JP2010076293A - Transfer film for forming metal pattern, and metal pattern forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of forming a metal pattern of excellent linearity, and a transfer film usable in the method. <P>SOLUTION: This transfer film for forming the metallic pattern is laminated with (A) a resist layer, (B) a metal foil layer formed by rolling, and (C) a pressure-sensitive adhesive layer in this order on a support film, and is constituted to make a flow direction of the resist layer (A) at the forming time substantially in parallel to an rolling direction of the metal foil layer (B). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a metal pattern forming transfer film and a metal pattern forming method.

  In recent years, there is an increasing demand for higher density and higher definition for pattern processing in circuit boards and display panels. Among such display panels that have been increasing in demand, particularly flat panel displays (hereinafter referred to as “FPD”) such as plasma display panels (hereinafter also referred to as “PDP”) and field emission displays (hereinafter also referred to as “FED”). ) Is attracting attention.

  FIG. 1 is a schematic diagram showing a cross-sectional shape of an AC type PDP. In FIG. 1, 101 and 102 are glass substrates disposed so as to face each other, 103 is a partition, and cells are partitioned by the glass substrate 101, the glass substrate 102, and the partition 103. 104 is a transparent electrode fixed to the glass substrate 101, 105 is a bus electrode formed on the transparent electrode 104 for the purpose of reducing the resistance of the transparent electrode 104, and 106 is an address electrode fixed to the glass substrate 102. It is. 107 is a fluorescent material held in the cell, 108 is a dielectric layer formed on the inner surface of the glass substrate 101 so as to cover the transparent electrode 104 and the bus electrode 105, and 109 is used to cover the address electrode 106. A dielectric layer is formed on the inner surface of the glass substrate 102, and 110 is a protective film made of, for example, magnesium oxide. In color PDPs, a color filter (red / green / blue) or a black matrix is provided between the glass substrate and the dielectric layer in order to obtain a high-contrast image. A partition may be provided.

It is desirable that the electrode used for such an FPD has a low resistance.
As a method for manufacturing an electrode, a method of forming an electrode with a conductive paste containing a conductive powder is generally used. However, according to this method, since it is inevitable that the binder or surfactant contained in the conductive paste remains as impurities in the electrode, the resistance of the electrode is increased by these impurities, and an electrode having a low resistance is formed. It was difficult to manufacture.

  Therefore, as a method of manufacturing an electrode having low resistance, a method of forming an electrode using a metal foil has been developed (see JP-A-57-40810). Since the metal foil is made of pure metal, it is possible to reduce the resistance of the electrode.

  However, the metal foil has low adhesion to the glass substrate. Therefore, in order to bond the metal foil to the glass substrate, a method of bonding the metal foil to the glass substrate by interposing a glass paste between the metal foil and the glass substrate has been developed (Japanese Patent Laid-Open No. 8-293259). See the official gazette).

  Specifically, a glass paste layer is provided on a glass substrate, a metal foil layer is provided thereon, and a resist layer (photosensitive resin layer) is further laminated thereon to form a laminate. The laminate is subjected to pattern processing to reveal the resist pattern on the resist layer. This is etched to form a metal foil pattern corresponding to the resist pattern. Then, this is baked and an electrode is manufactured by removing a resist layer.

As described above, Patent Document 2 discloses that a laminated body in which a glass paste layer, a metal layer, and a resist layer are laminated in this order on a glass substrate is disclosed.
Japanese Patent Laid-Open No. 57-40810 JP-A-8-293259

  By the way, as described above, high density and high definition are required for pattern processing in circuit boards and display panels, and in order to form a fine metal pattern, the linearity of the resist pattern is particularly important. It is.

  An object of this invention is to provide the transfer film which can be used for the method of forming the metal pattern excellent in linearity, and the method.

  As a result of diligent study to solve the above problems, the present inventors made the rolling direction of the metal foil formed by rolling and the straight part of the mask pattern of the mask used in the exposure process to the resist layer substantially parallel, Preferably, exposure is performed with the flow direction of the adhesive layer such as the resist layer and the glass paste layer being substantially parallel to the rolling direction, and development is performed after the exposure step to obtain a resist pattern with excellent linearity. It has been found that a metal pattern having excellent linearity can be obtained by performing an etching process using a pattern, and the present invention has been completed.

In addition, the said flow direction refers to the application direction, although the resist layer (A) and adhesion layer (C) of the transfer film for metal pattern formation of this invention are formed by the apply | coating method in this invention.
The present invention for solving the above object
On the support film, (A) a resist layer, (B) a metal foil formed by rolling, and (C) an adhesive layer are laminated in this order, and the flow direction during the formation of the resist layer (A) is: It is a transfer film for metal pattern formation characterized by being substantially parallel to the rolling direction of the metal foil (B).

The flow direction during the formation of the adhesive layer (C) is preferably substantially parallel to the rolling direction of the metal foil (B).
The metal foil (B) is preferably an aluminum foil.

The adhesive layer (C) is preferably formed from a glass paste, that is, a glass paste layer.
The present invention also provides
(C) an adhesive layer, (B) a metal foil formed by rolling, and (A) a resist layer on a glass substrate, the layer (C), the metal foil (B), and the layer (A) Step (1) for forming a laminated body sequentially laminated, and a mask in which the resist layer (A) is arranged so that a straight portion of the mask pattern is substantially parallel to the rolling direction of the metal foil (B) A step (2) of forming a latent image of the resist pattern through exposure processing, a step (3) of developing the resist layer (A) on which the latent image is formed to reveal the resist pattern, And a step (4) of forming a metal foil pattern corresponding to a resist pattern by etching the metal foil (B) after the development process.

In the metal pattern forming method, it is preferable that the flow direction when forming the resist layer (A) is substantially parallel to the rolling direction of the metal foil (B).
In the said metal pattern formation method, it is preferable that the flow direction at the time of formation of the said adhesion layer (C) is substantially parallel to the rolling direction of the said metal foil (B).

In the metal pattern forming method, the metal foil (B) is preferably an aluminum foil.
The step (4) is preferably performed by immersion in an etching solution.

Furthermore, it is more preferable that the steps (3) and (4) are performed by immersion in an etching solution.
Moreover, it is preferable to perform heat treatment after the step (2) and before the step (3), or after the step (3) and before the step (4).

Alternatively, it is preferable to perform an exposure process after the step (3) and before the step (4).
Moreover, when the said adhesion layer (C) is formed from the glass paste, the metal pattern formation method of this invention is further the process (5) which bakes the said laminated body after the said process (4). Including.

  According to the transfer film for forming a metal pattern and the metal pattern forming method of the present invention, a metal pattern having excellent linearity can be formed, and the metal pattern can be used as an electrode or the like. It can be suitably used as an electrode in a circuit board.

