WO2019164016A1 - Film de transfert, procédé de formation de motif de résine utilisant un film de transfert, et procédé de formation de motif de film durci - Google Patents

Film de transfert, procédé de formation de motif de résine utilisant un film de transfert, et procédé de formation de motif de film durci Download PDF

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WO2019164016A1
WO2019164016A1 PCT/JP2019/007370 JP2019007370W WO2019164016A1 WO 2019164016 A1 WO2019164016 A1 WO 2019164016A1 JP 2019007370 W JP2019007370 W JP 2019007370W WO 2019164016 A1 WO2019164016 A1 WO 2019164016A1
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transfer film
photosensitive resin
resin composition
compound
acid
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PCT/JP2019/007370
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English (en)
Japanese (ja)
Inventor
下田　浩一朗
智史 渋井
誠 中出
華菜子 水村
真由紀 吉田
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旭化成株式会社
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Publication of WO2019164016A1 publication Critical patent/WO2019164016A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • 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
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings

Definitions

  • the present invention relates to a photosensitive resin composition, a transfer film, a resin pattern manufacturing method using the transfer film, and a cured film pattern manufacturing method. More specifically, the present invention relates to a liquid crystal display device, an organic EL display device, a touch panel display device, an integrated circuit element, a solid-state imaging device, a planarization film of an electronic component such as a semiconductor element, formation of a protective film and an interlayer insulating film, or The present invention relates to a photosensitive resin composition suitable for a rigid printed wiring board, a solder resist of a flexible printed wiring board, or an interlayer insulating film, a transfer film, and a resin pattern manufacturing method using the same.
  • Touch panels are used not only for large electronic devices such as personal computers and televisions, but also for small electronic devices such as car navigation systems, mobile phones, and electronic dictionaries, and display devices such as OA / FA devices.
  • An electrode made of a material is provided.
  • ITO Indium-Tin-Oxide
  • indium oxide Indium oxide
  • tin oxide As the transparent conductive electrode material, ITO (Indium-Tin-Oxide), indium oxide, and tin oxide are known, and these materials have high visible light transmittance, so that electrode materials for substrates for liquid crystal display elements, etc. It is mainly used as.
  • Existing touch panel methods include resistive film method, optical method, pressure method, capacitance method, electromagnetic wave induction method, image recognition method, vibration detection method, ultrasonic method, etc. ing.
  • capacitive touch panels In recent years, the use of capacitive touch panels has been most advanced. In a capacitive touch panel, when a fingertip, which is a conductor, contacts the touch input surface, capacitive coupling occurs between the fingertip and the conductive film, thereby forming a capacitor. For this reason, the capacitive touch panel detects the coordinates of the contact position by capturing a change in charge at the contact position of the fingertip. In particular, the projected capacitive touch panel can detect multiple points on the fingertip, and thus has a good operability to give complicated instructions.
  • a plurality of X electrodes and a plurality of Y electrodes orthogonal to the plurality of X electrodes have a two-layer structure in order to express two-dimensional coordinates by the X axis and the Y axis.
  • ITO is used as the electrode material.
  • the frame area of the touch panel is an area where the touch position cannot be detected, reducing the area of the frame area is an important factor for improving the product value.
  • metal wiring is required to transmit a touch position detection signal, but in order to reduce the frame area, it is necessary to reduce the width of the metal wiring. Since the conductivity of ITO is not sufficiently high, copper is generally used for metal wiring.
  • corrosive components such as moisture and salt may enter the sensing region from the inside. If a corrosive component enters the inside of the touch panel, the metal wiring will corrode, which may increase the electrical resistance between the electrode and the drive circuit, or cause a disconnection. To prevent these, a protective film with an antirust effect on the metal wiring is necessary. Generally, there exists a tendency for the rust prevention effect of metal wiring to increase, so that the moisture permeability of a protective film is low.
  • the metal wiring for transmitting the detection signal is connected to other members at the terminal portion, it is necessary to ensure conduction, and the protective film must be removed from the terminal portion. For this reason, the protective film is required to have good developability, and it is required to have good detachability in various patterns such as circular holes.
  • a dilute alkaline aqueous solution such as an aqueous sodium carbonate solution is most often used, and development at a low temperature of less than 30 ° C. is desired in order to maintain the long-term stability of the developer concentration.
  • the photosensitive resin composition for forming the protective film is provided as a transfer film, not as a liquid resist.
  • a vacuum roll laminator is usually used in the process of attaching the transfer film to the substrate by the roll-to-roll method.
  • the temperature is applied to the photosensitive resin composition layer due to the heat of the roll after the transfer film is attached, and oxygen is not present in the environment for suppressing radical polymerization.
  • the photopolymerization initiator is cleaved, and the dark reaction proceeds to cause a significant decrease in developability. Therefore, the roll temperature of the vacuum roll laminate is required to be low, specifically, less than 100 ° C.
  • a protective film for protecting the wiring board surface or pattern circuit provided on the substrate in addition to the protective film, a photosensitive solder resist, a photosensitive film Various film-like photosensitive materials such as dry film resists are also used depending on the application.
  • Patent Document 1 Although the composition which combined two types of epoxy acrylate acid modified products is used as a photosensitive coverlay film, the description regarding low temperature developability, low temperature laminating property, or moisture permeability is not made
  • Patent Documents 2 and 3 a composition containing an acrylic copolymer having a weight average molecular weight of 30,000 or more or a carboxyl group-containing polyurethane having a weight average molecular weight of 10,000 and an epoxy acrylate acid modified product is photosensitive. Used as a conductive dry film solder resist. None of the documents describes low-temperature developability, low-temperature laminating properties, or adhesion to a substrate, and it is assumed that these performances are not all satisfied.
  • Patent Document 4 a composition containing an acrylic copolymer having a weight average molecular weight of 12,000 and a modified cresol novolac epoxy acrylate is used as a photosensitive dry film solder resist. There is no description of properties, low-temperature laminating properties or adhesion to a substrate. Moreover, although the solder resist of patent document 4 has provided the moisture resistance of a fixed level, the request
  • the transfer film has a tack property, a low temperature developability, a low temperature laminate property, a moisture permeability as a cured film, and a good adhesion to a conductor substrate, and a conductor portion such as an electrode. It is providing the photosensitive resin composition suitable for protection of a film, a transfer film, and its manufacturing method.
  • a transfer film for forming a conductor protective film comprising a support film and a photosensitive resin composition layer wherein the photosensitive resin composition layer comprises the following components: (A) Alkali-soluble resin (excluding acid-modified epoxy (meth) acrylate compounds); (B) a compound containing a carboxyl group and an ethylenically unsaturated group; (C) a photopolymerizable compound; and (D) a photopolymerizable initiator; Containing
  • the (A) alkali-soluble resin has a weight average molecular weight of 11,000 or more and 29,000 or less, and an acid value of 100 mgKOH / g or more
  • the compound (B) containing a carboxyl group and an ethylenically unsaturated group has a weight average molecular weight of 1,000 to 9,500, an acid value of 60 mgKOH / g or more, and a refractive index of 1.570 or more.
  • a conductor characterized in that the mass ratio (A) / (B) of the (A) alkali-soluble resin to the compound containing (B) a carboxyl group and an ethylenically unsaturated group is 0.18 to 6.0.
  • Transfer film for forming a protective film [2] Item 2. The transfer film according to Item 1, wherein the acid value of the alkali-soluble resin (A) is 200 mgKOH / g or less. [3] Item 3. The transfer film according to Item 1 or 2, wherein the acid value of the compound (B) containing a carboxyl group and an ethylenically unsaturated group is 200 mgKOH / g or less and the refractive index is 1.650 or less.
  • Item 4 The transfer film according to any one of Items 1 to 3, wherein the photosensitive resin composition layer has a hydroxyl value of 15.0 mgKOH / g or less.
  • Item 5 The transfer film according to Item 4, wherein the photosensitive resin composition layer has a hydroxyl value of 0.01 mgKOH / g or more.
  • Item 6 The transfer film according to any one of Items 1 to 5, wherein the refractive index of the photosensitive resin composition layer is 1.550 or more.
  • Item 7 The transfer film according to Item 6, wherein the refractive index of the photosensitive resin composition layer is 1.630 or less.
  • the (A) alkali-soluble resin contains a structure derived from (meth) acrylic acid in an amount of 12% by mass to 30% by mass and a structure derived from styrene or a derivative thereof in an amount of 30% by mass to 80% by mass.
  • Item 9 The transfer film according to any one of Items 1 to 8, wherein the compound (B) containing a carboxyl group and an ethylenically unsaturated group is an acid-modified epoxy (meth) acrylate compound.
  • Item 10 Item 10. The transfer film according to any one of Items 1 to 9, which is used for either a protective film for a touch panel or a protective film for a force sensor.
  • a conductor part protective film-forming transfer film comprising a support film and a photosensitive resin composition layer, wherein the photosensitive resin composition layer comprises the following (I) and (II):
  • the area ratio S ⁇ 50k of the region having the molecular weight M ⁇ 50000 is 1.0 to 9.0% when the area of the region having the molecular weight M ⁇ 2000 is 100%; and (II) tetrahydrofuran at 23 ° C.
  • the transfer film for forming a conductor protective film according to Item 16 wherein the acid value A1 is 200 mgKOH / g or less.
  • Item 18 The transfer film according to Item 16 or 17, which is used for either a touch panel protective film or a force sensor protective film.
  • a transfer film for forming a conductor protective film comprising a support film and a photosensitive resin composition layer wherein the photosensitive resin composition layer comprises the following components: (A) Alkali-soluble resin (excluding acid-modified epoxy (meth) acrylate compounds); (B) a compound containing a carboxyl group and an ethylenically unsaturated group; (C) a photopolymerizable compound; and (D) a photopolymerizable initiator; Containing
  • the (A) alkali-soluble resin has a weight average molecular weight of 11,000 or more and 29,000 or less, and an acid value of 100 mgKOH / g or more
  • the compound (B) containing a carboxyl group and an ethylenically unsaturated group has a weight average molecular weight of 1,000 to 9,500, an acid value of 60 mgKOH / g or more, and the following general formulas (1) to (3): ): Including at least the structure according to any one of A
  • Item 20 The transfer film according to Item 19, wherein the acid value of the (A) alkali-soluble resin is 200 mgKOH / g or less.
  • Item 21 The transfer film according to Item 19 or 20, wherein the acid value of the compound containing (B) a carboxyl group and an ethylenically unsaturated group is 200 mgKOH / g or less.
  • Item 20 The transfer film according to Item 19, wherein the photosensitive resin composition layer has a hydroxyl value of 15.0 mgKOH / g or less.
  • Item 23 Item 23.
  • Items (19) to (19), wherein the (A) alkali-soluble resin contains a structure derived from (meth) acrylic acid in an amount of 12% by mass to 30% by mass and a structure derived from styrene or a derivative thereof in an amount of 30% by mass to 80% by mass.
  • Item 27 The transfer film according to any one of Items 19 to 26, wherein the compound (B) containing a carboxyl group and an ethylenically unsaturated group is an acid-modified epoxy (meth) acrylate compound.
  • Item 28 The transfer film according to any one of Items 19 to 27, which is used for either a protective film for a touch panel or a protective film for a force sensor.
  • a pattern production method comprising producing a pattern by laminating, exposing and developing the transfer film according to any one of items 1 to 28 on a substrate. [30] 30.
  • a cured film pattern manufacturing method wherein a pattern obtained by the pattern manufacturing method according to item 29 is subjected to post-exposure processing and / or heat treatment.
  • a photosensitive resin composition and a transfer film in which the transfer film has good tack properties, low-temperature developability, low-temperature laminating properties, moisture permeability as a cured film, and good adhesion to a conductor substrate. be able to.
  • FIG. 1 is a differential molecular weight distribution curve obtained from the GPC elution curve of the photosensitive resin layer contained in the transfer film obtained in Example 5.
  • the (A) alkali-soluble resin according to the present embodiment is not limited as long as it contains a carboxyl group but does not contain an acid-modified epoxy (meth) acrylate compound.
  • the acid value (mgKOH / g) of the alkali-soluble resin is 100 or more, preferably 100 to 200.
  • the acid value is preferably 200 or less from the viewpoint of reducing moisture permeability and improving the rust prevention property of the conductor, and is 100 or more from the viewpoint of improving the low temperature developability, and the balance between the rust prevention property and the low temperature developability of the conductor. From the viewpoint, 110 to 180 is more preferable, and 120 to 160 is still more preferable.
  • the acid value is measured by a potentiometric titration method using a Hiranuma automatic titrator (COM-555) manufactured by Hiranuma Sangyo Co., Ltd., using 0.1 mol / L potassium hydroxide.
  • the alkali-soluble resin may have an ethylenically unsaturated group at the main chain terminal and / or side chain.
  • the weight average molecular weight of alkali-soluble resin is 11,000 or more and 29,000 or less from a viewpoint of applicability
  • the weight-average molecular weight of the alkali-soluble resin is determined based on the properties of the development aggregate, the tack properties when used as a transfer film, the properties of the unexposed film such as edge fuse properties, cut chip properties, etc. It is 11,000 or more from the viewpoint of adhesion to the substrate after film formation and curing on the substrate, and 29,000 or less from the viewpoint of low-temperature developability.
  • the edge fuse property is a phenomenon in which the photosensitive resin composition layer protrudes from the end face of the roll when the transfer film is wound into a roll shape.
  • the cut chip property is a phenomenon in which a chip flies when an unexposed film is cut with a cutter. If the scattered chips adhere to the upper surface of the transfer film or the like, it is transferred to a mask in the subsequent exposure process or the like, causing a defect.
  • the weight average molecular weight of the alkali-soluble resin is more preferably from 13,000 to 27,000, still more preferably from 15,000 to 26,000.
  • the measurement of the weight average molecular weight according to the present embodiment is performed using gel permeation chromatography (GPC) manufactured by JASCO Corporation set under the following conditions.
  • the obtained weight average molecular weight is a polystyrene equivalent value.
  • Pump Gulliver, PU-1580 type
  • Shodex registered trademark
  • RI Column temperature: 40 ° C
  • Flow rate 1.0 mL / min
  • Injection volume 0.02 mL
  • Moving bed solvent Tetrahydrofuran calibration curve: Calibration curve defined using polystyrene standard sample ⁇ Use of calibration curve based on polystyrene standard sample (Shodex STANDARD SM-105 manufactured by Showa Denko KK) ⁇
  • the hydroxyl value (mgKOH / g) of the alkali-soluble resin is preferably 40 or less, and more preferably 30 or less.
  • the moisture permeability of the cured product after the photosensitive resin composition is exposed and thermally cured can be lowered, so that the rust prevention property of the conductor is improved.
  • the hydroxyl value of alkali-soluble resin can be measured as follows. First, the (A) alkali-soluble resin solution to be measured for hydroxyl value is placed on an aluminum dish and heated at a temperature 10 ° C. higher than the boiling point of the solvent in the solution for 4 hours to completely remove the solvent. 1 g of the solid content of the alkali-soluble resin (A) thus obtained is precisely weighed, and 10 mL of 10% by mass acetic anhydride pyridine solution is added and dissolved uniformly, followed by heating at 100 ° C. for 1 hour. After heating, 10 mL of water and 10 mL of pyridine are added and heated at 100 ° C. for 10 minutes.
  • hydroxyl value (AB) ⁇ f ⁇ 28.05 / sample (g) + acid value ⁇ wherein A represents the amount (mL) of 0.1 mol / L potassium hydroxide ethanol solution used in the blank test. , B indicates the amount (mL) of 0.1 mol / L potassium hydroxide ethanol solution used for titration, and f indicates a factor. ⁇
  • the (A1) acrylic copolymer according to the present embodiment includes, for example, (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylonitrile, (meth) acrylamide, and styrene. And copolymers such as derivatives thereof.
  • copolymer in addition to the structural units already described, other monomers copolymerizable with those structural units may be contained as the structural units.
  • Other monomers include, for example, hydroxyalkyl (meth) acrylate, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, (meth) acrylic acid tetrahydrofurfuryl ester, dimethylaminoethyl (meth) acrylate Ester, (meth) acrylic acid diethylaminoethyl ester, (meth) acrylic acid glycidyl ester, (meth) acrylic acid benzyl ester, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetra Examples thereof include fluoropropyl (meth) acrylate, styrene and derivatives thereof.
  • styrene derivative examples include 4-methylstyrene, 4-hydroxystyrene, 4-methoxystyrene, 4-chlorostyrene, 4- (chloromethyl) styrene, and 4-vinylbenzoic acid.
  • a copolymer containing a structural unit is more preferable.
  • the structure derived from (meth) acrylic acid is 12% by mass or more and 30% by mass or less, and the structure derived from styrene or its derivative is 30 as (A1) acrylic copolymer in that both low temperature developability and moisture permeability reduction can be achieved. More preferably, the content is from 80% by weight to 80% by weight.
  • the acrylic copolymer is synthesized by radical polymerization by combining the above monomers in a specific weight ratio.
  • an azo polymerization initiator is preferably used as the photopolymerization initiator.
  • Examples of commercially available azo initiators include V-601 (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.).
  • the (A2) polyimide precursor according to the present embodiment does not mean only polyamic acid but also includes imidized part of the polyamic acid.
  • the polyimide precursor can be obtained, for example, by reacting a mixture of tetracarboxylic dianhydride and diamine in an organic solvent at a molar ratio of 0.8: 1 to 1.2: 1.
  • tetracarboxylic dianhydride A conventionally well-known tetracarboxylic dianhydride can be used.
  • tetracarboxylic dianhydride aromatic tetracarboxylic acid, aliphatic tetracarboxylic dianhydride, etc. can be applied.
  • limiting in the diamine to be used A conventionally well-known diamine can be used.
  • tetracarboxylic dianhydrides include biphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride, benzophenone-3,3 ′, 4,4′-tetracarboxylic dianhydride, oxydiphthalic acid Anhydride, diphenylsulfone-3,3 ′, 4,4′-tetracarboxylic dianhydride, ethylene glycol bis (trimellitic acid monoester acid anhydride), p-phenylenebis (trimellitic acid monoester acid anhydride) ), P-biphenylenebis (trimellitic acid monoester acid anhydride), m-phenylenebis (tomellitic acid monoester acid anhydride), o-phenylenebis (trimellitic acid monoester acid anhydride), pentanediol bis (Trimellitic acid monoester acid anhydride), decanediol bis (trimellitic acid monoester acid an
  • diamine examples include 1,3-bis (4-aminophenoxy) alkane, 1,4-bis (4-aminophenoxy) alkane, 1,5-bis (4-aminophenoxy) alkane, 1,4-diaminobenzene, 1,3-diaminobenzene, 2,4-diaminotoluene, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'- Diaminobiphenyl, 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, 3,7-diamino-dimethyldibenzothiophene-5 5-dioxide, 4,4′-diaminobenzophenone, 3,3′-diamino
  • the main chain terminal of the polyimide precursor is not particularly limited as long as it does not affect the performance, and may be an acid dianhydride or a terminal structure derived from a diamine used for producing the polyimide precursor.
  • the terminal may be sealed with other acid anhydrides or amine compounds.
  • a polyimide precursor having a polyimide structure and a polyamic acid structure as repeating units, respectively, is a step of reacting acid dianhydride and diamine in a non-equal molar amount to synthesize a first-stage polyimide portion (step 1), followed by 2 It can be produced by a step of synthesizing the polyamic acid portion at the stage (step 2).
  • step 1 is not necessarily included.
  • each process will be described.
  • the process of synthesizing the first stage polyimide portion will be described.
  • the step of synthesizing the first-stage polyimide portion is not particularly limited, and a known method can be applied. More specifically, the polyimide portion can be synthesized by the following method. First, diamine is dissolved and / or dispersed in a polymerization solvent, and acid dianhydride powder is added thereto. Then, a solvent that is azeotroped with water is added, and the mixture is heated and stirred for 0.5 to 96 hours, more preferably for 0.5 to 30 hours while removing by-product water azeotropically using a mechanical stirrer.
  • the polyimide part can be synthesized by adding a known imidization catalyst or without a catalyst.
  • the imidation catalyst is not particularly limited, but may be an acid anhydride such as acetic anhydride, ⁇ -valerolactone, ⁇ -butyrolactone, ⁇ -tetronic acid, ⁇ -phthalide, ⁇ -coumarin, and ⁇ -phthalido acid. Lactone compounds, and tertiary amines such as pyridine, quinoline, N-methylmorpholine, and triethylamine. Moreover, you may use 1 type, or 2 or more types of these mixtures as needed. Among these, a mixed system of ⁇ -valerolactone and pyridine and non-catalyst are particularly preferable from the viewpoint of high reactivity and reducing the influence on the next reaction.
  • the reaction solvent used in the synthesis of the polyimide part includes 2 or more carbon atoms such as dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether.
  • Particularly preferable solvents include ether compounds having 2 to 9 carbon atoms, ester compounds having 3 to 12 carbon atoms, aromatic hydrocarbon compounds having 6 to 10 carbon atoms, and 2 carbon atoms. Examples thereof include nitrogen-containing compounds having 10 or less carbon atoms. These can be arbitrarily selected in consideration of industrial productivity and influence on the next reaction.
  • the reaction temperature is preferably 100 ° C. or higher and 250 ° C. or lower.
  • the synthesis of the polyamic acid moiety at the second stage can be carried out by using the polyimide moiety obtained in Step 1 as a starting material and adding diamine and / or acid dianhydride for polymerization.
  • the polymerization temperature in the synthesis of the second stage polyamic acid moiety is preferably 0 ° C. or higher and 80 ° C. or lower.
  • the time required for the reaction varies depending on the purpose or reaction conditions, but is usually in the range of 30 minutes to 30 hours.
  • step 2 When performing step 2 without performing step 1, first, diamine is dissolved and / or dispersed in a polymerization solvent, and acid dianhydride powder is added thereto.
  • the polymerization solvent is the same as that exemplified in Step 1.
  • the polymerization temperature is preferably 0 ° C. or higher and 80 ° C. or lower.
  • the time required for the reaction is usually from 30 minutes to 30 hours.
  • a carboxyl group-containing polyimide is synthesized by mixing tetracarboxylic dianhydride and diamine in an organic solvent at a molar ratio of 0.8: 1 to 1.2: 1 and reacting them.
  • the skeleton is characterized by containing a carboxyl group even after imidization, but the polyamic acid structure may partially remain.
  • the carboxyl group-containing polyimide is usually synthesized using a carboxyl group-containing diamine. From the viewpoint of solubility in organic solvents or availability, 3,5-diaminobenzoic acid, 3,3′-dicarboxy-4,4′-diaminodiphenylmethane, or the like may be used as the carboxyl group-containing diamine. It can. These diamines may be used alone or in combination of two or more.
  • Examples of the tetracarboxylic dianhydride, the diamine used in combination with the carboxyl group-containing diamine, the solvent used for the synthesis, and the imidization catalyst are the same as those described above for the (A2) polyimide precursor.
  • the carboxyl group-containing polyurethane according to the present embodiment is a known disulfide compound, a carboxyl group-containing diol compound, and other diol compounds in an aprotic solvent having an activity corresponding to the respective reactivity. It is synthesized by adding a catalyst and heating.
  • the molar ratio of the diisocyanate and diol compound to be used is preferably 0.8: 1 to 1.2: 1. When an isocyanate group remains at the end of the polymer, the molar ratio can be determined by treating with an alcohol or an amine. Is synthesized in a form in which no isocyanate group remains.
  • Diisocyanate compounds include 2,4-tolylene diisocyanate, dimer of 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 4,4'- Aromatic diisocyanate compounds such as diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3,3′-dimethylhyphenyl-4,4′-diisocyanate: hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate, etc.
  • Aromatic diisocyanate compounds such as diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3,3′-dimethylhyphenyl-4,4′-diisocyanate: hexamethylene diisocyanate
  • Aliphatic diisocyanate compounds such as: isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4- (or 2 6)
  • Alicyclic diisocyanate compounds such as diisocyanate and 1,3- (isocyanatomethyl) cyclohexane; reaction product of diol and diisocyanate such as an adduct of 1 mol of 1,3-butylene glycol and 2 mol of tolylene diisocyanate The diisocyanate compound etc. which are are mentioned.
  • carboxyl group-containing diols examples include 3,5-dihydroxybenzoic acid, 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (2-hydroxyethyl) propionic acid, and 2,2-bis (3-hydroxy Propyl) propionic acid, bis (hydroxymethyl) acetic acid, bis (4-hydroxydiphenyl) acetic acid, 4,4-bis (4-hydroxydiphenyl) pentanoic acid, tartaric acid, N, N-dihydroxyethylglycine, N, N-bis (2-hydroxyethyl) -3-carboxy-propionamide and the like.
  • diol compounds used in combination with a carboxyl group-containing diol compound include high molecular weight diols such as polytetramethylene diol, polybutadiene diol, hydrogenated polybutadiene diol, polycarbonate diol, polyester diol, and polycaprolactone diol; or ethylene glycol, 1 , 2-propylene glycol, 1,3-propylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 1,4-butanediol, 2,2′-dimethyl-1,3-propanediol, diethylene glycol, Triethylene glycol, 1,5-pentamethylene glycol, dipropylene glycol, neopentyl glycol, 1,6-hexamethylene glycol, cyclohexane-1,4-dio , Cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, 2-butene-1
  • (B) Compound containing carboxyl group and ethylenically unsaturated group
  • (B) The compound containing carboxyl group and ethylenically unsaturated group according to the present embodiment has one or more carboxyl groups and one in the molecule.
  • (B1) epoxy (meth) acrylate acid modified material can be used conveniently.
  • the acid value (mgKOH / g) of the compound containing a carboxyl group and an ethylenically unsaturated group is 60 or more, preferably 60 to 200.
  • the acid value is preferably 200 or less from the viewpoint of reducing the moisture permeability of the cured film of the photosensitive resin composition and improving the rust prevention property of the conductor, and from the viewpoint of improving the low temperature developability of the photosensitive resin composition layer. From the viewpoint of balance of both performances, 70 to 170 is more preferable, and 80 to 150 is still more preferable.
  • the acid value is measured in the same manner as described above for the (A) alkali-soluble resin.
  • the weight average molecular weight of the compound containing a carboxyl group and an ethylenically unsaturated group is (A) compatible with an alkali-soluble resin, tackiness when used as a transfer film, and low-temperature developability. 1,000 or more and 9,500 or less.
  • the weight average molecular weight of the compound containing a carboxyl group and an ethylenically unsaturated group is 1,000 or more from the viewpoint of the properties of the unexposed film such as tackiness, edge fuse property and cut chip property when used as a transfer film. From the viewpoint of low temperature developability and low temperature laminating property of the photosensitive resin composition layer, it is 9,500 or less, preferably 2,000 or more and 8,000 or less.
  • the hydroxyl value (mgKOH / g) of the compound containing a carboxyl group and an ethylenically unsaturated group is preferably 30 or less, and more preferably 20 or less.
  • the moisture permeability of the cured product of the photosensitive resin composition can be lowered, so that the rust prevention property of the conductor is improved.
  • the measurement of the hydroxyl value is performed in the same manner as described above for the (A) alkali-soluble resin.
  • the compound (B) containing a carboxyl group and an ethylenically unsaturated group according to the present embodiment is 1) a refractive index of 1.570 or more, and / or 2) the following general formulas (1) to (3) It includes at least one of the skeletons represented by By satisfying the above 1) and / or 2), the moisture permeability of the cured product obtained from the photosensitive resin composition according to the present embodiment can be lowered, so that the rust prevention property of the conductor is improved.
  • the refractive index of the component (B) is preferably 1.570 or more, and preferably 1.650 or less from the viewpoint of low-temperature developability of the photosensitive resin composition layer.
  • the refractive index of the component (B) according to the present embodiment is measured by the following method.
  • an organic solvent having a boiling point of 200 ° C. or less at 1 atm that dissolves a compound containing a carboxyl group and an ethylenically unsaturated group for example, ethanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, propylene) Glycol-1-monomethyl ether-2-acetate
  • the solid content concentration is adjusted to 30 to 70% by mass.
  • the obtained solution was coated on a commercially available polyethylene terephthalate (PET) film (thickness 16 ⁇ m) with a bar coater, dried in a hot air oven at 100 ° C. for 10 minutes, and (B) carboxyl group and ethylenically unsaturated group.
  • PET polyethylene terephthalate
  • a layered product having a thickness of 5 ⁇ m is obtained.
  • Refractive index measurement is performed using a prism made by Metricon, Prism Coupler Model 2010 / M, laser beam wavelength: 532 nm, and in a state where a layer made of a compound containing (B) a carboxyl group and an ethylenically unsaturated group is in contact with the prism. Is called.
  • Epoxy (meth) acrylate acid-modified product is defined as a compound that satisfies the following two conditions, and is an acid-modified epoxy (meth) acrylate Also called a compound.
  • a compound containing two or more epoxy groups in the molecule can be synthesized as a starting material. ii) It contains one or more carboxyl groups and one or more (meth) acryloyl groups in the molecule.
  • a carboxyl group of a monocarboxylic acid having a (meth) acryloyl group is reacted with an epoxy group of a compound containing two or more epoxy groups in the molecule.
  • the monocarboxylic acid having a (meth) acryloyl group is, for example, acrylic acid or methacrylic acid.
  • Known reaction conditions can be applied to this reaction.
  • the epoxy group is cleaved by the reaction to generate a hydroxyl group.
  • the second reaction is a reaction between the hydroxyl group of the compound produced in the first reaction and a dicarboxylic acid anhydride.
  • a dicarboxylic acid anhydride either a saturated dicarboxylic acid anhydride or an unsaturated dicarboxylic acid anhydride can be used.
  • dicarboxylic anhydrides include, for example, succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydroanhydride.
  • Examples thereof include phthalic acid and methylbutenyl tetrahydrophthalic anhydride. Of these, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride and methyltetrahydrophthalic anhydride are particularly preferred. These dicarboxylic acid anhydrides can be used individually by 1 type, and 2 or more types can also be mixed and used for them. Known reaction conditions can also be used for the second reaction between the hydroxyl group and the anhydride group. By the reaction, the anhydride group is cleaved to produce an ester group and a carboxyl group.
  • the amount of the acid anhydride group of the dicarboxylic dianhydride in the second reaction is usually 60 to 100 parts by mole, preferably 75 parts by mole or more and 100 parts by mole or less with respect to 100 parts by mole of the hydroxyl group produced in the first reaction.
  • the epoxy (meth) acrylate modified product synthesized through the first and second reactions is further reacted with a compound having one epoxy group and one or more radically polymerizable unsaturated groups in the molecule. It is also possible to increase the content of ethylenically unsaturated groups (third reaction).
  • the compound having one epoxy group and one or more radically polymerizable unsaturated groups in the molecule include glycidyl acrylate, glycidyl methacrylate, and allyl glycidyl ether.
  • ⁇ Synthesis method (2)> As the first reaction, as in the above synthesis method (1), the carboxyl group of a monocarboxylic acid having a (meth) acryloyl group is reacted with the epoxy group of a compound containing two or more epoxy groups in the molecule. .
  • the monocarboxylic acid having a (meth) acryloyl group is, for example, acrylic acid or methacrylic acid.
  • Known reaction conditions can be applied to this reaction.
  • the epoxy group is cleaved by the reaction to generate a hydroxyl group.
  • the second reaction is a reaction between the hydroxyl group of the compound produced in the first reaction and a tetracarboxylic anhydride.
  • tetracarboxylic acid anhydrides include biphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride, benzophenone-3,3 ′, 4,4′-tetracarboxylic dianhydride, oxydiphthalic acid dianhydride , Diphenylsulfone-3,3 ′, 4,4′-tetracarboxylic dianhydride, ethylene glycol bis (trimellitic acid monoester anhydride), p-phenylenebis (trimellitic acid monoester acid anhydride) , P-biphenylenebis (trimellitic acid monoester acid anhydride), m-phenylenebis (tomellitic acid monoester acid anhydride), o-phenylenebis (trimellitic acid monoester acid anhydride), pentan
  • the third reaction is a reaction between the residual hydroxyl group of the compound produced in the second reaction and a dicarboxylic acid anhydride.
  • a dicarboxylic acid anhydride either a saturated dicarboxylic acid anhydride or an unsaturated dicarboxylic acid anhydride can be used.
  • dicarboxylic anhydrides include, for example, succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydroanhydride.
