CN100509951C - Thermoset resin composition and multi-layer printed circuit board using the resin composition - Google Patents
Thermoset resin composition and multi-layer printed circuit board using the resin composition Download PDFInfo
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- CN100509951C CN100509951C CNB2005100674965A CN200510067496A CN100509951C CN 100509951 C CN100509951 C CN 100509951C CN B2005100674965 A CNB2005100674965 A CN B2005100674965A CN 200510067496 A CN200510067496 A CN 200510067496A CN 100509951 C CN100509951 C CN 100509951C
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61G—TRANSPORT, PERSONAL CONVEYANCES, OR ACCOMMODATION SPECIALLY ADAPTED FOR PATIENTS OR DISABLED PERSONS; OPERATING TABLES OR CHAIRS; CHAIRS FOR DENTISTRY; FUNERAL DEVICES
- A61G17/00—Coffins; Funeral wrappings; Funeral urns
- A61G17/08—Urns
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- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47G—HOUSEHOLD OR TABLE EQUIPMENT
- A47G33/00—Religious or ritual equipment in dwelling or for general use
- A47G33/02—Altars; Religious shrines; Fonts for holy water; Crucifixes
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61G—TRANSPORT, PERSONAL CONVEYANCES, OR ACCOMMODATION SPECIALLY ADAPTED FOR PATIENTS OR DISABLED PERSONS; OPERATING TABLES OR CHAIRS; CHAIRS FOR DENTISTRY; FUNERAL DEVICES
- A61G17/00—Coffins; Funeral wrappings; Funeral urns
- A61G17/007—Coffins; Funeral wrappings; Funeral urns characterised by the construction material used, e.g. biodegradable material; Use of several materials
Abstract
The present invention provides a thermosetting resin composition which has smaller solidification shrinking and excellent crack resistance and insulation reliability and the like properties, further the invention provides a thermosetting resin composition which has excellent sealing property between the condensate filled in the hole part and the cover coating layer. The thermosetting resin composition provided by the invention is characterized in that the composition comprises the following components: (A) epoxy resin, (B) polyfunctional phenolic compound, (C) solidifying catalyst, (D) filling agent and (E) the thermosetting resin composition of the oxetane compound; the invention also provides a thermosetting resin composition containing the compound which is showed by the general formula (I) and includes the oxazine ring group.
Description
Technical field
The present invention relates to be used for the compositions of thermosetting resin of manufacturing of multilayer printed circuit board and the multilayer printed circuit board that uses said composition.In more detail, relate to permanent filling perforation such as via hole as printed circuit board (PCB)s such as multilager base plate and two sides substrates, through hole with the liquid thermosetting resin combination useful, that less, the anti-crackle of cure shrinkage is good of composition etc. and the multilayer printed circuit board that uses said composition.
Background technology
In recent years, printed circuit board (PCB) is just constantly development aspect the downsizing of the graph thinning of pattern and erection space, and then, for miniaturization and high performance corresponding to the machine that is provided with printed circuit board (PCB), wish printed circuit board (PCB) compactization further, therefore, printed circuit board (PCB) is at the resin insulating barrier of formation up and down of core material, and after forming necessary circuit, further form resin insulating barrier, lamination (build up) method direction in this mode that forms conductor circuit develops, and installation component is towards BGA (ball grid array) in addition, the direction of LGA area array types such as (grid arrays) develops.Recently,, then turn on hole portion and recess, to form liner and installation parts, on hole portion and recess, form the method for path for densification further.Under this situation, wish that exploitation is a kind of not only when filling orifice portion and recess, fillibility, abrasive property and cured article characteristic good, and the permanent filling perforation composition good with the adaptation of the lid coating that on hole portion and recess, forms.
In addition, in this manual, " hole portion " is meant, the term of general names such as via hole that will form in the manufacturing processed of printed circuit board (PCB) (via hole) and through hole.
Usually, as the permanent filling perforation printing ink of printed circuit board (PCB) since its cured article machinery, electricity and chemical aspect character good, therefore connectivity is also good, uses the thermosetting epoxy resin composition widely.In addition, in this composition epoxy resin,, contain a large amount of mineral fillers in order to reduce the thermal expansion of cured article.
