CN110225665A

CN110225665A - Photosensitive element, barrier layer form the manufacturing method for using resin combination, the forming method of resist pattern and printing distributing board

Info

Publication number: CN110225665A
Application number: CN201910501676.1A
Authority: CN
Inventors: 粂壮和; 小野博史; 松村辽
Original assignee: Hitachi Chemical Co Ltd
Current assignee: Lishennoco Co ltd
Priority date: 2015-07-30
Filing date: 2016-07-20
Publication date: 2019-09-10
Anticipated expiration: 2036-07-20
Also published as: KR20230129587A; TW201710796A; KR20180035827A; TWI705307B; CN107924130A; CN110161802A; JPWO2017018299A1; CN110225665B; CN110161802B; WO2017018299A1; JP6870612B2; MY196431A; KR102572426B1; CN107924130B

Abstract

The present invention provides a kind of photosensitive element, barrier layer formation resin combination, the forming method of resist pattern and the manufacturing method of printing distributing board.The photosensitive element successively has support membrane, barrier layer and photosensitive layer, and the alcohols of water-soluble resin and carbon number more than or equal to 3 is contained on above-mentioned barrier layer, can be improved the fissility of barrier layer and support membrane without using removing promotor.

Description

Photosensitive element, barrier layer form the formation side with resin combination, resist pattern The manufacturing method of method and printing distributing board

The application be the applying date be on July 20th, 2016, it is entitled " photosensitive application No. is 201680044650.3 Property element, barrier layer formed use resin combination, the forming method of resist pattern and printing distributing board manufacturing method " The divisional application of Chinese patent application.

Technical field

This disclosure relates to photosensitive element, barrier layer formed with resin combination, resist pattern forming method and The manufacturing method of printing distributing board.

Background technique

In the past, in the manufacturing field of printing distributing board, as the resist material for etching process or plating etc. Material, is widely used photosensitive polymer combination and has on support membrane and be formed by layer using photosensitive polymer combination The photosensitive element of (hereinafter also referred to as " photosensitive layer ").

Printing distributing board is to be manufactured using above-mentioned photosensitive element for example, by following step.That is, firstly, will The photosensitive layer of photosensitive element is laminated on the circuits formation substrate such as copper-clad laminated board.At this point, with photosensitive layer and support membrane The mode that the face of the face opposite side of contact is sealed at the face of the formation circuit of circuit formation substrate is laminated.In addition, lamination Such as (normal pressure laminating method) is carried out on substrate by the way that photosensitive layer heating is crimped on circuit formation.

Then, it using mask film etc., is exposed across desired region of the support membrane to photosensitive layer, to be produced from By base.Generated free radical by several response paths facilitates the cross-linking reaction of photopolymerizable compound, and (photocuring is anti- It answers).Next, film stripping will be supported, then the uncured portion of photosensitive layer is dissolved using developer solution or dispersion removes, thus shape At resist pattern.Next, implementing etching process or plating using resist pattern as resist and forming conductor figure (removal) is finally removed by case by the photocuring portion (resist pattern) of photosensitive layer.

In addition, in recent years, having studied and being exposed after removing support membrane before exposure to photosensitive layer, to be formed excellent The method of resist pattern.But when being exposed after removing support membrane to photosensitive layer, generated free radical meeting and air In oxygen contact, so that free radical promptly stabilizes (inactivation) so that the photocuring reaction of photopolymerizable compound be difficult into Row.Therefore, in the method, in order to mitigate the influence that film stripping will be supported to generate to be mixed into when being exposed with oxygen, grind Study carefully and (such as has been joined using the photosensitive element for having the barrier layer (barrier layer) with gas barrier property between support membrane and photosensitive layer According to Patent Documents 1 to 3).

Existing technical literature

Patent document

Patent document 1: No. 5483734 bulletins of Japanese Patent No.

Patent document 2: Japanese Unexamined Patent Publication 2013-24913 bulletin

Patent document 3: No. 5551255 bulletins of Japanese Patent No.

Summary of the invention

Subject to be solved by the invention

With regard to having the photosensitive element on the barrier layer containing water-soluble resin as recording in above patent document 1~3 For, due to the compatibility of water-soluble resin and support membrane height, thus the cementability sometimes between barrier layer and support membrane is strong.? In this case, removing support membrane becomes difficult, sometimes barrier layer or photosensitive when removing support membrane from the barrier layer of photosensitive element Layer can defect.

So far, it proposes by organic with being added in resin combination in the barrier layer formation containing water-soluble resin Silicon or fluorine system surfactant etc. remove promotor, to reduce the cementability between barrier layer and support membrane, improve barrier layer With the scheme of the fissility of support membrane.

However known there are the following problems: due to adding the removing promotor such as these surfactants, causing to be formed by It is muddy that barrier layer becomes easy generation.Further, since the removing promotor such as surfactant is present in barrier layer and support membrane Interface, thus from the viewpoint of long-range, it changes there are interface composition or the cementability between barrier layer and support membrane is sent out Changing, it is difficult to maintain stable support membrane fissility (fissility on barrier layer and support membrane) such problems.

The disclosure be made in view of project possessed by above-mentioned conventional art, even if its purpose is to provide one kind not It also can be improved photosensitive element, the barrier layer formation resin group of the fissility of barrier layer and support membrane using removing promotor Close object, the forming method of resist pattern and the manufacturing method of printing distributing board.

The method to solve the problem

To achieve the goals above, the disclosure provides a kind of photosensitive element, successively has support membrane, barrier layer and sense The alcohols of water-soluble resin and carbon number more than or equal to 3 is contained on photosphere, above-mentioned barrier layer.

The photosensitive element of the disclosure is by the alcohols in barrier layer containing carbon number more than or equal to 3, thus even if not It also can be improved the fissility of barrier layer and support membrane using removing promotor.According to such photosensitive element, can will prop up Support film is swimmingly removed from barrier layer, it is thus possible to inhibit the defect of barrier layer and photosensitive layer.Further, since even if not using Removing promotor also can be improved the fissility of barrier layer and support membrane, it is thus possible to inhibit because remove promotor there are due to draw The generation of the barrier layer muddiness risen and the ongoing change of support membrane fissility.Therefore it may also be said that by using the disclosure Photosensitive element is capable of forming resolution ratio and the excellent resist pattern of resist pattern shape.

In the photosensitive element of the above-mentioned disclosure, alcohols of the above-mentioned carbon number more than or equal to 3 can be containing by following chemical formula (1) at least one of the group of the composition of compound represented by compound represented by~(3) and the following general formula (4).According to this The photosensitive element of sample can more improve the fissility of barrier layer and support membrane.

[changing 1]

[changing 2]

[changing 3]

[changing 4]

[in general formula (4), R¹¹Indicate alkyl, R¹²Indicate alkylidene, R¹¹Group and R¹²The sum of the carbon number of group be greater than Or it is equal to 3.]

In the photosensitive element of the above-mentioned disclosure, dissolution of alcohols of the above-mentioned carbon number more than or equal to 3 for 20 DEG C of water Degree can be greater than or equal to 300mL/ water 100mL.According to such photosensitive element, it can more inhibit the layer point on barrier layer From being capable of providing practical excellent photosensitive element.

In the photosensitive element of the above-mentioned disclosure, the above-mentioned carbon number in above-mentioned barrier layer is greater than or equal to containing for 3 alcohols Amount more than 0 mass % and can be less than or equal to 2.0 mass % on the basis of the total amount on above-mentioned barrier layer.According to such photosensitive Property element, is able to suppress the diffusion of the alcohols in subsequent handling.

In the photosensitive element of the above-mentioned disclosure, above-mentioned water-soluble resin can contain polyvinyl alcohol.According to such photosensitive Property element, can more improve the gas barrier property on barrier layer, can more inhibit to generate by exposing active ray used The inactivation of free radical.

In the photosensitive element of the above-mentioned disclosure, above-mentioned support membrane can be polyester film.According to such photosensitive element, It can be improved the mechanical strength and heat resistance of support membrane, and be able to suppress the generated resistance when forming barrier layer on support membrane A problem that gauffer of barrier, it can be improved workability.

In addition, the disclosure also provides a kind of barrier layer formation resin combination, it is greater than containing water-soluble resin, carbon number Or alcohols and water equal to 3.According to such barrier layer formation resin combination, even if also can without using removing promotor It is enough to form the barrier layer excellent with the fissility of support membrane.

The barrier layer of the disclosure is formed in resin combination, and alcohols of the above-mentioned carbon number more than or equal to 3 can be containing by upper State at least one in the group of the composition of compound represented by compound represented by chemical formula (1)~(3) and above-mentioned general formula (4) Kind.According to such barrier layer formation resin combination, it is capable of forming the barrier layer more excellent with the fissility of support membrane.

The barrier layer of the disclosure is formed in resin combination, and alcohols of the above-mentioned carbon number more than or equal to 3 is for 20 DEG C The solubility of water can be greater than or equal to 300mL/ water 100mL.It, being capable of shape according to such barrier layer formation resin combination Stratification separation is able to the barrier layer inhibited.

The barrier layer of the disclosure is formed in resin combination, and above-mentioned carbon number is opposite more than or equal to the content of 3 alcohols 100~500 mass parts can be set as in 500 mass parts of water.According to such barrier layer formation resin combination, be capable of forming with The superior barrier layer of the fissility of support membrane, and since the dissolubility of water-soluble resin improves, it is thus possible to it is easily formed Barrier layer.

The barrier layer of the disclosure is formed in resin combination, and above-mentioned water-soluble resin can contain polyvinyl alcohol.According to this The barrier layer of sample, which is formed, uses resin combination, is capable of forming the more excellent barrier layer of gas barrier property.

In addition, the disclosure also provides a kind of forming method of resist pattern, have: using the photosensitive of the above-mentioned disclosure Property element, configures in order the process of photosensitive layer, barrier layer and support membrane on substrate since the substrate-side；Remove above-mentioned support Film, using active ray, above-mentioned photosensitive layer is exposed across above-mentioned barrier layer process；And it is removed from aforesaid substrate The uncured portion of above-mentioned photosensitive layer and the process on above-mentioned barrier layer.According to the forming method of such resist pattern, due to making Resist pattern is formed with the photosensitive element of the above-mentioned disclosure, it is thus possible to form resolution ratio and resist pattern shape is excellent Different resist pattern.

The disclosure further provides for a kind of manufacturing method of printing distributing board, has: resisting to by the above-mentioned disclosure The substrate that the forming method of erosion agent pattern forms resist pattern is etched or plating, to form conductor figure The process of case.According to the manufacturing method of such printing distributing board, due to the formation of the resist pattern by the above-mentioned disclosure Method forms resist pattern, it is thus possible to resolution ratio and the excellent resist pattern of resist pattern shape are formed, it can The manufacturing method for being suitable for the printing distributing board of densification of printing distributing board is provided.

The effect of invention

According to the disclosure, it is possible to provide a kind of stripping that can be improved barrier layer and support membrane without using removing promotor Photosensitive element, barrier layer formation resin combination, the forming method of resist pattern and printing distributing board from property Manufacturing method.

Detailed description of the invention

Fig. 1 is the schematic section for indicating an embodiment of photosensitive element for the disclosure.

Fig. 2 is the figure for schematically showing an example of manufacturing process of the printing distributing board using semi-additive process.

Specific embodiment

Hereinafter, the preferred embodiment of the disclosure is described in detail on one side referring to attached drawing on one side as needed.With Under embodiment in, it goes without saying that except be considered the case where especially expressing and in principle be obviously necessary situation etc. with Outside, constituent element (also include element step etc.) it is not necessary to.This is also the same for numerical value and range, should be interpreted that not The disclosure can be improperly restricted.

It should be noted that in the present specification, so-called methyl (acrylic acid) refers to acrylic acid and corresponding methyl At least one of acrylic acid.In addition, expression other similar for (methyl) acrylate etc. is also the same.

In addition, in the present specification, " process " this term refers not only to independent process, even if can not be with other works In the case that sequence is clearly distinguish, as long as can be realized the predictive role of the process, it is also contained in this term.

Further, in the present specification, the numberical range indicated using "~" is indicated recorded in the front and back comprising "~" Numerical value respectively as minimum value and maximum value range.In addition, in the numberical range recorded interim in the present specification, certain The upper limit or lower limit of the numberical range in one stage is alternatively at the upper limit or lower limit of the numberical range in other stages.This Outside, in numberical range documented in the present specification, the upper limit or lower limit of the numberical range is alternatively in embodiment Shown in be worth.In addition, in the present specification, " layer " this term in addition to forming by entire surface when being observed as plan view Other than the structure of shape, also comprising the structure for the shape being partly formed.

[photosensitive element]

As shown in Figure 1, the photosensitive element 1 of present embodiment successively has support membrane 2, barrier layer 3 and photosensitive layer 4, Other layers such as protective layer 5 can also be further equipped with.In addition, water-soluble resin is contained on above-mentioned barrier layer and carbon number is greater than or equal to 3 Alcohols.By using the photosensitive element of present embodiment, the fissility of barrier layer and support membrane can be improved.In addition, this The photosensitive element of embodiment is separated due to being able to suppress the layer on barrier layer, thus becomes practical excellent element.Hereinafter, Each layer in photosensitive element involved in present embodiment is described in detail.

< support membrane >

As the support membrane of present embodiment, can use without particular limitation.Such as it can enumerate: poly terephthalic acid The polyester films such as glycol ester (PET), polybutylene terephthalate (PBT) (PBT) and poly- 2,6- (ethylene naphthalate) (PEN), And the polyolefin films such as polypropylene and polyethylene.Wherein it is possible to use polyester film.By using polyester film as support membrane, from And have the tendency that the mechanical strength that can be improved support membrane and heat resistance.In addition, by using polyester film, to be able to suppress When forming barrier layer on support membrane a problem that the gauffer on generated barrier layer, the tendency of workability can be improved.This Outside, it from the viewpoint of being able to suppress resist pattern and generating small fall off, also can be used comprising particle (lubricant etc.) Polyester film.It, can be with particle (lubricant etc.) one in the case where using the polyester film comprising particle (lubricant etc.) Barrier layer is formed on the face of side.As such polyester film, can be used such as be mixed with particle (lubricant) polyester film, Two sides forms the polyester film of the layer containing particle (lubricant etc.) or forms the poly- of the layer containing particle (lubricant etc.) in one side Ester film.It should be noted that support membrane, which can be single layer, is also possible to multilayer.

As the method to particles such as support membrane additional lubricants, for example, the following methods can be used: being mixed in support membrane The method of particle (lubricant etc.)；It is being supported using method well known to roller coating, flow coat, spraying, curtain painting, dip-coating, slot die etc. The method of the layer containing particle (lubricant etc.) is formed on film.

The mist degree of support membrane can be 0.01~5.0%, 0.01~1.5%, 0.01~1.0% or 0.01~0.5%.It is logical The mist degree is crossed more than or equal to 0.01%, to have the tendency that easily fabricated support membrane itself, if it is less than or be equal to 5.0%, Then there is the tendency for being easy to detect the foreign matter in photosensitive layer when forming the photosensitive layer of photosensitive element.Here, " mist degree " is Refer to turbidity.Mist degree in the disclosure refers to the method according to 7105 defined of JIS K, uses commercially available turbidity meters (turbidity Meter) measurement value.It is commercially available turbid that mist degree can use such as NDH-5000 (Nippon Denshoku Industries Co., Ltd.'s system, trade name) etc. Degree meter is to measure.

In addition, support membrane can also be used from commercially available general industry in film, acquisition can be as the support membrane of photosensitive element The film used is suitably processed and is used.Specifically, can enumerate for example as " FB-40 " of PET film (Dongli Ltd.'s system, Product name), " A4100 ", " A1517 " (Toyo Boseki K. K's system, product name), " G2H " (Di Ren Du Pont membrane Co., Ltd. System, product name) etc..

The thickness of support membrane can for 1~200 μm, 1~100 μm, 1~60 μm, 5~60 μm, 10~60 μm, 10~50 μm, 10~40 μm, 10~30 μm or 10~25 μm.It is greater than or equal to 1 μm by the thickness of support membrane, is able to suppress removing support membrane When support membrane rupture.In addition, the thickness by support membrane is less than or equal to 200 μm, to there is the benefit being easy to get economically Tendency.

The barrier layer < >

The photosensitive element of present embodiment has barrier layer between support membrane and photosensitive layer.In addition, barrier layer is contained Water-soluble resin and carbon number are greater than or equal to 3 alcohols.Photosensitive element according to the present embodiment, even if in barrier layer not Support membrane also can be swimmingly removed from barrier layer in the case where the promotor containing removing, therefore across blocking after removing support membrane In the case that layer is exposed photosensitive layer, it is able to suppress the resolving power deterioration for being formed by resist pattern.Barrier layer can be with It is the layer formed using the barrier layer formation of aftermentioned present embodiment with resin combination, the barrier layer shape of present embodiment Contain the alcohols and water of water-soluble resin, carbon number more than or equal to 3 at resin combination.In addition, barrier layer can have water Dissolubility, it is possible to have to the dissolubility of developer solution.It should be noted that from can more improve by barrier layer bring choke From the viewpoint of property, the bonding force on support membrane and barrier layer can be smaller than the bonding force of barrier layer and photosensitive layer.That is, can also be with It says, when removing support membrane from photosensitive element, the removing unintentionally of barrier layer and photosensitive layer is inhibited.

(water-soluble resin)

Here, " water-soluble resin " refers to the resin for being less than or equal to 5g for the solubility of 25 DEG C of hexane 100mL.It should Solubility can be by mixing the water-soluble resin after 25 DEG C of hexane and drying, and whether there is or not white opacities to calculate for investigation.Specifically For, prepare respectively: the water-soluble resin A after being put into drying in the colorless and transparent glass container with ground glass stopper (g) with the mixed liquor of hexane (100mL-A) obtained from sample 1 and be simply placed in sample 2 obtained from hexane 100mL.It connects down Come, after sufficiently shaking the sample in hybrid glass container, confirms lather collapse.After confirmation at once diffusion daylight or with it is same Deng light under two containers are arranged, the state of the state of the liquid of sample 1 and the liquid of sample 2 is compared.It will Sample 1 and sample 2 are compared, will be initially observed sample 1 it is more muddy when or be initially observed solid component floating when adding Dosage A (g) is set as the water-soluble resin for the solubility of 25 DEG C of hexane 100mL.

As water-soluble resin, such as polyvinyl alcohol, polyvinylpyrrolidone, water-soluble poly acid imide can be enumerated Deng.From the gas barrier property for more improving barrier layer, and more inhibit through free radical caused by exposure active ray used From the perspective of inactivation, water-soluble resin may include polyvinyl alcohol.Polyvinyl alcohol for example can will be by vinyl acetate polyisocyanate polyaddition Obtained from polyvinyl acetate be saponified to obtain.The saponification degree of the polyvinyl alcohol used in the present embodiment can be big In or equal to 50 moles of %, it is greater than or equal to 70 moles of % or is greater than or equal to 80 moles of %.It should be noted that the saponification The upper limit of degree is 100 moles of %.It is greater than or equal to the polyvinyl alcohol of 50 moles of % by the inclusion of saponification degree, it can be more to have The gas barrier property for improving barrier layer, can more improve the tendency for being formed by the resolving power of resist pattern.It should be noted that " saponification degree " in this specification refers to according to JIS K6726 (1994) (examination of polyvinyl alcohol specified in Japanese Industrial Standards Proved recipe method) measurement value.

The different two or more poly- second such as saponification degree, viscosity, the degree of polymerization, modification kind also can be used together in above-mentioned polyvinyl alcohol Enol.The average degree of polymerization of polyvinyl alcohol can be 300~5000,300~3500 or 300~2000.In addition, above-mentioned water solubility Resin can be used alone or be applied in combination two or more.Water-soluble resin also may include such as polyvinyl alcohol and gather Vinyl pyrrolidone.In this case, polyvinyl alcohol and the mass ratio (PVA:PVP) of polyvinylpyrrolidone can be 40: 60~90:10,50:50~90:10 or 60:40~90:10.

From the viewpoint of improving gas barrier property, the barrier layer of present embodiment is formed with the water-soluble tree in resin combination Rouge content can be 50~300 mass parts, 60~250 mass parts, 70~200 mass parts, 80~150 relative to 500 mass parts of water Mass parts or 80~125 mass parts.

(carbon number is greater than or equal to 3 alcohols)

Carbon number more than or equal to 3 alcohols can be unary alcohol, can also for polyalcohols (aftermentioned polyol compound Except plasticizer).The carbon number of alcohols of the carbon number more than or equal to 3 refers to the sum of carbon number of the alcohols, can be less than or equal to 10, Less than or equal to 8, it is less than or equal to 7, is less than or equal to 6 or is less than or equal to 5.Alcohols of the carbon number more than or equal to 3 can contain Selected from by represented by following chemical formula (1)~(3) compound and the following general formula (4) represented by the group that forms of compound It is at least one.By being greater than or equal to 3 alcohols containing these carbon numbers, the removing of barrier layer and support membrane can be more improved Property.

[changing 5]

[changing 6]

[changing 7]

[changing 8]

In general formula (4), R¹¹Indicate alkyl, R¹²Indicate alkylidene.In addition, R¹¹Group and R¹²The sum of the carbon number of group More than or equal to 3.In addition, from the viewpoint of more being improved with the compatibility of water, R¹¹Group and R¹²Group carbon number it With can be less than or equal to 10, be less than or equal to 8, be less than or equal to 7, be less than or equal to 6 or be less than or equal to 5.R¹¹It is represented Alkyl can be carbon number 1~4 alkyl, R¹²Represented alkylidene can also be the alkylidene of carbon number 1~3.It should be noted that R¹¹Represented alkyl and R¹²Represented alkylidene respectively can have substituent group, can also not have substituent group.Have In the case where substituent group, R¹¹Group carbon number and R¹²The carbon number of group separately include the carbon number of substituent group.In addition, general formula (4) alcohols of the carbon number more than or equal to 3 represented by can also be 2- butoxy-ethyl alcohol or 1- methoxy-2-propanol.

Above-mentioned carbon number can be used alone or be applied in combination more than or equal to 3 alcohols two or more.In addition, from energy From the perspective of enough layer separation for more inhibiting barrier layer, solubility of alcohols of the carbon number more than or equal to 3 for 20 DEG C of water 300mL/ water 100mL can be greater than or equal to, be greater than or equal to 500mL/ water 100mL or be greater than or equal to 1000mL/ water 100mL。

" solubility of alcohols of the carbon number more than or equal to 3 for 20 DEG C of water " in this specification can be by by the alcohol Class is mixed with 20 DEG C of water, and whether there is or not gonorrhoeas to calculate for investigation.Specifically, preparing respectively: colourless with ground glass stopper In transparent glass container, it is put into sample 3 obtained from the mixed liquor of alcohols AmL and water (100-A) mL and is simply placed in water Sample 4 obtained from (100mL).Next, by glass container sample 3 and sample 4 respectively sufficiently shake mixing after, confirmation Lather collapse.Two containers are arranged under diffusion daylight or the light same with it at once after confirmation, it will be in sample 3 The state of liquid and the state of the liquid in sample 4 are compared.Sample 3 and sample 4 are compared, it will be observed that sample 3 The additive amount AmL of alcohols when more muddy is set as the alcohols for the solubility of 20 DEG C of water.

The barrier layer of present embodiment forms opposite more than or equal to the content of 3 alcohols with the carbon number in resin combination In 500 mass parts of water can for 100~500 mass parts, 110~480 mass parts, 120~460 mass parts, 125~440 mass parts, 125~420 mass parts or 125~400 mass parts.If the content is greater than or equal to 100 mass parts, it is formed by resistance The tendency that the fissility of barrier and support membrane improves then has the dissolubility of water-soluble resin if it is less than or equal to 500 mass parts It improves, is easily formed the tendency on barrier layer.

The content of alcohols of the carbon number more than or equal to 3 in the barrier layer of present embodiment (is formed with the total amount on barrier layer The barrier layer on barrier layer forms the solid component total amount of resin combination) on the basis of can be more than 0 mass % and to be less than or wait In 2.0 mass %, 0.001~2.0 mass % or 0.005~1.0 mass %.It is less than or equal to 2.0 matter by the content Measure %, to have the tendency that the alcohols being able to suppress in subsequent handling diffusion, by more than 0 mass %, thus have barrier layer and The tendency that the fissility of support membrane improves, by being greater than or equal to 0.001 mass %, to there is the removing of barrier layer and support membrane The tendency that property more improves.

Alcohols of the barrier layer formation resin combination of present embodiment containing carbon number less than 3.Containing carbon number In the case where alcohols less than 3, content can be 125~375 mass parts or 150~325 mass relative to 500 mass parts of water Part.It is greater than or equal to 125 mass parts by the content, to there is the dissolubility of water-soluble resin to improve, is easily formed barrier layer Tendency, by be less than or equal to 375 mass parts, thus have the fissility for being formed by barrier layer and support membrane improve incline To.In addition, the carbon number in the barrier layer of present embodiment is less than from the viewpoint of the raising of the fissility of barrier layer and support membrane The content of 3 alcohols can be 0.1~10 mass % on the basis of the total amount of the alcohols in barrier layer, or relative in barrier layer 100 mass parts of total amount of alcohols of the carbon number more than or equal to 3 can be 0.1~10 mass parts.

In addition, the barrier layer formation of present embodiment can be in the range for the effect for not interfering the disclosure with resin combination It is interior to contain additive well known to plasticizer, surfactant etc..In addition it is also possible in the range of not interfering the effect of the disclosure Contain removing promotor.

As plasticizer, such as from the viewpoint of improving extensibility, polyol compound can be contained.It can enumerate for example sweet The glycerols such as oil, two glycerol, triglycerin；Ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, two Propylene glycol, polypropylene glycol etc. (poly-) aklylene glycol class；Trimethylolpropane etc..These plasticizer can be used alone, Or it is applied in combination two or more.

Barrier layer in the photosensitive element of present embodiment for example can be by being coated with present embodiment on support membrane Barrier layer formation resin combination and be dried to be formed.

The thickness on barrier layer is not particularly limited.From the viewpoint of easily removing barrier layer, the thickness on barrier layer can be with Less than or equal to 12 μm, be less than or equal to 10 μm, be less than or equal to 8 μm, be less than or equal to 7 μm or be less than or equal to 6 μm.This Outside, from the viewpoint of barrier layer easy to form and resolving power, the thickness on barrier layer can also be greater than or equal to 1.0 μm, it is big In or be equal to 1.5 μm, be greater than or equal to 2 μm, be greater than or equal to 3 μm or be greater than or equal to 4 μm.

It should be noted that the barrier layer in present embodiment can have photonasty, but its photonasty and photosensitive layer Photonasty is compared to low.In addition, barrier layer can also not have photonasty.In the case where barrier layer does not have photosensitive situation, thoughts The tendency that the sensitivity stability of photosphere more improves.In addition, so-called " photonasty ", refers to and for example exposes to photosensitive layer Light, the heat treatment after being exposed as needed, then using the developer solution in the uncured portion for removing photosensitive layer to sense In the case that photosphere is developed, it is capable of forming resist pattern.

< photosensitive layer >

The photosensitive layer of present embodiment is to be formed by layer using aftermentioned photosensitive polymer combination.Photoresist group As long as closing the resin combination that object property changes (such as carrying out photocuring) because light irradiates, so that it may according to desired mesh Use, can be minus, be also possible to eurymeric.Photosensitive polymer combination can contain (A) binder polymer, (B) light Polymerizable compound and (C) Photoepolymerizationinitiater initiater.In addition, as needed can also containing (D) photosensitizer, (E) polymerization inhibitor or its His ingredient.Hereinafter, each ingredient used in the photosensitive polymer combination in present embodiment is described in detail.

((A) binder polymer)

(A) binder polymer (hereinafter also referred to as " (A) ingredient ") for example can be by making polymerizable monomer carry out free radical Polymerization is to manufacture.As above-mentioned polymerizable monomer, such as can enumerate: styrene, vinyltoluene and α-methylstyrene etc. exist The polymerizable styrene derivative replaced in alpha-position or aromatic ring；The acrylamides such as diacetone acrylamide；Third Alkene nitrile；The ethers of the vinyl alcohols such as vinyl n-butyl ether；(methyl) alkyl acrylate；(the first such as benzyl methacrylate Base) benzyl acrylate；(methyl) tetrahydrofurfuryl acrylate, (methyl) acrylate, (methyl) acrylic acid two Ethylamino ethyl ester, (methyl) glycidyl acrylate, (methyl) acrylic acid 2,2,2- trifluoro ethyl ester, (methyl) acrylic acid 2, 2,3,3- tetrafluoro propyl ester, (methyl) acrylic acid, α-bromopropene acid, α-chloroacrylic acid, β-furyl (methyl) acrylic acid, β-benzene second Alkenyl (methyl) acrylic acid, maleic acid, maleic anhydride；The horses such as monomethyl maleate, ethyl maleate, maleic acid list isopropyl ester Carry out acid monoester；Fumaric acid, cinnamic acid, alpha-cyano cinnamic acid, itaconic acid, crotonic acid and propiolic acid.They can be used alone it is a kind of, Or it is applied in combination two or more.

Among them, from the viewpoint of plasticity raising, (methyl) alkyl acrylate can be contained.As (methyl) third Olefin(e) acid Arrcostab, such as can enumerate: the alkyl of compound represented by the following general formula (II) and these compounds by hydroxyl, Epoxy group, halogen etc. replace resulting compound.

H₂C=C (R⁶)-COOR⁷ (II)

In logical formula (II), R⁶Indicate hydrogen atom or methyl, R⁷Indicate the alkyl of carbon number 1~12.As R⁷Represented carbon number 1~12 alkyl, such as methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, 11 can be enumerated The constitutional isomer of alkyl, dodecyl and these groups.

It as (methyl) alkyl acrylate represented by above-mentioned logical formula (II), such as can enumerate: (methyl) acrylic acid first Ester, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) amyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) heptylacrylate, (methyl) 2-ethyl hexyl acrylate, (methyl) 2-EHA, (methyl) third Olefin(e) acid nonyl ester, (methyl) decyl acrylate, (methyl) acrylic acid hendecane base ester, (methyl) dodecylacrylate etc..It Can be used alone a kind of or be applied in combination two or more.

In addition, (A) ingredient can contain carboxyl from the viewpoint of alkali-developable.(A) ingredient containing carboxyl can for example lead to Crossing makes to have the polymerizable monomer of carboxyl to carry out free radical polymerization with other polymerizable monomers to manufacture.There is carboxyl as above-mentioned Polymerizable monomer, can be (methyl) acrylic acid, can also be methacrylic acid.In addition, the acid value of (A) ingredient containing carboxyl can For 50~250mgKOH/g, 50~200mgKOH/g or 100~200mgKOH/g.

From the viewpoint of balance improves alkali-developable and alkali resistance well, the carboxyl-content of (A) ingredient (has carboxylic Fit rate of the polymerizable monomer of base relative to polymerizable monomer total amount used in binder polymer) it can be 12~50 matter Measure %, 12~40 mass %, 15~35 mass %, 15~30 mass % or 20~30 mass %.Be greater than in the carboxyl-content or When equal to 12 mass %, have the tendency that alkali-developable raising has alkali resistance is excellent to incline when being less than or equal to 50 mass % To.

It should be noted that in (A) ingredient be originated from carboxyl polymerizable monomer structural unit content due to It is related to the fit rate of the above-mentioned polymerizable monomer with carboxyl, thus can for 12~50 mass %, 12~40 mass %, 15~ 35 mass %, 15~30 mass % or 20~30 mass %.

In addition, styrene or styrene derived can be used in (A) ingredient from the viewpoint of adaptation and chemical-resistant Object is as polymerizable monomer.When using above-mentioned styrene or styrene derivative as when polymerizable monomer, from making adaptation and resistance to From the perspective of chemicals become better, (styrene or styrene derivative are relative to used in (A) ingredient for content The fit rate of polymerizable monomer total amount) it can be 10~60 mass %, 15~50 mass %, 30~50 mass %, 35~50 matter Measure % or 40~50 mass %.When the content is greater than or equal to 10 mass %, have the tendency that adaptation raising, being less than or When equal to 60 mass %, it is able to suppress the stripping film in development and becomes larger, be able to suppress the long-time of removing required time Tendency.

It should be noted that the content of the structural unit for being originated from styrene or styrene derivative in (A) ingredient due to It is related to the fit rate of above-mentioned styrene or styrene derivative, thus can for 10~60 mass %, 15~50 mass %, 30~ 50 mass %, 35~50 mass % or 40~50 mass %.

In addition, (methyl) benzyl acrylate conduct also can be used in (A) ingredient from the viewpoint of resolution ratio and aspect ratio Polymerizable monomer.From the viewpoint of further increasing resolution ratio and aspect ratio, (methyl) acrylic acid benzyl is originated from (A) ingredient The content of the structural unit of ester can for 15~50 mass %, 15~45 mass %, 15~40 mass %, 15~35 mass % or 20~30 mass %.

These binder polymers can be used alone or be applied in combination two or more.As being applied in combination two kinds (A) ingredient when above, such as can enumerate: the two or more binder polymers that are formed by different polymerizable monomers, again The different two or more binder polymers of the different two or more binder polymers and dispersion degree of average molecular weight.

(A) ingredient can be manufactured by usual way.Specifically, for example can be by making (methyl) acrylic acid alkyl Ester, (methyl) acrylic acid and styrene etc. carry out free radical polymerization to manufacture.

From the viewpoint of balance improves mechanical strength and alkali-developable well, the weight average molecular weight of (A) ingredient can It is 20,000~300,000,40,000~150,000,40,000~120,000 or 50,000~80,000.In (A) ingredient Weight average molecular weight be greater than or equal to 20,000 when, have the tendency that developer resistance is excellent, be less than or equal to 300,000 when, Have the tendency that being able to suppress developing time elongated.It should be noted that the weight average molecular weight in this specification is seeped using gel Saturating chromatography (GPC) is measured, and carries out the resulting value that converts by using standard curve made by standard polystyren.

Solid component total amount 100 mass parts of the content of above-mentioned (A) ingredient relative to (A) ingredient and aftermentioned (B) ingredient It can be 30~80 mass parts, 40~75 mass parts, 50~70 mass parts or 50~60 mass parts.The content of (if A) ingredient In the range, then the painting film property of photosensitive polymer combination and the intensity in photocuring portion become better.

((B) photopolymerizable compound)

Photosensitive polymer combination involved in present embodiment may include (B) photopolymerizable compound (hereinafter also referred to as " (B) ingredient ").It (B), then can be with as long as ingredient is able to carry out the compound of photopolymerization, is able to carry out the compound of photo-crosslinking It uses without particular limitation, such as the compound that intramolecular can be used that there is at least one ethylene unsaturated bond.

It as (B) ingredient, such as can enumerate: make polyalcohol and α, it is compound obtained from beta-unsaturated carboxylic acid reaction, double Phenol A type (methyl) acrylate compounds etc. bisphenol types (methyl) acrylate compounds, (first with urethane bond Base) carbamate monomers, Nonylphenoxy ethyleneoxy group (methyl) acrylate, nonyl benzene oxygen such as acrylate compounds Eight ethyleneoxy group of base (methyl) acrylate, the chloro- β-hydroxy propyl-Beta of γ-'-(methyl) acryloyl-oxyethyl-O-phthalic Acid esters, beta-hydroxyethyl-β '-(methyl) acryloyl-oxyethyl-phthalic acid ester, β-hydroxy propyl-Beta '-(methyl) acryloyl-oxy Base ethyl-phthalic acid ester and (methyl) alkyl acrylate.They can be used alone or be applied in combination two Kind or more.

Among the above, the viewpoint for the inhibition that resolving power, adaptation and resist end generate is improved well from balance It sets out, (B) ingredient can contain bisphenol type (methyl) acrylate compounds.As above-mentioned bisphenol type (methyl) acrylate chemical combination Object can be compound represented by the following general formula (III).

[changing 9]

In logical formula (III), R¹、R²、R³And R⁴Each independently represent hydrogen atom or methyl.X and Y are each independently represented Ethylidene or propylidene, XO and YO each independently represent oxygroup ethylidene (hereinafter, sometimes referred to as " EO yl ".) or oxygroup Asia third Base is (hereinafter, sometimes referred to as " PO yl ".).p₁、p₂、q₁And q₂Each independently represent 0~40 numerical value.Wherein, p₁+q₁And p₂+q₂ It is all larger than or equal to 1.When X is ethylidene, and Y is propylidene, p₁+p₂For 1~40, q₁+q₂It is 0~20.When X is propylidene, Y When for ethylidene, p₁+p₂For 0~20, q₁+q₂It is 1~40.Due to p₁、p₂、q₁And q₂Indicate the structural unit of EO base or PO base Quantity, therefore integer value is indicated in single molecule, the rational as average value is indicated in the aggregate of different kinds of molecules.It needs It is noted that EO base and PO base can continuously exist respectively with block fashion, can also randomly exist.

In logical formula (III), when X and Y is ethylidene, from the viewpoint of resolution ratio and adaptation are more excellent, p₁+ p₂+q₁+q₂It can be 1~20,1~10 or 1~7.

It as compound represented by logical formula (III), such as can enumerate: 2,2- bis- (4- ((methyl) acryloyl-oxy Quito second Oxygroup) phenyl) propane, 2,2- bis- (4- ((methyl) acryloyl-oxy Quito propoxyl group) phenyl) propane, the bis- (4- ((methyl) of 2,2- The more propoxyl group of acryloyl-oxy Quito ethyoxyl) phenyl) propane etc..They can be used alone or be applied in combination two kinds with On.

As bisphenol type (methyl) acrylate compounds that can be obtained with commercial system, such as can enumerate: 2,2- is bis- (4- (methacryloxy diethoxy) phenyl) propane (village Xin Zhong chemical industry Co. Ltd. system " BPE-200 "), 2,2- Bis- (4- (five ethyoxyl of methacryloxy) phenyl) propane (village Xin Zhong chemical industry Co. Ltd. system " BPE-500 " or days Vertical chemical conversion Co. Ltd. system " FA-321M "), bis- (4- (15 ethyoxyl of the methacryloxy) phenyl) propane of 2,2- are (in newly Village's chemical industry Co. Ltd. system " BPE-1300 "), bis- (4- (the more ethyoxyls of the methacryloxy) phenyl) propane of 2,2- (altogether Flourish society's Chemical Co., Ltd. system " BP-2EM " (EO base: 2.6 (average values))) etc..

From the viewpoint of more improving chemical-resistant, the content of bisphenol type (methyl) acrylate compounds relative to (A) the solid component total amount of ingredient and (B) ingredient can be 1~50 mass %, 3~40 mass %, 10~40 mass %, 20~40 Quality % or 30~40 mass %.

In addition, from the viewpoint of more improving chemical-resistant, the content of bisphenol type (methyl) acrylate compounds Solid component total amount relative to (B) ingredient can be 30~99 mass %, 50~97 mass %, 60~95 mass %, 70~95 Quality % or 80~90 mass %.

In addition, the solid component from the viewpoint of making resolution ratio become better, relative to (A) ingredient and (B) ingredient The sum of total amount, EO base and PO base be 1~7 by lead to formula (III) indicate compound content can be 1~50 mass %, 2~ 48 mass %, 3~45 mass %, 5~40 mass %, 10~30 mass % or 10~25 mass %.

In addition, can also contain makes polyalcohol and α from the viewpoint of more improving for the concave-convex tracing ability of substrate, Beta-unsaturated carboxylic acid is reacted and the compound that obtains.As such compound, intramolecular can be used that there is EO base and PO Polyalkylene glycol two (methyl) acrylate of both bases, dipentaerythritol (methyl) acrylate with EO base etc..Make Compound for dipentaerythritol (methyl) acrylate with EO base that can be obtained with commercial system, such as can enumerate: " the DPE Α -12 " etc. of Nippon Kayaku K. K's manufacture.From the standpoint of improving the resolution, with two Ji Wusi of EO base The content of alcohol (methyl) acrylate can be 1~10 mass %, 1.5~8 matter relative to the solid component total amount of (B) ingredient Measure %, 2~8 mass %, 2.5~8 mass % or 3~8 mass %.

It should be noted that in the molecule of polyalkylene glycol two (methyl) acrylate with both EO base and PO base Interior, EO base and PO base can continuously exist respectively with block fashion, can also randomly exist.In addition, PO base can be oxygroup Any one of n-propylene or oxygroup isopropylidene.It should be noted that the secondary carbon of propylidene can in (poly-) oxygroup isopropylidene To be bonded on oxygen atom, primary carbon can also be bonded on oxygen atom.

As polyalkylene glycol two (methyl) propylene with both EO base and PO base that can be obtained with commercial system Acid esters, such as can enumerate: there is EO base: 6 (average values) and PO base: polyalkylene glycol two (methyl) propylene of 12 (average values) Acid esters (" F Α -023M ", " the F Α -024M " of Hitachi Chemical Co., Ltd.'s manufacture) etc..In addition, from the bumps improved for substrate Tracing ability and resolving power from the perspective of, polyalkylene glycol two (methyl) acrylate with both EO base and PO base Content relative to (B) ingredient solid component total amount can for 1~15 mass %, 1.5~15 mass %, 2~13 mass % or 3~13 mass %.

Relative to 100 mass parts of solid component total amount of (A) ingredient and (B) ingredient, the content of (B) ingredient can be set as 20~ 70 mass parts, 25~60 mass parts or 30~50 mass parts.If the content of (B) ingredient is in the range, in addition to photonasty Other than the inhibition that the resolution ratio of resin combination, adaptation and resist end generate becomes more good, sensitivity and painting Film property also becomes more good.

((C) Photoepolymerizationinitiater initiater)

Photosensitive polymer combination involved in present embodiment can containing at least one (C) Photoepolymerizationinitiater initiater (hereinafter, Also referred to as " (C) ingredient ").It (C), can be from usual as long as the ingredient that ingredient can be such that (B) ingredient polymerize, then be not particularly limited It is suitable for selection in used Photoepolymerizationinitiater initiater.

It as (C) ingredient, such as can enumerate: 2- benzyl -2- dimethylamino -1- (4- morpholino phenyl)-butanone -1,2- The equal aromatic ketones of methyl-1-[4- (methyl mercapto) phenyl]-2- morpholinyl-acetone-1；The quinones such as alkyl-anthraquinone；Benzoin alkyl ether Equal benzoins ether compound；The benzoins compounds such as benzoin, alkyl benzoin；The benzils such as benzil dimethyl ketal are derivative Object；2- (Chloro-O-Phenyl) -4,5- diphenyl-imidazole dimer, 2- (o-fluorophenyl) -4,5- diphenyl-imidazole dimer etc. 2,4, 5- triarylimidazoles dimer；Acridine derivatives such as 9- phenylacridine, 1,7- (9,9 '-acridinyl) heptane etc..They can be single It solely uses a kind of or is applied in combination two or more.

Among them, from the viewpoint of resolving power raising, 2,4,5- triarylimidazoles dimers can be contained.As above-mentioned 2,4,5- triarylimidazoles dimers, such as can enumerate: 2- (Chloro-O-Phenyl) -4,5- diphenyl-imidazole dimer, 2- (adjacent chlorobenzene Base) -4,5- is double-(m-methoxyphenyl) imidazoles dimer and 2- (p-methoxyphenyl) -4,5- diphenyl-imidazole dimerization Body.Among them, from the stability-enhanced viewpoint of sensitivity, 2- (Chloro-O-Phenyl) -4,5- diphenyl-imidazole two can be contained Aggressiveness.

As 2,4,5- triarylimidazoles dimers, such as 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-tetraphenyls join miaow Azoles can be used as B-CIM (Baotugu Chemical Industrial Co., Ltd's manufacture, product name) and be obtained with commercial system.

From light sensitivity and adaptation is more improved, further more from the perspective of the light absorption of inhibition (C) ingredient, (C) ingredient can contain at least one of 2,4,5- triarylimidazoles dimers, can also contain 2- (2- chlorphenyl) -4,5- diphenyl Imidazoles dimer.It should be noted that the structure of 2,4,5- triarylimidazoles dimers can be symmetrical, it can also be asymmetric.

Relative to 100 mass parts of solid component total amount of (A) ingredient and (B) ingredient, the content of (C) ingredient can for 0.01~ 30 mass parts, 0.1~10 mass parts, 1~7 mass parts, 1~6 mass parts, 1~5 mass parts or 2~5 mass parts.(C) at When the content divided is greater than or equal to 0.01 mass parts, has the tendency that light sensitivity, resolving power and adaptation improve, be less than or equal to When 30 mass parts, have the tendency that resist pattern shape is excellent.

((D) photosensitizer)

Photosensitive polymer combination involved in present embodiment can containing (D) photosensitizer (hereinafter also referred to as " and (D) at Point ").By containing (D) ingredient, have the tendency that the absorbing wavelength of active ray used in exposure can be effectively utilized.

It as (D) ingredient, such as can enumerate: pyrazolines, dialkyl amido benzophenone, anthracene class, Coumarins, oxygen Miscellaneous anthrone class,Azole, benzoAzole, thiazoles, benzothiazoles, triazole type, stilbene class, triazines, thiophene-based, naphthalene two Carboximide class and triaryl amine.They can be used alone a kind of or are applied in combination two or more.From being capable of more effective land productivity From the perspective of the absorbing wavelength of the active ray used in exposure, (D) ingredient can contain pyrazolines, anthracene class or dioxane Base aminobenzophenone class, wherein dialkyl amido benzophenone can also be contained.As can be obtained with commercial system two Alkyl amino benzophenone, such as " EAB " etc. of Baotugu Chemical Industrial Co., Ltd's manufacture can be enumerated.

When containing (D) ingredient, content can relative to 100 mass parts of solid component total amount of (A) ingredient and (B) ingredient For less than or equal to 1.0 mass parts, be less than or equal to 0.5 mass parts, be less than or equal to 0.15 mass parts, be less than or equal to 0.12 Mass parts are less than or equal to 0.10 mass parts.The content of (if D) ingredient relative to the solid of (A) ingredient and (B) ingredient at Divide 100 mass parts of total amount to be less than or equal to 1.0 mass parts, is then able to suppress resist pattern shape and resist end generates The deterioration of property, can make the more good tendency of resolution ratio.In addition, from better photosensitivity is easy to get and high-resolution viewpoint goes out Hair, relative to 100 mass parts of solid component total amount of (A) ingredient and (B) ingredient, the content of (D) ingredient also may be greater than or wait In 0.01 mass parts.

((E) polymerization inhibitor)

Photosensitive polymer combination involved in present embodiment may include (E) polymerization inhibitor (hereinafter also referred to as " and (E) at Point ").By containing (E) ingredient, having can will be used to make photosensitive polymer combination photocuring required light exposure to be adjusted to most It is suitble to the tendency for the light exposure being exposed using projection exposure machine.

From the viewpoint of further increasing resolving power, (E) ingredient may include compound represented by the following general formula (I).

[changing 10]

In logical formula (I), R⁵Indicate halogen atom, hydrogen atom, the alkyl of carbon number 1~20, the naphthenic base of carbon number 3~10, amino, Aryl, sulfydryl, the alkyl thiol of carbon number 1~10, alkyl carbon number be 1~10 carboxyalkyl, carbon number 1~20 alkoxy or Heterocycle, m and n are selected in such a way that m is integer more than or equal to 2, n is integer and m+n=6 more than or equal to 0 Integer, when n is the integer more than or equal to 2, R⁵It may be the same or different respectively.It should be noted that aryl can by carbon number 1~ 20 alkyl replaces.

From the viewpoint of more improving the compatibility with (A) ingredient, R⁵It can be hydrogen atom or the alkyl of carbon number 1~20. As R⁵The alkyl of represented carbon number 1~20 can be the alkyl of carbon number 1~4.Go out from the viewpoint for further increasing resolving power Hair, m can be 2 or 3, can also be 2.

It as compound represented by above-mentioned logical formula (I), such as can enumerate: catechol；Resorcinol (Lei Suoxin)；1, 4- hydroquinone；3- methyl pyrocatechol, 4- methyl pyrocatechol, 3- ethyl catechol, 4- ethyl catechol, 3- propyl Catechol, 4- propyl catechol, 3- normal-butyl catechol, 4- normal-butyl catechol, 3- tert-butyl catechol, 4- The alkyl catechols such as tert-butyl catechol, 3,5- di-t-butylcatechol；2- methyl resorcinol, 4- methylresorcinol two Phenol, oreinol diphenol (orcin), 2- ethyl resorcinol, 4- ethyl resorcinol, 2- propyl diphenol, 4- propyl Resorcinol, 2- n-butyl resorcinol, Lucin, 2- tert-butyl resorcin, 4- tert-butyl resorcin Equal alkyl-resorcins；Methyl hydroquinone, ethyl hydroquinones, propyl hydroquinone, tert-butyl hydroquinone, bis- uncle of 2,5- The alkyl hydroquinone such as butylhydroquinone；Pyrogallol, phloroglucin etc..They, which can be used alone or combine, makes With two or more.

It, can be adjacent for alkyl from the viewpoint of further increasing resolving power among compound represented by above-mentioned logical formula (I) Benzenediol.

(E) content of ingredient relative to (A) ingredient and (B) ingredient 100 mass parts of solid component total amount can for 0.001~ 0.3 mass parts, 0.01~0.2 mass parts, 0.02~0.15 mass parts or 0.03~0.1 mass parts.By making (E) ingredient Content is less than or equal to 0.3 mass parts, can shorten the time for exposure, has the tendency that contribute to the raising of volume production efficiency. In addition, by making the content of (E) ingredient be greater than or equal to 0.001 mass parts, to there is the light reaction that can make photocuring portion to fill It point carries out, because reactivity improves, to be able to suppress resist bloating tendency and make the more good tendency of resolution ratio.

In addition, the content of (E) ingredient can be 0.03~0.4 mass relative to 100 mass parts of solid component of (A) ingredient Part, 0.05~0.4 mass parts, 0.05~0.2 mass parts or 0.05~0.1 mass parts.(E) ingredient content relative to (A) Ingredient be more than or equal to 0.05 mass parts in the case where, have inclining for the thermal stability that can be improved photosensitive polymer combination To, be less than or equal to 0.4 mass parts in the case where, have the tendency that the yellowing for being able to suppress photosensitive polymer combination.

(other compositions)

It, as needed, can be relative to (A) ingredient and (B) in photosensitive polymer combination involved in present embodiment Malachite green, Victoria pure blue, brilliant green of 100 mass parts of solid component total amount of ingredient respectively containing 0.01~20 mass parts And the dyestuffs such as crystal violet；Tribromo phenylsulfone, colorless crystal violet, diphenylamines, benzyl amine, triphenylamine, diethylaniline, o-chloraniline And the light color developing agent such as tert-butyl catechol；Heat colour developing preventing agent；The plasticizer such as para toluene sulfonamide；Pigment, filler, defoaming The additions such as agent, fire retardant, adaptation imparting agent, levelling agent, removing promotor, antioxidant, fragrance, imaging agent, thermal cross-linking agent Agent.These additives can be used alone or be applied in combination two or more.

In addition, in photosensitive polymer combination involved in present embodiment, in order to improve the processing of photosensitive composite Property, or viscosity and storage stability are adjusted, it can according to need at least one comprising organic solvent.As above-mentioned organic molten Agent can use commonly used organic solvent without particular limitation.Specifically, can for example enumerate methanol, ethyl alcohol, third Ketone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N,N-dimethylformamide, propylene glycol monomethyl ether etc. have Solvent or their mixed solvent.They can be used alone or be applied in combination two or more.

< protective layer >

The photosensitive element of present embodiment can also be on the face upper layer for the face opposite side of photosensitive layer contacted with barrier layer Folded protective layer.As protective layer, it is possible to use polymer film such as polyethylene, polypropylene etc..In addition, can be used and above-mentioned branch Support the same polymer film of film, it is possible to use different polymer films.

Hereinafter, to manufacture stack gradually Supported film, barrier layer, photosensitive layer and protective layer photosensitive element method into Row explanation.

The manufacturing method > of < photosensitive element

Firstly, for example, in such a way that solid component content becomes 10~20 mass %, to be heated up to 70~90 DEG C of water with The in the mixed solvent of alcohols slowly adds the water-soluble resin containing polyvinyl alcohol, and stirs 1 hour or so and make it uniformly Ground dissolution, the alcohols include the alcohols that carbon number is greater than or equal to 3, are greater than or equal to obtain containing polyvinyl alcohol and carbon number The barrier layer of 3 alcohols forms and uses resin combination.It is so-called " solid component " in this specification, refer to removing for resin combination Nonvolatile component other than the substance of the volatilizations such as water, organic solvent.That is, referring to non-volatile and remaining in drying process remove Ingredient other than water, organic solvent equal solvent, the room temperature for being also included within 25 DEG C or so is liquid, malt sugar shape and wax-like ingredient.

Next, barrier layer formation is coated on support membrane with resin combination, and it is dried and forms barrier layer. Coating of the above-mentioned barrier layer formation resin combination on support membrane can for example be applied by roller coating, the coating of unfilled corner wheel, intaglio plate Cloth, airblade coating, die coating, stick apply, method well known to spraying etc. carries out.

In addition, as long as at least part of water removal equal solvent, the barrier layer formation resin combination being coated with can be removed Drying be just not particularly limited, can be 5~30 minutes dry at 70~150 DEG C.After drying, from molten in the process prevented thereafter From the perspective of agent diffusion, the residual solvents amount in barrier layer can be set as being less than or equal to 2 mass %.

Next, can also be on the barrier layer for the support membrane for being formed with barrier layer, with barrier layer formation resin combination Coating similarly photosensitive resin coating composition and be dried, to form photosensitive layer over the barrier layer.Next, will Protective layer is laminated on the photosensitive layer formed in the above described manner, has support membrane, barrier layer, photosensitive layer so as to make successively With the photosensitive element of protective layer.In addition it is also possible to by the way that barrier layer person and shape on the protection layer will be formed on support membrane At there is photosensitive layer, person is bonded, to obtain the photosensitive element for successively having support membrane, barrier layer, photosensitive layer and protective layer.

The thickness of photosensitive layer in photosensitive element can be suitable for selection depending on the application, can be 1 with the thickness gauge after drying ~200 μm, 5~100 μm or 10~50 μm.It is greater than or equal to 1 μm by the thickness of photosensitive layer, so that industrial coating becomes It is easy, has the tendency that productivity raising.In addition, due to light sensitivity height, resisting when the thickness of photosensitive layer is less than or equal to 200 μm The photo-curable for losing agent bottom is excellent, thus has the tendency that being capable of forming resolution ratio and the excellent resist pattern of aspect ratio.

Melt viscosity of the photosensitive layer at 110 DEG C in photosensitive element can be according to the type of the substrate contacted with photosensitive layer And it is suitable for selection, it can be 50~10000Pas, 100~5000Pas or 200~1000Pas at 110 DEG C after dry. If melt viscosity at 110 DEG C is greater than or equal to 50Pas, gauffer and gap will not be generated in lamination process, there is life The tendency that yield improves.In addition, if melt viscosity at 110 DEG C is less than or equal to 10000Pas, then in lamination process It is improved with the cementability of substrate, is reduced the tendency of poor attachment.

The form of photosensitive element involved in present embodiment is not particularly limited.May be, for example, sheet, can also for Web-like is wound in the obtained shape of core.When being wound with web-like, can be wound in such a way that support membrane becomes outside.As Core, such as polyvinyl resin, acrylic resin, polystyrene resin, Corvic or ABS resin (propylene can be enumerated Nitrile-butadiene-styrene copolymer) etc. plastics etc..

End can be set from the viewpoint of the protection of end face in the end face that the photosensitive element of the web-like as above obtained is rolled up Face separator, in addition, damp proof end face separator also can be set from the viewpoint of resistance to edge-melting.As bundling method, can wrap Enter and is packed in the small black-film material of penetrability.

Photosensitive element involved in present embodiment can be suitably used for the formation side of for example aftermentioned resist pattern The manufacturing method of method and printing distributing board.

[forming method of resist pattern]

The forming method of resist pattern involved in present embodiment has: (i) uses above-mentioned photosensitive element, from base Plate side configures in order photosensitive layer, barrier layer and support membrane in the process on the substrate (hereinafter also referred to as " (i) photosensitive layer and resistance Barrier formation process ")；(ii) above-mentioned support membrane is removed, using active ray across above-mentioned barrier layer to above-mentioned photosensitive layer into The process of row exposure (hereinafter also referred to as " (ii) exposure process ")；And (iii) removes above-mentioned photosensitive layer from aforesaid substrate The process (hereinafter also referred to as " (iii) developing procedure ") in uncured portion and above-mentioned barrier layer, may also comprise other works as needed Sequence.It should be noted that so-called resist pattern, alternatively referred to as the photocured product pattern of photosensitive polymer combination, are also referred to as Relief pattern.In addition, the resist pattern in present embodiment may be used as resist according to purpose, can be used for protecting Other purposes such as film.

((i) photosensitive layer and barrier layer formation process)

In photosensitive layer and barrier layer formation process, photosensitive layer and blocking are formed on substrate using above-mentioned photosensitive element Layer.It as aforesaid substrate, is not particularly limited, the electricity for having insulating layer with the conductor layer being formed on insulating layer usually can be used Road forms the pressure pad (lead frame substrate) etc. with substrate or alloy base material etc..

As the method for forming photosensitive layer and barrier layer on substrate, such as when use has the photosensitive element of protective layer When, the photosensitive layer of photosensitive element can be crimped on substrate while being heated, thus in substrate after removing protective layer Upper formation photosensitive layer and barrier layer.It can get the laminated body for successively having substrate, photosensitive layer, barrier layer and support membrane as a result,.

When carrying out photosensitive layer and barrier layer formation process using photosensitive element, from adaptation and the viewpoint of tracing ability It sets out, can also carry out under reduced pressure.Heating when crimping can be carried out in 70~130 DEG C of temperature, crimping can 0.1~ 1.0MPa (1~10kgf/cm²) pressure under carry out, these conditions can be suitable for as needed selection.It should be noted that if will The photosensitive layer of photosensitive element is heated to 70~130 DEG C, then without carrying out the pre-heat treatment to substrate in advance, but in order to further mention High adhesion and tracing ability can also carry out the pre-heat treatment of substrate.

((ii) exposure process)

In exposure process, support membrane is removed, photosensitive layer is exposed across barrier layer using active ray.As a result, The exposure portion for having irradiated active ray can carry out photocuring and form photocuring portion (sub-image), in addition, not irradiating active ray Unexposed portion can also carry out photocuring and form photocuring portion.When forming photosensitive layer and barrier layer using above-mentioned photosensitive element When, after will be present in the support film stripping on photosensitive layer, it is exposed.By being exposed across barrier layer to photosensitive layer, energy Enough form resolving power and the excellent resist pattern of resist pattern shape.

As exposure method, well known Exposure mode can be applied, such as can be enumerated: across referred to as original image (artwork) Minus or eurymeric mask pattern, by image shape irradiation active ray method (in a manner of mask exposure)；LDI (laser directly at Picture, Laser Direct Imaging) Exposure mode；Or using being projected out the active ray of photomask image, across lens with The method (projection exposure mode) etc. of image shape irradiation.Wherein, from the viewpoint of resolving power is excellent, projection exposure side can be used Formula.That is, photosensitive element involved in present embodiment etc. is suitable for projection exposure mode.In addition, so-called projection exposure mode, Alternatively referred to as using the Exposure mode of the active ray of energy attenuation.

As the light source of active ray, as long as commonly used well known light source, then be not particularly limited, such as can Use: carbon arc lamp, mercury vapour arc lamp, ultrahigh pressure mercury lamp, high-pressure sodium lamp, xenon lamp, the gas lasers such as argon gas laser, YAG swash Semiconductor lasers such as the solid state lasers such as light device, gallium nitride blue-violet laser etc. effectively radiate the light source of ultraviolet light Deng.Furthermore, it is possible to use photoflood lamp bubble, sunlamp etc. effectively radiate the light source etc. of visible light.Among them, from flat From the perspective of weighing apparatus property improves resolving power and alignment well, it can be used the i ray for capableing of radiation exposure wavelength 365nm monochromatic The light source of light, the monochromatic light source of h ray for capableing of radiation exposure wavelength 405nm or the exposure that ihg hybrid ray can be radiated The light source of the active ray of wavelength, wherein the monochromatic light source of i ray for capableing of radiation exposure wavelength 365nm can be used.As Be capable of the monochromatic light source of i ray of radiation exposure wavelength 365nm, such as ultrahigh pressure mercury lamp can be enumerated etc..

((iii) developing procedure)

In developing procedure, the uncured portion and above-mentioned barrier layer of above-mentioned photosensitive layer are removed from substrate.Pass through work of developing Sequence forms the resist pattern that photocuring portion made of carrying out photocuring by above-mentioned photosensitive layer is constituted on substrate.Work as barrier layer When for water solubility, it can be washed and remove barrier layer, then be removed using developer solution uncured other than above-mentioned photocuring portion Portion, when barrier layer has dissolubility for developer solution, using developer solution by other than barrier layer and above-mentioned photocuring portion not Solidified portion removes together.Developing method can enumerate wet developing.

In the case where wet developing, developer solution corresponding with photosensitive polymer combination can be used, by well known Wet development method develops.As wet development method, such as can enumerate: impregnation method, it is outstanding to cover submergence mode, high pressure Spray pattern, it is most suitable from the viewpoint of improving resolving power using scrub, slap, scraping, the method for shaking impregnating etc. Be high-pressure fog mode.These wet development methods, which can be used alone, a kind of to be developed or combines two or more sides Method is developed.

Developer solution can be suitable for selection according to the composition of above-mentioned photosensitive polymer combination.Such as alkaline aqueous solution can be enumerated And organic solvent developer solution.

From the viewpoint of it is safe and stable, operational it is good, as developer solution, alkaline aqueous solution can be used.As alkali Property aqueous solution alkali, such as the alkali hydroxides such as hydroxide of lithium, sodium or potassium can be used, lithium, sodium, potassium or ammonium carbonate or carbon The carbonic acid alkali such as sour hydrogen salt, the alkali metal phosphates such as potassium phosphate, sodium phosphate, the alkali metal pyrophosphates such as sodium pyrophosphate, potassium pyrophosphate, Boratex, sodium metasilicate, tetramethylammonium hydroxide, ethanol amine, ethylenediamine, Diethylenetriamine, 2- amino -2- hydroxymethyl -1,3- Propylene glycol, 1,3-diamino-2-propanol and morpholine.

As the alkaline aqueous solution for development, sodium carbonate weak solution, 0.1~5 matter of 0.1~5 mass % can be used Measure the sodium tetraborate weak solution of the dilute potassium carbonate solution of %, the dilute solution of sodium hydroxide of 0.1~5 mass %, 0.1~5 mass % Deng.In addition, the pH of the alkaline aqueous solution for development can be set as 9~11 range, the temperature of alkaline aqueous solution can be according to photosensitive The developability of layer is adjusted.In addition, in alkaline aqueous solution, such as surfactant, defoaming agent can be mixed into, for promoting development A small amount of organic solvent etc..It should be noted that as organic solvent used in alkaline aqueous solution, such as can enumerate: 3- pyruvic alcohol, acetone, ethyl acetate, alkoxy with carbon number 1~4 alkoxyethanol, ethyl alcohol, isopropanol, butanol, diethyl Glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol monobutyl ether.

It as organic solvent used in organic solvent developer solution, such as can enumerate: 1,1,1- trichloroethanes, N- methyl Pyrrolidones, N,N-dimethylformamide, cyclohexanone, methyl iso-butyl ketone (MIBK) and gamma-butyrolacton.From prevent kindling viewpoint go out Hair, these organic solvents can add water in a manner of as the range of 1~20 mass % and organic solvent developer solution are made.

(other processes)

It also may include following process in the forming method of the resist pattern involved in present embodiment: in development work By after the removal of uncured portion in sequence, the heating or 0.2~10J/cm at 60~250 DEG C are carried out as needed²Light exposure under Exposure, to further solidify resist pattern.

[manufacturing method of printing distributing board]

The manufacturing method of printing distributing board involved in present embodiment includes to the formation by above-mentioned resist pattern The substrate that method forms resist pattern is etched or plating, thus the process for forming conductive pattern, according to It needs also to may include the other processes such as resist pattern removing step.The manufacture of printing distributing board involved in present embodiment Method is led by using the forming method of the resist pattern using above-mentioned photosensitive element so as to be suitably used for being formed Body pattern, wherein the method for being more suitably applied to form conductive pattern by plating.It should be noted that conductor figure Case is alternatively referred to as circuit.

In an etching process, it will be formed in having the resist pattern on the substrate of conductor layer as mask, will not resisted The conductor layer for losing the coating substrate of agent etches removal, to form conductive pattern.

The method of etching process is suitable for selection according to the conductor layer that should be removed.As etching solution, such as chlorination can be enumerated Copper solution, ferric chloride solution, alkaline etching etching solution, hydrogen peroxide system etching solution etc., from the viewpoint of etching factor is good, can make Use ferric chloride solution.

On the other hand, in plating, it will be formed in having resist pattern on the substrate of conductor layer as mask, Plated copper or solder etc. in the conductor layer for the substrate not being coated by resist.After plating, pass through aftermentioned resist figure The removal of case removes resist, is further etched to the conductor layer being coated by the resist, to form conductive pattern.

It can be electroplating processes as the method for plating, can also be chemical plating, wherein can be chemical plating. It as chemical plating, such as can enumerate: the copper plating such as copper sulphate plating, cupric pyrophosphate plating；High homogeneity (high Throw) the solder platings such as solder plating；Watt bath (watts bath) (nickel sulfate-nickel chloride) plating, nickel sulfamic acid plating Equal nickel plating；The golden plating such as hard gold plating, soft golden plating.

After above-mentioned etching process or plating, the resist pattern on substrate is removed.The removal of resist pattern Such as it can be removed by alkalinity aqueous solution more stronger than the alkaline aqueous solution for being used for above-mentioned developing procedure.As the highly basic The aqueous solution of property, such as 1~10 mass % sodium hydrate aqueous solution, 1~10 mass % potassium hydroxide aqueous solution can be used etc..It Among, it is possible to use 1~5 mass % sodium hydrate aqueous solution or potassium hydroxide aqueous solution.

As the removing method of resist pattern, such as impregnation method and spray pattern can be enumerated, they can individually make With also can be used together.

When removing resist pattern after implementing plating, further by etching process to being coated by resist Conductor layer is etched, and conductive pattern is formed, so as to manufacture desired printing distributing board.The side of etching process at this time Method is suitable for selection according to the conductor layer that should be removed.Such as above-mentioned etching solution can be applied.

The manufacturing method of printing distributing board involved in present embodiment can be applied not only to single layer printing distributing board Manufacture, also can be applied to the manufacture of multi-layer printed circuit board, further, it is also possible to be applied to the printed wiring with path through-hole The manufacture of plate etc..

The manufacturing method of printing distributing board involved in present embodiment can be suitably used for high-density packages substrate Manufacture, particularly the manufacture of the distributing board using semi-additive process.It should be noted that the system of the distributing board of semi-additive process will be utilized Make process one is illustrated in Fig. 2.

In Fig. 2 (a), prepare the substrate that conductor layer 40 is formed on insulating layer 50 (circuit is formed with substrate).Conductor layer 40 be, for example, layers of copper.In Fig. 2 (b), by above-mentioned photosensitive layer and barrier layer formation process, sense is formed in the conductor layer 40 of substrate Photosphere 30 and barrier layer 20.In Fig. 2 (c), by above-mentioned exposure process, irradiates and be projected out on photosensitive layer 30 across barrier layer 20 The active ray 80 of photomask image, to form photocuring portion on photosensitive layer 30.In Fig. 2 (d), by developing procedure, from Removal is formed by the region (comprising barrier layer) other than photocuring portion by above-mentioned exposure process on substrate, thus on substrate Form the resist pattern 32 as photocuring portion.In Fig. 2 (e), by 32 conduct of resist pattern that will be used as photocuring portion The plating of mask forms coating layer 60 in the conductor layer 40 for the substrate not being coated by resist.In Fig. 2 (f), using strong It, will be by by dodging erosion (flash etching) processing after the aqueous solution of alkali removes the resist pattern 32 as photocuring portion The conductor layer 40 that resist pattern 32 covers removes, thus formed comprising after etching process coating layer 62 and etching process after The conductive pattern 70 of conductor layer 42.Conductor layer 40 can be identical with the material of coating layer 60, can also be different.When conductor layer 40 and plating When layer 60 is identical material, conductor layer 40 can carry out integrated with coating layer 60.It should be noted that projection exposure in Fig. 2 Mode is illustrated, but mask exposure mode, LDI Exposure mode can be used together also to form resist pattern 32.

More than, the suitable embodiment of the disclosure is illustrated, but the disclosure is not by above embodiment Any restriction.

Embodiment

Hereinafter, carrying out more specific description to the disclosure based on embodiment, but the present disclosure is not limited to following embodiments.It needs Illustrate, unless otherwise specified, then " part " and " % " is quality criteria.

Firstly, synthesizing binder polymer (Α -1) shown in following table 1~3 according to synthesis example 1.

1 > of < synthesis example

By the methacrylic acid 125g, methyl methacrylate 25g, benzyl methacrylate 125g as polymerizable monomer And styrene 225g is mixed with azodiisobutyronitrile 1.5g, prepares solution a.

In addition, by azodiisobutyronitrile 1.2g be dissolved in methyl cellosolve 60g and toluene 40g mixed liquor (mass ratio 3: 2) in 100g, solution b is prepared.

On the other hand, into the flask for having blender, reflux cooler, thermometer, dropping funel and nitrogen ingress pipe Mixed liquor (hereinafter also referred to as " mixed liquor the x ") 400g for adding methyl cellosolve and toluene that mass ratio is 3:2, is blown on one side Nitrogen is stirred on one side, and is heated to 80 DEG C.

The mixed liquor x through 4 hours being added dropwise to above-mentioned solution a in the state that rate of addition is set as fixed in flask In, then stirred 2 hours at 80 DEG C.Then, in the state that rate of addition is set as fixed through 10 minutes by above-mentioned solution b drop It adds in the solution in the flask, then the solution in flask is stirred 3 hours at 80 DEG C.Further, made flask through 30 minutes Interior solution is warming up to 90 DEG C, after 90 DEG C keep the temperature 2 hours, is cooled to room temperature and obtains the molten of binder polymer (Α -1) Liquid.The solution of the binder polymer (Α -1) is to add nonvolatile component (solid component) after mixed liquor x and become 50 matter Prepared by the mode of amount %.

The weight average molecular weight of binder polymer (Α -1) is 50,000, acid value 163mgKOH/g.It should be noted that Acid value is measured by neutralization titration.Specifically, measuring in the following way: into the solution 1g of binder polymer Acetone 30g is added, after dissolving it equably, suitable be used as is added in the solution of Xiang Shangshu binder polymer and is referred to Show the phenolphthalein of agent, and is titrated using the KOH aqueous solution of 0.1N.Weight average molecular weight by gel permeation chromatography (GPC) into Row measurement, and converted by using the standard curve of standard polystyren to export.The condition of GPC described below.

- GPC condition-

Pump: Hitachi's L-6000 type (Hitachi Co., Ltd's system)

Chromatographic column: 3 total below (chromatographic column specification:It is Hitachi Chemical Co., Ltd. System)

Gelpack GL-R420

Gelpack GL-R430

Gelpack GL-R440

Elutriant: tetrahydrofuran

Sample solution concentration: the binder polymer 120mg that solid component is 50 mass % is chosen, the four of 5mL are dissolved in Sample is prepared in hydrogen furans.

Measuring temperature: 25 DEG C

Flow: 2.05mL/ minutes

Detector: Hitachi L-3300 type RI (Hitachi Co., Ltd's system, product name)

The barrier layer < forms the preparation > for using resin combination

Next, each ingredient shown in following table 1~table 3 is mixed with amount (unit: mass parts) shown in the table, To obtain barrier layer formation resin combination.It is set specifically, slowly addition is water-soluble into the water and alcohols of room temperature Rouge is heated to 90 DEG C after adding whole amount.After reaching 90 DEG C, stirs 1 hour, be cooled to room temperature, to obtain barrier layer Formation resin combination.It should be noted that the use level in addition to solvent in 1~table of table 3 is in terms of solid component Use level.

The preparation > of < photosensitive polymer combination

Next, each ingredient shown in following table 1~table 3 is mixed with amount (unit: mass parts) shown in the table, To obtain photosensitive polymer combination.

[table 1]

[table 2]

[table 3]

The details of each ingredient in 1~table of table 3 is as follows.

(water-soluble resin)

* 1: PVAC polyvinylalcohol -205 (Kuraray Co., Ltd.'s system, product name, saponification degree=87 mole %, average polymerization Degree=500)

* 2: PVAC polyvinylalcohol -203 (Kuraray Co., Ltd.'s system, product name, saponification degree=87 mole %, average polymerization Degree=300)

* 3: PVAC polyvinylalcohol -210 (Kuraray Co., Ltd.'s system, product name, saponification degree=87 mole %, average polymerization Degree=1000)

* 4: polyvinylpyrrolidone K-30 (Nippon Shokubai Co., Ltd's system, product name)

(A) ingredient: binder polymer

* 5:(A-1) (binder polymer obtained in synthesis example 1 (A-1))

Methacrylic acid/methyl methacrylate/benzyl methacrylate/styrene=25/5/25/45 (mass ratio), Weight average molecular weight=50,000, solid component=50 mass %, methyl cellosolve/toluene=3/2 (mass ratio) solution

(B) ingredient: the photopolymerizable compound with ethylene unsaturated bond

* 6:FA-321M (Hitachi Chemical Co., Ltd.'s system, product name)

Bis- (4- (five ethyoxyl of the methacryloxy) phenyl) propane of 2,2-

* 7:FA-024M (Hitachi Chemical Co., Ltd.'s system, product name)

EOPO is modified dimethylacrylate

* 8:BPE-200 (village Xin Zhong chemical industry Co. Ltd. system, product name)

Bis- (4- (methacryloxy diethoxy) phenyl) propane of 2,2-

* 9:BP-2EM (Kyoeisha Chemical Co., Ltd.'s system, product name)

Bis- (4- (the more ethyoxyls of the methacryloxy) phenyl) propane of 2,2-

* 10:DPEA-12 (Nippon Kayaku K. K's system, product name)

Ethylene-oxide-modified dipentaerythritol hexaacrylate

(C) ingredient: Photoepolymerizationinitiater initiater

* 11:B-CIM (Baotugu Chemical Industrial Co., Ltd's system, product name)

2,2 '-bis- (2- chlorphenyl) -4,4 ', 5,5 '-tetraphenyl bisglyoxalines

(D) ingredient: photosensitizer

* 12:EAB (Baotugu Chemical Industrial Co., Ltd's system, product name)

4,4 '-bis- (diethylamino) benzophenone

(E) ingredient: polymerization inhibitor

* 13:TBC (Dainippon Ink Chemicals's system)

4- tert-butyl catechol

[embodiment 1~15 and comparative example 1~7]

The production > of < photosensitive element

As the support membrane of photosensitive element, PET film shown in 1~table of table 3 is prepared.

The details of PET film shown in 1~table of table 3 is as follows.

FB40: there is biaxial orientation PET film (Dongli Ltd.'s system, the product of the 3-tier architecture of lubricant layer at the table back side Name, thickness: 16 μm)

A1517: one side have lubricant layer 2 layers of structure biaxial orientation PET film (Toyo Boseki K. K's system, Product name, thickness: 16 μm)

G2H: biaxial orientation PET film (Supreme Being people's Du Pont membrane strain formula of the single layer structure (lubricant is doped) containing lubricant Commercial firm's system, product name, thickness: 15.5 μm)

(production on barrier layer)

Next, barrier layer formation is coated on PET film (support with resin combination in such a way that thickness becomes uniform Film) on, and dry 10 minutes using 95 DEG C of hot wind convection type drying machine, formed it is dry after with a thickness of 5 μm of barrier layer.It needs When being noted that the two sides difference when the density of lubricant in PET film, is formed and stopped in the few one side of the lubricant of PET film Layer, when the one side of PET film has lubricant layer, the one side in the lubricant layer side of PET film forms barrier layer.

(production of photosensitive layer)

Next, on the barrier layer that photosensitive polymer combination is coated on support membrane in such a way that thickness becomes uniform, Dry 10 minutes using 100 DEG C of hot wind convection type drying machines, formed it is dry after with a thickness of 10 μm of photosensitive layer.

Next, polyethylene protective film (protective layer) (Tamapoly Co. Ltd. system, product name " NF-15 ") is bonded In on the photosensitive layer, the photosensitive element for being sequentially laminated with PET film (support membrane), barrier layer, photosensitive layer and protective layer is obtained.

The measurement > of < remaining alcohols amount

The amount for the remaining alcohols being formed by barrier layer is measured by gas-chromatography mass analysis.Gas-chromatography matter The determination condition for measuring analysis is as described below.It should be noted that project " the remaining alcohols in barrier layer of table 1, table 2 and table 3 Amount " indicates the amount of alcohols of the carbon number more than or equal to 3.It should be noted that " < 1.0 " is meant more than 0 and less than 1.0.

(determination condition of gas chromatography mass analysis)

Measurement device: GC/MS QP-2010 (Shimadzu Seisakusho Ltd.'s system, product name)

Chromatographic column: HP-5MS (Agilent Technologies Co. Ltd. system, product name)

Oven temperature (Oven Temp): it is heated after five minutes at 40 DEG C, is warming up to 300 DEG C with the ratio of 15 DEG C/min

Carrier gas: helium, 1.0mL/min

Interface temperature: 280 DEG C

Ion source temperature: 250 DEG C

Sample injection volume: 0.1mL

The production > of < laminated body

To copper-clad laminated board (substrate, the Hitachi as expoxy glass material for the copper foil for being laminated with 12 μm of thickness on two sides Manufactured at Co., Ltd., " MCL-E-67 ") copper surface carry out sour processing and washed after, be dried using air stream. Copper-clad laminated board is heated up to 80 DEG C, removes protective layer on one side, it on one side will be above-mentioned photosensitive in such a way that photosensitive layer contacts copper surface Property element is crimped on copper-clad laminated board respectively.Crimping is the hot-rolling using 110 DEG C, with 1.0m/ minutes under the pressure of 0.40MPa Roller speed carry out.So obtain the laminated body for being sequentially laminated with substrate, photosensitive layer, barrier layer and support membrane.By these layers Stack is used as the test film in test as shown below.As laminating machine, HLM-3000 (Laminator plants of formula meetings of great achievement are used Society's manufacture, product name).

The evaluation > of < support membrane fissility

Test film is placed 1 hour in the environment of 23 DEG C and humidity 50%.Then, in 135 degree of peel angle, removing speed Degree removed the PET film as support membrane from test film under conditions of 500mm/ seconds, evaluated support membrane according to evaluation criteria below Fissility.Show the results of the evaluation following table 4~table 6.

A: it is only thereafter easily released as the PET film of support membrane.

B: it is attached with barrier layer in a part for the support membrane being stripped, or support membrane can not be removed.

The evaluation > of < resolution ratio

In order to check resolution ratio, by support membrane after test film removing, 41 grades of Hitachi is loaded on the barrier layer of test film Stage exposure meter, and place that have line width/interval width be z/z's (z=2~20 (changing with 1 μm of interval)) (unit: μm) Wiring pattern uses the glass mask of pattern as resolution ratio evaluation, uses the projection exposure of the high-pressure sodium lamp with wavelength 365nm Machine (manufacture of Ushio Electric Co., Ltd, product name UX-2240SM-XJ01), after the development of 41 grades of stage exposure meters of Hitachi Remaining stage series become 8 grades when irradiation energy, photosensitive layer is exposed across barrier layer.After exposure, incited somebody to action in room temperature Test film is washed, and barrier layer is removed.Next, in 30 DEG C of aqueous sodium carbonates using 1 mass %, when with most short development Between 2 times of time by photosensitive layer spray development, remove unexposed portion.Here, most short developing time is by measuring unexposed portion It is found out by time that above-mentioned development treatment is completely removed.The line part in unexposed portion will be completely eliminated by development treatment The minimum value (unit: μm) in the width of interval between (exposure portion) is set as the index of resolution ratio evaluation.It should be noted that the numerical value It is smaller, then mean that resolution ratio is the better.It shows the result in following table 4~table 6.

The evaluation > of < resist pattern shape

For the substrate evaluated in the evaluation of above-mentioned resolution ratio, observed by scanning electron microscope (SEM) Line width/interval width is the cross sectional shape of the resist pattern of 10/10 (unit: μm).Using the cross sectional shape of resist pattern as The evaluation of resist pattern shape and be shown in following table 4~table 6.

For the photosensitive element of comparative example 1~7, the deterioration of support membrane fissility fails to form resist pattern, therefore nothing The evaluation of method progress resolution ratio and resist pattern shape.

The evaluation > of the < barrier layer solution transparency

Barrier layer formation resin combination as reference sample, in addition to not using embodiment 1~15 and comparative example 1~7 Other than alcohols in object, prepare in the same manner as the barrier layer formation resin combination of embodiment 1~15 and comparative example 1~7 Composition.Then, for embodiment 1~15 and comparative example 1~7 barrier layer formation with resin composition solution (hereinafter, also referred to as For " barrier layer solution ") and reference sample the transparency, observed, evaluated as follows by visual observation.Evaluation result is shown In following table 4~table 6.

A: compared with reference sample, the muddiness of barrier layer solution is equal extent or less.

B: compared with reference sample, barrier layer solution produces more muddiness.

The evaluation > of the barrier layer the < transparency

By the barrier layer formation resin combination of embodiment 1~15 and comparative example 1~7 in such a way that thickness becomes uniform Be coated on support membrane, dry 10 minutes using 95 DEG C of hot wind convection type drying machines, thus formed it is dry after with a thickness of 5 μm Barrier layer.Barrier layer formation resin combination as reference sample, in addition to not using embodiment 1~15 and comparative example 1~7 Other than alcohols in object, the barrier layer formation with embodiment 1~15 and comparative example 1~7 is prepared as group with resin combination Object is closed, forms barrier layer using the composition.Then, the appearance on barrier layer is observed by visual observation, is commented as follows Valence.It shows the results of the evaluation in following table 4~table 6.

A: compared with reference sample, muddy and gap generation degree is equal extent or less in barrier layer.

B: compared with reference sample, a part or entirety on barrier layer produce more muddiness or gap.

[table 4]

[table 5]

[table 6]

Using the projection exposure machine of high resolution, remaining stage series be 8 grades, little energy under conditions of be exposed When, it confirming in embodiment 1~15, the fissility on support membrane and barrier layer is high, and in contrast, being supported in comparative example 1~7 Film is low with the fissility on barrier layer.

Industrial availability

As described above, according to the disclosure, it is possible to provide a kind of to can be improved barrier layer without using removing promotor With the photosensitive element of the fissility of support membrane, barrier layer formation resin combination, resist pattern forming method and The manufacturing method of printing distributing board.

Symbol description

1: photosensitive element, 2: support membrane, 3,20: barrier layer, 4,30: photosensitive layer, 5: protective layer, 32: resist pattern, 40: conductor layer, 42: the conductor layer after etching process, 50: insulating layer, 60: coating layer, 62: the coating layer after etching process, 70: Conductive pattern, 80: active ray.

Claims

1. a kind of photosensitive element, successively has support membrane, barrier layer and photosensitive layer, water-soluble resin is contained on the barrier layer It is greater than or equal to 3 alcohols with carbon number, alcohols of the carbon number more than or equal to 3 contains selected from by following chemical formula (1)~(3) At least one of the group of the composition of compound represented by represented compound and the following general formula (4),

[changing 1]

[changing 2]

[changing 3]

[changing 4]

In general formula (4), R¹¹Indicate alkyl, R¹²Indicate alkylidene, R¹¹Group and R¹²The sum of the carbon number of group be greater than or equal to 3。

2. photosensitive element according to claim 1, the carbon number is more than or equal to 3 alcohols for the molten of 20 DEG C of water Xie Du is more than or equal to 300mL/ water 100mL.

3. photosensitive element according to claim 1 or 2, the carbon number in the barrier layer is greater than or equal to 3 alcohol The content of class more than 0 mass % and is less than or equal to 2.0 mass % on the basis of the total amount on the barrier layer.

4. photosensitive element according to claim 1 or 2, the water-soluble resin contains polyvinyl alcohol.

5. photosensitive element according to claim 1 or 2, the support membrane is polyester film.

6. photosensitive element according to claim 1 or 2, in the general formula (4), R¹¹Group and R¹²Group carbon number The sum of be less than or equal to 10.

7. photosensitive element according to claim 1 or 2, in the general formula (4), R¹¹Group and R¹²Group carbon number The sum of be less than or equal to 8.

8. photosensitive element according to claim 1 or 2, in the general formula (4), R¹¹Group and R¹²Group carbon number The sum of be less than or equal to 7.

9. photosensitive element according to claim 1 or 2, in the general formula (4), R¹¹Group and R¹²Group carbon number The sum of be less than or equal to 6.

10. photosensitive element according to claim 1 or 2, in the general formula (4), R¹¹Group and R¹²Group carbon The sum of number is less than or equal to 5.

11. photosensitive element according to claim 1 or 2, in the general formula (4), R¹¹Represented alkyl be carbon number 1~ 4 alkyl.

12. photosensitive element according to claim 1 or 2, in the general formula (4), R¹²Represented alkylidene is carbon number 1 ~3 alkylidene.

13. photosensitive element according to claim 1 or 2, compound represented by the general formula (4) is 2- butoxy- Ethyl alcohol or 1- methoxy-2-propanol.

14. photosensitive element according to claim 2, alcohols of the carbon number more than or equal to 3 is for 20 DEG C of water Solubility is greater than or equal to 500mL/ water 100mL.

15. photosensitive element according to claim 2, alcohols of the carbon number more than or equal to 3 is for 20 DEG C of water Solubility is greater than or equal to 1000mL/ water 100mL.

16. photosensitive element according to claim 3, the carbon number in the barrier layer is greater than or equal to 3 alcohols Content on the basis of the total amount on the barrier layer be 0.001~2.0 mass %.

17. photosensitive element according to claim 3, the carbon number in the barrier layer is greater than or equal to 3 alcohols Content on the basis of the total amount on the barrier layer be 0.005~1.0 mass %.

18. the saponification degree of photosensitive element according to claim 4, the polyvinyl alcohol is greater than or equal to 50 moles of %.

19. the saponification degree of photosensitive element according to claim 4, the polyvinyl alcohol is greater than or equal to 70 moles of %.

20. the saponification degree of photosensitive element according to claim 4, the polyvinyl alcohol is greater than or equal to 80 moles of %.

21. photosensitive element according to claim 4, the average degree of polymerization of the polyvinyl alcohol is 300~5000.

22. photosensitive element according to claim 4, the average degree of polymerization of the polyvinyl alcohol is 300~3500.

23. photosensitive element according to claim 4, the average degree of polymerization of the polyvinyl alcohol is 300~2000.

24. photosensitive element according to claim 1 or 2, the water-soluble resin includes polyvinyl alcohol and polyethylene Base pyrrolidones.

25. photosensitive element according to claim 24, the matter of the polyvinyl alcohol and the polyvinylpyrrolidone Amount is than being 40:60~90:10.

26. photosensitive element according to claim 24, the matter of the polyvinyl alcohol and the polyvinylpyrrolidone Amount is than being 50:50~90:10.

27. photosensitive element according to claim 24, the matter of the polyvinyl alcohol and the polyvinylpyrrolidone Amount is than being 60:40~90:10.