Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/44—Polycarbonates
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/67—Unsaturated compounds having active hydrogen
  • C08G18/675—Low-molecular-weight compounds
  • C08G18/6755—Unsaturated carboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
  • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
  • C08L75/04—Polyurethanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
  • C08L75/04—Polyurethanes
  • C08L75/06—Polyurethanes from polyesters
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
  • C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
  • C09D167/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl - and the hydroxy groups directly linked to aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
  • C09D175/04—Polyurethanes
  • C09D175/06—Polyurethanes from polyesters
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
• • 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
  • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
• • 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 thermosetting resin composition, a method for forming a protective film for a flexible wiring board, a flexible wiring board and an electronic component, and a method for manufacturing the flexible wiring board.
• resin compositions for example, sealants, solder resists, etc.
• resin compositions used for electronic parts have better heat resistance in order to cope with downsizing, thinning, and speeding up. It is required to have electrical properties and moisture resistance. Therefore, as a resin constituting the resin composition, a polyimide resin, a polyamideimide resin, or a polyamide resin has been used instead of an epoxy resin.
• these resins have a rigid resin structure and a cured film lacks flexibility. Therefore, when it uses for a thin film base material, there exists a problem that the base material after hardening is easy to warp largely, and is inferior in flexibility.
• Patent Document 4 discloses a thermosetting resin composition which is improved in low warpage, flexibility, solder heat resistance and tin plating resistance.
• the thermosetting resin composition of Patent Document 4 has excellent performance in terms of electrical insulation characteristics that maintain high electrical characteristics at high temperatures and high humidity.
• Patent Document 5 discloses a thermosetting resin composition having a low warpage, flexibility and bending resistance, which includes a polyamideimide-modified polyurethane, a curing agent and an organic solvent. Here, low warpage, flexibility, and electrical insulation characteristics under high temperature and high humidity are measured.
• thermosetting resin composition does not completely satisfy the bending resistance desired in the market, and an electric insulating protective film having further higher bending resistance has been desired.
• JP 62-106960 A Japanese Patent Laid-Open No. 8-12763 Japanese Unexamined Patent Publication No. 7-196798 JP 2006-117922 A Japanese Patent Laying-Open No. 2015-147940
• the conventional resin composition with improved warpage and flexibility is easy to infiltrate water molecules under high temperature and high humidity, and maintains high electrical characteristics. It was difficult. In order to impart high electrical properties, it is considered effective to introduce a rigid component into the resin structure and to have a high glass transition temperature, but according to this technique, the substrate after curing tends to warp greatly, In addition, problems such as poor flexibility occur.
• thermosetting resin composition described in Patent Document 4 provides a protective function against wiring breakage, although some improvement is recognized in terms of low warpage, flexibility, solder heat resistance and tin plating resistance. It was difficult.
• thermosetting resin composition described in Patent Document 5 has a certain degree of bending resistance, it is still not sufficient. Therefore, when the protective film of the flexible wiring board is formed, the present invention suppresses warping sufficiently while maintaining high electrical insulation reliability under high temperature and high humidity, and is excellent in bending resistance.
• the main object is to provide a thermosetting resin composition.
• the present inventors have flexible a curable composition having a specific structure and a compound having an imide bond and / or an amide bond as an essential component.
• the warp of the flexible wiring board when the printed curable composition is cured is small, and the protective film containing a cured product of this curable composition has flexibility and long-term electrical insulation properties.
• the present invention has been completed by finding that it has an excellent effect of suppressing breakage of a large wiring when the flexible wiring board covered with the protective film is shaken.
• Component A A compound having a structural unit represented by the following formula (1), having a bond of at least one of an imide bond and an amide bond, and having a functional group that reacts with a curing agent, A curable composition comprising (Component B) a curing agent, and (Component C) an organic solvent.
• each R 1 independently represents an organic residue derived from a diol having 3 to 36 carbon atoms
• each R 2 independently represents a phenylene group or a phenylene group having a substituent.
• Component A is (raw material a) a trivalent and / or tetravalent polycarboxylic acid derivative having an acid anhydride group, (raw material b) a polyol represented by the following formula (2), and (raw material) c)
• R 1 's each independently represents an organic residue derived from a diol having 3 to 36 carbon atoms, and each of the R 2 ' s independently represents a phenylene group or a substituted group. Represents a phenylene group having a group, and n represents an integer of 1 to 60.
• (Component A) in the curable composition defined by [3] is (raw material a) trivalent and / or tetravalent polycarboxylic acid derivative having an acid anhydride group, (raw material b) formula ( The polyol represented by 2) and (raw material c) polyisocyanate are used as raw materials, and the reaction is possible between many compounds corresponding to (raw material a), (raw material b), and (raw material c). Moreover, the polymer obtained will also change if the compounding ratio and reaction conditions of each monomer are changed. Therefore, the structure of the component A obtained is extremely diverse, and it is difficult to define with a specific structure, it can be said that it is common technical knowledge of those skilled in the art.
• the polymerization composition specified in [3] cannot be specified by its structure or characteristics, and can be specified for the first time by a process (production method). Or we think there are circumstances where it is impossible or nearly impractical to identify directly by property.
• Component A is at least (raw material a) a trivalent and / or tetravalent polycarboxylic acid derivative having an acid anhydride group, (raw material b) a polyol represented by the following formula (2), And (raw material c) a curable composition as described in [1] or [2], comprising a reaction product comprising polyisocyanate.
• R 1 's each independently represents an organic residue derived from a diol having 3 to 36 carbon atoms, and each of the R 2 ' s independently represents a phenylene group or a substituted group. Represents a phenylene group having a group, and n represents an integer of 1 to 60.
• composition according to any one of [1] to [7], comprising at least one fine particle selected from the group consisting of inorganic fine particles and organic fine particles.
• component (B) is contained in an amount of 1 to 55 parts by mass when the total amount of the component (A) and the component (B) is 100 parts by mass.
• the curable composition according to any one of [1] to [10] is applied to a part or all of a surface of a flexible wiring board in which wiring is formed on a flexible substrate.
• a flexible wiring board in which wiring is formed on a flexible substrate is partially or entirely covered with the overcoat film described in [12].
• Flexible wiring board [14] The flexible wiring board according to [13], wherein the wiring is tin-plated copper wiring.
• a method for producing a flexible wiring board covered with an overcoat film comprising the following (Step 1) and (Step 3) and optionally (Step 2); (Process 1) A step of forming a printed film on the pattern by printing the curable composition according to any one of [1] to [10] on at least a part of the wiring pattern portion of the flexible wiring board (step 2) A step of evaporating a part or all of the solvent in the printed film by placing the printed film obtained in step 1 in an atmosphere of 40 to 100 ° C. (step 3) A step of curing the printed film obtained in step 1 or the printed film obtained in step 2 at 100 to 170 ° C. to form an overcoat film. [16] An electronic component having the cured film according to [11].
• a protective film excellent in low warpage, flexibility, and long-term insulation reliability is obtained, and when the flexible wiring board covered with the cured film is shaken. It is possible to provide a protective film having a great effect of suppressing wiring breakage.
• the present invention is a protective film made of a cured product of the curable composition, and a flexible wiring board covered with the protective film, and warping is sufficiently suppressed while maintaining high insulation reliability.
• a flexible wiring board having excellent flexibility can be provided.
• the present invention (Component A) A compound having a structural unit represented by the following formula (1), having a bond of at least one of an imide bond and an amide bond, and having a functional group that reacts with a curing agent, (Component B) A curable composition containing a curing agent, and (Component C) an organic solvent.
• each R 1 independently represents an organic residue derived from a diol having 3 to 36 carbon atoms, and each R 2 independently represents a phenylene group or a phenylene group having a substituent.
• component A which is an essential component of the curable composition of the present invention has a structural unit represented by the formula (1) and has an imide bond.
• (Component A) may further have a urethane bond (—O—C ( ⁇ O) —NH—).
• Component A) has a functional group that reacts with the curing agent.
• Preferable functional groups that react with the curing agent include at least one functional group of a carboxyl group, a hydroxyl group, an acid anhydride group, an isocyanato group, an amide group, and an amino group.
• the isocyanato group is preferably protected with a blocking agent.
• other groups may be protected with a blocking agent, and those that react with the block body removed are regarded as functional groups.
• the wavy line is the end of the bond and represents the binding site with other bonds.
• R 1 is an organic residue derived from a diol having 3 to 36 carbon atoms.
• the organic residue derived from the diol is a divalent group in which two hydroxy groups are removed from the diol.
• diol having 3 to 36 carbons examples include 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, 1,5-propanediol, Pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,9- Nonanediol, 1,10-decanediol, 1,12-dodecanediol, hydrogenated dimer (C36) diol, chain diols such as diethylene glycol and triethylene glycol, 5-membered ring diols such as 1,2-cyclopentanedimethanol, 1,3-cyclopentanedimethanol and bis (hydroxymethyl) tricyclo [5.2
• R 1 is preferably a hydrocarbon group having 3 to 18 carbon atoms and a chain structure, and more preferably a hydrocarbon group having 4 to 9 carbon atoms and a chain structure. Particularly preferred are hydrocarbon groups having 4 to 6 carbon atoms and a chain structure.
• preferred diols capable of deriving the organic residue of R 1 include, for example, 1,3-propanediol, 1,2-propanediol, 1,4-ditandiol, 2-methyl-1, 3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1, Examples include 8-octanediol, 1,9-nonanediol, and 1,10-decanediol, and more preferable diols include, for example, 1,4-ditandiol, 2-methyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octan
• R 2 independently represents a phenylene group or a phenylene group having a substituent.
• the phenylene group include a 1,2-phenylene group, a 1,3-phenylene group, and a 1,4-phenylene group.
• the substituent of the phenylene group having a substituent include an alkyl group having 1 to 10 carbon atoms, specifically, a 3-methyl-1,2-phenylene group, a 4-methyl-1,2-phenylene group.
• examples of the phenylene group having a substituent include 3-bromo-1,2-phenylene group, 4-bromo-1,2-phenylene group, 4-bromo-1,3-phenylene group, and 2-bromo-1,4.
• Halogens such as -phenylene group, 3-chloro-1,2-phenylene group, 4-chloro-1,2-phenylene group, 4-chloro-1,3-phenylene group, 2-chloro-1,4-phenylene group A phenylene group containing
• 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group and phenylene group having an alkyl group as a substituent preferred are 1, A 2-phenylene group, a 1,3-phenylene group, and a 1,4-phenylene group are preferable, and a 1,2-phenylene group and a 1,3-phenylene group are particularly preferable.
• R 1 is 1,6-hexanediol or 3-methyl-1,5-pentanediol
• R 1 is an organic residue derived from 3-methyl-1,5-pentanediol.
• (Component A) can be synthesized, for example, by the following method.
• (Method 1) (Raw material b) Polyol represented by the following formula (2)
• R 1 s each independently represents an organic residue derived from a diol having 3 to 36 carbon atoms
• n R 2 s each independently represent a phenylene group or a substituent.
• n represents an integer of 1 to 60 independently.
• Raw material c A polyisocyanate is reacted with polyisocyanate to obtain a compound having a urethane bond and having an isocyanato group at the terminal, and the obtained polyisocyanate containing a compound having a urethane bond and having an isocyanato group at the terminal (raw material a) Acid anhydride group (see below)
• R 1, R 2 in the formula (2) are respectively the same as R 1, R 2 in the formula (1).
• N in the formula (2) represents an integer of 1 to 60.
• Preferred n is an integer of 1 to 45, particularly preferably an integer of 1 to 30.
• the average value of n is preferably 3 to 11, and more preferably 5 to 10.
• the number average molecular weight of the diol of the formula (2) is preferably 500 to 5000, more preferably 750 to 4000, and particularly preferably 1000 to 3000.
• the polyisocyanate (that is, (raw material c)) to be reacted with the polyol of (raw material b) is not particularly limited as long as it is a compound having two or more isocyanato groups.
• Specific examples of the polyisocyanate include 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis.
• (Isocyanatomethyl) cycloaliphatic polyisocyanates such as biuret of cyclohexane, norbornene diisocyanate and isophorone diisocyanate; diphenylmethane-2,4′-diisocyanate, 3,2′-dimethyldiphenylmethane-2,4′-diisocyanate, 3,3 '-Dimethyldiphenylmethane-2,4'-diisocyanate, 4,2'-dimethyldiphenylmethane-2,4'-diisocyanate, 4,3'-dimethyldiphenylmethane- , 4'-diisocyanate, 5,2'-dimethyldiphenylmethane-2,4'-diisocyanate, 5,3'-dimethyldiphenylmethane-2,4'-diisocyanate, 6,2'-dimethyldiphenylmethane-2,4'-diiso
• a polyisocyanate having a ring Chain aliphatic polyisocyanates such as biuret of hexamethylene diisocyanate, lysine triisocyanate, lysine diisocyanate, hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate and 2,2,4-trimethylhexanemethylene diisocyanate;
• Examples thereof include polyisocyanates having a heterocyclic ring such as isocyanurate of isophorone diisocyanate and isocyanurate of hexamethylene diisocyanate, and these may be used alone or in combination of two or more.
• polyisocyanates having an aromatic ring are preferable, and diphenylmethane-4,4′-diisocyanate, diphenylmethane-3,3′-diisocyanate, diphenylmethane-3,4 ′ are more preferable.
• -Polyisocyanates having an aromatic ring such as diisocyanate and diphenyl ether-4,4'-diisocyanate, and most preferred is diphenylmethane-4,4'-diisocyanate.
• the isocyanato group may be stabilized with a blocking agent in order to avoid changes over time.
• a blocking agent examples include hydroxy acrylate, methanol, alcohols such as 2-butanone oxime, phenol, and oxime, but there is no particular limitation.
• the reaction of the polyol (raw material b) and the polyisocyanate (raw material c) can be carried out by heating and reacting them in the presence of an organic solvent, preferably a non-nitrogen-containing polar solvent.
• non-nitrogen-containing polar solvent examples include ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, and triethylene glycol diethyl ether; sulfur-containing solvents such as dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, and sulfolane.
• An ester solvent such as ⁇ -butyrolactone and cellosolve acetate
• a ketone solvent such as cyclohexanone and methyl ethyl ketone
• an aromatic hydrocarbon solvent such as toluene and xylene.
• solvents it is preferable to select and use a solvent in which the resin to be generated can be dissolved. Moreover, it is preferable to use what is suitable as a solvent of a thermosetting resin composition as it is after a synthesis
• solvents cyclohexanone, ⁇ -butyrolactone, and diethylene glycol diethyl ether are particularly preferable in view of volatility and efficient reaction in a homogeneous system.
