CN102618164A - Method for increasing bonding force between conductive body and non-conductive macromolecule dielectric layer in printed circuit board substrate - Google Patents
Method for increasing bonding force between conductive body and non-conductive macromolecule dielectric layer in printed circuit board substrate Download PDFInfo
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- CN102618164A CN102618164A CN2012100459244A CN201210045924A CN102618164A CN 102618164 A CN102618164 A CN 102618164A CN 2012100459244 A CN2012100459244 A CN 2012100459244A CN 201210045924 A CN201210045924 A CN 201210045924A CN 102618164 A CN102618164 A CN 102618164A
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Abstract
The invention provides a method for increasing bonding force between a conductive body and a non-conductive macromolecule dielectric layer in a printed circuit board substrate. The method comprises the steps of performing rough treatment to the surface of the conductive body, soaking the conductive body in a silane solution with 0.01%-100% of volume concentration for seconds or minutes after the rough treatment or directly spraying the silane solution with 0.01%-100% of volume concentration onto the surface of the conductive body, and accordingly adding a silane layer on the surface. On the basis of existing methods, the method increases a process for forming the silane layer in one step, thereby increasing the bonding force between the conductive body and the non-conductive macromolecule dielectric layer and solving the board exploding problem caused by insufficient bonding force between the conductive body and the non-conductive macromolecule dielectric layer.
Description
Technical field
The present invention relates to printed circuit board base board, particularly in the printed circuit board base board, increase the method for bonding force between electrical conductor and the non-conductive polymer dielectric layer.
Background technology
Printed substrate (PCB) has become the electronics and IT products most important parts as the carrier of various components and parts and the hinge of circuit signal transmission.Along with the miniaturized of electronics and IT products and the environmental requirement of lead-free and halogen-freeization, PCB also develops to the direction of highly dense high glass transition point (Tg) and environmental protection.Especially in recent years; The enhancing of Along with people's environmental protection consciousness; Halogen flame is as the main base material of tellite; Discharge Dioxins (Dioxin), diphenylene-oxide carcinogenic substances such as (Dibenxofuran) in the products of combustion of its waste, and the Halogen product very big in the combustion processes amount of being fuming, can discharge problem such as highly toxic substance hydrogen halide and become increasingly conspicuous, and receive extensive concern.With it simultaneously, halogen-free flame retardants substitutes halogen flame gradually, becomes the main base material of printed wiring.
Yet, in the multilayer printed circuit board substrate,, usually can cause bonding force deficiency between layer and the layer, thereby cause plate bursting along with higher glass transition point of increasing use (high Tg) and Halogen sheet material.
The PCB substrate generally is by non-conductor or insulation layer: as glass/epoxy resin with the copper or the copper alloy pressing of each one deck form up and down.Multilayer circuit board mainly be by the internal layer with circuit, dielectric insulation material and up and down two copper faces produce via HTHP.And dielectric insulation material is generally the B attitude resin of partly drying (B-Stage resin) and is called as prepreg.Because untreated copper face can not produce good bonding force with dielectric layer, the surface treatment method that therefore produces various copper layers is to increase the bonding force of copper layer and dielectric layer.Wherein, mainly contain horizontal brown method and melanism method.
Wherein, the reaction mechanism of brown is:
2Cu+H
2SO
4+H
2O
2+nR
1+nR
2→CuSO
4+2H
2O+Cu(R
1+R
2)
In the brown groove, because H
2O
2Little erosion effect, make matrix copper surface deposit the thin organo-metallic film of last layer book immediately, increase the bonding force of PP and copper face.Yet the nano and micro relief of brown face is bad, test bonding force difference and cause plate bursting after the pressing.
Melanism is because of Cu
20 forms easily minute hand shape or featheriness crystallization, when high temperature, be easy to fracture and influence the sticking power of copper and interlaminar resin greatly, and with gummosis stain is scattered during pulling, to form electrical problem, and moisture content appears easily and form high hot after partial layering plate bursting.
Summary of the invention
In order to overcome the deficiency of prior art; The invention provides in printed circuit board base board, increase the method for bonding force between electrical conductor and the non-conductive polymer dielectric layer, this method is on the basis of original method; Increased one procedure; Thereby increased bonding force between electrical conductor and the non-conductive polymer dielectric layer, reduced because of bonding force between electrical conductor and the non-conductive polymer dielectric layer is not enough, and caused the plate bursting problem.
Technical scheme of the present invention is following: in the printed circuit board base board; Increase the method for bonding force between electrical conductor and the non-conductive polymer dielectric layer; Comprise: on the electrical conductor surface, do earlier coarse processing; After the coarse processing with said electrical conductor be immersed in volumetric concentration be solution of silane several seconds of 0.01%～100% to several minutes, or be 0.01%～100% solution of silane directly, thereby increase one deck silylation layer on its surface in said electrical conductor surface sprinkling volumetric concentration.
Described electrical conductor is gold and silver, tin, lead, aluminium, iron, cobalt, nickel, chromium, copper or zinc material.
Said non-conductive polymer dielectric layer is the material that spun glass and epoxy are counted fat (epoxy resin) or resol (phenol resin) composition, and it has FR-4, insulation, Halogen, High Tg characteristic.
Said non-conductive polymer dielectric materials is selected from a kind of or above-mentioned several kinds mixture in tetrafluoroethylene, epoxy resin, polyimide, poly-cyanate ester resin, the butylene terephthalate resin.
The form of construction work that said electrical conductor soaks in said solution of silane is the sea line transmission or vertically soaks operation.
Said coarse physics brush mill, the H of being treated to
2O
2/ H
2SO
4Chemical little erosion of tranquilizer, NA
2S
2O
8The little erosion of/H2SO4, KHSO
5KHSO
5K
2SO
4/ H
2SO
4Little erosion, KHSO
5KHSO
5K
2SO
4/ H
3PO
4Little erosion, in thick, ultra thick, melanism, first-generation H
2SO
4System's brown or s-generation nitric acid/formic acid system brown.
Said solution of silane is that silane is water-soluble, the solution of alcoholic solvent, ketones solvent, esters solvent or benzene kind solvent gained.
The essential substance of said silylation layer is silane, silane derivative, imidazoles-silane compound, imidazoles-silane compound verivate, imidazoles-silane-organic acid salt mixture, imidazoles-silane-organic acid salt mixture verivate, organic annular silane or organic annular silane verivate.
The general formula of said silane is Y (CH
2) nSiX
3, wherein, n=0～20; X represents halogen radical, methoxyl group, oxyethyl group, alkoxyl group, methoxy ethoxy or acetoxyl group; Y represents vinyl, amino, epoxy group(ing), methacryloxy, sulfydryl or urea groups.
Said silane is pressed functional group classification, be selected from epoxy radicals silicone hydride (epoxysilane), vinyl silanes (vinylsilane), propenyl silane (acrylsilane), amino silicic acid (aminosilane), hydrosulphonyl silane (mercaptosilane), silicon ester silane (estersilane), urea groups silane (ureidosilane), isocyanato silane (isocyanatosilane) polyvinyl silane (polyvinylsilane), methacryloxy silane (methacryloxysilane) and chloro silane (chlorosilane),, one or more the mixture in the siloxanes (siloxane).
