TW201125897A - Urethane-modified polyimide based flame retardant resin composition - Google Patents

Abstract

The present invention provides a urethane-modified polyimide based flame retardant resin composition which is soluble in non-nitrogenous solvent and stable in varnish, and has excellent low temperature/hardenability, low warpage, flexibility, printability and flame retardancy, as well as excellent heat resistance, chemical resistance, electronic properties, operation ability and economy. The urethane-modified polyimide based flame retardant resin composition of the present invention is characterized by comprising the following components, (A) an urethane-modified polyimide based resin having an urethane bond generated from required components of (a) trivalent and/or quadrivalent polycarboxylic acid derivate with anhydride group, (b) diol compound and (c) derivate of aliphatic polyamine residue and/or derivate of aromatic polyamine residue; (B) an epoxy resin having 2 or more of epoxy group per 1 molecule; (C) an inorganic or organic filler and (D) a non-halogen based flame retardant, in which (D) non-halogen based flame retardant contains component (D-1) with a weight loss ratio of 50% to 90% and component (D-2) with a weight loss ratio of 0% to 20% in air environment under 350 DEG C as required components.

Description

201125897 VI. Description of the Invention: [Technical Field] The present invention relates to a urethane-modified polyimine-based resin composition which has excellent heat resistance and flexibility and is suitable for a printing machine, a dispenser or A coating method such as a spin coater. The urethane-modified polyimine-based resin composition of the present invention is suitable 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. [Prior Art] The flexible printed wiring board is widely used for electronic device parts that require flexibility or small space, such as a device mounting substrate for a display device such as a liquid crystal display 'plasma display, or a mobile phone, a digital camera, a portable game machine, or the like. Inter-substrate relay cable, operation switch unit substrate, and the like. However, the solder resist layer, the surface protective layer, the interlayer insulating layer, or the adhesive layer of the constituent elements of the flexible printed wiring board are often coated and printed in a solution form. Therefore, a solvent-soluble closed-loop type polycondensate is proposed as a material. A composition of an imide resin. However, in the case of a solvent for varnishing a polyimine-based resin, a high-boiling nitrogen-based polar solvent such as N-methyl-2-pyrrolidone is used, and 20 (TC or higher) is required for drying/hardening. In the hardening step of time, there is a problem of thermal degradation of the electronic component. Further, after the varnish is applied to the substrate, if it is left for a long period of time, ink and coating film due to moisture absorption of the high-boiling nitrogen-based solvent may occur. Whitening and pores, the setting of working conditions has a complicated problem of 201125897. Furthermore, since the polyimide resin is generally high in modulus and hard, when laminated on a substrate such as a film or a copper foil, it is elastic. There is a problem in the subsequent steps due to the difference in the modulus, and there is a problem in the subsequent steps. Moreover, the cured film system lacks flexibility and has poor bendability. On the other hand, there are many cases where flame retardancy is required in electronic parts. A halogen-containing compound represented by decanoic acid or a heavy metal compound such as antimony trioxide which can be used as a flame retardant restricts the rise of the movement. Although the polyilylimide-based resin has a relatively high flame retardancy, it is relatively high in flame retardancy. Yuyao When the flame retardancy is high, the non-halogen flame retardant such as a pity compound, a nitrogen compound, or a hydrated metal compound (aluminum hydroxide or magnesium hydroxide) is used. However, compared with the halogen system, it is difficult. The flammable agent is not sufficiently flammable, and the phosphorus-based flame retardant represented by the phosphate ester has a problem of poor hydrolysis resistance or heat resistance. The resin is flexible and low-elastic as soluble in a non-nitrogen-based solvent. For the polyimine-based resin which is molded to impart low warpage and flexibility, for example, a polysoda-modified polyaniline-based resin has been proposed (see Patent Documents 1 and 2). A poly-polyimide-based resin, in order to low-elastic modulus, 'uses a high-priced diamine having a dimethyloxane bond as a starting material', which has a problem of poor economy. In the case of the improvement of the amount of the polymerization, there is a problem that the adhesion, the solvent resistance, and the chemical resistance are lowered. In order to improve these disadvantages, for example, a composition using a polycarbonate modified polyimine resin is proposed (see Patent Document 3 to 5). These polycarbonate modified polyimine systems The lipid-based improvement comes from the disadvantages of polyaza 201125897, and it has good printing suitability, but in the composition obtained from the resin, in order to reduce warpage, it is necessary to increase the polycarbonate modification of the polyimide resin. The amount of heat is lowered, and the varnish stability is low, and the varnish is solidified for several days during storage. In addition, in order to obtain low warpage, when low elastic modulus components are introduced, the flame retardancy is lowered. There are many cases. The coating film obtained from the composition proposed herein also does not have sufficient flame retardancy. As a soluble non-nitrogen solvent, the resin is flexible and has low elastic modulus and has low warpage. A composition of a polyimine-based resin composition that meets the flame retardancy standard of the UL standard, for example, a composition in which a hydrated metal compound is added to a polycarbonate-modified polyimide-based resin (see Patent) Documents 6 to 8). These polycarbonate-modified polyimine-based resin compositions have low warpage, bendability, and flame retardancy, but when low elastic modulus components are introduced to reduce warpage, Heat resistant There are many cases of reduced sexual and flame retardancy. The composition proposed herein is for a tape-receiving package (TAB, COF) using a relatively thick polyimide film substrate for use in a thin polyimide film of less than 1 mil (25 μm). In the use of a flexible printed wiring board (F PC) for a substrate, sufficient flame retardancy cannot be obtained. Further, when a thin polyimide film substrate is used, low warpage is also insufficient. On the other hand, Patent Document 9 proposes a polyimine-based resin which is selected from the group consisting of a polyether, a polyester, a polyacrylonitrile-butadiene copolymer, a polycarbonate diol, and a dimer acid. At least one component is used as a component of the copolymerization of 201125897. The monomer having an isophorone residue is an essential component, and Patent Document 10 proposes to contain a polyether as a copolymer component, and contains trimellitic acid and cyclohexane. A polyimide-based resin in which a carboxylic acid is used as an acid component, and a composition formed therefrom. Although it is expected that these polyimine-based resins are excellent in solubility in a non-nitrogen-based solvent, they are not suitable for low-warpage properties, solder heat resistance, or printing suitability as a flexible printed wiring board. Further, in the non-nitrogen-based reaction solvent, the varnish stability is low, and the resin is easily precipitated over time, and the low-boiling point having high solubility is further reprecipitated from the viewpoint of use. The solvent is completely replaced and the economy is poor. Further, since the compositions proposed by these are mainly alicyclic components, sufficient flame retardancy cannot be obtained. Patent Document 11 proposes a composition using a polyamidene-based resin containing a polyalkylene oxide adduct of bisphenol A. The polyimide composition is excellent in heat resistance, but it is insoluble in a non-nitrogen solvent, and it is difficult to say that it has low warpage and flexibility, and flame retardancy is not obtained. Patent Document 12 proposes a polyfluorinated imide system using a hydrated metal compound, a phosphorus compound or a nitrogen compound which is a non-halogen-based flame retardant as a pigment in a polyoxymethane-modified polyimide-based tree. Composition. This polyimine-based resin composition is used as a flexible printed wiring board, and it is expected to satisfy the UL standard flame retardancy standard in addition to characteristics such as solder heat resistance and printing suitability. In the same manner as in the case of the patent documents 7 to 8, the compound of the water-alloy 201125897, which has a large amount of flame retardant effect, has a high modulus of elasticity and has a problem of low warpage and reduced bendability. In order to improve the above disadvantages, Patent Document 13 proposes the use of a polysiloxane-diamine-modified resin composition of a specific monomer. The polyamidene resin composition does not contain an inorganic flame retardant, and it is expected that the low warpage property is not impaired, but the use of a high-priced monomer is economically inferior, and the adhesion due to the siloxane compound is also caused. problem. Patent Document 14 proposes a polyurethane resin composition using a phosphonic acid dialkyl ester metal salt as a non-halogen-based flame retardant and a polyamidene-based resin composition. The polyurethane resin composition is used as a flexible printed wiring board, and it is expected to meet the UL standard flame retardancy standard in addition to the characteristics such as solder heat resistance and printing suitability, but it is a flame retardant system. Since it is blended in a large amount as a material that is incompatible with the resin, the flexibility and low warpage are not necessarily sufficient to improve these disadvantages. For example, a non-halogen flame retardant proposed in a polyimide resin is blended. There is a composition of phosphazene dissolved in a polyimide resin (see Patent Documents 15 to 17). These polyimine-based resin compositions are used as flexible printed wiring boards, and are expected to satisfy flame retardancy and low warpage, in addition to characteristics such as solder heat resistance and printing suitability, but phosphazene-based flame retardants The single system does not exhibit a high degree of flame retardancy, and must be added in a large amount, and there is a problem that the flame retardant is oozing out. As described above, in the prior art, a polyilylimine-based resin composition is not obtained, which is suitable for simultaneously satisfying (1) non-nitrogen-based solvent solution 201125897, (3) low warpage property, solder resist layer , surface retention and varnish stability, (2) low temperature drying / hardening (4) bendability, (5) printing suitability, (6) flame retardant sheath, interlayer insulating layer or adhesive layer. CITATION LIST PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT JP-A-2007-96915 Patent Document No. JP-A-2008- 1986 [Patent Document 9: JP-A-2003-289594] Patent Document 1 特: JP-A-9- 3 2 8 5 5 0 Patent Document 11: Special Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The invention is intended to solve the problems of the prior art described above, and the object thereof is to solve the problems of the prior art described above. Providing a urethane-modified polyimine-based flame retardant resin composition, (1) Non-nitrogen solvent solubility and varnish stability, (2) Low temperature drying/curing property, (3) Low warpage, (4) Flexibility, (5) Printing suitability, (6) Flame retardancy It is excellent in suppressing the bleeding of the flame retardant, is excellent in heat resistance, chemical resistance, electrical properties, workability, and economy, and provides an electronic component obtained by using the composition. MEANS FOR SOLVING THE PROBLEMS The inventors of the present invention have made intensive efforts to achieve the above object, and have finally completed the present invention. That is, the present invention is composed of the following configurations (1) to (12). (1) A urethane-modified polyimine-based flame retardant resin composition comprising a urethane-modified polyimide-based flame retardant resin composition having the following composition, (A) (a) a trivalent and/or tetravalent polycarboxylic acid derivative having an acid anhydride group, (b) a diol compound, and (c) an aliphatic polyamine residue derivative and/or an aromatic polyamine residue derivative as A urethane-modified polyimine resin having a urethane bond formed by a necessary component, (B) an epoxy resin having two or more epoxy groups per molecule, (C) Inorganic or organic tanning materials, and (D) non-halogen flame retardants characterized by = -10- 201125897 (D) Non-halogen flame retardants containing a weight reduction rate of 350 ° C in an air environment It is 50% or more 90°/. The following component (D-1) and two components of component 0 (D-2) of 0% or more and 20% or less are essential components. (2) The urethane-modified polyimide-based flame retardant resin composition according to (1), wherein the weight reduction ratio of the (D-1) component is 60% or more and 85% or less '(D) - 2) The weight reduction rate of the component is 0% or more and 15% or less. (3) The urethane-modified polyimide-based flame retardant resin composition according to (1) or (2), wherein (D) the non-halogen flame retardant contains (A) urethane A phosphorus-based flame retardant in which an ester-modified polyimine-based resin is compatible. The urethane-modified polyimine-based flame retardant resin composition according to any one of (1) to (3) wherein the (D-1) component contains 9,10-dihydro- The 9-oxa-10-phenanthrene-10-oxide derivative '(D-2) component contains a phenoxyphosphazene compound. (5) The urethane-modified polyimine-based flame retardant resin composition according to any one of (1) to (3) wherein (D) the non-halogen-based flame retardant contains a sputum type Non-halogen flame retardant. The urethane-modified polyimine-based flame retardant resin composition according to any one of (1) to (3), wherein the (D-1) component contains 9,10 _Dihydro-9-oxa-10-phenanthrene-10-oxide derivative, (D_2) component containing a phosphonic acid metal salt of the following general formula [I], represented by the following formula [II] a reaction product of a bisphosphonate metal salt, a reaction product of a cyanamide derivative having at least one amine group with a phosphoric acid, or a cyanamide derivative having at least one amine group and a cyanuric acid, -11 - 201125897

0 0 〇^—R3_{1—Q

[1] In the formula [I] and the formula [II], R1 and R2 may be the same or different from each other, and are linear or branched C1 to C1() alkyl and/or cycloalkyl and/or aryl groups and / or aralkyl 'R1 and: R2 may be bonded to each other to form a ring together with adjacent phosphorus atoms; R3 is a linear or branched Cl~ClQ alkyl group, C6~ClQ cycloalkyl group, c6~C1G Aryl group, C6~c1Q alkyl extended aryl or CpC. aryl extended base ' Μ from Mg, Ca, Al, Sb, Sn, Ge, Ti, Ζη, Fe ' Zr ' Ce, Bi, Sr, Mn At least one selected cation of the group formed by Li, Na, K or a protonated nitrogen base, m is an integer of 1 to 4, n is an integer of 1 to 4, and X is an integer of 1 to 4). (7) The urethane-modified polyimide-based flame retardant resin composition according to any one of (1) to (6), wherein the (D·2) component is contained at 25. A phenoxyphosphazene compound which is a liquid under the conditions of (1, 1 3 · 251 Ρ Ρ &amp; </ RTI> (8) A urethane-modified polyimine of any one of (1) to (7) A flame retardant resin composition, wherein (b) the diol compound contains (b-fluorene) polyoxyalkylene glycol and/or (b-2) a polyalkylene oxide of bisphenol represented by the following formula [III] Additives. -12- 201125897

