KR102383138B1 - Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method of manufacturing touch panel - Google Patents

Abstract

[식(1) 중, R¹은 아크릴로일기 또는 메타크릴로일기를 나타낸다. R²는, 히드록실기를 함유하는 알킬렌기 또는 히드록실기를 가지는 폴리옥시알킬렌기를 나타낸다. R³은, 아크릴로일기, 메타크릴로일기, 알킬기 또는 아릴기를 나타낸다.](A) component: binder polymer, (B) component: photopolymerizable compound, and (C) component: (meth)acrylate compound which contains a photoinitiator, and the said (B) component is represented by following General formula (1) A photosensitive resin composition for ITO etching comprising a.

[In formula (1), R ¹ represents an acryloyl group or a methacryloyl group. R ² represents an alkylene group containing a hydroxyl group or a polyoxyalkylene group having a hydroxyl group. R ³ represents an acryloyl group, a methacryloyl group, an alkyl group, or an aryl group.]

Description

The photosensitive resin composition, the photosensitive element, the formation method of a resist pattern, and the manufacturing method of a touch panel TECHNICAL FIELD

The present disclosure relates to a photosensitive resin composition, a photosensitive element, a method for forming a resist pattern, and a method for manufacturing a touch panel.

In the range (view area) for displaying visual information, the touch sensor unit of the touch panel includes a sensor portion that detects position information by contact with a human finger or the like, and a lead-out wiring portion for transmitting position information to an external element. It consists of a set of components.

In the sensor portion, a pattern of electrodes having little absorption and scattering of visible light and having conductivity is formed. In addition, a metal having a small resistance value is used for each wiring in the lead wiring portion.

Such a sensor site|part and a lead-out wiring site|part are manufactured like FIG. 2 using a negative photosensitive resin composition, for example. Moreover, FIG. 2 is a schematic sectional drawing which shows the conventional manufacturing method of the touch sensor part of a touch panel. First, the photosensitive resin composition layer 16 is formed by application of the photosensitive resin composition on a supporting substrate 12 (a film substrate or glass substrate such as polyethylene terephthalate) having a transparent conductive layer 14 . It forms (photosensitive resin composition layer formation process) (FIG.2(a)). Next, actinic light is irradiated to a predetermined part of the photosensitive resin composition layer 16, and an exposure part is hardened (exposure process). Then, by removing an uncured part from on the transparent conductive layer 14, the resist pattern containing the hardened|cured material of the photosensitive resin composition is formed on the transparent conductive layer 14 (development process) (FIG. 2) (b)). The resist pattern is etched to remove a part of the transparent conductive layer 14 from the supporting substrate 12, and a pattern of the transparent conductive layer in the sensor portion is formed (etching step) (Fig. 2(c)). ). Next, the resist is peeled and removed from the transparent conductive layer 14 (peeling process) (FIG.2(d)). Then, in order to produce the lead-out wiring 18 from the pattern of the transparent conductive layer of the formed sensor part, a touch sensor part is manufactured by forming by screen printing using silver paste etc.

Moreover, with the narrowing of the frame (bezel) of a touch panel, narrowing of the wiring width and the pitch in a lead-out wiring site|part is calculated|required. In screen printing using silver paste, pattern formation with L/S (line width/space width) of 70/70 (unit: μm) is the limit, but in order to cope with the narrowing of the frame, L/S is 30/30 ( Unit: [mu]m) The following pattern formation is requested.

In order to manufacture a touch sensor part in which L/S is small as a pattern of outgoing wiring and the pitch of outgoing wiring is narrow, the formation method of the touch sensor part using the technique of photolithography is proposed (for example, refer patent document 1). . In the manufacturing method of this touch sensor part, first, on the support base material which has a transparent conductive layer and a metal layer, using the photosensitive resin composition, the 1st photosensitive resin composition layer is formed (1st photosensitive resin composition) layer forming process). Next, a predetermined portion of the photosensitive resin composition layer is irradiated with actinic light to harden the exposed portion (the first exposure step), and then, the uncured portion is removed from the metal layer, on the metal layer, on the photosensitive resin composition. A resist pattern containing a cured product is formed (first development step). Next, the metal layer and the transparent conductive layer are removed by etching (first etching step). Next, the resist pattern is peeled and removed from the metal layer (first peeling step). Then, a 2nd photosensitive resin composition layer is newly formed on a metal layer using the photosensitive resin composition (2nd photosensitive resin composition layer formation process). Next, a resist pattern is formed on the metal layer by irradiating actinic light to a predetermined portion of the photosensitive resin composition layer to harden the exposed portion (second exposure step), and then removing the uncured portion from the metal layer. (second developing step). Next, only the metal layer on which the unnecessary resist pattern is not formed in the sensor portion is removed by etching (the second etching step), and finally, the resist pattern is peeled off and removed to manufacture the touch sensor portion.

In such a method for manufacturing the touch sensor unit, by using the technique of photolithography, in principle, it is possible to make L/S 30/30 (unit: μm) or less, which greatly contributes to the reduction in thickness and weight of the touch panel. can do. On the other hand, the transparent conductive layer of the touch sensor unit is formed by, for example, forming a film of indium tin oxide (ITO) using a sputtering technique. In addition, the metal layer formed on the transparent conductive layer is formed using the technique of sputtering similarly to a transparent conductive layer, for example. The surfaces of the transparent conductive layer and the metal layer formed using the sputtering technique have very high smoothness. Since the adhesion between the metal layer having very high smoothness and the photosensitive resin composition may be lowered, copper, an alloy of copper and nickel, a molybdenum-aluminum-molybdenum laminate, an alloy of silver, palladium and copper, etc. are used. High adhesiveness is calculated|required of the photosensitive resin composition to be used with respect to a metal layer.

In addition, amorphous ITO is used for a transparent conductive layer from a viewpoint of the easiness of an etching process, for example. Here, since amorphous ITO has a high resistance value, the resistance value is lowered|hung by performing crystallization of ITO by heating (annealing) process, for example. However, using a film base material as a support base material of a touch panel part is calculated|required with thinning and weight reduction of a touch panel in recent years. When a film base material is used as a support base material, dimensional stability deteriorates, such as shrinkage|contraction of a film base material occurring when annealing is performed. Therefore, before forming the pattern of a transparent conductive layer, it is necessary to use crystalline ITO as a transparent conductive layer.

Amorphous ITO can be sufficiently dissolved with a weak acid such as oxalic acid. For crystalline ITO, it is necessary to use a strong acid such as concentrated hydrochloric acid (> 20% by mass) and to etch under heating conditions (about 40 to 50°C). there is Therefore, it is calculated|required by the photosensitive resin composition to be used that adhesiveness with a metal layer can be ensured by high acid resistance, ie, etching using a strong acid, and a metal is hard to be corroded by a strong acid.

As a technique for improving acid resistance (adhesiveness after immersion in a strong acid), a photosensitive resin composition comprising a specific epoxy compound, a photopolymerizable compound, and a photoinitiator as essential components has been proposed (for example, refer to Patent Document 2).

In addition, when the resist pattern L/S is set to 30/30 (unit: mu m) or less and a resist pattern having high resolution is formed, defects such as undulations, defects, and peeling of the resist pattern are likely to occur. Due to the occurrence of the defect, there is a possibility that a short circuit or disconnection may occur in the electrode and the lead wiring in the sensor portion. Therefore, it is calculated|required that undulations, defects, peeling, etc. do not generate|occur|produce in a resist pattern.

In order to reduce the defect of such a resist pattern, various photosensitive resin compositions are examined. For example, adding a specific crosslinking agent, a specific silane coupling agent, etc., using a binder polymer which has a specific structural unit as an essential component, etc. are proposed (for example, refer patent documents 3-7) .

Patent Document 1: Patent No. 4855536 Publication Patent Document 2: Patent No. 4219641 Publication Patent Document 3: Japanese Patent Laid-Open No. 2002-040645 Patent Document 4: Japanese Patent Laid-Open No. 2002-268215 Patent Document 5: Japanese Patent Laid-Open No. 2008-112146 Patent Document 6: Japanese Patent Laid-Open No. 2009-042720 Patent Document 7: Japanese Patent Laid-Open No. 2003-107695

However, since the photosensitive resin composition of patent document 2 has insufficient adhesiveness with a base material, it is difficult to form the resist pattern excellent in resolution, and the defect of a resist pattern may generate|occur|produce. Moreover, defects, such as peeling of a resist, and a defect, may generate|occur|produce in the photosensitive resin composition of patent documents 3-7 at the time of ITO etching. Moreover, when the photosensitive resin composition described in a prior art document evaluated adhesively using the cross-cut test method etc. with difficulty, it may not be able to say that the requested|required performance is fully satisfied.

This indication was made in order to solve such a subject, and an object of this disclosure is to provide the photosensitive resin composition from which the resist pattern excellent in adhesiveness to a base material can be formed.

MEANS TO SOLVE THE PROBLEM The present inventors discovered that the resist pattern excellent in adhesiveness to a base material can be formed by using the photosensitive resin composition for ITO etching containing a predetermined component, as a result of repeating earnest examination in order to solve the said subject. did.