Said silane is selected from methyltrimethoxy silane (methyltrimethoxysilane); Ethyl trimethoxy silane (ethyltrimethoxysilane); Propyl trimethoxy silicane (propyltrimethoxysilane); Normal-butyl Trimethoxy silane (n-butyltrimethoxysilane); Isobutyl-Trimethoxy silane (isobutyltri methoxysilane); Phenyltrimethoxysila,e (pentyltrimethoxysilane); Hexyl Trimethoxy silane (hexyltrimethoxysilane); Octyl group Trimethoxy silane (octyltrimethoxysilane); 7-octene-1-Ji Trimethoxy silane (7-oct-1-enyltrimethoxysilane); P-methylphenyl Trimethoxy silane (p-(methyl) phenyltrimethoxysilane); 3-cyclopentano-diallyl trimethoxy alkyl (3-cyclopent adienylpropyltrimethoxysilane); Vinyltrimethoxy silane (vinyltrimethoxysilane); Allyltrimethoxysilanis (allyltrimethoxysilane); 3-methoxymethoxy propyl silane (methox ypropyltrimethoxysilane); Union carbide A-162 (methyltriethoxysilane); Ethyl triethoxysilane (ethyltriethoxysilane); Propyl-triethoxysilicane (propyltriethoxysilane); Ne-butyltriethoxysilaneand (n-butyltriethoxysilane); Isobutyl-triethoxyl silane (isobutyltriethox ysilane); Isobutyl-Trimethoxy silane (isobutyltrimethoxysilane); Phenyl triethoxysilane (pentyltriethoxysilane); Phenyltrimethoxysila,e (pentyltrimethoxysilane); Hexyl triethoxyl silane (hexyltriethoxysilane); Hexyl Trimethoxy silane (hexyltrimethoxysilane); Octyltri-ethoxysilane (octyltriethoxysilane); Octyl group Trimethoxy silane (octyltrimethoxysila ne); 7-octene-1-ethyl triethoxy silicane alkane (7-oct-1-enyltriethoxysilane); 7-octene-1-Ji Trimethoxy silane (7-oct-1-enyltrimethoxysilane); P-methylphenyl triethoxyl silane (p-(methyl) phenyltriethoxysilane); P-methylphenyl Trimethoxy silane (p-(methyl) phenyltrimethoxysil ane); 3-cyclopentano-diallyl triethoxy alkyl (3-cyclopentadienylpropyltriethoxysilane); 3-cyclopentano-diallyl trimethoxy alkyl (3-cyclopentadienylpropyltrimethoxysilane); Vinyltriethoxysilane (vinyltriethoxysilane); Vinyltrimethoxy silane (vinyltrimethox ysilane); Allyltriethoxysilane (allyltriethoxysilane); Allyltrimethoxysilanis (all yltrimethoxysilane); 3-oxyethyl group methoxy base propyl silane (methoxypropyltriethoxysilane); 3 methoxymethoxy propyl silanes (methoxypropyltrimethoxysilane), methyl three isopropoxy silane (methyltriisopropoxysilane), ethyl three isopropoxy silane (ethyltriisopropoxysilane), propyl group three isopropoxy silane (propyltriisopropoxysilane), vinyl silane triisopropoxide (viny ltriisopropoxysilane), three tert.-butoxy vinyl silanes (vinyltris-t-butoxysilane), trifluoro propane Trimethoxy silane (3; 3; 3-trifluoropropyltrimethoxysilane), ten trifluoro octyltri-ethoxysilane (tridecafluoroctyltriethoxysilane), vinyl three (2-methoxy ethoxy) silane (vinyltris (2-methoxyethoxy) silane), vinyl trichloro silane (vinyltrichlorosilane), vinyl-dimethyl oxygen ylmethyl silane (vinyldimethoxymethylsilane), vinyl diethoxy methyl-monosilane (vinyldiethoxy methylsilane), 3-allyl oxygen propyl trimethoxy silicon (3-acryloxypropyltrimethoxysilane), methacryloxypropyl methyldiethoxysilane (3methacryloxypropylmethyldiethoxysilan e), 3-methacryloxypropyl methyl dimethoxysilane (3methacryloxypropylmethyldimet hoxysilane), 3-(methacryloxypropyl) propyl trimethoxy silicane (3-methacryloxypropyltrimet hoxysilane), 3-(methacryloxypropyl) propyl-triethoxysilicane (3-methacryloxypropyltrietho xysilane), 3-Racemic glycidol propyl trimethoxy silicane (3-glycidoxypropyltrimethoxysilane), β-(3; The 4-epoxy cyclohexane) ethyl trimethoxy silane (2-(3,4epoxycyclohexyl) ethyltrimethoxy silane), N-(2-amine ethyl)-3-amine propyl group trimethoxy silane (N-2-(aminoethyl)-3-aminopropyltri methoxysilane), N-(2-amine ethyl)-3-amine propyl group methyl dimethoxy oxosilane (N-2-(aminoethyl)-3-a minopropylmethyldimethoxysilane), 3-amine propyl group methyl trimethoxy oxosilane (3-aminopropyltri methoxysilane), 3-amine propyl group methyl three ethoxy silane (3-aminopropyltriethoxysilane), γ-An Bingjisanyiyangjiguiwan (3-aminopropyl) triethoxysilane), γ-aminopropyl dimethoxy-methyl silane (3-aminopropyl) dimethoxymethylsilane), γ-aminopropyl dimethoxy-ethyl silane (3-aminopr opyl) diethoxymethylsilane), the N-(2-aminoethyl-3-aminopropyl-3-methoxy silane (mixture of one or more in N-(2-amino ethyl)-3-aminopropyltrimethoxysilane), N-methyl aminopropyl trimethoxysilane (N-methyla minopropyltrimethoxysilane), N-methyl aminopropyl triethoxysilane (N-methylaminopropy ltriethoxysilane), 3-urea propyl-triethoxysilicane (3-ureidopropyltriethoxysilane), 3-mercaptopropyl trimethoxysilane (3-Mercaptopropyltriethoxysilane), 3-(4-phenyl ester) propyl trimethoxy silicane (3-(4-cyanatophenyl) propyltrimethoxysilane), polyvinyl triethyl silicane (pol yvinyl trimethyl silane) N-phenyl-3-amine propyl group methyl trimethoxy oxygen silicon (N-phenyl-3-aminopro pyltrimethoxysilane), 3-mercaptopropyl trimethoxysilane (3-mercaptopropyltrimethoxysilane), 3-r-chloropropyl trimethoxyl silane (3-chloropropyltrimethoxysilane), tetramethoxy-silicane (tet ramethoxysilane), tetraethoxysilane (tetraethoxysilane), tetrapropoxysilane (tetraprop oxysilane), four butoxy silanes (tetra-n-butoxysilane), diethoxymethyl [(3-Oxyranyle methoxy) propyl group] silane (gamma-glycidoxypropylmethyldimethoxysilane), 3-glycidyl ether oxygen base propyl group pentamethyl disilane (gamma-glycidoxypropylpylpentamethyldisilane), 3-glycidyl ether oxygen base propyl group methyldiethoxysilane (gamma-glycidoxypropylmethyldiethoxys ilane), 3-glycidyl ether oxygen base propyl-dimethyl diethoxy silane (gamma-glycidoxypropyldi methylethoxysilane) or the 3-glycidyl ether oxygen base propyl group-two trimethylsiloxy group methyl-monosilanes ((gam ma-glycidoxypropyl)-bis (trimethylsiloxy) methylsilane).
Said imidazoles silane compound is that imidazoles and silane react resulting mixtures or imidazoles and silane derivative through 80～200 ℃ of resulting mixtures of reaction through 80～200 ℃, and wherein, the chemical formula of said imidazoles is:
(1)?
The chemical formula of said silane or silane derivative is:
(2)
Reaction product is:
(3)?
(4)?
(5)
Mixture;
Wherein, wherein, R
1, R
2And R
3Represent the alkyl substituent of hydrogen base, thiazolinyl, phenolic group, phenyl or 1～20 carbon, R
2, R
3Can form aromatic nucleus, R
4, R
5Represent the alkyl substituent of 1～5 carbon, and n represents 1～3.
Said silane is the mixture of said compound (3), (4) and (5) or wherein a kind of.
