TW201233713A - Transparent polyimide siloxane, manufacturing method thereof and thin film thereof - Google Patents

Abstract

The present invention provides a transparent polyimide siloxane with the chemical structure of formula (I). The present invention also provides a method of manufacturing transparent polyimide siloxane, comprising: (A) providing a polyimide solution containing linear aliphatic flexible chain as the side chain; (B) adding the aminotrialkoxysilane into the polyimide solution of step (A); and (C) adding into the solution obtained from step (B) the trialkoxysilane with a double-bond functional group or a mixture of trialkoxysilane with double-bond functional group and the trialkoxysilane without the double-bond functional group. The present invention also provides a thin film of transparent polyimide siloxane which is characterized in that the thin film precursor solution contains the polyimide siloxane polymer with a chemical structure of formula (I). The present invention can be applied to a flexible LCD, a soft OLED, a plastic solar cell, an optical waveguide, an orientation film and a display insulation layer.

Description

201233713 VI. Description of the Invention: [Technical Field] The present invention provides a transparent polyimine oxime and a film thereof, which can be used in place of a glass substrate for flexible liquid crystal displays, flexible OLEDs, plastic solar cells, and light. Waveguide, alignment film, display insulation layer, etc. [Prior Art] The substrate material used in the conventional display is glass. The new generation of flexible display replaces glass with plastic. The plastic has light, thin and non-fragile properties, among which PNE is often used by users. (Polyethylene naphthalate), which has a melting point of 26 (TC, glass transition point φ. i2〇C, and PES (Polyether sulfone}, softening point of 2〇〇. 〇22〇°C '/NE and heat resistance of PES Still insufficient, it requires more than 230 C for IT 〇 and surface sputtering. 'High temperature is easy to cause shrinkage and discoloration of thermoplastic pne and pes. 、. In the currently available materials, poly phthalimide is preferred, and its heat resistance temperature can be It is required to reach 3 〇〇C, but generally the aromatic polyimine has low light transmittance in the visible light region, and exhibits a yellow or brown color, in order to reduce the coloring property. Adding transparency, it is necessary to reduce intramolecular and intermolecular charge transfer (Charge Transfer), which is commonly used to improve the colorless and transparent method of polyimine. ^丨·Introducing fluorine-containing groups 2. Large-volume groups 3. Importing Symmetrical structure 4. Reduction of conjugated double bond structure. ^ Republic of China Patent Publication No. 200615303 discloses an organic layered bismuthate treated with organic rust ions, which is dispersed in polyimine and can be made into a colorless transparent poly The imine film can be produced by using an aliphatic (C5~C16) diacid sulphate and an aliphatic (C6~C27) or a genus di-eily synthetic imine. After being washed with methanol, it is dissolved in a solvent, and then organic. The rust-treated bismuth salt is dispersed in a polyimine solution, and the obtained film has a penetrability, (color difference meter (10)- ing). The disadvantage is that the film has a transfer point of about 3103⁄4 or more, and the film is brittle and The dielectric constant is high. The Republic of China Patent Publication No. 200513432 discloses a method for producing a transparent high modulus aromatic 201233713 family of polyimine, which is obtained by adding nanoorganic clay to polylysine, and after being dispersed, the ring is made into a nanometer. Polyimine material In that the film-divided photometric test transmittance (4〇〇nm) about 20%, which is too low in transparency.

The Republic of China Patent Publication No. 1318634 discloses a highly transparent and image-sensitive photosensitive polyimide precursor for liquid crystal display devices, which is a C3~C3 脂 lipid cyclic tetraacid dianhydride and a diamine benzoate. Or diamine-based stearyl ester to obtain a polyamidamine, and then reacted with glyceryl methacrylate or allyl glycerol, and the resulting film is tested for transmittance (4 〇〇 nm) by a spectrophotometer. more than 90 percent. The disadvantage is that the poly-imine has a large number of rigid structures, and the film is brittle and has poor flexibility. The Republic of China Patent Publication No. 1298076 discloses a method for preparing a precursor solution of a polyamidene/iridium oxide composite material comprising an additive-ester monomer, which has a oxidized 11 group, which is sensitized and heated. Polymerization can be obtained as a film. The disadvantage is that the poly-amine end group is covalently bonded to the giant Ju Wei Yuan, and the transparency of the film is poor. Li "Republic of China Patent Notice 125 is only disclosed on the 7th - a multi-faceted silk polymer 7-imine composite material which is covalently bonded, and the composite material is "Subvalent financial bond, = dielectric constant and certain mechanical properties. The disadvantage is that it uses aromatic polyimide, which is poor in transparency and flexibility. 201233713 [Summary of the Invention] The neglected problem of the thin transparent polyienimine polymer and its composite material cannot be combined with high transparency and high flexibility; it is characterized by its characteristics and mechanical properties. The dielectric of the imine-wet yarn composition was not inked and discussed. The characteristics of the optical properties and high flexibility of the industry and the above problems, the present invention provides a transparent polyamine, which has the chemical structure shown by the formula (1):

