CN101192001B - Welding-proof film forming method and photosensitive composition - Google Patents

Welding-proof film forming method and photosensitive composition Download PDF

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Publication number
CN101192001B
CN101192001B CN2007101872549A CN200710187254A CN101192001B CN 101192001 B CN101192001 B CN 101192001B CN 2007101872549 A CN2007101872549 A CN 2007101872549A CN 200710187254 A CN200710187254 A CN 200710187254A CN 101192001 B CN101192001 B CN 101192001B
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alkyl
wavelength
laser
phenyl
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CN101192001A (en
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柴崎阳子
加藤贤治
有马圣夫
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Taiyo Holdings Co Ltd
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Taiyo Holdings Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2022—Multi-step exposure, e.g. hybrid; backside exposure; blanket exposure, e.g. for image reversal; edge exposure, e.g. for edge bead removal; corrective exposure
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers

Abstract

The invention relates to a method for producing a soldering resistance film comprising following steps: coating photosensitive composition onto a substrate and drying it, irradiating a first laser and a second laser with different wavelength from the first laser onto the dried coated film, forming a pattern latent image obtained by irradiation of the first laser and the second laser, and developing by the basic aqueous solution. In addition, the photosensitive composition forming the soldering resistance film is provided as following: Each 25 mum thickness of the dried coated film before explosion, displays an absorbency of 0.6-1.2 in a wave length range of 355-380nm, and displays an absorbency of 0.3-0.6 at a wave length of 450 nm.

Description

Soldering-resistance layer formation method and photosensitive composite
Technical field
The present invention relates to the formation method of following soldering-resistance layer, with photosensitive composite be applied to make its drying on the base material after, behind this dry coating irradiating laser, developing through alkaline aqueous solution forms soldering-resistance layer; The dry film that carries out drying after also relating to the photosensitive composite that is used for this method and being applied to said composition on the film carrier and obtain.
Background technology
The outermost layer of printed circuit board (PCB) is provided with the permanent diaphragm that is called soldering-resistance layer.In order to form this soldering-resistance layer, extensively employing can accurately form the photoetching process of fine pattern.Wherein, from environment aspect consideration etc., main flow is the photoetching process of alkali developable.
As a method in the photoetching process, that is widely known by the people is to use from producing the disposable exposure method of the light that ultraviolet lamp sends, and is disclosed in for example japanese kokai publication hei 01-141904 number.This disposable exposure method is to be applied to photosensitive composite on the base material and after making it drying, makes from producing the light that ultraviolet lamp sends across photomask this dry coating is carried out blanket exposure.Therefore, can form the pattern latent image in the very short time.Yet this disposable exposure method need make the aligned in position of photomask and base material, this aligned in position spended time.In addition, the thermal history size when base material forms because of its circuit changes, and is easy to generate the deviation of off-design value.With respect to this, photomask does not produce the change in size of above-mentioned that kind, therefore can not carry out the position correction corresponding with the deviation of this base material.Fine pattern receives the influence of deviation more more greatly, and the pattern latent image forms the difficulty that becomes accurately.In order to form pattern latent image accurately, measure the size of each base material after circuit forms respectively, correspondingly need make mask to each base material, very numerous and diverse.
With respect to this, the direct picture of using laser is based on the data from computer, uses the light of the single wavelength that LASER Light Source sends, and drying resistance weldering filmed directly describe pattern latent image (International Publication WO02/096969 number).In this direct picture,,,, can form the latent image of pattern accurately of expectation with the deviation of calculating machine maintenance positive deviation design load through measuring the size of the base material after circuit forms for the deviation of the design load of above-mentioned such departure from substrate size.Therefore, directly picture is than disposable exposure method, can be more accurately and easily form fine pattern latent image.
Yet, direct picture scan laser and describe the pattern latent image on base material.Therefore, the time that is used for forming on 1 base material through direct picture the pattern latent image is longer than disposable exposure method, and throughput rate also is in the variation tendency.Therefore, in order to boost productivity, require to can be used for the photosensitive composite of the ISO directly described at a high speed.The light sensitivity of photosensitive composite is low, then can not with directly describe at a high speed, i.e. laser radiation with the short time fully forms the pattern latent image.Common ultraviolet hardening photosensitive composite has the light sensitivity of 200mJ～600mJ.For filming with the dry resistance weldering of direct picture exposure thick film and it fully being solidified, this light sensitivity scope is lower.
In addition, the direct picture of laser is used single wavelength.Usually, when using shorter short wavelength's laser, the energy of light is high, thereby, have the advantage that can be cured rapidly, on the other hand, owing to have light to be difficult to penetrate into the tendency in deep, thereby, have the tendency that the curing depth of soldering-resistance layer reduces.When using longer long wavelength's laser, have the deep that light arrives the photosensitive composite dry coating, the advantage that curing depth uprises, on the other hand, because the energy step-down of light, thereby deterioration of efficiency and curing spended time.In addition, in the meantime, the curing that film coated surface receives oxygen easily hinders, thereby, have the tendency that can not obtain sufficient surface cure.
Summary of the invention
The objective of the invention is to; The formation method of soldering-resistance layer is provided, and this method has shorter short wavelength laser and longer long wavelength laser advantage separately, and; Remedy deficiency separately, can make by filming of forming of photosensitive composite and from the surface to the deep, solidify fully; And applicable to the photosensitive composite of the ISO of this method.
In order to solve above-mentioned purpose, according to a first aspect of the invention, the formation method of soldering-resistance layer is provided; It is characterized in that; With photosensitive composite be applied to make its drying on the base material after, this dry coating is shone the different laser more than 2 kinds of wavelength each other, form said more than 2 kinds laser shine the pattern latent image that obtains respectively; Then, develop through alkaline aqueous solution.
According to other aspects of the invention; The formation method of soldering-resistance layer is provided, it is characterized in that, with photosensitive composite be applied to make its drying on the base material after; This dry coating is shone the 1st laser and 2nd laser different with said the 1st optical maser wavelength; Form the pattern latent image that said the 1st laser and the 2nd laser both sides irradiation obtains, then, develop through alkaline aqueous solution.
According to other aspects of the invention, photosensitive composite is provided, it is characterized in that; This photosensitive composite is used for the formation method of the described soldering-resistance layer of claim 2; Wherein, the per 25 μ m thickness of dry coating before its exposure show 0.6～1.2 absorbance in the wavelength coverage of 355～380nm; And, under the wavelength of 405nm, show 0.3～0.6 absorbance.
In addition, according to other aspects of the invention, dry film is provided, carries out drying after it is applied to above-mentioned photosensitive composite on the film carrier and obtain.
Description of drawings
Fig. 1 is that the dry coating to photosensitive composite makes public, the synoptic diagram of the cross sectional shape of the soldering-resistance layer that obtains after it is developed.
Embodiment
Below, the present invention is described in further detail.
The formation method of soldering-resistance layer of the present invention be with photosensitive composite be applied to make its drying on the base material after; This dry coating is shone the different laser more than 2 kinds of wavelength each other; Form said more than 2 kinds laser shine the pattern latent image that obtains respectively, then, develop through alkaline aqueous solution.
Especially; The formation method of soldering-resistance layer of the present invention be with photosensitive composite be applied to make its drying on the base material after; This dry coating is shone the 1st laser and 2nd laser different with said the 1st optical maser wavelength; Form the pattern latent image that said the 1st laser and the 2nd laser both sides irradiation obtains, then, develop through alkaline aqueous solution.
Shine the different laser more than 2 kinds of wavelength each other through dry coating to photosensitive composite; For example; Shine the 1st laser and 2nd laser different with the 1st optical maser wavelength; The dry coating part that two laser radiations obtain can fully be solidified, and accurately forms pattern latent image (parts of two laser radiations).More than 2 kinds in the wavelength different laser irradiation, earlier which laser of irradiation can, no matter order.In addition, also can shine wavelength different laser more than 2 kinds simultaneously.
Below, describe for the form of using the 1st laser and the 2nd laser.
