CN1258696C - Photosensitive resin composition - Google Patents
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- CN1258696C CN1258696C CN 01816402 CN01816402A CN1258696C CN 1258696 C CN1258696 C CN 1258696C CN 01816402 CN01816402 CN 01816402 CN 01816402 A CN01816402 A CN 01816402A CN 1258696 C CN1258696 C CN 1258696C
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Abstract
A resist pattern having a film thickness of 1 to 100 mum and an aspect ratio (ratio of the line width to the film thickness of the resist pattern) of 3.5 or higher is provided in accordance with the present invention, the resist pattern being useful for increasing the density of a semiconductor package substrate circuit, and use of the resist pattern enabling a low conductor resistance to be maintained in fine wiring. This resist pattern can be produced using, for example, a photosensitive resin composition that includes (A) a binder polymer, (B1) a photopolymerizable compound having three ethylenically unsaturated bonds per molecule, (C) a photopolymerization initiator, and (D) either or both of a compound represented by general formula (I) and formula (II).
Description
Technical field
The present invention relates to resist pattern, photosensitive polymer combination, use its photosensitive element, the manufacture method of resist pattern and the manufacture method of conductor package substrate.
Background technology
In manufacturing such as printed circuit board (PCB), the conductor package substrate field, as the erosion resistant that burn into plating etc. is used, past is the photosensitive element that obtains with photosensitive polymer combination and support thereon and diaphragm of employing extensively.That is to say, photosensitive element is laminated on the copper base, behind pattern exposure, removes cured portion, after corrosion (decrement method) or electroplating (dosage method) processing formation pattern with developer solution, again cured portion is peeled off from substrate and removed, make circuit board and substrate with the method.
But, the densification requirement has been proposed for the live width/spacing (L/S) of circuit along with the miniaturization and the high performance of electronic device in recent years.And, need to use the photosensitive polymer combination of a kind of high sensitivity and low electrobath contaminative from operational point of view.
Highly sensitive Photoepolymerizationinitiater initiater is documented in No. the 11st, 786, the 220th, the 2nd, 027, No. 467 patent specifications of Germany, Europe and No. 589 prospectus and the spy opens in the flat 6-69631 equal sign patent gazette.And the 3rd, 479, put down in writing in No. 185 patent specification a kind of with electrobath contaminative itself that use as Photoepolymerizationinitiater initiater little 2,4,5-triarylimidazoles dimer and hydrogen donating compounds combine highly sensitive photosensitive polymer combination.
But the high sensitivity Photoepolymerizationinitiater initiater of putting down in writing in last each communique of note has electrobath contaminative problem, and use 2,4, the problem that exists under the dimeric occasion of 5-triarylimidazoles is: in case increase its use amount for adjusting to required sensitivity, will make live width chap against corrosion, and in case increase hydrogen for giving property compound use amount, will make and copper between adaptation and storage stability variation.
It is believed that the densification of the live width/spacing (L/S) of circuit at present proceeds to about 5～100 microns, wherein conductor package substrate such as BGA, CSP requires to have 30 microns following live width/spacings (L/S).Estimate that such densification requires also can further improve from now on.
On the other hand,,, can cause the resistance (conductor resistance) of circuit to increase, the signal that is called RC delay be transmitted to produce deleterious effect owing to will make circuit be higher than as above remarkable miniaturization though circuit distance shortens with the densification of copper circuit.This conductor resistance can be used following formula
(1) expression:
R=ρ L/A (1) (in the formula, R represents conductor resistance, and ρ represents the conductor resistance rate, and L represents conductor length, and A represents that cross-sectional area of conductor is long-pending).
Yet it is believed that in fine circuits, come the enlarged cross section area for the reduction that suppresses conductor resistance must increase copper film thickness.For example, obtain having same area of section with 10 microns copper circuit pattern widths and 15 microns copper film thickness copper circuit patterns under 6 microns pattern widths, copper film thickness must reach 25 microns.
Consider these aspects, for improve base plate for packaging processing with resolution against corrosion to adapt to the densification requirement, not only to the numerical value of live width/spacing (L/S), and the ratio of live width and the thickness of resist pattern, promptly shape is than also becoming essential condition.
In addition, peel off operability against corrosion after considering plating, necessary thickness against corrosion is generally 1.2 times of copper electroplating layer thickness, so for 6 microns copper circuit pattern widths, thickness against corrosion must reach 30 microns.Under this occasion, the shape ratio of the resist pattern that requires will reach 5.0.
Shape ratio described here is meant the ratio of live width and resist film thickness, promptly available following formula (2) expression:
The live width (micron) (2) of the thickness of shape ratio=resist pattern (micron)/resist pattern
In sum, though proposed requirement than the photosensitive polymer combination and the photosensitive element of resist pattern to making high shape, but the situation of prior art is, in case improve the adaptation of fine rule against corrosion and substrate, will resolution be worsened because of live width increases, be difficult to obtain have the sort of high-contrast of the exposed portion and the unexposed portion of enough shape ratios, and the resist pattern trend that atomisation pressure such as developer solution destroys when being developed in addition, thereby can not satisfy and go up summary and ask.
Summary of the invention
So the object of the invention be to provide a kind of can be used for suppressing fine circuits that conductor resistance reduces (promptly can suppress the fine circuits conductor resistance reduce with, to improve copper film thickness long-pending with enlarged cross section), the densification that is suitable for the conductor package substrate circuit is with the high resist pattern of resolution.
Another object of the present invention is to, provide a kind of and can be used to suppress fine circuits that conductor resistance reduces, be suitable for the densification of conductor package substrate circuit with the high resist pattern of resolution or the photosensitive polymer combination of resist pattern group manufacturing usefulness.
Another purpose of the present invention is, a kind of resist pattern that can be used to provide high resolving power, high shape ratio is provided, and provide sensitivity, resolution, anti-floating slag (generation of the カ of anti-ス system) and anti-plating good, be suitable for the photosensitive polymer combination that the densification of conductor package substrate circuit is used.
Another object of the present invention is, a kind of resist pattern that can be used to provide high resolving power, high shape ratio is provided, and provides sensitivity, resolution, anti-floating slag and anti-plating good, is suitable for the photosensitive element that the densification of conductor package substrate circuit is used.
Other the objective of the invention is to, a kind of fine circuits that conductor resistance reduces that can be used to suppress is provided, can be with the resolution that the densification that high productivity and good operability manufacturing are suitable for the conductor package substrate circuit is used the resist pattern manufacture method of high resist pattern.
The objective of the invention is at last, the manufacture method of the conductor package substrate that a kind of densification that can suppress fine circuits that conductor resistance reduces with high productivity and good operability manufacturing, be suitable for the conductor package substrate circuit uses is provided.
According to a first aspect of the present invention, a kind of thickness can be provided is 1～100 micron, shape is in the resist pattern more than 3.5 than the ratio of resist pattern thickness (live width with).
According to a second aspect of the present invention, can provide that a kind of can to make thickness be 1～100 micron, shape is in the photosensitive polymer combination of 3.5 above resist patterns than the ratio of resist pattern thickness (live width with).
According to a third aspect of the present invention, can provide 1～100 micron of a kind of utilization and thickness, shape to have the same widths space, can make and 1～100 micron of thickness, shape photosensitive polymer combination than the ratio of resist pattern thickness (live width with) resist pattern group that 3.5 above resist patterns are adjacent than the ratio of resist pattern thickness (live width with) resist pattern live width more than 3.5.
According to a fourth aspect of the present invention, a kind of photosensitive polymer combination can be provided, wherein contain (A) adhesive polymer, (B1) the optical polymerism compound of three ethene unsaturated links is arranged in the molecule, (C) Photoepolymerizationinitiater initiater and (D) one or both compounds in the compound of general formula (I) or general formula (II) expression
(m is 2～6 integer in the formula)
According to a fifth aspect of the present invention, a kind of photosensitive polymer combination can be provided, wherein contain (A) adhesive polymer, (B) has the optical polymerism compound of an ethene unsaturated link in the molecule at least, (C) Photoepolymerizationinitiater initiater and (E) leuco dye, the use level of described (E) composition, with respect to 100 weight portions (A) composition and (B) the composition total amount be 0.3～0.6 weight portion.
According to a sixth aspect of the present invention, a kind of photosensitive polymer combination can be provided, wherein contain (A) adhesive polymer, (B) have the optical polymerism compound of an ethene unsaturated link and (C) Photoepolymerizationinitiater initiater in the molecule at least, N as described (C) composition, N '-tetraalkyl-4,4 '-dicyano benzophenone content, with respect to 100 weight portions (A) composition and (B) the composition total amount be 0.04～0.08 weight portion.
According to a seventh aspect of the present invention, can provide a kind of at the photosensitive element that forms the resist layer formation of remembering the photosensitive polymer combination formation that the present invention relates on the support.
According to a eighth aspect of the present invention, a kind of manufacture method of using photosensitive polymer combination, shape that note the present invention relates to than the ratio of resist pattern thickness (live width with) 3.5 above resist patterns can be provided, comprising following operation:
I) on substrate, form the resist layer that forms by the photosensitive polymer combination that the present invention relates to, make dried thickness reach 1～100 micron operation;
Ii), make the operation that goes up note resist layer photocuring of exposed portion according to picture shape irradiation active ray;
Iii) remove the unexposed operation that goes up the note resist layer by the development selectivity.
According to a ninth aspect of the present invention, the manufacture method of a kind of shape than the ratio of resist pattern thickness (live width with) 3.5 above resist patterns can be provided, comprising following operation:
I) form the resist layer that is formed by photosensitive polymer combination on substrate, making under active ray wavelength 365nm delustring is resist layer below 0.5, and dried thickness reaches 1～100 micron operation;
Ii), make the operation that goes up note resist layer photocuring of exposed portion according to picture shape irradiation active ray;
Iii) remove the unexposed operation that goes up the note resist layer by the development selectivity.