  • Examples thereof include phthalic acid and methylbutenyl tetrahydrophthalic anhydride. Of these, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride and methyltetrahydrophthalic anhydride are particularly preferred. These dicarboxylic acid anhydrides can be used individually by 1 type, and 2 or more types can also be mixed and used for them. Known reaction conditions can be used for the third reaction between the hydroxyl group and the dicarboxylic anhydride group. By the reaction, the anhydride group is cleaved to produce an ester group and a carboxyl group, and an epoxy (meth) acrylate acid modified product can be obtained.
  • the total amount of acid anhydride groups in the tetracarboxylic dianhydride in the second reaction and the dicarboxylic anhydride in the third reaction is usually 60 to 100 moles per 100 moles of the hydroxyl group produced in the first reaction. Part, preferably 75 parts by mole or more and 100 parts by mole or less.
  • the second reaction and the third reaction can also be performed simultaneously. As a specific synthesis method, the method described in JP-A-06-001938 can be used.
  • the modified epoxy (meth) acrylate acid synthesized through the first to third reactions is further reacted with a compound having one epoxy group and one or more radically polymerizable unsaturated groups in the molecule. It is also possible to increase the content of ethylenically unsaturated groups (fourth reaction).
  • the compound having one epoxy group and one or more radically polymerizable unsaturated groups in the molecule include glycidyl acrylate, glycidyl methacrylate, and allyl glycidyl ether.
  • the epoxy (meth) acrylate modified product according to this embodiment can be obtained by the synthesis method (1), the synthesis method (2), or the like, but a commercially available product can also be used.
  • Commercially available epoxy (meth) acrylate modified products containing the general formula (1) include ZCR-1569H, ZCR-1601H, ZCR-1797H, ZCR-1798H (manufactured by Nippon Kayaku Co., Ltd.), etc.
  • Commercially available epoxy (meth) acrylate modified products containing formula (3) include FCA-954, FCA-293, FCA-506 (manufactured by Nagase ChemteX) or TR-B201, TR-B202 (Strong Changzhou) Electronic material company) etc. are mentioned.
  • Mass ratio A / B of (A) alkali-soluble resin and compound containing (B) carboxyl group and ethylenically unsaturated group according to the present embodiment ((A) mass of alkali-soluble resin / (B) carboxyl group and The mass of the compound containing an ethylenically unsaturated group is 0.18 to 6.0.
  • a / B is 0.18 or more, the tackiness of the transfer film is improved, and the adhesion to the conductor base material is improved.
  • a / B is 6.0 or less, the low temperature laminating property and the moisture permeability of the cured film are reduced. Surprisingly, the low temperature developability deteriorates when A / B is less than 0.18 and more than 6.0. From the viewpoint of balance of various performances, a more preferable range of A / B is 0.40 to 1.0.
  • the photopolymerizable compound according to the present embodiment is a compound having an ethylenically unsaturated double bond, for example, a compound having polymerizability by having an ethylenically unsaturated group in the structure thereof.
  • the compound having an ethylenically unsaturated double bond preferably includes (c1) a compound having three or more polymerizable groups in the molecule and / or (c2) a compound having one polymerizable group in the molecule. It is more preferable to contain.
  • the compound which has an ethylenically unsaturated double bond can be used in combination with compounds other than the above.
  • Component (c1) contains a compound having three or more polymerizable groups in the molecule, thereby increasing the crosslink density of the protective film, making it difficult for moisture to permeate, and reducing the moisture permeability of the cured film. Can do.
  • the compound having three or more polymerizable groups in the molecule has at least 3 moles of a group capable of adding an alkylene oxide group in the molecule as a central skeleton, and this group has an ethylene oxide group and a propylene oxide group. Alternatively, it can be obtained by converting an alcohol obtained by adding an alkylene oxide group such as a butylene oxide group into (meth) acrylate.
  • (meth) acrylic acid may be reacted directly with the central skeleton without modifying the central skeleton with an alkylene oxide group.
  • the compound that can be a central skeleton include glycerin, trimethylolpropane, pentaerythritol, diglycerin, ditrimethylolpropane, dipentaerythritol, and isocyanurate rings.
  • the photosensitive resin composition further preferably includes (c1) a compound having a molecular weight of 430 or less as the compound having three or more polymerizable groups in the molecule.
  • the molecular weight of the component (c1) is 430 or less, the low temperature developability of the photosensitive resin composition layer is improved.
  • Examples of the compound having a molecular weight of 430 or less include compounds having glycerin, trimethylolpropane, pentaerythritol and the like as a central skeleton.
  • the component (C) may contain pentaerythritol tetra (meth) acrylate or trimethylolpropane tri (meth) acrylate. preferable.
  • (C1) Without compound or in addition to (c1) compound, (c2) By including a compound having one polymerizable group in the molecule, (C) the entire compound having an ethylenically unsaturated double bond The reaction rate is improved, and the moisture permeability of the cured film can be expected to be reduced. Moreover, the improvement of the low temperature developability of the photosensitive resin composition layer may be seen.
  • (C2) As a compound having one polymerizable group in the molecule, a compound obtained by adding (meth) acrylic acid to one end of polyalkylene oxide, (meth) acrylic acid added to one end, and the other end And the like, and the like.
  • compound (c3) having an ethylenically unsaturated double bond for example, a compound having a (meth) acryloyl group at both ends of a polyalkylene oxide chain, or a polyethylene oxide chain and a polypropylene oxide chain And a compound having a (meth) acryloyl group at both ends of an alkylene oxide chain bonded to each other in a random or block manner, a compound having bisphenol A modified with an alkylene oxide and having a (meth) acryloyl group at both ends It is done.
  • the compound (c3) having an ethylenically unsaturated double bond is a urethane which is a reaction product of a diisocyanate compound and a compound having a hydroxyl group and a (meth) acryl group in one molecule.
  • Compounds and the like Compounds and the like.
  • Commercially available compounds having an ethylenically unsaturated double bond include A-TMMT (made by Shin-Nakamura Chemical Co., Ltd.) as pentaerythritol tetraacrylate, and POB-A (Kyoeisha Chemical Co., Ltd.) as m-phenoxybenzyl acrylate.
  • the content of the compound having an ethylenically unsaturated double bond in the photosensitive resin composition is the mass of the photosensitive resin composition from the viewpoints of resolution, conductor adhesion of the cured film, and moisture permeability reduction.
  • the reference is preferably 20% by mass to 60% by mass, and more preferably 30% by mass to 50% by mass.
  • the photopolymerization initiator (D) is a compound capable of generating radicals with active light and polymerizing an ethylenically unsaturated group-containing compound.
  • the photopolymerization initiator according to the present embodiment is a compound capable of generating radicals with active light and polymerizing an ethylenically unsaturated group-containing compound or the like.
  • benzophenone N, N, N ′, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N, N ′, N′-tetraethyl- 4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- Aromatic ketones such as (methylthio) phenyl] -2-morpholino-propanone-1, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide; benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether Benzoins such as benzoin, methylbenzoin and
  • oxime ester compounds are preferable from the viewpoints of improving the rust prevention property of the conductor, reducing the moisture permeability of the cured film, and improving the chemical resistance, and among these, compounds having a high molar extinction coefficient of 365 nm are more preferable.
  • an oxime initiator having a high absorption coefficient at a wavelength of 365 nm a highly sensitive protective film can be obtained by i-line exposure.
  • an oxime ester compound is preferable, and among these, a compound having a high molar extinction coefficient of 365 nm is more preferable.
  • a highly sensitive protective film can be obtained by i-line exposure. Thereby, high surface curability is obtained, it is speculated that the penetration of sodium ions in the development process as described above can be suppressed, and as a result, high rust prevention property of the conductor can be obtained.
  • 1,2-octanedione, 1-[(4-phenylthio) phenyl-, 2- (O-benzoyloxime)] (manufactured by BASF Japan Ltd., Irgacure Oxe01, product name) Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (manufactured by BASF Japan Ltd., Irgacure Oxe02), 1 -[4- (phenylthio) phenyl] -3-cyclopentylpropane-1,2-dione-2- (O-benzoyloxime) (TR-PBG-305, product name) from Changzhou Power Electronics New Materials Co., Ltd., and 1, 2-propanedione, 3-cyclohexyl-1- [9-ethyl-6- (2-furanylcarbonyl) -9H-
  • the content of the photopolymerization initiator in the photosensitive resin composition is 0.1% by mass to 10% by mass based on the mass of the photosensitive resin composition, and is a viewpoint of sensitivity and resolution. Therefore, the content is more preferably 0.3% by mass to 5% by mass. If the content of the photopolymerization initiator is in the range of 0.1% by mass to 10% by mass, the photosensitivity will be sufficient, and the absorption on the surface of the composition will increase when irradiated with actinic rays. Problems such as insufficient internal photocuring and a decrease in visible light transmittance can be suppressed.
  • Thermal crosslinking agent is a compound containing (A) an alkali-soluble resin, (B) a carboxyl group and an ethylenically unsaturated group or an unreacted (B) ethylenically unsaturated double bond by heat.
  • a thermal cross-linking agent added at the same time it means a compound causing an addition reaction or a condensation polymerization reaction.
  • the temperature at which the addition reaction or condensation polymerization reaction occurs is preferably 100 ° C to 150 ° C. The addition reaction or condensation reaction occurs during heat treatment after pattern formation by development.
  • thermal crosslinking agent examples include, but are not limited to, a blocked isocyanate compound, a diol compound, an epoxy compound, and a thermal crosslinking agent described in paragraph [0054] of International Publication No. 2016/047691.
  • the blocked isocyanate compound is a compound obtained by reacting a blocking agent with an isocyanate compound having two or more isocyanate groups in the molecule.
  • isocyanate compound examples include 1,6-hexane diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, and 2,6-tolylene diisocyanate.
  • the blocking agent examples include alcohols, phenols, ⁇ -caprolactam, oximes, active methylenes, mercaptans, amines, imides, acid amides, imidazoles, ureas, and carbamine.
  • examples include acid salts, imines, and sulfites.
  • blocked isocyanate compound examples include hexamethylene diisocyanate block isocyanate (for example, Duranate SBN-70D, SBB-70P, SBF-70E, TPA-B80E, 17B-60P, MF-B60B, E402- manufactured by Asahi Kasei Corporation).
  • hexamethylene diisocyanate block isocyanate for example, Duranate SBN-70D, SBB-70P, SBF-70E, TPA-B80E, 17B-60P, MF-B60B, E402- manufactured by Asahi Kasei Corporation.
  • a diol compound refers to a compound containing two hydroxyl groups per molecular chain.
  • the skeleton include those containing hydrocarbon groups such as aliphatic, aromatic and alicyclic groups.