That is, the 1st aspect of this indication contains (A) component: a binder polymer, (B) component: a photopolymerizable compound, and (C) component: a photoinitiator, and said (B) component , It relates to the photosensitive resin composition for ITO etching containing the (meth)acrylate compound represented by following General formula (1).

Here, in general formula (1), R< ¹ > represents an acryloyl group or a methacryloyl group. R ² represents an alkylene group containing a hydroxyl group or a polyoxyalkylene group having a hydroxyl group. R ³ represents an acryloyl group, a methacryloyl group, an alkyl group, or an aryl group.

Since the adhesiveness with respect to the base material which has very high smoothness of such a photosensitive resin composition improves significantly, in the object for ITO etching, the resist pattern excellent in adhesiveness can be formed.

The said (B) component may contain the bisphenol A type|mold di(meth)acrylate compound which has a (poly)oxyethylene group and a (poly)oxypropylene group. According to such a photosensitive resin composition, the acid resistance of a resist improves still more, and peeling by swelling of a resist can be suppressed further remarkably at the time of ITO etching.

The said (B) component may contain the urethane (meth)acrylate compound which has an isocyanurate group. Thereby, it becomes possible to provide flexibility to a resistor, and also improves the acid resistance of a resistor.

A second aspect of the present disclosure relates to a photosensitive element comprising a support and a photosensitive resin composition layer formed using the photosensitive resin composition according to the first aspect provided on one surface of the support. According to such a photosensitive element, since the photosensitive resin composition layer formed using the photosensitive resin composition which concerns on the 1st aspect is provided, since it has outstanding adhesiveness with respect to the board|substrate with high smoothness, it forms the pattern excellent in resolution. it becomes possible to do

A third aspect of the present disclosure is a first step of forming a photosensitive resin composition layer on a substrate by using the photosensitive resin composition according to the first aspect or the photosensitive element according to the second aspect; A second step of curing a part of the photosensitive resin composition layer by irradiation with actinic light to form a cured product region, and removing a region other than the cured product region of the photosensitive resin composition layer from the substrate Thus, it relates to a method of forming a resist pattern, comprising a third step of obtaining a resist pattern comprising the cured product region. According to such a resist pattern formation method, since it has excellent adhesiveness also with respect to the board|substrate with high smoothness, it becomes possible to form the pattern excellent in resolution.

A fourth aspect of the present disclosure is a laminated substrate comprising a supporting substrate, a transparent conductive layer containing indium tin oxide provided on one surface of the supporting substrate, and a metal layer provided on the transparent conductive layer, on the metal layer a first step of forming a resist pattern made of a cured product of the photosensitive resin composition according to the first aspect; and etching the metal layer and the transparent conductive layer to obtain the remainder of the transparent conductive layer and the A second step of forming a laminated pattern composed of the remainder of the metal layer, and removing the metal layer from a part of the laminated pattern to form a transparent electrode composed of the remainder of the transparent conductive layer and a metal wiring composed of the remainder of the metal layer It is related with the manufacturing method of the touch panel which has a 3rd process.

According to such a method for manufacturing a touch panel, since the resist pattern is formed of the photosensitive resin composition layer using the photosensitive resin composition according to the first aspect, peeling of the resist pattern in the etching process is sufficiently suppressed, It is possible to easily and efficiently manufacture a narrow-pitch touch panel (for example, a touch panel having outgoing wiring having an L/S of 30/30 or less).

The transparent conductive layer may contain crystalline indium tin oxide, and the etching by a strong acid may be sufficient as the etching in the said 2nd process. In the manufacturing method, since the resist pattern is formed from the photosensitive resin composition layer using the photosensitive resin composition according to the first aspect, peeling of the resist pattern is sufficiently suppressed even by etching with a strong acid. Therefore, the said manufacturing method is suitably applicable to manufacture of the touchscreen using the laminated|multilayer base material provided with the transparent conductive layer containing crystalline indium tin oxide.

ADVANTAGE OF THE INVENTION According to this indication, the photosensitive resin composition which can form the resist pattern excellent in adhesiveness with respect to the base material with high smoothness is provided. Moreover, according to this indication, the formation method of the photosensitive element using this photosensitive resin composition, a resist pattern, and the manufacturing method of a touch panel are provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic sectional drawing which shows one Embodiment of the photosensitive element of this indication.
2 is a schematic cross-sectional view showing a conventional method for manufacturing a touch panel.
3 is a schematic cross-sectional view showing an aspect of a method for manufacturing a touch panel of the present disclosure;
4 is a top view showing an aspect of a touch panel obtained by using the present disclosure.

Hereinafter, the form for implementing this indication is demonstrated in detail. However, this indication is not limited to the following embodiment. In addition, in this specification, (meth)acrylic acid means acrylic acid or methacrylic acid, and (meth)acrylate means an acrylate or the methacrylate corresponding to it.

In addition, in this specification, the (poly)oxyalkylene group means at least 1 sort(s) of the polyoxyalkylene group which an oxyalkylene group or two or more alkylene groups were connected by the ether bond. The (poly)oxyethylene group means at least one type of polyoxyethylene group in which an oxyethylene group or two or more ethylene groups are connected by an ether bond, and the (poly)oxypropylene group is an oxypropylene group or a poly(poly) group in which two or more propylene groups are connected by an ether bond. It means at least 1 sort(s) of an oxypropylene group. In addition, "EO modified" means that it is a compound which has a (poly)oxyethylene group, "PO modified" means that it is a compound which has a (poly)oxypropylene group, and "EO/PO modified" means that it is (poly) It means that it is a compound which has both an oxyethylene group and a (poly)oxypropylene group. In addition, when the term "layer" observes as a top view, in addition to the structure of the shape formed in the whole surface, the structure of the shape currently formed in part is also included.

In addition, the numerical range shown using "-" represents the range which includes the numerical value described before and after "-" as a minimum value and a maximum value, respectively. In addition, in the numerical range described in stages in this specification, the upper limit or lower limit of the numerical range of one stage may be substituted with the upper limit or lower limit of the numerical range of another stage. In addition, in the numerical range described in this specification, the upper limit or lower limit of the numerical range may be substituted with the value shown in the Example.

<Photosensitive resin composition>

The photosensitive resin composition for ITO etching which concerns on this embodiment (hereinafter, simply referred to as "photosensitive resin composition") is (A) component: binder polymer, (B) component: photopolymerizable compound, and (C) component: It is a photosensitive resin composition containing a photoinitiator and containing the (meth)acrylate compound which has following General formula (1) as (B) component.

Here, in general formula (1), R< ¹ > represents an acryloyl group or a methacryloyl group. R ² represents an alkylene group containing a hydroxyl group or a polyoxyalkylene group having a hydroxyl group. R ³ represents an acryloyl group, a methacryloyl group, an alkyl group, or an aryl group.

According to such a photosensitive resin composition, the resist pattern excellent in the adhesiveness to the base material with high smoothness can be formed. Moreover, even when the resist pattern obtained is a case where ITO is etched using hydrochloric acid, there exists a tendency for peeling or a defect to be hard to generate|occur|produce. Therefore, the photosensitive resin composition which concerns on this embodiment is suitable as an object for ITO etching, and especially for the object for etching of the transparent conductive layer containing crystalline ITO.

As a reason for such an effect to be exhibited, it is thought that the hydroxyl group of the metal layer in the outermost surface of a base material and the hydroxyl group contained in the said General formula (1) express high adhesiveness in order to form a hydrogen bond.

(A) Component: Binder Polymer

The photosensitive resin composition contains at least 1 type of binder polymer as (A) component. As a binder polymer, the polymer obtained by radical polymerization of a polymerizable monomer (monomer) is mentioned, for example.

Examples of the polymerizable monomer (monomer) include (meth)acrylic acid, (meth)acrylic acid ester, styrene, a polymerizable styrene derivative substituted at the α-position or an aromatic ring, acrylamide, acrylamide derivative, acrylonitrile, vinyl alcohol ether compounds, maleic acid, maleic anhydride, maleic acid monoesters, unsaturated carboxylic acid derivatives, and the like. As (meth)acrylic acid ester, (meth)acrylic acid alkylester, (meth)acrylic acid cycloalkyl ester, (meth)acrylic acid benzyl, (meth)acrylic acid benzyl derivative, (meth)acrylic acid furfuryl, (meth)acrylic acid tetrahydrofurfuryl , (meth) acrylate isobornyl, (meth) acrylate adamantyl, (meth) acrylate dicyclopentanyl, (meth) acrylate dimethylaminoethyl, (meth) acrylate diethylaminoethyl, (meth) acrylate glycidyl, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, α-bromoacrylic acid, α-chloroacrylic acid, (meth)acrylic acid dish Clopentenyloxyethyl, (meth)acrylic acid dicyclopentanyloxyethyl, (meth)acrylic acid isobornyloxyethyl, (meth)acrylic acid cyclohexyloxyethyl, (meth)acrylic acid adamantyloxyethyl, (meth)acrylic acid dish Clopentenyloxypropyloxyethyl, (meth)acrylic acid dicyclopentanyloxypropyloxyethyl, (meth)acrylic acid dicyclopentenyloxypropyloxyethyl, (meth)acrylic acid adamantyloxypropyloxyethyl, β-pril (meth)acrylic acid ) acrylic acid, β-styryl (meth)acrylic acid, and the like. Examples of the polymerizable styrene derivative substituted at the α-position or the aromatic ring include vinyltoluene and α-methylstyrene. As an acrylamide derivative, diacetone acrylamide etc. are mentioned. Vinyl-n-butyl ether etc. are mentioned as an ether compound of vinyl alcohol. Monomethyl maleate, monoethyl maleate, monoisopropyl maleate, etc. are mentioned as maleic acid monoester. Examples of the unsaturated carboxylic acid derivative include fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, and propiolic acid. These can be used individually or in combination of 2 or more types arbitrarily.

