CN110462515A

CN110462515A - The manufacturing method of photosensitive transfer printing material and wiring

Info

Publication number: CN110462515A
Application number: CN201780088772.7A
Authority: CN
Inventors: 藤本进二; 松田知树; 山田悟
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2017-03-30
Filing date: 2017-12-25
Publication date: 2019-11-15
Also published as: TW201837069A; TWI767974B; WO2018179641A1; JP6893550B2; JPWO2018179641A1

Abstract

A kind of manufacturing method of photosensitive transfer printing material and the wiring for having used photosensitive transfer printing material, the photosensitive transfer printing material has temporary support and photosensitive polymer combination layer, the photosensitive polymer combination layer contains component of polymer and photoacid generator comprising polymer, the polymer includes the Component units (a-1) with carboxyl protected group in the form of acetal, or the Component units (a-2) with phenolic hydroxyl group protected group in the form of acetal, component of polymer includes at least one of the Component units (b-1) with phenolic hydroxyl group and the Component units (b-2) with alcohol hydroxyl group, the ratio of the ratio and Component units (b-2) of shared Component units (b-1) adds up to 1 mole of % or more and 18 in total Component units of component of polymer Mole % or less.

Description

The manufacturing method of photosensitive transfer printing material and wiring

Technical field

The present invention relates to the manufacturing methods of a kind of photosensitive transfer printing material and wiring.

Background technique

In display device (organic electroluminescent (EL) display device for having the touch panels such as capacitive input device And liquid crystal display device etc.) in, it is equivalent to electrode pattern, edge wiring portion and the lead-out wiring of the sensor in visuognosis portion The conductive layers pattern such as partial wiring is set to inside touch panel.

When being usually formed patterned layer, since the operation quantity for obtaining required pattern form is few, it is widely used To the layer of the photosensitive polymer combination that uses photosensitive transfer printing material to be set on any substrate across with desired The method that the mask of pattern develops after being exposed.

Such as in Japanese Unexamined Patent Publication 2010-008972 bulletin, discloses a kind of plating forming object manufacture and put with eurymeric sense Ray resin combination, the polymer for containing Component units and the acid dissociation functional group with phenolic hydroxyl group, sense are put Ray acid producing agent and organic solvent, and contain radioactivity-sensitive acid producing agent 1~20 relative to 100 parts by weight of polymer Parts by weight.

Such as in Japanese Unexamined Patent Publication 2016-057612 bulletin, a kind of chemically amplified positive resist dry film is disclosed, Become soluble containing phenol resin and by radioactive ray or photoactinic work in aqueous alkali containing the effect by acid With and generate acid photoacid generator.

Such as in Japanese Unexamined Patent Publication 2015-180957 bulletin, a kind of chemically amplified positive photoetching compositions are disclosed, It contains resin and photosensitive acid generator compound with phenolic hydroxyl group.

Such as in Japanese Unexamined Patent Publication 2015-118202 bulletin, a kind of photosensitive transfer printing material is disclosed, there is support Body and photosensitive polymer combination layer, photosensitive polymer combination layer contain polymer and photoacid generator, and the polymer includes Component units with the acidic group protected by sour decomposability base, photosensitive polymer combination do not have ethylene cross-linked structure.

Such as in Japanese Unexamined Patent Publication 2006-003861 bulletin, a kind of positive light sensitivity anti-corrosion agent composition is disclosed, Containing in a molecule at least with the compounds of bis- (the trichloromethyl)-cyanuros of 1 4,6-, organic amine compound and Acid-sensitive copolymer.

Summary of the invention

The invention technical task to be solved

The one embodiment of the present invention project to be solved is to provide a kind of the molten of the unexposed portion relative to developer solution Solution property is low, and the photosensitive transfer printing material for deforming few eurymeric of obtained pattern form.

Another embodiment of the present invention project to be solved is to provide a kind of photosensitive transfer printing material for having used eurymeric The manufacturing method of the wiring of material.

For solving the means of technical task

Means for solving the problem includes following manner.

A kind of photosensitive transfer printing material of 1 > of < has temporary support and photosensitive polymer combination layer, described photosensitive Property resin composition layer contain component of polymer and photoacid generator comprising polymer, the polymer include have carboxyl with The Component units (a-1) of the protected group of the form of acetal or with phenolic hydroxyl group in the form of acetal protected group Component units (a-2), component of polymer include the Component units (b-1) with phenolic hydroxyl group and the composition with alcohol hydroxyl group At least one of unit (b-2), the ratio and structure of shared Component units (b-1) in total Component units of component of polymer 1 mole of % or more and 18 mole of % or less is added up at the ratio of unit (b-2).Wherein, when component of polymer does not include tool When having the polymer of Component units (a-1), the ratio of Component units (b-1) is not included within amounting to.

2 > of < photosensitive transfer printing material according to 1 > of <, wherein the acid value of component of polymer be 60mgKOH/g with Under.

3 > of < photosensitive transfer printing material according to 2 > of < 1 > or <, the wherein glass transition of component of polymer Temperature is 90 DEG C or less.

4 > of < photosensitive transfer printing material according to 2 > of < 1 > or <, the wherein glass transition of component of polymer Temperature is 60 DEG C or less.

5 > of < photosensitive transfer printing material according to any one of 1 > of <~<, 4 >, wherein Component units (a-1) be The Component units indicated with following formula A1.

[chemical formula 1]

In formula A1, R³¹And R³²Separately indicate hydrogen atom, alkyl or aryl, R³¹And R³²At least one of It is alkyl or aryl, R³³Indicate alkyl or aryl, R³¹Or R³²It can be with R³³It connects and forms cyclic ether, R³⁴Indicate hydrogen atom or first Base, X⁰Indicate singly-bound or arlydene.

6 > of < photosensitive transfer printing material according to any one of 1 > of <~<, 5 >, wherein Component units (a-2) be The Component units indicated with following formula A3.

[chemical formula 2]

In formula A3, R⁵¹And R⁵²Separately indicate hydrogen atom, alkyl or aryl, R⁵¹And R⁵²At least one of It is alkyl or aryl, R⁵³Indicate alkyl or aryl, R⁵¹Or R⁵²It can be with R⁵³It connects and forms cyclic ether, R⁵⁴Indicate hydrogen atom or first Base, X¹Indicate the linking group of singly-bound or divalent, R⁶²Indicate that substituent group, n indicate 0~4 integer.

7 > of < photosensitive transfer printing material according to any one of 1 > of <~<, 6 >, wherein Component units (b-1) be The Component units indicated with following formula B1.

[chemical formula 3]

In formula B1, R⁷⁰Indicate hydrogen atom or methyl, R⁷¹Indicate the linking group of singly-bound or divalent, R⁷²Independently earth's surface Show that halogen atom or alkyl, a indicate that 1~5 integer, b indicate that 0~4 integer, a+b are 5 or less.

8 > of < photosensitive transfer printing material according to any one of 1 > of <~<, 7 >, wherein Component units (b-2) be The Component units indicated with following formula B2.

[chemical formula 4]

In formula B2, R⁸⁰Indicate hydrogen atom or methyl, R⁸¹Indicate singly-bound or arlydene, R⁸²Indicate alkylidene.

9 > of < photosensitive transfer printing material according to any one of 1 > of <~<, 8 >, wherein component of polymer is into one Step is with the Component units from (methyl) alkyl acrylate with cyclic alkyl.

A kind of manufacturing method of wiring of 10 > of < successively includes following process: for substrate, making 1 > of <~<, 9 > Any one of described in photosensitive transfer printing material the photosensitive polymer combination layer process that is in contact with substrate and is bonded；To fitting The process that the photosensitive polymer combination layer of photosensitive transfer printing material after process carries out pattern exposure；To the process being exposed The process that photosensitive polymer combination layer afterwards is developed and forms pattern；And to the base being not configured in figuratum region The process that plate is etched.

Invention effect

According to an embodiment of the present invention, the dissolubility for being capable of providing a kind of unexposed portion relative to developer solution is low, And the photosensitive transfer printing material for deforming few eurymeric of obtained pattern form.

Another embodiment according to the present invention is capable of providing a kind of circuit of photosensitive transfer printing material for having used eurymeric The manufacturing method of wiring.

Detailed description of the invention

Fig. 1 is the synoptic diagram for indicating an example of layer structure of photosensitive transfer printing material of the invention.

Fig. 2 is the synoptic diagram for indicating pattern A.

Fig. 3 is the synoptic diagram for indicating pattern B.

Specific embodiment

Hereinafter, the embodiment to invention is illustrated.Grade explanation and embodiment exemplify embodiment, and unlimited Determine invention scope.

The numberical range for using "~" to indicate in this specification refers to the numerical value that will be recorded before and after "~" as lower limit value And the range that upper limit value includes.

When referring to the amount of each ingredient in composition in the present specification, if exist in the composition it is a variety of be equivalent to it is each at When the substance divided, as long as no specifying, then refer to the total amount of the existing many kinds of substance in the composition.

In this specification, " process " this term refers not only to independent process, even if can not be clear with other processes In the case where differentiation, as long as can be realized the desired purpose of process, it is included in this term.

In the label of group (atomic group) in the present specification, substitution and unsubstituted label are not indicated comprising having The substance of substituent group and substance without substituent group.Such as " alkyl " is not only (unsubstituted comprising the alkyl without substituent group Alkyl), also comprising with substituent group alkyl (substituted alkyl).

Chemical structural formula in this specification is also recorded using the schematic arrangement formula that hydrogen atom is omitted sometimes.

In the present specification, " (methyl) acrylic acid " indicate both acrylic acid and methacrylic acid or any one, " (first Base) acrylate " indicate both acrylate and methacrylate or any one.

In the present invention, " quality % " is identical as the meaning of " weight % ", and " mass parts " are identical as the meaning of " parts by weight ".

In the present invention, the group of preferably 2 or more mode is combined into preferred mode.

Weight average molecular weight (Mw) and number average molecular weight (Mn) in the present invention are logical as long as no rule is referred in particular to Crossing and having used TSKgel GMHxL, TSKgel G4000HxL, TSKgel G2000HxL (is TOSOH CORPORATION system ProductName) tubing string gel permeation chromatography (GPC) analytical equipment, use tetrahydrofuran (THF) as solvent, and pass through difference Show that refractometer is detected, the molecular weight that polystyrene is converted as standard substance.

In the present invention, when the content of " Component units " being carried out specific with mole %, " Component units " are set as and " list The meaning of body unit " is identical.In the present invention, " monomeric unit " can be modified after polymerisation.

Reference implementation mode is in the present invention come when illustrating attached drawing, the composition of the embodiment is not limited to shown in attached drawing Composition.Also, the size of the component in each figure is conceptual size, and the relativeness of the size between component is not limited to This.

< photosensitive transfer printing material >

Photosensitive transfer printing material of the invention has temporary support and the sense containing component of polymer and photoacid generator Photosensitive resin composition layer." component of polymer " indicates the polymer contained in photosensitive polymer combination layer in the present invention It is overall.The photosensitive polymer combination layer of present embodiment is the photosensitive polymer combination layer of eurymeric, sometimes referred to as " eurymeric sense Photosensitive resin composition layer ".

In photosensitive transfer printing material of the invention, the component of polymer of photosensitive polymer combination layer includes polymer, The polymer is comprising the Component units (a-1) with carboxyl protected group in the form of acetal or has phenolic hydroxyl group The Component units (a-2) of protected group in the form of acetal.

Hereinafter, above-mentioned polymer is referred to as " polymer A " sometimes, and the protection of acidic group will be protected in the form of acetal sometimes Base is referred to as " acetal type protecting group ".

In photosensitive transfer printing material of the invention, the component of polymer of photosensitive polymer combination layer includes to have phenol At least one of the Component units (b-1) of hydroxyl and the Component units (b-2) with alcohol hydroxyl group, in component of polymer The ratio of the ratio and Component units (b-2) of shared Component units (b-1) adds up to 1 mole of % or more in total Component units And 18 moles of % or less.

Wherein, when component of polymer does not include the polymer with Component units (a-1), not by Component units (b-1) Ratio be included in above-mentioned total within.In other words, when component of polymer do not include with Component units (a-1) polymer and When comprising polymer with Component units (a-2), component of polymer centainly has Component units (b-2), and it is total constitute it is single The ratio of shared Component units (b-2) is 1 mole of % or more and 18 mole of % or less in member.When component of polymer does not include tool When having the polymer of Component units (a-1), component of polymer can have Component units (b-1) that can also not have, but from by phase For the dissolubility in the unexposed portion of developer solution be suppressed to it is lower from the viewpoint of, component of polymer does not preferably have Component units (b-1)。

Hereinafter, the ratio of shared Component units (b-1) in total Component units of component of polymer is referred to as sometimes "Mb-1".The unit of Mb-1 is " mole % ".

Hereinafter, the ratio of shared Component units (b-2) in total Component units of component of polymer is referred to as sometimes "Mb-2".The unit of Mb-2 is " mole % ".

It is constituted in photosensitive transfer printing material of the invention, possessed by the component of polymer of photosensitive polymer combination layer single First (b-1) or Component units (b-2) can be Component units possessed by polymer A, be also possible to its different from polymer A Component units possessed by his polymer.Hereinafter, sometimes by as the other polymers different from polymer A, and have and constitute The polymer of at least one of unit (b-1) and Component units (b-2) is referred to as " polymer B ".

The dissolubility in the unexposed portion relative to developer solution of photosensitive transfer printing material of the invention is low, and obtained figure The deformation of case shape is few.The reason can be inferred as follows.

The inventors of the present invention have found that there are the following problems, and the process of roll-to-roll (roll-to-roll) is considered continuously right The process being wound up into after substrate implementation transfer printing process-exposure process-developing procedure of conveying on roller, but actually implement production In the case where, when being led to the problem of in any process, it is necessary to stop the conveying of substrate, at this point, stopping in transfer printing process, developing procedure The performance of part only significantly deteriorates, therefore has to abandon.