(In the formula [III], Ri is Ci to c2. The alkyl group, and 112 and R3 may be different from each other', and hydrogen or C, -c4 alkyl, m is an integer of 1 or more, and the above integer). (9) A urethane-modified polyfluorene flame retardant resin composition according to any one of (1) to (8), which further contains (E) a hardening accelerator. (10) A urethane-modified polyflammable resin composition according to any one of (1) to (9), which further contains (F) an ion scavenger. (11) The urethane-modified polyflammable resin composition according to any one of (1) to (10), wherein (A) the urethane-modified polyfluorene resin is made from an ether It is the reverse of at least one organic solvent selected from the group consisting of a solvent, an ester solvent, a ketone solvent, and an aromatic solvent. (12) A urethane-modified functional group flame retardant resin composition according to any one of (1) to (1), which has a rocking degree of 1.1 or more (13) - an electron A part, which is an electronic part having a solder resist layer, a surface-protected interlayer insulating layer or an adhesive layer, characterized by a urethane-modified polyfluorene of any one of the aforementioned layers (1) to (1 2) The imide-based composition is hardened and hardened. Advantageous Effects of Invention According to the present invention, it is possible to provide a urethane-modified polyg-based flame retardant resin composition which is (1) non-nitrogen solvent solubility and accommodating property, and (2) low temperature drying/curing property (3) low warpage, (4) bending 1 or i-based 1 amine imine imine amine hydrocarbon to obtain imine. The layer, the resin imide paint I' (5) •13- 201125897 _ out, stupid, and this acid-renewed polyamidene-based flame retardant resin composition as a film forming material ^ for flexibility Various electronic parts such as printed wiring boards are suitable for printing on the cover, (6) excellent in flame retardancy, and can suppress the flame retardant, and heat resistance, chemical resistance, electrical properties, workability, and economy are difficult to satisfy at the same time. . Therefore, the amine-based adhesive of the present invention can be applied to a wide range of fields of electronic equipment as a coating, a solder resist, an interlayer insulating film, and the like. [Embodiment] Mode for Carrying Out the Invention The present invention will be described in detail below. The urethane-modified polyimine-based flame retardant tree J 曰 composition of the present invention is characterized by comprising: (A) derived from (a) a trivalent and/or tetravalent polycarboxylic acid having an acid anhydride group a diol compound and a urethane complex having a urethane complex and a derivative of an aliphatic polyamine residue and/or an aromatic polystyrene residue as an essential component Polyimide-based resin, (B) epoxy resin having two or more epoxy groups per molecule, (C) inorganic or organic tantalum, and (D) non-halogen flame retardant, characterized It is: (D) Non-halogen-based flame retardant contains 35 (Γ (: weight reduction rate: 50% or more and 90% or less of the component (d -1) and 〇% or more and 2% or less) The component (D-2) has two components as essential components. -14 - 201125897 (a) a trivalent and/or tetravalent polydecanoic acid derivative having an acid anhydride group, which is usually composed of an isocyanate component or The amine component reacts to form a polyimide-based resin. The polycarboxylic acid derivative may be any of an aromatic, aliphatic or alicyclic group. (a) The amount of copolymerization of the component is relative to In terms of 100% by mole of all polyamine residue derivatives of the object, it is more preferably 30 mol% or more and 90 mol% or less, more preferably 35 mol% or more and 85 mol% in terms of molar ratio. When the amount of the copolymerization is less than the above range, the flame retardancy, the mechanical properties, and the heat resistance are not obtained. When the amount is more than the above range, since the component (b) described below cannot be copolymerized in a sufficient amount, the low warpage property is obtained. Or the solubility in a non-nitrogen-based solvent may be reduced. Examples of the aromatic polycarboxylic acid derivative include trimellitic anhydride, pyromellitic dianhydride, ethylene glycol double-dehydrated trimellitate, and propylene glycol. Dehydrated trimellitic acid ester, I,4-butanediol double-dehydrated trimellitic acid ester, hexanediol double-dehydrated trimellitic acid ester, polyethylene glycol double-dehydrated trimellitic acid ester, polypropylene glycol double dehydration Alkanediol double-dehydrated trimellitic acid vinegar such as trimellitic acid ester, hydroquinone double-dehydrated trimellitic acid ester, hydroquinone dioxirane adduct dehydrated trimellitic acid ester, 4,4'- Exophenyl bis-dehydrated trimellitate, 3,3,,4,4,-diphenyl ketone tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid Anhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridyl D-tetracarboxylic dianhydride, 3 , 4,9,10-decanetetracarboxylic dianhydride, 3,3',4,4,-diphenylphosphonium tetracarboxylic dianhydride, cross-linked triphenyl-3,3',4,4'- Tetracarboxylic dianhydride, 4,4,-oxydiphthalic dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis(2,3- or 3,4- Dicarboxyl 201125897 phenyl)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[4-(2,3- or 3,4-dicarboxyl) Phenoxy)phenyl]propane dianhydride '1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldioxanhydride dianhydride, 5-(2, 5-dioxotetrahydro-3-phenyl)-3-methylcyclohexene-1,2-diphthalic anhydride, 2,2-bis(4-hydroxyphenyl)propane dibenzoate _ 3,3',4,4'-tetracarboxylic dianhydride, 2,3,3,4-diphenyltetracarboxylic dianhydride, and the like. Further, 'as an aliphatic or alicyclic polycarboxylic acid derivative, for example, butane-1,2,3,4-tetracarboxylic dianhydride, pentane-12,4,5-tetracarboxylic dianhydride , cyclobutane tetracarboxylic dianhydride, hexahydrobenzene tetracarboxylic dianhydride, cyclohexanyl- ene- 2,3,5,6-tetracarboxylic dianhydride, 3-ethylcyclohex-1-ene -3-(1,2),5,6-tetracarboxylic dianhydride, 1-methyl-3-ethylcyclohexane-3_(1,2),5,6-tetracarboxylic dianhydride, 1 _Methyl_3-ethylcyclohex-1-en-3-(1,2),5,6-tetracarboxylic dianhydride, 1-ethylcyclohexane-1-(1,2),3 , 4-tetracarboxylic dianhydride, propylcyclohexane-^^"., decarboxylation of tetracarboxylic dianhydride, 1,3-dipropylcyclohexane·丨-(2,3), 3-(2 , 3)-tetracarboxylic dianhydride, dicyclohexyl-3,4,3',4,-tetracarboxylic dianhydride, bicyclo[2,2,1]heptane-2,3,5,6-tetra Carboxylic dianhydride, 1-propylcyclohexane-1-(2,3), 3,4-tetracarboxylic dianhydride, iota, 3-dipropylcyclohexane-1-(2,3), 3-(2,3)-tetracarboxylic dianhydride, dicyclohexyl-3,4,3',4'-tetracarboxylic dianhydride, bicyclo[m]heptane_2,3,5,6_four Carboxylic dianhydride, bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylate Acid dianhydride, hexahydrotrimellitic anhydride, etc. The trivalent or tetravalent polycarboxylic acid derivative may be used singly or in combination of two or more. When considering heat resistance, transparency, adhesion, solubility, and the like, the polycarboxylic acid derivative is -16-201125897 Preferred are pyromellitic dianhydride, trimellitic anhydride, ethyl alcohol double-dehydrated trimellitate, 3,3', 4,4,-diphenyl ketone tetracarboxylic dianhydride, 3,3', 4, 4'-biphenyltetracarboxylic dianhydride, 2,2-bis[4·(2,3_ or 3,4-di residue phenoxy)phenyl]propane dianhydride, more preferably trimellitic anhydride, B The diol bis-dehydrated trimellitate. The (b) diol compound which constitutes the bismuth component is a flexible component which imparts flexibility, low warpage, solubility, and the like in the polyimide resin. In the copolymerization, the elastic modulus of the resin can be lowered by copolymerizing the component (b), and the solubility (varnish) stability in the non-nitrogen solvent used as the polymerization solvent is increased. The amount of polymerization 'is preferably 1 〇 mol% or more and 70% by mole or less, more preferably 1 5 %, based on 100% by mole of all polyamine residue derivatives of the reaction target. When the amount of copolymerization is more than the above range, flame retardancy, mechanical properties, and heat resistance are not obtained, and when it is less than the above range, low warpage or in a non-nitrogen solvent The solubility of the component (b) is preferably a molecular weight of 500 or more and 3,000 or less, more preferably 800 or more and 2,000 or less. When the molecular weight is less than the above range, heat resistance, flexibility, and low warpage property are insufficient. When the molecular weight is more than the above range, the modification reaction does not proceed and the solubility is lowered. Examples of the diol compound include polyalkylene glycol, polyoxyalkylene glycol, polyalkylene oxide adduct of bisphenol, aliphatic/aromatic polyester diol, and aliphatic/aromatic polycarbonate. Glycols, polycaprolactone diols, -17- 201125897 polybutadiene polyols, hydrogenated polybutadiene polyols, hydrogenated diene polyols, polydimethyl siloxane diols, poly Methylphenyl decyl alcohol and the like. It is preferably a polyoxyalkylene glycol, a polyalkylene oxide-added aliphatic/aromatic polyester diol of bisphenol, or an aliphatic/aromatic polycarbonate, more preferably a polyoxyalkylene glycol (described later) (( Bl) a component), a polyalkylene oxide adduct of a bisphenol represented by the formula (component (b-2)). The other compound may, for example, be a bisphenol such as bisphenol A or bisphenol F, but the urethane bond may be dissociated when heated. As an aliphatic/aromatic polyester diol, it is obtained by dehydration condensation of a dicarboxylic alcohol or a reaction of a lower alcohol ester of a dicarboxylic acid with a diol, or a diol as an initiator. The ring-opener is obtained by a condensation reaction of a diol with a hydroxyalkanoic acid. Specific examples of the dicarboxylic acid component include succinic acid, glutaric acid, pimelic acid 'octanedioic acid, sebacic acid, sebacic acid, dodecane branic acid, tetradecanedioic acid, and eicosane. Diacid, 2-methylsuccinic acid adipic acid, 3-methyladipate, 3-methylpentanedicarboxylic acid, 2-alkanedicarboxylic acid, 3,8-dimethyldecane dicarboxylic acid Acid, 3,7-dimethyl decanoic acid, dimer acid 'hydrogenated dimer acid, or alkenyl succinic acid such as octenyl succinic acid, sesuccinic acid, octadecyl succinic acid, fumaric acid, Aliphatic dicarboxylic acids such as itaconic acid and their esters form aromatics such as terephthalic acid, isophthalic acid, phthalic acid, anthracene, and 4-naphthalene 2,6-naphthalene dicarboxylic acid. Dicarboxylic acid and their ester formations, 1,4-cyclohexanedicarboxylic acid, tetrahydrophthalic acid, hexahydro-isomeric isopentyl compound, and glycol ester diol [ΠΙ] In acid and diester exchange polymerization of acid, adipic acid, 2-methylmethyloctanedicarboxydienyl, maleic, formic acid, sexually derived phthalic acid-18- 201125897 acid, 1,2-ring Alicyclic dicarboxylic acid such as hexene dicarboxylic acid and the like 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- Pentyl glycol, 3-methyl-1,5-pentanediol, 1,6-hexanediol ' 1,7-heptanediol, trimethylpentanediol, 2-ethyl-1,3-hexyl Glycol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 2,4-diethyl-1,5-pentanediol, 1, 1〇-nonanediol, 2,2-diethyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, diethylene glycol, triethylene glycol, eicosane Aliphatic diol such as diol or neopentyl glycol hydroxytrimethyl acetate, alicyclic diol such as 1,4-cyclohexanedimethanol or tricyclodecane dimethanol, bisphenol A or double An aromatic ring-containing diol such as an ethylene oxide adduct of phenol S or a propylene oxide adduct, or a reduced product of a dimer acid. Specific examples of the hydroxyalkanoic acid component include 3-hydroxybutanoic acid, 4-hydroxypentanoic acid, and 5-hydroxyhexane acid. Examples of the lactone include γ-valerolactone, δ-valerolactone, ε-caprolactone, α-methyl-β-propiolactone, β-methyl-β-propiolactone, and 3-n-positive Propyl-δ-valerolactone, 6,6-dimethyl-δ-valerolactone, glycolide, lactide, and the like. The aliphatic/aromatic polycarbonate diol is obtained by transesterification of a diol with a carbonate compound, ring-opening polymerization of a cyclic carbonate compound, or diol and chloroformate or light. The reaction of gas is obtained. The aliphatic/aromatic polycarbonate diol is preferably an alkylene group having 50 mol% or more of an alkylene chain or more, and an alkylene group having a carbon number of 6 or more, and more preferably -19-201125897. More than % is an alkylene group having a carbon number of 6 or more. More preferably, 50 mol% or more of the alkylene chain contained in the preferred system is a polycarbonate diol having an alkylene group having a carbon number of 8 or more. The aliphatic/aromatic polycarbonate diol preferably has a plurality of kinds in the skeleton from the viewpoint of crystallization inhibition or solubility of the obtained urethane-modified polyimine-based resin. Alkyl extended polycarbonate diol. Also, a polycarbonate diol having an alkyl group having a side chain is preferred. Examples of the (b-fluorene) polyoxyalkylene glycol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and poly(neopentyl glycol/butanediol). The amount of the (b-Ι) component copolymerized is preferably such that the mass of the polyurethane formed from the (b-Ι) component and the polyamine residue derivative becomes a urethane-modified polyazide. The amine resin is 5% by mass or more and 70% by mass or less, more preferably 10% by mass or more and 40% by mass or less. When the amount of copolymerization is less than the above range, the modulus of elasticity is not sufficiently lowered, warpage occurs during lamination, and solubility in a non-nitrogen solvent is lowered, so that it is at 5 ° C to 30 ° C at 1 ° Within a month, there is a flaw in the precipitation of the resin. This tendency is particularly remarkable when γ-butyrolactone, glyme or cyclohexanone which is preferably used in the present invention is used as a solvent. On the other hand, when it exceeds the above range, flame retardancy, mechanical properties, and heat resistance are lowered. (b-2) The polyalkylene oxide adduct of bisphenol is a non-nitrogen solvent-soluble and flexible property to the modified polyimine-based resin, as shown by the following formula [m]. Examples of the polyalkylene oxide include polyethylene oxide, polypropylene oxide, and poly-20-201125897 tetrahydrofuran. It is preferred to use a number average molecular weight of 200 or more and 2 〇 0 〇 or less. Specifically, a polyethylene oxide adduct of bisphenol A, a polypropylene oxide adduct of bisphenol A, and the like can be given.