The 1st laser and the 2nd laser that are used for the formation method of soldering-resistance layer of the present invention can use semiconductor laser and Solid State Laser.The preferred royal purple laser (for example 405nm) of the side in the 1st laser and the 2nd laser particularly.Another laser is Ultra-Violet Laser normally.The light source of the 1st laser and the 2nd laser can be arranged in 1 laser irradiation device.
In the formation method of the soldering-resistance layer of the invention described above; Can suit to use the photosensitive composite of the present invention that is described below; The per 25 μ m thickness of dry coating before its exposure of this photosensitive composite; Wavelength coverage at 355～380nm shows 0.6～1.2 absorbance, and under the wavelength of 405nm, shows 0.3～0.6 absorbance.In more detail, show 0.6～1.2 absorbance in the wavelength coverage of 355～380nm of short wavelength side, absorb the light of incident in the skin section of dry coating in a large number through the dry coating before making public; The surface is solidified, and, through the absorbance of demonstration 0.3～0.6 under the wavelength of 405nm; Make the bottom of light transmission to dry coating; Obtain sufficient curing depth, thus, realize ISO.
At this; In the present invention; So-called " the per 25 μ m thickness of dry coating before the exposure show 0.6～1.2 absorbance in the wavelength coverage of 355～380nm, and under the wavelength of 405nm, show 0.3～0.6 absorbance " is meant: for coating also dry sensation photosensitiveness composition paste and the dry coating that obtains; The chart of the absorbance when making 4 different thickness and each dry coating thickness under wavelength 355～380nm; Calculate the absorbance of the dry coating of thickness 25 μ m from its approximate expression, resulting absorbance is in 0.6～1.2 scope, and; For coating and dry sensation photosensitiveness composition paste and the dry coating that obtains; The chart of the absorbance when making 4 different thickness and each dry coating thickness under wavelength 405nm is calculated the absorbance of the dry coating of thickness 25 μ m from its approximate expression, and resulting absorbance is in 0.3～0.6 scope.This will after describe in detail among the embodiment that states.
In addition; Among the present invention; So-called " the per 25 μ m thickness of dry coating before the exposure; the difference in the maximum absorbance of the wavelength coverage of 355～380nm and wavelength absorbance down at 405nm is 0.3 or more and less than 0.6 " are meant: for being coated with the dry coating that dry sensation photosensitiveness composition paste also obtains; The chart of the absorbance when making 4 different thickness and each dry coating thickness under wavelength 355～380nm; Calculate from its approximate expression thickness 25 μ m dry coating absorbance and obtain maximum absorbance, for coating and dry sensation photosensitiveness composition paste and the dry coating that obtains, the chart of the absorbance when making 4 different thickness and each dry coating thickness under wavelength 405nm; Calculate the absorbance of the dry coating of thickness 25 μ m from its approximate expression, the difference of the absorbance that is obtained by above-mentioned two absorbances is more than 0.3 and less than 0.6.This will after describe in detail among the embodiment that states.
In addition; Among the present invention; So-called " the per 25 μ m thickness of dry coating before making public show 0.6～1.0 absorbance under the wavelength of 355nm, and the absorbance that under the wavelength of 405nm, shows 0.3～0.5; and the difference of the absorbance under absorbance under the wavelength of 355nm and the wavelength at 405nm is more than 0.3 and less than 0.5 " and be meant: for the dry coating that is coated with and dry sensation photosensitiveness composition paste obtains; The chart of the absorbance when making 4 different thickness and each dry coating thickness under wavelength 355nm is calculated the absorbance of the dry coating of thickness 25 μ m from its approximate expression, and resulting absorbance is in 0.6～1.0 scope; And for coating and dry sensation photosensitiveness composition paste and the dry coating that obtains; The chart of the absorbance when making 4 different thickness and each dry coating thickness under wavelength 405nm is calculated the absorbance of the dry coating of thickness 25 μ m from its approximate expression, and resulting absorbance is in 0.3～0.5 scope; And, calculate with the absorbance of the dry coating of above-mentioned wavelength 355nm that obtains equally and the thickness 25 μ m under the 405nm and the difference of the absorbance that obtains is more than 0.3 and less than 0.5.This will after describe in detail among the embodiment that states.
Dry coating before the exposure of photosensitive composite of the present invention has, surface cure inadequate tendency insufficient in the light absorption of skin section under the situation of the absorbance of the wavelength coverage demonstration less than 0.6 of 355～380nm.Show to surpass under the situation of 1.2 absorbance, have surface cure and excessively carry out, hinder the tendency that light sees through to the bottom, so not preferred.In addition, the dry coating before the exposure is under the situation of the absorbance that shows less than 0.3 wavelength of 405nm under, and having is not dried, and the film light that absorbs is reflected by the Copper Foil on the substrate for example, and so the tendency of solder resist change in shape is not preferred.In addition, show surpassing under the situation of 0.6 absorbance, have the tendency that can not make light fully penetrate into the bottom of dry coating, this is not preferred.
In addition, its dry coating per 25 μ m thickness of photosensitive composite of the present invention before preferably making public, the difference of the absorbance under the maximum absorbance of the wavelength coverage of 355～380nm and wavelength at 405nm is more than 0.3 and less than 0.6.Difference through absorbance can effectively obtain above-mentioned surface cure and curing depth in this scope, can make the light sensitivity of photosensitive composite of the present invention higher.During the difference less than 0.3 of this absorbance, have, need the tendency of longer time shutter in order to obtain sufficient surface cure and curing depth.In addition, when surpassing 0.6, have the tendency that is difficult to obtain simultaneously sufficient surface cure and curing depth, this is not preferred.
In addition; The per 25 μ m thickness of its dry coating before photosensitive composite of the present invention preferably makes public; Under the wavelength of 355nm, show 0.6～1.0 absorbance; And the absorbance that under the wavelength of 405nm, shows 0.3～0.5, and the difference of the absorbance under absorbance under the wavelength of 355nm and the wavelength at 405nm is more than 0.3 and less than 0.5.
As photosensitive composite of the present invention, can use to comprise (A) and contain carboxylic acid resin, (B) Photoepolymerizationinitiater initiater and (C) photosensitive composite of pigment.
As containing carboxylic acid resin (A), can use the resin compound known commonly used that contains carboxyl in the molecule.In addition, from photo-curable, anti-development property aspect, what more preferably in molecule, have ethylenical unsaturated double bonds contains the carboxylic acid photoresist.
Specifically, the resin of enumerating below can enumerating out.
(1), thereby obtains containing the carboxylic acid resin through unsaturated carboxylic acid and the compounds that has unsaturated double-bond more than a kind in addition such as copolymerization (methyl) acrylic acid;
(2) multipolymer and (methyl) glycidyl acrylate, (methyl) acrylic acid 3 through making unsaturated carboxylic acid such as (methyl) acrylic acid and the compound that has unsaturated double-bond more than a kind in addition; 4-epoxycyclohexyl methyl esters etc. has reactions such as the compound, (methyl) acryloyl chloride of epoxy radicals and unsaturated double-bond; To this multipolymer addition ethylenically unsaturated group as side group, thereby obtain contain the carboxylic acid photoresist;
(3) make (methyl) glycidyl acrylate, (methyl) acrylic acid 3; Unsaturated carboxylic acid reactions such as the multipolymer that 4-epoxycyclohexyl methyl esters etc. has the compound of epoxy radicals and unsaturated double-bond and in addition a compound with unsaturated double-bond and (methyl) acrylic acid; Make the reaction of the secondary hydroxyl that generated and multi-anhydride, thus obtain contain the carboxylic acid photoresist;
(4) compound that makes multipolymer that maleic anhydride etc. has the acid anhydrides of unsaturated double-bond and in addition a compound with unsaturated double-bond and (methyl) acrylic acid 2-hydroxyl ethyl ester etc. have hydroxyl and unsaturated double-bond reacts, thus obtain contain the carboxylic acid photoresist;
(5) make unsaturated monocarboxylics reactions such as multi-functional epoxy compound and (methyl) acrylic acid, hydroxyl that is generated and saturated or unsaturated multi-anhydride reacted, thus obtain contain the carboxylic acid photoresist;
(6) make the reaction of hydroxyl polymer-containing such as polyvinyl alcohol derivative and saturated or unsaturated multi-anhydride after, the compound that has epoxy radicals and unsaturated double-bond in the carboxylic acid that is generated and a part is reacted, thus obtain containing hydroxyl contain the carboxylic acid photoresist;
(7) make and (for example have at least 1 alcohol hydroxyl group and 1 compound with reactive group epoxy reaction except that alcohol hydroxyl group in unsaturated monocarboxylic, a part such as multi-functional epoxy compound, (methyl) acrylic acid; Dihydromethyl propionic acid etc.) reaction; Make the reaction of reaction product and saturated or unsaturated multi-anhydride, thereby obtain containing the carboxylic acid photoresist;
(8) make unsaturated monocarboxylic reactions such as the multifunctional oxetane compound that has at least 2 oxetanes rings in a part and (methyl) acrylic acid; With the reaction of the primary hydroxyl in the resulting modification oxetane resin and saturated or unsaturated multi-anhydride, thus obtain contain the carboxylic acid photoresist; And
(9) make polyfunctional epoxy resin (for example, formaldehyde novolac type epoxy resin etc.) and unsaturated monocarboxylic (for example, (methyl) acrylic acid etc.) reaction after; Again with multi-anhydride (for example; Tetrabydrophthalic anhydride) reaction further with in the molecule has compound (for example, (methyl) glycidyl acrylate etc.) reaction of 1 oxirane ring and 1 above ethylenically unsaturated group with the carboxylic acid resin that contains who obtains thus; Thereby obtain containing carboxylic acid photoresist etc., but be not limited to these.
