CN1989457A - Photosensitive element, method of forming resist pattern with the same, and process for producing printed wiring board - Google Patents

Photosensitive element, method of forming resist pattern with the same, and process for producing printed wiring board Download PDF

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Publication number
CN1989457A
CN1989457A CNA2005800242940A CN200580024294A CN1989457A CN 1989457 A CN1989457 A CN 1989457A CN A2005800242940 A CNA2005800242940 A CN A2005800242940A CN 200580024294 A CN200580024294 A CN 200580024294A CN 1989457 A CN1989457 A CN 1989457A
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Prior art keywords
photosensitive element
photographic layer
methyl
bed course
mentioned
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Chinese (zh)
Inventor
久保田雅夫
吉回公博
高野真次
矶纯一
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Showa Denko Materials Co ltd
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Hitachi Chemical Co Ltd
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Publication of CN1989457A publication Critical patent/CN1989457A/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/095—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having more than one photosensitive layer
    • G03F7/0955—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having more than one photosensitive layer one of the photosensitive systems comprising a non-macromolecular photopolymerisable compound having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/0073—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces
    • H05K3/0079—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces characterised by the method of application or removal of the mask

Abstract

A photosensitive element which comprises a support film (10), a cushioning layer (12) formed on the support film (10), and a photosensitive layer (14) having a thickness of 10 m or smaller formed on the cushioning layer (12), characterized in that the photosensitive layer (14) is a layer comprising a binder polymer having a weight-average molecular weight of 10,000-100,000, a first photopolymerizable compound having at least one polymerizable, ethylenically unsaturated bond per molecule, and a first photopolymerization initiator and the cushioning layer (12) is a layer comprising a second photopolymerizable compound having at least one polymerizable, ethylenically unsaturated bond per molecule and a second photopolymerization initiator.

Description

Photosensitive element uses its formation method of resist pattern and the manufacture method of printed circuit board (PCB)
Technical field
The present invention relates to photosensitive element, use its formation method of resist pattern and the manufacture method of printed circuit board (PCB).
Background technology
In the past, in the manufacturing field of printed circuit board (PCB) or the Precision Machining field of metal etc.,, extensively adopted the photosensitive element (photosensitive element) of laminated photographic layer on the support film layer as used erosion resistants such as etching, plating.Photosensitive element generally is, goes up in support film (support film) and forms photographic layer (photosensitive layer) afterwards, laminated protective film (passivation film) and forming.
The using method of photosensitive element generally adopts following method.At first, after peeling off diaphragm, carry out crimping (lamination) by the mode of the direct contact substrate of photographic layer (copper base etc.)., make optical tool (photo tool) adherence that be formed with figure (patterning) in transparent thin-film on, irradiation (exposure) ultraviolet isoreactivity light (active ray) thereafter.Then, the spraying imaging liquid uses forming resist pattern (resist pattern) (video picture) to remove unexposed portion.
For removing unexposed used imaging liquid, usually,, use the alkaline video picture type of aqueous sodium carbonate or sodium bicarbonate aqueous solution etc. to become main flow at present so long as have the dissolving of certain degree or disperse the ability of photographic layer just can use.During video picture, it is dissolved or decompose in imaging liquid to form the photosensitive polymer combination of photographic layer.
On the substrate of printed circuit board (PCB), exist because of beating caused concavo-convex situation such as trace more.Therefore, when carrying out lamination,, preferably be attached at the transfer layer (photographic layer and support film etc.) on the substrate, substrate concavo-convex had sufficient tracing ability in order between photographic layer and substrate, not produce not bonding portion.When between photographic layer and substrate, having not bonding portion, after exposure, owing between etchant resist and substrate, produce not bonding portion, therefore, and for example, can be when the etching of carrying out thereafter, produce that conductor lacks or defective such as broken string.
In recent years, the distribution densification development along with printed circuit board (PCB) needs high resolving power.In order to realize that circuit forms the high resolving powerization with photosensitive element, the filming of photographic layer is effective, owing to follow the cause that the concavo-convex photographic layer amount of substrate surface can reduce, in photosensitive element in the past, not adhesive portion branch between substrate and photographic layer increases, and the problem that can not obtain enough manufacturing qualification rates is arranged.In addition, in the photosensitive element in the past, cause the flexibility deficiency of transfer layer integral body owing to the needed thickness of support film and hardness, transfer layer is difficult to follow the concavo-convex variation of substrate surface, its result, not bonding portion between substrate and photographic layer increases, and the problem that can not obtain enough manufacturing qualification rates is arranged.
For the purpose of improving the problems referred to above, the motion of all gimmicks was arranged once.For example have, after being coated with water distribution on the base material, the method for laminated photosensitive element (reference example as, patent documentation 1 and 2); Close aqueous resin with after forming bonding middle layer at layers on substrates, carry out the method (reference example as, patent documentation 3) of laminated photosensitive element; Use vacuum laminator (vaccume laminator), under reduced pressure carry out the motions such as method (reference example as, patent documentation 4 and 5) of laminated photosensitive element.
In addition, as the concavo-convex photosensitive element with tracing ability to substrate surface, motion has the photosensitive element that has thermoplastic resin, middle layer, photographic layer on support film (reference example as, patent documentation 6).
Moreover, when being had tracing ability, substrate surface concavo-convex obtain high-resolution photosensitive element, disclose the photosensitive element (reference example as, patent documentation 7) of have bed course on the support film (cushion layer), photographic layer.
Patent documentation 1: the Jap.P. spy opens clear 57-21890 communique
Patent documentation 2: the Jap.P. spy opens clear 57-21891 communique
Patent documentation 3: the Jap.P. spy opens clear 52-154363 communique
Patent documentation 4: the special public clear 53-31670 communique of Jap.P.
Patent documentation 5: the Jap.P. spy opens clear 51-63702 communique
Patent documentation 6: Japanese patent laid-open 5-80503 communique
Patent documentation 7: the Jap.P. spy opens the 2003-5364 communique
Summary of the invention
The problem that invention institute desire solves
Yet, in patent documentation 1 and 2 methods of being put down in writing, for making for the purpose of the water thin layer evenly adheres to essential matrix (substrate) surface clean that keeps.In addition, as have minor diameter through hole (through-hole), then moisture that is accumulated in the through hole and photographic layer react easily, and the problem that reduces video picture is arranged.
The method that patent documentation 3 is put down in writing has the problem that the video picture, fissility etc. of minor diameter through hole can reduce, and also has simultaneously because of the aqueous resin-coated problems such as cost increase that take place.
Patent documentation 4 and 5 methods of being put down in writing, because the price of device is high, the event that expends time in when vacuumizing forms seldom use at common circuit, only is used as the lamination (Iaminate) that conductor forms the used permanent mask in back.When carrying out the lamination of this permanent mask, still expect the tracing ability of conductor is improved.
In the photosensitive element that patent documentation 6 is put down in writing, though the concavo-convex tracing ability to substrate surface can obtain improvement, but on substrate after the lamination transfer layer, peel off support film when exposing, because thermoplastic resin and middle layer are present between photographic layer and the negative mask, therefore, have and be difficult to obtain high-resolution problem.
In the photosensitive element that patent documentation 7 is put down in writing, exist because film environment for use or keeping environment cause that optical polymerism compound contained in the photosensitive polymer combination or light trigger, adjuvant etc. shift (migrate) problem to bed course easily.Usually, photosensitive element at room temperature uses or keeping, even but problem still can take place under such environment, and can not obtain enough ageing stabilities.And when the part of the contained material of photographic layer was transferred to bed course, the suitable material proportion of photographic layer can change.That is, because the characteristic variations of photosensitive element is, circuit-formed manufacturing qualification rate takes place reduce problem.
The present invention is in view of problem that above-mentioned conventional art had and develop, and purpose is to provide has sufficient tracing ability to substrate surface that should lamination concavo-convex, simultaneously, and the photosensitive element of adherence, resolution and ageing stability excellence.In addition, the object of the invention is, the formation method of the resist pattern that uses above-mentioned photosensitive element and the manufacture method of printed circuit board (PCB) are provided.
Be used to solve the means of problem
For reaching above-mentioned purpose, the invention provides a kind of photosensitive element, it is characterized in that possessing support film, be formed at the bed course on this support film and be formed at the photographic layer of thickness below 10 μ m on this bed course; Above-mentioned photographic layer contains photosensitive polymer combination, it is 10 that described photosensitive polymer combination contains weight-average molecular weight, at least has 1 the 1st optical polymerism compound and the 1st Photoepolymerizationinitiater initiater that can carry out the ethene unsaturated link of polymerization in 000～100,000 binder polymkeric substance (binder polymer), the molecule; Above-mentioned bed course contains and has 1 the 2nd optical polymerism compound and the 2nd Photoepolymerizationinitiater initiater that can carry out the ethene unsaturated link of polymerization in the molecule at least.
According to this photosensitive element, owing to have the event of above-mentioned bed course, even when making the photosensitive polymer combination layer film for high resolving powerization, also can because of the existence of bed course when the lamination, make photographic layer along good so that its adherence of the concavo-convex tracing ability of substrate surface, thereby can fully suppress the generation of the not bonding portion between substrate and photographic layer.Moreover, above-mentioned bed course and since contain optical polymerism compound and Photoepolymerizationinitiater initiater so, can fully suppress the transfer of optical polymerism compound contained in the photographic layer or Photoepolymerizationinitiater initiater, thereby can obtain enough ageing stabilities toward bed course.Again, the weight-average molecular weight of contained binder polymkeric substance is 10,000～100,000 in the photographic layer, and it is residual to reduce the linear video picture that takes place in narrow place between resist pattern thus, and improves resolution.Thus, the side of resist pattern can be made good side again.Thereby, as use photosensitive element of the present invention, then can make concavo-convex tracing ability, adherence, resolution and ageing stability over-all properties reach high level, and can obtain enough manufacturing qualification rates.Again and since have excellent concavo-convex tracing ability so, can be on substrate laminated photographic layer and be unlikely the rising production cost and be unlikely generation bad because of the caused transfer printing (transfer) such as concavo-convex of tiny dust, bubble and substrate surface.
In photosensitive element of the present invention, above-mentioned support film thickness is preferably 5 to 20 μ m.In above-mentioned scope, then can obtain better concavo-convex tracing ability as support film thickness.
In photosensitive element of the present invention, above-mentioned binder polymkeric substance, preferable styrene and/or the styrene derivative of containing is as monomeric unit.Thus, except that can obtaining enough adherences, also can obtain excellent resistance to chemical reagents (anti-plating), be useful on the densification of P.e.c. and high resolving powerization.
In photosensitive element of the present invention, the preferable methacrylic acid that contains of above-mentioned binder polymkeric substance is as monomeric unit.Thus, except that can fully obtaining the effect of the invention described above, also can make excellent alkaline video picture fluidity, be useful on the densification of P.e.c. and high resolving powerization.
In photosensitive element of the present invention, the acid number of above-mentioned binder polymkeric substance is preferably 30～200mgKOH/ gram.Thus, except that the effect that can obtain the invention described above, also can obtain excellent alkaline video picture fluidity, be useful on the densification of P.e.c. and high resolving powerization.
Photosensitive element of the present invention is preferably, and contains to have the compound that 4～40 carbon numbers are 2～6 oxyalkylene (oxy alkylene) in the molecule, as above-mentioned the 1st optical polymerism compound and above-mentioned the 2nd optical polymerism compound.Thus, except that can fully obtaining the effect of the invention described above, also can obtain excellent light sensitivity (light sensitivity), resistance to chemical reagents and fissility are useful on the densification of P.e.c. and high resolving powerization.
Photosensitive element of the present invention is preferably, and contains bisphenol A-type (methyl) acrylate compounds or poly-alkane glycol two (methyl) acrylate, as above-mentioned the 1st optical polymerism compound and above-mentioned the 2nd optical polymerism compound.Thus, except that can fully obtaining the effect of the invention described above, also can obtain excellent light sensitivity, resistance to chemical reagents and fissility, be useful on the densification of P.e.c. and high resolving powerization.
At this, from obtaining the viewpoint of more excellent light sensitivity, resistance to chemical reagents and fissility, above-mentioned bisphenol A-type (methyl) acrylate compounds is preferably the compound with following general formula (1) expression.
Figure A20058002429400091
[in the formula, R 1And R 2Independent respectively expression hydrogen atom or methyl, X 1And Y 1Independent respectively expression carbon number is 2～6 alkylidene (alkylene), and p and q represent to satisfy the positive integer of p+q=4～40.]
Again, for the purpose of obtaining more excellent light sensitivity, resistance to chemical reagents and fissility, above-mentioned poly-alkane glycol two (methyl) acrylate is preferably the compound with following general formula (2) expression.
Figure A20058002429400092
[in the formula, R 3And R 4Independent respectively expression hydrogen atom or carbon number are 1～3 alkyl, X 2, X 3And Y 2The alkylidene (alkylene) of independent separately expression carbon number 2～6, s, t and u are represented the integer that satisfies s+t+u=4～40 selected from 0～30.]
Photosensitive element of the present invention as above-mentioned the 1st Photoepolymerizationinitiater initiater and above-mentioned the 2nd Photoepolymerizationinitiater initiater, is preferably and contains 2,4,5-triarylimidazoles dipolymer.Thus, can obtain resolution and adherence more fully, be useful on the densification of P.e.c. and high resolving powerization.
In the above-mentioned photographic layer in the photosensitive element of the present invention, during as 100 mass parts, the allotment amount of above-mentioned the 1st optical polymerism compound is 30～60 mass parts with above-mentioned binder polymkeric substance and above-mentioned the 1st optical polymerism total amount of compound.With respect to total amount 100 mass parts of above-mentioned binder polymkeric substance and above-mentioned the 1st optical polymerism compound, the allotment amount of above-mentioned the 1st Photoepolymerizationinitiater initiater is preferably 0.1～20 mass parts.Thus, except that can obtaining more fully resolution and adherence, also can obtain excellent light sensitivity, resistance to chemical reagents (anti-plating), physical strength and flexibility, be useful on the densification of P.e.c. and high resolving powerization.
In the photosensitive element of the present invention, above-mentioned bed course be preferably also contain ethene and can with the multipolymer of the monomer of ethylene copolymerization.Thus, can obtain concavo-convex more fully tracing ability, be useful aspect the qualification rate raising of printed circuit board (PCB).
At this, for the purpose of obtaining concavo-convex more fully tracing ability, above-mentioned multipolymer is preferably, the ratio of above-mentioned ethene is the vinyl-vinyl acetate copolymer of 60～90 quality % during as benchmark with the monomer total amount that constitutes this multipolymer, perhaps, with the monomer total amount that constitutes above-mentioned multipolymer during as benchmark the ratio of above-mentioned ethene be ethene-(methyl) ethyl acrylate copolymer of 60～90 quality %.
In the photosensitive element of the present invention, the thickness of above-mentioned bed course is preferably 1～100 μ m.Thus, can obtain concavo-convex more fully tracing ability, be useful on the qualification rate of printed circuit board (PCB) improves.
Photosensitive element of the present invention is preferably, and further has the protective film of this photographic layer of lining on above-mentioned photographic layer.Thus, except that can fully obtaining the effect of the invention described above, operational processes and keeping can be easier to.
Again, the invention provides a kind of formation method of resist pattern, it is characterized by and contain following operation: according to the laminated successively laminated operation that disposes the photosensitive element of the invention described above with the mode on the substrate that forms in circuit of above-mentioned photographic layer, above-mentioned bed course and above-mentioned support film, peel off the stripping process of above-mentioned support film and above-mentioned bed course from above-mentioned photographic layer, the irradiation active ray forms the exposure process of photocuring portion on above-mentioned photographic layer in the established part of above-mentioned photographic layer, and the video picture operation of removing the above-mentioned photographic layer beyond the above-mentioned photocuring portion.
As adopt the formation method of this resist pattern, then owing to use the event of the photosensitive element of the invention described above, concavo-convex tracing ability, adherence, resolution and ageing stability all can reach high level, can be formed on the useful resist pattern of densification and high resolving power aspect of P.e.c..
Moreover, the invention provides a kind of manufacture method of printed circuit board (PCB), it is characterized by, the circuit that will be formed with resist pattern with the formation method of above-mentioned resist pattern forms with substrate in addition etching or plating.
As adopt the manufacture method of this printed circuit board (PCB), then, can make densification and high resolving powerization and reach high-caliber printed circuit board (PCB) owing to form with the formation method of above-mentioned resist pattern of the present invention that resist pattern is dies.
The effect of invention
As adopt the present invention, then can provide substrate surface that should lamination concavo-convex had sufficient tracing ability, simultaneously, the photosensitive element of adherence, resolution and ageing stability excellence uses the formation method of resist pattern of this photosensitive element and the manufacture method of printing distributing board.
Description of drawings
Fig. 1 represents the typical section figure of a kind of suitable example of photosensitive element of the present invention.
A succession of process chart of a kind of suitable example of the formation method of Fig. 2 (a)～(e) expression resist pattern of the present invention.
Fig. 3: the typical section figure that represents the another kind of suitable example of photosensitive element of the present invention.
Symbol description
1,2 photosensitive elements
10 support film
12 bed courses
14 photographic layers
16 protective films
18 circuit form uses substrate
22 pattern masks
Embodiment
The best example of invention
Below, Yi Bian with reference to drawing, Yi Bian described in detail with regard to suitable example of the present invention.At this, in the following explanation, same or considerable part are given and prosign, the repetitive description thereof will be omitted.Again, (methyl) acrylic acid among the present invention means acrylic acid and the methacrylic acid corresponding with acrylic acid, and (methyl) acrylate means acrylate and the methacrylate corresponding with acrylate.
Fig. 1 represents the typical section figure of a kind of suitable example of photosensitive element of the present invention.Circuit shown in Fig. 1 forms with photosensitive element (below, be called for short photosensitive element) 1, has the structure that laminated successively bed course 12 and photographic layer 14 form on the support film 10 as supporter.The thickness of photographic layer 14 is below the 10 μ m, contain weight-average molecular weight 10, binder polymkeric substance in 000～100,000 scope has 1 the 1st optical polymerism compound and the 1st Photoepolymerizationinitiater initiater that can carry out the ethene unsaturated link of polymerization at least in the molecule.Again, bed course 12 contains and has 1 the 2nd optical polymerism compound and the 2nd Photoepolymerizationinitiater initiater that can carry out the ethene unsaturated link of polymerization in the molecule at least.
Below, just constitute each layer of photosensitive element 1 of the present invention, be illustrated.
Support film 10 as long as can support bed course 12 and photographic layer 14, then is not specially limited, and for example, polyethylene terephthalate, polypropylene, tygon, polyester etc. have the suitable uses such as thin polymer film of thermotolerance and solvent resistance.Again, support film 10 can be monolayer constructions will, also can have to contain the multi-ply construction of the film of multiple composition laminated.Moreover, also can on single face, implement processing such as embossing (emboss) processing, corona (corona) processing.
The thickness of support film 10 is not specially limited, and is preferably 2～100 μ m, is more preferred from 5～20 μ m, and the best is 8～16 μ m.During as thickness less than 2 μ m, then when peeling off removal support film 10 and bed course 12 from photosensitive element 1, the tendency that has support film 10 to break, and surpass 100 μ m as thickness, then the flexibility of photosensitive element 1 integral body reduces, and has the tendency that the concavo-convex tracing ability to object surface that should lamination reduces.
Photographic layer 14, contain the binder polymkeric substance (below, sometimes claim " (A) composition "), at least have 1 the 1st optical polymerism compound that can carry out the ethene unsaturated link of polymerization (below, sometimes claim " (B1) composition "), and the 1st Photoepolymerizationinitiater initiater (below, be called for short " (C1) composition " sometimes).
The binder polymkeric substance that belongs to above-mentioned (A) composition requires its weight-average molecular weight 10,000～100, in 000 scope.At this, (A) higher limit of the weight-average molecular weight of binder polymkeric substance is preferably 80,000, is more preferred from 60,000, further is more preferred from 30,000, and special good is 25,000.On the other hand, (A) lower limit of the weight-average molecular weight of binder polymkeric substance is preferably 15,000, is more preferred from 20,000.As weight-average molecular weight less than 10,000, photographic layer tender then, and surpass 100,000 as weight-average molecular weight, linear video picture residual (lack of resolution) then can take place.At this, weight-average molecular weight is by gel permeation chromatography, and uses the value after converting with polystyrene standard.
Above-mentioned (A) binder polymkeric substance can exemplify: acrylic resin, phenylethylene resin series, epoxy are that resin, acid amides are that resin, acid amides epoxy are that resin, alkyd (alkyd) are resin, phenol resin etc.Wherein, the viewpoint from alkaline video picture is preferably acrylic resin.These resins can use more than 2 kinds alone or in combination.
Above-mentioned (A) binder polymkeric substance for example, can carry out the incompatible manufacturing of radical polymerization by making polymerizable monomer.Above-mentioned polymerizable monomer, can exemplify: styrene, vinyltoluene, α-Jia Jibenyixi, p-methylstyrene, can carry out the styrene derivative of polymerization to ethyl styrene etc., acrylamide, vinyl cyanide, the ester class of vinyl alcohols such as vinyl n-butyl ether, (methyl) alkyl acrylate, (methyl) tetrahydrofurfuryl acrylate, (methyl) acrylic acid dimethylamino ethyl ester, (methyl) acrylic acid diethylamino ethyl ester, (methyl) glycidyl acrylate, 2,2,2-three fluoro ethyl (methyl) acrylate, 2,2,3, the 3-tetrafluoro is for propyl group (methyl) acrylate, (methyl) acrylic acid, alpha-brominated (methyl) acrylic acid, alpha-chloro (methyl) acrylic acid, β-furyl (methyl) acrylic acid, β-styryl (methyl) acrylic acid, maleic acid, maleic anhydride, monomethyl maleate, ethyl maleate, maleic acid monoesters such as maleic acid list isopropyl ester, fumaric acid, cinnamic acid, the alpha-cyano cinnamic acid, itaconic acid, crotonic acid, propiolic acid (propiolic acid) etc.These monomers can use more than 2 kinds alone or in combination.
Above-mentioned (methyl) alkyl acrylate can exemplify: (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) acrylic acid pentyl ester, (methyl) Hexyl 2-propenoate, (methyl) acrylic acid heptyl ester, (methyl) 2-ethyl hexyl acrylate, (methyl) 2-EHA and their constitutional isomer.These can use more than 2 kinds alone or in combination.
Above-mentioned (A) binder polymkeric substance from the viewpoint of alkaline video picture, is preferably and contains carboxyl, for example, carries out the incompatible manufacturing of radical polymerization by making polymerizable monomer and other polymerizable monomer with carboxyl.Above-mentioned polymerizable monomer with carboxyl is preferably methacrylic acid.
Again, above-mentioned (A) binder polymkeric substance from adherence, peel property and resistance to chemical reagents (anti-plating), is preferably and contains styrene and/or styrene derivative as monomeric unit.
With above-mentioned styrene and/or styrene derivative as monomer, in order to make the good binder polymkeric substance of adherence, peel property and resistance to chemical reagents (anti-plating), be preferably, with the monomer total amount as benchmark, the allotment amount of above-mentioned styrene and/or styrene derivative is 3～30 quality %, be more preferred from 4～28 quality %, special good is 5～27 quality %.As when allocating quantity not sufficient 3 quality %, the tendency of adherence variation is arranged then, when surpassing 30 quality %, then stripping film increases, the tendency that has splitting time to increase.
The acid number (acid value) of above-mentioned (A) binder polymkeric substance is preferably 30～200mg KOH/g, is more preferred from 45～150mg KOH/g.As the not enough 30mg KOH/g of acid number, the tendency that then has time of developing to increase, when surpassing 200mg KOH/g, the tendency that then has the anti-video picture fluidity of resist of photocuring to reduce.During video picture, when implementing the solvent video picture, be preferably the polymerizable monomer that a small amount of modulation has carboxyl again.
Again, as required, above-mentioned (A) binder polymkeric substance can have the photonasty group.
These binder polymkeric substance can use more than 2 kinds alone or in combination.Binder polymkeric substance when combination is used more than 2 kinds, can exemplify: the binder polymkeric substance more than 2 kinds that becomes branch to constitute by different copolymerizations, the binder polymkeric substance more than 2 kinds of different weight-average molecular weight, the binder polymkeric substance more than 2 kinds of different dispersion degree etc.Also can use the polymkeric substance with multi-mode (multimode) molecular weight distribution of Japanese patent laid-open 11-327137 communique record again.
Again, as when using binder polymkeric substance more than 2 compositions, the weight-average molecular weight of the binder polymkeric substance that then allotment amount is maximum is 10,000～100, and 000 gets final product.
Belong in the molecule of above-mentioned (B1) composition and have at least 1 the 1st optical polymerism compound that can carry out the ethene unsaturated link of polymerization, be not specially limited, be preferably and have the compound that 4～40 carbon numbers are 2～6 oxyalkylene in the molecule.
The oxyalkylene of above-mentioned carbon number 2～6 can exemplify: oxygen ethylidene, oxygen propylidene, oxygen isopropylidene, oxygen butylidene, oxygen pentylidene, oxygen hexylidene etc. from resolution, anti-plating, are preferably oxygen ethylidene or oxygen isopropylidene.
Again, in these (B1) the 1st optical polymerism compound, for example, bisphenol A-type (methyl) acrylate compounds or poly-alkane glycol two (methyl) acrylate especially preferably use.
Above-mentioned bisphenol A-type (methyl) acrylate compounds preferably exemplifies above-mentioned compound with general formula (1) expression.
In the above-mentioned general formula (1), R 1And R 2Independent separately expression hydrogen atom or methyl are preferably methyl.In the above-mentioned general formula (1), X 1And Y 1Independent separately expression carbon number is 2～6 alkylidene, and is preferably ethylidene or propylidene, is more preferred from ethylidene.In the above-mentioned general formula (1), p and q represent to satisfy the positive integer of p+q=4～40, are preferably p+q=6～34, are more preferred from p+q=8～30, and then are more preferred from p+q=8～28, and special good is p+q=8～20, and splendid is p+q=8～16, and the best is p+q=8～12.As p+q less than 4, then the intermiscibility with (A) binder polymkeric substance reduces, and the tendency of peeling off easily arranged when circuit forms with substrate upper strata pressure sensitivity photosensitiveness element, surpass 40 as p+q, then water wettability can increase, and the resist picture peels off easily when video picture is arranged, to the tendency of the anti-plating reduction of solder plating etc.
Above-mentioned carbon number is 2～6 alkylidene, can exemplify: ethylidene, propylidene, isopropylidene, butylidene, pentylidene, hexylidene etc. from resolution, anti-plating, are preferably ethylidene, isopropylidene.
Again; aromatic rings in the above-mentioned general formula (1) can have substituting group; and these substituting groups can exemplify: halogen atom; carbon number is 1～20 alkyl; carbon number is 3～10 naphthenic base; carbon number is 6～18 aryl; phenacyl; amino; carbon number is 1～10 alkyl amino; carbon number is 2～20 dialkylamino; nitro; cyano group; carbonyl; sulfydryl; carbon number is 1～10 alkane sulfydryl; allyl; hydroxyl; carbon number is 1～20 hydroxyalkyl; carboxyl; the carbon number of alkyl is 1～10 carboxyalkyl; the carbon number of alkyl is the acyl group 1～10; carbon number is 1～20 alkoxy; carbon number is 1～10 alkoxy carbonyl group; carbon number is 2～10 alkyl carbonyl; carbon number is 2～10 alkenyl; carbon number is 2～10 N-alkyl-carbamoyl or the group that contains heterocycle; by aryl that these substituting groups replaced etc.Above-mentioned substituting group can form condensed ring (condensed ring).Again, the hydrogen atom in these substituting groups can be by replacements such as above-mentioned substituting group such as halogen atoms.Again, respectively be 2 when above as substituent quantity, the substituting group more than 2 can be identical or inequality.
Compound with above-mentioned general formula (1) expression, can exemplify: 2, two (4-((methyl) acryloyl-oxy the gathers ethoxy) phenyl) propane, 2 of 2-, two (4-((methyl) acryloyl-oxy the gathers third oxygen) phenyl) propane, 2 of 2-, two (4-((methyl) acryloyl-oxy the gathers fourth oxygen) phenyl) propane, 2 of 2-, bisphenol A-type (methyl) acrylate compounds such as 2-two (4-(poly-third oxygen of the poly-ethoxy of (methyl) acryloyl-oxy) phenyl) propane etc.
Above-mentioned 2, two (4-((methyl) acryloyl-oxy the gathers ethoxy) phenyl) propane of 2-, can exemplify: 2, two (4-((methyl) acryloyl diethoxy) phenyl) propane of 2-, 2, two (4-((methyl) acryloyl-oxy three ethoxies) phenyl) propane of 2-, 2, two (4-((methyl) acryloyl tetrem oxygen) phenyl) propane of 2-, 2, two (4-((methyl) acryloyl-oxy five ethoxies) phenyl) propane of 2-, 2, two (4-((methyl) acryloyl six ethoxies) phenyl) propane of 2-, 2, two (4-((methyl) acryloyl-oxy seven ethoxies) phenyl) propane of 2-, 2, two (4-((methyl) acryloyl-oxy eight ethoxies) phenyl) propane of 2-, 2, two (4-((methyl) acryloyl-oxy nine ethoxies) phenyl) propane of 2-, 2, two (4-((methyl) acryloyl-oxy ten ethoxies) phenyl) propane of 2-, 2, two (4-((methyl) acryloyl-oxy 11 ethoxies) phenyl) propane of 2-, 2, two (4-((methyl) acryloyl-oxy ten diethoxies) phenyl) propane of 2-, 2, two (4-((methyl) acryloyl-oxy 13 ethoxies) phenyl) propane of 2-, 2, two (4-((methyl) acryloyl-oxy ten tetrem oxygen) phenyl) propane of 2-, 2, two (4-((methyl) acryloyl-oxy 15 ethoxies) phenyl) propane of 2-, 2, two (4-((methyl) acryloyl-oxy 16 ethoxies) phenyl) propane of 2-etc., wherein, 2, two (4-(the methacryloxypropyl five ethoxies) phenyl) propane of 2-, as BPE-500 (Xin Zhong village chemical industry (thigh) society system, the goods name) can on market, buy, and 2, two (4-(the methacryloxypropyl 15 ethoxies) phenyl) propane of 2-, can on market, buy as BPE-1300 (Xin Zhong village chemical industry (strain) system, goods name).These can use more than 2 kinds alone or in combination.
Above-mentioned 2,2-two (4-(poly-third oxygen of the poly-ethoxy of (methyl) acryloyl-oxy) phenyl) propane, can exemplify: 2, two (4-((methyl) acryloyl-oxy diethoxy 8 third oxygen) phenyl) propane, 2 of 2-, two (4-((methyl) acryloyl-oxy tetrem oxygen 4 third oxygen) phenyl) propane, 2 of 2-, two (4-((methyl) acryloyl-oxy six ethoxies 6 third oxygen) phenyl) propane of 2-etc.These compounds can use more than 2 kinds alone or in combination.
