WO2009054705A2 - Matériau de transfert de type film - Google Patents

Matériau de transfert de type film Download PDF

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Publication number
WO2009054705A2
WO2009054705A2 PCT/KR2008/006318 KR2008006318W WO2009054705A2 WO 2009054705 A2 WO2009054705 A2 WO 2009054705A2 KR 2008006318 W KR2008006318 W KR 2008006318W WO 2009054705 A2 WO2009054705 A2 WO 2009054705A2
Authority
WO
WIPO (PCT)
Prior art keywords
protective layer
film
resin protective
transfer material
adhesion
Prior art date
Application number
PCT/KR2008/006318
Other languages
English (en)
Other versions
WO2009054705A3 (fr
Inventor
Hee Wan Moon
Seung Je Jho
Byeong Il Lee
Original Assignee
Kolon Industries, Inc.
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.)
Filing date
Publication date
Application filed by Kolon Industries, Inc. filed Critical Kolon Industries, Inc.
Priority to JP2010530935A priority Critical patent/JP5483734B2/ja
Priority to CN2008801126086A priority patent/CN101836162B/zh
Priority claimed from KR1020080104904A external-priority patent/KR101115162B1/ko
Publication of WO2009054705A2 publication Critical patent/WO2009054705A2/fr
Publication of WO2009054705A3 publication Critical patent/WO2009054705A3/fr
Priority to HK11100873.9A priority patent/HK1146751A1/xx

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Classifications

    • 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
    • G03F7/16—Coating processes; Apparatus therefor
    • G03F7/161—Coating processes; Apparatus therefor using a previously coated surface, e.g. by stamping or by transfer lamination
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • G03F7/2014—Contact or film exposure of light sensitive plates such as lithographic plates or circuit boards, e.g. in a vacuum frame
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/0073—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces
    • H05K3/0082—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces characterised by the exposure method of radiation-sensitive masks
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/05—Patterning and lithography; Masks; Details of resist
    • H05K2203/0548—Masks
    • H05K2203/056—Using an artwork, i.e. a photomask for exposing photosensitive layers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
    • H05K3/061—Etching masks
    • H05K3/064—Photoresists

