TW200927795A - Flame-retardant polyimide-silicone resin composition - Google Patents

Abstract

This invention provides a polyimide-silicone resin composition having the advantage caused by the introduction of a polysiloxane and improved flame retardancy. The composition of this invention contains: (A) polyimide-silicone resin containing 10 to 25% by weight of silicon atom based on the weight of the polyimide-silicone resin, and phenyl groups of 5 to 70 mol % of organic groups bonded to the silicon atoms, and (B) a flame retardant of 1 to 200 pts. mass based on 100 pts. mass of the component (A).

Description

200927795 IX. OBJECTS OF THE INVENTION [Technical Fields of the Invention] The present invention relates to a polyamidene polyoxymethylene resin composition, and more particularly to a flame retardant having a specified flame retardant, and providing flexibility A composition of a cured product excellent in heat resistance and adhesion. [Prior Art] Since the polyimide resin has high heat resistance and excellent electrical insulating properties, it is widely used as a printed circuit board, a heat-resistant adhesive tape, an electric component, a protective film for a semiconductor material, an interlayer insulating film, and the like. However, since the quinone imine resin is only dissolved in a limited solvent, it is inconvenient in operation. Therefore, a method in which polypyramine which is relatively easy to be dissolved in various organic solvents is applied to a substrate and dehydrated and cyclized by a high temperature treatment to obtain a polyimine resin is employed. However, since high temperature and long-time heating is required by this method, thermal deterioration of the substrate is liable to occur. On the other hand, if the heating is insufficient, the poly-proline is left in the structure of the obtained oxime resin to become wet. The reason for the decrease in properties, corrosion resistance, etc. Therefore, instead of the poly-proline, a solution of the polyimine resin in an organic solvent is applied to the substrate, and the solvent is volatilized by heating to form a film of the polyimide film, for example, it is known to contain polyoxyl A polyalkylene polyisocyanate having an alkane moiety (Patent Documents 1 and 2). It has been found that these polyimine polysiloxanes are excellent in physical properties such as flexibility of a cured film, but are still inferior in flame retardancy. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The advantage of the polyoxymethane portion is to enhance the flame retardant polyimine polyoxymethylene resin composition.解决 Solution to the Problem The present inventors have found that the above object can be attained by a polyfluorene-polyoxyl resin having a predetermined amount of a ruthenium atom and a phenyl group in a siloxane skeleton. That is, the present invention contains (A) a polyamidene polyoxynene resin containing 10 to 25 wt% of a ruthenium atom by weight of the polyamidene polyoxyxylene resin, and bonded to an organic group of a ruthenium atom. 5 to 70 mol% is a phenyl polyimine polyoxyl resin, G and 1 to 200 parts by mass of (B) a flame retardant with respect to 1 part by mass of the component (A). Composition. EFFECT OF THE INVENTION The cured film obtained from the polyimide composition of the present invention has excellent flame retardancy and flexibility, and does not peel off from the substrate even when exposed to high temperature or high humidity. -5- 200927795 The best mode for carrying out the invention. The composition of the present invention (A) polyimine polyoxyl resin contains 1 to 25% by weight of germanium atoms relative to the weight of the resin, to 1 〇~20% by weight is preferred. If it is within this range, the high solubility to the solvent and the flexibility and flame retardancy of the cured product can be simultaneously established. The amount of ruthenium atom is determined by NMR or thermal ashing of the resin, and the ashing method for elemental analysis can be used to quantify ❹. Further, (A) the polyamidene polyoxy siloxane resin is bonded to the organic group of the sand atom. ~70% of the mole is phenyl, preferably 10~50% by mole, especially preferably 2〇~40mol%. It is particularly preferable to use a phenyl group as a diphenyl polysiloxane unit, that is, a unit represented by the following formula