(In the formula [III], 1^ is C^Czoalkylene, and R2 and R3 may be the same or different from each other, and represent hydrogen or a CpQ alkyl group, and m is an integer of 1 or more and an integer of η is 1 or more). The amount of the copolymerization of the component (b.2) is preferably such that the mass of the polyurethane formed from the component (b-2) and the derivative of the polyamine residue becomes a urethane-modified polyimine. The resin is 10% by mass or more and 75% by mass or less, more preferably 20% by mass or more and 70% by mass or less. When the amount of copolymerization is less than the above range, the solubility in a non-nitrogen solvent is lowered, so that it is 5. (:~3 0. (:: There is a resin precipitated within one month, and this tends to be γ-butyrolactone, glyme or cyclohexanone which is preferably used in the present invention. When the solvent is used in the above range, the flame retardancy, mechanical properties, and heat resistance are lowered. As the (c) aliphatic polyamine residue derivative, fat is used. The polyisocyanate and the aliphatic polyamine. Examples of the aliphatic polyisocyanate include hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and isocyanuric acid diisocyanate. The hexamethylene diisocyanate. The aliphatic polyamine may, for example, be hexamethylenediamine, 2,2,4-trimethylhexamethylenediamine or lysine diamine, preferably six. Methylene diamine. -21 - 201125897 As the (c) aromatic polyamine residue derivative constituting the component (A), an aromatic polyisocyanate or an aromatic polyamine is used. Examples of the aromatic polyisocyanate include aromatic polyisocyanate. 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, Diphenyl Ether-4,4'-Diisocyanate, Diphenylketone-4,4'-Diisocyanate, Diphenyl Mill-4,4-Diisocyanate, Toluene-2,4- Diisocyanate, toluene-2,6-diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, naphthalene-2,6-diisocyanate, 4,4'-[2,2 bis (4- Phenoxyphenyl)propane]diisocyanate, 3,3' or 2,2'-dimethylbiphenyl-4,4'-diisocyanate, 3,3'- or 2,2'-diethyl Biphenyl-4,4'-diisocyanate, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, 3,3'-diethoxybiphenyl-4,4'-diisocyanate, etc. When considering heat resistance, adhesion, solubility, cost, etc., the aromatic polyisocyanate is preferably diphenylmethane- 4,4'-diisocyanate, toluene-2,4-diisocyanate, m-xylylene diisocyanate, 3,3' or 2,2'-dimethylbiphenyl-4,4'-diisocyanate, More preferred is diphenylmethane-4,4'-diisocyanate or toluene-2,4-diisocyanate. Examples of the aromatic polyamine include diphenylmethane-2,4'-di-22-201125897 amine, 3,2'- or 3,3'- or 4-2'- or 4,3'- Or 5,2'- or 5,3'- or 6,2'- or 6,3,-dimethyldiphenylmethane-2,4,-diamine, 3,2'- or 3,3' -or 4,2,- or 4,3'- or 5,2,- or 5,3,- or 6,2,- or 6,3,-diethyldiphenylmethane-2,4,- Diamine, 3,2'- or 3,3'- or 4,2,- or 4,3'- or 5,2'- or 5,3'- or 6,2'- or 6,3'- Dimethoxydiphenylmethane-2,4'-diamine, diphenylmethane-4,4'-diamine 'diphenylmethane-3,3'.diamine, diphenylmethane-3, 4'-diamine, diphenyl ether-4,4'-diamine, diphenyl ketone-4,4'-diamine, diphenyl sulfonium-4,4'-diamine, toluene-2,4 -diamine, toluene-2,6-diamine 'm-xylylenediamine, p-xylylenediamine, naphthalene-2,6.diamine, 4,4,-[2,2 double (4 -phenoxyphenyl)propane]diamine, 3,3' or 2,2'-dimethylbiphenyl-4,4-diamine, 3,3'- or 2,2'-diethyl Biphenyl-4,4'-diamine, 3,3'-dimethoxybiphenyl-4,4'-diamine, 3,3'-diethoxybiphenyl-4,4, - Amine. The aromatic polyamine is preferably diphenylmethane-4,4'-diamine, toluene 2,4-diamine or m-xylylene, in view of heat resistance, adhesion, solubility, cost, and the like. Diamine, 3,3, or 2,2'-dimethylbiphenyl-4,4'-diamine, more preferably diphenylmethane-4,4'-diamine, toluene-2,4- Diamine. (c) The aliphatic polyamine residue derivative and/or the aromatic polyamine residue derivative may be used alone or in combination of two or more. The ratio of the aliphatic polyamine residue derivative and/or the aromatic polyamine residue derivative is not particularly limited, and the amount of the (b) diol compound can be considered, and the solubility and low warpage can be prevented. Suitable for setting. In the (A) urethane-modified polyimide resin, in addition to the fat-23-201125897 polyamine residue derivative and the aromatic polyamine residue derivative, the low warpage property is not impaired, In the range of heat resistance and flame retardancy, an alicyclic polyamine residue derivative may be more copolymerized as needed. Specifically, examples of the alicyclic polyamine residue derivative include isophorone diisocyanate, 4,4,-dicyclohexylmethane diisocyanate, and trans cyclohexane-1,4-diisocyanate. An alicyclic polyisocyanate such as hydrogenated m-xylylene diisocyanate or norbornene diisocyanate. When considering heat resistance, adhesion, solubility, cost, and the like, it is preferably isophorone diisocyanate or 4,4'·dicyclohexylylene diisocyanate. Further, a trifunctional or higher polyamine residue derivative may be used, and in order to avoid a change in the day, it may be stabilized by a blocking agent. When the trifunctional or higher polyamine residue derivative is a trifunctional or higher polyisocyanate, the terminal blocking agent may be an alcohol, a phenol, a hydrazine or the like, but is not particularly limited. These trifunctional or higher polyisocyanates may be used alone or in combination of two or more. When the isocyanate is excessively polymerized, the isocyanate group at the end of the resin may be sealed with a terminal blocking agent such as an alcohol, an internal amide or a hydrazine after completion of the polymerization. Further, in the component (A), an aliphatic, alicyclic or aromatic diacid may be further copolymerized as needed within a range not impairing the performance of the object. Examples of the aliphatic dicarboxylic acid include succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, sebacic acid, decanedioic acid, dodecanedioic acid, and eicosanedioic acid. , 2-methyl succinic acid, 2-methyladipate, 3-methyladipate, 3-methylpentanedicarboxylic acid, 2-methyloctanedicarboxylic acid, 3,8-dimethyl- 24- 201125897 Based on dicarboxylic acid, 3,7-dimethylindole dicarboxylic acid, 9,12-dimethylicosanedioic acid, fumaric acid, maleic acid 'dimer acid, hydrogenated dimer acid Examples of the alicyclic dicarboxylic acid include, for example, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, and 4,4. , -dicyclohexyl dicarboxylic acid, etc., and examples of the aromatic dicarboxylic acid include isophthalic acid, terephthalic acid, phthalic acid, naphthalene dicarboxylic acid, oxydibenzoic acid, and stilbene dicarboxylic acid. Wait. These dicarboxylic acids may be used alone or in combination of two or more. In view of heat resistance, adhesion, solubility, cost, and the like, the dicarboxylic acid is preferably sebacic acid, 1,4-cyclohexanedicarboxylic acid, dimer acid, or isophthalic acid. (A) A urethane-modified polyimine-based resin is a method in which a polydecanoic acid component having an acid anhydride group and an isocyanate component are produced by decarbonation (isocyanate method) or a group having an acid anhydride group The polycarboxylic acid component is produced by reacting with an amine to form a guanine acid, and a known method such as a method of ring closure (direct method). It is advantageous to industrially modify the urethane to a possible isocyanate system. When a (A) urethane-modified polyimine-based resin is produced by a cyanate ester method, a trivalent and/or tetravalent polycarboxylic acid derivative having an acid anhydride group of the component (a) and a component (b) The compounding amount of the diol compound is preferably such that the number of isocyanato groups / (number of acid anhydride groups + number of carboxylic acid groups + number of hydroxyl groups) = 〇·8〇~1·2〇. If it is outside the above range, it is difficult to increase the molecular weight of the urethane-modified polyimine-based resin. The heat resistance and the bendability are lowered, or the coating film becomes brittle. (聚合) The polymerization reaction of the urethane-modified polyimine-based resin is preferably at least 1 selected from the group consisting of an acid solvent, an ester solvent, a ketone solvent, and an aromatic hydrocarbon solution-25-201125897. In the presence of an organic solvent, for example, in the isocyanate method, the carbon dioxide gas generated by the removal of the free carbon dioxide gas from the reaction system is condensed by heating. Examples of the ether solvent include diethylene glycol dimethyl ether (diglyme), diethylene glycol diethyl ether (ethyl diglyme), and triethylene glycol II. A glyme such as methyl ether (triglyme) or triethylene glycol diethyl ether (ethyl triglyme), 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, two Examples of the ketone solvent include propylene glycol methyl ether acetate, propylene glycol diacetate, methyl benzoate, and ethyl benzoate. Examples thereof include methyl isobutyl ketone 'cyclopentanone, cyclohexanone, and isobutylene. Examples of the aromatic hydrocarbon solvent include phorone and the like, and examples thereof include toluene, xylene, and Solvesso. These may be used alone or in combination of two or more. In order to produce a varnish of the (A) urethane-modified polyimine-based resin, it is preferred to use a urethane-modified product which can be directly dissolved as a varnish after polymerization. A solvent of a polyimide resin. At this time, there is no complicated operation such as solvent replacement, and it can be manufactured inexpensively. The boiling point of the solvent is preferably 14 (TC or more and 230 ° C or less. When the temperature is lower than 140 ° C 'except for the volatilization of the solvent in the polymerization reaction, and for example, when performing screen printing, the solvent volatilizes rapidly and is clogged. The possibility of screen printing. If -26-201125897 exceeds 230 ° C, it is difficult to impart low-temperature drying / hardenability. Preferably, γ_τ lactone, cyclohexanone, diglyme, triglyme, Ethyl carbitol acetate 'is a low-temperature drying/curing property because of its high volatility', and it has excellent varnish stability, and can be efficiently reacted in a homogeneous system. The amount of solvent used is preferably generated. The urethane-modified polyimine-based resin is 0.8 to 5.0 times (mass ratio), more preferably 0.9 times to 2.0 times. When the amount used is less than the above range, the viscosity at the time of synthesis is too high due to When it is not possible to stir, the synthesis tends to be difficult, and if it exceeds the above range, the reaction rate tends to decrease. The method for producing a (fluorene) urethane-modified polyimine-based resin is exemplified as isocyanate. In the case of law, for example, using (1) (a) ingredients once, (b) component and (c) component, a batch reaction to obtain a urethane-modified polyimine resin, and (2) component (a) and/or component (b) After the amount of the component (c) is reacted to synthesize a urethane-modified oligomer having an isocyanate group at the terminal, the component (a) and/or the component (b) are added to cause a reaction to obtain a urethane modification. a method of using a polyimine-based resin, (3) reacting an excess amount of the component (a) and/or the component (b) with the component (c) to synthesize a carboxylic acid group and/or an acid anhydride group at the terminal and/or After the hydroxyl group-modified urethane-modified oligomer, the component (c) is added to obtain a urethane-modified polyimine-based resin by a reaction. When the isocyanate method is used, the reaction temperature is preferably It is 60 to 200 ° C, more preferably 100 to 18 0 ° C. When the reaction temperature is lower than the above range, the reaction time is -27-201125897, and if it exceeds the above range, monomer components may occur in the reaction. Decomposition. In addition, a three-dimensional reaction occurs to cause gelation. The reaction temperature can also be carried out in multiple stages. The reaction time can be in accordance with the batch. The scale, the reaction conditions used, and especially the reaction concentration are suitably selected. When the isocyanate method is used, in order to promote the reaction, triethylamine, lutidine, picoline, undecene, and triamethylene may be used. Amine (1,4-diazabicyclo[2.2.2]octane), oxime 81; amines such as 1,8-diazabicyclo[5.4.0]-7-undecene, sodium methoxide An alkali metal such as ethanol, sodium, potassium butoxide, potassium fluoride or sodium fluoride, an alkaline earth metal compound or a catalyst such as a metal such as titanium, cobalt, tin, zinc or aluminum or a semimetal compound. The logarithmic viscosity of the (A) urethane-modified polyimine-based resin is preferably 0.1 dl/g or more and 2.0 dl/g or less, more preferably 2 dl/g or more and 1.8 dl/g or less. When the logarithmic viscosity is less than the above range, the heat resistance is lowered or the coating film is brittle. Moreover, the paste has strong adhesiveness and the release property is deteriorated. On the other hand, when it is larger than the above range, it is hard to be dissolved in a solvent, and it is easily insolubilized during polymerization. Further, the viscosity of the varnish becomes high, the handling becomes difficult, or the adhesion to the substrate is lowered. Furthermore, it is impossible to increase the non-volatile concentration of the paste, and it becomes difficult to form a thick film. A urethane-modified polyimine-based resin having a logarithmic viscosity in this range can be obtained by appropriately adjusting polymerization conditions such as a monomer ratio and a polymerization temperature. The glass transition temperature of the (A) urethane-modified polyimine-based resin is preferably 20 ° C or higher, more preferably 6 〇 ° C or higher. When the temperature is lower than the above temperature, the heat resistance is insufficient, and the resin has a tendency to adhere. The upper limit is not particularly limited. From the viewpoint of solvent solubility, it is preferably 3 Å or less. The urethane-modified polyimine-based resin having a glass transition temperature in this range can be obtained by appropriately adjusting the polymerization conditions such as the monomer ratio by -28 to 201125897. The urethane-modified polyimine-based flame retardant resin composition of the present invention is cured by a (A) urethane-modified polyimine-based resin to improve the film after film formation. For the purpose of the property, (B) an epoxy resin having two or more epoxy groups per molecule. 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, and phenol. Novolak type epoxy resin, o-cresol novolak type epoxy resin, flexible epoxy resin, epoxidized polybutadiene, multifunctional epoxy resin, amine type epoxy resin, epoxy resin containing hetero ring , alicyclic epoxy resin, bisphenol S type epoxy resin, triglycidyl isocyanate, bisxylenol type epoxy resin, bisphenol type epoxy resin, naphthalene type epoxy resin, two rings A pentadiene type epoxy resin, a phosphorus-containing epoxy resin, etc. may be used individually or in combination of 2 or more types. Among these epoxy resins, bisphenol A type epoxy resin, bisphenol F type epoxy resin, benzoquinone novolak type epoxy resin having two more epoxy groups in one molecule, ortho-cresol A novolak type epoxy resin or an amine type epoxy resin is a non-halogen type, and is compatible with the urethane-modified polyimine resin of the component (A), solvent resistance, chemical resistance, and resistance. The point of improvement in wetness is preferred. (B) The amount of the epoxy resin used is preferably from 1 to 50 parts by mass based on 100 parts by mass of the urethane-modified polyimine-based resin. More preferably -29 - 201125897 is 2 to 40 The mass fraction is particularly preferably 3 to 30 parts by mass. When the amount of the epoxy resin is less than the above range, solder heat resistance, solvent resistance, chemical resistance, and moisture resistance tend to be lowered. When the amount exceeds the above range, low warpage, mechanical properties, heat resistance, and varnish are observed. The stability and the compatibility with the urethane-modified polyimine-based resin are lowered. (B) The total amount of the component (B) added to the component (A) is modified with a urethane. When the total nonvolatile content of the quinone imine resin composition is 100% by mass, it is preferably 40 to 90% by mass, and more preferably 45 to 80% by mass. In the epoxy resin (B), as the diluent, an epoxy compound having only one epoxy group in the molecule may be further contained. As a method of adding the epoxy resin (B), the epoxy resin added in advance may be added in the same solvent as the solvent contained in the urethane-modified polyimine-based resin, and may be added. It is directly added to the urethane-modified polyimide resin. Further, in the present invention, in addition to the epoxy resin, a conventionally used curing system such as a polyisocyanate, a cyanate ester, an oxetane or an acrylate may be used. The urethane-modified polyimine-based flame retardant resin composition of the present invention contains (C) an inorganic or organic tantalum in order to improve workability at the time of coating and printing and film properties after film formation. The (C) inorganic or organic coating material is not particularly limited as long as it is dispersed in the above-described aminoester-modified polyimine-based resin and can be imparted to a shaker. As such an inorganic material, for example, vermiculite 30-201125897 (Si〇2), alumina (Al2〇3), titanium dioxide (Ti〇2), oxidized giant (Ta205), chromium oxide (Zr02), nitrogen can be used. Huayu (S"N4), 钦 钡 (Bao.

