WO2011040749A2 - Dry film photoresist - Google Patents

Dry film photoresist Download PDF

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Publication number
WO2011040749A2
WO2011040749A2 PCT/KR2010/006612 KR2010006612W WO2011040749A2 WO 2011040749 A2 WO2011040749 A2 WO 2011040749A2 KR 2010006612 W KR2010006612 W KR 2010006612W WO 2011040749 A2 WO2011040749 A2 WO 2011040749A2
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WO
WIPO (PCT)
Prior art keywords
protective layer
dry film
resin protective
resin
film photoresist
Prior art date
Application number
PCT/KR2010/006612
Other languages
French (fr)
Korean (ko)
Other versions
WO2011040749A3 (en
Inventor
문희완
봉동훈
석상훈
Original Assignee
코오롱인더스트리 주식회사
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Priority claimed from KR1020090093493A external-priority patent/KR101258733B1/en
Priority claimed from KR1020090131963A external-priority patent/KR101262448B1/en
Application filed by 코오롱인더스트리 주식회사 filed Critical 코오롱인더스트리 주식회사
Priority to JP2012530789A priority Critical patent/JP5356603B2/en
Priority to CN201080043646.8A priority patent/CN102549499B/en
Publication of WO2011040749A2 publication Critical patent/WO2011040749A2/en
Publication of WO2011040749A3 publication Critical patent/WO2011040749A3/en

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/092—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers characterised by backside coating or layers, by lubricating-slip layers or means, by oxygen barrier layers or by stripping-release layers or means
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0752—Silicon-containing compounds in non photosensitive layers or as additives, e.g. for dry lithography
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds

Definitions

  • the present invention relates to a dry film photoresist having a multilayer structure.
  • Dry film photoresist has been used as an important material for the current electrical and electronic industries, especially printed circuit boards, since it was developed under the name RISTON by DuPont in 1968.
  • photoresist is used as a photoresist material for forming circuits on printed circuit boards, but dry film photo is used for the production of printed circuit boards of double-sided and multilayer boards requiring high density and high reliability. Resist is essentially used.
  • the dry film photoresist is mainly laminated in a two-layer structure of a base film and a photosensitive layer, and further a protective film is used to protect the photosensitive resin layer until the dry film photoresist is used. Include.
  • the support film uses a polyester film such as polyethylene terephthalate, and its thickness is about 25 ⁇ m.
  • a support film serves as a support of the photosensitive resin layer during the manufacture of the dry film photoresist, and facilitates handling during exposure of the photosensitive resin layer having adhesive force.
  • Photosensitive resin is divided into negative type and positive type by the reaction mechanism by light.
  • negative type photosensitive resin photocrosslinking reaction occurs at the exposed part, and unexposed part is washed with alkali, leaving a resist pattern.
  • a photolysis reaction occurs at an exposure site and is developed in an alkali, and an unexposed site remains to form a resist pattern.
  • the photosensitive resin layer is prepared to suit the purpose, including a photopolymerizable monomer, a photopolymerization initiator, a binder polymer, and the like.
  • a photosensitive resin layer is applied on a support film, and has a thickness of 15 to 100 ⁇ m, after application, to suit the purpose of use.
  • Such a photosensitive resin layer has various compositions according to the mechanical and chemical properties required for the photoresist and the conditions such as processing.
  • the protective film prevents damage to the resist during handling and serves as a protective cover to protect the photosensitive resin layer from foreign substances such as dust, and is laminated on the back surface where the support film of the photosensitive resin layer is not formed.
  • a protective film is first peeled off and laminated on a copper clad laminate (CCL) when applied to a printed circuit board, followed by a mask having a desired pattern. Is exposed by irradiation with ultraviolet (UV) light and then developed using a suitable solvent to wash away the uncured parts.
  • UV ultraviolet
  • the support film may be peeled off and then exposed, but the photosensitive resin layer may be tacky, and when the support film is peeled off, the mask may stick to the photosensitive resin layer, resulting in damage to the photosensitive resin layer.
  • the problem is that the resolution is lowered, the mask is contaminated, and the life of the mask is shortened.
  • the present invention improves the resolution by allowing the exposure process to be performed in a state where the support film is removed, and in particular, while adhering the support film and the resin protective layer to an appropriate level, the dry film photoresist does not damage the resin protective layer when removing the support film To provide.
  • One embodiment of the present invention comprises a support film, a resin protective layer and a photosensitive resin layer by laminating sequentially, the resin protective layer is a dry film photoresist comprising a water-soluble polymer and an alkoxy alcohol.
  • Another embodiment of the present invention further includes a release layer laminated on a support film, wherein the release layer includes at least one selected from a silicone resin, a fluorine resin, and an aliphatic wax, and the resin protective layer has a weight average.
  • Dry film photoresist comprising a polyvinyl alcohol having a molecular weight of 5000 to 300000.
  • Another embodiment of the present invention is a dry film photoresist wherein the resin protective layer comprises less than 30000ppm alkoxyalcohol.
  • Another embodiment of the present invention is a dry film photoresist wherein the alkoxyalcohol has an alkoxy group having 1 to 12 carbon atoms and an alcohol group having 1 to 12 carbon atoms.
  • Another embodiment of the present invention is a dry film photoresist that the alkoxy alcohol is butoxy ethanol.
  • Another embodiment of the present invention is a dry film photoresist in which the water-soluble polymer is dissolved in a solvent containing water and alkoxyalcohol and then coated on a support film to form a resin protective layer.
  • Another embodiment of the present invention is a dry film photoresist wherein the solvent comprises 1 to 43 parts by weight of alkoxyalcohol with respect to 100 parts by weight of water.
  • Another embodiment of the present invention is a dry film photoresist that the adhesion between the support film and the resin protective layer is 0.0005 to 0.01 N / cm.
  • Another embodiment of the present invention is a dry film photoresist, wherein the resin protective layer includes polysilicon in an amount of 0.01 to 3 parts by weight based on 100 parts by weight of a water-soluble polymer.
  • the polysilicon has a particle size of 1 ⁇ m or less upon dissolving 0.1 g of polysilicon under a condition of 80 ° C. for 6 hours in 100 g of any one solvent selected from water, alcohols, and mixtures thereof. Film photoresist.
  • Another embodiment of the present invention is a dry film photoresist wherein the resin protective layer has a haze of 3.0% or less.
  • Another embodiment of the present invention is a dry film photoresist wherein the resin protective layer has a developing time of 1 ⁇ m or less.
  • Another embodiment of the present invention is a dry film photoresist that the adhesion between the release layer and the resin protective layer is 0.0005 to 0.01 N / cm.
  • Another embodiment of the present invention is a dry film photoresist wherein the resin protective layer is less than 10 ⁇ m thickness.
  • Another embodiment of the present invention is a polyvinyl alcohol is a dry film photoresist having a degree of saponification of 75 to 97%.
  • the dry film photoresist according to the present invention can be subjected to the exposure process with the support film removed, thereby ultimately improving the resolution by preventing adverse effects of the exposure effect by the support film.
  • the resin protective layer according to the present invention can reduce the content of a wetting agent such as polysilicon to obtain a haze (lower effect) while reducing the cost, titrating the support film and the resin protective layer
  • a wetting agent such as polysilicon
  • the resin protective layer is not damaged, and the haze can be prevented, and the development time can be prevented from being lowered, thereby achieving a high resolution.
  • Example 1 is an electron micrograph taken at 1200 times magnification of the surface of a printed circuit board after the developing process manufactured in Example 1 of the present invention.
  • Example 2 is an electron micrograph taken at 1200 times magnification of the surface of a printed circuit board after the developing process manufactured in Example 5 of the present invention.
  • FIG. 3 is an electron micrograph taken at a magnification of 1200 times the surface of a printed circuit board after the developing process manufactured in Comparative Example 1.
  • a support film, a resin protective layer and a photosensitive resin layer are sequentially laminated and included, and the resin protective layer is to provide a dry film photoresist including a water-soluble polymer and an alkoxy alcohol.
  • the dry film photoresist of the present invention has a structure in which a support film, a release layer, a resin protective layer, and a photosensitive resin layer are sequentially stacked and included.
  • the support film serves as a support of the resin protective layer and the photosensitive resin layer, it is preferable to have sufficient mechanical properties. More specifically, the support film includes a polyester film such as polyethylene terephthalate film and polyethylene naphthalate film; Polyolefin-based films such as polyethylene films, and polypropylene films; Polyvinyl-based films such as copolymer films of polyvinylchloride and vinyl acetate, polytetrafluoroethylene films, and polytrifluoroethylene films; Polyimide film; Polyamide-based films such as 6,6-nylon; Polyacetate-based films such as cellulose triacetate film and cellulose diacetate film; Polyacrylate-based films such as alkyl poly (meth) acrylate films; Polyacrylic films such as (meth) acrylic acid ester copolymer films; These etc. are mentioned, Preferably, a polyethylene terephthalate is mentioned in consideration of mechanical properties and economics.
  • the thickness of the support film can be selected according to any purpose in the range of 10 to 100 ⁇ m.
  • the resin protective layer includes a water-soluble polymer and an alkoxy alcohol.
  • the resin protective layer includes a water-soluble polymer, so that water may be used as a solvent to dissolve the water-soluble polymer. Since the alkoxy alcohol has a smaller surface tension than water, the resin protective layer may be formed on the support film.
  • the coating liquid that is, a coating liquid containing a water-soluble polymer and an alkoxyalcohol is improved, the wetting property (wetting) can be improved to obtain an effect of forming a coating film well.
  • a wetting agent such as polysilicon may be added to the resin protective layer.
  • the wetting property may be improved even if the content of the wetting agent is reduced. Since the content of the tinting agent can be reduced, an economic effect of reducing the cost can be obtained.
  • polysilicon which can be used as a wetting agent
  • polysilicon has a higher solubility in alkoxy alcohol than water, thereby lowering haze and consequently high resolution. Can be implemented.
  • the alkoxyalcohol is preferably included with the water-soluble polymer in the resin protective layer.
  • the alkoxyalcohol described above is preferably included in the resin protective layer in an amount of 30000 ppm or less.
  • the content of the alkoxyalcohol refers to the content after the resin protective layer is formed on the support film and dried. Since the content of the alkoxyalcohol is required to be low in the resin protective layer, the lower the lower limit of the alkoxyalcohol is better. When the content of the alkoxyalcohol is within the above range, it may have physical properties of the resin protective layer above the desired level in the present invention.
  • the alkoxyalcohol preferably has an alkoxy group having 1 to 12 carbon atoms and an alcohol group having 1 to 12 carbon atoms, preferably an alkoxy group having 1 to 6 carbon atoms and an alcohol group having 1 to 6 carbon atoms.
  • alkoxyalcohol examples include 2-n-hexoxyethanol, 2- (2-methylpentoxy) ethanol, and 2- (3-methylphene.
  • Dry film photoresist comprises a resin protective layer formed by dissolving the water-soluble polymer in a solvent containing water and alkoxyalcohol and then coating it on a support film.
  • the water-soluble polymer When the water-soluble polymer is dissolved in the solvent to form a resin protective layer, the water-soluble polymer may be uniformly dissolved by water. Since the alkoxy alcohol has a smaller surface tension than water, a coating solution for forming a resin protective layer on the support film, that is, water-soluble.
  • wetting may be improved to obtain an effect of forming a coating film well.
  • the resin protective layer described above includes a water-soluble polymer and an alkoxy alcohol, and the resin protective layer may use water as a solvent due to the water-soluble polymer.
  • a water-soluble polymer has low solubility in alkoxy alcohols compared to water, and thus may be used with water. It is preferable. That is, since the water solubility of the alkoxyalcohol is lower than that of water, the content of the water-soluble polymer may decrease when the content of the alkoxyalcohol is increased, and the wettability is increased when the water content is increased to increase the content of the water-soluble polymer. Degradation problems may occur.
  • the resin protective layer preferably includes water together with the alkoxyalcohol, and when the alkoxyalcohol and the water are included in the solvent, the resin protective layer should be included in an appropriate level range.
  • the solvent may include 1 to 43 parts by weight of alkoxyalcohol based on 100 parts by weight of water.
  • content of the alkoxyalcohol with respect to 100 parts by weight of water is within the above range, it is possible to obtain an effect of improving the wettability while uniformly dissolving the water-soluble polymer in the content of the level desired by the present invention.
  • the haze of the resin protective layer may be 3.0% or less, and the developing speed per 1 ⁇ m may be 10 seconds or less.
  • UV ultraviolet
  • the developer is mostly composed of a water-soluble solvent. It is important that the resin protective layer is well dissolved in the water-soluble solvent of the developer so that the residue does not remain in the photosensitive resin layer after development, and this is one of the factors that improve the developability.
  • the water-soluble polymer included in the resin protective layer may decrease the solubility of the water-soluble polymer as the weight average molecular weight increases, so that the degree of washing in the developer.
  • This developability is also affected by the developing speed.
  • the developing speed of the resin protective layer is slow, a large difference in developing time due to the thickness deviation of the resin protective layer is caused. Since the adhesive force may be reduced by washing more than necessary, or the resolution may be reduced by less washing, the developing speed of the resin protective layer should have an appropriate speed in consideration of the phenomenon of the photosensitive resin layer in order to form a precise pattern.
  • the resin protective layer includes a water-soluble polymer having an appropriate weight average molecular weight in order to improve developability, and has an appropriate level of developing speed so that no residue remains and no damage is caused to the cured portion of the photosensitive resin layer. It is important.
  • the water-soluble polymer according to the present invention is preferably polyvinyl alcohol having a weight average molecular weight of 5000 to 300000, preferably 5000 to 15000, more preferably 5000 to 10000.
  • the weight average molecular weight is less than 5000, the coating on the film becomes difficult, and the strength is weak, so that it is difficult to perform the protective function of the photosensitive resin layer. If the weight average molecular weight exceeds 300,000, the development time becomes longer and the support film is laminated on the copper clad laminate. There is a risk of damage when peeling.
  • the polyvinyl alcohol preferably has a saponification degree of 75% to 97%.
  • the degree of saponification is a factor that affects the developability.
  • the resin protective layer has an appropriate developing time to form the photosensitive resin layer, thereby reducing the adhesion and the resolution.
  • the light scattering degree to the resin protective layer during exposure should be low, so the haze value is required to be low. This is because light passes through the resin protective layer when the photosensitive resin layer is exposed in the dry film photoresist.
  • the resin protective layer may have a haze value of 3.0% or less, preferably 0.001 to 3.0%. When the haze is in the range, the light transmittance may be increased to increase the resolution.
  • the haze of the resin protective layer is required to have a low value in order to lower the light scattering degree, a lower limit value is preferable, and in the case of more than 3%, the shape of the photosensitive resin layer that has been exposed and developed ( The side wall is not smooth and rough.
  • the resin protective layer may have a value in which the developing speed per ⁇ m is 10 seconds or less, preferably 0.1 to 10 seconds.
  • the resolution may be improved by having an optimum developing speed.
  • the lower the lower limit is, the more preferable, and when it exceeds 10 seconds, the development time according to the thickness deviation of the resin protective layer There is a problem that the difference occurs a lot of the photosensitive resin layer is washed more than necessary to reduce the adhesion, or less washed off the resolution.
  • the dry film photoresist of the present invention may be subjected to the exposure process by removing the support film before the exposure process, so that the damage on the photosensitive resin layer caused by contact with the mask when performing the exposure process with the conventional support film removed And it is possible to prevent the contamination of the mask, it is also possible to obtain the effect of preventing adverse effects due to particles contained in the support film.
  • the resin protective layer is required to have an appropriate level of adhesion with the support film in consideration of the case where the support film is removed, in that the surface of the resin protective layer should not be damaged when the support film is removed from the resin protective layer. It is preferable that the adhesive force between a support film and a resin protective layer is 0.0005-0.01 N / cm. In detail, when the adhesive force is within the range, when the protective film is removed during lamination, the support film and the resin protective layer are not separated, and the resin protective layer is damaged when the support film is removed before exposure. There is an advantage that can be removed without giving.
  • the resin protective layer according to the present invention may include polysilicon.
  • the polysilicon serves to impart releasability to the resin protective layer, and may also affect adhesion and haze between the support film and the resin protective layer.
  • the resin protective layer may be included in an amount of 0.01 to 3 parts by weight of polysilicon based on 100 parts by weight of the water-soluble polymer.
  • the content of polysilicon relative to 100 parts by weight of the water-soluble polymer is preferably carried out within the above range in consideration of ease of application on the support film and haze of the resin protective layer after drying.
  • Such polysilicon is soluble in any one solvent selected from water, alcohols and mixtures thereof. If the polysilicon is dissolved in an organic solvent, it does not dissolve in water and alcohols or a mixed solvent thereof, so that the particle size is significantly increased, which is not preferable in the present invention.
  • the polysilicon has a particle size of 1 ⁇ m or less when dissolved in 0.1 g of polysilicon under conditions of 80 ° C. for 6 hours in a solution-type particle size measuring device, and it is preferable to dissolve all polysilicon.
  • the particle size of the polysilicon is in the above range, it is possible to prevent a decrease in haze and to prevent a side wall from being lowered during circuit formation of the photosensitive resin layer.
  • the resin protective layer has a thickness of 10 ⁇ m or less, preferably 0.001 to 10 ⁇ m, more preferably 0.001 to 5 ⁇ m.
  • the present invention is required to have a low thickness of the resin protective layer in order to implement a high resolution, so the lower the lower limit is preferable, and therefore, by using a resin protective layer having a thickness of 10 ⁇ m or less, to minimize the separation distance with the mask.
  • a resin protective layer having a thickness of 10 ⁇ m or less to minimize the separation distance with the mask.
  • the release layer comprises at least one selected from silicone resins, fluorine resins, and aliphatic wax, the resin protection
  • the layer is to provide a dry film photoresist comprising polyvinyl alcohol having a weight average molecular weight of 5000 to 300000, preferably 5000 to 15000, more preferably 5000 to 10000.
  • the release layer is formed on the support film to bond the resin protective layer and the support film to an appropriate level, and at the same time serves to damage the surface of the resin protective layer when peeling off the support film from the resin protective layer.
  • the photosensitive resin layer of the dry film photoresist in which the support film, the resin protective layer and the photosensitive resin layer are sequentially laminated is a copper clad laminate.
  • CTL copper clad laminate.
  • the support film is peeled off from the resin protective layer.
  • the support film is There arises a problem that the support film and the resin protective layer is separated before the peeling process, the workability due to the process disruption is lowered, and the dry film photoresist is badly produced.
  • the support film and the resin protective layer are not separated before the support film is removed, the surface of the resin protective layer is damaged while the support film is peeled off, resulting in lower haze and adversely affect the development time. Problem occurs.
  • the release layer includes at least one selected from silicone resins, fluororesins, and aliphatic waxes.
  • the release layer is required to have a release force at an appropriate level between the release layer and the resin protective layer in consideration of the case of removing the support film from the resin protective layer as described above, when the release film is removed from the resin protective layer
  • the adhesive force between the release layer and the resin protective layer is preferably 0.0005 to 0.01 N / cm in that the layer should not damage the surface of the resin protective layer.
  • the protective film is removed from the dry film photoresist further including a protective film on the photosensitive resin layer to laminate the dry film photoresist on the copper clad laminate.
  • the method for forming such a resin protective layer is not particularly limited, and the resin protective layer forming composition may be dissolved in a solvent containing an organic solvent and water, and then formed by applying and drying the composition on a support film and / or a release layer. have.
  • composition of the photosensitive resin layer may vary depending on whether the dry film photoresist is applied in a negative type or a positive type.
  • the composition of the photosensitive resin layer according to such a negative type or positive type dry film photoresist may be generally selected as a photosensitive resin composition well known in the art.
  • the photosensitive resin layer may include an binder resin, a photopolymerizable compound, an ethylenically unsaturated compound, a photopolymerization initiator, and an additive.
  • an acrylic polymer such as polyester, polyurethane, or the like may be used.
  • methacrylic copolymer which is a kind of acrylic polymer is preferable.
  • Copolymers of ethylenically unsaturated carboxylic acids and other monomers can be used as desired.
  • methacrylic copolymer a methacrylic copolymer including an acetoacetyl group may also be used.
  • Methacrylic monomers usable for synthesizing the methacrylic copolymers include methyl methacrylate, methyl methacrylate, propyl methacrylate and butyl methacrylate.
  • monoacrylic acid such as acrylic acid, methacrylic acid, and crotonic acid is used.
  • maleic acid, fumaric acid, dicarboxylic acids such as itaconic acid, or anhydrides thereof, half esters, and the like may also be used.
  • acrylic acid and methacrylic acid are preferable.
  • copolymerizable monomers include acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, styrene, a-methylstyrene, Vinyl acetate, alkyl vinyl ether, and the like.
  • an ethylenically unsaturated compound may be a monofunctional, bifunctional, trifunctional or higher polyfunctional monomer.
  • the polyfunctional monomers include ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and propylene glycol dimethacrylate.
  • the monofunctional monomers include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, and 2-hydroxybutyl methacrylate.
  • 2-phenoxy-2-hydroxypropyl methacrylate, 2-methacryloyloxy-2 hydroxypropyl phthalate, 3 3-chloro-2-hydroxypropyl methacrylate, glycerin monomethacrylate, 2-methacryloyloxyethyl acid phosphate, Methacrylic acid of phthalic acid derivatives, N-methylol methacrylamide, and the like can be used.
  • the monofunctional monomer may be used together with the multifunctional monomer.
  • photopolymerization initiator examples include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, Benzoin phenyl ether, benzyl diphenyl disulfide, benzyl dimethyl ketal, anthraquinone, naphthoquinone, 3,3-dimethyl- 4-methoxybenzophenone (3,3-dimethyl-4-methoxybenzophenone), benzophenone, p, p'-bis (dimethylamino) benzophenone (p, p'-bis (dimethylamino) benzophenone), p, p'-bis (diethylamino) benzophenone (p, p'-bis (diethylamino) benzophenone), p, p'-diethylaminobenzophenone (p, p'-diethylaminobenzophenone
  • a softening agent such as vinyl chloride resin may be included.
  • the phthalic ester include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, and dioctyl phthalate.
  • dioctyl adipate diisobutyl adipate, dibutyl adipate, Diisodecyl adipate, dibutyl diglycodiate l adipate), dibutyl sebacate, dioctyl sebacate, and the like.
  • volatile organic glycerol glycerin
  • trimethylolpropane ethylene glycol
  • ethylene glycol ethylene glycol
  • diethylene glycol diethylene glycol
  • triethylene glycol propylene glycol
  • dipropylene glycol dipropylene glycol or lower alkyl ethers thereof
  • lower fatty acid esters higher fatty acids or their esters, higher fatty alcohols or esters thereof, and the like
  • the binder resin, the photopolymerizable compound, the photoinitiator, and the additive contained in the negative photosensitive resin described above can be appropriately mixed and used according to any purpose.
  • the photosensitive resin layer may include an alkali-soluble resin and a diazide-based photosensitive compound, specifically, a novolak resin may be used as the alkali-soluble resin, and more preferably, cresol furnace May comprise a volac resin.
  • the novolak resin can be obtained by polycondensation of phenol alone or a combination of an aldehyde and an acid catalyst.
  • the phenols are not particularly limited, and phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3, 5-xylenol, 2,3,5-trimethylphenol-xylenol, 4-t-butylphenol, 2-t-butylphenol, 3-t-butylphenol, 4-methyl-2-t-butylphenol Monovalent phenols; And 2-naphthol, 1,3-dihydroxy naphthalene, 1,7-dihydroxy naphthalene, 1,5-dihydroxy naphthalene, resorcinol, pyrocatechol, hydroquinone, bisphenol A, fluoroglucinol, Polyhydric phenols, such as a pyrogallol, etc. are mentioned, These can be selected individually and can be used in combination of 2 or more types. In particular, a combination of m-cresol and
  • the aldehydes are not particularly limited, but formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, alpha or beta-phenyl propylaldehyde, o-, m- or p-hydride Roxy benzaldehyde, glutaraldehyde, terephthalaldehyde, etc. are mentioned, It can be used individually or in combination of 2 or more types.
  • the cresol novolak resin preferably has a weight average molecular weight (based on the GPC method) of 2,000 to 30,000, and the cresol novolak resin has different physical properties such as photosensitivity and residual film ratio depending on the content ratio of meta / para cresol. As such, it may be desirable that the meta / para cresol content is mixed in a ratio of 4: 6 to 6: 4 by weight.
  • the content of the meta cresol in the cresol novolak resin exceeds the above range, the photoresist rate is increased while the residual film rate is drastically lowered.
  • the photosensitivity is slowed.
  • the cresol novolac resin may be used solely a cresol novolac resin having a meta / para cresol content of 4: 6 to 6: 4 by weight, and more preferably, different resins may be mixed. In this case, it is preferable to use a cresol novolac resin mixed with a cresol novolac resin having a weight average molecular weight of 8,000 to 30,000 and a novolac resin having a weight average molecular weight of 2,000 to 8,000 in a ratio of 7: 3 to 9: 1. .
  • weight average molecular weight is defined in terms of polystyrene equivalents, as determined by gel permeation chromatography (GPC) unless otherwise specified.
  • the diazide-based photosensitive compound acts as a dissolution inhibitor to reduce the solubility of alkali-soluble resin in alkali, and when irradiated with light, the diazide-based photosensitive compound is converted into alkali-soluble material to increase alkali solubility of alkali-soluble resin. do.
  • the exposed portion of the film type photodegradable transfer material of the present invention is developed.
  • the diazide photosensitive compound can be synthesized by esterification of a polyhydroxy compound and a quinone diazide sulfonic acid compound.
  • the esterification reaction for obtaining a diazide photosensitive compound is carried out by dioxane, acetone, tetrahydrofuran, methyl ethyl ketone, N-methylpyrrolidone, chloroform, triethylamine, N, and polyhydroxy compound and quinone diazide sulfonic acid compound.
  • a basic catalyst such as -methylmorpholine, N-methylpiperazine or 4-dimethylaminopyridine can be dropped and condensed, and then the obtained product can be washed, purified and dried.
  • the quinone diazide sulfonic acid compound is, for example, 1,2-benzoquinone diazide-4-sulfonic acid, 1,2-naphthoquinone diazide-4-sulfonic acid, 1,2-benzoquinone diazide-5-sulfonic acid and O-quinone diazide sulfonic acid compounds such as 1,2-naphthoquinone diazide-5-sulfone phase, other quinone diazide sulfonic acid derivatives, and the like.
  • the quinonediazide sulfonic acid compound itself has a function as a dissolution inhibiting agent that lowers the solubility of alkali-soluble resin in alkali. However, it is decomposed to be alkali-soluble at the time of exposure and thereby rather has the property of promoting dissolution of alkali-soluble resin in alkali.
  • polyhydroxy compound examples include trihydroxy benzophene such as 2,3,4-trihydroxy benzophenone, 2,2 ', 3-trihydroxy benzophenone, and 2,3,4'-trihydroxy benzophenone.
  • Trihydroxy benzophene such as 2,3,4,4'-tetrahydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxy benzophenone, and 2,3,4,5-tetrahydroxybenzophenone Rice field; 2,2 ', 3,4,4'-pentahydroxy benzophenone, 2,2', 3,4,5-pentahydroxy benzophenone ed pentahydroxy benzophenone; Hexahydroxy benzophenones such as 2,3,3 ', 4,4', 5'-hexahydroxybenzophenone and 2,2 ', 3,3', 4,5'-hexahydroxy benzophenone; Gallic acid alkyl esters; Oxyflavones etc. are mentioned.
  • diazide photosensitive compound obtained from these include 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinone diazide-5-sulfonate, 2,3,4-tri Hydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate and (1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxy Phenyl) ethyl] benzene) 1, 2- naphthoquinone diazide-5-sulfonate 1 or more types chosen are mentioned.
  • the diazide-based photosensitive compound may be advantageously 30 to 80 parts by weight based on 100 parts by weight of the alkali-soluble resin in the photoresist layer composition in view of developability or solubility.
  • the positive photosensitive resin layer described above may include a sensitivity enhancer, which is intended to improve sensitivity.
  • a sensitivity enhancer examples thereof include 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone and 1- [1- (4-hydroxyphenyl) isopropyl] -4- [ 1,1-bis (4-hydroxyphenyl) ethyl] benzene.
  • the sensitivity enhancer is included in an amount of 3 to 15 parts by weight based on 100 parts by weight of the alkali-soluble resin, it may be advantageous in terms of improving the photosensitive effect and margin of the window process.
  • the positive photosensitive resin layer may contain other components or additives such as a leveling agent, a filler, and an antioxidant.
  • a composition containing an alkali-soluble resin, a diazide-based photosensitive compound, etc. is dispersed in a predetermined amount of a solvent to be prepared and then applied.
  • a solvent examples include ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, and diethylene.
  • the dry film photoresist according to the present invention may further include a protective film on one surface of the photosensitive resin layer.
  • the protective film serves to protect the photosensitive resin layer from the outside, and when the dry film photoresist is easily applied to the post-process, the protective film needs proper release property and adhesion so as not to be released during storage and distribution.
  • the particle size of 0 ⁇ m means that the polysilicon was almost completely dissolved in the solvent and no particulate was found.
  • 'particle size 0 ⁇ ' means the same as described above.
  • a photosensitive resin composition was prepared in the composition and content used for UH-9200 series (Kolon). Specifically, the photoinitiators were dissolved in methyl ethyl ketone and methyl alcohol as solvents, and then photopolymerizable oligomers and binder polymers were added and mixed for 1 hour using a mechanical stirrer to prepare a photosensitive resin composition.
  • Example 2 The same procedure as in Example 1 was carried out except that ethoxyethanol was used instead of butoxyethanol. At this time, after drying the formed resin protective layer was measured by the method of measuring the residual solvent according to the following, the content of ethoxyethanol contained in the resin protective layer was 1100ppm.
  • Example 2 The same procedure as in Example 1 was repeated except that 95 g of distilled water and 5 g of butoxyethanol were used instead of 90 g of distilled water and 10 g of butoxyethanol. At this time, after drying the formed resin protective layer was measured by the method of measuring the residual solvent according to the following, the content of butoxyethanol contained in the resin protective layer was 900ppm.
  • Example 2 The same procedure as in Example 1 was repeated except that 80 g of distilled water and 20 g of butoxyethanol were used instead of 90 g of distilled water and 10 g of butoxyethanol. At this time, after drying the formed resin protective layer was measured by the method of measuring the residual solvent according to the following, the content of butoxyethanol contained in the resin protective layer was 1400ppm.
  • the support film is a polyethylene terephthalate film in which a release layer is formed by using a silicone resin on one surface of the support film by an in-line coating (ILC) method.
  • ILC in-line coating
  • the release layer on the support film may be formed by an off-line coating method in addition to the ILC method.
  • the ILC method and the off-line coating method are well known in the art to which the present invention pertains, and a detailed description thereof will be omitted.
  • a photosensitive resin composition was prepared in the composition and content used for UH-9200 series (Kolon). Specifically, the photoinitiators were dissolved in methyl ethyl ketone and methyl alcohol as solvents, and then photopolymerizable oligomers and binder polymers were added and mixed for 1 hour using a mechanical stirrer to prepare a photosensitive resin composition.
  • the photosensitive resin composition was coated on a 19 ⁇ m thick protective film (CY201-19 ⁇ m, KOLON) using a coating bar, and then dried at 80 ° C. for 6 minutes using a hot air oven to give a photosensitive water having a thickness of 15 ⁇ m. Formed strata.
  • a film-type photosensitive transfer material having a thickness of 53 ⁇ m was prepared by laminating at a pressure of 4 kgf / cm 2 at 50 ° C. such that the photosensitive resin layer of the dried (c) film and the resin protective layer of (a) were contacted.
  • a dry film photoresist was prepared in the same manner as in Example 5, except that the following procedure was carried out.
  • a dry film photoresist was prepared in the same manner as in Example 5, except that the following procedure was carried out.
  • a dry film photoresist was prepared in the same manner as in Example 5, except that the following procedure was carried out.
  • a dry film photoresist was prepared in the same manner as in Example 5, except that the following procedure was carried out.
  • a photosensitive resin composition was prepared in the composition and content used for UH-9200 series (Kolon). Specifically, photoinitiators were dissolved in methyl ethyl ketone and methyl alcohol as solvents, and then photopolymerizable oligomers and binder polymers were added and mixed for 1 hour using a stirring machine to prepare a photosensitive resin composition.
  • Example 2 The same procedure as in Example 1 was repeated except that acetone was used instead of butoxyethanol.
  • Example 2 The same procedure as in Example 1 was repeated except that tetrahydrofuran (THF) was used instead of butoxyethanol.
  • THF tetrahydrofuran
  • Example 5 The same procedure as in Example 5 was repeated except that tetrahydrofuran (THF) was used instead of butoxyethanol.
  • THF tetrahydrofuran
  • the weight average molecular weight, saponification degree, and residual solvent amount of the water-soluble polymers according to Examples 1 to 9 and Comparative Examples 2 to 4 were measured by the following method.
  • the weight average molecular weight of the water-soluble polymer is 40 ° C using GFC (Gel Filtration Chromatography; Varian GPC system), Stationary Phase is (Plgel Mixed D) ⁇ 2, Mobile Phase: THF, 1.0ml / min, Injection: 100 ⁇ l , Detection: Injecting PS Standard (Polymer Standards Service, Mp 723000,219000,89300,52200,30300,7000,5000,2960) dissolved in THF at 0.1% concentration under the conditions of RI and 40C was measured as a reference substance. . Samples were dissolved in THF at a concentration of 0.2% and filtered by 0.45 ⁇ m PTFE syringe filter.
  • the saponification degree of polyvinyl alcohol was measured in accordance with JIS K6726 method.
  • Residual solvent amount is measured by GC-Mass using headspace.
  • the dry film photoresist prepared according to Examples 1 to 9 and Comparative Examples 2 and 4 was cut into 7 cm ⁇ 7 cm and then peeled off the protective film to be laminated on a copper clad laminate having a size of 10 cm ⁇ 10 cm. It was.
  • the resin protective layer was peeled off, and the peeled resin protective layer was prepared using a Haze Meter (NIPPON DENSHOKU, NDH-2000), and the resin protective layer 5g After taking it into 22ml headspace vial and sealing it, Headspace condition (Incubation Temp .: 200 °C (Oven), Incubation Time: 30min, Syringe Temp .: 150 °C, Agitator speed: 250rpm, Fill Speed: 25ul / s, Fill Strokes: 0, Injection Speed: 700 ul / s, Pre Inject Delay: 0 ms, Post Inject Delay: 500 ms).
  • Headspace condition Incubation Temp .: 200 °C (Oven)
  • Incubation Time 30min
  • Syringe Temp . 150 °C
  • Agitator speed 250rpm
  • Fill Speed 25ul / s
  • Fill Strokes 0,
  • Injection Speed 700 ul / s
  • Pre Inject Delay 0 m
  • the protective film of the dry film photoresist specimen having a width of 3 cm and a length of 20 cm was removed, and the support film was removed after lamination at a speed of 2 m / min at 110 ° C. and 4 kgf / cm 2 on the copper-clad laminate.
  • the PET film After laminating a 4 cm wide, 25 cm long, 19 ⁇ m thick PET film (FDFR, manufactured by Kolon) at 110 ° C. and 4 kgf / cm 2 conditions at a rate of 2 m / min, the PET film began to be released.
  • the force required to release using a 10N load cell at a speed of 100 mm / min from the starting point of 5 cm to 8 cm was measured using UTM (4303 series, Instron).
  • the protective film of the dry film photoresist specimen having a width of 3 cm and a length of 20 cm was removed, and then laminated on the copper clad laminate at 110 ° C. at a speed of 2 m / min and a pressure of 4 kgf / cm 2. Then, the release force of the support film was measured using a UTM (4303 series, Instron) using a 10N load cell at a speed of 100 mm / min from a starting point of 5 cm to 8 cm at a starting point. At this time, releasing the support film means in the case of Examples 5 to 9 to release the release layer on one surface of the support film.
  • a universal testing machine was used to release a protective film of a dry film photoresist specimen having a width of 3 cm and a length of 20 cm, using a 10 N load cell at a speed of 100 mm / min from a starting point of 5 cm to 8 cm. , 4303 series, Instron).
  • the protective film of the dry film photoresist specimen having a width of 3 cm and a length of 20 cm was removed, and the support film was removed after lamination at a speed of 2 m / min at 110 ° C. and 4 kgf / cm 2 on the copper-clad laminate.
  • the removal of the support film means that in the case of Examples 1 to 5, the release layer on one surface of the support film was also removed.
  • Table 1 shows the results of measuring the adhesive strength of the dry film photoresist prepared by Examples 1 to 4 and Comparative Examples 1 to 4.
  • Conditions of lamination of the PET film is the same as the conditions that are bonded to the mask in the general exposure and the adhesive strength of the support film measured at this time in Table 1 is the resin protective layer in Examples 1 to 4 and Comparative Examples 2 to 4 And the adhesive force between the PET film and Comparative Example 1, the adhesive force between the photosensitive resin layer and the PET film.
  • Table 2 below shows the results of measuring the adhesive strength of the dry film photoresist prepared by Examples 5 to 9 and Comparative Example 1.
  • the conditions for lamination of the PET film are the same as the conditions for bonding with the mask during normal exposure.
  • the dry film photoresist prepared in Examples 1 to 9 and Comparative Examples 1 to 4 was formed on the printed circuit board by the following method, and then the characteristics of the dry film photoresist were evaluated.
  • a brush preprocessor is used for the copper clad laminate (CCL) to form new copper surfaces and to form the appropriate surface finish.
  • CCL copper clad laminate
  • the exposure was performed by irradiating with a UV exposure machine (Perkin Elmer OB-7120, 5KW parallel light). After the exposure, the printed circuit board was developed by passing through a developer.
  • the dry film photoresist prepared according to Examples 1 to 9 and Comparative Examples 1 to 4 was cut to a size of 7 cm ⁇ 7 cm, and then the protective film was peeled off and laminated on a copper clad laminate having a size of 10 cm ⁇ 10 cm. Then, after peeling off the support film of the laminated dry film photoresist, the resin protective layer was peeled off and the haze of the peeled resin protective layer was measured using a Haze Meter (NIPPON DENSHOKU, NDH-2000).
  • the printed circuit board after lamination of the dry film photoresist on the copper-clad laminate as shown in (a) is carried out at a pressure of 1.5 kgf / cm 2 under a condition of 30 ° C. (1% Na 2 CO 3).
  • a fan-type nozzle that sprays an aqueous solution) and a substrate having a distance of 15 cm After passing through a fan-type nozzle that sprays an aqueous solution) and a substrate having a distance of 15 cm, the time at which the laminated part is completely washed and removed by the developer is measured. , 'S min ').
  • the actual development time (hereinafter referred to as 'S del ') only of the photosensitive resin layer was calculated to be twice the minimum development time (S min ) of only the photosensitive resin layer.
  • the minimum development time (hereinafter referred to as 'P min ') of the film including the resin protective layer is a method of measuring the minimum development time (S min ) of the photosensitive resin layer was measured in the same way, a resin (referred to as' P del 'hereinafter), the protective layer the actual processing time of the film, including the processing time of the resin protection layer only on the actual developing time (S del) of the photosensitive resin layer only (hereinafter,' P tim '), which is shown in Equation 1 below.
  • Equation 2 Another expression of Equation 1 is expressed by Equation 2 below.
  • the minimum development time of the film including the resin protective layer and the minimum development time of the film not including the resin protective layer that is, the minimum development time of only the photosensitive resin layer, were measured, respectively.
  • the actual development time can be calculated.
  • the minimum development time S min of the photosensitive resin layer is determined by the minimum development time for the dry film photoresist of Comparative Example 1.
  • the developing time P tim of only the resin protective layer is calculated from Equations 1 and 2, and the value obtained by dividing the calculated developing time by the thickness of the resin protective layer is defined as the developing time per ⁇ m of the resin protective layer.
  • Examples 1 to 9 and Comparative Examples 2 to 4 were placed on a resin protective layer, and Comparative Example 1 was placed on a support film on a support film.
  • the exposure amount for obtaining 6 steps and 7 steps was measured using a photometer (UV-351, manufactured by ORC), and the values are shown in Table 3 below. At this time, the sensitivity was evaluated by the maximum number of units of the photosensitive resist remaining on the substrate after development.
  • the Kolon Test Artwork was used to evaluate the circuit properties by measuring the resolution, thin line adhesion, and 1/1 (Line / Space) resolution.
  • the resolution is a measure of how small the line width was developed when the unexposed areas were developed. The smaller this value, the higher the resolution.
  • the mask used for measuring the measured resolution was 0.5 ⁇ m up to 4 to 20 ⁇ m. The mask was formed at intervals of and a mask made with an interval of 400 ⁇ m was used for the resolution of the value to be implemented.
  • the thin line adhesion value is a measure of how small the line width after exposure is formed to form a straight line circuit without being eroded. The smaller the value, the better the fine line adhesion value, and the mask used for measuring the measured thin line adhesion value.
  • 1/1 resolution represents the value of the cleanest developed minimum line width with the distance between the circuit line and the circuit line 1: 1.
  • Table 3 shows the measurement results of the circuit properties according to the haze development time and exposure conditions, respectively.
  • the minimum development time (sec) means the minimum development time (P min ) of the film including the resin protective layer
  • the actual development time (sec) is the actual development of the film including the resin protective layer. It means time (P del ).
  • exceptionally * indicates the minimum development time (S min ) of the photosensitive resin layer only
  • ** ** means the actual development time (S del ) of the photosensitive resin layer only.
  • the development time per 1 ⁇ m of the resin protective layer is about 0.5 to 3 seconds.
  • FIGS. 1 to 3 are photographs of the printed circuit board surface to which the dry film photoresist according to Examples 1 and 5 is applied, the side and It can be seen that there is little surface irregularities and a very good pattern is formed.

Abstract

The present invention relates to a dry film photoresist, and more particularly to a dry film photoresist which can improve resolution by performing an exposure process in a removed state of a supporting film to prevent bad influence of an exposure effect due to the supporting film. In addition, the high resolution can be obtained by preventing the lowering of the transparency or the reduction of the developing speed while the exposure process is performed in presence of a resin protection layer. Particularly, the resin protection layer according to the present invention can reduce the manufacturing cost and the haze by reducing the wetting agent content such as polysilicon, can prevent the lowering of the haze by suppressing the damage of the resin protection layer, and can obtain the high resolution by preventing the reduction of the developing duration.

Description

드라이필름 포토레지스트Dry Film Photoresist
본 발명은 다층구조를 가지는 드라이필름 포토레지스트에 관한 것이다.The present invention relates to a dry film photoresist having a multilayer structure.
드라이필름 포토레지스트(dry film photoresist)은 1968년경에 미국 듀퐁사에 의해 'RISTON'이라는 상품명으로 개발된 이래 현재의 전기·전자 산업, 특히 인쇄회로기판 등의 가공에 중요한 재료로 사용되고 있다. Dry film photoresist has been used as an important material for the current electrical and electronic industries, especially printed circuit boards, since it was developed under the name RISTON by DuPont in 1968.
인쇄회로기판 상의 회로형성에 사용되는 포토레지스트 재료로는 전체의 약 50% 정도가 감광성 스크린 인쇄잉크가 사용되고 있으나, 고밀도와 고신뢰도가 요구되는 양면판 및 다층판의 인쇄회로기판 제작에는 드라이필름 포토레지스트가 필수적으로 사용되고 있다. About 50% of photoresist is used as a photoresist material for forming circuits on printed circuit boards, but dry film photo is used for the production of printed circuit boards of double-sided and multilayer boards requiring high density and high reliability. Resist is essentially used.
이 같은 드라이필름 포토레지스트는 지지체 필름(base film) 및 감광성 수지층(photosensitive layer)의 2층의 구조로 주로 적층되고, 드라이필름 포토레지스트의 사용하기 전까지 감광성 수지층을 보호하기 위하여 보호필름을 더 포함한다. The dry film photoresist is mainly laminated in a two-layer structure of a base film and a photosensitive layer, and further a protective film is used to protect the photosensitive resin layer until the dry film photoresist is used. Include.
일반적으로 지지체 필름은 폴리에틸렌 테레프탈레이트와 같은 폴리에스테르 필름을 사용하고, 그 두께는 25㎛ 정도이다. 이러한 지지체 필름은 드라이필름 포토레지스트를 제조하는 동안 감광성 수지층의 지지체 역할을 하는 것으로, 점착력을 갖고 있는 감광성 수지층의 노광시 취급이 용이하도록 하는 것이다. Generally, the support film uses a polyester film such as polyethylene terephthalate, and its thickness is about 25 μm. Such a support film serves as a support of the photosensitive resin layer during the manufacture of the dry film photoresist, and facilitates handling during exposure of the photosensitive resin layer having adhesive force.
감광성 수지는 광에 의한 반응 메커니즘에 의해 네가티브형과 포지티브형으로 나뉘는데, 네가티브형 감광성 수지의 경우는 노광된 부분에서 광가교 반응이 일어나고 미노광 부위는 알칼리에 씻겨 나가 레지스트 패턴이 남게 되며, 포지티브형 감광성 수지의 경우는 노광 부위에서 광분해 반응이 일어나 알칼리에 현상되며 미노광 부위가 남아 레지스트 패턴을 형성한다. Photosensitive resin is divided into negative type and positive type by the reaction mechanism by light. In the case of negative type photosensitive resin, photocrosslinking reaction occurs at the exposed part, and unexposed part is washed with alkali, leaving a resist pattern. In the case of the photosensitive resin, a photolysis reaction occurs at an exposure site and is developed in an alkali, and an unexposed site remains to form a resist pattern.
감광성 수지층은 광중합성 단량체, 광중합개시제, 바인더 폴리머 등을 포함하여 목적에 맞도록 제조된다. 이러한 감광성 수지층은 지지체 필름 위에 도포되며, 도포된 후 사용 목적에 알맞게 15 내지 100㎛까지의 두께를 갖는다. 이러한 감광성 수지층은 포토레지스트에 요구되는 기계적·화학적 성질과 가공 등의 조건에 따라 다양한 조성을 갖고 있다. The photosensitive resin layer is prepared to suit the purpose, including a photopolymerizable monomer, a photopolymerization initiator, a binder polymer, and the like. Such a photosensitive resin layer is applied on a support film, and has a thickness of 15 to 100 µm, after application, to suit the purpose of use. Such a photosensitive resin layer has various compositions according to the mechanical and chemical properties required for the photoresist and the conditions such as processing.
한편 보호필름은 취급시 레지스트의 손상을 방지해 주고, 먼지와 같은 이물질로부터 감광성 수지층을 보호하는 보호 덮게 역할을 하는 것으로서, 감광성 수지층의 지지체 필름이 형성되지 않은 이면에 적층된다. On the other hand, the protective film prevents damage to the resist during handling and serves as a protective cover to protect the photosensitive resin layer from foreign substances such as dust, and is laminated on the back surface where the support film of the photosensitive resin layer is not formed.
이와 같은 드라이필름 포토레지스트를 이용한 패턴 형성방법의 일예를 들면, 인쇄회로기판상에 적용시 먼저 보호필름을 벗겨내고 동장적층판(copper clad laminate; CCL) 상에 라미네이션(lamination)한 후 원하는 패턴의 마스크를 대고 자외선(UV)을 조사하여 노광(exposing)하고, 적절한 용제를 사용하여 경화되지 않은 부분을 씻어내는 현상(developing)과정을 거친다. As an example of a pattern forming method using such a dry film photoresist, a protective film is first peeled off and laminated on a copper clad laminate (CCL) when applied to a printed circuit board, followed by a mask having a desired pattern. Is exposed by irradiation with ultraviolet (UV) light and then developed using a suitable solvent to wash away the uncured parts.
통상적으로 이러한 조성을 가지는 드라이필름 포토레지스트를 이용하는 경우 노광 시에는 감광성 수지층에 지지체 필름이 부착된 채로 진행되므로 감광성 수지층과 마스크가 지지체 필름의 두께만큼 이격되어, 결과적으로는 해상도를 향상시키는데 한계가 있다. 또한, 자외선 광을 조사시켜 노광시키는 경우 자외선이 지지체 필름을 투과하게 되어 자외선 투과율에도 영향을 미치고, 지지체 필름 내부의 입자에 의한 자외선 산란 등으로 고해상도를 구현하는데 한계가 있다. In general, in the case of using a dry film photoresist having such a composition, since the support film is attached to the photosensitive resin layer during exposure, the photosensitive resin layer and the mask are separated by the thickness of the support film, and as a result, there is a limit to improving the resolution. have. In addition, when irradiated with ultraviolet light to expose the ultraviolet light is transmitted through the support film affects the ultraviolet transmittance, there is a limit in implementing a high resolution by ultraviolet scattering by the particles inside the support film.
이러한 점을 해결하기 위해 지지체 필름을 벗겨낸 후 노광할 수도 있으나, 감광성 수지층은 점착성을 갖고 있어 지지체 필름을 벗겨내면 마스크가 상기 감광성 수지층과 붙게 되므로 감광성 수지층에 손상이 가게 되며, 결과적으로는 해상도가 저하되고, 마스크가 오염되어 마스크의 수명이 단축되는 문제가 있다. In order to solve this problem, the support film may be peeled off and then exposed, but the photosensitive resin layer may be tacky, and when the support film is peeled off, the mask may stick to the photosensitive resin layer, resulting in damage to the photosensitive resin layer. The problem is that the resolution is lowered, the mask is contaminated, and the life of the mask is shortened.
따라서, 현실적으로 지지체 필름을 벗겨낸 후의 노광은 이루어지기 어렵고, 이로 인한 해상도 저하의 문제는 여전히 남아 있다. Therefore, in reality, the exposure after peeling off the support film is difficult to be achieved, and thus the problem of resolution reduction remains.
더욱이 인쇄회로기판의 고밀도화 및 반도체 패키징 기술의 발전에 따라 회로 선폭의 고밀도화가 진행됨으로써 이러한 미세회로기판에 적용할 수 있는 고해상의 드라이필름 포토레지스트에 대한 요구가 절실한 상황이다. Furthermore, as the density of printed circuit boards and semiconductor packaging technologies have increased, the density of circuit lines has been increased, so there is an urgent need for high resolution dry film photoresists applicable to such microcircuit boards.
본 발명은 지지체 필름을 제거한 상태에서 노광공정이 실시 가능하도록 하여 해상도를 향상시키고, 특히 지지체 필름과 수지 보호층을 적정 수준으로 접착시키면서 지지체 필름의 제거시 수지 보호층의 손상이 없는 드라이필름 포토레지스트를 제공하는 것이다.The present invention improves the resolution by allowing the exposure process to be performed in a state where the support film is removed, and in particular, while adhering the support film and the resin protective layer to an appropriate level, the dry film photoresist does not damage the resin protective layer when removing the support film To provide.
본 발명의 일 구현예는 지지체 필름, 수지 보호층 및 감광성 수지층을 순차적으로 적층하여 포함하고, 상기 수지 보호층은 수용성 고분자 및 알콕시알코올을 포함하는 드라이필름 포토레지스트이다. One embodiment of the present invention comprises a support film, a resin protective layer and a photosensitive resin layer by laminating sequentially, the resin protective layer is a dry film photoresist comprising a water-soluble polymer and an alkoxy alcohol.
본 발명의 다른 일 구현예는 지지체 필름 상에 적층된 이형층을 추가로 포함하고, 상기 이형층은 실리콘 수지, 불소 수지 및 지방족 왁스 중에서 선택된 1 종 이상인 것을 포함하고, 상기 수지 보호층은 중량평균분자량이 5000 내지 300000인 폴리비닐알코올을 포함하는 드라이필름 포토레지스트이다. Another embodiment of the present invention further includes a release layer laminated on a support film, wherein the release layer includes at least one selected from a silicone resin, a fluorine resin, and an aliphatic wax, and the resin protective layer has a weight average. Dry film photoresist comprising a polyvinyl alcohol having a molecular weight of 5000 to 300000.
본 발명의 다른 일 구현예는 상기 수지 보호층은 알콕시알코올을 30000ppm 이하로 포함하는 것인 드라이필름 포토레지스트이다. Another embodiment of the present invention is a dry film photoresist wherein the resin protective layer comprises less than 30000ppm alkoxyalcohol.
본 발명의 다른 일 구현예는 상기 알콕시알코올은 탄소수 1 내지 12의 알콕시기 및 탄소수 1 내지 12의 알코올기를 가지는 것인 드라이필름 포토레지스트이다. Another embodiment of the present invention is a dry film photoresist wherein the alkoxyalcohol has an alkoxy group having 1 to 12 carbon atoms and an alcohol group having 1 to 12 carbon atoms.
본 발명의 다른 일 구현예는 상기 알콕시알코올은 부톡시에탄올인 것인 드라이필름 포토레지스트이다. Another embodiment of the present invention is a dry film photoresist that the alkoxy alcohol is butoxy ethanol.
본 발명의 다른 일 구현예는 상기 수용성 고분자를 물 및 알콕시알코올을 포함하는 용매에 녹인 후 이를 지지체 필름 상에 코팅하여 수지 보호층을 형성하는 것인 드라이필름 포토레지스트이다. Another embodiment of the present invention is a dry film photoresist in which the water-soluble polymer is dissolved in a solvent containing water and alkoxyalcohol and then coated on a support film to form a resin protective layer.
본 발명의 다른 일 구현예는 상기 용매는 물 100 중량부에 대하여 알콕시알코올 1 내지 43중량부를 포함하는 것인 드라이필름 포토레지스트이다. Another embodiment of the present invention is a dry film photoresist wherein the solvent comprises 1 to 43 parts by weight of alkoxyalcohol with respect to 100 parts by weight of water.
본 발명의 다른 일 구현예는 상기 지지체 필름 및 수지 보호층 간의 점착력이 0.0005 내지 0.01 N/cm인 것인 드라이필름 포토레지스트이다. Another embodiment of the present invention is a dry film photoresist that the adhesion between the support film and the resin protective layer is 0.0005 to 0.01 N / cm.
본 발명의 다른 일 구현예는 상기 수지 보호층은 폴리실리콘을 포함하는 경우 수용성 고분자 100중량부에 대하여 폴리실리콘 0.01 내지 3중량부의 함량으로 포함하는 것인 드라이필름 포토레지스트이다. Another embodiment of the present invention is a dry film photoresist, wherein the resin protective layer includes polysilicon in an amount of 0.01 to 3 parts by weight based on 100 parts by weight of a water-soluble polymer.
본 발명의 다른 일 구현예는 상기 폴리실리콘은 물, 알코올류 및 이들의 혼합물 중에서 선택된 어느 하나의 용매 100g에 6시간 동안 80℃의 조건 하에서 폴리실리콘 0.1g 용해시 입도가 1㎛ 이하인 것인 드라이필름 포토레지스트이다. According to another embodiment of the present invention, the polysilicon has a particle size of 1 μm or less upon dissolving 0.1 g of polysilicon under a condition of 80 ° C. for 6 hours in 100 g of any one solvent selected from water, alcohols, and mixtures thereof. Film photoresist.
본 발명의 다른 일 구현예는 상기 수지 보호층은 헤이즈가 3.0% 이하인 것인 드라이필름 포토레지스트이다. Another embodiment of the present invention is a dry film photoresist wherein the resin protective layer has a haze of 3.0% or less.
본 발명의 다른 일 구현예는 상기 수지 보호층은 1㎛당 현상시간이 10초 이하인 것인 드라이필름 포토레지스트이다. Another embodiment of the present invention is a dry film photoresist wherein the resin protective layer has a developing time of 1 μm or less.
본 발명의 다른 일 구현예는 상기 이형층 및 수지 보호층 간의 점착력이 0.0005 내지 0.01 N/cm인 것인 드라이필름 포토레지스트이다. Another embodiment of the present invention is a dry film photoresist that the adhesion between the release layer and the resin protective layer is 0.0005 to 0.01 N / cm.
본 발명의 다른 일 구현예는 상기 수지 보호층은 두께가 10㎛ 이하인 것인 드라이필름 포토레지스트이다. Another embodiment of the present invention is a dry film photoresist wherein the resin protective layer is less than 10㎛ thickness.
본 발명의 다른 일 구현예는 상기 폴리비닐알코올은 검화도가 75 내지 97%인 것인 드라이필름 포토레지스트이다.Another embodiment of the present invention is a polyvinyl alcohol is a dry film photoresist having a degree of saponification of 75 to 97%.
본 발명에 따른 드라이필름 포토레지스트는 지지체 필름을 제거한 상태로 노광공정을 실시하는 것이 가능하여, 지지체 필름에 의한 노광 효과의 악영향을 방지함으로써 궁극적으로 해상도를 향상시킬 수 있다. The dry film photoresist according to the present invention can be subjected to the exposure process with the support film removed, thereby ultimately improving the resolution by preventing adverse effects of the exposure effect by the support film.
특히, 본 발명에 따른 수지 보호층은 폴리실리콘과 같은 웨팅제(wetting agent)의 함량을 줄일 수 있어 원가를 절감시키면서 헤이즈(haze)를 낮추는 효과를 얻을 수 있고, 지지체 필름과 수지 보호층을 적정 수준으로 접착시키면서 지지체 필름을 제거할 때 수지 보호층의 손상을 주지 않아 헤이즈의 저하를 방지할 수 있고, 현상시간의 저하도 발생하지 않아 고해상도를 달성할 수 있다. In particular, the resin protective layer according to the present invention can reduce the content of a wetting agent such as polysilicon to obtain a haze (lower effect) while reducing the cost, titrating the support film and the resin protective layer When the support film is removed while adhering at the level, the resin protective layer is not damaged, and the haze can be prevented, and the development time can be prevented from being lowered, thereby achieving a high resolution.
도 1은 본 발명의 실시예 1에서 제조된 현상 공정 후의 인쇄회로기판의 표면을 1200배로 확대하여 촬영한 전자현미경 사진이다. 1 is an electron micrograph taken at 1200 times magnification of the surface of a printed circuit board after the developing process manufactured in Example 1 of the present invention.
도 2는 본 발명의 실시예 5에서 제조된 현상 공정 후의 인쇄회로기판의 표면을 1200배로 확대하여 촬영한 전자현미경 사진이다. 2 is an electron micrograph taken at 1200 times magnification of the surface of a printed circuit board after the developing process manufactured in Example 5 of the present invention.
도 3은 비교예 1에서 제조된 현상 공정 후의 인쇄회로기판의 표면을 1200배로 확대하여 촬영한 전자현미경 사진이다. 3 is an electron micrograph taken at a magnification of 1200 times the surface of a printed circuit board after the developing process manufactured in Comparative Example 1. FIG.
본 발명의 일 구현예에 따르면, 지지체 필름, 수지 보호층 및 감광성 수지층을 순차적으로 적층하여 포함하고, 상기 수지 보호층은 수용성 고분자 및 알콕시알코올을 포함하는 드라이필름 포토레지스트를 제공하는 것이다. According to one embodiment of the present invention, a support film, a resin protective layer and a photosensitive resin layer are sequentially laminated and included, and the resin protective layer is to provide a dry film photoresist including a water-soluble polymer and an alkoxy alcohol.
본 발명의 드라이필름 포토레지스트는 지지체 필름, 이형층, 수지 보호층 및 감광성 수지층을 순차적으로 적층하여 포함하는 구조로 되어있다. The dry film photoresist of the present invention has a structure in which a support film, a release layer, a resin protective layer, and a photosensitive resin layer are sequentially stacked and included.
상기 지지체 필름은 수지 보호층과 감광성 수지층의 지지체 역할을 하므로 충분한 기계적 특성을 구비한 것이 바람직하다. 보다 구체적으로 지지체 필름으로는 폴리에틸렌테레프탈레이트 필름, 및 폴리에틸렌나프탈레이트 필름과 같은 폴리에스테르계 필름; 폴리에틸렌 필름, 및 폴리프로필렌 필름과 같은 폴리올레핀계 필름; 폴리비닐클로라이드와 비닐 아세테이트의 공중합체 필름, 폴리테트라플루오로에틸렌 필름, 및 폴리트리플루오로에틸렌 필름과 같은 폴리비닐계 필름; 폴리이미드계 필름; 6,6-나일론과 같은 폴리아미드계 필름; 셀룰로오스트리아세테이트 필름, 및 셀룰로오스디아세테이트 필름과 같은 폴리아세테이트계 필름; 알킬폴리(메트)아크릴레이트 필름과 같은 폴리아크릴레이트계 필름; (메트)아크릴산에스테르 공중합체 필름과 같은 폴리아크릴계 필름; 등을 들 수 있으며, 이들 중 기계적 특성 및 경제성을 고려하여 바람직하게는 폴리에틸렌테레프탈레이트를 들 수 있다. Since the support film serves as a support of the resin protective layer and the photosensitive resin layer, it is preferable to have sufficient mechanical properties. More specifically, the support film includes a polyester film such as polyethylene terephthalate film and polyethylene naphthalate film; Polyolefin-based films such as polyethylene films, and polypropylene films; Polyvinyl-based films such as copolymer films of polyvinylchloride and vinyl acetate, polytetrafluoroethylene films, and polytrifluoroethylene films; Polyimide film; Polyamide-based films such as 6,6-nylon; Polyacetate-based films such as cellulose triacetate film and cellulose diacetate film; Polyacrylate-based films such as alkyl poly (meth) acrylate films; Polyacrylic films such as (meth) acrylic acid ester copolymer films; These etc. are mentioned, Preferably, a polyethylene terephthalate is mentioned in consideration of mechanical properties and economics.
상기 지지체 필름의 두께는 10 내지 100㎛의 범위에서 임의의 목적에 따라 선택할 수 있다. The thickness of the support film can be selected according to any purpose in the range of 10 to 100 μm.
상기 수지 보호층은 수용성 고분자 및 알콕시알코올을 포함한다. The resin protective layer includes a water-soluble polymer and an alkoxy alcohol.
이를 구체적으로 설명하면 수지 보호층은 수용성 고분자를 포함하고 있어, 수용성 고분자를 용해시키기 위하여 용매로서 물을 사용할 수 있는데, 상기 알콕시알코올은 물보다 표면장력이 작기 때문에 지지체 필름에 수지 보호층을 형성하기 위한 코팅액, 즉 수용성 고분자 및 알콕시알코올을 포함하는 코팅액을 도포할 때 웨팅성(wetting)을 향상시켜 도막이 잘 형성되는 효과를 얻을 수 있다. Specifically, the resin protective layer includes a water-soluble polymer, so that water may be used as a solvent to dissolve the water-soluble polymer. Since the alkoxy alcohol has a smaller surface tension than water, the resin protective layer may be formed on the support film. When the coating liquid, that is, a coating liquid containing a water-soluble polymer and an alkoxyalcohol is improved, the wetting property (wetting) can be improved to obtain an effect of forming a coating film well.
또한, 이러한 웨팅성을 향상시키기 위하여 수지 보호층에 폴리실리콘과 같은 웨팅제를 첨가할 수 있는데, 수지 보호층에 알콕시알코올을 포함하는 경우 웨팅제의 함량을 줄여도 웨팅성을 향상시킬 수 있어, 웨팅제의 함량을 감소시킬 수 있어 원가가 절감되는 경제적인 효과를 얻을 수 있다. 특히 수용성 고분자를 포함하는 수지 보호층에 웨팅제로서 사용할 수 있는 폴리실리콘을 첨가하는 경우 폴리실리콘은 물보다 알콕시알코올에 대한 용해도(solubility)가 높기 때문에 헤이즈(haze)를 낮출 수 있고 결과적으로 고해상도를 구현할 수 있다. 이러한 점에서 상기 알콕시알코올은 수지 보호층에 수용성 고분자와 함께 포함되는 것이 바람직하다. In addition, in order to improve the wettability, a wetting agent such as polysilicon may be added to the resin protective layer. When the alkoxy alcohol is included in the resin protective layer, the wetting property may be improved even if the content of the wetting agent is reduced. Since the content of the tinting agent can be reduced, an economic effect of reducing the cost can be obtained. In particular, when polysilicon, which can be used as a wetting agent, is added to a resin protective layer containing a water-soluble polymer, polysilicon has a higher solubility in alkoxy alcohol than water, thereby lowering haze and consequently high resolution. Can be implemented. In this regard, the alkoxyalcohol is preferably included with the water-soluble polymer in the resin protective layer.
상술한 알콕시알코올은 30000ppm 이하의 함량으로 수지 보호층에 포함하는 것이 바람직하다. 상기 알콕시알코올의 함량은 수지 보호층이 지지체 필름 상에 형성되어 건조된 후의 함량을 의미하는 것으로 수지 보호층에 알콕시알코올의 함량이 낮을 것이 요구되므로 알콕시알코올의 하한값은 낮을수록 좋다. 상기 알콕시알코올의 함량이 상기 범위 내에 있는 경우 본 발명에서 원하는 수준 이상으로 수지 보호층의 물성을 가질 수 있다. The alkoxyalcohol described above is preferably included in the resin protective layer in an amount of 30000 ppm or less. The content of the alkoxyalcohol refers to the content after the resin protective layer is formed on the support film and dried. Since the content of the alkoxyalcohol is required to be low in the resin protective layer, the lower the lower limit of the alkoxyalcohol is better. When the content of the alkoxyalcohol is within the above range, it may have physical properties of the resin protective layer above the desired level in the present invention.
상기 알콕시알코올은 탄소수 1 내지 12의 알콕시기 및 탄소수 1 내지 12의 알코올기, 바람직하게는 탄소수 1 내지 6의 알콕시기 및 탄소수 1 내지 6의 알코올기를 가지는 것이 좋다. The alkoxyalcohol preferably has an alkoxy group having 1 to 12 carbon atoms and an alcohol group having 1 to 12 carbon atoms, preferably an alkoxy group having 1 to 6 carbon atoms and an alcohol group having 1 to 6 carbon atoms.
상기 알콕시알코올의 구체적인 예로는 2-n-헥소시에탄올(2-n-hexoxyethanol), 2-(2-메틸펜톡시)에탄올(2-(2-methylpentoxy)ethanol), 2-(3-메틸펜톡시)에탄올(2-(3-methylpentoxy)ethanol), 2-(2,3-디메틸부톡시)에탄올(2-(2,3-dimethylbutoxy)ethanol), 2-(2,2-디메틸부톡시)에탄올(2-(2,2-dimethylbutoxy)ethanol), 2-n-펜톡시에탄올(2-n-pentoxyethanol), 2-이소-펜톡시에탄올(2-iso-pentoxyethanol), 2-네오-펜톡시에탄올(2-neo-pentoxyethanol), 2-n-부톡시에탄올(2-n-butoxyethanol), 2-이소-부톡시에탄올(2-iso-butoxyethanol), 2-n-프로폭시에탄올(2-n-propoxyethanol), 2-이소-프로폭시에탄올(2-iso-propoxyethanol), 2-에톡시에탄올(2-ethoxyethanol), 2-메톡시에탄올(2-methoxyethanol), n-헥소시메탄올(n-hexoxymethanol), (2-메틸펜톡시)메탄올((2-methylpentoxy)methanol), (3-메틸펜톡시)메탄올((3-methylpentoxy)methanol), (2,3-디메틸부톡시)메탄올((2,3-dimethylbutoxy)methanol), (2,2-디메틸부톡시)메탄올((2,2-dimethylbutoxy)methanol), n-펜톡시메탄올(n-pentoxymethanol), 이소-펜톡시메탄올(iso-pentoxymethanol), 네오-펜톡시메탄올(neo-pentoxymethanol), n-부톡시메탄올(n-butoxymethanol), 이소-부톡시메탄올(iso-butoxymethanol), n-프로폭시메탄올(n-propoxymethanol), 이소-프로폭시메탄올(iso-propoxymethanol), 에톡시메탄올(ethoxymethanol), 메톡시메탄올(methoxymethanol) 등을 들 수 있다. 본 발명의 목적한 바에 따른 효과를 얻는 면에서 상기 알콕시알코올은 부톡시에탄올인 것이 바람직하다. Specific examples of the alkoxyalcohol include 2-n-hexoxyethanol, 2- (2-methylpentoxy) ethanol, and 2- (3-methylphene. 2- (3-methylpentoxy) ethanol), 2- (2,3-dimethylbutoxy) ethanol, 2- (2,2-dimethylbutoxy) Ethanol (2- (2,2-dimethylbutoxy) ethanol), 2-n-pentoxyethanol, 2-iso-pentoxyethanol, 2-neo-pentoxy Ethanol (2-neo-pentoxyethanol), 2-n-butoxyethanol, 2-iso-butoxyethanol, 2-n-propoxyethanol (2-n -propoxyethanol), 2-iso-propoxyethanol, 2-ethoxyethanol, 2-methoxyethanol, n-hexoxymethanol ), (2-methylpentoxy) methanol), (3-methylpentoxy) methanol, (2,3-dimethylbutoxy) methanol ((2, 3-dimethylbutoxy) methanol), (2,2-dimeth Methylol ((2,2-dimethylbutoxy) methanol), n-pentoxymethanol, iso-pentoxymethanol, neo-pentoxymethanol, n- N-butoxymethanol, iso-butoxymethanol, n-propoxymethanol, iso-propoxymethanol, ethoxymethanol, methoxymethanol And methoxymethanol. It is preferable that the said alkoxy alcohol is butoxy ethanol from the point which acquires the effect according to the objective of this invention.
본 발명에 따른 드라이필름 포토레지스트는 상기 수용성 고분자를 물 및 알콕시알코올을 포함하는 용매에 녹인 후 이를 지지체 필름 상에 코팅하여 형성된 수지 보호층을 포함하는 것이다. 상기 용매에 수용성 고분자를 녹여 수지 보호층을 형성하는 경우 물에 의해 수용성 고분자가 균일하게 녹을 수 있으며, 알콕시알코올은 물보다 표면장력이 작기 때문에 지지체 필름에 수지 보호층을 형성하기 위한 코팅액, 즉 수용성 고분자 및 알콕시알코올을 포함하는 코팅액을 도포할 때 웨팅성(wetting)을 향상시켜 도막이 잘 형성되는 효과를 얻을 수 있다. Dry film photoresist according to the invention comprises a resin protective layer formed by dissolving the water-soluble polymer in a solvent containing water and alkoxyalcohol and then coating it on a support film. When the water-soluble polymer is dissolved in the solvent to form a resin protective layer, the water-soluble polymer may be uniformly dissolved by water. Since the alkoxy alcohol has a smaller surface tension than water, a coating solution for forming a resin protective layer on the support film, that is, water-soluble. When the coating liquid containing the polymer and the alkoxyalcohol is applied, wetting may be improved to obtain an effect of forming a coating film well.
상술한 수지 보호층은 수용성 고분자 및 알콕시알코올을 포함하는데, 수지 보호층은 수용성 고분자로 인하여 물을 용매로 사용할 수 있는데, 이러한 수용성 고분자는 물에 비하여 알콕시알코올에 대한 용해도가 낮아 물과 함께 사용하는 것이 바람직하다. 즉, 수용성 고분자는 알콕시알코올에 대한 용해도가 물에 비하여 낮기 때문에 알콕시알코올의 함량이 증가하면 수용성 고분자의 함량이 감소될 수 있고, 수용성 고분자의 함량을 증가시키기 위하여 물의 함량을 증가시키는 경우 웨팅성이 저하되는 문제가 발생할 수 있다. 이러한 웨팅성이 저하되는 문제를 방지하기 위하여 수지 보호층에 웨팅제를 첨가시킬 수 있으나, 이러한 첨가제로 인하여 헤이즈가 높아지는 문제가 발생하게 된다. 이러한 면에서 상기 수지 보호층은 알콕시알코올과 함께 물을 포함하는 것이 바람직하고, 상기 용매에 알콕시알코올과 물을 포함하는 경우 적정 수준의 범위로 포함되어야 한다. The resin protective layer described above includes a water-soluble polymer and an alkoxy alcohol, and the resin protective layer may use water as a solvent due to the water-soluble polymer. Such a water-soluble polymer has low solubility in alkoxy alcohols compared to water, and thus may be used with water. It is preferable. That is, since the water solubility of the alkoxyalcohol is lower than that of water, the content of the water-soluble polymer may decrease when the content of the alkoxyalcohol is increased, and the wettability is increased when the water content is increased to increase the content of the water-soluble polymer. Degradation problems may occur. Although a wetting agent may be added to the resin protective layer in order to prevent such a problem of deterioration of the wettability, a problem of high haze occurs due to such an additive. In this respect, the resin protective layer preferably includes water together with the alkoxyalcohol, and when the alkoxyalcohol and the water are included in the solvent, the resin protective layer should be included in an appropriate level range.
