WO2017175642A1 - Photosensitive refractive index modulation film, method for forming cured film pattern, cured film and electronic component - Google Patents

Abstract

This photosensitive refractive index modulation film is provided with: a supporting film; a first resin layer which is provided on the supporting film and contains a di(meth)acrylate compound having a dicyclopentanyl structure or a dicyclopentenyl structure; and a second resin layer which is provided on the first resin layer and contains metal oxide particles and a polymer having an acid value of 150 mgKOH/g or more.

Description

Photosensitive refractive index adjusting film, method for forming cured film pattern, cured film and electronic component

The present invention relates to a photosensitive refractive index adjusting film, a method for forming a cured film pattern, a cured film, and an electronic component.

For large electronic devices such as personal computers and televisions, small electronic devices such as car navigation, mobile phones, smartphones, electronic dictionaries, and display devices such as OA (Office Automation, Office Automation) and FA (Factory Automation, Factory Automation) devices Liquid crystal display elements and touch panels (touch sensors) are used.

Various types of touch panels have been put to practical use, but in recent years, the use of projected capacitive touch panels has progressed. In general, in a projected capacitive touch panel, a plurality of X electrodes and a plurality of Y electrodes orthogonal to the X electrodes have a two-layer structure in order to express two-dimensional coordinates based on the X and Y axes. Forming. As a material for these electrodes, ITO (Indium-Tin-Oxide) is the mainstream.

Since the frame area of the touch panel is an area where the touch position cannot be detected, reducing the area of the frame area is an important factor for improving the product value. In general, a metal wiring such as copper is formed in the frame region in order to transmit a touch position detection signal.

By the way, when the touch panel is brought into contact with the fingertip, corrosive components such as moisture or salt may enter the inside from the sensing area. When a corrosive component enters the inside of the touch panel, the metal wiring corrodes, and there is a risk of an increase in electrical resistance between the electrode and the driving circuit, or disconnection.

In order to prevent corrosion of metal wiring, a photosensitive resin composition layer containing a di (meth) acrylate compound having a dicyclopentanyl structure or a dicyclopentenyl structure is provided on a touch panel substrate, and the photosensitive resin composition A method of forming a cured film of the photosensitive resin assembly that covers a part or all of the substrate after removing a part other than the predetermined part after curing a predetermined part of the physical layer by irradiation with actinic rays. (See Patent Document 1 below). According to this method, a cured film having a sufficiently low moisture permeability can be formed on the touch panel substrate.

On the other hand, the projected capacitive touch panel has a problem of so-called “bone appearance phenomenon” in which the electrode pattern is reflected on the screen in the sensing region.

As a method for suppressing the bone appearance phenomenon, the first curable transparent resin layer having a low refractive index adjusted to a specific refractive index range and the second curable transparent resin layer having a high refractive index are adjacent to each other. A transfer film is disclosed (see Patent Document 2 below).

JP2015-121929A International Publication No. 2014/084112 Pamphlet

When the present inventors examined the transfer film having a two-layer structure described in Patent Document 2 using the photosensitive resin composition described in Patent Document 1, poor connection occurs between touch panel circuits. It has been found. When the present inventors examined the cause of this connection failure, development residues of the first curable transparent resin layer and the second curable transparent resin layer remaining on the metal wiring were observed.

And when the di (meth) acrylate compound which has a dicyclopentanyl structure or a dicyclopentenyl structure contains in the 1st curable transparent resin layer, the present inventors are 2nd curable at the time of image development. It has been found that a slight development residue of the first curable transparent resin layer remaining on the transparent resin layer leads to a development residue causing the connection failure.

The present invention has been made in view of the above circumstances, and photosensitive refraction capable of forming a cured film having sufficiently low moisture permeability and a function of suppressing the appearance of bone phenomenon while suppressing poor connection of electrodes. It aims at providing the rate adjustment film, the formation method of a cured film pattern, a cured film, and an electronic component using the same.

The present inventors can suppress the inter-circuit connection failure of the touch panel while suppressing the corrosion of the metal wiring by combining the first resin layer having a specific composition and the second resin layer having a specific composition. As a result, the present invention has been completed.

The present invention, which is a specific means for solving the above problems, is as follows.

<1> A support film, a first resin layer containing a di (meth) acrylate compound having a dicyclopentanyl structure or a dicyclopentenyl structure provided on the support film, and the first resin layer And a second resin layer containing a polymer having an acid value of 150 mgKOH / g or more and metal oxide particles, and a photosensitive refractive index adjusting film.

