CN106966074A

CN106966074A - Photoresist layered product is rolled up

Info

Publication number: CN106966074A
Application number: CN201710224203.2A
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: 2017-07-21
Anticipated expiration: 2033-12-26
Also published as: MY176080A; KR20190018037A; JP6046746B2; CN106393838A; KR20150079919A; JP6315724B2; TWI522303B; CN106393838B; CN106966074B; WO2014104217A1; TW201431769A; TW201613817A; CN104903207A; TWI611990B; KR102191080B1; CN104903207B; JPWO2014104217A1; JP2017071445A; KR101950064B1

Abstract

The present invention is provided can roll up the photoresist layered product volume that end face simply removes foreign matter in unpacking from photoresist layered product.The photoresist layered product volume structure be; by photoresist layered product in core wound into rolls; to be configured in the way of making the end contact of volume end face guard block and the photoresist layered product wound; for volume end face guard block; there is adhesive composition with volume end contact side, photoresist layered product comprises at least supporting layer and is laminated in the photo-sensitive resin of the supporting layer.

Description

Photoresist layered product is rolled up

The application is the applying date for December 26, Application No. 2013800685642 in 2013, entitled " photosensitive Property laminated resin body volume " application divisional application.

Technical field

The present invention relates to photoresist layered product volume.

Background technology

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

Prior art literature

Patent document

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

The content of the invention

Problems to be solved by the invention

The problem to be solved by the present invention is that there is provided can be simply by foreign matter from photoresist layered product in unpacking Roll up the photoresist layered product volume that end face is removed.

The solution used to solve the problem

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

[1]

A kind of photoresist layered product volume, wherein, by photoresist layered product in core wound into rolls, roll up end Face guard block by with being configured in the way of the end contact of the photoresist layered product wound up,

The volume end face guard block has adhesive composition for the side with rolling up end contact,

The photoresist layered product comprises at least supporting layer and is laminated in the photo-sensitive resin of the supporting layer.

[2]

Photoresist layered product volume according to [1] item, it is characterised in that it is covered by shading sheet material.

[3]

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

[4]

Photoresist layered product volume according to any one of the item of [1]~[3], wherein,

The length of the core is longer than the width of the photoresist layered product,

The volume end face guard block is to be configured at the ring-type in the end face of the photoresist layered product of wound into rolls Sheet material, the ring-type sheet material is configured in the way of the extension through the core.

[5]

Photoresist layered product volume according to [4] 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 layered product volume according to [4] 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 protruded horizontally up, by the ring The front end for being present in the ring-type sheet material farthest from flat board in aerial part of shape sheet material, with 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 layered product volume according to any one of the item of [1]~[6], it is characterised in that the end face The bonding force of guard block and low-density polyethylene film is 5gf/inch~250gf/inch.

[8]

Photoresist layered product volume according to any one of the item of [1]~[7], 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 layered product volume according to any one of the item of [1]~[8], it is characterised in that described photosensitive Property resin bed be the layer for including photosensitive polymer combination, the photosensitive polymer combination include the alkali-soluble containing carboxyl Macromolecule, addition polymerization monomer, Photoepolymerizationinitiater initiater.

[10]

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

[11]

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

[12]

Photoresist layered product volume according to any one of the item of [9]~[11], it is characterised in that the light gathers Close initiator and include six aryl bisglyoxalines or derivatives thereof.

[13]

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

[14]

Photoresist layered product volume according to any one of the item of [1]~[13], it is characterised in that the bonding Agent composition contains adhesive and particle, and more than the 50 mass % of the particle have the 80 of the coating thickness of the adhesive composition ~120% diameter, and the particle content relative to 100 parts by weight of binder be 5 parts by weight to 30 parts by weight.

[15]

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

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

The photoresist layered product comprises 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 rolling up end contact,

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

[16]

The manufacture method of photoresist layered product volume according to [15] 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, and the ring is configured in the way of the extension through the core Shape sheet material.

[17]

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

[18]

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

[19]

A kind of packing method of photoresist layered product volume, it is characterised in that any in usage right requirement 15~18 Method manufacture photoresist layered product 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, it is the ring-type sheet material of film film roll of wound into rolls in core, wherein,

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

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

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

[21]

Ring-type sheet material according to [20] item, wherein, the film is photoresist layered product.

[22]

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

[23]

Ring-type sheet material according to any one of the item of [20]~[22], it is characterised in that itself and low density polyethylene (LDPE) The bonding force of film is 5gf/inch~250gf/inch.

[24]

Ring-type sheet material according to any one of the item of [20]~[23], 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 the item of [21]~[24], it is characterised in that the photo-sensitive resin The layer for including 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 [25] 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 [25] 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 the item of [25]~[27], it is characterised in that the Photoepolymerizationinitiater initiater Include six aryl bisglyoxalines or derivatives thereof.

[29]

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

[30]

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

[31]

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

The effect of invention

, can be simply by foreign matter from photonasty tree in unpacking if being rolled up using the photoresist layered product of the present invention Lipid layer stack volume end face is removed.

Brief description of the drawings

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

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

Fig. 3 is the signal for the embodiment for representing the photoresist layered product volume by the shading sheet material covering of tubular Figure.

