CN112987496A - Photosensitive resin composition and transfer film using the same - Google Patents

Photosensitive resin composition and transfer film using the same Download PDF

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Publication number
CN112987496A
CN112987496A CN202011462119.2A CN202011462119A CN112987496A CN 112987496 A CN112987496 A CN 112987496A CN 202011462119 A CN202011462119 A CN 202011462119A CN 112987496 A CN112987496 A CN 112987496A
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China
Prior art keywords
photosensitive resin
resin composition
component
dry film
film resist
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CN202011462119.2A
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Chinese (zh)
Inventor
樱井隆觉
西本秀昭
三个野原崇士
下田浩一朗
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Asahi Kasei Corp
Asahi Chemical Industry Co Ltd
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Asahi Kasei Corp
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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
    • 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
    • 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

Abstract

A photosensitive resin composition and a transfer film using the photosensitive resin composition. Provided is a dry film resist or a pattern forming method comprising the same, which improves the yield of an object or a pattern formed by a photolithography method, and a photosensitive resin laminate excellent in at least one of laminatability, minimum development time, resolution, undercut amount, Cu defect, and development residue. Providing a dry film resist comprising a support film and a photosensitive resin composition layer on the support film, the photosensitive resin composition comprising (A) an alkali-soluble resin, (B) a photopolymerizable compound comprising an ethylenically unsaturated bond, (C) a photopolymerization initiator, and (D) a dye, the maximum point load of a specific puncture test being 70gf or more; the component B contains a polyfunctional monomer having three or more functions and a difunctional monomer; and/or the acid value of the nonvolatile component of the photosensitive resin composition is denoted by A and the thickness of the photosensitive resin composition layer is denoted by T, and the ratio of the acid value A to the thickness T is 5 to 90.

Description

Photosensitive resin composition and transfer film using the same
Technical Field
The present invention relates to a photosensitive resin composition, a photosensitive resin laminate, a dry film resist, a resist pattern forming method, a wiring pattern forming method, and the like.
Background
In the past, the production of printed wiring boards, the precision processing of metals, and the like have been performed by photolithography. Photosensitive resin compositions used in photolithography are classified into negative-type compositions in which unexposed portions are dissolved and removed and positive-type compositions in which exposed portions are dissolved and removed.
In the photolithography method, when the photosensitive resin composition is coated on a substrate, any of the following methods may be used:
(1) a method of applying a photoresist solution to a substrate and drying it; and
(2) a method of laminating a photosensitive resin layer on a substrate using a photosensitive resin laminate in which a support, a layer containing a photosensitive resin composition (hereinafter also referred to as "photosensitive resin layer"), and a protective layer as required are sequentially laminated.
In the manufacture of printed circuit boards, the latter method is often used.
A method of forming a pattern using the photosensitive resin laminate will be briefly described below. First, the protective layer is peeled off from the photosensitive resin laminate. Next, a photosensitive resin layer and a support are laminated in this order on a substrate such as a copper-clad laminate or a copper sputtered film using a laminator. Next, the photosensitive resin layer is exposed through a photomask having a desired wiring pattern. Next, the support is peeled off from the exposed laminate, and the non-pattern portion is dissolved or dispersed and removed by a developer, thereby forming a resist pattern on the substrate.
Further, the wiring pattern can be obtained by subjecting the substrate having the resist pattern to etching treatment or plating treatment such as copper plating or solder plating.
Various photosensitive resin compositions have been studied for forming resist patterns or wiring patterns. For example, patent documents 1 and 2 describe a photosensitive resin composition containing a specific alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator.
Patent document 1 focuses on the formation of a photosensitive resin composition excellent in resist shape, minimum development time, and bleeding property, and a resist pattern and a wiring board using the same.
In patent document 2, the adhesiveness and resolution of a resist pattern and the suppression of the occurrence of resist smear are examined for a projection exposure system.
For example, patent documents 3 to 5 disclose a photosensitive resin composition which contains a compound having polyoxytetramethylene as a structural unit, can form a resist pattern even with a low exposure amount, and has excellent protrusion reliability (tent reliability) and etching resistance of a cured film formed.
Further, patent document 6 discloses a photosensitive resin composition which contains a compound having a polyalkyleneoxide as a structural unit, and which can form a resist pattern even with a low exposure amount, and a cured film formed therefrom is excellent in bump reliability and etching resistance.
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 6063200
Patent document 2: japanese patent No. 6432511
Patent document 3: international publication No. 2015/174467
Patent document 4: japanese patent laid-open publication No. 2018-31800
Patent document 5: japanese patent laid-open publication No. 2018-31799
Patent document 6: japanese patent No. 6673196
Disclosure of Invention
Problems to be solved by the invention
There is still a need for improving the yield of objects or patterns formed by photolithography using a photosensitive resin composition.
In addition, the conventional photosensitive resin composition has not obtained sufficient characteristics in terms of laminatability, minimum development time, resolution, amount of undercut (SE, Side etch), Cu defects, and development residues. Further, there are combinations of these characteristics that are difficult to achieve at the same time, and therefore, it is desired to achieve at the same time various characteristics.
In view of the above circumstances, an object of the present invention is to provide a photosensitive resin composition capable of improving the yield of an object or a pattern formed by a photolithography method, a photosensitive resin laminate and a resist or wiring pattern forming method using the same, and/or a photosensitive resin laminate excellent in at least one of laminatability, minimum development time, resolution, amount of undercut (SE), Cu defects, and development residues.
Means for solving the problems
The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that: the above problems can be solved by defining the composition of the photosensitive resin composition, the strength of the photosensitive resin composition measured by a unique test, and/or the relationship between the acid value of the nonvolatile component of the photosensitive resin composition and the thickness of the photosensitive resin layer.
The following illustrates an aspect of the present invention.
(1) A dry film resist having a support film and a layer formed on the support film comprising a photosensitive resin composition containing:
(A) alkali soluble resin,
(B) A photopolymerizable compound having an ethylenically unsaturated bond,
(C) Photopolymerization initiator, and
(D) the dye is a mixture of a dye and a water,
the weight average molecular weight of the component (A) is 60,000 or less, calculated by using a standard curve of polystyrene, and measured by Gel Permeation Chromatography (GPC), and
the photosensitive resin composition is a photosensitive resin composition having a maximum point load of 70gf or more, the maximum point load is a maximum point load at the time of a puncture test in which a photosensitive resin layer containing the photosensitive resin composition is laminated on a support at a thickness of 25 μm to produce a photosensitive resin laminate, the photosensitive resin laminate is laminated on a copper-clad laminate substrate having a 1.6mm thick through hole having a diameter of 6mm on which a copper foil having a thickness of 35 μm is laminated, exposure and development are performed to form a cured film, the support is peeled from the cured film, and a cylinder having a diameter of 2.0mm is punctured from the surface from which the support is peeled at a speed of 100 mm/min at a portion of the photosensitive resin layer corresponding to the center of the through hole.
(2) The dry film resist according to item 1, wherein the number of double bonds of the photosensitive resin composition is 1.50mmol/g or more based on the solid content of the photosensitive resin composition.
(3) The dry film resist according to item 1, wherein the photosensitive resin composition contains a trifunctional or higher multifunctional monomer as the component (B).
(4) The dry film resist according to item 1, wherein the photosensitive resin composition contains, as the component (B), (B-ii) which is a trifunctional or higher multifunctional monomer: a compound having a backbone derived from dipentaerythritol but not containing oxyalkylene groups.
(5) The dry film resist according to item 4, wherein the photosensitive resin composition further contains, as the component (B), a bifunctional monomer of (B-iii): a (meth) acrylate compound having a skeleton derived from bisphenol.
(6) The dry film resist according to any one of items 1 to 5, wherein the photosensitive resin composition further contains a plasticizer.
(7) The dry film resist according to any one of items 1 to 6, wherein the dye includes a leuco dye.
(8) The dry film resist according to any one of items 1 to 7, wherein the maximum point load is less than 250 gf.
(9) A dry film resist having a support film and a layer formed on the support film comprising a photosensitive resin composition containing:
(A) alkali soluble resin,
(B) Photopolymerizable compound having ethylenically unsaturated bond, and
(C) a photopolymerization initiator,
the photosensitive resin composition contains, as the component (B):
(B-ii) as a polyfunctional monomer having three or more functions: a compound having a skeleton derived from dipentaerythritol and containing no oxyalkylene group; and
(B-iii) as a bifunctional monomer: a (meth) acrylate compound having a skeleton derived from bisphenol.
(10) The dry film resist according to item 9, wherein the ratio of (B-ii)/(B-iii) is 10 to 80% by mass.
(11) The dry film resist according to item 9 or 10, wherein the ratio of the component (B-ii) to the component (B-iii) is 50% by mass or more.
(12) The dry film resist according to any one of items 9 to 11, further comprising, as the component (B), (B-i): (meth) acrylate compound having a skeleton derived from dipentaerythritol and containing an oxyalkylene group.
(13) The dry film resist according to any one of items 9 to 12, wherein the weight average molecular weight of the component (A) is 60,000 or less as calculated using a standard curve of polystyrene, as measured by Gel Permeation Chromatography (GPC).
(14) The dry film resist according to any one of items 9 to 13, wherein the photosensitive resin composition is a photosensitive resin composition having a maximum point load of 70gf or more, the maximum point load being a maximum point load at the time of a puncture test in which a photosensitive resin layer containing the photosensitive resin composition is laminated on a support at a thickness of 25 μm to prepare a photosensitive resin laminate, the photosensitive resin laminate is laminated on a copper-clad laminate substrate having a 1.6mm thick through hole having a diameter of 6mm on which a copper foil having a thickness of 35 μm is laminated, exposure and development are performed to form a cured film, the support is peeled from the cured film, and a portion of the photosensitive resin layer corresponding to the center of the through hole is punctured into a cylinder having a diameter of 2.0mm at a speed of 100 mm/min from a surface from which the support is peeled.
(15) The dry film resist according to any one of items 9 to 14, wherein the number of double bonds of the photosensitive resin composition is 1.50mmol/g or more based on the solid content of the photosensitive resin composition.
(16) The dry film resist according to any one of items 9 to 15, wherein the photosensitive resin composition further contains a plasticizer.
(17) The dry film resist according to any one of items 9 to 16, wherein the dye includes a leuco dye.
(18) The dry film resist according to any one of items 9 to 17, wherein the maximum point load is less than 250 gf.
(19) A method for forming a resist pattern, comprising the steps of:
laminating the dry film resist according to any one of items 1 to 18 on a substrate;
exposing the laminated dry film resist; and
and developing the exposed dry film resist.
(20) A method for forming a wiring pattern, comprising the steps of:
laminating the dry film resist according to any one of items 1 to 18 on a substrate;
exposing the laminated dry film resist;
developing the exposed dry film resist to form a resist pattern; and
and performing etching or plating treatment of the substrate on which the resist pattern is formed.
The following examples illustrate other aspects of the present invention.
(21) A photosensitive resin laminate comprising a support and a photosensitive resin composition layer formed on the support by using a photosensitive resin composition comprising (A) an alkali-soluble resin having no ethylenically unsaturated group in the main chain, (B) a photopolymerizable compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator,
when the acid value of the nonvolatile component of the photosensitive resin composition is expressed as A [ mgKOH/g ] and the thickness of the photosensitive resin composition layer is expressed as T [ mu ] m, the ratio (A/T) of the acid value A to the thickness T is 5 to 90.
(22) The photosensitive resin laminate of item 21, wherein the photosensitive resin composition further contains a compound having polyoxytetramethylene group as a structural unit as the component (D).
(23) The photosensitive resin laminate of item 21 or 22, wherein the photosensitive resin composition further contains a compound having a benzotriazole skeleton as the component (E).
(24) A photosensitive resin laminate according to any one of items 21 to 23, wherein the photosensitive resin composition contains a photopolymerizable compound having an ethylenically unsaturated bond of four or more functions as the component (B).
(25) The photosensitive resin laminate of item 22, wherein the ratio of the component (A) to the total of the component (B) and the component (D) [ (A) component/((B) component + (D) component) ] exceeds 0 and is 1.4 or less.
(26) The photosensitive resin laminate according to any one of items 21 to 25, wherein the weight average molecular weight of the component (A) is 20,000 or more.
(27) The photosensitive resin laminate according to any one of items 21 to 26, wherein an acid value (acid equivalent) of a nonvolatile portion of the photosensitive resin composition is more than 0 and 79.0 or less.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, since the defect of the pattern formed using the photosensitive resin composition is suppressed, the yield of the object or the pattern formed by the photolithography can be improved, and/or a photosensitive resin laminate excellent in at least one of the laminatability, minimum development time, resolution, undercut (SE), Cu defect, and development residue can be provided.
Detailed Description
The present embodiment (hereinafter, simply referred to as "embodiment") will be described in detail below. The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the present invention.
In the present specification, "(meth) acrylic acid" means acrylic acid or methacrylic acid, "(meth) acryloyl group" means acryloyl group or methacryloyl group, and "(meth) acrylate" means acrylate or methacrylate.
[ one embodiment of the present invention ]
< photosensitive resin composition >
One embodiment of the present invention provides a photosensitive resin composition. The photosensitive resin composition contains the following components:
(A) alkali soluble resin,
(B) Photopolymerizable compound having ethylenically unsaturated bond, and
(C) a photopolymerization initiator.
The photosensitive resin composition may contain, as desired, (D) a dye in addition to the components (a) to (C), and may further contain a plasticizer, an antioxidant, a stabilizer, and the like.
< first embodiment >
The photosensitive resin composition according to the first embodiment is characterized by comprising (A) to (C) components and (D) a dye, and by having a maximum point load of 70gf or more as measured in the following puncture test.
(puncture test)
A copper-clad laminate substrate having a support, a photosensitive resin composition, and a copper foil laminated thereon and having a thickness of 35 μm, a thickness of 1.6mm, and a through-hole having a diameter (phi) of 6mm was prepared. A photosensitive resin layer containing a photosensitive resin composition was laminated on a support at a thickness of 25 μm to prepare a photosensitive resin laminate, the photosensitive resin laminate was laminated on a copper-clad laminate substrate, exposure and development were performed to form a cured film, and then the support was peeled from the cured film, and a portion of the photosensitive resin layer corresponding to the center of the through-hole was pierced through a cylinder having a diameter (phi) of 2.0mm at a speed of 100 mm/min from the surface from which the support was peeled.
In the first embodiment, when the maximum point load of the cured film measured in the above-described puncture test is 70gf or more, the resolution, undercut amount, and peeling property of the resist pattern formed by the photolithography using the photosensitive resin composition are good, and the pattern defect is suppressed, so that the yield of the object or pattern formed by the photolithography tends to be improved. A more specific method for measuring the maximum point load by the puncture test will be described in detail in the following examples.
The inventors of the present invention do not wish to be bound by theory, but believe that there is a correlation between the puncture strength of the cured film of the photosensitive resin composition and the defect of the metal substrate in the puncture test. In the first embodiment, as an index for suppressing the defect of the object or the wiring pattern formed by the photolithography using the photosensitive resin composition to improve the yield, the maximum point load of 70gf or more in the puncture test was found. From the viewpoint of further improving the yield, the maximum point load in the puncture test is preferably 74gf or more, 78gf or more, and more preferably 85gf or more. It is clear from the general knowledge in the art that the higher the upper limit value of the maximum point load in the puncture test, the higher the upper limit value, and for example, the upper limit value may be less than 250gf or not more than 245 gf.
The maximum point load in the puncture test can be adjusted to the numerical value range described above by optimizing the composition of the photosensitive resin composition, or by using a plurality of components or by blending two or more components or three or more components as the component (B) in the photosensitive resin composition, or by optimizing the type and blending ratio, for example.