The form. When the amount of the phenyl group is less than the above lower limit 値, the flame retardancy is inferior, and if it exceeds the above upper limit 値, the modulus of elasticity of the cured product becomes high. The amount of the phenyl group can be measured by 29Si-NMR. The (A) polyamidene polyoxyalkylene resin is formed by two repeating units represented by the following formula (1). 200927795 Ο Ο II II •/\ΑΝ—γ.V VII II ο ο ο ο Μ 八 八 X X X X V V V V V V V V V 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 That is, the m and η systems respectively indicate the ratio of the repeating unit containing Υ and the repeating unit containing z, m+n=l. The Z series contains a phenyloxane unit, and the diphenyl fluoran unit is preferably a divalent group, and the η is a number of 0.4 to 0.8, preferably 0.5 to 0.8. The resin in which η is less than the lower limit 値 has a high modulus of elasticity of the cured product and a tendency to be insufficient in flexibility. On the other hand, when the above upper limit 値 is exceeded, the resin has a wrinkle feeling and is difficult to handle at room temperature. Further, in the present invention, the modulus of elasticity refers to the storage elastic modulus, and the measurement method will be described later. Although depending on the application, the modulus of elasticity is usually less than 1 GPa. The 〇Z system is preferably represented by the following formula (2). R1 / κ ·Λ / 0\ ψ -CH2CH2CH2-Si4〇-Si-^)-Si^(:)-Si-CH2CH2CH2- (2) R2\R4/A(^j)A R6 In the formula (2) R1 to R6 are a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms other than a phenyl group, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group, a cyclopentyl group, An aliphatic unsaturated group such as a cycloalkyl group such as a cyclohexyl group, a vinyl group or an allyl group. Among these, methyl and ethylene 200927795 are preferred. In the formula (2), a and b are each an integer of 1 to 40, but a+b is an integer of 2 to 50. It is preferable that a is an integer of 1 to 20 and b is an integer of 1 to 20. When a and b exceed the above upper limit, the solubility in the solvent is insufficient. Further, b/(a+b) is 0.1 to 〇8, preferably 0.1 to 0.6, and preferably 0.2 to 0.5. b/( a+b) is less than the lower limit 値', and the flame retardancy is insufficient. On the other hand, when the upper limit 値 is exceeded, the flexibility of the cured product is insufficient. © Z, the following formula (3) can also be used. Shower. R1 / R3\ AHsX / Q\ R5 ~CH,CH,CT,~Si4〇-Si^〇~Si-)(〇-Si—f〇-Si-CH2CH2CH2- (3) 'r6 Formula (3) (2) Part R3 is a vinyl group 'al+a2 is equal to the above a. It means that the ratio of a unit ratio of alkane having a vinyl group a2/(al+a2+b) is 0.1 to 0.6, to 0_1~0.4 Preferably, the cured product obtained from the resin in the above range is excellent in solvent resistance, and the polyacetal polyoxyl resin having the Z and the (C) organic peroxide described later are combined and blended. Further, a cured film exhibiting excellent solvent resistance can be formed. In the formula (1), the X-based tetravalent organic group can be induced from the acid dianhydride. Examples of X include, for example, the following formulas (4) to (9). Base. -8- 200927795

In the formula (1), the Y group does not contain a divalent group of a ruthenium atom, and is induced from a usual diamine. Examples of the hydrazine include aliphatic diamine residues such as tetramethylamine, 1,4-diamine-9-200927795-cyclohexane or 4,4'-diaminodicyclohexylmethane. Further, an aromatic diamine residue such as phenylenediamine, 4,4'-diaminodiphenyl ether or 2,2-bis(4-aminophenyl)propane may be used in combination of two or more kinds thereof. The aromatic diamine residue represented by the formula (10) is preferable, and in the formula, B is a group represented by any one of the formulae (1 1 ), (1 2 ) and (1 3 ).

(10)

(12)

(13) At least a portion of Y may be a group having a phenolic OH group. As such Y, for example, a group represented by the following formulas (14) to (18) can be mentioned. 200927795