As preferably above-mentioned (2), (5), (7), (9) in these resins contain the carboxylic acid photoresist, particularly from the aspect of photo-curable, cured coating film property, preferably above-mentioned (9) contain the carboxylic acid photoresist.
In addition, in this manual, (methyl) acrylic ester is meant the term of general name acrylic ester, methacrylate, and other is similarly expressed too.These acrylate compounds and methacrylate compound can be used separately also can mix more than 2 kinds and use.
Above-mentioned that kind contain carboxylic acid resin (A) owing on the side chain of trunk polymer, have carboxyl, thereby can develop through alkaline aqueous solution.
In addition, the above-mentioned acid value that contains carboxylic acid resin (A) is preferably in the scope of 40～200mgKOH/g, more preferably in the scope of 45～120mgKOH/g.When containing carboxylic acid resin's acid value deficiency 40mgKOH/g, alkali develops and becomes difficult, and this is not preferred.On the other hand, when surpassing 200mgKOH/g, developer solution excessively carries out the dissolving of exposure portion; Thereby make line thinner than required width; Sometimes exposure portion and unexposed are developed the liquid dissolving as broad as longly and peel off, and are difficult to carry out describing of normal resist pattern, so not preferred.
In addition, the above-mentioned weight-average molecular weight that contains carboxylic acid resin (A) is different because of resin matrix, but usually preferably in 2000～150000 scope, more preferably in 5000～100000 scope.During weight-average molecular weight less than 2000, dry to touch performance meeting variation, in addition, the moisture-proof variation of filming after the exposure produces film and reduces during development, and resolution is variation greatly.On the other hand, when weight-average molecular weight surpasses 150000, the remarkable variation of development property meeting, in addition, the storage-stable variation.
The combined amount that contains carboxylic acid resin (A) like this can be based on the gross mass of photosensitive composite of the present invention, from 20～60 quality %, preferably from the scope of 30～50 quality %, select.When combined amount less than 20 quality %, has the tendency that coating strength reduces, so not preferred.On the other hand, when combined amount surpassed 60 quality %, viscosity uprised, and so reductions such as coating are not preferred.
As Photoepolymerizationinitiater initiater (B), the alpha-aminoacetophenone that preferred to use the oxime ester that is selected from the group shown in (I) that has formula be Photoepolymerizationinitiater initiater, have a group shown in the formula (II) is that Photoepolymerizationinitiater initiater and the acylphosphine oxide with the group shown in the following formula (III) are the Photoepolymerizationinitiater initiater more than a kind in the group formed of Photoepolymerizationinitiater initiater.
Figure S2007101872549D00101
In the formula, R 1The expression hydrogen atom; Can be by the substituted phenyl of the alkyl of carbon number 1～6, phenyl or halogen atom; Can be replaced and also can have the alkyl of the carbon number 1～20 of 1 above oxygen atom by 1 above hydroxyl at the alkyl middle-of-chain; The naphthenic base of carbon number 5～8 can be by the alkanoyl or the benzoyl of the substituted carbon number 2～20 of the alkyl or phenyl of carbon number 1～6
R 2Expression can be by the substituted phenyl of the alkyl of carbon number 1～6, phenyl or halogen atom; Can be replaced and also can have the alkyl of the carbon number 1～20 of 1 above oxygen atom by 1 above hydroxyl at the alkyl middle-of-chain; The naphthenic base of carbon number 5～8; Can be by the alkanoyl or the benzoyl of the substituted carbon number 2～20 of the alkyl or phenyl of carbon number 1～6
R 3And R 4Alkyl or the aralkyl of representing carbon number 1～12 independently of one another,
R 5And R 6Represent the alkyl of hydrogen atom, carbon number 1～6 or the cyclic alkyl ether of both be combined intos independently of one another,
R 7And R 8Represent independently of one another carbon number 1～10 straight chain shape or branched-chain alkyl, cyclohexyl, cyclopentyl, aryl, or can be by the substituted aryl of halogen atom, alkyl or alkoxy, wherein, R 7And R 8In a side also can represent R-C (=O)-Ji, here, R is the alkyl of carbon number 1～20.
Oxime ester as having the group shown in the general formula (I) is a Photoepolymerizationinitiater initiater, preferably can enumerate out compound shown in the 2-shown in the following formula (IV) (acetoxyl group formamino) thioxanthene-9-one, the formula (V) and the compound shown in the formula (VI).
Figure S2007101872549D00111
In the formula, R 9The alkyl of expression hydrogen atom, halogen atom, carbon number 1～12, cyclopentyl, cyclohexyl, phenyl, benzyl, benzoyl, the alkanoyl of carbon number 2～12, the alkoxy carbonyl group or the carbobenzoxy of carbon number 2～12; Wherein, The carbon number that constitutes the alkyl of alkoxy is 2 when above; Alkyl can be replaced by 1 above hydroxyl, also can have 1 above oxygen atom at the alkyl middle-of-chain
R 10And R 12Expression can be by the substituted phenyl of the alkyl of carbon number 1～6, phenyl or halogen atom independently of one another; Can be replaced and also can have the alkyl of the carbon number 1～20 of 1 above oxygen atom by 1 above hydroxyl at the alkyl middle-of-chain; The naphthenic base of carbon number 5～8; Can be by the alkanoyl or the benzoyl of the substituted carbon number 2～20 of the alkyl or phenyl of carbon number 1～6
R 11The expression hydrogen atom; Can be by the substituted phenyl of the alkyl of carbon number 1～6, phenyl or halogen atom; Can be replaced and also can have the alkyl of the carbon number 1～20 of 1 above oxygen atom by 1 above hydroxyl at the alkyl middle-of-chain; The naphthenic base of carbon number 5～8 can be by the alkanoyl or the benzoyl of the substituted carbon number 2～20 of the alkyl or phenyl of carbon number 1～6.
Figure S2007101872549D00121
In the formula, R 13And R 14The alkyl of representing carbon number 1～1 2 independently of one another,
R 15, R 16, R 17, R 18And R 19The alkyl of representing hydrogen atom or carbon number 1～6 independently of one another,
M representes O, S, NH, and
M and n represent 0～5 integer.
In the middle of these, the more preferably compound shown in (acetoxyl group formamino) thioxanthene-9-one of the 2-shown in the formula (IV) and the formula (V).CGI-325, IRGACURE OXE01, IRGACURE OXE02 of CibaSpecialty Chemicals manufactured etc. are arranged as commercially available article.These oxime esters are that Photoepolymerizationinitiater initiater can use more than 2 kinds alone or in combination.
As aforementioned alpha-aminoacetophenone with the group shown in the general formula (II) is Photoepolymerizationinitiater initiater; Can enumerate out 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butane-1-ketone, 2-(dimethylamino)-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4-morpholinyl) phenyl]-1-butanone, N, N-dimethylamino benzoylformaldoxime etc.As commercially available article, can enumerate out IRGACURE 907, IRGACURE 369, IRGACURE 379 of Ciba SpecialtyChemicals manufactured etc.
Acylphosphine oxide as having the group shown in the general formula (III) is a Photoepolymerizationinitiater initiater, can enumerate out 2,4; 6-trimethylbenzoyl diphenyl phosphine oxide, two (2; 4,6-trimethylbenzoyl) phenyl phosphine oxide, two (2,6-dimethoxy benzoyl)-2; 4,4-trimethyl-amyl group phosphine oxide etc.As commercially available article, can enumerate out the Lucirin TPO of BASF AG's manufacturing, the IRGACURE 819 of Ciba Specialty Chemicals manufactured etc.
The combined amount of such Photoepolymerizationinitiater initiater (B) can be selected from the scope of the scope of 0.01～30 mass parts, preferred 0.5～15 mass parts with respect to the aforementioned carboxylic acid resin of containing of 100 mass parts (A).When less than 0.01 mass parts, photo-curable on the copper is not enough, films and peels off, and perhaps coating characteristic such as chemical proofing reduces, so not preferred.On the other hand, when surpassing 30 mass parts, have Photoepolymerizationinitiater initiater (B) and become violent in the light absorption of resistance weldering film coated surface, so the tendency that the deep curable reduces is not preferred.
In addition, aforementioned oxime ester with the group shown in the formula (I) is under the situation of Photoepolymerizationinitiater initiater, the expectation of its combined amount with respect to the aforementioned carboxylic acid resin of containing of 100 mass parts (A) preferably from the scope of 0.01～20 mass parts, more preferably select 0.01～5 the scope.Such oxime ester be Photoepolymerizationinitiater initiater (I) since with the interface and copper atom reaction of Copper Foil, the functionally inactive of Photoepolymerizationinitiater initiater sometimes, thereby, be that Photoepolymerizationinitiater initiater (II) waits and makes up use preferably with alpha-aminoacetophenone.
As the contained pigment of photosensitive composite of the present invention (C), preferred phthalocyanine blue series pigments.Discoveries such as the inventor for the light (laser) of the single wavelength of 405nm, when adding the photosensitive composite of phthalocyanine blue series pigments, obtain surface cure property with lower low exposure.The reason of the sensitization effect of this phthalocyanine blue series pigments is also indeterminate; But for example; In the photosensitive composite of the absorbance less than 0.3 of every thickness 25 μ m, add phthalocyanine blue and make absorbance, so just can obtain sufficient surface cure property and curing depth simultaneously to hang down exposure more than 0.3.In addition, this sensitization effect produces effect to the reactivity (improving gloss) on surface, and curing depth variation on the contrary.That is, play the effect of the light of reflex exposure.Also the stabilization to the soldering-resistance layer shape is effective in this effect.As the phthalocyanine blue series pigments, can enumerate out α type copper phthalocyanine indigo plant, α type monochloro copper phthalocyanine blue, beta-type copper phthalocyanine indigo plant, ε type copper phthalocyanine indigo plant, cobalt phthalocyanine blue, metal-free phthalocyanine blue etc.
The addition that is fit to of such pigment (C) is; As long as the absorbance of dry coating under the wavelength of 405nm of photosensitive composite is that per 25 μ m are 0.3～0.6 scope; Just can add arbitrarily, for example, containing carboxylic acid resin (A) with respect to 100 mass parts is the scope of 0.01～5 mass parts.
In addition; As other Photoepolymerizationinitiater initiaters, light-initiated auxiliary agent and sensitizer, can enumerate out benzoin compound, acetophenone compound, anthraquinone compounds, thioxanthones compound, ketal compound, benzophenone cpd, xanthone and tertiary amine compound etc. applicable to photosensitive composite of the present invention.
Enumerate the object lesson of benzoin compound, for example have, benzoin, benzoin methyl ether, benzoin ethylether, benzoin isopropyl ether.
Enumerate the object lesson of acetophenone compound, for example have, acetophenone, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy-2-phenyl acetophenone, 1,1-dichloroacetophenone.
Enumerate the object lesson of anthraquinone compounds, for example have, 2-methylanthraquinone, 2-EAQ, 2-tert-butyl group anthraquinone, 1-chloroanthraquinone.
Enumerate the object lesson of thioxanthones compound, for example have, 2,4-dimethyl thioxanthones, 2,4-diethyl thioxanthone, 2-clopenthixal ketone, 2,4-diisopropyl thioxanthones.
Enumerate the object lesson of ketal compound, for example have, acetophenone dimethyl ketal, benzil dimethyl ketal.
Enumerate the object lesson of benzophenone cpd, for example have, benzophenone, 4-benzoyl diphenyl sulfide, 4-benzoyl-4 '-methyldiphenyl thioether, 4-benzoyl-4 '-ethyl diphenyl sulfide, 4-benzoyl-4 '-propyl group diphenyl sulfide.
Enumerate the words of the object lesson of tertiary amine compound; For example have; Ethanolamine compound, compound with dialkyl amido benzene structure; For example; 4; 4 '-dimethylamino benzophenone (Japanese Cao Da corporate system NISSOCURE MABP), 4; 4 '-diethylamino benzophenone (Hodogaya Chemical Co.; LTD. make EAB) etc. dialkyl amido benzophenone, 7-(diethylamino)-4-methyl-2H-1-chromen-2-one (7-(diethylamino)-4-methylcoumarin) etc. contain the coumarin compound, 4-dimethylamino ethyl benzoate (the Japanese chemical drug KAYACURE EPA of company), 2-dimethylamino ethyl benzoate (the Quantacure DMB of International Bio-Synthetics manufactured), 4-dimethylamino benzoic acid (n-butoxy) ethyl ester (the Quantacure BEA of International Bio-Synthetics manufactured) of dialkyl amido, to dimethylamino benzoic acid isopentyl ethyl ester (Japanese chemical drug corporate system KAYACURE DMBI), 4-dimethylamino benzoic acid-2-Octyl Nitrite (Van Dyk corporate system Esolol 507), 4; 4 '-diethylamino benzophenone (Hodogaya Chemical Co., LTD. makes EAB) etc.
In the middle of above-mentioned, preferred thioxanthones compound and tertiary amine compound.The aspect of curable from the deep preferably comprises the thioxanthones compound in the composition of the present invention, wherein preferred 2,4-dimethyl thioxanthones, 2,4-diethyl thioxanthone, 2-clopenthixal ketone, 2, thioxanthones compounds such as 4-diisopropyl thioxanthones.
As the combined amount of such thioxanthones compound, contain carboxylic acid resin (A) with respect to 100 mass parts are above-mentioned, be preferably below 20 mass parts, more preferably the ratio below 10 mass parts.When the combined amount of thioxanthones compound was too much, the thick film curable reduced, so that the raising of the cost of product, so not preferred.
As tertiary amine compound, preferably have the compound of dialkyl amido benzene structure, wherein, preferred especially dialkyl amido benzophenone cpd, maximum absorption wavelength are at the coumarin compound that contains dialkyl amido of 350nm～410nm.As the dialkyl amido benzophenone cpd, preferred toxicity low 4,4 '-diethylamino benzophenone.Maximum absorption wavelength at the coumarin compound that contains dialkyl amido of 350nm～410nm since maximum absorption wavelength in the ultraviolet range; Thereby except less painted and water white solder resist photosensitive composite can be provided; Can also use coloring pigment, the painted soldering-resistance layer of the color that reflects coloring pigment itself is provided.Particularly 7-(diethylamino)-4-methyl-2H-1-chromen-2-one goes out excellent sensitization effect for the laser display of wavelength 400～410nm, so preferred.
As the combined amount of such tertiary amine compound, be preferably 0.1～20 mass parts, the ratio of 0.1～10 mass parts more preferably with respect to the aforementioned carboxylic acid photoresist (A) that contains of 100 mass parts.When the combined amount of tertiary amine compound is 0.1 mass parts when following, be in the tendency that can not obtain sufficient sensitization effect.When the combined amount of tertiary amine compound surpassed 20 mass parts, the light absorption in drying resistance weldering film coated surface that tertiary amine compound causes became acutely, has the tendency that the deep curable reduces.