Definitions

  • the present invention relates to a film type photosensitive transfer material.
  • a film type photosensitive transfer material is provided in the form of a dry film (hereinafter, referred to as "dry film photoresist”) .
  • the dry film photoresist is used for a printed wiring board, a printed circuit board (PCB) , IC packaging, a metal relief sculpture and so on, and generally includes a base film, a photosensitive resin layer and a cover film.
  • the base film plays a role in supporting the photosensitive resin layer and enabling the photosensitive resin layer which is adhesive to be easily handled in an exposure process.
  • the photosensitive resin layer is prepared to be adapted for end use from a photopolymerizable monomer, a photoinitiator, and a binder polymer.
  • the cover film is formed on the surface of the photosensitive resin layer opposite the surface where the base film is formed, and is thus responsible for preventing damage to the photosensitive resin layer.
  • An example of a process of forming a pattern using such a dry film photoresist includes the fabrication of a PCB composed of removing a cover film from a dry film photoresist, laminating the dry film photoresist on a copper clad laminate (CCL) , placing a mask having a desired pattern on the dry film photoresist, performing an exposure process using UV light, and then performing a development process for washing out an uncured portion using an appropriate solvent.
  • the exposure process is conducted in a state in which the base film 40 is attached to the photosensitive resin layer 20. In this case, because the mask 60 is spaced apart from the photosensitive resin layer 20 by a thickness of the base film 40, the resolution may be lowered.
  • the exposure process may be carried out after the base film is removed. If so, however, the mask may adhere to the photosensitive resin layer which is adhesive, because of the absence of the base film, undesirably damaging the photosensitive resin layer, thereby resulting in lowered resolution. Hence, it is actually difficult to conduct the exposure process after removal of the base film, and thus a problem in which the resolution is lowered still remains .
  • the present invention provides a film type photosensitive transfer material, which enables an exposure process to be performed even in the absence of a base film.
  • the present invention provides a film type photosensitive transfer material, in which an interval between a mask and a photosensitive resin layer is minimized upon an exposure process, thus increasing the resolution, and also provides a display substrate having a pattern formed using the same.
  • a film type photosensitive transfer material includes a base film, a resin protective layer, a photosensitive resin layer and a cover film, wherein the resin protective layer has adhesion of 0.005 kgf/cirf or less, in which the adhesion is defined as a force per unit area required to separate an additional polyethyleneterephthalate (PET) film, which has been laminated on the resin protective layer exposed due to removal of the base film, from a position of 5 cm to a position of 8 cm distant from a release starting point of the PET film.
  • PET polyethyleneterephthalate
  • the resin protective layer may be an alkali developable polymer layer.
  • the resin protective layer may have solubility of 5 g or less in methylethylketone at 25 ° C, in which the solubility is defined as a decrement in weight of the resin protective layer as a result of an operation of adding 50 g of the resin protective layer to 100 g of methylethylketone, performing stirring at 25 ° C for 1 hour and filtration using filter paper, and measuring the weight of the resin protective layer remaining on the filter paper.
  • the resin protective layer may be formed from a coating solution including a water-soluble polymer having a weight average molecular weight of 5,000-300,000.
  • adhesion between the cover film and the photosensitive resin layer may be smaller than adhesion between the base film and the resin protective layer.
  • the resin protective layer may have a thickness of 0.001-10 jMn.
  • the resin protective layer may have an adhesion change of 5000% or less as represented by Equation 1 below. Equation 1
  • first adhesion is defined as a force per unit area required to separate an additional polyethyleneterephthalate film, which has been laminated on the resin protective layer shortly after removal of the base film, from a position of 5 cm to a position of 8 cm distant from a release starting point of the polyethyleneterephthalate film
  • second adhesion is defined as a force per unit area required to separate an additional polyethyleneterephthalate film, which has been laminated on the resin protective layer, from a position of 5 cm to a position of 8 cm distant from a release starting point of the polyethyleneterephthalate film
  • the resin protective layer may be a polyvinylalcohol-based resin layer.
  • the resin protective layer may include at least one additive selected from among a wetting agent, a leveling agent, an antifoaming agent, a binder, and an adhesive.
  • the cover film may be a polyester film with or without a release layer.
  • the base film may be a polyester film with or without a release layer.
  • a display substrate which has a pattern formed using the aforementioned film type photosensitive transfer material, is provided.
  • the present invention can provide a film type photosensitive transfer material and a display substrate.
  • an exposure process can be performed after removal of a base film, and thus an interval between a mask and a photosensitive resin layer can be narrowed upon the exposure process, thereby further improving the resolution of a pattern.
  • the film type photosensitive transfer material according to the present invention allows the base film to be removed before the exposure process, and can be processed in sheets or can be applied to a roll-to-roll process without damage to the photosensitive resin layer.
  • the process of the present invention is simpler compared to a conventional process including performing an exposure process, eliminating impurities and removing a base film, and also, the manufacturing cost of the display substrate can be reduced.
  • FIG. 1 is a cross-sectional view showing the layer structure of a film type photosensitive transfer material according to a preferred embodiment of the present invention
  • FIG. 2 is a cross-sectional view showing a display substrate including the film type photosensitive transfer material according to the present invention, upon an exposure process;