(A) It is preferable that component has a structural unit derived from (meth)acrylic acid. When component (A) has a structural unit derived from (meth)acrylic acid, the content is excellent in resolution and peelability (resistor peelability after etching), based on the whole quantity of component (A) (100 mass) %, hereinafter the same), preferably 10 mass % to 60 mass %, more preferably 15 mass % to 50 mass %, still more preferably 20 mass % to 35 mass %.

Moreover, it is preferable that (A) component has a structural unit derived from the (meth)acrylic-acid alkylester from a viewpoint in which acryl developability and peelability improve further.

As (meth)acrylic acid alkylester, ester of (meth)acrylic acid and C1-C12 alkyl alcohol is preferable. As such (meth)acrylic acid alkylester, for example, (meth)acrylate methyl, (meth)acrylate, (meth)acrylic acid propyl, (meth)acrylate butyl, (meth)acrylate pentyl, (meth)acrylate hexyl and (meth)acrylic acid 2-ethylhexyl can be mentioned, These can be used individually or in combination of 2 or more types arbitrarily.

When the component (A) has a structural unit derived from alkyl (meth)acrylic acid alkylester, the content is 40% by mass to 90% by mass based on the total amount of the component (A) from the viewpoint of excellent resolution and adhesiveness. It is preferable that they are 50 mass % - 85 mass %, It is more preferable that they are 65 mass % - 80 mass %.

(A) From the point excellent in developability and adhesiveness, as for the acid value of component, it is preferable that they are 90 mgKOH/g - 250 mgKOH/g, It is more preferable that they are 100 mgKOH/g - 240 mgKOH/g, It is 120 mgKOH/g - 235 mgKOH/g It is more preferable, and it is especially preferable that it is 130 mgKOH/g - 230 mgKOH/g.

From the viewpoint of shortening the development time, the acid value is preferably 90 mgKOH/g or more, more preferably 100 mgKOH/g or more, still more preferably 120 mgKOH/g or more, and particularly preferably 130 mgKOH/g or more.

In addition, since the adhesiveness of the hardened|cured material of the photosensitive resin composition improves further, it is preferable that this acid value is 250 mgKOH/g or less, It is more preferable that it is 240 mgKOH/g or less, It is more preferable that it is 235 mgKOH/g or less, It is more preferable that it is 230 mgKOH/g or less Especially preferred. Moreover, when performing solvent image development, it is preferable to adjust in a small amount the polymerizable monomer (monomer) which has carboxyl groups, such as (meth)acrylic acid.

(A) When the weight average molecular weight (Mw) of the component is measured by gel permeation chromatography (GPC) (converted by a calibration curve using standard polystyrene), it is excellent in developability and adhesiveness, it is 10,000 to 20,000 It is preferable, it is more preferable that it is 20000-100000, It is still more preferable that it is 25000-80000, It is especially preferable that it is 30000-60000. From the point of excellent developability, it is preferable that it is 200000 or less, It is more preferable that it is 100000 or less, It is still more preferable that it is 80000 or less, It is especially preferable that it is 60000 or less. From a point excellent in adhesiveness, it is preferable that it is 10000 or more, It is more preferable that it is 20000 or more, It is still more preferable that it is 25000 or more, It is especially preferable that it is 30000 or more.

(A) From a point excellent in resolution and adhesiveness, it is preferable that it is 3.0 or less, It is more preferable that it is 2.8 or less, It is still more preferable that it is 2.5 or less, as for the dispersion degree (weight average molecular weight / number average molecular weight) of component.

(A) As a component, 1 type of binder polymer may be used independently and you may use it combining arbitrarily two or more types of binder polymers.

Content of (A) component in the photosensitive resin composition is 30 mass parts - 70 mass parts in 100 mass parts of total amounts of (A) component and (B) component at the point excellent in film formability, a sensitivity, and resolution It is preferable to set it as mass parts, It is more preferable to set it as 35 mass parts - 65 mass parts, It is especially preferable to set it as 40 mass parts - 60 mass parts. From the point of the formability of a film (photosensitive resin composition layer), it is preferable that this content is 30 mass parts or more, It is more preferable that it is 35 mass parts or more, It is especially preferable that it is 40 mass parts or more. Moreover, it is preferable that it is 70 mass parts or less, and, as for this content, it is more preferable that it is 65 mass parts or less, and it is still more preferable that it is 60 mass parts or less at the point which a sensitivity and a resolution improve in a balanced way.

(B) Component: Photopolymerizable compound

The photosensitive resin composition contains the compound represented by the said General formula (1) as (B) component.

In Formula (1), as an alkylene group which has one or more hydroxyl groups in R< ² >, it is a propylene group and trimethylene represented by the general formula -(CH2) _n- ( _n is an integer of 3-10). The group etc. in which one or more of the hydrogen atoms in a group, a tetramethylene group, etc. were substituted by the hydroxyl group are illustrated. It is preferable that the number of hydroxyl groups is 1 or 2. Further, in R ² , examples of the polyoxyalkylene group having a hydroxyl group include a group in which at least one hydrogen atom in the polyoxyalkylene group to which the above-described alkylene group is bonded by an ether bond is substituted with a hydroxyl group. do.

In Formula (1), in R< ³ >, as an alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, etc. which are a C1-C20 alkyl group are illustrated. In R ³ , examples of the aryl group include a phenyl group and a naphthyl group that are an aryl group having 6 to 10 carbon atoms.

Specific examples of the compound represented by the general formula (1) include 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3-acryroyloxypropyl (meth) acrylate and glycerin di ( meth) acrylate.

(B) It is preferable that component contains other photopolymerizable compounds other than the compound represented by General formula (1) further. There will be no restriction|limiting in particular as long as it is a compound which can photopolymerize other photopolymerizable compounds other than the compound represented by General formula (1). It is preferable that it is a radically polymerizable compound, and, as for other photopolymerizable compounds other than the compound represented by General formula (1), it is more preferable that it is a compound which has an ethylenically unsaturated bond. Examples of the compound having an ethylenically unsaturated bond include a compound having one ethylenically unsaturated bond in a molecule, a compound having two ethylenically unsaturated bonds in a molecule, and a compound having three or more ethylenically unsaturated bonds in a molecule. .

(B) It is preferable that component contains at least 1 sort(s) of the compound which has two ethylenically unsaturated bonds in a molecule|numerator. (B) When component contains the compound which has two ethylenically unsaturated bonds in a molecule|numerator, content of the compound which has two ethylenically unsaturated bonds in a molecule|numerator in 100 mass parts of total amounts of (A) component and (B) component , It is preferable that they are 5 mass parts - 60 mass parts, It is more preferable that they are 5 mass parts - 55 mass parts, It is still more preferable that they are 10 mass parts - 50 mass parts.

Examples of the compound having two ethylenically unsaturated bonds in the molecule include a bisphenol A di(meth)acrylate compound, a hydrogenated bisphenol A di(meth)acrylate compound, and a di(meth) urethane bond in the molecule. ) acrylate compounds, and polyalkylene glycol di(meth)acrylates having both (poly)oxyethylene groups and (poly)oxypropylene groups in the molecule, trimethylolpropane di(meth)acrylates, and the like. .

It is preferable that (B) component contains both the urethane (meth)acrylate compound which has a bisphenol A di(meth)acrylate compound and an isocyanurate group from a viewpoint of improving acid resistance further.

As a bisphenol A type|mold di(meth)acrylate compound, the compound represented by following formula (2) is mentioned.

In formula (2), R ⁴ and R ⁵ each independently represent a hydrogen atom or a methyl group. XO and YO each independently represent an oxyethylene group or an oxypropylene group. m ₁ , m ₂ , n ₁ and n ₂ each independently represent 0-40. However, both m ₁ +n ₁ and m ₂ +n ₂ are 1 or more. When XO is an oxyethylene group and YO is an oxypropylene group, m1 ₊ m2 is _1-40 , and _{n1 +} n2 is 0-20. When XO is an oxypropylene group and YO is an oxyethylene group, m1 ₊ m2 is 0-20, and _{n1 +} n2 is _1-40 . m ₁ , m ₂ , n ₁ and n ₂ represent the number of structural units of the structural unit. Therefore, an integer value is shown for a single molecule, and a rational number that is an average value is shown as an aggregate of a plurality of types of molecules. Hereinafter, it is the same about the number of structural units of a structural unit.

From the point of excellent acid resistance, in Formula (2), it is preferable that m< ₁ >+m< ₂ > is 8-40, It is more preferable that it is 8-20, It is still more preferable that it is 8-10.