As this composition, for example proposed, contain the solvent-free resin extender (opening flat 10-No. 75027 communiques (claim)) of bisphenol-type epoxy resin, imidazole curing agent with reference to the spy.This composition connectivity is good, the contraction that does not also exist the volatilization owing to organic solvent to cause, but because the catalyzer that imidazoles causes solidifies, the strain in the cured article is bigger, can't say so has enough insulating reliabilities and stable on heating material, and hope can further improve.
Summary of the invention
The present invention finishes in view of status, its basic purpose is: provide a kind of solvent-free or contain micro-organic solvent and liquable, cure shrinkage is less, the compositions of thermosetting resin of anti-crackle and characteristic goods such as insulating reliability, thermotolerance, and a kind of cured article of hole portion and good compositions of thermosetting resin of adaptation between the lid coating of being filled in further also is provided.
Again further, by with it as the weighting material that on substrate, forms conductor circuit and have the printed circuit board (PCB) of the hole portion of having filled weighting material by interlayer resin insulating layers, can also provide a kind of the existence to cause printed circuit board (PCB)s characteristic good, high reliability such as splitting, insulating reliability and thermotolerance owing to thermal stresses.
In order to realize aforementioned purpose, as general planning of the present invention, a kind of compositions of thermosetting resin is provided, it is characterized in that, contain: (A) Resins, epoxy, (B) multifunctional phenolic compound, (C) curing catalysts, (D) filler and (E) oxetane compound.And then the present invention also provides a kind of compositions of thermosetting resin, it is characterized in that, further contains the compound with the cyclic group of De Han oxazine shown in the following general formula (I) in above-mentioned composition,
In the formula, R
1Expression methyl, cyclohexyl and can substituted aryl.
In addition, in preferred embodiments, the oxetane compound (E) that is used for above-mentioned compositions of thermosetting resin is at normal temperatures for liquid, and its use level preferably is 10 quality % or following in whole composition.
Further, as other scheme, a kind of printed circuit board (PCB) also is provided, it is characterized in that: this printed circuit board (PCB) forms conductor circuit by interlayer resin insulating layers on substrate, and have the hole portion of having filled weighting material, the weighting material of filling above-mentioned hole portion is made of the cured article of above-mentioned compositions of thermosetting resin.
Compositions of thermosetting resin of the present invention is by using oxetane compound, and the coefficient of elasticity of its cured article reduces, and anti-crackle is good.And then, as preferred scheme,, can reduce or the organic solvent of decontamination operating environment by using liquid oxetane compound.Further,, can stop the situations such as splitting that cause owing to volatile compound residual after the multilayer printed circuit board manufacturing, the multilayer printed circuit board of high reliability can be provided by reducing or eliminate the content of this volatile compound.
Compositions of thermosetting resin of the present invention is characterised in that: containing (A) Resins, epoxy, (B) multifunctional phenolic compound, (C) curing catalysts and (D) in the thermosetting epoxy resin composition of filler, be combined with (E) oxetane compound.
Just, compositions of thermosetting resin of the present invention is by cooperating aforementioned oxetane compound (E), find to compare with the composition that constitutes by aforementioned epoxy resins (A), aforementioned multifunctional phenolic compound (B) and aforementioned curing catalysts (C), its cure shrinkage is less, and coefficient of elasticity reduces, and solidifies strain and obtains relaxing.And then by using liquid trimethylene oxide as aforementioned oxetane compound (E), electrical insulating property etc. can not reduce, can be under the situation of solvent-free or micro-organic solvent liquid stateization.
Find in addition, contain the compound of the cyclic group of De Han oxazine shown in the general formula (I) as described above, can improve cured article of in the portion of hole, filling and the adaptation of covering between the coating by in above-mentioned composition, further cooperating.
And then, also find, form conductor circuit and have the weighting material of the printed circuit board (PCB) of the hole portion of having filled filler by interlayer resin insulating layers by this compositions of thermosetting resin being used on substrate, can obtain can not producing the high reliability printed circuit board (PCB) of the characteristic goods such as situations such as splitting, insulating reliability and thermotolerance that cause owing to thermal stresses.
Below, each moiety of compositions of thermosetting resin of the present invention is described in detail.