• the amount of the solvent used is preferably 80 to 500 parts by mass with respect to 100 parts by mass of the total amount of raw materials for synthesizing the (A 1 -1) compound.
• the amount used is 80 to 500 parts by mass with respect to 100 parts by mass of the total amount of raw materials for synthesizing the (A 1 -1) compound, the viscosity at the time of synthesis does not become too high, and synthesis is difficult due to inability to stir It is preferable that the reaction rate is not extremely reduced.
• the reaction temperature is preferably 60 to 210 ° C., more preferably 70 to 190 ° C., and particularly preferably 80 to 180 ° C. If this temperature is less than 60 ° C, the reaction time tends to be too long, and if it exceeds 210 ° C, gelation tends to occur during the reaction.
• the reaction time can be appropriately selected depending on the capacity of the reaction vessel and the reaction conditions employed.
• the reaction may be performed in the presence of a catalyst such as a tertiary amine, an alkali metal, an alkaline earth metal, a metal such as tin, zinc, titanium, cobalt, or a metalloid compound.
• a catalyst such as a tertiary amine, an alkali metal, an alkaline earth metal, a metal such as tin, zinc, titanium, cobalt, or a metalloid compound.
• the blending ratio at the time of reacting the polyol of (raw material b) and the polyisocyanate of (raw material c) is appropriately adjusted according to the number average molecular weight of the (A 1 -1) compound to be produced. However, since the terminal of the resulting (A 1 -1) compound is an isocyanato group, it is necessary that the number of hydroxyl groups in (raw material b) ⁇ the number of isocyanate groups in (raw material c).
• the ratio of the number of isocyanato groups to the number of hydroxyl groups is preferably adjusted to be 1.01 or more. It is more preferable to adjust to 0.0 or less.
• the number average molecular weight of the (A 1 -1) compound having an isocyanato group at the terminal is preferably 500 to 30000, more preferably 1000 to 25000, and particularly preferably 1500 to 20000.
• the (A 1 -1) compound having an isocyanato group at the terminal and the (raw material a) trivalent and / or tetravalent polycarboxylic acid derivative having an acid anhydride group are reacted to form a urethane bond, an amide bond and / or Alternatively, a compound having an imide bond is generated.
• (raw material a) is a trivalent polycarboxylic acid derivative having an acid anhydride group, it has one set of acid anhydride and one carboxyl group.
• (raw material a) is a tetravalent polycarboxylic acid derivative having an acid anhydride group, it has two sets of acid anhydrides, or one set of acid anhydride groups and two carboxyl groups.
• the carboxyl group may form a derivative by forming an ester bond with alcohol.
• the polycarboxylic acid derivative means a polycarboxylic acid having an acid anhydride group or a derivative such as a carboxylic acid ester thereof.
• R 3 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenyl group.
• R 4 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a phenyl group, and Y 1 represents —CH 2 —, —CO—, —SO 2 —, or —O—. Represents.
• R 3 and R 4 are preferably a hydrogen atom, and Y 1 is preferably —CO— or —O—.
• trimellitic anhydride is particularly preferable from the viewpoint of cost.
• the tetravalent polycarboxylic acid derivative which has an acid anhydride group For example, the tetracarboxylic dianhydride represented by following General formula (5) can be mentioned. These can be used alone or in combination of two or more.
• Y 2 represents a tetravalent organic group.
• the tetracarboxylic dianhydride represented by the formula (5) is not particularly limited, and examples thereof include pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2 , 3,2 ′, 3′-benzophenone tetracarboxylic dianhydride, 2,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyltetracarboxylic dianhydride Anhydride, 2,2 ', 3,3'-diphenyltetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1
• the tetracarboxylic dianhydride is ethylene glycol bis (trimellitic anhydride) (TMEG), 3,3 ′, 4,4′-diphenyltetracarboxylic dianhydride (BPDA), pyromellitic dianhydride.
• TMEG ethylene glycol bis (trimellitic anhydride)
• BPDA 4,4′-diphenyltetracarboxylic dianhydride
• PMDA 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride
• ODPA 4,4′-oxydiphthalic dianhydride
• tetracarboxylic dianhydrides may be used alone or in combination of two or more.
• the (A 1 -1) compound is reacted with the (raw material a) together with a polyisocyanate other than the (A 1 -1) compound (hereinafter referred to as (A 1 -2) compound).
• a compound having a urethane bond and an amide bond and / or an imide bond may be obtained.
• the (A 1 -2) compound is not particularly limited as long as it is a polyisocyanate other than the (A 1 -1) compound, and examples thereof include the (raw material c). These can be used individually by 1 type or in combination of 2 or more types.
• the ratio of the total number of isocyanate groups of the combined isocyanate groups of isocyanate group and A 1 in -2 in A 1 -1 is not particularly limited, The range is preferably 0.9: 1.0 to 1.1: 1.0, and more preferably 0.95: 1.0 to 1.05: 1.0.
• an amine compound can be used in combination with the polyisocyanate.
• an amine compound the compound which converted the isocyanato group in the said polyisocyanate conversion into the amino group is mentioned. Conversion of the isocyanato group to an amino group can be performed by a known method.
• the total amount of the (A 1 -2) compound is an aromatic polyisocyanate.
• This aromatic polyisocyanate is particularly preferably diphenylmethane-4,4′-diisocyanate in consideration of the balance of solubility, mechanical properties and cost.
• the blending ratio when the (raw material c) polyisocyanate and the (raw material a) trivalent and / or tetravalent polycarboxylic acid derivative having an acid anhydride group are reacted is the ratio of the compound (A 2 -1) to be produced.
• the number average molecular weight is appropriately adjusted depending on how much the molecular weight is made.
• the terminal of the resulting (A 2 -1) compound is an isocyanato group
• the total number of the acid anhydride groups and the number of carboxyl groups in (raw material a) ⁇ the total number of isocyanato groups in (raw material c)
• the number of carboxyl groups includes R 3 and R 4 as hydrogen atoms, such as —COOR 3 in the compound represented by formula (3) and —COOR 4 in the compound represented by formula (4).
• (raw material a) and (raw material c) used in the synthesis method of (Method 2) are the same as (raw material a) and (raw material c) used in the synthesis method of (Method 1), respectively. used.
• the ratio of the number of isocyanato groups, the number of acid anhydride groups, and the total number of carboxyl groups (the number of isocyanato groups / the number of acid anhydride groups)
• the total number of carboxyl groups is preferably adjusted to be 1.01 or more, and is preferably adjusted to 2.0 or less.
• the number average molecular weight of the (A 2 -1) compound having an isocyanato group at the terminal is preferably 500 to 15000, more preferably 800 to 10,000, and particularly preferably 1,000 to 5,000.
• the (A 2 -1) compound having an isocyanato group at the terminal is reacted with the polyol represented by (raw material b) formula (2) to have a urethane bond and an amide bond and / or an imide bond. A compound is formed.
• the total number of isocyanate groups in A 2 -1, number of hydroxyl groups in the starting material b, and 2,2 number of hydroxyl groups in the polyol having a carboxyl group such as dimethylol propionic acid and 2,2-dimethylol butanoic acid is not particularly limited, but in the case of having an amide group in A 2 -1, it may be in the range of 0.9: 1.0 to 1.1: 1.0. More preferably, it is in the range of 0.95: 1.0 to 1.05: 1.0.
• (raw material b) used in the synthesis method of (Method 2) can be the same as (raw material b) described in (Method 1) above.
