WO2022138630A1 - 転写フィルム、積層体の製造方法、回路配線の製造方法 - Google Patents
転写フィルム、積層体の製造方法、回路配線の製造方法 Download PDFInfo
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- LXCJGJYAOVCKLO-UHFFFAOYSA-N n-cyclohexyl-n-hydroxynitrous amide Chemical compound O=NN(O)C1CCCCC1 LXCJGJYAOVCKLO-UHFFFAOYSA-N 0.000 description 1
- DAHPIMYBWVSMKQ-UHFFFAOYSA-N n-hydroxy-n-phenylnitrous amide Chemical compound O=NN(O)C1=CC=CC=C1 DAHPIMYBWVSMKQ-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
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- SKEQOTBKQUCUGK-UHFFFAOYSA-N o-(2-hydroxyethyl) propanethioate Chemical compound CCC(=S)OCCO SKEQOTBKQUCUGK-UHFFFAOYSA-N 0.000 description 1
- UCUPUEARJPTGKU-UHFFFAOYSA-N octadecyl 3-sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCS UCUPUEARJPTGKU-UHFFFAOYSA-N 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
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- 229920002114 octoxynol-9 Polymers 0.000 description 1
- LWNSNYBMYBWJDN-UHFFFAOYSA-N octyl 3-sulfanylpropanoate Chemical compound CCCCCCCCOC(=O)CCS LWNSNYBMYBWJDN-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 150000002916 oxazoles Chemical class 0.000 description 1
- 125000003566 oxetanyl group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 1
- 125000005506 phthalide group Chemical group 0.000 description 1
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
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- 229920002577 polybenzoxazole Polymers 0.000 description 1
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- 229920006267 polyester film Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
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- 229920005990 polystyrene resin Polymers 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- ZJLMKPKYJBQJNH-UHFFFAOYSA-N propane-1,3-dithiol Chemical compound SCCCS ZJLMKPKYJBQJNH-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 150000003219 pyrazolines Chemical class 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
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- 125000000168 pyrrolyl group Chemical group 0.000 description 1
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- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- RAPZEAPATHNIPO-UHFFFAOYSA-N risperidone Chemical compound FC1=CC=C2C(C3CCN(CC3)CCC=3C(=O)N4CCCCC4=NC=3C)=NOC2=C1 RAPZEAPATHNIPO-UHFFFAOYSA-N 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
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- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
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- 241000894007 species Species 0.000 description 1
- ACTRVOBWPAIOHC-XIXRPRMCSA-N succimer Chemical compound OC(=O)[C@@H](S)[C@@H](S)C(O)=O ACTRVOBWPAIOHC-XIXRPRMCSA-N 0.000 description 1
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- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- DGQOCLATAPFASR-UHFFFAOYSA-N tetrahydroxy-1,4-benzoquinone Chemical compound OC1=C(O)C(=O)C(O)=C(O)C1=O DGQOCLATAPFASR-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 150000004867 thiadiazoles Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
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- PJANXHGTPQOBST-VAWYXSNFSA-N trans-stilbene Chemical class C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
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- 239000013638 trimer Substances 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- LZTRCELOJRDYMQ-UHFFFAOYSA-N triphenylmethanol Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(O)C1=CC=CC=C1 LZTRCELOJRDYMQ-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- JODJRDDQVZMRIY-UHFFFAOYSA-N trityloxyboronic acid Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(OB(O)O)C1=CC=CC=C1 JODJRDDQVZMRIY-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 239000001018 xanthene dye Substances 0.000 description 1
- 150000007964 xanthones Chemical class 0.000 description 1
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- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/20—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by affixing prefabricated conductor pattern
Definitions
- the present invention relates to a method for manufacturing a transfer film and a laminate, and a method for manufacturing a circuit wiring.
- the etching resist film and various protective films are usually formed by a photolithography process using a photoresist.
- the photolithography process is a process of exposing a photoresist through a mask and then removing a portion soluble in a developer by development.
- the photoresist is a photoresist (negative type photoresist) that is cured by exposure
- the curing reaction proceeds in the mask opening, while the curing reaction is suppressed in the unexposed portion shielded by the mask. Therefore, the exposed portion and the unexposed portion have different solubility in the developing solution, and only the unexposed portion having high solubility in the developing solution is removed during the developing process.
- a negative photosensitive composition layer is arranged on an arbitrary substrate using a transfer film, and a mask is applied to the negative photosensitive composition layer.
- a method of developing after exposure through a film is widely used.
- a step of producing a first dry film having a photosensitive resin layer on a temporary support, an ultraviolet absorber is contained on a temporary support different from the temporary support. Includes a step of producing a second dry film having an ultraviolet absorbing layer, and a step of bonding the photosensitive resin layer of the first dry film and the ultraviolet absorbing layer of the second dry film.
- the ultraviolet absorbing layer is arranged on the side opposite to the temporary support side of the negative photosensitive composition layer.
- a transfer film in which the ultraviolet absorbing layer contains an ultraviolet absorber and a polymer having a ClogP value smaller than 2.1.
- the ultraviolet absorbing layer is arranged on the side opposite to the temporary support side of the negative photosensitive composition layer.
- the composition layer further contains an intermediate layer.
- the transfer film according to any one of [1] to [9], wherein the intermediate layer is arranged between the negative photosensitive composition layer and the temporary support.
- the transfer film according to [10], wherein the intermediate layer contains a water-soluble resin.
- the intermediate layer is one or more compounds selected from the group consisting of water-soluble cellulose derivatives, polyethers, polyhydric alcohols, alkylene oxide adducts of polyhydric alcohols, phenol derivatives, and amide compounds.
- the transfer film according to [11]. [13] The surface of the transfer film according to any one of [1] to [12] opposite to the temporary support is brought into contact with a substrate having a conductive layer, and the substrate, the conductive layer, and the composition are brought into contact with each other.
- the surface of the transfer film according to any one of [1] to [12] opposite to the temporary support is brought into contact with a substrate having a conductive layer, and the substrate, the conductive layer, and the composition are brought into contact with each other.
- the present invention it is possible to provide a transfer film capable of forming a pattern in which the tailing shape is suppressed. Further, according to the present invention, it is possible to provide a method for manufacturing a laminate and a method for manufacturing a circuit wiring using the transfer film.
- the numerical range represented by using “-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
- the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical range described in stages. ..
- the upper limit value or the lower limit value described in a certain numerical range may be replaced with the value shown in the examples.
- process is included in this term not only as an independent process but also as long as the intended purpose of the process is achieved even if it cannot be clearly distinguished from other processes. ..
- transparent means that the average transmittance of visible light having a wavelength of 400 to 700 nm is 80% or more, and is preferably 90% or more.
- the average transmittance of visible light is a value measured by using a spectrophotometer, and can be measured by, for example, a spectrophotometer U-3310 manufactured by Hitachi, Ltd.
- the weight average molecular weight (Mw) and the number average molecular weight (Mn) are TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (all trade names manufactured by Toso Co., Ltd.) as columns. ), THF (tetrahydrofuran) as the eluent, polystyrene as the standard material, and polystyrene as the standard material measured by a gel permeation chromatography (GPC) analyzer.
- GPC gel permeation chromatography
- the molecular weight of a compound having a molecular weight distribution is the weight average molecular weight (Mw).
- the ratio of the constituent units of the polymer is the mass ratio.
- the content of the metal element is a value measured by using an inductively coupled plasma (ICP) spectroscopic analyzer.
- the refractive index is a value measured using an ellipsometer at a wavelength of 550 nm.
- the hue is a value measured using a color difference meter (CR-221, manufactured by Minolta Co., Ltd.).
- (meth) acrylic is a concept that includes both acrylic and methacrylic
- (meth) acryloxy group is a concept that includes both an acryloxy group and a metaacryloxy group.
- alkali-soluble means that the solubility of sodium carbonate in 100 g of a 1% by mass aqueous solution at 22 ° C. is 0.1 g or more.
- water-soluble means that the solubility in 100 g of water having a liquid temperature of 22 ° C. and a pH of 7.0 is 0.1 g or more. Therefore, for example, the water-soluble resin is intended to be a resin satisfying the above-mentioned solubility conditions.
- the "solid content" of a composition means a component forming a composition layer formed by using the composition, and when the composition contains a solvent (organic solvent, water, etc.), the solvent is used. Means all ingredients except. Further, if the component forms a composition layer, the liquid component is also regarded as a solid content.
- the transfer film of the first aspect of the present invention is A transfer film having a temporary support and a composition layer including a negative photosensitive composition layer and an ultraviolet absorbing layer arranged on the temporary support.
- a polymer in which the ultraviolet absorbing layer is arranged on the side opposite to the temporary support side of the negative photosensitive composition layer, and the ultraviolet absorber and the ClogP value are smaller than 2.1 (hereinafter, also referred to as “specific polymer”). include.
- the features of the transfer film of the first aspect of the present invention are that the ultraviolet absorbing layer is arranged on the side opposite to the temporary support of the negative photosensitive composition layer, and that the ultraviolet absorbing layer is relatively hydrophilic.
- the point that it contains a specific polymer having a high property (a polymer having a ClogP value smaller than 2.1) can be mentioned.
- the presumed mechanism of action of the transfer film of the first aspect of the present invention is as follows.
- the transfer film of the first aspect has an ultraviolet absorbing layer on the side opposite to the temporary support of the negative photosensitive composition layer, and due to this structure, on the surface opposite to the temporary support.
- the transfer film of the first aspect is less likely to generate interference fringes due to the incident light from the exposure light source and the reflected light on the metal substrate in the negative photosensitive composition layer at the time of exposure, and in addition, is reflected. Light is unlikely to diffuse to an area (unexposed area) originally shielded by a mask.
- the ultraviolet absorbing layer of the transfer film of the first aspect contains a specific polymer having relatively high hydrophilicity, so that the residue of the ultraviolet absorbing layer during development (preferably alkaline development). It is also clarified that the shape of the formed pattern is unlikely to be a hemming shape due to this.
- the negative photosensitive composition layer is usually composed of a hydrophobic component in many cases.
- the ultraviolet absorbing layer in the transfer film is in the form of containing a specific polymer having a relatively high hydrophobicity
- the negative photosensitive composition layer and the ultraviolet absorbing layer are formed by a coating method. It has been found that when laminated, excessive interlayer mixing between the negative photosensitive composition layer and the ultraviolet absorbing layer may occur, and this also tends to cause the pattern shape to become a tailing shape. Further, even if the negative photosensitive composition layer and the ultraviolet absorbing layer are laminated by the transfer method, if the ultraviolet absorbing layer contains a specific polymer having a relatively high hydrophobicity, the negative photosensitive due to the interlayer movement of the components of both layers.
- the shape of the pattern formed by the transfer film is more excellent (in other words, the tailing shape is more suppressed) and / or the resolution of the transfer film is more excellent. Is better.
- the transfer film of the first aspect has a temporary support and a composition layer including a negative photosensitive composition layer and an ultraviolet absorbing layer arranged on the temporary support.
- the composition layer includes at least a negative photosensitive composition layer and an ultraviolet absorbing layer, but may include other layers other than the negative photosensitive composition layer and the ultraviolet absorbing agent. Examples of the other layers include an intermediate layer, a thermoplastic resin layer, a refractive index adjusting layer, and the like. Further, the transfer film of the first aspect may have a structure having a protective film on the composition layer.
- the negative photosensitive composition layer is a colored resin layer.
- the transfer film of the present invention may be used as a transfer film for a protective film or as a transfer film for an etching resist, as will be described later.
- the term "for protective film” means a protective film provided to cover the electrodes and / or the wiring for the purpose of protecting the electrodes and / or the wiring, and a protective film for insulating the electrodes (specifically). Is intended as a protective film for insulating electrodes such as bridge wiring).
- the composition of the transfer film is preferably, for example, the above-mentioned configurations (1) to (3).
- the composition of the transfer film is preferably, for example, the above-mentioned configurations (3) to (6).
- the maximum width of the waviness of the transfer film of the first aspect is preferably 300 ⁇ m or less, more preferably 200 ⁇ m or less, still more preferably 60 ⁇ m or less.
- the lower limit of the maximum width of the swell is 0 ⁇ m or more, preferably 0.1 ⁇ m or more, and more preferably 1 ⁇ m or more.
- the maximum width of the waviness of the transfer film of the first aspect is a value measured by the following procedure. First, the transfer film of the first aspect is cut in a direction perpendicular to the main surface so as to have a size of 20 cm in length ⁇ 20 cm in width to prepare a test sample.
- the transfer film of the first aspect has a protective film
- the protective film is peeled off.
- the test sample is placed on a stage having a smooth and horizontal surface so that the surface of the temporary support faces the stage.
- the surface of the sample sample was scanned with a laser microscope (for example, VK-9700SP manufactured by Keyence Co., Ltd.) for a range of 10 cm square in the center of the test sample to obtain a three-dimensional surface image, and the obtained 3 Subtract the minimum concave height from the maximum convex height observed in the 3D surface image.
- the above operation is performed on 10 test samples, and the arithmetic mean value thereof is defined as "the maximum waviness width of the transfer film of the first aspect".
- the transfer film of the first aspect of the present invention will be described with reference to an example of a specific embodiment.
- the following transfer film of the first A embodiment can be suitably used as a transfer film for a protective film
- the following transfer film of the first B embodiment can be suitably used as a transfer film for an etching resist. It is a composition.
- the transfer film 10 shown in FIG. 1 is a composition layer including a temporary support 1, an intermediate layer (intermediate layer A) 3, a negative photosensitive composition layer 5, an ultraviolet absorbing layer 7, and a refractive index adjusting layer 9. 2 and the protective film 11 are provided in this order.
- the transfer film 10 shown in FIG. 1 has a form in which the protective film 11 is arranged, but the protective film 11 may not be arranged.
- the transfer film 10 shown in FIG. 1 has a form in which the refractive index adjusting layer 9 is arranged, but the refractive index adjusting layer 9 may not be arranged.
- transfer film each element constituting the transfer film of the first A embodiment (hereinafter abbreviated as “transfer film”) will be described.
- Temporary support The transfer film has a temporary support.
- the temporary support is a member that supports the composition layer, and is finally removed by a peeling treatment.
- the temporary support may have a single-layer structure or a multi-layer structure.
- the temporary support is preferably a film, more preferably a resin film.
- the temporary support is preferably a film that is flexible and does not undergo significant deformation, shrinkage, or elongation under pressure, or under pressure and heating.
- the film include polyethylene terephthalate film (for example, biaxially stretched polyethylene terephthalate film), polymethylmethacrylate film, cellulose triacetate film, polystyrene film, polyimide film, and polycarbonate film.
- a polyethylene terephthalate film is preferable as the temporary support.
- the film used as the temporary support is free from deformation such as wrinkles and scratches.
- the temporary support is preferably highly transparent from the viewpoint that the pattern can be exposed through the temporary support, and the transmittance at 365 nm is preferably 60% or more, more preferably 70% or more. From the viewpoint of pattern formation during pattern exposure via the temporary support and transparency of the temporary support, it is preferable that the haze of the temporary support is small. Specifically, the haze value of the temporary support is preferably 2% or less, more preferably 0.5% or less, still more preferably 0.1% or less. From the viewpoint of pattern formation during pattern exposure via the temporary support and transparency of the temporary support, it is preferable that the number of fine particles, foreign substances, and defects contained in the temporary support is small.
- the number of fine particles, foreign matter, and defects having a diameter of 1 ⁇ m or more in the temporary support is preferably 50 pieces / 10 mm 2 or less, more preferably 10 pieces / 10 mm 2 or less, further preferably 3 pieces / 10 mm 2 or less, and 0. Pieces / 10 mm 2 are particularly preferred.
- the thickness of the temporary support is not particularly limited, but is preferably 5 to 200 ⁇ m, more preferably 5 to 150 ⁇ m, still more preferably 5 to 50 ⁇ m, and most preferably 5 to 25 ⁇ m from the viewpoint of ease of handling and versatility.
- the thickness of the temporary support can be calculated as an average value of any five points measured by cross-sectional observation with an SEM (Scanning Electron Microscope).
- the surface on the side in contact with the composition layer is surface-modified by UV irradiation, corona discharge, plasma, or the like. It may have been done.
- the exposure amount is preferably 10 to 2000 mJ / cm 2 , and more preferably 50 to 1000 mJ / cm 2 .
- the light sources include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, and light-emitting diodes that emit light in the wavelength band of 150 to 450 nm. LED) and the like. As long as the amount of light irradiation is within this range, the lamp output and illuminance are not particularly limited.
- Examples of the temporary support include a biaxially stretched polyethylene terephthalate film having a thickness of 16 ⁇ m, a biaxially stretched polyethylene terephthalate film having a thickness of 12 ⁇ m, and a biaxially stretched polyethylene terephthalate film having a thickness of 9 ⁇ m.
- Preferred forms of the temporary support include, for example, paragraphs [0017] to [0018] of JP-A-2014-085643, paragraphs [0019]-[0026] of JP-A-2016-0273363, and International Publication No. 2012 /.
- the description is given in paragraphs [0041] to [0057] of No. 081680 and paragraphs [0029] to [0040] of International Publication No. 2018/179370, and the contents of these publications are incorporated in the present specification.
- a layer containing fine particles may be provided on the surface of the temporary support from the viewpoint of imparting handleability.
- the lubricant layer may be provided on one side of the temporary support or on both sides.
- the diameter of the particles contained in the lubricant layer is preferably 0.05 to 0.8 ⁇ m.
- the film thickness of the lubricant layer is preferably 0.05 to 1.0 ⁇ m.
- Examples of commercially available temporary supports include Lumirror 16KS40, Lumirror 16FB40 (above, manufactured by Toray Industries, Inc.), Cosmoshine A4100, Cosmoshine A4300, and Cosmoshine A8300 (above, manufactured by Toyobo Co., Ltd.).
- the transfer film has a negative photosensitive composition layer.
- a pattern can be formed on the transferred body by transferring the negative photosensitive composition layer onto the transferred body and then exposing and developing the layer.
- the exposed portion becomes a cured film due to exposure, and the solubility in a developing solution is lowered.
- the components that can be contained in the negative photosensitive composition layer will be described.
- the negative photosensitive composition layer contains a binder polymer.
- the binder polymer include (meth) acrylic resin, styrene resin, epoxy resin, amide resin, amide epoxy resin, alkyd resin, phenol resin, ester resin, urethane resin, and the reaction of epoxy resin with (meth) acrylic acid.
- examples thereof include the obtained epoxy acrylate resin and the acid-modified epoxy acrylate resin obtained by reacting the epoxy acrylate resin with the acid anhydride.
- the binder polymer is a (meth) acrylic resin in that it is excellent in alkali developability and film forming property.
- the (meth) acrylic resin means a resin having a structural unit derived from the (meth) acrylic compound.
- the content of the structural unit derived from the (meth) acrylic compound is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, based on all the structural units of the (meth) acrylic resin. ..
- the (meth) acrylic resin may be composed of only a structural unit derived from the (meth) acrylic compound, or may have a structural unit derived from a polymerizable monomer other than the (meth) acrylic compound. .. That is, the upper limit of the content of the structural unit derived from the (meth) acrylic compound is 100% by mass or less with respect to all the structural units of the (meth) acrylic resin.
- Examples of the (meth) acrylic compound include (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylamide, and (meth) acrylonitrile.
- Examples of the (meth) acrylic acid ester include (meth) acrylic acid alkyl ester, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, (meth) acrylic acid diethylaminoethyl ester, and (meth) acrylic acid ester.
- Acrylic acid glycidyl ester (meth) acrylic acid benzyl ester, 2,2,2-trifluoroethyl (meth) acrylate, and 2,2,3,3-tetrafluoropropyl (meth) acrylate.
- Meta) Acrylic acid alkyl esters are preferred.
- the (meth) acrylamide include acrylamide such as diacetone acrylamide.
- the alkyl group of the (meth) acrylic acid alkyl ester may be linear or may have a branch. Specific examples include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, ( Heptyl acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, and (meth) acrylate.
- Examples thereof include (meth) acrylic acid alkyl esters having an alkyl group having 1 to 12 carbon atoms such as dodecyl.
- the alkyl group of the (meth) acrylic acid alkyl ester may be cyclic.
- the cyclic alkyl group may be monocyclic or polycyclic. Specific examples include cyclohexyl (meth) acrylate and the like.
- As the (meth) acrylic acid ester a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms is preferable, and methyl (meth) acrylate or ethyl (meth) acrylate is more preferable.
- the (meth) acrylic resin may have a structural unit other than the structural unit derived from the (meth) acrylic compound.
- the polymerizable monomer forming the structural unit is not particularly limited as long as it is a compound other than the (meth) acrylic compound that can be copolymerized with the (meth) acrylic compound, and is, for example, styrene, vinyltoluene, and ⁇ . -Styrene compounds such as methylstyrene which may have a substituent on the ⁇ -position or aromatic ring, vinyl alcohol esters such as acrylonitrile and vinyl-n-butyl ether, cinnamic acid, cinnamic acid anhydride, monomethyl maleate, maleic acid.
- Examples thereof include monoethyl and maleic acid monoesters such as monoisopropyl maleate, fumaric acid, cinnamic acid, ⁇ -cyanocinnamic acid, itaconic acid, and crotonic acid. These polymerizable monomers may be used alone or in combination of two or more.
- the (meth) acrylic resin preferably has a structural unit having an acid group from the viewpoint of improving the alkali developability.
- the acid group include a carboxy group, a sulfo group, a phosphoric acid group, and a phosphonic acid group.
- the (meth) acrylic resin more preferably has a structural unit having a carboxy group, and further preferably has a structural unit derived from the above-mentioned (meth) acrylic acid.
- the content of the structural unit having an acid group (preferably the structural unit derived from (meth) acrylic acid) in the (meth) acrylic resin is excellent in developability, and is based on the total mass of the (meth) acrylic resin. 10% by mass or more is preferable, and 20% by mass or more is more preferable.
- the upper limit is not particularly limited, but is preferably 50% by mass or less, more preferably 40% by mass or less, in terms of excellent alkali resistance.
- the (meth) acrylic resin has a structural unit derived from the above-mentioned (meth) acrylic acid alkyl ester.
- the content of the structural unit derived from the (meth) acrylic acid alkyl ester in the (meth) acrylic resin is preferably 50 to 90% by mass, preferably 60 to 90% by mass, based on all the structural units of the (meth) acrylic resin. More preferably, 65 to 90% by mass is further preferable, and 70 to 90% by mass is particularly preferable.
- the (meth) acrylic resin a resin having both a structural unit derived from (meth) acrylic acid and a structural unit derived from (meth) acrylic acid alkyl ester is preferable, and the structural unit derived from (meth) acrylic acid and the structural unit derived from (meth) acrylic acid are preferable.
- a resin composed only of structural units derived from the (meth) acrylic acid alkyl ester is more preferable.
- an acrylic resin having a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate, and a structural unit derived from ethyl acrylate is also preferable.
- the (meth) acrylic resin may have at least one selected from the group consisting of a structural unit derived from methacrylic acid and a structural unit derived from methacrylic acid alkyl ester in that the effect of the present invention is more excellent. It is preferable to have both a structural unit derived from methacrylic acid and a structural unit derived from an alkyl methacrylate ester.
- the total content of the structural units derived from methacrylic acid and the structural units derived from methacrylic acid alkyl ester in the (meth) acrylic resin is higher than that of all the structural units of the (meth) acrylic resin in that the effect of the present invention is more excellent.
- 40% by mass or more is preferable, and 60% by mass or more is more preferable.
- the upper limit is not particularly limited, and may be 100% by mass or less, preferably 80% by mass or less.
- the (meth) acrylic resin is at least one selected from the group consisting of a structural unit derived from methacrylic acid and a structural unit derived from methacrylic acid alkyl ester in that the effect of the present invention is more excellent, and acrylic acid. It is also preferable to have at least one selected from the group consisting of the structural unit derived from the acrylic acid alkyl ester and the structural unit derived from the acrylic acid alkyl ester. In that the effect of the present invention is more excellent, the total content of the structural unit derived from methacrylic acid and the structural unit derived from methacrylic acid alkyl ester is the structural unit derived from acrylic acid and the structural unit derived from acrylic acid alkyl ester.
- the mass ratio is preferably 60/40 to 80/20 with respect to the total content of the ester.
- the (meth) acrylic resin preferably has an ester group at the terminal in that the negative photosensitive composition layer after transfer is excellent in developability.
- the terminal portion of the (meth) acrylic resin is composed of a site derived from the polymerization initiator used in the synthesis.
- a (meth) acrylic resin having an ester group at the terminal can be synthesized by using a polymerization initiator that generates a radical having an ester group.
- the binder polymer is preferably, for example, a binder polymer having an acid value of 60 mgKOH / g or more from the viewpoint of developability.
- the binder polymer is, for example, a resin having a carboxy group having an acid value of 60 mgKOH / g or more (so-called carboxy group-containing resin) from the viewpoint that it is easily crosslinked with the crosslinked component by heating to form a strong film. More preferably, it is a (meth) acrylic resin having a carboxy group having an acid value of 60 mgKOH / g or more (so-called carboxy group-containing (meth) acrylic resin).
- the binder polymer is a resin having a carboxy group
- the three-dimensional crosslink density can be increased by adding a heat-crosslinkable compound such as a blocked isocyanate compound and heat-crosslinking.
- a heat-crosslinkable compound such as a blocked isocyanate compound and heat-crosslinking.
- the carboxy group of the resin having a carboxy group is dehydrated and made hydrophobic, the wet heat resistance can be improved.
- the carboxy group-containing (meth) acrylic resin having an acid value of 60 mgKOH / g or more is not particularly limited as long as the above acid value conditions are satisfied, and can be appropriately selected from known (meth) acrylic resins.
- carboxy group-containing acrylic resins having an acid value of 60 mgKOH / g or more paragraphs [0033] to [0052] of JP-A-2010-237589.
- a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more can be preferably used.
- the binder polymer is a styrene-acrylic copolymer.
- the styrene-acrylic copolymer refers to a resin having a structural unit derived from a styrene compound and a structural unit derived from a (meth) acrylic compound, and is a structural unit derived from the styrene compound.
- the total content of the structural units derived from the (meth) acrylic compound is preferably 30% by mass or more, more preferably 50% by mass or more, based on all the structural units of the copolymer.
- the lower limit of the content of the structural unit derived from the styrene compound is preferably 1% by mass or more, more preferably 5% by mass or more, and 20% by mass or more, based on all the structural units of the copolymer. More preferred.
- the upper limit is preferably 80% by mass or less, more preferably 60% by mass or less, and further preferably 50% by mass or less.
- the lower limit of the content of the structural unit derived from the (meth) acrylic compound is preferably 1% by mass or more, more preferably 5% by mass or more, based on 10% by mass, based on all the structural units of the copolymer. By mass or more is more preferable, and 20% by mass or more is particularly preferable.
- the upper limit is preferably 95% by mass or less, more preferably 60% by mass or less, and further preferably 30% by mass or less.
- the structural unit derived from the (meth) acrylic compound it is preferable to have both a structural unit derived from (meth) acrylic acid and a structural unit derived from the (meth) acrylic acid alkyl ester.
- the binder polymer preferably has an aromatic ring structure, and more preferably has a structural unit having an aromatic ring structure, in that the effect of the present invention is more excellent.
- the monomers forming the structural unit having an aromatic ring structure include a monomer having an aralkyl group, styrene, and a polymerizable styrene derivative (for example, methyl styrene, vinyl toluene, tert-butoxy styrene, acetoxy styrene, 4-vinyl benzoic acid). , Styrene dimer, styrene trimmer, etc.). Of these, a monomer having an aralkyl group or styrene is preferable.
- aralkyl group examples include a substituted or unsubstituted phenylalkyl group (excluding a benzyl group), a substituted or unsubstituted benzyl group and the like, and a substituted or unsubstituted benzyl group is preferable.
- Examples of the monomer having a phenylalkyl group include phenylethyl (meth) acrylate and the like.
- Examples of the monomer having a benzyl group include (meth) acrylate having a benzyl group, for example, benzyl (meth) acrylate, and chlorobenzyl (meth) acrylate; a vinyl monomer having a benzyl group, for example, vinylbenzyl chloride, and the like. Examples include vinylbenzyl alcohol. Of these, benzyl (meth) acrylate is preferable.
- the binder polymer has a structural unit (constituent unit derived from styrene) represented by the following formula (S) in that the effect of the present invention is more excellent.
- the content of the structural unit having an aromatic ring structure is 5 to 90 mass by mass with respect to all the structural units of the binder polymer in that the effect of the present invention is more excellent. % Is preferable, 10 to 70% by mass is more preferable, and 20 to 60% by mass is further preferable. Further, the content of the structural unit having an aromatic ring structure in the binder polymer is preferably 5 to 70 mol%, preferably 10 to 60 mol% with respect to all the structural units of the binder polymer in that the effect of the present invention is more excellent. Is more preferable, and 20 to 60 mol% is further preferable.
- the content of the structural unit represented by the above formula (S) in the binder polymer is preferably 5 to 70 mol% with respect to all the structural units of the binder polymer in that the effect of the present invention is more excellent. From 20 to 60 mol% is more preferable, 20 to 60 mol% is further preferable, and 20 to 50 mol% is particularly preferable.
- the above “constituent unit” shall be synonymous with the "monomer unit”. Further, in the present specification, the above-mentioned "monomer unit” may be modified after polymerization by a polymer reaction or the like. The same applies to the following.
- the binder polymer preferably has an aliphatic hydrocarbon ring structure in that the effect of the present invention is more excellent. That is, the binder polymer preferably has a structural unit having an aliphatic hydrocarbon ring structure.
- the aliphatic hydrocarbon ring structure may be monocyclic or polycyclic. Above all, it is more preferable that the binder polymer has a ring structure in which two or more aliphatic hydrocarbon rings are fused.
- Examples of the ring constituting the aliphatic hydrocarbon ring structure in the structural unit having the aliphatic hydrocarbon ring structure include a tricyclodecane ring, a cyclohexane ring, a cyclopentane ring, a norbornane ring, and an isoborone ring.
- a ring in which two or more aliphatic hydrocarbon rings are condensed is preferable because the effect of the present invention is more excellent, and a tetrahydrodicyclopentadiene ring (tricyclo [5.2.1.0 2,6 ] decane) is preferable. Ring) is more preferred.
- the monomer forming a structural unit having an aliphatic hydrocarbon ring structure examples include dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate.
- the binder polymer preferably has a structural unit represented by the following formula (Cy) in that the effect of the present invention is more excellent, and the structural unit represented by the above formula (S) and the following formula (S). It is more preferable to have a structural unit represented by Cy).
- RM represents a hydrogen atom or a methyl group
- RCy represents a monovalent group having an aliphatic hydrocarbon ring structure.
- the RM in the formula ( Cy ) is preferably a methyl group.
- the RCy in the formula ( Cy ) is preferably a monovalent group having an aliphatic hydrocarbon ring structure having 5 to 20 carbon atoms, and a fat having 6 to 16 carbon atoms, because the effect of the present invention is more excellent. It is more preferably a monovalent group having a group hydrocarbon ring structure, and even more preferably a monovalent group having an aliphatic hydrocarbon ring structure having 8 to 14 carbon atoms.
- the aliphatic hydrocarbon ring structure in RCy of the formula ( Cy ) has a cyclopentane ring structure, a cyclohexane ring structure, a tetrahydrodicyclopentadiene ring structure, a norbornane ring structure, or a norbornane ring structure, in that the effect of the present invention is more excellent. It is preferably an isoborone ring structure, more preferably a cyclohexane ring structure or a tetrahydrodicyclopentadiene ring structure, and even more preferably a tetrahydrodicyclopentadiene ring structure.
- the aliphatic hydrocarbon ring structure in RCy of the formula ( Cy ) is preferably a ring structure in which two or more aliphatic hydrocarbon rings are fused, in that the effect of the present invention is more excellent. It is more preferable that the ring is a condensed ring of ⁇ 4 aliphatic hydrocarbon rings.
- the binder polymer may have one type of structural unit having an aliphatic hydrocarbon ring structure alone, or may have two or more types.
- the content of the structural unit having an aliphatic hydrocarbon ring structure is higher than that of all the structural units of the binder polymer in that the effect of the present invention is more excellent. 5 to 90% by mass is preferable, 10 to 80% by mass is more preferable, and 20 to 70% by mass is further preferable.
- the content of the structural unit having an aliphatic hydrocarbon ring structure in the binder polymer is preferably 5 to 70 mol% with respect to all the structural units of the binder polymer in that the effect of the present invention is more excellent, and 10 to 10 to 60 mol% is more preferable, and 20 to 50 mol% is further preferable.
- the content of the structural unit represented by the above formula (Cy) in the binder polymer is preferably 5 to 70 mol% with respect to all the structural units of the binder polymer in that the effect of the present invention is more excellent. -60 mol% is more preferred, and 20-50 mol% is even more preferred.
- the total content of the structural unit having an aromatic ring structure and the structural unit having an aliphatic hydrocarbon ring structure is the present.
- 10 to 90% by mass is preferable, 20 to 80% by mass is more preferable, and 40 to 75% by mass is further preferable, based on all the structural units of the binder polymer.
- the total content of the structural unit having an aromatic ring structure and the structural unit having an aliphatic hydrocarbon ring structure in the binder polymer is 10 with respect to all the structural units of the binder polymer in that the effect of the present invention is more excellent.
- the total content of the structural unit represented by the above formula (S) and the structural unit represented by the above formula (Cy) in the binder polymer is the total structural unit of the binder polymer in that the effect of the present invention is more excellent.
- 10 to 80 mol% is preferable, 20 to 70 mol% is more preferable, and 40 to 60 mol% is further preferable.
- the molar amount nS of the structural unit represented by the above formula (S) and the molar amount nCy of the structural unit represented by the above formula (Cy) in the binder polymer are the following formulas in that the effect of the present invention is more excellent. It is preferable to satisfy the relationship shown in (SCy), more preferably to satisfy the following formula (SCy-1), and further preferably to satisfy the following formula (SCy-2).
- the binder polymer preferably has a structural unit having an acid group in that the effect of the present invention is more excellent.
- the acid group include a carboxy group, a sulfo group, a phosphonic acid group, and a phosphoric acid group, and a carboxy group is preferable.
- the structural unit having the acid group the structural unit derived from (meth) acrylic acid shown below is preferable, and the structural unit derived from methacrylic acid is more preferable.
- the binder polymer may have one type of structural unit having an acid group alone or two or more types.
- the content of the structural unit having an acid group is 5 to 50% by mass with respect to all the structural units of the binder polymer in that the effect of the present invention is more excellent. It is preferable, 5 to 40% by mass is more preferable, and 10 to 30% by mass is further preferable.
- the content of the constituent unit having an acid group in the binder polymer is preferably 5 to 70 mol%, preferably 10 to 50 mol%, based on all the constituent units of the binder polymer, in that the effect of the present invention is more excellent. More preferably, 20-40 mol% is even more preferable.
- the content of the structural unit derived from (meth) acrylic acid in the binder polymer is preferably 5 to 70 mol% with respect to all the structural units of the binder polymer in that the effect of the present invention is more excellent, and 10 to 50. More preferably, mol%, more preferably 20-40 mol%.
- the binder polymer preferably has a reactive group, and more preferably has a structural unit having a reactive group, in that the effect of the present invention is more excellent.
- a reactive group a radically polymerizable group is preferable, and an ethylenically unsaturated group is more preferable.
- the binder polymer preferably has a structural unit having an ethylenically unsaturated group in the side chain.
- the "main chain” represents a relatively longest binding chain among the molecules of the polymer compound constituting the resin, and the "side chain” refers to an atomic group branched from the main chain. show.
- an ethylenically unsaturated group an allyl group or a (meth) acryloxy group is more preferable. Examples of structural units having a reactive group include, but are not limited to, those shown below.
- the binder polymer may have one type of structural unit having a reactive group alone or two or more types.
- the lower limit of the content of the structural unit having a reactive group is that the effect of the present invention is more excellent with respect to all the structural units of the binder polymer.
- 5% by mass or more is preferable, 10% by mass or more is more preferable, 20% by mass or more is further preferable, 35% by mass or more is particularly preferable, and 40% by mass or more is most preferable.
- the upper limit is preferably 70% by mass or less, more preferably 60% by mass or less, and further preferably 50% by mass or less.
- the lower limit of the content of the structural unit having a reactive group in the binder polymer is preferably 5 mol% or more, preferably 10 mol%, based on all the structural units of the binder polymer, in that the effect of the present invention is more excellent.
- the above is more preferable, 20 mol% or more is further preferable, 35 mol% or more is particularly preferable, and 40 mol% or more is most preferable.
- the upper limit thereof is preferably 70 mol% or less, more preferably 60 mol% or less, still more preferably 50 mol% or less.
- a functional group such as a hydroxy group, a carboxy group, a primary amino group, a secondary amino group, an acetoacetyl group, and a sulfo group, an epoxy compound, and a blocked isocyanate are used.
- a functional group such as a hydroxy group, a carboxy group, a primary amino group, a secondary amino group, an acetoacetyl group, and a sulfo group, an epoxy compound, and a blocked isocyanate.
- examples thereof include a method of reacting a compound such as a compound, an isocyanate compound, a vinyl sulfone compound, an aldehyde compound, a methylol compound, and a carboxylic acid anhydride.
- a preferred example of a means for introducing a reactive group into a binder polymer is that a polymer having a carboxy group is synthesized by a polymerization reaction and then glycidyl (meth) acrylate is added to a part of the carboxy group of the obtained polymer by the polymer reaction.
- a means for introducing a (meth) acryloxy group into a polymer by reacting with the polymer By this means, a binder polymer having a (meth) acryloxy group in the side chain can be obtained.
- the polymerization reaction is preferably carried out under a temperature condition of 70 to 100 ° C., and more preferably carried out under a temperature condition of 80 to 90 ° C.
- an azo-based initiator is preferable, and for example, V-601 (trade name) or V-65 (trade name) manufactured by Wako Pure Chemical Industries, Ltd. is more preferable.
- the polymer reaction is preferably carried out under temperature conditions of 80 to 110 ° C. In the above polymer reaction, it is preferable to use a catalyst such as an ammonium salt.
- the polymers X1 to X4 shown below are preferable because the effects of the present invention are more excellent.
- the content ratios (a to d) and the weight average molecular weight Mw of each structural unit shown below can be appropriately changed depending on the intended purpose, but the following configuration is particularly effective in that the effect of the present invention is more excellent. Is preferable.
- Polymer X3 a: 30 to 65% by mass, b: 1.0 to 20% by mass, c: 5.0 to 25% by mass, d: 10 to 50% by mass.
- Polymer X4 a: 1.0 to 20% by mass, b: 20 to 60% by mass, c: 5.0 to 25% by mass, d: 10 to 50% by mass.
- the binder polymer may contain a polymer having a structural unit having a carboxylic acid anhydride structure (hereinafter, also referred to as “polymer X”).
- the carboxylic acid anhydride structure may be either a chain carboxylic acid anhydride structure or a cyclic carboxylic acid anhydride structure, but a cyclic carboxylic acid anhydride structure is preferable.
- a cyclic carboxylic acid anhydride structure As the ring having a cyclic carboxylic acid anhydride structure, a 5- to 7-membered ring is preferable, a 5-membered ring or a 6-membered ring is more preferable, and a 5-membered ring is further preferable.
- the structural unit having a carboxylic acid anhydride structure is a structural unit containing a divalent group obtained by removing two hydrogen atoms from the compound represented by the following formula P-1 in the main chain, or the following formula P-1. It is preferable that the monovalent group obtained by removing one hydrogen atom from the represented compound is a structural unit bonded directly to the main chain or via a divalent linking group.
- RA1a represents a substituent
- n1a RA1a may be the same or different
- Examples of the substituent represented by RA1a include an alkyl group.
- Z 1a an alkylene group having 2 to 4 carbon atoms is preferable, an alkylene group having 2 or 3 carbon atoms is more preferable, and an alkylene group having 2 carbon atoms is further preferable.
- n 1a represents an integer of 0 or more.
- Z 1a represents an alkylene group having 2 to 4 carbon atoms
- n 1a is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and even more preferably 0.
- a plurality of RA1a may be the same or different. Further, although a plurality of RA1a may be bonded to each other to form a ring, it is preferable that the RA1a are not bonded to each other to form a ring.
- a structural unit derived from an unsaturated carboxylic acid anhydride is preferable, a structural unit derived from an unsaturated cyclic carboxylic acid anhydride is more preferable, and an unsaturated aliphatic cyclic carboxylic acid is preferable.
- a structural unit derived from an acid anhydride is more preferable, a structural unit derived from maleic anhydride or an itaconic acid anhydride is particularly preferable, and a structural unit derived from maleic anhydride is most preferable.
- Rx represents a hydrogen atom, a methyl group, a CH 2 OH group, or CF 3 groups
- Me represents a methyl group.
- the structural unit having a carboxylic acid anhydride structure in the polymer X may be one kind alone or two or more kinds.
- the total content of the structural units having a carboxylic acid anhydride structure is preferably 0 to 60 mol%, more preferably 5 to 40 mol%, and further preferably 10 to 35 mol% with respect to all the structural units of the polymer X. preferable.
- the negative photosensitive composition layer may contain only one kind of polymer X, or may contain two or more kinds of polymer X.
- the effect of the present invention is more excellent, and the content of the polymer X is 0.1 with respect to the total mass of the negative photosensitive composition layer. It is preferably from 30% by mass, more preferably 0.2 to 20% by mass, still more preferably 0.5 to 20% by mass, still more preferably 1 to 20% by mass.
- the weight average molecular weight (Mw) of the binder polymer is preferably 5,000 or more, and more preferably 10,000 or more, in that the effect of the present invention is more excellent.
- the upper limit thereof is preferably 120,000 or less, more preferably 60,000 or less, further preferably 35,000 or less, and particularly preferably 30,000 or less.
- the acid value of the binder polymer is preferably 10 to 200 mgKOH / g, more preferably 60 to 200 mgKOH / g, further preferably 60 to 150 mgKOH / g, particularly preferably 70 to 150 mgKOH / g, and most preferably 70 to 125 mgKOH / g. ..
- the acid value of the binder polymer can be calculated from the average content of acid groups in the compound, for example, according to the method described in JIS K0070: 1992.
- the dispersity of the binder polymer is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, further preferably 1.0 to 4.0, and 1.0 to 3 from the viewpoint of developability. .0 is particularly preferred.
- the negative photosensitive composition layer may contain only one kind of binder polymer, or may contain two or more kinds of binder polymers.
- the content of the binder polymer is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and 25 to 20 to the total mass of the negative photosensitive composition layer in that the effect of the present invention is more excellent. 70% by mass is more preferable, and 25 to 60% by mass is particularly preferable.
- the negative photosensitive composition layer may contain a polymerizable compound.
- the polymerizable compound is a compound having a polymerizable group. Examples of the polymerizable group include a radically polymerizable group and a cationically polymerizable group, and a radically polymerizable group is preferable.
- the polymerizable compound preferably contains a radically polymerizable compound having an ethylenically unsaturated group (hereinafter, also simply referred to as “ethylenically unsaturated compound”).
- ethylenically unsaturated compound a (meth) acryloxy group is preferable.
- the ethylenically unsaturated compound in the present specification is a compound other than the binder polymer, and preferably has a molecular weight of less than 5,000.
- the number of ethylenically unsaturated groups in the ethylenically unsaturated compound is not particularly limited, but one or more is preferable, and two or more are more preferable.
- the upper limit is not particularly limited, but is, for example, 20 or less.
- a compound represented by the following formula (M) (simply referred to as “Compound M”) can be mentioned.
- Q2 - R1 - Q1 formula (M) Q 1 and Q 2 each independently represent a (meth) acryloyloxy group, and R 1 represents a divalent linking group having a chain structure.
- Q 1 and Q 2 in the formula (M) have the same group as Q 1 and Q 2 from the viewpoint of ease of synthesis. Further, Q 1 and Q 2 in the formula (M) are preferably acryloyloxy groups from the viewpoint of reactivity.
- R 1 in the formula (M) an alkylene group, an alkyleneoxyalkylene group (-L 1 -OL 1- ), or a polyalkylene oxyalkylene group (-(L)" is used because the effect of the present invention is more excellent.
- a hydrocarbon group having 2 to 20 carbon atoms or a polyalkyleneoxyalkylene group is more preferable, an alkylene group having 4 to 20 carbon atoms is further preferable, and an alkylene group having 6 to 20 carbon atoms is more preferable. Eighteen linear alkylene groups are particularly preferred.
- the hydrocarbon group may have a chain structure at least partially, and the portion other than the chain structure is not particularly limited, and is, for example, a branched chain, cyclic, or having 1 to 1 to carbon atoms.
- the alkylene group is more preferable, and the linear alkylene group is further preferable.
- the above L 1 independently represents an alkylene group, and an ethylene group, a propylene group, or a butylene group is preferable, and an ethylene group or a 1,2-propylene group is more preferable.
- p represents an integer of 2 or more, and is preferably an integer of 2 to 10.
- the number of atoms of the shortest connecting chain for connecting Q1 and Q2 in compound M is preferably 3 to 50, more preferably 4 to 40, in that the effect of the present invention is more excellent. 6 to 20 are more preferable, and 8 to 12 are particularly preferable.
- "the number of atoms in the shortest connecting chain connecting between Q1 and Q2" means the atoms in R1 connected to Q1 to the atoms in R1 connected to Q2 . The shortest number of atoms.
- the compound M examples include 1,3-butanediol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and 1,6-hexanediol di (meth) acrylate.
- the ester monomer can also be used as a mixture.
- 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, and 1,10-decanediol di (meth) are more excellent in the effect of the present invention. It is preferably at least one compound selected from the group consisting of acrylates and neopentyl glycol di (meth) acrylates, preferably 1,6-hexanediol di (meth) acrylates and 1,9-nonanediol di (1) -nonanediol di (meth) acrylates.
- it is at least one compound selected from the group consisting of a meta) acrylate and a 1,10-decanediol di (meth) acrylate, and the 1,9-nonanediol di (meth) acrylate, and More preferably, it is at least one compound selected from the group consisting of 1,10-decanediol di (meth) acrylate.
- a bifunctional or higher functional ethylenically unsaturated compound can be mentioned.
- the term "bifunctional or higher functional ethylenically unsaturated compound” means a compound having two or more ethylenically unsaturated groups in one molecule.
- a (meth) acryloyl group is preferable.
- a (meth) acrylate compound is preferable.
- the bifunctional ethylenically unsaturated compound is not particularly limited and may be appropriately selected from known compounds.
- Examples of the bifunctional ethylenically unsaturated compound other than the compound M include tricyclodecanedimethanol di (meth) acrylate and 1,4-cyclohexanediol di (meth) acrylate.
- NK ester A-DCP tricyclodecanedimethanol diacrylate
- NK ester A-DCP tricyclodecanedimenanol dimethacrylate
- NK ester DCP manufactured by Shin-Nakamura Chemical Industry Co., Ltd.
- 1,9-nonandiol diacrylate (trade name: NK ester A-NOD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
- 1,6 -Hexanediol diacrylate (trade name: NK ester A-HD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
- the trifunctional or higher functional ethylenically unsaturated compound is not particularly limited and may be appropriately selected from known compounds.
- Examples of the trifunctional or higher functional ethylenically unsaturated compound include dipentaerythritol (tri / tetra / penta / hexa) (meth) acrylate, pentaerythritol (tri / tetra) (meth) acrylate, and trimethylolpropane tri (meth) acrylate.
- Examples thereof include ditrimethylolpropane tetra (meth) acrylate, isocyanuric acid (meth) acrylate, and (meth) acrylate compound having a glycerintri (meth) acrylate skeleton.
- (tri / tetra / penta / hexa) (meth) acrylate is a concept including tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, and hexa (meth) acrylate.
- (tri / tetra) (meth) acrylate” is a concept that includes tri (meth) acrylate and tetra (meth) acrylate. Examples of commercially available trifunctional ethylenically unsaturated compounds include trimethylolpropane triacrylate (“A-TMPT” manufactured by Shin-Nakamura Chemical Industry Co., Ltd.).
- Examples of commercially available products of the tetrafunctional ethylenically unsaturated compound include pentaerythritol tetraacrylate (“A-TMMT” manufactured by Shin-Nakamura Chemical Industry Co., Ltd.).
- Examples of commercially available products of 5- or hexafunctional ethylenically unsaturated compounds include dipentaerythritol polyacrylate (“A-DPH” manufactured by Shin-Nakamura Chemical Industry Co., Ltd.).
- Examples of the polymerizable compound include caprolactone-modified compounds of (meth) acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Industry Co., Ltd., etc.), (Meta). ) An alkylene oxide-modified compound of an acrylate compound (KAYARAD (registered trademark) RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E, A-9300 manufactured by Shin-Nakamura Chemical Industry Co., Ltd., EBECRYL (registered trademark) manufactured by Daicel Ornex Co., Ltd. ) 135 etc.) and ethoxylated glycerin triacrylate (NK ester A-GLY-9E etc. manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) and the like.
- KAYARAD registered trademark
- RP-1040 manufactured by Nippon Kayaku Co., Ltd.,
- examples of the polymerizable compound include urethane (meth) acrylate compounds.
- examples of the urethane (meth) acrylate include urethane di (meth) acrylate, and examples thereof include propylene oxide-modified urethane di (meth) acrylate, and ethylene oxide and propylene oxide-modified urethane di (meth) acrylate.
- a urethane (meth) acrylate having trifunctionality or higher can also be mentioned.
- the lower limit of the number of functional groups 6-functionality or more is more preferable, and 8-functionality or more is further preferable.
- the upper limit of the number of functional groups is preferably 20 or less.
- trifunctional or higher functional urethane (meth) acrylates examples include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and U-15HA (manufactured by Shin Nakamura Chemical Industry Co., Ltd.). ), UA-1100H (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), AH-600 (trade name) manufactured by Kyoeisha Chemical Co., Ltd., and UA-306H, UA-306T, UA-306I, UA-510H. , And UX-5000 (both manufactured by Nippon Kayaku Co., Ltd.) and the like.
- One of the preferred embodiments of the polymerizable compound is an ethylenically unsaturated compound having an acid group.
- the acid group include a phosphoric acid group, a sulfo group, and a carboxy group, and among them, a carboxy group is preferable.
- a carboxy group is preferable.
- the ethylenically unsaturated compound having an acid group a 3- to 4-functional ethylenically unsaturated compound having an acid group [pentaerythritol tri and a tetraacrylate (PETA) skeleton introduced with a carboxy group (acid value: 80 to 80).
- the ethylenically unsaturated compound having an acid group at least one selected from the group consisting of a bifunctional or higher functional ethylenically unsaturated compound having a carboxy group and a carboxylic acid anhydride thereof is preferable.
- the ethylenically unsaturated compound having an acid group is at least one selected from the group consisting of a bifunctional or higher functional ethylenically unsaturated compound having a carboxy group and a carboxylic acid anhydride thereof, the developability and film strength are further improved. It will increase.
- the bifunctional or higher functional unsaturated compound having a carboxy group is not particularly limited and can be appropriately selected from known compounds.
- Examples of the bifunctional or higher functional unsaturated compound having a carboxy group include Aronix (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), Aronix (registered trademark) M-520 (manufactured by Toagosei Co., Ltd.), and the like.
- Aronix (registered trademark) M-510 manufactured by Toagosei Co., Ltd. can be mentioned.
- Examples of the polymerizable compound include a compound obtained by reacting a polyhydric alcohol with an ⁇ , ⁇ -unsaturated carboxylic acid, a compound obtained by reacting a glycidyl group-containing compound with an ⁇ , ⁇ -unsaturated carboxylic acid, and an ester.
- Urethane monomers such as (meth) acrylate compounds with bonds, ⁇ -chloro- ⁇ -hydroxypropyl- ⁇ '-(meth) acryloyloxyethyl-o-phthalate, ⁇ -hydroxyethyl- ⁇ '-(meth) acryloyloxyethyl Examples thereof include phthalic acid compounds such as -o-phthalate and ⁇ -hydroxypropyl- ⁇ '-(meth) acryloyloxyethyl-o-phthalate, and (meth) acrylic acid alkyl esters. These may be used alone or in combination of two or more.
- Examples of the compound obtained by reacting a polyvalent alcohol with an ⁇ , ⁇ -unsaturated carboxylic acid include 2,2-bis (4-((meth) acrylamide polyethoxy) phenyl) propane and 2,2-bis.
- Bisphenol A-based (meth) acrylate compounds such as (4-((meth) acrylamide polypropoxy) phenyl) propane and 2,2-bis (4-((meth) acrylamide polyethoxypolypropoxy) phenyl) propane , Polyethylene glycol di (meth) acrylate having 2 to 14 ethylene oxide groups, polypropylene glycol di (meth) acrylate having 2 to 14 propylene oxide groups, and 2 to 14 ethylene oxide groups.
- an ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure is preferable, and a tetramethylolmethanetri (meth) acrylate, a tetramethylolmethanetetra (meth) acrylate, a trimethylolpropanetri (meth) acrylate, or a trimethylolpropane tri (meth) acrylate is preferable.
- Di (trimethylolpropane) tetraacrylate is more preferred.
- Examples of the polymerizable compound include caprolactone-modified compounds of ethylenically unsaturated compounds (for example, KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin Nakamura Chemical Industry Co., Ltd., etc.).
- An alkylene oxide-modified compound of an ethylenically unsaturated compound for example, KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E, A-9300 manufactured by Shin Nakamura Chemical Industry Co., Ltd., EBECRYL manufactured by Daicel Ornex Co., Ltd. (registered trademark). ) 135 etc.), ethoxylated glycerin triacrylate (A-GLY-9E etc. manufactured by Shin Nakamura Chemical Industry Co., Ltd.) and the like.
- the polymerizable compound ethylenically unsaturated compound
- those containing an ester bond are preferable in that the negative photosensitive composition layer after transfer is excellent in developability.
- the ethylenically unsaturated compound containing an ester bond is not particularly limited as long as it contains an ester bond in the molecule, but is ethylenic having a tetramethylolmethane structure or a trimethylolpropane structure in that the effect of the present invention is excellent.
- An unsaturated compound is preferable, and tetramethylolmethanetri (meth) acrylate, trimethylolmethanetetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, or di (trimethylolpropane) tetraacrylate is more preferable.
- the ethylenically unsaturated compound includes an ethylenically unsaturated compound having an aliphatic group having 6 to 20 carbon atoms and the above-mentioned ethylenically unsaturated compound having a tetramethylol methane structure or a trimethylol propane structure. It preferably contains a saturated compound.
- the ethylenically unsaturated compound having an aliphatic structure having 6 or more carbon atoms include 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, and tricyclodecanedimethanoldi. Examples include (meth) acrylate.
- One of the preferred embodiments of the polymerizable compound is a polymerizable compound having an aliphatic hydrocarbon ring structure (preferably a bifunctional ethylenically unsaturated compound).
- a polymerizable compound having a ring structure in which two or more aliphatic hydrocarbon rings are condensed preferably a structure selected from the group consisting of a tricyclodecane structure and a tricyclodecene structure
- a bifunctional ethylenically unsaturated compound having a ring structure in which two or more aliphatic hydrocarbon rings are condensed is more preferable, and tricyclodecanedimethanol di (meth) acrylate is further preferable.
- a cyclopentane structure, a cyclohexane structure, a tricyclodecane structure, a tricyclodecene structure, a norbornane structure, or an isoborone structure is preferable from the viewpoint that the effect of the present invention is more excellent.
- the molecular weight of the polymerizable compound is preferably 200 to 3,000, more preferably 250 to 2,600, further preferably 280 to 2,200, and particularly preferably 300 to 2,200.
- the negative photosensitive composition layer preferably contains a bifunctional or higher functional ethylenically unsaturated compound and preferably contains a trifunctional or higher functional ethylenically unsaturated compound. It is more preferable to contain a tetrafunctional or higher functional ethylenically unsaturated compound in that the effect of the present invention is more excellent.
- the negative photosensitive composition layer has a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure and an aliphatic hydrocarbon ring. It preferably contains a binder polymer having a structural unit.
- the negative photosensitive composition layer contains a compound represented by the formula (M) and an ethylenically unsaturated compound having an acid group. , And more preferably 1,9-nonanediol diacrylate, tricyclodecanedimethanol diacrylate, and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group. And, it is more preferable to contain tricyclodecanedimethanol diacrylate and a succinic acid-modified form of dipentaerythritol pentaacrylate.
- the negative photosensitive composition layer includes a compound represented by the formula (M) and an ethylenically unsaturated compound having an acid group, which will be described later. It preferably contains a thermally crosslinkable compound, and more preferably contains a compound represented by the formula (M), an ethylenically unsaturated compound having an acid group, and a blocked isocyanate compound described later.
