TWI320045B - Solvent-free polyimidesilicone resin composition and a resin film composed of the same - Google Patents

Description

1320045 IX. Description of the invention: : [Technical field to which the invention belongs]: The present invention relates to the usefulness of the coating as a coating, a solvent-free polyamine, and an agent. Resin film.糸 '糸,, and, and hardened the composition - [prior art] - general 'because of the high heat resistance of the polyurethane resin... P brush circuit substrate or heat-resistant adhesive tape: material : Excellent as a resin varnish, it can also be used as a solvent for the electric 'face protection film, the sound is sewed and the 丄 丄 飞 飞 飞 飞 体 体 体 体 体 体 体 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚Bathing in various organic solvents, the polyaminic acid belonging to the precursor of the enamide is coated on the substrate, and the amine is cyclized to obtain the polyfluorene fnnI. μ, the hunter is treated by the same shirt to make it dehydrated. The method of polnmide resin. In addition, the method of "concentration of 提 醯 = 对 对 对 对 = = = = = = = = = 。 。 。 。 。 。 。 。 。 。 。 。 。 However, in this case, when a general-purpose method uses an α-imine resin, it is necessary to use a solvent to be diluted. In the case where the polyi imine resin is subjected to a coating operation or the like, a step such as heating is required for the solvent, and countermeasures against the exhaust gas or the like are also required. "Where/thin, in the composition of the polyamidoxime-based resin, it is proposed to use various kinds of (meth) (tetra) acid compounds which are pre-mixed with a reactive compound as a release agent. The solvent-free type of polyacetimimine 317457 6 1320045 eucalyptus composition (refer to the patent document 丨) which does not require a solvent removal step after the work, such as ', cloth, etc. When it is necessary to use a portion having such a thick resin composition, since the polyimine oxime ketone resin has a coloring property, the illuminating light 35 does not sufficiently penetrate the deep 4' when photohardening is performed, so that it is not sufficiently hardened. [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei 2 No. Hei. No. 2-3323〇5 SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] The present invention has been developed in view of the above circumstances to provide a kind of The imine (iv) resin composition is solvated to omit the removal of the solvent = process '^ can impart high adhesion to various shapes of the substrate and can be obtained; the thickness of the polysimine (four) resin composition, and The composition is hardened For the purpose of the present invention, the use of the above-mentioned members is also the object of the present invention. i...Μ ▲This article can use the hardened leather f'-type printed circuit board or heat-resistant adhesive tape, etc. A surface protective film, an interlayer insulating film, etc., which are made of a gas-receiving member and a semiconductor material, etc.... This is a person who has achieved the above-mentioned purpose, and has been dedicated to the present, and has been known as a poly-iminoleone. • The use of reactive diluents in the composition of the threshold 糸M 曰 可 可 可 基材 基材 基材 基材 基材 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应The inventors discovered that the coloring of the bismuth fluorene ketone resin and the structure of the light absorbing structure can produce the desired thickness of the 贝 而 元 成本 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 本 本 本 本 本 本 本The result of intensive research to achieve the above objectives is 317457 7 1320045. The fact that the specific molecular structure is introduced into the polyimine resin can achieve the above purpose. The light transmittance of the thinner Π1Π to π0· is (4) , (8) reactive month, and (c) light Seal initiation agent 'and contains substantially no solvent,

That is, the present invention provides a solventless resin composition and a resin film using the same, characterized in that it contains at least (a) having the following - (1-1) and Π-2) The repeating unit of the chitosan resin, which is measured on the ancient glass substrate with a thickness of 1 〇Mm.

(1-1)

, X is a tetravalent right-handed y W with organic oxime 俨έ 槿 earth, a divalent organic aryl lactane, and a divalent organic group of 纟°. 317 317457 8 1320045 The general formula (2) and the formula (1) and (1-2) are preferably those represented by (3), (4) or (5).

