KR101738193B1 - Urethane modified polyimide based flame retardant resin composition - Google Patents
Urethane modified polyimide based flame retardant resin composition Download PDFInfo
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- KR101738193B1 KR101738193B1 KR1020127011114A KR20127011114A KR101738193B1 KR 101738193 B1 KR101738193 B1 KR 101738193B1 KR 1020127011114 A KR1020127011114 A KR 1020127011114A KR 20127011114 A KR20127011114 A KR 20127011114A KR 101738193 B1 KR101738193 B1 KR 101738193B1
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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'
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- 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
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- 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
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- 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
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- 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
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- 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
Abstract
A urethane-modified polyimide flame retardant resin composition excellent in solubility and varnish stability, low temperature drying / curing property, low warpage property, bending property, printing suitability and flame retardancy and excellent in heat resistance, chemical resistance, electrical characteristics, workability and economy . The urethane-modified polyimide flame retardant resin composition of the present invention comprises (A) a tri- and / or tetra-valent polycarboxylic acid derivative (a) having an acid anhydride group, (b) a diol compound, and (c) an aliphatic polyamine residue derivative (B) an epoxy resin having two or more epoxy groups per molecule, (C) an inorganic or organic filler, and (D) a urethane-modified polyimide resin having an urethane bond, (D) a non-halogen flame retardant, wherein the non-halogen flame retardant comprises a component (D-1) having a weight loss rate at 350 占 폚 of 50% or more and 90% D-2) as an essential component.
Description
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 machine, 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.
At present, the flexible printed wiring board is a flexible printed wiring board that can be used for electronic device parts requiring flexibility and small space, for example, a device mounting board for a display device such as a liquid crystal display or a plasma display, a portable telephone, a digital camera, Inter-substrate relay cables, operation switch sub-boards, and the like.
However, since the solder resist layer, the surface protective layer, the interlayer insulating layer, or the adhesive layer, which are components of the flexible printed wiring board, are often coated and printed in the form of a solution, a closed loop type polyimide resin Have been proposed.
However, conventionally, since a high boiling point nitrogen polar solvent such as N-methyl-2-pyrrolidone is used as a solvent for making a polyimide resin varnish, A curing process is required and there is a problem that thermal degradation of the electronic member occurs. Further, when varnish is applied to a base material and left for a long period of time, ink, whitening of the coating film and voids may occur due to moisture absorption of the high boiling point nitrogen-based solvent, and there is a problem that setting of working conditions becomes complicated . Furthermore, since the polyimide resin is generally hard at a high modulus of elasticity, when it is laminated on a substrate such as a film or a copper foil, warpage or the like occurs due to a difference in modulus of elasticity. Further, the cured film has a problem in that the flexibility is poor and the flexibility is poor.
On the other hand, flame retardancy is often required for electronic parts. Regulatory movements are increasing in heavy metal compounds such as halogen-containing compounds typified by decabromoether and antimony trioxide, which have been conventionally used as flame retardants. The polyimide-based resin itself has a relatively high flame retardancy. However, when a high flame resistance such as UL standard is required, a non-halogen flame retardant such as a phosphorus compound, a nitrogen compound, a hydrated metal compound (aluminum hydroxide, magnesium hydroxide) do. However, these flame retardants have insufficient flame retardancy as compared with halogen-based flame retardants, and phosphorus-based flame retardants typified by phosphoric acid esters have a problem of poor hydrolysis resistance and heat resistance.
Polysiloxane-modified polyimide resins have been proposed as polyimide resins that are soluble in non-glycolide solvents and impart flexibility and flexibility to the resin by imparting low warpage and flexibility (see Patent Documents 1 and 2, for example) 2).
These polysiloxane-modified polyimide resins use a diamine having an expensive dimethylsiloxane bond as a starting material in order to lower the elastic modulus, resulting in a problem of low economic efficiency. In addition, there has been a problem that adhesion, solvent resistance, and chemical resistance are lowered as the amount of polysiloxane copolymerization increases.
In order to improve these drawbacks, for example, a composition using a polycarbonate-modified polyimide resin has been proposed (see Patent Documents 3 to 5).
These polycarbonate modified polyimide resins have improved defects derived from polysiloxane and have good printing suitability. However, in the composition obtained from this resin, in order to reduce warpage, the amount of polycarbonate modification of the polyimide resin is increased And the heat resistance tends to be lowered. In addition, the varnish stability was low, and the varnish hardened after a few days in storage. Further, in general, when introducing a low elastic modulus component to obtain low warpage property, the flame retardancy is often lowered in contrast to this. Sufficient flame retardancy could not be obtained for the coating film obtained from the composition proposed here.
As a polyimide resin composition which is soluble in a non-fluorine-based solvent and which has low flexibility and flexibility by making the resin flexible and has a low elastic modulus, and which satisfies the flammability criterion according to the UL standard, for example, a polycarbonate-modified polyimide- A composition containing a hydrated metal compound has been proposed (see Patent Documents 6 to 8).
These polycarbonate-modified polyimide-based resin compositions have low warpage, bendability and flame retardancy. However, when introducing a low elastic modulus component in order to reduce warpage, in many cases, heat resistance and flame retardancy are lowered.
The composition proposed here is for the use of a tape carrier package (TAB, COF) using a relatively thick polyimide film substrate and is used for a flexible printed wiring board FPC) applications, sufficient flame retardancy could not be obtained. In addition, when a thin polyimide film substrate is used, low warpability is not sufficient.
On the other hand, Patent Document 9 discloses that as the copolymerization component, at least one component selected from the group consisting of polyether, polyester, polyacrylonitrile-butadiene copolymer, polycarbonate diol and dimer acid is contained, And Patent Document 10 discloses a polyimide-based resin containing polyether as a copolymerization component, trimellitic acid and cyclohexanedicarboxylic acid as an acid component, and a polyimide-based resin containing Have been proposed.
Although these polyimide-based resins are expected to have excellent solubility in a non-zeolite-based solvent, they are not at the same time satisfactory in low warpage, solder heat resistance and printing suitability for flexible printed wiring boards. In addition, any of the polyimide-based resins, as the non-nitrogen-based reaction solvent, has low varnish stability, and the resin tends to precipitate with the lapse of time, and from the viewpoint of use, And economical efficiency was poor. In addition, these proposed compositions can not obtain sufficient flame retardancy because the alicyclic component is predominant.
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 a non-nitrogen-based solvent, and can not be said to have a low warpage and flexibility, and also has no flame retardance.
Patent Document 12 proposes a polyimide-based composition using, as a filler, a hydrated metal compound, a phosphorus compound and a nitrogen compound as a non-halogen flame retardant in a polysiloxane-modified polyimide resin. This polyimide resin composition is expected to satisfy the UL standards for flame retardancy in addition to the characteristics of solder heat resistance and printing suitability for use in flexible printed wiring boards. However, as described above, there is a problem in copolymerizing polysiloxane compounds there was. Also, as in Patent Documents 7 to 8, a large amount of a hydrated metal compound having a low flame retarding effect is contained in a large amount, resulting in an increase in the modulus of elasticity, resulting in a problem of low warpage and low flexibility.
Patent Document 13 proposes a siloxane-diamine-modified polyimide resin composition using a specific monomer in order to improve the drawbacks described above. This polyimide resin composition does not contain an inorganic flame retardant and is expected not to impair its low warpability. However, since an expensive monomer is used, the polyimide resin composition is inferior in economic efficiency and has problems such as adhesion due to a siloxane compound .
Patent Document 14 proposes a polyurethane resin composition and a polyimide resin composition using a dialkylphosphinate metal salt as a non-halogen flame retardant. This polyurethane resin composition is expected to satisfy the flammability standard according to the UL standard in addition to the properties such as solder heat resistance and printing suitability for use in a flexible printed wiring board. However, the flame retardant is not compatible with resins, Since the composition is compounded in a large amount, flexibility and low warpage are not always sufficient.
In order to improve these drawbacks, for example, a composition comprising a polyimide-based resin and a non-halogen flame retardant and phosphazene dissolved in a polyimide resin has been proposed (see Patent Documents 15 to 17). These polyimide resin compositions are expected to satisfy flame retardancy and low warpability in addition to characteristics such as solder heat resistance and printing suitability for a flexible printed wiring board. However, in order to exert a high flame retardancy with a phosphazene-based flame retardant alone , It is necessary to add a large amount of the flame retardant, thereby causing bleeding of the flame retardant.
(2) low temperature drying / curability; (3) low warpage; (4) flexibility; (5) printability; 6) A polyimide resin composition which can be applied as a solder resist layer, a surface protective layer, an interlayer insulating layer, or an adhesive layer satisfying both of flame retardancy has not been obtained.
Disclosure of Invention Technical Problem [8] The present invention has been made in order to solve the problems of the prior art described above, and its object is to provide a process for producing a low- Modified polyimide flame retardant resin composition excellent in heat resistance, chemical resistance, electrical characteristics, workability and economical efficiency and excellent in flame retardancy, To provide an electronic part which is obtained by using the above-
Means for Solving the Problems The present inventors have intensively studied in order to achieve the above object, and as a result, they have completed the present invention. That is, the present invention includes the following constitutions (1) to (12).
(1) A process for producing (1) a tri- and / or tetra-valent polycarboxylic acid derivative having (a) 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-based resin having a urethane bond,
(B) an epoxy resin having two or more epoxy groups per molecule,
(C) an inorganic or organic filler, and
(D) Non-halogen flame retardant
Modified polyimide flame retardant resin composition,
(D-1) having a weight loss rate of not less than 50% and not more than 90% at a temperature of 350 ° C and a component (D-2) of not less than 20% Wherein the urethane-modified polyimide-based flame-retardant resin composition is contained as a component.
(2) The urethane-modified polyurethane foam according to (1), wherein the weight loss ratio of the (D-1) component is 60% or more and 85% or less, Based flame retardant resin composition.
(3) The urethane-modified polyimide-based flame retardant resin composition according to (1) or (2), wherein the non-halogen-based flame retardant (D) comprises (A) a phosphorus-based flame retardant compatible with the urethane- Composition.
(4) The pharmaceutical composition according to (1), wherein the component (D-1) comprises a 9,10-dihydro-9-oxa-10-phenanthrene-10-oxide derivative and the component (D-2) comprises a phenoxyphosphazene compound A urethane-modified polyimide flame retardant resin composition according to any one of (1) to (3).
(5) The urethane-modified polyimide flame retardant resin composition according to any one of (1) to (3), wherein the non-halogen flame retardant (D) comprises a filler type non-halogen flame retardant.
