CN101974201B - Ultraviolet thick-film photoresist and film-forming resin thereof - Google Patents
Ultraviolet thick-film photoresist and film-forming resin thereof Download PDFInfo
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- CN101974201B CN101974201B CN2010102977516A CN201010297751A CN101974201B CN 101974201 B CN101974201 B CN 101974201B CN 2010102977516 A CN2010102977516 A CN 2010102977516A CN 201010297751 A CN201010297751 A CN 201010297751A CN 101974201 B CN101974201 B CN 101974201B
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- LBBUXLSCTZQVFR-UHFFFAOYSA-N CS(c1cccc(C2=O)c1C=CC2=[NH+][NH-])(=O)=O Chemical compound CS(c1cccc(C2=O)c1C=CC2=[NH+][NH-])(=O)=O LBBUXLSCTZQVFR-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses an ultraviolet thick-film photoresist. The photoresist is mainly prepared by the following steps of: mixing 10 to 35 parts of phenolic resin, 1 to 10 parts of silicon-containing copolymer film-forming resin, 5 to 20 parts of diazo naphthoquinone light-sensitive compound, 30 to 85 parts of solvent and a small number of other additives such as n-butylamine and a surfactant serving as raw materials; and filtering the mixture by using 5-micron, 1-micron and 0.2-micron filters. In a thick-film ultraviolet exposure positive photoresist which is applied to the embossing process of advanced packaging and the manufacturing of micro electro mechanical systems (MEMS) and is prepared by the invention, a one-step film thickness uniform adhesive spinning piece is up to 1 to 20 microns and a multi-step film thickness uniform adhesive spinning piece is up to 50 to 100 microns as required.
Description
Technical field
The present invention relates to thick film ultraviolet photolithographic glue composition and the film-forming resin thereof used in a kind of advanced person's encapsulation that is applicable to large-scale integrated circuit (silicon chip level encapsulation WLP) and microelectromechanical systems (MEMS, the Micro-Electronic Machine System) field.
Background technology
In the preparation process of large-scale integrated circuit, encapsulation is last one procedure, and encapsulation technology also develops rapidly as its preceding road technology.Encapsulation, i.e. the silicon chip level encapsulation (WLP, wafer level package) when encapsulation has developed into whole silicon wafer by one integrated circuit block single respectively of at present advanced encapsulation technology.In potting process, need multiple packaged material, the thick film uv-exposure positive photoresist that the present invention relates to is a necessary key function material in bump process (Bumping) process.
Microelectromechanical systems (MEMS) is meant and integrates microsensor, performer and signal processing and pilot circuit, interface circuit, communicates by letter and the miniature electronic Mechatronic Systems of power supply.The basic characteristics that have microminiaturization, intellectuality, multi-functional, high integration and be suitable for producing in enormous quantities.A brand-new technology field has been opened up in the development of MEMS technology, and the micro sensor, microactrator, micro parts, Micromechanical Optics device, vacuum microelectronic device, power electronic devices etc. that adopt the MEMS fabrication techniques all have the wide application prospect of ten minutes in Aeronautics and Astronautics, automobile, biomedicine, environmental monitoring, military affairs and all areas that almost people touched.The leading product in MEMS market are that pressure transmitter, jerkmeter, minisize gyroscopes, marking ink nozzle and hard drive are first-class at present.The method of manufacture of MEMS is to accomplish through the repeatedly photoetching and the related process of thick film ultraviolet photoresist.The thick film uv-exposure positive photoresist that the present invention relates to also be make the MEMS device have favorable mechanical performance, a key function material of adhesion property and anti-etching performance.
The thick film photolithography glue that is applied to advanced encapsulation and MEMS manufacturing is not high to resolution requirement, but requires very high to etch resistance and pattern side wall verticality.
Because the increase of photoresist material thickness; In photoetching process, not only require necessary photosensitivity, promptly exposure intensity can not be too big, and the time shutter can not be oversize; Simultaneously glued membrane electroplate and etching process in must remain unchanged shape, do not ftracture, good adhesivity, anti-plate and anti-etching performance promptly will be arranged.The general at present negativity ultraviolet photoresist that uses because highly cross-linked back molecular chain is very stiff, is prone to produce internal stress in postchannel process, and pattern distortion, glued membrane cracking occur, even the phenomenon that comes off, and can't reach processing requirement.In addition,, Hou Dao, often gets into trouble in removing photoresist operation because of the glued membrane after crosslinked is difficult to remove.
Summary of the invention
The object of the invention provides a kind of ultraviolet thick film photolithography glue and film-forming resin thereof.