According to a tenth aspect of the present invention, the manufacture method of a kind of shape than the ratio of resist pattern thickness (live width with) 3.5 above resist patterns can be provided, comprising following operation:
I) on substrate, form the resist layer that forms by photosensitive polymer combination, make dried thickness reach 1～100 micron formation operation;
Ii) see through the glass negative-appearing image and shine active ray, make the operation that goes up note resist layer photocuring of exposed portion according to picture shape;
Iii) remove the unexposed operation that goes up the note resist layer by the development selectivity.
According to a eleventh aspect of the present invention, the manufacture method of a kind of shape than the ratio of resist pattern thickness (live width with) 3.5 above resist patterns can be provided, comprising following operation:
I) on substrate, form the resist layer that forms by photosensitive polymer combination, make dried thickness reach 1～100 micron formation operation;
Ii), make the operation that goes up note resist layer photocuring of exposed portion according to picture shape irradiation parallel rays;
Iii) remove the unexposed operation that goes up the note resist layer by the development selectivity.
According to a twelveth aspect of the present invention, can provide a kind of use the photosensitive element that the present invention relates to of note, shape is than the manufacture method of the ratio of resist pattern thickness (live width with) 3.5 above resist patterns, comprising following operation:
I) will be layered on the substrate at the photosensitive element that the present invention relates to that the resist layer that forms on the support by the photosensitive polymer combination that the present invention relates to constitutes, make the operation of the surperficial driving fit of described resist layer and last note substrate;
Ii), make the operation that goes up note resist layer photocuring of exposed portion according to picture shape irradiation active ray;
Iii) remove the unexposed operation that goes up the note resist layer by the development selectivity.
According to a thirteenth aspect of the present invention, a kind of manufacture method of conductor package substrate can be provided, it is characterized in that the substrate of making resist pattern that adopts the dosage method that note be the present invention relates to forms circuit.
According to a fourteenth aspect of the present invention, a kind of manufacture method of conductor package substrate can be provided, it is characterized in that utilizing the decrement method to make utilizing and go up resist pattern manufacture method that note the present invention relates to and make the substrate of resist pattern and form circuit.
Now technique scheme of the present invention is summarized as follows:
1. photosensitive polymer combination, can utilize with 1～100 micron of thickness, shape be the space of the live width same widths of the resist pattern more than 3.5 than being live width to the ratio of resist pattern thickness, manufacturing and 1～100 micron of thickness, shape are the adjacent resist pattern group of resist pattern more than 3.5 than being live width to the ratio of resist pattern thickness, it is characterized in that
Contain:
(A) as constituting monomer, comprise the adhesive polymer of (methyl) acrylic acid and Arrcostab thereof,
(B) have in the molecule at least one ethene unsaturated link the optical polymerism compound and
(C) Photoepolymerizationinitiater initiater.
2. according to 1 described photosensitive polymer combination, wherein,, contain the optical polymerism compound that three ethene unsaturated links are arranged in (B1) molecule as described (B) composition.
3. according to 1 described photosensitive polymer combination, wherein,, contain (B2) 2, two (4-((methyl) propenyloxy group the gathers alkoxy) phenyl) propane of 2-as described (B) composition.
4. according to 1 described photosensitive polymer combination, wherein,, contain (B3) poly alkylene glycol two (methyl) acrylate as described (B) composition.
5. according to 1 described photosensitive polymer combination, wherein,, contain the compound that has at least one ethene unsaturated link and at least one phenyl or phenylene in (B4) molecule as described (B) composition.
6. according to 1～5 each described photosensitive polymer combination, wherein, as described (C) composition, contain 2,4,5-triarylimidazoles dimer.
7. according to 1～5 each described photosensitive polymer combination, wherein,, contain N, N '-tetraalkyl-4,4 '-diaminobenzophenone as described (C) composition.
8. according to 7 described photosensitive polymer combinations, wherein, described (C) N, N '-tetraalkyl-4, the use level of 4 '-diaminobenzophenone, with respect to 100 weight portions described (A) composition and (B) total amount of composition be 0.04～0.08 weight portion.
9. according to 1～5 each described photosensitive polymer combination, wherein, with respect to 100 weight portions described (A) composition and (B) total amount of composition, the use level of described (A) composition is 40～80 weight portions; The use level of described (B) composition is 20～60 weight portions; The use level of described (C) composition is 0.1～10 weight portion.
10. according to 1～5 each described photosensitive polymer combination, wherein,, also contain: by the compound of general formula (I) expression or by any compound or two kinds of compounds in the compound of general formula (II) expression as (D) composition.
(m is 2～6 integer in the formula)
11., wherein,, also contain leuco dye as (E) composition according to 1～5 each described photosensitive polymer combination.
12. according to 11 described photosensitive polymer combinations, wherein, the content of described (E) leuco dye with respect to 100 weight portions described (A) composition and (B) total amount of composition, is 0.3～0.6 weight portion.
13. according to 11 described photosensitive polymer combinations, wherein, described (E) leuco dye is a leuco crystal violet.
14. a photosensitive element is characterized in that, the resist layer that is formed by above-mentioned 1～13 each described photosensitive polymer combination forms on support.
15. the manufacture method of a resist pattern, the shape of this resist pattern is more than 3.5 than being live width to the ratio of resist pattern thickness, it is characterized in that, comprises following operation:
I) on substrate, form the resist layer that forms by 1～13 each described photosensitive polymer combination, make dried thickness reach 1～100 micron formation operation;
Ii), make the operation of the described resist layer photocuring of exposed portion according to picture shape irradiation active ray;
The iii) operation optionally remove unexposed described resist layer by developing.
16. according to the manufacture method of 15 described resist patterns, wherein, the absorbance when being formed on the wavelength 365nm of described active ray is the resist layer below 0.50, as described resist layer.
17. according to the manufacture method of 15 described resist patterns, wherein, picture shape is shone described active ray, makes the described resist layer photocuring of exposure portion by the glass negative film.
18., wherein,, make the described resist layer photocuring of exposure portion to picture shape irradiation parallel rays according to the manufacture method of 15 described resist patterns.
19. manufacture method according to 15 described resist patterns, wherein, described operation i) carries out according to the following stated: on support, form the resist layer that makes by 1～13 each described photosensitive polymer combination and obtain photosensitive element, the mode of resulting photosensitive element with the surperficial driving fit of above-mentioned resist layer and aforesaid substrate is layered on the substrate.
20. a resist pattern is characterized in that, this resist pattern is according to the manufacture method manufacturing of 15～19 each described resist patterns, and the thickness of resist layer is 1～100 micron, and the shape ratio is a live width to the ratio of resist pattern thickness is more than 3.5.
21. the manufacture method of a conductor package substrate is characterized in that, the substrate that adopts the dosage method to make the manufacture method of utilizing 15～19 each described resist patterns make resist pattern forms the loop.
Description of drawings
Fig. 1 is the synoptic diagram of a kind of photosensitive element embodiment that the present invention relates to of expression.
Fig. 2 is the synoptic diagram of a kind of operation example in the resist pattern manufacture method of representing the present invention relates to.
The synoptic diagram of Fig. 3 a kind of conductor package substrate manufacturing process example that to be expression the present invention relates to full dosage manufactured.
The synoptic diagram of Fig. 4 a kind of conductor package substrate manufacturing process example that to be expression the present invention relates to false add amount manufactured.
The synoptic diagram of Fig. 5 a kind of conductor package substrate manufacturing process example that to be expression the present invention relates to panel dosage manufactured.
Fig. 6 is the part amplification SEM photo that experimental example of the present invention obtains resist pattern.
Embodiment
Below describe embodiments of the present invention in detail.Wherein (methyl) acrylic acid described in the present invention is meant acrylic acid and corresponding with it methacrylic acid; described (methyl) acrylate is meant acrylate and corresponding with it methacrylate, and described (methyl) acryloyl group is meant acryloyl group and corresponding with it methacryl.
The resist pattern that the present invention relates to, thickness are 1～100 micron, and shape is in more than 3.5 than the ratio of resist pattern thickness (live width with).Satisfying this important document can provide a kind of high resolving power resist pattern that can suppress conductor resistance reduction in the fine circuits, can be used for the densification of conductor package substrate circuit.
As the means of making this resist pattern, note a method～methods such as h method are down for example arranged, undertaken by carrying out a method～h method or most appropriate combination respectively separately, can make this resist pattern.
Method a: as erosion resistant, use can be made thickness, and to be 1～100 micron, shape be in the photosensitive polymer combination of 3.5 above resist patterns than the ratio of resist pattern thickness (live width with).
Method b: as erosion resistant, use a kind of like this photosensitive polymer combination, said composition is utilized with 1～100 micron of thickness, shape has the space of same widths than the live width of the ratio of resist pattern thickness (live width with) 3.5 above resist patterns, can make 1～100 micron of thickness, shape than the ratio of resist pattern thickness (live width with) the resist pattern group that 3.5 above resist patterns are adjacent.
Method c: as erosion resistant, use and wherein contain (A) adhesive polymer, (B1) the optical polymerism compound of three ethene unsaturated links is arranged in the molecule, (C) Photoepolymerizationinitiater initiater and (D) one or both compounds in the compound of general formula (I) or general formula (II) expression.
(m is an integer in 2～6 in the formula)
Method d: as erosion resistant, use contains (A) adhesive polymer, (B) has the optical polymerism compound of an ethene unsaturated link in the molecule at least, (C) Photoepolymerizationinitiater initiater and (E) leuco dye, the use level of wherein said (E) composition, with respect to 100 weight portions (A) composition and (B) the composition total amount be the photosensitive polymer combination of 0.3～0.6 weight portion.
Method e: as erosion resistant, use contains (A) adhesive polymer, (B) have the optical polymerism compound of an ethene unsaturated link and (C) Photoepolymerizationinitiater initiater in the molecule at least, wherein as the N of described (C) composition, N '-tetraalkyl-4, the use level of 4 '-dicyano benzophenone, with respect to 100 weight portions (A) composition and (B) the composition total amount be the photosensitive polymer combination of 0.04～0.08 weight portion.
