CN100526404C - Resin composition for coating - Google Patents
Resin composition for coating Download PDFInfo
- Publication number
- CN100526404C CN100526404C CNB2005800015862A CN200580001586A CN100526404C CN 100526404 C CN100526404 C CN 100526404C CN B2005800015862 A CNB2005800015862 A CN B2005800015862A CN 200580001586 A CN200580001586 A CN 200580001586A CN 100526404 C CN100526404 C CN 100526404C
- Authority
- CN
- China
- Prior art keywords
- alkyl
- coating
- weight
- fluoro
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
- C09D123/26—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment
- C09D123/28—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
- C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C09D201/04—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
Landscapes
- Chemical & Material Sciences (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Laminated Bodies (AREA)
Abstract
Disclosed is a coating resin composition characterized by containing a fluorine surfactant, which is composed of a fluorinated alkyl group-containing vinyl polymer (A) having a fluorinated alkyl group (a1), an aromatic ring (a2) and an acidic group (a3), and a binder resin (B) having an aromatic ring (b1) and an acidic group (b2).
Description
Technical field
The present invention relates to the good resin composite for coating of a kind of uniformity of film of filming.
Background technology
In semiconductor element such as LSI, IC, VLSI and liquid-crystal display flat-panel monitor (FPD) manufacturing processes such as (LCD), the method as form fine pattern such as circuit and colored pattern on substrate generally adopts photolithography.In this method, form photosensitive film at silicon chip surface painting erosion resistant agent (photosensitive polymer combination), after shining this film and form latent image with ultraviolet ray, far ultraviolet rays yue, excimer laser, X ray isoreactivity energy-ray, its development is formed the image of negative or positive.At this moment, usually above-mentioned resist is that to be applied on the silicon chip and to make its thickness by method of spin coating etc. be about 1～2 μ m.Here, if the coating difference of resist, resulting thickness of filming is just inhomogeneous, also can produce the radial crawling that is commonly referred to as striped.The ununiformity of filming like this can produce the rectilinearity of fine pattern and the problem of reproducibility reduction etc. in the such field that requires meticulous pattern precision of thin film transistor (TFT) array of for example LSI or LCD.In addition, when manufacturing is used for the colour filter of color LCD etc., can produce the color of pixel inequality, the image that its result obtains on aforementioned display device also can produce problems such as irregular colour.
As the method that solves above-mentioned problem, use the method for in resist, adding fluorine class tensio-active agent at present, the scheme that has also proposed various fluorine class tensio-active agents is (for example, with reference to patent documentation 1.)。But substrate just maximizes in recent years, thereby also variation of coating process, even use the fluorine class tensio-active agent of record in existing fluorine class tensio-active agent or the patent documentation 1, also has the inadequate situation of its effect.That uses in particularly when large LCD is made etc. passes through Xia Feng ﹠amp; Also may not be abundant under the situation of fluorine class tensio-active agent even the homogeneity of the film that method of spin coating or slot coated method form is stated in the use.
As the composition that can tackle diversified coating process, proposed to be not only in method of spin coating the also good photosensitive color resin combination (for example, with reference to patent documentation 2) of resulting uniformity of film of filming in the slot coated method.Put down in writing in the above-mentioned patent documentation 2 by making and contained the fluorine class organic compound that the fluorine atom containing ratio is 3～40 weight % (so-called fluorine class tensio-active agent) in the above-mentioned composition, even there be not filming uniformly of uneven thickness in the small amount of liquid that can improve to the imbibition characteristic of substrate yet.But, in above-mentioned patent documentation 2, use commercially available fluorine class tensio-active agent, thereby in above-mentioned accurate purposes, still can produce uneven part (crawling).This can think because present known fluorine class tensio-active agent as typical additives is designed to and the consistency of resin maintenance widely, therefore, when in accurate purposes, using, with respect to resin with acidic-group and aromatic nucleus as in patent documentation 2, using, the consistency deficiency of described fluorine class tensio-active agent, its result can not show sufficient surfactivity ability.Resin with acidic-group and aromatic nucleus, except the photosensitive color resin combination that is used for 2 records of above-mentioned patent documentation, can also be used for spacer that the liquid crystal cell uses with the photosensitive polymer combination of photo-resist etc. etc. or the external coating (EC) agent of colour filter, various hard film coating agents etc.In these purposes, must be by method of spin coating, Xia Feng ﹠amp; Method of spin coating, slot coated method etc. form film.Consider from this point, expect a kind ofly can obtain the good resin composite for coating of filming of uniformity of film.
Patent documentation 1: Japanese patent laid-open 10-309455 communique (3-14 page or leaf)
Patent documentation 2: the Japanese Patent spy opens 2003-222997 communique (the 13rd page)
Summary of the invention
The problem that invention will solve
In view of above-mentioned such actual state, the object of the present invention is to provide the good resin composite for coating of a kind of uniformity of film of filming.
Solve the means of problem
People of the present invention study intensively repeatedly in order to solve above-mentioned problem, found that: a kind of resin composite for coating, it is characterized in that, said composition contains fluorine class tensio-active agent and has aromatic nucleus and the adhesive resin of acidic-group, described fluorine class tensio-active agent is made up of the polyvinyls that contains fluoro-alkyl with fluoro-alkyl, aromatic nucleus and acidic-group, when using this resin composite for coating, particularly lead to and crossing method of spin coating, slit; Methods such as method of spin coating, slot coated method form the film of thickness submicron～micro scale, during particularly several micron-sized film crawling can not take place, demonstrate good uniformity of film, thereby finish the present invention.
Promptly, the invention provides a kind of resin composite for coating, it is characterized in that containing fluorine class tensio-active agent and have aromatic nucleus (b1) and the adhesive resin (B) of acidic-group (b2), this fluorine class tensio-active agent is made up of the polyvinyls that contains fluoro-alkyl (A) with fluoro-alkyl (a1), aromatic nucleus (a2) and acidic-group (a3).
The invention effect
According to the present invention, can provide a kind of uniformity of film of filming good resin composite for coating.Described composition is suitable for the such field that requires meticulous pattern precision of tft array of following field: LSI or LCD; Manufacturing is used for the external coating (EC) agent of the colour filter of color LCD etc. or colour filter, spacer that the liquid crystal cell is used must be by method of spin coating, slit with photo-resist etc.; The film forming fields of method such as method of spin coating, slot coated method.
Embodiment
Describe the present invention below in detail.
Among the present invention, the fluoro-alkyl group that to be the group (perfluoroalkyl) that all replaced by fluorine atom of the hydrogen atom in the alkyl and part hydrogen atom in the alkyl replaced by fluorine atom (HCF for example
2CF
2CF
2CF
2-etc.) general name, can be any one group of straight chain shape, branching.In addition, the group (CF for example that in above-mentioned fluoro-alkyl, contains Sauerstoffatom
3-(OCF
2CF
2)
2-etc.) be also contained among the definition of fluoro-alkyl of the present invention.
The polyvinyls that contains fluoro-alkyl (A) that uses among the present invention is the polymkeric substance with at least 1 vinyl of at least 1 fluoro-alkyl (a1) and at least 1 aromatic nucleus (a2) and at least 1 acidic-group (a3).This polymkeric substance is called as so-called aggretion type fluorine class tensio-active agent.Molecular weight about above-mentioned polymkeric substance (A), good and prevent the good viewpoint of each other aggegation of fluoro-alkyl, the uniformity of film that gained is filmed, suppress the foaminess the above-mentioned composition and show that the viewpoint of defoaming considers from the consistency of the consistency of this polymkeric substance (A) and aftermentioned adhesive resin (B) and this polymkeric substance (A) and other compositions of blended as required, weight-average molecular weight is generally 1000～200000, be preferably 5000～100000, be preferably 8000～80000 especially.