Also, in exposure process, technically not yet establish on one side with constant speed convey substrate while across mask progress Exposure, and need to install the complicated devices such as the device of conveying for locally stopping substrate.Also, the inventors of the present invention infer, point The each process of transfer, exposure and development is not independently configured, and is embedded in the work of uncoiling and winding before and after each process Sequence is more satisfactory in the range of the prior art.

However, the inventors of the present invention's discovery is being transferred comprising this kind, in the method for each process of exposure and development, if image The layer for having used chemically amplified positive photosensitive polymer combination is formed, then generates the deformation of obtained pattern sometimes.When making When with previous resist other than chemically amplified positive photosensitive polymer combination, above-mentioned phenomenon is not found.

It is that the inventors of the present invention are furtherd investigate as a result, when finding that the phenomenon is using chemically amplified positive resin combination Characteristic phenomenon, find the photosensitive transfer printing material by being set as above structure, the deformation of obtained pattern form is reduced.

Although detailed discovery mechanism is indefinite, the deformation of obtained pattern form is especially amplified just using chemistry Show when type resin combination, the inventors of the present invention, which infer, whereby is due to the de- of the acetal type protecting group based on the acid generated The phenomenon that diffusion of compound from reaction and from the acetal type protecting group being detached from later.The inventors of the present invention's deduction, if Photosensitive polymer combination layer contains phenolic hydroxyl group or alcohol hydroxyl group, then phenolic hydroxyl group or alcohol hydroxyl group can be captured from having taken off From acetal type protecting group compound, therefore relatively reduce compound from the acetal type protecting group having disengaged to phase Nearly pixel diffusion, inhibits the generation based on the internal stress in the film with the volume change of above-mentioned diffusion, inhibits gained whereby The deformation of the pattern form arrived.

In the photosensitive polymer combination layer of photosensitive transfer printing material of the invention, when being inferred as Component units (b-1) institute At least one of alcohol hydroxyl group possessed by the phenolic hydroxyl group and Component units (b-2) having helps to capture from When the compound of the acetal type protecting group of disengaging, thus it is speculated that if M^b-1And M^b-2Less than 1 mole % of total, then be unable to fully capture come From in the compound for the acetal type protecting group having disengaged from, and the deformation of obtained pattern form can not be inhibited.It is examined from the viewpoint Consider, M^b-1And M^b-2Add up to 1 mole of % or more, more preferably 5 moles of % or more, further preferably 10 moles of % or more.

On the other hand, if M^b-1And M^b-2Total over 18 moles of %, then unexposed portion becomes readily soluble relative to developer solution Solution.From the dissolubility relative to the unexposed portion of developer solution is suppressed to it is lower from the viewpoint of, M^b-1And M^b-2Add up to 18 Mole % is hereinafter, more preferably 15 moles of % or less.

Side in photosensitive transfer printing material of the invention, as component of polymer contained in photosensitive polymer combination layer Formula, such as following 1st embodiment~the 5th embodiments can be enumerated.

- the 1 embodiment-

Component of polymer includes at least polymer A-I, and the polymer A-I includes that there is carboxyl to be protected in the form of acetal The Component units (a-1) and the Component units (b-1) with phenolic hydroxyl group of the group of shield and the composition list with alcohol hydroxyl group At least one of first (b-2).

- the 2 embodiment-

Component of polymer includes at least polymer A-II, and the polymer A-II includes to have phenolic hydroxyl group with the shape of acetal The Component units (a-2) of the protected group of state and Component units (b-2) with alcohol hydroxyl group.

- the 3 embodiment-

Component of polymer includes at least following polymer:

Polymer A-III, comprising the Component units (a-1) with carboxyl protected group in the form of acetal, and not Include the Component units (b-1) with phenolic hydroxyl group and the Component units (b-2) with alcohol hydroxyl group；And

Polymer B-I includes the Component units (b-1) with phenolic hydroxyl group.

- the 4 embodiment-

Component of polymer includes at least following polymer:

Polymer B-II includes the Component units (b-2) with alcohol hydroxyl group.

- the 5 embodiment-

Component of polymer includes at least following polymer:

Polymer A-IV, comprising the Component units (a-2) with phenolic hydroxyl group protected group in the form of acetal, and Not comprising the Component units (b-2) with alcohol hydroxyl group；And

Polymer B-II includes the Component units (b-2) with alcohol hydroxyl group.

In any of the 1st embodiment~the 5th embodiment, polymer A-I contained in component of polymer~ A-IV and polymer B-I~B-II can be only respectively a kind or two or more, component of polymer may include in addition to Other polymers other than polymer A-I~A-IV and polymer B-I~B-II.In addition, being equivalent to friendship for what is described below Although the compound of connection agent and dispersing agent is set as being high-molecular compound but the substance for being not included in component of polymer.

It is shared in total Component units of component of polymer in any of the 1st embodiment~the 5th embodiment Component units (b-1) ratio and Component units (b-2) ratio total be 1 mole of % or more and 18 mole of % with Under.Wherein, when component of polymer does not include the polymer with Component units (a-1), not by the ratio of Component units (b-1) Within above-mentioned total.

Hereinafter, being illustrated to the layer structure of photosensitive transfer printing material of the invention, constituent material of each layer etc..

Fig. 1 is diagrammatically denoted by an example of the layer structure of photosensitive transfer printing material of the invention.Photonasty shown in FIG. 1 turns Temporary support 10, photosensitive polymer combination layer 14 and cover film 16 are sequentially laminated in print material 100.Photoresist Composition layer 14 contains component of polymer and photoacid generator.

[temporary support]

Temporary support is support photosensitive polymer combination layer, and can be from the branch of photosensitive polymer combination layer removing Support body.

The temporary support being used in the present invention to photosensitive polymer combination layer carry out pattern exposure when can From the viewpoint of being exposed via temporary support to photosensitive polymer combination layer, preferably there is translucency.

The transmitance that the dominant wavelength of the light used in pattern exposure is indicated with translucency is 50% or more, is exposed in pattern The transmitance of the dominant wavelength of light used in light is from the viewpoint of improving exposure sensitivity, and preferably 60% or more, more preferably It is 70% or more.As the measuring method of transmitance, it can enumerate and utilize Otsuka Electronics Co., Ltd. MCPD The method that Series is measured.

As temporary support, glass substrate, resin film, paper etc. can be enumerated, is considered from the viewpoints such as intensity and flexibility, especially It is preferably resin film.As resin film, polyethylene terephthalate film can be enumerated, tri cellulose acetate membrane, polystyrene film, gathered Carbonic ester film etc..Wherein, especially preferably biaxial stretch-formed polyethylene terephthalate film.

The thickness of temporary support is not particularly limited, preferably 5 μm~200 μm of range, from handling easiness, is led to Considered with viewpoints such as property, more preferably 10 μm~150 μm of range.The thickness of temporary support from as supporter intensity, It is examined with viewpoints such as translucency required in flexible, the initial exposure process required by being bonded of wiring formation substrate Consider, is selected according to material.

Preferred embodiment about temporary support is for example 0017 section~the 0018 of Japanese Unexamined Patent Publication 2014-085643 bulletin On the books in section, the content of the bulletin is incorporated into this manual.

[photosensitive polymer combination layer]

Photosensitive polymer combination layer contains component of polymer and photoacid generator.Photosensitive transfer printing material of the invention is had Standby photosensitive polymer combination layer is positive type photosensitive organic compound layer, preferably chemically amplified positive photoresist group Close nitride layer.

In the photoacid generators such as the salt or oxime sulfonate compounds that describe below, incudes actinic ray and generate sour to poly- The deprotection of protected acidic group in polymer component plays a role as catalyst, therefore is generated by the effect of 1 light quantum Acid facilitate multiple deprotection reactions, quantum yield is greater than 1, for example, becoming the biggish value of the power such as 10, as so-called High sensitivity can be obtained in the result of chemistry amplification.

On the other hand, as photoactinic photoacid generator is incuded, in the case where using quinone diazide, by chain Photochemical reaction generates carboxyl, but its quantum yield is necessary for 1 hereinafter, not meeting chemical amplifying type.

Polymer A is by the effect to expose the acidic materials of the catalyst amount generated, carboxylic possessed by Component units (a-1) Base phenolic hydroxyl group possessed by protected group or Component units (a-2) in the form of acetal is protected in the form of acetal Group by deprotection reaction and become acidic group.By the acidic group, can be dissolved in developer solution.

Polymer in polymer A and polymer B with Component units (b-2) is preferably the polymerization of addition polymerization type Object.The grade polymer are more preferably the polymer with the Component units from (methyl) acrylic acid or its ester.The equal polymerization Object also can have the Component units other than the Component units from (methyl) acrylic acid or its ester, such as from benzene The Component units of ethylene or Component units etc. from vinyl compound.

In polymer B with Component units (b-1) polymer B be preferably ethylene phenols addition polymer or phenolic aldehyde it is clear Paint shaped phenol resin.

Hereinafter, the Component units for being formed in polymer contained in component of polymer are described in detail.

Component units (a-1)-with carboxyl protected group in the form of acetal

As Component units (a-1), from the viewpoint and inhibition figure of sensitivity and excellent in resolution when pattern formation From the viewpoint of the deformation of case shape, the Component units A1 that is preferably indicated with following formula A1.It is constituted possessed by polymer A single First A1 can be a kind, or two or more.

[chemical formula 5]

In formula A1, R³¹And R³²Separately indicate hydrogen atom, alkyl or aryl, R³¹And R³²In at least one A is alkyl or aryl, R³³Indicate alkyl or aryl, R³¹Or R³²It can be with R³³It connects and forms cyclic ether, R³⁴Indicate hydrogen atom or Methyl, X⁰Indicate singly-bound or arlydene.

In formula A1, R³¹Or R³²In the case where for alkyl, preferably carbon atom number be 1~10 alkyl.R³¹Or R³²For aryl In the case of, preferred phenyl.R³¹And R³²It is respectively preferably the alkyl of hydrogen atom or carbon atom number 1~4.

In formula A1, R³³Indicate alkyl or aryl, the preferably alkyl of carbon atom number 1~10, more preferable carbon atom number 1~6 Alkyl.

R³¹~R³³In alkyl and aryl can have substituent group.

In formula A1, R³¹Or R³²With R³³It can connect and form cyclic ether, preferably R³¹Or R³²With R³³It connects and is formed cyclic annular Ether.The number of rings of cyclic ether is not particularly limited, it is preferred that being 5 or 6, more preferably 5.

In formula A1, X⁰Indicate singly-bound or arlydene, preferably singly-bound.As arlydene, preferably biphenylene, arlydene can be with With substituent group.

In formula A1, R³⁴Indicate hydrogen atom or methyl, from the viewpoint of the Tg that can more reduce polymer A, preferably For hydrogen atom.R relative to the total amount of the Component units A1 contained in polymer A, in formula A1³⁴For the Component units of hydrogen atom Preferably 20 mass % or more.R in the formula A1 of total amount relative to Component units A1³⁴For the quality of the Component units of hydrogen atom Ratio can be by the intensity for the peak strength for being measured according to 13C- nuclear magnetic resoance spectrum (NMR) and being calculated by conventional method than Lai true Recognize.

Among the Component units A1 indicated with formula A1, from the viewpoint of sensitivity when more improving pattern formation, more It is preferred that the Component units A2 indicated with following formula A2.Component units A2 possessed by polymer A can be a kind, or 2 kinds with On.

[chemical formula 6]

In formula A2, R³⁴Indicate hydrogen atom or methyl, R³⁵~R⁴¹Separately indicate hydrogen atom or carbon atom number 1~4 Alkyl.

In formula A2, R³⁴It is preferred that hydrogen atom.

In formula A2, R³⁵~R⁴¹It is preferred that hydrogen atom.

As the concrete example of Component units (a-1), following Component units can be illustrated.R³⁴Indicate hydrogen atom or methyl.

[chemical formula 7]

The ratio of shared Component units (a-1) is preferably 10 moles of % or more in total Component units of component of polymer And 70 moles of % hereinafter, more preferably 20 moles of % or more and 60 mole of % hereinafter, further preferably 30 moles of % or more and 50 moles of % or less.

Component units (a-2)-with phenolic hydroxyl group protected group in the form of acetal

As Component units (a-2), from the viewpoint and inhibition figure of sensitivity and excellent in resolution when pattern formation From the viewpoint of the deformation of case shape, the Component units A3 that is preferably indicated with following formula A3.It is constituted possessed by polymer A single First A3 can be a kind, or two or more.

[chemical formula 8]

In formula A3, R⁵¹And R⁵²Separately indicate hydrogen atom, alkyl or aryl, R⁵¹And R⁵²In at least one A is alkyl or aryl, R⁵³Indicate alkyl or aryl, R⁵¹Or R⁵²It can be with R⁵³It connects and forms cyclic ether, R⁵⁴Indicate hydrogen atom or Methyl, X¹Indicate the linking group of singly-bound or divalent, R⁶²Indicate that substituent group, n indicate 0~4 integer.

In formula A3, work as R⁵¹And R⁵²When for alkyl, preferably carbon atom number be 1~10 alkyl.Work as R⁵¹And R⁵²For When aryl, preferably phenyl.It is preferred that R⁵¹And R⁵²Respectively hydrogen atom or the alkyl of carbon atom number 1~4.

In formula A3, R⁵³Indicate alkyl or aryl, the preferably alkyl of carbon atom number 1~10, more preferably carbon atom number 1 ~6 alkyl.

R⁵¹~R⁵³In alkyl and aryl can have substituent group.

In formula A3, R⁵¹Or R⁵²It can be with R⁵³It connects and forms cyclic ether, preferably R⁵¹Or R⁵²With R⁵³It connects and is formed cyclic annular Ether.The number of rings of cyclic ether is not particularly limited, and preferably 5 or 6, more preferably 5.

In formula A3, X¹Indicate the linking group of singly-bound or divalent, preferably singly-bound or alkylidene ,-C (=O) O- ,-C (=O) NRN- ,-O- or this etc. combination, more preferably singly-bound.Alkylidene can be straight chain and can have branch also to have ring Shape structure can also have substituent group.The carbon atom number of alkylidene is preferably 1~10, and more preferably 1~4.Work as X¹Comprising-C (= O) when O-, preferably carbon atom and and R contained in-C (=O) O-⁵⁴The mode of the carbon atom Direct Bonding of bonding.Work as X¹Packet When containing-C (=O) NRN-, carbon atom and and R contained in preferably-C (=O) NRN-⁵⁴The side of the carbon atom Direct Bonding of bonding Formula.RN indicates alkyl or hydrogen atom, the preferably alkyl or hydrogen atom of carbon atom number 1~4, more preferably hydrogen atom.

In formula A3, R is preferably comprised⁵¹~R⁵³Group and X¹To be bonded with phenyl ring with aligning mutually.

In formula A3, R⁶²Indicate substituent group, preferably alkyl or halogen atom.The carbon atom number of alkyl is preferably 1~10, more Preferably 1~4.

In formula A3, the integer of n expression 0~4, preferably 0 or 1, more preferably 0.

In formula A3, R⁵⁴Indicate hydrogen atom or methyl, from the viewpoint of the Tg that can more reduce polymer A, preferably For hydrogen atom.R relative to the total content of Component units A3 contained in polymer A, in formula A3⁵⁴For the Component units of hydrogen atom Preferably 20 mass % or more.R in the formula A3 of total amount relative to Component units A3⁵⁴For the quality of the Component units of hydrogen atom Ratio can be by the intensity for the peak strength for being measured according to 13C- nuclear magnetic resoance spectrum (NMR) and being calculated by conventional method than Lai true Recognize.

In the Component units indicated with formula A3, from the viewpoint of the deformation for inhibiting pattern form, more preferably with following formula The Component units A4 that A4 is indicated.Component units A4 possessed by polymer A can be a kind, or two or more.

[chemical formula 9]

In formula A4, R⁵⁴Indicate hydrogen atom or methyl, R⁵⁵~R⁶¹Separately indicate hydrogen atom or carbon atom number 1~4 Alkyl, R⁶²Indicate that substituent group, n indicate 0~4 integer.

In formula A4, R⁵⁴Preferably hydrogen atom.

In formula A4, R⁵⁵~R⁶¹Preferably hydrogen atom.

In formula A4, R⁶²Indicate substituent group, preferably alkyl or halogen atom.The carbon atom number of alkyl is preferably 1~10, more Preferably 1~4.

In formula A4, the integer of n expression 0~4, preferably 0 or 1, more preferably 0.

As the concrete example of Component units (a-2), following Component units can be illustrated.R⁵⁴Indicate hydrogen atom or methyl.

[chemical formula 10]

The ratio of shared Component units (a-2) is preferably 10 moles of % or more in total Component units of component of polymer And 70 moles of % hereinafter, more preferably 20 moles of % or more and 60 mole of % hereinafter, further preferably 30 moles of % or more and 50 moles of % or less.

Component units (b-1)-with phenolic hydroxyl group

As Component units (b-1), such as the composition from hydroxy styrenes or hydroxy styrenes derivative can be enumerated Component units in unit, novolak type phenol resin.

As Component units (b-1), from the viewpoint of the deformation for inhibiting pattern form, the composition that is preferably indicated with formula B1 Unit B 1.Component units B1 possessed by polymer A or polymer B can be a kind, or two or more.

[chemical formula 11]

As R⁷¹Divalent linking group, ester bond (- COO-), alkylidene that carbon atom is bonded with main chain can be enumerated.Make For alkylidene, the preferably alkylidene of the carbon atom number 1~6 with linear chain or branched chain.R⁷¹Preferably singly-bound, ester bond, more preferably Singly-bound.The linking group of divalent can have substituent group, as substituent group, can enumerate halogen atom, hydroxyl, alkoxy etc..

A indicates 1~5 integer, and from the viewpoint of easy to manufacture, a is preferably 1 or 2, more preferably 1.About in phenyl ring Hydroxyl bonding position, will be with R⁷¹When the carbon atom of bonding is set as benchmark (1), preferably it is bonded at 4.

R⁷²Halogen atom or alkyl are indicated, as alkyl, the preferably alkyl with linear chain or branched chain of carbon atom number 1~4. R⁷²From the viewpoint of easy to manufacture, preferably chlorine atom, bromine atom, methyl or ethyl.

B indicates 0~4 integer, and from the viewpoint of easy to manufacture, b is preferably 0 or 1, more preferably 0.

As the preferred concrete example of the Component units B1 indicated with formula B1, the structure from m- hydroxy styrenes can be enumerated At unit, from the Component units of p- hydroxy styrenes.That is, can enumerate polymer A or polymer B as preference has From the Component units in m- hydroxy styrenes and the form from least one of the Component units of p- hydroxy styrenes. As the preference of polymer B, poly- (m- hydroxy styrenes), poly- (p- hydroxy styrenes), poly- (m-/p- mixing hydroxyl can be enumerated Styrene).

As Component units (b-1), can also enumerate made of phenolic and the formaldehyde condensation polymer in novolak type phenol resin Component units.As phenolic, preferably phenolic aldehyde, m- cresols, p- cresols.That is, polymer B is such as phenolic aldehyde formaldehyde resin, m- Cresol formaldehyde resin, p- cresol formaldehyde resin, m-/p- cresols formaldehyde resin, phenolic aldehyde/cresols (can be m-, p- or m-/ Any of p- mixing) mix the novolak type phenol resins such as formaldehyde resin.

Component units (b-2)-with alcohol hydroxyl group

It is preferably indicated as Component units (b-2) from the viewpoint of the deformation for inhibiting pattern form with following formula B2 Component units B2.Component units B2 possessed by polymer A or polymer B can be a kind, or two or more.

[chemical formula 12]

R⁸¹Indicate singly-bound or arlydene, preferably singly-bound.As arlydene, preferably phenylene, arlydene, which can have, to be taken Dai Ji.

R⁸²Indicate that alkylidene, the preferably alkylidene with linear chain or branched chain of carbon atom number 1~6, more preferably carbon are former The alkylidene with linear chain or branched chain of subnumber 2~4.

As the preferred concrete example of the Component units B2 indicated with formula B2, the carbon atom number from alkylidene can be enumerated For the Component units of (methyl) acrylic acid hydroxy alkyl ester of 1~6 (preferably 2~4).Carbon atom number as alkylidene is 1~6 (methyl) acrylic acid hydroxy alkyl ester of (preferably 2~4) can enumerate (methyl) acrylic acid 2- hydroxyl ethyl ester, (methyl) acrylic acid 2- Hydroxypropyl acrylate, (methyl) acrylic acid 2- hydroxyl -1- methylhexyl, (methyl) acrylic acid 3- hydroxypropyl acrylate, (methyl) acrylic acid 2- hydroxyl fourth Ester, (methyl) acrylic acid 3- hydroxy butyl ester, (methyl) acrylic acid 4- hydroxy butyl ester etc..

Other Component units-

When polymer A and polymer B are addition polymer, from the viewpoint of resolution ratio and adaptation, preferably In polymeric composition comprising in (methyl) acrylic acid and (methyl) alkyl acrylate at least any one.Therefore, polymer Ingredient preferably has the Component units from (methyl) acrylic acid and the composition list from (methyl) alkyl acrylate In member at least any one.As (methyl) alkyl acrylate, it is however preferred to have (more preferably carbon is former for carbon atom number 4~12 Subnumber 4~8) straight chain, branched or cyclic alkyl (methyl) alkyl acrylate, more preferably have carbon atom number 4~ (methyl) alkyl acrylate of the cyclic alkyl of 12 (more preferably carbon atom numbers 4~8), further preferably (methyl) propylene Sour cyclohexyl.

By adjusting the type and content of above-mentioned Component units, the various characteristics of component of polymer can be adjusted, such as Glass transition temperature can be adjusted to 90 DEG C or less.

It shared Component units from (methyl) acrylic acid and is come from total Component units of component of polymer In the total ratio of the Component units of (methyl) alkyl acrylate be preferably 10 moles of % or more and 90 mole of % hereinafter, more excellent 20 moles of % or more and 70 mole of % are selected as hereinafter, further preferably 30 moles of % or more and 50 mole of % or less.

Component of polymer preferably comprises the Component units from (methyl) alkyl acrylate with cyclic alkyl, more Preferably comprise (methyl) acrylic acid from the cyclic alkyl with carbon atom number 4~12 (more preferably carbon atom number 4~8) The Component units of Arrcostab further preferably have the Component units from (methyl) acrylate base.It is preferred that above-mentioned structure It is included in component of polymer at unit as polymer A or the Component units of polymer B.

The ratio of shared above-mentioned Component units is preferably 10 moles of % or more in total Component units of component of polymer And 70 moles of % hereinafter, more preferably 20 moles of % or more and 60 mole of % hereinafter, further preferably 30 moles of % or more and 50 moles of % or less.

Component of polymer can further have from phenylethylene, (methyl) benzyl acrylate, unsaturated dicarboxylic Diester, bicyclic unsaturated compound, maleimide compound, unsaturated aromatic compound, conjugated diene based compound etc. The Component units of unsaturated compound.

Other Component units constitute the other polymers of any of simultaneously non-polymer A and polymer B, other polymerizations Object may be included in component of polymer.Wherein, the mass ratio of other polymers shared in component of polymer is preferably 20 matter Measure % hereinafter, more preferably 10 mass % hereinafter, more preferably 5 mass % hereinafter, not including substantially further preferably.

The various characteristics-of component of polymer

The acid value of component of polymer is preferably 60mgKOH/g or less.It is 60mgKOH/g hereinafter, photonasty tree by acid value Oil/fat composition layer has high adhesion, and transferability is more excellent.Acid value is more preferably 40mgKOH/g hereinafter, further preferably 20mgKOH/g or less.The lower limit value of acid value is preferably 0mgKOH/g or more, more preferably 5mgKOH/g or more, further preferably For 10mgKOH/g or more.

The acid value of component of polymer is the acid value for measuring each polymer contained in component of polymer, and with each polymer The average value (being weighted and averaged) that mass percent is weighted.Wherein, when can not will contained in component of polymer it is each poly- When conjunction object is according to type separated or when the polymer contained in component of polymer is a kind, from component of polymer totality It obtains sample and measures acid value to find out.

The acid value of polymer is measured according to JIS K0070 (1992) by neutralization titration.

The acid value of component of polymer can be single by adjusting Component units (b-1), Component units (b-2) and other compositions The type and content of member control in the preferred scope described.

The glass transition temperature (Tg) of component of polymer is preferably 90 DEG C or less.It is 90 DEG C hereinafter, photonasty by Tg Resin composition layer has high adhesion, and transferability is more excellent.Tg be more preferably 60 DEG C hereinafter, further preferably 40 DEG C with Under.The lower limit value of Tg is not particularly limited, preferably -20 DEG C or more, more preferably 0 DEG C or more, further preferably 20 DEG C More than.It is -20 DEG C or more by Tg, good patternability can be kept, and when using cover film, can inhibit removing and cover The decline of fissility when epiphragma.

The glass transition temperature of component of polymer is totally to obtain sample from component of polymer and measure glass transition Temperature is found out.When having distinguished each polymer contained in component of polymer, the glass transition temperature of each polymer can be measured Degree, and find out as the value that the following formula that is weighted by the mass percent with each polymer calculates.

[numerical expression 1]

Tg is the glass transition temperature (absolute temperature) of component of polymer, and rn is the mass percent of polymer n, Tgn It is the glass transition temperature (absolute temperature) of polymer n.

The glass transition temperature of component of polymer or each polymer is measured using differential scanning calorimetry (DSC). It is carried out on the basis of the method that specific measuring method is recorded in JIS K7121 (1987).Vitrifying in this specification Transition temperature is extrapolation glass transition initial temperature (Extrapolated Glass Transition Onset Temperature, hereinafter sometimes referred to as Tig.).

The measuring method of glass transition temperature is specifically described.

When seeking glass transition temperature, after being kept until device is stablized with low about 50 DEG C of the temperature of the Tg than anticipation, with Until 20 DEG C/min of heating speed are heated to high about 30 DEG C of the temperature of the temperature terminated than Glass Transition, and draw and show differential thermal Analyze (differential thermal analysis:DTA) curve or differential scanning calorimetry (differential Scanning calorimetry:DSC) curve.Glass transition initial temperature (Tig) is extrapolated as DTA curve or DSC curve In the reference line of low temperature side extend to the straight line of high temperature side and the slope of a curve in the change in ladder shape part of Glass Transition The temperature of intersection point as the tangent line drawn on maximum point and find out.

As the method by the Tg control of component of polymer at the preferred scope described, such as can enumerate according to polymer The mass ratio of the Tg of the homopolymer of each Component units and each Component units possessed by ingredient carry out FOX formula as guidance The method of control.

About FOX formula

The Tg of the homopolymer of 1st Component units is set as Tg1, by the quality in the component of polymer of the 1st Component units point Rate is set as W1, and the Tg of the homopolymer of the 2nd Component units is set as Tg2, by the quality in the component of polymer of the 2nd Component units point When rate is set as W2, the Tg0 (K) of component of polymer can be inferred according to following FOX formula.

FOX formula: 1/Tg0=(W1/Tg1)+(W2/Tg2)

In addition, can also adjust the Tg of component of polymer by adjusting the weight average molecular weight of component of polymer.

In component of polymer, the molecular weight as ingredient totality is the weight average molecular weight (Mw) to be converted with polystyrene, excellent It is selected as 60,000 or less.Mw by component of polymer is 60,000 hereinafter, by the melt viscosity of photosensitive polymer combination layer It is suppressed to lower, can be realized the fitting under low temperature (such as 130 DEG C or less) when being bonded with substrate.The Mw of component of polymer is excellent It is selected as 2,000~60,000, more preferably 3,000~50,000.

The ratio between number average molecular weight and weight average molecular weight of component of polymer (dispersion degree) are preferably 1.0~5.0, more excellent It is selected as 1.05~3.5.

The Mw of component of polymer can be measured by GPC (gel permeation chromatography), as measurement device, be able to use each The commercially available device of kind, the detailed content and determination techniques of device are well known to those skilled in the art.It is seeped about based on gel The measurement of the Mw of saturating chromatography (GPC) is able to use HLC (registered trademark) -8220GPC (TOSOH as measurement device CORPORATION system), as tubing string, it is able to use 1 TSKgel (registered trademark) Super HZM-M of series connection respectively (4.6mmID × 15cm, TOSOH CORPORATION system), Super HZ4000 (4.6mmID × 15cm, TOSOH CORPORATION system), Super HZ3000 (4.6mmID × 15cm, TOSOH CORPORATION system), Super HZ2000 The tubing string of (4.6mmID × 15cm, TOSOH CORPORATION system) is able to use THF (tetrahydrofuran) as eluent.Make For determination condition, sample solution concentration is set as 0.2 mass %, flow velocity is set as 0.35ml/min, the amount of injecting a sample into is set as 10 μ L And measuring temperature is set as 40 DEG C, and be able to use differential refractive index (RI) detector to carry out.Calibration curve is able to use TOSOH CORPORATION system " standard sample TSK standard, polystyrene ": " F-40 ", " F-20 ", " F-4 ", " F- 1 ", any of this 7 samples of " A-5000 ", " A-2500 " and " A-1000 " make.

The manufacturing method (synthetic method) of each polymer contained in component of polymer is not particularly limited, as an example, energy It is enough to carry out polymerization using polymerization initiator in the organic solvent comprising polymerizable monomer to be synthesized.Also, also can It is enough to be synthesized with so-called high molecular weight reactive.Each polymer contained in component of polymer is also possible to commercially available product.

Photosensitive polymer combination layer is from the viewpoint of showing good adaptation relative to substrate, relative to photonasty The gross mass of resin composition layer preferably includes component of polymer with the ratio of 50 mass of mass %~99.9 %, more preferably with 70 The ratio of the mass of quality %~98 % includes.

In the 1st embodiment, show the viewpoint of good adaptation relative to substrate from photosensitive polymer combination layer Considering, the amount of polymer A-I is preferably the 50 mass % of mass %~99.9 relative to the gross mass of photosensitive polymer combination layer, More preferably 70 mass of mass %~98 %.

In the 2nd embodiment, show the viewpoint of good adaptation relative to substrate from photosensitive polymer combination layer Consider, the amount of polymer A-II is preferably 50 matter of mass %~99.9 relative to the gross mass of photosensitive polymer combination layer Measure %, more preferably 70 mass of mass %~98 %.

In the 3rd embodiment, show the viewpoint of good adaptation relative to substrate from photosensitive polymer combination layer Consider, the total amount of polymer A-III and polymer B-I are preferably 50 matter relative to the gross mass of photosensitive polymer combination layer Measure the mass % of %~99.9, more preferably 70 mass of mass %~98 %.

In the 4th embodiment, show the viewpoint of good adaptation relative to substrate from photosensitive polymer combination layer Consider, the total amount of polymer A-III and polymer B-II are preferably 50 relative to the gross mass of photosensitive polymer combination layer The mass % of quality %~99.9, more preferably 70 mass of mass %~98 %.

In the 5th embodiment, show the viewpoint of good adaptation relative to substrate from photosensitive polymer combination layer Consider, the total amount of polymer A-IV and polymer B-II are preferably 50 matter relative to the gross mass of photosensitive polymer combination layer Measure the mass % of %~99.9, more preferably 70 mass of mass %~98 %.

Photoacid generator-

Photosensitive polymer combination layer contains photoacid generator.As the photoacid generator being used in the present invention, energy can be enumerated Enough compounds that acid is generated by actinic rays such as irradiation ultraviolet light, far ultraviolet, X-ray and charged particle beams.

As photoacid generator as used in the present invention, preferably with wavelength 300nm or more, preferably incude wavelength 300nm The actinic ray of~450nm and the compound for generating acid, but its chemical structure is unrestricted.Also, about not incuding directly Photoactinic photoacid generator of wavelength 300nm or more, if by with sensitizer simultaneously using incuding wavelength 300nm or more Actinic ray and generate acid, then can be combined with sensitizer and it is preferable to use.

It is more excellent as the photoacid generator that photoacid generator as used in the present invention, preferably generation pKa are 4 acid below Choosing generates the photoacid generator that pKa is 3 acid below, particularly preferably generates the photoacid generator that pKa is 2 acid below.The lower limit of pKa It is worth and not specially provided, but is for example preferably -10.0 or more.

As photoacid generator, ionic photoacid generator and nonionic photoacid generator can be enumerated.

Also, from the viewpoint of sensitivity and resolution ratio, as photoacid generator, preferably comprise selected from by being described below Salt compound and be described below oxime sulfonate compounds composition group at least one kind of compound, more preferably include oxime Sulfonate compound.

As the example of nonionic photoacid generator, it is sub- that trichloromethyl s-triazine, diazomethane compound, acyl can be enumerated Amine sulfonate compound and oxime sulfonate compounds etc..Among these, from the viewpoint of sensitivity, resolution ratio and adaptation, It is preferred that photoacid generator is oxime sulfonate compounds.These photoacid generators can be used alone a kind or combine two or more and use. As trichloromethyl s-triazine and the concrete example of diazomethane derivative, Japanese Unexamined Patent Publication 2011-221494 can be illustrated in The compound recorded in 0083 section of bulletin~0088 section.

It is the compound with oxime sulfonates structure as oxime sulfonate compounds, preferably comprises the oxime indicated with following formula The compound of sulfonate structure.

[chemical formula 13]

In above-mentioned formula, R²¹Indicate alkyl or aryl, * indicates to be bonded position with other atoms or other groups.

Compound containing the oxime sulfonates structure indicated with above-mentioned formula can also be substituted by any group, R²¹In alkyl It can be straight chain, or branched structure can also have ring structure.The substituent group of permission is illustrated below.

As R²¹Alkyl, the preferred straight or branched alkyl of carbon atom number 1~10.R²¹Alkyl can by carbon original The aryl of subnumber 6~11, the alkoxy of carbon atom number 1~10, naphthenic base (include the bridges such as 7,7- dimethyl -2- oxygen norborny Connect formula alcyl, preferably bicyclic alkyl etc.) or halogen atom substitution.

As R²¹Aryl, the preferred aryl of carbon atom number 6~18, more preferable phenyl or naphthyl.R²¹Aryl can be by 1 or more the group selected from the group being made of the alkyl, alkoxy and halogen atom of carbon atom number 1~4 replaces.

Compound containing the oxime sulfonates structure indicated with above-mentioned formula is it is also preferred that in Japanese Unexamined Patent Publication 2014-085643 public affairs The oxime sulfonate compounds recorded in 0078~0111 section of report.

As the example of ionic photoacid generator, Diaryl iodonium salt and triaryl sulfonium salts compounds can be enumerated Equal salt compounds, quaternary ammonium salt etc..Among this is equal, preferably salt compound, especially preferably triaryl sulfonium salts class And Diaryl iodonium salt.

As ionic photoacid generator, can also be preferably used in Japanese Unexamined Patent Publication 2014-085643 bulletin 0114~ The ionic photoacid generator recorded in 0133 section.

Photoacid generator can be used alone a kind, also can be used simultaneously two or more.

The content of photoacid generator in photosensitive polymer combination layer from the viewpoint of sensitivity, resolution ratio, relative to The gross mass of photosensitive polymer combination layer is preferably the 0.1 mass % of mass %~10, more preferably 0.5 matter of mass %~5 Measure %.

Solvent-

Photosensitive polymer combination layer may include solvent.

The photosensitive polymer combination of photosensitive polymer combination layer is formed in order to be readily formed photosensitive resin composition Nitride layer first adjusts the viscosity of photosensitive polymer combination containing solvent, then will wrap solvent-laden photosensitive polymer combination into Row coating and drying, can be preferably formed as photosensitive polymer combination layer whereby.

As for solvent of the invention, it is able to use well known solvent.As solvent, glycol monoalkyl can be illustrated Ethers, glycol dialkyl ether class, ethylene glycol monoalkyl ether acetate class, propylene-glycol monoalky lether class, propylene glycol dialkyl ether Class, propylene-glycol monoalky lether acetate esters, diethylene glycol dialkyl ether class, diethylene glycol monoalkyl ether acetate class, dipropyl two Alcohol monoalkyl ethers, dipropylene glycol dialkyl ether, dipropylene glycol monoalkylether acetate esters, esters, ketone, amides and interior Esters etc..Also, as the concrete example of solvent, can also enumerate 0174 section of Japanese Unexamined Patent Publication 2011-221494 bulletin~ The solvent recorded in 0178 section, these contents are incorporated into this specification.Solvent can be used only a kind, it is possible to use two or more.

Benzylisoeugenol, hexyl ether, ethylene glycol list phenyl ether acetic acid can further be added in a solvent as needed Ester, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, octanoic acid, 1- octanol, 1 nonyl alcohol, benzyl alcohol, Methyl phenyl ethers anisole, benzyl acetate, ethyl benzoate, diethy-aceto oxalate, diethyl maleate, ethylene carbonate or propylene carbonate etc. are molten Agent.

Can be used in solvent of the invention can be used alone, and more preferably use 2 kinds simultaneously.Using of more than two kinds molten In the case where agent, for example, preferred propylene-glycol monoalky lether acetate esters and dialkyl ether while use, oxalic acid esters with It is used while diethylene glycol dialkyl ether class or esters and butanediol alkylether acetates class while uses.

As solvent, the solvent of preferably 130 DEG C of boiling point 160 DEG C of solvent, the boiling points more than and less than 160 DEG C or more or it Mixture.As 130 DEG C of the boiling point solvents more than and less than 160 DEG C, propylene glycol monomethyl ether (boiling can be illustrated 146 DEG C of point), propylene glycol monoethyl ether acetate (158 DEG C of boiling point), propylene glycol methyl n-butyl ether (155 DEG C of boiling point) and propylene glycol Methyl n-propyl ether (131 DEG C of boiling point).As 160 DEG C of boiling point or more of solvent, 3- ethoxyl ethyl propionate (boiling point can be illustrated 170 DEG C), diethylene glycol methyl ethyl ether (176 DEG C of boiling point), propylene glycol monomethyl ether propionic ester (160 DEG C of boiling point), dipropylene glycol Methylether acetate (213 DEG C of boiling point), 3- methoxybutyl ether acetic acid ester (171 DEG C of boiling point), diethylene glycol diethyl ether (boiling point 189 DEG C), diethylene glycol dimethyl ether (162 DEG C of boiling point), propylene-glycol diacetate (190 DEG C of boiling point), diethylene glycol monoethyl ether second Acid esters (220 DEG C of boiling point), dipropylene glycol dimethyl ether (175 DEG C of boiling point) and 1,3 butylene glycol diacetate esters (232 DEG C of boiling point).

The content of solvent when as photosensitive resin coating composition, the total solid content in photosensitive polymer combination Every 100 mass parts be preferably 50 mass parts~1,900 mass parts, more preferably 100 mass parts~900 mass parts.

The content of solvent in photosensitive polymer combination layer is preferred relative to the gross mass of photosensitive polymer combination layer For 2 mass % hereinafter, more preferably 1 mass % is hereinafter, further preferably 0.5 mass % or less.

Other additives-

It, being capable of basis in photosensitive polymer combination layer in the present invention other than component of polymer and photoacid generator It needs comprising well known additive.

Plasticizer-

Photosensitive polymer combination layer can contain plasticizer for the purpose of improving plasticity.

The weight average molecular weight of plasticizer is preferably smaller than the polymer for constituting component of polymer.It is examined from the viewpoint for assigning plasticity Consider, the weight average molecular weight of plasticizer preferably 500 more than and less than 10,000, more preferable 700 more than and less than 5,000, further It is preferred that 800 more than and less than 4,000.

As long as plasticizer is the compound that plasticity is mixed and shown with component of polymer, be not particularly limited but from From the viewpoint of assigning plasticity, plasticizer preferably has alkylidene oxygroup in the molecule.It is contained in the alkylene oxide of plasticizer Base preferably has following structures.

[chemical formula 14]

In above-mentioned formula, R is the alkylidene of carbon atom number 2~8, and n indicates that 1~50 integer, * indicate and other atoms It is bonded position.

For example, (" compound X " can be set as the compound of the alkylidene oxygroup with above structure.), mix chemical combination Chemically amplified positive photosensitive polymer combination obtained from object X, component of polymer and photoacid generator with do not include compound X and The chemically amplified positive photosensitive polymer combination of formation does not meet the increasing in the present invention compared in the case where not improving plasticity Mould agent.For example, the surfactant arbitrarily added is not made with that can bring the amount of plasticity to photosensitive polymer combination usually With, therefore do not meet the plasticizer in this specification.

As plasticizer, such as the compound with following structures can be enumerated, but be not limited among the grade.

[chemical formula 15]

From the viewpoint of adaptation, the gross mass relative to photosensitive polymer combination layer is preferably the content of plasticizer The 1 mass % of mass %~50, more preferably 2 mass of mass %~20 %.Photosensitive polymer combination layer can be only comprising a kind of increasing Agent is moulded, also may include two or more.

Sensitizer-

Photosensitive polymer combination layer can also include sensitizer.

Sensitizer absorbs actinic ray and becomes electron excitation state.Sensitizer and light as electron excitation state produce acid Agent contact, and generate the effects of electronics is mobile, energy is mobile and fever.Thus photoacid generator causes chemical change and decomposes, from And generate acid.

By containing sensitizer, exposure sensitivity can be improved.

As sensitizer, be preferably selected from by anthracene derivant, acridone derivatives, thioxanthone derivates, coumarin derivative, The compound of the group of basicity styrene derivative and talan benzene derivative composition, more preferable anthracene derivant.

As anthracene derivant, preferably anthracene, 9,10- dibutoxy anthracene, 9,10-, bis- chrloroanthracene, 2- ethyl -9,10- dimethoxy Anthracene, 9- hydroxymethyl anthracene, 9- bromine anthracene, 9- chrloroanthracene, 9,10- dibromoanthracene, 2- ethyl anthracene or 9,10- dimethoxy anthracene.

As sensitizer, it can enumerate and record in 0139 section~0141 section of International Publication No. 2015/093271 Compound.

The content of sensitizer is preferably the 0 mass % of mass %~10 relative to the gross mass of photosensitive polymer combination layer, More preferably 0.1 mass of mass %~10 %.

Alkali compounds-

Photosensitive polymer combination layer preferably also includes alkali compounds.

As alkali compounds, it arbitrarily can chemically amplify and select and make in alkali compounds used in resist With.Such as aliphatic amine, aromatic amine, hetero ring type amine, quaternary ammonium hydroxide and the quaternary ammonium salt of carboxylic acid can be enumerated etc..As these Concrete example can enumerate the compound recorded in 0204 section~0207 section of Japanese Unexamined Patent Publication 2011-221494 bulletin, in these Appearance is incorporated into this specification.

Specifically, as aliphatic amine, such as Trimethylamine, diethylamide, triethylamine, diη-propyl can be enumerated Amine, three n-propyl amine, two n-pentyl amine, three n-pentyl amine, diethanol amine, triethanolamine, dicyclohexylamine and dicyclohexyl first Base amine etc..

As aromatic amine, such as aniline, benzyl amine, n,N-Dimethylaniline and diphenylamine can be enumerated etc..

As hetero ring type amine, such as pyridine, 2- picoline, 4- picoline, 2- ethylpyridine, 4- ethyl pyrrole can be enumerated Pyridine, 2- phenylpyridine, 4- phenylpyridine, N- methyl 4-phenyl pyridine, 4-dimethylaminopyridine, imidazoles, benzimidazole, 4- Methylimidazole, 2-Phenylbenzimidazole, 2,4,5- triphenylimidazolyl, nicotine, niacin, niacin amide, quinoline, 8- oxygen quinoline Quinoline, pyrazine, pyrazoles, pyridazine, purine, pyrrolidines, piperidines, piperazine, morpholine, 4- methyl morpholine, 1,5- diazabicyclo [4.3.0] -5- nonene and 1,8- diazabicyclo [5.3.0] -7- endecatylene etc..

As quaternary ammonium hydroxide, such as tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetra-n-butyl hydrogen-oxygen can be enumerated Change ammonium and four positive hexyloxy ammonium hydroxide etc..

As the quaternary ammonium salt of carboxylic acid, such as tetramethyl ammonium acetate, durol ammonium formate, acetic acid tetra-n-butyl ammonium can be enumerated And benzoic acid tetra-n-butyl ammonium etc..

Alkali compounds can be used alone a kind, can also use two or more simultaneously.The content of alkali compounds relative to The gross mass of photosensitive polymer combination layer is preferably the 0.001 mass % of mass %~5, more preferably 0.005 matter of mass %~3 Measure %.

Miscellaneous cyclic compound-

Photosensitive polymer combination layer in the present invention can include miscellaneous cyclic compound.

Miscellaneous cyclic compound in the present invention is not particularly limited.Such as it can be added in intramolecular as described below Compound with epoxy group or oxetanylmethoxy, the miscellaneous cyclic compound containing alkoxy methyl, other various cyclic ethers, ring-type Ester (lactone) etc. is further able to addition with silicon, sulphur, phosphine etc. containing acid plain monomer, cyclic amine, this nitrogen containing monomer of oxazoline group The monomer containing heteroatomic ring etc. of d electronics.

When adding miscellaneous cyclic compound, the additive amount of the miscellaneous cyclic compound in photosensitive polymer combination layer relative to The gross mass of photosensitive polymer combination layer is preferably the 0.01 mass % of mass %~50, more preferably 0.1 matter of mass %~10 Measure %, further preferably 1 mass of mass %~5 %.From the viewpoint of adaptation and etching patience, preferably above-mentioned model It encloses.Miscellaneous cyclic compound can be used only a kind, can also use two or more simultaneously.

As the concrete example of the compound in the molecule with epoxy group, bisphenol A type epoxy resin, Bisphenol F can be enumerated Type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, aliphatic epoxy resin etc..

It can be obtained as commercially available product as the compound in the molecule with epoxy group.For example, JER can be enumerated⁸²8、 JER1007, JER157S70 (Mitsubishi Chemical Corporation. system), JER157S65 (Mitsubishi Chemical Holdings Co., Ltd. system) etc., record in the 0189 of Japanese Unexamined Patent Publication 2011-221494 bulletin it is commercially available Product etc..

As other commercially available products, ADEKA RESIN EP-4000S, ADEKA RESIN EP-4003S, ADEK A RESIN EP-4010S, ADEKA RESIN EP-4011S (more than, ADEKA CORPORATION system), NC-2000, NC-3000, NC- 7300, XD-1000, EPPN-501, EPPN-502 (more than, ADEKA CORPORATION system), Denacol EX-611, EX- 612、EX-614、EX-614B、EX-622、EX-512、EX-521、EX-411、EX-421、EX-313、EX-314、EX-321、 EX-211、EX-212、EX-810、EX-811、EX-850、EX-851、EX-821、EX-830、EX-832、EX-841、EX-911、 EX-941、EX-920、EX-931、EX-212L、EX-214L、EX-216L、EX-321L、EX-850L、DLC-201、DLC-203、 DLC-204、DLC-205、DLC-206、DLC-301、DLC-402、EX-111、EX-121、EX-141、EX-145、EX-146、 EX-147, EX-171, EX-192 (the above Nagase Chemtex Corporation system), YH-300, YH-301, YH-302, YH-315, YH-324, YH-325 (more than, Nippon Steel Sumikin Kagaku Co., Ltd. system) CELLOXIDE 2021P、2081、2000、3000、EHPE3150、EPL GT400、CELVENUS B0134、B0177(DAICEL CORPORATION system) etc..

The compound with epoxy group can be used alone in the molecule, can also use two or more simultaneously.

In the molecule in the compound with epoxy group, bisphenol A type epoxy resin, bisphenol F type epoxy tree are more preferably enumerated Rouge, phenol novolak type epoxy resin and aliphatic epoxy resin, particularly preferably enumerate aliphatic epoxy resin.

As the concrete example of the compound in the molecule with oxa- ring group butyl, it is able to use Aron Oxetane OXT-201, OXT-211, OXT-212, OXT-213, OXT-121, OXT-221, OX-SQ, PNOX (more than, TOAGOSEI CO., LTD. it makes).

Also, the compound of packet oxygen-containing heterocycle butyl be preferably used alone or mixed with the compound with epoxy group and It uses.

From the viewpoint of etching patience and line width stability, in photosensitive polymer combination layer in the present invention, Miscellaneous cyclic compound is preferably the compound with epoxy group.

Alkoxysilane compound containing trialkylsilyl group in molecular structure-

Photosensitive polymer combination layer can contain alkoxysilane compound containing trialkylsilyl group in molecular structure.As alkoxysilane compound containing trialkylsilyl group in molecular structure, preferably lift Trialkoxy silane compound out.

As alkoxysilane compound containing trialkylsilyl group in molecular structure, such as gamma-amino propyl trimethoxy silicane, gamma-amino propyl three can be enumerated Ethoxysilane, γ-glycidoxypropyl group trialkoxy silane, γ-glycidoxypropyl alkyl-dialkoxysilanes, γ-methacryloxypropyl trialkoxy silane, γ-methacryloxypropyl alkyl-dialkoxysilanes, γ-chlorine Propyl trialkoxy silane, γ-mercaptopropyi trialkoxy silane, β-(3,4- epoxycyclohexyl) ethyltrialkoxysilanes, Ethylene trialkoxy silane.Among these, more preferable γ-glycidyloxypropyl silane or γ-metering system Propyl trialkoxy silane, further preferred γ-glycidyloxypropyl silane, particularly preferred 3- contracting Water glycerol oxygroup propyl trimethoxy silicane.These can be used alone a kind or combine two or more and use.

Surfactant-

From the viewpoint of film thickness uniformity, photosensitive polymer combination layer preferably comprises surfactant.As surface Activating agent is able to use any of anionic system, cationic system, nonionic system (nonionic) or both sexes, it is preferred that Surfactant be nonionic surfactant.

As the example of nonionic surfactants, polyoxyethylene higher alkyl ether, polyoxyethylene higher can be enumerated Higher aliphatic acid diesters class, the silicone-based, fluorine system surfactant of alkyl phenyl ethers, polyoxyethylene glycol.Also, by following quotient The name of an article can enumerate KP (Shin-Etsu Chemical Co., Ltd. system), Polyflow (Kyoeisha chemical Co., Ltd.'s system), Eftop (Jemco Inc. system), MAGAFAC (registered trademark, DIC CORPORATION system), Fluorad (Sumitomo 3M Limited system), AsahiGuard, Surflon (registered trademark, ASAHI GLASS CO., LTD. system), PolyFox (OMNOVA Solutions Inc. society system) and SH-8400 (Dow Corning Toray Co., Ltd. system) etc. are each Series.

Also, it as surfactant, can enumerate as preferred example with the Component units indicated with following Formulas I -1 (I-a) and Component units (I-b) the polyphenyl second of gel permeation chromatography measurement when, and by by tetrahydrofuran (THF) as solvent The weight average molecular weight (Mw) of alkene conversion is 1,000 or more and 10,000 copolymers below.

[chemical formula 16]

In Formulas I -1, R⁴⁰¹And R⁴⁰³Separately indicate hydrogen atom or methyl, R⁴⁰²Indicate carbon atom number 1 or more and 4 with Under straight-chain alkyl-sub, R⁴⁰⁴Indicate hydrogen atom or the alkyl below of carbon atom number 1 or more and 4, L indicate 3 or more carbon atom number and 6 alkylidenes below, p and q are the mass percent for indicating to be overlapped ratio, and p indicates 10 mass % or more and 80 mass % are below Numerical value, q indicate 20 mass % or more and 90 mass % numerical value below, and r indicates 1 or more and 18 integers below, s indicate 1 with Upper and 10 integers below, * expression are bonded position with other Component units.

The sum of p and q (p+q) are preferably p+q=100 i.e. 100 mass %.

L is preferably the branched alkylidene indicated with following formula (I-2).R in formula (I-2)⁴⁰⁵Indicate 1 or more carbon atom number And 4 alkyl below, from intermiscibility and relative to the wetability in face is applied from the viewpoint of, preferred carbon atom number 1 or more and 3 Alkyl below, the alkyl of more preferable carbon atom number 2 or 3.

[chemical formula 17]

The weight average molecular weight (Mw) of above-mentioned copolymer is more preferably 1,500 or more and 5,000 or less.

It is further possible to use the 0017 of No. 4502784 bulletins of Japanese Patent No., Japanese Unexamined Patent Publication 2009-237362 public affairs The surfactant recorded in 0060 section~0071 section of report.

Surfactant can be used alone a kind, can also use two or more simultaneously.

The additive amount of surfactant relative to the gross mass of photosensitive polymer combination layer be preferably 10 mass % hereinafter, The more preferably 0.001 mass % of mass %~10, further preferably 0.01 mass of mass %~3 %.

Other compositions-

Metal oxide particle, antioxidant, dispersion can also be added in photosensitive polymer combination layer in the present invention Agent, acid proliferation generator, development accelerant, conducting fibre, colorant, hot radical polymerization initiator, thermal acid generator, ultraviolet light are inhaled Receive additive well known to antisettling agent of agent, thickener, crosslinking agent and organic or inorganic etc..

About the preferred state of other compositions, respectively 0165 section of Japanese Unexamined Patent Publication 2014-085643 bulletin~ On the books in 0184 section, the content of the bulletin is incorporated into this specification.

The forming method-of photosensitive polymer combination layer

Each ingredient and solvent can be mixed with arbitrary proportion and with any means, and carry out stirring and dissolving to make It is ready for use on the photosensitive polymer combination to form photosensitive polymer combination layer.For example, also can be molten in advance respectively by each ingredient After solution is made in solvent in solution, obtained solution is mixed at a specific ratio to prepare composition.As above system Standby composition be provided in after capable of being also filtered with 0.2 μm of the filter etc. in aperture using.

By the way that photosensitive polymer combination to be coated in temporary support and make it dry, can obtain in temporary support With the photosensitive transfer printing material of photosensitive polymer combination layer on body.The coating method of photosensitive polymer combination is not special Limitation, can be coated in method well known to slot coated, spin coating, curtain painting, ink-jet application etc..It can also be in temporary support After other layers that upper formation describes below, photosensitive resin coating composition layer on it.

[other layers]

Photosensitive transfer printing material of the invention can have the layer other than photosensitive polymer combination layer (sometimes referred to as " other layers ".).As other layers, thermoplastic resin layer, contrast enhancing layer, middle layer, cover film etc. can be enumerated.

Photosensitive transfer printing material of the invention, can be in temporary support and photoresist from the viewpoint of transferability There is thermoplastic resin layer between composition layer.Preferred embodiment about thermoplastic resin layer is in Japanese Unexamined Patent Publication 2014- On the books in 0189 section of No. 085643 bulletin~0193 section, the content of the bulletin is incorporated into this manual.When of the invention It, can be in accordance in Japanese Unexamined Patent Publication 2006-259138 public affairs when photosensitive transfer printing material has other layer of thermoplastic resin layer etc. The production method of photosensitive transfer printing material recorded in 0094~0098 section of report makes.

Photosensitive transfer printing material of the invention is other than above-mentioned photosensitive polymer combination layer, additionally it is possible to have contrast Enhancement layer.Contrast enhancing layer (Contrast Enhancement Layer；CEL) before exposure to the absorption of exposure wavelength Greatly, but with being exposed it absorbs and gradually becomes smaller, be material (sometimes referred to as " the light achromicity that the transmitance containing light is got higher Pigment composition ".) layer.As light achromicity pigment composition, it is known to diazonium salt, stibazole (stilbazolium) salt, arylnitroso salt etc..As overlay film forming component, phenol resin etc. is used.In addition, as right Than degree enhancement layer, it is able to use 0004 section~0051 section, Japanese Unexamined Patent Publication 6- in Japanese Unexamined Patent Publication 6-097065 bulletin 0012 section of No. 332167 bulletins~0055 section, " photopolymer handbook " (photopolymerization forum volume, census of manufacturing meeting, 1989 Year), " light polymerization technique (Technology) " (hummock-Yong Song compile, THE NIKKAN KOGYO SHIMBUN, LTD., 1988 Year) in record material.

Photosensitive transfer printing material of the invention can have middle layer on photosensitive polymer combination layer, and in middle layer It is upper that there is CEL.Middle layer in order to prevent the mixing of CEL and positive type photosensitive organic compound layer and be arranged.

Photosensitive transfer printing material of the invention can have cover film for the purpose of protecting photosensitive polymer combination layer.

The manufacturing method > of < wiring

As long as the manufacturing method of wiring of the invention has used the manufacturer of photosensitive transfer printing material of the invention Rule is not particularly limited, and is preferably successively included following process: for substrate, being made the sense of photosensitive transfer printing material of the invention The process that photosensitive resin composition layer is in contact with substrate and is bonded；To the photonasty tree of the photosensitive transfer printing material after bonding process The process of oil/fat composition layer progress pattern exposure；Developed to come to the photosensitive polymer combination layer after the process being exposed The process for forming the process of pattern and the substrate being not configured in figuratum region being etched.

In the past, photosensitive polymer combination be divided into according to the difference of photosensitive system will irradiate photoactinic part as Image and remaining minus and will not irradiate photoactinic part as image remaining eurymeric.Pass through photograph in eurymeric Actinic ray is penetrated, such as generates emulsion of acid etc. using irradiation actinic ray to improve the dissolubility of exposure portion, therefore work as It is uncured in pattern exposure moment exposure portion and unexposed portion, it, can be by full when obtained pattern form is bad Face exposure etc. is recycled (reprocessing) to substrate.Therefore, from so-called re-workability it is excellent from the viewpoint of, be preferably positive Type.Also, remaining photosensitive polymer combination layer expose once again make the technology of different patterns if not Positive type photosensitive organic compound layer then cannot achieve, therefore in the manufacturing method of wiring of the invention, preferably lift The mode of progress 2 times or more exposures out.

[bonding process]

The manufacturing method of wiring of the invention, which preferably comprises, makes substrate photosensitive transfer printing material of the invention The process (bonding process) that photosensitive polymer combination layer is in contact with substrate and is bonded.

In bonding process, preferably photosensitive transfer printing material is set to contact and be bonded in the substrate for having conductive layer.

Also, in bonding process, the mode for preferably contacting conductive layer and photosensitive polymer combination layer is crimped.If For aforesaid way, then the photosensitive polymer combination layer that the pattern after exposure and development is formed can be preferably used as to conduction Etching resist when property layer is etched.

It is not particularly limited, is able to use well known as the method for crimping substrate and photosensitive transfer printing material Transfer method and laminating method.

Specifically, for example preferably stressing the photosensitive polymer combination layer of photosensitive transfer printing material to be stacked in conductive layer Above and by being carried out based on the pressurization of roller etc. or pressurization and heating.In fitting, be able to use stacking, it is vacuum laminated with And it can more improve productive automatic cutting and stacking well known to (Auto-Cut laminator) etc. is laminated.

Crimping pressure and temperature in bonding process are not particularly limited, can be according to conductive layer and photonasty Material, conveying speed and used press-connection machine of resin composition layer etc. are suitably set.Also, in photosensitive transfer printing When there is cover film on the photosensitive polymer combination layer of material, pressed after removing cover film from photosensitive polymer combination layer It connects.

When substrate is resin film, the crimping of roll-to-roll mode can be carried out.

Substrate-

It is laminated on substrate in the substrate of multiple conductive layers, substrate is preferably glass baseplate or film base material, more preferably For film base material.In the manufacturing method of wiring of the invention, when for touch panel wiring, substrate is especially preferably Flaky resin composition.

Also, substrate is preferably transparent.

The refractive index of substrate is preferably 1.50~1.52.

Substrate can be made of Mght-transmitting base materials such as glass baseplates, be able to use with Corning Incorporated Co., Ltd. gorilla glass (Gorilla Glass) is the strengthened glass etc. of representative.Also, it, can as the transparent substrate It is preferably used in Japanese Unexamined Patent Publication 2010-086684 bulletin, Japanese Unexamined Patent Publication 2010-152809 bulletin and Japanese Unexamined Patent Publication Material used in 2010-257492 bulletin.

When using film base material as substrate, substrate more preferably high using the not substrate of optical strain and transparency, Specific material can enumerate polyethylene terephthalate (polyethylene terephthalate；PET), poly- naphthalene diformazan Sour glycol ester, polycarbonate, triacetyl cellulose, cyclic olefin polymer.

Conductive layer-

As multiple conductive layers formed on the substrate, can enumerate in general wiring or touch panel wiring Used in arbitrary conductive layer.

As the material of conductive layer, metal and metal oxide etc. can be enumerated.

As metal oxide, ITO (Indium Tin Oxide, tin indium oxide), IZO (Indium Zinc can be enumerated Oxide, indium zinc oxide), SiO₂Deng.As metal, Al, Zn, Cu, Fe, Ni, Cr, Mo etc. can be enumerated.

In the manufacturing method of wiring of the invention, at least one conductive layer in multiple conductive layers is preferably comprised Metal oxide.

As conductive layer, it is preferably equivalent to the sensing in the visuognosis portion used in capacitance type touch panel The wiring of the electrode pattern or edge lead division of device.

Wiring, which is formed, uses substrate-

It is the substrate of conductive layer on the surface of the substrate.Electricity is set as by being formed to conductive layer progress pattern Road wiring.In this example, the base of multiple conductive layers such as metal oxide or metal is preferably provided on the film base materials such as PET Plate.

[exposure process]

In the manufacturing method of wiring of the invention, the sense to the photosensitive transfer printing material after bonding process is preferably comprised The process (exposure process) of photosensitive resin composition layer progress pattern exposure.

In exposure process, preferably on the substrate for being provided with film, carry out irradiation light across the mask with specific pattern Change ray.In this process, photoacid generator decomposes and generates acid.Through the catalysis of generated acid, in applying film component Contained sour decomposability base carries out hydrolyzable, generates acidic group such as carboxyl or phenolic hydroxyl group.

In the present invention, the detailed configuration and specific size of pattern are not particularly limited.Have to improve to have The display quality of the display device (such as touch panel) of the input unit of the circuit substrate manufactured in the present invention, and to the greatest extent may be used Area shared by lead-out wiring, at least part (especially electrode pattern and lead-out wiring of touch panel of pattern can be reduced Part) be preferably 100 μm of filaments below, more preferably 70 μm of filaments below.

Also, the exposure in exposure process can be for across the exposure of mask, or the digital of laser etc. is utilized and exposes Light, but preferably across the exposure of exposure mask.

The manufacturing method of the substrate of attached drawing case of the invention is photosensitive comprising making preferably between bonding process and exposure process Property transfer materials and exposure mask contact process.If aforesaid way, then the resolution ratio of obtained pattern is more excellent.

As actinic ray, visible light, ultraviolet light and electron beam, but preferably visible light or ultraviolet light can be enumerated, especially It is preferably ultraviolet light.

As photoactinic exposure light source is based on, it is able to use Cooper-Hewitt lamp, high-pressure mercury-vapor lamp, super-pressure mercury Lamp, fluorescent lamp, light-emitting diode (LED) light source, excimer laser generating device etc., can it is preferable to use g rays (436nm), i Ray (365nm), h ray (405nm) etc. have the actinic ray of wavelength 300nm or more and 450nm wavelength below.Also, As needed, it can also be filtered by the light splitting of long wavelength cutoff filter, short wavelength's cut-off filter, bandpass filter etc Device adjusts irradiation light.

As exposure device, it is able to use mirror surface projection alignment exposer (mirror projection aligner), step Into various modes such as machine, scanner, close induction type (proximity), contact (contact), microlens array, laser explosures Exposure machine.

Light exposure is suitably selected according to used photosensitive polymer combination layer, but preferably 5mJ/cm²~ 200mJ/cm², more preferably 10mJ/cm²~100mJ/cm²。

Also, it is also preferred that carrying out for the purpose of improving the rectangularity of pattern, linearity and before development hot place after exposure Reason.By the so-called process referred to as PEB (Post Exposure Bake, postexposure bake), when can reduce by exposing Pattern edge caused by the standing wave generated in photosensitive polymer combination layer it is coarse.

Pattern exposure can carry out temporary support after the removing of photosensitive polymer combination layer, can also be interim in removing It is exposed before supporter via temporary support, then removes temporary support.It is based on photoresist group in order to prevent The influence closed the mask contamination of contact of the nitride layer with mask and the foreign matter for being attached to mask is avoided to generate exposure, is not preferably shelled It is exposed from temporary support.Pattern exposure can be the exposure across mask, be also possible to that the number of laser etc. is utilized Code exposure.

(developing procedure)

The manufacturing method of wiring of the invention is preferably comprised to the photosensitive resin composition after the process being exposed Nitride layer is developed to form the process of pattern (developing procedure).The photosensitive polymer combination layer being exposed in developing procedure Development be able to use developer solution to carry out.

As developer solution, it is not particularly limited as long as the exposed portion that can remove photosensitive polymer combination layer, Such as developer solution well known to being able to use the developer solution recorded in Japanese Unexamined Patent Publication 5-072724 bulletin etc..Developer solution is preferred To make the exposed portion of photosensitive polymer combination layer carry out the developer solution of lysotype development behavior.As developer solution, preferably Aqueous alkali, such as more preferably include with 0.05mol/L (liter)~5mol/L concentration by the compound of pKa=7~13 Aqueous alkali.Developer solution can be further containing organic solvent, the surfactant etc. with water with Combination.As in the present invention In it is preferable to use developer solution, such as the developer solution recorded in 0194 section of International Publication No. 2015/093271 can be enumerated.

Be not particularly limited as visualization way, can for sheathed dip-type developing, spray development, spray and rotation development, Either one or two of immersion development etc..Here, being illustrated to spray development, developer solution is blown to photosensitive after exposure by spray Property resin composition layer, can remove exposed portion.Also, after development, preferably detergent etc. is sprayed by spraying It blows, removes development residue while being wiped with brush etc..The liquid temperature of developer solution is preferably 20 DEG C~40 DEG C.

It can develop immediately after exposure, but can more play inhibition figure if from the time being exposed to until developing length The effect of the deformation of case shape.It is being preferably from exposure by 0.5 hour or more from the time until being exposed to development, it is more excellent It is selected as in the mode by 1 hour or more, further preferably developed after 6 hours or more, more plays and inhibit this The effect of the deformation of pattern form in invention.

The manufacturing method of the substrate of attached drawing case of the invention may include the process cleaned after development by water etc. or Process well known to process that the substrate of obtained attached drawing case is dried etc..

The post-bake process heated is carried out to pattern obtained from developing moreover, can have.That toasts afterwards adds Heat preferably carries out in the environment of 8.1kPa~121.6kPa, more preferably carries out under the environment of 50.66kPa or more.Another party Face more preferably carries out under the environment of 111.46kPa or less, particularly preferably carries out under the environment of 101.3kPa or less.After dry Roasting temperature is preferably 80 DEG C~250 DEG C, more preferably 110 DEG C~170 DEG C, especially preferably 130 DEG C~150 DEG C.After toast Time be preferably 1 minute~30 minutes, more preferably 2 minutes~10 minutes, especially preferably 2 minutes~4 minutes.After toast It can carry out, can also be carried out in the case where nitrogen replaces environment under air environment.

The conveying speed of above-mentioned substrate when each process in the manufacturing method of wiring of the invention is not special Limitation, preferably 0.5m/min~10m/min when removing exposure, more preferably 2.0m/min~8.0m/min when removing exposure.

[etching work procedure]

The manufacturing method of wiring of the invention, which preferably comprises, loses the substrate being not configured in figuratum region Carve the process (etching work procedure) of processing.

In etching work procedure, it is against corrosion etching will to be used as by the pattern that photosensitive polymer combination layer is formed by developing procedure Agent carries out the etching process of substrate.

The etching of substrate can be to record in 0048 section of Japanese Unexamined Patent Publication 2010-152155 bulletin~0054 section is equal Method applies etching based on method well known to method of the dry-etchings such as well known plasma etching etc..

For example, the wet etching impregnated in etching solution usually carried out can be enumerated as engraving method.It is lost in wet type Etching solution used in quarter properly selects the etching solution of acid type or alkaline type according to etch target.

As the etching solution of acid type, it is single that hydrochloric acid, sulfuric acid, nitric acid, acetic acid, fluoric acid, oxalic acid or phosphoric acid etc. can be exemplified Mixed aqueous solution of salt such as aqueous solution, acid ingredient and the iron chloride of only acid ingredient, ammonium fluoride or potassinm permanganate etc..It is acid Ingredient can be used and be combined with the ingredient of a variety of acid ingredients.

As the etching solution of alkaline type, sodium hydroxide, potassium hydroxide, ammonia, organic amine or tetramethyl hydrogen-oxygen can be exemplified Change the mixed aqueous solution of the salt such as aqueous solution, alkali composition and potassinm permanganate of the individual alkali composition such as salt of organic amine of ammonium etc Deng.Alkali composition can be used and be combined with the ingredient of a variety of alkali compositions.

The temperature of etching solution is not particularly limited, but preferably 45 DEG C or less.In the present invention, it is used as etching mask The pattern of (etched pattern) preferably especially plays the etching solution of acidity and alkalinity in 45 DEG C of temperature regions below excellent Patience.It is therefore prevented that above-mentioned pattern is removed in etching work procedure, there is no being partially selectively etched for above-mentioned pattern.

After etching work procedure, for the pollution for preventing process line, the process (scavenger of cleaning base plate can be carried out as needed Sequence) and process (drying process) that substrate is dried.About cleaning process, such as can enumerate in room temperature (10 DEG C~35 DEG C) in cleaning in 10 seconds~300 seconds carried out to substrate with pure water.About drying process, such as use air blower and appropriate adjustment Air blower pressure (0.1kg/cm²~5kg/cm²Degree) it is dried.

