CN102405441B - Photosensitive resin laminate, method for forming resist pattern and conductor pattern manufacture method - Google Patents
Photosensitive resin laminate, method for forming resist pattern and conductor pattern manufacture method Download PDFInfo
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- CN102405441B CN102405441B CN201080017632.9A CN201080017632A CN102405441B CN 102405441 B CN102405441 B CN 102405441B CN 201080017632 A CN201080017632 A CN 201080017632A CN 102405441 B CN102405441 B CN 102405441B
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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
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/092—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers characterised by backside coating or layers, by lubricating-slip layers or means, by oxygen barrier layers or by stripping-release layers or means
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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
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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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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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
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
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- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Architecture (AREA)
- Structural Engineering (AREA)
- Materials For Photolithography (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
Disclosed is a photosensitive resin laminate which has high sensitivity, while being suppressed in sensitivity decrease (namely sensitivity change) due to the hold time, in other words, having good storage stability. Also disclosed is a method for forming a resist pattern, which comprises a step in which a photosensitive resin layer is formed using the photosensitive resin laminate on a substrateand the photosensitive resin layer is exposed and developed. Specifically, the photosensitive resin laminate contains at least a supporting film, a photosensitive resin layer that is composed of a photosensitive resin composition, and a protective film, and the protective film contains an antioxidant that has a structure represented by general formula (I) (wherein R1 and R2 each independently represents a hydrogen atom or an alkyl group having 1-6 carbon atoms). The phenol equivalent of the antioxidant is not more than 3.1 10-3, and the antioxidant content in the protective film is more than 1 ppm but 3,000 ppm or less.
Description
Technical field
The present invention relates to photosensitive-resin layered product and uses thereof, specifically, relate to and be suitable for printed-wiring board (PWB), BGA (Ball grid array, ball grid array) and CSP (Chipsize package, chip size packages) etc. semiconductor-sealing-purpose substrate, lead frame with substrate and COF (Chip on film covers brilliant film) with the photosensitive-resin layered product of the manufacturing of wiring board etc. and use its formation method of corrosion-resisting pattern and the manufacture method of conductive pattern.
Background technology
All the time; as being used to make semiconductor-sealing-purpose substrates such as printed-wiring board (PWB), BGA, CSP, lead frame, use the so-called dry film resist (being designated hereinafter simply as DF) that constitutes by supporter film, photo-sensitive resin and protective film with substrate, COF resist with wiring board etc.The photo-sensitive resin that DF is made of photosensitive polymer combination by lamination on the supporter film usually, so on this photo-sensitive resin lamination protective film and making.In order to form photo-sensitive resin used herein, use the photosensitive polymer combination of the alkali developable that utilizes weak alkaline aqueous solution at present usually as its developer solution.
In addition, as the supporter film, use the transparent membrane of the active light of transmission.As such film, can enumerate polyvinyl alcohol film, polycarbonate film, plasticon, pet film etc.Usually, use the pet film of flexible and intensity with appropriateness.
In addition, as protective film, use polyolefin films such as polyethylene film, polypropylene film sometimes and carried out surface-treated mylar etc. with silicone etc.From cost and with the viewpoint of the peel property of photo-sensitive resin, use polyolefin film (with reference to patent documentation 1～3) usually.
In order to use DF to make printed-wiring board (PWB); at first; peel off protective film from DF, use lamination DF on permanent circuit such as copper clad laminate, flexible substrate are made with substrate such as laminating machine then, carry out the exposure of photo-sensitive resin across Wiring pattern mask film etc.Then, peel off the supporter film as required, the photo-sensitive resin by developing solution dissolution or dispersion removal unexposed portion forms corrosion-resisting pattern on substrate.
Behind the formation corrosion-resisting pattern (after being patterning), make its operation that forms circuit roughly be divided into two kinds of methods.First method is, after the exposed portions serve that the copper face that copper clad laminate etc. is removed in etching is not covered by corrosion-resisting pattern, uses the alkaline aqueous solution stronger than developer solution to remove the etching method of corrosion-resisting pattern part.Second method is, after the plating that carries out copper, scolder, nickel or tin etc. with the exposed portions serve of above-mentioned same copper face handled, similarly remove the corrosion-resisting pattern part, and then to carrying out etched plating method by the copper face of removing copper clad laminate that the corrosion-resisting pattern part manifests etc.Use cupric chloride, iron chloride, cupric ammine complex solution etc. during etching.
From the viewpoint of throughput rate, in having used the patterning operation of DF, photo-sensitive resin usually becomes problem for the sensitivity of active ray.In addition, DF provides with the roller shape of being made up of this 3-tier architecture of supporter film, photo-sensitive resin and protective film usually, if carry out patterning after placing during for the roller shape, then may produce the problem that the sensitivity of photo-sensitive resin reduces.Reduce if the DF of such roller shape produces sensitivity through the retention time, then problem all the year round is the resolution and the adaptation reduction of corrosion-resisting pattern, causes goods bad.
Find in the patent documentation 4 that the amount of the antioxidant that protective film contained is the following and 0ppm of 180ppm when above, can obtain high sensitivity and the few photosensitive-resin layered product of change of sensitivity (being the sensitivity reduction) that the retention time produced.
The prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication hei 08-123018 communique
Patent documentation 2: Japanese kokai publication hei 11-153861 communique
Patent documentation 3: TOHKEMY 2002-323759 communique
Patent documentation 4: Japanese Patent Application 2004-267497 communique
Summary of the invention
The problem that invention will solve
But from making the viewpoint of protective film, when being raw material made membrane below the 180ppm with antioxidant amounting, easily because of heat causes material modification, therefore existing needs the throughput rate that suppresses heating, suppress protective film and the problem of made membrane.
The object of the present invention is to provide a kind of photosensitive-resin layered product; it forms the protective film lamination of antioxidant amounting more than 1ppm; it is highly sensitive, and the sensitivity that the retention time produced reduction (being change of sensitivity) is few, and promptly storage stability is good.In addition, the object of the present invention is to provide a kind of formation method of corrosion-resisting pattern and the manufacture method of conductive pattern, this method comprises following operation: use this photosensitive-resin layered product, form the operation of photo-sensitive resin on substrate; The operation that this photo-sensitive resin is exposed; With the operation that this photo-sensitive resin is developed.
The scheme that is used to deal with problems
The inventor etc. study in order to solve above-mentioned problem; found that; by with general formula described later (I) expression, antioxidant amounting be to make up more than 1ppm and the protective film below the 3000ppm and photo-sensitive resin; can obtain high sensitivity and can suppress the photosensitive-resin layered product that sensitivity that the retention time produces reduces, thereby finish the present invention.That is, the present invention is as described below.
[1] photo-sensitive resin and protective film that a kind of photosensitive-resin layered product, this layered product comprise the supporter film at least, are made of photosensitive polymer combination,
This protective film contains the antioxidant of the structure with following general formula (I) expression,
(in the formula, R
1And R
2The alkyl of representing hydrogen or carbon number 1～6 respectively independently.)
The phenol equivalent of this antioxidant is 3.1 * 10
-3Below,
The content of this antioxidant in this protective film is more than 1ppm and below the 3000ppm.
[2] according to above-mentioned [1] described photosensitive-resin layered product, wherein, this antioxidant is the compound of following general formula (II) expression.