Method f: use as erosion resistant to can be formed in that delustring is the photosensitive polymer combination of 0.50 following resist layer under the active ray wavelength 365nm, thickness was 1～100 micron after stacked formation resist layer made it dry on substrate, shine the resist layer photocuring that active ray makes exposed portion according to picture shape, remove unexposed resist layer by development.
Method g: on substrate, form the resist layer that photosensitive polymer combination constitutes, make dried thickness be in 1～100 micron, see through glass negative-appearing image pattern and shine the resist layer photocuring that active ray makes exposed portion according to picture shape, utilizing develops removes unexposed resist layer.
Method h: form the resist layer that photosensitive polymer combination constitutes on substrate, make dried thickness be in 1～100 micron, shine the resist layer photocuring that parallel rays makes exposed portion according to picture shape, utilizing develops removes unexposed resist layer.
Among last note method a and the method b, preferably containing as concrete gradation composition has the optical polymerism compound of three ethene unsaturated links and (D) goes up the represented compound of note general formula (I) or go up one or both compounds in the represented compound of note general formula (II) in (B1) molecule.
Among last note method c, method d and the method e, preferably also contain (B2) 2, two (4-((methyl) propenyloxy group gather alkoxy) phenyl) propane of 2-, (B3) poly alkylene glycol (methyl) acrylate and more than one compounds in the compound of at least one ethene unsaturated link and at least one phenyl or phenylene (B4) are arranged in the molecule.And, preferably contain 2,4,5-triarylimidazoles dimer as (C) Photoepolymerizationinitiater initiater.Among method d and the method e, preferably contain note (B1) composition in addition as last note (B) composition.
The resist pattern that below just the present invention relates to forms with each gradation composition in the preferred photosensitive polymer combination that uses and describes.
(A) as the resin glue polymkeric substance, for example can enumerate propylene resin, phenylethylene resin series, epoxy is that resin, acid amides are that resin, acid amides epoxy are that resin, alkyd are resin, phenol resin etc.Consider preferred propylene resin from the alkaline development performance.
And as (A) composition, can adopt the mode that makes polymerizable monomer radical polymerization to make.As this polymerizable monomer, for example can enumerate styrene, vinyltoluene, α-Jia Jibenyixi, p-methylstyrene, right-polymerism styrene derivatives such as ethyl styrene, acrylamide, vinyl cyanide, the ester class of vinyl alcohol such as vinyl n-butyl ether, (methyl) alkyl acrylate, (methyl) acrylic acid tetrahydro furfuryl ester, (methyl) acrylic acid dimethylamino ethyl ester, (methyl) acrylic acid diethylamino ethyl ester, (methyl) glycidyl acrylate, 2,2,2-trifluoroethyl (methyl) acrylate, 2,2,3,3-tetrafluoro propyl group (methyl) acrylate, (methyl) acrylic acid, alpha-brominated (methyl) acrylic acid, alpha-chloro (methyl) acrylic acid, β-furfuryl group (methyl) acrylic acid, β-styryl (methyl) acrylic acid, maleic acid, maleic anhydride, monomethyl maleate, ethyl maleate, maleic acids such as maleic acid list isopropyl ester are monoesters, fumaric acid, cinnamic acid, the alpha-cyano cinnamic acid, itaconic acid, butenoic acid, propiolic acid.These monomers may be used singly or two or more in combination.
As last note (methyl) alkyl acrylate, for example can enumerate (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 etc.These monomers may be used singly or two or more in combination.
Consider from the alkaline development performance among the present invention that (A) composition preferably contains the monomer of being with carboxyl as monomeric unit.This polymkeric substance for example can adopt the method manufacturing that makes the monomer free base polymerization with carboxyl and other polymerisms.Last note has preferred (methyl) acrylic acid of polymerizable monomer of carboxyl.And consider that from activity (A) composition preferably contains styrene or styrene derivative as polymerizable monomer.When containing styrene or styrene derivative with the copolymer composition form, for making adaptation and peel property all good, the ratio of styrene or styrene derivative in the polymkeric substance, more than the preferred 3 weight % of adaptation angle, big and splitting time is considered below the preferred 30 weight % from stripping film, more preferably 4～28 weight %, preferred especially 5～27 weight %.
(A) acid number of composition is preferably more than 30 milligrams of KOH/ grams from the development time viewpoint, considers below then preferred 200 milligrams of KOH/ gram from the anti-development fluidity viewpoint against corrosion of photocuring, more preferably 50～150 milligrams of KOH/ grams.
(A) weight-average molecular weight of composition is measured with gel permeation chromatography (GPC), from the numerical value that the working curve of polystyrene standard making is calculated, considers preferred 20 from anti-development fluidity viewpoint, more than 000, preferred below 300,000 from the development time viewpoint, more preferably 30,000～150,000.
These adhesive polymers may be used singly or two or more in combination.As the adhesive polymer that is used in combination under the occasion, for example can enumerate diverse two or more adhesive polymer, the different different two or more adhesive polymers two or more adhesive polymers different of two or more adhesive polymers, weight-average molecular weight of copolymer composition with dispersion degree.And can use the spy to open the polymkeric substance with multiplex mode molecular weight distribution of flat 11-327137 communique record.In addition, these adhesive polymers can also have the photonasty group in case of necessity.
As the optical polymerism compound that has an ethene unsaturated link in last note (B) molecule at least, for example can preferably use radical polymerization.So-called ethene unsaturated link, be meant can polymerization the ethene unsaturated link.Instantiation for example can be enumerated the various bisphenol-A of aftermentioned system (methyl) acrylate compounds of work (B2) composition, α, beta-unsaturated carboxylic acid reacts the compound that obtains with the compound of band glycidyl, the urethane monomers such as (methyl) acrylate compounds that urethane bond is arranged in the molecule, make the various Nonylphenoxy polyoxyethylene of aftermentioned (methyl) acrylate of (B4) composition, γ-chloro-β-hydroxy propyl-Beta '-(methyl) acrylic ethyl phthalic ester, phthalic acid based compounds such as beta-hydroxy alkyl-β '-(methyl) acrylic alkyl phthalate and (methyl) alkyl acrylate etc.These compounds can use separately or two or more composition uses.
As α, the compound that beta-unsaturated carboxylic acid and last note polyol reaction obtain, for example can enumerate the various poly alkylene glycol two of aftermentioned (methyl) acrylate, trimethylolpropane two (methyl) acrylate, as the aftermentioned of (B1) composition various three (methyl) acrylate compounds, tetramethylol methane four (methyl) acrylate, dipentaerythritol five (methyl) acrylate and dipentaerythritol six (methyl) acrylate etc. as (B3) composition.
As (methyl) acrylate compounds that urethane bond is arranged in the molecule, for example can enumerate (methyl) of hydroxyl propenyl monomer and isophorone diisocyanate, 2 are arranged on the β position, 6-toluene diisocyanate, 2,4-toluene diisocyanate, 1, addition reaction product between the diisocyanate cpds such as 6-hexamethylene diisocyanate, three ((methyl) propenyloxy group four ethylidene glycol isocyanates) hexa-methylene cyanurate, urethane two (methyl) acrylate of EO modification and urethane two (methyl) acrylate of EO/PO modification etc.As urethane two (methyl) acrylate of EO modification, for example can enumerate UA-11 (Xin Zhong village chemical industry Co., Ltd. makes, trade name) etc.And, for example can lift UA-13 (Xin Zhong village chemical industry Co., Ltd. makes, trade name) etc. as urethane two (methyl) acrylate of EO/PO modification.
In preferred embodiment, can use the optical polymerism compound that three ethene unsaturated links are arranged in (B1) molecule as last note (B) composition.Contain (B1) composition and can improve cross-linking density against corrosion, effectively prevent the destruction of resist pattern.
As (B1) composition, so long as just being not particularly limited of three ethene unsaturated links arranged in the molecule, for example can enumerate trimethylolpropane tris (methyl) acrylate, the trimethylolpropane tris of EO modification (methyl) acrylate, the trimethylolpropane tris of PO modification (methyl) acrylate, the trimethylolpropane tris of EO/PO modification (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite three (methyl) acrylate of EO modification, pentaerythrite three (methyl) acrylate of PO modification, pentaerythrite three (methyl) acrylate of EO/PO modification, tetra methylol propane three (methyl) acrylate, tetra methylol propane three (methyl) acrylate of EO modification, tetra methylol propane three (methyl) acrylate of PO modification, tetra methylol propane three (methyl) acrylate of EO/PO modification etc.As the commodity that can buy from the market, can enumerate for example ATMM-3 (Xin Zhong village chemical industry Co., Ltd. manufacturing, the trade name of tetramethylol methane triacrylate), TMPT21E and TMPT30E (the sample name that Xin Zhong village chemical industry Co., Ltd. makes, the trimethylol-propane trimethacrylate of EO modification).These may be used singly or two or more in combination.EO representative ring oxidative ethane wherein, the compound of EO modification has the ethylene oxide group block structure.And PO representative ring Ethylene Oxide, the compound of PO modification has the propylene oxide group block structure.
In other embodiment preferred, in order further to improve resolution, anti-floating slag and anti-plating, can use (B2) 2, two (4-((methyl) propenyloxy group the gathers alkoxy) phenyl) propane of 2-.As this (B2) composition, for example can enumerate 2, two (4-((methyl) propenyloxy group polyethoxy) phenyl) propane, 2 of 2-, two (4-((methyl) propenyloxy group the gathers propoxyl group) phenyl) propane, 2 of 2-, two (4-((methyl) propenyloxy group the gathers butoxy) phenyl) propane and 2 of 2-, two (4-((methyl) propenyloxy group polyethoxy the gathers propoxyl group) phenyl) propane of 2-.In (B2) composition, can be identical between a plurality of alkoxys, also can be different.And work as alkoxy by under the occasion that constitutes more than two, two above alkoxys can exist with disorganized form, or exist with block.As last note the compound of two above alkoxys is arranged, for example can enumerate 2, two (4-((methyl) propenyloxy group polyethoxy the gathers propoxyl group) phenyl) propane of 2-.These (B2) compositions may be used singly or two or more in combination.
