CN105785716A - Photoresist - Google Patents
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- CN105785716A CN105785716A CN201410844561.XA CN201410844561A CN105785716A CN 105785716 A CN105785716 A CN 105785716A CN 201410844561 A CN201410844561 A CN 201410844561A CN 105785716 A CN105785716 A CN 105785716A
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Abstract
The invention discloses a photoresist, and belongs to the field of metal etching. The photoresist comprises the following components in parts by weight: 5-30 parts of cured resin, 10-50 parts of alkali-soluble resin, 5-25 parts of a polymeric monomer, 0.5-8 parts of a photoinitiator, 2-10 parts of a free radical polymerization initiator and 20-70 parts of a solvent, wherein the cured resin has carbon-carbon double bonds. According to the photoresist disclosed by the invention, the double-bond conversion ratio and the crosslinking density are improved; the cured photoresist forms a very compact and stable crosslinking structure; decomposition of the photoresist caused by an alkali attack is avoided; and the etching resistance is improved. Furthermore, according to the photoresist, the cured resin with the carbon-carbon double bonds is adopted as light-cured resin and heat-cured resin at the same time, and does not react with a carboxyl group in the alkali-soluble resin, so that the storage stability of the photoresist is improved.
Description
Technical field
The present invention relates to metal etch technical field, particularly to a kind of photoresist.
Background technology
Photoresist is also known as photoresist, and it is under irradiation under ultraviolet ray, it is possible to crosslinking curing or degradation reaction occur.After photoresist generation photo-crosslinking curing reaction, there is the characteristic not corroded by metal etch liquid, often use it for metal etch field.Photoresist generally includes has the light-cured resin of double bond, light trigger, solvent and auxiliary agent alternatively.But such photoresist is under the photocuring effect that light trigger causes, solidifying the double bond in resin can not be fully crosslinked, causes that the resin crosslink density after solidifying is relatively low, affects its etch resistant performance.Thus, it is necessary to improve to improve its etch resistant performance to the composition of photoresist.
Prior art provides such a photoresist, including the composition of following weight fraction: alkali soluble resins 10%-60%, epoxy resin 2%-30%, polymerization single polymerization monomer 5%-30%, light trigger 0.5%-8%, solvent 20%-80% and pigment 0.1%-5%.This photoresist improves its etch resistant performance by carrying out heat cure after photocuring again.Particularly as follows: the photoresist of above-mentioned improvement composition is coated with on metallic substrates, it is warming up to 80-110 DEG C with dry out solvent, then mask plate is used to cover on the metal basal board being coated with photoresist, metal basal board is exposed, receiving the photoresist generation cross-linking and curing reaction in the exposure region of illumination on metal basal board, the region after solidification is provided with the characteristic that not developed liquid cleans and do not corroded by metal etch liquid.After development, on metal basal board, the developed liquid of unexposed portion cleans, and exposed portion is retained.Make thermosetting resin carry out heat cure by high temperature (such as, more than 120 DEG C) photoresist after development again, improve crosslink density further.Finally using metal etch liquid to corrode this metal basal board, the position that on metal basal board, unglazed photoresist covers is etched, and the position that the photoresist being cured covers is protected, and is not etched by.After having etched, exposed portion photoresist lift off, obtain the pattern corresponding with mask plate.
Inventor have found that prior art at least there is problems in that
On the one hand, the polymerization single polymerization monomer in the photoresist that prior art provides still suffers from undersaturated double bond after photocuring, and cannot obtain saturated through follow-up curing process, causes the photoresist crosslink density after solidification low, and anti-etching ability also declines therewith.
On the other hand, the photoresist that prior art provides exists simultaneously there is the alkali soluble resins having hydroxy-acid group and the epoxy resin with epoxide group, and hydroxy-acid group is easy and epoxide group generation ring-opening reaction, reduce the storage stability of this photoresist so that it is rotten.Further, in such photoresist dry out solvent process after film, epoxide group shifts to an earlier date heat cure after being heated, and causing develops in subsequent technique even cannot not develop only, ultimately results in product formation mass defect.
Summary of the invention
Embodiment of the present invention technical problem to be solved is in that, it is provided that a kind of photoresist with high crosslink density and stiff stability.Concrete technical scheme is as follows:
A kind of photoresist, composition including following weight portion: the solvent solidifying resin, the alkali soluble resins of 10-50 part, the polymerization single polymerization monomer of 5-25 part, the light trigger of 0.5-8 part, the radical polymerization initiator of 2-10 part, 20-70 part of 5-30 part, has carbon-carbon double bond in described solidification resin.
As preferably, described photoresist includes the composition of following weight portion: the solvent solidifying resin, the alkali soluble resins of 20-40 part, the polymerization single polymerization monomer of 10-20 part, the light trigger of 2-5 part, the radical polymerization initiator of 4-8 part, 40-60 part of 10-20 part.
Further, described photoresist also includes the composition of following weight portion: the pigment of 0.1-5 part and the auxiliary agent of 0-5 part.
Specifically, described alkali soluble resins is the phenylethylene/maleic anhydride copolymer resins of (methyl) acrylic copolymeric resin and/or esterification.
Specifically, described (methyl) acrylic copolymeric resin is carried out copolymerization by ethylene system unsaturated monomer and/or propylene unsaturated monomer and (methyl) acrylic acid and obtains.
Specifically, described ethylene system unsaturated monomer, described propylene unsaturated monomer are respectively provided with following construction unit:
Wherein, R is hydrogen or methyl；
R1For phenyl, hydroxy phenyl, aminomethyl phenyl, ethylphenyl, naphthyl or itrile group；
R2、R3Hydroxyalkyl, dialkylaminoalkyl group, phenyl, benzyl or the Laurel ester group be the alkyl with 1-8 carbon atom, having 1-8 carbon atom, wherein, the alkyl in described dialkylaminoalkyl group includes 1-8 carbon number；
R4For having the alkyl of 3-8 carbon atom.
Specifically, described solidification resin is acrylate ,-CH in described acrylate2=CH-COO-group and-CH2=CH (CH3) total number of-COO-group is be more than or equal to 2.
Specifically, described acrylate at least one in Epocryl, polyester acrylate resin, polyurethane acrylate resin.
Specifically, described polymerization single polymerization monomer is ethylene system unsaturated monomer and/or propylene unsaturated monomer.
Specifically, described radical polymerization initiator is at least one in 80 DEG C of half-life organic peroxy class initiator more than 1 hour, inorganic peroxy class initiator and azo-initiator.
Specifically, described light trigger at least one in benzoin class, acetophenones, aminoacetophenone class, acylphosphine oxide class, benzophenone, Anthraquinones, thioxanthene ketone, triarylimidazoles dimer class, acridine, the luxuriant class of diphenyl titanium, tertiary amines light trigger.
Specifically, described solvent at least one in lipid solvent, ether solvent, alcohols solvent, ketones solvent, aromatic solvents, petroleum solvent.
The technical scheme that the embodiment of the present invention provides has the benefit that
On the one hand, the photoresist of the said ratio that the embodiment of the present invention provides, by under ultraviolet light conditions, light trigger absorbs luminous energy and produces free radical, causes solidification resin to form high polymer with polymerization single polymerization monomer generation photo-crosslinking curing reaction.After developed, the part (that is the photoresist film formed after photo-crosslinking solidification) solidified through photo-crosslinking in photoresist is retained.Under heating condition, radical polymerization initiator decomposes in the photoresist film retained becomes free radical, cause and solidify in resin and polymerization single polymerization monomer without the photocuring reaction further polymerization crosslinking of double bond completely, further increase the crosslink density of this photoresist.The photoresist that the visible embodiment of the present invention provides is by photo-crosslinking curing reaction-heat cross-linking curing reaction, improve double bond conversion rate and crosslink density, the photoresist after solidification is made to form very fine and close and stable cross-linked structure, it is to avoid it is attacked by alkali and decomposes, and improves its anti-etching performance.On the other hand, the photoresist that the embodiment of the present invention provides adopts the solidification resin with carbon-carbon double bond simultaneously as light-cured resin and heat reactive resin, and it will not react with the hydroxy-acid group in alkali soluble resins, improves the storage stability of this photoresist.
Detailed description of the invention
For making technical scheme and advantage clearly, below embodiment of the present invention is described further in detail.
First aspect, embodiments provide a kind of photoresist, composition including following weight portion: the solvent solidifying resin, the alkali soluble resins of 10-50 part, the polymerization single polymerization monomer of 5-25 part, the light trigger of 0.5-8 part, the radical polymerization initiator of 2-10 part, 20-70 part of 5-30 part, has carbon-carbon double bond in described solidification resin.
Second aspect, embodiments providing a kind of photoresist with optimum ratio, it includes the composition of following weight portion: the solvent solidifying resin, the alkali soluble resins of 20-40 part, the polymerization single polymerization monomer of 10-20 part, the light trigger of 2-5 part, the radical polymerization initiator of 4-8 part, 40-60 part of 10-20 part.
It will be appreciated by persons skilled in the art that " radical polymerization initiator " in the embodiment of the present invention refers to the compounds that can resolve into free radical under heating condition.The embodiment of the present invention can be made described radical polymerization initiator, it is preferable that be interpreted as high temperature radical initiator 80 DEG C of half-life more than 1 hour radical polymerization initiator.
The photoresist of the said ratio that the embodiment of the present invention provides, it is possible to carry out photocuring and heat cure.Specifically, by the irradiation of ultraviolet light (or other luminous energy), light trigger absorbs luminous energy and produces free radical, thus causing the double bond and the double bond generation photo-crosslinking curing reaction in polymerization single polymerization monomer that solidify in resin, thus forming high polymer.Then under heating condition, radical polymerization initiator decomposes produces free radical, thus causing in solidification resin and polymerization single polymerization monomer without the photocuring reaction further polymerization crosslinking of double bond completely, further increases the crosslink density of this photoresist.Solidified by photo-crosslinking and heat cross-linking solidification improves double bond conversion rate and crosslink density, the photoresist after solidification is made to form very fine and close and stable cross-linked structure, greatly reduce its swelling solvability in acidity and alkalinous metal etching solution such that it is able to make the photoresist after solidification reach not only acidproof but also alkaline-resisting performance.Additionally, the heat decomposition temperature of the radical polymerization initiator of embodiment of the present invention employing is higher, its stability at normal temperatures is high, is beneficial to the storage stability that improve this photoresist.And, the photoresist that the embodiment of the present invention provides adopts the solidification resin with carbon-carbon double bond simultaneously as light-cured resin and heat reactive resin, and it will not react with the hydroxy-acid group in alkali soluble resins, improves the storage stability of this photoresist.
Visible, the photoresist that the embodiment of the present invention provides is by photo-crosslinking curing reaction and heat cross-linking curing reaction, making its internal structure finer and close, its adhesive force, resolution, elching resistant, resistance to drying performance and stable storing performance all can be significantly improved, and its range of application is wider.It is additionally, since above-mentioned each composition simple and easy to get, cheap, improve the economic and practical of embodiment of the present invention photoresist.
It is understood that be distributed on metal basal board by the photoresist that the embodiment of the present invention provides, after photo-initiated crosslinking solidification and thermal initiation cross-linking and curing reaction, this photoresist forms the extraordinary photoresist film of consistency on metallic substrates.The photoresist film formed not only acid resistance etching solution but also alkali resistance etching solution, namely there is extraordinary acidproof with alkaline-resisting characteristic, can be applied in the metal etch liquid of wider scope, and be more suitable for and be etched on the metal basal board (such as, aluminum, copper and rustless steel etc.) of wider scope.This photoresist film after overetch, by adopting Conventional solvents (such as DMF, N,N-dimethylacetamide, dimethyl sulfoxide etc.) namely peelable, finally forms desired pattern on metallic substrates.
Specifically, this solidification resin is acrylate, wherein, and-CH contained in this acrylate2=CH-COO-group and-CH2=CH (CH3) total number of-COO-group is be more than or equal to 2.For example, this acrylate at least one in Epocryl, polyester acrylate resin, polyurethane acrylate resin.
The solidification resin that the embodiment of the present invention provides has acryloxy (-CH simultaneously2=CH-COO-) and methacryloxy (-CH2=CH (CH3)-COO-).Owing to, in Light Curing, acryloxy reactivity is high, will with polymerization single polymerization monomer generation cross-linking reaction.And methacryloxy is relatively big by its steric hindrance, photopolymerizable reactive is low, is not involved in or less participates in Light Curing, is retained.The methacryloxy that retained and without photocuring complete reaction acryloxy by follow-up curing process by the free radical polymerization after radical polymerization initiator pyrolysis, form further crosslinking curing network.Based on this, the embodiment of the present invention controls solidifying acryloxy in resin as be more than or equal to 2 with the total of methacryloxy.