N2c~c~^~CB (2)

44)

It is preferably a polyimine sulfonate resin, and the z-system in the general formula (1 - 2) is 30% by mass in a ratio of 2, and the diamine residue R1/ represented by the formula (6) R3\ -CH2CH2CH2-Si4〇-Si-}-CH2CH2CH2- R2 \ R4/ (6) (wherein R1 to R4 are carbon number 1 to Saai a 僧勹di double 1 main 8 substitution or #substituted 〆仏The hydrocarbon group, * such hydrocarbon groups may be the same or different; and &amp; is an integer of 100 or more and i or more). ' 9 317457 1320045 A further preferred reactive diluent (T-based) acrylic compound. More preferably, the photopolymerization initiator is selected from the group consisting of acet〇phen〇ne Hebi, benz〇phen〇ne derivatives, benzoin ether derivatives, A photopolymerization initiator in a group of oxime (xan let one) derivatives. [Effects of the Invention] - The polyimine fluorenone resin composition of the present invention contains substantially no solvent in the use of a reactive diluent in the polyamidoxime ketone resin, so that the solvent can be removed. The process can also impart high standing to the various shapes of the substrate, and the desired thickness can be obtained because the polyamidoxime resin does not hinder the photohardening of the reactive diluent. [Embodiment] Hereinafter, the present invention will be described in detail. The polyimine fluorenone resin having the units of the general formulae (1-1) and (1-2) related to the present invention can be obtained by reacting an acid dianhydride with a diamine and a diamine sulfoxane. . The polyamic acid imide resin of the present invention is characterized in that it does not hinder the light absorption of the photopolymerization initiator, and the tetracarboxylic dianhydride as a raw material thereof is preferably light absorption in the ultraviolet to visible light field. Less, or difficult to form a charge transfer c〇mplex after ruthenium imidization. The aliphatic tetracarboxylic dianhydride or the alicyclic tetracarboxylic dianhydride is preferred insofar as it does not interfere with light absorption. The aliphatic tetracarboxylic dianhydride may, for example, be butane-1, 2丨3' 4-tetracarboxylic dianhydride or pentane ruthenium, 2, 4, 5-tetracarboxylic dianhydride or the like, and an alicyclic ring. The tetracarboxylic dianhydride of the formula may, for example, be 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 317457 10 1320045 cyclohexane-1,2,4,5-tetracarboxylic dianhydride, two Cyclohexyl-3,4,3,,4,-tetracarboxylic acid two-needle, ring [2·2.1]g-burning-2, 3, 5, 6-tetra-retensive dianhydride, 2, 3, 4 5~ Tetrahydrofuran tetracarboxylic dianhydride, bicyclo[2·2.2]-oct-7-ene-2, 3,5,6-tetracarboxylic dianhydride, and the like. It is also possible to use 1,3,3a,4,5,9b-hexanitro-5-(tetrahydro-2,5-di.indolyl-3-furanyl)-naphtho[u-c]furan-u- Diketone, nhjj, 9b-hexahydro-5-methyl-5-(tetrahydro-2,5-dioxo-3-indolyl)-naphtho[1,2-c]furan-indole, 3- An aliphatic tetracarboxylic acid diruthenium anhydride having an aromatic ring such as a diketone. Further, an aromatic tetracarboxylic dianhydride which is more excellent in heat resistance can be used without hindering the light absorption range of the photopolymerization initiator. The aromatic tetracarboxylic dianhydride may, for example, be pyromellitic dianhydride, 3, 3, 4, 4, diphenyl ketone tetracarboxylic acid monohydride, 3'3', 4, 4'-diphenyl Ethyl ether tetracarboxylic dianhydride, 4,4, hexafluoropropylene bismuthic acid dianhydride, 3, 3, 4, 4, _ dibenzoquinone tetrazoic acid dioxane and the like. These tetracarboxylic acid dianhydrides may be used singly or in combination of two or more. Among the other amines, it is preferred that the light absorption in the ultraviolet to visible light field is further difficult to form a charge transfer complex after imidization. It is preferable that the k-light absorption aspect is preferably an aliphatic diamine, but an aromatic aliphatic diamine which is more excellent in heat resistance can be used without hindering the light absorption range of the photopolymerization initiator. Tetramethylenediamine, u_diamine=, and !'4,-diaminodicyclohexylamine, etc., aromatic diamine, amine phenyl)propane, etc., can be used alone in the base _, 2 , 2 - double (4) is used in the form of J alone or in combination of two or more. In another aspect, in the present invention, a # ro oxirane residue. The diamino group 1320045 (6) represented by the general formula (6) (h2ch2ch2 - <= CH2CH2CH2_ wherein R i R4 is an unsubstituted or substituted monovalent hydrocarbon group having from 1 to 8 carbon atoms, For example, 'cycloalkyl, such as methyl, ethyl, propyl, butyl, pentyl, .2, etc., cycloalkyl, cyclohexyl, etc.; phenyl, xylyl-yl, fluorenyl An aralkyl group such as phenethyl, a 3, 3, 3_trifluoropropyl group, a 3' gas propyl group or the like, a 2-indolyl group such as 2-(trimethoxysulphonyl)ethyl In addition to the AM group, etc., an oxy group such as a methoxy group, an ethoxy group or a dioxy group, an aryloxy group such as a phenoxy group, or the like may be mentioned. Among them, a mercapto group or an ethyl group is preferred. Or a base of the formula (8) is an integer of i or more and ≤ or less. In the present invention, the polystyrene resin having a unit of the general formula (H) and (1-2) has a oxy-oxygen burn. The ratio of the part to the Z is preferably 30 Å or more, preferably 40% by mass or more. When the amount is not more than 3% by mass, the "water-removing imine (tetra)-based resin composition is difficult to dissolve = undrained when hunger. Furthermore, the upper limit can be appropriately adjusted to the ratio of the oxygen-burning component to the brewing In the amine ketone resin, 'lower: especially in the amount of (four) % or less. Therefore, in the above general formula (H): 1 2 wide and early (1_1) molar ratio, p ' and unit (b 2) Mohr == sub-amount of the organic portion of the resin is selected as in the above-mentioned dry circumference ' and q / (p + q) is preferably 〇 0.85. To 0.95, especially 〇.2 to 'polyacid The weight of the acetophenone resin is particularly 1., _ to 7 〇, _ is: the average molecular weight is 5'_ to ..., preferably. If the molecular weight is 5, 〇〇0 31745 12 1320045, the iron is below, then The hardened film obtained by the polyimine fluorenone resin composition is brittle, and when the molecular weight is 100 Å or more, the compatibility with the acrylic compound is deteriorated. Polyimine hydrazine _ resin manufacturing method According to a well-known method, first, the acid dianhydride, the diamine and the diaminopolyoxane are fed to the solvent, and the low temperature is reacted at a degree of 2G to 5G ° C to produce a polystyrene. The precursor of the amine resin is poly-branched acid. Secondly, the obtained poly-branched acid solution is warmed up, preferably 80 to 2 Torr (rc, particularly preferably 14 〇 to 18 〇. 〇 temperature, | Polyamide The amine can be subjected to a dehydration ring-closing reaction to prepare a solution of a polyamine resin, and the solution is poured into water, methanol, ethanol, acetonitrile, etc., and the diatoms are dried to form a polyimine stone. Ketone resin. Herein, the total of the diamine and diamine-based polyaniline of tetradecanoic dianhydride: 'It is preferable to use a specific molar ratio according to the molecular weight of the produced polyamidoxime resin. 〇. 95 to h 05, especially good at 0.98 to