As last note 2, two (4-((methyl) propenyloxy group polyethoxy) phenyl) propane of 2-, for example can enumerate 2, two (4-((methyl) propenyloxy group diethoxy) phenyl) propane of 2-, 2, two (4-((methyl) propenyloxy group triethoxy) phenyl) propane of 2-, 2, two (4-((methyl) propenyloxy group tetraethoxy) phenyl) propane of 2-, 2, two (4-((methyl) propenyloxy group five ethoxys) phenyl) propane of 2-, 2, two (4-((methyl) propenyloxy group six ethoxys) phenyl) propane of 2-, 2, two (4-((methyl) propenyloxy group seven ethoxys) phenyl) propane of 2-, 2, two (4-((methyl) propenyloxy group eight ethoxys) phenyl) propane of 2-, 2, two (4-((methyl) propenyloxy group nine ethoxys) phenyl) propane of 2-, 2, two (4-((methyl) propenyloxy group ten ethoxys) phenyl) propane of 2-, 2, two (4-((methyl) propenyloxy group 11 ethoxys) phenyl) propane of 2-, 2, two (4-((methyl) propenyloxy group ten diethoxies) phenyl) propane of 2-, 2, two (4-((methyl) propenyloxy group ten triethoxies) phenyl) propane of 2-, 2, two (4-((methyl) propenyloxy group ten tetraethoxies) phenyl) propane of 2-, 2, two (4-((methyl) propenyloxy group 15 ethoxys) phenyl) propane and 2 of 2-, two (4-((methyl) propenyloxy group 16 ethoxys) phenyl) propane of 2-etc.(Xin Zhong village chemical industry Co., Ltd. makes wherein can to have bought commodity BPE-500 by name on market, ProductName) 2, two (4-(the metacryloxy five ethoxys) phenyl) propane of 2-, commodity are called EPE-1300, and (Xin Zhong village chemical industry Co., Ltd. makes, ProductName) 2, two (4-(the metacryloxy 15 ethoxys) phenyl) propane of 2-.These compounds may be used singly or two or more in combination.
As last note 2, two (4-((methyl) propenyloxy group polyethoxy the gathers propoxyl group) phenyl) propane of 2-, for example can enumerate 2, two (4-((methyl) propenyloxy group diethoxy eight propoxyl group) phenyl) propane, 2 of 2-, two (4-((methyl) propenyloxy group tetraethoxy four propoxyl group) phenyl) propane and 2 of 2-, two (4-((methyl) propenyloxy group six ethoxys six propoxyl group) phenyl) propane of 2-etc.These compounds may be used singly or two or more in combination.
In other embodiment preferred,, can use (B3) poly alkylene glycol two (methyl) acrylate in order further to improve various etch resistant properties such as resolution, anti-floating slag and anti-plating.Specifically can enumerate the ethylidene number and be 2～14 polyglycol two (methyl) acrylate, propylidene number and be 2～14 polypropylene glycol two (methyl) acrylate, Aden's radix and be 2～14 polytetramethylene glycol two (methyl) acrylate, from sensitivity and the preferred diacrylate ester compounds of anti-floating slag angle.And from resolution and adaptation viewpoint, preferred polyethylene glycol dimethacrylate.These compounds may be used singly or two or more in combination.
In this (B3) composition, a plurality of alkylene glycol chains can be identical or different separately.Under the occasion that is made of two above alkylene glycol chains, two above alkylene glycol chains can exist with random fashion separately, or exist with block form.Have the compound of two above alkylene glycol chains as last note, can enumerate ethylidene number for example and be 2～14 and the propylidene number be 2～14 poly-ethylidene polytrimethylene glycol two (methyl) acrylate.
In the other preferred embodiment, in order further to improve anti-floating slag and peel property, can use the compound that at least one ethene unsaturated link and at least one phenyl or phenylene are arranged in (B4) molecule.This (B4) composition so long as at least one ethene unsaturated link is arranged in the molecule and molecule in also have the compound of at least one phenyl or phenylene just not have special restriction, for example can enumerate by the compound of remembering general formula (III) expression down
(in the formula, R represents hydrogen atom or methyl, and X represents 2～20 carbon atom alkyls, and s represents integer in 1～30) and phthalic acid based compound etc., the preferred compound of going up note general formula (III) expression.The phenyl of last note or phenylene can have any substituting group.The preferred ethylidene of X in the last note general formula (III).
As the substituting group in phenyl or the phenylene, the aryl, amino, the alkyl amino of 1～10 carbon atom, the dialkyl amido of 2～20 carbon atoms, nitro, cyano group, sulfydryl, the alkyl thiol of 1～10 carbon atom, allyl, the hydroxy alkyl of 1～20 carbon atom, alkyl carbon atoms number that for example can enumerate the naphthenic base of the alkyl of halogen atom, 1～20 carbon atom, 3～10 carbon atoms, 6～14 carbon atoms is that 1～10 carboxyalkyl, alkyl carbon atoms number are the alkoxy of 1～10 acyl group, 1～20 carbon atom or the group that contains heterocycle.And the hydrogen atom on the alkyl also can be replaced by halogen atom.From the viewpoint of anti-development fluidity, development and adaptation, the alkyl of preferred 1～20 carbon atom, the more preferably alkyl of 4～14 carbon atoms, especially preferably nonyl.Preferred 0～5 of the number of these replacements, more preferably 1～4, preferred especially 1～3, best 1～2.On keep in mind for the radix order and have under the occasion more than 2, two above substituting groups can be identical or different.
The compound of last note general formula (III) expression for example can be enumerated Nonylphenoxy polyoxyethylene (methyl) acrylate, Nonylphenoxy polyoxypropylene (methyl) acrylate, butyl phenoxy polyoxyethylene (methyl) acrylate, butyl phenoxy polyoxypropylene (methyl) acrylate.But from anti-floating slag viewpoint, preferred Nonylphenoxy polyoxyethylene acrylate.These materials may be used singly or two or more in combination.
As last note Nonylphenoxy polyoxyethylene (methyl) acrylate, for example can enumerate Nonylphenoxy four oxygen ethene (methyl) acrylate, Nonylphenoxy five oxygen ethene (methyl) acrylate, Nonylphenoxy hexaoxyethylene (methyl) acrylate, Nonylphenoxy seven oxygen ethene (methyl) acrylate, Nonylphenoxy eight oxygen ethene (methyl) acrylate, Nonylphenoxy nine oxygen ethene (methyl) acrylate, Nonylphenoxy ten oxygen ethene (methyl) acrylate, Nonylphenoxy 11 oxygen ethene (methyl) acrylate and Nonylphenoxy ten dioxy ethene (methyl) acrylate etc.The compound that can buy from the market can be enumerated commodity such as NP-8EA by name that Kyoeisha Chemical Co., Ltd. makes and NP-4EA.These compounds may be used singly or two or more in combination.
Below enumerate as (C) Photoepolymerizationinitiater initiater, benzophenone for example, N, N '-tetramethyl-4,4 '-diaminobenzophenone N such as (rice are sneered Le Shi ketone), N '-tetraalkyl-4,4 '-diaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholine subbase phenyl)-butanone-1,2-methyl isophthalic acid-ketone such as aromatic series such as [4-(methyl mercapto) phenyl]-2-morpholine subbase acetone-1 grade, quinones such as alkyl-anthraquinone, diphenylhydroxyethanone ether compounds such as diphenylhydroxyethanone alkyl ether, diphenylhydroxyethanone, diphenylhydroxyethanone compounds such as alkyl diphenyl ethanol ketone, benzyl derivatives such as benzyl dimethyl ketal, 2-(adjacent chlorophenyl)-4,5-diphenyl-imidazole dimer, 2-(adjacent chlorophenyl)-4,5-two (methoxyphenyl) imidazoles dimer, 2-(adjacent fluoro phenyl)-4,5-diphenyl-imidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenyl-imidazole dimer, 2-(p-methoxyphenyl)-4,2 of 5-diphenyl-imidazole dimer etc., 4,5-triarylimidazoles dimer, the 9-phenylacridine, 1,7-two (9,9 '-acridinyl) acridine derivatives such as heptane, N-phenylglycine, the N-phenylglycine derivant, coumarin series compounds etc.These compounds may be used singly or two or more in combination.The various characteristics of photosensitive polymer combinations such as high sensitivity and low electrobath contaminative depends on the kind and the quantity of the Photoepolymerizationinitiater initiater that uses.
In last note (C) composition,, especially, preferably use 2,4,5-triarylimidazoles dimer from adaptation and sensitivity viewpoint for further improving sensitivity, resolution and anti-plating.Wherein two 2,4, the substituting group in the 5-triarylimidazoles on the aryl both can identical formation enantiomeric compounds, also can differently form asymmetric compounds.
And preferably allocate N into, N '-tetraalkyl-4,4 '-diaminobenzophenone N such as (rice are sneered Le Shi ketone), N '-tetraalkyl-4,4 '-diaminobenzophenone.This N, N '-tetraalkyl-4, the use level of 4 '-diaminobenzophenone, from improving light penetration against corrosion, adjusting dullness to improve the viewpoint of bottom against corrosion curable, with respect to 100 weight portions (A) composition and (B) the composition total amount preferably account for 0.04～0.08 weight portion, more preferably account for 0.04～0.07 weight portion, especially preferably account for 0.045～0.06 weight portion, preferably account for 0.045～0.05 weight portion.
In some other embodiment preferred, in order effectively to suppress to produce unwanted gelatination because of light scatter etc., improving contrast and to obtain high shape ratio, can one or both materials use as (D) composition in the compound of the compound of note general formula (I) expression and last note general formula (II) expression with going up.From the viewpoint of resolution, more preferably use the compound of general formula (I) expression.This by using (D) composition can further improve resolution and anti-plating.
Each compound of last note general formula (I), (II) expression can have any substituting group, be can be identical or different between most substituting groups under the occasion of majority when these substituting groups.These substituent numbers are preferred 0～4, and more preferably 0～3, preferred especially 0～2, very preferred 0～1, preferably 1.
