CN107703717A - Positive type photosensitive organic compound, the manufacture method of metal line and layered product - Google Patents
Positive type photosensitive organic compound, the manufacture method of metal line and layered product Download PDFInfo
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- CN107703717A CN107703717A CN201710643741.5A CN201710643741A CN107703717A CN 107703717 A CN107703717 A CN 107703717A CN 201710643741 A CN201710643741 A CN 201710643741A CN 107703717 A CN107703717 A CN 107703717A
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- film
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/008—Azides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
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- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Materials For Photolithography (AREA)
Abstract
The present invention relates to positive type photosensitive organic compound, the manufacture method of metal line and layered product.The problem of the present invention is to provide：Positive type photosensitive organic compound, it is used to form organic film, used when the organic film forms metal line being etched to metal film as etching mask, and the permanent film of the metal line formed in the state of cured as coated etched uses, the permanent film entire surface that equably coated metal connects up, and the not position beyond coated metal wiring；The manufacture method of metal line, it uses the positive type photosensitive organic compound；And layered product, it has the permanent film for being solidified to form the positive type photosensitive organic compound and metal line.The present invention forms patterned above-mentioned organic film using following positive type photosensitive organic compounds, and the positive type photosensitive organic compound includes (A) Novolac resins, the compound of (B) containing quinone diazido and (C) colouring agent.
Description
Technical field
The present invention relates to：Positive type photosensitive organic compound, the positive type photosensitive organic compound are used to be formed through figure
The organic film of case, covered when the patterned organic film forms metal line being etched to metal film as etching
Mould uses, and the permanent film of the metal line formed in the state of cured as coated etched uses；Hardware cloth
The manufacture method of line, methods described use the positive type photosensitive organic compound；And layered product, the layered product have make this just
The permanent film and metal line that type photosensitive polymer combination is solidified to form.
Background technology
With the rapid popularization of smart mobile phone, plate information communication terminal, touch panel market develops rapidly.
For the touch panel, the electrode being made up of metal, wiring are formed in display surface sometimes.For example, make
For such electrode, the wire mesh electrode for having used Cu, Ag can be enumerated.However, form what is be made up of metal in display surface
In the case of electrode, wiring, the problem of easy visual identification of user that touch panel be present goes out metal electrode, metal line,
Even if assume make the metal electrode, the line width of metal line taper to human eye can not visual identification degree, also can still produce down
State problem：Cause the reflection that ambient occurs because the reflectivity of metal is high.
In order to solve the above problems, it is proposed that set reflectivity low on the metallic film of metal electrode, metal line etc.
Reflectivity controlling organization method.
It is known that there are following methods：Using photosensitive polymer combination, using photoetching process in transparent supporting mass
On metal level on patterned resin bed is set, then by etching will from the opening portion of patterned resin bed reveal
The metal level gone out is removed, and then resin bed is toasted, thus, sets being uniformly coated to etched metal level
Reflectivity controlling organization (toasted resin bed) (referring to patent document 1.).
That is, in the method described in patent document 1, patterned resin bed be also used as being used for by etch and
Form the etching mask and reflex control mechanism of metal line.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2016-071242 publications
The content of the invention
Invent problem to be solved
However, using the photosensitive polymer combination described in patent document 1, coated warp is formed using the above method
It is during reflectivity controlling organization (the toasted resin bed) on metal level (metal line) surface of etching, i.e., enabled to be equably coated to
The entire surface of metal line, remain on and position (typically pixel portion) beyond metal line be present by reflectivity controlling organization
Coated situation.In this case, because the transmission of the light in the position beyond metal line is obstructed, thus be difficult with having
The substrate of metal line manufactures the image display device for the image that can show high image quality.
The present invention be in view of above-mentioned problem and make, and it is an object of the present invention to provide：Positive type photosensitive organic compound, it is described just
Type photosensitive polymer combination is used to form patterned organic film, and the patterned organic film is carried out to metal film
Use as etching mask when etching and forming metal line, and formed in the state of cured as coated etched
The permanent film of metal line use, the positive type photosensitive organic compound can form the whole of equably coated metal wiring
The permanent film at the position beyond individual face and not coated metal wiring；The manufacture method of metal line, methods described are using this just
Type photosensitive polymer combination；And layered product, the layered product, which has, is solidified to form the positive type photosensitive organic compound
Permanent film and metal line.
It should be noted that in present specification, the entire surface of permanent film coated metal wiring refers to following states：Pin
Substrate with the metal line being coated to by permanent film is entered from the direction vertical there is provided the face of metal line with substrate
During row observation, do not observe metal line and expose.
When observing the section with metal line and the substrate of permanent film, a part for the side of metal line
It can expose.
Means for solving the problems
Inventors herein have recognized that contain the nitrine of quinone two by using comprising (A) Novolac resins, (B)
(quinonediazide) positive type photosensitive organic compound of the compound of base and (C) colouring agent is following through pattern to be formed
The organic film of change, above-mentioned problem is can solve the problem that, so as to complete the present invention, the patterned organic film enters to metal film
Row etching and is used as etching mask when forming metal line, and be used as in the state of cured and to be coated to etched and shape
Into metal line permanent film use.
That is, the 1st mode of the invention is positive type photosensitive organic compound, and the positive type photosensitive organic compound is used for
Patterned organic film is formed, the patterned organic film is made when forming metal line being etched to metal film
Used for etching mask, and the permanent film of the metal line formed in the state of cured as coated etched makes
With,
The positive type photosensitive organic compound include (A) Novolac resins, the compound of (B) containing quinone diazido,
(C) colouring agent.
The 2nd mode of the present invention is the manufacture method of metal line, and methods described includes following processes：
The process for being coated with the positive type photosensitive organic compound that is related to of the 1st mode on metal film and forming coated film；
The process being exposed to coated film regioselectivity；
The process that exposed coating film development is formed into etching mask；
The metal film on the surface with etching mask is etched, the coated hardware cloth of mask is etched so as to be formed
The process of line；And
Etching mask is toasted, so as to form the process of the permanent film of coated metal wiring.
The 3rd mode of the present invention is layered product, and the layered product includes metal line and permanent film,
Permanent film is contacted with metal line and coated metal wiring,
Permanent film is the film that the positive type photosensitive organic compound for being related to the 1st mode is solidified to form.
The effect of invention
By means of the invention it is possible to provide：Positive type photosensitive organic compound, the positive type photosensitive organic compound are used for
Patterned organic film is formed, the patterned organic film is made when forming metal line being etched to metal film
Used for etching mask, and the permanent film of the metal line formed in the state of cured as coated etched makes
With the positive type photosensitive organic compound can form the equably entire surface of coated metal wiring and not coated metal
The permanent film at the position beyond wiring；The manufacture method of metal line, methods described use the positive type photosensitive organic compound；
And layered product, the layered product have the permanent film for being solidified to form the positive type photosensitive organic compound and metal line.
Brief description of the drawings
[Fig. 1] is the figure for the summary for being shown schematically in the method that metal line is manufactured on substrate.
[Fig. 2] is one 's of the liquid crystal display device purposes for schematically showing the substrate manufactured in present embodiment
Figure.
Description of reference numerals
1 base plate for liquid crystal display device
10 substrates
11 metal films
12 coated films
13 colour filters
14 hyaline layers
15 photomasks
16 exposure lights
17 coated with resin layers
18 metal lines
19 transparent resin layers
20 liquid crystal layers
21 pixel electrodes
22 insulating barriers
23 array base paltes
BM black matrix"s
R, red (R) coloring film of G, B, green (G) coloring film, blueness (B) coloring film
Embodiment
《Positive type photosensitive organic compound》
Positive type photosensitive organic compound is used to form patterned organic film, and the patterned organic film is right
Metal film uses when being etched and forming metal line as etching mask, and as coated warp in the state of cured
The permanent film for the metal line for etching and being formed uses.
In addition, positive photosensitive resin composition includes (A) Novolac resins, the chemical combination of (B) containing quinone diazido
Thing and (C) colouring agent.
It should be noted that hereinafter, also positive type photosensitive organic compound is designated as " positive type composition ".
For forming the permanent film connected up as coated metal the method for patterned organic film that uses, later
Middle detailed description.
Hereinafter, to (A) Novolac resins, the compound of (B) containing quinone diazido, (C) colouring agent and other are optional
Composition illustrates.
＜ (A) Novolac resins ＞
As (A) Novolac resins, the various Novolac resins coordinated in the past in positive type composition can be used.As
(A) Novolac resins, preferably by aromatic compound (following, the letter for making there is phenolic hydroxyl in presence of an acid catalyst
Referred to as " phenols ".) and aldehydes carry out addition condensation obtained from Novolac resins.
Phenols
As phenols, for example, can enumerate：Phenol；The cresols class such as orthoresol, metacresol, paracresol；2,3 xylidine phenol,
The dimethylbenzene phenols such as 2,4- xylenols, 2,5- xylenols, 2,6- xylenols, 3,4- xylenols, 3,5- xylenols；
The ethyl phenols such as o-ethyl phenol, m-ethylphenol, paraethyl phenol；2- isopropyl-phenols, 3- isopropyl-phenols, 4- isopropyls
The induced by alkyl hydroxybenzene such as phenol, adjacent butylphenol, a butylphenol, p-butylphenol and p-t-butyl phenol；2,3,5- trimethyls
The trialkyl phenols such as phenol and 3,4,5- pseudocuminols；Resorcinol, catechol, hydroquinones, hydroquinone monomethyl
The polyatomic phenols such as ether, 1,2,3,-thrihydroxy-benzene and phloroglucin；The alkane such as alkyl-resorcin, alkyl catechol and alkyl hydroquinones
(carbon number of their alkyl is less than more than 14 to base polyatomic phenol.)；Alpha-Naphthol；Betanaphthol；Xenol；It is and double
Phenol A etc..These phenols can be used alone, and also can be combined and uses two or more.
