CN106393838A

CN106393838A - Photosensitive resin laminate roll

Info

Publication number: CN106393838A
Application number: CN201610799124.XA
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: 2017-02-15
Anticipated expiration: 2033-12-26
Also published as: JP2017071445A; KR20150079919A; KR101950064B1; JP6046746B2; TW201613817A; TW201431769A; JP6315724B2; CN104903207B; WO2014104217A1; KR102191080B1; CN106966074A; TWI522303B; TWI611990B; MY176080A; CN106393838B; KR20190018037A; CN104903207A; JPWO2014104217A1; CN106966074B

Abstract

Provided is a photosensitive resin laminate roll which enables foreign bodies to be easily eliminated from the end surfaces of the photosensitive resin laminate roll when said roll is being unpacked. This photosensitive resin laminate roll comprises: a photosensitive resin laminate wound into a roll shape onto a winding core; and roll end surface protective members disposed so as to be in contact with the end surfaces of the wound photosensitive resin laminate. The roll end surface protective members each have an adhesive composition on the side that is in contact with the roll end surface. The photosensitive resin laminate includes at least a support layer, and a photosensitive resin layer laminated on the support layer.

Description

Photoresist duplexer is rolled up

The application is to be December 26, Application No. CN201380068564.2 in 2013 applying date, invention entitled sense The divisional application of the application of photosensitive resin layer stack volume.

Technical field

The present invention relates to photoresist duplexer volume.

Background technology

In the past, the packaging as photosensitive element disclosed several ways.For example disclose to protect volume end face to 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 publication

Content of the invention

Problems to be solved by the invention

The invention solves the problems that problem be, provide unpacking when can simply by foreign body from photoresist duplexer The photoresist duplexer volume that volume end face removes.

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 configures according to the mode with the end contact of the photoresist duplexer winding up,

Described volume end face guard block has adhesive composition in the side being used for roll up end contact,

Described photoresist duplexer includes at least supporting layer and the photo-sensitive resin being laminated in this supporting layer.

[2]

Photoresist duplexer according to [1st] item is rolled up it is characterised in that it is covered by shading sheet material.

[3]

Photoresist duplexer volume according to [2nd] Xiang Shu is it is characterised in that described shading sheet material is tubular.

[4]

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

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

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

[5]

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

[6]

According to [4th] or [5] item photoresist duplexer volume it is characterised in that

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

[7]

Photoresist duplexer volume according to any one of [1st]～[6] item is it is characterised in that described 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 is it is characterised in that described volume end The base material of face guard block is 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 is it is characterised in that described photosensitive Property resin bed is the layer comprising photosensitive polymer combination, and described photosensitive polymer combination comprises the alkali-soluble containing carboxyl Macromolecule, addition polymerization monomer, Photoepolymerizationinitiater initiater.

[10]

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

[11]

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

[12]

Photoresist duplexer volume according to any one of [9th]～[11] item is it is characterised in that described light gathers Close initiator and comprise six aryl bisglyoxalines or derivatives thereof.

[13]

Photoresist duplexer volume according to any one of [1st]～[12] item is it is characterised in that described bonding It is resin that agent compositionss comprise acrylic acid (ester).

[14]

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

[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 winding up End contact mode configures volume end face guard block, wherein,

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

This photoresist duplexer includes at least supporting layer and the photo-sensitive resin being laminated in this supporting layer,

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

This volume end face guard block is following ring-type sheet material：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 The internal diameter of this ring-type sheet material is 1～1.1 times of core external diameter.

[16]

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

[17]

According to [15th] or [16] item photoresist duplexer volume manufacture method it is characterised in that

[18]

The manufacture method of the photoresist duplexer volume according to any one of [15th]～[17] item, its feature exists In described 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 require arbitrary in 15～18 Method described in manufactures photoresist duplexer volume, covers described photo-sensitive resin by the shading sheet material of tubular further Stack is rolled up.

[20]

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

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

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

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

[21]

Ring-type sheet material according to [20th] item, wherein, described 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 is 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 is it is characterised in that the base material that it has is no 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 is it is characterised in that described photo-sensitive resin The layer comprising photosensitive polymer combination, described photosensitive polymer combination comprise the alkali-soluble macromolecule containing carboxyl, Addition polymerization monomer, Photoepolymerizationinitiater initiater.

[26]

Ring-type sheet material according to [25th] item is it is characterised in that the described 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 described addition polymerization monomer comprise double Phenol A system (methyl) acrylate compounds.

[28]

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

[29]

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

[30]

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

[31]

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

The effect of invention

If using the present invention photoresist duplexer volume, unpacking when can simply by foreign body from photonasty tree Lipid layer stack volume end face removes.

Brief description

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

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

Fig. 3 is the signal representing the embodiment of photoresist duplexer volume being 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, can various modifications be carried out in the range of its main idea to implement.