According to the photosensitive refractive index adjusting film of the present invention, it is possible to form a cured film having a sufficiently low moisture permeability and a function of suppressing a bone appearance phenomenon while suppressing poor connection between circuits of the touch panel.

<2> The photosensitive refractive index adjusting film according to <1>, wherein the di (meth) acrylate compound having the dicyclopentanyl structure or the dicyclopentenyl structure is a compound represented by the following general formula (1). .

[In General Formula (1), R ¹ and R ² each independently represent a hydrogen atom or a methyl group, X represents a divalent group having a dicyclopentanyl structure or a dicyclopentenyl structure, and R ³ And R ⁴ each independently represents an alkylene group having 1 to 4 carbon atoms, n and m each independently represents an integer of 0 to 2, p and q each independently represents an integer of 0 or more, and p + q = 0 to 10 is selected. ]

<3> The photosensitive refractive index adjusting film according to <1> or <2>, wherein the polymer having an acid value of 150 mgKOH / g or more has a carboxyl group.

<4> The polymer having an acid value of 150 mgKOH / g or more is (meth) acrylic acid, (meth) acrylic acid glycidyl ester, (meth) acrylic acid benzyl ester, styrene, (meth) acrylic acid methyl ester, (meth) acrylic. <1> to <3> having structural units derived from at least one compound selected from the group consisting of acid ethyl ester, (meth) acrylic acid butyl ester, and (meth) acrylic acid-2-ethylhexyl ester The photosensitive refractive index adjustment film as described in any one of Claims.

<5> The photosensitive refractive index adjusting film according to any one of <1> to <4>, wherein the metal oxide particles are zirconium oxide or titanium oxide.

<6> The photosensitive refractive index adjusting film according to any one of <1> to <5>, wherein the first resin layer contains a binder polymer and a photopolymerization initiator.

<7> The photosensitive refractive index adjusting film according to <6>, wherein the photopolymerization initiator contains an oxime ester compound.

<8> The photosensitive refractive index adjusting film according to <6> or <7>, wherein the binder polymer has a carboxyl group.

<9> The binder polymer is (meth) acrylic acid, (meth) acrylic acid glycidyl ester, (meth) acrylic acid benzyl ester, styrene, (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meta <6> to <8> having a structural unit derived from at least one compound selected from the group consisting of :) butyl acrylate, and (meth) acrylic acid-2-ethylhexyl ester Photosensitive refractive index adjusting film.

<10> The photosensitive refractive index adjusting film according to any one of <1> to <9>, wherein the first resin layer contains a phosphoric ester having an ethylenically unsaturated group.

<11> The photosensitive refractive index adjusting film according to any one of <1> to <10>, wherein the refractive index of the second resin layer at a wavelength of 633 nm is 1.5 to 1.9.

<12> The photosensitive refractive index adjusting film according to any one of <1> to <11>, wherein the thickness of the second resin layer is 40 nm to 500 nm.

<13> Any one of <1> to <12>, wherein a minimum value of transmittance at a wavelength of 400 to 700 nm of the laminate including the first resin layer and the second resin layer is 90% or more. The photosensitive refractive index adjustment film of item.

<14> The photosensitive refractive index adjusting film according to any one of <1> to <13>, wherein the total thickness of the first resin layer and the second resin layer is 30 μm or less.

<15> Using the photosensitive refractive index adjusting film according to any one of <1> to <14>, the first resin layer and the second resin layer are in close contact with each other on a substrate. A step of laminating the second resin layer, a step of exposing predetermined portions of the first resin layer and the second resin layer on the substrate, and a step of removing portions other than the exposed predetermined portions. And a method for forming a cured film pattern.

<16> A cured film obtained by curing the second resin layer and the first resin layer of the photosensitive refractive index adjusting film according to any one of <1> to <14>.

<17> The cured film according to <16>, which is formed in a pattern.

<18> An electronic component having the cured film according to <16> or <17>.

According to the present invention, it is possible to provide a photosensitive refractive index adjusting film capable of forming a cured film functioning as a protective film or a refractive index adjusting film with good developability.

Further, according to the present invention, a photosensitive refractive index adjusting film capable of forming a cured film having sufficiently low moisture permeability and a function of suppressing bone appearance phenomenon while suppressing poor connection of electrodes, and A method for forming a cured film pattern, a cured film, and an electronic component can be provided.