In the photosensitive resin composition according to the first embodiment, it is preferable that the component (B) contains a polyfunctional monomer and/or a difunctional monomer having three or more functions from the viewpoints of improving the resolution, the amount of undercut, and the peelability of the resist pattern and suppressing pattern defects. From the same viewpoint, (B-ii) a compound having a skeleton derived from dipentaerythritol but not containing an oxyalkylene group is preferable as the polyfunctional monomer having three or more functions, and (B-iii) a (meth) acrylate compound having a skeleton derived from bisphenol is preferable as the difunctional monomer.
< second embodiment >
The photosensitive resin composition according to the second embodiment is characterized by containing, as the component (B):
(B-i) a (meth) acrylate compound having a skeleton derived from dipentaerythritol and containing an oxyalkylene group; and
(B-ii) a compound having a skeleton derived from dipentaerythritol and containing no oxyalkylene group.
In the photosensitive resin composition according to the second embodiment, when both the component (B-i) and the component (B-ii) are contained as the component (B), the resolution, the undercut amount, the puncture strength, and the peeling property of a resist pattern formed by a photolithography method using the photosensitive resin composition are good, and the pattern defect is suppressed, so that the yield of an object or a pattern formed by the photolithography method tends to be improved.
< third embodiment >
The photosensitive resin composition according to the third embodiment is characterized in that the component (B) contains:
(B-ii) a compound having a skeleton derived from dipentaerythritol and containing no oxyalkylene group as a polyfunctional monomer having three or more functions, and
(B-iii) a (meth) acrylate compound having a skeleton derived from bisphenol as a bifunctional monomer.
In the photosensitive resin composition according to the third embodiment, when both the component (B-ii) which is a multifunctional monomer having three or more functions and the component (B-iii) which is a difunctional monomer are contained as the component (B), the resolution, the undercut amount, the puncture strength, and the peeling property of the resist pattern formed by the photolithography using the photosensitive resin composition are good, and the pattern defect is suppressed, so that the yield of the object or the pattern formed by the photolithography tends to be improved.
The ratio of the component (B-ii)/component (B-iii) in the photosensitive resin composition according to the third embodiment is preferably 10 to 80% by mass, and/or the ratio of the components (B-ii) and (B-iii) in the component (B) is preferably 50% by mass or more, from the viewpoint of improving the resolution, undercut amount, puncture strength, and peeling properties of the resist pattern and suppressing pattern defects. From the same viewpoint, it is preferable that the component (B) according to the third embodiment contains the component (B-ii) and the component (B-iii) and further contains the component (B-i) described above.
The features described above in relation to the first, second and third embodiments may be combined or interchanged. The photosensitive resin composition according to the first, second, and third embodiments can be used for the implementation of photolithography, the production of a photosensitive resin laminate, the formation of a wiring pattern of a touch panel, and the like, and is preferably used for etching a substrate such as a copper-clad laminate, a copper sputtered film, and the like. Hereinafter, the respective components contained in the photosensitive resin composition according to the first, second and third embodiments will be described in order.
< A) alkali-soluble resin >
(A) The alkali-soluble resin is a polymer that is soluble in an alkaline solution. In addition, the (a) alkali-soluble resin preferably has a carboxyl group, more preferably has an acid equivalent of 100 to 600, and further preferably is a copolymer containing a carboxyl group-containing monomer as a copolymerization component. Further, (a) the alkali-soluble resin may be thermoplastic.
The acid equivalent of the (a) alkali-soluble resin is preferably 100 or more from the viewpoint of the development resistance of the photosensitive resin layer and the resolution and adhesion of the resist pattern, and is preferably 600 or less from the viewpoint of the development resistance and peeling property of the photosensitive resin layer. The acid equivalent of the alkali-soluble resin (A) is more preferably 200 to 500, and still more preferably 250 to 450. In one embodiment of the present invention, the acid equivalent means the mass (g) of the polymer having 1 equivalent of carboxyl group in the molecule, and can be measured by a potentiometric titration method using an automatic titration apparatus and a 0.1mol/L aqueous solution of sodium hydroxide, for example.
(A) Glass transition temperature (Tg) of alkali-soluble resin determined by the following numerical formula (I)total) Preferably 100 ℃ or lower.
Figure BDA0002832058100000111
{ in formula (II), WiTo the respective masses of the comonomers constituting the alkali-soluble resin,
Tgito obtain the glass transition temperature when the comonomers constituting the alkali-soluble resin are homopolymers,
Wtotalis the total mass of the alkali-soluble resin, and
n is the number of types of comonomers constituting the alkali-soluble resin. }
When a mixture of a plurality of polymers is used as the alkali-soluble resin (a), the glass transition temperature is a value determined as an average value of all the polymers.
The glass transition temperature Tg was determinediAs the glass transition temperature of a homopolymer formed from a comonomer forming the corresponding alkali-soluble resin, "Polymer handbook, Third edition, John wire, written by Brandrup, J.Immergut, E.H. was used&sons,1989, p.209Chapter VI Glass transition temperatures of polymers.
Tg of representative comonomersiAs shown below (all are literature values))。
Methacrylic acid: tg 501K
Benzyl methacrylate: tg 327K
Methyl methacrylate: tg 378K
Styrene: tg 373K
2-ethylhexyl acrylate: tg 223K
The glass transition temperature (Tg) as described abovetotal) The alkali-soluble resin of (3) is preferably a copolymer of an acid monomer and other monomers.
The glass transition temperature (Tg) of the alkali-soluble resin (A) determined by the above-mentioned numerical formula (I)total) The lower limit of (3) is not particularly limited. Glass transition temperature (Tg)total) The temperature may be 10 ℃ or higher, 30 ℃ or higher, 50 ℃ or higher, or 70 ℃ or higher.
On the other hand, the weight average molecular weight (Mw) of the component (a) of the alkali-soluble resin (a) is preferably 60,000 or less, which is calculated by measuring at least the component (a) by Gel Permeation Chromatography (GPC) using a standard curve of polystyrene. From the viewpoint of solubility in a developer, Mw of the (a) alkali-soluble resin is preferably 60,000 or less, while Mw of the (a) alkali-soluble resin is preferably 5,000 or more from the viewpoints of maintenance of uniform thickness, adhesiveness, hot-melt curling (edge curling) property, chipping property, and the like of a photosensitive resin laminate such as a dry film resist. From such a viewpoint, Mw of the alkali-soluble resin (a) is more preferably 10,000 or more and 55,000 or less. Further, the ratio of the Mw to the number average molecular weight (Mn) of the alkali-soluble resin (A), i.e., the dispersity (Mw/Mn) of the alkali-soluble resin (A) is preferably 1.0 to 6.0.
(A) The alkali-soluble resin is preferably obtained by polymerizing at least 1 first monomer described later. Further, (a) the alkali-soluble resin is more preferably obtained by copolymerizing at least 1 kind of first monomer with at least 1 kind of second monomer described later.
The first monomer is a monomer having a carboxyl group in the molecule. Examples of the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid half ester. Among these, (meth) acrylic acid is particularly preferable.
The second monomer is a monomer that is non-acidic and has at least 1 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, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and benzyl (meth) acrylate; vinyl alcohol esters such as vinyl acetate; and (meth) acrylonitrile, styrene, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, t-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene trimer, etc.), and the like. Among these, methyl (meth) acrylate, n-butyl (meth) acrylate, styrene, and benzyl (meth) acrylate are preferable.
Further, from the viewpoint of improving the resolution of the resist pattern, the (a) alkali-soluble resin preferably has an aromatic group in a side chain of its structure.
The (a) alkali-soluble resin having an aromatic group in a side chain may be prepared by using a compound having an aromatic group as the above-mentioned first monomer and/or second monomer. Examples of the aromatic group-containing monomer include benzyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, styrene, cinnamic acid, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene trimer, etc.). Of these, benzyl (meth) acrylate and styrene are preferable, and benzyl (meth) acrylate is more preferable.
(A) The alkali-soluble resin may be prepared by applying a known polymerization method, preferably addition polymerization, more preferably radical polymerization, to the above-mentioned first monomer and/or second monomer.
The content of the alkali-soluble resin (a) in the photosensitive resin composition (hereinafter, the same for each content unless otherwise specified) is preferably in the range of 10 to 90% by mass, more preferably in the range of 20 to 80% by mass, and still more preferably in the range of 30 to 60% by mass. The content of the (a) alkali-soluble resin is preferably 10 mass% or more from the viewpoint of maintaining the alkali developability of the photosensitive resin layer, and is preferably 90 mass% or less from the viewpoint of sufficiently exerting the performance as a resist material of a resist pattern formed by exposure.
[ B ] photopolymerizable Compound having ethylenically unsaturated group >
(B) The photopolymerizable compound having an ethylenically unsaturated group is a compound having polymerizability by having an ethylenically unsaturated group in its structure. In the first, second, and third embodiments, the photosensitive resin composition preferably contains a (meth) acrylate compound as the component (B), more preferably contains a poly (meth) acrylate compound, and further preferably contains a (meth) acrylate compound having a skeleton derived from dipentaerythritol represented by the following formula (II).
Figure BDA0002832058100000131
{ formula (II) wherein R10Represents a hydrogen atom, a (meth) acryloyl group or an alkylene oxide-modified (meth) acryloyl group, and contains at least 4 (meth) acryloyl groups in 1 molecule. }
In the general formula (II), the number of (meth) acryloyl groups in one molecule is 4 or more, preferably 5 or 6, from the viewpoint of obtaining sufficient cured film strength, resist shape, and resolution. As R10The alkylene oxide-modified (meth) acryloyl group of the group is modified with, for example, at least 1 selected from the group consisting of ethylene oxide, propylene oxide and butylene oxide, preferably with ethylene oxide and/or propylene oxide, and specifically may be- (C)2H4O)m-CO-CR＝CH2{ wherein R represents a hydrogen atom or a methyl group, and m is an integer of 1 to 30 }, - (C)3H6O)n-CO-CR＝CH2{ wherein R represents a hydrogen atom or a methyl group, and n is an integer of 1 to 30 }, - (C)2H4O)m-(C3H6O)n-CO-CR＝CH2{ wherein R represents a hydrogen atom or a methyl group, m is an integer of 1 to 30, n is an integer of 1 to 30, and (C)2H4O)mAnd (C)3H6O)nMay be arranged alternately, randomly or in blocks, etc.
The photosensitive resin composition according to the first embodiment preferably contains, as the component (B), from the viewpoint of adjusting the maximum point load in the puncture test to 70gf or more:
(B-i) a (meth) acrylate compound having a skeleton derived from dipentaerythritol and containing an oxyalkylene group; and
(B-ii) a compound having a skeleton derived from dipentaerythritol and containing no oxyalkylene group.
The photosensitive resin composition according to the second embodiment contains, as the component (B), from the viewpoints of resolution, undercut amount, puncture strength, and peeling property of a resist cured film, suppression of pattern defects, and improvement of yield:
(B-i) a (meth) acrylate compound having a skeleton derived from dipentaerythritol and containing an oxyalkylene group; and
(B-ii) a compound having a skeleton derived from dipentaerythritol and containing no oxyalkylene group.
When the photosensitive resin composition contains both the component (B-i) and the component (B-ii), the mass ratio of the two components (B-i) to (B-ii) is preferably 8:9 to 9:7 from the viewpoints of suppressing pattern defects, suppressing metal substrate defects, and improving yield.
In the first and second embodiments, the photosensitive resin composition preferably contains (B-iii) a (meth) acrylate compound having a skeleton derived from a bisphenol and containing an oxyalkylene group (excluding the (B-i) component therein) in addition to the (B-i) component and the (B-ii) component, from the viewpoint of the amount of undercut of the resist pattern and the puncture strength.
In the photosensitive resin composition according to the first embodiment, it is preferable that the component (B) contains one or both of the component (B-ii) which is a multifunctional monomer having three or more functions and the component (B-iii) which is a difunctional monomer, from the viewpoints of resolution of a resist pattern, an amount of undercut, peeling properties, and suppression of pattern defects.
In the photosensitive resin composition according to the third embodiment, it is preferable that the composition further contains the component (B-i) in addition to the components (B-ii) and (B-iii) from the viewpoints of resolution of a resist pattern, undercut amount, puncture strength, peeling property, and suppression of pattern defects.
In the photosensitive resin composition, the ratio of the mass of the component (B-iii) to the total mass of the components (B-i) and (B-ii) is preferably 0.9 to 1.8, more preferably 0.95 to 1.76, from the viewpoint of the maximum point load in the puncture test or the puncture strength of the resist pattern.
The (B-i) oxyalkylene group-containing (meth) acrylate compound having a dipentaerythritol-derived skeleton may be, for example, a compound having at least 4 alkylene oxide-modified (meth) acryloyl groups in 1 molecule in the general formula (II), and is preferably a compound having 5 and/or 6 alkylene oxide-modified (meth) acryloyl groups in 1 molecule in the general formula (II) from the viewpoint of the maximum point load of the puncture test or the puncture strength of the resist cured film.
In the general formula (II), R is the component (B-i) in view of the maximum point load in the puncture test or the puncture strength of the resist cured film10The alkylene oxide-modified (meth) acryloyl group of the group is preferably modified with at least 1 selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, pentylene oxide and hexylene oxide, more preferably modified with ethylene oxide and/or propylene oxide, and further preferably- (C)2H4O)m-CO-CR＝CH2{ wherein R represents a hydrogen atom or a methyl group, and m is an integer of 1 to 30 }, - (C)3H6O)n-CO-CR＝CH2{ wherein R represents a hydrogen atom or a methyl group, and n is an integer of 1 to 30 }, or- (C)2H4O)m-(C3H6O)n-CO-CR＝CH2{ wherein R represents a hydrogen atom or a methyl group, m is an integer of 1 to 30, n is an integer of 1 to 30, and (C)2H4O)mAnd (C)3H6O)nThe arrangement of (A) may be an alternating, random or block }, and is more preferably- (C)2H4O)m-CO-CR＝CH2{ wherein R represents a hydrogen atom or a methyl group, and m is an integer of 1 to 30 }. From the same viewpoint, in the general formula (II), the number of ethylene oxide repeats m and the number of propylene oxide repeats n are each preferably in the range of 3 to 27, more preferably 6 to 21, and still more preferably 9 to 16.
Specific examples of the component (B-i) include:
dipentaerythritol tetra (meth) acrylate of polyethylene glycol added with an average of 3 to 27 moles of ethylene oxide;
dipentaerythritol penta (meth) acrylate of polyethylene glycol added with an average of 3 to 27 moles of ethylene oxide;
dipentaerythritol hexa (meth) acrylate of polyethylene glycol added with an average of 3 to 27 moles of ethylene oxide;
dipentaerythritol tetra (meth) acrylate of polyethylene glycol added with an average of 3 to 27 moles of propylene oxide;
dipentaerythritol penta (meth) acrylate of polyethylene glycol added with an average of 3 to 27 moles of propylene oxide;
dipentaerythritol hexa (meth) acrylate of polyethylene glycol to which propylene oxide is added in an amount of 3 to 27 moles on average;
dipentaerythritol tetra-, penta-or hexa (meth) acrylate of polyethylene glycol to which ethylene oxide and propylene oxide are added alternately, randomly or in blocks, the average amount of ethylene oxide being 3 to 27 mol and the average amount of propylene oxide being 3 to 27 mol;
combinations of the above-listed compounds, and the like.
Among them, dipentaerythritol hexamethacrylate of polyethylene glycol to which ethylene oxide is added in an average amount of 12 to 15 moles is preferable from the viewpoints of resolution, undercut amount, puncture strength and peeling property of a resist cured film, suppression of pattern defects, and improvement of yield.
(B-ii) the compound having a backbone derived from dipentaerythritol but not containing oxyalkylene groups may be dipentaerythritol mono-or poly (meth) acrylate which is not modified with alkylene oxide, and is preferably dipentaerythritol poly (meth) acrylate which is not modified with alkylene oxide from the viewpoint of obtaining sufficient cured film strength, resist shape and resolution.