Photoresist duplexer volume is along its length in volume by the photoresist duplexer of strip (banding) Wind on core, and roll up end face guard block according to the end face (sense of described banding with the photoresist duplexer 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 comprises supporting layer 4, the photo-sensitive resin 5 being laminated in this supporting layer and arbitrary protective layer 6, and this duplexer 1 is wound In core 2.And, with two end contacts of the photoresist duplexer of this winding arrange volume end face guard block 3.? This, volume end face guard block 3 represents as ring-type sheet material.

(photoresist duplexer)

Photoresist duplexer includes at least supporting layer and the photo-sensitive resin being laminated on this supporting layer, preferably enters One step comprises the protective layer being laminated on photo-sensitive resin.Also comprise to be referred to as dry film against corrosion 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 use, preferably Transparent layer through 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..Can use after the stretching of these thin film as needed.From resolution Viewpoint is set out, and preferably 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, more enters 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 needing 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) manufactures for example can be included, Inc. manufactures R310-16, R340G16, レ Port リエステ Le Off ィ Le system (strain) manufacture FB40 (16 μm of thickness), FB60 (16 μm of films Thick) etc..

For protective layer, protective layer is substantially smaller than supporting layer, therefore, it is possible to hold with the closing force of photo-sensitive resin Change places stripping.For example, as protective layer it may be preferred to use polyethylene film, polypropylene film and stretched polypropene film etc.. Further, it is possible to use the excellent thin film of the 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. can be included 818th, GF-858 etc..

For photo-sensitive resin, photosensitive polymer combination can be coated supporting layer and drying is thus carry out layer Folded.The thickness of photo-sensitive resin is preferably 5～100 μm, and the preferred upper limit is 50 μm.Thickness due to photo-sensitive resin Closer to 5 μm, resolution is got over and is improved, and closer to 100 μm, film-strength is got over and improved, and therefore can be properly selected according to purposes.

Method as manufacturing photoresist duplexer, can adopt known method.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 so that it is dried, and stacking on supporting layer comprises the sense of this photosensitive polymer combination Photosensitive resin layer.It is 500～4000mPA second that photosensitive polymer combination blending liquid preferably add solvent to be 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 be suitably selectively using butanone, acetone, ethanol, methanol, propanol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetic acid Ester, toluene etc..Then, by being laminated protective layer on this photo-sensitive resin, photoresist duplexer can be made.

For photoresist duplexer, become web-like and use so that strip winds in core.Spooling length does not have It is particularly limited to, from the viewpoint of the weight of volume and process easness, 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 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 cylindric or cylindric. Because 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 the core of dustless process, preferably plastic resin.The material of plastic resin is 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., preferably 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 (being its axial length when using cylindric or columned core) compared with the width of photoresist duplexer, Ke Yixiang Same or shorter, but when winding photoresist duplexer, in order to may insure suitable extension in both sides, preferably roll up The length of core is more than the length of the width of photoresist duplexer.According to the mode running through this extension, annular lamina can be installed Material, therefore preferably.Alternatively, it is also possible to the bearing being referred to as core body support is embedded in this extension so that photo-sensitive resin The mode that stack volume does not move keeping photoresist duplexer volume under vacant state.

(volume end face guard block)

For volume end face guard block, join according to the mode with the end contact of the photoresist duplexer 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 run through the ring-type sheet material that configures of extension ground of core.Further preferably have and can substantially cover photonasty Laminated resin body rolls up the ring-type of the width of substantially overall size of end face.Volume end face guard block can be only used for being wound Photoresist duplexer one end, but be preferred for two ends.

When rolling up end face guard block for ring-type sheet material, for its ring internal diameter, use in order to core can be run through, preferably omit External diameter more than core.In addition, being moved slightly away from the center of core by making the center of ring-type sheet material, outer by this ring-type sheet material Week slightly exposes from the periphery of the photoresist duplexer of wound into rolls.So, the dismounting from ring-type sheet material becomes easy 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 During installation, (Japanese is not blocked to core：り pays I), thus preferably.More preferably more than 1.005 times, more preferably 1.01 more than again.From the viewpoint of protection is rolled up end face entirety and removed foreign body, 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 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 of the external diameter of duplexer volume, more preferably less than 1.05 times, more preferably less than 1.03 times.

For volume end face guard block base material, can include polyester, polyethylene terephthalate, polyphenylene sulfide, Polypropylene, nylon, respectively 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. The paper of plastic resin and dust-proof process, the good quality paper of dust-proof process, clean-keeping paper and, paper and foregoing plastics resin patch The material of conjunction, synthetic paper etc..Because photoresist duplexer is as resist layer or plating resist layer and permanent pattern For electronic material, therefore it has been preferable to carry out the material of dustless process.From the generation of electrostatic less, good to the tracing ability of end face, Foreign body removal is excellent and installation also excellent from the viewpoint of, 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 as material.Synthetic paper preferably will Polypropylene is 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 the viewpoint of installation, preferably 50 μm with On, 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, add it is also possible to be embossed to surface from the viewpoint of release property, soil resistance Work.For volume end face guard block, in the side of the end contact rolled up with photoresist duplexer, there is adhesive composition. Volume end face guard block is 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 partly in from the top of the farthest aforementioned cyclic sheet material of flat board and Flat board be 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 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 with foreign body from the tracing ability to volume end face From the viewpoint of 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 substantially horizontal direction (with vertical The orthogonal direction in direction) ring-type sheet material 3 is set on the substantial flat board 7 that stretches out.Now, will be provided with facing up of binding agent, Mode according to not fitted with flat board 7 is arranged.Half according to ring-type sheet material 3 is present in the air, that is, according in ring-type sheet material 3 The heart is located at the mode stationary ring sheet material being essentially linear edge existing for the end of flat board.When fixing, as Fig. 2 institute Show, it is possible to use fixed component 8 is fixed.Now, ring-type sheet material 3 will not be bent by affecting beyond gravity or Bending.From being present in the aerial part (part from end is exposed) of ring-type sheet material by L font scale mensure, distance is flat Hanging down between the imaginary plane that the face that the farthest top of ring-type sheet material in the edge of plate is contacted with ring-type sheet material with flat board is formed Nogata is to distance.Measure place and be set to Fushi City, Shizuoka,Japan County.

(adhesive composition)

For adhesive composition, can select to use when having peeled off volume end face guard block in photopolymer film Cull is not had on end face, the attachment of photoresist is not had when having peeled off volume end face guard block on volume end face guard block Known adhesive composition.

Wherein, from the viewpoint of foreign body removal with release property, preferably comprise the combination that acrylic acid (ester) is resin Thing.Photosensitive polymer combination is to comprise the alkali-soluble macromolecule containing carboxyl, addition polymerization monomer, photopolymerization initiation The photosensitive polymer combination of agent, adhesive composition comprises acrylic acid (ester) when being resin, from can further highly and Preferred from the viewpoint of tool foreign body removal and release property.

Granule is preferably comprised for adhesive composition, more than 50 mass % of this granule preferably there is this binding agent group The diameter of the 80～120% of the coating thickness of compound, and the content of this granule is 5 weight with respect 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 the viewpoint of release property, the diameter of granule is preferably more than 80%, from the viewpoint of viscosity, preferably Less than 120%.More preferably 90～110%, more preferably 100%.

For granule, even if can be generally the granule of Monosized powder in theory, but actually more in the case of be difficult to obtain ?.Preferably there is the granule of as narrow as possible, the i.e. sharp grading curve of particle size distribution.

Preferably more than 50 mass % of binding agent total amount be this binding agent coating thickness 80～120% 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 %.

It is 5 weight portions to 30 weight portions that the content of granule is preferably with respect to 100 parts by weight of binder.In situation about attaching Under, from the viewpoint of the de-bubbled of air, more than preferably 5 weight portions, 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 , 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 High.

As the bonding force of end face guard block and 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 this bonding force is measured in such a way.That is, with hand pressure roller in end face guard block Low-density polyethylene film (LDPE) sheet material is attached on the face of the layer being formed with adhesive composition.Low-density polyethylene film makes Use TAMAPOLY Co., the GF-858 that Ltd manufactures.It is cut into the rectangular strip of wide 1inch, length 15cm, in relative humidity 50%th, 23 degree Celsius adjust humidity 11 hours down.The Tensilon RTM-500 being manufactured using Orientec Co., Ltd, with negative Lotus sensor 1kg, draw speed 100mm/ minute carry out tension test.Now, with the bottom of Tensilon by the end face of sample Guard block blocks (fixation), with extension section, low-density polyethylene film is blocked (fixation), carries out tension test.Tension test In take the integral mean of load in the interval of stretching 10mm to 50mm, and take the average, as cementability of test number (TN) 2 times Value.

(manufacture method of photoresist duplexer volume)

Photoresist duplexer volume, from the viewpoint of suppressing the attachment of foreign body and photosensitive when suppressing transport, preferably makes 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 To cover photoresist volume 1 by photoresist volume 1 insertion cylinder, 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 folding into inside core the part longer than core 2, further The suppression attachment of foreign body and photosensitive, therefore preferably.

Shading sheet material is from contact, the bag that can protect the photoresist duplexer volume falling object light with being derived from such as component From the viewpoint of the gentle touchdown of packaging container, preferably polyethylene.Thickness 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 preferred black.

What photoresist duplexer volume preferably passed through to be formed with such protuberance chimeric with aforementioned core is referred to as core body A pair of part of support and be suspended vacantly.By being suspended vacantly, can prevent photoresist duplexer and packaging during transport from holding 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 part long for the ratio core of shading sheet material is folded into In core and according to the mode clamping this invagination part, core body support is installed further, then can suppress attachment and the sense of foreign body Light, therefore preferably.