[Metal pattern forming transfer film]
The transfer film for forming a metal pattern of the present invention comprises (A) a resist layer, (B) a metal foil formed by rolling (hereinafter also simply referred to as a metal foil (B)), and (C) an adhesive layer on a support film. Are stacked in this order, and the flow direction when forming the resist layer (A) is substantially parallel to the rolling direction of the metal foil (B), preferably, when forming the adhesive layer (C) The flow direction is substantially parallel to the rolling direction of the metal foil (B). Hereafter, each component of the transfer film for metal pattern formation of this invention is demonstrated.

<Support film>
The support film is preferably a resin film having heat resistance and solvent resistance and flexibility. Since the support film has flexibility, the paste-like composition can be applied by a roll coater, and the transfer film for forming a metal pattern of the present invention can be stored and supplied in a rolled state. it can.

  Examples of the resin forming the support film include polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyimide, polyvinyl alcohol, polyvinyl chloride, polyfluoroethylene, and other fluorine-containing resins, nylon, and cellulose.

  The thickness of a support film can be 20-100 micrometers, for example. The surface of the support film is preferably subjected to a release treatment. Thereby, peeling operation of a support film can be easily performed in the below-mentioned transfer process.

<(A) Resist layer>
There is no restriction | limiting in particular in the material which forms the resist layer (A) in this invention, A well-known photoresist composition can be used. The photoresist composition may be negative or positive. However, the negative type is preferable in that the exposure amount required for making it possible to develop more than the positive type (creating a pattern of a part having a high solubility and a part having a low solubility in the developer) is small.
The resist layer (A) in the present invention is formed from, for example, a resist composition containing a photosensitive monomer, a photopolymerization initiator, and a binder resin.

(Photosensitive monomer)
The photosensitive monomer is a substance that is polymerized by exposure and changes its solubility in a developing solution. For example, the photosensitive monomer is a substance that is polymerized by exposure to make the exposed part alkali-insoluble or alkali-insoluble. When a substance that becomes alkali-insoluble by exposure is used as the photosensitive monomer, there is an advantage that it becomes easy to provide contrast between the exposed part and the unexposed part, and it becomes easy to control the pattern shape and increase the definition. is there. Examples of the substance that becomes alkali-insoluble and the like by such exposure include an ethylenically unsaturated group-containing compound, preferably a polyfunctional (meth) acrylate.

Specific examples of the ethylenically unsaturated group-containing compound include di (meth) acrylates of alkylene glycol such as ethylene glycol and propylene glycol;
Di (meth) acrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol;
Di (meth) acrylates of both end hydroxylated polymers such as both end hydroxy polybutadiene, both end hydroxy polyisoprene, both end hydroxy polycaprolactone;
Poly (meth) acrylates of trihydric or higher polyhydric alcohols such as glycerin, 1,2,4-butanetriol, trimethylolalkane, tetramethylolalkane, pentaerythritol, dipentaerythritol;
Poly (meth) acrylates of polyalkylene glycol adducts of trihydric or higher polyhydric alcohols;
Poly (meth) acrylates of cyclic polyols such as 1,4-cyclohexanediol and 1,4-benzenediol;
List oligo (meth) acrylates such as polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, alkyd resin (meth) acrylate, silicone resin (meth) acrylate, and spiraline resin (meth) acrylate. These can be used alone or in combination of two or more.

Of these, trimethylolpropane triacrylate is particularly preferably used.
The molecular weight of the polyfunctional (meth) acrylate is preferably 100 to 2,000.
The content ratio of the photosensitive monomer in the resist composition is usually 5 to 100 parts by mass, and preferably 10 to 70 parts by mass with respect to 100 parts by mass of the binder resin.

(Photopolymerization initiator)
Specific examples of the photopolymerization initiator include benzyl, benzoin, benzophenone, camphorquinone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy- 2-phenylacetophenone, 2-methyl- [4 ′-(methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1- Carbonyl compounds such as ON;
Azo compounds or azide compounds such as azoisobutyronitrile and 4-azidobenzaldehyde;
Organic sulfur compounds such as mercaptan disulfide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide;
Organic peroxides such as benzoyl peroxide, di-tert-butyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, paraffin hydroperoxide;
1,3-bis (trichloromethyl) -5- (2′-chlorophenyl) -1,3,5-triazine, 2- [2- (2-furanyl) ethylenyl] -4,6-bis (trichloromethyl)- Trihalomethanes such as 1,3,5-triazine;
Examples thereof include imidazole dimers such as 2,2′-bis (2-chlorophenyl) 4,5,4 ′, 5′-tetraphenyl 1,2′-biimidazole. These can be used alone or in combination of two or more.
The content rate of the photoinitiator in the said resist composition is 5-100 mass parts normally with respect to 100 mass parts of said photosensitive monomers, Preferably it is 10-50 mass parts.

(Binder resin)
Although various resins can be used as the binder resin, it is preferable to use a binder resin containing an alkali-soluble resin in a proportion of 30 to 100% by mass. Here, “alkali-soluble” refers to the property of being dissolved in an alkaline developer and having a solubility to such an extent that the intended development processing is performed. When an alkali-soluble resin is used, for example, by changing the content of the carboxyl group-containing monomer in the binder resin, there is an advantage that the dissolution rate and pattern shape of the resist layer (A) in the alkaline developer can be controlled.

Specific examples of such alkali-soluble resins include (meth) acrylic resins, hydroxystyrene resins, novolac resins, and polyester resins.
Among such alkali-soluble resins, particularly preferred are the following copolymer of monomer (a) and monomer (c), monomer (a), monomer (b) and monomer (c): An acrylic resin such as

Monomer (I): Carboxyl group-containing monomers Acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, mesaconic acid, cinnamic acid, succinic acid mono (2- (meth) acryloyloxy) Ethyl), ω-carboxy-polycaprolactone mono (meth) acrylate, and the like.

Monomer (b): OH group-containing monomers (hydroxy) -containing monomers such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate; o-hydroxystyrene Phenolic hydroxyl group-containing monomers such as m-hydroxystyrene and p-hydroxystyrene.

Monomer (C): Other copolymerizable monomers (meth) methyl acrylate, (meth) ethyl acrylate, (meth) acrylate n-butyl, (meth) acrylate 2-ethylhexyl, (meth) acrylic acid (meth) acrylic acid esters other than the monomer (ii) such as n-lauryl, benzyl (meth) acrylate, glycidyl (meth) acrylate, cyclohexyl (meth) acrylate, and dicyclopentanyl (meth) acrylate; Acrylates having an α-hydroxymethyl group such as methyl-α- (hydroxymethyl) acrylate, ethyl-α- (hydroxymethyl) acrylate, n-butyl-α- (hydroxymethyl) acrylate; styrene, α-methylstyrene, etc. Aromatic vinyl monomers; conjugated die such as butadiene and isoprene A polymer unsaturated group such as (meth) acryloyl group at one end of a polymer chain such as polystyrene, poly (meth) acrylate, poly (meth) ethyl acrylate, poly (meth) acrylate benzyl, etc. Macromonomer etc.