Component (B-II) may be, for example, R in the formula (II)10The compound having a hydrogen atom and/or a (meth) acryloyl group preferably has 4 or more, more preferably 5 or 6, R as R from the viewpoint of the maximum point load in the puncture test or the puncture strength of the resist cured film10A (meth) acryloyl group of (a).
When a penta (meth) acrylate having 5 (meth) acryloyl groups and a hexa (meth) acrylate having 6 (meth) acryloyl groups are used in combination as the component (B-ii), the mass ratio of the penta (meth) acrylate is preferably 5 to 50 mass%, more preferably 10 to 40 mass%, or 30 to 40 mass%, from the viewpoint of the maximum point load in the puncture test or the puncture strength of the resist cured film.
Specific examples of the component (B-ii) include:
dipentaerythritol mono (meth) acrylate,
Dipentaerythritol di (meth) acrylate,
Dipentaerythritol tri (meth) acrylate,
Dipentaerythritol tetra (meth) acrylate,
Dipentaerythritol penta (meth) acrylate,
Dipentaerythritol hexa (meth) acrylate,
And combinations of at least two of the dipentaerythritol mono-and poly (meth) acrylates listed above.
Among them, a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate is preferable from the viewpoint of resolution, undercut amount, puncture strength and peeling property of the resist cured film, suppression of pattern defects, and improvement of yield, and the pentaacrylate mass ratio in the mixture is preferably 10 mass% or 30 to 40 mass%.
The (B-iii) acrylate compound having a skeleton derived from bisphenol is not repeated with the (B-i) component, and therefore, it preferably does not contain a dipentaerythritol skeleton and has a skeleton derived from bisphenol and a (meth) acryloyl group, and more preferably has a skeleton derived from bisphenol and has an oxyalkylene group and a (meth) acryloyl group.
The component (B-III) may be, for example, a compound represented by the following general formula (III).
Figure BDA0002832058100000181
{ in formula (II), X1～X8Each independently is a hydrogen atom or a halogen atom, preferably X1～X8Are each a hydrogen atom, R6And R7Each independently represents a hydrogen atom or a methyl group, R8And R9Each independently represents an alkylene group having 2 to 6 carbon atoms, n5And n6Each independently is 0 or a positive integer, and n5+n6Is 0 to 20. }
In the general formula (III), as R8And R9The alkylene group having 2 to 6 carbon atoms of (A) is preferably an ethylene group, a propylene group or a butylene group, and (R)8-O) -and- (R)9-O) -may be ethylene oxide, propylene oxide, butylene oxide, or a combination thereof, respectively.
Among the general formula (III), preferred is- (R)8-O) -and- (R)9-O) -are each- (C)2H4O)-、-(C3H6O) -or- (C2H4O)α-(C3H6O)β- { in the formula,. alpha. + β ═ n5Or n6，(C2H4O)αAnd (C)3H6O)βMay be arranged alternately, randomly or in blocks, and (C)2H4O)αAnd (C)3H6O)βAny of which may be quaternary carbon side }. The component (B-iii) containing these divalent groups is preferable from the viewpoint of resolution, undercut amount, puncture strength and peeling property of the resist cured film, suppression of pattern defects, and improvement of yield. From the same viewpoint, in the general formula (III), n5And n6Each independently is preferably a positive integer, more preferably an integer selected from 1 to 14, and n5+n6Preferably 2 to 20.
Specific examples of the component (B-iii) include a compound obtained by modifying bisphenol A with alkylene oxide and introducing (meth) acryloyl groups into both ends, a compound having (meth) acryloyl groups at both ends of bisphenol A, and the like. Further, the alkylene oxide modification includes ethylene oxide modification, propylene oxide modification, butylene oxide modification, pentylene oxide modification, hexylene oxide modification, and the like.
Specific examples of the ethylene oxide-modified bisphenol a having a (meth) acryloyl group at both ends include:
di (meth) acrylate of polyethylene glycol having an average of 1 mole of ethylene oxide added to each end of bisphenol a;
di (meth) acrylate of polyethylene glycol having an average of 2 moles of ethylene oxide added to each end of bisphenol a;
di (meth) acrylate of polyethylene glycol having an average of 3 moles of ethylene oxide added to each end of bisphenol a;
and di (meth) acrylates of polyethylene glycol obtained by adding an average of 5 moles of ethylene oxide to each end of bisphenol a.
These may be used alone, or 2 or more of them may be used in combination. Among the above-described components (B-iii), from the viewpoints of resolution, undercut amount, puncture strength, and suppression of chipping of the metal base material, a dimethacrylate of polyethylene glycol having an average of 5 moles of ethylene oxide added to each end of bisphenol a, a dimethacrylate of polyethylene glycol having an average of 1 mole of ethylene oxide added to each end of bisphenol a, and a bisphenol a dimethacrylate are preferable.
The photosensitive resin composition may contain, as an additional component (B), a photopolymerizable compound having an ethylenically unsaturated group in addition to the components (B-i) to (B-iii).
Specific examples of the component (B) to be added include: (meth) acrylate compounds other than the components (B-i) to (B-iii) include, for example, compounds obtained by converting alcohols obtained by adding polyoxyalkylene or modifying epsilon-caprolactone to glycerin, trimethylolpropane, pentaerythritol, diglycerin, ditrimethylolpropane, isocyanurate ring, or the like, into (meth) acrylate; or a compound obtained by directly reacting them with (meth) acrylic acid without modifying them with an oxyalkylene group or epsilon-caprolactone. More specifically, a triacrylate having an average of 3 moles of ethylene oxide added to each trimethylolpropane, a trimethacrylate having an average of 3 moles of ethylene oxide added to each trimethylolpropane, an epsilon-caprolactone-modified tris (acryloyloxyethyl) isocyanurate, and the like can be used.
The content of the photopolymerizable compound having an ethylenically unsaturated group (B) in the photosensitive resin composition is preferably in the range of 5 to 70 mass%, more preferably 20 to 60 mass%, and still more preferably 30 to 50 mass%. The content of the compound having an ethylenically unsaturated group (B) is preferably 5% by mass or more from the viewpoint of suppressing curing failure of the photosensitive resin layer and delay in development time, and is preferably 70% by mass or less from the viewpoint of suppressing peeling delay of the cured resist.
The total content of the component (B-i) and the component (B-ii) in the photosensitive resin composition is preferably in the range of 5 to 25% by mass, more preferably 10 to 20% by mass. When the total content of the component (B-i) and the component (B-ii) is within the above numerical range, the following tendency is exhibited: the adjustment of the maximum point load in the puncture test is facilitated, or the chipping of the pattern or the metal base material is suppressed, or the yield is improved.
When the photosensitive resin composition contains the component (B-ii) and the component (B-iii), the ratio of the component (B-ii)/the component (B-iii) is preferably 10 to 80% by mass, more preferably 12 to 78% by mass. The ratio of the component (B-ii) and the component (B-iii) among the component (B) contained in the photosensitive resin composition is preferably 50% by mass or more, more preferably 55% by mass or more, and the upper limit of the ratio is not limited, and may be, for example, 100% by mass or less than 100% by mass.
[ C ] photopolymerization initiator
(C) The photopolymerization initiator is a compound capable of generating radicals by actinic rays and polymerizing (B) a photopolymerizable compound having an ethylenically unsaturated group, or the like. In the photosensitive resin composition, as the (C) photopolymerization initiator, a photopolymerization initiator generally known in the art may be contained.
Examples of the photopolymerization initiator (C) include hexaarylbiimidazole compounds, N-aryl- α -amino acid compounds, quinone compounds, aromatic ketone compounds, acetophenone compounds, acylphosphine oxide compounds, benzoin ether compounds, dialkyl ketal compounds, thioxanthone compounds, dialkyl aminobenzoate compounds, oxime ester compounds, acridine compounds, dihydropyrazole derivatives, ester compounds of N-aryl amino acids, and halides.
Examples of the hexaarylbiimidazole compound include 2- (o-chlorophenyl) -4, 5-diphenylbiimidazole (otherwise known as 2,2 ' -bis (2-chlorophenyl) -4,4 ', 5,5 ' -tetraphenyl-1, 2 ' -biimidazole), 2 ', 5-tris (o-chlorophenyl) -4- (3, 4-dimethoxyphenyl) -4 ', 5 ' -diphenylbiimidazole, 2, 4-bis (o-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -diphenylbiimidazole, 2,4, 5-tris (o-chlorophenyl) -diphenylbiimidazole, 2- (o-chlorophenyl) -bis-4, 5- (3, 4-dimethoxyphenyl) biimidazole, and mixtures thereof, 2,2 ' -bis (2-fluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) biimidazole, 2 ' -bis (2, 3-difluoromethylphenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) biimidazole, 2 ' -bis (2, 4-difluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) biimidazole, 2 ' -bis (2, 5-difluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) biimidazole, 2 ' -bis (2, 6-difluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) biimidazole, 2,2 ' -bis (2,3, 4-trifluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) biimidazole, 2 ' -bis (2,3, 5-trifluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) biimidazole, 2 ' -bis (2,3, 6-trifluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) biimidazole, 2 ' -bis (2,4, 5-trifluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) biimidazole, 2 ' -bis (2,4, 6-trifluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) biimidazole, 2,2 ' -bis (2,3,4, 5-tetrafluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) biimidazole, 2 ' -bis (2,3,4, 6-tetrafluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) biimidazole, and 2,2 ' -bis (2,3,4,5, 6-pentafluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) biimidazole, and the like. Among them, 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer is preferable from the viewpoint of high sensitivity, resolution and adhesion.
Examples of the N-aryl- α -amino acid compound include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine. In particular, N-phenylglycine is preferable because it has a high sensitizing effect.
Examples of the quinone compound include 2-ethylanthraquinone, octaethylanthraquinone, 1, 2-benzoanthraquinone, 2, 3-benzoanthraquinone, 2-phenylanthraquinone, 2, 3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1, 4-naphthoquinone, 9, 10-phenanthrenequinone, 2-methyl-1, 4-naphthoquinone, 2, 3-dimethylanthraquinone, and 3-chloro-2-methylanthraquinone.
Examples of the aromatic ketone compound include benzophenone, michler's ketone [4, 4' -bis (dimethylamino) benzophenone ], 4 '-bis (diethylamino) benzophenone, 4-methoxy-4' -dimethylamino benzophenone, and the like.
Examples of the acetophenone compounds include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) one, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinoacetone-1, and the like. Examples of commercially available acetophenone compounds include Irgacure-907, Irgacure-369 and Irgacure-379 available from Ciba Specialty Chemicals, Inc. From the viewpoint of use as a sensitizer and adhesion, 4' -bis (diethylamino) benzophenone is preferable.
Examples of the acylphosphine oxide compound include 2,4, 6-trimethylbenzyldiphenylphosphine oxide, bis (2,4, 6-trimethylbenzoyl) phosphine oxide, bis (2, 6-dimethoxybenzoyl) -2,4, 4-trimethylpentylphosphine oxide and the like. Examples of commercially available products of the acylphosphine oxide compound include LUCIRIN TPO manufactured by BASF corporation and Irgacure-819 manufactured by Ciba Specialty Chemicals corporation.
Examples of the benzoin compound and the benzoin ether compound include benzoin, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, and ethyl benzoin.
Examples of the dialkyl ketal compound include benzil dimethyl ketal and benzil diethyl ketal.
Examples of the thioxanthone compound include 2, 4-diethylthioxanthone, 2, 4-diisopropylthioxanthone, and 2-chlorothioxanthone.
Examples of the dialkylaminobenzoate compounds include ethyl dimethylaminobenzoate, ethyl diethylaminobenzoate, ethyl-p-dimethylaminobenzoate, and 2-ethylhexyl-4- (dimethylamino) benzoate.
Examples of the oxime ester compound include 1-phenyl-1, 2-propanedione-2-O-benzoyl oxime, 1-phenyl-1, 2-propanedione-2- (O-ethoxycarbonyl) oxime, and the like. Examples of commercially available oxime ester compounds include CGI-325, Irgacure-OXE01 and Irgacure-OXE02 manufactured by Ciba Specialty Chemicals, Inc.
The acridine compound is preferably 1, 7-bis (9, 9' -acridinyl) heptane or 9-phenylacridine from the viewpoints of sensitivity, resolution, acquisition property, and the like.
As the dihydropyrazole derivative, 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -dihydropyrazole, 1-phenyl-3- (4-biphenyl) -5- (4-tert-butyl-phenyl) -dihydropyrazole, and 1-phenyl-3- (4-biphenyl) -5- (4-tert-octyl-phenyl) -dihydropyrazole are preferable from the viewpoints of adhesiveness and rectangularity of the resist pattern.
Examples of the ester compound of an N-arylamino acid include methyl ester of N-phenylglycine, ethyl ester of N-phenylglycine, N-propyl ester of N-phenylglycine, isopropyl ester of N-phenylglycine, 1-butyl ester of N-phenylglycine, 2-butyl ester of N-phenylglycine, t-butyl ester of N-phenylglycine, pentyl ester of N-phenylglycine, hexyl ester of N-phenylglycine, pentyl ester of N-phenylglycine, and octyl ester of N-phenylglycine.
Examples of the halide include amyl bromide, isoamyl bromide, isobutylene bromide, vinyl bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenylsulfone, carbon tetrabromide, tris (2, 3-dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1, 1-trichloro-2, 2-bis (p-chlorophenyl) ethane, a triazine chloride compound, and a diallylium iodide compound, and tribromomethylphenylsulfone is particularly preferable.
The content of the photopolymerization initiator (C) in the photosensitive resin composition is preferably 0.01 to 20% by mass, and more preferably 0.5 to 10% by mass. By adjusting the content of the photopolymerization initiator (C) within the above range, a photosensitive resin composition can be obtained which can obtain sufficient sensitivity, can sufficiently project light to the bottom of the resist, can obtain high resolution, and has an excellent balance with the amount of undercut of the conductor pattern.
As the photopolymerization initiator (C), a hexaarylbisimidazole compound is preferably used. In this case, the content of the hexaarylbisimidazole compound in the photosensitive resin composition is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass.
As the photopolymerization initiator (C), an aromatic ketone compound such as 4, 4' -bis (diethylamino) benzophenone and a hexaarylbisimidazole compound are preferably used in combination. In this case, the content of the aromatic ketone compound in the photosensitive resin composition is preferably 0.5% by mass or less, more preferably 0.01% by mass to 0.4% by mass, and the content of the hexaarylbisimidazole compound in the photosensitive resin composition is preferably 0.1% by mass to 10% by mass, more preferably 0.5% by mass to 5% by mass.
< D dye >
In order to impart suitable color developability and excellent sensitivity characteristics to the resist cured film, a dye is preferably contained as the (D) component in the photosensitive resin composition.
Examples of the dye include tris (4-dimethylaminophenyl) methane [ leuco crystal violet ], bis (4-dimethylaminophenyl) phenylmethane [ leuco malachite GREEN ], fuchsin, phthalocyanine GREEN, auramine base, parafuchsin, crystal violet, methyl orange, nile blue 2B, victoria blue, malachite GREEN (Aizen (registered trademark) MALACHITE GREEN, manufactured by pau chemical), alkali blue 20, and DIAMOND GREEN (Aizen (registered trademark) DIAMOND GREEN GH, manufactured by pau chemical). Among these, leuco dyes such as diamond green and leuco crystal violet are preferable from the viewpoint of improving coloring property, hue stability and exposure contrast. These can be used alone in 1 or a combination of 2 or more.
The content of the dye in the photosensitive resin composition is preferably in the range of 0.001 to 3% by mass, more preferably in the range of 0.01 to 2% by mass, and still more preferably in the range of 0.04 to 1% by mass. The content of the dye is preferably 0.001 mass% or more from the viewpoint of obtaining good colorability, and is preferably 3 mass% or less from the viewpoint of maintaining the sensitivity of the photosensitive resin layer. By setting the use ratio of the dye to this range, good color developability and sensitivity can be achieved.