(6) The composition according to the above (1), wherein component (D-1) comprises a 9,10-dihydro-9-oxa-10-phenanthrene-10-oxide derivative, A reaction product of a cyanamide derivative having at least one amino group with a phosphoric acid group or a reaction product of a cyanamide derivative having at least one amino group and a cyanuric acid, The urethane-modified polyimide flame retardant resin composition according to any one of (1) to (3) or (5),
(In the formulas [I] and formula [II], R 1 and R 2 may be the same or different from each other, and may be linear or branched C 1 -C 10 alkyl and / or cycloalkyl and / or aryl and / R 1 and R 2 may combine with each other to form a ring together with the adjacent phosphorus atom, R 3 is a linear or branched C 1 to C 10 alkylene, C 6 to C 10 cycloalkylene , C 6 to C 10 arylene, C 6 to C 10 alkylarylene or C 6 to C 10 arylalkylene and M is at least one element selected from the group consisting of Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe M is an integer of 1 to 4, n is an integer of 1 to 4, and Z is a cation selected from the group consisting of Zr, Ce, Bi, Sr, Mn, Li, Na, K and a protonated nitrogen base. And x is an integer of 1 to 4.)
(7) The urethane-modified polyurethane foam according to any one of (1) to (6), wherein the component (D-2) comprises a phenoxyphosphazene compound which is a liquid at 25 캜 under a condition of 1013.25 hPa Based flame retardant resin composition.
(8) The diol compound (b) is characterized by comprising a polyalkylene oxide adduct of bisphenol represented by the following formula (III): (b-1) a polyoxyalkylene glycol and / A urethane-modified polyimide flame retardant resin composition according to any one of (1) to (7).
(In formula [III], R 1 is an alkylene group of C 1 ~C 20, R 2 and R 3 may be the same or different from each other good, it represents an alkyl group of hydrogen or C 1 ~C 4, m is an integer of 1 or more And n is an integer of 1 or more.)
(9) The urethane-modified polyimide flame retardant resin composition according to any one of (1) to (8), further comprising (E) a curing accelerator.
(10) The urethane-modified polyimide flame retardant resin composition according to any one of (1) to (9), further comprising (F) an ion catcher.
(11) A process for producing a polyurethane resin, which comprises (A) reacting a urethane-modified polyimide resin in at least one organic solvent selected from the group consisting of an ether solvent, an ester solvent, a ketone solvent and an aromatic hydrocarbon solvent Modified polyimide flame retardant resin composition according to any one of (1) to (10).
(12) The urethane-modified polyimide flame retardant resin composition according to any one of (1) to (11), which has a thixotropic property of 1.1 or more in shinability.
(13) An electronic component having a solder resist layer, a surface protective layer, an interlayer insulating layer or an adhesive layer, wherein the layer is formed by drying the urethane-modified polyimide flame retardant resin composition described in any one of (1) And the cured product is obtained by curing.
According to the present invention, the following effects can be obtained: (1) solubility and varnish stability of a non-zeolitic solvent, (2) low temperature drying / curing property, (3) low warpability, (4) 6) A urethane-modified polyimide flame retardant resin composition excellent in flame retardance, suppressing bleed-out of a flame retardant, and excellent in heat resistance, chemical resistance, electrical characteristics, workability and economy 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 ink, and interlayer insulating film, as well as paints, coating agents, And can be used in a wide range of electronic devices.
Hereinafter, the present invention will be described in detail.
The urethane-modified polyimide-based flame retardant resin composition of the present invention,
(A) a polycarboxylic acid derivative (a) comprising a trivalent and / or tetravalent polycarboxylic acid derivative (a) 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-based resin having a urethane bond,
(B) an epoxy resin having two or more epoxy groups per molecule,
(C) an inorganic or organic filler, and
(D) Non-halogen flame retardant
≪ / RTI >
(D-1) having a weight loss of not less than 50% and not more than 90% and a component (D-2) having a weight decrease amount at 350 ° C of not less than 20% and not more than 20% As a component.
The trivalent and / or tetravalent polycarboxylic acid derivative (a) 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 derivatives may be aromatic, aliphatic or alicyclic.
The copolymerization amount of the component (a) is preferably from 30% by mole to 90% by mole, more preferably from 35% by mole to 85% by mole, based on 100% by mole of all the polyamine residue derivatives to be reacted. If the copolymerization amount is less than the above range, flame retardance, mechanical properties and heat resistance can not be obtained. If the copolymerization amount is more than the above range, copolymerization of the component (b) described below in a sufficient amount can not be carried out. There is a risk of degradation.
Examples of the aromatic polycarboxylic acid derivative include trimellitic acid anhydride, pyromellitic acid dianhydride, ethylene glycol bishydrohydrotrimellitate, propylene glycol bishydrohydrotrimellitate, 1,4-butanediol bisanhydrotrimellitate , Alkylene glycol bistehydrotrimellitates such as hexamethylene glycol bishydrohydrotrimellitate, polyethylene glycol bishydrohydrotrimellitate and polypropylene glycol bishydrohydrotrimellitate, hydroquinone bistinohydrotrimellitate, Hydroquinone bis-ethylene oxide adducts dianhydrotrimellitate, 4,4'-biphenylenebis anhydride trimellitate, 3,3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid Dianhydride, 2,3,5,6-pyridine tetracarboxylic acid dianhydride, 3,4,9,10-perylene tetracarboxylic acid dianhydride, 3,3 ', 4,4'-diphenylsulfone tetra Carboxylic acid dianhydride, m-terphenyl-3,3 ', 4,4'-tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 1,1,1,3,3,3 (2,3- or 3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3- or 3,4-dicarboxyphenyl) propane dianhydride , 2,2-bis [4- (2,3- or 3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2- Bis [3,4- dicarboxyphenoxy) phenyl] propane dianhydride, 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyl Disiloxane dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 2,2- Hydroxyphenyl) propane dibenzoate-3,3 ', 4,4'-tetracarboxylic acid dianhydride, 2,3,3', 4-biphenyl La, and the like dianhydride.
Examples of the aliphatic or alicyclic polycarboxylic acid derivative include butane-1,2,3,4-tetracarboxylic acid dianhydride, pentane-1,2,4,5-tetracarboxylic acid dianhydride, cyclo Butane tetracarboxylic acid dianhydride, hexahydro-pyromellitic dianhydride, cyclohexa-1-ene-2,3,5,6-tetracarboxylic acid dianhydride, 3-ethylcyclohexa- (1, 2), 5,6-tetracarboxylic acid dianhydride, 1-methyl-3-ethylcyclohexane-3- (1,2) 3-ethylcyclohex-1-en-3- (1,2), 5,6-tetracarboxylic dianhydride, 1-ethylcyclohexane-1- (1,2) Acid dianhydride, 1-propylcyclohexane-1- (2,3), 3,4-tetracarboxylic acid dianhydride, 1,3-dipropylcyclohexane-1- (2,3) , 3) -tetracarboxylic dianhydride, dicyclohexyl-3,4,3 ', 4'-tetracarboxylic dianhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetra Carboxylic acid dianhydride , 1-propylcyclohexane-1- (2,3), 3,4-tetracarboxylic acid dianhydride, 1,3-dipropylcyclohexane-1- (2,3) Tetracarboxylic dianhydride, dicyclohexyl-3,4,3 ', 4'-tetracarboxylic dianhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic acid Dianhydride, bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6- Tetrabromic acid dianhydride, hexahydrotrimellitic anhydride, and the like.
These trivalent or tetravalent polycarboxylic acid derivatives may be used singly or in combination of two or more kinds. Considering heat resistance, transparency, adhesion, solubility and cost, the polycarboxylic acid derivative is preferably selected from the group consisting of pyromellitic dianhydride, trimellitic anhydride, ethylene glycol bistinohydrotrimellitate, 3,3 ', 4,4 '- benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 2,2-bis [4- (2,3- or 3,4- Phenoxy) phenyl] propane dianhydride are preferable, and trimellitic anhydride and ethylene glycol bishydrohydrotrimellitate are more preferable.
The diol compound (b) constituting the component (A) is copolymerized as a flexible component imparting flexibility, low warpage and solubility to the polyimide resin. By copolymerizing the component (b), the elastic modulus of the resin is lowered, and the solubility (varnish) stability in a non-nitrogen-based solvent used as a polymerization solvent is increased.
The copolymerization amount of the component (b) is preferably from 10 mol% to 70 mol%, more preferably from 15 mol% to 65 mol%, based on 100 mol% of all the polyamine residue derivatives to be reacted. If the copolymerization amount is larger than the above range, flame retardancy, mechanical properties and heat resistance can not be obtained. If the copolymerization amount is less than the above range, there is a fear that the low bending property and the solubility in a non-nitric solvent are lowered.
The molecular weight of the component (b) is preferably from 500 to 3000, more preferably from 800 to 2,000. If the molecular weight is less than the above range, the heat resistance, flexibility and low warpability become insufficient. If the molecular weight is larger than the above range, the modification reaction may not proceed and the solubility may be lowered.
Examples of the diol compound include polyalkylene glycols, polyoxyalkylene glycols, polyalkylene oxide adducts of bisphenol, aliphatic / aromatic polyester diols, aliphatic / aromatic polycarbonate diols, polycaprolactone diols, polybutadiene Polyols, hydrogenated polybutadiene polyols, hydrogenated polyisoprene polyols, polydimethylsiloxane diols, polymethylphenylsiloxane diols, and the like. Preferably, polyoxyalkylene glycols, polyalkylene oxide adducts of bisphenol, aliphatic / aromatic polyester diols, aliphatic / aromatic polycarbonate diols, and more preferably polyoxyalkylene glycols (( (b-1) component) and a polyalkylene oxide adduct of bisphenol represented by the formula (III) (component (b-2)). Other diol compounds include bisphenols such as bisphenol A and bisphenol F, but these are undesirable because urethane bonds are dissociated at the time of heating.
Examples of the aliphatic / aromatic polyester diols include those obtained by dehydration condensation of a dicarboxylic acid and a diol or an ester exchange reaction between a lower alcohol esterified product of a dicarboxylic acid and a diol, , Or a condensation reaction of a diol with a hydroxyalkanoic acid.
Specific examples of the dicarboxylic acid component include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, brassylic acid, Dicarboxylic acid, 3-methyldicarboxylic acid, 3-methyldicarboxylic acid, 3-methyldicarboxylic acid, 3-methyldicarboxylic acid, Acid, 3,7-dimethyldecanedicarboxylic acid, dimeric acid, hydrogenated dimer acid, alkenyl succinic acid such as octenyl succinic acid, dodecenyl succinic acid, octadecenyl succinic acid, aliphatic such as fumaric acid, maleic acid and itaconic acid Dicarboxylic acids and ester-forming derivatives thereof, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 1,4-naphthalene dicarboxylic acid and 2,6-naphthalene dicarboxylic acid, and esters thereof Forming derivative, 1,4-cyclohexanedicarboxylic acid, tetrahydrophthalic acid , And the like hexahydro-isophthalic acid, 1,2-cyclohexene dicarboxylic aliphatic acids, such as dicarboxylic acids and their ester-forming derivatives thereof.