Ti02), barium carbonate (BaC03), lead titanate (Pb0. Ti〇2), lead zirconate titanate (PZT), lead zirconate titanate (PLZT), gallium oxide (Ga2 03 ), spinel ( MgO · Al2〇3), mullite (3Al2〇3 · 2Si02), cordierite (2MgO. 2A1203. 5Si〇2), talc (3Mg〇. 4Sl〇2. H2〇), aluminum titanate (Ti02- Al203), cerium oxide containing cerium oxide (Y2〇3_Zr02), barium strontium silicate (BaO·8Si02), boron nitride (BN), carbonated fishing (CaC03), calcium sulfate (CaS04), zinc oxide (ZnO) And magnesium titanate (Mg〇·Ti〇2) 'barium sulfate (BaS04), organic bentonite, carbon (C), etc., etc. These may be used individually or in combination of 2 or more types. From the viewpoint of the color tone, transparency, mechanical properties, and shake imparting of the obtained paste, fine particles of vermiculite are preferred. The inorganic material preferably has a particle diameter of 50 μm or less and a maximum particle diameter of ΙΟΟμηη or less, more preferably an average particle diameter of 20 μm or less, and most preferably an average particle diameter of 10 μm or less. The average particle diameter (median diameter) referred to herein is obtained by using a laser diffraction/scattering type particle size distribution measuring apparatus based on the volume. When the average particle diameter exceeds 50 μm, it is difficult to obtain a composition having sufficient shakeability, and the flexibility of the obtained coating film is lowered. When the maximum particle diameter exceeds 100 μm, the appearance and adhesion of the coating film tend to be insufficient. As the organic material, as long as it is dispersed in the above-described urethane-modified polyimide-based resin solution, it can be imparted to the shaker, and examples thereof include a polyimide resin particle and a benzopyrene. Amine resin particles, epoxy resin particles, and the like. -31- 201125897 (C) The amount of the inorganic or organic pigment used is preferably 0.5 to 25 mass when the total amount of the urethane-modified polyimine resin composition is 100% by mass. %, more preferably 2 to 15% by mass, particularly preferably 3 to 12% by mass. When the amount of the inorganic or organic pigment is less than 0.5% by mass, the printing property tends to be lowered. When the amount is more than 25 mass%, the mechanical properties such as the flexibility of the coating film and the transparency tend to be lowered. The urethane-modified polyimide-based flame retardant resin composition of the present invention contains (D) a non-halogen-based flame retardant in order to have flame retardancy. (D) The non-halogen-based flame retardant is characterized in that it contains a component (d-1) having a weight reduction rate of 550 % or less and an inert weight ratio of 5% to 90% in an air atmosphere, and 0% or more and 20% or less. The two components of the component (D-2) are essential components. The weight reduction rate of the component (D-!) is preferably 60% or more and 85% or less, and the weight reduction ratio of the component (D-2) is preferably 〇% or more and 15% or less. Specifically, the weight reduction rate refers to heating by a TGA (thermogravimetric analysis) at a temperature increase rate of 1 〇 ° C /min to a temperature of 1 ° C at a temperature of 1 ° C / min, and after 30 minutes, 1 〇 . (: / / The rate of temperature rise on the aluminum plate is heated to 600 ° C, the weight reduction rate at 150 ° C to 350 ° C. So by the blending weight loss rate of the flame retardant and A flame retardant having a small weight reduction rate is used as a non-halogen flame retardant, and a high flame retardancy can be achieved with a very small amount of addition. This reason is presumed to be due to the modification of a polyamidene resin by a urethane. The flame retardant agent having a high weight reduction rate is volatilized to produce a non-combustible environment, and at the same time, carbon is formed on the surface to suppress the occurrence of decomposition gas of the resin, and the anti-flammable agent having a low weight reduction rate and the anti-resin of the resin - 201125897 It is possible to combine it with the formation of a surface adiabatic structure to obtain efficient flame retardancy. Moreover, as a result, it is possible to suppress the composition of a flame retardant against a urethane-modified polyimide-based flame retardant resin. The (D) non-halogen-based flame retardant is not particularly limited as long as it affects the heat resistance, flexibility, and bleed (flowing juice) of the coating film formed by the object. A) urethane-modified polyimine resin compatible It is a flame retardant. The low warpage of the coating film can be improved by the action of the urethane-modified polyimine resin as a plasticizer. Further, in the present invention, it is called an amine. The urethane-modified polyimine-based resin-compatible phosphorus-based flame retardant is, for example, a Tg (glass transition temperature) for the urethane-modified polyimine-based resin alone. The behavior of the Tg reducer of the composition can be grasped, for example, by the position of the heat displacement of the DSC (differential scanning calorimetry) or the change of the peak position of the loss tangent in the DMA (Dynamic Viscoelasticity Measurement). As such a (D) non-halogen-based flame retardant, a non-halogen-based flame retardant which is incompatible with a urethane-modified polyimine-based resin and a solvent is preferably used. A dip-type flame retardant can improve the heat resistance of the coating film, in particular, physical heat resistance such as adhesion during heating or bleed out of the flame retardant. As a non-halogen flame retardant for the coating type, the following formula a metal phosphonic acid salt represented by [I], a metal bisphosphonate represented by the following formula [π], having at least 1 The reaction product of an amine-based cyanamide derivative with a phosphoric acid or a cyanamide derivative having at least one amine group and a cyanuric acid to form -33-201125897. Further, as a (D) non-halogen system The flame retardant is preferably a 9,10-dihydro-9-oxa-10-phenanthrene-10-oxide derivative from the viewpoints of flame retardancy, hydrolysis resistance, heat resistance or surface bleed out inhibition. a phenoxyphosphazene compound, a phosphonic acid metal salt represented by the following formula [I], a bisphosphonate metal salt represented by the following formula [π], and a cyanamide derivative having at least one amine group. a reaction product of a reaction product with a phosphoric acid, a cyanamide derivative having at least one amine group, and a cyanuric acid, and more preferably a component (D-1) containing 9,10-dihydro-9-oxa _10_ phenanthrene-10-oxide derivative, the component (D-2) contains a phenoxyphosphazene compound, a phosphonic acid metal salt represented by the following formula [I], and a compound represented by the following formula [II] A reaction product of a di-o-acid metal salt, a cyanamide derivative having at least one amine group, a phosphoric acid &amp; anti-reaction product, a cyanamide derivative having at least one amine group, and a trimeric acid.