• a polyol may be further added to form a urethane bond by a reaction between the terminal isocyanate group and the added polyol.
• (Method 3) In the synthesis method of (Method 3), first, (raw material c) polyisocyanate and (raw material a) a trivalent and / or tetravalent polycarboxylic acid derivative having an acid anhydride group are reacted to form an imide bond and an amide.
• a compound having at least one of the bonds and having an acid anhydride group and / or a carboxyl group at the terminal hereinafter referred to as “(A 3 -1) compound” is synthesized.
• the blending ratio when the (raw material c) polyisocyanate and the (raw material a) trivalent and / or tetravalent polycarboxylic acid derivative having an acid anhydride group are reacted is the ratio of the compound (A 3 -1) to be produced.
• the number average molecular weight is appropriately adjusted depending on how much the molecular weight is made.
• the terminal of the generated (A 3 -1) compound is an acid anhydride group and / or a carboxyl group
• the number of carboxyl groups includes R 3 and R 4 as hydrogen atoms, such as —COOR 3 in the compound represented by formula (3) and —COOR 4 in the compound represented by formula (4). Also includes the number of certain carboxyl groups.
• (raw material a) and (raw material c) used in the synthesis method of (Method 3) are the same as (raw material a) and (raw material c) used in the synthesis method of (Method 1), respectively. used.
• the ratio between the total number of acid anhydride groups and the number of carboxyl groups and the number of isocyanate groups (acid anhydride) is preferably adjusted to 1.01 or more, and more preferably to 2.0 or less.
• the number average molecular weight of the (A 3 -1) compound having an acid anhydride group and / or a carboxyl group at the terminal is preferably 500 to 15000, more preferably 800 to 10,000, and more preferably 1000 to 5000. It is particularly preferred.
• the ratio of the total number of acid anhydride groups in A 3 -1 to the number of hydroxyl groups in raw material b is not particularly limited, but should be in the range of 0.9: 1.0 to 1.1: 1.0. More preferably, it is in the range of 0.95: 1.0 to 1.05: 1.0.
• the (raw material b) used in the synthesis method of (Method 3) can be the same as the (raw material b) described in (Method 1). From the viewpoint of improving chemical resistance and electrical properties, and controlling functional groups such as acid value, a method for obtaining a compound having an isocyanato group at the terminal in the first reaction (that is, (Method 1) and (Method 2)) Is preferred.
• Non-nitrogen-containing polar solvent examples include ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, and triethylene glycol diethyl ether; sulfur-containing solvents such as dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, and sulfolane.
• An ester solvent such as ⁇ -butyrolactone and cellosolve acetate; a ketone solvent such as cyclohexanone and methyl ethyl ketone; and an aromatic hydrocarbon solvent such as toluene and xylene. These can be used alone or in combination of two or more.
• solvents it is preferable to select and use a solvent that can dissolve the resin to be produced. Moreover, it is preferable to use what is suitable as a solvent of a thermosetting composition as it is after a synthesis
• ⁇ -butyrolactone and a mixed solvent containing ⁇ -butyrolactone are preferable in order to perform the reaction in a homogeneous system efficiently.
• the amount of solvent used is preferably 0.8 to 5.0 times (mass ratio) with respect to the total amount of (Component A).
• the amount used is 0.8 to 5.0, it is preferable because the viscosity at the time of synthesis does not become too high and the reaction rate does not decrease.
• the reaction temperature is preferably 60 to 210 ° C., more preferably 70 to 190 ° C., and particularly preferably 80 to 180 ° C. If this temperature is less than 60 ° C, the reaction time tends to be too long, and if it exceeds 210 ° C, gelation tends to occur during the reaction.
• the reaction time can be appropriately selected depending on the capacity of the reaction vessel and the reaction conditions employed.
• the reaction may be performed in the presence of a catalyst such as a tertiary amine, an alkali metal, an alkaline earth metal, a metal such as tin, zinc, titanium, cobalt, or a metalloid compound.
• a catalyst such as a tertiary amine, an alkali metal, an alkaline earth metal, a metal such as tin, zinc, titanium, cobalt, or a metalloid compound.
• a catalyst such as a tertiary amine, an alkali metal, an alkaline earth metal, a metal such as tin, zinc, titanium, cobalt, or a metalloid compound.
• the number average molecular weight means a value measured by gel permeation chromatography (GPC) and converted using a standard polystyrene calibration curve.
• the number average molecular weight, mass average molecular weight, and degree of dispersion are defined as follows.
• the measurement conditions of GPC are as follows.
• Device name HPLC unit HSS-2000 manufactured by JASCO Corporation
• Mobile phase Tetrahydrofuran Flow rate: 1.0 mL / min
• Detector JASCO Corporation RI-2031Plus Temperature: 40.0 ° C
• Sample amount 100 ⁇ l of sample loop Sample concentration: adjusted to around 0.1% by mass.
• the acid value of (Component A) is preferably 10 to 50 mgKOH / g. Further, it is preferably 10 to 35 mg KOH / g, and particularly preferably 15 to 30 mg KOH / g. When the acid value of (Component A) is from 10 to 50 mgKOH / g, the warpage is not excessively large and the curing is sufficient, so that it is possible to suppress deterioration of weather resistance, flexibility, and the like.
• A represents the acid value (mgKOH / g)
• Vf represents the titration amount (mL) of the 0.1N KOH solution
• Wp represents the mass (g) of the solution containing (Component A).
• I represents the proportion (% by mass) of the nonvolatile content of the solution containing (Component A).
• the number average molecular weight of the component A thus obtained is preferably 5000 to 50000, more preferably 6000 to 40000, and particularly preferably 7000 to 25000.
• a number average molecular weight of 5,000 to 50,000 is preferable because a decrease in weather resistance or chemical resistance can be suppressed and solubility in a non-nitrogen-containing polar solvent can be maintained.
• the curable composition which concerns on this embodiment further contains the hardening
• the curing agent is a compound having two or more functional groups capable of reacting with the functional group of the component (A) in one molecule.
• the curing agent of the component (B) is an epoxy group or isocyanato that reacts with those functional groups. It preferably has a plurality of groups, hydroxyl groups and carboxyl groups.
• the epoxy group-containing compound used as a curing agent is one or more compounds having an epoxy group in one molecule, and at least one of them has two or more epoxy groups in one molecule. If included, there is no particular limitation.
• epoxy group-containing compound used as the curing agent examples include phenol novolac type epoxy resins, orthocresol novolak type epoxy resins, phenol, cresol, xylenol, resorcin, catechol, phenols and / or ⁇ -naphthol.
• Diglycy such as novolac type epoxy resin, bisphenol A, bisphenol F, bisphenol S, alkyl-substituted or unsubstituted biphenol, stilbene phenols Dil ether (bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, biphenyl type epoxy compound, stilbene type epoxy compound), glycidyl ether of alcohols such as butanediol, polyethylene glycol, polypropylene glycol, phthalic acid Glycidyl ester type epoxy resins of carboxylic acids such as isophthalic acid and tetrahydrophthalic
• a compound having two or more epoxy groups in one molecule and having an aromatic ring structure and / or an alicyclic structure is preferable.
• cyclopentadiene-modified phenolic resins of glycidyl ether i.e., tricyclo [5,2,1,0 2,6] have decane structure and aromatic ring structure and a compound having two or more epoxy groups
• 1,3-bis (1-adamantyl) -4,6-bis (glycidylyl) benzene 1- [2 ′, 4′-bis (glycidylyl) phenyl] adamantane, 1,3-bis (4′-glycidylylphenyl) adamantane and 1 Ep
• Component A when importance is attached to the reactivity with the aforementioned (Component A) of the present invention, among compounds having two or more epoxy groups in one molecule and having an aromatic ring structure and / or an alicyclic structure.
• glycidyl type or methyl glycidyl type epoxy resins such as those in which active hydrogen bonded to the nitrogen atom of aniline or bis (4-aminophenyl) methane is substituted with a glycidyl group, nitrogen of aminophenols such as p-aminophenol
• An amino group and an aromatic ring structure such as an active hydrogen bonded to an atom and an active hydrogen of a phenolic hydroxyl group substituted with a glycidyl group or an epoxy resin of a methyl glycidyl type, and two or more epoxy groups
• the compound which has is preferable, Especially preferably, it is a compound as described in following formula (7).
• examples of the compound having a plurality of isocyanate groups used as a curing agent that is, a polyisocyanate compound include diisocyanate compounds, triisocyanates, and other tetrafunctional or higher functional isocyanates.
• a polyisocyanate compound in which an isocyanato group is stabilized with a blocking agent. These can be used alone or in combination of two or more.
• the blocking agent includes alcohol, phenol, oxime, etc., but is not particularly limited.
• this blocked isocyanate for example, trade names “DURANATE 17B-60PX, TPA-B80E, MF-B60X, MF-K60X, E402-B80T” manufactured by Asahi Kasei Chemicals Corporation, trade names “Karenz MOI-BM, MOI-BP ”, trade names“ BL-3175, BL-4165, Desmo Cup 11, Desmo Cup-12 ”manufactured by Sumika Bayer Urethane Co., Ltd., and the like.
• the blocked isocyanate is preferably selected in accordance with the thermosetting temperature of (Component A), and BL-3175 is particularly preferable for low temperature curing.
• the hydroxyl group-containing compound used as the curing agent is one or more compounds having a hydroxyl group in one molecule, and at least one of them has a compound having two or more hydroxyl groups in one molecule. There is no particular limitation.
• hydroxyl group-containing compound used as the curing agent examples include polyhydric alcohols, and specific examples include ethylene glycol, glycerin, butanediol, pentaerythritol and the like.
• the carboxyl group-containing compound used as the curing agent is one or more compounds having a carboxyl group in one molecule, and at least one of them has a compound having two or more carboxyl groups in one molecule. If included, there is no particular limitation.
• carboxyl group-containing compound used as the curing agent examples include polyvalent carboxylic acids, and specific examples include phthalic acid, succinic acid, trimellitic acid, adipic acid, pyromellitic acid and the like.
• an epoxy group-containing compound, a polyisocyanate compound, a hydroxyl group-containing compound, and a carboxyl group-containing compound can be used alone or in combination, and can be selected according to the reactive group of (Component A).
• (Component A) has a hydroxy group
• (Component A) has a carboxyl group or an amino group
• an epoxy-containing compound is not limited to an epoxy group-containing compound, a polyisocyanate compound, a hydroxyl group-containing compound, and a carboxyl group-containing compound as long as it reacts with the reactive group of (Component A).
• the amount of (Component B) in the curable composition of the present invention is 1 to 55% by mass, preferably 2 to 45% by mass, based on the total amount of (Component A) and (Component B) in the curable composition. More preferably, it is 2.5 to 30% by mass.
• the amount of (Component B) in the curable composition of the present invention is 1 to 55% by mass based on the total mass of (Component A) and (Component B) in the curable composition. It is preferable from the viewpoint of the solvent resistance of the cured film, and the balance between the low warpage of the flexible wiring board characterized by being covered with the cured film, suitable electrical insulation reliability, and the effect of suppressing the wiring breakage. Can take.
• the amount of (Component A) in the curable composition of the present invention is 45 to 99% by mass, preferably 55 to 98%, based on the total amount of (Component A) and (Component B) in the curable composition. % By mass, more preferably 70 to 97.5% by mass.
• the amount of (Component A) in the curable composition of the present invention is 45 to 99% by mass based on the total amount of (Component A) and (Component B) in the curable composition. It is preferable from the viewpoint of the solvent resistance of the cured film, and it is possible to balance the low warpage of the flexible wiring board characterized by being covered with the cured film and the effect of suppressing wiring breakage.
• (Component C) which is an essential component of the curable composition of the present invention
• the organic solvent used as (Component C) is not particularly limited as long as it can dissolve (Component A) and (Component B).
• diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, Ether solvents such as diethylene glycol dibutyl ether, diethylene glycol butyl methyl ether, diethylene glycol isopropyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, tetraethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol dimethyl ether, ethylene glycol Monomethyl ether acetate, ethylene glycol monoe Ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether
• ⁇ -butyrolactone, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetate, and diethylene glycol monomethyl ether acetate are preferable, and ⁇ -butyrolactone and diethylene glycol are more preferable in consideration of the balance between screen printability and organic solvent volatility.
• the content of (Component C) in the curable composition of the present invention is (Component A), (Component B), (Component C), and (Component D) described later, which are components of the curable composition of the present invention.
• the total amount is preferably 25 to It is 75% by mass, more preferably 35 to 65% by mass.
• the total amount of (Component A), (Component B) and (Component C)) is in the range of 25 to 75% by mass. Since the viscosity is good for printing by the screen printing method and the spread due to bleeding of the curable composition after screen printing does not increase so much, as a result, the portion to be coated with the curable composition (that is, the shape of the printing plate) ), The printing area of the actual curable composition does not become too large.
• (Component C) is preferably contained in an amount of 0.5 to 20 parts by mass with respect to 100 parts by mass of (Component A).
• the curable composition of the present invention can and preferably includes at least one kind of fine particles selected from the group consisting of inorganic fine particles and organic fine particles which are (Component D).
• inorganic fine particles examples include silica (SiO 2 ), alumina (Al 2 O 3 ), titania (TiO 2 ), tantalum oxide (Ta 2 O 5 ), zirconia (ZrO 2 ), silicon nitride (Si 3 N 4 ).
• the organic fine particles are preferably heat-resistant resin fine particles having an amide bond, an imide bond, an ester bond or an ether bond.
• These resins are preferably polyimide resins or precursors thereof, polyamideimide resins or precursors thereof, or polyamide resins from the viewpoint of heat resistance and mechanical properties. These can be used alone or in combination of two or more.
• (Component D) can preferably include at least one selected from silica fine particles and hydrotalcite fine particles.
• the silica fine particles used in the curable composition of the present invention are defined to include fine particles that are physically coated with a powder or chemically surface-treated with an organic compound.
• the silica particles used in the curable composition of the present invention are not particularly limited as long as they are dispersed in the curable composition of the present invention to form a paste.
• Silica fine particles represented by these aerosils are sometimes used for imparting printability during screen printing, and in that case, they are used for the purpose of imparting thixotropy.
• hydrotalcite is a kind of naturally occurring clay minerals typified by Mg 6 Al 2 (OH) 16 CO 3 .4H 2 O and is a layered inorganic compound.
• the hydrotalcite may be a synthetic material, and such a hydrotalcite is an Mg / Al-based layered compound, and chloride ions (Cl ⁇ ) and ion are exchanged with a carbonate group between layers. / Or Anion of sulfate ion (SO 4 ⁇ ) can be immobilized. Using this function, chloride ions (Cl ⁇ ) and sulfate ions (SO 4 ⁇ ), which cause migration of copper and tin, can be captured and used for the purpose of improving insulation reliability. .