Wherein P is a divalent aliphatic having a side chain of C16 to C44; and Q is a divalent aliphatic selected from the group consisting of C16 to C44 having a side chain.

A is selected from:

B is _NH-C3H6-, -NH-C6H6; R is selected from: 201233713 - C3H600CCH = CH2 isobutyl, isooctyl, energy group; a c3h6oocch3c = ch2 vinyl, alkylene, octenyl, ring The group of hexane group and phenyl group contains at least one double bond η which is an integer selected from: 1 to 5 Å; m is an even number selected from 6 to 18. The invention relates to a transparent polyimine yttrium-oxygen fire, which is characterized in that the molecule has a soft-chain with a side-chain of a side-axis, which can reduce the crystallinity of the publication and increase the compatibility with the poly-stone. The polymer is imparted with high flexibility, low dielectric constant, low dielectric loss, low refractive index, high transparency, and high flatness. The invention of the invention is a kind of diarrhea (four) postal wealth Wei, whose ship has a nano-polysilicate structure at the end of the molecule, which imparts high transparency, high heat resistance, low dielectric constant, low dielectric loss and low thermal expansion to the polymer. Properties, low refractive index, mechanical properties. The invention is a kind of "Wei Weiwei", the nano-poly-wei of the ship at the end of the molecule has an unsaturated double structure, and the diacid of the polyimine chain can contain an unsaturated double bond structure. It can be converted into a thermosetting polymer from a thermoplastic polymer to a thermosetting polymer by thermal curing or radiation curing to achieve intermolecular cross-linking, which imparts low heat shrinkability, heat resistance and solvent resistance to the polymer. The invention provides a condensed polymer and a film thereof, which can replace the glass substrate, and is used for a replaceable liquid crystal display, a soft OLED, a plastic solar cell, an optical waveguide, an alignment film, a display insulating layer and the like. Compared with the efficacy of the prior art, the present invention provides a superior flexibility to the fluorinated yttrium imide and its thin 201233713, and has a linear n (four) (four) soft chain. Bijia-imine has superior transparency, and has an unsaturated double bond structure, which has superior heat-shrinkage U-life resistance than traditional poly-imine. This (4) provides transparent hetero-imide Wei-burn. Fat sputum or semi-mysters have a lower refractive index 'traditional consuming sub- argon ray rate is about </ br>, and each of the above is easy to ^ ^ into light reflection, so that the display light rate is reduced, combined to give polyimine The film has both high transparency, high heat resistance, low dielectric constant, low dielectric loss, low thermal expansion, low refractive index, high flexibility, solvent, mechanical properties, etc. The film and the film are inferior to the needs of the industry. [Embodiment] The object of the present invention is to provide a chemical structure as shown in (a):

&amp; I R

γ γο ΟΛΑΥΟ ΟΛ γο Ν

Wherein P is a C16~C44 divalent aliphatic having a side chain; Q is selected from the group consisting of: C16~C44 having a side chain of a divalent aliphatic, a heart, a ring, a ring, and a QN&lt;y A selected from: 201233713