상기 용매는 물 100 중량부에 대하여 알콕시알코올 1 내지 43중량부를 포함할 수 있다. 상기 물 100 중량부에 대한 알콕시알코올의 함량이 상기 범위 내에 있는 경우 수용성 고분자를 본 발명이 원하는 수준의 함량으로 균일하게 용해시키면서 웨팅성을 향상시키는 효과를 얻을 수 있다. The solvent may include 1 to 43 parts by weight of alkoxyalcohol based on 100 parts by weight of water. When the content of the alkoxyalcohol with respect to 100 parts by weight of water is within the above range, it is possible to obtain an effect of improving the wettability while uniformly dissolving the water-soluble polymer in the content of the level desired by the present invention.
상술한 구성을 포함하는 경우 상기 수지 보호층의 헤이즈가 3.0% 이하이고, 1㎛당 현상속도가 10초 이하일 수 있다. When the above-described configuration is included, the haze of the resin protective layer may be 3.0% or less, and the developing speed per 1 μm may be 10 seconds or less.
본 발명에 따른 드라이필름 포토레지스트를 패턴 형성방법에 이용하는 경우 일례를 들어 설명하면, 먼저 지지체 필름, 수지 보호층 및 감광성 수지층이 순차적으로 적층된 드라이필름 포토레지스트에서 감광성 수지층의 일면에 보호필름이 있는 경우 보호필름을 벗겨내고 감광성 수지층의 일면과 동장적층판(CCL) 상부가 닿도록 라미네이션(lamination)한다. 그 다음 지지체 필름을 제거하고 원하는 패턴의 마스크를 수지 보호층 상에 대고 자외선(UV)을 조사하여 노광(exposing)하고, 적절한 현생액을 사용하여 경화되지 않은 부분을 씻어내는 현상(developing)과정을 거친다. In the case of using the dry film photoresist according to the present invention in the pattern forming method, an example is described. First, a protective film on one surface of the photosensitive resin layer in a dry film photoresist in which a support film, a resin protective layer and a photosensitive resin layer are sequentially laminated. If present, peel off the protective film and lamination so that one surface of the photosensitive resin layer and the upper part of the copper clad laminate (CCL) are in contact with each other. Then, the support film is removed, the mask of the desired pattern is applied on the resin protective layer, exposed by ultraviolet (UV) exposure, and the developing process of washing off the uncured portion using a suitable supernatant is performed. Rough
현상액은 대부분 수용성 용매로 이루어져 있는데, 현상 후 잔여물이 감광성 수지층에 남아 있지 않도록 수지 보호층이 현상액의 수용성 용매에 잘 녹아 씻겨나가는 것이 중요하고, 이것은 현상성을 높이는 요소중의 하나이다. The developer is mostly composed of a water-soluble solvent. It is important that the resin protective layer is well dissolved in the water-soluble solvent of the developer so that the residue does not remain in the photosensitive resin layer after development, and this is one of the factors that improve the developability.
특히, 수지 보호층에 포함되는 수용성 고분자는 중량평균분자량이 증가할수록 용해도가 저하되어 현상액에 씻겨나가는 정도가 저하될 수 있다. In particular, the water-soluble polymer included in the resin protective layer may decrease the solubility of the water-soluble polymer as the weight average molecular weight increases, so that the degree of washing in the developer.
이러한 현상성은 또한 현상속도에도 영향을 받는데, 수지 보호층의 현상속도가 빠를수록 좋지만, 수지 보호층의 현상속도가 느리면 수지 보호층의 두께편차에 따른 현상시간의 차이가 많이 발생하게 되어 감광성 수지층이 필요이상으로 많이 씻겨 밀착력이 저하될 수 있고, 혹은 덜 씻겨나가 해상력이 저하될 수 있기 때문에 정밀한 패턴형성을 위하여 수지 보호층의 현상속도는 감광성 수지층의 현상을 고려하여 적절한 속도를 가져야 한다. This developability is also affected by the developing speed. The faster the developing speed of the resin protective layer is, the better. However, when the developing speed of the resin protective layer is slow, a large difference in developing time due to the thickness deviation of the resin protective layer is caused. Since the adhesive force may be reduced by washing more than necessary, or the resolution may be reduced by less washing, the developing speed of the resin protective layer should have an appropriate speed in consideration of the phenomenon of the photosensitive resin layer in order to form a precise pattern.
따라서, 수지 보호층은 현상성을 향상시키기 위하여 적정 수준의 중량평균분자량을 가지는 수용성 고분자를 포함하고, 잔여물이 남지 않고 감광성 수지층의 경화된 부분에 손상이 가지 않도록 적정한 수준의 현상속도를 가지는 것이 중요하다.Therefore, the resin protective layer includes a water-soluble polymer having an appropriate weight average molecular weight in order to improve developability, and has an appropriate level of developing speed so that no residue remains and no damage is caused to the cured portion of the photosensitive resin layer. It is important.
본 발명에 따른 수용성 고분자는 중량평균분자량이 5000 내지 300000, 바람직하게는 5000 내지 15000, 더욱 바람직하게는 5000 내지 10000인 폴리비닐알코올이 바람직하다. 상기 중량평균분자량이 5000미만이면 필름상의 도포가 곤란해지고, 강도가 약해 감광성 수지층의 보호 기능을 수행하기 힘들어 바람직하지 않으며, 300000을 초과하면 현상시간이 길어지고 동장적층판 상에 적층 후 지지체 필름을 박리시킬 때 손상될 우려가 있다.The water-soluble polymer according to the present invention is preferably polyvinyl alcohol having a weight average molecular weight of 5000 to 300000, preferably 5000 to 15000, more preferably 5000 to 10000. When the weight average molecular weight is less than 5000, the coating on the film becomes difficult, and the strength is weak, so that it is difficult to perform the protective function of the photosensitive resin layer. If the weight average molecular weight exceeds 300,000, the development time becomes longer and the support film is laminated on the copper clad laminate. There is a risk of damage when peeling.
상기 폴리비닐알코올은 검화도가 75%내지 97%인 것이 바람직하다. 상기 검화도는 현상성에 영향을 미치는 요소로서 상기 검화도가 상기 범위 내에 있는 경우 수지 보호층이 적절한 현상시간을 가져 감광성 수지층을 형성하는데 밀착력의 저하와 해상도의 저하를 가져오지 않는 효과가 있다. The polyvinyl alcohol preferably has a saponification degree of 75% to 97%. The degree of saponification is a factor that affects the developability. When the degree of saponification is within the above range, the resin protective layer has an appropriate developing time to form the photosensitive resin layer, thereby reducing the adhesion and the resolution.
한편, 해상도를 향상시키기 위한 방법 중의 하나로 패턴을 보다 세밀하게 형성시키는 것이 중요한데, 세밀한 패턴형성을 위해서는 노광시 수지 보호층으로의 광산란도가 낮아야 하므로 헤이즈 값이 낮을 것이 요구된다. 이는 드라이필름 포토레지스트에서 감광성 수지층을 노광하는 경우, 광이 수지 보호층을 통과하기 때문이다. On the other hand, as one of the methods for improving the resolution, it is important to form the pattern more precisely. In order to form a fine pattern, the light scattering degree to the resin protective layer during exposure should be low, so the haze value is required to be low. This is because light passes through the resin protective layer when the photosensitive resin layer is exposed in the dry film photoresist.
상기 수지 보호층은 헤이즈가 3.0% 이하, 바람직하게는 0.001 내지 3.0%인 값을 가질 수 있으며, 상기 헤이즈가 상기 범위 내에 있는 경우 노광시 광투과율을 높여 해상도를 향상시킬 수 있다. The resin protective layer may have a haze value of 3.0% or less, preferably 0.001 to 3.0%. When the haze is in the range, the light transmittance may be increased to increase the resolution.
이를 구체적으로 설명하면 상기 수지 보호층의 헤이즈는 광산란도를 낮추기 위하여 낮은 값을 가지는 것이 요구되므로, 하한값이 낮을수록 바람직하고, 3%를 초과하는 경우 노광, 현상과정을 거친 감광수지층의 형상(side wall)이 매끈하지 못하고 거칠게 되는 문제가 있다. Specifically, since the haze of the resin protective layer is required to have a low value in order to lower the light scattering degree, a lower limit value is preferable, and in the case of more than 3%, the shape of the photosensitive resin layer that has been exposed and developed ( The side wall is not smooth and rough.
상기 수지 보호층은 1㎛당 현상속도가 10초 이하, 바람직하게는 0.1 내지 10초인 값을 가질 수 있으며, 상기 범위 내에 있는 경우 최적의 현상속도를 가짐에 따라 해상도를 향상시킬 수 있다. The resin protective layer may have a value in which the developing speed per μm is 10 seconds or less, preferably 0.1 to 10 seconds. When the resin protective layer is in the above range, the resolution may be improved by having an optimum developing speed.
이를 구체적으로 설명하면 상기 수지 보호층의 현상속도는 현상성의 향상을 위하여 낮은 값을 가지는 것이 요구되므로, 하한값이 낮을수록 바람직하고, 10초를 초과하는 경우 수지 보호층의 두께편차에 따른 현상시간의 차이가 많이 발생하게 되어 감광성 수지층이 필요이상으로 많이 씻겨 밀착력이 저하될 수 있고, 혹은 덜 씻겨나가 해상력이 저하되는 문제가 있다.Specifically, since the development speed of the resin protective layer is required to have a low value for improving the developability, the lower the lower limit is, the more preferable, and when it exceeds 10 seconds, the development time according to the thickness deviation of the resin protective layer There is a problem that the difference occurs a lot of the photosensitive resin layer is washed more than necessary to reduce the adhesion, or less washed off the resolution.
또한, 본 발명의 드라이필름 포토레지스트은 노광공정 전 지지체 필름을 제거하여 노광공정이 실시가능하기 때문에 종래 지지체 필름을 제거한 상태에서 노광공정을 실시하는 경우 마스크와의 접촉으로 인하여 발생하는 감광성 수지층 상의 손상 및 마스크의 오염을 방지할 수 있으며, 지지체 필름 중에 포함된 입자로 인한 악영향을 방지하는 효과도 얻을 수 있다. In addition, the dry film photoresist of the present invention may be subjected to the exposure process by removing the support film before the exposure process, so that the damage on the photosensitive resin layer caused by contact with the mask when performing the exposure process with the conventional support film removed And it is possible to prevent the contamination of the mask, it is also possible to obtain the effect of preventing adverse effects due to particles contained in the support film.
상기 수지 보호층은 지지체 필름이 제거되는 경우를 고려하여 지지체 필름과 적정 수준으로 점착력을 가질 것이 요구되는데, 지지체 필름을 수지 보호층으로부터 떼어낼 때 수지 보호층의 표면에 손상을 주지 않아야 한다는 점에서 지지체 필름 및 수지 보호층 간의 점착력은 0.0005 내지 0.01 N/cm인 것이 바람직하다. 이를 구체적으로 설명하면 상기 점착력이 상기 범위 내에 있는 경우 라미네이션을 할 때 보호필름을 제거하는 경우 지지체 필름과 수지 보호층이 분리되지 않는 장점이 있고, 노광 전 지지체 필름을 제거할 때 수지 보호층에 손상을 주지 않고 제거할 수 있는 장점이 있다. The resin protective layer is required to have an appropriate level of adhesion with the support film in consideration of the case where the support film is removed, in that the surface of the resin protective layer should not be damaged when the support film is removed from the resin protective layer. It is preferable that the adhesive force between a support film and a resin protective layer is 0.0005-0.01 N / cm. In detail, when the adhesive force is within the range, when the protective film is removed during lamination, the support film and the resin protective layer are not separated, and the resin protective layer is damaged when the support film is removed before exposure. There is an advantage that can be removed without giving.
한편, 본 발명에 따른 수지 보호층은 폴리실리콘을 포함할 수 있다. Meanwhile, the resin protective layer according to the present invention may include polysilicon.
상기 폴리실리콘은 수지 보호층에 이형성을 부여하는 역할을 하며, 지지체 필름 및 수지 보호층 간의 점착력 및 헤이즈에도 영향을 미칠 수 있다. 상기 폴리실리콘을 수지 보호층에 포함하는 경우 상기 수지 보호층은 수용성 고분자 100중량부에 대하여 폴리실리콘 0.01 내지 3중량부의 함량으로 포함하는 것일 수 있다. 상기 수용성 고분자 100 중량부에 대한 폴리실리콘의 함량은 지지체 필름상의 도포의 용이함 및 건조 후 수지 보호층의 헤이즈를 고려한 면에서 상기 범위 내로 실시하는 것이 바람직하다. The polysilicon serves to impart releasability to the resin protective layer, and may also affect adhesion and haze between the support film and the resin protective layer. When the polysilicon is included in the resin protective layer, the resin protective layer may be included in an amount of 0.01 to 3 parts by weight of polysilicon based on 100 parts by weight of the water-soluble polymer. The content of polysilicon relative to 100 parts by weight of the water-soluble polymer is preferably carried out within the above range in consideration of ease of application on the support film and haze of the resin protective layer after drying.
이러한 폴리실리콘은 물, 알코올류 및 이들의 혼합물 중에서 선택된 어느 하나의 용매에 용해성을 가지는 것이다. 폴리실리콘이 유기용매에 녹는 것이라면 물 및 알코올류나 이들을 혼합한 용매에 녹지 않아 입도가 현저히 증가하여 본 발명에서는 바람직하지 않다. Such polysilicon is soluble in any one solvent selected from water, alcohols and mixtures thereof. If the polysilicon is dissolved in an organic solvent, it does not dissolve in water and alcohols or a mixed solvent thereof, so that the particle size is significantly increased, which is not preferable in the present invention.
상기 폴리실리콘은 용액방식의 입도측정기로 측정하여 상기 용매 100g에 6시간 동안 80℃의 조건 하에서 폴리실리콘 0.1g을 녹였을 때 입도가 1㎛ 이하를 가지는 것이며, 폴리실리콘을 모두 녹이는 것이 바람직한 면에서 입도의 하한값은 낮을수록 좋다. 상기 폴리실리콘의 입도가 상기 범위 내에 있는 경우 헤이즈의 저하를 방지하고, 감광성 수지층의 회로형성 시 형상(side wall)이 저하되는 것을 방지할 수 있다. The polysilicon has a particle size of 1 μm or less when dissolved in 0.1 g of polysilicon under conditions of 80 ° C. for 6 hours in a solution-type particle size measuring device, and it is preferable to dissolve all polysilicon. The lower the lower limit of the particle size, the better. When the particle size of the polysilicon is in the above range, it is possible to prevent a decrease in haze and to prevent a side wall from being lowered during circuit formation of the photosensitive resin layer.
상기 수지 보호층은 10㎛ 이하, 바람직하게는 0.001 내지 10㎛, 더 바람직하게는 0.001 내지 5㎛의 두께를 가지는 것이다. The resin protective layer has a thickness of 10 μm or less, preferably 0.001 to 10 μm, more preferably 0.001 to 5 μm.
상술한 바와 같이 노광시 마스크를 대고 빛을 조사시키는데, 마스크와 감광성 수지층과의 거리가 가까울수록 고해상도를 구현할 수 있다. 이를 위하여 감광성 수지층의 상부에 마스크를 대고 노광하는 것이 가장 좋으나, 감광성 수지층의 점착성으로 인해 마스크와 붙게 되므로 감광성 수지층이 손상될 뿐만 아니라 마스크도 오염되고, 이러한 문제로 인하여 종래에는 해상도를 향상시키는데 한계가 있었다. As described above, light is applied to the mask during exposure, and the closer the distance between the mask and the photosensitive resin layer is, the higher the resolution can be realized. For this purpose, it is best to expose the mask on top of the photosensitive resin layer, but since the adhesiveness of the photosensitive resin layer causes the mask to adhere to the mask, not only the photosensitive resin layer is damaged but also the mask is contaminated. There was a limit to.
본 발명은 고해상도를 구현하기 위하여 수지 보호층의 두께가 낮은 값을가지는 것이 요구되므로 하한값이 낮을수록 바람직하고, 따라서 10㎛ 이하의 두께를 가지는 수지 보호층을 사용함으로써, 마스크와의 이격거리를 최소화하고, 지지체 필름을 제거하고 노광을 실시하여도 감광성 수지층의 손상 및 마스크의 오염이 발생하지 않아, 종래 해상도를 향상시키는 데 있었던 한계를 극복할 수 있고, 따라서 고해상도를 구현할 수 있다. The present invention is required to have a low thickness of the resin protective layer in order to implement a high resolution, so the lower the lower limit is preferable, and therefore, by using a resin protective layer having a thickness of 10㎛ or less, to minimize the separation distance with the mask In addition, even when the support film is removed and subjected to exposure, damage to the photosensitive resin layer and contamination of the mask do not occur, so that the limitations of the conventional resolution can be overcome, and high resolution can thus be realized.
본 발명의 다른 일 구현예에 따르면, 상기 지지체 필름 상에 적층된 이형층을 추가로 포함하고, 상기 이형층은 실리콘 수지, 불소 수지, 및 지방족 왁스 중에서 선택된 1 종 이상인 것을 포함하고, 상기 수지 보호층은 중량평균분자량이 5000 내지 300000, 바람직하게는 5000 내지 15000, 더욱 바람직하게는 5000 내지 10000인 폴리비닐알코올을 포함하는 드라이필름 포토레지스트를 제공하는 것이다. According to another embodiment of the present invention, further comprising a release layer laminated on the support film, the release layer comprises at least one selected from silicone resins, fluorine resins, and aliphatic wax, the resin protection The layer is to provide a dry film photoresist comprising polyvinyl alcohol having a weight average molecular weight of 5000 to 300000, preferably 5000 to 15000, more preferably 5000 to 10000.
상기 이형층은 지지체 필름 상부에 형성되어 수지 보호층과 지지체 필름을 적정 수준으로 접착시키는 동시에 수지 보호층으로부터 지지체 필름을 떼어낼 때 수지 보호층의 표면에 손상을 주지 않는 역할을 한다. The release layer is formed on the support film to bond the resin protective layer and the support film to an appropriate level, and at the same time serves to damage the surface of the resin protective layer when peeling off the support film from the resin protective layer.
이를 구체적으로 설명하면, 일례로 드라이필름 포토레지스트를 패턴 형성방법에 이용하는 경우 앞서 설명한 바와 같이, 지지체 필름, 수지 보호층 및 감광성 수지층이 순차적으로 적층된 드라이필름 포토레지스트의 감광성 수지층이 동장적층판(CCL) 상부에 닿도록 라미네이션(lamination)한 후, 지지체 필름을 수지 보호층으로부터 떼어내는데, 지지체 필름의 상부에 이형층을 구비하지 않고 수지 보호층을 적층한 드라이필름 포토레지스트인 경우 지지체 필름을 떼어내는 공정 전에 지지체 필름과 수지 보호층이 분리되는 문제가 발생하여 공정상의 차질로 인한 작업성이 저하되고, 드라이필름 포토레지스트가 불량으로 제조되는 문제가 있다. 또한, 지지체 필름을 떼어내는 공정 전에 지지체 필름과 수지 보호층이 분리되지 않더라도 지지체 필름을 떼어내면서 수지 보호층의 표면에 손상을 주게 되어, 결과적으로 헤이즈가 저하되고 현상시간에 안 좋은 영향을 미쳐 해상도가 저하되는 문제가 발생한다. Specifically, when the dry film photoresist is used in the pattern forming method as an example, as described above, the photosensitive resin layer of the dry film photoresist in which the support film, the resin protective layer and the photosensitive resin layer are sequentially laminated is a copper clad laminate. (CCL) After lamination to reach the upper part, the support film is peeled off from the resin protective layer. In the case of a dry film photoresist in which a resin protective layer is laminated without a release layer on the upper part of the support film, the support film is There arises a problem that the support film and the resin protective layer is separated before the peeling process, the workability due to the process disruption is lowered, and the dry film photoresist is badly produced. In addition, even if the support film and the resin protective layer are not separated before the support film is removed, the surface of the resin protective layer is damaged while the support film is peeled off, resulting in lower haze and adversely affect the development time. Problem occurs.
상기 이형층은 실리콘 수지, 불소 수지, 및 지방족 왁스 중에서 선택된 1 종 이상인 것을 포함한다. The release layer includes at least one selected from silicone resins, fluororesins, and aliphatic waxes.
상기 이형층은 상술한 바와 같이 수지 보호층으로부터 지지체 필름을 제거하는 경우를 고려하여 이형층과 수지 보호층간에 적정 수준으로 이형력을 가질 것이 요구되는데, 지지체 필름을 수지 보호층으로부터 떼어낼 때 이형층으로 인하여 수지 보호층의 표면에 손상을 주지 않아야 한다는 점에서 이형층 및 수지 보호층 간의 점착력은 0.0005 내지 0.01 N/cm인 것이 바람직하다. 이를 구체적으로 설명하면 상기 점착력이 상기 범위 내에 있는 경우 라미네이션을 할 때 감광성 수지층 상부에 보호필름을 더 포함하는 드라이필름 포토레지스트에서 동장적층판 상부에 드라이필름 포토레지스트를 적층하기 위하여 보호필름을 제거하는 경우 지지체 필름과 수지 보호층이 분리되지 않는 장점이 있고, 노광 전 지지체 필름을 제거할 때 수지 보호층의 표면에 손상을 주지 않고 제거할 수 있는 장점이 있다. The release layer is required to have a release force at an appropriate level between the release layer and the resin protective layer in consideration of the case of removing the support film from the resin protective layer as described above, when the release film is removed from the resin protective layer The adhesive force between the release layer and the resin protective layer is preferably 0.0005 to 0.01 N / cm in that the layer should not damage the surface of the resin protective layer. In detail, when the adhesive force is within the range, when the lamination is performed, the protective film is removed from the dry film photoresist further including a protective film on the photosensitive resin layer to laminate the dry film photoresist on the copper clad laminate. In this case, there is an advantage that the support film and the resin protective layer is not separated, there is an advantage that can be removed without damaging the surface of the resin protective layer when removing the support film before exposure.
이러한 수지 보호층을 형성하는 방법으로는 특별히 한정되는 것은 아니며, 수지 보호층 형성용 조성물을 유기 용제 및 물을 포함한 용매에 용해하고 이를 지지체 필름 및/또는 이형층 상에 도포 및 건조하여 형성시킬 수 있다. The method for forming such a resin protective layer is not particularly limited, and the resin protective layer forming composition may be dissolved in a solvent containing an organic solvent and water, and then formed by applying and drying the composition on a support film and / or a release layer. have.
한편, 상기 감광성 수지층은 드라이필름 포토레지스트가 네가티브형 또는 포지티브형으로 적용되는 것에 따라 그 조성이 달라질 수 있다. 이러한 네가티브형 또는 포지티브형 드라이필름 포토레지스트에 따른 감광성 수지층의 조성은 통상적으로 본 발명이 속한 분야에서 널리 알려진 감광성 수지 조성으로 선택할 수 있다. Meanwhile, the composition of the photosensitive resin layer may vary depending on whether the dry film photoresist is applied in a negative type or a positive type. The composition of the photosensitive resin layer according to such a negative type or positive type dry film photoresist may be generally selected as a photosensitive resin composition well known in the art.
일례로 드라이필름 포토레지스트가 네거티브형일 경우 상기 감광성 수지층은 바인더 수지, 광중합성 화합물로 에틸렌계 불포화 화합물, 광중합 개시제 및 첨가제를 포함할 수 있다. For example, when the dry film photoresist is negative, the photosensitive resin layer may include an binder resin, a photopolymerizable compound, an ethylenically unsaturated compound, a photopolymerization initiator, and an additive.
상기 바인더 수지로는 아크릴계 폴리머(acrylic polymer), 폴리에스터(polyester), 폴리우레탄(polyurethane) 등이 사용될 수 있다. 이들 중 아크릴릭 폴리머의 일종인 메타크릴릭 코폴리머(methacrylic copolymer)가 바람직하다. 필요에 따라 에틸렌 불포화 카르복실산(ethylenically unsaturated carboxylic acid) 및 기타 모노머의 공중합체가 사용될 수 있다. 상기 메타크릴릭 코폴리머로는 아세토아세틸(acetoacetyl)기를 포함하는 메타크릴릭 코폴리머도 사용될 수 있다. 상기 메타크릴릭 코폴리머를 합성하기 위해 사용가능한 메타크릴릭 모노머(methacrylic monomer)로는 메칠메타크릴레이트(methylmethacrylate), 에칠메타클릴레이트(ethyl methacrylate), 프로필 메타크릴레이트(propyl methacrylate), 부칠메타클릴레이트(butyl methacrylate), 헥실 메타클릴레이트(hexyl methacrylate), 2-에칠헥실 메타크릴레이트(2-ethylhexyl methacrylate), 시클로헥실 메타크릴레이트(cyclohexyl methacrylate), 벤질 메타크릴레이트(benzylmethacrylate), 다이메칠아미노에칠 메타크릴레이트(dimethylaminoethyl methacrylate), 하드록시에칠 메타크릴레이트(hydroxyethyl methacrylate), 하이드록시프로필 메타크릴레이트(hydroxypropyl methacrylate), 글리시딜 메타크릴레이트(glycidyl methacrylate) 등을 들 수 있다. 상기 에칠렌 불포화 카르복실산(ethylenically unsaturated carboxylic acid)으로는 아크릴산(acrylic acid), 메타크릴산(methacrylic acid), 크로토닉산(crotonic acid)와 같은 모노아크릴산(monoacrylic acid)이 많이 쓰인다. 또한, 말레인산(maleic acid), 푸마르산(fumaric acid), 이타콘산(itaconic acid)과 같은 디카르복실산(dicarboxylic acid), 또는 이들의 무수물, 하프 에스터(half ester) 등도 사용될 수 있다. 이들 중 아크릴산과 메타크릴산이 바람직하다. 기타 공중합(copolymerzation) 가능한 모노머로는 아크릴아마이드(acrylamide), 메타크릴아마이드(methacrylamide), 아크릴로니트릴(acrylonitrile), 메타크릴로니트릴(methacrylonitrile), 스티렌(styrene), a-메칠스티렌(amethylstyrene), 비닐아세테이트(vinyl acetate), 알킬 비닐 에테르(alkyl vinyl ether) 등을 들 수 있다.As the binder resin, an acrylic polymer, polyester, polyurethane, or the like may be used. Of these, methacrylic copolymer (methacrylic copolymer) which is a kind of acrylic polymer is preferable. Copolymers of ethylenically unsaturated carboxylic acids and other monomers can be used as desired. As the methacrylic copolymer, a methacrylic copolymer including an acetoacetyl group may also be used. Methacrylic monomers usable for synthesizing the methacrylic copolymers include methyl methacrylate, methyl methacrylate, propyl methacrylate and butyl methacrylate. Butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, Dimethylaminoethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, glycidyl methacrylate, and the like. have. As the ethylenically unsaturated carboxylic acid, monoacrylic acid (monoacrylic acid) such as acrylic acid, methacrylic acid, and crotonic acid is used. In addition, maleic acid, fumaric acid, dicarboxylic acids such as itaconic acid, or anhydrides thereof, half esters, and the like may also be used. Of these, acrylic acid and methacrylic acid are preferable. Other copolymerizable monomers include acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, styrene, a-methylstyrene, Vinyl acetate, alkyl vinyl ether, and the like.
상기 광중합성 모노머로서 에틸렌계 불포화화합물로는 단관능 또는 2관능, 3관능 이상의 다관능 모노머가 사용될 수 있다. 상기 다관능 모노머로는 에칠렌글리콜디메타크릴레이트(ethylene glycol dimethacrylate), 디에칠렌글리콜디메타크릴레이트(diethylene glycol dimethacrylate), 테트라에칠렌글리콜디메타크릴레이트(tetraethylene glycol dimethacrylate), 프로필렌글리콜디메타크릴레이트(propylene glycol dimethacrylate), 폴리프로필렌글리콜디메타크릴레이트(polypropylene glycol dimethacrylate), 부칠렌글리콜디메타크릴레이트(butylene glycol dimethacrylate), 네오펜틸글리콜디메타크릴레이트(neopentyl glycol dimethacrylate), 1,6-헥산글리콜디메타크릴레이트(1,6-hexane glycoldimethacrylate), 트리메칠올프로판 트리메타크릴레이트(trimethyolpropane trimethacrylate), 글리세린 디메타크릴레이트(glycerin dimethacrylate), 펜타에리트리톨 디메타크릴레이트(pentaerythritol dimethacrylate), 펜타에리트리톨트리메타크릴레이트(pentaerythritol trimethacrylate), 디펜타에리트리톨 펜타메타크릴레이트(dipentaerythritolpentamethacrylate), 2,2-비스(4-메타크릴옥시디에톡시페닐)프로판(2,2-bis(4-methacryloxydiethoxyphenyl)propane), 2-하이드록시-3-메타크릴로일옥시프로필 메타크릴레이트(2-hydroxy-3-methacryloyloxypropyl methacrylate), 에틸렌글리콜 디글리시딜에테르 디메타크릴레이트(ethylene glycol diglycidylether dimethacrylate), 디에틸렌글리콜 디글리시딜에테르 디메타크릴레이트(diethylene glycol diglycidyl etherdimethacrylate), 프탈산 디글리시딜에스테르 디메타크릴레이트(phthalic acid diglycidyl ester dimethacrylate), 글리세린 폴리글리시딜에테르 폴리메타크릴레이트(glycerin polyglycidyl ether polymethacrylate) 등을 들 수 있다. 상기 단관능 모노머로는 2-하이드록시에틸 메타크릴레이트(2-hydroxyethyl methacrylate), 2-하이드록시프로필 메타크릴레이트(2-hydroxypropyl methacrylate), 2-하이드록시부틸 메타크릴레이트(2-hydroxybutyl methacrylate), 2-페녹시-2-하이드록시프로필 메타크릴레이트(2-phenoxy-2-hydroxypropyl methacrylate), 2-메타크릴로일옥시-2 하이드록시프로필 프탈레이트(2-methacryloyloxy-2-hydroxypropyl phthalate), 3-클로로-2-하이드록시프로필 메타크릴레이트(3-chloro-2-hydroxypropyl methacrylate), 글리세린 모노메타크릴레이트(glycerin monomethacrylate), 2-메타크릴로일옥시에틸산 포스페이트(2-methacryloyloxyethyl acid phosphate), 프탈산(phthalic acid) 유도체의 메타크릴레이트, N-메틸올 메타크릴아마이드(N-methylol methacrylamide) 등이 사용될 수 있다. 상기 단관능 모노머는 상기 다관능 모노머와 함께 사용될 수 있다. As the photopolymerizable monomer, an ethylenically unsaturated compound may be a monofunctional, bifunctional, trifunctional or higher polyfunctional monomer. The polyfunctional monomers include ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and propylene glycol dimethacrylate. (propylene glycol dimethacrylate), polypropylene glycol dimethacrylate, butylene glycol dimethacrylate, butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, 1,6-hexane 1,6-hexane glycoldimethacrylate, trimethylolpropane trimethacrylate, glycerin dimethacrylate, pentaerythritol dimethacrylate, penta Erythritol trimethacrylate (pentaerythritol trimethacrylate), Dipentaerythritol pentamethacrylate (dipentaerythritolpentamethacrylate), 2,2-bis (4-methacryloxydiethoxyphenyl) propane (2,2-bis (4-methacryloxydiethoxyphenyl) propane), 2-hydroxy-3-meta Cryloyloxypropyl methacrylate (2-hydroxy-3-methacryloyloxypropyl methacrylate), ethylene glycol diglycidylether dimethacrylate, ethylene glycol diglycidylether dimethacrylate (diethylene glycol diglycidyl ether dimethacrylate) diethylene glycol diglycidyl ether dimethacrylate, phthalic acid diglycidyl ester dimethacrylate, glycerine polyglycidyl ether polymethacrylate, and the like. The monofunctional monomers include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, and 2-hydroxybutyl methacrylate. 2-phenoxy-2-hydroxypropyl methacrylate, 2-methacryloyloxy-2 hydroxypropyl phthalate, 3 3-chloro-2-hydroxypropyl methacrylate, glycerin monomethacrylate, 2-methacryloyloxyethyl acid phosphate, Methacrylic acid of phthalic acid derivatives, N-methylol methacrylamide, and the like can be used. The monofunctional monomer may be used together with the multifunctional monomer.
상기 광중합개시제로는 벤조인 메틸에테르(benzoin methyl ether), 벤조인 에틸 에테르(benzoin ethyl ether), 벤조인 아이소프로필 에테르(benzoin isopropyl ether), 벤조인 n-부틸에테르(benzoin n-butyl ether), 벤조인 페닐에테르(benzoin phenyl ether), 벤질 디페닐 디설파이드(benzyl diphenyl disulfide), 벤질 디메칠 케탈(benzyl dimethyl ketal), 안트라퀴논(anthraquinone), 나프토퀴논(naphthoquinone), 3,3-디메칠-4-메톡시벤조페논(3,3-dimethyl-4-methoxybenzophenone), 벤조페논(benzophenone), p,p'-비스(디메칠아미노)벤조페논(p,p'-bis(dimethylamino)benzophenone), p,p'-비스(디에칠아미노)벤조페논(p,p'-bis(diethylamino)benzophenone), p,p'-디에칠아미노벤조페논(p,p'-diethylaminobenzophenone), 피발론 에틸에테르(pivalone ethyl ether), 1,1-디클로로 아세토페논(1,1-dichloroacetophenone), p-t-부틸디클로로아세토페논(p-t-butyldichloroacetophenone), 헥사아릴-이미다졸(hexaaryl- imidazole)의 다이머(dimer), 2,2'-디에톡시아세토페논(2,2'-diethoxyacetophenone), 2,2'-디에톡시-2-페닐아세토페논(2,2'-diethoxy-2-phenylacetophenone), 2,2'-디클로로-4-페녹시아세토페논(2,2'-dichloro-4-phenoxyacetophenone), 페닐 글리옥실레이트(phenyl glyoxylate), a-하이드록시-이소부틸페논(a-hydroxyisobutylphenone), 디벤조스판(dibenzospan), 1-(4-이소프로필페닐)-2-하이드록시-2-메틸-1-프로판온(1-(4-Examples of the photopolymerization initiator include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, Benzoin phenyl ether, benzyl diphenyl disulfide, benzyl dimethyl ketal, anthraquinone, naphthoquinone, 3,3-dimethyl- 4-methoxybenzophenone (3,3-dimethyl-4-methoxybenzophenone), benzophenone, p, p'-bis (dimethylamino) benzophenone (p, p'-bis (dimethylamino) benzophenone), p, p'-bis (diethylamino) benzophenone (p, p'-bis (diethylamino) benzophenone), p, p'-diethylaminobenzophenone (p, p'-diethylaminobenzophenone), pivalon ethyl ether ( pivalone ethyl ether), 1,1-dichloroacetophenone, pt-butyldichloroacetophenone, hexaaryl- Dimer of hexaaryl-imidazole, 2,2'-diethoxyacetophenone, 2,2'-diethoxy-2-phenylacetophenone (2,2'-diethoxy -2-phenylacetophenone), 2,2'-dichloro-4-phenoxyacetophenone, phenyl glyoxylate, a-hydroxy-isobutylphenone (2,2'-dichloro-4-phenoxyacetophenone) a-hydroxyisobutylphenone), dibenzospan, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl-1-propanone (1- (4-
isopropylphenyl)-2-hydroxy-2-methyl-1-propanone), 2-메틸-[4-(메틸티오)페닐]-2-모폴리노-1-프로판온(2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone), 트리-브로모페닐설폰(tri- bromophenylsulfone), 트리브로모메틸페닐설폰(tribromomethylphenylsulfone) 등이 사용될 수 있다. isopropylphenyl) -2-hydroxy-2-methyl-1-propanone), 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone (2-methyl- [4- (methylthio ) phenyl] -2-morpholino-1-propanone), tri-bromophenylsulfone, tribromomethylphenylsulfone, and the like can be used.
상기 첨가제로서 비닐 클로라이드 레진 등의 유연제를 포함할 수 있다. 그 구체적인 예로서, 프탈릭 에스테르(phthalic ester) 종류에는 디메틸 프탈레이트(dimethyl phthalate), 디에틸 프탈레이트(diethyl phthalate), 디부틸프탈레이트(dibutyl phthalate), 디헵틸 프탈레이트(diheptyl phthalate), 디옥틸 프탈레이트(dioctyl phthalate), 디이소데실 프탈레이트(diisodecyl phthalate), 부틸벤질프탈레이트(butylbenzyl phthalate), 디이소노닐 프탈레이트(diisononyl phthalate), 에틸프탈에틸 글리콜레이트(ethylphthalylethyl glycolate), 디메틸 이소프탈레이트(dimethylisophthalate), 디클로로헥실 프탈레이트(dichlorohexyl phthalate) 등이 있고, 지방산이나 아리마틱산(arimatic acid)의 에스테르들, 예를들면 디옥틸 아디페이트(dioctyl adipate), 디이소부틸 아디페이트(diisobutyl adipate), 디부틸 아디페이트(dibutyl adipate), 디이소데실 아디페이트(diisodecyl adipate), 디부틸 디글리콜 아디페이트(dibutyl diglycol adipate), 디부틸 세바캐이트(dibutyl sebacate), 디옥틸 세바캐이트(dioctyl sebacate) 등을 들 수 있다. 또한, 본 발명에서는 글리세롤 트리아세테이트(glycerol triacetate), 트리메틸 포스페이트(trimethyl phosphate), 트리에틸 포스페이트(triethyl phosphate), 트리부틸 포스페이트(tributyl phosphate), 트리옥틸 포스페이트(trioctylphosphate), 트리부톡시에틸 포스페이트(tributoxyethyl phosphate), 트리스-클로로에틸 포스페이트(tris-chloroethylphosphate), 트리스-디클로로프로필 포스페이트(tris-dichloropropyl phosphate), 트리페닐 포스페이트(triphenylphosphate), 트리크레실 포스페이트(tricresyl phosphate), 트리크실레닐 포스페이트(trixylenyl phosphate), 크레실 디페닐 포스페이트(cresyl diphenyl phosphate), 옥틸 디페닐 포스페이트(octyl diphenyl phosphate), 크실레닐 디페닐 포스페이트(xylenyl diphenyl phosphate), 트리로릴 포스페이트(trilauryl phosphate), 트리세틸 포스페이트(tricetylphosphate), 트리스테아릴 포스페이트(tristearyl phosphate), 트리올레일 포스페이트(trioleyl phosphate), 트리페닐 포스파이트(triphenyl phosphite), 트리스 트리데실 포스파이트(tris-tridecyl phosphite), 디부틸 하이드로젠 포스파이트(dibutyl hydrogen phosphite), 디부틸-부틸 포스포네이트(dibutyl-butyl phosphonate), 디(2-에틸헥실) 포스포네이트(di(2-ethylhexyl) 2-ethylhexyl phosphonate), 2-에틸헥실-2-에틸헥실 포스포네이트(2-ethylhexyl-2-ethylhexylphosphonate), 메틸산 포스페이트(methyl acid phosphate), 이소프로필산 포스페이트(isopropyl acid phosphate), 부틸산 포스페이트(butyl acid phosphate), 디부틸산 포스페이트(dibutyl acid phosphate), 모노부틸산 포스페이트(monobutyl acid phosphate), 옥틸산 포스페이트(octyl acid phosphate), 디옥틸 포스페이트(dioctyl phosphate), 이소데실산 포스페이트(isodecyl acid phosphate), 모노이소데실 포스페이트(monoisodecyl phosphate), 데카놀산 포스페이트(decanol acid phosphate) 등의 유연제를 사용할 수도 있다.As the additive, a softening agent such as vinyl chloride resin may be included. Specific examples of the phthalic ester include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, and dioctyl phthalate. phthalate, diisodecyl phthalate, butylbenzyl phthalate, diisononyl phthalate, ethylphthalyl ethyl glycolate, dimethyl isophthalate, dimethylisophthalate, dichlorohexyl phthalate dichlorohexyl phthalate, and esters of fatty acids or arimatic acid, such as dioctyl adipate, diisobutyl adipate, dibutyl adipate, Diisodecyl adipate, dibutyl diglycodiate l adipate), dibutyl sebacate, dioctyl sebacate, and the like. In the present invention, glycerol triacetate, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tributyl phosphate, trioctylphosphate, tributoxyethyl phosphate phosphate, tris-chloroethylphosphate, tris-dichloropropyl phosphate, triphenylphosphate, tricresyl phosphate, trixylenyl phosphate ), Cresyl diphenyl phosphate, octyl diphenyl phosphate, xylenyl diphenyl phosphate, trilauryl phosphate, tricetyl phosphate , Tristearyl phosphate phosphate, trioleyl phosphate, triphenyl phosphite, tris-tridecyl phosphite, dibutyl hydrogen phosphite, dibutyl-butyl phosphate Dibutyl-butyl phosphonate, di (2-ethylhexyl) 2-ethylhexyl phosphonate, 2-ethylhexyl-2-ethylhexyl phosphonate (2-ethylhexyl-2 -ethylhexylphosphonate, methyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, dibutyl acid phosphate, monobutyl acid phosphate ), Octyl acid phosphate, dioctyl phosphate, isodecyl acid phosphate, monoisodecyl phosphate, decanoic acid phosphate It may also be used, such as softeners (decanol acid phosphate).
기타, 휘발성 유기물인 글리세린(glycerin), 트리메틸올프로판(trimethylolpropane), 에틸렌글리콜(ethylene glycol), 디에틸렌글리콜(diethylene glycol), 트리에틸렌글리콜(triethylene glycol), 프로필렌글리콜(propylene glycol), 디프로필렌글리콜(dipropylene glycol) 또는 이들의 저급 알킬 에테르(alkyl ether), 저급 지방산 에스테르, 고급 지방산이나 이들의 에스테르, 고급 지방산 알콜 또는 이들의 에스테르 등도 본 발명의 유연제로 사용 가능하다. In addition, volatile organic glycerol (glycerin), trimethylolpropane (ethylene glycol), ethylene glycol (ethylene glycol), diethylene glycol (diethylene glycol), triethylene glycol (propylene glycol), dipropylene glycol (dipropylene glycol) or lower alkyl ethers thereof, lower fatty acid esters, higher fatty acids or their esters, higher fatty alcohols or esters thereof, and the like can also be used as the softening agent of the present invention.
상술한 네거티브형 감광성 수지에 포함되는 바인더 수지, 광중합성 화합물, 광중합 개시제 및 첨가제는 임의의 목적에 따라 적절히 혼합하여 사용할 수 있다. The binder resin, the photopolymerizable compound, the photoinitiator, and the additive contained in the negative photosensitive resin described above can be appropriately mixed and used according to any purpose.
한편 드라이필름 포토레지스트가 포지티브형일 경우에는 상기 감광성 수지층은 알칼리 가용성 수지 및 디아지드계 감광성 화합물을 포함할 수 있으며, 구체적으로 알칼리 가용성 수지로서 노볼락 수지를 사용할 수 있으며, 더욱 좋기로는 크레졸 노볼락 수지를 포함할 수 있다. 상기 노볼락 수지는 페놀 단독 또는 알데히드 및 산성 촉매와의 조합물을 중축합 반응시켜 얻을 수 있다. On the other hand, when the dry film photoresist is positive type, the photosensitive resin layer may include an alkali-soluble resin and a diazide-based photosensitive compound, specifically, a novolak resin may be used as the alkali-soluble resin, and more preferably, cresol furnace May comprise a volac resin. The novolak resin can be obtained by polycondensation of phenol alone or a combination of an aldehyde and an acid catalyst.
이때 페놀류로는 특별히 한정되는 것은 아니며, 페놀, o-크레졸, m-크레졸, p-크레졸, 2,3-크실레놀, 2,5-크실레놀, 3,4-크실레놀, 3,5-크실레놀, 2,3,5-트리메틸페놀-크실레놀, 4-t-부틸페놀, 2-t-부틸페놀, 3-t-부틸페놀, 4-메틸-2-t-부틸페놀 등 1가 페놀류; 및 2-나프톨, 1,3-디하이드록시 나프탈렌, 1,7-디하이드록시 나프탈렌, 1,5-디하이드록시 나프탈렌, 레조르시놀, 피로카테콜, 히드로퀴논, 비스페놀 A, 플루오로글루시놀, 피로갈롤 등 다가 페놀류 등을 들 수 있으며, 이들 중 선택하여 단독으로 또는 2종 이상 조합하여 사용할 수 있다. 특히 m-크레졸, p-크레졸의 조합이 바람직하다. The phenols are not particularly limited, and phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3, 5-xylenol, 2,3,5-trimethylphenol-xylenol, 4-t-butylphenol, 2-t-butylphenol, 3-t-butylphenol, 4-methyl-2-t-butylphenol Monovalent phenols; And 2-naphthol, 1,3-dihydroxy naphthalene, 1,7-dihydroxy naphthalene, 1,5-dihydroxy naphthalene, resorcinol, pyrocatechol, hydroquinone, bisphenol A, fluoroglucinol, Polyhydric phenols, such as a pyrogallol, etc. are mentioned, These can be selected individually and can be used in combination of 2 or more types. In particular, a combination of m-cresol and p-cresol is preferable.
상기 알데히드류로는 특별히 한정되는 것은 아니나, 포름알데히드, 트리옥산, 파라포름알데히드, 벤즈알데히드, 아세트알데히드, 프로필알데히드, 페닐아세트알데히드, 알파 또는 베타-페닐 프로필알데히드, o-, m- 또는 p-하이드록시벤즈알데히드, 글루타르알데히드, 테레프탈알데히드 등을 들 수 있으며, 단독으로 또는 2종 이상 조합하여 사용할 수 있다. The aldehydes are not particularly limited, but formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, alpha or beta-phenyl propylaldehyde, o-, m- or p-hydride Roxy benzaldehyde, glutaraldehyde, terephthalaldehyde, etc. are mentioned, It can be used individually or in combination of 2 or more types.
상기 크레졸 노볼락 수지는 중량평균분자량(GPC 측정법에 기준할 때)이 2,000 내지 30,000인 것이 바람직하며, 크레졸 노볼락 수지는 메타/파라 크레졸의 함량비에 따라 감광속도와 잔막률 등의 물성이 달라질 수 있으므로, 메타/파라 크레졸의 함량이 중량기준으로 4:6 내지 6:4 비율로 혼합된 것이 바람직할 수 있다. 상기 크레졸 노볼락 수지 중의 메타 크레졸의 함량이 상기 범위를 초과하면 감광속도가 빨라지면서 잔막율이 급격히 낮아지며, 파라 크레졸의 함량이 상기 범위를 초과하면 감광속도가 느려지는 단점이 있다. 상기 크레졸 노볼락 수지는 메타/파라 크레졸의 함량이 중량 기준으로 4:6 내지 6:4인 크레졸 노볼락 수지를 단독으로 사용할 수 있으나, 더욱 바람직하게는 서로 다른 수지를 혼합사용할 수 있다. 이 경우, 크레졸 노볼락 수지를 중량평균분자량이 8,000 내지 30,000인 크레졸 노볼락 수지와, 중량평균분자량이 2,000 내지 8,000인 노볼락 수지를 7:3 내지 9:1의 비율로 혼합사용하는 것이 바람직하다. The cresol novolak resin preferably has a weight average molecular weight (based on the GPC method) of 2,000 to 30,000, and the cresol novolak resin has different physical properties such as photosensitivity and residual film ratio depending on the content ratio of meta / para cresol. As such, it may be desirable that the meta / para cresol content is mixed in a ratio of 4: 6 to 6: 4 by weight. When the content of the meta cresol in the cresol novolak resin exceeds the above range, the photoresist rate is increased while the residual film rate is drastically lowered. When the content of the para cresol exceeds the above range, the photosensitivity is slowed. The cresol novolac resin may be used solely a cresol novolac resin having a meta / para cresol content of 4: 6 to 6: 4 by weight, and more preferably, different resins may be mixed. In this case, it is preferable to use a cresol novolac resin mixed with a cresol novolac resin having a weight average molecular weight of 8,000 to 30,000 and a novolac resin having a weight average molecular weight of 2,000 to 8,000 in a ratio of 7: 3 to 9: 1. .