  The copolymer of the monomer (a) and the monomer (c) and the copolymer of the monomer (a), the monomer (b) and the monomer (c) are due to the presence of a copolymer component derived from the monomer (a). , Having alkali solubility.

  The content of the copolymer component derived from the monomer (a) in these copolymers is preferably 5 to 60% by mass, particularly preferably 10 to 40% by mass, and the copolymer component derived from the monomer (b). The content of is preferably 1 to 50% by mass, particularly preferably 5 to 30% by mass. And the content rate of the copolymerization component derived from the monomer (c) is the content rate of the monomer (i) and the monomer (c) for making the binder resin have desired characteristics when the binder resin is produced. Since it is determined first, if the content ratio of the monomer (A) and the monomer (C) is determined, it is automatically determined as the remaining ratio.

  Particularly preferable compositions for the alkali-soluble resin used in the resist composition include methacrylic acid / benzyl methacrylate / cyclohexyl methacrylate, methacrylic acid / 2-hydroxypropyl methacrylate / n-butyl methacrylate, and methacrylic acid / Examples thereof include mono (2- (meth) acryloyloxyethyl) succinate / 2-hydroxypropyl methacrylate / n-butyl methacrylate.

  The molecular weight of the alkali-soluble resin is preferably 5,000 to 5,000,000, and more preferably 10,000 to 300,000. In addition, in this specification, a weight average molecular weight refers to the weight average molecular weight of polystyrene conversion measured by GPC (gel permeation chromatography).

  For example, it is preferable that the resist layer (A) constituting the metal pattern-forming transfer film of the present invention formed from the resist composition described above can be cured by heating or exposure. If the resist layer (A) can be cured, the resist layer (A) is cured before etching, thereby strengthening the adhesion between the resist layer (A) and the metal foil (B), and etching under strong conditions. Even if it processes, it can prevent that a resist layer (A) detach | leaves from metal foil (B).

The resist layer (A) includes, as optional components, pigments, thickeners, plasticizers, dispersants, development accelerators, adhesion assistants, antihalation agents, leveling agents, storage stabilizers, antifoaming agents, and antioxidants. Various additives such as an agent, an ultraviolet absorber, a sensitizer, and a chain transfer agent may be contained.
The thickness of the resist layer (A) constituting the metal pattern forming transfer film of the present invention is usually 0.1 to 40 μm, preferably 0.5 to 20 μm.

<(B) Metal foil formed by rolling>
The metal foil (B) formed by rolling that constitutes the transfer film for forming a metal pattern of the present invention refers to a foil that substantially does not contain components other than metal (99% by mass or more is metal). The metal foil (B) may be a laminate of a plurality of metal foils.

  The metal foil (B) usually has a thickness of 1 to 20 μm, preferably 3 to 15 μm, and more preferably 5 to 12 μm. When the thickness of the metal foil (B) is smaller than 1 μm, it tends to be difficult to reduce the resistance value of the electrode. If the thickness of the metal foil (B) is larger than 20 μm, it takes a long time to dissolve and remove the metal foil (B) during etching, and the resist layer (A) is peeled off from the metal foil (B) during that time. May cause problems.

  The type of metal constituting the metal foil (B) is not particularly limited as long as an electrode can be formed, but may be at least one metal element selected from the group consisting of Ag, Au, Al and Cu. Particularly preferred is Al. Also, an alloy based on these elements may be used.

<(C) Adhesive layer>
The adhesive layer (C) is interposed between the metal foil (B) and the substrate when the metal pattern is produced by the transfer film for forming a metal pattern of the present invention, and adheres the metal foil (B) to the substrate. It has a function. Preferred constituent materials for the adhesive layer (C) include thermosetting resin compositions and glass pastes.

(Thermosetting resin composition)
The thermosetting resin composition may be composed only of a thermosetting resin. Examples of the thermosetting resin include phenol resin, epoxy resin, urea resin, melamine resin, unsaturated polyester resin, polyurethane, polyimide, A (meth) acrylic resin, a polyester resin, etc. can be mentioned. A mixture of these may also be used.

Moreover, the composition containing the said resin and a crosslinking agent is also mentioned as a thermosetting resin composition.
Although there is no restriction | limiting in particular in the said crosslinking agent, The crosslinkable compound which has two or more ethylenically unsaturated bonds, an epoxy group, or (alkoxy) melamine group in the same molecule is preferable. These compounds can be appropriately used in combination with a crosslinking agent such as a radical generator, an acid generator, a basic catalyst, a polyvalent carboxylic acid anhydride or a catalyst depending on the conditions used.

Examples of the crosslinking agent having an ethylenically unsaturated bond include polyfunctional (meth) acrylates as preferable compounds.
Specifically, as a bifunctional (meth) acrylate, for example, Aronix M-210, M-240, M-6200 (manufactured by Toa Gosei Chemical Co., Ltd.), KAYARAD DD
DA, HX-220, R-604 (Nippon Kayaku Co., Ltd.), V260, V312, V335HP (Osaka Organic Chemical Co., Ltd.) (commercially available), etc.
Examples of trifunctional or higher functional (meth) acrylates include trimethylolpropane triacrylate, pentaerythritol triacrylate, trisacryloyloxyethyl phosphate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and the like. As these specific commercial products, Aronix M-309, M-400, M-405, M-450, M-7100, M-8030, M-8060 (Toa Gosei Chemical Co., Ltd.) )), KAYARAD DPHA, TMPTA, DPCA-20, DPCA-30, DPCA-60, DPCA-60, DPCA-120 (manufactured by Nippon Kayaku Co., Ltd.), V-295, V-300, V-360 , V-GPT, V- 3PA, V-400 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), PPZ (manufactured by Idemitsu Petrochemical Co., Ltd.) and the like.

Of these, polyfunctional (meth) acrylates having three or more functionalities such as Aronix M-400 and KAYARAD DPHA are preferably used. The above crosslinking agents having an ethylenically unsaturated bond can be used in combination of two or more.

As the crosslinking agent having an epoxy group, polyfunctional glycidyl ethers can be mentioned as preferred compounds.
Specifically, bisphenol A type epoxy resins such as Epicoat 1001, 1002, 1003, 1004, 1007, 1009, 1010, and 828 (trade name; manufactured by Yuka Shell Epoxy Co., Ltd.);
Bisphenol F type epoxy resin such as Epicoat 807 (trade name; manufactured by Yuka Shell Epoxy Co., Ltd.);
Epicote 152, 154 (trade name; manufactured by Yuka Shell Epoxy Co., Ltd.), EPPN 201, 202 (trade name; manufactured by Nippon Kayaku Co., Ltd.), and other phenol novolac type epoxy resins; EOCN102, 103S, 104S Cresol novolac epoxy resins such as 1020, 1025, 1027 (trade name; manufactured by Nippon Kayaku Co., Ltd.), Epicoat 180S75 (trade name; manufactured by Yuka Shell Epoxy Co., Ltd.);
Polyphenol type epoxy resins such as Epicoat 1032H60 and XY-4000 (trade name; manufactured by Yuka Shell Epoxy Co., Ltd.);
CY-175, 177, 179, Aldarite CY-182, 192, 184 (trade name; manufactured by Ciba-Geigy Co., Ltd.), ERL-4234, 4299, 4221, 4206 (trade name; U.C. C), Shodyne 509 (trade name; manufactured by Showa Denko KK), Epicron 200, 400 (trade name; manufactured by Dainippon Ink), Epicoat 871, 872 (trade name; oiled shell) Epoxy Co., Ltd.), ED-5661, 5562 (trade name; Celanese Coating Co., Ltd.) and other cyclic aliphatic epoxy resins;
Aliphatic polyglycidyl ethers such as Epolite 100MF (manufactured by Kyoeisha Oil Chemical Co., Ltd.) and Epiol TMP (manufactured by Nippon Oil & Fats Co., Ltd.) are included.