The scope. Further, the solvent used in the production of the polyamidoxime resin may, for example, be NN, N_, methyl-2-pyrrolidone, cyclohexanone, butyrolactone, ._4 ~~ '&quot; Wait. In addition, if you use together a mixture of toluene, diphenylbenzene, etc., ubene is easy to remove the imidization from the sea, you can use it alone! Two or more types are combined or combined. As the molecular weight of the polyamidite resin, it is also possible to add an amount of a monofunctional compound such as an acid or an aniline. In this case, the oxime oxime ketone resin is preferably 2 mol% or less. In the process of I imidization, a dehydrating agent and a ruthenium hydride 31745 13 ^ 1320045 catalyst are used, and if necessary, it can be imidized by heating to the left and right. In this method, as the dehydrating agent, for example, an acid anhydride such as acetic anhydride, dipropionic anhydride or difluoroacetic anhydride can be used. The amount of the dehydrating agent to be used is preferably from 1 to 1 mole per mole of the female 1 molar. As the brewing imidization catalyst, a tertiary amine such as a bite, a collidine, a dimethyl lint, or a diethylamine can be used. The amount of the ruthenium-based catalyst used, • relative to the dehydrating agent used, i.e., 5 to 1 Torr is preferred. The brewing imidization method is effective because the reaction liquid does not pass through the high temperature during the process, and the resin is not easily colored. The method of using at least one of a plurality of kinds of diamines and tetracarboxylic dianhydrides is not particularly limited, and examples thereof include a method in which all the raw materials are previously mixed and then copolymerized and condensed, and two or more kinds of the materials to be used are used. A method in which a diamine or a tetrabasic acid dianhydride-side is separately added to the reaction while being sequentially added. The polyimine fluorenone resin of the present invention thus synthesized is obtained by forming a film having a thickness of nick m on a quartz glass substrate, and having a wavelength of 35 〇 nm 纟 45 〇 nm in the visible Lu light absorption spectrum. The wavelength range is more than 80%. In the polyamidite composition of the present invention, a reactive diluent is further formulated. The reactive diluent can be a "methicone-like (meth)acrylic acid compound, an ethylene-based compound, etc., as long as it can be reacted by a photopolymerization initiator described later. In many cases, a mercapto)acrylic compound is preferred. Such a (meth)acrylic acid compound means = 夂酉曰 'methacrylate, acrylamide, methacrylamide, etc., ruthenium; valley % of the above-mentioned poly-imine alloy steel resin. 317457 14 1320045 The following: 1: The (meth)acrylic compound of the present invention is preferably used in the form of (meth) acrylate, or (meth) propylene as shown by - (6) CH2-CR3C00R2 (7) CH2=CR3C0NR2 ... \〇) (wherein R2 represents an alkyl group, preferably an alkyl group having a carbon number of i to 20, 10 to 10. R3* + 3 shop bucket, w 甘, 仏 仏 two i κ clothing not atom or sulfhydryl). Specific examples of the acrylic acid represented by the general formula (7) include acrylium acrylate, isobutyl acrylate, isobornyl acrylate, and the like. Examples of the decyl acrylate represented by the general formula (8) include N N — dioxin, acrylamide, N, N-diethyl acrylamide, and the like. , - In the general formula (7) and (8), the compound wherein R3 is a methyl group, that is, a mercaptopropane: acid compound, may be exemplified by methacrylic acid, methyl propyl methacrylate.酉夂 酉 、, methyl acetoacetate isobornyl, methyl propyl hydrazine = glycidyl glyceride, methyl methic acid 3, 4 - epoxy cyclohexyl ester, methacrylic acid Ethyl ester, 2-hydroxypropyl methacrylate, 2-yl butyl hydrazide, trifluoropropyl methacrylate, perfluorobutyl methacrylate, perfluorooctyl methacrylate An organic polyoxane having a methacryl group or the like. Further, as the acrylic compound, in order to improve the adhesion to the substrate or to improve the physical properties, a vinyl compound such as N_ethylglycol oxime or the like; a glycidyl acrylate/acrylic acid 3 may be suitably used. 4_Epoxycyclohexylmethyl (4) (4) acid compound containing epoxy group; 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, etc. hydroxy