[I] 2-

[II] (In the formula [I] and the formula [II], R1 and R2 may be the same or not related to each other, and are linear or branched (^~(:|()alkyl and/or a cycloalkyl group and/or a ##^ square group and/or an aralkyl group, and R1 and R2 may be bonded to each other to form a ring with the adjacent phosphorous name; C i 〇 anthracene R3 is linear or branched. (:!~(:,.alkyl, e-34-201125897, C6~C1() aryl, c6~C1G alkyl extended aryl or c6^ 伸院基' M system by Mg, Ca' Al , Sb, Sn, Ge, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K or a protonated group of at least one selected cation, m is an integer of 1 to 4 of 1 to 4, x is an integer of 1 to 4). As a 9,10-dihydro-9-oxa-10-phenanthrene-10-oxide derivative, a three-light (strand) HCA (9,10-dihydro-9) is exemplified. -oxa-1 (10-oxide), HCA-HQ (1 〇-(2,5-dihydroxyphenyl)-9,10-: hetero-10-phosphaphenanthrene-10-oxide), SANKO -BCA (10-benzyl 3 hydrogen-9-oxa-1〇-phosphaphenanthrene-10) oxide, dihydroxyphenyl)_9,1〇_dihydro-9-oxa-10-phosphaphenanthrene -10-oxide dihydroxy-2-naphthyl)_9,10-dihydro-9-oxa-10-phospha -10_ 2-(9,10-Dihydro-9-oxa "phosphonium phenanthrene-10-oxide-10J bis(2-hydroxyethyl) benzoate, 10-methyl-9,10 - Dihydro-9-oxaphenanthrene-10-oxide, 10-phenyl-9,10-dihydro-9-oxa-1〇-adjusted oxide, ethyl (3-(9,10·dihydrogen) -9-oxa-丨〇-phosphonium 10 -yl)methyl)-2,5-pyrrolidinedione, etc. 9,10-dihydro-9-oxa-10-phenanthrene-10 - Among the oxides, preferably with (A) urethane-modified poly(A), more preferably SANKO-BCA (10-benzyl-9, 1 〇-diaza _9 boxing Phenanthrene-10-oxide). HCA (9,10-dihydro-9-oxa-1〇- 氧化物 oxide), HCA-HQ(10-(2,5-dihydroxyphenyl)_9,1〇 _—白——里10-phosphaphenanthrene-10-oxide), etc., although it has the meaning of e c1() aryl Ti, Zn, nitrogen base, and η-based organisms, I-phosphonium-dihydro-9-oxo 9,10-diyl-6-methyl&gt; 10-(2,5-oxide, I)methylsuccinate:-10-phosphorus hetero- 1 0 -〇-oxide-derivative resin compatible ϊι雑-1 0 - pity: phenanthrene-10-9-oxa-reactivity, -35- 201125897 but due to surface bleed, or Compatibility allophanate-modified polyimide resin, a non-nitrogen-based difference in solubility in a solvent tends to also consider the performance of low warpage and the like appropriately selected. Examples of the phenoxyphosphazene compound include a cyclic phenoxyphosphazene manufactured by Otsuka Chemical Co., Ltd. under the trade names SPE-100, SPB-100L, and a trade name FP- manufactured by Fushimi Pharmaceutical Co., Ltd. Cyclic cyanophenoxyphosphazene of 300 or the like, cyclic hydroxyphenoxyphosphazene such as SPH-100 manufactured by Otsuka Chemical Co., Ltd., and chain phenoxyphosphazene and crosslinked phenoxy The phosphazene or the like, but the chain phosphazene has a substituent at the molecular end, and the phosphorus content is generally lowered as compared with the cyclic phosphazene. Therefore, in the present invention, a cyclic phosphazene is preferred, and a cyclic trimer and/or a tetramer phosphazene is more preferred. When a reactive phosphazene having a functional group reactive with a urethane-modified polyimine-based resin such as SPH-100 is used, it is preferred to enter the hardened system without oozing out of the surface. . Further, when a non-reactive phosphazene which does not have a functional group reactive with a urethane-modified polyimine-based resin is used, crystallinity occurs on the surface over time, and the use condition is excessive. When the free phosphorus is eluted by the influence of hydrolysis or the like, or the insulating property is lowered by the decomposition product, it is preferably a phosphazene which is liquid at 25 ° C and 1013.25 hPa, such as SPB-100L. Examples of the metal phosphonic acid salt include a dialkylphosphonic acid aluminum salt such as dimethylphosphonate, methyl ethylphosphinate or aluminum diethylphosphonate, and an alkylphenyl phenylphosphonate or a diphenyl group. Aromatic phosphonic acid aluminum salt such as aluminum phosphonate, methylphenylphosphonic acid, etc. -36-201125897, a hospital-based arylphosphonic acid aluminum salt, 1-hydroxylH-phosphorus-b-oxide aluminum carboxyl-1 The hydroxy-1H-n-phosphorus-1-oxide aluminum salt or the like may have an aluminum salt which replaces the fluorenic acid, a zinc salt corresponding to the aluminum salt, a calcium salt, a metal or the like. Specific examples of the bisphosphonate include an alkane bis(phosphonic acid) aluminum salt such as a sulfonate aluminum salt, and an ethane-L 2 - bis (methyl phosphine g or the like). An acid) aluminum salt, a zinc salt corresponding to the aluminum salt, and other metal salts, etc., that is, in the general formula [I] and the general formula [II], R1 and R2 are preferably the same or different linear or branched. (^~(:^^ and/or ring/or square group and/or aryl group, especially preferably ethyl or n-propyl, isopropyl, n-butyl, etc. which are the same or different from each other) Tributyl or n-pentyl. R1 and R2 are bonded to form a ring together with an adjacent phosphorus atom, and the above-mentioned phosphorus atom is used as a hetero ring of a hetero atom constituting a ring, and is usually a heterocyclic ring, preferably 5 to 16 The heterocyclic ring having the above-mentioned phosphorus atom may also be a bicyclic ring, and may have a substituent. R3 is a linear or branched C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C Base, C6~Ci 基 基 aryl or c6 〜 alkyl, alkyl is preferably methyl, ethyl, propyl, butyl, butyl, butyl Base, base, tenth Preferably, the cycloalkyl group is a cyclohexylene group or a ring-extension group, and the aryl group is preferably a phenyl or anthracene group, an alkyl aryl group is more salty, a 2-base group is extended, and the other bis-bis(phosphine oxime) Aluminium salt and calcium salt are mutually-based and methyl, phenyl or benzene-based, 20-membered heterocyclic ring, C10 aryl, and extensible n-hexyl dimethyl ketone is a-37-201125897 Ethylphenylene, tert-butylphenylene, methylnaphthyl, ethylnaphthyl or tert-butylnaphthyl 'arylalkylene is preferably phenylmethyl, phenylethyl, benzene a propyl or phenyl butyl group, etc. Μ is made of Mg, Ca, A1 ' Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K or protonated At least one selected cation of the group formed by the nitrogen base is preferably Mg, Ca, Al, Ti, or Zn ions. In the phosphonate or bisphosphonate, a polyvalent salt of such a phosphonic acid may also be contained. And/or a polymer or condensate of a polyvalent salt of a bisphosphonic acid. The average particle diameter of the phosphonate is preferably 10 or less, and particularly preferably 8 μηη or less, more preferably 5 μηι or less. More than 1 When 0 μηι is used, the amount of use for exhibiting sufficient flame retardancy is increased, which is economically disadvantageous, and causes deterioration in insulation reliability, flexibility, adhesion, appearance, etc. As such a preferred phosphonate Specifically, for example, aluminum diethylphosphonate commercially available under the trade names Exolit OP93 5 and OP93 0 manufactured by Clariant Japan Co., Ltd. is used. The average particle diameter (median diameter) of the phosphonates is laser-based. A diffraction/scattering particle size distribution measuring apparatus is obtained based on a volume. A reaction product of a cyanamide derivative having at least one amine group and a phosphoric acid, a cyanamide derivative having at least one amine group, and three In the reaction product of polycyanic acid, a cyanamide derivative having at least one amine group is a unit having an amine group and -N = C=N- or -N = C(-N&lt;)2. The compound may, for example, be an amine group-containing triad (melamine, melam, melem, melamine, guanidine-38-201125897 amine, acetamide, benzoguanamine, etc.) 1, 3, 5 - three-till, 3-amino-1, 2,4-tris-containing amine-containing 1,2,4-tri-trap, etc.), amine-containing a cyclic cyanamide derivative such as a triazole (an amine group-containing n4·triazole such as 2,5-diamino-1,3,4.triazole) or the like, and a hydrazine derivative. An acyclic cyanamide derivative or the like (such as a cyanamide or a carbazyl urea). Preferred cyanamide derivatives are amine-containing hydrazines, 3,5-tritraps, hydrazine or derivatives thereof, especially melamine or melamine condensation products. These may be used alone or in combination of two or more. The phosphoric acid to be reacted with the above cyanamide derivative is an inorganic phosphoric acid such as non-condensed phosphoric acid (orthophosphoric acid, metaphosphoric acid, phosphorous acid (phosphonic acid), hypophosphorous acid (phosphonic acid), or polyphosphoric acid). As the polyphosphoric acid, a condensed phosphoric acid such as pyrophosphoric acid, triphosphoric acid or tetraphosphoric acid is contained. The reaction product of a cyanamine derivative having at least one amine group and a phosphoric acid product, and a reaction product of a cyanamide derivative having at least one amine group and a cyanuric acid is preferably a condensation product containing melamine. a reaction product of a condensation product of a substance, melamine or melamine with phosphoric acid, a reaction product of a condensation product of melamine or melamine with a phosphoric acid condensate, and a condensation product of melamine or melamine with cyanuric acid At least one of the reaction products, more preferably melamine polyphosphate 'melamine polyphosphate, melam polyphosphate, dimelamine pyrophosphate, melamine cyanurate, best It is a melamine polyphosphate having a longer chain length and a melamine cyanurate having a condensation degree of 2 or more, particularly 10 or more and 50 or less. These may be used alone or in combination of two or more. Reaction of a reaction product of a cyanamide derivative having at least one amine group with a phosphoric acid, a cyanamide derivative having at least one amine group, and a cyanuric acid - 39 - 201125897 The average particle size of the product is preferably It is preferably 8μιη or less, and is preferably 8 μηι or less, more preferably 5 μπι or less. If the average particle diameter exceeds ι〇μηη, the amount of use for exhibiting sufficient flame retardancy increases, which is economically disadvantageous. In addition, it is a cause of deterioration in insulation reliability, bay curvature, adhesion, and appearance. As a reaction product of a reaction product of a cyanamide derivative having at least one amine group and a phosphoric acid, and a cyanamide derivative having at least one amine group and a cyanuric acid, as described above, specifically, for example, Product name: MELAPURE 200, MC25, manufactured by Nissan Chemical Industry Co., Ltd., product name PHOSMEL-200 manufactured by Nissan Chemical Industry Co., Ltd., and product name of STAMACE MC-5F, MC manufactured by Sanwa Chemical Co., Ltd. -5S, MC-2010N, etc. The phosphorus content of the urethane-modified polyimine-based flame retardant resin composition of the present invention is preferably from 1.4 to 7% by mass, and the amount of the component (D) is adjusted so as to be in this range. It is preferably 1.6% by mass or more and 4.8 by mass. /. More preferably, it is 2.0% by mass or more and 4 · 0% by mass or less. When the phosphorus content is less than the above range, good flame retardancy cannot be obtained, and if it exceeds the above range, the mechanical properties, heat resistance, adhesion, or insulating properties of the coating film may be lowered. The mixing ratio of the component (D-1) to the component (D-2) is such that the phosphorus content of the urethane-modified polyimide-based flame retardant resin composition and the necessary flame retardancy can be achieved. There is no particular limitation, and a range of (D1) (D-2) = 8 0: 20 to 40: 60 is preferably expressed by mass ratio. When the component (D-1) exceeds 80% by mass of the total of the component (D), the heat resistance of the coating film is likely to be impaired, and if -40 to 201125897 is less than 40% by mass, low warpage property is not obtained, and When phenoxyphosphazene is used in the component (D_2), there is a tendency to bleed out. In the present invention, for the purpose of further improving flame retardancy, triphenyl phosphate, tricresyl phosphate, xylylene phosphate, triethyl phosphate, tolyl diphenyl phosphate, xylyl phosphate may also be used. Diphenyl ester, tolyl bis(2,6-dimethylphenyl) phosphate, 2-ethylhexyl phosphate, dimethyl methyl phosphate, resorcinol bis(diphenol A bis(xylenyl) phosphate Ester, diethyl-anthracene, fluorene-bis(2-hydroxyethyl)aminomethyl phosphate, diethyl phosphate, phenyl phosphate, diphenyl phosphate, organophosphine oxide, phosphoniumamine, red phosphorus Phosphorus-based flame retardant, ammonium polyphosphate, triple well, amber decyl decylamine, tridecylamine, melem, melam, tris(β·cyanoethyl)isocyanate, acetamidine Nitrogen-based flame retardant such as guanidinamine, methylmercapto melamine sulfate, melemamine sulfate, meapyl sulfate, potassium diphenylsulfonium-3-sulfonate, metal salt of aromatic sulfonimide, polyphenylene A metal salt such as an alkali metal salt of ethylene sulfonate is a flame retardant, aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, barium hydroxide, magnesium carbonate, chromium hydroxide, tin oxide Hydrated metal-based flame retardant, vermiculite, alumina, cerium oxide, oxidized chin, oxidized violent, magnesium oxide, chromium oxide, zinc oxide, oxidized pin, oxidized cerium, cerium oxide, oxidized complex, tin oxide, oxidized shop, Nickel oxide, copper oxide, tungsten oxide, zinc borate, zinc metaborate, barium metaborate, zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, zinc stannate, etc., non-metallic flame retardant / flame retardant, polyfluorene A non-halogen flame retardant such as a flame retardant or a flame retardant auxiliary agent such as oxygen powder, which can be used alone or in combination of two or more types. The specific amount used is not a modification of the resulting urethane modification. Polyimide-based -41 - 201125897 The urethane-modified polybenzazole of the present invention is suitably set within the range of physical properties such as electrical properties, heat resistance, and environmental suitability of the resin composition or the cured coating film. The imide-based flame retardant resin composition may further contain (E) a curing accelerator in order to further improve properties such as adhesion, chemical resistance, and heat resistance. (E) The curing accelerator may promote the above amine group Acid ester modified polyimide resin, epoxy tree The curing reaction between the non-halogen-based flame retardant is not particularly limited. Specific examples of the (E) epoxy resin curing agent include an imidazole derivative, acetamylamine, and benzo. Indoleamines such as decylamine, diaminodiphenylmethane, m-phenylenediamine, m-xylylenediamine, diaminodiphenylphosphonium, cyanogenic hydrazine, urea, urea derivatives, melamine, polyfluorene Polyamines, such organic acid salts and/or epoxy adducts, amine complexes of boron trifluoride, ethyldiamine-S-three tillage, 2,4-diamino- Three-till derivatives such as S-tripper, 2,4-diamino-6-dimethylphenyl-S-tripper, trimethylamine, triethanolamine, N,N-dimethyloctylamine, N-benzyl Dimethylamine, pyridine, N-methylmorpholine, hexa(N-methyl)melamine '2,4,6-tris(dimethylaminophenol), tetramethylguanidine, DBU (1, a tertiary amine such as 8-diazabicyclo[5,4,0]-7-undecene) or DBN (1.5.diazabicyclo[4,3,0]-5-nonane), etc. Organic acid salt and / or tetraphenyl borate, polyvinyl phenol, polyvinyl phenol bromide, tributylphosphine, triphenyl phosphine, three -2 -Organic phosphines such as cyanoethyl phosphine, tri-n-butyl (2,5-dihydroxyphenyl) squarate bromide, hexadecyl tributyl sulphate, tetraphenyl platinic tetraphenyl borate, etc. Quaternary scale salts, benzyltrimethyl-42- 201125897 ammonium chloride, quaternary ammonium salts such as phenyltributylammonium chloride, the aforementioned polycarboxylic anhydride, diphenyl iodine tetrafluoroboric acid Ester, triphenylsulfonium hexafluoroantimonate, 2,4,6-triphenylthiopyranium hexafluorophosphate vinegar ' Irgacure 261 (made by Ciba Specialty Chemicals Co., Ltd.), Optomer SP-170 (ADEKA) Organic compound such as photocationic polymerization catalyst, styrene-maleic anhydride resin, phenyl isocyanate and dimethylamine, toluene diisocyanate, isophorone diisocyanate, etc. An equimolar reactant such as a polyisocyanate and dimethylamine. It can be used alone or in combination of two or more types. A hardening accelerator having a latent hardening property, for example, an organic acid salt of D B U, D B N and/or tetraphenyl borate or a photocationic polymerization catalyst or the like is preferable. (E) The amount of the curing accelerator to be used is preferably 0.1 to 20 parts by mass based on 100 parts by mass of the (A) urethane-modified polyimine resin. When it is more than 20 parts by mass, the storage stability of the urethane-modified polyimine-based flame retardant resin composition or the heat resistance of the coating film is likely to be lowered, and if it is less than 0.1 part by mass, the hardenability is obtained. Will decrease. In the urethane-modified polyimide-based flame retardant resin composition of the present invention, (F) an ion scavenger may be contained in order to further improve the insulation reliability under high temperature and high humidity. As the (F) ion scavenger, as long as it is in the hardened coating film of the urethane-modified polyimine-based flame retardant resin composition, impurities or hydrolyzable chlorine present in the ppm level can be trapped to reduce scratching. The insulation of the printed wiring board is not particularly limited, and examples thereof include an organic ion exchange resin and an inorganic ion exchanger (zeolite, -43-201125897 zirconium phosphate, hydrated lanthanum nitrate). , cerium oxide, magnesium aluminum hydrotalcite, hydroxyapatite, etc.). It can be used alone or in combination of two or more types. In consideration of heat resistance, chemical resistance, and the like, an inorganic ion exchanger is preferably used. Further, since the ions to be trapped may have a cation or an anion, it is preferable to use a two-ion exchange type inorganic ion exchanger or a cation exchange type inorganic ion exchanger and an anion exchange type inorganic ion exchanger. As the two ion-exchange type inorganic ion exchanger, a ruthenium-ruthenium or a chrome-ruthenium can be used. Further, a non-锑-铋 person can be cited. As the cation exchange type inorganic ion exchanger, a chromium group or a lanthanide can be used. As the anion exchange type