  Examples of (alkoxy) melamine cross-linking agents include hexamethylol melamine, hexabutyrol melamine, partially methylolated melamine and its alkylated product, tetramethylol benzoguanamine, partially methylolated benzoguanamine and its alkylated product. Can do.

The content rate of the crosslinking agent in a thermosetting resin composition is 1-1000 weight part normally with respect to 100 weight part of said thermosetting resins, Preferably it is 1-200 weight part.
Furthermore, a filler can be contained in the thermosetting resin composition in order to add strength and suppress shrinkage during thermosetting, and a solvent can be contained in order to improve applicability.

(Glass paste)
The pressure-sensitive adhesive layer (C) constituting the metal pattern-forming transfer film of the present invention can be formed using various conventionally known glass pastes, but is derived from a glass powder (a) and a monomer having a hydrophilic group. It is preferable to use a glass paste (C ′) containing a binder resin (b) whose constituent component is 5% by mass or less. Moreover, the said glass paste (C ') may contain a solvent (c) further.

((A) Glass powder)
The glass powder (a) constituting the glass paste (C ′) to be the adhesive layer (C) of the transfer film for forming a metal pattern of the present invention is preferably a glass powder having a softening point in the range of 400 to 600 ° C. A glass powder in the range of 450 to 580 ° C. is particularly preferable. Even if the glass powder has a softening point of less than 400 ° C. or more than 600 ° C., it is possible to form a pattern having a good pattern shape. However, when the softening point of the glass powder is less than 400 ° C., firing described later is performed. In the process, since the glass powder (a) melts at a stage where the organic substance such as the binder resin (b) is not completely decomposed and removed, a part of the organic substance remains in the formed glass sintered body. As a result, the obtained glass sintered body may be colored or volatiles may adversely affect the panel. On the other hand, when the softening point of the glass powder (a) exceeds 600 ° C., the glass substrate needs to be baked at a temperature higher than 600 ° C., so that the glass substrate is likely to be distorted.

Specific examples of suitable glass powder (a) include I. Boron oxide and zinc oxide (B ₂ O ₃ —ZnO system), II. Boron oxide, silicon oxide, aluminum oxide (B ₂ O ₃ —SiO ₂ —A
l ₂ O ₃ system), III. A mixture of boron oxide, silicon oxide, and zinc oxide (based on B ₂ O ₃ —SiO ₂ —ZnO), IV. Examples thereof include a mixture of boron oxide, silicon oxide, aluminum oxide, and zinc oxide (B ₂ O ₃ —SiO ₂ —Al ₂ O ₃ —ZnO system).
The average particle diameter (D50) of the glass powder (a) is usually 0.1 to 5 μm.

((B) Binder resin)
In the binder resin (b) contained in the glass paste (C ′) serving as the pressure-sensitive adhesive layer (C) in the present invention, the proportion of the component derived from the monomer having a hydrophilic group relative to the entire component is usually 5% by mass or less. And particularly preferably 0% by mass. When the binder resin (b) has more than 5% by mass of a component derived from a monomer having a hydrophilic group, the binder resin (b) is abundant during the development processing of the resist layer (A) described later. In order to absorb water, the adhesive layer (C) swells, the smoothness of the adhesive layer (C) is lost, and the transparency of the metal pattern tends to be impaired. Further, the adhesive layer (C) may be detached from the substrate due to swelling of the adhesive layer (C).

The “hydrophilic group” herein includes “strongly hydrophilic group” and “not very hydrophilic group”, and does not include “small hydrophilic group”. Here, “strongly hydrophilic group” means —SO ₃ H, —
SO ₃ M (M is an alkali metal or —NH _{4. The} same applies hereinafter), —OSO ₃ H, —OS
O ₃ M, —COOM, —NR ₃ X (R is an alkyl group, X is a halogen), and the like. “A group that is not very hydrophilic” refers to —COOH, —NH ₂ , —CN, —O.
H, -NHCONH _2, and - refers to (OCH ₂ CH _{2) n} or the like. The “small hydrophilic group” refers to —CH ₂ OCH ₃ , —OCH ₃ , —COOCH ₃ , and —CS.

  Specifically, examples of the monomer having a hydrophilic group include acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, mesaconic acid, cinnamic acid, and succinic acid mono (2- ( Carboxyl group-containing monomers such as (meth) acryloyloxyethyl), ω-carboxy-polycaprolactone mono (meth) acrylate, and 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meta ) Hydroxyl group-containing monomers such as 3-hydroxypropyl acrylate, polyethylene glycol mono (meth) acrylic acid, polyalkylene glycol-containing monomers such as polypropylene glycol mono (meth) acrylic acid, and o-hydroxystyrene, m-hydroxystyrene P-hydro It can be mentioned a phenolic hydroxyl group-containing monomers such as such as Shisuchiren.

  Moreover, as a monomer which does not correspond to the monomer which has a hydrophilic group, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, (meth) acrylate 2-ethylhexyl, ( (Meth) acrylates such as n-lauryl (meth) acrylate, benzyl (meth) acrylate, glycidyl (meth) acrylate, and dicyclopentanyl (meth) acrylate, styrene And aromatic vinyl monomers such as α-methylstyrene, and conjugated dienes such as butadiene and isoprene.

  As the binder resin (b) in the glass paste (C ′) serving as the pressure-sensitive adhesive layer (C) constituting the metal pattern forming transfer film of the present invention, a resin composed only of alkyl (meth) acrylate is most preferable.

  The content ratio of the binder resin (b) in the glass paste (C ′) is usually 5 to 300 parts by mass, preferably 10 to 100 parts by mass with respect to 100 parts by mass of the glass powder (a). More preferably, it is 20-75 mass parts.

(C) Solvent The solvent (c) can be contained in the glass paste (C ′) in order to give the adhesive layer (C) appropriate fluidity or plasticity and good film-forming properties. As the solvent used as the solvent (c), the affinity with the glass powder (a) and the solubility of the binder resin (b) are good, and an appropriate viscosity can be imparted to the adhesive layer (C). It is preferable that it can be evaporated and removed by drying.

  Specific examples of the solvent (c) include ether alcohols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether; acetic acid-n-butyl, acetic acid Saturated aliphatic monocarboxylic acid alkyl esters such as amyl; Lactic acid esters such as ethyl lactate and lactic acid-n-butyl; Methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, ethyl-3-ethoxypropionate, etc. And ether esters, terpineol, butyl carbitol acetate, butyl carbitol and the like.

  In the case where the resist layer (A) is heated and cured in order to strengthen the adhesion between the resist layer (A) and the metal foil (B), the adhesive layer (C) is formed from the glass paste (C ′). The solvent (c) contained in the adhesive layer (C) volatilizes during the heating, and foamy protrusions, so-called blisters, may be generated on the surface of the metal foil (B). Therefore, in order to prevent volatilization of such a solvent, a solvent having a boiling point higher by 10 to 120 ° C. than the heating temperature, preferably a solvent having a boiling point higher by 20 to 100 ° C., more preferably a boiling point higher by 30 to 70 ° C. It is preferable to use the solvent having as the solvent (c).

  For example, when ethyl-3-ethoxypropionate having a boiling point of 150 ° C. or higher is used as the solvent (c), if the heating temperature is 120 ° C., the solvent (c) Volatilization can be prevented and the heat curing of the resist layer (A) can be ensured.

  The glass paste (C ′) containing each component as described above is a paste-like composition having fluidity suitable for application, and its viscosity is usually 1,000 to 30,000 cP, preferably 3,000 to 10,000 cP.

The content rate of the solvent (c) in glass paste (C ') is 5-50 mass parts normally with respect to 100 mass parts of glass powder (a), Preferably, it is 10-40 mass parts.
The pressure-sensitive adhesive layer (C) constituting the metal pattern forming transfer film of the present invention is formed by applying the glass paste (C ′) on the metal foil (B).

The thickness of the pressure-sensitive adhesive layer (C) is usually 1 to 50 μm, preferably 5 to 40 μm.
The adhesive layer (C) may contain various additives such as a dispersant and a plasticizer as optional components.

<Method for producing transfer film for forming metal pattern>
The transfer film for forming a metal pattern of the present invention is formed by laminating a resist layer (A) on a support film so that the flow direction at the time of formation is substantially parallel to the rolling direction of the metal foil (B). The metal foil (B) formed by rolling is laminated on the resist layer (A), and the adhesive layer (C) is applied onto the metal foil (B) by a coating method, preferably the flow direction during the formation. Are laminated so as to be substantially parallel to the rolling direction of the metal foil (B).

  As described above, the flow direction refers to the direction of application of the resist layer (A) and the adhesive layer (C) of the transfer film for forming a metal pattern according to the present invention, which are formed by a coating method. In addition, “substantially parallel” specifically means that the angle formed between the flow direction when forming the resist layer (A) or the adhesive layer (C) and the rolling direction of the metal foil (B) is 0 ° to 30 °. , Preferably it points out in the range of 0-10 degrees.

In the lamination of the resist layer (A), the components contained in the resist layer (A) are kneaded to prepare a paste-like resist composition, and this is flowed on the support film in the flow direction of the resist layer (A). Can be carried out by coating so as to be substantially parallel to the rolling direction of the metal foil (B). Specifically, the resist composition may be applied on the support film substantially parallel to the rolling direction of the metal foil (B). Or you may laminate | stack metal foil (B) so that the application direction of a resist composition and the rolling direction of metal foil (B) may become substantially parallel. Examples of the method for applying the resist composition include various methods such as screen printing, roll coating, spin coating, and cast coating. After application, the resist composition is dried as necessary.

  Examples of the method of laminating the metal foil (B) on the resist layer (A) include a method of laminating a metal foil such as an aluminum foil on the resist layer (A). As described above, the metal foil (B) is formed by rolling, and a streak is formed in the rolling direction when the metal is rolled.

  For the lamination of the adhesive layer (C), the thermosetting resin composition or glass paste (C ′) is prepared, and the flow direction of the adhesive layer (C) is the metal foil (C) on the metal foil (B). The coating can be carried out so as to be substantially parallel to the rolling direction of B). Specifically, the thermosetting resin composition or the glass paste (C ′) may be applied on the metal foil (B) substantially parallel to the rolling direction of the metal foil (B). As a method for applying the thermosetting resin composition or the glass paste (C ′), one that can efficiently form a coating film having a large film thickness with excellent film thickness uniformity is preferable. Examples thereof include a coating method using a roll coater, a coating method using a doctor blade, a coating method using a curtain coater, and a coating method using a wire coater.

  In the transfer film for forming a metal pattern of the present invention, an adhesive layer (C) is laminated on a support film by a coating method, and a metal foil (B) is preferably formed on the adhesive layer (C), preferably an adhesive layer (C). Separately, the resist film (A) is laminated on the support film by a coating method so that the flow direction during formation of the metal foil and the rolling direction of the metal foil (B) are substantially parallel. The two films thus obtained were made so that the flow direction during the formation of the resist layer (A) and the rolling direction of the metal foil (B) were substantially parallel, and the metal foil (B) and the resist layer (A). It can also be manufactured by adhering them so that they are in contact with each other.

  Then, the transfer film for metal pattern formation obtained as needed is dried. The drying temperature is usually 50 to 150 ° C., and the drying time is usually 0.5 to 30 minutes. The amount of residual solvent in the metal pattern-forming transfer film after drying is usually 0.1 to 2% by mass, preferably 0.1 to 1% with respect to 100% by mass of the glass paste layer film and the resist layer film, respectively. % By mass.

  In the transfer film for forming a metal pattern of the present invention, a protective film can be provided on the adhesive layer (C). Examples of the protective film include a polyethylene film and a polyvinyl alcohol film.

[Metal pattern forming method]
The metal pattern forming method of the present invention includes (C) an adhesive layer, (B) a metal foil formed by rolling, and (A) a resist layer on a glass substrate, and the layer (C) and the metal foil (B ), And the step (1) for forming a laminate in which the layers (A) are laminated in this order, and the resist layer (A), the linear portion of the mask pattern is substantially the rolling direction of the metal foil (B). Step (2) of forming a latent image of a resist pattern by exposing through a mask arranged in parallel, and developing the resist layer (A) on which the latent image is formed to reveal the resist pattern And a step (4) of forming a metal foil pattern corresponding to a resist pattern by etching the metal foil (B) after the developing treatment. “Substantially parallel” is the same as “substantially parallel” in the description of the method for producing a transfer film for forming a metal pattern. Moreover, when the said adhesion layer (C) is formed from glass paste (C '), the metal pattern formation method of this invention is the process of baking the said laminated body after the said process (4) further. (5) is included. Each step will be described below.

<(I) Lamination process (1)>
In the laminating step (1), the metal foil (B) is laminated on the adhesive layer (C), and the resist layer (A) is laminated on the metal foil (B). It is the process of forming the laminated body containing these layers on a glass substrate.

The constituent materials of the resist layer (A), the metal foil (B), and the adhesive layer (C) are as described in the metal pattern forming transfer film of the present invention.
The glass substrate is preferably made of heat-resistant glass. For example, CP600V manufactured by Central Glass Co., Ltd. can be suitably used as the glass substrate. In addition, the surface of the glass substrate may be subjected to chemical treatment using a silane coupling agent, plasma treatment, and thin film formation treatment using an ion plating method, a sputtering method, a gas phase reaction method, a vacuum deposition method, or the like, if necessary. Pretreatment may be performed. When the chemical treatment is performed, the treatment liquid concentration is usually 0.1 to 5% by mass, the drying temperature is usually 80 to 140 ° C., and the drying time is usually 10 to 60 minutes.

The method for forming the laminate is not particularly limited as long as an electrode or the like can be produced. For example, for forming a metal pattern of the present invention including a resist layer (A), a metal foil (B), and an adhesive layer (C). Using the transfer film, the resist layer (A), metal foil (B), and adhesive layer (C) are transferred onto a glass substrate with the adhesive layer (C) in contact with the glass substrate using a heating roller or the like. A method can be mentioned. Here, as transfer conditions, for example, the surface temperature of the heating roller is 40 to 140 ° C., the roll pressure by the heating roller is 0.1 to 10 kg / cm ² , and the moving speed of the heating roller is 0.1 to 10 m / min. be able to. Such an operation (transfer process) can be performed by a laminator apparatus. The glass substrate may be preheated, and the preheat temperature can be set to 40 to 140 ° C., for example.

  Moreover, you may transfer these on a glass substrate sequentially using the transfer film provided with 1 layer or 2 layers of a resist layer (A), metal foil (B), and adhesion layer (C). For example, using a transfer film having only the metal foil (B) and the adhesive layer (C), the metal foil (B) and the adhesive layer (C) are brought into contact with the glass substrate. The resist layer (A) may be transferred onto the metal foil (B) using a transfer film which is transferred onto a glass substrate and further provided with a resist layer (A).

  Or like the case of the manufacturing method of the transfer film for metal pattern formation of the said invention, a thermosetting resin composition or a glass paste is apply | coated on a glass substrate, an adhesion layer (C) is formed, and on it. A metal foil (B) may be laminated, and a resist composition may be applied thereon to form a resist layer (A).

In the lamination step (1), other layers other than the resist layer (A), the metal foil (B), and the adhesive layer (C) may be provided as necessary.
Moreover, in this lamination process (1), it was more excellent in linearity that the flow direction of the said resist layer (A) and the adhesion layer (C) was substantially parallel with the rolling direction of the said metal foil (B). It is preferable from the viewpoint of obtaining a metal pattern. Therefore, the laminate is preferably formed using the metal pattern forming transfer film of the present invention.

<(Ii) Exposure latent image forming step (2)>
A pattern latent image is formed on the resist layer (A) by a method of selectively irradiating (exposure) radiation such as ultraviolet rays to the surface of the resist layer (A) through an exposure mask or a method of scanning with laser light. Form.

  The mask pattern of the exposure mask is generally a stripe having a width of 10 to 500 μm, although it varies depending on the panel design used. In the method for forming a metal pattern of the present invention, the exposure mask is arranged and used so that the straight line portion of the mask pattern is substantially parallel to the rolling direction of the metal foil (B), so that the linearity is excellent A metal pattern can be formed.

  Note that the straight line portion of the mask pattern refers to a portion inside the frame of the mask through which light passes during exposure. Further, the straight portion is substantially parallel to the rolling direction of the metal foil (B). If the mask pattern is a stripe, the shape of the pattern is a sequence of a plurality of rectangles. It indicates that it is substantially parallel to the rolling direction of B). When the mask pattern is not a stripe but a bent pattern, exposure is performed by arranging the mask so that the area of the pattern substantially parallel to the rolling direction of the metal foil (B) is maximized.

  As a radiation irradiation apparatus for performing exposure, an ultraviolet irradiation apparatus generally used in a photolithography method, an exposure apparatus used in manufacturing a semiconductor and a liquid crystal display device, a laser apparatus, and the like can be used. It is not particularly limited.

The light source output is usually 1 to 100 mW / cm ² , preferably 0.1 to 5 mW / cm ² . The exposure time is usually 0.05 to 1 minute. The exposure amount is usually 10 to 200 mJ / cm ² .

<(Iii) Development step (3)>
In this step, the laminate is developed to reveal a resist pattern on the resist layer (A).

  There are no particular restrictions on the development processing conditions, and depending on the type of the resist layer (A), the type, composition, and concentration of the developer, the development time, the development temperature, the development method (for example, dipping method, rocking method, shower method, A spray method, a paddle method, etc.), a developing device, and the like can be appropriately selected.

As the developer used in the developing step in the metal pattern forming method of the present invention, an alkali developer is preferably used.
As an active ingredient of the alkaline developer, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, ammonium dihydrogen phosphate , Inorganic such as potassium dihydrogen phosphate, sodium dihydrogen phosphate, lithium silicate, sodium silicate, potassium silicate, lithium carbonate, sodium carbonate, potassium carbonate, lithium borate, sodium borate, potassium borate, ammonia Alkaline compounds; tetramethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropyl Triethanolamine, and organic alkaline compounds such as ethanol amine.

  The alkaline developer can be prepared by dissolving one or more of the alkaline compounds in water. The concentration of the alkaline compound in the alkaline developer is usually from 0.001 to 10% by mass. After the development with an alkali developer, a washing process is usually performed. The development temperature is usually 20 to 50 ° C.

<(Iv) Etching step (4)>
The laminated body that has undergone the development step (3) is etched to dissolve and remove unnecessary portions of the metal foil (B), thereby forming a metal pattern corresponding to the resist pattern.

  There are no particular restrictions on the etching treatment conditions, and depending on the type of metal foil (B), the type / composition / concentration of the etchant, the treatment time, the treatment temperature, and the treatment method (for example, immersion method, rocking method, shower method) , Spray method, paddle method), processing apparatus, and the like can be appropriately selected.

  In the metal pattern forming method using the metal foil, it is necessary to dissolve and remove the metal foil made of substantially pure metal in the etching process. Therefore, the etching is more effective than the method using no metal such as the photosensitive paste method. It is necessary to carry out under strong conditions.

  The type of the etchant used in this etching step (4) is not particularly limited as long as it is a solution capable of etching the metal forming the metal foil (B). For example, an acidic aqueous solution or an alkaline aqueous solution can be used. . As the acidic aqueous solution, nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid and a mixed aqueous solution thereof can be used. As alkaline aqueous solution, the thing similar to the said alkali developing solution can be used.

  The concentration can be, for example, 0.01 to 10% by mass. Moreover, the temperature which processes with such an etching liquid can be 20-50 degreeC, for example, and processing time can be 1 to 60 minutes, for example.