At first, as aforementioned epoxy resins (A),, can use known habitual material so long as in a part, have 2 or above epoxy group(ing) just.Bisphenol A type epoxy resin for example, bisphenol-s epoxy resin, bisphenol f type epoxy resin, phenol phenolic varnish (phenol novolac) type Resins, epoxy, cresols phenolic varnish (cresol novolac) type Resins, epoxy, alicyclic epoxy resin, the diglycidylether of propylene glycol or polypropylene glycol, the glycerine polyglycidyl ether, the TriMethylolPropane(TMP) polyglycidyl ether, phenyl-1,3-diglycidyl ether, biphenyl-4,4 '-diglycidyl ether, 1,6-cylohexanediol diglycidyl ether, the diglycidylether of ethylene glycol or polyoxyethylene glycol, the sorbyl alcohol polyglycidyl ether, the anhydro sorbitol polyglycidyl ether, three (2,3-epoxypropyl) isocyanuric acid ester, has compound of 2 or above epoxy group(ing) etc. in a part such as triglycidyl group three (2-hydroxyethyl) isocyanuric acid ester.
Wherein, because easily alligatoring, preferred especially two functional Resins, epoxy, for example diglycidylether of bisphenol A type epoxy resin, bisphenol f type epoxy resin, hydrogenation bisphenol A type epoxy resin, hydrogenation bisphenol f type epoxy resin, propylene glycol or polypropylene glycol etc.It can cooperate the requirement that improves coating characteristic, uses separately or is used in combination 2 kinds or multiple.
Also have,,, just can use known habitual material so long as in a part, have 2 or above phenol hydroxyl as aforementioned multifunctional phenolic compound (B).Specifically can list, the resol of phenol phenolic varnish type resin, cresols phenolic varnish type resin, dihydroxyphenyl propane, allylation dihydroxyphenyl propane, Bisphenol F, dihydroxyphenyl propane, vinylphenol copolymer resins etc., particularly phenol resol is because its reactivity is higher, thermotolerance lifting effect is also higher, therefore preferably.
This multifunctional phenolic compound (B) in the presence of suitable curing catalysts (C), with aforementioned epoxy resins (A) addition reaction, so again with aforesaid oxetane compound (E) addition reaction.Thereby, the use level of multifunctional phenolic compound (B) is, total yield number with respect to the equivalents of the oxetanyl of the equivalents of the epoxy group(ing) of aforementioned epoxy resins (A) and aftermentioned oxetane compound (E) is 1:0.2～1:1.2, preferred 1:0.3～1:1.0.When the use level of aforementioned multifunctional phenolic compound (B) is counted 0.2 times of less than with respect to aforementioned total yield, unreacted Resins, epoxy (A) and oxetane compound (E) are residual, the oxetane compound (E) that particularly is difficult to catalytic curing is residual easily, can not get enough cured article characteristics, therefore not preferred.On the other hand, when the use level of aforementioned multifunctional phenolic compound surpassed 1.2 times, excessive multifunctional phenolic compound (B) remained in the cured article, and the cured article characteristic is reduced, and is therefore not preferred.
As aforementioned curing catalysts (C), it is the compound that curing catalysts constituted as aforementioned epoxy resins (A) and aforementioned multifunctional phenolic compound (B) and aftermentioned oxetane compound (E) and aforementioned multifunctional phenolic compound (B), can exemplify out in tertiary amine, tertiary ammonium salt, quaternary salt, tertiary phosphine, crown ether inner complex He the Phosphonium etc., can at random select among them, their can be used separately or be used in combination 2 kinds or multiple.
Wherein, as preferred catalyzer, can enumerate commodity 2E4MZ by name, C11Z, C17Z, imidazoles such as 2PZ, commodity are called 2MZ-A, the azines of imidazoles such as 2E4MZ-A, commodity are called 2MZ-OK, the isocyanurate of imidazoles such as 2PZ-OK, commodity are called 2PHZ, imidazoles methylol bodies such as 2P4MHZ (any one in the aforementioned trade(brand)name all is that four countries change into industry (strain) manufacturing), Dyhard RU 100 and derivative thereof, trimeric cyanamide and derivative thereof, Diaminomaleonitrile and derivative thereof, diethylenetriamine, Triethylenetetramine (TETA), tetren, two (hexylidene) triamine, trolamine, diaminodiphenyl-methane, amines such as organic acid dihydrazide, 1,8-diazabicyclo [5,4,0] (commodity are called DBU to undecylene-7, サ Application ア プ ロ (strain) makes), 3,9-two (3-aminopropyl)-2,4,8,10-four oxygen volutions [5,5] ten-carbene (commodity are called ATU, and aginomoto (strain) is made), perhaps triphenylphosphine, tricyclohexyl phosphine, tributylphosphine, organic phosphine compounds such as methyldiphenyl base phosphine etc.
In these curing catalysts, as known, because Dyhard RU 100, trimeric cyanamide, acetylguanamine, benzoguanamine, 3,9-two [2-(3,5-diamino-2,4,6-triazinyl) ethyl]-2,4,8,10-four oxygen volutions [5,5] guanamines such as ten-carbene and derivative thereof and their organic acid salt and epoxy adduct etc. have adaptation and the rust-preventing characteristic with copper, not only play effect, can also prevent the variable color of the copper of printed circuit board (PCB), therefore preferred the use as curing agent for epoxy resin.
The use level of these curing catalysts (C) is that the ratio of common amount gets final product, for example with aforementioned epoxy resins (A) as 100 quality %, then suitable use level is 0.1～10 quality %.
Used aforementioned filler (D) is used to relax because stress that cure shrinkage produces and adjustment coefficient of linear expansion can use any one to be used for the known habitual non-conductive material of common resin combination among the present invention.Can exemplify out: silica, settleability barium sulfate, talcum, lime carbonate, silicon nitride, aluminium nitride etc.Cooperate the requirement that improves coating characteristic, can or be used in combination 2 kinds or multiple their independent uses.In these mineral fillers, what agent of low hygroscopicity, low volumetric expansion were good especially is silica.No matter silica is that fused, crystalline or its mixture all are fine, from the angle of high fillibility, and preferred globular fused silica.
In addition, preferred 3～25 μ m of the median size of these fillers (D).If median size less than 3 μ m, then the effect of the coefficient of linear expansion of inhibition reduction cured article is less, on the other hand, if surpass 25 μ m, then is difficult to obtain defoaming and high fillibility, and is therefore not preferred.
The cooperation ratio of these fillers (D) is preferably 40～90 quality % of total composition, more preferably 55～75 quality %.If the cooperation ratio less than 40 quality % of filler (D), the cured article that then obtains can not show sufficient low bulk, and then abrasive property and adaptation are also insufficient.On the other hand,, then be difficult to pulp, can not realize printing and filling perforation fillibility if surpass 90 quality %.
In addition, also can not cause and to use metallic particles such as copper, gold and silver, palladium simultaneously under the situation of problem having electroconductibility.
As feature of the present invention, aforementioned oxetane compound (E) is a kind of compound that contains the trimethylene oxide ring shown in following general formula (II),
(in the formula, R
2The alkyl of expression hydrogen atom or carbonatoms 1～6.)
For example, be raw material with 3-ethyl-trimethylene oxide alcohols such as 3-methylol trimethylene oxide, can obtain the multifunctional oxetane compound of etherificate, esterification.As concrete compound, 3-ethyl-3-methylol trimethylene oxide (commodity that East Asia Synesis Company makes OXT-101 by name), 3-ethyl-3-(phenoxymethyl) trimethylene oxide (commodity that East Asia Synesis Company makes OXT-211 by name), 3-ethyl-3-(2-ethyl hexyl oxy methyl) trimethylene oxide (commodity that East Asia Synesis Company makes OXT-212 by name), 1,4-two { [(3-ethyl-3-oxa-cyclobutyl) methoxyl group] methyl } benzene (commodity that East Asia Synesis Company makes OXT-121 by name), two (3-ethyl-3-oxa-cyclobutylmethyl) ether (commodity that East Asia Synesis Company makes OXT-221 by name) etc.Can also enumerate the oxetane compound of phenol phenol aldehyde type.Wherein, liquid oxetane compound also has dilution effect, and is therefore preferred.From the angle of dilution effect and characteristic, more preferably liquid and two functional two (3-ethyl-3-oxa-cyclobutylmethyl) ethers (commodity that East Asia Synesis Company makes OXT-221 by name).
These liquid oxetane compounds (E) are with different with polyfunctional alcohol's synthetic poly epihydric alcohol ether compound isoreactivity thinner by Epicholorohydrin, owing in raw material, do not use the halogenide of Epicholorohydrin and so on, therefore has good, the little feature of electrology characteristic to skin irritation.
As the use level of above-mentioned oxetane compound (E), in whole composition, account for 10 quality % or following, preferred 2～8 quality %.When the use level of above-mentioned oxetane compound (E) surpassed 10 quality % in whole composition, the solidified nature of composition reduced, and the reduction of the thermotolerance of cured article, and is therefore not preferred.
In order to adjust the viscosity of composition, hot curing resin composition of the present invention can also add diluting solvent except the oxetane compound of above-mentioned liquid state.The cooperation ratio of diluting solvent is preferably 10 quality % or following of total composition, and more preferably 5 quality % or following further preferably do not add.If the cooperation ratio of diluting solvent surpasses 10 quality %, the influence of evaporation of volatile component is easy to generate bubble and crackle during then owing to heating process in the portion of hole.
As aforementioned diluting solvent, for example can enumerate ketones such as methylethylketone, pimelinketone; Arenes such as toluene, dimethylbenzene, durene; Glycol ethers such as methylcyclohexane, ethylene glycol butyl ether, methyl carbitol, ethyl carbitol, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, the single ether of dipropylene glycol, triglycol list ether; Ester classes such as the acid esterification thing of ethyl acetate, butylacetate and above-mentioned glycol ethers; Alcohols such as ethanol, propyl alcohol, ethylene glycol, propylene glycol; Aliphatic hydrocarbon such as octane, decane; Organic solvents such as oil series solvent such as sherwood oil, petroleum naphtha, hydrogenated naphtha, solvent naphtha.They can be used or are used in combination 2 kinds or multiple individually.
In addition, when carrying out non-electrolysis on the cured article at compositions of thermosetting resin of the present invention, in order to make the easy alligatoring of compositions of thermosetting resin, improve the stripping strength with coating, (Jian Cheng is the oxazine compound under the Yi can also to cooperate compound with the cyclic group of De Han oxazine shown in the following general formula (I).)。
In the formula, R
1For methyl, cyclohexyl, can substituted aryl.
Aforementioned oxetane compound is meant the compound with trimethylene oxide ring, this trimethylene oxide is obtained by phenolic compound, formalin and primary amine reaction, specifically can enumerate, change into B-a type benzoxazine that industry (strain) makes, change into F-a type benzoxazine that industry (strain) makes and by phenol resol and formalin and aniline derivatives De oxazine resin etc. by the four countries of Bisphenol F and formalin and aniline derivatives by the four countries of dihydroxyphenyl propane and formalin and aniline derivatives.Can or be used in combination 2 kinds or multiple with their independent uses.
By cooperating Zhe Zhong oxazine compound, even compositions of thermosetting resin of the present invention is in being filled into hole portions such as through-holes of printed circuit boards and via hole and recess, after the completely solidified,, can improve the adaptation of coating by also alligatoring easily such as potassium permanganate solutions.In addition, this kind oxazine compound produces the phenol hydroxyl by adding thermal-ring-opening polymerization, reacts with aforementioned epoxy resins (A).In addition, as this ring opening catalyst, as known, can use the weak acid and the strong acid that in ortho position or contraposition, do not have substituent phenols etc.
As the use level of Shang Shu oxazine compound, with respect to the organic composition in the 100 quality % compositions, it is preferably in the scope of 2.5～50 quality %.If contain 2.5 quality % in the not enough organic composition of use level of compound of Qian Shu oxazine ring, can not realize with respect to and coating between the effect of adaptation, therefore not preferred.In addition, when surpassing 50 quality %, in the portion of hole, produce space and crackle during curing easily, therefore not preferred yet.
And then in composition of the present invention, according in case of necessity, can be engaged in common silk screen printing with the phthalocyanine blue of using in the resist printing ink, phthalocyanine green, iodine is green, the diazonium Huang, Viola crystallina, titanium oxide, carbon black, known habitual tinting materials such as naphthalene is black, the quinhydrones of the storage stability when being used to pay keeping, hydroquinone monomethyl ether, tert-butyl catechol, pyrogallol, known habitual thermal polymerization inhibitor such as thiodiphenylamine, clay, kaolin, bentonite, known habitual thickening material such as montmorillonite or thixotropic agent, silicone-based, fluorine system, defoamer and/or flow agents such as macromolecular, imidazoles system, thiazole system, triazole system, adaptations such as silane coupling agent are paid known habitual additive kinds such as agent.
From the angle of fillibility, the viscosity of the compositions of thermosetting resin of the present invention that is made of above moiety is preferable under 25 ℃ at 1000dPas or following.Being used for the aforementioned oxetane compound (E) of this viscosity adjustment or the use level of aforementioned diluting solvent is 10 quality % or following of composition, can be reduced in the generation of crackle in the composition when filling after fixing thus.
Can utilize silk screen print method, rolling method of present use etc., the compositions of thermosetting resin of the present invention that as above obtains is filled in the via hole of printed circuit board (PCB).Then, heated about about 30～90 minutes down, be warming up to about 140～180 ℃ of heating curing in about about 30～90 minutes (final curing) then at about 70～130 ℃.Thus, can easily remove the unwanted part that this cured compositions is exposed from substrate surface by physical grinding, thereby can form flat surfaces.In addition, composition of the present invention not only can be as the permanent filling perforation printing ink of printed circuit board (PCB), owing to have the cause of the characteristic of above excellence, so also can perform well in other purposes such as sealing agent of tightness system of IC assembly.
[embodiment]
Below by enumerating embodiment and comparative example the present invention is carried out specific description, but the present invention is not subjected to the qualification of following embodiment.In addition, " part " of the following stated all is benchmark with weight not having under the situation about specifying.
Embodiment 1,2 and comparative example 1,2
After being pre-mixed the added ingredients shown in the following table 1, grind dispersion, obtain each compositions of thermosetting resin with 3 roll-type mixing rolls.
Table 1
Measure the viscosity under 25 ℃ of compositions of thermosetting resin of the foregoing description 1,2 and comparative example 1,2 by following method, be filled in the having or not and stripping strength of the having or not of fillibility, abrasive property, cure shrinkage, crackle, voids left of the cured article in the hole portion of circuit card then by following method evaluation, its result is as shown in table 2.
[performance evaluation]
Viscosity:
Collect each thermosetting epoxy resin composition of 0.2ml previous embodiment 1,2 and comparative example 1,2,, under the condition of 25 ℃, revolution 5rpm/ minute, measure with cone-plate type viscometer (manufacturing of TOKIMEC company).
Fillibility:
Forming on the glass epoxy substrate of through hole by the plate plating in advance, under following printing condition, be filled in the through hole by silk screen print method each thermosetting epoxy resin composition with previous embodiment 1,2 and comparative example 1,2.After the filling, put into the heated air circulation type drying oven, under 120 ℃, carry out 1 hour Procuring, obtain assess sample (I).Filling extent according to the cured article in the through hole that is filled into this assess sample is estimated fillibility.Metewand is as follows.
Zero: completely filled.
△: the composition of filling flows out towards periphery from the bottom of through hole.
*: the bottom (lack of fill) that is not filled into through hole.
(printing condition)
Squeegee: the thick 20mm of squeegee, 70 ° of hardness, oblique grinding: 23 °, editions: PET100 order Bias version, coining: 60kgf/cm
2, squeegee speed: 5cm/ second, squeegee angle: 80 °
Abrasive property:
With polishing machine aforementioned assess sample (I) is carried out physical grinding, after the Procuring, the easy degree of removing that does not need cured article is partly estimated.Metewand is as follows.
Zero: can easily grind
△: it is difficult slightly to grind
*: can not grind
Depression:
With polishing machine aforementioned assess sample (I) is carried out physical grinding, removing does not need part, makes its smoothing.Put into the heated air circulation type drying oven then, under 150 ℃, carry out 1 hour main curing, obtain assess sample (II).Depression situation to the through-hole section of this assess sample (II) is estimated.Metewand is as follows.
Zero: do not cave in
△: find small depression
*: find significantly depression
Crackle:
Cut off aforementioned assess sample (II) in through-hole section, with its section of observation by light microscope, the through hole note that will crack (crack) on sample is made NG, calculates the ratio with respect to the NG of observed hole count.The judge benchmark is as follows.
Zero: crackle residual rate 0%
△: crackle residual rate less than 50%
*: crackle residual rate 50% or more than
Space residual:
Cut off aforementioned assess sample (II) in through-hole section,, confirm in through hole, to have tight with its section of observation by light microscope.The through hole note of residual clearance is made NG, calculate ratio with respect to the NG of observed hole count.The judge benchmark is as follows.
Zero: space production rate 0%
△: space production rate 50% or below
*: the space production rate surpasses 50%
Stripping strength:
On glass epoxy substrate, apply by silk screen print method each thermosetting epoxy resin composition previous embodiment 1,2 and comparative example 1,2 comprehensively, making after the swelling of filming that was heating and curing under 150 ℃ 60 minutes by solvent or solvent and alkali, is that oxygenant carries out the asperities processing with potassium permanganate.On the face of this asperitiesization, carry out electroless plating copper and copper electroplating, make assess sample (III).Measure the stripping strength of the conductor layer of this assess sample (III) according to the method for record among the JIS C-6481.
Table 2
As can be seen from Table 2, cooperated the embodiment 1 of trimethylene oxide to compare with the comparative example 1 that does not cooperate organic solvent and oxetane compound, viscosity is lower, and fillibility is good.In addition, not only viscosity is low, fillibility is good to have used the embodiment 2 of compound of oxetane compound and oxygen heterocyclic ring butane ring simultaneously, and stripping strength improves.On the other hand, the same with prior composition, cooperated organic solvent to replace the comparative example 2 of oxetane compound on through-hole section, to have depression, the residual of space also appearred.
Claims (5)
1. compositions of thermosetting resin, it is characterized in that: contain: (A) Resins, epoxy, (B) multifunctional phenolic compound, (C) curing catalysts, (D) filler and (E) oxetane compound, wherein, the use level of described multifunctional phenolic compound (B) is, total yield number with respect to the equivalents of the oxetanyl of the equivalents of the epoxy group(ing) of Resins, epoxy (A) and oxetane compound (E) is 1:0.2～1:1.2 equivalent, the use level of described curing catalysts (C) is, Resins, epoxy (A) with respect to 100 quality % is 0.1～10 quality %, the use level of described oxetane compound (E) is 10 quality % or following in whole composition, and the use level of described filler (D) is 40～90 quality % of total composition.
2. the compositions of thermosetting resin of putting down in writing according to claim 1 is characterized in that: with respect to the organic composition of 100 quality % in the composition, further contain the compound of the cyclic group of De Han oxazine shown in the following general formula of having of 2.5～50 quality % (I),
In the formula, R
1Expression methyl, cyclohexyl and can substituted aryl.
3. the compositions of thermosetting resin of putting down in writing according to claim 1 is characterized in that: described oxetane compound (E) is at normal temperatures for liquid.
4. the compositions of thermosetting resin of putting down in writing according to claim 1 is characterized in that: the viscosity of described compositions of thermosetting resin is 1000dPas or following down in 25 ℃.
5. printed circuit board (PCB), it is characterized in that: this printed circuit board (PCB) forms conductor circuit by interlayer resin insulating layers on substrate, and have the hole portion of having filled weighting material, the weighting material of wherein filling above-mentioned hole portion is made of the cured article of described each compositions of thermosetting resin of being put down in writing of claim 1 to 4.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004129141A JP4620967B2 (en) | 2004-04-26 | 2004-04-26 | Thermosetting resin composition for permanent hole filling |
| JP129141/2004 | 2004-04-26 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1690119A CN1690119A (en) | 2005-11-02 |
| CN100509951C true CN100509951C (en) | 2009-07-08 |
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| CNB2005100674965A Active CN100509951C (en) | 2004-04-26 | 2005-04-26 | Thermoset resin composition and multi-layer printed circuit board using the resin composition |
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| Country | Link |
|---|---|
| JP (1) | JP4620967B2 (en) |
| KR (1) | KR101212389B1 (en) |
| CN (1) | CN100509951C (en) |
| TW (1) | TW200604246A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2090610A1 (en) | 2006-11-29 | 2009-08-19 | Toyo Boseki Kabushiki Kasisha | Oxetane-containing resin, and adhesive agent and resist agent each using the same |
| JP5221893B2 (en) * | 2007-05-07 | 2013-06-26 | 協立化学産業株式会社 | Method for producing laminated film |
| JP5344394B2 (en) * | 2008-07-10 | 2013-11-20 | 山栄化学株式会社 | Curable resin composition, halogen-free resin substrate and halogen-free build-up printed wiring board |
| JP2010180355A (en) | 2009-02-06 | 2010-08-19 | Taiyo Ink Mfg Ltd | Thermosetting resin composition, dry film, printed wiring board and preparation thereof |
| JP5889568B2 (en) | 2011-08-11 | 2016-03-22 | メルク、パテント、ゲゼルシャフト、ミット、ベシュレンクテル、ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ ＧｍｂＨ | Composition for forming tungsten oxide film and method for producing tungsten oxide film using the same |
| JP5876758B2 (en) * | 2012-03-23 | 2016-03-02 | 東京応化工業株式会社 | Ink composition and pattern forming method |
| US9315636B2 (en) | 2012-12-07 | 2016-04-19 | Az Electronic Materials (Luxembourg) S.A.R.L. | Stable metal compounds, their compositions and methods |
| US9201305B2 (en) | 2013-06-28 | 2015-12-01 | Az Electronic Materials (Luxembourg) S.A.R.L. | Spin-on compositions of soluble metal oxide carboxylates and methods of their use |
| US9296922B2 (en) | 2013-08-30 | 2016-03-29 | Az Electronic Materials (Luxembourg) S.A.R.L. | Stable metal compounds as hardmasks and filling materials, their compositions and methods of use |
| US9418836B2 (en) * | 2014-01-14 | 2016-08-16 | Az Electronic Materials (Luxembourg) S.A.R.L. | Polyoxometalate and heteropolyoxometalate compositions and methods for their use |
| US9409793B2 (en) * | 2014-01-14 | 2016-08-09 | Az Electronic Materials (Luxembourg) S.A.R.L. | Spin coatable metallic hard mask compositions and processes thereof |
| JP6374434B2 (en) * | 2016-04-21 | 2018-08-15 | 山栄化学株式会社 | Thermosetting resin composition and electronic component mounting substrate |
| KR102399362B1 (en) | 2017-09-06 | 2022-05-18 | 메르크 파텐트 게엠베하 | Spin-on inorganic oxide containing composition useful as hard mask and filling material with improved thermal stability |
| CN107960035A (en) * | 2017-11-13 | 2018-04-24 | 广东欧珀移动通信有限公司 | Method for producing shell, housing and mobile terminal |
| CN112126274A (en) * | 2020-09-16 | 2020-12-25 | 四川乐凯新材料有限公司 | Photocurable composition for PCB containing alkenyl ether and/or oxetane compound |
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| JP4177013B2 (en) * | 2002-04-03 | 2008-11-05 | ダイセル化学工業株式会社 | Method for curing thermosetting epoxy resin composition, cured product and use thereof |
| JP4204814B2 (en) * | 2002-06-28 | 2009-01-07 | ヘンケル コーポレイション | Thermosetting liquid resin composition |
| JP2004285125A (en) * | 2003-03-19 | 2004-10-14 | Daicel Chem Ind Ltd | Epoxy resin composition and its cured product |
| JP4492070B2 (en) * | 2003-09-12 | 2010-06-30 | 住友化学株式会社 | Curable resin composition and protective film comprising the composition |
-
2004
- 2004-04-26 JP JP2004129141A patent/JP4620967B2/en not_active Expired - Lifetime
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Also Published As
| Publication number | Publication date |
|---|---|
| JP4620967B2 (en) | 2011-01-26 |
| KR20060047455A (en) | 2006-05-18 |
| TWI367226B (en) | 2012-07-01 |
| CN1690119A (en) | 2005-11-02 |
| JP2005307101A (en) | 2005-11-04 |
| TW200604246A (en) | 2006-02-01 |
| KR101212389B1 (en) | 2012-12-13 |
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Application publication date: 20051102 Assignee: Taiyo Ink Mfg.Co., Ltd. Assignor: Taiyo Holding Co., Ltd. Contract record no.: 2011990000116 Denomination of invention: Thermoset resin composition and multi-layer printed circuit board used thereof Granted publication date: 20090708 License type: Common License Record date: 20110302 |
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