containing 317457 15 1320045 = 鲛化 & A fluorine-substituted alkylacrylic acid compound such as trifluoropropyl acrylate, perfluorobutylethyl acrylate, propylene oxide or perfluorooctylethyl acrylate, or an organic polyoxyalkylene having an acrylic group. The specialized s objects can be used singly or in combination of two or more. &quot; It is known that the addition of an alkoxysilane containing a (fluorenyl) acrylonitrile group as a component (b) may suppress the turbidity of the hardened film after light irradiation, and therefore is a useful raw material in the present invention. Specifically, propylene oxypropyl monooxane, propylene oxypropyl fluorenyl dimethoxy decane or the like propylene decane or methacryl methoxypropyl trioxane oxime, methyl propylene Methyl propylene decyl decane such as methoxypropyl methyl dimethoxy decane. The alkoxysilane containing a (meth) acrylonitrile group is added in a proportion of from 0 to 200 parts by mass, preferably from 1 part by mass to 1 part by mass, based on the mass% of the (poly)imine fluorenone resin. In addition, as the component (b), in addition to the mono(meth)acrylate, in order to improve the strength and adhesion, it is also possible to add di(meth)acrylate, multi-parametric B b (methyl) propyl. The composition of the present invention contains a photopolymerization initiator, and is preferably selected from the group consisting of an acetophenone derivative, a benzophenone derivative, and a benzoin ether from the viewpoint of productivity and rapid hardening. A photopolymerization initiator in a derivative or a xanthone derivative. Specific examples thereof include diethoxyethyl benzene, 2-hydroxy-2-methyl phenylpropan-1-one, and 2, 2-Dimethoxy-2-phenylethyl benzene, hydroxy-cyclohexyl ketone, isobutyl styrene ether, benzoin methylation, thioxanthone, isopropyl thiophene Tons of ketone, 2-methyl(methylthio)phenyl]-2-morpholinylpropane-ketone, 2_〒·yl 2_didecylamino-^ 317457 16 1320045 morpholinylphenyl)butanone -1, etc. ;· The ratio of the quinone imine ketone resin, the reactive diluent, and the photopolymerization / - J can be any ratio, but the preferred ratio is 100 parts by mass relative to (a) • ^ 醯 = acesulfame resin ( b) the reactive diluent is 20 to Bailey, and (c) the photopolymerization initiator is 1 to 200 parts by mass. More preferably, the ratio is 1 part by mass relative to the polyamidoxime resin. (5) The reactive thin-release agent is 30 illusions by mass, and (c) the photopolymerization initiator is 2 parts by mass. § When the polyimine oxime resin composition of the present invention is used continuously: Use a solid shape such as 臈 to perform photohardening, but it is preferable to have fluidity at 25 c from the viewpoint of easy handling. Specifically, the viscosity at 25 ° C is preferably i 〇〇〇〇 Pa · 5 or less, more preferably 〇 1 to 5000 Pa · s, particularly preferably from 0.1 to lOOOPa · s. Further, the base material to which the polyimine fluorenone resin composition of the present invention can be applied is a metal such as iron, copper, ruthenium or ruthenium, and may be an inorganic substance such as glass, or may be an epoxy resin. An organic resin such as an acrylic resin. The polyimine fluorenone-based resin composition of the present invention has the disadvantage of improving the solvent-dilution of the polyamidoxime varnish to date, since the (meth)acrylic compound which is itself a reactive compound is used as a diluent. Therefore, it becomes a composition of a polyamidene resin which does not substantially contain a solvent. Further, since the polyimine fluorenone resin in the present invention does not inhibit photopolymerization of the reactive diluent, the composition of the polyamidite resin of the present invention can be easily produced by light curing. A polyimide ketone/(meth)acrylic resin film having a desired thickness is obtained, and thus, the present invention is suitable for: 3] 7457 1320045, an electric and electronic device, a bulk wafer station or a coating material, and the like. [Embodiment] [Embodiment] The present invention is not limited to the following embodiments, and the present invention is not specifically described below. The embodiments are specifically described to be limited to the following embodiments. -[Synthesis Example 1]

