WO2021049241A1 - 感光性樹脂組成物、及び感光性エレメント - Google Patents
感光性樹脂組成物、及び感光性エレメント Download PDFInfo
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- WO2021049241A1 WO2021049241A1 PCT/JP2020/030719 JP2020030719W WO2021049241A1 WO 2021049241 A1 WO2021049241 A1 WO 2021049241A1 JP 2020030719 W JP2020030719 W JP 2020030719W WO 2021049241 A1 WO2021049241 A1 WO 2021049241A1
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- 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
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- 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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- 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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
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- 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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
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- 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
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- 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
- H05K3/18—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 using precipitation techniques to apply the conductive material
Definitions
- the present invention relates to a photosensitive resin composition, a photosensitive element using the photosensitive resin composition, a laminating method, a method for producing a conductor pattern, and the like.
- photolithography method first, a pattern exposure is performed on a photosensitive resin layer laminated on a substrate such as a copper-clad laminate or a flexible substrate.
- the exposed portion of the photosensitive resin layer is polymerized and cured (in the case of a negative type) or solubilized in a developing solution (in the case of a positive type).
- the unexposed portion (in the case of the negative type) or the exposed portion (in the case of the positive type) is removed with a developing solution to form a resist pattern on the substrate.
- the cured resist pattern (hereinafter, also referred to as “resist pattern”) is peeled off and removed from the substrate. By going through these steps, a conductor pattern is formed on the substrate.
- the process of forming a conductor pattern by etching or plating is roughly divided into two.
- the first method is a method in which the substrate surface (for example, a copper surface such as a copper-clad laminate) that is not covered by the resist pattern is removed by etching, and then the resist pattern portion is removed with an alkaline aqueous solution stronger than the developer.
- the second method is a method (plating method) in which the surface of the substrate is plated with copper, solder, nickel, tin, or the like, the resist pattern portion is similarly removed, and the surface of the substrate that appears is etched. In either case, cupric chloride, ferric chloride, cuprammonium complex solution or the like is used for etching.
- a substrate having various outer shapes for example, flat surface, uneven surface, non-planar surface, groove, preformed line / space, etc.
- DLP Digital Light Processing
- DI laser direct drawing
- composition of the photosensitive resin composition is synthesized using a pyridine compound or a cyanide compound (Patent Document 2) and 2- (2-hydroxyphenyl) -1H-benzimidazole as starting materials for improving the photosensitivity.
- Patent Document 2 a pyridine compound or a cyanide compound
- 2- (2-hydroxyphenyl) -1H-benzimidazole The use of nitrogen-containing compounds such as base generators (Patent Document 3) has also been studied.
- an object of the present invention is to provide a photosensitive resin composition capable of achieving both followability and adhesion to a substrate, and a method for producing a photosensitive element, a laminating method, and a conductor pattern using the same.
- the compound (D) has the following general formula (2A): ⁇ In the formula, R 1 is a monovalent organic group having 1 to 20 carbon atoms that does not contain an azo group, and R 3 is It is a monovalent organic group having 1 to 19 carbon atoms and does not contain an azo group.
- the photosensitive resin composition according to any one of [1] to [6] which is a compound represented by.
- a photosensitive element comprising a support and a layer formed on the support and made of the photosensitive resin composition according to any one of items [1] to [7].
- the present invention it is possible to provide a photosensitive element and a conductor pattern that can achieve both followability and adhesion to a substrate in lamination of a resist material and a substrate, and can achieve both followability and adhesion. Further, according to the present invention, it is possible to achieve both followability to a step and adhesion to a Cu substrate, particularly in vacuum lamination.
- Photosensitive resin composition One aspect of the present invention is a photosensitive resin composition.
- the photosensitive resin composition can be used in a photolithography method or in the production of a photosensitive element such as a dry film resist.
- the photosensitive resin composition is composed of (A) an alkali-soluble polymer; (B) a compound having an ethylenically unsaturated double bond; (C) a photopolymerization initiator; and (D) the following.
- the photosensitive resin composition may further include various additives such as discolorants, dyes, plasticizers, antioxidants, organic halogen compounds, nonionic surfactants, crosslinkers, stabilizers and the like. May include.
- the photosensitive resin composition can be used for lamination with a substrate, exposure using a photomask, or exposure using a direct drawing device without using a photomask (direct). It can be used to form a conductor pattern by imaging exposure) and development.
- the components of the photosensitive resin composition will be described below.
- Alkali-soluble polymer (A) Alkali-soluble polymer (A)
- the alkali-soluble polymer preferably contains a carboxyl group from the viewpoint of alkali solubility, and preferably contains a hydroxy group from the viewpoint of developability and peelability.
- the alkali-soluble polymer (A) typically contains a carboxyl group-containing monomer as a copolymerization component, has a carboxyl group content of 100 to 600 in acid equivalent, and has a weight average molecular weight of 5,000 to 500. 000 thermoplastic copolymers.
- the carboxyl group in the alkali-soluble polymer is necessary for the photosensitive resin composition to have developability and peelability with respect to a developing solution and a stripping solution composed of an alkaline aqueous solution.
- the acid equivalent is preferably 100 to 600, more preferably 250 to 450. From the viewpoint of ensuring compatibility with the solvent or other components in the photosensitive resin composition, particularly with (b) an addition-polymerizable monomer described later, 100 or more is preferable, and from the viewpoint of maintaining developability and peelability. It is preferably 600 or less.
- the acid equivalent means the mass (gram) of a thermoplastic copolymer having 1 equivalent of a carboxyl group therein.
- the acid equivalent is measured by a potentiometric titration method using a titrator (for example, Hiranuma reporting titrator (COM-555)) with a 0.1 mol / L NaOH aqueous solution.
- a titrator for example, Hiranuma reporting titrator (COM-555)
- COM-555 Hiranuma reporting titrator
- the weight average molecular weight of the thermoplastic copolymer is preferably 5,000 to 500,000. From the viewpoint of maintaining a uniform thickness of the dry film resist and obtaining resistance to a developing solution, 5,000 or more is preferable, and from the viewpoint of maintaining developability, 500,000 or less is preferable. More preferably, the weight average molecular weight is 20,000 to 100,000. The measurement conditions for the weight average molecular weight will be described in detail in the following examples.
- thermoplastic copolymer is preferably obtained by copolymerizing a copolymerization component composed of one or more of the first monomer described later and one or more of the second monomer described later.
- the first monomer is a monomer containing a carboxyl group in the molecule.
- the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid semi-ester.
- (meth) acrylic acid is particularly preferable.
- (meth) acrylic means acrylic or methacrylic. The same applies hereinafter.
- the second monomer is a non-acidic monomer having 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, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, and iso-butyl.
- methyl (meth) acrylate, n-butyl (meth) acrylate, styrene, and benzyl (meth) acrylate are particularly preferable.
- the amount of the alkali-soluble polymer (A) contained in the photosensitive resin composition according to the present embodiment (provided that it is based on the total solid content of the photosensitive resin composition. Unless otherwise specified below. Is the same for each contained component.) Is preferably 35% by mass or more from the viewpoint of developability, and is 40% by mass to 70% by mass from the viewpoint of balancing alkali developability and tackiness. More preferably, it is 40% by mass to 60% by mass, 41% by mass to 58% by mass, 42% by mass to 57% by mass, or 43% by mass to 56% by mass.
- a compound having an ethylenically unsaturated double bond can have a polymerizable property by having an ethylenically unsaturated double bond in its structure.
- the ethylenically unsaturated bond is preferably a terminal ethylenically unsaturated group from the viewpoint of addition polymerization.
- (B) Compounds having an ethylenically unsaturated double bond include the following (b 1 ) to (b 8 ): (B 1 ) The following general formula (I): ⁇ In the formula, R 1 and R 2 each independently represent a hydrogen atom or a methyl group, and m 1 is a number satisfying 2 to 40.
- the following general formula (II): ⁇ In the formula, R 3 and R 4 independently represent a hydrogen atom or a methyl group, A is C 2 H 4 , B is C 3 H 6 , and n 1 , n 2 , n 3 and n 4 is an integer satisfying the relationship of n 1 + n 2 + n 3 + n 4 2 to 50, and the sequence of repeating units of-(AO)-and-(BO)-is random. In the case of a block, either ⁇ (A—O) ⁇ or ⁇ (BO) ⁇ may be on the bisphenyl group side.
- An alkylene oxide-modified bisphenol type A di (meth) acrylate compound represented by (B 3 ) The following general formula (III): ⁇ In the formula, R 5 to R 7 independently represent a hydrogen atom or a methyl group, X represents an alkylene group having 2 to 6 carbon atoms, and m 2 , m 3 and m 4 independently represent each. , 0-40, m 2 + m 3 + m 4 is 1-40, and m 2 + m 3 + m 4 is greater than or equal to 2, then the plurality of X's are identical to each other.
- 63 may be the same or different ⁇ O-phthalate compound represented by; (B 7 )
- the compound having an ethylenically unsaturated double bond has an ethylene glycol di (meth) represented by (b 1 ) general formula (I) from the viewpoint of adjusting the peeling time of the resist pattern and the size of the peeled piece. ) It is preferable to contain an acrylate compound.
- m 1 is preferably 2 or more from the viewpoint of peeling time and peeling piece size, and preferably 20 or more from the viewpoint of suppressing short-circuit defects after the etching process, and has resolvability. From the viewpoint of plating resistance and etching resistance, it is preferably 40 or less. In photolithography including vacuum lamination, m 1 is preferably 2 to 29, 4 to 20, or 6 to 15 from the viewpoint of developability or resolution of the resist pattern.
- m 1 14 polyethylene glycol di (meth) acrylate
- m 1 23 polyethylene glycol di (meth).
- the compound having an ethylenically unsaturated double bond is an alkylene oxide-modified bisphenol type A di (meth) represented by (b 2) general formula (II) from the viewpoint of suppressing a short circuit after the etching process. It preferably contains an acrylate compound.
- B in the general formula (II) may be -CH 2 CH 2 CH 2- or -CH (CH 3 ) CH 2- .
- the hydrogen atom on the aromatic ring in the general formula (II) may be substituted with a hetero atom and / or a substituent.
- the hetero atom include a halogen atom and the like
- the substituent include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, and a phenacyl group.
- Examples thereof include an aryl group substituted with a substituent. These substituents may form a fused ring, or the hydrogen atom in these substituents may be substituted with a hetero atom such as a halogen atom. When the aromatic ring in the general formula (II) has a plurality of substituents, the plurality of substituents may be the same or different.
- R 3 and R 4 in the general formula (II) may be independently hydrogen atoms or methyl groups, respectively, but from the viewpoint of ensuring contrast immediately after exposure of the photosensitive resin layer composed of the photosensitive resin composition. preferably one or both of R 3 and R 4 is a hydrogen atom, more preferably both of R 3 and R 4 are hydrogen atoms.
- n 1 + n 3 is used when the component (b 2 ) forms the monomer (B1) in photolithography including vacuum lamination from the viewpoint of photosensitivity, developability or resolvability. It is preferably 3 to 30 or 5 to 20, and when the component (b 2 ) forms the (B2) monomer, it is preferably 3 to 30, and more preferably 5 to 20.
- alkylene oxide-modified bisphenol A type di (meth) acrylate compound represented by the general formula (II) is polyethylene glycol in which an average of 1 mol of ethylene oxide is added to both ends of bisphenol A.
- Di (meth) acrylate of polyethylene glycol with an average of 2 mol of ethylene oxide added to both ends of di (meth) acrylate and bisphenol A for example, in the case of dimethacrylate, a product name available from Nichiyu Co., Ltd.) "Blemmer PDBE-200", etc.
- di (meth) acrylate of polyethylene glycol with an average of 2 mol of ethylene oxide added to both ends of bisphenol A di (meth) acrylate of polyethylene glycol with an average of 2 mol of ethylene oxide added to both ends of bisphenol A
- polyethylene glycol with an average of 5 mol of ethylene oxide added to both ends of bisphenol A for example, in the case of dimethacrylate, a product name available from Nichiyu Co., Ltd.
- Di (meth) acrylate for example, in the case of diacrylate, the product name "A-BPE-10" available from Shin-Nakamura Chemical Industry Co., Ltd., etc., and in the case of dimethacrylate, obtained from Hitachi Kasei Co., Ltd. Possible product name "FA-321", product name "BPE-500” available from Shin-Nakamura Chemical Industry Co., Ltd., etc.), bisphenol A di-polyethylene glycol with an average of 7 mol of ethylene oxide added to both ends.
- Examples thereof include di (meth) acrylate of added polyalkylene glycol and di (meth) acrylate of polyalkylene glycol having an average of 15 mol of ethylene oxide and an average of 2 mol of propylene oxide added to both ends of bisphenol A.
- the compound (B) having an ethylenically unsaturated double bond preferably contains a tri (meth) acrylate compound represented by (b 3) general formula (III) from the viewpoint of resolution.
- X in formula (III) an alkylene group having 2 to 6 carbon atoms, e.g., -CH 2 CH 2 -, - CH 2 CH 2 CH 2 -, - CH (CH 3) CH 2 - and the like in Good.
- the component (b 3 ) is used as the monomer having the EO unit described above, the carbon number of at least one X in the general formula (III) is 2.
- (B 3 ) As a preferable specific example of the tri (meth) acrylate compound represented by the general formula (III), ethylene oxide (EO) -modified trimethylolpropane tri (meth) acrylate (EO average addition molar number: 2 to 40) , 3 to 35, 3 to 20, or 30 to 35), propylene oxide (PO) -modified trimethylolpropane tri (meth) acrylate (PO average addition molar number: 10 to 40), and the like.
- EO ethylene oxide
- PO propylene oxide
- the EO-modified trimethylolpropane tri (meth) acrylate having an average EO molar addition of 3 is, for example, in the case of triacrylate, the product name "A-TMPT-3EO” available from Shin Nakamura Chemical Industry Co., Ltd. And so on.
- the EO-modified trimethylolpropane tri (meth) acrylate having an average EO addition molar number of 9 can be, for example, the product name "Miramer M3160" available from Miwon Specialty Chemical Co., Ltd. in the case of triacrylate. ..
- the compound (B) having an ethylenically unsaturated double bond preferably contains a urethane di (meth) acrylate compound represented by (b 4) general formula (IV) from the viewpoint of resolution.
- Z represents a divalent organic group, for example, an alkylene group having 1 to 10 carbon atoms, an alkylene oxide group having 2 to 10 carbon atoms, and a number of carbon atoms which may have a substituent.
- a divalent alicyclic group of 3 to 10 may be used.
- Y represents an alkylene group having 2 to 6 carbon atoms, e.g., -CH 2 CH 2 -, - CH 2 CH 2 CH 2 -, - CH (CH 3) CH 2 - and the like in Good.
- urethane di (meth) acrylate compound represented by the general formula (IV) include a (meth) acrylic monomer having a hydroxyl group at the ⁇ -position, isophorone diisocyanate, 2,6-toluene diisocyanate, and 2, Addition reactants with diisocyanate compounds such as 4-toluene diisocyanate and 1,6-hexamethylene diisocyanate, tris ((meth) acryloxitetraethylene glycol isocyanate) hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate and EO, PO Modified urethane di (meth) acrylate can be mentioned.
- urethane compounds of hexamethylene diisocyanate and polypropylene glycol mono (meth) acrylate are preferable.
- EO represents ethylene oxide
- the EO-modified compound has a block structure of ethylene oxide groups.
- PO represents propylene oxide
- the PO-modified compound has a block structure of a propylene oxide group.
- Examples of the EO-modified urethane di (meth) acrylate include, for example, Shin Nakamura Chemical Industry Co., Ltd., trade name "UA-11” and the like.
- Examples of the EO and PO-modified urethane di (meth) acrylate include, for example, Shin-Nakamura Chemical Industry Co., Ltd., trade name "UA-13". These may be used alone or in combination of two or more.
- the compound having an ethylenically unsaturated double bond (B) preferably contains a hexa (meth) acrylate compound represented by the general formula (V) (b 5) from the viewpoint of resolution.
- the average value of all n is 6 or more, or n is 1 or more, respectively, in the general formula (V).
- the total value of n in the general formula (V) is preferably 180 or less, preferably 30 to 180, 30 to 36, from the viewpoint of photosensitivity, developability or resolution in photolithography including vacuum lamination. More preferably, it is 1 to 29, or 6 to 29.
- hexa (meth) acrylate compound represented by the general formula (V) are dipentaerythritol hexa (meth) acrylate and dipentaerythritol with a total of 1 to 36 mols of ethylene at the six ends.
- Hexa (meth) acrylates to which oxides have been added and hexa (meth) acrylates to which a total of 1 to 10 mol of ⁇ -caprolactone has been added to the six ends of dipentaerythritol can be mentioned.
- the compound having an ethylenically unsaturated double bond can include an o-phthalate compound represented by (b 6) general formula (VI) from the viewpoint of resolution.
- the o-phthalate compound represented by the general formula (VI) include ⁇ -chloro- ⁇ -hydroxypropyl- ⁇ '-(meth) acryloyloxyethyl-o-phthalate and ⁇ -hydroxyethyl- ⁇ '-(. Examples thereof include acryloyloxyethyl-o-phthalate and ⁇ -hydroxypropyl- ⁇ '-(meth) acryloyloxyethyl-o-phthalate.
- ⁇ -chloro- ⁇ -hydroxypropyl- ⁇ '-(meth) acryloyloxyethyl-o-phthalate is preferable. These may be used alone or in combination of two or more.
- the compound having an ethylenically unsaturated double bond is an epoxy (b 7 ) represented by the general formula (VII) from the viewpoint of photosensitivity, developability and resolvability in photolithography including vacuum lamination. It is preferable to contain a meta) acrylate compound, and it is more preferable to use the component (b 7 ) and the trimethylolpropane tri (meth) acrylate as the component (b 8) described later in combination. While not wishing to be bound by theory, (b 7) Formula components in (VII), hydroxy groups present in locations other than the polymerizable end is, it is conceivable to contribute to peeling of the resist pattern.
- the compound having an ethylenically unsaturated double bond may contain an addition-polymerizable monomer other than the components (b 1 ) to (b 7 ) as the component (b 8).
- the component (b 8 ) includes di (meth) acrylates other than the components (b 1 ), (b 2 ) and (b 7 ), for example, polypropylene glycol-polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth).
- examples thereof include polyalkylene glycol di (meth) acrylates such as acrylate and polybutylene glycol di (meth) acrylate.
- di (meth) of polyalkylene glycol in which ethylene oxide is further added to both ends by an average of 3 mol with respect to polypropylene glycol to which an average of 12 mol of propylene oxide is added. ) Acrylate may be used.
- component (b 8 ) the following: -Mono (meth) acrylate, for example, 4-nonylphenyl-heptaethylene glycol-dipropylene glycol (meth) acrylate (for example, in the case of acrylate, the product name "Dispanol LS-" available from NOF CORPORATION. 100A ") etc .; -Tri (meth) acrylate other than the component (b 3 ), for example, trimethylolpropane tri (meth) acrylate (for example, in the case of triacrylate, the product name "A-" available from Shin Nakamura Chemical Industry Co., Ltd.
- -Mono (meth) acrylate for example, 4-nonylphenyl-heptaethylene glycol-dipropylene glycol (meth) acrylate (for example, in the case of acrylate, the product name "Dispanol LS-" available from NOF CORPORATION. 100A ") etc .
- TMPT TMPT ", etc.), glycerin tri (meth) acrylate ethoxylated, tri (meth) acrylate isocyanurate, pentaerythritol tri (meth) acrylate, etc.; -Tetra (meth) acrylate, for example, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, pentaerythritol (poly) alkoxytetra (meth) acrylate, etc.; -Penta (meth) acrylate, for example, dipentaerythritol penta (meth) acrylate, etc .; -A compound obtained by reacting a polyhydric alcohol with an ⁇ , ⁇ -unsaturated carboxylic acid; and-A compound obtained by reacting
- the total amount of all the compounds having (B) ethylenically unsaturated double bonds in the photosensitive resin composition is preferably 1% by mass to 49% by mass. , More preferably 1% by mass to 44% by mass, 2% by mass to 47% by mass or 2% by mass to 42% by mass, still more preferably 4% by mass to 39% by mass, and particularly preferably 15% by mass to 38% by mass. %, 20% by mass to 35% by mass, or 30% by mass to 34% by mass.
- (C) Photopolymerization Initiator As the photopolymerization initiator, a photopolymerization initiator generally used in the field of photosensitive resins can be used. The amount of the (C) photopolymerization initiator in the photosensitive resin composition is 0.1% by mass to 20% by mass. This amount is 0.1% by mass or more from the viewpoint of sensitivity and 20% by mass or less from the viewpoint of resolution. The preferred content is 0.1% by mass to 15% by mass, more preferably 0.9% by mass to 10% by mass. (C) As the photopolymerization initiator, one type may be used alone, or two or more types may be used in combination.
- the (C) photopolymerization initiator is preferably at least one selected from the group consisting of an acridine derivative, an anthracene derivative, and a pyrazoline derivative.
- High sensitivity of the photosensitive composition to UV light can be achieved by using at least one selected from the group consisting of acridine derivatives, anthracene derivatives, and pyrazoline derivatives, and followability and adhesion in the vacuum lamination process. Tends to be good.
- the acridine derivative is more preferable among the (C) photopolymerization initiators.
- the photopolymerization initiator may contain any combination of an acridine derivative, anthracene derivative and pyrazoline derivative, and these derivatives may be used in combination with other photopolymerization initiators.
- Examples of acridine derivatives include 9-phenylacridine, 1,6-bis (9-acridinyl) hexane, 1,7-bis (9-acridinyl) heptane, 1,8-bis (9-acridinyl) octane, 1, Examples thereof include 9-bis (9-acridinyl) nonane, 1,10-bis (9-acridinyl) decane, 1,11-bis (9-acridinyl) undecane, and 1,12-bis (9-acridinyl) dodecane. Of these, 9-phenylacridine is preferable.
- N-aryl amino acids include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine and the like, with N-phenylglycine being preferred.
- anthracene derivative includes both anthracene and compounds derived from it.
- examples of the anthracene derivative include anthracene, 9,10-dialkoxyanthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 9,10-diphenylanthracene, and 2-ethyl.
- anthraquinone examples thereof include anthraquinone, octaethyl anthraquinone, 1,2-benz anthraquinone, 2,3-benz anthraquinone, 2-phenylanthraquinone, 2,3-diphenyl anthraquinone and 1-chloroanthraquinone.
- Examples of the pyrazoline derivative include 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline and 1- (4- (benzoxazole-2-yl)).
- the above derivative and a hexaarylbisimidazolyl derivative (hereinafter, also referred to as a dimer of a triarylimidazolyl derivative or a triarylimidazolyl dimer) are used in combination. You can also do it.
- triarylimidazolyl dimer examples include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer (hereinafter, 2,2'-bis (2-chlorophenyl) -4,4', 5, 5'-tetraphenyl-1,1'-bisimidazole), 2,2', 5-tris- (o-chlorophenyl) -4- (3,4-dimethoxyphenyl) -4', 5'- Diphenyl imidazolyl dimer, 2,4-bis- (o-chlorophenyl) -5- (3,4-dimethoxyphenyl) -diphenyl imidazolyl dimer, 2,4,5-tris- (o-chlorophenyl) -diphenyl Imidazolyl dimer, 2- (o-chlorophenyl) -bis-4,5- (3,4-dimethoxyphenyl) -imidazolyl dimer, 2,2'-
- (C) compounds that can be used as a photopolymerization initiator include, for example, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, and 2,3-dimethylanthraquinone.
- quinones such as 3-chloro-2-methylanthraquinone, benzophenones, Michelers ketones [4,4'-bis (dimethylamino) benzophenones], and aromatic ketones such as 4,4'-bis (diethylamino) benzophenones, Combinations of benzoin ethers such as benzoin, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, and ethyl benzoin, thioxanthones such as benzyl dimethyl ketal, benzyl diethyl ketal, 2,4-diethyl thioxanthone, and alkylaminobenzoic acid, and Examples thereof include oxime esters such as 1-phenyl-1,2-propanedione-2-O-benzoin oxime and 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime.
- Examples of the combination of the above-mentioned thioxanthones and alkylaminobenzoic acid include a combination of ethylthioxanthone and ethyl dimethylaminobenzoate, a combination of 2-chlorthioxanthone and ethyl dimethylaminobenzoate, and isopropylthioxanthone and dimethylamino.
- Examples include a combination with ethyl benzoate.
- a combination of a hexaarylbisimidazole derivative and an aromatic ketone is preferable.
- the photosensitive resin composition according to the embodiment of the present invention has the following general formula (1): as the compound (D).
- R 1 and R 2 are independently selected from the group consisting of monovalent organic groups having 1 to 20 carbon atoms and containing no azo group. ⁇ Includes compounds represented by.
- the C ⁇ N bond in the cyano group of the compound represented by the general formula (1) has a large dipole moment and easily interacts with copper (Cu). Therefore, the photosensitive resin composition interacts with the Cu surface such as a copper (Cu) substrate by containing the compound represented by the general formula (1) together with the components (A) to (C), and has adhesiveness.
- Cu copper
- the compound represented by the general formula (1) is preferably solid at 25 ° C. It is considered that the compound solid at 25 ° C. is softened by heating at the time of lamination with the substrate, and the flexibility is exhibited to improve the followability to the substrate. If the compound represented by the general formula (1) is liquid or waxy at 25 ° C., it is considered that there is no temperature response during lamination with the substrate.
- the molecular weight of the compound represented by the general formula (1) As a means for solidifying the compound represented by the general formula (1) at 25 ° C., it is preferable to control the molecular weight of the compound represented by the general formula (1) within an appropriate range, and the molecular weight is 100 g / g /. It is more preferable to control within the range of mol or more and 250 g / mol or less, and further preferably to control within the range of 111 g / mol or more and 240 g / mol or less.
- the molecular weight of the compound represented by the general formula (1) is 100 g / mol from the viewpoint of being in a solid state at 25 ° C. as described above and from the viewpoint of the followability of the photosensitive resin composition or the photosensitive element to the substrate. It is preferably 250 g / mol or less.
- this molecular weight is 100 g / mol or more, the compound represented by the general formula (1) becomes a solid at 25 ° C., and it is easy to obtain temperature responsiveness during lamination with a substrate.
- the molecular weight is 250 g / mol or less, the softening point of the compound represented by the general formula (1) and the photosensitive resin composition containing the compound is lowered, whereby flexibility is easily exhibited.
- the compound which was solid at 25 ° C. is softened by heating at the time of lamination and becomes flexible. Is expressed, which tends to improve the followability to the substrate.
- the molecular weight of the compound represented by the general formula (1) is more preferably in the range of 111 g / mol or more and 240 g / mol or less.
- R 1 and R 2 are independently selected from the group consisting of monovalent organic groups having 1 to 20 carbon atoms and containing no azo group.
- the carbon number of the groups R 1 and R 2 is preferably 1 to 19 from the viewpoint of adhesion to the substrate and followability in lamination, and in the case of a chain group, 1 to 16, 1 to 14, 1 It is more preferably ⁇ 12, 1 to 10, 1 to 9, 1 to 8 or 1 to 7, and in the case of a cyclic group, 3 to 19, 3 to 18, 3 to 15, 3 to 12, 3 to More preferably, it is 9, 3 to 8, 3 to 7, 6 to 18 or 6 to 12.
- the monovalent organic group having 1 to 20 carbon atoms may have a substituent, a hetero atom or a halogen atom, if desired.
- Examples of monovalent organic groups having 1 to 20 carbon atoms include the groups shown below: -For example, methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and Linear or branched alkyl groups such as n-decyl groups; -For example, unsaturateds such as vinyl, allyl, propenyl, 3-butenyl, 2-butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, octeny
- R 1 and R 2 are the same in the general formula (1), preferred combinations of R 1 and R 2 include aromatic groups such as benzyl groups and phenyl groups.
- R 1 and R 2 are different from each other in the general formula (1), the preferred combination of R 1 and R 2 can be: -Combination of linear alkyl groups with different carbon atoms; -Combination of linear alkyl group and branched chain alkyl group; ⁇ Combination of linear alkyl group and aromatic group; -Combination of branched chain alkyl group and aromatic group; The combination of - a linear alkyl group, a group having an amide bond and C 1 ⁇ 19 branched chain hydrocarbon group; - a straight-chain alkyl group, a combination of a group having a cyano group and a C 1 ⁇ 19 branched chain hydrocarbon group.
- R 1 and R 2 are independently selected from the group consisting of monovalent organic groups having 1 to 20 carbon atoms and containing no azo group.
- R 1 is a monovalent organic group having 1 to 20 carbon atoms that does not contain an azo group
- R 3 is It is a monovalent organic group having 1 to 19 carbon atoms and does not contain an azo group.
- the compound represented by is more preferable.
- the compound represented by the general formula (2) or (2A) has an amide bond in addition to the cyano group, thereby increasing the force of interaction with the Cu surface such as a Cu substrate and adhering to the substrate. Tends to be excellent.
- the groups R 1 and R 2 in the general formula (2) and the groups R 1 in the general formula (2A) may be the same as the groups R 1 and R 2 defined in the general formula (1), respectively. Further, the group R 3 in the general formula (2A) may be the same as the group R 2 defined in the general formula (1) as long as it has 1 to 19 carbon atoms.
- the photosensitive resin composition according to the embodiment of the present invention contains the compound (D) described above in an amount of 0.0001% by mass or more and 0.0150% by mass with respect to the total solid content of the photosensitive resin composition. It is preferably contained in an amount of 0.0001% by mass or more and 0.0100% by mass or less, more preferably 0.0001% by mass or more and 0.0050% by mass or less. Is even more preferable.
- the content of compound (D) is adjusted to the range of 0.0001 to 0.0150% by mass, the photosensitive element formed from the photosensitive resin composition is laminated on a stepped copper (Cu) substrate. At that time, there is a tendency that both step followability and Cu adhesion can be achieved at the same time.
- the photosensitive resin composition contains various additives such as discoloring agents, dyes, plasticizers, antioxidants, organic halogen compounds, and the like. It may further contain nonionic surfactants, cross-linking agents, stabilizers and the like.
- Discoloring agent examples include leuco dye and fluorane dye.
- examples of the leuco dye include leuco crystal violet, leuco malachite green and the like.
- the content of the discoloring agent in the photosensitive resin composition is preferably 0.01% by mass or more from the viewpoint of making it possible to recognize good colorability (that is, color development), and from the viewpoint of hue stability and a good image. From the viewpoint of obtaining characteristics, 5% by mass or less is preferable.
- dyes examples include Basic Green 1 [CAS: 633-03-4] (for example, Aizen Diamond Green GH, trade name, manufactured by Hodogaya Chemical Industry Co., Ltd.), malachite green oxalate [2437-29-].
- the amount of the dye in the photosensitive resin composition is preferably in the range of 0.001% by mass to 0.3% by mass, more preferably in the range of 0.01% by mass to 0.12% by mass. ..
- the amount of the dye is preferably 0.001% by mass or more from the viewpoint of making good colorability recognizable, and preferably 0.3% by mass or less from the viewpoint of maintaining sensitivity.
- plasticizer examples include polyethylene glycol, polypropylene glycol (for example, Mw ⁇ 2000), polyoxypropylene polyoxyethylene ether, polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether, polyoxyethylene polyoxypropylene monomethyl ether, and the like.
- Glycol esters such as polyoxyethylene monoethyl ether, polyoxypropylene monoethyl ether, polyoxyethylene polyoxypropylene monoethyl ether, phthalic acid esters such as diethyl phthalate, o-toluene sulfonic acid amide and p-toluene sulfone.
- sulfonamides such as acid amide, tributyl citrate, triethyl citrate, triethyl acetyl citrate, tri-n-propyl acetyl citrate, and tri-n-butyl acetyl citrate. Of these, sulfonamides are preferable.
- the amount of the plasticizer in the photosensitive resin composition is preferably 0.1% by mass to 50% by mass, more preferably 1% by mass to 20% by mass, and further preferably 3% by mass to 10% by mass. ..
- the amount of the plasticizer is preferably 0.1% by mass or more from the viewpoint of ensuring viscosity stability, suppressing delay in development time, and imparting flexibility or peelability to the cured film, and curing. It is preferably 50% by mass or less from the viewpoint of suppressing shortage and cold flow.
- antioxidants examples include triphenylphosphite (for example, manufactured by ADEKA Corporation, trade name: TPP), tris (2,4-di-t-butylphenyl) phosphite (for example, ADEKA Corporation). , Trade name 2112), Tris (monononylphenyl) phosphite (eg, ADEKA Corporation, trade name: 1178), and Bis (monononylphenyl) -dinonylphenyl phosphite (eg, ADEKA Corporation, Product name: 329K).
- the content of the antioxidant in the photosensitive resin composition is preferably in the range of 0.01 to 0.8% by mass, more preferably in the range of 0.01 to 0.3% by mass.
- the content is 0.01% by mass or more, the effect of excellent hue stability of the photosensitive resin composition is well exhibited, and the sensitivity of the photosensitive resin composition at the time of exposure is good. Further, when the content is 0.8% by mass or less, the color development property is suppressed, so that the hue stability is good and the adhesion is also good.
- Organic halogen compounds examples include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenyl sulfone, and carbon tetrabromide. , Tris (2,3-dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, and triazine chlorinated compounds.
- the amount of the organic halogen compound in the photosensitive resin composition is preferably 0.001% by mass to 3% by mass, more preferably 0.005% by mass to 2.5% by mass, or 0.01% by mass to 1. It is 0% by mass.
- Nonionic Surfactants As nonionic surfactants, sorbitan / fatty acid compounds such as polyoxyethylene sorbitan triolate (for example, Japanese emulsifier) are used from the viewpoints of low toxicity, emulsifying action, rust prevention and antistatic properties. Product names such as "New Call 3-85" available from Co., Ltd.) are preferable.
- the amount of the nonionic surfactant in the photosensitive resin composition is preferably 0.001% by mass to 3% by mass, more preferably 0.01% by mass to 2.5% by mass, and further preferably 0. It is 5% by mass to 2.0% by mass, or 1% by mass to 2% by mass.
- the cross-linking agent is a dithiol compound having a triazine skeleton from the viewpoint of water resistance or heat resistance, for example, 2- (dibutylamino) -1,3,5-triazine-4,6-dithiol (for example, Kawaguchi Chemical Industry Co., Ltd.).
- Product name "BSH” etc. available from Kogyo Co., Ltd.) is preferable.
- the amount of the cross-linking agent in the photosensitive resin composition is preferably 0.001% by mass to 3% by mass, more preferably 0.005% by mass to 2.5% by mass, and 0.01% by mass to 1.0% by mass. %, Or 0.02% by mass to 0.1% by mass.
- Stabilizers examples include radical polymerization inhibitors, thiadiazoles, thiadiazoles, benzotriazoles, and carboxybenzotriazoles from the viewpoint of improving the thermal stability and / or storage stability of the photosensitive resin composition. , And one or more compounds selected from the group consisting of cresols are preferred.
- radical polymerization inhibitor examples include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, and 2,2'-methylenebis.
- thiazoles examples include 2-mercaptobenzothiazole, 6-amino-2-mercaptobenzothiazole, 2-mercapto-5-methoxybenzothiazole, 5-chloro-2-mercaptobenzothiazole and the like.
- thiadiazoles examples include 2-amino-5-mercapto-1,3,4-thiadiazole and the like.
- benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-benzotriazole, and the like.
- Bis (N-2-ethylhexyl) aminomethylene-1,2,3-triltriazole, bis (N-2-hydroxyethyl) aminomethylene-1,2,3-benzotriazole, 1- (N, N-bis (N, N-bis) 2-Ethylhexyl) aminomethyl) -1,2,3-benzotriazole and the like can be mentioned.
- 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, N- (N, N-di-2-ethylhexyl) aminoethylenecarboxybenzotriazole, and 1- (2-di Examples thereof include a 1: 1 mixture of -n-butylaminomethyl) -5-carboxybenzotriazole and 1- (2-di-n-butylaminomethyl) -6-carboxybenzotriazole.
- cresols examples include 4,4'-butylidenebis (6-tert-butyl-m-cresol), and specifically, the product name "Antage W-300" available from Kawaguchi Chemical Industry Co., Ltd. Can be mentioned.
- the total amount of the stabilizer in the photosensitive resin composition is preferably 0.001% by mass to 4.0% by mass, more preferably 0.01% by mass to 2.0% by mass, and further preferably. Is 0.05% by mass to 1.9% by mass.
- the total amount is preferably 0.001% by mass or more from the viewpoint of imparting good storage stability to the photosensitive resin composition, and preferably 4.0% by mass or less from the viewpoint of maintaining good sensitivity. ..
- the photosensitive resin composition of the present invention may be used as a photosensitive resin composition preparation solution formed by adding a solvent to the photosensitive resin composition.
- Suitable solvents include ketones typified by methyl ethyl ketone (MEK) and alcohols such as methanol, ethanol and isopropyl alcohol. It is preferable to add a solvent to the photosensitive resin composition so that the viscosity of the photosensitive resin composition formulation is 500 mPa ⁇ sec to 4000 mPa ⁇ sec at 25 ° C.
- Photosensitive element (photosensitive resin laminate)> Another aspect of the present invention is a photosensitive resin laminate having a support and a photosensitive resin layer composed of the above-mentioned photosensitive resin composition according to the present invention laminated on the support (hereinafter, photosensitive). Also called an element).
- the photosensitive element may have a protective layer on the surface of the photosensitive resin layer opposite to the support forming side, if necessary.
- the photosensitive element is preferably a resist material having the form of a dry film (hereinafter, also referred to as a dry film resist) from the viewpoint of being used in a photolithography method.
- a transparent one that transmits the light emitted from the exposure light source is desirable.
- a support examples include polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethylmethacrylate copolymer film, and polystyrene film. , Polyacrylonitrile film, styrene copolymer film, polyamide film, cellulose derivative film and the like. If desired, stretches of these films can also be used as supports.
- the haze of the film used as a support is preferably 5 or less, and the thinner the haze, the more advantageous it is from the viewpoint of image formation and economy, but from the viewpoint of maintaining strength, it is 10 ⁇ m or more. It is preferably 30 ⁇ m.
- an important property of the protective layer used for the photosensitive element is that the protective layer has a smaller adhesion to the photosensitive resin layer than the support and can be easily peeled off.
- a polyethylene film, a polypropylene film, or the like is preferable as the protective layer.
- a film having excellent peelability shown in JP-A-59-202457 can be used as the protective layer.
- the thickness of the protective layer is preferably 10 ⁇ m to 100 ⁇ m, more preferably 10 ⁇ m to 50 ⁇ m.
- the thickness of the photosensitive resin layer in the photosensitive element is preferably 3 ⁇ m to 100 ⁇ m, more preferably 5 ⁇ m to 60 ⁇ m. The thinner the photosensitive resin layer, the higher the resolution, and the thicker the photosensitive resin layer, the higher the film strength. Therefore, it can be appropriately selected according to the intended use.
- the photosensitive resin composition used for forming the photosensitive resin layer is formed as the above-mentioned photosensitive resin composition preparation solution, and first coated on the support using a bar coater or a roll coater. After drying, a photosensitive resin layer made of a photosensitive resin composition is laminated on the support. Then, if necessary, the photosensitive element can be manufactured by laminating a protective layer on the photosensitive resin layer.
- Another aspect of the present invention is a method of laminating the above-mentioned photosensitive element of the present invention on a substrate.
- the lamination between the photosensitive element and the substrate is preferably vacuum lamination from the viewpoint of suppressing the generation of air bubbles (voids) or wrinkles in the laminate of the photosensitive element and the substrate, and specifically, the lamination is less than atmospheric pressure. It is preferably carried out under atmospheric pressure.
- the vacuum lamination can be performed by, for example, a diaphragm type laminator, a hydraulic press type laminator, or the like.
- the lamination between the dry film resist and the substrate is performed in the absence of the liquid, or the liquid is applied between the substrate and the dry film resist to apply the liquid to the substrate.
- Wet lamination that fills the gaps in the dry film resist with a liquid and vacuum lamination that is performed under a pressure lower than atmospheric pressure are possible.
- vacuum lamination is preferable from the viewpoint of the followability and adhesion of the dry film resist to the substrate. ..
- the vacuum lamination can be performed at a vacuum degree of, for example, 1 to 1000 Pa, preferably 50 to 500 Pa.
- ⁇ Resist pattern formation method> After the lamination described above, an exposure step of exposing the photosensitive resin layer of the photosensitive element; and a developing step of forming a resist pattern by developing the exposed photosensitive resin layer with a developing solution are performed in order of the resist pattern.
- a forming method can be provided. An example of a specific method for forming a resist pattern using the dry lamination and / or vacuum lamination described above is shown.
- the photosensitive resin composition in the photosensitive resin layer is exposed to active light using an exposure machine.
- the exposed portion of the photosensitive resin layer is polymerized and cured (when the photosensitive resin composition is a negative type) or solubilized in a developing solution (when the photosensitive resin composition is a positive type).
- Exposure can be performed after the support has been peeled off, if necessary.
- the amount of exposure is determined by the illuminance of the light source and the exposure time, and may be measured using a photometer.
- a maskless exposure method may be used.
- a photomask is not used and the exposure is performed directly on the substrate by a drawing device.
- a semiconductor laser having a wavelength of 350 nm to 410 nm, an ultrahigh pressure mercury lamp, or the like is used.
- the drawing pattern is controlled by a computer, and the exposure amount in this case is determined by the illuminance of the exposure light source and the moving speed of the substrate.
- the unexposed portion (when the photosensitive resin composition is a negative type) or the exposed portion (when the photosensitive resin composition is a positive type) in the photosensitive resin layer after exposure is subjected to a developing apparatus. Remove with a developer using. If there is a support on the photosensitive resin layer after exposure, this is excluded. Subsequently, the unexposed portion or the exposed portion is developed and removed using a developing solution composed of an alkaline aqueous solution to obtain a resist image.
- an aqueous solution such as Na 2 CO 3 or K 2 CO 3 is preferable.
- a Na 2 CO 3 aqueous solution having a concentration of 0.2% by mass to 2% by mass is generally used.
- a surface active agent, a defoaming agent, a small amount of an organic solvent for accelerating development, or the like may be mixed in the alkaline aqueous solution.
- the temperature of the developing solution in the developing step is preferably kept constant within the range of 20 ° C. to 40 ° C.
- the resist pattern can be obtained by the above-mentioned step, but in some cases, a heating step of 100 ° C. to 300 ° C. can be further performed. By carrying out this heating step, it is possible to further improve the chemical resistance of the pattern.
- a heating furnace of a type such as hot air, infrared rays, or far infrared rays can be used.
- Another aspect of the present invention is a method for manufacturing a conductor pattern including the above-mentioned lamination of a photosensitive element and a substrate. Also in the production of the conductor pattern, the lamination between the photosensitive element and the substrate is preferably performed at a pressure lower than the atmospheric pressure from the viewpoint of suppressing the generation of voids or wrinkles in the laminate of the photosensitive element and the substrate.
- An example of a method for manufacturing a conductor pattern using the dry lamination and / or vacuum lamination described above is shown below.
- the method for manufacturing a conductor pattern according to an embodiment of the present invention is carried out by using a metal plate or a metal film insulating plate as a substrate, forming a resist pattern by the above-mentioned resist pattern forming method, and then passing through a conductor pattern forming step.
- a conductor pattern forming step can be done.
- an exposure step of exposing the photosensitive resin layer after the above-mentioned dry lamination / vacuum lamination; a developing step of forming a resist pattern by developing the exposed photosensitive resin layer with a developing solution; and a resist pattern are formed.
- the conductor pattern forming step of etching or plating the substrate can be performed in this order.
- a conductor pattern is formed on the surface of the substrate exposed by development (for example, a copper surface) by a known etching method or plating method. Good.
- the resist pattern has a desired wiring pattern by further performing a peeling step of peeling the resist pattern from the substrate with an aqueous solution having a stronger alkalinity than the developing solution.
- a printed wiring board can be obtained.
- a copper-clad laminate or a flexible substrate is preferably used as the substrate.
- the alkaline aqueous solution for peeling (hereinafter, also referred to as “peeling liquid”) is not particularly limited, but an aqueous solution of NaOH or KOH having a concentration of 2% by mass to 5% by mass is generally used. It is possible to add a small amount of water-soluble solvent to the stripping solution.
- the temperature of the stripping liquid in the stripping step is preferably in the range of 40 ° C. to 70 ° C.
- a lead frame can be manufactured by using a metal plate such as copper, a copper alloy, or an iron-based alloy as a substrate, forming a resist pattern by the above-mentioned resist pattern forming method, and then performing the following steps. First, a step of etching the substrate exposed by development to form a conductor pattern is performed. Then, a peeling step of peeling the resist pattern by the same method as the above-described method for manufacturing a printed wiring board is performed to obtain a desired lead frame.
- a metal plate such as copper, a copper alloy, or an iron-based alloy
- the resist pattern formed by the resist pattern forming method of the present invention can be used as a protective mask member when the substrate is processed by the sandblasting method.
- the substrate at this time include glass, silicon wafers, amorphous silicon, polycrystalline silicon, ceramics, sapphire, and metal materials.
- a resist pattern is formed on these substrates by a method similar to the above-mentioned resist pattern forming method. After that, a blasting material is sprayed onto the formed resist pattern to cut it to a desired depth, and a stripping step of removing the resist pattern portion remaining on the substrate from the substrate with an alkaline stripping solution or the like is performed. A substrate having a fine uneven pattern on the top can be produced.
- blasting materials can be used as the blasting material used in the sandblasting step, and for example, fine particles having a particle size of 2 ⁇ m to 100 ⁇ m such as SiC, SiO 2 , Al 2 O 3 , CaCO 3, ZrO, glass, and stainless steel are used.
- a semiconductor package can be manufactured by using a wafer on which a large-scale integrated circuit (LSI) is formed as a substrate, forming a resist pattern on the wafer by the resist pattern forming method described above, and then performing the following steps. it can.
- LSI large-scale integrated circuit
- a step of forming a conductor pattern is performed by subjecting the openings exposed by development to columnar plating such as copper or solder.
- a peeling step of peeling the resist pattern by the same method as the above-mentioned manufacturing method of the printed wiring board is performed, and further, a step of removing the thin metal layer of the portion other than the columnar plating by etching is performed, which is desired.
- a semiconductor package can be obtained.
- An evaluation sample was prepared as follows.
- the content of compound (D) in Table 1 means a concentration based on the total amount of solids in the photosensitive resin composition.
- ⁇ Board surface preparation> As an image quality evaluation substrate, a 0.4 mm thick copper-clad laminate in which 35 ⁇ m rolled copper foil is laminated is jetted with a grinding agent (manufactured by Uji Denka Kogyo Co., Ltd., # 400) at a spray pressure of 0.2 MPa. After scrubbing, the surface of the substrate was washed with a 10 mass% H 2 SO 4 aqueous solution.
- a grinding agent manufactured by Uji Denka Kogyo Co., Ltd., # 400
- the evaluation substrate 2 hours after laminating was exposed to a direct drawing exposure machine (INPREX IP-88000, manufactured by Adtech Engineering Co., Ltd.) using a stofer 41-step step tablet.
- the exposure was performed with an exposure amount such that the maximum number of residual film stages when exposed and developed using the stofer 41-stage step tablet as a mask was 14.
- ⁇ Development> After peeling the polyethylene terephthalate film (support film) from the photosensitive element, use an alkaline developing machine (manufactured by Fuji Kiko Co., Ltd., a developing machine for dry film) to apply a 1% by mass Na 2 CO 3 aqueous solution at 30 ° C. for a predetermined time. The film was sprayed and developed. The time of the developing spray was set to twice the shortest developing time, and the time of the washing spray after development was set to twice the shortest developing time. At this time, the shortest time required for the photosensitive resin layer in the unexposed portion to be completely dissolved was defined as the shortest development time.
- GC gas chromatography
- FID hydrogen flame ionization detector
- a commercially available dry film resist (DFR) was used to laminate, expose, develop, etch, and peel the copper-clad laminate to prepare a pit substrate having a circular recess having a diameter of 310 ⁇ m and a depth of about 10 ⁇ m.
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Abstract
Description
[1]
(A)アルカリ可溶性高分子;
(B)エチレン性不飽和二重結合を有する化合物;
(C)光重合開始剤;及び
(D)下記一般式(1):
で表される化合物;
を含有する感光性樹脂組成物。
[2]
前記化合物(D)が25℃で固体である、項目[1]に記載の感光性樹脂組成物。
[3]
前記化合物(D)の分子量が、100g/mol以上250g/mol以下である、項目[1]又は[2]に記載の感光性樹脂組成物。
[4]
前記化合物(D)を、前記感光性樹脂組成物の固形分の総量に対して0.0001質量%以上0.0150質量%以下含有する、項目[1]~[3]のいずれかに記載の感光性樹脂組成物。
[5]
前記化合物(D)を、前記感光性樹脂組成物の固形分の総量に対して0.0001質量%以上0.0100質量%以下含有する、項目[1]~[4]のいずれかに記載の感光性樹脂組成物。
[6]
前記化合物(D)を、前記感光性樹脂組成物の固形分の総量に対して0.0001質量%以上0.0050質量%以下含有する、項目[1]~[5]のいずれかに記載の感光性樹脂組成物。
[7]
前記化合物(D)が、下記一般式(2A):
アゾ基を含まない炭素数1~19の1価の有機基である。}
で表される化合物である、[1]~[6]のいずれか一項に記載の感光性樹脂組成物。
[8]
支持体と、前記支持体上に形成された、項目[1]~[7]のいずれかに記載の感光性樹脂組成物から成る層とを備える、感光性エレメント。
[9]
ドライフィルムレジストである、項目[8]に記載の感光性エレメント。
[10]
項目[8]又は[9]に記載の感光性エレメントを大気圧未満の気圧下で基板にラミネートする方法。
[11]
導体パターンの製造方法であって、
項目[8]又は[9]に記載の感光性エレメントを大気圧未満の気圧下で基板にラミネートする工程を含む方法。
本発明の一態様は、感光性樹脂組成物である。感光性樹脂組成物は、フォトリソグラフィー法において使用されたり、ドライフィルムレジストなどの感光性エレメントの製造において使用されたりすることができる。
で表される化合物を含有する。
(A)アルカリ可溶性高分子は、アルカリ可溶性の観点から、カルボキシル基を含有することが好ましく、現像性及び剥離性の観点から、ヒドロキシ基を含むことが好ましい。(A)アルカリ可溶性高分子は、典型的には、カルボキシル基含有単量体を共重合成分として含む、カルボキシル基含有量が酸当量で100~600、かつ重量平均分子量が5,000~500,000の熱可塑性共重合体である。
(B)エチレン性不飽和二重結合を有する化合物は、その構造中にエチレン性不飽和二重を有することによって重合性を有することができる。エチレン性不飽和結合は、付加重合性の観点から、末端エチレン性不飽和基であることが好ましい。
(b1)下記一般式(I):
で表されるエチレングリコールジ(メタ)アクリレート化合物;
(b2)下記一般式(II):
で表されるアルキレンオキシド変性ビスフェノールA型ジ(メタ)アクリレート化合物;
(b3)下記一般式(III):
で表されるトリ(メタ)アクリレート化合物;
(b4)下記一般式(IV):
で表されるウレタンジ(メタ)アクリレート化合物;
(b5)下記一般式(V):
で表されるヘキサ(メタ)アクリレート化合物;
(b6)下記一般式(VI):
で表されるo-フタレート化合物;
(b7)下記式(VII):
で表されるエポキシ(メタ)アクリレート化合物;及び
(b8)上記(b1)~(b7)以外の付加重合性モノマー;
から成る群から選択される少なくとも1つを含んでよい。
・モノ(メタ)アクリレート、例えば、4-ノニルフェニル-ヘプタエチレングリコール-ジプロピレングリコール(メタ)アクリレート(例えば、アクリレートの場合には、日油(株)から入手可能な製品名「ディスパノールLS-100A」)等;
・(b3)成分以外のトリ(メタ)アクリレート、例えば、トリメチロールプロパントリ(メタ)アクリレート(例えば、トリアクリレートの場合には、新中村化学工業(株)から入手可能な製品名「A-TMPT」など)、エトキシ化グリセリントリ(メタ)アクリレート、エトキシ化イソシアヌル酸トリ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート等;
・テトラ(メタ)アクリレート、例えば、ジトリメチロールプロパンテトラ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールテトラ(メタ)アクリレート、ペンタエリスリトール(ポリ)アルコキシテトラ(メタ)アクリレート等;
・ペンタ(メタ)アクリレート、例えば、ジペンタエリスリトールペンタ(メタ)アクリレート等;
・多価アルコールにα,β-不飽和カルボン酸を反応させて得られる化合物;及び
・グリシジル基含有化合物にα,β-不飽和カルボン酸を反応させて得られる化合物;
が挙げられる。
(C)光重合開始剤としては感光性樹脂の分野で一般的に用いられる光重合開始剤を使用できる。感光性樹脂組成物中の(C)光重合開始剤の量は、0.1質量%~20質量%である。この量は、感度の観点から0.1質量%以上であり、解像度の観点から20質量%以下である。好ましい含有量は、0.1質量%~15質量%であり、0.9質量%~10質量%がより好ましい。(C)光重合開始剤としては、1種類単独で使用してもよいし、2種類以上組み合わせて用いてもよい。
本発明の一実施形態に係る感光性樹脂組成物は、化合物(D)として、下記一般式(1):
で表される化合物を含む。
・例えば、メチル、エチル、n-プロピル、i-プロピル、n-ブチル、s-ブチル、t-ブチル、n-ペンチル、ネオペンチル、n-ヘキシル、n-ヘプチル、n-オクチル、n-ノニル、及びn-デシル基などの直鎖又は分岐鎖アルキル基;
・例えば、ビニル、アリル、プロペニル、3-ブテニル、2-ブテニル、ペンテニル、シクロペンテニル、ヘキセニル、シクロヘキセニル、ヘプテニル、オクテニル、ノネニル、デセニル、エチニル、プロピニル、ブチニル、ペンチニル、及びヘキシニル基等の不飽和脂肪族炭化水素基;
・例えば、アルコキシ、エポキシ基等のヘテロ原子含有基;
・例えば、モノ-,ジ-又はトリ-フルオロメチル、モノ-,ジ-又はトリ-クロロメチル基等のハロゲン含有基;
・シクロプロピル、シクロブチル、シクロペンチル、シクロヘキシル、シクロヘプチル、及びシクロオクチル基等のシクロアルキル基;
・例えば、フェニル基、アリール基、ベンジル基、フェノキシ基、ベンゾイル基、ナフチル基、アントリル基、フェナントリル基などの芳香族基、及びこれらのハロゲン化物:
・アミド結合及びC1~19分岐鎖炭化水素基を有する基、例えば、下記式:
で表される基など;
・シアノ基及びC1~19分岐鎖炭化水素基を有する基、例えば、下記式:
で表される基など。
・互いに炭素数の異なる直鎖アルキル基同士の組み合わせ;
・直鎖アルキル基と分岐鎖アルキル基の組み合わせ;
・直鎖アルキル基と芳香族基の組み合わせ;
・分岐鎖アルキル基と芳香族基の組み合わせ;
・直鎖アルキル基と、アミド結合及びC1~19分岐鎖炭化水素基を有する基との組み合わせ;
・直鎖アルキル基と、シアノ基及びC1~19分岐鎖炭化水素基を有する基との組み合わせ。
アゾ基を含まない炭素数1~19の1価の有機基である。}
で表される化合物がより好ましい。
感光性樹脂組成物は、上記で説明された成分(A)~(D)に加えて、各種の添加剤、例えば、変色剤、染料、可塑剤、酸化防止剤、有機ハロゲン化合物、非イオン性界面活性剤、架橋剤、及び安定化剤などをさらに含んでよい。
変色剤としては、ロイコ染料及びフルオラン染料が挙げられる。ロイコ染料としては、例えばロイコクリスタルバイオレット、ロイコマラカイトグリーン等が挙げられる。感光性樹脂組成物中の変色剤の含有量としては、良好な着色性(すなわち発色性)が認識できるようにする観点から0.01質量%以上が好ましく、色相安定性の観点及び良好な画像特性を得る観点から5質量%以下が好ましい。
染料としては、例えば、ベイシックグリーン1[CAS:633-03-4](例えば、Aizen Diamond Green GH、商品名、保土谷化学工業(株)製)、マラカイトグリーンしゅう酸塩[2437-29-8](例えばAizen Malachite Green、商品名、保土谷化学工業(株)製)、ブリリアントグリーン[633-03-4]、フクシン[632-99-5]、メチルバイオレット[603-47-4]、メチルバイオレット2B[8004-87-3]、クリスタルバイオレット[548-62-9]、メチルグリーン[82-94-0]、ビクトリアブルーB[2580-56-5]、ベイシックブルー7[2390-60-5](例えば、Aizen Victoria Pure Blue BOH、商品名、保土谷化学工業(株)製)、ローダミンB[81-88-9]、ローダミン6G[989-38-8]、ベイシックイエロー2[2465-27-2]等が挙げられ、中でもベイシックグリーン1、マラカイトグリーンしゅう酸塩、及びベイシックブルー7が好ましい。
可塑剤としては、例えば、ポリエチレングリコール、ポリプロピレングリコール(例えばMw≒2000)、ポリオキシプロピレンポリオキシエチレンエーテル、ポリオキシエチレンモノメチルエーテル、ポリオキシプロピレンモノメチルエーテル、ポリオキシエチレンポリオキシプロピレンモノメチルエーテル、ポリオキシエチレンモノエチルエーテル、ポリオキシプロピレンモノエチルエーテル、ポリオキシエチレンポリオキシプロピレンモノエチルエーテル等のグリコール・エステル類、ジエチルフタレート等のフタル酸エステル類、o-トルエンスルホン酸アミド及びp-トルエンスルホン酸アミド等のスルホンアミド類、クエン酸トリブチル、クエン酸トリエチル、アセチルクエン酸トリエチル、アセチルクエン酸トリ-n-プロピル、及びアセチルクエン酸トリ-n-ブチルが挙げられる。中でも、スルホンアミド類が好ましい。
酸化防止剤としては、例えば、トリフェニルフォスファイト(例えば(株)ADEKA製、商品名:TPP)、トリス(2,4-ジ-t-ブチルフェニル)フォスファイト(例えば(株)ADEKA製、商品名2112)、トリス(モノノニルフェニル)フォスファイト(例えば(株)ADEKA製、商品名:1178)、及びビス(モノノニルフェニル)-ジノニルフェニルフォスファイト(例えば(株)ADEKA製、商品名:329K)が挙げられる。感光性樹脂組成物中の酸化防止剤の含有量は、好ましくは0.01~0.8質量%の範囲であり、より好ましくは、0.01~0.3質量%の範囲である。上記含有量が0.01質量%以上である場合、感光性樹脂組成物の色相安定性に優れる効果が良好に発現し、感光性樹脂組成物の露光時における感度が良好である。また、上記含有量が0.8質量%以下である場合、発色性が抑えられることで色相安定性が良好であるとともに密着性も良好である。
有機ハロゲン化合物としては、例えば、臭化アミル、臭化イソアミル、臭化イソブチレン、臭化エチレン、臭化ジフェニルメチル、臭化ベンジル、臭化メチレン、トリブロモメチルフェニルスルホン、四臭化炭素、トリス(2,3-ジブロモプロピル)ホスフェート、トリクロロアセトアミド、ヨウ化アミル、ヨウ化イソブチル、1,1,1-トリクロロ-2,2-ビス(p-クロロフェニル)エタン、及びクロル化トリアジン化合物が挙げられ、中でも特にトリブロモメチルフェニルスルホンが好ましく用いられる。感光性樹脂組成物中の有機ハロゲン化合物の量は、好ましくは0.001質量%~3質量%、より好ましくは0.005質量%~2.5質量%、又は0.01質量%~1.0質量%である。
非イオン性界面活性剤としては、低毒性、乳化作用、防錆性及び帯電防止性の観点から、ソルビタン・脂肪酸化合物、例えば、ポリオキシエチレンソルビタントリオレート(例えば、日本乳化剤(株)から入手可能な製品名「ニューコール3-85」など)が好ましい。感光性樹脂組成物中の非イオン性界面活性剤の量は、好ましくは0.001質量%~3質量%、より好ましくは0.01質量%~2.5質量%、さらに好ましくは、0.5質量%~2.0質量%、又は1質量%~2質量%である。
架橋剤としては、耐水性又は耐熱性の観点から、トリアジン骨格を有するジチオール化合物、例えば、2-(ジブチルアミノ)-1,3,5-トリアジン-4,6-ジチオール(例えば、川口化学工業(株)から入手可能な製品名「BSH」など)が好ましい。感光性樹脂組成物中の架橋剤の量は、好ましくは0.001質量%~3質量%、より好ましくは0.005質量%~2.5質量%、0.01質量%~1.0質量%、又は0.02質量%~0.1質量%である。
安定化剤としては、感光性樹脂組成物の熱安定性及び/又は保存安定性を向上させるという観点から、ラジカル重合禁止剤、チアゾール類、チアジアゾール類、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、及びクレゾール類から成る群から選ばれる1種以上の化合物が好ましい。
チアジアゾール類としては、例えば、2‐アミノ‐5‐メルカプト‐1,3,4‐チアジアゾール等が挙げられる。
本発明の感光性樹脂組成物は、これに溶媒を添加して形成した感光性樹脂組成物調合液として用いてもよい。好適な溶媒としては、メチルエチルケトン(MEK)に代表されるケトン類、並びにメタノール、エタノール、及びイソプロピルアルコール等のアルコール類が挙げられる。感光性樹脂組成物調合液の粘度が25℃で500mPa・sec~4000mPa・secとなるように、溶媒を感光性樹脂組成物に添加することが好ましい。
本発明の別の態様は、支持体と、支持体上に積層された、上述の本発明に係る感光性樹脂組成物から成る感光性樹脂層とを有する感光性樹脂積層体(以下、感光性エレメントともいう。)を提供する。感光性エレメントは、感光性樹脂層、及び該感光性樹脂層を支持する支持体に加え、必要により、感光性樹脂層の支持体形成側と反対側の表面に保護層を有していてもよい。感光性エレメントは、フォトリソグラフィー法に使用されるという観点から、ドライフィルムの形態を有するレジスト材料(以下、ドライフィルムレジストともいう。)であることが好ましい。
本発明の別の態様は、上述した本発明の感光性エレメントを基板にラミネートする方法である。
上記で説明されたラミネーション後に、感光性エレメントの感光性樹脂層を露光する露光工程;及び露光後の感光性樹脂層を現像液で現像することによってレジストパターンを形成する現像工程を順に行うレジストパターン形成方法を提供することができる。上記で説明されたドライラミネーション及び/又は真空ラミネーションを用いて、レジストパターンを形成する具体的な方法の一例を示す。
本発明の別の態様は、上述した感光性エレメントと基板のラミネーションを含む導体パターンの製造方法である。導体パターンの製造においても、感光性エレメントと基板のラミネーションは、感光性エレメントと基板の積層体におけるボイド又は皺の発生を抑制するという観点から、大気圧未満の気圧下で行われることが好ましい。上記で説明されたドライラミネーション及び/又は真空ラミネーションを用いる導体パターンの製造方法の一例を以下に示す。
なお、本発明に従い上記のような方法で導体パターンを製造した後、レジストパターンを、現像液よりも強いアルカリ性を有する水溶液により基板から剥離する剥離工程を更に行うことにより、所望の配線パターンを有するプリント配線板を得ることができる。プリント基板の製造においては、基板として、好ましくは銅張積層板又はフレキシブル基板を用いる。剥離用のアルカリ水溶液(以下、「剥離液」ともいう。)について特に制限はないが、2質量%~5質量%の濃度の、NaOH又はKOHの水溶液が一般的に用いられる。剥離液には少量の水溶性溶媒を加えることが可能である。剥離工程における剥離液の温度は、40℃~70℃の範囲内であることが好ましい。
基板として銅、銅合金、又は鉄系合金等の金属板を用い、前述のレジストパターン形成方法によってレジストパターンを形成した後に以下の工程を経ることにより、リードフレームを製造できる。先ず、現像により露出した基板をエッチングして導体パターンを形成する工程を行う。その後、レジストパターンを上述のプリント配線板の製造方法と同様の方法で剥離する剥離工程を行って、所望のリードフレームを得る。
本発明のレジストパターン形成方法によって形成されるレジストパターンは、サンドブラスト工法により基板に加工を施す時の保護マスク部材として使用することができる。このときの基板としては、ガラス、シリコンウエハー、アモルファスシリコン、多結晶シリコン、セラミック、サファイア、金属材料等が挙げられる。これらの基板上に、前述のレジストパターン形成方法と同様の方法によって、レジストパターンを形成する。その後、形成されたレジストパターン上からブラスト材を吹き付けて、目的の深さに切削するサンドブラスト処理工程、基板上に残存したレジストパターン部分をアルカリ剥離液等で基板から除去する剥離工程を経て、基板上に微細な凹凸パターンを有する基材を製造することができる。サンドブラスト処理工程に用いるブラスト材としては公知のものを使用でき、例えばSiC、SiO2、Al2O3、CaCO3、ZrO、ガラス、ステンレス等の粒径2μm~100μmの微粒子が用いられる。
基板として、大規模集積回路(LSI)が形成されたウェハを用いて、これに前述のレジストパターン形成方法によってレジストパターンを形成した後に、以下の工程を経ることによって、半導体パッケージを製造することができる。先ず、現像により露出した開口部に銅、はんだ等の柱状のめっきを施して、導体パターンを形成する工程を行う。その後、レジストパターンを上述のプリント配線板の製造方法と同様の方法で剥離する剥離工程を行って、更に、柱状めっき以外の部分の薄い金属層をエッチングにより除去する工程を行うことにより、所望の半導体パッケージを得ることができる。
評価用サンプルを以下のように作製した。
後掲する表1に示す成分(但し、各成分の数字は固形分としての配合量(質量部)を示す。)、及び固形分濃度55%になるように計量したメチルエチルケトンを十分に攪拌、混合して、感光性樹脂組成物調合液を得た。表1中に示した成分の詳細を表2及び表3に示す。支持フィルムとして16μm厚のポリエチレンテレフタラートフィルム(東レ(株)製、16FB40)を用い、その表面にバーコーターを用いて、この調合液を均一に塗布し、95℃の乾燥機中で2分30秒間乾燥して、感光性樹脂層を形成した。感光性樹脂層の乾燥厚みは25μmであった。
次いで、感光性樹脂層のポリエチレンテレフタラートフィルムを積層していない側の表面上に、保護層として19μm厚のポリエチレンフィルム(タマポリ(株)製、GF-18)を貼り合わせて感光性エレメントを得た。
なお、表1中の化合物(D)の含有量は、感光性樹脂組成物中の固形分全量を基準とした濃度を意味する。
画像性の評価基板として、35μm圧延銅箔を積層した0.4mm厚の銅張積層板を、スプレー圧0.2MPaで研削剤(宇治電化学工業(株)製、#400)を用いてジェットスクラブ研磨した後、10質量%H2SO4水溶液で基板表面を洗浄した。
感光性エレメントのポリエチレンフィルム(保護層)を剥がしながら、50℃に予熱した銅張積層板に、ホットロールラミネーター(旭化成(株)社製、AL-700)により、感光性エレメントをロール温度105℃でラミネートした。エアー圧は0.35MPaとし、ラミネート速度は1.5m/minとした。
ラミネート後2時間経過した評価用基板に、直接描画露光機((株)アドテックエンジニアリング製、INPREX IP―8 8000)により、ストーファー41段ステップタブレットを用いて露光した。露光は、前記ストーファー41段ステップタブレットをマスクとして露光、現像したときの最高残膜段数が14段となる露光量で行った。
感光性エレメントからポリエチレンテレフタレートフィルム(支持フィルム)を剥離した後、アルカリ現像機((株)フジ機工製、ドライフィルム用現像機)を用い、30℃の1質量%Na2CO3水溶液を所定時間に亘ってスプレーして現像を行った。現像スプレーの時間は最短現像時間の2倍の時間とし、現像後の水洗スプレーの時間は最短現像時間の2倍の時間とした。この際、未露光部分の感光性樹脂層が完全に溶解するのに要する最も短い時間を最短現像時間とした。
サンプルの評価方法を以下に説明する。
感光性樹脂組成物中の化合物(D)含有量は、(株)島津製作所製のガスクロマトグラフィー(以下、GCと略記する)を用いた内部標準法で求めた。検出器は水素炎イオン化検出器(以下、FIDと略記する)であり、かつ内部標準にはn-ドデカンを使用した。
銅張積層板に、市販のドライフィルムレジスト(DFR)を使ってラミネート、露光、現像、エッチング、及び剥離を行ない、直径310μm、深さ約10μmの円形窪みが形成されたピット基板を作製した。このピット基板に、上記で得られた感光性エレメントをロール式熱真空ラミネーター((株)エム・シー・ケー製、MVR-250)を用いて、ロール温度80℃、シリンダー圧0.4MPa、真空度=100Pa、及び速度1m/分の条件下で、感光性エレメント(膜厚=25μm)の保護フィルムが剥離された面をラミネートした。その際に、感光性エレメントが追従しきれずにピット内部に残ったエアーの直径10点の平均値を算出し、次の基準に沿って評価を行った。評価が「可」以上であれば合格とした。
(評価基準)
優:100μm以下
良:100μm超150μm以下
可:150μm超200μm以下
不可:200μm超
上述の露光工程において、露光部と未露光部の幅がxμm:200μmの比率のラインパターンを有する描画データを使用して露光した。上述の現像条件に従って現像し、硬化レジストラインが正常に形成されている最小ライン幅を光学顕微鏡により測定した。この測定を4本のラインについて行い、その4つの線幅の平均値を密着性の値として求め、次の基準に沿って評価を行った。評価が「可」以上であれば合格とした。
(評価基準)
優:7μm以下
良:7μm超9μm以下
可:9μm超11μm以下
不可:12μm超
実施例1~15及び比較例1~2の評価結果を表1~3に示す。
Claims (11)
- 前記化合物(D)が25℃で固体である、請求項1に記載の感光性樹脂組成物。
- 前記化合物(D)の分子量が、100g/mol以上250g/mol以下である、請求項1又は2に記載の感光性樹脂組成物。
- 前記化合物(D)を、前記感光性樹脂組成物の固形分の総量に対して0.0001質量%以上0.0150質量%以下含有する、請求項1~3のいずれか一項に記載の感光性樹脂組成物。
- 前記化合物(D)を、前記感光性樹脂組成物の固形分の総量に対して0.0001質量%以上0.0100質量%以下含有する、請求項1~4のいずれか一項に記載の感光性樹脂組成物。
- 前記化合物(D)を、前記感光性樹脂組成物の固形分の総量に対して0.0001質量%以上0.0050質量%以下含有する、請求項1~5のいずれか一項に記載の感光性樹脂組成物。
- 支持体と、前記支持体上に形成された、請求項1~7のいずれか一項に記載の感光性樹脂組成物から成る層とを備える、感光性エレメント。
- ドライフィルムレジストである、請求項8に記載の感光性エレメント。
- 請求項8又は9に記載の感光性エレメントを大気圧未満の気圧下で基板にラミネートする方法。
- 導体パターンの製造方法であって、
請求項8又は9に記載の感光性エレメントを大気圧未満の気圧下で基板にラミネートする工程を含む方法。
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JP2008122924A (ja) * | 2006-10-17 | 2008-05-29 | Jsr Corp | スペーサー形成用感放射線性樹脂組成物、スペーサーおよびその形成方法 |
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JP6237084B2 (ja) | 2013-10-07 | 2017-11-29 | Jsr株式会社 | 硬化性組成物、硬化膜及びその形成方法、並びに塩基発生剤 |
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