WO2011062137A1 - ウレタン変性ポリイミド系難燃樹脂組成物 - Google Patents
ウレタン変性ポリイミド系難燃樹脂組成物 Download PDFInfo
- Publication number
- WO2011062137A1 WO2011062137A1 PCT/JP2010/070282 JP2010070282W WO2011062137A1 WO 2011062137 A1 WO2011062137 A1 WO 2011062137A1 JP 2010070282 W JP2010070282 W JP 2010070282W WO 2011062137 A1 WO2011062137 A1 WO 2011062137A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- urethane
- flame retardant
- modified polyimide
- resin composition
- acid
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- 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
- C08G73/1035—Preparatory processes from tetracarboxylic acids or derivatives and diisocyanates
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/343—Polycarboxylic acids having at least three carboxylic acid groups
- C08G18/345—Polycarboxylic acids having at least three carboxylic acid groups having three carboxylic acid groups
-
- 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
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- 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
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4808—Mixtures of two or more polyetherdiols
-
- 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
- C08G18/48—Polyethers
- C08G18/487—Polyethers containing cyclic groups
- C08G18/4879—Polyethers containing cyclic groups containing aromatic groups
-
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
-
- 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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0066—Flame-proofing or flame-retarding additives
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1545—Six-membered rings
-
- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/5399—Phosphorus bound to nitrogen
-
- 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
Definitions
- the present invention relates to a urethane-modified polyimide resin composition having excellent heat resistance and flexibility and suitable for a coating method such as a printing press, a dispenser or a spin coater.
- the urethane-modified polyimide resin composition of the present invention is useful for a solder resist layer, a surface protective layer, an interlayer insulating layer, or an adhesive layer of a flexible printed wiring board of an electronic component.
- flexible printed wiring boards are electronic device parts that require flexibility and small space, for example, device mounting boards for display devices such as liquid crystal displays and plasma displays, and boards for mobile phones, digital cameras, portable game machines, etc. Widely used for relay cables, operation switch board, etc.
- polyimide resins are generally hard with a high elastic modulus, when laminated on a substrate such as a film or a copper foil, warping or the like occurs due to a difference in elastic modulus, which causes a problem in the subsequent process.
- the cured film lacks flexibility and has a problem of poor flexibility.
- a polysiloxane-modified polyimide resin has been proposed as a polyimide resin that is soluble in a non-nitrogen solvent and imparts low warpage and flexibility by making the resin flexible and low elastic modulus. (See Patent Documents 1 and 2).
- polysiloxane-modified polyimide resins use expensive diamine having a dimethylsiloxane bond as a starting material in order to lower the elastic modulus, and have a problem of poor economic efficiency.
- polysiloxane copolymerization amount increases, there is a problem that adhesion, solvent resistance, and chemical resistance decrease.
- compositions using a polycarbonate-modified polyimide resin have been proposed (see Patent Documents 3 to 5).
- polycarbonate-modified polyimide resins have improved defects derived from polysiloxane and have good printability.
- a polyimide resin polycarbonate is used to reduce warpage. It was necessary to increase the amount of modification, and the heat resistance tended to decrease. Moreover, varnish stability was low and the varnish sometimes solidified within a few days during storage. Furthermore, in general, when a low elastic modulus component is introduced in order to obtain low warpage, the flame retardancy often decreases in contradiction. The coating film obtained from the composition proposed here could not obtain sufficient flame retardancy.
- polycarbonate-modified polyimide resin compositions have low warpage, flexibility and flame retardancy, but when introducing a low elastic modulus component to reduce warpage, the heat resistance and flame retardancy are contradictory. Often decreases.
- the proposed composition is intended for tape carrier package (TAB, COF) applications using relatively thick polyimide film substrates, and flexible printed wiring using thin polyimide film substrates of 1 mil (25 ⁇ m) or less.
- TAB tape carrier package
- FPC substrate
- Patent Document 9 contains at least one component selected from the group consisting of polyether, polyester, polyacrylonitrile-butadiene copolymer, polycarbonate diol, and dimer acid as a copolymer component, and an isophorone residue.
- a polyimide resin having an essential component as a component is proposed.
- Patent Document 10 discloses a polyimide resin containing a polyether as a copolymer component, trimellitic acid as an acid component, and cyclohexanedicarboxylic acid, and a composition comprising the same. Proposed.
- polyimide resins are expected to be excellent in solubility in non-nitrogen solvents, but they did not satisfy low warpage, solder heat resistance and printability at the same time as flexible printed wiring board applications.
- any of the polyimide resins is a non-nitrogen reaction solvent, the varnish stability is low, the resin is likely to precipitate over time, and for the purpose of use, it is further re-precipitated to a highly soluble low-boiling solvent. The total replacement of was performed, and it was inferior in economic efficiency.
- these proposed compositions mainly consist of alicyclic components, sufficient flame retardancy cannot be obtained.
- Patent Document 11 proposes a composition using a polyimide resin containing a polyalkylene oxide adduct of bisphenol A. Although this polyimide resin composition is excellent in heat resistance, it is not soluble in non-nitrogen solvents, it cannot be said that it has low warpage and flexibility, and flame retardancy was not obtained. .
- Patent Document 12 proposes a polyimide composition in which a hydrated metal compound, a phosphorus compound, and a nitrogen compound as non-halogen flame retardants are used as fillers in a polysiloxane-modified polyimide resin.
- This polyimide-based resin composition is expected to satisfy the flame retardance standards according to UL standards in addition to properties such as solder heat resistance and printability for flexible printed circuit board applications. There was a problem due to copolymerization of siloxane compounds. Further, as in Patent Documents 7 to 8, when a large amount of a hydrated metal compound having a low flame retardant effect is contained, there is a problem that the elastic modulus is increased and low warpage and flexibility are lowered.
- Patent Document 13 proposes a siloxane diamine-modified polyimide resin composition using a special monomer in order to improve the above-mentioned drawbacks.
- This polyimide-based resin composition does not contain an inorganic flame retardant, and is expected not to impair the low warpage.
- an expensive monomer since an expensive monomer is used, it is inferior in economic efficiency and has adhesiveness caused by a siloxane compound. There was a problem.
- Patent Document 14 proposes a polyurethane resin composition and a polyimide resin composition using a dialkyl phosphinate metal salt as a non-halogen flame retardant.
- This polyurethane-based resin composition is expected to satisfy the standards of flame retardancy according to UL standards in addition to properties such as solder heat resistance and printability for flexible printed circuit board applications. Since they are not compatible with each other and are blended in a large amount as a filler, flexibility and low warpage are not always sufficient.
- the present invention was devised in order to solve the above-mentioned problems of the prior art, and its purpose is (1) non-nitrogen solvent solubility and varnish stability, (2) low temperature drying / curing property, (3) Low warpage, (4) Flexibility, (5) Printability, (6) Excellent flame retardancy, suppresses bleed out of flame retardant, heat resistance, chemical resistance, electrical properties, workability and An object of the present invention is to provide a urethane-modified polyimide-based flame retardant resin composition excellent in economy and an electronic component obtained by using the composition.
- the present invention comprises the following configurations (1) to (12).
- (1) (a) a trivalent and / or tetravalent polycarboxylic acid derivative having an acid anhydride group, (b) a diol compound, and (c) an aliphatic polyamine residue derivative and / or an aromatic polyamine residue derivative A urethane-modified polyimide resin having a urethane bond produced as an essential component, (B) an epoxy resin having two or more epoxy groups per molecule; (C) inorganic or organic filler, and (D) non-halogen flame retardant, A urethane-modified polyimide flame retardant resin composition containing (D) A non-halogen flame retardant comprises two components: a component (D-1) having a weight loss rate of 50% to 90% at 350 ° C.
- a urethane-modified polyimide-based flame retardant resin composition characterized by comprising (2) The weight reduction rate of component (D-1) is 60% or more and 85% or less, and the weight reduction rate of component (D-2) is 0% or more and 15% or less (1)
- the component (D-1) contains a 9,10-dihydro-9-oxa-10-phenanthrene-10-oxide derivative, and the component (D-2) contains a phenoxyphosphazene compound (1) )
- a urethane-modified polyimide flame retardant resin composition To (3), a urethane-modified polyimide flame retardant resin composition.
- the urethane-modified polyimide-based flame retardant resin composition according to any one of (1) to (3) or (5), which comprises the reaction product of (In Formula [I] and Formula [II], R 1 and R 2 may be the same or different from each other, and linear or branched C 1 -C 10 alkyl and / or cycloalkyl and / or Aryl and / or aralkyl, R 1 and R 2 may be bonded to each other to form a ring with an adjacent phosphorus atom, R 3 is linear or branche
- the (b) diol compound contains (b-1) polyoxyalkylene glycol and / or (b-2) a polyalkylene oxide adduct of bisphenol represented by the following general formula [III]
- the urethane-modified polyimide flame retardant resin composition according to any one of (1) to (7).
- R 1 is a C 1 -C 20 alkylene group
- R 2 and R 3 may be the same or different from each other, and represent hydrogen or a C 1 -C 4 alkyl group.
- a urethane-modified polyimide resin is obtained by reaction in at least one organic solvent selected from the group consisting of ether solvents, ester solvents, ketone solvents, and aromatic hydrocarbon solvents.
- the present invention (1) non-nitrogen solvent solubility and varnish stability, (2) low temperature drying / curing properties, (3) low warpage, and (4) bending, which have been difficult to satisfy at the same time.
- a resin composition can be provided. Therefore, the urethane-modified polyimide flame retardant resin composition of the present invention is useful as a film forming material for overcoat inks for various electronic parts such as flexible printed wiring boards, solder resist inks, interlayer insulating films, and paints. It can be used in a wide range of electronic equipment as coating agents, adhesives, etc.
- the urethane-modified polyimide flame retardant resin composition of the present invention is (A) (a) a trivalent and / or tetravalent polycarboxylic acid derivative having an acid anhydride group, (b) a diol compound, (c) an aliphatic polyamine residue derivative and / or an aromatic polyamine residue derivative A urethane-modified polyimide resin having a urethane bond produced as an essential component; (B) an epoxy resin having two or more epoxy groups per molecule; (C) inorganic or organic filler, and (D) non-halogen flame retardant, Containing (D) A non-halogen flame retardant comprises two components: a component (D-1) having a weight loss of 50% to 90% at 350 ° C. in an air atmosphere and a component (D-2) having a component weight of 0% to 20%. Is contained as an essential component.
- a trivalent and / or tetravalent polycarboxylic acid derivative having an acid anhydride group constituting the component (A) generally reacts with an isocyanate component or an amine component to form a polyimide resin.
- the polycarboxylic acid derivative any of aromatic, aliphatic and alicyclic can be used.
- the copolymerization amount of the component (a) is preferably 30 mol% or more and 90 mol% or less, and 35 mol% or more and 85 mol% or less, in a molar ratio with respect to 100 mol% of all polyamine residue derivatives to be reacted. Is more preferable. If the copolymerization amount is less than the above range, flame retardancy, mechanical properties and heat resistance cannot be obtained. If the copolymerization amount is more than the above range, the component (b) described later cannot be copolymerized in a sufficient amount. And solubility in non-nitrogen solvents may be reduced.
- aromatic polycarboxylic acid derivatives include trimellitic anhydride, pyromellitic dianhydride, ethylene glycol bisan hydrotrimellitate, propylene glycol bisan hydrotrimellitate, 1,4-butanediol bisan.
- Alkylene glycol bisanhydro trimellitates such as hydrotrimellitate, hexamethylene glycol bisanhydro trimellitate, polyethylene glycol bisan hydrotrimellitate, polypropylene glycol bisan hydrotrimellitate, hydroquinone bisan hydrotrimellitate , Hydroquinone bisethylene oxide adduct dianhydrotrimellitate, 4,4'-biphenylenebisanhydrotrimellitate, 3,3 ', 4,4'-benzophenone tetracarbo Acid dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic Acid dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 3,3 ', 4,
- Examples of the aliphatic or alicyclic polycarboxylic acid derivatives include butane-1,2,3,4-tetracarboxylic dianhydride and pentane-1,2,4,5-tetracarboxylic dianhydride.
- polycarboxylic acid derivatives may be used alone or in combination of two or more.