상기 및 이하에서 "중량평균분자량"은 특정한 언급이 없는 한 겔투과크로마토크래피(GPC)에 의해 결정되는, 폴리스티렌 당량의 환산치로 정의된다. Above and below "weight average molecular weight" is defined in terms of polystyrene equivalents, as determined by gel permeation chromatography (GPC) unless otherwise specified.
한편 포토레지스트층 조성 중 디아지드계 감광성 화합물은 알칼리 가용성 수지의 알칼리에 대한 용해도를 감소시키는 용해억제제로서 작용하며, 광이 조사되면 알칼리 가용성 물질로 바뀌어 알칼리 가용성 수지의 알칼리 용해도를 증가시키는 역할을 하게 된다. 이와 같이 광조사로 인한 용해도의 변화로 인하여 본 발명의 필름형 광분해성 전사재료는 노광 부위가 현상된다. In the composition of the photoresist layer, the diazide-based photosensitive compound acts as a dissolution inhibitor to reduce the solubility of alkali-soluble resin in alkali, and when irradiated with light, the diazide-based photosensitive compound is converted into alkali-soluble material to increase alkali solubility of alkali-soluble resin. do. As such, due to the change in solubility due to light irradiation, the exposed portion of the film type photodegradable transfer material of the present invention is developed.
상기 디아지드계 감광성 화합물은 폴리하이드록시 화합물과 퀴논디아지드 술폰산 화합물과의 에스테르화 반응에 의해 합성할 수 있다. 디아지드계 감광성 화합물을 얻기 위한 에스테르화 반응은 폴리하이드록시 화합물과 퀴논디아지드 술폰산 화합물을 디옥산, 아세톤, 테트라하이드로퓨란, 메틸에틸케톤, N-메틸피롤리돈, 클로로포름, 트리에틸아민, N-메틸몰포린, N-메틸피페라진 또는 4-디메틸아미노피리딘과 같은 염기성 촉매를 적하하여 축합시킨 후, 얻어진 생성물을 세정, 정제, 건조시켜 얻을 수 있다. The diazide photosensitive compound can be synthesized by esterification of a polyhydroxy compound and a quinone diazide sulfonic acid compound. The esterification reaction for obtaining a diazide photosensitive compound is carried out by dioxane, acetone, tetrahydrofuran, methyl ethyl ketone, N-methylpyrrolidone, chloroform, triethylamine, N, and polyhydroxy compound and quinone diazide sulfonic acid compound. A basic catalyst such as -methylmorpholine, N-methylpiperazine or 4-dimethylaminopyridine can be dropped and condensed, and then the obtained product can be washed, purified and dried.
이때 퀴논디아지드 술폰산 화합물로는 일예로 1,2-벤조퀴논 디아지드-4-술폰산, 1,2-나프토퀴논 디아지드-4-술폰산, 1,2-벤조퀴논 디아지드-5-술폰산 및 1,2-나프토퀴논 디아지드-5-술폰상 등의 o-퀴논 디아지드 술폰산화합물 및 그 외의 퀴논 디아지드 술폰산 유도체 등을 들 수 있다. 상기 퀴논디아지드 술폰산 화합물은 스스로 알칼리 중에서 알칼리 가용성 수지의 용해도를 낮게 하는 용해 저지제로서의 기능을 가진다. 그러나 노광시 알칼리 가용성이기 위해 분해하고 그로 인해 오히려 알칼리에서 알칼리 가용성 수지의 용해를 촉진시키는 특성을 갖는다. The quinone diazide sulfonic acid compound is, for example, 1,2-benzoquinone diazide-4-sulfonic acid, 1,2-naphthoquinone diazide-4-sulfonic acid, 1,2-benzoquinone diazide-5-sulfonic acid and O-quinone diazide sulfonic acid compounds such as 1,2-naphthoquinone diazide-5-sulfone phase, other quinone diazide sulfonic acid derivatives, and the like. The quinonediazide sulfonic acid compound itself has a function as a dissolution inhibiting agent that lowers the solubility of alkali-soluble resin in alkali. However, it is decomposed to be alkali-soluble at the time of exposure and thereby rather has the property of promoting dissolution of alkali-soluble resin in alkali.
상기 폴리하이드록시 화합물로서는 2,3,4-트리하이드록시 벤조페논, 2,2',3-트리하이드록시 벤조페논, 2,3,4'-트리하이드록시 벤조페논 등의 트리하이드록시 벤조페논류; 2,3,4,4'-테트라하이드록시벤조페논, 2,2',4,4'-테트라하이드록시 벤조페논, 2,3,4,5-테트라하이드록시벤조페논 등 테트라하이드록시 벤조페논류; 2,2',3,4,4'-펜타하이드록시 벤조페논, 2,2',3,4,5-펜타하이드록시 벤조페논 ed 펜타하이드록시 벤조페논류; 2,3,3',4,4',5'-헥사하이드록시벤조페논, 2,2',3,3',4,5'-헥사하이드록시 벤조페논 등 헥사하이드록시 벤조페논류; 갈산알킬에스테르류; 옥시플라본류 등을 들 수 있다. Examples of the polyhydroxy compound include trihydroxy benzophene such as 2,3,4-trihydroxy benzophenone, 2,2 ', 3-trihydroxy benzophenone, and 2,3,4'-trihydroxy benzophenone. Rice field; Tetrahydroxy benzophene such as 2,3,4,4'-tetrahydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxy benzophenone, and 2,3,4,5-tetrahydroxybenzophenone Rice field; 2,2 ', 3,4,4'-pentahydroxy benzophenone, 2,2', 3,4,5-pentahydroxy benzophenone ed pentahydroxy benzophenone; Hexahydroxy benzophenones such as 2,3,3 ', 4,4', 5'-hexahydroxybenzophenone and 2,2 ', 3,3', 4,5'-hexahydroxy benzophenone; Gallic acid alkyl esters; Oxyflavones etc. are mentioned.
이들로부터 얻어진 디아지드계 감광성 화합물의 구체적인 일예로는 2,3,4,4'-테트라하이드록시벤조페논-1,2-나프토퀴논디아지드-5-설포네이트, 2,3,4-트리하이드록시벤조페논-1,2-나프토퀴논디아지드-5-설포네이트 및 (1-[1-(4-하이드록시페닐)이소프로필]-4-[1,1-비스(4-하이드록시페닐)에틸]벤젠)-1,2-나프토퀴논디아지드-5-설포네이트 중에서 선택된 1종 이상을 들 수 있다. Specific examples of the diazide photosensitive compound obtained from these include 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinone diazide-5-sulfonate, 2,3,4-tri Hydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate and (1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxy Phenyl) ethyl] benzene) 1, 2- naphthoquinone diazide-5-sulfonate 1 or more types chosen are mentioned.
이러한 디아지드계 감광성 화합물은 포토레지스트층 조성 중 알칼리 가용성 수지 100중량부에 대해 30 내지 80중량부인 것이 현상성이나 용해성 측면에서 유리할 수 있다. The diazide-based photosensitive compound may be advantageously 30 to 80 parts by weight based on 100 parts by weight of the alkali-soluble resin in the photoresist layer composition in view of developability or solubility.
상술한 포지티브형 감광성 수지층은 감도증진제를 포함할 수 있는데, 이는 감도를 향상시키기 위한 것이다. 이의 일예로는 2,3,4-트리하이드록시벤조페논, 2,3,4,4'-테트라하이드록시벤조페논 및 1-[1-(4-하이드록시페닐)이소프로필]-4-[1,1-비스(4-하이드록시페닐)에틸]벤젠 중에서 선택된 1종 이상일 수 있다. 상기 감도증진제를 포함할 때 그 함량은 알칼리 가용성 수지 100중량부를 기준으로 3 내지 15중량부인 것이 감광 효과 향상 및 윈도우 공정 마진 측면에서 유리할 수 있다. The positive photosensitive resin layer described above may include a sensitivity enhancer, which is intended to improve sensitivity. Examples thereof include 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone and 1- [1- (4-hydroxyphenyl) isopropyl] -4- [ 1,1-bis (4-hydroxyphenyl) ethyl] benzene. When the sensitivity enhancer is included in an amount of 3 to 15 parts by weight based on 100 parts by weight of the alkali-soluble resin, it may be advantageous in terms of improving the photosensitive effect and margin of the window process.
그밖에 포지티브형 감광성 수지층은 레벨링제, 충진제, 산화방지제 등의 기타 성분이나 첨가제를 포함할 수 있다. In addition, the positive photosensitive resin layer may contain other components or additives such as a leveling agent, a filler, and an antioxidant.
한편 알칼리 가용성 수지, 디아지드계 감광성 화합물 등을 포함하는 조성물을 일정량의 용제에 분산시켜 조액한 후 도포하게 되는데, 이때 용매의 일예로는 에틸 아세테이트, 부틸 아세테이트, 에틸렌글리콜 모노에틸에테르 아세테이트, 디에틸렌글리콜 모노에틸에테르 아세테이트, 프로필렌글리콜 모노에틸에테르 아세테이트, 아세톤, 메틸에틸 케톤, 에틸 알코올, 메틸 알코올, 프로필 알코올, 이소프로필 알코올, 벤젠, 톨루엔, 시클로펜타논, 시클로헥사논, 에틸렌글리콜, 크실렌, 에틸렌글리콜 모노에틸에테르 및 디에틸렌글리콜 모노에틸에테르로 이루어진 군으로부터 선택된 1종 이상을 들 수 있다. On the other hand, a composition containing an alkali-soluble resin, a diazide-based photosensitive compound, etc. is dispersed in a predetermined amount of a solvent to be prepared and then applied. At this time, examples of the solvent include ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, and diethylene. Glycol monoethyl ether acetate, propylene glycol monoethyl ether acetate, acetone, methyl ethyl ketone, ethyl alcohol, methyl alcohol, propyl alcohol, isopropyl alcohol, benzene, toluene, cyclopentanone, cyclohexanone, ethylene glycol, xylene, ethylene And at least one selected from the group consisting of glycol monoethyl ether and diethylene glycol monoethyl ether.
본 발명에 따른 드라이필름 포토레지스트는 감광성 수지층의 일면에 보호필름을 더 포함할 수 있다. 상기 보호필름은 감광성 수지층을 외부로부터 보호하는 역할을 하는 것으로서, 드라이필름 포토레지스트를 후공정에 적용할 때는 용이하게 이탈되면서, 보관 및 유통할 때에는 이형되지 않도록 적당한 이형성과 점착성을 필요로 한다. The dry film photoresist according to the present invention may further include a protective film on one surface of the photosensitive resin layer. The protective film serves to protect the photosensitive resin layer from the outside, and when the dry film photoresist is easily applied to the post-process, the protective film needs proper release property and adhesion so as not to be released during storage and distribution.
이하 본 발명의 바람직한 실시예 및 비교예를 설명한다.　 그러나 하기한 실시예는 본 발명의 바람직한 일 실시예일뿐 본 발명이 하기한 실시예에 한정되는 것은 아니다. Hereinafter, preferred examples and comparative examples of the present invention will be described. However, the following examples are only preferred embodiments of the present invention and the present invention is not limited to the following examples.
실시예EXAMPLE 1 내지 9 및  1 to 9 and 비교예Comparative example 1 내지 4 1 to 4
<실시예 1><Example 1>
(a) 중량평균분자량이 22000, 검화도가 87%인 폴리비닐알코올(KURARAY사, PVA205) 20g, 및 부톡시에탄올(2-n-butoxyethanol) 용매 100g에 폴리실리콘 0.1g를 녹였을 때 입도가 0㎛인 폴리실리콘(BYK사, BYK-349, 건조후 고형분대비 0.25%) 0.05g을 증류수 90g, 부톡시에탄올(2-n-butoxyethanol) 10g에 넣고 80℃에서 6시간 교반하여 완전히 녹여 수지 보호층용 조성물을 제조하였다. 이를 두께 16㎛인 지지체 필름(헤이즈 2.3%, 표면처리 없음, 폴리에틸렌테레프탈레이트 필름, FDFR-16㎛, KOLON) 위에 코팅 바를 이용하여 코팅한 후, 열풍오븐을 이용하여 80℃에서 10분간 건조하여 두께 3㎛의 수지 보호층을 형성하였다. 형성된 수지 보호층을 건조시킨 후 하기에 따른 잔류용매량 측정 방법으로 측정한 결과, 수지 보호층에 포함된 부톡시에탄올의 함량은 1200ppm이였다. (a) Particle size when 20 g of polyvinyl alcohol (KURARAY Co., PVA205) having a weight average molecular weight of 22000, 87% saponification, and 0.1 g of polysilicon were dissolved in 100 g of 2-n-butoxyethanol solvent. 0.05 g of 0 μm polysilicon (BYK, BYK-349, 0.25% of solid content after drying) was added to 90 g of distilled water and 10 g of 2-n-butoxyethanol and stirred at 80 ° C. for 6 hours to completely dissolve the resin. The layer composition was prepared. This was coated on a support film having a thickness of 16 μm (haze 2.3%, no surface treatment, polyethylene terephthalate film, FDFR-16 μm, KOLON) using a coating bar, and then dried at 80 ° C. for 10 minutes using a hot air oven to obtain a thickness. The resin protective layer of 3 micrometers was formed. After drying the formed resin protective layer, the residual solvent measured according to the following As a result of measuring by the method, the content of butoxyethanol contained in the resin protective layer was 1200 ppm.
이때, 상기 폴리실리콘을 상기 용매에 6시간 동안 80℃의 조건 하에서 녹였을 때 입도가 0㎛라는 의미는 폴리실리콘이 용매에 거의 완전히 용해되어 입자상이 발견되지 않았음을 의미하며, 이하 특별한 언급이 없는 한, '입도가 0㎛'은 상기와 같이 동일한 의미를 뜻한다.In this case, when the polysilicon was dissolved in the solvent for 6 hours at 80 ° C., the particle size of 0 μm means that the polysilicon was almost completely dissolved in the solvent and no particulate was found. Unless otherwise specified, 'particle size 0 占' means the same as described above.
(b) UH-9200 series(Kolon)에 사용된 조성 및 함량으로 감광성 수지 조성물을 제조하였다. 구체적으로는, 광개시제류를 용매인 메틸에틸케톤과 메틸알코올에 녹인 후, 광중합성 올리고머류와 바인더 폴리머를 첨가하여 교반기계(mechanical stirrer)를 이용하여 1시간 동안 혼합하여 감광성 수지 조성물을 제조하였다. (b) A photosensitive resin composition was prepared in the composition and content used for UH-9200 series (Kolon). Specifically, the photoinitiators were dissolved in methyl ethyl ketone and methyl alcohol as solvents, and then photopolymerizable oligomers and binder polymers were added and mixed for 1 hour using a mechanical stirrer to prepare a photosensitive resin composition.
(c) 상기 감광성 수지 조성물을 19㎛ 두께의 보호필름(실리콘이 이형처리된 폴리에틸렌테레프탈레이트 필름, CY201-19um, KOLON) 상에 코팅 바를 이용하여 코팅한 후, 열풍오븐을 이용하여 80℃에서 6분간 건조하여 두께 15㎛의 감광성 수지층을 형성하였다. (c) coating the photosensitive resin composition on a 19 μm thick protective film (silicon-released polyethylene terephthalate film, CY201-19um, KOLON) using a coating bar, and then using a hot air oven at 80 ° C. It dried for 1 minute and formed the photosensitive resin layer of 15 micrometers in thickness.
(d) 건조가 완료된 (c) 필름의 감광성 수지층과 상기 (a)의 수지 보호층이 접하도록 50℃에서 압력 4kgf/㎠로 라미네이션하여 두께 53㎛의 필름형 감광성 전사재료를 제조하였다. (d) Lamination was carried out at a pressure of 4kgf / ㎠ at 50 ℃ to contact the photosensitive resin layer of the dried (c) film and the resin protective layer of (a) to prepare a film-type photosensitive transfer material having a thickness of 53㎛.
<실시예 2><Example 2>
부톡시에탄올 대신 에톡시에탄올을 사용하는 것을 제외하고는 실시예 1과 동일하게 실시하였다. 이때, 형성된 수지 보호층을 건조시킨 후 하기에 따른 잔류용매량 측정방법으로 측정한 결과, 수지 보호층에 포함된 에톡시에탄올의 함량은 1100ppm이였다.The same procedure as in Example 1 was carried out except that ethoxyethanol was used instead of butoxyethanol. At this time, after drying the formed resin protective layer was measured by the method of measuring the residual solvent according to the following, the content of ethoxyethanol contained in the resin protective layer was 1100ppm.
<실시예 3><Example 3>
증류수 90g 및 부톡시에탄올 10g 대신 증류수 95g 및 부톡시에탄올 5g을 사용하는 것을 제외하고는 실시예 1과 동일하게 실시하였다. 이때, 형성된 수지 보호층을 건조시킨 후 하기에 따른 잔류용매량 측정방법으로 측정한 결과, 수지 보호층에 포함된 부톡시에탄올의 함량은 900ppm이였다. The same procedure as in Example 1 was repeated except that 95 g of distilled water and 5 g of butoxyethanol were used instead of 90 g of distilled water and 10 g of butoxyethanol. At this time, after drying the formed resin protective layer was measured by the method of measuring the residual solvent according to the following, the content of butoxyethanol contained in the resin protective layer was 900ppm.
<실시예 4><Example 4>
증류수 90g 및 부톡시에탄올 10g 대신 증류수 80g 및 부톡시에탄올 20g을 사용하는 것을 제외하고는 실시예 1과 동일하게 실시하였다. 이때, 형성된 수지 보호층을 건조시킨 후 하기에 따른 잔류용매량 측정방법으로 측정한 결과, 수지 보호층에 포함된 부톡시에탄올의 함량은 1400ppm이였다. The same procedure as in Example 1 was repeated except that 80 g of distilled water and 20 g of butoxyethanol were used instead of 90 g of distilled water and 10 g of butoxyethanol. At this time, after drying the formed resin protective layer was measured by the method of measuring the residual solvent according to the following, the content of butoxyethanol contained in the resin protective layer was 1400ppm.
<실시예 5>Example 5
(a) 중량평균분자량이 22000, 검화도가 87%인 폴리비닐알코올(KURARAY사, PVA205) 20g, 및 폴리실리콘(BYK사, BYK-349, 건조후 고형분대비 0.25%) 0.05g을 증류수 90g, 부톡시에탄올(2-n-butoxyethanol) 10g에 넣고 80℃에서 6시간 교반하여 완전히 녹여 수지 보호층용 조성물을 제조하였다.　 (a) 20 g of polyvinyl alcohol (KURARAY, PVA205) having a weight average molecular weight of 22000 and 87% saponification, and 0.05 g of polysilicon (BYK, BYK-349, 0.25% of the solid content after drying), 90 g of distilled water, It was added to 10 g of butoxyethanol (2-n-butoxyethanol) and stirred at 80 ° C. for 6 hours to completely dissolve to prepare a composition for a resin protective layer.
이를 두께 16㎛인 지지체 필름(CY201-16㎛, KOLON) 위에 코팅 바를 이용하여 코팅한 후, 열풍오븐을 이용하여 80℃에서 10분간 건조하여 두께 3㎛의 수지 보호층을 형성하였다.　 이 때, 상기 지지체 필름은 ILC(in-line coating) 방법에 의해 지지체 필름의 일면에 실리콘 수지를 사용하여 이형층이 형성된 폴리에틸렌테레프탈레이트 필름이다. 참고로, 지지체 필름 상의 이형층은 ILC 방법 이외에 오프-라인 코팅(off line coating) 방법에 의해 형성할 수 있다. 이러한 ILC 방법 및 오프-라인 코팅 방법은 본 발명이 속한 분야에 널리 알려진 방법으로 구체적인 설명은 생략하기로 한다. This was coated on a support film (CY201-16 μm, KOLON) having a thickness of 16 μm using a coating bar, and then dried at 80 ° C. for 10 minutes using a hot air oven to form a resin protective layer having a thickness of 3 μm. In this case, the support film is a polyethylene terephthalate film in which a release layer is formed by using a silicone resin on one surface of the support film by an in-line coating (ILC) method. For reference, the release layer on the support film may be formed by an off-line coating method in addition to the ILC method. The ILC method and the off-line coating method are well known in the art to which the present invention pertains, and a detailed description thereof will be omitted.
(b) UH-9200 series(Kolon)에 사용된 조성 및 함량으로 감광성 수지 조성물을 제조하였다.　 구체적으로는, 광개시제류를 용매인 메틸에틸케톤과 메틸알코올에 녹인 후, 광중합성 올리고머류와 바인더 폴리머를 첨가하여 교반기계(mechanical stirrer)를 이용하여 1시간 동안 혼합하여 감광성 수지 조성물을 제조하였다. (b) A photosensitive resin composition was prepared in the composition and content used for UH-9200 series (Kolon). Specifically, the photoinitiators were dissolved in methyl ethyl ketone and methyl alcohol as solvents, and then photopolymerizable oligomers and binder polymers were added and mixed for 1 hour using a mechanical stirrer to prepare a photosensitive resin composition.
(c) 상기 감광성 수지 조성물을 19㎛ 두께의 보호필름(CY201-19㎛, KOLON) 상에 코팅 바를 이용하여 코팅한 후, 열풍오븐을 이용하여 80℃에서 6분간 건조하여 두께 15㎛의 감광성 수지층을 형성하였다. (c) The photosensitive resin composition was coated on a 19 μm thick protective film (CY201-19 μm, KOLON) using a coating bar, and then dried at 80 ° C. for 6 minutes using a hot air oven to give a photosensitive water having a thickness of 15 μm. Formed strata.
(d) 건조가 완료된 (c) 필름의 감광성 수지층과 상기 (a)의 수지 보호층이 접하도록 50℃에서 압력 4kgf/㎠로 라미네이션하여 두께 53㎛의 필름형 감광성 전사재료를 제조하였다.　 (d) A film-type photosensitive transfer material having a thickness of 53 μm was prepared by laminating at a pressure of 4 kgf / cm 2 at 50 ° C. such that the photosensitive resin layer of the dried (c) film and the resin protective layer of (a) were contacted.
<실시예 6><Example 6>
아래와 같이 실시한 것을 제외하고는 실시예 5와 동일한 방법으로 드라이필름 포토레지스트를 제조하였다.　 A dry film photoresist was prepared in the same manner as in Example 5, except that the following procedure was carried out.
(a) 중량평균분자량이 75000, 검화도가 87%인 폴리비닐알코올(KURARAY사, PVA217) 10g, 및 폴리실리콘(BYK사, BYK-349, 건조후 고형분대비 0.25%) 0.025g을 증류수 90g, 부톡시에탄올 10g에 넣고 80℃에서 6시간 교반하여 완전히 녹여 수지 보호층용 조성물을 제조하였다.　 이를 두께 16㎛ 지지체 필름(CY201-16㎛, KOLON) 위에 코팅 바를 이용하여 코팅한 후, 열풍오븐을 이용하여 80℃에서 10분간 건조하여 두께 3㎛의 수지 보호층을 형성하였다. (a) 10 g of polyvinyl alcohol (KURARAY, PVA217) having a weight average molecular weight of 75000, saponification degree of 87%, and 0.025 g of polysilicon (BYK, BYK-349, 0.25% of solid content after drying), 90 g of distilled water, It was added to 10 g of butoxyethanol and stirred at 80 ° C. for 6 hours to completely dissolve to prepare a resin protective layer composition. This was coated on a 16 μm thick support film (CY201-16 μm, KOLON) using a coating bar, and then dried at 80 ° C. for 10 minutes using a hot air oven to form a resin protective layer having a thickness of 3 μm.
<실시예 7><Example 7>
아래와 같이 실시한 것을 제외하고는 실시예 5와 동일한 방법으로 드라이필름 포토레지스트를 제조하였다. A dry film photoresist was prepared in the same manner as in Example 5, except that the following procedure was carried out.
(a) 중량평균분자량이 22000, 검화도가 87%인 폴리비닐알코올(KURARAY사, PVA205) 20g, 및 폴리실리콘(BYK사, BYK-349, 건조후 고형분대비 0.25%) 0.05g을 증류수 90g, 에톡시에탄올 10g에 넣고 80℃에서 6시간 교반하여 완전히 녹여 수지 보호층용 조성물을 제조하였다.　 이를 두께 50㎛인 지지체 필름(F-50, 동신화학) 위에 코팅 바를 이용하여 코팅한 후, 열풍오븐을 이용하여 80℃에서 20분간 건조하여 두께 10㎛의 수지 보호층을 형성하였다. 이 때, 상기 지지체 필름은 불소 수지를 사용하여 이형층을 형성한 것을 제외하고는 실시예 5와 동일한 방법으로 제조한 폴리에틸렌테레프탈레이트 필름이다.(a) 20 g of polyvinyl alcohol (KURARAY, PVA205) having a weight average molecular weight of 22000 and 87% saponification, and 0.05 g of polysilicon (BYK, BYK-349, 0.25% of the solid content after drying), 90 g of distilled water, It was added to 10 g of ethoxyethanol and stirred at 80 ° C. for 6 hours to completely dissolve to prepare a composition for a resin protective layer. It was coated on a support film (F-50, Dongshin Chemical) having a thickness of 50 μm using a coating bar, and then dried at 80 ° C. for 20 minutes using a hot air oven to form a resin protective layer having a thickness of 10 μm. At this time, the support film is a polyethylene terephthalate film prepared in the same manner as in Example 5 except that the release layer was formed using a fluorine resin.
<실시예 8><Example 8>
아래와 같이 실시한 것을 제외하고는 실시예 5와 동일한 방법으로 드라이필름 포토레지스트를 제조하였다. A dry film photoresist was prepared in the same manner as in Example 5, except that the following procedure was carried out.
(a) 중량평균분자량이 22000, 검화도가 87%인 폴리비닐알코올(KURARAY사, PVA205) 20g, 및 폴리실리콘(BYK사, BYK-349, 건조후 고형분대비 0.25%) 0.05g을 증류수 99.5g, 부톡시에탄올(2-n-butoxyethanol) 0.5g에 넣고 80℃에서 6시간 교반하여 완전히 녹여 수지 보호층용 조성물을 제조하였다.　 이를 두께 16㎛인 지지체 필름(CY201-16㎛, KOLON) 위에 코팅 바를 이용하여 코팅한 후, 열풍오븐을 이용하여 80℃에서 10분간 건조하여 두께 3㎛의 수지 보호층을 형성하였다.　(a) 20 g of polyvinyl alcohol (KURARAY, PVA205) having a weight average molecular weight of 22000 and 87% saponification, and 0.05 g of polysilicon (BYK, BYK-349, 0.25% of the solid content after drying) 99.5 g of distilled water , Butoxyethanol (2-n-butoxyethanol) was added to 0.5g and stirred for 6 hours at 80 ℃ completely dissolved to prepare a composition for the resin protective layer. This was coated on a support film (CY201-16 μm, KOLON) having a thickness of 16 μm using a coating bar, and then dried at 80 ° C. for 10 minutes using a hot air oven to form a resin protective layer having a thickness of 3 μm.
<실시예 9>Example 9
아래와 같이 실시한 것을 제외하고는 실시예 5와 동일한 방법으로 드라이필름 포토레지스트를 제조하였다.　 A dry film photoresist was prepared in the same manner as in Example 5, except that the following procedure was carried out.
(a) 중량평균분자량이 75000, 검화도가 87%인 폴리비닐알코올(KURARAY사, PVA217) 10g을 증류수 68g, 부톡시에탄올 32g에 넣고 80℃에서 6시간 교반하여 완전히 녹여 수지 보호층용 조성물을 제조하였다.　 이를 두께 16㎛ 지지체 필름(CY201-16㎛, KOLON) 위에 코팅 바를 이용하여 코팅한 후, 열풍오븐을 이용하여 80℃에서 10분간 건조하여 두께 3㎛의 수지 보호층을 형성하였다. (a) 10 g of polyvinyl alcohol (KURARAY Co., PVA217) having a weight average molecular weight of 75000 and saponification degree of 87% was added to 68 g of distilled water and 32 g of butoxyethanol and stirred at 80 ° C. for 6 hours to completely dissolve to prepare a composition for a resin protective layer. It was. This was coated on a 16 μm thick support film (CY201-16 μm, KOLON) using a coating bar, and then dried at 80 ° C. for 10 minutes using a hot air oven to form a resin protective layer having a thickness of 3 μm.
<비교예 1>Comparative Example 1
(a) UH-9200 series(Kolon)에 사용된 조성 및 함량으로 감광성 수지 조성물을 제조하였다.　 구체적으로는, 광개시제류를 용매인 메틸에틸케톤과 메틸알코올에 녹인 후, 광중합성 올리고머류와 바인더 폴리머를 첨가하여 교반기계를 이용하여 1시간 동안 혼합하여 감광성 수지 조성물을 제조하였다. (a) A photosensitive resin composition was prepared in the composition and content used for UH-9200 series (Kolon). Specifically, photoinitiators were dissolved in methyl ethyl ketone and methyl alcohol as solvents, and then photopolymerizable oligomers and binder polymers were added and mixed for 1 hour using a stirring machine to prepare a photosensitive resin composition.
(b) 상기 감광성 수지 조성물을 두께 16㎛인 지지체 필름(헤이즈 2.3%, 이형층 없음, 폴리에틸렌테레프탈레이트 필름, FDFR-16㎛, KOLON) 위에 코팅 바를 이용하여 코팅한 후, 열풍오븐을 이용하여 80℃에서 10분간 건조하여 두께 15㎛의 감광성 수지층을 형성하였다. (b) coating the photosensitive resin composition on a support film having a thickness of 16 μm (haze 2.3%, no release layer, polyethylene terephthalate film, FDFR-16 μm, KOLON) using a coating bar, and then using a hot air oven. It dried at 10 degreeC for 10 minutes, and formed the photosensitive resin layer of 15 micrometers in thickness.
(c) 건조가 완료된 (b) 필름의 감광성 수지층과 두께가 19㎛인 보호필름(CY201-19㎛, KOLON)의 이형층이 접하도록 50℃에서 압력 4kgf/㎠로 라미네이션하여 두께 50㎛의 드라이필름 포토레지스트를 제조하였다. (c) laminating at 50 ° C. at a pressure of 4 kgf / cm 2 at a temperature of 50 ° C. such that the photosensitive resin layer of the dried film (b) and the release layer of the protective film (CY201-19 μm, KOLON) having a thickness of 19 μm were in contact with each other. A dry film photoresist was prepared.
<비교예 2>Comparative Example 2
부톡시에탄올 대신 아세톤을 사용하는 것을 제외하고는 실시예 1과 동일하게 실시하였다. The same procedure as in Example 1 was repeated except that acetone was used instead of butoxyethanol.
<비교예 3>Comparative Example 3
부톡시에탄올 대신 테트라하이드로푸란(THF)을 사용하는 것을 제외하고는 실시예 1과 동일하게 실시하였다. The same procedure as in Example 1 was repeated except that tetrahydrofuran (THF) was used instead of butoxyethanol.
<비교예 4><Comparative Example 4>
부톡시에탄올 대신 테트라하이드로푸란(THF)을 사용하는 것을 제외하고는 실시예 5와 동일하게 실시하였다. The same procedure as in Example 5 was repeated except that tetrahydrofuran (THF) was used instead of butoxyethanol.
상기 실시예 1 내지 9 및 비교예 2 내지 4에 따른 수용성 고분자의 중량평균 분자량, 검화도 및 잔류용매량은 하기 방법으로 측정하였다. The weight average molecular weight, saponification degree, and residual solvent amount of the water-soluble polymers according to Examples 1 to 9 and Comparative Examples 2 to 4 were measured by the following method.
중량평균분자량 측정Weight average molecular weight measurement
수용성 고분자의 중량평균분자량은 GFC(Gel Filtration Chromatography; Varian GPC system)를 이용하여 40℃의 온도, Stationary Phase는 (Plgel Mixed D) × 2, Mobile Phase : THF, 1.0ml/min, Injection : 100㎕,　 Detection : RI, 40C 의 조건 하에서 PS Standard(Polymer Standards Service사, Mp 723000,219000,89300,52200,30300,7000,5000,2960)를 0.1％ 농도로 THF에 녹여 주입한 것을 기준물질로 측정하였다. 시료는 0.2％ 농도로 THF에 녹인 후 0.45㎛　PTFE syringe filter로 여과하여 주입하였다.The weight average molecular weight of the water-soluble polymer is 40 ° C using GFC (Gel Filtration Chromatography; Varian GPC system), Stationary Phase is (Plgel Mixed D) × 2, Mobile Phase: THF, 1.0ml / min, Injection: 100µl , Detection: Injecting PS Standard (Polymer Standards Service, Mp 723000,219000,89300,52200,30300,7000,5000,2960) dissolved in THF at 0.1% concentration under the conditions of RI and 40C was measured as a reference substance. . Samples were dissolved in THF at a concentration of 0.2% and filtered by 0.45 μm PTFE syringe filter.
검화도Safflower 측정 Measure
폴리비닐알코올의 검화도는 JIS K6726 방법에 따라 측정하였다. The saponification degree of polyvinyl alcohol was measured in accordance with JIS K6726 method.
잔류용매량Residual solvent 측정 Measure
잔류용매량 측정은 Headspace를 이용한 GC-Mass로 측정한다. 잔류용매량을 측정하기 위한 시료로서 실시예 1 내지 9 및 비교예 2 와 4에 따라 제조된 드라이필름 포토레지스트를 7cm×7cm 크기로 자른 후 보호필름을 벗겨내어 10cm×10cm 크기의 동장적층판에 라미네이션하였다. 그 다음 라미네이션된 드라이필름 포토레지스트의 지지체 필름을 벗겨낸 후 수지 보호층을 벗겨내고 Haze Meter(NIPPON DENSHOKU사, NDH-2000)을 이용하여 상기 벗겨낸 수지 보호층을 준비하였고, 이 수지 보호층 5g을 취하여 22ml Headspace vial에 넣고 밀봉한 후 Headspace 조건(Incubation Temp. : 200℃ (oven), Incubation Time : 30min, Syringe Temp. : 150℃, Agitator speed : 250rpm, Fill Speed : 25ul/s, Fill Strokes : 0, Injection Speed : 700 ul/s, Pre Inject Delay : 0 ms, Post inject Delay : 500ms)에서 측정하였다. 시료의 측정조건은 아래와 같다.Residual solvent amount is measured by GC-Mass using headspace. As a sample for measuring the amount of residual solvent, the dry film photoresist prepared according to Examples 1 to 9 and Comparative Examples 2 and 4 was cut into 7 cm × 7 cm and then peeled off the protective film to be laminated on a copper clad laminate having a size of 10 cm × 10 cm. It was. Then, after peeling off the support film of the laminated dry film photoresist, the resin protective layer was peeled off, and the peeled resin protective layer was prepared using a Haze Meter (NIPPON DENSHOKU, NDH-2000), and the resin protective layer 5g After taking it into 22ml headspace vial and sealing it, Headspace condition (Incubation Temp .: 200 ℃ (Oven), Incubation Time: 30min, Syringe Temp .: 150 ℃, Agitator speed: 250rpm, Fill Speed: 25ul / s, Fill Strokes: 0, Injection Speed: 700 ul / s, Pre Inject Delay: 0 ms, Post Inject Delay: 500 ms). The measurement conditions of the sample are as follows.
Instrument : Varian 4000 GC/MS + CombiPAL injectorInstrument: Varian 4000 GC / MS + CombiPAL injector
Stationary Phase : VF-5ms (30m × 0.25mm × 0.25um)Stationary Phase: VF-5ms (30m × 0.25mm × 0.25um)
Mobile Phase : He, 1mL/minMobile Phase: He, 1mL / min
Injection : Headpspace- 200ul (splitless) , 250℃Injection: Headpspace- 200ul (splitless), 250 ℃
Temperature : From 40℃ (5min) to 240℃ (5min) @ 10℃/min Temperature: From 40 ℃ (5min) to 240 ℃ (5min) @ 10 ℃ / min
Detection : EI mode (28 ~ 500m/z Full scan)Detection: EI mode (28 ~ 500m / z Full scan)
상기 실시예 1 내지 9 및 비교예 1 내지 4에 의하여 제조된 드라이필름 포토레지스트의 점착력을 다음과 같이 측정하였다. The adhesion of the dry film photoresist prepared by Examples 1 to 9 and Comparative Examples 1 to 4 was measured as follows.
점착력 측정Adhesive force measurement
<지지체 필름과 수지 보호층간 점착력><Adhesion between support film and resin protective layer>
폭 3㎝, 길이 20㎝의 드라이필름 포토레지스트 시편의 보호 필름을 제거하여 동장적층판에 110℃, 4㎏f/㎠ 조건하에서 2m/min 속도로 라미네이션한 후 지지체 필름을 제거하였다. 여기에 폭 4㎝, 길이 25㎝, 두께 19㎛의 PET 필름(FDFR, Kolon사 제조)을 110℃, 4㎏f/㎠ 조건하에서 2m/min 속도로 라미네이션한 후, 상기 PET 필름을 이형시키기 시작하여 시작점에서 5㎝ 지점부터 8㎝ 지점까지 100mm/min의 속도로 10N load cell을 사용하여 이형시키는데 필요한 힘을 UTM(4303 series, Instron사)을 사용하여 측정하였다.  The protective film of the dry film photoresist specimen having a width of 3 cm and a length of 20 cm was removed, and the support film was removed after lamination at a speed of 2 m / min at 110 ° C. and 4 kgf / cm 2 on the copper-clad laminate. After laminating a 4 cm wide, 25 cm long, 19 μm thick PET film (FDFR, manufactured by Kolon) at 110 ° C. and 4 kgf / cm 2 conditions at a rate of 2 m / min, the PET film began to be released. The force required to release using a 10N load cell at a speed of 100 mm / min from the starting point of 5 cm to 8 cm was measured using UTM (4303 series, Instron).
<이형층과 수지 보호층간 점착력><Adhesion between release layer and resin protective layer>
폭 3㎝, 길이 20㎝의 드라이필름 포토레지스트 시편의 보호필름을 제거한 뒤 110℃에서 속도 2m/min, 압력 4㎏f/㎠ 으로 동장적층판에 라미네이션하였다. 이후 지지체 필름을 이형시키면서 시작점에서 5㎝ 지점부터 8㎝ 지점까지 100mm/min의 속도로 10N load cell을 사용하여 이형시키는데 필요한 힘을 UTM(4303 series, Instron사)을 사용하여 측정하였다. 이때, 상기 지지체 필름을 이형시킨다는 것은 실시예 5 내지 9인 경우 지지체 필름의 일면에 있는 이형층을 이형시키는 것을 의미한다. The protective film of the dry film photoresist specimen having a width of 3 cm and a length of 20 cm was removed, and then laminated on the copper clad laminate at 110 ° C. at a speed of 2 m / min and a pressure of 4 kgf / cm 2. Then, the release force of the support film was measured using a UTM (4303 series, Instron) using a 10N load cell at a speed of 100 mm / min from a starting point of 5 cm to 8 cm at a starting point. At this time, releasing the support film means in the case of Examples 5 to 9 to release the release layer on one surface of the support film.
<감광성 수지층과 보호필름간의 점착력><Adhesion between the photosensitive resin layer and the protective film>
폭 3㎝, 길이 20㎝의 드라이필름 포토레지스트 시편의 보호필름을 이형시키면서 시작점에서 5㎝ 지점부터 8㎝ 지점까지 100mm/min의 속도로 10N load cell을 사용하여 이형시키는데 필요한 힘을 만능시험기(UTM, 4303 series, Instron사)를 사용하여 측정하였다.A universal testing machine (UTM) was used to release a protective film of a dry film photoresist specimen having a width of 3 cm and a length of 20 cm, using a 10 N load cell at a speed of 100 mm / min from a starting point of 5 cm to 8 cm. , 4303 series, Instron).
<지지체 필름을 벗긴 후 수지 보호층과 PET의 점착력><Adhesion between resin protective layer and PET after peeling support film>
폭 3㎝, 길이 20㎝의 드라이필름 포토레지스트 시편의 보호 필름을 제거하여 동장적층판에 110℃, 4㎏f/㎠ 조건하에서 2m/min 속도로 라미네이션한 후 지지체 필름을 제거하였다. 이때, 상기 지지체 필름을 제거했다는 것은 실시예 1 내지 5인 경우 지지체 필름의 일면에 있는 이형층도 함께 제거했다는 것을 의미한다. The protective film of the dry film photoresist specimen having a width of 3 cm and a length of 20 cm was removed, and the support film was removed after lamination at a speed of 2 m / min at 110 ° C. and 4 kgf / cm 2 on the copper-clad laminate. At this time, the removal of the support film means that in the case of Examples 1 to 5, the release layer on one surface of the support film was also removed.
여기에 폭 4㎝, 길이 25㎝, 두께 19㎛의 PET 필름(FDFR, Kolon사 제조)을 110℃, 4㎏f/㎠ 조건하에서 2m/min 속도로 라미네이션한 후, 상기 PET 필름을 이형시키기 시작하여 시작점에서 5㎝ 지점부터 8㎝ 지점까지 100mm/min의 속도로 10N load cell을 사용하여 이형시키는데 필요한 힘을 UTM(4303 series, Instron사)을 사용하여 측정하였다. After laminating a 4 cm wide, 25 cm long, 19 μm thick PET film (FDFR, manufactured by Kolon) at 110 ° C. and 4 kgf / cm 2 conditions at a rate of 2 m / min, the PET film began to be released. The force required to release using a 10N load cell at a speed of 100 mm / min from the starting point of 5 cm to 8 cm was measured using UTM (4303 series, Instron).
하기 표 1은 실시예 1 내지 4 및 비교예 1 내지 4에 의하여 제조된 드라이필름 포토레지스트의 점착력을 측정한 결과를 나타낸 것이다. Table 1 shows the results of measuring the adhesive strength of the dry film photoresist prepared by Examples 1 to 4 and Comparative Examples 1 to 4.
상기 PET 필름의 라미네이션 할 때의 조건은 일반적인 노광 시의 마스크와 접착되는 조건과 동일하며 하기 표 1에서 이때 측정된 지지체 필름의 점착력은 실시예 1 내지 4 및 비교예 2 내지 4의 경우 수지 보호층과 PET 필름간의 점착력이며, 비교예 1의 경우 감광성 수지층과 PET 필름간의 점착력이다. Conditions of lamination of the PET film is the same as the conditions that are bonded to the mask in the general exposure and the adhesive strength of the support film measured at this time in Table 1 is the resin protective layer in Examples 1 to 4 and Comparative Examples 2 to 4 And the adhesive force between the PET film and Comparative Example 1, the adhesive force between the photosensitive resin layer and the PET film.
또한, 하기 표 2는 실시예 5 내지 9 및 비교예 1에 의하여 제조된 드라이필름 포토레지스트의 점착력을 측정한 결과를 나타낸 것이다. 상기 PET 필름의 라미네이션 할 때의 조건은 일반적인 노광 시의 마스크와 접착되는 조건과 동일하다. In addition, Table 2 below shows the results of measuring the adhesive strength of the dry film photoresist prepared by Examples 5 to 9 and Comparative Example 1. The conditions for lamination of the PET film are the same as the conditions for bonding with the mask during normal exposure.
표 1
점착력(N/cm)
감광성 수지층과 보호 필름간 점착력 지지체 필름과 수지 보호층간 점착력 지지체 필름을 벗긴 후 수지 보호층과 보호필름의 점착력
실시예 1 0.0017 0.0027 0.0010
2 0.0017 0.0027 0.0010
3 0.0017 0.0027 0.0010
4 0.0017 0.0027 0.0010
비교예 1 0.0017 0.0047* 0.0043**
2 필름 형성 불가
3
4
Table 1
Adhesion (N / cm)
Adhesive force between the photosensitive resin layer and the protective film Adhesion between Support Film and Resin Protective Layer Adhesion between resin protective layer and protective film after peeling support film
EXAMPLE One 0.0017 0.0027 0.0010
2 0.0017 0.0027 0.0010
3 0.0017 0.0027 0.0010
4 0.0017 0.0027 0.0010
Comparative example One 0.0017 0.0047 * 0.0043 **
2 No film formation
3
4
(주) 상기 표 1에서 예외적으로 *은 지지체 필름과 감광성 수지층간의 점착력을 의미하고, **은 지지체 필름을 벗긴 후 감광성 수지층과 보호필름간의 점착력을 의미한다. (Note) The exceptional * in Table 1 means the adhesive force between the support film and the photosensitive resin layer, ** means the adhesive force between the photosensitive resin layer and the protective film after peeling off the support film.
표 2
점착력(N/cm)
감광성 수지층과 보호 필름간 점착력 이형층과 수지 보호층간 점착력 지지체 필름을 벗긴 후 수지 보호층과 PET의 점착력
실시예 5 0.0017 0.0019 0.0010
6 0.0017 0.0020 0.0009
7 0.0017 0.0020 0.0010
8 0.0017 0.0018 0.0010
9 0.0017 0.0021 0.0011
비교예 1 0.0017 0.0047* 0.0043**
TABLE 2
Adhesion (N / cm)
Adhesive force between the photosensitive resin layer and the protective film Adhesion between release layer and resin protective layer Adhesion between resin protective layer and PET after peeling support film
EXAMPLE 5 0.0017 0.0019 0.0010
6 0.0017 0.0020 0.0009
7 0.0017 0.0020 0.0010
8 0.0017 0.0018 0.0010
9 0.0017 0.0021 0.0011
Comparative example One 0.0017 0.0047 * 0.0043 **
(주) 상기 표 2에서 예외적으로 *은 지지체 필름과 감광성 수지층간의 점착력을 의미하고, **은 지지체 필름을 벗긴 후 감광성 수지층과 PET 필름간의 점착력을 의미한다.(Note) The exceptional * in Table 2 means the adhesive force between the support film and the photosensitive resin layer, ** indicates the adhesive force between the photosensitive resin layer and the PET film after peeling off the support film.
상기 측정 결과, 실시예 1 내지 4와 비교예 1에서는 감광성 수지층과 보호필름간의 이형력 및 수지 보호층과 지지체 필름간의 이형력이 작업성을 저해하지 않는 범위에 있는 것을 알 수 있으며, 비교예 2와 4는 실시예에서 사용한 알콕시알코올이 아닌 물과 상용성이 있는 용매를 사용하였으나 수지 보호층의 주된 물질인 폴리비닐알코올과의 상용성이 많이 떨어져 침전현상이 일어났기 때문에 드라이필름 포토레지스트로 사용할 수 없는 필름의 형성이 불가하였고, 따라서 본 발명에서 사용 불가능한 용매로 볼 수 있다. As a result of the measurement, in Examples 1 to 4 and Comparative Example 1, it can be seen that the release force between the photosensitive resin layer and the protective film and the release force between the resin protective layer and the support film are in a range that does not impair workability. 2 and 4 used solvents that were compatible with water, not the alkoxy alcohols used in the examples. However, due to the incompatibility with polyvinyl alcohol, which is the main material of the resin protective layer, precipitation occurred. The formation of unacceptable films was not possible and can therefore be seen as solvents not usable in the present invention.
또한, 실시예 5 내지 9의 경우 감광성 수지층과 보호필름간의 이형력 및 수지 보호층과 지지체 필름의 일면에 있는 이형층간의 점착력은 작업성을 저해하지 않는 범위에 있는 것을 알 수 있다. In addition, in Examples 5 to 9, it can be seen that the release force between the photosensitive resin layer and the protective film and the adhesive force between the release layer on one surface of the resin protective layer and the support film are in a range that does not impair workability.
이로부터 실시예 1 내지 9인 경우 수지 보호층과 노광 조건에서 일반적으로 사용되는 마스크 재질간의 점착력이 매우 낮은 것을 알 수 있으며 따라서 노광시 취급이 용이함을 알 수 있다. From this, in Examples 1 to 9 it can be seen that the adhesion between the resin protective layer and the mask material generally used in the exposure conditions is very low, and therefore it can be seen that the handling is easy during exposure.
특성 평가Property evaluation
이후 상기 실시예 1 내지 9 및 비교예 1 내지 4에서 제조된 드라이필름 포토레지스트를 다음과 같은 방법으로 인쇄회로기판에 형성한 후, 드라이필름 포토레지스트의 특성을 평가하였다. Thereafter, the dry film photoresist prepared in Examples 1 to 9 and Comparative Examples 1 to 4 was formed on the printed circuit board by the following method, and then the characteristics of the dry film photoresist were evaluated.
(1) 인쇄회로기판 상의 형성(1) Formation on a printed circuit board
동장적층판(CCL)에 브러시 전처리기를 사용하여 새로운 동면을 형성하고 적절한 표면조도를 형성한다. 이후 5% 황산용액에서 산처리 후 수세, 건조를 하여 라미네이터에 투입하였다. 라미네이터는 Hakuto Mach 610i를 사용하였으며 110℃에서 압력 4㎏f/㎠, 속도 2m/min로 실시예 1 내지 6 및 비교예 1 내지 7에서 제조된 드라이필름 포토레지스트를 동장적층판에 라미네이션하였으며, 이때 예열은 실시하지 않았다. 이후 UV 노광기(Perkin Elmer OB-7120, 5KW 평행광)로 조사하여 노광을 실시하였다. 노광을 마친 인쇄회로기판을 현상기를 통과시켜 현상하였다. A brush preprocessor is used for the copper clad laminate (CCL) to form new copper surfaces and to form the appropriate surface finish. After acid treatment in 5% sulfuric acid solution, washed with water, dried and added to the laminator. The laminator used Hakuto Mach 610i, and the dry film photoresist prepared in Examples 1 to 6 and Comparative Examples 1 to 7 at 110 ° C. at a pressure of 4 kgf / cm 2 and a speed of 2 m / min. Did not carry. Then, the exposure was performed by irradiating with a UV exposure machine (Perkin Elmer OB-7120, 5KW parallel light). After the exposure, the printed circuit board was developed by passing through a developer.
이때 수지 보호층을 포함한 실시예 1 내지 6의 경우 노광공정 전에 지지체 필름을 벗겨내었으며 수지 보호층이 포함되지 않은 비교예 1의 경우 지지체 필름을 현상 공정 전에 벗겨내었다. In this case, in Examples 1 to 6 including the resin protective layer, the support film was peeled off before the exposure process, and in Comparative Example 1 in which the resin protective layer was not included, the support film was peeled off before the developing process.
(a) 헤이즈(a) haze
실시예 1 내지 9 및 비교예 1 내지 4에 따라 제조된 드라이필름 포토레지스트를 7cm×7cm 크기로 자른 후 보호필름을 벗겨내어 10cm×10cm 크기의 동장적층판에 라미네이션하였다. 그 다음 라미네이션된 드라이필름 포토레지스트의 지지체 필름을 벗겨낸 후 수지 보호층을 벗겨내고 Haze Meter(NIPPON DENSHOKU사, NDH-2000)을 이용하여 상기 벗겨낸 수지 보호층의 헤이즈를 측정하였다. The dry film photoresist prepared according to Examples 1 to 9 and Comparative Examples 1 to 4 was cut to a size of 7 cm × 7 cm, and then the protective film was peeled off and laminated on a copper clad laminate having a size of 10 cm × 10 cm. Then, after peeling off the support film of the laminated dry film photoresist, the resin protective layer was peeled off and the haze of the peeled resin protective layer was measured using a Haze Meter (NIPPON DENSHOKU, NDH-2000).
(b) 현상시간(b) Development time
수지 보호층을 포함하지 않는 경우, 상기 (a)와 같이 드라이필름 포토레지스트를 동장적층판에 라미네이션을 마친 인쇄회로기판을 온도 30℃인 조건에서 압력 1.5kgf/㎠으로 현상액(1% Na2CO3 수용액)을 분사하는, 팬(fan) 타입의 노즐과 기판의 간격이 15㎝인 현상기에 통과시켜 라미네이션 된 부위가 현상액에 완전히 씻겨서 제거되는 시간을 측정하여 이를 감광성 수지층만의 최소현상시간(이하, 'Smin'로 함)이라 하였다. 또한, 감광성 수지층만의 실제현상시간(이하, 'Sdel'로 함)은 감광성 수지층만의 최소현상시간(Smin)의 두배의 시간으로 산정하였다. When the resin protective layer is not included, the printed circuit board after lamination of the dry film photoresist on the copper-clad laminate as shown in (a) is carried out at a pressure of 1.5 kgf / cm 2 under a condition of 30 ° C. (1% Na 2 CO 3). After passing through a fan-type nozzle that sprays an aqueous solution) and a substrate having a distance of 15 cm, the time at which the laminated part is completely washed and removed by the developer is measured. , 'S min '). In addition, the actual development time (hereinafter referred to as 'S del ') only of the photosensitive resin layer was calculated to be twice the minimum development time (S min ) of only the photosensitive resin layer.
한편, 수지 보호층을 포함하는 필름인 경우, 수지 보호층을 포함하는 필름의 최소현상시간(이하, 'Pmin'로 함)은 감광성 수지층만의 최소현상시간(Smin)을 측정하는 방법과 동일하게 측정하였고, 수지 보호층을 포함하는 필름의 실제현상시간(이하, 'Pdel'로 함)은 감광성 수지층만의 실제현상시간(Sdel)에 수지 보호층만의 현상시간(이하, 'Ptim'로 함)을 추가해 주어야 하며, 이를 나타내면 다음 수식 1과 같다. On the other hand, in the case of the film including the resin protective layer, the minimum development time (hereinafter referred to as 'P min ') of the film including the resin protective layer is a method of measuring the minimum development time (S min ) of the photosensitive resin layer was measured in the same way, a resin (referred to as' P del 'hereinafter), the protective layer the actual processing time of the film, including the processing time of the resin protection layer only on the actual developing time (S del) of the photosensitive resin layer only (hereinafter,' P tim '), which is shown in Equation 1 below.
<수식 1><Equation 1>
Pdel = Sdel + Ptim Pdel = Sdel + Ptim             
= Smin × 2 + Ptim = S min × 2 + P tim
상기 수식 1을 달리 표현하면 하기 수식 2로 표현된다. Another expression of Equation 1 is expressed by Equation 2 below.
<수식 2><Formula 2>
Pdel = Pmin + Smin Pdel                  = Pmin + Smin             
따라서, 수지 보호층을 포함하는 필름의 최소현상시간과 수지 보호층을 포함하지 않는 필름의 최소현상시간, 즉 감광성 수지층만의 최소현상시간을 각각 측정하여 이들 값으로부터 수지 보호층을 포함하는 필름의 실제현상시간을 산출할 수 있다. Therefore, the minimum development time of the film including the resin protective layer and the minimum development time of the film not including the resin protective layer, that is, the minimum development time of only the photosensitive resin layer, were measured, respectively. The actual development time can be calculated.
여기서, 감광성 수지층만의 최소현상시간(Smin)은 비교예 1의 드라이필름 포토레지스트에 대한 최소현상시간으로 가름한다. Here, the minimum development time S min of the photosensitive resin layer is determined by the minimum development time for the dry film photoresist of Comparative Example 1.
상기 수식 1 및 수식 2로부터 수지 보호층만의 현상시간(Ptim)을 산출하며, 산출된 현상시간을 수지 보호층의 두께로 나눈 값을 수지 보호층의 1㎛당 현상시간으로 정의한다. The developing time P tim of only the resin protective layer is calculated from Equations 1 and 2, and the value obtained by dividing the calculated developing time by the thickness of the resin protective layer is defined as the developing time per μm of the resin protective layer.
(c) 감도와 노광량 (c) sensitivity and exposure dose
노광시 실시예 1 내지 9 및 비교예 2 내지 4의 경우에는 수지 보호층 상에, 비교예 1의 경우에는 지지체 필름상에 감도기(21단 Stouffer Step Tablet)을 위치시킨 후, 감도 5단, 6단, 7단을 얻기 위한 노광량을 광량계(UV-351, ORC사 제조)를 사용하여 측정하였으며, 그 값은 하기 표 3에 나타내었다. 이때 감도는 현상 후 기판에 남아있는 감광성 레지스트의 최대 단위 개수로 평가하였다. In the case of exposure, Examples 1 to 9 and Comparative Examples 2 to 4 were placed on a resin protective layer, and Comparative Example 1 was placed on a support film on a support film. The exposure amount for obtaining 6 steps and 7 steps was measured using a photometer (UV-351, manufactured by ORC), and the values are shown in Table 3 below. At this time, the sensitivity was evaluated by the maximum number of units of the photosensitive resist remaining on the substrate after development.
(2) 회로물성: 해상도, 세션밀착력, 1/1(Line/Space)해상도(2) Circuit Properties: Resolution, Session Adhesion, 1/1 (Line / Space) Resolution
Kolon Test Artwork를 이용하여 해상도, 세선밀착력, 1/1(Line/Space)해상도를 측정하여 회로물성을 평가하였다. The Kolon Test Artwork was used to evaluate the circuit properties by measuring the resolution, thin line adhesion, and 1/1 (Line / Space) resolution.
본 실험에서 해상도는 미노광부위가 현상될 때 얼마나 작은 선폭까지 현상되었는지 정도를 측정한 값으로 이 값이 작을수록 해상도가 높으며, 측정된 해상도의 측정에 사용된 마스크는 4 내지 20㎛까지 0.5㎛의 간격으로 형성되어 있으며 구현하고자 하는 값의 해상도에 간격 400㎛로 만들어진 마스크를 사용하였다. 세선밀착력 값은 노광부위가 현상 후 얼마나 작은 선폭까지 침식을 받지 않고 직선의 회로를 형성하는가를 측정한 값으로 이 값이 작을수록 세선밀착력 값이 좋으며, 측정된 세선밀착력 값의 측정에 사용된 마스크는 4 내지 20㎛까지 0.5㎛의 간격으로 형성되어 있으며 구현하고자 하는 값의 세선밀착력 값에 간격 400㎛로 만들어진 마스크를 사용하였다. 또한 1/1 해상도는 회로라인과 회로라인 사이의 간격을 1:1로 하여 깨끗하게 현상된 최소 선폭을 측정한 값을 나타낸 것이다. In this experiment, the resolution is a measure of how small the line width was developed when the unexposed areas were developed. The smaller this value, the higher the resolution. The mask used for measuring the measured resolution was 0.5 μm up to 4 to 20 μm. The mask was formed at intervals of and a mask made with an interval of 400 μm was used for the resolution of the value to be implemented. The thin line adhesion value is a measure of how small the line width after exposure is formed to form a straight line circuit without being eroded. The smaller the value, the better the fine line adhesion value, and the mask used for measuring the measured thin line adhesion value. Was formed at intervals of 0.5 μm to 4 to 20 μm, and a mask made of 400 μm was used for the fine wire adhesion value of the value to be realized. In addition, 1/1 resolution represents the value of the cleanest developed minimum line width with the distance between the circuit line and the circuit line 1: 1.
(3) 표면 분석(3) surface analysis
실시예 1, 실시예 5 및 비교예 1의 드라이필름 포토레지스트를 적용한 인쇄회로기판을 상기와 같이 노광 및 현상공정을 거친 뒤, 표면을 전자현미경으로 촬영하여 각각 도 1, 도 2 및 도 3에 나타내었다. After the exposure and development processes of the printed circuit board to which the dry film photoresist of Example 1, Example 5 and Comparative Example 1 were applied as described above, the surface of the printed circuit board was photographed by electron microscopy, respectively, in FIGS. 1, 2 and 3, respectively. Indicated.
하기 표 3은 헤이즈 현상시간 및 노광조건에 따른 회로물성의 측정 결과를 각각 나타낸 것이다. Table 3 shows the measurement results of the circuit properties according to the haze development time and exposure conditions, respectively.
표 3
헤이즈(%) 1㎛당현상시간(sec) 현상시간 노광 조건 회로 물성
최소현상시간(sec) 실제현상시간(sec) 노광에너지(mJ/㎠) 감도(sst/21sst) 해상도(㎛) 세선밀착력(㎛) 1/1해상도(㎛)
실시예 1 0.80 1 11 19 50 5 7 13 9
60 6 9 11 9
70 7 9 8 9
실시예 2 0.80 1 11 19 50 5 7 13 9
60 6 9 11 9
70 7 9 8 9
실시예 3 0.80 1 11 19 50 5 7 13 9
60 6 9 11 9
70 7 9 8 9
실시예 4 0.80 1 11 19 50 5 7 13 9
60 6 9 11 9
70 7 9 8 9
실시예 5 0.12 1 11 19 50 5 7 13 9
60 6 9 11 9
70 7 9 8 9
실시예 6 0.12 3 17 25 50 5 7 13 9
60 6 9 11 9
70 7 9 8 9
실시예 7 0.81 1 18 26 50 5 8 13 9
60 6 10 11 10
70 7 11 8 11
실시예 8 0.79 1 11 19 50 5 8 13 8
60 6 9 11 10
70 7 9 9 9
실시예 9 0.10 3 17 25 50 5 7 14 9
60 6 10 11 9
70 7 9 9 9
비교예 1 측정불가 측정불가 8* 16** 50 5 8 13 10
60 6 11 13 11
70 7 13 8 13
비교예 2 측정불가
비교예 3 측정불가
비교예 4 측정불가
TABLE 3
Haze (%) Development time per 1㎛ (sec) Developing time Exposure conditions Circuit properties
Minimum developing time (sec) Actual development time (sec) Exposure energy (mJ / ㎠) Sensitivity (sst / 21sst) Resolution (μm) Fine wire adhesion (㎛) 1/1 Resolution (μm)
Example 1 0.80 One 11 19 50 5 7 13 9
60 6 9 11 9
70 7 9 8 9
Example 2 0.80 One 11 19 50 5 7 13 9
60 6 9 11 9
70 7 9 8 9
Example 3 0.80 One 11 19 50 5 7 13 9
60 6 9 11 9
70 7 9 8 9
Example 4 0.80 One 11 19 50 5 7 13 9
60 6 9 11 9
70 7 9 8 9
Example 5 0.12 One 11 19 50 5 7 13 9
60 6 9 11 9
70 7 9 8 9
Example 6 0.12 3 17 25 50 5 7 13 9
60 6 9 11 9
70 7 9 8 9
Example 7 0.81 One 18 26 50 5 8 13 9
60 6 10 11 10
70 7 11 8 11
Example 8 0.79 One 11 19 50 5 8 13 8
60 6 9 11 10
70 7 9 9 9
Example 9 0.10 3 17 25 50 5 7 14 9
60 6 10 11 9
70 7 9 9 9
Comparative Example 1 Not measurable Not measurable 8 * 16 ** 50 5 8 13 10
60 6 11 13 11
70 7 13 8 13
Comparative Example 2 Not measurable
Comparative Example 3 Not measurable
Comparative Example 4 Not measurable
(주) 상기 표 2에서 최소현상시간(sec)은 수지 보호층을 포함하는 필름의 최소현상시간(Pmin)을 의미하며, 실제현상시간(sec)은 수지 보호층을 포함하는 필름의 실제현상시간(Pdel)을 의미한다. 다만, 예외적으로 *은 감광성 수지층만의 최소현상시간(Smin)을 의미하고, **은 감광성 수지층만의 실제현상시간(Sdel)을 의미한다. Note: In Table 2, the minimum development time (sec) means the minimum development time (P min ) of the film including the resin protective layer, and the actual development time (sec) is the actual development of the film including the resin protective layer. It means time (P del ). However, exceptionally * indicates the minimum development time (S min ) of the photosensitive resin layer only, ** ** means the actual development time (S del ) of the photosensitive resin layer only.
상기 측정 결과, 같은 단수를 구현하기 위해 필요한 노광량은 실시예 1 내지 9와 비교예 1은 차이가 거의 없었으며, 회로물성 측정 결과는 실시예 1 내지 9의 경우 해상도를 비롯하여 비교예 1에 비하여 더욱 우수한 결과를 보였고, 특히 비교예 1은 수지 보호층이 없기 때문에 헤이즈 측정이 불가하였고, 비교예 2 내지 4는 필름이 형성되지 않아 측정할 수 없었다. As a result of the measurement, the amount of exposure required to achieve the same number of stages was almost no difference between Examples 1 to 9 and Comparative Example 1, and the measurement results of the physical properties of the Examples 1 to 9 were higher than those of Comparative Example 1 including the resolution. Excellent results were observed, and in particular, Comparative Example 1 had no haze measurement because there was no resin protective layer, and Comparative Examples 2 to 4 could not be measured because no film was formed.
한편 본 발명의 수지 보호층을 포함한 드라이필름 포토레지스트의 경우 수지 보호층의 1㎛당 현상시간이 0.5 내지 3초 정도인 것을 알 수 있다.On the other hand, in the dry film photoresist including the resin protective layer of the present invention it can be seen that the development time per 1 μm of the resin protective layer is about 0.5 to 3 seconds.
또한 도 1 내지 도 3의 전자현미경 사진을 통한 표면 관찰 결과, 실시예 1 및 실시예 5에 의한 드라이필름 포토레지스트를 적용한 인쇄회로기판 표면 사진인 도 1 및 2의 경우, 비교예 1보다 측면 및 표면의 요철이 거의 없고 매우 우수한 패턴을 형성하였음을 알 수 있다. In addition, as a result of surface observation through the electron micrographs of FIGS. 1 to 3, in the case of FIGS. 1 and 2, which are photographs of the printed circuit board surface to which the dry film photoresist according to Examples 1 and 5 is applied, the side and It can be seen that there is little surface irregularities and a very good pattern is formed.
결론적으로 표 1 내지 3으로부터 본 발명의 드라이필름 포토레지스트를 적용한 경우, 점착력 면에서 지지체 필름과 감광성 수지층이 적층된 비교예 1과 마찬가지로 작업성을 저해하지 않는 범위에 있으면서 노광시 취급이 용이할 뿐만 아니라 해상도가 향상되는 것을 알 수 있다. In conclusion, in the case of applying the dry film photoresist of the present invention from Tables 1 to 3, it can be easily handled during exposure while in the range of not impairing workability as in Comparative Example 1 in which the support film and the photosensitive resin layer are laminated in terms of adhesive force. In addition, it can be seen that the resolution is improved.
본 발명의 단순한 변형 또는 변경은 모두 이 분야의 통상의 지식을 가진 자에 의하여 용이하게 실시될 수 있으며 이러한 변형이나 변경은 모두 본 발명의 영역에 포함되는 것으로 볼 수 있다.　All simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (15)

  1. 지지체 필름, 수지 보호층 및 감광성 수지층을 순차적으로 적층하여 포함하고, A support film, a resin protective layer, and a photosensitive resin layer are sequentially laminated and included,
    상기 수지 보호층은 수용성 고분자 및 알콕시알코올을 포함하는 드라이필름 포토레지스트. The resin protective layer is a dry film photoresist comprising a water-soluble polymer and an alkoxy alcohol.
  2. 제 1 항에 있어서, 상기 지지체 필름 상에 적층된 이형층을 추가로 포함하고, 상기 이형층은 실리콘 수지, 불소 수지 및 지방족 왁스 중에서 선택된 1 종 이상인 것을 포함하고, 상기 수지 보호층은 중량평균분자량이 5000 내지 300000인 폴리비닐알코올을 포함하는 드라이필름 포토레지스트. The method of claim 1, further comprising a release layer laminated on the support film, wherein the release layer comprises at least one selected from a silicone resin, a fluorine resin and an aliphatic wax, wherein the resin protective layer is a weight average molecular weight Dry film photoresist containing the polyvinyl alcohol of 5000 to 300000.
  3. 제1항에 있어서, 상기 수지 보호층은 알콕시알코올을 30000ppm 이하로 포함하는 것인 드라이필름 포토레지스트. The dry film photoresist of claim 1, wherein the resin protective layer contains 30000 ppm or less of alkoxy alcohol.
  4. 제1항에 있어서, 상기 알콕시알코올은 탄소수 1 내지 12의 알콕시기 및 탄소수 1 내지 12의 알코올기를 가지는 것인 드라이필름 포토레지스트. The dry film photoresist of claim 1, wherein the alkoxy alcohol has an alkoxy group having 1 to 12 carbon atoms and an alcohol group having 1 to 12 carbon atoms.
  5. 제4항에 있어서, 상기 알콕시알코올은 부톡시에탄올인 것인 드라이필름 포토레지스트.The dry film photoresist of claim 4, wherein the alkoxyalcohol is butoxyethanol.
  6. 제1항에 있어서, 상기 수용성 고분자를 물 및 알콕시알코올을 포함하는 용매에 녹인 후 이를 지지체 필름 상에 코팅하여 수지 보호층을 형성하는 것인 드라이필름 포토레지스트. The dry film photoresist of claim 1, wherein the water-soluble polymer is dissolved in a solvent containing water and an alkoxy alcohol, and then coated on the support film to form a resin protective layer.
  7. 제6항에 있어서, 상기 용매는 물 100 중량부에 대하여 알콕시알코올 1 내지 43중량부를 포함하는 것인 드라이필름 포토레지스트.The dry film photoresist of claim 6, wherein the solvent comprises 1 to 43 parts by weight of alkoxyalcohol based on 100 parts by weight of water.
  8. 제1항에 있어서, 상기 지지체 필름 및 수지 보호층 간의 점착력이 0.0005 내지 0.01 N/cm인 것인 드라이필름 포토레지스트. The dry film photoresist of claim 1, wherein the adhesive force between the support film and the resin protective layer is 0.0005 to 0.01 N / cm.
  9. 제1항에 있어서, 상기 수지 보호층은 수용성 고분자 100중량부에 대하여 폴리실리콘을 0.01 내지 3중량부의 함량으로 포함하는 것인 드라이필름 포토레지스트. The dry film photoresist of claim 1, wherein the resin protective layer contains polysilicon in an amount of 0.01 to 3 parts by weight based on 100 parts by weight of the water-soluble polymer.
  10. 제9항에 있어서, 상기 폴리실리콘은 물, 알코올류 및 이들의 혼합물 중에서 선택된 어느 하나의 용매 100g에 6시간 동안 80℃의 조건 하에서 폴리실리콘 0.1g 용해시 입도가 1㎛ 이하인 것인 드라이필름 포토레지스트.The dry film photo of claim 9, wherein the polysilicon has a particle size of 1 μm or less when dissolved in 0.1 g of polysilicon under a condition of 80 ° C. for 6 hours in 100 g of any one selected from water, alcohols, and mixtures thereof. Resist.
  11. 제1항 또는 제2항에 있어서, 상기 수지 보호층은 헤이즈가 3.0% 이하인 것인 드라이필름 포토레지스트. The dry film photoresist of claim 1, wherein the resin protective layer has a haze of 3.0% or less.
  12. 제1항 또는 제2항에 있어서, 상기 수지 보호층은 1㎛당 현상시간이 10초 이하인 것인 드라이필름 포토레지스트. The dry film photoresist of claim 1, wherein the resin protective layer has a developing time of 1 μm or less.
  13. 제2항에 있어서, 상기 이형층 및 수지 보호층 간의 점착력이 0.0005 내지 0.01 N/cm인 것인 드라이필름 포토레지스트. The dry film photoresist of claim 2, wherein the adhesive force between the release layer and the resin protective layer is 0.0005 to 0.01 N / cm.
  14. 제1항 또는 제2항에 있어서, 상기 수지 보호층은 두께가 10㎛ 이하인 것인 드라이필름 포토레지스트. The dry film photoresist of claim 1, wherein the resin protective layer has a thickness of 10 μm or less.
  15. 제2항에 있어서, 상기 폴리비닐알코올은 검화도가 75 내지 97%인 것인 드라이필름 포토레지스트. The dry film photoresist of claim 2, wherein the polyvinyl alcohol has a degree of saponification of 75% to 97%.
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JP2013505484A (en) 2013-02-14

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