- the negative photosensitive composition layer is a bifunctional ethylenically unsaturated compound (preferably) from the viewpoint of suppressing development residue and rust prevention.
- the mass ratio of the content of the bifunctional ethylenically unsaturated compound and the trifunctional or higher functional ethylenically unsaturated compound is preferably 10:90 to 90:10, more preferably 30:70 to 70:30.
- the content of the bifunctional ethylenically unsaturated compound is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, based on the total amount of all the ethylenically unsaturated compounds.
- the bifunctional ethylenically unsaturated compound in the negative photosensitive composition layer is preferably 10 to 60% by mass, more preferably 15 to 40% by mass.
- the negative photosensitive composition layer is bifunctional ethylenically having compound M and an aliphatic hydrocarbon ring structure from the viewpoint of rust resistance. It preferably contains an unsaturated compound. Further, as one of the preferred embodiments of the negative photosensitive composition layer, the negative photosensitive composition layer contains the compound M and an acid from the viewpoints of substrate adhesion, development residue inhibitory property, and rust resistance.
- an ethylenically unsaturated compound having a group it is preferable to contain an ethylenically unsaturated compound having a group, and more preferably to contain a compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, and an ethylenically unsaturated compound having an acid group.
- Compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, a trifunctional or higher functional ethylenically unsaturated compound, and an ethylenically unsaturated compound having an acid group are more preferably contained.
- the negative type photosensitive composition layer contains a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, a trifunctional or higher functional ethylenically unsaturated compound, an ethylenically unsaturated compound having an acid group, and a urethane (meth) acrylate compound.
- the negative type photosensitive composition layer has a negative type photosensitive composition layer, and the negative type photosensitive composition layer has substrate adhesion, development residue suppressing property, and rust resistance.
- 1,9-nonanediol diacrylate and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group 1,9-nonandiol diacrylate, tricyclodecanedimethanol diacrylate, and , Polyfunctional ethylenically unsaturated compounds having a carboxylic acid group, preferably 1,9-nonanediol diacrylate, tricyclodecanedimethanol diacrylate, dipentaerythritol hexaacrylate, and ethylene having a carboxylic acid group.
- a sex unsaturated compound it is more preferable to contain a sex unsaturated compound, and it is particularly preferable to contain a 1,9-nonanediol diacrylate, a tricyclodecanedimethanol diacrylate, an ethylenically unsaturated compound having a carboxylic acid group, and a urethane acrylate compound. ..
- the ratio of the content of the polymerizable compound having a molecular weight of 300 or less among the polymerizable compounds contained in the negative photosensitive composition layer is the negative photosensitive composition layer.
- the content of all the polymerizable compounds contained in the sex composition layer 30% by mass or less is preferable, 25% by mass or less is more preferable, and 20% by mass or less is further preferable.
- the negative photosensitive composition layer may contain a monofunctional ethylenically unsaturated compound as the ethylenically unsaturated compound.
- the content of the bifunctional or higher functional ethylenically unsaturated compound in the ethylenically unsaturated compound is 60 to 100% by mass with respect to the total content of all the ethylenically unsaturated compounds contained in the negative photosensitive composition layer. Is preferable, 80 to 100% by mass is more preferable, and 90 to 100% by mass is further preferable.
- the polymerizable compound (particularly, the ethylenically unsaturated compound) may be used alone or in combination of two or more.
- the lower limit of the content of the ethylenically unsaturated compound in the negative photosensitive composition layer is preferably 1% by mass or more, more preferably 5% by mass or more, based on the total mass of the negative photosensitive composition layer. , 20% by mass or more is more preferable, 35% by mass or more is particularly preferable, and 40% by mass or more is most preferable.
- the upper limit is not particularly limited, but is preferably 70% by mass or less, more preferably 60% by mass or less, and further preferably 55% by mass or less.
- the negative photosensitive composition layer may contain a polymerization initiator.
- a photopolymerization initiator is preferable, and a known photopolymerization initiator can be used.
- the photopolymerization initiator include a photopolymerization initiator having an oxime ester structure (hereinafter, also referred to as “oxym-based photopolymerization initiator”) and a photopolymerization initiator having an ⁇ -aminoalkylphenone structure (hereinafter, “ ⁇ -”.
- Photopolymerization initiator hereinafter, also referred to as “acylphosphine oxide-based photopolymerization initiator”
- photopolymerization initiator having an N-phenylglycine structure hereinafter, “N-phenylglycine-based photopolymerization initiator”. Also referred to as "agent").
- the photopolymerization initiator is selected from the group consisting of an oxime-based photopolymerization initiator, an ⁇ -aminoalkylphenone-based photopolymerization initiator, an ⁇ -hydroxyalkylphenone-based polymerization initiator, and an N-phenylglycine-based photopolymerization initiator. It is preferable to contain at least one selected from the group consisting of an oxime-based photopolymerization initiator, an ⁇ -aminoalkylphenone-based photopolymerization initiator, and an N-phenylglycine-based photopolymerization initiator. Is more preferable.
- photopolymerization initiator is described in, for example, paragraphs [0031] to [0042] of JP-A-2011-095716 and paragraphs [0064]-[0081] of JP-A-2015-014783.
- a polymerization initiator may be used.
- photopolymerization initiators include 1- [4- (phenylthio) phenyl] -1,2-octanedione-2- (O-benzoyloxime) [trade name: IRGACURE (registered trademark) OXE-01, BASF.
- the photopolymerization initiator may be used alone or in combination of two or more. When two or more kinds are used in combination, an oxime-based photopolymerization initiator and at least one selected from an ⁇ -aminoalkylphenone-based photopolymerization initiator and an ⁇ -hydroxyalkylphenone-based polymerization initiator may be used. preferable.
- the content of the photopolymerization initiator is preferably 0.1% by mass or more, preferably 0.5% by mass or more, based on the total mass of the negative photosensitive composition layer. Is more preferable, and 1.0% by mass or more is further preferable.
- the upper limit thereof is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the negative photosensitive composition layer.
- the negative photosensitive composition layer may contain a heterocyclic compound.
- the heterocycle contained in the heterocyclic compound may be either a monocyclic or polycyclic complex.
- Examples of the hetero atom contained in the heterocyclic compound include a nitrogen atom, an oxygen atom, and a sulfur atom.
- the heterocyclic compound preferably has at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom, and more preferably has a nitrogen atom.
- heterocyclic compound examples include a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazole compound, a triazine compound, a rhonin compound, a thiazole compound, a benzothiazole compound, a benzoimidazole compound, a benzoxazole compound, and a pyrimidine compound.
- the heterocyclic compound is at least one selected from the group consisting of a triazole compound, a benzotriazole compound, a tetrazole compound, a thiaziazole compound, a triazine compound, a rhonin compound, a thiazole compound, a benzimidazole compound, and a benzoxazole compound.
- Species compounds are preferred, and at least one compound selected from the group consisting of triazole compounds, benzotriazole compounds, tetrazole compounds, thiathazole compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, and benzoxazole compounds is more preferred.
- heterocyclic compound Preferred specific examples of the heterocyclic compound are shown below.
- examples of the triazole compound and the benzotriazole compound include the following compounds.
- Examples of the tetrazole compound include the following compounds.
- thiadiazole compounds include the following compounds.
- Examples of the triazine compound include the following compounds.
- Examples of the loadonin compound include the following compounds.
- Examples of the thiazole compound include the following compounds.
- benzothiazole compound examples include the following compounds.
- Examples of the benzimidazole compound include the following compounds.
- benzoxazole compound examples include the following compounds.
- the heterocyclic compound may be used alone or in combination of two or more.
- the content of the heterocyclic compound is preferably 0.01 to 20.0% by mass, preferably 0, based on the total mass of the negative photosensitive composition layer. .10 to 10.0% by mass is more preferable, 0.30 to 8.0% by mass is further preferable, and 0.50 to 5.0% by mass is particularly preferable.
- the negative photosensitive composition layer may contain an aliphatic thiol compound.
- an en-thiol reaction can occur between the aliphatic thiol compound and the ethylenically unsaturated compound. As a result, the curing shrinkage of the formed film is suppressed and the stress is relieved.
- aliphatic thiol compound a monofunctional aliphatic thiol compound or a polyfunctional aliphatic thiol compound (that is, a bifunctional or higher functional aliphatic thiol compound) is preferable.
- aliphatic thiol compound a polyfunctional aliphatic thiol compound is preferable from the viewpoint of adhesion of the formed pattern (particularly, adhesion after exposure).
- polyfunctional aliphatic thiol compound means an aliphatic compound having two or more thiol groups (also referred to as “mercapto groups”) in the molecule.
- the polyfunctional aliphatic thiol compound a low molecular weight compound having a molecular weight of 100 or more is preferable. Specifically, the molecular weight of the polyfunctional aliphatic thiol compound is more preferably 100 to 1,500, and even more preferably 150 to 1,000.
- the number of functional groups of the polyfunctional aliphatic thiol compound for example, 2 to 10 functionalities are preferable, 2 to 8 functionalities are more preferable, and 2 to 6 functionalities are further preferable, from the viewpoint of adhesion of the formed pattern.
- polyfunctional aliphatic thiol compound examples include trimethylolpropanetris (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), and the like.
- the polyfunctional aliphatic thiol compounds include trimethylolpropane tris (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, and 1,3,5-. At least one compound selected from the group consisting of tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione is preferred.
- Examples of the monofunctional aliphatic thiol compound include 1-octanethiol, 1-dodecanethiol, ⁇ -mercaptopropionic acid, methyl-3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, and n-. Examples thereof include octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, and stearyl-3-mercaptopropionate.
- the negative photosensitive composition layer may contain one type of aliphatic thiol compound alone, or may contain two or more types of aliphatic thiol compounds.
- the content of the aliphatic thiol compound is preferably 5% by mass or more, preferably 5 to 50% by mass, based on the total mass of the negative photosensitive composition layer. % Is more preferable, 5 to 30% by mass is further preferable, and 8 to 20% by mass is particularly preferable.
- the negative photosensitive composition layer preferably contains a heat-crosslinkable compound from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film.
- the heat-crosslinkable compound having an ethylenically unsaturated group which will be described later, is not treated as an ethylenically unsaturated compound, but is treated as a heat-crosslinkable compound.
- the heat-crosslinkable compound include an epoxy compound, an oxetane compound, a methylol compound, and a blocked isocyanate compound. Among them, the blocked isocyanate compound is preferable from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film.
- the blocked isocyanate compound reacts with a hydroxy group and a carboxy group, for example, when at least one of the binder polymer and the radically polymerizable compound having an ethylenically unsaturated group has at least one of the hydroxy group and the carboxy group, The hydrophilicity of the formed film tends to decrease, and the function as a protective film tends to be strengthened.
- the blocked isocyanate compound refers to "a compound having a structure in which the isocyanate group of isocyanate is protected (so-called masked) with a blocking agent".
- the dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100 to 160 ° C, more preferably 130 to 150 ° C.
- the dissociation temperature of the blocked isocyanate means "the temperature of the heat absorption peak associated with the deprotection reaction of the blocked isocyanate when measured by DSC (Differential scanning calorimetry) analysis using a differential scanning calorimeter".
- DSC Different scanning calorimeter
- a differential scanning calorimeter model: DSC6200 manufactured by Seiko Instruments, Inc. can be preferably used.
- the differential scanning calorimeter is not limited to this.
- the blocking agent having a dissociation temperature of 100 to 160 ° C. for example, at least one selected from oxime compounds is preferable from the viewpoint of storage stability.
- the blocked isocyanate compound preferably has an isocyanurate structure, for example, from the viewpoint of improving the brittleness of the membrane and improving the adhesion to the transferred body.
- the blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by subjecting hexamethylene diisocyanate to isocyanurate to protect it.
- a compound having an oxime structure using an oxime compound as a blocking agent is easier to set the dissociation temperature in a preferable range than a compound having no oxime structure, and has less development residue. It is preferable because it is easy to do.
- the blocked isocyanate compound may have a polymerizable group.
- the polymerizable group is not particularly limited, and a known polymerizable group can be used, and a radically polymerizable group is preferable.
- the polymerizable group include a (meth) acryloxy group, a (meth) acrylamide group, an ethylenically unsaturated group such as a styryl group, and a group having an epoxy group such as a glycidyl group.
- an ethylenically unsaturated group is preferable
- a (meth) acryloxy group is more preferable
- an acryloxy group is further preferable.
- blocked isocyanate compound a commercially available product can be used.
- examples of commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP (all manufactured by Showa Denko KK), and blocks.
- Examples thereof include the Duranate series of molds (for example, Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Co., Ltd.).
- the heat-crosslinkable compound may be used alone or in combination of two or more.
- the content of the heat-crosslinkable compound is preferably 1 to 50% by mass, preferably 5 to 30% by mass, based on the total mass of the negative-type photosensitive composition layer. More preferably by mass.
- the negative photosensitive composition layer may contain a surfactant.
- the surfactant include the surfactants described in paragraph [0017] of Japanese Patent No. 4502784 and paragraphs [0060] to [0071] of JP-A-2009-237362.
- a nonionic surfactant As the surfactant, a nonionic surfactant, a fluorine-based surfactant, or a silicone-based surfactant is preferable.
- fluorine-based surfactants include, for example, Megafuck F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144. , F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F -558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP.
- the fluorine-based surfactant has a molecular structure having a functional group containing a fluorine atom, and when heat is applied, the portion of the functional group containing the fluorine atom is cut off and the fluorine atom volatilizes. Can also be suitably used.
- fluorine-based surfactants include the Megafuck DS series manufactured by DIC Corporation (The Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), for example, Megafuck. DS-21 can be mentioned.
- the fluorine-based surfactant it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound. Further, as the fluorine-based surfactant, a block polymer can also be used.
- the fluorine-based surfactant has a structural unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups).
- a fluorine-containing polymer compound containing a structural unit derived from a (meth) acrylate compound can also be preferably used.
- a fluorine-based surfactant a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used. Examples thereof include Megafuck RS-101, RS-102, RS-718K, RS-72-K (all manufactured by DIC Corporation) and the like.
- a compound having a linear perfluoroalkyl group having 7 or more carbon atoms such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS), may be used. It is preferably a surfactant derived from an alternative material.
- Nonionic surfactants include glycerol, trimethylolpropane, and trimethylolethane, and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, and polyoxyethylene stearyl ether.
- silicone-based surfactant examples include a linear polymer composed of a siloxane bond and a modified siloxane polymer having an organic group introduced into a side chain or a terminal.
- surfactants include EXP. S-309-2, EXP. S-315, EXP. S-503-2, EXP. S-505-2 (all manufactured by DIC Co., Ltd.), DOWSIL 8032 ADDITIVE, Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torre Silicone SH21PA, Torre Silicone SH28PA, Torre Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400 ( Above, manufactured by Toray Dow Corning Co., Ltd.), X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF- 642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002, KP-101, KP-103, KP-104, KP-105, KP-
- BYK331, BYK333, BYK345, BYK347, BYK348, BYK349, BYK370, BYK377, BYK378, BYK323 (all manufactured by Big Chemie) and the like.
- the surfactant may be used alone or in combination of two or more.
- the content of the surfactant is preferably 0.01 to 3.0% by mass, preferably 0, based on the total mass of the negative photosensitive composition layer. 0.01 to 1.0% by mass is more preferable, and 0.05 to 0.80% by mass is further preferable.
- the negative photosensitive composition layer may contain a polymerization inhibitor.
- the polymerization inhibitor means a compound having a function of delaying or prohibiting a polymerization reaction.
- a known compound used as a polymerization inhibitor can be used.
- polymerization inhibitor examples include phenothiazines, bis- (1-dimethylbenzyl) phenothiazine, and phenothiazine compounds such as 3,7-dioctylphenothiazine; bis [3- (3-tert-butyl-4-hydroxy-5-.
- Methylphenyl) propionic acid [ethylenebis (oxyethylene)] 2,4-bis [(laurylthio) methyl] -o-cresol, 1,3,5-tris (3,5-di-t-butyl-4-) Hydroxybenzyl), 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis- (n-octylthio) -6- (4-hydroxy-3) , 5-Di-t-butylanilino) -1,3,5-triazine, and hindered phenolic compounds such as pentaerythritol tetrakis 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate; 4 -Nitroso compounds such as nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine, and N-nitrosophenylhydroxylamine or salts thereof
- At least one selected from the group consisting of a phenothiazine compound, a nitroso compound or a salt thereof, and a hindered phenol compound is preferable as the polymerization inhibitor because the effect of the present invention is more excellent, and phenothiazine and bis [ 3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid], [ethylenebis (oxyethylene)] 2,4-bis [(laurylthio) methyl] -o-cresol, 1,3 5-Tris (3,5-di-t-butyl-4-hydroxybenzyl), p-methoxyphenol, and N-nitrosophenylhydroxylamine aluminum salts are more preferred.
- the polymerization inhibitor may be used alone or in combination of two or more.
- the content of the polymerization inhibitor is preferably 0.001 to 5.0% by mass with respect to the total mass of the negative photosensitive composition layer. 01 to 3.0% by mass is more preferable, and 0.02 to 2.0% by mass is further preferable.
- the content of the polymerization inhibitor is preferably 0.005 to 5.0% by mass, more preferably 0.01 to 3.0% by mass, and 0.01 to 1.0 with respect to the total mass of the polymerizable compound. Mass% is more preferred.
- the negative photosensitive composition layer may contain a hydrogen donating compound.
- the hydrogen donating compound has an action of further improving the sensitivity of the photopolymerization initiator to active light rays and suppressing the inhibition of the polymerization of the polymerizable compound by oxygen.
- Examples of the hydrogen donating compound include amines and amino acid compounds.
- Examples of amines include M.I. R. "Journal of Polymer Society" by Sander et al., Vol. 10, pp. 3173 (1972), JP-A-44-020189, JP-A-51-081022, JP-A-52-134692, JP-A-59-138205. Examples thereof include the compounds described in Japanese Patent Application Laid-Open No. 60-0843305, Japanese Patent Application Laid-Open No. 62-018537, Japanese Patent Application Laid-Open No. 64-033104, and Research Disclosure No. 33825.
- examples thereof include dimethylaniline and p-methylthiodimethylaniline.
- at least one selected from the group consisting of 4,4'-bis (diethylamino) benzophenone and tris (4-dimethylaminophenyl) methane is used as amines because the effect of the present invention is more excellent. preferable.
- amino acid compound examples include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine.
- N-phenylglycine is preferable as the amino acid compound because the effect of the present invention is more excellent.
- Examples of the hydrogen donor compound include an organometallic compound (tributyltin acetate, etc.) described in Japanese Patent Publication No. 48-042965, a hydrogen donor described in Japanese Patent Publication No. 55-0344414, and JP-A-6. Sulfur compounds (Tritian and the like) described in JP-A-308727 can also be mentioned.
- organometallic compound tributyltin acetate, etc.
- Sulfur compounds Tritian and the like
- the hydrogen donating compound may be used alone or in combination of two or more.
- the content of the hydrogen donating compound is such that the curing rate is improved by the balance between the polymerization growth rate and the chain transfer. 0.01 to 10.0% by mass is preferable, 0.01 to 8.0% by mass is more preferable, and 0.03 to 5.0% by mass is further preferable, based on the total mass of the above.
- the negative photosensitive composition layer may contain a predetermined amount of impurities.
- impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogen and ions thereof.
- halide ions, sodium ions, and potassium ions are easily mixed as impurities, so the following content is preferable.
- the content of impurities in the negative photosensitive composition layer is preferably 80 ppm or less, more preferably 10 ppm or less, still more preferably 2 ppm or less on a mass basis.
- the content of impurities in the negative photosensitive composition layer can be 1 ppb or more or 0.1 ppm or more on a mass basis.
- a material having a low impurity content is selected as a raw material for the negative photosensitive composition layer, and contamination of the negative photosensitive composition layer is prevented during formation of the negative photosensitive composition layer. , Cleaning and removal.
- the amount of impurities can be kept within the above range.
- the impurities can be quantified by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.
- ICP Inductively Coupled Plasma
- the content of these compounds in the negative photosensitive composition layer is preferably 100 ppm or less, more preferably 20 ppm or less, still more preferably 4 ppm or less on a mass basis.
- the lower limit is based on mass and can be 10 ppb or more, and can be 100 ppb or more.
- the content of these compounds can be suppressed in the same manner as the above-mentioned metal impurities. Further, it can be quantified by a known measurement method.
- the water content in the negative photosensitive composition layer is preferably 0.01 to 1.0% by mass, more preferably 0.05 to 0.5% by mass, from the viewpoint of improving reliability and laminating property.
- the negative photosensitive composition layer may contain residual monomers of each structural unit of the binder polymer (eg, alkali-soluble resin) described above.
- the content of the residual monomer is preferably 5,000 mass ppm or less, more preferably 2,000 mass ppm or less, and 500 mass ppm or less with respect to the total mass of the binder polymer from the viewpoint of patterning property and reliability. Is more preferable.
- the lower limit is not particularly limited, but 1 mass ppm or more is preferable, and 10 mass ppm or more is more preferable.
- the residual monomer of each structural unit of the binder polymer is preferably 3,000 mass ppm or less, preferably 600 mass ppm or less, based on the total mass of the negative photosensitive composition layer from the viewpoint of patterning property and reliability. More preferably, 100 mass ppm or less is further preferable.
- the lower limit is not particularly limited, but is preferably 0.1 mass ppm or more, and more preferably 1 mass ppm or more.
- the amount of residual monomer of the monomer when synthesizing the binder polymer by the polymer reaction is also preferably in the above range.
- the content of glycidyl acrylate is preferably in the above range.
- the amount of the residual monomer can be measured by a known method such as liquid chromatography and gas chromatography.
- the negative photosensitive composition layer may contain a component other than the above-mentioned components (hereinafter, also referred to as “other component”).
- Other components include, for example, colorants, antioxidants, and particles (eg, metal oxide particles).
- other additives described in paragraphs [0058] to [0071] of JP-A-2000-310706 can also be mentioned.
- metal oxide particles are preferable.
- the metal in the metal oxide particles also includes metalloids such as B, Si, Ge, As, Sb, and Te.
- the average primary particle size of the particles is, for example, preferably 1 to 200 nm, more preferably 3 to 80 nm, from the viewpoint of transparency of the cured film.
- the average primary particle size of the particles is calculated by measuring the particle size of 200 arbitrary particles using an electron microscope and arithmetically averaging the measurement results. When the shape of the particle is not spherical, the longest side is the particle diameter.
- the negative photosensitive composition layer may contain only one kind of particles having different metal species and sizes, or two or more kinds.
- the negative photosensitive composition layer does not contain particles, or when the negative photosensitive composition layer contains particles, the content of the particles is relative to the total mass of the negative photosensitive composition layer. , 0% by mass and 35% by mass or less, and more preferably 0% by mass and 10% by mass or less with respect to the total mass of the negative photosensitive composition layer, which does not contain particles or contains particles.
- Particles are not contained, or the content of particles is more preferably more than 0% by mass and 5% by mass or less with respect to the total mass of the negative photosensitive composition layer, and the particles are not contained or the particles are contained.
- the amount is more preferably more than 0% by mass and 1% by mass or less with respect to the total mass of the negative photosensitive composition layer, and it is particularly preferable that the amount does not contain particles.
- the negative photosensitive composition layer may contain a trace amount of a colorant (pigment, dye, etc.), but for example, from the viewpoint of transparency, it is preferable that the layer does not contain a colorant substantially.
- the content of the colorant is preferably less than 1% by mass, more preferably less than 0.1% by mass, based on the total mass of the negative photosensitive composition layer. preferable.
- the antioxidant examples include 1-phenyl-3-pyrazolidone (also known as phenidone), 1-phenyl-4,4-dimethyl-3-pyrazolidone, and 1-phenyl-4-methyl-4-hydroxymethyl-.
- 3-Pyrazoridones such as 3-pyrazolidone; polyhydroxybenzenes such as hydroquinone, catechol, pyrogallol, methylhydroquinone, and chlorhydroquinone; paramethylaminophenol, paraaminophenol, parahydroxyphenylglycine, and paraphenylenediamine. Be done.
- 3-pyrazolidones are preferable, and 1-phenyl-3-pyrazolidone is more preferable as the antioxidant because the effect of the present invention is more excellent.
- the content of the antioxidant is preferably 0.001% by mass or more, preferably 0.005% by mass, based on the total mass of the negative photosensitive composition layer. % Or more is more preferable, and 0.01% by mass or more is further preferable.
- the upper limit is not particularly limited, but is preferably 1% by mass or less.
- the thickness of the negative photosensitive composition layer is not particularly limited, but is often 30 ⁇ m or less, and is preferably 20 ⁇ m or less, more preferably 15 ⁇ m or less, still more preferably 10 ⁇ m or less, in that the effect of the present invention is more excellent. 9.0 ⁇ m or less is particularly preferable. As the lower limit, 0.60 ⁇ m or more is preferable, and 1.5 ⁇ m or more is more preferable, because the strength of the film obtained by curing the negative photosensitive composition layer is excellent.
- the thickness of the negative photosensitive composition layer can be calculated as, for example, an average value of any five points measured by cross-sectional observation with a scanning electron microscope (SEM).
- the refractive index of the negative photosensitive composition layer is preferably 1.47 to 1.56, more preferably 1.49 to 1.54.
- the negative photosensitive composition layer is preferably achromatic. Specifically, the total reflection (incident angle 8 °, light source: D-65 (2 ° field)) has an L * value of 10 to 90 in the CIE1976 (L *, a *, b *) color space.
- the a * value is preferably ⁇ 1.0 to 1.0
- the b * value is preferably ⁇ 1.0 to 1.0.
- the pattern (cured film of the negative photosensitive composition layer) obtained by curing the negative photosensitive composition layer is preferably achromatic.
- the total reflection (incident angle 8 °, light source: D-65 (2 ° field)) has a pattern L * value of 10 to 90 in the CIE1976 (L *, a *, b *) color space.
- the a * value of the pattern is preferably ⁇ 1.0 to 1.0
- the b * value of the pattern is preferably ⁇ 1.0 to 1.0.
- the moisture permeability of the pattern (cured film of the negative photosensitive composition layer) obtained by curing the negative photosensitive composition layer at a film thickness of 40 ⁇ m is 500 g / m 2/24 hr or less from the viewpoint of rust prevention. It is preferably 300 g / m 2/24 hr or less, and even more preferably 100 g / m 2/24 hr or less.
- the moisture permeability is determined by exposing the negative photosensitive composition layer with an i-line at an exposure amount of 300 mJ / cm 2 and then post-baking at 145 ° C. for 30 minutes to obtain a negative photosensitive composition layer. Is measured with a cured film.
- the dissolution rate of the negative photosensitive composition layer in a 1.0% aqueous solution of sodium carbonate is preferably 0.01 ⁇ m / sec or more, more preferably 0.10 ⁇ m / sec or more, and 0. 20 ⁇ m / sec or more is more preferable. From the viewpoint of the edge shape of the pattern, 5.0 ⁇ m / sec or less is preferable, 4.0 ⁇ m / sec or less is more preferable, and 3.0 ⁇ m / sec or less is further preferable. Specific preferable numerical values are, for example, 1.0 ⁇ m / sec, 0.8 ⁇ m / sec and the like.
- the dissolution rate of the negative photosensitive composition layer in a 1.0 mass% sodium carbonate aqueous solution per unit time shall be measured as follows.
- a negative-type photosensitive composition layer (within a film thickness of 1.0 to 10 ⁇ m) formed on a glass substrate from which the solvent has been sufficiently removed is subjected to a negative solution using a 1.0 mass% sodium carbonate aqueous solution at 25 ° C.
- shower development is performed until the mold photosensitive composition layer is completely melted (however, the maximum is 2 minutes). It is obtained by dividing the film thickness of the negative photosensitive composition layer by the time required for the negative photosensitive composition layer to melt completely. If it does not melt completely in 2 minutes, calculate in the same way from the amount of change in film thickness up to that point.
- a shower nozzle of 1/4 MINJJX030PP manufactured by Ikeuchi Co., Ltd. is used, and the shower pressure is 0.08 MPa. Under the above conditions, the shower flow rate per unit time is 1,800 mL / min.
- the swelling ratio of the negative photosensitive composition layer after exposure to a 1.0 mass% sodium carbonate aqueous solution is preferably 100% or less, more preferably 50% or less, and further preferably 30% or less from the viewpoint of improving pattern formation. preferable.
- the swelling rate of the negative photosensitive composition layer after exposure to a 1.0 mass% sodium carbonate aqueous solution shall be measured as follows.
- the negative photosensitive composition layer (within a film thickness of 1.0 to 10 ⁇ m) formed on the glass substrate from which the solvent has been sufficiently removed is exposed to 500 mj / cm 2 (i-line measurement) with an ultrahigh pressure mercury lamp. ..
- the glass substrate is immersed in a 1.0 mass% sodium carbonate aqueous solution at 25 ° C., and the film thickness is measured after 30 seconds. Then, the rate at which the film thickness after immersion increases with respect to the film thickness before immersion is calculated.
- Specific preferable numerical values include, for example, 13%, 25% and the like.
- the number of foreign substances having a diameter of 1.0 ⁇ m or more in the negative photosensitive composition layer is preferably 10 pieces / mm 2 or less, and more preferably 5 pieces / mm 2 or less. preferable.
- the number of foreign substances shall be measured as follows. From the normal direction of the surface of the negative photosensitive composition layer, any five regions (1 mm ⁇ 1 mm) on the surface of the negative photosensitive composition layer are visually observed using an optical microscope. Then, the number of foreign substances having a diameter of 1.0 ⁇ m or more in each region is measured, and they are arithmetically averaged to calculate the number of foreign substances.
- aqueous solution of 1.0 mass% sodium carbonate is It is preferably 60% or less, more preferably 30% or less, further preferably 10% or less, and most preferably 1% or less.
- the haze shall be measured as follows. First, a 1.0% by mass sodium carbonate aqueous solution is prepared, and the liquid temperature is adjusted to 30 ° C. A 1.0 cm3 negative photosensitive composition layer is placed in 1.0 L of an aqueous sodium carbonate solution. Stir at 30 ° C.
- the haze of the solution in which the negative photosensitive composition layer is dissolved is measured.
- the haze is measured using a haze meter (product name "NDH4000", manufactured by Nippon Denshoku Kogyo Co., Ltd.), a liquid measuring unit, and a liquid measuring cell having an optical path length of 20 mm.
- the transfer film has an ultraviolet absorbing layer.
- the ultraviolet absorbing layer contains an ultraviolet absorber and a polymer having a ClogP value smaller than 2.1 (hereinafter, also referred to as “specific polymer”). If the ultraviolet absorber is a polymer and the ClogP value is less than 2.1, this polymer is not included in the specific polymer.
- the ultraviolet absorbing layer is a layer capable of absorbing ultraviolet rays (specifically, a layer capable of absorbing ultraviolet rays having a wavelength of 450 nm or less).
- UV rays such as i-line (365 nm) and j-line (313 nm), 248 nm which is the exposure wavelength of the KrF exposure apparatus, and 193 nm which is the exposure wavelength of the ArF exposure apparatus.
- H line (405 nm) and i line (365 nm) are more preferable.
- the transmittance of the ultraviolet absorbing layer at a wavelength of 365 nm is preferably 70% or less, more preferably 50% or less, still more preferably 40% or less because the effect of the present invention is more excellent. ..
- the lower limit is preferably, for example, 20% or more.
- the transmittance of the ultraviolet absorbing layer at a wavelength of 405 nm is preferably 70% or less, more preferably 50% or less, still more preferably 40% or less, because the effect of the present invention is more excellent. ..
- the lower limit is preferably, for example, 20% or more.
- the transmittance can be measured using an ultraviolet-visible spectroscopic altimeter (for example, UV-1800 manufactured by Shimadzu Corporation).
- the optical density (OD value, wavelength 365 nm) of the ultraviolet absorbing layer is preferably 0.1 to 0.6, more preferably 0.1 to 0.4, in that the effect of the present invention is more excellent.
- a spectroscope UV4100 (trade name) manufactured by Hitachi High-Technology Co., Ltd. can be used.
- the ultraviolet absorber is a compound capable of absorbing ultraviolet rays, and has an ultraviolet absorbing property capable of absorbing light having at least a part of the photosensitive wavelength of the photopolymerization initiator that can be contained in the negative photosensitive composition layer. Is preferable.
- the molar extinction coefficient of the ultraviolet absorber to light having a wavelength of 365 nm is preferably 5,000 to 100,000 (L / (mol ⁇ cm)), preferably 10,000 to 80,000 (L / (mol ⁇ cm)). cm)) is more preferable, and 15,000 to 50,000 (L / (mol ⁇ cm)) is even more preferable.
- the molar extinction coefficient of the ultraviolet absorber shall be measured by the following method.
- the compound to be measured is a 4 ⁇ 10-6 (g / mL) solution using N, N-dimethylformamide.
- the UV absorber is preferably a UV absorber that is dispersed and / or soluble in water.
- examples of the ultraviolet absorber include a polymer ultraviolet absorber and a polymer-coated ultraviolet absorber.
- the polymer ultraviolet absorber is a polymer having an ultraviolet absorbing structure, and specific examples thereof include a polymer containing a structural unit derived from a monomer having an ultraviolet absorbing structure.
- a triazine structure, a benzotriazole structure, a benzophenone structure, or a salicylic acid structure is preferable, and a triazine structure is more preferable.
- the polymer containing a structural unit derived from a monomer having an ultraviolet absorbing structure is preferably a (meth) acrylic resin.
- the (meth) acrylic resin is formed of a monomer for forming a (meth) acrylic resin as an alkali-soluble resin that can be contained in the thermoplastic resin layer of the transfer film of the first B embodiment described later.
- the content of the structural unit derived from the monomer having an ultraviolet absorbing structure in the polymer ultraviolet absorber is preferably 10 to 80% by mass, preferably 30 to 70% by mass, based on the total mass of the polymer. It is more preferable to have it.
- the weight average molecular weight of the polymer UV absorber is preferably 5,000 to 200,000, more preferably 7,000 to 150,000, and even more preferably 10,000 to 100,000.
- the polymer-coated ultraviolet absorber is an ultraviolet absorber in a form coated with a polymer, and examples thereof include polymer particles containing an ultraviolet absorber.
- the polymer include (meth) acrylic resin, polyester, polyurethane, polyolefin, siloxane resin, fluoropolymer and the like, and (meth) acrylic resin is preferable.
- the (meth) acrylic resin a (meth) acrylic resin as an alkali-soluble resin that can be contained in the thermoplastic resin layer of the transfer film of the first B embodiment described later is preferable.
- the content of the ultraviolet absorber in the polymer-coated ultraviolet absorber is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, and further preferably 40 to 60% by mass, based on the total amount of the polymer-coated ultraviolet absorber.
- the content of the polymer in the polymer-coated UV absorber is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, still more preferably 40 to 60% by mass, based on the total amount of the polymer-coated UV absorber.
- the weight average molecular weight of the polymer (for example, acrylic resin) in the polymer-coated UV absorber is preferably 5,000 to 200,000, more preferably 7,000 to 150,000, and further preferably 10,000 to 100,000. preferable.
- the upper limit of the median diameter (D50) is preferably 500 nm or less, more preferably 400 nm or less, further preferably 200 nm or less, and particularly preferably 100 nm or less.
- the lower limit of the median diameter is preferably 10 nm or more, and more preferably 20 nm or more.
- the median diameter can be calculated from the particle size distribution by dynamic light scattering measurement.
- particles may be particles which are in a state where they can be dispersed in water by subjecting carbon black to a dispersion treatment.
- the form of the dispersion treatment is not particularly limited, and examples thereof include particles in which carbon black is coated with a polymer and particles in which the surface of carbon black is surface-modified with a dispersant.
- the upper limit of the median diameter (D50) of the particles is preferably 500 nm or less, more preferably 400 nm or less, further preferably 200 nm or less, and particularly preferably 100 nm or less.
- the lower limit of the median diameter is preferably 10 nm or more, and more preferably 20 nm or more.
- the median diameter can be calculated from the particle size distribution by dynamic light scattering measurement.
- UV absorbers Commercially available products of UV absorbers include, for example, TWBK-2581 (manufactured by Taisei Kako Co., Ltd.), Tinuvin (registered trademark) 9945-DW, 400-DW, 477-DW, 479-DW (both manufactured by BASF). , Newcoat (registered trademark) UVA-204W, UVA-101, UVA-102, UVA-103, UVA-104, (both manufactured by Shin Nakamura Chemical Industry Co., Ltd.) and the like.
- ultraviolet absorber only one type may be used alone, or two or more types may be used in combination.
- the content of the ultraviolet absorber is preferably 0.001 to 50% by mass, more preferably 0.1 to 30% by mass, and 5 to 30% by mass with respect to the total mass of the ultraviolet absorbing layer. It is more preferably 5 to 20% by mass, and particularly preferably 5 to 20% by mass.
- the ultraviolet absorbing layer contains a polymer (specific polymer) having a ClogP value smaller than 2.1.
- the ClogP of the specific binder is preferably 2.0 or less, more preferably 1.9 or less, in that the effect of the present invention is more excellent.
- the lower limit is not particularly limited, but is preferably 1.0 or more.
- ClogP is a value obtained by calculation of the common logarithm logP of 1-octanol and the partition coefficient P to water.
- known methods can be used, but unless otherwise specified, the ClogP program incorporated in ChemBioDrow Ultra 12.0 of Cambridge software is used in the present specification.
- the I / O value in the organic conceptual diagram of the specific binder is preferably 0.75 or less, more preferably less than 0.70, and 0.65 or less in that the effect of the present invention is more excellent. Is more preferable.
- the lower limit is not particularly limited, but is preferably 0.2 or more.
- the I / O value is the ratio of the inorganic value (I) to the organic value (O) in the organic conceptual diagram (hereinafter, also referred to as “I / O value”).
- the I / O value of the specific binder is obtained by the following method.
- I / of each monomer constituting the specific binder Calculate the O value. For each monomer constituting the specific binder, the product of the "I / O value” and the "mol% with respect to all the constituent units of the specific binder” is calculated, and these are totaled to obtain the I / O value of the specific polymer.
- the SP value in the solubility parameter of the specific binder is preferably 18.0 (MPa) 1/2 or more, and is larger than 20.0 (MPa) 1/2 in that the effect of the present invention is more excellent. Is more preferable.
- the upper limit thereof is not particularly limited, but is preferably 22 (MPa) 1/2 or less.
- the SP value means a value represented by the following Fedors equation (1).
- EV Evaporation energy
- v Molar volume
- ⁇ e i Evaporation energy of each atom or atomic group
- ⁇ v i Molar volume of each atom or atomic group
- the SP value is calculated by the following formula.
- ⁇ 1 , ..., ⁇ m are SP values of each monomer constituting the copolymer, and are values obtained by the above formula (1).
- the (meth) acrylic resin means a resin having a structural unit derived from the (meth) acrylic compound.
- the content of the structural unit derived from the (meth) acrylic compound is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, based on all the structural units of the (meth) acrylic resin. ..
- the (meth) acrylic resin may be composed of only a structural unit derived from the (meth) acrylic compound, or may have a structural unit derived from a polymerizable monomer other than the (meth) acrylic compound. .. That is, the upper limit of the content of the structural unit derived from the (meth) acrylic compound is 100% by mass or less with respect to all the structural units of the (meth) acrylic resin.
- Examples of the (meth) acrylic compound include (meth) acrylic acid and (meth) acrylic acid ester.
- (meth) acrylic acid ester (meth) acrylic acid alkyl ester or (meth) acrylic acid allyl is preferable, and (meth) acrylic acid allyl is more preferable.
- the alkyl group of the (meth) acrylic acid alkyl ester may be linear or may have a branch.
- Specific examples include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, ( Heptyl acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, and (meth) acrylate.
- Examples thereof include (meth) acrylic acid alkyl esters having an alkyl group having 1 to 12 carbon atoms such as dodecyl. Further, the alkyl group of the (meth) acrylic acid alkyl ester may be cyclic. The cyclic alkyl group may be monocyclic or polycyclic. Specific examples include cyclohexyl (meth) acrylate and the like.
- the (meth) acrylic resin may have a structural unit other than the structural unit derived from the (meth) acrylic compound as long as the ClogP value satisfies the above range.
- the (meth) acrylic resin preferably has a structural unit having an acid group in that the effect of the present invention is more excellent.
- the acid group include a carboxy group, a sulfo group, a phosphoric acid group, and a phosphonic acid group.
- the content of the constituent unit having an acid group (preferably the constituent unit derived from (meth) acrylic acid) in the (meth) acrylic resin is the total mass of the (meth) acrylic resin in that the effect of the present invention is more excellent. On the other hand, 10% by mass or more is preferable.
- the upper limit is not particularly limited, but is preferably 50% by mass or less, more preferably 40% by mass or less, in terms of excellent alkali resistance.
- the (meth) acrylic resin has one or more of the above-mentioned structural units derived from the (meth) acrylic acid alkyl ester and the structural units derived from the (meth) allyl acrylic acid.
- the content of one or more structural units derived from the (meth) acrylic acid alkyl ester and the structural unit derived from allyl (meth) acrylic acid in the (meth) acrylic resin is the total content of the (meth) acrylic resin.
- 50 to 90% by mass is preferable, 60 to 90% by mass is more preferable, and 65 to 90% by mass is further preferable.
- Suitable forms of the (meth) acrylic resin include a structural unit derived from (meth) acrylic acid, a structural unit derived from a (meth) acrylic acid alkyl ester, and a structural unit derived from allyl (meth) acrylic acid. It is preferable that the resin has one or more kinds, and the constituent unit derived from (meth) acrylic acid, the constituent unit derived from (meth) acrylic acid alkyl ester, and the constituent unit derived from (meth) acrylic acid allyl. A resin composed of one or more kinds is more preferable.
- the acid value of the specific polymer is preferably 10 to 200 mgKOH / g, more preferably 60 to 200 mgKOH / g, further preferably 60 to 150 mgKOH / g, particularly preferably 70 to 150 mgKOH / g, and particularly preferably 100 to 150 mgKOH / g. Is the most preferable.
- the acid value of the specific polymer can be calculated from the average content of acid groups in the compound according to, for example, the method described in JIS K0070: 1992.
- the weight average molecular weight of the specific polymer is preferably 5,000 to 100,000, more preferably 7,000 to 50,000, still more preferably 10,000 to 50,000.
- the dispersity of the binder polymer is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, further preferably 1.0 to 4.0, and 1.0 to 3 from the viewpoint of developability. .0 is particularly preferred.
- the specific polymer only one kind may be used alone, or two or more kinds may be used in combination.
- the content of the specific polymer is, for example, preferably 20 to 95% by mass, more preferably 40 to 95% by mass, and 50 to 90% by mass with respect to the total mass of the ultraviolet absorbing layer. Is more preferable, and 60 to 90% by mass is particularly preferable.
- the content ratio of the ultraviolet absorber to the specific polymer is more preferably 0.05 to 0.4, and more preferably 0.1 to 0.3. Is more preferable.
- the ultraviolet absorbing layer may contain other components other than the ultraviolet absorber and the specific polymer. Examples of other components include polymerizable compounds, polymerization initiators, surfactants and the like. As a preferable aspect of the ultraviolet absorbing layer, it is also preferable that it is photocurable.
- the photocurable ultraviolet absorbing layer preferably contains an ethylenically unsaturated compound, and more preferably contains an ethylenically unsaturated compound and a photopolymerization initiator.
- the ultraviolet absorbing layer contains a polymerizable compound (preferably an ethylenically unsaturated compound)
- the content of the polymerizable compound preferably an ethylenically unsaturated compound
- the strength of the ultraviolet absorbing layer is more excellent.
- the UV absorbing layer contains a polymerization initiator (preferably a photopolymerization initiator), the content of the polymerization initiator (preferably a photopolymerization initiator) is such that the strength of the UV absorbing layer is more excellent in that it absorbs UV light. It is preferably 0.1 to 10% by mass, more preferably 0.5 to 10% by mass, still more preferably 0.5 to 5% by mass, based on the total mass of the layer.
- a polymerization initiator preferably a photopolymerization initiator
- the ultraviolet absorbing layer may contain a surfactant.
- the content of the surfactant is preferably 0.01 to 3% by mass, more preferably 0.05 to 1% by mass, based on the total mass of the ultraviolet absorbing layer. It is more preferably 0.1 to 0.8% by mass.
- Examples of the polymerizable compound, the polymerization initiator, and the surfactant that may be contained in the ultraviolet absorbing layer include the negative-type photosensitive composition layer of the above-mentioned 1A embodiment or the negative-type photosensitive of the first B embodiment described later. Examples thereof include polymerizable compounds, polymerization initiators, and surfactants that may be contained in the composition layer.
- the ultraviolet absorbing layer may optionally contain other components.
- Other components include, for example, metal oxide particles, cross-linking agents other than heterocyclic compounds, alkoxysilane compounds, antioxidants, dispersants, acid growth agents, development accelerators, conductive fibers, colorants, and thermal radical generation. Examples thereof include known additives such as agents, thermoacid generators, thickeners, and organic or inorganic anti-precipitation agents.
- the thickness of the ultraviolet absorbing layer is preferably 0.05 to 5.0 ⁇ m, more preferably 0.05 to 2.0 ⁇ m, further preferably 0.1 to 1.0 ⁇ m, and particularly preferably 0.1 to 0.5 ⁇ m. , 0.1-0.4 ⁇ m is most preferred.
- the transfer film preferably has an intermediate layer (intermediate layer A) between the temporary support and the negative photosensitive composition layer in that the peelability of the temporary support is further improved.
- the intermediate layer is preferably a water-soluble resin layer containing a water-soluble resin.
- the intermediate layer preferably has an oxygen blocking ability. It is preferable that the intermediate layer has an oxygen blocking ability because the sensitivity at the time of exposure is improved, the time load of the exposure machine is reduced, and the productivity is improved. In addition, there is an advantage that oxygen inhibition is less likely to occur in the polymerization reaction during exposure.
- the intermediate layer is preferably a layer that exhibits low oxygen permeability and is dispersed or dissolved in water or an alkaline aqueous solution (1% by mass aqueous solution of sodium carbonate at 22 ° C.).
- the intermediate layer preferably contains a resin.
- the resin preferably contains a water-soluble resin in part or in whole.
- the resin that can be used as the water-soluble resin include polyvinyl alcohol-based resin, polyvinylpyrrolidone-based resin, cellulose-based resin (for example, water-soluble cellulose derivative such as hydroxypropyl cellulose and hydroxypropyl methyl cellulose), acrylamide-based resin, and polyether.
- examples thereof include based resins (for example, polyalkylene oxide-based resins such as polyethylene glycol and polypropylene glycol), gelatin, vinyl ether-based resins, polyamide resins, and resins such as copolymers thereof.
- the water-soluble resin a (meth) acrylic acid / vinyl compound copolymer or the like can also be used.
- a copolymer of (meth) acrylic acid / vinyl compound a copolymer of (meth) acrylic acid / allyl (meth) acrylic acid is preferable, and a copolymer of methacrylic acid / allyl methacrylate is more preferable.
- the composition ratio (mol%) is preferably 90/10 to 20/80, preferably 80/20 to 30/70. More preferred.
- the lower limit of the weight average molecular weight of the water-soluble resin is preferably 5,000 or more, more preferably 7,000 or more, and even more preferably 10,000 or more.
- the upper limit thereof is preferably 200,000 or less, more preferably 100,000 or less, and even more preferably 50,000 or less.
- the dispersity (Mw / Mn) of the water-soluble resin is preferably 1 to 10, more preferably 1 to 5.
- the water-soluble resin preferably contains one or more of polyvinyl alcohol and polyvinylpyrrolidone in terms of further improving the peelability of the temporary support and / or having more excellent oxygen blocking ability, and the polyvinyl alcohol is preferably used. It is more preferable to contain polyvinyl alcohol and polyvinylpyrrolidone. It is also preferable to use one or more of polyvinyl alcohol and polyvinylpyrrolidone in combination with one or more of water-soluble cellulose derivatives and polyethers, and one or more of polyvinyl alcohol and polyvinylpyrrolidone and water-soluble cellulose derivatives. It is more preferable to use them together.
- the water-soluble cellulose derivative is not particularly limited, and examples thereof include hydroxyethyl cellulose, hydroxypropylmethyl cellulose, hydroxypropyl cellulose, methyl cellulose, and ethyl cellulose.
- the polyethers include polyethylene glycol and polypropylene glycol.
- the water-soluble resin may be used alone or in combination of two or more.
- the content of the water-soluble resin is not particularly limited, but is 50% by mass with respect to the total mass of the intermediate layer in that the peelability of the temporary support is further improved and / or the oxygen blocking ability is more excellent.
- the above is preferable, and 70% by mass or more is more preferable.
- the upper limit is not particularly limited, but is, for example, 100% by mass or less, preferably 99.9% by mass or less, more preferably 99.8% by mass or less, and further preferably 99% by mass or less.
- the intermediate layer may have components other than the above resin.
- the upper limit of the molecular weight of the other components is not particularly limited, and is preferably less than 5,000, more preferably 4,000 or less, further preferably 3,000 or less, and particularly preferably 2,000 or less. , 500 or less is the most preferable.
- the lower limit is, for example, 60 or more.
- polyhydric alcohols alkylene oxide adducts of polyhydric alcohols, phenol derivatives, and amide compounds are preferable, and polyhydric alcohols are preferable, because the peelability of the temporary support is further improved. Classes or phenol derivatives are more preferred.
- the number of hydroxyl groups contained in the polyhydric alcohol is not particularly limited, and is preferably 2 to 10, for example.
- polyhydric alcohols include glycerin, diglycerin, diethylene glycol and the like.
- alkylene oxide adduct of polyhydric alcohols include compounds obtained by adding ethylene oxide, propylene oxide and the like to the above-mentioned polyhydric alcohols.
- the average number of additions is not particularly limited, and is, for example, 1 to 100, preferably 2 to 50, and more preferably 2 to 20.
- examples of the phenol derivative include bisphenol A and bisphenol S.
- examples of the amide compound include N-methylpyrrolidone and the like.
- the above-mentioned other components may be used alone or in combination of two or more.
- the content of the above other components is not particularly limited, but is preferably 0.1% by mass or more, preferably 0.5% by mass or more, based on the total mass of the intermediate layer in terms of further improving the peelability of the temporary support. Is more preferable, and 1% by mass or more is further preferable.
- the upper limit is not particularly limited, but for example, it is preferably less than 30% by mass, more preferably 10% by mass or less, and further preferably 5% by mass or less.
- Compounds selected from the group consisting of polyethers, polyhydric alcohols, alkylene oxide adducts of polyhydric alcohols, phenol derivatives, and amide compounds preferably water-soluble cellulose derivatives, polyethers, phenol derivatives, and glycerin. It is preferable to include a compound selected from the group consisting of (hereinafter, also referred to as “compound X”).
- the compound X tends to be unevenly distributed on the surface of the intermediate layer on the temporary support side, and / or WBL (weak) due to the mixing of the intermediate layer and the negative photosensitive composition layer. boundary layer) It becomes difficult to form a layer, and the surface free energy on the temporary support side of the intermediate layer and the arithmetic mean roughness on the same surface are easily adjusted to more appropriate values.
- the temporary support is temporarily supported without causing cohesive failure of the intermediate layer when the temporary support is peeled off. Peeling is likely to occur at the interface between the body and the intermediate layer.
- the composition of the intermediate layer is more preferably one or more of polyvinyl alcohol and polyvinylpyrrolidone, and more preferably one or more of a water-soluble cellulose derivative and polyethers as compound X, further suppressing the plasticization of the intermediate layer. It is more preferable to contain one or more of polyvinyl alcohol and polyvinylpyrrolidone in terms of ease of use, and a water-soluble cellulose derivative as compound X, and one or more of polyvinyl alcohol and polyvinylpyrrolidone in that the temporary support peeling property is more excellent. And, it is particularly preferable to contain hydroxypropylmethyl cellulose as the compound X. Further, polyvinyl alcohol and polyvinylpyrrolidone are preferably used in combination.
- the total content of polyvinyl alcohol and polyvinylpyrrolidone is preferably 50% by mass or more with respect to the total mass of the intermediate layer in that the peelability of the temporary support is further improved. 70% by mass or more is more preferable.
- the upper limit is not particularly limited, but is, for example, 100% by mass or less, preferably 99.9% by mass or less, more preferably 99.8% by mass or less, and further preferably 99% by mass or less.
- the content of polyvinyl alcohol is preferably 5 to 95% by mass with respect to the total mass of the intermediate layer.
- the compounding ratio (mass ratio) of polyvinyl alcohol and polyvinylpyrrolidone is preferably 5/95 to 95/5, more preferably 20/80 to 80/20. , 25/75 to 70/25 are more preferable.
- the content of the compound X is not particularly limited, but 0.1% by mass or more with respect to the total mass of the intermediate layer in that the peelability of the temporary support is further improved. Is preferable, 0.5% by mass or more is more preferable, and 0.8% by mass or more is further preferable.
- the upper limit is preferably less than 30% by mass, more preferably 15% by mass or less.
- the content of the compound X is less than 30% by mass with respect to the total mass of the intermediate layer, the phase separation of the intermediate layer forming component is likely to be suppressed, and the surface roughening of the intermediate layer due to this is unlikely to occur. Therefore, it is superior in resolution.
- the transfer film preferably has a refractive index adjusting layer.
- a known refractive index adjusting layer can be applied.
- the material contained in the refractive index adjusting layer include a binder polymer, a polymerizable compound, a metal salt, and particles.
- the method for controlling the refractive index of the refractive index adjusting layer is not particularly limited, and for example, a method using a resin having a predetermined refractive index alone, a method using a resin and particles, and a composite of a metal salt and a resin are used. Is mentioned.
- binder polymer and the polymerizable compound examples include the binder polymer and the polymerizable compound described in the section of the above-mentioned "negative photosensitive composition layer".
- the particles include metal oxide particles and metal particles.
- the type of the metal oxide particles is not particularly limited, and examples thereof include known metal oxide particles.
- the metal in the metal oxide particles also includes metalloids such as B, Si, Ge, As, Sb, and Te.
- the average primary particle size of the particles is, for example, preferably 1 to 200 nm, more preferably 3 to 80 nm, from the viewpoint of transparency of the cured film.
- the average primary particle size of the particles is calculated by measuring the particle size of 200 arbitrary particles using an electron microscope and arithmetically averaging the measurement results. When the shape of the particle is not spherical, the longest side is the particle diameter.
- the metal oxide particles include zirconium oxide particles (ZrO 2 particles), Nb 2 O 5 particles, titanium oxide particles (TiO 2 particles), silicon dioxide particles (SiO 2 particles), and composites thereof. At least one selected from the group consisting of particles is preferable. Among these, as the metal oxide particles, for example, at least one selected from the group consisting of zirconium oxide particles and titanium oxide particles is more preferable because the refractive index can be easily adjusted.
- metal oxide particles include calcined zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT% -F04), calcined zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT% -F74).
- Fired Zirconium Oxide Particles (CIK Nanotech Co., Ltd., Product Name: ZRPGM15WT% -F75), Fired Zirconium Oxide Particles (CIK Nanotech Co., Ltd., Product Name: ZRPGM15WT% -F76), Zirconium Oxide Particles (Nano Teen OZ-S30M, Nissan) Examples include (manufactured by Chemical Industry Co., Ltd.) and zirconium oxide particles (Nano Teen OZ-S30K, manufactured by Nissan Chemical Industry Co., Ltd.).
- the particles may be used alone or in combination of two or more.
- the content of the particles in the refractive index adjusting layer is preferably 1 to 95% by mass, more preferably 20 to 90% by mass, still more preferably 40 to 85% by mass, based on the total mass of the refractive index adjusting layer.
- the content of the titanium oxide particles is preferably 1 to 95% by mass, more preferably 20 to 90% by mass, and 40 to 85% by mass with respect to the total mass of the refractive index adjusting layer. % Is more preferable.
- the refractive index of the refractive index adjusting layer is preferably higher than that of the negative photosensitive composition layer.
- the refractive index of the refractive index adjusting layer is preferably 1.50 or more, more preferably 1.55 or more, further preferably 1.60 or more, and particularly preferably 1.65 or more.
- the upper limit of the refractive index of the refractive index adjusting layer is preferably 2.10 or less, more preferably 1.85 or less, and even more preferably 1.78 or less.
- the refractive index is a refractive index having a wavelength of 550 nm at 25 ° C.
- the thickness of the refractive index adjusting layer is preferably 50 to 500 nm, more preferably 55 to 110 nm, and even more preferably 60 to 100 nm.
- the thickness of the refractive index adjusting layer is calculated as an average value of any five points measured by cross-sectional observation with a scanning electron microscope (SEM).
- the transfer film may have a protective film.
- a resin film having heat resistance and solvent resistance can be used, and examples thereof include a polyolefin film such as a polypropylene film and a polyethylene film, a polyester film such as a polyethylene terephthalate film, a polycarbonate film, and a polystyrene film. Be done.
- a resin film made of the same material as the above-mentioned temporary support may be used.
- a polyolefin film is preferable, a polypropylene film or a polyethylene film is more preferable, and a polyethylene film is further preferable.
- the thickness of the protective film is preferably 1 to 100 ⁇ m, more preferably 5 to 50 ⁇ m, further preferably 5 to 40 ⁇ m, and particularly preferably 15 to 30 ⁇ m.
- the thickness of the protective film is preferably 1 ⁇ m or more in terms of excellent mechanical strength, and preferably 100 ⁇ m or less in terms of relatively low cost.
- the number of fish eyes having a diameter of 80 ⁇ m or more contained in the protective film is 5 / m 2 or less.
- fish eye refers to foreign substances, undissolved substances, oxidative deterioration substances, etc. of the material when the material is thermally melted, kneaded, extruded, and used to produce a film by a biaxial stretching method, a casting method, or the like. Was incorporated into the film.
- the number of particles having a diameter of 3 ⁇ m or more contained in the protective film is preferably 30 particles / mm 2 or less, more preferably 10 particles / mm 2 or less, and further preferably 5 particles / mm 2 or less. As a result, it is possible to suppress defects caused by the unevenness caused by the particles contained in the protective film being transferred to the negative photosensitive composition layer or the conductive layer.
- the arithmetic mean roughness Ra of the surface of the protective film opposite to the surface in contact with the composition layer is preferably 0.01 ⁇ m or more, more preferably 0.02 ⁇ m or more, and more preferably 0.03 ⁇ m from the viewpoint of imparting windability. The above is more preferable. On the other hand, less than 0.50 ⁇ m is preferable, 0.40 ⁇ m or less is more preferable, and 0.30 ⁇ m or less is further preferable.
- the protective film has a surface roughness Ra of the surface in contact with the composition layer of preferably 0.01 ⁇ m or more, more preferably 0.02 ⁇ m or more, still more preferably 0.03 ⁇ m or more, from the viewpoint of suppressing defects during transfer. On the other hand, less than 0.50 ⁇ m is preferable, 0.40 ⁇ m or less is more preferable, and 0.30 ⁇ m or less is further preferable.
- the transfer film preferably satisfies one or more of preferred embodiments 1, preferred embodiments 2, preferred embodiments 3, preferred embodiments 4, and preferred embodiments 5, and more preferably all of them.
- “Breaking elongation of the cured film obtained by curing the negative photosensitive composition layer” is performed by exposing the negative photosensitive composition layer having a thickness of 20 ⁇ m to 120 mJ / cm 2 with an ultrahigh pressure mercury lamp and curing it, and then using a high pressure mercury lamp.
- the cured film after further exposure at 400 mJ / cm 2 and heated at 145 ° C. for 30 minutes is measured by a tensile test.
- the "arithmetic mean roughness Ra of the surface of the temporary support on the negative photosensitive composition layer side” can be measured by the following method. Using a three-dimensional optical profiler (New View7300, Zygo), a surface profile of the object to be measured is obtained under the following conditions.
- the measurement and analysis software Microscope Application of MetroPro ver8.3.2 is used.
- the Surface Map screen is displayed using the above software, and histogram data is obtained in the Surface Map screen. From the obtained histogram data, the arithmetic mean roughness Ra of the surface of the object to be measured is obtained.
- the method for measuring the "arithmetic mean roughness Ra of the surface of the protective film on the negative photosensitive composition layer side" is the measurement of the "arithmetic mean roughness Ra of the surface of the temporary support on the negative photosensitive composition layer side". It is carried out in the same way as the method.
- the transfer film it is preferable that the physical characteristics of the temporary support, the negative photosensitive composition layer, and the protective film satisfy all of the following conditions (P1) to (P3).
- P1 The breaking elongation of the cured film obtained by curing the negative photosensitive composition layer at 120 ° C. is 15% or more.
- P2 The arithmetic mean roughness Ra of the surface of the temporary support on the negative photosensitive composition layer side is 50 nm or less.
- the arithmetic mean roughness Ra of the surface of the protective film on the negative photosensitive composition layer side is 150 nm or less.
- the physical characteristics of the temporary support of the transfer film and the negative photosensitive composition layer preferably satisfy the following formula (1).
- X represents the value (%) of the elongation at break at 120 ° C. of the cured film obtained by curing the negative photosensitive composition layer
- Y represents the negative photosensitive composition of the temporary support. It represents the value (nm) of the arithmetic mean roughness Ra of the surface on the material layer side.
- the value represented by X ⁇ Y is preferably 750 or less.
- the photosensitive physical characteristics of the transfer film preferably satisfy the following condition (P4).
- P4 The breaking elongation at 120 ° C. is more than twice as large as the breaking elongation at 23 ° C. of the cured film obtained by curing the negative photosensitive composition layer.
- the physical characteristics of the temporary support of the transfer film and the negative photosensitive composition layer preferably satisfy the following formula (2).
- Y represents the value (nm) of the arithmetic mean roughness Ra of the surface of the surface of the temporary support on the negative photosensitive composition layer side
- Z represents the negative photosensitive of the protective film. It represents the value (nm) of the arithmetic mean roughness Ra of the surface on the composition layer side.
- the method for producing the transfer film of the first A embodiment is not particularly limited, and a known method can be used.
- a method for producing the transfer film 10 for example, a coating film for forming an intermediate layer (intermediate layer A) is applied to the surface of the temporary support 1 to form a coating film, and the coating film is further dried.
- the step of forming the intermediate layer (intermediate layer A) 3 and the coating film for forming a negative photosensitive composition layer are applied to the surface of the intermediate layer (intermediate layer A) 3 to form a coating film, and further, this coating film is formed.
- a negative-type photosensitive composition layer 5 To form a negative-type photosensitive composition layer 5 and to apply a composition for forming an ultraviolet absorbing layer on the surface of the negative-type photosensitive composition layer 5 to form a coating film, and further to form a coating film.
- a coating film by applying a composition for forming a refractive index adjusting layer on the surface of the ultraviolet absorbing layer 7 and a step of forming the ultraviolet absorbing layer 7, and further drying this coating film to adjust the refractive index. Examples thereof include a step of forming the layer 9 and a method including.
- the transfer film 10 is manufactured by crimping the protective film 11 onto the refractive index adjusting layer 9 of the laminate manufactured by the above-mentioned manufacturing method.
- the method for producing the transfer film of the first A embodiment includes a step of providing the protective film 11 so as to be in contact with the surface of the refractive index adjusting layer 9 opposite to the side having the temporary support 1. 1. It is preferable to manufacture a transfer film 10 including an intermediate layer (intermediate layer A) 3, a negative photosensitive composition layer 5, an ultraviolet absorbing layer 7, a refractive index adjusting layer 9, and a protective film 11. After the transfer film 10 is manufactured by the above-mentioned manufacturing method, the transfer film 10 may be wound up to prepare and store the transfer film in the form of a roll.
- the roll-type transfer film can be provided as it is in the bonding process with the substrate in the roll-to-roll method described later.
- the refractive index adjusting layer 9 is formed on the protective film 11, and then the ultraviolet absorbing layer 7 is formed on the surface of the refractive index adjusting layer 9, and the ultraviolet absorbing layer 7 is formed.
- a method may be used in which a negative photosensitive composition layer 5 is formed on the surface thereof, and an intermediate layer (intermediate layer A) 3 is further formed on the surface of the negative photosensitive composition layer 5.
- an intermediate layer (intermediate layer A) 3, a negative photosensitive composition layer 5, and an ultraviolet absorbing layer 7 are formed on the temporary support 1 and separately protected.
- a method may be used in which the refractive index adjusting layer 9 is formed on the film 11 and the ultraviolet absorbing layer 7 and the refractive index adjusting layer 9 are bonded to each other.
- composition for forming an intermediate layer (intermediate layer A) and a method for forming an intermediate layer (intermediate layer A) preferably contains various components for forming the intermediate layer (intermediate layer A) described above and, if necessary, a solvent.
- the preferable range of the content of each component with respect to the total solid content of the composition is the content of each component with respect to the total mass of the intermediate layer (intermediate layer A) described above. It is the same as the preferable range of.
- the solvent is not particularly limited as long as it can dissolve or disperse the components contained in the composition for forming the intermediate layer (intermediate layer A), and is at least one selected from the group consisting of water and a water-miscible organic solvent. Is preferable, and a mixed solvent of water or a water-miscible organic solvent is more preferable.
- the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin, and alcohols having 1 to 3 carbon atoms are preferable, and methanol or ethanol is more preferable.
- the solvent may be used alone or in combination of two or more.
- the content of the solvent is preferably 50 to 2,500 parts by mass, more preferably 50 to 1,900 parts by mass, and even more preferably 100 to 900 parts by mass with respect to 100 parts by mass of the total solid content of the composition.
- the method for forming the intermediate layer is not particularly limited as long as it can form a layer containing the above components, and for example, known coating methods (bar coat coating, slit coating, spin coating, curtain coating). , And inkjet coating, etc.).
- the negative photosensitive composition layer in the transfer film is a component constituting the above-mentioned negative photosensitive composition layer (for example, a binder polymer, a polymerizable compound, a polymerization initiator, etc.). It is desirable that the film is formed by a coating method using a negative photosensitive composition layer-forming composition containing a solvent. Specifically, as a method for producing a transfer film of the first A embodiment, a negative-type photosensitive composition layer-forming composition is applied onto a temporary support to form a coating film, and the coating film is dried. Is preferable in this method to form a negative photosensitive composition layer.
- An organic solvent is preferable as the solvent that can be contained in the composition for forming the negative photosensitive composition layer.
- the organic solvent include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (also known as 1-methoxy-2-propyl acetate), diethylene glycol ethyl methyl ether, cyclohexanone, methyl isobutyl ketone, ethyl lactate, methyl lactate, and caprolactam. , N-propanol, and 2-propanol.
- an organic solvent having a boiling point of 180 to 250 ° C. can be used, if necessary.
- the solvent may be used alone or in combination of two or more.
- the total solid content of the negative-type photosensitive composition layer-forming composition is preferably 5 to 80% by mass, more preferably 5 to 70% by mass, based on the total mass of the negative-type photosensitive composition layer-forming composition. It is preferable, and 5 to 65% by mass is more preferable. That is, the content of the solvent in the composition for forming the negative photosensitive composition layer is preferably 20 to 95% by mass, preferably 30 to 95% by mass, based on the total mass of the composition for forming the negative photosensitive composition layer. 95% by mass is more preferable, and 35 to 95% by mass is further preferable.
- the viscosity of the composition for forming a negative photosensitive composition layer at 25 ° C. is, for example, preferably 1 to 50 mPa ⁇ s, more preferably 2 to 40 mPa ⁇ s, and further preferably 3 to 30 mPa ⁇ s from the viewpoint of coatability. preferable. Viscosity is measured using a viscometer.
- a viscometer manufactured by Toki Sangyo Co., Ltd. (trade name: VISCOMETER TV-22) can be preferably used.
- the viscometer is not limited to the above-mentioned viscometer.
- the surface tension of the negative photosensitive composition layer forming composition at 25 ° C. is, for example, preferably 5 to 100 mN / m, more preferably 10 to 80 mN / m, and 15 to 40 mN / m from the viewpoint of coatability. More preferred.
- Surface tension is measured using a tensiometer.
- a surface tension meter manufactured by Kyowa Interface Science Co., Ltd. (trade name: Acoustic Surface Tensiometer CBVP-Z) can be preferably used.
- the tensiometer is not limited to the above-mentioned tensiometer.
- Examples of the method for applying the negative photosensitive composition layer forming composition include a printing method, a spray method, a roll coating method, a bar coating method, a curtain coating method, a spin coating method, and a die coating method (that is, a slit coating method). Law).
- drying means removing at least a part of the solvent contained in a composition.
- drying method include natural drying, heat drying, and vacuum drying.
- the above methods can be applied alone or in combination.
- the drying temperature is preferably 80 ° C. or higher, more preferably 90 ° C. or higher.
- the upper limit thereof is preferably 130 ° C. or lower, more preferably 120 ° C. or lower. It can also be dried by continuously changing the temperature.
- the drying time is preferably 20 seconds or longer, more preferably 40 seconds or longer, and even more preferably 60 seconds or longer.
- the upper limit is not particularly limited, but is preferably 600 seconds or less, and more preferably 300 seconds or less.
- the composition for forming an ultraviolet absorbing layer preferably contains the above-mentioned various components forming the ultraviolet absorbing layer and a solvent.
- the preferable range of the content of each component with respect to the total solid content of the composition is the same as the preferable range of the content of each component with respect to the total mass of the ultraviolet absorbing layer described above.
- the solvent is not particularly limited as long as it can dissolve or disperse the components contained in the composition for forming an ultraviolet absorbing layer, and at least one selected from the group consisting of water and a water-miscible organic solvent is preferable, and water is preferable.
- a mixed solvent of water and a water-miscible organic solvent is more preferable.
- the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin, and alcohols having 1 to 3 carbon atoms are preferable, and methanol or ethanol is more preferable.
- the solvent may be used alone or in combination of two or more.
- the content of the solvent is preferably 50 to 2,500 parts by mass, more preferably 50 to 1,900 parts by mass, and even more preferably 100 to 900 parts by mass with respect to 100 parts by mass of the total solid content of the composition.
- the method for forming the ultraviolet absorbing layer is not particularly limited as long as it can form a layer containing the above components, and for example, known coating methods (bar coat coating, slit coating, spin coating, curtain coating, and inkjet coating) are used. Etc.).
- composition for forming a refractive index adjusting layer and a method for forming the refractive index adjusting layer preferably contains various components forming the above-mentioned refractive index adjusting layer and a solvent.
- the preferable range of the content of each component with respect to the total solid content of the composition is the same as the preferable range of the content of each component with respect to the total mass of the refractive index adjusting layer described above. be.
- the solvent is not particularly limited as long as it can dissolve or disperse the components contained in the refractive index adjusting layer, and at least one selected from the group consisting of water and a water-miscible organic solvent is preferable, with water or water.
- a mixed solvent with a water-miscible organic solvent is more preferable.
- the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin, and alcohols having 1 to 3 carbon atoms are preferable, and methanol or ethanol is more preferable.
- the solvent may be used alone or in combination of two or more.
- the content of the solvent is preferably 50 to 2,500 parts by mass, more preferably 50 to 1,900 parts by mass, and even more preferably 100 to 900 parts by mass with respect to 100 parts by mass of the total solid content of the composition.
- the method for forming the refractive index adjusting layer is not particularly limited as long as it can form a layer containing the above components, and for example, known coating methods (slit coating, spin coating, curtain coating, inkjet coating, etc.) can be used. Can be mentioned.
- the transfer film of the first A embodiment can be manufactured.
- the method of attaching the protective film to the refractive index adjusting layer is not particularly limited, and known methods can be mentioned.
- Examples of the device for adhering the protective film to the refractive index adjusting layer include a vacuum laminator and a known laminator such as an auto-cut laminator. It is preferable that the laminator is provided with an arbitrary heatable roller such as a rubber roller and can be pressurized and heated.
- the transfer film 30 shown in FIG. 2 includes a temporary support 21, a thermoplastic resin layer 23, an intermediate layer (intermediate layer B) 25, a negative photosensitive composition layer 27, and an ultraviolet absorbing layer 29. And the protective film 31 in this order.
- the transfer film 30 shown in FIG. 2 has a form in which the protective film 31 is arranged, but the protective film 31 may not be arranged.
- the transfer film 30 shown in FIG. 2 has a form in which the thermoplastic resin layer 23 and the intermediate layer (intermediate layer B) 25 are arranged, but at least one of the thermoplastic resin layer 23 and the intermediate layer (intermediate layer B) 25 is arranged.
- the transfer film 30 shown in FIG. 2 may have a form in which an intermediate layer (intermediate layer A) is arranged between the temporary support 21 and the thermoplastic resin layer 23.
- the intermediate layer (intermediate layer A) is the same as the intermediate layer (intermediate layer A) included in the transfer film of the first A embodiment described above.
- transfer film each element constituting the transfer film of the first B embodiment (hereinafter, may be abbreviated as “transfer film”) will be described.
- the temporary support 21, the ultraviolet absorbing layer 29, and the protective film 31 include the temporary support 1, the ultraviolet absorbing layer 9, and the protective film 11 of the above-mentioned first A embodiment. The same is mentioned, and the preferred embodiment is also the same.
- Negative Photosensitive Composition Layer In display devices equipped with a touch panel such as a capacitance type input device (organic electroluminescence (EL) display device, liquid crystal display device, etc.), the electrode pattern corresponding to the sensor of the visual recognition part, the peripheral wiring part, and the wiring of the take-out wiring part are wired. Etc. are provided inside the touch panel.
- a negative photosensitive composition layer is provided on a substrate using a transfer film or the like, and a mask having a desired pattern for the negative photosensitive composition layer is used. A method of developing after exposure is widely adopted. In the negative photosensitive composition layer, the exposed portion becomes a cured film due to exposure, and the solubility in a developing solution is lowered.
- the negative photosensitive composition layer preferably contains a binder polymer, a polymerizable compound, and a polymerization initiator. Further, it is also preferable that the binder polymer contains an alkali-soluble resin (polymer A or the like which is an alkali-soluble resin) as a part or the whole thereof. That is, in one embodiment, the negative photosensitive composition layer preferably contains a binder polymer containing an alkali-soluble resin, a polymerizable compound, and a polymerization initiator. Such a negative photosensitive composition layer has a binder polymer: 10 to 90% by mass; a polymerizable compound: 5 to 70% by mass; a polymerization initiator: 0, based on the total mass of the negative photosensitive composition layer. It preferably contains 0.01 to 20% by mass.
- each component will be described in order.
- the negative photosensitive composition layer preferably contains the polymer A as the binder polymer.
- the polymer A is preferably an alkali-soluble resin.
- the acid value of the polymer A is preferably 220 mgKOH / g or less, more preferably less than 200 mgKOH / g, from the viewpoint of better resolution by suppressing the swelling of the negative photosensitive composition layer due to the developing solution. More preferably less than 190 mgKOH / g.
- the lower limit of the acid value of the polymer A is not particularly limited, but 60 mgKOH / g or more is preferable. In terms of more excellent developability, 120 mgKOH / g or more is more preferable, 150 mgKOH / g or more is further preferable, and 170 mgKOH / g or more is particularly preferable.
- the acid value (mgKOH / g) is the mass [mg] of potassium hydroxide required to neutralize 1 g of the sample.
- the acid value can be calculated from the average content of acid groups in the compound, for example, according to the method described in JIS K0070: 1992.
- the acid value of the polymer A may be adjusted according to the type of the structural unit constituting the polymer A and the content of the structural unit containing the acid group.
- the weight average molecular weight of the polymer A is preferably 5,000 to 500,000. When the weight average molecular weight is 500,000 or less, it is preferable from the viewpoint of improving resolution and developability.
- the weight average molecular weight is more preferably 100,000 or less, further preferably 60,000 or less, particularly preferably 35,000 or less, and most preferably 30,000 or less.
- the weight average molecular weight is 5,000 or more, the viewpoint of controlling the properties of the developed aggregate and the properties of the unexposed film such as the edge fuse property and the cut chip property when the negative photosensitive resin laminate is used. Is preferable.
- the weight average molecular weight is more preferably 10,000 or more.
- the edge fuse property refers to the degree of ease with which the negative photosensitive composition layer protrudes from the end face of the roll when it is wound into a roll as a negative photosensitive resin laminate.
- the cut chip property refers to the degree of ease of chip flying when the unexposed film is cut with a cutter. When this chip adheres to the upper surface of the negative photosensitive resin laminate or the like, it is transferred to the mask in a later exposure process or the like, which causes a defective product.
- the dispersity of the polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, still more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0. ..
- the degree of dispersion is intended to be the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight).
- the weight average molecular weight and the number average molecular weight are values measured by gel permeation chromatography.
- the polymer A preferably contains a structural unit based on a monomer having an aromatic hydrocarbon group.
- aromatic hydrocarbon groups include substituted or unsubstituted phenyl groups and substituted or unsubstituted aralkyl groups.
- the content of the structural unit based on the monomer having an aromatic hydrocarbon group in the polymer A is preferably 20% by mass or more, more preferably 30% by mass or more, based on the total mass of the polymer A.
- the upper limit is not particularly limited, but is preferably 95% by mass or less, and more preferably 85% by mass or less.
- the average value of the content of the structural unit based on the monomer having an aromatic hydrocarbon group is within the above range.
- the monomer having an aromatic hydrocarbon group examples include a monomer having an aralkyl group, styrene, and a polymerizable styrene derivative (for example, methyl styrene, vinyl toluene, tert-butoxy styrene, acetoxy styrene, 4-vinyl scent). Acids, styrene dimers, styrene trimers, etc.). Of these, a monomer having an aralkyl group or styrene is preferable.
- the content of the structural unit based on styrene is 20 to 70% by mass with respect to the total mass of the polymer A. Is preferable, 25 to 65% by mass is more preferable, 30 to 60% by mass is further preferable, and 30 to 55% by mass is particularly preferable.
- the negative photosensitive composition layer contains a plurality of types of polymers A, the content of the structural unit having an aromatic hydrocarbon group is determined as a weight average value.
- aralkyl group examples include a substituted or unsubstituted phenylalkyl group (excluding a benzyl group), a substituted or unsubstituted benzyl group and the like, and a substituted or unsubstituted benzyl group is preferable.
- Examples of the monomer having a phenylalkyl group include phenylethyl (meth) acrylate and the like.
- Examples of the monomer having a benzyl group include (meth) acrylate having a benzyl group, for example, benzyl (meth) acrylate, and chlorobenzyl (meth) acrylate; a vinyl monomer having a benzyl group, for example, vinylbenzyl chloride, and the like. Examples include vinylbenzyl alcohol. Of these, benzyl (meth) acrylate is preferable.
- the monomer component having an aromatic hydrocarbon group in the polymer A is benzyl (meth) acrylate
- the content of the structural unit based on the benzyl (meth) acrylate is the total mass of the polymer A.
- 25 to 95% by mass is preferable, 50 to 95% by mass is more preferable, 60 to 90% by mass is further preferable, 70 to 90% by mass is particularly preferable, and 75 to 90% by mass is most preferable.
- the polymer A containing a structural unit based on a monomer having an aromatic hydrocarbon group includes a monomer having an aromatic hydrocarbon group, at least one of the first monomers described later, and / or described below. It is preferably obtained by polymerizing with at least one of the second monomers.
- the polymer A containing no structural unit based on a monomer having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one of the first monomers described later, and is preferably the first single amount. It is more preferable to obtain it by copolymerizing at least one kind of the body and at least one kind of the second monomer described later.
- the first monomer is a monomer having a carboxyl group in the molecule.
- the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic acid anhydride, maleic acid semi-ester and the like. .. Among these, (meth) acrylic acid is preferable.
- the content of the structural unit based on the first monomer in the polymer A is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and 15 to 30% by mass with respect to the total mass of the polymer A. % Is more preferable.
- the content is 5% by mass or more from the viewpoint of developing good developability and controlling edge fuseability. It is preferable that the content is 50% by mass or less from the viewpoint of high resolution of the resist pattern and the shape of the resist pattern, and further from the viewpoint of chemical resistance of the resist pattern.
- the second monomer is a monomer that is non-acidic and has at least one polymerizable unsaturated group in the molecule.
- Examples of the second monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate.
- Tart-butyl (meth) acrylates 2-hydroxyethyl (meth) acrylates, 2-hydroxypropyl (meth) acrylates, cyclohexyl (meth) acrylates, and (meth) acrylates such as 2-ethylhexyl (meth) acrylates; acetic acid.
- examples thereof include esters of vinyl alcohols such as vinyl; and (meth) acrylonitrile. Of these, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, or n-butyl (meth) acrylate is preferable, and methyl (meth) acrylate is more preferable.
- the content of the structural unit based on the second monomer in the polymer A is preferably 1% by mass or more, more preferably 5% by mass or more, and further preferably 15% by mass or more, based on the total mass of the polymer A. It is preferable, and 17% by mass or more is particularly preferable.
- the upper limit is preferably 60% by mass or less, more preferably 50% by mass or less, and further preferably 45% by mass or less.
- 1 to 60% by mass is preferable, 5 to 60% by mass is more preferable, 15 to 50% by mass is further preferable, and 17 ⁇ 45% by mass is particularly preferable.
- the polymer A contains a monomer-based structural unit having an aralkyl group and / or a styrene-based monomer-based structural unit, it suppresses line width thickening and deterioration of resolution when the focal position shifts during exposure. It is preferable from the viewpoint of For example, a copolymer containing a methacrylic acid-based constituent unit, a benzyl methacrylate-based constituent unit, and a styrene-based constituent unit, a methacrylic acid-based constituent unit, a methyl methacrylate-based constituent unit, a benzyl methacrylate-based constituent unit, and a styrene.
- the polymer A has a structural unit based on a monomer having an aromatic hydrocarbon group of 25 to 55% by mass, a structural unit based on the first monomer of 20 to 35% by mass, and a second component. It is preferably a polymer containing 15 to 45% by mass of a constituent unit based on a monomer. In another embodiment, the polymer contains 70 to 90% by mass of a structural unit based on a monomer having an aromatic hydrocarbon group and 10 to 25% by mass of a structural unit based on the first monomer. Is preferable.
- the structural unit based on the monomer having an aromatic hydrocarbon group is 25 to 70% by mass
- the structural unit based on the first monomer is 15 to 25% by mass
- the second unit amount is preferably a polymer containing 1 to 5% by mass of a body-based structural unit.
- the polymer A may have any of a linear structure, a branched structure, and an alicyclic structure in the side chain.
- a monomer having a group having a branched structure in the side chain or a monomer having a group having an alicyclic structure in the side chain a branched structure or an alicyclic structure can be introduced into the side chain of the polymer A. ..
- the group having an alicyclic structure may be a monocyclic ring or a polycyclic ring.
- the monomer containing a group having a branched structure in the side chain include isopropyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and (. Isoamyl (meth) acrylate, tert-amyl (meth) acrylate, sec-amyl (meth) acrylate, 2-octyl (meth) acrylate, 3-octyl (meth) acrylate and tert-octyl (meth) acrylate. And so on.
- isopropyl (meth) acrylate, isobutyl (meth) acrylate, and tert-butyl methacrylate are preferable, and isopropyl methacrylate or tert-butyl methacrylate are more preferable.
- the monomer having a group having an alicyclic structure in the side chain include a monomer having a monocyclic aliphatic hydrocarbon group and a monomer having a polycyclic aliphatic hydrocarbon group.
- a (meth) acrylate having an alicyclic hydrocarbon group having 5 to 20 carbon atoms can be mentioned.
- More specific examples include (meth) acrylic acid (bicyclo [2.2.1] heptyl-2), (meth) acrylic acid-1-adamantyl, (meth) acrylic acid-2-adamantyl, (meth). -3-Methyl-1-adamantyl acrylate, -3,5-dimethyl-1-adamantyl (meth) acrylate, -3-ethyladamantyl (meth) acrylate, -3-methyl-5-methyl (meth) acrylate Ethyl-1-adamantyl, (meth) acrylic acid-3,5,8-triethyl-1-adamantyl, (meth) acrylic acid-3,5-dimethyl-8-ethyl-1-adamantyl, (meth) acrylic acid 2 -Methyl-2-adamantyl, 2-ethyl-2-adamantyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, o
- (meth) acrylic acid esters (meth) acrylic acid cyclohexyl, (meth) acrylic acid (nor) boronyl, (meth) acrylic acid isobornyl, (meth) acrylic acid-1-adamantyl, (meth) acrylic acid -2-adamantyl, fentyl (meth) acrylate, 1-mentyl (meth) acrylate, or tricyclodecane (meth) acrylate is preferred, cyclohexyl (meth) acrylate, (nor) bornyl, (meth) acrylate, Isobornyl (meth) acrylate, -2-adamantyl (meth) acrylate, or tricyclodecane (meth) acrylate are more preferred.
- the polymer A preferably has a reactive group, and more preferably has a structural unit having a reactive group.
- the polymer A may be used alone or in combination of two or more.
- two kinds of polymer A containing a structural unit based on a monomer having an aromatic hydrocarbon group may be mixed and used, or based on a monomer having an aromatic hydrocarbon group. It is preferable to use a mixture of the polymer A containing a structural unit and the polymer A not containing a structural unit based on a monomer having an aromatic hydrocarbon group.
- the ratio of the polymer A containing the structural unit based on the monomer having an aromatic hydrocarbon group is preferably 50% by mass or more, preferably 70% by mass or more, based on the total mass of the polymer A. More preferably, 80% by mass or more is preferable, and 90% by mass or more is more preferable.
- a radical polymerization initiator such as benzoyl peroxide and azoisobutyronitrile is prepared by diluting the above-mentioned one or more monomers with a solvent such as acetone, methyl ethyl ketone, and isopropanol. Is preferably added in an appropriate amount and heated and stirred. In some cases, a part of the mixture is added dropwise to the reaction solution for synthesis. After completion of the reaction, a solvent may be further added to adjust the concentration to a desired level.
- a solvent may be further added to adjust the concentration to a desired level.
- the synthesis means bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.
- the glass transition temperature Tg of the polymer A is preferably 30 to 135 ° C.
- the Tg of the polymer A is preferably 130 ° C. or lower, more preferably 120 ° C. or lower, and particularly preferably 110 ° C. or lower.
- the polymer A having a Tg of 30 ° C. or higher from the viewpoint of improving the edge fuse resistance.
- the Tg of the polymer A is more preferably 40 ° C. or higher, further preferably 50 ° C. or higher, particularly preferably 60 ° C. or higher, and most preferably 70 ° C. or higher.
- the alkali-soluble resin described in the description of the thermoplastic resin layer described later may be used.
- the negative photosensitive composition layer may contain a resin other than the above as the polymer A.
- resins include acrylic resin, styrene-acrylic copolymer, polyurethane resin, polyvinyl alcohol, polyvinyl formal, polyamide resin, polyester resin, polyamide resin, epoxy resin, polyacetal resin, polyhydroxystyrene resin, polyimide resin, and poly. Examples thereof include benzoxazole resin, polysiloxane resin, polyethyleneimine, polyallylamine, and polyalkylene glycol.
- the content of the polymer A is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, further preferably 30 to 70% by mass, and even more preferably 40 to 40% by mass, based on the total mass of the negative photosensitive composition layer. 60% by mass is particularly preferable. It is preferable that the content of the polymer A is 90% by mass or less from the viewpoint of controlling the developing time. On the other hand, it is preferable that the content of the polymer A is 10% by mass or more from the viewpoint of improving the edge fuse resistance.
- the negative photosensitive composition layer preferably contains a polymerizable compound.
- the polymerizable compound is a compound other than the above-mentioned polymer A, and preferably has a molecular weight of less than 5,000.
- the polymerizable group of the polymerizable compound is not particularly limited as long as it is a group involved in the polymerization reaction, and is an ethylenically unsaturated group such as a vinyl group, an acryloyl group, a methacryloyl group, a styryl group, and a maleimide group.
- Groups having a cationically polymerizable group such as an epoxy group and an oxetane group.
- a group having an ethylenically unsaturated group is preferable, and an acryloyl group or a metaacryloyl group is more preferable.
- the number of polymerizable groups in the polymerizable compound is not particularly limited, but one or more is preferable, and two or more are more preferable.
- the upper limit is not particularly limited, but is, for example, 20 or less.
- a compound having one or more ethylenically unsaturated groups is preferable, and two in one molecule, because the negative photosensitive composition layer is more excellent in photosensitivity.
- the compound having the above ethylenically unsaturated group (polyfunctional ethylenically unsaturated compound) is more preferable.
- the number of ethylenically unsaturated groups contained in one molecule of the ethylenically unsaturated compound is preferably 6 or less, more preferably 3 or less, and 2 or less in terms of excellent resolution and peelability. More preferred.
- the content of the bifunctional ethylenically unsaturated compound in the negative photosensitive composition layer with respect to the total mass of the polymerizable compound is 20 from the viewpoint of excellent peelability with respect to the total mass of the negative photosensitive composition layer.
- the upper limit is not particularly limited and may be 100% by mass. That is, all the polymerizable compounds may be bifunctional ethylenically unsaturated compounds.
- a (meth) acrylate compound having a (meth) acryloyl group as a polymerizable group is preferable.
- the negative photosensitive composition layer preferably contains a polymerizable compound B1 having an aromatic ring and two ethylenically unsaturated groups.
- the polymerizable compound B1 is a bifunctional ethylenically unsaturated compound having one or more aromatic rings in one molecule among the above-mentioned polymerizable compounds B.
- the mass ratio of the content of the polymerizable compound B1 to the total mass of the polymerizable compound in the negative photosensitive composition layer is preferably 40% or more, more preferably 50% by mass or more, from the viewpoint of better resolution. , 55% by mass or more is more preferable, and 60% by mass or more is particularly preferable.
- the upper limit is not particularly limited, but from the viewpoint of peelability, for example, it is 100% by mass or less, preferably 99% by mass or less, more preferably 95% by mass or less, further preferably 90% by mass or less, and particularly preferably 85% by mass or less. preferable.
- aromatic ring contained in the polymerizable compound B1 examples include aromatic hydrocarbon rings such as benzene ring, naphthalene ring and anthracene ring, thiophene ring, furan ring, pyrrole ring, imidazole ring, triazole ring and pyridine ring. Heterocycles and fused rings thereof are mentioned, and aromatic hydrocarbon rings are preferable, and benzene rings are more preferable.
- the aromatic ring may have a substituent.
- the polymerizable compound B1 may have only one aromatic ring or may have two or more aromatic rings.
- the polymerizable compound B1 preferably has a bisphenol structure from the viewpoint of improving the resolution by suppressing the swelling of the negative photosensitive composition layer due to the developing solution.
- the bisphenol structure include a bisphenol A structure derived from bisphenol A (2,2-bis (4-hydroxyphenyl) propane) and a bisphenol derived from bisphenol F (2,2-bis (4-hydroxyphenyl) methane).
- examples thereof include an F structure and a bisphenol B structure derived from bisphenol B (2,2-bis (4-hydroxyphenyl) butane), and a bisphenol A structure is preferable.
- Examples of the polymerizable compound B1 having a bisphenol structure include a compound having a bisphenol structure and two polymerizable groups (preferably (meth) acryloyl groups) bonded to both ends of the bisphenol structure. Both ends of the bisphenol structure and the two polymerizable groups may be directly bonded or may be bonded via one or more alkyleneoxy groups. As the alkyleneoxy group added to both ends of the bisphenol structure, an ethyleneoxy group or a propyleneoxy group is preferable, and an ethyleneoxy group is more preferable.
- the number of alkyleneoxy groups added to the bisphenol structure is not particularly limited, but is preferably 4 to 16 per molecule, more preferably 6 to 14.
- the polymerizable compound B1 having a bisphenol structure is described in paragraphs 0072 to 0080 of JP-A-2016-224162, and the contents described in this publication are incorporated in the present specification.
- the polymerizable compound B1 a bifunctional ethylenically unsaturated compound having a bisphenol A structure is preferable, and 2,2-bis (4-((meth) acryloxypolyalkoxy) phenyl) propane is more preferable.
- 2,2-bis (4-((meth) acryloxypolyalkoxy) phenyl) propane examples include 2,2-bis (4- (methacryloxydiethoxy) phenyl) propane (FA-324M, Hitachi Chemical Co., Ltd.).
- polymerizable compound B1 a compound represented by the following general formula (B1) is also preferable.
- R 1 and R 2 independently represent a hydrogen atom or a methyl group, respectively.
- A represents C 2 H 4 .
- B represents C 3 H 6 .
- n1 and n3 are independently integers of 1 to 39, and n1 + n3 are integers of 2 to 40.
- n2 and n4 are independently integers of 0 to 29, and n2 + n4 are integers of 0 to 30.
- the sequence of constituent units of-(AO)-and-(BO)- may be random or block. In the case of a block, either ⁇ (A—O) ⁇ or ⁇ (BO) ⁇ may be on the bisphenyl group side.
- n1 + n2 + n3 + n4 is preferably 2 to 20, more preferably 2 to 16, and even more preferably 4 to 12. Further, n2 + n4 is preferably 0 to 10, more preferably 0 to 4, further preferably 0 to 2, and particularly preferably 0.
- the polymerizable compound B1 may be used alone or in combination of two or more.
- the content of the polymerizable compound B1 is preferably 10% by mass or more, more preferably 20% by mass or more, based on the total mass of the negative photosensitive composition layer, from the viewpoint of better resolution.
- the upper limit is not particularly limited, but from the viewpoint of transferability and edge fusion (a phenomenon in which the photosensitive resin exudes from the end of the transfer member), 70% by mass or less is preferable, and 60% by mass or less is more preferable.
- the negative photosensitive composition layer may contain a polymerizable compound other than the above-mentioned polymerizable compound B1.
- the polymerizable compound other than the polymerizable compound B1 is not particularly limited and may be appropriately selected from known compounds.
- a compound having one ethylenically unsaturated group in one molecule monoofunctional ethylenically unsaturated compound
- a bifunctional ethylenically unsaturated compound having no aromatic ring and a trifunctional or higher ethylenically unsaturated compound. Examples include compounds.
- Examples of the monofunctional ethylenically unsaturated compound include ethyl (meth) acrylate, ethylhexyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinate, polyethylene glycol mono (meth) acrylate, and polypropylene glycol mono (meth) acrylate. , And phenoxyethyl (meth) acrylate.
- Examples of the bifunctional ethylenically unsaturated compound having no aromatic ring include alkylene glycol di (meth) acrylate, polyalkylene glycol di (meth) acrylate, urethane di (meth) acrylate, and trimethylolpropane diacrylate. ..
- Examples of the alkylene glycol di (meth) acrylate include tricyclodecanedimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), tricyclodecanedimethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and the like.
- 1,9-Nonandiol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), ethylene glycol dimethacrylate , 1,10-decanediol diacrylate, and neopentyl glycol di (meth) acrylate.
- the polyalkylene glycol di (meth) acrylate include polyethylene glycol di (meth) acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di (meth) acrylate.
- Examples of the urethane di (meth) acrylate include propylene oxide-modified urethane di (meth) acrylate, and ethylene oxide and propylene oxide-modified urethane di (meth) acrylate.
- Examples of commercially available products include 8UX-015A (manufactured by Taisei Fine Chemical Industry Co., Ltd.), UA-32P (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and UA-1100H (manufactured by Shin Nakamura Chemical Industry Co., Ltd.).
- Examples of the trifunctional or higher functional ethylenically unsaturated compound include dipentaerythritol (tri / tetra / penta / hexa) (meth) acrylate, pentaerythritol (tri / tetra) (meth) acrylate, and trimethylolpropane tri (meth).
- Examples thereof include acrylates, trimethylolpropane tetra (meth) acrylates, trimethylolethanetri (meth) acrylates, isocyanuric acid tri (meth) acrylates, glycerintri (meth) acrylates, and alkylene oxide modified products thereof.
- (tri / tetra / penta / hexa) (meth) acrylate) is a concept including tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, and hexa (meth) acrylate.
- (Tri / tetra) (meth) acrylate” is a concept that includes tri (meth) acrylate and tetra (meth) acrylate.
- Examples of the ethylenically unsaturated compound having 5 to 6 or more functionalities include dipentaerythritol polyacrylate (“A-DPH” manufactured by Shin-Nakamura Chemical Industry Co., Ltd.).
- the negative photosensitive composition layer preferably contains the above-mentioned polymerizable compound B1 and a trifunctional or higher ethylenically unsaturated compound, and the above-mentioned polymerizable compound B1 and two or more trifunctional or higher. It is more preferable to contain an ethylenically unsaturated compound.
- the negative photosensitive composition layer preferably contains the above-mentioned polymerizable compound B1 and two or more trifunctional ethylenically unsaturated compounds.
- alkylene oxide-modified product of the trifunctional or higher ethylenically unsaturated compound examples include caprolactone-modified (meth) acrylate compound (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd. and A-9300-1CL manufactured by Shin-Nakamura Chemical Industry Co., Ltd.).
- KAYARAD registered trademark
- DPCA-20 Nippon Kayaku Co., Ltd.
- A-9300-1CL manufactured by Shin-Nakamura Chemical Industry Co., Ltd.
- alkylene oxide-modified (meth) acrylate compound (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Industry Co., Ltd., EBECRYL (registered trademark) 135 manufactured by Daicel Ornex Co., Ltd., etc.), Acrylate glycerin triacrylate (A-GLY-9E manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), Aronix (registered trademark) TO-2349 (manufactured by Toa Synthetic Co., Ltd.), Aronix M-520 (manufactured by Toa Synthetic Co., Ltd.), and Aronix M- 510 (manufactured by Toa Synthetic Co., Ltd.) can be mentioned.
- a polymerizable compound having an acid group (carboxy group or the like) may be used.
- the acid group may form an acid anhydride group.
- Polymerizable compounds having an acid group include Aronix (registered trademark) TO-2349 (manufactured by Toagosei), Aronix (registered trademark) M-520 (manufactured by Toagosei), and Aronix (registered trademark) M-510 (registered trademark). Toagosei Co., Ltd.).
- the polymerizable compound compound having an acid group for example, the compounds described in paragraphs 0025 to 0030 of JP-A-2004-239942 may be used.
- the polymerizable compound may be used alone or in combination of two or more.
- the lower limit of the content of the polymerizable compound in the negative photosensitive composition layer is preferably 1% by mass or more, more preferably 5% by mass or more, more preferably 20% by mass, based on the total mass of the negative photosensitive composition layer. By mass or more is more preferable, 35% by mass or more is further preferable, and 40% by mass or more is particularly preferable.
- the upper limit is not particularly limited, but is preferably 70% by mass or less, more preferably 60% by mass or less, and further preferably 55% by mass or less.
- the molecular weight (weight average molecular weight when having a molecular weight distribution) of the ethylenically unsaturated compound (including the polymerizable compound B1) is preferably 200 to 3,000, more preferably 280 to 2,200, and 300 to 2, 200 is more preferred.
- the negative photosensitive composition layer preferably contains a polymerization initiator.
- the polymerization initiator is selected according to the type of the polymerization reaction, and examples thereof include a thermal polymerization initiator and a photopolymerization initiator.
- the polymerization initiator may be a radical polymerization initiator or a cationic polymerization initiator.
- the negative photosensitive composition layer preferably contains a photopolymerization initiator.
- the photopolymerization initiator is a compound that initiates the polymerization of a polymerizable compound by receiving active rays such as ultraviolet rays, visible rays and X-rays.
- the photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used. Examples of the photopolymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator, and a photoradical polymerization initiator is preferable.
- Examples of the photoradical polymerization initiator include a photopolymerization initiator having an oxime ester structure, a photopolymerization initiator having an ⁇ -aminoalkylphenone structure, a photopolymerization initiator having an ⁇ -hydroxyalkylphenone structure, and an acylphosphine oxide. Examples thereof include a photopolymerization initiator having a structure and a photopolymerization initiator having an N-phenylglycine structure.
- the negative photosensitive composition layer contains 2,4,5-triarylimidazole dimer as a photoradical polymerization initiator from the viewpoints of photosensitive, visibility of exposed and unexposed areas, and resolution. It preferably contains at least one selected from the group consisting of the body and its derivatives.
- the two 2,4,5-triarylimidazole structures in the 2,4,5-triarylimidazole dimer and its derivatives may be the same or different.
- Derivatives of the 2,4,5-triarylimidazole dimer include, for example, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di.
- the photoradical polymerization initiator for example, the polymerization initiator described in paragraphs 0031 to 0042 of JP-A-2011-95716 and paragraphs 0064-0081 of JP-A-2015-14783 may be used.
- photoradical polymerization initiator examples include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisyl (p, p'-dimethoxybenzyl), and TAZ-110 (trade name:).
- Examples of commercially available photoradical polymerization initiators include 1- [4- (phenylthio)] -1,2-octanedione-2- (O-benzoyloxime) (trade name: IRGACURE® OXE-01). , BASF), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] etanone-1- (O-acetyloxime) (trade name: IRGACURE OXE-02, BASF) IRGACURE OXE-03 (BASF), IRGACURE OXE-04 (BASF), 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4) -Morphorinyl) Phenyl] -1-butanone (trade name: Omnirad 379EG, manufactured by IGM Resins B.V.), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1
- Examples of commercially available photo-radical polymerization initiators include alkylphenone compounds having the trade name “Omnirad 379” (manufactured by IGM Resins B.V.).
- the photocationic polymerization initiator is a compound that generates an acid by receiving active light rays.
- a compound that is sensitive to active light having a wavelength of 300 nm or more, preferably a wavelength of 300 to 450 nm and generates an acid is preferable, but its chemical structure is not limited.
- a photocationic polymerization initiator that is not directly sensitive to active light with a wavelength of 300 nm or more is also a sensitizer if it is a compound that is sensitive to active light with a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. Can be preferably used in combination with.
- a photocationic polymerization initiator that generates an acid having a pKa of 4 or less is preferable, a photocationic polymerization initiator that generates an acid having a pKa of 3 or less is more preferable, and an acid having a pKa of 2 or less is used.
- the generated photocationic polymerization initiator is particularly preferred.
- the lower limit of pKa is not particularly defined, but is preferably -10.0 or higher, for example.
- Examples of the photocationic polymerization initiator include an ionic photocationic polymerization initiator and a nonionic photocationic polymerization initiator.
- Examples of the ionic photocationic polymerization initiator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts.
- the ionic photocationic polymerization initiator described in paragraphs 0114 to 0133 of JP-A-2014-085643 may be used.
- nonionic photocationic polymerization initiator examples include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds.
- trichloromethyl-s-triazines the diazomethane compound and the imide sulfonate compound
- the compounds described in paragraphs 0083 to 0088 of JP-A-2011-22149 may be used.
- the oxime sulfonate compound the compound described in paragraphs 0084 to 0088 of International Publication No. 2018/179640 may be used.
- the negative photosensitive composition layer preferably contains a photoradical polymerization initiator, and more preferably contains at least one selected from the group consisting of 2,4,5-triarylimidazole dimers and derivatives thereof. preferable.
- the photopolymerization initiator may be used alone or in combination of two or more.
- the content of the photopolymerization initiator is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and more preferably 1.0% by mass, based on the total mass of the negative photosensitive composition layer. % Or more is more preferable.
- the upper limit is not particularly limited, but is preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, still more preferably 5% by mass or less, based on the total mass of the negative photosensitive composition layer. ..
- the negative photosensitive composition layer has a maximum absorption wavelength of 450 nm or more in the wavelength range of 400 to 780 nm at the time of color development from the viewpoints of visibility of exposed and unexposed areas, pattern visibility after development, and resolution. It is also preferable to include a dye (also referred to as "dye N") whose maximum absorption wavelength is changed by an acid, a base, or a radical. When the dye N is contained, the detailed mechanism is unknown, but the adhesion to the adjacent layer (for example, a water-soluble resin layer) is improved, and the resolution is more excellent.
- the term "the maximum absorption wavelength is changed by an acid, a base, or a radical” means that the dye in a color-developing state is decolorized by an acid, a base, or a radical, and the dye in a decolorized state is decolorized. It may mean any aspect of a mode in which a color is developed by an acid, a base, or a radical, and a mode in which a dye in a color-developing state changes to a color-developing state of another hue.
- the dye N may be a compound that changes its color from the decolorized state by exposure and may be a compound that changes its color from the decolorized state by exposure.
- it may be a dye whose color development or decolorization state changes due to the generation and action of an acid, a base, or a radical in the negative photosensitive composition layer by exposure, and the negative type by the acid, the base, or the radical. It may be a dye whose color development or decolorization state changes by changing the state (for example, pH) in the photosensitive composition layer. Further, it may be a dye that changes the state of color development or decolorization by directly receiving an acid, a base, or a radical as a stimulus without going through exposure.
- the dye N is preferably a dye whose maximum absorption wavelength is changed by an acid or a radical, and more preferably a dye whose maximum absorption wavelength is changed by a radical. ..
- the negative photosensitive composition layer is a negative photosensitive composition layer
- the negative photosensitive composition layer is a radical as the dye N from the viewpoint of visibility and resolution of the exposed portion and the non-exposed portion. It is preferable to contain both a dye whose maximum absorption wavelength changes depending on the temperature and a photoradical polymerization initiator.
- the dye N is preferably a dye that develops color by an acid, a base, or a radical.
- a photoradical polymerization initiator, a photocationic polymerization initiator (photoacid generator), or a photobase generator is added to a negative photosensitive composition layer, and a photoradical is applied after exposure.
- a radical-reactive dye, an acid-reactive dye, or a base-reactive dye for example, a leuco dye
- a radical-reactive dye, an acid-reactive dye, or a base-reactive dye for example, a leuco dye
- the dye N preferably has a maximum absorption wavelength of 550 nm or more in the wavelength range of 400 to 780 nm at the time of color development, more preferably 550 to 700 nm. It is more preferably ⁇ 650 nm. Further, the dye N may have only one maximum absorption wavelength in the wavelength range of 400 to 780 nm at the time of color development, or may have two or more. When the dye N has two or more maximum absorption wavelengths in the wavelength range of 400 to 780 nm at the time of color development, the maximum absorption wavelength having the highest absorbance among the two or more maximum absorption wavelengths may be 450 nm or more.
- the maximum absorption wavelength of the dye N is the transmission spectrum of the solution containing the dye N (liquid temperature 25 ° C.) in the range of 400 to 780 nm using a spectrophotometer: UV3100 (manufactured by Shimadzu Corporation) in an atmospheric atmosphere. Is measured and the wavelength at which the intensity of light is minimized (maximum absorption wavelength) is detected.
- Examples of the dye that develops or decolorizes by exposure include leuco compounds.
- Examples of the dye that is decolorized by exposure include a leuco compound, a diarylmethane dye, an oxadin dye, a xanthene dye, an iminonaphthoquinone dye, an azomethin dye, and an anthraquinone dye.
- As the dye N a leuco compound is preferable from the viewpoint of visibility of the exposed portion and the non-exposed portion.
- the leuco compound examples include a leuco compound having a triarylmethane skeleton (triarylmethane dye), a leuco compound having a spiropyran skeleton (spiropylan dye), a leuco compound having a fluorane skeleton (fluorane dye), and a diarylmethane skeleton.
- triarylmethane dye a leuco compound having a triarylmethane skeleton
- spiropyran skeleton a leuco compound having a spiropyran skeleton
- fluorane dye fluorane skeleton
- diarylmethane skeleton examples include a diarylmethane skeleton having a diarylmethane skeleton.
- leuco compound (diarylmethane dye) having a leuco compound (diarylmethane dye), a leuco compound having a rhodamine lactam skeleton (lodamine lactam dye), a leuco compound having an indrill phthalide skeleton (indrill phthalide dye), and a leuco auramine skeleton.
- Leuco compounds (leuco-auramine-based dyes) can be mentioned.
- triarylmethane-based dyes or fluorane-based dyes are preferable, and leuco compounds (triphenylmethane-based dyes) or fluorane-based dyes having a triphenylmethane skeleton are more preferable.
- the leuco compound preferably has a lactone ring, a surujin ring, or a sultone ring from the viewpoint of visibility of the exposed portion and the non-exposed portion.
- the lactone ring, sultin ring, or sulton ring of the leuco compound is reacted with the radical generated from the photoradical polymerization initiator or the acid generated from the photocationic polymerization initiator to change the leuco compound into a closed ring state.
- the color can be decolorized, or the radical compound can be changed to an open ring state to develop a color.
- the leuco compound is preferably a compound having a lactone ring, a sultone ring, or a sultone ring, and the lactone ring, the sultone ring, or the sultone ring is opened by a radical or an acid to develop a color, and the lactone ring is provided, and the radical or the leuco compound is used.
- a compound in which the lactone ring is opened by an acid to develop a color is more preferable.
- Examples of the dye N include the following dyes and leuco compounds. Specific examples of the dyes among the dyes N include Brilliant Green, Ethyl Violet, Methyl Green, Crystal Violet, Basic Fuxin, Methyl Violet 2B, Kinaldine Red, Rose Bengal, Metanyl Yellow, Timor Sulfophthalein, Xylenol Blue, and Methyl.
- leuco compound among the dyes N include p, p', p "-hexamethyltriaminotriphenylmethane (leucocrystal violet), Pergascript Blue SRB (manufactured by Ciba Geigy), crystal violet lactone, and malakite green lactone.
- the dye N is preferably a dye whose maximum absorption wavelength is changed by radicals from the viewpoints of visibility of exposed and unexposed areas, pattern visibility after development, and resolution, and is a dye that develops color by radicals. It is more preferable to have.
- As the dye N leuco crystal violet, crystal violet lactone, brilliant green, or Victoria pure blue-naphthalene sulfonate is preferable.
- the dye N may be used alone or in combination of two or more.
- the content of the dye N is 0.1 mass with respect to the total mass of the negative photosensitive composition layer from the viewpoints of visibility of the exposed portion and the non-exposed portion, pattern visibility after development, and resolution. % Or more is preferable, 0.1 to 10% by mass is more preferable, 0.1 to 5% by mass is further preferable, and 0.1 to 1% by mass is particularly preferable.
- the content of the dye N means the content of the dye when all of the dye N contained in the total mass of the negative photosensitive composition layer is in a colored state.
- a method for quantifying the content of dye N will be described by taking a dye that develops color by radicals as an example.
- a solution prepared by dissolving 0.001 g and 0.01 g of the dye in 100 mL of methyl ethyl ketone is prepared.
- Irradicure OXE01 (trade name, BASF Japan Co., Ltd.), a photoradical polymerization initiator, is added to each of the obtained solutions, and radicals are generated by irradiating with light of 365 nm to bring all the dyes into a colored state.
- the absorbance of each solution having a liquid temperature of 25 ° C. is measured using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation), and a calibration curve is prepared.
- UV3100 UV3100, manufactured by Shimadzu Corporation
- the absorbance of the solution in which all the dyes are colored is measured by the same method as above except that 3 g of the negative photosensitive composition layer is dissolved in methyl ethyl ketone instead of the dye. From the absorbance of the obtained solution containing the negative photosensitive composition layer, the content of the dye contained in the negative photosensitive composition layer is calculated based on the calibration curve.
- the negative type photosensitive composition layer 3 g is the same as 3 g of the total solid content in the composition for forming the negative type photosensitive composition layer.
- the negative photosensitive composition layer is a negative photosensitive composition layer
- the heat-crosslinkable compound having an ethylenically unsaturated group which will be described later, is not treated as a polymerizable compound, but is treated as a heat-crosslinkable compound.
- the heat-crosslinkable compound include a methylol compound and a blocked isocyanate compound. Of these, a blocked isocyanate compound is preferable from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film.
- the blocked isocyanate compound reacts with a hydroxy group and a carboxy group, for example, when the resin and / or the polymerizable compound has at least one of the hydroxy group and the carboxy group, the hydrophilicity of the formed film decreases.
- the function tends to be enhanced.
- the blocked isocyanate compound refers to "a compound having a structure in which the isocyanate group of isocyanate is protected (so-called masked) with a blocking agent".
- the dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100 to 160 ° C, more preferably 130 to 150 ° C.
- the dissociation temperature of the blocked isocyanate means "the temperature of the heat absorption peak associated with the deprotection reaction of the blocked isocyanate when measured by DSC (Differential scanning calorimetry) analysis using a differential scanning calorimeter".
- DSC Different scanning calorimeter
- a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Co., Ltd. can be preferably used.
- the differential scanning calorimeter is not limited to this.
- the blocking agent having a dissociation temperature of 100 to 160 ° C. for example, at least one selected from oxime compounds is preferable from the viewpoint of storage stability.
- the blocked isocyanate compound preferably has an isocyanurate structure, for example, from the viewpoint of improving the brittleness of the membrane and improving the adhesion to the transferred body.
- the blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by subjecting hexamethylene diisocyanate to isocyanurate to protect it.
- a compound having an oxime structure using an oxime compound as a blocking agent is more likely to have a dissociation temperature in a preferable range than a compound having no oxime structure, and has less development residue. It is preferable from the viewpoint of easy operation.
- the blocked isocyanate compound may have a polymerizable group.
- the polymerizable group is not particularly limited, and a known polymerizable group can be used, and a radically polymerizable group is preferable.
- the polymerizable group include an ethylenically unsaturated group such as a (meth) acryloxy group, a (meth) acrylamide group, and a styryl group, and a group having an epoxy group such as a glycidyl group.
- an ethylenically unsaturated group is preferable, a (meth) acryloxy group is more preferable, and an acryloxy group is further preferable.
- blocked isocyanate compound a commercially available product can be used.
- examples of commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP (all manufactured by Showa Denko KK), and block type.
- examples thereof include the Duranate series (for example, Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Co., Ltd.).
- the blocked isocyanate compound a compound having the following structure can also be used.
- the heat-crosslinkable compound may be used alone or in combination of two or more.
- the content of the heat-crosslinkable compound is preferably 1 to 50% by mass, preferably 5 to 30% by mass, based on the total mass of the negative-type photosensitive composition layer. More preferably by mass.
- the negative photosensitive composition layer may contain known additives in addition to the above components, if necessary.
- the additive include radical polymerization inhibitors, sensitizers, plasticizers, heterocyclic compounds (triazole and the like), benzotriazoles, carboxybenzotriazoles, pyridines (isonicotinamide and the like), purine bases (adenine and the like). ), And a surfactant.
- Each additive may be used alone or in combination of two or more.
- the negative photosensitive composition layer may contain a radical polymerization inhibitor.
- the radical polymerization inhibitor include the thermal polymerization inhibitor described in paragraph 0018 of Japanese Patent No. 4502784. Of these, phenothiazine, phenoxazine, or 4-methoxyphenol is preferable.
- examples of other radical polymerization inhibitors include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, diphenylnitrosamine and the like. It is preferable to use the nitrosophenylhydroxyamine aluminum salt as a radical polymerization inhibitor so as not to impair the sensitivity of the negative photosensitive composition layer.
- the preferred content of the radical polymerization inhibitor is the same as in the first A embodiment.
- benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-benzotriazole, and the like. Examples thereof include bis (N-2-ethylhexyl) aminomethylene-1,2,3-tolyltriazole and bis (N-2-hydroxyethyl) aminomethylene-1,2,3-benzotriazole.
- carboxybenzotriazoles examples include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, and N- (N, N-di-2-ethylhexyl) aminomethylene.
- Carboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzotriazole, and N- (N, N-di-2-ethylhexyl) Aminoethylene carboxybenzotriazole and the like can be mentioned.
- a commercially available product such as CBT-1 (Johoku Chemical Industry Co., Ltd., trade name) can be used.
- the total content of the benzotriazols and the carboxybenzotriazols is preferably 0.01 to 3% by mass, preferably 0.05 to 1% by mass, based on the total mass of the negative photosensitive composition layer. Is more preferable.
- the content is 0.01% by mass or more, the storage stability of the negative photosensitive composition layer is more excellent.
- the content is 3% by mass or less, the maintenance of sensitivity and the suppression of dye decolorization are more excellent.
- the negative photosensitive composition layer may contain a sensitizer.
- the sensitizer is not particularly limited, and known sensitizers, dyes and pigments can be used.
- Examples of the sensitizer include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, and triazole compounds (for example). 1,2,4-triazole), stilben compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridin compounds.
- the sensitizer may be used alone or in combination of two or more.
- the content of the sensitizer can be appropriately selected depending on the purpose, but the sensitivity to the light source is improved and the curing rate is improved by the balance between the polymerization rate and the chain transfer. From the viewpoint, 0.01 to 5% by mass is preferable, and 0.05 to 1% by mass is more preferable with respect to the total mass of the negative photosensitive composition layer.
- the negative photosensitive composition layer may contain at least one selected from the group consisting of a plasticizer and a heterocyclic compound.
- the plasticizer and the heterocyclic compound include the compounds described in paragraphs 097 to 0103 and 0111 to 0118 of International Publication No. 2018/179640.
- the negative photosensitive composition layer preferably contains a surfactant. Examples of the surfactant include the same surfactants as those in the first A embodiment, and the preferred embodiments are also the same.
- the negative photosensitive composition layer includes metal oxide particles, antioxidants, dispersants, acid growth agents, development accelerators, conductive fibers, ultraviolet absorbers, thickeners, cross-linking agents, and organic or inorganic materials. It may further contain known additives such as anti-precipitation agents. Additives contained in the negative photosensitive composition layer are described in paragraphs 0165 to 0184 of JP-A-2014-085643, and the contents of this publication are incorporated in the present specification.
- the water content in the negative photosensitive composition layer is preferably 0.01 to 1.0% by mass, more preferably 0.05 to 0.5% by mass, from the viewpoint of improving reliability and laminateability.
- the layer thickness (thickness) of the negative photosensitive composition layer is generally 0.1 to 300 ⁇ m, preferably 0.2 to 100 ⁇ m, more preferably 0.5 to 50 ⁇ m, and 0.5 to 15 ⁇ m. Is more preferable, 0.5 to 10 ⁇ m is particularly preferable, and 0.5 to 8 ⁇ m is most preferable. As a result, the developability of the negative photosensitive composition layer can be improved, and the resolution can be improved. Further, in one embodiment, 0.5 to 5 ⁇ m is preferable, 0.5 to 4 ⁇ m is more preferable, and 0.5 to 3 ⁇ m is further preferable.
- the transmittance of light having a wavelength of 365 nm in the negative photosensitive composition layer is preferably 10% or more, more preferably 30% or more, still more preferably 50% or more.
- the upper limit is not particularly limited, but is preferably 99.9% or less.
- the negative photosensitive composition layer may contain a predetermined amount of impurities.
- impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogen and ions thereof.
- halide ions, sodium ions, and potassium ions are likely to be mixed as impurities, so the following content is preferable.
- the content of impurities in the negative photosensitive composition layer is preferably 80 ppm or less, more preferably 10 ppm or less, still more preferably 2 ppm or less on a mass basis.
- the content of impurities may be 1 ppb or more, or 0.1 ppm or more, on a mass basis.
- the impurities can be quantified by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.
- ICP Inductively Coupled Plasma
- the content of compounds such as benzene, formaldehyde, trichlorethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N, N-dimethylformamide, N, N-dimethylacetamide, and hexane in the negative photosensitive composition layer is , Preferably less.
- the content of these compounds with respect to the total mass of the negative photosensitive composition layer is preferably 100 ppm or less, more preferably 20 ppm or less, still more preferably 4 ppm or less on a mass basis.
- the lower limit can be 10 ppb or more and 100 ppb or more with respect to the total mass of the negative photosensitive composition layer on a mass basis.
- the content of these compounds can be suppressed in the same manner as the above-mentioned metal impurities. Further, it can be quantified by a known measurement method.
- the water content in the negative photosensitive composition layer is preferably 0.01 to 1.0% by mass, more preferably 0.05 to 0.5% by mass, from the viewpoint of improving reliability and laminateability.
- the negative photosensitive composition layer may be a colored resin layer containing a pigment.
- the liquid crystal display window of an electronic device may have a cover glass having a black frame-shaped light-shielding layer formed on the peripheral edge of the back surface of a transparent glass substrate or the like to protect the liquid crystal display window. be.
- a colored resin layer can be used to form such a light-shielding layer.
- the pigment may be appropriately selected according to the desired hue, and can be selected from black pigments, white pigments, and chromatic pigments other than black and white. Among them, when forming a black pattern, a black pigment is preferably selected as the pigment.
- the black pigment a known black pigment (organic pigment, inorganic pigment, etc.) can be appropriately selected as long as the effect of the present invention is not impaired.
- the black pigment for example, carbon black, titanium oxide, titanium carbide, iron oxide, titanium oxide, graphite and the like are preferably mentioned from the viewpoint of optical density, and carbon black is particularly preferable.
- carbon black from the viewpoint of surface resistance, carbon black having at least a part of the surface coated with a resin is preferable.
- the particle size of the black pigment is preferably 0.001 to 0.1 ⁇ m, more preferably 0.01 to 0.08 ⁇ m in terms of number average particle size.
- the particle size refers to the diameter of a circle when the area of the pigment particles is obtained from a photographic image of the pigment particles taken with an electronic microscope and a circle having the same area as the area of the pigment particles is considered, and the number average particle size. Is an average value obtained by obtaining the above particle size for any 100 particles and averaging the obtained 100 particle sizes.
- the white pigment described in paragraphs 0015 and 0114 of JP-A-2005-007765 can be used as the white pigment.
- the white pigments as the inorganic pigment, titanium oxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, or barium sulfate are preferable, and titanium oxide or zinc oxide is more preferable. Titanium oxide is preferable, and titanium oxide is more preferable.
- rutile-type or anatase-type titanium oxide is more preferable, and rutile-type titanium oxide is particularly preferable.
- the surface of titanium oxide may be treated with silica, alumina, titania, zirconia, or an organic substance, or may be subjected to two or more treatments.
- the catalytic activity of titanium oxide is suppressed, and heat resistance, fading and the like are improved.
- at least one of alumina treatment and zirconia treatment is preferable as the surface treatment of the surface of titanium oxide, and both alumina treatment and zirconia treatment are particularly preferable. ..
- the negative photosensitive composition layer when the negative photosensitive composition layer is a colored resin layer, the negative photosensitive composition layer may further contain a chromatic pigment other than the black pigment and the white pigment from the viewpoint of transferability. preferable.
- a chromatic pigment when a chromatic pigment is contained, the particle size of the chromatic pigment is preferably 0.1 ⁇ m or less, more preferably 0.08 ⁇ m or less, in that the dispersibility is more excellent.
- chromatic pigments include Victoria Pure Blue BO (Color Index (hereinafter CI) 42595), Auramine (CI41000), Fat Black HB (CI26150), and Monolite.
- Pigment Red 180 C.I. I. Pigment Red 192, C.I. I. Pigment Red 215, C.I. I. Pigment Green 7, C.I. I. Pigment Blue 15: 1, C.I. I. Pigment Blue 15: 4, C.I. I. Pigment Blue 22, C.I. I. Pigment Blue 60, C.I. I. Pigment Blue 64, and C.I. I. Pigment Violet 23 and the like. Above all, C.I. I. Pigment Red 177 is preferred.
- the content of the pigment is preferably more than 3% by mass and 40% by mass or less, preferably more than 3% by mass and 35% by mass, based on the total mass of the negative type photosensitive composition layer. More preferably, it is more preferably 5% by mass or more and 35% by mass or less, and particularly preferably 10% by mass or more and 35% by mass or less.
- the content of the pigment other than the black pigment is preferably 30% by mass or less with respect to the black pigment. It is more preferably from 20% by mass, still more preferably from 3 to 15% by mass.
- the negative photosensitive composition layer contains a black pigment and the negative photosensitive composition layer is formed of a composition for forming a negative photosensitive composition layer
- a black pigment preferably carbon black
- the dispersion liquid may be prepared by adding a mixture obtained by previously mixing a black pigment and a pigment dispersant to an organic solvent (or vehicle) and dispersing it with a disperser.
- the pigment dispersant may be selected depending on the pigment and the solvent, and for example, a commercially available dispersant can be used.
- the vehicle refers to a portion of the medium in which the pigment is dispersed when the pigment is dispersed, and is a liquid, a binder component that holds the black pigment in a dispersed state, and a solvent component that dissolves and dilutes the binder component. (Organic solvent) and.
- the disperser is not particularly limited, and examples thereof include known dispersers such as a kneader, a roll mill, an attritor, a super mill, a dissolver, a homomixer, and a sand mill. Further, it may be finely pulverized by mechanical grinding using frictional force.
- disperser and fine pulverization the description of "Encyclopedia of Pigments" (Kunizo Asakura, First Edition, Asakura Shoten, 2000, 438, 310) can be referred to.
- thermoplastic resin layer is usually arranged between the temporary support and the negative photosensitive composition layer.
- the thermoplastic resin layer is usually arranged between the temporary support and the negative photosensitive composition layer.
- the thermoplastic resin layer contains resin.
- the resin contains a thermoplastic resin in part or in whole. That is, in one embodiment, it is also preferable that the resin of the thermoplastic resin layer is a thermoplastic resin.
- the thermoplastic resin is preferably an alkali-soluble resin.
- alkali-soluble resin include acrylic resin, polystyrene resin, styrene-acrylic copolymer, polyurethane resin, polyvinyl alcohol, polyvinyl formal, polyamide resin, polyester resin, polyamide resin, epoxy resin, polyacetal resin, and polyhydroxystyrene resin.
- an acrylic resin is preferable from the viewpoint of developability and adhesion to an adjacent layer.
- the acrylic resin is at least selected from the group consisting of a structural unit derived from (meth) acrylic acid, a structural unit derived from (meth) acrylic acid ester, and a structural unit derived from (meth) acrylic acid amide. It means a resin having one kind of structural unit.
- the acrylic resin the total content of the structural unit derived from (meth) acrylic acid, the structural unit derived from (meth) acrylic acid ester, and the structural unit derived from (meth) acrylic acid amide is the total content of the acrylic resin. It is preferably 50% by mass or more with respect to the mass.
- the total content of the structural unit derived from (meth) acrylic acid and the structural unit derived from (meth) acrylic acid ester is preferably 30 to 100% by mass, preferably 50 to 100% by mass, based on the total mass of the acrylic resin. 100% by mass is more preferable.
- the alkali-soluble resin is preferably a polymer having an acid group.
- the acid group include a carboxy group, a sulfo group, a phosphoric acid group, and a phosphonic acid group, and a carboxy group is preferable.
- the alkali-soluble resin is more preferably an alkali-soluble resin having an acid value of 60 mgKOH / g or more, and further preferably a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more.
- the upper limit of the acid value of the alkali-soluble resin is not particularly limited, but is preferably 300 mgKOH / g or less, more preferably 250 mgKOH / g or less, further preferably 200 mgKOH / g or less, and particularly preferably 150 mgKOH / g or less.
- the carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more is not particularly limited and can be appropriately selected from known resins and used.
- an alkali-soluble resin which is a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more, described in paragraphs 0033 to 0052 of JP-A-2010-237589.
- Acrylic can be mentioned.
- the copolymerization ratio of the structural unit having a carboxy group in the carboxy group-containing acrylic resin is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and 12 to 30% by mass with respect to the total mass of the acrylic resin. Is more preferable.
- an acrylic resin having a structural unit derived from (meth) acrylic acid is particularly preferable from the viewpoint of developability and adhesion to an adjacent layer.
- the alkali-soluble resin may have a reactive group.
- the reactive group may be any addition-polymerizable group, and an ethylenically unsaturated group; a polycondensable group such as a hydroxy group and a carboxy group; a polyadditive reactive group such as an epoxy group and a (block) isocyanate group may be used. Can be mentioned.
- the weight average molecular weight (Mw) of the alkali-soluble resin is preferably 1,000 or more, more preferably 10,000 to 100,000, and even more preferably 20,000 to 50,000.
- the alkali-soluble resin may be used alone or in combination of two or more.
- the content of the alkali-soluble resin is preferably 10 to 99% by mass, more preferably 20 to 90% by mass, based on the total mass of the thermoplastic resin layer from the viewpoint of developability and adhesion to the adjacent layer. 40 to 80% by mass is more preferable, and 50 to 75% by mass is particularly preferable.
- the thermoplastic resin layer contains a dye having a maximum absorption wavelength of 450 nm or more in the wavelength range of 400 to 780 nm at the time of color development and whose maximum absorption wavelength is changed by an acid, a base, or a radical (also referred to simply as “dye B”). Is preferable.
- the preferred embodiment of the dye B is the same as the preferred embodiment of the dye N described above, except for the points described later.
- the dye B is preferably a dye whose maximum absorption wavelength is changed by an acid or a radical, and more preferably a dye whose maximum absorption wavelength is changed by an acid, from the viewpoint of visibility and resolution of the exposed part and the non-exposed part. ..
- the thermoplastic resin layer contains both a dye whose maximum absorption wavelength changes depending on the acid as the dye B and a compound that generates an acid by light, which will be described later. It is preferable to include it.
- the dye B may be used alone or in combination of two or more.
- the content of the dye B is preferably 0.2% by mass or more, more preferably 0.2 to 6% by mass, based on the total mass of the thermoplastic resin layer from the viewpoint of visibility of the exposed portion and the non-exposed portion. , 0.2 to 5% by mass, more preferably 0.25 to 3.0% by mass.
- the content of the dye B means the content of the dye when all of the dye B contained in the thermoplastic resin layer is in a colored state.
- a method for quantifying the content of dye B will be described by taking a dye that develops color by radicals as an example.
- a solution prepared by dissolving 0.001 g and 0.01 g of the dye in 100 mL of methyl ethyl ketone is prepared.
- Irradicure OXE01 (trade name, BASF Japan Co., Ltd.), a photoradical polymerization initiator, is added to each of the obtained solutions, and radicals are generated by irradiating with light of 365 nm to bring all the dyes into a colored state.
- thermoplastic resin layer (3 g) is the same as the solid content of the composition (3 g).
- the thermoplastic resin layer may contain a compound (also simply referred to as “compound C”) that generates an acid, a base, or a radical by light.
- a compound that receives an active ray such as ultraviolet rays and visible rays to generate an acid, a base, or a radical is preferable.
- known photoacid generators, photobase generators, and photoradical polymerization initiators photoradical generators can be used.
- thermoplastic resin layer may contain a photoacid generator from the viewpoint of resolution.
- the photoacid generator include a photocationic polymerization initiator that may be contained in the negative-type photosensitive composition layer described above, and the same preferred embodiments are used except for the points described below.
- the photoacid generator preferably contains at least one compound selected from the group consisting of an onium salt compound and an oxime sulfonate compound from the viewpoint of sensitivity and resolution, and preferably contains sensitivity, resolution and adhesion. From the viewpoint of sex, it is more preferable to contain an oxime sulfonate compound. Further, as the photoacid generator, a photoacid generator having the following structure is also preferable.
- the thermoplastic resin layer may contain a photoradical polymerization initiator.
- a photoradical polymerization initiator include a photo-radical polymerization initiator which may be contained in the negative-type photosensitive composition layer described above, and the preferred embodiment is also the same.
- the thermoplastic resin composition may contain a photobase generator.
- the photobase generator is not particularly limited as long as it is a known photobase generator, and for example, 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoyl hydroxylamide, O-carbamoyloxime, [[(2, 6-Dinitrobenzyl) Oxy] carbonyl] cyclohexylamine, bis [[(2-nitrobenzyl) oxy] carbonyl] hexane 1,6-diamine, 4- (methylthiobenzoyl) -1-methyl-1-morpholinoetan, (4) -Morholinobenzoyl) -1-benzyl-1-dimethylaminopropane, N- (2-nitrobenzyloxycarbonyl) pyrrolidine, hexaammine cobalt (III) tris (triphenylmethylborate), 2-benzyl-2-dimethylamino- 1- (4
- Compound C may be used alone or in combination of two or more.
- the content of the compound C is preferably 0.1 to 10% by mass, preferably 0.5 to 5% by mass, based on the total mass of the thermoplastic resin layer from the viewpoint of visibility and resolution of the exposed and unexposed areas. More preferably by mass.
- the thermoplastic resin layer preferably contains a plasticizer from the viewpoints of resolution, adhesion to adjacent layers, and developability.
- the plasticizer preferably has a smaller molecular weight (weight average molecular weight when it is an oligomer or a polymer and has a molecular weight distribution) than that of an alkali-soluble resin.
- the molecular weight (weight average molecular weight) of the plasticizer is preferably 200 to 2,000.
- the plasticizer is not particularly limited as long as it is a compound that is compatible with an alkali-soluble resin and exhibits plasticity, but from the viewpoint of imparting plasticity, the plasticizer preferably has an alkyleneoxy group in the molecule, and is a polyalkylene glycol. Compounds are more preferred. It is more preferable that the alkyleneoxy group contained in the plasticizer has a polyethyleneoxy structure or a polypropyleneoxy structure.
- the plasticizer preferably contains a (meth) acrylate compound from the viewpoint of resolution and storage stability.
- the alkali-soluble resin is an acrylic resin and the plasticizer contains a (meth) acrylate compound.
- the (meth) acrylate compound used as a plasticizer include the (meth) acrylate compound described as the polymerizable compound contained in the above-mentioned negative photosensitive composition layer.
- both the thermoplastic resin layer and the negative photosensitive composition layer contain the same (meth) acrylate compound. Is preferable. This is because the thermoplastic resin layer and the negative photosensitive composition layer each contain the same (meth) acrylate compound, so that the diffusion of components between the layers is suppressed and the storage stability is improved.
- the (meth) acrylate compound may not polymerize even in the exposed portion after exposure from the viewpoint of adhesion between the thermoplastic resin layer and the adjacent layer.
- the (meth) acrylate compound used as a plasticizer two or more (meth) in one molecule from the viewpoint of the resolution of the thermoplastic resin layer, the adhesion to the adjacent layer, and the developability.
- Polyfunctional (meth) acrylate compounds having an acryloyl group are preferred.
- a (meth) acrylate compound having an acid group or a urethane (meth) acrylate compound is also preferable.
- the plasticizer may be used alone or in combination of two or more.
- the content of the plasticizer is preferably 1 to 70% by mass with respect to the total mass of the thermoplastic resin layer from the viewpoints of the resolution of the thermoplastic resin layer, the adhesion to the adjacent layer, and the developability. 10 to 60% by mass is more preferable, and 20 to 50% by mass is further preferable.
- the thermoplastic resin layer may contain a sensitizer.
- the sensitizer is not particularly limited, and examples thereof include a sensitizer that may be contained in the negative photosensitive composition layer described above.
- the sensitizer may be used alone or in combination of two or more.
- the content of the sensitizer can be appropriately selected depending on the purpose, but from the viewpoint of improving the sensitivity to the light source and the visibility of the exposed and non-exposed areas, it is 0.01 with respect to the total mass of the thermoplastic resin layer. It is preferably from 5% by mass, more preferably 0.05 to 1% by mass.
- thermoplastic resin layer may contain a known additive such as a surfactant, if necessary. Further, the thermoplastic resin layer is described in paragraphs 0189 to 0193 of JP-A-2014-085643, and the contents described in this publication are incorporated in the present specification.
- the layer thickness of the thermoplastic resin layer is not particularly limited, but is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, from the viewpoint of adhesion to adjacent layers.
- the upper limit is not particularly limited, but from the viewpoint of developability and resolvability, 20 ⁇ m or less is preferable, 10 ⁇ m or less is more preferable, and 8 ⁇ m or less is further preferable.
- Intermediate layer (intermediate layer B) In the transfer film 30, the intermediate layer (intermediate layer B) 25 is present between the thermoplastic resin layer 23 and the negative photosensitive composition layer 27, so that the thermoplastic resin layer 23 and the negative photosensitive composition are formed. It is possible to suppress the mixing of components that may occur during the coating formation of the layer 27 and the storage after the coating formation.
- a water-soluble resin layer containing a water-soluble resin can be used.
- an oxygen blocking layer having an oxygen blocking function which is described as a “separation layer” in JP-A-5-07724, can also be used.
- the intermediate layer (intermediate layer B) is an oxygen blocking layer
- the sensitivity at the time of exposure is improved, the time load of the exposure machine is reduced, and the productivity is improved, which is preferable.
- the oxygen blocking layer used as the intermediate layer (intermediate layer B) may be appropriately selected from the known layers described in the above publications and the like. Of these, an oxygen blocking layer that exhibits low oxygen permeability and is dispersed or dissolved in water or an alkaline aqueous solution (1% by mass aqueous solution of sodium carbonate at 22 ° C.) is preferable.
- the intermediate layer (intermediate layer B) is preferably a water-soluble resin layer containing a water-soluble resin.
- the intermediate layer (intermediate layer B) is a water-soluble resin layer, various components that may be contained in the water-soluble resin layer will be described.
- the water-soluble resin layer contains a resin.
- the resin contains a water-soluble resin in part or in whole.
- the resin that can be used as the water-soluble resin include polyvinyl alcohol-based resin, polyvinylpyrrolidone-based resin, cellulose-based resin, acrylamide-based resin, polyethylene oxide-based resin, gelatin, vinyl ether-based resin, polyamide resin, and their co-weight. Examples include resins such as coalescing.
- a (meth) acrylic acid / vinyl compound copolymer or the like can also be used as the water-soluble resin.
- the copolymer of (meth) acrylic acid / vinyl compound a copolymer of (meth) acrylic acid / allyl (meth) acrylic acid is preferable, and a copolymer of methacrylic acid / allyl methacrylate is more preferable.
- the water-soluble resin is a copolymer of (meth) acrylic acid / vinyl compound
- the composition ratio (mol%) is preferably 90/10 to 20/80, preferably 80/20 to 30/70. More preferred.
- the lower limit of the weight average molecular weight of the water-soluble resin is preferably 5,000 or more, more preferably 7,000 or more, and even more preferably 10,000 or more.
- the upper limit thereof is preferably 200,000 or less, more preferably 100,000 or less, and even more preferably 50,000 or less.
- the dispersity (Mw / Mn) of the water-soluble resin is preferably 1 to 10, more preferably 1 to 5.
- the resin in the water-soluble resin layer (intermediate layer B) is one surface of the water-soluble resin layer (intermediate layer B) in terms of further improving the ability of the water-soluble resin layer (intermediate layer B) to suppress interlayer mixing. It is preferable that the resin is different from the resin contained in the layer arranged on the side and the resin contained in the layer arranged on the other surface side. For example, when the polymer A is contained in the negative photosensitive composition layer 27 and the thermoplastic resin (alkali-soluble resin) is contained in the thermoplastic resin layer 23, the water-soluble resin layer (intermediate layer B) 25 is contained.
- the resin is preferably a resin different from the polymer A and the thermoplastic resin (alkali-soluble resin).
- the water-soluble resin preferably contains polyvinyl alcohol, and more preferably contains both polyvinyl alcohol and polyvinylpyrrolidone, in terms of further improving the oxygen blocking property and the ability to suppress interlayer mixing.
- the water-soluble resin may be used alone or in combination of two or more.
- the content of the water-soluble resin is not particularly limited, but is 50% by mass or more with respect to the total mass of the water-soluble resin layer (intermediate layer B) in terms of further improving the oxygen blocking property and the ability to suppress interlayer mixing. It is preferable that 70% by mass or more is more preferable, 80% by mass or more is further preferable, and 90% by mass or more is particularly preferable.
- the upper limit is not particularly limited, but is preferably 99.9% by mass or less, and more preferably 99.8% by mass or less.
- the water-soluble resin layer (intermediate layer B) may optionally contain a known additive such as a surfactant.
- the layer thickness of the water-soluble resin layer (intermediate layer B) is not particularly limited, but is preferably 0.1 to 5 ⁇ m, more preferably 0.5 to 3 ⁇ m.
- the thickness of the water-soluble resin layer (intermediate layer B) is within the above range, the oxygen blocking property is not lowered and the ability to suppress interlaminar mixing is excellent. Further, it is possible to suppress an increase in the time for removing the water-soluble resin layer (intermediate layer B) during development.
- the method for producing the transfer film of the first B embodiment is not particularly limited, and a known method can be used.
- a method for producing the transfer film 30 for example, a thermoplastic resin composition is applied to the surface of the temporary support 21 to form a coating film, and the coating film is further dried to form the thermoplastic resin layer 23. And a step of applying a water-soluble resin composition to the surface of the thermoplastic resin layer 23 to form a coating film, and further drying the coating film to form an intermediate layer (intermediate layer B) 25.
- a negative-type photosensitive composition layer-forming composition is applied to the surface of the layer (intermediate layer B) 25 to form a coating film, and the coating film is further dried to form a negative-type photosensitive composition layer 27.
- the transfer film 30 is manufactured by crimping the protective film 31 onto the ultraviolet absorbing layer 29 of the laminate manufactured by the above-mentioned manufacturing method.
- the method for producing the transfer film of the first B embodiment includes a step of providing the protective film 31 so as to be in contact with the surface of the ultraviolet absorbing layer 29 opposite to the side having the temporary support 21. It is preferable to manufacture a transfer film 30 including a thermoplastic resin layer 23, an intermediate layer (intermediate layer B) 25, a negative photosensitive composition layer 27, an ultraviolet absorbing layer 29, and a protective film 31.
- the transfer film 30 may be wound up to prepare and store the transfer film in the form of a roll.
- the roll-type transfer film can be provided as it is in the bonding process with the substrate in the roll-to-roll method described later.
- the ultraviolet absorbing layer 29, the negative photosensitive composition layer 27, and the intermediate layer (intermediate layer B) 25 are formed on the protective film 31, and then the intermediate layer is formed.
- a method of forming the thermoplastic resin layer 23 on the surface of the (intermediate layer B) 25 may be used.
- the method for forming the thermoplastic resin layer on the temporary support is not particularly limited, and a known method can be used. For example, it can be formed by applying a composition for forming a thermoplastic resin layer on a temporary support and drying it if necessary.
- the composition for forming the thermoplastic resin layer preferably contains the above-mentioned various components for forming the thermoplastic resin layer and a solvent.
- the preferable range of the content of each component with respect to the total solid content of the composition is the same as the preferable range of the content of each component with respect to the total mass of the thermoplastic resin layer described above. be.
- the solvent is not particularly limited as long as each component other than the solvent can be dissolved or dispersed, and a known solvent can be used.
- the solvent include the same solvents as those contained in the composition for forming a negative photosensitive composition layer described later, and the preferred embodiments are also the same.
- the content of the solvent is preferably 50 to 1,900 parts by mass, more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content of the composition.
- thermoplastic resin layer is not particularly limited as long as it can form a layer containing the above components, and for example, known coating methods (slit coating, spin coating, curtain coating, inkjet coating, etc.) can be used. Can be mentioned.
- the water-soluble resin composition preferably contains various components forming the above-mentioned intermediate layer B (water-soluble resin layer) and a solvent.
- the preferable range of the content of each component with respect to the total solid content of the composition is the preferable range of the content of each component with respect to the total mass of the intermediate layer B (water-soluble resin layer) described above. It is the same.
- the solvent is not particularly limited as long as it can dissolve or disperse the water-soluble resin, and at least one selected from the group consisting of water and a water-soluble organic solvent is preferable, and water or a water-soluble organic solvent is preferable.
- a mixed solvent with a solvent is more preferable.
- the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin, and alcohols having 1 to 3 carbon atoms are preferable, and methanol or ethanol is more preferable.
- the solvent may be used alone or in combination of two or more.
- the content of the solvent is preferably 50 to 2,500 parts by mass, more preferably 50 to 1,900 parts by mass, and even more preferably 100 to 900 parts by mass with respect to 100 parts by mass of the total solid content of the composition.
- the method for forming the intermediate layer B is not particularly limited as long as it can form a layer containing the above components, and for example, known coating methods (slit coating, spin coating, curtain coating, and curtain coating). Inkjet coating, etc.).
- the negative photosensitive composition layer containing the components (for example, a binder polymer, a polymerizable compound, a polymerization initiator, etc.) constituting the above-mentioned negative photosensitive composition layer and a solvent in terms of excellent productivity. It is preferably formed by a coating method using a forming composition. Specifically, as a method for producing a transfer film according to the first B embodiment, a composition for forming a negative photosensitive composition layer is applied onto an intermediate layer (intermediate layer B) to form a coating film, and the coating film is formed. A method of forming a negative photosensitive composition layer by subjecting the film to a drying treatment is preferable.
- the composition for forming the negative photosensitive composition layer preferably contains various components and a solvent for forming the negative photosensitive composition layer described above.
- the preferable range of the content of each component with respect to the total solid content of the composition is the content of each component with respect to the total mass of the negative photosensitive composition layer described above. It is the same as the preferable range of.
- the solvent is not particularly limited as long as each component other than the solvent can be dissolved or dispersed, and a known solvent can be used.
- alkylene glycol ether solvent for example, alkylene glycol ether solvent, alkylene glycol ether acetate solvent, alcohol solvent (methanol, ethanol, etc.), ketone solvent (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbon solvent (toluene, etc.), aprotonic polarity.
- examples thereof include a solvent (N, N-dimethylformamide, etc.), a cyclic ether solvent (tetratetra, etc.), an ester solvent (npropyl acetate, etc.), an amide solvent, a lactone solvent, and a mixed solvent containing two or more of these.
- the solvent preferably contains at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent.
- a mixed solvent containing at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent and at least one selected from the group consisting of a ketone solvent and a cyclic ether solvent is more preferable.
- a mixed solvent containing at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent, a ketone solvent, and at least three types of a cyclic ether solvent is more preferable.
- alkylene glycol ether solvent examples include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether (propylene glycol monomethyl ether acetate, etc.), propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether, and the like. And dipropylene glycol dialkyl ether.
- alkylene glycol ether acetate solvent examples include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate.
- the solvent described in paragraphs 0092 to 0094 of International Publication No. 2018/179640 and the solvent described in paragraph 0014 of JP-A-2018-177789 may be used, and the contents thereof are described in the present specification. Will be incorporated into.
- the solvent may be used alone or in combination of two or more.
- the content of the solvent is preferably 50 to 1,900 parts by mass, more preferably 50 to 1200 parts by mass, still more preferably 50 to 900 parts by mass with respect to 100 parts by mass of the total solid content of the composition.
- Examples of the method for applying the negative photosensitive composition layer forming composition include a printing method, a spray method, a roll coating method, a bar coating method, a curtain coating method, a spin coating method, and a die coating method (that is, a slit coating method). Law).
- the drying temperature is preferably 80 ° C. or higher, more preferably 90 ° C. or higher.
- the upper limit thereof is preferably 130 ° C. or lower, more preferably 120 ° C. or lower. It can also be dried by continuously changing the temperature.
- the drying time is preferably 20 seconds or longer, more preferably 40 seconds or longer, and even more preferably 60 seconds or longer.
- the upper limit is not particularly limited, but is preferably 600 seconds or less, and more preferably 300 seconds or less.
- the composition for forming an ultraviolet absorbing layer preferably contains the above-mentioned various components forming the ultraviolet absorbing layer and a solvent.
- the preferable range of the content of each component with respect to the total solid content of the composition is the same as the preferable range of the content of each component with respect to the total mass of the ultraviolet absorbing layer described above.
- the solvent is not particularly limited as long as it can dissolve or disperse the components contained in the composition for forming an ultraviolet absorbing layer, and at least one selected from the group consisting of water and a water-miscible organic solvent is preferable, and water is preferable.
- a mixed solvent of water and a water-miscible organic solvent is more preferable.
- the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin, and alcohols having 1 to 3 carbon atoms are preferable, and methanol or ethanol is more preferable.
- the solvent may be used alone or in combination of two or more.
- the content of the solvent is preferably 50 to 2,500 parts by mass, more preferably 50 to 1,900 parts by mass, and even more preferably 100 to 900 parts by mass with respect to 100 parts by mass of the total solid content of the composition.
- the method for forming the ultraviolet absorbing layer is not particularly limited as long as it can form a layer containing the above components, and for example, known coating methods (bar coat coating, slit coating, spin coating, curtain coating, and inkjet coating) are used. Etc.).
- the transfer film of the first B embodiment can be manufactured.
- the method of attaching the protective film to the ultraviolet absorbing layer is not particularly limited, and known methods can be mentioned.
- Examples of the device for adhering the protective film to the ultraviolet absorbing layer include a vacuum laminator and a known laminator such as an auto-cut laminator. It is preferable that the laminator is provided with an arbitrary heatable roller such as a rubber roller and can be pressurized and heated.
- the transfer film of the second aspect of the present invention is A transfer film having a temporary support and a composition layer including a negative photosensitive composition layer and an ultraviolet absorbing layer arranged on the temporary support.
- the ultraviolet absorbing layer is arranged on the side opposite to the temporary support side of the negative photosensitive composition layer.
- the dissolution rate of the ultraviolet absorbing layer calculated by the following measuring method is 60% or more.
- the thickness T1 of the composition layer is measured.
- the ultraviolet absorbing layer is removed from the composition layer, the thickness T2 of the composition layer after the removal of the ultraviolet absorbing layer is measured, and the thickness T2 is subtracted from the thickness T1 to obtain the ultraviolet absorbing layer.
- Thickness T3 is obtained.
- a transfer film with the ultraviolet absorbing layer exposed is prepared and immersed in ion-exchanged water at 25 ° C. for 60 seconds. After the immersion, the thickness T4 of the composition layer in the transfer film is measured. Then, the thickness T5 of the dissolved portion of the ultraviolet absorbing layer is obtained by subtracting the thickness T4 from the thickness T1, and the dissolution rate of the ultraviolet absorbing layer is calculated by the thickness T5 / the thickness T3 ⁇ 100.
- the features of the transfer film of the second aspect of the present invention are that the ultraviolet absorbing layer is arranged on the side opposite to the temporary support of the negative photosensitive composition layer, and the predetermined conditions of the ultraviolet absorbing layer.
- the point that the solubility in water is 60% or more is mentioned.
- the transfer film of the second aspect of the above configuration it is possible to form a pattern in which the tailing shape is suppressed.
- the presumed mechanism of action of the transfer film of the second aspect of the present invention is as follows.
- the transfer film of the second aspect has an ultraviolet absorbing layer on the side opposite to the temporary support of the negative photosensitive composition layer, and due to this structure, on the surface opposite to the temporary support.
- a transfer film When a transfer film is laminated on a substrate so as to be in contact with a substrate (for example, a metal substrate) to form a pattern, even if the incident light from the exposure light source is reflected by the substrate, the reflected light is reflected by the ultraviolet absorbing layer. Can be absorbed. As a result, in the transfer film of the second aspect, interference fringes due to the incident light from the exposure light source and the reflected light on the metal substrate are less likely to occur in the negative photosensitive composition layer at the time of exposure, and the reflected light is not generated. , It is difficult to diffuse into the area (unexposed area) originally shielded by the mask.
- the ultraviolet absorbing layer of the transfer film of the second aspect as a layer having high solubility in water (in other words, a layer having relatively high hydrophilicity). It has also been clarified that the residue of the ultraviolet absorbing layer is less likely to remain during (alkaline development), and due to this, the shape of the formed pattern is less likely to be a tailed shape.
- the negative photosensitive composition layer is usually composed of a hydrophobic component in many cases.
- the ultraviolet absorbing layer in the transfer film is a layer having low solubility in water (in other words, a layer having relatively high hydrophobicity)
- it is negative-type photosensitive by the coating method. It was found that when the composition layer and the ultraviolet absorbing layer are laminated, excessive interlayer mixing between the negative photosensitive composition layer and the ultraviolet absorbing layer may occur, and the shape of the pattern tends to be a tailed shape. is doing. Further, even if the negative photosensitive composition layer and the ultraviolet absorbing layer are laminated by the transfer method, if the ultraviolet absorbing layer is a relatively hydrophobic layer, the negative photosensitive due to the interlaminar movement of the components of both layers.
- the shape of the pattern formed by the transfer film is more excellent (in other words, the tailing shape is more suppressed) and / or the resolution of the transfer film is more excellent. Is better.
- FIG. 3A is a schematic view of the transfer film 40 after the protective film is peeled off.
- the transfer film 40 after peeling off the protective film has a temporary support 41 and a composition layer 42 arranged on the temporary support 41.
- the composition layer 42 is composed of an intermediate layer 43, a negative photosensitive composition layer 45, and an ultraviolet absorbing layer 47 in this order from the temporary support 41 side.
- the thickness T1 of the composition layer 42 arranged on the temporary support 41 in the transfer film 40 is measured.
- the thickness T1 is measured using a stylus type film thickness meter (for example, "DekTak150" manufactured by Bruker). Further, in measuring the thickness T1, any five points are measured and calculated as the average value of each measured value.
- Each thickness such as the thickness T2 and the thickness T4, which will be described later, is also measured by the same procedure as the thickness T1.
- the ultraviolet absorbing layer 47 is removed from the composition layer 42, and the thickness T2 of the composition layer 42A after the ultraviolet absorbing layer 47 is removed is measured.
- the removing method for removing the ultraviolet absorbing layer 47 from the composition layer 42 include tape peeling, wiping with pure water, and the like.
- the thickness T3 of the ultraviolet absorbing layer 47 is obtained by subtracting the thickness T2 from the thickness T1 (see the thickness T3 in FIG. 3A).
- a transfer film 40 (in other words, a transfer film 40 in which the ultraviolet absorbing layer 47 is exposed) is separately prepared after the protective film is peeled off, and this is placed in ion-exchanged water at 25 ° C. 60. Soak for a second, and after soaking, the transfer film 20 is sufficiently dried.
- ion-exchanged water ion-exchanged water having a neutral pH (preferably ion-exchanged water having a pH of around 7.0, preferably ion-exchanged water having a pH of 6.0 to 8.0) is used. use.
- the drying temperature is, for example, preferably 20 to 100 ° C, more preferably 20 to 80 ° C.
- the drying time is preferably 1 minute to 5 minutes, more preferably 1 minute to 2 minutes.
- the thickness T4 of the composition layer 42B in the transfer film 40 after immersion is measured.
- the thickness T5 of the dissolved portion of the ultraviolet absorbing layer 47 is obtained by subtracting the thickness T4 from the thickness T1, and the dissolution rate (%) of the ultraviolet absorbing layer 47 is calculated by the thickness T5 / thickness T3 ⁇ 100.
- the solubility of the ultraviolet absorbing layer is 60% or more, and 80% or more is preferable, 90% or more is more preferable, and 95% or more is further preferable, because the effect of the present invention is more excellent.
- the upper limit is 100% or less.
- the transfer film of the second aspect will be described.
- the structure of the transfer film of the second aspect is the same as that of the transfer film of the first aspect except that the structure of the ultraviolet absorbing layer is different, and the preferred embodiment is also the same.
- the method for producing the transfer film of the second aspect is the same as the method for producing the transfer film of the first aspect, and the preferred embodiment thereof is also the same.
- the ultraviolet absorbing layer included in the transfer film of the second aspect will be described.
- the transfer film has an ultraviolet absorbing layer.
- the ultraviolet absorbing layer is a layer capable of absorbing ultraviolet rays (specifically, a layer capable of absorbing ultraviolet rays having a wavelength of 450 nm or less). It is preferable to be able to absorb ultraviolet rays such as i-line (365 nm) and j-line (313 nm), 248 nm which is the exposure wavelength of the KrF exposure apparatus, and 193 nm which is the exposure wavelength of the ArF exposure apparatus. , H line (405 nm) and i line (365 nm) are more preferable.
- the ultraviolet absorbing layer preferably contains an ultraviolet absorber.
- the transmittance of the ultraviolet absorbing layer at a wavelength of 365 nm is preferably 70% or less, more preferably 50% or less, still more preferably 40% or less because the effect of the present invention is more excellent. ..
- the lower limit is preferably, for example, 20% or more.
- the transmittance of the ultraviolet absorbing layer at a wavelength of 405 nm is preferably 70% or less, more preferably 50% or less, still more preferably 40% or less, because the effect of the present invention is more excellent. ..
- the lower limit is preferably, for example, 20% or more.
- the transmittance can be measured using an ultraviolet-visible spectroscopic altimeter (for example, UV-1800 manufactured by Shimadzu Corporation).
- the optical density (OD value, wavelength 365 nm) of the ultraviolet absorbing layer is preferably 0.1 to 0.6, more preferably 0.1 to 0.4, in that the effect of the present invention is more excellent.
- a spectroscope UV4100 (trade name) manufactured by Hitachi High-Technology Co., Ltd. can be used.
- the ultraviolet absorber is a compound capable of absorbing ultraviolet rays, and has an ultraviolet absorbing property capable of absorbing light having at least a part of the photosensitive wavelength of the photopolymerization initiator that can be contained in the negative photosensitive composition layer. Is preferable.
- the molar extinction coefficient of the ultraviolet absorber to light having a wavelength of 365 nm is preferably 5,000 to 100,000 (L / (mol ⁇ cm)), preferably 10,000 to 80,000 (L / (mol ⁇ cm)). cm)) is more preferable, and 15,000 to 50,000 (L / (mol ⁇ cm)) is even more preferable.
- the molar extinction coefficient of the ultraviolet absorber shall be measured by the following method.
- the compound to be measured is a 4 ⁇ 10-6 (g / mL) solution using N, N-dimethylformamide.
- the UV absorber is preferably a UV absorber that is dispersed and / or soluble in water.
- examples of the ultraviolet absorber include a polymer ultraviolet absorber and a polymer-coated ultraviolet absorber.
- the polymer ultraviolet absorber is a polymer having an ultraviolet absorbing structure, and specific examples thereof include a polymer containing a structural unit derived from a monomer having an ultraviolet absorbing structure.
- a triazine structure, a benzotriazole structure, a benzophenone structure, or a salicylic acid structure is preferable, and a triazine structure is more preferable.
- the polymer containing a structural unit derived from a monomer having an ultraviolet absorbing structure is preferably a (meth) acrylic resin.
- the (meth) acrylic resin is formed of a monomer for forming a (meth) acrylic resin as an alkali-soluble resin that can be contained in the thermoplastic resin layer of the transfer film of the first B embodiment described above. It is preferable to have it.
- the content of the structural unit derived from the monomer having an ultraviolet absorbing structure in the polymer ultraviolet absorber is preferably 10 to 80% by mass, preferably 30 to 70% by mass, based on the total mass of the polymer. It is more preferable to have it.
- the weight average molecular weight of the polymer UV absorber is preferably 5,000 to 200,000, more preferably 7,000 to 150,000, and even more preferably 10,000 to 100,000.
- the polymer-coated ultraviolet absorber is an ultraviolet absorber in a form coated with a polymer, and examples thereof include polymer particles containing an ultraviolet absorber.
- the polymer include (meth) acrylic resin, polyester, polyurethane, polyolefin, siloxane resin, fluoropolymer and the like, and (meth) acrylic resin is preferable.
- the (meth) acrylic resin the (meth) acrylic resin as the alkali-soluble resin in the thermoplastic resin layer of the transfer film of the first B embodiment is preferable.
- the content of the ultraviolet absorber in the polymer-coated ultraviolet absorber is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, and further preferably 40 to 60% by mass, based on the total amount of the polymer-coated ultraviolet absorber.
- the content of the polymer in the polymer-coated UV absorber is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, still more preferably 40 to 60% by mass, based on the total amount of the polymer-coated UV absorber.
- the weight average molecular weight of the polymer (for example, acrylic resin) in the polymer-coated UV absorber is preferably 5,000 to 200,000, more preferably 7,000 to 150,000, and further preferably 10,000 to 100,000. preferable.
- the upper limit of the median diameter (D50) is preferably 500 nm or less, more preferably 400 nm or less, further preferably 200 nm or less, and particularly preferably 100 nm or less.
- the lower limit of the median diameter is preferably 10 nm or more, and more preferably 20 nm or more.
- the median diameter can be calculated from the particle size distribution by dynamic light scattering measurement.
- particles may be particles which are in a state where they can be dispersed in water by subjecting carbon black to a dispersion treatment.
- the form of the dispersion treatment is not particularly limited, and examples thereof include particles in which carbon black is coated with a polymer and particles in which the surface of carbon black is surface-modified with a dispersant.
- the upper limit of the median diameter (D50) of the particles is preferably 500 nm or less, more preferably 400 nm or less, further preferably 200 nm or less, and particularly preferably 100 nm or less.
- the lower limit of the median diameter is preferably 10 nm or more, and more preferably 20 nm or more.
- the median diameter can be calculated from the particle size distribution by dynamic light scattering measurement.
- UV absorbers Commercially available products of UV absorbers include, for example, TWBK-2581 (manufactured by Taisei Kako Co., Ltd.), Tinuvin (registered trademark) 9945-DW, 400-DW, 477-DW, 479-DW (both manufactured by BASF). , Newcoat (registered trademark) UVA-204W, UVA-101, UVA-102, UVA-103, UVA-104, (both manufactured by Shin Nakamura Chemical Industry Co., Ltd.) and the like.
- ultraviolet absorber only one type may be used alone, or two or more types may be used in combination.
- the content of the ultraviolet absorber is preferably 0.001 to 50% by mass, more preferably 0.1 to 30% by mass, and 5 to 30% by mass with respect to the total mass of the ultraviolet absorbing layer. It is more preferably 5 to 20% by mass, and particularly preferably 5 to 20% by mass.
- the ultraviolet absorbing layer has a dissolution rate of 60% or more calculated by the above-mentioned measuring method.
- the ultraviolet absorbing layer contains a polymer having a ClogP value smaller than 2.1 (hereinafter, also referred to as “specific polymer”). If the ultraviolet absorber is a polymer and the ClogP value is less than 2.1, this polymer is not included in the specific polymer.
- the ClogP of the specific binder is preferably 2.0 or less, more preferably 1.9 or less, in that the effect of the present invention is more excellent.
- the lower limit is not particularly limited, but is preferably 1.0 or more.
- ClogP is a value obtained by calculation of the common logarithm logP of 1-octanol and the partition coefficient P to water.
- known methods can be used, but unless otherwise specified, the ClogP program incorporated in ChemBioDrow Ultra 12.0 of Cambridge software is used in the present specification.
- the I / O value in the organic conceptual diagram of the specific binder is preferably 0.75 or less, more preferably less than 0.70, and 0.65 or less in that the effect of the present invention is more excellent. Is more preferable.
- the lower limit is not particularly limited, but is preferably 0.2 or more.
- the I / O value is the ratio of the inorganic value (I) to the organic value (O) in the organic conceptual diagram (hereinafter, also referred to as “I / O value”).
- the I / O value of the specific binder is obtained by the following method.
- I / of each monomer constituting the specific binder Calculate the O value. For each monomer constituting the specific binder, the product of the "I / O value” and the "mol% with respect to all the constituent units of the specific binder” is calculated, and these are totaled to obtain the I / O value of the specific polymer.
- the SP value in the solubility parameter of the specific binder is preferably 18.0 (MPa) 1/2 or more, and is larger than 20.0 (MPa) 1/2 in that the effect of the present invention is more excellent. Is more preferable.
- the upper limit thereof is not particularly limited, but is preferably 22 (MPa) 1/2 or less.
- the SP value means a value represented by the following Fedors equation (1).
- EV Evaporation energy
- v Molar volume
- ⁇ e i Evaporation energy of each atom or atomic group
- ⁇ v i Molar volume of each atom or atomic group
- the SP value is calculated by the following formula.
- ⁇ 1 , ..., ⁇ m are SP values of each monomer constituting the copolymer, and are values obtained by the above formula (1).
- the (meth) acrylic resin means a resin having a structural unit derived from the (meth) acrylic compound.
- the content of the structural unit derived from the (meth) acrylic compound is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, based on all the structural units of the (meth) acrylic resin. ..
- the (meth) acrylic resin may be composed of only a structural unit derived from the (meth) acrylic compound, or may have a structural unit derived from a polymerizable monomer other than the (meth) acrylic compound. .. That is, the upper limit of the content of the structural unit derived from the (meth) acrylic compound is 100% by mass or less with respect to all the structural units of the (meth) acrylic resin.
- Examples of the (meth) acrylic compound include (meth) acrylic acid and (meth) acrylic acid ester.
- (meth) acrylic acid ester (meth) acrylic acid alkyl ester or (meth) acrylic acid allyl is preferable, and (meth) acrylic acid allyl is more preferable.
- the alkyl group of the (meth) acrylic acid alkyl ester may be linear or may have a branch.
- Specific examples include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, ( Heptyl acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, and (meth) acrylate.
- Examples thereof include (meth) acrylic acid alkyl esters having an alkyl group having 1 to 12 carbon atoms such as dodecyl. Further, the alkyl group of the (meth) acrylic acid alkyl ester may be cyclic. The cyclic alkyl group may be monocyclic or polycyclic. Specific examples include cyclohexyl (meth) acrylate and the like.
- the (meth) acrylic resin may have a structural unit other than the structural unit derived from the (meth) acrylic compound as long as the ClogP value satisfies the above range.
- the (meth) acrylic resin preferably has a structural unit having an acid group in that the effect of the present invention is more excellent.
- the acid group include a carboxy group, a sulfo group, a phosphoric acid group, and a phosphonic acid group.
- the content of the constituent unit having an acid group (preferably the constituent unit derived from (meth) acrylic acid) in the (meth) acrylic resin is the total mass of the (meth) acrylic resin in that the effect of the present invention is more excellent. On the other hand, 10% by mass or more is preferable, and 20% by mass or more is more preferable.
- the upper limit is not particularly limited, but is preferably 50% by mass or less, more preferably 40% by mass or less, in terms of excellent alkali resistance.
- the (meth) acrylic resin has one or more of the above-mentioned structural units derived from the (meth) acrylic acid alkyl ester and the structural units derived from the (meth) allyl acrylic acid.
- the content of one or more structural units derived from the (meth) acrylic acid alkyl ester and the structural unit derived from allyl (meth) acrylic acid in the (meth) acrylic resin is the total content of the (meth) acrylic resin.
- 50 to 90% by mass is preferable, 60 to 90% by mass is more preferable, 65 to 90% by mass is further preferable, and 70 to 90% by mass is particularly preferable.
- Suitable forms of the (meth) acrylic resin include a structural unit derived from (meth) acrylic acid, a structural unit derived from a (meth) acrylic acid alkyl ester, and a structural unit derived from allyl (meth) acrylic acid. It is preferable that the resin has one or more kinds, and the constituent unit derived from (meth) acrylic acid, the constituent unit derived from (meth) acrylic acid alkyl ester, and the constituent unit derived from (meth) acrylic acid allyl. A resin composed of one or more kinds is more preferable.
- the acid value of the specific polymer is preferably 10 to 200 mgKOH / g, more preferably 60 to 200 mgKOH / g, further preferably 60 to 150 mgKOH / g, particularly preferably 70 to 150 mgKOH / g, and particularly preferably 100 to 150 mgKOH / g. Is the most preferable.
- the acid value of the specific polymer can be calculated from the average content of acid groups in the compound according to, for example, the method described in JIS K0070: 1992.
- the weight average molecular weight of the specific polymer is preferably 5,000 to 100,000, more preferably 7,000 to 50,000, still more preferably 10,000 to 50,000.
- the dispersity of the binder polymer is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, further preferably 1.0 to 4.0, and 1.0 to 3 from the viewpoint of developability. .0 is particularly preferred.
- the specific polymer only one kind may be used alone, or two or more kinds may be used in combination.
- the content of the specific polymer is, for example, preferably 20 to 95% by mass, more preferably 40 to 95% by mass, and 50 to 90% by mass with respect to the total mass of the ultraviolet absorbing layer. Is more preferable, and 60 to 90% by mass is particularly preferable.
- the content ratio of the ultraviolet absorber to the specific polymer is more preferably 0.05 to 0.4, and more preferably 0.1 to 0.3. Is more preferable.
- the ultraviolet absorbing layer may contain other components other than the ultraviolet absorber and the specific polymer. Examples of other components include polymerizable compounds, polymerization initiators, surfactants and the like. As a preferable aspect of the ultraviolet absorbing layer, it is also preferable that it is photocurable.
- the photocurable ultraviolet absorbing layer preferably contains an ethylenically unsaturated compound, and more preferably contains an ethylenically unsaturated compound and a photopolymerization initiator.
- the ultraviolet absorbing layer contains a polymerizable compound (preferably an ethylenically unsaturated compound)
- the content of the polymerizable compound preferably an ethylenically unsaturated compound
- the strength of the ultraviolet absorbing layer is more excellent.
- the UV absorbing layer contains a polymerization initiator (preferably a photopolymerization initiator), the content of the polymerization initiator (preferably a photopolymerization initiator) is such that the strength of the UV absorbing layer is more excellent in that it absorbs UV light. It is preferably 0.1 to 10% by mass, more preferably 0.5 to 10% by mass, still more preferably 0.5 to 5% by mass, based on the total mass of the layer.
- a polymerization initiator preferably a photopolymerization initiator
- the ultraviolet absorbing layer may contain a surfactant.
- the content of the surfactant is preferably 0.01 to 3% by mass, more preferably 0.05 to 1% by mass, based on the total mass of the ultraviolet absorbing layer. It is more preferably 0.1 to 0.8% by mass.
- the polymerizable compound, the polymerization initiator, and the surfactant which may be contained in the ultraviolet absorbing layer may contain the above-mentioned negative photosensitive composition layers of the first A embodiment and the first B embodiment.
- examples thereof include sex compounds, polymerization initiators, and surfactants.
- the ultraviolet absorbing layer may optionally contain other components.
- Other components include, for example, metal oxide particles, cross-linking agents other than heterocyclic compounds, alkoxysilane compounds, antioxidants, dispersants, acid growth agents, development accelerators, conductive fibers, colorants, and thermal radical generation. Examples thereof include known additives such as agents, thermoacid generators, thickeners, and organic or inorganic anti-precipitation agents.
- the thickness of the ultraviolet absorbing layer is preferably 0.05 to 5.0 ⁇ m, more preferably 0.05 to 2.0 ⁇ m, further preferably 0.1 to 1.0 ⁇ m, and particularly preferably 0.1 to 0.5 ⁇ m. , 0.1-0.4 ⁇ m is most preferred.
- the composition layer can be transferred to the transferred body.
- the transfer films of the first aspect and the second aspect are preferably used for manufacturing a touch panel.