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 in the range of its main idea to implement.

Photoresist layered product volume is along its length in volume by the photoresist layered product of strip (banding) Wound on core, and roll up the end face (sense of the banding of the end face guard block according to the photoresist layered product with being wound The width end side of photosensitive resin layer stack) contact mode configure photoresist layered product volume.

Fig. 1 represents the schematic diagram of an embodiment of this photoresist layered product 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 layered product 1 is wound In core 2.Moreover, setting volume end face guard block 3 with two end contacts of the photoresist layered product of the winding. This, volume end face guard block 3 is represented as ring-type sheet material.

(photoresist layered product)

Photoresist layered product comprises 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 layered product 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 for 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 film, polyvinylidene chloride film, vinylidene chloride Copolymerization film, polymethyl methacrylate copolymer film, polystyrene film, polyacrylonitrile film, styrol copolymer are thin Film, polyamide film, cellulose derivative film etc..Used after can these films be stretched as needed.From resolution ratio Viewpoint is set out, and preferably mist degree is less than 5 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.On the thickness of supporting layer, relatively thin layer is favourable in terms of image formative and economy , but from thermal contraction grade when needing to maintain photosensitive resin coating composition layer, preferably use 10 μm~30 μm Thickness.GR19, GR16, Mitsubishi Plastics, Inc. manufacture of Supreme Being people's DuPont Film (strain) manufacture 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, the closing force of protective layer and photo-sensitive resin is substantially smaller than supporting layer, therefore, it is possible to hold Change places stripping.For example, as protective layer, it is preferable to use polyethylene film, polypropylene film and stretched polypropene film etc.. Further, it is possible to use the excellent film of fissility disclosed in Japanese Unexamined Patent Application 59-202457 publications.The thickness of protective layer is excellent Elect 10~100 μm, more preferably 10~50 μm as.For example, GF-18, GF- of Tamapoly Co., Ltd.s manufacture can be included 818th, GF-858 etc..

For photo-sensitive resin, photosensitive polymer combination can be coated on to supporting layer and drying is 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 ratio 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 layered product, known method can be used.For example, prepare in advance by Photosensitive polymer combination for photo-sensitive resin is mixed with solvent as photosensitive polymer combination blending liquid, uses rod Painting machine or roll coater are applied to supporting layer and dry it, and stacking includes the sense of the photosensitive polymer combination on supporting layer Photosensitive resin layer.It is 500~4000mPA seconds that photosensitive polymer combination blending liquid, which preferably adds solvent and is blended at 25 DEG C,. From the viewpoint of photosensitive polymer combination blending fluid viscosity, drying property, residual solvent amount, coating, foaminess, in solvent Can suitably selectively using MEK, acetone, ethanol, methanol, propyl alcohol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, Toluene etc..Then, by being laminated protective layer on the photo-sensitive resin, photoresist layered product can be made.

For photoresist layered product, so that strip is wound in core and is turned into web-like and is used.Spooling length does not have It is particularly limited to, from the viewpoint of the weight and processing easness of volume, preferably below 320m.If 1 photo-sensitive resin The base material more at most efficiency that can be laminated of stack volume is higher, therefore from the viewpoint of productivity ratio, spooling length be 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 cylindric. Because photoresist layered product as etching or plating resist layer and permanent pattern is used for electronic material, therefore it is preferable to carry out The core of the core of dustless processing, preferably plastic resin.The material of plastic resin be preferably gently, it is excellent strength, dustless Material.Polypropylene (PP) resin, acrylonitrile-butadiene-styrene (ABS) (ABS) resin, nylon resin, polyvinyl chloride tree can be used Fat etc., preferably ABS resin.The diameter of core is not particularly limited, and photoresist layered product volume is being installed on into laminater In the case of, in order to be installed on device, core is preferably 2~5inch, more preferably 3inch diameter.The length of core (using cylindric or columned core when be its axial length) compared with the width of photoresist layered product, Ke Yixiang It is same or shorter, but when winding photoresist layered product, in order to may insure appropriate extension in both sides, preferably roll up The length of core is more than the length of the width of photoresist layered product.Annular lamina can be installed in the way of through the extension Material, therefore preferably.Alternatively, it is also possible to which the bearing for being referred to as core body support is embedded in into the extension and so that photo-sensitive resin The mode that stack volume is not moved takes care of photoresist layered product volume under vacant state.

(volume end face guard block)

For volume end face guard block, by with matching somebody with somebody in the way of the end contact of the photoresist layered product 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 influence, these, it is preferred to according to the end contact with the photoresist layered product of winding Mode through core the ring-type sheet material that configures of extension ground.Photonasty can substantially be covered by further preferably having 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 layered product, but it is preferred for two ends.

When it is ring-type sheet material to roll up end face guard block, for its ring internal diameter, in order to be used through core, preferably omit More than the external diameter of core.In addition, by being moved slightly away from the center of ring-type sheet material and the center of core, thus ring-type sheet material is outer Week slightly has from the periphery of the photoresist layered product of wound into rolls exposes.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 more than 1.001 times progress of the ring internal diameter for core external diameter (Japanese is not blocked to core during installation：Zhang り pay I), thus preferably.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 matter, preferably ring internal diameter is 1.1 times of the external diameter of core 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 layered product volume, preferably wound into rolls More than 0.99 times of the external diameter of photoresist layered product, 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 of the external diameter of layered product volume, more preferably more preferably less than 1.05 times, less than 1.03 times.