In these phenols, metacresol and paracresol are more preferably used in combination by preferably metacresol and paracresol.It is in this case, logical
Both mixing ratios are overregulated, can adjust the susceptibility as positive type composition, the heat resistance of the coated with resin layer 17 formed
Etc. various characteristics.The mixing ratio of metacresol and paracresol is not particularly limited, excellent in terms of the mass ratio of metacresol/paracresol
Elect less than more than 3/7 8/2 as.When the ratio of metacresol is more than 3/7, the susceptibility as positive type composition can be improved, is 8/2
When following, the heat resistance of coated with resin layer 17 can be improved.
Aldehydes
As aldehydes, for example, formaldehyde, paraformaldehyde (paraformaldehyde), furfural, benzaldehyde, nitro can be enumerated
Benzaldehyde and acetaldehyde etc..These aldehydes can be used alone, and also can be combined and uses two or more.
Acid catalyst
As acid catalyst, for example, the inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and phosphorous acid can be enumerated；Formic acid,
The organic acids such as oxalic acid, acetic acid, dithyl sulfate and p-methyl benzenesulfonic acid；And metallic salt such as zinc acetate etc..These acid catalysis
Agent can be used alone, and also can be combined and uses two or more.
Molecular weight
For the weight average molecular weight (Mw to be converted according to polystyrene of (A) Novolac resins；Hereinafter, it is also referred to as " heavy
Average molecular weight ".) for, the viewpoint such as developability, resolution ratio from positive type composition considers, preferably more than 1000, more preferably
More than 2000, more preferably more than 3000, additionally, it is preferred that be less than 50000, more preferably less than 40000, it is further excellent
Elect less than 30000 as, be still more preferably less than 20000.
(A) decentralization (weight average molecular weight Mw/ number-average molecular weight Mn) of Novolac resins is preferably less than more than 1 20, more
Preferably less than more than 2 17, particularly preferably less than more than 3 15, more preferably less than more than 4 12.
By making the decentralization of (A) Novolac resins be less than more than 1 20, passed through so as to utilize using positive type composition
Metal line is equably coated to by the permanent film (coated with resin layer) formed by aftermentioned method, also, can not form metal
The position of wiring is not easy coated by permanent film (coated with resin layer).
From the aspect of the effect for being particularly easy to obtain the present invention, the decentralization of (A) Novolac resins is preferably more than 2
Less than 17, more preferably less than more than 3 15, particularly preferably less than more than 4 12.
In addition, from the aspect of better mobility, it is also preferred that the decentralization of (A) Novolac resins is more than 5 and is
Less than 20.
It should be noted that in this specification, weight average molecular weight Mw, number-average molecular weight Mn may be defined as GPC (gel infiltrations
Chromatogram) measure according to polystyrene convert relative value.
In addition, in the case of using a variety of (A) Novolac resins, these a variety of (A) Novolac can be combined with
GPC (gel permeation chromatography) measure is carried out in the state of resin, decentralization is determined by obtained figure.
, can be different by least two kinds of weight average molecular weight according to polystyrene conversion as (A) Novolac resins
Novolac resin combinations use.By the way that the Novolac resin combinations of the different sized molecules amount of weight average molecular weight are used, from
And many excellent specific properties such as developability, resolution ratio, film forming can be assigned to positive type composition.
On (A) Novolac resins, the combination of the resin different as weight average molecular weight, it is not particularly limited, it is preferably heavy
The resin for the lower molecular wt side that average molecular weight is less than more than 1,000 10000 and weight average molecular weight are more than 5,000 50000
The combination of the resin of following high weight average molecular weight side, more preferably weight average molecular weight be less than more than 2,000 8000 it is low it is heavy divide equally
The resin of son amount side, the combination with weight average molecular weight for the resin of less than more than 8,000 40000 high weight average molecular weight side, enter one
Walk the resin for the lower molecular wt side that preferable weight-average molecular weight is less than more than 3,000 7000, be 10000 with weight average molecular weight
The combination of the resin of high weight average molecular weight side of the above below 20000.
As (A) Novolac resins, when the different resin of weight average molecular weight is applied in combination, respective containing ratio is without spy
Not limiting, the containing ratio of the resin of lower molecular wt side in the total amount of (A) Novolac resins is preferably more than 5 mass %,
More preferably more than 10 mass %, more preferably more than 15 mass %, on the other hand, preferably below 50 mass %, more
Preferably below 40 mass %.
The containing ratio of (A) Novolac resins in whole solid state components of positive type composition is preferably more than 40 mass %,
More preferably more than 45 mass %, more preferably more than 50 mass %, preferably below 90 mass %, more preferably 85 matter
Measure below %.By making the containing ratio of (A) Novolac resins within the above range, so as to moderately bond eurymeric combination
The lyophily relative to metal ingredient is played while the other compositions included in thing, as a result, usable positive type composition is formed
With the adaptation of metal line also excellent permanent film (coated with resin layer).
Positive type composition can also include other beyond (A) Novolac resins in addition to comprising (A) Novolac resins
Resin.The species of other resins is not particularly limited, as long as will not the light such as the susceptibility of excessive damage's positive type composition, resolution ratio
Carve characteristic.
As the preference of other resins, (A1) alkaline soluble acrylic resin can be enumerated.(A1) Alkali-soluble acrylic
Resin plays a role in the permanent film (coated with resin layer) for using positive type composition to be formed as plasticizer, suppresses permanent
Cracked in film.
As (A1) alkaline soluble acrylic resin, the alkali being engaged to usually as plasticizer in positive type composition can be used
Soluble acrylic resin.
As (A1) alkaline soluble acrylic resin, more specifically, can enumerate containing 30 moles of more than %, 90 moles of % with
Under 50 moles of below % of construction unit and 2 moles of more than % based on the polymerizable compound with ehter bond based on
The resin of the construction unit of the polymerizable compound of carboxyl.
As the polymerizable compound with ehter bond, (methyl) acrylic acid 2- methoxy acrylates, the second of methoxyl group three can be enumerated
Glycol (methyl) acrylate, (methyl) acrylic acid 3- methoxybutyls, ethyl carbitol (methyl) acrylate, phenoxy group gather
Ethylene glycol (methyl) acrylate, methoxyl group polypropylene glycol (methyl) acrylate and (methyl) acrylic acid tetrahydro furfuryl ester etc.
The free-radical polymerised compounds such as (methyl) acrylic acid derivative with ehter bond and ester bond.In these, preferably using acrylic acid
2- methoxy acrylates and methoxy triethylene acrylate.These compounds can be used alone, can also mix it is two or more and
Use.
As the polymerizable compound with carboxyl, the monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid can be enumerated；
The dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid；And butanedioic acid 2- methylacryloyl epoxides ethyl ester, maleic acid 2- methyl
Acryloyl group epoxide ethyl ester, phthalic acid 2- methylacryloyl epoxide ethyl esters and hexahydrophthalic acid 2- metering systems
Acyloxy ethyl ester etc. has the free-radical polymerised compounds such as the methacrylic acid derivative of carboxyl and ester bond.It is excellent in these
Choosing uses acrylic acid and methacrylic acid.These compounds can be used alone, and can also mix two or more and use.
(A1) content of the unit for deriving from the polymerizable compound with ehter bond in alkaline soluble acrylic resin is preferred
For 30 moles of more than %, 90 moles of below %, 80 moles of below % of more preferably 40 moles of more than %.By the way that above-mentioned model will be included
(A1) alkaline soluble acrylic resin of the unit for deriving from the polymerizable compound with ehter bond of amount in enclosing is as plasticizer
It is engaged in positive type composition, so as to suppress to be produced in the permanent film (coated with resin layer) formed using positive type composition
Raw crackle, and easily form uniform permanent film (coated with resin layer).
(A1) content of the construction unit based on the polymerizable compound with carboxyl in alkaline soluble acrylic resin is excellent
Elect 2 moles of more than %, 50 moles of below %, 40 moles of below % of more preferably 5 moles of more than % as.By the way that above-mentioned model will be included
(A1) alkaline soluble acrylic resin of the construction unit based on the polymerizable compound with carboxyl of amount in enclosing is as plasticising
Agent is engaged in positive type composition, so that the developability of positive type composition becomes good.
(A1) weight average molecular weight according to polystyrene conversion of alkaline soluble acrylic resin is preferably more than 10000
Less than 800000, more preferably less than more than 30,000 500000.
In addition, when (A) Novolac resins and (A1) alkaline soluble acrylic resin are applied in combination, (A) Novolac trees
The decentralization of the mixture of fat and (A1) alkaline soluble acrylic resin is preferably less than more than 1 20, more preferably more than 2 17 with
Under, more preferably less than more than 3 15, particularly preferably less than more than 4 12.
In addition, from the aspect of better mobility, it is also preferred that (A) Novolac resins and (A1) alkali solubility propylene
The decentralization of the mixture of acid resin is more than 5 and is less than 20.
For the purpose for moderately controlling physical/chemical properties, (A1) alkaline soluble acrylic resin can also include and be based on it
The construction unit of his free-radical polymerised compound.So-called herein " other free-radical polymerised compounds ", refer to foregoing gather
Free-radical polymerised compound beyond conjunction property compound.
