WO2011040749A2 - Photoréserve à film sec - Google Patents

Photoréserve à film sec 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
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English (en)
Korean (ko)
Other versions
WO2011040749A3 (fr
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/ko
Priority claimed from KR1020090131963A external-priority patent/KR101262448B1/ko
Application filed by 코오롱인더스트리 주식회사 filed Critical 코오롱인더스트리 주식회사
Priority to CN201080043646.8A priority Critical patent/CN102549499B/zh
Priority to JP2012530789A priority patent/JP5356603B2/ja
Publication of WO2011040749A2 publication Critical patent/WO2011040749A2/fr
Publication of WO2011040749A3 publication Critical patent/WO2011040749A3/fr

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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.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
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  • Structural Engineering (AREA)
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  • Manufacturing Of Printed Circuit Boards (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention porte sur une photoréserve à film sec, et, plus particulièrement, sur une photoréserve à film sec qui peut améliorer une définition par réalisation d'un processus d'exposition dans un état retiré d'un film de support afin d'éviter une influence défavorable d'un effet d'exposition dû au film de support. De plus, la définition élevée peut être obtenue par prévention de la diminution de la transparence ou de la réduction de la vitesse de développement tandis que le processus d'exposition est effectué en présence d'une couche de protection en résine. En particulier, la couche de protection en résine selon la présente invention peut réduire le coût de fabrication et le voile par réduction de la teneur en agent mouillant tel que du polysilicium, peut empêcher la diminution du voile par suppression de la détérioration de la couche de protection de résine, et peut obtenir la définition élevée par prévention de la réduction de la durée de développement.
PCT/KR2010/006612 2009-09-30 2010-09-29 Photoréserve à film sec WO2011040749A2 (fr)

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WO2024075158A1 (fr) * 2022-10-03 2024-04-11 株式会社レゾナック Élément photosensible, procédé de formation de motif de résine photosensible et procédé de fabrication de carte de circuit imprimé

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US20040234889A1 (en) * 2001-12-28 2004-11-25 Shunsuke Okuyama Laminated film
US6664025B2 (en) * 2002-02-12 2003-12-16 Kodak Polychrome Graphics Llc Visible radiation sensitive composition
US6849372B2 (en) * 2002-07-30 2005-02-01 Kodak Polychrome Graphics Method of manufacturing imaging compositions
WO2006009076A1 (fr) * 2004-07-20 2006-01-26 Hitachi Chemical Company, Ltd. Élément photosensible, méthode de conception de modèle résistant et procédé de production de tableau de cadrage imprimé
KR100860901B1 (ko) * 2004-08-11 2008-09-29 히다치 가세고교 가부시끼가이샤 감광성 수지 조성물 및 이것을 이용한 감광성 필름
CN101111803B (zh) * 2005-02-02 2011-07-20 可隆株式会社 正性干膜光致抗蚀剂以及用于制备该光致抗蚀剂的组合物
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CN102549499A (zh) 2012-07-04

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