For roll up 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 (LDPE), high density polyethylene (HDPE), hard Polyvinyl chloride, soft PVC, glassine paper, acetate, Triafol T, polystyrene, makrolon, polyimides etc. Plastic resin and the paper of dust-proof processing, the good quality paper of dust-proof processing, clean-keeping paper and, paper and foregoing plastics resin paste Material, synthetic paper closed etc..Because photoresist layered product is as resist layer or plating resist layer and permanent pattern For electronic material, therefore the material of dustless processing has been preferable to carry out it.From the generation of electrostatic less, it is good to the tracing ability of end face, Foreign matter removal is excellent and installation it is also excellent from the viewpoint of, preferred substrates are the paper of dust-proof processing, dust-proof processing Good quality paper, clean-keeping paper and, paper fitted with foregoing plastics resin material, synthetic paper is as material.Synthetic paper preferably will Polypropylene is used as main material.

When base material be the paper of dust-proof processing, the good quality paper of dust-proof processing, 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 the viewpoint of installation, preferably 50 μm with On, from the viewpoint of the tracing ability to end face, foreign matter 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 the viewpoint of release property, soil resistance, surface can also be embossed and added Work.For volume end face guard block, there is adhesive composition in the side for the end contact rolled up with photoresist layered product. Volume end face guard block is preferably to overlook circular ring-type sheet material.

For aforementioned cyclic sheet material, aforementioned cyclic sheet material, which is present in aerial mode according to its half and is arranged on, to be protruded horizontally up Flat board on, by the top for being present in aforementioned cyclic sheet material farthest from flat board in aerial part of aforementioned cyclic sheet material, with Flat board with the distance between the face of aforementioned cyclic sheet material contact side is set to deflection distance H (mm), aforementioned cyclic sheet material external diameter When half is set to R (mm), H/R is preferably 0.06~0.59.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.Gone from the tracing ability to rolling up end face with foreign matter From the viewpoint of property, preferably more than 0.06.More preferably more than 0.1, more preferably more than 0.15.

Deflection distance H assay method 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, the face-up of adhesive is will be provided with, Set in the way of not fitted with flat board 7.Half according to ring-type sheet material 3 is present in the air, i.e., according in ring-type sheet material 3 The heart be located at flat board end present in be essentially linear edge mode stationary ring sheet material.When fixed, such as Fig. 2 institutes Show, fixed component 8 can also be used to be fixed.Now, ring-type sheet material 3 will not by influenceed beyond gravity and bend or Bending.From the aerial part (part exposed from end) of ring-type sheet material, distance is present in by L fonts scale measure flat Hanging down between the imaginary plane that the farthest top of ring-type sheet material in the edge of plate is formed with the face contacted with ring-type sheet material of flat board Nogata is to distance.Determine place and be set to Fushi City, Shizuoka,Japan County.

(adhesive composition)

For adhesive composition, it can select to use when having peeled off volume end face guard block in photopolymer film There is no cull on end face, there is no the attachment of photoresist on volume end face guard block when having peeled off volume end face guard block Known adhesive composition.

Wherein, preferably it is the combination of resin comprising acrylic acid (ester) from the viewpoint of foreign matter removal and release property Thing.Photosensitive polymer combination is to include 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 can highly having concurrently From the viewpoint of foreign matter removal and release property and it is preferred that.

Particle is preferably comprised for adhesive composition, more than the 50 mass % of the particle are preferably to have the adhesive group 80~120% diameter of the coating thickness of compound, and the particle content relative to 100 parts by weight of binder be 5 weight Part to 30 parts by weight.It should be noted that the diameter of particle uses micro- sem observation, for arbitrary 100 particles, observe Its maximum gauge, and calculate its average value.

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

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

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

The content of particle is 5 parts by weight to 30 parts by weight preferably relative to 100 parts by weight of binder.In the situation of attaching Under, from the viewpoint of the de-bubbled of air, it is more than preferably 5 parts by weight, from the viewpoint of cementability, preferably 30 with Under.More preferably 10 parts by weight are to 25 parts by weight.When the material of particle is glass, 15~30 parts by weight are suitable, plastics It is preferably 5~25 parts by weight in the case of system.

The material of particle is preferably plastics, inorganic material.As plastics, polymethacrylates system, poly- first can be included Base methyl acrylate 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, silica (silicate mineral), calcium carbonate can be included.

The bonding force of adhesive can by reducing the overall softening temperature of composition, improve the polarity of resin component and carry It is high.