In general, fluoro-alkyl is hydrophobicity and oleophobic property.Thereby, bring into play function in order to make compound as tensio-active agent with fluoro-alkyl, must keep the consistency of the various media (solution or resin) that added with it.That is, be necessary in above-mentioned promoting agent, to import close media group (lipophilicity group and/or hydrophilic radical).Usually, it is not specific using the media of fluorine class tensio-active agent.Thereby when the close media group of design, it is favourable selecting to keep with respect to the close media group of the consistency of media widely under many situations.In addition, fluorine class tensio-active agent is because the surfactivity ability height that fluoro-alkyl brought, therefore usually addition with respect to media is few, does not consider the consistency of resinous principle contained in described fluorine class tensio-active agent and the media when stating close media group in design.In addition, with respect to the kind of target media and during the option table surface-active agent, though will confirm consistency (be exactly solvability this moment), the common consistency of not paying close attention to respect to the resin in the media with respect to solution.That is, only exist to select in the prior art with media in solvent compatible (dissolving) and in resin the situation of the compatible tensio-active agent of difficulty.In the field that requires good uniformity of film etc., coating and the superficiality after the film forming that resin etc. are included in the nonvolatile component in the media are important but in fact.Thereby, if be the tensio-active agent of compatible with solvent (dissolving), can not give full play to its function as tensio-active agent.That is, even tensio-active agent is compatible (dissolving) in solution, if solvent or water volatilization and the concentration (resin concentration) of nonvolatile component is uprised in the drying step in coating or after coating can cause the coating bad order.On the other hand, must under low nonvolatile component, low viscosity, be coated with, thickness is that submicron～micro scale, particularly several micron-sized films form in the operations, very big (film among the present invention is meant submicron～micro scale to tensio-active agent to the influence of coating outward appearance.)。During the close media group of the present invention in selecting fluorine class tensio-active agent, select and the consistency of modified resin and fluorine class tensio-active agent in view of the functional group that constitutes resin, its result can improve the homogeneity of film.
Fluoro-alkyl (a1) in the above-mentioned polyvinyls (A) that contains fluoro-alkyl is in order to bring into play the surfactivity ability that prevents crawling and necessary.From the high viewpoint of the effect of surfactivity ability, the carbonatoms in the fluoro-alkyl (a1) is generally 1～20 integer, is preferably 3～12 integer, is preferably 6～10 integer especially, in addition, is preferably straight catenate perfluoroalkyl.And, fluorine atom containing ratio in the polymkeric substance is high more, the surfactivity ability is good more, but the tensio-active agent high in view of the fluorine atom containing ratio is low with respect to the consistency of resin or solvent, fluorine atom containing ratio in the above-mentioned polymkeric substance (A) is generally 5～50 weight %, be preferably 7～35 weight %, be preferably 10～30 weight % especially.In addition, the fluorine atom containing ratio in the above-mentioned polymkeric substance (A) can be by behind the combustion decomposition polymkeric substance (A), and water or buck extraction resolvent come quantitative fluorinion concentration to calculate by ion chromatography.
In addition, aromatic nucleus (a2) in the above-mentioned polymkeric substance (A) and acidic-group (a3) are necessary in order to improve with the consistency of aftermentioned adhesive resin (B).Above-mentioned aromatic nucleus (a2) is not particularly limited, and for example, can enumerate substituent phenyl ring or naphthalene nucleus such as can having alkyl, can also be 2 or 2 structures that above aromatic nucleus is formed by connecting of biphenyl backbone etc.Further, in above-mentioned polymkeric substance (A), can also contain aromatic nucleus different more than 2 kinds or 2 kinds (a2).Wherein, from taking into account above-mentioned polymkeric substance (A) and the consistency of aftermentioned adhesive resin (B) and the viewpoint of surfactivity ability, preferred phenyl ring.The measuring method of the containing ratio of the aromatic nucleus (a2) in the above-mentioned polymkeric substance (A) uses FT-IR.At first, change the copolymerization ratio of methacrylic acid benzyl ester and methyl methacrylate, in mibk (MIBK) with azo isobutyronitrile (AIBN) as initiator, synthesizing weight-average molecular weight by radical polymerization is 30000 multipolymer.Use resulting multipolymer to carry out FT-IR and measure, based on be derived from C=C key in the aromatic nucleus at 1500cm
-1Near peak intensity, pre-rendered typical curve.The containing ratio of the aromatic nucleus (a2) in the above-mentioned polymkeric substance of measuring based on this typical curve (A) is preferably 10～40 weight %, is preferably 20～35 weight % especially.
As above-mentioned acidic-group (a3), for example, can enumerate carboxyl, hydroxyl, phosphate, sulfonic group etc.The substituting group that these groups can be used as above-mentioned fluoro-alkyl (a1) or above-mentioned aromatic nucleus (a2) is present in the polymkeric substance (A), and its location in polymkeric substance (A) without limits.In addition, in above-mentioned polymkeric substance (A), acidic-group different more than 2 kinds or 2 kinds (a3) can be arranged.Wherein, from taking into account the consistency and the surfactivity ability of above-mentioned polymkeric substance (A) and adhesive resin described later (B) easily, and the good viewpoint of the storage stability of the resin composite for coating of gained is set out, preferred carboxyl or hydroxyl, the few viewpoint of foaming during from the modulation above-mentioned composition, preferred hydroxyl.In addition, as the content of the acidic-group (a3) in the above-mentioned polymkeric substance (A), acid number is preferably 2～100mgKOH/g, preferred especially 7～70mgKOH/g, and hydroxyl value is preferably 20～200mgKOH/g, preferred especially 30～130mgKOH/g.
Manufacture method as above-mentioned polymkeric substance (A) is not particularly limited, but regulate weight-average molecular weight easily, easily and introduce the viewpoint of above-mentioned essential functional group's (fluoro-alkyl, aromatic nucleus, acidic-group) easily from easy acquisition industrial raw material, manufacture method, preferably monomer class (I) is carried out copolymerization, wherein this monomer class (I) vinyl monomer (x3) of comprising the vinyl monomer (x1) that contains fluoro-alkyl, the vinyl monomer (x2) that contains aromatic nucleus and containing acidic-group.
The vinyl monomer that contains fluoro-alkyl (x1) in the above-mentioned monomer (I), the containing ratio that contains the vinyl monomer (x2) of aromatic nucleus and contain the vinyl monomer (x3) of acidic-group are not particularly limited, but preferably select as one sees fit according to above-mentioned preferred fluorine atom containing ratio, aromatic nucleus containing ratio, acid number.Particularly, the vinyl monomer that contains fluoro-alkyl (x1) in the above-mentioned monomer class (I), the vinyl monomer (x2) that contains aromatic nucleus, and the total amount that contains the vinyl monomer (x3) of acidic-group is 60 weight % or more than it, and, the above-mentioned containing ratio that contains the vinyl monomer (x1) of fluoro-alkyl in the above-mentioned monomer class (I) is generally 3～50 weight %, be preferably 10～40 weight %, the above-mentioned containing ratio that contains the vinyl monomer (x2) of aromatic nucleus is generally 40～90 weight %, be preferably 50～80 weight %, the above-mentioned containing ratio that contains the vinyl monomer (x3) of acidic-group is generally 0.1～30 weight %, is preferably 0.5～7 weight %.Further, can also be as required and be used as the monomer class (x4) of the monomeric set of aftermentioned other one or more, and the viewpoint that its usage ratio of time spent is never damaged effect of the present invention is set out, in above-mentioned monomer class (I), preferably account for 40 weight % or below it, especially preferably account for 20 weight % or below it.
As the above-mentioned vinyl monomer (x1) that contains fluoro-alkyl, its structure is not particularly limited, and can use all cpds, for example, can enumerate following general formula (x1-1), (x1-2) represented compound.
[Chemical formula 1]
(in the formula, R
f 1, R
f 2, R
f 3The carbonatoms that is identical or differs from one another is 1～20 fluoro-alkyl, R
1Be hydrogen atom, methyl, chlorine atom or fluorine atom, X
1, X
2, X
3The divalent linking group that is identical or differs from one another, m
1, m
2, m
3Be 0 or 1 identical or differently.)