Specific examples of the diol component include ethylene glycol, propylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,5- Methyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, trimethylpentanediol, 2-ethyl-1,3-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2,4-diethyl-1,5-pentanediol, 1,10-decanediol, 2,2- Aliphatic diols such as ethyl-2-butyl-1,3-propanediol, diethylene glycol, triethylene glycol, eicosanic diol and neopentyl glycol hydroxypivalate; aliphatic diols such as 1,4-cyclohexanedimethanol, tricyclodecane Alicyclic diols such as dimethanol, dienes containing aromatic rings such as ethylene oxide adducts of bisphenol A or bisphenol S or adducts of propylene oxide, and reducers of dimer acids.
Specific examples of the hydroxyalkanoic acid component include 3-hydroxybutanoic acid, 4-hydroxypentanoic acid, 5-hydroxyhexanoic acid, and the like.
Examples of the lactone include? -Valerolactone,? -Valerolactone,? -Caprolactone,? -Methyl-? - propiolactone,? -Methyl-? - propiolactone, 3-n- Lactone, 6,6-dimethyl-delta-valerolactone, glycolide, and lactide.
The aliphatic / aromatic polycarbonate diol is obtained by a transesterification reaction between a diol and a carbonate compound, a ring-opening cyclic carbonate ester compound by ring-opening polymerization, or a reaction between a diol and a chloroformic ester or phosgene.
As the aliphatic / aromatic polycarbonate diol, it is preferable that at least 50 mol% of the alkylene chain contained is an alkylene group having 6 or more carbon atoms, and more preferably 90 mol% or more is an alkylene group having 6 or more carbon atoms. Most preferably, at least 50 mol% of the alkylene chain contained is a polycarbonate diol having at least 8 carbon atoms.
The aliphatic / aromatic polycarbonate diol described above is preferably a polycarbonate diol having a plurality of alkylene groups in its skeleton from the viewpoints of inhibition of crystallization and solubility of the resulting urethane-modified polyimide resin. Likewise, a polycarbonate diol having an alkylene group containing a side chain is preferred.
Examples of the polyoxyalkylene glycol (b-1) include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and poly (neopentyl glycol / tetramethylene glycol).
The copolymerization amount of the component (b-1) is preferably 5% by mass or more and 70% by mass or less of the urethane-modified polyimide-based resin as the polyurethane comprising the component (b-1) and the polyamine residue derivative, And more preferably not less than 40% by mass. When the copolymerization amount is less than the above range, the modulus of elasticity is not sufficiently lowered, and warpage occurs in the case of lamination, or the solubility in a non-nitrogen-based solvent is lowered, so that the resin may be precipitated within 5 months . This tendency is remarkable particularly when? -Butyrolactone, glyme or cyclohexanone preferably used in the present invention is used as a solvent. On the other hand, if it exceeds the above range, flame retardancy, mechanical properties and heat resistance may be lowered.
(b-2) The polyalkylene oxide adduct of bisphenol is represented by the following chemical formula [III], and imparts solubility and flexibility to the modified polyimide resin. Examples of the polyalkylene oxide include polyethylene oxide, polypropylene oxide, and polytetramethylene oxide. And preferably has a number average molecular weight of 200 or more and 2000 or less. Specifically, polyethylene oxide adducts of bisphenol A and polypropylene oxide adducts of bisphenol A can be given.
(In formula [III], R 1 is C 1 ~C 20 alkylene group, R 2 and R 3 represents an alkyl group may be the a is hydrogen or a C 1 ~C 4, different from each other may be the same, m is an integer number of 1 or more, and , and n is an integer of 1 or more.
The copolymerization amount of the component (b-2) is preferably 10% by mass or more and 75% by mass or less of the urethane-modified polyimide-based resin as the polyurethane comprising the component (b-2) and the polyamine residue derivative, And more preferably not less than 70% by mass. If the copolymerization amount is less than the above range, the solubility in the non-nitrogen-based solvent is lowered, and therefore there is a possibility that the resin is precipitated within 5 months at 30 ° C within one month. This tendency is remarkable particularly when? -Butyrolactone, glyme or cyclohexanone preferably used in the present invention is used as a solvent. On the other hand, if it exceeds the above range, flame retardancy, mechanical properties and heat resistance may be lowered.
As the aliphatic polyamine residue derivative (c) constituting the component (A), an aliphatic polyisocyanate or an aliphatic polyamine is used. Examples of the aliphatic polyisocyanate include hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate and lysine diisocyanate. Preferably hexamethylene diisocyanate. Examples of the aliphatic polyamines include hexamethylenediamine, 2,2,4-trimethylhexamethylenediamine, lysine diamine, and the like. Preferably hexamethylenediamine.
As the aromatic polyamine residue derivative (c) constituting the component (A), an aromatic polyisocyanate and an aromatic polyamine are used. Examples of the aromatic polyisocyanate include 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'- 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-4,4'-diisocyanate, diphenylmethane-3,3'-diisocyanate, diphenylmethane-3,4'-diisocyanate, diphenylether-4,4'-diisocyanate, benzo Diisocyanate, diphenylsulfone-4,4'-diisocyanate, tolylene-2,4-diisocyanate, tolylene-2,6-diisocyanate, m-xylylene diisocyanate, p - xylylene diisocaine Diisocyanate, 4,4 '- [2,2bis (4-phenoxyphenyl) propane] diisocyanate, 3,3'- or 2,2'-dimethylbiphenyl- Diisocyanate, 3,3'- or 2,2'-diethylbiphenyl-4,4'-diisocyanate, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, 3'-diethoxybiphenyl-4,4'-diisocyanate, and the like. Considering heat resistance, adhesion, solubility, cost, and the like, the aromatic polyisocyanate is diphenylmethane-4,4'-diisocyanate, tolylene-2,4-diisocyanate, m-xylylene diisocyanate, '- or 2,2'-dimethylbiphenyl-4,4'-diisocyanate is preferable, and diphenylmethane-4,4'-diisocyanate and tolylene-2,4-diisocyanate are more preferable.
Examples of the aromatic polyamines 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 4,3'- 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, diphenylether-4,4'-diamine, benzophenone- Diamine, tolylene-2,4-diamine, tolylene-2,6-diamine, m-xylylenediamine, p-xylylenediamine, naphthalene-2,6-diamine , 4,4 '- [2,2bis (4-phenoxyphenyl) propane] diamine, 3,3'- or 2,2'-dimethylbiphenyl-4,4'-diamine, 2,2'-diethylbiphenyl-4,4'-diamine, 3,3'-dimethoxybiphenyl -4,4'-diamine, 3,3'-diethoxybiphenyl-4,4'-diamine, and the like. Considering heat resistance, adhesion, solubility, cost, and the like, the aromatic polyamine is preferably diphenylmethane-4,4'-diamine, tolylene-2,4-diamine, m-xylylenediamine, 2,2'-dimethylbiphenyl-4,4'-diamine is preferable, and diphenylmethane-4,4'-diamine and tolylene-2,4-diamine are more preferable.
The aliphatic polyamine residue derivative (c) and / or the aromatic polyamine residue derivative (c) may be used singly 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 may be appropriately set within a range in which the solubility and low warpability are not impaired in balance with the amount of the diol compound (b).
In the urethane-modified polyimide resin (A), aliphatic polyamine residue derivatives and aromatic polyamine residue derivatives, as well as alicyclic polyamine residue derivatives, may be copolymerized even if they are copolymerized, as long as they do not impair the low warpability, heat resistance and flame retardancy none. Specific examples of the alicyclic polyamine residue derivatives include isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, transcyclohexane-1,4-diisocyanate, hydrogenated m-xylylene diisocyanate, Norbornenedisocyanate, and other alicyclic polyisocyanates. Considering heat resistance, adhesion, solubility, cost, and the like, isophorone diisocyanate and 4,4'-dicyclohexylmethane diisocyanate are preferable.
A polyamine residue derivative having three or more actions may be used, or a block stabilizer that is stabilized to avoid the change with the passage of time may be used. When the trifunctional or higher polyamine residue derivative is a triisocyanate or higher polyisocyanate, examples of the blocking agent include alcohols, phenols, oximes, and the like, but there is no particular limitation. These trifunctional or higher polyisocyanates may be used singly or in combination of two or more. When polymerization is carried out in excess of isocyanate, the isocyanate group at the terminal of the resin may be blocked with a blocking agent such as alcohols, lactams or oximes after completion of the polymerization.
On the other hand, in the component (A), aliphatic, alicyclic, and aromatic dicarboxylic acids may be copolymerized as necessary within a range that does not impair the desired performance. Examples of the aliphatic dicarboxylic acid include aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedioic acid, dodecanedioic acid, eicosanic acid, , 3-methyladipic acid, 3-methylpentanedicarboxylic acid, 2-methyloctanedicarboxylic acid, 3,8-dimethyldecanedicarboxylic acid, 3,7-dimethyldecanedicarboxylic acid, Dicarboxylic acid, 12-dimethylhexanoic acid, 12-dimethylhexanoic acid, fumaric acid, maleic acid, dimeric acid and hydrogenated dimeric acid. Examples of the alicyclic dicarboxylic acid include 1,4-cyclohexanedicarboxylic acid, Hexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, and 4,4'-dicyclohexyldicarboxylic acid. Examples of the aromatic dicarboxylic acid include isophthalic acid, terephthalic acid, orthophthalic acid , Naphthalene dicarboxylic acid, oxydibenzoic acid, stilbene dicarboxylic acid, and the like. These dicarboxylic acids may be used singly or in combination of two or more kinds. Considering heat resistance, adhesion, solubility and cost, the dicarboxylic acids are preferably sebacic acid, 1,4-cyclohexanedicarboxylic acid, dimeric acid and isophthalic acid.
The urethane-modified polyimide resin (A) is obtained by reacting a polycarboxylic acid component having an acid anhydride group with a method of producing a polycarboxylic acid component having an acid anhydride group from an isocyanate component by decarboxylic acid (isocyanate method) Followed by cyclization to form amic acid, followed by ring closure (direct method). Industrially, isocyanate method capable of urethane modification is advantageous.