Attack, attack, X CF,

R is selected from the group consisting of: —c3h6oocch=ch2, 3 6 3 2 , a vinyl group, an allyl group, an octenyl group, an isoisooctylcyclohexanyl group, a group of the present group, and at least one double bond functional group; π is an integer selected from: 1 to 50; m is an even number selected from 6 to 18. The invention is -_日妹神绿, its special wealth in the molecule and has a 2-chain heterotic soft chain, which can reduce the crystallity of the molecule, the matter and the poly, the polyether, the flexibility, the low dielectric Constant, low dielectric loss, low refractive index, high transparency, high flatness. There is a lion _ _ Wei, its ship is at the end of the molecule with constant, low dielectric high refractive properties, high age resistance, low dielectric -, electric enthalpy, low thermal expansion, low refractive index, mechanical properties. Too t=r kind of transparent polyamidite oxime, which is characterized by a cut-like structure with a slit at the end of the molecule, and the disulfide 201233713 needle of the Wei chain can contain a forest saturated double bond structure, via oiling Or the (four), inter-molecular cross-linking 'filament polymerization _ is an oily polymer, giving the polymer low heat shrinkability, heat resistance, solvent resistance. The invention relates to a transparent polyimine oxime, which is a solvent-soluble flexible polyimine which is combined with a weiweiwu. The soluble flexible imine molecule has a terminal group which is broken. The polyimine and the polyoxane are combined with a polyimine or a guanamine structure. The transparent polyamidene derivative of the present invention has a nano-polysulfide structure at the molecular end, and the three alkoxy groups containing a double bond functional group include: vinyl diethoxy oxime, vinyl three曱 methoxy decane, 3 ethyl phenyl triethoxy sulphur, 3-vinyl benzene trimethoxy wei, 4 - vinyl phenyl triethoxy oxane, ethylene benzene trimethoxy wei, Dilute propyl triethoxy wei, allyl trimethoxy sulphur, 4-bromopropyl phenyl triethoxy wei, 4, propyl phenyl trimethoxy sulphur, dilute propyl ethyl tri Oxy Wei, allyl ethyl trimethoxy Wei, propyl propyl diethoxy decane, allyl propyl trimethoxy decane, allyl butyl triethoxy sulphur, allyl Butyl trimethoxy wei, 3-methyl propyl propyl ethyl triethoxy sulphur, 3 · decyl allyl ethyl trimethoxy wei, 3 曱 lyl propyl propyl triethoxy stone Xishou, 3-mercaptopropylpropyltrimethoxy-Wei, 3-methyl-propylpropylbutyltriethoxy-xanthine, 3·methyl-hydroxypropyl-t-trimethoxy-Wei, 3 _methylmethyl propyl ethyl triethyl Oxyoxan &amp;, 3-methylmethylallylethyltrimethoxysulfide, 3-methylmethylallylpropyltriethoxysulfate, 3-methylmethyldip Propyltrimethoxy zeshi, 201233713 3-methylmethyl propyl butyl triethoxy hydride, 3 • methyl decyl propyl butyl trimethoxy sulphur, 3-(mercapto propylene oxime Oxy)ethyltrimethoxyxanthene 9,3 (methylpropanoloxy)ethyldiethoxy sylvestre, 3_(methacryloxy)oxypropyltrimethoxy sulphur, 3 -(decyl propylene methoxy) propyl trimethoxy zeoxime, 3-(methyl propylene oxy) butyl diethoxy decane, 3-(methacryloxy) butyl trimethoxy Basear, 3_(mercaptopropyloxy)butyltriethoxy; ^, 3_(acryloxy)ethyltrimethoxycarbazide, 3-(acryloxy)ethyltriethoxy Baseline, 3-((propyleneoxy)propyltrimethoxyoxycyclodecane, 3-(propyleneoxy)propyltriethoxydecane, 3-(methacryloxy)butyldimethoxyl Decane, 3-(acryloxy)butyltriethoxydecane, 7-octenyltrimethoxyxanthine, 7-octyl Alkyl triethoxylate is burned. The present invention synthesizes a transparent polyamidiamine oxirane polymer, and the dioxin-based sulphur-burning which uses the unreacted double bond functional group includes: a calcined tribasin, a cycloalkyl trialkyl decane, a stupid base Examples of trialkyl decanes include isobutyl trimethoxy decane, isobutyl diethoxy sulphur, cyclohexyl trimethoxy sulphur, cyclohexyl triethoxy sulphur, φ phenyl Trimethoxy decane, phenyl triethoxy decane, isooctyl trimethoxy decane, isooctyl triethoxy decane, and the like. The invention synthesizes a transparent polyamidiamine oxirane polymer, and the aminotrialkyl decane used specifically includes: 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3- Amine phenyl trimethoxy decane, 3-aminophenyl triethoxy oxalate, and the like. The transparent polyimine oxime of the present invention has a polyhedral sesquioxalic oligomer (Poly oligomeric silsesquioxane POSS) structure, and its shape can be a cage structure. Part of the cage structure, ladder structure, 201233713 irregular structure, etc., where „! is an even number of 6~18, common examples of cage structure include:

The invention synthesizes a transparent polyimine oxime, and the tetracarboxylic dianhydride package used includes .1,2,3,4-cyclopentane|tetracarboxylic dianhydride, 1,2,3,4-ring Butadiene tetracarboxylic dianhydride, 1,24 5 -cyclohexane tetracarboxylic dianhydride, dibutyl dianhydride, bicyclooctene 2,3,5, ^ tetraacid dianhydride, bicyclooctane-2,3 ,5,6-tetracarboxylic dianhydride, 5-(2,5-dioxotetrahydrofuran-3-yl)methylcyclohexene-1,2-dianhydride, 4-(2,5-di Oxotetrafluorofuran _3_yl)tetrahydronaphthalene 丨,2• dianhydride, 4,4_hexafluoroisopropylidene dicarboxylic acid dianhydride, 1-(trifluoromethylidene) 2,3, 5,6_ stearic acid dianhydride, hydrazine, 4_bis(trifluoromethyl)-2,3,5,6-benzenetetracarboxylic dianhydride, etc. The present invention synthesizes a transparent polyamidite The two-valent fatty amines having a side chain used include: 3-methylheptanediamine, 4,4-dimercaptoheptanediamine, 4-methylstilbenediamine, 5-nonyldecanediamine, 2 , 5-dimercaptohexanediamine, 2,5-dimethylheptanediamine, 2,2-dimercaptopropane diamine, fatty amine dimer, etc. The present invention synthesizes - a kind of transparent polyimine The divalent fatty amine with side chains used in the hospital can be mixed with other diamines including: diaminocyclohexane Pyrithion, diaminocyclohexyl ether, isophorone diamine, i,3-diaminocyclohexane, I 3 bis (aminomethyl) cyclohexane, diaminodiphenyl ether, dicyclohexyl Amine, etc. The present invention is a synthetic-species organic porphyrin and its fine organic 12 201233713 solvent includes at least - selected from: N, N - dimethylformamide, N, N - dimethyl Indoleamine, N-methyl+comparative ketone, dimethyl sulphate, bis-f-butylamine, methyl ethyl hydride, decyl isobutyl butyl, diisobutyl ketone, methyl isobutyl ketone, ring fine, ring Benzyl, diisobutyl ketone, tetrahydrofuran, tetramethyl urea, No. 2 burning vinegar, gas, two gas, two ethylene glycol monohexyl hydrazine, propylene glycol monothiol bond, propylene glycol monoethyl Ethyl ether, propylene glycol monopropyl sulphate, n-butyl sulphate acetate, diethylene glycol monobutyl sulphuric acid, toluene, xylene, etc. • The present invention synthesizes a transparent polyamidene oxime, amidoxime catalyst Triethylamine, tripropylamine, tributylamine, hydrazine, methyl hydrazine, dimethyl benzylamine, other secondary amines, phenol, benzoic acid, toluenesulfonic acid, other acids may be used. The invention provides a method for producing a kind of diarrhea, which comprises: (A) providing a polyaniline solution containing a linear aliphatic soft bond of a side chain (8) adding an amine trioxyl group Wei In the polyamidimine solution of the step (4), the ruthenium i 77 solution has a dioxin group; the group of the polyamidamine solution; (the ruthenium group containing the double bond functional group, or A mixture of a tri-oxo-oxygen and a non-reactive Wei-functional trioxane-containing mixture having a double bond functional group is added to the solution of the step (8) to obtain a polyamidimide molecule having a double bond S π group Surface-enhanced oxygen oligo oligo-clear transparent polythene imine oxime-oxygen 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 The polyimine solution is a (2) to 201233713 divalent fatty amine having a side chain. The invention relates to a method for producing a transparent polyamidooxane, wherein the aminotrioxyalkyl decane of the step (B) is selected from the group consisting of: 3-aminopropyltrimethoxy decane, 3-aminopropyl Triethoxy oxime, 3-aminophenyl trimethoxy decane, 3-aminophenyl triethoxy decane. A method for producing a transparent polyimine oxime of the present invention, wherein the step ((:) comprises a double bond functional group-containing trialkoxy decane and a non-reactive double bond functional group of a trioxyalkyl sulfonium alkane mixture The content of the trialkoxy decane containing a double bond functional group is from 10% to 100%. The object of the present invention is to provide a film of a transparent album, which is characterized in that the film precursor contains polyphthalamide. The chemical structure of the amine stone oxime institute is as shown in formula (1) (1)

Bu tr^〇3/2 long m HO

+si〇3/2yR2] wherein P is a divalent aliphatic having a side chain of C16 to C44; and Q is a divalent aliphatic selected from the group consisting of .C16 to C44 having a side chain.