X among above-mentioned general formula (x1-1), (x1-2)
1, X
2, X
3(linking group of divalent) is not particularly limited, and for example, can enumerate following group.
[Chemical formula 2]
(in the formula, n is 1～10 integer, R
2It for hydrogen atom or carbonatoms 1～6 alkyl.)
Perhaps
[chemical formula 3]
As above-mentioned monomer (x1), for example, can enumerate following structural formula (x1-1-1)～(x1-1-55) and (x1-2-1) represented compound.
[chemical formula 4]
x1-1-1：CH
2＝CHCOOCH
2CH
2C
8F
17
x1-1-2：
x1-1-3：CH
2＝CHCOOCH
2CH
2C
12F
25
x1-1-4：
x1-1-5：CH
2＝CHCOOCH
2CH
2C
10F
21
x1-1-6：
x1-1-7：CH
2＝CHCOOCH
2CH
2C
6F
13
x1-1-8：
x1-1-9：CH
2＝CHCOOCH
2CH
2C
4F
9
x1-1-10：
x1-1-11：
x1-1-12：
x1-1-13：
x1-1-14：
x1-1-15：CH
2＝CHCOOCH
2CF
3
[chemical formula 5]
x1-1-16：CH
2＝CHCOOCH
2C
8F
17
x1-1-17：
x1-1-18：
x1-1-19：CH
2＝CHCOOCH
2C
20F
41
x1-1-20：
x1-1-21：
x1-1-22：
x1-1-23：CH
2＝CHCOOCH
2(CH
2)
6CF(CF
3)
2
x1-1-24：
x1-1-25：
x1-1-26：CH
2＝CHCOOCH
2(CF
2)
2H
x1-1-27：
x1-1-28：CH
2＝CHCOOCH
2(CF
2)
4H
x1-1-29：CH
2＝CHCOOCH
2CF
2H
x1-1-30：
[chemical formula 6]
x1-1-31：CH
2＝CHCOOCH
2(CF
2)
6H
x1-1-32：
x1-1-33：CH
2＝CHCOOCH
2(CF
2)
8H
x1-1-34：
x1-1-35：CH
2＝CHCOOCH
2(CF
2)
10H
x1-1-36：CH
2＝CHCOOCH
2(CF
2)
12H
x1-1-37：CH
2＝CHCOOCH
2(CF
2)
14H
x1-1-38：CH
2＝CHCOOCH
2(CF
2)
18H
x1-1-39：
x1-1-40：CH
2＝CHCOOCH
2CH
2(CF
2)
7H
x1-1-41：
x1-1-42：
x1-1-43：
x1-1-44：CH
2＝CHCOOCH
2C
2F
5
x1-1-45：
[chemical formula 7]
x1-1-46：
x1-1-47：
x1-1-48：
x1-1-49：
x1-1-50：
x1-1-51：
x1-1-52：CH
2＝CHCOO(CH
2)
2(CF
2)
8CF(CF
3)
2
x1-1-53：
x1-1-54：
x1-1-55：
x1-2-1：
Can only use a kind as above-mentioned monomer (x1), also can the utilization structure different mixtures of compound more than 2 kinds or 2 kinds.In addition, the carbonatoms in the fluoro-alkyl in the above-mentioned monomer (x1) is preferably 3～12 integer, is preferably 6～10 integer especially, in addition, and preferred straight catenate perfluoroalkyl.
The above-mentioned vinyl monomer (x2) that contains aromatic nucleus has vinyl simultaneously and can contain the compound of the structure of aromatic nucleus such as substituent phenyl ring or naphthalene nucleus so long as have at same intramolecularly, just can not have especially restrictedly and uses.For example, can enumerate vinylbenzene, (methyl) vinylformic acid benzyl ester, (methyl) vinylformic acid phenoxy ethyl, (methyl) vinylformic acid-2-hydroxyl-3-phenoxy group propyl ester, (methyl) vinylformic acid phenoxy group-macrogol ester, (methyl) vinylformic acid Nonylphenoxy-macrogol ester etc., wherein, from the good viewpoint of consistency of the polyvinyls that contains fluoro-alkyl (A) Yu the adhesive resin described later (B) of gained, preferred (methyl) vinylformic acid benzyl ester.In addition, (methyl) acrylate among the present invention just is meant acrylate and/or methacrylic ester if do not specify.
Above-mentioned monomer (x2) can only use a kind of, the mixture of two or more also can utilization structure different compounds.
As the above-mentioned vinyl monomer (x3) that contains acidic-group,, just can not have especially restrictedly and use so long as have the compound that has the structure of acidic-groups such as vinyl and carboxyl, hydroxyl, phosphate, sulfonic group at same intramolecularly simultaneously.For example, can enumerate vinylformic acid, methacrylic acid, toxilic acid, maleic anhydride, fumaric acid, methylene-succinic acid, Ba Dousuan, 2-(methyl) acryloxy ethyl succsinic acid, 2-(methyl) acryloxy phthalic acid, carboxylic vinyl monomers such as 2-(methyl) acryloxy hexahydrobenzene dioctyl phthalate, (methyl) vinylformic acid-2-hydroxyl ethyl ester, (methyl) vinylformic acid-2-hydroxypropyl acrylate, (methyl) vinylformic acid-2-hydroxy butyl ester, (methyl) vinylformic acid-4-hydroxy butyl ester, 2-hydroxyethyl acrylamide, (methyl) vinylformic acid-2-hydroxyl-3-phenoxy group propyl ester, glycerine list (methyl) acrylate, the vinyl monomer of the hydroxyl of alkylene glycol mono (methyl) acrylate etc., single (acryloxy ethyl) acid phosphoric acid ester, the vinyl monomer of phosphorous acidic groups such as single (methacryloxyethyl) acid phosphoric acid ester, 2-acrylamide-2-methyl propane sulfonic acid, partly sulfonated vinylbenzene etc. contain sulfonic vinyl monomer etc.Wherein, from the good viewpoint of the storage stability of resulting resin composite for coating, the preferred vinyl monomer that contain acidic-group of acidic groups that use as carboxyl or hydroxyl, in addition, from the few viewpoint of time foaming of modulating above-mentioned resin combination, preferably use the vinyl monomer of hydroxyl.
As above-mentioned monomer class (I), in the scope of not damaging effect of the present invention, can be as required further also with other monomers (x4).
As above-mentioned other monomers (x4), so long as the monomer of energy and above-mentioned monomer (x1), (x2), (x3) copolymerization just can use various monomers.For example, the carbonatoms that can enumerate alkyl is (methyl) alkyl acrylate of 1～18, promptly (methyl) acrylic acid methyl esters, ethyl ester, propyl ester, butyl ester, monooctyl ester, 2-(ethyl hexyl) ester, the last of the ten Heavenly stems ester, dodecyl ester, stearyl ester etc.
It is acrylic acid to enumerate (methyl), carbonatoms 3～18 contain the ether oxyalkyl ester, methoxy ethyl ester for example, the ethoxyethyl group ester, the methoxy-propyl ester, methyl Sheep's-parsley ester, ethyl Sheep's-parsley ester, butyl Sheep's-parsley ester etc., be further used as the monomer that contains bridge shape key, (methyl) vinylformic acid two cyclopentyloxy ethyl esters for example, (methyl) vinylformic acid isobornyl oxygen base ethyl ester, (methyl) isobornyl acrylate, (methyl) vinylformic acid diamantane ester, (methyl) vinylformic acid dimethyladamantane ester, (methyl) vinylformic acid two cyclopentyl esters, (methyl) vinylformic acid two cyclopentenes esters etc., in addition, the alkyl carbon atoms number is 1～18 alkyl vinyl ether, for example, methylvinylether, propyl vinyl ether, dodecyl vinyl etc., (methyl) acrylic acid glycidyl ester, it is glycidyl methacrylate, glycidyl acrylate etc., the vinylbenzene macromonomer 4500 that also has サ-ト マ-company to make, the macromonomers such as NK ester M-230G that Xin Zhong village chemical industry Co., Ltd. makes etc.