  • Specific examples of the diol compound include polytetramethylene diol (for example, P4TMG650, PTMG850, PTMG1000, PTMG1300, PTMG1500, PTMG1800, PTMG2000, and PTMG3000 manufactured by Mitsubishi Chemical Corporation), polybutadiene diol (for example, Nippon Soda Co., Ltd.) Manufactured by G-1000, G-2000, and G-3000), hydrogenated polybutadiene diol (for example, GI-1000, GI-2000, and GO-3000 manufactured by Nippon Soda Co., Ltd.), polycarbonate diol (for example, Asahi Kasei) DURANOL T5651, DURANOL T5652, DURANOL T4671
  • the thermal crosslinking agent is preferably a blocked isocyanate compound from the viewpoint of storage stability of the transfer film and reduced moisture permeability of the cured film, and is further used in combination with a diol compound from the viewpoint of low-temperature developability of the photosensitive resin composition layer. It is more preferable.
  • the content of the thermal crosslinking agent in the photosensitive resin composition is 0.2% by mass to 40% by mass based on the mass of the photosensitive resin composition, and from the viewpoint of developability and low water permeability.
  • the content is more preferably 1% by mass to 30% by mass, and further preferably 2% by mass to 20% by mass.
  • the block isocyanate compound is a carboxyl group or hydroxyl group of a compound containing (A) an alkali-soluble resin or (B) a carboxyl group and an ethylenically unsaturated group, or a combined diol compound in a heat treatment after pattern formation by development. Since it reacts with the hydroxyl group, the moisture permeability of the cured film is lowered, and the rust prevention property for protecting the substrate, the electrode and the like is improved.
  • the blocked isocyanate compound is crosslinked with (A) an alkali-soluble resin and / or (B) a compound containing a carboxyl group and an ethylenically unsaturated group, thereby increasing the crosslinking density of the cured film and reducing the water diffusibility. Therefore, it is considered that the moisture permeability of the cured film is lowered and the rust prevention property of the conductor is improved. Moreover, since the isocyanate group is sealed with the blocking agent in the blocked isocyanate, the reaction with the (A) alkali-soluble resin or diol compound at room temperature is suppressed, and the stability of the photosensitive resin composition and the transfer film is improved. Kept.
  • the diol compound Since the diol compound has a hydrophilic hydroxyl group, the developability is good. In addition, in the heat treatment after pattern formation by development, the hydroxyl group of the diol compound reacts with the blocked isocyanate compound, so that excellent rust resistance of the conductor is maintained.
  • the molecular weight of the diol compound is preferably from 300 to 3,000, more preferably from 500 to 2,000, from the viewpoint of developability.
  • the moisture permeability of the cured film is deteriorated, which may be a factor that impairs the rust prevention performance of the conductor.
  • the diol compound is preferably added so that the hydroxyl value of the photosensitive resin composition is 20 mgKOH / g or less, and more preferably 15.0 mgKOH / g or less. Since the moisture permeability of the hardened
  • the (F) rosin ester compound according to the present embodiment is a rosin acid that is a non-volatile component of rosin, a rosin acid that is a tricyclic diterpenoid having 20 carbon atoms, a dimer of rosin acid, a hydrogenated product of rosin acid, and A compound having an ester bond by reacting a compound selected from the group consisting of disproportionates of rosin acid (hereinafter collectively referred to as “rosin acid derivative”) with any of a hydroxyl compound, a phenol compound, and a glycidyl compound, It is a compound having an ester bond by glycidylating a rosin acid derivative and reacting either a carboxyl compound or a phenol compound.
  • rosin acid derivative a compound selected from the group consisting of disproportionates of rosin acid
  • rosin ester compounds include, for example, Arakawa Chemical Co., Ltd. products such as the ester gum series, pine crystal series, super ester series, pencel series, beam set 101, etc.
  • the company's products include the Harrier Star Series, Neotor Series, and Harituck Series.
  • the rosin ester compound has a cycloaliphatic structure and an ester structure, so that the hydrophobicity is increased, but (A) an alkali-soluble resin, (B) a carboxyl group and ethylene in the photosensitive resin composition. Since the compatibility with the compound containing a polymerizable unsaturated group, (C) the photopolymerizable compound, and (D) the photopolymerization initiator is good, the developability as a composition is not hindered. It has excellent performance balance of low temperature developability, moisture permeability of cured film, and rust prevention of conductor.
  • the acid value of the (F) rosin ester compound is more preferably 20 mgKOH / g or less.
  • the acid value of the (F) rosin ester compound is more preferably 20 mgKOH / g or less.
  • the above-mentioned products of Arakawa Chemical Co., Ltd. and Harima Kasei Co., Ltd. For example, Pine Crystal KE-100, Ester Gum 105, Super Ester A-115, Super Ester A-125, Pencel A, Pencel C, Pencel D-125, Pencel D-135, Pencel D-160, Beam Set 101, Harrier Star S, Neotol 125HK, Haritac F105, Haritac FK125, Haritac PCJ, and the like.
  • the rosin ester compound (F) preferably has a softening point of 100 ° C. or higher.
  • Specific examples of compounds satisfying these conditions include, for example, ester gum 105, Superester A-115, Superester A-125, Pencel A, Pencel C, Pencel D-125, Pencel D-135, Pencel D-160, Neotol 125HK, etc., with a softening point of 110 ° C. or higher
  • Particularly preferred specific compounds satisfying these conditions are Superester A-115, Superester A-125, Pencel A, Pencel C, Pencel D-125, Pencel D-135, Pencel D-160, Neotol 125HK is mentioned.
  • the rosin ester compound may be used alone or in combination of two or more.
  • the content of the rosin ester compound in the photosensitive resin composition is 1% by mass to 20% by mass with respect to 100% by mass of the total solid content of the photosensitive resin composition. From 5% by mass to 20% by mass, more preferably from 5% by mass to 15% by mass from the viewpoint of adhesion to the substrate. (F) When the content of the rosin ester compound is in the range of 1% by mass to 20% by mass, the performance balance between the low temperature developability of the transfer film and the moisture permeability of the cured film is good.
  • the rust preventive agent according to the present embodiment refers to a compound having a rust preventive effect, such as a substance that forms a film on a metal surface to prevent corrosion or rust of the metal.
  • heterocyclic compounds containing N, S, O and the like are preferable.
  • heterocyclic compounds containing N, S, O and the like are preferable.
  • the derivatives described here include compounds in which a substituent is introduced into the base structure.
  • a substituent is introduced into the base structure.
  • transduced the substituent into tetrazole is contained.
  • the substituent is not particularly limited.
  • the substituent may be a hydrocarbon group (saturated or unsaturated, may be linear or branched, and may include a cyclic structure in its structure), or a hydroxyl group or a carbonyl group.
  • Carboxyl groups amino groups, amide groups, nitro groups, cyano groups, thiol groups, and substituents containing one or more functional groups having heteroatoms such as halogen (fluorine, chlorine, bromine, iodine, etc.) groups.
  • halogen fluorine, chlorine, bromine, iodine, etc.
  • the heterocyclic compound has a heterocyclic ring composed of C and N and / or S, and the number of N atoms in the same heterocyclic ring is 3 or less, or S A compound having 3 or less atoms or a total number of N and S atoms of 3 or less is preferred.
  • More preferred heterocyclic compounds are triazole and its derivatives, imidazole and its derivatives, imidazoline and its derivatives, thiazole and its derivatives, isothiazole and its derivatives, thiadiazole and its derivatives, thiophene and its derivatives, and the like.
  • the compound is more preferably benzotriazole and its derivatives, and imidazole and its derivatives.
  • Triazoles such as 1,2,3-triazole, 1,2,4-triazole, etc .
  • Triazole derivatives such as 3-mercaptotriazole, 3-amino-5-mercaptotriazole, benzotriazole, 1H-benzotriazole-1-acetonitrile, 1- [N, N-bis (2-ethylhexyl) aminomethyl] benzotriazole, 1- (2-di-n-butylaminomethyl) -5-carboxybenzotriazole, 1- (2-di-n-butylaminomethyl) -6-carboxybenzotriazole, 1H-benzotriazole-1-methanol, 5 -Met
  • Imidazole Imidazole derivatives such as undecyl imidazole, benzimidazole, 5-carboxybenzimidazole, 6-bromobenzimidazole, 5-chlorobenzimidazole, 2-hydroxybenzimidazole, 2- (1-hydroxymethyl) benzimidazole, 2 -Methylbenzimidazole, 5-nitrobenzimidazole, 2-phenylbenzimidazole, 2-aminobenzimidazole, 5-aminobenzimidazole, 5-amino-2-mercaptobenzimidazole, etc .; An imidazoline; an imidazoline derivative such as 2-undecylimidazoline, 2-propyl-2-imidazoline, 2-phenylimidazoline; Thiazole; thiazole derivatives such as 2-amino-4-methylthiazole, 5- (2-hydroxyethyl) -4-methylthiazole, benzothiazole, 2-mercaptobenzothiazole, 2-amino
  • Isothiazole isothiazole derivatives such as 3-chloro-1,2-benzisothiazole; Thiadiazoles such as 1,2,3-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole and the like; thiadiazole derivatives such as 4-amino-2,1,3-benzothiadiazole, 2-amino -5-mercapto-1,3,4-thiadiazole, 2-amino-5-methyl-1,3,4-thiadiazole, 2-amino-1,3,4-thiadiazole, 5-amino-1,2,3 -Thiadiazole, 2-mercapto-5-methyl-1,3,4-thiadiazole, etc .; Thiophene; thiophene derivatives such as 2-thiophenecarboxylic acid, methyl 3-amino-2-thiophenecarboxylate, 3-methylbenzothiophene and the like.
  • benzotriazole, 5-carboxybenzotriazole, 1-hydroxybenzotriazole, and 5-chlorobenzotriazole are particularly preferable from the viewpoints of rust prevention of the conductor and low-temperature developability of the transfer film.
  • component (G) tetrazole and its derivatives, triazole and its derivatives, indazole and its derivatives, and thiadiazole and its derivatives are preferable from the viewpoint of the rust prevention property of the conductor and the adhesion between the cured film and the base material.
  • tetrazole examples include 1H-tetrazole.
  • tetrazole derivatives include 5-amino-1H-tetrazole, 5-methyl-1H-tetrazole, 1-methyl-5-ethyl-1H-tetrazole, 1-methyl-5-mercapto-1H-tetrazole, 1- Examples include phenyl-5-mercapto-1H-tetrazole, 1- (dimethylaminoethyl) -5-mercapto-1H-tetrazole, and 5-phenyl-1H-tetrazole.
  • indazole is 1H-indazole.
  • indazole derivatives include 5-aminoindazole, 6-aminoindazole, 1-benzyl-3-hydroxy-1H-indazole, 5-bromoindazole, 6-bromoindazole, 6-hydroxyindazole, 3-carboxyindazole and 5-nitroindazole. And indazole.
  • triazole and its derivatives and thiadiazole and its derivatives are as already described above.
  • 5-amino-1H-tetrazole, 5-carboxybenzotriazole, 5-aminoindazole and 5-amino-1,2, 3-thiadiazole is particularly preferred.
  • 1 type of the antirust agent demonstrated above may be used independently, and 2 or more types may be used together.
  • the content of the rust inhibitor in the photosensitive resin composition is preferably 0.05% by mass or more based on the mass of the photosensitive resin composition from the viewpoint of rust prevention of the conductor or low temperature developability of the transfer film. It is 10% by mass, more preferably 0.1% by mass to 5% by mass, and still more preferably 0.2% by mass to 3% by mass.