It is a schematic cross section which shows the photosensitive refractive index adjustment film which concerns on one Embodiment of this invention. It is a schematic cross section which shows the laminated body which equips the base material with a transparent electrode pattern with the cured film pattern formed using the photosensitive refractive index adjustment film which concerns on one Embodiment of this invention. It is a schematic plan view which shows the electronic component which concerns on one Embodiment of this invention.

Hereinafter, embodiments for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In the present specification, “(meth) acrylic acid” means acrylic acid or methacrylic acid, and “(meth) acrylate” means acrylate or a corresponding methacrylate. “A or B” only needs to include one of A and B, or may include both.

In addition, in this specification, the term “process” is not limited to an independent process, and even if it cannot be clearly distinguished from other processes, the term “process” is used as long as the intended action of the process is achieved. included. The numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.

Furthermore, in the present specification, the content of each component in the composition is the sum of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. Means quantity. In addition, the exemplary materials may be used alone or in combination of two or more unless otherwise specified.

<Photosensitive refractive index adjusting film>
The photosensitive refractive index adjusting film of the present invention includes a support film, a first resin layer containing a di (meth) acrylate compound having a dicyclopentanyl structure or a dicyclopentenyl structure provided on the support film, And a second resin layer containing a polymer having an acid value of 150 mgKOH / g or more and metal oxide particles provided on the first resin layer.

Hereinafter, preferred embodiments of the photosensitive refractive index adjusting film of the present invention will be described.

FIG. 1 is a schematic cross-sectional view showing an embodiment of the photosensitive refractive index adjusting film of the present invention. The photosensitive refractive index adjusting film 1 shown in FIG. 1 includes a support film 10, a first resin layer 20 provided on the support film, and a second resin provided on the first resin layer 20. And a resin layer 30. The photosensitive refractive index adjusting film may include a protective film 40 provided on the opposite side of the second resin layer 30 from the first resin layer 20 as shown in FIG.

FIG. 2 is a schematic cross-sectional view showing an embodiment in which the photosensitive refractive index adjusting film of the present invention is used for a substrate with a transparent electrode pattern. In FIG. 2, the cured film 32 of the second resin layer is provided on the substrate 50 with the transparent electrode pattern 50a such as ITO so as to cover the pattern 50a, and the cured film 22 of the first resin layer is formed thereon. The transparent laminated body 100 is provided. That is, FIG. 2 shows the laminated body 100 which equips the base material 50 with the transparent electrode pattern 50a with the cured film pattern 60 formed using the photosensitive refractive index adjustment film which concerns on one Embodiment of this invention.

By using the photosensitive refractive index adjustment film, for example, a cured film satisfying both the function of protecting the metal wiring in the transparent electrode or the frame area in the touch panel and the function of suppressing the visualization of the transparent electrode pattern or improving the visibility of the sensing area. It can be formed in a lump.

<Support film>
As the support film 10, for example, a polymer film can be used. Examples of the polymer film include films of polyethylene terephthalate, polycarbonate, polyethylene, polypropylene, polyethersulfone, cycloolefin polymer, and the like.

The thickness of the support film 10 is preferably 5 to 100 μm, preferably 10 to 70 μm, from the viewpoint of ensuring coverage and suppressing the reduction in resolution when irradiated with actinic rays through the support film 10. Is more preferably 15 to 40 μm, and particularly preferably 15 to 35 μm.

<First resin layer>
The first resin layer 20 is preferably a photosensitive resin layer from the viewpoint of easily forming a cured film having a desired shape. The first resin layer 20 includes a binder polymer (hereinafter also referred to as (A) component), a photopolymerizable compound (hereinafter also referred to as (B) component), and a photopolymerization initiator (hereinafter referred to as (C) component). It is preferably formed from a photosensitive resin composition containing

(Binder polymer)
As the component (A), a binder polymer having a carboxyl group is preferably used from the viewpoint of enabling patterning by alkali development.

The (A) component is preferably a copolymer having a structural unit derived from (meth) acrylic acid and (meth) acrylic acid alkyl ester. The copolymer may contain in the structural unit other monomers that can be copolymerized with the (meth) acrylic acid and the (meth) acrylic acid alkyl ester. Specific examples include (meth) acrylic acid glycidyl ester, (meth) acrylic acid benzyl ester, and styrene.

In addition, the component (A) may have an ethylenically unsaturated group. In addition, the (A) component which has an ethylenically unsaturated group shall not be included in (B) component in this specification.