As the bonding force of end face guard block and low-density polyethylene film, from foreign matter removal and the viewpoint of installation Set 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 end face guard block It is formed with attaching low-density polyethylene film (LDPE) sheet material on the face of the layer of adhesive composition.Low-density polyethylene film makes Use TAMAPOLY Co., the GF-858 of Ltd manufactures.Wide 1inch, length 15cm rectangular strip are cut into, in relative humidity 50%th, 23 degree Celsius adjust down humidity 11 hours.Use Orientec Co., the Tensilon RTM-500 of Ltd manufactures, with negative Lotus sensor 1kg, draw speed carry out tension test in 100mm/ minutes.Now, with Tensilon bottom by the end face of sample Guard block blocks (fixation), is blocked low-density polyethylene film (fixation) with extension section, carries out tension test.Tension test In take the integral mean of load in stretching 10mm to 50mm interval, and being averaged for test number (TN) 2 times is taken, as cementability Value.

(manufacture method of photoresist layered product volume)

Photoresist layered product volume from suppress foreign matter attachment with suppress transport when it is photosensitive from the viewpoint of, preferably make Covered with shading sheet material.Shading sheet material is referred to as light-proofness film.Shading sheet material can be according to being wound in photonasty The mode of laminated resin body volume covers photoresist layered product 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 way that the part longer than core 2 be folded into inside core, further Suppress the attachment of foreign matter and photosensitive, therefore preferably.

Shading sheet material from can protect photoresist layered product volume with the contact from the light falling object of such as component, wrap From the viewpoint of the gentle touchdown of packaging container, preferred polyethylene.Thickness is from the suitable intensity of maintenance and suppresses pin hole Viewpoint is set out, preferably more than 10 μm, 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 layered product volume preferably by be formed with it is with foregoing 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, it can prevent that photoresist layered product holds with packaging during transport The contact of the ground wall of device.As core body support, for example, it can include Japanese Unexamined Patent Publication 2004-42952 and Japanese Unexamined Patent Publication 2003- Core body support described in 89477.

During using shading sheet material covering photoresist layered product volume, if the long part of the ratio core of shading sheet material is folded into Core body support is further installed in core and in the way of the invagination part is clamped, then can suppress the attachment and sense of foreign matter 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.

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

(a) the alkali-soluble macromolecule containing carboxyl

(a) the alkali-soluble macromolecule containing carboxyl will preferably contain α, and the monomer of β-unsaturation carboxyl is 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 developer solution or stripper containing aqueous alkali, 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 ratio and adaptation The viewpoint of raising and from ensure with the other compositions in solvent or photosensitive polymer combination, particularly and following (b) addition From the viewpoint of the compatibility of polymerizable monomer, the high molecular acid equivalent of the alkali-soluble of (a) containing carboxyl be preferably 100 with On, from the viewpoint of developability and fissility are improved, preferably less than 600.The measure of acid equivalent is to use flat natural pond industry The flat natural pond automatic titration device (COM-555) of (strain) manufacture is simultaneously entered using 0.1mol/L sodium hydroxide according to potentiometric titration Capable.

(a) the high molecular weight average molecular weight of the alkali-soluble containing carboxyl is preferably 5,000~500,000.From maintenance sense The thickness of photosensitive resin layer stack is uniform and obtains to the viewpoint of the patience of developer solution and goes out from the viewpoint for suppressing edge-melting Hair, weight average molecular weight is preferably 5, more than 000, in addition, from the viewpoint of developability is maintained, preferably 500, less than 000.It is molten While referring to the phenomenon for oozing out photosensitive polymer combination during photoresist layered product wound into rolls from volume end face.The sense oozed out Photosensitive resin composition sometimes under volume state can across supporting layer protective layer with from another layer adjacent of photo-sensitive resin 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 layered product of web-like sometimes, is peeled off in lamination from end face, is dispersed as resist bits.If anti- Erosion agent bits are attached to the substrate after lamination, then resist bits will attach to the mask of following exposure, be exposed solidification, Exposure, the defect as pattern are covered in the case of negative resist.

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 alkali-soluble containing carboxyl is 250,000.Weight average molecular weight in this specification is Refer to and polystyrene (the Shodex STANDARD SM- of Showa Denko K.K. manufactures are used by gel permeation chromatography (GPC) 105) weight average molecular weight that standard curve determination is obtained.

(a) the high molecular weight average molecular weight of the alkali-soluble containing carboxyl can use JASCO Corporation to manufacture Gel permeation chromatography be measured under the following conditions：

Differential refraction detector：RI-1530

Pump：PU-1580

Degasser：DG-980-50

Post insulating box：CO-1560

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

Eluent：THF.

(a) the alkali-soluble macromolecule containing carboxyl is preferably comprising 1 in aftermentioned first monomer or second comonomer The monomer for planting the above is used as the (co) polymer of composition.

First monomer is carboxylic acid or acid anhydrides with a polymerism unsaturated group in molecule.It can such as include (methyl) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride and acid half ester.Wherein, particularly preferably (methyl) acrylic acid.

Second comonomer is the monomer with least one polymerism unsaturated group in nonacid and molecule.It can include For example (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (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 polymerize Deng.Wherein, preferably (methyl) methyl acrylate, (methyl) n-butyl acrylate, styrene and (methyl) benzyl acrylate, from point From the viewpoint of resolution, particularly preferably using styrene.