• Examples of commercial products of hydrotalcite include STABIACE HT-1, STABIACE HT-7, and STABIACE HT-P from Sakai Chemical Co., Ltd., DHT-4A, DHT-4A2, and DHT-4C from Kyowa Chemical Industry Co., Ltd. Is mentioned.
• the average particle diameter of these inorganic fine particles and / or organic fine particles is preferably 0.01 to 10 ⁇ m, more preferably 0.1 to 5 ⁇ m.
• the blending amount of (Component D) is 0.1 to 60% by mass, preferably 0.3 to 4%, based on the total amount of (Component A), (Component B), (Component C) and (Component D).
• the content is 55% by mass, and more preferably 0.5 to 40% by mass.
• the curable composition Since the viscosity of the product is good for printing by the screen printing method and the spread due to bleeding of the curable composition after screen printing does not increase so much, as a result, the portion where the curable composition is to be applied (that is, the printing plate) The actual printed area of the curable composition does not become too large.
• (Component D) is preferably contained in an amount of 1 to 30 parts by mass with respect to 100 parts by mass of (Component A).
• (Component D) is preferably contained in an amount of 1 to 30 parts by mass with respect to 100 parts by mass of (Component A).
• the curable composition of the present invention can and preferably includes an antifoaming agent for the purpose of eliminating or suppressing the generation of bubbles during printing.
• the content of the antifoaming agent is the total amount of (Component A), (Component B), (Component C) and (Component D) (provided that (Component D) is not included in the curable composition of the present invention).
• the antifoaming agent is preferably contained in an amount of 0.2 to 10 parts by mass with respect to 100 parts by mass of (Component A).
• the curable composition of the present invention can and preferably includes a curing accelerator.
• the curing accelerator is not particularly limited as long as it is a compound that accelerates the reaction between an epoxy group and a carboxyl group.
• melamine, acetoguanamine, benzoguanamine, 2,4-diamino-6-methacryloyloxyethyl-S Triazines such as triazine, 2,4-methacryloyloxyethyl-s-triazine, 2,4-diamino-6-vinyl-s-triazine, 2,4-diamino-6-vinyl-s-triazine and isocyanuric acid adducts
• imidazole 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1-benzyl-2-methylimidazole, 2-phenyl-4-methylimidazole 1-cyanoethyl-2 Methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-amino
• curing accelerators may be used alone or in combination of two or more.
• preferred curing accelerators in view of achieving both curing acceleration and electrical insulation performance, preferred are melamine, imidazole compounds, cycloamidine compounds, derivatives of cycloamidine compounds, phosphine compounds and amines. More preferred are melamine, 1,5-diazabicyclo (4.3.0) nonene-5 and salts thereof, and 1,8-diazabicyclo (5.4.0) undecene-7 and salts thereof.
• the blending amount of these curing accelerators is not particularly limited as long as the curing acceleration effect can be achieved.
• the curable composition of the present invention contains It is preferably blended in the range of 0.05 to 5 parts by mass, more preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the total amount of (Component A) and (Component B) as essential components of the present invention Part.
• the blending amount is in the range of 0.05 to 5 parts by mass with respect to 100 parts by mass of the total amount of (Component A) and (Component B), it can be cured in a short time and the curability of the present invention.
• the electrical insulation characteristics and water resistance of the overcoat film obtained by curing the composition are improved.
• the curable composition of the present invention includes a phenolic antioxidant, a phosphite antioxidant, a thioether antioxidant, and the like.
• An antioxidant can be added.
• a leveling agent a colorant such as a dye or a pigment, a flame retardant, and a lubricant are added to the curable composition of the present invention in order to improve workability during coating and film properties before and after film formation. You can also.
• the method for producing the curable composition of the present invention is not particularly limited as long as (Component A), (Component B) and (Component C) and, if necessary, other components can be dissolved or dispersed in an organic solvent.
• the curable composition of the present invention may be produced by producing a main agent containing at least (Component A) and a curing agent containing at least (Component B), and then blending the main agent and the curing agent. .
• the curable composition of the present invention improves the screen printability and prevents the composition from flowing and not having a constant film thickness after printing the curable composition.
• the thixotropy index is desirably 1.1 or more at 25 ° C., more preferably in the range of 1.1 to 3.0, and particularly preferably in the range of 1.1 to 2.5.
• there are a method of adjusting the thixotropy index using the inorganic fine particles and organic fine particles there are a method of adjusting the thixotropy index using a polymer additive, and the like. The method of adjusting the thixotropy index using inorganic fine particles or organic fine particles is preferred.
• the “thixotropic index” described in this specification is a rotation at 25 ° C. measured using a cone / plate viscometer (manufactured by Brookfield, model: DV-II + Pro, spindle model number: CPE-52). It is defined as the ratio of the viscosity at several rpm and the viscosity at 10 rpm at 25 ° C.
• the curable composition preferably has a viscosity at 25 ° C. of 20 Pa ⁇ s to 80 Pa ⁇ s, more preferably 30 Pa ⁇ s to 50 Pa ⁇ s, as measured by a rotary viscometer.
• a viscosity is less than 20 Pa ⁇ s, there is a tendency that the flow of the composition after printing becomes large and the film thickness tends to be reduced, and when it exceeds 80 Pa ⁇ s, the transfer property of the composition to the substrate is increased. There is a tendency that voids and pinholes in the printed film increase with decreasing.
• the cured film of the present invention includes a cured product that can be obtained by curing the curable composition of the present invention.
• the electronic component of this invention has the said cured film.
• the overcoat film of the present invention is an overcoat film for a flexible wiring board containing a cured product of the curable composition of the present invention. More specifically, the curable composition of the present invention is wired on a flexible substrate. This is an overcoat film for a flexible wiring board obtained by applying and curing a part or all of the surface on which the wiring is formed of the formed flexible wiring board.
• the flexible wiring board of the present invention is a flexible wiring board in which a part or all of the surface on which the wiring is formed of the flexible wiring board formed by wiring on the flexible substrate is covered with the overcoat film. is there.
• the wiring covered with the overcoat film is preferably a tin-plated copper wiring in view of the oxidation prevention and economical aspect of the wiring.
• the manufacturing method of the flexible wiring board of this invention is a manufacturing method of the flexible wiring board coat
• Step 1 ′ Step of forming a printed film on the pattern by printing the curable composition of the present invention on at least a part of the wiring pattern portion of the flexible wiring board (Step 2 ′) Obtained in Step 1 ′
• the curable composition of the present invention can be used, for example, as an ink for an overcoat film for insulation protection of wiring, and the cured product of the present invention can be used as an overcoat film for insulation protection.
• the cured product of the present invention can be used as an overcoat film for insulation protection.
• a flexible wiring board such as a chip-on-film (COF)
• COF chip-on-film
• the overcoat film of the flexible wiring board can be formed through the following step 1 and step 3 and step 2 as necessary.
• Process 1 The process of forming a printed film on this pattern by printing the curable composition of this invention in at least one part of the wiring pattern part of a flexible wiring board (process 2) A step of evaporating a part or all of the solvent in the printed film by placing the printed film obtained in step 1 in an atmosphere of 40 to 100 ° C. (step 3) A step of curing the printed film obtained in step 1 or the printed film obtained in step 2 at 100 to 170 ° C. to form an overcoat film.
• the temperature at which the solvent in the printed film is evaporated by placing the printed film obtained in Step 1 in an atmosphere of 40 to 100 ° C., which is carried out in Step 2, depends on the evaporation rate of the solvent and the subsequent operation (100 to 100 ° C.). In consideration of a rapid transition to an operation of curing by heating at 170 ° C., the temperature is usually 40 to 100 ° C., preferably 60 to 100 ° C., and more preferably 70 to 90 ° C.
• the time for evaporating the solvent in the printed film by placing the printed film obtained in Step 1 in the atmosphere of 40 to 100 ° C. carried out in Step 2 is not particularly limited, but preferably 10 to 120. Minutes, more preferably 20 to 100 minutes.
• thermosetting evaporating the solvent in the printed film by placing the printed film obtained in Step 1 in an atmosphere of 40 to 100 ° C.
• the process proceeds to Step 3 and is heated at 100 to 170 ° C. to cure and form an overcoat film, and the curing reaction and the solvent removal may be performed together.
• the conditions for the thermosetting performed here are preferably 105 to 160 ° C., more preferably 110 from the viewpoint of preventing diffusion of the plating layer and obtaining low warpage and flexibility suitable as a protective film.
• ⁇ 150 ° C There is no particular limitation on the heat curing time for curing by heating to form an overcoat film, but it is preferably 10 to 150 minutes, more preferably 15 to 120 minutes.
• a flexible wiring board in which wiring is formed on a flexible substrate a flexible wiring board in which a part or all of the surface on which the wiring is formed is covered with the overcoat film can be obtained. it can.
• the curable composition of the present invention is blended with the above-described optional components as necessary, and is uniformly mixed, and as a film forming material, an overcoat ink for semiconductor elements and various electronic components, solder resist ink, interlayer insulation Besides being useful as a film, it can also be used as a paint, a coating agent, an adhesive and the like.
• A represents the acid value (mgKOH / g)
• Vf represents the titration amount (mL) of the 0.1N KOH solution
• Wp represents the mass (g) of the solution containing (Component A).
• I represents the ratio (mass%) of the component (A) of the solution containing (component A).
• the hydroxyl value was 53.1 mg-KOH / g.
• the terminal acid anhydride group-containing imide prepolymer having a solid content concentration of 30% by mass was heated to 100 ° C. and stirred to obtain 908.7 parts by mass of polyester diol ( ⁇ ) and 1018.7 parts by mass of ⁇ -butyrolactone. Was added and stirred.
• 2.4 parts by mass of 4-dimethylaminopyridine (DMAP) was added as a catalyst and reacted at 100 ° C. for 8 hours.
• DMAP 4-dimethylaminopyridine
• compound (A-1) a solution of a compound having an imide bond and a hydroxyl group having a solid content concentration of 40% by mass was obtained.
• the number average molecular weight of the compound (A-1) was 15000, the degree of dispersion was 4.0, and the acid value of the solid content was 25 mgKOH / g.
• the terminal acid anhydride group-containing imide prepolymer having a solid content concentration of 30% by mass was heated to 100 ° C. and stirred, and a polyester polyol of 3-methyl-1,5-pentanediol: isophthalic acid (manufactured by Kuraray Co., Ltd.).
• Product name 908.7 parts by mass of Kuraray polyol P-2030 (*) and 1018.7 parts by mass of ⁇ -butyrolactone were added and stirred.
• 2.4 parts by mass of 4-dimethylaminopyridine (DMAP) was added as a catalyst and reacted at 100 ° C. for 8 hours.
• compound (A-2) a solution of a compound having an imide bond and a hydroxyl group (hereinafter referred to as “compound (A-2)”) having a solid content concentration of 40% by mass was obtained.
• the number average molecular weight of the compound (A-2) was 15000, the degree of dispersion was 4.0, and the acid value of the solid content was 25 mgKOH / g.
• TDI Cosmonate T-80 (Mitsui Chemical Polyurethane Co., Ltd.)
• DBU 1,8-diazabicyclo [5.4.0] -7-undecene
• the terminal acid anhydride group-containing imide prepolymer having a solid content concentration of 30% by mass was heated to 100 ° C. and stirred to obtain 908.7 parts by mass of polyester diol ( ⁇ ) and 1054.8 parts by mass of ⁇ -butyrolactone. Was added and stirred.
• 2.4 parts by mass of 4-dimethylaminopyridine (DMAP) was added as a catalyst and reacted at 100 ° C. for 8 hours.
• DMAP 4-dimethylaminopyridine
• compound (A-3) a solution of a compound having an imide bond and a hydroxyl group having a solid content concentration of 40% by mass was obtained.
• the number average molecular weight of the compound (A-3) was 15000, the degree of dispersion was 4.0, and the acid value of the solid content was 26 mgKOH / g.
• TDI Cosmonate T-80 (Mitsui Chemical Polyurethane Co., Ltd.)
• DBU 1,8-diazabicyclo [5.4.0] -7-undecene
• the terminal acid anhydride group-containing imide prepolymer having a solid content concentration of 30% by mass was heated to 100 ° C. and stirred, and a polyester polyol of 3-methyl-1,5-pentanediol: isophthalic acid (manufactured by Kuraray Co., Ltd.). Trade name: Kuraray polyol P-2030) 908.7 parts by mass and ⁇ -butyrolactone 1054.8 parts by mass were added and stirred. To this, 2.4 parts by mass of 4-dimethylaminopyridine (DMAP) was added as a catalyst and reacted at 100 ° C. for 8 hours.
• DMAP 4-dimethylaminopyridine
• compound (A-4) a solution of a compound having an imide bond and a hydroxyl group (hereinafter referred to as “compound (A-4)”) having a solid content concentration of 40% by mass was obtained.
• the number average molecular weight of the compound (A-4) was 15000, the degree of dispersion was 4.0, and the acid value of the solid content was 26 mgKOH / g.
• reaction solution was raised to 180 ° C. and reacted at 180 ° C. for 2 hours. Subsequently, the temperature of the reaction solution was lowered to 120 ° C., 5.61 g of 2-butanone oxime (manufactured by Wako Pure Chemical Industries, Ltd.) was added, the reaction was terminated, and the mixture was cooled to room temperature, whereby an amide having a solid content concentration of 40% by mass was obtained.
• a solution of a compound having a bond and an imide bond and a block isocyanate group hereinafter referred to as “compound (A-5)”) was obtained.
• the number average molecular weight of the obtained compound (A-5) was 10,500, the degree of dispersion was 3.1, and the acid value of the solid content was 19 mgKOH / g.
• reaction solution was raised to 180 ° C. and reacted at 180 ° C. for 2 hours. Subsequently, the temperature of the reaction solution was lowered to 120 ° C., 5.61 g of 2-butanone oxime (manufactured by Wako Pure Chemical Industries, Ltd.) was added, the reaction was terminated, and the mixture was cooled to room temperature, whereby an amide having a solid content concentration of 40% by mass was obtained.
• a solution of a compound having a bond and an imide bond and a block isocyanate group hereinafter referred to as “compound (A-6) was obtained.
• the number average molecular weight of the obtained compound (A-6) was 10,500, the degree of dispersion was 3.1, and the acid value of the solid content was 19 mgKOH / g.
• the temperature of the reaction solution is lowered to 80 ° C., 16.40 g (0.158 mol) of neopentyl glycol (manufactured by Kanto Chemical Co., Ltd.) as a diol is added, and the temperature is raised to 120 ° C. to dissolve all the raw materials for 4 hours. Reacted. Thereafter, the temperature of the reaction solution is lowered to 80 ° C., and 9.67 g (0.105 mol) of glycerin (manufactured by Kanto Chemical Co., Ltd.) as a triol and 39.10 g of ⁇ -butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) are added. The temperature was raised to 0 ° C.
• reaction was allowed to proceed.
• the reaction is carried out while confirming the presence of the isocyanate group in the reaction solution by IR measurement.
• the reaction is terminated, and the reaction mixture is cooled to room temperature.
• a solution of a compound having an amide bond, an imide bond and a hydroxyl group (hereinafter referred to as “compound (A-7)”) was obtained.
• the number average molecular weight of the obtained compound (A-7) was 10,000, the degree of dispersion was 4.3, the acid value of the solid content was 17 mgKOH / g, and the hydroxyl value was 10 mgKOH / g.
• a polycarbonate diol compound trade name: DURANOL T5650E: manufactured by Asahi Kasei Chemicals Corporation
• Mn 500
• compound (CA-1) 4-dimethylaminopyridine (DMAP) was added as a catalyst and reacted at 100 ° C. for 8 hours. Thereafter, by cooling to room temperature, a solution of a compound having an imide bond, a carboxyl group, and a hydroxyl group (hereinafter referred to as “compound (CA-1)”) having a solid content concentration of 40% by mass was obtained.
• the number average molecular weight of the compound (CA-1) was 13,500, the degree of dispersion was 4.0, and the acid value of the solid content was 36 mgKOH / g.
• a reaction vessel equipped with a stirrer, a thermometer, and a condenser contains a structural unit derived from 1,4-cyclohexanedimethanol and a structural unit derived from 1,6-hexasandiol in a molar ratio of 1: 1.
• Polycarbonate diol UM-CARB90 (1/1) (manufactured by Ube Industries Co., Ltd.) 161.44 g (0.179 mol) is added, and MILIONATE MT (manufactured by Nippon Polyurethane Industry Co., Ltd.) which is 4,4′-diphenylmethane diisocyanate 53.
• the temperature of the reaction solution was raised to 180 ° C. and reacted at 180 ° C. for 2 hours. Subsequently, the temperature of the reaction solution was lowered to 120 ° C., 3.13 g of 2-butanone oxime (manufactured by Wako Pure Chemical Industries, Ltd.) was added, the reaction was terminated, and the mixture was cooled to room temperature, whereby an amide having a solid content concentration of 40% by mass was obtained.
• a solution of a compound having a bond, an imide bond and a carboxyl group hereinafter referred to as “compound (C ⁇ -2)”) was obtained.
• the compound (C ⁇ -2) obtained had a number average molecular weight of 9,200, a dispersity of 3.1, and an acid value of solid content of 31 mgKOH / g.
• a reaction vessel equipped with a stirrer, a thermometer, and a condenser contains a structural unit derived from 1,4-cyclohexanedimethanol and a structural unit derived from 1,6-hexasandiol in a molar ratio of 3: 1.
• the temperature of the reaction solution is lowered to 80 ° C., 16.40 g (0.158 mol) of neopentyl glycol (manufactured by Kanto Chemical Co., Ltd.) as a diol is added, and the temperature is raised to 120 ° C. to dissolve all raw materials, and 4 hours Reacted. Thereafter, the temperature of the reaction solution is lowered to 80 ° C., and 9.67 g (0.105 mol) of glycerin (manufactured by Kanto Chemical Co., Ltd.) as a triol and 26.07 g of ⁇ -butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) are added. The temperature was raised to 0 ° C.
• reaction was allowed to proceed.
• the reaction is carried out while confirming the presence of the isocyanate group in the reaction solution by IR measurement.
• the reaction is terminated, and 177.1 g of ⁇ -butyrolactone is added to obtain a solid concentration of 40
• the obtained compound (CA-3) had a number average molecular weight of 8000, a degree of dispersion of 4.4, an acid value of solid content of 27 mgKOH / g, and a hydroxyl value of 16 mgKOH / g.
• composition example 2 of curing agent solution ⁇ B-2 solution>
• an epoxy resin mainly composed of N, N-diglycidyl-4- (glycidyloxy) aniline manufactured by Mitsubishi Chemical Corporation, grade name: JER630, epoxy equivalent 98 g / eqv) ) 16.85 parts by mass and 18.25 parts by mass of diethylene glycol diethyl ether were added and stirring was started.
• curable composition F1 a curable composition
• Examples 2 to 8 and Comparative Examples 1 to 3 The curable composition was formulated according to the composition shown in Table 2 by the same method as in Example 1.
• the formulations prepared in Examples 2 to 8 of the curable composition were respectively prepared as the curable compositions F2 to F8, and the formulations prepared in Comparative Examples 1 to 3 of the curable composition were respectively used as the curable compositions G1 to G3.
• a block isocyanate “7950” manufactured by Baxenden corresponding to (Component B) was further blended.
• Table 2 shows the composition of the curable compositions F1 to F8 and the curable compositions G1 to G3.
• Table 3 shows a summary of the parts by mass of the components of the curable compositions F1 to F8 and the curable compositions G1 to G3.
• the number of epoxy groups / the number of carboxyl groups in Tables 2 and 3 was calculated from the acid value.
• a flexible copper-clad laminate manufactured by Sumitomo Metal Mining Co., Ltd., grade name: Esperflex, copper thickness: 8 ⁇ m, polyimide thickness: 38 ⁇ m
• the curable composition F1 was applied by screen printing so as to have a thickness of 15 ⁇ m, held at room temperature for 10 minutes, and cured by placing it in a 120 ° C. hot air circulating dryer for 60 minutes.
• the protective PET film on the backing of the prepared test piece was peeled off, cut into a strip shape with a width of 10 mm with a cutter knife, bent about 180 degrees so that the coating surface was on the outside, and 0.5 ⁇ using a compressor. Compressed at 0.2 MPa for 3 seconds. The bent part was bent and observed with a 30-fold microscope to confirm the presence or absence of cracks.
• Table 4 The same evaluation was performed using the curable compositions F2 to F8 and the curable compositions G1 to G3. The results are also shown in Table 4.
• the curable composition F1 was applied to a substrate by screen printing with a # 180 mesh polyester plate, and the substrate was placed in a hot air circulation dryer at 80 ° C. for 30 minutes. Then, the applied curable composition F1 was cured by placing the substrate in a 120 ° C. hot air circulation dryer for 60 minutes. As the substrate, a 25 ⁇ m-thick polyimide film [Kapton (registered trademark) 100EN, manufactured by Toray DuPont Co., Ltd.] was used.
• the cured coating film was cut with a circle cutter to a diameter of 50 mm ⁇ together with the substrate. What is cut into a circle exhibits a deformation in which the vicinity of the center warps in a convex or concave shape.
• the one that has been cut with a circle cutter and has a cured film formed on the substrate is placed in a convex state after 1 hour, that is, with the cured film formed on the substrate so that the vicinity of the center is in contact with the horizontal plane.
• the maximum and minimum values of the warp height from the horizontal plane were measured, and the average value was obtained.
• the sign indicates the direction of warping.
• the curable composition of the present invention is excellent in flexibility, wire breakage suppression and long-term electrical insulation reliability, and the cured product is useful as an insulating protective film for flexible wiring boards.
• the curable composition of the present invention can be suitably used for insulation protection of flexible wiring boards.

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