% A flask equipped with a mixer and a thermometer with a gas replacement device is fed to 1' 3, 3a, 4' 5, m (tetrahydro-2, 5 - 2 @同基-3_fur:yl)~ 蔡Π , 2-c] Furan-Umug ((M Moer) and meso-acetamide 25〇g and toluene_. Next, in the above flask: "mouth 2, 2'-{2 - hydroxyl_3 one ( 3, 5_ Dimercapto-4-ylamino)-benzyl-5-methylidenephenylcarboxamide 12.6 g (0.025 mol), maintained at 50 Torr for 3 hours. Furthermore, at room temperature The average value of a in the diamino sulfoxane (general formula 6) was 18.6 g (0. 〇75 mol), and the mixture was stirred at room temperature for 12 hours after completion of the dropwise addition. After adding a reflux condenser to the water receiver, 20.4 g of acetic anhydride and 26.4 g of pyridine were added, and the temperature was raised to 5 〇t: and the temperature was maintained for 3 hours. ' ^ The obtained solution was put into itself as a poor solvent. The resin was re-sinked in the alcohol; the poly-iminofluorenone resin having a zeoxime amount of 62% by mass was obtained, and the infrared absorption spectrum of the resin was measured, and the unreacted functional group was not observed. Absorption caused by amino acids, And 1 720cm wavelength 1780cm confirmed at the absorption due to imide stuffed. The resulting 317,457 Shang "JZ / WU tree" aliphatic "has the formula ~ II eight square \ / x \ II ίί Ο ο