When the (A) urethane-modified polyimide resin is produced by an isocyanate method, the amount of the tri- and / or tetra-valent polycarboxylic acid derivative having an acid anhydride group as component (a) and the diol compound of component (b) , The number of isocyanate groups / (number of acid anhydride groups + number of carboxylic acid groups + number of hydroxyl groups) = 0.80 to 1.20. If it is out of the above range, it becomes difficult to increase the molecular weight of the urethane-modified polyimide resin, resulting in deterioration of heat resistance and bending property, and the coating film may be fragile.
The polymerization reaction of the (A) urethane-modified polyimide resin is preferably carried out in the presence of at least one organic solvent selected from an ether solvent, an ester solvent, a ketone solvent and an aromatic hydrocarbon solvent, Followed by heating and condensing while removing carbon dioxide generated from the glass from the reaction system.
Examples of the ether solvents include diethylene glycol dimethyl ether (diglyme), diethylene glycol diethyl ether (ethyl diglyme), triethylene glycol dimethyl ether (triglyme), triethylene glycol diethyl ether (ethyltriglyme ), And examples of the ester solvent include γ-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 monobutyl ether acetate, 3-methoxybutyl acetate, dipropylene glycol methyl ether acetate, propylene glycol diacetate, methyl Benzoate, ethyl benzoate and the like, As tongye solvent, such as and the like methyl isobutyl ketone, cyclopentanone, cyclohexanone, isophorone, aromatic hydrocarbon solvents, for example there may be mentioned toluene, xylene, Solvesso cattle and the like. These may be used singly or in combination of two or more.
In order to produce the varnish of the urethane-modified polyimide resin (A), it is preferable to select and use a solvent which dissolves the resulting urethane-modified polyimide resin so as to be used as a varnish after the polymerization. In this case, troublesome operations such as solvent replacement and the like are eliminated, and production can be made at a 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 占 폚, the solvent may volatilize during the polymerization reaction. In addition, for example, when screen printing is performed, there is a possibility that the volatilization of the solvent is accelerated and clogging occurs. When it exceeds 230 캜, it becomes difficult to impart low temperature drying / curability. In order to impart relatively high volatility, low-temperature drying / curability, excellent varnish stability, and efficient reaction in a homogeneous system, it is preferable to use γ-butyrolactone, cyclohexanone, diglyme, triglyme, Ethyl carbitol acetate is preferred.
The amount of the solvent to be used is preferably 0.8 to 5.0 times (mass ratio) of the resulting urethane-modified polyimide resin, more preferably 0.9 to 2.0 times. If the amount is less than the above range, the viscosity at the time of synthesis tends to be too high, and synthesis becomes difficult due to inability to stir. When the amount exceeds the above range, the reaction rate tends to decrease.
As the process for producing the urethane-modified polyimide resin (A), in the case of the isocyanate method, for example, (1) the components (a), (b) and (c) (2) A method for producing a urethane-modified polyimide resin, which comprises reacting the component (a) and / or the component (b) with an excessive amount of the component (c) to synthesize a urethane- modified oligomer having an isocyanate group at the terminal (3) A method of reacting an excess amount of the component (a) and / or the component (b) and the component (c) Modified urethane oligomer having a carboxylic acid group and / or an acid anhydride group and / or a hydroxyl group at the end thereof, and then the component (c) is further reacted to obtain an urethane-modified polyimide resin.
In the case of the isocyanate method, the reaction temperature is preferably from 60 to 200 캜, and more preferably from 100 to 180 캜. If the reaction temperature is lower than the above range, the reaction time becomes excessively long. If the reaction temperature exceeds the above range, the monomer component may be decomposed during the reaction. Further, a three-dimensional reaction occurs and gelation tends to occur. The reaction temperature may be set in multiple stages. The reaction time can be appropriately selected depending on the scale of the batch, the reaction conditions employed, and in particular, the reaction concentration.
In the isocyanate method, triethylamine, lutidine, picoline, undecene, triethylenediamine (1,4-diazabicyclo [2.2.2] octane), DBU (1,8-diazabicyclo [ Cyclo [5.4.0] -7-undecene), alkali metals such as lithium methylate, sodium methylate, sodium ethylate, potassium butoxide, potassium fluoride and sodium fluoride, alkaline earth metal compounds, , Tin, zinc, aluminum or the like, or a semi-metal compound.
The logarithmic viscosity of the urethane-modified polyimide resin (A) is preferably from 0.1 dl / g to 2.0 dl / g, more preferably from 0.2 dl / g to 1.8 dl / g. If the logarithmic viscosity is less than the above range, the heat resistance may be lowered or the coating film may be fragile. Also, the tackiness of the paste is strong and the plate separation is deteriorated. On the other hand, if it is larger than the above range, it is difficult to dissolve in a solvent and is liable to be insolubilized during polymerization. Further, the viscosity of the varnish becomes high, so that handling becomes difficult or adhesiveness to a substrate deteriorates. Moreover, the concentration of the non-volatile component of the paste can not be increased, and it becomes difficult to form a thick film. The urethane-modified polyimide resin having an logarithmic viscosity in this range can be obtained by suitably adjusting the polymerization conditions such as the monomer ratio and the polymerization temperature.
The glass transition temperature of the urethane-modified polyimide resin (A) is preferably 20 占 폚 or higher, and more preferably 60 占 폚 or higher. Below the temperature, there is a fear that the heat resistance is insufficient and the resin is blocked. The upper limit is not particularly limited, but 300 占 폚 or lower is preferable from the viewpoint of solvent solubility. The urethane-modified polyimide resin having a glass transition temperature within this range can be obtained.
The urethane-modified polyimide flame retardant resin composition of the present invention comprises (A) an epoxy resin having two or more epoxy groups per molecule (B) for the purpose of improving the film properties after film formation by curing the urethane-modified polyimide resin Containing resin.
Examples of the epoxy resin as the component (B) include bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, brominated bisphenol A type epoxy resin, phenol novolak type epoxy resin, Epoxy resin, epoxy resin, epoxylated polybutadiene, polyfunctional epoxy resin, amine type epoxy resin, heterocyclic ring containing epoxy resin, alicyclic epoxy resin, bisphenol S type epoxy resin, triglycidyl isocyanurate, A cyanine type epoxy resin, a bisphenol type epoxy resin, a naphthalene type epoxy resin, a dicyclopentadiene type epoxy resin, and a phosphorus containing epoxy resin. These resins may be used singly or in combination of two or more kinds.
Of these epoxy resins, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin having more than two epoxy groups in one molecule, o-cresol novolak type epoxy resin, amine type epoxy resin, , Which is preferable in view of compatibility with the urethane-modified polyimide resin of component (A), solvent resistance, chemical resistance and moisture resistance.
The amount of the epoxy resin (B) to be used is preferably from 1 to 50 parts by mass, more preferably from 2 to 40 parts by mass, and particularly preferably from 3 to 30 parts by mass, per 100 parts by mass of the urethane-modified polyimide resin. If the blending amount of the epoxy resin is less than the above range, the solder heat resistance, solvent resistance, chemical resistance and moisture resistance tends to be lowered. If the blending amount exceeds the above range, the solder tends to have low warpage, mechanical properties, heat resistance, varnish stability, The compatibility with the resin tends to be lowered.
The addition amount of the component (A) plus the component (B) is preferably 40 to 90 mass%, based on 100 mass% of the entire non-volatile components in the urethane-modified polyimide resin composition. And more preferably 45 to 80 mass%.
The epoxy resin (B) may further contain, as a diluent, an epoxy compound having only one epoxy group in one molecule.
As the method for adding the epoxy resin (B), the epoxy resin added in advance may be added after dissolving in the same solvent as the solvent contained in the urethane-modified polyimide resin, or may be added directly to the urethane-modified polyimide resin.
On the other hand, in the present invention, in addition to the epoxy resin, known curing systems such as polyisocyanate, cyanate ester, oxetane, and acrylate may be used in combination.
The urethane-modified polyimide flame retardant resin composition of the present invention contains (C) an inorganic or organic filler in order to improve workability in coating, printing, and film properties after film formation.
The inorganic or organic filler (C) is not particularly limited as long as it can be dispersed in the urethane-modified polyimide resin to give thixotropic properties. Examples of the inorganic filler, for example, silica (SiO 2), alumina (Al 2 O 3), titania (TiO 2), tantalum oxide (Ta 2 O 5), zirconia (ZrO 2), silicon nitride (Si 3 N 4), barium titanate (BaO · TiO 2), barium carbonate (BaCO 3), lead titanate (PbO · TiO 2), lead zirconate titanate (PZT), titanate zirconate scattering tannap (PLZT), gallium oxide (Ga 2 O 3), spinel (MgO · Al 2 O 3) , mullite (3Al 2 O 3 · 2SiO 2 ), cordierite (2MgO · 2Al 2 O 3 · 5SiO 2), talc (3MgO · 4SiO 2 · H 2 O), aluminum titanate (TiO 2 -Al 2 O 3 ), yttria-containing zirconia (Y 2 O 3 -ZrO 2 ), barium silicate (BaO · 8SiO 2 ), boron nitride (BN), calcium carbonate (CaCO 3 ) 4), zinc (ZnO), magnesium titanate (MgO · TiO 2), barium sulfate (BaSO 4), may be used an organic bentonite, carbon (C) and the like, which, even if used alone oxide used in combination of two or more It does not matter. Silica fine particles are preferable in terms of hue, transparency, mechanical properties and thixotropic property of the obtained paste.
The inorganic filler preferably has an average particle diameter of 50 mu m or less and a maximum particle diameter of 100 mu m or less, more preferably 20 mu m or less, and most preferably 10 mu m or less. The average particle diameter (median diameter) referred to herein is determined on the basis of volume by using a laser coater-scattering particle size distribution measuring apparatus. When the average particle diameter exceeds 50 占 퐉, it becomes difficult to obtain a composition having sufficient thixotropy, and the bending property of the obtained coating film is lowered. If the maximum particle diameter exceeds 100 占 퐉, the appearance and adhesion of the coating film tend to become insufficient.
The organic filler is not particularly limited as long as it can be dispersed in the urethane-modified polyimide resin solution to give thixotropic properties, and examples thereof include polyimide resin particles, benzoguanamine resin particles and epoxy resin particles.
The amount of the inorganic or organic filler (C) to be used is preferably 0.5 to 25% by mass when the total amount of the non-volatile components in the urethane-modified polyimide resin composition is 100% by mass. More preferably 2 to 15% by mass, and particularly preferably 3 to 12% by mass. When the blending amount of the inorganic or organic filler is less than 0.5 mass%, the printing property tends to be lowered. When the blending amount exceeds 25 mass%, mechanical properties such as flexibility of the coating film and transparency tend to be lowered.
The urethane-modified polyimide flame retardant resin composition of the present invention contains (D) a non-halogen flame retardant to have flame retardancy. The non-halogen flame retardant (D) is prepared by mixing two components, that is, a component (D-1) having a weight loss rate of at least 50% and at most 90% at 350 ° C and a component (D-2) As a component. The weight reduction ratio of the component (D-1) is preferably 60% or more and 85% or less, and the weight reduction ratio of the component (D-2) is preferably 0% or more and 15% or less.
Specifically, the above-mentioned weight reduction rate is measured by heating from room temperature to 100 占 폚 at a heating rate of 10 占 폚 / min in an air atmosphere by TGA (thermogravimetric analysis), holding for 30 minutes, Lt; 0 > C to 350 < 0 > C when heated on an aluminum pan. By combining a flame retardant having a large weight reduction rate and a flame retardant having a small weight reduction ratio as a non-halogen flame retardant, high flame retardancy can be achieved with a very small addition amount. This is because the flame retardant having a higher weight loss rate than that of the urethane-modified polyimide resin is volatilized to produce an incombustible atmosphere, an effect of suppressing the generation of resin decomposition gas by forming a char on the surface, And the reaction with the resin and the formation of the surface heat insulating structure are combined to obtain an efficient flame retardancy. As a result, it is possible to suppress the influence of the flame retardant on properties other than heat resistance, flexibility, bleed-out (juicing), etc. of the coating film containing the urethane-modified polyimide flame retardant resin composition.
Such a non-halogen flame retardant (D) is not particularly limited, but it preferably contains (A) a phosphorus-based flame retardant commonly used in a urethane-modified polyimide resin. By acting as a plasticizer of the urethane-modified polyimide resin, the low warpability of the coating film can be improved.
On the other hand, in the present invention, the phosphorus-based flame retardant commonly used in the urethane-modified polyimide-based resin means that the Tg of the composition compounded with respect to the Tg (glass transition temperature) of the urethane-modified polyimide- The behavior can be determined by, for example, a change in the position of the heat quantity displacement of the DSC (differential scanning calorimetry) or a change in the peak position of the loss tangent in the DMA (dynamic viscoelasticity measurement).
The non-halogen flame retardant (D) preferably contains a urethane-modified polyimide resin and a filler-type non-halogen flame retardant which is not compatible with a solvent. By mixing the filler type flame retardant, it is possible to improve the heat resistance of the coating film, in particular the physical heat resistance such as blocking during heating and the bleeding out of the flame retardant.
Examples of the filler-type non-halogen flame retardant include a phosphinic acid metal salt represented by the following chemical formula [I], a diphosphinic acid metal salt represented by Chemical Formula [II], a reaction product of a cyanamide derivative having at least one amino group and a phosphoric acid, Or a reaction product of a cyanamide derivative having at least one amino group with cyanuric acid.
Examples of the non-halogen flame retardant (D) include 9,10-dihydro-9-oxa-10-phenanthrene-10-oxide derivatives, phenoxyphosphine oxide and the like in view of flame retardance, hydrolysis resistance, heat resistance and surface bleed- A spazen compound, a phosphinic acid metal salt represented by the following formula [I], a diphosphinic acid metal salt represented by the following formula [II], a reaction product of a cyanamide derivative having at least one amino group and a phosphoric acid group, (D-1) comprises a 9,10-dihydro-9-oxa-10-phenanthrene-10-oxide derivative, and the reaction product of ) Component is a phenoxyphosphazene compound, a phosphinic acid metal salt represented by the following chemical formula [I], a diphosphinic acid metal salt represented by the following chemical formula [II], a reaction product of a cyanamide derivative having at least one amino group and a phosphoric acid, At least one It is more preferable to include the cyanamide derivative having an amino group and a reaction product of cyanuric acid.
(In the formulas [I] and formula [II], R 1 and R 2 may be the same or different and are each a linear or branched C 1 -C 10 alkyl and / or cycloalkyl and / or aryl and / R 1 and R 2 may combine with each other to form a ring together with the adjacent phosphorus atom, R 3 is a linear or branched C 1 to C 10 alkylene, a C 6 to C 10 cycloalkylene , C 6 to C 10 arylene, C 6 to C 10 alkylarylene or C 6 to C 10 arylalkylene and M is at least one element selected from the group consisting of Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe M is an integer of 1 to 4, n is an integer of 1 to 4, and Z is a cation selected from the group consisting of Zr, Ce, Bi, Sr, Mn, Li, Na, K and a protonated nitrogen base. And x is an integer of 1 to 4.)
Examples of the 9,10-dihydro-9-oxa-10-phenanthrene-10-oxide derivative include HCA (9,10-dihydro-9-oxa-10-phosphaphenanthrene- Oxide), HCA-HQ (10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide), SANKO-BCA -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide), 10- (2,5-dihydroxy-6-methylphenyl) -9,10-dihydro- -10-phosphaphenanthrene-10-oxide, 10- (2,5-dihydroxy-2-naphthyl) -9,10-dihydro-9-oxa- (2-hydroxyethyl) ester of 2- (9,10-dihydro-9-oxa-10-phosphapenanthrene-10-oxide-10-yl) methyl succinate, 10-phosphaphenanthrene-10-oxide, 10-phenyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, ethyl (3- 10-dihydro-9-oxa-10-phosphapenanthrene-10-oxide-10-yl) methyl) -2, 5-pyrrolidinedione And the like.
Of these 9,10-dihydro-9-oxa-10-phenanthrene-10-oxide derivatives, those which are compatible with the urethane-modified polyimide resin (A) are preferable, and SANKO-BCA (10-benzyl- -Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide). HCA (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide), HCA-HQ (10- (2,5-dihydroxyphenyl) -9,10-dihydro- Oxa-10-phosphaphenanthrene-10-oxide) have reactivity with an epoxy resin, but they may cause bleeding on the surface, have compatibility with a urethane-modified polyimide resin and solubility in a non- It tends to fall. Therefore, it is appropriately selected in consideration of the performance such as low warpage.
Examples of the phenoxyphosphazene compound include cyclic phenoxyphosphazenes such as SPE-100 and SPB-100L manufactured by Otsuka Chemical Co., Ltd., and cyclic cyano compounds such as FP-300 (trade name, manufactured by Fushimi- Cyclic phenoxyphosphazenes such as Phenoxyphosphazene and SPH-100 (trade name) manufactured by Otsuka Chemical Co., Ltd., and chain phenoxyphosphazenes and crosslinked phenoxyphosphazenes. Other examples include chain phosphazenes Generally has a phosphorus content lower than that of cyclic phosphazene because it has a substituent at the molecular end. Therefore, in the present invention, cyclic phosphazene is preferable, and cyclic trimer and / or tetramer phosphazene is more preferable. When a reactive phosphazene having a functional group reactive with a urethane-modified polyimide resin such as SPH-100 is used, since it is inserted in the curing system, no bleeding occurs on the surface, which is preferable.
When a non-reactive phosphazene having no functional group reactive with the urethane-modified polyimide resin is used, the crystallinity may cause bleeding on the surface over time, or may cause the surface to undergo bleeding under severe conditions of use, It is preferable to use phosphazene liquid, such as SPB-100L or the like, under the conditions of 25 ° C and 1013.25 hPa, since phosphorus in the glass may be eluted or the decomposition product may deteriorate the insulating properties.
Examples of the phosphinic acid metal salt include dialkylphosphinic acid Al salts such as dimethylphosphinic acid Al, methylethylphosphinic acid Al and diethylphosphinic acid Al, arylphosphinic acid Al salts such as phenylphosphinic acid Al and diphenylphosphinic acid Al, 1-oxide Al salt, 2-carboxy-1-hydroxy-1H-phosphoran-1-oxide Al salt and the like An Al salt of an alkylene phosphinic acid which may have a substituent, a Zn salt and a Ca salt corresponding to these Al salts, and other metals.
Specific examples of the diphosphonic acid salt include alkane bis (phosphinic acid) Al salts such as ethane-1,2-bis (phosphinic acid) Al salt and ethane-1,2-bis (methylphosphinic acid) Bis (alkylphosphinic acid) Al salts, Zn salts and Ca salts corresponding to these Al salts, and other metal salts.
That is, in the chemical formula [I] and chemical formula [II], R 1 and R 2 may be the same or different and may be linear or branched C 1 -C 10 alkyl and / or cycloalkyl and / Or an aryl group and / or an aralkyl group. Particularly preferably, they may be the same or different from each other, and examples thereof include a methyl group, ethyl group, n-propyl group, isopropyl group, n- butyl group, to be.
The ring formed by 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 hetero ring having 4 to 20 membered hetero rings, It can be called a circle. The hetero ring having the phosphorus atom may be a bicyclo ring or may have a substituent.
R 3 is straight or branched of the C 1 ~C 10 alkylene group, C 6 ~C 10 cycloalkyl group, C 6 ~C 10 aryl group, C 6 ~C 10 of the alkylaryl group or a C 6 ~ An alkylene group having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms, and preferably an alkylene group having 1 to 10 carbon atoms, such as a methylene group, an ethylene group, an n-propylene group, an isopropylene group, Examples of the n-dodecylene group and the cycloalkylene group include a cyclohexylene group, a cyclohexadimethylene group, an arylene group, a phenylene group or a naphthylene group, and an alkylarylene group include a methylphenylene group, an ethylphenylene group, a tert- , A methylnaphthylene group, an ethylnaphthylene group or a tert-butylnaphthylene group, and an arylalkylene group include a phenylmethylene group, a phenylethylene group, a phenylpropylene group and a phenylbutylene group.
M is at least one member selected from the group consisting of Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K and a protonated nitrogen base And is preferably selected from Mg, Ca, Al, Ti and Zn ions.
The phosphinates and diphosphates also include polymers or condensates of polyvalent salts of these phosphonic acids and / or polyvalent salts of diphosphonic acids.
The average particle size of phosphinic acid salts is preferably 10 탆 or less, more preferably 8 탆 or less, and further preferably 5 탆 or less. If the average particle diameter exceeds 10 占 퐉, the use amount for exhibiting sufficient flame retardancy increases, which is economically disadvantageous. Further, insulation reliability, bendability, adhesion, appearance and the like deteriorate. Specific examples of such phosphinic acid salts include diethylphosphinic acid aluminum, which is commercially available as EXOLIT OP935 and OP930 (trade name, manufactured by Clariant Japan K.K.).
The average particle diameter (median diameter) of phosphinic acid salts is determined on the basis of volume by using a laser coagulation / scattering type particle size distribution measuring apparatus.
A cyanamide derivative having at least one amino group in the reaction product of a cyanamide derivative having at least one amino group and a phosphoric acid group, a reaction product of a cyanamide derivative having at least one amino group and cyanuric acid, = C = N- or -N = C (-N <) is a compound having a unit represented by 2, and an amino group-containing triazine jinryu (melamine, melram, melrem, melon, guanamine, acetonitrile guanamine, benzoguanamine of Amino group-containing 1,3,5-triazine and 3-amino-1,2,4-triazine), amino group-containing triazoles (2,5-diamino- 1,3,4-triazole, and other amino group-containing 1,3,4-triazoles) and the like, guanidines (guanidine, guanidine derivatives (dicyandiamide, guanyl urea etc.) And cyclic cyanamide derivatives. Preferred cyanamide derivatives are amino group-containing 1,3,5-triazine derivatives, guanidine or derivatives thereof, in particular condensation products of melamine or melamine. These may be used singly or in combination of two or more.
The phosphoric acid to be reacted with the cyanamide derivative is an inorganic phosphoric acid such as non-condensed phosphoric acid (orthophosphoric acid, metaphosphoric acid, phosphorous acid (phosphonic acid), hypophosphoric acid (phosphinic acid)) and polyphosphoric acid. Examples of polyphosphoric acid include condensed phosphoric acids such as pyrophosphoric acid, tricinic acid, and sine acid.
As a reaction product of a cyanamide derivative having at least one amino group and a phosphoric acid derivative, a cyanamide derivative having at least one amino group and a cyanuric acid, a condensation product of melamine, a condensation product of melamine or melamine, A reaction product of a condensation product of melamine or melamine and a condensation product of phosphoric acid, and a reaction product of condensation product of melamine or melamine and cyanuric acid, and more preferably, at least one of melamine polyphosphate, melem polyphosphate Melamine polyphosphate, melamine polyphosphate, melamine polyphosphate and melamine cyanurate. Most preferred are melamine polyphosphate and melamine cyanurate having a chain length of 2 or more, particularly 10 or more and 50 or less. These may be used singly or in combination of two or more.
The average particle diameter of the reaction product of the cyanamide derivative having at least one amino group and the phosphoric acid group, the reaction product of the cyanamide derivative having at least one amino group and the cyanuric acid is preferably not more than 10 mu m, more preferably not more than 8 mu m , More preferably not more than 5 mu m. When the average particle size exceeds 10 占 퐉, the amount of use for expressing sufficient flame retardancy increases, which is economically disadvantageous. Further, insulation reliability, bending property, adhesion, appearance and the like are deteriorated. Specific examples of such a reaction product of a cyanamide derivative having at least one amino group with a phosphoric acid derivative and a cyanamide derivative having at least one amino group and cyanuric acid include MELAPURE 200 manufactured by Chiba Specialty Chemicals , MC25, Nosan Kagaku Kogyo Co., Ltd., PHOSMEL-200, Sanwa Chemical Co., Ltd. MPP-A, and Sakaikakakuko STABIACE MC-5F, MC-5S and MC-2010N.
The content of phosphorus in the urethane-modified polyimide flame retardant resin composition of the present invention is preferably 1.4 to 7.0 mass%, and the addition amount of the component (D) is controlled so as to be within this range. Preferably 1.6 mass% or more and 4.8 mass% or less, and more preferably 2.0 mass% or more and 4.0 mass% or less. If the phosphorus content is less than the above range, good flame retardancy can not be obtained. If the phosphorus content is out of the above range, the mechanical properties, heat resistance, adhesion and insulation properties of the coating film may be deteriorated.
The mixing ratio of the component (D-1) and the component (D-2) is not particularly limited as long as phosphorus content in the urethane-modified polyimide flame retardant resin composition and required flame retardancy can be achieved, -1): (D-2) = 80: 20 to 40: 60. When the content of the component (D-1) exceeds 80 mass% of the entirety of the component (D), the heat resistance of the coating film tends to be impaired. When the content is less than 40 mass%, the low-warp property can not be obtained. If you use Sipo Spazen, there is a risk of bleeding out.
In the present invention, for the purpose of further improving the flame retardancy, triphenylphosphate, tricresylphosphate, trixylenylphosphate, triethylphosphate, cresyldiphenylphosphate, xylylenediphenylphosphate, (Xylylenyl) phosphate, 2-ethylhexyl phosphate, dimethyl methyl phosphate, resorcinol bis (diphenol A bis (dicredyl) phosphate, diethyl- Phosphorus flame retardants such as phosphate, diethylphosphinate, phenylphosphinate, diphenylphosphinate, organic phosphine oxide, phosphoric acid amide, and red phosphorus, ammonium polyphosphate, triazine, succinoguanamine, , Nitrogen-based flame retardants such as melamine, tris (? -Cyanoethyl) isocyanurate, acetoguanamine, guanyl melamine sulfate, melamine sulfate and melamine sulfate, potassium diphenylsulfone-3-sulfonate, Based flame retardants such as aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, barium hydroxide, basic magnesium carbonate, zirconium hydroxide and tin oxide, metal oxide flame retardants such as silica, aluminum oxide, iron oxide Titanium oxide, manganese oxide, magnesium oxide, zirconium oxide, zinc oxide, molybdenum oxide, cobalt oxide, bismuth oxide, chromium oxide, tin oxide, antimony oxide, nickel oxide, copper oxide, tungsten oxide, zinc borate, zinc metaborate, Halogen flame retardants such as inorganic flame retardants / flame retardant additives such as barium metaborate, barium metaborate, zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate and zinc stearate, silicone powder and the like may be used in combination. The amount of specific use may be selected from the range of Bullet-modified polyimide resin composition and the electrical properties of the cured coating film, the range in heat resistance, does not damage the various physical properties such as environmental compatibility, there is no correlation to properly set.
The urethane-modified polyimide flame retardant resin composition of the present invention may further contain a curing accelerator (E) in order to further improve properties such as adhesion, chemical resistance and heat resistance.
The (E) curing accelerator is not particularly limited as long as it can accelerate the curing reaction between the above-mentioned urethane-modified polyimide resin, epoxy resin and non-halogen flame retardant.
Specific examples of the epoxy resin curing agent (E) include, for example, imidazole derivatives, guanamine derivatives such as acetoguanamine and benzoguanamine, diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, Polyamines such as sulfone, dicyandiamide, urea, urea derivatives, melamine and polybasic hydrazide, organic acid salts and / or epoxy adducts thereof, amine complexes of boron trifluoride, ethyldiamino-S-triazine, 2 , Triazine derivatives such as 4-diamino-S-triazine and 2,4-diamino-6-xylyl-S-triazine, amines such as trimethylamine, triethanolamine, N, Benzyldimethylamine, pyridine, N-methylmorpholine, hexa (N-methyl) melamine, 2,4,6-tris (dimethylaminophenol), tetramethylguanidine, DBU (1,8-diazabicyclo [ , 0] -7-undecene) and DBN (1,5-diazabicyclo [4,3,0] -5-nonene), organic acid salts thereof and / or tetraphenyl Organic phosphines such as boronate, polyvinylphenol, polyvinylphenol bromide, tributylphosphine, triphenylphosphine and tris-2-cyanoethylphosphine, tri-n-butyl (2,5- Quaternary phosphonium salts such as tetraphenylphosphonium bromide, hexadecyltributylphosphonium chloride and tetraphenylphosphonium tetraphenylboronate; quaternary ammonium salts such as benzyltrimethylammonium chloride and phenyltributylammonium chloride; Diphenyl iodonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, 2,4,6-triphenylthiopyrylium hexafluorophosphate, Irgacure 261 (manufactured by Chiba Chemical Co., (Manufactured by Specialty Chemicals Co., Ltd.) and Optoma SP-170 (manufactured by ADEKA Corporation), styrene-maleic anhydride resin, equimolar reaction products of phenyl isocyanate and dimethylamine, Cyanate, and the like can be mentioned equimolar reaction product of an organic polyisocyanate with dimethyl amine, such as isophorone diisocyanate. These may be used singly or in combination of two or more kinds. Preferred are curing accelerators having latent curing properties, and include organic acid salts of DBU and DBN and / or tetraphenylboronate, and photo cationic polymerization catalysts.
The amount of the (E) curing accelerator to be used is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the (A) urethane-modified polyimide resin. When the amount is more than 20 parts by mass, the storage stability of the urethane-modified polyimide flame retardant resin composition and the heat resistance of the coating film are likely to be deteriorated. When the amount is less than 0.1 part by mass, the curability may be deteriorated.
The urethane-modified polyimide flame retardant resin composition of the present invention may contain (F) an ion catcher in order to further improve the insulation reliability under high temperature and high humidity.
As the ionic catcher (F), impurity ions and hydrolyzable chlorine present in ppm order in a cured coating film of a urethane-modified polyimide flame retardant resin composition are captured to reduce insulation failure of a flexible printed wiring board and improve its insulation reliability (Zeolite, zirconium phosphate, bismuth hydrate, bismuth hydrate, antimony oxide, magnesium aluminum hydrotalcite, hydroxyapatite, etc.) can be mentioned. These may be used singly or in combination of two or more kinds. It is preferable to use an inorganic ion exchanger in consideration of heat resistance, chemical resistance and the like. Since the ions to be trapped are both cationic and anionic, it is preferable to use an ion exchange material of both ion exchange type or a combination of a cation exchange type inorganic ion exchange material and an anion exchange type inorganic ion exchange material .
As the inorganic ion exchanger of both ion exchange type, antimony-bismuth type or zirconium-bismuth type can be used. And non-antimony-bismuth-based ones. As the cation exchange type inorganic ion exchanger, zirconium-based ones or antimony-based ones can be used. As the anion exchange type inorganic ion exchanger, a bismuth type or a magnesium-aluminum type can be used. Of the anion exchange type inorganic ion exchangers, those containing no heavy metals such as antimony and bismuth are more preferable because of their high ion exchange capacity and high environmental compatibility.
The blending amount of the ion exchanger is preferably in the range of 1.0 to 15.0% by weight based on the whole amount of the composition. When the blending amount of the inorganic ion exchanger is less than 1.0% by weight, the ion trapping rate becomes 50% or less, and there is a possibility that a sufficient effect by mixing the inorganic ion exchanger can not be obtained. When the compounding amount of the inorganic ion exchanger is about 15.0 wt%, the ion trapping rate becomes 80% or more. However, even when the compounding amount of the inorganic ion exchanger is further increased, the ion trapping rate is not increased, At the same time, there is a concern that heat resistance, chemical resistance, low warpage, and bending property may occur. When the cation exchange type and the anion exchange type are used together, the ratio of the cation exchange type to the anion exchange type ion trapping agent is preferably set in the range of 20:80 to 60:40 by weight.
The urethane-modified polyimide flame retardant resin composition of the present invention may further contain additives such as a coloring pigment, a dye, a polymerization inhibitor, a thickener, a defoaming agent, a leveling agent, a coupling agent / adhesion promoter, a heat stabilizer, an antioxidant, Known additives such as an antioxidant, an antioxidant, an antioxidant, an absorbent, a light stabilizer, a light shielding agent, a light extinguishing agent, a metal deactivator, an antistatic agent, an antioxidant, a plasticizer and a compatibilizer.
The urethane-modified polyimide flame retardant resin composition of the present invention is obtained by blending the components (A), (B), (C), (D), (E), and (F) And mixing them uniformly 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. A plurality of kneading by three main rolls is preferable.
The urethane-modified polyimide flame retardant resin composition of the present invention preferably has a viscosity in a B-type viscometer to be described later at 25 캜 in the range of 50 dPa s to 2000 dPa 하고, more preferably in the range of 100 dPa 쨌 s to 800 dPa 의 Range is more preferable. If the viscosity is less than 50 dPa · s, the outflow of the paste after printing becomes large and the film thickness tends to be thinned. When the viscosity exceeds 2000 Pa · s, the transferability of the paste to the base material is lowered at the time of printing, so that a faint portion is generated, and voids and pinholes in the printed film tend to increase.
The degree of irregularity (thixotropy) is also important, and in the urethane-modified polyimide flame retardant resin composition of the present invention, the aspect ratio is preferably 1.1 or more, more preferably 1.8 or more in the measuring method described below. The upper limit is preferably 10.0 or less, more preferably 9.0 or less. When the aspect ratio is less than 1.1, the outflow of the paste after printing becomes large and the film thickness tends to be thinned. If it is more than 10.0, the paste tends not to flow. The degree of irregularity can be adjusted by the addition amount of the component (C) as the urethral enhancer.
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, it is preferable to use a method such as a screen printing method, a spray coating method, a roll coating method, an electrostatic coating method, a curtain coat method, a dip coating method and the like by a method such as a printed wiring board, a flexible printed wiring board (FPC) , The coating film is preliminarily dried at 60 to 120 占 폚 and then dried at 120 to 200 占 폚. The drying may be performed 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 a semiconductor device, an overcoat ink for various electronic parts, a solder resist ink, an interlayer insulating film, a paint, a coating agent, Can be used.
Example
In order to show the effect of the present invention, the following examples are given, but the present invention is not limited thereto. On the other hand, the characteristic values described in the examples were measured by the following methods.
<Logarithmic viscosity>
The urethane-modified polyimide resin was dissolved in N-methyl-2-pyrrolidone so that the polymer concentration was 0.5 g / dl, and the solution viscosity was measured at 30 캜 by a Ubbeledesh type viscometer. The logarithmic viscosity was defined by the following equation.
(Logarithmic viscosity) = (ln? Rel) / C
ln: natural algebra
ηrel: The viscosity ratio (-) of the solution to the pure solvent by the measurement of the solvent dropping time
C: concentration of solution (g / dl)
≪ 350 DEG C weight reduction rate >
About 15 mg each of a flame retardant and a urethane-modified polyimide resin were respectively taken and kept in an air atmosphere (20 ml / min) at a temperature raising rate of 10 캜 / minute from room temperature to 100 캜 and held for 30 minutes, The weight reduction rate at 150 ° C to 350 ° C was obtained by heating the aluminum pan at 10 ° C / min up to 600 ° C.
Used device; Shimazu Seisakusho Co., Ltd. DTTC-60 simultaneous measurement of heat and thermogravimetry
<Continuous printing property>
The resin precipitation and viscosity increase from the paste when the urethane-modified polyimide flame retardant resin composition was screen-printed for 30 minutes continuously by the method described in Example 19 were evaluated based on the following criteria.
(Judgment) ○: Faint part occurrence, resin precipitation, ink viscosity rise Not confirmed
X: Faint part occurrence, precipitation of resin, increase in ink viscosity
<Urbanism>
Using Brookfield BH type rotational viscometer, the following procedure was used. A paste containing a urethane-modified polyimide flame-retardant resin composition was placed in a light-shielding bottle (100 ml) having a wide mouth and the liquid temperature was adjusted to 25 ° C ± 0.5 ° C using a constant temperature water bath. Subsequently, a glass rod was used to stir the mixture for 12 to 15 seconds for 40 times, and then a predetermined rotor was provided, and the scale was read for 5 minutes and then rotated at 20 rpm for 3 minutes. The viscosity was calculated by multiplying this scale by the coefficient of the conversion table. Likewise, the viscosity measured at 25 ° C and 2 rpm was also calculated, and from these values, the following variables were calculated according to the following equations.
Viscosity = viscosity (2 rpm) / viscosity (20 rpm)
<Port life of ink>
After the urethane-modified polyimide flame retardant resin composition was allowed to stand at 25 占 폚 for one month in a sealed state, the presence or absence of precipitation or gelation of the resin was evaluated based on the following criteria.
(Judgment) ○: No abnormality
?: With precipitate
×: solidification
<Content of phosphorus>
Measured by wet decomposition molybdenum blue colorimetry method. An appropriate amount of a sample obtained by curing the urethane-modified polyimide flame retardant resin composition at 165 占 폚 for 2 hours was taken in an Erlenmeyer flask according to the phosphorus concentration in the sample, and 3 ml of sulfuric acid, 0.5 ml of perchloric acid and 3.5 ml of nitric acid were added, Lt; / RTI > When the solution became transparent, the solution was further heated to give white smoke, and the solution was cooled to room temperature. The decomposed solution was transferred to a 50 ml volumetric flask, and 5 ml of 2% ammonium molybdate solution and 2 ml of a 0.2% ml, and the mixture was mixed with pure water, and the contents were well mixed. The flask was placed in a boiling water bath for 10 minutes. After heating and coloring, it was water-cooled to room temperature and deaerated with ultrasonic waves. The solution was collected in 10 mm of the absorbing cell and the absorbance was measured with a spectrophotometer (wavelength: 830 nm) did. The phosphorus content was obtained from the calibration curve prepared earlier.
<Flammability>
A polyimide film having a thickness of 25 占 퐉 was used as a substrate, and the resulting laminated film having a thickness of 15 占 퐉 was evaluated for flame retardancy according to the UL94 standard. The flame retardancy is UL standard, preferably VTM-2 or higher, and VTM-0 is the most preferable.
<Bleed out>
The laminated film obtained by using the polyimide film as a substrate was cut into 10 cm x 10 cm. 25 ° C and 65% humidity for 24 hours, sealed in a polyethylene bag and allowed to stand in a constant temperature bath at 25 ° C for 1 week to 1 month, and visually confirmed by touching the surface with a hand, . ≪ / RTI >
(Judgment) ◎: Bleed water after 3 months, no sense of tag
○: Bleed water even after one month, no sense of tag
Δ: slightly bleed water after 1 month, there is a feeling of tackiness
X: remarkable bleed water after 1 week, there is a sense of tag
≪ Low warpability &
The laminated film obtained by using the polyimide film as a substrate was cut into 10 cm x 10 cm. The sample whose humidity was adjusted at 25 ° C and 65% for 24 hours was placed on a horizontal glass plate in a downward convex state, and the height average of four corners was evaluated based on the following judgment criteria.
(Judgment) O: less than 2 mm in height
?: Less than 10 mm in height
×: Height 10 mm or more
<Flexibility>
The laminated film obtained using the polyimide film as a base material was evaluated in accordance with JIS-K5400. The diameter of the shaft was 2 mm, and the presence of cracks was confirmed.
<Line insulation resistance>
A comb pattern having a line length of 50 占 퐉 was formed on a CCL (trade name: viroflex) manufactured by Toyobo Co., Ltd., washed with 1% sulfuric acid, and then washed and dried. Paste was printed on the circuit, and the obtained solder resist layer was heated and cured at 160 DEG C for 120 minutes. And the line-to-line insulation resistance at the time when the direct current voltage was 100 V was measured. 10 or more is preferable.
≪ Soldering heat resistance &
The laminated film obtained by using the copper foil as a base was immersed in a soldering bath at 260 DEG C for 30 seconds in accordance with JIS-C6481, and the presence or absence of external appearance such as peeling or swelling was evaluated based on the following judgment criteria.
(Judgment) ○: Appearance No abnormality
△: Appearance is slightly abnormal
X: Abnormal front view
≪ Adhesion >
The laminated film obtained by using the copper foil as the base material was subjected to a peeling test with a cellophane tape (registered trademark) in accordance with JIS-K5600 by making a checkerboard scale of 1 mm of 1 mm, and the peeling state of the checkerboard scale was observed. A laminated film obtained by using a polyimide film as a substrate was similarly subjected to a peeling test, and the peeling state of the checkerboard scale was evaluated based on the following criteria.
(Judgment) ○: No peeling at 100/100
?: 70 to 99/100
×: 0 to 70/100
<Pencil hardness>
The laminated film obtained by using the copper foil as the base material was evaluated in accordance with JIS-K5400. The pencil hardness is preferably 2H or more, and more preferably 3H or more.
≪ My PCT property &
The laminated film obtained using a polyimide film as a substrate was allowed to stand under an atmosphere of 121 占 폚 and 2 atm for 48 hours to evaluate whether or not appearance abnormality such as peeling or dissolution was judged based on the following judgment criteria.
(Judgment) ○: Appearance No abnormality
△: Appearance is slightly abnormal
X: Abnormal front view
<Chemical resistance>
The laminated film obtained by using a polyimide film as a substrate was immersed in each solvent of 10% HCl, 10% NaOH, isopropanol, and methyl ethyl ketone for 10 seconds to determine the presence or absence of appearance abnormality such as peeling or dissolution based on the following judgment criteria I appreciated.
(Judgment)?: No abnormality in appearance even when immersed in all solvents
&Amp; cir &: Appearance slightly abnormal when immersed in at least one solvent
≪ / RTI > < RTI ID = 0.0 > x: < / RTI >
Manufacturing example One
166.0 parts by mass of trimellitic acid anhydride (purity: 99.9%, trimellitic acid content: 0.1%), polypropylene oxide adduct of bisphenol A (manufactured by Sanyo Chemical Industries, Ltd.) , 86.3 parts by mass of a polypropylene glycol (trade name: Newpol BP-5P, molecular weight 533, manufactured by Kasukogyo Co., Ltd.), 108 parts by mass of a polypropylene glycol (trade name: SANNIX PPG2000 manufactured by Sanyo Chemical Industries, Ltd., molecular weight: 2000), hexamethylene diisocyanate , 125.1 parts by mass of diphenylmethane-4,4'-diisocyanate, 493.5 parts by mass of? -Butyrolactone and 1.5 parts by mass of 1,8-diazabicyclo [5.4.0] -7- The mixture was heated in an atmosphere of nitrogen from 30 ° C to 160 ° C for 5 hours, diluted with 246.8 parts of diglyme and cooled to room temperature to obtain a thick brown urethane-modified polyimide resin having a nonvolatile content of 40% by mass Resin solution A-1 Obtained.
Manufacturing example 2 to 5
The raw materials described in Table 1 were polymerized in the same manner as in Example 1 and then cooled to room temperature to obtain thick brown urethane-modified polyimide resin solutions A-2 to A-5 having a nonvolatile content of 40 mass%.
Manufacturing example 6
86.3 parts by mass of trimellitic anhydride (purity: 99.9%, trimellitic acid content: 0.1%) and 184.4 parts by mass of ethylene glycol bishydrohydrotrimellitate were added to a four liter two liter separable flask equipped with a stirrer, a cooling tube, , 342.4 parts by mass of polycaprolactone diol (PLACCEL220, trade name, manufactured by Daicel Chemical Industries, Ltd.), 250.3 parts by mass of diphenylmethane-4,4'-diisocyanate, 784.3 parts by mass of? -Butyrolactone, And 1.5 parts by mass of 1,8-diazabicyclo [5.4.0] -7-undecene as a catalyst, the reaction mixture was heated from 30 DEG C to 120 DEG C in a nitrogen stream and reacted for 5 hours. Then, 392.1 parts by mass of diglyme And diluted. The solution was cooled to room temperature to obtain a thick brown urethane-modified polyimide resin solution A-6 having a non-volatile content of 40 mass%.
Manufacturing example 7 to 8
The raw materials described in Table 1 were polymerized in the same manner as in Example 6, and then cooled to room temperature to obtain thick brown urethane-modified polyimide resin solutions A-7 to A-8 having a nonvolatile content of 40 mass%.
Example One
7.2 parts by mass of jER152 (trade name of phenol novolak type epoxy resin manufactured by Japan Epoxy Resin Co., Ltd.) was added to 48.8 parts by mass of the resin component of the urethane-modified polyimide resin solution A-1 obtained in Production Example 1, Diluted. 3.2 parts by mass of AEROSIL # 300 (hydrophilic silica fine particles manufactured by Nippon Aerosil Co., Ltd.) as a filler, 19.1 parts by mass of SANKO-BCA (manufactured by Sanko Co., Ltd.) as a non-halogen flame retardant, , 0.5 part by mass of Ucat 5002 (manufactured by SANA PRO Co., Ltd.) as a curing accelerator, 1.5 parts by mass of PLOREN AC-326F (manufactured by Kayeishakagaku Co., Ltd.) as a defoaming agent, 0.5 parts by weight of BYK-358 (manufactured by Beck Chemicals) as a leveling agent, and then kneaded roughly first, followed by repeating kneading three times using a high-speed triple-roll, uniformly dispersing the filler, A paste containing a urethane-modified polyimide flame retardant resin composition was obtained. The viscosity was adjusted with diglyme to give a solution viscosity of 130 poise and a degree of variability of 2.5. Subsequently, a paste containing 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 占 퐉 so as to have a thickness of 15 占 퐉 after drying. Dried at 80 ° C for 10 minutes, and then heated at 150 ° C for 120 minutes in an air atmosphere to obtain a laminated film. The obtained copper foil of the laminated film was removed by etching with a ferric chloride solution to obtain a film. Similarly, a polyimide film having a thickness of 25 占 (Apical NPI manufactured by Kaneka) was applied and dried and heated to obtain a laminated film. The composition and the laminated film thus obtained are shown in Table 2 in detail.
Example 2-18
Using the raw materials listed 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. The composition and the laminated film thus obtained are shown in Table 2 and Table 3 in detail.
Example 19
On the copper circuit (L / S = 50/50) obtained by the subtractive method from a CCL (trade name: viroflex, copper foil 18 μm, base 20 μm) manufactured by Toyobo Co., Ltd., the urethane-modified polyimide Based resin composition was printed with a predetermined pattern at a printing speed of 5 cm / sec in an SUS mesh plate (150 mesh, manufactured by Murakami Corporation, emulsion thickness 30 占 퐉) at 80 占 폚 for 6 minutes, C for 60 minutes to obtain a flexible printed wiring board having a coverlay (coating film) containing a urethane-modified polyimide resin composition. The thickness of the coating was 15 mu m. The resulting flexible printed wiring board was excellent in flexibility and flexibility.
Comparative Example 1 to 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 described in Table 4 were used. Table 4 shows the obtained composition and the laminated film in detail and the evaluation results.
As is apparent from Tables 2 to 4, the cured coating films formed from the urethane-modified polyimide flame retardant resin compositions of the present invention of Examples 1 to 18 are curable at low temperature, free from warpage, and have flexibility, flame retardancy, heat resistance, , Electrical properties, and adhesion to substrates. On the other hand, in Comparative Examples 1 to 3 and 5 to 7, the characteristics and blending amount of the flame retardant were out of the range of the present invention, and in Comparative Example 4, the urethane-modified polyimide resin deviated from the range of the present invention. The cured coating film formed from the modified polyimide resin flame retardant resin composition was inferior in each characteristic.
The urethane-modified polyimide flame retardant resin composition of the present invention is useful as an overcoat ink for various electronic parts such as a flexible printed wiring board, a solder resist ink, an interlayer insulating film, a paint, a coating agent, It can be used in a wide range of devices.
Claims (13)
(B) an epoxy resin having two or more epoxy groups per molecule,
(C) an inorganic or organic filler, and
(D) Non-halogen flame retardant
Modified polyimide flame retardant resin composition,
(D) a non-halogen flame retardant contains two components: a component (D-1) having a weight loss rate at 350 ° C of 50% or more and 90% or less and a component (D-2) Wherein the component (D-1) comprises 10-benzyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- Modified polyimide flame retardant resin composition.
(In formula [III], R 1 is an alkylene group of C 1 ~C 20, R 2 and R 3 may be the same or different from each other good, it represents an alkyl group of hydrogen or C 1 ~C 4, m is an integer of 1 or more And n is an integer of 1 or more.
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| JPJP-P-2009-263541 | 2009-11-19 | ||
| JP2009263541 | 2009-11-19 | ||
| PCT/JP2010/070282 WO2011062137A1 (en) | 2009-11-19 | 2010-11-15 | Urethane modified polyimide based flame retardant resin composition |
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| JP (1) | JP5768372B2 (en) |
| KR (1) | KR101738193B1 (en) |
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| JP5659806B2 (en) * | 2011-01-14 | 2015-01-28 | 三菱レイヨン株式会社 | Epoxy resin composition, prepreg and fiber reinforced composite material |
| WO2012176806A1 (en) * | 2011-06-21 | 2012-12-27 | 三菱瓦斯化学株式会社 | Flameproofed alicyclic polyimide resin composition and thin-walled molded body of same |
| WO2013021895A1 (en) * | 2011-08-05 | 2013-02-14 | 積水化学工業株式会社 | Conductive material and connection structure |
| JP5958529B2 (en) | 2012-02-24 | 2016-08-02 | 日立化成株式会社 | Semiconductor device and manufacturing method thereof |
| US9803111B2 (en) * | 2012-02-24 | 2017-10-31 | Hitachi Chemical Company, Ltd. | Adhesive for semiconductor, fluxing agent, manufacturing method for semiconductor device, and semiconductor device |
| US8552095B1 (en) * | 2012-09-25 | 2013-10-08 | Sabic Innovations Plastics IP B.V. | Flame-retardant polymer composition and article |
| JP2014101501A (en) * | 2012-10-26 | 2014-06-05 | Nitto Denko Corp | Polyamide-imide resin composition |
| JP2014101502A (en) * | 2012-10-26 | 2014-06-05 | Nitto Denko Corp | Polyamide-imide resin composition |
| JP2014101500A (en) * | 2012-10-26 | 2014-06-05 | Nitto Denko Corp | Polyamide-imide resin composition |
| CN103897395A (en) * | 2014-03-28 | 2014-07-02 | 哈尔滨工程大学 | Preparation method of hydrotalcite and polyimide composite foam material |
| JP2016121201A (en) * | 2014-12-24 | 2016-07-07 | 東洋紡株式会社 | Urethane-modified polymide resin solution |
| CN107849210B (en) * | 2015-08-11 | 2020-09-11 | 东洋纺株式会社 | Urethane-modified polyimide resin solution |
| JP6070911B1 (en) * | 2015-08-11 | 2017-02-01 | 東洋紡株式会社 | Urethane-modified polyimide resin solution |
| CN109071955B (en) * | 2016-04-22 | 2021-10-15 | 日保丽公司 | Curable composition, cured film using same, and overcoat film |
| WO2018235756A1 (en) * | 2017-06-22 | 2018-12-27 | 大京化学株式会社 | Flame-retardant processing of polyester-based synthetic fiber structure |
| UY37974A (en) * | 2017-11-20 | 2019-06-28 | Lanxess Deutschland Gmbh | ALUMINUM GLASSES CONTAINING DICARBONIC DIESTERS |
| CN111417683B (en) * | 2018-03-20 | 2023-07-25 | 积水化学工业株式会社 | Curable resin composition, adhesive film, coverlay film, and flexible copper-clad laminate |
| JP6844570B2 (en) * | 2018-03-29 | 2021-03-17 | 信越化学工業株式会社 | Silicone rubber-silicone modified polyimide resin laminate |
| JP7135919B2 (en) * | 2019-02-13 | 2022-09-13 | 味の素株式会社 | resin composition |
| CN113754696A (en) * | 2020-06-01 | 2021-12-07 | 华中师范大学 | Phosphaphenanthrene derivative, preparation and flame-retardant application |
| CN111621260B (en) * | 2020-06-18 | 2022-01-25 | 株洲时代新材料科技股份有限公司 | Polyamide acid coating adhesive and preparation method thereof |
| KR102200259B1 (en) * | 2020-07-24 | 2021-01-11 | 와이제이종합건설 주식회사 | Method for waterproof of concrete structures using polyurea to enhance nonflammabiltiy and heat-barrier property |
| CN112227965B (en) * | 2020-12-09 | 2021-04-06 | 东营市金亿来石油机械有限公司 | High-temperature-resistant coated sucker rod |
| CN117603529B (en) * | 2024-01-18 | 2024-03-22 | 汕头市嘉祥塑料制品厂有限公司 | Antibacterial milk powder cover and preparation method thereof |
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| CN102639640B (en) | 2014-06-11 |
| TWI462953B (en) | 2014-12-01 |
| KR20120105438A (en) | 2012-09-25 |
| CN102639640A (en) | 2012-08-15 |
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| JPWO2011062137A1 (en) | 2013-04-04 |
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