CN105646830B - A kind of light sensitive polyurethane and its preparation method and application - Google Patents
A kind of light sensitive polyurethane and its preparation method and application Download PDFInfo
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- CN105646830B CN105646830B CN201410626995.2A CN201410626995A CN105646830B CN 105646830 B CN105646830 B CN 105646830B CN 201410626995 A CN201410626995 A CN 201410626995A CN 105646830 B CN105646830 B CN 105646830B
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Abstract
The present invention discloses a kind of light sensitive polyurethane and its preparation method and application, wherein preparation method includes the following steps：A, polyalcohol is dissolved, polyhydric alcohol solutions is made；Acrylic acid derivative is dissolved again, and is added dropwise in above-mentioned polyhydric alcohol solutions, after reacting a period of time, filtration washing, and be dried, it is for use that light sensitivity diol compound is made；B, light sensitivity diol compound obtained above and diisocyanate compound, the bifunctional compound containing active hydrogen and catalyst are dissolved in organic solvent and are reacted, reprecipitation is filtered and washed, and obtains prepared light sensitive polyurethane.The light sensitive polyurethane material with good insulating performance is obtained through the invention, and it is applied on TFTs devices, the incompatible situation of flexible display where improving traditional insulating materials and TFTs devices, and the light sensitive polyurethane prepared by the present invention has the characteristics that surfacing, impurity concentration be low, transparent and homogeneous.
Description
Technical field
The present invention relates to chemical material fields more particularly to a kind of light sensitive polyurethane and its preparation method and application.
Background technology
In the prior art, it is mainly inorganic material with the insulating layer material in flexible display on TFTs, such as：
SiO2、SiNx、Al2O3、Ta2O5There is higher dielectric constant Deng, these inorganic material, the threshold voltage of transistor can be reduced
And leakage current, and material source is easy to get, therefore be used widely.But even if these inorganic material are under conditions of vacuum
It is also required to higher processing temperature, this is not inconsistent with the technological requirement for making TFTs in flexible display substrate, in addition, inorganic material
Expect the TFTs insulating layer materials being processed into, rough surface, impurity concentration height and semiconductor and flexible display substrate compatibility
Poor and cost is higher.
Therefore, the existing technology needs to be improved and developed.
Invention content
In view of above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a kind of light sensitive polyurethane and its preparation sides
Method and application, it is intended to solving the TFTs insulating layer materials that inorganic material is processed into the prior art need to carry out at high temperature, and its
Rough surface, impurity concentration height and semiconductor and flexible display substrate poor compatibility and the higher problem of cost.
Technical scheme is as follows：
A kind of preparation method of light sensitive polyurethane, wherein include the following steps：
A, polyalcohol is dissolved, polyhydric alcohol solutions is made；Acrylic acid derivative is dissolved again, and is added dropwise to above-mentioned polyalcohol
In solution, after reacting a period of time, filtration washing, and be dried, it is for use that light sensitivity diol compound is made；
B, by light sensitivity diol compound obtained above and diisocyanate compound, containing the difunctional of active hydrogen
Compound and catalyst, which are dissolved in organic solvent, to be reacted, and reprecipitation is filtered and washed, and it is poly- to obtain prepared light sensitivity
Urethane；
The general formula of the polyalcohol is R (OH)n, wherein n=3,4.
The preparation method of a kind of light sensitive polyurethane, wherein the acrylic acid derivative includes：General formula isAcryloyl chloride class compound, general formula be (R2CO)2The acrylic acid compound anhydride and general formula of O be
Acrylic acid methanol esters compounds in it is one or more.
The preparation method of a kind of light sensitive polyurethane, wherein the diisocyanate compound includes fragrance
One in (cyclo) aliphatic diisocyanates class compound, aliphatic diisocyanate class compound and alicyclic diisocyanate class compound
Kind is a variety of.
The preparation method of a kind of light sensitive polyurethane, wherein the bifunctional compound containing active hydrogen is extremely
Include-OH ,-SH ,-NH ,-NH less2With more than two compounds in CH- acidic-groups.
A kind of preparation method of light sensitive polyurethane, wherein the bifunctional compound packet containing active hydrogen
Include the mixture of difunctional macromolecular active hydrogen compounds and difunctional small molecule active hydrogen compounds.
The preparation method of a kind of light sensitive polyurethane, wherein the organic solvent includes：
Low boiling point ketones solvent：Acetone, butanone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone, tetrahydrofuran and 1,4- bis-
It is one or more in six ring of oxygen；
High boiling solvent：N-Methyl pyrrolidone, n,N-Dimethylformamide, n,N-dimethylacetamide and dimethyl are sub-
It is one or more in sulfone.
A kind of preparation method of the light sensitive polyurethane, wherein by mass percentage, the addition of the catalyst
Amount accounts for the 0.01-0.06% of reactant gross mass in step B.
The preparation method of a kind of light sensitive polyurethane, wherein the number-average molecular weight of the light sensitive polyurethane is
5000-10000。
A kind of light sensitive polyurethane, wherein be prepared by above-mentioned preparation method.
A kind of application of light sensitive polyurethane, wherein the light sensitive polyurethane is applied to the insulating layer of TFT devices.
Advantageous effect：In the present invention by by homemade light sensitivity diol compound and diisocyanate compound etc. into
Row reaction, obtains the light sensitive polyurethane material with good insulating performance, and applied on TFTs devices, improves biography
The insulating materials of the system situation incompatible with the flexible display where TFTs devices, and the light sensitivity prepared by the present invention is poly-
Urethane has the characteristics that surfacing, impurity concentration be low, transparent and homogeneous.
Description of the drawings
Fig. 1 is a kind of flow chart of light sensitive polyurethane preparation method preferred embodiment of the present invention.
Fig. 2 is the flow chart that flexibility TFTs devices are prepared using light sensitive polyurethane of the present invention as insulating layer.
Specific implementation mode
A kind of light sensitive polyurethane of present invention offer and its preparation method and application, to make the purpose of the present invention, technical side
Case and effect are clearer, clear, and the present invention is described in more detail below.It should be appreciated that specific reality described herein
It applies example to be only used to explain the present invention, be not intended to limit the present invention.
Polyurethane is one kind by polyisocyanates（OCN-R-NCO）And polyalcohol（HO-R1-OH）It reacts and there are multiple ammonia
Carbamate（-NH-COO-）The high-molecular organic material of segment.By making light sensitivity diatomic alcohol compounds by oneself in the present invention, and
Itself and diisocyanate compound etc. are subjected to series reaction, prepared light sensitive polyurethane film out is as TFTs
Insulating layer material, with the spies such as insulation performance is good, transparent and homogeneous, patterning, surface roughness is low, impurity concentration is low
Point.
In present pre-ferred embodiments, a kind of preparation method of light sensitive polyurethane is provided, as shown in Figure 1 comprising
Following steps：
S100, polyalcohol is dissolved, polyhydric alcohol solutions is made；Acrylic acid derivative is dissolved again, and is added dropwise to above-mentioned more
In first alcoholic solution, after reacting a period of time, filtration washing, and be dried, it is for use that light sensitivity diol compound is made；
S200, by light sensitivity diol compound obtained above and diisocyanate compound, double officials containing active hydrogen
Compound can be rolled into a ball and catalyst is dissolved in organic solvent and is reacted, reprecipitation is filtered and washed, and is obtained prepared photosensitive
Property polyurethane；
The general formula of the polyalcohol is R (OH)n, wherein n=3,4.
Light sensitive polyurethane in the present invention be using first prepare light sensitivity diol compound further with diisocyanate
What ester type compound and the common reaction of other bifunctional compounds containing active hydrogen were prepared.It is prepared by secondary response
The light sensitive polyurethane gone out has simple processing, good insulating, surface roughness low, the light as TFTs insulating layer materials
After quick property polyurethane material film can direct ultraviolet light writing in patterning, enormously simplify the manufacture craft of TFTs, and it adds
Work is at low cost, reproducible, mutually compatible with the manufacture craft of flexible display, makes the carrier mobility of the TFTs of gained and opens
Powered-down stream is relatively high.
Specifically, be in step S100 by general formula be R (OH) n, wherein n=3,4 polyalcohol, which is dissolved in solvent, to be made
Polyhydric alcohol solutions are for use, then acrylic acid derivative are dissolved in solvent, acrylic acid derivative solution is made, and will be made
Acrylic acid derivative solution is slowly added dropwise into above-mentioned polyhydric alcohol solutions, after reacting a period of time, filtration washing, and done
It is dry, it is for use to separate and collect obtained light sensitivity diol compound.
Preferably, can be added catalyst or polymerization inhibitor in the step s 100, the catalyst can be sodium hydroxide or
Triethylamine, the polymerization inhibitor can be hydroquinones.Catalyst, which is added, can promote extent of reaction, and polymerization inhibitor is added can be with
Effectively acrylic acid derivative is prevented to polymerize.
The polyalcohol used in the present invention is R (OH) for general formulanPolyalcohol, wherein n=3,4.It is more in preferred embodiment
First alcohol includes 2- ethyl -2- methylols -1,3- propylene glycol/trimethylolpropane, 2- methylol -1,3- propylene glycol, isophthalic front three
It is one or more in alcohol, glycerine or pentaerythrite.
In addition, the acrylic acid derivative includes：General formula isAcryloyl chloride class compound, general formula be
(R2CO)2The acrylic acid compound anhydride and general formula of O beAcrylic acid methanol esters compounds in one kind or
It is a variety of.It can be facilitated and R (OH) using the acrylic acid derivative of above-mentioned three kinds of general structuresnReaction, and the light sensitivity of its preparation
Polyurethane has good insulating properties and transparent and homogeneous.
Preferably, the acryloyl chloride class compound includes one in methacrylic chloride, acryloyl chloride or cinnamoyl chloride
Kind is a variety of；Acrylic anhydride derivatives quasi-compound includes acrylic anhydride, methacrylic anhydride, maleic anhydride, dimethyl Malaysia
It is one or more in acid anhydrides or cinnamic anhydride；Acrylic acid methanol ester derivant class compound includes methyl methacrylate or third
It is one or more in e pioic acid methyl ester.
Above-mentioned polyalcohol and acrylic acid derivative carry out series reaction in the present invention, carry out preliminary condensation reaction, are formed
Light sensitivity diol compound.As object before the reaction of step S200.
In step s 200, using the light sensitivity diol compound and diisocyanates made by above-mentioned steps S100
It closes object and other bifunctional compounds containing active hydrogen is reacted, the light sensitive polyurethane of the present invention is made.
Specifically, by appropriate light sensitivity diol compound, diisocyanate compound and other pairs containing active hydrogen
Functional compounds are dissolved in organic solvent, and a small amount of catalyst is added and carries out catalysis reaction, under the protection of inert gas
Reaction a period of time, washing of precipitate is finally carried out, obtain light sensitive polyurethane, after being repeated several times dissolving precipitation, can obtained
To more pure light sensitive polyurethane material.
Obtained light sensitive polyurethane material in the present invention, be made into after light sensitive polyurethane film be exposed it is aobvious
Shadow and baking can get the polyurethane film insulating layer of patterning, transparent and homogeneous, high quality.Compared to traditional TFTs insulating layers
Material, the polyurethane insulating layer and the compatibility of TFTs and flexible substrates prepared by the present invention are preferable, and TFTs devices of gained
The carrier mobility and switching current of part are higher, and carrier mobility reaches 1.3 cm2/Vs, and switching current ratio reaches
105, so that the overall performance of flexible display device is improved.
Preferably, the diisocyanate compound employed in present pre-ferred embodiments includes aromatic diisocyanates
It is one or more in ester type compound, aliphatic diisocyanate class compound or alicyclic diisocyanate class compound.
Include that 1,6- hexyl diisocyanates, 2,4- toluene two are different as suitable diisocyanate in reactant of the present invention
Cyanate, 2,6- toluene di-isocyanate(TDI)s, 1,4- phenyl diisocyanates, 4,4'Methyl diphenylene diisocyanate, 2,4- bis-
Methylenebis phenyl isocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4,4'Dicyclohexyl methyl hydride two
Isocyanates, benzene dimethylene diisocyanate, tetramethylxylylene diisocyanate, cyclohexyl -1,4- diisocyanates
Ester, Methylcyclohexyl diisocyanate, how -1,5- diisocyanate, 3,3'Dimethyl -4,4'Biphenyl diisocyanate or ring
It is one or more in hexyl dimethylene diisocyanate.
It is highly preferred that using 1,6- hexyl diisocyanates, 2,4- toluene di-isocyanate(TDI)s, 2,6- toluene di-isocyanate(TDI)s
Or it is one or more as reactant in isophorone diisocyanate, the light sensitive polyurethane in the present invention can be made to have more
Excellent insulation performance.
In addition, the bifunctional compound of the present invention containing active hydrogen, which includes at least ,-OH ,-SH ,-NH ,-NH2With
More than two compounds in CH- acidic-groups.
In a preferred embodiment of the present invention, the bifunctional compound containing active hydrogen includes that difunctional macromolecular is lived
Sprinkle the mixture of hydrogen compound and difunctional small molecule active hydrogen compounds.
Specifically, difunctional macromolecular active hydrogen compounds refers to molecular weight between 400-6000 in the present invention
Including at least having-OH ,-SH ,-NH ,-NH2With more than two compounds in CH- acidic-groups.Such as polyether diols, polyester
Glycol, polyamide diol, polyester-polyamide glycol, polyacetals glycol, poly- (alkylene ether) glycol, polythiaether glycol or makrolon
It is one or more in glycol.
Further, the polyether diols is prepared by epoxide carries out polycondensation reaction with polyalcohol.Epoxy
Compound is (chlorination or bromination) ethylene oxide, (chlorination or bromination) propylene oxide, (chlorination or bromination) epoxy butane or tetrahydrochysene
The condensation polymer and its block of furans, random and alternate copolymer or the graft copolymer with other polymers, such as ethylene oxide,
The random copolymer of propylene oxide, under high pressure with the graft copolymer of olefin polymer；And polyalcohol is ethylene glycol, 1,2- third
The small molecules glycol such as glycol and 1,4- butanediols.
Further, the polyester-diol, polyesteramide glycol and polyamide diol are by saturated or unsaturated polynary
Prepared by carboxylic acid is with saturated or unsaturated polyol reaction.Saturated or unsaturated polybasic carboxylic acid includes adipic acid, fourth two
It is one or more in acid, phthalic acid or maleic acid；
Wherein, the suitable polyalcohol for preparing polyester-diol include ethylene glycol, 1,2-PD, 1,4-butanediol,
It is one or more in neopentyl glycol, hexylene glycol or trimethylolpropane；For preparing the amido alcohol such as second of polyesteramide glycol
Hydramine etc.；For the diamines such as ethylenediamine and hexamethylene diamine etc. for preparing polyesteramide glycol and polyamide diol.It is double in the present invention
Functional group's active hydrogen compounds is most preferably undersaturated polyester-diol, polyesteramide glycol and polyamide diol.
Further, the polyacetals glycol is the reaction product using 1,4-butanediol or hexylene glycol and formaldehyde；Institute
The polythiaether glycol stated is that thiodiglycol and the polycondensation of ethylene oxide, propylene oxide, epoxy butane or tetrahydrofuran was used to produce
Object.
In addition, other suitable difunctional macromolecular active hydrogen compounds further include bisphenol-A, polybutadiene in the present invention
It is one or more in base glycol, polysiloxane group glycol or fluorinated diol.
Difunctional small molecule active hydrogen compounds includes small molecule dihydric alcohol, small molecule diamine and small point in the present invention
Sub- binary acid.
Further, small molecule dihydric alcohol includes dibromoneopentyl glycol, ethylene glycol, propylene glycol, neopentyl glycol, Isosorbide-5-Nitrae-fourth two
Alcohol, Isosorbide-5-Nitrae-butylene glycol, 1,6- hexylene glycols, furyl dimethyl carbinol, diglycol and N methyldiethanol amine, phenyl two
Isopropanolamine, N- ethyldiethanolamines, N- propyl diethanol amine, N- methyl dipropanolamines, two butanolamine of N- methyl, N- butyl two
It is one or more in the glycol amine of the N- such as butanolamine substitutions.
Further, small molecule diamine includes ethylenediamine, Putriscine, cyclohexanediamine, 1,6- hexamethylene diamines, the third two
It is one or more in amine, two sub- ethylene triamines, Sanya ethylene tetramine or polyethylene polyamine.
Further, small molecule binary acid includes mainly 2,2- dihydromethyl propionic acids, diamines yl carboxylic acid, tartaric acid, lemon
Acid, ethylenediamine base ethanesulfonic acid, 2- sulfonic acid -1,4-butanediol, 2,4-, bis- anilinesulfonic acids, N, N- bis- (ethoxy)-glycine, two
(methylol) propionic acid, N, it is one or more in N- bis- (ethoxy) -2-aminoethanesulfonic acid, can also be by the three of low molecular weight
Prepared by first alcohol (such as glycerine) and dibasic acid anhydride (such as maleic anhydride or succinic anhydride) contains a carboxyl and two hydroxyls
Half ester compound.
In present pre-ferred embodiments, the organic solvent used in step S200 includes：
Low boiling point (100 DEG C of atmospheric boiling point <) ketones solvent such as acetone, butanone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), hexamethylene
It is one or more in ketone, tetrahydrofuran, 1,4- dioxane；
Or high boiling solvent such as N-Methyl pyrrolidone, n,N-Dimethylformamide, n,N-dimethylacetamide, diformazan
It is one or more in base sulfoxide.
Organic solvent is used for dissolving light sensitivity diol compound, diisocyanate compound, the two-tube energy containing active hydrogen
Group's compound etc. need to have good dissolubility, and all be not easy to cure under conditions of high temperature or low temperature, can keep good
Solubility property.
In addition, being not particularly limited to catalyst type added in step S200 in the present invention, such as can be used organic
In tin catalyst, amines catalyst it is one or more come promote reaction progress.
Specifically, the organic tin catalyst is Mono-n-butyltin, Dibutyltin oxide, dibutyl oxalic acid
It is one or more in tin, oxalic acid tin, stannous octoate, two tin octoates or dibutyl tin dilaurate；The amines catalyst
Selected from triethylamine, two sub- ethylene triamines, triethylenediamine, five methyl diethylentriamine, tetramethyl diamino ethyl ether or
It is one or more in DMIZ 1,2 dimethylimidazole.
By mass percentage, the addition of the catalyst accounts for the 0.01- of reactant gross mass in step S200
0.06%.The preferred triethylenediamine of catalyst in the present invention accounts for reactant gross mass in step S200 of the present invention
0.03%。
The number-average molecular weight of light sensitive polyurethane prepared by the present invention is 5000-100000.Preferably, institute of the present invention
The number-average molecular weight of the light sensitive polyurethane of preparation is 20000, and molecular weight may be used gel permeation chromatography and be measured,
This is not repeated.
In addition, light sensitive polyurethane made of the present invention also provides one kind prepared by the above method.
Light sensitive polyurethane in the present invention can be by inkjet printing when being used as insulating layer, spin coating and various known
Prepared light sensitive polyurethane is filmed coating method etc.（Light sensitive polyurethane insulating layer of thin-film）.Pass through inkjet printing
The light sensitive polyurethane insulating layer of formation directly can form patterned film by one step of ultraviolet radiation-curable；And pass through spin coating
Or coating method is formed by light sensitive polyurethane insulating layer material, is formed a film by ultraviolet radiation-curable, can further make
Patterned film is formed with developing technique.
Further, during light sensitive polyurethane insulating layer of thin-film ultraviolet light cures, when photosensitive group isOrWhen, when exposure, need to add photosensitizer.By mass percentage, the dosage of the photosensitizer
For the 0.3%-8% of light sensitive polyurethane quality.
Further, photosensitizer includes -1 acetone of 2- hydroxy-2-methyl -1- phenyl, 2,2- dimethoxy -2- phenyl benzene
Ethyl ketone, 2- methyl-1s-(4- methyl mercaptos phenyl) -2- morpholinyl -1- acetone, 1- hydroxycyclohexyl phenyl ketones, 2,2- dimethoxies
Bis- (2,4,6- trimethylbenzoyls) phosphine oxides of base-phenyl ketone, phenyl, 2- phenyl benzyl -2- dimethyl amines -1- (4- morpholines
Benzyl phenyl) it is one or more in butanone, 2,4- dimethyl thioxanthone or 2,4- diethyl thioxanthones.
And in developing technique, developer solution used be propylene-glycol monoalky lether, propylene glycol alkyl ether acetic acid ester, cyclopentanone,
Butyl acetate, methyl iso-butyl ketone (MIBK), 2,4- dimethyl benzenes, 4-methyl-2 pentanone, cyclohexanone, 2-HEPTANONE, ethylene glycol monoethyl ether second
In acid esters, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, butyrolactone or n,N-Dimethylformamide
It is one or more.
The present invention also provides a kind of application of light sensitive polyurethane, that is, use it for the exhausted of TFT devices in flexible display
Edge layer.
The present invention also provides a kind of preparation sides by photosensitive insulative layer film for TFT devices in flexible display
Method, as shown in Fig. 2, it includes the following steps：
1, in carrier substrates 100（Glass or silicon chip）On prepare flexible base board 200, the flexible base board 200 can be PI,
PET or PEN any one or more ofs, and prepared flexible base board 200 is started the cleaning processing；
2, on flexible base board 200 prepare and patterned metal conductive layer be used as grid 300, the metal can for ITO,
The film of any formation in copper, molybdenum, titanium, silver, gold, tantalum, tungsten, chromium simple substance or aluminium alloy, or it is thin by the above single-layer metal
Two layers or more of the film that film is constituted；
3, according to the aforementioned method for preparing light sensitive polyurethane film, insulating layer is formed on grid 300 after patterning
Material 400；
5, using metal oxide TFT or organic tft as active layer 500；
6, source/drain electrode 600 is prepared by magnetically controlled DC sputtering mode at room temperature, and passes through photoetching and lift-off etc.
Technique realizes patterning, and used source/drain electrode metal formed by any one of aluminium, copper, molybdenum or titanium simple substance, or by with
Two layers or more of the film that upper metal simple-substance is constituted as the alloy material of main body and its above single layer metal firms.
The present invention is prepared for that patterned new material light sensitive polyurethane can be write direct, and applies in flexible display
When in part as the insulating layer in TFTs, have good insulating property (properties), and the carrier mobility of gained TFTs devices and
Switching current is higher（Carrier mobility reaches 1.3 cm2/Vs or so, and switching current ratio has reached 105 or so）So that it is aobvious
Show that the overall performance of device is improved.
The solution of the present invention is further illustrated below by specific embodiment：
Embodiment one：
1, light sensitive polyurethane building-up process
(1) synthesis of 2,2- dihydroxymethyls (methyl) methyl acrylate
2- ethyls -2- methylols -1,3-PD of 6.50 g is dissolved in 25 mL dichloromethane, 1 mL tri- is added
Ethamine（N(Et)3）, then the methacrylic chloride of 1.00 g is dissolved in 20 mL dichloromethane by ice bath stirring, nitrogen is protected
It is slowly added dropwise in above-mentioned solution, is added dropwise under shield within 1.5 hours or so, then proceed to react 5 hours under ice bath, room temperature is anti-
It after answering 30 hours, filters, washing, is evaporated to obtain 2,2- dihydroxymethyls (methyl) methyl acrylate after anhydrous sodium sulfate drying.
(2) synthesis of light sensitive polyurethane
By 2.62 g (10 mmol) dicyclohexyl methyl hydride-, 4,4 '-diisocyanate, 0.61 g (3 mmol) 2,2- bis-
Methylol (methyl) methyl acrylate, 1.29 g (5 mmol) hydroxyethyl terephthalate, 2g (2 mmol) ethylene oxide are poly-
Ether glycol（Mw=1000）, the dibutyl tin laurate of catalytic amount (0.10 g)（DBTL）It is dissolved in the anhydrous tetrahydrochysene furans of 30 mL
It mutters（THF）（Preferred solvent）In, lead to nitrogen protection, 70 DEG C of reactions are stood after 6 hours to room temperature, are precipitated with 300 mL n-hexanes,
Light sensitive polyurethane white solid is obtained, gained powder is redissolved in anhydrous tetrahydro furan, then through n-hexane repeated precipitation
Washing can obtain purer polyurethane products three times.
2, light sensitive polyurethane film preparation
Light sensitive polyurethane prepared by the present invention is dissolved in tetrahydrofuran（THF）In solvent, addition accounts for the poly- ammonia of light sensitivity
- 1 acetone of photosensitizer 2- hydroxy-2-methyl -1- phenyl that ester ratio is 0.3% is configured to the solution that mass fraction is 8%, uses hole
The polytetrafluoroethylene (PTFE) ultrafiltration membrance filter that diameter is 0.22 μm, is then spun on substrate, and forward rotary speed is 500 rpm,
Time be 5 s, after rotate rotary speed be 2500 rpm, the time be 20 s, film thickness 600nm.Then put it into 60 DEG C of vacuum
Oven temperature is adjusted to 120 DEG C of baking polyurethane films 10 by dry 20 min to remove solvent with the mode of temperature programming in baking oven
Min, subsequent natural cooling.
This light sensitive polyurethane film, 5 min of time for exposure are exposed, exposure power is 200 W, wavelength 200-400nm
Mixing wave band；After exposure, its film is developed with butyrolactone, developing time 90s；It is dried after finally being carried out at 120 DEG C, when
Between be 30min, to obtain patterned, homogeneous and transparent, high quality, patterned cross-linked polyurethane thin dielectric film.
Embodiment two：
1, light sensitive polyurethane building-up process
(1) synthesis of 2,3- dihydroxycinnamic acids propyl ester
The glycerine of 4.60 g is dissolved in 20 mL anhydrous methylene chlorides, is then dissolved the cinnamic anhydride of 1.66 g
It in 20 mL anhydrous methylene chlorides, is slowly added dropwise in above-mentioned solution, is added dropwise within 0.5 hour or so, is to slowly warm up to flow back
It after reaction 1 hour, filters, washing, is evaporated to obtain 2,3- dihydroxycinnamic acid propyl ester after anhydrous sodium sulfate drying.
(2) synthesis of light sensitive polyurethane
By 1.68 g (10 mmol) 1,6- hexyl diisocyanates（HDI）, 0.89 g (4 mmol) 2,3- dihydroxy
Propyl cinnamate, 0.31 g (3 mmol) neopentyl glycol (NPG), 2.40g (3 mmol) are poly-（Isophthalic anhydride-co- horses
Carry out acid anhydrides-co- butanediols）Esterdiol（Mw=800）, it is anhydrous that the triethylenediamine of catalytic amount (0.15 g) is dissolved in 40 mL
Tetrahydrofuran（THF）（Preferred solvent）In, lead to nitrogen protection, 70 DEG C reaction 6 hours after stand to room temperature, with 300 mL n-hexanes
Precipitation is to get to light sensitive polyurethane white solid, and gained powder is redissolved in anhydrous tetrahydro furan, then repeatedly through n-hexane
Washing of precipitate can obtain purer polyurethane products three times.
2, light sensitive polyurethane film preparation
Light sensitive polyurethane prepared by the present invention is dissolved in butanone solvent, the solution that mass fraction is 5% is configured to,
The polytetrafluoroethylene (PTFE) ultrafiltration membrance filter for being 0.22 μm with aperture, then then puts it into 60 by its inkjet printing on substrate
Oven temperature is adjusted to 120 DEG C of baking polyurethane by dry 20 min to remove solvent with the mode of temperature programming in DEG C vacuum drying oven
10 min of film, subsequent natural cooling.
This light sensitive polyurethane material film, 4 min of time for exposure are exposed, exposure power is 500 W, wavelength 200-
The mixing wave band of 400nm；It is dried after finally being carried out at 120 DEG C, time 30min, to obtain patterned, transparent and homogeneous
, high quality, patterned cross-linked polyurethane thin dielectric film.
Embodiment three：
1, light sensitive polyurethane building-up process
(1) synthesis of 3,5- dihydroxymethyls acrylic acid benzyl alcohol ester
Three methanol of isophthalic of 5.00 g is dissolved in 20 mL toluene, 10 mg sodium hydroxides are added（NaOH）Catalyst,
Then a certain amount of hydroquinone polymerization inhibitor starts to be vigorously stirred, heating, when temperature reaches 85 DEG C.Then by 0.85 g's
Methyl acrylate is dissolved in 20 mL toluene, is slowly added dropwise in above-mentioned solution under nitrogen protection, is dripped within 1.5 hours or so
Finish, then proceed to reaction 8 hours, the maximum temperature in whole process is 100 DEG C, collects the product that reaction distillation goes out.Then will
Liquid filtering after reaction in flask is isolated filtrate obtained by catalyst and polymerization inhibitor and is evaporated under reduced pressure, and interception is corresponding
High alcohol ester fraction obtains 3, the 5- dihydroxymethyl acrylic acid benzyl alcohol esters of water white transparency
(2) synthesis of light sensitive polyurethane
By 2.50 g (10 mmol) 4,4'Methyl diphenylene diisocyanate（MDI）, 0.67 g (3 mmol) 3,
5- dihydroxymethyl acrylic acid benzyl alcohol esters, 0.34 g (3 mmol) cyclohexanediamine, 4.00 g (4 mmol) tetrahydrofuran polyether
Glycol（Mw=1000）, the Dibutyltin oxide of catalytic amount (0.10 g) is dissolved in 40 mL anhydrous tetrahydro furans（THF）（It is preferred that
Solvent）In, lead to nitrogen protection, 70 DEG C of reactions are stood after 6 hours to room temperature, are precipitated to get to light sensitivity with 200 mL n-hexanes
Polyurethane white solid, gained powder is redissolved in anhydrous tetrahydro furan, then can be obtained three times through the washing of n-hexane repeated precipitation
Purer polyurethane products.
2, light sensitive polyurethane film preparation
Light sensitive polyurethane prepared by the present invention is dissolved in tetrahydrofuran（THF）In solvent, addition accounts for the poly- ammonia of light sensitivity
The photosensitizer 2 that ester ratio is 0.5%, 2- dimethoxy -2- phenyl acetophenones are configured to the solution that mass fraction is 10%, use hole
The polytetrafluoroethylene (PTFE) ultrafiltration membrance filter that diameter is 0.22 μm, is then spun on substrate, and forward rotary speed is 500 rpm,
Time be 10 s, after rotate rotary speed be 2000 rpm, the time be 30 s, film thickness 500nm.Then put it into 60 DEG C of vacuum
Oven temperature is adjusted to 120 DEG C of baking polyurethane films 10 by dry 20 min to remove solvent with the mode of temperature programming in baking oven
Min, subsequent natural cooling.
This light sensitive polyurethane material film, 5 min of time for exposure are exposed, exposure power is 1000 W, wavelength 200-
The mixing wave band of 400nm；After exposure, its film is developed with cyclohexanone, developing time 120s；Finally carried out at 120 DEG C
After dry, time 30min, to obtain patterned, homogeneous and transparent, high quality, patterned cross-linked polyurethane film
Insulating layer.
It should be understood that the application of the present invention is not limited to the above for those of ordinary skills can
With improvement or transformation based on the above description, all these modifications and variations should all belong to the guarantor of appended claims of the present invention
Protect range.
Claims (10)
1. a kind of preparation method of light sensitive polyurethane, which is characterized in that include the following steps：
A, polyalcohol is dissolved, polyhydric alcohol solutions is made；Acrylic acid derivative is dissolved again, and is added dropwise to above-mentioned polyhydric alcohol solutions
In, after reacting a period of time, filtration washing, and be dried, it is for use that light sensitivity diol compound is made；
B, by light sensitivity diol compound obtained above and diisocyanate compound, the difunctional chemical combination containing active hydrogen
Object and catalyst, which are dissolved in organic solvent, to be reacted, and reprecipitation is filtered and washed, and obtains prepared light sensitive polyurethane；
The general formula of the polyalcohol is R (OH)n, wherein n=3,4；
The polyalcohol includes 2- ethyl -2- methylols -1,3- propylene glycol/trimethylolpropane, 2- methylols -1,3- the third two
It is one or more in alcohol, three methanol of isophthalic, glycerine or pentaerythrite；
The acrylic acid derivative includes：Acryloyl chloride class compound, acrylic acid compound anhydride and acrylic acid methanol esters
It closes one or more in object;
The acryloyl chloride class compound includes one or more in methacrylic chloride, acryloyl chloride or cinnamoyl chloride；Third
Olefin(e) acid acid anhydride derivatives quasi-compound includes acrylic anhydride, methacrylic anhydride, maleic anhydride, dimethyl maleic anhydride or cinnamic acid
It is one or more in acid anhydride；Acrylic acid methanol ester derivant class compound includes in methyl methacrylate or methyl acrylate
It is one or more.
2. a kind of preparation method of light sensitive polyurethane according to claim 1, which is characterized in that the acrylic acid derives
Object includes：General formula isAcryloyl chloride class compound, general formula be (R2CO)2The acrylic acid compound anhydride and general formula of O
ForAcrylic acid methanol esters compounds in it is one or more.
3. a kind of preparation method of light sensitive polyurethane according to claim 1, which is characterized in that the diisocyanate
Class compound includes aromatic diisocyanate class compound, aliphatic diisocyanate class compound and alicyclic diisocyanate
It is one or more in ester type compound.
4. a kind of preparation method of light sensitive polyurethane according to claim 1, which is characterized in that described to contain active hydrogen
Bifunctional compound include at least have-OH ,-SH ,-NH ,-NH2With more than two compounds in CH- acidic-groups；
The difunctional macromolecular active hydrogen compounds is polyether diols, polyester-diol, polyamide diol, polyester-polyamide
It is one or more in glycol, polyacetals glycol, poly- (alkylene ether) glycol, polythiaether glycol or polycarbonate glycol.
5. a kind of preparation method of light sensitive polyurethane according to claim 4, which is characterized in that described containing active hydrogen
Bifunctional compound includes the mixed of difunctional macromolecular active hydrogen compounds and difunctional small molecule active hydrogen compounds
Close object.
6. a kind of preparation method of light sensitive polyurethane according to claim 1, which is characterized in that the organic solvent packet
It includes：
Low boiling point ketones solvent：Acetone, butanone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone, tetrahydrofuran and 1,4- dioxies six
It is one or more in ring；
High boiling solvent：In N-Methyl pyrrolidone, n,N-Dimethylformamide, n,N-dimethylacetamide and dimethyl sulfoxide (DMSO)
It is one or more.
7. a kind of preparation method of light sensitive polyurethane according to claim 1, which is characterized in that by mass percentage
Meter, the addition of the catalyst account for the 0.01-0.06% of reactant gross mass in step B.
8. a kind of preparation method of light sensitive polyurethane according to claim 1, which is characterized in that the poly- ammonia of light sensitivity
The number-average molecular weight of ester is 5000-10000.
9. a kind of light sensitive polyurethane, which is characterized in that be prepared by claim 1-8 any one of them preparation methods.
10. a kind of application of light sensitive polyurethane, which is characterized in that by light sensitive polyurethane application as claimed in claim 9
In the insulating layer of TFT devices.
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| CN108373527B (en) * | 2018-02-27 | 2020-01-14 | 华南理工大学 | Preparation method and application of hyperbranched polyester-based polyurethane medical adhesive |
| CN110172327B (en) * | 2019-05-31 | 2021-09-14 | 山东领科新材料科技有限公司 | Photocuring composite adhesive and production process thereof |
| CN110540771A (en) * | 2019-09-06 | 2019-12-06 | 江门市阪桥电子材料有限公司 | Photosensitive solder resist material with short exposure time and preparation method thereof |
| CN114395129B (en) * | 2021-12-22 | 2023-07-14 | 山东一诺威新材料有限公司 | Preparation method of polyether polyol with photodegradation characteristics |
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