CN1114629C - Copolymer containing unsaturated bond branched chain and its photoresist composition - Google Patents
Copolymer containing unsaturated bond branched chain and its photoresist composition Download PDFInfo
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- CN1114629C CN1114629C CN 99126266 CN99126266A CN1114629C CN 1114629 C CN1114629 C CN 1114629C CN 99126266 CN99126266 CN 99126266 CN 99126266 A CN99126266 A CN 99126266A CN 1114629 C CN1114629 C CN 1114629C
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Abstract
The present invention relates to a copolymer containing unsaturated bond branched chains, which can be used as photosensitive resin. The present invention is a copolymer of a monomer containing unsaturated bonds and an anhydride monomer containing unsaturated bonds. Acid anhydride functional groups with 0.01 to 100 mole percentage in the copolymer are monoesterified through the esterification ring opening reaction with alcohol containing unsaturated bonds to generate carboxylic acid groups. Carboxylic acid groups with 0.01 to 100 mole percentage in the copolymer are changed into ester groups through the ring opening reaction with epoxy-ethylic compounds by epoxy groups. The present invention also relates to a photoresist composition containing the copolymer and an application thereof to the production of printed circuit boards, and the copolymer has the characteristics of favorable photosensitivity, analytic degree and electroplating resistance.
Description
The present invention relates to a kind of multipolymer, particularly relate to a kind of multipolymer that the key side chain is closed in insatiable hunger that contains, the invention still further relates to the photo-corrosion-resisting agent composition that contains this multipolymer.
Along with the continuous progress of integrated circuit manufacture process and structure packing technique, printed circuit board (PCB) (printedcircuit board; PCB) develop towards directions such as high-density distribution, thin typeization, high electrical specification, size stabilization, graph thinning and low prices.Wherein for reaching high requirement of resolving circuit, the photo-resist characteristic is one of important factor.The dry film photo-resist of usage quantity maximum is owing to coating thickness thicker (about 25-50 μ m) at present, and its resolution is more than 5mil (100 μ m), and price is higher, and under the trend of PCB high-density distribution and multiple stratification, its use will be restricted; And the coating thickness of liquid photoresist approaches (about 5-15 μ m), and resolution is preferable, and between 25-50 μ m, price is also low than the dry film photo-resist.Both relatively, the dry film photo-resist at thickness, make aspects such as the line width limit, circuit resolution, adherence and sticking power all not as liquid photoresist.Outer-layer circuit still adopts the dry film photo-resist at present, and internal layer circuit is then towards using the liquid photoresist direction to develop.In several years of future, owing to be subjected to the trend of the fine and closely woven requirement of circuit is influenced, liquid photoresist certainly will become follow-on photo-resist with replacing the dry film photo-resist.
Generally speaking, the application of liquid photoresist composition on printed circuit board (PCB) can be divided into two kinds, and a kind of is as pattern photo-resist (pattern resist), in order to define the line pattern of copper on the printed circuit board (PCB); A kind of is as green lacquer (solder mask or solderresist), in order to the protection copper wire.
The pattern photo-corrosion-resisting agent composition mainly comprises: the reactive monomer of photoresist, Photoepolymerizationinitiater initiater and photopolymerization, its application mode is as described below.The pattern photo-corrosion-resisting agent composition is coated on the copper clad laminate, after the drying figuratum egative film (mask) is covered post-exposure on the photo-corrosion-resisting agent composition, make that the resin in the photo-corrosion-resisting agent composition that exposes produces photocuring reaction.Follow the photo-resist part of develop unexposed to remove (promptly uncured).Then the copper that goes out of etch exposed goes China ink (stripping) so that the photo-resist on the copper cash is removed at last, obtains the copper cash of patterning.Another kind of mode is that after removing unexposed photo-resist, plating Sn/Pb removes China ink, serves as that the cover curtain comes etch copper with the Sn/Pb pattern then, removes Sn/Pb at last again, and obtains the copper cash of patterning.
Green lacquer photo-corrosion-resisting agent composition then is to be coated on the copper cash of patterning, and it is the protective layer that is used as copper cash.In green lacquer photo-corrosion-resisting agent composition, also can add Resins, epoxy and thermal curing agents usually, so that photoresist can carry out the thermofixation reaction after heating, to increase the hardness of protective layer.
The multipolymer of vinylbenzene and maleic anhydride monoesters (copolymer of styrene andmonoester of maleic anhydride) is a kind of photoresist that is usually used in printed circuit board (PCB), and the research to it is quite extensive in recent years.United States Patent (USP) the 5th, 114 No. 830,5,087, No. 552,5,609, No. 991 and 5,698, has all carried out relevant research for No. 370 to this.Its making method is, earlier with vinylbenzene and maleic anhydride with the copolymerization of radical polymerization mode, then, close or alcohols that insatiable hunger is closed makes maleic anhydride base mono-esterification on the multipolymer with full.
