CN105504677A - Dry film, cured product and printed wiring board - Google Patents

Abstract

The invention provides a dry film, a cured product and a printed wiring board, and specifically relates to a dry film with a resin layer, the dry film has good heat resistance and low warping degree of the cured product, and has excellent crack resistance, the stripping performance of the dry film with a carrier film is excellent, and fracture and power dropping are restrained. The invention also relates to a printed wiring board provided with a cured product obtained by curing the dry film. The dry film is characterized by comprising a resin layer which includes a thermosetting resin component; at least one of a curing agent and a curing accelerator; a maleimide compound; and at least two fillers. The boiling points of the least two fillers are all more than 100 DEG C, and the difference between any two boiling points is more than 5 DEG C.

Description

Dry film, cured article and printed circuit board (PCB)

Technical field

The present invention relates to dry film, cured article and printed circuit board (PCB), specifically, relate to thermotolerance, low warpage properties and the resistance to anti-thread breakage excellence with cured article and excellent with the separability of carrier film, inhibit break and dry linting resin layer dry film, the resin layer of this dry film is solidified and the cured article that obtains and the printed circuit board (PCB) possessing this cured article.

Background technology

In recent years, as the manufacture method of multilayer printed circuit board, the manufacturing technology that the conductor layer of inner layer circuit board is alternately piled up the lamination mode of resin insulating barrier and conductor layer receives publicity.Such as, the manufacturing process of following multilayer printed circuit board is proposed: epoxy resin coating composition on the inner layer circuit board being formed with circuit, after being heating and curing, utilize coarse agent to form concavo-convex uneven surface on surface, form conductor layer (with reference to patent documentation 1 and patent documentation 2) by plating.In addition, propose the manufacturing process of following multilayer printed circuit board: be formed with the adhesive sheet of inner layer circuit board upper strata pressure ring epoxy resin composition of circuit, be heating and curing, then utilize coarse agent to form concavo-convex uneven surface on surface, form conductor layer (with reference to patent documentation 3) by plating.

When limit is described with reference to the example of Fig. 1 limit to the formation method utilizing the Rotating fields of the multilayer printed circuit board of existing lamination method, first, inner conductor pattern 3 and resin insulating barrier 4 is pre-formed on the two sides of insulated substrate 1, outer contact pattern 8 is formed on the two sides of resultant layer laminated substrate X, the resin combination of the insulativity such as composition epoxy resin is set by coating etc. thereon, make it be heating and curing, thus form resin insulating barrier 9.Then, through hole hole 21 etc. is suitably set, then forms conductor layer on the surface of resin insulating barrier 9 by electroless plating etc., on conductor layer, then conventionally form the circuit pattern of regulation, outermost layer conductive pattern 10 can be formed.

As in multilayer printed circuit board, the resin insulating barrier that is arranged at interlayer is (following, interlayer insulating film) one of formation method, as as described in aforementioned patent literature 3, use by carrying out thermofixation after the dry film lamination with resin layer thus the method formed, the hot curing resin compositions such as composition epoxy resin be coated withs and drying and obtaining by described resin layer on film.

Prior art document

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 7-304931 publication (claims)

Patent documentation 2: Japanese Unexamined Patent Publication 7-304933 publication (claims)

Patent documentation 3: Japanese Unexamined Patent Publication 2010-1403 publication (claims)

Summary of the invention

the problem that invention will solve

As one of compounding heat-curing resin composition in dry film, use liquid-state epoxy resin (such as, patent documentation 3).When comprising liquid-state epoxy resin, the excellent adhesion of dry film, does not break or dry linting.But, when comprising liquid-state epoxy resin, when carrier film being peeled off from resin layer, have that resin layer is attached to carrier film and part or all is stripped such problem.In addition, due to containing liquid-state epoxy resin, the second-order transition temperature (Tg) of cured article declines, and therefore there is the problem that cannot obtain sufficient thermotolerance.In addition, also exist and produce the such problem of warpage when actual installation.

And then with the high performance of electronics, the requirement for the long-term reliability of printed circuit board (PCB) improves further, require the dry film with the resin layer of the cured article that can form resistance to anti-thread breakage excellence.

Therefore, the object of the invention is to, provide a kind of there is cured article thermotolerance, low warpage properties and resistance to anti-thread breakage excellence and excellent with the separability of carrier film, inhibit break and dry linting resin layer dry film, the resin layer of this dry film is solidified and the cured article that obtains and the printed circuit board (PCB) possessing this cured article.

for the scheme of dealing with problems

The present inventor etc. conduct in-depth research in view of the foregoing, found that: be more than 100 DEG C by compounding maleimide compound and boiling point and the different 2 kinds of solvents of boiling point, can solve aforementioned problems, thus complete the present invention.

That is, the feature of dry film of the present invention is, it has resin layer, and described resin layer contains: heat-curing resin composition; Solidifying agent and curing catalyst at least any one; Maleimide compound; Filler; At least 2 kinds of solvents, the boiling point of aforementioned at least 2 kinds of solvents is more than 100 DEG C, and boiling point differs more than 5 DEG C.

For dry film of the present invention, preferably, to comprise the resin layer total amount of the dry film of aforementioned solvents for benchmark, the ratio of the residual content of aforementioned solvents is less than 0.1 ~ 4 % by weight.

For dry film of the present invention, preferably, aforementioned at least 2 kinds of solvents are at least 2 kinds in the group that forms of aromatic hydrocarbons that to be selected from by DMF, toluene, methoxypropanol, methyl iso-butyl ketone (MIBK), pimelinketone and carbon number be more than 8.

For dry film of the present invention, preferably, aforementioned curing agent comprises at least a kind in resol, cyanate ester resin and the active ester resin with triazine structure.

For dry film of the present invention, preferably, it contains epoxy compounds as aforementioned hot curable resin composition.

For dry film of the present invention, preferably, it is for the manufacture of printed circuit board (PCB).

The feature of cured article of the present invention is, the solidification of the resin layer of aforementioned dry film obtains by it.

The feature of printed circuit board (PCB) of the present invention is, it possesses said curing thing.

the effect of invention

According to the present invention, thermotolerance, low warpage properties and the resistance to anti-thread breakage excellence with cured article can be provided and excellent with the separability of carrier film, inhibit break and dry linting resin layer dry film, the resin layer of this dry film is solidified and the cured article that obtains and the printed circuit board (PCB) possessing this cured article.

Accompanying drawing explanation

Fig. 1 is the partial cross section figure of the concise and to the point formation that the multilayer printed circuit board utilizing existing lamination method to make is shown.

Fig. 2 is the schematic side view that 2 test tubes used are shown during the liquid state of epoxy resin judges.

description of reference numerals

1 insulated substrate

3 inner conductor patterns

3a connection section

4,9 resin insulating barriers

8 outer contact patterns

10 outermost layer conductive patterns

20 through holes

21 through hole holes

22 connection sections

The liquid judgement test tube of 30a

30b temperature measuring test tube

31 graticules (A line)

32 graticules (B line)

33a, 33b rubber plug

34 thermometers

X multilayer board

Embodiment

Dry film of the present invention is the dry film with resin layer, and described resin layer contains: heat-curing resin composition; Solidifying agent and curing catalyst at least any one; Filler; Maleimide compound; At least 2 kinds of solvents, the boiling point of aforementioned at least 2 kinds of solvents is more than 100 DEG C, and boiling point differs more than 5 DEG C.Boiling-point difference is such as 5 ~ 130 DEG C.

If only use boiling point lower than the solvent of 100 DEG C, then the resin layer of dry film is too dry, and flexibility is poor, breaks or dry linting.

On the other hand, though when only using a kind of boiling point to be the solvent of more than 100 DEG C, use be 2 kinds but the difference of boiling point is less than the solvent of 5 DEG C time, even if carry out dry solvent also excessive residual, therefore peel off carrier film time, resin layer is also stripped, so separability is poor.And then, easily produce bubble, be difficult to form smooth resin layer.In addition, when wanting reduce residual solvents and at high temperature carry out drying, although drying process carries out, thermofixation is also excessively carried out.

But, be more than 100 DEG C by compounding boiling point and boiling point differs 2 kinds of solvents of more than 5 DEG C, can obtain having excellent with the separability of carrier film, inhibit and break and the dry film of resin layer of dry linting.

In addition, dry film of the present invention by resin layer containing maleimide compound, thus the flexibility with dry film obtains maintaining and the second-order transition temperature of cured article (Tg) is high, the resin layer of thermotolerance and resistance to anti-thread breakage also excellence.And then the warpage of the substrate that the cured article of this resin layer produces when the installation of semi-conductor chip is few, low warpage properties is also excellent.That is, the warpage during high temperature such when the installation of semi-conductor chip can be reduced.

Below, each composition for the resin layer of dry film of the present invention is described.

[heat-curing resin composition]

The resin layer of dry film of the present invention contains heat-curing resin composition.Heat-curing resin composition has the resin that can produce the functional group of curing reaction because of heat.Heat-curing resin composition is not particularly limited, compound, the i.e. episulfide resin etc. in epoxy compounds, multifunctional oxetane compound, molecule with more than 2 thioether groups can be used.

Above-mentioned epoxy compounds is the compound with epoxy group(ing), can use existing known any epoxy compounds.Can enumerate: there is in molecule the multi-functional epoxy compound etc. in 2 functionality epoxy compoundss of 2 epoxy group(ing), molecule with multiple epoxy group(ing).It should be noted that, also can be 2 functional epoxide compound through hydrogenation.

As epoxy compounds, such as can use: bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-A epoxy resin, brominated bisphenol a type epoxy resin, bisphenol-s epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, the phenolic resin varnish type epoxy resin of dihydroxyphenyl propane, biphenyl type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene-type epoxy resin, triphenylmethane type epoxy resin, alicyclic epoxy resin, aliphatics chain epoxy resin, phosphorous epoxy resin, anthracene type epoxy resin, norbornene-type epoxy resin, diamantane type epoxy resin, fluorenes type epoxy resin, amino-benzene phenol-type epoxy resin, amino first phenol-type epoxy resin, alkylbenzene phenol-type epoxy resin etc.These epoxy resin can be used alone a kind or combine two or more use.

Epoxy compounds can be solid epoxy resin, semi-solid state epoxy resin, liquid-state epoxy resin any one.In this specification sheets, solid epoxy resin refers at 40 DEG C to be the epoxy resin of solid state, and semi-solid state epoxy resin to refer at 20 DEG C as solid state, is liquid epoxy resin at 40 DEG C, and liquid-state epoxy resin refers at 20 DEG C to be liquid epoxy resin.

Liquid judgement makes " the liquid confirmation method " of the attached sheet the 2nd of (Heisei autonomous province in the first year makes No. 1) to carry out according to the province of the test and proterties that relate to hazardous product.

(1) device

Water Tank with Temp.-controlled:

Use possesses stirrer, well heater, thermometer, automatic temperature regulator (can with ± 0.1 DEG C of control temperature) and the degree of depth is the tank of more than 150mm.

It should be noted that, the judgement of the epoxy resin used in embodiment described later all uses YamatoScientificCo., Ltd. the Low Constant Temperature Water Baths (model BU300) manufactured and the combination of Constant Temperature Devices Thermo-Mate (model BF500), about 22 liters of tap water are joined in Low Constant Temperature Water Baths (model BU300), connect the power supply of the Thermo-Mate (model BF500) be mounted thereon, be set as design temperature (20 DEG C or 40 DEG C), with Thermo-Mate (model BF500) by water temperature inching to design temperature ± 0.1 DEG C, as long as but for the device of same adjustment can be carried out, just can use arbitrarily.

Test tube:

As test tube, as shown in Figure 2, use: liquid judgement test tube 30a and temperature measuring test tube 30b, describedly liquidly judge that test tube 30a is as internal diameter 30mm, the test tube of the flat round tube type transparent glass of high 120mm, the place that 55mm and 85mm is high at the bottom of distance pipe marks graticule 31 respectively, 32, by airtight for the mouth rubber plug 33a of test tube, described temperature measuring test tube 30b with liquid judge test tube 30a as same size and in the same manner as mark graticule, utilize central authorities have for inserting/the rubber plug 33b in the hole of support temperature meter is by airtight for the mouth of test tube, thermometer 34 is inserted in rubber plug 33b.Below, graticule high for 55mm at the bottom of distance pipe is called the graticule that at the bottom of " A line ", distance pipe, 85mm is high to be called " B line ".

As thermometer 34, " " thermometer (SOP-58 scale range 20 ~ 50 DEG C) of the cold test of middle regulation, as long as but can measure the device of the temperature range of 0 ~ 50 DEG C for petroleum-type test glass thermometer to use JISB7410 (1982).

(2) the enforcement order tested

The sample placing more than 24 hours under the normal atmosphere of temperature 20 ± 5 DEG C is put in the temperature measuring test tube 30b shown in liquid state judgement test tube 30a and Fig. 2 (b) shown in Fig. 2 (a) respectively until A line.2 test tubes 30a, 30b are erectly rested in Low Constant Temperature Water Baths in undersurface mode with B line.Make the lower end of thermometer 30mm below A line.

Specimen temperature keeps this state 10 minutes after reaching design temperature ± 0.1 DEG C.After 10 minutes, taken out by liquid state judgement test tube 30a, flatly fell immediately on the testing table of level from Low Constant Temperature Water Baths, the front end measuring invisible spectro liquid level with stopwatch moves to time of B line and record from A line.For sample, be that situation within 90 seconds is judged to be liquid state, situation more than 90 seconds is judged to be solid state by the time measured at a set temperature.

As solid epoxy resin, can enumerate: the naphthalene type epoxy resin such as the NC-7000 (the multifunctional solid epoxy resin containing naphthalene skeleton) that the EXA4700 (4 officials' energy naphthalene type epoxy resin) that the HP-4700 (naphthalene type epoxy resin) that Dainippon Ink Chemicals manufactures, Dainippon Ink Chemicals manufacture, Nippon Kayaku K. K manufacture; The phenols such as EPPN-502H (trisphenol epoxy resin) that Nippon Kayaku K. K manufactures and the epoxide (triphen phenol-type epoxy resin) of condenses of aromatic aldehyde with phenolic hydroxyl group; The Dicyclopentadiene (DCPD) aralkyl-type epoxy resin such as the EPICLONHP-7200H (the multifunctional solid epoxy resin containing Dicyclopentadiene (DCPD) skeleton) that Dainippon Ink Chemicals manufactures; The biphenyl aralkyl-type epoxy resin such as the NC-3000H (the multifunctional solid epoxy resin containing biphenyl backbone) that Nippon Kayaku K. K manufactures; Biphenyl/the phenol novolak type epoxy resin such as the NC-3000L that Nippon Kayaku K. K manufactures; The phenolic resin varnish type epoxy resins such as the EOCN-104S that EPICLONN660, EPICLONN690 that Dainippon Ink Chemicals manufactures, Nippon Kayaku K. K manufacture; The biphenyl type epoxy resins such as the YX-4000 that Mitsubishi chemical Co., Ltd manufactures; The phosphorous epoxy resins such as the TX0712 that Nippon Steel & Sumitomo Metal Corporation manufactures; Three (2, the 3-epoxypropyl) isocyanuric acid esters etc. such as the TEPIC that Nissan Chemical Ind Ltd manufactures.

As semi-solid state epoxy resin, can enumerate: the bisphenol A type epoxy resins such as the ELA-134 that jER834, jER872 that the EPOTOHOTOYD-134 that the AralditeAER280 that EPICLON860, EPICLON900-IM that Dainippon Ink Chemicals manufactures, EPICLONEXA-4816, EPICLONEXA-4822, Asahi Kasei Corporation manufacture, Toto Kasei KK manufacture, japan epoxy resin Co., Ltd. manufacture, Sumitomo Chemical Company Ltd manufacture; Dainippon Ink Chemicals manufactures the naphthalene type epoxy resin such as EPICLONHP-4032; Dainippon Ink Chemicals manufactures the phenol novolak type epoxy resin etc. such as EPICLONN-740.

As liquid-state epoxy resin, can enumerate: bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol AF type epoxy resin, phenol novolak type epoxy resin, tert-butyl catechol type epoxy resin, glycidyl amine type epoxy resin, amino-benzene phenol-type epoxy resin, alicyclic epoxy resin etc.

As above-mentioned multifunctional oxetane compound, can enumerate: two [(3-methyl-3-oxetanylmethoxy methoxyl group) methyl] ether, two [(3-ethyl-3-oxetanylmethoxy methoxyl group) methyl] ether, 1, two [(3-methyl-3-oxetanylmethoxy methoxyl group) methyl] benzene of 4-, 1, two [(3-ethyl-3-oxetanylmethoxy methoxyl group) methyl] benzene of 4-, vinylformic acid (3-methyl-3-oxetanylmethoxy) methyl esters, vinylformic acid (3-ethyl-3-oxetanylmethoxy) methyl esters, methacrylic acid (3-methyl-3-oxetanylmethoxy) methyl esters, methacrylic acid (3-ethyl-3-oxetanylmethoxy) methyl esters, the multifunctional trimethylene oxide classes such as their oligopolymer or multipolymer, and oxa-cyclobutanol and the following etherate etc. with the resin of hydroxyl, described resin is novolac resin, poly-(4-Vinyl phenol), Cardo type bisphenols, calixarene kind, Resorcinol calixarene kind, or silsesquioxane etc.In addition, the multipolymer etc. of unsaturated monomer and (methyl) alkyl acrylate with trimethylene oxide ring can also be enumerated.

As above-mentioned episulfide resin, such as, can enumerate bisphenol A-type episulfide resin etc.In addition, also can use: utilize same synthetic method that the Sauerstoffatom of the epoxy group(ing) of epoxy resin is replaced into sulphur atom and the episulfide resin etc. obtained.

Heat-curing resin composition is preferably epoxy compounds.And then, in order to the high and cured article of resistance to anti-thread breakage excellence of second-order transition temperature (Tg) can be obtained, be preferably in solid epoxy resin and semi-solid state epoxy resin at least any one.Wherein, from the aspect of resin layer of physical properties excellent that can form flexibility excellence, cured article, semi-solid state epoxy resin is more preferably.As epoxy compounds, from viewpoints such as the desirable physical property of cured article, preferred fragrance family epoxy resin.Wherein, more preferably naphthalene type epoxy compounds, biphenyl type epoxy compound.It should be noted that, in this specification sheets, fragrant family epoxy resin refers to the epoxy resin in its molecule with aromatic nucleus skeleton.

Heat-curing resin composition can be used alone a kind or combinationally use two or more.The compounding amount of heat-curing resin composition, not comprise the resin layer total amount benchmark of the dry film of solvent, is preferably 10 ~ 50 % by weight, is more preferably 10 ~ 40 % by weight, more preferably 10 ~ 35 % by weight.In addition, about the compounding amount of liquid-state epoxy resin during compounding liquid-state epoxy resin, in order to make the operability such as the separability of carrier film become good, be preferably 0 ~ 45 % by weight relative to heat-curing resin ingredient weight, be more preferably 0 ~ 30 % by weight, be particularly preferably 0 ~ 5 % by weight.

[solidifying agent]

The resin layer of dry film of the present invention can contain solidifying agent.As solidifying agent, resol, poly carboxylic acid and acid anhydrides thereof, cyanate ester resin, active ester resin etc. can be enumerated.Solidifying agent can be used alone a kind or combine two or more use.

As above-mentioned resol, can be used alone a kind or combinationally use two or more following resin: polyphenylene oxide resin, phenol resol resins, alkylphenol novolac resin, bisphenol A novolac resin, dicyclopentadiene type phenol resin, Xylok type resol, terpene modified resol, cresols/naphthol resin, polyvinylphenol class, phenol/naphthol resin, there is the resol of biphenyl structural, there is the resol of naphthyl alcohol structure, there is the cresol novolac resin of triazine structure, there is the existing known resins such as the phenol resol resins of triazine structure.

In resol, the cresol novolac resin with triazine structure, the phenol resol resins etc. with triazine structure are had to the resol of triazine structure, because the second-order transition temperature (Tg) of the cured article of resin layer becomes better, therefore preferably.In addition, when use has the resol of triazine structure, improve further from the view point of the water-absorbent of the cured article of resin layer, preferably combination uses cresol novolac resin, dicyclopentadiene type phenol resin, phenol resol resins, has other solidifying agent such as other resol, cyanate ester resin, active ester resin such as the resol of biphenyl structural.

Above-mentioned poly carboxylic acid and acid anhydrides thereof are compound and the acid anhydrides thereof in a part with more than 2 carboxyls, such as, can enumerate the resin that (methyl) acrylic acid multipolymer, the multipolymer of maleic anhydride, the condenses of diprotic acid etc. and carboxylic acid terminal's imide resin etc. have carboxylic acid terminal.

Above-mentioned cyanate ester resin is the compound in a part with more than 2 cyanate ester based (-OCN).Cyanate ester resin can use existing known any resin.As cyanate ester resin, such as, can enumerate phenol novolak type cyanate ester resin, alkylphenol phenolic varnish type cyanate ester resin, dicyclopentadiene-type cyanate ester resin, bisphenol A cyanate ester resin, bisphenol-f type cyanate ester resin, bisphenol S type cyanate ester resin.In addition, can be the prepolymer of a part through triazine.For cyanate ester resin, become better and the cured article of the resin layer of water-absorbent excellence due to second-order transition temperature (Tg) can be obtained, therefore preferably.

Above-mentioned active ester resin is the resin in a part with more than 2 active ester groups.Active ester resin can be obtained by the condensation reaction of carboxylic acid cpd and oxy-compound usually.Wherein, as oxy-compound, preferably use the active ester resin that oxybenzene compound or naphthol compound obtain.As oxybenzene compound or naphthol compound, can enumerate: Resorcinol, Resorcinol, dihydroxyphenyl propane, Bisphenol F, bisphenol S, phenolphthalin, the dihydroxyphenyl propane that methylates, the Bisphenol F that methylates, the bisphenol S that methylates, phenol, ortho-cresol, meta-cresol, p-cresol, pyrocatechol, naphthyl alcohol, 2-Naphthol, 1,5-dihydroxy naphthlene, 1,6-dihydroxy naphthlene, 2,6-dihydroxy naphthlenes, dihydroxy benaophenonel, trihydroxybenzophenone, tetrahydroxybenzophenone, Phloroglucinol, benzene triol, dicyclopentadienyl biphenol, phenol novolacs etc.For active ester resin, become better and the cured article of the resin layer of water-absorbent excellence due to second-order transition temperature (Tg) can be obtained, therefore preferably.

In addition, as solidifying agent, ester ring type olefin polymer can be used.As the concrete example of the manufacture method of ester ring type olefin polymer, following method can be enumerated: (1) will have carboxyl and/or acid anhydride (hereinafter referred to as " method that the ester ring type alkene of carboxyl etc. ") is polymerized together with other monomers as required; (2) aromatic olefin with carboxyl etc. is polymerized together with other monomers as required, the aromatic moiety of (being total to) polymkeric substance obtained is carried out to the method for hydrogenation; (3) by the ester ring type alkene without carboxyl etc. and the method for monomer copolymerization with carboxyl etc.; (4) by not there is the aromatic olefin of carboxyl etc. and there is the monomer copolymerization of carboxyl etc., the aromatic moiety of the multipolymer obtained is carried out to the method for hydrogenation; (5) in the ester ring type olefin polymer without carboxyl etc., the method with the compound of carboxyl etc. is imported by modified-reaction; Or (6) by the carboxylic acid ester groups with the ester ring type olefin polymer of carboxylic acid ester groups obtained as aforementioned (1) ~ (5) by the method etc. being converted into carboxyl such as being such as hydrolyzed.

In solidifying agent, preferred resol, cyanate ester resin, active ester resin, ester ring type olefin polymer, more preferably have the resol of triazine structure, cyanate ester resin, active ester resin.

Solidifying agent can combine two or more.Such as can by cyanate ester resin and active ester resin combination, also can by cyanate ester resin, active ester resin and phenolic resin composition.By combination resol, the adaptation with circuit can be improved.

For above-mentioned solidifying agent, preferably carry out compounding with following ratio: the epoxy group(ing) etc. of heat-curing resin composition can carry out the functional group of thermofixation reaction, with and this functional group reactions solidifying agent in the ratio of functional group be functional group's (equivalence ratio)=0.2 ~ 2 of functional group/can the carry out thermofixation reaction of solidifying agent.By being set in above-mentioned scope by functional group's (equivalence ratio) of the functional group of solidifying agent/can carry out thermofixation reaction, the roughening of the film surface in de-smear operation can be prevented.More preferably functional group's (equivalence ratio)=0.2 ~ 1.5 of functional group/can the carry out thermofixation reaction of solidifying agent, functional group's (equivalence ratio)=0.3 ~ 1.0 of the functional group of further preferred consolidation agent/can carry out thermofixation reaction.

[maleimide compound]

The resin layer of dry film of the present invention contains maleimide compound.Maleimide compound is the compound with maleimide skeleton, can use existing known any maleimide compound.Maleimide compound preferably has more than 2 maleimide skeletons, be more preferably N, N '-1, 3-penylene bismaleimides, N, N '-1, 4-penylene bismaleimides, N, N '-4, 4-ditan bismaleimides, 1, two (maleimide) ethane of 2-, 1, 6-bisinaleimidohexane, 1, 6-bismaleimides-(2, 2, 4-trimethylammonium) hexane, 2, 2 '-bis--[4-(4-maleimidephenoxy) phenyl] propane, 3, 3 '-dimethyl-5, 5 '-diethyl-4, 4 '-ditan bismaleimides, 4-methyl isophthalic acid, 3-penylene bismaleimides, two (3-ethyl-5-methyl-4-maleimide phenyl) methane, dihydroxyphenyl propane diphenyl ether bismaleimides, polyphenylene methane maleimide, and their oligopolymer, and have in the diamines condenses of maleimide skeleton at least any one.Aforementioned oligopolymer is by making the monomer in above-mentioned maleimide compound and maleimide compound condensation and the oligopolymer obtained.Maleimide compound can be used alone a kind or combinationally use two or more.

In maleimide compound, more preferably in the condenses of phenylmethane maleimide and bismaleimide amine oligomer at least any one.Above-mentioned bismaleimide amine oligomer is preferably by the condensation of phenylmethane bismaleimides and 4,4-diaminodiphenyl-methane and the oligopolymer obtained.As the commercially available product of the condenses of phenylmethane maleimide, the large BMI-2300 etc. with changing into Co., Ltd.'s manufacture can be enumerated.In addition, as the commercially available product of bismaleimide amine oligomer, the large DAIMAID-100H etc. with changing into Co., Ltd.'s manufacture can be enumerated.

In addition, maleimide compound is preferably the maleimide compound shown in following general formula (I).

In above-mentioned general formula (I), R ¹~ R ³separately represent hydrogen atom, halogen atom or organic group, n represents the integer of 0 ~ 1.In above-mentioned general formula (I), R ¹~ R ³be preferably hydrogen atom.

Above-mentioned maleimide compound is preferably the mixture of the maleimide compound shown in above-mentioned general formula (I).In addition, high and the linear expansivity of the cured article of resin layer becomes lower from the viewpoint of the solvability of this mixture, therefore, the mean value of the n in the above-mentioned general formula (I) of this mixture is more preferably 0.1 ~ 1.The mean value of n is larger, and the solvability of this mixture becomes higher.When the mean value of n is the mixture of the maleimide compound of 0.1 ~ 1, even if make the resin layer thermofixation of dry film at low temperatures, also can form the cured article that second-order transition temperature (Tg) is high, also can use the thin base material that thermotolerance is low.

Not comprise the resin layer total amount of the dry film of solvent and filler for benchmark, the compounding amount of maleimide compound is preferably 2 ~ 50 % by weight.When being more than 2 % by weight, the linear expansivity step-down of cured article, the second-order transition temperature (Tg) of cured article becomes higher in addition.Be more preferably more than 10 % by weight.In addition, when being below 50 % by weight, breaking tenacity uprises.

[filler]

The resin layer of dry film of the present invention contains filler.By containing filler, make hot strength consistent with the conductor layer of the copper be positioned at around insulation layer etc., thus the thermal property of dry film can be improved.As filler, existing known whole inorganic filler and organic filler can be used, be not limited to predetermined substance, but the preferred mineral filler suppressing the cure shrinkage of film, be conducive to improving the characteristic such as adaptation, hardness.As mineral filler, such as, can enumerate: the pigment extenders such as barium sulfate, barium titanate, soft silica, crystallinity silicon-dioxide, fused silica, spherical silicon dioxide, talcum, clay, magnesiumcarbonate, calcium carbonate, aluminum oxide, aluminium hydroxide, silicon nitride, aluminium nitride; The metal-powders such as copper, tin, zinc, nickel, silver, palladium, aluminium, iron, cobalt, gold, platinum.In these mineral fillers, be preferably difficult to be roughened silicon-dioxide, barium sulfate that liquid corrodes, little from proportion especially, in the composition can, aspect that low heat expansion property excellent compounding with height ratio, preferred spherical silicon dioxide.

As filler, also can be average line coefficient of thermal expansion between 30 DEG C to 150 DEG C the be filler of less than 300ppb/ DEG C.As the concrete example of such filler, the average line coefficient of thermal expansion can enumerated between 30 DEG C to 150 DEG C be less than 300ppb/ DEG C, glass filler, zirconium phosphate system filler, trichroite system filler, silicon oxidation system filler, tungsten wire array system filler and the manganese nitride system filler etc. of titanium doped type etc.As the commercially available product of titanium doped type glass filler, can enumerate " AZ filler " that Asahi Glass Co., Ltd manufactures, as the commercially available product of zirconium phosphate system filler, can enumerate " ZWP " that KCMCorporation Co., Ltd. manufactures, as the commercially available product of broken shape glass filler, " DL7400 " of Nippon Electric Glass Co., Ltd's manufacture etc. can be enumerated.

In addition, as filler, the filler that thermal expansivity is negative value can be used.As such filler, such as, can enumerate zirconium phosphate (the ULTRA series that Toagosei Co., Ltd manufactures), phosphoric acid tungsten wire array (Zr ₂(WO ₄) (PO ₄) ₂, ZWP), LaCu ₃fe ₄o ₁₂(A position ordered-form perovskite structure oxide, with reference to Japan's table 2010/101153 publication again), Bi _1-xln _xniO ₃(Ln=La, Nd, Eu, Dy, perovskite structure oxide), Al ₂o ₃tiO ₂(Lotek that AGCCERAMICSCo., Ltd. manufacture), Li ₂oAl ₂o ₃nSiO ₂beta spodumene sosoloid (NEOCERAM that Nippon Electric Glass Co., Ltd manufactures), Faujasite zeolite (faujasite; Na, Ca _0.5, Mg _0.5, K) _x[Al _xsi _12-xo ₂₄] 16H ₂o), LiAlSiO ₄, PbTiO ₃, Sc ₂w ₃o ₁₂, Lu ₂w ₃o ₁₂, ZrW ₂o ₈, Mn ₃xN (X=Cu-Sn, Zn-Sn etc.) etc.

The median size of filler be preferably less than 3 μm, more preferably less than 1 μm be desirable.It should be noted that, median size can utilize laser diffraction formula particle size distribution analyzer to obtain.

Not comprise the resin layer total amount of the dry film of solvent for benchmark, the compounding amount of filler is preferably 1 ~ 90 % by weight, is more preferably 10 ~ 90 % by weight, and more preferably 30 ~ 80 % by weight.When the compounding amount of filler is more than 1 % by weight, can suppress thermal expansion, improve thermotolerance, on the other hand, when being below 90 % by weight, the hardness of cured article improves, and can suppress the generation of crackle further.

In addition, not comprise the resin layer total amount of the dry film of solvent for benchmark, when the compounding amount of filler is more than 60 % by weight, although containing maleimide compound, the low cured article of water-absorbent also can be obtained.So by improving the compounding amount of filler, linear expansivity is low, and the suppression that the warpage of second-order transition temperature (Tg), substrate reduces and crackle produces becomes better.Be more preferably 60 ~ 90 % by weight, more preferably 60 ~ 80 % by weight.

[solvent]

The resin layer of dry film of the present invention contains boiling point and is more than 100 DEG C and boiling point differs 2 kinds of solvents of more than 5 DEG C.Aforementioned solvents is not particularly limited, and boiling point can be used to be the existing known solvent of more than 100 DEG C.In the present invention, when the boiling point of solvent has an amplitude, initial boiling point ~ terminal during distillation is set to boiling point.

As the solvent that boiling point is more than 100 DEG C, can enumerate: the methoxypropanol such as isobutyl alcohol, toluene, methyl iso-butyl ketone (MIBK), propyl carbinol, butylacetate, 2-methoxypropanol, isobutyl acetate, zellon, ethylene glycol monomethyl ether, methyl butyl ketone, primary isoamyl alcohol, ethylene glycol monomethyl ether, DMF (DMF), ethylene glycol monomethyl ether acetate, turps, pimelinketone, ethylene glycol monobutyl ether, gamma-butyrolactone etc.

In addition, as the solvent that boiling point is more than 100 DEG C, can enumerate: dimethylbenzene, petroleum petroleum naphtha, the Swasol1000 (carbon number 8 ~ 10: high boiling point aromatic hydrocarbons) that Maruzen Petrochemical Co., Ltd. manufactures, Swasol1500 (high boiling point aromatic hydrocarbons), StandardSekiyuOsakaHatsubaishoCO., LTD. the Solvesso100 (carbon number 9 ~ 10: high boiling point aromatic hydrocarbons) manufactured, Solvesso150 (carbon number 10 ~ 11: high boiling point aromatic hydrocarbons), the Solvent#100 that three common KCCs manufacture, Solvent#150, ShellChemicalsJapanLtd. the ShellsolA100 manufactured, ShellsolA150, No. Ipzole100 (aromatic hydrocarbons of carbon number 9 is main component) that Idemitsu Kosen Co., Ltd. manufactures, No. Ipzole150 (aromatic hydrocarbons of carbon number 10 is main component) etc.The aromatic component of high boiling point aromatic hydrocarbons preferably containing 99 more than capacity %.In addition, for high boiling point aromatic hydrocarbons, preferred benzene, toluene and dimethylbenzene are less than 0.01 capacity % respectively.

The resin layer of dry film of the present invention can be the solvent more than 3 kinds of more than 100 DEG C containing boiling point, in this case, as long as the boiling point of any 2 kinds of solvents is different.Boiling point is in the solvent of more than 100 DEG C, and preferred boiling point is the solvent of 100 ~ 230 DEG C, more preferably the solvent of 100 ~ 220 DEG C.When boiling point is below 230 DEG C, after thermofixation or anneal, solvent is difficult to residue in the resin layer of dry film.Solvent more preferably toluene, DMF, methoxypropanol, methyl iso-butyl ketone (MIBK), pimelinketone, petroleum petroleum naphtha, carbon number is the aromatic hydrocarbons of more than 8.Wherein, the more preferably combination of toluene and hexanaphthene, toluene and the combination of methyl iso-butyl ketone (MIBK) and the combination of pimelinketone and methyl iso-butyl ketone (MIBK).

Relative to resin layer 100 weight part of dry film not comprising solvent, the compounding amount of the solvent before drying is preferably 10 ~ 150 weight parts, is more preferably 25 ~ 100 weight parts.When the compounding amount of solvent is more than 10 weight parts, solvability improves, and the adjustment of the amount of residual solvent becomes easy, and on the other hand, when being below 150 weight parts, the control of the thickness of resin layer becomes easy.

To wrap the resin layer total amount of solvent-laden dry film for benchmark, the ratio of the residual content of the compounding amount of dried solvent, i.e. solvent is preferably 0.1 ~ 4 % by weight, is more preferably 0.3 ~ 3 % by weight.

The resin layer of dry film of the present invention can containing the solvent of boiling point lower than 100 DEG C.As the solvent of boiling point lower than 100 DEG C, can enumerate: Anaesthetie Ether, dithiocarbonic anhydride, acetone, chloroform, methyl alcohol, normal hexane, ethyl acetate, 1,1,1-trichloroethane, tetracol phenixin, methyl ethyl ketone, isopropyl alcohol, trieline, isopropyl acetate etc.

(macromolecule resin)

In order to the resistance to anti-thread breakage of cured article of the flexibility of dry film and the resin layer of dry film becomes good, the resin layer of dry film of the present invention is preferably containing macromolecule resin.As macromolecule resin, preferably use following thermoplastic resin and rubber-like particles.

(thermoplastic resin)

In order to improve the physical strength of the solidification tunicle obtained further, the resin layer of dry film of the present invention can also contain thermoplastic resin.Thermoplastic resin preferably dissolves in solvent.When dissolving in solvent, the flexibility of dry film improves, the generation that can suppress to break, dry linting.

As thermoplastic resin, the various acid anhydrides of hydroxyl in the hydroxy ethers portion existed in the condenses of thermoplasticity polyhydroxy polyether resin, epoxy chloropropane and various 2 trifunctional phenol compounds and phenoxy resin or its skeleton can be enumerated, phenoxy resin, polyvinyl acetal resin, polyamide resin, polyamide-imide resin, segmented copolymer etc. that acyl chlorides carries out esterification and obtains.Thermoplastic resin can be used alone a kind or combine two or more use.

Polyvinyl acetal resin such as can by obtaining polyvinyl alcohol resin acetalation with aldehyde.As above-mentioned aldehyde, be not particularly limited, such as, can enumerate formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde etc.

As the concrete example of phenoxy resin, can enumerate: YX8100, YX6954, YL7213, YL7218 etc. that FX280, FX293 that Toto Kasei KK manufactures, Mitsubishi chemical Co., Ltd manufacture.As the concrete example of polyvinyl acetal resin, the S-LEKKS series that Sekisui Chemical Co., Ltd manufactures can be enumerated, as polyamide resin, the KS5000 series of Hitachi Chemical Co., Ltd.'s manufacture, the BP series of Nippon Kayaku K. K's manufacture can be enumerated, and then as polyamide-imide resin, the KS9000 series etc. that Hitachi Chemical Co., Ltd. manufactures can be enumerated.

When thermoplasticity polyhydroxy polyether resin has fluorene skeleton, there is high glass transition point and excellent heat resistance, therefore the low coefficient of thermal expansion caused by semi-solid state or solid epoxy resin is maintained, and maintain this glass transition point, gained curing overlay film balance has low coefficient of thermal expansion and high glass transition point well concurrently.

In addition, thermoplasticity polyhydroxy polyether resin has hydroxyl, therefore good adaptation is demonstrated to base material and conductor, and the curing overlay film obtained is difficult to be roughened agent erosion, but the roughening liquid of the form of the aqueous solution is easily impregnated into the interface of curing overlay film and filler, therefore due to roughened, the filler on curing overlay film surface easily comes off, and easily forms good uneven surface.

As thermoplastic resin, segmented copolymer can be used.Segmented copolymer refers to that the two or more polymkeric substance covalent linkage of different in kind is connected to form the multipolymer of the molecular structure of long-chain.

As segmented copolymer, preferred A-B-A type or A-B-A ' type segmented copolymer.In A-B-A type and A-B-A ' type segmented copolymer, preferably be made up of following polymer unit: the B of central authorities is soft segment, second-order transition temperature (Tg) is low, preferably lower than 0 DEG C, its outside two A or A ' be hard block, second-order transition temperature (Tg) is high, is preferably more than 0 DEG C.Second-order transition temperature (Tg) measures (DSC) by means of differential scanning calorimetry and measures.

In addition, in A-B-A type and A-B-A ' type segmented copolymer, the segmented copolymer that the polymer unit that polymer unit is formed, B is less than-20 DEG C by second-order transition temperature (Tg) that preferably A or A ' is more than 50 DEG C by Tg is further formed.

In addition, in A-B-A type and A-B-A ' type segmented copolymer, A or A ' is preferably high with the consistency of above-mentioned heat-curing resin composition, and B is preferably low with the consistency of above-mentioned heat-curing resin composition.Think by so making the block at two ends and substrata compatible, the block of central authorities and the inconsistent segmented copolymer of matrix, thus easily show specific structure in matrix.

In thermoplastic resin, preferred phenoxy resin, polyvinyl acetal resin, there is thermoplasticity polyhydroxy polyether resin, the segmented copolymer of fluorene skeleton.

For the compounding amount of thermoplastic resin, be 1 ~ 20 % by weight relative to the resin layer entirety not comprising solvent, be preferably the ratio of 1 ~ 10 % by weight.The compounding amount of thermoplastic resin, when above-mentioned scope is outer, is difficult to obtain uniform uneven surface state.

(rubber-like particles)

And then the resin layer of dry film of the present invention can contain rubber-like particles as required.As such rubber-like particles, can enumerate: polybutadiene rubber, polyisobutylene rubber, urethane-modified polybutadiene rubber, epoxide modified polybutadiene rubber, acrylonitrile modified polybutadiene rubber, carboxy-modified polybutadiene rubber, carried out acrylonitrile butadiene rubber and their cross-linked rubbery particle, the nucleocapsid type rubber particle etc. of modification with carboxyl or hydroxyl, can be used alone a kind or combinationally use two or more.These rubber-like particles in order to improve gained solidification tunicle flexibility or improve resistance to anti-thread breakage, maybe oxygenant can be utilized to carry out surface roughening process, to improve and the dhering strength of Copper Foil etc. adds.

The median size of rubber-like particles is preferably the scope of 0.005 ~ 1 μm, is more preferably the scope of 0.2 ~ 1 μm.The median size of the rubber-like particles in the present invention can use dynamic light scattering determination.Such as can measure as follows: utilize ultrasonic wave etc. to make rubber-like particles be scattered in suitable organic solvent equably, FPRA-1000 (Otsuka Electronics Co., Ltd. is used to manufacture), the size-grade distribution of rubber-like particles is made, using its median particle diameter as median size with weight basis.

The compounding amount of rubber-like particles is preferably 0.5 ~ 10 % by weight relative to the resin layer entirety not comprising solvent, and more preferably 1 ~ 5 % by weight.When more than 0.5 % by weight, can obtain resistance to anti-thread breakage, the dhering strength with conductive pattern etc. can be improved.When less than 10 % by weight, thermal expansivity (CTE) reduces, and second-order transition temperature (Tg) rises, and curing characteristics improves.

[curing catalyst]

The resin layer of dry film of the present invention can contain curing catalyst.Curing catalyst can promote that thermofixation is reacted, and uses to improve the characteristics such as adaptation, chemical proofing, thermotolerance further.As the concrete example of such curing catalyst, can enumerate: imidazole and its derivants; The guanidine amines such as methyl guanamines, benzoguanamine; The polyamines classes such as diaminodiphenyl-methane, mphenylenediamine, m-xylene diamine, diamino diphenyl sulfone, Dyhard RU 100, urea, urea derivative, trimeric cyanamide, polynary hydrazides; Their organic acid salt and/or epoxy adduct; The amine complex of boron trifluoride; The pyrrolotriazine derivatives classes such as ethyl diamino-s-triazine, 2,4-diamino-s-triazine, 2,4-diamino-6-xylyl-s-triazine; Trimethylamine, trolamine, N, N-dimethyl octyl amine, N-benzyl dimethyl amine, pyridine, N-methylmorpholine, six (N-methyl) trimeric cyanamide, 2, the amines such as 4,6-tri-(Dimethylaminophenol), tetramethyl guanidine, Metha Amino Phenon; The Polyphenols such as polyvinylphenol, polyvinylphenol bromide, phenol novolacs, alkylphenol phenolic varnish; The organic phosphine classes such as tributylphosphine, triphenylphosphine, three-2-cyano ethyl phosphines; Three normal-butyls (2,5-dihydroxy phenyl) phosphonium bromide, phosphonium hexadecanyl-3-butyl chloride phosphonium salt class; The quaternary ammonium salts such as benzyl trimethyl ammonium chloride, phenyl tributyl ammonium chloride; Aforementioned polybasic acids acid anhydride; The light cationic polymerisation catalysts such as phenylbenzene iodine a tetrafluoro borate, triphenylsulfonium hexafluoro antimonate, 2,4,6-triphenyl thio-pyrylium hexafluorophosphates; Phenylethylene-maleic anhydride resin; The organic multiple isocyanate such as reaction with same mole thing, tolylene diisocyanate, isophorone diisocyanate of phenyl isocyanate and dimethyl amine and the existing known curing catalyst such as reaction with same mole thing, metal catalyst of dimethyl amine.In curing catalyst, from the aspect that can obtain BHAST patience, excellently select phosphonium salt class.

Curing catalyst can be used alone a kind or mix two or more use.The use of curing catalyst not necessarily, but when wanting especially to promote solidification, preferably can use with the scope of 0.01 ~ 5 weight part relative to heat-curing resin composition 100 weight part.

When metal catalyst, relative to heat-curing resin composition 100 weight part, convert in metal, be preferably 10 ~ 550ppm, be preferably 25 ~ 200ppm.

(tinting material)

The resin layer of dry film of the present invention can contain tinting material.By containing tinting material, when dry film of the present invention is used for the formation on the top layers such as solder mask, the disguise of circuit etc. can be improved.As tinting material, the usual known tinting materials such as red, blue, green, yellow, white, black can be used, can be pigment, dyestuff, pigment any one.Specifically, mark can be enumerated and have Colour Index (C.I.; Dyeing man association can will (TheSocietyofDyersandColourists) distribution) tinting material of numbering.But, from the view point of minimizing carrying capacity of environment and the impact on human body, preferably not halogen-containing tinting material.

As red stain, monoazo system, tetrazo system, azo lake system, benzimidazolone Xi, perylene system, diketopyrrolo-pyrrole system, condensation azo system, anthraquinone system, quinacridone etc. can be enumerated.As blue colorant, have metal replace or without replace phthalocyanine system, anthraquinone system, there is the compound being categorized as pigment (Pigment) in pigment system.As green colourant, have equally metal replace or without replace phthalocyanine system, anthraquinone Xi, perylene system.As yellow colorants, monoazo system, tetrazo system, condensation azo system, benzimidazolone system, isoindolinone system, anthraquinone system etc. can be enumerated.As white color agents, the titanium oxide such as rutile-type, Detitanium-ore-type etc. can be enumerated.As black colorant, the pigment, moly-sulfide, bismuth sulfide etc. of the black system of titanium, carbon black system, graphite system, iron oxide, anthraquinone system, cobalt oxide system, cupric oxide system, manganese system, weisspiessglanz system, magnesium oxide-nickel series, perylene system, aniline system can be enumerated.In addition, for the object of adjustment tone, purple, the tinting material such as orange, dark brown can be added.

Tinting material can be used alone a kind or combinationally use two or more.The compounding amount of tinting material is not particularly limited, overall relative to the resin layer not comprising solvent, is preferably 0.1 ~ 10 % by weight, is more preferably 0.1 ~ 5 % by weight.

(other compositions)

The resin layer of dry film of the present invention can also use as required: the existing known thickening materials such as asbestos, Orben, Bentone, fine particle silica; The adaptation imparting agents such as the defoamers such as silicon-type, fluorine system, macromolecular and/or flow agent, thiazole system, triazole system, silane coupling agent; Fire retardant; The existing known additive kind of titanic acid ester system, aluminium system.

Dry film of the present invention can manufacture as follows: be coated with the hot curing resin composition for the formation of resin layer on a carrier film and drying, lamination protective film as required, form dry coating, can manufacture thus.Herein, heat-curable composition refer to containing heat-curing resin composition, solidifying agent and curing catalyst at least any one, the composition of maleimide compound, filler and at least 2 kinds of solvents, the boiling point of at least 2 kinds of solvents is more than 100 DEG C, and boiling point differs more than 5 DEG C.

As the material of carrier film, the tinsel etc. that polyester, polycarbonate, polyimide and the release papers such as polyolefine, polyethylene terephthalate, PEN such as polyethylene, polypropylene (PP), polyvinyl chloride, Copper Foil, aluminium foil are such can be enumerated.It should be noted that, delustring process, corona treatment can be implemented to carrier film, in addition can also implement demoulding process.The thickness of carrier film is preferably 8 ~ 60 μm.

As the material of protective membrane, the material same with the material used in carrier film can be used, be suitably PET or PP.The appropriate thickness of protective membrane is 5 ~ 50 μm.

Herein, as the coating process of hot curing resin composition, the known methods such as silk screen print method can be used.In addition, as volatile dry method, the known method using heated air circulation type drying oven etc. can be utilized.

In addition, printed circuit board (PCB) of the present invention possesses cured article dry film solidification of the present invention obtained.Below its manufacture method is described, but is not limited thereto.

About cured article of the present invention, after peeling off protective membrane from dry film of the present invention, dry film heated lamination of the present invention is integrally formed on the internal layer circuit substrate being formed with circuit.Then solidifying in an oven or utilizing hot plate to suppress makes it solidify, and obtains cured article of the present invention.

In above-mentioned operation, for the method that lamination or hot plate are suppressed, the micro concavo-convex caused by internal layer circuit disappears when heating and melting, keeps this state to be cured, and therefore, finally can obtain the multi-ply wood of flat surfaces state, therefore preferably.In addition, when lamination or hot plate compacting are carried out to the base material and dry film of the present invention that are formed with internal layer circuit, also can by Copper Foil or to be formed with the base material of circuit simultaneously stacked.

Hot curing resin composition is layered in after on circuit substrate, thermofixation is carried out to resin layer, insulation layer can be formed on circuit substrate thus.The condition of thermofixation is suitably selected according to the kind, content etc. of the resinous principle in resin layer, but preferably selects in the scope of 30 ~ 120 minutes at 20 ~ 180 minutes, more preferably 160 DEG C ~ 210 DEG C at 150 DEG C ~ 220 DEG C.In addition, by carrying out thermofixation with not peeling off carrier film, can prevent the impurity such as dirt, dust from adhering to.

The substrate so obtained utilizes CO ₂semiconductor laser or the drill bit perforates such as laser, UV-YAG laser.Hole can be following any one: the communicating pores (through hole) for the purpose of the surface making substrate and backside; Partial hole (applying shape via (conformalvia)) for the purpose of being connected with the interlayer of resin layer with by resin layer.The stripping of carrier film is before and after laser processing.When peeling off carrier film before laser processing, easily obtain the processing footpath as the design load of the mask diameters (aperture) of laser, and there is no carrier film, therefore, it is possible to low power carries out the processing of resin layer.On the other hand, when peeling off carrier film after laser machining, can suppress in the damage adding the fragment (resin fragmentation) produced man-hour, the resin layer surface caused by laser.

After perforate, in order to remove be present in hole inwall, the residue (smear) of bottom, performance and the anchoring effect of conductor layer (metal. plating layer formed afterwards), to form the uneven surface of micro concavo-convex shape on surface as object, carry out with commercially available de-smear liquid (coarse agent) or the roughening liquid containing oxygenants such as permanganate, dichromate, ozone, hydrogen peroxide/sulfuric acid, nitric acid simultaneously.Carry out glue slag under with the state of carrier film when removing, the damage of the resin layer surface caused by de-smear can be suppressed.

Then, eliminate the overlay film surface of the hole of residue, the cured article of generation micro concavo-convex shape uneven surface at formation de-smear liquid after, form circuit by the method for residues (subtractivemethod), semi-additive process (semi-additivemethod) etc.In any means, after implementing electroless plating or electrolysis plating or after two kinds of plating, in order to remove stress, the raising intensity of metal, the thermal treatment being called as annealing of about 10 ~ 60 minutes can be implemented at about 80 ~ 180 DEG C.

As metal deposition used herein, also copper, tin, solder, nickel etc. can be combinationally used without particular limitation.In addition, also plating used herein can be replaced with substitutes such as the sputterings of metal.

Dry film of the present invention can be suitable for the manufacture of printed circuit board (PCB).Particularly can be suitable for the formation of the permanent insulation layer of the printed circuit board (PCB)s such as interlayer insulating film, solder mask, tectum.The dry film of the application of the invention, stickup wiring, thus can running board be formed.In addition, the sealing resin as semi-conductor chip also can be applicable to using.

[embodiment]

Below, illustrate that embodiments of the invention, comparative example and test example are specifically described the present invention, but the present invention is not limited to following embodiment certainly.It should be noted that, " part " and " % " is as long as no being particularly limited to below, all refers to weight basis.

(embodiment 1 ~ 30 and comparative example 1 ~ 4)

Utilize the formula shown in following table 1 ~ 5 by compounding for each composition, mixing dispersion, be adjusted to viscosity 0.5 ~ 20dPas (rotational viscosimeter 5rpm, 25 DEG C).Then, bar coater is used with the thickness of dry film for the mode of latter 40 μm of drying coats carrier film (PET film; The Lumirror38R75 that Dongli Ltd. manufactures: thickness 38 μm).Then, use heated air circulation type drying oven to carry out drying, obtain the dry coating in one side with heat-curing resin layer.For drying conditions, under the time shown in table and temperature, carry out drying.Then, protective film is folded on the resin layer, obtains dry film.

[table 1]

[table 2]

[table 3]

[table 4]

[table 5]

﹡ 1: (Nippon Kayaku K. K manufactures biphenyl/phenol novolak type epoxy resin; Epoxy equivalent (weight) 280 ~ 290g/eq; Solid-state; Softening temperature 70 DEG C)

﹡ 2: (Dainippon Ink Chemicals manufactures naphthalene type epoxy resin; Epoxy equivalent (weight) 145 ~ 157g/eq; Semi-solid state)

﹡ 3: (Nippon Steel & Sumitomo Metal Corporation manufactures liquid BPA type BPF type epoxy resin; Epoxy equivalent (weight) 160 ~ 170g/eq; Liquid)

﹡ 4: (SABICInovativePlastics company manufactures PPO to polyphenylene oxide resin; Hydroxyl equivalent 850g/eq)

﹡ 5: phenol resol resins (bright and change into Co., Ltd. manufacture; Hydroxyl equivalent 104 ~ 108g/eq; Softening temperature 82 ~ 86 DEG C)

﹡ 6: containing biphenyl backbone phenol resol resins (bright and change into Co., Ltd. manufacture; Hydroxyl equivalent 201 ~ 220g/eq; Softening temperature 64 ~ 85 DEG C)

﹡ 7: containing cresol novolac resin (Dainippon Ink Chemicals's manufacture of triazine; Hydroxyl equivalent 151g/eq; Nitrogen content 18%)

﹡ 8: containing phenol resol resins (Dainippon Ink Chemicals's manufacture of triazine; Hydroxyl equivalent 125g/eq; Nitrogen content 12%)

﹡ 9: (Dainippon Ink Chemicals manufactures active ester resin; Active ester equivalent 223g/eq)

﹡ 10: (Dainippon Ink Chemicals manufactures active ester resin; Active ester equivalent 223g/eq; Softening temperature 152 DEG C)

﹡ 11: (LonzaJapan Co., Ltd. manufactures bisphenol A dicyanate; Cyanate equivalent 232g/eq)

﹡ 12: (LonzaJapan Co., Ltd. manufactures phenol novolak type multifunctional cyanate ester; Cyanate equivalent 124g/eq)

﹡ 13: (Daiwa Kasei Industry Co., Ltd. manufactures the condenses of phenylmethane maleimide; Softening temperature 70 ~ 145 DEG C)

﹡ 14:3, (Daiwa Kasei Industry Co., Ltd. manufactures 3 '-dimethyl-5,5 '-diethyl-4,4 '-ditan bismaleimides; Softening temperature 160 ~ 170 DEG C)

﹡ 15:2,2 '-bis--[4-(4-maleimidephenoxy) phenyl] propane (KIChemicalIndustryCo., Ltd. manufacture)

﹡ 16: (ADMATECHSCO., LTD. manufacture spherical silicon dioxide; Median size 0.5 μm)

﹡ 17:2-ethyl-4-methylimidazole (Shikoku Chem's manufacture)

﹡ 18: phosphonium salt (manufacture of Bei Xing Industry Co., Ltd)

﹡ 19:4-aminopyridine (Koei Chemical Co., Ltd.'s manufacture)

﹡ 20: (Wako Pure Chemical Industries, Ltd. manufactures zinc naphthenate (II) mineral turpentine; Zn content 8%)

﹡ 21: (Mitsubishi chemical Co., Ltd manufactures phenoxy resin; Second-order transition temperature 130 DEG C)

﹡ 22: (Sekisui Fine Chemical Co., Ltd. manufactures polyvinyl alcohol contracting acetyl acetaldehyde (polyvinylacetoacetal); Second-order transition temperature 107 DEG C)

﹡ 23: core shell rubber particles (AicaKogyoCompany manufacture)

﹡ 24: toluene (boiling point 110 DEG C)

﹡ 25: methyl iso-butyl ketone (MIBK) (boiling point 116 DEG C)

﹡ 26:2-methoxypropanol (boiling point 118 DEG C)

﹡ 27: pimelinketone (boiling point 150 DEG C)

﹡ 28:N, dinethylformamide (boiling point 153 DEG C)

﹡ 29:Ipzole150 (boiling point 184 ~ 205 DEG C)

﹡ 30: methyl ethyl ketone (boiling point 79.5 DEG C)

﹡ 31: hexane (boiling point 69 DEG C)

Utilize evaluation method shown below, the dry film of Evaluation operation example 1 ~ 30 and comparative example 1 ~ 4.Evaluation result is shown in table 6 ~ 10.

The mensuration > of the residual content (%) of the organic solvent in < dry film

After peeling off carrier film and protective membrane from the dry film of each embodiment and comparative example, gather the resin layer of about 1.2g, put into the container of band stopper, the quality (W) of the resin layer that precise gathers.In this container, the 3-ethoxyl ethyl propionate 1 as internal standard substance is added, this quality of precise (We) with transfer pipet.Then, add acetone 5ml by quantitative transfer pipet and cover stopper, fully vibrate container, and the resin layer of collection is dissolved.Then, with this liquid of metre filter in 0.5 μm, aperture, analyzed the composition of filtrate by vapor-phase chromatography (TRACEGCULTRA that ThermoFisherScientificK.K. manufactures), obtained the quality (Ws) of the organic solvent relative to internal standard substance 1g by the typical curve made separately.Calculated the residual content of organic solvent according to following formula by above-mentioned value.

Residual content (quality %)=(We × Ws/W) × 100 of organic solvent

In addition, by residual content, the easy degree adopting the adjustment of the residual content of the organic solvent in following metewand evaluation dry film.

It should be noted that, the condition determination in vapor-phase chromatography is as described below.At post: capillary column DB-1MS (30m × 0.25mm), detector: MS (ITQ900) that AgilentTechnologies company manufactures, carrier gas: helium, sampler temperature: 300 DEG C, detector temperature: 230 DEG C, column temperature condition: at initial temperature 50 DEG C, keep 2 minutes in 50 DEG C after sample injects, be warming up to 300 DEG C with 10 DEG C/min, keep 10 minutes after reaching 300 DEG C.

◎：0.3～2.5％

Zero: more than 2.5% and be less than 3.0%

More than △: 0.1% and be less than 0.3% or more than 3.0% and be less than 4.0%

×: except 0.1 ~ 4.0%

Flexibility (pliability test) > of < dry film

According to JISK5600-5-1 (ISO1519), use the round shape plug flexing machine that BYK-Gardner company manufactures, start to produce the minimum diameter of the plug broken and from the stripping of carrier film according to the dry film of each embodiment and comparative example, evaluate the flexibility of dry film.Metewand is as described below.When the flexibility of dry film is good, the flexibility of resin layer is high, can suppress to break and dry linting.

◎: under following diameter, there is no the stripping of the breaking of generation tree lipid layer, dry linting, carrier film.

Zero: be less than in the scope of 5mm more than 2mm, there is no the stripping of the breaking of generation tree lipid layer, dry linting, carrier film.

△: be less than in the scope of 5mm more than 2mm, the stripping of the breaking of generation tree lipid layer, dry linting and carrier film.

×: under above diameter, the stripping of the breaking of generation tree lipid layer, dry linting and carrier film.

< gas bubbles left >

After peeling off protective membrane from the dry film of each embodiment and comparative example; use intermittent vacuum pressure level press MVLP-500 (manufacture of Ming Ji Co., Ltd.), be laminated on the comb pattern of L (line: wiring width)/S (space: interval width)=100/100 μm with thick 35 μm of the conductor of copper.At 5kgf/cm ², 80 DEG C, 1 minute, carry out heated lamination, then, with hot plate press at 10kgf/cm under the condition of 1Torr ², flatten under the condition of 80 DEG C, 1 minute.After lamination, confirm that 20 places boundary member that is whether online and space enters air and in resin layer, produces hole (space).Metewand is as described below.When resin layer is clamminess, that is, when the separability difference of following carrier film, enter bubble between resin layer and comb pattern, space becomes many.In this situation, easily crack.

Zero: do not confirm space.

△: the space confirming 1 ~ 4 place.

×: the space confirming more than 5 places.

The separability > of < carrier film

Under the condition same with the test of above-mentioned gas bubbles left, after the dry film of each embodiment of lamination and comparative example, peel off carrier film, whether visual judgement is attached with the resin combination from resin layer on a carrier film.Metewand is as described below.

◎: do not adhere to resin combination on a carrier film, and the touch dry of resin surface is good.

Zero: do not adhere to resin combination on a carrier film.

△: be attached with a small amount of resin combination on a carrier film.

×: be attached with more resin combination on a carrier film.

The consistency > of < maleimide compound, epoxy resin and solvent

As described below, investigate the consistency between the epoxy resin of each embodiment and comparative example and maleimide compound solvability in a solvent and mutual resin.

By compounding for epoxy resin, maleimide compound and the solvent ratio respectively with identical with the ratio in table used in each embodiment and comparative example.Then, stirring heating at than the low-boiling temperature of each composition makes it dissolve.

After making the mixture heating for dissolving of resin and solvent, cooling, until room temperature, makes the film that 1mm is thick.Under 25 times, observe the film made from opticmicroscope, in the scope of 1cm × 1cm, confirm whether solids is separated out.

Zero: the big particle not observing more than 20 μm completely.

×: the big particle observing more than 1 more than 20 μm.

<DSC measures >

Peel off the protective membrane of the dry film of each embodiment and comparative example; cut lower 10mg resin layer; weigh in special aluminium dish, immediately SeikoInstrumentsInc. manufacture DSC-6200 in, be warming up to 300 DEG C with heat-up rate 5 DEG C/min from 30, carry out DSC mensuration for each sample.For each sample, schemed to confirm exothermic peak temperature by the DSC obtained.

Zero: all exothermic peak temperatures are all less than 190 DEG C.

△: the 1 exothermic peak is less than 190 DEG C, and the 2nd exothermic peak is more than 190 DEG C.

< second-order transition temperature (Tg) and thermal expansivity (CTE (α 1)) >

Protective membrane is peeled off from the dry film of previous embodiment and comparative example; at GTS-MP paper tinsel (FurukawaCircuitFoilCo.; Ltd. manufacture) glossy surface side (Copper Foil) on, utilize the method same with the method recorded in above-mentioned < gas bubbles left > be laminated on Copper Foil.Then, in heated air circulation type drying oven, at 220 DEG C, resin layer is made to solidify 60 minutes.About the composition not containing maleimide compound recorded in comparative example, at 180 DEG C, resin layer is made to solidify 60 minutes.Then, after peeling off cured article from Copper Foil, sample is cut into size up (size of 3mm × 10mm), is supplied in the TMA6100 that SeikoInstrumentsInc. manufactures.For TMA measure, under test increases the weight of 5g, by sample with the heat-up rate of 10 DEG C/min from room temperature, METHOD FOR CONTINUOUS DETERMINATION 2 times.The intersection point of 2 different for the thermal expansivity of the 2nd time tangent lines is set to second-order transition temperature (Tg), and the thermal expansivity (CTE (α 1)) as the region of below Tg is evaluated.Can say that Tg is higher, thermotolerance is higher.

The evaluation of second-order transition temperature (Tg)

◎ ◎: Tg is more than 250 DEG C.

◎: Tg is more than 220 DEG C and is less than 250 DEG C.

Zero: Tg is more than 200 DEG C and is less than 220 DEG C.

×: Tg is less than 200 DEG C.

The evaluation of thermal expansivity (CTE (α 1))

◎: be less than 15ppm.

Zero: more than 15ppm ~ be less than 20ppm.

The mensuration > of < water-intake rate

For the dry film of each embodiment and comparative example, the method same with the method recorded in above-mentioned < second-order transition temperature (Tg) and thermal expansivity (CTE (α 1)) > is adopted to be solidified by resin layer.Then, after peeling off cured article from Copper Foil, sample is cut into size up (size of 50mm × 50mm), at 100 DEG C, then carries out drying in 2 hours, remove moisture completely, carry out the mensuration of quality (W1) with precision balance.Then, sample be impregnated in the distilled water that management is 23 DEG C ± 2 DEG C, carry out the mensuration of the quality (W2) after 24 hours.Water-intake rate is obtained by (W2-W1)/W1 × 100 (%).

◎ ◎: be less than 0.3%.

More than ◎: 0.3% and be less than 0.7%.

More than zero: 0.7% and be less than 1.4%.

×: more than 1.4%.

The disguised > of < circuit

As circuit substrate, use the two sides copper-clad laminated board (MCL-E-679FGR, Hitachi Chemical Co., Ltd. manufacture) being formed with the 400mm × 300mm × thick 0.8mm of the conductive layer of thick 10 μm of copper, use treatment agent (CZ-8100+CL-8300, MECCo., LTD. manufacture) pre-treatment is implemented to it, form the profile (profile) being equivalent to copper etch quantity 1 μm.Implement on the copper-clad laminated board of pre-treatment at this, use intermittent vacuum pressure level press MVLP-500 (manufacture of Ming Ji Co., Ltd.), at 5kgf/cm ², 80 DEG C, 1 minute, under the condition of 1Torr, by the dry film lamination of each embodiment and comparative example on the copper of copper-clad laminated board.Then, peel off carrier film, heat in heated air circulation type drying oven, resin layer is solidified, forms cured film thus, make evaluation substrate.Now, about the composition comprising maleimide compound, solidify 60 minutes at 220 DEG C, about the composition not containing maleimide compound, solidify 60 minutes at 180 DEG C.Use each substrate for evaluation, by the variable color of visual confirmation from the copper circuit in cured film, the disguise for circuit is evaluated.

◎: unconfirmed to variable color.

Zero: confirm few variable color.

The warpage of < substrate evaluates >

As pre-treatment, use MECCo., LTD. the CZ-8101 manufactured, to total thickness be 100 μm, the copper-clad plate of the size of 200 × 200mm (copper of side is thick=20 μm, MCL-E-679FGR, Hitachi Chemical Co., Ltd.) be equivalent to the etching of 1 μm.Then, by the dry film lamination of embodiment, comparative example at the surface of copper-clad plate and the back side.Then, after peeling off carrier film, in heated air circulation type drying oven, resin layer is solidified, obtain the substrate on the surface of substrate and the back side with hot curing resin composition.Now, about the composition comprising maleimide compound, solidify 60 minutes at 220 DEG C, about the composition not containing maleimide compound, solidify 60 minutes at 180 DEG C.

Then, the CO of Via.Mechanics, Ltd. is used ₂laser machine: LC-2K212, forms the laser via in 65 μm, footpath, top, 50 μm, footpath, the end in the one side of substrate.The process zone of laser is 1 unit with 50 × 50mm, and one side is formed about 10,000 holes.Then, cleaning as laser via, uses AtotechCo., Ltd. the SAP liquid manufactured: SecuringanthSAP, carries out swelling 5 minutes at 60 DEG C, carries out process in 20 minutes with permanganic acid at 80 DEG C, carry out reduction treatment in 5 minutes at 40 DEG C, carry out cleaning at the bottom of through hole.Then, use the electroless nickel bath of commercially available product and chemical gilding bath, under nickel plating 0.5 μm, the condition of gold-plated 0.03 μm, carry out plating, to implementing gold-plated process bottom laser via.

The substrate obtained is cut into the process zone 50 × 50mm of laser via.Then, on the face defining through hole, live thousand metal Co., Ltd. manufacture thousand live tin ball (ECOSOLDERBALL) ( ), as gap holding material silica bead be configured in the installation region 20 × 20mm of virtual chip (TEG chip, size 20 × 20mm × 1mmt) in the mode forming uniform thickness.Installation region is set to the substantial middle of the substrate of 50 × 50mm.

Then, carry virtual chip in the region being configured with tin ball, at the surface temperature 260 DEG C of substrate, carry out 1 reflow treatment, obtain the substrate that warpage is evaluated.The evaluation method of warpage is as follows: by the substrate that the obtains diagonal lines precise cutting along 50 × 50mm, using the difference of maxima and minima in the cross section in diagonal lines region as amount of warpage.

◎: the amount of warpage of substrate is less than 100 μm.

Zero: the amount of warpage of substrate is more than 100 μm and is less than 200 μm.

×: the amount of warpage of substrate is more than 200 μm.

< cold cycling (suppression of crackle) >

Use intermittent vacuum pressure level press MVLP-500 (manufacture of Ming Ji Co., Ltd.), at 5kgf/cm ², 80 DEG C, 1 minute, under the condition of 1Torr, by the dry film lamination of each embodiment and comparative example on the copper of copper-clad laminated board.Afterwards, peel off carrier film, heat in heated air circulation type drying oven, resin layer is solidified.Now, about the composition comprising maleimide compound, solidify 60 minutes at 220 DEG C, about the composition not containing maleimide compound, solidify 60 minutes at 180 DEG C.

Then, CO is used ₂laser machine (HitachiVia.Mechanics, Ltd. manufacture), to push up 65 μm, footpath, the mode in 50 μm, footpath, the end carries out through hole formation.

Then, process successively according to the order of commercially available wet type permanganic acid de-smear (manufacture of ATOTECH company), electroless copper (THRU-CUPPEA, C. Uyemura & Co Ltd manufacture), copper electroplating process, copper plating treatment is implemented, to make to fill up throughhole portions on the resin layer with copper thickness 25 μm.Then, be cured in heated air circulation type drying oven, obtain through the completely crued test substrate implementing copper plating treatment.Will-65 DEG C at 30 minutes, 150 DEG C 30 minutes as 1 circulation, thermal history is applied to the test substrate obtained.After 2000 and 3000 circulations, in order to by the bottom of observation by light microscope through hole, the state of wall, cut through hole centre portions with precision gas cutting machine and grind, carrying out the observation of cross section state.Metewand is evaluated according to following.Observe via count and be set to 100 holes.

◎ ◎: 2000 circulation and 3000 circulations all do not have crackle to produce.

◎: 2000 circulations do not have crackle to produce.3000 circulation generation 1 places or 2 place's crackles.

Zero: 2000 circulation does not crack.3000 circulation generation 3 ~ 5 place crackles.

×: 2000 circulations crack.

[table 6]

[table 7]

[table 8]

[table 9]

[table 10]

﹡ 32: when peeling off carrier film after lamination, is attached with the resin deriving from resin layer in a large number on a carrier film, therefore cannot carry out testing of characteristic.

﹡ 33: dried dry film does not have flexibility, produces dry linting, breaks, therefore cannot test.

From the result shown in above-mentioned table 6 ~ 10, when the dry film of embodiment 1 ~ 30, the thermotolerance of cured article, low warpage properties and resistance to anti-thread breakage excellence can be obtained and excellent with the separability of carrier film, inhibit and break and the resin layer of dry linting.

On the other hand, although although for being containing solvent of more than two kinds but only the dry film of the comparative example 1 of the solvent of more than 100 DEG C containing a kind of boiling point and containing boiling point of more than two kinds and be the solvent of more than 100 DEG C but the dry film of the almost identical comparative example 3 of its boiling point, the separability of known carrier film is poor, during stripping carrier film, a large amount of resin layers is also stripped, therefore can not be durable as dry film.In addition, the resin layer of the dry film of comparative example 1,3 is clamminess, and produces gas bubbles left when being therefore laminated on base material.

As solvent, for the dry film being only less than the comparative example 2 of the solvent of 100 DEG C containing boiling point, although the separability of carrier film is excellent, resin layer does not have flexibility, produces and breaks and dry linting.

For the dry film of comparative example 4 not containing maleimide compound, the thermotolerance of cured article is low, resistance to anti-thread breakage also poor.In addition, the warpage of substrate is also large.

Claims (8)

1. a dry film, is characterized in that, it has resin layer, and described resin layer contains: heat-curing resin composition; Solidifying agent and curing catalyst at least any one; Maleimide compound; Filler; At least 2 kinds of solvents,

The boiling point of described at least 2 kinds of solvents is more than 100 DEG C, and boiling point differs more than 5 DEG C.

2. dry film according to claim 1, is characterized in that, to comprise the resin layer total amount of the dry film of described solvent for benchmark, the ratio of the residual content of described solvent is 0.1 ~ 4 % by weight.

3. dry film according to claim 1, it is characterized in that, described at least 2 kinds of solvents are at least 2 kinds in the group that forms of aromatic hydrocarbons that to be selected from by DMF, toluene, methoxypropanol, methyl iso-butyl ketone (MIBK), pimelinketone and carbon number be more than 8.

4. dry film according to claim 1, is characterized in that, described solidifying agent comprises at least a kind in resol, cyanate ester resin and the active ester resin with triazine structure.

5. dry film according to claim 1, is characterized in that, it contains epoxy compounds as described heat-curing resin composition.

6. the dry film according to any one in Claims 1 to 5, is characterized in that, it is for the manufacture of printed circuit board (PCB).

7. a cured article, is characterized in that, the solidification of the resin layer of the dry film described in any one in claim 1 ~ 6 obtains by it.

8. a printed circuit board (PCB), is characterized in that, it possesses cured article according to claim 7.