(a) the alkali-soluble macromolecule containing carboxyl preferably by by above-mentioned monomer mix and with solvent such as acetone, In MEK or the solution of isopropanol, appropriate addition radical polymerization initiator such as benzoyl peroxide, azo Isobutyronitrile carries out heating stirring, so as to synthesize.Sometimes while in reaction solution be added dropwise mixture it is a part of while synthesized.Also have When reaction terminate after add solvent 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 alkali-soluble macromolecule of particularly preferred (a) containing carboxyl, the copolymerization ratio of 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, it can include containing methyl-prop E pioic acid methyl ester, methacrylic acid and styrene contain methyl methacrylate, methacrylic acid as the polymer of copolymer composition With polymer of the n-butyl acrylate as copolymer composition, and contain benzyl methacrylate, methyl methacrylate and third Olefin(e) acid 2- ethylhexyls are used as polymer of copolymer composition etc..

The high molecular content of the alkali-soluble of (a) containing carboxyl in photosensitive polymer combination 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) containing carboxyl The high molecular content of alkali-soluble is from the alkali-developable of maintenance photosensitive polymer combination, by resisting formed by exposure, development The viewpoint that corrosion figure case for example has sufficient patience as the characteristic of resist layer in indentation, etching and various electroplating work procedures goes out Hair, preferably more than 20 mass % have sufficiently soft from the corrosion-resisting pattern after the photosensitive polymer combination before solidification, solidification From the viewpoint of soft, preferably below 90 mass %.

(b) addition polymerization monomer

(b) addition polymerization monomer is the chemical combination for having at least one ethylenic unsaturated bond that can polymerize in intramolecular Thing.Ethylenic unsaturated bond is preferably terminal ethylenic unsaturated group.And then, 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 carbon-to-carbon unsaturated double-bond with (methyl) acryloyl group or from (methyl) acryloyl group and chemical combination Thing.As specific example, the polyethylene glycol for the oxirane that the average Unit 2 of addition are distinguished at the two ends of bisphenol-A can be included Two (methacrylic acid) ester two (methacrylic acid) esters NK ester BPE-200 of manufacture (Xin Zhong villages chemical industry (strain)) or double Distinguish dimethylacrylate (the Xin Zhong villages chemistry work of the polyethylene glycol of the oxirane of the average Unit 5 of addition in phenol A two ends The NK ester BPE-500 of industry (strain) manufacture), distinguish at the two ends of bisphenol-A the oxirane of the average Unit 6 of addition and average 2 single Two (methacrylic acid) esters of the PAG of the expoxy propane of member, to distinguish at the two ends of bisphenol-A addition average 15 single Two (methacrylic acid) esters of the PAG of the expoxy propane of the oxirane of member and average Unit 2.

As (b) addition polymerization monomer, in addition to above-mentioned compound, it can use with least one olefinic not The known compound of saturated group.Such as the glycol DPG acrylate of 4- nonyls phenyl seven, acrylic acid 2- can be included Hydroxyl -3- phenoxy propyls ester, the own glycol acrylate of phenoxy group, phthalic anhydride and acrylic acid 2- hydroxypropyl acrylates it is half-esterification The reactant (Japanese catalyst chemistry manufacture, trade name OE-A 200) of compound and expoxy propane, the Asia third of 4- n-octyls epoxide five 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, glycerine three (methyl) acrylate, pentaerythrite five (methyl) propylene Double (the ethyoxyls of 4- methacryloxies five 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, isocyanurate compound containing carbamate groups Deng.They can be used alone, and can also be used in combination of two or more, can also be with 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 The scope for dividing total amount to be used as benchmark to be 5~75 mass %, more preferably 15~70 mass %.From resolution ratio, adaptation and copper cash Formative from the viewpoint of, the content of (b) addition polymerization monomer is more than 5 mass %, 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 triggers Agent and the material used, particularly preferably using six aryl bisglyoxalines (hereinafter also referred to triarylimidazoles dimer).

As triarylimidazoles dimer, for example, it 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- couples-(Chloro-O-Phenyl) -5- (3,4- bis- Methoxyphenyl)-diphenyl-imidazole dimer,

2,4,5- tri--(Chloro-O-Phenyl)-diphenyl-imidazole dimer, 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- difluoromethyls 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- tetrafluoros phenyl) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-imidazoles dimer, 2, 2 '-bis--(2,3,4,6- tetrafluoros 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, it is for resolution ratio or solid Changing film strength against corrosion has the Photoepolymerizationinitiater initiater of 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, acridine compounds or pyrazoline chemical combination can be used Thing.As acridine compounds, acridine, 9- phenylacridines, 9- (4- tolyls)-acridine, 9- (4- methoxyphenyls) can be included Acridine, 9- (4- hydroxyphenyls) acridine, 9- ethyls acridine, 9- chloroethyls acridine, 9- methoxyacridines, 9- ethyoxyl acridines,

9- (4- aminomethyl phenyls) acridine, 9- (4- ethylphenyls) acridine, 9- (4- n-propyls 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- diethylaminos 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, preferably 1- phenyl -3- (4- tert-butyl-styrenes base) -5- (4- tbutyl-phenyls) - Pyrazoline, 1- (4- (benzoxazole -2- bases) phenyl) -3- (4- tert-butyl-styrenes base) -5- (4- tbutyl-phenyls)-pyrazoles Quinoline, 1- phenyl -3- (4- xenyls) -5- (4- tbutyl-phenyls)-pyrazoline, (4- is tertiary pungent by 1- phenyl -3- (4- xenyls) -5- Base-phenyl)-pyrazoline.