(in the formula, R
1And R
2The alkyl of representing hydrogen or carbon number 1～6 respectively independently, R
3The alkyl of expression carbon number 10～30.)
[3] according to above-mentioned [1] or [2] described photosensitive-resin layered product, wherein, this phenol equivalent is 2.0 * 10
-3Below.
[4] according to each described photosensitive-resin layered product in above-mentioned [1]～[3], wherein, this protective film is a polyethylene film.
[5] a kind of formation method of corrosion-resisting pattern, it forms the method for corrosion-resisting pattern for each described photosensitive-resin layered product in use above-mentioned [1]～[4],
This method comprises following operation:
Lamination, peel off this protective film, and meanwhile on substrate this photo-sensitive resin of lamination, thereby on this substrate, form this photo-sensitive resin;
Exposure process exposes to formed this photo-sensitive resin on this substrate;
Developing procedure develops to the photo-sensitive resin after this exposure, thereby forms corrosion-resisting pattern on this substrate.
[6] a kind of manufacture method of conductive pattern, it makes the method for conductive pattern for each described photosensitive-resin layered product in use above-mentioned [1]～[4],
This method comprises following operation:
Lamination, peel off this protective film, and meanwhile on substrate this photo-sensitive resin of lamination, thereby on this substrate, form this photo-sensitive resin;
Exposure process exposes to formed this photo-sensitive resin on this substrate;
Developing procedure develops to the photo-sensitive resin after this exposure, thereby forms corrosion-resisting pattern on this substrate;
Conductive pattern forms operation, and the substrate that is formed with this corrosion-resisting pattern is carried out etching or plating.
The effect of invention
According to the present invention, the content of the antioxidant by using above-mentioned general formula (I) expression is for more than 1ppm and the protective film below the 3000ppm, can provide a kind of high sensitivity and sensitivity that the retention time produced to reduce few photosensitive-resin layered product.In addition, according to the present invention, a kind of formation method of corrosion-resisting pattern and the manufacture method of conductive pattern can be provided, this method may further comprise the steps: use this photosensitive-resin layered product, on substrate, form photo-sensitive resin, and this photo-sensitive resin is exposed and develops.
Embodiment
Below, the present invention is specifically described.
＜photosensitive-resin layered product 〉
In a mode; the invention provides a kind of photosensitive-resin layered product; photo-sensitive resin and protective film that this layered product comprises the supporter film at least, is made of photosensitive polymer combination; this protective film contains the antioxidant of the structure with following general formula (I) expression, and the phenol equivalent of this antioxidant is 3.1 * 10
-3Below, the content of this antioxidant in this protective film is more than 1ppm and below the 3000ppm.The typical case, photosensitive-resin layered product of the present invention is supporter film, protective film and the photo-sensitive resin layered product that forms of lamination successively.Need to prove; the typical case; photosensitive-resin layered product of the present invention is made of supporter film, photo-sensitive resin and protective film; but; for example between photo-sensitive resin and supporter film, can also exist not have more than one resin bed photosensitive, that can develop.
(in the formula, R
1And R
2The alkyl of representing hydrogen or carbon number 1～6 respectively independently.)
[support film]
The supporter film that uses in the photosensitive-resin layered product of the present invention is as long as the supporter performance function of photo-sensitive resin, be preferably the flatness height, for the high organic polymer thin film of the transmittance of the active ray that is used to expose.
The mist degree of supporter film is preferably below 5.0, more preferably below 3.0, more preferably below 1.0.Mist degree is 5.0 when following, and the transmittance of active ray is good.The value of above-mentioned mist degree for utilizing haze meter (for example, the HAZE METER NDH2000 of Japanese electric look industry manufacturing) to measure.
The thickness of supporter film is preferably 5～25 μ m, is preferably 9～16 μ m especially.From keeping the viewpoint as the intensity of supporter film, this thickness is preferably more than the 5 μ m, from keep the viewpoint of the resolution of photo-sensitive resin well in order to make fine distribution, is preferably below the 25 μ m.The value of the thickness of putting down in writing in this instructions for utilizing micrometer (for example, the digital display standard of three rich manufacturings outside micrometer MDE-MJ) to measure.
As the example of preferred supporter film, can enumerate the film of polyethylene terephthalate, polybutylene terephthalate, PEN, polyvinyl alcohol (PVA), Polyvinylchloride, vinyl chloride copolymer, polyvinylidene chloride, vinylidene chloride copolymer, polymethyl methacrylate copolymer, polystyrene, polyacrylonitrile, styrol copolymer, polyamide, cellulose derivative etc.The preferred polyethylene terephthalate that uses.
[protective film]
As protective film, use the flatness height, compare the film low with the supporter film with the cohesive of photo-sensitive resin.The typical case, protective film is an organic polymer thin film.
The thickness of protective film is preferably 10～60 μ m, is preferably 15～50 μ m especially.From the viewpoint of the flatness that keeps protective film self, this thickness is preferably more than the 10 μ m, from keeping the viewpoint as the operability of the film that constitutes photosensitive-resin layered product, is preferably below the 60 μ m.
As the preferred example of protective film, can enumerate polyolefin such as tygon, polypropylene; Polyester or handle the polyester that has improved fissility by silicone-treated or alkyd (alkyd); Deng film.Usually use polyolefin film,, preferably use polyethylene film from the viewpoint of operability and cost.
Among above-mentioned, polyolefin film is by after according to inflation forming process or cast film forming process of utilizing the T mould etc. polyolefin resin being pushed, and carries out stretch processing, thereby made membrane obtains.
Among the present invention, it is 3.1 * 10 that protective film contains structure and phenol equivalent with following general formula (I) expression
-3Following antioxidant (below, also abbreviate antioxidant as).
(in the formula, R
1And R
2The alkyl of representing hydrogen or carbon number 1～6 respectively independently.)
The inventor etc. think; when the manufacturing lamination has (typical case's contact laminating) photosensitive-resin layered product of photo-sensitive resin and protective film; perhaps, As time goes on the antioxidant that exists in the protective film can flow out (oozing out) after the manufacturing of photosensitive-resin layered product, and part moves to photo-sensitive resin.Can be understood as, move by this, this antioxidant suppresses the free radical polymerization in the photo-sensitive resin when exposure, thereby photo-sensitive resin can't show the original sufficient sensitivity as resist.In addition, can be understood as, with roller shape keeping photosensitive-resin layered product the time, As time goes on, the seepage discharge of antioxidant increases, and sensitivity reduces.Therefore, for the few photosensitive-resin layered product of the change of sensitivity that obtains having sufficient sensitivity, the retention time produced simultaneously (being that sensitivity reduces), need make the antioxidant that protective film contains be difficult to move to photo-sensitive resin.Discoveries such as the inventor, to contain structure and phenol equivalent with above-mentioned general formula (I) expression in the protective film be 3.1 * 10 by making
-3Following antioxidant can prevent the outflow (oozing out) of antioxidant.
From the viewpoint of the outflow (oozing out) that prevents antioxidant, the phenol equivalent of the antioxidant that uses among the present invention is 3.1 * 10
-3Below, be preferably 2.0 * 10
-3Below.In addition, as the lower limit of this phenol equivalent, effectiveness and dispersed viewpoint from as antioxidant are preferably 4.0 * 10
-4More than, more preferably 1.0 * 10
-3More than, most preferably be 1.5 * 10
-3More than.As the antioxidant of phenol equivalent in above-mentioned scope, can the compound of the alkyl chain with long-chain be shown example, from the viewpoint of the outflow (oozing out) that prevents antioxidant, this compound advantageous particularly.
Here said phenol equivalent is meant the value that the number of the structure (being phenyl or alkyl-substituted phenyl) that above-mentioned general formula (I) is represented gets divided by the molecular weight of antioxidant.Thereby as by making the phenol equivalent in specialized range of the present invention, can prevent the reason of oozing out of antioxidant, consider as follows: contain the alkyl chain of long-chain by making antioxidant, thereby the compatibility of the formation polymkeric substance of antioxidant and protective film (for example polyolefin) improves; Perhaps, because the large volume of the alkyl chain of long-chain, thereby antioxidant extremely reduces to the translational speed of photo-sensitive resin; Perhaps produce this both situation simultaneously.Need to prove, when calculating the phenol equivalent, the number of the structure of above-mentioned general formula (I) expression, by utilizing phenol and 4-nitroaniline and nitrite reaction this phenomenon that develops the color, by the absorbance of 550nm methods such as content carries out are quantitatively confirmed that the molecular weight of antioxidant is for example confirmed by gas chromatography-mass spectrum device (GC-MS).
As the more preferred example of the structure of above-mentioned general formula (I) expression, can enumerate 3,5-di-t-butyl-4-hydroxyphenyl.
Preferred example as the antioxidant that uses among the present invention, can enumerate IRGANOX 1076, IRGANOX 1135, IRGANOX 565 and IRGANOX259 (more than, Specialty Chemicals) and Sumilizer GP and Sumilizer GS etc.
From suppressing the viewpoint of the sensitivity reduction that the retention time produced, the antioxidant that uses among the present invention is preferably the compound of following general formula (II) expression.R
3Carbon number more preferably 15～25.
(in the formula, R
1And R
2The alkyl of representing hydrogen or carbon number 1～6 respectively independently, R
3The alkyl of expression carbon number 10～30.)
The content of the antioxidant in the protective film is more than 1ppm, preferably more than 180ppm.By making this content, thereby be difficult to take place because of the material modification due to the heat more than 1ppm, heating-up temperature and mixing power in the mixing operation of polymkeric substance in the time of therefore can not reducing the protective film made membrane, and can make protective film with good throughput rate.This content is more preferably more than the 300ppm, more preferably more than the 400ppm.Viewpoint from the change of sensitivity that prevents photoresist is limited to below the 3000ppm on the content of the antioxidant in the protective film, is preferably below the 2000ppm, more preferably below the 1000ppm.
When making protective film, for example,, thereby carry out the control of the content of the antioxidant in the protective film by the dosage of control antioxidant with respect to the formation polymkeric substance (for example polyolefin resin) of protective film.The above-mentioned content of the antioxidant in the protective film is the value that is converted by dosage.Need to prove that the above-mentioned content of the antioxidant in the protective film for example also can directly be confirmed by the GC-MS method.
Need to prove, among the present invention, in not damaging the scope of performance that high sensitivity and sensitivity that the retention time produced reduces few photosensitive-resin layered product, except structure and the phenol equivalent with above-mentioned general formula (I) expression is 3.1 * 10
-3Outside the following antioxidant, can also be suitably also with the antioxidant that appends of other kinds.As the antioxidant that appends that can use, for example can enumerate following material.
2, the 6-di-tert-butyl-4-methy phenol, alkylated phenol, 4,4 '-thiobis-(the 6-tert-butyl group-3-methylphenol), 4,4 '-butylidene is two-and (the 6-tert-butyl group-3-methylphenol), 2,2 '-di-2-ethylhexylphosphine oxide-(4-methyl-6-tert butyl phenol), 2,2 '-di-2-ethylhexylphosphine oxide-(4-ethyl-6-tert-butyl phenol), 2,6-di-t-butyl-4-ethyl-phenol, 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, four (methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester) methane, dilauryl thiodipropionate, distearylthiodi-propionate, propane thioic acid two myristins.
In addition, also can enumerate triethylene glycol-two (3-(the 3-tert-butyl group-5-methyl-4-hydroxyphenyl) propionic esters), 2,4-pair-(n-octyl sulfo-)-6-(4-hydroxyl-3, the 5-di-tert-butyl aniline)-1,3, the 5-triazine, (3-(3 for pentaerythrite-four, 5-di-t-butyl-4-hydroxyphenyl) propionic ester), 2,2-sulfo--di ethylene bis (3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester), N, N '-hexa-methylene two (3,5-di-t-butyl-4-hydroxyl-hydrocinnamamide), phosphoric acid (3,5-di-t-butyl-4-hydroxyl-benzyl) diethylester, 1,3,5-trimethyl-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, three-(3, the 5-di-tert-butyl-4-hydroxyl benzyl)-isocyanuric acid ester, the octyl group diphenylamine, 2, two [(octylsulfo) the methyl]-orthoresols of 4-etc.
In addition, be antioxidant as hydrazine, also can use N, N '-two (3-(3,5-di-t-butyl-4-hydroxyphenyl) propiono) hydrazine etc.In addition, in addition, also can utilize existing known phenol is that antioxidant, phosphite ester are that antioxidant, thioether are antioxidant, heavy metal deactivator etc.
As mentioned above, the antioxidant that appends that protective film contained is performance effect when protective film is shaped preferably, and does not suppress the optical free radical polymerization of photosensitive polymer combination.The preferred content of the antioxidant that appends in the protective film is below the 180ppm.
On the other hand, the high sensitivityization of photo-sensitive resin also can realize by the kind of the Photoepolymerizationinitiater initiater in the photosensitive polymer combination and the research of use level, for example, if increase the use level of Photoepolymerizationinitiater initiater, then the amount of the scum silica frost in the developer solution increases, and storage stability also worsens.From suppress sensitivity that the retention time produced through the time viewpoint that changes, be exceedingly useful with the specific protective film that used the antioxidant that is difficult to move to photo-sensitive resin as the material of photosensitive-resin layered product.
About protective film, antioxidant that in the present invention, uses and the above-mentioned antioxidant that appends,, can also further contain antistatic agent, lubricant, antiblocking agent, filling agent etc. as adjuvant.For example, by when making protective film, suitably being blended in the raw material, can make and contain these adjuvants in the protective film.
[photo-sensitive resin]
Photo-sensitive resin is the layer that is made of photosensitive polymer combination.As photosensitive polymer combination, preferably can use following composition, the acid equivalent that said composition contains (a) carboxyl be 100～600 and weight-average molecular weight be 5000～500000 binder resin (below, be also referred to as (a) binder resin), (b) optical polymerism unsaturated compound and (c) Photoepolymerizationinitiater initiater.From the viewpoint of corrosion-resisting pattern formation performance, above-mentioned composition is favourable.
((a) binder resin)
(a) binder resin is that 100～600 amount contains carboxyl with the acid equivalent of carboxyl preferably.The acid equivalent of carboxyl more preferably 300～400.The acid equivalent of the carboxyl of putting down in writing in this instructions is meant the quality (gram) of the resin (for example linear polymer) of the carboxyl that wherein has 1 equivalent.In order to give development and the fissility of photo-sensitive resin to alkaline aqueous solution, (a) carboxyl in the binder resin is necessary.From the viewpoint of development patience, resolution and adaptation, this acid equivalent is preferably more than 100, and the viewpoint from development and fissility is preferably below 600.
(a) weight-average molecular weight of binder resin is preferably 5000～500000.This weight-average molecular weight more preferably 10000～200000.From the viewpoint of resolution, (a) weight-average molecular weight of binder resin is preferably below 500000, and the viewpoint from edge fusing (edge fuse) is preferably more than 5000.
Need to prove, use automatic titration device (for example, the flat natural pond automatic titration device (COM-555) that flat natural pond industry (strain) is made), adopt the NaOH of 0.1mol/L, carry out the mensuration of acid equivalent by potential difference titration.
In addition, about weight-average molecular weight, utilize gel permeation chromatograph (for example, the gel permeation chromatograph (GPC) that Japan beam split Co., Ltd. makes (pump: Gulliver, PU-1580 type, post: clear and 4 series connection of Shodex (registered trademark) (KF-807, KF-806M, KF-806M, KF-802.5), mobile phase solvent that electrician's (strain) makes: tetrahydrofuran, use are based on the calibration curve of polystyrene standard sample)), obtain as the weight-average molecular weight of polystyrene conversion.
The typical case, (a) binder resin can obtain by the polymerization of following first monomer or the copolymerization of following first monomer and second monomer.First monomer and second monomer can use more than a kind or 2 kinds respectively.
First monomer is carboxylic acid or the acid anhydrides that has a polymerism unsaturated group in the molecule.For example, can enumerate (methyl) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, maleic acid half ester etc.
Second monomer is nonacid, have a polymerism unsaturated group in the molecule, it can be from the patience the operation of the development, etching and the plating that keep photo-sensitive resin, the aspect of the various characteristics such as flexible of cured film that photo-sensitive resin is solidified to form is selected.As second monomer, for example, can enumerate (methyl) alkyl acrylates such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 2-hydroxypropyl acrylate, (methyl) vinyl cyanide etc.In addition, from high-resolution viewpoint, be preferably vinyl compound (for example, styrene) with phenyl.
(a) binder resin preferably synthesizes as follows: dilute above-mentioned monomer (potpourri more than a kind or 2 kinds) with acetone, MEK, isopropyl alcohol equal solvent, in resulting solution, add radical polymerization initiators such as an amount of benzoyl peroxide, azo isobutyronitrile, carry out heated and stirred and synthesize.Also this potpourri of part can be dripped in reactant liquor on one side, Yi Bian synthesize.Can also finish the back in reaction and further add solvent, be adjusted to desired concentration.As synthetic method, except above-mentioned solution polymerization, also can adopt bulk polymerization, suspension polymerization or emulsion polymerization.
The content of (a) binder resin in the photosensitive polymer combination is preferably 20～90 quality %, more preferably 30～70 quality %.From making by exposure and the corrosion-resisting pattern forms of developing has characteristic as resist, viewpoint such as sufficient patience protuberance (tenting), etching and the various plating operation for example, above-mentioned content is preferably 20～90 quality %.
((b) optical polymerism unsaturated compound)
As (b) optical polymerism unsaturated compound, can preferably use have the optical polymerism unsaturated group, the compound of (methyl) acrylic for example.As (b) optical polymerism unsaturated compound that can use, for example, can enumerate 1,6-hexanediol two (methyl) acrylate, 1,4-cyclohexanediol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, polyglycol two (methyl) acrylate, 2-two (to hydroxyphenyl) propane two (methyl) acrylate, glycerine three (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, polyoxyethyl propyl trimethylolpropane tris (methyl) acrylate, polyoxy ethyl trimethylolpropane tris (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, trihydroxymethylpropanyltri diglycidyl ether three (methyl) acrylate, bisphenol A diglycidyl ether two (methyl) acrylate, β-hydroxy propyl-Beta '-(acryloxy) propyl group phthalic ester, phenoxy group polyglycol (methyl) acrylate, Nonylphenoxy polyglycol (methyl) acrylate, Nonylphenoxy poly alkylene glycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate etc.
In addition, as (b) optical polymerism unsaturated compound, also can enumerate carbamate compounds with (methyl) acrylic.As this carbamate compounds, for example, can enumerate hexamethylene diisocyanate, toluene diisocyanate, 2,2, have the carbamate compounds etc. of the compound (for example acrylic acid 2-hydroxypropyl acrylate, oligomeric propylene glycol monomethyl acrylate etc.) of hydroxyl and (methyl) acrylic in diisocyanate cpd such as 4-trimethyl hexamethylene diisocyanate and a part.The reactant that hexamethylene diisocyanate and oligomeric propylene glycol monomethyl acrylate (Japanese grease (strain) manufacturing, BLEMMER PP 1000) arranged specifically.
In addition, (b) the optical polymerism unsaturated compound is preferably the compound of following general formula (III) or following general formula (IV) expression.
(in the formula, R
4And R
5Represent hydrogen or CH respectively independently
3, n
1, n
2And n
3Represent 3～20 integer respectively independently.)
(in the formula, R
6And R
7Represent hydrogen or CH respectively independently
3, A represents C
2H
4, B represents CH
2CH (CH
3), n
4+ n
5The integer of expression 2～30, n
6+ n
7The integer of expression 0～30, n
4And n
5Represent 1～29 integer respectively independently, n
6And n
7Represent 0～29 integer respectively independently.-(A-O)-and-(B-O)-the arrangement of repetitive can also can be block for random, when be block ,-(A-O)-with-(B-O)-order be that any all can in the xenyl side.)
Reduce few viewpoint from the sensitivity that retention time produced of DF, such compound is preferred.In addition, can and with the two or more above-mentioned general formulas (III) or (IV) compound of expression, and then, can also be with more than one these compounds and above-mentioned other optical polymerism unsaturated compounds usefulness also.
In the compound of above-mentioned general formula (III) expression, from the viewpoint of boiling point and foul smell, n
1, n
2And n
3Being independently respectively is preferred more than 3.In addition, from the viewpoint by the caused sensitivity of concentration at the photolytic activity position of per unit mass, n
1, n
2And n
3Being independently respectively is preferred below 20.
Object lesson as the compound of above-mentioned general formula (III) expression, for example, can enumerate in addition in the polypropylene glycol of average 12 moles epoxypropane, respectively the preferred example of the dimethylacrylate of the glycol of average 3 moles of ethylene oxide of further addition conduct at two ends.
In the compound of above-mentioned general formula (IV) expression, from the viewpoint of sensitivity, n
4+ n
5And n
6+ n
7It is preferred being respectively below 30.
As the object lesson of the compound of above-mentioned general formula (IV) expression, can enumerate at the two ends of bisphenol-A the dimethylacrylate of the poly alkylene glycol of average 2 moles epoxypropane of addition respectively and average 6 moles oxirane, distinguish the dimethylacrylate (the NK ESTER BPE-500 that Xin Zhong village chemical industry (strain) is made) of the polyglycol of the average 5 moles oxirane of addition at the two ends of bisphenol-A, with the dimethylacrylate (Xin Zhong village chemical industry (strain) is made NK ESTER BPE-200) of the polyglycol of the average 2 moles oxirane of addition etc. respectively at the two ends of bisphenol-A.
The content of (b) optical polymerism unsaturated compound in the photosensitive polymer combination is preferably in the scope of 3～70 quality %.From the viewpoint of sensitivity, this content is preferably more than the 3 quality %, from the viewpoint of edge fusing, is preferably below the 70 quality %.This content is 10～60 quality % more preferably, more preferably 15～55 quality %.
((c) Photoepolymerizationinitiater initiater)
As (c) Photoepolymerizationinitiater initiater, can use normally used Photoepolymerizationinitiater initiater in optical polymerism resin synthetic.From highly sensitive viewpoint, (c) Photoepolymerizationinitiater initiater preferably contains 2,4 of following general formula (V) expression, 5-triarylimidazoles dipolymer.
(in the formula, X, Y and Z represent hydrogen, alkyl, alkoxy or halogen base respectively independently, and p, q and r represent 1～5 integer respectively independently.)
In the compound of above-mentioned general formula (V) expression, 22,4 of bondings, the covalent bond of 5-triphenyl imidazole radicals is positioned at 1,1 '-, 1,2 '-, 1,4 '-, 2,2 '-, 2,4 '-or 4,4 '-position from the viewpoint of synthetic easiness, is preferably placed at the compound of 1,2 '-position.
As 2,4,5-triarylimidazoles dipolymer, for example, can enumerate 2-(Chloro-O-Phenyl)-4,5-diphenyl-imidazole dipolymer, 2-(Chloro-O-Phenyl)-4,5-couple-(m-methoxyphenyl) imidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenyl-imidazole dipolymer etc., particularly, from the viewpoint of storage stability, preferred 2-(Chloro-O-Phenyl)-4,5-diphenyl-imidazole dipolymer.
As (c) Photoepolymerizationinitiater initiater, from the viewpoint of sensitivity, resolution and the adaptation of photosensitive polymer combination, preferred and with above-mentioned general formula (V) represent 2,4,5-triarylimidazoles dipolymer and p-aminophenyl ketone.As p-aminophenyl ketone, for example, can enumerate to aminobenzophenone, to the amino benzophenone of butyl, to the dimethylamino benzoylformaldoxime, to dimethylamino benzophenone, p, p '-two (ethylamino) benzophenone, p, p '-two (dimethylamino) benzophenone [Michler's keton], p, p '-two (diethylamino) benzophenone, p, p '-two (dibutylamino) benzophenone etc.
In addition, as (c) Photoepolymerizationinitiater initiater, except the compound shown in above-mentioned, can also use other Photoepolymerizationinitiater initiaters.As other Photoepolymerizationinitiater initiaters, can use by activation such as various active rays, for example ultraviolet rays and cause the compound arbitrarily of the polymerization of resin raw material.
As other Photoepolymerizationinitiater initiaters, for example, can enumerate quinones such as 2-EAQ, 2-tert-butyl group anthraquinone; Aromatic series ketones such as benzophenone; Benzoin ethers such as benzoin, benzoin methyl ether, benzoin ethylether; Acridine compounds such as 9-phenylacridine; Ketal classes such as benzil dimethyl ketal, benzil diethyl ketal; Deng.
In addition, for example, also can enumerate thioxanthones, 2, the combination of tertiary amine compound such as thioxanthene ketone such as 4-diethyl thioxanthone, 2-clopenthixal ketone and dimethylaminobenzoic acid alkyl ester compound.
In addition, also can enumerate 1-phenyl-1,2-propanedione-2-O-benzoyl oxime, 1-phenyl-1, oxime ester classes such as 2-propanedione-2-(O-ethoxy carbonyl) oxime etc.In addition, can also use N-aryl-alpha-amino acid compound.Wherein, be preferably N-phenylglycine especially.
The content of (c) Photoepolymerizationinitiater initiater in the photosensitive polymer combination is preferably 0.1 quality %～20 quality %, more preferably 1～10 quality %.If this content is lower than 0.1 quality %, then there is the low tendency of sensitivity.In addition, if this content surpasses 20 quality %, produce the photographic fog of photo-sensitive resin during then easily because of exposure by the diffraction of light of photomask, the tendency that its result exists resolution to reduce.
Photosensitive polymer combination can contain coloring materials such as dyestuff, pigment.As the coloring material that can use, for example, can enumerate magenta, phthalocyanine green, auramine alkali, the green S of alkoxide, paramagenta, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green (AIZENAIZEN (registered trademark) the MALACHITE GREEN that Baotugu Chemical Industrial Co., Ltd makes), alkali blue 20, diamond green (AIZEN (registered trademark) the DIAMOND GREEN GH that Baotugu Chemical Industrial Co., Ltd makes) etc.
Photosensitive polymer combination can contain the color appearance system dyestuff that develops the color by illumination.As the color appearance system dyestuff that can use, for example, can enumerate the combination of leuco dye or fluoran dyes and halogen compounds.
As leuco dye, for example, can enumerate three (4-dimethylamino-2-aminomethyl phenyl) methane [leuco crystal violet], three (4-dimethylamino-2-aminomethyl phenyl) methane [procrypsis malachite green] etc.
As halogen compounds, can enumerate bromo pentane, bromo isopentane, bromo isobutylene, bromoethylene, bromo diphenyl-methane, benzal bromide, methylene bromide, trisbromomethyl benzene sulfone, carbon tetrabromide, three (2, the 3-dibromopropyl) phosphate, trichloroacetamide, iodo-pentane, iodo isobutane, 1,1,1-three chloro-2, two (rubigan) ethane of 2-, carbon trichloride, triaizine compounds etc.
As triaizine compounds, can enumerate 2,4,6-three (trichloromethyl) s-triazine, 2-(4-methoxyphenyl)-4, two (trichloromethyl) s-triazine of 6-etc.
In this color appearance system dyestuff, the combination of the combination of trisbromomethyl benzene sulfone and leuco dye and triaizine compounds and leuco dye is useful.
For the thermal stability and the storage stability that improve photosensitive polymer combination, photosensitive polymer combination preferably contains radical polymerization inhibitor.
As radical polymerization inhibitor, for example, can enumerate p methoxy phenol, quinhydrones, pyrogallol, naphthylamines, tert-butyl catechol, stannous chloride, 2,6-di-t-butyl-paracresol, 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol), 2,2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert butyl phenol), diphenyl nitrosamine, pentaerythrite 3,5-di-t-butyl-4-hydroxyphenylpropionic acid four esters (ethylenebis (oxygen ethene) two [3-(a 5-tertiary butyl-4-hydroxy-tolyl) propionic esters] (the system IRGANOX245 of the different chemicals of western Bart company limited)) etc.
In addition, as other adjuvants that are used to improve storage stability, can enumerate to the both sides of bisphenol-A respectively addition the compound, benzotriazole, carboxyl benzotriazole, 1-(2-dialkyl amido) carboxyl benzotriazole etc. of the further addition epoxypropane in both sides of polypropylene glycol of average 1 mole epoxypropane.
In addition, as required, photosensitive polymer combination can contain adjuvants such as plastifier.As this adjuvant, for example, can enumerate phthalates such as diethyl phthalate and para toluene sulfonamide, polypropylene glycol, polyalkylene glycol monoalkyl ether etc.
From the viewpoint of effect such as sensitivity is good, thick 0.1～40 μ m that is preferably of the film of photo-sensitive resin.From making the viewpoint of above-mentioned better effects if, thick 0.1～15 μ m more preferably of this film, more preferably 0.1～5 μ m.
[manufacturing of photosensitive-resin layered product]
Photosensitive-resin layered product of the present invention for example can be made by the following method.Above-mentioned photosensitive polymer combination is dissolved in the appropriate solvent such as MEK, to described supporter film, and utilizes drying process to remove solvent resulting photosensitive polymer combination solution coat, at supporter film upper strata pressure sensitivity photosensitiveness resin bed.Next, by utilizing the methods such as thermo-compressed of laminating machine, at the described protective film of surface laminated this photo-sensitive resin and surface opposite side supporter film laminating side.Thus, the photosensitive-resin layered product that is had the laminar structure of supporter film, photo-sensitive resin and protective film successively.As mentioned above, compare with the supporter film, the closing force of protective film and photo-sensitive resin is littler, protective film easily can be peeled off from photo-sensitive resin, and this characteristic is the key property as protective film.
The formation method of＜corrosion-resisting pattern 〉
In other modes, the invention provides a kind of formation method of corrosion-resisting pattern, it forms the method for corrosion-resisting pattern for the photosensitive-resin layered product that uses the invention described above, this method comprises following operation: lamination, peel off this protective film on one side, one side this photo-sensitive resin of lamination on substrate, thus this photo-sensitive resin on this substrate, formed; Exposure process exposes to formed this photo-sensitive resin on this substrate; Developing procedure develops to the photo-sensitive resin after this exposure, thereby forms corrosion-resisting pattern on this substrate.Below, the object lesson about the formation method of corrosion-resisting pattern of the present invention is described.
(A) lamination:
In this operation; peel off the protective film of photosensitive-resin layered product on one side, on one side the surface (for example copper face) of photo-sensitive resin and substrate is stacked, make both bonding; and it is passed through up and down between 1 pair of hot-rolling so that both laminations, thereby with photo-sensitive resin and substrate crimping.Thus, on substrate, form photo-sensitive resin.
The temperature of above-mentioned hot-rolling is preferably 50～120 ℃, and laminate speed is preferably 0.1～6.0m/ minute.1 pair of hot-rolling clamps by cylinder or spring up and down.About roller pressure, the pressure gauge with the unit length of hot-rolling is preferably 0.1～1.0MPa/cm, more preferably 0.2～0.5MPa/cm.
As laminating machine, use following laminating machine: the 1 segmentation laminating machine that utilizes 1 pair of laminating roll; Utilize the multisection type laminating machine of the laminating roll more than 2 pairs; The part of institute's lamination is covered with container, and utilize vacuum pump to make its decompression or for the vacuum laminator of vacuum etc.
In addition, before lamination,, can carry out various processing (pre-treatment) in order to improve the adaptation of substrate and photo-sensitive resin.For example, as the method that makes the substrate surface roughening with physics mode, can enumerate polishing roll and grind.In addition, the acidic liquid that will have the ability of corrosion copper is used as pretreatment liquid, and is heated to 25～50 ℃ as required, utilizes this pretreatment liquid by infusion process or gunite treatment substrate.
As pretreatment liquid, can enumerate the aqueous solution of aqueous solution, ammonium persulfate or sodium peroxydisulfate of mixed liquor, ammonium persulfate or sodium peroxydisulfate of sulfuric acid and aquae hydrogenii dioxidi and mixed liquor, nitric acid and nitric acid slaine and organic acid mixture aqueous solution, acetate slaine and the organic acid mixture aqueous solution etc. of sulfuric acid.As this organic acid, can enumerate formic acid, acetate, malic acid, acrylic acid, glycollic acid, maleic acid, itaconic acid, maleic anhydride etc.
Can also preferably use as chemical milling agent, soft etchant or the commercially available medicament of surface roughening agent, this medicament contains mentioned component.As an example, can enumerate CPE-900 and CPE-500 (being Mitsubishi's gas chemistry manufacturing, trade name) and CZ-8100 and CB-801 (being MAG's manufacturing, trade name).
(B) exposure process:
In this operation, formed photo-sensitive resin on the substrate is exposed.Preferably, the photomask of describing desired conductive pattern is placed on the supporter film across small gap, perhaps with the state of this supporter film driving fit, utilize ultraviolet light source to expose.In addition, also can use projecting lens to make photomask look like to be imaged on the photo-sensitive resin exposes.Projected light mask picture and under the situation that photo-sensitive resin is exposed can be peeled off the supporter film and, also can photo-sensitive resin be exposed with the state that has the supporter film the photo-sensitive resin exposure from photo-sensitive resin.As ultraviolet light source, can enumerate high-pressure sodium lamp, ultrahigh pressure mercury lamp, ultraviolet fluorescent lamp, carbon arc lamp, xenon lamp etc.In order to obtain finer corrosion-resisting pattern, preferably use parallel light source.
(C) developing procedure:
In this operation, the photo-sensitive resin after the exposure is developed, thereby on substrate, form corrosion-resisting pattern.Do not peel off under the situation of supporter film during exposure, peel off the supporter film from photo-sensitive resin.Then, use alkaline developer that photo-sensitive resin is developed.Specifically, under the situation that photo-sensitive resin is made of negative light-sensitive resin combination, dissolving or disperse to remove unexposed portion, under the situation that photo-sensitive resin is made of positive type photosensitive organic compound, dissolving or disperse to remove exposed portion.Thus, on substrate, form corrosion-resisting pattern.
As the alkaline aqueous solution that uses in the developing procedure, can enumerate the aqueous solution of sodium carbonate, sal tartari, NaOH, potassium hydroxide etc.The most general aqueous sodium carbonate that is to use 0.2～2.0 quality %.About the washing water after developing, from adaptation, the resolution of corrosion-resisting pattern with prevent to be preferably the viewpoint of trailing and to take off Ionized water.For example can preferably enumerate tap water.
By above operation, can form desired corrosion-resisting pattern.
The manufacture method of＜conductive pattern 〉
In other modes, the invention provides a kind of manufacture method of conductive pattern, it makes the method for conductive pattern for the photosensitive-resin layered product that uses the invention described above, this method comprises following operation: lamination, peel off this protective film on one side, one side this photo-sensitive resin of lamination on substrate, thus this photo-sensitive resin on this substrate, formed; Exposure process exposes to formed this photo-sensitive resin on this substrate; Developing procedure develops to the photo-sensitive resin after this exposure, thereby forms corrosion-resisting pattern on this substrate; Conductive pattern forms operation, and the substrate that is formed with this corrosion-resisting pattern is carried out etching or plating.In the manufacture method of conductive pattern, lamination, exposure process and developing procedure can be implemented equally with these operations in the formation method of above-mentioned corrosion-resisting pattern.In the manner, after forming corrosion-resisting pattern, further pass through following operation, thereby can make conductive pattern.
(D) conductive pattern forms operation:
In this operation, the residual corrosion-resisting pattern that on substrate, forms by above-mentioned developing procedure, with etching solution the substrate surface (for example copper face) of the part that do not covered by corrosion-resisting pattern is carried out etching with this state, perhaps the plating that carries out copper, scolder, nickel or tin etc. for the substrate surface (for example copper face) of the part that is not covered by corrosion-resisting pattern is handled.Form conductive pattern thus.
Stripping process:
Need to prove, after the manufacture method by conductive pattern of the present invention forms conductive pattern, typical case, the stripping process that utilizes alkaline stripper that corrosion-resisting pattern is removed from substrate.As the alkaline aqueous solution that uses in the stripping process, use than the used stronger alkaline aqueous solution of alkaline aqueous solution alkalescence in developing.As the alkaline aqueous solution of peeling off usefulness, can enumerate the aqueous solution of NaOH, potassium hydroxide, organic amine compound etc.The most general NaOH that is to use 1～5 quality % or the aqueous solution of potassium hydroxide.
Embodiment
Below, by embodiment the example of embodiments of the present invention is described in detail.
1) manufacturing of photosensitive-resin layered product
Use rod to be coated with machine the mixed solution of the composition shown in the table 1 is uniformly applied on the supporter film, in 95 ℃ dryer dry 1 minute, forming thickness was the photo-sensitive resin of 10 μ m.And then the protective film that on photo-sensitive resin, bonds, obtain photosensitive-resin layered product.The supporter film uses R340G (manufacturing of Mitsubishi Chemical mylar Co., Ltd., polyethylene terephthalate, thickness 16 μ m).In addition, the protective film used thickness is that high-pressure process low-density polyethylene film (Asahi Chemical Corp's manufacturing, LS2340S) or the thickness of 22 μ m are the polypropylene film of 20 μ m.
The antioxidant that protective film contained that uses in each embodiment and comparative example shown in table 2～5 is octadecyl-3-(3; 5-di-t-butyl-4-hydroxyphenyl) propionic ester; and phenylpropionic acid; 3; 5-two (1; the 1-dimethyl ethyl)-the 4-hydroxyl; C7-C9-side chain Arrcostab; 1; 6-hexanediol-two (3 (3; 5-di-t-butyl-4-hydroxyphenyl) propionic ester); 2; the 6-di-tert-butyl-4-methy phenol; 2; 6-di-t-butyl-4-ethyl-phenol; dilauryl thiodipropionate; the amount of three (2, the 4-di-tert-butyl-phenyl) phosphite ester; the measurement result of melt flow rate of each protective film (being designated hereinafter simply as MFR) and density; and the result of the sensitivity test of photosensitive-resin layered product and retention time sensitivity test.In addition, in the table 1 with shorthand notation (detailed content of the composition of the formation photosensitive polymer combination of the expression of P-1～C-3) is shown in described later＜symbol description 〉.
2) wiring board is made
(whole face)
With lamination the copper clad laminate of the thick rolled copper foils of 35 μ m as substrate, the wet type polishing roll is carried out on the surface of this substrate grinds (3M (strain) manufacturings, trade name Scotch-Brite (registered trademark) #600,2 companies).
(lamination)
Peel off the protective film of photosensitive-resin layered product on one side, Yi Bian use laminating machine AL-70 (Asahi Chemical Industry's manufacturing, trade name) at substrate upper strata pressure sensitivity photosensitiveness resin bed.Lamination is laminate speed: 1.5m/ minute, laminating roll temperature: 105 ℃, lamination pressure: 0.35MPa/cm.
(exposure)
By mask film, utilize ultrahigh pressure mercury lamp (ORC MANUFACTURING CO., LTD. makes HMW-201KB) with 100mJ/cm
2The exposure photo-sensitive resin.
(development)
After peeling off the supporter film, spray about 20 seconds of the aqueous sodium carbonate of 30 ℃ 1 quality %, unexposed portion is removed in dissolving, thereby photo-sensitive resin is developed.
[MFR determination method]
According to JIS K7210:1999 method, implement MFR and measure with 190 ℃, load 2.16kg for polyethylene film, implement MFR and measure with 230 ℃, load 2.16kg for polypropylene film.
[densitometry]
Implement density measurement according to JIS K7112:1999 method.
[phenol equivalent]
The antioxidant (the antioxidant kind of nominal) that contains about employed protective film calculates the number of the structure of above-mentioned general formula (I) expression divided by molecular weight.
[oxidation preventive content]
Be meant that structure and phenol equivalent with above-mentioned general formula (I) expression in the employed protective film are 3.1 * 10
-3The value that the dosage of following antioxidant gets divided by the dosage of the raw material of the protective film except that antioxidant.
[sensitivity test]
The photosensitive-resin layered product of the state of the protective film shown in table 2～5 that bondd was preserved 5 hours under 23 ℃, 50% environment; peel off on one side protective film, on one side the photo-sensitive resin of lamination on the copper clad laminate is exposed, develops by the stage metraster in Stouffer system 21 rank.With the highest residual film exponent number of resulting curing resist as sensitivity.
[retention time sensitivity test]
The photosensitive-resin layered product of the state of the protective film shown in table 2～5 that bondd is preserved under 23 ℃, 50% environment, 2 week the back by estimating sensitivity with the same method of above-mentioned sensitivity test.
＜symbol description 〉
P-1: the methyl ethyl ketone solution of the terpolymer of methyl methacrylate 50 weight %, methacrylic acid 25 weight %, styrene 25 weight % (solid component concentration 35 weight %, weight-average molecular weight 50,000, acid equivalent 344)
M-1: at the two ends of bisphenol-A respectively addition the dimethylacrylate of poly alkylene glycol of average 2 moles epoxypropane and average 6 moles oxirane
M-2: at the two ends of bisphenol-A respectively addition the dimethylacrylate (Xin Zhong village chemical industry (strain) is made NK ESTER BPE-200) of polyglycol of average 2 moles oxirane
M-3: the reactant of hexamethylene diisocyanate and oligomeric propylene glycol monomethyl acrylate (Japanese grease (strain) manufacturing, BLEMMER PP1000) is the urethane polypropylene glycol dimethacrylate
M-4: trimethylolpropane triacrylate
M-5: three oxygen ethyl trimethylolpropane triacrylates (Xin Zhong village chemical industry (strain) is made NK ESTER A-TMPT-3EO)
A-1:4,4 '-two (lignocaine) benzophenone
A-2:2-(Chloro-O-Phenyl)-4,5-diphenyl-imidazole dipolymer
B-1: diamond green (Baotugu Chemical Industrial Co., Ltd makes AIZEN (registered trademark) DIAMOND GREEN GH)
B-2: leuco crystal violet
C-1: para toluene sulfonamide
C-2: benzotriazole
C-3: ethylenebis (oxygen ethene) two [3-(a 5-tertiary butyl-4-hydroxy-tolyl) propionic esters] (the system IRGANOX245 of the different chemicals of western Bart company limited))
[table 1]
[table 2]
[table 3]
[table 4]
[table 5]
Utilizability on the industry
The present invention is suitable for semiconductor-sealing-purpose substrates such as printed-wiring board (PWB), BGA and CSP, lead frame with substrate and the COF manufacturing with wiring board etc.
