CN109070573A

CN109070573A - The manufacturing method of laminated body and the manufacturing method of distributing board

Info

Publication number: CN109070573A
Application number: CN201680084120.1A
Authority: CN
Inventors: 森田正树; 中村小夏; 井上康雄; 吉江重充; 高根泽伸; 藤本大辅
Original assignee: Hitachi Chemical Co Ltd
Current assignee: Showa Denko Materials Co ltd
Priority date: 2015-06-03
Filing date: 2016-11-01
Publication date: 2018-12-21
Also published as: JP2016221953A; TW201808645A; WO2017175413A1; KR20180133393A

Abstract

The present invention relates to a kind of manufacturing methods of laminated body, it has the process for forming resin composition layer on substrate, obtaining laminated body, the substrate contains glass substrate or silicon wafer, the resin composition layer with a thickness of 10 μm hereinafter, the resin composition layer contains with the epoxy resin from the structural unit that carbon number is 3 or more alkylene glycols and containing ester group compound.

Description

The manufacturing method of laminated body and the manufacturing method of distributing board

Technical field

The present invention relates to the manufacturing method of laminated body and the manufacturing methods of distributing board.

Background technique

In recent years, the miniaturization, lightweight of electronic equipment and multifunction obviously improve, at the same time, LSI, chip portion The highly integrated continuous development of part etc..Moreover, its form is also rapidly to multi-pipe pin, miniaturization variation.Therefore, it is in distributing board The packing density of electronic component is improved, the exploitation of fine wiring is developed.

As one of the method for coping with fine wiring requirement, it is known that form conductor layer on the resin layer by plating Method.For example, the circuit forming method as the distributing board of accumulation mode as in patent document 1, main to use half Addition process.This method is after carrying out chemical plating and forming chemical plating coating, using electrolytic coating (plating) only necessary Circuit is carried out on part to be formed, and later, the chemical plating coating on the part for being located at not formed Wiring pattern is removed.

This method is compared with the past since the conductor layer removed is thin, and the etch amount for being not susceptible to conductor layer is few, electric The thin problem in road (Wiring pattern), is advantageous fine wiring.In this method, by the surface roughness institute band of resin layer The anchoring effect come has been to ensure that the situation of the bonding force of resin layer and coating layer (copper plate), is its surface roughness Ra height Up to 0.5 μm or more of situation.

The adaptation that inner layer circuit board and outer circuit are improved under this situation, in patent document 2 proposes in advance It is laminated with the composite layer plate of insulating resin layer and chemical plating adhesive layer.In addition, also proposed and plate in patent document 3 The composition of the excellent addition process distributing board bonding agent of the bonding force of copper.

Existing technical literature

Patent document

Patent document 1: No. 3290296 bulletins of Japanese Patent No.

Patent document 2: Japanese Unexamined Patent Publication 1-99288 bulletin

Patent document 3: Japanese Unexamined Patent Publication 2001-123137 bulletin

Patent document 4: No. 4657554 bulletins of Japanese Patent No.

Summary of the invention

The technical problems to be solved by the invention

In previous accumulation mode, since chemical plating enters the depths of roughening shape, therefore, it is difficult to remove, for shape It is 10 μm of fine circuits below at width, since the surface roughness of resin layer is big, it some times happens that insulation fault (short trouble) opens the problems such as bad.It thus, also can not qualification rate the case where manufacturing distributing board well.On the other hand, When reducing roughening shape (keeping surface smoothened), the formation of fine wiring is advantageous, but it some times happens that and conductor The failure that the bonding force of layer (chemical plating coating etc.) reduces, circuit (route) is peeling-off etc..It is therefore desirable to which it is flat to develop surface Wiring plate material (material for constituting distributing board) sliding and that high bonding force is shown to conductor layer, that is, having can take into account and conductor layer Bonding force and fine wiring formative resin layer wiring plate material.

However, expectation is thinned wiring plate material for the slimming of distributing board.From this point of view, it examines Consider the thickness that the resin layer being configured on substrate is thinned.But when the thickness of resin layer is thinned, there are the bumps because of substrate, tree The tendency that the flatness on the surface of rouge layer reduces, fine wiring formative reduces.

The present invention completes in view of the above fact, its purpose is to provide to resin layer carry out it is thin layer while, it is micro- Thin wiring formative is excellent and the manufacturing method of resin layer and the cementability of conductor layer also excellent laminated body.In addition, this hair Bright purpose, which also resides in, provides the manufacturer for the distributing board for having used the laminated body obtained by the manufacturing method of the laminated body Method.

For solving the means of technical problem

It is that the present inventors are studied in order to solve the above problems as a result, it has been found that, can solve this by following present invention Technical problem.

The manufacturing method of laminated body of the invention has the work for forming resin composition layer on substrate, obtaining laminated body Sequence, wherein the substrate contains glass substrate or silicon wafer, the resin composition layer with a thickness of 10 μm hereinafter, the tree Oil/fat composition layer contains: having the epoxy resin of the structural unit for the alkylene glycol for being 3 or more from carbon number and containing ester Close object.

The manufacturing method of laminated body through the invention, can obtain to resin layer carry out it is thin layer while, it is fine Wiring formative is excellent and the cementability of resin layer and conductor layer (chemical plating copper layer) also excellent laminated body.By this hair The manufacturing method of bright laminated body can obtain while carrying out thin layer to resin layer, even if surface roughness Ra is small, right Conductor layer also shows the laminated body of high cementability.The manufacturing method of laminated body through the invention can be able to carry out The laminated body of wiring densification.

However, in previous wiring plate material, since substrate and resin layer lack cementability etc., when having solder reflow The situation of heat resistance deficiency when removing, installation.Multilayer is manufactured using glass substrate for example, disclosing in above patent document 4 The method of printed base plate.But since resin layer is low with the cementability of glass substrate, when high temperature because of coefficient of thermal expansion difference caused by Stress, can be peeling-off between resin layer and glass substrate, thus the heat resistance that flows back is insufficient.On the other hand, through the invention The manufacturing method of laminated body can obtain the excellent laminated body of soldering heat resistance (soldering reflux heat resistance).That is, through the invention Laminated body manufacturing method, can obtain to resin layer carry out it is thin layer while, fine wiring formative it is excellent and Cementability between resin layer and substrate is also excellent, soldering excellent heat resistance laminated body.

The alkylene glycol that the carbon number is 3 or more is preferably hexylene glycol.The ester group equivalent containing ester group compound is opposite In 1 equivalent of epoxy group of the epoxy resin, preferably 0.3~1.5 equivalent.

The thickness of the glass substrate is preferably 200 μm or less.

The manufacturing method of laminated body of the invention be preferably by spin-coating method formed the resin composition layer in the way of.

The manufacturing method of laminated body of the invention, which can be also further equipped with, carries out heat cure, shape to the resin composition layer At the process of resin cured matter layer.The manufacturing method of laminated body of the invention can also be further equipped with to the resin cured matter The process of layer irradiation ultraviolet light.The manufacturing method of laminated body of the invention is preferably the purple for using maximum wavelength to be 300~450nm Outside line lamp irradiates the mode of the ultraviolet light under atmospheric environment.The surface roughness (Ra) of the resin cured matter layer is preferred It is 0.2 μm or less.

The manufacturing method of distributing board of the invention has following process: being manufactured using the manufacturing method of laminated body of the invention The process of laminated body；With the process for forming conductor layer on the laminated body.

Invention effect

According to the present invention it is possible to provide to resin layer carry out it is thin layer while, fine wiring formative it is excellent and The manufacturing method of also excellent, soldering excellent heat resistance the laminated body of cementability between resin layer and substrate；And it uses and has passed through The manufacturing method of the distributing board (printing distributing board etc.) for the laminated body that the manufacturing method of the laminated body obtains.

Specific embodiment

Present embodiment is described in detail below.In this specification, the numberical range for using "~" to indicate is indicated The numerical value that "~" front and back is recorded respectively is as minimum value and maximum value and the range that is included.Piecewise is remembered in this specification In the numberical range of load, the upper limit or lower limit of certain section of numberical range is also alternatively at the upper limit of the numberical range of other sections Value or lower limit value.In the numberical range recorded in this explanation, the upper limit or lower limit of numberical range can also be substituted for reality Apply value shown in example." A or B " can contain any one of A and B, can also contain the two.Exemplary material is simultaneously in this specification It is not particularly limited, can be used alone or two or more is applied in combination.In this specification, each ingredient in composition contains When amount has multiple substances for being equivalent to each ingredient in the composition, as long as being not particularly limited, refer to present in composition The total amount of multiple substance.

The manufacturing method > of < laminated body

The manufacturing method of the laminated body of present embodiment has forms resin composition layer (containing resin combination on substrate The layer of object), obtain laminated body laminated body formation process.In present embodiment, the substrate contains glass substrate or silicon wafer, The resin composition layer with a thickness of 10 μm hereinafter, resin composition layer contain with from carbon number be 3 or more alkylene The epoxy resin of the structural unit of glycol and contain ester group compound.It is obtained by the manufacturing method of the laminated body of present embodiment Laminated body can be used for manufacturing distributing board.Resin composition layer and substrate can be one layer or more respectively.

Laminated body formation process can also have resin composition layer solidification, form resin cured matter layer (insulation Resin layer etc.) curing process.Curing process, which for example can also be, to carry out heat cure to resin composition layer, forms resin solidification The heat curing processes of nitride layer.In heat curing processes, such as by being heated to resin composition layer, obtaining resin cured matter Layer.Heat-curing resin (epoxy resin etc.) in resin cured matter layer, such as its constituent is fully cured or thermosetting 90% or more of the property changed resin is cured (such as the heat-curing resin more than 90% is cured).

In curing process, preferably in the manufacture of laminated body without pressurization.Occur when at this point it is possible to inhibit manufacture disconnected It splits.It is manufactured in addition, the laminated body of present embodiment can use pressurization；Resin combination can also be coated on substrate And be dried, obtain resin composition layer, it then heated and is pressurizeed using pressurization, solidified, manufacture laminated body.

Laminated body formation process can also have the ultraviolet light to resin cured matter layer irradiation ultraviolet light after curing process Irradiation process.In ultraviolet light irradiation process, by irradiating ultraviolet light to resin cured matter layer, the table of resin cured matter layer can be made The functional group modification in face improves bonding force.

(laminated body formation process)

[resin composition layer]

Resin composition layer is before a part for becoming distributing board layer, on supporter, on glass substrate or silicon wafer Exist Deng with uncured or semi-cured state (so-called B-stage state).For example, in resin composition layer, as resin combination The heat-curing resin (epoxy resin etc.) of the constituent of nitride layer is uncured or semi-cured state.Heat-curing resin is consolidated Change degree can use to be measured by the reactivity of differential scanning calorimeter measurement." B-stage state " refer to curing degree be 5~ 90% state.

The resin composition layer of present embodiment contains the structure that (A) has the alkylene glycol for being 3 or more from carbon number The epoxy resin (hereinafter sometimes referred to as " (A) ingredient ") of unit and (B) containing ester group compound (hereinafter sometimes referred to as " and (B) at Point ").The resin composition layer of present embodiment can also further contain (C) curing accelerator (hereinafter sometimes referred to as " and (C) at Point ").

In laminated body formation process, formed on substrate using resin combination at least containing (A) ingredient and (B) ingredient Resin composition layer.As the forming method of resin composition layer, can enumerate such as coating, laminar manner.

The preparation method of the resin combination of present embodiment is not particularly limited, and known preparation side can be used Method.For example, (A) ingredient, (B) ingredient and various composition used as needed can be added in a solvent, then using super Sound wave dispersing mode, high pressure impact type dispersing mode, high speed rotation dispersing mode, ball mill mode, high speed shear dispersing mode, The various mixing machines such as rotation-revolution formula dispersing mode, are mixed, are stirred, to be prepared into varnish.In addition to solvent in the varnish Except solid component concentration from the viewpoint of coating etc. is excellent, preferably 20~70 mass %.

When forming resin composition layer by coating, coating method is not particularly limited.Such as it can use spin-coating method, leaching Stain method, spray coating method, mist layer spray coating method, flow coat method, curtain coating processes, rolling method, knife coating, scraper for coating method, gas scrape cutter painting Cloth method (air doctor coating), stick coating method, silk screen print method, gravure printing method, flexographic printing process, flexible version printing Resin combination is coated on substrate by method, brushing etc..From the viewpoint of the thickness for being easy to be thinned resin composition layer, preferably Spin-coating method.

When forming resin composition layer by coating, preferably wave solvent dried coating film after coating resin combination Hair.Though because the type of each ingredient in composition, proportion, film thickness etc. difference due to it is different, from improving workability Viewpoint is set out, and is carried out 1~30 minute or so preferably at 40~180 DEG C.

It, can be with due to directly forming resin composition layer on substrate when forming resin composition layer by coating The thickness of gained resin composition layer is further thinned.

Using spin-coating method when forming resin composition layer on substrate, such as by forming this on substrate using spin-coating method After the film of the resin combination (varnish) of embodiment, 80~180 DEG C or so at a temperature of carry out 1~10 minute or so It is dried, the substrate of resin composition layer can be made.The temperature of drying process be 80 DEG C or more and the time be 1 minute with When upper, drying is sufficiently carried out, and can inhibit to generate gap in resin cured matter layer, therefore preferably.In addition, here by The state of solvent volatilization dry, in varnish, is the uncured state for not carrying out curing process, the combination of so-called uncured resin Nitride layer.

As long as spin coating device, which has, supports substrate to be coated, the turntable rotated and the upper table in the turntable Face is formed as trench can adsorb and keep the ordinary device of the vacuum flow path of substrate, then is not particularly limited.

The thickness of the resin composition layer formed by spin coating can be adjusted by adjusting varnish viscosity.As clear The viscosity of paint, is not particularly limited, preferably 1~1000cP.In addition, the revolving speed of spin coating is also not particularly limited, preferably 100~ The range of 5000rpm.

When forming resin composition layer using laminar manner, the pressurizations such as vacuum lamination, roll lamination lamination pair can be passed through The carrier film of resin is laminated with substrate, to manufacture.Make the carrier film of resin according to resin combination and substrate surface The mode on opposite is contacted, such as is laminated using vacuum pressed laminated stack device, so as to form resin combination Nitride layer.

When using vacuum pressed laminated stack device, preferable temperature is 50~170 DEG C or so, pressure is 0.2MPa or more. Preferred pressure value is same as heating temperature, changes with the difference of the thickness of substrate, remaining copper rate (residual quantity of copper) etc., but Preferably 1.0MPa or less.In addition, the imbedibility in inner layer circuit board becomes be more good when vacuum degree is 15hPa or less. The vacuum degree the low the more preferred, but in view of the ability of device, to shadows caused by productivity such as the waiting time for reaching specified value When ringing, the preferably range of 5~10hPa.Being thermally compressed the time is preferably 10~90 seconds or so.Being thermally compressed the time is 10 seconds or more When, the resin imbedibility in internal layer circuit becomes more excellent.When the thermo-compression bonding time is 90 seconds or less, productivity becomes more Well.The preferred thermo-compression bonding time is 20~60 seconds.

The resin combination of present embodiment for the formation for resin composition layer, can be coated on a carrier film, It is saved with the state of the carrier film of resin.Specifically, the varnish of the resin combination containing present embodiment is applied Cloth on a carrier film after, such as 80~180 DEG C or so at a temperature of be dried 1~10 minute or so, to obtain band The carrier film of resin.When the temperature of drying process is 80 DEG C or more and the time of drying process is 1 minute or more, drying is fully It carries out, can further suppress and generate gap in resin.The temperature of drying process is the time of 180 DEG C or less and drying process When being 10 minutes or less, dry excessively progress can be further suppressed, resin flow reduces.

As apparatus for coating, comma coater, bar coater, kiss coater, roll coater, intaglio plate coating can be used Well known to a person skilled in the art apparatus for coating for machine, die coating machine etc., preferably suitable according to the thickness of made resin composition layer Work as selection.In addition, resin can also be by semi-solid preparation in the carrier film of above-mentioned resin.Above-mentioned carrier film becomes to manufacture aftermentioned tree Supporter when oil/fat composition layer is removed during manufacturing printing distributing board by removing etc..

As carrier film, the film being molded of plastic material, metal foil (copper foil, aluminium foil etc.), processing release paper etc. can be enumerated, preferably Use the film being molded of plastic material.As plastic material, polyethylene terephthalate (PET), poly- naphthalene diformazan can be enumerated The polyester such as sour glycol ester (PEN)；Polycarbonate (PC)；The acrylic resins such as polymethyl methacrylate (PMMA)；Ring-type is poly- Alkene；Triafol T (TAC)；Polyether sulfone (PES)；Polyether-ketone；Polyimides etc..Wherein, it is preferably selected from poly- terephthaldehyde One or more of sour glycol ester (PET) and polyethylene naphthalate (PEN), more preferably cheap poly terephthalic acid Glycol ester (PET).

The thickness of carrier film is not particularly limited, preferably 10~200 μm of range, more preferably 20~60 μm of model It encloses, further preferably 20~50 μm of range.

As carrier film, the carrier film with release layer on the face with resin-bonded with release layer also can be used. As release agent used in the release layer in the carrier film with release layer, can enumerate for example selected from alkyd resin, polyolefin tree The release agent of one or more of rouge, polyurethane resin and organic siliconresin.

In present embodiment, commercially available product is can be used in the carrier film with release layer.As commercially available product, Lintec plants can be enumerated " PET501010 " of formula commercial firm, " SK-1 ", " AL-5 ", " AL-7 " etc..

The thickness of resin composition layer from the viewpoint of reach it is thin layer, be 10 μm or less.The thickness of resin composition layer Degree from the viewpoint of can be easily achieved it is thin layer, preferably smaller than 10 μm, more preferably 5 μm or less, be more preferably 3 μm or less.The thickness of resin composition layer is from the viewpoint of further increasing the adhesive strength with conductor layer, and preferably 0.1 μm Above, it is more preferably 0.5 μm or more, further preferably 1 μm or more.

Hereinafter, being illustrated to constituents such as (A) in resin combination~(C) ingredients.

{ (A) epoxy resin }

(A) ingredient is the epoxy resin of the structural unit with the alkylene glycol for being 3 or more from carbon number.Pass through (A) Ingredient has the structural unit for the alkylene glycol for being 3 or more from carbon number, and the flexibility of resin combination improves, is easy to reach It is thin layer.

Epoxy resin as (A) ingredient has 2 or more epoxy groups for example in 1 molecule.(A) ingredient can be There is the structural unit for the alkylene glycol for being 3 or more from carbon number in main chain.In addition, from the viewpoint of improving flexibility, Structural unit from carbon number for 3 or more alkylene glycol preferably continuously repeats 2 or more.(A) ingredient is from further increasing From the perspective of heat resistance, preferably aromatic epoxy resin.

As (A) ingredient, cresol novolak type epoxy resin, phenol novolak type epoxy resin, naphthols can be enumerated Phenolic resin varnish type epoxy resin, aralkyl phenolic resin varnish type epoxy resin, biphenyl phenolic resin varnish type epoxy resin, bisphenol-A type ring Oxygen resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, bis-phenol T-type epoxy resin, bisphenol Z type epoxy resin, tetrabromo are double Phenol A type epoxy resin, biphenyl type epoxy resin, tetramethyl biphenyl type epoxy resin, triphen type epoxy resin, tetraphenyl type ring Oxygen resin, naphthols aralkyl-type epoxy resin, naphthalene glycol aralkyl-type epoxy resin, naphthols aralkyl-type epoxy resin, fluorenes type Epoxy resin, the epoxy resin with bicyclopentadiene skeleton, in skeleton with ethylene linkage unsaturated group epoxy resin, rouge Ring type type epoxy resin etc..(A) ingredient can be used alone, and go out from insulating reliability and the more excellent viewpoint of heat resistance Hair, can be applied in combination two or more.

As (A) ingredient, can specifically enumerate bisphenol A type epoxy resin (Mitsubishi chemical Co., Ltd's system " jER828EL ", " YL980 " etc.), bisphenol f type epoxy resin (Mitsubishi chemical Co., Ltd's system " jER806H ", " YL983U " etc.) etc..

(A) carbon number of the alkylene glycol of ingredient is from the viewpoint of further increasing flexibility, and preferably 4 or more, more excellent It is selected as 5 or more, further preferably 6 or more.(A) carbon number of the alkylene glycol of ingredient is excellent from the viewpoint of treatability is excellent It is selected as 15 or less, more preferably 10 or less, further preferably 8 or less.Alkylene from these viewpoints, as (A) ingredient Alkylene glycol that alkylene glycol that glycol, preferably carbon number are 3~15, more preferable carbon number are 3~10, further preferred carbon number are 4 ~8 alkylene glycol, particularly preferred hexylene glycol.There is the structure from hexylene glycol as (A) ingredient, such as in preferred main chain The bisphenol A type epoxy resin of unit.1,6-HD divinyl ether can be used for example from the structural unit of hexylene glycol It obtains.

The concrete example of (A) ingredient as the structural unit in main chain with the alkylene glycol for being 3 or more from carbon number Son can be enumerated for example in structural unit shown in the structural unit shown in the following general formula (I) and the following general formula (II) At least one kind of epoxy resin.As the asphalt mixtures modified by epoxy resin with structural unit shown in structural unit shown in formula (I) and formula (II) Rouge can enumerate epoxy resin shown in such as the following general formula (III).

[chemical formula number 1]

[chemical formula number 2]

[in logical formula (I), (- O-R₁- O-) indicate from carbon number be 3 or more alkylene glycol structural unit, preferably such as It is upper described.In logical formula (II), R₂Indicate carbon number be 1~10 aliphatic alkyl or singly-bound, preferably carbon number be 1~5 aliphatic Alkyl.]

[chemical formula number 3]

[in formula (III), (- R₃- O-) indicate from carbon number be 3 or more alkylene glycol structural unit, preferably as above It is described.R₄Indicate carbon number be 1~10 aliphatic alkyl, preferably carbon number be 1~5 aliphatic alkyl.In addition, n expression 1~ It 15, is preferably 2~10].

When forming resin composition layer with laminar manner, from the viewpoint of workability is excellent, as (A) ingredient, preferably Temperature in lamination occurs below the ingredient of melting.For example, when being laminated using vacuum laminator or roll lamination machine, it is excellent The fusing point for selecting (A) ingredient in resin combination is 170 DEG C or less.

(A) epoxide equivalent of ingredient and be not limited, preferably 50~3000, more preferably 80~2000, further preferably It is 100~1000.In addition, epoxide equivalent can be measured according to JIS K7236, the epoxy group relative to every 1 equivalent is indicated Epoxy resin quality.

(A) content of ingredient is not particularly limited, from further increasing resin layer (resin composition layer or resin cured matter Layer) with from the perspective of the adaptation of glass substrate or silicon wafer, with the gross mass (total solid content) of resin combination for base It standard, preferably 10 mass % or more, more preferably 15 mass % or more, is more preferably 20 mass % or more, particularly preferred For 30 mass % or more, it is highly preferred be 40 mass % or more.In addition, the content of (A) ingredient is (total with the gross mass of resin combination Solid component) on the basis of, preferably 80 mass % or less, more preferably 75 mass % or less, further preferably 70 mass % Below.

{ (B) contains ester group compound }

What it is as (B) ingredient is the compound containing ester group containing ester group compound.(B) ingredient can be used as consolidating for (A) ingredient Agent uses.As (B) ingredient, it can enumerate and contain 1 or more ester group in such as 1 molecule and epoxy resin cure can be made Compound, can be in 1 molecule with 1 or more ester group resin.

(B) ingredient preferably has at least one kind of in aliphatic chain and aromatic ring.As (B) ingredient, example can be enumerated The ester compounds such as obtained by aliphatic or aromatic carboxylic acid and aliphatic or aromatic hydroxy compound.Wherein, by aliphatic The ester compounds that carboxylic acid and aliphatic hydroxy compound obtain by containing aliphatic chain, can be improved in organic solvent can Dissolubility and compatibility with epoxy resin.The ester compounds obtained by aromatic carboxylic acid and aromatic hydroxy compound are by having Aromatic ring can be further improved heat resistance.

As (B) ingredient, active form can also be used to contain ester group compound.Contain ester group compound as active form, can lift UV active type is containing ester group compound etc. out.UV active type containing ester group compound is lived by ultraviolet irradiation The compound containing ester group of property.

As (B) ingredient it is preferable to use compound, can enumerate for example using following mixtures as raw material, pass through fragrance The condensation reaction of race's carboxylic acid and phenolic hydroxyl group and the aromatic ester obtained, the mixture are with carboxyl substituted aromatic compound In the hydrogen atom of (benzene, naphthalene, biphenyl, diphenyl propane, diphenyl methane, diphenyl ether, diphenyl sulfonic acid, benzophenone etc.) Aromatic carboxylic acid obtained from 2~4, with replaced in the hydrogen atom of the aromatic compound with hydroxyl 1 obtained from Unitary phenol system compound replaces polynary phenol system obtained from 2~4 in the hydrogen atom of the aromatic compound with hydroxyl The mixture of compound.

As unitary phenol system compound, phenol, various cresols, alpha-Naphthol, betanaphthol etc. can be enumerated.As polynary phenol system Close object, can enumerate quinhydrones, resorcinol, catechol, 4,4 '-xenols, 4,4 '-dihydroxydiphenyl ethers, bisphenol-A, Bisphenol F, Bisphenol S, bisphenol Z, brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, methylation bisphenol S, various dihydroxy naphthlenes, various dihydroxy Benzophenone, various trihydroxybenzophenones, various tetrahydroxybenzophenones, fluoro glycine etc..It, can as aromatic carboxylic acid Enumerate phthalic acid, M-phthalic acid, terephthalic acid (TPA), benzene tricarbonic acid etc..

As the commercially available product of (B) ingredient, " EXB-9451 ", " EXB-9460 ", " EXB- of Dainippon Ink Chemicals can be enumerated 9460S ", " EXB-9470 ", " EXB-9480 ", " EXB-9420 ", " BPN80 " of Mitsui Chemicals, Inc etc..

(B) ingredient can be used alone, and also can be used in combination two or more.

(B) the ester group equivalent (ester group equivalent, active ester groups equivalent) of ingredient is worked as preferably with respect to the epoxy group 1 of (A) ingredient Amount is following ranges.(B) the ester group equivalent of ingredient is from the viewpoint of viscosity and curability become more abundant, and preferably 0.3 More than equivalent, more than more preferably 0.4 equivalent, more than further preferably 0.5 equivalent.(B) the ester group equivalent of ingredient is from obtaining Further adequately from the perspective of curability, heat resistance and chemical reagent resistance, below preferably 1.5 equivalents, more preferably Below 1.25 equivalents, below further preferably 0.9 equivalent, below particularly preferably 0.6 equivalent.From these viewpoints, (B) The ester group equivalent of ingredient is preferably 0.3~1.5 equivalent, more preferably 0.3~1.25 equivalent, further preferably 0.4~1.25 Equivalent, particularly preferably 0.5~0.9 equivalent, it is highly preferred be 0.5~0.6 equivalent.

{ (C) curing accelerator }

The resin combination of present embodiment can be further containing the curing accelerator as (C) ingredient.(C) ingredient example The common curing accelerator for epoxy resin cure can be used in for example epoxy resin curing accelerator.Furthermore, it is possible to by phase When the compound in both (B) ingredient and (C) ingredient belongs to (B) ingredient.(C) ingredient can be used alone, can also group It closes and uses two or more.

As (C) ingredient, such as imidazole compound can be used；Organic phosphine based compound；Organic phosphite system Close object；Phosphonium salt compound；Amine compound；With the salt of bicyclic (the 5,4,0) -7- endecatylene of bis- nitrine of 1.8- etc.；Quaternization Close object etc..

As the specific example of (C) ingredient, 2-methylimidazole, 2-ethyl-4-methylimidazole, 1- benzyl -2- first can be enumerated The imidazoles such as base imidazoles, 2- octadecyl imidazoles, 2- undecyl imidazole, 1- cyano ethyl -2- phenylimidazole trimellitic acid salt Based compound；The organic phosphines based compound such as triphenylphosphine, tributylphosphine；Organic Asia such as Trimethyl phosphite, triethyl phosphite Phosphate based compound；The phosphonium salt compounds such as three phenyl-bromide Phosphonium of second base, tetraphenylphosphoniphenolate tetraphenyl borate salts；Trialkylamine (example Such as triethylamine and tri-butylamine), 4-dimethylaminopyridine, benzyldimethylamine, 2,4,2,4,6- tri- (dimethylaminomethyl) Bicyclic (the 5.4.0) -7- endecatylene (DBU) of phenol, bis- nitrine of 1,8-, diaminodiphenyl-methane, diamino diphenyl sulfone, two The amine systems chemical combination such as aminodiphenyl base ether, p-phenylenediamine, m-phenylene diamine (MPD), o-phenylenediamine, 1,5- diaminonaphthalene, two methylene phenylenediamines Object；The salt of DBU and terephthalic acid (TPA), 2,6 naphthalene dicarboxylic acid etc.；Etamon chloride, 4-propyl ammonium chloride, tetrabutylammonium chloride, Quarternary ammonium salt compounds such as tetrabutylammonium bromide, four hexyl ammonium bromides, benzyltrimethylammonium chloride etc..These substances can individually make With a kind, two or more can also be applied in combination.

(C) content of ingredient is following ranges preferably with respect to 100 mass parts of (A) ingredient.(C) content of ingredient is from ring The solidification of oxygen resin become more sufficiently, from the perspective of heat resistance becomes better, more than preferably 0.02 mass parts, more preferably For more than 0.1 mass parts, more than further preferably 0.2 mass parts, more than particularly preferably 0.3 mass parts.(C) ingredient contains It measures from the viewpoint of further increasing the treatability with the storage stability of resin combination and resin composition layer, Preferably 1.5 below the mass, more preferably 1.3 below the mass, further preferably 1 below the mass, particularly preferably 0.5 below the mass.From these viewpoints, the content of (C) ingredient be preferably 0.02~1.5 mass parts, more preferably 0.1~ 1.5 mass parts, further preferably 0.2~1.5 mass parts, particularly preferably 0.3~1.3 mass parts, it is highly preferred be 0.3~1 Mass parts, very preferably 0.3~0.5 mass parts.

{ other compositions }

[epoxy resin other than (A) ingredient]

The resin combination of present embodiment is also containing the epoxy resin other than (A) ingredient.Other than (A) ingredient Epoxy resin, from the more excellent viewpoint of heat resistance, preferably with the aralkyl nobolak type epoxy tree of biphenyl structural Rouge.Aralkyl phenolic resin varnish type epoxy resin with biphenyl structural refers to the aromatic ring in molecule containing biphenyl derivatives Aralkyl phenolic resin varnish type epoxy resin can enumerate the epoxy resin for example with structural unit shown in following formula (i).As tool There is the epoxy resin of structural unit shown in formula (i), epoxy resin shown in such as the following general formula (ii) can be enumerated.

[chemical formula number 4]

[chemical formula number 5]

[in formula (ii), p indicate 1~5.]

As the commercially available product of the epoxy resin with structural unit shown in formula (i), Nippon Kayaku K. K's system can be enumerated Trade name " NC-3000 " (p=1.7), " NC-3000H " (p=2.8) etc..

[curing agent]

It, can be with (B) ingredient, and with having the function of epoxy resin cure in the resin combination of present embodiment Can known curing agent (except (B) ingredient).As this curing agent, such as phenol system curing agent, cyanate system solidification can be enumerated Agent and acid anhydrides system curing agent.

Be not particularly limited as phenol system curing agent, be preferably selected from cresol novolak type curing agent, biphenyl type curing agent, One or more of phenol system curing agent of phenol novolak type curing agent, naphthols ether type curing agent and the skeleton containing triazine.Phenol system is solid Agent can be used alone, two or more can also be applied in combination.

As the commercially available product of phenol system curing agent, can enumerate KA-1160, KA-1163, KA-1165 (is Dainippon Ink Chemicals System, trade name) etc. cresol novolak types curing agent (cresol novolak type phenolic resin)；MEH-7700,MEH-7810, The biphenyl types curing agent such as MEH-7851 (being bright and chemical conversion Co. Ltd. system, trade name)；TD2090 (Dainippon Ink Chemicals's system, quotient The name of an article) etc. phenol novolak types curing agent；The naphthols ether type curing agent such as EXB-6000 (Dainippon Ink Chemicals's system, trade name)； The phenol system curing agent of the skeletons containing triazine such as LA3018, LA7052, LA7054, LA1356 (being Dainippon Ink Chemicals's system, trade name) Deng.

It is not particularly limited as cyanate system curing agent, it is (oligomeric that bisphenol A dicyanate, polyphenyl phenol cyanate can be enumerated (3- methylene -1,5- phenylenecyanate), 4,4 '-di-2-ethylhexylphosphine oxides (2,6- 3,5-dimethylphenyl cyanate), 4,4 '-ethylenes Bis- (4- cyanate) phenyl-propanes of phenyl dicyanate, hexafluoro bisphenol-a dicyanate, 2,2-, bis- (the 4- cyanate phenyl first of 1,1- Alkane), it is bis- (4- cyanate -3,5- 3,5-dimethylphenyl) methane, bis- (4- cyanate phenyl -1- (methyl the ethylidene)) benzene of 1,3-, double (4- cyanate phenyl) thioether, bis- (4- cyanate phenyl) ethers etc..It is not particularly limited as acid anhydrides system curing agent, neighbour can be enumerated Phthalate anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methyl hexahydro are adjacent Phthalate anhydride, methylnadic anhydride, hydrogenating methyl carbic anhydride, trialkyl tetrabydrophthalic anhydride, laurylene base Succinic anhydride, 5- (2,5- dioxotetrahydro -3- furyl) -3- methyl -3- cyclohexyl -1,2- dicarboxylic anhydride, trimellitic anhydride, Pyromellitic dianhydride etc..

The resin combination of present embodiment within the scope without prejudice to the object of the present invention, can also further contain as needed There are solvent, inorganic filler, various adding ingredients (such as levelling agent, antioxidant, fire retardant, thixotropy conferring agents, tackifier) Deng.

[solvent]

The resin combination of present embodiment can contain solvent.As solvent, can enumerate methyl ethyl ketone, dimethylbenzene, toluene, Acetone, ethylene glycol monomethyl ether, cyclohexanone, ethyl ethoxy-c acid esters, N,N-dimethylformamide, N, N- dimethylacetamide Amine, propylene glycol monomethyl ether etc..Solvent can be used alone, and can also be mixed with two or more.Solvent is relative to described The use ratio of resin combination can be the ratio used in the past, can also be formed according to the film of target resin composition layer Equipment adjust usage amount.

[inorganic filler]

The resin combination of present embodiment can contain from the viewpoint of inhibiting coefficient of thermal expansion and improving coating strength Inorganic filler.As inorganic filler, can be used for example silica (such as fused silica and except fused silica with Outer silica), talcum, aluminium oxide, aluminium hydroxide, barium sulfate, calcium hydroxide, fumed silica (Aerosil), carbonic acid The inorganic fillers such as calcium, it is preferable to use silica from the viewpoint of the excellent viewpoint of dielectric property and low thermal expansion.It is inorganic to fill out Material can be used singly or in combination of two or more.

The content of inorganic filler is not particularly limited, preferably with respect to the solid component of resin combination in addition to the solvents Total amount is following ranges.The content of inorganic filler is excellent from the viewpoint of being able to suppress thermal expansion coefficient and dielectric loss increase It is selected as 1 mass % or more, more preferably 3 mass % or more, further preferably 5 mass % or more.The content of inorganic filler from In internal layer circuit formed insulating resin when necessary mobility become sufficiently, be difficult to generate be not filled by place from the perspective of, Preferably 60 mass % or less, more preferably 50 mass % or less, further preferably 40 mass % or less.Go out from these viewpoints Hair, the content of inorganic filler are preferably 1~60 mass %, more preferably 3~50 mass %, further preferably 5~40 matter Measure %.These inorganic fillers are also handled using coupling agent from the purpose for improving dispersibility, can pass through kneading The mixing that the known methods such as machine, ball mill, ball mill, three roller kneading machines carry out, is dispersed in resin combination in heterogeneity.

In order to improve the dispersibility of inorganic filler, it is preferable to use coupling agent is surface-treated inorganic filler.As idol Join agent, silane system, titanate esters system, aluminium system coupling agent etc. can be enumerated.Wherein, preferably silane series coupling agent.As silane system idol Join agent, N- phenyl-gamma-amino propyl trimethoxy silicane, gamma-amino propyl trimethoxy silicane, gamma-amino propyl can be enumerated Triethoxysilane, γ-(2- amino-ethyl) TSL 8330, three second of γ-(2- amino-ethyl) aminopropyl Oxysilane, γ-anilino- propyl trimethoxy silicane, γ-anilino- propyl-triethoxysilicane, N- β-(N- vinyl benzyl Base amino-ethyl)-gamma-amino propyl trimethoxy silicane, N- β-(N- vinylbenzylaminoethyl)-gamma-amino propyl three The amino silane compounds such as Ethoxysilane；γ-glycidoxypropyltrimewasxysilane, γ-glycidoxypropyl third The epoxy silane compounds such as ethyl triethoxy silicane alkane, β-(3,4- epoxycyclohexyl) ethyl trimethoxy silane；γ-glycidol Oxygroup propyl trimethoxy silicane, γ-glycidoxypropyl vinylethoxysilane, γ-mercaptopropyi trimethoxy Silane, γ-Mercaptopropyltriethoxysilane, γ-ureido-propyl trimethoxy silane, γ-ureidopropyltriethoxysilane, Compounds such as γ-methacryloxypropyl trimethoxy silane etc..

[glass substrate]

As the raw material of glass substrate, the glass such as alkali silicate glass, alkali-free glass, quartz glass can be used for example Glass, but from the viewpoint of low heat expansion, preferably alkali silicate glass.In addition, the raw material as glass substrate, from low-heat From the perspective of dilatancy, the preferred high glass of silicon component ratio.The thickness of glass substrate is not particularly limited, preferably following Range.The thickness of glass substrate is from the viewpoint of the slimming of laminated body and excellent in workability, and preferably 200 μm or less, more Preferably 150 μm or less, further preferably 120 μm or less, particularly preferably 100 μm or less.The thickness of glass substrate is from From the perspective of the easiness of reason is excellent, preferably 30 μm or more, more preferably 50 μm or more.For example, the thickness of glass substrate From the viewpoint of the slimming of laminated body and excellent in workability, preferably 200 μm or less, more preferably 30~200 μm.Glass The thickness of substrate is from the viewpoint of the easiness of processing is excellent, and more preferably 50~150 μm.In addition, the thickness of glass substrate From the viewpoint of the slimming of laminated body, preferably 30~120 μm, more preferably 30~100 μm.

As glass substrate, by using the low thermal expansion rate with silicon chip for equal extent and high elastic modulus person, easily In inhibition warpage, it is difficult to produce fracture.In particular, this laminated body is by the glass substrate high with heat resistance, 100 DEG C~ In temperature region lower than the Tg of resin cured matter, there is low heat expansion significantly.In addition, resin cured matter layer is by containing Inorganic filling material, resin cured matter layer become low heat expansion, high resiliency person, and the laminated body containing the resin cured matter layer becomes For more low expansion, more high elastic modulus person.

The coefficient of thermal expansion of glass substrate is from the viewpoint of the warpage of inhibition layer stack, and preferably 8ppm/ DEG C or less, more excellent It is selected as 6ppm/ DEG C or less, further preferably 4ppm/ DEG C or less.In addition, the lower limit of the coefficient of thermal expansion is not particularly limited, Preferably 1ppm/ DEG C or more.

Dynamic storage modulus of the glass substrate at 40 DEG C is the bigger the better, preferably 20GPa or more, more preferably 25GPa It above, is more preferably 30GPa or more.

[silicon wafer]

As substrate, silicon wafer can be applied.The diameter of chip is, for example, 50~300mm.In addition, the thickness of silicon wafer is examined When considering the practicabilities such as ease of handling, the simplicity in manufacturing process, preferably 0.5~1mm or so.

(curing process)

In curing process, such as the solidfied material by making resin combination heat cure, resin combination can be obtained.Thermosetting Change processing can be on the basis of the temperature and time of the annealing of plating, circuit layer after considering etc. suitably It carries out.The condition of heat cure is from obtaining in plating later and the cementability of circuit layer becomes be more good and into one It is preferably following from the perspective of the resin cured matter layer of the curing degree of erosion when step inhibition plating in alkali process liquid Range.Heating temperature is preferably 150 DEG C or more, more preferably 160 DEG C or more.Heating temperature is preferably 220 DEG C or less, more excellent It is selected as 200 DEG C or less.Heating time is preferably 20 minutes or more, more preferably 30 minutes or more.Heating time is preferably 120 points Below clock, it is more preferably 90 minutes or less, further preferably 80 minutes or less.The condition of heat cure can be 150~220 DEG C It descends 20~80 minutes, be also possible at 160~200 DEG C 30~120 minutes.When using the support film for implementing demoulding processing, Support film can also be removed after being heating and curing.

(ultraviolet light irradiation process)

After above-mentioned curing process, can also solidfied material (resin cured matter layer) to resin combination carry out ultraviolet light photograph Penetrate processing.It is not particularly limited as ultraviolet light irradiation condition., it is preferable to use maximum wavelength is from the viewpoint of being easy process 300~450nm ultraviolet radiator (maximum wavelength be 300~450nm in the range of radiate ultraviolet light ultraviolet radiator), big Ultraviolet light is irradiated under air pressure environment, more preferably using the ultraviolet radiator that maximum wavelength is 300~450nm, under atmospheric pressure environment Reach 1000~5000mJ/cm according to light quantity²The mode of range irradiate ultraviolet light.Light quantity (the mJ/cm²) use " illumination (mW/ cm²) × irradiation time (second) " is indicated.The temperature of resin cured matter layer when ultraviolet light irradiates is preferably 50~80 DEG C of left sides The right side, more preferably 60~70 DEG C.

For irradiating the method for ultraviolet light due to different with ultraviolet device, it is not particularly limited, but consider When productivity, the preferred ultraviolet light radiation modality of conveying type.In ultraviolet radiator, as being 300~450nm with maximum wavelength Range person can enumerate mercury short-arc lamp, high-pressure sodium lamp, capillary type uhp lamp, high-pressure lamp, metal halide lamp etc..These lamps In, the wide metal halide lamp of the wavelength of preferably ultraviolet light.

Using the maximum wavelength with ultraviolet light be 300~450nm range ultraviolet radiator purpose and versatility and The wavelength domain of ultraviolet light is related.That is, because the ultraviolet radiator for being 300~450nm usually using display maximum wavelength is as transmission The ultraviolet lamp (such as post-exposure device of solid resist) of formula.In addition, dress is irradiated in the transmission of metal halide type It sets since ultraviolet wavelengths are wide, do not need special device, by replacing these devices, effect of the invention can be played Fruit.The light quantity of ultraviolet light is 1000mJ/cm²When above, even do not have to oxidisability coarsening solution to resin cured matter layer at Reason, also becomes sufficiently with the bonding force of plating conductor, and the light quantity of ultraviolet light is 5000mJ/cm²When following, which is able to It shows, be economically also advantageous well.Light quantity is more preferably 2000~4000mJ/cm², further preferably 3000~ 4000mJ/cm²。

In this way, carrying out ultraviolet treatment with irradiation, resin solidification later by carrying out heat cure processing to resin composition layer Nitride layer without forming concaveconvex shape using coarsening solutions such as previous sodium permanganate systems used, can also even show conductor layer High bonding force, therefore the qualification rate that wiring can be inhibited to be formed reduces.Furthermore, it is possible to be carried out at washing without using coarsening solution Reason and liquid waste processing, are also advantageous in cost.

In addition, in order to remove the residue at via hole bottom, even utilizing the coarsening solutions such as sodium permanganate system in present embodiment It is handled, concaveconvex shape is also small, and can easily be ensured that the high bonding force to conductor layer.

The thickness of resin cured matter layer is not particularly limited, and is relatively increased from by substrate (glass substrate etc.) thickness And from the perspective of can be easily implemented low thermal expansion rate and the high elastic modulus of laminated body, preferably 10 μm or less, More preferably less than 10 μm, further preferably 5 μm or less, particularly preferably 3 μm or less.The thickness of resin cured matter layer from into From the perspective of one step improves peel strength, preferably 0.1 μm or more, more preferably 0.5 μm or more, further preferably 1 μm It above, is more preferably 2 μm or more.

Be formed in resin cured matter layer conductor layer (circuit layer etc.) side surface (face that is in contact with carrier film or With the face of contact at the surface of opposite side) surface roughness Ra from the viewpoint of being easy the miniaturization of wiring, preferably 0.2 μm or less, more preferably 0.15 μm or less, further preferably 0.1 μm or less, be particularly preferably 0.05 μm or less.Rough surface The lower limit of degree Ra is not particularly limited, from the viewpoint of further increasing peel strength, preferably 0.001 μm.Resin solidification The ultra-deep measuring shape microscope of Co., Ltd.'s Keyence corporation can be used for example in the surface roughness Ra of nitride layer " VK-8500 type " is measured.

The resin cured matter layer formed in present embodiment is easy to although the concaveconvex shape of resin cured matter layer surface is small High bonding force is shown to conductor layer.Though its mechanism is simultaneously indefinite, speculate when irradiating ultraviolet light to resin cured matter layer, By irradiating ultraviolet light, the ester group containing ester group compound of (B) ingredient decomposed, it is oxygen-containing to be formed on the surface of resin cured matter layer Base, the oxygen-containing group lead to the bonding force high to conductor layer.Wherein, it is formed in the oxygen atom of the oxygen-containing group of resin cured matter layer surface Amount can use x-ray photoelectron optical spectroscopy and be measured.

The resin cured matter layer formed in present embodiment not only highly keeps the viscous of resin cured matter layer and conductor layer Relay, the bonding force for also highly keeping concave-convex small glass substrate and resin cured matter layer.Thus, it is possible to up to the present Fine circuits are carried out on impossible glass substrate to be formed.

Specifically, can for example be preferably used for forming line width and being spaced (L/S) is 10 μm/10 μm wirings below, It is more preferably used in form especially 5 μm/5 μm or less and then 3 μm/3 μm wirings below.

Storage modulus of the laminated body of present embodiment at 40 DEG C is preferably 1~80GPa.Storage modulus is 1GPa or more When, the fracture that protects substrate (glass substrate etc.), further suppress laminated body.When storage modulus is 80GPa or less, inhibit Because of stress caused by the difference of substrate (glass substrate etc.) and the coefficient of thermal expansion of resin cured matter layer, stacking is further suppressed The warpage and fracture of body.From these viewpoints, the storage modulus of resin cured matter layer be more preferably 3~70GPa, further it is excellent It is selected as 5~60GPa.

The laminated body of present embodiment can be the layer with metal foil with metal foils such as copper, aluminium in one or two sides Stack.As long as metal foil uses user on the way in electrically insulating material, then it is not particularly limited.

The manufacturing method of the laminated body with metal foil is not particularly limited.For example, by using gold as support film Belong to foil, the laminated body with metal foil can be manufactured.Alternatively, it is also possible to by 1 or multiple (such as 2~20) pass through above-mentioned layer It presses or the laminated body of coating acquisition is overlapped, it is cascading into shape with the composition progress for being configured with metal foil in its one or two sides, from And manufacture the laminated body with metal foil.

Molding condition can apply electrically insulating material laminated body or multiple-plate method, and multistage can be used for example and add Pressure, multistage vacuum pressed, progressive forming machine, autoclave forming machine etc., temperature be 100~250 DEG C or so, pressure be 2~ 100MPa or so and heating time are to be formed in the range of 0.1~5 hour or so.

(other processes)

After carrying out heat cure processing or ultraviolet light irradiation process, can according to need progress resin cured matter layer and/ Or the process that via hole is formed on substrate (glass substrate etc.).Thus, it is possible to form via hole in resin cured matter layer etc., pass through Through-hole etc..Via hole is the electrical connection for interlayer and is arranged, it is contemplated that the characteristic of resin cured matter layer, using use bore, The known method of laser, plasma etc. is formed.For example, can irradiate laser from carrier film in the presence of carrier film, set Via hole is formed in rouge solidified material layer.

As laser light source, carbon dioxide laser, YAG laser, UV laser, excimer laser etc. can be enumerated.Wherein, from adding From the perspective of work speed and cost are excellent, preferably carbon dioxide laser.

Perforation processing can be used commercially available laser aid and be implemented.It, can as commercially available carbon dioxide laser device Enumerate such as LC-2E21B/1C of Viamechanics Co. Ltd. system, the ML605GTWII of Mitsubishi Electric Corporation and The substrate of Panasonic Welding Systems Co. Ltd. system punches laser machine.

It is formed after the process of the via hole, oxidant can be used as needed is handled and (go residue treatment work Sequence).It goes in residue treatment process, such as the residue that via hole bottom is generated removes.As oxidant, preferably permanganate (potassinm permanganate, sodium permanganate etc.), bichromate, ozone, hydrogen peroxide/sulfuric acid, nitric acid etc., more preferable potassinm permanganate cross manganese The sodium hydrate aqueous solutions such as sour sodium (alkalinity crosses mangaic acid aqueous solution).

As oxidant, oxidisability coarsening solution can be used.As oxidisability coarsening solution, chromium/sulfuric acid roughening can be used Liquid, alkali cross mangaic acid coarsening solution (sodium permanganate coarsening solution etc.), sodium fluoride/chromium/sulfuric acid coarsening solution, boron fluoric acid coarsening solution etc..In addition, When being handled using oxidisability coarsening solution, can be immersed in solvent or lye or their mixed liquor (is in general molten Swollen liquid or prepreg solution) in, then handled using oxidisability coarsening solution.As above-mentioned solvent, the solvent of alcohol system can be used (diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, isopropanol etc.).In addition, as long as lye is shown when being dissolved in the water The solution for showing alkalinity, then be not particularly limited, sodium hydroxide solution, potassium hydroxide solution etc. can be used.In addition, can also mix molten Agent or lye, can be used for example containing sodium hydroxide and diethylene glycol monobutyl ether composition (such as sodium hydroxide 3g/L and The composition of diethylene glycol monobutyl ether 300mL/L) person.

It is described to go residue treatment process that carry out between curing process and ultraviolet light irradiation process, it can also be in ultraviolet light It is carried out between irradiation process and conductor layer formation process (aftermentioned).

In addition, being also possible to the original sample that resin cured matter layer has carrier film when going residue treatment process described in carrying out.Band When having the original sample of carrier film, the bumps of resin cured matter layer surface caused by can preventing because of coarsening solution become larger, in resin solidification In nitride layer, wiring it is further miniaturization become possible.As long as that is, not carrying out residue treatment process, or by setting Make the table of resin cured matter layer with carrying out the methods of residue treatment process in the state of carrier film on rouge solidified material layer surface Face and the discontiguous embodiment of coarsening solution can then be easily prevented from the concave-convex of the surface of resin cured matter layer and increase.

The laminated body of present embodiment can be the multi-layer laminate containing multiple laminated bodies.The manufacture of the multi-layer laminate There is no particular restriction for method.For example, can by removing bonding agent made of support film and protective film from above-mentioned adhesive film, By the multiple stackings of the laminated body of present embodiment, multiple stratification is carried out.

In addition, can also be cascading into shape by being overlapped, carrying out by multiple (such as 2~20) laminated bodies, to manufacture multilayer Laminated body.Specifically, multistage pressurization, multistage vacuum pressed, progressive forming machine, autoclave forming machine etc. can be used, in temperature Degree for 100~250 DEG C or so, pressure be 2~100MPa or so and heating time be 0.1~5 hour or so in the range of carry out Forming.

The manufacturing method > of < distributing board

The distributing board (printing distributing board etc.) of present embodiment is at least one face of the laminated body of present embodiment It is formed equipped with conductor layer (wiring etc.).The distributing board of present embodiment is for example formed as follows: using the resin group of present embodiment Object is closed, is formed after uncured resin layer on substrate, heat cure is carried out to it, then irradiates ultraviolet light, obtains insulation solidification Resin layer forms conductor layer using being plated on the insulation curing resin layer.The distributing board of present embodiment can also be containing The composition (multi-layer printed circuit board etc.) of multiple laminated bodies.

Then, the manufacturing method of the distributing board of present embodiment is illustrated.

The manufacturing method of the distributing board of present embodiment has following process: (a) passing through the laminated body of present embodiment Manufacturing method manufacture laminated body laminated body formation process (using at least containing the resin combination of (A) ingredient and (B) ingredient, Resin composition layer is formed on the substrate containing glass substrate or silicon wafer, the process for obtaining laminated body)；(b) described The conductor layer formation process of conductor layer is formed on laminated body (in the resin cured matter layer of laminated body).

Laminated body formation process for example can also be with the following process: carrying out heat cure to resin composition layer, forms resin The heat curing processes of solidified material layer；With the ultraviolet light irradiation process to resin cured matter layer irradiation ultraviolet light.Conductor layer forms work Sequence for example has following process: forming plating shielding layer as the 1st conductor layer in resin cured matter layer by chemical plating Chemical plating process；The 2nd conductor layer, acquisition circuit layer (layer containing the 1st conductor layer and the 2nd conductor layer) are formed with by plating Electroplating work procedure.

Circuit layer for example can implement plating later by implementing chemical plating to resin cured matter layer to obtain.At this point, Circuit layer has the plating shielding layer (the 1st conductor layer) obtained by chemical plating and (the 2nd leads by the way that the conductor layer obtained is electroplated Body layer).It can also be by plating shielding layer and conductor layer (the 2nd conductor layer) integration.

Conductor material used in circuit layer is not particularly limited.Such as circuit layer contain selected from gold, platinum, palladium, silver, copper, The metal of one or more of aluminium, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium.Circuit layer can be single metal layer, be also possible to Alloy-layer.As alloy-layer, can enumerate for example by the alloy of two or more metal in above-mentioned group (such as nickel-chromium alloy, Copper-nickel alloy and copper-titanium alloy) formed layer.

The thickness of circuit layer is different with the design of desired distributing board, in general preferably 3~35 μm, more preferably It is 5~30 μm.

Circuit layer can be formed by plating.For example, the existing public affairs such as subtractive process, semi-additive process, fully-additive process can be passed through Know technology, is plated on the surface of resin cured matter layer and is formed.

It, first can be with using plating method when carrying out circuit fabrication in the resin cured matter layer of the laminated body of present embodiment Carry out roughening treatment.As coarsening solution at this time, chromium/sulfuric acid coarsening solution can be used, alkali crosses mangaic acid coarsening solution, sodium fluoride/chromium/ The oxidisability coarsening solutions such as sulfuric acid coarsening solution, boron fluoric acid coarsening solution.Two will be contained as swelling solution as roughening treatment, such as first The aqueous solution of ethylene glycol monobutyl ether and NaOH are heated to 70 DEG C, carry out impregnation 5 minutes to laminated body.Then, as thick KMnO will be contained by changing liquid₄80 DEG C are heated to the aqueous solution of NaOH, is carried out impregnation 10 minutes.Then, at room temperature in and Liquid (such as stannous chloride (SnCl₂) aqueous hydrochloric acid solution) in carry out impregnation 5 minutes, neutralized.

After roughening treatment, the plating catalyst imparting for adhering to palladium processing is carried out.Plating catalyst imparting processing passes through leaching Stain carries out in the plating catalyst liquid of palladium chloride system.Then, it by being immersed in chemical plating covering liquid, carries out in plating With chemical plating coating (conductor layer, plating screening being precipitated in the whole surface of resin cured matter layer with a thickness of 0.3~1.5 μm or so Cover layer) chemical plating processing.Well known chemical plating covering liquid can be used in chemical plating covering liquid used in chemical plating processing, and It is not particularly limited.Chemical plating is preferably electroless copper.

Conductor material used in plating shielding layer is not particularly limited.For example, can enumerate with it is excellent in the circuit layer Select the identical material of conductor material used.In addition, the thickness of plating shielding layer is also not particularly limited.The thickness of plating shielding layer It such as can be 0.1~2 μm.

Then, electroplating processes are carried out, form the circuit of desired thickness on desirable position.Electroplating processes can lead to It crosses well known method to carry out, be not particularly limited.Plating is preferably copper facing.Circuit layer can for example pass through semi-additive process, Quan Jia It is plated on the surface of resin cured matter layer and is formed at the known technology such as method.Hereinafter, display utilizes semi-additive process shape At the example of circuit layer.

It is right through chemical plating on the plating shielding layer for being formed in resin cured matter layer surface in chemical plating process Wiring pattern desired by Ying Yu forms the plating resist (mask pattern) for exposing a part of plating shielding layer.Pass through Plating is formed after conductor layer on the plating shielding layer of exposing, and plating resist is removed.Later, it will be not required to by etching etc. The plating shielding layer wanted removes, and can form circuit layer.As plating resist, well known plating resist can be used, and It is not particularly limited.It is solid since the excellent resin of surface smoothness can be formed in the manufacturing method of the distributing board of present embodiment Compound layer, therefore circuit layer can be formed with fine Wiring pattern in resin cured matter layer.

These methods can also be repeated, multi-layer wiring board is made.When manufacturing multi-layer wiring board, the bonding can be passed through The above-mentioned multiple stackings of laminated body for being formed with conductor layer (Wiring pattern etc.) are carried out multiple stratification by agent.Later, brill can also be utilized Processing or laser processing form through hole or blind via hole；And interlayer wiring is formed using plating or conductive paste.In this way, can To manufacture multi-layer printed circuit board.

The adhesive strength of circuit layer and resin cured matter layer is not particularly limited, and preferably 0.6kN/m or more, is more preferably 0.7kN/m or more, further preferably 0.8kN/m or more.The upper limit of adhesive strength is simultaneously not limited, for example, can for 10kN/m with Under.Wherein, adhesive strength is that the flaky resin solidified material layer that width is 10mm, length is 100mm has been shelled about in vertical direction The size of loading when 50mm.

Embodiments of the present invention are explained above, but these are for illustrating example of the invention, are not to incite somebody to action The scope of the present invention is only defined in these embodiments.The present invention within the scope of its spirit, can by with difference Implemented in the various modes of above embodiment.

Embodiment

Then, the present invention is illustrated in further detail using embodiment, but the present invention is not appointed by these examples What is limited.

1 > of < embodiment

(1) production of epoxy resin ((A) ingredient)

Bisphenol-A 228g (1.00 moles) and 1,6-HD diethyl are put into the flask with thermometer and blender Alkene ether 170g (1.00 moles) after being warming up to 120 DEG C with 1 hour time, reacts it 6 hours, obtains Transparent semisolid modified multicomponent phenols 398g.

Then, above-mentioned modified multicomponent phenol is put into the flask for being equipped with thermometer, dropping funel, cooling tube and blender Class 398g, epoxychloropropane 925g (10 moles) and n-butanol 185g, make it dissolve.Later, implement nitrogen purging on one side, on one side It is warming up to after 65 DEG C, is decompressed to the pressure that azeotropic occurs, 49 mass % sodium hydrate aqueous solutions were added dropwise with 5 hours times 122g (1.5 moles).Then, continue stirring in 0.5 hour under this condition.It during this period, will using Dean-Stark trap The fraction seperation gone out by azeotropic distillation, water phase is removed, its reaction is made while returning to organic phase in reaction system. Later, unreacted epoxychloropropane is evaporated under reduced pressure and is distilled off.First is added in resulting thick epoxy resin Base isobutyl ketone 1000g and n-butanol 100g are dissolved.In turn, 10 mass % sodium hydrate aqueous solutions are added in the solution 20g after reacting it 2 hours, is washed 3 times repeatedly.Then, passed through by azeotropic to being dehydrated in system After secondary filter, solvent is distilled off under reduced pressure, obtains the epoxy resin 425g of transparency liquid.Epoxide equivalent is 403.

(2) preparation of resin combination

By epoxy resin ((A) ingredient) 49 mass parts made in above-mentioned (1), active form " EXB-9460 " containing ester base resin ((B) ingredient, Dainippon Ink Chemicals's system, trade name, ester group equivalent: 223) 14 mass parts and 1- cyano ethyl -2- phenylimidazole Trimellitic acid salt ((C) ingredient, Shikoku Chem's system, trade name " 2PZ-CNS ") 0.15 mass parts are dissolved in first In ethyl ketone (MEK, solvent) 95 mass parts, obtain resin combination (varnish).

(3) formation, heat cure and ultraviolet treatment with irradiation of B- stage resin layer

It is using Co., Ltd. O's shigane spin coater " SC-308S " that the resin combination obtained in above-mentioned (2) is (clear Paint) (spin coating) (spincoating conditions, 1st:500rpm-30 seconds, 2nd:600rpm-10 seconds) are coated in Nippon Electric Glass Co., Ltd On the very thin glass substrate " OA-10G " (trade name, with a thickness of 100 μm) of system.By being dried 10 minutes at 100 DEG C, make Make the glass baseplate of the resin for the resin composition layer (B- stage resin layer) for having with a thickness of 4 μm.At 170 DEG C, 60 minutes Condition of cure under to resin layer carry out heat cure processing then using conveying type ultraviolet lamp, utilize metal halide Object lamp (maximum wavelength: 350~380nm) reaches 3000mJ/cm according to light quantity²Mode irradiate ultraviolet light, obtain insulating resin Layer.

(4) chemical plating processing and electroplating processes

As the pre-treatment of chemical plating, will contain diethylene glycol monobutyl ether: 200mL/L's and NaOH:5g/L is water-soluble Liquid (swelling solution) is heated to after 80 DEG C, and the substrate with insulating resin layer obtained in above-mentioned (3) is impregnated in the aqueous solution Processing 5 minutes.Then, the substrate with insulating resin layer is immersed at 60 DEG C and adjusts liquid " CLC-601 " (Hitachi's chemical conversion strain formula Commercial firm's system, trade name) in after 5 minutes, washed, be immersed in prepreg solution " Pre Dip Neogant B " at room temperature 2 minutes in (AtotechJapan Co. Ltd. system, trade name).Then, the substrate with insulating resin layer is being changed at 35 DEG C Learn plating catalyst " Activator Neogant 834 " (Atotech Japan Co. Ltd. system, trade name, Alkali Seeda impregnation after five minutes, is washed in).Then, at 35 DEG C by the substrate with insulating resin layer in electroless copper Dipping 15 minutes, Jin Erjin in liquid " Printgant MSK-DK plating liquid " (Atotech Japan Co. Ltd. system, trade name) The plating of row copper sulphate.Later, the annealing that 30 minutes are carried out at 170 DEG C, forms thickness on the surface of insulating resin layer For 20 μm of plating conductor layer.

(5) formation of circuit layer

In order to remove the place etching that do not need of plating conductor layer, grind first with the polishing roll of #600 by copper surface Oxidation overlay film remove.Then, after forming etching resist film, processing is performed etching, later by etching resist film It removes, to form circuit layer.In turn, in order to carry out multiple stratification, the surface of circuit layer is immersed in containing sub- chlorine at 85 DEG C Sour sodium: 50g/L, NaOH:20g/L and tertiary sodium phosphate: 20 minutes in the aqueous solution of 10g/L, being washed later, is done at 80 DEG C Dry 20 minutes, the bumps of copper oxide are formed on the surface of circuit layer.

(6) production of multi-layer wiring board

The process for repeating above-mentioned (3)~(5), the multi-layer wiring board of 3 layers of production.Wherein, it will be formed in outermost circuit Layer is referred to as outer circuit layer (the 3rd circuit layer).

< embodiment 2~7,11,13 and 14 >

Other than being changed the composition of resin combination as shown in table 1 and table 2, carry out similarly to Example 1 Operation, makes various multi-layer wiring boards.

8 > of < embodiment

As shown in table 2, the spherical silicon dioxide " SO-25R " for being 0.5 μm added with average grain diameter used as inorganic filler The quantitative change of solvent is 151 mass parts by the resin combination of (Co., Ltd.'s Admatechs system, trade name), in addition to this, into The operation of row similarly to Example 1, makes multi-layer wiring board.

9 > of < embodiment

Using resin combination similarly to Example 1, using method similarly to Example 1, from B- stage resin layer Formation carry out to heat cure.Then, on the substrate with insulating resin layer, Hitachi Viamechanics CO is utilized₂Swash Light processing machine " LCO-1B21 type ", beam diameter be 80 μm, frequency 500Hz, pulse width be 5 μ sec, transmitting number be 7 Under the conditions of process interlayer connection via hole.It later, the use of lamp is metal halide lamp to the substrate with insulating resin layer Conveying type ultraviolet lamp (maximum wavelength: 350~380nm), reaches 3000mJ/cm according to light quantity²Mode irradiate purple Outside line.

Then, in order to carry out chemical roughening to insulating resin layer, diethylene glycol monobutyl ether will be contained: 200mL/L and The aqueous solution (swelling solution) of NaOH:5g/L is heated to after 80 DEG C, is divided in substrate 5 of the wherein impregnation with insulating resin layer Clock.Then, KMnO will be contained₄: the aqueous solution (coarsening solution) of 60g/L and NaOH:40g/L is heated to 80 DEG C, will be with insulating resin Substrate impregnation 10 minutes in the aqueous solution of layer.Then, at room temperature, as neutralizer (SnCl₂: it is 30g/L, dense Degree is the H of 98 mass %₂SO₄: 300mL/L) aqueous solution in substrate of the impregnation with insulating resin layer 5 minutes, in progress With.Later, operation similarly to Example 1 is carried out, multi-layer wiring board is made.

10 > of < embodiment

In addition to the lamp for irradiating ultraviolet light becomes the conveying type ultraviolet lamp (maximum wavelength 310 of high-pressure sodium lamp ~370nm) except, operation similarly to Example 1 is carried out, multi-layer wiring board is made.Wherein, ultraviolet irradiation and embodiment 1 similarly reaches 3000mJ/cm according to light quantity²Mode carry out.

12 > of < embodiment

Further the resin combination of embodiment 1 is diluted with solvent, makes varnish.Then, (Co., Ltd.) is utilized Very thin glass substrate " the OA-10G " (commodity of Oshigane spin coater (SC-308S) in Nippon Electric Glass Co., Ltd Name, with a thickness of 100 μm) on be coated with (spin coating) (spincoating conditions, 1st:1000rpm-10 seconds, 2nd:1600rpm-20 seconds, 3rd: 1800rpm-5 seconds) varnish.By being dried 10 minutes at 100 DEG C, the resin composition layer having with a thickness of 1 μm is made The glass baseplate of the resin of (B- stage resin layer).In addition to this, operation similarly to Example 1 is carried out, production multilayer is matched Line plate.

1 > of < comparative example

In addition to the composition of resin combination is become table 3 composition (be not used composition of the active form containing ester group compound) it Outside, operation similarly to Example 1 is carried out, multi-layer wiring board is made.

2 > of < comparative example

In addition to the composition of resin combination to be become to the composition of table 3 (as (A) ingredient, using without from alkylene Epoxy resin, that is, phenol novolak type epoxy resin (" N-770 ", Dainippon Ink Chemicals's system, commodity of the structural unit of glycol Name, hydroxyl equivalent: 190) composition) except, operation similarly to Example 1 is carried out, multi-layer wiring board is made.

3 > of < comparative example

In addition to the composition of resin combination to be become to the composition of table 3 (as (B) ingredient, without using active form containing ester It closes object and uses phenol novolak type resin (" TD-2131 ", Dainippon Ink Chemicals's system, trade name, hydroxyl equivalent: group 105) At) except, operation similarly to Example 1 is carried out, multi-layer wiring board is made.

4 > of < comparative example

Instead of very thin glass substrate, (glass substrate is free of using the copper-plated plywood in glass cloth quality epoxy resin two sides Substrate, Hitachi Chemical Co., Ltd.'s system, trade name " MCL-E679F "), in addition to this, carry out identical with embodiment 12 behaviour Make, makes multi-layer wiring board.

< evaluation method >

The evaluation of each Examples and Comparative Examples is carried out using method as shown below.

(1) with the adhesive strength of outer circuit layer (90 degree remove, units: kN/m)

The part that formation width is 10mm in a part of outer layer circuit layer, length is 100mm, one end is removed, It is clamped with clip, measures loading when having shelled about 50mm in vertical direction at room temperature.

(2) the insulating resin bed roughness (surface average roughness, unit: μm) in copper facing etching removing face

Make the test film that processing is performed etching to outer layer circuit layer, removes copper.The test film is cut into 2mm square Left and right, using the ultra-deep measuring shape microscope " VK-8500 type " of Co., Ltd.'s Keyence corporation, in test film 3 points of different location are surveyed under conditions of measured length is 149 μm, multiplying power is 2000 times, resolution ratio is 0.05 μm It is fixed, measured length is subtracted to the surface roughness of the value as insulating resin layer in minimum portion for the roughness maximum portion in 149 μm (Ra), the average value of 3 positions is calculated.

(3) soldering heat resistance

Multi-layer wiring board is cut into 25mm square, make immediately later its float on be adjusted to 288 DEG C ± 2 DEG C soldering bath In, research to the time (unit: second) expanded.

By the composition of resin combination, the thickness of resin composition layer and evaluation result is shown in table in 1~table 3.Comparative example 4 In, crawling has occurred, surface average roughness is compared with embodiment and other comparative examples, it will be apparent that big.

The details of each ingredient is as described below in table.

A1: the epoxy resin (production in embodiment 1 (1) on skeleton with hexylene glycol.With the structure from hexylene glycol The epoxy resin of unit.Epoxy resin with structural unit shown in structural unit shown in formula (I) and formula (II))

A2: phenol novolak type epoxy resin, " N-770 " (Dainippon Ink Chemicals's system, compares ingredient at trade name)

B1: active form contains ester group compound, " EXB-9460 " (Dainippon Ink Chemicals's system, trade name, ester group equivalent: 223)

C1: curing accelerator, imidazole derivatives compounds, 1- cyano ethyl -2- phenylimidazole trimellitic acid salt (four countries Chemical conversion industry Co. Ltd. system, trade name " 2PZ-CNS ")

C2: curing accelerator (triphenylphosphine)

D1: cresol novolak type phenolic resin, " KA-1165 " (Dainippon Ink Chemicals's system, compares ingredient at trade name)

D2: phenol novolak type resin, " TD-2131 " (Dainippon Ink Chemicals's system, compares ingredient at trade name)

E1: methyl ethyl ketone (MEK)

F1: inorganic filler, the spherical silicon dioxide that average grain diameter is 0.5 μm, " SO-25R " (Co., Ltd. Admatechs System, trade name)

F2: inorganic filler, silica filler, " AEROSIL R972 " (Japanese Aerosil Co. Ltd. system, trade name, Specific surface area: 110 ± 20m²/g)

Table 1

Table 2

Table 3

By table 1 and table 2 it is found that in the distributing board of embodiment, even if the state small in the surface roughness of insulating resin layer Under, it is also good with the adhesive strength of outer layer copper, it is suitable for fine wiring.In addition, even 1 μm of film product (embodiment 12), Insulating resin layer can also be film-made.In addition we know, 288 DEG C of soldering heat resistance is also excellent, and Pb-free solder installation is also excellent.

Industrial availability

Through the invention, even if not only in the state that the concaveconvex shape of insulating resin layer surface is small, to conductor layer also table Reveal high bonding force, and is even carried out to remove the residue at via hole bottom using coarsening solutions such as sodium permanganate systems Processing, the roughening concaveconvex shape of insulating resin layer surface is also small, and may insure the bonding force high to conductor layer.In addition, 1 μm film product in can also be filmed.

The good and soldering heat resistance using the distributing board of resin combination production of the invention and the adhesive strength of conductor layer Also excellent.

Claims

1. a kind of manufacturing method of laminated body has the process for forming resin composition layer on substrate, obtaining laminated body, In,

The substrate contains glass substrate or silicon wafer,

The resin composition layer with a thickness of 10 μm hereinafter,

The resin composition layer contains: the epoxy resin of the structural unit with the alkylene glycol for being 3 or more from carbon number, And contain ester group compound.

2. the manufacturing method of layered product according to the claim 1, wherein the alkylene glycol that the carbon number is 3 or more is for oneself Glycol.

3. the manufacturing method of laminated body according to claim 1 or 2, wherein the ester group equivalent containing ester group compound 1 equivalent of epoxy group relative to the epoxy resin is 0.3~1.5 equivalent.

4. the manufacturing method of laminated body described in any one of claim 1 to 3, wherein the thickness of the glass substrate It is 200 μm or less.

5. the manufacturing method of laminated body according to any one of claims 1 to 4, wherein formed by spin-coating method described Resin composition layer.

6. the manufacturing method of laminated body according to any one of claims 1 to 5 is further equipped with to the resin group Close the process that nitride layer carries out heat cure, forms resin cured matter layer.

7. the manufacturing method of laminated body according to claim 6 is further equipped with and irradiates to the resin cured matter layer The process of ultraviolet light.

8. the manufacturing method of laminated body according to claim 7, wherein using maximum wavelength be 300~450nm it is ultraviolet Line lamp irradiates the ultraviolet light under atmospheric pressure environment.

9. the manufacturing method of the laminated body according to any one of claim 6~8, wherein the resin cured matter layer Surface roughness Ra is 0.2 μm or less.

10. a kind of manufacturing method of distributing board, has:

Utilize the process of the manufacturing method manufacture laminated body of laminated body described in any one of claim 6~9；With

The process of conductor layer is formed on the laminated body.