These Photoepolymerizationinitiater initiaters, light-initiated auxiliary agent and sensitizer can use separately or as the potpourri more than 2 kinds.
The total amount of these Photoepolymerizationinitiater initiaters, light-initiated auxiliary agent and sensitizer is divided the aforementioned carboxylic acid resin of containing (A) the preferably scope below 35 mass parts with respect to 100 quality.When surpassing 35 mass parts, the light absorption with them causes the tendency of deep curable reduction.
In order to give thermotolerance, can cooperate and have 2 above ring-type ethers and/or cyclic thioether base in the molecule Thermocurable composition (D) of (below, abbreviate ring-type (sulphur) ether as) in the photosensitive composite of the present invention.
The Thermocurable composition (D) that has 2 above ring-types (sulphur) ether in 1 molecule like this is the compound that has any one or two kinds of groups in 2 above three-membered rings, four-membered ring or pentacyclic ring-type ether or the cyclic thioether base in the molecule, and can enumerate the compound that has at least 2 above epoxy radicals in the molecule for example and be the compound that has at least 2 above oxetanyls in multi-group epoxy compound (D-1), 1 molecule and be the compound that has 2 above thioether groups in polyfunctional group oxetane compound (D-2), 1 molecule is episulfide resin (D-3) etc.
As above-mentioned multi-group epoxy compound (D-1); For example can enumerate out; Bisphenol A type epoxy resin; EPIKOTE 828, EPIKOTE 834, EPIKOTE 1001, EPIKOTE 1004 like the japan epoxy resin manufactured; EPICLON 840, EPICLON 850, EPICLON 1050, EPICLON 2055 that big Japanese ink chemical industrial company makes; Dongdu changes into EP OTOTE YD-011, YD-013, YD-127, the YD-128 of manufactured, D.E.R.317, D.E.R.331, D.E.R.661, D.E.R.664 that Dow Chemical makes, Araldite 6071, Araldite 6084, Araldite GY250, Araldite GY260 that Xiba Special Chemical Product Co.,Ltd makes; Sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA-128 that Sumitomo Chemical Co. Ltd. makes, (all being trade name) such as the A.E.R.330 that industrial group of Asahi Chemical Industry makes, A.E.R.331, A.E.R.661, A.E.R.664; Brominated epoxy resin; EPIKOTE YL903 like the japan epoxy resin manufactured; EPICLON 152, EPICLON 165 that big Japanese ink chemical industrial company makes; Dongdu changes into EPOTOTE YDB-400, the YDB-500 of manufactured, the D.E.R.542 that Dow Chemical makes, the Araldite 8011 that Xiba Special Chemical Product Co.,Ltd makes; Sumi-Epoxy ESB-400, ESB-700 that Sumitomo Chemical Co. Ltd. makes, (all being trade name) such as the A.E.R.711 that industrial group of Asahi Chemical Industry makes, A.E.R.714; Phenolic resin varnish type epoxy resin; EPIKOTE 152, EPIKOTE 154 like the japan epoxy resin manufactured; D.E.N.431, D.E.N.438 that Dow Chemical makes; EPICLON N-730, EPICLON N-770, EPICLON N-865 that big Japanese ink chemical industrial company makes; Dongdu changes into EPOTOTE YDCN-701, the YDCN-704 of manufactured; Araldite ECN1235, Araldite ECN1273, Araldite ECN1299, Araldite XPY307 that Xiba Special Chemical Product Co.,Ltd makes; EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, the RE-306 of Japan's chemical drug manufactured, Sumi-Epoxy ES CN-195X, ESCN-220 that Sumitomo Chemical Co. Ltd. makes, (all being trade name) such as the A.E.R.ECN-235 that industrial group of Asahi Chemical Industry makes, ECN-299; Bisphenol f type epoxy resin; The EPICLON 830 that makes like big Japanese ink chemical industrial company; The EPIKOTE 807 of japan epoxy resin manufactured; Dongdu changes into EPOTOTE YDF-170, YDF-175, the YDF-2004 of manufactured, (all being trade names) such as Araldite XPY306 that Xiba Special Chemical Product Co.,Ltd makes; Bisphenol-A epoxy resin changes into EPOTOTEST-2004, ST-2007, ST-3000 (trade name) of manufactured etc. like Dongdu; Glycidyl amine type epoxy resin; EPIKOTE 604 like the japan epoxy resin manufactured; Dongdu changes into the EPOTOTE YH-434 of manufactured; The Araldite MY720 that Xiba Special Chemical Product Co.,Ltd makes, (all being trade name) such as Sumi-Epoxy ELM-120 that Sumitomo Chemical Co. Ltd. makes; The Araldite CY-350 hydantoins type epoxy resin such as (trade names) that Xiba Special Chemical Product Co.,Ltd makes; The Celloxide 2021 that Daicel chemical industrial company makes, (all being trade name) alicyclic epoxy resins such as the AralditeCY 175 that Xiba Special Chemical Product Co.,Ltd makes, CY 179; The YL-933 of japan epoxy resin manufactured, (all being trade name) three hydroxyphenyl methane type epoxy resin such as the T.E.N.EPPN-501 that Dow Chemical makes, EPPN502; (all being trade name) di-cresols type or united phenol-type epoxy resin or their potpourris such as the YL-6056 of japan epoxy resin manufactured, YX-4000, YL-6121; The EBPS-200 of Japan's chemical drug manufactured, the EXA-1514 bisphenol-s epoxy resins such as (trade names) that the EPX-30 that Asahi Electro-Chemical Co. Ltd makes, big Japanese ink chemical industrial company make; The EPIKOTE 157S bisphenol-A phenolic varnish type epoxy resin such as (trade names) of japan epoxy resin manufactured; (all being trade name) four phenolic hydroxyl group ethane type epoxy resin such as Araldite 163 that the EPIKOTE YL-931 of japan epoxy resin manufactured, Xiba Special Chemical Product Co.,Ltd make; (all being trade name) hetero ring type epoxy resin such as TEPIC that the Araldite PT810 that Xiba Special Chemical Product Co.,Ltd makes, daily output chemical industrial company make; The o-phthalic acid diglycidyl ester resins such as BLEMMER DGT that Nof Corp. makes; Dongdu changes into the four glycidyl group xylenols ethane resin such as ZX-1063 of manufactured; ESN-190, ESN-360 that chemical company of Nippon Steel makes, the HP-4032 that big Japanese ink chemical industrial company makes, EXA-4750, EXA-4700 etc. contain the epoxy resin of naphthyl; The HP-7200 that big Japanese ink chemical industrial company makes, HP-7200H etc. have the epoxy resin of bicyclopentadiene skeleton; GMA copolymerization such as the CP-50S that Nof Corp. makes, CP-50M are epoxy resin; Further can enumerate the copolymerization epoxy resin of cyclohexyl maleimide and GMA; The epoxy resin of epoxide modified polybutadiene rubber derivant (for example the PB-3600 that makes of Daicel chemical industry etc.), CTBN modification (for example Dongdu changes into the YR-102, YR-450 of manufactured etc.) etc., but be not limited to these materials.These epoxy resin can use separately or make up more than 2 kinds and use.Preferred especially phenolic resin varnish type epoxy resin, hetero ring type epoxy resin, bisphenol A type epoxy resin or their potpourri in the middle of these.
As aforementioned polyfunctional group oxetane compound (D-2); Can enumerate out two [(3-methyl-3-oxetanes ylmethoxy) methyl] ethers, two [(3-ethyl-3-oxetanes ylmethoxy) methyl] ether, 1; Two [(3-methyl-3-oxetanes ylmethoxy) methyl] benzene, 1 of 4-; Two [(3-ethyl-3-oxetanes ylmethoxy) methyl] benzene of 4-, acrylic acid (3-methyl-3-oxetanyl) methyl esters, acrylic acid (3-ethyl-3-oxetanyl) methyl esters, methacrylic acid (3-methyl-3-oxetanyl) methyl esters, methacrylic acid (3-ethyl-3-oxetanyl) methyl esters, their polyfunctional group oxetanes classes such as oligomer or multipolymer; In addition, also have oxetanes and novolac resin, gather the etherate etc. that (para hydroxybenzene ethene), cardo type bisphenols, calixarene kind, resorcinol calixarenes (calixresorcinarene) type or silsesquioxane (silsesquioxane) etc. have the resin formation of hydroxyl.Other example can also be enumerated the multipolymer of unsaturated monomer with oxetanes ring and (methyl) alkyl acrylate etc.
