CN101319314B - Thin-layer metal membrane material and method of producing the same - Google Patents

Thin-layer metal membrane material and method of producing the same Download PDF

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Publication number
CN101319314B
CN101319314B CN200810110607XA CN200810110607A CN101319314B CN 101319314 B CN101319314 B CN 101319314B CN 200810110607X A CN200810110607X A CN 200810110607XA CN 200810110607 A CN200810110607 A CN 200810110607A CN 101319314 B CN101319314 B CN 101319314B
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layer
polymer layer
group
compound
image shape
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CN101319314A (en
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松本洋介
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Fujifilm Corp
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
    • C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
    • C23C18/1886—Multistep pretreatment
    • C23C18/1893—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1603—Process or apparatus coating on selected surface areas
    • C23C18/1607—Process or apparatus coating on selected surface areas by direct patterning
    • C23C18/1608—Process or apparatus coating on selected surface areas by direct patterning from pretreatment step, i.e. selective pre-treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1655—Process features
    • C23C18/166—Process features with two steps starting with addition of reducing agent followed by metal deposition
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2073—Multistep pretreatment
    • C23C18/2086—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/42—Coating with noble metals
    • C23C18/44—Coating with noble metals using reducing agents
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Materials For Photolithography (AREA)
  • Laminated Bodies (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Chemically Coating (AREA)
  • Preparing Plates And Mask In Photomechanical Process (AREA)

Abstract

The present invention provides a thin layer metal film material and the manufacturing method thereof, wherein the thin layer metal film material comprises a bearing structure which is composed of an interlayer, a polymeric layer and prills. The interlayer is formed by coupling agents provided with polymeric groups; the polymeric layer is image-shaped and directly combined with the surface of the interlayer, and the polymeric layer is formed by contacting composition including compound having crosslinking groups with the interlayer, then exerting energy to the composition according to an image shape; the prills are included in the image-shaped polymeric layer. According to the invention, a thin layer metal film material having image-shaped metal film is provided, wherein the image-shaped metal film is provided with high-density prills, besides, the metal film has good adhesiveness to the bearing structure.

Description

Thin-layer metal membrane material and method of manufacture thereof
Technical field
The present invention relates to a kind of thin-layer metal membrane material and method of manufacture thereof, more particularly, the present invention relates to a kind ofly be applicable to light screening material, especially be applicable to the thin-layer metal membrane material and the method for manufacture thereof of photomask.
Background technology
In recent years, the metal membrane material that is formed with thin-layer metal membrane in the desired zone on base material is applied in relating to a plurality of fields such as metal wiring, electrode, magneticsubstance.
In addition, above-mentioned metal membrane material also can be used as photomask.So-called photomask is meant the master that adopts photoetching technique will be when the pattern transfer that forms on the flat board is to other flat board used.Photomask in the past, employing be chromium blank or glass dry plate (this glass dry plate applies silver emulsion and obtains photo photosensitive material and form on the glass support thing).
The chromium blank is through with after the glass grinding, adopts the splash method to form mf above that, further adopts turner to come coated feel photosensitiveness resist to make (for example with reference to japanese kokai publication hei 1-154060 communique).Because above-mentioned grinding and splash need cost, so the costing an arm and a leg of chromium blank.In addition, there is following point in this method: the operation of chromium being carried out etch processes is numerous and diverse, and owing to need to use deleterious chromium, this is unsatisfactory on environment.
In addition, the film toughness of glass dry plate is poor, and this also is a problem (for example with reference to a japanese kokai publication hei 5-53253 communique).
In addition; The known method that such manufacturing metal membrane material is arranged; This method is: make to have polymerization and cause position (this polymerization causes position can cause Raolical polymerizable through photodestruciton) and combine with base material with the compound of base material combining site, and at this with after the unsaturated compound that Raolical polymerizable can take place contacts, carry out the image shape and make public; Form graftomer and generate the zone; Generate metals ion or the reduction of the metals ion in the metal-salt in the zone with joining this graftomer,, thereby make the metal membrane material (for example with reference to TOHKEMY 2005-275173 communique) of the metallic membrane that has the image shape so that metal separates out.
Adopt this method, can obtain the metallic membrane (metal pattern) of the high image shape of meticulous and resolving power and electroconductibility.But, in this technology, have more high-density metal particulate metallic membrane for forming with lower energy, do not study.
As stated; In order to obtain being formed with in the desired zone on base material the metal membrane material of thin-layer metal membrane; People expect a kind of like this technology; This technology can form with lower energy have high-density metal particulate and the excellent metallic membrane of adhesivity, however up to the present as yet the someone such technology is provided.
Summary of the invention
The problem that invention will solve
The present invention considers the problem that exists in the above-mentioned conventional art, and to realize that following purpose is as problem.
That is, the object of the present invention is to provide a kind of thin-layer metal membrane material, wherein in the metallic membrane of this image shape, have the high-density metal particle, and this metallic membrane has excellent adhesivity for support with metallic membrane of image shape.
In addition; Another object of the present invention is to provide a kind of method of manufacture of thin-layer metal membrane material; This method of manufacture can easily have the thin-layer metal membrane material of the metallic membrane of image shape with low-yield manufacturing; Wherein in the metallic membrane of this image shape, have the high-density metal particle, and this metallic membrane has excellent adhesivity for support.
The means of dealing with problems
Above-mentioned problem is to solve through following thin-layer metal membrane material and method of manufacture thereof.
That is, first kind of thin-layer metal membrane material of the present invention is characterized in that, contains: support; On this support, has the middle layer that the coupling agent of polymerizable group forms through employing; The polymer layer of image shape; This polymer layer is by through after will containing compound compositions with crosslinkable groups and said middle layer contacting, thereby polymkeric substance on this interlayer surfaces constitutes according to image shape directly being combined in of applying that energy generates to said composition; And, be included in the metallic particles in the polymer layer of this image shape.
First kind of thin-layer metal membrane material of the present invention, preferably through after first kind or second kind of method of manufacture manufacturing of the thin-layer metal membrane material of the present invention stated.
Second kind of thin-layer metal membrane material of the present invention is characterized in that, contains: support; The polymer layer of image shape; This polymer layer is by passing through on said support; After will containing coupling agent with polymerizable group and the compound compositions with crosslinkable groups and this support contacting, thereby the lip-deep polymkeric substance of above-mentioned support constitutes according to image shape directly being combined in of applying that energy generates to said composition; And, be included in the metallic particles in the polymer layer of this image shape.
Second kind of thin-layer metal membrane material of the present invention, preferably through after the third or the 4th kind of method of manufacture manufacturing of the thin-layer metal membrane material of the present invention stated.
First kind of method of manufacture of thin-layer metal membrane material of the present invention is characterized in that having following operation: form the operation in middle layer, in this operation, adopt the coupling agent with polymerizable group on support, to form the middle layer; Form the operation of the polymer layer of image shape; In this operation, pass through on said middle layer; After will containing compound compositions and this middle layer contacting with crosslinkable groups; Apply energy to said composition according to the image shape, generate and directly be combined in the polymkeric substance on this interlayer surfaces, and then form the polymer layer of image shape; And precipitating metal particulate operation is also reduced this metals ion with the precipitating metal particle through in said polymer layer, adding metals ion in this operation.
In addition, second kind of method of manufacture of thin-layer metal membrane material of the present invention is characterized in that having following operation: form the operation in middle layer, in this operation, have the coupling agent of polymerizable group and on support, form the middle layer through employing; Form the operation of the polymer layer of image shape; In this operation, pass through on this middle layer; The compsn that will contain compound with crosslinkable groups and metals ion is with after said middle layer contacts; Apply energy to said composition according to the image shape, generate and directly be combined in the polymkeric substance on this interlayer surfaces, and then form the polymer layer of image shape; And, precipitating metal particulate operation, in this operation through with the reduction of the metals ion that contains in the said polymer layer with the precipitating metal particle.
The third method of manufacture of thin-layer metal membrane material of the present invention; It is characterized in that having following operation: form the operation of the polymer layer of image shape, in this operation, pass through on support; After will containing coupling agent with polymerizable group and compound compositions and said support contacting with crosslinkable groups; Apply energy to said composition according to the image shape, generate and directly be combined in the lip-deep polymkeric substance of said support, and then form the polymer layer of image shape; And precipitating metal particulate operation is also reduced this metals ion with the precipitating metal particle through in said polymer layer, adding metals ion in this operation.
The 4th kind of method of manufacture of thin-layer metal membrane material of the present invention; It is characterized in that; Has following operation: the operation that forms the polymer layer of image shape; Through on support, the compsn that will contain the coupling agent with polymerizable group, the compound with crosslinkable groups and metals ion applies energy to said composition according to the image shape with after said support contacts in this operation; Generate and directly be combined in the lip-deep polymkeric substance of this support, and then form the polymer layer of image shape; And, precipitating metal particulate operation, in this operation through with the reduction of the metals ion that contains in the said polymer layer with the precipitating metal particle.
In the present invention, said containing preferably also contained photodestruciton type radical polymerization initiator in the compound compositions with crosslinkable groups.
In addition, the polymerizable group in the said coupling agent with polymerizable group is preferably identical functional group with crosslinkable groups in the said compound with crosslinkable groups.
Also have, in the present invention, said coupling agent with polymerizable group preferably has acryl or methacryloyl.
In addition, said compound with crosslinkable groups preferably has acryl or methacryloyl, perhaps preferably has vinyl or epoxy group(ing).
In the present invention, said metallic particles preferably has absorption to the light in the wavelength region more than the 365nm.
In addition, the thickness of said polymer layer is preferably in the scope more than 200nm, below the 2000nm.
In this manual, so-called " image shape " be meant, by the zone that has polymer layer with there is not the two-dimentional form that the zone constituted of polymer layer.For example, as in the situation of photomask, the zone that has polymer layer is as light shielding part at thin-layer metal membrane material of the present invention, and the zone that does not have a polymer layer is as non-light shielding part.Here, light shielding part mainly is that the light of 300nm～400nm is not seen through.In addition, non-light shielding part preferably can make the transmitance of the light of 300nm～400nm reach more than 90%.Also have,, be preferably 150nm～1 μ m though will change according to the purposes of photomask as the thickness of the slice of light shielding part and non-light shielding part.
Though effect of the present invention is indeterminate, can infer according to following situation.
Polymer layer of the present invention can form through following method: for example, support is combined with the coupling agent with polymerizable group, form the middle layer thus, this middle layer is contacted with the compound with crosslinkable groups, and apply energy to said composition.More particularly; Through applying energy to said composition; Can make between the compound in the compsn to react to each other, simultaneously, the compound with crosslinkable groups in the said composition reacted with the coupling agent with polymerizable group with crosslinkable groups.Also have, the coupling agent with polymerizable group just begins reaction on being added into support the time, and combines with support.Thus, make formed polymer layer and support have excellent adhesivity.
In being provided with the situation of layer that contains photopolymerization initiation position as the middle layer; Fully after the exposure, if the Photoepolymerizationinitiater initiater position does not produce radical or cationic words, the middle layer just can not stick on the support; So; If this Photoepolymerizationinitiater initiater position is active low, needs exposure for a long time, thereby postponed the adhesion of middle layer and support.On the other hand; In the present invention; Need be through not applying energy to produce radical or positively charged ion in the middle layer; As long as in containing the compound compositions with crosslinkable groups, produce radical or positively charged ion, this crosslinkable groups can promptly combine through copolymerization with the polymerizable group in this middle layer, thereby can form the big polymer layer of film thickness.
In addition, through applying energy, can form the polymer layer that has the image shape of excellent adhesion with support with the image shape.
In addition, as stated, if form the big polymer layer of film thickness, the amount of the metals ion that contains in this polymer layer so also increases thereupon, therefore can access and contain more high-density metal particulate polymer layer.
The invention effect
According to the present invention, a kind of thin-layer metal membrane material with metallic membrane of image shape can be provided, wherein in this metallic membrane, have the high-density metal particle, and this metallic membrane has excellent adhesivity for support.
In addition,, a kind of method of manufacture of thin-layer metal membrane material can be provided according to the present invention, through this method, can be easily with the above-mentioned thin-layer metal membrane material of low-yield manufacturing.
Preferred forms of the present invention
Below the present invention is elaborated.
First kind of thin-layer metal membrane material of the present invention (below, describe as " thin-layer metal membrane material of the present invention (1) "), it is characterized in that, contain: support; Middle layer, this middle layer adopt the coupling agent with polymerizable group to form on said support; The polymer layer of image shape; This polymer layer be by through with said middle layer with contain compound compositions and contact with crosslinkable groups after, constitute thereby apply the polymkeric substance that directly is combined on this interlayer surfaces that energy generates according to the image shape to said composition; And, be included in the metallic particles in the polymer layer of this image shape.
Thin-layer metal membrane material of the present invention (1), preferably according to after first kind or second kind of method of manufacture manufacturing of the thin-layer metal membrane material of the present invention stated.
In addition, second kind of thin-layer metal membrane material of the present invention (below, describe as " thin-layer metal membrane material of the present invention (2) "), it is characterized in that, contain: support; The polymer layer of image shape; This polymer layer is by passing through on this support; With this support with after the compound compositions that contains the coupling agent with polymerizable group and have a crosslinkable groups contacts, thereby the lip-deep polymkeric substance of this support constitutes according to image shape directly being combined in of applying that energy generates to said composition; And, be included in the metallic particles in the polymer layer of this image shape.
Thin-layer metal membrane material of the present invention (2), preferably according to after the third or the 4th kind of method of manufacture manufacturing of the thin-layer metal membrane material of the present invention stated.
First kind of method of manufacture of thin-layer metal membrane material of the present invention (below; Describe as " method of manufacture of thin-layer metal membrane material of the present invention (1) "); It is characterized in that; Comprise following operation: (a) adopting coupling agent to form the operation (below, be called " (a) middle layer forms operation ") in middle layer on the support with polymerizable group; (b1) on this middle layer; With this middle layer with contain compound compositions and contact with crosslinkable groups after; Apply energy to said composition according to the image shape; Generate and directly be combined in the polymkeric substance on this interlayer surfaces, and then the operation of the polymer layer of formation image shape (below, be called " (b1) polymer layer forms operation "); And, (c1) in this polymer layer, add metals ion after, with this metals ion reduction with precipitating metal particulate operation (below, be called " (c1) metallic particles is separated out operation ").
In addition; Second kind of method of manufacture of thin-layer metal membrane material of the present invention (below; Describe as " method of manufacture of thin-layer metal membrane material of the present invention (2) "); It is characterized in that, comprise following operation: (a) on support, adopt coupling agent to form the operation ((a) middle layer forms operation) in middle layer with polymerizable group; (b2) on this middle layer; With this middle layer with after the compsn that contains compound with crosslinkable groups and metals ion contacts; Apply energy to said composition according to the image shape; Generate and directly be combined in the polymkeric substance on this interlayer surfaces, and then the operation of the polymer layer of formation image shape (below, be called " (b2) polymer layer forms operation "); And, (c2) with the reduction of the metals ion that contains in this polymer layer with precipitating metal particulate operation (below, be called " (c2) metallic particles is separated out operation ").
In addition; The third method of manufacture of thin-layer metal membrane material of the present invention (below, describe as " method of manufacture of thin-layer metal membrane material of the present invention (3) "), it is characterized in that; Comprise following operation: (b3) on support; This support with after the compound compositions that contains the coupling agent with polymerizable group and have a crosslinkable groups contacts, is applied energy to said composition according to the image shape, generate and directly be combined in the lip-deep polymkeric substance of said support; And then the operation of the polymer layer of formation image shape (below, be called " (b3) polymer layer forms operation "); And, in this polymer layer, add metals ion after, with this metals ion reduction with precipitating metal particulate operation (below, suitably be called " (c3) metallic particles is separated out operation ").
In addition; The 4th kind of method of manufacture of thin-layer metal membrane material of the present invention (below, describe as " method of manufacture of thin-layer metal membrane material of the present invention (4) "), it is characterized in that; Comprise following operation: (b4) on support; This support with after the compsn that contains the coupling agent with polymerizable group, the compound with crosslinkable groups and metals ion contacts, is applied energy to said composition according to the image shape, generate and directly be combined in the lip-deep polymkeric substance of said support; And then the operation of the polymer layer of formation image shape (below, be called " (b4) polymer layer forms operation "); And, with the reduction of the metals ion that contains in this polymer layer with precipitating metal particulate operation (below, suitably be called " (c4) metallic particles is separated out operation ").
Below, through each operation in method of manufacture (1)～(4) of thin-layer metal membrane material of the present invention thin-layer metal membrane material of the present invention (1) and (2) are elaborated.
[(a) middle layer forms operation]
As follows, the method for manufacture of thin-layer metal membrane material of the present invention (1) and (2) comprise that (a) middle layer forms operation.
In this operation, on support, adopt coupling agent to form the middle layer with polymerizable group.
At first, describe for the coupling agent that adopts in this operation with polymerizable group.
So-called coupling agent with polymerizable group is meant the compound with polymerizable group and substituting group (this substituting group can form chemical bond with support).For not having special qualification with the substituting group that support forms chemical bond; As long as this substituting group can pass through covalent linkage, ionic linkage and hydrogen bond and support forms chemical bond; But consider from the angle of bonding strength, preferably can form the substituting group of covalent linkage.
Wherein, the substituting group as forming chemical bond with support is preferably the alkoxyl group that is selected from the element among Si, Ti, Zr, the Al, or halide group.
Below, as coupling agent, be that example describes with compound with polymerizable group and silane coupled group with polymerizable group.
There is not special qualification for compound, as long as it is that normally used silane coupling agent and its intramolecularly have polymerizable group, for example preferably with the represented compound of formula (1) with polymerizable group and silane coupled group.
General formula (1)
Figure S200810110607XD00081
In above-mentioned general formula (1), R 1, R 2And R 3Represent hydroxyl, alkoxyl group, acyloxy, amido or halogen atom independently of one another.
As above-mentioned alkoxyl group, can enumerate methoxyl group, oxyethyl group, propoxy-, butoxy, pentyloxy, benzyloxy, cyclohexyl oxygen base, Buddha's warrior attendant alkoxyl group, 2,4-dimethyl--3-pentyloxy, phenoxy etc.
As the acyl group in the above-mentioned acyloxy, can enumerate formyl radical, ethanoyl, propionyl group, butyryl radicals, isobutyryl, pentanoyl, isovaleryl, valeryl, caproyl, lauroyl, benzoyl-, methoxy aroyl, malonyl-, cyclohexyl-carbonyl etc.
As above-mentioned amido, can enumerate kharophen, formamido group, benzamido-etc.
As above-mentioned halogen atom, can enumerate chlorine, bromine, iodine etc.
In addition, the X in the general formula (1) representes polymerizable group.As this polymerizable group, can enumerate free-radical polymerised group, cationically polymerizable group etc., but consider from aspects such as keeping quality, light sensitivity, be preferably free-radical polymerised group.
As above-mentioned free-radical polymerised group, be preferably acryloxy, methacryloxy, acrylamido, methacrylamido.
As above-mentioned cationically polymerizable group, can enumerate cyclic ethers base (epoxy group(ing), oxa-cyclobutyl etc.), vinyl, lactone group, '-aziridino etc., wherein, be preferably vinyl or epoxy group(ing).
Y in the general formula (1) representes binding group that polymerizable group and silane coupled group are coupled together; It there is not special qualification; So long as do not hinder polymerization or silane coupled functional group to get final product, for example can be alkylidene group, arylidene, alkenylene, alkynylene etc.
As the object lesson of the represented compound of above-mentioned general formula (1), can enumerate the silica-based propyl ester of methylacrylic acid trimethoxy, the silica-based propyl ester of vinylformic acid trimethoxy, the silica-based propyl ester of methylacrylic acid trichlorine, the silica-based propyl ester of vinylformic acid trichlorine, the silica-based own ester of methylacrylic acid trimethoxy, the silica-based own ester of methylacrylic acid tribromo etc.
Wherein, the aspects such as internal homogeneity when reacting with support are considered, are preferably silica-based propyl ester of methylacrylic acid trimethoxy or the silica-based propyl ester of vinylformic acid trimethoxy.
In this operation, will have the coupling agent of above-mentioned polymerizable group and suitable solvent and be mixed with liquid composition, methods such as employing coating touch said composition on the support and distribute, and form membranaceous middle layer through removing to desolvate.In this film process, through linked reaction takes place, the coupling agent with polymerizable group is combined on the surface of support through coupling group, thereby forms the middle layer.
Consequently, through the present invention, can access middle layer with polymerizable group.
Solvent for when preparing above-mentioned liquid composition, being adopted does not have special qualification; As long as its boiling point below 150 ℃, can be enumerated water, acetone, methylethylketone, hexanaphthene, ETHYLE ACETATE, THF, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, glycol dimethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, methyl ethyl diketone, pimelinketone, methyl alcohol, ethanol, 1-methoxyl group-2-propyl alcohol, 3-methoxypropanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, acetate 3-methoxyl group propyl ester etc.
At this moment, the concentration of the coupling agent with polymerizable group in the liquid composition is preferably 0.01 quality %～30 quality %, is preferably the dizzy % of 0.1 matter～15 quality % especially.
From the reaction that prevents polymerizable group and need keep film-forming properties the aspect is considered to prevent that film from peeling off etc., the coated weight of the liquid composition when making coupling agent with polymerizable group and support carry out coupling in dried quality, is preferably 0.1～20g/m 2, 0.5～15g/m more preferably 2
In addition, when liquid composition was contacted with support, the liquid temperature of liquid composition was preferably 0 ℃～100 ℃.Be preferably 1 second duration of contact～50 hours, more preferably 10 seconds～10 hours.
Middle layer of the present invention is through removing behind the solvent in the liquid composition and film forming, at this moment, preferably heats so that film solidifies.
Heating temperature and time can be selected according to the condition of the solvent thorough drying that can make coating; But consider from the angle that is fit to make; Temperature is preferably below 100 ℃; Be preferably time of drying in 30 minutes, more preferably, it is that 40～80 ℃, time of drying are in 10 minutes that heating condition is chosen as drying temperature.
[support]
Especially, the support among the present invention is no matter it adopts Any shape, material, as long as the purposes of being applicable to.More particularly; As said support; Be preferably the plate object of dimensional stabilizing; For example; (for example can comprise glass substrate, paper, plastics; Vilaterm, Vestolen PP 7052, PS etc.) paper that forms behind the paper, metal sheet (for example, aluminium, zinc, copper etc.), plastics film (for example, secondary cellulose acetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, nitrocellulose, polyethylene terephthalate, Vilaterm, PS, Vestolen PP 7052, polycarbonate, polyvinyl acetal, polyimide, epoxy resin, bimaleimide resin, ppe, liquid crystalline polymers, tetrafluoroethylene etc.) and aforesaid metal laminate or the vapor deposition that form behind the lamination or plastics film etc.
As the support that uses among the present invention, be preferably epoxy resin or polyimide resin.
In addition, as in the situation of photomask, this support is preferably selected glass substrate for use at thin-layer metal membrane material of the present invention.
And the thickness of said glass substrate is preferably 0.1mm～20mm.
[(b1) forming operation] with (b2) polymer layer
In the present invention, form in the situation of operation at (b1) polymer layer, use be to contain compound compositions with crosslinkable groups, to form polymer layer; In addition, form in the situation of operation at (b2) polymer layer, use be to contain the compound with crosslinkable groups and the compsn of metals ion, to form polymer layer.
Specifically; In this operation, on the middle layer, in the above-mentioned compsn any one contacted with this middle layer; Apply energy to said composition according to the image shape then; Make polymerizable group and compound reaction in the middle layer, generating the polymkeric substance that directly is combined on this interlayer surfaces, and then form the polymer layer of image shape with said crosslinkable groups.
Below; With the compound compositions that contains that is adopted in (b1) operation with crosslinkable groups; And containing of (b2) being adopted in the operation compound with crosslinkable groups and the compsn of metals ion be referred to as " reactive composition ", and it is elaborated.
[compound] with crosslinkable groups
At first, compound with crosslinkable groups (below, abbreviate " cross-linked compound " as) is described.
As the cross-linked compound that uses among the present invention, as long as crosslinkable groups wherein has free-radical polymerised group or cationically polymerizable group, no matter it is monomer, oligopolymer, or polymkeric substance all can.Wherein, the preferred compound that metals ion is had high-affinity that adopts perhaps preferably has the compound (below, suitably be called " specific cross-linked compound ") of crosslinkable groups and adsorption of metal ions group.
As the crosslinkable groups that is contained in the above-mentioned cross-linked compound; As stated; Can enumerate free-radical polymerised group or cationically polymerizable group etc., but preferably select with above-mentioned (a) operation in polymerizable group in the formed middle layer group with sufficient copolymerization property.Particularly, the polymerizable group in the preferred said coupling agent with polymerizable group is identical functional group with crosslinkable groups in the above-mentioned compound with crosslinkable groups.
As above-mentioned free-radical polymerised group, be preferably acryloxy, methacryloxy, acrylamido, methacrylamido.
In addition,, for example, cyclic ethers base (epoxy group(ing), oxa-cyclobutyl etc.), vinyl, lactone group, '-aziridino etc. be can enumerate, vinyl or epoxy group(ing) wherein are preferably as above-mentioned cationically polymerizable group.
In the present invention, consider the preferred compound that adopts with free-radical polymerised group from aspects such as keeping quality, light sensitivity.
As the vinyl compound of one of compound with cationically polymerizable group, its concrete example can be enumerated distyryl compound, alkyl vinyl ether compound, thiazolinyl vinyl ether compound, aryl vinyl ether compound, polyfunctional vinyl compound, propenyl compound, pseudoallyl compound, cationically polymerizable nitrogenous compound etc.
In addition, as the epoxy compounds of one of compound with cationically polymerizable group, its concrete example can be enumerated various glycidyl ether type epoxy compoundss, alicyclic epoxy compound, epoxidized ethylene based compound etc.
In addition; As the adsorption of metal ions group in the cross-linked compound of the present invention, can enumerate nitrogen-containing functional group such as cyanic acid, isocyano-, amino, imino-, hydrazine, imidazolyl, imido grpup, urea groups, pyridyl, ammonium, pyrrolidone-base, cyanato, isocyanide acyl group, sulphur cyanato, different sulphur cyanato, carboxamido-group, triazine ring structure, formamyl, diazanyl carbonyl, the group that contains the isocyanide urea structure, carbamate groups, nitro, nitroso-group, azo-group, diazo, amidino groups, azido-, cyanate ester based (R-O-CN) etc.; Such as hydroxyl (also comprising phenol), ether, carbonyl, carboxyl, peroxycarboxyl groups, ester group, contain the N-oxide structure group, contain the S-oxide structure group, contain the oxygen-containing functional group of the group etc. of N-hydroxyl structure; Such as sulfydryl, thioether group, thioureido, thiocarbonyl (チ オ キ シ), sulfoxide group, sulfuryl, sulfurous acid ester group, the group of sulfur-bearing imide (sulfoximine) structure, the group that contains sulfoxonium (sulfoxonium) salt structure, thiocarboxyl group, dithiocarboxy, sulfoxylic acid ester group, sulfino, sulfinyl (sulfeno), oxygen base carbonyl (oxycarbonyl), contain the sulfur-bearing functional group of the group etc. of sulphonate structure; Such as phosphorous functional groups such as phosphine (phosphine) base, phosphino-(phosphino), phosphono, hydroxyl phosphoryls; Such as acidic groups such as carboxylic acid group, sulfonic group, phosphates; The group that contains halogen atoms such as chlorine, bromine, fluorine; And unsaturated alkyl such as alkene, alkynes, phenyl ring etc.Wherein, because the adsorptivity of carboxyl or its an alkali metal salt and metals ion is high, so preferred carboxyl or its an alkali metal salt.
Molecular weight for said cross-linked compound does not have special qualification, as long as this molecular weight can be so that this compound can be dissolved in the general solvent when applying, and can get final product through removing by filter unwanted solid.
Monomer as the specific cross-linked compound that uses among the present invention; Specifically, for example can enumerate (methyl) vinylformic acid or its an alkali metal salt and amine salt, methylene-succinic acid or its an alkali metal salt and amine salt, styrene sulfonic acid or its an alkali metal salt and amine salt, (methyl) vinylformic acid 2-sulfo group ethyl ester or its an alkali metal salt and amine salt, 2-acrylamido-2-methyl propane sulfonic acid or its an alkali metal salt and amine salt, phosphorus acyloxy polyoxyethylene glycol list (methyl) propenoate or its an alkali metal salt and amine salt, polyoxyethylene glycol list (methyl) propenoate, (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) acrylic amide, N-monomethylol (methyl) acrylic amide, N-dihydroxymethyl (methyl) acrylic amide, allyl amine or its hydrogen halide hydrochlorate, N-vinyl pyrrolidone, vinyl imidazole, vinyl pyridine, vinyl thiophene, vinylbenzene, to have carbonatoms such as (methyl) ethyl propenoate, (methyl) n-butyl acrylate etc. be (methyl) propenoate of 1～24 alkyl etc.
In addition, as the macromonomer of spendable specific cross-linked compound among the present invention, can adopt known method to make by above-mentioned monomer.As the method for manufacture of the macromonomer that uses in this embodiment, for example in the 2nd chapter " マ Network ロ モ ノ マ one is synthetic " of September in 1989 " マ Network ロ モ ノ マ one chemical と industry " (hero also under the editor mountain) that ア イ on the 20th ピ one シ one press issues, various method of manufacture have been proposed.
The weight-average molecular weight of useful this macromonomer is 500～500,000, is preferably 1000～50,000 especially.
As the polymkeric substance of spendable specific cross-linked compound among the present invention, preferably in this polymkeric substance, introduce alkene addition polymerization property unsaturated groups (polymerizable group) such as adsorption of metal ions group and vinyl, allyl group, (methyl) acryl.This polymkeric substance at least endways or on side chain, have alkene addition polymerization property unsaturated group further preferably has alkene addition polymerization property unsaturated group on side chain, more preferably reach endways on side chain, all to have alkene addition polymerization property unsaturated group.
The weight-average molecular weight of useful this macromolecular compound is 500～500,000, is preferably 1000～50,000 especially.
As the compound method of macromolecular compound, can enumerate following method: i) will have the monomer of adsorption of metal ions group and have the method for the monomer copolymerization of 2 above polymerizable groups with adsorption of metal ions group and polymerizable group; Monomer that ii) will have an adsorption of metal ions group and monomer copolymerization with polymerizable group precursor, the processing through alkali etc. is to introduce the method for two keys then; Iii) make polymkeric substance with adsorption of metal ions group and monomer reaction, to introduce the method for polymerizable group with polymerizable group.
Consider that from being suitable for the synthetic angle preferred compound method is: ii) will have the monomer and the monomer copolymerization with polymerizable group precursor of adsorption of metal ions group, the processing through alkali etc. is to introduce the method for polymerizable group then; Iii) make polymkeric substance with adsorption of metal ions group and monomer reaction, to introduce the method for polymerizable group with polymerizable group.
As at above-mentioned i) and compound method ii) in the monomer that adopted with adsorption of metal ions group; Can enumerate for example (methyl) vinylformic acid or its an alkali metal salt and amine salt, methylene-succinic acid or its an alkali metal salt and amine salt; More particularly; For example can enumerate (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) acrylic amide, N-monomethylol (methyl) acrylic amide, N-dihydroxymethyl (methyl) acrylic amide, allyl amine or its hydrogen halide hydrochlorate, 3-vinyl propionic acid or its an alkali metal salt and amine salt, vinyl sulfonic acid or its an alkali metal salt and amine salt, (methyl) vinylformic acid 2-sulfo group ethyl ester, polyoxyethylene glycol list (methyl) propenoate, 2-acrylamido-2-methyl propane sulfonic acid, phosphorus acyloxy polyoxyethylene glycol list (methyl) propenoate, N-vinyl pyrrolidone (structure shown in the hereinafter), SSS, vinyl TRIMETHOXY BENZOIC ACID (FOR MANUFACTURING OF T.M. etc.In general, can use have carboxyl, the monomer of sulfonic group, phosphate, amino or its salt, hydroxyl, carboxamido-group, phosphino-, imidazolyl, pyridyl or functional groups such as their salt and ether.Particularly, owing to have the monomer of carboxyl or its an alkali metal salt and the adsorptivity height of metals ion, so the preferred monomer that uses with carboxyl or its an alkali metal salt.
Figure S200810110607XD00141
At above-mentioned i) compound method in, as can with above-mentioned monomer with 2 above polymerizable groups with monomer copolymerization of adsorption of metal ions group, can enumerate (methyl) allyl acrylate, methylacrylic acid 2-allyl group oxygen base ethyl ester.
In addition; As the monomer that in above-mentioned compound method ii), is adopted with polymerizable group precursor; Can use the compound put down in writing in methylacrylic acid 2-(3-chloro-1-carbonyl propoxy-) ethyl ester or the TOHKEMY 2003-335814 communique (i-1～i-60); Wherein, preferred especially following compound (i-1).
Figure S200810110607XD00142
Compound (i-1)
In addition; Utilize with above-mentioned compound method iii) in carboxyl, amino or its salt, hydroxyl, and the reaction of functional groups such as epoxy group(ing) during in the polymkeric substance that adopted with the introducing polymerizable group with adsorption of metal ions group; As the monomer that is adopted, can enumerate (methyl) vinylformic acid, (methyl) glycidyl acrylate, allyl glycidyl ether, (methyl) vinylformic acid 2-isocyanide acyl group ethyl ester etc. with polymerizable group.
In above-mentioned compound method ii); After making monomer and having the monomer generation copolymerization of polymerizable group precursor, for example can adopt the method for putting down in writing in the TOHKEMY 2003-335814 communique with the method for introducing polymerizable group through the processing of alkali etc. with adsorption of metal ions group.
In the present invention; As specific cross-linked compound, preferred use have acidic groups such as carboxylic acid group's (carboxyl), sulfonic group, phosphate, its an alkali metal salt or amino polymkeric substance (below be called " the bridging property polymkeric substance that contains polar group ") as the adsorption of metal ions group.
Particularly, as the bridging property polymkeric substance that contains polar group, preferably, those contain have the carboxylic acid group (carboxyl), sulfonic group, phosphate, they an alkali metal salt or amino unit and after unitary multipolymer shown in the general formula (1) stated.In addition, this multipolymer also can be also to contain other unitary terpolymer.
As having carboxylic acid group's (carboxyl), sulfonic group, phosphate, their an alkali metal salt or amino unit; Get final product so long as have the formed unit of the monomer of these functional groups (repeating unit); Specifically, can enumerate above-mentioned at i) and ii) employed formed unit such as monomer in the compound method with adsorption of metal ions group.
In addition, contain about formation polar group the bridging property polymkeric substance by the unit shown in the general formula (1), with constitute after the bridging property polymkeric substance that contains cyanic acid stated by the unit synonym shown in the general formula (1), its preferred example is also identical.
Here, in containing the bridging property polymkeric substance of polar group,, have carboxylic acid group's (carboxyl), sulfonic group, phosphate or amino unit and the represented shared ratio in unit of general formula (1) and distinguish preferred in following scope with respect to all copolymer compositions.
Promptly; From considering with the adsorptivity aspect of metals ion; Have 10 moles of % to 95 mole of % that carboxylic acid group's (carboxyl), sulfonic group, phosphate, their an alkali metal salt or amino unit preferably account for all copolymer compositions, more preferably account for 30 moles of % to 70 mole of %.
In addition, from reactive (solidified nature, polymerizability) and synthetic angle consideration easily, the represented unit of general formula (1) preferably accounts for 2 moles of % to 20 mole of % of all copolymer compositions, more preferably accounts for 5 moles of % to 10 mole of %.
The molecular weight (Mw) of the bridging property polymkeric substance that contains polar group among the present invention is preferably 5000 to 50000, and more preferably 7000 to 25000.
Though below show the object lesson [example compound (1)～(21)] of the bridging property polymkeric substance that contains polar group among the present invention, the present invention is not limited thereto.
Figure S200810110607XD00171
Figure S200810110607XD00181
Figure S200810110607XD00191
In addition, among the present invention,, also can adopt to have with cyanic acid as the polymkeric substance of adsorption of metal ions group (below, be called " cross-linked polymer that contains cyanic acid ") as said specific cross-linked compound.
The cross-linked polymer that contains cyanic acid among the present invention for example is preferably and contains unitary multipolymer shown in the unit and following formula (2) shown in following formula (1).
Figure S200810110607XD00201
In above-mentioned formula (1) and formula (2), R 1～R 5Represent Wasserstoffatoms independently of one another, perhaps replace or unsubstituted alkyl; X, Y and Z represent singly-bound independently of one another, replace or unsubstituted divalent organic group ester group, carboxamido-group, perhaps ether; L 1And L 2Expression independently of one another replaces or unsubstituted divalent organic group.
At R 1～R 5In the situation for replacement or unsubstituted alkyl,, can enumerate methyl, ethyl, propyl group, butyl as unsubstituted alkyl; In addition, as substituted alkyl, can enumerate by substituted methyl, ethyl, propyl group, butyl such as methoxyl group, hydroxyl, chlorine atom, bromine atoms, fluorine atoms.
Also have, as R 1, be preferably Wasserstoffatoms, methyl, or by hydroxyl or the substituted methyl of bromine atoms.
As R 2, be preferably Wasserstoffatoms, methyl, or by hydroxyl or the substituted methyl of bromine atoms.
As R 3, be preferably Wasserstoffatoms.
As R 4, be preferably Wasserstoffatoms.
As R 5, be preferably Wasserstoffatoms, methyl.
In X, Y and Z situation,, can enumerate replacement or unsubstituted aliphatic group, replacement or unsubstituted aromatics base as this divalent organic group for replacement or unsubstituted divalent organic group.
As replacing or unsubstituted aliphatic group, be preferably methylene radical, ethylidene, propylidene, butylidene, perhaps by substituted these groups such as methoxyl group, hydroxyl, chlorine atom, bromine atoms, fluorine atoms.
As replacing or the unsubstituted aromatics base, be preferably unsubstituted phenyl, perhaps by substituted phenyl such as methoxyl group, hydroxyl, chlorine atom, bromine atoms, fluorine atoms.
Wherein, be preferably-(CH 2) n-(n is 1～3 integer), more preferably-CH 2-.
L 1Be preferably the divalent organic group with carbamate groups or urea groups, wherein, preferably its total carbon atom number is 1～9.In addition, here, so-called L 1Total carbon atom number be meant L 1The total carbon atom number that contains in represented replacement or the unsubstituted divalent organic group.
L 1Structure, more particularly, be preferably following formula (1-1) or the represented structure of formula (1-2).
Figure S200810110607XD00211
In above-mentioned formula (1-1) and the formula (1-2), R aAnd R bExpression independently of one another replaces or unsubstituted methylene radical, ethylidene, propylidene or butylidene.
In addition, L 2Be preferably straight chain, side chain or cyclic alkylidene group, aromatic base, the group that perhaps forms after these moiety combinations.In addition, can also this alkylidene group and aromatic base be made up through ether, ester group, carboxamido-group, carbamate groups, the such group of urea groups.Wherein, L 2Total carbon atom number be preferably 1～15, and L 2Be preferably unsubstituted above-mentioned group especially.In addition, here, so-called L 2Total carbon atom number be meant L 2The total carbon atom number that contains in represented replacement or the unsubstituted divalent organic group.
Specifically, can enumerate methylene radical, ethylidene, propylidene, butylidene, phenylene, and, also have the group that forms after these moiety combinations by substituted these groups such as methoxyl group, hydroxyl, chlorine atom, bromine atoms, fluorine atoms.
In as the cross-linked polymer that contains cyanic acid among the present invention, the represented unit of above-mentioned formula (1) is preferably the represented unit of following formula (3).
Figure S200810110607XD00221
In the above-mentioned formula (3), R 1And R 2Represent Wasserstoffatoms independently of one another, perhaps replace or unsubstituted alkyl; Z representes singly-bound, replacement or unsubstituted divalent organic group, ester group, carboxamido-group or ether; W representes nitrogen-atoms or Sauerstoffatom; L 1Expression replaces or unsubstituted divalent organic group.
R in the formula (3) 1And R 2With the R in the above-mentioned formula (1) 1And R 2Same meaning, its preferred example is also identical.
Z same meaning in Z in the formula (3) and the above-mentioned formula (1), its preferred example is also identical.
In addition, the L in the formula (3) 1With the L in the above-mentioned formula (1) 1Same meaning, its preferred example is also identical.
In as the cross-linked polymer that contains cyanic acid among the present invention, the represented unit of above-mentioned formula (3) is preferably the represented unit of following formula (4).
In the formula (4), R 1And R 2Represent Wasserstoffatoms independently of one another, perhaps replace or unsubstituted alkyl; V and W represent nitrogen-atoms or Sauerstoffatom independently of one another; L 1Expression replaces or unsubstituted divalent organic group.
R in the formula (4) 1And R 2With the R in the above-mentioned formula (1) 1And R 2Same meaning, its preferred example is also identical.
L in the formula (4) 1With the L in the above-mentioned formula (1) 1Same meaning, its preferred example is also identical.
In above-mentioned formula (3) and the formula (4), W is preferably Sauerstoffatom.
In addition, in above-mentioned formula (3) and the formula (4), L 1Be preferably unsubstituted alkylidene group, perhaps have the divalent organic group of carbamate groups or urea groups, wherein, preferred especially total carbon atom number is 1～9.
In addition, in as the cross-linked polymer that contains cyanic acid among the present invention, the represented unit of above-mentioned formula (2) is preferably the represented unit of following formula (5).
Figure S200810110607XD00231
In the above-mentioned formula (5), R 2The expression Wasserstoffatoms perhaps replaces or unsubstituted alkyl; U representes nitrogen-atoms or Sauerstoffatom; L 2Expression replaces or unsubstituted divalent organic group.
R in the formula (5) 2With the R in the above-mentioned formula (1) 1And R 2Same meaning is preferably Wasserstoffatoms.
In addition, the L in the formula (5) 2With the L in the above-mentioned formula (2) 2Same meaning is preferably straight chain, side chain or cyclic alkylidene group, aromatic base, perhaps the group that constitutes of these moiety combinations.
Particularly, in formula (5), with position that cyanic acid is connected on, L 2Be preferably and have divalent organic group straight chain, side chain or the cyclic alkylidene group, wherein, the total carbon atom number of this divalent organic group is preferably 1～10.
In addition, as other preferred embodiment, with position that cyanic acid is connected on, the L in the formula (5) 2Be preferably the divalent organic group with aromatic base, wherein, the total carbon atom number of this divalent organic group is preferably 6～15.
The cross-linked polymer that contains cyanic acid among the present invention is by the represented unit of above-mentioned formula (1)～formula (5) polymkeric substance that constitute, that on its side chain, have polymerizable group and cyanic acid.
This contains the cross-linked polymer of cyanic acid, for example can adopt following method synthetic.
The kind of polyreaction can be enumerated radical polymerization, cationoid polymerisation, anionoid polymerization.Consider from the angle of reaction control, preferably adopt radical polymerization, cationoid polymerisation.
The cross-linked polymer that contains cyanic acid of the present invention; 1) form the polymerization methods of main polymer chain and on side chain, introduce in the polymerization methods condition of different of polymerizable group; And 2) form in the polymerization methods of the main polymer chain situation identical with the polymerization methods of on side chain, introducing polymerizable group, the compound method that both adopt is different.
1) forms the polymerization methods of main polymer chain and the polymerization methods condition of different of on side chain, introducing polymerizable group
Form the polymerization methods of main polymer chain and have following two kinds of embodiments: 1-1) form main polymer chain, and the polymerization methods of introducing polymerizable group is the embodiment of radical polymerization on side chain through cationoid polymerisation with the polymerization methods condition of different of on side chain, introducing polymerizable group; 1-2) through the incompatible formation main polymer chain of radical polymerization, and the polymerization methods of introducing polymerizable group is the embodiment of cationoid polymerisation on side chain.
1-1) form the main chain of polymkeric substance through cationoid polymerisation, and the polymerization methods of on side chain, introducing polymerizable group is the embodiment of radical polymerization
Among the present invention, forming main polymer chain through cationoid polymerisation, and the polymerization methods of introducing polymerizable group is in the embodiment of radical polymerization on side chain, the monomer that is adopted can be enumerated following compound.
Be used to form the unitary monomer that contains polymerizable group
The employed unitary monomer that contains polymerizable group that is used to form in this embodiment; Can enumerate (methyl) vinylformic acid vinyl ester, (methyl) allyl acrylate, 4-(methyl) acryl butyl vinyl ether, 2-(methyl) acryl ethyl vinyl ether, 3-(methyl) acryl propyl vinyl ether, (methyl) acryloxy Diethylene Glycol vinyl ether, (methyl) acryloxy triethylene glycol vinyl ether, (methyl) acryl α-terpinol, 1-(methyl) acryloxy-2-methyl-2-propylene, 1-(methyl) acryloxy-3-methyl-3-butylene, 3-methylene radical-2-(methyl) acryloxy-norbornane, 4,4 '-ethylene phenol two (methyl) propenoate, methacrylaldehyde two (methyl) acryl acetal, right-((methyl) acryl methyl) vinylbenzene, (methyl) allyl acrylate, 2-(brooethyl) vinyl acrylate, 2-(methylol) allyl acrylate etc.
Be used to form the unitary monomer that contains cyanic acid
Used being used to form contains the unitary monomer of cyanic acid in this embodiment, can enumerate 2-cyano ethyl vinyl ether, cyano methyl vinyl ether, 3-cyanic acid propyl vinyl ether, 4-cyanic acid butyl vinyl ether, 1-(right-cyano-benzene oxygen)-2-vinyloxy group ethane, 1-(neighbour-cyano-benzene oxygen)-2-vinyloxy group ethane, 1-(-cyano-benzene oxygen)-2-vinyloxy group ethane, 1-(right-cyano-benzene oxygen)-3-vinyloxy group propane, 1-(right-cyano-benzene oxygen)-4-vinyloxy group butane, neighbour-cyanic acid benzyl vinyl ether ,-cyanic acid benzyl vinyl ether, right-the cyanic acid benzyl vinyl ether, allyl group cyaniding thing, allyl cyanide guanidine-acetic acid and following shown in compound etc.
Figure S200810110607XD00251
General cationic polymerization process of putting down in writing in the method that polymerization method can use record in experimental chemistry lecture " polymer chemistry " the 2nd chapter-4 (p74) and " Gao Fen He Cheng experiment method " (the grand row work in big Tianjin) the 7th chapter (p195).In addition; In cationoid polymerisation; Can adopt protonic acid, metal halide, organometallic compound, organic salt, MOX, solid acid and halogen as initiator; Wherein,, initiator that can synthetic macromolecule weight polymers highly active as having preferably uses metal halide and organometallic compound.
Specifically, can enumerate boron trifluoride, boron trichloride, aluminum chloride, alchlor, titanium tetrachloride, tin tetrachloride, Tin tetrabromide, phosphorus pentafluoride, antimony chloride, molybdenum chloride, tungsten chloride, iron(ic)chloride, ethyl aluminum dichloride, aluminium diethyl monochloride, dichloromethyl aluminium, a Chlorodimethyl aluminium, trimethylaluminium, trimethylammonium zinc, methyl Grignard reagent.
1-2) through the incompatible formation main polymer chain of radical polymerization, and the polymerization methods of introducing polymerizable group is the embodiment of cationoid polymerisation on side chain
Among the present invention, passing through the incompatible formation main polymer chain of radical polymerization, and the polymerization methods of introducing polymerizable group is in the embodiment of cationoid polymerisation on side chain, the monomer that is adopted can be enumerated following compound.
Be used to form the unitary monomer that contains polymerizable group
Can adopt and above-mentioned 1-1) embodiment in cited being used to form contain the identical monomer of unitary monomer of polymerizable group.
Be used to form the unitary monomer that contains cyanic acid
That in this embodiment, uses is used to form the unitary monomer that contains cyanic acid; Can enumerate (methyl) vinylformic acid cyanic acid methyl esters, (methyl) 2 cyanoethyl acrylate, (methyl) vinylformic acid 3-cyanic acid propyl ester, (methyl) vinylformic acid 2-cyanic acid propyl ester, (methyl) vinylformic acid 1-cyanic acid ethyl ester, (methyl) vinylformic acid 4-cyanic acid butyl ester, (methyl) vinylformic acid 5-cyanic acid pentyl ester, the own ester of (methyl) vinylformic acid 6-cyanic acid, (methyl) vinylformic acid 7-cyanic acid heptyl ester, (methyl) vinylformic acid 8-cyanic acid monooctyl ester, 3-(brooethyl) 2 cyanoethyl acrylate, 3-(methylol) 2 cyanoethyl acrylate, (methyl) vinylformic acid right-cyanobenzene ester, (methyl) vinylformic acid neighbour-cyanobenzene ester, (methyl) vinylformic acid between-cyanobenzene ester, 5-(methyl) acryl-2-itrile group-norbornylene, 6-(methyl) acryl-2-itrile group-norbornylene, 1-cyanic acid-1-(methyl) acryl hexanaphthene, 1; Between 1-dimethyl--1-cyanic acid-(methyl) propenoate, 1-methyl isophthalic acid-ethyl-1-cyanic acid-(methyl) propenoate, (methyl) vinylformic acid neighbour-cyanic acid benzyl ester, (methyl) vinylformic acid-and cyanic acid benzyl ester, (methyl) vinylformic acid be right-cyanic acid benzyl ester, vinylformic acid 1-cyanic acid suberyl ester, vinylformic acid 2-cyanobenzene ester, vinylformic acid 3-cyanobenzene ester, cyanoacetic acid vinyl acetate, 1-cyanic acid-1-cyclopropane carboxylic acid vinyl acetate, cyanoacetic acid allyl ester, 1-cyanic acid-1-cyclopropane carboxylic acid allyl propionate, N, N-dicyano methyl (methyl) acrylic amide, N-cyano-phenyl (methyl) acrylic amide, allyl cyanide ylmethyl ether, allyl group-neighbour-cyanic acid benzylic ether, allyl group--cyanic acid benzylic ether, allyl group-right-cyanic acid benzylic ether etc.
In addition, also can use a part of hydrogen that has in above-mentioned monomer to be replaced afterwards and the monomer of the structure that forms by hydroxyl, alkoxyl group, halogen, cyanic acid etc.
General free radical polymerisation process of putting down in writing in the method that polymerization method can use record in experimental chemistry lecture " polymer chemistry " the 2nd chapter-2 (p34) and " Gao Fen He Cheng experiment method " (the grand row work in big Tianjin) the 5th chapter (p125).In addition; Initiator for radical polymerization; Known have must be heated to more than 100 ℃ just can initiated polymerization high-temperature initiator, be heated to 40～100 ℃ can initiated polymerization common initiator, redox initiator that can initiated polymerization under extremely low temperature etc.; But consider from the angle of the convenient processing degree of the stability of initiator, polyreaction, preferably use common initiator.
As common initiator, it is two-2 to enumerate Lucidol, lauroyl peroxide, peroxo-dithionate, Diisopropyl azodicarboxylate, azo, the 4-methyl pentane nitrile.
2) form the polymerization methods of main polymer chain and the identical situation of polymerization methods of on side chain, introducing polymerizable group
Form the polymerization methods of main polymer chain and have following two kinds of embodiments with the identical situation of polymerization methods of on side chain, introducing polymerizable group: 2-1) both are the embodiment of cationoid polymerisation; 2-2) both are the embodiment of radical polymerization.
2-1) both are the embodiment of cationoid polymerisation
Be in the embodiment of cationoid polymerisation at both,, can adopt and above-mentioned 1-1 as monomer with cyanic acid) embodiment in cited being used to form contain the identical monomer of unitary monomer of cyanic acid.
In addition; The angle that gelation takes place from prevent polymerization process is considered; Preferred adopt is, synthetic in advance polymkeric substance with cyanic acid, then with this polymkeric substance and compound with polymerizable group (below; Suitably be called " reactive compounds ") reaction, to introduce the method for polymerizable group.
In addition, in order to react with reactive compounds, said polymkeric substance with cyanic acid preferably has reactive group as follows.
In addition, polymkeric substance and reactive compounds with cyanic acid are preferably suitably selected, so that they have the combination of following functional group.
Specifically; As described combination, can enumerate (reactive group of polymkeric substance, the functional group of reactive compounds)=(carboxyl, carboxyl), (carboxyl, epoxy group(ing)), (carboxyl, NCO), (carboxyl, halogeno-benzyl), (hydroxyl, carboxyl), (hydroxyl, epoxy group(ing)), (hydroxyl, NCO), (hydroxyl, halogeno-benzyl), (NCO, hydroxyl), (NCO, carboxyl) etc.
As reactive compounds, specifically, can adopt compound as follows here.
That is, allyl alcohol, 4-hydroxybutyl vinyl ether, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, hydroxyl triethylene glycol vinyl ether, α-terpinol, 2-methyl-2-propyl alcohol, 3-methyl-3-butanols, 3-methylene radical-2-hydroxyl norbornane, right-(chloromethyl) vinylbenzene.
2-2) both are the embodiment of radical polymerization
Be in the embodiment of radical polymerization at both,, following method arranged: i) will have the monomer of cyanic acid and have the method for the monomer copolymerization of polymerizable group as compound method; Ii) make monomer with cyanic acid and the monomer copolymerization with two key precursors, the processing through alkali etc. is to introduce the method for pair keys then; Iii) make polymkeric substance with cyanic acid and monomer reaction, to introduce the method for two keys (introducing polymerizable group) with polymerizable group.From being applicable to that the synthetic angle considers, preferably: ii) make monomer with cyanic acid and the monomer copolymerization with two key precursors, the processing through alkali etc. is to introduce the method for pair keys then; Iii) make polymkeric substance with cyanic acid and monomer reaction, to introduce the method for polymerizable group with polymerizable group.
At above-mentioned i) compound method in the monomer that adopted with polymerizable group, can enumerate (methyl) allyl acrylate and following shown in compound etc.
As the monomer that in above-mentioned compound method ii), is adopted, can enumerate the represented compound of following formula (a) etc. with two key precursors.
Figure S200810110607XD00282
In the above-mentioned formula (a), A representes to have organic atomic radical of polymerizable group; R 1～R 3Represent Wasserstoffatoms independently of one another, perhaps any monovalent organic radical group; B and C represent can be through eliminating the leavings group that reaction is removed, and here, so-called elimination reaction is meant under the effect of alkali, sloughs C, and the reaction that B is left away.Preferred B is sloughed with cationic form with anionic form, C.
The represented compound of formula (a) specifically can be enumerated following compound.
Figure S200810110607XD00291
Figure S200810110607XD00301
In addition, in above-mentioned compound method ii), when two key precursors being converted into two key, can adopt as follows passing through to eliminate the method that B, the represented leavings group of C are removed in reaction, that is, under the effect of alkali, slough C, and the reaction that B is left away.
Figure S200810110607XD00302
As the alkali that in above-mentioned elimination reaction, is adopted,, can enumerate alkali-metal hydrogenate, oxyhydroxide or carbonate as preferred example; Organic amine compound; The metal alkyl oxide.The preferred example of alkali-metal hydrogenate, oxyhydroxide or carbonate can be enumerated sodium hydride, hydrolith, potassium hydride KH, sodium hydroxide, Pottasium Hydroxide, calcium hydroxide, salt of wormwood, yellow soda ash, saleratus, sodium hydrogencarbonate etc.The preferred example of organic amine compound can be enumerated Trimethylamine, triethylamine, diethylmethyl amine, TBuA, triisobutyl amine, three hexyl amines, trioctylphosphine amine, N, N-dimethylcyclohexylamine, N, N-diethyl cyclohexylamine, N-methyl bicyclic hexylamine, N-ethyl dicyclohexyl amine, tetramethyleneimine, 1-crassitude, 2; 5-dimethyl pyrrolidine, piperidines, 1-methyl piperidine, 2,2,6; 6-tetramethyl piperidine, piperazine, 1, the peaceful ring of 4-lupetazin, quinoline is fixed, 1,4-diazabicyclo [2; 2; 2]-and octane, urotropin, morpholine, 4-methylmorpholine, pyridine, picoline, 4-dimethylaminopyridine, lutidine, 1,8-diazabicyclo [5,4; 0]-and 7-hendecene (DBU), N, N '-dicyclohexyl carbon imide (DCC), diisopropyl ethyl amine, Schiff alkali etc.The preferred example of metal alkyl oxide can be enumerated sodium methylate, sodium ethylate, potassium tert.-butoxide etc.These alkali can use separately, also can two or more mixing use.
In addition; In above-mentioned elimination reaction; The solvent that is adopted when giving (interpolation) alkali; Can enumerate for example ethylene dichloride, pimelinketone, methylethylketone, acetone, methyl alcohol, ethanol, propyl alcohol, butanols, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, acetate 2-methoxyl group ethyl ester, 1-methoxyl group-2-propyl alcohol, acetate 1-methoxyl group-2-propyl ester, N, dinethylformamide, DMAC N,N, DMSO 99.8MIN., toluene, ETHYLE ACETATE, methyl lactate, ethyl lactate, water or the like.These solvents can use separately, also can two or more mixing use.
With respect to the amount of the particular functional group in the compound (B, the represented leavings group of C), the consumption of alkali can be below equivalent, also can be more than the equivalent.In addition, in the situation of using excessive alkali, eliminate the remaining alkali in reaction back, preferably add acid etc. in order to remove.
In above-mentioned compound method iii); As with the monomer with polymerizable group of polymer reaction with cyanic acid; According to the difference of the kind of the reactive group in the polymkeric substance with cyanic acid and difference, can use the monomer of functional group with following combination.
That is, (reactive group of polymkeric substance, monomeric functional group)=(carboxyl, carboxyl), (carboxyl, epoxy group(ing)), (carboxyl, NCO), (carboxyl, halogeno-benzyl), (hydroxyl, carboxyl), (hydroxyl, epoxy group(ing)), (hydroxyl, NCO), (hydroxyl, halogeno-benzyl), (NCO, hydroxyl), (NCO, carboxyl) etc.
Specifically, can use following monomer.
Figure S200810110607XD00311
In adopting the above method institute synthetic cross-linked polymer that contains cyanic acid of the present invention, with respect to all copolymer compositions, the unitary ratio that contains the unitary ratio of polymerizable group and contain cyanic acid is preferably in following scope.
That is, with respect to all copolymer compositions, the unitary ratio that contains polymerizable group is preferably in the scope of 5 moles of %～50 mole %, more preferably in the scope of 5 moles of %～40 mole %.If ratio is 5 moles below the %, then reactive (hardening, polymerizability) can reduce; If ratio is 50 moles more than the %, be difficult to synthesize thereby gelation takes place easily when then synthetic.
In addition, with respect to all copolymer compositions, the unitary ratio that contains cyanic acid is preferably in the scope of 1 mole of %～95 mole %, more preferably in the scope of 10 moles of %～95 mole %.
Also have, the cross-linked polymer that contains cyanic acid among the present invention except having the unit that contains cyanic acid and containing the unit of polymerizable group, can also have other unit.As being used to form other unitary monomers, only otherwise damage effect of the present invention, can use any monomer.
But, make as previously mentioned polymerizable group and polymer reaction with the situation of introducing these polymerizable groups in, be difficult to 100% when introducing, can residual a spot of reactive part, these parts also might become the 3rd kind of unit.
Specifically; In passing through the situation of the incompatible formation main polymer chain of radical polymerization; Can use unsubstituted (methyl) esters of acrylic acids such as (methyl) ethyl propenoate, (methyl) Bing Xisuandingzhi, (methyl) NSC 11786, (methyl) 2-EHA, (methyl) cyclohexyl acrylate, (methyl) benzyl acrylate, (methyl) vinylformic acid stearyl; (methyl) vinylformic acid 2; 2; 2-trifluoro ethyl ester, (methyl) vinylformic acid 3; 3, halogen substituted (methyl) esters of acrylic acids such as 3-trifluoro propyl ester, (methyl) vinylformic acid 2-chloroethene ester, ammonium substituted (methyl) esters of acrylic acids such as 2-(methyl) acryloxy ethyl-trimethyl salmiac; (methyl) acrylic amides such as butyl (methyl) acrylic amide, sec.-propyl (methyl) acrylic amide, octyl group (methyl) acrylic amide, dimethyl-(methyl) acrylic amide; Vinylbenzene, vinyl TRIMETHOXY BENZOIC ACID (FOR MANUFACTURING OF T.M., right-styrenics such as vinyl benzyl chlorination ammonium, vinyl compound classes such as N-VCz, vinyl-acetic ester, N-vinyl acetamide, N-caprolactam, and other (methyl) vinylformic acid dimethylamino ethyl ester, (methyl) vinylformic acid diethylamino ethyl ester, (methyl) vinylformic acid 2-ethylmercapto group-ethyl ester, (methyl) vinylformic acid, (methyl) vinylformic acid 2-hydroxy methacrylate etc.
In addition, also can use the macromonomer that obtains by above-mentioned monomer.
Forming through cationoid polymerisation in the situation of main polymer chain; Can use ethyl vinyl ether, butyl vinyl ether, IVE, cyclohexyl vinyl ether, ethylene glycol vinyl ether, two (terepthaloyl moietie) vinyl ether, 1; Vinyl ethers such as 4-butyleneglycol vinyl ether, 2-chloroethyl vinyl ether, 2-ethylhexyl vinyl ether, vinyl-acetic ester, 2-vinyl oxygen base tetrahydropyrans, phenylformic acid vinyl ester, butyric acid vinyl ester; Styrenics such as vinylbenzene, right-chloro-styrene, p-methoxystyrene, end such as allyl alcohol, 4-hydroxyl-1-butylene is the compound of vinyl etc.
The molecular weight (Mw) of the cross-linked polymer that contains cyanic acid among the present invention is preferably 3000～200,000, and more preferably 4000～100,000.
Below show the object lesson of the cross-linked polymer that contains cyanic acid among the present invention, but be not limited thereto.
Also have, the weight-average molecular weight of these object lessons is all in 3000～100000 scope.
The polymkeric substance that obtains in embodiment 1-1)
Figure S200810110607XD00341
The polymkeric substance that obtains in embodiment 1-2)
Figure S200810110607XD00351
The polymkeric substance that obtains in embodiment 2-1)
Figure S200810110607XD00361
The polymkeric substance that obtains in embodiment 2-2)
Figure S200810110607XD00371
The polymkeric substance that obtains in embodiment 2-2)
Figure S200810110607XD00381
Here; For example; The compound 2-2-11 of above-mentioned concrete example adopts following method synthetic: vinylformic acid and 2 cyanoethyl acrylate are dissolved in (for example) N-Methyl pyrrolidone; Adopt (for example) Diisopropyl azodicarboxylate (AIBN)) carry out radical polymerization as polymerization starter; Adopt the catalyzer of benzyltriethylammoinium chloride and so on then, and under the state of the polymerization terminator that adds Tert. Butyl Hydroquinone and so on, SY-Monomer G is carried out addition reaction and the synthetic compound 2-2-11 that obtains.
Here; For example; The compound 2-2-19 of above-mentioned concrete example adopts following method synthetic: with monomer shown in following and vinylformic acid right-cyanic acid benzyl ester is dissolved in N; In the solvent of N-DMAA and so on, adopt the polymerization starter of azo-bis-iso-dimethyl and so on to carry out radical polymerization, adopt the alkali of triethylamine and so on to remove hydrochloric acid and synthetic obtaining then.
Figure S200810110607XD00391
In addition, in the present invention, also can use in advance and introduce the cross-linked compound that metals ion is arranged at intramolecularly, to form polymer layer.In addition; As the metals ion that is introduced in this cross-linked compound, can enumerate silver ions, copper (I) ion, copper (II) ion, palladium (II) ion, palladium (IV) ion, aluminum ion, nickel ion, iron (II) ion, iron (III) ion, ruthenium ion, rhodium ion, tin ion etc.Wherein, consider preferred silver ions, palladium ion from being easy to the reductive angle.
Introduce the cross-linked compound that metals ion is arranged as intramolecularly, can enumerate vinylformic acid silver, vinylformic acid copper (I), vinylformic acid copper (II), vinylformic acid palladium (II), 3-acryloxy propionic silver etc.
In addition, introduce the cross-linked compound that metals ion is arranged, also can adopt polymkeric substance as follows [example compound (M1) and (M2)] etc. as intramolecularly.
Figure S200810110607XD00392
In the reactive composition that this operation adopted, the cross-linked compound among the present invention preferably accounts for 30 quality %～99 quality %, more preferably accounts for 40 quality %～70 quality %.
In addition, these cross-linked compounds can a kind of independent use, also can two or morely share.
[metals ion]
In (b2) polymer layer forms operation, need to use except containing above-mentioned compound with crosslinkable groups, also contain the reactive composition of metals ion, to form polymer layer.
As the metals ion that can adopt, can enumerate silver ions, copper (I) ion, copper (II) ion, palladium (II) ion, palladium (IV) ion, aluminum ion, nickel ion, iron (II) ion, iron (III) ion, ruthenium ion, rhodium ion, tin ion etc. here.Wherein, consider, be preferably silver ions, palladium ion from being easy to the reductive angle.
In addition, have in the situation of adsorption of metal ions group, can metals ion be incorporated in this compound through the salt exchange at said cross-linked compound.
In the reactive composition that in this operation, is adopted, the content of the metals ion among the present invention is preferably 1 quality %～30 quality %, more preferably 2 quality %～10 quality %.
In addition, these metals ions can a kind of independent use, also can two or morely share.
In the reactive composition that in this operation, is adopted, except above-mentioned composition, as required, can also add polymerization starter, sensitizer, chain-transfer agent, polymerization terminator etc.In addition; Carrying out in the polymeric situation through applying the reactive composition that energy makes in this operation to be adopted; Can be without polymerization starter, and adopt with this reactive composition in the corresponding light of absorbing wavelength of the cross-linked compound that contained shine with initiated polymerization.For example, in employing has with the situation of acryloxy as the cross-linked compound of crosslinkable groups, preferably adopt the light of 254nm.
Below, the various compositions that when polymer layer forms, adopted, add in the reactive composition are described.
[polymerization starter]
The polymerization starter that is adopted among the present invention; Can be according to purpose; From the known thermal polymerization that can realize the polymerization initiating power through applying certain energy (for example, the irradiation of the irradiation of active ray, heating, electron rays etc.), Photoepolymerizationinitiater initiater etc., suitably select.Wherein, from being well suited for utilizing photopolymerisable angle to consider aspect the manufacturing suitability, preferably adopt Photoepolymerizationinitiater initiater.In other words, the optical polymerism composition of the reactive composition among the present invention for adopting Photoepolymerizationinitiater initiater to form.
As the Photoepolymerizationinitiater initiater among the present invention, can adopt the radical polymerization initiator of hydrogen-abstraction, the radical polymerization initiator of photodestruciton type etc.
Radical polymerization initiator as hydrogen-abstraction; For example, can adopt known free-radical generating agent such as acetophenones, benzophenone, Elisabeth Micheler ketone (Michler ' s ketone), benzoyl-benzoic ether, bitter almond oil camphor class, α-acyl oximido ester, tetramethylthiuram monosulfide, trichloromethyl triazine and thioxanthone.In addition, under rayed, also can play the effect of free-radical generating agent usually as the sulfosalt of light acid producing agent and salt compounded of iodine etc., therefore, they also can be used for the present invention.
Has the such structure of singly-bound that fracture takes place in the radical polymerization initiator of photodestruciton type in addition, under the effect of light.As the singly-bound that fracture takes place under the effect of light, can enumerate α scission reaction, βLie Xie reaction, the light that can utilize carbonyl and freely transfer the scission reaction of reaction, phenacylate, the scission reaction of sulfimide, the scission reaction of sulfonyl ester, the imido scission reaction of scission reaction, benzyl of N-hydroxyl sulfonyl ester, active halid scission reaction etc. and the singly-bound of fracture.Through these reactions, can the singly-bound that under the effect of light, can rupture be broken off.As the singly-bound that can rupture, can enumerate C-C key, C-O key, S-N key, C-N key, N-O key and C-C1 key etc.
As having the singly-bound that under the effect of light, can break off but also can produce the polymerization starter of radical, can enumerate the polymerization starter that contains following radicals.
That is, can enumerate for example aromatic series ketone group, phenacylate base, sulfimide base, sulphonyl ester group, N-hydroxyl sulphonyl ester group, benzyl imide, trichloromethyl, chloro benzyl, oxime ester base etc.
In addition, in the present invention, also can adopt the positively charged ion thermal polymerization.As this positively charged ion thermal polymerization; Any material with positively charged ion thermopolymerization initiation (for example comprising known materials such as CP-66 that Asahi Denka Kogyo K. K produces, CP-77) be can use, the salt, silanol aluminium complex of sulfosalt, ammonium salt, microcosmic salt etc. etc. for example can be used.As sulfosalt class thermal polymerization, can use CP-66 that for example rising sun electrochemical industry (strain) produces, CP-77 etc.
In addition, the temperature of reaction in the crosslinked reaction of the formation of adopting above-mentioned positively charged ion thermopolymerization to be carried out is not had special qualification, can suitably set, as long as can form crosslinked.
Do not have special qualification for the polymerization starter that is adopted in this operation, can select accordingly, can be used yet with following sensitizer according to the energy that is applied.
In addition, as polymerization starter used in this operation, what preferably use is to being used for the polymerizable group that cross-linked compound contained of reactive composition, can show the polymerization starter of polymerization initiating power.
In the reactive composition that this operation adopted, Photoepolymerizationinitiater initiater of the present invention preferably accounts for 0.01 quality %～20 quality %, more preferably accounts for 0.1 quality %～10 quality %.
In addition, these polymerization starters can a kind of independent use, also can two or morely share.
[sensitizer]
Do not have special qualification for the sensitizer that uses among the present invention, according to the energy that is applied in (especially exposure wavelength), can be from known sensitizer appropriate selection.
Specifically; (for example can enumerate for example known Ppolynuclear aromatic class (for example Bi 、 perylene, benzophenanthrene), xanthene class; Resorcinolphthalein, eosin, tetraiodofluorescein, rhodamine B, RB), the cyanines class (for example; Indoles carbon cyanines, sulphur carbon cyanines, oxygen carbon cyanines), part cyanines class (for example; Part cyanines, carbon part cyanines), thiazides (for example; Thionine, methylene blue, toluidine blue), acridine (for example; SP 15 Lemon Yellow, chloroflavin, trypaflavine), the anthraquinone class (for example; Anthraquinone), side type (for example, side), acridine ketone (for example, dihydroketoacridine, chloro-acridine ketone, N-methylacridine ketone, N-butyl dihydroketoacridine, N-butyl-chloro-acridine ketone etc.), coumarins are (for example; 3-(2-cumarone formyl radical)-7-diethyl amino coumarin, 3-(2-cumarone formyl radical)-7-(1-pyrrolidyl) tonka bean camphor, 3-benzoyl--7-diethyl amino coumarin, 3-(2-anisoyl)-7-diethyl amino coumarin, 3-(4-dimethylamino benzoyl-)-7-diethyl amino coumarin, 3; 3 '-carbonyl two (5,7-two positive propoxy tonka bean camphors), 3,3 '-carbonyl two (7-diethyl amino coumarin), 3-benzoyl--ayapanins, 3-(2-furancarbonyl)-7-diethyl amino coumarin, 3-(4-diethylamino cinnamoyl)-7-diethyl amino coumarin, 7-methoxyl group-3-(3-pyridyl carbonyl) tonka bean camphor, 3-benzoyl--5; 7-dipropoxy tonka bean camphor, and other are such as the coumarin compound of record in japanese kokai publication hei 5-19475 communique, japanese kokai publication hei 7-271028 communique, TOHKEMY 2002-363206 communique, TOHKEMY 2002-363207 communique, TOHKEMY 2002-363208 communique, the TOHKEMY 2002-363209 communique etc. etc.).
As the combination of Photoepolymerizationinitiater initiater and sensitizer, can enumerate the electron transfer type initiator system combinations of putting down in writing in the TOHKEMY 2001-305734 communique for example such as [(1) power supply subtype initiator and enhanced sensitivity pigment, (2) receive electron type initiator and enhanced sensitivity pigment, (3) power supply subtype initiator, enhanced sensitivity pigment and receive electron type initiator (ternary initiator system)].
The addition of sensitizer in the used reactive composition is preferably 10 quality %～500 quality % with respect to polymerization starter, more preferably 50 quality %～200 quality % in this operation.
In addition, these sensitizers can a kind of independent use, also can two or morely share.
[thermopolymerization terminator]
In the used reactive composition of this operation, also can add the thermopolymerization terminator.Add the thermopolymerization terminator and be in order to prevent reactive composition generation thermopolymerization or to pass in time and polymerization takes place; Through adding the thermopolymerization terminator; Can improve the chemicalstability when the preparation reactive composition, perhaps improve the chemicalstability when storing before use.
As the thermopolymerization terminator; Can enumerate right-methoxyphenol, Resorcinol, benzoquinones, neighbour-toluquinone, right-toluquinone, tert-butyl catechol, pyrogallol, 2-dihydroxy benaophenonel, 4-methoxyl group 2-dihydroxy benaophenonel, cuprous chloride, phenothiazine, fluorine quinone (Off ロ ラ ニ Le), chloranil, naphthylamines, pyridine, right-monomethylaniline, β-Nai Fen, 2, the aluminium salt of 6-di-t-butyl-p-Cresol, oil of mirbane, dinitrobenzene, TNP, N-nitroso-group phenyl azanol or ammonium salt, methylene blue organic copper, wintergreen oil, aryl phosphate ester etc.
Consider that from the angle of thermostability and light sensitivity with respect to the solid substance of reactive composition, the preferred addition of thermopolymerization terminator is 0.001 quality %～10 quality %, more preferably 0.01 quality %～3 quality %.
[solvent]
In order to make it be easier to contact with support or middle layer, the reactive composition that contains above-mentioned each composition is preferably liquid composition.In order to prepare this liquid composition, preferably use suitable solvent.
Do not have special qualification for solvent used herein,, but be preferably aqueous solvents such as water, water-soluble solvent as long as it can perhaps disperse the cross-linked compound dissolving as staple, or their mixture.
As operable solvent; Can enumerate for example water, such as the alcoholic solvent of methyl alcohol, ethanol, propyl alcohol, terepthaloyl moietie, glycerine, propylene glycol monomethyl ether etc., such as the acid of acetate etc.; Ketones solvent such as acetone, methylethylketone, pimelinketone etc.; Such as the amide solvent of methane amide, N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone etc., such as the nitrile solvents of acetonitrile, propionitrile etc., such as esters solvent of acetate methyl, ETHYLE ACETATE etc. etc.
Wherein, The cross-linked polymer that contains cyanic acid in employing forms in the situation of compsn; Said solvent is preferably amide solvent, ketones solvent, nitrile solvents, specifically, is preferably acetone, N,N-DIMETHYLACETAMIDE, methylethylketone, pimelinketone, acetonitrile, propionitrile, N-Methyl pyrrolidone.
In addition, when coating contains the compsn of the cross-linked polymer with cyanic acid, consider that preferred boiling point is 50～150 ℃ a solvent from the angle of being convenient to handle.In addition, these solvents can a kind of independent use, also can two or more mixing use.
This tensio-active agent in addition, as required, can in this liquid composition, add tensio-active agent, as long as can be dissolved in the solvent.As this type of tensio-active agent; For example can enumerate aniorfic surfactant such as the dodecyl Supragil GN; Cationic surfactant such as dodecyl trimethyl ammonium chloride; Such as polyoxyethylene nonylphenol (as commercially available article; エ マ Le ゲ Application 910 that Kao Corp produces etc. is for example arranged), the non-ionics of polyoxyethylene 20 sorbitan monolaurate (, trade(brand)name " polysorbas20 " etc. for example being arranged), polyoxyethylene lauryl ether etc. as commercially available article.
(embodiment that compsn contacts with the middle layer)
In this operation; As the method that the above-mentioned reactive composition that contains cross-linked compound is contacted with the middle layer; Can adopt arbitrary method; Specifically, can enumerate that the support that is formed with the middle layer is immersed in the method in the liquid reactive composition, or the reactive composition of liquid state is coated in the method on the middle layer.
In addition, consider that preferably, the reactive composition of liquid state is coated on the middle layer, drying is to form the such embodiment of polymerizability layer from property be prone to handled and the angle of making efficient.
When forming the polymerizability layer, the coated weight of this polymerizability layer by being converted into solid substance, is preferably 0.1～10g/m 2, be preferably 0.5～5g/m especially 2
(applying of energy)
In this operation, react directly to be combined in the polymkeric substance of interlayer surfaces with compound in order to make the polymerizable group in the middle layer with crosslinkable groups, need carry out applying of energy.
As the means that apply energy that can adopt, can enumerate means such as for example active ray irradiation, heating, electron rays irradiation here.Wherein, for can be easily and apply energy accurately, preferably adopt the pattern exposure method as the method that applies energy the image shape.
-pattern exposure-
Can make polymerizable group and compound reaction in the middle layer as long as carry out pattern exposure, specifically, preferably adopt the laser of 360nm～700nm wavelength to carry out pattern exposure with crosslinkable groups.
In addition, the exposure that needs depends on the coupling agent with polymerizable group, the compound with crosslinkable groups, Photoepolymerizationinitiater initiater and enhanced sensitivity pigment, but is preferably 25mJ/cm 2～400mJ/cm 2
As pattern exposure, for example can adopt the scan exposure that utilizes negative ray (CRT) to carry out.In the cathode tube that in this exposure, uses, can use can be luminous in SPECTRAL REGION as required various twinklers.For example, can use any one or two or more mixing of emitting red light body, green emitting body, blue-light emitting body to use.SPECTRAL REGION is not limited only to above-mentioned redness, green and blue, also can use the fluor that sends yellow, orange, purple light.
In addition, in this operation, can use various laser beams to carry out pattern exposure.For example preferred adopt use monochromatic high-density light (laser such as gas laser, photodiode, semiconductor laser, semiconductor laser, or be the Solid State Laser of exciting light source and second harmonic illuminating source (SHG) that non-linear optic crystal combines etc. with the semiconductor laser) the scan exposure mode.In addition, also can use KrF PRK, ArF PRK, F2 laser etc.
Receive the restriction of conditions of exposure by the resolving power of the polymer layer of the formed image shape of the present invention.In other words, in the pattern exposure process that forms polymer layer,, can form and the corresponding pattern with high precision of making public through applying the pattern with high precision exposure.As the exposure method that forms pattern with high precision, can enumerate the beam flying exposure of adopting optical system, the exposure of employing mask etc.Resolving power according to the pattern of hoping to obtain is selected corresponding exposure method.
As the pattern with high precision exposure, specifically, can enumerate the exposure of the step unit that adopts i line step unit (ス テ Star パ), g line step unit, KrF step unit, ArF step unit and so on etc.
According to above to (b1) perhaps (b2) polymer layer form the explanation that operation is carried out, can form by the polymer layer that directly is combined in the formed image shape of polymkeric substance on this interlayer surfaces on the middle layer.
In addition, adopting (b2) polymer layer to form in the situation of operation, can form the polymer layer that contains metals ion.
[(b3) reaching (b4), polymer layer forms operation]
In the present invention, polymer layer formation operation is different with (b1) and (b2), also can directly on support, form the polymer layer of image shape.
Below, reaching (b4) to (b3), polymer layer formation operation describes.
In the present invention; In the situation of carrying out (b3) polymer layer formation operation; Use contains coupling agent with polymerizable group and the compound compositions with crosslinkable groups; On the support with after this support contacts, apply energy to said composition according to the image shape, so that support reacts said composition and the coupling agent with polymerizable group; And coupling agent with polymerizable group and the compound with crosslinkable groups are also reacted, and then form the polymer layer of image shape.At this moment, as required, can adopt methods such as heating to handle, can form the polymer layer that directly is combined in the lip-deep image shape of this support.
In addition; In the situation of carrying out (b4) polymer layer formation operation; Use contains coupling agent with polymerizable group, has the compound of crosslinkable groups and the compsn of metals ion; On the support with said composition with after this support contacts, apply energy to said composition according to the image shape, so that support reacts with the coupling agent with polymerizable group; And coupling agent with polymerizable group and the compound with crosslinkable groups are also reacted, and then form the polymer layer of image shape.At this moment, as required, can adopt methods such as heating to handle, can form the polymer layer that directly is combined in the lip-deep image shape of this support.
Form used coupling agent in the operation at (b3) polymer layer with polymerizable group, identical with the coupling agent that in above-mentioned (a) operation, is adopted with polymerizable group; In addition, form used compound in the operation, with identical at above-mentioned (b1) and the compound that (b2) adopted in the operation with crosslinkable groups with crosslinkable groups at (b3) polymer layer.
In addition, form used coupling agent in the operation with polymerizable group at (b4) polymer layer, identical with coupling agent used in above-mentioned (a) operation with polymerizable group; In addition, form used compound with crosslinkable groups and metals ion in the operation at (b4) polymer layer, with above-mentioned (b1) and (b2) in the operation used compound with crosslinkable groups and metals ion identical.Its preferred example is also identical.
In addition; When in the compsn that this operation adopted, containing coupling agent simultaneously and having the compound of crosslinkable groups with polymerizable group; In reactive composition; Concentration with coupling agent of polymerizable group is preferably 0.1 quality %～50 quality %, is preferably 5 quality %～20 quality % especially.
In addition; When in the compsn that this operation adopted, containing coupling agent simultaneously and having the compound of crosslinkable groups with polymerizable group; In reactive composition; Concentration with compound (cross-linked compound) of crosslinkable groups is preferably 20 quality %～90 quality %, is preferably 50 quality %～80 quality % especially.
In addition, in the reactive composition that this operation adopted, also can add and constitute above-mentioned (b1) and (b2) various any composition (polymerization starter, sensitizer, chain-transfer agent, polymerization terminator etc.) of used reactive composition in the operation.In addition, the preferred addition of these any compositions is also with aforementioned identical.
As making the contacted embodiment of reactive composition used in this operation and support; Can adopt arbitrary method, specifically, can enumerate that support is immersed in the method in the liquid reactive composition; Or the reactive composition of liquid state is coated in the method on the support; Can also adopt reactive composition to be coated on the support with liquid state, and dry, the method for formation polymerizability layer.In addition, the coated weight of the preferred coated weight of this polymerizability layer when at above-mentioned (b1) and (b2) forming the polymerizability layer in the operation is identical.
In addition, when adopting reactive composition to form the polymerizability layer, also can the coupling base from the coupling agent with polymerizable group be combined with support.
In this operation, after making above-mentioned reactive composition on the support and this support contacts, apply energy to said composition.The method that applies energy with above-mentioned (b1) and (b2) adopted in the operation to apply ENERGY METHOD identical, its embodiment preferred is also identical.
According to above to (b3) perhaps (b4) polymer layer form the explanation that operation is carried out, can on support, form by the polymer layer that directly is combined in the formed image shape of the lip-deep polymkeric substance of this support.
In addition, adopting (b4) polymer layer to form in the situation of operation, can form the polymer layer that contains metals ion.
In addition, in (b1)～(b4) polymer layer forms operation, after above-mentioned reactive composition applies energy,, as required, can carry out heat treated in order to promote combining of support and coupling agent with polymerizable group.For polymer layer, this heat treated can after carry out before the development stated, also can after carry out after the development stated.But, in the situation of the polymer layer that forms the image shape, consider from the angle that becomes more meticulous of image, preferably after developing, carry out heat treated.
Heating temperature is preferably 40 ℃～150 ℃, more preferably 60 ℃～80 ℃.
In the present invention; To having support by the formed polymer layer of above method; Carry out processing such as solvent impregnated or solvent cleaning, to remove unreacted reactive composition or not to be combined in (this processing are also referred to as development treatment) such as homopolymer on support or the middle layer.
When carrying out this processing, specifically, can adopt water, acetone, aqueous sodium hydroxide solution, sodium bicarbonate aqueous solution, hydrochloric acid, methylethylketone, acetone, ethanol.In addition, after carrying out processing such as solvent impregnated or solvent cleaning, preferably carry out drying treatment.
In addition, when carrying out this processing, also can adopt industrial wipers such as Bemcot.In addition, consider, also can adopt means such as UW from the angle of removing homopolymer.
After these processing, unreacted reactive composition and the homopolymer that is not combined on support or the middle layer are removed, the polymkeric substance of only remaining mortise on support or middle layer.
The thickness of formed polymer layer is preferably 200nm～2000nm, and more preferably 500nm～1500nm further is preferably 600nm～1000nm.The thickness of polymer layer can contain more metal particle in this polymer layer in this scope the time, so preferred.
Particularly, be used for the situation of photomask, can contain the metallic particles that to realize sufficient opacifying property, so the thickness of polymer layer be preferably in above-mentioned scope at thin-layer metal membrane material of the present invention.In addition, when the not enough 200nm of the thickness of polymer layer, the amount of the metallic particles that is contained is insufficient, therefore sometimes can not obtain sufficient opacifying property.In addition, when the thickness of polymer layer surpassed 2000nm, when the photomask of use made made public, the resolving power of image reduced.
In the present invention, after making the compsn that contains cross-linked compound at least and the middle layer contacting, can come the thickness of polymer layer is adjusted to the amount (exposure during pattern exposure) of its energy that applies through control.
The thickness of polymer layer can be measured through AFM (NPX100M001, セ イ コ one イ Application ス Star Le メ Application Star Co., Ltd. make).
[(c1)～(c4) metallic particles is separated out operation]
At (c1) of the present invention perhaps in (c3) operation, after perhaps adding metals ion in the formed polymer layer of (b3) operation through above-mentioned (b1), with this metals ion reduction with the precipitating metal particle.
In addition, at (c2) perhaps in (c4) operation since through above-mentioned (b2) perhaps (b4) operation in polymer layer, contained metals ion, this metals ion is reduced with the precipitating metal particle.
Be used for the situation of photomask at this thin-layer metal membrane, consider that from the angle of light shielding ability preferably, the metallic particles of being separated out has absorption to the light in the employed exposure wavelength scope, especially preferably the light to the above wavelength of 365nm has absorption.
As method at above-mentioned (c1) and the adding metals ion that (c3) adopted in the operation; Can adopt and to contain metal ion solution and be coated in the perhaps method on the formed polymer layer of (b3) operation, also can adopt the support that will be formed with polymer layer to be immersed in the method in this solution through above-mentioned (b1).
Metals ion used herein is identical with metals ion in the reactive composition used in above-mentioned (b2) operation.Its preference is also identical.
In addition, contain that the concentration of metals ion is preferably 0.1 quality %～10 quality % in the metal ion solution.
Also have, have no particular limits,, preferably make water, methyl alcohol, ethanol, propyl alcohol, THF, pyridine, ammoniacal liquor etc. as long as this solvent can dissolve the metallic compound as metal ion source for the solvent that uses in this solution.
Above-mentionedly contain metal ion solution and contacted time of polymer layer, can suitably determine according to the concentration of the composition of polymer layer, metals ion, purposes etc., usually preferably between 10 seconds～10 minutes.
The salt exchange in addition,, in polymer layer, contains in the situation of polymkeric substance, owing to can be introduced metals ion in this polymkeric substance with adsorption of metal ions group through this contact.
Through above-mentioned method, after introducing metals ion in the polymer layer,, get final product the precipitating metal particle through with the reduction of the metals ion in this polymer layer.
During ion, can adopt reductive agent in the reducing metal.Have no particular limits for this reductive agent, can the reduction of the metals ion in the polymer layer can be adopted general reductive agent as long as it has enough reducing powers.For example, can adopt organic reducing agents such as formaldehyde, acetaldehyde, hydrazine, and NaBH 4, LiAlH 4, metal, semi-metal reductive agent such as borine.
In addition, as the reduction of metal ion method, have the support that is formed with polymer layer is immersed in the method in the solution that contains above-mentioned reductive agent, this method is easy, is suitable for using.The solvent that uses in the solution as reductive agent need be considered reactivity, danger of the reductive agent that is adopted etc., can adopt common solvent such as water, methyl alcohol, acetone, toluene, THF.
Time of immersion can suitably determine according to the concentration of metal ions in the polymer layer, the content of reductive agent in the solution.Usually be preferably 1 second～600 seconds.
(c1)～(c4) operation among the present invention can be carried out before above-mentioned development treatment respectively, also can after developing, carry out.Yet consider that from the angle of carrying out development treatment easily being preferably in develops carries out afterwards.
Through above method, can access the polymer layer of the image shape that contains metallic particles.
By the resulting thin-layer metal membrane material of the present invention (thin-layer metal membrane material of the present invention), only in being formed with the zone of polymer layer, there is metallic particles.Therefore; Except being that light shielding part is used as this representational application of photomask with the polymer layer that contains metallic particles, thin-layer metal membrane material of the present invention can also be used as electric wiring substrate, light reflecting material, finishing material, metallic particles transfer printing with material, colour filter.
The photomask that is suitable for for thin-layer metal membrane material of the present invention does not have special qualification, as long as its opacifying property height and weather resistance are good, for example, goes for the photomask of LSI, LCD, PWB, PDP, assembly etc.
[embodiment]
Below, the present invention will be described through embodiment, Comparative Examples, but the present invention is not limited to these embodiment.
(synthetic example 1: polymer P 1 (aforementioned exemplary compound (1)) synthetic with polymerizable group and adsorption of metal ions group)
With ROHM (molecular-weight average 7; 200) 18g is dissolved among DMAc (N,N-DIMETHYLACETAMIDE) 300g; To wherein adding Resorcinol 0.41g, 2-methacryloxyethyl isocyanic ester 29.3g and dibutyl tin dilaurate 0.25g, reacted 4 hours down at 65 ℃.Then, reaction solution is joined in the ETHYLE ACETATE so that polymer precipitation is fully clean with it, obtain having the polymer P 1 (aforementioned exemplary compound (1)) of polymerizable group and adsorption of metal ions group.The acid number of resulting polymer P 1 is 10.50meq/g.
(synthetic example 2: intramolecularly is introduced into the polymer P with polymerizable group 2 (aforementioned exemplary compound (M2)) synthetic of metals ion)
With ROHM (molecular-weight average 7; 200) 18g is dissolved among DMAc (N,N-DIMETHYLACETAMIDE) 300g; To wherein adding Resorcinol 0.41g, 2-methacryloxyethyl isocyanic ester 29.3g and dibutyl tin dilaurate 0.25g, reacted 4 hours down at 65 ℃.This moment, the acid number of resulting polymkeric substance was 10.50meq/g.Then; Adopt the aqueous sodium hydroxide solution of 1 mol that carboxyl is neutralized; Add the Silver Nitrate of 1 mol again; Then this mixed solution is joined in the hexane so that polymer precipitation is fully clean with it, obtain the polymer P with polymerizable group 2 (aforementioned exemplary compound (M2)) that intramolecularly is introduced into metals ion.
[embodiment 1]
[middle layer formation operation]
After the glass substrate of thickness 2mm cleaned with acetone, zero(ppm) water, the ultraviolet and ozone that adopts ultraviolet and ozone cleaner (UV42 type, Japanese レ one ザ one Electronics Co., Ltd make) to carry out 5 minutes was handled.Then, the acryloxy propyl trimethoxy silicane is dissolved in the methylethylketone, is mixed with the solution of 10.0 quality %.This solution is spin-coated on the above-mentioned glass substrate.Spinner at first rotated 5 seconds with the speed of 300rpm, rotated 20 seconds with the speed of 1000rpm then.After the spin coating, heated 1 hour down, and clean its surface with methylethylketone at 100 ℃.Obtain having the glass substrate in middle layer thus, as substrate A1.
[polymer layer formation operation]
With synthetic routine 1 of 0.25g resultingly have the polymer P 1 of polymerizable group and adsorption of metal ions group, the Irgacure (R) 369 of 2.5mg is dissolved in the mixed solvent of N,N-DIMETHYLACETAMIDE (DMAc) 2.0g and acetonitrile 1.0g, is mixed with liquid reactive composition.The reactive composition that this is liquid is spin-coated on the interlayer surfaces of substrate A1.Spinner at first rotated 5 seconds with the speed of 300rpm, rotated 20 seconds with the speed of 1000rpm then.
Afterwards, substrate A1 was descended dry 5 minutes at 80 ℃, obtain the polymerizability layer.
(exposure)
Employing has the laser explosure machine of 405nm emission wavelength, according to predetermined pattern, with 120mJ/cm 2The intensity substrate A1 that will be formed with the polymerizability layer make public.After the exposure, the limit is with cleansing tissue (Bemcot, little Tianjin Industry Co., Ltd make) wiping polymerizability laminar surface gently, and the limit is cleaned with acetone, carries out wiping with nitrogen again.
Through above method, obtained being formed with the glass substrate of the polymer layer of the image shape that constitutes by the polymkeric substance that directly is combined on the interlayer surfaces above that.This glass substrate of polymer layer with image shape is as substrate B1.
Adopt AFM (Na ノ ピ Network ス 1000, セ イ コ one イ Application ス Star Le メ Application Star society makes, and uses the AFM cantilever) to observe the pattern of resulting substrate B1.The result can confirm: on the surface of glass substrate, formed the slice of wide 10 μ m and the space of wide 10 μ m and replaced the pattern that exists.
In addition, the thickness of the polymer layer of image shape is 1000nm.
[metallic particles is separated out operation]
The substrate B1 that obtains dipping in 0.1% aqueous solution of Silver Nitrate (making with the pure medicine of light Co., Ltd.) was flooded 10 minutes in Superlysoform after 5 minutes again.Afterwards, repeatedly wash, it is cleaned, obtain having the substrate of the polymer layer that contains metallic particles with 50mL moisture.
Obtain the thin-layer metal membrane material of embodiment 1 thus.
< evaluation >
Through the zone of measuring the formation polymer layer and the absorbancy that does not form the zone of polymer layer, and the pencil intensity of polymer layer (thin-layer metal membrane), resulting thin-layer metal membrane material is estimated.
Measure the absorbancy of polymer layer (thin-layer metal membrane) when 365nm of resulting thin-layer metal membrane material through following measuring method, its result is 3.5.In addition, measure its absorbancy when the 400nm through following measuring method, its result is 3.4.
In addition, the absorbancy of zone when 365nm that does not form polymer layer is below 0.2, and the absorbancy when 400nm is below 0.1.
The measuring method of-absorbancy-
Using the visible and near-infrared spectrophotometer (UV-3600, Shimadzu Corporation) and the obtained metal thin film material was measured absorbance.Absorbancy when 365nm is more than 3.5, is the practical standard that no problem thin-layer metal membrane material (photomask).
[embodiment 2]
[polymer layer formation operation]
Adopt the method same with embodiment 1; Obtain having the glass substrate of the polymer layer of image shape, difference is to replace the used polymer P with adsorption of metal ions group 1 that is obtained by synthetic example 1 among the embodiment 1 with the polymer P with polymerizable group 3 that intramolecularly is introduced into metals ion.
With this glass substrate of polymer layer with image shape as substrate B2.
In addition, the thickness of the polymer layer of image shape is 960nm.
[metallic particles is separated out operation]
Resulting substrate B2 was flooded in Superlysoform 10 minutes.Afterwards, repeatedly clean, it is cleaned, obtain having the substrate of the polymer layer that contains metallic particles with the moisture of 50mL.
Obtain the thin-layer metal membrane material of embodiment 2 thus.
< evaluation >
Measure the absorbancy of polymer layer (thin-layer metal membrane) when 365nm of resulting thin-layer metal membrane material through following measuring method, consequently 3.1.In addition, measure its absorbancy when the 400nm, consequently 3.0 through said measuring method.
In addition, the absorbancy of zone when 365nm that does not form polymer layer is below 0.1, and the absorbancy when 400nm is below 0.1.
[embodiment 3]
[polymer layer formation operation]
After the glass substrate of thickness 2mm cleaned with acetone, zero(ppm) water, carry out 5 minutes ultraviolet and ozone processing with ultraviolet and ozone cleaner (UV42 type, Japanese レ one ザ one Electronics Co., Ltd make).
Then; With 0.25g by synthetic example 1 resultingly have the polymer P 1 of polymerizable group and adsorption of metal ions group, Irgacure (R) 369 and the acryloxy propyl trimethoxy silicane 0.05g of 2.5mg is dissolved in the mixed solvent of N,N-DIMETHYLACETAMIDE (DMAc) 2.0g and acetonitrile 1.0g, is mixed with liquid reactive composition.The reactive composition that this is liquid is spin-coated on the glass baseplate surface that above-mentioned ozonize crosses.Spinner at first rotated 5 seconds with the speed of 300rpm, rotated 20 seconds with the speed of 1000rpm then.
Afterwards, substrate was descended dry 5 minutes at 80 ℃, obtain the polymerizability layer.
(exposure)
The substrate that will be formed with the polymerizability layer adopts with embodiment 1 same method and makes public, and obtains having the glass substrate of the polymer layer of image shape.With this glass substrate of polymer layer with image shape as substrate B3.
The thickness of the polymer layer of image shape is 800nm.
[metallic particles is separated out operation]
Resulting substrate B3 through with embodiment 1 same method metallic particles being separated out, is obtained having the substrate of the polymer layer that contains metallic particles.
< evaluation >
Measure the absorbancy of polymer layer (thin-layer metal membrane) when 365nm of resulting thin-layer metal membrane material through following measuring method, consequently 2.7.In addition, measure its absorbancy when the 400nm, consequently 2.6 through following measuring method.
In addition, the absorbancy of zone when 365nm that does not form polymer layer is below 0.1, and the absorbancy when 400nm is below 0.1.
[Comparative Examples 1]
Adopt with embodiment 1 same method and make substrate A2, the acryloxy propyl trimethoxy silicane that difference is adopted when being to replace in embodiment 1 making to have the substrate A1 in middle layer with the octyl group Trimethoxy silane.
Adopt the method same, use resulting substrate A2, carry out polymer layer and form operation with embodiment 1., observe the thickness of resulting polymer layer with AFM here, the result shows in the image that is formed by resulting polymer layer and has a lot of defectives, and the thickness of polymer layer is below the 10nm.
Then, adopt and to carry out metallic particles with embodiment 1 same method and separate out operation.
For through the resulting material of above method, adopt the mensuration of carrying out absorbancy with embodiment 1 same method.The result is as shown in table 1.
[Comparative Examples 2]
After the glass substrate of thickness 2mm cleaned with acetone, zero(ppm) water, the ultraviolet and ozone that adopts ultraviolet and ozone cleaner (UV42 type, Japanese レ one ザ one Electronics Co., Ltd make) to carry out 5 minutes was handled.Then, the compound with polymerization initiation position and substrate bonded position as follows is dissolved in the dry toluene, is mixed with the solution of 1.0 quality %.This solution is spin-coated on the above-mentioned glass substrate.Spinner at first rotated 5 seconds with the speed of 300rpm, rotated 20 seconds with the speed of 1000rpm then.After the spin coating, heated 60 seconds down at 100 ℃, and with toluene and its surface of acetone.Spinner rotated 5 seconds with the speed of 300rpm earlier again, rotated 20 seconds with the speed of 1000rpm then.Then, glass substrate was descended dry 10 minutes at 100 ℃, clean its surface with toluene, acetone, water successively, use air gun dry then.Obtain being combined with the glass substrate of the compound of following structure thus, as substrate A3.
Figure S200810110607XD00551
Adopt the method same, use resulting substrate A3 to carry out polymer layer and form operation with embodiment 1., observe the thickness of resulting polymer layer with AFM here, its result is 80nm.
Then, adopt and to carry out metallic particles with embodiment 1 same method and separate out operation.
Adopt with embodiment 1 same method and measure absorbancy by the above resulting material of method.The result is as shown in table 1.
Table 1
The thickness of polymer layer (nm) The absorbancy of polymer layer when 365nm
Embodiment 1 1000 ?3.5
Embodiment 2 960 ?3.1
Embodiment 3 800 ?2.7
Comparative Examples 1 Below 10 ?0.2
Comparative Examples 2 80 ?0.3
Can find out that by table 1 through the polymer layer (thin-layer metal membrane) that embodiment obtains, film thickness is big and absorbancy is high.
Like this, can know that even apply the energy of same amount, the film thickness of formed polymer layer increases significantly in an embodiment by the comparison of embodiment and Comparative Examples.Therefore can know,, in the situation that coupling agent that will have polymerizable group and the compounds with crosslinkable groups are used, can form highly sensitive to reaction, even and apply the low-yield big polymer layer of film thickness that also can form according to the present invention.The result can obtain having high-density metal particulate metallic membrane, and can obtain good absorbancy.

Claims (20)

1. thin-layer metal membrane material, it contains:
Support;
On this support, adopt the middle layer that has the coupling agent of polymerizable group and form;
The polymer layer of image shape; This polymer layer is by through after will containing compound compositions with crosslinkable groups and said middle layer contacting, thereby polymkeric substance on this interlayer surfaces constitutes according to image shape directly being combined in of applying that energy generates to said composition; And,
Be included in the metallic particles in the polymer layer of this image shape.
2. thin-layer metal membrane material, it contains:
Support;
The polymer layer of image shape; This polymer layer is by passing through on said support; After will containing coupling agent with polymerizable group and the compound compositions with crosslinkable groups and this support contacting, thereby the lip-deep polymkeric substance of above-mentioned support constitutes according to image shape directly being combined in of applying that energy generates to said composition; And,
Be included in the metallic particles in the polymer layer of this image shape.
3. claim 1 or 2 described thin-layer metal membrane materials, the wherein said compound compositions with crosslinkable groups that contains also contains photodestruciton type radical polymerization initiator.
4. claim 1 or 2 described thin-layer metal membrane materials, the polymerizable group in the wherein said coupling agent with polymerizable group is identical functional group with crosslinkable groups in the said compound with crosslinkable groups.
5. claim 1 or 2 described thin-layer metal membrane materials, wherein said coupling agent with polymerizable group has acryl or methacryloyl.
6. claim 1 or 2 described thin-layer metal membrane materials, wherein said compound with crosslinkable groups has acryl or methacryloyl.
7. claim 1 or 2 described thin-layer metal membrane materials, wherein said compound with crosslinkable groups has vinyl or epoxy group(ing).
8. claim 1 or 2 described thin-layer metal membrane materials, wherein said metallic particles has absorption to the light in the wavelength region more than the 365nm.
9. claim 1 or 2 described thin-layer metal membrane materials is characterized in that, the film thickness of said polymer layer is more than the 200nm and below the 2000nm.
10. the method for manufacture of a thin-layer metal membrane material, it comprises following operation:
Form the operation in middle layer, in this operation, adopt coupling agent on support, to form the middle layer with polymerizable group;
Form the operation of the polymer layer of image shape; In this operation, pass through on said middle layer; After will containing compound compositions and this middle layer contacting with crosslinkable groups; Apply energy to said composition according to the image shape, generate and directly be combined in the polymkeric substance on this interlayer surfaces, and then form the polymer layer of image shape; And,
Precipitating metal particulate operation is also reduced this metals ion with the precipitating metal particle through in said polymer layer, adding metals ion in this operation.
11. the method for manufacture of a thin-layer metal membrane material, it comprises following operation:
Form the operation in middle layer, in this operation, have the coupling agent of polymerizable group and on support, form the middle layer through employing;
Form the operation of the polymer layer of image shape; In this operation, pass through on this middle layer; The compsn that will contain compound with crosslinkable groups and metals ion is with after said middle layer contacts; Apply energy to said composition according to the image shape, generate and directly be combined in the polymkeric substance on this interlayer surfaces, and then form the polymer layer of image shape; And,
Precipitating metal particulate operation, in this operation through with the reduction of the metals ion that contains in the said polymer layer with the precipitating metal particle.
12. the method for manufacture of a thin-layer metal membrane material, it comprises following operation:
Form the operation of the polymer layer of image shape; In this operation, pass through on support; After will containing coupling agent with polymerizable group and compound compositions and said support contacting with crosslinkable groups; Apply energy to said composition according to the image shape, generate and directly be combined in the lip-deep polymkeric substance of said support, and then form the polymer layer of image shape; And,
Precipitating metal particulate operation is also reduced this metals ion with the precipitating metal particle through in said polymer layer, adding metals ion in this operation.
13. the method for manufacture of a thin-layer metal membrane material, it comprises following operation:
Form the operation of the polymer layer of image shape; In this operation, pass through on support; The compsn that will contain the coupling agent with polymerizable group, the compound with crosslinkable groups and metals ion is with after said support contacts; Apply energy to said composition according to the image shape, generate and directly be combined in the lip-deep polymkeric substance of this support, and then form the polymer layer of image shape; And,
Precipitating metal particulate operation, in this operation through with the reduction of the metals ion that contains in the said polymer layer with the precipitating metal particle.
14. the method for manufacture of any described thin-layer metal membrane material in the claim 10～13, the wherein said compound compositions with crosslinkable groups that contains also contains photodestruciton type radical polymerization initiator.
15. the method for manufacture of any described thin-layer metal membrane material in the claim 10～13, the polymerizable group in the wherein said coupling agent with polymerizable group is identical functional group with crosslinkable groups in the said compound with crosslinkable groups.
16. the method for manufacture of any described thin-layer metal membrane material in the claim 10～13, wherein said coupling agent with polymerizable group has acryl or methacryloyl.
17. the method for manufacture of any described thin-layer metal membrane material in the claim 10～13, wherein said compound with crosslinkable groups has acryl or methacryloyl.
18. the method for manufacture of any described thin-layer metal membrane material in the claim 10～13, wherein said compound with crosslinkable groups has vinyl or epoxy group(ing).
19. the method for manufacture of any described thin-layer metal membrane material in the claim 10～13, wherein said metallic particles has absorption to the light in the wavelength region more than the 365nm.
20. the method for manufacture of any described thin-layer metal membrane material in the claim 10～13, the film thickness of wherein said polymer layer are more than the 200nm and below the 2000nm.
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