[stripping process]

The manufacturing method of wiring of the invention includes by photosensitive polymer combination layer preferably after etching work procedure The process (stripping process) removed using stripper.After etching work procedure, remain the photonasty that pattern is formed Resin composition layer.If not needing photosensitive polymer combination layer, remaining whole photosensitive polymer combination layers are removed i.e. It can.

As the method for using stripper to be removed, for example, can enumerate be preferably 30 DEG C~80 DEG C, more preferably 50 DEG C~80 DEG C of strippers in stirring in will be impregnated 5 minutes~30 minutes with the substrate of photosensitive polymer combination layer etc. Method.

As stripper, such as can enumerate the inorganic alkali composition such as sodium hydroxide or potassium hydroxide or tertiary amine or quaternary ammonium salt Etc. organic base compositions be dissolved in water, dimethyl sulfoxide, N- methylpyrrole pyridine ketone or this etc. stripper in mixed solutions.It can be used Stripper is removed by spray-on process, spray process or sheathed immersion method etc..

The manufacturing method of wiring of the invention can be as needed by exposure process, developing procedure and etching work procedure weight It is 2 times or more multiple.

As the example of exposure process, developing procedure and other processes in the present invention, in Japanese Unexamined Patent Publication 2006-023696 The method recorded in 0035 section~0051 section of number bulletin in the present invention also can be it is preferable to use.

The manufacturing method of wiring of the invention may include other any processes.For example, following process can be enumerated, but simultaneously It is not limited to the processes such as this.

[process for reducing luminous ray reflectivity]

The manufacturing method of wiring of the invention can be comprising carrying out reducing electric conductivity possessed by substrate such as substrate The process of the processing of some or all of luminous ray reflectivity of layer.

As the processing for reducing luminous ray reflectivity, oxidation processes etc. can be enumerated.For example, carrying out oxidation processes to copper Copper oxide is made, to carry out melanism, can reduce luminous ray reflectivity whereby.About reduction luminous ray reflectivity The preferred embodiment of processing, at 0017 section~0025 section of Japanese Unexamined Patent Publication 2014-150118 bulletin and Japanese Unexamined Patent Publication 2013- On the books in No. 206315 0041 section, 0042 section, 0048 section and 0058 section of bulletin, the content of the bulletin is incorporated into this specification In.

[process of insulating film is formed on the substrate being etched and forms the work of new conductive layer on insulating film Sequence]

The manufacturing method of wiring of the invention is it is also preferred that be included on substrate for example in established wiring (quilt The conductive layer of etching) on the process that forms the process of insulating film and form new conductive layer on insulating film.

The process for forming insulating film is not particularly limited, and can enumerate the well known method for forming permanent film.Also, The photosensitive material with insulating properties can be used, form the insulating film of desired pattern by photolithography.

The process that new conductive layer is formed on insulating film is not particularly limited.It can be used conductive photosensitive Property material, forms the new conductive layer of desired pattern by photolithography.

The manufacturing method of wiring of the invention can be formed new conductive layer by method same as described above Etching resist is simultaneously etched, and can also be etched additionally by well known method.

The circuit substrate that the manufacturing method of wiring through the invention obtains can only have 1 layer of circuit cloth on substrate Line can also have 2 layers or more of wiring.

In the manufacturing method of wiring of the invention, it is also preferred that substrate is respectively provided with multiple conductions on the surface of two sides Property layer gradually or is formed simultaneously circuit to the conductive layer formed on the surface of the two sides of substrate.It, can by this kind of structure It is formed on the surface of the side of substrate and is formed with the first conductive pattern (the first wiring) and the shape on the surface of the other side At the wiring for having the second conductive pattern (second circuit wiring), touch panel wiring is preferably formed.

< wiring and circuit substrate >

Wiring of the invention is the wiring of the manufacturing method manufacture of wiring through the invention.

Circuit substrate of the invention is the wiring of the manufacturing method manufacture with wiring through the invention Substrate.

The purposes of circuit substrate of the invention is not particularly limited, such as preferably touch panel circuit substrate.

[input unit and display device]

The device of wiring as the manufacturing method manufacture for having wiring through the invention, can enumerate input Device.

As long as input unit of the invention is the electricity at least with the manufacturing method manufacture of wiring through the invention The input unit of road wiring, preferably capacitance type touch panel.

Display device of the invention is preferably provided with input unit of the invention.Display device of the invention is preferably Organic Electricity The image display devices such as photoluminescence display device and liquid crystal display device.

[touch panel and touch panel display device]

Touch panel of the invention is the circuit cloth at least with the manufacturing method manufacture of wiring through the invention The touch panel of line.Touch panel of the invention preferably at least has transparent substrate, electrode and insulating layer or protective layer.

Touch panel display device of the invention is the manufacturing method manufacture at least with wiring through the invention Wiring touch panel display device, it is however preferred to have the touch panel display device of touch panel of the invention.

It can be resistance as the detection method in touch panel and touch panel display device of the invention of the invention Any in mode well known to film mode, electrostatic capacitance method, ultrasonic mode, electromagnetic induction method and optical mode etc. It is a.Wherein, preferably electrostatic capacitance method.

As touch panel type, so-called inline type (such as the figure in Japanese Unexamined Patent Application Publication 2012-517051 bulletin can be enumerated 5, the inline type recorded in Fig. 6, Fig. 7, Fig. 8), so-called outer insert-type (such as remembers in Figure 19 of special open 2013-168125 bulletin The outer insert-type carried, the outer insert-type recorded in Fig. 1 and Fig. 5 of Japanese Unexamined Patent Publication 2012-089102 bulletin), OGS (One Glass Solution, monolithic glass touch-control) type, TOL (Touch-on-Lens, eyeglass touch-control) type is (such as in Japanese Unexamined Patent Publication 2013- The TOL type recorded in Fig. 2 of No. 054727 bulletin), other structures (such as Fig. 6 in Japanese Unexamined Patent Publication 2013-164871 bulletin The structure of middle record), various outer hung type (so-called GG, G1G2, GFF, GF2, GF1, G1F etc.).

As touch panel of the invention and touch panel display device of the invention, can apply in " newest touch Panel technology " (on July 6th, 2009, Techno Times Co., Ltd.), " technology and exploitation of touch panel " (three paddy heros two Chief editor, in December, 2004, CMC publish), FPD International 2009Forum T-11 give a lecture textbook, Cypress It is constituted disclosed in Semiconductor Corporation application note (application note) AN2292 etc..

Embodiment

Embodiment is enumerated below, and more specific description is carried out to embodiments of the present invention.Material shown in following embodiment Material, usage amount, ratio, process content and processing sequence etc. can then be fitted without departing from the purport of embodiments of the present invention When being changed.Therefore, the range of embodiments of the present invention is not limited to concrete example as shown below.As long as no special Specified, then " part " and " % " is quality criteria.

In following example, following abbreviation respectively indicates following compound.

ATHF:2- tetrahydrofuran base acrylate (composite)

MATHF:2- tetrahydrofuran methyl acrylate (composite)

MAEVE:1- ethoxyethyl methacrylates (Wako Pure Chemical Industries, Ltd. system)

PHSTHF:4- (2- tetrahydrofuran base oxygroup) styrene (composite)

PHSEVE:1- ethoxyethyl group oxygroup styrene (composite)

PHS: 4-Vinyl phenol (composite)

CrNv: formaldehyde novolac (structure is polymer B -3 as shown below)

HEMA:2- hydroxyethyl methacrylate (Tokyo Chemical Industry Co., Ltd. system)

HPMA: hydroxy propyl methacrylate (2- hydroxy propyl methacrylate, methacrylic acid 2- hydroxyl -1- methyl Ethyl ester mixture) (Tokyo Chemical Industry Co., Ltd. system)

AA: acrylic acid (Tokyo Chemical Industry Co., Ltd. system)

CHA: acrylate base (Tokyo Chemical Industry Co., Ltd. system)

PGMEA: propylene glycol monomethyl ether (SHOWA DENKO K.K. system)

V-601: 2,2 '-azo of dimethyl bis- (2 Methylpropionic acid esters) (Wako Pure Chemical Industries, Ltd. it makes)

[synthesis of ATHF]

Acrylic acid (72.1 parts, 1.0 molar equivalents), hexane (72.1 parts) are added in 3 mouthfuls of flasks and is cooled to 20 DEG C.Drop Fall camphorsulfonic acid (0.0070 part, 0.03 mM of equivalent), 2- dihydrofuran (70.1 parts, 1.0 molar equivalents) and at 20 DEG C ± 2 After being stirred 1.5 hours in DEG C, it is warming up to 35 DEG C and stir within 2 hours.Kyoward 200 is successively paved in suction filter (aluminium hydroxide adsorbent, Kyowa Chemical Industry Co., Ltd. system), Kyoward 1000 (hydrotalcite system absorption Agent, Kyowa Chemical Industry Co., Ltd. system) after, filtered fluid has been obtained by the way that reaction solution to be filtered. After hydroquinone monomethyl ether (MEHQ, 0.0012 part) is added in obtained filtered fluid, by being concentrated under reduced pressure in 40 DEG C, obtain 140.8 parts of the acrylic acid tetrahydrofuran -2- base (ATHF) (yield 99.0%) as colorless oil is arrived.

[synthesis of MATHF]

Methacrylic acid (86.1 parts, 1.0 molar equivalents), hexane (86.1 parts) are added in 3 mouthfuls of flasks and is cooled to 20 ℃.Drip camphorsulfonic acid (0.0070 part, 0.03 mM of equivalent), 2- dihydrofuran (70.1 parts, 1.0 molar equivalents) and 20 After being stirred 1.5 hours in DEG C ± 2 DEG C, it is warming up to 35 DEG C and stir within 2 hours.Kyoward is successively paved in suction filter 200, after Kyoward 1000, filtered fluid has been obtained by the way that reaction solution to be filtered.It is added in obtained filtered fluid After MEHQ (0.0012 part), by being concentrated under reduced pressure in 40 DEG C, the methacrylic acid four as colorless oil has been obtained 156.2 parts of hydrogen furans -2- base (MATHF) (yield 98.0%).

[synthesis of PHS]

Acetic acid 4- vinyl phenyl ester (25.0 parts, 0.154 molar equivalent), ethyl acetate (34.2 are added in 3 mouthfuls of flasks Part) and be cooled to 5 DEG C.28% methanol solution of sodium methylate (59.5 parts) is dripped to have carried out stirring for 2 hours afterwards.Ethyl acetate is added (100 parts), water (200 parts), ammonium chloride (33.0 parts) carry out liquid separation operation to be extracted organic layer.By obtained organic layer It is sequentially cleaned with saturated aqueous ammonium chloride, saturated salt solution, by being concentrated under reduced pressure in 40 DEG C, has obtained conduct 17.0 parts of the 4-Vinyl phenol (PHS) (yield 91.9%) of yellow oil.

[synthesis of PHSTHF]

4-Vinyl phenol (120.0 parts, 1.0 molar equivalents), hexane (86.1 parts) are added in 3 mouthfuls of flasks and is cooled to 20℃.Drip camphorsulfonic acid (0.0070 part, 0.03 mM of equivalent), 2- dihydrofuran (70.1 parts, 1.0 molar equivalents) and After being stirred 1.5 hours in 20 DEG C ± 2 DEG C, it is warming up to 35 DEG C and stir within 2 hours.It is successively paved in suction filter After Kyoward 200, Kyoward 1000, filtered fluid has been obtained by the way that reaction solution to be filtered.In obtained filtering After MEHQ (0.0012 part) is added in liquid, by being concentrated under reduced pressure in 40 DEG C, the 4- (2- as colorless oil has been obtained Tetrahydrofuran base oxygroup) 186.3 parts of styrene (PHSTHF) (yield 98.0%).

[synthesis of PHSEVE]

4-Vinyl phenol (120.0 parts, 1.0 molar equivalents), hexane (86.1 parts) are added in 3 mouthfuls of flasks and is cooled to 20℃.Drip camphorsulfonic acid (0.0070 part, 0.03 mM of equivalent), ethyl vinyl ether (72.1 parts, 1.0 molar equivalents) simultaneously After being stirred 1.5 hours in 20 DEG C ± 2 DEG C, it is warming up to 35 DEG C and stir within 2 hours.It is successively paved in suction filter After Kyoward 200, Kyoward 1000, filtered fluid has been obtained by the way that reaction solution to be filtered.In obtained filtering After MEHQ (0.0012 part) is added in liquid, by being concentrated under reduced pressure in 40 DEG C, the 1- second as colorless oil has been obtained 188.2 parts of oxygroup ethyl oxygroup styrene (PHSEVE) (yield 98.0%).

[synthesis of polymer A-1]

PGMEA (75.0 parts) are added in 3 mouthfuls of flasks, 90 DEG C are warming up under nitrogen environment.ATHF (39.02 will be mixed with Part), HEMA (4.47 parts), AA (1.48 parts), CHA (55.03 parts), V-601 (4.1 parts), PGMEA (75.0 parts) solution spend It has dropped within 2 hours in 3 mouthfuls of flask solution for being maintained at 90 DEG C ± 2 DEG C.After drippage, by stirring 2 in 90 DEG C ± 2 DEG C Hour and obtained polymer A-1 (40.0 mass % of solid component concentration).

[synthesis of polymer A-2~A-18 and polymer B -1]

Type by monomer etc. changes like that as shown in table 1, and other conditions are then with side identical with polymer A-1 Method is synthesized.The solid component concentration of polymer 40 mass % have been set as.The Component units of table 1 are (by monomer polymerization At monomeric unit) content unit be mol%.

[polymer B -2~B-3]

Polymer B -2: poly(4-hydroxystyrene), Maruka Lyncur M S-1 (MARUZEN PETROCHEMICAL System), the PGMEA solution of 40 mass % of solid component concentration.

Polymer B -3: structure as shown below formaldehyde phenolic resin varnish (Meiwa Plastic Industries, Ltd. make), the PGMEA solution of 40 mass % of solid component concentration.

[chemical formula 18]

[photoacid generator]

Photoacid generator C-1: compound (BASF JAPAN LTD. system, the Irgacure PAG- of structure as shown below 103)

[chemical formula 19]

Photoacid generator C-2: the compound of structure as shown below (is in Japanese Unexamined Patent Publication 2013-047765 bulletin The compound recorded in 0227 section, and synthesized according to the method recorded in 0204 section.)

[chemical formula 20]

Photoacid generator C-3: structure as shown below compound (be International Publication No. 2014/020984 0090 The compound recorded in section, and synthesized according to the method recorded in 0161 section.)

[chemical formula 21]

Photoacid generator C-4: the compound of structure as shown below (is in Japanese Unexamined Patent Publication 2012-163937 bulletin The compound recorded in 0208 section, and synthesized according to the method recorded in 0212 section.)

[chemical formula 22]

[sensitizer]

Sensitizer E-1: structure as shown below compound (Kawasaki Kasei Chemicals Ltd. system, ANTHRACURE (registered trademark) UVS-1331), " Bu " indicates butyl in following structures.

[chemical formula 23]

[surfactant]

Surfactant F-1: the compound of structure as shown below

[chemical formula 24]

[alkali compounds]

Alkali compounds D-1: compound (Tokyo Chemical the Industry Co., Ltd. of structure as shown below System, CMTU)

[chemical formula 25]

1 > of < embodiment

[preparation of photosensitive polymer combination]

It is deployed according to consisting of, and is filtered with the polytetrafluoroethylene (PTFE) filter in 0.2 μm of aperture, whereby Photosensitive polymer combination is arrived.

424.5 parts of PGMEA

237.0 parts of polymer A-1

5.0 parts of photoacid generator C-1

0.1 part of surfactant F-1

0.1 part of alkali compounds D-1

[production of photosensitive transfer printing material]

(" PET (A) " is also referred to as below in 50 μm of thickness of polyethylene terephthalate film for becoming temporary support.) on, Photosensitive polymer combination is coated in such a way that dry film thickness becomes 3.0 μm by slit-shaped nozzle.Then, In It has been dried in 100 DEG C of convection oven (convection oven) 2 minutes, finally as cover film to polyethylene film (Tredegar Co., Ltd. system, OSM-N) is crimped, to make photosensitive transfer printing material.

< embodiment 2~10,12 and 13 >

Such as the record of table 1, polymer A-1 is changed to any of polymer A-2~A-10, and uses photoacid generator Any of C-1~C-3 has made embodiment 2~10,12 and 13 in the same manner as example 1 in addition to this Photosensitive transfer printing material.

11 > of < embodiment

By the composition of photosensitive polymer combination be changed to it is as shown below like that, in addition to this with same as Example 1 Mode has made the photosensitive transfer printing material of embodiment 11.

432.0 parts of PGMEA

224.5 parts of polymer A-8

5.0 parts of photoacid generator C-4

5.0 parts of sensitizer E-1

0.1 part of surfactant F-1

0.1 part of alkali compounds D-1

14 > of < embodiment

By the composition of photosensitive polymer combination be changed to it is as shown below like that, in addition to this with same as Example 1 Mode has made the photosensitive transfer printing material of embodiment 14.

424.5 parts of PGMEA

189.6 parts of polymer A-11

47.4 parts of polymer B -1

5.0 parts of photoacid generator C-1

0.1 part of surfactant F-1

0.1 part of alkali compounds D-1

15 > of < embodiment

By the composition of photosensitive polymer combination be changed to it is as shown below like that, in addition to this with same as Example 1 Mode has made the photosensitive transfer printing material of embodiment 15.

424.5 parts of PGMEA

213.3 parts of polymer A-11

23.7 parts of polymer B -2

5.0 parts of photoacid generator C-1

0.1 part of surfactant F-1

0.1 part of alkali compounds D-1

16 > of < embodiment

Photoacid generator C-1 is changed to photoacid generator C-3, has made reality in a manner of identical with embodiment 15 in addition to this Apply the photosensitive transfer printing material of example 16.

17 > of < embodiment

Polymer B -2 is changed to polymer B -3, has made embodiment in a manner of identical with embodiment 15 in addition to this 17 photosensitive transfer printing material.

18 > of < embodiment

Polymer A-11 is changed to polymer A-18, has made implementation in a manner of identical with embodiment 14 in addition to this The photosensitive transfer printing material of example 18.

1~7 > of < comparative example

Polymer A-1 is changed to such as any of polymer A-11~A-17 documented in table 1, in addition to this with Mode same as Example 1 has made the photosensitive transfer printing material of comparative example 1~7.

8 > of < comparative example

By the composition of photosensitive polymer combination be changed to it is as shown below like that, in addition to this with same as Example 1 Mode has made the photosensitive transfer printing material of comparative example 8.

424.5 parts of PGMEA

142.2 parts of polymer A-11

94.8 parts of polymer B -1

5.0 parts of photoacid generator C-1

0.1 part of surfactant F-1

0.1 part of alkali compounds D-1

9 > of < comparative example

By the composition of photosensitive polymer combination be changed to it is as shown below like that, in addition to this with same as Example 1 Mode has made the photosensitive transfer printing material of comparative example 9.

424.5 parts of PGMEA

189.6 parts of polymer A-11

47.4 parts of polymer B -2

5.0 parts of photoacid generator C-1

0.1 part of surfactant F-1

0.1 part of alkali compounds D-1

10 > of < comparative example

Polymer B -2 is changed to polymer B -3, has made comparative example in a manner of identical with comparative example 9 in addition to this 10 photosensitive transfer printing material.

< performance evaluation >

It is made with thickness 500nm by sputtering method using on 188 μm of thickness polyethylene terephthalate (PET) film There is the pet substrate of the attached layers of copper of layers of copper, has carried out following evaluation.

[transferability evaluation]

The photosensitive transfer printing material made is cut into 50cm square, peels cover film off, with 90 DEG C of roll temperature, line pressure 0.6MPa, linear velocity 3.6m/min stacking condition be laminated on the pet substrate of attached layers of copper.Measure photoresist group Nitride layer and the closely sealed area of layers of copper are closed, the face of the closely sealed area/cutting transfer materials of photosensitive polymer combination layer is passed through Product (%) has found out closely sealed area ratio.

5:95% or more

4:90% is more than and less than 95%

3:85% is more than and less than 90%

2:80% is more than and less than 85%

1: less than 80%

[pixel deformation evaluation]

By the photosensitive transfer printing material made with the stacking item of line pressure 0.6MPa, linear velocity (stacking speed) 3.6m/min Part is laminated on the pet substrate of attached layers of copper.In addition, when above-mentioned transferability is evaluated as 4 or less at 90 DEG C of roll temperature, Until the evaluation of above-mentioned transferability, which becomes, determines 5, roll temperature is improved to have made sample.

Temporary support is not removed and line and space pattern (line-and-space across 3 μm~20 μm of line width Pattern it after) (duty ratio (duty ratio) 1:1) mask is exposed with extra-high-pressure mercury vapour lamp, is placed 6 hours at 23 DEG C Remove temporary support afterwards to be developed.Development uses 28 DEG C of 1.0 mass % aqueous sodium carbonates, with spray develop into It has gone 40 seconds.The line and space pattern that 10 μm are formed by the above method find out the ratio between line width and space width as 1:1's Light exposure observes the deformation of the front end of 5 μm of the line and space pattern in its light exposure by scanning electron microscope (SEM) Amount, has carried out the evaluation of pixel deformation.3 the above are the grades that can be actually used.

5: not observing pixel deformation

4: pixel deformation is less than 0.5 μm

3: pixel deformation is 0.5 μm more than and less than 1.0 μm

2: pixel deformation is 1.0 μm more than and less than 3.0 μm

1: pixel deformation is 3.0 μm or more or the residual without pixel

[residual film ratio evaluation]

By the photosensitive transfer printing material made with the stacking item of line pressure 0.6MPa, linear velocity (stacking speed) 3.6m/min Part is laminated on the pet substrate of attached layers of copper.In addition when transferability is evaluated as 4 or less at 90 DEG C of roll temperature, until Until transferability evaluation becomes judgement 5, roll temperature is improved to have made sample.

Temporary support is removed, using 28 DEG C of 1.0 mass % aqueous sodium carbonates, is carried out with 40 seconds developing times Spray development.The ratio of film thickness after the development of film thickness before finding out relative to development, and carried out the evaluation of residual film ratio.It is residual Film rate is higher, then refers to that unexposed portion is more difficult to dissolve relative to developer solution.

5:98% or more

4:90% is more than and less than 98%

3:80% is more than and less than 90%

2:50% is more than and less than 80%

1: less than 50%

101 > of < embodiment

In 100 μ m-thick PET base materials, as the 2nd layer of conductive layer by tin indium oxide (ITO) by sputtering with 150nm thickness is formed a film, on it as the 1st layer conductive layer and by copper by vacuum vapour deposition with 200nm thickness progress Film forming, has been made circuit forming board whereby.

Photosensitive transfer printing material 1 (line the pressure 0.8MPa, linear velocity 3.0m/ obtained in embodiment 1 has been laminated in layers of copper Min, 90 DEG C of roll temperature).Temporary support is not removed and is used and is provided with along the knot for being unidirectionally connected with conductive layer liner The pattern shown in Fig. 2 of structure is (below also referred to as " pattern A ".) light shield carried out contact patterns exposure.Pattern A shown in Fig. 2 In, solid line portion SL and grey portion G are light shielding parts, and dotted line part DL illustrates the frame of alignment hypothetically.

Then temporary support removed, developed and is washed to have obtained pattern A.Then copper etchant solution is used After (KANTO CHEMICAL CO., INC. Cu-02) etches layers of copper, ITO etching solution (KANTO is used CHEMICAL CO., INC. ITO-02) ITO layer is etched, it has been obtained whereby by copper (solid line portion SL) and ITO (ash Color portion G) substrate of pattern A is depicted together.

Then, pattern shown in Fig. 3 (hereinafter referred to as " pattern B " is provided with using with the state being aligned.) opening portion Light shield has carried out pattern exposure, development and washing.In pattern B shown in Fig. 3, grey portion G is light shielding part, and dotted line part DL assumes Illustrate to property the frame of alignment.

Then, layers of copper is etched using Cu-02, and uses stripper (KANTO CHEMICAL CO., INC. system KP-301) wiring substrate has been obtained to remove remaining photosensitive polymer combination layer.

Wiring substrate has been obtained whereby.When being observed with microscope, no peeling and missing etc., are perfectly to scheme Case.

Symbol description

10- temporary support, 14- photosensitive polymer combination layer, 16- cover film, 100- photosensitive transfer printing material, SL- Solid line portion, G- grey portion, DL- dotted line part.

Claims

1. a kind of photosensitive transfer printing material, comprising:

Temporary support；And

Photosensitive polymer combination layer, containing component of polymer and photoacid generator comprising polymer, the polymer includes tool There are the Component units (a-1) of carboxyl protected group in the form of acetal or is protected in the form of acetal with phenolic hydroxyl group Group Component units (a-2),

The component of polymer includes the Component units (b-1) with phenolic hydroxyl group and the Component units with alcohol hydroxyl group At least one of (b-2),

The ratio of the shared Component units (b-1) and the Component units in total Component units of the component of polymer (b-2) ratio add up to 1 mole of % or more and 18 mole of % hereinafter,

Wherein, the composition is not single when the component of polymer does not include the polymer with the Component units (a-1) The ratio of first (b-1) is included within the total.

2. photosensitive transfer printing material according to claim 1, wherein

The acid value of the component of polymer is 60mgKOH/g or less.

3. photosensitive transfer printing material according to claim 1 or 2, wherein

The glass transition temperature of the component of polymer is 90 DEG C or less.

4. photosensitive transfer printing material according to claim 1 or 2, wherein

The glass transition temperature of the component of polymer is 60 DEG C or less.

5. photosensitive transfer printing material according to any one of claims 1 to 4, wherein

The Component units (a-1) are the Component units indicated with following formula A1,

In formula A1, R³¹And R³²Separately indicate hydrogen atom, alkyl or aryl, R³¹And R³²At least one of be alkane Base or aryl, R³³Indicate alkyl or aryl, R³¹Or R³²Optionally and R³³It connects and forms cyclic ether, R³⁴Indicate hydrogen atom or first Base, X⁰Indicate singly-bound or arlydene.

6. photosensitive transfer printing material according to any one of claims 1 to 5, wherein

The Component units (a-2) are the Component units indicated with following formula A3,

In formula A3, R⁵¹And R⁵²Separately indicate hydrogen atom, alkyl or aryl, R⁵¹And R⁵²At least one of be alkane Base or aryl, R⁵³Indicate alkyl or aryl, R⁵¹Or R⁵²Optionally and R⁵³It connects and forms cyclic ether, R⁵⁴Indicate hydrogen atom or first Base, X¹Indicate the linking group of singly-bound or divalent, R⁶²Indicate that substituent group, n indicate 0~4 integer.

7. photosensitive transfer printing material described according to claim 1~any one of 6, wherein

The Component units (b-1) are the Component units indicated with following formula B1,

In formula B1, R⁷⁰Indicate hydrogen atom or methyl, R⁷¹Indicate the linking group of singly-bound or divalent, R⁷²Separately indicate halogen Atom or alkyl, a indicate that 1~5 integer, b indicate that 0~4 integer, a+b are 5 or less.

8. photosensitive transfer printing material according to any one of claims 1 to 7, wherein

The Component units (b-2) are the Component units indicated with following formula B2,

9. photosensitive transfer printing material described according to claim 1~any one of 8, wherein

The component of polymer further includes the Component units from (methyl) alkyl acrylate with cyclic alkyl.

10. a kind of manufacturing method of wiring successively includes following process:

For substrate, make the photosensitive polymer combination of photosensitive transfer printing material according to any one of claims 1 to 9 The process that layer is contacted and is bonded with the substrate；

Pattern exposure is carried out to the photosensitive polymer combination layer of the photosensitive transfer printing material after the bonding process Process；

The process developed to the photosensitive polymer combination layer after the process for carrying out the exposure and form pattern；With And

The process that the substrate in the region for being not configured with the pattern is etched.