Claims (5)
1. photo-sensitive resin and protective film that photosensitive-resin layered product, this layered product comprise the supporter film at least, are made of photosensitive polymer combination,
This protective film contains the antioxidant of the structure with following general formula (I) expression,
In the formula, R
1And R
2The alkyl of representing hydrogen or carbon number 1～6 respectively independently,
The phenol equivalent of this antioxidant is 3.1 * 10
-3Below,
The content of this antioxidant in this protective film is more than the 300ppm and below the 3000ppm,
This antioxidant is the compound of following general formula (II) expression,
In the formula, R
1And R
2Represent the alkyl of hydrogen or carbon number 1～6 respectively independently, R3 represents the alkyl of carbon number 10～30.
2. photosensitive-resin layered product according to claim 1, wherein, this phenol equivalent is 2.0 * 10
-3Below.
3. photosensitive-resin layered product according to claim 1, wherein, this protective film is a polyethylene film.
4. the formation method of a corrosion-resisting pattern, it forms the method for corrosion-resisting pattern for using the described photosensitive-resin layered product of claim 1,
This method comprises following operation:
Lamination, peel off this protective film, and meanwhile on substrate this photo-sensitive resin of lamination, thereby on this substrate, form this photo-sensitive resin;
Exposure process exposes to formed this photo-sensitive resin on this substrate;
Developing procedure develops to the photo-sensitive resin after this exposure, thereby forms corrosion-resisting pattern on this substrate.
5. the manufacture method of a conductive pattern, it makes the method for conductive pattern for using the described photosensitive-resin layered product of claim 1,
This method comprises following operation:
Lamination, peel off this protective film, and meanwhile on substrate this photo-sensitive resin of lamination, thereby on this substrate, form this photo-sensitive resin;
Exposure process exposes to formed this photo-sensitive resin on this substrate;
Developing procedure develops to the photo-sensitive resin after this exposure, thereby forms corrosion-resisting pattern on this substrate;
Conductive pattern forms operation, and the substrate that is formed with this corrosion-resisting pattern is carried out etching or plating.
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| PCT/JP2010/057015 WO2010123005A1 (en) | 2009-04-20 | 2010-04-20 | Photosensitive resin laminate |
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| JP5662758B2 (en) * | 2010-10-15 | 2015-02-04 | 旭化成イーマテリアルズ株式会社 | Photosensitive resin laminate |
| JP5579568B2 (en) * | 2010-10-15 | 2014-08-27 | 旭化成イーマテリアルズ株式会社 | Photosensitive resin laminate |
| JP5579567B2 (en) * | 2010-10-15 | 2014-08-27 | 旭化成イーマテリアルズ株式会社 | Photosensitive resin laminate |
| JP5579566B2 (en) * | 2010-10-15 | 2014-08-27 | 旭化成イーマテリアルズ株式会社 | Photosensitive resin laminate |
| JP2012163603A (en) * | 2011-02-03 | 2012-08-30 | Hitachi Chem Co Ltd | Photosensitive resin composition, photosensitive element, method for manufacturing resist pattern, and method for manufacturing printed wiring board |
| JP5826006B2 (en) * | 2011-12-01 | 2015-12-02 | 旭化成イーマテリアルズ株式会社 | Photosensitive resin composition |
| JP6113976B2 (en) * | 2012-08-29 | 2017-04-12 | 旭化成株式会社 | Photosensitive resin composition |
| JPWO2016104585A1 (en) * | 2014-12-25 | 2017-10-05 | 日立化成株式会社 | Photosensitive resin composition, photosensitive element using the same, resist pattern forming method, and printed wiring board manufacturing method |
| JP6829859B2 (en) * | 2015-04-21 | 2021-02-17 | 株式会社北陸濾化 | Mask forming method, printed wiring board manufacturing method using this, electroformed parts manufacturing method and screen printing plate making manufacturing method |
| JP2019133143A (en) * | 2018-01-30 | 2019-08-08 | 旭化成株式会社 | Photosensitive resin laminate and method for manufacturing resist pattern |
| JP7317550B2 (en) * | 2018-05-01 | 2023-07-31 | 旭化成株式会社 | Photosensitive laminate and manufacturing method thereof |
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| JP2000112133A (en) * | 1998-09-30 | 2000-04-21 | Toray Gosei Film Kk | Photoresist cover film for photosensitive plate |
| JP2002060426A (en) * | 2000-08-18 | 2002-02-26 | Japan Polyolefins Co Ltd | Protective film and process for manufacturing the same |
| JP2002323760A (en) * | 2001-04-25 | 2002-11-08 | Asahi Kasei Corp | Photopolymeric resin laminate |
| JP2003231759A (en) * | 2002-02-13 | 2003-08-19 | Japan Polyolefins Co Ltd | Method for manufacturing polyethylene as protective film and protective film manufactured by using it |
| CN1666150A (en) * | 2002-07-03 | 2005-09-07 | 住友电木株式会社 | Photosensitive compositions based on polycyclic polymers |
| JP2006113557A (en) * | 2004-09-14 | 2006-04-27 | Asahi Kasei Electronics Co Ltd | Method for manufacturing photosensitive resin laminate |
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| JP2004325980A (en) * | 2003-04-28 | 2004-11-18 | Kanegafuchi Chem Ind Co Ltd | Photosensitive resin composition and photosensitive dry film resist having favorable storage stability, and its use |
| US20060199920A1 (en) * | 2003-04-15 | 2006-09-07 | Koji Okada | Photosensitive resin composition capable of being developed with aqueous developer and photosensitive dry film resist, and use thereof |
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2010
- 2010-04-20 TW TW99112363A patent/TWI430036B/en active
- 2010-04-20 KR KR1020137033708A patent/KR101617507B1/en active IP Right Grant
- 2010-04-20 KR KR1020117020312A patent/KR20110118803A/en active Application Filing
- 2010-04-20 WO PCT/JP2010/057015 patent/WO2010123005A1/en active Application Filing
- 2010-04-20 CN CN201080017632.9A patent/CN102405441B/en active Active
- 2010-04-20 JP JP2010097102A patent/JP4620174B2/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000112133A (en) * | 1998-09-30 | 2000-04-21 | Toray Gosei Film Kk | Photoresist cover film for photosensitive plate |
| JP2002060426A (en) * | 2000-08-18 | 2002-02-26 | Japan Polyolefins Co Ltd | Protective film and process for manufacturing the same |
| JP2002323760A (en) * | 2001-04-25 | 2002-11-08 | Asahi Kasei Corp | Photopolymeric resin laminate |
| JP2003231759A (en) * | 2002-02-13 | 2003-08-19 | Japan Polyolefins Co Ltd | Method for manufacturing polyethylene as protective film and protective film manufactured by using it |
| CN1666150A (en) * | 2002-07-03 | 2005-09-07 | 住友电木株式会社 | Photosensitive compositions based on polycyclic polymers |
| JP2006113557A (en) * | 2004-09-14 | 2006-04-27 | Asahi Kasei Electronics Co Ltd | Method for manufacturing photosensitive resin laminate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102405441A (en) | 2012-04-04 |
| JP4620174B2 (en) | 2011-01-26 |
| KR20140007018A (en) | 2014-01-16 |
| WO2010123005A1 (en) | 2010-10-28 |
| TW201042398A (en) | 2010-12-01 |
| KR20110118803A (en) | 2011-11-01 |
| JP2010271709A (en) | 2010-12-02 |
| TWI430036B (en) | 2014-03-11 |
| KR101617507B1 (en) | 2016-05-02 |
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