Α is selected from: 14 201233713

Attack, attack, X

R is selected from the group consisting of: -C3H600CCH=CH2, a c3h6oocch3c=ch2 group of ethylene, propyl, octyl, isobutyl, isooctyl, cyclohexyl, phenyl, having at least one double bond a functional group; η is an integer selected from the group consisting of: 1 to 50; m is an even number selected from the group consisting of 6 to 18. The invention relates to a method for manufacturing a transparent polyimine oxime oxime film, which comprises adding a phthalocyanine to a photoinitiator, and can select a Rolling coating and a flow coating. (Flow coating), Dip coating, spray coating, spin coating, curtain coating (C: mercury eQating), etc., applied to non-mineral steel sheets or PET The film 'via rc~2〇 (rc pre-baked, and then cured by radiation irradiation can be obtained - transparent poly- 醯 之 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , Low scale dirt, low refractive index, heat, solvent resistance, mechanical properties, etc. High flexibility, and in the manufacture of a transparent polyimide fiber of the present invention, the use of the light from 15 201233713 The agent includes benzophenone, 4,4,-bis(N,N-:ethylamino)benzidine 4,_bis(N'N-methylamino)diphenylfluorene, phenyl Biphenyl fine, 卜丝_卜苯(四) Cyclohexene, benzyl carbaryl, 2 benzyl-2_(diamine) _4, hydrazinophenyl hydrazine, 2-methyl-2 -(Methylthio)- 4,--------------------------- F-mercapto-4-methyldiphenylsulfonium, benzoin, shrub, 2_glycolyl-2-benzoylpropane, 2-carbyl-2-(4,-isopropyl)benzhydrylpropyl Burning, 4_ butyl beryllyl triglyceride, 4 phenoxy phenyl hydrazine, benzoic acid methyl vinegar, 1, bis (9-丫定基)-ship, 9 - n-butyl-3,6-bis(2-morphinyl-isobutyl)-carty, trimethyl benzhydryldiphenylphosphine oxide, etc. The object of the present invention is to provide a transparent polyimide stone Oxygen-fired film, which is used for flexible liquid crystal display, soft OLED, solar cell, optical waveguide, alignment film, display insulating layer. Example 1 5-(2,5-dioxotetrahydrofol ··3_yl)methylcyclohexene _i,2_dianhydride 13.2g, 4,4-hexafluoroisopropylidene dicarboxylic acid dianhydride 22 2g, r-butyrolactone, diisobutyl The ketone 60g is placed in a four-reaction reaction flask equipped with mechanical solution, condensation f, drying tube, steaming device and gas, and the reaction temperature is lowered in an ice bath. 5~1Q. Fatty amine second frequency 48 and 2nd idiot Qg^ small amount into 'reaction 3 hours after adding dimethyl chloramine 〇. 3g, heated to 16 (H8 (rc total Buddha removes water, can A poly-imine solution containing a linear chain of _$ soft chain, which has a guanidine conversion of 95% and a weight molecular weight of 339 Å by GPC. 16 201233713 Lowering the temperature of the poly-imine solution to 40 °C, adding 3_aminopropyltrimethoxy oxylate 17.9g 'reaction for 3 hours, adding 44 4g of ethylene trioxane oxylate, 71.2g of isobutyl-methoxy sulphur, water 5克混合均均。 The solution was coated with a photoinitiator (Irgacure 184) 2. 5g mixed uniformly, the solution was coated with a photo-initiator (Irgacure 184) 2. 5g Spread on a stainless steel plate and bake at 100 C for 30 minutes '12 依. (: baked for 30 minutes, 16 〇 it is baked for 30 minutes, 180 it is baked for 1 hour, hardened by ultraviolet light to make a film of 1 〇〇#m thickness, measure it

Transparency, thermal decomposition temperature, refractive index, dielectric constant, dielectric loss, folding resistance, and solvent resistance are shown in Table 1. Example 2 5-(2,5-dioxotetrahydrofuran-3-yl)methylcyclohexene oxime, 2 dianhydride 13.2 g, 1,4-bis(trifluoromethyl)_2 , 3,5,6-benzenetetracarboxylic dianhydride i7.7g, 7*-butyrolactone 60g, diisobutyl -6 〇g, placed in a mechanical stirring, condensing tube, drying tube, distillation and nitrogen In a four-neck reaction flask, the reaction temperature was lowered to 5~i〇°c in an ice bath, and the mixture was mixed with an average amount of 48.24§ and diaminocyclohexanyl-G.g. After the reaction, the reaction is carried out for 3 hours, and then dimethyl benzylamine hydrazine is added. 3 g, heated to 160-180 C to azeotropically remove water, and a polyetherimine solution containing a linear aliphatic soft chain of a side chain can be obtained. The amination rate was 94%, the weight molecular weight was 31,800 G by GPC, the temperature of the polyimine solution was lowered to 4ITC, and the 3-aminopropyltrimethoxy decane oxime was added. 9g, the reaction was carried out for 3 hours, and the olefin was added. Base trimethoxy oxane 48 〇g, isobutyl dimethoxy decane 71.2g, water lg reaction for 24 hours, the reaction temperature is raised to 11 〇〇c 201233713 to remove water and alcohol 'a polyimide stone 5克混混。 Oxygen igniting solution, adding light initiator Urgacure 184) 2. 5g mixed Evenly, the solution was applied to a stainless steel plate, baked in a lOOt for 30 minutes, baked at 120 ° C for 30 minutes, and 16 (TC baked for 30 minutes, 2 〇〇 ° (: baked for 1 hour, hardened by ultraviolet light) The thickness of the crucible was measured, and its transparency, thermal decomposition temperature, refractive index, dielectric constant, dielectric loss, folding endurance, and solvent resistance were measured, and the data are shown in Table 1. Synthesis Example 3 • 4_(2) ,5-dioxotetrahydrofuran-3-yl)tetrahydronaphthalene-1,2-dianhydride 15. 0g, 1 (monofluoroindolyl)-2,3,5,6-tetracarboxylic acid-if M.3g, γ-butene g 6〇g, diisobutyl _j 6〇g, placed in a four-reaction reaction flask equipped with mechanical stirring, condensing tube, drying tube, distillation receiver, nitrogen, with ice The reaction temperature of the bath was reduced to 5~1〇〇c, and after stirring, the fatty amine dimer 48.24 § and diaminocyclohexyl hydrazine were added in small portions in portions, and after 3 hours, didecylbenzylamine was added. 〇3g, heated to 16〇18〇.〇Azeotropic removal of water' can be obtained as a kind of poly-imine solution containing lining of the thief line, the amide amination rate is 95%, measured by GPC Its weight molecular weight is 31〇2〇. The temperature was lowered to 40 t; 3 -aminopropyltrimethoxycarbazide. 9 g was added, and the reaction was carried out for 3 hours 'addition of 3 · (acryloxy) propyl trimethoxy decane 6 〇. 6 g, cyclohexane 81.6g of trimethoxy oxalate, water lg reaction % hours, the reaction temperature is raised to the moisture of the silk and the alcohol can be used to add the photoinitiator (I chature round 2 々 mixed Sentence, the solution is coated on a non-fine plate, baked in boots for 30 minutes, thieves baked for 3 minutes (10) Μ 3 〇 minutes, baked for 1 hour, hardened by ultraviolet light to make a film of 1 〇〇 thickness , 18 201233713, i amount of its monthly penetration, thermal decomposition temperature, refractive index, dielectric constant, dielectric loss, folding resistance, and solvent solubility, the data is shown in Table 1. Example 4 Double-doped bismuth-2,3,5,6-tetracarboxylic acid two-pin 12 々, anthracycline-burning _2,3,5,6-tetracarboxylic dianhydride*12.5g, r-butyroline 6〇g, diisobutyl _6, placed in a four-port reaction bottle equipped with mechanical search and condensing tube, drying tube, _ receiver, nitrogen, the reaction fox down to 5~l in ice bath (Tc After the mixing is uniform, the fatty amine is in a quantity of 5 〇. 92g of a small amount is added to the ruthenium. After the reaction for 3 hours, the dimethyl hydrazinium is added. 3g, heated to 16 〇 18 〇. Azeotropic removal of water A 'polyimine solution containing a side-like tester, which has a hydrazide ratio of 95% and a molecular weight of 29980 as measured by GPC. The temperature of the polyimine solution is lowered to 4 ( Rc, add a3_aminophenyltrimethoxy oxetane 21. 5g, react for 3 hours, add 3_(mercapto propylene methoxy) propyl trimethoxy decane 154.8g, phenyl trimethoxy decane 5克混合均均Apply the solution to a stainless steel plate, sequentially in a lOOt: roast for 30 minutes. I2 (Tc baked for 30 minutes, 160 ° C for 30 minutes, 200 ° C for 1 hour, cured by UV light to make a film of 1 〇〇 / / m thickness, measuring its transparency, thermal decomposition temperature, refractive index, The electric constant, the dielectric loss, the folding endurance, and the solvent resistance are shown in Table 1. Example 5 Dibutyl dianhydride 9. 9 g, 1,2,3,4-cyclobutane tetracarboxylic acid Anhydride 9.8g, r-butyrolactone 60g, diisobutyl ketone 60g, placed in a four-reaction reaction flask equipped with mechanical stirring, condensing tube, drying tube, steaming 19 201233713 Gu Yu, gas, will be ice bath The reaction temperature is lowered to 5~1 〇. 匸, after the homogenization is evenly mixed, the fatty amine dimer is 50.92 g in small portions, and after 3 hours, 3 g of dinonylbenzylamine hydrazine is added and heated to 160 to 180. Azeotropic removal of water gives a solution of a linear aliphatic soft chain containing a side chain, which has a hydrazide ratio of 95% and a weight molecular weight of 27930 as measured by GPC. The temperature was lowered to 4 (rc, 2,5-aminophenyltrimethoxy oxime was added to 21.15 g, and the reaction was carried out for 3 hours, and allyltrimethoxy decane was added, 32 〇g, octenyl group, trioxetoxy group. 54.0 g of decane, 54.0 g of isooctyltrimethoxy decane, and 24 g of water ig reaction, the reaction temperature is raised to remove water and alcohol, and a solution of polyamidiamine oxirane can be obtained, and a photoinitiator (Irgacure) is added. 184) 2.5g mixed evenly, the solution was coated on a stainless steel plate, followed by (10). c baked for 3G minutes, (10). c grilled for another minute, 160 C baked for 30 minutes ' 2 〇 (Tc baked H, when, by The film was cured by ultraviolet light irradiation to measure its transparency, thermal decomposition temperature, refractive index, dielectric constant, dielectric loss, folding resistance, and solvent resistance. The data are shown in Table 1. Φ Comparative example (2'5-oxotetrahydrofuran-3-yl)nonylcyclohexene_ι,2_dianhydride 261 7 purchased internally, xylene 2〇g 'fitted with machinery Stirring, condensing tube, '°, tube: recording and nitrogen, four-neck reaction flask, the reaction temperature was reduced to 5 10 C in an ice bath. After mixing evenly, the diamine group was added in small batches. , after adding people - methyl ketamine G 3g 'heated to (10) ~ (10). C azeotropic removal of water 〇浔 A poly-imine solution of a linear aliphatic soft chain containing a side chain having a brewing amination rate of 93% and a weight molecular weight of 18020 as measured by GPC. 20 201233713 Reduce the temperature of the brewing imine solution to 4 (rc, add 3_aminopropyl triacetate called 'reaction for 3 hours', add ethylene trimethoxyjuxate, isobutyl dimethyl group Wei 7Ug, The water lg is reacted for 24 hours, the reaction temperature is raised to remove the water and the alcohol, and the polyimine yttrium oxide solution is obtained, and the photoinitiator (gacurel 84) is added. Do not bake on the shaft for 30 minutes, the boots for 3 minutes, and the boots for 1 minute. The film is cured by UV light and the thickness is measured. The transparency, thermal decomposition temperature and refractive index are measured. , dielectric constant, dielectric loss 'folding resistance, financial solvent, the data is shown in Table 1.

Heat resistance (Td): measured by TGA (Q500) manufactured by TA Corporation, and expressed by the heat decomposition temperature of 5% thermal weight loss. Dielectric constant (Dk): 0 dielectric loss (Dk) measured by Agilent LCR Meter (E-4991A) / 1 GHz: measured by Agilent LCR Meter (E-4991A) 1 GHz 21 201233713. Refractive index (RI): The refractive index was measured by an Abbe refractometer at a temperature of 25 t. Surface roughness: measured by SURFCOM 480A, manufactured by ACCRETECH, and expressed as roughness average (//m). Fold-resistant 〇 411'): Determined according to the method of 1113 05016 8.7 Solvent resistance: Soaked in methyl ethyl ketone solvent for one hour, according to its swelling condition is divided into: Liangzhu, △, and difference X. • It can be seen from Table 1 that Examples 1 to 5 show better transparency, heat resistance, folding resistance, low dielectric property, flatness, and low refractive index relative to the comparative examples, and the transparent polyimine oxime and its The film is suitable for replacing the glass substrate, and is used for a flexible liquid crystal display, a soft OLED, a plastic solar cell, an optical waveguide, an alignment film, a display insulating layer, and the like. The present invention has been described in connection with the above specific embodiments and comparative examples, and those skilled in the art will be able to make various changes based on the above description, and thus do not limit the scope of the claims of the present invention. [Simple description of the schema] Helmet 22 201233713 [Simple description of the diagram]

[Main component symbol description] None

twenty three

Claims (1)

201233713 VII. Patent application scope: 1. A transparent polyimine oxime having a chemical structure as shown in formula (I): Wherein P is a C16~C44 divalent aliphatic having a side chain; Q is a divalent aliphatic selected from the group consisting of C16 to C44 with a side chain. B is selected from the group consisting of: -NH-C3H6-, -NH-C6H6; R is selected from the group consisting of: one (^OOCCbCH2, one C^OOCCHpCH2, vinyl, allyl, octenyl, isobutyl, isooctyl, The group of cyclohexane group and phenyl group contains at least one double bond functional group; η is an integer selected from: 1 to 50; 24 201233713 m is an even number selected from: 6 to 18. 2. The invention relates to a method for producing an imine oxime, comprising: (A) providing a polyamilimine solution containing a linear aliphatic soft chain of a side chain; (B) adding an amine-based trioxynase to the step (A); In a polyamidimine solution, a polyamidimine solution having a trialkoxyalkyl group at the molecular end is obtained; (C) a tri-oxygen group containing a double bond functional group or a double bond functional group a mixture of trisethoxy decane and a dialkoxy decane having no double bond functional group, added to the solution obtained in the step (B), to obtain a polyamidimide molecule having a double bond functional group polyhedron sesquiterpene A transparent polyimine oxime of an oligomer group. 3. Manufacture of a transparent polyamidoxane as described in claim 2 The method wherein the step (A) - a linear aliphatic soft chain-containing polyimine solution containing a side chain is a C16 to C44 divalent fatty amine having a side chain. 4. A transparent one of the second item of the patent application A method for producing a polyamidooxane, wherein the aminotrioxyalkyl decane of the step (B) is selected from the group consisting of: 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane And a method for producing a transparent polyimine oxime, according to the second aspect of the invention, wherein Percentage of trialkoxy decane containing double bond functional groups in the dioxo oxime mixture of the double bond functional group containing the double bond functional group in step (C) and the unreacted double bond functional group b group It is 1〇%~10〇%. 6. -A kind of osakasaki rainbow fresh Wei _, which is characterized by _ precursor liquid contains poly 25 201233713 醯 imine deciduous hospital, its chemical structure is as shown in formula (1): (One) Wherein P is a divalent aliphatic having a side chain of C16 to C44; and Q is a divalent aliphatic selected from the group consisting of C16 to C44 having a side chain. A is selected from: B is selected from the group consisting of: -NH-C3H6-, -NH-C6H6; R is selected from the group consisting of: -C3H60CXXH=CH2, -C3H6〇〇CCH3〇CH2, vinyl, allyl, octenyl, isobutyl, iso The group of octyl, cyclohexane, and phenyl groups contains at least one double bond functional group; η is an integer selected from the group consisting of: 1 to 50; and m is an even number selected from 6 to 18. 26 201233713 7. A thin film of transparent polyamidoxane as described in claim 6 for use in flexible liquid crystal displays, flexible OLEDs, plastic solar cells, optical waveguides, alignment films, displays Insulation. 27