As the compound (D-3) that has 2 above cyclic thioether bases in the aforementioned molecule, for example can enumerate the bisphenol A-type episulfide resin YL 7000 of japan epoxy resin manufactured etc.In addition, also can use with same synthetic method the oxygen atom of the epoxy radicals in the phenolic resin varnish type epoxy resin is replaced into episulfide resin of sulphur atom etc.
The combined amount that has the Thermocurable composition (D) of 2 above ring-types (sulphur) ether in the aforementioned molecule is preferably 0.6～2.0 equivalent, the scope of 0.8～1.5 equivalent more preferably with respect to the aforementioned carboxylic acid resin's of containing 1 equivalent carboxyl.Have in the molecule under the situation of combined amount less than 0.6 equivalent of Thermocurable composition (D) of 2 above ring-types (sulphur) ether, can residual carboxyl in soldering-resistance layer, make declines such as thermotolerance, alkali resistance, electrical insulating property, so not preferred.On the other hand, surpassing under the situation of 2.0 equivalents,, causing the reductions such as intensity of filming, so not preferred because low-molecular-weight ring-type (sulphur) ether can remain in the dry coating.
Use under the situation of the Thermocurable composition (D) that has 2 above ring-types (sulphur) ether in the above-mentioned molecule, preferably contain thermal curing catalyst.As such thermal curing catalyst, imidazoles, glyoxal ethyline, 2-ethyl imidazol(e), 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-imdazole derivatives such as 2-ethyl-4-methylimidazole are for example arranged; Dicyandiamide, benzyl dimethyl amine, 4-(dimethylamino)-N, N-dimethyl benzyl amine, 4-methoxyl-N, N-dimethyl benzyl amine, 4-methyl-N, amines such as N-dimethyl benzyl amine; Hydrazide compounds such as hexane diacid hydrazides, decanedioic acid hydrazides; Phosphorus compounds such as triphenylphosphine etc.; And commercially available thermal curing catalyst for example has, and four countries change into 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, the 2P4MHZ (being the trade name of imidazole compound all) that industrial group makes; The U-CAT3503N of SAN-APRO manufactured, U-CAT3502T (being the trade name of the block isocyanate compound of dimethyl amine all), DBU, DBN, U-CATSA102, U-CAT5002 (being two ring type amidine compound and salt thereof all) etc.Be not particularly limited in above-claimed cpd; So long as the thermal curing catalyst of epoxy resin or oxetane compound, maybe can promote that the material of reaction of epoxy radicals and/or oxetanyl and carboxyl is just passable, can use separately or mix more than 2 kinds and use.In addition; Also can use guanamine, acetyl guanamine, benzo guanamine, melamine, 2; 4-diamido-6-methacryloxyethyl s-triazine, 2-vinyl-2; 4-diamido s-triazine, 2-vinyl-4; 6-diamido s-triazine isocyanuric acid addition product, 2,4-diamido-Striazine derivatives such as 6-methacryloxyethyl s-triazine isocyanuric acid addition product preferably is used in combination these compounds that also play the tackifiers effect with the aforementioned hot curing catalysts.
The combined amount of these thermal curing catalysts is just enough with the ratio of common amount, for example contains the Thermocurable composition (D) that has 2 above ring-types (sulphur) ether in carboxylic acid resin (A) or the molecule with respect to 100 mass parts and is preferably 0.1～20 mass parts, 0.5～15.0 mass parts more preferably.
Photosensitive composite of the present invention also can cooperate inorganic filling material as required in order to improve its physical strength of filming etc.Known inorganic or organic filler commonly used be can use as such filler, barium sulphate, spherical silica and talcum especially preferably used.In addition, also can use NANOCRYL (trade name) XP 0396, XP 0596, XP 0733, XP 0746, XP 0765, XP 0768, XP 0953, XP 0954, XP 1045 (all being marque names), NANOPOX (trade name) XP 0516 of Hanse-Chemie manufactured, XP 0525, the XP 0314 (all being marque names) of the Hanse-Chemie manufactured that in the compound with 1 above ethylenically unsaturated group, aforementioned polyfunctional epoxy resin (D-1), is dispersed with the nanometer silica.These can separately or make up two or more uses.
The combined amount of these fillers is preferably below 300 mass parts with respect to the aforementioned carboxylic acid resin of containing of 100 mass parts (A), and more preferably 0.1～300 mass parts is preferably 0.1～150 mass parts especially.When the combined amount of aforementioned filler surpassed 300 mass parts, the viscosity of photosensitive composite uprised, and printing reduces, and perhaps solidfied material becomes fragile, so not preferred.
In addition, photosensitive composite of the present invention perhaps is used to be applied to the viscosity on substrate or the carrier film in order to adjust for synthetic aforementioned carboxylic acid resin (A), the modulation group compound of containing, can be with an organic solvent.
As such organic solvent, can enumerate out ketone, aromatic hydrocarbon based, glycol ethers, glycol ether acetates, ester class, alcohols, aliphatic hydrocarbon, oil series solvent etc.Specifically, can enumerate out ketones such as MEK, cyclohexanone; Toluene, xylene, tetramethylbenzene etc. are aromatic hydrocarbon based; Glycol ethers such as cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, BC, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, DPG diethyl ether, Triethylene glycol ethyl ether; Ethers such as ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetic acid esters, propylene glycol methyl ether acetate, propylene-glycol ethyl ether acetic acid esters, propylene glycol butyl ether acetic acid esters; Alcohols such as ethanol, propyl alcohol, monoethylene glycol, propylene glycol; Aliphatic hydrocarbon such as octane, decane; Oil series solvents such as sherwood oil, naphtha, hydrotreated naphtha, solvent naphtha.These organic solvents can be used alone or in combination more than 2 kinds.
Photosensitive composite of the present invention also can mix known hot polymerization inhibitors commonly used such as quinhydrones, hydroquinone monomethyl ether, tert-butyl catechol, 1,2,3,-thrihydroxy-benzene, phenothiazine as required; Known thickening agents commonly used such as fine particle silica, organobentonite, smectite; The foam-breaking agent and/or the levelling agent of silicone-based, fluorine system, macromolecular etc.; The silane coupling agent of imidazoles system, thiazole system, triazole system etc., anti-oxidant, the additive kind known commonly used that rust preventive etc. are such.
For example photosensitive composite of the present invention is adjusted to the viscosity that is suitable for coating process with aforementioned organic solvent; The methods such as method, silk screen print method, curtain coating method that are coated with through dip coating, flow coat method, rolling method, rod are applied on the substrate that is formed with circuit; Under about 60～100 ℃ temperature, make organic solvent volatile dry contained in the composition (temporary transient dry), can form tack-free filming thus.The dry coating of this photosensitive composite of the present invention preferably has the thickness of 15～100 μ m.In addition,, make its drying, can obtain dry film through photosensitive composite of the present invention is applied on the carrier film.To fit on the substrate as the material that winding film obtains, peel off carrier film, thus, can form soldering-resistance layer being formed with on the substrate of circuit.Then, with direct drawing apparatus (laser direct imaging device), describe the pattern latent image after, through alkaline aqueous solution (for example, 0.3～3% aqueous sodium carbonate), unexposed is developed, form soldering-resistant pattern.And then; Under the situation that contains the Thermocurable composition; Make its heat curing through being heated to for example about 140～180 ℃ temperature; Thereby ring-type (sulphur) ether that has the Thermocurable composition (D) of 2 above ring-types (sulphur) ether in the aforementioned carboxylic acid resin's of containing (A) carboxyl and the molecule reacts, and can obtain the cured coating film of each excellents such as thermotolerance, chemical proofing, anti-hydroscopicity, adaptation, electrical characteristics.
As the base material that is used for aforesaid substrate; Can enumerate the high-frequency circuit that uses paper phenolics, paper epoxy resin, glass cloth epoxy resin, glass polyimide, glass cloth/nonwoven fabrics epoxy resin, glass cloth/paper epoxy resin, synthon epoxy resin, fluoro-tygon-PPO-cyanate etc. copper clad laminate with all models (FR-4 etc.) of materials such as copper clad laminate, and polyimide film, PET film, glass substrate, ceramic substrate, wafer board etc.
The volatile dry that behind coating photosensitive composite of the present invention, carries out; Can use heated air circulation type drying oven, IR stove, hot plate, convective oven etc. (use have the air heat mode of utilizing steam thermal source device and make the method for the hot air convection contact in the dryer and through nozzle the hot blast in the dryer be ejected into the mode of supporter) carry out.
As the light source of the exposure device that is used for photosensitive composite of the present invention, can use semiconductor laser, Solid State Laser.In addition, its exposure is generally 5～100mJ/cm because of the thick grade of dry coating of photosensitive composite of the present invention is different 2, be preferably 5～60mJ/cm 2, further preferably be 5～30mJ/cm 2Scope.As direct drawing apparatus, can use PENTAX Company manufacturing, Hitachi ViaMechanics, the device that Ltd. makes, Ball Semiconductor Inc. makes.
As aforementioned developing method, infusion process capable of using, spray process, gunite, brushing method etc. as developer solution, can be used the alkaline aqueous solution of potassium hydroxide, NaOH, sodium carbonate, sal tartari, sodium phosphate, sodium silicate, ammonia, TMAH etc.
Embodiment
Below, illustrative embodiments specifies the present invention, but the present invention is not limited to following embodiment.
< containing the synthetic of carboxylic acid resin >
In having 2 liters detachable flask of stirring machine, thermometer, reflux condenser, tap funnel and nitrogen ingress pipe, add 660g formaldehyde novolac type epoxy resin (Japanese chemical drug (strain) manufacturing, EOCN-104S, 92 ℃ of softening points, epoxide equivalent=220g/ equivalent), 421.3g carbitol acetic acid esters and 180.6g solvent naphtha as solvent; Be heated to 90 ℃ and stirring, dissolving.Then, temporarily be cooled to 60 ℃, add 216g acrylic acid, 4.0g, under 100 ℃, make its reaction 12 hours, obtain the reaction product that acid number is 0.2mgKOH/g as the triphenylphosphine of catalysts, 1.3g methylnaphthohydroquinone as polymerization inhibitor.To wherein adding the 241.7g tetrabydrophthalic anhydride, be heated to 90 ℃ and make its reaction 6 hours.Thus, obtain the solution that contains the carboxylic acid resin of nonvolatile component=65 quality %, solid constituent acid number=77mgKOH/g, two key equivalent (the g weight of the resin of per 1 mole of unsaturated group)=400g/ equivalent, weight-average molecular weight=7000.Below, this solution that contains the carboxylic acid resin is called A-1 varnish.
< modulation of photosensitive composite 1～7 >
Cooperate the composition shown in the table 1 with the amount shown in the table 1 (mass parts), and stir, make its dispersion, obtain photosensitive composite respectively with three roller roller mills.
Table 1
Figure 2007101872549A00800241
Figure 2007101872549A00800251
The absorbance of the soldering-resistance layer of photosensitive composite 1～7 formation is used in investigation.That is, be applied to glass plate on coating machine each photosensitive composite after, use the heated air circulation type drying oven, 80 ℃ dry 30 minutes down, on glass plate, make its dry coating.For the dry coating of each photosensitive composite on this glass plate, use ultraviolet-visible pectrophotometer (Japanese beam split Co., Ltd. makes, Ubest-V-570DS) and integrating sphere device (Japanese beam split Co., Ltd. makes, ISN-470), the mensuration absorbance.In addition, for the glass plate same, measure the absorbance baseline of the wavelength coverage of 300～500nm with the glass plate that is coated with each photosensitive composite.Deduct baseline from the absorbance of the glass plate of the band dry coating of made, thereby calculate the absorbance of dry coating.The coating thickness of coating machine coating is divided 4 phasic changes and carries out this operation,, obtain the absorbance when dry soldering-resistance layer is thick to be 25 μ m from this chart.The result is shown in table 2.
Table 2
Figure 2007101872549A00800261
Then, for photosensitive composite 1,, this dry coating is made public through the exposure method of the embodiment shown in the table 31 with embodiment 2 and comparative example 1～4.
Table 3
Figure 2007101872549A00800262
At this, in order to investigate all character of formed soldering-resistance layer, test as follows, estimate.
(1) surface cure property
The copper-clad base plate of the thick 355 μ m of copper is carried out after polishing roll grinds, and washing makes its drying.Then, photosensitive composite 1 is applied on this substrate, with 80 ℃ heated air circulation type kiln drieds 60 minutes through silk screen print method.After the drying,, this drying resistance weldering filmed make public through embodiment 1 and 2 and the exposure method of comparative example 1～4.Exposing patterns uses the blanket exposure pattern.After the exposure, use 1 quality % aqueous sodium carbonate, under 30 ℃, 0.2MPa, carried out for 60 seconds and develop, then, under 150 ℃, carry out heat curing in 60 minutes as developer solution.
The evaluation of the glossiness when using Grossmeters micro-tri-gloss (BYK Gardher manufactured) that the surface cure property of the cured coating film that obtains is like this carried out 60 ° of incident angles.As evaluation criterion, this numerical value is above to be good with glossiness 50, and not enough this numerical value is bad.This evaluation result is shown in table 4.
(2) curing depth and cross sectional shape
With the width of the μ m/300 μ m of line/at interval=300 and copper thick be that the circuit pattern substrate of 70 μ m carries out respectively washing drying after polishing roll grinds.Through silk screen print method photosensitive composite 1 is applied on this circuit pattern substrate, with 80 ℃ heated air circulation type kiln drieds 30 minutes.After the drying,, this dry coating is made public through embodiment 1 and 2 and the exposure method of comparative example 1～4.Exposing patterns uses the pattern of line of describing the width of 30/40/50/60/70/80/90/100 μ m in above-mentioned spacer portion respectively successively.After the exposure, use 1.0 quality % aqueous sodium carbonates to develop, thereby obtain soldering-resistant pattern.Then, with high-pressure sodium lamp with 1000mJ/cm 2The exposure irradiating ultraviolet light after, make its heat curing 60 minutes.At this moment, with of the evaluation of residual minimum feature as curing depth.
In addition, the design load of the live width through observing cured coating film is the cross section of the line portion of 100 μ m, carries out the evaluation of cross sectional shape.At this, the thickness of the soldering-resistance layer that copper is thick when being 70 μ m is 65 μ m.According to the synoptic diagram of Fig. 1, estimate with five grade pair cross-sections of A～E shape.Among the figure, 1a representes the design load of live width, and 1b representes the shape of the soldering-resistance layer behind the exposure imaging, and 1c representes substrate.The state of each evaluation is following, that is,
A estimates: by the perfect condition of design width
B estimates: the corrosion that produces the superficial layer that anti-development property deficiency etc. causes
C estimates: the undercutting state
D estimates: the line chap that generation halation etc. causes
E estimates: the line chap and the undercutting that produce superficial layer
At this, undercutting and halation all are the terms of the deviation of expression off-design value.Undercutting representes that particularly the bottom is thinner than design load, and halation representes that any or both in top, the bottom are thicker than design load.
Particularly in A estimates, the online upper and lower of the deviation of off-design value is all in 5 μ m.
Only A does not estimate, and C estimates, D estimates all is the level that can be used as solder resist.With respect to this, during B evaluation, E estimated, line, undercut portions were peeled off easily, were to be difficult to be evaluated as the level that can not use as the level, particularly E of solder resist.
Evaluation result is shown in table 4 in the lump.
Table 4
Figure 2007101872549A00800281
Can know from table 4 and to know, use under the situation of embodiment 1 and 2 exposure method of exposure method of the present invention,, obtain excellent cross sectional shape, curing depth and surface cure property with low exposure and short exposure time.On the other hand, under the situation of the exposure method that uses comparative example 1～4, solidify in order to make composition, need higher exposure and longer time shutter, in addition, the cross sectional shape of resulting soldering-resistance layer, curing depth and surface cure property are insufficient.
In addition, also its dry coating is made public, form soldering-resistance layer for photosensitive composite 2～7.In order to investigate all character of formed soldering-resistance layer, as exposure method, use the method and the above-mentioned test likewise of embodiment 1 and 2, estimate.Will be for being shown in table 5 together for the evaluation result that cooperates example 1 in the evaluation result of these tests and the table 4.
Table 5
Figure 2007101872549A00800291
Figure 2007101872549A00800292
Can know from the result of table 5; In the formation method of soldering-resistance layer of the present invention; More preferably use the photosensitive composite (1～5) that shows below absorbance: the per 25 μ m thickness of dry coating before its exposure; Under the wavelength coverage of 355～380nm, demonstrate the absorbance of 0.6～1.2 scope, and under 405nm, demonstrate the absorbance of 0.3～0.6 scope.
Embodiment 3
With the photosensitive composite 1 shown in the MEK dilution table 1; Be applied on the carrier film; With 80 ℃ heated air circulation type kiln drieds 30 minutes, forming thickness was the light solidifying/heat solidifying resin composition layer of 25 μ m, fitted above that and went up film (cover film) and obtain dry film.Then, peel off film, forming heat lamination gained dry film on the figuratum copper clad laminate.Then, under the condition of the embodiment shown in the table 31 and 2, implement exposure, remove carrier film after, developed for 60 seconds with the aqueous sodium carbonate of 1wt%, obtain image.Carry out 60 minutes heat curing again with 150 ℃ heated air circulation type drying oven, make the test substrate.For resulting test substrate,, each characteristic is carried out evaluation test with aforementioned test method and evaluation method with curing overlay film.Coming to the same thing of the photosensitive composite 1 of result and table 5.

Claims (6)

1. the formation method of the soldering-resistant pattern of printed circuit board (PCB) is characterized in that, photosensitive composite is applied on the printed circuit board (PCB); Behind the volatile dry; This dry coating is shone the laser and the laser with wavelength of 405nm of the wavelength with 355nm, the laser that forms the wavelength of the said 355nm of having shines the pattern latent image that obtains respectively with the laser with wavelength of 405nm, then; Develop through alkaline aqueous solution
Said photosensitive composite comprises (A) and contains carboxylic acid resin, (B) Photoepolymerizationinitiater initiater and (C) pigment; The combined amount of said (B) Photoepolymerizationinitiater initiater is 0.01～30 mass parts with respect to the said carboxylic acid resin of containing of 100 mass parts (A); It is 0.01～5 mass parts that the combined amount of said (C) pigment contains the carboxylic acid resin with respect to 100 mass parts said (A); In said each scope, regulate combined amount of said (B) Photoepolymerizationinitiater initiater and the combined amount of said (C) pigment respectively; The per 25 μ m thickness of dry coating before the exposure of said photosensitive composite show 0.6～1.2 absorbance in the wavelength coverage of 355～380nm, and; Under the wavelength of 405nm, show 0.3～0.6 absorbance
Wherein, Said Photoepolymerizationinitiater initiater (B) is that the oxime ester that is selected from the group shown in (I) that has formula is a Photoepolymerizationinitiater initiater, alpha-aminoacetophenone with the group shown in the formula (II) is that Photoepolymerizationinitiater initiater and the acylphosphine oxide with the group shown in the formula (III) are the Photoepolymerizationinitiater initiater more than a kind in the group formed of Photoepolymerizationinitiater initiater
Figure FSB00000614583800011
In the formula, R 1The expression hydrogen atom; Can be by the substituted phenyl of the alkyl of carbon number 1～6, phenyl or halogen atom; Can be replaced and also can have the alkyl of the carbon number 1～20 of 1 above oxygen atom by 1 above hydroxyl at the alkyl middle-of-chain; The naphthenic base of carbon number 5～8 can be by the alkanoyl or the benzoyl of the substituted carbon number 2～20 of the alkyl or phenyl of carbon number 1～6
R 2Expression can be by the substituted phenyl of the alkyl of carbon number 1～6, phenyl or halogen atom; Can be replaced and also can have the alkyl of the carbon number 1～20 of 1 above oxygen atom by 1 above hydroxyl at the alkyl middle-of-chain; The naphthenic base of carbon number 5～8; Can be by the alkanoyl or the benzoyl of the substituted carbon number 2～20 of the alkyl or phenyl of carbon number 1～6
R 3And R 4Alkyl or the aralkyl of representing carbon number 1～12 independently of one another,
R 5And R 6Represent the alkyl of hydrogen atom, carbon number 1～6 or the cyclic alkyl ether of both be combined intos independently of one another,
R 7And R 8Represent independently of one another carbon number 1～10 straight chain shape or branched-chain alkyl, cyclohexyl, cyclopentyl, aryl, or can be by the substituted aryl of halogen atom, alkyl or alkoxy, wherein, R 7And R 8In a side also can represent R-C (=O)-Ji, here, R is the alkyl of carbon number 1～20.
2. the formation method of the soldering-resistant pattern of printed circuit board (PCB) according to claim 1 is characterized in that, the side in the laser of the laser of the wavelength of the said 355nm of having and the wavelength with 405nm is a royal purple laser.
3. the formation method of the soldering-resistant pattern of printed circuit board (PCB) according to claim 1; It is characterized in that; The per 25 μ m thickness of said dry coating before the exposure of said photosensitive composite, the difference of the absorbance under the maximum absorbance of the wavelength coverage of 355～380nm and wavelength at 405nm is more than 0.3 and less than 0.6.
4. the formation method of the soldering-resistant pattern of printed circuit board (PCB) according to claim 1; It is characterized in that; The per 25 μ m thickness of said dry coating before the said photosensitive composite exposure show 0.6～1.0 absorbance under the wavelength of 355nm, and the absorbance that under the wavelength of 405nm, shows 0.3～0.5; And the difference of the absorbance under absorbance under the wavelength of 355nm and the wavelength at 405nm is more than 0.3 and less than 0.5.
5. the formation method of the soldering-resistant pattern of printed circuit board (PCB) according to claim 1 is characterized in that, said oxime ester with the group shown in the formula (I) is the compound that Photoepolymerizationinitiater initiater comprises formula (IV)
6. the formation method of the soldering-resistant pattern of printed circuit board (PCB) according to claim 1 is characterized in that, said oxime ester with the group shown in the formula (I) is the compound that Photoepolymerizationinitiater initiater comprises formula (V),
Figure FSB00000614583800032
In the formula, R 9The alkyl of expression hydrogen atom, halogen atom, carbon number 1～12, cyclopentyl, cyclohexyl, phenyl, benzyl, benzoyl, the alkanoyl of carbon number 2～12, the alkoxy carbonyl group or the carbobenzoxy of carbon number 2～12; Wherein, The carbon number that constitutes the alkyl of alkoxy is 2 when above; Alkyl can be replaced by 1 above hydroxyl, also can have 1 above oxygen atom at the alkyl middle-of-chain
R 10And R 12Expression can be by the substituted phenyl of the alkyl of carbon number 1～6, phenyl or halogen atom independently of one another; Can be replaced and also can have the alkyl of the carbon number 1～20 of 1 above oxygen atom by 1 above hydroxyl at the alkyl middle-of-chain; The naphthenic base of carbon number 5～8; Can be by the alkanoyl or the benzoyl of the substituted carbon number 2～20 of the alkyl or phenyl of carbon number 1～6
R 11The expression hydrogen atom; Can be by the substituted phenyl of the alkyl of carbon number 1～6, phenyl or halogen atom; Can be replaced and also can have the alkyl of the carbon number 1～20 of 1 above oxygen atom by 1 above hydroxyl at the alkyl middle-of-chain; The naphthenic base of carbon number 5～8 can be by the alkanoyl or the benzoyl of the substituted carbon number 2～20 of the alkyl or phenyl of carbon number 1～6.
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