(photosensitive polymer combination)

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

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

(a) alkali-soluble macromolecule containing carboxyl

A () alkali-soluble macromolecule containing carboxyl preferably will contain α, 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 with respect 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 wherein with the carboxyl of 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 Improve viewpoint and from guarantee with the other compositions solvent or photosensitive polymer combination, particularly with following (b) addition From the viewpoint of the compatibility of polymerizable monomer, the high molecular acid equivalent of (a) alkali-soluble containing carboxyl be preferably 100 with On, from the viewpoint of developability and fissility improve, preferably less than 600.The mensure of acid equivalent is using flat natural pond industry Flat natural pond automatic titration device (COM-555) that (strain) manufactures simultaneously is entered according to potentiometric titration using the sodium hydroxide of 0.1mol/L Row.

A the high molecular weight average molecular weight of () alkali-soluble containing carboxyl is preferably 5,000～500,000.Feel from maintaining The thickness of photosensitive resin layer stack uniformly and obtains the viewpoint of the patience to developer solution and goes out from the viewpoint of suppression edge-melting Send out, weight average molecular weight is preferably 5, more than 000, in addition, from the viewpoint of maintaining developability, preferably 500, less than 000.Molten While referring to ooze out the phenomenon of photosensitive polymer combination during 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.Photosensitive resin composition after photosensitive polymer combination after adhesion, i.e. edge-melting 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 this resist bits will attach to the mask next exposing, and is 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 (a) alkali-soluble 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 use polystyrene (the Shodex STANDARD SM- that Showa Denko K.K. manufactures by gel permeation chromatography (GPC) 105) weight average molecular weight that standard curve determination obtains.

A the high molecular weight average molecular weight of () alkali-soluble 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 () alkali-soluble macromolecule containing carboxyl preferably comprises in aftermentioned first monomer or second comonomer 1 Plant above monomer as the (co) polymer of composition.

First monomer is carboxylic acid or the anhydride in molecule with a polymerism unsaturated group.For example can 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 nonacid and molecule in there is the monomer of at least one polymerism unsaturated group.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 acrylate, (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.

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

For particularly preferred (a) the alkali-soluble macromolecule containing carboxyl, the copolymerization ratio of the first monomer and second comonomer Example is 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 (a) alkali-soluble containing carboxyl, for example, can include containing methyl-prop E pioic acid methyl ester, methacrylic acid and styrene as the polymer of copolymer composition, containing methyl methacrylate, methacrylic acid With n-butyl acrylate as copolymer composition polymer, and contain benzyl methacrylate, methyl methacrylate and third Olefin(e) acid 2- Octyl Nitrite is as the polymer etc. of copolymer composition.

The high molecular content of the alkali-soluble containing carboxyl for (a) in photosensitive polymer combination is with photosensitive resin composition The scope that the solid constituent total amount of thing is 20～90 mass % as benchmark, 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 for example has the viewpoint of sufficient patience in indentation, etching and various electroplating work procedure and goes out as the characteristic of resist layer Send out, more than preferably 20 mass %, the corrosion-resisting pattern after the photosensitive polymer combination before solidification, 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 in intramolecular with the ethylenic unsaturated bond that at least one can be polymerized 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 have (methyl) acryloyl group or from (methyl) acryloyl group carbon-to-carbon unsaturated double-bond and chemical combination Thing.As specific example, the Polyethylene Glycol of the oxirane of average Unit 2 can be included in the difference addition of the two ends of bisphenol-A Two (methacrylic acid) ester two (methacrylic acid) ester (the NK ester BPE-200 that Xin Zhong village chemical industry (strain) manufactures) or double The addition dimethylacrylate of the Polyethylene Glycol of oxirane of average Unit 5 (Xin Zhong village chemistry work is distinguished at the two ends of phenol A The NK ester BPE-500 that industry (strain) manufactures), in the two ends of the bisphenol-A respectively oxirane of the average Unit 6 of addition and average 2 single Two (methacrylic acid) ester of the poly alkylene glycol of expoxy propane of unit, at the two ends of bisphenol-A, respectively addition average 15 is single Two (methacrylic acid) ester of the poly alkylene glycol of expoxy propane of the oxirane of unit and average Unit 2.