When the photosensitive resin composition contains a bisphenol A type di(meth)acrylate compound as (B) component, as content of a bisphenol A type di(meth)acrylate compound, the total amount of (A) component and (B) component 100 It is preferable that they are 1 mass part - 50 mass parts in mass parts, and it is more preferable that they are 5 mass parts - 50 mass parts.

As a urethane (meth)acrylate compound which has an isocyanurate group, the compound represented by the following general formula (3) is mentioned.

In formula (3), R ⁹ , R ¹⁰ and R ¹¹ independently represent a hydrogen atom or a methyl group. l, m, and n are each independently 0-40, and 1+m+n is 1 or more. XO represents an oxyethylene group or an oxypropylene group. 1, m, and n represent the number of structural units of a structural unit.

From a viewpoint of developability and acid resistance, it is preferable that 1+m+n is 3-30, It is more preferable that it is 3-20, It is still more preferable that it is 3-15.

Moreover, as a commercially available thing among the compounds represented by the said General formula (3), UA-21 (The Shin-Nakamura Chemical Co., Ltd. make, brand name) etc. are mentioned.

When the photosensitive resin composition contains the urethane (meth)acrylate compound which has an isocyanurate group as (B) component, as content of the urethane (meth)acrylate compound which has an isocyanurate group, (A) component and ( B) It is preferable that they are 1 mass part - 50 mass parts in 100 mass parts of total amounts of a component, and it is more preferable that they are 5 mass parts - 50 mass parts.

The photosensitive resin composition may further contain the compound which has one ethylenically unsaturated bond in a molecule|numerator in addition to the compound which has two ethylenically unsaturated bonds in a molecule|numerator as (B)component.

Examples of the compound having one ethylenically unsaturated bond in the molecule include nonylphenoxypolyethyleneoxyacrylate, phthalic acid-based compounds and (meth)acrylic acid alkyl esters. Among these, it is preferable to contain at least any 1 type of nonylphenoxy polyethyleneoxy acrylate or a phthalic acid type compound from a viewpoint of improving the resolution, adhesiveness, resist shape, and peeling characteristic after hardening in a balanced way.

Examples of the phthalic acid compound having one ethylenically unsaturated bond in the molecule include γ-chloro-β-hydroxypropyl-β′-methacryloyloxyethyl-o-phthalate, 2-acryloyloxyethyl -2-hydroxyethyl-phthalic acid and 2-acryroyloxyethylphthalic acid are mentioned.

When the photosensitive resin composition contains the compound which has one ethylenically unsaturated bond in a molecule|numerator as (B) component, content of the compound which has one ethylenically unsaturated bond in a molecule|numerator of (A) component and (B) component It is preferable that they are 1 mass part - 30 mass parts in 100 mass parts of total amounts, It is more preferable that they are 3 mass parts - 25 mass parts, It is still more preferable that they are 10 mass parts - 20 mass parts.

It is preferable that content of the whole (B) component in the photosensitive resin composition shall be 30 mass parts - 70 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component, 35 mass parts - 65 mass parts It is more preferable to use it, and it is especially preferable to set it as 35 mass parts - 50 mass parts. When this content is 30 mass parts or more, there exists a tendency for a sensitivity and resolution to improve in a well-balanced way. There exists a tendency for it to become easy to form a film (photosensitive resin composition layer) as it is 70 mass parts or less, and there exists a tendency to become easy to obtain a favorable resist shape.

(C) Component: Photoinitiator

The photosensitive resin composition contains at least 1 type of photoinitiator as (C)component. There will be no restriction|limiting in particular as long as a photoinitiator can superpose|polymerize (B) component, Usually, it can select suitably from the photoinitiator used.

(C) As a component, an aromatic ketone, quinones, a benzoin ether compound, a benzoin compound, a benzyl derivative, a 2,4,5- triaryl imidazole dimer, an acridine derivative, etc. are mentioned. Examples of the aromatic ketone include benzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-methyl-1-[4-(methylthio)phenyl]-2- Morpholino propanone-1 etc. are mentioned. As quinones, an alkyl anthraquinone etc. are mentioned. Benzoin alkyl ether etc. are mentioned as a benzoin ether compound. Benzoin, alkylbenzoin, etc. are mentioned as a benzoin compound. Benzyl dimethyl ketal etc. are mentioned as a benzyl derivative. Examples of the 2,4,5-triarylimidazole dimer include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-fluorophenyl)-4,5- A diphenylimidazole dimer etc. are mentioned. Examples of the acridine derivative include 9-phenylacridine and 1,7-(9,9'-acridinyl)heptane. These can be used individually or in combination of 2 or more types.

(C) It is preferable that a component contains at least 1 sort(s) of a 2,4,5- triaryl imidazole dimer from a viewpoint of improving a sensitivity and adhesiveness further, 2-(o-chlorophenyl)-4 It is more preferable to include a ,5-diphenylimidazole dimer. The structure of the 2,4,5-triaryl imidazole dimer may be symmetrical or asymmetrical may be sufficient as it.

It is preferable that content of (C)component in the photosensitive resin composition is 0.1 mass part - 10 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component, and it is more that they are 1 mass part - 7 mass parts It is preferable, It is more preferable that they are 2 mass parts - 6 mass parts, It is especially preferable that they are 3 mass parts - 5 mass parts. When this content is 0.1 mass part or more, there exists a tendency for a favorable sensitivity, resolution, or adhesiveness to become easy to be acquired, and when it is 10 mass parts or less, there exists a tendency for a favorable resist shape to become easy to be obtained.

(Other ingredients)

The photosensitive resin composition may contain components other than the said (A)-(C)component as needed. For example, the photosensitive resin composition is selected from the group consisting of a silane coupling agent, a sensitizing dye, bis[4-(dimethylamino)phenyl]methane, bis[4-(diethylamino)phenyl]methane, and leuco crystal violet. It may contain at least 1 type.

(D)Component: Silane coupling agent

The photosensitive resin composition may further contain a silane coupling agent as (D)component. As the silane coupling agent, (D1) component: a silane compound having a mercaptoalkyl group, (D2) component: a silane compound having an amino group (preferably a silane compound having a ureido group), (D3) component: (meth)acryl and a silane compound having a hydroxy group.

By using component (D1) as component (D), the photosensitive resin composition has excellent adhesion to a substrate with high smoothness and excellent acid resistance that is difficult to cause peeling or the like even by ITO etching with hydrochloric acid It can form a resist pattern. It shows the excellent effect that it can be said.

Moreover, the photosensitive resin composition may contain silane coupling agents other than (D1) component as (D)component.

For example, the photosensitive resin composition can use together (D1)component and (D3)component as (D)component. When the photosensitive resin composition contains only the (D1) component as the (D) component, a resist exhibiting excellent adhesion can be obtained, while developing residues on the copper substrate or the like are easy to occur (that is, formed on the copper substrate) The resist tends to be difficult to peel off after etching), and the etching time tends to be increased. On the other hand, when the photosensitive resin composition contains (D1) component and (D3) component as (D)component, generation|occurrence|production of the image development residue with respect to a copper substrate etc. is suppressed while maintaining outstanding adhesiveness, and shortening of etching time is aimed at can do.

Moreover, the photosensitive resin composition may contain all the (D1) component, (D2) component, and (D3) component as (D)component. According to such a photosensitive resin composition, higher adhesiveness can be implement|achieved, suppressing generation|occurrence|production of the image development residue with respect to a copper substrate etc.

(D1) As a component, the silane compound (mercaptoalkyl alkoxysilane) which has a mercapto alkyl group and an alkoxy group is preferable, As such (D1) component, mercaptopropylmethyldimethoxysilane, mercaptopropyltrimethoxysilane and mercaptopropyltriethoxysilane. Among these, the mercaptopropyl trimethoxysilane which hydrolysis occurs easily and which can crosslink at 3 points|pieces is most preferable with respect to adhesive expression.

(D2) As a component, the silane compound which has a primary amino group at the terminal is preferable, As such (D2) component, 3-aminopropyl methoxysilane, aminopropyl ethoxysilane, N-2-( Aminoethyl)-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, ureidomethyltrimethoxysilane, ureidomethyltriethoxysilane, 2 -Ureidoethyltrimethoxysilane, 2-ureidoethyltriethoxysilane, 4-ureidobutyltrimethoxysilane, 4-ureidobutyltriethoxysilane, etc. are mentioned. Among these, in consideration of the reactivity with the binder polymer, a silane compound having a low reactivity with a carboxylic acid group such as a ureido group is preferable, and when used in combination with component (D1), the effect of inhibiting the development residue is particularly remarkable. Most preferred is 3-ureidopropyltriethoxysilane.

(D3) As a component, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltri and ethoxysilane. Among these, 3-methacryloxypropyl trimethoxysilane which is easy to raise|generate hydrolysis and which can bridge|crosslink at 3 points|pieces is most preferable with respect to adhesive expression.

It is preferable that content of (D)component in the photosensitive resin composition is 0.01 mass part - 10 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component from the point excellent in adhesiveness, 0.05 mass It is more preferable that they are parts - 5 mass parts, and it is still more preferable that they are 0.1 mass parts - 3 mass parts. (D) There exists a tendency for sclerosis|hardenability in a resist bottom part to be improved, fully suppressing the image development residue with respect to a copper substrate etc. as content of a component is in the said range. By fully hardening to a resist bottom part, while a favorable resist shape is obtained, the tolerance with respect to an etching liquid becomes still more favorable.

(E) Ingredient: sensitizing dye

It is preferable that the photosensitive resin composition further contains a sensitizing dye as (E) component. As a sensitizing dye, it is a dialkylamino benzophenone compound, a pyrazoline compound, an anthracene compound, a coumaline compound, a xanthone compound, a thioxanthone compound, an oxazole compound, a benzoxazole compound, a thiazole compound, benzothia, for example. A sol compound, a triazole compound, a stilbene compound, a triazine compound, a thiophene compound, a naphthalimide compound, a triarylamine compound, and an amino acridine compound are mentioned. These can be used individually or in combination of 2 or more types. It is preferable to contain a pyrazoline compound from a viewpoint of further improving the hardening degree of a resistor bottom part and being excellent in adhesiveness.

It is preferable to add 0.01-5 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component from a viewpoint of improving the hardening degree of a resist bottom part and improving adhesiveness further, 0.01-1 mass part addition It is more preferable to do it, and it is especially preferable to add 0.01-0.2 mass part.

In addition, the photosensitive resin composition includes a polymerizable compound (such as an oxetane compound) having at least one cationically polymerizable cyclic ether group in the molecule, a cationic polymerization initiator, a dye, a photochromic agent, a thermal color development inhibitor, a plasticizer, a pigment, It may contain a filler, an antifoaming agent, a flame retardant, a stabilizer, an adhesion-imparting agent, a leveling agent, a peeling accelerator, antioxidant, a fragrance|flavor, an imaging agent, a thermal crosslinking agent, etc. These can be used individually or in combination of 2 or more types. Examples of the dye include malachite green, victoria pure blue, brilliant green, and methyl violet. Examples of the photochromic agent include tribromophenylsulfone, diphenylamine, benzylamine, triphenylamine, diethylaniline and o-chloroaniline. Examples of the plasticizer include p-toluenesulfonamide.

When the photosensitive resin composition contains other components (components other than (A)-(D) component), these content is 0.01 mass each with respect to 100 mass parts of total amounts of (A) component and (B) component, respectively It is preferable to set it as part - about 20 mass parts.

[Solution of photosensitive resin composition]

The photosensitive resin composition may be a liquid composition further containing at least 1 sort(s) of an organic solvent. As an organic solvent, an alcohol solvent, a ketone solvent, a glycol ether solvent, an aromatic hydrocarbon solvent, aprotic polar solvent, etc. are mentioned. As an alcohol solvent, methanol, ethanol, etc. are mentioned. Acetone, methyl ethyl ketone, etc. are mentioned as a ketone solvent. Examples of the glycol ether solvent include methyl cellosolve, ethyl cellosolve, and propylene glycol monomethyl ether. Toluene etc. are mentioned as an aromatic hydrocarbon solvent. Examples of the aprotic polar solvent include N,N-dimethylformamide and the like. These may be used individually or in mixture of 2 or more types.

Content of the organic solvent contained in the photosensitive resin composition can be suitably selected according to the objective etc. For example, the photosensitive resin composition can be used as a liquid composition (henceforth the photosensitive resin composition containing an organic solvent is also called "coating liquid") from which solid content becomes about 30 mass % - 60 mass %.

The photosensitive resin composition layer which is a coating film of the photosensitive resin composition can be formed by apply|coating a coating liquid on surfaces, such as a support body and a metal plate mentioned later, and drying it. There is no restriction|limiting in particular as a metal plate, According to the objective etc., it can select suitably. As a metal plate, the metal plate which consists of metals, such as iron-type alloys, such as copper, a copper-type alloy, nickel, chromium, iron, and stainless steel, is mentioned. As a preferable metal plate, the metal plate which consists of metals, such as copper, a copper-type alloy, and an iron-type alloy, is mentioned.

The thickness in particular of the photosensitive resin composition layer to be formed is not restrict|limited, According to the use, it can select suitably. It is preferable that the thickness (thickness after drying) of the photosensitive resin composition layer is about 1 micrometer - about 100 micrometers.

When the photosensitive resin composition layer is formed on a metal plate, you may coat|cover the surface on the opposite side to the metal plate of the photosensitive resin composition layer with a protective layer. As a protective layer, polymer films, such as polyethylene and a polypropylene, etc. are mentioned.

<Photosensitive element>

The photosensitive element (hereinafter, simply referred to as "photosensitive element") according to the present embodiment includes a support and a photosensitive resin composition layer formed using the photosensitive resin composition provided on one surface of the support. According to such a photosensitive element, since the photosensitive resin composition layer formed using the photosensitive resin composition is provided, a resist pattern having sufficient adhesion to a substrate with high smoothness and excellent acid resistance can be efficiently formed. there is. The photosensitive element may have other layers, such as a protective layer, as needed.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic sectional drawing which shows one Embodiment of the photosensitive element of this indication. In the photosensitive element 10 shown in FIG. 1, the support body 2, the photosensitive resin composition layer 4 formed using the photosensitive resin composition, and the protective layer 6 are laminated|stacked in this order. The photosensitive resin composition layer 4 can also be called a coating film of the photosensitive resin composition. In addition, as for a coating film, the photosensitive resin composition is a thing of a non-hardened state.

The photosensitive element 10 can be obtained as follows, for example. On the support 2, a coating liquid, which is a photosensitive resin composition containing an organic solvent, is applied to form an application layer, and the photosensitive resin composition layer 4 is formed by drying (removing at least a part of the organic solvent from the application layer). to form Next, by covering the surface of the photosensitive resin composition layer 4 on the opposite side to the support 2 with the protective layer 6, the support 2 and the photosensitive resin composition layer 4 laminated on the support 2 And the photosensitive element 10 provided with the protective layer 6 laminated|stacked on the photosensitive resin composition layer 4 can be obtained. In addition, the photosensitive element 10 does not necessarily need to be equipped with the protective layer 6 .

As the support body 2, a film made of a polymer having heat resistance and solvent resistance such as polyester and polyolefin can be used. Polyethylene terephthalate etc. are mentioned as polyester. Polypropylene, polyethylene, etc. are mentioned as polyolefin.

It is preferable that they are 1 micrometer - 100 micrometers, as for the thickness of the support body 2, it is more preferable that they are 5 micrometers - 50 micrometers, It is more preferable that they are 5 micrometers - 30 micrometers. When the thickness of the support body 2 is 1 micrometer or more, when peeling the support body 2, it can suppress that the support body 2 is torn. Moreover, when it is 100 micrometers or less, the fall of the resolution is suppressed.

As the protective layer 6, it is preferable that the adhesive force with respect to the photosensitive resin composition layer 4 is smaller than the adhesive force with respect to the photosensitive resin composition layer 4 of the support body 2. Specifically, as the protective layer 6, a film made of a polymer having heat resistance and solvent resistance, such as polyester or polyolefin, can be used. Polyethylene terephthalate etc. are mentioned as polyester. Polypropylene, polyethylene, etc. are mentioned as polyolefin. As a commercially available thing, polypropylene films, such as Alpan MA-410 and E-200 made by Oji Seishi Co., Ltd., made by Shin-Etsu Film Co., Ltd., PS series polyethylene terephthalate, such as PS-25 made by Teijin Co., Ltd. A phthalate film, NF-15A of Tamapoli is mentioned. In addition, the protective layer 6 may be the same as that of the support body 2 .

The thickness of the protective layer 6 is preferably 1 µm to 100 µm, more preferably 5 µm to 50 µm, still more preferably 5 µm to 30 µm, and particularly preferably 15 µm to 30 µm. . When the thickness of the protective layer 6 is 1 μm or more, the protective layer 6 is torn when the photosensitive resin composition layer 4 and the support 2 are laminated on the substrate while the protective layer 6 is peeled off. can be restrained If it is 100 micrometers or less, it is excellent in handleability and cheapness.

The photosensitive element 10 can be specifically manufactured, for example as follows. A step of preparing a coating solution containing the photosensitive resin composition, a step of applying the coating solution on the support (2) to form an application layer, and drying the coating layer to form a photosensitive resin composition layer (4) It can be manufactured by a manufacturing method including a process.

Coating of the coating liquid on the support body 2 can be performed by known methods such as roll coating, comma coating, gravure coating, air knife coating, die coating, and bar coating.

The drying of the application layer is not particularly limited as long as at least a part of the organic solvent can be removed from the application layer. For example, it is preferable to carry out at 70 degreeC - 150 degreeC for about 5 minutes - 30 minutes. After drying, it is preferable that the amount of the organic solvent remaining in the photosensitive resin composition layer 4 shall be 2 mass % or less from a viewpoint of preventing the diffusion of the organic solvent in a subsequent process.

The thickness of the photosensitive resin composition layer 4 in the photosensitive element 10 can be suitably selected according to a use. As thickness after drying, it is preferable that they are 1 micrometer - 100 micrometers, It is more preferable that they are 1 micrometer - 50 micrometers, It is still more preferable that they are 5 micrometers - 40 micrometers. When the thickness of the photosensitive resin composition layer 4 is 1 micrometer or more, industrial coating becomes easy. If it is 100 micrometers or less, there exists a tendency for adhesiveness and resolution to be fully acquired.

The shape of the photosensitive element 10 is not particularly limited. For example, a sheet shape may be sufficient and the shape wound up in roll shape to the core may be sufficient. When winding up in roll shape, it is preferable to wind up so that the support body 2 may become an outer side. Examples of the winding core include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and ABS resin (acrylonitrile-butadiene-styrene copolymer). In the end face of the roll-shaped photosensitive element roll obtained in this way, it is preferable to provide an end face separator from the standpoint of end face protection, and it is preferable to provide a moisture proof end face separator from the standpoint of edge fusion resistance. As a packing method, it is preferable to wrap with a black sheet with low moisture permeability and to pack.

The photosensitive element 10 can be suitably used for the formation method of the resist pattern mentioned later, for example.

<Method of forming resist pattern>

The method for forming a resist pattern according to the present embodiment includes (i) a photosensitive resin composition layer forming step of forming a photosensitive resin composition layer on a substrate using a photosensitive resin composition or a photosensitive element, (ii) a photosensitive resin composition layer an exposure step of curing a part of the region by irradiation with actinic light to form a cured product region, (iii) removing a region other than the cured product region of the photosensitive resin composition layer from the substrate, It has a developing process of forming the resist pattern which consists of hardened|cured material (hardened|cured material area|region) of a resin composition. The method of forming the resist pattern may further include other steps as needed. Hereinafter, each process is demonstrated in detail.

(i) photosensitive resin composition layer forming step

In the photosensitive resin composition layer forming process, the photosensitive resin composition layer is formed on a base material using the photosensitive resin composition.

As a method of forming the photosensitive resin composition layer on a base material, after apply|coating the coating liquid containing the photosensitive resin composition on a base material, for example, the method of drying is mentioned.

Moreover, as a method of forming the photosensitive resin composition layer on a base material, for example, after removing a protective layer from a photosensitive element as needed, the method of laminating the photosensitive resin composition layer of the photosensitive element on a base material is mentioned. Lamination can be performed by crimping|bonding to a base material, heating the photosensitive resin composition layer of a photosensitive element. By this lamination, the laminated body in which the base material, the photosensitive resin composition layer, and the support body were laminated|stacked in this order can be obtained.

Lamination is preferably performed at a temperature of, for example, 70° C. to 130° C., and preferably performed by crimping at a pressure of about 0.1 MPa to 1.0 MPa (about 1 kgf/cm ² to 10 kgf/cm ² ). Such conditions can be suitably adjusted as needed. When laminating, the base material may be preheated, and the photosensitive resin composition layer may be heated at 70 degreeC - 130 degreeC.

(ii) exposure process

At an exposure process, by irradiating actinic light to a part of area|region of the photosensitive resin composition layer, the exposure part irradiated with actinic light is photocured, and a latent image is formed. Here, when a photosensitive element is used in the photosensitive resin composition layer forming step, a support is present on the photosensitive resin composition layer, but when the support has transmittance to actinic light, actinic light can be irradiated through the support. On the other hand, when a support body shows light-shielding property with respect to actinic light, after removing a support body, actinic light is irradiated to the photosensitive resin composition layer.

As an exposure method, the method (mask exposure method) of irradiating actinic light in an image image through the negative or positive mask pattern called artwork is mentioned. Moreover, you may employ|adopt the method of irradiating actinic light into an image by direct drawing exposure methods, such as an LD1 (Laser Direct Imaging) exposure method and a DLP (Digital Light Processing) exposure method.

The wavelength (exposure wavelength) of the actinic light is preferably within the range of 340 nm to 430 nm, more preferably within the range of 350 nm to 420nm, from the viewpoint of more reliably obtaining the effects of the present disclosure.

(iii) development process

In the developing step, regions other than the cured product region of the photosensitive resin composition layer (that is, the uncured portion of the photosensitive resin composition layer) are removed from the substrate by developing treatment to form a resist pattern made of the cured product of the photosensitive resin composition layer. formed on the substrate. In addition, when a support body exists on the photosensitive resin composition layer which passed through the exposure process, after removing a support body, the image development process is implemented. Although there exist wet image development and dry image development in a developing process, wet image development is used suitably.

In wet image development, it develops by a well-known image development method using the developing solution corresponding to the photosensitive resin composition. As a developing method, the method using a dip method, a paddle method, a spray method, brushing, slapping, scraping, swing immersion, etc. is mentioned, From a viewpoint of resolution improvement, the high pressure spray method is the most suitable. You may develop combining these 2 or more types of methods.

A developing solution can be suitably selected according to the structure of the photosensitive resin composition. Examples of the developer include an alkaline aqueous solution, an aqueous developer, and an organic solvent developer.

As alkaline aqueous solution used for image development, 0.1 mass % - 5 mass % sodium carbonate solution, 0.1 mass % - 5 mass % potassium carbonate solution, 0.1 mass % - 5 mass % sodium hydroxide solution, 0.1 mass % - 5 mass % sodium tetraborate solution A solution or the like is preferred. The pH of the alkaline aqueous solution is preferably in the range of 9 to 11. In addition, the temperature is adjusted according to the alkali developability of the photosensitive resin composition layer. In the alkaline aqueous solution, a surface active agent, an antifoaming agent, or a small amount of an organic solvent for accelerating image development may be mixed.

In the resist pattern formation method, after removing the unexposed portion, the resist pattern is further cured by heating at about 60°C to 250°C and/or exposing at about 0.2J/cm ² to 10J/cm ² if necessary. You may have a further process.

<Method for manufacturing touch panel>

The manufacturing method of the touch panel which concerns on this embodiment has the process of etching the base material in which the resist pattern was formed by the said resist pattern formation method. An etching process is performed with respect to the conductor layer of a base material, etc. using the formed resist pattern as a mask. A touch panel is manufactured by forming the pattern of lead wiring and a transparent electrode by an etching process.

3 is a schematic cross-sectional view showing an aspect of a method for manufacturing a touch panel of the present disclosure. The manufacturing method of this aspect is a laminated base material provided with the support base material 22, the transparent conductive layer 24 provided on one surface of the support base material 22, and the metal layer 26 provided on the transparent conductive layer 24. A first step of forming a resist pattern 29 made of a cured product of the photosensitive resin composition on the metal layer 26, etching the metal layer 26 and the transparent conductive layer 24, A second step of forming a laminated pattern (24+26 in Fig. 3(d)) composed of the remainder of 24) and the remainder of the metal layer 26, and removing the metal layer from a part of the laminated pattern, thereby forming the transparent conductive layer 24 ) has a third step of forming a transparent electrode composed of the remainder of the metal layer and a metal wiring composed of the remainder of the metal layer.

In a 1st process, first, as shown to Fig.3 (a), the transparent conductive layer 24 provided on the support base material 22, the transparent conductive layer 24 provided on one surface of the support base material 22, and the transparent conductive layer 24 top The photosensitive resin composition layer 28 is formed using the photosensitive resin composition on the metal layer 26 of the laminated base material provided with the metal layer 26 provided. The photosensitive resin composition layer 28 may be equipped with the support body on the surface on the opposite side to the metal layer 26. As shown in FIG.

Examples of the metal layer 26 include a metal layer made of copper, an alloy of copper and nickel, a molybdenum-aluminum-molybdenum laminate, an alloy of silver, palladium, and copper, and the like. Among these, the metal layer containing copper or the alloy of copper and nickel can be used suitably from a viewpoint from which the effect of this indication is acquired still more notably.

The transparent conductive layer 24 contains indium tin oxide (ITO). It is preferable that the transparent conductive layer 24 contains crystalline ITO from a viewpoint that annealing process becomes unnecessary.

Next, a part of the region of the photosensitive resin composition layer 28 is cured by irradiation of actinic light to form a cured product region, and regions other than the cured product region of the photosensitive resin composition layer are removed from the laminated substrate. Thereby, as shown in FIG.3(b), the resist pattern 29 is formed on the laminated base material.

In a 2nd process, the metal layer 26 and the transparent conductive layer 24 of the area|region which are not masked by the resist pattern 29 are removed from the support base material 22 by an etching process.

The etching method is appropriately selected depending on the layer to be removed. For example, as an etching liquid for removing a metal layer, a cupric chloride solution, a ferric chloride solution, a phosphoric acid solution, etc. are mentioned. In addition, oxalic acid, hydrochloric acid, aqua regia, etc. are used as an etching liquid for removing a transparent conductive layer.

When the transparent conductive layer 24 contains crystalline ITO, it is necessary to use a strong acid such as concentrated hydrochloric acid as an etchant for removing the transparent conductive layer 24. In the manufacturing method of this aspect, the resist pattern Since it consists of a hardened|cured material of the said photosensitive resin composition, peeling of a resist pattern, etc. are fully suppressed even under the etching process by strong acid.

FIG. 3( c ) is a view showing after etching treatment, in FIG. 3( c ), the remainder of the metal layer 26 , the remainder of the transparent conductive layer 24 , and the resist pattern 29 on the support substrate 22 . A laminate made of the remainder of is formed. In the manufacturing method of this aspect, the resist pattern 29 is removed from this laminated body.

