CN110312965A - The manufacturing method of photosensitive transfer printing material and circuit layout - Google Patents

Abstract

Photosensitive transfer printing material successively has temporary support, middle layer and photosensitive polymer combination layer; above-mentioned photosensitive polymer combination layer contains polymer and photoacid generator; the polymer includes the Component units with the acidic group protected by sour decomposability base; above-mentioned middle layer contains resin C; the resin C is water-soluble or alkali solubility, and includes the Component units with phenolic hydroxyl group or the alcohol hydroxyl group for being not directly attached to main chain.Also, provide a kind of manufacturing method of circuit layout for having used above-mentioned photosensitive transfer printing material.

Description

The manufacturing method of photosensitive transfer printing material and circuit layout

Technical field

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

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 part and the extraction 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.

For example, disclosing a kind of photosensitive transfer printing material in Japanese Unexamined Patent Publication 2015-118202 bulletin, the photonasty turns Print material is characterized in that, with supporter and photosensitive polymer combination layer, above-mentioned photosensitive polymer combination layer includes It (A) include component of polymer and (B) comprising the polymer with the Component units (a1) for the acidic group protected by sour decomposability base Photoacid generator, above-mentioned photosensitive polymer combination do not have ethylene cross-linked structure.

Summary of the invention

The invention technical task to be solved

The project that one embodiment of the present invention wants to solve is that the deformation for providing a kind of obtained pattern form is few Photosensitive transfer printing material.

Also, the project that another embodiment of the present invention wants to solve, which is to provide, a kind of has used above-mentioned photonasty to turn Print the manufacturing method of the circuit layout of material.

For solving the means of technical task

For solving the scheme of the above subject, including following manner.

A kind of photosensitive transfer printing material of 1 > of < successively has temporary support, middle layer, photosensitive polymer combination layer, Above-mentioned photosensitive polymer combination layer contains polymer and photoacid generator, and the polymer includes to have to be protected by sour decomposability base Acidic group Component units, above-mentioned middle layer contains resin C, and the resin C is water-soluble or alkali solubility, and includes with phenol Hydroxyl or be not directly attached to main chain alcohol hydroxyl group Component units.

2 > of < photosensitive transfer printing material according to above-mentioned 1 > of <, wherein

Further there is thermoplastic resin layer between above-mentioned temporary support and above-mentioned middle layer.

3 > of < photosensitive transfer printing material according to above-mentioned 1 > of < or 2 > of <, wherein

Above-mentioned resin C is selected from by linear phenol-aldehyde resin, modified cellulose resin and acrylic compounds tree with hydroxyl At least one kind of resin in the group of rouge composition.

4 > of < photosensitive transfer printing material according to any of above-mentioned 1 > of <~<, 3 >, wherein

Above-mentioned middle layer further contains the water-soluble or alkali-soluble resin D in addition to above-mentioned resin C.

5 > of < photosensitive transfer printing material according to above-mentioned 4 > of <, wherein

Above-mentioned resin D is selected from by polyacrylic acid, Sodium Polyacrylate, polyacrylamide, polyethylene oxide, polyethyleneimine At least one kind of resin in the group of amine, polyvinyl alcohol and polyvinylpyrrolidone composition.

6 > of < photosensitive transfer printing material according to above-mentioned 4 > of < or 5 > of <, wherein

Above-mentioned resin D is at least one kind of resin in the group being made of polyvinyl alcohol and polyvinylpyrrolidone.

7 > of < photosensitive transfer printing material according to any of above-mentioned 4 > of <~<, 6 >, wherein

The mass ratio that contains of above-mentioned resin C and above-mentioned resin D in above-mentioned middle layer are resin C: resin D=5:1~1: 2。

8 > of < photosensitive transfer printing material according to above-mentioned 7 > of <, wherein

The mass ratio that contains of above-mentioned resin C and above-mentioned resin D in above-mentioned middle layer are resin C: resin D=4:1~2: 1。

9 > of < photosensitive transfer printing material according to any of above-mentioned 1 > of <~<, 8 >, wherein

Component units with the acidic group protected by above-mentioned sour decomposability base are the Component units indicated with following formula A.

[chemical formula 1]

In formula A, R³¹And R³²Separately indicate hydrogen atom, alkyl or aryl, at least R³¹And R³²Any of be alkane Base or aryl, R³³Indicate alkyl or aryl, R³¹Or R³²With R³³It can connect and form cyclic ether, R³⁴Indicate hydrogen atom or first Base, X⁰Indicate singly-bound or arlydene.

10 > of < photosensitive transfer printing material according to any of above-mentioned 1 > of <~<, 9 >, wherein

The glass transition temperature of above-mentioned polymer in above-mentioned photosensitive polymer combination layer is 90 DEG C or less.

A kind of manufacturing method of circuit layout of 11 > of < successively includes following process: for substrate, make above-mentioned 1 > of <~ The above-mentioned photosensitive polymer combination layer of photosensitive transfer printing material described in any of 10 > of < is contacted and is pasted with aforesaid substrate The process of conjunction；Pattern is carried out to the above-mentioned photosensitive polymer combination layer of the above-mentioned photosensitive transfer printing material after above-mentioned bonding process The process of exposure；Developed to the above-mentioned photosensitive polymer combination layer after the above-mentioned process being exposed and forms pattern Process；And to the process that the aforesaid substrate in the region for being not configured with above-mentioned pattern is etched.

A kind of manufacturing method of circuit layout of 12 > of < successively includes following process: for substrate, make above-mentioned 1 > of <~ The above-mentioned photosensitive polymer combination layer of photosensitive transfer printing material described in any of 10 > of < is contacted and is pasted with aforesaid substrate The process of conjunction；The process for removing the temporary support of above-mentioned photosensitive transfer printing material；To above-mentioned photosensitive polymer combination layer into The process of row pattern exposure；The process developed to above-mentioned photosensitive polymer combination layer and form pattern；And to not matching The process that the aforesaid substrate being equipped in the region of above-mentioned pattern is etched.

Invention effect

According to an embodiment of the present invention, it is capable of providing a kind of few photonasty turn of the deformation of obtained pattern form Print material.

Also, another embodiment according to the present invention is capable of providing and a kind of has used above-mentioned photosensitive transfer printing material The manufacturing method of circuit layout.

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, being illustrated to the contents of the present invention.In addition, being illustrated while referring to additional attached drawing, still Symbol omits sometimes.

Also, the numberical range for using "~" to indicate in this specification refers to the numerical value recorded before and after "~" under The range that limit value and upper limit value include.

Also, in this specification, " (methyl) acrylic acid " indicate both acrylic acid and methacrylic acid or any one, " (methyl) acrylate " indicate both acrylate and methacrylate or any one.

Moreover, in this specification, about the amount of each ingredient in composition, when in composition there are 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 for many kinds of substance being present in 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 this specification, substitution and unsubstituted label are not indicated not only comprising not having The group of substituted base, but also include the group with substituent group.For example, " alkyl " not only includes the alkane without substituent group Base (unsubstituted alkyl), also comprising the alkyl (substituted alkyl) with substituent group.

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

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

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

Also, the weight average molecular weight (Mw) and number-average molecular weight (Mn) in the present invention as long as no refer in particular to rule be with Having used TSKgel GMHxL, TSKgel G4000HxL, TSKgel G2000HxL (is TOSOH CORPORATION ProductName) tubing string gel permeation chromatography (GPC) analytical equipment, pass through solvent THF (tetrahydrofuran), differential refractometer carry out Detection, and the molecular weight that polystyrene is converted as standard substance.

(photosensitive transfer printing material)

Photosensitive transfer printing material of the invention successively has temporary support, middle layer, photosensitive polymer combination layer, on It states photosensitive polymer combination layer and contains polymer and photoacid generator, the polymer includes to have to be protected by sour decomposability base The Component units of acidic group, above-mentioned middle layer contain resin C, and the resin C is water-soluble or alkali solubility, and includes with phenol hydroxyl Base or be not directly attached to main chain alcohol hydroxyl group Component units.

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.In addition, When using the 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 the detailed discovery mechanism of said effect is indefinite, the deformation of obtained pattern form is especially being used Show when chemically amplified positive resin combination, it is by the sour decomposability base based on the acid generated that the inventors of the present invention, which infer, whereby Disengaging reaction and the compound from the sour decomposability base being detached from later diffusion caused by phenomenon.Moreover, this hair Bright people etc., which infers that middle layer passes through, to be contained for water-soluble or alkali solubility and includes with phenolic hydroxyl group or to be not directly attached to main chain Alcohol hydroxyl group Component units resin C, will be from the compound for the sour decomposability base having disengaged from by middle layer Above-mentioned hydroxyl is captured, and the compound relatively reduced whereby from the sour decomposability base having disengaged from expands to close pixel It dissipates, and inhibits the generation of the internal stress in the film based on the volume change associated with above-mentioned diffusion, inhibit whereby obtained The deformation of pattern form.

Hereinafter, photosensitive transfer printing material of the invention is described in detail.

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, middle layer 12, photosensitive polymer combination layer 14 and cover film 16 are sequentially laminated in print material 100.

Middle layer 12 contains resin C, and the resin C is water-soluble or alkali solubility, and includes with phenolic hydroxyl group or not straight It is connected to the Component units of the alcohol hydroxyl group of main chain in succession.

Photosensitive polymer combination layer 14 contains polymer and photoacid generator, and the polymer includes to have by sour decomposability The Component units of the acidic group of base protection.

Hereinafter, the constituent material etc. to photosensitive transfer printing material of the invention is illustrated.In addition, in the present specification, Sometimes the above structure in the following address present invention.

Sometimes it will be referred to as " specific aggregation comprising the polymer with the Component units for the acidic group protected by sour decomposability base Object ".

Above-mentioned photosensitive polymer combination layer is positive type photosensitive organic compound layer, sometimes referred to as " positive light sensitivity tree Oil/fat composition layer ".

< temporary support >

Temporary support is support middle layer and photosensitive polymer combination layer, and can be from middle layer or photonasty tree The supporter of oil/fat composition layer removing.

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.In addition, the upper limit value of above-mentioned transmitance is 100%.As the measuring method of transmitance, utilization can be enumerated The method that Otsuka Electronics Co., Ltd. MCPD 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, with required by being bonded of circuit layout formation substrate The viewpoints such as required translucency consider in flexible, initial exposure process, are 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.

< middle layer >

Photosensitive transfer printing material of the invention has between temporary support and photosensitive polymer combination layer containing tree The middle layer of rouge C, the resin C are water-soluble or alkali solubilities, and include with phenolic hydroxyl group or to be not directly attached to main chain The Component units of alcohol hydroxyl group are (also referred to simply as " resin C ".).

In addition, the inventors of the present invention's discovery is when using only the Component units comprising having the alcohol hydroxyl group for being directly connected in main chain Resin for example as polyvinyl alcohol resin when, generate the deformation of obtained pattern form.The inventors of the present invention infer, direct It is connected in the alcohol hydroxyl group of main chain, due to the steric hindrance of main chain, can not be captured by above-mentioned hydroxyl from having disengaged from Sour decomposability base compound, to be unable to get sufficient effect.

Also, in the present invention, " main chain " indicates relatively longest in the molecule of high-molecular compound for constituting resin It is bonded chain, " side chain " indicates the carbochain from branched main chain.

Resin C-

Resin C is water-soluble or alkali solubility, and includes with phenolic hydroxyl group or to be not directly attached to the alcohol hydroxyl group of main chain Component units resin, preferably repeat comprising above-mentioned Component units resin.As Component units, by resin C With a large amount of above-mentioned hydroxyls, more inhibit the deformation of obtained pattern form.

In addition, in the present invention, " water solubility " indicates solvable in the water of pH7.0 in 25 DEG C, and " alkali solubility " indicates It is solvable in the aqueous alkali of pH8.5 or more in 25 DEG C.

Also, above-mentioned " water-soluble or alkali solubility " can be any of water-soluble or alkali solubility, or water-soluble And alkali solubility.

As resin C, the resin comprising the Component units with phenolic hydroxyl group can be enumerated and do not connected directly comprising having It is connected to the resin of the Component units of the alcohol hydroxyl group of main chain.

As the resin comprising the Component units with phenolic hydroxyl group, such as phenol formaldehyde resin, metacresol first can be enumerated Urea formaldehyde, paracresol formaldehyde resin, m-/p- cresols formaldehyde resin, phenol/cresols (can be in m-, p- or m-/p- mixing Either one or two of) mix linear phenol-aldehyde resins, pyrogallol acetone resin, the polyhydroxystyrene resins such as formaldehyde resin etc..

As the resin comprising having the Component units for the alcohol hydroxyl group for being not directly attached to main chain, modified fibre can be enumerated Plain resin, acrylic resin (such as homopolymer or copolymer of hydroxyalkyl (methyl) acrylate), starch with hydroxyl Class, glycogen class, chitin kind, agar carbohydrate, carragheen class, general Shandong door screen polysaccharide, Arabic gum, rubber made from soybean cake etc..

Among this is equal, from the viewpoint of the deformation for inhibiting pattern form, resin C is preferably selected from by line style phenolic aldehyde tree At least one kind of resin of the group of rouge, modified cellulose resin and the acrylic resin composition with hydroxyl, is more preferably selected from By at least one kind of resin for the group that modified cellulose resin and the acrylic resin with hydroxyl form, further preferably Modified cellulose resin.

Also, as modified cellulose resin, from the viewpoint of the deformation for inhibiting pattern form, preferably hydroxyalkylation Cellulose.

As hydroxyalkylated celluloses, hydroxymethyl cellulose, hydroxyethyl cellulose, poly-hydroxyethyl chemical fibre dimension are preferably enumerated Element, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, glyoxalated hydroxypropyl methyl cellulose, hydroxypropyl methyl cellulose are adjacent Phthalic acid ester etc..

Wherein, it from the viewpoint of the deformation for inhibiting pattern form, is preferably selected from by hydroxypropyl cellulose and hydroxypropyl At least one kind of resin of the group of ylmethyl cellulose composition, more preferably hydroxypropyl methyl cellulose.

The weight average molecular weight of resin C from inhibit pattern form deformation and exposure after developer solution in dissolubility with And from the viewpoint of transferability, preferably 1,000 or more, more preferably 2,000~100,000, further preferably 10,000 ~50,000.

Above-mentioned middle layer can individually contain a kind of resin C, can also contain two or more.

Dissolution in developer solution of the content of resin C in middle layer from the deformation for inhibiting pattern form and after exposing From the viewpoint of property and transferability, the gross mass relative to middle layer be preferably 10 mass % or more and 100 mass % hereinafter, More preferably 20 mass % or more and 100 mass % hereinafter, further preferably 40 mass % or more and 100 mass % hereinafter, Especially preferably 65 mass % or more and 85 mass % or less.

Resin D-

Photosensitive transfer printing material of the invention from the viewpoint of the dissolubility and transferability in the developer solution after exposure, Preferably further containing the water-soluble or alkali-soluble resin D other than above-mentioned resin C.

As resin D, polyamide, epoxy resin, polyacetal resin, the acrylic acid other than resin C can be enumerated Resinoid, polyurethane resin, polyvinyl alcohol, polyvinyl formal, polyester resin, polyethyleneimine, gathers polystyrene resin Allyl amine, polyalkylene glycol etc..

Wherein, as resin D, from the viewpoint of the dissolubility and transferability in the developer solution after exposure, preferably Selected from by polyacrylic acid, Sodium Polyacrylate, polyacrylamide, polyethylene oxide, polyethyleneimine, polyvinyl alcohol and polyethylene At least one kind of resin of the group of base pyrrolidones composition, more preferably selected from by polyvinyl alcohol and polyvinylpyrrolidone group At group at least one kind of resin.

The weight average molecular weight of resin D is from the viewpoint of the dissolubility and transferability in the developer solution after exposure, preferably It is 1,000 or more, more preferably 2,000~100,000, further preferably 10,000~50,000.

Above-mentioned middle layer can individually contain a kind of resin D, can also contain two or more.

Dissolution in developer solution of the content of resin D in middle layer from the deformation for inhibiting pattern form and after exposing From the viewpoint of property and transferability, the gross mass relative to middle layer is preferably 1 mass % or more and 80 mass % hereinafter, more Preferably 5 mass % or more and 50 mass % are hereinafter, further preferably 10 mass % or more and 40 mass % are hereinafter, especially excellent It is selected as 15 mass % or more and 35 mass % or less.

Also, the content of the resin D in middle layer is preferably changed from the viewpoint of the deformation for inhibiting pattern form with quality Calculating is the content of resin C or less.

Also, the resin C and resin D in above-mentioned middle layer containing mass ratio from inhibit pattern form deformation and From the viewpoint of the dissolubility and transferability in developer solution after exposure, preferably resin C: resin D=5:1~1:2, it is more excellent It is selected as 4:1~2:1, further preferably 3.5:1~2.5:1.

Other additives-

Above-mentioned middle layer in the present invention is other than resin C and resin D, additionally it is possible to add as needed comprising well known Add agent.

As other additives, preferably enumerate describe below used in the photosensitive polymer combination layer other add Add agent.

The thickness-of middle layer

The thickness of above-mentioned middle layer is preferably 0.1 μm~10 μm, more excellent from the viewpoint of the deformation for inhibiting pattern form It is selected as 0.2 μm~8 μm, especially preferably 0.5 μm~5 μm.

Also, it is preferred that the thickness of above-mentioned middle layer is thinner than the thickness of above-mentioned photosensitive polymer combination layer.

The forming method-of middle layer

The forming method of middle layer is not particularly limited, can be by each ingredient and solvent with special ratios and with any Method is mixed, and carry out stirring and dissolving come prepare be used to form middle layer middle layer formation composition (also referred to as " in Between layer composition ".).For example, after capable of being also made each ingredient being made to be dissolved in the solution in solvent in advance respectively, it will be obtained Solution is mixed to prepare composition with special ratios.Composition produced above can be in the filter using 5 μm of aperture Etc. be provided in after being filtered using.

It, can be easily in temporary support by the way that middle layer composition is coated on temporary support and is made it dry Form middle layer.

Coating method is not particularly limited, can be in method well known to slot coated, spin coating, curtain painting, ink-jet application etc. It is coated.

Other layers (such as thermoplastic resin layer etc.) are described and at it below in addition, can also be formed in temporary support Upper coating middle layer.

< photosensitive polymer combination layer >

Photosensitive transfer printing material of the invention successively has temporary support, middle layer, photosensitive polymer combination layer, on It states photosensitive polymer combination layer and contains polymer and photoacid generator, the polymer includes to have to be protected by sour decomposability base The Component units of acidic group.

Also, the photosensitive polymer combination layer in the present invention is positive type photosensitive organic compound layer, preferably chemical Amplified positive photosensitive polymer combination layer.

In the photoacid generators such as the salt or oxime sulfonate compounds that describe below, incudes dynamic rays (actinic ray) and give birth to At acid play a role to the deprotection of the protected acidic group in above-mentioned particular polymers as catalyst, therefore pass through 1 light The acid that the effect of quantum generates facilitates multiple deprotection reactions, and quantum yield is greater than 1, for example, becoming the larger of the power such as 10 Value, as it is so-called chemistry amplification result high sensitivity can be obtained.

On the other hand, the photoacid generator as induction dynamic rays, 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.

Contain the component of polymer-comprising the polymer with the Component units for the acidic group protected by sour decomposability base

Above-mentioned photosensitive polymer combination layer includes polymer (also referred to as " particular polymers ".), the polymer includes Component units (also referred to as " Component units A " with the acidic group protected by sour decomposability base.).

Also, can also include other than the polymer with Component units A in above-mentioned photosensitive polymer combination layer Other polymers.In the present invention, also by with Component units A polymer and other polymers be referred to as " polymer at Point ".

Tool of the above-mentioned particular polymers by the effects of the acidic materials of the catalyst amount generated by exposure, in particular polymers There is the Component units A for the acidic group protected by sour decomposability base to be become acidic group by deprotection reaction.Pass through the acidic group, Neng Goujin Row curing reaction.

The preferred embodiment of Component units A is illustrated below.

Above-mentioned photosensitive polymer combination layer can be further containing in addition to comprising having the acidic group protected by sour decomposability base Component units polymer other than polymer.

Also, it is preferred that whole polymer contained in above-mentioned component of polymer is had including at least what is described below respectively The polymer of the Component units of acidic group.

Also, above-mentioned chemically amplified positive photosensitive polymer combination can further include the polymer in addition to the grade. Above-mentioned component of polymer in the present invention then refers to the object of the other polymers comprising being added as needed as long as no specifying Matter.Even also not wrapped in addition, the compound for being equivalent to the crosslinking agent and dispersing agent that describe below is set as high-molecular compound Substance contained in above-mentioned component of polymer.

Particular polymers are preferably addition polymerization type resin, are more preferably had from (methyl) acrylic acid or its ester The polymer of Component units.Alternatively, it is also possible to have other than the Component units from (methyl) acrylic acid or its ester Component units, such as the Component units from styrene or the Component units from vinyl compound etc..

Above-mentioned photosensitive polymer combination layer is from the dissolubility in the deformation and developer solution for inhibiting pattern form and turns It include that there is the structure indicated with following formula A1 as above-mentioned Component units A preferably as component of polymer from the viewpoint of print property It include to have to indicate with following formula A1 as above-mentioned Component units A more preferably as component of polymer at the polymer of unit A1 Component units A1, and glass transition temperature be 90 DEG C of particular polymers below, further preferably be used as component of polymer Comprising as above-mentioned Component units A with the Component units A1 indicated with following formula A1 and the structure with acidic group described below At unit B, and glass transition temperature is 90 DEG C of particular polymers below.

Particular polymers contained in above-mentioned photosensitive polymer combination layer can be only a kind, or two or more.

< < Component units A > >

Above-mentioned component of polymer includes polymer, and the polymer is included at least with the acidic group protected by sour decomposability base Component units A.Include the polymer with Component units A by above-mentioned component of polymer, it is high sensitivity can be made Chemically amplified positive photosensitive polymer combination layer.

The well known group that is able to use " by the acidic group that sour decomposability base is protected " in the present invention is decomposed as acidic group and acid Property base, is not particularly limited.As specific acidic group, carboxyl and phenolic hydroxyl group can be enumerated.Also, it is protected as by sour decomposability base The acidic group of shield, be able to use by acid be easier decompose group (for example, the ester group of the radical protection indicated with formula A1, Functional group, the acetals such as oxinane ester group or tetrahydrofuran ester group system) or by the group of the more difficult decomposition of acid (for example, the tert-butyl ester The carbonic acid three-level alkyl such as the three-levels such as base alkyl, t-butyl carbonate base ester group).

Among these, as above-mentioned sour decomposability base, it is however preferred to have the group for the structure protected in the form of acetal.

< < Component units A > >

It is above-mentioned have examined by the Component units A for the acidic group that sour decomposability base is protected from the viewpoint of sensitivity and resolution ratio Consider, the Component units A1 preferably indicated with following formula A1.

[chemical formula 2]

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.

Further, 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.Arlydene can have substituent group.

It is the Component units with the carboxyl protected by sour decomposability base with the Component units A1 that above-mentioned formula A1 is indicated.It is specific Polymer includes the Component units A1 indicated with formula A1, and the sensitivity in pattern formation is excellent whereby, and resolution ratio is more excellent It is different.

In formula A1, R³⁴Indicate hydrogen atom or methyl, it is excellent from the viewpoint of the Tg that can more reduce particular polymers It is selected as hydrogen atom.

More specifically, the R preferably with respect to the total amount for the Component units A1 for being contained in particular polymers, in formula A³⁴For hydrogen The Component units of atom are 20 mass % or more.

In addition, the R in formula A1 in Component units A1³⁴For the content (content ratio: quality of the Component units of hydrogen atom Than) can by by conventional method from¹³C- nuclear magnetic resoance spectrum spectrum (NMR) measures the intensity ratio of the peak strength calculated to confirm.

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 indicated with following formula A2.

[chemical formula 3]

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 preferred concrete example of the Component units A1 comprising the carboxyl protected by sour decomposability base indicated with formula A1, Following Component units can be illustrated.In addition, R³⁴Indicate hydrogen atom or methyl.

[chemical formula 4]

Also, as above-mentioned Component units A, from the viewpoint of the deformation for inhibiting pattern form, preferably with following formula The Component units that A3 is indicated.

[chemical formula 5]

In formula A3, R^B1And R^B2Separately indicate hydrogen atom, alkyl or aryl, R^B1And R^B2In at least one A is alkyl or aryl, R^B3Indicate alkyl or aryl, R^B1Or R^B2It can be with R^B3It connects and forms cyclic ether, R^B4Indicate hydrogen atom or Methyl, X^BIndicate the linking group of singly-bound or divalent, R^B12Indicate that substituent group, n indicate 0~4 integer.

In formula A3, work as R^B1Or R^B2When for alkyl, preferably carbon atom number be 1~10 alkyl.Work as R^B1Or R^B2For aryl When, preferably phenyl.R^B1And R^B2It is preferred that being respectively the alkyl of hydrogen atom or carbon atom number 1~4.

In formula A3, R^B3Indicate alkyl or aryl, the preferably alkyl of carbon atom number 1~10, more preferably carbon atom number 1 ~6 alkyl.

Also, R^B1~R^B3In alkyl and aryl can have substituent group.

In formula A3, R^B1Or R^B2It can be with R^B3It connects and forms cyclic ether, preferably R^B1Or R^B2With R^B3It 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, X^BIndicate 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 X^BComprising-C (= O) when O-, preferably carbon atom and and R contained in-C (=O) O-^B4The mode of the carbon atom Direct Bonding of bonding.Work as X^BPacket When containing-C (=O) NRN-, carbon atom and and R contained in preferably-C (=O) NRN-^B4The 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 comprised^B1~R^B3Group and X^BWith mutual para-linkage.

In formula A3, R^B12Indicate 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, R^B4Indicate hydrogen atom or methyl, from the viewpoint of the Tg for more reducing particular polymers, preferably Hydrogen atom.

More specifically, the total content relative to Component units A contained in particular polymers, the R in formula A3^B4For hydrogen original The Component units of son are preferably 20 mass % or more.

In addition, the R in formula A3 in Component units A^B4For the content (content ratio: mass ratio) of the Component units of hydrogen atom It can be confirmed by the intensity ratio for the peak strength for being measured according to 13C- nuclear magnetic resoance spectrum (NMR) and being calculated by conventional method.

In the Component units indicated with formula A3, from the viewpoint of the deformation for inhibiting pattern form, more preferably with following The Component units that formula A4 is indicated.

[chemical formula 6]

In formula A4, R^B4Indicate hydrogen atom or methyl, R^B5~R^B11Separately indicate hydrogen atom or carbon atom number 1~ 4 alkyl, R^B12Indicate that substituent group, n indicate 0~4 integer.

In formula A4, R^B4Preferably hydrogen atom.

In formula A4, R^B5~R^B11Preferably hydrogen atom.

In formula A4, R^B12Indicate 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 preferred concrete example of the Component units A4 indicated with formula A4, following Component units can be illustrated.In addition, R^B4Table Show hydrogen atom or methyl.

[chemical formula 7]

The Component units A contained in particular polymers can be a kind, be also possible to two or more.

The content of Component units A in particular polymers relative to the gross mass of particular polymers be preferably 20 mass % with On, the more preferably 20 mass % of mass %~90, further preferably 30 mass of mass %~70 %.

The content (content ratio: mass ratio) of Component units A in particular polymers can be by measuring according to 13C-NMR And confirmed by the intensity ratio of the peak strength of conventional method calculating.

Also, on the basis of whole component of polymer is resolved into Component units (monomeric unit), Component units A's Ratio is preferably the 5 mass % of mass %~80 relative to the gross mass of component of polymer, more preferably 10 matter of mass %~80 Measure %, especially preferably 30 mass of mass %~70 %.

< < Component units B > >

Above-mentioned particular polymers preferably comprise the Component units B with acidic group.

Component units B is the acidic group comprising for example sour decomposability base protection of unprotected base, i.e., without the acid of protecting group The Component units of base.Particular polymers include Component units B, and the sensitivity in pattern formation becomes well, in pattern whereby Become to be easily soluble in the developer solution of alkalinity in developing procedure after exposure, can be realized the shortening of developing time.

Acidic group in this specification indicates that pKa is 12 proton dissociation groups below.Acidic group is preferably by being capable of forming The monomer of acidic group is embedded into polymer as the Component units (Component units B) comprising acidic group.From the sight for improving sensitivity Point considers that the pKa of acidic group is preferably 10 hereinafter, more preferably 6 or less.Also, the pKa of acidic group is preferably -5 or more.

Particular polymers include Component units A and the Component units B with the carboxyl for being not protected base protection as copolymerization Glass transition temperature is simultaneously set as 90 DEG C hereinafter, the positive type photosensitive organic compound layer containing particular polymers by synthesis point In, resolution ratio while with the holding of good level containing transferability, from the fissility of temporary support, when pattern is formed And sensitivity is better.

As above-mentioned acidic group, carboxyl, sulfoamido, phosphonic acid base, sulfonic group, phenolic hydroxyl group and sulfonyl acid imide can be illustrated Base etc..Wherein, it is preferably selected from least one kind of acidic group for the group being made of carboxyl and phenolic hydroxyl group.

Importing the Component units with acidic group to particular polymers can have the monomer of acidic group to carry out by being copolymerized.

The Component units with acidic group as Component units B are more preferably from the Component units of styrene or acidic group It is substituted by the Component units of the Component units from vinyl compound or the Component units from (methyl) acrylic acid.

From when pattern formation sensitivity is better etc. that viewpoints consider, as Component units B, preferably with the structure of carboxyl At unit or with the Component units of phenolic hydroxyl group.

Monomer with the acidic group for being capable of forming Component units B is not limited to the example described.

The Component units B for being contained in particular polymers can be only a kind, or two or more.

Gross mass of the particular polymers relative to particular polymers preferably comprises having for 0.1 mass of mass %~20 % The Component units (Component units B) of acidic group more preferably include the 0.5 mass % of mass %~15, further preferably include 1 mass % ~10 mass %.If above range, then patternability is better.

The content (content ratio: mass ratio) of Component units B in particular polymers can by by conventional method from¹³C- NMR measures the intensity ratio of the peak strength calculated to confirm.

< < other Component units > >

In the range of not damaging the effect of photosensitive transfer printing material of the invention, particular polymers are in addition to the structure that has described It can also include in addition other Component units (hereinafter sometimes referred to as Component units C at unit A and Component units B.).

As the monomer for forming Component units C, it is not particularly limited, such as phenylethylene, (methyl) can be enumerated It is alkyl acrylate, (methyl) acrylic acid cyclic alkyl ester, (methyl) benzyl acrylate, unsaturated dicarboxylic diester, bicyclic Unsaturated compound, maleimide compound, unsaturated aromatic compound, conjugated diene based compound, unsaturated single carboxylic Acid, unsaturated dicarboxylic, unsaturated dicarboxylic acid anhydride, the group with aliphatic ring type skeleton, other unsaturated compounds.

Using Component units C, adjust in type and content at least any one, thus, it is possible to adjust each of particular polymers Kind characteristic.In particular, thus, it is possible to the Tg of particular polymers is easily adjusted to 90 DEG C by the way that Component units C is suitably used Below.

Particular polymers can only include a kind of Component units C, also may include two or more.

Component units C can specifically be enumerated styrene, t-butoxystyrene, methyl styrene, Alpha-Methyl benzene Ethylene, acetoxy-styrene, methoxy styrene, ethoxystyrene, chlorostyrene, vinylbenzoate, ethylene Yl benzoic acid ethyl ester, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) propylene Isopropyl propionate, (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 2- hydroxypropyl, (methyl) benzyl acrylate, (methyl) Isobornyl acrylate, acrylonitrile or ethylene glycol single acetyl acetic acid esters (methyl) acrylate etc. are polymerize and the composition that is formed Unit.Additionally it is possible to enumerate the chemical combination recorded in 0021 section~0024 section of Japanese Unexamined Patent Publication 2004-264623 bulletin Object.

Also, from the viewpoint of the electrical characteristics for improving obtained transfer materials, as Component units C, preferably have The Component units of aromatic rings or Component units with aliphatic ring type skeleton.As the monomer for waiting Component units is formed, have For body, styrene, t-butoxystyrene, methyl styrene, α-methylstyrene, two ring penta of (methyl) acrylic acid can be enumerated Ester, (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate and (methyl) benzyl acrylate etc..Wherein, as composition Unit C preferably enumerates the Component units from (methyl) cyclohexyl acrylate.

Also, from the viewpoint of adaptation, as the monomer for forming Component units C, such as preferably (methyl) acrylic acid Arrcostab.Wherein, from the viewpoint of adaptation, more preferably there is (methyl) alkyl acrylate of the alkyl of carbon atom number 4~12 Base ester.Specifically, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) can be enumerated N-butyl acrylate and (methyl) 2-EHA.

Gross mass of the content of Component units C relative to particular polymers, preferably 70 mass % are hereinafter, more preferable 60 matter % is measured hereinafter, further preferred 50 mass % or less.Can be 0 mass % as lower limit value, it is preferred that for 1 mass % with On, more preferably 5 mass % or more.

If in above range, then resolution ratio and adaptation are more improved.

From the dissolubility relative to developer solution and the viewpoint for the physics physical property for optimizing above-mentioned photosensitive polymer combination layer Consider, as Component units C, the preferred particular polymers composition list that also includes the ester with the acidic group in above-mentioned Component units B Member.

Wherein, as Component units B, particular polymers include the Component units with carboxyl, further preferably comprising having carboxylic The Component units C of perester radical as combined polymerization ingredient, such as more preferably comprising from (methyl) acrylic acid Component units B and From the Component units of (methyl) cyclohexyl acrylate, (methyl) 2-EHA or (methyl) n-butyl acrylate The polymer of c.

Hereinafter, the preferred example of the particular polymers in the present invention is enumerated, but the present invention is not limited to examples below Show.In addition, the ratio of the Component units in following exemplary compounds, weight average molecular weight in order to obtain preferred physical property and suitably select It selects.

[chemical formula 8]

The glass transition temperature of < < polymer: Tg > >

It is preferred that the glass transition temperature (Tg) of the particular polymers in the present invention is 90 DEG C or less.By Tg be 90 DEG C with Under, above-mentioned photosensitive polymer combination layer has high adaptation, and transferability is more excellent.

Above-mentioned Tg is more preferably 60 DEG C hereinafter, further preferably 40 DEG C or less.

Also, what the lower limit value of above-mentioned Tg was not particularly limited, it is preferred that -20 DEG C or more, more preferably -10 DEG C with On.Be -20 DEG C or more by the Tg of particular polymers, keep good patternability and for example using cover film the case where Under, fissility when can inhibit removing cover film reduces.

Moreover, from the viewpoint of transferability, the glass transition temperature of the above-mentioned component of polymer totality in the present invention (Tg) be preferably 90 DEG C hereinafter, more preferably 60 DEG C hereinafter, further preferably 40 DEG C or less.

The glass transition temperature of polymer is able to use Differential Scanning Calorimeter measurement (DSC) to measure.

Method of the specific measuring method to be recorded in JIS K 7121 (1987) or JIS K 6240 (2011) On the basis of carry out.Glass transition temperature in this specification is using extrapolation glass transition initial temperature (hereinafter, sometimes referred to as Tig)。

More specific description is carried out to the measuring method of glass transition temperature.

In the case where finding out glass transition temperature, protected in about 50 DEG C of the Tg lower than polymer of at a temperature of device of anticipation It keeps steady after determining, with heating speed: 20 DEG C/min are heated to about 30 DEG C of temperature higher than the temperature for terminating glass transition, draw DTA curve or DSC curve out.

Glass transition temperature Tg in glass transition initial temperature (Tig) i.e. this specification of extrapolating is used as DTA song The straight line and the change in ladder shape part by glass transition that the reference line of low temperature side in line or DSC curve extends to high temperature side The temperature of intersection point of the slope of a curve tangent line that becomes maximum point-rendering find out.

As the method for the preferred range for being adjusted to have described by the Tg of polymer, such as from polymer as a purpose Each Component units homopolymer Tg and each Component units mass ratio, and with FOX formula be guidance, can control as a purpose Particular polymers Tg.

About FOX formula,

The Tg for being included in the homopolymer of the 1st Component units of polymer is set as Tg1, by the copolymer of the 1st Component units In mass fraction be set as W1, the Tg of the homopolymer of the 2nd Component units is set as Tg2, will be in the copolymer of the 2nd Component units When mass fraction is set as W2, the Tg0 (K) of the copolymer comprising the 1st Component units and the 2nd Component units can be according to formula below To estimate.

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

Using the FOX formula described, the type and mass fraction of each Component units of the adjustment package contained in copolymer can be obtained To the copolymer with desired Tg.

Also, by adjusting the weight average molecular weight of polymer, the Tg of polymer can be also adjusted.

The molecular weight of < < polymer: Mw > >

The molecular weight of particular polymers with polystyrene convert Weight-average molecular meter, preferably 60,000 or less.Pass through spy The weight average molecular weight for determining polymer is 60,000 hereinafter, the melt viscosity of photosensitive polymer combination layer is inhibited to be lower, and above-mentioned Substrate can be realized the fitting under low temperature (such as 130 DEG C or less) when being bonded.

Also, the weight average molecular weight of particular polymers is preferably 2,000~60,000, more preferably 3,000~50,000.

In addition, the weight average molecular weight of particular polymers can be measured by GPC (gel permeation chromatography), filled as measurement It sets, is able to use various commercially available devices, the content and determination techniques of device are well known for those skilled in the art.

Measurement about the weight average molecular weight based on gel permeation chromatography (GPC) is able to use HLC as measurement device (registered trademark) -8220GPC (TOSOH CORPORATION system) is able to use and 1 is connected in series respectively as tubing string TSKgel (registered trademark) Super HZM-M (4.6mmID × 15cm, TOSOH CORPORATION system), Super HZ4000 (4.6mmID × 15cm, TOSOH CORPORATION system), Super HZ3000 (4.6mmID × 15cm, TOSOH CORPORATION system), the tubing string of Super HZ 2000 (4.6mmID × 15cm, TOSOH CORPORATION system), as washing De- liquid, is able to use THF (tetrahydrofuran).

Also, as determination condition, sample solution concentration is set as 0.2 mass %, flow velocity is set as to 0.35ml/min, by sample Injection rate is set as 10 μ l and measuring temperature is set as 40 DEG C, and is able to use differential refractive index (RI) detector to carry out.

Calibration curve be able to use TOSOH CORPORATION system " standard sample TSK standard, This 7 samples of polystyrene ": " F-40 ", " F-20 ", " F-4 ", " F-1 ", " A-5000 ", " A-2500 " and " A-1000 " Any of make.

The number-average molecular weight of particular polymers and the ratio (dispersion degree) preferably 1.0~5.0, more preferable 1.05 of weight average molecular weight ~3.5.

The manufacturing method > > of < < particular polymers

The manufacturing method (synthetic method) of particular polymers is not particularly limited, if but enumerate an example, comprising being used for It forms the polymerizable monomer of the Component units A1 indicated with formula A, be used to form the polymerism list of the Component units B with acidic group Body includes to be able to use polymerization in the organic solvent for the polymerizable monomer for being used to form other Component units C and draw also according to needs Hair agent is polymerize to synthesize.Also, it can also be synthesized by so-called high molecular weight reactive.

Above-mentioned photoresist group from the viewpoint of showing good adaptation relative to aforesaid substrate, in the present invention Total solid content of the nitride layer relative to photosensitive polymer combination layer is closed, preferably with the ratio packet of 50 mass of mass %~99.9 % Containing above-mentioned component of polymer, more preferably include with the ratio of 70 mass of mass %~98 %.

Also, from the viewpoint of showing good adaptation relative to aforesaid substrate, above-mentioned photosensitive polymer combination Total solid content of the layer relative to photosensitive polymer combination layer preferably includes upper with the ratio of 50 mass of mass %~99.9 % Particular polymers are stated, more preferably include with the ratio of 70 mass of mass %~98 %.

< < other polymers > >

In the range of not damaging the effect of photosensitive transfer printing material of the invention, in above-mentioned photosensitive polymer combination layer As component of polymer other than particular polymers, it can further include without containing with the poly- of the formula A Component units (a) indicated It closes object (sometimes referred to as " other polymers ".).When above-mentioned photosensitive polymer combination layer includes other polymers, other polymerizations The use level of object in total polymer ingredient be preferably 50 mass % hereinafter, more preferably 30 mass % hereinafter, further preferably For 20 mass % or less.

Above-mentioned photosensitive polymer combination layer can only include a kind of other polymers other than particular polymers, can also be with Comprising two or more.

As other polymers, such as it is able to use polycarboxylated styrene, is also able to use commercially available SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P and SMA 3840F (more than, Sartomer Company, Inc system), ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920 and ARUFON UC-3080 (more than, TOAGOSEI CO., LTD. system) and Joncryl 690, Joncryl 678, Joncryl 67 and Joncryl 586 (more than, BASF AG's system) etc..

Photoacid generator-

Above-mentioned photosensitive polymer combination layer contains photoacid generator.

As photoacid generator as used in the present invention, for can by irradiation ultraviolet light, far ultraviolet, X-ray and The radioactive ray such as charged particle beam come generate acid compound.

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 comprising is indicated with following formula (B1) Oxime sulfonates structure compound.

[chemical formula 9]

In formula (B1), R²¹Indicate alkyl or aryl, * indicates to be bonded position with other atoms or other groups.

Compound containing the oxime sulfonates structure indicated with formula (B1) 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 formula (B1) 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, the salinization such as Diaryl iodonium salt and triaryl sulfonium salts class can be enumerated Close object, quaternary ammonium salt etc..Among these, preferred salt compound, particularly preferred triaryl sulfonium salts class and diaryl iodonium salt Class.

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 above-mentioned photosensitive polymer combination layer is from the viewpoint of sensitivity, resolution ratio, phase Gross mass for above-mentioned photosensitive polymer combination layer is preferably the 0.1 mass % of mass %~10, more preferably 0.5 mass % ~5 mass %.

Solvent-

Above-mentioned photosensitive polymer combination layer may include solvent.

Also, the photosensitive polymer combination of above-mentioned photosensitive polymer combination layer is formed in order to be readily formed above-mentioned sense Photosensitive resin composition layer first adjusts the viscosity of photosensitive polymer combination containing solvent, then will wrap solvent-laden photonasty Resin combination is coated and dries, and can be preferably formed as above-mentioned 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.

Also, benzylisoeugenol, hexyl ether, second two also can be further added in the solvent described as needed Alcohol list phenyl ether acetate, 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 equal solvent.

Solvent may be used alone or in combination of two or more.

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.

Also, as solvent, preferably 130 DEG C of boiling point 160 DEG C of solvent, boiling points more than and less than 160 DEG C or more it is molten Agent or their mixture.

As 130 DEG C of the boiling point solvents more than and less than 160 DEG C, propylene glycol monomethyl ether (boiling point can be illustrated 146 DEG C), 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 first Base n-propyl ether (131 DEG C of boiling point).

As 160 DEG C of boiling point or more of solvent, 3- ethoxyl ethyl propionate (170 DEG C of boiling point), diethylene glycol can be illustrated Methyl ethyl ether (176 DEG C of boiling point), propylene glycol monomethyl ether propionic ester (160 DEG C of boiling point), (boiling of dipropylene glycol methyl ether acetic acid esters Point 213 DEG C), 3- methoxybutyl ether acetic acid ester (171 DEG C of boiling point), diethylene glycol diethyl ether (189 DEG C of boiling point), diethylene glycol Dimethyl ether (162 DEG C of boiling point), propylene-glycol diacetate (190 DEG C of boiling point), diethylene glycol monoethyl ether acetic acid esters (boiling point 220 DEG C), 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.

Also, the content of the solvent in above-mentioned photosensitive polymer combination layer is relative to above-mentioned photosensitive polymer combination layer Gross mass, preferably 2 mass % hereinafter, more preferably 1 mass % hereinafter, further preferably 0.5 mass % or less.

Other additives-

It, can in above-mentioned photosensitive polymer combination layer in the present invention other than particular polymers and photoacid generator It as needed include well known additive.

(plasticizer)

To improve the purpose of plasticity, above-mentioned photosensitive polymer combination layer can contain plasticizer.

It is preferred that the weight average molecular weight of above-mentioned plasticizer is less than the weight average molecular weight of particular polymers.

From the viewpoint of assigning plasticity, the weight average molecular weight of plasticizer preferably 500 is more excellent more than and less than 10,000 Select 700 more than and less than 5,000, further preferred 800 more than and less than 4,000.

As long as plasticizer is the compound that plasticity is mixed and shown with particular polymers, 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 10]

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

In addition, for example, (" compound X " can be set as the compound of the alkylidene oxygroup with above structure.), mixing Chemically amplified positive photosensitive polymer combination obtained from compound X, particular polymers and photoacid generator with do not include chemical combination Object X and the chemically amplified positive photosensitive polymer combination that is formed does not meet the present invention compared in the case where not improving plasticity In plasticizer.For example, the surfactant arbitrarily added is usually can not bring plasticity to photosensitive polymer combination It measures and uses, therefore do not meet the plasticizer in this specification.

As above-mentioned plasticizer, such as the compound with following structures can be enumerated, but it's not limited to that.

[chemical formula 11]

For the content of plasticizer from the viewpoint of adaptation, the gross mass relative to above-mentioned photosensitive polymer combination layer is excellent It is selected as the 1 mass % of mass %~50, more preferably 2 mass of mass %~20 %.

Above-mentioned photosensitive polymer combination layer can only include a kind of plasticizer, also may include two or more.

(sensitizer)

Above-mentioned 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 above-mentioned sensitizer, 0139 section~0141 Duan Zhongji at International Publication No. 2015/093271 can be enumerated The compound of load.

The content of sensitizer is preferably 0 matter of mass %~10 relative to the gross mass of above-mentioned photosensitive polymer combination layer Measure %, more preferably 0.1 mass of mass %~10 %.

(alkali compounds)

Above-mentioned chemically amplified positive photosensitive polymer combination 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..

Above-mentioned alkali compounds can be used alone, and can also use two or more simultaneously.

The content of alkali compounds is preferably 0.001 mass % relative to the gross mass of above-mentioned photosensitive polymer combination layer ~5 mass %, more preferably 0.005 mass of mass %~3 %.

(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 Containing acid plain monomer, cyclic amine, this nitrogen containing monomer of oxazoline group, be further able to addition silicon, sulphur, phosphine etc. has ester (lactone) etc. The monomer containing heteroatomic ring etc. of atom with 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 above-mentioned photosensitive polymer combination layer is preferably the 0.01 mass % of mass %~50, and more preferably 0.1 mass %~ 10 mass %, further preferably 1 mass of mass %~5 %.It is preferably above-mentioned from the viewpoint of adaptation and etching patience Range.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 novolac 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, can enumerate JER828, 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, ADEKA 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 comprising 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)

Above-mentioned photosensitive polymer combination layer can contain alkoxysilane compound containing trialkylsilyl group in molecular structure.It is excellent as alkoxysilane compound containing trialkylsilyl group in molecular structure Elect trialkoxy silane compound.

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 alkoxy 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, above-mentioned photosensitive polymer combination layer preferably comprises surfactant.As Surfactant is able to use any of anionic system, cationic system, nonionic system (nonionic) or both sexes, still Preferred surfactant is 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 (Kyoei sha chemical Co., Ltd. system), Eftop (Jemco Inc. system), MAGAFAC (DIC CORPORATION system), Fluorad (Sumitomo 3M Limited system), AsahiGuard, Surflon (ASAHI GLASS CO., LTD. system), PolyFox (OMNOVA Solutions Inc. society system) and each series such as SH-8400 (Dow Corning Toray Co., Ltd. system).

Also, as surfactant, the Component units comprising indicating with following Formulas I -1 can be enumerated as preferred example A and Component units B, and the polystyrene conversion of gel permeation chromatography measurement when by by tetrahydrofuran (THF) as solvent Weight average molecular weight (Mw) is 1,000 or more and 10,000 copolymers below.

[chemical formula 12]

In formula (I-1), R⁴⁰¹And R⁴⁰³Separately indicate hydrogen atom or methyl, R⁴⁰²Indicate carbon atom number 1 or more and 4 Straight-chain alkyl-sub below, R⁴⁰⁴Indicate that 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 % or less Numerical value, q indicates that 20 mass % or more and 90 mass % numerical value below, r indicate that 1 or more and 18 integers below, s indicate 1 Above and 10 integers below, * expression are bonded position with other structures.

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

[chemical formula 13]

The weight average molecular weight (Mw) of 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 is preferably 10 mass % relative to the gross mass of above-mentioned photosensitive polymer combination layer 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.

(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, preparation respectively dissolves each ingredient in advance After the solution of solvent, composition can also be prepared by mixing obtained solution with specified ratio.Group as prepared above Closing also can be for using after object is filtered using the filter etc. in 0.2 μm of aperture.

By the way that photosensitive polymer combination to be coated on the intermediate layer and make it dry, can obtain in temporary support Photosensitive transfer printing material of the invention with photosensitive polymer combination layer.

Coating method is not particularly limited, can be in method well known to slot coated, spin coating, curtain painting, ink-jet application etc. It is coated.

In addition, photosensitive resin coating combines on it after capable of also forming other layers described below on the intermediate layer Nitride layer.

Other layer of > of <

Photosensitive transfer printing material of the invention can have the layer in addition to above-mentioned photosensitive polymer combination layer (hereinafter, having When be referred to as " other layers ").As other layers, contrast enhancing layer, cover film, thermoplastic resin layer etc. can be enumerated.

Thermoplastic resin layer, cover film etc.-

Photosensitive transfer printing material of the invention is from the viewpoint of transferability, preferably in above-mentioned temporary support and among the above Further there is thermoplastic resin layer between interbed.

Also, photosensitive transfer printing material of the invention can have for the purpose of protecting above-mentioned photosensitive polymer combination layer There is cover film.

About thermoplastic resin layer preferred embodiment 0189~0193 section of Japanese Unexamined Patent Publication 2014-085643 bulletin, Preferred embodiment about other floor is on the books respectively in 0194~0196 section of Japanese Unexamined Patent Publication 2014-085643 bulletin, should The content of bulletin is incorporated into this manual.

Wherein, from the viewpoint of transferability, thermoplastic resin layer is preferably comprised selected from by acrylic resin and benzene At least one kind of thermoplastic resin of the group of ethylene/acrylic acid copolymer composition.

It, can be in accordance in Japanese Unexamined Patent Publication when photosensitive transfer printing material of the invention has other layer of thermoplastic resin layer etc. The production method of the photosensitive transfer printing material recorded in 0094~0098 section of 2006-259138 bulletin makes.

For example, when production has the photosensitive transfer printing material of the invention of thermoplastic resin layer, in temporary support Lysate (thermoplastic resin layer coating fluid) dissolved with organic thermoplastic polymer and additive is coated and makes it It is dry come after thermoplastic resin layer is arranged, will be so that thermoplastic resin layer is dissolved molten in obtained thermoplastic resin layer Resin and additive are added in agent and the preparation solution (middle layer composition) for preparing is coated and is made it dry come in being laminated Interbed.The photosensitive resin composition further prepared the solvent for dissolving middle layer is used in established middle layer Object is coated and makes it dry that photosensitive polymer combination layer is laminated, whereby being capable of preferred fabrication photonasty of the invention turn Print material.

Contrast enhancing layer-

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 gradually becomes smaller, is the material (referred to as light achromicity pigment composition) that the transmitance containing light is got higher Layer.As light achromicity pigment composition, it is known to which diazonium salt, stibazole (stilbazolium) salt, aryl are sub- Nitro salt etc..As overlay film forming component, phenol resin etc. is used.

In addition, spend enhancement layer as a comparison, be able to use 0004 section of Japanese Unexamined Patent Publication 6-097065 bulletin~ 0051 section, 0012 section~0055 section of Japanese Unexamined Patent Publication 6-332167 bulletin, photopolymer handbook, photopolymerization forum compile, Census of manufacturing meeting (1989), light polymerization technique (Technology), hummock, forever pine volume, THE NIKKAN KOGYO The material recorded in SHIMBUN, LTD. (1988).

(manufacturing method of circuit layout)

As long as the manufacturing method of circuit layout 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: relative to substrate, being made photosensitive transfer printing material of the invention The process that above-mentioned photosensitive polymer combination layer is contacted and is bonded with aforesaid substrate；To the above-mentioned photonasty after above-mentioned bonding process The process that the above-mentioned photosensitive polymer combination layer of transfer materials carries out pattern exposure；To upper after the above-mentioned process being exposed Photosensitive polymer combination layer is stated to be developed to form the process of pattern and to being not configured in the region of above-mentioned pattern The process that aforesaid substrate is etched.

Also, the manufacturing method of circuit layout of the invention preferably successively includes following process: relative to substrate, making this hair The process that the above-mentioned photosensitive polymer combination layer of bright photosensitive transfer printing material is contacted and is bonded with aforesaid substrate；It removes above-mentioned The process of the temporary support of photosensitive transfer printing material；The process that pattern exposure is carried out to above-mentioned photosensitive polymer combination layer； Developed above-mentioned photosensitive polymer combination layer come the process for forming pattern；And to the region for being not configured with above-mentioned pattern In the process that is etched of aforesaid substrate.

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 in eurymeric Actinic ray is irradiated, such as generates emulsion of acid etc. to improve the dissolubility of exposure portion, therefore using irradiation actinic ray When uncured in pattern exposure moment exposure portion and unexposed portion, when obtained pattern form is bad, can pass through Blanket exposure etc. is recycled (reprocessing) to substrate.Therefore, from so-called re-workability it is excellent from the viewpoint of, preferably Eurymeric.If also, expose once again to remaining photosensitive polymer combination layer to make the technology of different patterns not It is that photosensitive polymer combination layer then cannot achieve, therefore in the manufacturing method of circuit layout of the invention, preferably enumerate The mode of progress 2 times or more exposures.

< bonding process >

The manufacturing method of circuit layout of the invention, which is preferably comprised, makes photosensitive transfer printing material of the invention relative to substrate The above-mentioned photosensitive polymer combination layer process (bonding process) that contacts and be bonded with aforesaid substrate.

In above-mentioned bonding process, above-mentioned photosensitive transfer printing material is preferably made to contact and paste with the substrate for having conductive layer It closes.

Also, in above-mentioned bonding process, preferably contact above-mentioned conductive layer and above-mentioned photosensitive polymer combination layer Mode crimp.It, then can be by the photosensitive polymer combination layer of the formation of the pattern after exposure and development if aforesaid way Etching resist when being preferably used as being etched conductive layer.

It is not particularly limited, can make as the method for crimping above-mentioned substrate and above-mentioned photosensitive transfer printing material With well known transfer method and laminating method.

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

Crimping pressure and temperature in above-mentioned bonding process are not particularly limited, can be according to conductive layer and sense Material, conveying speed and used press-connection machine of photosensitive resin composition layer etc. are suitably set.Also, in photonasty When there is cover film on the photosensitive polymer combination layer of transfer materials, it is laggard that cover film is removed from photosensitive polymer combination layer Row crimping.

When above-mentioned 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 circuit layout of the invention, when for touch panel circuit layout, 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 circuit layout 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 circuit layout 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 electrode pattern of device or the wiring of edge lead division.

(circuit layout, which is formed, uses substrate)

The circuit layout formation substrate that is used in the present invention is preferably conductive layer on the surface of the substrate Substrate.Circuit layout is set as by being formed to conductive layer progress pattern.In this example, it is preferably set on the film base materials such as PET It is equipped with the substrate of multiple conductive layers such as metal oxide or metal.

< exposure process >

In the manufacturing method of circuit layout of the invention, preferably comprise to the above-mentioned photosensitive transfer printing after above-mentioned bonding process The above-mentioned photosensitive polymer combination layer of material carries out the process (exposure process) of pattern exposure.

In above-mentioned exposure process, preferably on the substrate for being provided with film, shone across the mask with specific pattern Penetrate actinic ray.In this process, photoacid generator decomposes and generates acid.By the catalysis of generated acid, film at Acid decomposability base contained in point 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 It can reduce and draw area shared by wiring, at least part (the especially electrode pattern of touch panel and extraction wiring of pattern Part) be preferably 100 μm of filaments below, more preferably 70 μm of filaments below.

Also, the exposure in above-mentioned exposure process can be for across the exposure of mask, or the number of laser etc. is utilized Code exposure, but preferably across the exposure of exposure mask.

The manufacturing method of the substrate of attached drawing case of the invention is preferably wrapped between above-mentioned bonding process and above-mentioned exposure process Containing the process for contacting above-mentioned photosensitive transfer printing material and exposure mask.If aforesaid way, then point of obtained pattern Resolution is more excellent.

Moreover, the manufacturing method of circuit layout of the invention is preferably wrapped between above-mentioned bonding process and above-mentioned exposure process Process containing the temporary support for removing above-mentioned photosensitive transfer printing material.At this point, the surface of above-mentioned photosensitive transfer printing material becomes Middle layer, but middle layer and exposure mask can also contacted to be exposed, it also can be across tens of μm of distances below It is exposed.Contact middle layer and exposure mask to be exposed.

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.

In addition, pattern exposure can be laggard from middle layer and the removing of photosensitive polymer combination layer by temporary support Row, can also be exposed via temporary support before removing temporary support, remove temporary support later.In order to prevent The mask contamination of contact of the based intermediate layer with mask and the influence for avoiding the foreign matter for being attached to mask from generating exposure, it is excellent Choosing is not removed temporary support and is exposed.In addition, pattern exposure can be the exposure across mask, it is also possible to be utilized The digital exposure of laser etc..

< developing procedure >

The manufacturing method of circuit layout of the invention is preferably comprised to the above-mentioned photonasty after the above-mentioned process being exposed Resin composition layer is developed to form the process of pattern (developing procedure).

Also, in developing procedure, the middle layer for the part being exposed and the photosensitive polymer combination layer one being exposed It rises and is removed.

Moreover, the middle layer in unexposed portion is also gone in the form for dissolving or dispersing in developer solution in developing procedure It removes.

The development of the above-mentioned photosensitive polymer combination layer being exposed in above-mentioned developing procedure can using developer solution come It carries out.

As developer solution, do not limited particularly as long as the exposed portion that can remove above-mentioned photosensitive polymer combination layer System, such as developer solution well known to being able to use the developer solution recorded in Japanese Unexamined Patent Publication 5-072724 bulletin etc..In addition, aobvious Shadow liquid is preferably the developer solution for making the exposed portion of above-mentioned photosensitive polymer combination layer carry out lysotype development behavior.As aobvious Shadow liquid, preferably aqueous alkali, such as more preferably by the compound of pKa=7~13 with 0.05mol/L (liter)~5mol/L The aqueous alkali that concentration includes.Developer solution can be further containing organic solvent, the surfactant etc. with water with Combination.Make For in the present invention it is preferable to use developer solution, such as can enumerate and be recorded in 0194 section of International Publication No. 2015/093271 Developer solution.

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 and middle layer, can remove exposed portion.Also, detergent etc. preferably after development, is passed through into spray Leaching removes development residue while being wiped with brush etc. to be blown.The liquid temperature of developer solution is preferably 20 DEG C~40 ℃。

Also, the mode long from the time being exposed to until developing, which can be played more, inhibits the pattern form in the present invention The effect of deformation.Can develop immediately after exposure, but from be exposed to development until time preferably from exposure through 0.5 hour or more is spent, is more preferably passed through 1 hour or more, the mode further preferably developed after 6 hours or more In, more play the effect for inhibiting the deformation of the pattern form in the present invention.

Also, the manufacturing method of the substrate of attached drawing case of the invention may include the work cleaned after development by water etc. Process well known to sequence or the 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.

The heating toasted afterwards preferably carries out in the environment of 8.1kPa~121.6kPa, more preferably 50.66kPa's or more It is carried out under environment.On the other hand, it is more preferably carried out under the environment of 111.46kPa or less, particularly preferably in 101.3kPa or less In the environment of carry out.

The temperature toasted afterwards is preferably 80 DEG C~250 DEG C, and more preferably 110 DEG C~170 DEG C, especially preferably 130 DEG C~ 150℃。

The time toasted afterwards is preferably 1 minute~30 minutes, more preferably 2 minutes~10 minutes, especially preferably 2 minutes ~4 minutes.

Baking can carry out under air environment afterwards, can also carry out in the case where nitrogen replaces environment.

The conveying speed of above-mentioned substrate when each process in the manufacturing method of circuit layout 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 circuit layout of the invention is preferably comprised to the above-mentioned base in the region for being not configured with above-mentioned pattern The process (etching work procedure) that plate is etched.

In above-mentioned etching work procedure, the pattern that above-mentioned developing procedure is formed by above-mentioned photosensitive polymer combination layer will be passed through The etching process of aforesaid substrate is carried out as etching resist.

The etching of aforesaid substrate can be to remember in 0048 section of Japanese Unexamined Patent Publication 2010-152155 bulletin~0054 section of grade The method of load 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 above-mentioned etching work procedure, for the pollution for preventing process line, the process that cleaning aforesaid substrate can be carried out as needed (cleaning process) and the process that aforesaid substrate is dried (drying process).About cleaning process, such as can enumerate normal Cleaning in warm (10 DEG C~35 DEG C) with pure water to substrate progress 10 seconds~300 seconds.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 circuit layout of the invention includes by above-mentioned photoresist preferably after above-mentioned etching work procedure The process (stripping process) that composition layer is removed using stripper.

After above-mentioned etching work procedure, remain the above-mentioned photosensitive polymer combination layer that pattern is formed.If being not required to Above-mentioned photosensitive polymer combination layer is wanted, then removes the above-mentioned photosensitive polymer combination layer of remaining whole.

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 with the substrate of above-mentioned photosensitive polymer combination layer etc. impregnate 5 minutes~30 points The method of clock.

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..

Also, the manufacturing method of circuit layout of the invention can be as needed by exposure process, developing procedure and etching Process is repeated 2 times above.

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 circuit layout 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.

The process > of < reduction luminous ray reflectivity

The manufacturing method of circuit layout 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 the preferred embodiment for the processing for reducing luminous ray reflectivity, in Japanese Unexamined Patent Publication 2014-150118 bulletin In 0017 section~0025 section and 0041 section, 0042 section, 0048 section and 0058 section of Japanese Unexamined Patent Publication 2013-206315 bulletin On the books, the content of the bulletin is incorporated into this manual.

< forms the process of insulating film on the aforesaid substrate being etched and forms new conductive layer on insulating film Process >

The manufacturing method of circuit layout of the invention is for example matched in established circuit it is also preferred that being included on aforesaid substrate The process of insulating film is formed on line (the above-mentioned conductive layer being etched) and the work of new conductive layer is formed on insulating film Sequence.

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.

Also, the manufacturing method of circuit layout of the invention can pass through above-mentioned new conductive layer same as described above Method forms etching resist and is etched, and can also be etched additionally by well known method.

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

Also, in the manufacturing method of circuit layout of the invention, it is also preferred that substrate be respectively provided on the surface of two sides it is more A conductive layer gradually or is formed simultaneously circuit to the conductive layer formed on the surface of the two sides of substrate.It is tied by this kind Structure can be formed in and be formed with the first conductive pattern (the first circuit layout) and the table in the other side on the surface of the side of substrate It is formed with the circuit layout of the second conductive pattern (second circuit wiring) on face, preferably forms touch panel circuit layout.

(circuit layout and circuit substrate)

Circuit layout of the invention is the circuit layout of the manufacturing method manufacture of circuit layout through the invention.

Circuit substrate of the invention is the circuit layout of the manufacturing method manufacture with circuit layout 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 circuit layout as the manufacturing method manufacture for having circuit layout 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 circuit layout 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 EL The image display devices such as display device and liquid crystal display device.

(touch panel and touch panel display device)

Touch panel of the invention is that at least there is the circuit of the manufacturing method manufacture of circuit layout through the invention to match The touch panel of line.Also, touch panel of the invention preferably at least has transparent substrate, electrode and insulating layer or protection Layer.

Touch panel display device of the invention is that at least have the manufacturing method manufacture of circuit layout through the invention Circuit layout 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 of the invention and touch panel display device 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 touching control panel, 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-control Panel technology " (on July 6th, 2009, the distribution of Techno Times Co., Ltd.), three paddy hero two is edited, " the skill of touch panel Art and exploitation " (in December, 2004, CMC publish), 2009 Forum T-11 of FPD International lecture textbook, It is tied disclosed in Cypress Semiconductor Corporation application note (application note) AN2292 etc. Structure.

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 in addition, not having It specifies, then " part ", " % " are quality criteria.

(polymer in photosensitive polymer combination layer)

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)

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

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

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

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

The 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.

The 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%).

The 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.

The 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%).

The 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%).

The synthesis example > 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 (38.70 will be mixed with Part), AA (1.47 parts), CHA (59.83 parts), V-601 (4.1 parts), PGMEA (75.0 parts) solution spend and drop onto for 2 hours It is maintained in 90 DEG C ± 2 DEG C of 3 mouthfuls of flask solution.After drippage, obtained and being stirred 2 hours in 90 DEG C ± 2 DEG C Polymer A-1 (40.0 mass % of solid component concentration).

The synthesis example > of < polymer A-2~A-5

Type by monomer etc. is changed as shown in following tables, and other conditions are then in method identical with A-1 It is synthesized.The solid component concentration of polymer 40 mass % have been set as.Each Component units of table 1 are (by each monomer polymerization Made of monomeric unit) content unit be mol%.

[table 1]

[photoacid generator]

B-1:BASF JAPAN LTD. Irgacure PAG-103, following compounds

[chemical formula 14]

B-2: the compound of structure shown in following (is 0227 Duan Zhongji in Japanese Unexamined Patent Publication 2013-047765 bulletin The compound of load, and synthesized according to the method recorded in 0227 section.)

[chemical formula 15]

B-3: the compound of structure shown in following is (according in International Publication No. 20,14/,020,984 0160 Duan Zhongji The method of load is synthesized.)

[chemical formula 16]

B-4: the compound of structure shown in following (is 0208 Duan Zhongji in Japanese Unexamined Patent Publication 2012-163937 bulletin The compound of load, and synthesized according to the method recorded in 0212 section.)

[chemical formula 17]

[sensitizer]

E-1:Kawasaki Kasei Chemicals Ltd. ANTHRACURE (registered trademark) UVS-1331, it is following Compound is (in addition, Bu indicates butyl.)

[chemical formula 18]

[surfactant]

E-1: the compound of structure shown in following

[chemical formula 19]

[alkali compounds]

D-1: the compound (CMTU) of structure shown in following

[chemical formula 20]

The synthesis example > of < polymer C-1

In following example, following abbreviation respectively indicates following compound.

AANa: sodium acrylate (Tokyo Chemical Industry Co., Ltd. system)

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

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

PGME (75.0 parts) are added in 3 mouthfuls of flasks, 90 DEG C are warming up under nitrogen environment.AANa (45.37 will be mixed with Part), HEMA (54.63 parts), V-601 (4.1 parts), PGME (75.0 parts) solution spend to have dropped onto for 2 hours and be maintained at 90 DEG C In ± 2 DEG C of 3 mouthfuls of flask solution.After drippage, polymer C-1 has been obtained and stirring 2 hours in 90 DEG C ± 2 DEG C (40.0 mass % of solid component concentration).

(embodiment 1)

The preparation > of < middle layer composition

It mixed, dissolved according to consisting of, and be filtered with the polytetrafluoroethylene (PTFE) filter in 5.0 μm of aperture, To obtain middle layer composition (5.0 mass % of solid component concentration).

Ion exchange water: 47.5 mass parts

Methanol: 47.5 mass parts

Hydroxypropyl methyl cellulose (HPMC, Shin-Etsu Chemical Co., Ltd. TC-5E): 5.0 mass parts

The 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, thus Photosensitive polymer combination is arrived.

PGMEA:424.5 mass parts

Polymer A-1:237.0 mass parts

Photoacid generator B-1:5.0 mass parts

Surfactant E-1:0.1 mass parts

Alkali compounds D-1:0.1 mass parts

The 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, middle layer composition is coated in such a way that dry film thickness becomes 1.0 μm by slit-shaped nozzle.Later, 100 DEG C convection oven (convection oven) in dried 2 minutes, then utilize slit-shaped to spray photosensitive polymer combination Mouth is coated in such a way that dry film thickness becomes 3.0 μm.Later, 2 minutes have been dried in 100 DEG C of convection oven, most Polyethylene film (Tredegar Co., Ltd. system, OSM-N) is crimped as cover film afterwards, to make photosensitive Property transfer materials.

(embodiment 2)

Middle layer combination has been made in the way of forming documented by the mass ratio of the content in solid component becomes table 2 Object has made photosensitive transfer printing material in the same manner as example 1 in addition to this.

(embodiment 3~25 and 27~31)

The preparation > of < thermoplastic resin composition H1

Methanol: 11.1 mass parts

Propylene glycol methyl ether acetate: 6.36 mass parts

Methyl hexyl ketone: 52.4 mass parts

Methyl methacrylate/2- ethylhexyl acrylate/benzyl methacrylate/methacrylic acid copolymer is (altogether Poly- ratio of components (molar ratio)=55/11.7/4.5/28.8, molecular weight=70 DEG C of 100,000, Tg ≈): 5.83 mass parts

Styrene/acrylic acid co-polymer (copolymerization composition ratios (molar ratio)=63/37, weight average molecular weight=10,000, Tg ≈ 100 DEG C): 13.6 mass parts

Monomer 1 (ethylene oxide (EO) modified bisphenol A dimethylacrylate (EO10 molar equivalent), ProductName: BPE- 500, Shin-Nakamura Chemical Co., Ltd. systems): 9.1 mass parts

Fluorine system polymer: 0.54 mass parts

Above-mentioned fluorine system polymer is 40 parts of C₆F₁₃CH₂CH₂OCOCH=CH₂With 55 parts of H (OCH (CH₃)CH₂)₇OCOCH=CH₂ With 5 parts of H (OCHCH₂)₇OCOCH=CH₂Copolymer, weight average molecular weight be 30,000,30 mass % solution (product of methyl hexyl ketone Name: Megaface F780F, DIC Corporation system).

The preparation > of < middle layer composition

Middle layer combination has been made in the way of forming documented by the mass ratio of the content in solid component becomes table 2 Object has carried out mixing, dissolution in the same manner as example 1 in addition to this, and with the polytetrafluoroethylene (PTFE) mistake in 5.0 μm of aperture Filter is filtered, and has respectively obtained the middle layer composition (solid component concentration of embodiment 3~25 and 27~31 whereby 5.0 mass %).

The production > of < photosensitive transfer printing material

In 50 μm of thickness of the polyethylene terephthalate film (PET (A)) for becoming temporary support, by thermoplastic resin Oil/fat composition H1 is coated in such a way that dry film thickness becomes 5.0 μm by slit-shaped nozzle.Later, in 100 DEG C of pair Dried 2 minutes in stream baking oven, later by middle layer composition using slit-shaped nozzle in such a way that dry film thickness is as 1.0 μm It is coated with.Later, it has been dried in 100 DEG C of convection oven 2 minutes, photosensitive polymer combination is then utilized into slit Shape nozzle is coated in such a way that dry film thickness becomes 3.0 μm.Later, 2 points have been dried in 100 DEG C of convection oven Clock is finally crimped polyethylene film (Tredegar Co., Ltd. system, OSM-N) as cover film, thus production Photosensitive transfer printing material.

(embodiment 26)

B-4 is used as photoacid generator, and is added to the sensitizer of 5.0 mass parts, and the additive amount of polymer is subtracted Lack 5.0 mass parts, makes photosensitive transfer printing material in a manner of identical with embodiment 23 in addition to this.

(embodiment 32 and 33)

Used following thermoplastic resin composition H2 or H3 respectively as thermoplastic resin composition, in addition to this with The identical mode of embodiment 17 has made the photosensitive transfer printing material of embodiment 32 and 33.

The preparation > of < thermoplastic resin composition H2

Methanol: 11.1 mass parts

Propylene glycol methyl ether acetate: 6.36 mass parts

Methyl hexyl ketone: 52.4 mass parts

Styrene/acrylic acid co-polymer (copolymerization composition ratios (molar ratio)=63/37, weight average molecular weight=10,000, Tg ≈ 100 DEG C): 19.43 mass parts

Monomer 1 (ProductName: BPE-500, Shin-Nakamura Chemical Co., Ltd. system): 9.1 mass parts

Fluorine system polymer (ProductName: Megaface F780F, DIC Corporation system): 0.54 mass parts

The preparation > of < thermoplastic resin composition H3

Methanol: 11.1 mass parts

Propylene glycol methyl ether acetate: 6.36 mass parts

Methyl hexyl ketone: 52.4 mass parts

Methyl methacrylate/2- ethylhexyl acrylate/benzyl methacrylate/methacrylic acid copolymer is (altogether Poly- ratio of components (molar ratio)=55/11.7/4.5/28.8, molecular weight=70 DEG C of 100,000, Tg ≈): 19.43 mass parts

Monomer 1 (ProductName: BPE-500, Shin-Nakamura Chemical Co., Ltd. system): 4.6 mass parts

Fluorine system polymer (ProductName: Megaface F780F, DIC Corporation system): 0.54 mass parts

(comparative example 1 and 5~8)

It is not coated with thermoplastic resin composition and middle layer composition and is respectively coated documented photosensitive in following table 2 Property resin combination, made respectively in the same manner as example 1 in addition to this comparative example 1 and 5~8 photonasty turn Print material.

(comparative example 2~4)

Respectively using the middle layer composition recorded in following table 2, distinguished in addition to this in mode same as Example 3 The photosensitive transfer printing material of comparative example 2~4 is made.

[performance evaluation]

It has used and sputtering legal system is passed through with thickness 500nm on 188 μm of thickness polyethylene terephthalate (PET) film Make the pet substrate for having the attached layers of copper of layers of copper.

< transferability evaluates >

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 evaluates >

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

< developing solution dissolution evaluates >

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 with 300mJ/cm²Light exposure carried out blanket exposure, placed 1 hour in 23 DEG C After remove temporary support, using 28 DEG C of 1.0 mass % aqueous sodium carbonates, sprayed while changing developing time Leaching development.The evaluation for carrying out developing solution dissolution by finding out the time since development until residual film disappears.

5: the time since development until residual film disappears was less than 5 seconds

4: the time since development until residual film disappears was 5 seconds more than and less than 10 seconds

3: the time since development until residual film disappears was 10 seconds more than and less than 30 seconds

2: the time since development until residual film disappears was 30 seconds more than and less than 60 seconds

1: the time since development until residual film disappears is 60 seconds or more

[table 2]

In addition, the value of the content (quality %) of each resin of the middle layer in table 2 indicates in above-mentioned middle layer composition The ratio in 5.0 mass parts of resin used.

Also, the detailed content for the contracted notation recorded in table 2 is as follows.

HPMC: hydroxypropyl methyl cellulose, Shin-Etsu Chemical Co., Ltd. TC-5E low molecular weight type

HPMCH: hydroxypropyl methyl cellulose, Shin-Etsu Chemical Co., Ltd. TC-5S high molecular weight type

HPC: hydroxypropyl cellulose, NIPPON SODA CO., LTD. Nisso HPC SSL molecular weight 40,000

HPCH: hydroxypropyl cellulose, NIPPON SODA CO., LTD. Nisso HPC L molecular weight 140,000

PhNv: phenol novolaks, ASAHI YUKIZAI CORPORATION RM-25

PA: acrylic resin (polymer C-1), sodium acrylate/acrylic acid hydroxyl ethyl ester copolymer (molar ratio=50: 50), molecular weight 20,000

PVA: polyvinyl alcohol, Kuraray Co., Ltd. KURARAY PVA-205

PVP: polyvinylpyrrolidone, NIPPON SHOKUBAI CO., LTD. polyvinylpyrrolidone K-30

PAA: polyacrylic acid, TOAGOSEI CO., LTD. Aron A-10SL

PAANa: Sodium Polyacrylate, TOAGOSEI CO., LTD. Aron A-210

PEO: polyethylene oxide, MEISEI CHEMICAL WORKS, LTD. ALK0X L-6

PEI: polyethyleneimine, NIPPON SHOKUBAI CO., LTD. EPOMIN SP-018

(embodiment 41)

To use the photosensitive transfer printing material of the middle layer and photosensitive polymer combination recorded in embodiment 1 with The method recorded in embodiment 1 is made, and pixel deformation evaluation and developing solution dissolution evaluation in carried out under Change is stated, has carried out identical performance evaluation in addition to this.

< pixel deformation evaluates >

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, determining that 5 are until the evaluation of above-mentioned transferability becomes in the stacking Only, roll temperature is improved to have made sample.

After having removed temporary support, make 3 μm~20 μm of line width of line and space pattern (Duty ratio 1:1) mask and intermediate Layer contact, after being exposed with extra-high-pressure mercury vapour lamp, is developed after placing 6 hours in 23 DEG C.Development uses 28 DEG C 1.0 mass % aqueous sodium carbonates have been carried out 40 seconds with spray development.10 μm of line and space diagram are formed by the above method Case, finding out the ratio between line width and space width becomes the light exposure of 1:1, observes its exposure by scanning electron microscope (SEM) The deflection of the front end of 5 μm of line and space pattern in amount, has carried out the evaluation of pixel deformation.3 the above are can actually make Grade.

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 remains without pixel

< developing solution dissolution evaluates >

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.

After removing temporary support, with 300mJ/cm²Light exposure carried out blanket exposure, placed 1 hour in 23 DEG C Between after, using 28 DEG C of 1.0 mass % aqueous sodium carbonates, spray development has been carried out while changing developing time.Pass through The evaluation for finding out the time since development until residual film disappears to carry out developing solution dissolution.

5: the time since development until residual film disappears was less than 5 seconds

4: the time since development until residual film disappears was 5 seconds more than and less than 10 seconds

3: the time since development until residual film disappears was 10 seconds more than and less than 30 seconds

2: the time since development until residual film disappears was 30 seconds more than and less than 60 seconds

1: the time since development until residual film disappears is 60 seconds or more

(embodiment 42~44)

The photosensitive transfer printing material of the middle layer and photosensitive polymer combination recorded in embodiment 2~4 will have been used Material is made in the method recorded in embodiment 1, in pixel deformation evaluation and developing solution dissolution evaluation, is carried out Change identical with the evaluation of embodiment 41, has carried out identical performance evaluation in addition to this.

[table 3]

(embodiment 101)

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.

In addition, solid line portion SL and grey portion G are light shielding part, the hypothetical earth's surface of dotted line part DL in pattern A shown in Fig. 2 The frame of alignment is shown.

Temporary support is removed later, is developed, 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 is provided with (below also referred to as " pattern B " using with the state being aligned.) opening portion Light shield carried out pattern exposure, development, washing.

In addition, grey portion G is light shielding part in pattern B shown in Fig. 3, dotted line part DL illustrates the frame of alignment hypothetically.

Later, layers of copper is etched using Cu-02, and is shelled using stripper (10 mass % sodium hydrate aqueous solution) Circuit layout substrate has been obtained from remaining photosensitive polymer combination layer.

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

(embodiment 102~133)

The photosensitive transfer printing material obtained in embodiment 2~33 is used to carry out comment identical with embodiment 101 respectively Valence is perfect pattern as a result without peeling and missing etc..

(embodiment 141)

In 100 μ m-thick PET base materials as the 2nd layer conductive layer and by tin indium oxide (ITO) by sputtering with 150nm Thickness is formed a film, above as the 1st layer conductive layer and by copper by vacuum vapour deposition with 200nm thickness carried out at Circuit forming board has been made in film 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).Removing temporary support has simultaneously carried out contact patterns exposure using the light shield for the structure for being provided with pattern A Light.Pattern exposure so is carried out after removing temporary support, has carried out evaluation identical with embodiment 101 in addition to this.

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

(embodiment 142~144)

The photosensitive transfer printing material obtained in embodiment 2~4 is used to carry out comment identical with embodiment 141 respectively Valence is perfect pattern as a result without peeling or missing etc..

Symbol description

10- temporary support, 12- middle layer, 14- photosensitive polymer combination layer, 16- cover film, SL- solid line portion, G- Grey portion, DL- dotted line part.

Claims (12)

1. a kind of photosensitive transfer printing material, successively includes

Temporary support；

Middle layer；And

Photosensitive polymer combination layer,

The photosensitive polymer combination layer contains polymer and photoacid generator, and the polymer includes to have by sour decomposability base The Component units of the acidic group of protection,

The middle layer contains resin C, and the resin C is water-soluble or alkali solubility, and includes with phenolic hydroxyl group or not direct It is connected to the Component units of the alcohol hydroxyl group of main chain.

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

Between the temporary support and the middle layer, further there is thermoplastic resin layer.

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

The resin C is selected from by linear phenol-aldehyde resin, modified cellulose resin and acrylic resin group with hydroxyl At group at least one kind of resin.

4. photosensitive transfer printing material described in any one of claim 1 to 3, wherein

The middle layer further contains the water-soluble or alkali-soluble resin D other than the resin C.

5. photosensitive transfer printing material according to claim 4, wherein

The resin D is to be selected from by polyacrylic acid, Sodium Polyacrylate, polyacrylamide, polyethylene oxide, polyethyleneimine, gather At least one kind of resin in the group of vinyl alcohol and polyvinylpyrrolidone composition.

6. photosensitive transfer printing material according to claim 4 or 5, wherein

The resin D is at least one kind of resin in the group being made of polyvinyl alcohol and polyvinylpyrrolidone.

7. the photosensitive transfer printing material according to any one of claim 4~6, wherein

The mass ratio that contains of the resin C and the resin D in the middle layer are resin C: resin D=5:1~1:2.

8. photosensitive transfer printing material according to claim 7, wherein

The mass ratio that contains of the resin C and the resin D in the middle layer are resin C: resin D=4:1~2:1.

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

The Component units with the acidic group protected by sour decomposability base are the Component units indicated with following formula A,

In formula A, R³¹And R³²Separately indicate hydrogen atom, alkyl or aryl, at least R³¹And R³²Any of be alkane Base or aryl, R³³Indicate alkyl or aryl, R³¹Or R³²Optionally with R³³It connects and forms cyclic ether, R³⁴Indicate hydrogen atom or first Base, X⁰Indicate singly-bound or arlydene.

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

The glass transition temperature of the polymer in the photosensitive polymer combination layer is 90 DEG C or less.

11. a kind of manufacturing method of circuit layout successively includes following process:

Relative to substrate, make the photoresist group of photosensitive transfer printing material according to any one of claims 1 to 10 Close the process that nitride 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 being exposed and form pattern；With And

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

12. a kind of manufacturing method of circuit layout successively includes following process:

Relative to substrate, make the photoresist group of photosensitive transfer printing material according to any one of claims 1 to 10 Close the process that nitride layer is contacted and is bonded with the substrate；

The process for removing the temporary support of the photosensitive transfer printing material；

The process that pattern exposure is carried out to the photosensitive polymer combination layer；

The process developed to the photosensitive polymer combination layer and form pattern；And

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