- the surface of the transfer film on the opposite side of the temporary support is brought into contact with the substrate having the conductive layer, and the substrate, the conductive layer, the composition layer, and the temporary support are provided.
- the bonding process for obtaining a substrate with a composition layer having bodies in this order The peeling process to peel off the temporary support and An exposure process for pattern exposure of the exposed composition layer, and It is preferable to use a method for producing a laminate, which comprises a developing step of developing an exposed composition layer to form a pattern.
- a method for producing a laminate which comprises a developing step of developing an exposed composition layer to form a pattern.
- the bonding step the surface of the transfer film opposite to the temporary support is brought into contact with the substrate having the conductive layer and bonded, and the substrate, the conductive layer, the composition layer, and the temporary support are provided in this order. This is a step of obtaining a substrate with a composition layer. If the transfer film has a protective film, the protective film is peeled off and then the bonding step is performed.
- the conductive layer and the surface of the composition layer are pressure-bonded so as to be in contact with each other.
- the crimping method is not particularly limited, and a known transfer method and laminating method can be used. Above all, it is preferable that the surface of the composition layer is superposed on the substrate having the conductive layer, and pressurization and heating by a roll or the like are performed.
- a known laminator such as a vacuum laminator and an auto-cut laminator can be used for bonding.
- the laminating temperature is not particularly limited, but is preferably 70 to 130 ° C., for example.
- the substrate having a conductive layer has a conductive layer on the substrate, and any layer may be formed if necessary. That is, the substrate having the conductive layer is a conductive substrate having at least a substrate and a conductive layer arranged on the substrate.
- the substrate examples include a resin substrate, a glass substrate, and a semiconductor substrate. Preferred embodiments of the substrate are described, for example, in paragraph [0140] of WO 2018/155193, the contents of which are incorporated herein.
- the material of the resin substrate cycloolefin polymer and polyimide are preferable.
- the thickness of the resin substrate is preferably 5 ⁇ m to 200 ⁇ m, more preferably 10 to 100 ⁇ m.
- the conductive layer is at least one layer selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer from the viewpoint of conductivity and fine wire forming property. It is preferable to have it. Further, only one conductive layer may be arranged on the substrate, or two or more layers may be arranged. When two or more conductive layers are arranged, it is preferable to have conductive layers made of different materials. Preferred embodiments of the conductive layer are described, for example, in paragraph [0141] of WO 2018/155193, the contents of which are incorporated herein.
- a substrate having at least one of a transparent electrode and a routing wire is preferable.
- the above-mentioned substrate can be suitably used as a touch panel substrate.
- the transparent electrode may function suitably as a touch panel electrode.
- the transparent electrode is preferably composed of a metal oxide film such as ITO (indium tin oxide) and IZO (indium zinc oxide), a metal mesh, and a fine metal wire such as a metal nanowire.
- the thin metal wire include thin wires such as silver and copper. Of these, silver conductive materials such as silver mesh and silver nanowires are preferable.
- Metal is preferable as the material of the routing wiring.
- the metal that is the material of the routing wiring include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, and alloys composed of two or more of these metal elements.
- copper, molybdenum, aluminum, or titanium is preferable, and copper is particularly preferable.
- the protective film for a touch panel formed by using the negative photosensitive composition layer in the transfer film of the first aspect and the second aspect directly or / or directly connects the electrode and / or the wiring for the purpose of protecting the electrode and / or the wiring. It may be provided so as to cover it via another layer, or it may be provided as a protective film for insulating between electrodes (specifically, a protective film for insulating between electrodes such as bridge wiring). You may.
- the peeling step is a step of peeling the temporary support from the substrate with the composition layer.
- the peeling method is not particularly limited, and a mechanism similar to the cover film peeling mechanism described in paragraphs [0161] to [0162] of JP2010-072589 can be used.
- the exposure step is a step of pattern-exposing the exposed composition layer.
- the "pattern exposure” refers to an exposure in a form of exposure in a pattern, that is, a form in which an exposed portion and a non-exposed portion are present.
- the positional relationship between the exposed area and the unexposed area in the pattern exposure is not particularly limited and is appropriately adjusted. It may be exposed from the side opposite to the substrate of the composition layer, or may be exposed from the substrate side of the composition layer.
- any light source in a wavelength range capable of curing at least the negative photosensitive composition layer (for example, 365 nm or 405 nm) can be appropriately selected and used.
- the main wavelength of the exposure light for pattern exposure is preferably 365 nm.
- the main wavelength is the wavelength having the highest intensity.
- Examples of the light source include various lasers, light emitting diodes (LEDs), ultra-high pressure mercury lamps, high pressure mercury lamps, and metal halide lamps.
- the exposure amount is preferably 5 to 200 mJ / cm 2 , more preferably 10 to 200 mJ / cm 2 .
- a protective film pattern that protects at least a part of the conductive layer is formed on the conductive layer on the substrate.
- the developing step is a step of developing the exposed composition layer to form a pattern.
- the development of the composition layer can be carried out using a developing solution.
- An alkaline aqueous solution is preferable as the developing solution.
- the alkaline compound that can be contained in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrapropylammonium hydroxide. Do, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide) can be mentioned.
- Examples of the development method include paddle development, shower development, spin development, and dip development, and shower development is preferable.
- a preferred embodiment of the developer used in the developing step is, for example, the developer described in paragraph [0194] of International Publication No. 2015/093271. Further, as a preferable aspect of the developing method for carrying out the developing step, for example, the developing method described in paragraph [0195] of International Publication No. 2015/093271 can be mentioned.
- the developing step is preferably a step of repeatedly using the developing solution by circulating the developing solution, the developing method is shower development, and the developing solution is circulated by circulating the developing solution. It is preferable that the process is used repeatedly.
- Specific embodiments for carrying out the above-mentioned development step include, for example, the development method described in JP-A-2012-137574.
- the method for producing the laminate may include a step of exposing the pattern obtained by the development step (post-exposure step) and / or a step of heating (post-baking step).
- post-exposure step a step of exposing the pattern obtained by the development step
- post-baking step a step of heating
- the exposure amount of the post exposure is preferably 100 to 5000 mJ / cm 2 , more preferably 200 to 3000 mJ / cm 2 .
- the post-bake temperature is preferably 80 to 250 ° C, more preferably 90 to 160 ° C.
- the post-baking time is preferably 1 to 180 minutes, more preferably 10 to 60 minutes.
- the laminate produced by the method for producing a laminate of the present invention can be applied to various devices.
- the device provided with the laminated body include an input device and the like, and a touch panel is preferable, and a capacitive touch panel is more preferable.
- the input device can be applied to a display device such as an organic electroluminescence display device and a liquid crystal display device.
- the pattern formed from the composition layer is preferably used as a touch panel electrode or a protective film for the touch panel wiring. That is, the composition layer contained in the transfer film is preferably used for forming the electrode protective film for the touch panel or the wiring protective film for the touch panel.
- Circuit wiring can also be manufactured by using the transfer films of the first aspect and the second aspect.
- the method for manufacturing the circuit wiring is not particularly limited as long as it is the method for manufacturing the circuit wiring using the transfer film described above.
- the surface of the transfer film on the opposite side of the temporary support is brought into contact with the substrate having the conductive layer, and the substrate, the conductive layer, the composition layer, and the temporary support are provided.
- the bonding process for obtaining a substrate with a composition layer having bodies in this order The peeling process to peel off the temporary support and An exposure process for pattern exposure of the exposed composition layer, and A developing process that develops the exposed composition layer to form a resin pattern, It is preferable that the manufacturing method includes an etching step of etching a conductive layer in a region where a resin pattern is not arranged.
- the bonding step, peeling step, exposure process, and developing step in the circuit wiring manufacturing method are the same as the bonding step, peeling step, exposure step, and developing step in the above-mentioned laminated body manufacturing method, and are preferred embodiments. Is the same.
- the method for manufacturing a circuit wiring includes a substrate, a conductive layer (a conductive layer possessed by the substrate), and a resin pattern (more preferably, the bonding step, the peeling step, the exposure step, and the developing step.
- a step (etching step) of etching a conductive layer in a region where a resin pattern is not arranged is included in a laminate in which resin patterns manufactured by a manufacturing method) are laminated in this order.
- the resin pattern obtained from the negative photosensitive composition layer by the developing step is used as an etching resist, and the conductive layer is etched.
- a method of etching treatment a known method can be applied.
- an acidic or alkaline etching solution may be appropriately selected according to the etching target.
- the acidic etching solution include an aqueous solution of an acidic component alone selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid and phosphoric acid, and the acidic component, ferric chloride, ammonium fluoride and Examples thereof include a mixed aqueous solution with a salt selected from potassium permanganate.
- the acidic component may be a component in which a plurality of acidic components are combined.
- the alkaline etching solution includes an aqueous solution of an alkaline component alone selected from sodium hydroxide, potassium hydroxide, ammonia, an organic amine, and a salt of an organic amine (tetramethylammonium hydroxide, etc.), and an alkaline component and a salt. Examples thereof include a mixed aqueous solution with (potassium permanganate, etc.).
- the alkaline component may be a component in which a plurality of alkaline components are combined.
- the removing step is not particularly limited and can be performed as needed, but it is preferably performed after the etching step.
- the method for removing the remaining resin pattern is not particularly limited, and examples thereof include a method for removing by chemical treatment, and a method for removing with a removing liquid is preferable.
- a method for removing the negative photosensitive composition layer a substrate having a resin pattern remaining in the removing liquid during stirring having a liquid temperature of preferably 30 to 80 ° C., more preferably 50 to 80 ° C. is 1 to 1 to 1. A method of soaking for 30 minutes can be mentioned.
- the removing liquid examples include a removing liquid in which an inorganic alkaline component or an organic alkaline component is dissolved in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixed solution thereof.
- examples of the inorganic alkaline component include sodium hydroxide and potassium hydroxide.
- examples of the organic alkali component include a primary amine compound, a secondary amine compound, a tertiary amine compound and a quaternary ammonium salt compound.
- the removing liquid may be used and removed by a known method such as a spray method, a shower method and a paddle method.
- the method for manufacturing the circuit wiring may include any process (other process) other than the above-mentioned process.
- a step of reducing the visible light reflectance described in paragraph [0172] of International Publication No. 2019/022089 a new conductive layer is provided on the insulating film described in paragraph [0172] of International Publication No. 2019/022089. Examples thereof include steps of forming, but the process is not limited to these steps.
- the method for manufacturing a circuit wiring may include a step of reducing the visible light reflectance of a part or all of the plurality of conductive layers of the base material.
- the treatment for reducing the visible light reflectance include an oxidation treatment.
- the visible light reflectance of the conductive layer can be lowered by oxidizing copper to copper oxide and blackening the conductive layer.
- the treatment for reducing the visible light reflectance is described in paragraphs 0017 to 0025 of JP-A-2014-150118 and paragraphs 0041, 0042, 0048 and 0058 of JP-2013-206315. , The contents of these publications are incorporated herein.
- the method for manufacturing a circuit wiring includes a step of forming an insulating film on the surface of the circuit wiring and a step of forming a new conductive layer on the surface of the insulating film.
- a second electrode pattern insulated from the first electrode pattern can be formed.
- the step of forming the insulating film is not particularly limited, and examples thereof include a known method of forming a permanent film.
- an insulating film having a desired pattern may be formed by photolithography using a photosensitive material having an insulating property.
- the step of forming the new conductive layer on the insulating film is not particularly limited, and for example, a new conductive layer having a desired pattern may be formed by photolithography using a photosensitive material having conductivity.
- a substrate having a plurality of conductive layers on both surfaces of the base material it is also preferable to use a substrate having a plurality of conductive layers on both surfaces of the base material, and to form a circuit sequentially or simultaneously on the conductive layers formed on both surfaces of the base material.
- a circuit wiring for a touch panel in which a first conductive pattern is formed on one surface of a base material and a second conductive pattern is formed on the other surface. It is also preferable to form the touch panel circuit wiring having such a configuration from both sides of the base material by roll-to-roll.
- the circuit wiring manufactured by the method of manufacturing the circuit wiring can be applied to various devices.
- Examples of the device provided with the circuit wiring manufactured by the above manufacturing method include an input device, a touch panel is preferable, and a capacitance type touch panel is more preferable.
- the input device can be applied to a display device such as an organic EL display device and a liquid crystal display device.
- SP value, I / O value, and LogP value of binder The SP value, I / O value, and LogP value of the binder were measured by the methods described above.
- the binder contained in the ultraviolet absorbing layer of the transfer film of the example corresponds to compounds 11 to 14.
- SR-454 Ethoxylation (3) Trimethylolpropane triacrylate (“SR-454” manufactured by Tomoe Engineering Co., Ltd., trifunctional acrylate)
- A-DCP Tricyclodecanedimethanol diacrylate
- A-DCP manufactured by Shin Nakamura Chemical Industry Co., Ltd., bifunctional acrylate
- TO-2349 Mixture of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and succinic acid derivative of dipentaerythritol pentaacrylate ("Aronix TO-2349" manufactured by Toagosei Co., Ltd., 5 or 6 functional acrylate)
- -AD-TMP Ditrimethylolpropane tetra
- MTBD1 1,4-bis (3-mercaptobutyryloxy) butane (Showa Denko "Karensu MT (registered trademark) BD1", bifunctional thiol)
- Duranate TPA-B80E Blocked isocyanate compound ("Duranate (registered trademark) TPA-B80E” manufactured by Asahi Kasei Chemicals Co., Ltd. " ⁇ Benzimidazole: manufactured by Tokyo Chemical Industry Co., Ltd.
- TWBK-2581 Water-based carbon black dispersion ("TWBK-251" manufactured by Taisei Kako Co., Ltd., solid content concentration: about 15% by mass)
- TINUVIN477-DW Hydroxyphenyltriazine aqueous dispersion (BASF's "TINUVIN477-DW", solid content concentration: about 80% by mass)
- TINUVIN 329 2- (2H-benzotriazole-2-yl) -4- (1,1,3,3-tetramethylbutyl) (BASF's "TINUVIN 329")
- 4-88 LA Polyvinyl alcohol ("4-88 LA” manufactured by Kuraray Co., Ltd.)
- PVP K30 Polyvinylpyrrolidone ("PVP K30” manufactured by Fujifilm Corporation)
- Metro's 60SH03 Water-soluble cellulose derivative
- F444 Surfactant
- composition for forming an ultraviolet absorbing layer Various components were mixed based on the composition and the blending amount shown in Table 2 to prepare a composition (coating liquid) for forming an ultraviolet absorbing layer.
- the numerical values corresponding to the components shown in Table 2 represent the blending amount (parts by mass) of each component.
- composition for forming an intermediate layer Various components were mixed based on the composition and the blending amount shown below to prepare a composition (coating liquid) for forming an intermediate layer.
- the numerical values corresponding to the components shown in Table 2 represent the blending amount (parts by mass) of each component in the solid content.
- Transfer films were prepared so as to have the configurations shown in Table 2. Specifically, it is as follows.
- the composition for forming an ultraviolet absorbing layer having the composition shown in Table 2 is applied onto the negative photosensitive composition layer using a bar coater so as to have the film thickness shown in Table 2 after drying.
- a coating film was dried in an oven at 90 ° C. to form an ultraviolet absorbing layer.
- polyethylene terephthalate (16KS40: trade name, manufactured by Toray Industries, Inc.) having a thickness of 16 ⁇ m was pressure-bonded to the surface of the above-mentioned ultraviolet absorbing layer as a protective film to prepare a transfer film of Example 1.
- the composition for forming an ultraviolet absorbing layer having the composition shown in Table 2 is applied onto the negative photosensitive composition layer using a bar coater so as to have the film thickness shown in Table 2 after drying.
- a bar coater so as to have the film thickness shown in Table 2 after drying.
- the obtained coating film was dried in an oven at 100 ° C. for 2 minutes to form an ultraviolet absorbing layer.
- polyethylene terephthalate (16KS40: trade name, manufactured by Toray Industries, Inc.) having a thickness of 16 ⁇ m was pressure-bonded to the surface of the above-mentioned ultraviolet absorbing layer as a protective film to prepare a transfer film of Comparative Example 1.
- a transfer film of the transfer film of Comparative Example 3 was produced by the same method as in Example 1 except that the ultraviolet absorbing layer was not formed.
- the composition layer in No. 4 is a three layer of an intermediate layer, a negative photosensitive composition layer, and an ultraviolet absorbing layer), and the thickness T1 was measured. Further, in the measurement of the thickness T1, any five points were measured and calculated as the average value of each measured value. Each thickness such as the thickness T2 and the thickness T4, which will be described later, is also measured by the same procedure as the thickness T1.
- a commercially available tape was pressed against the exposed ultraviolet absorbing layer by peeling off the protective film, and then the tape was peeled off to peel off the ultraviolet absorbing layer from the transfer film. Then, using a stylus type film thickness meter, the thickness T2 of the composition layer after the ultraviolet absorbing layer was peeled off was measured. Next, the thickness T3 of the ultraviolet absorbing layer was obtained by subtracting the thickness T2 from the thickness T1. Next, a new transfer film was prepared separately, and the protective film was peeled off. Then, the transfer film from which the protective film was peeled off (in other words, the transfer film with the ultraviolet absorbing layer exposed) was immersed in ion-exchanged water at 25 ° C. for 60 seconds.
- the thickness T4 of the composition layer in the transfer film was measured using a stylus type film thickness meter. Then, the thickness T5 of the dissolved ultraviolet absorbing layer was obtained by subtracting the thickness T4 from the thickness T1, and the dissolution rate (%) of the ultraviolet absorbing layer was calculated by the thickness T5 / thickness T3 ⁇ 100.
- OD value of UV absorption layer The optical density (OD) (wavelength 365 nm) of the transfer film was measured by a spectroscope UV4100 (manufactured by Hitachi High-Technology Co., Ltd.). Next, the optical density (OD) of the transfer film having no ultraviolet absorbing layer or the transfer film from which the ultraviolet absorbing layer was removed was measured in the same manner, and the optical density (OD) of the ultraviolet absorbing layer was calculated from the difference.
- the OD value is a numerical value indicating the light-shielding ability, and the larger the value is, the higher the light-shielding property of the ultraviolet absorbing layer is.
- ⁇ Method of measuring the transmittance of the ultraviolet absorbing layer (wavelength 365 nm, wavelength 405 nm)> (Transmittance of UV absorbing layer at wavelength of 365 nm)
- the transmittance (%) of the transfer film having an ultraviolet absorbing layer at a wavelength of 365 nm was measured by an ultraviolet-visible spectrophotometer (UV-1800 manufactured by Shimadzu Corporation).
- UV-1800 ultraviolet-visible spectrophotometer
- the transmittance (%) of the transfer film having no ultraviolet absorbing layer or the transfer film from which the ultraviolet absorbing layer has been removed is measured in the same manner, and the transmittance (%) of the ultraviolet absorbing layer at a wavelength of 365 nm is determined by the difference. Calculated.
- the transmittance (%) of the ultraviolet absorbing layer at a wavelength of 405 nm was calculated by the same method except that the wavelength of 365 nm was changed to a wavelength of 405 nm.
- each exposure mask having a pattern of line 1 ⁇ m / space 1 ⁇ m to line 50 ⁇ m / space 50 ⁇ m was brought into close contact with the surface exposed after the temporary support was peeled off.
- a negative type photosensitive composition layer was exposed at 100 mJ / cm 2 using a high-pressure mercury lamp exposure machine (MAP-1200L manufactured by Dainippon Kaken Co., Ltd., main wavelength: 365 nm). Then, shower development was carried out for 30 seconds with a 1% by mass sodium carbonate aqueous solution having a liquid temperature of 25 ° C. to form a pattern on the Ni-plated layer.
- MAP-1200L manufactured by Dainippon Kaken Co., Ltd., main wavelength: 365 nm
- FIG. 4 shows a schematic cross-sectional view of a pattern having a tailed shape.
- the "hem length (one side)" is intended to be the distance L between the intersection Q when a perpendicular line is drawn from the end ET of the upper surface FT of the pattern to the lower surface FB of the pattern and the end EB of the lower surface FB of the pattern.
- the hem length was measured for each of the two sides (sides indicated by the white arrows in FIG. 2) in the cross-sectional shape of the pattern.
- the hem lengths of 10 places were arbitrarily measured for each side surface to calculate the average value, and of the two average values obtained, the larger value was evaluated based on the following evaluation criteria.
- A The hem length (one side) is 0.5 ⁇ m or less.
- B The hem length (one side) is larger than 0.5 ⁇ m and 1.0 ⁇ m or less.
- C The hem length (one side) is larger than 1.0 ⁇ m.
- a conductive substrate having Ni plating (thickness 100 nm) on the glass was prepared. After peeling off the protective film of the produced transfer film, the Ni plating layer and the ultraviolet absorbing layer come into contact with each other under laminating conditions of a substrate temperature of 80 ° C., a rubber roller temperature of 110 ° C., a linear pressure of 3 N / cm, and a transport speed of 2 m / min. As described above, it was laminated on the conductive substrate. Next, the temporary support is peeled off, and an exposure mask having a predetermined line ( ⁇ m) / space ( ⁇ m) pattern (note that the line width and the space width are 1: 1) is peeled off from the temporary support.
- a negative type photosensitive composition layer was exposed at 100 mJ / cm 2 using a high-pressure mercury lamp exposure machine (MAP-1200L manufactured by Dainippon Kaken Co., Ltd., main wavelength: 365 nm). Then, shower development was carried out for 30 seconds with a 1% by mass sodium carbonate aqueous solution having a liquid temperature of 25 ° C. to form a pattern on the Ni-plated layer.
- the minimum line width at which the pattern obtained by the above procedure can be decomposed without development residue was evaluated as "resolution". The smaller the minimum line width, the better the resolution. Table 2 shows the measurement results.
- the transfer film of the example can form a pattern having excellent resolution and suppressed tailing shape.
- the specific polymer of the ultraviolet absorbing layer (polymer having ClogP smaller than 2.1) has an I / O value smaller than 0.70 and / or has an SP value of 2. It was clarified that the resolution was better when it was larger than 0.0 (MPa) 1/2 .
- the comparison between Example 1 and Examples 8 and 9 it was confirmed that when the OD value of the ultraviolet absorbing layer is 0.5 or less, the tailing shape of the pattern can be further suppressed. In particular, when the OD value of the ultraviolet absorbing layer is 0.4 or less, it has been clarified that the resolution is more excellent. Further, from the comparison between Example 1 and Examples 8 and 9, it was confirmed that when the film thickness of the ultraviolet absorbing layer is 0.30 ⁇ m or less, the tailing shape of the pattern can be further suppressed.
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Abstract
Description
フォトリソグラフィープロセスとは、フォトレジストに対してマスクを介して露光した後、現像によって現像液に可溶な部分を除去するプロセスである。例えば、フォトレジストが露光により硬化するフォトレジスト(ネガ型フォトレジスト)である場合、マスク開口部においては硬化反応が進む一方、マスクで遮蔽された未露光部においては硬化反応が抑制される。このため、露光部と未露光部とでは現像液に対する溶解性が異なり、現像処理の際に、現像液に対する溶解性の高い未露光部のみが除去される。
これに対して、特許文献1の転写フィルムは、紫外線吸収層を導入し、且つ、仮支持体、感光性樹脂層(以下「感光性組成物層」ともいう。)、及び紫外線吸収層の順に配置する構成により、露光時に感光性組成物層内において露光光源からの入射光と金属基板での反射光とによる干渉縞(定在波)が発生することを抑制して、パターンの形状の改善(裾引きの抑制)を図っている。一方、今般、本発明者らは上記特許文献1を参照して転写フィルムを作製して検討したところ、上記転写フィルムにより形成されるパターンは、依然として裾引きをしている場合があり、更なる改善の余地があることを明らかとした。
また、本発明は、上記転写フィルムを使用した積層体の製造方法及び回路配線の製造方法を提供することを課題とする。
上記紫外線吸収層が、上記ネガ型感光性組成物層の上記仮支持体側とは反対側に配置されており、
上記紫外線吸収層が、紫外線吸収剤及びClogP値が2.1より小さいポリマーを含む、転写フィルム。
〔2〕 仮支持体と、上記仮支持体上に配置された、ネガ型感光性組成物層及び紫外線吸収層を含む組成物層と、を有する転写フィルムであり、
上記紫外線吸収層が、上記ネガ型感光性組成物層の上記仮支持体側とは反対側に配置されており、
上記紫外線吸収層の後述する測定方法により算出される溶解率が、60%以上である、転写フィルム。
〔3〕 上記紫外線吸収層が、紫外線吸収剤及びClogP値が2.1より小さいポリマーを含む、〔2〕に記載の転写フィルム。
〔4〕 上記ポリマーのSP値が20.0(MPa)1/2より大きい、〔1〕又は〔3〕に記載の転写フィルム。