Further, can enumerate the monomer that contains siloxane chain etc. of the monomer that vinyl fatty esters such as vinyl cyanide, vinylchlorid, vinylidene chloride, N-vinyl pyrrolidone, vinyl sulfonic acid, vinyl acetate between to for plastic, 3-(methyl) acryloxy propyl trimethoxy silicane etc. contain silane coupled base, (methyl) acrylate that contains the polydimethylsiloxane chain etc.
The method that makes above-mentioned monomer class (I) copolymerization can make in all sorts of ways without any restriction.For example, can use radical polymerization, cationic polymerization, anionic polymerization, wait by solution polymerization, mass polymerization, letex polymerization respectively and make, particularly radical polymerization is because easier and industrial preferred.
The polymerization starter that can be used is not particularly limited in this case, for example, can enumerate azo-compound, the Mn (acac) of superoxide, AIBN, phenylazo triphenyl methanes etc. such as benzoyl peroxide, peroxidation two acyls
3Deng metallo-chelate etc.The consumption of polymerization starter is not particularly limited, and can wait as one sees fit according to the weight-average molecular weight of desired multipolymer and select, be 0.1～5mol% with respect to monomer class (I) usually, be preferably 0.3～3mol%.
Further, can also use chain-transfer agents such as lauryl mercaptan, 2 mercapto ethanol, ethylenebis dithiocarbamate oxyacetic acid, octylsulfo oxyacetic acid as required, also the additive as chain-transfer agent etc. such as the mercaptan compound that contains the coupling base of γ-Qiu Jibingjisanjiayangjiguiwan etc. can be used in addition.
In addition, in the present invention, can also be by the photopolymerization in the presence of photosensitizers or light trigger, carried out or by being that the polymerization of energy source obtains random or segmented copolymer with radioactive rays or hotwork.
Polymerization can be in the presence of the solvent or do not exist under any one condition of solvent and implement, but from the preferably enforcement in the presence of solvent of viewpoint of processing ease.As above-mentioned solvent, for example can use alcohols such as ethanol, Virahol, propyl carbinol, isopropylcarbinol, the trimethyl carbinol, the ketone of acetone, methylethylketone, mibk etc., the ester class of ritalin, vinyl acetic monomer, N-BUTYL ACETATE etc., the polar solvent of dimethyl formamide, dimethyl sulfoxide (DMSO) etc., 1,1, the halogen solvent of 1-trichloroethane, chloroform etc., the ethers of tetrahydrofuran (THF), diox etc., the fragrant same clan organic solvent of benzene,toluene,xylene etc., any one in the fluoro inert liq class of PFO, perfluor tri-n-butylamine etc. in addition.
In addition, also without any restriction, can join in the lump in the reaction vessel, also can the limit monomer class (I) be added drop-wise in the solvent limit and carry out polyreaction the adding mode of reaction materials such as monomer class (I), polymerization starter, solvent.The viewpoint of the heating that particularly calm polymerization easy to control brings and obtaining easily has the viewpoint of the multipolymer of even composition and sets out, the dropping solution that preferred modulation can solvent-laden monomer class (I) uniform mixing obtains, limit should drip drips of solution and be added in the reaction solvent limit and carry out polyreaction.
The multipolymer that obtains by aforesaid method can separate by the whole bag of tricks of various post processing, solvent cleaning, redeposition operation etc., purification operations.In addition, can be only with a kind of multipolymer as the fluorine class tensio-active agent that uses among the present invention, also can use two or more simultaneously.
The adhesive resin that uses among the present invention (B) so long as have at least one aromatic nucleus (b1) and at least a resin of at least one acidic-group (b2) just passable, its structure is not particularly limited.In addition, also can be as adhesive resin (B) also with the resin that has different structure more than 2 kinds or 2 kinds.
As above-mentioned aromatic nucleus (b1), for example, can enumerate and optional have substituent phenyl ring or naphthalene nucleus, can also be 2 or 2 structures that above aromatic nucleus is formed by connecting of biphenyl backbone etc.Further, can also contain aromatic nucleus different more than 2 kinds or 2 kinds (b1) in the above-mentioned adhesive resin (B).Wherein, from good with the consistency of the above-mentioned polyvinyls (A) that contains fluoro-alkyl, can obtain the good viewpoint of filming of uniformity of film, preferably can have substituent phenyl ring.As above-mentioned substituting group, for example, can enumerate carbonatoms and be 1～10 alkyl, hydroxyl, alkoxyl group, carboxyl, sulfonic group, fluorine atom etc.In addition, aromatic nucleus (a2) in the above-mentioned polyvinyls (A) that contains fluoro-alkyl and the aromatic nucleus (b1) in the adhesive resin (B) comprise that substituent having or not can be identical, also can differ from one another, without any restriction.
As above-mentioned acidic-group (b2), for example, can enumerate carboxyl, hydroxyl, phosphate, sulfonic group etc.The substituting group that these groups for example can be used as on the above-mentioned aromatic nucleus (b1) is present in the adhesive resin (B), and its location without limits.In addition, in above-mentioned adhesive resin (B), also can have acidic-group different more than 2 kinds or 2 kinds (b2).Wherein, from with good, the resulting uniformity of film of filming of consistency of the above-mentioned polyvinyls (A) that contains fluoro-alkyl good viewpoint and the good viewpoint of storage stability of resulting resin composite for coating, acidic-group (b2) is preferably carboxyl or hydroxyl, and the few viewpoint of foaming is preferably hydroxyl during from the modulation above-mentioned composition.In addition, acidic-group (a3) in the above-mentioned polyvinyls (A) that contains fluoro-alkyl can be identical with the acidic-group (b2) in the adhesive resin (B), also can differ from one another, without any restriction, but from the better viewpoint of consistency, preferably identical acidic-group.
Above-mentioned adhesive resin (B) is the principal constituent of coating material, known to inventor etc., adhesive resin (B) and the combination that contains the polyvinyls (A) of fluoro-alkyl is carried out optimization, is very important concerning obtaining the even coating of film.The selection of adhesive resin (B) mainly according to the purposes of resin composite for coating, follow desired characteristic of this purposes (for example, mechanical characteristic, resistance to chemical reagents, optical characteristics, elching resistant) and manufacturing process etc. to decide.
For example, under the situation of the positive light anti-etching agent of use i ray, use novolac resin, use the hydroxy styrenes resin under the situation of the photo-resist of use KrF ray as adhesive resin (B), and, be used in combination sensitizer respectively as various reactive compounds.On the other hand, under the situation of colored resist, for example, as soluble acrylic resin in adhesive resin (B) use non-photosensitive and the alkaline aqueous solution [for example, (methyl) vinylformic acid benzyl ester and (methyl) acrylic copolymer, (methyl) vinylformic acid benzyl ester (methyl) vinylformic acid (methyl) acrylic acid alkyl polyoxyethylene ester copolymer etc.], and as the photosensitivity polymerization composition that has reactive compound with it, use polyfunctional acrylic ester etc., further be used in combination Photoepolymerizationinitiater initiater.The antireflection coating agents on colour filter external coating (EC) agent, polaroid surface etc. are not attended by developing procedure in it uses.Promptly in the Yi Shang purposes, (B) (for example uses so-called light-cured resin as adhesive resin, acrylic resin, vinylformic acid oligomer, Acrylic Acid Monomer, Resins, epoxy, acrylic modified epoxy resin, epoxy modified acrylic resin, polyurethane modified acrylic resin, polyester modification acrylic resin etc.), described adhesive resin (B) and Photoepolymerizationinitiater initiater are used in combination to make the coating agent, and be applied on whole of target substrate surface, and whole photocuring used.