inorganic ion exchanger, a lanthanide or a magnesium-aluminum system can be used. In the anion exchange type inorganic ion exchanger, it is more preferable that it does not contain heavy metals such as ruthenium or osmium, because of high ion exchange energy 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 total amount of the composition. When the amount of the inorganic ion exchanger is less than 1.0% by weight, the ion trapping rate is 50% or less, and sufficient effect due to the combination of the inorganic ion exchangers is not obtained. In addition, when the amount of the inorganic ion exchanger is about 15.0% by weight, the ion trapping rate is 80% or more. However, even if the amount of the inorganic ion exchanger is increased, the ion trapping rate is not increased. There is a problem in cost, and there is a problem in heat resistance, chemical resistance, low warpage, or bendability. Further, when the cation exchange type and the anion exchange type are used, the ratio of the cation exchange type to the anion exchange type ion trapping agent is preferably -•44- 201125897 set at a weight ratio of 20:80 to 60:40. range. In the urethane-modified polyimide-based flame retardant resin composition of the present invention, if necessary, a coloring pigment, a dye, a polymerization inhibitor, a tackifier, an antifoaming agent, a leveling agent, or the like may be added. Coupling agent/adhesion imparting agent, thermal stabilizer, antioxidant, slip agent, ultraviolet absorber, light stabilizer, sunscreen agent, matting agent, metal inerting agent, antistatic agent, anti-aging agent, plasticizer, compatibilization A well-known additive for the agent. The urethane-modified polyimide-based flame retardant resin composition of the present invention can be blended by the above (A), (B), (C), (D), (E), (F) The components and other optional components as needed are uniformly mixed by 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. It is preferably a plurality of kneading by three rolls. The viscosity of the urethane-modified polyimine-based flame retardant resin composition of the present invention measured by a B-type viscometer described later is preferably in the range of 50 ° C to 2,000 dPa·s at 25 ° C. Good for l〇〇dPa. s ~ 8 0 0 d P a . s ~ range. If the viscosity is less than 50 d P a . s, the flow of the paste after printing becomes large, and the film thickness tends to be thin. When the viscosity exceeds 200 Pa·s, the transfer property of the paste to the substrate is lowered during printing, and the pores and pinholes in the printed film tend to increase. The degree of rocking (shake) is also important, and the degree of turbulence of the urethane-modified polyimide-based flame retardant resin composition of the present invention is preferably 1.1 or more, more preferably in the measurement method described later. It is 1.8 or more. The upper limit is preferably 1 0. 〇 below, -45 - 201125897 is preferably 9.0 or less. When the degree of shaking is less than 1.1, the paste after printing becomes large, and the film thickness tends to be thin. If it exceeds 1〇.〇, the tendency of IJ to flow. The degree of shake can be adjusted by the amount of addition of the shake imparting agent I. The urethane-modified polyimide-based flame-retardant tree of the present invention is hardened as follows, for example, as a solder resist, and is obtained as a printed wiring board, a flexible printed wiring board (FPC), and a coating. (COF) or the like 'coating the composition of the present invention by 5 to 8 〇μΠι by a method such as screen printing, spray coating, roll coating, mounting, curtain coating, dip coating, etc. The film is prepared to dry at 120 to 200 ° C at 60 ° to 120 ° C for formal drying. The drying system can be in an air environment. The urethane-modified polyimine resin composition of the present invention thus obtained is used as a film forming material, and can be applied to a surface of a semiconductor for various electronic parts, such as ink, solder resist ink, and interlayer. Used as a coating, a coating agent, an adhesive, or the like. EXAMPLES In order to demonstrate the effects of the present invention, the following examples are given, but are not limited at all. Further, the ones described in the examples were measured by the following methods. &lt;Logarithmic viscosity&gt; The urethane-modified polyimine resin was dissolved in N-pyrrolidone so that the polymer concentration became 55 g/dl, and the flow of the paste was not (C) Adipogenic composition. After the film of the crystalline film is electrostatically coated, or the inert type of flame retardant element or the edge film, the present invention is methyl-2-3 0 ° C by -46- 201125897 by Ubbelodhe type viscosity tube To determine the viscosity of the solution. The logarithmic viscosity is defined by the following formula. (logarithmic viscosity) = (lnr(rel)/C η : natural logarithm η rel : viscosity ratio of solution to pure solvent measured by solvent drop time (-) C : concentration of solution (g/dl) &lt;350 °C Weight reduction rate > About 15 mg of flame retardant alone and urethane-modified polyimide resin were collected, and the ambient temperature was raised at 10 ° C / min in an air atmosphere (20 ml / min). After heating to 100 °C, hold for 30 minutes, and then heat it to 60 °C at a heating rate of 10 °C /min on an aluminum pan to obtain 150 °C to 350 °C. The weight reduction rate of C. The device used: Shimadzu Corporation's differential heat and thermal weight simultaneous measurement device DTG-60 &lt;Continuous printability&gt; The amine group was evaluated according to the following criteria by the method described in Example 19. When the formate-modified polyimine-based flame retardant resin composition was continuously screen-printed for 30 minutes, the resin of the paste was precipitated and the viscosity was increased. (Judgement) 〇: No scratches, resin precipitation, and printing were observed. Increased ink viscosity X: scratches, resin precipitation, ink viscosity increase &lt;shake degree&gt; -47- 201125897 Using Brook Field BH type rotary viscometer, the order is measured. The paste tank made of ester-modified polyimine-based flame retardant resin composition in the wide-mouth type light-shielding bottle (l〇〇ml) adjusts the liquid temperature to 2 5 °C ± 0.5 ° C. Then, after stirring for 40 times in 15 seconds, the specified rotor was set, and the scale was rotated at 20 rpin for 3 minutes. The viscosity was calculated by calculating the coefficient of the table. The viscosity at 25 °C is calculated according to the following equation: The degree of shake = viscosity (2 rpm) / viscosity (20 rpm) &lt; pot life of ink &gt; modification of urethane After the bismuth imine-based flame retardant resin was allowed to stand at 25 ° C for one month, no resin precipitation or gelation was determined according to the following judgments. (Judgement) 〇: no abnormality Δ: precipitates x: solidified &lt; phosphorus contained Rate> Determined by wet decomposition and molybdenum blue colorimetric method. The amount of phosphorus in the sample is determined by taking an appropriate amount of the amine urethane-based flame retardant resin composition hardened at 1 6 5 ° C for 2 hours. Add 3ml of sulfuric acid, 〇5ml of perchloric acid and 3.5ml of heat to the heat for a half-day heating decomposition. If the solution becomes transparent, the following process The sample obtained by using the carboxylic acid and the constant temperature water 5 glass rod for 1 2 to 5 minutes, and reading the scale multiplied by 2 rpm to evaluate the composition obtained by formulating the modified ester in the conical flask , Nitric acid, electricity, then add -48- 201125897 heat to produce white sulfuric acid, cool to room temperature, decompose this into a 50 m 1 volumetric flask, add 5 m 1 of 2% ammonium molybdate Solution and 2 m 1 [barium sulphate solution, add pure water to the mark, mix the contents of the bottle thoroughly and immerse in the boiling water bath for 10 minutes. After heating the color, the water is cooled, and the ultrasonic wave is degassed. A l〇mm dissolved spectrophotometer (wavelength 8 3 Onm) was collected in the absorption box, and the blank test solution was measured. The phosphorus content was determined from the previously prepared calibration curve. &lt;flammability&gt; The polyimide film having a thickness of 25 μm was used as a base material, and the laminate film having a thickness of 15 μm was evaluated for its flame retardancy according to the UL94 standard. 0 ° &lt;exudation&gt; The laminate obtained by using a polyimide film as a substrate was thin ί lOcm x 10 cm. The sample was sealed in a vinyl bag which was subjected to 65% humidity control at 25 ° C for 24 hours, and placed in a thermostat at 25 ° C for ~1 month. The surface was visually touched and touched with a finger, and the adhesion was evaluated according to the following judgment. sense. (Judgement) ◎: No exudate or sticky feeling even after 3 months: No exudate or sticky feeling even after 1 month △ : Exudate and sticky feeling after 1 month X : 1 Significant exudate and sticky sensation moved to 0.2% after the week. The room temperature is burned to the liquid, and the flammability obtained by the light absorption is used. VTM- Moche into a poly 1 week benchmark -49- 201125897 &lt;low warpage&gt; 稹lOcmxlOcm obtained from a polyimide film as a substrate » will be conditioned at 25 〇C by 65% 24 The samples of the hour were placed on a horizontal glass plate in a 1&quot; convex state, and the average of the heights of the four corners was evaluated based on the following criteria. (Judgement) 〇: Height is less than 2 mm △: Height is less than 1 〇mm χ: Height is l〇mm or more &lt;Flexibility&gt; For laminated film obtained from polyimide film as a substrate, according to JIS-K5400 Conduct an evaluation. The diameter of the mandrel was 2 mm, and it was confirmed whether or not cracks occurred. <Insulation resistance between wires> A comb pattern of 50 μm η was prepared on a 2-layer CCL (trade name Viloflex) manufactured by Toyobo Co., Ltd., washed with 1% sulfuric acid, and washed with water. The paste was completely printed on the circuit, and the obtained solder resist layer was heat-hardened under conditions of 160 ° C for 120 minutes. The line-to-line insulation resistance when the DC voltage was applied at 100 V was measured. It is preferably 10 or more of the power of 10 or more. &lt;Heat-resistance and heat resistance&gt; The laminated film obtained by using a copper foil as a base material was immersed in a solder bath of 260 C for 30 seconds in accordance with ns_C64 8 , and the appearance abnormality such as peeling or foaming was evaluated based on the following criteria. . -50- · 201125897 (Judgement) 〇: No appearance abnormality △: Abnormal appearance X: Overall appearance abnormality &lt;Adhesiveness&gt; A laminated film obtained by using copper foil as a base material was produced in accordance with JIS-K5 600 ' A 1 mm checkerboard was subjected to a peeling test by Cellotape (registered trademark) to observe the peeling state of the checkerboard. The laminate film obtained by using the polyimide film as a substrate was subjected to a peeling test in the same manner, and the peeling state of the checkerboard was evaluated based on the following criteria. (Judgement) 〇: 1 0 0 / 1 0 0 No peeling Δ : 70 ～ 99/100 X : 0 ～ 70/100 &lt; pencil hardness&gt; For laminated film obtained from copper foil, according to ns-K5 400 to evaluate. The pencil hardness is preferably 2 Η or more, more preferably 3 Η or more. <PCT resistance> The laminated film obtained by using a polyimide film as a substrate was allowed to stand in an environment of 1 21 ° C and 2 atm for 48 hours, and the appearance abnormality such as peeling or dissolution was evaluated based on the following criteria. (Judgement) 〇: No appearance abnormality -51 - 201125897 △: Abnormal appearance X: Overall appearance abnormality &lt;Chemical resistance&gt; The laminated film obtained by using a polyimide film as a substrate is 10% HC 1, Each of the solvents of 10% N a Ο Η, isopropyl alcohol, and methyl ethyl ketone was immersed for 1 sec., and the appearance abnormality such as peeling or dissolution was evaluated based on the following criteria. (Judgement) 〇: No abnormality in appearance even when immersed in all the solvents △ · When immersed in at least one solvent, the tip has a slight appearance abnormality X: When immersed in at least one solvent, there is a general appearance abnormality. 166.0 parts by mass of trimellitic anhydride (purity of 99.9%, trimellitic acid content of 0.1%) and 86.3 parts by mass of bisphenol A were placed in a four-port, two-liter separable flask equipped with a stirrer, a cooling tube, a nitrogen introduction tube, and a thermometer. Polypropylene oxide adduct (trade name: Newpol BP-5P, manufactured by Sanyo Chemical Industries Co., Ltd., molecular weight 5 3 3 ), and 108 parts by mass of polypropylene glycol (Sannix PPG2000, manufactured by Sanyo Chemical Industries Co., Ltd.) Molecular weight 20 00), 84.1 parts by mass of hexamethylene diisocyanate, 125.1 parts by mass of diphenylmethane-4,4'-diisocyanate, 493.5 parts by mass of γ·butyrolactone, and 1.5 parts by mass as a catalyst The 1,8-diazabicyclo[5.4·0]-7-undecene was heated from a liquid temperature of 30 ° C to 16 under a nitrogen stream (after TC was reacted for 5 hours), adding 24 6.8 parts by mass. Diethylene glycol dimethyl ether for dilution -52-201125897, After cooling to room temperature, a thick brown urethane-modified polyimine resin solution A-1 having a nonvolatile content of 40% by mass was obtained. Production Examples 2 to 5 Using the raw materials described in Table 1, After polymerization in the same manner as in Example 1, the mixture was cooled to room temperature to obtain a thick brown urethane-modified polyimine-based resin solution Α-2 to Α-5 having a nonvolatile content of 40% by mass. 6 In a four-port, two-liter separable flask equipped with a stirrer, a cooling tube, a nitrogen inlet tube, and a thermometer, 86.3 parts by mass of trimellitic anhydride (purity of 99.9%, trimellitic acid content 〇%) and 184.4 parts by mass of B were charged. Diol double-dehydrated trimellitate, 342.4 parts by mass of polycaprolactone diol (trade name PLACCEL 220 manufactured by Daicel Chemical Industry Co., Ltd., molecular weight 2000), 2 5 0.3 parts by mass of diphenylmethane_4 , 4'-diisocyanate, 7.83% by mass of γ-butyrolactone, and 1.5 parts by mass of 1,8-diazabicyclo[5.4.01-7-Η^-eneene as a catalyst in nitrogen After flowing down from the liquid internal temperature of 30 ° C to 120 ° C and reacting for 5 hours, 392.1 parts by mass of diethylene glycol dicarboxylic acid was added for the reaction. After releasing to room temperature, a thick brown urethane-modified polyimine resin solution A-6 was obtained in a non-volatile content of 40% by mass. The production examples 7 to 8 were as described in Table 1. The raw material was polymerized in the same manner as in Example 6, and then cooled to room temperature to obtain a thick brown urethane-modified polyimine-based resin solution A-7 to A-8 having a nonvolatile content of 40% by mass. -53-201125897 [Table 1] Manufacturing Example 1 Manufacturing Example 2 Manufacturing Example 3 Manufacturing Example 4 Manufacturing Example 5 Manufacturing Example 6 Manufacturing Example 7 Manufacturing Example 8 A-1 A-2 A-3 A-4 A-5 A-6 A-7 A-8 (a) component (% by mole) TMA 80 70 65 19 80 42 35 50 TMEG 0 0 0 19 0 42 35 50 (b) Component (b-1) component (% by mole) PTMG85 0 0 0 5 8 0 0 5 0 PPG1000 0 10 0 0 0 0 0 0 PPG2000 5 0 0 0 0 0 0 0 (b-2) component (mole%) BP-5P 15 20 30 54 20 0 0 0 (Mo Ear %) C-2090 0 0 0 0 0 0 30 0 PCL220 0 0 0 0 0 16 0 0 (c Cheng cent (mole / 〇) HDI 50 50 50 0 50 0 0 0 MDI 50 50 50 100 50 100 100 100 〇1疋11 (review %) 23.7 25.2 11.3 13.2 0.0 48.4 67.8 0.0 0&gt;2 volumes (% by weight, 23.6 30.7 47.0 62.1 37.9 0.0 0.0 0 .0 logarithmic viscosity (dl/g) 0.32 0.35 0.33 0.36 0.38 0.38 0.36 0.36 C-2090: Polycarbonate diol made of Kuraray (molecular weight 2000) PCL220 : Polycaprolactone diol manufactured by Daicel Chemical Industry (molecular weight 2000) PTMG850: Mitsubishi Chemical Polybutanediol (molecular weight 850) PPG2000: Sannen Chemical Industrial Sannix PP (molecular weight 2000) PPG 1 000: Sanni Chemical Co., Ltd. Sannix PP (molecular weight 1000) BP-5P: Sanyo Chemical Industry Newpol (molecular weight 533) TMA: trimellitic anhydride TMEG: ethylene glycol double-dehydrated trimellitic acid ester HDI: 1,6-hexamethylene diisocyanate MDI: diphenylmethane diisocyanate Example 1 The urethane modified product obtained in Production Example 1 was changed. The resin of the polyimine-based resin solution A-1 was divided into 48.8 parts by mass, and 7.2 parts by mass of jER152 (trade name of -54-201125897 of phenol novolak type epoxy resin made of Japanese epoxy resin) was added. Diethylene glycol dimethyl ether was diluted. Further, 3.2 parts by mass of A er 〇si 1 # 3 0 0 (hydrophilic vermiculite particles manufactured by Aer 〇si 1 (Japanese)) and 19.1 parts by mass were added as non-halogen flame retardants. SANKO-BCA (Sanko (manufacturing)), 19.2 parts by mass of SPE-1 (manufactured by Otsuka Chemical Co., Ltd.), 0.5 parts by mass of ucat 5 002 as a hardening accelerator (Sanapr〇) System), 1_5 parts by mass of Fi〇ren AC-326F (manufactured by Kyoeisha Chemical Co., Ltd.) and 质量·5 parts by mass as a leveling agent - 3 5 8 (ΒΥΚ化学(股) )), first, coarse-kneading, followed by high-speed 3 rolls, repeating 3 times of mixing to make the material uniformly dispersed, and obtaining a urethane-modified polyimine-based flame retardant with vibration. A paste formed by a resin composition. The viscosity was adjusted with diglyme to give a solution viscosity of 130 poise and a rocking degree of 2.5. Next, the paste obtained by coating the obtained urethane-modified polyimine-based flame retardant resin composition on the shiny side of the electrolytic copper foil having a thickness of 114 Å was used to make the thickness after drying 15 μm. After drying at 80 C hot air for 1 minute, it was heated at 150 ° C for 120 minutes in an air atmosphere to obtain a laminated film. Further, the copper foil of the obtained laminated film was removed by uranium chloride solution to obtain a film. Similarly, it was coated on NPI of a polyimide film having a thickness of 25 mm, dried and heated, and the resultant was dried and heated to obtain a laminated film. Table 2 shows the details and evaluation results of the laminated film. Example 2~

A laminate was obtained in the same manner as in Example 1 to obtain a film of -55 to 201125897. Tables 2 and 3 show the results of evaluation of the obtained composition and laminated film. Example 1 9 Modified by carbamate obtained in Example 5 on a copper circuit (L/S = 50/50) obtained by subtractive conversion of two layers of CCL (trade name Viloflex, copper substrate 20 μηι) manufactured by Toyobo Co., Ltd. Polyimide-based resin composition paste, SUS mesh plate (MURAKAMI Co., Ltd. emulsion thickness 30μηι), printing at a printing speed of 5 cm / sec, drying at 80 ° C for 6 minutes, at 165 ° C The hard clock was heated to obtain a flexible printed wiring board to which a cover layer (film) made of a urethane-modified polyimine-based tree was applied. The film f 1 5 μιη. The obtained flexible printed wiring board is soft and bent. I: 匕 Comparative Examples 1 to 7 In addition to the raw materials described in Table 4, a urethane-modified polyimine-based difficult material or a laminated film was obtained by the operation of the example. The composition, product details and evaluation results obtained are shown in Table 4. The details are detailed with the box 1 8 μιη, , and the 150 mm mesh formed by the embodiment, in the case of cavitation, 60 parts of the fat composition, the thickness is excellent, and the example 1 is the same as the resin layer film -56- 201125897 [csm] 1 Embodiment 91 1 A-5 | 48.8 OJ &lt;N CO | 19.1 | ο ο ο ο ο ο I 19.2 I Ο ο Ο Ο Ο Ο Ο ο ο ο ο ο ο ο ο ο ο ο ο Τ—ΙΟ ο I 100.0 | ο LO 1 Embodiment 8 1 1 A-4 | 53.4 Ο) in CO ool 21.0 I ο ο ο ο ο c gt ζ〇Ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο c&gt; ο ο CD τ— ιη ο [100.0 I CO CD Example 7 1 A-4 1 53.4 σ&gt; Bu· LO CO I 21.0 I ο Ο ο ο ο ο ο ο I 11·6 | Ο Ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 ρ ο ο ο ο ο ο ο ο ο 10 τ τ 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 ο ο ο I 21.0 I ο ο ο ό ο ό ο ο Ι ο ο ο ο ιη ^ Γ ι ο 100.0 | ο inch 1 embodiment 4 | CO &lt; 48.8 CVJ CM CO | 19.1 ρ ο ρ ο ρ ο ο ο 丨19.2 I ο ο Ο ο ρ ο ο ό ο ο ο ο ο ο ο ο ο ο - Ι Ω ο | 100.0 | ο 1 embodiment 3| 1 A-2 | 48.8 CM CN CO | 19.1 ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ρ c&gt; ο d ΙΟ Τ - ιη ο | 100.0 J ο (NT - 丨 Example 2 | 1 A-2 1 48.8 CM &lt; N CO | 19.1 | ο ο ο ο ο ο L 19.2" ο ο ρ ο ο LO ο ο ο ο ο LO τ — ιη ο | 100.0 | ο LO i Tie τ— &lt; 48.8 &lt;N CN CO I 19.1 ο ο ο ο ρ ο I 19.2 I ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο -100 SPB-100L SPH-100 ΡΧ-200 ΟΡ-935 MC-2010N PHOSMEL-200 MGZ-3 UCAT5002 ΙΧΕ-100 IXE-700F Floren AC-326F ΒΥΚ-358 Total Price Quantities) ---- Q CN Q (8) Main agent (B) Epoxy resin (c) Dip material (D-1) (D-2) (Ε) Hardening accelerator (F Sub-catchant defoamer leveling agent 35CTC weight reduction (D igniting agent -^- 201125897 CO CsJ &lt;] T-CO 〇ΙΟ — 1 VTM-0 I &lt; 〇〇1.2χ1012 〇&lt; 〇X CO 〇 〇LO CO 〇 T T — 〇LO — 1 VTM-0 1 ◎ &lt;] 〇|8.0χ1013| 〇〇〇I CO 〇〇LO CO 〇00 τ—〇卜CO | VTM-0 ◎ 〇〇|2.1χ1013 〇〇〇X CO 〇〇in CO 〇05 τ~ 〇in inch 1 VTM-0 &lt; 〇〇6.0χ1012 〇〇〇X CO 〇〇00 CSJ 〇Ο c\i 〇布 CO 1 VTM-0 j &lt ;〇〇3.5χ1012| 〇〇〇X CM 0 〇00 CN 〇ο c\i 〇LO — | VTM-0 ◎ 〇〇3·5χ1012| COCO 〇〇in CO 〇τ~ CO 〇CN — VTM-0 〇〇〇5·0χ1012| Completion CO 〇〇LO CO 〇τ— oi 〇LO — | VTM-0 &lt; 〇〇5_0χ1012| COCO 〇〇CO CO 〇m oi 〇 In — | VTM-0 &lt; 〇〇2.0χ1012 Completion CO 〇〇(A)(wt%) Continuous Printing Shake Degree Applicable Period Neighbor Content (% by mass) Flame retardant bleed Low warpage Sexual line Resistance (Ω) Resistance to soldering heat adhesion Cu on the i-bonded PI film on the bell pencil hardness PCT resistance I chemical resistance _ (in the air) Ink characteristics Coating film characteristics 1 豳 屮铠铋 & chain &lt;n冏M : u.ooz-Liixl 听 屮铠豳铋 chain &lt;0 credit: 00&quot;73&gt;&lt; ^^_^·Η·^^:ε-ζ91ΛΙ gl^J!«_BfHltf^Rna : IA1CVI Inch-Hi2m6!H 0^0 氍m stepping on 3⁄4撇Η Delete B: oocvl--lLUIAISOHd II 氍 alkali inlay 1!|Installation shaft 锵撇H#^ Dry: N05CN-OIAI 瑕氍 稍 igHitce!Jeo:LOco6- d〇flidzirM^Am : 8ίοε-&gt;ΙΛω -81? 浒芨酹铋琳翠骚-κ 蘅 铋蝌 铋蝌 起 揉 ϋ ϋ ϋ 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 Feeding 氍璲&lt;n氅铋蝌Λ35-Κ: ooCSI-xd 0000ooTHds, Ίοοτωο-ω, 00TLUQ.S 淋淋111 State: ddl·-松州驻松 A3&gt;嫲-0&quot;7骶-0&quot;7 Carbonyl 嫲-6-^::1-01/6铋米111:&lt;〇工,&lt;〇9 W litigationlli!SOJav^[n:00col!SOJavS5莸莸璲赃璲赃螽铋嘁·嘁鹏- 14tn:cslsT-Qrllli 201125897 [ε £ 00 ϊ 习 I A-7 I 55.4 ιο 00 Ο 00 I 13-1 I Ο d ο ο ο ο ο ο Ο ο Ο ο Ο ο Ο ο Ο ο LO ο ο OJ ο c\i ιη τ— LO d I 100.0 I ο CM in CO 〇I Example 17| I A-7 | 56.9 CO 〇6 ο CO I 14.5 I ο ο ο ο ο ο ο ο ο ο ο ο ό I 105 I ο ο ο ο ο ο LO ο ο CN ο cvi ΙΟ τ — ΙΟ d 100.0 I ο (Ν LO CO 〇I Example 16| I A-6 | 46.7 &lt;N 00 | 18.1 ο ο ο ο ο ο ο ο ο ο ο I I I I I I I I I I I I CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN | C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C A-4 46.7 CN 00 I 17-0 ο d&gt; ο ό ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο CN LO CO 〇I Embodiment 14| 3 46.7 &lt;N 00 I 17.0 I ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο τ τ — τ — 100.0 ο LO LO CO 〇 Example 13 I A-4 I 55.4 LO 〇 6 CO ai 卜 σ ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο - Τ - ο 00 ο C0 V τ - 100.0 | ο CM LO CO 〇 Example 12 X - &lt; 48.8 &lt; N CM CO I 19.1 | ο ο ο ο ο ο ο ο ο ο ο ο ο 19 I LT 19 19 19 19 τ τ LT LT LT 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 11 11 0.0 11 0.0 11 11 11 11 11 11 11 11 11 04 CO q ό ο ο | 19.1 | ο ό L1^2J ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο 1〇| L A-6I 53.4 in CO I 21.0 ο ο 〇 ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο 〇Manufacturing example m Distillation 赖mm mm jER-152 Aerosil 300 BCA HCA ΤΡΡ CN4 Soil 1 Ο) Ξ SPE-100 SPB-100L SPH-100 ΡΧ-200 ΟΡ-935 MC-2010N PHOSMEL-200 MGZ-3 UCAT5002 ΙΧΕ -100 IXE-700F Floren AC-326F ΒΥΚ-358 Total (parts by mass) X—»&gt; Τ Ι Q x—N, t C\T 1 Q y—*«s &lt;. Continuous printability (A injection) (B) Epoxy resin (c) Dipping material (D-1) ... I (D-2) (Ε) hardening accelerator (F scorpion trapping agent defoamer leveling agent 350 °c military halo reduction?嫉Sf order\Ink characteristics (D傩燃剂-6LO- 201125897

201125897 [Inch® 1 Comparative Example 7 1 I A-7 I 59.5 LO 00 CM CO 〇o Ο d ο ο I 26.3 I ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο τ τ—in d 100.0 CD CS4 ο CO Comparative Example 6 τ— &lt; 48.8 CN CM &lt;ri od ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ΙΟ τ—in d 100.0 I Τ—CO CO Comparative Example 5 A-3 75.5 00 σί OJ CO od ο d ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ιη X—d 100.0 I in 00 OJ Comparative Example 4 00 &lt; 48.8 &lt; 48.8 &lt; Ν CN CO 19.1 ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ρ C) LO χ—in d 100.0 o in Comparative Example 3 A-3 48.8 CN 卜 CM CO oo ο ο ο ό ο ο | 19.2 ο ο ο ο | 19.1 | ο ο ο ο ο ο ο ο LO Ο ο ο ο ο LO τ — mo 100.0 I 5-14 00 CM Comparative Example 2 A-3 48.8 OJ CN CO 38.3 ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο LO χ—in d 100.0 o I 00 eg Comparative Example 1 T— &lt; 48.8 CN CN CO od ο ο ο ο ο ο 3 ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο Resin jER-152 Aerosil 300 BCA HCA ΤΡΡ &lt;Ν i φ D) Ξ SPE-100 SPB-100L SPH-100 ΡΧ-200 ΟΡ-935 MC-2010N PHOSMEL-200 MGZ-3 UCAT5002 ΙΧΕ-100 IXE-700F Floren AC-326F BYK-358 Total (parts by mass) (D-1)(wt%) (D-2)(wt%) •o*—»s &lt; (8) Main agent (B) Epoxy resin (c)塡Material (D-1) (D-2) (Ε化化剂(F 漓 捕捉 捕捉 消 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 - s 201125897 〇CX) τ— 〇ο I NOT I ◎ XX CN T- X τ- — 〇0 〇 〇 X 〇CD oi 0 ο | NOT ◎ X 〇3.0χ1012 〇&lt; Completion CsJ 〇0 〇00 〇CO τ— 1 NOT I &lt; X 〇8.1x10^1 Completion CN 〇〇〇τ— c\i 〇ιη 1 VTM-0 &lt; XX 1.1χ1012 〇&lt;] X 00 〇〇〇CN c\i 〇—1 NOT XX 〇|3.5χ1011 I &lt; Completion eg &lt; 〇CO c\i 〇τ—inch' | NOT I 〇〇 〇3.5χ1012| &lt; Completion &lt; X 〇oc\i 〇&lt;Ν L〇| VTM-2 ) XX 〇[6.0x1012| 〇&lt; Completion OJ 〇〇Continuous Printing Shake Degree Applicable _ Content ratio (% by mass) Flame retardant bleed Low warpage bending Inter-line insulation resistance (Ω) Resistance to soldering heat adhesion Cu on the adhesion PI film Pencil hardness pct resistance Chemical resistance Ink characteristics 1 _i Coating Characteristics-s-201125897 As can be seen from Tables 2 to 4, the hardened coating film formed of the urethane-modified polyamidene-based flame retardant resin composition of the present invention can be used at low temperatures. Curing 'warp-free' flexibility, flame retardancy, heat resistance, chemical resistance, electrical properties, and excellent adhesion to a substrate. On the other hand, in the comparative examples 1 to 3 and 5 to 7, the characteristics and the blending amount of the flame retardant were outside the range of the present invention. In the comparative example 4, the urethane-modified polyimide-based resin was used in the present invention. In addition to the scope of the invention, the cured coating film formed of the urethane-modified polyimine resin-based flame retardant resin composition is inferior in various properties. INDUSTRIAL APPLICABILITY The urethane-modified polyimide-based flame retardant resin composition of the present invention is suitable as a film forming material, and can be applied to various electronic parts for flexible printed wiring boards. Ink-resistant solder ink, interlayer insulating film, can also be used as a coating, coating agent, adhesive, etc. in a wide range of electronic equipment. [Simple description of the diagram] None. [Main component symbol description] Αττ tear. -63-

Claims (1)

201125897 VII. Patent application scope: 1. A urethane-modified polyimine-based flame retardant resin composition, which is composed of a urethane-modified polyimine-based flame retardant resin having the following composition (A) A (a) trivalent and/or tetravalent polycarboxylic acid derivative having an acid anhydride group, (b) a diol compound, and (c) an aliphatic polyamine residue derivative and/or an aromatic a urethane-modified polyimine-based resin having a urethane bond formed as an essential component of an amine residue derivative, and (B) having two or more epoxy groups per molecule Epoxy resin, (C) inorganic or organic tantalum, and (〇) non-primary flame retardant, characterized by: (D) Non-halogen flame retardant containing 35 〇t weight loss in air The component (D - 1 ) having a ratio of 50% or more and 90% or less and the component (D-2) of 0% or more and 20% or less are essential components. 2. The urethane-modified polyimide-based flame retardant resin composition according to the first aspect of the patent application, wherein the weight reduction ratio of the component (D-1) is 60% or more and 85% or less, (D- 2) The weight reduction rate of the component is 0% or more and 15% or less. 3. A urethane-modified polyimine-based flame retardant resin composition according to claim 1 or 2, wherein (D) a non-halogen flame retardant contains (A) a urethane A phosphorus-based flame retardant compatible with a modified polyimine-based resin. 4. The urethane-modified polyimide-based flame retardant resin composition according to any one of claims 1 to 3, wherein the (D-1) component contains 9,10--64-201125897 A dihydro-9-oxa-10-phenanthr #10 oxide derivative, and the component (D-2) contains a phenoxyphosphazene compound. 5. The urethane-modified polyimide-based flame retardant resin composition according to any one of claims 1 to 3, wherein the (D) non-dental-based flame retardant system is contained A non-halogen flame retardant. 6. The urethane-modified polyimine-based flame retardant resin composition according to any one of claims 1 to 3 or 5, wherein the (D-1) component contains 9,10-dihydrogen -9-oxa-10-phenanthrene-10-oxide derivative, the component (D-2) contains a phosphonic acid metal salt represented by the following formula [I], and the following formula [Π] a reaction product of a metal phosphonate, a reaction product of a cyanamide derivative having at least one amine group with a phosphoric acid, or a cyanamide derivative having at least one amine group and a cyanuric acid, [I] 2- Μχ&quot;^ [II] η (In the formula [I] and the formula [II], R1 and R2 may be the same or different from each other, and are linear or branched alkyl and/or cycloalkyl and/or aryl groups. And/or aralkyl groups 'R1 and R2 may be bonded to each other to form a ring together with adjacent phosphorus atoms; R3 is linear or branched (:!~C1() alkyl group, C6~C10 cycloalkyl group , C6~C1Q aryl, C6~C1Q alkyl aryl or C6~-65- 201125897 c10 arylalkyl, Μ from Mg, Ca, Λ1, sb, Sn, Ge, Ti, Zn, Fe, Zr At least one selected cation of the group of Ce, Bi, Sr, Mn, Li, Na, K or a protonated nitrogen base, an integer of 1 to 4, an integer of η of 1 to 4, and an X system The urethane-modified polyimide-based flame retardant resin composition according to any one of claims 1 to 6, wherein the component (D-2) is contained in 25. (:, a phenoxyphosphazene compound which is a liquid under the conditions of 1013.25 hPa. 8) The urethane-modified polyimine which is any one of the above claims 1 to 7 is flame retardant. a resin composition in which (b) a diol compound contains (b- Ι) polyoxyalkylene glycol and/or (b-2) a polyalkylene oxide adduct of bisphenol represented by the following formula [ΙΠ], (In the formula [III], the compound is C^Czoalkylene, and R2 and R3 may be the same or different from each other, and represent hydrogen or a Ci~C4 courtyard group, m is an integer of 1 or more, and η is an integer of 1 or more). The urethane-modified polyimine-based flame retardant resin composition according to any one of claims 1 to 8, which further contains a (?) hardening accelerator. The urethane-modified polyimine-based flame retardant resin composition according to any one of claims 1 to 9, which further comprises (F) an ion trapping agent. -66- 201125897 1 1. A urethane-modified polyimine-based flame retardant resin composition according to any one of claims 1 to 10, wherein (Α) urethane is modified The polyimine-based resin is obtained by reacting 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. The urethane-modified polyimine-based flame retardant resin composition according to any one of claims 1 to 11, which has a rocking degree of a shearing degree of 1.1 or more. An electronic component, which is an electronic component having a solder resist layer, a surface protective layer, an interlayer insulating layer or an adhesive layer, characterized in that the layer is as described in any one of claims 1 to 12. The urethane-modified polyimine-based flame retardant resin composition is obtained by drying and hardening. -67- 201125897 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: 〇 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: