0 Plasticizer Triethylene glycol diacetate (Aldrich) 3.0 menstruum Methyl ethyl ketone 13.0

Example 4 Furtherance Content (parts by weight) Remarks Binder polymer BP-3 (m = 6) 160.0 25wt% in MEK Photoinitiator Benzophenone 4,4 '-(bisdiethylmamino) benzophenone luke crystal violet toluene sulfonic acid monohydrate diamond green GH 2.03.03.00.50.5 Photopolymerizable monomer 50ADET-1800 (Keeping in Japan) PU-280 (Miwon Co., Ltd.) PU-210 (Miwon Co., Ltd.) 10.020.010.0 Plasticizer Triethylene glycol diacetate (Aldrich) 3.0 menstruum Methyl ethyl ketone 13.0

Example 5 Furtherance Content (parts by weight) Remarks Binder polymer BP-4 ( l = 2) 160.0 25wt% in MEK Photoinitiator Benzophenone 4,4 '-(bisdiethylmamino) benzophenone luke crystal violet toluene sulfonic acid monohydrate diamond green GH 2.03.03.00.50.5 Photopolymerizable monomer 50ADET-1800 (Keeping in Japan) PU-280 (Miwon Co., Ltd.) PU-210 (Miwon Co., Ltd.) 10.020.010.0 Plasticizer Triethylene glycol diacetate (Aldrich) 3.0 menstruum Methyl ethyl ketone 13.0

Example 6 Furtherance Content (parts by weight) Remarks Binder polymer BP-4 ( l = 3) 160.0 25wt% in MEK Photoinitiator Benzophenone 4,4 '-(bisdiethylmamino) benzophenone luke crystal violet toluene sulfonic acid monohydrate diamond green GH 2.03.03.00.50.5 Photopolymerizable monomer 50ADET-1800 (Keeping in Japan) PU-280 (Miwon Co., Ltd.) PU-210 (Miwon Co., Ltd.) 10.020.010.0 Plasticizer Triethylene glycol diacetate (Aldrich) 3.0 menstruum Methyl ethyl ketone 13.0

Comparative Example 1 Furtherance Content (parts by weight) Remarks Binder polymer BP-5 (CAP) 160.0 25wt% in MEK Photoinitiator Benzophenone 4,4 '-(bisdiethylmamino) benzophenone luke crystal violet toluene sulfonic acid monohydrate diamond green GH 2.03.03.00.50.5 Photopolymerizable monomer 50ADET-1800 (Keeping in Japan) PU-280 (Miwon Co., Ltd.) PU-210 (Miwon Co., Ltd.) 10.020.010.0 Plasticizer Triethylene glycol diacetate (Aldrich) 3.0 menstruum Methyl ethyl ketone 13.0

Comparative Example 2 Furtherance Content (parts by weight) Remarks Binder polymer BP-6 (HPMCAP) 160.0 25wt% in MEK Photoinitiator Benzophenone 4,4 '-(bisdiethylmamino) benzophenone luke crystal violet toluene sulfonic acid monohydrate diamond green GH 2.03.03.00.50.5 Photopolymerizable monomer 50ADET-1800 (Keeping in Japan) PU-280 (Miwon Co., Ltd.) PU-210 (Miwon Co., Ltd.) 10.020.010.0 Plasticizer Triethylene glycol diacetate (Aldrich) 3.0 menstruum Methyl ethyl ketone 13.0

After the mixed solution of the photosensitive resin composition was prepared according to Examples 1 to 6, the coating solution was coated on a 20 micron polyester film with a uniform thickness (40 μm) using a coating bar, and then heated for about 5 minutes at 80 ° C. in a hot air oven. After drying to some extent, a polyethylene film was laminated thereon to complete the sandblast resist, which is a photosensitive resin composition.

The finished sandblast resist was laminated using a hot pressing roller after removing the polyethylene film on the white lip material. The adhesion and resolution of the resist were measured using a 10-200 μm photomask divided into 5 μm units. In the case of adhesion, the pattern of the photomask is Line / Space = x: 400 (unit: 탆) and in the case of resolution, Line / Space = 400: x (unit: 탆). The sensitivity used as a measure of reactivity was measured on the basis of resist using a 21-step tablet from Stouffer Graphic Arts Equipment Co. Sandblast resistance, which is an important property of sandblast resist, was measured by laminating dry film on glass substrate and exposing 100mJ / cm2 (exposure energy received by real dry film = UV energy measured under photomask) using 5kW parallel light exposure machine. After the polyethylene film was removed, the abrasive was sprayed at a pressure of 1.5 kg / cm 2 using a sandblast nozzle to measure the time taken for the film of the dry film to be completely removed. Here the distance between the sandblast nozzles and the substrate is 1 cm.

The results are shown in Table 10 below.

From the results of Table 10, when comparing Comparative Examples 1 and 2, compared to CAP (cellulose acetate phthalate) used in Comparative Example 1 HPMCAP (hydroxypropylmethyl cellulose acetate phthalate) used in Comparative Example 2 is better in the adhesion of the dry film As mentioned above, the hydroxy group, which can show good adhesion with the bulkhead material of the plasma display pannel (PDP), has a lot of steric hindrance that is directly attached to the rigid hexagonal ring compound structure in the case of CAP. In comparison with the HPMCAP, the hydroxyl group is farther away from the main cellulose skeleton than the CAP, so that the HMCAP is less steric hindrance, and therefore, it is considered that the HPMCAP exhibits relatively good adhesion to the bulkhead material.

In the case of Example 1, the carboxylic acid moiety (carbozylic acid moiety) is added to the molecular structure of the binder polymer, even here, the adhesion of the adhesion due to the increase in the content of carboxylic acid having excellent interaction with the partition material of SiO ₂ basic structure It can be seen that the improvement is shown.

Examples 3 and 4 show an example of the difference in adhesion between the hydroxy group and the hexagonal cyclic compound of cellulose, which induces adhesion to the partition material. In Example 3, the hexagonal cyclic compound of the hydroxy group and cellulose The distance between the two is almost similar to the distance between the hydroxy hydroxy of hydroxypropyl of Comparative Example 2 and the hexagonal ring compound of cellulose, so that the difference in adhesion is almost similar to that of Comparative Example 2, but in the case of Example 4, Positioned sufficiently apart from the compound, the hydroxyl group was able to interact sufficiently with the barrier material, thus exhibiting excellent adhesion.

In Examples 5 and 6, the hydroxy group is sufficiently separated from the hexagonal cyclic compound of cellulose, thereby providing sufficient adhesion to the partition material and introducing ethylene oxide into the spacer to increase hydrophilicity. .

As described in detail above, when the dry film resist using the photosensitive resin composition prepared by applying a specific series of cellulose derivatives as a binder polymer according to the present invention is used for the sandblast resist used in the manufacture of the PDP underlay, sandblast resist and As the adhesion to the barrier material can be strengthened and the adhesion to the barrier material is remarkably improved, the adhesion of the black lip material as well as the white lip material can be improved, and thus the adhesion of the dry film can be easily improved. have.

Claims (4)

In the photosensitive resin composition for sandblast resist containing a cellulose derivative as an alkali-soluble binder polymer, and containing a reactive oligomer, a photoinitiator, a plasticizer, and other additives, The binder polymer is R ₁ , R ₂ , R ₃ , R ₄ , R ₅ or R ₆ is H, , Cellulose derivatives represented by the formula (1); R ₁ , R ₂ , R ₃ , R ₄ , R ₅ or R ₆ are H, , Cellulose derivatives represented by the formula (1); R ₁ , R ₂ , R ₃ , R ₄ , R ₅ or R ₆ are H, (m is an integer of 3 to 10), Cellulose derivatives represented by the formula (1); And R ₁ , R ₂ , R ₃ , R ₄ , R ₅ or R ₆ are H, (l is an integer from 2 to 10), , A photosensitive resin composition for sandblast resist, characterized in that selected from the cellulose derivative represented by the formula (1). Formula 1 The total molecular weight of all molecules is 30,000 to 100,000. The photosensitive resin composition for sandblast resist according to claim 1, wherein the binder polymer has an average molecular weight of 30,000 to 100,000 and an acid value of 50 to 250 mg / KOH. The photosensitive resin composition for sandblast resist according to claim 1, wherein the binder polymer and the reactive monomer are included in a weight ratio of 70:30 to 5:95. A photosensitive film comprising the photosensitive resin composition of claim 1 as a photoresist layer.