〇 II shows the structure

Ο II A

Ο II Here 0.25 \ / \ wN~z&quot; II II 〇 Ο Table 0.75 Y indicates

€H2CH2CH2-Si-|〇-Si-|cH2CH2CH2 Further, the weight average molecular weight (in terms of polystyrene) of the resin was measured by a gel permeation chromatograph (GpC) using tetrahydrofuran as a solvent, and it was 24,000. A film having a thickness of 100 μm was formed on a quartz glass substrate, and as a result of measuring the light transmittance of 19 317 457 1320045, the light transmittance at a wavelength of 350 nm to 450 nm was 80% or more. The absorption spectrum of the film is shown in the figure. [Synthesis Example 2] .- For a flask equipped with a stirrer, a thermometer, and a nitrogen gas displacement device, feed L 3, 3a, 4, 5, 9b-hexahydro-5-(tetrahydro-2, 5-dione group) 3-furanyl-naphtho[1,2-c]furan-1,3-dione 30. 〇g (〇. 1 mole) and ΛΝ-dimethylethenamine 25Gg and toluene 1 () Gg. Next, 2,2-{2-hydroxy-3-(3,5-didecyl-4-amino)-benzyl-5-methyldiphenylm6g (Q.) was added to the above flask. G6 Mo), the temperature of the reaction system was maintained at 5 (rc) for 3 hours. Further, at room temperature, the diamine oxime (the average value of a in the general formula (6) was 1 G) was 36.6 g ( (). G4 Mo), and stirred at room temperature for 12 hours after completion of the dropwise addition. Next, the flask was charged with a reflux condenser with a water receiver, and then 20.4 g of phthalic anhydride and 26.4 g of pyridine were added, and the temperature was raised to 5 ( After rc, the enthalpy temperature was maintained for 3 hours. The VIII solution φ # obtained the solution was injected into the methanol of the poor solvent, and the resin was re-suppressed to obtain 11 polyoxyimide 11 lipids having an oxygen burning amount of 38% by mass. As a result of the infrared absorption spectrum of the resin, no polystyryl having an unreacted functional group was observed. The absorption was carried out at the wavelengths of 178 〇cnfl and 172 〇, and the absorption by the quinone imine was confirmed. The obtained resin ' has the structure of the following formula: ’' 317457 20 1320045

4 0·

Y represents OH OH

z represents R1/R3' CH2CH2CH2-Si-i〇-Si-j-CH2CH2CH2-R2 \ R4. Further, the weight average molecular weight of the resin is determined by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent (converted into The result of polystyrene is 20,000. A film having a film thickness of 100/zm was formed on a quartz glass substrate, and the light transmittance was measured. The light having a wavelength of 350 nm to 450 nm penetrated 21 317 457 ί 32 〇〇 45 80% or more. [Synthesis Example 3] - In the flask N equipped with a stirrer, a thermometer, and a nitrogen gas replacement device, 2, 3, cyclobutane tetracarboxylic dianhydride 19·6 g (0.1 mol) and 'N - Yinji et al. 25 g and benzene 100 g. Next, in the above flask

Γ加·! 2-Hydroxy-3_(3,5-di-f-yl 4-aminobenzyl H-diphenyl M 12.6g (G·025 mole), maintaining the reaction system at 5 generations Hour. In addition, 'diamine-based oxyhydrogen (the general formula &amp; average value of 10) 68. 6g (〇. 〇75 mol) was added at room temperature, and the mixture was stirred at room temperature for 12 hours after the completion of the dropwise addition. The flask is equipped with a reflux cooler with a water receiver, and then added (4)...g, and the temperature is raised to 5 〇. After maintaining the temperature, the resulting solution is put into a methanol solvent which is itself a poor solvent. % of the brewed imine (IV) resin: = «The result of the infrared absorption of the fat, the absorption caused by the unreacted polyamic acid is not shown, and the money is mGcr丨 and 172〇 The resulting absorption has a structure as shown in the following formula 2. 八Ο 〇 II II M/C\ 八_N\入N——YV VII II ο Ο

0II.C

0II

.X 0.25 CII 0 N—2- CII 〇 0.75 Here, X means 22 317457 1320045

Y means

-CH2CH2CH2-Si-(〇4r r2\^ •CH, CH2CH2 - and the result of measuring the weight average molecular weight of U resin (converted to polystyrene) by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent , 22000. A film with a thickness of 100//in is formed on a quartz glass substrate, and the light transmittance of _, j 疋, the light transmittance of the wavelength 35 〇 leg to 45 〇 is 80% or more. Synthesis Example 4] In a flask equipped with a stirrer, a thermometer, and a nitrogen gas replacement device, 3, 3, 4, 4'-diphenylphosphonium tetracarboxylic dianhydride 59.7 g (〇· 167 mol), Cyclohexanone 400 g. Next, diamine-based oxime (General formula (6) &amp; = mean 1G) 121.6 g (G.133 mol), bis[4-(3-aminophenoxy) Phenyl] 碉14·4g (0.033 mol) is dissolved in cyclohexanone, and the temperature of one side of the reaction system does not exceed 5 (rc ' is dripped in the above-mentioned burnt view. Drop 23 3,7457 @ 1320045 After searching for another 10 hours at room temperature.