Yet, when this multipolymer through mono-esterification is applied in the printed circuit board (PCB) photo-resist processing procedure, exist the sensitivity of light deficiency, can glue egative film after the coating drying of photo-resist, not good to the copper tack in electroplating process, and can't obtain problems such as high-res.
Therefore, purpose of the present invention is and addresses the above problem, and a kind of multipolymer that key Zhi Jian is closed in insatiable hunger that contains is provided, and it can be used as photoresist, has high sensitivity of light, under extremely low UV exposure energy, also has high resolution.
Another object of the present invention provides a kind of photoresist with high glass-transition temperature (Tg) and good flexibility.
A further object of the present invention provides a kind of photo-corrosion-resisting agent composition, when it is coated on the printed circuit board (PCB), after drying and the illumination, do not have the problem of after-tacking egative film, for the copper on the printed circuit board (PCB) good tack is arranged, and have good anti-electroplating characteristic.
For achieving the above object, of the present inventionly contain the multipolymer that the key side chain is closed in insatiable hunger, it is to contain insatiable hunger to close the monomer of key and contain the multipolymer that the anhydride monomers of key is closed in insatiable hunger, the anhydride functional group that 0.01 to 100 molar percentage arranged in this multipolymer is contained alcohols that insatiable hunger closes key through the esterification ring-opening reaction and mono-esterification, and generation carboxylic acid group, there is the carboxylic acid group of 0.01 to 100 molar percentage to be become ester group through the epoxy ring-opening reaction in this multipolymer by the epoxy ethyl compound, this epoxy ethyl compound comprises that containing insatiable hunger closes the epoxy ethyl compound of key and/or contain heteroatomic epoxy ethyl compound, this heteroatoms is selected from silicon, nitrogen, phosphorus and sulphur, wherein this contains insatiable hunger and closes the monomer of key and do not have anhydride group.
Photo-corrosion-resisting agent composition of the present invention comprises by weight:
(a) 100 parts of the invention described above contains the multipolymer that the key side chain is closed in insatiable hunger;
(b) 1 to 25 part Photoepolymerizationinitiater initiater; And
(c) reactive monomer of 1 to 100 part photopolymerization.
The present invention contains insatiable hunger, and to close the method for making of multipolymer of key side chain as described below.At first, close the monomer of key and contain insatiable hunger and close the anhydride monomers of key and carry out copolymerization with containing insatiable hunger, this contains insatiable hunger and closes the monomer of key and do not have anhydride group.Then, above-mentioned multipolymer is closed the alcohols reaction of key with containing insatiable hunger, thus make anhydride functional group in the multipolymer via the esterification ring-opening reaction mono-esterification, and produce the carboxylic acid group.Then, utilize again and contain insatiable hunger and close the epoxy ethyl compound of key and/or contain heteroatomic epoxy ethyl compound and carry out epoxy ring-opening with the carboxylic acid group and react, and obtain the multipolymer that the key side chain is closed in insatiable hunger that contains of the present invention.
Above-mentionedly to contain insatiable hunger and close the preparation method of the multipolymer of key side chain and be more readily understood in order to make, below illustrate with the reaction of vinylbenzene, maleic anhydride, methacrylic acid-2-hydroxy methacrylate (hydroxyethylmethacrylate) and glytidyl methacrylate (glycidyl methacrylate).At first, make vinylbenzene (contain the monomer that key is closed in insatiable hunger, do not have anhydride group) and maleic anhydride (containing the anhydride monomers that key is closed in insatiable hunger) carry out copolymerization.Then, with the reaction of above-mentioned multipolymer and methacrylic acid-2-hydroxy methacrylate (containing the alcohols that key is closed in insatiable hunger), thereby make anhydride functional group in the multipolymer through the esterification ring-opening reaction and mono-esterification, and produce the carboxylic acid group.Then, utilize glytidyl methacrylate (containing the epoxy ethyl compound that key is closed in insatiable hunger) and carboxylic acid group to carry out the epoxy ring-opening reaction again, and obtain suc as formula the multipolymer shown in (I):
Wherein x, y, z, m represent the mol ratio of each repeated structural unit, and between 0.1 to 0.9, y and m are respectively between 0 to 0.9 respectively for x+y+z+m=1.0, x and z.
As mentioned above, if at styrene-maleic anhydride copolymer behind mono-esterification, use simultaneously contains insatiable hunger closes the epoxy ethyl compound of key (as the acrylic acid epoxy propyl ester) and contains heteroatomic epoxy ethyl compound [as 3-R-GLYCIDOL propyl trimethoxy silicane (3-glycidyl oxypropyltrimethoxy silane)] to carry out the epoxy ring-opening reaction with the carboxylic acid group, then can obtain suc as formula the multipolymer shown in (II):
Wherein x, y, z, m, n represent the mol ratio of each repeated structural unit, x+y+z+m+n=1.0, x and z respectively between 0.1 to 0.9, y, m, and n is respectively between 0 to 0.9.
By the structure of formula (I) and formula (II), there are two kinds to contain insatiable hunger and close the side chain of two keys and be introduced in this multipolymer, so, when carrying out photocuring by illumination, because the ratio height of two keys in the multipolymer, thereby make its sensitivity of light be improved.And the introducing of side chain also can increase the flexibility of multipolymer.As for the introducing that contains the heteroatoms side chain, have and help adhering to the copper surface.
Be applicable to and of the present inventionly contain insatiable hunger and close the monomer of key and can be vinylbenzene, vinyl toluene, acrylic acid or the like, esters of acrylic acid, methacrylic, methyl acrylic ester or ethene ethers etc.
Be applicable to and of the present inventionly contain insatiable hunger and close the anhydride monomers of key and can be maleic anhydride, methyl maleic anhydride, interior-5-norbornylene-2,3-dicarboxylic anhydride (endo-5-norbornene-2,3-dicarboxylic anhydride) or suitable-1,2,3,6-tetrahydrochysene phthalate anhydride (cis-1,2,3,6-tetrahydrophthalic anhydride) etc.
Be applicable to and of the present inventionly contain insatiable hunger and close the alcohols of key and can be methacrylic acid-2-hydroxy methacrylate, 2-Hydroxy ethyl acrylate (hydroxyethyl acrylate), styryl carbinol (cinnamicalcohol), vinyl carbinol (allyl alcohol), geraniol (citronellol), 3-methyl butene-[3] alcohol or 2-hexene-[1] alcohol etc.
According to the present invention, be used for the epoxy ethyl compound of carboxylic acid group's reaction of after esterification, being produced with the anhydride functional group, can use separately to contain insatiable hunger and close the epoxy ethyl compound of key or use separately and contain heteroatomic epoxy ethyl compound, also can use simultaneously to contain insatiable hunger and close the epoxy ethyl compound of key and contain heteroatomic epoxy ethyl compound.
Be applicable to and of the present inventionly contain insatiable hunger and close the epoxy ethyl compound of key and can be acrylic acid epoxy propyl ester (glycidyl acrylate), glytidyl methacrylate, p-epoxy styrene (p-epoxy-styrene), p-glycidyl vinylbenzene (p-glycidyl-styrene) or allyl glycidyl ether (allyl glycidyl ether) etc.
Be applicable to the epoxy ethyl compound that heteroatomic epoxy ethyl compound can be silicon atoms that contains of the present invention, concrete example comprises 3-R-GLYCIDOL propyl trimethoxy silicane, and β-(3,4-epoxy group(ing) cyclohexyl) ethyl trimethoxy silane [β-(3,4-epoxycyclohexyl) ethyltrimethoxysilane].
Of the present inventionly contain the multipolymer that the key side chain is closed in insatiable hunger, its weight-average molecular weight is preferable between 5000 to 250000, and acid number is preferably between 50 to 250.
The present invention contains insatiable hunger and closes the multipolymer of key side chain and can be used as photoresist, when the reactive monomer that cooperates Photoepolymerizationinitiater initiater (photoinitiator) and photopolymerization uses together, promptly becomes photo-corrosion-resisting agent composition.In said composition, the consumption of Photoepolymerizationinitiater initiater is 1 to 25 weight part preferably, and the consumption of the reactive monomer of photopolymerization is 1 to 100 weight part preferably, and copolymer comprised 100 weight parts that contain unsaturated bond branched chain of the present invention.
Be applicable to that Photoepolymerizationinitiater initiater of the present invention can be bitter almond oil camphor, bitter almond oil camphor alkyl oxide, benzil (benzil), ketal, acetophenone compound, benzophenone, 4,4 '-dimethyl-amino-benzophenone (4,4 '-dimethylamino-benzophenone), thioxanthone compound (thioxanthones) or morpholino acetonide (morpholino-propanones) etc.
The reactive monomer that is applicable to photopolymerization of the present invention can be multi-functional (methyl) acrylate monomer, and concrete example comprises diacrylate TEG ester (tetraethylene glycoldiacrylate), dimethacrylate TEG ester (tetraethylene glycoldimethacrylate), diacrylic acid pentyl diol ester (neopentylglycoldiacrylate), dimethacrylate DOPCP (neopentylglycol dimethylacrylate), poly-ethylene glycol diacrylate (polyethylene glycol diacrylate), polydimethyl vinylformic acid glycol ester (polyethylene glycol dimethylacrylate), the dihydroxyphenyl propane diol ester of diacrylate ethoxylation (ethoxylated bisphenol A glycoldiacrylate), the dihydroxyphenyl propane diol ester of dimethacrylate ethoxylation (ethoxylatedbisphenol A glycol dimethyl acrylate), trimethylolpropane trimethacrylate (trimethylolpropane trimethacrylate), Viscoat 295 (trimethylolpropane triacrylate), pentaerythritol triacrylate (pentaerythritol triacrylate), the Viscoat 295 of ethoxylation (ethoxylated trimethylolpropane triacrylate), glyceryl propoxy-triacrylate (glyceryl propoxy triacrylate), pentaerythritol tetracrylate (pentaerythritol tetraacrylate) and five vinylformic acid dipentaerythritol ester (dipentaerythritol pentaacrylate).
In order to make photo-corrosion-resisting agent composition of the present invention except being undertaken the photocuring reaction by illumination, also can after being heated, carry out the thermofixation reaction, and make the resin after the curing have higher hardness, can further comprise in the photo-corrosion-resisting agent composition of the present invention by weight 1 to 50 part Resins, epoxy and 0.1 to 30 part thermal curing agents.
Be applicable to that Resins, epoxy of the present invention can be the glycidyl ether of bisphenol type (bisphenol typeepoxy), the glycidyl ether of two diphenol types (biphenyl type epoxy), phenolic aldehyde polyglycidyl ether (phenolic novolac epoxy), alkyl glycidyl ether (cresol novolacepoxy), naphthalene is glycidyl ether (naphthalene epoxy), dicyclo penta diphenol glycidyl ether (dicyclopendiene novolac epoxy), ring-shaped fat class glycidyl ether (cycloaliphatic epoxy), isocyanic ester glycidyl ether (isocyanate epoxy), the polyhydroxy phenol polyglycidyl ether, the Resins, epoxy of bromination (brominated epoxy resin), or its mixture.
The object lesson of the glycidyl ether of bisphenol type comprise dihydroxyphenyl propane glycidyl ether, Bisphenol F glycidyl ether (
), dihydroxyphenyl propane D glycidyl ether (
), the bisphenol S glycidyl ether (
), tetramethyl-dihydroxyphenyl propane glycidyl ether, tetramethyl-Bisphenol F glycidyl ether, tetramethyl-dihydroxyphenyl propane D glycidyl ether, tetramethyl-bisphenol S glycidyl ether, tetrabromo-bisphenol glycidyl ether, tetrachlorobisphenol A glycidyl ether.
The object lesson of the glycidyl ether of two diphenol types comprises 4,4 '-diphenol glycidyl ether (
), 3,3 '-dimethyl-4-4 '-diphenol glycidyl ether, 3,3 ', 5,5 '-tetramethyl--4,4 '-diphenol glycidyl ether.
The object lesson of phenolic aldehyde polyglycidyl ether comprises phenolic aldehyde polyglycidyl ether, cresols phenolic aldehyde polyglycidyl ether, bisphenol-A phenolic polyglycidyl ether, tetrabromo-bisphenol phenolic aldehyde polyglycidyl ether.
The object lesson of polyhydroxy phenol polyglycidyl ether comprises three (phenyl-4-hydroxyl) methane polyglycidyl ether, three (phenyl-4-hydroxyl) ethane polyglycidyl ether, three (phenyl-4-hydroxyl) propane polyglycidyl ether, three (phenyl-4-hydroxyl) butane polyglycidyl ether, three (phenyl-3-methyl-4-hydroxyl) methane polyglycidyl ether, three (phenyl-3,5-dimethyl-4-hydroxyl) methane polyglycidyl ether, four (phenyl-4-hydroxyl) ethane polyglycidyl ether, four (phenyl-3,5-dimethyl-4-hydroxyl) ethane polyglycidyl ether.
Be applicable to that thermal curing agents of the present invention can be aliphatics amine, aromatic amine, polyamide-based, Dicyanodiamide class (dicyandiamides), imidazoles or anhydrides, or the like.
In addition, photo-corrosion-resisting agent composition of the present invention also further comprises other additive, and cellosolve for example is as methylcyclohexane; Dyestuff,, 4 "-three (dimethylamino) triphenyl methane, phthalocyanine green as 4,4, or the like.
Below in conjunction with embodiment in detail method of the present invention, feature and advantage are described in detail, but are not in order to restriction the present invention.
Embodiment 1
With 104g vinylbenzene and 98g maleic anhydride mixed dissolution in 30g methyl ethyl ketone (methylethyl ketone; MEK) in, obtain monomer solution.Under 75 ℃, this monomer solution was splashed in 3 hours in the reactor that 270g methyl ethyl ketone (the initiator dibenzoyl peroxide that wherein contains part by weight 3%) is housed.After dropwising, mixture 75 ℃ of following insulation reaction 5 hours, is obtained phenylethylene/maleic anhydride copolymer solution.
The phenylethylene/maleic anhydride copolymer solution of gained is heated to 75 ℃, in wherein adding 2g quinhydrones and 4g imidazoles, treat that the mode that drips splashed in the reactor in 2 hours with 65g methacrylic acid-2-hydroxy methacrylate utilization again behind the temperature-stable, again in 75 ℃ of following insulation reaction 5 hours.Then, temperature is risen to 100 ℃, added 10.8g glytidyl methacrylate and 1g benzyl dimethyl amine insulation reaction 5 hours.The molecular weight of the photoresist that obtains (Mw) is 35000, acid number 109mgKOH/g, 145 ℃ of second-order transition temperatures.
Coat on the copper clad laminate after each composition shown in the table 1 ground via three running rollers, after three minutes, the egative film that will have pattern is positioned on the photo-resist, does not have egative film to after-tack phenomenon, again with ultraviolet light source (energy 70mJ/cm in 80 ℃ of oven dry
2) irradiation.Then, under 30 ℃, with 1%Na
2CO
3Developing liquid developing 60 seconds, light not illuminated portion can dissolve fully.Can be carried out photocuring by the part that illumination is mapped to, hardness and is 100% (recording with hundred lattice methods of testing) to the tack of copper more than 3H.
Table 1 composition weight percent (%) photoresist (solid) 25 methylcyclohexanes 25 Viscoat 295 20.5Irgucure 907 (Photoepolymerizationinitiater initiater, Ciba company sells)
(1)42-isopropyl thioxanthone (Photoepolymerizationinitiater initiater) 1 dyestuff
(2)1 methyl ethyl ketone
(3)23.5 annotate: (1) Irgucune 907 is 2-methyl-4 '-methyl sulfenyl-2-morpholino Propiophenone (2-methy1-4 ' methylthio-2-morpholine-propiphenone);
(2) dyestuff is 4,4,4 "-three (dimethylamino) triphenyl methane [(4,4,4 "-tris (dimethylamino)-tripheynlmethane)];
(3) methyl ethyl ketone act as dissolving that helps Irgucune 907 and the drying of filming.
Embodiment 2
104g vinylbenzene and 98g maleic anhydride mixed dissolution (among the γ-butyrolactone), are obtained monomer solution in the 30g gamma-butyrolactone.Under 75 ℃, this monomer solution was splashed in 3 hours in the reactor of the mixed solvent [the initiator A IBN (azobis isobutyronitrile) that wherein contains part by weight 3%] that 180g gamma-butyrolactone and 90g Virahol are housed.After dropwising, mixture 75 ℃ of following insulation reaction 8 hours, is obtained phenylethylene/maleic anhydride copolymer solution.
Phenylethylene/maleic anhydride copolymer solution is heated to 75 ℃, adds 1g quinhydrones and 4g imidazoles, treat that the mode that drips splashed in the reactor in 2 hours with 104g methacrylic acid-2-hydroxy methacrylate utilization again behind the temperature-stable, again in 75 ℃ of following insulation reaction 5 hours.Then, temperature is risen to 100 ℃, added 14.7g glytidyl methacrylate and 1g Tetramethylammonium chloride (tetramethylammonium chloride) insulation reaction 5 hours.The molecular weight of the photoresist that obtains (Mw) is 27299, acid number 146mg KOH/g, 130 ℃ of second-order transition temperatures.
Coat on the copper clad laminate after composition shown in the table 2 ground via three running rollers, after three minutes, the egative film that will have pattern is positioned on the photo-resist, does not have egative film to after-tack phenomenon, again with ultraviolet light source (energy 450mJ/cm in 80 ℃ of oven dry
2) irradiation.Then, under 30 ℃, with 1%Na
2CO
3Developing liquid developing 60 seconds, light not illuminated portion can dissolve fully.Can be carried out photocuring by the part that illumination is mapped to, hardness and is 100% to the tack of copper more than 3H.Then, again the copper clad laminate behind the photocuring was carried out thermofixation 30 minutes in 150 ℃ of baking ovens, the coating after the thermofixation has the above hardness of 5H as a result.
Table 2 composition weight percent (%) photoresist (solid) 25 methylcyclohexanes 25 5 vinylformic acid dipentaerythritol ester 20 cresol novolak epoxies 6 (EEW
(1)200g/eq, Mw 4000) benzyl dimethyl amine (thermal curing agents) 0.6Irgucure 907 (Photoepolymerizationinitiater initiater) 42-isopropyl thioxanthone (Photoepolymerizationinitiater initiater) 1 phthalocyanine green (phthalocyanine green) 1 methyl ethyl ketone 23.5 (1) EEW are epoxy equivalent (weight), expression contains the weight epoxy gram number of 1 gram equivalent of epoxy group(ing).
Embodiment 3
104g vinylbenzene and 98g maleic anhydride mixed dissolution in the 30g gamma-butyrolactone, are obtained monomer solution.Under 75 ℃, this monomer solution was added dropwise in 3 hours in the reactor of the mixed solvent (the initiator A IBN that wherein contains part by weight 3%) that 180g gamma-butyrolactone and 90g Virahol are housed.After dropwising, mixture 75 ℃ of following insulation reaction 8 hours, is obtained phenylethylene/maleic anhydride copolymer solution.
Phenylethylene/maleic anhydride copolymer solution is heated to 75 ℃, adds 1g quinhydrones and 4g imidazoles, treat that the mode that drips splashed in the reactor with 104g methacrylic acid-2-hydroxy methacrylate utilization again behind the temperature-stable in 2 hours, again in 75 ℃ of following insulation reaction 5 hours.Then, temperature is risen to 100 ℃, add 88g glytidyl methacrylate, 37g 3-R-GLYCIDOL propyl trimethoxy silicane and 1g Tetramethylammonium chloride in 100 ℃ of following insulation reaction 5 hours.
Coat on the copper clad laminate after composition shown in the table 1 (but wherein use by embodiment 3 gained photoresist) ground via three running rollers, in 80 ℃ the oven dry three minutes after, the egative film that will have pattern is positioned on the photo-resist, there is not egative film to after-tack phenomenon, again with ultraviolet light source (energy 75mJ/cm
2) irradiation.Then, under 30 ℃, with 1%Na
2CO
3Developing liquid developing 60 seconds, light not illuminated portion can dissolve fully.Can be carried out photocuring by the part that illumination is mapped to, hardness and is 100% to the tack of copper more than 3H.Then, again the copper clad laminate behind the photocuring is soaked in tart 10%CuCl
2To remove the copper that exposes, found that coating is 100% for the tack of the copper that does not expose in the etching solution.
Advantage of the present invention is as follows:
1. contain insatiable hunger and close in the copolymer structure of key side chain of the present invention, close the importing of key side chain and can improve sensitivity of light, make photo-corrosion-resisting agent composition under extremely low UV exposure energy, also have high resolution owing to contain insatiable hunger.As for the importing that contains the heteroatoms side chain, have adhering to of resin after helping solidify and copper surface;
2. of the present inventionly contain insatiable hunger and close the multipolymer of key side chain and have high second-order transition temperature (Tg) and good flexibility;
3. photo-corrosion-resisting agent composition of the present invention is coated printed circuit board (PCB), after drying and the illumination, do not have the problem of after-tacking egative film, good tack is arranged for the copper on the printed circuit board (PCB).
Being preferred embodiment of the present invention only below, is not in order to limiting the present invention, any person skilled in the art without departing from the spirit and scope of the present invention, the various changes of being done all belong to scope of the present invention with retouching.
Claims (20)
1. one kind contains the multipolymer that the key side chain is closed in insatiable hunger, it is to contain insatiable hunger to close the monomer of key and contain the multipolymer that the anhydride monomers of key is closed in insatiable hunger, the anhydride functional group that 0.01 to 100 molar percentage arranged in this multipolymer by one contain alcohols that insatiable hunger closes key via the esterification ring-opening reaction mono-esterification, and generation carboxylic acid group, there is the carboxylic acid group of 0.01 to 100 molar percentage to be become ester group via the epoxy ring-opening reaction in this multipolymer by an epoxy ethyl compound, this epoxy ethyl compound comprises that containing insatiable hunger closes the epoxy ethyl compound of key and/or contain heteroatomic epoxy ethyl compound, this heteroatoms is selected from silicon, nitrogen, phosphorus and sulphur, wherein this contains insatiable hunger and closes the monomer of key and do not have anhydride group; Its weight-average molecular weight is between 5000 to 250000, and acid number is between 50 to 250.
2. according to the multipolymer that the key side chain is closed in insatiable hunger that contains of claim 1, wherein saidly contain the monomer that insatiable hunger closes and be selected from vinylbenzene, vinyl toluene, acrylic acid or the like, esters of acrylic acid, methacrylic, methyl acrylic ester and ethene ethers.
3. according to the multipolymer that the key side chain is closed in insatiable hunger that contains of claim 2, wherein saidly contain insatiable hunger to close the monomer of key be vinylbenzene.
4. according to the multipolymer that the key side chain is closed in insatiable hunger that contains of claim 1, wherein saidly contain insatiable hunger and close the anhydride monomers of key and be selected from maleic anhydride, methyl maleic anhydride, interior-5-norbornylene-2,3-dicarboxylic anhydride and suitable-1,2,3,6-tetrahydrochysene phthalate anhydride.
5. according to the multipolymer that the key side chain is closed in insatiable hunger that contains of claim 4, wherein saidly contain insatiable hunger to close the anhydride monomers of key be maleic anhydride.
6. according to the multipolymer that the key side chain is closed in insatiable hunger that contains of claim 1, wherein saidly contain insatiable hunger and close the alcohols of key and be selected from methacrylic acid-2-hydroxy methacrylate, 2-Hydroxy ethyl acrylate, styryl carbinol, vinyl carbinol, geraniol, 3-methyl butene-[3] alcohol and 2-hexene-[1] alcohol.
7. according to the multipolymer that the key side chain is closed in insatiable hunger that contains of claim 6, wherein saidly contain insatiable hunger to close the alcohols of key be methacrylic acid-2-hydroxy methacrylate.
8. according to the multipolymer that the key side chain is closed in insatiable hunger that contains of claim 1, the insatiable hunger that contains described in the base is closed the epoxy ethyl compound of key and is selected from acrylic acid epoxy propyl ester, glytidyl methacrylate, p-epoxy styrene, p-glycidyl vinylbenzene and allyl glycidyl ether.
According to Claim 8 contain the multipolymer that the key side chain is closed in insatiable hunger, wherein saidly contain insatiable hunger to close the epoxy ethyl compound of key be glytidyl methacrylate.
10. according to the multipolymer that the key side chain is closed in insatiable hunger that contains of claim 1, the wherein said epoxy ethyl compound that to contain heteroatomic epoxy ethyl compound be silicon atoms.
11. according to the multipolymer that the key side chain is closed in insatiable hunger that contains of claim 10, the epoxy ethyl compound of wherein said silicon atoms is 3-R-GLYCIDOL propyl trimethoxy silicane or β-(3,4-epoxy group(ing) cyclohexyl) ethyl trimethoxy silane.
12. according to the multipolymer that the key side chain is closed in insatiable hunger that contains of claim 11, the epoxy ethyl compound of wherein said silicon atoms is a 3-R-GLYCIDOL propyl trimethoxy silicane.
13. a photo-corrosion-resisting agent composition comprises following component by weight:
(a) 100 parts as claimed in claim 1ly contain the multipolymer that the key side chain is closed in insatiable hunger;
(b) 1 to 25 part Photoepolymerizationinitiater initiater; And
(c) reactive monomer of 1 to 100 part photopolymerization.
14. photo-corrosion-resisting agent composition according to claim 13, wherein said Photoepolymerizationinitiater initiater is selected from bitter almond oil camphor, bitter almond oil camphor alkyl oxide, benzil, ketal, acetophenone compound, benzophenone, 4,4 '-dimethylamino benzophenone, thioxanthone compound and morpholino acetonide.
15. according to the photo-corrosion-resisting agent composition of claim 13, the reactive monomer of wherein said photopolymerization is multi-functional acrylate monomer or methacrylate monomer.
16. according to the photo-corrosion-resisting agent composition of claim 15, the reactive monomer of wherein said photopolymerization is selected from diacrylate TEG ester, dimethacrylate TEG ester, diacrylic acid pentyl diol ester, the dimethacrylate DOPCP, poly-ethylene glycol diacrylate, polydimethyl vinylformic acid glycol ester, the dihydroxyphenyl propane diol ester of diacrylate ethoxylation, the dihydroxyphenyl propane diol ester of dimethacrylate ethoxylation, trimethylolpropane trimethacrylate, Viscoat 295, pentaerythritol triacrylate, the Viscoat 295 of ethoxylation, glyceryl propoxy-triacrylate, pentaerythritol tetracrylate and five vinylformic acid dipentaerythritol ester.
17. according to the photo-corrosion-resisting agent composition of claim 13, base further comprises following component by weight:
(d) 1 to 50 part Resins, epoxy; And
(e) 0.1 to 30 part thermal curing agents.
18. photo-corrosion-resisting agent composition according to claim 17, glycidyl ether, phenolic aldehyde polyglycidyl ether, alkyl glycidyl ether, naphthalene that wherein said Resins, epoxy is selected from the glycidyl ether of bisphenol type, two diphenol types are the Resins, epoxy of glycidyl ether, dicyclo penta diphenol glycidyl ether, ring-shaped fat class glycidyl ether, isocyanic ester glycidyl ether, polyhydroxy phenol polyglycidyl ether, bromination, and composition thereof.
19. according to the photo-corrosion-resisting agent composition of claim 17, wherein said thermal curing agents is selected from aliphatics amine, aromatic amine, polyamide-based, Dicyanodiamide class, imidazoles and anhydrides.
20. the method that the multipolymer of key side chain is closed in insatiable hunger that contains of making claim 1, it comprises:
(a) will contain insatiable hunger and close the monomer of key and contain insatiable hunger and close the anhydride monomers of key and carry out copolymerization, wherein this contains insatiable hunger and closes the monomer of key and do not have anhydride group;
(b) multipolymer that will go on foot poly-(a) gained closes the alcohols reaction of key with containing insatiable hunger, make the anhydride functional group of 0.01 to 100 molar percentage in the multipolymer via the esterification ring-opening reaction mono-esterification, and produce the carboxylic acid group; And
(c) with the multipolymer of step (b) gained and the reaction of epoxy ethyl compound, make that the hydroxy-acid group of 0.01 to 100 molar percentage becomes ester group via the epoxide group ring-opening reaction in the multipolymer, contain the multipolymer that the key side chain is closed in insatiable hunger and obtain this,
Wherein said epoxy ethyl compound comprises that containing insatiable hunger closes the epoxy ethyl compound of key and/or contain heteroatomic epoxy ethyl compound, and this heteroatoms is selected from silicon, nitrogen, phosphorus and sulphur.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99126266 CN1114629C (en) | 1999-12-22 | 1999-12-22 | Copolymer containing unsaturated bond branched chain and its photoresist composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99126266 CN1114629C (en) | 1999-12-22 | 1999-12-22 | Copolymer containing unsaturated bond branched chain and its photoresist composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1303876A CN1303876A (en) | 2001-07-18 |
| CN1114629C true CN1114629C (en) | 2003-07-16 |
Family
ID=5284363
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 99126266 Expired - Lifetime CN1114629C (en) | 1999-12-22 | 1999-12-22 | Copolymer containing unsaturated bond branched chain and its photoresist composition |
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| Country | Link |
|---|---|
| CN (1) | CN1114629C (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100440431C (en) * | 2003-03-04 | 2008-12-03 | 东京応化工业株式会社 | Immersion liquid for immersion exposure process and resist pattern forming method using such immersion liquid |
| CN101942067B (en) * | 2010-08-17 | 2013-03-13 | 浙江大学 | Anhydride esterification segmented pectinate copolymer, preparation method thereof and application for serving as crude oil pour point depressants and viscosity reducer |
| CN103130955B (en) * | 2013-03-07 | 2015-06-17 | 京东方科技集团股份有限公司 | Photosensitive oligomer for photoresist, preparation method and negative photoresist composition thereof |
| KR101378026B1 (en) * | 2013-04-26 | 2014-03-25 | 금호석유화학주식회사 | Polymer for resist and resist composition comprising the same |
| CN103497325B (en) | 2013-08-20 | 2015-07-22 | 京东方科技集团股份有限公司 | Polyester compounds, preparation method thereof and photoresist composition |
| CN106810632A (en) * | 2015-11-30 | 2017-06-09 | 大东树脂化学股份有限公司 | Styrene-acid anhydride-acrylate copolymer containing ester group or amide groups and preparation method thereof and purposes |
| JP7074051B2 (en) * | 2016-03-08 | 2022-05-24 | 住友ベークライト株式会社 | Polymer manufacturing method, negative photosensitive resin composition manufacturing method, resin film manufacturing method, electronic device manufacturing method and polymer |
| CN109581814A (en) * | 2017-09-29 | 2019-04-05 | 互耐普勒斯有限公司 | Low temperature curing type Photosensitve resin composition |
-
1999
- 1999-12-22 CN CN 99126266 patent/CN1114629C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1303876A (en) | 2001-07-18 |
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