〔5〕 上記ポリマーの有機概念図におけるI/O値が0.70より小さい、〔1〕、〔3〕、又は〔4〕に記載の転写フィルム。
〔6〕 上記紫外線吸収層の波長365nmにおける透過率が、20~70%である、〔1〕~〔5〕のいずれかに記載の転写フィルム。
〔7〕 上記紫外線吸収層の波長405nmにおける透過率が、20~70%である、〔1〕~〔6〕のいずれかに記載の転写フィルム。
〔8〕 上記紫外線吸収層が光硬化性である、〔1〕~〔7〕のいずれかに記載の転写フィルム。
〔9〕 上記紫外線吸収層の厚みが5.0μm以下である、〔1〕~〔8〕のいずれかに記載の転写フィルム。
〔10〕 上記組成物層が、更に中間層を含み、
上記中間層が、上記ネガ型感光性組成物層と上記仮支持体の間に配置されている、〔1〕~〔9〕のいずれかに記載の転写フィルム。
〔11〕 上記中間層が、水溶性樹脂を含む、〔10〕に記載の転写フィルム。
〔12〕 上記中間層が、水溶性セルロース誘導体、ポリエーテル類、多価アルコール類、多価アルコール類のアルキレンオキサイド付加物、フェノール誘導体、及びアミド化合物からなる群から選ばれる1種以上の化合物を含む、〔11〕に記載の転写フィルム。
〔13〕 〔1〕~〔12〕のいずれかに記載の転写フィルムの上記仮支持体とは反対側の表面を、導電層を有する基板に接触させ、上記基板、上記導電層、上記組成物層、及び、上記仮支持体をこの順に有する組成物層付き基板を得る貼合工程と、
上記仮支持体を剥離する剥離工程と、
露出した上記組成物層をパターン露光する露光工程と、
露光した上記組成物層を現像してパターンを形成する現像工程と、を有する積層体の製造方法。
〔14〕 上記露光工程が、露出した上記組成物層とマスクとを接触させて露光処理を実施する工程である、〔13〕に記載の積層体の製造方法。
〔15〕 〔1〕~〔12〕のいずれかに記載の転写フィルムの上記仮支持体とは反対側の表面を、導電層を有する基板に接触させ、上記基板、上記導電層、上記組成物層、及び、上記仮支持体をこの順に有する組成物層付き基板を得る貼合工程と、
上記仮支持体を剥離する剥離工程と、
露出した上記組成物層をパターン露光する露光工程と、
露光した上記組成物層を現像して樹脂パターンを形成する現像工程と、
上記樹脂パターンが配置されていない領域における上記導電層をエッチング処理するエッチング工程と、を含む、回路配線の製造方法。
また、本発明によれば、上記転写フィルムを使用した積層体の製造方法及び回路配線の製造方法を提供できる。
本明細書において、「~」を用いて表される数値範囲は、「~」の前後に記載される数値を下限値及び上限値として含む範囲を意味する。
本明細書において、段階的に記載されている数値範囲において、ある数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。また、本明細書に記載されている数値範囲において、ある数値範囲で記載された上限値又は下限値は、実施例に示されている値に置き換えてもよい。
本明細書において、可視光の平均透過率は、分光光度計を用いて測定される値であり、例えば、日立製作所株式会社製の分光光度計U-3310を用いて測定できる。
本明細書において、特段の断りがない限り、分子量分布がある化合物の分子量は、重量平均分子量(Mw)である。
本明細書において、特段の断りがない限り、ポリマーの構成単位の比は質量比である。
本明細書において、特段の断りがない限り、金属元素の含有量は、誘導結合プラズマ(ICP:Inductively Coupled Plasma)分光分析装置を用いて測定した値である。
本明細書において、特段の断りがない限り、屈折率は、波長550nmでエリプソメーターを用いて測定した値である。
本明細書において、特段の断りがない限り、色相は、色差計(CR-221、ミノルタ株式会社製)を用いて測定した値である。
本発明の第1態様の転写フィルムは、
仮支持体と、上記仮支持体上に配置された、ネガ型感光性組成物層及び紫外線吸収層を含む組成物層と、を有する転写フィルムであり、
紫外線吸収層が、ネガ型感光性組成物層の仮支持体側とは反対側に配置されており、紫外線吸収剤及びClogP値が2.1より小さいポリマー(以下「特定ポリマー」ともいう。)を含む。
上記構成の第1態様の転写フィルムによれば、裾引き形状が抑制されたパターンを形成できる。本発明の第1態様の転写フィルムの推定される作用機序は、以下のとおりである。
第1態様の転写フィルムは、ネガ型感光性組成物層の仮支持体とは反対側に紫外線吸収層を有しており、この構造に起因して、仮支持体とは反対側の面で基板(例えば金属基板)に接触するように転写フィルムを基板上にラミネートしてパターン形成を実施する際、露光光源からの入射光が基板で反射したとしても、その反射光は、紫外線吸収層で吸収され得る。この結果として、第1態様の転写フィルムは、露光時にネガ型感光性組成物層内において露光光源からの入射光と金属基板での反射光とによる干渉縞が発生しにくく、更に加えて、反射光は、本来マスクで遮蔽された領域(未露光部)に拡散しにくい。すなわち、転写フィルムが所定位置に紫外線吸収層を備えることで、露光光源からの入射光の基板での反射に起因したパターンの形状故障が抑制され得る。
また、今般、本発明者らは、第1態様の転写フィルムの上記紫外線吸収層が比較的親水性の高い特定ポリマーを含むことで、現像(好ましくはアルカリ現像)の際に紫外線吸収層の残渣が残りにくく、これにも起因して、形成されるパターンの形状が裾引き形状になりにくいことも明らかとしている。なお、ネガ型感光性組成物層は、通常、疎水的な成分で構成される場合が多い。今般の発明者らの検討によれば、転写フィルム中の紫外線吸収層が比較的疎水性の高い特定ポリマーを含む形態とした場合、塗布法によりネガ型感光性組成物層と紫外線吸収層とを積層すると、ネガ型感光性組成物層と紫外線吸収層との過度な層間混合が生じ得て、これによってもパターンの形状が裾引き形状となり易いことを知見している。また、転写法によりネガ型感光性組成物層と紫外線吸収層とを積層しても、紫外線吸収層が比較的疎水性の高い特定ポリマーを含む場合、両層の成分の層間移動によってネガ型感光性組成物層と紫外線吸収層との過度な層間混合が生じ得ることを明らかとしている。これに対して、上記紫外線吸収層が比較的親水性の高い特定ポリマーを含む場合、ネガ型感光性組成物層と紫外線吸収層との過度な層間混合を抑制でき、この点もパターンの形状故障の抑制に寄与し得ることも明らかとした。
第1態様の転写フィルムは、仮支持体と、上記仮支持体上に配置された、ネガ型感光性組成物層及び紫外線吸収層を含む組成物層と、を有する。
上記組成物層は、ネガ型感光性組成物層及び紫外線吸収層を少なくとも含むが、ネガ型感光性組成物層及び紫外線吸収剤以外の他の層を含んでもよい。
上記他の層としては、例えば、中間層、熱可塑性樹脂層、及び、屈折率調整層等が挙げられる。
また、第1態様の転写フィルムは、組成物層上に保護フィルムを有する構成であってもよい。
(1)「仮支持体/ネガ型感光性組成物層/紫外線吸収層/屈折率調整層/保護フィルム」
(2)「仮支持体/中間層A/ネガ型感光性組成物層/紫外線吸収層/屈折率調整層/保護フィルム」
(3)「仮支持体/ネガ型感光性組成物層/紫外線吸収層/保護フィルム」
(4)「仮支持体/中間層A/ネガ型感光性組成物層/紫外線吸収層/保護フィルム」
(5)「仮支持体/熱可塑性樹脂層/中間層B/ネガ型感光性組成物層/紫外線吸収層/保護フィルム」
(6)「仮支持体/中間層A/熱可塑性樹脂層/中間層B/ネガ型感光性組成物層/紫外線吸収層/保護フィルム」
なお、紫外線吸収層とネガ型感光性組成物層とは隣接して配置されるのが好ましい。
なお、上記各構成において、ネガ型感光性組成物層が着色樹脂層であることも好ましい。
本発明の転写フィルムは、後述するように保護膜用の転写フィルムとして使用されてもよいし、エッチングレジスト用の転写フィルムとして使用されてもよい。
なお、「保護膜用」とは、電極及び/又は配線を保護する目的で、電極及び/又は配線を覆うように設けられる保護膜、及び、電極間を絶縁するための保護膜(具体的にはブリッジ配線等の電極間を絶縁するための保護膜)を意図する。
保護膜用の転写フィルムとする場合、転写フィルムの構成としては、例えば、上述した(1)~(3)の構成であるのが好ましい。また、エッチングレジスト用の転写フィルムとする場合、転写フィルムの構成としては、例えば、上述した(3)~(6)の構成であるのが好ましい。
第1態様の転写フィルムのうねりの最大幅は、以下の手順により測定される値である。
まず、第1態様の転写フィルムを縦20cm×横20cmのサイズとなるように主面に垂直な方向に裁断し、試験サンプルを作製する。なお、第1態様の転写フィルムが保護フィルムを有する場合には、保護フィルムを剥離する。次いで、表面が平滑で且つ水平なステージ上に、上記試験サンプルを仮支持体の表面がステージに対向するように静置する。静置後、試験サンプルの中心10cm角の範囲について、試料サンプルの表面をレーザー顕微鏡(例えば、(株)キーエンス社製 VK-9700SP)で走査して3次元表面画像を取得し、得られた3次元表面画像で観察される最大凸高さから最低凹高さを引き算する。上記操作を10個の試験サンプルについて行い、その算術平均値を「第1態様の転写フィルムのうねり最大幅」とする。
以下において、第1A実施形態の転写フィルムの実施形態の一例について説明する。
図1に示す転写フィルム10は、仮支持体1と、中間層(中間層A)3、ネガ型感光性組成物層5、紫外線吸収層7、及び、屈折率調整層9を含む組成物層2と、保護フィルム11とを、この順に有する。
なお、図1で示す転写フィルム10は保護フィルム11を配置した形態であるが、保護フィルム11は、配置されなくてもよい。
また、図1で示す転写フィルム10は屈折率調整層9を配置した形態であるが、屈折率調整層9は、配置されなくてもよい。
また、図1で示す転写フィルム10は中間層(中間層A)3を配置した形態であるが、中間層(中間層A)3は、配置されなくてもよい。
以下において、第1A実施形態の転写フィルム(以下「転写フィルム」と略記する。)を構成する各要素について説明する。
転写フィルムは、仮支持体を有する。
仮支持体は、組成物層を支持する部材であり、最終的には剥離処理により除去される。
仮支持体は、フィルムであることが好ましく、樹脂フィルムであることがより好ましい。仮支持体としては、可撓性を有し、かつ、加圧下、又は、加圧及び加熱下において、著しい変形、収縮、又は、伸びを生じないフィルムが好ましい。
上記フィルムとしては、例えば、ポリエチレンテレフタレートフィルム(例えば、2軸延伸ポリエチレンテレフタレートフィルム)、ポリメチルメタクリレートフィルム、トリ酢酸セルロースフィルム、ポリスチレンフィルム、ポリイミドフィルム、及び、ポリカーボネートフィルムが挙げられる。
なかでも、仮支持体としては、ポリエチレンテレフタレートフィルムが好ましい。
また、仮支持体として使用するフィルムには、シワ等の変形、及び、傷等がないことが好ましい。
仮支持体を介するパターン露光時のパターン形成性、及び、仮支持体の透明性の点から、仮支持体のヘイズは小さい方が好ましい。具体的には、仮支持体のヘイズ値が、2%以下が好ましく、0.5%以下がより好ましく、0.1%以下が更に好ましい。
仮支持体を介するパターン露光時のパターン形成性、及び、仮支持体の透明性の点から、仮支持体に含まれる微粒子、異物、及び、欠陥の数は少ない方が好ましい。仮支持体中における直径1μm以上の微粒子、異物、及び、欠陥の数は、50個/10mm2以下が好ましく、10個/10mm2以下がより好ましく、3個/10mm2以下が更に好ましく、0個/10mm2が特に好ましい。
また、滑剤層の膜厚は、0.05~1.0μmが好ましい。仮支持体の市販品としては、ルミラー16KS40、ルミラー16FB40(以上、東レ株式会社製)、コスモシャインA4100、コスモシャインA4300、及びコスモシャインA8300(以上、東洋紡株式会社製)が挙げられる。
転写フィルムは、ネガ型感光性組成物層を有する。
ネガ型感光性組成物層を被転写体上に転写した後、露光及び現像を行うことにより、被転写体上にパターンを形成できる。なお、ネガ型感光性組成物層では、露光により露光部が硬化膜となって現像液に対する溶解性が低下する。
以下、ネガ型感光性組成物層が含み得る成分について述べる。
ネガ型感光性組成物層は、バインダーポリマーを含む。
バインダーポリマーとしては、例えば、(メタ)アクリル樹脂、スチレン樹脂、エポキシ樹脂、アミド樹脂、アミドエポキシ樹脂、アルキド樹脂、フェノール樹脂、エステル樹脂、ウレタン樹脂、エポキシ樹脂と(メタ)アクリル酸との反応で得られるエポキシアクリレート樹脂、及び、エポキシアクリレート樹脂と酸無水物との反応で得られる酸変性エポキシアクリレート樹脂が挙げられる。
なお、本明細書において、(メタ)アクリル樹脂とは、(メタ)アクリル化合物に由来する構成単位を有する樹脂を意味する。(メタ)アクリル化合物に由来する構成単位の含有量は、(メタ)アクリル樹脂の全構成単位に対して、50質量%以上が好ましく、70質量%以上がより好ましく、90質量%以上が更に好ましい。
(メタ)アクリル樹脂は、(メタ)アクリル化合物に由来する構成単位のみで構成されていてもよく、(メタ)アクリル化合物以外の重合性単量体に由来する構成単位を有していてもよい。すなわち、(メタ)アクリル化合物に由来する構成単位の含有量の上限は、(メタ)アクリル樹脂の全構成単位に対して、100質量%以下である。
(メタ)アクリル酸エステルとしては、例えば、(メタ)アクリル酸アルキルエステル、(メタ)アクリル酸テトラヒドロフルフリルエステル、(メタ)アクリル酸ジメチルアミノエチルエステル、(メタ)アクリル酸ジエチルアミノエチルエステル、(メタ)アクリル酸グリシジルエステル、(メタ)アクリル酸ベンジルエステル、2,2,2-トリフルオロエチル(メタ)アクリレート、及び、2,2,3,3-テトラフルオロプロピル(メタ)アクリレートが挙げられ、(メタ)アクリル酸アルキルエステルが好ましい。
(メタ)アクリルアミドとしては、例えば、ジアセトンアクリルアミド等のアクリルアミドが挙げられる。
また、(メタ)アクリル酸アルキルエステルのアルキル基としては、環状であってもよい。環状アルキル基としては、単環でも多環でもよい。具体例としては、(メタ)アクリル酸シクロヘキシル等が挙げられる。
(メタ)アクリル酸エステルとしては、炭素数1~4のアルキル基を有する(メタ)アクリル酸アルキルエステルが好ましく、(メタ)アクリル酸メチル又は(メタ)アクリル酸エチルがより好ましい。
上記構成単位を形成する重合性単量体としては、(メタ)アクリル化合物と共重合可能な(メタ)アクリル化合物以外の化合物であれば特に制限されず、例えば、スチレン、ビニルトルエン、及び、α-メチルスチレン等のα位又は芳香族環に置換基を有してもよいスチレン化合物、アクリロニトリル及びビニル-n-ブチルエーテル等のビニルアルコールエステル、マレイン酸、マレイン酸無水物、マレイン酸モノメチル、マレイン酸モノエチル、及び、マレイン酸モノイソプロピル等のマレイン酸モノエステル、フマル酸、ケイ皮酸、α-シアノケイ皮酸、イタコン酸、並びに、クロトン酸が挙げられる。
これらの重合性単量体は、1種又は2種以上を組み合わせて用いてもよい。
なかでも、(メタ)アクリル樹脂は、カルボキシ基を有する構成単位を有することがより好ましく、上記の(メタ)アクリル酸に由来する構成単位を有することが更に好ましい。
(メタ)アクリル樹脂における(メタ)アクリル酸アルキルエステルに由来する構成単位の含有量は、(メタ)アクリル樹脂の全構成単位に対して、50~90質量%が好ましく、60~90質量%がより好ましく、65~90質量%が更に好ましく、70~90質量%が特に好ましい。
また、(メタ)アクリル樹脂としては、メタクリル酸に由来する構成単位、メタクリル酸メチルに由来する構成単位、及び、アクリル酸エチルに由来する構成単位を有するアクリル樹脂も好ましい。
(メタ)アクリル樹脂におけるメタクリル酸に由来する構成単位及びメタクリル酸アルキルエステルに由来する構成単位の合計含有量は、本発明の効果がより優れる点で、(メタ)アクリル樹脂の全構成単位に対して、40質量%以上が好ましく、60質量%以上がより好ましい。上限は特に制限されず、100質量%以下であってもよく、80質量%以下が好ましい。
本発明の効果がより優れる点で、メタクリル酸に由来する構成単位及びメタクリル酸アルキルエステルに由来する構成単位の合計含有量は、アクリル酸に由来する構成単位及びアクリル酸アルキルエステルに由来する構成単位の合計含有量に対して、質量比で60/40~80/20が好ましい。
なお、(メタ)アクリル樹脂の末端部は、合成に用いた重合開始剤に由来する部位により構成される。末端にエステル基を有する(メタ)アクリル樹脂は、エステル基を有するラジカルを発生する重合開始剤を用いることにより合成できる。
バインダーポリマーは、例えば、現像性の点から、酸価60mgKOH/g以上のバインダーポリマーであることが好ましい。
また、バインダーポリマーは、例えば、加熱により架橋成分と熱架橋し、強固な膜を形成しやすいという点から、酸価60mgKOH/g以上のカルボキシ基を有する樹脂(いわゆる、カルボキシ基含有樹脂)であることがより好ましく、酸価60mgKOH/g以上のカルボキシ基を有する(メタ)アクリル樹脂(いわゆる、カルボキシ基含有(メタ)アクリル樹脂)であることが更に好ましい。
バインダーポリマーがカルボキシ基を有する樹脂であると、例えば、ブロックイソシアネート化合物等の熱架橋性化合物を添加して熱架橋することで、3次元架橋密度を高めることができる。また、カルボキシ基を有する樹脂のカルボキシ基が無水化され、疎水化すると、湿熱耐性が改善し得る。
例えば、特開2011-095716号公報の段落[0025]に記載のポリマーのうち、酸価60mgKOH/g以上のカルボキシ基含有アクリル樹脂、特開2010-237589号公報の段落[0033]~[0052]に記載のポリマーのうち、酸価60mgKOH/g以上のカルボキシ基含有アクリル樹脂等を好ましく使用できる。
なお、本明細書において、スチレン-アクリル共重合体とは、スチレン化合物に由来する構成単位と、(メタ)アクリル化合物に由来する構成単位とを有する樹脂を指し、上記スチレン化合物に由来する構成単位、及び、上記(メタ)アクリル化合物に由来する構成単位の合計含有量は、上記共重合体の全構成単位に対して、30質量%以上が好ましく、50質量%以上がより好ましい。
また、スチレン化合物に由来する構成単位の含有量の下限値としては、上記共重合体の全構成単位に対して、1質量%以上が好ましく、5質量%以上がより好ましく、20質量%以上が更に好ましい。また、上限値としては、80質量%以下が好ましく、60質量%以下がより好ましく、50質量%以下が更に好ましい。
また、上記(メタ)アクリル化合物に由来する構成単位の含有量の下限値としては、上記共重合体の全構成単位に対して、1質量%以上が好ましく、5質量%以上がより好ましく、10質量%以上が更に好ましく、20質量%以上が特に好ましい。また、その上限値としては、95質量%以下が好ましく、60質量%以下がより好ましく、30質量%以下が更に好ましい。
また、上記(メタ)アクリル化合物に由来する構成単位として、(メタ)アクリル酸に由来する構成単位及び(メタ)アクリル酸アルキルエステルに由来する構成単位の両者を有するのが好ましい。
芳香環構造を有する構成単位を形成するモノマーとしては、アラルキル基を有するモノマー、スチレン、及び重合可能なスチレン誘導体(例えば、メチルスチレン、ビニルトルエン、tert-ブトキシスチレン、アセトキシスチレン、4-ビニル安息香酸、スチレンダイマー、及びスチレントリマー等)が挙げられる。なかでも、アラルキル基を有するモノマー、又はスチレンが好ましい。アラルキル基としては、置換又は非置換のフェニルアルキル基(ベンジル基を除く)、及び置換又は非置換のベンジル基等が挙げられ、置換又は非置換のベンジル基が好ましい。
また、バインダーポリマーにおける芳香環構造を有する構成単位の含有量は、本発明の効果がより優れる点で、バインダーポリマーの全構成単位に対して、5~70モル%が好ましく、10~60モル%がより好ましく、20~60モル%が更に好ましい。
更に、バインダーポリマーにおける上記式(S)で表される構成単位の含有量は、本発明の効果がより優れる点で、バインダーポリマーの全構成単位に対して、5~70モル%が好ましく、10~60モル%がより好ましく、20~60モル%が更に好ましく、20~50モル%が特に好ましい。
なお、本明細書において、「構成単位」の含有量をモル比で規定する場合、上記「構成単位」は「モノマー単位」と同義であるものとする。また、本明細書において、上記「モノマー単位」は、高分子反応等により重合後に修飾されていてもよい。以下においても同様である。
なかでも、本発明の効果がより優れる点で、2環以上の脂肪族炭化水素環が縮環した環が好ましく、テトラヒドロジシクロペンタジエン環(トリシクロ[5.2.1.02,6]デカン環)がより好ましい。
脂肪族炭化水素環構造を有する構成単位を形成するモノマーとしては、ジシクロペンタニル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、及び、イソボルニル(メタ)アクリレートが挙げられる。
また、バインダーポリマーは、本発明の効果がより優れる点で、下記式(Cy)で表される構成単位を有することが好ましく、上記式(S)で表される構成単位、及び、下記式(Cy)で表される構成単位を有することがより好ましい。
式(Cy)におけるRCyは、本発明の効果がより優れる点で、炭素数5~20の脂肪族炭化水素環構造を有する一価の基であることが好ましく、炭素数6~16の脂肪族炭化水素環構造を有する一価の基であることがより好ましく、炭素数8~14の脂肪族炭化水素環構造を有する一価の基であることが更に好ましい。
また、式(Cy)のRCyにおける脂肪族炭化水素環構造は、本発明の効果がより優れる点で、シクロペンタン環構造、シクロヘキサン環構造、テトラヒドロジシクロペンタジエン環構造、ノルボルナン環構造、又は、イソボロン環構造であることが好ましく、シクロヘキサン環構造、又は、テトラヒドロジシクロペンタジエン環構造であることがより好ましく、テトラヒドロジシクロペンタジエン環構造であることが更に好ましい。
更に、式(Cy)のRCyにおける脂肪族炭化水素環構造は、本発明の効果がより優れる点で、2環以上の脂肪族炭化水素環が縮環した環構造であることが好ましく、2~4環の脂肪族炭化水素環が縮環した環であることがより好ましい。
更に、式(Cy)におけるRCyは、本発明の効果がより優れる点で、式(Cy)における-C(=O)O-の酸素原子と脂肪族炭化水素環構造とが直接結合する基、すなわち、脂肪族炭化水素環基であることが好ましく、シクロヘキシル基、又は、ジシクロペンタニル基であることがより好ましく、ジシクロペンタニル基であることが更に好ましい。
バインダーポリマーが脂肪族炭化水素環構造を有する構成単位を有する場合、脂肪族炭化水素環構造を有する構成単位の含有量は、本発明の効果がより優れる点で、バインダーポリマーの全構成単位に対して、5~90質量%が好ましく、10~80質量%がより好ましく、20~70質量%が更に好ましい。
また、バインダーポリマーにおける脂肪族炭化水素環構造を有する構成単位の含有量は、本発明の効果がより優れる点で、バインダーポリマーの全構成単位に対して、5~70モル%が好ましく、10~60モル%がより好ましく、20~50モル%が更に好ましい。
更に、バインダーポリマーにおける上記式(Cy)で表される構成単位の含有量は、本発明の効果がより優れる点で、バインダーポリマーの全構成単位に対して、5~70モル%が好ましく、10~60モル%がより好ましく、20~50モル%が更に好ましい。
また、バインダーポリマーにおける芳香環構造を有する構成単位及び脂肪族炭化水素環構造を有する構成単位の総含有量は、本発明の効果がより優れる点で、バインダーポリマーの全構成単位に対して、10~80モル%が好ましく、20~70モル%がより好ましく、40~60モル%が更に好ましい。
更に、バインダーポリマーにおける上記式(S)で表される構成単位及び上記式(Cy)で表される構成単位の総含有量は、本発明の効果がより優れる点で、バインダーポリマーの全構成単位に対して、10~80モル%が好ましく、20~70モル%がより好ましく、40~60モル%が更に好ましい。
また、バインダーポリマーにおける上記式(S)で表される構成単位のモル量nSと上記式(Cy)で表される構成単位のモル量nCyは、本発明の効果がより優れる点で、下記式(SCy)に示す関係を満たすことが好ましく、下記式(SCy-1)を満たすことがより好ましく、下記式(SCy-2)を満たすことが更に好ましい。
0.2≦nS/(nS+nCy)≦0.8 式(SCy)
0.30≦nS/(nS+nCy)≦0.75 式(SCy-1)
0.40≦nS/(nS+nCy)≦0.70 式(SCy-2)
上記酸基としては、カルボキシ基、スルホ基、ホスホン酸基、及び、リン酸基が挙げられ、カルボキシ基が好ましい。
上記酸基を有する構成単位としては、下記に示す、(メタ)アクリル酸由来の構成単位が好ましく、メタクリル酸由来の構成単位がより好ましい。
バインダーポリマーが酸基を有する構成単位を有する場合、酸基を有する構成単位の含有量は、本発明の効果がより優れる点で、バインダーポリマーの全構成単位に対して、5~50質量%が好ましく、5~40質量%がより好ましく、10~30質量%が更に好ましい。
また、バインダーポリマーにおける酸基を有する構成単位の含有量は、本発明の効果がより優れる点で、バインダーポリマーの全構成単位に対して、5~70モル%が好ましく、10~50モル%がより好ましく、20~40モル%が更に好ましい。
更に、バインダーポリマーにおける(メタ)アクリル酸由来の構成単位の含有量は、本発明の効果がより優れる点で、バインダーポリマーの全構成単位に対して、5~70モル%が好ましく、10~50モル%がより好ましく、20~40モル%が更に好ましい。
反応性基としては、ラジカル重合性基が好ましく、エチレン性不飽和基がより好ましい。また、バインダーポリマーがエチレン性不飽和基を有している場合、バインダーポリマーは、側鎖にエチレン性不飽和基を有する構成単位を有することが好ましい。
本明細書において、「主鎖」とは、樹脂を構成する高分子化合物の分子中で相対的に最も長い結合鎖を表し、「側鎖」とは、主鎖から枝分かれしている原子団を表す。
エチレン性不飽和基としては、アリル基又は(メタ)アクリロキシ基がより好ましい。
反応性基を有する構成単位の一例としては、下記に示すものが挙げられるが、これらに限定されない。
バインダーポリマーが反応性基を有する構成単位を有する場合、反応性基を有する構成単位の含有量の下限値としては、本発明の効果がより優れる点で、バインダーポリマーの全構成単位に対して、5質量%以上が好ましく、10質量%以上がより好ましく、20質量%以上が更に好ましく、35質量%以上が特に好ましく、40質量%以上が最も好ましい。また、その上限値としては、70質量%以下が好ましく、60質量%以下がより好ましく、50質量%以下が更に好ましい。
また、バインダーポリマーにおける反応性基を有する構成単位の含有量の下限値は、本発明の効果がより優れる点で、バインダーポリマーの全構成単位に対して、5モル%以上が好ましく、10モル%以上がより好ましく、20モル%以上が更に好ましく、35モル%以上が特に好ましく、40モル%以上が最も好ましい。また、その上限値としては、70モル%以下が好ましく、60モル%以下がより好ましく、50モル%以下が更に好ましい。
反応性基をバインダーポリマーに導入する手段の好ましい例としては、カルボキシ基を有するポリマーを重合反応により合成した後、高分子反応により、得られたポリマーのカルボキシ基の一部にグリシジル(メタ)アクリレートを反応させて、(メタ)アクリロキシ基をポリマーに導入する手段が挙げられる。この手段により、側鎖に(メタ)アクリロキシ基を有するバインダーポリマーを得ることができる。
上記重合反応は、70~100℃の温度条件で行うことが好ましく、80~90℃の温度条件で行うことがより好ましい。上記重合反応に用いる重合開始剤としては、アゾ系開始剤が好ましく、例えば、富士フイルム和光純薬(株)製のV-601(商品名)又はV-65(商品名)がより好ましい。上記高分子反応は、80~110℃の温度条件で行うことが好ましい。上記高分子反応においては、アンモニウム塩等の触媒を用いることが好ましい。
(ポリマーX1) a:20~60質量%、b:10~50質量%、c:5.0~25質量%、d:10~50質量%。
(ポリマーX2) a:20~60質量%、b:10~50質量%、c:5.0~25質量%、d:10~50質量%。
(ポリマーX3) a:30~65質量%、b:1.0~20質量%、c:5.0~25質量%、d:10~50質量%。
(ポリマーX4) a:1.0~20質量%、b:20~60質量%、c:5.0~25質量%、d:10~50質量%。
カルボン酸無水物構造は、鎖状カルボン酸無水物構造、及び、環状カルボン酸無水物構造のいずれであってもよいが、環状カルボン酸無水物構造であることが好ましい。
環状カルボン酸無水物構造の環としては、5~7員環が好ましく、5員環又は6員環がより好ましく、5員環が更に好ましい。
Z1aとしては、炭素数2~4のアルキレン基が好ましく、炭素数2又は3のアルキレン基がより好ましく、炭素数2のアルキレン基が更に好ましい。
n1aは、0以上の整数を表す。Z1aが炭素数2~4のアルキレン基を表す場合、n1aは、0~4の整数であることが好ましく、0~2の整数であることがより好ましく、0であることが更に好ましい。
n1aが2以上の整数を表す場合、複数存在するRA1aは、同一でも異なっていてもよい。また、複数存在するRA1aは、互いに結合して環を形成してもよいが、互いに結合して環を形成していないことが好ましい。
ネガ型感光性組成物層が重合体Xを含む場合、本発明の効果がより優れる点で、重合体Xの含有量は、ネガ型感光性組成物層の全質量に対して、0.1~30質量%が好ましく、0.2~20質量%がより好ましく、0.5~20質量%が更に好ましく、1~20質量%が更に好ましい。
なお、バインダーポリマーの酸価は、例えば、JIS K0070:1992に記載の方法に従って、化合物中における酸基の平均含有量から算出できる。バインダーポリマーの分散度は、現像性の観点から、1.0~6.0が好ましく、1.0~5.0がより好ましく、1.0~4.0が更に好ましく、1.0~3.0が特に好ましい。
バインダーポリマーの含有量は、本発明の効果がより優れる点で、ネガ型感光性組成物層の全質量に対して、10~90質量%が好ましく、20~80質量%がより好ましく、25~70質量%が更に好ましく、25~60質量%が特に好ましい。
ネガ型感光性組成物層は、重合性化合物を含んでもよい。
重合性化合物は、重合性基を有する化合物である。重合性基としては、例えば、ラジカル重合性基、及び、カチオン重合性基が挙げられ、ラジカル重合性基が好ましい。
エチレン性不飽和基としては、(メタ)アクリロキシ基が好ましい。
なお、本明細書におけるエチレン性不飽和化合物は、上記バインダーポリマー以外の化合物であり、分子量5,000未満であることが好ましい。
エチレン性不飽和化合物中のエチレン性不飽和基の個数としては特に制限されないが、1個以上が好ましく、2個以上がより好ましい。上限値は特に制限されないが、例えば、20個以下である。
Q2-R1-Q1 式(M)
式(M)中、Q1及びQ2はそれぞれ独立に、(メタ)アクリロイルオキシ基を表し、R1は鎖状構造を有する二価の連結基を表す。
また、式(M)におけるQ1及びQ2は、反応性の点から、アクリロイルオキシ基であることが好ましい。
式(M)におけるR1としては、本発明の効果がより優れる点で、アルキレン基、アルキレンオキシアルキレン基(-L1-O-L1-)、又は、ポリアルキレンオキシアルキレン基(-(L1-O)p-L1-)が好ましく、炭素数2~20の炭化水素基、又は、ポリアルキレンオキシアルキレン基がより好ましく、炭素数4~20のアルキレン基が更に好ましく、炭素数6~18の直鎖アルキレン基が特に好ましい。
上記炭化水素基は、少なくとも一部に鎖状構造を有していればよく、上記鎖状構造以外の部分としては、特に制限はなく、例えば、分岐鎖状、環状、又は、炭素数1~5の直鎖状アルキレン基、アリーレン基、エーテル結合、及び、それらの組み合わせのいずれであってもよく、アルキレン基、又は、2以上のアルキレン基と1以上のアリーレン基とを組み合わせた基が好ましく、アルキレン基がより好ましく、直鎖アルキレン基が更に好ましい。
なお、上記L1は、それぞれ独立に、アルキレン基を表し、エチレン基、プロピレン基、又は、ブチレン基が好ましく、エチレン基又は1,2-プロピレン基がより好ましい。pは2以上の整数を表し、2~10の整数であることが好ましい。
本明細書において、「Q1とQ2の間を連結する最短の連結鎖の原子数」とは、Q1に連結するR1における原子からQ2に連結するR1における原子までを連結する最短の原子数である。
上記化合物のなかでも、本発明の効果がより優れる点で、1,6-ヘキサンジオールジ(メタ)アクリレート、1,9-ノナンジオールジ(メタ)アクリレート、1,10-デカンジオールジ(メタ)アクリレート、及び、ネオペンチルグリコールジ(メタ)アクリレートからなる群から選ばれた少なくとも1種の化合物であることが好ましく、1,6-ヘキサンジオールジ(メタ)アクリレート、1,9-ノナンジオールジ(メタ)アクリレート、及び、1,10-デカンジオールジ(メタ)アクリレートからなる群から選ばれた少なくとも1種の化合物であることがより好ましく、1,9-ノナンジオールジ(メタ)アクリレート、及び、1,10-デカンジオールジ(メタ)アクリレートからなる群から選ばれた少なくとも1種の化合物であることが更に好ましい。
本明細書において、「2官能以上のエチレン性不飽和化合物」とは、一分子中にエチレン性不飽和基を2個以上有する化合物を意味する。上記エチレン性不飽和基としては、(メタ)アクリロイル基が好ましい。2官能以上のエチレン性不飽和化合物としては、(メタ)アクリレート化合物が好ましい。
上記化合物M以外の2官能のエチレン性不飽和化合物としては、トリシクロデカンジメタノールジ(メタ)アクリレート、及び、1,4-シクロヘキサンジオールジ(メタ)アクリレートが挙げられる。
3官能以上のエチレン性不飽和化合物としては、ジペンタエリスリトール(トリ/テトラ/ペンタ/ヘキサ)(メタ)アクリレート、ペンタエリスリトール(トリ/テトラ)(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、ジトリメチロールプロパンテトラ(メタ)アクリレート、イソシアヌル酸(メタ)アクリレート、及び、グリセリントリ(メタ)アクリレート骨格の(メタ)アクリレート化合物が挙げられる。
3官能のエチレン性不飽和化合物の市販品としては、例えば、トリメチロールプロパントリアクリレート(新中村化学工業社製「A-TMPT」等が挙げられる。
また、4官能のエチレン性不飽和化合物の市販品としては、例えば、ペンタエリスリトールテトラアクリレート(新中村化学工業社製「A-TMMT」)等が挙げられる。
また、5又は6官能のエチレン性不飽和化合物の市販品としては、ジペンタエリスリトールポリアクリレート(新中村化学工業社製「A-DPH」)等が挙げられる。
ウレタン(メタ)アクリレートとしては、ウレタンジ(メタ)アクリレートが挙げられ、例えば、プロピレンオキサイド変性ウレタンジ(メタ)アクリレート、並びに、エチレンオキサイド及びプロピレンオキサイド変性ウレタンジ(メタ)アクリレートが挙げられる。
また、ウレタン(メタ)アクリレートとしては、3官能以上のウレタン(メタ)アクリレートも挙げられる。官能基数の下限としては、6官能以上がより好ましく、8官能以上が更に好ましい。なお、官能基数の上限としては、20官能以下が好ましい。3官能以上のウレタン(メタ)アクリレートとしては、例えば、8UX-015A(大成ファインケミカル(株)製)、UA-32P(新中村化学工業(株)製)、U-15HA(新中村化学工業(株)製)、UA-1100H(新中村化学工業(株)製)、共栄社化学(株)製のAH-600(商品名)、並びに、UA-306H、UA-306T、UA-306I、UA-510H、及びUX-5000(いずれも日本化薬(株)製)等が挙げられる。
酸基を有するエチレン性不飽和化合物としては、酸基を有する3~4官能のエチレン性不飽和化合物〔ペンタエリスリトールトリ及びテトラアクリレート(PETA)骨格にカルボキシ基を導入したもの(酸価:80~120mgKOH/g)〕、酸基を有する5~6官能のエチレン性不飽和化合物(ジペンタエリスリトールペンタ及びヘキサアクリレート(DPHA)骨格にカルボキシ基を導入したもの〔酸価:25~70mgKOH/g)〕等が挙げられる。
これら酸基を有する3官能以上のエチレン性不飽和化合物は、必要に応じ、酸基を有する2官能のエチレン性不飽和化合物と併用してもよい。
酸基を有するエチレン性不飽和化合物が、カルボキシ基を有する2官能以上のエチレン性不飽和化合物及びそのカルボン酸無水物からなる群から選ばれる少なくとも1種であると、現像性及び膜強度がより高まる。
カルボキシ基を有する2官能以上のエチレン性不飽和化合物は、特に制限されず、公知の化合物の中から適宜選択できる。
カルボキシ基を有する2官能以上のエチレン性不飽和化合物としては、アロニックス(登録商標)TO-2349(東亞合成(株)製)、アロニックス(登録商標)M-520(東亞合成(株)製)、アロニックス(登録商標)M-510(東亞合成(株)製)が挙げられる。
これらは単独で又は2種類以上を組み合わせて使用される。
なかでも、テトラメチロールメタン構造又はトリメチロールプロパン構造を有するエチレン性不飽和化合物が好ましく、テトラメチロールメタントリ(メタ)アクリレート、テトラメチロールメタンテトラ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、又は、ジ(トリメチロールプロパン)テトラアクリレートがより好ましい。
エステル結合を含むエチレン性不飽和化合物としては、分子内にエステル結合を含むものであれば特に制限されないが、本発明の効果が優れる点で、テトラメチロールメタン構造又はトリメチロールプロパン構造を有するエチレン性不飽和化合物が好ましく、テトラメチロールメタントリ(メタ)アクリレート、テトラメチロールメタンテトラ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、又は、ジ(トリメチロールプロパン)テトラアクリレートがより好ましい。
炭素数6以上の脂肪族構造を有するエチレン性不飽和化合物としては、1,9-ノナンジオールジ(メタ)アクリレート、1,10-デカンジオールジ(メタ)アクリレート、及び、トリシクロデカンジメタノールジ(メタ)アクリレートが挙げられる。
上記重合性化合物としては、2環以上の脂肪族炭化水素環が縮環した環構造(好ましくは、トリシクロデカン構造及びトリシクロデセン構造からなる群から選択される構造)を有する重合性化合物が好ましく、2環以上の脂肪族炭化水素環が縮環した環構造を有する2官能エチレン性不飽和化合物がより好ましく、トリシクロデカンジメタノールジ(メタ)アクリレートが更に好ましい。
上記脂肪族炭化水素環構造としては、本発明の効果がより優れる点から、シクロペンタン構造、シクロヘキサン構造、トリシクロデカン構造、トリシクロデセン構造、ノルボルナン構造、又は、イソボロン構造が好ましい。
2官能のエチレン性不飽和化合物と、3官能以上のエチレン性不飽和化合物の含有量の質量比は10:90~90:10が好ましく、30:70~70:30がより好ましい。
全てのエチレン性不飽和化合物の合計量に対する、2官能のエチレン性不飽和化合物の含有量は、20~80質量%が好ましく、30~70質量%がより好ましい。
ネガ型感光性組成物層における2官能のエチレン性不飽和化合物は、10~60質量%が好ましく、15~40質量%がより好ましい。
また、ネガ型感光性組成物層の好適態様の一つとして、ネガ型感光性組成物層は、基板密着性、現像残渣抑制性、及び、防錆性の点から、化合物M、及び、酸基を有するエチレン性不飽和化合物を含むことが好ましく、化合物M、脂肪族炭化水素環構造を有する2官能エチレン性不飽和化合物、及び、酸基を有するエチレン性不飽和化合物を含むことがより好ましく、化合物M、脂肪族炭化水素環構造を有する2官能エチレン性不飽和化合物、3官能以上のエチレン性不飽和化合物、及び、酸基を有するエチレン性不飽和化合物を含むことが更に好ましく、化合物M、脂肪族炭化水素環構造を有する2官能エチレン性不飽和化合物、3官能以上のエチレン性不飽和化合物、酸基を有するエチレン性不飽和化合物、及び、ウレタン(メタ)アクリレート化合物を含むことが特に好ましい。
また、ネガ型感光性組成物層の好適態様の一つとして、ネガ型感光性組成物層は、ネガ型感光性組成物層は、基板密着性、現像残渣抑制性、及び、防錆性の点から、1,9-ノナンジオールジアクリレート、及び、カルボン酸基を有する多官能エチレン性不飽和化合物を含むことが好ましく、1,9-ノナンジオールジアクリレート、トリシクロデカンジメタノールジアクリレート、及び、カルボン酸基を有する多官能エチレン性不飽和化合物を含むことが好ましく、1,9-ノナンジオールジアクリレート、トリシクロデカンジメタノールジアクリレート、ジペンタエリスリトールヘキサアクリレート、及び、カルボン酸基を有するエチレン性不飽和化合物を含むことが更に好ましく、1,9-ノナンジオールジアクリレート、トリシクロデカンジメタノールジアクリレート、カルボン酸基を有するエチレン性不飽和化合物、及び、ウレタンアクリレート化合物を含むことが特に好ましい。
上記エチレン性不飽和化合物における2官能以上のエチレン性不飽和化合物の含有量は、ネガ型感光性組成物層に含まれる全てのエチレン性不飽和化合物の総含有量に対し、60~100質量%が好ましく、80~100質量%がより好ましく、90~100質量%が更に好ましい。
ネガ型感光性組成物層におけるエチレン性不飽和化合物の含有量の下限値としては、ネガ型感光性組成物層の全質量に対して、1質量%以上が好ましく、5質量%以上がより好ましく、20質量%以上が更に好ましく、35質量%以上が特に好ましく、40質量%以上が最も好ましい。また、その上限値としては特に制限されないが、70質量%以下が好ましく、60質量%以下がより好ましく、55質量%以下が更に好ましい。
ネガ型感光性組成物層は、重合開始剤を含んでもよい。
重合開始剤としては、光重合開始剤が好ましく、公知の光重合開始剤を使用できる。
光重合開始剤としては、オキシムエステル構造を有する光重合開始剤(以下、「オキシム系光重合開始剤」ともいう。)、α-アミノアルキルフェノン構造を有する光重合開始剤(以下、「α-アミノアルキルフェノン系光重合開始剤」ともいう。)、α-ヒドロキシアルキルフェノン構造を有する光重合開始剤(以下、「α-ヒドロキシアルキルフェノン系重合開始剤」ともいう。)、アシルフォスフィンオキサイド構造を有する光重合開始剤(以下、「アシルフォスフィンオキサイド系光重合開始剤」ともいう。)、及び、N-フェニルグリシン構造を有する光重合開始剤(以下、「N-フェニルグリシン系光重合開始剤」ともいう。)等が挙げられる。
ネガ型感光性組成物層において、光重合開始剤の含有量は、ネガ型感光性組成物層の全質量に対して、0.1質量%以上であるのが好ましく、0.5質量%以上であるのがより好ましく、1.0質量%以上であるのが更に好ましい。また、その上限値としては、ネガ型感光性組成物層の全質量に対して、10質量%以下であるのが好ましく、5質量%以下であるのより好ましい。
ネガ型感光性組成物層は、複素環化合物を含んでもよい。
複素環化合物が有する複素環は、単環及び多環のいずれの複素環でもよい。
複素環化合物が有するヘテロ原子としては、窒素原子、酸素原子、及び、硫黄原子が挙げられる。複素環化合物は、窒素原子、酸素原子、及び、硫黄原子からなる群より選ばれる少なくとも1種の原子を有することが好ましく、窒素原子を有することがより好ましい。
上記のなかでも、複素環化合物としては、トリアゾール化合物、ベンゾトリアゾール化合物、テトラゾール化合物、チアジアゾール化合物、トリアジン化合物、ローダニン化合物、チアゾール化合物、ベンゾイミダゾール化合物、及び、ベンゾオキサゾール化合物からなる群より選ばれる少なくとも1種の化合物が好ましく、トリアゾール化合物、ベンゾトリアゾール化合物、テトラゾール化合物、チアジアゾール化合物、チアゾール化合物、ベンゾチアゾール化合物、ベンゾイミダゾール化合物、及び、ベンゾオキサゾール化合物からなる群より選ばれる少なくとも1種の化合物がより好ましい。
トリアゾール化合物及びベンゾトリアゾール化合物としては、以下の化合物が挙げられる。
ネガ型感光性組成物層が複素環化合物を含む場合、複素環化合物の含有量は、ネガ型感光性組成物層の全質量に対して、0.01~20.0質量%が好ましく、0.10~10.0質量%がより好ましく、0.30~8.0質量%が更に好ましく、0.50~5.0質量%が特に好ましい。
ネガ型感光性組成物層は、脂肪族チオール化合物を含んでもよい。
ネガ型感光性組成物層が、脂肪族チオール化合物を含む場合、脂肪族チオール化合物とエチレン性不飽和化合物との間でエン-チオール反応が生じ得る。この結果として、形成される膜の硬化収縮が抑えられ、応力が緩和される。
ネガ型感光性組成物層は、得られる硬化膜の強度、及び、得られる未硬化膜の粘着性の点から、熱架橋性化合物を含むことが好ましい。なお、本明細書においては、後述するエチレン性不飽和基を有する熱架橋性化合物は、エチレン性不飽和化合物としては扱わず、熱架橋性化合物として扱うものとする。
熱架橋性化合物としては、エポキシ化合物、オキセタン化合物、メチロール化合物、及び、ブロックイソシアネート化合物が挙げられる。なかでも、得られる硬化膜の強度、及び、得られる未硬化膜の粘着性の点から、ブロックイソシアネート化合物が好ましい。
ブロックイソシアネート化合物は、ヒドロキシ基及びカルボキシ基と反応するため、例えば、バインダーポリマー及びエチレン性不飽和基を有するラジカル重合性化合物の少なくとも一方が、ヒドロキシ基及びカルボキシ基の少なくとも一方を有する場合には、形成される膜の親水性が下がり、保護膜としての機能が強化される傾向がある。
なお、ブロックイソシアネート化合物とは、「イソシアネートのイソシアネート基をブロック剤で保護(いわゆる、マスク)した構造を有する化合物」を指す。
ブロックイソシアネートの解離温度とは、「示差走査熱量計を用いて、DSC(Differential scanning calorimetry)分析にて測定した場合における、ブロックイソシアネートの脱保護反応に伴う吸熱ピークの温度」を意味する。
示差走査熱量計としては、例えば、セイコーインスツルメンツ(株)製の示差走査熱量計(型式:DSC6200)を好適に使用できる。但し、示差走査熱量計は、これに限定されない。
これらのなかでも、解離温度が100~160℃であるブロック剤としては、例えば、保存安定性の点から、オキシム化合物から選ばれる少なくとも1種が好ましい。
イソシアヌレート構造を有するブロックイソシアネート化合物は、例えば、ヘキサメチレンジイソシアネートをイソシアヌレート化して保護することにより得られる。
イソシアヌレート構造を有するブロックイソシアネート化合物のなかでも、オキシム化合物をブロック剤として用いたオキシム構造を有する化合物が、オキシム構造を有さない化合物よりも解離温度を好ましい範囲にしやすく、かつ、現像残渣を少なくしやすいという点から好ましい。
重合性基としては、特に制限はなく、公知の重合性基を用いることができ、ラジカル重合性基が好ましい。
重合性基としては、(メタ)アクリロキシ基、(メタ)アクリルアミド基、及び、スチリル基等のエチレン性不飽和基、並びに、グリシジル基等のエポキシ基を有する基が挙げられる。
なかでも、重合性基としては、エチレン性不飽和基が好ましく、(メタ)アクリロキシ基がより好ましく、アクリロキシ基が更に好ましい。
ブロックイソシアネート化合物の市販品の例としては、カレンズ(登録商標) AOI-BM、カレンズ(登録商標) MOI-BM、カレンズ(登録商標) MOI-BP等(以上、昭和電工(株)製)、ブロック型のデュラネートシリーズ(例えば、デュラネート(登録商標) TPA-B80E、デュラネート(登録商標) WT32-B75P等、旭化成ケミカルズ(株)製)が挙げられる。
ネガ型感光性組成物層が熱架橋性化合物を含む場合、熱架橋性化合物の含有量は、ネガ型感光性組成物層の全質量に対して、1~50質量%が好ましく、5~30質量%がより好ましい。
ネガ型感光性組成物層は、界面活性剤を含んでもよい。
界面活性剤としては、例えば、特許第4502784号公報の段落[0017]、及び、特開2009-237362号公報の段落[0060]~[0071]に記載の界面活性剤が挙げられる。
フッ素系界面活性剤の市販品としては、例えば、メガファック F-171、F-172、F-173、F-176、F-177、F-141、F-142、F-143、F-144、F-437、F-475、F-477、F-479、F-482、F-551-A、F-552、F-554、F-555-A、F-556、F-557、F-558、F-559、F-560、F-561、F-565、F-563、F-568、F-575、F-780、EXP.MFS-330、EXP.MFS-578、EXP.MFS-578-2、EXP.MFS-579、EXP.MFS-586、EXP.MFS-587、EXP.MFS-628、EXP.MFS-631、EXP.MFS-603、R-41、R-41-LM、R-01、R-40、R-40-LM、RS-43、TF-1956、RS-90、R-94、RS-72-K、DS-21(以上、DIC株式会社製)、フロラード FC430、FC431、FC171(以上、住友スリーエム(株)製)、サーフロンS-382、SC-101、SC-103、SC-104、SC-105、SC-1068、SC-381、SC-383、S-393、KH-40(以上、AGC(株)製)、PolyFox PF636、PF656、PF6320、PF6520、PF7002(以上、OMNOVA社製)、フタージェント 710FL、710FM、610FM、601AD、601ADH2、602A、215M、245F、251、212M、250、209F、222F、208G、710LA、710FS、730LM、650AC、681、683(以上、(株)NEOS製)、U-120E(ユニケム株式会社)等が挙げられる。
また、フッ素系界面活性剤としては、フッ素原子を含有する官能基を持つ分子構造を有し、熱を加えるとフッ素原子を含有する官能基の部分が切断されてフッ素原子が揮発するアクリル系化合物も好適に使用できる。このようなフッ素系界面活性剤としては、DIC(株)製のメガファック DSシリーズ(化学工業日報(2016年2月22日)、日経産業新聞(2016年2月23日))、例えばメガファック DS-21が挙げられる。
また、フッ素系界面活性剤としては、フッ素化アルキル基またはフッ素化アルキレンエーテル基を有するフッ素原子含有ビニルエーテル化合物と、親水性のビニルエーテル化合物との重合体を用いることも好ましい。
また、フッ素系界面活性剤としては、ブロックポリマーも使用できる。
また、フッ素系界面活性剤としては、フッ素原子を有する(メタ)アクリレート化合物に由来する構成単位と、アルキレンオキシ基(好ましくはエチレンオキシ基、プロピレンオキシ基)を2以上(好ましくは5以上)有する(メタ)アクリレート化合物に由来する構成単位と、を含む含フッ素高分子化合物も好ましく使用できる。
また、フッ素系界面活性剤としては、エチレン性不飽和基を側鎖に有する含フッ素重合体も使用できる。メガファック RS-101、RS-102、RS-718K、RS-72-K(以上、DIC株式会社製)等が挙げられる。
ノニオン系界面活性剤としては、グリセロール、トリメチロールプロパン、及びトリメチロールエタン並びにそれらのエトキシレート及びプロポキシレート(例えば、グリセロールプロポキシレート、グリセロールエトキシレート等)、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル、ポリエチレングリコールジラウレート、ポリエチレングリコールジステアレート、ソルビタン脂肪酸エステル、プルロニック(登録商標) L10、L31、L61、L62、10R5、17R2、25R2(以上、BASF社製)、テトロニック 304、701、704、901、904、150R1、HYDROPALAT WE 3323(以上、BASF社製)、ソルスパース 20000(以上、日本ルーブリゾール(株)製)、NCW-101、NCW-1001、NCW-1002(以上、富士フイルム和光純薬(株)製)、パイオニン D-1105、D-6112、D-6112-W、D-6315(以上、竹本油脂(株)製)、オルフィンE1010、サーフィノール104、400、440(以上、日信化学工業(株)製)等が挙げられる。
ネガ型感光性組成物層が界面活性剤を含む場合、界面活性剤の含有量は、ネガ型感光性組成物層の全質量に対して、0.01~3.0質量%が好ましく、0.01~1.0質量%がより好ましく、0.05~0.80質量%が更に好ましい。
ネガ型感光性組成物層は、重合禁止剤を含んでもよい。
重合禁止剤とは、重合反応を遅延又は禁止させる機能を有する化合物を意味する。重合禁止剤としては、例えば、重合禁止剤として用いられる公知の化合物を使用できる。
なかでも、本発明の効果がより優れる点で、重合禁止剤としては、フェノチアジン化合物、ニトロソ化合物又はその塩、及び、ヒンダードフェノール化合物からなる群より選ばれる少なくとも1種が好ましく、フェノチアジン、ビス[3-(3-tert-ブチル-4-ヒドロキシ-5-メチルフェニル)プロピオン酸]、[エチレンビス(オキシエチレン)]2,4-ビス〔(ラウリルチオ)メチル〕-o-クレゾール、1,3,5-トリス(3,5-ジ-t-ブチル-4-ヒドロキシベンジル)、p-メトキシフェノール、及び、N-ニトロソフェニルヒドロキシルアミンアルミニウム塩がより好ましい。
ネガ型感光性組成物層が重合禁止剤を含む場合、重合禁止剤の含有量は、ネガ型感光性組成物層全質量に対して、0.001~5.0質量%が好ましく、0.01~3.0質量%がより好ましく、0.02~2.0質量%が更に好ましい。重合禁止剤の含有量は、重合性化合物全質量に対しては、0.005~5.0質量%が好ましく、0.01~3.0質量%がより好ましく、0.01~1.0質量%が更に好ましい。
ネガ型感光性組成物層は、水素供与性化合物を含んでもよい。
水素供与性化合物は、光重合開始剤の活性光線に対する感度を一層向上させる、及び、酸素による重合性化合物の重合阻害を抑制する等の作用を有する。
なかでも、本発明の効果がより優れる点で、アミン類としては、4,4’-ビス(ジエチルアミノ)ベンゾフェノン、及び、トリス(4-ジメチルアミノフェニル)メタンからなる群より選ばれる少なくとも1種が好ましい。
なかでも、本発明の効果がより優れる点で、アミノ酸化合物としては、N-フェニルグリシンが好ましい。
ネガ型感光性組成物層が水素供与性化合物を含む場合、水素供与性化合物の含有量は、重合成長速度と連鎖移動のバランスとによる硬化速度の向上の点から、ネガ型感光性組成物層の全質量に対して、0.01~10.0質量%が好ましく、0.01~8.0質量%がより好ましく、0.03~5.0質量%が更に好ましい。
ネガ型感光性組成物層は、所定量の不純物を含んでもよい。
不純物の具体例としては、ナトリウム、カリウム、マグネシウム、カルシウム、鉄、マンガン、銅、アルミニウム、チタン、クロム、コバルト、ニッケル、亜鉛、スズ、ハロゲン及びこれらのイオンが挙げられる。なかでも、ハロゲン化物イオン、ナトリウムイオン、及び、カリウムイオンは不純物として混入し易いため、下記の含有量にすることが好ましい。
ネガ型感光性組成物層は、上述したバインダーポリマー(例えば、アルカリ可溶性樹脂)の各構成単位の残存モノマーを含む場合がある。
残存モノマーの含有量は、パターニング性、及び、信頼性の点から、バインダーポリマーの全質量に対して、5,000質量ppm以下が好ましく、2,000質量ppm以下がより好ましく、500質量ppm以下が更に好ましい。下限は特に制限されないが、1質量ppm以上が好ましく、10質量ppm以上がより好ましい。
バインダーポリマーの各構成単位の残存モノマーは、パターニング性、及び、信頼性の点から、ネガ型感光性組成物層の全質量に対して、3,000質量ppm以下が好ましく、600質量ppm以下がより好ましく、100質量ppm以下が更に好ましい。下限は特に制限されないが、0.1質量ppm以上が好ましく、1質量ppm以上がより好ましい。
残存モノマーの量は、液体クロマトグラフィー、及び、ガスクロマトグラフィー等の公知の方法で測定できる。
ネガ型感光性組成物層は、既述の成分以外の成分(以下、「他の成分」ともいう。)を含んでもよい。他の成分としては、例えば、着色剤、酸化防止剤、及び、粒子(例えば、金属酸化物粒子)が挙げられる。また、他の成分としては、特開2000-310706号公報の段落[0058]~[0071]に記載のその他の添加剤も挙げられる。
粒子としては、金属酸化物粒子が好ましい。
金属酸化物粒子における金属には、B、Si、Ge、As、Sb、及び、Te等の半金属も含まれる。
粒子の平均一次粒子径は、例えば、硬化膜の透明性の点から、1~200nmが好ましく、3~80nmがより好ましい。
粒子の平均一次粒子径は、電子顕微鏡を用いて任意の粒子200個の粒子径を測定し、測定結果を算術平均することにより算出される。なお、粒子の形状が球形でない場合には、最も長い辺を粒子径とする。
ネガ型感光性組成物層は、粒子を含まないか、或いは、ネガ型感光性組成物層が粒子を含む場合には、粒子の含有量がネガ型感光性組成物層の全質量に対して、0質量%超35質量%以下が好ましく、粒子を含まないか、或いは、粒子の含有量がネガ型感光性組成物層の全質量に対して、0質量%超10質量%以下がより好ましく、粒子を含まないか、或いは、粒子の含有量がネガ型感光性組成物層の全質量に対して0質量%超5質量%以下が更に好ましく、粒子を含まないか、或いは、粒子の含有量がネガ型感光性組成物層の全質量に対して0質量%超1質量%以下が更に好ましく、粒子を含まないことが特に好ましい。
ネガ型感光性組成物層は、微量の着色剤(顔料、染料等)を含んでもよいが、例えば、透明性の点からは、着色剤を実質的に含まないことが好ましい。
ネガ型感光性組成物層が着色剤を含む場合、着色剤の含有量は、ネガ型感光性組成物層の全質量に対して、1質量%未満が好ましく、0.1質量%未満がより好ましい。
酸化防止剤としては、例えば、1-フェニル-3-ピラゾリドン(別名:フェニドン)、1-フェニル-4,4-ジメチル-3-ピラゾリドン、及び、1-フェニル-4-メチル-4-ヒドロキシメチル-3-ピラゾリドン等の3-ピラゾリドン類;ハイドロキノン、カテコール、ピロガロール、メチルハイドロキノン、及び、クロルハイドロキノン等のポリヒドロキシベンゼン類;パラメチルアミノフェノール、パラアミノフェノール、パラヒドロキシフェニルグリシン、及び、パラフェニレンジアミンが挙げられる。
なかでも、本発明の効果がより優れる点で、酸化防止剤としては、3-ピラゾリドン類が好ましく、1-フェニル-3-ピラゾリドンがより好ましい。
ネガ型感光性組成物層の厚みは、特に制限されないが30μm以下の場合が多く、本発明の効果がより優れる点で、20μm以下が好ましく、15μm以下がより好ましく、10μm以下が更に好ましく、3.0μm以下が特に好ましい。下限としては、ネガ型感光性組成物層を硬化して得られる膜の強度が優れる点で、0.60μm以上が好ましく、1.5μm以上がより好ましい。
ネガ型感光性組成物層の厚みは、例えば、走査型電子顕微鏡(SEM)による断面観察により測定した任意の5点の平均値として算出できる。
ネガ型感光性組成物層の屈折率は、1.47~1.56が好ましく、1.49~1.54がより好ましい。
ネガ型感光性組成物層は無彩色であることが好ましい。具体的には、全反射(入射角8°、光源:D-65(2°視野))が、CIE1976(L*,a*,b*)色空間において、L*値は10~90であることが好ましく、a*値は-1.0~1.0であることが好ましく、b*値は-1.0~1.0であることが好ましい。
具体的には、全反射(入射角8°、光源:D-65(2°視野))が、CIE1976(L*,a*,b*)色空間において、パターンのL*値は10~90であることが好ましく、パターンのa*値は-1.0~1.0であることが好ましく、パターンのb*値は-1.0~1.0であることが好ましい。
ネガ型感光性組成物層を硬化して得られるパターン(ネガ型感光性組成物層の硬化膜)の膜厚40μmでの透湿度は、防錆性の観点から、500g/m2/24hr以下であることが好ましく、300g/m2/24hr以下であることがより好ましく、100g/m2/24hr以下であることが更に好ましい。
なお、透湿度は、ネガ型感光性組成物層を、i線によって露光量300mJ/cm2にて露光した後、145℃、30分間のポストベークを行うことにより、ネガ型感光性組成物層を硬化させた硬化膜で測定する。
ネガ型感光性組成物層の炭酸ナトリウム1.0%水溶液に対する溶解速度は、現像時の残渣抑制の観点から、0.01μm/秒以上が好ましく、0.10μm/秒以上がより好ましく、0.20μm/秒以上が更に好ましい。パターンのエッジ形状の観点から、5.0μm/秒以下が好ましく、4.0μm/秒以下がより好ましく、3.0μm/秒以下が更に好ましい。具体的な好ましい数値としては、例えば、1.0μm/秒、0.8μm/秒等である。1.0質量%炭酸ナトリウム水溶液に対するネガ型感光性組成物層の単位時間あたりの溶解速度は、以下のように測定するものとする。
ガラス基板に形成した、溶剤を十分に除去したネガ型感光性組成物層(膜厚1.0~10μmの範囲内)に対し、25℃の1.0質量%炭酸ナトリウム水溶液を用いて、ネガ型感光性組成物層が溶け切るまでシャワー現像を行う(但し、最長で2分までとする)。
ネガ型感光性組成物層の膜厚を、ネガ型感光性組成物層が溶け切るまでに要した時間で割り算することで求める。なお、2分で溶け切らない場合は、それまでの膜厚変化量から同様に計算する。(株)いけうち製1/4MINJJX030PPのシャワーノズルを使用し、シャワーのスプレー圧は0.08MPaとする。上記条件の時、単位時間当たりのシャワー流量は1,800mL/minとする。
露光後のネガ型感光性組成物層の1.0質量%炭酸ナトリウム水溶液に対する膨潤率は、パターン形成性向上の観点から、100%以下が好ましく、50%以下がより好ましく、30%以下が更に好ましい。
なお、露光後のネガ型感光性組成物層の1.0質量%炭酸ナトリウム水溶液に対する膨潤率は、以下のように測定するものとする。
ガラス基板に形成した、溶媒を十分に除去したネガ型感光性組成物層(膜厚1.0~10μmの範囲内)に対し、超高圧水銀灯で500mj/cm2(i線測定)で露光する。25℃でガラス基板ごと、1.0質量%炭酸ナトリウム水溶液に浸漬し、30秒経過時点での膜厚を測定する。そして、浸漬後の膜厚が浸漬前の膜厚に対して増加した割合を計算する。
具体的な好ましい数値としては、例えば、13%、25%等が挙げられる。
パターン形成性の観点から、ネガ型感光性組成物層中の直径1.0μm以上の異物の数は、10個/mm2以下であることが好ましく、5個/mm2以下であることがより好ましい。異物個数は以下のように測定するものとする。ネガ型感光性組成物層の表面の法線方向から、ネガ型感光性組成物層の面上の任意の5か所の領域(1mm×1mm)を、光学顕微鏡を用いて目視にて観察して、各領域中の直径1.0μm以上の異物の数を測定して、それらを算術平均して異物の数として算出する。
現像時での凝集物発生抑止の観点から、1.0質量%炭酸ナトリウムの30℃水溶液1.0リットルに1.0cm3のネガ型感光性組成物層を溶解させて得られる溶液のヘイズは60%以下であることが好ましく、30%以下であることがより好ましく、10%以下であることが更に好ましく、1%以下であることが最も好ましい。
なお、ヘイズは以下のように測定するものとする。
まず、1.0質量%の炭酸ナトリウム水溶液を準備し、液温を30℃に調整する。炭酸ナトリウム水溶液1.0Lに1.0cm3のネガ型感光性組成物層を入れる。気泡を混入しないように注意しながら、30℃で4時間撹拌する。撹拌後、ネガ型感光性組成物層が溶解した溶液のヘイズを測定する。ヘイズは、ヘイズメーター(製品名「NDH4000」、日本電色工業社製)を用い、液体測定用ユニット及び光路長20mmの液体測定専用セルを用いて測定される。
転写フィルムは、紫外線吸収層を有する。
紫外線吸収層は、紫外線吸収剤とClogP値が2.1より小さいポリマー(以下「特定ポリマー」ともいう)を含む。なお、紫外線吸収剤がポリマーであり且つClogP値が2.1より小さい場合、このポリマーは、特定ポリマーには含まれない。
紫外線吸収層は、紫外線を吸収可能な層(具体的には、波長450nm以下の紫外線を吸収可能な層)であり、例えば、高圧水銀灯が発光するg線(435nm)、h線(405nm)、i線(365nm)、及びj線(313nm)等の紫外線、KrF露光装置での露光波長である248nm、並びに、ArF露光装置での露光波長である193nm等の波長の紫外線を吸収できるのが好ましく、h線(405nm)及びi線(365nm)を吸収できるのがより好ましい。
紫外線吸収層の波長405nmにおける透過率としては、本発明の効果がより優れる点で、70%以下であるのが好ましく、50%以下であるのがより好ましく、40%以下であるのが更に好ましい。なお、下限値としては、例えば、20%以上であるのが好ましい。
透過率は、紫外可視分光高度計(例えば、(株)島津製作所製UV-1800)を使用して測定できる。
また、紫外線吸収層の光学濃度(OD値、波長365nm)としては、本発明の効果がより優れる点で、0.1~0.6が好ましく、0.1~0.4がより好ましい。
光学濃度(OD値)の測定は、例えば、(株)日立ハイテクノロジー製の分光器UV4100(商品名)を使用できる。
紫外線吸収剤としては、紫外線を吸収可能な化合物であり、ネガ型感光性組成物層に含まれ得る光重合開始剤の感光波長の少なくとも一部の波長の光を吸収可能な紫外線吸収特性を有することが好ましい。
紫外線吸収剤の波長365nmの光に対するモル吸光係数としては、5,000~100,000(L/(mol・cm))であるのが好ましく、10,000~80,000(L/(mol・cm))であるのがより好ましく、15,000~50,000(L/(mol・cm))であるのが更に好ましい。
紫外線吸収剤のモル吸光係数は、以下の方法により測定するものとする。
測定対象の化合物をN,N-ジメチルホルムアミドを用いて4×10-6(g/mL)の溶液とする。この溶液を、(株)島津製作所製UV測定装置UV2550を用いて365nmでの吸光度を測定する。得られた吸光度等より、式:[モル吸光係数]=[吸光度]/[溶液の質量濃度/吸光性化合物の分子量]によりモル吸光係数を算出する。
紫外線吸収剤としては、例えば、高分子紫外線吸収剤及びポリマー被覆型紫外線吸収剤等が挙げられる。
紫外線吸収構造としては、トリアジン構造、ベンゾトリアゾール構造、ベンゾフェノン構造、又は、サリチル酸構造が好ましく、トリアジン構造がより好ましい。
また、紫外線吸収構造を有する単量体に由来する構成単位を含むポリマーは、(メタ)アクリル樹脂であるのが好ましい。なお、上記(メタ)アクリル樹脂としては、後述する第1B実施形態の転写フィルムの熱可塑性樹脂層に含まれ得るアルカリ可溶性樹脂としての(メタ)アクリル樹脂を形成するためのモノマーで形成されているのが好ましい。
高分子紫外線吸収剤中、紫外線吸収構造を有する単量体に由来する構成単位の含有量としては、ポリマーの全質量に対し、10~80質量%であるのが好ましく、30~70質量%であるのがより好ましい。
上記ポリマーとしては、(メタ)アクリル樹脂、ポリエステル、ポリウレタン、ポリオレフィン、シロキサン樹脂、及びフッ素ポリマー等が挙げられ、(メタ)アクリル樹脂が好ましい。なお、上記(メタ)アクリル樹脂としては、後述する第1B実施形態の転写フィルムの熱可塑性樹脂層中に含まれ得るアルカリ可溶性樹脂としての(メタ)アクリル樹脂が好ましい。
ポリマー被覆型紫外線吸収剤における紫外線吸収剤の含有量は、ポリマー被覆型紫外線吸収剤の全量に対し、20~80質量%が好ましく、30~70質量%がより好ましく、40~60質量%が更に好ましい。
ポリマー被覆型紫外線吸収剤におけるポリマーの含有量は、ポリマー被覆型紫外線吸収剤の全量に対し、20~80質量%が好ましく、30~70質量%がより好ましく、40~60質量%が更に好ましい。
ポリマー被覆型紫外線吸収剤が粒子である場合、そのメジアン径(D50)の上限値としては、500nm以下が好ましく、400nm以下がより好ましく、200nm以下が更に好ましく、100nm以下が特に好ましい。また、メジアン径の下限値としては、10nm以上であるのが好ましく、20nm以上であるのがより好ましい。メジアン径は、動的光散乱測定による粒度分布から算出できる。
紫外線吸収層は、ClogP値が2.1より小さいポリマー(特定ポリマー)を含む。
特定バインダーのClogPは、本発明の効果がより優れる点で、2.0以下が好ましく、1.9以下がより好ましい。また、その下限値としては特に制限されないが、1.0以上であるのが好ましい。
本明細書において、ClogPとは、1-オクタノール及び水への分配係数Pの常用対数logPを計算によって求めた値である。
上記ClogPの計算に用いる方法及びソフトウェアについては公知のものを使用できるが、特に断らない限り、本明細書では、Cambridge soft社のChemBioDraw Ultra 12.0に組み込まれたClogPプログラムを用いることとする。
本明細書において、I/O値とは、有機概念図における有機性値(O)に対する無機性値(I)の比(以下「I/O値」ともいう)である。
特定バインダーのI/O値は次の方法によって求める。甲田善生著、有機概念図-基礎と応用-(1984)13ページ等に記載されている有機性(O値)、無機性(I値)を元に、特定バインダーを構成する各モノマーのI/O値を算出する。特定バインダーを構成する各モノマーについて、その「I/O値」と「特定バインダーの全構成単位に対するモル%」の積を算出し、これらを合計して、特定ポリマーのI/O値とする。
SP値(δ)=(EV/v)1/2=(ΣΔei/ΣΔvi)1/2・・・式(1)
EV:蒸発エネルギー
v:モル体積
Δei:各原子又は原子団の蒸発エネルギー
Δvi:各原子又は原子団のモル体積
また、本明細書において、特定バインダーポリマーが異なるm(mが2以上の整数)種類のモノマーを共重合させて得たポリマーである場合、SP値は、下記式によって計算される。
SP値(δ)=X1δ1+・・・+Xmδm
X1、・・・、Xmは、共重合体を構成する各モノマーのモル%であり、且つ、X1+・・・Xm=100モル%である。
δ1、・・・、δmは、共重合体を構成する各モノマーのSP値であり、上記式(1)で求めた値である。
なお、(メタ)アクリル樹脂とは、上述のとおり、(メタ)アクリル化合物に由来する構成単位を有する樹脂を意味する。(メタ)アクリル化合物に由来する構成単位の含有量は、(メタ)アクリル樹脂の全構成単位に対して、50質量%以上が好ましく、70質量%以上がより好ましく、90質量%以上が更に好ましい。
(メタ)アクリル樹脂は、(メタ)アクリル化合物に由来する構成単位のみで構成されていてもよく、(メタ)アクリル化合物以外の重合性単量体に由来する構成単位を有していてもよい。すなわち、(メタ)アクリル化合物に由来する構成単位の含有量の上限は、(メタ)アクリル樹脂の全構成単位に対して、100質量%以下である。
(メタ)アクリル酸アルキルエステルのアルキル基としては、直鎖状でも分岐を有していてもよい。具体例としては、例えば、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸プロピル、(メタ)アクリル酸ブチル、(メタ)アクリル酸ペンチル、(メタ)アクリル酸ヘキシル、(メタ)アクリル酸ヘプチル、(メタ)アクリル酸オクチル、(メタ)アクリル酸2-エチルヘキシル、(メタ)アクリル酸ノニル、(メタ)アクリル酸デシル、(メタ)アクリル酸ウンデシル、及び、(メタ)アクリル酸ドデシル等の炭素数が1~12のアルキル基を有する(メタ)アクリル酸アルキルエステルが挙げられる。
また、(メタ)アクリル酸アルキルエステルのアルキル基としては、環状であってもよい。環状アルキル基としては、単環でも多環でもよい。具体例としては、(メタ)アクリル酸シクロヘキシル等が挙げられる。
(メタ)アクリル樹脂における酸基を有する構成単位(好ましくは(メタ)アクリル酸に由来する構成単位)の含有量は、本発明の効果がより優れる点で、(メタ)アクリル樹脂の全質量に対して、10質量%以上が好ましい。また、上限値は特に制限されないが、アルカリ耐性に優れる点で、50質量%以下が好ましく、40質量%以下がより好ましい。
特定ポリマーの重量平均分子量としては、5,000~100,000が好ましく、7,000~50,000がより好ましく、10,000~50,000が更に好ましい。
バインダーポリマーの分散度は、現像性の観点から、1.0~6.0が好ましく、1.0~5.0がより好ましく、1.0~4.0が更に好ましく、1.0~3.0が特に好ましい。
特定ポリマーの含有量は、紫外線吸収層の全質量に対して、例えば、20~95質量%であるのが好ましく、40~95質量%であるのがより好ましく、50~90質量%であるのが更に好ましく、60~90質量%であるのが特に好ましい。
また、特定ポリマーに対する紫外線吸収剤の含有量比(紫外線吸収剤の含有量/特定ポリマの含有量)としては、0.05~0.4であるのがより好ましく、0.1~0.3であるのが更に好ましい。
紫外線吸収層の好適な一態様としては、光硬化性であるのも好ましい。光硬化性の紫外線吸収層としては、エチレン性不飽和化合物を含むのが好ましく、エチレン性不飽和化合物及び光重合開始剤を含むのがより好ましい。
紫外線吸収層が重合性化合物(好ましくは、エチレン性不飽和化合物)を含む場合、重合性化合物(好ましくは、エチレン性不飽和化合物)の含有量は、紫外線吸収層の強度がより優れる点で、紫外線吸収層の全質量に対し、1~70質量%が好ましく、10~70質量%がより好ましく、15~60質量%が更に好ましく、15~40質量%が特に好ましい。
紫外線吸収層が重合開始剤(好ましくは、光重合開始剤)を含む場合、重合開始剤(好ましくは、光重合開始剤)の含有量は、紫外線吸収層の強度がより優れる点で、紫外線吸収層の全質量に対し、0.1~10質量%が好ましく、0.5~10質量%がより好ましく、0.5~5質量%が更に好ましい。
紫外線吸収層が界面活性剤を含む場合、界面活性剤の含有量は、紫外線吸収層の全質量に対して、0.01~3質量%が好ましく、0.05~1質量%がより好ましく、0.1~0.8質量%が更に好ましい。
他の成分としては、例えば、金属酸化物粒子、ヘテロ環状化合物以外の架橋剤、アルコキシシラン化合物、酸化防止剤、分散剤、酸増殖剤、現像促進剤、導電性繊維、着色剤、熱ラジカル発生剤、熱酸発生剤、増粘剤、及び、有機又は無機の沈殿防止剤等の公知の添加剤が挙げられる。
転写フィルムは、仮支持体の剥離性がより向上する点で、仮支持体とネガ型感光性組成物層との間に中間層(中間層A)を有しているのが好ましい。
中間層としては、水溶性樹脂を含む水溶性樹脂層であるのが好ましい。
また、中間層としては、酸素遮断能を有していることが好ましい。中間層が酸素遮断能を有することで、露光時の感度が向上し、露光機の時間負荷が低減して生産性が向上するため好ましい。また、露光の際の重合反応において酸素阻害が生じにくい利点もある。
中間層としては、なかでも、低い酸素透過性を示し、水又はアルカリ水溶液(22℃の炭酸ナトリウムの1質量%水溶液)に分散又は溶解する層であるのが好ましい。
上記樹脂は、その一部又は全部として、水溶性樹脂を含むのが好ましい。
水溶性樹脂として使用可能な樹脂としては、例えば、ポリビニルアルコール系樹脂、ポリビニルピロリドン系樹脂、セルロース系樹脂(例えば、ヒドロキシプロピルセルロース及びヒドロキシプロピルメチルセルロース等の水溶性セルロース誘導体)、アクリルアミド系樹脂、ポリエーテル系樹脂(例えば、ポリエチレングリコール及びポリプロピレングリコール等のポリアルキレンオキサイド系樹脂)、ゼラチン、ビニルエーテル系樹脂、ポリアミド樹脂、及びこれらの共重合体等の樹脂が挙げられる。
また、水溶性樹脂としては、(メタ)アクリル酸/ビニル化合物の共重合体等も使用できる。(メタ)アクリル酸/ビニル化合物の共重合体としては、(メタ)アクリル酸/(メタ)アクリル酸アリルの共重合体が好ましく、メタクリル酸/メタクリル酸アリルの共重合体がより好ましい。水溶性樹脂が(メタ)アクリル酸/ビニル化合物の共重合体である場合、各組成比(モル%)としては、例えば、90/10~20/80が好ましく、80/20~30/70がより好ましい。
水溶性樹脂の分散度(Mw/Mn)は、1~10が好ましく、1~5がより好ましい。
また、ポリビニルアルコール及びポリビニルピロリドンの1種以上と、水溶性セルロース誘導体及びポリエーテル類の1種以上とを併用するのも好ましく、ポリビニルアルコール及びポリビニルピロリドンの1種以上と、水溶性セルロース誘導体とを併用するのがより好ましい。
ポリエーテル類としては、ポリエチレングリコール及びポリプロピレングリコール等が挙げられる。
水溶性樹脂の含有量は特に制限されないが、仮支持体の剥離性がより向上する点で、及び/又は、酸素遮断能がより優れる点で、中間層の全質量に対して、50質量%以上が好ましく、70質量%以上がより好ましい。なお、その上限値としては特に制限されないが、例えば、100質量%以下であり、99.9質量%以下が好ましく、99.8質量%以下がより好ましく、99質量%以下が更に好ましい。
なお、上記他の成分の分子量の上限値としては特に制限されず、5,000未満が好ましく、4,000以下がより好ましく、3,000以下が更に好ましく、2,000以下が特に好ましく、1,500以下が最も好ましい。なお、下限値としては、例えば、60以上である。
多価アルコール類が含む水酸基の個数としては特に制限されず、例えば、2~10個が好ましい。
多価アルコール類としては、例えば、グリセリン、ジグリセリン、及びジエチレングリコール等が挙げられる。
多価アルコール類のアルキレンオキサイド付加物としては、上述の多価アルコール類にエチレンオキサイド及びプロピレンオキサイド等を付加した化合物が挙げられる。なお、平均付加数は特に制限されず、例えば、1~100であり、2~50が好ましく、2~20がより好ましい。
フェノール誘導体としては、ビスフェノールA及びビスフェノールS等が挙げられる。
アミド化合物としては、N-メチルピロリドン等が挙げられる。
上記他の成分の含有量は特に制限されないが、仮支持体の剥離性がより向上する点で、中間層の全質量に対して、0.1質量%以上が好ましく、0.5質量%以上がより好ましく、1質量%以上が更に好ましい。なお、その上限値としては特に制限されないが、例えば、30質量%未満が好ましく、10質量%以下がより好ましく、5質量%以下が更に好ましい。
中間層の組成は、特に、ポリビニルアルコール及びポリビニルピロリドンの1種以上と、化合物Xとして水溶性セルロース誘導体及びポリエーテル類の1種以上とを含むのがより好ましく、中間層の可塑化をより抑制し易い点で、ポリビニルアルコール及びポリビニルピロリドンの1種以上と、化合物Xとして水溶性セルロース誘導体を含むのが更に好ましく、仮支持体剥離性がより優れる点で、ポリビニルアルコール及びポリビニルピロリドンの1種以上と、化合物Xとしてヒドロキシプロピルメチルセルロースを含むのが特に好ましい。
また、ポリビニルアルコール及びポリビニルピロリドンは、両者を併用するのが好ましい。
中間層が上記組成である場合、ポリビニルアルコール及びポリビニルピロリドンの合計含有量としては、仮支持体の剥離性がより向上する点で、中間層の全質量に対して、50質量%以上が好ましく、70質量%以上がより好ましい。なお、その上限値としては特に制限されないが、例えば、100質量%以下であり、99.9質量%以下が好ましく、99.8質量%以下がより好ましく、99質量%以下が更に好ましい。
また、中間層が上記組成である場合、ポリビニルアルコールの含有量としては、中間層の全質量に対して、5~95質量%であるのが好ましい。
また、中間層が上記組成である場合、ポリビニルアルコールとポリビニルピロリドンとの配合比(質量比)としては、5/95~95/5であるのが好ましく、20/80~80/20が更に好ましく、25/75~70/25が更に好ましい。
また、中間層が上記組成である場合、化合物Xの含有量は特に制限されないが、仮支持体の剥離性がより向上する点で、中間層の全質量に対して、0.1質量%以上が好ましく、0.5質量%以上がより好ましく、0.8質量%以上が更に好ましい。上限値としては、30質量%未満が好ましく、15質量%以下がより好ましい。化合物Xの含有量が、中間層の全質量に対して30質量%未満である場合、中間層形成成分の相分離が抑制されやすく、これに起因する中間層の表面の粗面化が生じにくいため、解像性により優れる。
転写フィルムは、屈折率調整層を有しているのが好ましい。
屈折率調整層としては、公知の屈折率調整層を適用できる。屈折率調整層に含まれる材料としては、例えば、バインダーポリマー、重合性化合物、金属塩、及び、粒子が挙げられる。
屈折率調整層の屈折率を制御する方法は、特に制限されず、例えば、所定の屈折率の樹脂を単独で用いる方法、樹脂と粒子とを用いる方法、及び、金属塩と樹脂との複合体を用いる方法が挙げられる。
金属酸化物粒子の種類は特に制限はなく、公知の金属酸化物粒子が挙げられる。金属酸化物粒子における金属には、B、Si、Ge、As、Sb、及び、Te等の半金属も含まれる。
粒子の平均一次粒子径は、電子顕微鏡を用いて任意の粒子200個の粒子径を測定し、測定結果を算術平均することにより算出される。なお、粒子の形状が球形でない場合には、最も長い辺を粒子径とする。
これらのなかでも、金属酸化物粒子としては、例えば、屈折率を調整しやすいという点から、酸化ジルコニウム粒子及び酸化チタン粒子からなる群から選ばれる少なくとも1種がより好ましい。
屈折率調整層における粒子の含有量は、屈折率調整層全質量に対し、1~95質量%が好ましく、20~90質量%がより好ましく、40~85質量%が更に好ましい。
金属酸化物粒子として酸化チタンを用いる場合、酸化チタン粒子の含有量は、屈折率調整層全質量に対して、1~95質量%が好ましく、20~90質量%がより好ましく、40~85質量%が更に好ましい。
屈折率調整層の屈折率は、1.50以上が好ましく、1.55以上がより好ましく、1.60以上が更に好ましく、1.65以上が特に好ましい。屈折率調整層の屈折率の上限は、2.10以下が好ましく、1.85以下がより好ましく、1.78以下が更に好ましい。
なお、上記屈折率は、25℃における波長550nmの屈折率である。
屈折率調整層の厚みは、走査型電子顕微鏡(SEM)による断面観察により測定した任意の5点の平均値として算出する。
転写フィルムは、保護フィルムを有していてもよい。
保護フィルムとしては、耐熱性及び耐溶剤性を有する樹脂フィルムを用いることができ、例えば、ポリプロピレンフィルム及びポリエチレンフィルム等のポリオレフィンフィルム、ポリエチレンテレフタレートフィルム等のポリエステルフィルム、ポリカーボネートフィルム、並びに、ポリスチレンフィルムが挙げられる。
また、保護フィルムとして上述の仮支持体と同じ材料で構成された樹脂フィルムを用いてもよい。
なかでも、保護フィルムとしては、ポリオレフィンフィルムが好ましく、ポリプロピレンフィルム又はポリエチレンフィルムがより好ましく、ポリエチレンフィルムが更に好ましい。
保護フィルムの厚みは、機械的強度に優れる点で、1μm以上が好ましく、比較的安価となる点で、100μm以下が好ましい。
なお、「フィッシュアイ」とは、材料を熱溶融し、混練、押し出し、2軸延伸及びキャスティング法等の方法によりフィルムを製造する際に、材料の異物、未溶解物、及び、酸化劣化物等がフィルム中に取り込まれたものである。
これにより、保護フィルムに含まれる粒子に起因する凹凸がネガ型感光性組成物層又は導電層に転写されることにより生じる欠陥を抑制することができる。
保護フィルムは、転写時の欠陥抑制の点から、組成物層と接する面の表面粗さRa、0.01μm以上が好ましく、0.02μm以上がより好ましく、0.03μm以上が更に好ましい。一方で、0.50μm未満が好ましく、0.40μm以下がより好ましく、0.30μm以下が更に好ましい。
転写フィルムは、仮支持体、ネガ型感光性組成物層、及び保護フィルムの各物性が以下の態様を示すのが好ましい。
転写フィルムは、好適態様1、好適態様2、好適態様3、好適態様4、及び好適態様5の1つ以上を満たすのが好ましく、いずれも満たすのがより好ましい。
「仮支持体のネガ型感光性組成物層側の表面の算術平均粗さRa」は以下の方法によって測定できる。3次元光学プロファイラー(New View7300、Zygo社)を用いて、以下の条件にて測定対象物の表面プロファイルを得る。測定及び解析ソフトウェアとしては、MetroPro ver8.3.2のMicroscope Applicationを用いる。次に、上記ソフトウェアを用いてSurface Map画面を表示し、Surface Map画面中でヒストグラムデータを得る。得られたヒストグラムデータから、測定対象物の表面の算術平均粗さRaを得る。
「保護フィルムのネガ型感光性組成物層側の表面の算術平均粗さRa」の測定方法は、「仮支持体のネガ型感光性組成物層側の表面の算術平均粗さRa」の測定方法と同様にして実施される。
転写フィルムは、仮支持体、ネガ型感光性組成物層、及び保護フィルムの各物性は、下記(P1)~(P3)の各条件をいずれも満たすのが好ましい。
(P1)ネガ型感光性組成物層を硬化した硬化膜の120℃における破断伸びが15%以上である。
(P2)仮支持体のネガ型感光性組成物層側の表面の算術平均粗さRaが50nm以下である。
(P3)保護フィルムのネガ型感光性組成物層側の表面の算術平均粗さRaが150nm以下である。
転写フィルムの仮支持体及びネガ型感光性組成物層の各物性は、下記式(1)を満たすことが好ましい。
X×Y<1500 式(1)
ここで、式(1)中、Xは、ネガ型感光性組成物層を硬化した硬化膜の120℃における破断伸びの値(%)を表し、Yは、仮支持体のネガ型感光性組成物層側の表面の算術平均粗さRaの値(nm)を表す。
上記式(1)において、X×Yで表される値は、750以下であるのが好ましい。
転写フィルムの感光性の物性は、下記条件(P4)を満たすことが好ましい。
(P4)ネガ型感光性組成物層を硬化した硬化膜の23℃での破断伸びに対し、120℃での破断伸びが2倍以上大きい。
転写フィルムの仮支持体及びネガ型感光性組成物層の各物性は、下記式(2)を満たすことが好ましい。
Y ≦ Z 式(2)
ここで、式(2)中、Yは、仮支持体のネガ型感光性組成物層側の表面の算術平均粗さRaの値(nm)を表し、Zは、保護フィルムのネガ型感光性組成物層側の表面の算術平均粗さRaの値(nm)を表す。
第1A実施形態の転写フィルムの製造方法は特に制限されず、公知の方法を使用できる。
上記の転写フィルム10の製造方法としては、例えば、仮支持体1の表面に中間層(中間層A)用形成用組成物を塗布して塗膜を形成し、更にこの塗膜を乾燥して中間層(中間層A)3を形成する工程と、中間層(中間層A)3の表面にネガ型感光性組成物層形成用組成物を塗布して塗膜を形成し、更にこの塗膜を乾燥してネガ型感光性組成物層5を形成する工程と、ネガ型感光性組成物層5の表面に紫外線吸収層形成用組成物を塗布して塗膜を形成し、更にこの塗膜を乾燥して紫外線吸収層7を形成する工程と、紫外線吸収層7の表面に屈折率調整層形成用組成物を塗布して塗膜を形成し、更にこの塗膜を乾燥して屈折率調整層9を形成する工程と、を含む方法が挙げられる。
第1A実施形態の転写フィルムの製造方法としては、屈折率調整層9の仮支持体1を有する側とは反対側の面に接するように保護フィルム11を設ける工程を含むことにより、仮支持体1、中間層(中間層A)3、ネガ型感光性組成物層5、紫外線吸収層7、屈折率調整層9、及び、保護フィルム11を備える転写フィルム10を製造することが好ましい。
上記の製造方法により転写フィルム10を製造した後、転写フィルム10を巻き取ることにより、ロール形態の転写フィルムを作製及び保管してもよい。ロール形態の転写フィルムは、後述するロールツーロール方式での基板との貼合工程にそのままの形態で提供できる。
また、上記の転写フィルム10の製造方法としては、仮支持体1上に、中間層(中間層A)3、ネガ型感光性組成物層5、及び紫外線吸収層7を形成し、別途、保護フィルム11上に屈折率調整層9を形成し、紫外線吸収層7と屈折率調整層9とを貼り合わせて形成する方法であってもよい。
中間層(中間層A)形成用組成物としては、上述した中間層(中間層A)を形成する各種成分と、必要に応じて溶剤とを含むのが好ましい。なお、中間層(中間層A)形成用組成物において、組成物の全固形分に対する各成分の含有量の好適範囲は、上述した中間層(中間層A)の全質量に対する各成分の含有量の好適範囲と同じである。
溶剤としては、中間層(中間層A)形成用組成物に含まれる成分を溶解又は分散可能であれば特に制限されず、水及び水混和性の有機溶剤からなる群より選択される少なくとも1種が好ましく、水又は水と水混和性の有機溶剤との混合溶剤がより好ましい。
水混和性の有機溶剤としては、例えば、炭素数1~3のアルコール、アセトン、エチレングリコール、及びグリセリンが挙げられ、炭素数1~3のアルコールが好ましく、メタノール又はエタノールがより好ましい。
溶剤は、1種単独で使用してもよく、2種以上使用してもよい。
溶剤の含有量は、組成物の全固形分100質量部に対して、50~2,500質量部が好ましく、50~1,900質量部がより好ましく、100~900質量部が更に好ましい。
生産性に優れる点で、転写フィルム中のネガ型感光性組成物層は、上述したネガ型感光性組成物層を構成する成分(例えば、バインダーポリマー、重合性化合物、及び、重合開始剤等)及び溶剤を含むネガ型感光性組成物層形成用組成物を使用して塗布法により形成されるのが望ましい。第1A実施形態の転写フィルムの製造方法としては、具体的には、仮支持体上にネガ型感光性組成物層形成用組成物を塗布して塗膜を形成し、この塗膜に乾燥処理を施してネガ型感光性組成物層を形成する方法であるのが好ましい。
ネガ型感光性組成物層形成用組成物の全固形分量は、ネガ型感光性組成物層形成用組成物の全質量に対して、5~80質量%が好ましく、5~70質量%がより好ましく、5~65質量%が更に好ましい。
つまり、ネガ型感光性組成物層形成用組成物中の溶剤の含有量としては、ネガ型感光性組成物層形成用組成物の全質量に対して、20~95質量%が好ましく、30~95質量%がより好ましく、35~95質量%が更に好ましい。
乾燥温度としては、80℃以上が好ましく、90℃以上がより好ましい。また、その上限値としては130℃以下が好ましく、120℃以下がより好ましい。温度を連続的に変化させて乾燥させることもできる。
また、乾燥時間としては、20秒以上が好ましく、40秒以上がより好ましく、60秒以上が更に好ましい。また、その上限値としては特に制限されないが、600秒以下が好ましく、300秒以下がより好ましい。
紫外線吸収層形成用組成物としては、上述した紫外線吸収層を形成する各種成分と溶剤とを含むのが好ましい。なお、紫外線吸収層形成用組成物において、組成物の全固形分に対する各成分の含有量の好適範囲は、上述した紫外線吸収層の全質量に対する各成分の含有量の好適範囲と同じである。
溶剤としては、紫外線吸収層形成用組成物に含まれる成分を溶解又は分散可能であれば特に制限されず、水及び水混和性の有機溶剤からなる群より選択される少なくとも1種が好ましく、水又は水と水混和性の有機溶剤との混合溶剤がより好ましい。
水混和性の有機溶剤としては、例えば、炭素数1~3のアルコール、アセトン、エチレングリコール、及びグリセリンが挙げられ、炭素数1~3のアルコールが好ましく、メタノール又はエタノールがより好ましい。
溶剤は、1種単独で使用してもよく、2種以上使用してもよい。
溶剤の含有量は、組成物の全固形分100質量部に対して、50~2,500質量部が好ましく、50~1,900質量部がより好ましく、100~900質量部が更に好ましい。
屈折率調整層形成用組成物としては、上述した屈折率調整層を形成する各種成分と溶剤とを含むのが好ましい。なお、屈折率調整層形成用組成物において、組成物の全固形分に対する各成分の含有量の好適範囲は、上述した屈折率調整層の全質量に対する各成分の含有量の好適範囲と同じである。
溶剤としては、屈折率調整層に含まれる成分を溶解又は分散可能であれば特に制限されず、水及び水混和性の有機溶剤からなる群より選択される少なくとも1種が好ましく、水又は水と水混和性の有機溶剤との混合溶剤がより好ましい。
水混和性の有機溶剤としては、例えば、炭素数1~3のアルコール、アセトン、エチレングリコール、及びグリセリンが挙げられ、炭素数1~3のアルコールが好ましく、メタノール又はエタノールがより好ましい。
溶剤は、1種単独で使用してもよく、2種以上使用してもよい。
溶剤の含有量は、組成物の全固形分100質量部に対して、50~2,500質量部が好ましく、50~1,900質量部がより好ましく、100~900質量部が更に好ましい。
保護フィルムを屈折率調整層に貼り合わせる方法は特に制限されず、公知の方法が挙げられる。
保護フィルムを屈折率調整層に貼り合わせる装置としては、真空ラミネーター、及び、オートカットラミネーター等の公知のラミネーターが挙げられる。
ラミネーターはゴムローラー等の任意の加熱可能なローラーを備え、加圧及び加熱ができるものであることが好ましい。
以下において、第1B実施形態の転写フィルムの実施形態の一例について説明する。
図2に示す転写フィルム30は、仮支持体21と、熱可塑性樹脂層23、中間層(中間層B)25、ネガ型感光性組成物層27、及び紫外線吸収層29を含む組成物層22と、保護フィルム31とを、この順に有する。
なお、図2で示す転写フィルム30は保護フィルム31を配置した形態であるが、保護フィルム31は、配置されなくてもよい。
また、図2で示す転写フィルム30は、熱可塑性樹脂層23及び中間層(中間層B)25を配置した形態であるが、熱可塑性樹脂層23及び中間層(中間層B)25の少なくとも1つは、配置されなくてもよい。
また、図2で示す転写フィルム30は、仮支持体21と熱可塑性樹脂層23との間に、中間層(中間層A)を配置した形態であってもよい。なお、中間層(中間層A)とは、上述の第1A実施形態の転写フィルムが備える中間層(中間層A)と同じである。
以下において、第1B実施形態の転写フィルム(以下「転写フィルム」略記することもある。)を構成する各要素について説明する。
なお、第1B実施形態の転写フィルムにおいて、仮支持体21、紫外線吸収層29、及び保護フィルム31としては、上述した第1A実施形態の仮支持体1、紫外線吸収層9、及び保護フィルム11と同じものが挙げられ、好適態様も同じである。
静電容量型入力装置等のタッチパネルを備えた表示装置(有機エレクトロルミネッセンス(EL)表示装置及び液晶表示装置等)では、視認部のセンサーに相当する電極パターン、周辺配線部分及び取り出し配線部分の配線等の導電層パターンがタッチパネル内部に設けられている。一般的にパターン化した層の形成には、転写フィルム等を用いて基板上にネガ型感光性組成物層を設け、このネガ型感光性組成物層に対して所望のパターンを有するマスクを介して露光した後、現像する方法が広く採用されている。なお、ネガ型感光性組成物層では、露光により露光部が硬化膜となって現像液に対する溶解性が低下する。
つまり、一態様において、ネガ型感光性組成物層は、アルカリ可溶性樹脂を含むバインダーポリマー、重合性化合物、及び重合開始剤を含むのが好ましい。このようなネガ型感光性組成物層は、ネガ型感光性組成物層の全質量を基準として、バインダーポリマー:10~90質量%;重合性化合物:5~70質量%;重合開始剤:0.01~20質量%を含むことが好ましい。
以下において、各成分を順に説明する。
ネガ型感光性組成物層は、バインダーポリマーとして、重合体Aを含むのが好ましい。
重合体Aは、アルカリ可溶性樹脂であることが好ましい。
重合体Aの酸価は、現像液によるネガ型感光性組成物層の膨潤を抑制することにより、解像性がより優れる観点から、220mgKOH/g以下が好ましく、200mgKOH/g未満がより好ましく、190mgKOH/g未満が更に好ましい。
重合体Aの酸価の下限は特に制限されないが、60mgKOH/g以上が好ましい。現像性がより優れる点で、なかでも、120mgKOH/g以上がより好ましく、150mgKOH/g以上が更に好ましく、170mgKOH/g以上が特に好ましい。
重合体Aの酸価は、重合体Aを構成する構成単位の種類及び酸基を含む構成単位の含有量により調整すればよい。
一方で、重量平均分子量が5,000以上の場合、現像凝集物の性状、並びにネガ型感光性樹脂積層体とした場合のエッジフューズ性及びカットチップ性等の未露光膜の性状を制御する観点から好ましい。重量平均分子量は、10,000以上がより好ましい。エッジフューズ性とは、ネガ型感光性樹脂積層体としてロール状に巻き取った場合に、ロールの端面からの、ネガ型感光性組成物層のはみ出し易さの程度をいう。カットチップ性とは、未露光膜をカッターで切断した場合に、チップの飛び易さの程度をいう。このチップがネガ型感光性樹脂積層体の上面等に付着すると、後の露光工程等でマスクに転写して、不良品の原因となる。重合体Aの分散度は、1.0~6.0が好ましく、1.0~5.0がより好ましく、1.0~4.0が更に好ましく、1.0~3.0が特に好ましい。なお、分散度とは、数平均分子量に対する重量平均分子量の比(重量平均分子量/数平均分子量)を意図する。また、重量平均分子量及び数平均分子量は、ゲルパーミエーションクロマトグラフィを用いて測定される値である。
重合体Aにおける第一の単量体に基づく構成単位の含有量は、重合体Aの全質量に対して、5~50質量%が好ましく、10~40質量%がより好ましく、15~30質量%が更に好ましい。
上記含有量を5質量%以上にすることは、良好な現像性を発現させる観点、エッジフューズ性を制御する等の観点から好ましい。上記含有量を50質量%以下にすることは、レジストパターンの高解像性及びスソ形状の観点から、更にはレジストパターンの耐薬品性の観点から好ましい。
重合体Aにおける第二の単量体に基づく構成単位の含有量は、重合体Aの全質量に対して、1質量%以上が好ましく、5質量%以上がより好ましく、15質量%以上が更に好ましく、17質量%以上が特に好ましい。なお、上限値としては、60質量%以下が好ましく、50質量%以下がより好ましく、45質量%以下が更に好ましい。
重合体Aにおける第二の単量体に基づく構成単位の含有量の一態様としては、1~60質量%が好ましく、5~60質量%がより好ましく、15~50質量%が更に好ましく、17~45質量%が特に好ましい。
一態様において、重合体Aは、芳香族炭化水素基を有する単量体に基づく構成単位を25~55質量%、第一の単量体に基づく構成単位を20~35質量%、第二の単量体に基づく構成単位を15~45質量%含む重合体であることが好ましい。また、別の態様において、芳香族炭化水素基を有する単量体に基づく構成単位を70~90質量%、第一の単量体に基づく構成単位を10~25質量%含む重合体であることが好ましい。また、別の態様において、芳香族炭化水素基を有する単量体に基づく構成単位を25~70質量%、第一の単量体に基づく構成単位を15~25質量%、第二の単量体に基づく構成単位を1~5質量%含む重合体であることが好ましい。
側鎖に分岐構造を有する基を含むモノマーの具体例としては、(メタ)アクリル酸イソプロピル、(メタ)アクリル酸イソブチル、(メタ)アクリル酸sec-ブチル、(メタ)アクリル酸tert-ブチル、(メタ)アクリル酸イソアミル、(メタ)アクリル酸tert-アミル、(メタ)アクリル酸sec-アミル、(メタ)アクリル酸2-オクチル、(メタ)アクリル酸3-オクチル及び(メタ)アクリル酸tert-オクチル等が挙げられる。これらのなかでも、(メタ)アクリル酸イソプロピル、(メタ)アクリル酸イソブチル、メタクリル酸tert-ブチルが好ましく、メタクリル酸イソプロピル又はメタクリル酸tert-ブチルがより好ましい。
側鎖に脂環構造を有する基を含むモノマーの具体例としては、単環の脂肪族炭化水素基を有するモノマー、及び、多環の脂肪族炭化水素基を有するモノマーが挙げられる。また、炭素原子数5~20個の脂環式炭化水素基を有する(メタ)アクリレートが挙げられる。より具体的な例としては、(メタ)アクリル酸(ビシクロ〔2.2.1]ヘプチル-2)、(メタ)アクリル酸-1-アダマンチル、(メタ)アクリル酸-2-アダマンチル、(メタ)アクリル酸-3-メチル-1-アダマンチル、(メタ)アクリル酸-3,5-ジメチル-1-アダマンチル、(メタ)アクリル酸-3-エチルアダマンチル、(メタ)アクリル酸-3-メチル-5-エチル-1-アダマンチル、(メタ)アクリル酸-3,5,8-トリエチル-1-アダマンチル、(メタ)アクリル酸-3,5-ジメチル-8-エチル-1-アダマンチル、(メタ)アクリル酸2-メチル-2-アダマンチル、(メタ)アクリル酸2-エチル-2-アダマンチル、(メタ)アクリル酸3-ヒドロキシ-1-アダマンチル、(メタ)アクリル酸オクタヒドロ-4,7-メンタノインデン-5-イル、(メタ)アクリル酸オクタヒドロ-4,7-メンタノインデン-1-イルメチル、(メタ)アクリル酸-1-メンチル、(メタ)アクリル酸トリシクロデカン、(メタ)アクリル酸-3-ヒドロキシ-2,6,6-トリメチル-ビシクロ〔3.1.1〕ヘプチル、(メタ)アクリル酸-3,7,7-トリメチル-4-ヒドロキシ-ビシクロ〔4.1.0〕ヘプチル、(メタ)アクリル酸(ノル)ボルニル、(メタ)アクリル酸イソボルニル、(メタ)アクリル酸フェンチル、(メタ)アクリル酸-2,2,5-トリメチルシクロヘキシル、及び(メタ)アクリル酸シクロヘキシル等が挙げられる。これら(メタ)アクリル酸エステルのなかでも、(メタ)アクリル酸シクロヘキシル、(メタ)アクリル酸(ノル)ボルニル、(メタ)アクリル酸イソボルニル、(メタ)アクリル酸-1-アダマンチル、(メタ)アクリル酸-2-アダマンチル、(メタ)アクリル酸フェンチル、(メタ)アクリル酸1-メンチル、又は(メタ)アクリル酸トリシクロデカンが好ましく、(メタ)アクリル酸シクロヘキシル、(メタ)アクリル酸(ノル)ボルニル、(メタ)アクリル酸イソボルニル、(メタ)アクリル酸-2-アダマンチル、又は(メタ)アクリル酸トリシクロデカンがより好ましい。
2種以上を使用する場合には、芳香族炭化水素基を有する単量体に基づく構成単位を含む重合体Aを2種類混合使用すること、又は芳香族炭化水素基を有する単量体に基づく構成単位を含む重合体Aと芳香族炭化水素基を有する単量体に基づく構成単位を含まない重合体Aとを混合使用することが好ましい。後者の場合、芳香族炭化水素基を有する単量体に基づく構成単位を含む重合体Aの使用割合は、重合体Aの全質量に対して、50質量%以上が好ましく、70質量%以上がより好ましく、80質量%以上が好ましく、90質量%以上がより好ましい。
その他の樹脂としては、アクリル樹脂、スチレン-アクリル系共重合体、ポリウレタン樹脂、ポリビニルアルコール、ポリビニルホルマール、ポリアミド樹脂、ポリエステル樹脂、ポリアミド樹脂、エポキシ樹脂、ポリアセタール樹脂、ポリヒドロキシスチレン樹脂、ポリイミド樹脂、ポリベンゾオキサゾール樹脂、ポリシロキサン樹脂、ポリエチレンイミン、ポリアリルアミン、及びポリアルキレングリコールが挙げられる。
ネガ型感光性組成物層は、重合性化合物を含むのが好ましい。
ここで、重合性化合物とは、上記重合体A以外の化合物であり、分子量5,000未満であることが好ましい。
重合性基としては、エチレン性不飽和基を有する基が好ましく、アクリロイル基又はメタアクリロイル基がより好ましい。
重合性化合物中の重合性基の個数としては特に制限されないが、1個以上が好ましく、2個以上がより好ましい。上限値は特に制限されないが、例えば、20個以下である。
また、解像性及び剥離性により優れる点で、エチレン性不飽和化合物が一分子中に有するエチレン性不飽和基の数は、6個以下が好ましく、3個以下がより好ましく、2個以下が更に好ましい。
ネガ型感光性組成物層中、重合性化合物の全質量に対する2官能エチレン性不飽和化合物の含有量は、ネガ型感光性組成物層の全質量に対して、剥離性に優れる観点から、20質量%以上が好ましく、40質量%超がより好ましく、55質量%以上が更に好ましい。上限は特に制限されず、100質量%であってもよい。即ち、重合性化合物が全て2官能エチレン性不飽和化合物であってもよい。
エチレン性不飽和化合物としては、重合性基として(メタ)アクリロイル基を有する(メタ)アクリレート化合物が好ましい。
ネガ型感光性組成物層は、芳香環及び2個のエチレン性不飽和基を有する重合性化合物B1を含むことも好ましい。重合性化合物B1は、上述した重合性化合物Bのうち、一分子中に1個以上の芳香環を有する2官能エチレン性不飽和化合物である。
重合性化合物B1は、芳香環を1個のみ有してもよく、2個以上の芳香環を有してもよい。
ビスフェノール構造としては、例えば、ビスフェノールA(2,2-ビス(4-ヒドロキシフェニル)プロパン)に由来するビスフェノールA構造、ビスフェノールF(2,2-ビス(4-ヒドロキシフェニル)メタン)に由来するビスフェノールF構造、及びビスフェノールB(2,2-ビス(4-ヒドロキシフェニル)ブタン)に由来するビスフェノールB構造が挙げられ、ビスフェノールA構造が好ましい。
ビスフェノール構造の両端と2個の重合性基とは、直接結合してもよく、1個以上のアルキレンオキシ基を介して結合してもよい。ビスフェノール構造の両端に付加するアルキレンオキシ基としては、エチレンオキシ基又はプロピレンオキシ基が好ましく、エチレンオキシ基がより好ましい。ビスフェノール構造に付加するアルキレンオキシ基の付加数は特に制限されないが、1分子あたり4~16個が好ましく、6~14個がより好ましい。
ビスフェノール構造を有する重合性化合物B1については、特開2016-224162号公報の段落0072~0080に記載されており、この公報に記載の内容は本明細書に組み込まれる。
2,2-ビス(4-((メタ)アクリロキシポリアルコキシ)フェニル)プロパンとしては、例えば、2,2-ビス(4-(メタクリロキシジエトキシ)フェニル)プロパン(FA-324M、日立化成社製)、2,2-ビス(4-(メタクリロキシエトキシプロポキシ)フェニル)プロパン、2,2-ビス(4-(メタクリロキシペンタエトキシ)フェニル)プロパン(BPE-500、新中村化学工業社製)、2,2-ビス(4-(メタクリロキシドデカエトキシテトラプロポキシ)フェニル)プロパン(FA-3200MY、日立化成社製)、2,2-ビス(4-(メタクリロキシペンタデカエトキシ)フェニル)プロパン(BPE-1300、新中村化学工業社製)、2,2-ビス(4-(メタクリロキシジエトキシ)フェニル)プロパン(BPE-200、新中村化学工業社製)、及びエトキシ化(10)ビスフェノールAジアクリレート(NKエステルA-BPE-10、新中村化学工業社製)が挙げられる。
一態様において、n1+n2+n3+n4は、2~20が好ましく、2~16がより好ましく、4~12が更に好ましい。また、n2+n4は、0~10が好ましく、0~4がより好ましく、0~2が更に好ましく、0が特に好ましい。
重合性化合物B1の含有量は、解像性がより優れる観点から、ネガ型感光性組成物層の全質量に対して、10質量%以上が好ましく、20質量%以上がより好ましい。上限は特に制限されないが、転写性及びエッジフュージョン(転写部材の端部から感光性樹脂が滲み出す現象)の観点から、70質量%以下が好ましく、60質量%以下がより好ましい。
重合性化合物B1以外の重合性化合物は、特に制限されず、公知の化合物の中から適宜選択できる。例えば、一分子中に1個のエチレン性不飽和基を有する化合物(単官能エチレン性不飽和化合物)、芳香環を有さない2官能エチレン性不飽和化合物、及び3官能以上のエチレン性不飽和化合物が挙げられる。
アルキレングリコールジ(メタ)アクリレートとしては、例えば、トリシクロデカンジメタノールジアクリレート(A-DCP、新中村化学工業社製)、トリシクロデカンジメタノールジメタクリレート(DCP、新中村化学工業社製)、1,9-ノナンジオールジアクリレート(A-NOD-N、新中村化学工業社製)、1,6-ヘキサンジオールジアクリレート(A-HD-N、新中村化学工業社製)、エチレングリコールジメタクリレート、1,10-デカンジオールジアクリレート、及びネオペンチルグリコールジ(メタ)アクリレートが挙げられる。
ポリアルキレングリコールジ(メタ)アクリレートとしては、例えば、ポリエチレングリコールジ(メタ)アクリレート、ジプロピレングリコールジアクリレート、トリプロピレングリコールジアクリレート、及びポリプロピレングリコールジ(メタ)アクリレートが挙げられる。
ウレタンジ(メタ)アクリレートとしては、例えば、プロピレンオキサイド変性ウレタンジ(メタ)アクリレート、並びに、エチレンオキサイド及びプロピレンオキサイド変性ウレタンジ(メタ)アクリレートが挙げられる。市販品としては、例えば、8UX-015A(大成ファインケミカル社製)、UA-32P(新中村化学工業社製)、及びUA-1100H(新中村化学工業社製)が挙げられる。
ここで、「(トリ/テトラ/ペンタ/ヘキサ)(メタ)アクリレート」は、トリ(メタ)アクリレート、テトラ(メタ)アクリレート、ペンタ(メタ)アクリレート、及びヘキサ(メタ)アクリレートを包含する概念であり、「(トリ/テトラ)(メタ)アクリレート」は、トリ(メタ)アクリレート及びテトラ(メタ)アクリレートを包含する概念である。
なお、5~6官能以上のエチレン性不飽和化合物としては、ジペンタエリスリトールポリアクリレート(新中村化学工業社製「A-DPH」)等が挙げられる。
一態様において、ネガ型感光性組成物層は、上述した重合性化合物B1及び3官能以上のエチレン性不飽和化合物を含むことも好ましく、上述した重合性化合物B1及び2種以上の3官能以上のエチレン性不飽和化合物を含むことがより好ましい。この場合、重合性化合物B1と3官能以上のエチレン性不飽和化合物の質量比は、(重合性化合物B1の合計質量):(3官能以上のエチレン性不飽和化合物の合計質量)=1:1~5:1が好ましく、1.2:1~4:1がより好ましく、1.5:1~3:1が更に好ましい。
また、一態様において、ネガ型感光性組成物層は、上述した重合性化合物B1及び2種以上の3官能のエチレン性不飽和化合物を含むことが好ましい。
酸基を有する重合性化合物としては、アロニックス(登録商標)TO-2349(東亞合成社製)、アロニックス(登録商標)M-520(東亞合成社製)、及びアロニックス(登録商標)M-510(東亞合成社製)が挙げられる。酸基を有する重合性化合物化合物として、例えば、特開2004-239942号公報の段落0025~0030に記載の化合物を用いてもよい。
ネガ型感光性組成物層における重合性化合物の含有量の下限値としては、ネガ型感光性組成物層の全質量に対して、1質量%以上が好ましく、5質量%以上がより好ましく、20質量%以上が更に好ましく、35質量%以上が更に好ましく、40質量%以上が特に好ましい。また、その上限値としては特に制限されないが、70質量%以下が好ましく、60質量%以下がより好ましく、55質量%以下が更に好ましい。
ネガ型感光性組成物層は、重合開始剤を含むのが好ましい。
重合開始剤は、重合反応の形式に応じて選択され、例えば、熱重合開始剤、及び光重合開始剤が挙げられる。
重合開始剤は、ラジカル重合開始剤でもカチオン重合開始剤でもよい。
光重合開始剤は、紫外線、可視光線及びX線等の活性光線を受けて、重合性化合物の重合を開始する化合物である。光重合開始剤としては、特に制限されず、公知の光重合開始剤を使用できる。
光重合開始剤としては、例えば、光ラジカル重合開始剤及び光カチオン重合開始剤が挙げられ、光ラジカル重合開始剤が好ましい。
2,4,5-トリアリールイミダゾール二量体の誘導体としては、例えば、2-(o-クロロフェニル)-4,5-ジフェニルイミダゾール二量体、2-(o-クロロフェニル)-4,5-ジ(メトキシフェニル)イミダゾール二量体、2-(o-フルオロフェニル)-4,5-ジフェニルイミダゾール二量体、2-(o-メトキシフェニル)-4,5-ジフェニルイミダゾール二量体、及び2-(p-メトキシフェニル)-4,5-ジフェニルイミダゾール二量体が挙げられる。
2,4,5-トリアリールイミダゾール二量体の誘導体としては、例えば、2,2’-ビス(2-クロロフェニル)-4,4’,5,5’-テトラフェニル-1,2’-ビイミダゾールも挙げられる。
また、光ラジカル重合開始剤の市販品としては、商品名「Omnirad 379」(IGM Resins B.V.社製)のアルキルフェノン系化合物が挙げられる。
光カチオン重合開始剤としては、pKaが4以下の酸を発生する光カチオン重合開始剤が好ましく、pKaが3以下の酸を発生する光カチオン重合開始剤がより好ましく、pKaが2以下の酸を発生する光カチオン重合開始剤が特に好ましい。pKaの下限値は特に定めないが、例えば、-10.0以上が好ましい。
イオン性光カチオン重合開始剤として、例えば、ジアリールヨードニウム塩類及びトリアリールスルホニウム塩類等のオニウム塩化合物、並びに、第4級アンモニウム塩類が挙げられる。
イオン性光カチオン重合開始剤としては、特開2014-085643号公報の段落0114~0133に記載のイオン性光カチオン重合開始剤を用いてもよい。
光重合開始剤の含有量は、特に制限されないが、ネガ型感光性組成物層の全質量に対し、0.1質量%以上が好ましく、0.5質量%以上がより好ましく、1.0質量%以上が更に好ましい。上限は特に制限されないが、ネガ型感光性組成物層の全質量に対し、20質量%以下が好ましく、15質量%以下が更に好ましく、10質量%以下がより好ましく、5質量%以下が更に好ましい。
ネガ型感光性組成物層は、露光部及び非露光部の視認性、現像後のパターン視認性、及び解像性の観点から、発色時の波長範囲400~780nmにおける最大吸収波長が450nm以上であり、且つ、酸、塩基、又はラジカルにより最大吸収波長が変化する色素(「色素N」ともいう)を含むことも好ましい。色素Nを含むと、詳細なメカニズムは不明であるが、隣接する層(例えば水溶性樹脂層)との密着性が向上し、解像性により優れる。
具体的には、色素Nは、露光により消色状態から変化して発色する化合物であってもよいし、露光により発色状態から変化して消色する化合物であってもよい。この場合、露光により酸、塩基、又はラジカルがネガ型感光性組成物層内において発生し作用することにより、発色又は消色の状態が変化する色素でもよく、酸、塩基、又はラジカルによりネガ型感光性組成物層内の状態(例えばpH)が変化することで発色又は消色の状態が変化する色素でもよい。また、露光を介さずに、酸、塩基、又はラジカルを刺激として直接受けて発色又は消色の状態が変化する色素でもよい。
ネガ型感光性組成物層がネガ型感光性組成物層である場合は、ネガ型感光性組成物層は、露光部及び非露光部の視認性並びに解像性の観点から、色素Nとしてラジカルにより最大吸収波長が変化する色素、及び光ラジカル重合開始剤の両者を含むことが好ましい。
また、露光部及び非露光部の視認性の観点から、色素Nは、酸、塩基、又はラジカルにより発色する色素であることが好ましい。
また、色素Nは、発色時の波長範囲400~780nmにおける極大吸収波長を1つのみ有していてもよく、2つ以上有していてもよい。色素Nが発色時の波長範囲400~780nmにおける極大吸収波長を2つ以上有する場合は、2つ以上の極大吸収波長のうち吸光度が最も高い極大吸収波長が450nm以上であればよい。
露光により消色する色素としては、例えば、ロイコ化合物、ジアリールメタン系色素、オキザジン系色素、キサンテン系色素、イミノナフトキノン系色素、アゾメチン系色素、及びアントラキノン系色素が挙げられる。
色素Nとしては、露光部及び非露光部の視認性の観点から、ロイコ化合物が好ましい。
なかでも、トリアリールメタン系色素又はフルオラン系色素が好ましく、トリフェニルメタン骨格を有するロイコ化合物(トリフェニルメタン系色素)又はフルオラン系色素がより好ましい。
色素Nのうち染料の具体例としては、ブリリアントグリーン、エチルバイオレット、メチルグリーン、クリスタルバイオレット、ベイシックフクシン、メチルバイオレット2B、キナルジンレッド、ローズベンガル、メタニルイエロー、チモールスルホフタレイン、キシレノールブルー、メチルオレンジ、パラメチルレッド、コンゴーフレッド、ベンゾプルプリン4B、α-ナフチルレッド、ナイルブルー2B、ナイルブルーA、メチルバイオレット、マラカイトグリーン、パラフクシン、ビクトリアピュアブルー-ナフタレンスルホン酸塩、ビクトリアピュアブルーBOH(保土谷化学工業社製)、オイルブルー#603(オリヱント化学工業社製)、オイルピンク#312(オリヱント化学工業社製)、オイルレッド5B(オリヱント化学工業社製)、オイルスカーレット#308(オリヱント化学工業社製)、オイルレッドOG(オリヱント化学工業社製)、オイルレッドRR(オリヱント化学工業社製)、オイルグリーン#502(オリヱント化学工業社製)、スピロンレッドBEHスペシャル(保土谷化学工業社製)、m-クレゾールパープル、クレゾールレッド、ローダミンB、ローダミン6G、スルホローダミンB、オーラミン、4-p-ジエチルアミノフェニルイミノナフトキノン、2-カルボキシアニリノ-4-p-ジエチルアミノフェニルイミノナフトキノン、2-カルボキシステアリルアミノ-4-p-N,N-ビス(ヒドロキシエチル)アミノ-フェニルイミノナフトキノン、1-フェニル-3-メチル-4-p-ジエチルアミノフェニルイミノ-5-ピラゾロン、及び1-β-ナフチル-4-p-ジエチルアミノフェニルイミノ-5-ピラゾロンが挙げられる。
色素Nとしては、ロイコクリスタルバイオレット、クリスタルバイオレットラクトン、ブリリアントグリーン、又はビクトリアピュアブルー-ナフタレンスルホン酸塩が好ましい。
色素Nの含有量は、露光部及び非露光部の視認性、現像後のパターン視認性、及び解像性の観点から、ネガ型感光性組成物層の全質量に対して、0.1質量%以上が好ましく、0.1~10質量%がより好ましく、0.1~5質量%が更に好ましく、0.1~1質量%が特に好ましい。
メチルエチルケトン100mLに、色素0.001g及び0.01gを溶かした溶液を調製する。得られた各溶液に、光ラジカル重合開始剤Irgacure OXE01(商品名、BASFジャパン株式会社)を加え、365nmの光を照射することによりラジカルを発生させ、全ての色素を発色状態にする。その後、大気雰囲気下で、分光光度計(UV3100、(株)島津製作所製)を用いて、液温が25℃である各溶液の吸光度を測定し、検量線を作成する。
次に、色素に代えてネガ型感光性組成物層3gをメチルエチルケトンに溶かすこと以外は上記と同様の方法で、色素を全て発色させた溶液の吸光度を測定する。得られたネガ型感光性組成物層を含む溶液の吸光度から、検量線に基づいてネガ型感光性組成物層に含まれる色素の含有量を算出する。
なお、ネガ型感光性組成物層3gとは、ネガ型感光性組成物層形成用組成物中の全固形分の3gと同様である。
ネガ型感光性組成物層がネガ型感光性組成物層である場合、得られる硬化膜の強度、及び得られる未硬化膜の粘着性の観点から、熱架橋性化合物を含むことが好ましい。なお、本明細書においては、後述するエチレン性不飽和基を有する熱架橋性化合物は、重合性化合物としては扱わず、熱架橋性化合物として扱うものとする。
熱架橋性化合物としては、メチロール化合物、及びブロックイソシアネート化合物が挙げられる。なかでも、得られる硬化膜の強度、及び得られる未硬化膜の粘着性の観点から、ブロックイソシアネート化合物が好ましい。
ブロックイソシアネート化合物は、ヒドロキシ基及びカルボキシ基と反応するため、例えば、樹脂及び/又は重合性化合物等が、ヒドロキシ基及びカルボキシ基の少なくとも一方を有する場合には、形成される膜の親水性が下がり、ネガ型感光性組成物層を硬化した膜を保護膜として使用する場合の機能が強化される傾向がある。
なお、ブロックイソシアネート化合物とは、「イソシアネートのイソシアネート基をブロック剤で保護(いわゆる、マスク)した構造を有する化合物」を指す。
ブロックイソシアネートの解離温度とは、「示差走査熱量計を用いて、DSC(Differential scanning calorimetry)分析にて測定した場合における、ブロックイソシアネートの脱保護反応に伴う吸熱ピークの温度」を意味する。
示差走査熱量計としては、例えば、セイコーインスツルメンツ社製の示差走査熱量計(型式:DSC6200)を好適に使用できる。但し、示差走査熱量計は、これに限定されない。
これらのなかでも、解離温度が100~160℃であるブロック剤としては、例えば、保存安定性の観点から、オキシム化合物から選ばれる少なくとも1種が好ましい。
イソシアヌレート構造を有するブロックイソシアネート化合物は、例えば、ヘキサメチレンジイソシアネートをイソシアヌレート化して保護することにより得られる。
イソシアヌレート構造を有するブロックイソシアネート化合物のなかでも、オキシム化合物をブロック剤として用いたオキシム構造を有する化合物が、オキシム構造を有さない化合物よりも解離温度を好ましい範囲にしやすく、且つ、現像残渣を少なくしやすいという観点から好ましい。
重合性基としては、特に制限はなく、公知の重合性基を用いることができ、ラジカル重合性基が好ましい。
重合性基としては、(メタ)アクリロキシ基、(メタ)アクリルアミド基、及びスチリル基等のエチレン性不飽和基、並びに、グリシジル基等のエポキシ基を有する基が挙げられる。
なかでも、重合性基としては、エチレン性不飽和基が好ましく、(メタ)アクリロキシ基がより好ましく、アクリロキシ基が更に好ましい。
ブロックイソシアネート化合物の市販品の例としては、カレンズ(登録商標) AOI-BM、カレンズ(登録商標) MOI-BM、カレンズ(登録商標) MOI-BP等(以上、昭和電工社製)、ブロック型のデュラネートシリーズ(例えば、デュラネート(登録商標) TPA-B80E、デュラネート(登録商標) WT32-B75P等、旭化成ケミカルズ社製)が挙げられる。
また、ブロックイソシアネート化合物として、下記の構造の化合物を用いることもできる。
ネガ型感光性組成物層が熱架橋性化合物を含む場合、熱架橋性化合物の含有量は、ネガ型感光性組成物層の全質量に対して、1~50質量%が好ましく、5~30質量%がより好ましい。
ネガ型感光性組成物層は、上記成分以外に、必要に応じて公知の添加剤を含んでもよい。
添加剤としては、例えば、ラジカル重合禁止剤、増感剤、可塑剤、ヘテロ環状化合物(トリアゾール等)、ベンゾトリアゾール類、カルボキシベンゾトリアゾール類、ピリジン類(イソニコチンアミド等)、プリン塩基(アデニン等)、及び界面活性剤が挙げられる。
各添加剤は、1種単独で使用してもよく、2種以上使用してもよい。
ラジカル重合禁止剤としては、例えば、特許第4502784号公報の段落0018に記載された熱重合防止剤が挙げられる。なかでも、フェノチアジン、フェノキサジン、又は4-メトキシフェノールが好ましい。その他のラジカル重合禁止剤としては、ナフチルアミン、塩化第一銅、ニトロソフェニルヒドロキシアミンアルミニウム塩、及びジフェニルニトロソアミン等が挙げられる。ネガ型感光性組成物層の感度を損なわないために、ニトロソフェニルヒドロキシアミンアルミニウム塩をラジカル重合禁止剤として使用することが好ましい。
ラジカル重合禁止剤の好ましい含有量は、第1A実施形態と同様である。
(N,N-ジ-2-エチルヘキシル)アミノエチレンカルボキシベンゾトリアゾール等が挙げられる。カルボキシベンゾトリアゾール類としては、例えば、CBT-1(城北化学工業株式会社、商品名)等の市販品を使用できる。
増感剤は、特に制限されず、公知の増感剤、染料及び顔料を使用できる。増感剤としては、例えば、ジアルキルアミノベンゾフェノン化合物、ピラゾリン化合物、アントラセン化合物、クマリン化合物、キサントン化合物、チオキサントン化合物、アクリドン化合物、オキサゾール化合物、ベンゾオキサゾール化合物、チアゾール化合物、ベンゾチアゾール化合物、トリアゾール化合物(例えば、1,2,4-トリアゾール)、スチルベン化合物、トリアジン化合物、チオフェン化合物、ナフタルイミド化合物、トリアリールアミン化合物、及びアミノアクリジン化合物が挙げられる。
ネガ型感光性組成物層が増感剤を含む場合、増感剤の含有量は、目的により適宜選択できるが、光源に対する感度の向上、及び重合速度と連鎖移動のバランスによる硬化速度の向上の観点から、ネガ型感光性組成物層の全質量に対して、0.01~5質量%が好ましく、0.05~1質量%がより好ましい。
可塑剤及びヘテロ環状化合物としては、国際公開第2018/179640号の段落0097~0103及び0111~0118に記載された化合物が挙げられる。
ネガ型感光性組成物層は、界面活性剤を含むことが好ましい。界面活性剤としては、第1A実施形態の界面活性剤と同じものが挙げられ、好適態様も同じである。
ネガ型感光性組成物層に含まれる添加剤については特開2014-085643号公報の段落0165~0184に記載されており、この公報の内容は本明細書に組み込まれる。
また、一態様において、0.5~5μmが好ましく、0.5~4μmがより好ましく、0.5~3μmが更に好ましい。
ネガ型感光性組成物層は、所定量の不純物を含んでもよい。
不純物の具体例としては、ナトリウム、カリウム、マグネシウム、カルシウム、鉄、マンガン、銅、アルミニウム、チタン、クロム、コバルト、ニッケル、亜鉛、スズ、ハロゲン及びこれらのイオンが挙げられる。なかでも、ハロゲン化物イオン、ナトリウムイオン、及びカリウムイオンは不純物として混入し易いため、下記の含有量にすることが好ましい。
下限は、質量基準で、ネガ型感光性組成物層の全質量に対して、10ppb以上とすることができ、100ppb以上とすることができる。これら化合物は、上記の金属の不純物と同様の方法で含有量を抑制できる。また、公知の測定法により定量できる。
ネガ型感光性組成物層は、顔料を含む着色樹脂層となっていてもよい。
近年の電子機器が有する液晶表示窓には、液晶表示窓を保護するために、透明なガラス基板等の裏面周縁部に黒色の枠状遮光層が形成されたカバーガラスが取り付けられている場合がある。このような遮光層を形成するために着色樹脂層が使用され得る。
顔料としては、所望とする色相に合わせて適宜選択すればよく、黒色顔料、白色顔料、黒色及び白色以外の有彩色の顔料の中から選択できる。なかでも、黒色系のパターンを形成する場合には、顔料として黒色顔料が好適に選択される。
ここで、粒径とは、電子顕微鏡で撮影した顔料粒子の写真像から顔料粒子の面積を求め、顔料粒子の面積と同面積の円を考えた場合の円の直径を指し、数平均粒径は、任意の100個の粒子について上記の粒径を求め、求められた100個の粒径を平均して得られる平均値である。
また、酸化チタンの表面は、シリカ処理、アルミナ処理、チタニア処理、ジルコニア処理、又は有機物処理が施されていてもよく、二つ以上の処理が施されてもよい。これにより、酸化チタンの触媒活性が抑制され、耐熱性及び褪光性等が改善される。
加熱後のネガ型感光性組成物層の厚みを薄くする観点から、酸化チタンの表面への表面処理としては、アルミナ処理及びジルコニア処理の少なくとも一方が好ましく、アルミナ処理及びジルコニア処理の両方が特に好ましい。
有彩色の顔料としては、例えば、ビクトリア・ピュアーブルーBO(Color Index(以下C.I.)42595)、オーラミン(C.I.41000)、ファット・ブラックHB(C.I.26150)、モノライト・エローGT(C.I.ピグメント・エロー12)、パーマネント・エローGR(C.I.ピグメント・エロー17)、パーマネント・エローHR(C.I.ピグメント・エロー83)、パーマネント・カーミンFBB(C.I.ピグメント・レッド146)、ホスターバームレッドESB(C.I.ピグメント・バイオレット19)、パーマネント・ルビーFBH(C.I.ピグメント・レッド11)、ファステル・ピンクBスプラ(C.I.ピグメント・レッド81)、モナストラル・ファースト・ブルー(C.I.ピグメント・ブルー15)、モノライト・ファースト・ブラックB(C.I.ピグメント・ブラック1)及びカーボン、C.I.ピグメント・レッド97、C.I.ピグメント・レッド122、C.I.ピグメント・レッド149、C.I.ピグメント・レッド168、C.I.ピグメント・レッド177、C.I.ピグメント・レッド180、C.I.ピグメント・レッド192、C.I.ピグメント・レッド215、C.I.ピグメント・グリーン7、C.I.ピグメント・ブルー15:1、C.I.ピグメント・ブルー15:4、C.I.ピグメント・ブルー22、C.I.ピグメント・ブルー60、C.I.ピグメント・ブルー64、及びC.I.ピグメント・バイオレット23等が挙げられる。なかでも、C.I.ピグメント・レッド177が好ましい。
分散液は、黒色顔料と顔料分散剤とをあらかじめ混合して得られる混合物を、有機溶剤(又はビヒクル)に加えて分散機で分散させることによって調製されるものでもよい。顔料分散剤は、顔料及び溶剤に応じて選択すればよく、例えば市販の分散剤を使用することができる。なお、ビヒクルとは、顔料分散液とした場合に顔料を分散させている媒質の部分を指し、液状であり、黒色顔料を分散状態で保持するバインダー成分と、バインダー成分を溶解及び希釈する溶剤成分(有機溶剤)と、を含む。
第1B実施形態においても、第1A実施形態で記載した、仮支持体、ネガ型感光性組成物層及び保護フィルムの関係を満たすことが好ましい。
熱可塑性樹脂層は、通常、仮支持体とネガ型感光性組成物層との間に配置される。転写フィルムが熱可塑性樹脂層を備えることで、転写フィルムと基板との貼合工程における基板への追従性が向上して、基板と転写フィルムとの間の気泡の混入を抑制できる。この結果として、熱可塑性樹脂層に隣接する層(例えば仮支持体)との密着性を担保できる。
熱可塑性樹脂としては、アルカリ可溶性樹脂であることが好ましい。
アルカリ可溶性樹脂としては、例えば、アクリル樹脂、ポリスチレン樹脂、スチレン-アクリル系共重合体、ポリウレタン樹脂、ポリビニルアルコール、ポリビニルホルマール、ポリアミド樹脂、ポリエステル樹脂、ポリアミド樹脂、エポキシ樹脂、ポリアセタール樹脂、ポリヒドロキシスチレン樹脂、ポリイミド樹脂、ポリベンゾオキサゾール樹脂、ポリシロキサン樹脂、ポリエチレンイミン、ポリアリルアミン、及びポリアルキレングリコールが挙げられる。
ここで、アクリル樹脂は、(メタ)アクリル酸に由来する構成単位、(メタ)アクリル酸エステルに由来する構成単位、及び(メタ)アクリル酸アミドに由来する構成単位からなる群から選ばれた少なくとも1種の構成単位を有する樹脂を意味する。