Said imidazoles is selected from imidazoles (imidazole), aminooimidazole (aminoimidazole), diamino-imidazoles (diaminoimidazole), monomethyl imidazoles (monomethylimidazole), 2-alkyl imidazole (2-alkylimidazole), 2; The 4-dialkylimidazolium (2,4-dialkylimidazole), 4-vinyl imidazole (4-vinylimidazole), glyoxal ethyline (2-methylimidazole), 2-ethyl imidazol(e) (2-ethylimidazole), 2-undecyl imidazole (one or more mixtures in 2-undecylimidazole0,2-heptadecyl imidazoles (2-heptadecylimidazole), benzoglyoxaline (benzimidazole), benzotriazole (benzotriazole), pyridine (pridine), the 2-ethyl-4-methylimidazole (2-ethyl-4-methylimidazole).
Silane in the said imidazoles silane compound is selected from 3-Racemic glycidol propyl trimethoxy silicane (3-glycidoxypropyltrimethoxysilane); 3 Racemic glycidol propyl group dialkoxy silicanes (3-glycidoxypropyldialkoxysilane); 3-Racemic glycidol propyl group oxyethyl group dimethylsilane (3-glycidoxypropylethoxydimethylsilane); One or more mixtures in the 3-Racemic glycidol propyl group alkoxyl group dialkyl silane (3-glycidoxypropylalkoxydialkylsilane).
The mixture of said (3), (4) and (5) also with following compound,
Wherein, R
6, R
7, R
8Represent the alkyl substituent of hydrogen base, thiazolinyl, phenolic group, phenyl or 1～20 carbon, R
7, R
8Can form aromatic nucleus, R
9, R
10Possibly be the alkyl substituent of 1～5 carbon, and o represents 1～10, p represents 1～3.
Said imidazoles-silane-organic acid salt mixture is the reaction product of imidazoles-silane compound and organic acid salt; Said imidazoles-silane-organic acid salt mixture verivate is the reaction product of imidazoles-silane derivative and organic acid salt,
Wherein, the chemical formula of said imidazoles is:
(6)?
The chemical formula of said silane is:
(7)?
The chemical formula of said imidazoles-silane compound or imidazoles-silane compound verivate is:
(8)?
The chemical formula of said imidazoles-silane-organic acid mixture or said imidazoles-silane-organic acid mixture verivate is:
(9)?
Wherein, R
1, R
2And R
3Represent the alkyl substituent of hydrogen base, thiazolinyl or 1～20 carbon, R
2, R
3Also represent fragrant cyclic group, R
4, R
5Represent the alkyl substituent of 1～5 carbon, m represents 1～10, and n represents 1～3.
Said imidazoles is selected from imidazoles (imidazole), 2-alkyl imidazole (2-alkylimidazole), 2; The 4--dialkylimidazolium (2,4-dialkylimidazole), 4-vinyl imidazole (4-vinylimidazole),, one or more the mixture in the benzoglyoxaline (benzimidazole), benzotriazole (benzotriazole), pyridine (pridine), glyoxal ethyline (2-methylimidazole), 2-ethyl imidazol(e) (2-ethylimidazole), 2-undecyl imidazole (2-undecylimidazole), 2-heptadecyl imidazoles (2-heptadecylimidazole), 2-ethyl-4-methylimidazole (2-ethyl-4-methylimidazole).
Said silane is selected from 3-Racemic glycidol propyl trialkoxy silane (3-glycidoxypropyltrialkoxysila nes); 3-Racemic glycidol propyl group dialkoxy alkyl silane (3-glycidoxypropyldialkoxyalkylsilane s); 3-Racemic glycidol propyl group alkoxyl group dialkyl silane (3-glycidoxypropylalkoxydialkylsilanes); 3-Racemic glycidol propyl trimethoxy silicane (3-glycidoxypropyltrimethoxysilane); 3-Racemic glycidol propyl-triethoxysilicane (3-glycidoxypropyltriethoxysilane); 3-Racemic glycidol propyl group dialkoxy alkyl silane (3-glycidoxypropyldialkoxyalkylsilane); 3-Racemic glycidol propyl group dimethyl ethoxy methyl-monosilane (3-glycidoxypropyldimethoxymethylsilane); The mixture of one or more in 3-Racemic glycidol propyl group alkoxyalkyl silane (3-glycidoxypropylalkoxydialkylsilane) or the 3-Racemic glycidol propyl group oxyethyl group dimethylsilane (3-glycidoxypropylethoxydimethylsilane).
Organic acid described in said imidazoles-silane-organic acid mixture or imidazoles-silane-organic acid mixture verivate is organic monocarboxylic acid, saturated fatty monocarboxylic acid, unsaturated fatty acids monocarboxylic acid or fragrance bunch monocarboxylic acid or its analogue.
Said organic acid is one or more the mixture in vinylformic acid, isopropylformic acid, methylacrylic acid, sad, formic acid, oxoethanoic acid, Ba Dousuan, acetate, propionic acid, phenylformic acid, Whitfield's ointment, hexahydrobenzoic acid, o-toluic acid, toluylic acid or the p-tert-butyl benzoic acid.
Said organic acid is a methylacrylic acid.
Said silane is that organic annular silane (organosilicic silane) or organic ring silicon derivative and alkylene silane (olefin-based silane) stir the 2hrs afterreaction 40～90 ℃ intensification and produces, and reaction formula is following:
Wherein, R
1Representative is the alkyl substituent of hydroxyl or 1～5 carbon; R
2Represent the alkyl substituent of hydrogen base or 1～10 carbon, and this alkyl aerobic optionally; X has two hydroxyls at least in (1) and (2), and n is 2 at least, and m is 1 at least; R
3Represent the alkyl substituent of 1～5 carbon, R
4Representative is hydroxyl-or the alkyl substituent of 1～5 carbon, R
5Represent the alkyl substituent of hydrogen base or 1～10 carbon, and this alkyl aerobic optionally, L represents 2～3.
Said organic annular silane is selected from vinyl silanes (vinyl-based silanes), propenyl silane (acryli c-based silanes) and methacrylic base silane (methacrylic-based silanes); Wherein, vinyl silanes comprises vinyltrimethoxy silane (vinyltrimethoxysilane), vinyltriethoxysilane (v inyltriethoxysilane), vinyl trichlorine base silane (vinyltrichlorosilane), vinyl trialkyl oxysilane (vinyltrialkoxysilanes), vinyl dialkoxy alkyl silane (vinyldialkoxyalkylsilan es), vinyl three (dimethoxy oxyethyl group) silane (vinyltris (beta-methoxyethoxy) silane), vinyl-dimethyl oxygen ylmethyl silane (vinyldimethoxymethylsilane), vinyl diethoxymethyl silane (vinyldiethoxymethylsilane); Propenyl silane (acrylic-based silanes) comprises 3-allyl oxygen propyl trimethoxy silicon (gamma-acryloxypropyltrimethoxysilane); Methylpropenyl silane comprises (methacrylic-based silanes); Methacryloxypropyl trimethoxy silane (gamma-methacryloxypropyltrimethoxysilane); 3-methacryloxypropyl methyl dimethoxysilane (gamma-methacryloxypropylmethyldimethoxysilane); The mixture of one or more in 3-(methacryloxypropyl) propyl group methyldiethoxysilane (gamma-methacryloxypropylmethyldiethoxysilane) or the 3-methacryloxypropyl triethoxyl silane (gamma-methacryloxypropyltriethoxysilane).
The mass ratio of organic annular silane and silane described in the mixture of said organic annular silane and silane is 99: 1～1: 99.