For achieving the above object, first kind of technical scheme that the present invention adopts is: a kind of film-forming resin, and said film-forming resin is made up of resol and silicon-containing copolymer film-forming resin two portions;
Said resol is by general molecular formula (I), (II) and at least a methylphenol and formaldehyde (III) get through polycondensation, and its molecular-weight average is 6000～50000;
In the formula: R
1Be CH
3
Said silicon-containing copolymer film-forming resin is got through copolyreaction under the condition that radical initiator exists by the monomer that meets chemical general formula (IV), the monomer that meets the monomer of chemical general formula (V) and meet chemical general formula (VI), and its molecular-weight average is 5000～150000;
In the formula: R
2Be H or CH
3R
3Be that carbonatoms is 1～20 alkyl; R
4Be that carbonatoms is 1～20 alkyl; R
5Be that OH, carbonatoms are that 1～20 alkyl or carbonatoms are 1～20 alkoxyl group; N=1～5;
In the formula: R
6Be H or CH
3R
7Be that H, carbonatoms are that 1～20 alkyl, carbonatoms are that 3～8 naphthenic base or carbonatoms are 1～20 hydroxyalkyl;
In the formula: R
8Be H, OH, OCH
3Or OCOCH
3
For achieving the above object, second kind of technical scheme that the present invention adopts is: mainly be made up of the material of following mass parts:
11～45 parts of film-forming resins;
5～20 parts of light-sensitive compounds;
30～85 parts of solvents;
Said light-sensitive compound is for meeting chemical general formula (VII), (VIII), (IX) and at least a compound (X);
In the formula: o=10～1000; P=1～5; R
9Be
Perhaps
Said solvent is YLENE, methyl-phenoxide, propylene glycol monomethyl ether (HOCH
2CH
2OCH
3), dihydroxypropane single-ether, 1-Methoxy-2-propyl acetate (CH
3OCH
2CH
2CH
3OOCCH
3), tirethylene glycol methyl ether (HOCH
2CH
2OCH
2CH
2OCH
2CH
2OCH
3), at least a in tirethylene glycol ether, N-BUTYL ACETATE, acetic acid peopentyl ester, ethyl lactate, gamma-butyrolactone and the N-Methyl pyrrolidone.
Related content in the technique scheme is explained as follows:
1, in the such scheme, described methylphenol is Ortho Cresol, p-cresol, m-cresol, 2,3-xylenol, 3,5-xylenol, 2; 4-xylenol, 2,6-xylenol, 2,3; 5-pseudocuminol or 2.
2, in the such scheme, the said monomer that meets chemical general formula (IV) has:
Methylacrylic acid propyl trialkoxy silane ester;
Vinylformic acid propyl trialkoxy silane ester;
Methylacrylic acid propyl group dialkoxy silicane ester;
Vinylformic acid propyl group dialkoxy silicane ester;
Methylacrylic acid ethyl trialkoxy silane ester;
Vinylformic acid ethyl trialkoxy silane ester;
Methylacrylic acid ethyl dialkoxy silicane ester;
Vinylformic acid ethyl dialkoxy silicane ester;
Methylacrylic acid methyl trialkoxy silane ester;
Vinylformic acid methyl trialkoxysilane ester;
Methylacrylic acid methyl dialkoxy silicane ester;
Vinylformic acid methyl dialkoxy silicane ester;
Wherein, said alkoxyl group is that carbonatoms is 1～20 alkoxyl group.
3, in the such scheme, the said monomer that meets chemical general formula (V) has: vinylformic acid, methylacrylic acid, methyl acrylate, TEB 3K, ethyl propenoate, Jia Jibingxisuanyizhi, senecioate-hydroxyl ethyl ester, methylacrylic acid-beta-hydroxy ethyl ester, Propylene glycol monoacrylate, Rocryl 410, vinylformic acid glyceryl ester, glyceral methacrylate, vinylformic acid ring pentyl ester, methylacrylic acid ring pentyl ester, cyclohexyl acrylate, cyclohexyl methacrylate.
4, in the such scheme, the said monomer that meets chemical general formula (VI) has: para hydroxybenzene ethene, to acetoxy-styrene, to methoxy styrene, a hydroxy styrenes, an acetoxy-styrene, meta-methoxy vinylbenzene.
5, in the such scheme; The compound method of resol (cresol-formaldehyde resin): resol is by general addition polymerization method preparation, and promptly cresols and formaldehyde (the 31-37% aqueous solution) heat (90～120 ℃) reactive polymeric and resin in the presence of acid or alkaline catalysts.This moment, the resin average molecular weight range was 4,000 to 6,000.Residual formaldehyde and moisture (100～160 ℃) are removed in air distillation then.Because be the molecular weight of control resin, the molar ratio of cresols and formaldehyde generally is controlled at about 1: 0.8, makes cresols excessive.Therefore reacting the later stage must remove remaining cresols from system.The simplest method is that (160～220 ℃, 30～60mmHg) method is removed remaining cresols and residual formaldehyde and moisture content in the high temperature molecular distillation.Polyreaction is proceeded under this high temperature, and resin becomes the melting state, and stopped reaction is with control molecular resin amount, discharging immediately in good time.This moment, the resin average molecular weight range was 6,000 to 50,000.Melting resin cooling curing, through pulverize resin product.Remaining phenol content is less than 1% in the solid resin.