As (b) addition polymerization monomer, in addition to above-mentioned compound, it is possible to use there is at least one olefinic not The known compound of saturated group.Such as 4- nonyl phenyl seven glycol dipropylene glycol acrylate, acrylic acid 2- can be included Hydroxyl -3- phenoxy propyl ester, phenoxy group own glycol acrylate, phthalic anhydride and acrylic acid 2- hydroxypropyl acrylate half-esterification The reactant (Japanese catalyst chemistry manufacture, trade name OE-A 200) of compound and expoxy propane, 4- n-octyl epoxide five Asia third Base butanediol acrylate, 1,6-HD (methyl) acrylate, 1,4- cyclohexanediol 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 (4- methacryloxy five ethyoxyl 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 containing carbamate groups, multifunctional (methyl) acrylate of 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 is become with the solid of photosensitive polymer combination Point scope that total amount is 5～75 mass % as benchmark, more preferably 15～70 mass %.From resolution, 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 such as photopolymerization usually as photoresist can be suitably used and cause 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 dimer (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- Dimethoxyphenyl) -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 dimer, 2- (Chloro-O-Phenyl)-bis- -4,5- (3,4- dimethoxies Base phenyl)-imidazoles dimer, 2,2 '-bis--(2- fluorophenyl) -4,4 ', 5,5 '-four-(3- methoxyphenyl)-imidazoles dimer, 2,2 '-bis--(2,3- difluoromethyl phenyl) -4,4 ', 5,5 '-four-(3- methoxyphenyl)-imidazoles dimer, 2,2 '-bis--(2, 4- difluorophenyl) -4,4 ', 5,5 '-four-(3- methoxyphenyl)-imidazoles dimer,

2,2 '-bis--(2,5- difluorophenyl) -4,4 ', 5,5 '-four-(3- methoxyphenyl)-imidazoles dimer, 2,2 ' - Double-(2,6- difluorophenyl) -4,4 ', 5,5 '-four-(3- methoxyphenyl)-imidazoles dimer, 2,2 '-bis--(2,3,4- trifluoro Phenyl) -4,4 ', 5,5 '-four-(3- methoxyphenyl)-imidazoles dimer, 2,2 '-bis--(2,3,5- trifluorophenyl) -4,4 ', 5, 5 '-four-(3- methoxyphenyl)-imidazoles dimer,

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

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

2- (Chloro-O-Phenyl) -4,5- diphenyl-imidazole dimer especially can be preferably used, it 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 permissible 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- phenylacridine, 9- (4- tolyl)-acridine, 9- (4- methoxyphenyl) can be included Acridine, 9- (4- hydroxyphenyl) acridine, 9- ethyl acridine, 9- chloroethyl acridine, 9- methoxyacridine, 9- ethyoxyl acridine,

9- (4- aminomethyl phenyl) acridine, 9- (4- ethylphenyl) acridine, 9- (4- n-pro-pyl phenyl) acridine, 9- (the positive fourth of 4- Base phenyl) acridine, 9- (4- tert-butyl-phenyl) acridine, 9- (4- ethoxyl phenenyl) acridine, 9- (4- acetylphenyl) acridine, 9- (4- dimethylaminophenyl) acridine, 9- (4- chlorphenyl) acridine,

9- (4- bromophenyl) acridine, 9- (3- aminomethyl phenyl) acridine, 9- (3- tert-butyl-phenyl) acridine, 9- (3- acetyl group Phenyl) acridine, 9- (3- dimethylaminophenyl) acridine, 9- (3- diethylamino phenyl) acridine, 9- (3- chlorphenyl) acridine, 9- (3- bromophenyl) acridine, 9- (2- pyridine radicals) acridine, 9- (3- pyridine radicals) acridine, 9- (4- pyridine radicals) acridine.Wherein, preferably 9- phenylacridine.

As pyrazoline compounds, preferably 1- phenyl -3- (4- tert-butyl-styrene base) -5- (4- tbutyl-phenyl) - Pyrazoline, 1- (4- (benzothiazole -2- base) phenyl) -3- (4- tert-butyl-styrene base) -5- (4- tbutyl-phenyl)-pyrazoles Quinoline, 1- phenyl -3- (4- xenyl) -5- (4- tbutyl-phenyl)-pyrazoline, (4- is tertiary pungent for 1- phenyl -3- (4- xenyl) -5- Base-phenyl)-pyrazoline.

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

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, thioxanthene ketone class and the benzoic combination of alkyl amino, 1- benzene The oxime esters such as base -1,2- propanedione -2-O- cupron, 1- phenyl -1,2- propanedione -2- (O- ethoxy carbonyl) oxime.

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 of base thiaxanthone 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 using N- aryl amino acid.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 The scope that total amount is 0.01～30 mass % as benchmark, preferred lower limit is 0.05% mass %, 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 obtaining abundant light sensitivitys during the photopolymerization of row, the content of (c) Photoepolymerizationinitiater initiater is more than 0.01 mass %, from Light is made fully to be transmitted to the bottom surface (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, the 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..

In the case of containing above-mentioned coloring material, the addition of coloring material is become with the solid of photosensitive polymer combination 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；For when below 1 mass %, having the effect maintaining storage stability.

In addition, in order to give visual image by exposure it is also possible to contain 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 crystallizes can to include three (4- dimethylamino -2- aminomethyl phenyl) methane Purple], three (4- dimethylamino -2- aminomethyl phenyl) 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- dibromopropyl) ester, trichloroacetamide, n-amyl iodide, double (rubigan) ethane of the chloro- 2,2- of isobutyl iodide, 1,1,1- tri-, 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 as benchmark, preferably respectively 0.1～10 mass %.

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

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

As benzotriazole, for example, can include 1,2,3- benzotriazole, chloro- 1,2, the 3- benzotriazole of 1-, double (N-2- Ethylhexyl) aminomethylene-l, 2,3 triazole, double (N-2- ethylhexyl) aminomethylene -1,2,3- tolytriazole, Double (N-2- ethoxy) aminomethylene-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- (N, N- bis- -2- ethylhexyl) aminomethylene carboxyl benzo three Azoles, N- (N, N- bis- -2- ethoxy) aminomethylene carboxyl benzotriazole, N- (N, N- bis- -2- ethylhexyl) aminoethylene Carboxyl benzotriazole.

The total addition of radical polymerization inhibitor, benzotriazole and/or carboxyl benzotriazole class is with photoresist group 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 the viewpoint of giving storage stability to photosensitive polymer combination, this total addition is excellent Elect more than 0.001 mass % as, 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 and bisphenol-A is carried out 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, tributyl citrate, triethyl citrate, acetyl group The plasticizer of triethyl citrate, acetyl citrate three n-propyl 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 is 3 mass %, and the preferred upper limit is 30 mass %.From Suppression 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, it is specifically described further in an embodiment, but be not limited to this.

First, the manufacture method that the sample for evaluation of embodiment and comparative example is described, secondly, represents with regard to gained sample Evaluation methodology and evaluation result.Here, employing 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 duplexer

By the compositionss 1 shown in table 1 below, (wherein, the numeral of each composition is denoted as the compounding amount (matter of solid constituent Amount part).Abbreviation in table 1 is consistent with table 2.) and solvent fully stir, mix, make photosensitive polymer combination Blending liquid, (Mitsubishi Plastics, Inc. manufacture the pet film of preparation 16 μ m-thick R310) as supporter, using die coating machine, photosensitive polymer combination blending liquid is equably coated this poly terephthalic acid The surface of glycol ester thin film is simultaneously dried, and then forms photo-sensitive resin.The thickness of photo-sensitive resin is 15 μm.Connect , on photo-sensitive resin, the surface that is not laminated pet film, laminating is as protective layer The polyethylene film (GF-858 that TAMAPOLY CO., LTD. manufacture) of 33 μ m-thick, 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 compositionss 7～10, the thickness of photo-sensitive resin is set to 10 μm in addition, with photoresist stacking Body 1 is similarly made, and obtains photoresist duplexer 7～10.

The making ＞ of ＜ photoresist duplexer volume

Ring-type sheet material uses the sheet material shown in table 3～table 5.For the bonding containing acrylic acid (ester) resin for the ring-type sheet material Agent compositionss, in case of no particular description, will directly 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, B-1 with M-8 shown in table 2 is become with solid Divide ratio for 45:55 and 40:60 mode is compounded, and coats base material and is dried, adjusts, so that dried thickness is 15μm.

Photoresist duplexer 1 otch is wide 495mm, internal diameter 77mm, external diameter 88mm, length 530mm ABS tree Fat core (core body) is upper to wind 300m.The external diameter of the photoresist duplexer of wound into rolls is 180mm.

The photoresist duplexer 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 on bar-shaped stainless steel support according to the fixing other end in the way of holding level.

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

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

Turn back one end of light-proofness polyethylene tube, so that the end face of web-like photoresist duplexer is exposed, 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, installs and design for the convex mode chimeric with core body 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 shown in table 3～5.

(1) foreign body removal

From photoresist duplexer volume, ring-type sheet material is peeled off, be confirmed whether have foreign body to be attached to ring-type sheet material.As follows It is labeled grade.

○：Foreign body is attached to ring-type sheet material.Volume end face attaches other adhesive tapes and is peeled off it is impossible to be confirmed to have different Thing adheres to.

△：Foreign body is attached to ring-type sheet material, but when attaching other adhesive tapes and peeled off on rolling up end face, confirms viscous The attachment of foreign body is also had 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 having foreign body.

(2) ring-type sheet material installation

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

○：Ring-type sheet material can be simply installed.When being attached at volume end face, do not attach with can there is no fold.

△：Ring-type sheet material is attached, is installed on support or the aspect of core requires time for.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 requires time for.When stripping is not intended to portion The ring-type sheet material that attached on position and when attaching again, ring-type sheet material is stretched deformation or rupture, and makes to be attached at volume end face and become Obtain difficult.

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

After content production volume as described in the making ＞ of above-mentioned ＜ photoresist duplexer volume, broken seal.Unpacking Afterwards, in the same manner as also when installing, whether end face is installed on to ring-type sheet material and observes, 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, has from the stripping of 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 volume as described in the making ＞ of above-mentioned ＜ photoresist duplexer volume, broken seal, with wearing The handss having resin-made glove peel off ring-type sheet material.Mark grade is carried out as follows to operability when peeling off.

○：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 ＜ photoresist duplexer volume Lipid layer stack.Remove foreign body from the end face of whole volumes, randomly make four position attachments of total of volume end face different from this is 14 Thing.Afterwards, whole volumes is installed and peels off with ring-type sheet material, calculates the foreign body being attached to volume end face.

[table 1]

[table 2]

B-1	Methacrylic acid 25 mass %, methyl methacrylate 50 mass %, terpolymer (weight average molecular weight 50000, the acid of styrene 25 mass % Equivalent 344)
		B-2	Methacrylic acid 25 mass %, methyl methacrylate 65 mass %, the terpolymer (weight average molecular weight of butyl acrylate 10 mass % 70000th, acid equivalent 344)
B-3	Methacrylic acid 25 mass %, methyl methacrylate 65 mass %, the terpolymer (weight average molecular weight of butyl acrylate 10 mass % 120000th, acid equivalent 344)
		M-1	Trimethylolpropane triacrylate
M-2	Hexamethylene diisocyanate and the carbamate compound of five trimethylene glycol monomethacrylates
		M-3	Three epoxide ethyl trimethylolpropane triacrylate
M-4	Distinguish two (methyl of the poly alkylene glycol of the expoxy propane of the average Unit 2 of addition and the oxirane of average Unit 6 at the two ends of bisphenol-A Acrylic acid) ester
		M-5	Distinguish two (methacrylic acid) ester of the Polyethylene Glycol of the oxirane of each average Unit 2 of addition at the two ends of bisphenol-A
M-6	Two (methacrylic acid) ester in 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 being obtained by the oxirane of average Unit 9
M-8	Distinguish two (methacrylic acid) ester of the Polyethylene Glycol of the oxirane of each average Unit 5 of addition at the two ends of bisphenol-A
		I-1	2- (Chloro-O-Phenyl) -4,5- diphenyl-imidazole dimer
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 polyoxyethylene of average 18 moles of oxirane [two (1- phenethyl) phenyl ether]
P-4	Polyoxyethylene sorbitan trioleate (Japanese emulsifying agent Co., Ltd. manufactures, Newcol 3-85)
		X-1	(N, N- dibutylamino) carboxyl benzotriazole
X-2	Double [3- (the 3- the tert-butyl group) -5- methyl -4- hydroxy phenyl] propionic ester of triethylene glycol
		X-3	Nitrosophenylhydroxylamine aluminium salt
X-4	2- di-n-butyl amino -4,6- disulfide group-s-triazine
		X-5	3- glycidoxy-propyltrimethoxy silane

[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, make photoresist duplexer volume in the same manner as photoresist duplexer volume 1, as photoresist stacking Body volume 2～6.When rolling up, using photoresist, the evaluation that 2～6 carry out (1)～(5), obtain and using photo-sensitive resin stack Roll up same result 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 external diameter 176mm beyond, with photoresist duplexer volume 1 in the same manner as make photoresist stacking Body is rolled up, and rolls up 7～10 as photoresist duplexer.The external diameter of the photoresist duplexer of wound into rolls is 176mm.When rolling up, using photoresist, the evaluation that 7～10 carry out (1)～(5), obtain rolling up 1 with using photo-sensitive resin stack When same result.

Industrial applicability

For above-mentioned photoresist duplexer volume, due to easily foreign body can be removed in unpacking, therefore in essence Useful in close equipment, the processing of electronic material, also useful as the permanent pattern in loading precision equipment, electronic material.

Description of reference numerals

1 photoresist duplexer

2 core

Volume 3 end face guard blocks (ring-type sheet material)

4 supporting layers

5 photo-sensitive resins

6 protective layers

7 flat boards

8 fixed components

9 shading sheet materials

10 photoresist duplexer volumes.

Claims

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

Wherein, described photoresist duplexer is rolled up enough to lower important document：

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

Described photoresist duplexer includes at least supporting layer and the photo-sensitive resin being laminated in this supporting layer；And

Described ring-type sheet material is present in aerial mode according to its half and is arranged on the flat board protruding horizontally up, by described annular lamina Material be present in aerial partly in connect with described ring-type sheet material with flat board from the front end of the farthest described ring-type sheet material of flat board When the distance between face of tactile side is set to deflection distance H (mm), the half of described ring-type sheet material external diameter is set to R (mm), H/R is Less than 0.59.

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

3. photoresist duplexer volume according to claim 2 is it is characterised in that described shading sheet material is tubular.

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

5. according to claim 1 or 4 photoresist duplexer volume it is characterised in that

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

6. the photoresist duplexer volume according to any one of Claims 1 to 5 is it is characterised in that described end face is protected Shield part is 5gf/inch～250gf/inch with the bonding force of low-density polyethylene film.

7. the photoresist duplexer volume according to any one of claim 1～6 is it is characterised in that described volume end face The base material of guard block is dust-free paper, low dirt paper, synthetic paper or, the material fitted with resin base material of paper.

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

9. photoresist duplexer according to claim 8 volume is it is characterised in that the described alkali-soluble containing carboxyl Macromolecule is the material of styrene or derivatives thereof copolymerization.

10. photoresist duplexer volume according to claim 8 or claim 9 is it is characterised in that described addition polymerization monomer Comprise bisphenol-A system (methyl) acrylate compounds.

Photoresist duplexer volume any one of 11. according to Claim 8～10 is it is characterised in that described light gathers Close initiator and comprise six aryl bisglyoxalines or derivatives thereof.

The 12. photoresist duplexers volumes according to any one of claim 1～11 are it is characterised in that described bonding It is resin that agent compositionss comprise acrylic acid (ester).

The 13. photoresist duplexers volumes according to any one of claim 1～12 are it is characterised in that described bonding Agent compositionss contain binding agent and granule, more than 50 mass % of this granule have this adhesive composition coating thickness 80 ～120% diameter, and the content of this granule is 5 weight portions to 30 weight portions with respect to 100 parts by weight of binder.

A kind of manufacture methods of 14. photoresist duplexers volumes it is characterised in that

The photoresist duplexer of wound into rolls in core, with the end face with the photoresist duplexer winding up Contact and configure in the way of running through the extension of described core volume end face guard block, wherein, methods described meets following wanting Part,

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

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

The manufacture method of 15. photoresist duplexers according to claim 14 volumes is it is characterised in that described annular lamina The internal diameter of material is 1.001～1.1 times of the external diameter of described core, configures described ring in the way of running through the extension of described core Shape sheet material.

16. according to claims 14 or 15 photoresist duplexers volume manufacture method it is characterised in that

The manufacture method of the 17. photoresist duplexer volumes according to any one of claim 14～16, its feature exists In described ring-type sheet material is 5gf/inch～250gf/inch with the bonding force of low-density polyethylene film.

A kind of 18. packing methods of photoresist duplexer volume are it is characterised in that usage right requires any one of 14～17 Described method manufactures photoresist duplexer volume, covers described photoresist stacking by the shading sheet material of tubular further Body is rolled up.

A kind of 19. ring-type sheet materials, it is the ring-type sheet material of thin film film rolling of wound into rolls in core, wherein, described Ring-type sheet material meets following important document,

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

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

Described ring-type sheet material and the end contact of the thin film of described winding, have in the side with this end contact for the described ring-type sheet material There is adhesive composition, configured in film rolling in the way of running through the extension of described core；

20. ring-type sheet materials according to claim 19, wherein, described thin film is photoresist duplexer.

21. ring-type sheet materials according to claim 19 or 20 it is characterised in that

The 22. ring-type sheet materials according to any one of claim 19～21 are it is characterised in that it is thin with Low Density Polyethylene The bonding force of film is 5gf/inch～250gf/inch.

The 23. ring-type sheet materials according to any one of claim 19～22 are it is characterised in that the base material that it has is dustless Paper, low dirt paper, synthetic paper or, the material fitted with resin base material of paper.

The 24. ring-type sheet materials according to any one of claim 20～23 are it is characterised in that described photo-sensitive resin is Comprise the layer of photosensitive polymer combination, described photosensitive polymer combination comprises the alkali-soluble macromolecule containing carboxyl, adds Become polymerizable monomer, Photoepolymerizationinitiater initiater.

25. ring-type sheet materials according to claim 24 are it is characterised in that the described alkali-soluble macromolecule containing carboxyl is The material of styrene or derivatives thereof copolymerization.

The 26. ring-type sheet materials according to claim 24 or 25 are it is characterised in that described addition polymerization monomer comprises bis-phenol A system (methyl) acrylate compounds.

27. ring-type sheet materials according to any one of claim 24～26 are it is characterised in that described Photoepolymerizationinitiater initiater bag Containing six aryl bisglyoxalines or derivatives thereof.

28. ring-type sheet materials according to any one of claim 19～27 are it is characterised in that described adhesive compositionss bag (ester) containing acrylic acid is resin.

The 29. ring-type sheet materials according to any one of claim 19～28 are it is characterised in that described adhesive compositionss contain Have binding agent and a granule, more than 50 mass % of this granule have this adhesive composition coating thickness 80～120% Diameter, and the content of this granule is 5 weight portions to 30 weight portions with respect to 100 parts by weight of binder.

A kind of 30. film rolling, it possesses the ring-type sheet material described in being covered, claim 19～29 by shading sheet material.