CN101377620A - Photosensitive resin composition for flexible wiring circuit board and flexible wiring circuit board obtained by using the same - Google Patents
Photosensitive resin composition for flexible wiring circuit board and flexible wiring circuit board obtained by using the same Download PDFInfo
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Abstract
The invention aims to provide a photosensitive resin composition for a flexible circuit board having excellent flame retardancy and with non-halogenation for consideration of environmental aspects, and a flexible circuit board obtained by using the same. The photosensitive resin composition includes (A) a linear polymer containing a carboxyl group obtained by addition polymerizing an ethylenic unsaturated compound; (B) a polymerizable compound containing an ethylenic unsaturated group; (C) a photopolymerization initiator; and (D) a phosphorated epoxy resin containing phosphorous atoms at not less than 2 % by weight based on a total molecular weight thereof.
Description
Technical field
The present invention relates to the flexible circuitry substrate with photosensitive polymer combination (being designated hereinafter simply as " photosensitive polymer combination ") and with the flexible circuitry substrate with solder resist of its acquisition.
Background technology
For the flexible circuitry substrate that electron devices such as semiconductor element fixedly are installed by scolding tin, to be the regulation shape with having formed the polyimide film stamping-out that is called as tectal bond layer, and the material that stamping-out goes out pasted on the conductive pattern, perhaps the thermotolerance material that will be called as solder resist by silk screen print method or exposure imaging method is arranged on necessary position, covers insulation course (comprising solder mask layer) thereby be provided with on conductive pattern.
For this flexible circuitry substrate, characteristics such as the anti-scolding tin thermotolerance when requiring to have, insulativity, anti-flammability and inhibition flexible circuitry substrate generation warpage with the scolding tin installing device.
In the past, form material as above-mentioned covering insulation course, in order to improve anti-scolding tin thermotolerance etc., having proposed for example is the aqueous photonasty anticorrosive additive material (referring to patent documentation 1,2,3) of major component with bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenolic resin varnish type epoxy resin.
On the other hand, the flexible circuitry substrate also requires to have the high flame retardant of regulation such as UL specification.At this requirement, what carried out is by forming the compound that compounding in the material contains halogens such as bromine and give anti-flammability covering insulation course in the past.
[patent documentation 1] spy opens flat 7-207211 communique
[patent documentation 2] spy opens flat 8-134390 communique
[patent documentation 3] spy opens flat 9-5997 communique
Summary of the invention
The compound that contains halogens about above-mentioned use is given the mode of anti-flammability, known when making the circuit base plate that has adopted this compound carry out Actual combustion, can produce toxic gas, consider, require to give anti-flammability by halogen-freeization mode from aspects such as environmental protection.But actual conditions are, for flexible circuitry substrate thin, that specific surface area is big, still being unrealized to form covers the photosensitive polymer combination that insulation course forms material, and described covering insulation course forms material and gives anti-flammability by halogen-freeization and form.
The present invention makes in light of this situation, and purpose provides the photosensitive polymer combination with excellent flame retardancy that forms by halogen-freeization mode, considered the environmental protection aspect and with the flexible circuitry substrate of its acquisition.
In order to achieve the above object, first main points of the present invention are to comprise the photosensitive polymer combination of following (A)～(D) composition.
(A) make the ethene unsaturated compound carry out the carboxylic line polymer that addition polymerization forms.
(B) contain the polymerizable compound of ethene unsaturated group.
(C) Photoepolymerizationinitiater initiater.
(D) phosphorus atoms content is the above phosphorous epoxy resin that forms of 2 weight % of total molecular weight.
Second main points of the present invention are a kind of flexible circuitry substrate, this substrate forms in the following manner: the photosensitive polymer combination with above-mentioned first main points on the conductor circuit pattern forms the photosensitive polymer combination layer, by it being exposed, develops to the pattern of regulation, cover insulation course thereby form.
That is, the inventor etc. have carried out a series of researchs repeatedly in order to obtain possessing the photosensitive polymer combination of excellent flame retardancy by halogen-freeization mode.Can to give the photonasty anticorrosive additive material with anti-flammability in order probing into, and can not damage the halogen-free flame retardants of various rerum naturas (insulating reliability, development etc.), further investigate.Found that, if use the above-mentioned ethene unsaturated compound that makes to carry out carboxylic line polymer [(A) composition], the polymerizable compound [(B) composition] that contains the ethene unsaturated group and the phosphorus atoms content of addition polymerization formation phosphorous epoxy resin [(D) composition] as the above formation of 2 weight % of total molecular weight, then owing to use the above-mentioned epoxy resin that contains the specified quantitative phosphorus atoms, therefore can not damage as the rerum natura of photonasty anticorrosive additive material give anti-flammability, can improve the feature of environmental protection by halogen-freeization realization, thereby finish the present invention.
As mentioned above, the present invention contains the above-mentioned ethene unsaturated compound that makes to carry out the photosensitive polymer combination that carboxylic line polymer [(A) composition], the polymerizable compound [(B) composition] that contains the ethene unsaturated group and above-mentioned phosphorus atoms content that addition polymerization forms are the phosphorous epoxy resin [(D) composition] that forms more than the 2 weight % of total molecular weight.Therefore, realize anti-flammability by halogen-freeization mode.Thereby the photosensitive polymer combination of the application of the invention forms solder resist on the conductor circuit pattern, can obtain considering the flexible circuitry substrate that has been endowed excellent flame retardancy of environmental protection aspect.This flexible circuitry substrate by just having formed installation base plate behind the electron devices such as installation LSI, diode, transistor, capacitor such as scolding tin, can be mounted in the mini-plants such as portable phone and use.
If the glass transition temperature as the carboxylic line polymer of (A) composition is below 55 ℃, then can possess the effect that excellent inhibition warpage takes place.
In addition, if the content of (D) composition is set at the scope of 10～20 weight % of whole nonvolatile component of photosensitive polymer combination, then when giving more excellent flame, can also obtain to suppress the effect that the circuit base plate warpage takes place.
If bisphenol-A class (methyl) acrylate compounds that uses general formula (2) expression just can obtain the material of sensitivity and alkali-developable excellence as the above-mentioned polymerizable compound [(B) composition] that contains the ethene unsaturated group.
And, if use ring-type phosphorus-nitrogen compound [(E) composition] (phosphazene), warpage then can not take place, improve anti-flammability, and by using simultaneously with above-mentioned (D) composition, can obtain anti-flammability and low warpage properties, this two aspect of soldering resistance.But preferred above-mentioned ring-type phosphorus-nitrogen compound [(E) composition] is below the 20 weight % of whole nonvolatile component of photosensitive polymer combination.This is because if the addition of this ring-type phosphorus-nitrogen compound [(E) composition] more than 20 weight %, then occurs the tendency that the crystallization frosting is separated out from the teeth outwards under hot and humid condition.
Description of drawings
[Fig. 1] (a) reaches (b) is the key diagram of representing the assay method of amount of warpage.
Embodiment
Photosensitive polymer combination of the present invention is to use the ethene unsaturated compound is carried out carboxylic line polymer (A composition), the polymerizable compound (B composition) that contains the ethene unsaturated group, Photoepolymerizationinitiater initiater (C composition) and the specific epoxy resin (D composition) that addition polymerization forms and the composition that obtains.
Above-mentioned carboxylic line polymer (A composition) is that the ethene unsaturated compound is carried out addition polymerization and the polymkeric substance that obtains, can obtain by (methyl) acrylic acid, carboxylic styrene derivative, maleic anhydride etc. are carried out copolymerization.The line polymer that obtains by this method because can at random control acid equivalent, the starting monomer kind is abundant, therefore easily glass transition temperature rerum naturas such as (Tg) is designed.
The weight-average molecular weight of above-mentioned carboxylic linear polymer (A composition) is preferably 5000～100000 scope, and more preferably 6000～80000, be preferably 7000～60000 scope especially.That is, this is because if weight-average molecular weight less than 5000, and then rerum natura such as scolding tin thermotolerance has the tendency of variation, if surpass 100000, then alkali-developable has the tendency of variation.
In addition, the acid equivalent of above-mentioned carboxylic linear polymer (A composition) is preferably 200～900 scope, and more preferably 250～850,300～800 scope more preferably.That is, this is because if acid equivalent less than 200 then can promote the copper oxidation under hot and humid, is not preferred therefore, if surpass 900, then alkali-developable has the tendency of variation.
And as above-mentioned carboxylic linear polymer (A composition), in order to give the effect of its thermotolerance and inhibition warpage, preference is as containing benzene oxygen ethyl (methyl) acrylate as copolymer composition.
Therefore, as above-mentioned carboxylic linear polymer (A composition), for example can enumerate that benzene oxygen ethyl (methyl) acrylate, (methyl) acrylic acid and other vinyl monomer carry out copolymerization and the polymkeric substance that obtains.
As other above-mentioned vinyl monomer, for example can enumerate (methyl) acrylic acid Arrcostabs such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate; (methyl) 2-EHA, (methyl) acrylic acid tetrahydrofuran methyl esters, (methyl) dimethylaminoethyl acrylate, (methyl) acrylic acid diethylamino ethyl ester, styrene, α-styrene, vinyltoluene, N-vinyl pyrrolidone, (methyl) acrylic acid 2-hydroxyl ethyl ester, acrylamide, vinyl cyanide, methacrylonitrile, N-phenylmaleimide, cyclohexyl maleimide etc.These monomers may be used singly or in combination of two or more kinds.
As the copolymerization amount of benzene oxygen ethyl (methyl) acrylate of above-mentioned copolymer composition, be preferably set to 20～92 weight % of copolymer composition total amount, the scope of 30～90 weight % more preferably.That is, this is because if copolymerization quantity not sufficient 20 weight %, and then anti-flammability has the tendency of decline, if surpass 92 weight %, though then can obtain anti-flammability, the alkali-developable of the solder resist after the curing has the tendency of variation.
In addition, as (methyl) of above-mentioned copolymer composition acrylic acid copolymerization amount, be preferably set to 8～40 weight % of copolymer composition total amount, the scope of 10～35 weight % more preferably.That is, this is because if copolymerization quantity not sufficient 8 weight %, has then that development time is elongated, the tendency of operability variation, if surpass 40 weight %, then hot and humid the tendency that promotes the copper oxidation is arranged down.
As the copolymerization amount of other vinyl monomer of above-mentioned copolymer composition, be preferably set to 0～72 weight % of copolymer composition total amount, the scope of 0～60 weight % more preferably.That is, this is that then anti-flammability and development have the tendency of variation because if the copolymerization amount surpasses 72 weight %.
What illustrated is to introduce ethene unsaturated group etc. by high molecular weight reactive in above-mentioned carboxylic linear polymer (A composition) after polymerization.But in the present invention, when introducing ethene unsaturated group etc. by high molecular weight reactive, the value of following glass transition temperature (Tg) refers to the measured value of the glass transition temperature (Tg) of introducing the line polymer before the ethene unsaturated group.In addition, after polymerization, when on the carboxyl of the multipolymer that uses above-mentioned each monomer component to obtain, introducing the ethene unsaturated group with reaction such as glycidyl acrylate, consider the carboxyl amount that disappears because of the reaction after introducing, preferably increase above-mentioned (methyl) acrylic acid copolymerization amount.Ethene unsaturated compound as can introduce carboxyl on the line polymer of ethene unsaturated compound is not limited to above-mentioned (methyl) acrylic acid, for example can use styrene derivative, maleic anhydride derivant etc.
In addition, as above-mentioned specific carboxylic linear polymer (A composition), preferably its glass transition temperature is below 55 ℃, and special preferred glass transition temperature is 30～55 ℃.Promptly, this be because if glass transition temperature above 55 ℃, then photosensitive polymer combination often has the tendency that warpage takes place after cure shrinkage, if 30 ℃ of less thaies, then photosensitive polymer combination solution coat, dried dry coating have generation viscosity, the tendency of the problem of operability variation occurs.As mentioned above, the invention is characterized in and use the material that possesses following characteristic that promptly as the carboxylic linear polymer of A composition, glass transition temperature is below 55 ℃.Above-mentioned glass transition temperature for example can followingly be measured.Promptly, determination of viscoelasticity such as the ARES galvanometer that can use テ イ-エ イ イ Application ス Star Le メ Application ト society to make, at frequency 1Hz, 5 ℃/minute of programming rates are obtained the glass transition temperature (Tg) as tan δ value when measuring under the condition that the mensuration temperature is 0～150 ℃.
The polymerizable compound that contains the ethene unsaturated group (B composition) that uses with above-mentioned A composition has no particular limits, but when it is bisphenol-A class (methyl) acrylate compounds of general formula (2) expression, characteristics such as scolding tin thermotolerance, folding resistance, alkali-developable are harmonious excellent, are preferred therefore.
[in the formula (2), R
1And R
2Be respectively hydrogen atom or methyl, can be identical or different mutually.In addition, Y
1And Y
2Be respectively that carbon number is 2～6 alkylidene.P and q are selected from that to make p+q be 4～40 positive integer.]
In above-mentioned formula (2), be 2～6 alkylidene as carbon number, for example can enumerate ethylidene, propylidene, isopropylidene, butylidene, isobutylidene, pentylidene, inferior neopentyl, hexylidene etc.Preferred especially ethylidene.
Above-mentioned isopropylidene is-CH (CH
3) CH
2The group of-expression, in the above-mentioned general formula (2) ,-(O-Y
1)-and-(Y
2-O)-the bonding direction have methylene and oxygen bonding and methylene not with two kinds of situations of oxygen bonding, can be a kind of bonding direction, also can be that two kinds of bonding directions are mixed and existed.
Above-mentioned-(O-Y
1)-and-(Y
2-O)-repetitive be respectively 2 when above, plural Y
1And plural Y
2Can be identical or different mutually.Work as Y
1And Y
2When constituting, two or more-(O-Y by two or more alkylidenes
1)-and-(Y
2-O)-and can exist by random fashion, also can exist by block fashion.
In addition, in above-mentioned general formula (2), but can have substituting group more than 1 on the position of substitution of two phenyl ring, have more than 2 under the substituent situation, these substituting groups can be identical or different mutually.As this substituting group, the carbon number that can enumerate carbon number for example and be 1～20 alkyl, carbon number and be 3～10 naphthenic base, carbon number and be 6～14 aryl, amino, nitro, cyano group, sulfydryl, allyl, carbon number and be 1～10 alkyl thiol, carbon number and be 1～20 hydroxy alkyl, alkyl is that the carbon number of 1～10 carboxyalkyl, alkyl is that 1～10 acyl group, carbon number are 1～20 alkoxy or the group that contains heterocycle etc.
In above-mentioned general formula (2), repeat number p, q are selected from that to make p+q be 4～40 positive integer, are more preferably to be selected from that to make p+q be 4～15 positive integer, and preferably being selected from especially and making p+q is 5～13 positive integer.That is, this is because if p+q less than 4, and then not only warpage increases, and folding resistance has the tendency of minimizing, if p+q surpasses 40, then photosensitive polymer combination shows water wettability on the whole, and hot and humid insulating reliability down has variation to be inclined to.
Bisphenol-A class (methyl) acrylate compounds as above-mentioned general formula (2) expression, specifically, can enumerate 2,2 '-two [4-(methyl) acryloxy diethoxy phenyl] propane, 2,2 '-two [4-(methyl) acryloxy tetrem oxygen phenyl] propane, 2,2 '-two [4-(methyl) acryloxy five ethoxyphenyls] propane, 2,2 '-two [4-(methyl) acryloxy diethoxy eight propoxy phenyls] propane, 2,2 '-two [4-(methyl) acryloxy triethoxy eight propoxy phenyls] propane etc.These compounds may be used singly or in combination of two or more kinds.
As the Photoepolymerizationinitiater initiater that uses with above-mentioned A and B composition (C composition), can enumerate and for example replace or unsubstituted multinuclear quinones (2-EAQ, 2-tert-butyl group anthraquinone, the prestox anthraquinone, 1,2-benzo anthraquinone, 2,3-diphenyl anthraquinone etc.), α-ketaldonyl alcohols (benzoin, hexamethylacetone etc.), ethers, α-hydrocarbon substituted aromatic acyloin class (α-phenyl-benzoin, α, α-diethoxy acetophenone etc.), aromatic series ketone (benzophenone, N, N '-tetraethyl-4,4,4 ' of 4 '-diaminobenzophenone etc.-two dialkyl amido benzophenone etc.), thioxanthene ketone (2-methyl thioxanthones, 2, the 4-diethyl thioxanthone, the 2-clopenthixal ketone, the 2-isopropyl thioxanthone, 2-ethyl thioxanthones etc.), 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-morpholino propane-1-ketone etc.These initiating agents can use separately, and also two or more kinds may be used.
The specific epoxy resin (D composition) that uses with above-mentioned A～C composition is the phosphorous epoxy resin that forms more than the 2 weight % of phosphorus atoms content as total molecular weight.Above-mentioned D composition has been the material of fire retardant effect, does not contain halogens, therefore can reach the effect of having considered the feature of environmental protection by non-halogenated mode.And, give anti-flammability with can not damaging rerum naturas such as insulating reliability and development, be preferred.
In above-mentioned D composition,, then be difficult to give enough anti-flammabilitys if phosphorus atoms content arrives 2 weight % of not enough total molecular weight less.What illustrated is, though there is no particular limitation for the content of above-mentioned phosphorus atoms, the content of phosphorus atoms is when 5 weight % are above, sometimes with the intermiscibility variation of epoxy resin.
As above-mentioned D composition, except for example Journal of Applied Polymer Science73, contain outside the fire-retarded epoxy resin of nitrogen-atoms and phosphorus atoms when introducing in 353 (1999), can enumerate the phosphorous epoxy resin that contains the diphenyl phosphoester skeleton structure of following general formula (1) expression.
[in the formula (1), X is the substituent aromatic group with at least 2 terminal band epoxy radicals.]
In above-mentioned formula (1), about X, as substituent aromatic groups, can enumerate the derivant, bisphenol derivative of novolac resin for example etc., and in 1 molecule, also can contain a plurality of diphenyl phosphoester skeleton structures with at least 2 terminal band epoxy radicals.
The phosphorous epoxy resin that contains the diphenyl phosphoester skeleton structure as this general formula (1) expression, the epoxy resin of following structural formula (1a) expression that provides among the epoxy resin that provides in No. 3613724 communique of Japan special permission, No. 3533973 communique of special permission, the Journal of Applied Polymer Science 73,1231 (1999) etc. can be provided particularly.
As above-mentioned phosphorous epoxy resin (D composition), its epoxide equivalent is 300～500 o'clock, considers it is preferred from the warpage and the soldering resistance aspect that cause because of cure shrinkage.In addition, preferably using weight-average molecular weight is material below 1000.
In the present invention, except that above-mentioned A～D composition,, can use ring-type phosphorus-nitrogen compound (E composition) in order further to obtain anti-flammability simultaneously, suppress warpage and to obtain soldering resistance.As above-mentioned ring-type phosphorus-nitrogen compound (E composition), can enumerate the ring-type phenoxy group phosphorus-nitrogen compound of following general formula (3) expression etc. particularly.
[in the formula (3), n is 3～10 positive number.]
In above-mentioned formula (3), repeat number n is 3～10, more preferably 3～5.
The ring-type phenoxy group phosphorus-nitrogen compound of this general formula (3) expression for example can be used as the acquisitions such as SPE-100 that Da mound chemistry society makes.
When in photosensitive polymer combination of the present invention, using above-mentioned A～D composition, and when further using the E composition, the content of each composition preferably as following mode set.At first, the content of above-mentioned A composition is preferably set to 30～60 weight % of whole photosensitive polymer combinations.That is, this is that then developing powder is sometimes slack-off because if be lower than 30 weight %, if surpass 60 weight %, the exposure position had the film of generation residual when then alkali developed, or anti-flammability easily becomes not enough tendency.
The content of above-mentioned B composition is preferably set to 10～40 weight % of whole photosensitive polymer combinations, more preferably 15～30 weight %.That is, this is because if less than 10 weight %, and the sensitivity when then photosensitive polymer combination being exposed has the tendency of variation, if surpass 40 weight %, then alkali-developable has the tendency of variation.
The content of above-mentioned C composition is preferably set to the scope of 1～10 weight % of whole photosensitive polymer combinations, more preferably 3～8 weight %.That is, this is because if less than 1 weight %, and then sensitivity has the tendency that becomes not enough, if surpass 10 weight %, then alkali-developable has the tendency of variation.
The content of above-mentioned D composition is preferably set to 10～20 weight % in whole nonvolatile component of photosensitive polymer combination, more preferably 15～20 weight %.That is, this is because if less than 10 weight %, and then anti-flammability has not enough tendency, if surpass 20 weight %, then the warpage of flexible circuitry substrate has the tendency that becomes big.
The content of above-mentioned E composition is preferably set to below the 20 weight % of whole photosensitive polymer combinations, more preferably 5～20 weight %.That is, this is that then as mentioned above, the E composition is separated out tendency because if surpass 20 weight %.
According to necessity, can also be in photosensitive polymer combination of the present invention suitable other adjuvant beyond above-mentioned each composition of compounding, promptly, pigment such as phthalocyanine green, phthalocyanine blue, fillers such as silicon dioxide, barium sulphate, talcum, defoamer, levelling agent, fire retardant, stabilizing agent, 2-amino-5-sulfydryl-1,3,4-thiadiazoles or 5-amino-adaptation imparting agents such as 1-H-tetrazolium, rust preventive such as benzotriazole, epoxy resin outside above-mentioned D composition and the E composition, thermal cross-linking agents such as blocked isocyanate etc.These materials may be used singly or in combination of two or more kinds.These other adjuvants preferably use in the scope of whole 0.01～20 weight % of photosensitive polymer combinations.
Photosensitive polymer combination of the present invention can mix above-mentioned each composition by being mixed with formation regulation content and form.Can mix use with organic solvent according to necessity.As above-mentioned organic solvent, have no particular limits, can use for example TC acetic acid esters, diethylene glycol single-butyl ether acetic acid esters, TC, diethylene glycol monomethyl ether, solvent oil, N-Methyl pyrrolidone, gamma-butyrolacton, butyl cellosolve, ethyl cellosolve, methyl cellosolve, toluene, dimethylbenzene, Lay (mesitylene), acetone, methyl ethyl ketone, methyl isobutyl ketone equal solvent or their mixed solvent.
When using above-mentioned organic solvent, its use amount has no particular limits, and can mix about 0～200 weight portion with respect to photosensitive polymer combination 100 weight portions and use.
The energy storage elastic modulus of the photosensitive polymer combination that obtains thus under [ultraviolet ray (UV) exposure back] after the curing 50 ℃ is preferably below the 1GPa, more preferably 0.1～1GPa.That is, this is because if surpass 1GPa, and the warpage after then photosensitive polymer combination solidifies has to become greatly to be inclined to.What illustrated is that the energy storage elastic modulus after the above-mentioned curing under (UV exposes back) 50 ℃ is for example to use solid determination of viscoelasticity device, at frequency 1Hz, 5 ℃/minute of programming rates, measure 0～150 ℃ of temperature, when stretch mode is measured down, the numerical value that obtains by the value that reads under 50 ℃.
Like this, photosensitive polymer combination of the present invention can be used as flexible circuitry substrate solder resist material.
When using with the solder resist material, for example can followingly use as above-mentioned flexible circuitry substrate.Next coming in order describe.
At first, conductor circuit pattern at the flexible circuitry substrate forms on the surface, be coated with photosensitive polymer combination of the present invention so that dried thickness is 5～50 μ m with silk screen print method, spraying process, rolling method, electrostatic coating method, after under 5～120 ℃ dry about 3～60 minutes, be provided with according to making negative mask pattern film or positive mask pattern case film directly contact or not contact, shine active ray then with coating.
As the light source of above-mentioned active ray, can use known various light source, for example the effective lamp of irradiation ultraviolet radiation such as carbon arc lamp, mercury vapour arc lamp, extra-high-pressure mercury vapour lamp, high-pressure mercury-vapor lamp, xenon lamp, metal halide lamp.In addition, also can use photoflood lamp, sunlamp etc. can effectively shine the device of visible light.
Then, use developer solutions such as alkaline aqueous solution, remove unexposed portion and develop preparation resist pattern by for example spraying, shake known methods such as dipping, brushing, scouring.
As the alkaline aqueous solution that uses in the above-mentioned development, can use the sodium carbonate lean solution of 0.1～5 weight %, the sal tartari lean solution of 0.1～5 weight %, the dilute solution of sodium hydroxide of 0.1～5 weight %, the sodium tetraborate lean solution of 0.1～5 weight % etc.
In addition, ultraviolet ray irradiation, heating can be carried out in order to improve scolding tin thermotolerance, chemical-resistant etc. by high-pressure mercury-vapor lamp according to necessity in the back of developing.Above-mentioned ultraviolet irradiation amount is preferably set to 0.2～10J/cm
2About, in addition, above-mentioned heating is preferably in the scope about 100～180 ℃ to be carried out 15～120 minutes.The order of this ultraviolet ray irradiation and heating can be that any at first carries out, and also can only adopt the ultraviolet ray irradiation and add any that pine for and handle.
Formed the flexible circuit board of solder resist in such a way, by the fixing electron devices such as LSI, diode, transistor, capacitor are installed that wait of scolding tin, formed installation base plate afterwards, for example be installed in the small-sized machine such as portable phone etc.
Below, enumerate embodiment simultaneously and comparative example describes embodiment.But the present invention is not limited to these embodiment.
Embodiment
[synthesis example 1]
[polymkeric substance (carboxylic line polymer) a's is synthetic]
At first, in blanket of nitrogen, 291g TC acetic acid esters (feeding intake for the first time) is added in 1 liter of separate type flask, be heated to 130 ℃ while stirring.Be incubated after 30 minutes, 243g benzene oxygen ethyl propylene acid esters, 100g methacrylic acid, 158g methyl methacrylate, 158g TC acetic acid esters (feeding intake for the second time), 8.0g are carried out mixed dissolution as the azoisobutyronitrile of catalyzer, the solution that forms was added drop-wise to separate in the flask with 3 hours reacts.Insulation is after 2 hours down at 80 ℃, and cooling obtains polymer solution a (solid concentration 53 weight %).
[polymkeric substance (carboxylic line polymer) b～e's is synthetic]
The use amount (each input amount) of TC acetic acid esters is become following the amount of Table 1.In addition, each monomer component and the use amount of using thereof become following table 2.What illustrated is that the ア ロ ニ Star Network ス in the table 2 is the N-acrylyl oxy-ethyl hexahydrophthalic phthalimide that the synthetic society in East Asia makes.For synthesis condition (temperature, time etc.) in addition, by with the above-mentioned synthesis example 1 identical polymkeric substance b～e that synthesized.In addition, measure glass transition temperature and the weight-average molecular weight of resulting polymkeric substance a～e as follows, be shown in together in the following table 2.
[mensuration of glass transition temperature]
On the polyethylene terephthalate film of having carried out demoulding processing with organic siliconresin, coating, dry (120 ℃ * 30 minutes) are by the polymer solution that said method obtains, and making dried thickness is about 20 μ m.And then after peeling off the polymer film that obtains from polyethylene terephthalate film, use 50 ℃ roll-type laminating machine, carry out overlapping pressing.For the thickness that obtains is the film of about 300 μ m, and the ARES that uses テ イ-エ イ イ Application ス Star Le メ Application ト society to make is at parallel-plate diameter 7.9mm, load 200g, frequency 6.3rad/ second under the condition that programming rate is 5 ℃/minute, is to measure under 0～150 ℃ measuring temperature.Obtain the glass transition temperature as tan δ value (Tg) that obtains.
[mensuration of weight-average molecular weight]
Measure the weight-average molecular weight of the polymkeric substance that obtains by said method by following condition.
Determinator: GPC (the Dong Caoshe system, HLC-8120GPC)
Column dimension: diameter 6.0mm * 15cm * 3 piece (adding up to 45cm)
Column temperature: 40 ℃
Eluent: 10ml (LiBr)+10ml (phosphoric acid/dimethyl formamide (DMF))
Flow velocity: 0.4m/min
Inlet pressure: 4.7Pa
Injection rate IR: 20 μ l
Detecting device: differential refractometer (RI)
Standard specimen: polyoxyethylene (PEO)
Data processing equipment: Dong Caoshe system, GPC-8020
Table 1 (g)
Table 2 (g)
* the numerical value in () is weight % in the table.
Then, prepare the various compositions shown in following.
[polymerizable compound that contains the ethene unsaturated group]
B1: the BPE500 that chemistry society in Xin Zhong village makes, the bisphenol A-type methacrylate of oxirane modification [p+q=10 in the above-mentioned formula (2), R
1=H, R
2=H, Y
1=CH
2CH
2, Y
2=CH
2CH
2]
B2: trimethylolpropane triacrylate (TMPTA)
[Photoepolymerizationinitiater initiater]
C1: チ バ ガ イ ギ-society's system, Irgacure907
C2: Japanese chemical drug society system, KAYACURE DETS-X
[phosphorous epoxy resin]
D1: Dongdu changes into society's system, FX-305 (phosphorus atoms content 3.0 weight %, epoxide equivalent 485)
D2: Dongdu changes into society's system, FX-305C (phosphorus atoms content 2.6 weight %, epoxide equivalent 382)
[epoxy resin]
Big Japanese イ Application キ society system, triethylene glycol divinyl ether modified bisphenol A type epoxy resin
[ring-type phosphorus-nitrogen compound]
Da mound chemistry society system, in the SPE-100[formula (3), n=3～4]
[pigment]
Phthalocyanine blue
[adaptation imparting agent]
5-amino-1-H-tetrazolium
[defoamer]
CBC マ テ リ ア Le ズ society system, モ ダ Off ロ-(acrylic copolymer)
[embodiment 1～6, comparative example]
By each composition shown in the following table 3 being carried out compounding in ratio shown in this table, preparation photosensitive polymer combination (what illustrated is that the numerical value in the table 3 is the weight of non-volatile content).
Table 3
(g)
Use each photosensitive polymer combination obtain like this, carry out evaluating characteristics by method shown in following.The result is shown in the following table 4 together.
[the energy storage elastic modulus after the curing]
On the polyethylene terephthalate film of having carried out demoulding processing with polyorganosiloxane resin, coating, dry (80 ℃ * 30 minutes) above-mentioned photosensitive polymer combination solution are so that dried thickness is about 20 μ m.Driving fit thickness is the polyethylene terephthalate system coverlay of 38 μ m on above-mentioned desiccated surface, carries out 300mJ/cm with extra-high-pressure mercury vapour lamp from covering face
2Exposure.Then, peel off coverlay after, use 25 ℃ 1 weight % aqueous sodium carbonate under pressure 0.2MPa, to develop 90 seconds, cleaned 30 seconds with tap water again.It is carried out 150 ℃ * 30 minutes thermal treatment in hot air circular drying machine.Peel off above-mentioned polyethylene terephthalate film of having carried out after the demoulding is handled then, make wide 5mm, the about 20 μ m of thickness, the sample of long 30mm.Use this sample, utilize solid determination of viscoelasticity device RSA2 (レ オ メ ト リ Star Network サ イ エ Application テ イ Off イ Star Network society system), in 0～150 ℃ of scope, press 5 ℃/minute of programming rates, frequency 1Hz, chuck spacing 22.6mm condition is measured stretching energy storage elastic modulus, with the energy storage elastic modulus of 50 ℃ of numerical value down after as curing.
[warpage]
At thickness be on the polyimide film of 12.5 μ m the above-mentioned photosensitive polymer combination solution of coating so that dried thickness is 20 μ m.In addition, by identical,, on polyimide film, make the photosensitive polymer combination rete until the drying process that carries out 150 ℃ * 30 minutes with the method for energy storage elastic modulus after said determination solidifies.Then, go up the circular specimen 1 of stamping-out from above-mentioned film (double-layer structure of polyimide film+photosensitive polymer combination film) as figure (1a) diameter 20mm that is shown as.Then, shown in figure (1b), in the sample of making 1, the minimum edge of the edge spacing minimum of mensuration sample 1 is intermarginal apart from L (mm), pass through following formula: [amount of warpage (mm)=20 (mm)-minor face is intermarginal apart from L (mm)] calculates the amount of warpage of film, estimates by following standard.
Zero: amount of warpage is less than 5mm.
*: amount of warpage is more than the 5mm.
[alkali-developable]
Be on the Copper Foil of 35 μ m through degreasing, soft etching, the thickness that carried out surfacing, coating, dry (80 ℃ * 30 minutes) above-mentioned photosensitive polymer combination solution are so that dried thickness is about 20 μ m, and then driving fit thickness is the polyethylene terephthalate film of 38 μ m thereon, and the extra-high-pressure mercury vapour lamp of using 250W is with 300mJ/cm
2Exposure carry out ultraviolet ray irradiation.Then, peel off above-mentioned polyethylene terephthalate film, use 25 ℃ 1 weight % aqueous sodium carbonate under pressure 0.2MPa, to develop 90 seconds.Unexposed portion after visualization is developed is estimated by following standard.
Zero: the residue that does not have photosensitive polymer combination.
*: the residue that has photosensitive polymer combination.
[anti-flammability]
Be on the face of polyimide film of 12.5 μ m at thickness, coating, dry (80 ℃ * 30 minutes) above-mentioned photosensitive polymer combination solution are so that dried thickness is 20 μ m, and then driving fit thickness is the polyethylene terephthalate film of 38 μ m thereon, and the extra-high-pressure mercury vapour lamp of using 250W is with 300mJ/cm
2Exposure carry out ultraviolet ray irradiation.On the other hand, on another face of above-mentioned polyimide film, by being coated with drying (80 ℃ * 30 minutes) photosensitive polymer combination solution so that dried thickness is 20 μ m with above-mentioned same mode, driving fit thickness is the polyethylene terephthalate film of 38 μ m thereon, and the extra-high-pressure mercury vapour lamp of using 250W is with 300mJ/cm
2Exposure carry out ultraviolet ray irradiation.Then, peel off two polyethylene terephthalate film, use 25 ℃ 1 weight % aqueous sodium carbonate under pressure 0.2MPa, to develop 90 seconds, cleaned 30 seconds with tap water again, then it is carried out 150 ℃ * 30 minutes thermal treatment in hot air circular drying machine.Estimate its anti-flammability according to device (the smart mechanism of Japan is made society of institute system, No.1031, HVUL UL combustion testing chamber), method (VTM method) based on flame retardant test specification UL94.With VTM-0 is qualified.
[insulativity]
Preparation is directly to have formed the bias voltage test (bias test) of thickness 10 μ m, L/S (pattern wide/pattern spacing)=50 μ m/50 μ m flexible circuit board with comb type copper pattern on the polyimide film of 25 μ m at thickness, to its degreasing, soft etching, the copper surface is repaired.Then, coating on above-mentioned flexible circuitry substrate, dry (80 ℃ * 30 minutes) above-mentioned photosensitive polymer combination solution are so that dry back thickness is 20 μ m, driving fit thickness is the polyethylene terephthalate film of 38 μ m thereon, with the extra-high-pressure mercury vapour lamp of 250W, with 300mJ/cm
2The exposure irradiation ultraviolet radiation.Peel off polyethylene terephthalate film then, use 25 ℃ 1 weight % aqueous sodium carbonate under pressure 0.2MPa, to develop 90 seconds, cleaned 30 seconds with ion exchange water then, in hot air circular drying machine, carry out 150 ℃ * 30 minutes thermal treatment afterwards, make insulativity test printed-wiring board (PWB).This insulativity is tested the constant temperature and humidity cabinet of putting into 85 ℃ * 85%RH with printed-wiring board (PWB), between two electrodes of comb type pattern, apply the voltage of 50V, in groove, measure insulation resistance, estimate by following standard until through 1000 hours.
Zero: even still be shown as 10 through 1000 hours insulating resistance values
6More than the Ω.
*: be shown as less than 10 with interior insulating resistance value at 1000 hours
6Ω.
[scolding tin thermotolerance]
Use through degreasing, soft etching, the thickness that has carried out surfacing is that Copper Foil and the thickness of 10 μ m is the polyimide film of 25 μ m, making thickness is two layers of base material (polyimide films of Copper Foil+thickness 25 μ m of thickness 10 μ m) of 35 μ m, on the Copper Foil of these two layers of base materials, be coated with, dry (80 ℃ * 30 minutes) above-mentioned photosensitive polymer combination solution is so that dry back thickness is 20 μ m, driving fit thickness is the polyethylene terephthalate film of 38 μ m thereon, see through and be formed with the glass mask of bearing pattern on one side for the square of 5mm, with the extra-high-pressure mercury vapour lamp of 250W, with 300mJ/cm
2The exposure irradiation ultraviolet radiation.Peel off polyethylene terephthalate film then, use 25 ℃ 1 weight % aqueous sodium carbonate under pressure 0.2MPa, to develop 90 seconds, after cleaning 30 seconds with ion exchange water then, in hot air circular drying machine, carry out 150 ℃ * 30 minutes thermal treatment, make scolding tin heat-resistance test substrate.
After then being coated with rosin based Off ラ Star Network ス MH-820V ( system ラization is ground society's system), in 260 ℃ solder bath, flooding and pay the scolding tin processing 10 seconds.Estimate by following standard by visual then.
Zero: do not take place that scolding tin pierces, the arching upward, peel off of solder resist.
*: taken place that scolding tin pierces or the arching upward and peel off of solder resist.
Table 4
By The above results as can be known, the embodiment goods can obtain alkali-developable, insulativity, all good flexible circuitry substrate of scolding tin thermotolerance.And, can also obtain all excellent result of anti-flammability.And having used glass transition temperature is that the embodiment goods of the polymkeric substance below 55 ℃ have suppressed amount of warpage effectively.
Relative therewith, the comparative example goods have obviously obtained relatively poor result in the anti-flammability evaluation.
Claims (7)
1, flexible circuitry substrate photosensitive polymer combination is characterized in that containing following (A)～(D) composition:
(A) the ethene unsaturated compound is carried out the carboxylic line polymer that addition polymerization forms;
(B) contain the polymerizable compound of ethene unsaturated group;
(C) Photoepolymerizationinitiater initiater;
(D) phosphorus atoms content is the phosphorous epoxy resin that forms more than the 2 weight % of total molecular weight.
2, the described flexible circuitry substrate of claim 1 photosensitive polymer combination wherein, is below 55 ℃ as the glass transition temperature of the carboxylic line polymer of above-mentioned (A) composition.
3, claim 1 or 2 described flexible circuitry substrate photosensitive polymer combinations, wherein, above-mentioned (D) composition is the phosphorous epoxy resin that contains the diphenyl phosphoester skeleton structure of following general formula (1) expression,
In the formula (1), X is the substituent aromatic group with at least 2 terminal band epoxy radicals.
4, claim 1 or 2 described flexible circuitry substrate photosensitive polymer combinations, wherein, the content of above-mentioned (D) composition is set at the scope of flexible circuitry substrate with 10～20 weight % of whole nonvolatile component of photosensitive polymer combination.
5, claim 1 or 2 described flexible circuitry substrate photosensitive polymer combinations wherein, are bisphenol-A class (methyl) acrylate compounds of following general formula (2) expression as the polymerizable compound that contains the ethene unsaturated group of above-mentioned (B) composition,
In the formula (2), R
1And R
2Be respectively hydrogen atom or methyl, can be identical or different mutually; In addition, Y
1And Y
2Be respectively that carbon number is 2～6 alkylidene; P and q are selected from that to make p+q be 4～40 positive integer.
6, claim 1 or 2 described flexible circuitry substrate photosensitive polymer combinations, wherein, except above-mentioned (A)～(D) composition, contain following (E) composition:
(E) ring-type phosphorus-nitrogen compound.
7, flexible circuitry substrate, this substrate forms in the following manner: use claim 1 or 2 described flexible circuitry substrates to form the photosensitive polymer combination layer with photosensitive polymer combination on the conductor line pattern, cover insulation course by its exposure imaging being become the pattern of regulation, forming.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2006234136 | 2006-08-30 | ||
| JP2006234136 | 2006-08-30 | ||
| JP2007180838 | 2007-07-10 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101872124A (en) * | 2009-04-27 | 2010-10-27 | 日东电工株式会社 | Photosensitive polymer combination, use the method for making of its flexible circuit board and this circuit substrate |
| CN101995772A (en) * | 2009-08-07 | 2011-03-30 | 日东电工株式会社 | Photosensitive resin composition, flexible circuit board employing the same, and circuit board production method |
-
2007
- 2007-08-29 CN CN 200710148536 patent/CN101377620A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101872124A (en) * | 2009-04-27 | 2010-10-27 | 日东电工株式会社 | Photosensitive polymer combination, use the method for making of its flexible circuit board and this circuit substrate |
| CN101872124B (en) * | 2009-04-27 | 2013-07-10 | 日东电工株式会社 | Photosensitive resin composition, flexible circuit board employing the same, and circuit board production method |
| CN101995772A (en) * | 2009-08-07 | 2011-03-30 | 日东电工株式会社 | Photosensitive resin composition, flexible circuit board employing the same, and circuit board production method |
| CN101995772B (en) * | 2009-08-07 | 2013-02-27 | 日东电工株式会社 | Photosensitive resin composition, flexible circuit board employing the same, and circuit board production method |
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