As other such free-radical polymerised compounds, (methyl) methyl acrylate, (methyl) acrylic acid can be used
Ethyl ester and (methyl) butyl acrylate etc. (methyl) alkyl-acrylates；(methyl) acrylic acid 2- hydroxy methacrylates and (methyl)
Acrylic acid 2- hydroxy propyl esters etc. (methyl) hydroxyalkyl acrylates class；(methyl) phenyl acrylate and (methyl) acrylic acid benzyl
Ester etc. (methyl) benzyl acrylate class；The dicarboxylic diester class such as diethyl maleate and dibutyl fumarate；Styrene and
The aromatic compound containing vinyl such as α-methylstyrene；The aliphatic compound containing vinyl such as vinyl acetate；
Butadiene and isoprene equiconjugate alkadiene；The polymerizable compound containing itrile group such as acrylonitrile and methacrylonitrile；Chlorine
The polymerizable compound containing chlorine such as ethene and vinylidene chloride；And acrylamide and Methacrylamide etc. contain amido link
Polymerizable compound etc..These compounds can be used alone, and can also mix two or more and use.It is special in these compounds
Not preferred n-butyl acrylate, benzyl methacrylate and methyl methacrylate etc..(A1) in alkaline soluble acrylic resin
The content of construction unit based on other free-radical polymerised compounds is preferably shorter than 50 mass %, more preferably less than 40 matter
Measure %.
As the polymer solvent used when synthesizing (A1) alkaline soluble acrylic resin, for example, ethanol and diethyl can be used
The alcohols such as glycol；The alkyl of the polyalcohols such as ethylene glycol single methyl ether, diethylene glycol monomethyl ether and diethylene glycol ethyl methyl ether
Ethers；The alkylether acetates class of the polyalcohol such as ethylene glycol monoethyl ether acetate and methyl proxitol acetate；Toluene and two
Toluene etc. is aromatic hydrocarbon；The ketone such as acetone and methyl iso-butyl ketone (MIBK)；And esters such as ethyl acetate and butyl acetate etc..These
In polymer solvent, particularly preferably using the alkyl ether of polyalcohol and the alkylether acetates class of polyalcohol.
The polymerization catalyst used during as synthesis (A1) alkaline soluble acrylic resin, can be used common radical polymerization
Initiator, for example, can be used 2, the azo-compound such as 2 '-azobis isobutyronitrile；And benzoyl peroxide and di-t-butyl mistake
Organic peroxides such as oxide etc..
On positive type composition, for the use level in the case of comprising (A1) alkaline soluble acrylic resin, relatively
In the mass parts of (A) Novolac resins 100, preferably below 30 mass parts, more preferably below 20 mass parts.
Compound ＞s of the ＜ (B) containing quinone diazido
Positive type composition, which includes, (B) compound containing quinone diazido.As the chemical combination of (B) containing quinone diazido
Thing, can suitably it be selected from the compound with quinone diazido coordinated in various positive type compositions in the past.
As the preferable concrete example of the compound of (B) containing quinone diazido, following substances can be enumerated and contain quinone two
Complete carboxylate, partial esterification thing, amidate or partial amides compound that the sulfonic acid of azido is formed etc., the material is：
2,3,4- trihydroxybenzophenones, 2,4,4 '-trihydroxybenzophenone, 2,4,6- trihydroxybenzophenones, 2,3,6- trihydroxies
Benzophenone, 2,3,4- trihydroxies -2 '-methyl benzophenone, 2,3,4,4 '-tetrahydroxybenzophenone, 2,2 ', 4,4 '-four hydroxyls
Base benzophenone, 2,3 ', 4,4 ', 6- pentahydroxybenzophenones, 2,2 ', 3,4,4 '-pentahydroxybenzophenone, 2,2 ', 3,4,5-
Pentahydroxybenzophenone, 2,3 ', 4,4 ', 5 ', 6- hexahydroxys benzophenone, 2,3,3 ', 4,4 ', 5 '-hexahydroxy benzophenone etc.
Polyhydroxy benzophenone class；Double (2,4- dihydroxy phenyls) methane, double (2,3,4- trihydroxies phenyl) methane, 2- (4- hydroxy benzenes
Base) -2- (4 '-hydroxy phenyl) propane, 2- (2,4- dihydroxy phenyls) -2- (2 ', 4 '-dihydroxy phenyl) propane, 2- (2,3,4-
Trihydroxy phenyl) -2- (2 ', 3 ', 4 '-trihydroxy phenyl) propane, 4,4 '-{ 1- [4- (2- (4- hydroxy phenyls) -2- propyl group) benzene
Base] ethylidene } bis-phenol and 3,3 '-dimethyl-{ 1- [4- (2- (3- methyl -4- hydroxy phenyls) -2- propyl group) phenyl] ethylidene }
Double [(more) hydroxy phenyl] alkanes such as bis-phenol；Three (4- hydroxy phenyls) methane, double (4- hydroxyl -3,5- 3,5-dimethylphenyls) -4-
Hydroxy phenyl methane, double (4- hydroxyl -2,5- 3,5-dimethylphenyls) -4- hydroxy phenyls methane, double (4- hydroxyl -3,5- dimethyl benzenes
Base) -2- hydroxy phenyls methane, double (4- hydroxyl -2,5- 3,5-dimethylphenyls) -2- hydroxy phenyls methane, double (4- hydroxyls -2,5- two
Aminomethyl phenyl) -3,4- dihydroxy benzenes methylmethane and double (4- hydroxyl -3,5- 3,5-dimethylphenyls) -3,4- dihydroxy benzenes methylmethanes etc.
Three (hydroxy phenyl) methane classes or its methyl substitute；Double (3- cyclohexyl -4- hydroxy phenyls) -3- hydroxy phenyls methane, double (3-
Cyclohexyl -4- hydroxy phenyls) it is -2- hydroxy phenyls methane, double (3- cyclohexyl -4- hydroxy phenyls) -4- hydroxy phenyls methane, double
(5- cyclohexyl -4- hydroxy-2-methyls phenyl) -2- hydroxy phenyls methane, double (5- cyclohexyl -4- hydroxy-2-methyls phenyl) -3-
Hydroxy phenyl methane, double (5- cyclohexyl -4- hydroxy-2-methyls phenyl) -4- hydroxy phenyls methane, double (3- cyclohexyl -2- hydroxyls
Phenyl) -3- hydroxy phenyls methane, double (5- cyclohexyl -4- hydroxy-3-methyls phenyl) -4- hydroxy phenyls methane, double (5- hexamethylenes
Base -4- hydroxy-3-methyls phenyl) -3- hydroxy phenyls methane, double (5- cyclohexyl -4- hydroxy-3-methyls phenyl) -2- hydroxy benzenes
Methylmethane, double (3- cyclohexyl -2- hydroxy phenyls) -4- hydroxy phenyls methane, double (3- cyclohexyl -2- hydroxy phenyls) -2- hydroxyls
Phenylmethane, double (5- cyclohexyl -2- hydroxy-4-methyls phenyl) -2- hydroxy phenyls methane and it is double (5- cyclohexyl -2- hydroxyls -
4- aminomethyl phenyls) double (cyclohexyl hydroxy phenyl) (hydroxy phenyl) methane classes such as -4- hydroxy phenyl methane or its methyl substitute；
Phenol, p methoxy phenol, xylenol, quinhydrones, naphthols, catechol, 1,2,3,-thrihydroxy-benzene, 1,2,3,-thrihydroxy-benzene monomethyl ether, company
Benzenetriol -1,3- dimethyl ethers, gallic acid, aniline, 4-aminodiphenylamine (p-aminodiphenylamine) and 4,
4 '-diaminobenzophenone etc. has the compound of hydroxyl or amino；And Novolac, 1,2,3,-thrihydroxy-benzene-acetone resin and right
Copolymer that the homopolymer or 4-Vinyl phenol of hydroxy styrenes are formed with copolymerizable monomer etc..These (B) contain quinone two
The compound of azido can be used alone, and also can be combined and uses two or more.
As the above-mentioned sulfonic acid containing quinone diazido that the compound of (B) containing quinone diazido can be used as to use, do not have
There is special limitation, for example, naphthoquinones -1,2- diazido -5- sulfonic acid (naphthoquinone-1,2-diazido-5- can be enumerated
Sulfonic acid), the naphthoquinones diazido sulfonic acid such as naphthoquinones -1,2- diazido -4- sulfonic acid；Adjacent anthraquinone diazido sulfonic acid
Deng preferred naphthoquinones diazido sulfonic acid.The above-mentioned esterification of sulfonic acid (preferably naphthoquinones diazido sulfonic acid) containing quinone diazido
Thing can be completely dissolved in the used solvent generally when using positive type composition in the form of a solution, and with (A) Novolac trees
The compatibility of fat is good.If being engaged to these compounds as the compound of (B) containing quinone diazido in positive type composition,
Then it is readily obtained the positive type composition of high sensitive.
On the manufacture method of the above-mentioned carboxylate as the compound of (B) containing quinone diazido, it is not particularly limited,
For example, following methods can be enumerated：Addition is folded containing quinone two in the form of the sulfonic acid chloride such as naphthoquinones -1,2- diazido sulfonic acid chlorides
The sulfonic acid of nitrogen base, in the solvent of dioxane etc, in triethanolamine, alkali carbonate, alkali metal hydrogencarbonate
Deng being condensed it in the presence of alkali, so as to carry out esterification or partial esterification completely.
For the content of the compound of (B) containing quinone diazido, from the aspect of the susceptibility of positive type composition,
Relative to the mass parts of (A) Novolac resins 100, preferably more than 5 mass parts, more preferably more than 10 mass parts, it is preferably
Below 100 mass parts, more preferably below 50 mass parts, more preferably below 30 mass parts.