In the printed substrate; Increase the method for bonding force between electrical conductor and the non-conductive polymer dielectric layer; Comprise: on metal sheet surface, do earlier coarse processing; Then said non-conductive polymer dielectric material plate being immersed in volumetric concentration is the several seconds or several minutes in 0.01%～100% the solution of silane, or is 0.01%～100% solution of silane in said non-conductive polymer dielectric material plate surface sprinkling volumetric concentration directly, thereby increases one deck silylation layer on its surface.
A kind of printed substrate comprises electrical conductor and the non-conductive polymer dielectric layer that presses together with this electrical conductor, also has one deck silylation layer between said electrical conductor and the said non-conductive polymer dielectric layer.
Of the present invention in printed circuit board base board; Increase the method for bonding force between electrical conductor and the non-conductive polymer dielectric layer; On the basis of original method, increased the operation of step increase silylation layer, thereby increased bonding force between electrical conductor and the non-conductive polymer dielectric layer; Reduced because of bonding force between electrical conductor and the non-conductive polymer dielectric layer is not enough, and caused the plate bursting problem.
Description of drawings
The internal layer copper foil surface of Fig. 1, undressed sample 1;
The SEM figure of the internal layer copper foil surface of the sample 2 after Fig. 2, the processing;
The SEM figure of the internal layer copper foil surface of the sample 3 after Fig. 3, the processing;
The SEM figure of the internal layer copper foil surface of the sample 4 after Fig. 4, the processing;
The SEM figure of the internal layer copper foil surface of the sample 5 after Fig. 5, the processing;
The SEM figure of the internal layer copper foil surface of the sample 6 after Fig. 6, the processing.
Specific embodiment
Along with electronic product develops to lightening direction day by day, add intensive electronic circuit, cause the inner layer metal plate, promptly the roughness of electrical conductor reduces, and then causes the reliability problem of bonding force.Another fermentation; Halogen-free flame retardants substitutes halogen flame gradually; Become the main base material of printed wiring; Electronics industry non-conductive polymer dielectric layer material commonly used has FR-4, insulation, Halogen, High Tg characteristic at present; Count fat (epoxy resin) or resol (phenol resin) material is main with spun glass and epoxy, like mixture of polytetrafluoroethylene (PTFE), epoxy resin (EPOXY RESIN), polyimide (POLYIMIDE), poly-cyanate ester resin (POLYCYANATE ESTER), butylene terephthalate resin (BUTADIENE TEREPHTHALATE RESIN) or above-mentioned different materials etc.Be to improve metal sheet, i.e. electrical conductor, surfaceness and bonding force; The present invention is employed in the little erosion roughened layer that increases by a crystal lattice level on the matrix metal plate surface; Use the increase surfaceness, then be coated with a last silylation layer again, with the bonding force of increase with macromolecular material.
Described electrical conductor is the mixture of gold and silver, tin, lead, aluminium, iron, cobalt, nickel, chromium, copper or zinc material or above-mentioned material, and especially the electrical conductor with the Copper Foil material is the most commonly used.
The form of construction work that said electrical conductor soaks in said solution of silane is the sea line transmission or vertically soaks operation.
For bright essence of the present invention in detail specifically; The present invention is that metal substrate is representative with the electrical conductor of matrix Copper Foil material; Be provided with 6 samples,, on the matrix copper foil surface, increase little erosion roughened layer of a crystal lattice level through the different processes process; Then different silylation layer in coating then detects thermotolerance, wet fastness and the bonding force poundage of products therefrom.
The used reagent of this experiment is following:
Solution of silane:
1, epoxy radicals silicone hydride methyltrimethoxy silane solution: getting methyltrimethoxy silane, is to mix at 1.5: 97.5 with water by volume;
2, vinyl silanes vinyltrimethoxy silane solution: get vinyltrimethoxy silane, mixed in 10: 90 by volume with methyl alcohol;
3, propenyl silane 3-(methacryloxypropyl) propyl trimethoxy silicane solution: getting 3-(methacryloxypropyl) propyl trimethoxy silicane, is to mix at 20: 80 with acetone by volume;
4, aminosilane 3-amine propyl group methyl trimethoxy oxosilane solution: get 3-amine propyl group methyl trimethoxy oxosilane and ETHYLE ACETATE and mixed in 30: 70 by volume;
5, hydrosulphonyl silane 3-mercaptopropyltriethoxysilane solution: get 3-mercaptopropyltriethoxysilane and phenol and be by volume and mix at 40: 60;
6, silicon ester silane 3-(4-phenyl ester) propyl trimethoxy silicane solution: get 3-(4-phenyl ester) propyl trimethoxy silicane and water and be by volume and mix at 50: 50;
7, urea groups silane 3-(4-phenyl ester) propyl trimethoxy silicane solution: get 3-(4-phenyl ester) propyl trimethoxy silicane and ethanol and be by volume and mix at 60: 40;
8, isocyanato silane 3-NCO propyl-triethoxysilicane solution: get 3-NCO propyl-triethoxysilicane and isopropylcarbinol and be by volume and mix at 70: 30;
9, polyvinyl silane Vilaterm trimethyl silane solution: get Vilaterm trimethyl silane and butanone and mixed in 20: 80 by volume;
10, imidazoles silane imidazoles-3-glycidyl ether oxygen base propyl trimethoxy silicane mixture solution: get imidazoles-3-glycidyl ether oxygen base propyl trimethoxy silicane, mixed in 10: 90 by volume with glyceryl ester;
11, the imidazoles silane compound is said product (a 4) solution: getting said imidazoles silane compound product (4), is to mix at 0.5: 99.5 with water by volume;
12, imidazoles-silane-organic acid salt mixture imidazoles-3-3-glycidyl ether oxygen base propyl trimethoxy silicane monocarboxylate solution: get imidazoles-3-3-glycidyl ether oxygen base propyl trimethoxy silicane monocarboxylate, mixed in 99.5: 0.5 by volume with water.
Roughening solution:
Electron Material Co., Ltd of the lucky company of Dongguan City benevolence product, model fC1520: mainly contain H
2O
2/ H
2SO
4With organic acid, it is 2.5% solution that water is diluted to concentration with this product.
Electron Material Co., Ltd of the lucky company of Dongguan City benevolence product, model fC669: mainly contain HNO
3With organic acid, stoste is used.
Horizontal brown solution:
Electron Material Co., Ltd of the lucky company of Dongguan City benevolence product, model fC1020R mainly contains H
2O
2/ H
25O
4With BTA, it is 10% solution that water is diluted to concentration with this product.
Electron Material Co., Ltd of the lucky company of Dongguan City benevolence product, model fC1028R mainly contains HNO
3/ HCOOH and BTA, it is 10% solution that water is diluted to concentration with this product.
Concrete experimentation is following:
Sample 1: adopt undressed matrix copper coin, its surface is as shown in Figure 1.
Sample 2: the treating processes of sample 2 is following:
Alkali takes off: get 12 matrix copper coins, and these 12 matrix copper coins are carried out alkali respectively take off, be about to the matrix copper coin and mainly containing NaOH, NaCO
3Soak 2min in the alkali precipitation liquid Deng compound, solution temperature is 50 ℃;
In bulk processing: thick solution product in getting promptly that Electron Material Co., Ltd of the lucky company of Dongguan City benevolence produces; Model fC1520; It is 2.5% solution that water is made into into concentration, and solution temperature is controlled at 30～40 ℃, and 12 matrix copper coins after alkali is taken off soak 30sec in this solution; Certainly, also available other companies in thick solution replace fc1520;
Increase silylation layer: with 12 matrix copper coins after the middle bulk processing, be immersed in above-mentioned 12 kinds of solution of silane respectively at level under the room temperature, take out behind the immersion 20sec, oven dry is preserved.Its surface is as shown in Figure 2.
