WO2008018352A1 - composition polyimide photosensible, composition de résine photosensible positive, ET FPC - Google Patents

composition polyimide photosensible, composition de résine photosensible positive, ET FPC Download PDF

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Publication number
WO2008018352A1
WO2008018352A1 PCT/JP2007/065135 JP2007065135W WO2008018352A1 WO 2008018352 A1 WO2008018352 A1 WO 2008018352A1 JP 2007065135 W JP2007065135 W JP 2007065135W WO 2008018352 A1 WO2008018352 A1 WO 2008018352A1
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WO
WIPO (PCT)
Prior art keywords
diamine
photosensitive
solvent
resin
soluble
Prior art date
Application number
PCT/JP2007/065135
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English (en)
Japanese (ja)
Inventor
Masaya Kakimoto
Shuhei Maeda
Akira Mizoguchi
Original Assignee
Sumitomo Electric Industries, Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2006216281A external-priority patent/JP2008040273A/ja
Priority claimed from JP2007033070A external-priority patent/JP2008197418A/ja
Priority claimed from JP2007034945A external-priority patent/JP2008195892A/ja
Priority claimed from JP2007191035A external-priority patent/JP2009025725A/ja
Application filed by Sumitomo Electric Industries, Ltd. filed Critical Sumitomo Electric Industries, Ltd.
Publication of WO2008018352A1 publication Critical patent/WO2008018352A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/1025—Preparatory processes from tetracarboxylic acids or derivatives and diamines polymerised by radiations
    • 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
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0393—Flexible materials
    • 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
    • H05K3/285—Permanent coating compositions
    • H05K3/287—Photosensitive compositions

Definitions

  • Photosensitive polyimide composition positive photosensitive resin composition
  • the present invention relates to a photosensitive polyimide composition and a positive photosensitive resin composition used for forming a protective film or the like of an FPC (flexible printed wiring board).
  • the present invention also relates to a method for producing the photosensitive polyimide composition and a method for producing a soluble polyimide resin used as a component of the photosensitive polyimide composition.
  • the present invention further relates to a protective film that is formed of the photosensitive polyimide composition and functions as a cover lay of FPC, and an FPC having the protective film.
  • the present invention further relates to a photosensitive resin film obtained from the positive photosensitive resin composition, an FPC production method using the positive photosensitive resin composition, and an FPC obtained by the production method.
  • FPCs are provided with a protective film (coverlay) on the outer surface to protect the wiring.
  • This protective film covers the wiring, the element portion, and the like, but on the other hand, it is necessary to expose the pad portion and the connection portion.
  • FPC insulating protective film hereinafter simply referred to as “protective film”. A method using a conductive resin composition has been adopted.
  • a negative photosensitive resin composition called a solder resist (for example, acrylic epoxy type) is widely used.
  • solder resist for example, acrylic epoxy type
  • these have the disadvantage that the remaining film portion after development is crosslinked and cured, so that it has the disadvantage that it is hard and brittle and does not have sufficient flexibility. It is used. Therefore, recently, as an alternative, a flexible protective film having excellent heat resistance has been desired. From a resin (solvent soluble heat resistant resin) that has excellent heat resistance and solvent solubility (solvent soluble heat resistant resin) and a positive photosensitive agent. A method using a photosensitive resin composition is proposed. It has been proposed.
  • a soluble polyimide resin using a hydroxyl-containing diamine is disclosed in Japanese Patent No. 2935994 (Patent Document 1) and Japanese Patent Application Laid-Open No. 10-224017 (Patent Document 2). Etc. are proposed.
  • the polyimide resin is provided with solubility and alkali developability by using a monomer component which is inherently insoluble in a solvent and containing a certain proportion of diamine having a hydroxyl group.
  • Examples of the diamine having a hydroxyl group include a compound S represented by the following structural formula.
  • the soluble polyimide resin is obtained by condensing a diamine containing a diamine having a hydroxyl group as described above and an aromatic tetracarboxylic dianhydride in a molar ratio of approximately 1: 1.
  • pyridine is used as a catalyst for promoting the reaction.
  • Patent Document 3 771 Publication, Patent Document 3
  • Patent Document 1 Japanese Patent No. 2935994
  • Patent Document 2 Japanese Patent Laid-Open No. 10-224017
  • Patent Document 3 WO 99/19771
  • the photosensitive polyimide composition for forming a protective film has a characteristic that, in addition to the flexibility and heat resistance, development residue (remaining omission during development) hardly occurs in the exposed area ( Developability) and a force S that requires non-exposed portions (that is, portions that serve as a protective film) to be less susceptible to deterioration due to the meshing performed for the formation of connection portions, etc.
  • developability the exposed area
  • a force S that requires non-exposed portions (that is, portions that serve as a protective film) to be less susceptible to deterioration due to the meshing performed for the formation of connection portions, etc.
  • the unexposed area is likely to deteriorate during development, leading to whitening of the surface. Deteriorated by the pre-treatment liquid of the cookie. This phenomenon is greatly deteriorated in the force S generated by both electrolytic gold plating and electroless gold plating, particularly in the electroless gold plating process.
  • the protective film is required to improve the adhesive strength, particularly the adhesive strength with copper, but the conventional protective film is bonded to the copper foil constituting the FPC. There is also a problem that the force is not yet sufficient, and the developing solution may penetrate into the opening to cause deterioration of the film.
  • the first problem of the present invention is a photosensitive polyimide composition containing a soluble polyimide resin, which deteriorates even in the gold plating process ⁇ , particularly, it is difficult to cause spot defects (that is, by exposure and development). (When patterning, there is little occurrence of spot discoloration on the coating surface), and furthermore, a protective film having sufficient adhesion to copper foil can be formed, and the same as conventional photosensitive polyimide compositions. It is to provide a photosensitive polyimide composition that maintains developability and hardly causes problems such as residue warpage.
  • the present invention further provides a method for producing this photosensitive polyimide composition, a force formed by this photosensitive polyimide composition, which hardly resists deterioration in the gold plating process, and a sufficient adhesive strength to copper foil. It is providing the protective film of FPC which has these, and FPC which has this protective film.
  • This problem can be prevented by introducing a rigid component into the soluble polyimide resin to improve the softening temperature.
  • a rigid component into the soluble polyimide resin to improve the softening temperature.
  • warpage is increased and peeling is likely to occur in a crosscut test due to a decrease in adhesion.
  • the second problem of the present invention is to provide a positive-type photosensitive resin composition that does not cause such a problem of the prior art.
  • the present inventor has also shown that the soluble polyimide resin used as the base resin of the conventional photosensitive polyimide composition has a wide molecular weight distribution (dispersion) and two peaks in the low molecular weight region and the high molecular weight region. It was found to have a mountain distribution and a high content of low molecular weight components. And since the high molecular weight component is difficult to dissolve in the solvent, the low molecular weight component is easy to dissolve. Therefore, a residue (residual portion) is generated on the exposed portion of the FPC substrate. As a result of diligent investigation, the surface of the polyimide resin is considered to be easily degraded. I found out that they can be compatible.
  • the inventor further provides a method for synthesizing a soluble polyimide resin by condensation of an aromatic tetracarboxylic dianhydride and diamine! /, And the aromatic tetracarboxylic dianhydride and the above-mentioned Polymerization (condensation) is started in a state where a part of silicone diamine is insoluble and suspended in the reaction solvent, and these molecular weight ranges and molecular weight distributions are reduced by dissolving them as the polymerization proceeds. It has been found that a soluble polyimide resin can be easily synthesized. In the conventional synthesis method, the molecular weight and molecular weight distribution are easily changed for each synthesis (polymerization) lot.
  • the present inventor further added a crosslinkable melamine as a thermosetting agent to a positive photosensitive resin composition
  • a positive photosensitive resin composition comprising a solvent-soluble heat-resistant resin, for example, the above-described soluble polyimide resin, and a positive photosensitive agent.
  • a compound is added, a positive photosensitive patterning is possible in the same way as when it is not added, and when this melamine compound is added, a positive pattern is formed by an afterbeta after development. It is possible to crosslink the resin to increase the softening temperature and improve the high temperature elasticity.
  • spot discoloration is formed by the following mechanism. That is, at the time of development, the developing solution soaks into a defective portion on the coating film to form a minute crack or hole, and soaking further progresses between the coating film and the substrate. Conductor (copper, etc.) oxidation occurs at the part where the penetration occurred after baking after development. As a result, the conductor is colored and observed as spot discoloration.
  • the polymer constituting the coating film may interact with the pyridine to increase the affinity of the coating film for the developer, which may promote the penetration of the developer. I thought there was.
  • the first aspect of the present invention is:
  • the diamine containing S, silicone diamine, and diamine having a hydroxyl group, and the diamine having a hydroxyl group is 6FAP.
  • the photosensitive polyimide composition is characterized in that the content of 6FAP is 1 to 50 mol% with respect to the total diamine (Claim 1).
  • the photosensitive polyimide composition according to the first aspect contains a soluble polyimide resin, which is a condensate of aromatic tetracarboxylic dianhydride and diamine, as a base polymer.
  • the condensate of aromatic tetracarboxylic dianhydride and diamine means a reaction product obtained by condensing aromatic tetracarboxylic dianhydride and diamine in an equimolar amount of about 1: 1.
  • the diamine used for the synthesis of the soluble polyimide resin is a mixture of a silicone diamine and a diamine having a hydroxyl group, and other diamines added if necessary. The developability is obtained by the hydroxyl group of the diamine having a hydroxyl group.
  • Jiamin having a hydroxyl group is a 6FAP, and characterized in that the content of 6FAP is 1 to 50 mol 0/0 for all Jiamin To do.
  • the diamine having a hydroxyl group is 6FAP, developability is further improved.
  • the developability, heat resistance, and resistance to plating can be improved. Therefore, it is possible to obtain excellent developability, heat resistance, and meticulous resistance with the photosensitive polyimide composition of the first embodiment having both of the characteristics.
  • the soluble polyimide resin constituting the photosensitive polyimide composition of the first aspect comprises an aromatic tetracarboxylic dianhydride, silicone diamine, 6FAP, and other diamine added as necessary, as a solvent. It can be produced by dissolving and heating to cause a condensation reaction. If the same solvent as the solvent of the photosensitive polyimide composition is used as the solvent, it is preferable because a solvent replacement operation is not necessary in the production of the photosensitive polyimide composition. Accordingly, examples of the solvent include those described later as the solvent for the photosensitive polyimide composition.
  • the invention according to claim 2 is a preferred embodiment of the photosensitive polyimide composition of the first embodiment, and the weight average molecular weight of the soluble polyimide resin that is the base polymer of the photosensitive polyimide composition is 20000 to 50000 2.
  • the soluble polymer having such an average molecular weight and molecular weight distribution.
  • a mid resin as a base polymer, it is difficult for the development residue to be generated during development, and the insulating film pattern obtained from the parenthesis composition has excellent heat resistance, solvent resistance, and mechanical strength. Insulating film patterns satisfying the required characteristics can be obtained.
  • the molecular weight distribution force distribution is small and the dispersion is small, the effect of hardly causing the development residue and excellent heat resistance, solvent resistance, and mechanical strength becomes remarkable.
  • the single peak distribution means that the molecular weight distribution curve has substantially one peak.
  • the dispersion represents the extent of the molecular weight distribution, and specifically is a value of (weight average molecular weight / number average molecular weight).
  • the weight average molecular weight, number average molecular weight, and molecular weight distribution curve are values measured by GPC and calculated using standard polystyrene (TSK standard polystyrene).
  • TSK standard polystyrene standard polystyrene
  • a soluble polyimide resin having such an average molecular weight and molecular weight distribution can be produced by the method described in claim 18 described later.
  • the second aspect of the present invention provides:
  • the soluble polyimide resin contains the diamine power S, silicone diamine and diamine having a hydroxyl group, and the soluble polyimide resin has a weight average molecular weight of 20000 to 50,000, a molecular weight distribution of one peak distribution, and a dispersion of 2.0 or less. It is a photosensitive polyimide composition characterized in that (Claim 3).
  • the photosensitive polyimide composition of the second aspect also contains a soluble polyimide resin that is a condensate of aromatic tetracarboxylic dianhydride and diamine as a base polymer, and the diamine includes silicone diamine and hydroxyl group. Containing diamine.
  • a soluble polyimide resin that is a condensate of aromatic tetracarboxylic dianhydride and diamine as a base polymer, and the diamine includes silicone diamine and hydroxyl group. Containing diamine.
  • the meaning and action of the condensate of aromatic tetracarboxylic dianhydride and diamine are the same as in the first embodiment.
  • the soluble polyimide resin as the base polymer has a weight average molecular weight in the range of 20000 to 50000, a molecular weight distribution of one peak distribution, and a dispersion of 2. It is 0 or less.
  • the photosensitive polyimide composition of the second aspect is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)
  • the aromatic tetracarboxylic dianhydride and the silicone diamine are condensed in a solvent that dissolves only a part of the aromatic tetracarboxylic dianhydride and the silicone diamine. And then, it is produced by a method for producing a soluble polyimide resin, characterized in that it is carried out by dissolving aromatic tetra force rubonic acid dianhydride and silicone diamine in the solvent while raising the temperature. Yes (claim 18).
  • This soluble polyimide resin production method is the same as the conventional polyimide resin production method in that it has a condensation reaction step of condensing aromatic tetracarboxylic dianhydride and diamine.
  • the aromatic tetracarboxylic dianhydride and diamine are condensed in a solvent that dissolves only a part of the aromatic tetracarboxylic dianhydride and silicone diamine.
  • condensation is started in a state where the aromatic tetracarboxylic dianhydride and the silicone diamine are suspended, and then the aromatic tetracarboxylic acid 2 anhydrous and the silicone diamine are used in the solvent while raising the temperature. It is characterized in that it is dissolved and further condensed.
  • Examples of the solvent that dissolves only a part of the aromatic tetracarboxylic dianhydride and the silicone diamine include ⁇ -petit-mouth rataton.
  • the invention according to claim 19 is a preferred embodiment of the method for producing the soluble polyimide resin, wherein the aromatic tetracarboxylic acid 2 anhydrous is 4,4′-oxydiphthalic acid dianhydride ( 19.
  • Silicone diamine and OPDA react gradually and dissolve in y-petit mouth ratatones as the temperature rises.
  • the reaction is performed at that temperature for a predetermined time. After that, stop heating and let it cool naturally to near room temperature.
  • the fourth aspect of the present invention is as follows.
  • a photosensitive polyimide composition containing a soluble polyimide resin, a positive photosensitive agent and a solvent for dissolving them,
  • the soluble polyimide resin is a condensate of aromatic tetracarboxylic dianhydride and diamine
  • the diamine contains a diamine having a hydroxyl group.
  • a photosensitive polyimide composition (claim 9), wherein the content power of pyridine contained in the photosensitive polyimide composition is 0.05% by weight or less.
  • the photosensitive polyimide composition of the fourth embodiment contains a soluble polyimide resin that is a condensate of aromatic tetracarboxylic dianhydride and diamine, and the diamine contains diamine having a hydroxyl group.
  • aromatic tetracarboxylic dianhydride and diamine condensate and its The action and the like are the same as in the first embodiment.
  • the photosensitive polyimide composition according to the fourth aspect is characterized in that the content of pyridine contained therein is 0.05% by weight or less. Pyridine is used as a catalyst for the condensation reaction of aromatic tetracarboxylic acid dihydrate and diamine. As a result, the conventional photosensitive polyimide composition contains pyridine. It was found that the problem of spot discoloration can be greatly reduced by removing from the photosensitive polyimide composition and making its content 0.05% by weight or less based on the total weight of the photosensitive polyimide composition.
  • pyridine removal step for removing pyridine from the reaction system until the content is 0.05% by weight or less
  • It can be produced by a production method (Claim 17) comprising a step of mixing the soluble polyimide resin, a positive photosensitive agent and a solvent.
  • a condensation reaction step of condensing an aromatic tetracarboxylic dianhydride and diamine to obtain a soluble polyimide resin, and mixing the obtained soluble polyimide resin and a positive photosensitive agent are performed.
  • the point which has a process is the same as the manufacturing method of the conventional photosensitive polyimide composition.
  • the production method of the present invention is characterized by having a pyridine removal step of removing pyridine from the reaction system after the condensation step until the content thereof is 0.05% by weight or less.
  • the method for removing pyridine is not particularly limited.
  • the condensation of aromatic tetracarboxylic dianhydride and diamine is usually carried out using a solvent, and after completion of the reaction, the solvent S is removed to remove pyridine and adjust the concentration.
  • the amount of pyridine in the system can be reduced, and the content can be reduced to 0.05% by weight or less by adjusting the conditions.
  • pyridine can also be removed by a method of reprecipitation and purification using a solvent insoluble in the resin such as methanol and again dissolving in a solvent such as ⁇ -petit-mouth rataton.
  • the invention according to claim 10 is a preferred embodiment of the photosensitive polyimide composition of the fourth embodiment.
  • the weight average molecular weight of the soluble polyimide resin that is a base polymer of the photosensitive polyimide composition is 20000 to 50000.
  • the weight average molecular weight of the soluble polyimide resin that is a base polymer is 20000 to 50000.
  • the weight average molecular weight is in the range of 25000-45000.
  • the copolymerization ratio of the diamine having a hydroxyl group used in the production of the photosensitive polyimide composition that is, the hydroxyl group in the total diamine used in the condensation.
  • the ratio of diamine having a dimer is preferably in the range of 1 to 50 mol%.
  • the developing property of the film pattern is low, and a concentrated alkaline solution or an organic solvent is required as a developer, while copolymerization of a diamine having a hydroxyl group.
  • the range of 1 to 50 mol% is preferable from the viewpoints of image resistance, matt resistance and the like.
  • the invention according to claim 12 is characterized in that the diamine having a hydroxyl group is 6FAP, or the photosensitive polyimide according to any one of claims 9 to 11 It is a composition.
  • the diamine having a hydroxyl group used in the production of the photosensitive polyimide composition is the one used in the conventional photosensitive polyimide composition, that is, the above-described examples.
  • 6FAP is preferable in order to obtain excellent developability. By using 6FAP, film deterioration and film loss during development can be reduced.
  • the diamine component used for the synthesis of the soluble polyimide resin of the fourth aspect can further contain a silicone diamine, and is synthesized using the diamine component containing both the diamine having a hydroxyl group and the silicone diamine.
  • the soluble polyimide resin is preferably used.
  • the silicone component contains silicone diamine. By containing silicone diamine, it is possible to improve the flame retardance of the protective film, the adhesion to copper constituting the wiring, the flexibility, etc. with the force S.
  • the silicone diamine is a compound having a siloxane group in the skeleton and two primary amino groups at its ends and the like, for example, represented by the following structural formula (III) Is widely adopted.
  • a represents a number of 1 to about 10,000.
  • those represented by the following structural formulas are also exemplified.
  • a + b (a if not including formula force 3 ⁇ 4) is a number from 1 to about 10,000.
  • silicone diamines include: Toray Dow Cowing. Silicone BY16 — 853U, BY16-853C, Shin-Etsu Chemical X—22—1660B—3, KF—8010, X—22—161A X-22-161B and the like.
  • the invention according to claim 13 is a preferred embodiment of the photosensitive polyimide composition of the first, second and fourth aspects, wherein the diaminergic silicone diamine is all diamine.
  • the content of the silicone diamine is preferably 5 to 60 mol% with respect to the total diamine.
  • the molecular weight of silicone diamine is about 500 to about 1000, it is preferably 10 to 60 mol% with respect to the total diamine! /. If it exceeds 60 mol%, the glass transition temperature of the film decreases and heat resistance decreases, whereas if it exceeds 5 mol%, the warpage of the film tends to increase. The More preferably, it is the range of 30-50 mol%. However, heat resistance and film warpage are also affected by the structure and content of other diamines.
  • the above-mentioned diamine power silicone diamine is used in an amount of 5 to 60 And containing 1 to 50 mol% of diamine having a hydroxyl group based on the total diamine.
  • the invention of claim 14 is a preferred embodiment of the photosensitive polyimide composition of the first, second and fourth embodiments, wherein the silicone diamine has a weight average molecular weight.
  • the diamine that can be used in the production of the photosensitive polyimide composition has the above-mentioned hydroxyl group.
  • other diamines can be included within the scope not departing from the gist of the present invention.
  • diamines include, for example, bis (3aminopropyl) ether ethane, 3,3, -diamino-4,4'dihydroxydiphenylsulfone, 4,4'diamino3,3'dihydroxybiphenyl, 2,2bis.
  • 1,3-bis (3-aminophenoxy) benzene (hereinafter referred to as “1,3-APB”) represented by the following structural formula (IV) is a viewpoint of transparency and flexibility. More preferably used.
  • BAPSM bis [4- (3aminophenoxy) phenyl] sulfone
  • 1, 4 APB 1,4-bis (3-aminophenoxy) benzene
  • BAPSM bis [4- (3aminophenoxy) phenyl] sulfone
  • 1, 4 APB 1,4-bis (3-aminophenoxy) benzene
  • 1,3-APB and diammine represented by the following structural formula can also be used.
  • the invention according to claim 15 is a preferred embodiment of the photosensitive polyimide composition according to the first, second and fourth embodiments, wherein the aromatic tetracarboxylic dianhydride is 4,
  • the aromatic tetracarboxylic dianhydride constituting the soluble polyimide compound is 3, 3 ', 4, 4' biphenyltetracarboxylic dianhydride, 3, 3 ', 4, 4'-benzophenone tetracarboxylic dianhydride, 4, 4'-oxydiphthalic dianhydride, 3, 3' , 4, 4'-diphenylsulfone tetracarboxylic dianhydride, bicyclo (2, 2, 2) -otato 7-ene 2, 3, 5, 6 tetracarboxylic dianhydride, 1, 2, 4, 5 Cyclohexanetetracarboxylic dianhydride, pyromellitic dianhydride, 2,2 bis (3,4 dicarboxylicoxyphenyl) hexafluoropropane dianhydride, 5 (2,5 dixotetrahydro) Furyl)
  • OPDA force represented by the following structural formula (V) is preferable from the viewpoint of transparency and flexibility, and therefore, an aromatic tetracarboxylic dianhydride containing OPDA is preferably used.
  • the soluble polyimide resin used in the photosensitive polyimide composition of the present invention has already been imidized at the stage of synthesis. Therefore, heating for forming an imide ring is unnecessary, and a heat treatment step may be performed if necessary after pattern formation. This is done to evaporate residual solvent contained in the pattern. Therefore, heating at a high temperature necessary to form an imide ring is not necessary.
  • the photosensitive polyimide composition of the present invention contains a positive-type photosensitive agent and a solvent that dissolves the soluble polyimide resin and the positive-type photosensitive agent together with the soluble polyimide resin.
  • di-type photosensitizers include naphthoquinone diazide compounds, and particularly preferred are naphthoquinone diazide sulfonyl esters of aromatic polyhydroxy compounds.
  • aromatic polyhydroxy compounds examples include 2, 3, 4-trihydroxybenzophenone, 2, 3, 4, monotrihydroxybenzophenone, 2, 4, 6 trihydroxybenzophenone, 2, 3 , 4, 4, —tetrahydroxybenzophenone, nopolac resin and the like.
  • the naphthoquinone diazide sulfonyl compounds that form esters with aromatic polyhydroxy compounds include 1,2-naphthoquinone-1,2 diazide-1,5 sulfonic acid, 1,2 naphthoquinone-1,2 diazido-1,4-sulfonic acid, 6-diazodihydro 5-oxo1 naphthalene Examples include sulfonic acid. Specific product names include PC-5, NT-200, 4N T-300 manufactured by Toyo Gosei Co., Ltd., DTEP-300, DTEP-350 manufactured by Daito Chemix.
  • the amount of the positive photosensitive agent needs to be adjusted depending on the film thickness of the coating film, the type of the photosensitive agent, etc., but it is 5 to 30 parts by weight based on 100 parts by weight of the soluble polyimide resin. It is preferable to do this. If the amount is less than 5 parts by weight, sufficient sensitivity may not be obtained and a residue may be generated. If the amount exceeds 30 parts by weight, the heat resistance and solvent resistance of the resin film formed by curing of the composition will decrease. There is a case. 10 to 20 parts by weight is more preferable.
  • the photosensitive polyimide composition of the present invention can be obtained by mixing the soluble polyimide resin thus produced and a positive photosensitive agent. This mixing step can be performed in the same manner as in the case of a conventional photosensitive polyimide composition, for example, by dissolving the soluble polyimide resin and the positive photosensitive agent in a solvent.
  • N-methyl-2-pyrrolidone N, N'-dimethylacetamide, dimethylformamide, dimethyl sulfoxide, acetonitrile, diglyme, ⁇ butyrolataton , ⁇ - valerolataton, phenol , toluene, dioxane, tetrahydrofuran, Examples include sulfolane and hexamethylphosphoramide. Among these, 7 petit-mouth rataton is preferably used from the viewpoint of high volatility and odor. The amount used is preferably 1 to 20 times (weight ratio) of the soluble polyimide resin.
  • Soluble polyimide resin as solvent It is preferable to use the same solvent as that used for the synthesis because the solvent replacement operation is not necessary in the production of the photosensitive polyimide composition. Therefore, like the case where the soluble polyimide resin is synthesized by the method of claim 19, ⁇ - if petit port la out emissions is used in the synthesis, also ⁇ - Petit port as a solvent of a photosensitive polyimide composition Rataton Is preferred.
  • the photosensitive polyimide composition of the present invention obtained as described above can be used for forming a protective film of FPC.
  • the present invention further provides a protective film for covering the wiring of the FPC, the curing of the photosensitive polyimide composition according to any one of claims 1 to 3 or claim 9 to claim 16.
  • a protective film (claim 20) characterized by comprising a material.
  • This protective film is provided on the outer surface of the FPC and covers them in order to protect the wiring, the element portion, and the like.
  • the photosensitive polyimide composition is applied to the entire surface of the FPC, and if necessary, the solvent is removed by heating (prebaking) to remove the solvent.
  • prebaking heating
  • a pattern is formed (patterned) through an exposure process in which only a predetermined portion is irradiated with an actinic ray such as ultraviolet rays through a mask or the like, and a development process in which development is performed with an alkaline developer. It is formed by the method of removing.
  • alkali developer examples include sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, ammonium hydrogen carbonate, tetramethyl ammonium hydroxy.
  • a basic solution in which a salt ( ⁇ ) or the like is dissolved in water or alcohol, or a solution in which a basic compound is increased by further adding an amine compound to this solution is used.
  • the development time is suitably about 4 to 30 minutes. In less than 4 minutes, it is difficult to obtain good development results. On the other hand, if it exceeds 30 minutes, pattern peeling or the like tends to occur.
  • the power that can further reduce the occurrence of spot discoloration by setting the development time within 30 minutes When the photosensitive polyimide composition of the fourth aspect is used, even if the development time exceeds 30 minutes. The occurrence of spot discoloration can be reduced to a practical level.
  • the present invention further provides FPC (Claim 21) having the protective film according to Claim 20.
  • FPC Fraim 21
  • the third aspect of the present invention provides:
  • a positive photosensitive resin composition comprising a solvent-soluble heat-resistant resin, a positive photosensitive agent, a thermosetting agent, and a solvent,
  • thermosetting agent is a melamine-based curing agent
  • the solvent-soluble heat-resistant resin is a positive photosensitive resin composition characterized in that it is a polyimide resin or a polyamide-imide resin containing diamine having a hydroxyl group as a structural unit (claim 4).
  • the positive-type photosensitive resin composition of the third aspect includes a thermosetting agent that causes a crosslinking reaction by heating to cure the resin.
  • a thermosetting agent that causes a crosslinking reaction by heating to cure the resin.
  • patterning is performed by exposure and development. Heat curing can be performed later.
  • a protective film that is resistant to thermal deformation can be obtained, and when a reinforcing plate is pressed after the protective film is formed (for example, adhesion is performed under conditions of about 180 ° C ⁇ 30 minutes),
  • adhesion is performed under conditions of about 180 ° C ⁇ 30 minutes
  • the positive photosensitive resin composition of the third aspect is characterized by using a melamine curing agent as the thermosetting agent.
  • Other possible thermo-curing agents include epoxy-based curing agents and isocyanate-based curing agents.
  • epoxy-based curing agents development that shortens the life of the positive photosensitive resin composition.
  • problems such as possible deterioration due to alkali at the time.
  • an isocyanate curing agent there are problems such as poor storage stability.
  • a melamine curing agent it is preferable because it has characteristics such as excellent storage stability of the positive photosensitive resin composition!
  • the invention according to claim 6 is the positive photosensitive resin composition according to the third aspect, wherein the melamine-based curing agent power is a methylolmelamine-based compound represented by the following structural formula (I). It is characterized by this.
  • W represents —NY Y, Y and Y are each independently hydrogen, —CH— ⁇ .
  • ⁇ to ⁇ each independently represent hydrogen or —CH ⁇
  • ⁇ represents hydrogen or an alkyl group having 6 to 6 carbon atoms.
  • the methylol melamine-based compound represented by the above formula is particularly excellent in storage stability, excellent developability, and resistance to mesh as compared with an epoxy-based curing agent and an isocyanate-based curing agent. This is preferable.
  • Examples of the methylone melamine compound represented by the above formula include hexamethylol melamine, alkylated hexamethylol melamine, partially methylolated melamine and its alkylated product, tetramethylol benzoguanamine, alkylated tetramethylol benzoguanamine, It is possible to list partially methylolated benzoguanamine and its alkylated compounds.
  • thermosetting agents such as an epoxy-based curing agent and an isocyanate-based curing agent may be used in combination as long as the gist of the present invention is not impaired.
  • the solvent-soluble heat-resistant resin constituting the positive photosensitive resin composition of the present invention is soluble in an alkaline aqueous solution used as an organic solvent developer and has excellent heat resistance. Specifically, it is a soluble polyimide resin or a soluble polyamideimide resin containing diamine having a hydroxyl group in its constituent unit.
  • the soluble polyimide resin comprises an aromatic tetracarboxylic dianhydride and a diamine containing a diamine having a hydroxyl group. It can be obtained by condensation in equimolar amounts.
  • the acid anhydride as a raw material of the soluble polyamideimide generally used is an aromatic tricarboxylic rubonic acid anhydride as described below, with an aromatic tetracarboxylic dianhydride added.
  • the invention of claim 5 is the positive photosensitive resin composition according to the third aspect, wherein the polyimide resin or polyamideimide resin strength S, the aromatic tetracarboxylic dianhydride, or the aromatic tricarboxylic anhydride.
  • the present invention provides a positive photosensitive resin composition characterized by being a condensed product of an acid anhydride obtained by adding aromatic tetracarboxylic dianhydride to diamine and diamine.
  • Examples of the diamine having a hydroxyl group include compounds represented by the following structural formulas as in the first, second and fourth embodiments (claim 7).
  • the copolymerization ratio of the diamine having a hydroxyl group that is, the ratio of the diamine having a hydroxyl group in the total diamine used for the condensation is also the same as in the first, second and fourth embodiments; A range of 50 mono% is preferable, and the reason is the same.
  • the diamine constituting the soluble polyimide resin or the soluble polyamideimide resin may contain a silicone diamine. Examples of the silicone diamine that are similar to each other include the silicone diamines exemplified above, and the effects of the blending are also the same.
  • the diamine may contain other diamines in addition to the diammine having a hydroxyl group and the silicone diamine, as long as the gist of the present invention is not impaired.
  • the diamine exemplified in the case of the fourth embodiment can be used in the same manner.
  • the solvent-soluble heat-resistant resin is a soluble polyamideimide resin
  • examples of the aromatic tricarboxylic acid anhydride that is a raw material of the soluble polyamideimide resin include trimellitic anhydride (TMA), 2- (3 , 4 dicarboxyphenyl) -2- (3 carboxyphenyl) propan anhydride, (3, 4-dicarboxyphenyl) (3-carboxyphenyl) methane anhydride, (3,4-dicarboxy) Phenyl) (3-carboxyphenyl) ether anhydride, 3, 3,, 4 tricarboxybenzophenone anhydride, 1,2,4-butanetricarboxylic acid anhydride, 2,3,5-naphthalenetricarboxylic acid anhydride 2, 3, 6-naphthalene tricarboxylic acid anhydride, 1, 2, 4 naphthalene tricarboxylic acid anhydride, 2, 2 ', 3 biphenyl tricarboxy
  • the weight average molecular weight by GPC measurement of the soluble polyimide and / or soluble polyamideimide constituting the positive photosensitive resin composition of the third aspect is preferably in the range of 20000 to 50000.
  • the weight average molecular weight exceeds this range, the printability of the composition may be deteriorated, or the remaining portion may be lost during development.
  • the weight average molecular weight is less than this range, problems such as film deterioration during development and insufficient mechanical strength of the film may occur.
  • the soluble polyimide resin-soluble polyamideimide constituting the positive photosensitive resin composition of the third aspect includes an acid component such as aromatic tetracarboxylic acid dianhydride and aromatic tricarboxylic acid anhydride exemplified above. It is possible to obtain diamine by condensing it in a reaction solvent. This condensation reaction is carried out under the same conditions as in the synthesis of conventional polyimide-polyamideimide.
  • a reaction solvent methyl benzoate, ethyl benzoate, methyl ethyl ketone
  • MEK MEK
  • acetone ⁇ -butyrolatatane
  • ⁇ -methylpyrrolidone ⁇ , ⁇ ⁇ ⁇ ⁇ -dimethylacetamide, toluene, xylene and the like.
  • the solvent-soluble heat-resistant resin and the positive photosensitive agent produced as described above are mixed in a solvent constituting the positive photosensitive resin composition. It is obtained by doing.
  • the invention according to claim 8 is characterized in that the positive photosensitive agent is a quinonediazide compound. It is a photosensitive resin composition.
  • a quinonediazide compound is used as a positive photosensitive agent, even if a melamine curing agent is included in the composition, patterning is possible with the same sensitivity and developability as in the case where the melamine curing agent is not included.
  • Preferred examples of the quinonediazide compound used as the positive photosensitive agent include naphthoquinonediazide compounds exemplified in the case of the first, second and fourth embodiments, particularly naphthoquinonediazidesulfonyl esters of aromatic polyhydroxy compounds.
  • the same solvents as those exemplified in the case of the first, second and fourth aspects are preferably exemplified. It is preferable to use the same solvent as the solvent used for the synthesis of the solvent-soluble heat-resistant resin as the solvent does not require a solvent replacement operation in the production of the positive photosensitive resin composition.
  • the content of the thermosetting agent in the positive photosensitive resin composition is preferably in the range of 1 part by weight to 50 parts by weight with respect to 100 parts by weight of the solvent-soluble heat-resistant resin. 2 to 20 parts by weight. If the thermosetting agent is less than 1 part by weight, curing will be insufficient, and it will be easy to cause scratches during pressing (adhesion) of the reinforcing plate and damage to the protective film during solder reflow. On the other hand, if it exceeds 50 parts by weight, the shrinkage due to curing increases, and the substrate tends to warp.
  • the positive photosensitive agent is preferably in the range of 5 to 50 parts by weight, more preferably 10 to 40 parts by weight with respect to 100 parts by weight of the solvent-soluble heat-resistant resin. If it is less than 5 parts by weight or more than 50 parts by weight, patterning may be difficult.
  • the concentration of the solids such as a solvent-soluble heat-resistant resin, positive photosensitive agent and thermosetting agent is 10 to 50% by weight, and the amount of the solvent is within this range. It is determined.
  • the positive photosensitive resin composition obtained in this way has developability comparable to that of conventional positive photosensitive resin compositions and is less likely to cause problems such as residues. It is. On the other hand, it is also excellent in resistance to scratches, and it is difficult for deterioration and defects to occur in the plating process.
  • the invention described in claim 22 is obtained by forming the positive photosensitive resin composition of the third aspect and heating the resulting film to remove the solvent. This is a photosensitive resin film.
  • the positive photosensitive resin composition of the third aspect can be used for forming a protective film of FPC and also for forming a photosensitive resin film.
  • This photosensitive resin film is formed by depositing a positive photosensitive resin composition by, for example, a method such as coating on a PET film which has been subjected to an appropriate release treatment, and the resulting film is then heated to 90 ° C. It is possible to manufacture by removing the solvent in the composition by heating to the extent.
  • This photosensitive resin film can be used as a photosensitive dry film resist.
  • a method for producing an FPC protective film (coverlay) using the positive-type photosensitive resin composition of the third aspect comprises applying this composition onto an FPC substrate on which wiring is formed. After film formation, the obtained film is heated to remove the solvent, then exposed through a mask and further developed to obtain a positive pattern, and then heated to a temperature higher than the curing temperature of the melamine curing agent, Solvent soluble It is carried out by crosslinking a heat resistant resin.
  • the invention of claim 23 provides the positive photosensitive resin composition of the third aspect, that is, the positive photosensitive resin composition of claim 4 to claim 8, or the wiring of the positive photosensitive resin composition of any one of claims 4 to 8.
  • a step of coating on an FPC substrate formed with a film, a step of heating the obtained film to remove the solvent, and exposing the positive photosensitive resin composition from which the solvent has been removed through a mask A method for producing an FPC comprising: a step, a step of developing after exposure, and a step of heating after development to a temperature equal to or higher than a curing temperature of the melamine curing agent.
  • the method of applying the positive photosensitive resin composition onto the FPC substrate is not particularly limited, and can be performed, for example, by screen printing. Besides, spin coating, spray coating, die coating, doctor Examples include knife coating and flexographic printing.
  • the step of heating the obtained film to remove the solvent (so-called pre-beta), the step of exposing the positive photosensitive resin composition from which the solvent has been removed through a mask, and the step of developing after exposure are generally followed. This can be done under the same conditions as when manufacturing protective films for FPC using conventional positive photosensitive resin compositions.
  • Developers and the like are the same alkaline developers as conventional ones, for example, inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia water, ethylamine, n-propylamine and the like.
  • 1st amine such as dimethylamine, triethanolamine, 3rd amine such as triethylamine, triethanolamine, tetramethylammonium hydroxide, tetraethyl
  • Aqueous solutions of ammonium hydroxide and corin can be used.
  • This FPC manufacturing method has a step of heating a film remaining after development to a temperature higher than the curing temperature of the melamine curing agent. By this heating, the solvent-soluble heat-resistant resin forming this film is cross-linked with a melamine curing agent, the softening temperature and the high temperature elastic modulus are improved, and the excellent effects as described above are obtained.
  • the heating temperature is equal to or higher than the temperature at which crosslinking with the melamine curing agent is performed, and is usually in the range of about 130 to 200 ° C. This temperature range is almost the same as the after-beta temperature when an FPC protective film is produced using a conventional positive photosensitive resin composition.
  • the resin constituting the positive photosensitive resin composition of the present invention is a soluble polyimide
  • the soluble polyimide is often already imidized at the stage of synthesis. Therefore, heating at a high temperature necessary for imide ring formation is unnecessary.
  • the present invention further provides, as claim 24, an FPC manufactured by the method for manufacturing an FPC according to claim 23.
  • This FPC has a protective film with an improved softening temperature and high-temperature elastic modulus. It can be used to generate scratches during pressing (adhesion) of the reinforcing plate, as well as during protective reflow or manual soldering. Damage is suppressed.
  • the invention's effect is suppressed.
  • the photosensitive polyimide composition of the first aspect When used for forming a protective film of FPC, etc., it has developability comparable to that of conventional photosensitive polyimide compositions, and is not warped. It is difficult to cause problems. In addition, the protective film formed using the photosensitive polyimide composition of the first aspect hardly deteriorates even in the gold plating process and has a sufficient adhesive force to the copper foil. [0115]
  • the photosensitive polyimide composition of the second embodiment is used for forming a protective film of FPC, etc., and in the process of forming the protective film of FPC, the development is comparable to the conventional photosensitive polyimide composition. It is difficult for problems such as residues to occur.
  • an FPC protective film with excellent adhesion resistance, resistance to deterioration even in the gold plating process, especially resistance to spot discoloration, and sufficient adhesion to copper foil. Can do.
  • the photosensitive polyimide composition of the second embodiment makes it possible to achieve both excellent developability and matt resistance.
  • the photosensitive polyimide composition of the second aspect can be easily produced by the method for producing a photosensitive polyimide composition according to claims 18 and 19.
  • the positive-type photosensitive resin composition of the third aspect has developability comparable to that of conventional positive-type photosensitive resin compositions and is less likely to cause problems such as residues. It is also excellent in the plating property, and it is difficult for deterioration and defects to occur in the plating process. Furthermore, by applying this positive photosensitive resin composition onto a substrate and crosslinking the resin by heating, a protective film having a high softening temperature and a high high temperature elastic modulus can be formed. It is possible to suppress problems such as the occurrence of wrinkles during pressing (adhesion) of the reinforcing plate, damage to the protective film during solder reflow or correction by hand solder.
  • the use of the photosensitive polyimide composition of the fourth aspect reduces the occurrence of spot discoloration on the coating surface when patterning is performed by exposure and development to form a protective film for FPC.
  • the power to lose S Further, the photosensitive polyimide composition of the fourth aspect can be easily produced by the method for producing a photosensitive polyimide composition according to claim 17.
  • FIG. 1 is a GPC chart of a varnish obtained in Example 2 or Comparative Example 5.
  • the present invention is not limited to this example.
  • the concentration of pyridine in the varnish was determined using GC-MS (apparatus: Shimadzu GC17A, column: UA-1 (inner diameter 0.25 mm, film thickness 0.25 ⁇ 111, length 30 m), injection temperature: 250. C, injection amount: 2 Quantitative determination by 1) was 0. 02% by weight based on the total amount of varnish 1. Furthermore, varnishes 2 to 5 were produced in the same manner except that the pressure reducing time was changed. Similarly, the pyridine concentration was quantitatively determined as follows.
  • Varnish 4 0. 10 weight 0/0
  • Varnish 5 2.90 Weight 0/0
  • 1, 2 naphthoquinone-2 diazido 5 sulfone as a photosensitizer Ester (Daito - Chemix Ltd., DTEP- 300) was added and mixed 15 weight 0/0 (15 phr) with respect to the resin solid content, a photosensitive polyimide composition (photosensitive ink 1-5) were formulated.
  • the photosensitive polyimide composition was applied onto a copper foil having a thickness of 18 m by screen printing, and then pre-betaged at 90 ° C. for 30 minutes to obtain a film having a thickness of 12 to 15 m. This film was exposed to 800 mj / cm 2 of ultraviolet rays through a predetermined mask.
  • the sample subjected to patterning was subjected to a general electrolytic gold plating treatment. That is, the steps shown below were performed in the order shown below, and the samples were sequentially stacked in the tank of each step and then dried.
  • Each of the photosensitive inks 1 to 5 is applied onto a copper foil having a thickness of 18 111, 4 cm X 1.5 cm, and dried to form a coating film having a thickness of 12 to; After irradiating with light through a mask, development was performed with the developer described above, and the state after gold plating was observed by the above-described method to determine the number of spots per sample. In practice, 40 samples were evaluated and the average number of spots per piece was calculated. The results and evaluations based on the following criteria are shown in Table 1.
  • ⁇ Spot power observed, less than 0.5 per sample.
  • ⁇ The number of observed spots is 0.5 to 1.0 per sample piece.
  • X The number of spots observed is greater than 1.0 per sample piece.
  • Example 1 Varnish 1 0. 02 0. 017 0. 2 ⁇ Comparative Example 1 Varnish 2 0. 06 0. 052 0. 9 ⁇ Comparative Example 2 Varnish 3 0. 08 0. 07 2. 8 X Comparative Example 3 Varnish 4 0. 10 0. 09 1. 1 X Comparative Example 4 Varnish 5 2. 90 2. 52 12.9 X
  • the spot discoloration numbers shown in Table 1 are the results when gold plating is further performed after development. In consideration of the fact that spot discoloration is newly formed by the gold plating process and that the spot discoloration does not disappear due to the gold plating process, the number of spot discoloration generated by development is a smaller value than that shown in Table 1. Become. As shown in Table 1, when the residual pyridine concentration is 0.02% by weight with respect to the varnish, the number of spot discoloration is low and practical use is possible, while the residual pyridine concentration is 0.06% by weight with respect to the varnish. In the case of 0.08% by weight, 0.10% by weight, and 2.90% by weight, the number of spot discoloration is large and cannot be used practically.
  • the dispersion (Mw / Mn), which is the ratio between the weight average molecular weight (Mw) and the number average molecular weight (Mn), of the obtained varnish was measured by GPC (HLC-8220GPC, manufactured by Tosoh Corporation). TSKgel GMHHR-H manufactured by Tosoh Corporation was used as the column, and the carrier solvent was LiMP dissolved in NMP at a concentration of 0.1 N.
  • the molecular weight is a converted value calculated using standard polystyrene (TSK standard polystyrene).
  • Figure 1 shows the GPC chart of the varnish obtained.
  • the resulting varnish was mixed with 15 phr of 1,2-naphthoquinone-2-diazido 5-sulfonic acid ester (manufactured by Toyo Gosei Co., Ltd., hereinafter referred to as PC 5) as a photosensitizer, and mixed with a photosensitive polyimide composition ( Photosensitive ink) was prepared.
  • the photosensitive ink was applied on a copper foil having a thickness of l S ⁇ m by screen printing and then pre-betaged to obtain a coating having a thickness of 12 to 15 m.
  • the film was exposed to 1000 mj / cm 2 of mercury lamp light through a predetermined mask.
  • ⁇ It is possible to clearly pattern up to L / S of ⁇ ⁇ m or less, and there is no deterioration of the film or penetration into the interface.
  • ⁇ Force that can be put in the patterning area The power at which residues can be seen in the exposed area and the deterioration of the film can be seen.
  • Each photosensitive ink is applied onto a copper foil having a thickness of 18 m, dried to form a resist film having a thickness of 12 to 15 m, and irradiated with light through a predetermined mask. After developing on the development line, electroless gold plating is applied. The condition after the plating was observed and evaluated according to the following criteria. The results are shown in Table 2.
  • ⁇ Spot power S observed, 0.3 or less per sample piece.
  • ⁇ The number of spots observed is greater than 0.3 and less than 1.0 per sample.
  • X The number of spots observed is greater than 1.0 per sample piece.
  • a varnish was prepared in the same manner as in Example 2 except that a mixed solvent in which 40 g of methyl benzoate was mixed with 100 g of ⁇ -butyral rataton instead of 140 g of ⁇ -butyrolatatone as a solvent was used.
  • the silicone diamine and OPDA were completely dissolved from the beginning of the reaction, and the suspended portion was not strong.
  • the varnish of Comparative Example 5 thus obtained was measured in the same manner as the varnish of Example 2. The results are also shown in Table 2.
  • Figure 1 shows the GPC chart of the varnish obtained.
  • the reaction was the same as in Example 2 except that instead of 140 g of the solvent ⁇ -butyroratatone 140 g, a mixed solvent of 100 g of ⁇ -butyrolactaton mixed with 40 g of methyl benzoate was used, and ABPS was used instead of 6FAP. To produce a varnish. Also in this reaction, the silicone diamine and OPDA were completely dissolved from the beginning of the reaction, and the suspended portion was not strong.
  • Example 4 As shown in Table 2, according to the photosensitive polyimide compositions of Examples 2 and 3 which are the products of the present invention, it is possible to achieve both excellent developability and scratch resistance. With a photosensitive polyimide composition, it is difficult to achieve both excellent developability and resistance to plating. In particular, in the case where 6FAP is not used and in Comparative Example 6, the resistance to the plating is inferior. [0146] Example 4
  • tan ⁇ is measured in an air atmosphere at a heating rate of 10 ° C / min, and the temperature at the maximum value of tan ⁇ is measured.
  • the lath transition temperature (Tg) was used.
  • TG DTA differential heat .simultaneous thermogravimetric measuring device: Seiko Instruments Inc., TG / DT
  • A220 a temperature that reduces 5% weight (Td) at a heating rate of 10 ° C / min in an air atmosphere.
  • Example 3 Based on the formulation shown in Table 3, the varnishes of Examples 5 to 12 and Comparative Examples 7 to 15 were obtained in the same manner as Example 4, and the same measurements as those of Example 4 were performed. The results are also shown in Table 4.
  • SiOn represents silicone diamine
  • the molar ratio is the molar ratio of each component in the diamine
  • mol% is the molar ratio expressed in%.
  • the total number of moles of diamine is the same as that of OPDA.
  • Example 4 4 7 1 33 58 8 Comparative example 8 4 7 (1) 33 58 8 Example 5 2 3 1 33 50 17 Comparative example 9 2 3 (1) 33 50 17 Example 6 1 1 1 33 33 33 33 Comparison Example 10 1 1 (1) 33 33 33 Comparative example 11 1 1 50 50
  • Example 10 8 3 1 67 25 8
  • Example IV 4 I 1 67 17 17
  • Example IV 2 8 1 3 j 67 8 25
  • the results in Table 4 show that the warpage and glass transition temperature are greatly influenced by the amount of silicone diamine.
  • the amount of silicone diamine is small, the warpage increases. However, even in the case of about 33 mol% with respect to the total diamine (Examples 4 to 6), the warpage is not significant, and it can be used for applications such as a protective film.
  • the amount of silicone diamine is large, the glass transition temperature is lowered. In the case of about 67 mol% with respect to the total diamine (Examples 10 to 12), the glass transition temperature is about 45 ° C. A certain force that can be used In order to obtain better heat resistance, a higher glass transition temperature is desired.
  • the results in Table 4 indicate that about 60 mol% or less is preferable based on the total diamine.
  • Example 5 Based on the formulation shown in Table 5, the varnishes of Examples 13 to 19 and Comparative Examples 16 to 17 were obtained in the same manner as in Example 4 (as shown in Table 5, some examples and comparisons).
  • APB was replaced with BA PSM
  • OPDA was replaced with benzophenone tetracarboxylic acid (BTDA)
  • 6FAP was replaced with ABPS.
  • a photosensitive polyimide composition photosensitive ink
  • screen printing, pre-beta, exposure, and development developer: 3% NaOH + 3% ethanolamine aqueous solution
  • FPC for evaluation was obtained.
  • Example 1 8 1 (25) 1 (25) OPDA replaced with BTDA
  • Example 1 9 2 (50) 1 (25) 1 (25)
  • Each of the photosensitive inks was applied onto a migration evaluation double-sided plate having a copper foil pattern of 18 m in thickness, and dried to form an insulating film having a thickness of 12 to 15 ⁇
  • development with a developer was performed to create an FPC for evaluation. This was placed under a high temperature and high humidity of 85 ° C and relative humidity of 85% RH, a 50V DC voltage was applied between the conductors for 1000 hours, the state of the resist film was observed, and the following criteria were evaluated. The results are shown in Table 6.
  • Each photosensitive ink is applied onto a copper foil having a thickness of 18 m, dried to form a resist film having a thickness of 12 to 15 m, irradiated with light through a predetermined mask, and then developed. After developing with the solution, (a) electroless gold plating, (b) electrolytic gold plating. Observe the post-mesh condition and Evaluation was based on the criteria shown. The results are shown in Table 6.
  • silicone diamine KF8010 is 33.20 g (0.04 mol)
  • the amount of 1,3—APB is 11.69 g (0.04 mol)
  • the solvent added to adjust the solid content concentration ⁇ butyrolatatone amount is 50 g
  • Each positive photosensitive resin composition obtained in this way was applied on a 38 m thick copper foil by screen printing, and then pre-beta (90 ° C x 30 minutes). The solvent was removed to obtain a film having a thickness of 12 to 15 m. This film was exposed to 1000 mj / cm 2 of mercury lamp light through a predetermined mask. Then, develop for 7 minutes at room temperature using a developer that is 2.3% NaOH + 0.5% ethanolamine aqueous solution (40 ° C), rinse with pure water, and dry. The developability was evaluated.
  • ⁇ ⁇ Can pattern up to 50 m or less L / S, and no deterioration of film or penetration into the interface.
  • ⁇ The power that can be applied to L / S patterning of about 100 m Deterioration of the film is observed.
  • Each of the positive photosensitive resin compositions obtained in the above was applied on a copper foil having a thickness of 38, im by screen printing, and then pre-beta (90 ° CX 30 minutes), the solvent in the composition was removed, and a film having a thickness of about 25 ⁇ 111 was obtained.
  • This film was immersed in a developing solution of 2.3% NaOH + 0.5% ethanolamine aqueous solution (40 ° C.) at room temperature for 7 minutes. After washing with pure water, after-beta was performed at 120 ° C for 1 hour + 220 ° C for 30 minutes, and the copper foil was dissolved with an acid to obtain a film having a thickness of about 25 m.
  • the resulting film was subjected to dynamic viscosity measurement, and the softening temperature, the elastic modulus at 180 ° C. ( ⁇ ′ @ 180 ° C.), and the tan ⁇ peak temperature were measured by the following methods. These results are shown in Table 8.
  • the temperature at which the elastic modulus begins to decrease was defined as the softening temperature, and the elastic modulus at 180 ° C was defined as E '@ 180 ° C.

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Abstract

L'invention concerne une composition polyimide photosensible contenant une résine polyimide soluble qui est un condensat d'un dianhydrure tétracarboxylique aromatique avec diamines, un photosensibilisateur à action positive, et un solvant dans lequel la résine et le photosensibilisateur sont dissous, la composition polyimide photosensible présentant une teneur en pyridine inférieure ou égale à 0,05 % en poids. La composition polyimide photosensible peut être une composition dans laquelle les diamines comprennent une siliconediamine et une diamine hydroxylée et la résine polyimide soluble possède un poids moléculaire moyen de 20.000-50.000 et une distribution de poids moléculaire ayant un pic et un rapport dispersif inférieur ou égal à 2,0. La composition de résine photosensible positive comprend une résine résistante thermiquement soluble dans un solvant qui est une résine polyimide soluble ou une résine polyamide-imide soluble, un photosensibilisateur à action positive, un agent de cuisson thermique, et un solvant, et est caractérisé en ce que l'agent de cuisson thermique est un agent de vulcanisation de type mélamine.
PCT/JP2007/065135 2006-08-08 2007-08-02 composition polyimide photosensible, composition de résine photosensible positive, ET FPC WO2008018352A1 (fr)

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
JP2006-216281 2006-08-08
JP2006216281A JP2008040273A (ja) 2006-08-08 2006-08-08 感光性ポリイミドシリコーン組成物、保護膜、及びフレキシブルプリント配線板
JP2007033070A JP2008197418A (ja) 2007-02-14 2007-02-14 感光性ポリイミド組成物及びその製造方法
JP2007-033070 2007-02-14
JP2007034945A JP2008195892A (ja) 2007-02-15 2007-02-15 感光性ポリイミド組成物、並びに、可溶性ポリイミド樹脂の製造方法及び感光性ポリイミド組成物の製造方法
JP2007-191035 2007-07-23
JP2007191035A JP2009025725A (ja) 2007-07-23 2007-07-23 ポジ型感光性樹脂組成物及び前記ポジ型感光性樹脂組成物より得られる樹脂フィルム、並びに、ｆｐｃの製造方法及びｆｐｃ
JP2007-034945 2007-12-20

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WO2008018352A1 true WO2008018352A1 (fr) 2008-02-14

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2009125845A1 (ja) * 2008-04-10 2011-08-04 ソニーケミカル＆インフォメーションデバイス株式会社 フレキシブル配線板の製造方法
JP2014062255A (ja) * 2013-10-30 2014-04-10 Nippon Kayaku Co Ltd ポリイミド樹脂

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JPH11100501A (ja) * 1997-09-29 1999-04-13 Toray Ind Inc ポジ型感光性樹脂組成物の製造方法
JP2003337415A (ja) * 2002-05-17 2003-11-28 Hitachi Chemical Dupont Microsystems Ltd 感光性重合体組成物、レリーフパターンの製造法および電子部品
JP2004212678A (ja) * 2002-12-27 2004-07-29 Kyocera Chemical Corp 感光性樹脂組成物及びポジ型パターン形成方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11100501A (ja) * 1997-09-29 1999-04-13 Toray Ind Inc ポジ型感光性樹脂組成物の製造方法
JP2003337415A (ja) * 2002-05-17 2003-11-28 Hitachi Chemical Dupont Microsystems Ltd 感光性重合体組成物、レリーフパターンの製造法および電子部品
JP2004212678A (ja) * 2002-12-27 2004-07-29 Kyocera Chemical Corp 感光性樹脂組成物及びポジ型パターン形成方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2009125845A1 (ja) * 2008-04-10 2011-08-04 ソニーケミカル＆インフォメーションデバイス株式会社 フレキシブル配線板の製造方法
JP2014062255A (ja) * 2013-10-30 2014-04-10 Nippon Kayaku Co Ltd ポリイミド樹脂

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