Because resin is the melting state, not only produces smell during discharging, operation such as the cleaning of the stirring of high-temperature material, discharging, cooling, pulverizing, reaction kettle is all very difficult.For the flow process that simplifies the operation, be convenient to the cleaning of material processing and reaction kettle, the health and protection environment of enhancing productivity and protecting the operator; After polyaddition reaction finishes, directly add the solvent that uses when preparing photoresist solution in the later process, make in the synthetic resins operation stage and just form resin solution; So both simplified resin synthesis phase production technique; Also saved the solution preparation process in back road, saved cost greatly, saved time and save trouble.Solid content calculating amount of resin and quantity of solvent according to solution during the preparation photoresist material get final product.
6, in the such scheme, the compound method of said silicon-containing copolymer film-forming resin: by comonomer under the condition that radical initiator exists, through in solvent, carrying out free radical copolymerization and suitable aftertreatment is prepared from.The initiator of the free radical copolymerization that can supply select for use has azo-initiator, like Diisopropyl azodicarboxylate (AIBN), and ABVN (ABVN) etc.; The peroxide initiator, like Lucidol (BPO), the trimethylacetic acid peroxo-tert-butyl ester (TBPPI) etc.
7, in the such scheme, the mass ratio of said resol and said silicon-containing copolymer film-forming resin is 10～35: 1～10.
8, in the such scheme, said chemical general formula (VII), (VIII), (IX) and the light-sensitive compound (X) of meeting has: 2,3, and 4-trihydroxy-benzophenone-5-DNQ sulphonate; 2,3,4-trihydroxy-benzophenone-4-DNQ sulphonate; 2,3,4,4 '-tetrahydroxybenzophenone-5-DNQ sulphonate; 2,3,4,4 '-tetrahydroxybenzophenone-4-DNQ sulphonate; Poly phenolic aldehyde-5-DNQ sulphonate; Poly phenolic aldehyde-4-DNQ sulphonate; Poly bis-phenol aldehyde-5-DNQ sulphonate; Poly bis-phenol aldehyde-4-DNQ sulphonate.
9, in the such scheme, said YLENE is p-Xylol, o-Xylol, m-xylene or their mixture.
Because the technique scheme utilization, the present invention compared with prior art has advantage and effect:
1, the present invention makes is applied in the bump process process of advanced encapsulation and the thick film uv-exposure positive photoresist of MEMS in making, and the once even glue of its thickness gets rid of sheet and can reach 1～20 micron as required, and repeatedly even glue gets rid of sheet and can reach 50～100 microns.
2, the present invention in the film-forming resin that with resol is the basis, add a kind of alkali soluble the multipolymer of the propenoate that contains silicone couplet and substituted phenylethylene in order to increase adhesion, snappiness, verticality of side wall and the mechanical property of membrane-forming agent, reach in bump process is made with MEMS and prevent the purpose that glued membrane cracking, pattern are out of shape even come off.
Embodiment
Below in conjunction with embodiment the present invention is further described:
Embodiment one～12: siliceous I-line ultraviolet photoresist and film-forming resin thereof
One, resol part:
(1), the monomer of resol and the mass fraction in film-forming resin thereof are as shown in the table:
| The monomer of addition polycondensation | |
| Embodiment one | M-cresol, p-cresol, formaldehyde |
| Embodiment two | M-cresol, Ortho Cresol, formaldehyde |
| Embodiment three | M-cresol, Ortho Cresol, formaldehyde |
| Embodiment four | M-cresol, p-cresol, Ortho Cresol, formaldehyde |
| Embodiment five | M-cresol, p-cresol, 3,5-xylenol, formaldehyde |
| Embodiment six | M-cresol, 2,4-xylenol, formaldehyde |
| Embodiment seven | Ortho Cresol, p-cresol, 2,3,5-pseudocuminol, formaldehyde |
| Embodiment eight | 3,5-xylenol, formaldehyde |
| Embodiment nine | Ortho Cresol, 2,4-xylenol, formaldehyde |
| Embodiment ten | 2,3,5-pseudocuminol, formaldehyde |
| Embodiment 11 | 2,3,5-pseudocuminol, p-cresol, formaldehyde |
| Embodiment 12 | 2,6-xylenol, formaldehyde |
(2), the compound method of the resol of embodiment one:
The m-cresol that in 1000 ml flasks that heating stirrer, TM, reflux exchanger and nitrogen gangway be housed, adds 100 grams (0.93mol); 150 gram (1.39mol) p-cresols, 150 gram (37%) formalins (1.85mol) and 3.2 gram oxalic acid.Begin to stir and be heated to 90～95 ℃, under this temperature, keep reaction 3 hours.Changeing back the stream device then is the simple distillation device, slowly heats the unreacted cresols of air distillation, formaldehyde and water, until 120～130 ℃.After this, the gradual slow underpressure distillation makes vacuum pressure reach 30～60mmHg at last, and temperature reaches 180 ℃, stops 30 minutes, about 15 minutes, makes temperature reach 200～220 ℃ at last, and reaction so far finishes.Stop heating, remove vacuum, as soon as possible resin is put into cooling curing in tetrafluoroethylene or the Stainless Steel Disc, obtain the Powdered resol of 210 grams after the pulverizing, molecular-weight average is 7000～29000, remaining phenol＜1% in the solid resin.