＜ (C) colouring agents ＞
The optical density of the permanent film (coated with resin layer) formed using positive type composition via aftermentioned method is, for example, 0.10/
More than μm.From the viewpoint of such optical density is reached, positive type composition includes (C) colouring agent.
As (C) colouring agent, it is not particularly limited, for example, it is preferable to use Colour Index (C.I.；The Society of
Dyers and Colourists companies issue) in be classified as pigment (Pigment) compound, specifically, preferably make
With the material numbered with Colour Index (C.I.) as described below.
As the example for the yellow uitramarine that can suitably use, (following, the also " C.I. of C.I. pigment yellows 1 can be enumerated
Pigment yellow ", only record numbering.)、3、11、12、13、14、15、16、17、20、24、31、53、55、60、61、65、71、73,74、
81、83、86、93、95、97、98、99、100、101、104、106、108、109、110、113、114、116、117、119、120、
125、126、127、128、129、137、138、139、147、148、150、151、152、153、154、155、156、166、167、
168th, 175,180 and 185.
As the example for the orange pigment that can suitably use, (following, the also " C.I. of C.I. pigment oranges 1 can be enumerated
Pigment orange ", only record numbering.)、5、13、14、16、17、24、34、36、38、40、43、46、49、51、55、59、61、63、64、
71 and 73.
As the example for the violet pigment that can suitably use, C.I. pigment violet 1s (following, also " C.I. can be enumerated
Pigment violet ", only record numbering.), 19,23,29,30,32,36,37,38,39,40 and 50.
As the example for the red pigment that can suitably use, (following, the also " C.I. of C.I. paratoneres 1 can be enumerated
Paratonere ", only record numbering.)、2、3、4、5、6、7、8、9、10、11、12、14、15、16、17、18、19、21、22、23、30、
31、32、37、38、40、41、42、48：1、48：2、48：3、48：4、49：1、49：2、50：1、52：1、53：1、57、57：1、57：
2、58：2、58：4、60：1、63：1、63：2、64：1、81：1、83、88、90：1、97、101、102、104、105、106、108、
112、113、114、122、123、144、146、149、150、151、155、166、168、170、171、172、174、175、176、
177、178、179、180、185、187、188、190、192、193、194、202、206、207、208、209、215、216、217、
220th, 223,224,226,227,228,240,242,243,245,254,255,264 and 265.
As the example for the blue pigment that can suitably use, C.I. pigment blue 1s (following, also " C.I. can be enumerated
Alizarol saphirol ", only record numbering.)、2、15、15：3、15：4、15：6th, 16,22,60,64 and 66.
As can suitably use it is above-mentioned outside tone pigment example, C.I. pigment Green 7s, C.I. face can be enumerated
Expect the viridine greens such as green 36, C.I. naphthol greens 37, C.I. pigment browns 23, C.I. pigment brown 25s, C.I. pigment browns 26, C.I. pigment
The black pigments such as brown 28 grade browns, C.I. pigment blacks 1, C.I. pigment blacks 7.
In addition, positive type composition, which preferably comprises opacifier, is used as (C) colouring agent.(C) when colouring agent is opacifier, as screening
Photo etching, preferably using black pigment, violet pigment.As black pigment, the example of violet pigment, carbon black can be enumerated, be face
Material, lactams series pigments, titanium are black, the metal oxide of copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver etc., composite oxides, metal
The various pigment such as sulfide, metal sulfate or metal carbonate (whether organic matter or inorganic matter).
As carbon black, channel black (channel black), furnace black (furnace black), hot tearing charcoal can be used
Carbon black known to black (thermal black), lampblack (lamp black) etc..In addition, it is possible to use through resin-coated carbon black.
As carbon black, it is also preferable to implement the carbon black for the processing for importing acidic-group.It is fed to the acidity of carbon black
Group is the acid functional group for showing the definition based on Bronsted.As the concrete example of acidic-group, can enumerate carboxyl,
Sulfonic group, phosphate etc..The acidic-group for being fed to carbon black can forming salt.Cation with acidic-group forming salt there is no harm in
Hinder and be not particularly limited in the range of the purpose of the present invention.As the example of cation, each metal ion species, nitrogen can be enumerated
The cation of compound, ammonium ion etc., the preferably alkali metal ion such as sodium ion, potassium ion, lithium ion, ammonium ion.
In the carbon black of the processing described above for implementing and importing acidic-group, have and be selected from by carboxylic acid group, carboxylate
The carbon black of more than a kind functional group in the group of group, sulfonic group and sulfonate groups composition is preferable.
The method that acidic-group is imported into carbon black is not particularly limited.As the method for importing acidic-group, for example, can
Enumerate following method.
Method 1)：Pass through direct method of substitution (wherein utilizing the concentrated sulfuric acid, oleum, chlorosulfonic acid etc.), indirect method of substitution (its
It is middle to utilize sulphite, bisulfites etc.), sulfonic group is imported into carbon black.
Method 2)：Make that there is the organic compound of amino and acidic-group to carry out diazo coupling with carbon black.
Method 3)：Make to have organising for halogen atom and acidic-group using inferior (Williamson) etherification method of William
Compound is reacted with the carbon black with hydroxyl.
Method 4)：Make with halo carbonyl and by the organic compound of the acidic-group of protection group protection and with hydroxyl
Carbon black is reacted.
Method 5)：Using the organic compound for the acidic-group protected with halo carbonyl and by protection group, for carbon black
Friedel-Crafts reaction is carried out, is then deprotected.
In the above method, from the processing for importing acidic-group easily carry out and it is safe from the aspect of, preferably method
2).As method 2) in the organic compound with amino and acidic-group that uses, be preferably bonded with aromatic group
The compound of amino and acidic-group.As the example of such compound, the aminobenzene of p-aminobenzene sulfonic acid etc can be enumerated
The aminobenzoic acid of sulfonic acid, PABA etc.
The molal quantity for being fed to the acidic-group of carbon black does not limit especially in the range of without prejudice to the purpose of the present invention
System.Relative to carbon black 100g, the molal quantity for being fed to the acidic-group of carbon black is preferably more than 1mmmol below 200mmol,
More preferably more than 5mmol below 100mmol.
Carbon black for having imported acidic-group, resin can be utilized to implement coating treatment.In use comprising through resin quilt
In the case of the photosensitive polymer combination of the carbon black covered, the light-proofness that light-proofness is excellent, surface reflectivity is low is easily formed
Permanent film (coated with resin layer).
As the example available for the resin for being coated to carbon black, can enumerate：Phenolic resin, melmac, dimethylbenzene tree
The thermosetting resins such as fat, diallyl phthalate resin, sweet phthalein (glyptal) resin, epoxy resin, alkylbenzene resin；
Polystyrene, makrolon, polyethylene terephthalate, polybutylene terephthalate (PBT), Noryl, polysulfones,
PPTA, polyamidoimide, polyimides, PABM, polyether sulfone polyphenylene
The thermoplastic resins such as sulfone, polyarylate, polyether-ether-ketone.Relative to carbon black quality and resin quality total for, on carbon black
The amount of coating of resin be preferably more than 1 mass % below 30 mass %.
In addition, as opacifier, further preferably series pigments.As the concrete example of series pigments, following formula (c-1) can be enumerated
The series pigments that the series pigments and following formula (c-3) that the series pigments of expression, following formula (c-2) represent represent.In commercially available product
In, preferably use the conducts such as product the name K0084 and K0086, pigment black 21,30,31,32,33 and 34 of BASF AG
Series pigments.
[chemical formula 1]
In formula (c-1), Rc1And Rc2The alkylidene that carbon number is less than more than 13, R are represented independently of one anotherc3And Rc4Respectively
From independently expression hydrogen atom, hydroxyl, methoxyl group or acetyl group.
[chemical formula 2]
In formula (c-2), Rc5And Rc6The alkylidene that carbon number is less than more than 17 is represented independently of one another.
[chemical formula 3]
In formula (c-3), Rc7And Rc8It is each independently hydrogen atom, the alkyl that carbon number is less than more than 1 22, also may be used
Include hetero atom N, O, S or P.Rc7And Rc8For alkyl when, the alkyl can be straight-chain, or branched.
The compound example of compound, the compound that formula (c-2) represents and formula (c-3) expression that above-mentioned formula (c-1) represents
Method synthesis as described in using Japanese Unexamined Patent Application 62-1753 publications, Japanese Patent Publication 63-26784 publications.That is,
By -3,5,9,10- tetracarboxylic acids or its dianhydride and amine as raw material, heating response is carried out in water or organic solvent.Then,
Obtained rough thing is subjected to reprecipitation in sulfuric acid, or tied again in water, organic solvent or their in the mixed solvent
Crystalline substance, it can thus be concluded that arriving object.
In order that series pigments disperse well in positive type composition, the average grain diameters of series pigments be preferably 10nm with
Upper below 1000nm.
In addition, as opacifier, lactams series pigments can be also included.As lactams series pigments, for example, can enumerate following
The compound that formula (c-4) represents.
[chemical formula 4]
In formula (c-4), XcDouble bond is represented, as geometric isomer, is each independently E bodies or Z bodies, Rc9Independently of one another
Represent hydrogen atom, methyl, nitro, methoxyl group, bromine atoms, chlorine atom, fluorine atom, carboxyl or sulfonic group, Rc10Independently of one another
Represent hydrogen atom, methyl or phenyl, Rc11Hydrogen atom, methyl or chlorine atom are represented independently of one another.
The compound that formula (c-4) represents can be used alone or combine two or more and use.
From the aspect of the compound represented from easy to manufacture formula (c-4), Rc9It is preferred that 6 of dihydroindolone ring are bonded to,
Rc11It is preferred that it is bonded to 4 of dihydroindolone ring.From the same viewpoint, Rc9、Rc10And Rc11Preferably hydrogen atom.
For the compound that formula (c-4) represents, as geometric isomer, there are EE bodies, ZZ bodies, EZ bodies, can be it
In the mixture of any single compound or these geometric isomers.
The compound that formula (c-4) represents is for example using International Publication No. 2000/24736, International Publication No. 2010/
Method manufacture described in No. 081624.
In order that lactams series pigments disperse well in positive type composition, the average grain diameter of lactams series pigments is preferred
For more than 10nm below 1000nm.
In addition, using silver-colored tin (AgSn) alloy as the particulate (hereinafter referred to as " AgSn alloy particles " of principal component.) it is also preferred that making
Used for opacifier.For the AgSn alloy particles, as long as AgSn alloys are principal component, as other metals into
Point, for example, Ni, Pd, Au etc. can be included.
The average grain diameter of the AgSn alloy particles is preferably more than 1nm below 300nm.
When AgSn alloys are represented by chemical formula AgxSn, the scope that can obtain the x of the stable AgSn alloys of chemical property is 1
≤ x≤10, the scope that can obtain the x of chemical stability and blackness simultaneously are 3≤x≤4.
Herein, obtain for above-mentioned x scope when AgSn alloys in Ag mass ratio, result is：
In the case of x=1, Ag/AgSn=0.4762
In the case of x=3,3Ag/Ag3Sn=0.7317
In the case of x=4,4Ag/Ag4Sn=0.7843
In the case of x=10,10Ag/Ag10Sn=0.9008.
Therefore, for the AgSn alloys, in the case of the Ag containing below the mass % of more than 47.6 mass % 90,
Chemical property is stable, in the case of the Ag containing below the mass % of more than 73.17 mass % 78.43, may correspond to Ag amounts and
Effectively obtain chemical stability and blackness.
The AgSn alloy particles can utilize common particulate synthetic method to make.As particulate synthetic method, it is anti-gas phase can be enumerated
Ying Fa, spray pyrolysis, send method, liquid phase reactor method, freeze-drying, hydrothermal synthesis method etc. forth.
Although AgSn alloy particles are the high materials of insulating properties, but in order to further improve insulating properties, it is also possible to dielectric film
Cover surface.As the material of such dielectric film, preferably metal oxide or organic high molecular compound.
As metal oxide, the metal oxide with insulating properties, such as silica (titanium dioxide can be suitably used
Silicon), aluminum oxide (alundum (Al2O3)), zirconium oxide (zirconium dioxide), yittrium oxide (yttria), titanium oxide (titanium dioxide)
Deng.
In addition, as organic high molecular compound, the resin with insulating properties can be suitably used, such as polyimides,
Polyethers, polyacrylate, polyamino compound etc..
For the thickness of dielectric film, in order to fully improve the insulating properties on AgSn alloy particles surface, preferably 1nm with
Upper below 100nm thickness, more preferably more than 5nm below 50nm.
Dielectric film can be readily formed by process for modifying surface or the paint-on technique on surface.Especially with four ethoxies
During the alkoxide such as base silane, three aluminium ethylates, the dielectric film of uniform film thickness can be formed at a lower temperature, thus preferably.
As opacifier, the above-mentioned series pigments that can be used alone, lactams series pigments, AgSn alloy particles, can also incite somebody to action
They are applied in combination.
In addition, for purpose for adjusting tone etc., opacifier can not only include above-mentioned black pigment, violet pigment, also
Include the pigment of the tone such as red, blue, green, yellow.The pigment of tone outside black pigment, violet pigment can be from known pigment
Appropriate selection.For example, the pigment as the tone outside black pigment, violet pigment, can be used above-mentioned various pigment.On
The usage amount of the pigment of tone outside black pigment, violet pigment, for the gross mass of opacifier, preferably 15 matter
Below % is measured, more preferably below 10 mass %.
In order that above-mentioned (C) colouring agent is uniformly dispersed in positive type composition, dispersant can be further used.As
Such dispersant, preferably using polyethyleneimine amine system, polyurethane resin system, acrylic resin macromolecule dispersing agent.Especially
It is, in the case where using carbon black as (C) colouring agent, to be preferably used as dispersant using the dispersant of acrylic resin.
It should be noted that according to the species of dispersant, the manufacturing condition of display device, the difference of use condition, because dividing
Powder and caused volatile ingredient is possible to have undesirable effect display device, therefore, in the case of without using dispersant
It is also preferable to carry out decentralized processing to (C) colouring agent.
In addition, inorganic pigment and organic pigment can individually using or and use two or more.And use in the case of, phase
For the mass parts of total amount 100 of inorganic pigment and organic pigment, preferably made with the scope below more than 10 mass parts 80 mass parts
With organic pigment, organic pigment is more preferably used with the scope below more than 20 mass parts 40 mass parts.
It should be noted that in positive type composition, as (C) colouring agent, in addition to pigments, it is possible to use dyestuff.Should
Dyestuff can suitably select from known material.
As the dyestuff that can be applicable in positive type composition, for example, can enumerate azo dyes, metal complex azo dyestuff,
Anthraquinone dye, triphenhlmethane dye, xanthene dye, cyanine dye, naphthoquinone dyestuff, quinoneimine dye, methine dyes, phthalocyanine dye
Material etc..
In addition, for these dyestuffs, by carrying out color lake (into salinization) it can be made to be scattered in organic solvent etc., from
And used as (C) colouring agent.
In addition to these dyestuffs, such as Japanese Unexamined Patent Publication 2013-225132 publications, Japanese Unexamined Patent Publication will also be preferred
2014-178477 publications, Japanese Unexamined Patent Publication 2013-137543 publications, Japanese Unexamined Patent Publication 2011-38085 publications, Japanese Unexamined Patent Publication
Dyestuff described in 2014-197206 publications etc. etc..
These dyestuffs also can be further with foregoing pigment (for example, series pigments, lactams series pigments, AgSn alloys be micro-
Grain etc.) it is applied in combination.
The usage amount of (C) colouring agent in positive type composition is not particularly limited.For example, following amounts can be used：Rear
After being toasted in the permanent film formation process stated, the permanent film (coated with resin layer) that optical density is more than 0.10/ μm can be formed
Amount.
For the usage amount of (C) colouring agent in the positive type composition, for example, relative to (A) Novolac resins
100 mass parts, preferably more than 1 mass parts, more preferably more than 3 mass parts, more preferably more than 5 mass parts, in addition,
Preferably below 60 mass parts, more preferably below 50 mass parts, more preferably below 45 mass parts, still more preferably
Below 40 mass parts.
In addition, the optical density of the permanent film (coated with resin layer) formed using positive type composition via aftermentioned method is more preferably
For less than more than 0.20/ μm 2.0/ μm, more preferably less than more than 0.30/ μm 1.0/ μm.
For (C) colouring agent, it is preferred that presence or absence of making it under conditions of dispersant with appropriate dense
Degree is scattered and after dispersion liquid is made, be added in positive type composition.
＜ crosslinking agents ＞
Positive type composition can contain crosslinking agent.Crosslinking agent can be appropriate from the compound that can make (A) Novolac resin crosslinks
Selection, for example, melamine compound can be used；The amine system crosslinking agent such as hexa, urea derivative；Epoxide.
By making positive type composition contain such crosslinking agent, so as to form the permanent of water resistance, heat resistance and excellent solvent resistance
Film (coated with resin layer).
As melamine compound, can be used it is being acted on as crosslinking agent with (A) Novolac resins, have
From the compound of chemical constitution obtained by melamine-derived, for example, the compound that following formula (I)s represent can be used.
[chemical formula 5]
(in formula, R1~R6Hydrogen atom or-CH are represented independently of one another2-O-R7The group of expression, R7It is former for hydrogen atom or carbon
Subnumber be less than more than 1 10 alkyl, R1~R6In at least one be-CH2-O-R7The group of expression.)
In above-mentioned formula (I), preferably R1~R6Middle-the CH for having more than 22-O-R7The group of expression.
As R7The alkyl of expression, more preferably methyl, ethyl, n-propyl, isopropyl, normal-butyl, the tert-butyl group, n-hexyl
Deng the alkyl that carbon number is less than more than 16.
The melamine compound represented as above-mentioned formula (I), can be enumerated：Hexamethylolmelamine, six hydroxyl butyl three
Poly cyanamid and part methylolated melamine and their alkylates；Tetra methylol benzoguanamine and part methylolation
Benzoguanamine and their alkylates；Etc..
As epoxide, can be used it is being acted on as crosslinking agent with (A) Novolac resins, there is epoxy
The compound of base.As epoxide, the multi-functional epoxy compound with more than 2 epoxy radicals preferably in 1 molecule.Need
It is noted that in this specification, the silane coupler with epoxy radicals in its structure in silane coupler described later is not
Belong to the epoxide for being used as crosslinking agent.
As epoxide, preferably phenol Novolac types epoxy resin, cresols Novolac types epoxy resin, bis-phenol
A types epoxy resin, bisphenol f type epoxy resin, multifunctional alicyclic epoxy resin, the more glycidyl ethers of aliphatic etc..
Above-mentioned crosslinking agent can be used alone, and also can be combined and uses two or more.
Relative to the mass parts of (A) Novolac resins 100, the content of crosslinking agent can be more than 3 mass parts, can be 10
More than mass parts, can be more than 15 mass parts.In addition, relative to the mass parts of (A) Novolac resins 100, the content of crosslinking agent
It can be below 40 mass parts, can be below 30 mass parts, can be below 25 mass parts.Under the content of crosslinking agent is above-mentioned
When more than limit value, the crosslinking of resin easily becomes abundant, and when being below above-mentioned higher limit, the bin stability of positive type composition holds
Easily become good.
(silane coupler)
Positive type composition can contain silane coupler.
Silane coupler can via the alkoxy and/or reactive group for being bonded to silicon atom and with (A) Novolac resins
Possessed phenolic hydroxyl reaction, therefore can be played a role as crosslinking agent so that formed forever using positive type composition
Long film (coated with resin layer) close mode, so as to can not only improve water resistance, solvent resistance, heat resistance of permanent film etc., but also
Permanent film and the adaptation of metal line can be improved.
As silane coupler, for example, MTMS, MTES, ethyl front three can be enumerated
TMOS, ethyl triethoxysilane, n-propyl trimethoxy silane, n-propyl triethoxysilane, normal-butyl trimethoxy
The monoalkyltrialkoxysi.anes such as base silane, ne-butyltriethoxysilaneand；Dimethyldimethoxysil,ne, dimethyl diethoxy
The dialkyl dialkoxy silicanes such as base silane；Single phenyl tri-alkoxy such as phenyltrimethoxysila,e, phenyl triethoxysilane
Silane；The diphenyl dialkoxy silicane such as dimethoxydiphenylsilane, diphenyl diethoxy silane；Vinyl trimethoxy
The mono-vinyl trialkoxy silane such as silane, VTES；3- methacryloxypropyl trimethoxy silicon
Alkane, 3- methacryloxypropyls, 3- methacryloyloxypropyl methyls dimethoxysilane, 3- first
Base acryloxypropyl diethoxy silane etc. (methyl) acryloxyalkyl monoalkyl dialkoxy silicane；3- third
Alkene acryloxypropylethoxysilane trimethoxy silane etc. (methyl) acryloxyalkyl trialkoxy silane；3- aminopropyl trimethoxies
Silane, APTES, 3- triethoxysilyls-N- (1,3- dimethyl-butane
(butylidene)) the trialkoxy silane containing amino such as propyl group amine, N- phenyl -3- TSL 8330s；3-
Glycidoxypropyltrime,hoxysilane, 3- glycidoxypropyl group triethoxysilanes etc. contain non-ester ring type epoxy radicals
Alkyltrialkoxysilaneand；3- glycidoxypropyl diethoxy silanes etc. contain the alkyl list of non-ester ring type epoxy radicals
Alkyl-dialkoxysilanes；2- (3,4- epoxycyclohexyls) ethyl trimethoxy silane, 2- (3,4- epoxycyclohexyls) ethyl three
The alkyltrialkoxysilaneand containing ester ring type epoxy radicals such as Ethoxysilane；2- (3,4- epoxycyclohexyls) ethyl-methyl diethyl
The alkyl monoalkyl dialkoxy silicane containing ester ring type epoxy radicals such as TMOS；((3- ethyl -3- oxetanylmethoxies) methoxy
Base) propyl trimethoxy silicane, ((3- ethyl -3- oxetanylmethoxies) methoxyl group) propyl-triethoxysilicane etc. contain oxa- ring
The alkyltrialkoxysilaneand of butyl；The mercaptoalkyl trialkoxy silane such as 3-mercaptopropyi trimethoxy silane；3- sulfydryls third
The mercaptoalkyl monoalkyl dialkoxy silicane such as ylmethyl dimethoxysilane；The urea groups alkane such as 3- ureidopropyltriethoxysilanes
Base trialkoxy silane；The isocyanate-yl alkyl trialkoxy silanes such as 3- NCO propyl-triethoxysilicanes；3- tri-
The alkyltrialkoxysilaneand containing anhydride group such as trimethoxysilylpropyl succinic anhydride；The N- tert-butyl groups -3- (3- trimethoxies
Base silylpropyl) alkyltrialkoxysilaneand containing imide such as succinimide；Etc..Silane coupler can be single
Solely use, also can be combined two or more and use.
In silane coupler, the preferred silane coupler with reactive group.
As the silane coupler with reactive group, it is however preferred to have vinyl, amino, epoxy radicals or oxa- ring fourth
The silane coupler of base.From the compatibility with developer solution it is high, can reduce residue (undissolved and remain), can especially be formed with it is golden
From the viewpoint of the permanent film (coated with resin layer) of the excellent adhesion of category, the more preferably silane coupler with epoxy radicals.
As the silane coupler with epoxy radicals, silane coupler with non-ester ring type epoxy radicals and with ester ring type
The silane coupler of epoxy radicals preferably uses.
Relative to the mass parts of (A) Novolac resins 100, the content of silane coupler can be more than 0.1 mass parts, can
Think more than 0.5 mass parts, can be more than 1 mass parts.It is in addition, even relative to the mass parts of (A) Novolac resins 100, silane
The content for joining agent can be below 10 mass parts, can be below 7 mass parts, it can be 3 mass below 5 mass parts that can be
Below part.
When the content of silane coupler is more than above-mentioned lower limit, easily formed with the excellent adhesion of metal line forever
Long film (coated with resin layer).
When the content of silane coupler is below above-mentioned higher limit, easily suppress because of the silane coupler during preservation each other
Condensation reaction and cause development when produce residue situation.
＜ other compositions ＞
Positive type composition can contain sensitizer, adaptation enhancer, surface in the range of without prejudice to the purpose of the present invention
The various additives such as activating agent, plasticizer.
Sensitizer
As sensitizer, it is not particularly limited, can be arbitrarily selected from the sensitizer generally used in positive type composition
Select.As sensitizer, for example, compound with phenolic hydroxyl that molecular weight is less than 1000 etc. can be enumerated.
Adaptation enhancer
, can be from the material that can improve permanent film (coated with resin layer) and the adaptation of metal line as adaptation enhancer
In suitably select.For example, the hydroxy alkyl nitrogen-containing heterocycle compounds such as 2- hydroxyethyl pyridines can be used to be improved as the adaptation
Agent.
Surfactant
In order to improve coating, defoaming and levelling (leveling) property etc., positive type composition can contain surfactant.
As surfactant, for example, can be used with BM-1000, BM-1100 (BM Chemie company systems), Megafac F142D,
Megafac F172, Megafac F173, Megafac F183 (big Japanese ink chemical industrial company system), Fluorad FC-
135th, Fluorad FC-170C, Fluorad FC-430, Fluorad FC-431 (Sumitomo 3M Ltd. systems), Surflon
S-112, Surflon S-113, Surflon S-131, Surflon S-141, Surflon S-145 (Asahi Glass company system),
SH-28PA, SH-190, SH-193, SZ-6032, SF-8428 (Toray Silicone company systems), BYK-310, BYK-330
The silicon systems or fluorine system surfactant that titles such as (BYK Chemie Japan company systems) is commercially sold.
Relative to the mass parts of (A) Novolac resins 100, the content of surfactant is preferably more than 0.05 mass parts 5 matter
Measure below part.
＜ solvents ＞
For positive type composition, preferably above-mentioned each composition is dissolved in appropriate solvent and made as a solution
With.As such solvent, can enumerate：Ethylene glycol single methyl ether, ethylene glycol monomethyl ether, ethylene glycol monopropyl ether and second two
The ethylene glycol alkyl ether class such as alcohol single-butyl ether；Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl
The diethylene glycol dialkyl ether class such as ether and diethylene glycol dibutyl ether；Methylcellosolve acetate and ethyl cellosolve acetate
Deng ethylene glycol alkyl ether acetate esters；Propylene glycol monomethyl ether, propylene glycol monoethyl acetic acid esters and propane diols list third
The propylene glycol alkyl ether acetic acid esters such as base ether acetic acid ester；The ketones such as acetone, methyl ethyl ketone, cyclohexanone and methyl amyl ketone；First
Benzene and dimethylbenzene etc. are aromatic hydrocarbon；The ring type ethers such as dioxane；And 2 hydroxy propanoic acid methyl esters, 2 hydroxy propanoic acid second
Ester, 2- hydroxy-2-methyls ethyl propionate, ethoxy ethyl acetate, hydroxyl ethyl acetate, 2- hydroxy-3-methyls methyl butyrate, second
Sour 3- methoxybutyls, acetic acid 3- methyl -3- methoxybutyls, Ethyl formate, ethyl acetate, butyl acetate, acetoacetate first
Esters such as ester and ethyl acetoacetate etc..These solvents can be used alone, and can also mix two or more and use.
The content of solvent in positive type composition be contemplated that the viscosity of positive type composition, coating and suitably adjust.Specifically
For, can be to cause the solid component concentration of positive type composition to turn into preferably more than 5 mass % below 50 mass %, more preferably
Below the mass % of more than 10 mass % 30 mode uses solvent.
The preparation method ＞ of ＜ positive type compositions
Positive type composition can be prepared by following manner：After coordinating above-mentioned each composition with defined ratio, utilization is common
Method is mixed and is stirred.In addition, as needed, further it can be filtered using screen cloth, molecular filter etc..
《The manufacture method of metal line》
The manufacture method of metal line is to include the method for following processes：
The process that foregoing positive type photosensitive organic compound is coated with metal film and forms coated film；
The process being exposed to coated film regioselectivity；
The process that exposed coating film development is formed into etching mask；
The metal film on the surface with etching mask is etched, the coated hardware cloth of mask is etched so as to be formed
The process of line；And
Etching mask is toasted, so as to form the process of the permanent film of coated metal wiring.
Hereinafter, the process that foregoing positive type photosensitive organic compound is coated with metal film and forms coated film is designated as
" coated film formation process ".
The process being exposed to coated film is designated as " exposure process " by regioselectivity.
The process developed to exposed coated film and form etching mask is designated as " etching mask formation process ".
To having the metal film of etching mask to be etched on the surface the coated metal of mask will be etched so as to be formed
The process of wiring is designated as " metal line formation process ".
Etching mask will be toasted and be designated as that " permanent film is formed so as to form the process of the permanent film of coated metal wiring
Process ".
Hereinafter, each operation that reference picture 1 includes to the manufacture method of metal line illustrates.
It should be noted that in Fig. 1, for using with colour filter 13 and on colour filter 13 across hyaline layer 14 and shape
Into the substrate of metal film 11 illustrated as the situation of substrate 10.
＜ coated film formation process ＞
In coated film formation process, as shown in Fig. 1 (a) and Fig. 1 (b), in the substrate 10 with metal film 11
In, foregoing positive type composition is coated with metal film 11 and forms coated film 12.
Hereinafter, substrate and coating method are illustrated.
(substrate)
As substrate 10, as long as there is the base for the metal film 11 for being used to manufacture metal line 18 on the layer of translucency
Plate, it is possible to use without particular limitation.
As the typical case of substrate 10, can enumerate with colour filter 13 and directly formed on colour filter 13 or across
The substrate of hyaline layer 14 and the metal film 11 of formation.
In addition, it also may be preferable for using on the face with TFT, directly with or across 1 layer of colour filter 13, hyaline layer 14 etc.
More than functional layer and with metal film 11 substrate.
It should be noted that the mode of substrate 10 with hyaline layer 14 is shown with Fig. 1 (a)~Fig. 1 (f).Omit
To the diagram of the structure of the substrate 10 beyond metal film 11, colour filter 13 and hyaline layer 14.
The material of metal film 11 in substrate 10, manufacture method etc. are not particularly limited, can be from existing known various materials
Suitably selected in matter and various manufacture methods.From the viewpoint of the electric conductivity that appropriateness is presented, the metal film 11 preferably comprises silver
(Ag), copper (Cu) or their alloy.
It should be noted that, although showing the metal film of individual layer in Fig. 1, but examined from the viewpoint that desired characteristic is presented
Consider, can will be laminated with film that the various metals such as molybdenum (Mo), molybdenum alloy form as the metal film 11 in substrate 10.
In addition, as form metal film 11 metal, can use titanium (Ti), chromium (Cr), manganese (Mn), iron (Fe), nickel (Ni),
Zinc (Zn), tungsten (W), golden (Au) etc..
The material of colour filter 13 in substrate 10, manufacture method etc. are not particularly limited, can be from existing known various materials
Suitably selected in matter and various manufacture methods.Colour filter 13 is generally in the region marked off by black matrix" (in Fig. 1 not shown)
The interior light transmitting colored film (not shown in Fig. 1) with RGB etc..
The sectional view of one of the liquid crystal display device purposes of the substrate manufactured in present embodiment is shown in Fig. 2.
Base plate for liquid crystal display device 1 shown in Fig. 2 is substrate obtained from being processed to substrate 10, is sequentially laminated with
Array base palte 23, insulating barrier 22, liquid crystal layer 20, transparent resin layer 19, colour filter 13, hyaline layer 14, metal line 18, coated tree
Lipid layer 17 (permanent film).The substrate can for example be suitably used for On-Cell touch panels.
Colour filter 13 has black matrix" BM and red colored film R, green coloring film G and blue-colored film B.
In addition, on insulating barrier 22, in the red colored film R, green coloring film G and blue-colored film with colour filter 13
The opening position of B position correspondence is formed with pixel electrode 21.
In addition, for black matrix" BM, coated with resin layer 17, with metal line 18 for, when overlooking substrate, they with
Overlap mode is formed.
Pass through the component for generally having the base plate for liquid crystal display device 1 and backlight etc. in liquid crystal display device
Combine and suitably connected up, so as to manufacture liquid crystal display device.
It should be noted that the base plate for liquid crystal display device 1 shown in Fig. 2 is the liquid crystal cell (liquid after liquid crystal injection
Crystal cell), liquid crystal layer 20 is included in the structure.In this case, due to the temperature resistance problem of liquid-crystal compounds used,
Consequently, it is possible to produce to enter the substrate 10 with coated with resin layer 17 with high temperature in permanent film formation process described later
The problem of row baking is such.
In view of the above situation, in present embodiment, the baking temperature in permanent film formation process described later is preferably set to be
Less than more than 80 DEG C 150 DEG C such low temperature and implement.Under such temperature conditionss, coated tree can be also formed well
Lipid layer 17.
(coating method)
Positive type composition described above is coated on metal film 11 and forms coated film 12.The thickness of coated film 12 does not have
There are special limitation, preferably less than more than 0.1 μm 10 μm.
As the coating method of positive type composition, spin-coating method, slot coated method, rolling method, silk screen print method, painting can be used
The methods of applicator method.Preferred pair coated film 12 carries out prebake conditions.The species of each composition of the prebake conditions in photosensitive layer, match somebody with somebody
Composition and division in a proportion example, coating film thickness etc. it is different and different, generally, temperature be less than more than 70 DEG C 150 DEG C, preferably more than 80 DEG C 140
Below DEG C, the time is less than 60 minutes more than 2 minutes Zuo You.
Next, by the substrate 10 with the coated film 12 being formed as described above for exposure process.
＜ exposure process ＞
In exposure process, as shown in Fig. 1 (c), to the formation metal line 18 in coated film 12, (it is through pattern
The metal film of change) position beyond position be exposed.
As described above, coated film 12 is formed using positive type composition.For the coating formed by positive type composition
For film 12, exposed position is become soluble in alkaline-based developer.Therefore, by exposure, so that in coated film 12
Formation metal line 18 position beyond position become soluble in developer solution.
In exposure process, across the photomask 15 of predetermined pattern corresponding with the pattern of metal line 18, regioselectivity
Ground is to the irradiation exposure light 16 of coated film 12 being formed as described above.
As exposure light 16, active ray or radioactive ray can be used, such as wavelength is more than 300nm below 500nm's
Ultraviolet or luminous ray.
As the line source of radioactive ray, low pressure mercury lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, metal halide lamp, argon gas can be used
Laser etc..In addition, radioactive ray include microwave, infrared ray, luminous ray, ultraviolet, X ray, gamma-rays, electron ray, matter
Sub- ray, neutron ray, ion irradiation etc..The exposure of radioactive ray is according to the composition of positive type composition, the thickness of coated film 12
Deng it is different and different, such as be 100mJ/cm during using ultrahigh pressure mercury lamp2Above 10000mJ/cm2Below.
＜ etching mask formation process ＞
The coated film 12 exposed as shown in Fig. 1 (c) in etching mask formation process regioselectivity
In it is developed, thus, as shown in Fig. 1 (d), form patterned coated film 12, it is made as etching mask
Coated with resin layer 17.Now, as developer solution, alkaline aqueous solution can be used.
As developer solution, for example, can be used sodium hydroxide, potassium hydroxide, sodium carbonate, sodium metasilicate, sodium metasilicate, ammoniacal liquor,
Ethylamine, n-propyl amine, diethylamide, di-n-propyl amine, triethylamine, methyidiethylamine, dimethylethanolamine, three ethanol
Amine, TMAH, tetraethyl ammonium hydroxide, pyrroles, piperidines, 1,8- diazabicyclos [5,4,0] -7- endecatylenes,
The aqueous solution of the bases such as 1,5- diazabicyclos [4,3,0] -5- nonanes.In addition, it will can also add in the aqueous solution of above-mentioned bases
The aqueous solution is used as developer solution obtained from adding the water-miscible organic solvents such as appropriate methanol, ethanol, known surfactant.
Developing time also according to the composition of positive type composition, coated film 12 thickness etc. it is different and different, usually 1 point
More than clock less than 30 minutes.Developing method can be fluid containing method, infusion process, sheathed immersion development method (puddle method),
Any method in spray development method etc..
After development, the water displacement wash of less than 90 seconds more than 30 seconds is carried out, is dried using air cannon, baking oven etc..As above
Operate describedly, so as to form the coated with resin layer 17 as patterned coated film 12 on metal film 11.
＜ metal line formation process ＞
In metal line formation process, as shown in Fig. 1 (d) and Fig. 1 (e), work is formed using in etching mask
The coated with resin layer 17 formed in sequence is used as etching mask, is removed the metal film 11 exposed from etching mask by etching,
Form metal line 18.
Engraving method is not particularly limited, and can suitably be selected according to the material of metal film 11.Engraving method can be wet
Formula etches or dry-etching, Wet-type etching are low and preferred due to cost.
It should be noted that as shown in Fig. 1 (e), lower etch (under etch) occurs in etching sometimes,
That is, near the end of the coated with resin layer 17 as etching mask and the contact surface of metal film 11, metal film 11 is etched.
＜ permanent film formation process ＞
In permanent film formation process, the coated with resin layer 17 formed as shown in Fig. 1 (e) is toasted.Baking
It can carry out between etching mask formation process and metal line formation process, can also be carried out after metal line formation process.
By being toasted to coated with resin layer 17, first soften so as to coated with resin layer 17, then by cooling and
Solidified and close mode, as a result, coated with resin layer 17 forms permanent film.Coated with resin layer 17 is toasted and formed forever
The water resistance of film, heat resistance, solvent resistance etc. are excellent long.