As Photoepolymerizationinitiater initiater in addition to the foregoing, for example, it can include 2- EAQs, octaethyl anthraquinone, 1,2- Benzo anthraquinone, 2,3- benzos anthraquinone, 2- phenyl anthraquinone, 2,3- diphenyl anthraquinone, 1- chloroanthraquinones, 1,4- naphthoquinones, 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 aromatic series ketone such as ketone, the benzoin such as benzoin, benzoin ethyl ether, benzoin phenylate, methylbenzoin and ethyl benzoin Ethers,

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

It should be noted that as the combination of above-mentioned thioxanthene ketone class and alkyl amino benzoic acid, such as second can be included The combination of the combination of base thioxanthones and dimethyl amino benzoate, CTX and dimethyl amino benzoate with And the combination of isopropyl thioxanthone and dimethyl amino benzoate.Alternatively, it is also possible to use N- aryl amino acids.It is used as N- The example of aryl amino acid, can include N-phenylglycine, N- Methyl-N-phenyls 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 Total amount as benchmark be 0.01~30 mass % scope, preferred lower limit is 0.05% mass %, further preferably 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 Obtained during capable photopolymerization from the viewpoint of abundant sensitivity, the content of (c) Photoepolymerizationinitiater initiater is more than 0.01 mass %, from Light is set fully to be transmitted to the bottom surface (i.e. the part away from light source) of photosensitive polymer combination, obtain good discrimination during photopolymerization It is below 30 mass % from the viewpoint of rate and adaptation.

(e) other additives

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

In the case of containing above-mentioned coloring material, the addition of coloring material with the solid of photosensitive polymer combination into Total amount is divided to be used 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, in order to assign visual image by exposing, colour developing can also be contained 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, can including three (4- dimethylamino -2- aminomethyl phenyls) methane, [procrypsis is crystallized It is purple], three (4- dimethylamino -2- aminomethyl phenyls) methane [leucomalachite green] and fluoran dyes.Wherein, procrypsis knot is being used 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, 1,1,1- tri- chloro- 2,2- double (rubigan) ethane, six Chloroethanes, 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, respectively preferably 0.1~10 mass %.

In addition, heat endurance and storage stability in order to improve photosensitive polymer combination, preferably in photoresist In composition containing radical polymerization inhibitor or in the group being made up of benzotriazole and carboxyl benzotriazole class at least More than a kind of compound.

As such radical polymerization inhibitor, for example, it can include p methoxy phenol, quinhydrones, pyrogallol, naphthylamines, tertiary fourth Base catechol, stannous chloride, 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, it can include 1,2,3- BTAs, 1- chloro- 1,2,3- BTAs, 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, it can include 4- carboxyls -1,2,3- BTAs, 5- carboxyls -1,2,3- benzene And triazole, (N, N- dibutylamino) carboxyl benzotriazole, N- (- 2- the ethylhexyls of N, N- bis-) aminomethylene carboxyl benzo three Azoles, N- (- 2- the ethoxys of N, N- bis-) aminomethylene carboxyl benzotriazole, N- (- 2- the ethylhexyls of N, N- bis-) aminoethylene Carboxyl benzotriazole.

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

In photosensitive polymer combination, other plasticizer can be contained as needed.As such plasticizer, for example It can include and bisphenol-A is subjected to the modified compound of polyoxy alkylidene.

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, ATBC, triethyl citrate, acetyl group The plasticizer of triethyl citrate, the n-propyl of acetyl citrate three and acetyl tributyl citrate etc..Particularly preferably make With sorbitan derivatives and polyalkylene glycols.

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

Embodiment

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

First, the preparation method for illustrating embodiment and the sample for evaluation of comparative example, secondly, is represented on gained sample Evaluation method 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 makes as follows.

The making ＞ of ＜ photoresist layered products

By the composition 1 shown in table 1 below, (wherein, the numeral of each composition is denoted as the compounding amount (quality of solid constituent Part).It is consistent in abbreviation and table 2 in table 1.) and solvent fully stir, mix, be made photosensitive polymer combination tune Liquid is closed, prepares the pet film (R310 of Mitsubishi Plastics, Inc. manufactures) of 16 μ m-thicks As supporter, photosensitive polymer combination blending liquid is equably coated on 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 On photo-sensitive resin, surface without stacking pet film, fit and be used as 33 μm of protective layer Thick polyethylene film (GF-858 of TAMAPOLY CO., LTD. manufactures), obtains photoresist layered product 1.

In addition, in above-mentioned photoresist layered product 1, in addition to composition 1 is set into composition 2~6, with photonasty Laminated resin body 1 is similarly made, and obtains photoresist layered product 2~6.In above-mentioned photoresist layered product 1, remove Composition 1 is set to composition 7~10, the thickness of photo-sensitive resin is set to beyond 10 μm, is laminated with photoresist Body 1 is similarly made, and obtains photoresist layered product 7~10.