- polycarboxylic acid derivatives are pyromellitic dianhydride, trimellitic anhydride, ethylene glycol bisanhydro trimellitate, 3, 3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 2,2-bis [4- (2,3- or 3, 4-dicarboxyphenoxy) phenyl] propane dianhydride is preferred, trimellitic anhydride, and ethylene glycol bisanhydro trimellitate are more preferred.
- the (b) diol compound constituting the component (A) is copolymerized as a flexible component that imparts flexibility, low warpage, solubility and the like to the polyimide resin.
- the elastic modulus of the resin decreases, and the solubility (varnish) stability in the non-nitrogen solvent used as the polymerization solvent increases.
- the amount of copolymerization of component (b) is preferably 10 mol% or more and 70 mol% or less, and 15 mol% or more and 65 mol% or less in terms of a molar ratio to 100 mol% of all polyamine residue derivatives to be reacted. Is more preferable. If the amount of copolymerization is more than the above range, flame retardancy, mechanical properties and heat resistance cannot be obtained, and if it is less than the above range, low warpage and solubility in non-nitrogen solvents may be reduced.
- the molecular weight of the component (b) is preferably a number average molecular weight of 500 or more and 3000 or less, more preferably 800 or more and 2000 or less. When the molecular weight is less than the above range, the heat resistance, flexibility and low warpage are insufficient, and when it exceeds the above range, the modification reaction does not proceed and the solubility may be lowered.
- diol compound examples include polyalkylene glycol, polyoxyalkylene glycol, polyalkylene oxide adduct of bisphenol, aliphatic / aromatic polyester diols, aliphatic / aromatic polycarbonate diols, polycaprolactone diols, and polybutadiene polyols. , Hydrogenated polybutadiene polyols, hydrogenated polyisoprene polyol, polydimethylsiloxane diol, polymethylphenylsiloxane diol, and the like.
- polyoxyalkylene glycols polyalkylene oxide adducts of bisphenol, aliphatic / aromatic polyester diols, and aliphatic / aromatic polycarbonate diols
- polyoxyalkylene glycols ((b- 1) Component), a polyalkylene oxide adduct of bisphenol represented by the general formula [III] (component (b-2)).
- Other diol compounds include bisphenols such as bisphenol A and bisphenol F, but these are not preferred because the urethane bond dissociates during heating.
- Aliphatic / aromatic polyester diols include those obtained by dehydration condensation of dicarboxylic acid and diol or transesterification of lower alcohol ester of dicarboxylic acid with diol, and ring-opening polymerization of lactone compounds using diol as an initiator. Or obtained by a condensation reaction between a diol and a hydroxyalkanoic acid.
- dicarboxylic acid component examples include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, eicosanedioic acid, and 2-methylsuccinic acid.
- diol component examples include ethylene glycol, propylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, neopentyl glycol, and 1,5-pentane.
- Diol 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, trimethylpentanediol, 2-ethyl-1,3-hexanediol, 1,8-octanediol, 2 -Methyl-1,8-octanediol, 1,9-nonanediol, 2,4-diethyl-1,5-pentanediol, 1,10-decanediol, 2,2-diethyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, diethylene glycol, triethyleneglycol Aliphatic diols such as eicosan diol and neopentyl glycol hydroxypivalate, alicyclic diols such as 1,4-cyclohexanedimethanol and
- hydroxyalkanoic acid component examples include 3-hydroxybutanoic acid, 4-hydroxypentanoic acid, 5-hydroxyhexanoic acid and the like.
- lactone examples include ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -methyl- ⁇ -propiolactone, ⁇ -methyl- ⁇ -propiolactone, 3-n-propyl- ⁇ -valerolactone, 6 , 6-dimethyl- ⁇ -valerolactone, glycolide, lactide and the like.
- Aliphatic / aromatic polycarbonate diols obtained by transesterification of diol and carbonate compound, obtained by ring-opening polymerization of cyclic carbonate compound, or obtained by reaction of diol and chloroformate or phosgene It is.
- 50 mol% or more of the alkylene chain contained is preferably an alkylene group having 6 or more carbon atoms, and 90 mol% or more is an alkylene group having 6 or more carbon atoms. Further preferred. Most preferably, it is a polycarbonate diol in which 50 mol% or more of the alkylene chain contained is an alkylene group having 8 or more carbon atoms.
- the aliphatic / aromatic polycarbonate diol is preferably a polycarbonate diol having a plurality of types of alkylene groups in its skeleton. Similarly, a polycarbonate diol having an alkylene group containing a side chain is preferred.
- polyoxyalkylene glycol examples include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly (neopentyl glycol / tetramethylene glycol), and the like.
- the copolymerization amount of the component (b-1) is preferably such that the mass of the polyurethane comprising the component (b-1) and the polyamine residue derivative is 5% by mass or more and 70% by mass or less of the urethane-modified polyimide resin. More preferably, it is 10 mass% or more and 40 mass% or less. If the copolymerization amount is less than the above range, the elastic modulus does not decrease sufficiently, warping occurs when laminated, and the solubility in non-nitrogen solvents decreases. May be deposited. This tendency is particularly noticeable when ⁇ -butyrolactone, glymes and cyclohexanone preferably used in the present invention are used as a solvent. On the other hand, when the above range is exceeded, flame retardancy, mechanical properties, and heat resistance may deteriorate.
- the polyalkylene oxide adduct of bisphenol is represented by the following general formula [III], and imparts non-nitrogen solvent solubility and flexibility to the modified polyimide resin.
- the polyalkylene oxide include polyethylene oxide, polypropylene oxide, and polytetramethylene oxide. Preferably, those having a number average molecular weight of 200 or more and 2000 or less are used. Specific examples include a polyethylene oxide adduct of bisphenol A and a polypropylene oxide adduct of bisphenol A.
- R 1 represents a C 1 -C 20 alkylene group
- R 2 and R 3 represent hydrogen or a carbon C 1 -C 4 alkyl group, which may be the same or different from each other
- m is an integer of 1 or more
- n is an integer of 1 or more.
- the copolymerization amount of the component (b-2) is preferably such that the mass of the polyurethane comprising the component (b-2) and the polyamine residue derivative is 10% by mass or more and 75% by mass or less of the urethane-modified polyimide resin. More preferably, it is 20 mass% or more and 70 mass% or less. If the copolymerization amount is less than the above range, the solubility in a non-nitrogen solvent decreases, and therefore the resin may precipitate within 5 months at 5 to 30 ° C. This tendency is particularly noticeable when ⁇ -butyrolactone, glymes and cyclohexanone preferably used in the present invention are used as a solvent. On the other hand, when the above range is exceeded, flame retardancy, mechanical properties, and heat resistance may deteriorate.
- aliphatic polyisocyanate and aliphatic polyamine are used as the (c) aliphatic polyamine residue derivative constituting the component (A).
- aliphatic polyisocyanate examples include hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate. Hexamethylene diisocyanate is preferred.
- aliphatic polyamine examples include hexamethylene diamine, 2,2,4-trimethylhexamethylene diamine, and lysine diamine. Hexamethylenediamine is preferred.
- Aromatic polyisocyanates include, for example, diphenylmethane-2,4'-diisocyanate, 3,2'- or 3,3'- or 4,2'- or 4,3'- or 5,2'- or 5, 3'- or 6,2'- or 6,3'-dimethyldiphenylmethane-2,4'-diisocyanate, 3,2'- or 3,3'- or 4,2'- or 4,3'- or 5 2,2'- or 5,3'- or 6,2'- or 6,3'-diethyldiphenylmethane-2,4'-diisocyanate, 3,2'- or 3,3'- or 4,2'- or 4,3'- or 5,2'- or 5,3'- or 6,2'- or 6,3'-dimethoxydiphenylmethane-2,4'-diisocyanate, diphenylmethane-4
- aromatic polyisocyanates are diphenylmethane-4,4′-diisocyanate, tolylene-2,4-diisocyanate, m-xylylene diisocyanate, 3,3 ′.
- 2,2′-dimethylbiphenyl-4,4′-diisocyanate is preferable, and diphenylmethane-4,4′-diisocyanate and tolylene-2,4-diisocyanate are more preferable.
- aromatic polyamines examples include diphenylmethane-2,4'-diamine, 3,2'- or 3,3'- or 4,2'- or 4,3'- or 5,2'- or 5,3. '-Or 6,2'- or 6,3'-dimethyldiphenylmethane-2,4'-diamine, 3,2'- or 3,3'- or 4,2'- or 4,3'- or 5, 2'- or 5,3'- or 6,2'- or 6,3'-diethyldiphenylmethane-2,4'-diamine, 3,2'- or 3,3'- or 4,2'- or 4 , 3'- or 5,2'- or 5,3'- or 6,2'- or 6,3'-dimethoxydiphenylmethane-2,4'-diamine, diphenylmethane-4,4'-diamine, diphenylmethane-3 , 3'-diamine, diphenylmethane-3,4'-diamine, diphenyl
- the aromatic polyamine is diphenylmethane-4,4′-diamine, tolylene-2,4-diamine, m-xylylenediamine, 3,3 ′ or 2,2'-dimethylbiphenyl-4,4'-diamine is preferred, and diphenylmethane-4,4'-diamine and tolylene-2,4-diamine are more preferred.
- the aliphatic polyamine residue derivative and / or the aromatic polyamine residue derivative may be used alone or in combination of two or more.
- the ratio of the aliphatic polyamine residue derivative and / or the aromatic polyamine residue derivative is not particularly limited, and is appropriately set within the range where the solubility and low warpage are not impaired in consideration of the amount of the diol compound (b). I do not care.
- the alicyclic in addition to the aliphatic polyamine residue derivative and the aromatic polyamine residue derivative, the alicyclic may be further added as necessary as long as the low warpage, heat resistance, and flame retardancy are not impaired.
- a group polyamine residue derivative may be copolymerized.
- examples of the alicyclic polyamine residue derivative include isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, transcyclohexane-1,4-diisocyanate, hydrogenated m-xylylene diisocyanate, and norbornylene diisocyanate.
- alicyclic polyisocyanates such as Considering heat resistance, adhesion, solubility, cost, etc., isophorone diisocyanate and 4,4′-dicyclohexylmethane diisocyanate are preferable.
- a polyamine residue derivative having three or more functional groups may be used, or one stabilized with a blocking agent necessary for avoiding changes over time may be used.
- the trifunctional or higher functional polyamine residue derivative is a trifunctional or higher functional polyisocyanate
- examples of the blocking agent include alcohol, phenol, and oxime, but there is no particular limitation. These trifunctional or higher functional polyisocyanates may be used alone or in combination of two or more.
- the isocyanate group at the end of the resin can be blocked with a blocking agent such as alcohols, lactams or oximes after completion of the polymerization.
- aliphatic, alicyclic, and aromatic dicarboxylic acids may be further copolymerized as necessary as long as the target performance is not impaired.
- the aliphatic dicarboxylic acid include succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedioic acid, dodecanedioic acid, eicosanedioic acid, 2-methylsuccinic acid, 2-methyladipic acid, 3 -Methyladipic acid, 3-methylpentanedicarboxylic acid, 2-methyloctanedicarboxylic acid, 3,8-dimethyldecanedicarboxylic acid, 3,7-dimethyldecanedicarboxylic acid, 9,12-dimethyleicosane diacid, fumaric acid, Maleic acid, dimer acid, hydrogenated dimer acid and the like.
- alicyclic dicarboxylic acid examples include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 4, 4'-dicyclohexyl dicarboxylic acid and the like
- aromatic dicarboxylic acids include Example, if isophthalic acid, terephthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, oxydibenzoic acid, stilbene dicarboxylic acid and the like. These dicarboxylic acids may be used alone or in combination of two or more. In view of heat resistance, adhesion, solubility, cost, etc., the dicarboxylic acids are preferably sebacic acid, 1,4-cyclohexanedicarboxylic acid, dimer acid, and isophthalic acid.
- a urethane-modified polyimide resin is a method of producing by decarboxylation from a polycarboxylic acid component having an acid anhydride group and an isocyanate component (isocyanate method), or reacting a polycarboxylic acid component having an acid anhydride group with an amine. It is produced by a known method such as a method (direct method) of ring-closing after making it into an amic acid. Industrially, an isocyanate method capable of urethane modification is advantageous.