Next, the flask was filled with water to add 40.8 g of anhydrous acetic acid and the hydrazine was connected to °. After the reflux cooler, the temperature was 3 hours. After 52 々 ' and heating to 5 rc, the obtained solution was kept in itself. The resulting precipitate was dried, iminofluorenone. As a result of measuring the infrared absorption spectrum of the resin in which the resin was precipitated in a solvent of a poor solvent and the amount of the oxime was 61% by mass, the absorption by the polyaminic acid having an unreacted ruthenium group was not observed. At the wavelength of 1720 cm_1, the absorption caused by the quinone imine was confirmed. The obtained resin had a structure as shown in the following formula. θ ”

Here, X means 0 0 II II 八八_VVN_ c C II II 0 0 0.75

Y means

317457 24 1320045 OT2eH2C: Hi4^)~CH2CH2CH2- and 'the result of measuring the weight average molecular weight (converted to polystyrene) of the resin by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent, - 30,000 A film having a film thickness of 100 μm was formed on a quartz glass substrate, and as a result of measuring the light transmittance of the light, the light transmittance of the wavelength of 35 〇 nm to 45 〇 (10) was 80% or less. The absorption spectrum of the film is as shown in Fig. 2. • [Example 1] Stir the synthesis example in a k bottle! The polyimine stone synthesized in the same process is 5 〇g of resin, 100 g of propyl acetoacetate, 5 g of propylene oxypropyl trimethoxy decane, 2'2-methoxy- 2-phenyl phenyl 5 g of benzene was brewed to obtain a composition of a polyamidite synthon resin as a target. The composition has a viscosity of ..s. The adhesion test of the hardened film obtained from the obtained polyimine ketone resin composition was evaluated by the square peel test. This result is expressed in the form. Here, the method of the square-grain peeling test is as follows. The method of the square format peeling test is applied to a glass plate in such a manner that it can be a thickness of imm, and uv (ultraviolet) irradiation (accumulated light amount of 1000 mJ/m 2 ) is performed using a high pressure mercury lamp to obtain a hardening. Membrane. The hardened film was exposed to 8 〇 'C /95/RH (relative humidity) under high temperature and humidity conditions for 24 hours, and the method of the expanded format peeling test (JIS K5400) was used to evaluate the glass plates before and after exposure. The connection between the two. [Example 2] 317457 25 1320045 Stirring the synthesis of the iranium sulphate synthase synthesized in the synthesis example i in a crucible, 5 〇 "produced ethyl acesulfame ethyl ester 5 〇 g, 2-hydroxy-&quot; -Phenyldioxane + ketone 5g 'The composition of the polyimine oxime ketone tree which is the target material. The viscosity of the composition is 80 Pa · s. The adhesion of the hardened film obtained by the imide (iv) resin composition was shown in Table 1. [Example 3] The polyimine sulfonate resin synthesized in Synthesis Example 2 was stirred in a flask. g, acetoacetate ethoxypropyl methoxypropyl trimethoxy to find &amp; 2-yl-2-methyl + phenylpropanol-bu _ 5g, the desired polyamidiamine oxime A ketone resin composition. The viscosity of the composition was s. The adhesion of the cured film obtained from the obtained (iv) imine 7 (tetra) resin composition was evaluated by a square peel test. The results are shown in Table i. Example 4] In the flask, 50 g of the polyamidite copper resin synthesized in Synthesis Example 3, 5 g of ethyl acrylate, and propylene methoxypropyl group were mixed. The methoxy decane was prepared by using 2 g of 2 #工基2~·methyl-1-phenylpropane- ketone as a target material, and the viscosity of the composition was determined. The square format peeling test evaluated the adhesion of the hardened film obtained from the obtained polyanilin resin composition. The results are shown in Table 1. [Comparative Example 1] Stirring in a flask was synthesized in Synthesis Example 4. The composition of the polyaniline (tetra) resin which is obtained as a target product is obtained by agitation of anthraquinone ketone resin 5 〇 g, 100 g of propyl ethyl acetoacetate, 2,2-dimethoxy-2-phenylethyl acetophenone. The composition 317457 26 1320045 ^ degree is H) Pa · s. According to the test evaluation _ the resin composition of the hardened film made of adhesion. Will: two are not in Table 1 〇 meaning [Table 1 ] S-~~-_ —-------- Before exposure (number of peeling / number of test pieces) After exposure (number of peeling / number of test pieces) οΤΓοο ~ ------~--__ ο/ Loo Example 1 ~~~~^---- Example 2 oTToo Example 3 ------ 0/100 0/100 Package Case 4 οΤΓοό oTToo-~ Comparative Example 1 Γοο/Τοο~ ' Γοο /Γοο~~ ------ (hardening near the substrate) ---- ---- (The hardening is poor in the vicinity of the substrate) [Simplified description of the drawing] The first embodiment shows the transmittance spectrum of the chitosan resin synthesized in Synthesis Example 1. Fig. 2 is a synthesis example 4. The penetration rate spectrum of the synthesized polyimine stone enamel resin. 317457 27