  • ⁇ Other ingredients> in addition to components (A) to (G), as other component (H), an oligomer having a carboxyl group and an ethylenically unsaturated group, an aluminum salt to which 3 mol of nitrosophenylhydroxylamine has been added, etc.
  • Polymerization inhibitors, antioxidants, adhesion aids, leveling agents, fillers, antifoaming agents, flame retardants, etc. can also be included in the photosensitive resin composition, and these can be used alone or in combination of two or more. Can be used.
  • GPC gel permeation chromatography
  • S ⁇ 50k is in the range of 1.0 to 9.0%, a photosensitive resin composition having excellent low-temperature developability can be provided.
  • S ⁇ 50k is preferably in the range of 2.5 to 6.7% from the viewpoint of low-temperature developability.
  • the component belonging to the region of molecular weight M ⁇ 50000 in the differential molecular weight distribution curve contains an aromatic ring.
  • the component having a molecular weight M ⁇ 50000 and containing an aromatic ring can be derived from, for example, the components (A1) to (A4) described above.
  • the high molecular weight component of the photosensitive resin composition in the present embodiment includes an acidic functional group and has a refractive index n2 of 1.560 or more.
  • the refractive index of the photosensitive resin composition layer is preferably 1.550 or more.
  • it is preferable that the refractive index of the photosensitive resin composition layer is 1.630 or less.
  • 10.0 g of the photosensitive resin composition or its layer was precisely weighed as a sample in a 100 mL Erlenmeyer flask, 30.0 g of tetrahydrofuran (THF) was added thereto, the container was sealed, Stir with a stirrer for 1 hour. After removing insolubles by filtration, 60.0 g of cyclohexane (Cy) is added dropwise to the THF solution over 10 minutes, and the mixture is stirred at 23 ° C. for 1 hour.
  • THF tetrahydrofuran
  • the acid value is measured in the same manner as described above for (A) the alkali-soluble resin.
  • a method for measuring the refractive index n2 of a component insoluble in a THF / Cy mixed solvent is shown below.
  • an organic solvent for example, ethanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol
  • a solution dissolved in propylene glycol-1-monomethyl ether-2-acetate At this time, the solid content concentration is adjusted to 10 to 70% by mass.
  • the resulting solution can be applied to any substrate that is resistant to the solution.
  • PET polyethylene terephthalate
  • the organic component constituting the photosensitive resin composition in the present embodiment has a molecular weight (M) of an insoluble component when the mass ratio of tetrahydrofuran (THF) / cyclohexane (Cy) mixed solvent is 1 / 1.3.
  • M molecular weight of an insoluble component when the mass ratio of tetrahydrofuran (THF) / cyclohexane (Cy) mixed solvent is 1 / 1.3.
  • the acid value A1 is 100 mgKOH / g or more and / or
  • the refractive index n1 is 0.005 or less smaller than the n2.
  • acid value A1 is 200 mgKOH / g or less.
  • 10.0 g of the photosensitive resin composition or its layer was precisely weighed as a sample in a 100 mL Erlenmeyer flask, 39.1 g of tetrahydrofuran (THF) was added thereto, the container was sealed, Stir with a stirrer for 1 hour. After removing insolubles by filtration, 50.9 g of cyclohexane (Cy) is added dropwise to the THF solution over 10 minutes, and the mixture is stirred at 23 ° C. for 1 hour.
  • THF tetrahydrofuran
  • the hydroxyl value (mgKOH / g) of the photosensitive resin composition in the present embodiment is preferably 20 or less, and more preferably 15.0 or less. Since the moisture permeability of the hardened
  • the refractive index of the photosensitive resin composition in the present embodiment is preferably 1.550 or more. Moreover, it is preferable that the refractive index of the photosensitive resin composition layer is 1.630 or less.
  • the photosensitive resin layer according to the present embodiment has a thickness of 40 ⁇ m or less, and the absorbance at a wavelength of 365 nm of the photosensitive resin layer is 0.01 to 0.05 per 1 ⁇ m of the thickness of the photosensitive resin layer. It is preferable. Since the flexibility deteriorates if the film thickness of the photosensitive resin layer is too thick, the thickness of the photosensitive resin layer is preferably 40 ⁇ m or less, from the viewpoint of following the unevenness of the wiring, and from the viewpoint of ensuring rust prevention, 3 ⁇ m or more is preferable.
  • the transfer film includes a photosensitive resin layer made of a photosensitive resin composition and a support film. Specifically, a layer made of the above-described photosensitive resin composition is laminated on the support film. If necessary, the transfer film may have a protective film on the surface of the photosensitive resin layer opposite to the support film side.
  • the support film used in this embodiment is preferably a transparent film that transmits light emitted from the exposure light source.
  • support films include polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, and polymethyl methacrylate copolymer film.
  • the haze of the support film is preferably 5 or less. The smaller the thickness of the support film, the more advantageous in terms of resolution and economy. However, in order to maintain the strength, the thickness is preferably 10 ⁇ m to 30 ⁇ m.
  • the protective film used for the transfer film is sufficiently smaller in adhesion to the photosensitive resin layer than the support film and can be easily peeled off.
  • a protective layer a polyethylene film, a polypropylene film, etc. can be used preferably, for example.
  • the production method of the transfer film includes a step of applying a coating liquid on a support (for example, a support film) and drying, and further includes a step of laminating a protective film on the photosensitive resin layer as necessary.
  • the coating liquid can be obtained by uniformly dissolving the photosensitive resin composition described above in a solvent.
  • Examples of the solvent that dissolves the photosensitive resin composition include ketones typified by methyl ethyl ketone (MEK); alcohols typified by methanol, ethanol, or isopropanol.
  • MEK methyl ethyl ketone
  • the solvent is preferably added to the photosensitive resin composition so that the viscosity of the solution of the photosensitive resin composition applied onto the support is 10 mPa ⁇ s to 800 mPa ⁇ s at 25 ° C.
  • Application methods include, for example, doctor blade coating method, Meyer bar coating method, roll coating method, screen coating method, spinner coating method, inkjet coating method, spray coating method, dip coating method, gravure coating method, curtain coating method, die coating Examples thereof include a coating method.
  • the drying temperature is preferably 50 ° C. to 130 ° C.
  • the drying time is preferably 30 seconds to 30 minutes.
  • the transfer film is preferably used to form a protective film for the conductor portion.
  • the conductor portion is made of a copper electrode, nickel, palladium, silver, titanium, molybdenum, and the like.
  • An alloy electrode with copper or a transparent electrode is more preferable.
  • the transfer film can be used as a protective film for the lead-out wiring in the frame area of the touch panel (touch sensor or force sensor) and as a protective film for the copper electrode in the sensing area.
  • Formation of the resin pattern using the transfer film includes the following steps: A laminating step of laminating the transfer film described above on a substrate; An exposure step for exposing the laminated photosensitive resin laminate; and a development step for developing the exposed transfer film; It can carry out by the manufacturing method of the resin pattern containing this. Furthermore, in order to use the resin pattern as a protective film for the conductor part, a process for forming a cured film pattern by subjecting the resin pattern to post-exposure treatment and / or heat treatment after the development step is included as a method for producing the resin pattern. Is preferred.
  • a base material in which copper wiring is formed on a copper clad laminate, a glass base material, a transparent resin base material with a transparent electrode (for example, ITO, Ag nanowire base material, etc.), or a metal electrode (for example, Cu , Al, Ag, Ni, Mo, and at least two kinds of alloys thereof, or the like can be used.
  • a touch panel substrate or a touch sensor substrate (for example, a force sensor) can be used.
  • a flexible copper-clad laminate, a touch panel electrode forming substrate, or a touch sensor electrode forming substrate is formed by forming a copper layer, a transparent electrode, or a metal layer as a raw material of a metal electrode on a flexible film. It is a material.
  • the film which consists of film raw materials such as a polyimide, polyester (PET, PEN), a cycloolefin polymer (COP), is mentioned, for example.
  • the thickness of the film is preferably 10 ⁇ m to 100 ⁇ m.
  • the alloy containing copper as a main component other than pure copper can be used.
  • the “main component” means that at least 50% by mass of the alloy is copper.
  • the alloy metal for example, an alloy of nickel, palladium, silver, titanium, molybdenum or the like and copper can be cited.
  • the thickness of the copper layer is preferably 50 nm to 2 ⁇ m. From the viewpoint of the uniformity of the copper layer, the thickness of the copper layer is more preferably 100 nm or more.
  • a photosensitive resin layer is formed on the copper layer of the substrate by performing a process of laminating a transfer film on the substrate as described above.
  • the transfer film has a protective layer
  • the protective layer is preferably peeled off, and then the transfer film is heat-pressed and laminated on the substrate surface with a laminator.
  • the transfer film may be laminated only on one side of the substrate surface, or may be laminated on both sides.
  • the heating temperature is generally about 40 ° C to 160 ° C.
  • the thermocompression bonding may be performed using a two-stage laminator provided with two rolls, or may be performed by repeatedly passing the transfer film and the substrate through the roll a plurality of times. .
  • the roll temperature is preferably 40 ° C. to 100 ° C., more preferably 40 ° C. to 80 ° C.
  • an exposure process is performed using an exposure machine. If necessary, the support film is peeled off from the transfer film, and the photosensitive resin layer is exposed with active light through a photomask.
  • the exposure amount is determined by the light source illuminance and the exposure time. The exposure amount may be measured using a light meter. Examples of the exposure machine include a scattered light exposure machine using an ultra-high pressure mercury lamp as a light source, a parallel light exposure machine with adjusted parallelism, and a proximity exposure machine that provides a gap between a mask and a workpiece.
  • an exposure machine a projection type exposure machine with a mask to image size ratio of 1: 1, a reduction projection exposure machine called a high illumination stepper (registered trademark), or a concave mirror called a mirror projection aligner (registered trademark) is used.
  • the used exposure machine can be mentioned.
  • Direct drawing exposure is a method in which exposure is performed by drawing directly on a substrate without using a photomask.
  • the light source for example, a solid laser having a wavelength of 350 nm to 410 nm, a semiconductor laser, or an ultrahigh pressure mercury lamp is used.
  • the drawing pattern is controlled by a computer.
  • the exposure amount in this case is determined by the light source illuminance and the moving speed of the substrate.
  • a developing process is performed using a developing device. After exposure, when there is a support film on the photosensitive resin layer, the support film is removed as necessary, and then the unexposed portion is developed and removed using a developer of an alkaline aqueous solution to obtain a resin pattern.
  • an aqueous solution (alkaline aqueous solution) of Na 2 CO 3 or K 2 CO 3 is preferably used.
  • the alkaline aqueous solution is appropriately selected according to the characteristics of the photosensitive resin layer, but a Na 2 CO 3 aqueous solution having a concentration of about 0.2% by mass to 2% by mass and about 20 ° C. to 40 ° C. is generally used.
  • the developer temperature is preferably less than 30 ° C.
  • a surface active agent, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like may be mixed in the alkaline aqueous solution.
  • an amine-based alkaline aqueous solution such as a tetramethylammonium hydroxide (TMAH) aqueous solution can also be used.
  • TMAH tetramethylammonium hydroxide
  • an aqueous solution of Na 2 CO 3 of 1% by mass and 25 ° C. to 30 ° C. is particularly preferable.
  • Examples of the developing method include known methods such as alkaline water spraying, showering, rocking immersion, brushing, and scraping.
  • the base of the alkaline aqueous solution remaining in the resin pattern is treated with an acid treatment (neutralization treatment) using known methods such as spraying, rocking immersion, brushing, and scraping using an organic acid, an inorganic acid or an aqueous acid solution thereof. )can do. Furthermore, after the acid treatment (neutralization treatment), a step of washing with water can be performed.
  • a post-exposure step and / or a heating step may be further performed.
  • the exposure amount in the post exposure treatment is preferably 200mJ / cm 2 ⁇ 1,000mJ / cm 2, it is preferable to carry out the treatment at 40 ° C. ⁇ 200 ° C.
  • the heating step from the viewpoint of the manufacturing process, heat treatment time Is preferably 60 minutes or less.
  • a heating furnace of an appropriate method such as hot air, infrared rays, far infrared rays, or the like can be used.
  • an atmosphere of the heat treatment an N 2 atmosphere or an N 2 / O 2 atmosphere can be given. .
  • the transfer film has good tack, low-temperature laminating properties, low-temperature developability, moisture permeability of the cured film, and adhesion to the conductor base material, and the conductor parts such as wiring and electrodes
  • a photosensitive resin composition and a transfer film suitable for protection can be provided.
  • Such a transfer film is suitable as a solder resist for a protective film such as a wiring for a touch panel, a touch sensor or a force sensor, an electrode, or a printed wiring board.
  • the touch panel display device By forming the cured film of the transfer film according to the present embodiment on the touch panel substrate, the touch panel display device having the cured film of the transfer film, and the cured film of the transfer film and the touch sensor and / or the force sensor are included.
  • An apparatus can be provided.
  • the base material used for a touch panel, a touch sensor, or a force sensor for example, a glass plate, a plastic plate, a plastic film, a ceramic plate etc., is mentioned.
  • electrodes for touch panel such as ITO, Cu, Al, Ag, Ni, Mo and an alloy containing at least two of them, or metal wiring, which is a target for forming a protective film, are provided.
  • An insulating layer may be provided between the electrodes.
  • the touch panel substrate having the touch panel electrode can be obtained, for example, by the following procedure. After a metal film is formed on a touch panel substrate such as polyester or COP film by sputtering in the order of ITO and Cu, an etching photosensitive film is pasted on the metal film to form a desired resist pattern, which is unnecessary Cu is removed with an etching solution such as an iron chloride aqueous solution, and the resist pattern is further removed and removed.
  • a metal film is formed on a touch panel substrate such as polyester or COP film by sputtering in the order of ITO and Cu
  • an etching photosensitive film is pasted on the metal film to form a desired resist pattern, which is unnecessary Cu is removed with an etching solution such as an iron chloride aqueous solution, and the resist pattern is further removed and removed.
  • the method for forming a cured film as a protective film on a touch panel substrate is a first step of laminating the transfer film according to the present embodiment on the touch panel substrate, and a predetermined portion of the protective film is irradiated with actinic rays.
  • a touch panel display device having a cured film of the transfer film, or a cured film of the transfer film and a touch sensor and / or a force sensor is provided.
  • An apparatus can be suitably provided.
  • the copolymer composition, weight average molecular weight, acid value, and hydroxyl value of the resulting acrylic copolymer are shown in Table 1.
  • the measurement of the weight average molecular weight of an acrylic copolymer, an acid value, and a hydroxyl value was performed by the method described in the detail of said ⁇ (A) alkali-soluble resin>.
  • Table 2 shows the weight average molecular weight, acid value, and hydroxyl value of the compound containing the carboxyl group and the ethylenically unsaturated group.
  • the measurement of the weight average molecular weight of the compound containing a carboxyl group and an ethylenically unsaturated group, an acid value, and a hydroxyl value was performed by the method described in the detail of said ⁇ (A) alkali-soluble resin>.
  • the refractive index measurement of the compound containing a carboxyl group and an ethylenically unsaturated group was performed by the following method.
  • ⁇ Refractive index evaluation method> Using the 532 nm laser light source with the refractive index measuring device (Prism Coupler Model 2010 / M, manufactured by Metricon), the sample produced by the above method was used at any four locations in the plane direction of the sample, and any four in the vertical direction. The refractive index of the place was measured and the average value was computed. The refractive index measurement results are shown in Table 2. Next, a method for producing an evaluation transfer film of Examples and Comparative Examples will be described, and further, an evaluation method for the obtained transfer film and an evaluation result thereof will be shown.
  • the photosensitive resin composition preparation liquid was uniformly applied to the surface of a 16 ⁇ m-thick polyethylene terephthalate film (FB40, manufactured by Toray Industries, Inc.) as a support using a blade coater, and 10% in a dryer at 95 ° C. It was dried for a minute to form a uniform photosensitive resin layer on the support.
  • the thickness of the photosensitive resin layer was 8 ⁇ m and 40 ⁇ m.
  • a transfer film for evaluation was obtained by laminating a 33 ⁇ m thick polyethylene film (manufactured by Tamapoly Co., Ltd., GF-858) as a protective film on the surface of the photosensitive resin layer.
  • Tables 1 to 3 show the names of the material components in the photosensitive resin composition preparations represented by abbreviations in Tables 4 to 6.
  • GPC measurement of photosensitive resin composition The protective film of the transfer film obtained above was peeled off, 0.30 g of the photosensitive resin layer was weighed from the transfer film, and this was dissolved in 20 g of THF. GPC was measured using gel permeation chromatography (GPC) manufactured by JASCO Corporation under the following conditions to obtain a GPC elution curve.
  • GPC gel permeation chromatography
  • the differential molecular weight distribution curve of Example 5 is shown in FIG. Tables 4 to 6 show R 20k / 5k values and S ⁇ 50k values of Examples 1 to 22 and Comparative Examples 1 to 10.
  • the suspended solution was subjected to solid-liquid separation with a high-speed centrifuge at 5000 rpm for 10 minutes, and the supernatant was removed by decantation.
  • Measurement of acid value A2 1.0 g of the insoluble component obtained above was precisely weighed and dissolved in 9.0 g of THF.
  • the refractive index was measured using a prism coupler (laser refractive index measurement model 2010, laser light wavelength: 532 nm) manufactured by Metricon, with the insoluble component layer in contact with the prism.
  • the acid value A1 and the refractive index n1 are also measured by the acid value A2 and the refractive index. The same method as that for measuring n2 was used.
  • hydroxyl value of photosensitive resin composition The hydroxyl value of the photosensitive resin composition layer constituting the transfer film was measured as follows. First, 1 g of the photosensitive resin composition which is a measurement target of the hydroxyl value was collected from the transfer film and precisely weighed. 10 mL of a 10% by mass acetic anhydride pyridine solution was added to the precisely weighed photosensitive resin composition to dissolve it uniformly and heated at 100 ° C. for 1 hour. After heating, 10 mL of water and 10 mL of pyridine are added and heated at 100 ° C. for 10 minutes.
  • the tack property of the transfer film was evaluated as follows. First, the prepared transfer film is allowed to stand for 24 hours in an environment of 23 ° C. and 50% RH, and then the protective film is peeled off at a speed of 10 cm / second, so that the photosensitive resin composition is attached to the surface of the protective film. Was confirmed visually. Next, absorbent cotton was rubbed on the surface of the photosensitive resin composition layer after peeling the protective film, and the surface of the photosensitive resin composition layer was visually observed.
  • B The photosensitive resin composition does not adhere to the surface of the peeled protective film, but the lint of absorbent cotton sticks to the surface of the photosensitive resin composition layer.
  • C The photosensitive resin composition adheres to the surface of the peeled protective film.
  • the laminating property of the transfer film was evaluated as follows. While removing the protective film of the transfer film, a hot roll laminator (VA-400III, manufactured by Taisei Laminator Co., Ltd.) is formed on the copper surface (size: 5 cm ⁇ 10 cm) of the substrate on which the resin, ITO and sputtered copper are laminated in this order. Was laminated under the condition of a roll temperature of 80 ° C. The air pressure was set to 0.4 MPa, and the laminating speed was set to 1.5 m / min. Evaluation was carried out as A when the transfer film was adhered to the copper surface of the substrate and as B when it was not adhered at 80 ° C.
  • VA-400III manufactured by Taisei Laminator Co., Ltd.
  • sample preparation method The sample after the evaluation of the laminate property was used as it was.
  • a sample laminated at a roll temperature of 100 ° C. was prepared.
  • the laminated sample was allowed to stand for 15 minutes, and then a PET mask and a stuber 21-step tablet on the support film (optical density 0.00 was the first step, and the optical density was 0.15 for each step.
  • Incremental step tablets were placed side by side, the optimum exposure amount of each composition was determined from the PET mask and step tablet side, and exposure was performed with a parallel light exposure machine (HMW-801, manufactured by Oak Manufacturing Co., Ltd.).
  • the PET mask As the PET mask, a mask having a pattern in which an unexposed portion becomes a circular hole was used. Next, after leaving still for 15 minutes or more, the support is peeled off, and using a developing device manufactured by Fuji Kiko Co., Ltd., a 1% by mass Na of 28 ° C. to 30 ° C. at a developing spray pressure of 0.12 MPa with a full cone type nozzle. A 2 CO 3 aqueous solution was sprayed for 45 seconds and developed to dissolve and remove the unexposed portions of the photosensitive resin layer.
  • the water washing step is carried out at the same time as the development step with a flat type nozzle at a water washing spray pressure of 0.12 MPa, and the water washed sample is dried by air blow to prepare a sample for evaluation of developability.
  • the optimum exposure amount is defined as an exposure amount such that the number of steps remaining in the film when the exposure is performed through the stuber 21-step tablet becomes 7 to 8 steps.
  • Moisture permeability test ⁇ sample preparation method> While peeling off the protective film of the transfer film having a thickness of the photosensitive resin layer of 40 ⁇ m, Lamination was performed on 4 filter papers (manufactured by Advantech) using a hot roll laminator (manufactured by Taisei Laminator Co., Ltd., VA-400III). The roll temperature was set to 80 ° C. (100 ° C. when the above-described evaluation of the laminate property was “x”), the air pressure was set to 0.4 MPa, and the lamination speed was set to 1.0 m / min. After leaving still for 15 minutes, the optimal exposure amount of each composition was exposed to the whole surface with the scattered light exposure machine from the support film side of the protective film.