- (A) In the case of producing a urethane-modified polyimide resin by an isocyanate method, (a) a trivalent and / or tetravalent polycarboxylic acid derivative having an acid anhydride group as a component and a diol compound as a component (b)
- the polymerization reaction of the urethane-modified polyimide resin is preferably carried out in the presence of at least one organic solvent selected from ether solvents, ester solvents, ketone solvents, and aromatic hydrocarbon solvents, for example, isocyanate.
- organic solvent selected from ether solvents, ester solvents, ketone solvents, and aromatic hydrocarbon solvents, for example, isocyanate.
- carbon dioxide gas that is liberated and generated is removed from the reaction system by heat condensation.
- ether solvent examples include glymes such as diethylene glycol dimethyl ether (diglyme), diethylene glycol diethyl ether (ethyl diglyme), triethylene glycol dimethyl ether (triglyme), and triethylene glycol diethyl ether (ethyl triglyme).
- solvent examples include ⁇ -butyrolactone, propylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate (butyl cellosolve acetate), ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate (ethyl carbitol acetate).
- Diethylene glycol examples include butyl ether acetate, 3-methoxybutyl acetate, dipropylene glycol methyl ether acetate, propylene glycol diacetate, methyl benzoate, and ethyl benzoate.
- ketone solvents include methyl isobutyl ketone, cyclopentanone, cyclohexanone, and isophorone.
- aromatic hydrocarbon solvent examples include toluene, xylene, and solvesso. These may be used alone or in combination of two or more.
- (A) In order to produce a varnish of a urethane-modified polyimide resin, it is preferable to select and use a solvent that dissolves the urethane-modified polyimide resin to be produced so that it can be used as it is as a varnish after polymerization. In this case, complicated operations such as solvent replacement are eliminated, and it becomes possible to manufacture at low cost.
- the boiling point of the solvent is preferably 140 ° C. or higher and 230 ° C. or lower. If the temperature is lower than 140 ° C., the solvent may be volatilized during the polymerization reaction. For example, when screen printing is performed, the solvent may volatilize quickly and the plate may be clogged.
- ⁇ -butyrolactone, cyclohexanone, diglyme, triglyme, ethyl carbitol are relatively high volatility, can provide low temperature drying / curing properties, have excellent varnish stability, and perform reaction efficiently and uniformly.
- Acetate is preferred.
- the amount of the solvent used is preferably 0.8 to 5.0 times (mass ratio) of the urethane-modified polyimide resin to be produced, and more preferably 0.9 to 2.0 times. If the amount used is less than the above range, the viscosity at the time of synthesis is too high, and the synthesis tends to be difficult due to the inability to stir, and if it exceeds the above range, the reaction rate tends to decrease.
- component and / or (b) component is added and reacted to obtain a urethane-modified polyimide resin, (3) excess (a) component and / or (b) component, and (c) )
- the component (c) is added and reacted to obtain a urethane-modified polyimide resin. Law, and the like.
- the reaction temperature is preferably 60 to 200 ° C, more preferably 100 to 180 ° C.
- the reaction time becomes too long, and when it exceeds the above range, the monomer component may be decomposed during the reaction. In addition, a three-dimensional reaction occurs and gelation is likely to occur.
- the reaction temperature may be performed in multiple stages. The reaction time can be appropriately selected depending on the scale of the batch, the reaction conditions employed, particularly the reaction concentration.
- the logarithmic viscosity of the urethane-modified polyimide resin is preferably from 0.1 dl / g to 2.0 dl / g, more preferably from 0.2 dl / g to 1.8 dl / g.
- the logarithmic viscosity is less than the above range, the heat resistance may be lowered or the coating film may be brittle.
- the tackiness of the paste is strong and the separation of the plate is poor.
- it is larger than the above range it will be difficult to dissolve in the solvent and it will be insoluble during the polymerization.
- the viscosity of a varnish becomes high and handling becomes difficult or adhesiveness with a base material falls.
- the nonvolatile content concentration of the paste cannot be increased, and it becomes difficult to form a thick film.
- the polymerization conditions such as the monomer ratio and the polymerization temperature, a urethane-modified polyimide resin having a logarithmic viscosity in this range can be obtained.
- the glass transition temperature of the urethane-modified polyimide resin is preferably 20 ° C. or higher, more preferably 60 ° C. or higher. If it is less than the said temperature, heat resistance may run short and there exists a possibility that resin may block. Although an upper limit is not specifically limited, 300 degrees C or less is preferable from a solvent solubility viewpoint. By appropriately adjusting the polymerization conditions such as the monomer ratio, a urethane-modified polyimide resin having a glass transition temperature in this range can be obtained.
- the urethane-modified polyimide-based flame retardant resin composition of the present invention is (B) by curing two or more urethane-modified polyimide-based resins for the purpose of improving film properties after film formation.
- An epoxy resin having an epoxy group is contained.
- component (B) epoxy resin examples include bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, brominated bisphenol A type epoxy resin, phenol novolac type epoxy resin, and o-cresol novolac.
- Type epoxy resin flexible epoxy resin, epoxidized polybutadiene, polyfunctional epoxy resin, amine type epoxy resin, heterocycle-containing epoxy resin, alicyclic epoxy resin, bisphenol S type epoxy resin, triglycidyl isocyanurate, bixylenol type Examples include epoxy resins, bisphenol-type epoxy resins, naphthalene-type epoxy resins, dicyclopentadiene-type epoxy resins, phosphorus-containing epoxy resins, etc., and these may be used alone or in combination of two or more.
- bisphenol A type epoxy resin bisphenol F type epoxy resin, phenol novolac type epoxy resin having more than two epoxy groups in one molecule, o-cresol novolac type epoxy resin, amine type epoxy resin are It is a non-halogen type, and is preferred in terms of compatibility with the urethane-modified polyimide resin of component (A), solvent resistance, chemical resistance, and moisture resistance.
- the amount of the epoxy resin used is preferably 1 to 50 parts by mass, more preferably 2 to 40 parts by mass, and particularly preferably 3 to 30 parts by mass with respect to 100 parts by mass of the urethane-modified polyimide resin. If the amount of the epoxy resin is less than the above range, solder heat resistance, solvent resistance, chemical resistance, and moisture resistance tend to decrease. If the amount exceeds the above range, low warpage, mechanical properties, heat resistance, varnish stability And compatibility with urethane-modified polyimide resin tends to decrease.
- the combined use amount of the component (A) and the component (B) is preferably 40 to 90% by mass when the nonvolatile content of the urethane-modified polyimide resin composition is 100% by mass. More preferably, it is 45 to 80% by mass.
- the epoxy resin may further contain an epoxy compound having only one epoxy group in one molecule as a diluent.
- epoxy resin As an addition method of the epoxy resin, it may be added after dissolving the epoxy resin added in advance in the same solvent as that contained in the urethane-modified polyimide resin, or directly to the urethane-modified polyimide resin. It may be added.
- the urethane-modified polyimide flame retardant resin composition of the present invention contains (C) an inorganic or organic filler in order to improve the workability during coating and printing and the film properties after film formation.
- the inorganic or organic filler is not particularly limited as long as it can be dispersed in the urethane-modified polyimide resin and can impart thixotropic properties.
- examples of such inorganic fillers include silica (SiO 2 ), alumina (Al 2 O 3 ), titania (TiO 2 ), tantalum oxide (Ta 2 O 5 ), zirconia (ZrO 2 ), and silicon nitride (Si 3 ).
- the inorganic filler those having an average particle size of 50 ⁇ m or less and a maximum particle size of 100 ⁇ m or less are preferable, an average particle size of 20 ⁇ m or less is more preferable, and an average particle size of 10 ⁇ m or less is most preferable.
- the average particle diameter (median diameter) here is determined on a volume basis using a laser diffraction / scattering particle size distribution measuring apparatus. When the average particle diameter exceeds 50 ⁇ m, it becomes difficult to obtain a composition having sufficient thixotropy, and the flexibility of the resulting coating film decreases. When the maximum particle diameter exceeds 100 ⁇ m, the appearance and adhesion of the coating film tend to be insufficient.
- any organic filler may be used as long as it can be dispersed in the above urethane-modified polyimide resin solution to impart thixotropy, and examples thereof include polyimide resin particles, benzoguanamine resin particles, and epoxy resin particles.
- the amount of the inorganic or organic filler used is preferably 0.5 to 25% by mass when the entire nonvolatile content of the urethane-modified polyimide resin composition is 100% by mass. More preferably, it is 2 to 15% by mass, and particularly preferably 3 to 12% by mass. If the blending amount of the inorganic or organic filler is less than 0.5% by mass, the printability tends to be lowered, and if it exceeds 25% by mass, the mechanical properties such as the flexibility of the coating film and the transparency tend to be lowered. .
- the urethane-modified polyimide flame retardant resin composition of the present invention contains (D) a non-halogen flame retardant in order to have flame retardancy.
- the non-halogen flame retardant is composed of two components: a component (D-1) having a weight loss rate of 50% or more and 90% or less at 350 ° C in an air atmosphere and a component (D-2) having a proportion of 0% or more and 20% or less Is contained as an essential component.
- the weight reduction rate of the component (D-1) is preferably 60% to 85%, and the weight reduction rate of the component (D-2) is preferably 0% to 15%.
- the weight reduction rate is determined by heating from room temperature to 100 ° C. at a heating rate of 10 ° C./min and holding for 30 minutes in an air atmosphere by TGA (thermogravimetric analysis), and then at a heating rate of 10 ° C. / The weight reduction rate from 150 ° C. to 350 ° C. when heated on an aluminum pan to 600 ° C. per minute.
- TGA thermogravimetric analysis
- non-halogen flame retardant is not particularly limited, but (A) preferably contains a phosphorus flame retardant that is compatible with the urethane-modified polyimide resin.
- a plasticizer for the urethane-modified polyimide resin By acting as a plasticizer for the urethane-modified polyimide resin, the low warpage of the coating film can be improved.
- the phosphorus-based flame retardant that is compatible with the urethane-modified polyimide resin is, for example, a lower Tg of the blended composition than the Tg (glass transition temperature) of the urethane-modified polyimide meter resin alone.
- the behavior can be grasped by, for example, the change of the calorimetric displacement position of DSC (Differential Scanning Calorimetry) and the peak position of the loss tangent in DMA (Dynamic Viscoelasticity Measurement).
- such a (D) non-halogen flame retardant includes a urethane-modified polyimide resin and a filler-type non-halogen flame retardant that is incompatible with the solvent.
- a filler-type flame retardant By blending a filler-type flame retardant, the heat resistance of the coating film, particularly physical heat resistance such as blocking during heating, and the bleed-out of the flame retardant can be improved.
- Examples of the filler-type non-halogen flame retardant include a phosphinic acid metal salt represented by the following general formula [I], a diphosphinic acid metal salt represented by the following general formula [II], and a cyanamide derivative having at least one amino group. And a reaction product of a cyanamide derivative having at least one amino group and cyanuric acid.
- non-halogen flame retardants include 9,10-dihydro-9-oxa-10-phenanthrene-10-oxide from the viewpoints of flame retardancy, hydrolysis resistance, heat resistance and surface bleed out suppression.
- the reaction product is preferably a reaction product of a cyanamide derivative having at least one amino group and cyanuric acid, and the component (D-1) is a 9,10-dihydro-9-oxa-10-phenanthrene-10-oxide derivative.
- the component (D-2) is a phenoxyphosphazene compound, a phosphinic acid metal salt represented by the following general formula [I], A diphosphinic acid metal salt represented by [II], a reaction product of a cyanamide derivative having at least one amino group and phosphoric acid, a reaction product of a cyanamide derivative having at least one amino group and cyanuric acid Is more preferable.
- R 1 and R 2 may be the same or different from each other, and linear or branched C 1 -C 10 alkyl and / or cycloalkyl and / or Aryl and / or aralkyl, R 1 and R 2 may be bonded to each other to form a ring with an adjacent phosphorus atom, R 3 is linear or branched C 1 -C 10 alkylene, C 6 arylene cycloalkylene, C 6 ⁇ C 10 of ⁇ C 10, aryl alkylene alkylarylene or C 6 ⁇ C 10 of C 6 ⁇ C 10, M is, Mg, Ca, Al, Sb , Sn, Ge, A cation selected from at least one member selected from the group consisting of Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K or a protonated nitrogen base, and m is an integer of 1 to 4 Yes, Is an integer of 1-4, x is an integer of 1 to 4 Yes, Is an integer
- 9,10-dihydro-9-oxa-10-phenanthrene-10-oxide derivatives examples include HCA (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) from Sanko Co., Ltd.