In addition, in foregoing metal line formation process, occur following situations sometimes：The end of coated with resin layer 17 occurs
Bottom the lower etch that excessively carries out of etching, the width at the top (side of coated with resin layer 17) of metal line 18 becomes the bottom of than
The narrow width in portion (side of hyaline layer 14).
In this case, it is preferred that implement permanent film formation process after metal line formation process.The reason is that by forever
Heating in long film formation process, coated with resin layer 17 soften, coated with resin layer 17 according to the surface configuration of metal line 18 and
Deform.As a result, as shown in Fig. 1 (f), the coated with resin closely sealed with the substantially whole surface of metal line 18 is formed
Layer 17 is used as permanent film, and therefore, metal line 18 is not easy by user's visual identification of image display device.
Baking heater such as using heating plate, baking oven is carried out.The temperature of baking is not particularly limited, it is contemplated that
Form heat resistance of material of substrate 10 etc. and suitably determine.As baking temperature, for example, preferably more than 80 DEG C 400 DEG C with
Under, more preferably less than more than 150 DEG C 300 DEG C.
It should be noted that when substrate 10 has the liquid crystal cell comprising liquid crystal layer 20, baking temperature is preferably more than 80 DEG C
Less than 150 DEG C.
Baking time is preferably less than 60 minutes more than 15 minutes, more preferably less than 30 minutes.
By forming metal line 18 according to method described above, so as to can obtain following layered products, the layered product
Including metal line 18 and permanent film (coated with resin layer 17), and permanent film (coated with resin layer 17) contacts simultaneously with metal line 18
Coated metal wiring 18.
In the layered product, the coated with resin layer 17 as permanent film will not excessively cover pixel portion, and well
The whole surface of coated metal wiring 18.Therefore, by using the layered product, metal line 18 can be manufactured and be not easy visually to be known
Not, the image display device of the image of high-quality can be shown.
[embodiment]
Hereinafter, embodiment is shown further to specifically describe the present invention, but the scope of the present invention is not by these embodiments
Limitation.
(embodiment 1)
By the mass parts of Novolac resins 100, the mass parts of sensitizer 13, the mass of compound 22.6 containing quinone diazido
Part and the pigment for being 27 mass % for whole solid state component quality equably dissolve, are scattered in propylene glycol monomethyl
In ether acetic acid ester so that solid component concentration is 20 mass %, obtains positive type composition.
It should be noted that contain the 2- hydroxyls for for whole solid state components being 1 mass % in positive type composition
Base ethylpyridine and the silicon systems surfactant (BYK-310, the BYK that are 0.4 mass % for whole solid state components
Chemie company systems).
As Novolac resins, the cresols type Novolac trees that weight average molecular weight is 4700, decentralization is 4.5 have been used
Fat.
As sensitizer, phenolic resin (trade name has been used：TrisP-PA-MF, Honshu Chemical Ind's system).
As the compound containing quinone diazido, having used makes 2,3,4,4'-Tetrahydroxybenzophenone and naphthoquinones -1,2-
Compound obtained from diazido -5- sulfonic acid is esterified.
As pigment, the red of the imperial state's pigment company system for being 14.9 mass % has been used for whole solid state components
The blue pigment of color pigment and the imperial state's pigment company system for being 12.1 mass % for whole solid state components.
Obtained positive type composition is coated on to the gold of the substrate with colour filter and metal film (Al films) using spin coater
Belong on film, then carry out 60 seconds prebake conditions in 90 DEG C, so as to form the photosensitive layer that thickness is 1.5 μm.
Across L/S=1：1 and width be 3 μm of photomask, use exposure device (MPA-600FA, 365mW, 100mJ/
cm2, Canon company systems), obtained photosensitive layer is exposed.
Next, TMAH (TMAH) aqueous solution that concentration is 2.38 mass % is carried out as developer solution
Development, forms the coated with resin layer for being patterned as regulation shape.
Using the coated with resin layer of formation as etching mask, carried out using Al nitration mixture etchant (phosphoric acid/nitric acid/acetic acid)
Etching, so as to form patterned metal level as metal line.The surface of metal line is coated to by coated with resin layer.
The rear baking of 5 minutes is carried out to the substrate after etching in 120 DEG C, coated with resin layer is turned into permanent film.Thus, obtain
To the substrate with metal line and permanent film (coated with resin layer).
It should be noted that as substrate, following substrate has tentatively been used.
I.e., first, line width is set on a face of glass substrate for 5 μm of black matrix" and RGB pattern, in glass
Sputtering forms the aluminium lamination that thickness is 0.2 μm on the surface in another face of substrate, and substrate is made.
The optical density of the coated with resin layer of formation is 0.60/ μm.
In addition, the shape of the permanent film of formation is observed using microscope, as a result, the thickness of permanent film is substantially equal
It is even, the face is carried out from the direction vertical with the face for foring metal line of substrate from when, not by permanent film above pixel
It is coated to, does not observe that metal line exposes.
It should be noted that in the case where substrate is applied into image display device, pixel is equivalent to making backlight etc.
The transmittance section that the light that light source is sent passes through.
(comparative example 1)
By the dissolving of the mass parts of acrylic resin 100, the mass parts of photoacid generator 3 and the mass parts of colouring agent 5, it is scattered in propane diols
In monomethyl ether acetate so that solid component concentration is 12 mass %, obtains positive type composition.
As acrylic resin, 40 moles of % of 1- ethoxyethyl groups ether, the methacrylic acid (3- of 4-Vinyl phenol are used
Ethyloxetane -3- bases) 35 moles of % of methyl esters, 15 moles of % of methyl methacrylate and methacrylic acid 2- hydroxyl second
20 moles of % of ester copolymer.The weight average molecular weight of the acrylic resin is 6000, decentralization 7.2.
As photoacid generator, triarylsulfonium salt (trade name has been used：DTS-105, Midori Kagaku Co., Ltd.s
System).
As colouring agent, following black pigments have been used：Use the mass parts of dispersant 0.65 and polymer (metering system
3.7 ten thousand) random copolymer of acid benzyl ester (72 moles of %) and methacrylic acid (28 moles of %), weight average molecular weight are, by carbon black
13.1 mass parts are scattered in black pigment obtained from the mass parts of propylene glycol monomethyl ether 79.53.
Using obtained positive type composition, operate similarly to Example 1, metal line and permanent is formed on substrate
Film.
The optical density of the permanent film of formation is 0.60/ μm.
In addition, the shape of the permanent film of formation is observed using microscope, as a result, the thickness of permanent film is substantially equal
It is even, the face is carried out from the direction vertical with the face for foring metal line of substrate from when, although do not observe hardware cloth
Line exposes, but in the region near the metal line above pixel, throughout sees the position being coated to by permanent film.
Claims (5)
1. positive type photosensitive organic compound, the positive type photosensitive organic compound is used to form patterned organic film,
Used when the patterned organic film forms metal line being etched to metal film as etching mask, and
The permanent film of the metal line formed in the state of cured as coated etched uses,
The positive type photosensitive organic compound include (A) Novolac resins, the compound of (B) containing quinone diazido and
(C) colouring agent.
2. positive type photosensitive organic compound as claimed in claim 1, wherein, the Weight-average molecular of (A) the Novolac resins
Measure as less than more than 1,000 50000.
3. the manufacture method of metal line, methods described includes following processes：
The process for being coated with the positive type photosensitive organic compound described in claim 1 or 2 on metal film and forming coated film；
The process being exposed to the coated film regioselectivity；
The process that the exposed coating film development is formed into etching mask；
The metal film on the surface with the etching mask is etched, is coated to so as to be formed by the etching mask
Metal line process；And
The etching mask is toasted, so as to form the process of the permanent film of the coated metal line.
4. the manufacture method of metal line as claimed in claim 3, wherein, it is described to be etched to Wet-type etching.
5. layered product, the layered product includes metal line and permanent film,
The permanent film contacts with the metal line and is coated to the metal line,
The permanent film is the film for being solidified to form the positive type photosensitive organic compound described in claim 1 or 2.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016155877A JP6756541B2 (en) | 2016-08-08 | 2016-08-08 | Substrate manufacturing method |
| JP2016-155877 | 2016-08-08 | ||
| JP2017115467A JP6878160B2 (en) | 2017-06-12 | 2017-06-12 | Positive photosensitive resin composition, metal wiring manufacturing method, and laminate |
| JP2017-115467 | 2017-06-12 |
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| CN107703717A true CN107703717A (en) | 2018-02-16 |
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| CN201710643741.5A Active CN107703717B (en) | 2016-08-08 | 2017-07-31 | Positive photosensitive resin composition, method for producing metal wiring, and laminate |
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| CN111624852A (en) * | 2019-02-28 | 2020-09-04 | 东京应化工业株式会社 | Photosensitive resin composition and method for etching glass substrate |
| CN115877661A (en) * | 2022-12-16 | 2023-03-31 | 徐州博康信息化学品有限公司 | High-adhesion epoxy I-line negative photoresist and preparation and use methods thereof |
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| CN111624852A (en) * | 2019-02-28 | 2020-09-04 | 东京应化工业株式会社 | Photosensitive resin composition and method for etching glass substrate |
| CN115877661A (en) * | 2022-12-16 | 2023-03-31 | 徐州博康信息化学品有限公司 | High-adhesion epoxy I-line negative photoresist and preparation and use methods thereof |
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| Publication number | Publication date |
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| TW201809904A (en) | 2018-03-16 |
| TWI740998B (en) | 2021-10-01 |
| CN107703717B (en) | 2023-01-24 |
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