(3), the compound method of the resol of embodiment two:
The m-cresol that in 1000 ml flasks that heating stirrer, TM, reflux exchanger and nitrogen gangway be housed, adds 100 grams (0.93mol); 150 gram (1.39mol) Ortho Cresols, 150 gram (37%) formalins (1.85mol) and 3.2 gram oxalic acid.Begin to stir and be heated to 90-95 ℃, under this temperature, keep reaction 3 hours.Changeing back the stream device then is the simple distillation device, slowly heats the unreacted cresols of air distillation, formaldehyde and water, until 120～130 ℃.After this, the gradual slow underpressure distillation makes vacuum pressure reach 30～60mmHg at last, and temperature reaches 180 ℃, stops 30 minutes, about 15 minutes, makes temperature reach 200～220 ℃ at last, and reaction so far finishes.Sampling and measuring molecular resin amount and remaining phenol.Change the simple distillation device into reflux, close vacuum.Carefully slowly adding 250 gram tirethylene glycol methyl ethers when preparation photoresist material (or used other solvents) makes high sticking melting attitude resin become resin solution.Stop heating then, be chilled to room temperature, obtain concentration and be 45% be easy to shift the phenol resin solution of being convenient to join glue.Molecular weight is 7000-29000, remaining phenol＜1% in the solid resin.
(4), the compound method of the resol of embodiment three:
The compound method identical according to embodiment one, preparation solid resin or resin solution.Raw material is: 150 gram (1.39mol) m-cresols, 100 gram (0.93mol) p-cresols, 150 gram (37%) formalins (1.85mol) and 3.2 gram oxalic acid.Obtain 220 gram pulverulent solids resol, average molecular resin amount is 2.2 ten thousand, remaining phenol＜1% in the solid resin.
Or being dissolved in 250 gram solvents, to obtain concentration be 47% phenol resin solution.Molecular-weight average is 2.2 ten thousand, remaining phenol＜1% in the solid resin.
(5), the compound method of the resol of embodiment four:
The compound method identical according to embodiment one, preparation solid resin or resin solution.Raw material is: the m-cresol of 150 grams (1.39mol), 50 gram (0.46mol) p-cresols, 50 gram (0.46mol) Ortho Cresols, 150 gram (37%) formalins (1.85mol) and 3.2 gram oxalic acid.Obtain 220 gram pulverulent solids resol (three), molecular-weight average is 2.1 ten thousand, remaining phenol＜1% in the solid resin.
Or being dissolved in 250 gram solvents, to obtain concentration be 47% phenol resin solution.Molecular-weight average is 2.1 ten thousand, remaining phenol＜1% in the solid resin.
(6), the compound method of the resol of embodiment five:
The compound method identical according to embodiment one, preparation solid resin or resin solution.Raw material is: the m-cresol of 125 grams (1.15mol), 75 gram (0.69mol) p-cresols, 50 gram 3.5-xylenol (0.41mol), 150 gram (37%) formalins (1.85mol) and 3.2 gram oxalic acid.Obtain 200 gram pulverulent solids resol, average molecular resin amount is 1.9 ten thousand, remaining phenol＜1% in the solid resin.
Or being dissolved in 250 gram solvents, to obtain concentration be 44% phenol resin solution, and molecular-weight average is 1.9 ten thousand, remaining phenol＜1% in the solid resin.
(7), the compound method of the resol of embodiment six:
The compound method identical according to embodiment one, preparation solid resin or resin solution.Raw material is: the m-cresol of 150 grams (1.39mol), 100 grams 2,4-xylenol (0.93mol), 150 gram (37%) formalins (1.85mol) and 3.2 gram oxalic acid.Obtain 210 gram pulverulent solids resol, the resin molecular-weight average is 1.3 ten thousand, remaining phenol＜1% in the solid resin.
Or being dissolved in 250 gram solvents, to obtain concentration be 46% phenol resin solution, and molecular-weight average is 1.3 ten thousand, remaining phenol＜1% in the solid resin.
(8), the compound method of the resol of embodiment seven:
The compound method identical according to embodiment one, preparation solid resin or resin solution.Raw material is: the Ortho Cresol of 125 grams (1.16mol), 75 gram (0.69mol) p-cresols, 60 grams 2,3,5-pseudocuminol (0.44mol), 150 gram (37%) formalins (1.85mol) and 3.2 gram oxalic acid.Obtain 200 gram pulverulent solids resol, the resin molecular-weight average is 1.2 ten thousand, remaining phenol＜1% in the solid resin.
Or being dissolved in 250 gram solvents, to obtain concentration be 44% phenol resin solution, and molecular-weight average is 1.2 ten thousand, remaining phenol＜1% in the solid resin.
The compound method of the resol of embodiment eight～embodiment 12 is identical with embodiment's one.Two, silicon-containing copolymer film-forming resin part
(1) meets the monomer of chemical general formula (IV)
Embodiment one: KH-570 silane coupling agent, chemical name are γ-(methacryloxy) propyl trimethoxy silicane, and structural formula is CH
2=CC (CH
3) COO (CH
2)
3Si (OCH
3)
3
Embodiment two: vinylformic acid trimethoxy ethylsilane ester, and structural formula is:
CH
2＝CHCOO(CH
2)
2Si(OCH
3)
3
Embodiment three: the KH-570 silane coupling agent
Embodiment four: vinylformic acid propyl group dibutoxy silicon ester
Embodiment five: methylacrylic acid methyl diethoxy silane ester
Embodiment six: vinylformic acid methyl dipropoxy silicon ester
Embodiment seven: methylacrylic acid ethyl diethoxy silane ester
Embodiment eight: vinylformic acid ethyl tripropoxy silicon ester
Embodiment nine: methylacrylic acid methyl Trimethoxy silane ester
Embodiment ten: vinylformic acid ethyl diamyl TMOS ester
Embodiment 11: methylacrylic acid ethyl trimethoxy silane ester
Embodiment 12: vinylformic acid methylmethane TMOS ester
(2), the monomer that meets chemical general formula (V)
Embodiment one: methylacrylic acid-beta-hydroxy ethyl ester, methylacrylic acid
Embodiment two: Rocryl 410, TEB 3K, methylacrylic acid
Embodiment three: methylacrylic acid-beta-hydroxy ethyl ester, Bing Xisuandingzhi, para hydroxybenzene ethene
Embodiment four: vinylformic acid glyceryl ester
Embodiment five: Propylene glycol monoacrylate
Embodiment six: Jia Jibingxisuanyizhi
Embodiment seven: cyclohexyl methacrylate
Embodiment eight: cyclohexyl acrylate
Embodiment nine: glyceral methacrylate
Embodiment ten: vinylformic acid ring pentyl ester, vinylformic acid
Embodiment 11: ethyl propenoate
Embodiment 12: methylacrylic acid, methyl acrylate
(3), the monomer that meets chemical general formula (VI)
Embodiment one: vinylbenzene
Embodiment two: to acetoxy-styrene
Embodiment three: meta-methoxy vinylbenzene, para hydroxybenzene ethene
Embodiment four: an acetoxy-styrene
Embodiment five: to acetoxy-styrene, meta-methoxy vinylbenzene
Embodiment six: to acetoxy-styrene
Embodiment seven: to acetoxy-styrene
Embodiment eight: a hydroxy styrenes
Embodiment nine: para hydroxybenzene ethene
Embodiment ten: vinylbenzene
Embodiment 11: to methoxy styrene, vinylbenzene
Embodiment 12: a hydroxy styrenes, vinylbenzene
(4), the compound method of the silicon-containing copolymer film-forming resin of embodiment one:
In 1000 ml flasks that electric mixer, temperature regulator, reflux exchanger and import and export of nitrogen be housed, add 50 gram methylacrylic acid-beta-hydroxy ethyl esters; 10 gram vinylformic acid propyl trimethoxy silicane esters (KH-570), 80 gram vinylbenzene, 20 gram methylacrylic acids and 300 gram methyl alcohol; Under agitation fed nitrogen 5 minutes; Reacting by heating material to 65～70 ℃ add the mixed solution of 3.0 gram Diisopropyl azodicarboxylates (AIBN) and 50 gram methyl alcohol, continue under reflux state, to react 16～20 hours.Cooling reaction liquid to room temperature and slowly dropping to lets its deposition in 3 liters of heptane under agitation.Filter and collect white solid product.Then this white solid is dissolved in 300 milliliters of acetone and forms clear solution, this drips of solution is added form deposition in 3 liters of heptane under agitation again.The solid collected by filtration product.This product in 45 ℃ of dryings, gets 125 gram copolymer products under vacuum, yield is about 78%, and gel osmoticing chromatogram analysis gained molecular weight of copolymer is 7.8 ten thousand, and molecular-weight average is distributed as 1.82.
(5), the compound method of the silicon-containing copolymer film-forming resin of embodiment two:
Raw material consists of: 40 gram Rocryl 410s, and 80 gram TEB 3Ks, 30 gram methylacrylic acids, 10 gram vinylformic acid trimethoxy ethylsilane esters, 20 restrain acetoxy-styrene, 300 gram methyl alcohol and 3.0 gram Diisopropyl azodicarboxylates (AIBN).Get copolymer products 120 grams, molecular-weight average is 7.2 ten thousand, MWD 1.80.
(6), the compound method of the silicon-containing copolymer film-forming resin of embodiment three:
Raw material consists of: 35 gram methylacrylic acid-beta-hydroxy ethyl esters, 60 gram Bing Xisuandingzhis, 55 gram para hydroxybenzene ethene, 10 gram vinylformic acid trimethoxy propyl silane esters, 3.0 gram Diisopropyl azodicarboxylates (AIBN), 300 gram methyl alcohol.Get copolymer 1 25 grams, molecular-weight average 7.1 ten thousand, MWD 1.86.
(7), the compound method of the silicon-containing copolymer film-forming resin of embodiment four～12 is with embodiment one.
Three, photosensitizers 2,3,4-trihydroxy-benzophenone-5-DNQ sulphonate; 2,3,4-trihydroxy-benzophenone-4-DNQ sulphonate; 2,3,4,4 '-tetrahydroxybenzophenone-5-DNQ sulphonate; 2,3,4,4 '-tetrahydroxybenzophenone-4-DNQ sulphonate; Poly phenolic aldehyde-5-DNQ sulphonate; Poly phenolic aldehyde-4-DNQ sulphonate; Poly bis-phenol aldehyde-5-DNQ sulphonate; Poly bis-phenol aldehyde-4-DNQ sulphonate
Embodiment one: 2,3,4-trihydroxy-benzophenone-5-DNQ sulphonate, 2,3,4,4 '-tetrahydroxybenzophenone-5-DNQ sulphonate
Embodiment two: 2,3,4-trihydroxy-benzophenone-5-DNQ sulphonate, 2,3,4,4 '-tetrahydroxybenzophenone-4-DNQ sulphonate
Embodiment three: 2,3,4-trihydroxy-benzophenone-4-DNQ sulphonate, 2,3,4,4 '-tetrahydroxybenzophenone-5-DNQ sulphonate
Embodiment four: 2,3,4-trihydroxy-benzophenone-4-DNQ sulphonate, 2,3,4,4 '-tetrahydroxybenzophenone-4-DNQ sulphonate
Embodiment five: 2,3,4-trihydroxy-benzophenone-4-DNQ sulphonate, 2,3,4,4 '-tetrahydroxybenzophenone-5-DNQ sulphonate, poly phenolic aldehyde-5-DNQ sulphonate
Embodiment six: 2,3,4-trihydroxy-benzophenone-4-DNQ sulphonate, 2,3,4,4 '-tetrahydroxybenzophenone-5-DNQ sulphonate, poly bis-phenol aldehyde-4-DNQ sulphonate
Embodiment seven: poly bis-phenol aldehyde-5-DNQ sulphonate
Embodiment eight: 2,3,4,4 '-tetrahydroxybenzophenone-5-DNQ sulphonate
Embodiment nine: poly phenolic aldehyde-5-DNQ sulphonate
Embodiment ten: 2,3,4-trihydroxy-benzophenone-4-DNQ sulphonate
Embodiment 11: poly bis-phenol aldehyde-4-DNQ sulphonate
Embodiment 12: poly phenolic aldehyde-5-DNQ sulphonate
Four, solvent
Embodiment one: MIBK, ethyl lactate
Embodiment two: the tirethylene glycol methyl ether
Embodiment three: methyl ethyl ketone, N-BUTYL ACETATE
Embodiment four: dihydroxypropane single-ether
Embodiment five: tirethylene glycol methyl ether, N-BUTYL ACETATE, ethyl lactate
Embodiment six: MIBK
Embodiment seven: N-BUTYL ACETATE
Embodiment eight: acetic acid peopentyl ester, N-BUTYL ACETATE
Embodiment nine: the tirethylene glycol methyl ether
Embodiment ten: 1-Methoxy-2-propyl acetate
Embodiment 11: the tirethylene glycol ether
Embodiment 12: ethyl lactate
Five, the preparation of photoresist material and photoetching test
Join glue: according to different exposure requirements and thickness requirement, the prescription of adjustment photoresist material, preparation as follows.By resol (calculating 10～35 parts) with solid; Contain the propenoate of silicone couplet and the multipolymer of substituted phenylethylene (1～10 part); Light-sensitive compound (5～20 parts), solvent (30～85 parts) and a spot of for example 0.1 part of n-Butyl Amine 99,0.12 part of tensio-active agent; Be mixed with solution, stir more than 16 hours.Again through 5 microns, 1 micron, the filtration of 0.2 micron membranes.
Photoetching: even glue,, toast 105 ℃, 5～30 minutes by rotating speed 300-2000 rev/min.Exposure, g-line, I-line or g-line/I-line mix, 10～30mW/cm
2, 10～100 seconds; Develop AZ400K/ pure water, 1: 3,50～1200 seconds, 23 ℃.
Explain: join the operation that glue, photoetching and all relate to light-sensitive compound and all must under gold-tinted, carry out, prevent that exposure lost efficacy.
Table 1. is joined glue and photoetching test-results
Physicals comprises etch resistance, verticality of side wall, interlayer adhesion, toughness, physical strength of glued membrane etc.
Photosensitizers in the Comparative Examples is 2,3,4,4 '-tetrahydroxybenzophenone-5-DNQ sulphonate, and solvent is an ethyl lactate, other is all identical with embodiment.
The foregoing description only is explanation technical conceive of the present invention and characteristics, and its purpose is to let the personage who is familiar with this technology can understand content of the present invention and enforcement according to this, can not limit protection scope of the present invention with this.All equivalences that spirit is done according to the present invention change or modify, and all should be encompassed within protection scope of the present invention.
Claims (6)
1. film-forming resin, it is characterized in that: said film-forming resin is made up of resol and silicon-containing copolymer film-forming resin two portions, and the mass ratio of said resol and said silicon-containing copolymer film-forming resin is 10～35: 1～10;
Said resol is by general molecular formula (I), (II) and at least a methylphenol and formaldehyde (III) get through polycondensation, and its molecular-weight average is 6000～50000;
In the formula: R
1Be CH
3
Said silicon-containing copolymer film-forming resin is got through copolyreaction under the condition that radical initiator exists by the monomer that meets chemical general formula (IV), the monomer that meets the monomer of chemical general formula (V) and meet chemical general formula (VI), and its molecular-weight average is 5000～150000;
In the formula: R
2Be H or CH
3R
3Be that carbonatoms is 1～20 alkyl; R
4Be that carbonatoms is 1～20 alkyl; R
5Be that OH, carbonatoms are that 1～20 alkyl or carbonatoms are 1～20 alkoxyl group; N=1～5;
In the formula: R
6Be H or CH
3R
7Be that H, carbonatoms are that 1～20 alkyl, carbonatoms are that 3～8 naphthenic base or carbonatoms are 1～20 hydroxyalkyl;
In the formula: R
8Be H, OH, OCH
3Or OCOCH
3
2. film-forming resin according to claim 1 is characterized in that: described methylphenol is Ortho Cresol, p-cresol, m-cresol, 2,3-xylenol, 3; 5-xylenol, 2,4-xylenol, 2,6-xylenol, 2; 3; 5-pseudocuminol or 2.
3. film-forming resin according to claim 1 is characterized in that: the said monomer that meets chemical general formula (IV) has:
Methylacrylic acid propyl trialkoxy silane ester;
Vinylformic acid propyl trialkoxy silane ester;
Methylacrylic acid propyl group dialkoxy silicane ester;
Vinylformic acid propyl group dialkoxy silicane ester;
Methylacrylic acid ethyl trialkoxy silane ester;
Vinylformic acid ethyl trialkoxy silane ester;
Methylacrylic acid ethyl dialkoxy silicane ester;
Vinylformic acid ethyl dialkoxy silicane ester;
Methylacrylic acid methyl trialkoxy silane ester;
Vinylformic acid methyl trialkoxysilane ester;
Methylacrylic acid methyl dialkoxy silicane ester;
Vinylformic acid methyl dialkoxy silicane ester;
Wherein, said alkoxyl group is that carbonatoms is 1～20 alkoxyl group.
4. film-forming resin according to claim 1 is characterized in that: the said monomer that meets chemical general formula (V) has: vinylformic acid, methylacrylic acid, methyl acrylate, TEB 3K, ethyl propenoate, Jia Jibingxisuanyizhi, senecioate-hydroxyl ethyl ester, methylacrylic acid-beta-hydroxy ethyl ester, Propylene glycol monoacrylate, Rocryl 410, vinylformic acid glyceryl ester, glyceral methacrylate, vinylformic acid ring pentyl ester, methylacrylic acid ring pentyl ester, cyclohexyl acrylate, cyclohexyl methacrylate.
5. film-forming resin according to claim 1 is characterized in that: the said monomer that meets chemical general formula (VI) has: para hydroxybenzene ethene, to acetoxy-styrene, to methoxy styrene, a hydroxy styrenes, an acetoxy-styrene, meta-methoxy vinylbenzene.
6. ultraviolet thick film photolithography glue is characterized in that: mainly be made up of the material of following mass parts:
11～45 parts of film-forming resins;
5～20 parts of light-sensitive compounds;
30～85 parts of solvents;
Arbitrary claim is said in said film-forming resin such as the claim 1～5;
Said light-sensitive compound is for meeting chemical general formula (VII), (VIII), (IX) and at least a compound (X);
In the formula: o=101000; P=1～5; R
9Be
Perhaps
Said solvent is at least a in YLENE, methyl-phenoxide, propylene glycol monomethyl ether, dihydroxypropane single-ether, 1-Methoxy-2-propyl acetate, tirethylene glycol methyl ether, tirethylene glycol ether, N-BUTYL ACETATE, acetic acid peopentyl ester, ethyl lactate, gamma-butyrolactone and the N-Methyl pyrrolidone.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010102977516A CN101974201B (en) | 2010-09-30 | 2010-09-30 | Ultraviolet thick-film photoresist and film-forming resin thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102977516A CN101974201B (en) | 2010-09-30 | 2010-09-30 | Ultraviolet thick-film photoresist and film-forming resin thereof |
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| Publication Number | Publication Date |
|---|---|
| CN101974201A CN101974201A (en) | 2011-02-16 |
| CN101974201B true CN101974201B (en) | 2012-10-31 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104592436B (en) * | 2014-11-25 | 2018-05-08 | 昆山西迪光电材料有限公司 | Film-forming resin containing sesquiterpene lactone and its positivity 248nm photoresists |
| TWI643901B (en) * | 2015-12-16 | 2018-12-11 | 財團法人工業技術研究院 | Photo-imprinting resin composition, photo-imprinting resin film and patterning process |
| CN107127292B (en) * | 2017-06-28 | 2019-12-27 | 济南圣泉集团股份有限公司 | Binder for 3D printing and preparation method and application thereof |
| CN109062008B (en) * | 2018-08-21 | 2022-03-11 | 西陇科学股份有限公司 | Ultraviolet positive photoresist |
| CN111303362B (en) * | 2018-12-12 | 2023-05-30 | 上海飞凯材料科技股份有限公司 | Phenolic resin, preparation method thereof and photoresist |
| CN111484586A (en) * | 2020-04-27 | 2020-08-04 | 江苏准信自动化科技股份有限公司 | Linear phenolic resin for photoresist and preparation method thereof |
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| US5204216A (en) * | 1990-02-20 | 1993-04-20 | Basf Aktiengesellschaft | Radiation-sensitive mixture |
| CN1693323A (en) * | 2005-05-24 | 2005-11-09 | 苏州华飞微电子材料有限公司 | Film formed resin with copolymer of containing silicon coupling agent and 193 nm photoetching gule |
| WO2006006581A1 (en) * | 2004-07-14 | 2006-01-19 | Jsr Corporation | Photosensitive insulating resin composition, cured product thereof and use thereof |
| CN1818781A (en) * | 2006-03-13 | 2006-08-16 | 苏州华飞微电子材料有限公司 | Dark ultraviolet negative photoresist and filming resin |
| CN1818782A (en) * | 2006-03-13 | 2006-08-16 | 苏州华飞微电子材料有限公司 | Dark ultraviolet negative photoresist and filming resin |
| CN1828418A (en) * | 2006-03-27 | 2006-09-06 | 苏州华飞微电子材料有限公司 | 193nm photoresist containing silicon coupling agent and its filming resin |
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| US5204216A (en) * | 1990-02-20 | 1993-04-20 | Basf Aktiengesellschaft | Radiation-sensitive mixture |
| WO2006006581A1 (en) * | 2004-07-14 | 2006-01-19 | Jsr Corporation | Photosensitive insulating resin composition, cured product thereof and use thereof |
| CN1693323A (en) * | 2005-05-24 | 2005-11-09 | 苏州华飞微电子材料有限公司 | Film formed resin with copolymer of containing silicon coupling agent and 193 nm photoetching gule |
| CN1818781A (en) * | 2006-03-13 | 2006-08-16 | 苏州华飞微电子材料有限公司 | Dark ultraviolet negative photoresist and filming resin |
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| CN1828418A (en) * | 2006-03-27 | 2006-09-06 | 苏州华飞微电子材料有限公司 | 193nm photoresist containing silicon coupling agent and its filming resin |
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