- HCA-HQ (10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide), SANKO-BCA (10-benzyl-9,10-dihydro- 9-oxa-10-phosphaphenanthrene-10-oxide), 10- (2,5-dihydroxy-6-methylphenyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5-dihydroxy-2-naphthyl) -9,10-dihydro-9-oxa-10-phosphaf Nanthrene-10-oxide, 2- (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide-10-yl) methylsuccinic acid bis (2-hydroxyethyl) ester, 10-methyl-9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-
- 9,10-dihydro-9-oxa-10-phenanthrene-10-oxide derivatives those which are compatible with (A) urethane-modified polyimide resin are preferred, and SANKO-BCA (10-benzyl-9,10 -Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) is more preferred.
- HCA (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide), HCA-HQ (10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa-10- Phosphaphenanthrene-10-oxide) has reactivity with epoxy resins, but tends to cause bleed on the surface, compatibility with urethane-modified polyimide resins, and poor solubility in non-nitrogen solvents. For this reason, it is appropriately selected in consideration of performance such as low warpage.
- phenoxyphosphazene compound examples include cyclic phenoxyphosphazenes such as trade names SPE-100 and SPB-100L manufactured by Otsuka Chemical Co., Ltd., and cyclic cyanophenoxyphosphazenes such as trade names FP-300 manufactured by Fushimi Pharmaceutical Co., Ltd. Cyclic hydroxyphenoxyphosphazenes such as the trade name SPH-100 manufactured by Otsuka Chemical Co., Ltd., and other chain phenoxyphosphazenes, cross-linked phenoxyphosphazenes, etc. are mentioned. Since chain phosphazenes have substituents at the molecular ends, they are generally cyclic.
- phosphazenes are preferable, and cyclic trimers and / or tetrameric phosphazenes are more preferable.
- a reactive phosphazene having a functional group that reacts with a urethane-modified polyimide resin such as SPH-100 is used, it is incorporated into a curing system, so that it does not cause bleeding on the surface, which is preferable.
- phosphazene when using non-reactive phosphazene that does not have a functional group that reacts with urethane-modified polyimide resin, the crystalline one may bleed on the surface over time or may be affected by hydrolysis under severe conditions. In this case, free phosphorus may be eluted and the insulating properties may be degraded by decomposition products. Therefore, it is preferable to use phosphazene that is liquid under conditions of 25 ° C. and 1013.25 hPa, such as SPB-100L. Is preferred.
- phosphinic acid metal salts include Al dimethylphosphinic acid Al, methylethylphosphinic acid Al, diethylphosphinic acid Al, and other dialkylphosphinic acid Al salts, phenylphosphinic acid Al, diphenylphosphinic acid Al, and other arylphosphinic acid Al salts, methyl Alkylarylphosphinic acid Al salt such as phenylphosphinic acid Al, 1-hydroxy-1H-phosphorane-1-oxide Al salt, 2-carboxy-1-hydroxy-1H-phosphorane-1-oxide Al salt, etc.
- Examples include Al salts of alkylenephosphinic acid that may be used, Zn salts corresponding to these Al salts, Ca salts, and other metals.
- diphosphinic acid salt examples include alkane bis (phosphinic acid) Al salt such as ethane-1,2-bis (phosphinic acid) Al salt, ethane-1,2-bis (methylphosphinic acid) Al salt, and the like.
- alkanebis (alkylphosphinic acid) Al salts examples include alkanebis (alkylphosphinic acid) Al salts, Zn salts corresponding to these Al salts, Ca salts, and other metal salts.
- R 1 and R 2 may be the same or different from each other, and may be a linear or branched C 1 to C 10 alkyl group and And / or a cycloalkyl group and / or an aryl group and / or an aralkyl group, particularly preferably mutually the same or different, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group , Tert-butyl group, n-pentyl group or phenyl group.
- the ring formed by combining R 1 and R 2 together with the adjacent phosphorus atom is a heterocycle having the phosphorus atom as a hetero atom constituting the ring, and is usually a 4- to 20-membered heterocyclic ring, preferably a 5- to 16-membered ring.
- a heterocycle is mentioned.
- the heterocyclic ring having a phosphorus atom may be a bicyclo ring or may have a substituent.
- R 3 represents a linear or branched C 1 to C 10 alkylene group, a C 6 to C 10 cycloalkylene group, a C 6 to C 10 arylene group, a C 6 to C 10 alkylarylene group, or a C 6.
- C 10 arylalkylene group and preferable alkylene groups are methylene group, ethylene group, n-propylene group, isopropylene group, n-butylene group, tert-butylene group, n-pentylene group, n-octylene.
- n-dodecylene group and cycloalkylene group are cyclohexylene group, cyclohexadimethylene group, arylene group is phenylene group or naphthylene group, and alkylarylene group is methylphenylene group, ethylphenylene group, tert- Butylphenylene group, methylnaphthylene group, ethylnaphthylene group, or ter Examples of the t-butylnaphthylene group and arylalkylene group include a phenylmethylene group, a phenylethylene group, a phenylpropylene group, and a phenylbutylene group.
- M is at least one selected from the group consisting of Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K, or a protonated nitrogen base. Cations selected, preferably Mg, Ca, Al, Ti, Zn ions.
- the phosphinic acid salt and diphosphinic acid salt include polyvalent salts of these phosphinic acids and / or polymers or condensates of the polyvalent salts of diphosphinic acids.
- the average particle size of the phosphinates is preferably 10 ⁇ m or less, more preferably 8 ⁇ m or less, and even more preferably 5 ⁇ m or less.
- the average particle diameter exceeds 10 ⁇ m, the amount used for developing sufficient flame retardancy increases, which is economically disadvantageous. In addition, insulation reliability, flexibility, adhesion, appearance and the like are deteriorated.
- Specific examples of such preferred phosphinic acid salts include aluminum diethylphosphinate, which is commercially available from Clariant Japan Co., Ltd. under the trade names Exolite OP935 and OP930.
- the average particle diameter (median diameter) of the phosphinates can be determined on a volume basis using a laser diffraction / scattering particle size distribution analyzer.
- a reaction product of a cyanamide derivative having at least one amino group and phosphoric acid, a reaction product of a cyanamide derivative having at least one amino group and cyanuric acid, and a cyanamide derivative having at least one amino group are amino And a group having a unit represented by —N ⁇ C ⁇ N— or —N ⁇ C (—N ⁇ ) 2 , and amino group-containing triazines (melamine, melam, melem, melon, guanamine, acetoguanamine, Amino group-containing 1,3,5-triazines such as benzoguanamine, amino group-containing 1,2,4-triazines such as 3-amino-1,2,4-triazine), amino group-containing triazoles (2, Cycyanamides such as amino group-containing 1,3,4-triazoles such as 5-diamino-1,3,4-triazole) And acyclic cyanamide derivatives such as derivatives and guanidines (guanidine, guanidine derivatives
- the phosphoric acid to be reacted with the cyanamide derivative is non-condensed phosphoric acid (orthophosphoric acid, metaphosphoric acid, phosphorous acid (phosphonic acid), hypophosphorous acid (phosphinic acid), etc.), inorganic phosphoric acid such as polyphosphoric acid.
- Polyphosphoric acid includes condensed phosphoric acids such as pyrophosphoric acid, triphosphoric acid, and tetraphosphoric acid.
- reaction product of a cyanamide derivative having at least one amino group and phosphoric acid and as a reaction product of a cyanamide derivative having at least one amino group and cyanuric acid is a condensation product of melamine, melamine or melamine Containing at least one of a condensation product and phosphoric acid reaction product, a melamine or melamine condensation product and phosphoric acid condensate reaction product, and a melamine or melamine condensation product and cyanuric acid reaction product More preferred are melamine polyphosphate, melem polyphosphate, melam polyphosphate, dimelamine pyrophosphate, melamine cyanurate, and most preferred is a longer condensation degree of 2 or more, especially 10 or more and 50 or less. Melamine polyphosphate and melamine with chain length It is an isocyanurate. These may be used alone or in combination of two or more.
- the average particle size of the reaction product of the cyanamide derivative having at least one amino group and phosphoric acid, the reaction product of the cyanamide derivative having at least one amino group and cyanuric acid is preferably 10 ⁇ m or less, and more preferably Is 8 ⁇ m or less, more preferably 5 ⁇ m or less.
- the average particle diameter exceeds 10 ⁇ m, the amount used for developing sufficient flame retardancy increases, which is economically disadvantageous. In addition, insulation reliability, flexibility, adhesion, appearance, and the like are deteriorated.
- reaction product of a cyanamide derivative having at least one amino group and phosphoric acid and a reaction product of a cyanamide derivative having at least one amino group and cyanuric acid include, for example, Ciba Specialty Trade names MELAPURE 200, MC25, manufactured by Tea Chemical Co., Ltd., trade names PHOSMEL-200, manufactured by Nissan Chemical Industries, Ltd., trade names MPP-A, manufactured by Sanwa Chemical Co., Ltd., trade names STABIACE MC-5F, MC-5S, MC manufactured by Sakai Chemical Industries -2010N and the like.
- the phosphorus content in the urethane-modified polyimide flame retardant resin composition of the present invention is preferably 1.4 to 7.0% by mass, and the addition amount of the component (D) is adjusted so as to be in this range. Preferably they are 1.6 mass% or more and 4.8 mass% or less, More preferably, they are 2.0 mass% or more and 4.0 mass% or less. If the phosphorus content is less than the above range, good flame retardancy cannot be obtained, and if it exceeds the above range, the mechanical properties, heat resistance, adhesion and insulation properties of the coating film may be lowered.
- the blending ratio of the component (D-1) and the component (D-2) is not particularly limited as long as the phosphorus content in the urethane-modified polyimide flame retardant resin composition and the required flame retardancy can be achieved.
- non-halogen flame retardants may be used in combination, or these may be used alone or in combination of two or more. You may set suitably in the range by which various physical properties, such as an electrical property of a coating film, heat resistance, and environmental suitability, are not impaired.
- the urethane-modified polyimide flame retardant resin composition of the present invention can further contain (E) a curing accelerator in order to further improve the properties such as adhesion, chemical resistance and heat resistance.
- the curing accelerator is not particularly limited as long as it can accelerate the curing reaction between the urethane-modified polyimide resin, epoxy resin and non-halogen flame retardant.
- epoxy resin curing agent examples include, for example, imidazole derivatives, guanamines such as acetoguanamine, benzoguanamine, diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, urea derivatives.
- guanamines such as acetoguanamine, benzoguanamine, diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, urea derivatives.
- Organic phosphines such as tri-n-butyl (2,5-dihydroxyphenyl) phosphonium bromide, hexadecyltributylphosphonium chloride, tetraphenylphosphonium tetraphenylboroate, benzyltrimethylammonium chloride, Quaternary ammonium salts such as phenyltributylammonium chloride, the above polycarboxylic acid anhydrides, diphenyliodonium tetrafluoroboroate, triphenylsulfonium hexafluoroantimonate, 2,4,6-triphenylthiopyrylium hexafluorophosphate, Irgacure 261 (manufactured by Ciba Specialty Chemicals), Optoma-SP-170 (manufactured by ADEKA Co., Ltd.) And an equimolar reaction product of organic poly
- a curing accelerator having latent curability and examples thereof include DBU, DBN organic acid salts and / or tetraphenylboronate, and a photocationic polymerization catalyst.
- the amount of curing accelerator used is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of (A) urethane-modified polyimide resin. If it exceeds 20 parts by mass, the storage stability of the urethane-modified polyimide-based flame retardant resin composition and the heat resistance of the coating film are likely to be reduced, and if it is less than 0.1 parts by mass, the curability may be reduced.
- the urethane-modified polyimide flame retardant resin composition of the present invention can contain (F) an ion catcher in order to further improve the insulation reliability under high temperature and high humidity.
- the impure ions and hydrolyzable chlorine present in the order of ppm are captured in the cured coating film of the urethane-modified polyimide flame retardant resin composition to reduce the insulation failure of the flexible printed circuit board,
- organic ion exchange resin, inorganic ion exchanger zeolite, zirconium phosphate, hydrated bismuth nitrate, antimony oxide, magnesium aluminum hydrotalcite, hydroxy Apatite. You may use these individually or in combination of 2 or more types. In view of heat resistance and chemical resistance, it is preferable to use an inorganic ion exchanger.