Wherein, viewpoint from easy realization effect of the present invention, as the preferred especially acrylic copolymer that has aromatic nucleus and carboxyl simultaneously of adhesive resin (B), for example (methyl) vinylformic acid benzyl ester and (methyl) acrylic acid multipolymer and (methyl) vinylformic acid benzyl ester and (methyl) vinylformic acid and other monomeric multiple copolymers.And the acid number of adhesive resin (B) is preferably 30～400mgKOH/g, and weight-average molecular weight preferably in 1000～300000 scope, is preferably 5000～200000 especially.
Resin composite for coating of the present invention, so long as comprise the above-mentioned polyvinyls (A) of fluoro-alkyl and the resin combination of adhesive resin (B) of containing, in addition without any restriction.Also other compositions can be contained according to purposes, for example, in photosensitive color resin combination etc., tinting material (pigment, dyestuff etc.), dispersion agent etc. can be further contained.The polyvinyls that contains fluoro-alkyl (A) that uses among the present invention is owing to have an aromatic nucleus, so good with the consistency of organic based colorant (pigment) of general use.In addition, as required, can also in resin combination of the present invention, add other compositions, for example the various additives of the bounding force reinforcer of necessary reactive compounds, solvent, other tensio-active agents, preserving stabilizer, softening agent, fluorescent agent, developer, thickening material, thixotropic agent, resin dissolves inhibitor, silane coupling agent etc. etc. under the situation about using as photo-resist.
For example, the example of operable composition during as negative type photoresist, can enumerate can be by the vinyl monomer class of rayed addition polymerization and the combination of Photoepolymerizationinitiater initiater.As the object lesson of this vinyl monomer class, can enumerate Viscoat 295, tetramethylol methane tetraacrylate, Dipentaerythritol five acrylate, dipentaerythritol acrylate etc.The example of operable composition when the positive light anti-etching agent can be enumerated and is fit to benzoquinones two nitrine compounds that the adhesive resin with the novolac resin class is used in combination etc.
Can there be any all kinds of SOLVENTS that restrictedly uses as above-mentioned solvent, for example, can enumerate acetone, methylethylketone, pimelinketone, cyclopentanone, suberone, 2-heptanone, methyl iso-butyl ketone (MIBK), the ketone of butyrolactone etc., methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, the trimethyl carbinol, amylalcohol, enanthol, octanol, nonyl alcohol, the alcohols of decyl alcohol etc., glycol dimethyl ether, the ethers of ethylene glycol diethyl ether diox etc., ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, the pure ethers of propylene glycol monopropyl ether etc., ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, butylacetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl-butyrate, ethyl butyrate, butyl butyrate, the ester class of propyl butyrate etc., 2-oxo methyl propionate, ethyl 2-oxopropanoate, 2-oxo propyl propionate, 2-oxo butyl propionate, 2-methoxypropionic acid methyl esters, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, monocarboxylate's class of 2-methoxy propyl acid butyl ester etc., cellosolve acetate, methylcellosolve acetate, ethyl cellosolve acetate, the propyl cellosolve acetic ester, cellosolve ester classes such as butyl cellosolve acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, the propandiols of propylene glycol monobutyl ether acetic ester etc., diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Diethylene Glycol classes such as diethylene glycol ethylmethyl ether, trieline, the fluorocarbon solvent, HCFC, the halogenated hydrocarbon of HFC etc., the complete fluorinated solvents class that PFO is such, toluene, the fragrant same clan organic solvent of dimethylbenzene etc., N,N-DIMETHYLACETAMIDE, dimethyl formamide, the N-methylacetamide, the polar solvent of N-Methyl pyrrolidone etc. etc., can use separately, also can mix solvents different more than 2 kinds or 2 kinds and use.
Wherein, from the coating of gained resin composite for coating and the good viewpoint of balance of drying property, preferably using boiling point under normal pressure is 80～200 ℃ solvent.
As the blending ratio of above-mentioned solvent, can be according to the adjusting that suit of the thickness of coating necessity during resin composite for coating and coating condition.But with respect to the resinous principle in the resin composite for coating that amounts to 100 weight parts [adhesive resin (B) and as required also the above-mentioned various reactive compounds of usefulness], above-mentioned solvent is generally 10～10000 weight parts, is preferably 50～2000 weight parts.
Can use pigment such as redness, green, blueness, black and dyestuff etc. as above-mentioned tinting material with being not particularly limited.Consider preferred pigments from thermotolerance, photostabilization aspect, the median size of pigment is 0.005～3 μ m usually, and 0.01～1 μ m is considered to be preferably in particularly good from the coating of resin composite for coating and the aspect of filming that obtain having the transparency.
As above-mentioned dispersion agent, so long as effective dispersion agent just is not particularly limited during the toner that is scattered here and there etc.For example, can enumerate the intermediate of pigment, the intermediate of dyestuff, polyamide-based compound, polyurethanes compound, acrylic compounds, polyester compound etc.
The above-mentioned content that contains the polyvinyls (A) of fluoro-alkyl in the resin composite for coating of the present invention, can according to coating on substrate during above-mentioned resin combination required thickness, coating condition wait as one sees fit and select.Usually in the above-mentioned resin combination of per 100 weight parts, the polyvinyls (A) that contains fluoro-alkyl is 0.0005～10 weight part, is preferably 0.005～5 weight part, more preferably 0.05～1 weight part.
In addition, when using the low polyvinyls that contains fluoro-alkyl (A) of fluorine atom containing ratio,, can give full play to effect of the present invention by increasing the content of the polyvinyls that contains fluoro-alkyl (A) in the resin composite for coating of the present invention.
In the manufacturing of resin composite for coating of the present invention, the method for mixing the above-mentioned polyvinyls (A) that contains fluoro-alkyl without limits.For example, can be set forth in advance and add the also method of mixed ethylene base polymer (A) in above-mentioned each mixture of ingredients of uniform mixing, or when making the photosensitive color resin combination, carry out usually, when the so-called colored paste of tinting material dispersive being prepared in the method etc. of interpolation polyvinyls (A) with adhesive resin (B), dispersion agent and solvent etc., after polyvinyls (A) dissolved in advance or being dispersed in specific separate constituent in the resin composite for coating or the multiple composition, the method for modulation above-mentioned composition etc.
As the coating process of resin composite for coating of the present invention, can be suitable for the whole bag of tricks and be not particularly limited.For example be fit to use method of spin coating, rolling method, dip coating, spraying method, spread coating, curtain to be coated with method, slot coated method, Xia Feng ﹠amp; Method of spin coating etc. are particularly suitable for using method of spin coating, Xia Feng ﹠amp; The film coated method of method of spin coating, slot coated method etc.In addition, the method for filming for formation also is not particularly limited, and can select according to purposes of resin composite for coating etc.As the method that obtains target film, preferably and as required and other reactive compounds of usefulness etc., take the circumstances into consideration to select to use seasoning (japanning), thermofixation reaction, photocuring reaction etc. according to adhesive resin (B).
In addition, the purposes of resin composite for coating of the present invention also is not particularly limited.Be particularly suitable in the manufacturing of the colour filter of the LCD panel manufacturing usefulness of Personal Computer, PDA (portable information terminal), TV, portable phone, video recorder etc. or crystal liquid substrate, perhaps in various semi-conductive manufacturings such as LSI, IC, using in photolithographic various fields with, PS version.Particularly its photosensitive color resin composition for color, colour filter that is used as the liquid-crystal display manufacturing usefulness of the meticulous colored pattern of needs with external coating (EC) agent, liquid crystal cell with spacer material, optical thin film during with antireflection film material, various hard Coating Materials etc., can easily bring into play effect of the present invention, be most preferred purposes.
Embodiment
Below by enumerate concrete synthesis example, embodiment illustrates in greater detail the present invention.In addition, " part " among the embodiment and " % " are benchmark with weight unless otherwise specified.
Synthesis example 1
In the glass flask that has whipping appts, condenser, thermometer, dropping funnel, add 200 parts of methyl iso-butyl ketone (MIBK) (MIBK), stir down with the air in the abundant replacement(metathesis)reaction container of nitrogen.Then, be warmed up to 90 ℃, dripped the mixture of monomer class (I-1), 100 parts of MIBK, 4.0 parts of azobis isobutyronitriles (AIBN) under same temperature through 2 hours with dropping funnel, wherein monomer class (I-1) has been mixed 20 parts the vinyl monomer that contains fluoro-alkyl (x1-1-1), 78 parts of methacrylic acid benzyl esters, 2 parts of methacrylic acids.After drip finishing, under same temperature, keep carrying out in 10 hours polyreaction, desolventizing under 80 ℃ of decompressions then, dry residual solids component obtains multipolymer (A-1).Using tetrahydrofuran (THF) (THF) as moving phase, measure the weight-average molecular weight of gained multipolymer by gel permeation chromatography (GPC), is 10900 with the scaled value of polystyrene.
Synthesis example 2
Except in synthesis example 1, change monomer class (I-1) into form monomer class (I-2) in addition, adopt with the same method of synthesis example 1 and synthesized multipolymer (A-2) by 20 parts of vinyl monomers (x1-1-7) that contain fluoro-alkyl, 78 parts of methacrylic acid benzyl esters, 2 parts of methacrylic acids.The weight-average molecular weight of gained multipolymer (A-2) is 10200.
Synthesis example 3
Except in synthesis example 1, change monomer class (I-1) into form monomer class (I-3) in addition, adopt with the same method of synthesis example 1 and synthesized multipolymer (A-3) by 20 parts of vinyl monomers (x1-1-1) that contain fluoro-alkyl, 55 parts of methacrylic acid benzyl esters, 25 parts of 2-hydroxyethyl methacrylates.The weight-average molecular weight of gained multipolymer (A-3) is 11000.
Synthesis example 4
Except in synthesis example 1, change monomer class (I-1) into form monomer class (I-4) in addition, adopt with the same method of synthesis example 1 and synthesized multipolymer (A-4) by 35 parts of vinyl monomers (x1-1-1) that contain fluoro-alkyl, 63 parts of methacrylic acid benzyl esters, 2 parts of methacrylic acids.The weight-average molecular weight of gained multipolymer (A-4) is 11600.
Synthesis example 5
Except in synthesis example 1, change monomer class (I-1) into form monomer class (I-5) in addition, adopt with the same method of synthesis example 1 and synthesized multipolymer (A-5) by 10 parts of vinyl monomers (x1-1-1) that contain fluoro-alkyl, 80 parts of methacrylic acid benzyl esters, 10 parts of methacrylic acids.The weight-average molecular weight of gained multipolymer (A-5) is 10700.
Synthesis example 6
Except in synthesis example 1, change monomer class (I-1) into form monomer class (I-6) in addition, adopt with the same method of synthesis example 1 and synthesized multipolymer (A-6) by 20 parts of vinyl monomers (x1-1-1) that contain fluoro-alkyl, 70 parts of methacrylic acid benzyl esters, 10 parts of methacrylic acids.The weight-average molecular weight of gained multipolymer (A-6) is 10000.
Synthesis example 7
Except in synthesis example 1, change monomer class (I-1) into form monomer class (I-7) in addition, adopt with the same method of synthesis example 1 and synthesized multipolymer (A-7) by 20 parts of vinyl monomers (x1-1-1) that contain fluoro-alkyl, 48 parts of methacrylic acid benzyl esters, 2 parts of methacrylic acids, 30 parts of methyl methacrylates.The weight-average molecular weight of gained multipolymer (A-7) is 12000.
Synthesis example 8
Except in synthesis example 1, change monomer class (I-1) into form monomer class (I-8) in addition, adopt with the same method of synthesis example 1 and synthesized multipolymer (A-8) by 20 parts of vinyl monomers (x1-1-1) that contain fluoro-alkyl, 65 parts of methacrylic acid benzyl esters, 2 parts of methacrylic acids, 13 parts of 2-hydroxyethyl methacrylates.The weight-average molecular weight of gained multipolymer (A-8) is 12300.
Synthesis example 9
In the glass flask that has whipping appts, condenser, thermometer, dropping funnel, add 100 parts of methyl iso-butyl ketone (MIBK), stir down with the air in the abundant replacement(metathesis)reaction container of nitrogen.Then, be warmed up to 80 ℃, dripped the mixture of monomer class (I-9), 50 parts of MIBK, 1.0 parts of AIBN under same temperature through 2 hours with dropping funnel, wherein monomer class (I-9) has been mixed 20 parts the vinyl monomer that contains fluoro-alkyl (x1-1-1), 78 parts of methacrylic acid benzyl esters, 2 parts of methacrylic acids.After drip finishing, under same temperature, keep carrying out in 10 hours polyreaction, desolventizing under 80 ℃ of decompressions then, dry residual solids component obtains multipolymer (A-9).The weight-average molecular weight of gained multipolymer (A-9) is 46500.
Synthesis example 10
Except in synthesis example 9, change monomer class (I-9) into form monomer class (I-10) in addition, adopt with the same method of synthesis example 9 and synthesized multipolymer (A-10) by 20 parts of vinyl monomers (x1-1-1) that contain fluoro-alkyl, 55 parts of methacrylic acid benzyl esters, 25 parts of 2-hydroxyethyl methacrylates.The weight-average molecular weight of gained multipolymer (A-10) is 48000.
Synthesis example 11(vinyl monomer that contains fluoro-alkyl of record is synthetic in above-mentioned patent documentation 1)
Except in synthesis example 1, monomer class (I-1) changed into by 20 parts of vinyl monomers (x1-1-1) that contain fluoro-alkyl, 30 parts of different stearyl esters of vinylformic acid, 42 parts molecular weight be about monomer class (I-11) that single terminal acrylate of the multipolymer of 400 oxyethane and propylene oxide, 8 parts of methyl methacrylates form in addition, adopt with the same method of synthesis example 1 and synthesized multipolymer (A-11).The weight-average molecular weight of gained multipolymer (A-11) is 11000.
Synthesis example 12(vinyl monomer that contains fluoro-alkyl of record is synthetic in above-mentioned patent documentation 1)
Except in synthesis example 1, monomer class (I-1) changed into by 20 parts of ethylene unsaturated monomers (x1-1-1) that contain fluoro-alkyl, 30 parts of different stearyl esters of vinylformic acid, 42 parts molecular weight be about monomer class (I-12) that single terminal acrylate of 500 and one terminal polyethylene oxide for methyl, 8 parts of methyl methacrylates form in addition, adopt and method that synthesis example 1 is same has been synthesized multipolymer (A-12).The weight-average molecular weight of gained multipolymer (A-12) is 12200.
Synthesis example 13
Except in synthesis example 9, change monomer class (I-9) into form monomer class (I-13) in addition, adopt with the same method of synthesis example 9 and synthesized multipolymer (A-13) by 30 parts of vinyl monomers (x1-1-1) that contain fluoro-alkyl, 30 parts of methacrylic acids, 40 parts of methyl methacrylates.The weight-average molecular weight of gained multipolymer (A-13) is 46000.
The synthetic fluorine atom containing ratio, aromatic nucleus containing ratio, the acid number/hydroxyl value that contain the polyvinyls of fluoro-alkyl is recorded in the table 1 according to the method described above.
[table 1]
The character of fluorine class tensio-active agent
| The polyvinyls that contains fluoro-alkyl | Fluorine atom containing ratio (%) | Aromatic nucleus containing ratio (%) | Acid number/hydroxyl value (mg/KOH) |
| A-1 | 12.5 | 34 | 13/0 |
| A-2 | 11.2 | 34 | 13/0 |
| A-3 | 12.5 | 24 | 0/108 |
| A-4 | 21.8 | 27 | 13/0 |
| A-5 | 6.2 | 35 | 65/0 |
| A-6 | 12.5 | 31 | 65/0 |
| A-7 | 12.5 | 21 | 13/0 |
| A-8 | 18.7 | 28 | 13/56 |
| A-9 | 12.5 | 34 | 13/0 |
| A-10 | 12.5 | 24 | 0/108 |
| A-11 | 12.5 | 0 | 0/59 |
| A-12 | 12.5 | 0 | 0/0 |
| A-13 | 18.7 | 0 | 196/0 |
Embodiment 1～10 and comparative example 1～3
In the high speed dispersor of the zirconia ball that to have added 200 parts of diameters be 0.5mm, add 8.0 parts of C.I. Pigment reds 254 as tinting material, 2.5 part ア ジ ス パ-PB814 (trade name as the polyester dispersion agent, monosodium glutamate Co., Ltd. makes), 25.0 part methacrylic acid/methacrylic acid benzyl ester=13/87 (weight ratio) multipolymer (acid number 84mgKOH/g as adhesive resin (B), weight-average molecular weight 22000) propylene glycol methyl ether acetate solution (nonvolatile component is 39.7 weight %), 64.5 part propylene glycol methyl ether acetate as solvent, carry out 8 hours dispersion with rotating speed 2000rpm, obtain the red pigment dispersion liquid.Then, with respect to 100 parts of these red pigment dispersion liquids, interpolation also mixes 7.0 parts of dipentaerythritol acrylates as photopolymerization monomer, 0.3 part of イ Le ガ キ ュ ア #369 (trade name as Photoepolymerizationinitiater initiater, チ バ ス ペ シ ヤ リ テ イ-ケ ミ カ Le ズ Co., Ltd. makes), behind 0.11 part of fluorine class tensio-active agent by the multipolymer that obtains in the synthesis example 1～14 (A-1)～(A-13) form, with the aperture is the strainer filtration of 1.0 μ m, makes resin composite for coating (embodiment 1～10 and comparative example 1～3).About the coating of gained resin combination, carry out following experiment.Evaluation result is shown in Table 2.
Comparative example 4(the fluorine class tensio-active agent that uses in the above-mentioned patent documentation 2)
Except using メ ガ Off ア ッ Network R-30 (the fluoropropenes acid oligomer that contains perfluoroalkyl that big Japanese イ Application キ KCC makes), similarly to carry out the coating evaluation with the foregoing description 1～10 and comparative example 1～3 as the fluorine class tensio-active agent.
Comparative example 5(the fluorine class tensio-active agent that uses in the above-mentioned patent documentation 2)
Except the C that uses the big Japanese イ Application キ of メ ガ Off ア ッ Network F-143[KCC to make
8F
17SO
2N (R) CH
2CH
2O (CH
2CH
2O)
nH (R is an alkyl, the average out to 15 of n)] as beyond the fluorine class tensio-active agent, similarly carry out the coating evaluation with the foregoing description 1～10 and comparative example 1～3.
Comparative example 6
Except using the C of non-polymeric type
6F
13CH
2CH
2SCH
2CH
2COONH
4Beyond fluorine class tensio-active agent, similarly carry out the coating evaluation with the foregoing description 1～10 and comparative example 1～3.
The test method of coating
Add 1ml on the square sheet glass of 12cm middle body by the synthetic resin composite for coating of aforesaid method, be rotated coating with rotating speed 600rpm, 30 seconds condition of rotational time.Under 90 ℃, make its heat drying 3 minutes then, filmed the condition of surface that the visual observation gained is filmed with the high pressure mercury vapour lamp curing of 120W/cm.
Judgement criteria
1: do not observe the generation crawling.
2: observe the practical crawling slightly of no problem degree takes place.
3: observe part generation crawling.
4: observe remarkable generation crawling.
In addition, above-mentioned 4 numerals, numerical value is more little preferred more with regard to ecbatic.
In addition, although this coating process is a method of spin coating, rotating speed is lower, thus in the rotary coating solvent disperse lessly, be about 15～30%.[when rotating with high speed (2000～3000 rotating speed) usually, 85～95% solvent disperses when rotated.] thereby, except the coating spot that shearing force produced (in rotary coating, becoming the crawling of problem) of accompanying rotation, can also observe having or not of solvent seasoning spot in the drying process of the problem that in rotary coating, is regarded as especially simultaneously.
[table 2]
The evaluation result of filming of resin composite for coating
| Fluorine class tensio-active agent | The coating outward appearance | |
| Embodiment 1 | A-1 | 1 |
| Embodiment 2 | A-2 | 2 |
| Embodiment 3 | A-3 | 1 |
| Embodiment 4 | A-4 | 1 |
| Embodiment 5 | A-5 | 2 |
| Embodiment 6 | A-6 | 1 |
| Embodiment 7 | A-7 | 2 |
| Embodiment 8 | A-8 | 1 |
| Embodiment 9 | A-9 | 1 |
| Embodiment 10 | A-10 | 1 |
| Comparative example 1 | A-11 | 3 |
| Comparative example 2 | A-12 | 3 |
| Comparative example 3 | A-13 | 4 |
| Comparative example 4 | メガフアックR-30 | 3 |
| Comparative example 5 | メガフアックF-143 | 4 |
| Comparative example 6 | C 6F 13CH 2CH 2SCH 2CH 2COONH 4 | 4 |
Embodiment 11～20, comparative example 7～12
In container, add the 25.0 parts of methacrylic acid as adhesive resin (B)/methacrylic acid benzyl ester=13/87 (weight ratio) multipolymer (acid number 84mgKOH/g, weight-average molecular weight is 22000) propylene glycol methyl ether acetate solution (nonvolatile component is 39.7 weight %), 64.5 parts of propylene glycol methyl ether acetates as solvent, add respectively and mix 0.11 part of fluorine class tensio-active agent and メ ガ Off ア ッ Network R-30, F-143 and C by the multipolymer that obtains in the synthesis example 1～13 (A-1)～(A-13) form
6F
13CH
2CH
2SCH
2CH
2COONH
4Then, be the strainer filtration of 1.0 μ m with the aperture, make resin composite for coating (embodiment 11～20 and comparative example 7～12).
The test method of coating
Add 1ml on the square sheet glass of 12cm middle body by the synthetic resin composite for coating of aforesaid method, be rotated coating with rotating speed 600rpm, 30 seconds condition of rotational time.Under 90 ℃, make its heat drying 3 minutes, the condition of surface that visual observation is filmed then.The results are shown in the table 3.
Judgement criteria
1: do not observe the generation crawling.
2: observe the practical crawling slightly of no problem degree takes place.
3: observe part generation crawling.
4: observe remarkable generation crawling.
The test method of defoaming
50g is joined in the vial of 100cc by the synthetic resin composite for coating of aforesaid method and plug tight.With manual mode with its reciprocating vibration 10 times after, measure up to the bubble froth breaking of foaming and the time till exposing liquid level.The result is recorded in the table 3.
[table 3]
The evaluation result of filming of resin composite for coating
| Fluorine class tensio-active agent | The coating outward appearance | Liquid level exposes the time (s) | |
| Embodiment 11 | A-1 | 1 | 95 |
| Embodiment 12 | A-2 | 2 | 70 |
| Embodiment 13 | A-3 | 1 | 130 |
| Embodiment 14 | A-4 | 1 | 140 |
| Embodiment 15 | A-5 | 2 | 90 |
| Embodiment 16 | A-6 | 1 | 180 |
| Embodiment 17 | A-7 | 2 | 110 |
| Embodiment 18 | A-8 | 1 | 110 |
| Embodiment 19 | A-9 | 1 | 250 |
| Embodiment 20 | A-10 | 1 | 280 |
| Comparative example 7 | A-11 | 3 | 190 |
| Comparative example 8 | A-12 | 3 | 300 |
| Comparative example 9 | A-13 | 4 | 420 or more than it |
| Comparative example 10 | メガフアックR-30 | 3 | 120 |
| Comparative example 11 | メガフアックF-143 | 4 | 330 |
| Comparative example 12 | C 6F 13CH 2CH 2SCH 2CH 2COONH 4 | 4 | 420 or more than it |
Industrial applicibility
Can provide the uniformity of film of filming good resin composite for coating by the present invention. Above-mentioned composition can be suitable for requiring meticulous pattern precision the field, need in the film forming field etc.
Claims (8)
1. resin composite for coating is characterized in that said composition contains:
The fluorine class tensio-active agent of forming by the polyvinyls that contains fluoro-alkyl (A), the described polyvinyls (A) that contains fluoro-alkyl has fluoro-alkyl (a1), aromatic nucleus (a2) and acidic-group (a3), and the weight-average molecular weight of described polymkeric substance (A) is 1000～200000; And
Adhesive resin (B), it has aromatic nucleus (b1) and acidic-group (b2).
2. resin composite for coating according to claim 1, the described fluorine atom containing ratio that contains the polyvinyls (A) of fluoro-alkyl is 7～35 weight %, the aromatic nucleus containing ratio of measuring with the FT-IR method is 10～40 weight %, acid number is that 2～100mgKOH/g and/or hydroxyl value are 20～200mgKOH/g, and weight-average molecular weight is 5000～100000.
3. resin composite for coating according to claim 1, the described polyvinyls (A) that contains fluoro-alkyl is the multipolymer that obtains by polymerization single polymerization monomer class (I), the vinyl monomer (x3) that this monomer class (I) comprises the vinyl monomer (x1) that contains fluoro-alkyl, the vinyl monomer (x2) that contains aromatic nucleus and contains acidic-group.
4. resin composite for coating according to claim 3, the vinyl monomer that contains fluoro-alkyl (x1) in the above-mentioned monomer class (I), contain the vinyl monomer (x2) of aromatic nucleus and contain acidic-group vinyl monomer (x3) add up to 60 weight % or more than it, and the containing ratio of the vinyl monomer that contains fluoro-alkyl (x1) in above-mentioned monomer class (I) is 3～50 weight %, the containing ratio that contains the vinyl monomer (x2) of aromatic nucleus is 40～90 weight %, and the containing ratio that contains the vinyl monomer (x3) of acidic-group is 0.1～30 weight %.
5. resin composite for coating according to claim 4, the described vinyl monomer (x2) that contains aromatic nucleus is (methyl) vinylformic acid benzyl ester.
6. resin composite for coating according to claim 4, the acidic-group in the described vinyl monomer (x3) that contains acidic-group is carboxyl or hydroxyl.
7. resin composite for coating according to claim 1, described adhesive resin (B) is the acrylic polymers with aromatic nucleus and carboxyl.
8. resin composite for coating according to claim 1, the described blending ratio of polyvinyls (A) in resin composite for coating that contains fluoro-alkyl is 0.0005～10 weight %.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP053078/2004 | 2004-02-27 | ||
| JP2004053078 | 2004-02-27 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1906258A CN1906258A (en) | 2007-01-31 |
| CN100526404C true CN100526404C (en) | 2009-08-12 |
Family
ID=34908728
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005800015862A Active CN100526404C (en) | 2004-02-27 | 2005-02-23 | Resin composition for coating |
Country Status (4)
| Country | Link |
|---|---|
| KR (1) | KR101099399B1 (en) |
| CN (1) | CN100526404C (en) |
| TW (1) | TWI346683B (en) |
| WO (1) | WO2005083019A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4759483B2 (en) * | 2006-09-25 | 2011-08-31 | Ａｚエレクトロニックマテリアルズ株式会社 | Photoresist composition, method of applying photoresist composition, and method of forming resist pattern |
| CN101271271B (en) * | 2007-03-21 | 2012-01-11 | 新应材股份有限公司 | Positive photoresist |
| CN103319959B (en) * | 2013-06-09 | 2015-11-18 | 广州市承信公路工程检验有限公司 | Bridge cable protective polyethylene priming paint and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1115113A (en) * | 1993-12-22 | 1996-01-17 | Rca汤姆森许可公司 | CRT electrophotographic screening method using an organic photoconductor |
| CN1144226A (en) * | 1990-11-27 | 1997-03-05 | 博士伦有限公司 | Method for preparing surface active random copolymer |
| JP2003222997A (en) * | 2001-11-22 | 2003-08-08 | Fujifilm Arch Co Ltd | Photosensitive colored resin composition, method for producing the same and method for producing color filter |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3716946B2 (en) * | 1996-05-08 | 2005-11-16 | 大日本インキ化学工業株式会社 | Thermosetting powder coating resin composition |
| JP2004002733A (en) * | 2002-03-28 | 2004-01-08 | Dainippon Ink & Chem Inc | Coating composition |
-
2005
- 2005-02-23 KR KR1020067011155A patent/KR101099399B1/en active IP Right Grant
- 2005-02-23 CN CNB2005800015862A patent/CN100526404C/en active Active
- 2005-02-23 TW TW094105415A patent/TWI346683B/en active
- 2005-02-23 WO PCT/JP2005/002912 patent/WO2005083019A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1144226A (en) * | 1990-11-27 | 1997-03-05 | 博士伦有限公司 | Method for preparing surface active random copolymer |
| CN1115113A (en) * | 1993-12-22 | 1996-01-17 | Rca汤姆森许可公司 | CRT electrophotographic screening method using an organic photoconductor |
| JP2003222997A (en) * | 2001-11-22 | 2003-08-08 | Fujifilm Arch Co Ltd | Photosensitive colored resin composition, method for producing the same and method for producing color filter |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1906258A (en) | 2007-01-31 |
| TW200609308A (en) | 2006-03-16 |
| TWI346683B (en) | 2011-08-11 |
| WO2005083019A1 (en) | 2005-09-09 |
| KR101099399B1 (en) | 2011-12-27 |
| KR20060126493A (en) | 2006-12-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5281412B2 (en) | Black matrix pigment dispersion composition and black matrix pigment dispersion resist composition containing the same | |
| CN101331157B (en) | Fluorine-containing polymer, negative photosensitive composition and partition wall | |
| CN101379132B (en) | Curable composition, color filter, and liquid crystal display device | |
| JP6960304B2 (en) | A pigment dispersion composition for a black matrix and a pigment dispersion resist composition for a black matrix containing the same. | |
| JP2018123274A (en) | Alkali-soluble resin, photosensitive resin composition and use therefor | |
| TWI557185B (en) | Novel compound, polymer, colorant including the same, photosensitive resin composition including the same, and color filter | |
| CN104932199A (en) | Radiation-sensitive composition, cured film, display device and colorants dispersion | |
| CN103635541A (en) | Dye dispersion, photosensitive resin composition for color filter, color filter, liquid crystal display device, and organoluminescent display device | |
| CN110998443A (en) | Photosensitive resin composition and method for producing same | |
| TWI791651B (en) | Black pigment dispersion composition and black pigment dispersion resist composition containing the same | |
| JP5932435B2 (en) | Blue pigment dispersion composition for color filter and blue pigment dispersion resist composition for color filter containing the same | |
| JP6543453B2 (en) | Pigment dispersion composition for black matrix | |
| JP5737553B2 (en) | Fluorosurfactant, coating composition using the same, and resist composition | |
| JP6113466B2 (en) | Black matrix pigment dispersion composition and black matrix pigment dispersion resist composition containing the same | |
| JP4403355B2 (en) | Color resist composition | |
| TW201829489A (en) | Resin composition for color filter, method for producing same, and color filter | |
| CN104231150A (en) | Alkali-soluble resin polymer and preparation method thereof | |
| CN100526404C (en) | Resin composition for coating | |
| JP5637539B2 (en) | Pigment dispersant and method for producing the same, pigment colorant composition, and pigment colorant composition for color filter | |
| JP5297010B2 (en) | Coloring composition for pixel formation, method for producing color filter, and color filter | |
| JP3753151B2 (en) | Resin composition for coating | |
| JP7564294B2 (en) | Colored composition and colored resist composition | |
| CN106967043A (en) | Compound, polymer, colouring agent, photosensitive resin composition, photo-sensitive resin and colored filter | |
| JPH1046050A (en) | Pigment dispersion and coating agent composition using the same | |
| JP3590481B2 (en) | Pigment dispersion and coating composition using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |