CN104903207B

CN104903207B - Photoresist duplexer is rolled up

Info

Publication number: CN104903207B
Application number: CN201380068564.2A
Authority: CN
Inventors: 小谷雄三
Original assignee: Asahi Kasei Kogyo KK
Current assignee: Asahi Kasei Corp
Priority date: 2012-12-27
Filing date: 2013-12-26
Publication date: 2017-04-05
Anticipated expiration: 2033-12-26
Also published as: CN106966074B; MY176080A; KR20150079919A; TWI522303B; KR101950064B1; JP6315724B2; KR102191080B1; KR20190018037A; JPWO2014104217A1; WO2014104217A1; TW201431769A; TWI611990B; CN106966074A; TW201613817A; CN106393838A; JP6046746B2; CN104903207A; JP2017071445A; CN106393838B

Abstract

The present invention is provided and can roll up the photoresist duplexer volume that foreign body is simply removed by end face from photoresist duplexer in unpacking.The structure of photoresist duplexer volume is; by photoresist duplexer in core wound into rolls; by make volume end face guard block with the end contact of the photoresist duplexer for being wound in the way of configure; for volume end face guard block; there is adhesive composition with volume end contact side, photoresist duplexer includes at least supporting layer and the photo-sensitive resin for being laminated in the supporting layer.

Description

Photoresist duplexer is rolled up

Technical field

The present invention relates to photoresist duplexer volume.

Background technology

In the past, several ways were disclosed as the packaging of photosensitive element.For example disclose to protect volume end face and set Put the packaging (patent documentation 1) of end face guard block.

Prior art literature

Patent documentation

Patent documentation 1：Japanese Unexamined Patent Publication 2005-41537 publications

The content of the invention

Problems to be solved by the invention

The invention solves the problems that problem be, there is provided unpacking when can be simply by foreign body from photoresist duplexer The photoresist duplexer volume that volume end face is removed.

For solution to problem

Above-mentioned problem can be solved by the technical scheme below of the present invention.I.e. the present invention is as follows：

[1]

A kind of photoresist duplexer volume, wherein, by photoresist duplexer in core wound into rolls, roll up end Face guard block according to configuring with the mode of the end contact of the photoresist duplexer for winding up,

The volume end face guard block for volume end contact side there is adhesive composition,

The photoresist duplexer includes at least supporting layer and is laminated in the photo-sensitive resin of the supporting layer.

[2]

Photoresist duplexer volume according to [1st] item, it is characterised in which is covered by shading sheet material.

[3]

Rolled up according to the photoresist duplexer of [2nd] Xiang Shu, it is characterised in that the shading sheet material is tubular.

[4]

Photoresist duplexer volume according to any one of [1st]～[3] item, wherein,

The length of the core is longer than the width of the photoresist duplexer,

The volume end face guard block is the ring-type of the end face for being configured at the photoresist duplexer in wound into rolls Sheet material, the ring-type sheet material are configured in the way of the extension through the core.

[5]

Photoresist duplexer volume according to [4th] item, it is characterised in that the internal diameter of the ring-type sheet material is volume 1～1.1 times of core external diameter.

[6]

Photoresist duplexer volume according to [4th] or [5] item, it is characterised in that

The ring-type sheet material is present in aerial mode according to its half and is arranged on the flat board for protruding horizontally up, by the ring Shape sheet material is present in aerial part from the front end of the farthest ring-type sheet material of flat board and flat board and the annular lamina When the distance between face of material contact side is set to deflection distance H (mm), the half of the ring-type sheet material external diameter and is set to R (mm), H/R For 0.06～0.59.

[7]

Photoresist duplexer volume according to any one of [1st]～[6] item, it is characterised in that the volume end Face guard block is 5gf/inch～250gf/inch with the bonding force of low-density polyethylene film.

[8]

Photoresist duplexer volume according to any one of [1st]～[7] item, it is characterised in that the volume end The base material of face guard block be dust-free paper, low dirt paper, synthetic paper or, the material fitted with resin base material of paper.

[9]

Photoresist duplexer volume according to any one of [1st]～[8] item, it is characterised in that described photosensitive Property resin bed is the layer comprising photosensitive polymer combination, and the photosensitive polymer combination includes the alkali-soluble containing carboxyl Macromolecule, addition polymerization monomer, Photoepolymerizationinitiater initiater.

[10]

Photoresist duplexer volume according to [9th] item, it is characterised in that the alkali-soluble containing carboxyl Macromolecule is the material of styrene or derivatives thereof copolymerization.

[11]

Photoresist duplexer volume according to [9th] or [10] item, it is characterised in that the addition polymerization list Body includes bisphenol-A system (methyl) acrylate compounds.

[12]

Photoresist duplexer volume according to any one of [9th]～[11] item, it is characterised in that the light gathers Initiator is closed comprising six aryl bisglyoxalines or derivatives thereof.

[13]

Photoresist duplexer volume according to any one of [1st]～[12] item, it is characterised in that the bonding Agent compositionss are resin comprising acrylic acid (ester).

[14]

Photoresist duplexer volume according to any one of [1st]～[13] item, it is characterised in that the bonding Agent compositionss contain binding agent and granule, more than 50 mass % of the granule 80 of the coating thickness with the adhesive composition ～120% diameter, and the content of the granule relative to 100 parts by weight of binder be 5 weight portions to 30 weight portions.

[15]

A kind of manufacture method of photoresist duplexer volume, it is characterised in that

The photoresist duplexer of wound into rolls in core, with the photoresist duplexer for winding up End contact mode configures volume end face guard block, wherein,

The length of the core is longer than the width of the photoresist duplexer,

The photoresist duplexer includes at least supporting layer and is laminated in the photo-sensitive resin of the supporting layer,

The volume end face guard block has adhesive composition in the side with volume end contact,

The volume end face guard block is following ring-type sheet materials：With one or be divided into the state of some being wound into a roll The end face configuration of the photoresist duplexer of shape, after being configured on the end face of photoresist duplexer of wound into rolls 1～1.1 times for core external diameter of the internal diameter of the ring-type sheet material.

[16]

The manufacture method of the photoresist duplexer volume according to [15th] item, it is characterised in that the annular lamina The internal diameter of material is 1.001～1.1 times of the external diameter of the core, in the way of the extension through the core configures the ring Shape sheet material.

[17]

The manufacture method of the photoresist duplexer volume according to [15th] or [16] item, it is characterised in that

[18]

The manufacture method of the photoresist duplexer volume according to any one of [15th]～[17] item, its feature exist In the ring-type sheet material is 5gf/inch～250gf/inch with the bonding force of low-density polyethylene film.

[19]

A kind of packing method of photoresist duplexer volume, it is characterised in that usage right is arbitrary in requiring 15～18 Method manufacture photoresist duplexer volume described in, further covers the photo-sensitive resin by the shading sheet material of tubular Stack is rolled up.

[20]

A kind of ring-type sheet material, which is the ring-type sheet material of thin film film rolling of wound into rolls in core, wherein,

The length of the core is longer than the width of the thin film,

1～1.1 times for core external diameter of the internal diameter of the ring-type sheet material, and

The end contact of the ring-type sheet material and the thin film of the winding, in the ring-type sheet material and the end contact Side has adhesive composition, is configured in film rolling in the way of the extension through the core.

[21]

Ring-type sheet material according to [20th] item, wherein, the thin film is photoresist duplexer.

[22]

Ring-type sheet material according to [20th] or [21] item, it is characterised in that

[23]

Ring-type sheet material according to any one of [20th]～[22] item, it is characterised in that itself and Low Density Polyethylene The bonding force of thin film is 5gf/inch～250gf/inch.

[24]

Ring-type sheet material according to any one of [20th]～[23] item, it is characterised in that its base material having is nothing Dirt paper, low dirt paper, synthetic paper or, the material fitted with resin base material of paper.

[25]

Ring-type sheet material according to any one of [21st]～[24] item, it is characterised in that the photo-sensitive resin The layer comprising photosensitive polymer combination, the photosensitive polymer combination comprising the alkali-soluble macromolecule containing carboxyl, Addition polymerization monomer, Photoepolymerizationinitiater initiater.

[26]

Ring-type sheet material according to [25th] item, it is characterised in that the alkali-soluble macromolecule containing carboxyl is The material of styrene or derivatives thereof copolymerization.

[27]

Ring-type sheet material according to [25th] or [26] item, it is characterised in that the addition polymerization monomer is comprising double Phenol A systems (methyl) acrylate compounds.

[28]

Ring-type sheet material according to any one of [25th]～[27] item, it is characterised in that the Photoepolymerizationinitiater initiater Comprising six aryl bisglyoxalines or derivatives thereof.

[29]

Ring-type sheet material according to any one of [20th]～[28] item, it is characterised in that described adhesive compositionss It is resin comprising acrylic acid (ester).

[30]

Ring-type sheet material according to any one of [20th]～[29] item, it is characterised in that described adhesive compositionss Containing binding agent and granule, more than 50 mass % of the granule 80～120% of the coating thickness with the adhesive composition Diameter, and the content of the granule relative to 100 parts by weight of binder be 5 weight portions to 30 weight portions.

[31]

A kind of film rolling, which possesses the ring-type sheet material described in being covered by shading sheet material, [20]～[30].

The effect of invention

If using the photoresist duplexer volume of the present invention, can be simply by foreign body from photonasty tree in unpacking Lipid layer stack volume end face is removed.

Description of the drawings

Fig. 1 be by photoresist duplexer in core wound into rolls, and roll up end face guard block according to institute One embodiment of the photoresist duplexer volume that the mode of the end contact of the photoresist duplexer of winding is configured Schematic diagram.

Fig. 2 is the figure of half R of the external diameter for representing deflection distance H and ring-type sheet material.

Fig. 3 is the signal of the embodiment for representing the photoresist duplexer volume covered by the shading sheet material of tubular Figure.

Specific embodiment

Hereinafter, describe in detail for preferred embodiment of the present invention (hereinafter referred to as " embodiment ").Need explanation , the invention is not restricted to following embodiment, various modifications can be carried out to implement in the range of its main idea.

Photoresist duplexer volume is along its length in volume by the photoresist duplexer of strip (banding) Wind on core, and end face guard block is rolled up according to the end face (sense of the banding with the photoresist duplexer for being wound The width end side of photosensitive resin layer stack) the photoresist duplexer volume that configures of the mode that contacts.

Fig. 1 represents the schematic diagram of an embodiment of this photoresist duplexer volume 10.Here, photo-sensitive resin Stack 1 includes supporting layer 4, the photo-sensitive resin 5 for being laminated in the supporting layer and arbitrary protective layer 6, and the duplexer 1 is wound In core 2.And, volume end face guard block 3 is set with two end contacts of the photoresist duplexer of the winding. This, volume end face guard block 3 is represented as ring-type sheet material.

(photoresist duplexer)

Photoresist duplexer includes at least supporting layer and the photo-sensitive resin being laminated on the supporting layer, preferably enters One step includes the protective layer being laminated on photo-sensitive resin.It is also against corrosion comprising dry film is referred to as in photoresist duplexer Agent, the photosensitive film of dry film photoresist.

As long as supporting layer supports the structure of photo-sensitive resin.As the supporting layer that can be used, preferably Through the transparent layer of the light launched from exposure light source.As such supporting layer, polyethylene terephthalate can be included Ester film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer thin film, polyvinylidene chloride film, vinylidene chloride Copolymerization thin film, polymethyl methacrylate copolymer thin film, polystyrene film, polyacrylonitrile thin film, styrol copolymer are thin Film, polyamide film, cellulose derivative film etc..To can use after these thin film stretchings as needed.From resolution Viewpoint is set out, and preferred mist degree is less than 5 thin film.More preferably mist degree is less than 3, and further preferred mist degree is less than 2.5, is more entered The preferred mist degree of one step is less than 1.With regard to the thickness of supporting layer, relatively thin layer is favourable in terms of image formative and economy , but from the thermal contraction grade needed when maintaining photosensitive resin coating composition layer, preferably use 10 μm～30 μm Thickness.GR19, GR16, Mitsubishi Plastics that Supreme Being people's DuPont Film (strain) is manufactured, Inc. manufactures can for example be included R310-16, R340G16, East レ Port リエステ Le Off ィ Le system (strain) manufacture FB40 (16 μm of thickness), FB60 (16 μm of films It is thick) etc..

For protective layer, protective layer is substantially smaller than supporting layer with the closing force of photo-sensitive resin, therefore, it is possible to hold Change places stripping.For example, as protective layer, it may be preferred to using polyethylene film, polypropylene film and stretched polypropene film etc.. Further, it is possible to use the excellent thin film of fissility disclosed in Japanese Unexamined Patent Application 59-202457 publication.The thickness of protective layer is excellent Elect 10～100 μm as, more preferably 10～50 μm.For example, GF-18, GF- of the manufacture of Tamapoly Co., Ltd.s can be included 818th, GF-858 etc..

For photo-sensitive resin, photosensitive polymer combination can be coated supporting layer and be dried so as to carry out layer It is folded.The thickness of photo-sensitive resin is preferably 5～100 μm, and the preferred upper limit is 50 μm.Due to the thickness of photo-sensitive resin Closer to 5 μm, resolution is more improved, and closer to 100 μm, film-strength is more improved, therefore can be properly selected according to purposes.

As the method for manufacture photoresist duplexer, known method can be adopted.For example, prepare in advance by Photosensitive polymer combination for photo-sensitive resin is mixed with solvent as photosensitive polymer combination blending liquid, using rod Painting machine or roll coater are applied to supporting layer and are dried which, sense of the stacking comprising the photosensitive polymer combination on supporting layer Photosensitive resin layer.It is 500～4000mPA seconds that photosensitive polymer combination blending liquid preferably add solvent to be blended at 25 DEG C. From from the viewpoint of photosensitive polymer combination blending fluid viscosity, drying property, residual solvent amount, coating, foaminess, in solvent Can suitably selectively using butanone, acetone, ethanol, methanol, propanol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, Toluene etc..Then, by protective layer being laminated on the photo-sensitive resin, can make photoresist duplexer.

For photoresist duplexer, become web-like and use so that strip is wound in core.Spooling length does not have It is particularly limited to, from from the viewpoint of the weight and process easness of volume, preferably below 320m.If 1 photo-sensitive resin The stack base material more at most efficiency that can be laminated of volume is higher, therefore from from the viewpoint of productivity ratio, spooling length preferably 100m with On.

(core)

Core is also sometimes referred to as core body.Its shape is not particularly limited, and can be cylindrical shape, or and it is cylindric. As photoresist duplexer is used for electronic material as etching or plating resist layer and permanent pattern, therefore it is preferable to carry out The core of dustless process, the core of preferred plastic resin.The material of plastic resin preferably light, excellent strength, dustless Material.Polypropylene (PP) resin, acrylonitrile-butadiene-styrene (ABS) (ABS) resin, nylon resin, polrvinyl chloride tree can be used Fat etc., preferred ABS resin.The diameter of core is not particularly limited, and photoresist duplexer volume is being installed on laminater In the case of, in order to be installed on device, core is preferably the diameter of 2～5inch, more preferably 3inch.The length of core (when using cylindric or columned core be its axial length) compared with the width of photoresist duplexer, Ke Yixiang It is same or shorter, but when photoresist duplexer is wound, in order to may insure appropriate extension in both sides, preferably roll up Length of the length of core more than the width of photoresist duplexer.Annular lamina can be installed according to the mode through the extension Material, therefore preferably.Alternatively, it is also possible to the bearing for being referred to as core body support is embedded in the extension and so that photo-sensitive resin The mode that stack volume is not moved takes care of photoresist duplexer volume under vacant state.

(volume end face guard block)

For volume end face guard block, according to matching somebody with somebody with the mode of the end contact of the photoresist duplexer for being wound Put.It is not particularly limited as its shape, as long as at least a portion of end face will be rolled up with certain area and end contact The shape of covering protection does not just affect, these, it is preferred to according to the end contact with the photoresist duplexer of winding Mode through core extension ground configuration ring-type sheet material.Further preferably have and can substantially cover photonasty The ring-type of the width of the substantially overall size of laminated resin body volume end face.Volume end face guard block can be only used for what is wound One end of photoresist duplexer, but it is preferred for two ends.

It is when it is ring-type sheet material to roll up end face guard block, for its ring internal diameter, in order to use through core, preferred to omit More than the external diameter of core.In addition, being moved slightly away from the center of core by making the center of ring-type sheet material, thus ring-type sheet material is outer Week slightly exposes from the periphery of the photoresist duplexer of wound into rolls.So, become easy from the dismounting of ring-type sheet material Set out, ring internal diameter is preferably slightly larger than the external diameter of core.Specifically, when ring internal diameter is carried out for more than 1.001 times of core external diameter (Japanese is not blocked to core during installation：Zhang り pay I), thus it is preferred that.More preferably more than 1.005 times, more preferably 1.01 more than again.From protection volume end face entirety and from the viewpoint of removing foreign body, 1.1 times for the external diameter of core of preferred ring internal diameter Hereinafter, more preferably less than 1.05 times, more preferably less than 1.03 times.

For ring external diameter, in order to cover the end face of photoresist duplexer volume, preferably wound into rolls More than 0.99 times of the external diameter of photoresist duplexer, more preferably more than 1 times.In addition, from suppression to covering photonasty tree From the viewpoint of the attachments of packaging material such as the cylindrical pipe of light-proofness of lipid layer stack volume, ring external diameter is preferably photoresist Less than 1.1 times, more preferably less than 1.05 times, more preferably less than 1.03 times of the external diameter of duplexer volume.

For volume end face guard block base material, can include polyester, polyethylene terephthalate, polyphenylene sulfide, Polypropylene, respectively nylon, tensionless winkler foundation, stretching, biaxial stretch-formed material and Low Density Polyethylene, high density polyethylene (HDPE), hard Polrvinyl chloride, soft PVC, cellophane, acetate, Triafol T, polystyrene, Merlon, polyimides etc. Plastic resin and the paper of dust-proof process, the good quality paper of dust-proof process, clean-keeping paper and, paper and foregoing plastics resin patch The material that closes, synthetic paper etc..As photoresist duplexer is used as resist layer or plating resist layer and permanent pattern For electronic material, therefore the material of dustless process has been preferable to carry out it.From the generation of electrostatic less, it is good to the tracing ability of end face, From the viewpoint of foreign body removal is excellent and installation is also excellent, preferred substrates are the paper of dust-proof process, dust-proof process Good quality paper, clean-keeping paper and, paper fit with foregoing plastics resin material, synthetic paper is used as material.Synthetic paper preferably will Polypropylene is used as main material.

When base material be the paper of dust-proof process, the good quality paper of dust-proof process, clean-keeping paper and, paper and foregoing plastics tree During the material of fat laminating, the thickness of base material is preferably 50～500 μm.From from the viewpoint of installation, preferably 50 μm with On, from from the viewpoint of the tracing ability to end face, foreign body removal, preferably less than 500 μm, more preferably 60～200 μm, enter One step is preferably 60～150 μm.

For volume end face guard block, from from the viewpoint of release property, soil resistance, it is also possible to surface is embossed and is added Work.For volume end face guard block, there is adhesive composition in the side of the end contact rolled up with photoresist duplexer. Volume end face guard block preferably overlooks circular ring-type sheet material.

For aforementioned cyclic sheet material, aforementioned cyclic sheet material is present in aerial mode according to its half and is arranged on and protrudes horizontally up Flat board on, by aforementioned cyclic sheet material be present in aerial part from the top of the farthest aforementioned cyclic sheet material of flat board and Flat board is set to deflection distance H (mm), aforementioned cyclic sheet material external diameter with the distance between the face of aforementioned cyclic sheet material contact side When half is set to R (mm), H/R is preferably 0.06～0.59.From from the viewpoint of the volume end face installation of ring-type sheet material, H/R is excellent Elect less than 0.59 as.More preferably less than 0.5, more preferably less than 0.45.Go from the tracing ability to rolling up end face with foreign body From the viewpoint of except property, preferably more than 0.06.More preferably more than 0.1, more preferably more than 0.15.

The assay method of deflection distance H is as follows.First, as shown in Fig. 2 along substantial horizontal direction (with it is vertical The orthogonal direction in direction) ring-type sheet material 3 is set on the substantial flat board 7 that stretches out.Now, facing up for binding agent is will be provided with, Mode according to not fitted with flat board 7 is arranged.Half according to ring-type sheet material 3 is present in the air, i.e., according in ring-type sheet material 3 The heart is located at the mode stationary ring sheet material for being essentially linear edge existing for the end of flat board.When fixed, such as Fig. 2 institutes Show, it is also possible to be fixed using fixed component 8.Now, ring-type sheet material 3 will not be bent by affecting beyond gravity or Bending.From the aerial part (from the part that end is exposed) of ring-type sheet material, distance is present in by L fonts scale measure flat Hanging down between the imaginary plane formed with the face contacted with ring-type sheet material of flat board by the farthest top of ring-type sheet material in the edge of plate Nogata is to distance.Determine place and be set to Fushi City, Shizuoka,Japan County.

(adhesive composition)

For adhesive composition, can select to use when volume end face guard block has been peeled off in photopolymer film No cull on end face, the attachment for not having photoresist when volume end face guard block has been peeled off on volume end face guard block Known adhesive composition.

Wherein, from from the viewpoint of foreign body removal with release property, preferably it is the combination of resin comprising acrylic acid (ester) Thing.Photosensitive polymer combination is comprising the alkali-soluble macromolecule containing carboxyl, addition polymerization monomer, Photoepolymerizationinitiater initiater Photosensitive polymer combination, when adhesive composition is resin comprising acrylic acid (ester), from further highly can having concurrently From the viewpoint of foreign body removal and release property it is preferred that.

For adhesive composition preferably comprises granule, more than 50 mass % of the granule preferably with the binding agent group The diameter of the 80～120% of the coating thickness of compound, and the content of the granule is 5 weight relative to 100 parts by weight of binder Part is to 30 weight portions.It should be noted that the diameter of granule uses micro- sem observation, for arbitrary 100 granules, observe Its maximum gauge, and calculate its meansigma methods.

From from the viewpoint of release property, the diameter of granule is preferably more than 80%, from from the viewpoint of viscosity, preferably Less than 120%.More preferably 90～110%, more preferably 100%.

For granule, though generally can be the granule of Monosized powder in theory, but it is actually more in the case of be difficult to obtain .It is preferred that the granule of the grading curve for having particle size distribution as narrow, i.e. sharp as possible.

It is preferred that more than 50 mass % of binding agent total amount being the 80～120% of the coating thickness of binding agent diameter.From From the viewpoint of the balance of release property and viscosity, more than more preferably 70 mass %, more than more preferably 80 mass %.

The content of granule be preferably relative to 100 parts by weight of binder be 5 weight portions to 30 weight portions.In situation about attaching Under, from from the viewpoint of the de-bubbled of air, more than preferably 5 weight portions, from from the viewpoint of cementability, preferably 30 weights Below amount part.More preferably 10 weight portions are to 25 weight portions.When the material of granule is glass, 15～30 weight portions are suitable , it is plastic in the case of be preferably 5～25 weight portions.

The material of granule is preferably plastics, inorganic material.As plastics, polymethacrylates system, poly- first can be included Base acrylic acid methyl ester. system, polystyrene, polystyrene acrylic acid (ester) system, polyethylene-based, polypropylene-based, polystyrene fourth two Alkene system, polystyrene divinylbenzene system, polyurethane series, polyphenyl substituted melamine system, melamine series.As inorganic material, Glass, silicon dioxide (silicate mineral), Calcium Carbonate can be included.

The bonding force of binding agent can be carried by reducing the overall softening temperature of compositionss, improving the polarity of resinous principle It is high.

As volume end face guard block and the bonding force of low-density polyethylene film, from the sight of foreign body removal and installation Point sets out, preferably 5gf/inch～250gf/inch, more preferably 50gf/inch～240gf/inch.

It should be noted that the bonding force is measured in such a way.That is, with hand pressure roller in volume end face guard block Formation have adhesive composition layer face on attach low-density polyethylene film (LDPE) sheet material.Low-density polyethylene film Using TAMAPOLY Co., the GF-858 of Ltd manufactures.The rectangular strip of wide 1inch, length 15cm is cut into, in relative humidity 50%th, 23 degree Celsius adjust humidity 11 hours down.Using Orientec Co., the Tensilon RTM-500 of Ltd manufactures, with negative Lotus sensor 1kg, draw speed 100mm/ minutes carry out tension test.Now, with the bottom of Tensilon by the volume end of sample Face guard block blocks (fixation), and low-density polyethylene film is blocked (fixation) with extension section, carries out tension test.Stretching examination The integral mean of load is taken in the interval of stretching 10mm to 50mm in testing, and take the average of test number (TN) 2 times, as bonding The value of property.

(manufacture method of photoresist duplexer volume)

Photoresist duplexer volume is preferably made from from the viewpoint of suppressing the attachment of foreign body and photosensitive during suppression transport Covered with shading sheet material.Shading sheet material is referred to as light-proofness thin film.Shading sheet material can be according to being wound in photonasty The mode of laminated resin body volume covers photoresist duplexer volume.As shown in figure 3, when shading sheet material 9 is tubular, due to can Photoresist volume 1 is covered so that photoresist is rolled up in 1 insertion tube, therefore preferably.In addition, the length of cylinder is than photonasty tree When the core 2 of lipid layer stack volume 1 is long, as shown in figure 3, can be by the part longer than core 2 be folded into inside core, further Suppress the attachment of foreign body and photosensitive, therefore preferably.

Shading sheet material from can protect photoresist duplexer volume the contact with from such as component light falling object, wrap From the viewpoint of the gentle touchdown of packaging container, preferably polyethylene.Thickness is from the suitable intensity of maintenance and suppresses pin hole Viewpoint is set out, preferably more than 10 μm, from from the viewpoint of treatability, preferably less than 300 μm.More preferably 20～200 μm, More preferably 30～130 μm.In order to improve light-proofness and it is preferred that black.

Photoresist duplexer volume preferably by be formed with it is with aforementioned core chimeric as convex portion be referred to as core body A pair of parts of support and be suspended vacantly.By being suspended vacantly, when can prevent transport, photoresist duplexer is held with packaging The contact of the ground wall of device.As core body support, for example, can include Japanese Unexamined Patent Publication 2004-42952 and Japanese Unexamined Patent Publication 2003- Core body support described in 89477.

When covering photoresist duplexer volume using shading sheet material, if the ratio core of shading sheet material long part is folded into Core body support is further installed in core and according to the mode for clamping the invagination part, then can suppress the attachment and sense of foreign body Light, therefore preferably.

(photosensitive polymer combination)

Photosensitive polymer combination preferably comprises the alkali-soluble macromolecule of (a) containing carboxyl；(b) addition polymerization list Body；(c) Photoepolymerizationinitiater initiater.

Roll up when ring-type sheet material is peeled off from volume end face end face cull is few, photosensitive polymer combination is to ring-type sheet material From the viewpoint of attachment also tails off, preferred photosensitive polymer combination includes above-mentioned (a)～(c).

The alkali-soluble macromolecule of (a) containing carboxyl

A the alkali-soluble macromolecule of () containing carboxyl will preferably contain α, the monomer of β-unsaturation carboxyl is used as aggregating into Point, the high molecular acid equivalent of alkali-soluble is 100～600, and weight average molecular weight is 5,000～500,000.In order that photonasty Resin combination has developability or fissility relative to the developer solution containing aqueous alkali or stripper, and the alkali containing carboxyl is solvable Carboxyl in property macromolecule is necessary.Acid equivalent refers to the high molecular quality of alkali-soluble of the wherein carboxyl with 1 equivalent. The preferred lower limit of acid equivalent is 250, and the preferred upper limit is 450.From the raising of resistance to developability, resolution and adaptation The viewpoint of raising and from guaranteeing and other compositions in solvent or photosensitive polymer combination, particularly and following (b) addition From the viewpoint of the compatibility of polymerizable monomer, (a) the high molecular acid equivalent of the alkali-soluble containing carboxyl be preferably 100 with On, from the viewpoint of improving from developability and fissility, preferably less than 600.The measure of acid equivalent is using flat natural pond industry The flat natural pond automatic titration device (COM-555) the sodium hydroxide using 0.1mol/L that (strain) is manufactured is entered according to potentiometric titration Capable.

A the high molecular weight average molecular weight of the alkali-soluble of () containing carboxyl is preferably 5,000～500,000.From maintenance sense The thickness of photosensitive resin layer stack is uniform and obtains the viewpoint of the patience to developer solution and goes out from the viewpoint for suppressing edge-melting Send out, weight average molecular weight is preferably 5, more than 000, in addition, from from the viewpoint of maintaining developability, preferably 500, less than 000.It is molten While the phenomenon of photosensitive polymer combination is oozed out when referring to photoresist duplexer wound into rolls from volume end face.The sense oozed out Photosensitive resin composition sometimes can be across supporting layer protective layer and the photo-sensitive resin from adjacent another layer under volume state The photosensitive polymer combination adhesion oozed out.The photosensitive resin composition after photosensitive polymer combination, i.e. edge-melting after adhesion Thing leaves the photoresist duplexer of web-like sometimes, peels off from end face in lamination, becomes resist bits and disperses.If anti- Erosion agent bits are attached to the substrate after lamination, then the resist bits will attach to the mask of following exposure, be exposed solidification, In the case of negative resist, masking exposure, becomes the defect of pattern.

It is further preferred that the lower limit of the high molecular weight average molecular weight of the alkali-soluble of (a) containing carboxyl is 20,000, (a) The upper limit of the high molecular weight average molecular weight of the alkali-soluble containing carboxyl is 250,000.Weight average molecular weight in this specification is Refer to by gel permeation chromatography (GPC) using polystyrene (the Shodex STANDARD SM- of Showa Denko K.K. manufactures 105) weight average molecular weight that standard curve determination is obtained.

A the high molecular weight average molecular weight of the alkali-soluble of () containing carboxyl can be manufactured using JASCO Corporation Gel permeation chromatography be measured under the following conditions：

Differential refraction detector：RI-1530

Pump：PU-1580

Degasser：DG-980-50

Post calorstat：CO-1560

Post：It is followed successively by KF-8025, KF-806M × 2, KF-807

Eluent：THF.

A the alkali-soluble macromolecule of () containing carboxyl is preferably comprising 1 in aftermentioned first monomer or second comonomer Plant the (co) polymer of the monomer as composition of the above.

First monomer is the carboxylic acid with a polymerism unsaturated group or anhydride in molecule.Can for example include (methyl) acrylic acid, fumaric acid, cinnamic acid .beta.-methylacrylic acid, itaconic acid, maleic anhydride and acid half ester.Wherein, particularly preferably (methyl) acrylic acid.

Second comonomer be it is nonacid, and molecule in have at least one polymerism unsaturated group monomer.Can include For example (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) Isobutyl 2-propenoate, (methyl) tert-butyl acrylate, (methyl) acrylic acid 2- hydroxyl second Ester, (methyl) acrylic acid 2- hydroxypropyl acrylates, (methyl) cyclohexyl acrylate, (methyl) 2-EHA, (methyl) propylene The esters of the vinyl alcohols such as acid benzyl ester, vinylacetate；(methyl) acrylonitrile, styrene and the styrene derivative that can be polymerized Deng.Wherein, preferably (methyl) acrylic acid methyl ester., (methyl) n-butyl acrylate, styrene and (methyl) benzyl acrylate, from point From the viewpoint of resolution, particularly preferably using styrene.

The alkali-soluble macromolecule of (a) containing carboxyl preferably by by above-mentioned monomer mix and with solvent such as acetone, In the solution of butanone or isopropanol, appropriate addition radical polymerization initiator such as benzoyl peroxide, azo Isopropyl cyanide carries out heated and stirred, so as to synthesize.Sometimes while the Deca mixture in reactant liquor it is a part of while synthesized.Also have When add solvent after reaction terminates again, adjust to desired concentration.As synthetic method, in addition to polymerisation in solution, Polymerisation in bulk, suspension polymerisation or emulsion polymerization can also be used.

For the copolymerization ratio of the alkali-soluble macromolecule of particularly preferred (a) containing carboxyl, the first monomer and second comonomer Example is that the first monomer is 10～60 mass %, and second comonomer is 40～90 mass %, even more preferably the first monomer For 15～35 mass %, and second comonomer is 65～85 mass %.

As the high molecular more specifically example of the alkali-soluble of (a) containing carboxyl, for example, can include containing methyl-prop The polymer of e pioic acid methyl ester, methacrylic acid and styrene as copolymer composition, containing methyl methacrylate, methacrylic acid With n-butyl acrylate as copolymer composition polymer, and contain benzyl methacrylate, methyl methacrylate and third Polymer etc. of the olefin(e) acid 2- Octyl Nitrites as copolymer composition.

The high molecular content of alkali-solubles of (a) in photosensitive polymer combination containing carboxyl is with photosensitive resin composition The solid constituent total amount of thing is used as the scope that benchmark is 20～90 mass %, preferably 40～60 mass %.A () is containing carboxyl Formation is anti-from the alkali-developable of maintenance photosensitive polymer combination, by exposure, development for the high molecular content of alkali-soluble Corrosion figure case as resist layer characteristic for example indentation, etching and various electroplating work procedures in have sufficient patience viewpoint go out Send out, more than preferably 20 mass %, the corrosion-resisting pattern after photosensitive polymer combination, solidification from before solidification has sufficiently soft From the viewpoint of soft, below preferably 90 mass %.

(b) addition polymerization monomer

B () addition polymerization monomer is the chemical combination for having at least one ethylenic unsaturated bond that can be polymerized in intramolecular Thing.Ethylenic unsaturated bond is preferably terminal ethylenic unsaturated group.Further, from high-resolution, edge-melting and pitting viewpoint Set out, as (b) addition polymerization monomer, preferably use at least one bisphenol-A system (methyl) acrylate compounds.

In this specification, bisphenol-A system (methyl) acrylate compounds refer to the-C from bisphenol-A₆H₄-C(CH₃)₂- C₆H₄- group and have (methyl) acryloyl group or be derived from (methyl) acryloyl group carbon-to-carbon unsaturated double-bond and chemical combination Thing.As specific example, can include and the Polyethylene Glycol of the oxirane of the average Unit 2 of addition be distinguished at the two ends of bisphenol-A Two (methacrylic acid) ester two (methacrylic acid) ester (the NK ester BPE-200 that Xin Zhong villages chemical industry (strain) manufacture) or double Distinguish the addition dimethylacrylate of the Polyethylene Glycol of the oxirane of average Unit 5 (Xin Zhong villages chemistry work in the two ends of phenol A NK ester BPE-500 that industry (strain) is manufactured), in the oxirane of the two ends difference average Unit 6 of addition of bisphenol-A and average 2 single It is two (methacrylic acid) ester of the poly alkylene glycol of the expoxy propane of unit, average 15 single in the two ends difference addition of bisphenol-A Two (methacrylic acid) ester of the poly alkylene glycol of the expoxy propane of the oxirane and average Unit 2 of unit.

As (b) addition polymerization monomer, in addition to above-mentioned compound, it is possible to use with least one olefinic not The known compound of saturated group.Such as seven glycol dipropylene glycol acrylate of 4- nonyls phenyl, acrylic acid 2- can be included Hydroxyl -3- phenoxy propyl esters, the own glycol acrylate of phenoxy group, phthalic anhydride and acrylic acid 2- hydroxypropyl acrylates it is half-esterification Compound and the reactant of expoxy propane (Japanese catalyst chemistry manufacture, trade name OE-A 200), five Asia third of 4- n-octyls epoxide Base butanediol acrylate, 1,6-HD (methyl) acrylate, 1,4- cyclohexanediols two (methyl) acrylate, polypropylene glycol Polyether polyols two (methyl) acrylate, the 2- such as two (methyl) acrylate, Polyethylene Glycol two (methyl) acrylate Two (p-hydroxybenzene) propane two (methyl) acrylate, glycerol three (methyl) acrylate, tetramethylolmethane five (methyl) propylene Double (five ethyoxyls of 4- methacryloxies of acid esters, trihydroxymethylpropanyltri diglycidyl ether three (methyl) acrylate, 2,2- Phenyl) propane, hexamethylene diisocyanate and nonyl trimethylene glycol monomethacrylates carbamate compound etc. Multifunctional (methyl) acrylate of multifunctional (methyl) acrylate containing carbamate groups, isocyanurate compound Deng.They can be used alone, it is also possible to be used in combination of two or more, it is also possible to bisphenol-A system (methyl) acroleic acid esterification Compound is applied in combination.

The content of (b) addition polymerization monomer in photosensitive polymer combination with the solid of photosensitive polymer combination into Point total amount is used as the scope that benchmark is 5～75 mass %, more preferably 15～70 mass %.From resolution, adaptation and copper cash Formative from the viewpoint of, (b) content of addition polymerization monomer be 5 mass % more than, from the sight of the flexibility of cured film Point sets out, and is below 75 mass %.

(c) Photoepolymerizationinitiater initiater

As (c) Photoepolymerizationinitiater initiater, the photopolymerization for example usually as photoresist can be suitably used and caused Agent and the material that uses, particularly preferably use six aryl bisglyoxalines (hereinafter also referred to triarylimidazoles dimer).

As triarylimidazoles dimer, for example, can include：2- (Chloro-O-Phenyl) -4,5- diphenyl-imidazole dimers (hereinafter also referred to " 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-tetraphenyl -1,1 '-bisglyoxaline "), 2,2 ', 5-, tri--(adjacent chlorine Phenyl) -4- (3,4- Dimethoxyphenyls) -4 ', 5 '-diphenyl-imidazole dimer, 2,4- pair-(Chloro-O-Phenyl) -5- (3,4- bis- Methoxyphenyl)-diphenyl-imidazole dimer,

2,4,5- tri--(Chloro-O-Phenyl)-diphenyl-imidazole dimers, 2- (Chloro-O-Phenyl)-bis- -4,5- (3,4- dimethoxies Base phenyl)-imidazoles dimer, 2,2 '-bis--(2- fluorophenyls) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-imidazoles dimer, 2,2 '-bis--(2,3- difluoromethyl phenyl) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-imidazoles dimer, 2,2 '-it is bis--(2, 4- difluorophenyls) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-imidazoles dimer,

2,2 '-bis--(2,5- difluorophenyls) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-imidazoles dimer, 2,2 ' - Double-(2,6- difluorophenyls) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-imidazoles dimer, 2,2 '-bis--(2,3,4- trifluoros Phenyl) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-imidazoles dimer, 2,2 '-bis--(2,3,5- trifluorophenyls) -4,4 ', 5, 5 '-four-(3- methoxyphenyls)-imidazoles dimer,

2,2 '-bis--(2,3,6- trifluorophenyls) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-imidazoles dimer, 2,2 ' - Double-(2,4,5- trifluorophenyls) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-imidazoles dimer, 2,2 '-bis--(2,4,6- tri- Fluorophenyl) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-imidazoles dimer,

2,2 '-bis--(2,3,4,5- tetrafluoro phenyl) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-imidazoles dimer, 2, 2 '-bis--(2,3,4,6- tetrafluoro phenyl) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-imidazoles dimer and 2,2 '-bis--(2, 3,4,5,6- pentafluorophenyl groups) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-imidazoles dimer etc..

2- (Chloro-O-Phenyl) -4,5- diphenyl-imidazole dimers can be especially preferably used, which is for resolution or solid Change the Photoepolymerizationinitiater initiater that film strength against corrosion has high effect.These Photoepolymerizationinitiater initiaters can be used alone, or can be with It is used in combination of two or more.Alternatively, it is also possible to be applied in combination with following acridine compounds, pyrazoline compounds etc..

In a preferred embodiment, as (c) Photoepolymerizationinitiater initiater, it is possible to use acridine compounds or pyrazoline chemical combination Thing.As acridine compounds, acridine, 9- phenylacridines, 9- (4- tolyls)-acridine, 9- (4- methoxyphenyls) can be included Acridine, 9- (4- hydroxyphenyl) acridine, 9- ethyl acridines, 9- chloroethyl acridines, 9- methoxyacridines, 9- ethyoxyl acridines,

9- (4- aminomethyl phenyls) acridine, 9- (4- ethylphenyls) acridine, 9- (4- n-pro-pyl phenyl) acridine, 9- (the positive fourths of 4- Base phenyl) acridine, 9- (4- tert-butyl-phenyls) acridine, 9- (4- ethoxyl phenenyls) acridine, 9- (4- acetylphenyls) acridine, 9- (4- dimethylaminophenyls) acridine, 9- (4- chlorphenyls) acridine,

9- (4- bromophenyls) acridine, 9- (3- aminomethyl phenyls) acridine, 9- (3- tert-butyl-phenyls) acridine, 9- (3- acetyl group Phenyl) acridine, 9- (3- dimethylaminophenyls) acridine, 9- (3- diethylamino phenyl) acridine, 9- (3- chlorphenyls) acridine, 9- (3- bromophenyls) acridine, 9- (2- pyridine radicals) acridine, 9- (3- pyridine radicals) acridine, 9- (4- pyridine radicals) acridine.Wherein, preferably 9- phenylacridines.

As pyrazoline compounds, preferred 1- phenyl -3- (4- tert-butyl-styrene bases) -5- (4- tbutyl-phenyls) - Pyrazoline, 1- (4- (benzoxazole -2- bases) phenyl) -3- (4- tert-butyl-styrene bases) -5- (4- tbutyl-phenyls)-pyrazoles Quinoline, 1- phenyl -3- (4- xenyls) -5- (4- tbutyl-phenyls)-pyrazoline, (4- is tertiary pungent for 1- phenyl -3- (4- xenyls) -5- Base-phenyl)-pyrazoline.

As Photoepolymerizationinitiater initiater in addition to the foregoing, can for example include 2-ethyl-anthraquinone, octaethyl anthraquinone, 1,2- Benzo anthraquinone, 2,3- benzo anthraquinones, 2- phenyl anthraquinones, 2,3- diphenyl anthraquinones, 1-chloroanthraquinone, 1,4- naphthoquinone, 9,10- phenanthrenequione, The quinones such as 2-MNQ, 2,3- dimethyl anthraquinone and 3- chloro-2-methyl anthraquinones,

Benzophenone, Michler's keton [4,4 '-bis- (dimethylamino) benzophenone] and 4,4 '-bis- (diethylamino) hexichol The benzoins such as the aromatic series ketone such as ketone, benzoin, benzoin ethyl ether, benzoin phenylate, methylbenzoin and ethyl benzoin Ethers,

Benzil dimethyl ketal, benzil diethyl ketal, thioxanthene ketone class and the benzoic combination of alkyl amino, 1- benzene The oxime esters such as base -1,2- propanedione -2-O- cuprons, 1- phenyl -1,2- propanedione -2- (O- ethoxy carbonyls) oximes.

It should be noted that as above-mentioned thioxanthene ketone class and the benzoic combination of alkyl amino, such as second can be included The combination of the combination, CTX and dimethyl amino benzoate of base thiaxanthone and dimethyl amino benzoate with And the combination of isopropyl thioxanthone and dimethyl amino benzoate.Alternatively, it is also possible to using N- aryl amino acids.As N- The example of aryl amino acid, can include N-phenylglycine, N- Methyl-N-phenyl glycine, N- ethyl, N-phenyl glycine Deng.Wherein, particularly preferred N-phenylglycine.

The content of (c) Photoepolymerizationinitiater initiater in photosensitive polymer combination is with the solid constituent of photosensitive polymer combination Used as the scope that benchmark is 0.01～30 mass %, preferred lower limit is 0.05% mass % to total amount, it is further preferred under Limit is 0.1 mass %, and the preferred upper limit is 15 mass %, and the further preferred upper limit is 10 mass %.From using expose into From the viewpoint of abundant light sensitivitys are obtained during capable photopolymerization, (c) content of Photoepolymerizationinitiater initiater is more than 0.01 mass %, from Light is made fully to be transmitted to the bottom surface (i.e. away from the part of light source) of photosensitive polymer combination, obtain good discrimination during photopolymerization From the viewpoint of rate and adaptation, it is below 30 mass %.

(e) other additives

In photosensitive polymer combination in addition to the composition of above-mentioned (a)～(c), various additives can be contained.Specifically For, such as coloring material such as dyestuff, pigment.As such coloring material, for example, can include phthalocyanine green, crystal violet, first Base orange, Nile blue 2B, Victoria blue, peacock green, alkali blue 20, diamond green etc..

Containing in the case of above-mentioned coloring material, the addition of coloring material with the solid of photosensitive polymer combination into Divide total amount as benchmark, preferably 0.001～1 mass %.When the addition of coloring material is more than 0.001 mass %, have Improve the effect of treatability；During for below 1 mass %, with the effect for maintaining storage stability.

In addition, giving visual image in order to pass through exposure, it is also possible to containing colour developing in photosensitive polymer combination Agent.As such colour developing based dye, the combination of leuco dye or fluoran dyes and halogen compounds can be included.

For example, as leuco dye, [procrypsis is crystallized can to include three (4- dimethylamino -2- aminomethyl phenyls) methane It is purple], three (4- dimethylamino -2- aminomethyl phenyls) methane [leucomalachite green] and fluoran dyes.Wherein, tied using procrypsis In the case of crystalviolet, contrast is good, is preferred.

As aforementioned halogen compound, n-amyl bromide, isoamyl bromide, brominated isobutylene, ethylene bromide, hexichol can be included Ylmethyl bromine, dibromomethylbenzene (benzal bromide), methylene bromide, trisbromomethyl phenyl sulfone, carbon tetrabromide, tricresyl phosphate (2, 3- dibromopropyls) ester, trichloroacetamide, n-amyl iodide, isobutyl iodide, double (rubigan) ethane of tri- chloro- 2,2- of 1,1,1-, six Ethyl chloride, chloro triaizine compounds etc..

In the case of containing these dyestuffs, the content of the dyestuff in photosensitive polymer combination is with photosensitive resin composition The solid constituent total amount of thing is used as benchmark, preferably respectively 0.1～10 mass %.

Additionally, the heat stability and storage stability in order to improve photosensitive polymer combination, preferably in photoresist In group in compositionss containing radical polymerization inhibitor or selected from benzotriazole and carboxyl benzotriazole class composition at least More than a kind of compound.

As such radical polymerization inhibitor, for example, can include p methoxy phenol, hydroquinone, pyrogallol, naphthylamines, tertiary fourth Base catechol, Cu-lyt., 2,6- di-t-butyls-paracresol, 2,2 '-di-2-ethylhexylphosphine oxide (4- methyl-6-tert-butylphenols), 2, 2 '-methylene-bis(4-ethyl-6-t-butyl phenol), nitrosophenylhydroxylamine aluminium salt, diphenyl nitrosamine.

As benzotriazole, for example, can include chloro- 1,2, the 3- benzotriazole of 1,2,3- benzotriazole, 1-, double (N-2- Ethylhexyl) aminomethylene-l, 2,3 triazole, double (N-2- ethylhexyls) aminomethylene -1,2,3- tolytriazoles, Double (N-2- ethoxys) aminomethylenes-l, 2,3 triazole.

As carboxyl benzotriazole class, for example, can include 4- carboxyl -1,2,3- benzotriazole, 5- carboxyl -1,2,3- benzene And triazole, (N, N- dibutylamino) carboxyl benzotriazole, N- (bis- -2- ethylhexyls of N, N-) aminomethylene carboxyl benzo three Azoles, N- (bis- -2- ethoxys of N, N-) aminomethylene carboxyl benzotriazole, N- (bis- -2- ethylhexyls of N, N-) aminoethylene Carboxyl benzotriazole.

The total addition of radical polymerization inhibitor, benzotriazole and/or carboxyl benzotriazole class is with photoresist group Used as benchmark, preferably 0.001～3 mass %, preferred lower limit is 0.05 mass % to the solid constituent total amount of compound, more excellent The upper limit of choosing is 1 mass %.From from the viewpoint of giving storage stability to photosensitive polymer combination, the total addition is excellent Elect more than 0.001 mass % as, from from the viewpoint of maintaining light sensitivitys, below preferably 3 mass %.

In photosensitive polymer combination, other plasticizers can be contained as needed.As such plasticizer, for example Can include carries out the modified compound of polyoxy alkylidene by bisphenol-A.

In addition, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan can for example be used The sorbitan derivatives such as alcohol oleate；The polyalkylene glycols such as Polyethylene Glycol, polypropylene glycol；Phthalic acid diethyl The phthalates such as ester；Orthotoluene sulfonamide, para toluene sulfonamide, tributyl citrate, triethyl citrate, acetyl group The plasticizer of triethyl citrate, three n-propyl of acetyl citrate and acetyl tributyl citrate etc..Particularly preferably make With sorbitan derivatives and polyalkylene glycols.

The content of the plasticizer in photosensitive polymer combination using the solid constituent total amount of photosensitive polymer combination as Benchmark, preferably 1 mass %～50 mass %, preferred lower limit are 3 mass %, and the preferred upper limit is 30 mass %.From Suppress developing time delay, to cured film give flexibility from the viewpoint of, more than preferably 1 mass %, in addition from suppression From the viewpoint of solidification deficiency or cold flow, below preferably 50 mass %.

Embodiment

Hereinafter, further it is specifically described in embodiment, but is not limited to this.

First, the manufacture method for illustrating the sample for evaluation of embodiment and comparative example, secondly, represents with regard to gained sample Evaluation methodology and evaluation result.Here, having used ring-type sheet material as volume end face guard block.

(embodiment 1～12, comparative example 1)

1. the making of sample for evaluation

Sample for evaluation in embodiment and comparative example is made as follows.

The making ＞ of ＜ photoresist duplexers

By the compositionss 1 shown in table 1 below, (wherein, the numeral of each composition is denoted as the compounding amount (quality of solid constituent Part).Abbreviation in table 1 is consistent with table 2.) and solvent fully stir, mix, make photosensitive polymer combination tune Liquid is closed, prepares the pet film (R310 of Mitsubishi Plastics, Inc. manufacture) of 16 μ m-thicks As supporter, photosensitive polymer combination blending liquid is equably coated into the polyethylene terephthalate using die coating machine The surface of ester film is simultaneously dried, and then forms photo-sensitive resin.The thickness of photo-sensitive resin is 15 μm.Then, exist Photo-sensitive resin, be not laminated on the surface of pet film, fit as 33 μm of protective layer Thick polyethylene film (GF-858 of TAMAPOLY CO., LTD. manufacture), obtains photoresist duplexer 1.

In addition, in above-mentioned photoresist duplexer 1, in addition to compositionss 1 are set to compositionss 2～6, with photonasty Laminated resin body 1 is similarly made, and obtains photoresist duplexer 2～6.In above-mentioned photoresist duplexer 1, remove Compositionss 1 are set to into compositionss 7～10, the thickness of photo-sensitive resin is set to into 10 μm in addition, be laminated with photoresist Body 1 is similarly made, and obtains photoresist duplexer 7～10.

The making ＞ of ＜ photoresists duplexer volume

Ring-type sheet material is using the sheet material shown in 3～table of table 5.For the bonding containing acrylic acid (ester) resin of ring-type sheet material Agent compositionss, in case of no particular description, directly will be peeled off using Elleair TackNS80/SBG85S/ again The adhesive composition of (manufacture of Elleair Texel Co., Ltd.).

For sample F and G, adhesive composition is adjusted as follows.That is, by the B-1 shown in table 2 and M-8 with solid into Divide than being 45:55 and 40:60 mode is compounded, and is coated base material and is dried, adjusts, so that dried thickness is 15μm。

By 1 otch of photoresist duplexer be width 495mm, internal diameter 77mm, external diameter 88mm, length 530mm ABS trees 300m is wound in fat core (core body).The external diameter of the photoresist duplexer of wound into rolls is 180mm.

The photoresist duplexer for making to be wound in core body and becoming web-like is maintained on bar-shaped stainless steel support, should Stainless steel support can be designed in the way of holding level on bar-shaped stainless steel support according to the fixed other end.

Become the photosensitive of web-like using periphery 500mm, long 800mm, thick 80 μm cylindrical shape light-proofness polyethylene tube covering Property laminated resin body.

The photoresist duplexer of the aforementioned web-like covered by light-proofness polyethylene tube is dismantled from support, according to width In the buffer part that 330mm, high 100mm and upper bend can be designed in the way of fixed volume for concavity, volume is set.

Turn back one end of light-proofness polyethylene tube, expose the end face of web-like photoresist duplexer, annular lamina is installed Material.The other end similarly installs ring-type sheet material, has made photoresist duplexer volume 1.

Light-proofness polyethylene tube is folded in core body, it is that the convex mode chimeric with core body is designed to install according to central part Core body support, photoresist volume 1 is packed.

2. metewand

By following assessment item and metewand, photoresist duplexer volume is evaluated and marked grade.Comment Valency result is illustrated in table 3～5.

(1) foreign body removal

Roll up from photoresist duplexer and ring-type sheet material is peeled off, be confirmed whether have foreign body to be attached to ring-type sheet material.It is as follows It is labeled grade.

○：Foreign body is attached to ring-type sheet material.Other adhesive tapes are attached on volume end face and is peeled off, it is impossible to which confirmation has different Thing adheres to.

△：Foreign body is attached to ring-type sheet material, but when attaching other adhesive tapes on end face is rolled up and being peeled off, confirms viscous Also there is the attachment of foreign body on crossed belt.

×：Foreign body is not adhered to ring-type sheet material.If attaching other adhesive tapes on volume end face and being peeled off, confirm To the attachment for having foreign body.

(2) ring-type sheet material installation

Content production volume as described in the making ＞ of above-mentioned ＜ photoresists duplexer volume, annular membrane is installed on Installation during volume end face, is carried out as follows mark grade.

○：Ring-type sheet material simply can be installed.When being attached at volume end face, can the attaching of no fold ground.

△：The time is needed in terms of attaching ring-type sheet material, be installed on support or core.When being attached at volume end face, one Part produces fold or air inlet.

×：Aspect by the attaching of ring-type sheet material, on being installed on support or core needs the time.When stripping is not intended to position On the ring-type sheet material that attached and when attaching again, ring-type sheet material is stretched and deformation or ruptures, and makes to be attached at volume end face and become It is difficult.

(3) the packaging material adhesion of ring-type sheet material

After content production volume as described in the making ＞ of above-mentioned ＜ photoresists duplexer volume, broken seal.Unpacking Afterwards, also with install when in the same manner as, whether end face is installed on to ring-type sheet material and is observed, be carried out as follows mark grade.

○：It is installed with the same manner as when installing.

△：During unpacking, ring-type sheet material is attached at light-proofness cylindrical shape polyethylene sheets, with what is peeled off from a part of end face Position.

×：During unpacking, ring-type sheet material is attached at light-proofness cylindrical shape polyethylene sheets, with light-proofness cylindrical shape polythene strip Material is together peeled off.

(4) removal of ring-type sheet material

After content production as described in the makings ＞ of above-mentioned ＜ photoresists duplexer volume is rolled up, broken seal, with wearing The handss for having resin-made glove peel off ring-type sheet material.Operability during to peeling off is carried out as follows mark grade.

○：Ring-type sheet material can be easily peeled off in 5 seconds.

△：The stripping of ring-type sheet material needs the time of more than 5 seconds.

(5) foreign body number

The photonasty tree of 14 web-likes of content production as described in the making ＞ of above-mentioned ＜ photoresists duplexer volume Lipid layer stack.Foreign body is removed from the end face of all volumes, from this 14, randomly makes four position attachments of total of volume end face different Thing.Afterwards, whole volumes is installed and is peeled off ring-type sheet material, calculating is attached to the foreign body of volume end face.

[table 1]

[table 2]

B-1	25 mass % of methacrylic acid, 50 mass % of methyl methacrylate, the terpolymer (weight average molecular weight 50000, acid equivalent 344) of 25 mass % of styrene
		B-2	25 mass % of methacrylic acid, 65 mass % of methyl methacrylate, the terpolymer (weight average molecular weight 70000, acid equivalent 344) of 10 mass % of butyl acrylate
B-3	25 mass % of methacrylic acid, 65 mass % of methyl methacrylate, the terpolymer (dividing equally in amount 120000, acid equivalent 344 again) of 10 mass % of butyl acrylate
		M-1	Trimethylolpropane triacrylate
M-2	The carbamate compound of hexamethylene diisocyanate and five trimethylene glycol monomethacrylates
		M-3	Three epoxide ethyl trimethylolpropane triacrylates
M-4	Two (methacrylic acid) ester of the poly alkylene glycol of the oxirane of the expoxy propane and average Unit 6 of the average Unit 2 of addition is distinguished at the two ends of bisphenol-A
		M-5	Two (methacrylic acid) ester of the Polyethylene Glycol of the oxirane of each average Unit 2 of addition is distinguished at the two ends of bisphenol-A
M-6	In two (methacrylic acid) ester of the poly alkylene glycol of the oxirane of each average Unit 3 of two ends addition of the expoxy propane of average Unit 12
		M-7	The diacrylate of the Polyethylene Glycol obtained by the oxirane of average Unit 9
M-8	Two (methacrylic acid) ester of the Polyethylene Glycol of the oxirane of each average Unit 5 of addition is distinguished at the two ends of bisphenol-A
		I-1	2- (Chloro-O-Phenyl) -4,5- diphenyl-imidazole dimers
I-2	4,4 '-bis- (diethylamino) benzophenone
		D-1	Peacock green
D-2	Leuco crystal violet
		P-1	Para toluene sulfonamide
P-2	The polypropylene glycol of weight average molecular weight 2000
		P-3	The addition Polyethylene oxide of average 18 moles of oxirane [three (1- phenethyls) phenyl ether]
P-4	Polyoxyethylene sorbitan trioleate (Japanese emulsifying agent Co., Ltd. manufacture, Newcol 3-85)
		X-1	(N, N- dibutylamino) carboxyl benzotriazole
X-2	Double [3- (the 3- the tert-butyl groups) -5- methyl -4- hydroxy phenyls] propionic esters of triethylene glycol
		X-3	Nitrosophenylhydroxylamine aluminium salt
X-4	2- di-n-butyls amino -4,6 disulfide groups-s-triazine
		X-5	3- glycidoxy-propyltrimethoxy silanes

[table 3]

[table 4]

[table 5]

Except photoresist duplexer 1 is made photoresist duplexer 2～6, on ring-type sheet material using sample B In addition, photoresist duplexer volume is made in the same manner as photoresist duplexer volume 1, be laminated as photoresist Body volume 2～6.Using photoresist volume 2～6 carry out the evaluation of (1)～(5) when, obtain with using photo-sensitive resin stack Roll up result same when 1.

Except photoresist duplexer 1 is made photoresist duplexer 7～10, on ring-type sheet material using sample B, external diameter 180mm is set to into external diameter 176mm beyond, with photoresist duplexer volume 1 in the same manner as make photoresist stacking Body is rolled up, as photoresist duplexer volume 7～10.The external diameter of the photoresist duplexer of wound into rolls is 176mm.When carrying out the evaluation of (1)～(5) using photoresist volume 7～10, obtain rolling up 1 with using photo-sensitive resin stack When same result.

Industrial applicability

For above-mentioned photoresist duplexer is rolled up, due to easily foreign body being removed in unpacking, therefore in essence It is useful in close equipment, the processing of electronic material, it is also useful as the permanent pattern loaded in precision equipment, electronic material.

Description of reference numerals

1 photoresist duplexer

2 core

The end face guard blocks (ring-type sheet material) of volume 3

4 supporting layers

5 photo-sensitive resins

6 protective layers

7 flat boards

8 fixed components

9 shading sheet materials

10 photoresist duplexers are rolled up

Claims

1. a kind of photoresist duplexer volume, wherein, by photoresist duplexer in core wound into rolls, roll up end face Guard block according to configuring with the mode of the end contact of the photoresist duplexer for winding up,

Wherein, the photoresist duplexer is rolled up and be enough to lower important document：

The length of the core is longer than the width of the photoresist duplexer,

The volume end face guard block is in the ring-type sheet material for having adhesive composition with the side of volume end contact, to pass through The mode for wearing the extension of the core is configured；

The photoresist duplexer includes at least supporting layer and is laminated in the photo-sensitive resin of the supporting layer；

The ring-type sheet material is present in aerial mode according to its half and is arranged on the flat board for protruding horizontally up, by the annular lamina Material is present in aerial part connecing with the ring-type sheet material from the front end of the farthest ring-type sheet material of flat board and flat board When the distance between face of tactile side is set to deflection distance H, the half of the ring-type sheet material external diameter and is set to R, H/R is more than 0.06, Wherein, the unit of H, R is mm；And the volume end face guard block and the bonding force of low-density polyethylene film are 5gf/inch ～250gf/inch.

2. photoresist duplexer according to claim 1 is rolled up, it is characterised in which is covered by shading sheet material.

3. photoresist duplexer according to claim 2 is rolled up, it is characterised in that the shading sheet material is tubular.

4. photoresist duplexer according to claim 1 is rolled up, it is characterised in that the internal diameter of the ring-type sheet material is volume 1～1.1 times of core external diameter.

5. photoresist duplexer according to claim 1 is rolled up, it is characterised in that

The ring-type sheet material is present in aerial mode according to its half and is arranged on the flat board for protruding horizontally up, by the annular lamina Material is present in aerial part connecing with the ring-type sheet material from the front end of the farthest ring-type sheet material of flat board and flat board When the distance between face of tactile side is set to deflection distance H, the half of the ring-type sheet material external diameter and is set to R, H/R is 0.06～ 0.59, wherein, the unit of H, R is mm.

6. photoresist duplexer according to claim 1 is rolled up, it is characterised in that the base of the volume end face guard block Material be dust-free paper, low dirt paper, synthetic paper or, the material fitted with resin base material of paper.

7. the photoresist duplexer according to any one of claim 1～6 is rolled up, it is characterised in that the photonasty Resin bed is the layer comprising photosensitive polymer combination, and it is high that the photosensitive polymer combination includes the alkali-soluble containing carboxyl Molecule, addition polymerization monomer, Photoepolymerizationinitiater initiater.

8. photoresist duplexer according to claim 7 is rolled up, it is characterised in that the alkali-soluble containing carboxyl Macromolecule is the material of styrene or derivatives thereof copolymerization.

9. photoresist duplexer according to claim 7 is rolled up, it is characterised in that the addition polymerization monomer is included Bisphenol-A system (methyl) acrylate compounds.

10. photoresist duplexer according to claim 7 is rolled up, it is characterised in that the Photoepolymerizationinitiater initiater is included Six aryl bisglyoxalines or derivatives thereof.

The 11. photoresist duplexer volumes according to any one of claim 1～6, it is characterised in that described adhesive Compositionss are resin comprising acrylic acid (ester).

The 12. photoresist duplexer volumes according to any one of claim 1～6, it is characterised in that described adhesive Compositionss contain binding agent and granule, and more than 50 mass % of the granule 80 of the coating thickness with the adhesive composition～ 120% diameter, and the content of the granule relative to 100 parts by weight of binder be 5 weight portions to 30 weight portions.

A kind of 13. manufacture methods of photoresist duplexer volume, it is characterised in that

The photoresist duplexer of wound into rolls in core, with the end face with the photoresist duplexer for winding up Contact, and volume end face guard block is configured in the way of the extension through the core, wherein, methods described meet it is following will Part,

The length of the core is longer than the width of the photoresist duplexer,

The volume end face guard block is following ring-type sheet materials：With one or be divided into the state of some in wound into rolls The end face configuration of photoresist duplexer, the ring after being configured on the end face of photoresist duplexer of wound into rolls 1～1.1 times for core external diameter of the internal diameter of shape sheet material；

The manufacture method of 14. photoresist duplexer volumes according to claim 13, it is characterised in that the annular lamina The internal diameter of material is 1.001～1.1 times of the external diameter of the core, in the way of the extension through the core configures the ring Shape sheet material.

The manufacture method of 15. photoresist duplexer volumes according to claim 13, it is characterised in that

16. a kind of packing methods of photoresist duplexer volume, it is characterised in that usage right requires any one of 13～15 Described method manufacture photoresist duplexer volume, further covers the photoresist stacking by the shading sheet material of tubular Body is rolled up.

A kind of 17. ring-type sheet materials, which is the ring-type sheet material of thin film film rolling of wound into rolls in core, wherein, it is described Ring-type sheet material meets following important document,

The length of the core is longer than the width of the thin film,

The end contact of the ring-type sheet material and the thin film of the winding, is had with the side of the end contact in the ring-type sheet material There is adhesive composition, be configured in film rolling in the way of the extension through the core；

The ring-type sheet material is present in aerial mode according to its half and is arranged on the flat board for protruding horizontally up, by the annular lamina Material is present in aerial part connecing with the ring-type sheet material from the front end of the farthest ring-type sheet material of flat board and flat board When the distance between face of tactile side is set to deflection distance H, the half of the ring-type sheet material external diameter and is set to R, H/R is more than 0.06, Wherein, the unit of H, R is mm；And the bonding force of the ring-type sheet material and low-density polyethylene film be 5gf/inch～ 250gf/inch。

18. ring-type sheet materials according to claim 17, wherein, the thin film is photoresist duplexer.

19. ring-type sheet materials according to claim 17, it is characterised in that

20. ring-type sheet materials according to claim 17, it is characterised in that the base material which has is dust-free paper, low dirt paper, closes Into paper or, the material fitted with resin base material of paper.

21. ring-type sheet materials according to claim 18, it is characterised in that the photoresist duplexer is included at least and propped up Support layer and be laminated in the photo-sensitive resin of the supporting layer, the photo-sensitive resin is comprising photosensitive polymer combination Layer, the photosensitive polymer combination cause comprising the alkali-soluble macromolecule containing carboxyl, addition polymerization monomer, photopolymerization Agent.

22. ring-type sheet materials according to claim 21, it is characterised in that the alkali-soluble macromolecule containing carboxyl is The material of styrene or derivatives thereof copolymerization.

23. ring-type sheet materials according to claim 21, it is characterised in that the addition polymerization monomer includes bisphenol-A system (methyl) acrylate compounds.

24. ring-type sheet materials according to claim 21, it is characterised in that the Photoepolymerizationinitiater initiater joins miaow comprising six aryl Azoles or derivatives thereof.

The 25. ring-type sheet materials according to any one of claim 17～20, it is characterised in that described adhesive compositionss bag (ester) containing acrylic acid is resin.

The 26. ring-type sheet materials according to any one of claim 17～20, it is characterised in that described adhesive compositionss contain There are binding agent and granule, more than 50 mass % of the granule 80～120% of the coating thickness with the adhesive composition Diameter, and the content of the granule relative to 100 parts by weight of binder be 5 weight portions to 30 weight portions.

A kind of 27. film rolling, which possesses the ring-type sheet material described in covered by shading sheet material, claim 17～26.