  • the support film After leaving still for 30 minutes, the support film is peeled off, exposed with an exposure amount of 350 mJ / cm 2 from the photosensitive layer side with a scattered light exposure machine, and then processed at 150 ° C. for 30 minutes in a hot air circulating oven. A sample was prepared. The optimum exposure amount has the same definition as in the sample preparation method for developing property evaluation.
  • B moisture permeability 201-250 g / (m 2 ⁇ day)
  • C Moisture permeability of 251 to 300 g / (m 2 ⁇ day)
  • Adhesion evaluation (cross cut test) ⁇ Sample preparation method> While peeling off the protective film of the transfer film having a photosensitive resin layer thickness of 8 ⁇ m, a hot roll laminator (Daisei Laminator (3cm ⁇ 3cm)) is formed on the alloy surface (size: 3 cm ⁇ 3 cm) of the substrate on which the resin and sputtered copper nickel alloy are laminated in this order. Laminate using VA-400III) manufactured by KK The roll temperature was 80 ° C. (the level of the above-mentioned laminating evaluation is 100 ° C.), the air pressure was 0.4 MPa, and the laminating speed was 1.0 m / min.
  • the optimal exposure amount of each composition was exposed to the whole surface with the scattered light exposure machine from the support film side of the protective film.
  • the optimum exposure amount has the same definition as in the sample preparation method for developing property evaluation.
  • the support film was peeled off, and using a developing device manufactured by Fuji Kiko Co., Ltd., a 1% by mass Na 2 CO at 30 ° C. with a developing spray pressure of 0.12 MPa using a full cone type nozzle. Three aqueous solutions were sprayed for 45 seconds and developed, and the unexposed portion of the photosensitive resin layer was dissolved and removed.
  • the water washing step was performed at the same time as the development step with a water spray pressure of 0.12 MPa with a flat type nozzle, and the washed sample was dried by air blow.
  • the developed sample is exposed with a light exposure of 350 mJ / cm 2 from the photosensitive resin layer side with a scattered light exposure machine, and then processed at 150 ° C. for 30 minutes in a hot air circulating oven for evaluation of adhesion. A sample was made.
  • ⁇ Evaluation method> The sample after the above treatment was subjected to a 100 mass cross-cut test with reference to JIS standard K5400.
  • Example 1 to 22 satisfy the requirements specified in the present invention, so that tackiness as a transfer film, low-temperature laminating property and low-temperature developability, and moisture permeability as a cured film are achieved. It is shown that the adhesiveness with the conductor base material is excellent. Further, Example 5 and Example 6 are the difference between the component (B-1) and the component (B-2). By adjusting the hydroxyl value of the composition to 15 mgKOH / g or less, the cured film It turns out that it is excellent in moisture permeability.
  • Comparative Examples 1 to 10 shown in Table 5 do not satisfy any of the requirements stipulated in the present invention. Therefore, tackiness as a transfer film, low temperature laminating or low temperature developability, and as a cured film It has been shown that either the moisture permeability or the adhesion to the conductor base material is inferior.
  • Comparative Example 1 and Comparative Example 9 are photosensitive resin compositions having an A / B mass ratio increased to 6.38. The low-temperature laminating property and low-temperature developability of the transfer film and the moisture permeability of the cured product were each Example 1. The result was inferior to 2.
  • Comparative Examples 2 and 3 are photosensitive resin compositions in which the A / B mass ratio was lowered to 0 to 0.12, but the tackiness and low-temperature developability of the transfer film, and the close contact with the conductor substrate as a cured film The result was inferior.
  • Comparative Example 4 contains (A′-1), which does not satisfy the molecular weight definition of the component (A) defined in the present invention, but the low-temperature developability is inferior to Example 10. became.
  • the component (B) was not blended in the photosensitive resin composition of Comparative Example 5, the results were inferior in low-temperature laminating properties and low-temperature developability as a transfer film.
  • Comparative Example 6 the component (A) was not added and only the component (B-3) was increased.
  • Example 17 Compared with Example 17 or Example 18, the tackiness as a transfer film, the low temperature developability, and It became a result inferior to adhesiveness with the conductor base material as a cured film.
  • the component (A) was not added, and instead the weight average molecular weight and acid value satisfied the definition of the component (A), and the skeleton of any one of the general formulas (1) to (3)
  • the component (B′-1) which is a modified epoxy acrylate acid not included in the structure, was added, but the tackiness and low-temperature developability as a transfer film were poor. From this, it was found that the epoxy acrylate modified product is not compatible with the component (A) of the present invention.
  • Comparative Example 8 does not satisfy the requirements of the weight average molecular weight and refractive index of the component (B) of the present invention, and does not contain any skeleton of the general formulas (1) to (3) in the structure (B′-2 ) Component was added, but the low temperature developability as a transfer film and the moisture permeability of the cured film were inferior.
  • the component (A′-3) that does not satisfy the acid value of the component (A) of the present invention was added, but the results were poor in low-temperature developability and adhesion as a transfer film. . Further, since the component (A′-3) has a high hydroxyl value, the moisture permeability was inferior.
  • the A / B mass ratio which is a requirement defined in the present invention, is in the range of 0.18 to 6.0, as tackiness as a transfer film, low-temperature laminating property, low-temperature developability, and curing. It was found to be important for satisfying the moisture permeability as a film and the adhesion to the conductor base material.
  • the present inventors believe that the low-temperature developability as a transfer film is a surprising result in that both the A / B mass ratio is significantly deteriorated when the A / B mass ratio is less than 0.18 and more than 6.0. Think.
  • Examples 1 to 22 and Comparative Examples 1, 4, 5, and 7 to 9 are excellent in adhesion to the conductor base material.
  • S ⁇ 50k in the differential molecular weight distribution curve of GPC is in the range of 0.2 to 9.0%;
  • S ⁇ 50k was 0.2%, but the adhesion with the conductor base material was slightly inferior.
  • S ⁇ 50k was 0%, but the adhesion to the conductor substrate was inferior.
  • both the rust prevention property and the low-temperature developability are good, and it is suitable for the protection of conductor parts such as wiring and electrodes, and the touch panel, touch sensor, or force. It can be widely used as a protective film for wiring, electrodes and the like for sensor applications and solder resist applications for printed wiring boards.

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Abstract

La présente invention concerne : une composition de résine photosensible qui est appropriée pour la protection d'une partie conductrice telle qu'une électrode et qui permet à un film de transfert d'avoir une propriété d'adhérence satisfaisante, une aptitude au développement à basse température, une propriété de stratification à basse température, une perméabilité à l'humidité lorsqu'elle se présente sous la forme d'un film durci, et une adhérence à un matériau de base conducteur ; un film de transfert ; et son procédé de production. Le film de transfert servant à former un film protecteur destiné à une partie conductrice comprend un film de support et une couche de composition de résine photosensible. La couche de composition de résine photosensible comprend (A) une résine soluble dans les alcalis (à l'exclusion de composés époxy (méth)acrylate modifiés par un acide), (B) un composé contenant un groupe carboxyle et un groupe à insaturation éthylénique, (C) un composé photopolymérisable, et (D) un initiateur photopolymérisable. La résine soluble dans les alcalis (A) a un poids moléculaire moyen en poids variant de 11 000 à 29 000 et une valeur acide qui n'est pas inférieure à 100 mg de KOH/g. Le composé (B) a un poids moléculaire moyen en poids variant de 1 000 à 9 500, une valeur acide qui n'est pas inférieure à 60 mg de KOH/g, et un indice de réfraction qui n'est pas inférieur à 1,570. Le rapport de la masse de la résine (A) à la masse du composé (B) varie de 0,18 à 6,0.
PCT/JP2019/007370 2018-02-26 2019-02-26 Film de transfert, procédé de formation de motif de résine utilisant un film de transfert, et procédé de formation de motif de film durci WO2019164016A1 (fr)

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WO2021070520A1 (fr) * 2019-10-11 2021-04-15 富士フイルム株式会社 Composition, procédé de production de composition, film durci, film de transfert et procédé de fabrication de panneau tactile
CN112964167A (zh) * 2020-07-21 2021-06-15 西安工程大学 一种基于石墨烯的分段检测传感器的制备方法
WO2022075090A1 (fr) * 2020-10-05 2022-04-14 富士フイルム株式会社 Film de transfert, procédé de production de stratifié et procédé de production de câblage de circuit

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JP2013232011A (ja) * 2013-08-02 2013-11-14 Taiyo Holdings Co Ltd 感光性樹脂組成物及びその硬化物
JP2014153623A (ja) * 2013-02-12 2014-08-25 Rohm & Haas Denshi Zairyo Kk ネガ型感放射線性樹脂組成物
JP2015064612A (ja) * 2010-12-28 2015-04-09 太陽インキ製造株式会社 光硬化性樹脂組成物、そのドライフィルム及び硬化物並びにそれらを用いたプリント配線板
WO2016199868A1 (fr) * 2015-06-09 2016-12-15 旭化成株式会社 Composition de résine aqueuse pour panneau tactile, film de transfert, film durci stratifié, procédé de production de motif de résine et dispositif d'affichage à panneau tactile
WO2017159543A1 (fr) * 2016-03-15 2017-09-21 東レ株式会社 Composition de résine photosensible, film durci, stratifié, élément de panneau tactile, et procédé de fabrication d'un film durci

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JP2011075923A (ja) * 2009-09-30 2011-04-14 Taiyo Holdings Co Ltd 光硬化性樹脂組成物、そのドライフィルム及び硬化物並びにそれらを用いたプリント配線板
JP2015064612A (ja) * 2010-12-28 2015-04-09 太陽インキ製造株式会社 光硬化性樹脂組成物、そのドライフィルム及び硬化物並びにそれらを用いたプリント配線板
JP2014153623A (ja) * 2013-02-12 2014-08-25 Rohm & Haas Denshi Zairyo Kk ネガ型感放射線性樹脂組成物
JP2013232011A (ja) * 2013-08-02 2013-11-14 Taiyo Holdings Co Ltd 感光性樹脂組成物及びその硬化物
WO2016199868A1 (fr) * 2015-06-09 2016-12-15 旭化成株式会社 Composition de résine aqueuse pour panneau tactile, film de transfert, film durci stratifié, procédé de production de motif de résine et dispositif d'affichage à panneau tactile
WO2017159543A1 (fr) * 2016-03-15 2017-09-21 東レ株式会社 Composition de résine photosensible, film durci, stratifié, élément de panneau tactile, et procédé de fabrication d'un film durci

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021070520A1 (fr) * 2019-10-11 2021-04-15 富士フイルム株式会社 Composition, procédé de production de composition, film durci, film de transfert et procédé de fabrication de panneau tactile
CN112964167A (zh) * 2020-07-21 2021-06-15 西安工程大学 一种基于石墨烯的分段检测传感器的制备方法
CN112964167B (zh) * 2020-07-21 2024-02-13 西安工程大学 一种基于石墨烯的分段检测传感器的制备方法
WO2022075090A1 (fr) * 2020-10-05 2022-04-14 富士フイルム株式会社 Film de transfert, procédé de production de stratifié et procédé de production de câblage de circuit

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