Specifically, this alkali soluble resins is the phenylethylene/maleic anhydride copolymer resins of (methyl) acrylic copolymeric resin and/or esterification.
In order to enable to use alkaline-based developer to be washed down by uncured photoresist in follow-up developing process, reach the purpose of development, this photoresist is developed, the embodiment of the present invention uses the alkali soluble resins with hydroxy-acid group, so that this hydroxy-acid group in developing process with alkaline reaction, generate water miscible salt, make alkali soluble resins be dissolved in developer solution.Based on this, embodiment of the present invention operating weight number is 10-50 part, it is preferable that (methyl) acrylic copolymeric resin of 20-40 part and/or the phenylethylene/maleic anhydride copolymer resins of esterification are as alkali soluble resins.
Obtain more specifically, this (methyl) acrylic copolymeric resin is carried out copolymerization by ethylene system unsaturated monomer and/or propylene unsaturated monomer with (methyl) acrylic acid.Wherein, the weight average molecular weight being somebody's turn to do (methyl) acrylic copolymeric resin is 10000-200000, it is preferable that 50000-150000；Its acid number is 50-250, it is preferable that 100-200.
Alkali soluble resins contains suitable acid number, it is ensured that have enough hydroxy-acid groups and alkaline reaction in developing process, makes the photoresist of non-ultra-violet curing to wash down by developed liquid, reaches the purpose of development.Based on this, the acid number of (methyl) acrylic copolymeric resin is controlled at 50-250 by the embodiment of the present invention, it is preferable that 100-200.Owing to its physical property and processing characteristics are had important impact by the size of the weight average molecular weight of resin.After the weight average molecular weight of resin only reaches certain numerical value, just can show certain physical property.Therefore, the weight average molecular weight of resin can as the selection gist of process conditions various in the course of processing.And by (methyl) acrylic copolymeric resin matrix material as photoresist in the embodiment of the present invention, the hardness of photoresist, adhesive force, resolution and elching resistant etc. are all had important impact by it.Based on this, the weight average molecular weight of (methyl) acrylic copolymeric resin is controlled at 10000-200000 by the embodiment of the present invention, preferred 50000-150000, (methyl) acrylic copolymeric resin of above-mentioned weight average molecular weight is more conducive to prepared photoresist and has more excellent hardness, adhesive force, resolution and elching resistant.
Preferably, in order to control the weight average molecular weight of prepared (methyl) acrylic copolymeric resin between 10000-200000, this ethylene system unsaturated monomer, propylene unsaturated monomer are respectively provided with following construction unit:
Wherein, R is hydrogen or methyl；
R1For phenyl, hydroxy phenyl, aminomethyl phenyl, ethylphenyl, naphthyl or itrile group；
R2、R3Hydroxyalkyl, dialkylaminoalkyl group, phenyl, benzyl or the Laurel ester group be the alkyl with 1-8 carbon atom, having 1-8 carbon atom, wherein, the alkyl in described dialkylaminoalkyl group includes 1-8 carbon number；
R4For having the alkyl of 3-8 carbon atom.
Specifically, the maleic anhydride of styrene copolymer resins of this esterification carries out esterification by alcohol and phenylethylene/maleic anhydride copolymer resins and obtains.The concrete synthetic method of the maleic anhydride of styrene copolymer resins of this esterification includes: maleic anhydride and styrene are carried out polyreaction and obtains maleic anhydride of styrene copolymer resins；Then, under catalyst existent condition, make the alcohol with 1-10 carbon atom carry out esterification with the anhydride group in maleic anhydride of styrene copolymer resins, obtain the maleic anhydride of styrene copolymer resins of esterification.Wherein, the weight average molecular weight of the maleic anhydride of styrene copolymer resins of this esterification is 10000-200000, it is preferable that 20000-150000；Its acid number is 50-250, it is preferable that 100-200.
For example, the above-mentioned alcohol with 1-10 carbon atom can be propanol, butanol, amylalcohol, hexanol, enanthol, capryl alcohol, nonyl alcohol, decanol, isopropanol, sec-butyl alcohol, sec-amyl alcohol, secondary hexyl alcohol, second enanthol, sec-octyl alcohol, second nonyl alcohol, second decanol, the tert-butyl alcohol, and their combination etc..Preferred methanol, butanol, sec-butyl alcohol, sec-octyl alcohol, and do not limit above alcohols.The embodiment of the present invention is by being defined the alcohol of the above-mentioned 1-10 of having carbon atom, the alcohol being intended to ensure to carry out esterification with maleic anhydride of styrene copolymer resins is liquid condition, the alcohol of solution state serve not only as esterification reactant and can also as reaction medium, reaction can not only be made gentleer, be highly beneficial for improving the reaction rate of esterification.
Specifically, this polymerization single polymerization monomer is ethylene system unsaturated monomer and/or propylene unsaturated monomer.As preferably, the degree of functionality of this ethylene system unsaturated monomer and/or propylene unsaturated monomer is be more than or equal to 1.
Polymerization single polymerization monomer is under ultraviolet light conditions, it is possible to by free radical polymerization, occurs photo-crosslinking curing reaction to form high polymer, thus forming the photoresist film of densification.Polymerization single polymerization monomer appropriate in photoresist can ensure that the compactness and mechanical strength that solidify photoresist film.Based on this, in the embodiment of the present invention, polymerization single polymerization monomer weight is 5-25 part of this photoresist weight, it is preferable that 10-20 part, and is particularly limited as ethylene system unsaturated monomer and/or propylene unsaturated monomer.For example, this polymerization single polymerization monomer at least one in following material: simple function (methyl) esters of acrylic acids such as (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) 2-(Acryloyloxy)ethanol, (methyl) lauryl acrylate, glycidyl methacrylate, list (methyl) polyalkylene glycol acrylate ester；1,3-butanediol two (methyl) acrylate, 1,4-butanediol two (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate, glycerol two (methyl) acrylate, tripropylene glycol diacrylate, two senses (methyl) esters of acrylic acid such as hexanediol diester acrylates, polyethylene glycol 200 two (methyl) acrylate, PEG400 two (methyl) acrylate, Macrogol 600 two (methyl) acrylate；Trifunctional (methyl) esters of acrylic acids such as glycerol three (methyl) acrylate, tetramethylolmethane monohydroxy three (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, ethoxyquin trimethylolpropane tris (methyl) acrylate；Tetramethylol methane tetraacrylate etc. four sense (methyl) esters of acrylic acid；Dipentaerythritol monohydroxy five (methyl) acrylate, dipentaerythritol six (methyl) acrylate contour sense (methyl) esters of acrylic acid；Styrene, oxybenzene ethylene, α-methyl styrene, vinyltoluene, vinyl naphthalene, vinyl-dimethyl benzene, divinylbenzene, divinyl toluene, divinyl naphthalene, divinyl pyridine, divinyl silane, trivinyl silane, dimethyl divinyl silane, divinylmethyl silane, methyl trivinyl silane, divinyl phenyl silane, trivinyl phenyl silane, trivinyl silane, tetravinyl silane, poly-(methyl vinyl silicone), ethylene system unsaturated monomers such as poly-(methyl hydrogen siloxane), but do not limit above kind.
Light trigger decomposes generation free radical under ultraviolet light, thus causing the solidification resin with double bond and polymerization single polymerization monomer to produce photo-crosslinking, forms high polymer, thus forming the photoresist film of densification.Based on this, in the embodiment of the present invention, light trigger is defined to 0.5-8 weight portion, it is preferable that 2-5 weight portion.It will be understood by those skilled in the art that, light trigger in the embodiment of the present invention is prior art, for instance this light trigger can be selected from least one in following material: the benzoin classes such as benzoin, benzoin methyl ether, benzoin dimethyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butylether, benzoin alkylether, alpha-hydroxymethyl benzoin ether；1-Phenylethanone., 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy-2-phenyl acetophenone, 1, acetophenones, 2-hydroxy-2-methyl-1-phenylacetone, 2-methyl isophthalic acid-(4-methyl mercapto phenyl)-2-morpholine-1-acetone, 2-dimethylamino-2-benzyl-1-[4-(4-morpholinyl) phenyl]-1-butanone, the N such as 1-dichloroacetophenone, the aminoacetophenone class such as N-dimethyl amine benzoylformaldoxime；2; 4; 6-trimethylbenzoy-dipheny phosphine oxide, 2; 4; 6-trimethylbenzoyl phenyl phosphinic acid ethyl ester, phenyl double; two (2; 4,6-trimethylbenzoyl) the acylphosphine oxide class such as phosphine oxide, acylphosphine oxide, trimethylbenzoyl diethyl phosphonate, trimethylbenzoyl diphenyl phosphine oxide, bis(benzoylphenyl) phosphine oxide；The benzophenones such as benzophenone, 4-methyl benzophenone, 4,4'-bis-(lignocaine) benzophenone (michaelis ketone), 4,4'-bis-(dimethylamino) benzophenone；The Anthraquinones such as 2-methylanthraquinone, 2-ethyl-anthraquinone, 2-tert-butyl group base anthraquinone, 1-chloroanthraquinone；The thioxanthene ketones such as CTX, 2-methyl thiaxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthones, ITX；2,2', 4,4'-tetra-(2-chlorphenyls)-5,5'-bis-(3,4-Dimethoxyphenyl) diimidazole and 2,2', 5-tri-(2-chlorphenyl)-4-(3, the 2,4,5-triarylimidazoles dimer classes such as 4-Dimethoxyphenyl-4', 5'-diphenyl diimidazole；The acridines such as double; two (9-acridinyl) heptane of 9-phenylacridine, 1,7-；Camphorquinone；The luxuriant classes of titanium such as fluorinated diphenyl titanium luxuriant and double; two (pentafluorophenyl group) titanium is luxuriant；The tertiary amines such as triethylamine, triethanolamine, but do not limit with photoinitiator kind.
Specifically, this radical polymerization initiator is at least one in 80 DEG C of half-life organic peroxy class initiator more than 1 hour, inorganic peroxy class initiator and azo-initiator.For example, this radical polymerization initiator high is selected from least one in following material: hydrogen peroxide, dibenzoyl peroxide, cumyl peroxide, methyl ethyl ketone peroxide, di-tert-butyl peroxide, peroxide-2-ethyl hexanoic acid tert-butyl, peroxide acetic acid butyl ester, peroxidized t-butyl perbenzoate, tert-butyl hydroperoxide-3, 3, 5-trimethylace tonitric ester, peroxidized t-butyl perbenzoate, 1, 1-di-t-butyl hexamethylene, 2, 2-bis-(tert-butyl hydroperoxide) butane, two tertiary amyl peroxide, double, two (t-butylperoxyisopropyl) benzene, DIBHP, isopropyl benzene hydroperoxide, tertiary amyl hydrogen peroxide, tert-butyl hydroperoxide, azodiisobutyronitrile, potassium peroxydisulfate, Ammonium persulfate..Preferred cumyl peroxide, di-tert-butyl peroxide, methyl ethyl ketone peroxide, but do not limit above compound.
In the embodiment of the present invention, radical polymerization initiator, that is high temperature radical initiator is by thermally decomposing, produce free radical, free radical causes and solidifies in resin and polymerization single polymerization monomer the unreacted further crosslinking curing of double bond completely in photopolymerization reaction process, thus formed crosslinking degree more greatly, finer and close film.Use high temperature free radical to carry out heat cure and improve double bond conversion rate, add crosslink density, be finally reached anti-etching purpose.Further, high temperature radical initiator has higher decomposition temperature, and therefore it at room temperature has good stability, so that photoresist has good stable storing performance.
Specifically, this solvent at least one in lipid solvent, ether solvent, alcohols solvent, ketones solvent, aromatic solvents, petroleum solvent.It will be understood by those skilled in the art that, solvent described in the embodiment of the present invention is prior art, by using solvent to be dissolved and mix homogeneously by other each compositions so that prepared photoresist reaches desirable viscosity, is beneficial to spraying, roller coat or silk-screen to metal basal board.
For example, this solvent is selected from least one in following material: the esters solvents such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, dihydroxypropane single-ether acetate or propyleneglycol monobutyl ether acetate, ethyl acetate, butyl acetate；The ether solvents such as glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether；The alcohols solvents such as normal propyl alcohol, isopropanol, n-butyl alcohol, isobutanol；The ketones solvents such as butanone, Ketohexamethylene, isophorone；The aromatic solvent such as toluene, dimethylbenzene；Petroleum, the oxidation petroleum solvent such as Petroleum, solvent naphtha.Preferred propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, butanone, dipropylene glycol monomethyl ether, but do not limit above compound.
Further, in order to improve the identification of photoresist and improve the performance of prepared photoresist film, in the embodiment of the present invention, this photoresist also includes the composition of following weight portion: the pigment of 0.1-5 part and the auxiliary agent of 0-5 part.
It will be appreciated by persons skilled in the art that pigment used by the embodiment of the present invention is for conventional coloring pigment, such as phthalein viridescent, phthalocyanine blue, crystal violet etc., but do not limit above compound.The weight of this pigment is 0.1-5 part of this photoresist weight, it is preferable that 0.5-2 part.It is higher that pigment enables to prepared photoresist resolution, it is simple to its application in metal etch field.
Specifically, above-mentioned auxiliary agent at least one in stabilizer, levelling agent, defoamer, anticrater agent, adhesion promoter and surface slipping agent.The weight of this auxiliary agent is 0-5 part of this photoresist weight, it is preferable that 0.5-2 part, so that prepared photoresist film is finer and close, smooth, adhesive force is higher.
Visible, that the embodiment of the present invention provides photoresist, forms photoresist film by photocuring-heat cure, compactness is high, it is capable of withstanding acid solution to attack and alkaline solution attack, meets acid etching technique and the requirement of alkali etching technique simultaneously, and meet the demand of different metal substrate.Meanwhile, the adhesive force that the photoresist film formed is good to different metal base material, and the feature with being easily peeled property can be peeled off by Conventional solvents.This photoresist can form desired pattern on metallic substrates, has higher resolution.Visible, embodiment of the present invention photoresist adaptability is extensive, has higher industrial value.
Hereinafter will be further described through the present invention by specific embodiment.
The unreceipted condition person of operating process in specific examples below, all conventionally the condition of condition or manufacturer's suggestion carries out.Raw materials used unreceipted production firm and specification person be can pass through city available from conventional products.
Embodiment 1
Present embodiments provide a kind of photoresist, this photoresist include following weight portion composition: the epoxy novolac acrylic resin of 15 weight portions, the alkali soluble resins of 24 weight portions, the trimethylolpropane trimethacrylate of 10 weight portions, 2-methyl isophthalic acid-(4-methyl mercapto phenyl)-2-morpholine-1-acetone of 5 weight portions, the cumyl peroxide of 4 weight portions, the propylene glycol methyl ether acetate of 40 weight portions, the crystal violet of 0.1 weight portion, the 2,6 ditertiary butyl p cresol of 0.5 weight portion, 1.4 weight portions levelling agent.By by filtering after each composition Homogeneous phase mixing of said ratio, the desired photoresist of the present embodiment can be obtained.
Wherein, epoxy novolac acrylic resin is generated by after methacrylic acid and the same novolac epoxy resin of acrylic acid (F-44, epoxide equivalent is between 210-250) esterification.
Alkali soluble resins is that (this acrylic copolymeric resin is closed formed by the mass fraction respectively acrylic acid of 20% and the methyl methacrylate copolymer of 80% acrylic copolymeric resin, weight average molecular weight is 100,000 (Mw), molecular weight distributing index is 1.93, and acid number is 180mgKOH/g).
In following embodiment, the preparation method of photoresist uniform embodiment 1 is identical, namely by by filtering after each composition Homogeneous phase mixing in the photoresist of specific proportioning, obtaining the desired photoresist of each embodiment.
Comparative example 1
The photoresist that the present embodiment provides does not include solidifying resin and radical polymerization initiator, all the other compositions all identical with other compositions in the photoresist that embodiment 1 provides (surplus uses solvent to supplement).
Comparative example 2
The photoresist that the present embodiment provides is a kind of commercially available photoresist, and this photoresist uses epoxy resin and epoxy hardener to carry out hot setting.It includes the composition of following weight portion: the novolac epoxy resin (F-44 of 15 weight portions, epoxide equivalent 210-250), (this resin is closed formed by the acrylic acid of 20% and the methyl methacrylate copolymer of 80% acrylic copolymeric resin of 24 weight portions, weight average molecular weight is 100, 000 (Mw), molecular weight distributing index is 1.93, acid number is 180mgKOH/g), the trimethylolpropane trimethacrylate of 10 weight portions, the 2-methyl isophthalic acid of 5 weight portions-(4-methyl mercapto phenyl)-2-morpholine-1-acetone, the ethylenediamine of 4 weight portions, the propylene glycol methyl ether acetate of 40 weight portions, the crystal violet of 0.1 weight portion, the 2 of 0.5 weight portion, 6-ditertbutylparacresol, the levelling agent of 1.4 weight portions.
Embodiment 2
Present embodiments provide a kind of photoresist, this photoresist include following weight portion composition: the polyester acrylate resin of 5 weight portions, the alkali soluble resins of 20 weight portions, the trimethylolpropane trimethacrylate of 11 weight portions, 2-methyl isophthalic acid-(4-methyl mercapto phenyl)-2-morpholine-1-acetone of 1 weight portion, the ITX of 0.5 weight portion, the tert-butyl hydroperoxide of 10 weight portions, the propylene glycol methyl ether acetate of 40 weight portions, the butanone of 10 weight portions, the phthalein viridescent of 0.1 weight portion, the MEHQ of 1 weight portion, 1 weight portion defoamer.
Wherein, polyester acrylate resin is commercially available Changxing 6320 (purchased from Changxing Chemical Industry Co Ltd).Alkali soluble resins is the copolymer resins (weight average molecular weight is 30,000 (Mw), and molecular weight distributing index is 2.03, and acid number is 170mgKOH/g) of the maleic anhydride of styrene of sec-butyl alcohol esterification.
Embodiment 3
Present embodiments provide a kind of photoresist, this photoresist include following weight portion composition: the bisphenol-A epoxy acrylic resin of 30 weight portions, the alkali soluble resins of 23 weight portions, the dipentaerythritol monohydroxypentaacryande of 5 weight portions, 4,4'-bis-(lignocaine) benzophenone of 3 weight portions, the benzophenone of 2 weight portions, the dibenzoyl peroxide of 2 weight portions, the propylene glycol monomethyl ether of 33.5 weight portions, the phthalein viridescent of 0.4 weight portion, the 3-tertiary butyl-4-hydroxyanisol of 0.1 weight portion, 1 weight portion anticrater agent.
Wherein, bisphenol-A epoxy acrylic resin is generated by after the same bisphenol A epoxide resin of methacrylic acid and acrylic acid (E-44, epoxide equivalent 210-250) esterification.Alkali soluble resins is the copolymer of phenylethylene/maleic anhydride of methanol, sec-octyl alcohol and decanol esterification, wherein methanol, sec-octyl alcohol and decanol relative to maleic anhydride monomer amount make consumption respectively 10%, 70%, 20%；The weight average molecular weight of this alkali soluble resins is 150,000, and acid number is 250mgKOH/g.
Embodiment 4
Present embodiments provide a kind of photoresist, this photoresist include following weight portion composition: the cresol novolak epoxy acrylic resin of 10 weight portions, the alkali soluble resins of 40 weight portions, tetramethylolmethane monohydroxy three (methyl) acrylate of 10 weight portions, the benzoin dimethyl ether of 6 weight portions, the ITX of 2 weight portions, the peroxidized t-butyl perbenzoate of 7 weight portions, the butanone of 24 weight portions, the phthalocyanine blue of 2 weight portions, double, two (the 2 of 2 weight portions, 4-DI-tert-butylphenol compounds) pentaerythritol diphosphites, the levelling agent of 1 weight portion, the defoamer of 2 weight portions.
Wherein, cresol novolak epoxy acrylic resin is generated by after methacrylic acid and acrylic acid and cresol novolak epoxy resins (epoxide equivalent is 210-250) esterification.This alkali soluble resins is that (this acrylic copolymeric resin is formed by the 1-Octyl acrylate combined polymerization of the mass fraction respectively acrylic acid of 10%, the methyl methacrylate of 50% and 40% for the acrylic copolymeric resin of 10 weight portions, weight average molecular weight is 50,000 (Mw), molecular weight distributing index is 2.10, acid number is 100mgKOH/g) and the copolymer of maleic anhydride of styrene of sec-butyl alcohol esterification of 30 weight portions (weight average molecular weight is 60,000, acid number is 150mgKOH/g).
Embodiment 5
Present embodiments provide a kind of photoresist, this photoresist include following weight portion composition: the polyurethane acrylate resin of 10 weight portions, the alkali soluble resins of 30 weight portions, the trimethylolpropane trimethacrylate of 15 weight portions, 2-methyl isophthalic acid-(4-methyl mercapto phenyl)-2-morpholine-1-acetone of 3 weight portions, the ITX of 1 weight portion, the cumyl peroxide of 5 weight portions, the propylene glycol methyl ether acetate of 30 weight portions, the phthalein viridescent of 5 weight portions, the 3-tertiary butyl-4-hydroxyanisol of 0.5 weight portion, 0.5 weight portion defoamer.
Wherein, polyurethane acrylate resin is Changxing 6197 (purchased from Changxing Chemical Industry Co Ltd).Alkali soluble resins is that (this acrylic copolymeric resin is formed by the cyclopentenes combined polymerization of the acrylic acid of 5%, the acrylic acid methyl ester. of 50% and 45% for the acrylic copolymeric resin of 5 weight portions, weight average molecular weight is 10,000 (Mw), molecular weight distributing index is 2.10, acid number is 50mgKOH/g) (weight average molecular weight is 50 for the copolymer of maleic anhydride of styrene that is esterified with the sec-butyl alcohol of 25 weight portions, 000, acid number is 150mgKOH/g).
Embodiment 6
Present embodiments provide a kind of photoresist, this photoresist include following weight portion composition: the epoxy novolac acrylic resin of 20 weight portions, the alkali soluble resins of 24 weight portions, the trimethylolpropane trimethacrylate of 10 weight portions, the 1 of 10 weight portions, 6-hexanediyl ester, the phenyl of 2 weight portions double, two (2, 4, 6-trimethylbenzoyl) phosphine oxide, the methyl ethyl ketone peroxide of 5 weight portions, the propylene glycol methyl ether acetate of 20 weight portions, the dipropylene glycol monomethyl ether of 5.4 weight portions, the dimethylbenzene of 3 weight portions, the phthalein of 0.5 weight portion is dark green, the MEHQ of 0.1 weight portion.
Wherein, bisphenol-A epoxy acrylic resin is generated by after methacrylic acid and acrylic acid and bisphenol A epoxide resin (E-44, epoxide equivalent 210-250) esterification.Alkali soluble resins is that (this acrylic copolymeric resin is formed by the cyclo-octene combined polymerization of the methacrylic acid of 30%, the styrene of 50% and 20% for the acrylic copolymeric resin of 4 weight portions, weight average molecular weight is 20,000 (Mw), molecular weight distributing index is 2.10, acid number is 250mgKOH/g) (weight average molecular weight is 150 for the copolymer of maleic anhydride of styrene that is esterified with the sec-butyl alcohol of 20 weight portions, 000, acid number is 150mgKOH/g).
Embodiment 7
Embodiments provide a kind of photoresist, this photoresist include following weight portion composition: the epoxy novolac acrylic resin of 12 weight portions, the alkali soluble resins of 50 weight portions, the dipentaerythritol acrylate of 5 weight portions, the fluorinated diphenyl titanium of 0.5 weight portion is luxuriant, the cumyl peroxide of 8 weight portions, the propylene glycol methyl ether acetate of 20 weight portions, the phthalein of 0.5 weight portion is dark green, 3-tertiary butyl-the 4-hydroxyanisol of 0.5 weight portion, the levelling agent of 2 weight portions, the slipping agent of 0.5 weight portion, the adhesion promoter of 0.5 weight portion, the anticrater agent of 0.5 weight portion.
Wherein, epoxy novolac acrylic resin is generated by after methacrylic acid and the same novolac epoxy resin of acrylic acid (F-44, epoxide equivalent 210-250) esterification.Alkali soluble resins be 30 weight portions acrylic copolymeric resin (this acrylic copolymeric resin by 20% acrylic acid and 80% methyl methacrylate copolymer close formed, weight average molecular weight is 100,000 (Mw), molecular weight distributing index is 1.93, acid number is 180mgKOH/g) and the copolymer of maleic anhydride of styrene of sec-butyl alcohol esterification of 20 weight portions (weight average molecular weight is 24,000, acid number is 150).
Embodiment 8
Present embodiments provide a kind of photoresist, this photoresist include following weight portion composition: the epoxy novolac acrylic resin of 30 weight portions, the alkali soluble resins of 10 weight portions, the trimethylolpropane trimethacrylate of 15 weight portions, the 1 of 10 weight portions, 6-butanediol diacrylate, the 2-methyl isophthalic acid of 1 weight portion-(4-methyl mercapto phenyl)-2-morpholine-1-acetone, the ITX of 1 weight portion, the cumyl peroxide of 4.5 weight portions, the propylene glycol methyl ether acetate of 25 weight portions, the phthalein of 1 weight portion is dark green, 3-tertiary butyl-the 4-hydroxyanisol of 0.5 weight portion, the levelling agent of 1 weight portion, the defoamer agent of 1 weight portion.
Wherein, bisphenol-A epoxy acrylic resin is generated by after methacrylic acid and acrylic acid and bisphenol A epoxide resin (E-44, epoxide equivalent is 210-250) esterification.Alkali soluble resins is that (this acrylic copolymeric resin is closed formed by the acrylic acid of 25% and the methyl methacrylate copolymer of 75% acrylic copolymeric resin, weight average molecular weight is 200,000 (Mw), molecular weight distributing index is 2.23, and acid number is 220mgKOH/g).
Embodiment 9
Present embodiments provide a kind of photoresist, this photoresist include following weight portion composition: the epoxy novolac acrylic resin of 10 weight portions, the alkali soluble resins of 25 weight portions, the trimethylolpropane trimethacrylate of 10 weight portions, the dipentaerythritol acrylate of 5 weight portions, the 2-methyl isophthalic acid of 1.5 weight portions-(4-methyl mercapto phenyl)-2-morpholine-1-acetone, the benzophenone of 0.5 weight portion, the cumyl peroxide of 5 weight portions, the propylene glycol methyl ether acetate of 38 weight portions, the butanone of 3 weight portions, the phthalein of 0.1 weight portion is dark green, 3-tertiary butyl-the 4-hydroxyanisol of 0.5 weight portion, the adhesion promoter of 1.4 weight portions.
Wherein, epoxy novolac acrylic resin is generated by after methacrylic acid and acrylic acid and novolac epoxy resin (F-44, epoxide equivalent is 210-250) esterification.Alkali soluble resins is that (this acrylic copolymeric resin is closed formed by the mass fraction respectively acrylic acid of 20% and the methyl methacrylate copolymer of 80% acrylic copolymeric resin, weight average molecular weight is 100,000 (Mw), molecular weight distributing index is 2.01, and acid number is 180mgKOH/g).
Embodiment 10
Embodiments provide a kind of photoresist, this photoresist include following weight portion composition: the epoxy novolac acrylic resin of 5 weight portions, the alkali soluble resins of 15 weight portions, the trimethylolpropane trimethacrylate of 6 weight portions, the dipentaerythritol acrylate of 5 weight portions, the 2-methyl isophthalic acid of 2 weight portions-(4-methyl mercapto phenyl)-2-morpholine-1-acetone, the dimethoxybenzoin of 1 weight portion, the Ammonium persulfate. of 4 weight portions, the propylene glycol methyl ether acetate of 40 weight portions, the Petroleum of 10 weight portions, the dimethylbenzene of 10 weight portions, the phthalein of 0.2 weight portion is dark green, 3-tertiary butyl-the 4-hydroxyanisol of 0.5 weight portion, the levelling agent of 1.3 weight portions.
Wherein, epoxy novolac acrylic resin is generated by after methacrylic acid and acrylic acid and novolac epoxy resin (F-44, epoxide equivalent 210-250) esterification.This alkali soluble resins is that (this acrylic copolymeric resin is closed formed by the acrylic acid of 20% and the methyl methacrylate copolymer of 80% acrylic copolymeric resin, weight average molecular weight is 100,000 (Mw), molecular weight distributing index is 2.01, and acid number is 180mgKOH/g).
Embodiment 11
Present embodiments provide a kind of photoresist; this photoresist include following weight portion composition: the epoxy novolac acrylic resin of 6 weight portions, the alkali soluble resins of 13 weight portions, the trimethylolpropane trimethacrylate of 5 weight portions, the divinylbenzene of 2 weight portions, 1 weight portion 2; 4,6-trimethylbenzoy-dipheny phosphine oxides, the azodiisobutyronitrile of 2 weight portions, the propylene glycol methyl ether acetate of 70 weight portions, the phthalein viridescent of 0.5 weight portion, the 3-tertiary butyl-4-hydroxyanisol of 0.1 weight portion, 0.4 weight portion slipping agent.
Wherein, epoxy novolac acrylic resin is generated by after methacrylic acid and acrylic acid and novolac epoxy resin (F-44, epoxide equivalent is 210-250) esterification.This alkali soluble resins is that (this resin is closed formed by the acrylic acid of 20% and the methyl methacrylate copolymer of 80% acrylic copolymeric resin, weight average molecular weight is 150,000 (Mw), molecular weight distributing index is 2.16, and acid number is 180mgKOH/g).
Embodiment 12
The present embodiment adopts the method for roller coat, respectively the photoresist that embodiment 1-11 and comparative example 1-2 provides is coated to three kinds of metal basal boards (this metal basal board respectively copper metal basal board, aluminum metal substrate and stainless steel metal substrate), then it is coated with the metal basal board of photoresist to put into and the baking oven of 100 DEG C carries out front baking process 8 minutes, after its dry tack free, obtains the photoresist film that thickness is about 15 microns.Use 100mJ/cm2Ultraviolet light (UV light) this photoresist film is exposed, be then the NaCO of 1% by concentration3Carrying out developing, (development temperature is 30 DEG C, and pressure 1 is .8kg/m2, the time is 40s), it is thus achieved that the photoetching agent pattern corresponding with mask plate.Metal basal board after development is put in the baking oven of 180 DEG C and carry out after bake process 10 minutes, then the metal basal board that after bake processed is put into (acidic ferric chloride etching solution) in acidic etching liquid or in alkaline etching liquid the NaOH aqueous solution of 10% (concentration be) be etched, re-use organic solvent and the metal basal board after etching is carried out striping process, finally obtain the metal basal board with pattern corresponding with mask plate.
In above-mentioned processing procedure, it is utilized respectively the following methods performance to the various embodiments described above and the photoresist of comparative example and tests:
1) storage stability
By photoresist room temperature storage 6 months at 25 DEG C, test its viscosity.Calculate the changing value relative to initial viscosity of the viscosity after it stores 6 months.Adopt the test of Brookfield viscosity tester.
Evaluation criterion: viscosity B coefficent value is excellent less than or equal to 10%；Viscosity B coefficent value is 10-50% is good；Viscosity B coefficent value is 50-100% is；Viscosity B coefficent value is poor more than 100%.
2) resistance to dryness
Metal basal board after coating photoresist is put into preliminary drying in the baking oven of 100 DEG C process 15 minutes, after being cooled to room temperature, then at the NaCO of 1%3Carry out develop (development temperature 30 DEG C, pressure 1.8kg/cm2, time 40s), observe the cull situation on substrate after development.
Evaluation criterion: it is excellent for not having cull completely；Cull area is good less than 5%；Cull area is in 5-10% is；Cull area is poor more than 10%.
3) resolution
The metal basal board of baking use resolution test egative film carry out UV exposure, then at the NaCO of 1%3Carry out develop (development temperature 30 DEG C, pressure 1.8kg/cm2, time 40s), observe the circuit after development and resolve situation to evaluate resolution.
Evaluation criterion: 40 μm can be resolved with line for excellent；It is good for resolving 40-60 μm of circuit；Can resolve during 60-100 μm of circuit be；100 μm of Above Transmission Lines can be resolved for poor.
4) acidproof etch capabilities
Metal basal board after development is put into after bake in the baking oven of 180 DEG C process 10 minutes, then the metal basal board of after bake is put into acidic ferric chloride etching solution (50 DEG C).Take out washing after etching 30min, dry up, observe ink pellet surface situation of change.
Evaluation criterion: it is excellent for not having any defect；Defect area is good less than or equal to the 5% of the gross area；During defect area less than or equal to the 15% of the gross area is；Defect area is poor more than 15%.
5) alkaline-resisting etch capabilities
Metal basal board after development is put into after bake in the baking oven of 180 DEG C process 10 minutes, again the substrate of after bake is put in alkaline etching liquid (45 DEG C, 25% sodium hydrate aqueous solution) and be etched, after etching 30min, take out washing, dry up, observe ink pellet surface situation of change.
Evaluation criterion: it is excellent for not having any defect；Defect area is good less than or equal to the 5% of the gross area；During defect area less than or equal to the 15% of the gross area is；Defect area is poor more than 15%.
The test result of any of the above performance of photoresist is as shown in table 1:
The performance test table of table 1 photoresist
As shown in Table 1, compare the photoresist that comparative example 1 provides, the photoresist that embodiment of the present invention 1-11 provides have higher acidproof/ability of alkali resistance etching；Comparing the photoresist that comparative example 2 provides, the photoresist that embodiment of the present invention 1-11 provides has higher storage stability, resistance to drying performance and resolution.Visible, photoresist that embodiment of the present invention 1-11 provides not only have excellent acidproof/performance of alkali resistance etching, and be respectively provided with preferably adhesive force, resolution and stripping performance on the metal bases such as copper, aluminum and rustless steel.Therefore, the embodiment of the present invention photoresist suitability is extensive, is beneficial to large-scale industrial and utilizes.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the scope of the invention, all within the spirit and principles in the present invention, any amendment of making, equivalent replacement, improvement etc., should be included within protection scope of the present invention.
Claims (12)
1. a photoresist, composition including following weight portion: the solvent solidifying resin, the alkali soluble resins of 10-50 part, the polymerization single polymerization monomer of 5-25 part, the light trigger of 0.5-8 part, the radical polymerization initiator of 2-10 part, 20-70 part of 5-30 part, has carbon-carbon double bond in described solidification resin.
2. photoresist according to claim 1, it is characterized in that, described photoresist includes the composition of following weight portion: the solvent solidifying resin, the alkali soluble resins of 20-40 part, the polymerization single polymerization monomer of 10-20 part, the light trigger of 2-5 part, the radical polymerization initiator of 4-8 part, 40-60 part of 10-20 part.
3. photoresist according to claim 1 and 2, it is characterised in that described photoresist also includes the composition of following weight portion: the pigment of 0.1-5 part and the auxiliary agent of 0-5 part.
4. photoresist according to claim 3, it is characterised in that described solidification resin is acrylate ,-CH in described acrylate2=CH-COO-group and-CH2=CH (CH3) total number of-COO-group is be more than or equal to 2.
5. photoresist according to claim 4, it is characterised in that described acrylate at least one in Epocryl, polyester acrylate resin, polyurethane acrylate resin.
6. photoresist according to claim 3, it is characterised in that described polymerization single polymerization monomer is ethylene system unsaturated monomer and/or propylene unsaturated monomer.
7. photoresist according to claim 3, it is characterised in that described radical polymerization initiator is at least one in 80 DEG C of half-life organic peroxy class initiator more than 1 hour, inorganic peroxy class initiator and azo-initiator.
8. photoresist according to claim 3, it is characterised in that described alkali soluble resins is the phenylethylene/maleic anhydride copolymer resins of (methyl) acrylic copolymeric resin and/or esterification.
9. photoresist according to claim 8, it is characterised in that described (methyl) acrylic copolymeric resin is carried out copolymerization by ethylene system unsaturated monomer and/or propylene unsaturated monomer with (methyl) acrylic acid and obtains.
10. photoresist according to claim 9, it is characterised in that described ethylene system unsaturated monomer, described propylene unsaturated monomer are respectively provided with following construction unit:
Wherein, R is hydrogen or methyl；
R1For phenyl, hydroxy phenyl, aminomethyl phenyl, ethylphenyl, naphthyl or itrile group；
R2、R3Hydroxyalkyl, dialkylaminoalkyl group, phenyl, benzyl or the Laurel ester group be the alkyl with 1-8 carbon atom, having 1-8 carbon atom, wherein, the alkyl in described dialkylaminoalkyl group includes 1-8 carbon number；
R4For having the alkyl of 3-8 carbon atom.
11. photoresist according to claim 1; it is characterized in that, described light trigger at least one in benzoin class, acetophenones, aminoacetophenone class, acylphosphine oxide class, benzophenone, Anthraquinones, thioxanthene ketone, triarylimidazoles dimer class, acridine, the luxuriant class of diphenyl titanium, tertiary amines light trigger.
12. photoresist according to claim 1, it is characterised in that described solvent at least one in lipid solvent, ether solvent, alcohols solvent, ketones solvent, aromatic solvents, petroleum solvent.
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| CN107817651A (en) * | 2017-09-19 | 2018-03-20 | 合肥惠科金扬科技有限公司 | One kind is used for TFT LCD photoetching compositions |
| US20190369494A1 (en) * | 2016-12-05 | 2019-12-05 | Arkemea Inc. | Initiator blends and photocurable compositions containing such initiator blends useful for 3d printing |
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Application publication date: 20160720 |
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| RJ01 | Rejection of invention patent application after publication |