  • FIG. 3 is a cross-sectional view showing a display substrate including a conventional film type photosensitive transfer material having a three-layer structure, upon an exposure process;
  • FIG. 4 is a 80Ox magnified electron microscope image showing the surface of a PCB after a development process, manufactured in the example of the present invention
  • FIG. 5 is a 60Ox magnified electron microscope image showing the surface of a PCB after a development process, manufactured in the comparative example
  • FIGS. 6 to 8 are (150Ox, 200Ox, 250Ox magnified) electron microscope images showing the surfaces of PCBs after a development process, manufactured in Examples 5 to 7, respectively.
  • FCCL flexible copper clad laminate
  • FIG. 1 illustrates a film type photosensitive transfer material according to an embodiment of the present invention.
  • the film type photosensitive transfer material according to the present invention has a structure including a cover film 10, a photosensitive resin layer 20, a resin protective layer 30, and a base film 40.
  • each of the cover film 10 and/or the base film 40 may have a release layer on at least one surface thereof.
  • FIG. 2 illustrates the cross-section of the layer structure of a display substrate including the film type photosensitive transfer material according to the present invention, upon an exposure process.
  • the cover film 10 is removed from the film type photosensitive transfer material, the film type photosensitive transfer material is laminated on a FCCL 50 such that the photosensitive resin layer of the transfer material and the FCCL face each other, the base film 40 is removed, and then a mask is placed on the resin protective layer, after which an exposure process and a development process are performed.
  • a display substrate for example, a printed wiring board, a PCB and the like
  • the cover film 10 is removed from the film type photosensitive transfer material
  • the film type photosensitive transfer material is laminated on a FCCL 50 such that the photosensitive resin layer of the transfer material and the FCCL face each other
  • the base film 40 is removed, and then a mask is placed on the resin protective layer, after which an exposure process and a development process are performed.
  • the base film of the present invention functions as a support of the resin protective layer and the photosensitive resin layer and thus should have adequate mechanical properties.
  • material for the base film include polyester including polyethyleneterephthalate, polyethylenenaphthalate and so on, polyethylene, polypropylene, polyimide, polyamide, cellulose triacetate, cellulose diacetate, alkyl poly (meth) acrylate, (meth) acrylic acid ester copolymer, copolymer of polyvinyl chloride and vinyl acetate, polytetrafluoroethylene, and polytrifluoroethylene. Particularly useful is polyethyleneterephthalate.
  • the thickness of the base film is set to 10-100 ⁇ m and preferably 15-30 ⁇ m, but is not limited thereto.
  • the base film may have a release layer for controlling releasability.
  • a release layer for controlling releasability.
  • particular limitations are not imposed on the forming process and composition of the release layer, as long as the release layer satisfies surface properties able to prevent damage to the resin protective layer while exhibiting adhesion between the base film and the resin protective layer greater than adhesion between the cover film and the photosensitive resin layer.
  • the resin protective layer is disposed between the base film and the photosensitive resin layer.
  • the film type photosensitive transfer material according to the embodiment of the present invention including such a resin protective layer may be subjected to an exposure process after the base film has been removed and a mask has been then placed on the resin protective layer.
  • the resin protective layer should be easily detached from the base film and should not adhere with the mask.
  • the resin protective layer is required to have low adhesion to the extent that defects do not occur even when resin protective layers are stacked or the FCCL and the resin protective layer come into contact with each other in a sheet processing process or a roll-to-roll process after the exposure process.
  • the mask include polyethyleneterephthalate (PET) , glass, etc. Accordingly, a PET film is laminated on the resin protective layer of the present invention exposed due to removal of the base film and then must also be easily separated therefrom.
  • the resin protective layer of the present invention may have adhesion of 0.005 kgf/cuf or less, the adhesion being defined as the force per unit area required to separate an additional PET film, which has been laminated on the resin protective layer exposed due to the removal of the base film, from a position of 5 cm to a position of 8 cm distant from the release starting point of the PET film.
  • the adhesion is determined in a manner such that a cover film is removed from a film type photosensitive transfer material sample having a width of 3 cm and a length of 20 cm, the transfer material sample is laminated on a FCCL at a rate of 2 m/min under conditions of 110 ° C and 4 kgf/cilf, and then a base film is removed, after which a PET film having a width of 4 cm, a length of 25 cm and a thickness of 19 (M is laminated on the layer exposed due to the removal of the base film at a rate of 2 m/min under conditions of 110 °C and 4 kgf/cnf and then the force per unit area required to separate the PET film from a position of 5 cm to a position of 8 cm distant from the release starting point of the PET film is measured using a universal testing machine (UTM) .
  • UPM universal testing machine
  • the resin protective layer has adhesion greater than 0.005 kgf/cin 2
  • the mask which is applied on the resin protective layer is not easy to remove again therefrom and thus the surface of the resin protective layer may be damaged, making it difficult to obtain favorable effects by the exposure process after removal of the base film.
  • the resin protective layer should block introduction of oxygen which impedes the polymerization of the photosensitive resin layer in the exposure process, and further, should be eliminated in the development process after the exposure process.
  • the resin protective layer may be an alkali developable polymer layer.
  • the term "alkali developable polymer" indicates that a polymer is developed by a diluted alkali solution, for example, Na2CO3, NaOH or KOH.
  • the resin protective layer may be prepared from a composition including a water-soluble polymer selected from among water-soluble salts of polyvinylether maleic anhydride, water-soluble salts of cellulose ether, water-soluble salts of carboxyalkyl cellulose, water-soluble salts of carboxyalkyl starch, polyvinylalcohol, polyvinylpyrrolidone, various types of polyacrylamide, water-soluble salts of polyamide, water-soluble salts of polyacrylic acid, polyethyleneglycol, polypropyleneglycol, gelatin, poly (ethyleneoxide) , and starch.
  • a water-soluble polymer selected from among water-soluble salts of polyvinylether maleic anhydride, water-soluble salts of cellulose ether, water-soluble salts of carboxyalkyl cellulose, water-soluble salts of carboxyalkyl starch, polyvinylalcohol, polyvinylpyrrolidone, various types of polyacrylamide, water-soluble salts of polyamide,
  • a weight average molecular weight of the polymer of the composition may range from 5,000 to 300,000. If the weight average molecular weight is less than 5000, it is difficult to apply the composition in the form of a film and a function of protecting the photosensitive resin layer becomes deteriorated due to low strength. Conversely, if the weight average molecular weight exceeds 300,000, a development time is increased and there is worry about damage to the resin protective layer upon removal of the base film after the lamination on the FCCL.
  • the resin protective layer may have solubility of 5 g or less in methylethylketone (MEK) at 25 ° C in order to prevent the component diffusion between the photosensitive resin layer and the resin protective layer during distribution of products and to prolong the shelf life of products.
  • MEK methylethylketone
  • the solubility in MEK is defined as a decrement in the weight of the resin protective layer resulting from adding 50 g of a resin protective layer to 100 g of MEK, performing stirring at 25 ° C for 1 hour and then filtration using filter paper, and measuring the weight of the resin protective layer remaining on the filter paper.
  • the exposure process may be performed after removal of the base film in a post process.
  • the properties of the resin protective layer exposed to the external environment may change due to moisture absorption.
  • the resin protective layer may have an adhesion change of 5000% or less as represented by Equation 1 below. Equation 1
  • first adhesion is defined as the force per unit area required to separate an additional PET film, which has been laminated on the resin protective layer shortly after removal of the base film, from a position of 5 cm to a position of 8 cm distant from the release starting point of the PET film
  • second adhesion is defined as the force per unit area required to separate an additional PET film, which has been laminated on the resin protective layer, from a position of 5 cm to a position of 8 cm distant from the release starting point of the PET film
  • the resin protective layer may be a polyvinylalcohol-based resin layer.
  • the polyvinylalcohol- based resin layer will be understood as a resin layer including at least 10 wt% of polyvinylalcohol resin.
  • the resin protective layer is a polyvinylalcohol-based resin layer
  • applicability may vary depending on the type of base film.
  • a wetting agent may be further included.
  • an additive for controlling releasability for example, a wetting agent, a leveling agent, an antifoaming agent, a binder, and an adhesive agent, may be used.
  • the additive is not particularly limited, and any additive may be used as long as the adhesion between the cover film and the photosensitive resin layer may be adjusted to be smaller than the adhesion between the base film and the resin protective layer.
  • the process of forming the resin protective layer is not particularly limited, and includes dissolving the composition for forming the resin protective layer in an organic solvent or water and preferably water, thus preparing a composition solution, applying the composition solution on the base film, and then drying it.
  • the exposure process is performed in a state in which the resin protective layer is formed, and thus, in order to increase the resolution, it is preferred that the resin protective layer be thinner.
  • the thickness of the resin protective layer may be set to 0.001-10 ⁇ m.
  • a composition for the photosensitive resin layer includes a binder polymer, a photopolymerizable monomer, a photoinitiator, and other additives, and may vary depending on the properties and nature of PCBs.
  • the process of forming the photosensitive resin layer which is disposed to be in contact with the above resin protective layer is not particularly limited and includes applying the photosensitive resin layer on the cover film and then attaching it to the resin protective layer formed on the base film.
  • the thickness of the photosensitive resin layer may be set to 10-100 ⁇ m depending on the type of PCBs.
  • the cover film should have releasability adequate for easily separating it upon application of the film type transfer material to a post process and for preventing the separation thereof upon storage and distribution.
  • the photosensitive resin layer is applied on the cover film and is then laminated on the resin protective layer formed on the base film, thus manufacturing a film type photosensitive transfer material.
  • the cover film may be a polyester film. Taking into consideration releasability, particularly useful is a polyester film having a release layer.
  • An example of the process of forming the release layer includes but is not limited to coating or printing of silicone.
  • the release layer is not particularly limited in terms of the forming process and composition, as long as the adhesion between the cover film and the photosensitive resin layer is smaller than that between the base film and the resin protective layer and the surface properties of the photosensitive resin layer are not degraded.
  • a polyolefin film 15-25 ⁇ m thick may be used as the cover film.
  • Methacrylic acid, acrylic acid and methyl methacrylate (MAA) were polymerized at a weight ratio of 20:10:70 under conditions of a MEK solvent, a 1% AIBN polymerization initiator, a reaction temperature of 80 ° C, a reaction time of 4 hours and a 3% AIBN post initiator, thus preparing an acrylic acid polymer (weight average MW: 70,000, solid content: 50%).
  • a film type photosensitive transfer material having a thickness of 57 ⁇ m was manufactured in the same manner as in Example 1, with the exception that polyethyleneglycol (weight average MW: 20,000, available from Sigma-Aldrich) diluted to 200 cps with secondary distilled water was used as the composition for a resin protective layer.
  • polyethyleneglycol weight average MW: 20,000, available from Sigma-Aldrich
  • a film type photosensitive transfer material having a thickness of 55.5 ⁇ m was manufactured in the same manner as in Example 1, with the exception that the composition for a resin protective layer was applied to a thickness of 0.5 jMii.
  • Example 4 A film type photosensitive transfer material having a thickness of 56 ⁇ m was manufactured in the same manner as in Example 1, with the exception that a PET film having a silicone release layer (thickness: 19 ⁇ m, CY201-19 ⁇ m, available from Kolon) was used as the cover film, in lieu of OPP.
  • a photosensitive resin composition was prepared with components and amounts used for UH-9200 series (available from Kolon) , applied on a PET film 19 ⁇ m thick (FDFR, available from Kolon) using a coating bar, and then dried in a convection oven at 80 ° C for 6 min, thus forming a photosensitive resin layer 15 ⁇ m thick. Then, the dried film was laminated on a polyester film (23 ⁇ m) at 25 ° C under pressure of 4 kgf/cirf, thus manufacturing a film type photosensitive transfer material having a thickness of 57 ⁇ m.
  • the force per unit area required to separate the cover film of the film type photosensitive transfer material sample having a width of 3 cm and a length of 20 cm from a position of 5 cm to a position of 8 cm distant from the release starting point of the cover film was measured using a UTM (4303 series, available from Instron) .
  • the cover film was removed from the film type photosensitive transfer material sample having a width of 3 cm and a length of 20 cm, after which the transfer material sample was laminated on a CCL at a rate of 2 m/min at 110 " C under pressure of 4 kgf/ ⁇ if. Thereafter, the force per unit area required to separate the base film from a position of 5 cm to a position of 8 cm distant from the release starting point of the base film was measured using a UTM (4303 series, available from Instron) .
  • the cover film was removed from the film type photosensitive transfer material sample having a width of 3 cm and a length of 20 cm, the transfer material sample was laminated on a CCL at a rate of 2 m/min under conditions of 110 ° C and 4 kgf/cnf, and then the base film was removed.
  • a PET film (FDFR, available from Kolon) having a width of 4 cm, a length of 25 cm and a thickness of 19 ⁇ m was laminated on the layer exposed due to removal of the base film at a rate of 2 m/min under conditions of 110 ° C and 4 kgf/cnf, after which the force per unit area required to separate the PET film from a position of 5 cm to a position of 8 cm distant from the release starting point of the PET film was measured using a UTM (4303 series, available from Instron) .
  • the PET film was laminated under the same conditions as those for attaching a mask in a typical exposure process.
  • the adhesion thus measured corresponds to the adhesion between the resin protective layer and the PET film in the examples and Comparative Example 2 and to the adhesion between the photosensitive resin layer and the PET film in Comparative Example 1.
  • the cover film was removed from the film type photosensitive transfer material sample having a width of 3 cm and a length of 20, the transfer material sample was laminated on a CCL at a rate of 2 m/min under conditions of
  • a PET film (FDFR, available from Kolon) having a width of 4 cm, a length of 25 cm and a thickness of 19 ⁇ m was laminated on the layer exposed due to removal of the base film at a rate of 2 m/min under conditions of 110 ° C and 4 kgf/cirf, and then the force per unit area required to separate the PET film from a position of 5 cm to a position of 8 cm distant from the release starting point of the PET film was measured using a UTM (4303 series, available from Instron) . The adhesion thus measured was defined as the first adhesion.
  • the base film was removed from the transfer material sample, the transfer material sample was allowed to stand for 240 hours under conditions of temperature of 25 ° C and humidity of 50%, an additional PET film was laminated on the resin protective layer of the transfer material sample through the process as above, and then the force per unit area required to separate the PET film from a position of 5 cm to a position of 8 cm distant from the release starting point of the PET film was measured using a UTM (4303 series, available from Instron) . The adhesion thus measured was defined as the second adhesion.
  • the adhesion between the photosensitive resin layer and the cover film and the adhesion between the resin protective layer and the base film could be seen to fall within a range of not degrading workability.
  • the adhesion could be seen to be much lower than in the comparative example.
  • the adhesion between the resin protective layer of the examples and the mask material typically used under exposure conditions is very low, and therefore the transfer material of the present invention can be easily handled in the exposure process.
  • the film type photosensitive transfer material of the above examples and comparative example was applied on a PCB through the following procedures, and the properties thereof were measured.
  • a surface of a CCL was pre-treated with a brush, thus forming a new copper surface having an appropriate roughness, after which the CCL was acid-treated with 5% sulfuric acid solution, washed with water, dried, and then loaded into a laminator.
  • used as the laminator was Hakuto Mach 61Oi.
  • the film type photosensitive transfer material of the examples and comparative example was laminated on the CCL at a rate of 2 m/min at 110 ° C under pressure of 4kgf/citf. In this case, pre-heating was not conducted. Thereafter, an exposure process was conducted using a UV light source (Perkin Elmer OB-7120, 5 Kw collimated light) .
  • the PCB was passed through a developing machine, thus developing it.
  • the base film was peeled off before the exposure process.
  • the base film was peeled off after the exposure process before the development process.
  • a Stouffer 21-step tablet was placed on the resin protective layer in Examples 1 to 4 and on the base film in Comparative Example 1, after which the exposure dose for obtaining 5-step, 6-step and 7-step sensitivity was measured using a light irradiance meter (UV- 351, available from ORC) .
  • UV- 351, available from ORC a light irradiance meter
  • the period of time required to completely wash out the lamination portion of the PCB, which had been laminated on the CCL, by a developer through a developing machine was determined to be a minimum development time.
  • the actual development time was estimated by doubling the minimum development time.
  • the actual development time was calculated by adding the time required to develop the resin protective layer to the minimum development time.
  • the resolution, the fine line adhesion, the 1/1 (line/space) resolution were measured, thus evaluating the circuit properties.
  • the resolution was determined by measuring the minimum spacewidth of the circuit pattern resulting from developing the unexposed portion of the substrate. As the spacewidth thus measured was smaller, the resolution was evaluated to be superior.
  • the mask used for the measurement of the resolution was formed with a pattern at intervals of 0.5 ⁇ m to 4-20 ⁇ m. A desired resolution was determined using a mask having a pattern at intervals of 400 ⁇ m. Further, the fine line adhesion was determined by measuring the minimum spacewidth of the linear circuit pattern without corrosion resulting from developing the exposed portion of the substrate.
  • the mask used for the measurement of the fine line adhesion was formed with a pattern at intervals of 0.5 ⁇ m to 4-20 ⁇ m.
  • a desired fine line adhesion was determined using a mask having a pattern at intervals of 400 ⁇ m.
  • the 1/1 resolution was determined by measuring the minimum spacewidth cleanly developed under conditions in which the intervals between two adjacent circuit lines were set to 1:1. (7) Surface Analysis
  • the film type photosensitive transfer material including the resin protective layer according to the present invention the development time of the resin protective layer was about 0.5-3 sec per 1 ⁇ m thickness of the resin protective layer.
  • the roughness of the side and surface was seen to be smaller despite higher magnification compared to FIG. 5 using the transfer material of Comparative Example 1.
  • a photosensitive resin composition was prepared with components and amounts used for UH-9200 series (available from Kolon) . Specifically, a photoinitiator was dissolved in MEK and methyl alcohol solvents, mixed with a photopolymerizable oligomer and a binder polymer and then stirred for 1 hour using a mechanical stirrer, thus preparing a photosensitive resin composition.
  • the photosensitive resin composition was applied on a cover film 19 ⁇ m thick (PET film having silicone release layer, CY201-19 ⁇ m, available from Kolon) using a coating bar, and then dried in a convection oven at 80 ° C for 6 min, thus forming a photosensitive resin layer 15 ⁇ m thick.
  • a cover film 19 ⁇ m thick PET film having silicone release layer, CY201-19 ⁇ m, available from Kolon
  • the photosensitive resin layer of (d) was laminated on the resin protective layer of (b) to be in contact with each other at 50 ° C under pressure of 4 kgf/cin 2 , thus completing a film type photosensitive transfer material having a thickness of 55 ⁇ m as illustrated in FIG. 1.
  • a photoinitiator was dissolved in MEK and methyl alcohol solvents, mixed with a photopolymerizable oligomer and a binder polymer and then stirred for 1 hour using a mechanical stirrer, thus preparing a photosensitive resin composition.
  • the photosensitive resin composition was applied on a cover film 19 ⁇ m thick (PET film having silicone release layer, CY201-19 jM, available from Kolon) using a coating bar, and then dried in a convection oven at 80 ° C for 6 min, thus forming a photosensitive resin layer 15 [M thick.
  • the photosensitive resin layer of (d) was laminated on the resin protective layer of (b) to be in contact with each other at 50 ° C under pressure of 4 kgf/cin 2 , thus completing a film type photosensitive transfer material having a thickness of 55 ⁇ m as illustrated in FIG. 1.
  • Example 7 (a) 20 g of PVA205 (available from Kuraray, Japan) was added to 100 g of distilled water and then stirred at 80 ° C for 6 hours to completely dissolve, thus obtaining a composition for a resin protective layer, which was then applied on a base film 19 ⁇ m thick (PET film having silicone release layer, CY201-19 ⁇ m, available from Kolon) using a coating bar and dried in a convection oven at 80 " C for 10 min, thus forming a resin protective layer 10 ⁇ m thick.
  • PVA205 available from Kuraray, Japan
  • a photoinitiator was dissolved in MEK and methyl alcohol solvents, mixed with a photopolymerizable oligomer and a binder polymer, and then stirred for 1 hour using a mechanical stirrer, thus preparing a photosensitive resin composition.
  • the photosensitive resin composition was applied on a cover film 19 ⁇ m thick (PET film having silicone release layer, CY201-19 ⁇ m, available from Kolon) using a coating bar, and then dried in a convection oven at 80°C for 6 min, thus forming a photosensitive resin layer 15 ⁇ m thick.
  • a cover film 19 ⁇ m thick PET film having silicone release layer, CY201-19 ⁇ m, available from Kolon
  • the photosensitive resin layer of (d) was laminated on the resin protective layer of (b) to be in contact with each other at 50 ° C under pressure of 4 kgf/cuf, thus completing a film type photosensitive transfer material having a thickness of 63 ⁇ m as illustrated in FIG. 1.
  • the force per unit area required to separate the cover film of the film type photosensitive transfer material sample having a width of 3 cm and a length of 20 cm from a position of 5 cm to a position of 8 cm distant from the release starting point of the cover film was measured using a UTM (4303 series, available from Instron) .
  • the cover film was removed from the film type photosensitive transfer material sample having a width of 3 cm and a length of 20 cm, after which the transfer material sample was laminated on a CCL at a rate of 2 m/min at 110 " C under pressure of 4 kgf/ ⁇ if. Thereafter, the force per unit area required to separate the base film from a position of 5 cm to a position of 8 cm distant from the release starting point of the base film was measured using a UTM (4303 series, available from Instron) .
  • the cover film was removed from the film type photosensitive transfer material sample having a width of 3 cm and a length of 20 cm, the transfer material sample was laminated on a CCL at a rate of 2 m/min under conditions of
  • a PET film (FDFR, available from Kolon) having a width of 4 cm, a length of 25 cm and a thickness of 19 ⁇ m was laminated on the layer exposed due to removal of the base film at a rate of 2 m/min under conditions of 110 ° C and 4 kgf/cuf, after which the force per unit area required to separate the PET film from a position of 5 cm to a position of 8 cm distant from the release starting point of the PET film was measured using a UTM (4303 series, available from Instron) .
  • the PET film was laminated under the same conditions as those for attaching a mask in a typical exposure process.
  • the adhesion thus measured corresponds to the adhesion between the resin protective layer and the PET film.
  • the cover film was removed from the film type photosensitive transfer material sample having a width of 3 cm and a length of 20 cm, the transfer material sample was laminated on a CCL at a rate of 2 m/min under conditions of
  • a PET film (FDFR, available from Kolon) having a width of 4 cm, a length of 25 cm and a thickness of 19 [M was laminated on the layer exposed due to removal of the base film at a rate of 2 m/min under conditions of 110 ° C and 4 kgf/ ⁇ if, after which the force per unit area required to separate the PET film from a position of 5 cm to a position of 8 cm distant from the release starting point of the PET film was measured using a UTM (4303 series, available from Instron) . The adhesion thus measured was defined as the first adhesion.
  • the base film was removed from the transfer material sample, the transfer material sample was allowed to stand for 240 hours under conditions of temperature of 25 ° C and humidity of 50%, an additional PET film was laminated on the resin protective layer of the transfer material sample through the process as above, and then the force per unit area required to separate the PET film from a position of 5 cm to a position of 8 cm distant from the release starting point of the PET film was measured using a UTM (4303 series, available from Instron) . The adhesion thus measured was defined as the second adhesion.
  • Solubility of Resin protective layer in MEK was determined by adding 50 g of the resin protective layer to 100 g of MEK, performing stirring at 25 ° C for 1 hour and then filtration using filter paper, and measuring the weight of the resin protective layer remaining on the filter paper. The solubility was defined as a decrement in the weight of the resin protective layer.
  • the adhesion between the photosensitive resin layer and the cover film and the adhesion between the resin protective layer and the base film could be seen to fall within a range of not degrading workability.
  • the resin protective layer could be seen to have low adhesion with the PET film used as the mask. Thereby, the adhesion between the resin protective layer of the examples and the mask material typically used under exposure conditions is very low and thus the transfer material according to the present invention can be easily handled upon the exposure process.
  • the resin protective layer had low solubility of 5 g or less in MEK.
  • particularly useful as the resin protective layer is a polyvinylalcohol resin layer.
  • the resin protective layer had a low adhesion change of 5000% or less. Even after a lapse of a predetermined period of time following removal of the base film in a post process using the film type photosensitive transfer material, problems in which the resin protective layer adheres with the mask attributable to moisture absorption can be prevented.
  • a surface of a CCL was pre-treated with a brush, thus forming a new copper surface having an appropriate roughness, after which the CCL was acid-treated with 5% sulfuric acid solution, washed with water, dried, and then loaded into a laminator.
  • the laminator was Hakuto Mach 61Oi.
  • the film type photosensitive transfer material of the examples and comparative example was laminated on the CCL at a rate of 2 m/min at 110 ° C under pressure of 4 kgf/cnf. In this case, pre-heating was not conducted. Thereafter, an exposure process was conducted using a UV light source (Perkin Elmer OB-7120, 5 Kw collimated light) . After completion of the exposure process, the PCB was passed through a developing machine, thus developing it.
  • a UV light source Perkin Elmer OB-7120, 5 Kw collimated light
  • the base film was peeled off before the exposure process.
  • the period of time required to completely wash out the lamination portion of the PCB, which had been laminated on the CCL, by a developer through a developing machine was determined to be a minimum development time.
  • the actual development time was estimated by doubling the minimum development time.
  • the actual development time was calculated by adding the time required to develop the resin protective layer to the minimum development time.
  • the resolution was determined by measuring the minimum spacewidth of the circuit pattern resulting from developing the unexposed portion of the substrate. As the spacewidth thus measured was smaller, the resolution was evaluated to be superior.
  • the mask used for the measurement of the resolution was formed with a pattern at intervals of 0.5 ⁇ m to 4-20 ⁇ m. A desired resolution was determined using a mask having a pattern at intervals of 400 ⁇ m.
  • the fine line adhesion was determined by measuring the minimum spacewidth of the linear circuit pattern without corrosion resulting from developing the exposed portion of the substrate. As the spacewidth thus measured was smaller, the fine line adhesion was evaluated to be superior.
  • the mask used for the measurement of the fine line adhesion was formed with a pattern at intervals of 0.5 ⁇ m to 4-20 ⁇ m.
  • a desired fine line adhesion was determined using a mask having a pattern at intervals of 400 ⁇ m. Furthermore, the 1/1 resolution was determined by measuring the minimum spacewidth cleanly developed under conditions in which the intervals between two adjacent circuit lines were set to 1:1.
  • (8) Surface Analysis The PCB to which the film type photosensitive transfer material of Examples 5 to 7 was applied was exposed and developed as above, after which the surface thereof was observed using an electron microscope. The results are shown in FIGS. 6 to 8.
  • the development time of the resin protective layer was about 0.5-3 sec per 1 ⁇ m thickness of the resin protective layer.
  • FIGS. 6 to 8 showing the surface image of the PCB including the film type photosensitive transfer material of Examples 5 to 6, the roughness of the side and surface was seen to be smaller despite higher magnification compared to FIG. 5 using the transfer material of Comparative Example 1. Therefore, in the case where the film type photosensitive transfer material according to the present invention is applied, handling in the exposure process becomes easy and the resolution can be improved .

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials For Photolithography (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Manufacturing Of Printed Circuit Boards (AREA)

Abstract

L'invention concerne un matériau de transfert photosensible de type film comprenant un film de base, une couche protectrice de résine, une couche de résine photosensible et un film de revêtement, la couche protectrice de résine présentant une adhérence de 0,005 kgf /cm2 ou moins. Lorsqu'on applique le matériau de transfert photosensible sur une carte de circuit imprimé, on peut exécuter un processus d'exposition selon un état permettant de retirer le film de base et donc de réduire l'intervalle entre un masque et la couche de résine photosensible, ce qui permet d'améliorer la résolution d'un motif. Le matériau de transfert photosensible de type film permet de retirer le film de base avant l'exécution du processus d'exposition, peut être traité sous forme de feuilles et appliqué selon un procédé rouleau à rouleau.
PCT/KR2008/006318 2007-10-25 2008-10-24 Matériau de transfert de type film WO2009054705A2 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2010530935A JP5483734B2 (ja) 2007-10-25 2008-10-24 フィルム型感光性転写材料
CN2008801126086A CN101836162B (zh) 2007-10-25 2008-10-24 薄膜型转印材料
HK11100873.9A HK1146751A1 (en) 2007-10-25 2011-01-27 Film type transfer material

Applications Claiming Priority (4)

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KR10-2007-0107798 2007-10-25
KR20070107798 2007-10-25
KR10-2008-0104904 2008-10-24
KR1020080104904A KR101115162B1 (ko) 2007-10-25 2008-10-24 필름형 감광성 전사재료

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CN102549500A (zh) * 2009-09-28 2012-07-04 可隆工业株式会社 干膜光致抗蚀剂
CN102549499A (zh) * 2009-09-30 2012-07-04 可隆工业株式会社 干膜光致抗蚀剂
CN110534647A (zh) * 2019-08-28 2019-12-03 云谷（固安）科技有限公司 柔性衬底、显示基板和显示面板

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EP0267807A2 (fr) * 1986-11-14 1988-05-18 Morton International, Inc. Laminé photosensible
JP2890770B2 (ja) * 1990-09-20 1999-05-17 東洋紡績株式会社 フレキソ印刷版用粘着防止層組成物
JP2001159817A (ja) * 1999-12-03 2001-06-12 Hitachi Chem Co Ltd 感光性樹脂組成物、これを用いた感光性エレメント、レジストパターンの製造法及びプリント配線板の製造法
WO2007125992A1 (fr) * 2006-04-28 2007-11-08 Asahi Kasei Emd Corporation Stratifie de resine photosensible

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JP2992128B2 (ja) * 1991-06-21 1999-12-20 日本合成化学工業株式会社 フォトレジストフィルム
JP3241144B2 (ja) * 1993-02-19 2001-12-25 日立化成工業株式会社 感光性樹脂組成物積層体、レジストパターンの製造法、基板、プリント配線板の製造法、プリント配線板及び機器

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EP0267807A2 (fr) * 1986-11-14 1988-05-18 Morton International, Inc. Laminé photosensible
JP2890770B2 (ja) * 1990-09-20 1999-05-17 東洋紡績株式会社 フレキソ印刷版用粘着防止層組成物
JP2001159817A (ja) * 1999-12-03 2001-06-12 Hitachi Chem Co Ltd 感光性樹脂組成物、これを用いた感光性エレメント、レジストパターンの製造法及びプリント配線板の製造法
WO2007125992A1 (fr) * 2006-04-28 2007-11-08 Asahi Kasei Emd Corporation Stratifie de resine photosensible

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102549500A (zh) * 2009-09-28 2012-07-04 可隆工业株式会社 干膜光致抗蚀剂
JP2013505483A (ja) * 2009-09-28 2013-02-14 コーロン インダストリーズ インク ドライフィルムフォトレジスト
CN102549499A (zh) * 2009-09-30 2012-07-04 可隆工业株式会社 干膜光致抗蚀剂
JP2013505484A (ja) * 2009-09-30 2013-02-14 コーロン インダストリーズ インク ドライフィルムフォトレジスト
CN102549499B (zh) * 2009-09-30 2013-09-11 可隆工业株式会社 干膜光致抗蚀剂
CN110534647A (zh) * 2019-08-28 2019-12-03 云谷（固安）科技有限公司 柔性衬底、显示基板和显示面板
CN110534647B (zh) * 2019-08-28 2023-12-26 云谷（固安）科技有限公司 柔性衬底、显示基板和显示面板

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