Above-mentioned poly-alkane glycol two (methyl) acrylate can preferably exemplify: with the compound of above-mentioned general formula (2) expression.
In the above-mentioned general formula (2), R 3And R 4Independent separately expression hydrogen atom or carbon number are 1～3 alkyl, are preferably methyl.In the above-mentioned general formula (2), X 2, X 3And Y 2Independent separately expression carbon number is 2～6 alkylidene, is preferably ethylidene or propylidene.In the above-mentioned general formula (2), s, t and u represent the integer that satisfies s+t+u=4～40 selected to be preferably s+t+u=5～30 from 0～30, are more preferred from s+t+u=8～23, and special good is s+t+u=10～15.As s+t+u less than 4, then because the boiling point of this compound can reduce, the tendency that has the foul smell of photographic layer to strengthen as surpassing 40, then because the concentration at the photoreactivity position of per unit mass can reduce, has the tendency that can not obtain the susceptibility in the practicality.
Again, as the oxyalkylene ((Y in the above-mentioned general formula (2) 1-O) s-,-(Y 2-O) t-and-(Y 3-O) u-), for example, when containing aerobic ethylidene and oxygen propylidene, when these exist when a plurality of, a plurality of oxygen ethylidene and oxygen propylidene do not need each to exist with continuous blocked, and can random (random) formula exist yet.
Moreover, when being the oxygen isopropylidene, then can be that the secondary carbon (secondarycarbon) of propylidene combines with oxygen atom as oxyalkylene, also can be primary carbon (primary carbon) combines with oxygen atom.
These can exemplify with the preferable example of the compound of general formula (2) expression: with the compound of following general formula (3)～(5) expression.Wherein, these compounds can use more than 2 kinds alone or in combination.
Figure A20058002429400161
[in the formula, R 3And R 4Independent separately expression hydrogen atom or carbon number are 1～3 alkyl, and EO represents ethylene glycol, and PO represents propylene-glycol-based, m 1, m 2And n 1Expression is selected from 1～30 satisfies m 1+ m 2+ n 1=4～40 integer.]
[in the formula, R 3And R 4Independent separately expression hydrogen atom or carbon number are 1～3 alkyl, and EO represents ethylene glycol, and PO represents propylene-glycol-based, m 3, n 2And n 3Expression is selected from 1～30 satisfies m 3+ n 2+ n 3=4～40 integer.]
Figure A20058002429400171
[in the formula, R 3And R 4Independent separately expression hydrogen atom or carbon number are 1～3 alkyl, and EO represents ethylene glycol, and PO represents propylene-glycol-based, m 4And n 4Expression is selected from 1～30 satisfies m 4+ n 4=4～40 integer.]
Carbon number is 1～3 alkyl in above-mentioned general formula (3)～(5), can exemplify: methyl, ethyl, n-pro-pyl, isopropyl etc.
Sum (the m of the repeat number of ethylene glycol in above-mentioned general formula (3)～(5) 1+ m 2, m 3And m 4) be preferably 1～30 integer, be more preferred from 1～10 integer and then be more preferred from 4～9 integer, special good be 5～8 integer.Surpass 30 as repeat number, the tendency of covering hole fiduciary level (tent reliability) and the deterioration of resist shape is then arranged.
Sum (the n of the repeat number of propylene-glycol-based in above-mentioned general formula (3)～(5) 1, n 2+ n 3And n 4) be preferably 1～30 integer, be more preferred from 5～20 integer and then be more preferred from 8～16 integer, special good be 10～14 integer.Surpass 30 as repeat number, then have resolution to worsen, and the tendency of sludge (sludge) takes place.
Concrete example with the compound of above-mentioned general formula (3) expression can exemplify: R 3And R 4Be methyl, m 1+ m 2=4 (mean values), n 1(Hitachi changes into industry (strain) system, trade name: FA-023M) etc. to the vinyl compound of=12 (mean values).
Concrete example with the compound of above-mentioned general formula (4) expression can exemplify: R 3And R 4Be methyl, m 3=6 (mean values), n 2+ n 3(Hitachi changes into industry (strain) system, trade name: FA-024M) etc. to the vinyl compound of=12 (mean values).
Concrete example with the compound of above-mentioned general formula (5) expression can exemplify: R 3And R 4Be hydrogen atom, m 4=1 (mean value), n 4The vinyl compound of=9 (mean values) (Xin Zhong village chemical industry (strain) system, sample name: NK ester HEMA-9P) etc.
These compounds can use more than 2 kinds alone or in combination.
(B1) the 1st optical polymerism compound except that the as above illustrated optical polymerism compound with ethene unsaturated link, also preferably contains the optical polymerism compound with other ethene unsaturated link.For example, nonyl benzene oxygen gathers poly-alkylene oxide group (methyl) acrylate of nonyl benzene oxygen such as inferior ethoxyl (methyl) acrylate, poly-inferior propoxyl group (methyl) acrylate of nonyl benzene oxygen, poly-inferior propoxyl group (methyl) acrylate of the poly-inferior ethoxyl of nonyl benzene oxygen, γ-chloro-β-hydroxy propyl-Beta '-(methyl) acryloxy ethyl phthalic ester, β-hydroxyalkyl-β '-phthalic acid based compounds such as (methyl) acryloxyalkyl phthalic ester, (methyl) alkyl acrylate etc.
Again, in the photographic layer 14, can contain the optical polymerism compound except that above-mentioned (B1) the 1st optical polymerism compound, can exemplify: make α, beta-unsaturated carboxylic acid and the compound that contains glycidyl react the compound of gained, have the urethanes monomers such as (methyl) acrylate compounds of urethane bonds etc. in the molecule.
The 1st Photoepolymerizationinitiater initiater that belongs to above-mentioned (C1) composition, can exemplify: benzophenone, N, N '-tetramethyl-4,4 '-diaminobenzophenone N such as (Michler's ketons), N '-tetraalkyl-4,4 '-diaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone-1,2-methyl isophthalic acid-aromatic ketone such as [4-(methyl mercapto) phenyl]-2-morpholino base-acetone-1 grade, quinones such as alkyl-anthraquinone, benzoin ether compounds such as benzoin alkylether, benzoin, benzoin compounds such as alkyl benzene acyloin, benzyl dimethyl ketal benzyl derivatives such as (ketal), 2-(adjacent chlorophenyl)-4,5-diphenyl-imidazole dipolymer, 2-(adjacent chlorophenyl)-4,5-two (anisyl) imidazole dimer, 2-(adjacent fluoro phenyl)-4,5-diphenyl-imidazole dipolymer, 2-(guaiacyl)-4,5-diphenyl-imidazole dipolymer, 2-(p-methoxyphenyl)-4,5-diphenyl-imidazole dipolymer etc. 2,4,5-triarylimidazoles dipolymer, the 9-phenylacridine, 1, acridine derivatives such as two (9, the 9 '-acridinyl) heptane of 7-, the N-phenylglycine derivant, α-phenylglycine, cumarin (Network マ リ Application) based compound etc.In addition, 22,4, the substituting group of the aryl of 5-triarylimidazoles can be identical and offer the compound of symmetry, also can be inequality and offer asymmetrical compound.Again,, be more preferred from 2,4,5-triarylimidazoles dipolymer from adherence and sensitivity.These compounds can use more than 2 kinds alone or in combination.
In the photographic layer 14, (A) the allotment amount of binder polymkeric substance with respect to (A) composition and (B1) total amount 100 mass parts of composition, is preferably 40～70 mass parts, is more preferred from 50～60 mass parts.As allocate quantity not sufficient 40 mass parts, and the inadequate tendency of resolution and light sensitivity is then arranged, surpass 70 mass parts, the tendency that then has the photocuring thing to become fragile as the allotment amount.
Again, (B1) the allotment amount of the 1st optical polymerism compound with respect to (A) composition and (B1) total amount 100 mass parts of composition, is preferably 30～60 mass parts, is more preferred from 40～50 mass parts.As allocate quantity not sufficient 30 mass parts, the tendency that then has the photocuring thing to become fragile surpasses 60 mass parts as the allotment amount, and the inadequate tendency of resolution and light sensitivity is then arranged.
Moreover (C1) the allotment amount of the 1st Photoepolymerizationinitiater initiater with respect to (A) composition and (B1) total amount 100 mass parts of composition, is preferably 0.1～20 mass parts, is more preferred from 0.2～10 mass parts.As when allocating quantity not sufficient 0.1 mass parts, the inadequate tendency of light sensitivity being arranged then, when surpassing 20 mass parts as the allotment amount, then when exposure, the absorption on the composition surface can increase and the inner inadequate tendency of photocuring arranged.
Again, photographic layer 14 can contain adjuvant except above-mentioned (A)～(C1) composition (below, claim " (D1) composition " sometimes).(D1) adjuvant can exemplify: have at least 1 optical polymerism compound (oxetane compound (oxetane) etc.) that can carry out the ring-type ether of cationic polymerization in the molecule, cationic polymerization initiators, peacock green dyestuffs such as (Malachite green), tribromo-benzene base sulfone, leuco crystal violet light developers such as (leuco crystal violet), the heat colour developing prevents agent, plasticizers such as para toluene sulfonamide, pigment, filling agent, defoamer, fire retardant, stabilizing agent, adherence invests agent, the leveling agent, peel off promoter, antioxidant, spices, preparation (imaging agent), thermal cross-linking agent etc.These adjuvants with respect to (A) composition and (B1) total amount 100 mass parts of composition, contain about 0.01～20 mass parts separately.These adjuvants can use more than 2 kinds alone or in combination.
Form the photosensitive polymer combination that contains above-mentioned (A)～(D1) composition of photographic layer 14 usefulness, as required, be dissolvable in water methyl alcohol, ethanol, acetone, methyl ethyl ketone, methyl Cellosolve, ethyl Cellosolve, toluene, N, the mixed solvent of dinethylformamide, propylene glycol monomethyl ether equal solvent or these solvents, the solution of making solid constituent and being about 30～60 quality % uses, thereby forms photographic layer.
The thickness of photographic layer 14 must be below 10 μ m.At this, the higher limit of the thickness of photographic layer 14 is preferably 8 μ m, is more preferred from 6 μ m, and special good is 3 μ m.On the other hand, the lower limit of the thickness of photographic layer 14 is preferably 1 μ m, and special good is 2 μ m.Surpass 10 μ m as thickness, the tendency that can not obtain sufficient resolution is then arranged.
Bed course 12 contains and has at least 1 the 2nd optical polymerism compound that can carry out the ethene unsaturated link of polymerization (below, claim " (B2) composition " sometimes) and the 2nd Photoepolymerizationinitiater initiater (below, claim " (C2) composition " sometimes).
Bed course 12 contains this (B2) composition and reaches (C2) composition, can fully suppress (B1) composition contained in the photographic layer 14 and (C1) transfer of the past bed course of composition thus, the result, and photosensitive element can obtain sufficient ageing stability.Do not reach (C2) composition as not containing this (B2) composition in the bed course 12, then the material that particularly molecular weight is little can be transferred to bed course 12 from photographic layer 14, thereby the characteristic of photosensitive element 1 has the tendency of deterioration.
Herein, above-mentioned (B2) the 2nd optical polymerism compound can use and the same compound of above-mentioned the 1st optical polymerism compound.Again, above-mentioned (C2) the 2nd Photoepolymerizationinitiater initiater can use and the same initiating agent of above-mentioned the 1st Photoepolymerizationinitiater initiater.The 2nd optical polymerism compound and the 2nd Photoepolymerizationinitiater initiater separately can be identical or inequality with the 1st optical polymerism compound and the 1st Photoepolymerizationinitiater initiater.In addition, for the purpose of obtaining more fully ageing stability, the 2nd optical polymerism compound and the 2nd Photoepolymerizationinitiater initiater are preferably, and contain contained material of the 1st optical polymerism compound and the contained material of the 1st Photoepolymerizationinitiater initiater respectively.
Again, bed course 12 is preferably, and contains ethene and can carry out the multipolymer of the monomer of copolymerization with this ethene.Again, above-mentioned multipolymer is preferably, vinyl-vinyl acetate copolymer and/or ethene-(methyl) ethyl acrylate copolymer.
Herein, with the ethene components in proportions of the monomer component total amount in the above-mentioned vinyl-vinyl acetate copolymer as benchmark, and with the ethene components in proportions of the monomer component total amount in above-mentioned ethene-(methyl) ethyl acrylate copolymer as benchmark, any is preferably 60～90 quality %, be more preferred from 60～80 quality %, special good is 60～70 quality %.As the ratio less than 60 quality % of above-mentioned ethene, then when using any multipolymer, the adherence that bed course 12 and photographic layer are 14 is too high and have and peel off difficult tendency.On the other hand, surpass 90 quality % as the ratio of ethene, then when using any multipolymer, the adherence that bed course 12 and photographic layer are 14 is low excessively, and the tendency that is difficult to make the photosensitive film 1 that contains bed course 12 is arranged.
Moreover bed course 12 can contain adjuvant (below, sometimes claim " (D2) composition "), should (D2) adjuvant can use with above-mentioned photographic layer 14 in the same adjuvant of (D1) adjuvant.
The thickness of bed course 12 is preferably 1～100 μ m, is more preferred from 10～50 μ m, and special good is 15～40 μ m.As thickness less than 1 μ m, then the concavo-convex tracing ability to the object surface that should carry out lamination has the tendency of reduction, surpasses 100 μ m as thickness, the tendency that then has cost to rise.
Again, photosensitive element 1 is preferably, and (on the F1) further possesses protective film on photographic layer 14.Here, Fig. 3 represents the typical section figure of another suitable example of photosensitive element of the present invention.Photosensitive element 2 shown in Fig. 3 has the structure that laminated successively bed course 12, photographic layer 14 and protective film 16 form on support film 10.
Because protective film 16 was stripped from before being laminated to photosensitive element on the substrate, therefore, preferably have pliability and can strippingly be adhered to photographic layer 14, and not because of the protective film of the temperature damaged of drying oven.This protective film 16; can exemplify: polyolefin such as polyester such as paper, processing release paper, polyester terephthalate, polymethylpentene, polypropylene, tygon, polyvinyl fluoride, Polyvinylchloride etc. contain the film of polyvinyl, nylon polyamide such as (Nylon), cellophane celluloses such as (cellophene), polystyrene of halogen etc.; these can be transparent or nontransparent, also can implement the demoulding and handle.The protective film of buying easily on the market 16 can exemplify: the NF-13 (trade name) of E-200H (trade name), マ Port リ (strain) system of Oji Paper (strain) system etc.
The thickness of protective film 16 is not specially limited, if the size when considering that photosensitive element 1 is rolled into roller (roll) shape then is preferably and makes 10～30 μ m, is more preferred from 10～25 μ m, and special good is 10～20 μ m.
The relation of the interlayer bonding force between bed course 12, support film 10 and the photographic layer 12 is preferably, interlayer bonding force (a1) between support film 10 and the bed course 12 is greater than the interlayer bonding force (a2) between bed course 12 and the photographic layer 14, thus, peeling off between bed course 12 and the photographic layer 14 can be carried out easily.
Again; when possessing protective film 16 on the photographic layer 14; the interlayer bonding force (a3) that is preferably between protective film 16 and the photographic layer 14 is little less than the interlayer bonding force (a2) between bed course 12 and the photographic layer 14, and thus, peeling off between protective film 16 and the photographic layer 14 can be carried out easily.
Above-mentioned interlayer bonding force can use flow graph (rheometer) etc., 23 ℃ of temperature, measures under the condition of humidity 60% as 180 ℃ of peel strengths.
Wherein, the relative bed course 12 of interlayer bonding force (a1) between support film 10 and the bed course 12 and the ratio { (a1)/(a2) } of the interlayer bonding force (a2) between the photographic layer 14; and the relative protective film of interlayer bonding force (a2) between bed course 12 and the photographic layer 14 and the ratio { (a2)/(a3) } of the interlayer bonding force (a3) between the photographic layer 14; be preferably more than 1.05; be more preferred from more than 1.5, special good is more than 2.0.As the ratio less than 1.05 of these interlayer bonding forces, then peel off tendency at the interlayer different with required interlayer.
The method of laminated bed course 12 and photographic layer 14 on support film 10; be not specially limited; can exemplify: (1) is on support film 10 after the laminated bed course 12; then carry out the method for laminated photographic layer 14; (2) method of laminated bed course 12 of while and photographic layer 14 on support film 10; (3) with laminated on the support film structure of bed course 12 and the structure of laminated thoughts photosphere 14 is fitted on protective film 16 method arranged; (4) behind laminated photographic layer on the protective film 16; then; the method of laminated successively bed course 12 and support film 10; (5) laminated photographic layer 14 of while and bed course 12 on protective film 16; then, carry out the method etc. of laminated support film 10.Wherein, the qualification rate viewpoint when making from promoting resist pattern is preferably the method for above-mentioned (3).
Prepared like this photosensitive element 1 can be rolled into the keeping of roller shape.Again, photosensitive element 1 as required, also can have middle layers such as adhesive linkage, light absorbing zone, gas barrier (gas barrier) layer or the protective seam inequality with above-mentioned protective film 16 except that support film 10, bed course 12, photographic layer 14.
Above-mentioned photographic layer 14 is preferably 5～75% to the ultraviolet transmitance of wavelength 365nm, is more preferred from 7～60%, and special good is 10～40%.As this transmitance less than 5%, the tendency of adherence deterioration is then arranged, surpass 75% as this transmitance, the tendency of resolution deteriorates is then arranged.Above-mentioned transmitance, available UV spectrometer is measured, and above-mentioned UV spectrometer can exemplify: 228A type W rays (beam) spectrophotometer of (strain) Hitachi system etc.
Secondly, with regard to the formation method of resist pattern of the present invention, with reference to (a) among the figure 2～(e) be illustrated.
Fig. 2 (a)～(e) is a series of process chart of a kind of suitable example of the formation method of expression resist pattern of the present invention.At first, shown in Fig. 2 (a), use roller (roller) 20, the photosensitive element of laminated successively support film 10, bed course 12 and photographic layer 14 is pressed photographic layer 14 contact circuits form mode crimping with substrate 18, shown in Fig. 2 (b), carry out forming with the laminated operation of laminated successively photographic layer 14 on the substrate 18 with bed course 12 and base film 10 at circuit.Here, when on photographic layer 14, having protective film, then peel off protective film and implement laminated operation afterwards again as if photosensitive element 1.Then, shown in Fig. 2 (c), implement to peel off the stripping process of bed course 12 and support film 10, form with the laminated substrate that possesses photographic layer 14 on the substrate 18 to obtain circuit.
Secondly, shown in Fig. 2 (d),, implement established part irradiation active ray, to form the exposure process of photocuring portion to the photographic layer in the laminated substrate 14 by using the pattern mask 22 that ultraviolet isoreactivity light is had transparent part.Then, shown in Fig. 2 (e), implement to remove the video picture operation of photocuring portion photographic layer 14 in addition, to form resist pattern 24.
In the above-mentioned laminated operation,, can exemplify: on one side photographic layer 14 is heated to about 70～130 ℃, on one side with (1～10kgf/cm about 0.1～1MPa with photographic layer 14 laminated methods on circuit formation usefulness substrate 18 2About) pressure with photographic layer 14 be crimped on circuit form with on the substrate 18 to carry out laminated method.At this moment, from the viewpoint of adherence and tracing ability, can under reduced pressure carry out laminated.For the purpose of further improving laminated property, can under reduced pressure carry out circuit and form the thermal pretreatment of using substrate 18 again.In addition, usually, circuit forms with the laminated surface of substrate 18 metal covering normally, is not specially limited.Moreover, circuit form can have with substrate 18 surfaces concavo-convex, can be by use photosensitive element 1 of the present invention, carry out lamination well with concavo-convex tracing ability.
Finished laminated photosensitive element 1 in this way, in above-mentioned stripping process, removed support membrane 10 and bed course 12 from photographic layer 14.Then, in above-mentioned exposure process,, shine active ray by the portrait shape through the negative or positive type pattern mask 22 that is called former figure (artwork) to photographic layer 14.As the light source of active ray, can use known light source, for example, carbon arc lamp (carbon arc lamp), mercury vapor arc lamp, extra-high-pressure mercury vapour lamp, high-pressure mercury-vapor lamp, xenon arc lamp (Xenon arc lamp) etc. are the ultraviolet lamp of radiation effectively.Also can use the lamp of taking a picture with effective radiation such as tack bulb, sunlamp (solar lamp) visible light again.
Above-mentioned video picture operation is undertaken by following manner: video picture forms resist pattern by enforcement removals such as wet type video picture, dry type video picture unexposed (photocuring portion).During the wet type video picture, using alkaline aqueous solution, water system imaging liquid, organic solvent is the pairing imaging liquids of photosensitive resin composition such as imaging liquid, for example, adopt spraying, shake dipping, brush (brushing), scrape known method such as (scrapping) and carry out video picture.
Imaging liquid can use safety and stable such as alkaline aqueous solution, the imaging liquid that operability is good.The alkali of above-mentioned alkaline aqueous solution (base) for example can use: as the alkali hydroxides such as oxyhydroxide of lithium, sodium or potassium; Carbonic acid alkali such as the carbonate of lithium, sodium, potassium or ammonium or supercarbonate; Alkali metal phosphate such as potassium phosphate, sodium phosphate; Alkali metal pyrophosphate such as sodium pyrophosphate, potassium pyrophosphate etc.Again, the used alkaline aqueous solution of video picture is preferably the lean solution of 0.1～5 quality % sodium carbonate, the lean solution of 0.1～5 quality % sal tartari, the lean solution of 0.1～5 quality % NaOH, the lean solution of 0.1～5 quality % sodium tetraborate etc.Again, the pH value of the alkaline aqueous solution that video picture is used is preferably 9～11, and its temperature is then regulated according to the video picture of photosensitive polymer combination layer 14.In alkaline aqueous solution, can add a small amount of organic solvent that surfactant, defoamer, promotion video picture use etc. again.
Above-mentioned water system imaging liquid is water or the imaging liquid that is made of the organic solvent of alkaline aqueous solution and more than one.Herein, with regard to the alkali of the alkaline aqueous solution in the water system imaging liquid, except that above-mentioned alkali, also can exemplify: borax or sodium silicate, tetramethylammonium hydroxide, monoethanolamine, ethylenediamine, diethylene triamine, 2-amino-2-hydroxymethyl-1, ammediol, 1,3-diamino-propanol-2-morpholine etc.The preferable pH 8～12 that is adjusted in the scope that can fully carry out the resist video picture of the pH value of imaging liquid, the better pH 9～10 that is adjusted to.
With regard to above-mentioned organic solvent, can exemplify: tri acetylacetonate alcohol, acetone, ethyl acetate, have alcoxyl ethanol that carbon number is 1～4 alkoxy, ethanol, isopropyl alcohol, butanols, diethylene glycol monomethyl ether, TC, diethylene glycol single-butyl ether etc.These organic solvents can use more than 2 kinds alone or in combination.The concentration of organic solvent is preferably 2～90 quality % usually, and its temperature then can be regulated according to video picture.Also can add surfactant, defoamer etc. on a small quantity in the water system imaging liquid again.
With regard to above-mentioned organic solvent is imaging liquid, can exemplify: 1,1,1-three chloro ethane, N-Methyl pyrrolidone, N, dinethylformamide, cyclohexanone, hexone, gamma-butyrolacton etc.These organic solvents for the purpose of preventing to catch fire, are preferably in the scope of 1～20 quality % and add water.
Again, in the video picture operation, as required, also can be also with the developing method more than 2 kinds.The video picture mode has dipping (dipping) mode, stirring (バ ト Le) mode, spray pattern, mode such as brushes, scrapes, and the high-pressure fog mode is optimum aspect the resolution raising.
As the processing after the video picture, also can implement heating or 0.2～10mJ/cm about 60～250 ℃ as required 2About exposure, make resist pattern further solidify the back thus and use.
In the manufacture method of printed circuit board (PCB) of the present invention, will form with substrate in addition etching or plating according to the resulting circuit that is formed with resist pattern of the formation method of the resist pattern of the invention described above.
Circuit form with the etching of substrate or plating be resist pattern with video picture as mask, and circuit formation is implemented with the mode that substrate surface carries out etching or plating according to known method in the past.
Used etching solution in above-mentioned etching for example can use, and copper chloride solution, ferric chloride solution, alkaline etch solution, hydrogen peroxide are etching solution etc., from the good angle of etching factor (etch factor), are preferably the use ferric chloride solution.
Coating method when implementing above-mentioned plating can exemplify: copper-plating methods such as copper sulphate plating, cupric pyrophosphate plating, plating such as high homogeneous solder plating (Ha イ ス ロ one は ん だ め つ I) solder method, watt is bathed nickel plating methods such as (Watt ' sbath) (nickelous sulfate-nickel chloride) plating, nickel sulfamic acid plating, gold-plated firmly (hard goldplating) soft gold-plated gold-plated methods such as (soft gold plating) etc.
After implementing etching or plating, resist pattern for example can, by being peeled off with the stronger alkaline aqueous solution of alkaline aqueous solution than video picture.This alkaline aqueous solution for example can be used: the potassium hydroxide aqueous solution of 1～10 quality % sodium hydrate aqueous solution, 1～10 quality % etc.The mode of peeling off can exemplify: impregnation method, spray pattern etc., impregnation method and spray pattern can be used separately, and also can and use.In addition, be formed with the printed circuit board (PCB) of resist pattern, can be multilayer board.
Again, be to form when implementing plating as above-mentioned plating with substrate to possessing the circuit that insulation course is arranged and be formed at the conductor layer on the insulation course, then need to remove the conductor layer beyond the figure.This removal method can exemplify: after peeling off resist pattern, etching method gently, perhaps, behind above-mentioned plating, then implement solder plating etc., peeling off resist pattern then uses and uses scolder that circuit part is covered, then, only use can the etched conductors layer the method handled of etching solution etc.
Embodiment
Below, according to embodiment and comparative example the present invention being described more specifically, the present invention is not limited by following embodiment.
[synthesizing of binder polymer A]
In the flask that possesses stirring machine, reflux cooler, thermometer, tap funnel and nitrogen ingress pipe, and the mixed liquor of adding methyl Cellosolve/toluene (mass ratio: 3/2) 350g, stir and be heated to 80 ℃ while purge nitrogen.On the other hand, prepare to have mixed the solution (below, title " solution a ") of methacrylic acid 150g, methyl methacrylate 300g as copolymerization monomer and styrene 150g and azoisobutyronitrile 9.0g.Then, to the mixed liquor that is heated to above-mentioned methyl Cellosolve/toluene of 80 ℃ (mass ratio: 3/2), with behind 4 hours solution a that drip, on one side stir on one side down at 80 ℃ and to be incubated 2 hours.And then, will be at the mixed liquor of methyl Cellosolve/toluene (mass ratio: 3/2) be dissolved with the solution of azoisobutyronitrile 1.2g among the 50g, dripped in the flask with 10 minutes.After 3 hours, heated to 90 ℃ 80 ℃ of insulations while the solution that stirs after dripping with 30 minutes.In 90 ℃ of insulations cooling after 2 hours, make the solution of binder polymer A.The nonvolatile component of the solution of binder polymer A (solid constituent) is 60 quality %, and the weight-average molecular weight of binder polymer A is 20,000.Here, weight-average molecular weight is measured by gel permeation chromatography (GPC), and the typical curve of use polystyrene standard converts and derives.In addition, the condition of GPC is as described below.
(GPC) condition
Pump: the L-6000 of Hitachi type ((strain) Hitachi system, trade name)
Chromatographic column: Gelpack GL-R420+Gelpack GL-R430+Gelpack GL-R440 (totally 3) (more than, Hitachi changes into industry (strain) system, trade name)
Eluent: tetrahydrofuran
Measure temperature: 25 ℃
Flow: 2.05ml/ minute
Detecting device: the L-3300 of Hitachi type RI ((strain) Hitachi system, trade name)
[synthesizing of binder polymer B]
Except that the addition of the azoisobutyronitrile in solution a is made as 3.0g, all the other then when synthetic with the binder polymer A identical method synthesize, make binder polymkeric substance (B) solution.The nonvolatile component (solid constituent) of binder polymer B solution is 60 quality %, and the weight-average molecular weight of binder polymer B is 60,000.
[binder polymkeric substance C's is synthetic]
(mass ratio: amount 3/2) is made as 550g with the mixed liquor that originally adds the methyl Cellosolve/toluene of flask, and the addition of the azoisobutyronitrile among the solution a is made as 0.6g, in addition, all the other then when synthetic with the binder polymer A identical method synthesize, make the solution of binder polymkeric substance C.The nonvolatile component (solid constituent) of binder polymkeric substance C solution is 50 quality %, and the weight-average molecular weight of binder polymkeric substance C is 150,000.
With weight-average molecular weight and the acid number of binder polymer A, B and C, summary sheet is shown in Table 1.
[table 1]
The binder polymer A The binder polymer B Binder polymkeric substance C
Methacrylic acid 25 25 25
Methyl methacrylate 50 50 50
Styrene 25 25 25
Weight-average molecular weight 20,000 60,000 150,000
Acid number (mg KOH/g) 163 163 163
[making of photographic layer material]
Material shown in the setup sheet 2 is to make photographic layer material (I), (II) and (III).Wherein, the unit of the allotment amount of each material in the table 2 is a mass parts.
[table 2]
The photographic layer material
(I) (II) (III)
(A) composition The solution of binder polymer A 150 (solid constituents: 90) - -
The solution of binder polymer B - 150 (solid constituents: 90) -
The solution of binder polymkeric substance C - - 180 (solid constituents: 90)
(B1) composition 2, two (4-(the methacryloxypropyl 15 ethoxies) phenyl) propane of 2- 30.0 30.0 30.0
The EO modification nonyl phenyl acrylate (repetitive of glycol chain: 8) 10.0 10.0 10.0
(C1) composition N, N '-tetraethyl-4,4 '-diaminobenzophenone 0.15 0.15 0.15
2-(adjacent chlorophenyl)-4,5-diphenyl-imidazole dipolymer 3.0 3.0 3.0
Adjuvant Leuco crystal violet 0.5 0.5 0.5
Peacock green 0.05 0.05 0.05
Para toluene sulfonamide 4.0 4.0 4.0
Solvent Acetone 10.0 10.0 10.0
Toluene 10.0 10.0 10.0
Methyl alcohol 3.0 3.0 3.0
Dinethylformamide 3.0 3.0 3.0
[making of course]
Material shown in the setup sheet 3 is to make course (I), (II), (III) and (IV).Herein, the unit of the allotment amount of each material in the table 3 is a mass parts.
[table 3]
Composition Material Course
(I) (II) (III) (IV)
Major component Ai Fafu lux (エ バ Off レ Star Network ス) EEA A70 (chemicals (デ ユ Port Application Port リ ケ ミ Le) society's system is gathered by Mitsui Du Pont) 15 15 15 15
(B2) composition 2, two (4-(the methacryloxypropyl 15 ethoxies) propane of 2- 1 1 1 -
The EO modification nonyl phenyl acrylate (repetitive of glycol chain: 8) 1 - 1 -
(C2) composition 2-(adjacent chlorophenyl)-4,5-diphenyl-imidazole dipolymer 0.3 0.3 - -
Solvent Toluene 85 85 85 85
Dinethylformamide 1 1 - -
(embodiment 1～3 and comparative example 1～2)
[making of photosensitive element]
Embodiment 1, and photographic layer material (I) and course (II) are made up, and makes photosensitive element according to the following step.
At first, as support film, prepare polyethylene terephthalate (PET) film (trade name: G2-16 of thickness 16 μ m, Supreme Being people's (strain) system), thereon so that dried thickness reaches the even coated mat layer material of the mode of 10 μ m (II), in 115 ℃ hot air convection formula dryer dry 10 minutes to form bed course.Then, on bed course so that dried thickness reaches the even photosensitive coated layer material of the mode of 10 μ m (I), in 100 ℃ hot air convection formula dryer dry 10 minutes to form photographic layer.Then,, prepare the biaxial stretch-formed polypropylene film (trade name: E-200H, Oji Paper (strain) system) of thickness 20 μ m, this frlml laminating on photographic layer, is made the photosensitive element of embodiment 1 as protective film.The photosensitive element of gained so that support film be in the outside mode batched.
Again, among the embodiment 2, photographic layer material (I) and course (II) are used in combination, simultaneously, make cushion thickness reach 20 μ m; Among the embodiment 3, photographic layer material (II) and course (II) are used in combination, simultaneously, make cushion thickness reach 20 μ m; In the comparative example 1, photographic layer material (I) and course (II) are used in combination, simultaneously, make bed course and photographic layer thickness reach 20 μ m; In the comparative example 2, photographic layer material (I) and course (IV) are used in combination, simultaneously, make cushion thickness reach 20 μ m, in addition, all the other make the photosensitive element of embodiment 2～3 and comparative example 1～2 then according to similarly to Example 1 mode.
(embodiment 4～9 and comparative example 3～8)
[making of photosensitive element]
Among the embodiment 4, photographic layer material (I) and course (I) are made up, made photosensitive element according to the following step.
At first, as support film, prepare polyethylene terephthalate (PET) film (trade name: G2-16 of thickness 16 μ m, Supreme Being people's (strain) system), and thereon so that dried thickness reaches the even coated mat layer material of the mode of 10 μ m (I), in 115 ℃ hot air convection formula dryer dry 10 minutes to form bed course.Then, prepare the PET film (trade name: G2-16 of another thickness 16 μ m, Supreme Being people's (strain) system), and thereon so that dried thickness reaches the even photosensitive coated layer material of the mode of 6 μ m (I), in 100 ℃ of hot air convection formula dryers dry 10 minutes to form photographic layer.Then, so that the mode that bed course and photographic layer can be bonding (so that the PET film can be in the mode in the outside) is fitted mutually, make the photosensitive element of embodiment 4.Wherein, with the PET film of photographic layer side as protective film.
Again, in embodiment 5～9 and comparative example 3～7, shown in table 5 and 6 mode removed changes the material and the thickness of photographic layer, and beyond the material and thickness of bed course, and all the other then by step similarly to Example 4, make photosensitive element.Thus, make the photosensitive element of embodiment 5～9 and comparative example 3～7.
Again, in comparative example 8, prepare the PET film (trade name: G2-16, Supreme Being people's (strain) system) of thickness 16 μ m, and thereon so that dried thickness reaches the even photosensitive coated layer material of the mode of 6 μ m (I), in 100 ℃ hot air convection formula dryer dry 10 minutes to form photographic layer.Then,, prepare the biaxial stretch-formed polypropylene film (trade name: E-200H, Oji Paper (strain) system) of thickness 20 μ m, this frlml laminating on photographic layer, is made the photosensitive element of comparative example 8 as protective film.[making of printed circuit board (PCB) A (evaluation of adherence and resolution)]
Use the photosensitive element of embodiment 1～9 and comparative example 1～8 respectively, make printed circuit board (PCB) A according to the following step, and carry out the evaluation of adherence and resolution.Wherein, after the photosensitive element use 12 hours with interior element.
At first, use have the brush that is equivalent to #600 muller (three open (strain) system, (Hitachi changes into industry (strain) system to grind on the single face the laminated glass epoxy substrate that the Copper Foil of thickness 35 μ m arranged, trade name: copper surface MCL-E67-35S), after the washing, in addition dry with airflow, make copper-clad laminate.
Then; after the gained copper-clad laminate is warmed to 80 ℃; (Hitachi changes into industry (strain) system to use heat zone press (laminator); HLM-3000); peel off the protective film of photosensitive element on one side; one side towards copper-clad laminate, is laminated to photographic layer on the copper-clad laminate so that the support film side can contact the mode of roller.
At this moment, setting laminating roll speed is 1.5m/ minute, and the laminating roll temperature is 110 ℃, and the cylinder pressure of roller is 0.4MPa.
Then, after lamination is finished, be cooled to 23 ℃ after, peel off the support film and the bed course of photosensitive element.Under the situation of the photosensitive element of comparative example 8, only peel off support film herein.
Then, ((unit: the resolution evaluation of the circuitous pattern μ m) is with bearing mask 400/6～400/47 to have Stouffer 21 lattice metraster and line width (line width)/interval width (space width) to use negative mask, and has line width/interval width in 6/400～47/400 (unit: the adherence evaluation of the circuitous pattern μ m) is with bearing mask), and Ou Ke (オ one Network) makes system exposure machine (the pattern EXM-1201 of institute's (strain), the mercury short light modulation exposes so that the residual lattice number after the video picture of Stouffer 21 lattice exposures lattice table reaches 6.0 energy.
Then, use 1 quality % aqueous sodium carbonate (30 ℃), by the time of developing shown in table 4～6 to the photosensitive element video picture (atomisation pressure: 0.18MPa), thereby on copper-clad laminate, form resist pattern of spraying.
Herein, to use the resolution evaluation to be measured as resolution with the value of the residual minimum interval width of the no video picture of the negative formed resist pattern of mask, and will use the adherence evaluation with the formed resist pattern of negative mask be unlikely that generation is crawled or breach under formed minimum resist width measured as adherence.These results are shown in table 4～6.Wherein, this value is more little, and expression resolution and adherence are excellent more.
[making of printed circuit board (PCB) B (evaluation of concavo-convex tracing ability)]
Use the photosensitive element of embodiment 1～9 and comparative example 1～8 respectively, make printed circuit board (PCB) B according to following step, to implement the evaluation of concavo-convex tracing ability.Herein, after the photosensitive element use 12 hours with interior element.
At first, use RY-3210 (trade name as photosensitive element, Hitachi changes into industry (strain) system), use line width/interval width 1 as negative mask, 000/100 (unit: negative mask μ m), in addition, all the other then by the mode same with the making of printed circuit board (PCB) A, make the copper-clad laminate that is formed with resist pattern.
Secondly, the copper-clad laminate of gained was flooded 1～30 minute in the ammonium persulfate aqueous solution (30 ℃) of 100g/L, again resist pattern is used stripper (3 quality % sodium hydrate aqueous solutions, 50 ℃, atomisation pressure: 0.18MPa) peeled off, make that to have recessed be 1～15 μ m deeply, recessed wide be the concavo-convex tracing ability evaluation substrate of the jog of 100 μ m.
The concavo-convex tracing ability evaluation of gained is heated after 80 ℃ with substrate; (Hitachi changes into industry (strain) system to use the heat zone press; HLM-3000); while the protective film of peeling off photosensitive element with photographic layer towards base material be laminated on the aforesaid substrate so that the support film side can contact the mode of roller.At this moment, make laminating roll the axle parallel with the length direction of substrate recess.Again, at this moment, setting laminating roll speed is 1.5m/ minute, and the laminating roll temperature is 110 ℃, and the cylinder pressure of roller is 0.4MPa.
After lamination is finished, be cooled to 23 ℃ after, peel off the support film and the bed course of photosensitive element.Under the situation of the photosensitive element of comparative example 8, only peel off support film herein.
Then, use negative mask (to have Stouffer 21 lattice metraster, and line width/interval width is in 100/100 (unit: the negative mask of the circuitous pattern μ m)), and Ou Ke makes system exposure machine (the pattern EXM-1201 of institute's (strain), the mercury short light modulation), be that 6.0 energy exposes with the residual lattice number of Stouffer 21 lattice metraster after video picture.
Then, use 1 quality % aqueous sodium carbonate (30 ℃), press the spraying video picture (atomisation pressure: 0.18MPa), and on copper-clad laminate, form resist pattern that the time of developing shown in table 4～6 is implemented photosensitive element.
Then, with cupric chloride etching solution (2mol/L CuCl 22N HCl aqueous solution; 50 ℃) spraying (atomisation pressure: 0.2MPa) in 100 second; the copper of the part of not protected by resist with dissolving (etching); re-use stripper (3 quality % sodium hydrate aqueous solutions; 50 ℃, atomisation pressure: 0.2MPa) peel off resist pattern, to make concavo-convex tracing ability evaluation with the printed circuit board (PCB) B that is formed with copper wire (line) on the substrate.
Under the situation that photosensitive element is not followed with the jog on the substrate with concavo-convex tracing ability evaluation, owing to can produce the space between resist and substrate, therefore, etching solution immerses the cross section of resist and recess, copper wire is dissolved so that copper wire can not be continuous, thereby can cause disconnection defect.This recess depths (μ m) that is confirmed to be disconnection defect is measured as concavo-convex tracing ability, and its result is shown in table 4～6.Herein, this value is big more, represents that concavo-convex tracing ability is excellent more.
[making of printed circuit board (PCB) C (evaluation of ageing stability)]
Use the photosensitive element of embodiment 1～9 and comparative example 1～8 respectively, make printed circuit board (PCB) C according to following step.After use this moment 12 hours with interior element, and after making through the element of 30 days (at 23 ℃, the dark place keeping 60%RH (relative humidity) under), estimate ageing stability by comparing both.
At first, (Hitachi changes into industry (strain) system with the laminated glass epoxy substrate that the Copper Foil of thickness 35 μ m arranged on the single face, trade name: copper surface MCL-E67-35S), the muller (three open (strain) system) that use has the suitable brush of #600 grinds, the washing back makes copper-clad laminate with the airflow drying.
Then; the copper-clad laminate that gained is sent out is heated after 80 ℃; (Hitachi changes into industry (strain) system to use the heat zone press; HLM-3000); peel off the protective film of photosensitive element on one side; one side towards copper-clad laminate, is laminated to photographic layer on the copper-clad laminate so that the support film side can contact the mode of roller.
At this moment, setting laminating roll speed is 1.5m/ minute, and the laminating roll temperature is 110 ℃, and the cylinder pressure of roller is 0.4MPa.
Then, after lamination is finished, be cooled to 23 ℃ after, peel off the support film and the bed course of photosensitive element.Under the situation of the photosensitive element of comparative example 8, then only peel off support film herein.
Then, use negative mask (to have Stouffer 21 lattice metraster, (unit: the resolution evaluation of circuitous pattern μ m) is with bearing mask 400/6～400/47 for line width/interval width, and line width/interval width is in 6/400～47/400 (unit: the adherence evaluation of circuitous pattern μ m) is with bearing mask), and Ou Ke makes system exposure machine (the pattern EXM-1201 of institute's (strain), the mercury short light modulation), so that adopt to make back 12 hours Stouffer 21 lattice metraster during with interior photosensitive element can the residual lattice number after video picture be that 6.0 energy exposes.Exposure energy after the use during through 30 days photosensitive element is set at and makes back 12 hours with the same exposure energy of interior photosensitive element.
Then, use 1 quality % aqueous sodium carbonate (30 ℃), press time of developing shown in table 4～6 and implement spraying video picture (atomisation pressure: 0.18MPa), on copper-clad laminate, form resist pattern.
For 12 hours situations after the use with interior photosensitive element, and use is after leave standstill the situation of the photosensitive element of preserving 30 days in the following dark place of room temperature (23 ℃, 60%RH), to use the resolution evaluation to be measured as resolution with the value of the residual minimum interval width of the no video picture of the negative formed resist pattern of mask, and will use the adherence evaluation with the negative formed resist pattern of mask be unlikely that generation is crawled and breach under formed minimum resist width measured as adherence.Wherein, this value is littler, and expression resolution and adherence are more excellent.Again, because 12 hours resolution and adherences during with interior photosensitive element are the results who comes to the same thing with above-mentioned [making of printed circuit board (PCB) A (evaluation of adherence and resolution)] gained after the use, therefore, only will use result to be shown in table 4～6 through the situation of the photosensitive element after 30 days.
Again, to use after leave standstill the residual lattice number of the photosensitive element situation of preserving 30 days (23 ℃, 60%RH, dark place) and measure.Its result is shown in table 4～6.Here, after the use 12 hours during with interior photosensitive element and use after leave standstill (23 ℃ of preservations, 60%RH, residual lattice number identical (6.0) during the dark place) photosensitive element, and do not observe the situation of the characteristic variations of resolution and adherence, can be evaluated as the ageing stability excellence, and each situation inequality of residual lattice number, resolution and adherence, it is not enough then can be evaluated as ageing stability.
[table 4]
Project Embodiment 1 Embodiment 2 Embodiment 3 Comparative example 1 Comparative example 2
Photographic layer Material (I) (I) (II) (I) (I)
Thickness (μ m) 10 10 10 20 10
Bed course Material (II) (II) (II) (II) (IV)
Thickness (μ m) 10 20 20 20 20
Time of developing (second) 10 10 10 25 10
Adherence (μ m) 6 6 6 10 6
Resolution (μ m) 6 6 10 12 6
Concavo-convex tracing ability (μ m) 6 8 8 12 8
Stability Residual lattice number 6.0 6.0 6.0 6.0 4.0
Adherence (μ m) 6 6 6 10 18
Resolution (μ m) 6 6 10 12 15
[table 5]
Project Embodiment 4 Embodiment 5 Embodiment 6 Embodiment 7 Embodiment 8 Embodiment 9
Photographic layer Material (I) (I) (I) (I) (I) (II)
Thickness (μ m) 6 6 10 10 10 10
Bed course Material (I) (I) (I) (II) (II) (II)
Thickness (μ m) 10 20 10 10 20 20
Time of developing (second) 6 6 10 10 10 10
Adherence (μ m) 6 6 6 6 6 6
Resolution (μ m) 6 6 6 6 6 10
Concavo-convex tracing ability (μ m) 5 7 6 6 8 8
Stability Residual lattice number 6.0 6.0 6.0 6.0 6.0 6.0
Adherence (μ m) 6 6 6 6 6 6
Resolution (μ m) 6 6 6 6 6 10
[table 6]
Project Comparative example 3 Comparative example 4 Comparative example 5 Comparative example 6 Comparative example 7 Comparative example 8
Photographic layer Material (III) (I) (I) (I) (I) (I)
Thickness (μ m) 10 6 6 10 20 6
Bed course Material (I) (III) (IV) (IV) (II) -
Thickness (μ m) 20 20 20 20 20 -
Time of developing (second) 10 6 6 10 25 6
Adherence (μ m) 6 6 6 6 10 6
Resolution (μ m) 15 6 6 6 12 6
Concavo-convex tracing ability (μ m) 8 7 7 8 12 1
Stability Residual lattice number 6.0 4.5 4.5 5.0 6.0 6.0
Adherence (μ m) 6 20 25 12 10 6
Resolution (μ m) 15 15 20 10 12 6
By result shown in table 4～6 as can be known, the photosensitive element of embodiment 1～9 with the photosensitive element comparison of comparative example 1～8, confirm its adherence, resolution and concavo-convex tracing ability excellence, and ageing stability is also good.
Utilizability on the industry
As mentioned above, as adopt the present invention, then can provide and concavo-convexly have enough tracing abilities to what should carry out laminated substrate surface, simultaneously, the photosensitive element of adherence, resolution ratio and ageing stability excellence, and the formation method of the resist pattern that uses this photosensitive element and the manufacture method of printed circuit board (PCB) are provided.

Claims (17)

1. a photosensitive element is characterized in that possessing support film, is formed at the bed course on this support film and is formed at the photographic layer of thickness below 10 μ m on this bed course;
Described photographic layer contains weight-average molecular weight and is 10,000～100,000 binder polymkeric substance, has 1 the 1st optical polymerism compound and the 1st Photoepolymerizationinitiater initiater that can carry out the ethene unsaturated link of polymerization in the molecule at least;
Described bed course contains and has 1 the 2nd optical polymerism compound and the 2nd Photoepolymerizationinitiater initiater that can carry out the ethene unsaturated link of polymerization in the molecule at least.
2. photosensitive element as claimed in claim 1 is characterized in that, the thickness of this support film is 5～20 μ m.
3. photosensitive element as claimed in claim 1 or 2 is characterized in that, this binder polymkeric substance contains styrene and/or styrene derivative as monomeric unit.
4. as each described photosensitive element in the claim 1～3, it is characterized in that this binder polymkeric substance contains methacrylic acid as monomeric unit.
5. as each described photosensitive element in the claim 1～4, it is characterized in that the acid number of this binder polymkeric substance is 30～200mgKOH/g.
6. as each described photosensitive element in the claim 1～5, it is characterized in that, contain that to have 4～40 carbon numbers in molecule be that the compound of 2～6 oxyalkylene is as the 1st optical polymerism compound and the 2nd optical polymerism compound.
7. as each described photosensitive element in the claim 1～6, it is characterized in that, contain bisphenol A-type (methyl) acrylate compounds or poly-alkane glycol two (methyl) acrylate as the 1st optical polymerism compound and the 2nd optical polymerism compound.
8. photosensitive element as claimed in claim 7 is characterized in that, this bisphenol A-type (methyl) acrylate compounds is the compound with following general formula (1) expression,
[in the formula, R 1And R 2Independent separately expression hydrogen atom or methyl, X 1And Y 1Independent separately expression carbon number is 2～6 alkylidene, and p and q represent to satisfy the positive integer of p+q=4～40].
9. photosensitive element as claimed in claim 7 is characterized in that, this poly-alkane glycol two (methyl) acrylate compounds is the compound with following general formula (2) expression,
[in the formula, R 3And R 4Independent separately expression hydrogen atom or carbon number are 1～3 alkyl, X 2, X 3And Y 2Independent separately expression carbon number is 2～6 alkylidene, s, t and u represent to select from 0～30 satisfy s+t+u=4～40 integer].
10. as each described photosensitive element in the claim 1～9, it is characterized in that contain 2,4,5-triarylimidazoles dipolymer is as the 1st Photoepolymerizationinitiater initiater and the 2nd Photoepolymerizationinitiater initiater.
11. as each described photosensitive element in the claim 1～10, it is characterized in that, in this photographic layer, with this binder polymkeric substance and the 1st optical polymerism total amount of compound during as 100 mass parts, the allotment amount of the 1st optical polymerism compound is 30～60 mass parts, and with respect to the total amount of this binder polymkeric substance He the 1st optical polymerism compound of 100 mass parts, the allotment amount of the 1st Photoepolymerizationinitiater initiater is 0.1～20 mass parts.
12. as each described photosensitive element in the claim 1～11, it is characterized in that, this bed course also contain ethene and can with the multipolymer of the monomer of this ethylene copolymerization.
13. photosensitive element as claimed in claim 12, it is characterized in that, this multipolymer is, the ratio of this ethene is the vinyl-vinyl acetate copolymer of 60～90 quality % during as benchmark with the monomer total amount, perhaps be that the ratio of this ethene is ethene-(methyl) ethyl acrylate copolymer of 60～90 quality % during as benchmark with the monomer total amount.
14., it is characterized in that the thickness of this bed course is 1～100 μ m as each described photosensitive element in the claim 1～13.
15., it is characterized in that on this photographic layer, also possessing the protective film of this photographic layer of lining as each described photosensitive element in the claim 1～14.
16. the formation method of a resist pattern is characterized in that containing following operation:
According to forming the laminated operation that is configured each described photosensitive element in the claim 1～15 with the mode on the substrate in circuit with this photographic layer, this bed course and this support film are laminated successively,
Peel off the stripping process of this support film and this bed course from this photographic layer,
The irradiation active ray makes the exposure process that forms photocuring portion on this photographic layer in the established part of this photographic layer, and
Remove the video picture operation of this photocuring portion this photographic layer in addition.
17. the manufacture method of a printed circuit board (PCB) is characterized in that, the circuit that method is formed with resist pattern of forming by the described resist pattern of claim 16 is formed with substrate and carries out etching or plating.
CNA2005800242940A 2004-07-20 2005-07-14 Photosensitive element, method of forming resist pattern with the same, and process for producing printed wiring board Pending CN1989457A (en)

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JP4147920B2 (en) * 2002-11-29 2008-09-10 日立化成工業株式会社 Photosensitive resin composition, photosensitive element using the same, resist pattern forming method, and printed wiring board manufacturing method

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