-11 - 200927795 Resin, (D) epoxy resin, and (E) epoxy resin hardening aid, which will be described later, can further form a cured film exhibiting excellent solvent resistance. Suitably, the weight average molecular weight of the (A) polyamidene polyoxycene resin measured by GPC using polystyrene as a standard sample is 5,000 to 150,000, preferably 20, 〇〇〇 1 to 150,000. When the molecular weight is less than the above lower limit ,, the toughness of the cured film ′′, that is, the comprehensive strength of the flexibility and the mechanical strength is insufficient, and conversely, when it is larger than the above upper limit ,, the solubility in the solvent or the operability is poor. . Polyimine polyoxyalkylene resins can be produced by known methods. First, an acid dianhydride for inducing X, a diamine for inducing Y, and a diamine polyoxyalkylene for inducing Z are added to the solvent to carry out the reaction at a low temperature, that is, at a temperature of 20 to 50 ° C. A poly-proline which is a precursor of a polyimine resin. Next, the obtained poly-proline solution is heated to 80 to 200 ° C, preferably at a temperature of 1 40 to 1 80 ° C, by dehydration ring closure reaction of polyamido acid decylamine. A solution of a polyamidene polyoxyl resin can be obtained. © Adding this solution to a solvent of water, methanol, ethanol, acetonitrile, and drying the obtained precipitate to obtain a polyamidene polyoxyl resin. In this case, the ratio of the total of the diamine and the diamine polyoxymethane to the tetracarboxylic dianhydride is preferably 0.9 5 to 1 · 5 5 in the molar ratio range, and is 0. 9 8 to 1.02. good. Further, examples of the solvent used in the production of the polythenimine polyoxyalkylene resin include N-methyl-2-pyrrolidone, cyclohexanone, butane vinegar, and N,N-dimethylacetamide. Further, the water produced by the oxime imidization of the aromatic/fragrance: group hydrocarbons such as toluene or xylene may be easily removed by azeotropy. These solvents may be used alone or in combination of two or more. -12- 200927795 In addition, a material for adjusting the molecular weight of the polyamidene polyoxymethylene resin to add a functional group such as phthalic anhydride or aniline. In this case, the amount is 2 mol% or less relative to the polyamidene polyoxyl resin. In addition, during the imidization process, a dehydrated imidization catalyst may be added, and if necessary, heated to 50 °. C is about to make a method of amination. In this method, as the dehydrating agent, an acid anhydride such as ©, propionic anhydride or trifluoroacetic anhydride can be used. The dehydrating agent is used in an amount of 1 mole of diamine, preferably 1 to 10 moles. As the quinone imine, a tertiary amine such as pyridine, collidine, lutidine or triethylamine can be used. The hydrazine imidization amount is preferably 0.5 to 10% with respect to 1 mol of the dehydrating agent. The present invention is effective in that the reaction liquid is not exposed to a high-resistance resin in the step. When at least one of a plurality of diamines and tetracarboxylic dianhydrides is used, the anti-relation is not particularly limited. For example, a method of preliminarily mixing all the raw materials, or a method of causing condensation, or two or more kinds of diamines and tetracarboxylic acids to be used may be used. Under the individual reaction, the method of adding sequentially. In the present invention, the (A) polyamidene polyoxyxene resin is difficult to be used for use in electronic equipment, aircraft, 0A machines, etc., by adding (B) a flame retardant by adding (B) a flame retardant. (B) a flame retardant, for example, tetrabromoimine, tetrabromobenzenedodecyldiphenyl ether, tetrabromobisphenol A, hexabromocyclododecane, brominated olefin, bis(pentabromobenzene) Ethyl, poly(dibromopropyl ether), six, may also be added in a suitable amount. The agent and the hydrazine anhydride are relative catalysts. The methyl contact is a temperature, and the method is a copolymerization of dianhydride, which is flammable. As an acid anhydride, polystyrene bromide, etc.-13-200927795, a halogen-containing organic compound, triphenyl phosphate, trimethylphenol phosphate, trimethylphenyl phosphate, cresyl phenyl phosphate, 2-ethylhexyl Phosphorous compounds such as diphenyl phosphate, tri-dichloropropyl phosphate, tri-chloropropyl orthoate, poly-p-acids, red phosphorus, or antimony trioxide, antimony tetroxide, antimony pentoxide, Inorganic flame retardants such as sodium citrate, aluminum hydroxide, magnesium hydroxide, etc. 'In this case, triphenyl phosphate, trimethyl phosphate, trimethylphenyl phosphate, cresyl phenyl phosphate are used. should. © (B) A flame retardant is preferably used in an amount of from 3 to 100 parts by mass, more preferably from 3 to 50 parts by mass, per 100 parts by mass of the (A) polyimine polyfluorene resin. It is best to use 10 to 20 parts by mass. (A) A combination of hydrazine and a phenyl group to impart a hardened material excellent in flame retardancy. When the flame retardant is less than the above lower limit, it is difficult to improve the flame retardancy. On the other hand, when the temperature is more than the above upper limit, the cured film has a poor appearance and a decrease in physical properties such as flexibility. The Z system is (C) an organic peroxy ruthenium compound used in combination with the above formula (3), and examples thereof include diisoindole peroxide, dilaurin peroxide, and diphenyl hydrazine peroxide. Mercapto peroxide, t-butyl peroxy neodecanoate, t-butyl peroxytrimethyl acetate, t-butyl peroxy 2-ethylhexanoate, t-butyl peroxybenzoate , alkyl peroxy esters such as t-amyl peroxy neodecanoate, t-amyl peroxyacetate, t-butyl peroxyisopropyl carbonate, t-amyl peroxy 2-ethylhexyl carbonate, etc. Monoperoxycarbonate, bis(2-ethylhexyl)peroxydicarbonate, 1,6-bis(4-tert-butylperoxycarbonyloxy)hexane, bis(4-tert-butylcyclohexyl) Peroxydicarbonate such as peroxydicarbonate, 1,1-di(tert-butylperoxy) 3,3,5-trimethylcyclohexane, n--14-200927795 butyl-4,4- Peroxyketal, di- cumenyl, di-tert-butyl, etc. of di(tert-butylperoxy)butyrate, 1,1-di(tert-pentyl) 3,3,5-trimethylcyclohexane Peroxide, dialkyl peroxide of 2,5-dimethyl-2,5-di(tert-butylhexyne-3, etc., 1,1,3,3 -4 a hydroperoxide such as methyl butyrate or t-butyl hydroperoxide, but preferably a carbonate or peroxydicarbonate. It is shown that these peroxides have a polyamidene polyoxyl resin. Good compatibility. 〇 (c) The compounding amount of the organic peroxide is preferably 1 to 5 parts by mass, based on 1 part by mass of the (A) polyamidene polyoxyl resin. When the blending amount exceeds the above upper limit 値, the stability of the composition is deteriorated, or the cured product is deteriorated. Further, as the (D) epoxy used in combination with the polyphenyleneimine polyoxyl resin having a phenyl group of the above formulas (14) to (18), for example, a phenol novolac type epoxy resin or a cresol novolac resin may be mentioned. Bisphenol A type epoxy resin such as resin, diglycidyl bisphenol A, bisphenol F type epoxy resin such as glycidyl bisphenol F, triphenylmethane type epoxy such as trisphenol glycidyl ether a cyclic aliphatic ring such as a resin or a 3,4-epoxymethyl-3,4-epoxycyclohexanecarboxylate, monoglycidylphthalate or diglycidylhexahydrobenzene A glycidyl ester such as dimethyl diglycidyl phthalate is a glycidyl diamine diphenylmethane, a triglycidyl pair of phenol, a diglycidyl aniline or a diglycidyl toluidine. A glycidylamine resin such as tetraoleyl bisaminomethylcyclohexane or an oxygen resin can be used alone or in combination with two or more kinds of peroxy Oxides peroxygen chloride. I single peroxygen; and (amount of 0.1 to 3 parts of the preservation of phenolic hydroxy resin, type epoxy resin, dipropane triylcyclohexyloxy tree Acid ester, lipid, tetraamino benzene glycidyl bromide ring. In addition, -15-200927795 'As needed, can also add a monofunctional epoxy compound containing one epoxy group in one molecule. It is preferably 0.1 to 50 parts by mass, more preferably 5 to 40 parts by mass, per 100 parts by mass of the (A) polyamidiamine polyoxyl resin. If it is less than the above lower limit, it is not sufficient. On the other hand, when the above-mentioned upper limit 値 is exceeded, the flame retardancy and strength of the cured film are lowered. Φ For the purpose of promoting the above epoxy resin reaction, each (E) hardening accelerator may be used. Examples of the curing accelerator include an organic phosphine compound such as triphenylphosphine or tricyclohexylphosphine, trimethylhexamethylenediamine, diaminodiphenylmethane, and 2-(dimethylamino group). Amino compounds such as methyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol, triethanolamine, etc., 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole and 2 - an imidazole compound such as phenyl-4,5-dihydroxymethylimidazole. As such a hardening accelerator, 2,4,6-tris(dimethylamine) Methyl)phenol or 2-methylimidazole is preferred. The amount of such hardening accelerator is 11 by mass relative to 1 part by mass of the polyamidene polyoxyl resin and the total amount of the epoxy compound. When the amount is more than 10 parts by mass or more, the operable period of the composition is deteriorated. The composition of the present invention is excellent in workability, and a varnish dissolved in a solvent can be used. The component may be compatible. Examples of suitable solvents include ethers such as tetrahydrofuran and anisole; cyclohexanone '2-butanone, methyl isobutyl ketone, 2-heptanone, and 2-octene ketone. Ketones such as acetophenone; esters of butyl acetate, methyl benzoate, 7-butyrolactone, etc.; butyl cellosolve acetate, propylene glycol monomethyl ether acetate, etc.-16-200927795 Cellulose ; N,N-dimethylformamide 'N,N-dimethylacetamide, N-methyl-2-pyrrolidone and other amides and aromatic hydrocarbons such as toluene, xylene, etc. Classes, esters and cellosolves are preferred, with cyclohexanone, r-butyrolactone, propylene glycol monomethyl ether acetate, N-methyl-2-pyrrolidone good. These solvents may be used alone or in combination of two or more. The amount of the solvent to be added to the composition of the present invention is usually in the range of 1 to 40% by weight based on the solubility of the resin, the workability at the time of coating, the thickness of the film, and the like. When the composition is stored, a higher concentration can be prepared in advance and diluted to the desired concentration when used. Other heat conductive materials, anti-aging agents, ultraviolet absorbers, adhesion improvers, surfactants, storage stability improvers, ozone deterioration preventers, light stabilizers may be added without damaging the object of the present invention. , tackifiers, plasticizers, decane crosslinkers, antioxidants, thermal stabilizers, conductivity imparting agents, antistatic agents, radiation blocking agents, nucleating agents, slip agents, pigments, metal passivators, physical property adjusters, etc. . The polyimine polyoxymethylene resin composition of the present invention is applied to a substrate, and when the solvent having a low boiling point is used, the solvent is volatilized at a temperature of 80 to 120 ° C, and may be about 1 500 to 2 0 0. The temperature of °C is heated for 1 to 4 hours to harden. The obtained cured film has low flexibility and low flexibility. Since it has both flame retardancy, solvent resistance and heat resistance, it can be effectively used as a protective film for various electrons, electrical components or substrates. Embodiments -17- 200927795

It is limited to the following embodiments. I. Synthesis of Polyimine Polyoxyl Oxide [Synthesis Example 1] 3, 3', 4 in a flask equipped with a 3, 3, 4 thermometer and a nitrogen substitution device equipped with a stirrer and a thermometer 35_8 g (0.1 mol) , 4'-diphenylphosphonium tetracarboxylic dianhydride and 4 〇〇 〇 〇 n_methyl_2·pralines. Next, 'adjust the dissolved 90.9 g (0.075 mol) of the diamine oxirane of formula (19), 5.4 g (0.025 mol) of 4,4'-(3,3'-dihydroxy)diamine. The solution of the phenyl group in the 11-methyl-2-pyrrolidone of 1 § 'make the temperature of the reaction system not more than 5 Torr, and drip into the above flask. After the completion of the dropwise addition, the mixture was further stirred at room temperature for 1 hr. Next, a reflux condenser equipped with a water receiving container was placed in the flask to add 30 g of xylene, and the temperature was raised to 150 ° C, and the temperature was maintained for 6 hours to obtain a yellow-brown solution. After cooling the thus obtained solution to room temperature (25 ° C 〇), it was added to methanol, and the resulting precipitate was dried to obtain repeating units represented by the following formulas (20-1) and (20-2), respectively. The resulting polyamidene polyoxyl resin.

Ch3 D-Si-CH2CH2CH, NH, (19) 03⁄4

-18- 200927795

When the infrared absorption spectrum of the obtained resin was measured, the absorption based on the unreacted poly-proline was not observed, and it was confirmed that the absorption was based on the quinone imine group at 1,780 cm·1 and 1,7 20^^1. The weight average molecular weight (polystyrene conversion) of the resin was measured by a gel permeation chromatography (GPC) using tetrahydrofuran as a solvent to 40,000. Further, the amount of ruthenium measured by the ashing method was 16% by weight, and the amount of diphenyl siloxane in the oxirane was determined by 29 Si_NMR to be 30% by mole. This resin is a polyimine resin (a). [Synthesis Example 2]

In a flask equipped with a stirrer, a thermometer and a nitrogen substitution device, 35.86 (0.1 mol) of 3,3',4,4'-diphenyltrifluoride dianhydride and 4008 of η-methyl-2-pyrrolidone were added. . Next, the 4,4'-(3,3'-dihydroxy)diamine dissolved in 73.5 g (0.06 mol) of the diamine oxirane of the formula (21) and 4.3 g (0.02 mol) were dissolved. a solution of bisphenyl and 8.2 g (0.02 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane in 1 g of η·methyl-2-pyrrolidone, The temperature of the reaction system was not more than 5 Torr, and it was dropped into the above flask. After the completion of the dropwise addition, the mixture was further stirred at room temperature for 10 hours. Next, after installing a reflux condenser with a water receiving container in the flask, 30 g of xylene was added, and the temperature was raised to 150 ° C, and the temperature was maintained for 6 hours to obtain a yellow-brown solution. After cooling the thus obtained solution to room temperature (25 ° C -19-200927795), it is added to methanol to 'dry the obtained precipitates' to obtain the following formulas (22-1), (22-2), ( 22-3) The polyimine polyfluorene resin formed by the repeating unit shown.

(22-3) ❹ When the infrared absorption spectrum of the obtained resin was measured, the absorption based on the unreacted poly-proline was not observed, and it was confirmed that the absorption was based on the ruthenium group at 1,780 cm·1 and 1,720 cm-1. When the weight average molecular weight (in terms of polystyrene) of the resin was measured in the same manner as in Synthesis Example 1, it was 39,000. Further, the amount of ruthenium measured by the ashing method was 14% by weight, and the amount of diphenyl siloxane in the oxirane was determined by 29Si_NMR to be 29 mol%. This resin is a polyimine resin (b). -20- 200927795 [Synthesis Example 3]

In a flask equipped with a stirrer, a thermometer and a nitrogen substitution device, 44.4 g (〇.l mole) of 4,4'-hexafluoro-p-propyl bisphthalic acid dianhydride and 4 〇Og of η-methyl group were added. 2_pyrrolidone. Next, the 2,2-bis[4-(4-aminobenzene) dissolved in 95.4 g (0.075 mol) of the diamine oxirane of the formula (23) and 103 g (0. 〇25 mol) were dissolved. A solution of oxy)phenyl]propane in 1 〇〇g of η-methyl-2-pyrrolidone, such that the temperature of the reaction system does not exceed 50 ° C, is dropped into the above flask. After the completion of the dropwise addition, the mixture was further stirred at room temperature for 1 hour. Next, after installing a reflux condenser with a water receiving container in the flask, 30 g of xylene was added, and the temperature was raised to 15 (rc, and the temperature was maintained for 6 hours to obtain a yellow-brown solution. The solution thus obtained was cooled to room temperature ( After 2 5 ° C), it is added to methanol and the resulting precipitate is dried.

At the time of 'polyimide polyoxyl resin which was formed by the following formula (2 4 - 1 position)

, (24-2), repeat 单 OH, -Si-ch2ch2ch: nh, (23) CH.,

(24-2) -21 - 200927795 When the infrared absorption spectrum of the obtained resin was measured, absorption based on unreacted poly-proline was not observed, and it was confirmed that the absorption was based on yttrium imine at 1,780 cm·1 and 1,720 cm·1. . When the weight average molecular weight of the resin (in terms of polystyrene) was measured in the same manner as in Synthesis Example 1, it was 39,000. Further, the amount of oxime measured by the ashing method was 14% by weight. The amount of diphenyl decane in the oxirane was determined by 29si-NMR to be 30 mol%. This resin is a polyimine oxime resin (C). [Synthesis Example 4] In a flask equipped with a stirrer, a thermometer, and a nitrogen substitution device, 35.8 § (0.1 mol) of 3,3',4,4'-diphenyltetracarboxylic dianhydride and 30 〇8 were added. Η-methyl-2 - 啦略院嗣. The acceptor's adjustment of 63.0 g (0.075 mol) of the diamine oxirane of formula (25), 5.4 g (0.025 mol) of 4,4'-(3,3'-dihydroxy) A solution of the aminobiphenyl in 1〇(11-methyl-indole-2-pyrrolidone) such that the temperature of the reaction system does not exceed 50 ° C, and is dropped into the above flask. After the completion of the dropwise addition, the mixture is further stirred at room temperature. 10 hours. Next, after installing a reflux condenser with a water receiving container in the flask, 30 g of xylene was added, and the temperature was raised to 15 (TC, and the temperature was maintained for 6 hours to obtain a yellow-brown solution. The solution thus obtained was cooled to After being added to methanol at room temperature (25 ° C), the obtained precipitate is dried to obtain a polyimine polyamine which is obtained by repeating units represented by the following formulas (26-1) and (26-2), respectively. Oxygenated resin. -22- 200927795 CH, /ch,\ch,

Si-C 十 Si O 十 Si-CH2CH2CH: NH2 (25) CH., XCHysCH.,

When the infrared absorption spectrum of the obtained resin was measured, the absorption based on the unreacted poly-proline was not observed, and the absorption of UeOcnT1 and 1,720 cm-1 based on the quinone imine group was confirmed. When the weight average molecular weight (in terms of polystyrene) of the resin was measured in the same manner as in Synthesis Example 1, it was 40,000. Further, the amount of ruthenium measured by the ashing method was 20% by weight. This resin is a poly-gumamine resin (d). [Synthesis Example 5] 35.8 g (0-1 mol) of 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride and 3 〇0 g were placed in a flask equipped with a stirrer, a thermometer, and a nitrogen substitution device. N-methyl-2-pyrrolidone. Next, 'adjust and dissolve 66.6 g (0.075 mol) of the diamine oxirane of formula (27), 5.4 g (0.025 mol) of 4,4,-(3,3,-dihydroxy)diamine. a solution of phenyl in 1 〇 (^ 11-methyl-2-pyrrolidone such that the temperature of the reaction system does not exceed 50 t, and -23-200927795 is added to the above flask. After the completion of the dropwise addition, further Stir at room temperature for 1 hour. Then, after installing a reflux condenser with a water receiving container in the flask, 30 g of xylene was added, and the temperature was raised to 150 ° C, and the temperature was maintained for 6 hours to obtain a yellow-brown solution. After the solution thus obtained is added to room temperature (25 ° C), it is added to methanol to "dry the obtained precipitate" to obtain repeating units represented by the following formulas (28-1) and (28-2), respectively. Polyimine polyoxymethylene resin.

PS-2)

When the infrared absorption spectrum of the obtained resin was measured, the absorption based on the unreacted polyimidic acid did not occur, and it was confirmed that the absorption was based on the iminoimine group at 1,780 cm·1 and 1,720 cm·1. When the weight average molecular weight (in terms of polystyrene) of the resin was measured in the same manner as in Synthesis Example 1, it was 39,000. Further, the amount of ruthenium measured by the ashing method was 19% by weight. This resin is a polyimine resin (e). -24- 200927795 [Synthesis Example 6] In a flask equipped with a stirrer, a thermometer, and a nitrogen substitution device, 35.8 g (〇.l mole) of 3,3,4,4,diphenyltriamine tetracarboxylic acid was added. Anhydride and 4 〇〇g of η-methyl-2-pyrrolidone. Next, 4,4'-(3,3) of the diamine-based oxirane represented by the above formula (19) dissolved in 243 g (〇〇2 mol), 1 〇.8 g (〇.〇5 mol) was adjusted. '-Dihydroxy)diaminobiphenyl and 123g (003 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propene in i〇〇g φ η-甲A solution of pyridine-2-pyrrolidone was introduced so that the temperature of the reaction system did not exceed 50 ° C and was dropped into the above flask. After the completion of the dropwise addition, the mixture was further stirred at room temperature for 10 hours. Next, after installing a reflux condenser with a water receiving container in the flask, 30 g of xylene was added thereto, and the temperature was raised to 150 ° C, and the temperature was maintained for 6 hours to obtain a yellow-brown solution. The solution thus obtained is cooled to room temperature (25: (:), and added to methanol to 'dry the obtained precipitate' to obtain the following formulas (29-1), (29-2), (29-3, respectively). The polyimine polyfluorene resin formed by the repeating unit shown.

-25- 200927795

When the infrared absorption spectrum of the obtained resin was measured by SiCH2 (H2CHr-CHj (29-3), the absorption of the poly-proline was not observed based on the unreacted oxime, and it was confirmed that it was 1,780 cm·1 and 1,720 cm·1 based on the quinone imine. In the same manner as in Synthesis Example 1, when the weight average molecular weight (in terms of polystyrene) of the resin was measured, it was 31, 〇00. Further, the amount measured by the ashing method was 7 wt%, and 29Si-NMR was used. The amount of diphenyl sulfoxane in the oxalate was measured to be 30 mol %. The resin was used as the polyimide resin (f). The resin composition was prepared to prepare each resin composition having the composition shown in Table 1, The method is evaluated by ©. In addition, the parts in the table are all parts by mass. Evaluating the flame retardancy on the steel plate coated with the release agent, coating each polyimine polysiloxane resin composition so that the thickness after drying is 100/zm, heated at 8 〇t for 3 , minutes, and then heated by 18 (TC for 1 hour to form a polyimide film hardened film. For the obtained test piece 'qualified by UL94 flame retardancy test v_0 benchmark, evaluation Flame retardant -26- 200927795 Elasticity will be applied to the steel coated with release agent Coating each polyimine polyoxymethylene resin composition so that the thickness after drying is 1 0 0 /Z m, heating at 80 ° C for 30 minutes ' and then heating at 180 ° C for 1 hour to form poly The amine resin cured film was measured by a tensile mode of a viscoelasticity measuring device DMS6100 (manufactured by Seiko Instruments Co., Ltd.) to determine the storage modulus of 25 t. © Evaluation of adhesion on a copper substrate and an aluminum substrate, respectively, coating each polyimine The polyoxyxylene resin composition was dried to a thickness of 100 " m, heated at 80 ° C for 30 minutes, and further heated at 18 ° for 1 hour to form a polyimide film of a polyimide resin. For this test piece, The checkerboard peeling test (JISK5400) was carried out to evaluate the adhesion. The number 値 (molecular/denominator) in Table 2 indicates the number of divisions (molecular) per division number of 100 (denominator), that is, 1 0 0 /1 00 means that it is not peeled at all, and 0/100 means that it is completely peeled off. ❹ -27- 200927795 [1« Solvent (parts) 〇〇〇 inch inch Ο ο ο inch ο inch ο inch Ο ο Ο ο ο Ο XUXU ffi U Κ U ffi υ κ υ ffi υ υ a υ υ pin ~ m ^ uni 1 1 (N 〇 (N 〇1 1 1 1 1 1 CN ο (Ν (Ν Ο 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 ^js g 1 1 1 1 1 1 Organic peroxide (parts) 1 1 1 1 1 1 1 1 1 1 1 1 I 1 1 1 1 1 1 1 1 1 1 1 1 1 1 3 1 1 1 1 1 1 0 1 1 1 1 1 1 1 1 1 Epoxy resin (parts) 1 1 1 W- ) 1 1 1 1 1 1 ^Ti yri 1 1 1 t 1 1 1 1 1 1 1 1 1 1 1 S 0 1 1 1 1 1 1 Flame retardant (parts) 1 1 1 ίΤί ο m in 3 1 1 1 3 3 3 Polyimine polyoxane (parts) 〇〇ο Τ·*Η ο ^•Η ο Τ*"Η ο τ~Η Ο ο ο ο 3 SWWS Example 1 Example 2 Implementation Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Reference Example 1 Reference Example 2 00 .. s ##«&-: (6 <nfin.· -cI - s Guanxixi 111: (3) -28- 200927795 [Table 2] Flame retardant storage elastic modulus (MPa) Moisture-resistant adhesive moisture-resistant adhesive copper aluminum copper aluminum Example 1 Qualified 150 100/100 100/100 100/100 100/ 100 Example 2 Qualified 170 100/100 100/100 100/100 100/100 Example 3 Qualified 420 100/100 100/100 100/100 100/100 Example 4 Qualified 80 100/100 100/100 100/100 100 /100 Comparative Example 1 Failed 150 100/100 100/100 100/100 100/100 Comparative Example 2 Unqualified 50 100/100 100/100 100/100 100/100 Comparative Example 3 Unqualified 70 100/100 100/100 100/ 100 100/100 Comparative Example 4 Qualified 2200 100/100 100/100 100/100 100/100 Reference Example 1 Film is brittle and cannot be measured Reference Example 2 A uniform test piece cannot be obtained but cannot be measured. As can be seen from Table 2, it is known from the present embodiment. Any of the cured films obtained from the composition has a low modulus of elasticity and is excellent in flame retardancy. On the other hand, the compositions of Comparative Examples 2 and 3 did not contain a phenyl group and were inferior in flame retardancy. The polyamidene polyoxymethylene resin in the composition of Comparative Example 4 had a small amount of ruthenium, and the cured product had poor flexibility. Since the composition of the reference example 1 has a small polymer content, the strength of the coating film is insufficient, and the composition of Reference Example 2 is precipitated as a flame retardant magnesium hydroxide in the composition, and a uniform cured product cannot be obtained. Can't get meaningful data. Industrial Applicability The polyimine resin composition of the present invention is effective as a protective film for electrons, electrical components, or substrates that require flame retardancy. -29-

Claims (1)

200927795 X. Patent Application No. 1_ A composition characterized in that (A) is a polyamidene polyoxyn resin and (B) a flame retardant, wherein the (A) polyamidene polyoxyl resin contains (A) The weight of the polyfluorene iodide resin is 1 〇 25% by weight of the ruthenium atom 'and 5 to 70 mole % of the organic group bonded to the ruthenium atom is phenyl' relative to 100 parts by mass (A) (B) The flame retardant is 1 to 2 parts by mass. 2- The composition of claim 1, wherein the (A) polyamidene polyoxyl resin is formed by two repeating units represented by the following formula (1), 0II .C 0 / \ / \ _N X 广Υ· c C 0 0 Ο 0II II 八/c\ Vx\ /Ν—ζ· c cII II ο ο η (i) [In the formula (1), the χ is a tetravalent organic group, and the γ system is not a divalent organic group containing a ruthenium atom, η is a number of 0.4 to 0.8, and n+m=l, ψ/ψ\/(^\ ψ -CH2CH2CH2-(4) 卜CH2CH2CH2- (2) R2 \ R4/a\( ^j/b R6 2 is a divalent group represented by the following formula (2), and the number of carbons other than the phenyl group in the formula (2), R1 to R6, is a substituted or unsubstituted one-valent hydrocarbon group of 8 to 8 , a and b are each an integer of 丨~40, but a+b is an integer of 2 to 50, 0.1Sb/(a+b) $〇_8)]. -30- 200927795 3. As claimed in the patent scope The composition according to Item 1 or Item 2, wherein (B) the flame retardant is at least one selected from the group consisting of triphenyl phosphate, tricresyl phosphate, tricresyl phosphate, and tolylphenyl phosphate. For example, the composition of the first or second aspect of the patent application contains 5 parts by mass of the (A) polyamidene polyoxyl resin. 2 5 parts by mass of (B) flame retardant 5. For the composition of the first or second paragraph of the patent application, wherein Ο (A) polyiminoimine polyoxyl resin has a weight average measured by GPC The molecular weight (in terms of polystyrene) is 5,000 to 150,000. 6 · The composition of the second item of the patent application, wherein the Z system is represented by the following formula: (In the formula (3), regarding Ri to R6 and b, as defined above, al and a2 are integers of 1 to 40, but al + a2 + b is an integer of 2 to 50, 0.1^a2/(al+ A2+b) '0.6). 7. The composition of claim 2, wherein at least a portion of γ is a divalent group represented by any one of the following formulas (14) to (18), -31 - 200927795 OH OH OH OH o O -s- -0- (18) 8 · The composition of claim 6 of the patent application, which further contains a catalytic amount of (C) organic peroxide. -32- 200927795 9. The composition of claim 7, wherein the composition further comprises a phenolic hydroxyl group in the (A) component of 1 mole, and the amount of the epoxy group is 0.2 to 10 moles (D). An epoxy resin, and (E) an epoxy resin hardening accelerator 〇1 〇. A film formed by hardening a composition according to any one of claims 1 to 9. ❹ -33- 200927795 VII. Designated representative map: (1) The representative representative of the case is: None (2), the representative symbol of the representative figure is simple: No 8. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: none