< other ingredients >
The photosensitive resin composition preferably contains additives such as a plasticizer, an antioxidant, and a stabilizer, as desired.
Examples of the plasticizer include glycol esters such as polyethylene glycol, polypropylene glycol, polyoxypropylene polyoxyethylene ether, polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether, polyoxyethylene monoethyl ether, polyoxypropylene monoethyl ether, polyoxyethylene polyoxypropylene monoethyl ether, and polyoxyethylene polyoxypropylene monoethyl ether; sorbitan derivatives such as polyoxyethylene sorbitan laurate and polyoxyethylene sorbitan oleate; phthalic acid esters such as diethyl phthalate; o-toluenesulfonamide, p-toluenesulfonamide, tributyl citrate, triethyl acetylcitrate, tri-n-propyl acetylcitrate, tri-n-butyl acetylcitrate, propylene glycol to which propylene oxide is added on both sides of bisphenol a, ethylene glycol to which ethylene oxide is added on both sides of bisphenol a, polyoxyethylene glyceryl ether, polyoxypropylene glyceryl ether, and the like.
Among them, from the viewpoint of suppressing the delay of the peeling time, p-toluenesulfonamide, polypropylene glycol in which propylene oxide having an average of 3 units is added to each of both ends of bisphenol a, and polyoxypropylene glycerin ether are preferable, and from the viewpoint of the puncture strength of the resist pattern, the solubility of the release sheet, or the plating resistance, polyoxypropylene glycerin ether having a weight average molecular weight of 3000 is more preferable, and polyoxypropylene glycerin ether having a weight average molecular weight of 3000 is further preferable.
The content of the plasticizer in the photosensitive resin composition is preferably in the range of 0.1 to 3 mass%, more preferably 0.15 to 2 mass%. From the viewpoints of suppressing the delay of the development time, imparting flexibility to the cured film, and easily adjusting the maximum point load by the puncture test, the content is preferably 0.1 mass% or more. On the other hand, from the viewpoint of suppressing insufficient curing and edge melting, the content is preferably 3% by mass or less.
Examples of the antioxidant include triphenyl phosphite (e.g., TPP, trade name, manufactured by Asahi Denka Kogyo Co., Ltd.), tris (2, 4-di-t-butylphenyl) phosphite (e.g., 2112, manufactured by Asahi Denka Co., Ltd.), tris (monononylphenyl) phosphite (e.g., 1178, manufactured by Asahi Denka Kogyo Co., Ltd.), bis (monononylphenyl) dinonylphenyl phosphite (e.g., 329K, manufactured by Asahi Denka Ltd.), and the like. These can be used alone in 1 or a combination of 2 or more.
The content of the antioxidant in the photosensitive resin composition is preferably in the range of 0.01 to 0.8% by mass, and more preferably in the range of 0.01 to 0.3% by mass. The content of the antioxidant is preferably 0.01% by mass or more from the viewpoint of satisfactorily expressing the hue stability of the resist pattern and improving the sensitivity of the photosensitive resin layer, and the content of the antioxidant is preferably 0.8% by mass or less from the viewpoint of satisfactorily expressing the hue stability and improving the adhesion while suppressing the color development of the resist pattern.
From the viewpoint of improving the thermal stability and/or storage stability of the photosensitive resin composition, a stabilizer is preferably used. Examples of the stabilizer include at least 1 compound selected from the group consisting of a radical polymerization inhibitor, a benzotriazole compound, a carboxybenzotriazole compound, and an alkylene oxide compound having a glycidyl group. These can be used alone in 1 or a combination of 2 or more.
Examples of the radical polymerization inhibitor include p-methoxyphenol, hydroquinone, biphenyltriol, naphthylamine, t-butylcatechol, cuprous chloride, 2, 6-di-t-butyl-p-cresol, 2 '-methylenebis (4-methyl-6-t-butylphenol), 2' -methylenebis (4-ethyl-6-t-butylphenol), triethylene glycol bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate ], nitrosophenylhydroxylamine aluminum salt (for example, an aluminum salt to which 3 moles of nitrosophenylhydroxylamine is added), and diphenylnitrosamine. Among these, triethylene glycol bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate ] or an aluminum salt to which 3 moles of nitrosophenylhydroxylamine is added is preferable. Further, they may be used alone in 1 kind or in combination of 2 or more kinds.
Examples of the benzotriazole include 1,2, 3-benzotriazole, 1-chloro-1, 2, 3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1, 2, 3-tolyltriazole, bis (N-2-hydroxyethyl) aminomethylene-1, 2, 3-benzotriazole, 1:1 mixture of 1- (2-di-N-butylaminomethyl) -5-carboxybenzotriazole and 1- (2-di-N-butylaminomethyl) -6-carboxybenzotriazole, and the like. Of these, a 1:1 mixture of 1- (2-di-n-butylaminomethyl) -5-carboxybenzotriazole and 1- (2-di-n-butylaminomethyl) -6-carboxybenzotriazole is preferred. Further, they may be used alone in 1 kind or in combination of 2 or more kinds.
Examples of the carboxybenzotriazole include 4-carboxy-1, 2, 3-benzotriazole, 5-carboxy-1, 2, 3-benzotriazole, N- (N, N-di-2-ethylhexyl) aminomethylene carboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylene carboxybenzotriazole and N- (N, N-di-2-ethylhexyl) aminoethylene carboxybenzotriazole. These can be used alone in 1 or a combination of 2 or more.
Examples of the alkylene oxide compound having a glycidyl group include neopentyl glycol diglycidyl ether (e.g., EPOLIGHT 1500NP manufactured by honor chemical corporation), nonaethylene glycol diglycidyl ether (e.g., EPOLIGHT 400E manufactured by honor chemical corporation), diglycidyl ether of a 2-mol adduct of bisphenol a-propylene oxide (e.g., EPOLIGHT 3002 manufactured by honor chemical corporation), and 1, 6-hexanediol diglycidyl ether (e.g., EPOLIGHT 1600 manufactured by honor chemical corporation). These can be used alone in 1 or a combination of 2 or more.
The total content of the radical polymerization inhibitor, the benzotriazole, the carboxybenzotriazole, and the glycidyl group-containing alkylene oxide compound in the photosensitive resin composition is preferably in the range of 0.001 to 3 mass%, and more preferably in the range of 0.05 to 1 mass%. The total content is preferably 0.001 mass% or more from the viewpoint of imparting good storage stability to the photosensitive resin composition, and is preferably 3 mass% or less from the viewpoint of maintaining the sensitivity of the photosensitive resin layer.
The number of double bonds in the photosensitive resin composition according to the first, second and third embodiments is preferably 1.50mmol/g or more based on the solid content of the photosensitive resin composition. By setting the number of double bonds to such a range, the puncture strength or resolution of the coating film becomes good. On the other hand, if the number of double bonds in the photosensitive resin composition is too high, the storage stability of the composition may be impaired. From the viewpoint of avoiding this, the number of double bonds of the photosensitive resin composition is more preferably 4.00mmol/g or less.
The number of double bonds (number of ethylenically unsaturated bonds) of the photosensitive resin composition can be adjusted depending on the blending ratio of the component (B), the molecular weight of the component (B), the number of functional groups of the component (B), and the like in the photosensitive resin composition. That is, the embodiment in which the number of double bonds of the photosensitive resin composition is in the above range is a preferable embodiment in which the compounding ratio of the component (B), the molecular weight of the component (B), the number of functional groups of the component (B), and the like are appropriately adjusted in the embodiment in which the maximum point load in the puncture test is in the above range. This preferable embodiment easily exerts the effect of the present invention.
[ other aspects of the invention ]
Another aspect of the present invention provides a photosensitive resin laminate having a support and a photosensitive resin composition layer formed on the support using a photosensitive resin composition containing (a) an alkali-soluble resin having no ethylenically unsaturated group in a main chain, (B) a photopolymerizable compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator.
In addition, the photosensitive resin laminate according to another aspect of the present invention is characterized in that when the acid value of the nonvolatile component of the photosensitive resin composition is represented by a [ mgKOH/g ] and the thickness of the photosensitive resin composition layer is represented by T [ μm ], the ratio (a/T) of the acid value a to the thickness T is 5 or more and 90 or less.
If the ratio (A/T) of the acid value A to the thickness T is less than 5 (for example, 5.0), the minimum development time and resolution are insufficient. On the other hand, if the ratio (a/T) is greater than 90, the undercut (SE) and Cu defects are insufficient. By setting the ratio (a/T) to 5 or more and 90 or less, the lamination property, minimum development time, resolution, undercut (SE), Cu defects, and development residues of the photosensitive resin laminate become excellent. The ratio (a/T) is preferably 12 (e.g., 12.0) or more and less than 70, and more preferably 12 (e.g., 12.0) or more and less than 50.
In another embodiment of the present invention, the acid value (acid equivalent) of the nonvolatile portion of the photosensitive resin composition is a mass (g) of the polymer having 1 equivalent of carboxyl group in the molecule, and is a value calculated from a value measured by NMR. Specifically, the measurement value is measured by the measurement method in the example described later.
Hereinafter, each component constituting the photosensitive resin composition layer will be described.
< A) alkali-soluble resin having no ethylenically unsaturated group in the main chain >
(A) The alkali-soluble resin having no ethylenically unsaturated group in the main chain is a polymer that can be dissolved in an alkaline solution. In addition, (a) the alkali-soluble resin having no ethylenically unsaturated group in the main chain preferably has a carboxyl group, more preferably an acid equivalent of 100 to 600, and further preferably a copolymer comprising a carboxyl group-containing monomer as a copolymerization component. Further, (a) the alkali-soluble resin having no ethylenically unsaturated group in the main chain may be thermoplastic.
The acid equivalent of the nonvolatile component of the photosensitive resin composition containing (a) the alkali-soluble resin having no ethylenically unsaturated group in the main chain is preferably more than 0, and the acid equivalent of the nonvolatile component of the photosensitive resin composition is preferably 79.0 or less from the viewpoints of the development resistance of the photosensitive resin layer, the resolution and adhesion of the resist pattern, and further the developability and peeling property of the photosensitive resin layer.
Further, the acid value (acid equivalent) of the nonvolatile component of the photosensitive resin composition containing (a) the alkali-soluble resin having no ethylenically unsaturated group in the main chain is more preferably more than 0 and 78.0 or less, and further preferably more than 0 and 76.0 or less.
The acid value in the above range corresponds to a so-called "low acid value" as compared with the prior art. In another aspect of the present invention, in recent years, particularly when the reduction in thickness of the photosensitive resin layer is required, the "reduction in thickness of the photosensitive resin layer" and the "low acid value" are realized.
Conventionally, it has been known that the hydrophobicity of a resist is increased as a method for high resolution (low SE). On the other hand, if the hydrophobicity of the resist is increased, the solubility in the developer is lowered, and therefore, the developing time tends to be longer. In this regard, when the molecular weight of the resin is reduced to shorten the development time, Cu defects (film strength) may be easily reduced.
In contrast, in another embodiment of the present invention in which "thinning of the photosensitive resin layer" and "low acid value" are realized, it is easy to achieve a balance between various effects.
(A) Glass transition temperature (Tg) of alkali-soluble resin having no ethylenically unsaturated group in the main chain, which is determined by the following numerical formula (I)total) Preferably 100 ℃ or lower.
Figure BDA0002832058100000281
{ in formula (II), WiTo the respective masses of the comonomers constituting the alkali-soluble resin,
Tgito obtain the glass transition temperature when the comonomers constituting the alkali-soluble resin are homopolymers,
Wtotalis the total mass of the alkali-soluble resin, and
n is the number of types of comonomers constituting the alkali-soluble resin. }
When a mixture of a plurality of polymers is used as the (a) alkali-soluble resin containing no ethylenically unsaturated group in the main chain, the glass transition temperature is a value determined as an average value of all the polymers.
The glass transition temperature Tg was determinediAs the glass transition temperature of a homopolymer formed from a comonomer forming the corresponding alkali-soluble resin, "Polymer handbook, Third edition, John wire, written by Brandrup, J.Immergut, E.H. was used&sons,1989, p.209Chapter VI Glass transition temperatures of polymers.
Tg of representative comonomersiAs shown below (all values are literature values).
Methacrylic acid: tg 501K
Benzyl methacrylate: tg 327K
Methyl methacrylate: tg 378K
Styrene: tg 373K
2-ethylhexyl acrylate: tg 223K
The glass transition temperature (Tg) as described abovetotal) Alkali of (2)The soluble resin is preferably a copolymer of an acid monomer and another monomer.
The glass transition temperature (Tg) of the alkali-soluble resin having no ethylenically unsaturated group in the main chain of (A) determined by the above formula (I)total) The lower limit of (3) is not particularly limited. Glass transition temperature (Tg)total) The temperature may be 10 ℃ or higher, 30 ℃ or higher, 50 ℃ or higher, or 70 ℃ or higher.
(A) The alkali-soluble resin having no ethylenically unsaturated group in the main chain preferably has a weight average molecular weight of 5,000 to 500,000. From the viewpoint of uniformly maintaining the thickness of the photosensitive resin laminate such as a dry film resist and obtaining resistance to a developer, (a) the weight average molecular weight of the alkali-soluble resin not containing an ethylenically unsaturated group in the main chain is preferably 5,000 or more, while from the viewpoint of maintaining the developability of the photosensitive resin laminate such as a dry film resist and the like, (a) the weight average molecular weight of the alkali-soluble resin not containing an ethylenically unsaturated group in the main chain is preferably 500,000 or less. The weight average molecular weight (Mw) of the alkali-soluble resin (A) having no ethylenically unsaturated group in the main chain is more preferably 10,000 to 200,000, and still more preferably 20,000 to 100,000 or 23,000 to 50,000. Further, the ratio of Mw to the number average molecular weight (Mn) of the alkali-soluble resin (A) having no ethylenically unsaturated group in the main chain, i.e., the dispersity (Mw/Mn) of the alkali-soluble resin (A) having no ethylenically unsaturated group in the main chain is preferably 1.0 to 6.0.
(A) The alkali-soluble resin having no ethylenically unsaturated group in the main chain is preferably obtained by polymerizing at least 1 first monomer described later. Further, (a) the alkali-soluble resin having no ethylenically unsaturated group in the main chain is more preferably obtained by copolymerizing at least 1 first monomer with at least 1 second monomer described later.
The first monomer is a monomer having a carboxyl group in the molecule. Examples of the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, β -carboxyethyl (meth) acrylate, and maleic acid half ester. Among these, (meth) acrylic acid is particularly preferable.
Examples of the second monomer include an unsaturated aromatic compound (which may be referred to as an "aromatic monomer"), an alkyl (meth) acrylate, an aralkyl (meth) acrylate, a conjugated diene compound, a polar monomer, and a crosslinkable monomer. Among these, unsaturated aromatic compounds are preferable from the viewpoint of improving the resolution of the resist pattern.
Examples of the unsaturated aromatic compound include benzyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, styrene, cinnamic acid, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene trimer, etc.). Of these, benzyl (meth) acrylate and styrene are preferable, and benzyl (meth) acrylate is more preferable.
The alkyl (meth) acrylate is a concept including both a chain alkyl ester and a cyclic alkyl ester, and specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, n-tetradecyl (meth) acrylate, stearyl (meth) acrylate, and cyclohexyl (meth) acrylate.
Examples of the aralkyl (meth) acrylate include benzyl (meth) acrylate; examples of the conjugated diene compound include 1, 3-butadiene, isoprene, 2, 3-dimethyl-1, 3-butadiene, 2-phenyl-1, 3-butadiene, 1, 3-pentadiene, 2-methyl-1, 3-pentadiene, 1, 3-hexadiene, 4, 5-diethyl-1, 3-octadiene, and 3-butyl-1, 3-octadiene. Examples of the polar monomer include hydroxyl group-containing monomers such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and pentenol; amino group-containing monomers such as 2-aminoethyl methacrylate; amide group-containing monomers such as (meth) acrylamide and N-methylol (meth) acrylamide; cyano group-containing monomers such as acrylonitrile, methacrylonitrile, α -chloroacrylonitrile, and α -cyanoethyl acrylate; epoxy group-containing monomers such as glycidyl (meth) acrylate and 3, 4-epoxycyclohexyl (meth) acrylate.
Examples of the crosslinkable monomer include trimethylolpropane triacrylate and divinylbenzene.
(A) The alkali-soluble resin having no ethylenically unsaturated group in the main chain can be prepared by applying a known polymerization method, preferably addition polymerization, more preferably radical polymerization, to the above-mentioned first monomer and/or second monomer.
The content of the alkali-soluble resin (a) having no ethylenically unsaturated group in the main chain thereof in the photosensitive resin composition (hereinafter, unless otherwise specified, the same applies to each component contained) is preferably in the range of 10 to 90% by mass, more preferably in the range of 20 to 80% by mass, and still more preferably in the range of 30 to 60% by mass. The content of the alkali-soluble resin (a) having no ethylenically unsaturated group in the main chain is preferably 10 mass% or more from the viewpoint of maintaining the alkali developability of the photosensitive resin layer, and the content of the alkali-soluble resin (a) having no ethylenically unsaturated group in the main chain is preferably 90 mass% or less from the viewpoint of sufficiently exerting the performance as a resist material of a resist pattern formed by exposure.
[ B ] photopolymerizable Compound having ethylenically unsaturated bond >
(B) The photopolymerizable compound having an ethylenically unsaturated bond is a compound having polymerizability by having an ethylenically unsaturated bond, specifically an ethylenically unsaturated group in its structure.
The photosensitive resin composition may have 1 or more olefinic double bonds as the component (B). Preference is given to using compounds having more than 2 olefinic double bonds.
Specific examples of the component (B) include di (meth) acrylates of polyalkylene glycols obtained by adding an average of 2 to 15 moles of alkylene oxide to each end of bisphenol A, tri (meth) acrylates of polyalkylene triols obtained by adding an average of 3 to 25 moles of alkylene oxide to trimethylolpropane; a compound obtained by converting an alcohol obtained by adding a polyoxyalkylene group or modifying an epsilon-caprolactone to glycerin, trimethylolpropane, pentaerythritol, diglycerol, ditrimethylolpropane, an isocyanurate ring, or the like, into a (meth) acrylate; or a compound obtained by reacting them directly with (meth) acrylic acid without modification with an oxyalkylene group or epsilon-caprolactone; a tetra (meth) acrylate of a polyhydric alcohol having an average of 4 to 35 moles of alkylene oxide added to pentaerythritol; and hexa (meth) acrylate of a polyhydric alcohol obtained by adding an alkylene oxide to dipentaerythritol in an amount of 4 to 30 moles on average. These can be used alone in 1 or a combination of 2 or more.
The content of the photopolymerizable compound having an ethylenically unsaturated group (B) in the photosensitive resin composition is preferably in the range of 5 to 70 mass%, more preferably 20 to 60 mass%, and still more preferably 30 to 50 mass%. The content of the compound having an ethylenically unsaturated group (B) is preferably 5% by mass or more from the viewpoint of suppressing curing failure of the photosensitive resin layer and delay in development time, and the content of the compound having an ethylenically unsaturated group (B) is preferably 70% by mass or less from the viewpoint of suppressing peeling delay of the cured resist.
[ C ] photopolymerization initiator
(C) The photopolymerization initiator is a compound capable of generating radicals by actinic rays and polymerizing (B) a photopolymerizable compound having an ethylenically unsaturated group, or the like. In the photosensitive resin composition, as the (C) photopolymerization initiator, a photopolymerization initiator generally known in the art may be contained.
Examples of the photopolymerization initiator (C) include hexaarylbiimidazole compounds, N-aryl- α -amino acid compounds, quinone compounds, aromatic ketone compounds, acetophenone compounds, acylphosphine oxide compounds, benzoin ether compounds, dialkyl ketal compounds, thioxanthone compounds, dialkyl aminobenzoate compounds, oxime ester compounds, acridine compounds, dihydropyrazole derivatives, ester compounds of N-aryl amino acids, and halides.
Examples of the hexaarylbiimidazole compound include 2- (o-chlorophenyl) -4, 5-diphenylbiimidazole (otherwise known as 2,2 ' -bis (2-chlorophenyl) -4,4 ', 5,5 ' -tetraphenyl-1, 2 ' -biimidazole), 2 ', 5-tris (o-chlorophenyl) -4- (3, 4-dimethoxyphenyl) -4 ', 5 ' -diphenylbiimidazole, 2, 4-bis (o-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -diphenylbiimidazole, 2,4, 5-tris (o-chlorophenyl) -diphenylbiimidazole, 2- (o-chlorophenyl) -bis-4, 5- (3, 4-dimethoxyphenyl) biimidazole, and mixtures thereof, 2,2 ' -bis (2-fluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) biimidazole, 2 ' -bis (2, 3-difluoromethylphenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) biimidazole, 2 ' -bis (2, 4-difluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) biimidazole, 2 ' -bis (2, 5-difluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) biimidazole, 2 ' -bis (2, 6-difluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) biimidazole, 2,2 ' -bis (2,3, 4-trifluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) biimidazole, 2 ' -bis (2,3, 5-trifluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) biimidazole, 2 ' -bis (2,3, 6-trifluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) biimidazole, 2 ' -bis (2,4, 5-trifluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) biimidazole, 2 ' -bis (2,4, 6-trifluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) biimidazole, 2,2 ' -bis (2,3,4, 5-tetrafluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) biimidazole, 2 ' -bis (2,3,4, 6-tetrafluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) biimidazole, and 2,2 ' -bis (2,3,4,5, 6-pentafluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) biimidazole, and the like. Among them, 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer is preferable from the viewpoint of high sensitivity, resolution and adhesion.
Examples of the N-aryl- α -amino acid compound include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine. In particular, N-phenylglycine is preferable because it has a high sensitizing effect.
Examples of the quinone compound include 2-ethylanthraquinone, octaethylanthraquinone, 1, 2-benzoanthraquinone, 2, 3-benzoanthraquinone, 2-phenylanthraquinone, 2, 3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1, 4-naphthoquinone, 9, 10-phenanthrenequinone, 2-methyl-1, 4-naphthoquinone, 2, 3-dimethylanthraquinone, and 3-chloro-2-methylanthraquinone.
Examples of the aromatic ketone compound include benzophenone, michler's ketone [4, 4' -bis (dimethylamino) benzophenone ], 4 '-bis (diethylamino) benzophenone, 4-methoxy-4' -dimethylamino benzophenone, and the like.
Examples of the acetophenone compounds include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) one, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinoacetone-1, and the like. Examples of commercially available acetophenone compounds include Irgacure-907, Irgacure-369 and Irgacure-379 available from Ciba Specialty Chemicals, Inc. From the viewpoint of use as a sensitizer and adhesion, 4' -bis (diethylamino) benzophenone is preferable.
Examples of the acylphosphine oxide compound include 2,4, 6-trimethylbenzyldiphenylphosphine oxide, bis (2,4, 6-trimethylbenzoyl) phosphine oxide, bis (2, 6-dimethoxybenzoyl) -2,4, 4-trimethylpentylphosphine oxide and the like. Examples of commercially available products of the acylphosphine oxide compound include LUCIRIN TPO manufactured by BASF corporation and Irgacure-819 manufactured by Ciba Specialty Chemicals corporation.
Examples of the benzoin compound and the benzoin ether compound include benzoin, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, and ethyl benzoin.
Examples of the dialkyl ketal compound include benzil dimethyl ketal and benzil diethyl ketal.
Examples of the thioxanthone compound include 2, 4-diethylthioxanthone, 2, 4-diisopropylthioxanthone, and 2-chlorothioxanthone.
Examples of the dialkylaminobenzoate compounds include ethyl dimethylaminobenzoate, ethyl diethylaminobenzoate, ethyl-p-dimethylaminobenzoate, and 2-ethylhexyl-4- (dimethylamino) benzoate.
Examples of the oxime ester compound include 1-phenyl-1, 2-propanedione-2-O-benzoyl oxime, 1-phenyl-1, 2-propanedione-2- (O-ethoxycarbonyl) oxime, and the like. Examples of commercially available oxime ester compounds include CGI-325, Irgacure-OXE01 and Irgacure-OXE02 manufactured by Ciba Specialty Chemicals, Inc.
The acridine compound is preferably 1, 7-bis (9, 9' -acridinyl) heptane or 9-phenylacridine from the viewpoints of sensitivity, resolution, acquisition property, and the like.
As the dihydropyrazole derivative, 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -dihydropyrazole, 1-phenyl-3- (4-biphenyl) -5- (4-tert-butyl-phenyl) -dihydropyrazole, and 1-phenyl-3- (4-biphenyl) -5- (4-tert-octyl-phenyl) -dihydropyrazole are preferable from the viewpoints of adhesiveness and rectangularity of the resist pattern.
Examples of the ester compound of an N-arylamino acid include methyl ester of N-phenylglycine, ethyl ester of N-phenylglycine, N-propyl ester of N-phenylglycine, isopropyl ester of N-phenylglycine, 1-butyl ester of N-phenylglycine, 2-butyl ester of N-phenylglycine, t-butyl ester of N-phenylglycine, pentyl ester of N-phenylglycine, hexyl ester of N-phenylglycine, pentyl ester of N-phenylglycine, and octyl ester of N-phenylglycine.
Examples of the halide include amyl bromide, isoamyl bromide, isobutylene bromide, vinyl bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenylsulfone, carbon tetrabromide, tris (2, 3-dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1, 1-trichloro-2, 2-bis (p-chlorophenyl) ethane, a triazine chloride compound, and a diallylium iodide compound, and tribromomethylphenylsulfone is particularly preferable.
The content of the photopolymerization initiator (C) in the photosensitive resin composition is preferably 0.01 to 20% by mass, and more preferably 0.5 to 10% by mass. By adjusting the content of the photopolymerization initiator (C) within the above range, a photosensitive resin composition can be obtained which can obtain sufficient sensitivity, can sufficiently project light to the bottom of the resist, can obtain high resolution, and has an excellent balance with the amount of undercut of the conductor pattern.
As the photopolymerization initiator (C), a hexaarylbisimidazole compound is preferably used. In this case, the content of the hexaarylbisimidazole compound in the photosensitive resin composition is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass.
As the photopolymerization initiator (C), an aromatic ketone compound such as 4, 4' -bis (diethylamino) benzophenone and a hexaarylbisimidazole compound are preferably used in combination. In this case, the content of the aromatic ketone compound in the photosensitive resin composition is preferably 0.5% by mass or less, more preferably 0.01% by mass to 0.4% by mass, and the content of the hexaarylbisimidazole compound in the photosensitive resin composition is preferably 0.1% by mass to 10% by mass, more preferably 0.5% by mass to 5% by mass.
< Compound (D) having polyoxytetramethylene group as a structural Unit >
Since the compound having polyoxytetramethylene group as a structural unit has high flexibility, appropriate flexibility can be imparted to the resist pattern formed. Thus, the resist film is less likely to be chipped due to the process load, and therefore Cu chipping can be reduced. Further, since the compound having polyoxytetramethylene group as a structural unit has high hydrophobicity, it can be used for a photosensitive resin laminate to improve resolution and reduce undercut. For the foregoing reasons, it is preferable to use a compound having polyoxytetramethylene group as a structural unit.
Examples of the compound having polyoxytetramethylene as a structural unit include polytetramethylene glycol, polytetramethylene glycol dimethacrylate, polytetramethylene glycol diacrylate, 2-bis (4- ((meth) acryloyloxypolytetramethyleneoxy) phenyl) propane, polytetramethylene glycol trimethylolpropane tri (meth) acrylate, urethane reactants of hydroxyethyl (meth) acrylate and polytetramethylene glycol with a diisocyanate compound or a triisocyanate compound, and the like. Among these, polytetramethylene glycol dimethacrylate compounds are preferable. Further, they may be used alone in 1 kind or in combination of 2 or more kinds.
From the viewpoint of alkali developability, the total content of the (D) compound having a polyoxytetramethylene group as a structural unit in the photosensitive resin composition is preferably in the range of 0.5 to 50% by mass, and more preferably in the range of 1 to 40% by mass.
< Compound having benzotriazole skeleton >
From the viewpoint of improving the thermal stability and/or storage stability of the photosensitive resin composition, a compound having a benzotriazole skeleton is preferably used. Examples of the compound having a benzotriazole skeleton include benzotriazoles and carboxybenzotriazoles.
Examples of the benzotriazole include 1,2, 3-benzotriazole, 1-chloro-1, 2, 3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1, 2, 3-tolyltriazole, bis (N-2-hydroxyethyl) aminomethylene-1, 2, 3-benzotriazole, 1:1 mixture of 1- (2-di-N-butylaminomethyl) -5-carboxybenzotriazole and 1- (2-di-N-butylaminomethyl) -6-carboxybenzotriazole, and the like. Of these, a 1:1 mixture of 1- (2-di-n-butylaminomethyl) -5-carboxybenzotriazole and 1- (2-di-n-butylaminomethyl) -6-carboxybenzotriazole is preferred. Further, they may be used alone in 1 kind or in combination of 2 or more kinds.
Examples of the carboxybenzotriazole include 4-carboxy-1, 2, 3-benzotriazole, 5-carboxy-1, 2, 3-benzotriazole, N- (N, N-di-2-ethylhexyl) aminomethylene carboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylene carboxybenzotriazole and N- (N, N-di-2-ethylhexyl) aminoethylene carboxybenzotriazole. These can be used alone in 1 or a combination of 2 or more.
(E) The total content of the compound having a benzotriazole skeleton in the photosensitive resin composition is preferably in the range of 0.001 to 3% by mass, and more preferably in the range of 0.05 to 1% by mass. The total content is preferably 0.001 mass% or more from the viewpoint of imparting good storage stability to the photosensitive resin composition, and is preferably 3 mass% or less from the viewpoint of maintaining the sensitivity and resolution of the photosensitive resin layer.
In the photosensitive resin composition, the ratio of the component (a) to the total of the components (B) and (D) [ (a) component/((B) component + (D) component) ] is preferably 1.4 or less. Solubility in an alkaline aqueous solution and mechanical strength of the resist film are improved, and minimum development time and Cu defects can be improved.
From the viewpoint of resistance to hot edge melting, the lower limit of the above ratio is preferably 0.5 or more.
< other ingredients >
The photosensitive resin composition preferably contains a coloring material such as a dye, and additives such as an antioxidant and a stabilizer, as desired.
Examples of the dye include tris (4-dimethylaminophenyl) methane [ leuco crystal violet ], bis (4-dimethylaminophenyl) phenylmethane [ leuco malachite GREEN ], fuchsin, phthalocyanine GREEN, auramine base, parafuchsin, crystal violet, methyl orange, nile blue 2B, victoria blue, malachite GREEN (Aizen (registered trademark) MALACHITE GREEN, manufactured by pau chemical), alkali blue 20, and DIAMOND GREEN (Aizen (registered trademark) DIAMOND GREEN GH, manufactured by pau chemical). Among these, diamond green and leuco crystal violet are preferable from the viewpoint of improving colorability, color stability and exposure contrast. These can be used alone in 1 or a combination of 2 or more.
The content of the dye in the photosensitive resin composition is preferably in the range of 0.001 to 3% by mass, more preferably in the range of 0.01 to 2% by mass, and still more preferably in the range of 0.04 to 1% by mass. The content of the dye is preferably 0.001 mass% or more from the viewpoint of obtaining good colorability, and is preferably 3 mass% or less from the viewpoint of maintaining the sensitivity of the photosensitive resin layer.