The making ＞ of ＜ photoresists layered product volume

Ring-type sheet material uses the sheet material shown in 3~table of table 5.For the bonding containing acrylic acid (ester) resin of ring-type sheet material Agent composition, in case of no particular description, directly will be peeled off again using Elleair TackNS80/SBG85S/ 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 on base material and is dried, adjusts, so that dried thickness is 15μm。

By the otch of photoresist layered product 1 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 layered product of wound into rolls is 180mm.

Make to be wound in core body and the photoresist layered product as web-like is maintained on bar-shaped stainless steel support, should Stainless steel support is designed on bar-shaped stainless steel support in the way of the fixed other end can keep level.

It is photosensitive as web-like using periphery 500mm, long 800mm, thick 80 μm cylindrical shape light-proofness polyethylene pipe covering Property laminated resin body.

The photoresist layered product of the foregoing web-like covered by light-proofness polyethylene pipe is dismantled from support, according to width Volume is set in the buffer part that the mode that 330mm, high 100mm and upper bend can fix volume for concavity is designed.

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

Light-proofness polyethylene pipe is folded into core body, installation is convex according to central part, the mode chimeric with core body is designed Core body support, photoresist volume 1 is packed.

2. metewand

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

(1) foreign matter removal

Ring-type sheet material is peeled off from photoresist layered product volume, is confirmed whether have foreign matter to be attached to ring-type sheet material.It is as follows It is labeled grade.

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

△：Foreign matter 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 matter on crossed belt.

×：Foreign matter 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 matter.

(2) ring-type sheet material installation

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

○：Ring-type sheet material can be simply installed.When being attached at volume end face, it can attach no fold.

△：The time is needed in terms of attaching by 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 ring-type sheet material is attached, being installed in support or core needs the time.When stripping is not intended to position On the ring-type sheet material that is attached and when attaching again, ring-type sheet material, which is stretched, deformation or to be broken, and making to be attached at volume end face becomes It is difficult.

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

After content production volume described in the making ＞ rolled up as above-mentioned ＜ photoresists layered product, 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, mark grade is carried out as follows.

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

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

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

(4) removal of ring-type sheet material

After the content production described in makings ＞ rolled up as above-mentioned ＜ photoresists layered product is rolled up, broken seal, with wearing The hand for having resin-made gloves peels 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 matter number

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

[table 1]

[table 2]

B-1	The mass % of methacrylic acid 25, the mass % of methyl methacrylate 50, the mass % of styrene 25 terpolymer (weight average molecular weight 50000, acid equivalent 344)
		B-2	The mass % of methacrylic acid 25, the mass % of methyl methacrylate 65, the mass % of butyl acrylate 10 terpolymer (weight average molecular weight 70000, acid equivalent 344)
B-3	The mass % of methacrylic acid 25, the mass % of methyl methacrylate 65, the mass % of butyl acrylate 10 terpolymer (weight average molecular weight 120000, acid equivalent 344)
		M-1	Trimethylolpropane triacrylate
M-2	The amino methyl carboxylate of hexamethylene diisocyanate and five trimethylene glycol monomethacrylates
		M-3	Three epoxide ethyl trimethylolpropane triacrylates
M-4	Two (methacrylic acid) esters of the PAG of the expoxy propane of the average Unit 2 of addition and the oxirane of average Unit 6 are distinguished at the two ends of bisphenol-A
		M-5	Two (methacrylic acid) esters of the polyethylene glycol of the oxirane of each average Unit 2 of addition are distinguished at the two ends of bisphenol-A
M-6	In two (methacrylic acid) esters of poly- its glycol of alkylene 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) esters of the polyethylene glycol of the oxirane of each average Unit 5 of addition are 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 polyoxyethylene [three (1- phenethyls) phenyl ethers] of the average 18 moles oxirane of addition
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 group-s-triazine
		X-5	3- glycidoxy-propyltrimethoxy silanes

[table 3]

[table 4]

[table 5]

Except photoresist layered product 1 is made into photoresist layered product 2~6, sample B is used on ring-type sheet material In addition, make photoresist layered product in the same manner as photoresist layered product volume 1 to roll up, be laminated as photoresist Body volume 2~6.When rolling up the evaluation that 2~6 carry out (1)~(5) using photoresist, obtain with using photo-sensitive resin stack Roll up result same when 1.

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

Industrial applicability

For above-mentioned photoresist layered product volume, due to easily foreign matter can be 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 being fitted into precision equipment, electronic material.

Description of reference numerals

1 photoresist layered product

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 layered products are rolled up

Claims

1. a kind of photoresist layered product volume, wherein, by photoresist layered product in core wound into rolls, roll up end face Guard block by with being configured in the way of the end contact of the photoresist layered product wound up,

The volume end face guard block is run through by the core,

The volume end face guard block have with the side of the end contact of the photoresist layered product wound up it is viscous Mixture composite,

2. photoresist layered product volume according to claim 1, it is characterised in that it is covered by shading sheet material.

3. photoresist layered product volume according to claim 2, it is characterised in that the shading sheet material is tubular.

4. rolled up according to photoresist layered product according to any one of claims 1 to 3, wherein,

The volume end face guard block is to be configured at the ring-type sheet material in the end face of the photoresist layered product of wound into rolls, The ring-type sheet material is configured in the way of the extension through the core.

5. photoresist layered product volume according to claim 4, 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. the photoresist layered product volume according to claim 4 or 5, 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 protruded horizontally up, by the annular lamina The front end for being present in the ring-type sheet material farthest from flat board in aerial part of material, connect with the ring-type sheet material with flat board When the distance between the face for touching 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 is 0.06~0.59.

7. rolled up according to photoresist layered product according to any one of claims 1 to 6, it is characterised in that the end face is protected The bonding force for protecting part and low-density polyethylene film is 5gf/inch~250gf/inch.

8. rolled up according to photoresist layered product according to any one of claims 1 to 7, it is characterised in that the volume end face The base material of guard block be dust-free paper, low dirt paper, synthetic paper or, the material fitted with resin base material of paper.

9. rolled up according to photoresist layered product according to any one of claims 1 to 8, it is characterised in that the photonasty Resin bed is the layer for including photosensitive polymer combination, and the photosensitive polymer combination is high comprising the alkali-soluble containing carboxyl Molecule, addition polymerization monomer, Photoepolymerizationinitiater initiater.

10. photoresist layered product volume according to claim 9, it is characterised in that the alkali containing carboxyl is solvable Property macromolecule be styrene or derivatives thereof copolymerization material.

11. the photoresist layered product volume according to claim 9 or 10, it is characterised in that the addition polymerization list Body includes bisphenol-A system (methyl) acrylate compounds.

12. the photoresist layered product volume according to any one of claim 9~11, it is characterised in that the light gathers Close initiator and include six aryl bisglyoxalines or derivatives thereof.

13. the photoresist layered product volume according to any one of claim 1~12, it is characterised in that the bonding Agent composition is resin comprising acrylic acid (ester).

14. the photoresist layered product volume according to any one of claim 1~13, it is characterised in that the bonding Agent composition contains adhesive and particle, and more than the 50 mass % of the particle have the 80 of the coating thickness of the adhesive composition ~120% diameter, and the particle content relative to 100 parts by weight of binder be 5 parts by weight to 30 parts by weight.

15. a kind of manufacture method of photoresist layered product volume, it is characterised in that

The photoresist layered product of wound into rolls in core, with the end face with the photoresist layered product wound up Way of contact configuration volume end face guard block, wherein,

The volume end face guard block is run through by the core,

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

16. the manufacture method of photoresist layered product volume according to claim 15, 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, and the ring is configured in the way of the extension through the core Shape sheet material.

17. the manufacture method of the photoresist layered product volume according to claim 15 or 16, it is characterised in that

18. the manufacture method of the photoresist layered product volume according to any one of claim 15~17, its feature exists In the bonding force of the ring-type sheet material and low-density polyethylene film is 5gf/inch~250gf/inch.

19. a kind of packing method of photoresist layered product volume, it is characterised in that usage right requirement any one of 15~18 Described method manufacture photoresist layered product volume, further covers the photoresist by the shading sheet material of tubular and is laminated Body is rolled up.

20. a kind of ring-type sheet material, it is the ring-type sheet material of film film roll of wound into rolls in core, wherein,

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

The ring-type sheet material configured in the way of the core runs through and with the end contact of the film of the winding,

The ring-type sheet material has adhesive composition in the side with the end contact of the film of the winding, with through the volume The mode of the extension of core is configured on film roll.

21. ring-type sheet material according to claim 20, wherein, the film is photoresist layered product.

22. the ring-type sheet material according to claim 20 or 21, it is characterised in that

23. the ring-type sheet material according to any one of claim 20~22, it is characterised in that it is thin with low density polyethylene (LDPE) The bonding force of film is 5gf/inch~250gf/inch.

24. the ring-type sheet material according to any one of claim 20~23, it is characterised in that its base material having is dustless Paper, low dirt paper, synthetic paper or, the material fitted with resin base material of paper.

25. the ring-type sheet material according to any one of claim 21~24, it is characterised in that the photo-sensitive resin is Layer comprising photosensitive polymer combination, the photosensitive polymer combination includes the alkali-soluble macromolecule containing carboxyl, added Into polymerizable monomer, Photoepolymerizationinitiater initiater.

26. ring-type sheet material according to claim 25, it is characterised in that the alkali-soluble macromolecule containing carboxyl is The material of styrene or derivatives thereof copolymerization.

27. the ring-type sheet material according to claim 25 or 26, it is characterised in that the addition polymerization monomer includes bis-phenol A systems (methyl) acrylate compounds.

28. the ring-type sheet material according to any one of claim 25~27, it is characterised in that the Photoepolymerizationinitiater initiater bag Containing six aryl bisglyoxalines or derivatives thereof.

29. the ring-type sheet material according to any one of claim 20~28, it is characterised in that described adhesive composition bag (ester) containing acrylic acid is resin.

30. the ring-type sheet material according to any one of claim 20~29, it is characterised in that described adhesive composition contains There are adhesive and particle, more than the 50 mass % of the particle have the 80~120% of the coating thickness of the adhesive composition Diameter, and the particle content relative to 100 parts by weight of binder be 5 parts by weight to 30 parts by weight.

31. a kind of film roll, it possesses the ring-type sheet material described in covered by shading sheet material, claim 20~30.