Substituting group as last note, for example can enumerate halogen atoms such as fluorine, chlorine, bromine, astatine, the naphthenic base of the alkyl of 1～20 carbon atom, 3～10 carbon atoms, can be by aryl such as the phenyl of the alkyl of amino or 1～20 carbon atom replacement, naphthyls, amino, sulfydryl, alkyl carbon atoms number are the alkoxy of 1～10 alkyl thiol, the carboxyalkyl that the alkyl carbon atoms number is 1～10,1～20 carbon atom and the group that heterocyclic group forms, wherein preferred alkyl.
Alkyl as 1～20 carbon atom of last note, for example can enumerate methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, sec-butyl, the tert-butyl group, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, tridecyl, myristyl, pentadecyl, cetyl, nonadecyl, eicosyl and isomeride thereof, butyl such as wherein preferred normal-butyl, sec-butyl, the tert-butyl group, the more preferably tert-butyl group.As the naphthenic base of 3～10 carbon atoms of last note, can enumerate cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, ring octyl group ring octyl group etc.By the aryl that 1～20 carbon atom alkyl replaces, can enumerate aminomethyl phenyl, ethylphenyl, propyl group phenyl etc. as last note.
Alkyl thiol as 1～10 carbon atom of last note.For example can enumerate methyl mercapto, ethyl sulfydryl, propyl group sulfydryl etc.As the carboxyalkyl of 1～10 carbon atom alkyl of last note, for example can enumerate ethyloic, carboxyethyl, carboxylic propyl group, carboxylic butyl etc.As the alkoxy of 1～20 carbon atom of last note, for example can enumerate methoxyl, ethoxy, propoxyl group etc.As the group that last note is made of heterocycle, for example can enumerate Oxyranyle, furyl, thienyl, pyrrole radicals, thiazolyl, indyl, quinolyl etc.
In the last note general formula (I), m is an integer in 2～6, integer in preferred 2～4, more preferably integer in 2～3, preferably 2.M will worsen less than 2 o'clock resolution.
Compound as this general formula (I) expression, for example can enumerate catechol, resorcinol, 1, the 4-quinhydrones, the 2-methyl pyrocatechol, the 3-methyl pyrocatechol, the 4-methyl pyrocatechol, 2-ethyl catechol, 3-ethyl catechol, 4-ethyl catechol, 2-propyl group catechol, 3-propyl group catechol, 4-propyl group catechol, 2-normal-butyl catechol, 3-normal-butyl catechol, 4-normal-butyl catechol, the 2-tert-butyl catechol, the 3-tert-butyl catechol, the 4-tert-butyl catechol, 3, alkyl catechols such as 5-di-t-butyl catechol, the 2-methylresorcinol, cresorcinol, the 2-ethyl resorcinol, the 4-ethyl resorcinol, 2-propyl group resorcinol, 4-propyl group resorcinol, the 2-n-butyl resorcinol, the 4-n-butyl resorcinol, the 2-tert-butyl resorcin, alkyl-resorcins such as 4-tert-butyl resorcin, methylnaphthohydroquinone, the ethyl quinhydrones, the propyl group quinhydrones, tertiary butylated hydroquinone, 2.5-alkyl quinhydrones such as di-tert-butyl hydroquinone, pyrogallol, fluoro glucin etc., wherein preferred catechol, the alkyl catechol, alkyl quinhydrones or quinhydrones especially preferably use the 4-tert-butyl catechol in the alkyl catechol.These compounds may be used singly or two or more in combination.As the compound of last note general formula (II) expression, for example can enumerate adjacent benzo quinhydrones and to the benzo quinhydrones.
In some preferred embodiments, can use (E) leuco dye, suitably select the use level of this (E) composition, can improve all degree of cure of resist layer as the hydrogen donor.The instantiation of leuco dye, for example can enumerate leuco crystal violet, (three (4-dimethylaminophenyl) methane), three (4-diethylamino-2-aminomethyl phenyl) methane, colourless peacock green, colourless aniline, colourless methyl violet etc., give the viewpoint that the ability height does not make resolution worsen from hydrogen, preferred leuco crystal violet.Its use level with respect to 100 weight portions (A) composition and (B) the composition total amount preferably account for 0.3～0.6 weight portion, more preferably account for 0.3～0.5 weight portion, especially preferably account for 0.35～0.45 weight portion.
In other embodiment preferred, in order to improve light penetration against corrosion, to adjust absorbance to improve the curing row of bottom against corrosion, reach the purpose of resolution and high shape ratio, can use a kind of like this photosensitive polymer combination, this composition can be formed on common light-sensitive surface exposure and be in 0.50 following resist layer with absorbance under the main output wavelength 365mm of active ray in the exposure machine.As long as the absorbance of resist layer (photosensitive resin composition layer) is in below 0.50, just can after drying, be in any resist layer thickness of setting in 1～100 micrometer range by thickness.
The preferred use level of each composition below is described.(A) use level of composition, the viewpoint of film performance from the hardness (fragility) of photocuring thing and when making photosensitive element and using, preferably account for more than 40 weight portions with respect to 100 weight portions (A) composition and (B) total amount of composition, preferably be in below 80 weight portions from luminous sensitivity, more preferably be between 45～70 weight portions.
(B) use level of composition, from the luminous sensitivity angle see preferably 100 weight portions (A) composition with (B) account for more than 20 weight portions the composition general assembly (TW), preferably be in below 60 weight portions from the hardness (fragility) of photocuring thing.More preferably be between 30～55 weight portions.
(B) (B1) components in proportions in the composition is considered preferably to be in more than the 2 weight % from sensitivity and resolution viewpoint, preferably is in below the 40 weight % more excellent being in 3～35 weight portion scopes from splitting time.(B) (B2) components in proportions in the composition is considered preferably to be in more than the 10 weight % from the resolution viewpoint, preferably is in below the 90 weight % more excellent being in 20～80 weight portion scopes from splitting time.(B) (B3) components in proportions in the composition is considered preferably to be in more than the 5 weight % from sensitivity and fine rule adaptation viewpoint, preferably is in below the 60 weight % more excellent being in 10～30 weight portion scopes from cohesiveness.(B) (B4) components in proportions in the composition is considered preferably to be in more than the 4 weight % from the splitting time viewpoint, preferably is in below the 20 weight % more excellent being in 6～12 weight portion scopes from fine rule adaptation angle.
(C) use level of composition, from the luminous sensitivity viewpoint preferably 100 weight portions (A) composition with (B) account for more than 0.1 weight portion the composition total amount, preferably account for below 10.0 weight portions from the curable and the scum silica frost generation consideration of bottom against corrosion, more preferably be in 0.6～6.0 weight portion scope.
(D) use level of composition, is considered preferably to be in more than 0.001 weight portion from resolution with respect to 100 weight portions (A) composition for (B) composition total amount, below preferred 3 weight portions of sensitivity, more preferably is between 0.01～0.1 weight portion.
Photosensitive polymer combination, can also further contain cationic polymerization initiators in case of necessity, photodevelopers such as malachite green and other dyes, tribromo-benzene sulfone, leuco crystal violet, heat colour developing inhibitor, to plastifier such as toluene sulfonamide, pigment, filling agent, defoamer, fire retardant, stabilizing agent, sealant, levelling agent, peel off promoter, antioxidant, spices, preparation, thermal cross-linking agent etc., its content can respectively account for 0.01～20 weight portion with respect to 100 weight portions (A) composition and (B) total amount of composition.These materials may be used singly or two or more in combination.
The photosensitive polymer combination that uses among the present invention, can as required it be dissolved in methyl alcohol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, in dinethylformamide, propylene glycol monomethyl ether equal solvent or its mixed solvent, make and be coated with after solid shape is divided into solution about 30～60 weight %.Its purposes is not particularly limited, and is coated on the metal surfaces such as copper, aldary, iron, ferroalloy after the drying so that liquid state is against corrosion, covers with diaphragm in case of necessity and uses, and perhaps preferably uses with the photosensitive element form.
The following photosensitive element that the present invention relates to reference to description of drawings promptly forms the photosensitive element that resist layer that the photosensitive polymer combination related to by the invention described above forms constitutes on support.
Fig. 1 is the synoptic diagram of a kind of photosensitive element embodiment of expression, and photosensitive element 1 comprises support 11 and the resist layer 12 (photosensitive polymer combination layer) that forms thereon.
As support 11, the polymer film that for example can preferably use for example polyethylene terephthalate, polypropylene, tygon, polyester etc. to have thermotolerance and solvent resistance.And as preferred 1～100 micron of the thickness of the polymer film of support.
There is no particular restriction to the method that forms resist layer 12 on the support 11, but more preferably the photosensitive polymer combination solution coat is being obtained after the drying on the support 11.The resist layer thickness of coating is different according to purposes, but dried thickness preferably is in 1～100 micron, more preferably is in 3～80 microns, especially preferably is in 5～50 microns, extremely preferably is in 10～45 microns, is preferably 20～40 microns.Coating can be adopted roll coater, industrial coating machine, runner gravure coating machine, air roll coator, mold pressing coating machine, rod to be coated with known methods such as machine to carry out.Drying can be carried out 5～30 minutes under 70～150 ℃ of temperature.And residual organic solvent amount in against corrosion, from preventing from subsequent handling, to produce the viewpoint of organic solvent diffusion, preferably be in below the 2 weight %.
The resist layer 12 of photosensitive element 1 preferably covers with the film formed diaphragm (not shown) of polymkeric substance such as tygon, polypropylene.Also can adopt a kind of support of doing in any polymer film, and with another kind as diaphragm, be layered on the resist layer two sides.In addition as the clinging power between preferred resist layer of diaphragm and diaphragm less than clinging power between resist layer and support, and preferably use low flake film.The thickness of diaphragm is preferably greater than 5 microns from the intensity viewpoint, and from cheap angle preferably less than 30 microns.
These supporting films and diaphragm so can not make it inexpungible surface treatment, still also can carry out surface treatment owing to must remove from resist layer afterwards in case of necessity.For example can carry out the electrostatic prevention processing to these supports and diaphragm in case of necessity.
By support and resist layer, and two-layer or three layers of photosensitive element of constituting of diaphragm in case of necessity, also can have middle layer such as not shown cushion, adhesive linkage, light absorbing zone, barrier layer for gases and protective seam etc.
The photosensitive element that obtains so for example can be directly or behind stacked diaphragm on the resist layer surface, preserves after being rolled into tubular on the cylindric volume core.At this moment, preferably reel to such an extent that make support be in outermost.And preferably on the end face of the photosensitive element cylinder that is curled, spacer is set, for the purpose of the protection end face, the damp proof spacer of end face is set preferably.And, be preferably packaged in the low black sheet material of water permeability as bundling method.As the volume core, for example can enumerate polyvinyl resin, acrylic resin, polystyrene resin, Corvic, ABS resin plastic substances such as (acrylonitrile-butadiene-styrene copolymers).
Following reference schematically illustrates Fig. 2 of an example of its operation, and the manufacture method of the resist pattern that the present invention relates to is described.
At first, as operation (i), the resist layer that formation is made of the resin combination any against corrosion of the invention described above on substrate (circuit form use substrate) 2 is for example shown in Fig. 2 (A), stacked above-mentioned photosensitive element on substrate 2 makes resist layer 12 and substrate 2 surperficial driving fits.Before existing under the occasion of diaphragm (not shown), be stacked, resist layer 12 surfaces of photosensitive element 1 should remove diaphragm.As laminating method, for example can enumerate and adopt one side that resist layer 12 is heated to about 70～130 ℃, on one side with the layered manner of (about 1～10 kilogram/square centimeter) pressure about 0.1～1MPa to substrate 2 pressurizations.And can be under reduced pressure stacked.Wherein stacked substrate 2 surfaces are common metal coverings, and there is no particular restriction to it.And,,, also can carry out thermal pretreatment to substrate in order further to improve stacked performance though needn't carry out thermal pretreatment to substrate if resist layer is heated to 70～130 ℃ as described above.
After resist layer forms and stops, (ii) shine active ray as operation according to picture shape, the above-mentioned resist layer of exposed portion is solidified, as method according to image irradiation active ray, for example shown in Fig. 2 (B), active ray is seen through be called erect image or the negative-appearing image type mask pattern 3 of former figure to be radiated on the resist layer 12, can make resist layer 12 Photosettings of exposed portion like this with picture shape.As the light source of active ray, can use known light source, for example carbon arc lamp, mercury-vapor lamp, high-pressure mercury-vapor lamp, xenon lamp etc. can effectively penetrate the light fixture of ultraviolet ray, visible light.As exposure machine, from obtaining the viewpoint preferred parallel light exposure machine of resolution, high shape ratio.As mask pattern, for example can enumerate PET mask pattern and glass mask pattern, but from preventing scattering and refraction and the viewpoint preferred glass mask pattern that obtains resolution, high shape ratio.Wherein operation exposure (ii) as long as do not hinder light to irradiation on the resist layer 12 (under the occasion of support for the transparency), can expose under the state that has support 11.Also can directly expose without mask pattern with the method that laser is described.
After the exposure, after existing under the occasion of support on the photosensitive polymer combination layer, removing support, as operation (iii), remove unexposed resist layer, shown in Fig. 2 (C), form Figure 121 against corrosion by the development selectivity.Develop and adopt wet developing method and dry process development method to carry out, use the developer solutions corresponding such as alkaline aqueous solution, water system developer solution, organic solvent under the occasion of employing wet developing, carry out with impregnated, atomizing, grooming formula, rove wiping formula known methods such as (ス ラ ッ PVC Application グ) with the composition of resist layer.Can and use two or more developing methods in case of necessity.As last note alkaline aqueous solution, can enumerate for example 0.1～5 weight % sodium carbonate lean solution, 0.1～5 weight % sal tartari lean solution, 0.1～5 weight % dilute solution of sodium hydroxide etc.The pH of alkaline aqueous solution preferably is between 9～11, and its temperature can be regulated according to the developing performance of photosensitive polymer combination layer.But also can in alkaline aqueous solution, add surfactant, defoamer, organic solvent etc.
As the processing after developing, also can under 60～250 ℃ of left and right sides temperature, heat or utilize 0.2～10J/cm in case of necessity
2The exposure of left and right sides intensity is further solidified resist pattern.
Resist pattern of the present invention, in order when forming fine copper circuit, to satisfy requirement to the copper circuit densification by reducing circuitous resistance, thickness is that the shape ratio should be in more than 3.5 under 1～100 micron the occasion, preferred more than 3.8, more preferably more than 4.0, preferred especially more than 4.3, preferred more especially more than 4.5, extremely preferred more than 4.8, best more than 5.0.The upper limit of shape ratio, preferred about 10.0 from the angle of easy manufacturing, more preferably about 8.0, be preferably set to 6.0 especially.The shape ratio is as using optical microscope, scanning electron microscope mensuration such as (SEM)." the resist pattern live width " that adopts when calculating about the shape ratio preferably is decided to be the live width of remembering mask pattern from measuring consideration.
In order further to improve effect of the present invention, the thickness of resist pattern is preferably 1～100 micron, more preferably 3～80 microns, preferred especially 5～50 microns, extremely preferred 10～45 microns, is preferably 20～40 microns.
Below explanation forms the method for circuit with resist pattern of the present invention.Form with resist pattern of the present invention under the occasion of circuit, make mask, with known method treatment substrate surfaces such as corrosion and plating with the resist pattern that has developed.
Up to now, though mainly adopt decrement method (サ Block ト ラ Network テ イ Block), promptly with the circuit that corrodes as mask on the method formation printed circuit board (PCB) that forms copper circuit against corrosion, but when corrosion is owing to produce lateral encroaching (side etch) when vertically being corroded, so be unfavorable for the formation of fine circuits.In order to reduce the influence of this side etch,, make live width/at interval (L/S) reach below 30 microns but very difficulty though utilize the method for copper layer attenuate might form fine pattern to a certain extent.Based on these reasons, it is believed that it is effective adopting dosage method (ア デ イ テ イ Block) for the conductor package substrate that requires to form the finest copper circuit.
In the manufacture method of conductor package substrate of the present invention, the shape ratio is in more than 3.5 resist pattern of the present invention under 1～100 micron occasion because of thickness is set in, so compare with the decrement method of corroding, adopt the dosage method of electrochemical plating to be more suitable for making circuit.Therefore in the manufacture method of the conductor package substrate that relates to of the present invention, adopted the dosage method, below with reference to an example of Fig. 3～this operation of Fig. 5 illustrative.
The dosage method can be divided three kinds of the dosage method of helping (Off Le ア デ イ テ イ Block), false add amount method (セ ミ ア デ イ テ イ Block) and panel dosage methods (パ ネ Le ア デ イ テ イ Block) substantially.Full dosage method, as shown in Figure 3, be after forming Figure 121 against corrosion on the substrate (circuit form use substrate) 2, between this resist pattern by carrying out formation coating 4 such as electroless plating, peel off then and remove resist layer 121 and obtain circuit pattern, make the method for conductor package substrate 5.False add amount method, as shown in Figure 4, be to utilize electroless plating etc. to form on the substrate 2 of coating 4 in advance, after forming Figure 121 against corrosion, between this resist pattern, carry out formation coating 4 such as metallide again, peel off then and remove resist layer 121, corrode fast at last, with the metallide pattern do mask corrosion in advance the coating of electroless plating etc. obtain circuit pattern, make the method for conductor package substrate 5.Panel dosage method as shown in Figure 5, is to form the required coating such as electroless plating 4 of circuit on substrate 2, form Figure 121 against corrosion thereon after, corrode to peel off and remove resist layer 121, obtain circuit pattern, make the method for conductor package substrate 5.False add amount method is effective especially among the present invention.
As plating, for example can enumerate copper facing, zinc-plated, nickel plating, gold-plated etc.Peeling off of resist pattern removed, and can adopt than developing with the stronger alkaline aqueous solution of alkaline aqueous solution alkalescence.As strong alkaline aqueous solution, for example can use the sodium hydrate aqueous solution of 1～10 weight %, the potassium hydroxide aqueous solution of 1～10 weight % etc.And for example can adopt impregnation method, spray pattern etc. as peeling off mode.
Wherein when using resist pattern of the present invention, but do not use under note dosage method and the occasion with the decrement method formation circuit that corrodes, for example can use copper chloride solution, ferric chloride solution, alkaline corrosion solution, hydrogen peroxide for the corrosion of metal surface is corrosive liquid etc.
And can be suitable for circuit densification this point from resist pattern of the present invention, though preferably be used in the manufacturing of conductor package substrate, also can be used among the manufacturing of printed circuit board (PCB).Printed circuit board (PCB) under this occasion both can be a multilayer board, also can be the printed circuit board (PCB) of band minor diameter through hole.
The resist pattern that the present invention relates to so can form the fine circuits that suppresses the conductor resistance reduction with it, is applicable to the densification of conductor package substrate circuit because of having high resolving power and high shape ratio.
Photosensitive polymer combination that the present invention relates to and photosensitive element, can form as pattern and use erosion resistant, can provide to be suitable for the high resolving power that the densification of conductor package substrate circuit uses and the resist pattern and the resist pattern group of high shape ratio, and sensitivity, resolution, anti-floating slag, anti-plating, operability and throughput rate are all good.
Manufacture method according to the resist pattern that the present invention relates to, can make the resist pattern of high resolving power and high shape ratio with good operability and throughput rate, adopt it to form and suppress the fine circuits that conductor resistance reduces, can be used for the densification of conductor package substrate circuit.
Manufacture method according to the conductor package substrate that the present invention relates to, by making mask with the resist pattern of high resolving power and high shape ratio, can form with good operability and throughput rate and suppress the fine circuits that conductor resistance reduces, thereby can be suitable for the densification of conductor package substrate circuit.
Followingly further describe the present invention with reference to embodiment.
[experimental example 1～7]
Mix according to the composition shown in the table 1, obtained solution A.
Then with (B) composition shown in the table 2 and (C) composition be dissolved in the solution A that obtains, obtained the photosensitive polymer combination solution of each experimental example.
The compound that uses in the table 2 below is shown.
A-TMM-3 (Xin Zhong village chemical industry Co., Ltd. makes, trade name): the tetramethylol methane triacrylate that is expressed from the next
TMPT21E (Hitachi Chemical Co., Ltd.'s perparation of specimen name): the trimethylol-propane trimethacrylate of the EO modification that is expressed from the next
BPE500 (Xin Zhong village chemical industry Co., Ltd. makes, trade name): the compound of p+q=10 in the following formula (2, two (4-(the metacryloxy five ethoxys) phenyl) propane of 2-)
BP (EO) 14MA: the compound of p+q=14 in the following formula (2, two (4-(the metacryloxy seven ethoxys) phenyl) propane of 2-)
4G (Xin Zhong village chemical industry Co., Ltd. makes, trade name): TEG dimethylacrylate
9G (Xin Zhong village chemical industry Co., Ltd. makes, trade name): nine ethylene glycol dimethacrylates
9PG (Xin Zhong village chemical industry Co., Ltd. makes, trade name): nine propylene glycol dimethylacrylates
NP-4EA (Kyoeisha Chemical Co., Ltd. makes, trade name): the Nonylphenoxy four oxygen ethylene-acrylates that are expressed from the next
NP-8EA (Kyoeisha Chemical Co., Ltd. makes, trade name): the Nonylphenoxy eight oxygen ethylene-acrylates that are expressed from the next
Catechol: the compound that following formula is represented
4-tert-butyl catechol: the compound that following formula is represented
2,5 di tert butylhydroquinone: the compound that following formula is represented
2,6-di-tert-butyl hydroquinone: the compound that following formula is represented
Photosensitive polymer combination solution homogeneous with each experimental example is coated on the tygon polyethylene terephthalate film of 16 microns of thickness then, with dry 10 minutes of 100 ℃ of hot air convection formula dryers, has obtained photosensitive element.The thickness of the resist layer that obtains (photosensitive polymer combination layer) is 30 microns.Measure the dullness of resist layer under the ultraviolet ray of 365nm wavelength that obtains with UV spectrophotometer (Hitachi makes, U-3410 type spectrophotometer).At first the photosensitive element that will obtain above places the sample side, and supporting film is placed the reference side, and the dullness between METHOD FOR CONTINUOUS DETERMINATION 700～300nm reads the method for 365nm place numerical value and measures.The dullness of resist layer under wavelength 365nm ultraviolet ray is 1.2 in the experimental example 1～7.
On the other hand, get copper plywood (Hitachi Chemical Co., Ltd.'s manufacturing that the two sides is laminated with the glass epoxy resin material of Copper Foil (35 microns of thickness), trade name MCL-E-61), with buffing machine (three open Co., Ltd. makes) polishing with suitable #600 brush, the washing back is dry in airflow, the copper plywood that obtains is heated to 80 ℃, will go up note resist layer and be heated to 110 ℃ one side it be laminated to this copper lip-deep on one side, the test film of each experimental example obtained.
Sensitivity
Use has the parallel rays exposure machine (オ-Network company produces, the HMW-590 type) of high-pressure sodium lamp, and the 41 grades of step weakeners (ス ト-Off ァ-41 section ス テ ッ プ Block レ ッ ト) that will make negative-appearing image (ネ ガ) usefulness place on the test film, with 60J/cm
2, 120J/cm
2, 240J/cm
2The exposure exposure.After the exposure, peel off and remove tygon polyethylene terephthalate film, spray with 1 weight % aqueous sodium carbonate down, remove unexposed portion at 30 ℃.
Measure the progression that forms the step weakener of photocuring film on the copper plywood, estimate the sensitivity of photosensitive polymer combination, so that 15 grades of 41 grades of step weakeners (O.D.=0.05) solidify required exposure (J/cm
2) as sensitivity.What obtain the results are shown among the table 3.Numeral muting sensitivity more is high more.
Resolution
Make negative-appearing image with the glass mask pattern, each test film is exposed and develop with the exposure that determines above.Observe the pattern after developing, from obtaining resolution (micron) with live width and the remaining live width of alternate form (micron).The figure of merit of resolution is the smaller the better.
The shape ratio
According to the thickness (30 microns) of resist layer and on the live width (resolution) remembered, obtain the shape ratio according to following formula (2).
Splitting time
Test film to through exposure (15 grade/41) irradiation suitable with sensitivity separately develops with 1 weight % sodium hydrate aqueous solution.After placing diel, with stirrer stirring on one side the test film that obtain be immersed in the 3 weight % sodium hydrate aqueous solutions that remain on 45 ℃ temperature under on one side, the time (second) that begins to peel off measured.Splitting time is short more good more.
The scum silica frost generation
With the unexposed film of 0.5 square metre of each test film, be dissolved in 1 liter of 1 weight % aqueous sodium carbonate, this solution was circulated 90 minutes under 30 ℃ in the spray development machine.Place after 2 minutes, observe the oily product that adheres on the wall of developing machine, with standard evaluation scum silica frost generation shown in following.The big more characteristic of numerical value is good more.
3: no oily product
2: a small amount of oily product
1: a large amount of oily products
Anti-plating
Use mask and the exposure (15 grade/41) suitable to each test film exposure, develop with 1 weight % aqueous sodium carbonate with sensitivity separately.After this sample degreasing, washing, at 3.0A/dm
2Electroplated 30 minutes in copper sulphate down, behind washing and fluoboric acid dipping, at 1.5A/dm
2Zinc-plated 10 minutes down, washing.Be blown into air and remove moisture content,, observe to have or not and acutely peel off and peel off with the fragrant adhesive tape of match fine jade (the ponding chemistry is made 24 mm wides) sealing.
Well: do not peel off
Bad: as to peel off
The evaluation result of each experimental example is shown among the table 3.
Table 1
| Use level/weight portion | ||
| (A) composition | Multipolymer (weight-average molecular weight=45 that methacrylic acid/methyl methacrylate/styrene (29/46/25 weight ratio) is formed, 000) methyl cellosolve/toluene solution is Gu shape is divided acid number=189mgKOH/g | Gu shape is divided 52 (solution 120) |
| (C) | 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl double imidazole | 3.0 |
| 4,4 '-two (diethylamino) benzophenone | 0.3 | |
| (E) composition | Leuco crystal violet | 0.2 |
| Dyestuff | Peacock green | 0.08 |
| Solvent | Acetone | 10 |
| Toluene | 7 | |
| N, | 3 | |
| | 3 | |
Table 2
| Use level/weight portion | Experimental example | |||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | ||
| (B1) composition | A-TMM -3 | 10 | - | - | - | 10 | 10 | - |
| TMPT21E | - | 10 | 10 | 10 | - | - | - | |
| (B2) composition | 4G | 10 | 10 | 10 | - | - | - | - |
| 9G | - | - | - | 10 | 10 | 10 | - | |
| 9PG | - | - | - | - | - | - | 10 | |
| (B3) composition | BPE-500 | 20 | 20 | - | - | 20 | 20 | 20 |
| BP(EO) 14MA | - | - | 20 | 20 | - | - | - | |
| (B4) composition | NP-4EA | 8 | 8 | - | - | 8 | 8 | 8 |
| NP-8EA | - | - | 8 | 8 | - | - | 18 | |
| (D) composition | Catechol | 0.05 | - | - | 0.05 | - | - | 0.05 |
| The 4-tert-butyl catechol | - | 0.05 | - | - | - | - | - | |
| 2,5 di tert butylhydroquinone | - | - | 0、05 | - | - | - | - | |
| (monovalence oxybenzene compound) 2,6 ditertiary butyl p cresol | - | - | - | - | - | 0.05 | - | |
Table 3
| Experimental example | |||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | |
| Thickness (micron) | 30 | 30 | 30 | 30 | 30 | 30 | 30 |
| Sensitivity (mJ/cm 2) | 150 | 150 | 150 | 150 | 70 | 80 | 150 |
| Resolution (micron) | 8.6 | 7 | 8.6 | 7 | 15 | 15 | 10 |
| The shape ratio | 3.5 | 4.3 | 3.5 | 4.3 | 2.0 | 2.0 | 3.0 |
| Splitting time (second) | 50 | 50 | 55 | 55 | 40 | 50 | 40 |
| The scum | 3 | 3 | 3 | 3 | 3 | 3 | 3 |
| Anti-plating | Well | Well | Well | Well | Well | Well | Well |
[experimental example 8～12]
Composition shown in the mixture table 4 has obtained solution B.
Then with (B) composition shown in the table 4 and (D) composition be dissolved in the solution B that obtains, obtained the photosensitive polymer combination solution of each experimental example.
The compound that uses in the table 5 below is shown.
SR454 (サ-ト マ-Co., Ltd.'s system): the trimethylolpropane triacrylate of the EO modification that following formula is represented
Except that using this photosensitive polymer combination, obtained photosensitive element equally with experimental example 1 grade, estimated sensitivity, resolution, splitting time, scum silica frost generation and the anti-plating of each test film equally.Evaluation result is shown among the table 6.The dullness of the resist layer of experimental example 8～12 under wavelength 365nm ultraviolet ray is 0.38.
Table 4
| Use level/weight portion | ||
| (A) composition | Multipolymer (weight-average molecular weight=50 that methacrylic acid/methyl methacrylate/styrene/methacrylic acid butyl ester/ethyl acrylate (32/22/30/8/10 weight ratio) is formed, 000) methyl cellosolve/toluene solution is Gu shape is divided acid number=194mgKOH/g | Gu shape is divided 58 (solution 130) |
| (C) | 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl double imidazole | 3.2 |
| 4,4 '-two (diethylamino) benzophenone | 0.05 | |
| (E) composition | Leuco crystal violet | 0.4 |
| Dyestuff | Peacock green | 0.04 |
| Solvent | Acetone | 10 |
| Toluene | 7 | |
| N, | 3 | |
| | 3 | |
Table 5
| Use level/weight portion | Experimental example | ||||||
| 8 | 9 | 10 | 11 | 12 | |||
| (B1) | SR454 | 4 | 4 | 8 | - | - | |
| TMPT21E | - | - | - | 8 | 4 | ||
| (B2) composition | 4G | - | 6 | 6 | 6 | - | |
| 9G | 6 | - | - | - | 6 | ||
| (B3) composition | BPE-500 | - | 28 | - | 24 | 28 | |
| BP(EO)14MA | 28 | - | 24 | - | - | ||
| (B4) composition | NP- | 4 | 4 | 4 | 4 | 4 | |
| (D) composition | The 4-tert-butyl catechol | 0.04 | 0.04 | 0.04 | 0.04 | 0.04 | |
Table 6
| Experimental example | |||||
| 8 | 9 | 10 | 11 | 12 | |
| Thickness (micron) | 30 | 30 | 30 | 30 | 30 |
| Sensitivity (mJ/cm 2) | 190 | 190 | 190 | 190 | 190 |
| Resolution (micron) | 6.2 | 6.2 | 6.2 | 6.2 | 5.5 |
| The shape ratio | 4.8 | 4.8 | 4.8 | 4.8 | 5.4 |
| Splitting time (second) | 50 | 50 | 50 | 55 | 50 |
| The scum | 3 | 3 | 3 | 3 | 3 |
| Anti-plating | Well | Well | Well | Well | Well |
The shape that obtains of Fig. 6 (A) and Fig. 6 (B) (6.2 microns of (A) live widths, (B) live width is 5.5 microns) expression experimental example 8～12 is than the part SEM photo that is 4.8～5.4 resist pattern.As can be seen from Figure 6, can access that resist pattern does not destroy, the rectangular cross section shape does not have flange, the resist pattern of high resolving power, high shape ratio.
Last note experimental example can obtain shape than more than 3.5, all good resist pattern of characteristic such as sensitivity, resolution, splitting time, scum silica frost generation, anti-plating.The resist pattern of these high shape ratios can form fine copper circuit, and conductor package substrate is made function admirable, can form the copper circuit of enough sectional areas, and resistance is little.
The application discloses, be willing to that with spy that on September 27th, 2000 submitted to the theme that spy that the spy who submits in 2000-293255, on October 20th, 2000 is willing to submit on 2000-320168 and September 11 calendar year 2001 is willing to put down in writing among the 2001-275523 is relevant, by with reference to quoting wherein disclosure.
Should be noted that except that the content that has illustrated, never deviate from novelty of the present invention and favorable characteristics sets out, also can execute mode and make various modifications and changes last document.Therefore relevant this modifications and changes all should be included in the present invention's scope required for protection.
Claims (20)
1. photosensitive polymer combination, can utilize with 1～100 micron of thickness, shape be the space of the live width same widths of the resist pattern more than 3.5 than being live width to the ratio of resist film thickness, manufacturing and 1～100 micron of thickness, shape are the adjacent resist pattern group of resist pattern more than 3.5 than being live width to the ratio of resist pattern thickness, it is characterized in that
Contain:
(A) as constituting monomer, comprise the adhesive polymer of (methyl) acrylic acid and Arrcostab thereof,
(B) have in the molecule at least one ethene unsaturated link the optical polymerism compound and
(C) Photoepolymerizationinitiater initiater, and
With respect to 100 weight portions described (A) composition and (B) total amount of composition, the use level of described (A) composition is 40～80 weight portions; The use level of described (B) composition is 20～60 weight portions; The use level of described (C) composition is 0.1～10 weight portion.
2. photosensitive resin composition according to claim 1 is characterized in that, as described (B) composition, contains the optical polymerism compound that three ethene unsaturated links are arranged in (B1) molecule.
3. photosensitive resin composition according to claim 1 is characterized in that, as described (B) composition, contains (B2) 2, two (4-((methyl) propenyloxy group the gathers alkoxy) phenyl) propane of 2-.
4. photosensitive resin composition according to claim 1 is characterized in that, as described (B) composition, contains (B3) poly alkylene glycol two (methyl) acrylate.
5. photosensitive resin composition according to claim 1 is characterized in that, as described (B) composition, contains the compound that has at least one ethene unsaturated link and at least one phenyl or phenylene in (B4) molecule.
6. according to each described photosensitive polymer combination of claim 1～5, it is characterized in that, as described (C) composition, contain 2,4,5-triarylimidazoles dimer.
7. according to each described photosensitive polymer combination of claim 1～5, it is characterized in that,, contain N, N '-tetraalkyl-4,4 '-diaminobenzophenone as described (C) composition.
8. photosensitive polymer combination according to claim 7, it is characterized in that described (C) N, N '-tetraalkyl-4,4 '-use level of diaminobenzophenone, with respect to 100 weight portions described (A) composition and (B) total amount of composition be 0.04～0.08 weight portion.
9. according to each described photosensitive polymer combination of claim 1～5, it is characterized in that also contain (D) composition, it comprises: by the compound of general formula (I) expression or by any compound or two kinds of compounds in the compound of general formula (II) expression.
M is 2～6 integer in the formula
10. according to each described photosensitive polymer combination of claim 1～5, it is characterized in that, also contain leuco dye, as (E) composition.
11. photosensitive polymer combination according to claim 10 is characterized in that, the content of described (E) leuco dye with respect to 100 weight portions described (A) composition and (B) total amount of composition, is 0.3～0.6 weight portion.
12. photosensitive polymer combination according to claim 10 is characterized in that, described (E) leuco dye is a leuco crystal violet.
13. a photosensitive element is characterized in that, forms the resist layer that requires 1～12 each described photosensitive resin composition to form by aforesaid right on support.
14. the manufacture method of a resist pattern, the shape of this resist pattern is more than 3.5 than being live width to the ratio of resist pattern thickness, it is characterized in that, comprises following operation:
I) on substrate, form the resist layer that forms by each described photosensitive polymer combination of claim 1～12, make dried thickness reach 1～100 micron formation operation;
Ii), make the operation of the described resist layer photocuring of exposed portion according to picture shape irradiation active ray;
Iii) optionally remove unexposed described resist layer operation by developing.
15. the manufacture method of resist pattern according to claim 14 is characterized in that, the absorbance when being formed on the wavelength 365nm of described active ray is the resist layer below 0.50, as described resist layer.
16. the manufacture method of resist pattern according to claim 14 is characterized in that, by the glass negative film picture shape is shone described active ray, makes the described resist layer photocuring of exposure portion.
17. the manufacture method of resist pattern according to claim 14 is characterized in that, to picture shape irradiation parallel rays, makes the described resist layer photocuring of exposure portion.
18. the manufacture method of resist pattern according to claim 14, it is characterized in that, described operation i) carries out according to the following stated: on support, form the resist layer that makes by each described photosensitive polymer combination of claim 1～12 and obtain photosensitive element, the mode of resulting photosensitive element with the surperficial driving fit of above-mentioned resist layer and aforesaid substrate is layered on the substrate.
19. a resist pattern is characterized in that, this resist pattern is according to the manufacture method manufacturing of each described resist pattern of claim 14～18, and the thickness of resist layer is 1～100 micron, and the shape ratio is a live width to the ratio of resist pattern thickness is more than 3.5.
20. the manufacture method of a conductor package substrate is characterized in that, the substrate that adopts the dosage method to make the manufacture method of utilizing each described resist pattern of claim 14～18 make resist pattern forms the loop.
Applications Claiming Priority (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000275523A JP3594540B2 (en) | 2000-09-11 | 2000-09-11 | Solar cell module |
| JP293255/00 | 2000-09-27 | ||
| JP293255/2000 | 2000-09-27 | ||
| JP2000293255 | 2000-09-27 | ||
| JP2000320168 | 2000-10-20 | ||
| JP320168/00 | 2000-10-20 | ||
| JP320168/2000 | 2000-10-20 | ||
| JP275523/2001 | 2001-09-11 | ||
| JP275523/01 | 2001-09-11 |
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| CN1466706A CN1466706A (en) | 2004-01-07 |
| CN1258696C true CN1258696C (en) | 2006-06-07 |
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| CN 01816402 Expired - Fee Related CN1258696C (en) | 2000-09-11 | 2001-09-26 | Photosensitive resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105182688A (en) * | 2008-06-02 | 2015-12-23 | 日立化成工业株式会社 | Photosensitive Resin Composition, Photosensitive Element, Resist Pattern Manufacturing Method, And Printed Circuit Board Manufacturing Method |
| CN105425544A (en) * | 2008-04-28 | 2016-03-23 | 日立化成工业株式会社 | Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for manufacturing printed wiring board |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2005285946A (en) * | 2004-03-29 | 2005-10-13 | Nippon Mektron Ltd | Manufacturing method of circuit board |
| MY148552A (en) | 2005-10-25 | 2013-04-30 | Hitachi Chemical Co Ltd | Photosensitive resin composition, photosensitive element comprising the same, method of forming resist pattern, and process for producing printed wiring board |
| TW200745749A (en) * | 2006-02-21 | 2007-12-16 | Hitachi Chemical Co Ltd | Photosensitive resin composition, method for forming resist pattern, method for manufacturing printed wiring board, and method for producing substrate for plasma display panel |
| TWI503625B (en) * | 2013-08-23 | 2015-10-11 | Ind Tech Res Inst | Photosensitive composition and photoresist |
| US9155201B2 (en) * | 2013-12-03 | 2015-10-06 | Eastman Kodak Company | Preparation of articles with conductive micro-wire pattern |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105425544A (en) * | 2008-04-28 | 2016-03-23 | 日立化成工业株式会社 | Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for manufacturing printed wiring board |
| CN105182688A (en) * | 2008-06-02 | 2015-12-23 | 日立化成工业株式会社 | Photosensitive Resin Composition, Photosensitive Element, Resist Pattern Manufacturing Method, And Printed Circuit Board Manufacturing Method |
| CN105182688B (en) * | 2008-06-02 | 2019-11-12 | 日立化成株式会社 | The manufacturing method of photosensitive polymer combination, photosensitive element, the manufacturing method of resist figure and printed circuit board |
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