Claims (1)

1320043⁄4 $8年9./0曰 Amendment of the scope of the present application. · Patent Application No. 94133468 (September 10, 1998) A solvent-free resin composition characterized by containing (a) having the following general A polyimine fluorenone resin represented by the formula (1-1) and (1-2), which has a wavelength of from 350 nm to 450 nm measured on a quartz glass substrate to have a thickness of 1 Å #m. Light transmittance is above, (b) reactive diluent, and (c) photopolymerization initiation N \ OMMncv .X CMMno o=c OMNMC /CMno N- Y- \ ΟΠΙΟ U-/; ο s inflammation (where X is a tetravalent organic group, and one is an organic oxane moiety) is a known organic group (an organic group), and escapes the general formula (1-1 ( 2), formula (8) 'The formula (4) or the formula (5) is selected from the group consisting of _1 or more than 317457 (13⁄4 28 (2) 1320045, H2c-c-c-CH2 u) (5) • 2. For the solvent-free polyamidite ester composition of the patent application range f丨, wherein the ratio of polyimine 矽g to z in the resin is ^% by mass or more' And 2 of the general formula (1) is a diamine residue represented by the general formula (8), ry r\ CH2CH2CH2-Si-^〇-Si-^-CH2CH2CH2-(8) (wherein R to R are carbon numbers to 8) The substituted or unsubstituted -valent hydrocarbon group' may be the same or different; and 3 is 29 317457 (revision) 1320045 an integer from 1 to 100). 3. The solvent-free polyimidazolium ketone resin composition as described in the second or second aspect of the patent scope, wherein the reactive diluent of the component (b) is a mercaptopropionate compound. 4. The solvent-free polyimine fluorenone resin composition according to the invention of claim 3, wherein the photopolymerization initiator of the component (c) is selected from the group consisting of acetaminophen and diphenyl ketone derivatives. A photopolymerization initiator for a benzoin ether derivative or an oxime ketone derivative. 5. The solvent-free polyimine oxime ketone tree ruthenium composition according to the scope of the patent application, wherein (a) the poly(indenylene fluorenone resin) is 1 part by mass, (b) The reactive diluent is 2 to 2 parts by mass, and the photopolymerization initiator is 1 to 200 parts by mass. 6. The solvent-free polyimine oxime ketone tree sap composition according to the scope of the patent application, wherein (a) is a component of (b) relative to (a) polythenimine fluorenone resin The content of the oxyalkylene containing (fluorenyl) acrylonitrile group is from α to 1 part by mass. 7. The solvent-free polyimine oxime ketone resin composition according to the scope of the patent application, wherein the composition has a viscosity at 25 〇c. 8. The solvent-free polyimine fluorenone resin composition of claim </ RTI> wherein the composition has a viscosity of 252⁄4 as i〇〇〇〇pa s s. A resin film which is a solvent-free polyimine fluorenone resin composition according to any one of the first to eighth aspects of the invention. 317457 (revised edition) 30 1320045 t 10. An electronic component using the resin film of claim 9 of the patent application. 31 317457 (revised edition)