- ions to be captured include both cations and anions
- an ion exchange type inorganic ion exchanger is used, or a cation exchange type inorganic ion exchanger and an anion exchange type inorganic ion exchanger are used. It is desirable to use together.
- an antimony-bismuth type or a zirconium-bismuth type can be used.
- Non-antimony-bismuth type materials are also included.
- a zirconium-based one or an antimony-based one can be used.
- a bismuth type or a magnesium-aluminum type can be used.
- those not containing heavy metals such as antimony and bismuth are more preferable because they have high ion exchange capacity and high environmental harmony.
- the compounding amount of the ion exchanger is preferably in the range of 1.0 to 15.0% by weight with respect to the total amount of the composition. If the blending amount of the inorganic ion exchanger is less than 1.0% by weight, the ion trapping rate may be 50% or less, and a sufficient effect due to blending of the inorganic ion exchanger may not be obtained. In addition, when the blending amount of the inorganic ion exchanger is about 15.0% by weight, the ion trapping rate becomes 80% or more, but even if the blending amount of the inorganic ion exchanger is further increased, the ion trapping rate does not increase.
- the ratio of the cation exchange type to the anion exchange type ion scavenger is in the range of 20:80 to 60:40 by weight. It is preferable to set to.
- the urethane-modified polyimide flame retardant resin composition of the present invention further includes a color pigment, a dye, a polymerization inhibitor, a thickener, an antifoaming agent, a leveling agent, a coupling agent / adhesion imparting agent, Known and commonly used heat stabilizers, antioxidants, lubricants, UV absorbers, light stabilizers, light-shielding agents, quenchers, metal deactivators, antistatic agents, anti-aging agents, plasticizers, compatibilizers, etc. Additives can be added.
- the urethane-modified polyimide flame retardant resin composition of the present invention includes the components (A), (B), (C), (D), (E), and (F) described above, and other blending components as necessary. And is uniformly mixed with a roll mill, a bead mill, a mixer or the like. The mixing method is not particularly limited as long as sufficient dispersion of each component can be obtained. Multiple kneading with three rolls is preferred.
- the viscosity with a B-type viscometer described later is preferably in the range of 50 dPa ⁇ s to 2000 dPa ⁇ s at 25 ° C., and more preferably in the range of 100 dPa ⁇ s to 800 dPa ⁇ s. preferable.
- the viscosity is less than 50 dPa ⁇ s, there is a tendency for the paste to flow out after printing and the film thickness to be reduced.
- the viscosity exceeds 2000 Pa ⁇ s, the transferability of the paste to the base material is reduced during printing, and there is a tendency for voids and pinholes in the printed film to increase.
- the degree of thixotropy is also important, and the urethane-modified polyimide flame retardant resin composition of the present invention preferably has a degree of throttling of 1.1 or more, more preferably 1.8 or more, in the measurement method described later.
- the upper limit is preferably 10.0 or less, and more preferably 9.0 or less. If the degree of change is less than 1.1, the flow of paste after printing increases and the film thickness tends to be reduced. If it exceeds 10.0, the paste tends not to flow.
- the degree of change can be adjusted by the amount of component (C) added as a change degree imparting agent.
- the urethane-modified polyimide flame retardant resin composition of the present invention is cured, for example, as a solder resist as follows to obtain a cured product. That is, on printed wiring boards, flexible printed wiring boards (FPC), chip-on-films (COF), etc., by screen printing, spray coating, roll coating, electrostatic coating, curtain coating, dip coating, etc.
- the composition of the present invention is applied to a thickness of 5 to 80 ⁇ m, and the coating film is pre-dried at 60 to 120 ° C. and then dried at 120 to 200 ° C. Drying may be in air or in an inert atmosphere.
- the urethane-modified polyimide flame-retardant resin composition of the present invention thus obtained is useful as a film forming material for semiconductor elements and overcoat inks for various electronic components, solder resist inks, interlayer insulating films, It can also be used as a paint, coating agent, adhesive or the like.
- ⁇ 350 ° C weight loss rate About 15 mg each of flame retardant alone and urethane-modified polyimide resin were sampled and heated from room temperature to 100 ° C. at a heating rate of 10 ° C./min in an air atmosphere (20 ml / min) and held for 30 minutes, and then the heating rate It heated on the aluminum pan to 10 degreeC / 600 to 600 degreeC, and calculated
- a sample obtained by curing a urethane-modified polyimide flame retardant resin composition at 165 ° C. for 2 hours is weighed into an Erlenmeyer flask in an appropriate amount according to the phosphorus concentration in the sample, 3 ml of sulfuric acid, 0.5 ml of perchloric acid Then, 3.5 ml of nitric acid was added, and the mixture was gradually decomposed by heating with an electric heater over a half day.
- the obtained laminated film having a thickness of 15 ⁇ m was evaluated for flame retardancy according to the UL94 standard.
- the flame retardancy is preferably VTM-2 or higher according to UL standards, and most preferably VTM-0.
- the laminated film obtained using the polyimide film as a base material was evaluated according to JIS-K5400.
- the diameter of the mandrel was 2 mm, and the presence or absence of cracks was confirmed.
- a comb-shaped pattern with a line spacing of 50 ⁇ m was formed on a two-layer CCL (trade name Viroflex) manufactured by Toyobo, washed with 1% sulfuric acid, and then washed with water and dried. The entire surface of the paste was printed on the circuit, and the obtained solder resist layer was heated and cured at 160 ° C. for 120 minutes. The insulation resistance between lines when a DC voltage of 100 V was applied was measured. 10 8 or more is preferable.
- the laminated film obtained using the copper foil as a base material was evaluated according to JIS-K5400.
- the pencil hardness is preferably 2H or higher, and more preferably 3H or higher.
- Production Examples 2-5 Polymerization was conducted in the same manner as in Example 1 using the raw materials listed in Table 1, and then cooled to room temperature to obtain dark brown urethane-modified polyimide resin solutions A-2 to A-5 having a nonvolatile content of 40% by mass. .
- Production Examples 7-8 Polymerization was conducted in the same manner as in Example 6 using the raw materials shown in Table 1, and then cooled to room temperature to obtain dark brown urethane-modified polyimide resin solutions A-7 to A-8 having a nonvolatile content of 40% by mass. .
- Example 1 Based on 48.8 parts by mass of the resin content of the urethane-modified polyimide resin solution A-1 obtained in Production Example 1, jER152 (trade name of phenol novolac type epoxy resin manufactured by Japan Epoxy Resin Co., Ltd.) 7.2 masses Part was added and diluted with diglyme.
- jER152 trade name of phenol novolac type epoxy resin manufactured by Japan Epoxy Resin Co., Ltd.
- Aerosil # 300 hydrophilic silica fine particles manufactured by Nippon Aerosil Co., Ltd.
- SANKO-BCA manufactured by Sanko Co., Ltd.
- SPE -100 Otsuka Chemical Co., Ltd.
- Ucat5002 San Apro Co., Ltd.
- Floren AC-326F Kyoeisha Chemical Co., Ltd.
- BYK-358 by Big Chemie Co., Ltd.
- a paste made of a urethane-modified polyimide flame retardant resin composition having a uniformly dispersed filler and thixotropic properties was obtained.
- the viscosity was adjusted with diglyme, the solution viscosity was 130 poise and the throttling was 2.5.
- the paste made of the obtained urethane-modified polyimide flame retardant resin composition was applied to the glossy surface of an electrolytic copper foil having a thickness of 18 ⁇ m so as to have a thickness of 15 ⁇ m after drying. After drying with hot air at 80 ° C. for 10 minutes, a laminated film was obtained by heating at 150 ° C. for 120 minutes in an air atmosphere.
- the film was obtained by carrying out the etching removal of the copper foil of the obtained laminated
- Examples 2-18 Using the raw materials described in Tables 2 and 3, a urethane-modified polyimide flame retardant resin composition and a laminated film were obtained in the same manner as in Example 1. Tables 2 and 3 show details and evaluation results of the obtained compositions and laminated films.
- a paste made of a polyimide resin composition was printed on a SUS mesh plate (Murakami Co., Ltd. 150 mesh, emulsion thickness 30 ⁇ m) at a printing speed of 5 cm / sec and dried at 80 ° C. for 6 minutes in an air atmosphere.
- the flexible printed wiring board which gave the coverlay (coating) which consists of a urethane-modified polyimide resin composition was obtained by heat-curing for 60 minutes at 165 degreeC.
- the thickness of the coating was 15 ⁇ m.
- the obtained flexible printed wiring board was excellent in flexibility and flexibility.
- Comparative Examples 1-7 A urethane-modified polyimide flame retardant resin composition and a laminated film were obtained in the same manner as in Example 1 except that the raw materials listed in Table 4 were used. Table 4 shows details and evaluation results of the obtained composition and laminated film.
- the cured coating films formed from the urethane-modified polyimide flame retardant resin compositions of Examples 1 to 18 of the present invention can be cured at low temperature, have no warpage, are flexible, and have difficulty. Excellent in flame resistance, heat resistance, chemical resistance, electrical properties, and adhesion to the substrate.
- Comparative Examples 1 to 3, 5 to 7, the characteristics and blending amount of the flame retardant are out of the scope of the present invention, and in Comparative Example 4, the urethane-modified polyimide resin is out of the scope of the present invention. Therefore, the cured coating film formed from these urethane-modified polyimide resin flame retardant resin compositions was inferior in each characteristic.
- the urethane-modified polyimide flame retardant resin composition of the present invention is useful as a film forming material for overcoat inks for various electronic parts such as flexible printed wiring boards, solder resist inks, interlayer insulating films, paints, and coating agents. It can be used as an adhesive in a wide range of electronic devices.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Epoxy Resins (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
Abstract
Description
(1)(a)酸無水物基を有する3価及び/又は4価のポリカルボン酸誘導体、(b)ジオール化合物、及び(c)脂肪族ポリアミン残基誘導体及び/又は芳香族ポリアミン残基誘導体を必須の成分として生成されるウレタン結合を有するウレタン変性ポリイミド系樹脂、
(B)1分子あたり2個以上のエポキシ基を有するエポキシ樹脂、
(C)無機あるいは有機フィラー、及び
(D)非ハロゲン系難燃剤、
を含有するウレタン変性ポリイミド系難燃樹脂組成物であって、
(D)非ハロゲン系難燃剤が、空気雰囲気下350℃における重量減少率が50%以上90%以下の成分(D-1)と0%以上20%以下の成分(D-2)の2成分を必須の成分として含むことを特徴とするウレタン変性ポリイミド系難燃樹脂組成物。
(2)(D-1)成分の重量減少率が60%以上85%以下であり、(D-2)成分の重量減少率が0%以上15%以下であることを特徴とする(1)に記載のウレタン変性ポリイミド系難燃樹脂組成物。
(3)(D)非ハロゲン系難燃剤が、(A)ウレタン変性ポリイミド系樹脂に相溶するリン系難燃剤を含むことを特徴とする(1)又は(2)に記載のウレタン変性ポリイミド系難燃樹脂組成物。
(4)(D-1)成分が9,10-ジヒドロ-9-オキサ-10-フェナントレン-10-オキシド誘導体を含み、(D-2)成分がフェノキシホスファゼン化合物を含むことを特徴とする(1)から(3)のいずれかに記載のウレタン変性ポリイミド系難燃樹脂組成物。
(5)(D)非ハロゲン系難燃剤がフィラー型の非ハロゲン系難燃剤を含むことを特徴とする(1)から(3)のいずれかに記載のウレタン変性ポリイミド系難燃樹脂組成物。
(6)(D-1)成分が9,10-ジヒドロ-9-オキサ-10-フェナントレン-10-オキシド誘導体を含み、(D-2)成分が下記一般式[I]で表されるホスフィン酸金属塩、下記一般式[II]で表されるジホスフィン酸金属塩、少なくとも1つのアミノ基を有するシアナミド誘導体とリン酸類との反応生成物、又は少なくとも1つのアミノ基を有するシアナミド誘導体とシアヌル酸類との反応生成物を含むことを特徴とする(1)~(3)又は(5)のいずれか一項に記載のウレタン変性ポリイミド系難燃樹脂組成物。
(式[I]及び式[II]中、R1及びR2は互いに同じであっても異なってもよく、線状又は分岐状のC1~C10のアルキル及び/又はシクロアルキル及び/又はアリール及び/又はアラルキルであり、R1及びR2は互いに結合して隣接するリン原子とともに環を形成しても良い。R3は線状又は分岐状のC1~C10のアルキレン、C6~C10のシクロアルキレン、C6~C10のアリーレン、C6~C10のアルキルアリーレン又はC6~C10のアリールアルキレンであり、Mは、Mg、Ca、Al、Sb、Sn、Ge、Ti、Zn、Fe、Zr、Ce、Bi、Sr、Mn、Li、Na、K又はプロトン化した窒素塩基からなる群の少なくとも1種から選択されるカチオンであり、mは1~4の整数であり、nは1~4の整数であり、xは1~4の整数である。)
(7)(D-2)成分が、25℃、1013.25hPaの条件下で液体であるフェノキシホスファゼン化合物を含むことを特徴とする(1)から(6)のいずれか一項に記載のウレタン変性ポリイミド系難燃樹脂組成物。
(8)(b)ジオール化合物が、(b-1)ポリオキシアルキレングリコール、及び/又は(b-2)下記一般式[III]で表されるビスフェノールのポリアルキレンオキサイド付加体を含むことを特徴とする(1)から(7)のいずれか一項に記載のウレタン変性ポリイミド系難燃樹脂組成物。
(式[III]中、R1はC1~C20のアルキレン基であり、R2及びR3は互いに同じであっても異なってもよく、水素またはC1~C4のアルキル基を表し、mは1以上の整数であり、nは1以上の整数である。)
(9)(E)硬化促進剤をさらに含有することを特徴とする(1)から(8)のいずれか一項に記載のウレタン変性ポリイミド系難燃樹脂組成物。
(10)(F)イオンキャッチャーをさらに含有することを特徴とする(1)から(9)のいずれか一項に記載のウレタン変性ポリイミド系難燃樹脂組成物。
(11)(A)ウレタン変性ポリイミド系樹脂が、エーテル系溶媒、エステル系溶媒、ケトン系溶媒、及び芳香族炭化水素系溶媒からなる群から選ばれる少なくとも1種の有機溶媒中で反応させて得られるものであることを特徴とする(1)から(10)のいずれか一項に記載のウレタン変性ポリイミド系難燃樹脂組成物。
(12)揺変度で1.1以上のチクソトロピー性を有することを特徴とする(1)から(11)のいずれか一項に記載のウレタン変性ポリイミド系難燃樹脂組成物。
(13)ソルダーレジスト層、表面保護層、層間絶縁層又は接着剤層を有する電子部品であって、前記層が(1)から(12)のいずれか一項に記載のウレタン変性ポリイミド系難燃樹脂組成物を乾燥硬化して得られるものであることを特徴とする電子部品。
本発明のウレタン変性ポリイミド系難燃樹脂組成物は、
(A)(a)酸無水物基を有する3価及び/又は4価のポリカルボン酸誘導体、(b)ジオール化合物、(c)脂肪族ポリアミン残基誘導体及び/又は芳香族ポリアミン残基誘導体を必須の成分として生成されるウレタン結合を有するウレタン変性ポリイミド系樹脂、
(B)1分子あたり2個以上のエポキシ基を有するエポキシ樹脂、
(C)無機あるいは有機フィラー、及び
(D)非ハロゲン系難燃剤、
を含有し、
(D)非ハロゲン系難燃剤が、空気雰囲気下350℃における重量減少量が50%以上90%以下の成分(D-1)と0%以上20%以下の成分(D-2)の2成分を必須の成分として含むことを特徴とする。
(式[I]及び式[II]中、R1及びR2は互いに同じであっても異なってもよく、線状又は分岐状のC1~C10のアルキル及び/又はシクロアルキル及び/又はアリール及び/又はアラルキルであり、R1及びR2は互いに結合して隣接するリン原子とともに環を形成しても良い。R3は線状又は分岐状のC1~C10のアルキレン、C6~C10のシクロアルキレン、C6~C10のアリーレン、C6~C10のアルキルアリーレン又はC6~C10のアリールアルキレンであり、Mは、Mg、Ca、Al、Sb、Sn、Ge、Ti、Zn、Fe、Zr、Ce、Bi、Sr、Mn、Li、Na、K又はプロトン化した窒素塩基からなる群の少なくとも1種から選択されるカチオンであり、mは1~4の整数であり、nは1~4の整数であり、xは1~4の整数である。)
ウレタン変性ポリイミド系樹脂を、ポリマー濃度が0.5g/dlとなるようにN-メチル-2-ピロリドンに溶解し、30℃にてウベローデ型粘度管により溶液粘度を測定した。対数粘度は以下の式により定義した。
(対数粘度)=(lnηrel)/C
ln:自然対数
ηrel:溶媒落下時間測定による純溶媒に対する溶液の粘度比(-)
C:溶液の濃度(g/dl)
難燃剤単独およびウレタン変性ポリイミド系樹脂を、それぞれ約15mg採取し、空気雰囲気下(20ml/分)、昇温速度10℃/分で常温から100℃まで加熱し30分保持した後、昇温速度10℃/分で600℃まで、アルミニウムパン上で加熱し、150℃から350℃における重量減少率を求めた。
使用装置;島津製作所製示差熱・熱重量同時測定装置DTG-60
ウレタン変性ポリイミド系難燃樹脂組成物を、実施例19に記載の方法で30分連続スクリーン印刷した際の、ペーストからの樹脂析出、粘度上昇を以下の判定基準に基づいて評価した。
(判定)○:かすれ、樹脂析出、インク粘度上昇認められず
×:かすれ、樹脂析出、インク粘度上昇あり
ブルックフィールドBH型回転粘度計を用いて、次の手順で測定した。広口型遮光瓶(100ml)にウレタン変性ポリイミド系難燃樹脂組成物からなるペーストを入れ、恒温水槽を用いて液温を25℃±0.5℃に調整した。次いで、ガラス棒を用いて12~15秒かけて40回撹拌した後、所定のローターを設置して、5分静置した後、20rpmで3分回転させたときの目盛りを読み取った。粘度は、この目盛りに換算表の係数をかけて算出した。同じく25℃、2rpmで測定した粘度も算出し、これらの値から次式に従って揺変度を計算した。
揺変度=粘度(2rpm)/粘度(20rpm)
ウレタン変性ポリイミド系難燃樹脂組成物を、密閉下、25℃×1ヶ月放置した後、樹脂の析出やゲル化の有無を以下の判定基準に基づいて評価した。
(判定)○:異常なし
△:析出物あり
×:固化
湿式分解・モリブデンブルー比色法により測定した。ウレタン変性ポリイミド系難燃樹脂組成物を165℃×2時間硬化させて得られた試料を、試料中のリン濃度にあわせて適当量、三角フラスコに量りとり、硫酸3ml、過塩素酸0.5mlおよび硝酸3.5mlを加え、電熱器で半日かけて徐々に加熱分解した。溶液が透明になったら、さらに加熱して硫酸白煙を生じさせ、室温まで放冷し、この分解液を50mlメスフラスコに移し、2%モリブデン酸アンモニウム溶液5mlおよび0.2%硫酸ヒドラジン溶液2mlを加え、純水にてメスアップし、内容物をよく混合した。沸騰水浴中に10分間フラスコをつけて加熱発色した後、室温まで水冷し、超音波にて脱気し、溶液を吸収セル10mmに採り、分光光度計(波長830nm)にて空試験液を対照にして吸光度を測定した。先に作成しておいた検量線からリン含有量を求めた。
厚さ25μmのポリイミドフィルムを基材として、得られた15μm厚みの積層フィルムについて、UL94規格に従い難燃性を評価した。難燃性はUL規格でVTM-2以上が好ましく、VTM-0が最も好ましい。
ポリイミドフィルムを基材として得られた積層フィルムを10cm×10cmに切り出した。25℃、65%で24時間調湿したサンプルをポリエチレン製袋に入れ密封して25℃の恒温槽に1週間~1ヶ月放置し、目視と表面を指触してタック感の有無を以下の判定基準に基づいて評価した。
(判定)◎:3ヶ月後もブリード物、タック感なし
○:1ヶ月後もブリード物、タック感なし
△:1ヶ月後にわずかにブリード物、タック感がある
×:1週間後に顕著なブリード物、タック感がある
ポリイミドフィルムを基材として得られた積層フィルムを10cm×10cmに切り出した。25℃、65%で24時間調湿したサンプルを下に凸の状態で水平なガラス板に載せ、四隅の高さの平均を以下の判定基準に基づいて評価した。
(判定)○:高さ2mm未満
△:高さ10mm未満
×:高さ10mm以上
ポリイミドフィルムを基材として得られた積層フィルムについて、JIS-K5400に準じて評価を行った。心棒の直径は2mmとし、クラック発生の有無を確認した。
東洋紡製2層CCL(商品名バイロフレックス)上に線間50μmの櫛型パターンを作成し、1%硫酸洗浄した後、水洗乾燥した。回路上にペーストを全面印刷し、得られたソルダーレジスト層を160℃、120分の条件で加熱硬化させた。直流電圧100V印加時の線間絶縁抵抗を測定した。10の8乗以上が好ましい。
銅箔を基材として得られた積層フィルムを、JIS-C6481に準じて260℃の半田浴に30秒間浸漬し、剥がれや膨れ等の外観異常の有無を以下の判定基準に基づいて評価した。
(判定)○:外観異常なし
△:わずかに外観異常あり
×:全面外観異常あり
銅箔を基材として得られた積層フィルムに、JIS-K5600に準じて、1mmの碁盤目を100ヶ所作り、セロテープ(登録商標)による剥離試験を行い、碁盤目の剥離状態を観察した。ポリイミドフィルムを基材として得られた積層フィルムについても同様に剥離試験を行い、碁盤目の剥離状態を以下の判定基準に基づいて評価した。
(判定)○:100/100で剥離なし
△:70~99/100
×:0~70/100
銅箔を基材として得られた積層フィルムについて、JIS-K5400に準じて評価した。鉛筆硬度は2H以上が好ましく、3H以上がさらに好ましい。
ポリイミドフィルムを基材として得られた積層フィルムを、121℃、2atmの雰囲気下に48時間放置し、剥がれや溶解等の外観異常の有無を以下の判定基準に基づいて評価した。
(判定)○:外観異常なし
△:わずかに外観異常あり
×:全面外観異常あり
ポリイミドフィルムを基材として得られた積層フィルムを、10%HCl、10%NaOH、イソプロパノール、メチルエチルケトンの各溶媒に10秒間浸漬し、剥がれや溶解等の外観異常の有無を以下の判定基準に基づいて評価した。
(判定)○:全ての溶媒に浸漬しても外観異常なし
△:少なくとも一種の溶媒に浸漬した場合にわずかに外観異常
あり
×:少なくとも一種の溶媒に浸漬した場合に全面外観異常あり
攪拌機、冷却管、窒素導入管及び温度計を備えた4ツ口2リットルセパラブルフラスコに、トリメリット酸無水物(純度99.9%、トリメリット酸含有量0.1%)166.0質量部、ビスフェノールAのポリプロピレンオキサイド付加体(三洋化成工業(株)製の商品名ニューポールBP-5P、分子量533)86.3質量部、ポリプロピレングリコール(三洋化成工業(株)製の商品名サンニックスPPG2000、分子量2000)108質量部、ヘキサメチレンジイソシアネート84.1質量部、ジフェニルメタン-4,4′-ジイソシアネート125.1質量部、γ-ブチロラクトン493.5質量部、及び触媒として1,8-ジアザビシクロ[5.4.0]-7-ウンデセン1.5質量部を仕込み、窒素気流下、液内温30℃から160℃まで昇温し5時間反応させた後、ジグライムを246.8質量部加えて希釈し、室温まで冷却することで不揮発分40質量%の濃褐色ウレタン変性ポリイミド系樹脂溶液A-1を得た。
表1に記載した原料を使用し、実施例1と同様に重合した後、室温まで冷却することで不揮発分40質量%の濃褐色ウレタン変性ポリイミド系樹脂溶液A-2~A-5を得た。
攪拌機、冷却管、窒素導入管及び温度計を備えた4ツ口2リットルセパラブルフラスコに、トリメリット酸無水物(純度99.9%、トリメリット酸含有量0.1%)86.3質量部、エチレングリコールビスアンヒドロトリメリテート184.4質量部、ポリカプロラクトンジオール(ダイセル化学工業(株)製の商品名PLACCEL220、分子量2000)342.4質量部、ジフェニルメタン-4,4′-ジイソシアネート250.3質量部、γ-ブチロラクトン784.3質量部、及び触媒として1,8-ジアザビシクロ[5.4.0]-7-ウンデセン1.5質量部を仕込み、窒素気流下、液内温30℃から120℃まで昇温し5時間反応させた後、ジグライムを392.1質量部加えて希釈し、室温まで冷却することで不揮発分40質量%の濃褐色ウレタン変性ポリイミド系樹脂溶液A-6を得た。
表1に記載した原料を使用し、実施例6と同様に重合した後、室温まで冷却することで不揮発分40質量%の濃褐色ウレタン変性ポリイミド系樹脂溶液A-7~A-8を得た。
製造例1で得られたウレタン変性ポリイミド系樹脂溶液A-1の樹脂分48.8質量部に対して、jER152(ジャパンエポキシレジン(株)製フェノールノボラック型エポキシ樹脂の商品名)7.2質量部を加え、ジグライムで希釈した。さらに、フィラーとしてアエロジル#300(日本アエロジル(株)製親水性シリカ微粒子)を3.2質量部、非ハロゲン系難燃剤としてSANKO-BCA(三光(株)製)を19.1質量部、SPE-100(大塚化学(株)製)を19.2質量部、硬化促進剤としてUcat5002(サンアプロ(株)製)を0.5質量部、消泡剤としてフローレンAC-326F(共栄社化学(株)製)を1.5質量部、レベリング剤としてBYK-358(ビックケミー(株)製)を0.5質量部加え、まず粗混練りし、次いで高速3本ロールを用いて3回混練りを繰り返すことで、均一にフィラーが分散しチキソトロピー性を有するウレタン変性ポリイミド系難燃樹脂組成物からなるペーストを得た。ジグライムで粘度を調整したところ、溶液粘度が130ポイズ、揺変度は2.5であった。次に、厚さ18μmの電解銅箔の光沢面に、得られたウレタン変性ポリイミド系難燃樹脂組成物からなるペーストを乾燥後の厚さ15μmになるよう塗布した。80℃で10分熱風乾燥した後、空気雰囲気下、150℃で120分加熱して積層フィルムを得た。また、得られた積層フィルムの銅箔を塩化第二鉄溶液でエッチング除去することにより、フィルムを得た。同様に厚さ25μのポリイミドフィルム(カネカ製アピカルNPI)に塗布、乾燥加熱し、積層フィルムを得た。得られた組成物、積層フィルムの詳細と評価結果を表2に示す。
表2及び表3に記載した原料を使用し、実施例1と同様にウレタン変性ポリイミド系難燃樹脂組成物、積層フィルムを得た。得られた組成物、積層フィルムの詳細と評価結果を表2及び表3に示す。
東洋紡製2層CCL(商品名バイロフレックス、銅箔18μm、基材20μm)からサブトラクティブ法で得られた銅回路(L/S=50/50)上に、実施例5で得られたウレタン変性ポリイミド系樹脂組成物からなるペーストをSUSメッシュ版(株式会社ムラカミ製150メッシュ、乳剤厚30μm)で、印刷速度5cm/秒にて所定パターンを印刷し、空気雰囲気中で80℃で6分間乾燥した後、165℃にて60分加熱硬化することで、ウレタン変性ポリイミド系樹脂組成物からなるカバーレイ(被膜)を施したフレキシブルプリント配線板を得た。被膜の厚みは15μmであった。得られたフレキシブルプリント配線板は、柔軟性、屈曲性に優れたものであった。
表4に記載した原料を使用したほかは、実施例1と同様な操作でウレタン変性ポリイミド系難燃樹脂組成物、積層フィルムを得た。得られた組成物、積層フィルムの詳細と評価結果を表4に示す。
Claims (13)
- (A)(a)酸無水物基を有する3価及び/又は4価のポリカルボン酸誘導体、(b)ジオール化合物、及び(c)脂肪族ポリアミン残基誘導体及び/又は芳香族ポリアミン残基誘導体を必須の成分として生成されるウレタン結合を有するウレタン変性ポリイミド系樹脂、
(B)1分子あたり2個以上のエポキシ基を有するエポキシ樹脂、
(C)無機あるいは有機フィラー、及び
(D)非ハロゲン系難燃剤、
を含有するウレタン変性ポリイミド系難燃樹脂組成物であって、
(D)非ハロゲン系難燃剤が、空気雰囲気下350℃における重量減少率が50%以上90%以下の成分(D-1)と0%以上20%以下の成分(D-2)の2成分を必須の成分として含むことを特徴とするウレタン変性ポリイミド系難燃樹脂組成物。 - (D-1)成分の重量減少率が60%以上85%以下であり、(D-2)成分の重量減少率が0%以上15%以下であることを特徴とする請求項1に記載のウレタン変性ポリイミド系難燃樹脂組成物。
- (D)非ハロゲン系難燃剤が、(A)ウレタン変性ポリイミド系樹脂に相溶するリン系難燃剤を含むことを特徴とする請求項1又は2に記載のウレタン変性ポリイミド系難燃樹脂組成物。
- (D-1)成分が9,10-ジヒドロ-9-オキサ-10-フェナントレン-10-オキシド誘導体を含み、(D-2)成分がフェノキシホスファゼン化合物を含むことを特徴とする請求項1から3のいずれかに記載のウレタン変性ポリイミド系難燃樹脂組成物。
- (D)非ハロゲン系難燃剤がフィラー型の非ハロゲン系難燃剤を含むことを特徴とする請求項1から3のいずれかに記載のウレタン変性ポリイミド系難燃樹脂組成物。
- (D-1)成分が9,10-ジヒドロ-9-オキサ-10-フェナントレン-10-オキシド誘導体を含み、(D-2)成分が下記一般式[I]で表されるホスフィン酸金属塩、下記一般式[II]で表されるジホスフィン酸金属塩、少なくとも1つのアミノ基を有するシアナミド誘導体とリン酸類との反応生成物、又は少なくとも1つのアミノ基を有するシアナミド誘導体とシアヌル酸類との反応生成物を含むことを特徴とする請求項1~3又は5のいずれか一項に記載のウレタン変性ポリイミド系難燃樹脂組成物。
(式[I]及び式[II]中、R1及びR2は互いに同じであっても異なってもよく、線状又は分岐状のC1~C10のアルキル及び/又はシクロアルキル及び/又はアリール及び/又はアラルキルであり、R1及びR2は互いに結合して隣接するリン原子とともに環を形成しても良い。R3は線状又は分岐状のC1~C10のアルキレン、C6~C10のシクロアルキレン、C6~C10のアリーレン、C6~C10のアルキルアリーレン又はC6~C10のアリールアルキレンであり、Mは、Mg、Ca、Al、Sb、Sn、Ge、Ti、Zn、Fe、Zr、Ce、Bi、Sr、Mn、Li、Na、K又はプロトン化した窒素塩基からなる群の少なくとも1種から選択されるカチオンであり、mは1~4の整数であり、nは1~4の整数であり、xは1~4の整数である。) - (D-2)成分が、25℃、1013.25hPaの条件下で液体であるフェノキシホスファゼン化合物を含むことを特徴とする請求項1から6のいずれか一項に記載のウレタン変性ポリイミド系難燃樹脂組成物。
- (E)硬化促進剤をさらに含有することを特徴とする請求項1から8のいずれか一項に記載のウレタン変性ポリイミド系難燃樹脂組成物。
- (F)イオンキャッチャーをさらに含有することを特徴とする請求項1から9のいずれか一項に記載のウレタン変性ポリイミド系難燃樹脂組成物。
- (A)ウレタン変性ポリイミド系樹脂が、エーテル系溶媒、エステル系溶媒、ケトン系溶媒、及び芳香族炭化水素系溶媒からなる群から選ばれる少なくとも1種の有機溶媒中で反応させて得られるものであることを特徴とする請求項1から10のいずれか一項に記載のウレタン変性ポリイミド系難燃樹脂組成物。
- 揺変度で1.1以上のチクソトロピー性を有することを特徴とする請求項1から11のいずれか一項に記載のウレタン変性ポリイミド系難燃樹脂組成物。
- ソルダーレジスト層、表面保護層、層間絶縁層又は接着剤層を有する電子部品であって、前記層が請求項1から12のいずれか一項に記載のウレタン変性ポリイミド系難燃樹脂組成物を乾燥硬化して得られるものであることを特徴とする電子部品。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201080052655.3A CN102639640B (zh) | 2009-11-19 | 2010-11-15 | 氨基甲酸酯改性聚酰亚胺系阻燃树脂组合物 |
JP2010546986A JP5768372B2 (ja) | 2009-11-19 | 2010-11-15 | ウレタン変性ポリイミド系難燃樹脂組成物 |
KR1020127011114A KR101738193B1 (ko) | 2009-11-19 | 2010-11-15 | 우레탄 변성 폴리이미드계 난연 수지 조성물 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2009-263541 | 2009-11-19 | ||
JP2009263541 | 2009-11-19 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011062137A1 true WO2011062137A1 (ja) | 2011-05-26 |
Family
ID=44059615
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2010/070282 WO2011062137A1 (ja) | 2009-11-19 | 2010-11-15 | ウレタン変性ポリイミド系難燃樹脂組成物 |
Country Status (5)
Country | Link |
---|---|
JP (1) | JP5768372B2 (ja) |
KR (1) | KR101738193B1 (ja) |
CN (1) | CN102639640B (ja) |
TW (1) | TWI462953B (ja) |
WO (1) | WO2011062137A1 (ja) |
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012144672A (ja) * | 2011-01-14 | 2012-08-02 | Mitsubishi Rayon Co Ltd | エポキシ樹脂組成物、プリプレグおよび繊維強化複合材料 |
WO2012176806A1 (ja) * | 2011-06-21 | 2012-12-27 | 三菱瓦斯化学株式会社 | 難燃化された脂環式ポリイミド樹脂組成物およびその薄肉成型体 |
WO2013021895A1 (ja) * | 2011-08-05 | 2013-02-14 | 積水化学工業株式会社 | 導電材料及び接続構造体 |
WO2014065367A1 (ja) * | 2012-10-26 | 2014-05-01 | 日東電工株式会社 | ポリアミドイミド樹脂組成物 |
WO2014065365A1 (ja) * | 2012-10-26 | 2014-05-01 | 日東電工株式会社 | ポリアミドイミド樹脂組成物 |
WO2014065366A1 (ja) * | 2012-10-26 | 2014-05-01 | 日東電工株式会社 | ポリアミドイミド樹脂組成物 |
JPWO2013125086A1 (ja) * | 2012-02-24 | 2015-07-30 | 日立化成株式会社 | 半導体用接着剤、フラックス剤、半導体装置の製造方法及び半導体装置 |
JP2015530452A (ja) * | 2012-09-25 | 2015-10-15 | サビック グローバル テクノロジーズ ベスローテン フェンノートシャップ | 難燃性ポリマー組成物および物品 |
JP2016121201A (ja) * | 2014-12-24 | 2016-07-07 | 東洋紡株式会社 | ウレタン変性ポリイミド系樹脂溶液 |
US9425120B2 (en) | 2012-02-24 | 2016-08-23 | Hitachi Chemical Company, Ltd | Semiconductor device and production method therefor |
JP6070911B1 (ja) * | 2015-08-11 | 2017-02-01 | 東洋紡株式会社 | ウレタン変性ポリイミド系樹脂溶液 |
WO2017026174A1 (ja) * | 2015-08-11 | 2017-02-16 | 東洋紡株式会社 | ウレタン変性ポリイミド系樹脂溶液 |
WO2019181721A1 (ja) * | 2018-03-20 | 2019-09-26 | 積水化学工業株式会社 | 硬化性樹脂組成物、接着剤、接着フィルム、カバーレイフィルム、及び、フレキシブル銅張積層板 |
CN111295344A (zh) * | 2017-11-20 | 2020-06-16 | 朗盛德国有限责任公司 | 含有二碳酸二酯的铝容器 |
JP2020132679A (ja) * | 2019-02-13 | 2020-08-31 | 味の素株式会社 | 樹脂組成物 |
WO2024101296A1 (ja) * | 2022-11-08 | 2024-05-16 | 富士フイルム株式会社 | 樹脂組成物、硬化物、積層体、硬化物の製造方法、積層体の製造方法、半導体デバイスの製造方法、及び、半導体デバイス |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103897395A (zh) * | 2014-03-28 | 2014-07-02 | 哈尔滨工程大学 | 水滑石与聚酰亚胺复合泡沫材料的制备方法 |
CN109071955B (zh) * | 2016-04-22 | 2021-10-15 | 日保丽公司 | 固化性组合物、使用该组合物的固化膜及外涂膜 |
US20200115527A1 (en) * | 2017-06-22 | 2020-04-16 | Daikyo Chemical Co., Ltd. | Flame retardant treatment of polyester based synthetic fiber structure |
JP6844570B2 (ja) * | 2018-03-29 | 2021-03-17 | 信越化学工業株式会社 | シリコーンゴム−シリコーン変性ポリイミド樹脂積層体 |
CN113754696A (zh) * | 2020-06-01 | 2021-12-07 | 华中师范大学 | 磷杂菲衍生物、制备及阻燃应用 |
CN111621260B (zh) * | 2020-06-18 | 2022-01-25 | 株洲时代新材料科技股份有限公司 | 一种聚酰胺酸涂层胶及其制备方法 |
KR102200259B1 (ko) * | 2020-07-24 | 2021-01-11 | 와이제이종합건설 주식회사 | 차열성 및 난연성을 향상시킨 콘크리트 구조물에 대한 폴리우레아 방수 공법 |
CN112227965B (zh) * | 2020-12-09 | 2021-04-06 | 东营市金亿来石油机械有限公司 | 一种耐高温包覆抽油杆 |
CN117603529B (zh) * | 2024-01-18 | 2024-03-22 | 汕头市嘉祥塑料制品厂有限公司 | 一种抑菌性奶粉盖及其制备方法 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002129033A (ja) * | 2000-10-31 | 2002-05-09 | Otsuka Chem Co Ltd | 難燃性樹脂組成物及びその成形体 |
JP2002235001A (ja) * | 2001-02-09 | 2002-08-23 | Toyobo Co Ltd | 耐熱性組成物 |
JP2005047995A (ja) * | 2003-07-30 | 2005-02-24 | Kaneka Corp | 難燃性を向上させた耐熱性樹脂組成物およびその利用 |
JP2007270137A (ja) * | 2006-03-09 | 2007-10-18 | Showa Denko Kk | 熱硬化性樹脂組成物及びその用途 |
JP2008297388A (ja) * | 2007-05-30 | 2008-12-11 | Toyobo Co Ltd | 変性ポリイミド系樹脂組成物、該組成物を含有するペースト及び該ペーストから得られる電子部品 |
JP2009096915A (ja) * | 2007-10-18 | 2009-05-07 | Hitachi Chem Co Ltd | 熱硬化性樹脂組成物、これを用いたフレキシブル基板及び電子部品 |
JP2009185200A (ja) * | 2008-02-07 | 2009-08-20 | Hitachi Chem Co Ltd | 樹脂組成物及びこれらを用いたフレキシブル配線板 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006251715A (ja) * | 2005-03-14 | 2006-09-21 | Kaneka Corp | 難燃性を有する感光性樹脂組成物及び感光性ドライフィルムレジスト |
WO2008119693A1 (en) * | 2007-04-03 | 2008-10-09 | Basf Se | Dopo flame retardant compositions |
JP5289309B2 (ja) | 2007-05-11 | 2013-09-11 | 三井化学株式会社 | 樹脂組成物、ドライフィルム、およびそれから得られる加工品 |
-
2010
- 2010-11-15 KR KR1020127011114A patent/KR101738193B1/ko active IP Right Grant
- 2010-11-15 WO PCT/JP2010/070282 patent/WO2011062137A1/ja active Application Filing
- 2010-11-15 JP JP2010546986A patent/JP5768372B2/ja active Active
- 2010-11-15 CN CN201080052655.3A patent/CN102639640B/zh active Active
- 2010-11-18 TW TW099139636A patent/TWI462953B/zh active
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002129033A (ja) * | 2000-10-31 | 2002-05-09 | Otsuka Chem Co Ltd | 難燃性樹脂組成物及びその成形体 |
JP2002235001A (ja) * | 2001-02-09 | 2002-08-23 | Toyobo Co Ltd | 耐熱性組成物 |
JP2005047995A (ja) * | 2003-07-30 | 2005-02-24 | Kaneka Corp | 難燃性を向上させた耐熱性樹脂組成物およびその利用 |
JP2007270137A (ja) * | 2006-03-09 | 2007-10-18 | Showa Denko Kk | 熱硬化性樹脂組成物及びその用途 |
JP2008297388A (ja) * | 2007-05-30 | 2008-12-11 | Toyobo Co Ltd | 変性ポリイミド系樹脂組成物、該組成物を含有するペースト及び該ペーストから得られる電子部品 |
JP2009096915A (ja) * | 2007-10-18 | 2009-05-07 | Hitachi Chem Co Ltd | 熱硬化性樹脂組成物、これを用いたフレキシブル基板及び電子部品 |
JP2009185200A (ja) * | 2008-02-07 | 2009-08-20 | Hitachi Chem Co Ltd | 樹脂組成物及びこれらを用いたフレキシブル配線板 |
Cited By (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012144672A (ja) * | 2011-01-14 | 2012-08-02 | Mitsubishi Rayon Co Ltd | エポキシ樹脂組成物、プリプレグおよび繊維強化複合材料 |
EP2725067A4 (en) * | 2011-06-21 | 2015-01-14 | Mitsubishi Gas Chemical Co | FIRE-RESISTANT ALICYCLIC POLYIMIDE RESIN COMPOSITION AND THIN-WALLED FORM BODY THEREOF |
WO2012176806A1 (ja) * | 2011-06-21 | 2012-12-27 | 三菱瓦斯化学株式会社 | 難燃化された脂環式ポリイミド樹脂組成物およびその薄肉成型体 |
JPWO2012176806A1 (ja) * | 2011-06-21 | 2015-02-23 | 三菱瓦斯化学株式会社 | 難燃化された脂環式ポリイミド樹脂組成物およびその薄肉成型体 |
EP2725067A1 (en) * | 2011-06-21 | 2014-04-30 | Mitsubishi Gas Chemical Company, Inc. | Flameproofed alicyclic polyimide resin composition and thin-walled molded body of same |
JP5162728B1 (ja) * | 2011-08-05 | 2013-03-13 | 積水化学工業株式会社 | 導電材料及び接続構造体 |
WO2013021895A1 (ja) * | 2011-08-05 | 2013-02-14 | 積水化学工業株式会社 | 導電材料及び接続構造体 |
US9425120B2 (en) | 2012-02-24 | 2016-08-23 | Hitachi Chemical Company, Ltd | Semiconductor device and production method therefor |
JPWO2013125086A1 (ja) * | 2012-02-24 | 2015-07-30 | 日立化成株式会社 | 半導体用接着剤、フラックス剤、半導体装置の製造方法及び半導体装置 |
JP2015530452A (ja) * | 2012-09-25 | 2015-10-15 | サビック グローバル テクノロジーズ ベスローテン フェンノートシャップ | 難燃性ポリマー組成物および物品 |
WO2014065365A1 (ja) * | 2012-10-26 | 2014-05-01 | 日東電工株式会社 | ポリアミドイミド樹脂組成物 |
WO2014065366A1 (ja) * | 2012-10-26 | 2014-05-01 | 日東電工株式会社 | ポリアミドイミド樹脂組成物 |
WO2014065367A1 (ja) * | 2012-10-26 | 2014-05-01 | 日東電工株式会社 | ポリアミドイミド樹脂組成物 |
JP2016121201A (ja) * | 2014-12-24 | 2016-07-07 | 東洋紡株式会社 | ウレタン変性ポリイミド系樹脂溶液 |
JP6070911B1 (ja) * | 2015-08-11 | 2017-02-01 | 東洋紡株式会社 | ウレタン変性ポリイミド系樹脂溶液 |
WO2017026174A1 (ja) * | 2015-08-11 | 2017-02-16 | 東洋紡株式会社 | ウレタン変性ポリイミド系樹脂溶液 |
KR20180039580A (ko) * | 2015-08-11 | 2018-04-18 | 도요보 가부시키가이샤 | 우레탄 변성 폴리이미드계 수지 용액 |
KR102533436B1 (ko) | 2015-08-11 | 2023-05-17 | 도요보 엠씨 가부시키가이샤 | 우레탄 변성 폴리이미드계 수지 용액 |
CN111295344A (zh) * | 2017-11-20 | 2020-06-16 | 朗盛德国有限责任公司 | 含有二碳酸二酯的铝容器 |
WO2019181721A1 (ja) * | 2018-03-20 | 2019-09-26 | 積水化学工業株式会社 | 硬化性樹脂組成物、接着剤、接着フィルム、カバーレイフィルム、及び、フレキシブル銅張積層板 |
JPWO2019181721A1 (ja) * | 2018-03-20 | 2021-02-04 | 積水化学工業株式会社 | 硬化性樹脂組成物、接着剤、接着フィルム、カバーレイフィルム、及び、フレキシブル銅張積層板 |
JP7265474B2 (ja) | 2018-03-20 | 2023-04-26 | 積水化学工業株式会社 | 硬化性樹脂組成物、接着剤、接着フィルム、カバーレイフィルム、及び、フレキシブル銅張積層板 |
JP2020132679A (ja) * | 2019-02-13 | 2020-08-31 | 味の素株式会社 | 樹脂組成物 |
JP7135919B2 (ja) | 2019-02-13 | 2022-09-13 | 味の素株式会社 | 樹脂組成物 |
WO2024101296A1 (ja) * | 2022-11-08 | 2024-05-16 | 富士フイルム株式会社 | 樹脂組成物、硬化物、積層体、硬化物の製造方法、積層体の製造方法、半導体デバイスの製造方法、及び、半導体デバイス |
Also Published As
Publication number | Publication date |
---|---|
CN102639640B (zh) | 2014-06-11 |
JP5768372B2 (ja) | 2015-08-26 |
CN102639640A (zh) | 2012-08-15 |
JPWO2011062137A1 (ja) | 2013-04-04 |
TWI462953B (zh) | 2014-12-01 |
TW201125897A (en) | 2011-08-01 |
KR101738193B1 (ko) | 2017-05-19 |
KR20120105438A (ko) | 2012-09-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5768372B2 (ja) | ウレタン変性ポリイミド系難燃樹脂組成物 | |
JP5743042B1 (ja) | ポリウレタン樹脂組成物およびこれを用いた接着剤組成物、積層体、プリント配線板 | |
JP5224204B1 (ja) | 熱硬化性樹脂組成物 | |
JP2012144653A (ja) | ウレタン変性ポリイミド系難燃樹脂組成物 | |
US7935752B2 (en) | Thermosetting resin composition and uses thereof | |
KR102285047B1 (ko) | 폴리카보네이트이미드계 수지 페이스트 및 상기 페이스트를 경화하여 얻어지는 솔더 레지스트층, 표면 보호층, 층간 절연층 또는 접착층을 갖는 전자 부품 | |
JP5223458B2 (ja) | ウレタン変性ポリイミド系樹脂組成物、該組成物からなるペースト及び該ペーストから得られる電子部品 | |
JP2008297388A (ja) | 変性ポリイミド系樹脂組成物、該組成物を含有するペースト及び該ペーストから得られる電子部品 | |
JP5610301B2 (ja) | 熱硬化性樹脂組成物 | |
KR102422913B1 (ko) | 폴리카보네이트이미드 수지 및 그것을 포함하는 수지 조성물 | |
CN107922615B (zh) | 聚碳酸酯酰亚胺树脂和使用了其的糊剂 | |
JP7310808B2 (ja) | ポリカーボネートイミド樹脂、およびこれを用いたペースト |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201080052655.3 Country of ref document: CN |
|
ENP | Entry into the national phase |
Ref document number: 2010546986 Country of ref document: JP Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 10831531 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 20127011114 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 10831531 Country of ref document: EP Kind code of ref document: A1 |