Sample 3: the treating processes of sample 3 is following:
Alkali takes off: get 12 matrix copper coins, and these 12 matrix copper coins are carried out alkali respectively take off, be about to the matrix copper coin and mainly containing NaOH, NaCO
3Soak 2min in the alkali precipitation liquid Deng compound, solution temperature is 50 ℃;
Ultra thick: get the ultra thick solution product that Electron Material Co., Ltd of the lucky company of Dongguan City benevolence produces, model fC669: solution temperature is controlled at 35～45 ℃, and 12 matrix copper coins after alkali is taken off soak 30sec in this solution; Certainly, also the ultra thick solution of available other companies replaces fC669; ,
Increase silylation layer: with 12 matrix copper coins after the middle bulk processing, respectively at vertically being immersed under the room temperature in above-mentioned 12 kinds of solution of silane, take out behind the immersion 20sec, oven dry is preserved.Its surface is as shown in Figure 3.
Sample 4: the treating processes of sample 4 is following:
Alkali takes off: get 12 matrix copper coins, and these 12 matrix copper coins are carried out alkali respectively take off, be about to the matrix copper coin and mainly containing NaOH, NaCO
3Soak 2min in the alkali precipitation liquid Deng compound, solution temperature is 50 ℃;
Melanism: the matrix copper coin after alkali taken off is mainly containing NaOH/H
3PO
4Solution in soak 5min, solution temperature is 50 ℃;
Reduction: the matrix copper coin after the melanism is soaked 5min in the solution that mainly contains NaOH/DMAB, solution temperature is 30 ℃;
Increase silylation layer: with 12 matrix copper coins after the middle bulk processing, be immersed in above-mentioned 12 kinds of solution of silane respectively at level under the room temperature, take out behind the immersion 20sec, oven dry is preserved.Its surface is as shown in Figure 4.
Sample 5: the treating processes of sample 5 is following:
Alkali takes off: get 12 matrix copper coins, and these 12 matrix copper coins are carried out alkali respectively take off, be about to the matrix copper coin and mainly containing NaOH, NaCO
3Soak 2min in the alkali precipitation liquid Deng compound, solution temperature is 50 ℃;
Di-the Dai brown: get the ultra thick solution product that Electron Material Co., Ltd of the lucky company of Dongguan City benevolence produces; Model fC1020R: it is 10% solution that water is diluted to concentration with this product; Solution temperature is controlled at 35～45 ℃, and 12 matrix copper coins after alkali is taken off soak 60sec in this solution; Certainly, also the ultra thick solution of available other companies replaces fC1020R;
Increase silylation layer: with 12 matrix copper coins after the middle bulk processing, respectively at vertically being immersed under the room temperature in above-mentioned 12 kinds of solution of silane, take out behind the immersion 20sec, oven dry is preserved, and its surface is as shown in Figure 5.
Sample 6: the treating processes of sample 6 is following:
Alkali takes off: get 12 matrix copper coins, and these 12 matrix copper coins are carried out alkali respectively take off, be about to the matrix copper coin and mainly containing NaOH, NaCO
3Soak 2min in the alkali precipitation liquid Deng compound, solution temperature is 50 ℃;
S-generation brown: get the product that Electron Material Co., Ltd of the lucky company of Dongguan City benevolence produces; Model fC1028R: it is 10% solution that water is diluted to concentration with this product; Solution temperature is controlled at 35～45 ℃, and 12 matrix copper coins after alkali is taken off soak 60sec in this solution; Certainly, also the ultra thick solution of available other companies replaces fC1028R;
Increase silylation layer: with 12 matrix copper coins after the middle bulk processing, respectively at vertically being immersed under the room temperature in above-mentioned 12 kinds of solution of silane, take out behind the immersion 20sec, oven dry is preserved, and its surface is as shown in Figure 6.
Be applicable in the printed circuit board base board according to the invention that the essential substance that increases the silylation layer of the method for bonding force between electrical conductor and the non-conductive polymer dielectric layer has silane, silane derivative, imidazoles-silane compound, imidazoles-silane compound verivate, imidazoles-silane-organic acid salt mixture, imidazoles-silane-organic acid salt mixture verivate, organic annular silane or organic annular silane verivate.
The general formula of said silane is Y (CH
2) nSiX
3, wherein, n=0～20; X represents halogen radical, methoxyl group, oxyethyl group, alkoxyl group, methoxy ethoxy or acetoxyl group; Y represents vinyl, amino, epoxy group(ing), methacryloxy, sulfydryl or urea groups.
Said silane is pressed functional group classification, be selected from epoxy radicals silicone hydride (epoxysilane), vinyl silanes (vinylsilane), propenyl silane (acrylsilane), amino silicic acid (aminosilane), hydrosulphonyl silane (mercaptosilane), silicon ester silane (estersilane), urea groups silane (ureidosilane), isocyanato silane (isocyanatosilane) polyvinyl silane (polyvinylsilane), methacryloxy silane (methacryloxysilane) and chloro silane (chlorosilane),, one or more the compound among the hallgen-carbonsilane, siloxanes (siloxane).
Said silane is selected from methyltrimethoxy silane (methyltrimethoxysilane); Ethyl trimethoxy silane (ethyltrimethoxysilane); Propyl trimethoxy silicane (propyltrimethoxysilane); Normal-butyl Trimethoxy silane (n-butyltrimethoxysilane); Isobutyl-Trimethoxy silane (isobutyltri methoxysilane); Phenyltrimethoxysila,e (pentyltrimethoxysilane); Hexyl Trimethoxy silane (hexyltrimethoxysilane); Octyl group Trimethoxy silane (octyltrimethoxysilane); 7-octene-1-Ji Trimethoxy silane (7-oct-1-enyltrimethoxysilane); P-methylphenyl Trimethoxy silane (p-(methyl) phenyltrimethoxysilane); 3-cyclopentano-diallyl trimethoxy alkyl (3-cyclopent adienylpropyltrimethoxysilane); Vinyltrimethoxy silane (vinyltrimethoxysilane); Allyltrimethoxysilanis (allyltrimethoxysilane); 3-methoxymethoxy propyl silane (methox ypropyltrimethoxysilane); Union carbide A-162 (methyltriethoxysilane); Ethyl triethoxysilane (ethyltriethoxysilane); Propyl-triethoxysilicane (propyltriethoxysilane); Ne-butyltriethoxysilaneand (n-butyltriethoxysilane); Isobutyl-triethoxyl silane (isobutyltriethox ysilane); Isobutyl-Trimethoxy silane (isobutyltrimethoxysilane); Phenyl triethoxysilane (p entyltriethoxysilane); Phenyltrimethoxysila,e (pentyltrimethoxysilane); Hexyl triethoxyl silane (hexyltriethoxysilane); Hexyl Trimethoxy silane (hexyltrimethoxysilane); Octyltri-ethoxysilane (octyltriethoxysilane); Octyl group Trimethoxy silane (octyltrimethoxysila ne); 7-octene-1-ethyl triethoxy silicane alkane (7-oct-1-enyltriethoxysilane); 7-octene-1-Ji Trimethoxy silane (7-oct-1-enyltrimethoxysilane); P-methylphenyl triethoxyl silane (p-(methyl) phenyltriethoxysilane); P-methylphenyl Trimethoxy silane (p-(methyl) phenyltrimethoxysil ane); 3-cyclopentano-diallyl triethoxy alkyl (3-cyclopentadienylpropyltriethoxysilane); 3-cyclopentano-diallyl trimethoxy alkyl (3-cyclopentadienylpropyltrimethoxysilane); Vinyltriethoxysilane (vinyltriethoxysilane); Vinyltrimethoxy silane (vinyltrimethox ysilane); Allyltriethoxysilane (allyltriethoxysilane); Allyltrimethoxysilanis (allyltrimethoxysilane); 3-oxyethyl group methoxy base propyl silane (methoxypropyltriethoxysilane); 3 methoxymethoxy propyl silanes (methoxypropyltrimethoxysilane), methyl three isopropoxy silane (methyltriisopropoxysilane), ethyl three isopropoxy silane (ethyltriisopropoxysilane), propyl group three isopropoxy silane (propyltriisopropoxysilane), vinyl silane triisopropoxide (viny ltriisopropoxysilane), three tert.-butoxy vinyl silanes (vinyltris-t-butoxysilane), trifluoro propane Trimethoxy silane (3; 3; 3-trifluoropropyltrimethoxysilane), ten trifluoro octyltri-ethoxysilane (tridecafluoroetyltriethoxysilane), vinyl three (2-methoxy ethoxy) silane (vinyltris (2-methoxyethoxy) silane), vinyl trichloro silane (vinyltrichlorosilane), vinyl-dimethyl oxygen ylmethyl silane (vinyldimethoxymethylsilane), vinyl diethoxy methyl-monosilane (vinyldiethoxy methylsilane), 3-allyl oxygen propyl trimethoxy silicon (3-acryloxypropyltrimethoxysilane), methacryloxypropyl methyldiethoxysilane (3methacryloxypropylmethyldiethoxysilan e), 3-methacryloxypropyl methyl dimethoxysilane (3methacryloxypropylmethyldimet hoxysilane), 3-(methacryloxypropyl) propyl trimethoxy silicane (3-methacryloxypropyltrimet hoxysilane), 3-(methacryloxypropyl) propyl-triethoxysilicane (3-methacryloxypropyltrietho xysilane), 3-Racemic glycidol propyl trimethoxy silicane (3-glycidoxypropyltrimethoxysilane), β-(3; The 4-epoxy cyclohexane) ethyl trimethoxy silane (2-(3,4epoxycyclohexyl) ethyltrimethoxy silane), N-(2-amine ethyl)-3-amine propyl group trimethoxy silane (N-2-(aminoethyl)-3-aminopropyltri methoxysilane), N-(2-amine ethyl)-3-amine propyl group methyl dimethoxy oxosilane (N-2-(aminoethyl)-3-a minopropylmethyldimethoxysilane), 3-amine propyl group methyl trimethoxy oxosilane (3-aminopropyltri methoxysilane), 3-amine propyl group methyl three ethoxy silane (3-aminopropyltriethoxysilane), γ-An Bingjisanyiyangjiguiwan (3-aminopropyl) triethoxysilane), γ-aminopropyl dimethoxy-methyl silane (3-aminopropyl) dimethoxymethylsilane), γ-aminopropyl dimethoxy-ethyl silane (3-aminopr opyl) diethoxymethylsilane), the N-(2-aminoethyl-3-aminopropyl-3-methoxy silane (mixture of one or more in N-(2-amino ethyl)-3-aminopropyltrimethoxysilane), N-methyl aminopropyl trimethoxysilane (N-methyla minopropyltrimethoxysilane), N-methyl aminopropyl triethoxysilane (N-methylaminopropy ltriethoxysilane), 3-urea propyl-triethoxysilicane (3-ureidopropyltriethoxysilane), 3-mercaptopropyl trimethoxysilane (3-Mercaptopropyltriethoxysilane), 3-(4-phenyl ester) propyl trimethoxy silicane (3-(4-cyanatophenyl) propyltrimethoxysilane), polyvinyl triethyl silicane (pol yvinyl trimethyl silane) N-phenyl-3-amine propyl group methyl trimethoxy oxygen silicon (N-phenyl-3-aminopro pyltrimethoxysilane), 3-mercaptopropyl trimethoxysilane (3-mercaptopropyltrimethoxysilane), 3-r-chloropropyl trimethoxyl silane (3-chloropropyltrimethoxysilane), tetramethoxy-silicane (tet ramethoxysilane), tetraethoxysilane (tetraethoxysilane), tetrapropoxysilane (tetraprop oxysilane), four butoxy silanes (tetra-n-butoxysilane), diethoxymethyl [(3-Oxyranyle methoxy) propyl group] silane (gamma-glycidoxypropylmethyldimethoxysilane), 3-glycidyl ether oxygen base propyl group pentamethyl disilane (gamma-glycidoxypropylpylpentamethyldisilane), 3-glycidyl ether oxygen base propyl group methyldiethoxysilane (gamma-glycidoxypropylmethyldiethoxys ilane), 3-glycidyl ether oxygen base propyl-dimethyl diethoxy silane (gamma-glycidoxypropyldi methylethoxysilane) or the 3-glycidyl ether oxygen base propyl group-two trimethylsiloxy group methyl-monosilanes ((gam ma-glycidoxypropyl)-bis (trimethylsiloxy) methylsilane).
After sample 1～6 used above-mentioned silane treatment respectively, the thermotolerance of test sample 1～6, wet fastness and pulling force poundage.
Wherein, stable on heating detection method and standard are: roasting 30mins under 200 ℃ of bakings, and the difference whether oxidation and degree of oxidation are arranged on the internal layer copper surface is with following coded representation: 1: the aterrimus oxidation is arranged; 2: the brown oxidation is arranged; 3: some oxidations, 4: slight oxidation, 5: not oxidation fully.
The detection method of wet fastness is to do wicking (288 ℃, 10sec, 3 times) plate bursting test behind 80 ℃, 95%RH, 24Hrs
The detection method of pulling force poundage does; According to IPC tensile test flow process.
Detect the gained experimental data like table a, b, c, d, e, f is shown in g and the h.
Thermotolerance, wet fastness and the pulling force poundage of sample 1-6 after table a handles with the epoxy radicals silicone hydride methyltrimethoxy silane
B) thermotolerance, wet fastness and the pulling force poundage of the sample 1-6 after handling with the vinyl silanes vinyltrimethoxy silane
C) thermotolerance, wet fastness and the pulling force poundage of the sample 1-6 after handling with propenyl silane 3-(methacryloxypropyl) propyl trimethoxy silicane
D) thermotolerance, wet fastness and the pulling force poundage of the sample 1-6 after handling with aminosilane 3-amine propyl group methyl trimethoxy oxosilane
E) thermotolerance, wet fastness and the pulling force poundage of the sample 1-6 after handling with hydrosulphonyl silane 3-mercaptopropyltriethoxysilane
F) thermotolerance, wet fastness and the pulling force poundage of the sample 1-6 after handling with silicon ester silane 3-(4-phenyl ester) propyl trimethoxy silicane
G) thermotolerance, wet fastness and the pulling force poundage of the sample 1-6 after handling with urea groups silane 3-(4-phenyl ester) propyl trimethoxy silicane
H) thermotolerance, wet fastness and the pulling force poundage of the sample 1-6 after handling with isocyanato silane 3-NCO propyl-triethoxysilicane
I) thermotolerance, wet fastness and the pulling force poundage of the sample 1-6 after handling with polyvinyl silane Vilaterm trimethyl silane
Except that above-mentioned silane, be applicable in the printed circuit board base board according to the invention, increase the imidazoles silane compound or the imidazoles silane compound verivate in addition of the method for bonding force between electrical conductor and the non-conductive polymer dielectric layer.Said imidazoles silane compound is that imidazoles and silane react resulting mixtures or imidazoles and silane derivative through 80～200 ℃ of resulting mixtures of reaction through 80～200 ℃, and wherein, the chemical formula of said imidazoles is:
(1)?
The chemical formula of said silane or silane derivative is:
(2)
Reaction product is:
(3)?
(4)?
(5)
Mixture;
Wherein, wherein, R
1, R
2And R
3Represent the alkyl substituent of hydrogen base, thiazolinyl, phenolic group, phenyl or 1～20 carbon, R
2, R
3Can form aromatic nucleus, R
4, R
5Represent the alkyl substituent of 1～5 carbon, and n represents 1～3.
Said silane is the mixture of said compound (3), (4) and (5) or wherein a kind of.
Said imidazoles is selected from imidazoles (imidazole), aminooimidazole (aminoimidazole), diamino-imidazoles (diaminoimidazole), monomethyl imidazoles (monomethylimidazole), 2-alkyl imidazole (2-alkylimidazole), 2; The 4-dialkylimidazolium (2,4-dialkylimidazole), 4-vinyl imidazole (4-vinylimidazole), glyoxal ethyline (2-methylimidazole), 2-ethyl imidazol(e) (2-ethylimidazole), the 2-undecyl imidazole (mixture of one or more in 2-undecylimidazole0,2-heptadecyl imidazoles (2-heptadecylimidazole), benzoglyoxaline (benzimidazole), benzotriazole (benzotriazole), pyridine (pridine), the 2-ethyl-4-methylimidazole (2-ethyl-4-methylimidazole).
Silane in the said imidazoles silane compound is selected from 3-Racemic glycidol propyl trimethoxy silicane (3-glycidoxypropyltrimethoxysilane); 3 Racemic glycidol propyl group dialkoxy silicanes (3-glycidoxypropyldialkoxysilane); 3-Racemic glycidol propyl group oxyethyl group dimethylsilane (3-glycidoxypropylethoxydimethylsilane); The mixture of one or more in the 3-Racemic glycidol propyl group alkoxyl group dialkyl silane (3-glycidoxypropylalkoxydialkylsilane).
Behind the mixture and following compound of said (3), (4) and (5), also having increases combining with joint efforts between said electrical conductor and the said non-conductive polymer dielectric layer
Wherein, R
6, R
7, R
8Represent the alkyl substituent of hydrogen base, thiazolinyl, phenolic group, phenyl or 1～20 carbon, R
7, R
8Can form aromatic nucleus, R
9, R
10Possibly be the alkyl substituent of 1～5 carbon, and o represents 1～10, p represents 1～3.
What obtain after the reaction is the mixture of (3), (4) and (5); Can use this mixture or handle matrix copper coin in the printed substrate pressure programming according to the invention as coating through special purifying arbitrary single composition later; Detect thermotolerance, wet fastness and the bonding force of product with above-mentioned identical method, the gained result is shown in Table I and J.
I) with thermotolerance, wet fastness and the pulling force poundage of the sample 1-6 after imidazoles silane imidazoles-3-glycidyl ether oxygen base propyl trimethoxy silicane mixture process
J) with the imidazoles silane compound be thermotolerance, wet fastness and the pulling force poundage of the sample 1-6 after product (4) is handled
Said imidazoles-silane-organic acid salt mixture is the reaction product of imidazoles-silane compound and organic acid salt; Said imidazoles-silane-organic acid salt mixture verivate is the reaction product of imidazoles-silane derivative and organic acid salt,
Wherein, the chemical formula of said imidazoles is:
(6)?
The chemical formula of said silane is:
(7)?
The chemical formula of said imidazoles-silane compound or imidazoles-silane compound verivate is:
(8)?
The chemical formula of said imidazoles-silane-organic acid mixture or said imidazoles-silane-organic acid mixture verivate is:
(9)?
Wherein, R
1, R
2And R
3Represent the alkyl substituent of hydrogen base, thiazolinyl or 1～20 carbon, R
2, R
3Also can represent fragrant cyclic group, R
4, R
5Represent the alkyl substituent of 1～5 carbon, m represents 1～10, and n represents 1～3.
Said imidazoles is selected from imidazoles (imidazole), 2-alkyl imidazole (2-alkylimidazole), 2; The 4-dialkylimidazolium (2,4-dialkylimidazole), 4-vinyl imidazole (4-vinylimidazole),, a kind of or its mixture in the benzoglyoxaline (benzimidazole), benzotriazole (benzotriazole), pyridine (pridine), glyoxal ethyline (2-methylimidazole), 2-ethyl imidazol(e) (2-ethylimidazole), 2-undecyl imidazole (2-undecylimidazole), 2-heptadecyl imidazoles (2-heptadecylimidazole), 2-ethyl-4-methylimidazole (2-ethyl-4-methylimidazole).
Said silane is selected from 3-Racemic glycidol propyl trialkoxy silane (3-glycidoxypropyltrialkoxysila nes); 3-Racemic glycidol propyl group dialkoxy alkyl silane (3-glycidoxypropyldialkoxyalkylsilane s); 3-Racemic glycidol propyl group alkoxyl group dialkyl silane (3-glycidoxypropylalkoxydialkylsilanes); 3-Racemic glycidol propyl trimethoxy silicane (3-glycidoxypropyltrimethoxysilane); 3-Racemic glycidol propyl-triethoxysilicane (3-glycidoxypropyltriethoxysilane); 3-Racemic glycidol propyl group dialkoxy alkyl silane (3-glycidoxypropyldialkoxyalkylsilane); 3-Racemic glycidol propyl group dimethyl ethoxy methyl-monosilane (3-glycidoxypropyldimethoxymethylsilane); The mixture of one or more in 3-Racemic glycidol propyl group alkoxyalkyl silane (3-glycidoxypropylalkoxydialkylsilane) or the 3-Racemic glycidol propyl group oxyethyl group dimethylsilane (3-glycidoxypropylethoxydimethylsilane).
Organic acid described in said imidazoles-silane-organic acid mixture or imidazoles-silane-organic acid mixture verivate is organic monocarboxylic acid, saturated fatty monocarboxylic acid, unsaturated fatty acids monocarboxylic acid or fragrance bunch monocarboxylic acid and analogue thereof.
Said organic acid is selected from a kind of or its mixture in vinylformic acid, isopropylformic acid, methylacrylic acid, sad, formic acid, oxoethanoic acid, Ba Dousuan, acetate, propionic acid, phenylformic acid, Whitfield's ointment, hexahydrobenzoic acid, o-toluic acid, toluylic acid or the p-tert-butyl benzoic acid.
Said organic acid is a methylacrylic acid.
Said silane is that organic annular silane (organosilicic silane) or organic ring silicon derivative and alkylene silane (olefin-based silane) stir the 2hrs afterreaction 40～90 ℃ intensification and produces, and reaction formula is following:
Wherein, R
1Representative is the alkyl substituent of hydroxyl or 1～5 carbon; R
2Represent the alkyl substituent of hydrogen base or 1～10 carbon, and this alkyl aerobic optionally; X has two hydroxyls at least in (1) and (2), and n is 2 at least, and m is 1 at least; R
3Represent the alkyl substituent of 1～5 carbon, R
4Representative is hydroxyl-or the alkyl substituent of 1～5 carbon, R
5Represent the alkyl substituent of hydrogen base or 1～10 carbon, and this alkyl aerobic optionally, L represents 2～3.
Said organic annular silane is selected from vinyl silanes (vinyl-based silanes), propenyl silane (acryli c-based silanes) and methacrylic base silane (methacrylic-based silanes); Wherein, vinyl silanes comprises vinyltrimethoxy silane (vinyltrimethoxysilane), vinyltriethoxysilane (v inyltriethoxysilane), vinyl trichlorine base silane (vinyltrichlorosilane), vinyl trialkyl oxysilane (vinyltrialkoxysilanes), vinyl dialkoxy alkyl silane (vinyldialkoxyalkylsilan es), vinyl three (dimethoxy oxyethyl group) silane (vinyltris (beta-methoxyethoxy) silane), vinyl-dimethyl oxygen ylmethyl silane (vinyldimethoxymethylsilane), vinyl diethoxymethyl silane (vinyldiethoxymethylsilane); Propenyl silane (acrylic-based silanes) comprises 3-allyl oxygen propyl trimethoxy silicon (gamma-acryloxypropyltrimethoxysilane); Methylpropenyl silane comprises (methacrylic-based silanes); Methacryloxypropyl trimethoxy silane (g amma-methacryloxypropyltrimethoxysilane); 3-methacryloxypropyl methyl dimethoxysilane (gamma-methacryloxypropylmethyldimethoxysilane); A kind of or its mixture in 3-(methacryloxypropyl) propyl group methyldiethoxysilane (gamma-methacryloxypropylmethyldiethoxysilane) or the 3-methacryloxypropyl triethoxyl silane (gamma-methacryloxypropyltriethoxysilane).
The mass ratio of organic annular silane and silane described in the mixture of said organic annular silane and silane is 99: 1～1: 99.
Product imidazoles-3-glycidyl ether oxygen base propyl trimethoxy silicane monocarboxylate verivate so that above-mentioned reaction obtains is handled matrix copper coin in the printed substrate pressure programming according to the invention as coating; Detect thermotolerance, wet fastness and the bonding force of product with above-mentioned identical method, the gained result is as shown in table 1.
Table 1 is handled thermotolerance, wet fastness and pulling force poundage behind the sample 1-6 with imidazoles-silane-organic acid salt mixture imidazoles-3-3-glycidyl ether oxygen base propyl trimethoxy silicane monocarboxylate verivate
In the printed circuit board base board; Increase the method for bonding force between electrical conductor and the non-conductive polymer dielectric layer; Comprise: on metal sheet surface, do earlier coarse processing; After said non-conductive polymer dielectric material plate is immersed in volumetric concentration is the several seconds or several minutes in 0.01%～100% the solution of silane, or be 0.01%～100% solution of silane directly, thereby increase one deck silylation layer on its surface in said non-conductive polymer dielectric material plate surface sprinkling volumetric concentration.
A kind of printed circuit board base board comprises electrical conductor and the non-conductive polymer dielectric layer that presses together with this electrical conductor, also has one deck silylation layer between said electrical conductor and the said non-conductive polymer dielectric layer.
Above content is to combine concrete embodiment to the further explain that the present invention did, and can not assert that practical implementation of the present invention is confined to these explanations.For the those of ordinary skill of technical field under the present invention, under the prerequisite that does not break away from the present invention's design, its framework form can be flexible and changeable, can the subseries product.Just make some simple deduction or replace, all should be regarded as belonging to the scope of patent protection that the present invention is confirmed by claims of being submitted to.
Claims (5)
1. in the printed circuit board base board; Increase the method for bonding force between electrical conductor and the non-conductive polymer dielectric layer; Comprise: earlier on the electrical conductor surface, do coarse processing, it is characterized in that, after the coarse processing said electrical conductor being immersed in volumetric concentration is that solution of silane several seconds of 0.01%～100% was to several minutes; Or be 0.01%～100% solution of silane directly, thereby increase one deck silylation layer on its surface in said electrical conductor surface sprinkling volumetric concentration;
The essential substance of said silylation layer is imidazoles-silane compound, imidazoles-silane compound verivate, imidazoles-silane-organic acid salt mixture, imidazoles-silane-organic acid salt mixture verivate;
Said imidazoles-silane compound is that imidazoles and silane react resulting mixtures or imidazoles and silane derivative through 80～200 ℃ of resulting mixtures of reaction through 80～200 ℃, and wherein, the chemical formula of said imidazoles is:
The chemical formula of said silane or silane derivative is:
Reaction product is:
Mixture;
Wherein, wherein, R
1, R
2And R
3Represent the alkyl substituent of hydrogen base, thiazolinyl, phenolic group, phenyl or 1～20 carbon, R
2, R
3Can form aromatic nucleus, R
4, R
5Represent the alkyl substituent of 1～5 carbon, and n represents 1～3.
2. the method for bonding force is characterized in that between increase electrical conductor as claimed in claim 1 and the non-conductive polymer dielectric layer, and said silane is the mixture of said compound (3), (4) and (5) or wherein a kind of.
3. the method for bonding force between increase electrical conductor as claimed in claim 1 and the non-conductive polymer dielectric layer; It is characterized in that; Said imidazoles is selected from imidazoles (imidazole), aminooimidazole (aminoimidazole), diamino-imidazoles (diaminoimidazole), monomethyl imidazoles (monomethylimidazole), 2-alkyl imidazole (2-alkylimidazole), 2; The 4-dialkylimidazolium (2,4-dialkylimidazole), 4-vinyl imidazole (4-vinylimidazole), glyoxal ethyline (2-methylimidazole), 2-ethyl imidazol(e) (2-ethylimidazole), the 2-undecyl imidazole (mixture of 2-undecylimidazole0,2-heptadecyl imidazoles (2-heptadecylimidazole), benzoglyoxaline (benzimidazole), benzotriazole (benzotriazole), pyridine (pridine), 2-ethyl-4-methylimidazole (2-ethyl-4-methylimidazole) or several kinds.
4. the method for bonding force between increase electrical conductor as claimed in claim 1 and the non-conductive polymer dielectric layer; It is characterized in that the silane in the said imidazoles silane compound is selected from one or more the mixture in 3-Racemic glycidol propyl trimethoxy silicane (3-glycidoxypropyltrimethoxysilane), 3 Racemic glycidol propyl group dialkoxy silicanes (3-glycidoxypropyldialkoxysilane), 3-Racemic glycidol propyl group oxyethyl group dimethylsilane (3-glycidoxypropylethoxydimethylsilane), the 3-Racemic glycidol propyl group alkoxyl group dialkyl silane (3-glycidoxypropylalkoxydialkylsilane).
5. the method for bonding force is characterized in that between increase electrical conductor as claimed in claim 1 and the non-conductive polymer dielectric layer, the mixture of said (3), (4) and (5) also with following compound,
Wherein, R
6, R
7, R
8Represent the alkyl substituent of hydrogen base, thiazolinyl, phenolic group, phenyl or 1～20 carbon, R
7, R
8Can form aromatic nucleus, R
9, R
10, R
11Be the alkyl substituent of 1～5 carbon, and o represents 1～10, p represents 1～3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100459244A CN102618164A (en) | 2010-08-03 | 2010-08-03 | Method for increasing bonding force between conductive body and non-conductive macromolecule dielectric layer in printed circuit board substrate |
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| CN 201010244089 Division CN101917826B (en) | 2010-08-03 | 2010-08-03 | Method for increasing bonding force between conductor and non-conductive polymer dielectric layer in substrate of printed circuit board |
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| KR20150128725A (en) * | 2013-03-15 | 2015-11-18 | 다우 코닝 코포레이션 | 2-aminoimidazole-functional silicone compositions and methods of making the same |
| CN106626580A (en) * | 2015-10-28 | 2017-05-10 | 财团法人工业技术研究院 | Composite laminated plate |
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| US6506314B1 (en) * | 2000-07-27 | 2003-01-14 | Atotech Deutschland Gmbh | Adhesion of polymeric materials to metal surfaces |
| CN1599742A (en) * | 2001-12-06 | 2005-03-23 | 株式会社日矿材料 | Organic carboxylic acid salt composition, process for preparation thereof and additives for epoxy resins |
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| KR20150128725A (en) * | 2013-03-15 | 2015-11-18 | 다우 코닝 코포레이션 | 2-aminoimidazole-functional silicone compositions and methods of making the same |
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| CN106626580A (en) * | 2015-10-28 | 2017-05-10 | 财团法人工业技术研究院 | Composite laminated plate |
| US10751975B2 (en) | 2015-10-28 | 2020-08-25 | Industrial Technology Research Institute | Composite laminate |
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