アクリル樹脂としては、(メタ)アクリル酸に由来する構成単位、(メタ)アクリル酸エステルに由来する構成単位、及び(メタ)アクリル酸アミドに由来する構成単位の合計含有量が、アクリル樹脂の全質量に対して50質量%以上であることが好ましい。
なかでも、(メタ)アクリル酸に由来する構成単位及び(メタ)アクリル酸エステルに由来する構成単位の合計含有量が、アクリル樹脂の全質量に対して、30~100質量%が好ましく、50~100質量%がより好ましい。
酸基としては、カルボキシ基、スルホ基、リン酸基、及びホスホン酸基が挙げられ、カルボキシ基が好ましい。
アルカリ可溶性樹脂は、現像性の観点から、酸価60mgKOH/g以上のアルカリ可溶性樹脂がより好ましく、酸価60mgKOH/g以上のカルボキシ基含有アクリル樹脂が更に好ましい。
アルカリ可溶性樹脂の酸価の上限は、特に制限されないが、300mgKOH/g以下が好ましく、250mgKOH/g以下がより好ましく、200mgKOH/g以下が更に好ましく、150mgKOH/g以下が特に好ましい。
例えば、特開2011-095716号公報の段落0025に記載のポリマーのうち酸価60mgKOH/g以上のカルボキシ基含有アクリル樹脂であるアルカリ可溶性樹脂、特開2010-237589号公報の段落0033~0052に記載のポリマーのうちの酸価60mgKOH/g以上のカルボキシ基含有アクリル樹脂、及び特開2016-224162号公報の段落0053~0068に記載のバインダーポリマーのうちの酸価60mgKOH/g以上のカルボキシ基含有アクリル樹脂が挙げられる。
上記カルボキシ基含有アクリル樹脂におけるカルボキシ基を有する構成単位の共重合比は、アクリル樹脂の全質量に対して、5~50質量%が好ましく、10~40質量%がより好ましく、12~30質量%が更に好ましい。
アルカリ可溶性樹脂としては、現像性及び隣接する層との密着性の観点から、(メタ)アクリル酸に由来する構成単位を有するアクリル樹脂が特に好ましい。
アルカリ可溶性樹脂の含有量は、現像性及び隣接する層との密着性の観点から、熱可塑性樹脂層の全質量に対して、10~99質量%が好ましく、20~90質量%がより好ましく、40~80質量%が更に好ましく、50~75質量%が特に好ましい。
熱可塑性樹脂層は、発色時の波長範囲400~780nmにおける最大吸収波長が450nm以上であり、酸、塩基、又はラジカルにより最大吸収波長が変化する色素(単に「色素B」ともいう。)を含むことが好ましい。
色素Bの好ましい態様は、後述する点以外は、上述した色素Nの好ましい態様と同様である。
熱可塑性樹脂層は、露光部及び非露光部の視認性並びに解像性の観点から、色素Bとしての酸により最大吸収波長が変化する色素、及び後述する光により酸を発生する化合物の両者を含むことが好ましい。
色素Bの含有量は、露光部及び非露光部の視認性の観点から、熱可塑性樹脂層の全質量に対して、0.2質量%以上が好ましく、0.2~6質量%がより好ましく、0.2~5質量%が更に好ましく、0.25~3.0質量%が特に好ましい。
メチルエチルケトン100mLに、色素0.001g及び0.01gを溶かした溶液を調製する。得られた各溶液に、光ラジカル重合開始剤Irgacure OXE01(商品名、BASFジャパン株式会社)を加え、365nmの光を照射することによりラジカルを発生させ、全ての色素を発色状態にする。その後、大気雰囲気下で、分光光度計(UV3100、(株)島津製作所製)を用いて、液温が25℃である各溶液の吸光度を測定し、検量線を作成する。
次に、色素に代えて熱可塑性樹脂層0.1gをメチルエチルケトンに溶かすこと以外は上記と同様の方法で、色素を全て発色させた溶液の吸光度を測定する。得られた熱可塑性樹脂層を含む溶液の吸光度から、検量線に基づいて熱可塑性樹脂層に含まれる色素の量を算出する。
なお、熱可塑性樹脂層3gとは、組成物の固形分の3gと同様である。
熱可塑性樹脂層は、光により酸、塩基、又はラジカルを発生する化合物(単に「化合物C」ともいう。)を含んでもよい。
化合物Cとしては、紫外線及び可視光線等の活性光線を受けて、酸、塩基、又はラジカルを発生する化合物が好ましい。
化合物Cとしては、公知の、光酸発生剤、光塩基発生剤、及び光ラジカル重合開始剤(光ラジカル発生剤)を使用できる。
熱可塑性樹脂層は、解像性の観点から、光酸発生剤を含んでもよい。
光酸発生剤としては、上述したネガ型感光性組成物層が含んでもよい光カチオン重合開始剤が挙げられ、後述する点以外は好ましい態様も同じである。
また、光酸発生剤としては、以下の構造を有する光酸発生剤も好ましい。
熱可塑性樹脂層は、光ラジカル重合開始剤を含んでもよい。
光ラジカル重合開始剤としては、上述したネガ型感光性組成物層が含んでもよい光ラジカル重合開始剤が挙げられ、好ましい態様も同じである。
熱可塑性樹脂組成物は、光塩基発生剤を含んでもよい。
光塩基発生剤としては、公知の光塩基発生剤であれば特に制限されず、例えば、2-ニトロベンジルシクロヘキシルカルバメート、トリフェニルメタノール、O-カルバモイルヒドロキシルアミド、O-カルバモイルオキシム、[[(2,6-ジニトロベンジル)オキシ]カルボニル]シクロヘキシルアミン、ビス[[(2-ニトロベンジル)オキシ]カルボニル]ヘキサン1,6-ジアミン、4-(メチルチオベンゾイル)-1-メチル-1-モルホリノエタン、(4-モルホリノベンゾイル)-1-ベンジル-1-ジメチルアミノプロパン、N-(2-ニトロベンジルオキシカルボニル)ピロリジン、ヘキサアンミンコバルト(III)トリス(トリフェニルメチルボレート)、2-ベンジル-2-ジメチルアミノ-1-(4-モルホリノフェニル)-ブタノン、2,6-ジメチル-3,5-ジアセチル-4-(2-ニトロフェニル)-1,4-ジヒドロピリジン、及び2,6-ジメチル-3,5-ジアセチル-4-(2,4-ジニトロフェニル)-1,4-ジヒドロピリジンが挙げられる。
化合物Cの含有量は、露光部及び非露光部の視認性並びに解像性の観点から、熱可塑性樹脂層の全質量に対して、0.1~10質量%が好ましく、0.5~5質量%がより好ましい。
熱可塑性樹脂層は、解像性、隣接する層との密着性、及び現像性の観点から、可塑剤を含むことが好ましい。
可塑剤は、アルカリ可溶性樹脂よりも分子量(オリゴマー又はポリマーであり分子量分布を有する場合は重量平均分子量)が小さいことが好ましい。可塑剤の分子量(重量平均分子量)は、200~2,000が好ましい。
可塑剤は、アルカリ可溶性樹脂と相溶して可塑性を発現する化合物であれば特に制限されないが、可塑性付与の観点から、可塑剤は、分子中にアルキレンオキシ基を有することが好ましく、ポリアルキレングリコール化合物がより好ましい。可塑剤に含まれるアルキレンオキシ基は、ポリエチレンオキシ構造又はポリプロピレンオキシ構造を有することがより好ましい。
可塑剤として用いられる(メタ)アクリレート化合物としては、上述したネガ型感光性組成物層に含まれる重合性化合物として記載した(メタ)アクリレート化合物が挙げられる。
転写フィルムにおいて、熱可塑性樹脂層とネガ型感光性組成物層とが直接接触して積層される場合、熱可塑性樹脂層及びネガ型感光性組成物層がいずれも同じ(メタ)アクリレート化合物を含むことが好ましい。同じ(メタ)アクリレート化合物を熱可塑性樹脂層及びネガ型感光性組成物層がそれぞれ含むことで、層間の成分拡散が抑制され、保存安定性が向上するためである。
また、可塑剤として用いられる(メタ)アクリレート化合物としては、熱可塑性樹脂層の解像性、隣接する層との密着性、及び現像性の観点から、一分子中に2個以上の(メタ)アクリロイル基を有する多官能(メタ)アクリレート化合物が好ましい。
更に、可塑剤として用いられる(メタ)アクリレート化合物としては、酸基を有する(メタ)アクリレート化合物又はウレタン(メタ)アクリレート化合物も好ましい。
可塑剤の含有量は、熱可塑性樹脂層の解像性、隣接する層との密着性、及び現像性の観点から、熱可塑性樹脂層の全質量に対して、1~70質量%が好ましく、10~60質量%がより好ましく、20~50質量%が更に好ましい。
熱可塑性樹脂層は、増感剤を含んでもよい。
増感剤としては、特に制限されず、上述したネガ型感光性組成物層が含んでもよい増感剤が挙げられる。
増感剤の含有量は、目的により適宜選択できるが、光源に対する感度の向上、並びに、露光部及び非露光部の視認性の観点から、熱可塑性樹脂層の全質量に対して、0.01~5質量%が好ましく、0.05~1質量%がより好ましい。
熱可塑性樹脂層は、上記成分以外に、必要に応じて界面活性剤等の公知の添加剤を含んでもよい。
また、熱可塑性樹脂層については、特開2014-085643号公報の段落0189~0193に記載されており、この公報に記載の内容は本明細書に組み込まれる。
転写フィルム30において、中間層(中間層B)25は、熱可塑性樹脂層23とネガ型感光性組成物層27との間に存在することにより、熱可塑性樹脂層23及びネガ型感光性組成物層27の塗布形成の際及び塗布形成後の保存の際に生じ得る成分の混合を抑制できる。
中間層(中間層B)としては、水溶性樹脂を含む水溶性樹脂層が使用できる。
また、中間層(中間層B)としては、特開平5-072724号公報に「分離層」として記載されている、酸素遮断機能のある酸素遮断層も使用できる。中間層(中間層B)が酸素遮断層であると、露光時の感度が向上し、露光機の時間負荷が低減し、生産性が向上するため、好ましい。
中間層(中間層B)として用いられる酸素遮断層は、上記公報等に記載された公知の層から適宜選択すればよい。中でも、低い酸素透過性を示し、水又はアルカリ水溶液(22℃の炭酸ナトリウムの1質量%水溶液)に分散又は溶解する酸素遮断層が好ましい。
上記樹脂は、その一部又は全部として、水溶性樹脂を含む。
水溶性樹脂として使用可能な樹脂としては、例えば、ポリビニルアルコール系樹脂、ポリビニルピロリドン系樹脂、セルロース系樹脂、アクリルアミド系樹脂、ポリエチレンオキサイド系樹脂、ゼラチン、ビニルエーテル系樹脂、ポリアミド樹脂、及びこれらの共重合体等の樹脂が挙げられる。
また、水溶性樹脂としては、(メタ)アクリル酸/ビニル化合物の共重合体等も使用できる。(メタ)アクリル酸/ビニル化合物の共重合体としては、(メタ)アクリル酸/(メタ)アクリル酸アリルの共重合体が好ましく、メタクリル酸/メタクリル酸アリルの共重合体がより好ましい。
水溶性樹脂が(メタ)アクリル酸/ビニル化合物の共重合体である場合、各組成比(モル%)としては、例えば、90/10~20/80が好ましく、80/20~30/70がより好ましい。
水溶性樹脂の分散度(Mw/Mn)は、1~10が好ましく、1~5がより好ましい。
水溶性樹脂の含有量は特に制限されないが、酸素遮断性、並びに、層間混合抑制能をより向上させる点で、水溶性樹脂層(中間層B)の全質量に対して、50質量%以上が好ましく、70質量%以上がより好ましく、80質量%以上が更に好ましく、90質量%以上が特に好ましい。なお、その上限値としては特に制限されないが、例えば、99.9質量%以下が好ましく、99.8質量%以下が更に好ましい。
水溶性樹脂層(中間層B)は、任意で、界面活性剤等の公知の添加剤を含んでもよい。
第1B実施形態の転写フィルムの製造方法は特に制限されず、公知の方法を使用できる。
上記の転写フィルム30の製造方法としては、例えば、仮支持体21の表面に熱可塑性樹脂組成物を塗布して塗膜を形成し、更にこの塗膜を乾燥して熱可塑性樹脂層23を形成する工程と、熱可塑性樹脂層23の表面に水溶性樹脂組成物を塗布して塗膜を形成し、更にこの塗膜を乾燥して中間層(中間層B)25を形成する工程と、中間層(中間層B)25の表面にネガ型感光性組成物層形成用組成物を塗布して塗膜を形成し、更にこの塗膜を乾燥してネガ型感光性組成物層27を形成する工程と、ネガ型感光性組成物層27の表面に紫外線吸収層形成用組成物を塗布して塗膜を形成し、更にこの塗膜を乾燥して紫外線吸収層29を形成する工程と、を含む方法が挙げられる。
第1B実施形態の転写フィルムの製造方法としては、紫外線吸収層29の仮支持体21を有する側とは反対側の面に接するように保護フィルム31を設ける工程を含むことにより、仮支持体21、熱可塑性樹脂層23、中間層(中間層B)25、ネガ型感光性組成物層27、紫外線吸収層29、及び保護フィルム31を備える転写フィルム30を製造することが好ましい。
上記の製造方法により転写フィルム30を製造した後、転写フィルム30を巻き取ることにより、ロール形態の転写フィルムを作製及び保管してもよい。ロール形態の転写フィルムは、後述するロールツーロール方式での基板との貼合工程にそのままの形態で提供できる。
仮支持体上に熱可塑性樹脂層を形成する方法としては特に制限されず、公知の方法が使用できる。例えば、仮支持体上に熱可塑性樹脂層形成用組成物を塗布し、そして、必要に応じて乾燥させることにより形成できる。
熱可塑性樹脂層形成用組成物としては、上述した熱可塑性樹脂層を形成する各種成分と溶剤とを含むのが好ましい。なお、熱可塑性樹脂層形成用組成物において、組成物の全固形分に対する各成分の含有量の好適範囲は、上述した熱可塑性樹脂層の全質量に対する各成分の含有量の好適範囲と同じである。
溶剤としては、溶剤以外の各成分を溶解又は分散可能であれば特に制限されず、公知の溶剤を使用できる。溶剤としては、後述するネガ型感光性組成物層形成用組成物が含む溶剤と同様のものが挙げられ、好適態様も同じである。
溶剤の含有量は、組成物の全固形分100質量部に対して、50~1,900質量部が好ましく、100~900質量部がより好ましい。
水溶性樹脂組成物としては、上述した中間層B(水溶性樹脂層)を形成する各種成分と溶剤とを含むのが好ましい。なお、水溶性樹脂組成物において、組成物の全固形分に対する各成分の含有量の好適範囲は、上述した中間層B(水溶性樹脂層)の全質量に対する各成分の含有量の好適範囲と同じである。
溶剤としては、水溶性樹脂を溶解又は分散可能であれば特に制限されず、水及び水混和性の有機溶剤からなる群より選択される少なくとも1種が好ましく、水又は水と水混和性の有機溶剤との混合溶剤がより好ましい。
水混和性の有機溶剤としては、例えば、炭素数1~3のアルコール、アセトン、エチレングリコール、及びグリセリンが挙げられ、炭素数1~3のアルコールが好ましく、メタノール又はエタノールがより好ましい。
溶剤を、1種単独で使用してもよく、2種以上使用してもよい。
溶剤の含有量は、組成物の全固形分100質量部に対して、50~2,500質量部が好ましく、50~1,900質量部がより好ましく、100~900質量部が更に好ましい。
生産性に優れる点で、上述したネガ型感光性組成物層を構成する成分(例えば、バインダーポリマー、重合性化合物、及び、重合開始剤等)、及び、溶剤を含むネガ型感光性組成物層形成用組成物を使用して塗布法により形成されるのが望ましい。
第1B実施形態の転写フィルムの製造方法としては、具体的には、中間層(中間層B)上にネガ型感光性組成物層形成用組成物を塗布して塗膜を形成し、この塗膜に乾燥処理を施してネガ型感光性組成物層を形成する方法であるのが好ましい。
溶剤としては、溶剤以外の各成分を溶解又は分散可能であれば特に制限されず、公知の溶剤を使用できる。具体的には、例えば、アルキレングリコールエーテル溶剤、アルキレングリコールエーテルアセテート溶剤、アルコール溶剤(メタノール及びエタノール等)、ケトン溶剤(アセトン及びメチルエチルケトン等)、芳香族炭化水素溶剤(トルエン等)、非プロトン性極性溶剤(N,N-ジメチルホルムアミド等)、環状エーテル溶剤(テトラヒドロフラン等)、エステル溶剤(酢酸nプロピル等)、アミド溶剤、ラクトン溶剤、並びにこれらの2種以上を含む混合溶剤が挙げられる。
アルキレングリコールエーテルアセテート溶剤としては、例えば、エチレングリコールモノアルキルエーテルアセテート、プロピレングリコールモノアルキルエーテルアセテート、ジエチレングリコールモノアルキルエーテルアセテート、及びジプロピレングリコールモノアルキルエーテルアセテートが挙げられる。
溶剤としては、国際公開第2018/179640号の段落0092~0094に記載された溶剤、及び特開2018-177889公報の段落0014に記載された溶剤を用いてもよく、これらの内容は本明細書に組み込まれる。
溶剤を、1種単独で使用してもよく、2種以上使用してもよい。
溶剤の含有量は、組成物の全固形分100質量部に対し、50~1,900質量部が好ましく、50~1200質量部が更に好ましく、50~900質量部が更に好ましい。
乾燥温度としては、80℃以上が好ましく、90℃以上がより好ましい。また、その上限値としては130℃以下が好ましく、120℃以下がより好ましい。温度を連続的に変化させて乾燥させることもできる。
また、乾燥時間としては、20秒以上が好ましく、40秒以上がより好ましく、60秒以上が更に好ましい。また、その上限値としては特に制限されないが、600秒以下が好ましく、300秒以下がより好ましい。
紫外線吸収層形成用組成物としては、上述した紫外線吸収層を形成する各種成分と溶剤とを含むのが好ましい。なお、紫外線吸収層形成用組成物において、組成物の全固形分に対する各成分の含有量の好適範囲は、上述した紫外線吸収層の全質量に対する各成分の含有量の好適範囲と同じである。
溶剤としては、紫外線吸収層形成用組成物に含まれる成分を溶解又は分散可能であれば特に制限されず、水及び水混和性の有機溶剤からなる群より選択される少なくとも1種が好ましく、水又は水と水混和性の有機溶剤との混合溶剤がより好ましい。
水混和性の有機溶剤としては、例えば、炭素数1~3のアルコール、アセトン、エチレングリコール、及びグリセリンが挙げられ、炭素数1~3のアルコールが好ましく、メタノール又はエタノールがより好ましい。
溶剤は、1種単独で使用してもよく、2種以上使用してもよい。
溶剤の含有量は、組成物の全固形分100質量部に対して、50~2,500質量部が好ましく、50~1,900質量部がより好ましく、100~900質量部が更に好ましい。
保護フィルムを紫外線吸収層に貼り合わせる方法は特に制限されず、公知の方法が挙げられる。
保護フィルムを紫外線吸収層に貼り合わせる装置としては、真空ラミネーター、及び、オートカットラミネーター等の公知のラミネーターが挙げられる。
ラミネーターはゴムローラー等の任意の加熱可能なローラーを備え、加圧及び加熱ができるものであることが好ましい。
本発明の第2態様の転写フィルムは、
仮支持体と、上記仮支持体上に配置された、ネガ型感光性組成物層及び紫外線吸収層を含む組成物層と、を有する転写フィルムであり、
上記紫外線吸収層が、上記ネガ型感光性組成物層の上記仮支持体側とは反対側に配置されており、
上記紫外線吸収層の下記測定方法により算出される溶解率が、60%以上である。
上記組成物層の厚みT1を測定する。次いで、上記組成物層から上記紫外線吸収層を除去し、上記紫外線吸収層を除去した後の上記組成物層の厚みT2を測定し、上記厚みT1から上記厚みT2を差し引くことにより上記紫外線吸収層の厚みT3を求める。また、別途、上記紫外線吸収層を露出させた転写フィルムを準備して、これを25℃のイオン交換水に60秒間浸漬する。浸漬後、上記転写フィルム中の上記組成物層の厚みT4を測定する。そして、上記厚みT1から上記厚みT4を差し引くことにより上記紫外線吸収層の溶解した分の厚みT5を求め、上記厚みT5/上記厚みT3×100により、上記紫外線吸収層の溶解率を算出する。
上記構成の第2態様の転写フィルムによれば、裾引き形状が抑制されたパターンを形成できる。本発明の第2態様の転写フィルムの推定される作用機序は、以下のとおりである。
第2態様の転写フィルムは、ネガ型感光性組成物層の仮支持体とは反対側に紫外線吸収層を有しており、この構造に起因して、仮支持体とは反対側の面で基板(例えば金属基板)に接触するように転写フィルムを基板上にラミネートしてパターン形成を実施する際、露光光源からの入射光が基板で反射したとしても、その反射光は、紫外線吸収層で吸収され得る。この結果として、第2態様の転写フィルムは、露光時にネガ型感光性組成物層内において露光光源からの入射光と金属基板での反射光とによる干渉縞が発生しにくく、また、反射光は、本来マスクで遮蔽された領域(未露光部)に拡散もしにくい。すなわち、転写フィルムが所定位置に紫外線吸収層を備えることで、露光光源からの入射光の基板での反射に起因したパターンの形状故障が抑制され得る。また、今般、本発明者らは、第2態様の転写フィルムの紫外線吸収層を水への溶解性の高い層(言い換えると、比較的親水性の高い層)とすることで、現像(好ましくはアルカリ現像)の際に紫外線吸収層の残渣が残りにくく、これにも起因して、形成されるパターンの形状が裾引き形状になりにくいことも明らかとしている。なお、ネガ型感光性組成物層は、通常、疎水的な成分で構成される場合が多い。今般の発明者らの検討によれば、転写フィルム中の紫外線吸収層を水への溶解性が低い層(換言すると、比較的疎水性の高い層)とした場合、塗布法によりネガ型感光性組成物層と紫外線吸収層とを積層すると、ネガ型感光性組成物層と紫外線吸収層との過度な層間混合が生じ得て、これによってもパターンの形状が裾引き形状になり易いことを知見している。また、転写法によりネガ型感光性組成物層と紫外線吸収層とを積層しても、紫外線吸収層が比較的疎水性の高い層である場合、両層の成分の層間移動によってネガ型感光性組成物層と紫外線吸収層との過度な層間混合が生じ得ることを明らかとしている。これに対して、転写フィルム中の紫外線吸収層が比較的親水性の高い層である場合、ネガ型感光性組成物層と紫外線吸収層との過度な層間混合を抑制でき、この点もパターンの形状故障の抑制に寄与し得ることも明らかとした。
なお、以下においては、仮支持体と、仮支持体上に配置された、中間層、ネガ型感光性組成物層、及び紫外線吸収層を含む組成物層と、保護フィルムとを備えた態様の転写フィルムを一例として、紫外線吸収層の溶解率の測定方法について説明する。
図3Aは、保護フィルムを剥離後の転写フィルム40の模式図である。保護フィルムを剥離後の転写フィルム40は、仮支持体41と、仮支持体41上に配置された組成物層42とを有する。組成物層42は、仮支持体41側から順に、中間層43、ネガ型感光性組成物層45、及び紫外線吸収層47により構成されている。
まず、転写フィルム40中の仮支持体41上に配置された組成物層42の厚みT1を測定する。厚みT1は、触針式膜厚計(例えば、ブルッカー社製の「DekTak150」等)を使用して測定する。また、厚みT1の測定にあたっては、任意の5か所を測定し、各測定値の平均値として算出する。なお、後述する厚みT2及び厚みT4等の各厚みについても、厚みT1と同様の手順で測定する。
イオン交換水としては、中性のpHを有するイオン交換水(好ましくは、pHが7.0付近のイオン交換水であり、好ましくは、pHが6.0~8.0のイオン交換水)を使用する。
乾燥温度としては、例えば、20~100℃が好ましく、20~80℃がより好ましい。また、乾燥時間としては、1分~5分が好ましく、1分~2分がより好ましい。
そして、図3Dに示すように、浸漬後の転写フィルム40中の組成物層42Bの厚みT4を測定する。そして、厚みT1から厚みT4を差し引くことにより紫外線吸収層47の溶解した分の厚みT5を求め、厚みT5/厚みT3×100により、紫外線吸収層47の溶解率(%)を算出する。
第2態様の転写フィルムの構成としては、紫外線吸収層の構成が異なる点以外は、第1態様の転写フィルムと同じであり、その好適態様も同じである。
なお、第2態様の転写フィルムの製造方法としては、第1態様の転写フィルムの製造方法と同じであり、その好適態様も同じである。
以下においては、第2態様の転写フィルムが含む紫外線吸収層について説明する。
転写フィルムは、紫外線吸収層を有する。
紫外線吸収層は、紫外線を吸収可能な層(具体的には、波長450nm以下の紫外線を吸収可能な層)であり、例えば、高圧水銀灯が発光するg線(435nm)、h線(405nm)、i線(365nm)、及びj線(313nm)等の紫外線、KrF露光装置での露光波長である248nm、並びに、ArF露光装置での露光波長である193nm等の波長の紫外線を吸収できるのが好ましく、h線(405nm)及びi線(365nm)を吸収できるのがより好ましい。
紫外線吸収層としては、紫外線吸収剤を含むのが好ましい。
紫外線吸収層の波長405nmにおける透過率としては、本発明の効果がより優れる点で、70%以下であるのが好ましく、50%以下であるのがより好ましく、40%以下であるのが更に好ましい。なお、下限値としては、例えば、20%以上であるのが好ましい。
透過率は、紫外可視分光高度計(例えば、(株)島津製作所製UV-1800)を使用して測定できる。
また、紫外線吸収層の光学濃度(OD値、波長365nm)としては、本発明の効果がより優れる点で、0.1~0.6が好ましく、0.1~0.4がより好ましい。
光学濃度(OD値)の測定は、例えば、(株)日立ハイテクノロジー製の分光器UV4100(商品名)を使用できる。
紫外線吸収剤としては、紫外線を吸収可能な化合物であり、ネガ型感光性組成物層に含まれ得る光重合開始剤の感光波長の少なくとも一部の波長の光を吸収可能な紫外線吸収特性を有することが好ましい。
紫外線吸収剤の波長365nmの光に対するモル吸光係数としては、5,000~100,000(L/(mol・cm))であるのが好ましく、10,000~80,000(L/(mol・cm))であるのがより好ましく、15,000~50,000(L/(mol・cm))であるのが更に好ましい。
紫外線吸収剤のモル吸光係数は、以下の方法により測定するものとする。
測定対象の化合物をN,N-ジメチルホルムアミドを用いて4×10-6(g/mL)の溶液とする。この溶液を、(株)島津製作所製UV測定装置UV2550を用いて365nmでの吸光度を測定する。得られた吸光度等より、式:[モル吸光係数]=[吸光度]/[溶液の質量濃度/吸光性化合物の分子量]によりモル吸光係数を算出する。
紫外線吸収剤としては、例えば、高分子紫外線吸収剤及びポリマー被覆型紫外線吸収剤等が挙げられる。
紫外線吸収構造としては、トリアジン構造、ベンゾトリアゾール構造、ベンゾフェノン構造、又は、サリチル酸構造が好ましく、トリアジン構造がより好ましい。
また、紫外線吸収構造を有する単量体に由来する構成単位を含むポリマーは、(メタ)アクリル樹脂であるのが好ましい。なお、上記(メタ)アクリル樹脂としては、上述の第1B実施形態の転写フィルムの熱可塑性樹脂層中に含まれ得るアルカリ可溶性樹脂としての(メタ)アクリル樹脂を形成するためのモノマーで形成されているのが好ましい。
高分子紫外線吸収剤中、紫外線吸収構造を有する単量体に由来する構成単位の含有量としては、ポリマーの全質量に対し、10~80質量%であるのが好ましく、30~70質量%であるのがより好ましい。
上記ポリマーとしては、(メタ)アクリル樹脂、ポリエステル、ポリウレタン、ポリオレフィン、シロキサン樹脂、及びフッ素ポリマー等が挙げられ、(メタ)アクリル樹脂が好ましい。なお、上記(メタ)アクリル樹脂としては、上述の第1B実施形態の転写フィルムの熱可塑性樹脂層アルカリ可溶性樹脂としての(メタ)アクリル樹脂が好ましい。
ポリマー被覆型紫外線吸収剤における紫外線吸収剤の含有量は、ポリマー被覆型紫外線吸収剤の全量に対し、20~80質量%が好ましく、30~70質量%がより好ましく、40~60質量%が更に好ましい。
ポリマー被覆型紫外線吸収剤におけるポリマーの含有量は、ポリマー被覆型紫外線吸収剤の全量に対し、20~80質量%が好ましく、30~70質量%がより好ましく、40~60質量%が更に好ましい。
ポリマー被覆型紫外線吸収剤が粒子である場合、そのメジアン径(D50)の上限値としては、500nm以下が好ましく、400nm以下がより好ましく、200nm以下が更に好ましく、100nm以下が特に好ましい。また、メジアン径の下限値としては、10nm以上であるのが好ましく、20nm以上であるのがより好ましい。メジアン径は、動的光散乱測定による粒度分布から算出できる。
また、紫外線吸収層は、上述の測定方法により算出される溶解率が60%以上である。
紫外線吸収層の溶解率を上述の数値範囲とする手段としては、例えば、紫外線吸収層に、ClogP値が2.1より小さいポリマー(以下「特定ポリマー」ともいう)を含むのが好ましい。なお、紫外線吸収剤がポリマーであり且つClogP値が2.1より小さい場合、このポリマーは、特定ポリマーには含まれない。
特定バインダーのClogPは、本発明の効果がより優れる点で、2.0以下が好ましく、1.9以下がより好ましい。また、その下限値としては特に制限されないが、1.0以上であるのが好ましい。
本明細書において、ClogPとは、1-オクタノール及び水への分配係数Pの常用対数logPを計算によって求めた値である。
上記ClogPの計算に用いる方法及びソフトウェアについては公知のものを使用できるが、特に断らない限り、本明細書では、Cambridge soft社のChemBioDraw Ultra 12.0に組み込まれたClogPプログラムを用いることとする。
本明細書において、I/O値とは、有機概念図における有機性値(O)に対する無機性値(I)の比(以下「I/O値」ともいう)である。
特定バインダーのI/O値は次の方法によって求める。甲田善生著、有機概念図-基礎と応用-(1984)13ページ等に記載されている有機性(O値)、無機性(I値)を元に、特定バインダーを構成する各モノマーのI/O値を算出する。特定バインダーを構成する各モノマーについて、その「I/O値」と「特定バインダーの全構成単位に対するモル%」の積を算出し、これらを合計して、特定ポリマーのI/O値とする。
SP値(δ)=(EV/v)1/2=(ΣΔei/ΣΔvi)1/2・・・式(1)
EV:蒸発エネルギー
v:モル体積
Δei:各原子又は原子団の蒸発エネルギー
Δvi:各原子又は原子団のモル体積
また、本明細書において、特定バインダーポリマーが異なるm(mが2以上の整数)種類のモノマーを共重合させて得たポリマーである場合、SP値は、下記式によって計算される。
SP値(δ)=X1δ1+・・・+Xmδm
X1、・・・、Xmは、共重合体を構成する各モノマーのモル%であり、且つ、X1+・・・Xm=100モル%である。
δ1、・・・、δmは、共重合体を構成する各モノマーのSP値であり、上記式(1)で求めた値である。
なお、(メタ)アクリル樹脂とは、上述のとおり、(メタ)アクリル化合物に由来する構成単位を有する樹脂を意味する。(メタ)アクリル化合物に由来する構成単位の含有量は、(メタ)アクリル樹脂の全構成単位に対して、50質量%以上が好ましく、70質量%以上がより好ましく、90質量%以上が更に好ましい。
(メタ)アクリル樹脂は、(メタ)アクリル化合物に由来する構成単位のみで構成されていてもよく、(メタ)アクリル化合物以外の重合性単量体に由来する構成単位を有していてもよい。すなわち、(メタ)アクリル化合物に由来する構成単位の含有量の上限は、(メタ)アクリル樹脂の全構成単位に対して、100質量%以下である。
(メタ)アクリル酸アルキルエステルのアルキル基としては、直鎖状でも分岐を有していてもよい。具体例としては、例えば、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸プロピル、(メタ)アクリル酸ブチル、(メタ)アクリル酸ペンチル、(メタ)アクリル酸ヘキシル、(メタ)アクリル酸ヘプチル、(メタ)アクリル酸オクチル、(メタ)アクリル酸2-エチルヘキシル、(メタ)アクリル酸ノニル、(メタ)アクリル酸デシル、(メタ)アクリル酸ウンデシル、及び、(メタ)アクリル酸ドデシル等の炭素数が1~12のアルキル基を有する(メタ)アクリル酸アルキルエステルが挙げられる。
また、(メタ)アクリル酸アルキルエステルのアルキル基としては、環状であってもよい。環状アルキル基としては、単環でも多環でもよい。具体例としては、(メタ)アクリル酸シクロヘキシル等が挙げられる。
(メタ)アクリル樹脂における酸基を有する構成単位(好ましくは(メタ)アクリル酸に由来する構成単位)の含有量は、本発明の効果がより優れる点で、(メタ)アクリル樹脂の全質量に対して、10質量%以上が好ましく、20質量%以上がより好ましい。また、上限値は特に制限されないが、アルカリ耐性に優れる点で、50質量%以下が好ましく、40質量%以下がより好ましい。
特定ポリマーの重量平均分子量としては、5,000~100,000が好ましく、7,000~50,000がより好ましく、10,000~50,000が更に好ましい。
バインダーポリマーの分散度は、現像性の観点から、1.0~6.0が好ましく、1.0~5.0がより好ましく、1.0~4.0が更に好ましく、1.0~3.0が特に好ましい。
特定ポリマーの含有量は、紫外線吸収層の全質量に対して、例えば、20~95質量%であるのが好ましく、40~95質量%であるのがより好ましく、50~90質量%であるのが更に好ましく、60~90質量%であるのが特に好ましい。
また、特定ポリマーに対する紫外線吸収剤の含有量比(紫外線吸収剤の含有量/特定ポリマの含有量)としては、0.05~0.4であるのがより好ましく、0.1~0.3であるのが更に好ましい。
紫外線吸収層の好適な一態様としては、光硬化性であるのも好ましい。光硬化性の紫外線吸収層としては、エチレン性不飽和化合物を含むのが好ましく、エチレン性不飽和化合物及び光重合開始剤を含むのがより好ましい。
紫外線吸収層が重合性化合物(好ましくは、エチレン性不飽和化合物)を含む場合、重合性化合物(好ましくは、エチレン性不飽和化合物)の含有量は、紫外線吸収層の強度がより優れる点で、紫外線吸収層の全質量に対し、1~70質量%が好ましく、10~70質量%がより好ましく、15~60質量%が更に好ましく、15~55質量%が特に好ましい。
紫外線吸収層が重合開始剤(好ましくは、光重合開始剤)を含む場合、重合開始剤(好ましくは、光重合開始剤)の含有量は、紫外線吸収層の強度がより優れる点で、紫外線吸収層の全質量に対し、0.1~10質量%が好ましく、0.5~10質量%がより好ましく、0.5~5質量%が更に好ましい。
紫外線吸収層が界面活性剤を含む場合、界面活性剤の含有量は、紫外線吸収層の全質量に対して、0.01~3質量%が好ましく、0.05~1質量%がより好ましく、0.1~0.8質量%が更に好ましい。
他の成分としては、例えば、金属酸化物粒子、ヘテロ環状化合物以外の架橋剤、アルコキシシラン化合物、酸化防止剤、分散剤、酸増殖剤、現像促進剤、導電性繊維、着色剤、熱ラジカル発生剤、熱酸発生剤、増粘剤、及び、有機又は無機の沈殿防止剤等の公知の添加剤が挙げられる。
上述した第1態様及び第2態様の転写フィルムを用いることにより、被転写体へ組成物層を転写することができる。
なかでも、第1態様及び第2態様の転写フィルムは、タッチパネルの製造に用いられることが好ましい。
なかでも、本発明の積層体の製造方法は、転写フィルムが有する仮支持体とは反対側の表面を、導電層を有する基板に接触させ、基板、導電層、組成物層、及び、仮支持体をこの順に有する組成物層付き基板を得る貼合工程と、
仮支持体を剥離する剥離工程と、
露出した組成物層をパターン露光する露光工程と、
露光した組成物層を現像してパターンを形成する現像工程と、を有する、積層体の製造方法であるのが好ましい。
以下、上記工程の手順について詳述する。
貼合工程は、転写フィルムが有する仮支持体とは反対側の表面を、導電層を有する基板に接触させて貼り合わせ、基板、導電層、組成物層、及び、仮支持体をこの順に有する組成物層付き基板を得る工程である。なお、転写フィルムが保護フィルムを有する構成である場合、保護フィルムを剥がしてから貼合工程を実施する。
上記圧着の方法としては特に制限はなく、公知の転写方法、及び、ラミネート方法を使用できる。なかでも、組成物層の表面を導電層を有する基板に重ね、ロール等による加圧及び加熱が行われることが好ましい。
貼り合せには、真空ラミネーター、及び、オートカットラミネーター等の公知のラミネーターを使用できる。
ラミネート温度としては特に制限されないが、例えば、70~130℃であるのが好ましい。
基板の好ましい態様としては、例えば、国際公開第2018/155193号の段落[0140]に記載があり、この内容は本明細書に組み込まれる。樹脂基板の材料としては、シクロオレフィンポリマー及びポリイミドが好ましい。樹脂基板の厚みは5μm~200μmが好ましく、10~100μmがより好ましい。
また、基板上には導電層を1層のみ配置してもよいし、2層以上配置してもよい。導電層を2層以上配置する場合は、異なる材質の導電層を有することが好ましい。
導電層の好ましい態様としては、例えば、国際公開第2018/155193号の段落[0141]に記載があり、この内容は本明細書に組み込まれる。
透明電極は、タッチパネル用電極として好適に機能し得る。透明電極は、ITO(酸化インジウムスズ)、及び、IZO(酸化インジウム亜鉛)等の金属酸化膜、並びに、金属メッシュ、及び、金属ナノワイヤー等の金属細線により構成されることが好ましい。
金属細線としては、銀、銅等の細線が挙げられる。なかでも、銀メッシュ、銀ナノワイヤー等の銀導電性材料が好ましい。
引き回し配線の材質である金属としては、金、銀、銅、モリブデン、アルミニウム、チタン、クロム、亜鉛、及び、マンガン、並びに、これらの金属元素の2種以上からなる合金が挙げられる。引き回し配線の材質としては、銅、モリブデン、アルミニウム、又は、チタンが好ましく、銅が特に好ましい。
剥離工程は、組成物層付き基板から仮支持体を剥離する工程である。
剥離方法は特に制限されず、特開2010-072589号公報の段落[0161]~[0162]に記載されたカバーフィルム剥離機構と同様の機構を使用できる。
露光工程は、露出した組成物層をパターン露光する工程である。
なお、ここで、「パターン露光」とは、パターン状に露光する形態、すなわち、露光部と非露光部とが存在する形態の露光を指す。
パターン露光における露光領域と未露光領域との位置関係は特に制限されず、適宜調整される。
組成物層の基板とは反対側から露光してもよいし、組成物層の基板側から露光してもよい。
露光量は、5~200mJ/cm2が好ましく、10~200mJ/cm2がより好ましい。
現像工程は、露光された組成物層を現像して、パターンを形成する工程である。
上記組成物層の現像は、現像液を用いて行うことができる。
現像液として、アルカリ性水溶液が好ましい。アルカリ性水溶液に含まれ得るアルカリ性化合物としては、例えば、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラプロピルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド、及び、コリン(2-ヒドロキシエチルトリメチルアンモニウムヒドロキシド)が挙げられる。
また、現像工程を実施する現像方式の好適な一態様としては、例えば、国際公開第2015/093271号の段落[0195]に記載の現像方式が挙げられる。
上記積層体の製造方法は、上記現像工程によって得られたパターンを、露光する工程(ポスト露光工程)、及び/又は、加熱する工程(ポストベーク工程)を有していてもよい。
ポスト露光工程及びポストベーク工程の両方を含む場合、ポスト露光の後、ポストベークを実施することが好ましい。ポスト露光の露光量は、100~5000mJ/cm2が好ましく、200~3000mJ/cm2がより好ましい。ポストベークの温度は、80~250℃が好ましく、90~160℃がより好ましい。ポストベークの時間は、1~180分が好ましく、10~60分がより好ましい。
本発明の積層体の製造方法により製造される積層体は、種々の装置に適用することができる。上記積層体を備えた装置としては、例えば、入力装置等が挙げられ、タッチパネルであることが好ましく、静電容量型タッチパネルであることがより好ましい。また、上記入力装置は、有機エレクトロルミネッセンス表示装置、液晶表示装置等の表示装置に適用することができる。
積層体がタッチパネルに適用される場合、組成物層から形成されるパターンは、タッチパネル用電極又はタッチパネル用配線の保護膜として用いられることが好ましい。つまり、転写フィルムに含まれる組成物層は、タッチパネル用電極保護膜又はタッチパネル用配線保護膜の形成に用いられることが好ましい。
第1態様及び第2態様の転写フィルムを用いることにより、回路配線も製造できる。
回路配線の製造方法は、上記の転写フィルムを用いる回路配線の製造方法であれば、特に制限されない。
なかでも、本発明の回路配線の製造方法は、転写フィルムが有する仮支持体とは反対側の表面を、導電層を有する基板に接触させ、基板、導電層、組成物層、及び、仮支持体をこの順に有する組成物層付き基板を得る貼合工程と、
仮支持体を剥離する剥離工程と、
露出した組成物層をパターン露光する露光工程と、
露光された組成物層を現像して樹脂パターンを形成する現像工程と、
樹脂パターンが配置されていない領域における導電層をエッチング処理するエッチング工程と、を含む製造方法であるのが好ましい。
回路配線の製造方法における貼合工程、剥離工程、露光工程、及び現像工程については、上述した積層体の製造方法における貼合工程、剥離工程、露光工程、及び現像工程と同じであり、好適態様も同じである。
回路配線の製造方法は、基板、導電層(基板が有する導電層)、及び、樹脂パターン(より好ましくは、上記貼合工程と、上記剥離工程と、上記露光工程と、上記現像工程とを含む製造方法により製造された樹脂パターン)がこの順で積層された積層体において、樹脂パターンが配置されていない領域にある導電層をエッチング処理する工程(エッチング工程)を含む。
上記エッチング工程では、上記現像工程によりネガ型感光性組成物層から得られる樹脂パターンを、エッチングレジストとして使用し、導電層のエッチング処理を行う。
エッチング処理の方法としては、公知の方法を適用でき、例えば、特開2017-120435号公報の段落[0209]~[0210]に記載の方法、特開2010-152155号公報の段落[0048]~[0054]等に記載の方法、エッチング液に浸漬するウェットエッチング法、及び、プラズマエッチング等のドライエッチングによる方法が挙げられる。
酸性のエッチング液としては、例えば、塩酸、硫酸、硝酸、酢酸、フッ酸、シュウ酸及びリン酸から選択される酸性成分単独の水溶液、並びに、酸性成分と、塩化第2鉄、フッ化アンモニウム及び過マンガン酸カリウムから選択される塩との混合水溶液が挙げられる。酸性成分は、複数の酸性成分を組み合わせた成分であってもよい。
アルカリ性のエッチング液としては、水酸化ナトリウム、水酸化カリウム、アンモニア、有機アミン、及び、有機アミンの塩(テトラメチルアンモニウムハイドロオキサイド等)から選択されるアルカリ成分単独の水溶液、並びに、アルカリ成分と塩(過マンガン酸カリウム等)との混合水溶液が挙げられる。アルカリ成分は、複数のアルカリ成分を組み合わせた成分であってもよい。
回路配線の製造方法においては、残存する樹脂パターンを除去する工程(除去工程)を行うことが好ましい。
除去工程は、特に制限されず、必要に応じて行うことができるが、エッチング工程の後に行うことが好ましい。
残存する樹脂パターンを除去する方法としては特に制限されないが、薬品処理により除去する方法が挙げられ、除去液を用いて除去する方法が好ましい。
ネガ型感光性組成物層の除去方法としては、液温が好ましくは30~80℃、より好ましくは50~80℃である撹拌中の除去液に、残存する樹脂パターンを有する基板を、1~30分間浸漬する方法が挙げられる。
また、除去液を使用し、スプレー法、シャワー法及びパドル法等の公知の方法により除去してもよい。
回路配線の製造方法は、上述した工程以外の任意の工程(その他の工程)を含んでもよい。
例えば、国際公開第2019/022089号の段落[0172]に記載の可視光線反射率を低下させる工程、国際公開第2019/022089号の段落[0172]に記載の絶縁膜上に新たな導電層を形成する工程等が挙げられるが、これらの工程に制限されない。
回路配線の製造方法は、基材が有する複数の導電層の一部又は全ての可視光線反射率を低下させる処理を行う工程を含んでもよい。
可視光線反射率を低下させる処理としては、酸化処理が挙げられる。基材が銅を含む導電層を有する場合、銅を酸化処理して酸化銅とし、導電層を黒化することにより、導電層の可視光線反射率を低下させることができる。
可視光線反射率を低下させる処理については、特開2014-150118号公報の段落0017~0025、並びに、特開2013-206315号公報の段落0041、段落0042、段落0048及び段落0058に記載されており、これらの公報に記載の内容は本明細書に組み込まれる。
回路配線の製造方法は、回路配線の表面に絶縁膜を形成する工程と、絶縁膜の表面に新たな導電層を形成する工程と、を含むことも好ましい。
上記の工程により、第一の電極パターンと絶縁した第二の電極パターンを形成することができる。
絶縁膜を形成する工程としては、特に制限されず、公知の永久膜を形成する方法が挙げられる。また、絶縁性を有する感光性材料を用いて、フォトリソグラフィにより所望のパターンの絶縁膜を形成してもよい。
絶縁膜上に新たな導電層を形成する工程は、特に制限されず、例えば、導電性を有する感光性材料を用いて、フォトリソグラフィにより所望のパターンの新たな導電層を形成してもよい。
回路配線の製造方法により製造される回路配線は、種々の装置に適用することができる。上記の製造方法により製造される回路配線を備えた装置としては、例えば、入力装置が挙げられ、タッチパネルが好ましく、静電容量型タッチパネルがより好ましい。また、上記入力装置は、有機EL表示装置及び液晶表示装置等の表示装置に適用できる。
なお、特に断りのない限り、「部」及び、「%」は質量基準である。
〔ネガ型感光性組成物層形成用組成物(以下「ネガ型感光性組成物」と略記する。)及び紫外線吸収層形成用組成物に含まれる各種成分〕
以下において、実施例及び比較例の各転写フィルム中に含まれるネガ型感光性組成物層を形成するためのネガ型感光性組成物、及び、紫外線吸収層を形成するための紫外線吸収層形成用組成物に使用される各種成分について説明する。
(バインダーの種類)
表2にて示すバインダーポリマーを以下に示す。
バインダーのSP値、I/O値、及びClogP値の各数値については、既述の方法により測定した。なお、実施例の転写フィルムの紫外線吸収層に含まれるバインダーは、化合物11~14が該当する。
・BPE-500:エトキシ化ビスフェノールAジメタクリレート(新中村化学工業社製「BPE-500」、2官能アクリレート)
・SR-454:エトキシ化(3)トリメチロールプロパントリアクリレート(巴工業株式会社製「SR-454」、3官能アクリレート)
・A-DCP:トリシクロデカンジメタノールジアクリレート(新中村化学工業社製「A-DCP」、2官能アクリレート)
・TO-2349:ジペンタエリスリトールヘキサアクリレート、ジペンタエリスリトールペンタアクリレート、及びジペンタエリスリトールペンタアクリレートのコハク酸誘導体との混合物(東亞合成社製「アロニックスTO-2349」、5又は6官能アクリレート)
・AD-TMP:ジトリメチロールプロパンテトラアクリレート(新中村化学工業社製「AD-TMP」、4官能アクリレート)
・B-CIM :2,2’-ビス(2-クロロフェニル)-4,4’,5,5’-テトラフェニルビイミダゾール(黒金化成社製「B-CIM」)
・OXE-02:オキシムエステル系光重合開始剤(BASF社製「Irgacure OXE02」)
・4,4-ビス(ジエチルアミノ)ベンゾフェノン:三洋貿易社製「SB-PI」
・ロイコクリスタルバイオレット:東京化成工業社製
・MTBD1:1,4-ビス(3-メルカプトブチリルオキシ)ブタン(昭和電工社製「カレンズMT(登録商標)BD1」、2官能チオール)
・デュラネートTPA-B80E:ブロックイソシアネート化合物(旭化成ケミカルズ社製「デュラネート(登録商標)TPA-B80E」
・ベンゾイミダゾール:東京化成工業社製
・メガファックF552:フッ素系界面活性剤、DIC社製
・メガファックF444:フッ素系界面活性剤、DIC社製
・メガファックF551:フッ素系界面活性剤、DIC社製
・TWBK-2581:水系カーボンブラック分散液(大成化工社製「TWBK-2581」、固形分濃度:約15質量%)
・TINUVIN477-DW:ヒドロキシフェニルトリアジン水分散液(BASF社製「TINUVIN477-DW」、固形分濃度:約80質量%)
・TINUVIN329:2-(2H-ベンゾトリアゾール-2-イル)-4-(1,1,3,3-テトラメチルブチル)(BASF社製「TINUVIN 329」)
・アセトン:三菱ケミカル社製
・トルエン:三菱ケミカル社製
・メタノール:三菱ガス化学製
・MEK:メチルエチルケトン、三協化学社製
・MMPGAc:1-メトキシ-2-プロピルアセテート、昭和電工株式会社製
以下において、実施例及び比較例の各転写フィルム中に含まれる中間層を形成するための中間層形成用組成物に使用される各種成分について説明する。
・PVP K30:ポリビニルピロリドン(富士フイルム社製「PVP K30」)
・メトローズ 60SH03:水溶性セルロース誘導体(信越化学工業社製「メトローズ 60SH03」)
・F444:界面活性剤(DIC社製「F444」)
表2に示す組成及び配合量に基づいて各種成分を混合して、ネガ型感光性組成物(塗布液)を調製した。なお、表2に記載された成分に対応する数値は、各成分の配合量(質量部)を表す。
表2に示す組成及び配合量に基づいて各種成分を混合して、紫外線吸収層形成用組成物(塗布液)を調製した。なお、表2に記載された成分に対応する数値は、各成分の配合量(質量部)を表す。
以下に示す組成及び配合量に基づいて各種成分を混合して、中間層形成用組成物(塗布液)を調製した。なお、表2に記載された成分に対応する数値は、各成分の固形分における配合量(質量部)を表す。
表2に示す構成となるように、転写フィルムを各々作製した。具体的には以下のとおりである。
厚み16μmのポリエチレンテレフタレートフィルム(仮支持体、16KS40:商品名、東レ(株)社製)の上に、バーコーターを用いて、乾燥後に表2に記載の膜厚となるように、表2に示す組成の中間層形成用組成物を塗布して塗膜を形成した。得られた塗膜を90℃のオーブンで乾燥させて、中間層を形成した。
その後、上記中間層上に、バーコーターを用いて、乾燥後に表2に記載の膜厚となるように、表2に示す組成のネガ型感光性組成物を塗布して塗膜を形成した。得られた塗膜を80℃のオーブンで乾燥させて、ネガ型感光性組成物層を形成した。
次に、上記ネガ型感光性組成物層上に、バーコーターを用いて、乾燥後に表2に記載の膜厚となるように、表2に示す組成の紫外線吸収層形成用組成物を塗布して塗膜を形成した。得られた塗膜を90℃のオーブンで乾燥させて、紫外線吸収層を形成した。
そして、上述の紫外線吸収層の表面に、保護フィルムとして、厚み16μmのポリエチレンテレフタレート(16KS40:商品名、東レ(株)社製)を圧着し、実施例1の転写フィルムを作製した。
ネガ型感光性組成物及び紫外線吸収層形成用組成物の組成及び配合を表2に記載するものに変更し、且つ、乾燥後のネガ型感光性組成物層及び紫外線吸収層の膜厚が表2に記載の膜厚になるように調整したこと以外は、実施例1と同様の方法により、実施例2~9の転写フィルムの転写フィルムを作製した。
厚み16μmのポリエチレンテレフタレートフィルム(仮支持体、16KS40:商品名、東レ(株)社製)の上に、バーコーターを用いて、乾燥後に表2に記載の膜厚となるように、表2に示す組成の中間層形成用組成物を塗布して塗膜を形成した。得られた塗膜を90℃のオーブンで乾燥させて、中間層を形成した。
その後、上記中間層上に、バーコーターを用いて、乾燥後に表2に記載の膜厚となるように、表2に示す組成のネガ型感光性組成物を塗布して塗膜を形成した。得られた塗膜を100℃のオーブンで2分間乾燥させて、ネガ型感光性組成物層を形成した。
次に、上記ネガ型感光性組成物層上に、バーコーターを用いて、乾燥後に表2に記載の膜厚となるように、表2に示す組成の紫外線吸収層形成用組成物を塗布して塗膜を形成した。得られた塗膜を100℃のオーブンで2分間乾燥させて、紫外線吸収層を形成した。
そして、上述の紫外線吸収層の表面に、保護フィルムとして、厚み16μmのポリエチレンテレフタレート(16KS40:商品名、東レ(株)社製)を圧着し、比較例1の転写フィルムを作製した。
(第一のドライフィルムの作製)
厚み16μmのポリエチレンテレフタレートフィルム(仮支持体、16KS40:商品名、東レ(株)社製)の上に、バーコーターを用いて、乾燥後に表2に記載の膜厚となるように、表2に示す組成の中間層形成用組成物を塗布して塗膜を形成した。得られた塗膜を90℃のオーブンで乾燥させて、中間層を形成した。
その後、上記中間層上に、バーコーターを用いて、乾燥後に表2に記載の膜厚となるように、表2に示す組成のネガ型感光性組成物を塗布して塗膜を形成した。得られた塗膜を100℃のオーブンで2分間乾燥させて、ネガ型感光性組成物層を形成した。このようにして、第一のドライフィルムを作製した。
(第二のドライフィルムの作製)
厚み16μmのポリエチレンテレフタレート(16KS40:商品名、東レ(株)社製)の上に、バーコーターを用いて、乾燥後に表2に記載の膜厚となるように、表2に示す組成の紫外線吸収層形成用組成物を塗布して塗膜を形成した。得られた塗膜を100℃のオーブンで2分間乾燥させて、紫外線吸収層を形成した。このようにして、第二のドライフィルムを作製した。
(転写フィルムの作製)
第一のドライフィルムと第二のドライフィルムとを、紫外線吸収層とネガ型感光性組成物層とが対向するようにラミネーターを用いて23℃で貼り合せて、転写フィルムを作製した。
紫外線吸収層を形成しなかった以外は実施例1と同様の方法により、比較例3の転写フィルムの転写フィルムを作製した。
ネガ型感光性組成物及び紫外線吸収層形成用組成物の組成及び配合を表2に記載するものに変更し、且つ、乾燥後のネガ型感光性組成物層及び紫外線吸収層の膜厚が表2に記載の膜厚になるように調整したこと以外は、実施例1と同様の方法により、比較例4の転写フィルムの転写フィルムを作製した。
得られた実施例及び比較例の各転写フィルムについて、以下に示す測定を実施した。表2に、測定結果を示す。
触針式膜厚計(ブルッカー社製の「DekTak150」(以下同様))を使用して、保護フィルムを剥離した転写フィルム中の組成物層(なお、実施例1~9、比較例1、2、4における組成物層は、中間層、ネガ型感光性組成物層、及び紫外線吸収層の3層である。)の厚みT1を測定した。また、厚みT1の測定にあたっては、任意の5か所を測定し、各測定値の平均値として算出した。なお、後述する厚みT2及び厚みT4等の各厚みについても、厚みT1と同様の手順で測定する。
次いで、保護フィルムを剥離して露出した紫外線吸収層に市販のテープを圧着した後、テープを剥離することによって、転写フィルムから紫外線吸収層を剥離した。そして、触針式膜厚計を使用して、紫外線吸収層の剥離後の組成物層の厚みT2を測定した。次いで、厚みT1から厚みT2を差し引くことにより紫外線吸収層の厚みT3を求めた。
次に、別途、新たに転写フィルムを準備し、保護フィルムを剥離した。次いで、保護フィルムを剥離した転写フィルム(言い換えると、紫外線吸収層を露出させた転写フィルム)を、25℃のイオン交換水に60秒間浸漬した。浸漬後、転写フィルムを乾燥させた後(乾燥温度:80℃、乾燥時間:2分)、触針式膜厚計を使用して、転写フィルム中の組成物層の厚みT4を測定した。そして、厚みT1から厚みT4を差し引くことにより紫外線吸収層の溶解した分の厚みT5を求め、厚みT5/厚みT3×100により、紫外線吸収層の溶解率(%)を算出した。
転写フィルムの光学濃度(OD)(波長365nm)を分光器UV4100((株)日立ハイテクノロジー製)によって測定した。次に、紫外線吸収層を有さない転写フィルム、又は、紫外線吸収層を除去した転写フィルムの光学濃度(OD)を同様に測定し、差分により紫外線吸収層の光学濃度(OD)を算出した。なお、OD値は遮光能力を示す数値であり、数値が大きい程、紫外線吸収層が高遮光性であることを示す。
(紫外線吸収層の波長365nmにおける透過率)
紫外線吸収層を有する転写フィルムの波長365nmにおける透過率(%)を紫外可視分光高度計((株)島津製作所製UV-1800)によって測定した。次に、紫外線吸収層を有さない転写フィルム、又は、紫外線吸収層を除去した転写フィルムの透過率(%)を同様に測定し、差分により紫外線吸収層の波長365nmにおける透過率(%)を算出した。
波長365nmを波長405nmにかえた以外は同様の方法で、紫外線吸収層の波長405nmにおける透過率(%)を算出した。
得られた実施例及び比較例の各転写フィルムについて、以下に示す評価を実施した。表2に、評価結果を示す。
(パターン形状)
ガラス上にNiメッキ(厚み100nm)を施した導電性基板を用意した。
作製した転写フィルムの保護フィルムを剥離した後、基材温度80℃、ゴムローラー温度110℃、線圧3N/cm、搬送速度2m/minのラミネート条件で、Niメッキ層と紫外線吸収層とが接するように上記導電性基板上にラミネートした。
次に、仮支持体を剥離し、ライン1μm/スペース1μm~ライン50μm/スペース50μmのパターンを有する各露光マスクを、仮支持体の剥離後に露出する面に密着させた。次いで、高圧水銀灯露光機((株)大日本科研製MAP-1200L、主波長:365nm)を使用し、100mJ/cm2でネガ型感光性組成物層を露光した。
その後、液温が25℃の1質量%炭酸ナトリウム水溶液で30秒間のシャワー現像を行い、Niメッキ層上にパターンを形成した。
図4に、裾引き形状を有するパターンの断面模式図を示す。「裾長さ(片側)」とは、パターン上面FTの端部ETからパターン下面FBに垂線を引いたときの交点Qと、パターン下面FBの端部EBとの距離Lを意図する。裾長さの測定は、パターンの断面形状における2つの側面(図2中の白抜き矢印で指示した側面)毎に実施した。各側面毎に、任意で10か所の裾長さを測定して平均値を算出し、得られた2つの平均値のうち、より大きい数値を下記評価基準に基づいて評価した。
「A」:裾長さ(片側)が、0.5μm以下である。
「B」:裾長さ(片側)が、0.5μmより大きく、1.0μm以下である。
「C」:裾長さ(片側)が、1.0μmより大きい。
(解像性)
ガラス上にNiメッキ(厚み100nm)を施した導電性基板を用意した。
作製した転写フィルムの保護フィルムを剥離した後、基材温度80℃、ゴムローラー温度110℃、線圧3N/cm、搬送速度2m/minのラミネート条件で、Niメッキ層と紫外線吸収層とが接するように上記導電性基板上にラミネートした。
次に、仮支持体を剥離し、所定のライン(μm)/スペース(μm)のパターンを有する露光マスク(なお、ライン幅及びスペース幅は1:1である。)を、仮支持体の剥離後に露出する面に密着させた。次いで、高圧水銀灯露光機((株)大日本科研製MAP-1200L、主波長:365nm)を使用し、100mJ/cm2でネガ型感光性組成物層を露光した。
その後、液温が25℃の1質量%炭酸ナトリウム水溶液で30秒間のシャワー現像を行い、Niメッキ層上にパターンを形成した。
上記手順により得られたパターンが現像残渣無く分解し得る最小線幅を「解像度」として評価を実施した。最小線幅が小さいほど、解像度がより優れる。表2に測定結果を示す。
なお、表2中、「um」は、「μm」を意味する。
また、実施例1~5の対比から、紫外線吸収層の特定ポリマー(ClogPが2.1より小さいポリマー)が、更に、I/O値が0.70より小さい、及び/又は、SP値が2.0(MPa)1/2より大きい場合、解像性がより優れることが明らかとなった。
また、実施例1と、実施例8及び実施例9との対比から、紫外線吸収層のOD値が0.5以下である場合、パターンの裾引き形状をより抑制できることが確認された。特に、紫外線吸収層のOD値が0.4以下である場合、解像性がより優れることが明らかとなった。
また、実施例1と、実施例8及び実施例9との対比から、紫外線吸収層の膜厚が0.30μm以下である場合、パターンの裾引き形状をより抑制できることが確認された。
2、22、42、42A、42B 組成物層
3、43 中間層(中間層A)
5、25、45 ネガ型感光性組成物層
7、29、47 紫外線吸収層
9 屈折率調整層
10、30、40 転写フィルム
11、31 保護フィルム
23 熱可塑性樹脂層
27 中間層(中間層B)
T1、T2、T3、T4、T5 厚み
Claims (15)
- 仮支持体と、前記仮支持体上に配置された、ネガ型感光性組成物層及び紫外線吸収層を含む組成物層と、を有する転写フィルムであり、
前記紫外線吸収層が、前記ネガ型感光性組成物層の前記仮支持体側とは反対側に配置されており、
前記紫外線吸収層が、紫外線吸収剤及びClogP値が2.1より小さいポリマーを含む、転写フィルム。 - 仮支持体と、前記仮支持体上に配置された、ネガ型感光性組成物層及び紫外線吸収層を含む組成物層と、を有する転写フィルムであり、
前記紫外線吸収層が、前記ネガ型感光性組成物層の前記仮支持体側とは反対側に配置されており、
前記紫外線吸収層の下記測定方法により算出される溶解率が、60%以上である、転写フィルム。
(溶解率)
前記組成物層の厚みT1を測定する。次いで、前記組成物層から前記紫外線吸収層を除去し、前記紫外線吸収層を除去した後の前記組成物層の厚みT2を測定し、前記厚みT1から前記厚みT2を差し引くことにより前記紫外線吸収層の厚みT3を求める。また、別途、前記紫外線吸収層を露出させた転写フィルムを準備して、これを25℃のイオン交換水に60秒間浸漬する。浸漬後、前記転写フィルム中の前記組成物層の厚みT4を測定する。そして、前記厚みT1から前記厚みT4を差し引くことにより前記紫外線吸収層の溶解した分の厚みT5を求め、前記厚みT5/前記厚みT3×100により、前記紫外線吸収層の溶解率を算出する。 - 前記紫外線吸収層が、紫外線吸収剤及びClogP値が2.1より小さいポリマーを含む、請求項2に記載の転写フィルム。
- 前記ポリマーのSP値が20.0(MPa)1/2より大きい、請求項1又は3に記載の転写フィルム。
- 前記ポリマーの有機概念図におけるI/O値が0.70より小さい、請求項1、3、又は4に記載の転写フィルム。
- 前記紫外線吸収層の波長365nmにおける透過率が、20~70%である、請求項1~5のいずれか1項に記載の転写フィルム。
- 前記紫外線吸収層の波長405nmにおける透過率が、20~70%である、請求項1~6のいずれか1項に記載の転写フィルム。
- 前記紫外線吸収層が光硬化性である、請求項1~7のいずれか1項に記載の転写フィルム。
- 前記紫外線吸収層の厚みが5.0μm以下である、請求項1~8のいずれか1項に記載の転写フィルム。
- 前記組成物層が、更に中間層を含み、
前記中間層が、前記ネガ型感光性組成物層と前記仮支持体の間に配置されている、請求項1~9のいずれか1項に記載の転写フィルム。 - 前記中間層が、水溶性樹脂を含む、請求項10に記載の転写フィルム。
- 前記中間層が、水溶性セルロース誘導体、ポリエーテル類、多価アルコール類、多価アルコール類のアルキレンオキサイド付加物、フェノール誘導体、及びアミド化合物からなる群から選ばれる1種以上の化合物を含む、請求項11に記載の転写フィルム。
- 請求項1~12のいずれか1項に記載の転写フィルムの前記仮支持体とは反対側の表面を、導電層を有する基板に接触させ、前記基板、前記導電層、前記組成物層、及び、前記仮支持体をこの順に有する組成物層付き基板を得る貼合工程と、
前記仮支持体を剥離する剥離工程と、
露出した前記組成物層をパターン露光する露光工程と、
露光した前記組成物層を現像してパターンを形成する現像工程と、を有する積層体の製造方法。 - 前記露光工程が、露出した前記組成物層とマスクとを接触させて露光処理を実施する工程である、請求項13に記載の積層体の製造方法。
- 請求項1~12のいずれか1項に記載の転写フィルムの前記仮支持体とは反対側の表面を、導電層を有する基板に接触させ、前記基板、前記導電層、前記組成物層、及び、前記仮支持体をこの順に有する組成物層付き基板を得る貼合工程と、
前記仮支持体を剥離する剥離工程と、
露出した前記組成物層をパターン露光する露光工程と、
露光した前記組成物層を現像して樹脂パターンを形成する現像工程と、
前記樹脂パターンが配置されていない領域における前記導電層をエッチング処理するエッチング工程と、を含む、回路配線の製造方法。
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WO2016167228A1 (ja) * | 2015-04-15 | 2016-10-20 | 日立化成株式会社 | 感光性導電フィルム、導電パターンの形成方法、導電パターン付き基材、及びタッチパネルセンサ |
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WO2020137284A1 (ja) * | 2018-12-27 | 2020-07-02 | 富士フイルム株式会社 | 導電性転写材料、パターンつき基板の製造方法、回路基板の製造方法、積層体、及びタッチパネル |
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WO2016167228A1 (ja) * | 2015-04-15 | 2016-10-20 | 日立化成株式会社 | 感光性導電フィルム、導電パターンの形成方法、導電パターン付き基材、及びタッチパネルセンサ |
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