For the removal of the resist pattern 29, for example, an aqueous solution that is more alkaline than the alkaline aqueous solution used in the above-described developing step can be used. As this strongly alkaline aqueous solution, 1-10 mass % sodium hydroxide aqueous solution, 1-10 mass % potassium hydroxide aqueous solution, etc. are used. Especially, it is preferable to use 1-10 mass % sodium hydroxide aqueous solution or potassium hydroxide aqueous solution, and it is more preferable to use 1-5 mass % sodium hydroxide aqueous solution or potassium hydroxide aqueous solution. As a peeling method of a resist pattern, an immersion method, a spray method, etc. are mentioned, These may be used individually or may be used together.

Fig. 3(d) is a view showing after resist pattern peeling, and in Fig. 3(d), a laminated pattern composed of the remainder of the metal layer 26 and the remainder of the transparent conductive layer 24 on the support substrate 22 . is formed.

In the third step, a transparent electrode composed of the remainder of the metal wiring of the metal layer 26 and the remainder of the transparent conductive layer 24 by removing a portion of the metal layer 26 for forming the metal wiring from this lamination pattern. to form In addition, in this aspect, although the method of performing etching is employ|adopted as a method of removing the metal layer 26 in a 3rd process, the method of removing the metal layer 26 in a 3rd process is not necessarily limited to etching. .

At a 3rd process, first, the photosensitive resin composition layer 30 is formed on the laminated base material which passed through the 2nd process (FIG.3(e)). Next, through exposure and development of the photosensitive resin composition layer 30, the resist 31 which consists of a hardened|cured material of the photosensitive resin composition layer 30 is formed (FIG.3(f)). In addition, the layer containing the photosensitive resin composition which concerns on this embodiment mentioned above may be sufficient as the photosensitive resin composition layer, and the layer containing the conventionally well-known photosensitive resin composition for etchings may be sufficient as it.

Next, the metal layer 26 is removed from the part in which the resist 31 is not formed in the lamination|stacking pattern by an etching process. At this time, the same thing as the etching liquid for removing the above-mentioned metal layer can be used as an etching process liquid.

Fig. 3(g) is a view showing after etching treatment, and in Fig. 3(g), a transparent electrode made of the remainder of the transparent conductive layer 24 is formed on the supporting base material 22, and a part of the transparent electrode is formed. A laminate comprising a metal layer 26 and a resist 31 is formed on the transparent electrode. By removing the resist 31 from this laminate, as shown in FIG. A metal wiring consisting of the negative is formed.

4 : is a top view which shows one aspect of the touch panel obtained using this indication. In the touch panel 100, the X electrodes 52 and the Y electrodes 54, which are transparent electrodes, are alternately arranged side by side, and the X electrodes 52 provided in the same column in the longitudinal direction are connected to one lead wire 56. Each of the Y electrodes 54 provided in the same column in the width direction are respectively connected by a single lead-out wiring 57 .

As mentioned above, although preferred embodiment of this indication was described, this indication is not limited to the said embodiment.

Example

Hereinafter, although an Example demonstrates this indication in more detail, this indication is not limited to an Example.

(Preparation Example 1: Preparation of Binder Polymer (A-1))

A solution obtained by mixing 30 g of methacrylic acid as a polymerizable monomer (monoma), 35 g of methyl methacrylate, and 35 g of butyl methacrylate (mass ratio of 30/35/35), 0.5 g of azobisisobutyronitrile, and 10 g of acetone was called "solution a". A solution obtained by dissolving 0.6 g of azobisisobutyronitrile in 30 g of acetone was referred to as "solution b".

Into a flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel and a nitrogen gas introduction tube, 100 g of a mixed solution (mass ratio of 4:1) of 80 g of acetone and 20 g of propylene glycol monomethyl ether (mass ratio: 4:1) is introduced, and nitrogen gas is blown into the flask and stirred. While heating, it heated up to 80 degreeC.

The solution a was added dropwise to the mixture in the flask at a constant dropping rate over 4 hours, and then the solution in the flask was stirred at 80 DEG C for 2 hours. Then, the solution b was added dropwise to the solution in the flask at a constant dropping rate over 10 minutes, and then the solution in the flask was stirred at 80 DEG C for 3 hours. Further, the temperature of the solution in the flask was raised to 90 DEG C over 30 minutes, kept at 90 DEG C for 2 hours, and then cooled to obtain a solution of a binder polymer (A-1).

The nonvolatile matter (solid content) of the binder polymer (A-1) was 42.8 mass %, the weight average molecular weight was 50000, the acid value was 195 mgKOH/g, and the dispersion degree was 2.58.

In addition, the weight average molecular weight and dispersion degree were measured by the gel permeation chromatography method (GPC), and were derived|led-out by converting using the analytical curve of standard polystyrene. The conditions of GPC are shown below.

GPC conditions

Pump: Hitachi/L-6000 type (manufactured by Hitachi, Ltd.)

Column: Total of 3 below, Column specification: 10.7mmΦ×300mm

Gelpack GL-R440

Gelpack GL-450

Gelpack GL-R400M (above, made by Hitachi, Ltd., brand name)

Eluent: tetrahydrofuran (THF)

Sample concentration: 120 mg of a resin solution having a solid content of 40% by mass was collected and dissolved in 5 mL of THF to prepare a sample.

Measuring temperature: 40℃

Injection volume: 200 μL

Pressure: 49Kgf/cm ² (4.8 MPa)

Flow: 2.05 mL/min

Detector: Hitachi L-3300 type RI (manufactured by Hitachi, Ltd.)

An Example and a comparative example were implemented with the following method.

(Preparation of photosensitive resin composition (coating liquid))

By mixing each component shown in Table 1 with the compounding quantity (mass part) shown in a compounding table, the coating liquid of the photosensitive resin composition of an Example and a comparative example was obtained. The compounding quantity of (A) component in a table|surface is the mass (solid content) of a non-volatile matter. In addition, "-" means unmixed. The detail of each component shown in Table 1 is as follows.

((A) component)

A-1: Binder polymer (A-1) obtained in Preparation Example 1

((B) component)

FA-321M: 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (manufactured by Hitachi Sei Co., Ltd., trade name)

UA-11: polyoxyethylene urethane dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name)

UA-131: polyoxyethylene polyoxypropylene urethane dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name)

UA-21: tris (methacryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name)

FA-3200MY: polyoxyalkylenated bisphenol A dimethacrylate (manufactured by Hitachi, Ltd., trade name)

R-128H: 2-hydroxy-3-phenoxypropyl acrylate (manufactured by Nippon Gayaku Co., Ltd., trade name)

FA-MECH: γ-chloro-β-hydroxypropyl-β′-methacryloyloxyethyl-o-phthalate (manufactured by Hitachi Chemical Co., Ltd., trade name)

((C)component)

B-CIM: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (manufactured by Hampford, trade name)

((D)component: silane coupling agent)

AY43-031: 3-Ureidopropylethoxysilane (Toray Dow Corning Co., Ltd., trade name)

KBM-803: 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name)

SZ-6030: methacryloxypropyl trimethoxysilane (Toray Dow Corning Co., Ltd. make, brand name)

((E) component: sensitizing dye)

EAB: 4,4'-bis(diethylamino)benzophenone (manufactured by Hodogaya Chemical Co., Ltd., trade name)

PZ-501D: 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)pyrazoline

(Other components: other than (A) to (E) components)

LCV: Roico Crystal Violet (manufactured by Yamada Chemical Co., Ltd., trade name)

TBC: 4-t-butylcatechol (manufactured by DIC Corporation, trade name "DIC-TBC-5P")

F-806P: bis(N,N-2-ethylhexyl)aminomethyl-5-carboxy-1,2,3-benzotriazole (manufactured by Sanwagasei Co., Ltd., trade name)

AZCV-PW: [4-bis(4-dimethylaminophenyl)methylene｝-2,5-cyclohexadiene-1-iridene] (Hodogaya Chemical Co., Ltd., trade name)

<Production of photosensitive element>

The coating liquid of the photosensitive resin composition obtained above was applied to a uniform thickness on a polyethylene terephthalate film (manufactured by Toray Corporation, product name "FB-40") having a thickness of 16 µm, respectively, at 70 ° C. and 110 ° C. It dried sequentially with a hot-air convection dryer, and the film thickness after drying formed the photosensitive resin composition layer whose film thickness is 15 micrometers. A protective layer (manufactured by Tamapoli Co., Ltd., product name "NF-15A") is pasted on this photosensitive resin composition layer, and a polyethylene terephthalate film (support body), a photosensitive resin composition layer, and a protective layer are laminated in this order. A photosensitive element was obtained.

<Production of laminated substrate>

A transparent conductive layer made of crystalline ITO was formed on the upper layer of the polyethylene terephthalate material, and a metal layer made of copper was formed on the upper layer, and the outermost surface of the metal layer was provided with a film base material subjected to a rust prevention treatment. After heating this film base material (hereinafter referred to as "substrate") and raising the temperature to 80°C, the photosensitive element produced above was laminated (laminated) on the surface of the metal layer of the base material. Lamination was carried out under conditions of a temperature of 110° C. and a lamination pressure of 4 kgf/cm ² (0.4 MPa), while the protective layer was removed so that the photosensitive resin composition layer of the photosensitive element was in close contact with the surface of the metal layer of the substrate. In this way, the laminated base material in which the photosensitive resin composition layer and the support body were laminated|stacked on the metal layer surface of a base material was obtained.

<Evaluation of sensitivity>

The obtained laminated base material was left to cool until it became 23 degreeC. Next, the laminated substrate is divided into three regions, and on a support in one region, a concentration region of 0.00 to 2.00, a concentration step of 0.05, a tablet size of 20 mm × 187 mm, and a size of each step of 3 mm × 12 mm 41 A photo tool having a step-step tablet was closely attached. The exposure was performed using a parallel light exposure machine (manufactured by Oaksei Co., Ltd., product name "EXM-1201") using a short arc UV lamp (manufactured by Oaksei Co., Ltd., product name "AHD-5000R") as a light source, The photosensitive resin composition layer was exposed through a photo tool and a support with an energy amount (exposure amount) of 100 mJ/cm ² . At this time, the other unused area|region was covered with a black sheet. Moreover, about each other area|region, it exposed with the energy amount of 200 mJ/cm ² and 400 mJ/cm ² individually by the same method. In addition, the measurement of illuminance used the ultraviolet illuminometer (The Ushio Denki Co., Ltd. make, product name "UIT-150") to which a 405 nm compatible probe was applied.

After exposure, the support body was peeled from the laminated base material, the photosensitive resin composition layer was exposed, and the unexposed part was removed by spraying a 30 degreeC 1 mass % sodium carbonate aqueous solution for 16 second. In this way, the resist pattern which consists of a hardened|cured material of the photosensitive resin composition was formed on the metal layer surface of a base material. From the remaining number of stages (number of steps) of the step tablet obtained as a resist pattern (cured film) at each exposure amount, a calibration curve between the exposure amount and the number of steps is created, and the exposure amount at which the number of steps becomes 17 is obtained. The sensitivity of the composition was evaluated. The sensitivity is expressed by the exposure amount at which the number of steps obtained from the calibration curve becomes 17 steps, and it means that the sensitivity is so good that the exposure amount is small. The results are shown in Table 3.

<Evaluation of adhesion>

Residual of the 41-step step tablet using a mask pattern with a line width (L)/space width (S) (hereinafter referred to as “L/S”) of 8/400 to 47/400 (unit: μm) It exposed with respect to the photosensitive resin composition layer of the said laminated|multilayer base material with the energy amount used as 17 stages|stages. After exposure, the same development process as evaluation of the said sensitivity was implemented.

After development, the space portion (unexposed portion) is removed cleanly, and the line portion (exposed portion) is formed without meandering or defects. By this, adhesiveness was evaluated. It means that adhesiveness is so favorable that this numerical value is small. The results are shown in Table 3.

<Evaluation of resolution>

Using a mask pattern having an L/S of 8/8 to 47/47 (unit: μm), the photosensitive resin composition layer of the laminated substrate was exposed with an energy amount such that the remaining number of stages of a 41-step tablet was 17. . After exposure, the same development process as evaluation of the said sensitivity was implemented.

After development, the space portion (unexposed portion) is cleanly removed, and the line portion (exposed portion) is formed without meandering or defects. evaluated. It means that the resolution is so good that this numerical value is small. The results are shown in Table 3.

<Evaluation of etch-resistance property>

The etching resistance of the resist pattern was evaluated as follows. Using a mask pattern having an L/S of 8/400 to 47/400 (unit: μm), the photosensitive resin composition layer of the laminated substrate was exposed with an energy amount such that the remaining number of stages of a 41-step tablet was 17. . After exposure, the same development process as evaluation of the said sensitivity was performed, and the pattern-formed base material was obtained.

The obtained base material was etched using a cupric chloride solution until the metal layer on the surface disappeared. After that, it was washed with water and dried. Furthermore, the base material from which the surface metal layer was removed was immersed in 25 mass % hydrogen chloride aqueous solution for 2 minutes, and it was made to wash and dry with water after that.

After the transparent conductive layer is removed by etching, the metal layer and the transparent conductive layer in the space portion (unexposed portion) are cleanly removed, and the line portion (exposed portion) is formed without meandering or defects in the formed resist pattern. The minimum value among the values of line width/space width evaluated the adhesiveness after etching. It means that etching resistance is so high that this numerical value is small, and adhesiveness is favorable. The results are shown in Table 3.

<Adhesive evaluation of cured film by cross-cut test>

PET negative: Using a 60 mm x 45 mm square (beta: no pattern), the photosensitive resin composition layer of the said laminated base material was exposed with the energy amount at which the remaining number of stages of a 41-stage tablet becomes 17 stages. After exposure, the same development process as evaluation of the said sensitivity was performed, and the cured film of 60 mm x 45 mm square was obtained. In order to evaluate the adhesiveness of a cured film, based on Japanese Industrial Standards JISK-5600-5-6 (1999), the cross-cut test was implemented. Specifically, first, the 25th cross-cut (6 vertical and horizontal cuts each) of the cured film was carried out at intervals of 1 mm. Next, the presence or absence of peeling of a cured film was investigated by peeling off an adhesive tape, after affixing an adhesive tape to one crosscut location, and it evaluated in 6 grades of the class 0 to the class 5 shown in Table 2. The results are shown in Table 3.

It turned out that Examples 1-7 which have the compound of General formula (1) as a photopolymerizable compound have favorable adhesiveness by a crosscut test compared with Comparative Examples 1 and 2 which do not contain the compound of General formula (1). . In particular, in Examples 3 and 4 containing a pyrazoline compound as a sensitizing dye, class 0 adhesiveness was shown.

As can be seen from Table 3, Examples 1-4 and 7 containing an EO·PO-modified bisphenol A di(meth)acrylate compound and a urethane (meth)acrylate having an isocyanurate group are Comparative Example 1 and 2, it turned out that the adhesiveness after etching improves.

2… support, 4... A photosensitive resin composition layer, 6... protective layer, 10... A photosensitive element, 12... support substrate, 14 . . . Transparent conductive layer, 16... A photosensitive resin composition layer, 18... lead-out wiring, 22... support substrate, 24 . . . A transparent conductive layer, 26... metal layer, 28... The photosensitive resin composition layer, 29... resist pattern, 30... A photosensitive resin composition layer, 31... register, 52... Transparent electrode (X electrode), 54... Transparent electrode (Y electrode), 56, 57... Outgoing wiring, 100... touch panel.

Claims (7)

(A) A component: a binder polymer,
(B) Component: A photopolymerizable compound, and
(C)component: A photoinitiator is contained,
The component (B) contains a (meth)acrylate compound represented by the following general formula (1), and a bisphenol A-type di(meth)acrylate compound having a (poly)oxyethylene group and a (poly)oxypropylene group The photosensitive resin composition for ITO etching.

[In general formula (1), R ¹ represents an acryloyl group or a methacryloyl group. R ² represents an alkylene group containing a hydroxyl group or a polyoxyalkylene group having a hydroxyl group. R ³ represents an acryloyl group, a methacryloyl group, an alkyl group, or an aryl group.] According to claim 1,
The photosensitive resin composition in which the said (B) component further contains the urethane (meth)acrylate compound which has an isocyanurate group. (A) A component: a binder polymer,
(B) Component: A photopolymerizable compound, and
(C)component: A photoinitiator is contained,
The photosensitive resin composition in which the said (B) component further contains the (meth)acrylate compound represented by following General formula (1), and the urethane (meth)acrylate compound which has an isocyanurate group.

[In general formula (1), R1 represents an acryloyl group or a methacryloyl group. R2 represents an alkylene group containing a hydroxyl group or a polyoxyalkylene group having a hydroxyl group. R3 represents an acryloyl group, a methacryloyl group, an alkyl group or an aryl group.] A photosensitive element comprising a support and a photosensitive resin composition layer formed using the photosensitive resin composition according to claim 1 or 2 provided on one surface of the support. A 1st process of forming a photosensitive resin composition layer on a base material using the photosensitive resin composition of Claim 1 or 2;
a second step of curing a part of the photosensitive resin composition layer by irradiation with actinic light to form a cured product region;
A third step of removing a region other than the cured product region of the photosensitive resin composition layer from the substrate to obtain a resist pattern comprising the cured product region
A method of forming a resist pattern having a. On the metal layer of a laminated substrate comprising a supporting substrate, a transparent conductive layer containing indium tin oxide provided on one surface of the supporting substrate, and a metal layer provided on the transparent conductive layer, the metal layer according to claim 1 or 2 A first step of forming a resist pattern comprising a cured product of the photosensitive resin composition described above;
a second step of etching the metal layer and the transparent conductive layer to form a laminated pattern comprising the remainder of the transparent conductive layer and the remainder of the metal layer;
A third step of removing the metal layer from a part of the lamination pattern to form a transparent electrode comprising the remainder of the transparent conductive layer and a metal wiring comprising the remainder of the metal layer
Having, a method of manufacturing a touch panel. 7. The method of claim 6,
The transparent conductive layer contains crystalline indium tin oxide,
The method for manufacturing a touch panel, wherein the etching in the second step is etching with a strong acid.

Images