  If the type of the resist layer (A) is selected so that the same solution as that used in the developing step (3) can be used as the etching solution, the developing step (3) and the etching step (4) are selected. ) Can be performed continuously in one process, and the production efficiency can be improved by simplifying the process.

  As described above, when an alkali-soluble resin is used as the binder resin contained in the resist layer (A), the alkali solubility of the resist layer (A) can be adjusted. By adjusting the developing solution and the etching solution to the same alkaline solution, the developing step (3) and the etching step (4) can be performed continuously in one step. In this case, for the reason described above, it is preferable to perform the development step (3) and the etching step (4) by treating the laminate with a solution that is an etchant and a developer.

In the present invention, the resist layer (A) may be peeled off from the metal foil (B) during the etching step (4).
In order to prevent this, it is effective to cure the resist layer (A) and strengthen the adhesion between the resist layer (A) and the metal foil (B). Examples of the method for curing the resist layer (A) include heat curing for heating the laminate to cure the resist layer (A), and exposure curing for exposing the laminate to cure the resist layer (A). Can do. That is, in the present invention, is the heat curing step performed after the latent exposure image forming step (2) and before the developing step (3), or after the developing step (3) and before the etching step (4)? Alternatively, it is preferable to carry out an exposure curing step after the development step (3) and before the etching step (4).

The temperature for heat curing is usually 100 to 300 ° C, preferably 120 to 300 ° C. The curing time is usually 10 to 120 minutes.
In exposure curing, a method of performing irradiation (exposure) of radiation such as ultraviolet rays is preferable. As a radiation irradiation apparatus, the thing similar to what is used by the said exposure latent image formation process (2) can be used.

As a method of curing the resist layer (A), heat curing is preferable to exposure curing in that the resist layer (A) can be more effectively prevented from peeling from the metal foil (B).
Further, as described above, when the adhesive layer (C) is formed from the glass paste (C ′) when the resist layer (A) is cured by heating, the solvent (c) contained in the adhesive layer (C) is volatilized. In addition, foamy protrusions, so-called blisters, may be generated on the surface of the metal foil (B). In order to prevent such volatilization of the solvent (c), it is conceivable to use the solvent (c) having a boiling point higher than the heating temperature as described above.

<(V) Firing step (5)>
When the adhesive layer (C) is formed from the glass paste (C ′), the laminate subjected to the etching step (4) is baked to burn off the organic substance in the resist layer (A). Then, the resist layer (A) remaining on the patterned metal foil (B) is removed. A metal pattern is formed by this process. Moreover, the adhesion layer (C) and the glass substrate are integrated by this baking. The said metal pattern can be used conveniently as an electrode, especially an electrode in a display panel or a circuit board.

  The temperature of the baking treatment needs to be a temperature at which the organic substance in the resist layer (A) is burned out, and is usually 400 to 600 ° C. The firing time is usually 10 to 90 minutes.

  Examples of the present invention will be described below, but the present invention is not limited to these examples. In the following, “part” means “part by mass”. Moreover, each evaluation method in an Example is shown below.

[Example 1]
(1) Preparation of transfer film As glass powder, B ₂ O ₃ —ZnO frit (softening point 485 ° C., particle size (D50) 2.5 um) 1
00 parts, n-butyl methacrylate / 2-ethylhexyl methacrylate = 40/60 (mass%) copolymer (Mw = 100,000) 32 parts as binder resin, dioctyl azelate 2 parts as plasticizer Further, 15 parts of ethyl-3-ethoxypropionate was used as a solvent, and these were kneaded with a stirring deaerator and then dispersed with a three roll to prepare a glass paste.

  This glass paste was applied onto a support film (width 200 mm, length 300 mm, thickness 38 μm) made of a PET film by a blade coater to form an adhesive layer having a thickness of 40 μm.

The aluminum foil was laminated so that the flow direction during the formation of the adhesive layer was parallel to the rolling direction of the 12 μm thick aluminum foil to form a laminate of the 52 μm thick aluminum foil and the adhesive layer.
As alkali-soluble resin, benzyl methacrylate / cyclohexyl methacrylate / methacrylic acid = 50/35/15 (mass%) copolymer (Mw = 30,000) 100 parts, polypropylene glycol diacrylate (n ≈12, 33.3 parts of Toa Gosei "M270") and 16.6 parts of trimethylolpropane EO-modified triacrylate (n ≒ 2, "M360" Toagosei), and 2-benzyl-2 as a photopolymerization initiator 15 parts of dimethylamino-1- (4-morpholinophenyl) -butan-1-one (“IRG.369” manufactured by Ciba Special Chemicals) were used. These were kneaded with a stirring deaerator and then dispersed with a three roll to prepare a resist composition. This resist composition was applied onto a support film (width 200 mm, length 300 mm, thickness 38 μm) made of a PET film by a blade coater to form a resist layer having a thickness of 10 μm.

With the two films obtained by the above operation, the resist layer and the aluminum foil are in contact with each other with the flow direction of the resist layer parallel to the rolling (flow) direction of the laminate of the aluminum foil and the adhesive layer. And a laminate having a thickness of 62 μm was formed.
As described above, a transfer film for forming a metal pattern was prepared.

(2) Formation of metal pattern (i) Lamination process The support film in contact with the adhesive layer of the transfer film for forming a metal pattern is peeled off, and the transfer film is heated at a surface temperature of 90 ° C. and heated roller roll pressure 0.2 kg / By transferring on the glass substrate under the transfer conditions of cm ² , heating roller moving speed 1.0m / min,
A laminate in which an adhesive layer, a metal foil, and a resist layer were laminated in this order was formed.

(Ii) Exposure latent image forming step The i-line (ultraviolet light having a wavelength of 365 nm) is applied to the resist layer of the laminate by an ultrahigh pressure mercury lamp through a striped negative exposure mask having a line width of 90 μm and a space width of 90 μm. Was irradiated. The exposure amount at that time was 200 mJ / cm ^{2 in} terms of illuminance measured by a 365 nm sensor. The mask pattern of the exposure mask was oriented so as to be parallel to the rolling direction of the metal foil.

(Iii) Development step The laminated body that has undergone the exposure latent image formation step is subjected to a development process for 60 seconds by a shower method using a 0.3 mass% sodium carbonate aqueous solution at a liquid temperature of 30 ° C as a developer, Water washing was performed using ultrapure water.

(Iv) Heat-curing step After the developing step, the laminate was heated at 120 ° C. for 60 minutes to cure the resist layer.

(V) Etching Step The laminate that had undergone the heat curing step was immersed in an etching solution of a liquid temperature of 25 ° C. and a 4% by mass sodium hydroxide aqueous solution for 20 minutes.

(Vi) Firing process The laminated body which passed through the said etching process was baked for 20 minutes in the temperature atmosphere of 570 degreeC within the baking furnace.
As a result, an aluminum foil pattern having a pattern width of about 90 μm and a thickness of 12 μm could be obtained on the glass substrate.