Examples of the antioxidant include triphenyl phosphite (e.g., TPP, trade name, manufactured by Asahi Denka Kogyo Co., Ltd.), tris (2, 4-di-t-butylphenyl) phosphite (e.g., 2112, manufactured by Asahi Denka Co., Ltd.), tris (monononylphenyl) phosphite (e.g., 1178, manufactured by Asahi Denka Kogyo Co., Ltd.), bis (monononylphenyl) dinonylphenyl phosphite (e.g., 329K, manufactured by Asahi Denka Ltd.), and the like. These can be used alone in 1 or a combination of 2 or more.
The content of the antioxidant in the photosensitive resin composition is preferably in the range of 0.01 to 0.8% by mass, and more preferably in the range of 0.01 to 0.3% by mass. The content of the antioxidant is preferably 0.01% by mass or more from the viewpoint of satisfactorily expressing the hue stability of the resist pattern and improving the sensitivity of the photosensitive resin layer, and the content of the antioxidant is preferably 0.8% by mass or less from the viewpoint of satisfactorily expressing the hue stability and improving the adhesion while suppressing the color development of the resist pattern.
From the viewpoint of improving the thermal stability and/or storage stability of the photosensitive resin composition, a stabilizer is preferably used. Examples of the stabilizer include at least 1 compound selected from the group consisting of a radical polymerization inhibitor and an alkylene oxide compound having a glycidyl group. These can be used alone in 1 or a combination of 2 or more.
Examples of the radical polymerization inhibitor include p-methoxyphenol, hydroquinone, biphenyltriol, naphthylamine, t-butylcatechol, cuprous chloride, 2, 6-di-t-butyl-p-cresol, 2 '-methylenebis (4-methyl-6-t-butylphenol), 2' -methylenebis (4-ethyl-6-t-butylphenol), triethylene glycol bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate ], nitrosophenylhydroxylamine aluminum salt (for example, an aluminum salt to which 3 moles of nitrosophenylhydroxylamine is added), and diphenylnitrosamine. Among these, triethylene glycol bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate ] or an aluminum salt to which 3 moles of nitrosophenylhydroxylamine is added is preferable. Further, they may be used alone in 1 kind or in combination of 2 or more kinds.
Examples of the alkylene oxide compound having a glycidyl group include neopentyl glycol diglycidyl ether (e.g., EPOLIGHT 1500NP manufactured by honor chemical corporation), nonaethylene glycol diglycidyl ether (e.g., EPOLIGHT 400E manufactured by honor chemical corporation), diglycidyl ether of a 2-mol adduct of bisphenol a-propylene oxide (e.g., EPOLIGHT 3002 manufactured by honor chemical corporation), and 1, 6-hexanediol diglycidyl ether (e.g., EPOLIGHT 1600 manufactured by honor chemical corporation). These can be used alone in 1 or a combination of 2 or more.
The total content of the radical polymerization inhibitor and the glycidyl group-containing alkylene oxide compound in the photosensitive resin composition is preferably in the range of 0.001 to 3% by mass, and more preferably in the range of 0.05 to 1% by mass. The total content is preferably 0.001 mass% or more from the viewpoint of imparting good storage stability to the photosensitive resin composition, and is preferably 3 mass% or less from the viewpoint of maintaining the sensitivity of the photosensitive resin layer.
[ photosensitive resin composition blending liquid ]
A photosensitive resin composition blend liquid can be formed by adding a solvent to the photosensitive resin composition of the present application. Suitable solvents include, for example, ketones such as acetone and Methyl Ethyl Ketone (MEK); and alcohols such as methanol, ethanol, and isopropanol. The solvent is preferably added to the photosensitive resin composition so that the viscosity of the photosensitive resin composition mixture liquid becomes 500 mPasec to 4000 mPasec at 25 ℃.
[ photosensitive resin laminate, Dry film resist, and transfer film ]
The photosensitive resin composition or the photosensitive resin composition blend liquid of the present application can be used to provide a photosensitive resin laminate. The photosensitive resin laminate comprises a support film (support) and a layer formed on the support film and containing the photosensitive resin composition. The photosensitive resin laminate may have a protective layer on the surface opposite to the support film side, if necessary. From the viewpoint of remarkably exerting the effect of the present invention, the photosensitive resin laminate is preferably a dry film resist or a transfer film, and more preferably a dry film resist.
Among these, from the viewpoint of suppressing pattern defects, improving the yield of a formed product or a formed pattern by a photolithography method, and/or excelling in at least one of the laminatability, minimum development time, resolution, undercut, Cu defects, and development residue, particularly preferred is a dry film resist having:
supporting the film; and
a photosensitive layer containing a composition formed on the support film, the composition comprising:
(A) alkali soluble resin,
(B) A compound having an ethylenically unsaturated bond,
(C) A photopolymerization initiator,
(D) The dye is a mixture of a dye and a water,
the component (B) includes:
(B-ii) a compound having a dipentaerythritol skeleton but no oxyalkylene group; and
(B-iii) a compound having a skeleton derived from a bisphenol,
(B) the components (B-ii) and (B-iii) are 50% by mass or more, and the ratio of component (B-ii)/component (B-iii) is 10 to 80% by mass. In addition, the particularly preferable composition of the dry film resist may be combined with or interchanged with a composition of a photosensitive resin laminate in which the ratio (a/T) of the acid value a of the nonvolatile component of the photosensitive resin composition to the thickness T of the photosensitive resin layer is within the numerical range of the present application.
The support film is preferably a transparent film through which light emitted from the exposure light source is transmitted. Examples of such a support film include a polyethylene terephthalate film, a polyvinyl alcohol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, a vinylidene chloride copolymer film, a polymethyl methacrylate copolymer film, a polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, and a cellulose derivative film. These films may be stretched, if necessary.
The haze of the support film is preferably 5 or less. The support film is preferably 10 to 30 μm in thickness in view of its function of maintaining strength, although it is advantageous in terms of image formability and economy when the thickness is small.
The layer of the photosensitive resin composition described above (hereinafter also referred to as "photosensitive resin layer") may contain or be composed of a photosensitive resin composition. The film thickness of the layer of the photosensitive resin composition in the photosensitive resin laminate is preferably 0.5 to 25 μm, more preferably 1 to 25 μm, and still more preferably 1 to 20 μm, from the viewpoint of the resolution of the resist pattern, the undercut amount, the puncture strength, or the peelability. From the same viewpoint, the upper limit of the film thickness is particularly preferably 16 μm or less, and most preferably 10 μm or less.
An important characteristic of the protective layer used for the photosensitive resin laminate is that it has an appropriate adhesive force. In other words, the adhesion force of the protective layer to the photosensitive resin layer is preferably sufficiently smaller than the adhesion force of the support film to the photosensitive resin layer, and the protective layer can be easily peeled from the photosensitive resin laminate. As the protective layer, for example, a polyethylene film, a polypropylene film, a polyethylene terephthalate film, a polyester film, or the like can be used. Further, a release layer suitable for peeling the protective film from the photoresist layer may be provided on one surface of the protective layer film. The release layer is generally classified into an organosilicon compound and a non-organosilicon compound, and the organosilicon compound can be exemplified by: a condensation reaction type organic silicon resin obtained by reacting silanol polydimethylsiloxane at two ends with polymethylhydrosiloxane or polymethylmethoxysiloxane; an addition reaction type silicone resin obtained by reacting a dimethylsiloxane-methylvinylsiloxane copolymer or a dimethylsiloxane-methylhexenylsiloxane copolymer with polymethylhydrogensiloxane; ultraviolet-curable or electron-ray-curable silicone resins obtained by curing acrylic silicones, epoxy-containing silicones, and the like with ultraviolet rays or electron rays; modified silicone resins, for example, epoxy-modified silicone resins (silicone epoxy resins), polyester-modified silicone resins (silicone polyesters), acrylic-modified silicone resins (silicone acrylics), phenol-modified silicone resins (silicone phenols), alkyd-modified silicone resins (silicone alkyds), melamine-modified silicone resins (silicone melamines), and the like. Examples of the non-organic silicon compound include alkyd (also referred to as alkyd) resins, long-chain alkyl resins, acrylic resins, and polyolefin resins. The thickness of the release layer is preferably in the range of 0.001 to 2 μm, more preferably 0.005 to 1 μm, and further preferably 0.01 to 0.5. mu.m. If the film thickness exceeds 2 μm, the appearance of the coating film may deteriorate and the curing of the coating film may become insufficient, and if the film thickness is less than 0.001 μm, sufficient releasability may not be obtained. The thickness of the protective layer is preferably 10 to 100 μm, and more preferably 10 to 50 μm.
[ method for producing photosensitive resin laminate ]
The photosensitive resin laminate can be produced by sequentially laminating a photosensitive resin layer and a protective layer as required on a support film. As the method, a known method can be used. For example, a photosensitive resin composition used for the photosensitive resin layer is mixed with a solvent in which the photosensitive resin composition is dissolved to form a photosensitive resin composition mixed solution (coating solution) in a uniform solution state. Next, a photosensitive resin layer can be laminated on the support film (support) by applying a coating liquid on the support film using a bar coater or a roll coater, followed by drying. If necessary, a protective layer is laminated on the photosensitive resin layer, whereby a photosensitive resin laminate can be produced.
[ method of Forming resist Pattern ]
Another aspect of the present invention provides a method for forming a resist pattern, including the steps of:
a step of laminating the photosensitive resin laminate of the present application to a substrate (laminating step);
a step (exposure step) of exposing the laminated photosensitive resin laminate; and
and a step (developing step) of developing the exposed photosensitive resin laminate.
[ method for Forming Wiring Pattern ]
Another aspect of the present invention provides a wiring pattern forming method including the steps of:
a step (etching or plating step) of performing etching or plating treatment of the substrate on which the resist pattern is formed by the resist pattern forming method.
An example of a method for forming a resist and a wiring pattern using the photosensitive resin laminate and the base material will be described below.
(laminating step)
The lamination process may be performed as follows: in the case where the photosensitive resin laminate has a protective layer, the protective layer is peeled off from the laminate, and then the photosensitive resin layer is laminated on the surface of the substrate by thermocompression bonding using, for example, a laminator.
Examples of the material of the substrate include copper (Cu), stainless steel (SUS), glass, Indium Tin Oxide (ITO), and a flexible substrate on which a conductive thin film is laminated. Examples of the conductive thin film include ITO, copper-nickel alloy, and silver. Examples of the material constituting the flexible base include polyethylene terephthalate (PET).
The substrate used may be a copper wiring formed on a copper-clad laminate, a substrate made of glass alone, or a transparent electrode (e.g., ITO, Ag nanowire substrate, etc.) or a metal electrode (e.g., Cu, Al, Ag, Ni, Mo, and an alloy of at least 2 of these) formed on a transparent resin substrate. In addition, the use base material may have a through hole for corresponding to the multilayer substrate.
From the viewpoint of remarkably exerting the effect of the present invention, the base material used is preferably a copper-clad laminate substrate, and more preferably a copper-clad laminate substrate in which a copper foil having a thickness of 35 μm is laminated, and which has a thickness of 1.6mm and a through hole having a diameter of 6 mm.
The photosensitive resin layer may be laminated on only one surface of the substrate, or may be laminated on both surfaces of the substrate as necessary. The heating temperature at the time of lamination is preferably 40 to 160 ℃, more preferably 80 to 120 ℃. The adhesion of the resulting resist pattern to the substrate can be improved by performing the thermal compression bonding 2 or more times. When the pressure bonding is performed 2 times or more, a two-stage laminator having two rollers may be used, or a laminate of the substrate and the photosensitive resin layer may be repeatedly passed through the rollers and pressure bonded.
(Exposure Process)
In the exposure step, the photosensitive resin layer is exposed using an exposure machine. From the viewpoint of the puncture strength of the obtained resist film, it is preferable to peel the support from the photosensitive resin laminate and then perform the exposure. By performing this exposure in a pattern, a resist film (resist pattern) having a desired pattern can be obtained after a developing step described later. The pattern-like exposure may be performed by any of a method of performing exposure through a photomask and a maskless exposure.
When exposure is performed through a photomask, the exposure amount is determined by the illuminance of the light source and the exposure time. The exposure amount may be measured using a light meter. In the maskless exposure, exposure is performed on a substrate directly by a writing apparatus without using a photomask. As the light source, a semiconductor laser having a wavelength of 350nm to 410nm, an ultra-high pressure mercury lamp, or the like can be used. In the maskless exposure, a drawing pattern is controlled by a computer, and the exposure amount is determined by the illuminance of an exposure light source and the moving speed of the substrate.
From the viewpoint of improving the resolution of the resist pattern, reducing the amount of undercut, or improving the yield of the resist or wiring pattern, it is preferable to perform exposure through a photomask.
(developing step)
In the developing step, the non-pattern portion of the photosensitive resin layer is removed with a developer. In the developing step, a developing solution composed of an aqueous alkali solution is used, and in the case of using a negative photosensitive resin composition, a resist pattern is obtained by dissolving and removing an unexposed portion, and in the case of using a positive photosensitive resin composition, a resist pattern is obtained by dissolving and removing an exposed portion.
As the aqueous alkali solution, for example, Na is preferably used2CO3、K2CO3And the like. The aqueous alkali solution is selected depending on the characteristics of the photosensitive resin composition layer, and is preferably usedNa having a concentration of 0.2 to 2 mass%2CO3An aqueous solution. A surfactant, a defoaming agent, a small amount of an organic solvent for promoting development, and the like may be mixed into the aqueous alkali solution. The temperature of the developing solution in the developing step is preferably kept at a fixed temperature in the range of 18 to 40 ℃.
If desired, a heating step of heating the resulting resist pattern at 100 to 300 ℃ may be performed after the developing step. By performing this heating step, the chemical resistance of the resist pattern may be improved. The heating may be performed by a heating furnace using a suitable method such as hot air, infrared rays, or far infrared rays.
(etching or plating step)
After the resist pattern is formed by the above-described method for forming a resist pattern, a wiring pattern can be formed on the substrate by performing etching or plating treatment of the substrate on which the resist pattern is formed. From the viewpoint of remarkably exhibiting the effect of the present invention, it is preferable to perform at least the etching step.
The etching step can be performed by, for example, spraying an etching solution from above the resist pattern according to a known etching method to etch the surface of the substrate not covered with the resist pattern. Examples of the etching method include acid etching and alkali etching, and the etching method is performed according to the photosensitive resin laminate used. The etching liquid may be, for example, an aqueous hydrochloric acid solution, an aqueous ferric chloride solution, or a mixture thereof. The etching solution may be sprayed.
The plating step may be performed by performing metal plating (for example, based on a copper sulfate plating solution) or solder plating on the surface of the base material exposed by the development according to a known plating method.
After the etching step and/or the plating step, the photosensitive resin laminate may be treated with an aqueous solution having a stronger alkalinity than the developer to peel off the resist pattern from the substrate. The stripping solution may be, for example, an aqueous solution of NaOH or KOH having a concentration of about 2 to 5% by mass and a temperature of about 40 to 70 ℃.
The evaluation values of the various parameters described above are measured by the measurement method in the embodiment described below unless otherwise specified.
The embodiments of the present invention have been described above, but the present invention is not limited to these embodiments, and can be appropriately modified within a range not departing from the gist of the present invention.
Examples
The present invention will be specifically described below based on examples, but the present invention is not limited to these examples.
[ one embodiment of the present invention ]
<1 > preparation of photosensitive resin composition >
A photosensitive resin composition was prepared by mixing a plurality of components according to the composition shown in table 1 (wherein the number of each component represents the amount of blending (parts by mass) in terms of solid content).
The names of the components, the solvents used, and the like, which are indicated in table 1 by abbreviations, are shown in table 2. The weight average molecular weight (Mw) shown in Table 2 is a weight average molecular weight measured by Gel Permeation Chromatography (GPC) using a standard curve of polystyrene (Shodex STANDARD SM-105, manufactured by Showa Denko K.K.). The weight average molecular weight (Mw) and the number average molecular weight (Mn) can be measured by the following conditions using gel permeation chromatography manufactured by japan spectrography.
Differential refractometer: RI-1530
A pump: PU-1580
A degassing device: DG-980-50
Column oven: CO-1560
Column: KF-8025, KF-806 MX 2 and KF-807
Eluent: THF (tetrahydrofuran)
<2 > production of photosensitive resin laminate
Ethanol as a solvent was added to the photosensitive resin composition until the solid content reached 58 mass%, followed by stirring and mixing, and the obtained photosensitive resin composition solution was uniformly applied to a polyethylene terephthalate film (FB-40, manufactured by Toray corporation; polyethylene terephthalate film of 16 μm) having a thickness of 25 μm using a bar coater, and dried in a drier at 95 ℃ for 5 minutes to form a photosensitive resin layer (dry film) having a thickness of 5 μm to 25 μm. Subsequently, a polyethylene film (GF-858, manufactured by Tamapy Co.) having a thickness of 33 μm was attached to the surface of the photosensitive resin layer to obtain a photosensitive resin laminate.
<3. production of evaluation substrate >
< lamination >
The photosensitive resin laminate was laminated on a PET substrate with a copper layer at a roll temperature of 105 ℃ by a hot roll laminator (manufactured by Asahi Chemicals Co., Ltd., AL-700) while peeling the polyethylene film. The air pressure was set to 0.35MPa, and the lamination speed was set to 1.5 m/min.
< Exposure >
The polyethylene terephthalate film as a support for the photosensitive resin layer was peeled from the laminated evaluation substrate, and the resultant was exposed to 120mJ/cm using an exposure machine (parallel light exposure machine (HMW-801, manufactured by ORC)) equipped with an ultrahigh-pressure mercury lamp using a chromium glass photomask2The evaluation substrate was exposed to the light of (1).
< development >
Using a developing apparatus manufactured by FUJI machinist, a nozzle of dense cone (dense cone) type was used to spray 1 mass% Na of 30 ℃ to the evaluation substrate after development for a predetermined period of time at a spray pressure of 0.15MPa2CO3The photosensitive resin layer is developed with an aqueous solution to dissolve and remove the unexposed portion of the photosensitive resin layer. At this time, the minimum time required for the photosensitive resin layer of the unexposed portion to be completely dissolved was measured as the minimum development time, and development was performed in a time 2 times the minimum development time to produce a resist pattern. In this case, the water washing step was performed using a flat nozzle at a water washing ejection pressure of 0.15MPa, taking the same time as the developing step.
< etching >
The developed evaluation substrate was etched with an etching apparatus manufactured by FUJI machine company using a dense cone type nozzle at a spray pressure of 0.15MPa and a temperature of 30 ℃ using an aqueous solution having a hydrochloric acid concentration of 2 mass% and containing iron chloride of 2 mass% for 60 seconds.
< peeling >
The etched evaluation substrate was treated with a NaOH aqueous solution having a concentration of 3 mass% for 30 seconds using a stripping apparatus manufactured by FUJI machine corporation under a condition of a spray pressure of 0.15MPa and a temperature of 50 ℃ by using a dense cone type nozzle, and the resist pattern was stripped off and removed from the evaluation substrate.
<4. evaluation method >
< evaluation of image Property >
After laminating a photosensitive resin laminate having a thickness of 5 μm of the photosensitive resin layer on the PET substrate with a copper layer by the method described in < laminating > above, the evaluation substrate obtained therefrom was exposed through a chrome glass mask having a line pattern in which the width ratio of the exposed portion to the unexposed portion was 1:1 over 15 minutes. Thereafter, development was performed in a time 2 times the minimum development time, and the resolution was graded as follows, using the minimum mask width in which the cured resist lines were normally formed as the value of the resolution. Note that, the width of the minimum mask normally formed without collapse of the cured resist pattern or adhesion of the cured resists was evaluated.
Very good (apparently good): the value of resolution is 3 μm or less;
o (good): a resolution value exceeding 3 μm and not more than 4 μm;
x (bad): the resolution value exceeds 4 μm.
< amount of undercut (SE) >
The following substrates were used for evaluating the amount of undercut: the evaluation substrate was obtained after 15 minutes from the time when the photosensitive resin laminate having a photosensitive resin layer thickness of 5 μm was laminated on the PET substrate with a copper layer by the method described in < laminating >.
The laminate evaluation substrate was exposed to a pattern of 10 μm/10 μm in line/space, and then developed by the method described in < development >.
First, the resist top width Wr (μm) of the pattern was measured by an optical microscope.
Next, the substrate having the line/space pattern was etched by a dipping method in an aqueous solution containing 2 mass% of hydrochloric acid and 2 mass% of ferric chloride at a temperature of 30 ℃ for a time 1.5 times as long as the minimum etching time. Here, the minimum etching time means a minimum time required to completely dissolve and remove the copper foil on the substrate under the above conditions.
After the etching, the cured film on the substrate was peeled off and removed at a temperature of 50 ℃ using a NaOH aqueous solution having a concentration of 3 mass% as a peeling liquid, and the top width Wc (μm) of the thus obtained copper line pattern was measured by an optical microscope.
Then, the amount of side etching is calculated by the following formula, and the amount of side etching is graded as follows.
Lateral erosion (μm) — (Wr-Wc) ÷ 2
Very good (apparently good): the amount of side etching is less than 3 μm;
o (good): the amount of side etching exceeds 3 μm and is 3.5 μm or less;
Δ (allowed): the amount of side etching exceeds 3.5 μm and is 4.0 μm or less;
x (bad): the amount of undercut exceeds 4.0 μm.
< evaluation of puncture Strength >
The following were used as the evaluation substrates: a copper-clad laminate substrate 1.6mm thick, on which a 35 μm copper foil was laminated, was flattened by surface treatment using a jet-cleaning grinder to obtain a body in which 1008 through-holes 6mm in diameter were formed.
On the flattened substrate, while the polyethylene film of the photosensitive resin laminate having a thickness of 25 μm of the photosensitive resin layer was peeled off, the laminate was laminated on both sides of the flattened substrate by a hot roll laminator (AL-70, manufactured by asahi chemical corporation) under conditions of a roll temperature of 105 ℃, an air pressure of 0.35MPa and a lamination speed of 1.5 m/min.
Using a substrate after 15 minutes from the lamination, the laminated substrate was exposed to 120mJ/cm using an exposure machine (parallel light exposure machine (HMW-801, manufactured by ORC)) having an ultra-high pressure mercury lamp2After exposing the evaluation substrate with the exposure amount of (2), the evaluation substrate is exposed to light<Development>The method as described in (1)And (5) line development. The developed substrate was conditioned overnight in a room with a temperature of 25 ℃ and a humidity of 50%.
After leaving the substrate, the polyethylene terephthalate film as a support for peeling the photosensitive resin layer from the obtained substrate was pierced into a 2.0mm diameter cylinder from the surface from which the support was peeled at a rate of 100 mm/min at a portion of the photosensitive resin layer corresponding to the center of the 6mm diameter through hole, and the maximum point load was measured by TENSILON (RTM-500, manufactured by ORIENTEC). The maximum point load was measured at 10 points for the portion of the photosensitive resin layer corresponding to the center of the through hole of 6mm phi, and the average value of the maximum 5 points among them was taken as the maximum point load in the puncture test. The obtained maximum point load was evaluated according to the following criteria.
Very good (apparently good): the puncture strength is more than 90 gf;
o (good): a puncture strength of 80gf or more and less than 90 gf;
Δ (allowed): a puncture strength of 70gf or more and less than 80 gf;
x (bad): the puncture strength is less than 70 gf.
< evaluation of copper (Cu) defects >
For the evaluation of copper (Cu) defects, the following substrates were used: the evaluation substrate was obtained after 15 minutes from the time when the photosensitive resin laminate having a photosensitive resin layer thickness of 5 μm was laminated on the PET substrate with a copper layer by the method described in < laminating >.
The laminate evaluation substrate was exposed to a pattern of 10 μm/10 μm in line/space, and then developed by the method described in < development >. Next, the substrate having the line/space pattern was etched by a dipping method in an aqueous solution containing 2 mass% of hydrochloric acid and 2 mass% of ferric chloride at a temperature of 30 ℃ for a time 1.5 times as long as the minimum etching time. Here, the minimum etching time means a minimum time required to completely dissolve and remove the copper foil on the substrate under the above conditions.
After the etching, the cured film on the substrate was peeled off and removed at a temperature of 50 ℃ using a NaOH aqueous solution having a concentration of 3 mass% as a peeling liquid, and the line pattern of the copper thus obtained was measured and observed by an optical microscope and classified as follows.
O: the copper wire pattern has no defect and high linearity.
X: defects are present in the copper line pattern, and linearity is low.
The evaluation results of examples 1 to 13 and comparative examples 1 to 3 are also shown in Table 1. The comparison of examples 1 to 13 with comparative examples 1 to 3 is considered as follows: the photosensitive resin film having a puncture strength of 70gf or more shows good results in terms of suppression of copper (Cu) defects during etching.
[ Table 1]
Figure BDA0002832058100000501
[ Table 2]
Figure BDA0002832058100000511
[ other aspects of the invention ]
<1 > preparation of photosensitive resin composition >
Photosensitive resin compositions were prepared by mixing the compounds shown in tables 3 to 5. The values in tables 3 to 5 represent the amounts of solid components.
The names of the components, the solvents used, and the like, which are indicated in tables 3 to 5 by short names, are shown in table 6.
The acid value (acid equivalent) of the nonvolatile portion of the photosensitive resin composition is a value calculated from a value measured by NMR.
In this example, the photosensitive resin composition was dissolved in THF, reprecipitated with n-hexane, and separated into a precipitate and a solution side, and the precipitate was dried and solidified. Dissolving the obtained precipitate in deuterated acetone, and performing1H-NMR measurement. The integral value of each component in the precipitate was calculated from the area ratio of each component obtained, and the weight ratio (wt%) of methacrylic acid in the precipitate was calculated from the following formula.
The weight ratio of methacrylic acid (integrated value of methacrylic acid)/(integrated value derived from precipitate component) was totaled)
Further, the acid value of the nonvolatile component of the photosensitive resin composition was calculated from the following formula.
Acid value of nonvolatile component of photosensitive resin composition
{ (weight ratio of methacrylic acid × 1000 × 56/86) × precipitate weight }/weight of photosensitive resin composition dissolved in THF
The method of calculating the acid value (acid equivalent) of the nonvolatile component is exemplified when the acid component contained in the alkali-soluble resin is methacrylic acid. On the other hand, when an acid component other than methacrylic acid is contained as the acid component in the alkali-soluble resin, the acid value (acid equivalent) of the nonvolatile component of the photosensitive resin composition may be measured by the above-mentioned calculation method.
<2 > production of photosensitive resin laminate
Acetone as a solvent was added to the photosensitive resin composition until the solid content reached 58 mass%, the mixture was sufficiently stirred and mixed, and the solution of the photosensitive resin composition was uniformly applied to a polyethylene terephthalate film (FB-40, manufactured by Toray corporation, 16 μm polyethylene terephthalate film) having a thickness of 25 μm as a support film (support) by using a bar coater, and dried in a dryer at 95 ℃ for 5 minutes to form a photosensitive resin layer (dry film) having a thickness of 1 to 20 μm. Subsequently, a polyethylene film (GF-858, manufactured by Tamapy Co.) having a thickness of 33 μm was attached to the surface of the photosensitive resin layer to obtain a photosensitive resin laminate. The thickness of the photosensitive resin layer was measured by using a film thickness meter (ID-C112B, Mitutoyo Co.).
<3. production of evaluation substrate >
(lamination)
The photosensitive resin laminate was laminated on a PET substrate with a copper layer at a roll temperature of 105 ℃ by a hot roll laminator (AL-700, manufactured by Asahi Chemicals Co., Ltd.) while peeling the polyethylene film. The air pressure was set to 0.35MPa, and the lamination speed was set to 1.5 m/min.
(Exposure)
The supporting film was peeled off, and the evaluation substrate was exposed using a chrome glass photomask using an exposure machine (parallel light exposure machine (HMW-801, manufactured by ORC)) equipped with an ultrahigh-pressure mercury lamp.
(development)
Using a developing apparatus manufactured by FUJI machinist, a dense cone type nozzle was used at a spray pressure of 0.15MPa with 1% by mass of Na at 23 deg.C2CO3The aqueous solution was spray-developed for 30 seconds to dissolve and remove the unexposed portion of the photosensitive resin layer. In the water washing step, the treatment was performed for the same time as the developing step using a flat nozzle at a water washing ejection pressure of 0.15 MPa.
(etching)
Using an etching apparatus manufactured by FUJI machinist, a dense cone type nozzle was used to etch for 60 seconds at a spray pressure of 0.15MPa, a temperature of 30 ℃, a hydrochloric acid concentration of 2 mass%, and an iron chloride concentration of 2 mass%.
(peeling)
Using a stripping apparatus manufactured by FUJI machinist, stripping was performed by treating with a NaOH aqueous solution having a concentration of 3% by mass for 30 seconds at a spray pressure of 0.15MPa and a temperature of 50 ℃ using a dense cone type nozzle.
<4. evaluation method >
(image character)
After laminating a photosensitive resin laminate having a photosensitive layer thickness of 1 to 20 μm by the method described in the above (laminating), the evaluation substrate obtained therefrom was exposed through a chrome glass mask having a line pattern with a width ratio of exposed portions to unexposed portions of 1:1 for 15 minutes. Thereafter, the resist pattern was developed by the method described in (development).
The minimum mask width in which the cured resist line to be produced was normally formed was set as a value of resolution, and the resolution was graded as follows. Note that, the width of the minimum mask normally formed without collapse of the cured resist pattern or adhesion of the cured resists was evaluated.
Very good: the resolution value is 2 μm or less.
O: the resolution value exceeds 2 μm and is 3 μm or less.
X: the resolution value exceeds 3 μm.
(amount of lateral erosion (SE))
The following substrates were used for evaluating the amount of undercut: a photosensitive resin laminate having a photosensitive resin layer thickness of 1 to 20 μm was laminated on a PET substrate with a copper layer by the method described in the above (lamination), and the resulting laminate was evaluated after 15 minutes.
The laminate evaluation substrate was exposed to a pattern of 10 μm/10 μm in line/space, and then developed by the method described in (development).
The resist top width Wr (μm) of the pattern thus produced was measured by an optical microscope.
Next, the substrate having the line/space pattern was etched by a dipping method in an aqueous solution containing 2 mass% of hydrochloric acid and 2 mass% of ferric chloride at a temperature of 30 ℃ for a time 1.5 times as long as the minimum etching time. Here, the minimum etching time means a minimum time required to completely dissolve and remove the copper foil on the substrate under the above conditions.
After the etching, the cured film on the substrate was peeled off and removed at a temperature of 50 ℃ using a NaOH aqueous solution having a concentration of 3 mass% as a peeling liquid, and the top width Wc (μm) of the thus obtained copper line pattern was measured by an optical microscope.
Then, the amount of side etching is calculated by the following formula, and the amount of side etching is graded as follows.
Lateral erosion (μm) — (Wr-Wc) ÷ 2
Very good (apparently good): the amount of undercut is 2.5 μm or less.
O (good): the amount of undercut exceeds 2.5 μm and is 3.0 μm or less.
Δ (allowed): the amount of undercut exceeds 3.0 μm and is 3.5 μm or less.
X (bad): the amount of undercut exceeds 3.5 μm.
(evaluation of copper (Cu) Defect)
For the evaluation of copper (Cu) defects, the following substrates were used: a photosensitive resin laminate having a photosensitive resin layer thickness of 1 to 20 μm was laminated on a PET substrate with a copper layer by the method described in the above (lamination), and the resulting laminate was evaluated after 15 minutes.
The laminate evaluation substrate was exposed to a pattern of 10 μm/10 μm in line/space, and then developed by the method described in (development). Next, the substrate having the line/space pattern was etched by a dipping method in an aqueous solution containing 2 mass% of hydrochloric acid and 2 mass% of ferric chloride at a temperature of 30 ℃ for a time 1.5 times as long as the minimum etching time. Here, the minimum etching time means a minimum time required to completely dissolve and remove the copper foil on the substrate under the above conditions.
After the etching, the cured film on the substrate was peeled off and removed at a temperature of 50 ℃ using a NaOH aqueous solution having a concentration of 3 mass% as a peeling liquid, and the line pattern of the copper thus obtained was measured and observed by an optical microscope and classified as follows.
O: the copper wire pattern has no defect and high linearity.
And (delta): the copper wire pattern was slightly defective, and the linearity was slightly lowered.
X: the copper wire pattern has a large number of defects, and linearity is reduced.
(minimum development time)
The method described in the above (laminating) is used to laminate a photosensitive resin laminate having a photosensitive layer thickness of 1 to 20 μm on a copper-clad laminate substrate having a copper foil thickness of 18 μm and a thickness of 0.4mm, thereby obtaining a laminate. After removing the support film laminated on the photosensitive layer, spray development was performed at 23 ℃ for a predetermined time using a 1.0 mass% sodium carbonate aqueous solution.
The surface of the substrate after development was observed, and the time during which no development residue remained was evaluated as the minimum development time according to the following criteria.
Very good (apparently good): the minimum development time is within 15 s.
O (good): the minimum development time is within 20 s.
Δ (allowed): the minimum development time is within 25 s.
X (bad): the minimum development time is within 30 s.
(development residue test of photosensitive layer)
The method described in the above (laminating) is used to laminate a photosensitive resin laminate having a photosensitive layer thickness of 1 to 20 μm on a copper-clad laminate substrate having a copper foil thickness of 18 μm and a thickness of 0.4mm, thereby obtaining a laminate. In N2Stored at 60 ℃ for 3 hours under an atmosphere. The stored substrate was taken out, the support film laminated on the photosensitive layer was removed, and then spray development was performed using a 1.0 mass% aqueous solution of sodium carbonate at 23 ℃ for a minimum development time × 1.2 times. The surface of the substrate after development was observed, and the development residue was evaluated as follows.
O: no development residue was present on the substrate surface.
And (delta): development residue was slightly generated on the substrate surface.
X: developing residue is generated on the surface of the substrate.
The compositions of the photosensitive resin compositions and the evaluation results of the laminates for the examples and comparative examples are shown in tables 3 to 5. The names of the components, solvents used, and the like, which are indicated in tables 3 to 5 by short are shown in table 6.
[ Table 3]
Example 14 Example 15 Example 16 Example 17 Example 18 Example 19 Example 20 Example 21 Example 22 Example 23 Example 24
Component A-1 20 20 20 20 20 20 20 20 20 20 20
Component A-2
Component A-3 20 20 20 20 20 20 20 20 20 20 20
Component A-4
Component A-5
Component A-6
Component B-1 7 7 7 7 7 7 7 7 7 7 7
Component B-2 10 10 10 10 10 10 10 10 10 10 10
Component B-3 10 10 10 10 10 10 10 10 10 10 10
Component B-4
Component B-5
Component B-6 3 3 3 3 3 3 3 3 3 3
Component B-7
Component C-1 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5
Component D-1 12 12 12 6 3 12 12 12
Component D-2 12
Component D-3 12
Component D-4 12
Component E-1 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01
Component E-2
Component F-1 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08
Component G-1 0.14 0.14 0.14 0.14 0.14 0.14 0.14 0.14 0.14 0.14 0.14
Component H-1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1
Acid value (mgKOH/g) 71 68.5 68.5 73.6 76.5 68.5 68.5 68.5 68.5 68.5 68.5
Film thickness (um) 5 5 5 5 5 3 1 7 5 5 5
Acid value/film thickness 14.2 13.7 13.7 14.7 15.3 22.8 68.5 9.8 13.7 13.7 13.7
Minimum development time Δ ○ ○ ◎ ◎ ◎ ◎ Δ ○ ◎ ◎
Resolution ratio ◎ ◎ ◎ ◎ ○ ◎ ◎ ○ ◎ ◎ ◎
SE ◎ ◎ ◎ ○ ○ ◎ ○ ◎ ○ ○ ○
Cu defect ○ ○ ○ Δ Δ ○ ○ ○ ○ Δ Δ
Development residue test ○ ○ Δ ○ ○ ○ ○ ○ ○ ○ ○
[ Table 4]
Practical embodiment 25 Example 26 Example 27 Example 28 Example 29 Example 30 Example 31 Example 32 Example 33 Example 34 Example 35
Component A-1 20 20 20 20 20 20 20 20 20 20 30
Component A-2 20
Component A-3 20 20 20 20 20 20 30
Component A-4 20
Component A-5 20
Component A-6 20
Component B-1 7 7 7 7 7 7 7 7 7 7
Component B-2 10 10 10 10 10 10 10 10 10 10 10
Component B-3 10 10 10 10 10 10 10 10 10 10 10
Component B-4 7
Component B-5 3
Component B-6 3 3 3 3 3 3 3 3 3
Component B-7 3
Component C-1 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5
Component D-1 12 12 12 12 12 12 12 12 12 12 12
Component D-2
Component D-3
Component D-4
Component E-1 0.01 0.01 0.01 0.01 0.07 0.01 0.01 0.01 0.01
Component E-2 0.01
Component F-1 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08
Component G-1 0.14 0.14 0.14 0.14 0.14 0.14 0.14 0.14 0.14 0.14 0.14
Component H-1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1
Acid value (mgKOH/g) 68.5 60.8 63.8 73.9 68.4 68.5 68.5 68.5 68.5 68.5 83.3
Film thickness (um) 5 5 5 5 5 5 5 5 5 5 5
Acid value/film thickness 13.7 12.2 12.8 14.8 13.7 13.7 13.7 13.7 13.7 13.7 16.7
Minimum development time ◎ ◎ ○ ◎ ○ ○ ○ ◎ ○ ○ ◎
Resolution ratio ◎ ◎ ◎ ◎ ◎ ◎ ◎ ○ ◎ ○ ○
SE ◎ ◎ ◎ ◎ ○ ○ ○ ○ ◎ ◎ ○
Cu defect ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○
Development residue test ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○
[ Table 5]
Comparative example 4 Comparative example 5 Comparative example 6 Comparative example 7 Comparative example 8
Component A-1 20 20 40 40 40
Component A-2
Component A-3 20 20 40 40 40
Component A-4
Component A-5
Component A-6
Component B-1 7 7 7 7 7
Component B-2 10 10 10 10 10
Component B-3 10 10 10 22 10
Component B-4
Component B-5
Component B-6 3 3 3 3 3
Component B-7
Component C-1 2.5 2.5 2.5 2.5 2.5
Component D-1 12 12 12 12
Component D-2
Component D-3
Component D-4
Component E-1 0.01 0.01 0.01 0.01 0.01
Component E-2
Component F-1 0.08 0.08 0.08 0.08 0.08
Component G-1 0.14 0.14 0.14 0.14 0.14
Component H-1 0.1 0.1 0.1 0.1 0.1
Acid value (mgKOH/g) 68.5 68.5 93.3 93.3 93.3
Film thickness (um) 20 15 20 20 1
Acid value/film thickness 3.4 4.6 4.7 4.7 93
Minimum development time × × × Δ ◎
Resolution ratio - - - × ○
SE - - - × ×
Cu defect - - - × ×
Development residue test - - - ○ ○
[ Table 6]
Figure BDA0002832058100000601
As can be seen from the table: in comparative examples 4 to 7 in which the ratio (A/T) of the acid value A to the thickness T was less than 5, the minimum development time and the resolution were insufficient. In the case of the film thickness of 20 μm or 15 μm, the developability was not good when the development time was 30 seconds or more, and therefore, other items could not be evaluated. On the other hand, in comparative example 8 in which the ratio (a/T) was greater than 90, although development was possible without PTMG due to a high acid value, Cu defects, resolution, and undercut (SE) were insufficient due to the absence of PTMG. In particular, when the film is thick, the resolution is relatively good by adjusting the acid value to 90mgKOH/g or more, but when the film is thin, the resolution tends to deteriorate.
On the other hand, in the examples in which the ratio (a/T) of the acid value a to the thickness T was 5 or more and 90 or less, sufficiently good results were obtained in the minimum development time, resolution, undercut, Cu defect, and development residue tests.
Industrial applicability
The photosensitive resin composition, the photosensitive resin laminate, and the dry film resist of the present invention can suppress the defect of a pattern formed using them, and therefore can improve the yield of an object or a pattern formed by photolithography, and/or are excellent in the laminatability, minimum development time, resolution, amount of undercut (SE), Cu defect, and development residue, and can be widely used for forming a resist pattern or a wiring pattern.

Claims (27)

1. A dry film resist having a support film and a layer formed on the support film comprising a photosensitive resin composition containing:
(A) alkali soluble resin,
(B) A photopolymerizable compound having an ethylenically unsaturated bond,
(C) Photopolymerization initiator, and
(D) the dye is a mixture of a dye and a water,
characterized in that the weight average molecular weight of the component (A) is 60,000 or less as calculated by using a standard curve of polystyrene by measuring the component (A) by Gel Permeation Chromatography (GPC), and the weight average molecular weight is
The photosensitive resin composition is a photosensitive resin composition having a maximum point load of 70gf or more, the maximum point load being a maximum point load at the time of a puncture test in which a photosensitive resin layer containing the photosensitive resin composition is laminated on a support at a thickness of 25 [ mu ] m to produce a photosensitive resin laminate, the photosensitive resin laminate is laminated on a copper-clad laminate substrate having a 1.6mm thick through hole having a diameter of 6mm on which a copper foil having a thickness of 35 [ mu ] m is laminated, exposure and development are performed to form a cured film, the support is peeled from the cured film, and a portion of the photosensitive resin layer corresponding to the center of the through hole is punctured at a speed of 100 mm/min through a 2.0 mm-diameter cylinder from the surface from which the support is peeled.
2. The dry film resist according to claim 1, wherein the number of double bonds of the photosensitive resin composition is 1.50mmol/g or more based on the solid content of the photosensitive resin composition.
3. The dry film resist according to claim 1, wherein the photosensitive resin composition contains a multifunctional monomer having a trifunctional or higher functionality as the component (B).
4. The dry film resist according to claim 1, wherein the photosensitive resin composition contains, as the component (B), a compound (B-ii) having a skeleton derived from dipentaerythritol and containing no oxyalkylene group, as a polyfunctional monomer having three or more functions.
5. The dry film resist according to claim 4, wherein the photosensitive resin composition further contains (B-iii) a (meth) acrylate compound having a skeleton derived from bisphenol as the difunctional monomer as the component (B).
6. The dry film resist according to any one of claims 1 to 5, wherein the photosensitive resin composition further contains a plasticizer.
7. The dry film resist according to any one of claims 1 to 6, wherein a leuco dye is contained as the dye.
8. The dry film resist according to any one of claims 1 to 7, wherein the maximum point load is less than 250 gf.
9. A dry film resist having a support film and a layer formed on the support film comprising a photosensitive resin composition containing:
(A) alkali soluble resin,
(B) Photopolymerizable compound having ethylenically unsaturated bond, and
(C) a photopolymerization initiator,
the photosensitive resin composition is characterized by containing, as the component (B):
(B-ii) a compound having a skeleton derived from dipentaerythritol and containing no oxyalkylene group as a polyfunctional monomer having three or more functions; and
(B-iii) a (meth) acrylate compound having a skeleton derived from bisphenol as a bifunctional monomer.
10. The dry film resist according to claim 9, wherein the ratio of (B-ii)/(B-iii) is 10 to 80 mass%.
11. The dry film resist according to claim 9 or 10, wherein a ratio of the (B-ii) and the (B-iii) among the component (B) is 50% by mass or more.
12. The dry film resist according to any one of claims 9 to 11, further comprising (B-i) a (meth) acrylate compound having a skeleton derived from dipentaerythritol and comprising an oxyalkylene group as the (B) component.
13. The dry film resist according to any one of claims 9 to 12, wherein the weight average molecular weight of the component (a) is 60,000 or less as calculated using a standard curve of polystyrene, as measured by Gel Permeation Chromatography (GPC).
14. The dry film resist according to any one of claims 9 to 13, wherein the photosensitive resin composition is a photosensitive resin composition having a maximum point load of 70gf or more, the maximum point load being a maximum point load at the time of a puncture test in which a photosensitive resin layer containing the photosensitive resin composition is laminated on a support at a thickness of 25 μm to prepare a photosensitive resin laminate, the photosensitive resin laminate is laminated on a copper-clad laminate substrate having a 1.6mm thick through hole having a diameter of 6mm on which a copper foil having a thickness of 35 μm is laminated, exposure and development are performed to form a cured film, the support is peeled from the cured film, and a portion of the photosensitive resin layer corresponding to the center of the through hole is punctured into a cylinder having a diameter of 2.0mm at a speed of 100 mm/min from a surface from which the support is peeled.
15. The dry film resist according to any one of claims 9 to 14, wherein the number of double bonds of the photosensitive resin composition is 1.50mmol/g or more based on the solid content of the photosensitive resin composition.
16. The dry film resist according to any one of claims 9 to 15, wherein the photosensitive resin composition further contains a plasticizer.
17. The dry film resist according to any one of claims 9 to 16, wherein a leuco dye is contained as the dye.
18. The dry film resist according to any one of claims 9 to 17, wherein the maximum point load is less than 250 gf.
19. A method for forming a resist pattern, comprising the steps of:
a step of laminating the dry film resist according to any one of claims 1 to 18 on a substrate;
exposing the laminated dry film resist; and
and developing the exposed dry film resist.
20. A method for forming a wiring pattern, comprising the steps of:
a step of laminating the dry film resist according to any one of claims 1 to 18 on a substrate;
exposing the laminated dry film resist;
developing the exposed dry film resist to form a resist pattern; and
and performing etching or plating treatment of the substrate on which the resist pattern is formed.
21. A photosensitive resin laminate comprising a support and a photosensitive resin composition layer formed on the support using a photosensitive resin composition comprising (A) an alkali-soluble resin having no ethylenically unsaturated group in the main chain, (B) a photopolymerizable compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator,
when the acid value of the nonvolatile component of the photosensitive resin composition is expressed as A [ mgKOH/g ] and the thickness of the photosensitive resin composition layer is expressed as T [ mu ] m, the ratio of the acid value A to the thickness T, namely A/T, is 5 to 90.
22. The photosensitive resin laminate according to claim 21, further comprising a compound having polyoxytetramethylene group as a structural unit as the component (D).
23. The photosensitive resin laminate according to claim 21 or 22, further comprising a compound having a benzotriazole skeleton as the component (E).
24. The photosensitive resin laminate according to any one of claims 21 to 23, wherein the photosensitive resin composition comprises, as the component (B): a photopolymerizable compound containing an ethylenically unsaturated bond having four or more functions.
25. The photosensitive resin laminate according to claim 22, wherein the ratio of the component (a) to the total of the component (B) and the component (D), i.e., (a) component/((B) component + (D) component), is more than 0 and 1.4 or less.
26. The photosensitive resin laminate according to any one of claims 21 to 25, wherein the weight average molecular weight of the component (A) is 20,000 or more.
27. The photosensitive resin laminate according to any one of claims 21 to 26, wherein an acid value of a nonvolatile component of the photosensitive resin composition, that is, an acid equivalent, exceeds 0 and is 79.0 or less.
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