[Example 2 and Comparative Examples 1-2]
The pattern width is about 90 μm on the glass substrate in the same manner as in Example 1 except that the rolling direction of the aluminum foil, the linear portion of the mask pattern, and the flow direction when forming the adhesive layer are changed as shown in Table 1 below. An aluminum foil pattern having a thickness of 12 μm was obtained.

[Example 3]
(1) Preparation of transfer film for forming metal pattern n-Butyl methacrylate / benzyl methacrylate = 30/70 (mass%) copolymer (Mw = 100,000) as binder resin, 100 parts as cross-linking agent A thermosetting resin composition was prepared by using 50 parts of pentaerythritol hexaacrylate and 40 parts of methoxypropyl acetate as a solvent, kneading them with a stirring defoaming apparatus, and then dispersing them with three rolls. .

  This thermosetting resin composition was applied onto a support film (width 200 mm, length 300 mm, thickness 38 μm) made of a PET film with a blade coater to form an adhesive layer having a thickness of 5 μm.

The aluminum foil was laminated so that the flow direction during the formation of the adhesive layer was parallel to the rolling direction of the 12 μm thick aluminum foil to form a laminate of the 17 μm thick aluminum foil and the adhesive layer.
As alkali-soluble resin, benzyl methacrylate / cyclohexyl methacrylate / methacrylic acid = 50/35/15 (mass%) copolymer (Mw = 30,000) 100 parts, photosensitive monomer as polypropylene glycol acrylate (n≈ 12, 33.3 parts of Toa Gosei "M270") and 16.6 parts of trimethylolpropane EO-modified triacrylate (n≈2, "M360" Toagosei), and 2-benzyl-2- After 15 parts of dimethylamino-1- (4-morpholinophenyl) -butan-1-one (“IRG.369” manufactured by Ciba Special Chemicals) were kneaded with a stirring deaerator, A resist composition was prepared by dispersing with this roll. This resist composition was applied onto a supporting film (width 200 mm, length 300 mm, thickness 38 μm) made of a PET film by a blade coater to form a resist layer having a thickness of 10 μm.

With the two films obtained by the above operation, the resist layer and the aluminum foil are in contact with each other with the flow direction of the resist layer parallel to the rolling (flow) direction of the laminate of the aluminum foil and the adhesive layer. And a laminated body having a thickness of 27 μm was formed.
As described above, a transfer film for forming a metal pattern was prepared.

(2) Pattern formation (i) Lamination process By transferring the metal pattern forming transfer film onto a substrate having a surface roughness Ra of about 5000 mm, an adhesive layer, a metal layer, and a resist layer are formed on the substrate. A laminated body was formed by laminating in this order.

(Ii) Exposure latent image forming step The i-line (ultraviolet light having a wavelength of 365 nm) is applied to the resist layer of the laminate by an ultrahigh pressure mercury lamp through a striped negative exposure mask having a line width of 90 μm and a space width of 90 μm. Was irradiated. The exposure amount at that time was 200 mJ / cm ^{2 in} terms of illuminance measured by a 365 nm sensor. The mask pattern of the exposure mask was oriented so as to be parallel to the rolling direction of the metal foil.

(Iii) Development step The laminated body that has undergone the exposure latent image formation step is subjected to a development process by a shower method for 60 seconds using a 0.3 mass% sodium carbonate aqueous solution at a liquid temperature of 30 ° C as a developer, Water washing was performed using ultrapure water.

(Iv) Heat-curing step After the developing step, the laminate was heated at 250 ° C. for 60 minutes to cure the resist layer.

(V) Etching Step The laminate that had undergone the development step was immersed in an etching solution of a liquid temperature of 25 ° C. and a 4% by mass sodium hydroxide aqueous solution for 20 minutes to form a pattern.

(3) Edge roughness measurement The line pattern of the line and space pattern obtained in Examples 1 to 3 and Comparative Examples 1 and 2 was observed with a microscope (ECLIPSE L200 manufactured by NIKON).

  Randomly measure the line width of 10 line patterns for the observed line pattern shape in each sample, and calculate the average line width and the maximum, minimum, and standard deviation of the observed line widths. Evaluated as linearity. The evaluation results are shown in Table 1.

It is a schematic diagram which shows the cross-sectional shape of alternating current type FPD (specifically, PDP).

Explanation of symbols

DESCRIPTION OF SYMBOLS 101 Glass substrate 102 Glass substrate 103 Partition 104 Transparent electrode 105 Bus electrode 106 Address electrode 107 Fluorescent substance 108 Dielectric layer 109 Dielectric layer 110 Protective film

Claims (13)

On the support film, (A) a resist layer, (B) a metal foil formed by rolling, and (C) an adhesive layer are laminated in this order,
A transfer film for forming a metal pattern, wherein a flow direction when forming the resist layer (A) is substantially parallel to a rolling direction of the metal foil (B).   The transfer film for forming a metal pattern according to claim 1, wherein the flow direction during the formation of the adhesive layer (C) is substantially parallel to the rolling direction of the metal foil (B).   The said metal foil (B) is an aluminum foil, The transfer film for metal pattern formation of Claim 1 or 2 characterized by the above-mentioned.   The said adhesion layer (C) is formed from the glass paste, The transfer film for metal pattern formation in any one of Claims 1-3 characterized by the above-mentioned. (C) an adhesive layer, (B) a metal foil formed by rolling, and (A) a resist layer on a glass substrate, the layer (C), the metal foil (B), and the layer (A) A step (1) of forming a laminated body sequentially laminated;
A step of exposing the resist layer (A) through a mask arranged so that a linear portion of the mask pattern is substantially parallel to the rolling direction of the metal foil (B), thereby forming a latent image of the resist pattern ( 2) and
A step (3) of developing the resist layer (A) on which a latent image is formed to reveal a resist pattern;
And (4) forming a metal foil pattern corresponding to a resist pattern by etching the metal foil (B) after the developing treatment.   The metal pattern forming method according to claim 5, wherein a flow direction at the time of forming the resist layer (A) is substantially parallel to a rolling direction of the metal foil (B).   The metal pattern forming method according to claim 5 or 6, wherein a flow direction when forming the adhesive layer (C) is substantially parallel to a rolling direction of the metal foil (B).   The metal pattern (B) according to any one of claims 5 to 7, wherein the metal foil (B) is an aluminum foil.   The metal pattern forming method according to claim 5, wherein the step (4) is performed by immersion in an etching solution.   The metal pattern forming method according to claim 5, wherein the steps (3) and (4) are performed by immersion in an etching solution.   The heat treatment is performed after the step (2) and before the step (3), or after the step (3) and before the step (4). Metal pattern forming method.   The metal pattern forming method according to claim 5, wherein an exposure process is performed after the step (3) and before the step (4). The adhesive layer (C) is formed from a glass paste,
Furthermore, the process (5) of baking the said laminated body is included after the said process (4), The metal pattern formation method in any one of Claims 5-12 characterized by the above-mentioned.

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