Examples of the (meth) acrylic acid alkyl ester include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid-2-ethylhexyl ester, (meth) acrylic And acid hydroxyl ethyl ester. Among these, (meth) acrylic acid, (meth) acrylic acid glycidyl ester, (meth) acrylic acid benzyl ester, styrene, (meth) from the viewpoints of alkali developability (particularly with respect to an inorganic alkaline aqueous solution), patternability, and transparency. Binder polymer having a structural unit derived from at least one compound selected from the group consisting of :) methyl acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate Is preferred.

The weight average molecular weight of the component (A) is preferably 10,000 to 200,000, more preferably 15,000 to 150,000, and more preferably 30,000 to 150,000 from the viewpoint of resolution. More preferably, it is particularly preferably 30,000 to 100,000, and most preferably 40,000 to 100,000. The weight average molecular weight can be measured by a gel permeation chromatography method with reference to the examples of the present specification.

The acid value of the component (A) is preferably 75 mgKOH / g or more from the viewpoint of easily forming a cured film having a desired shape by alkali development. Further, from the viewpoint of achieving both controllability of the cured film shape and rust prevention of the cured film, it is preferably 75 to 200 mgKOH / g, more preferably 75 to 150 mgKOH / g, and 75 to 120 mgKOH. More preferably, it is / g. In addition, an acid value can be measured with reference to the Example of this-application specification.

The hydroxyl value of the component (A) is preferably 50 mgKOH / g or less, more preferably 45 mgKOH / g or less, from the viewpoint of further improving rust prevention. The hydroxyl value can be measured with reference to the examples in the present specification.

(Photopolymerizable compound)
(B) As a photopolymerizable compound which is a component, the di (meth) acrylate compound which has a dicyclopentanyl structure or a dicyclopentenyl structure is included. Di (meth) having a dicyclopentanyl structure or a dicyclopentenyl structure from the viewpoint of suppressing corrosion of the metal wiring and the transparent electrode when a laminate including the first resin layer and the second resin layer is formed. As the acrylate compound, a compound represented by the following general formula (1) is preferably included.

[In General Formula (1), R ¹ and R ² each independently represent a hydrogen atom or a methyl group, X represents a divalent group having a dicyclopentanyl structure or a dicyclopentenyl structure, and R ³ And R ⁴ each independently represents an alkylene group having 1 to 4 carbon atoms, n and m each independently represents an integer of 0 to 2, p and q each independently represents an integer of 0 or more, and p + q = 0 to 10 is selected. ]

In the general formula (1), R ³ and R ⁴ are preferably each independently an ethylene group or a propylene group, and more preferably an ethylene group. The propylene group may be either an n-isopropylene group or an isopropylene group.

In the above general formula (1), n and m indicate how much a methylene group is added in the molecule. p and q indicate how much an alkoxy group having 1 to 4 carbon atoms is added to the molecule. When p + q is 2 or more, two or more R ³ and R ⁴ may be the same or different.

The compound represented by the general formula (1) realizes low moisture permeability of the film because the divalent group having a dicyclopentanyl structure or dicyclopentenyl structure contained in X has a bulky structure. Therefore, it is considered that the corrosion resistance of the metal wiring and the transparent electrode is improved.

The dicyclopentanyl structure and the dicyclopentenyl structure can also be referred to as a tricyclodecane skeleton and a tricyclodecene skeleton, respectively. The “tricyclodecane skeleton” and the “tricyclodecene skeleton” refer to the following structures (where each bond is an arbitrary position).

Examples of the compound represented by the general formula (1) include tricyclodecane dimethanol diacrylate represented by the following formula (2). This is available as A-DCP (manufactured by Shin-Nakamura Chemical Co., Ltd., product name).

[In the general formula (1), a compound in which X is a divalent group having a dicyclopentanyl structure, m = n = 1, p = q = 0]

The content of the di (meth) acrylate compound having a dicyclopentanyl structure or a dicyclopentenyl structure is 50 with respect to 100 parts by mass of the total amount of the component (B) from the viewpoint of suppressing corrosion of the metal wiring and the transparent electrode. It is preferably at least part by mass, more preferably at least 70 parts by mass, and even more preferably at least 80 parts by mass.

As the photopolymerizable compound as the component (B), a photopolymerizable compound having an ethylenically unsaturated group different from the compound represented by the general formula (1) can be used. Examples of the photopolymerizable compound having an ethylenically unsaturated group include a monofunctional vinyl monomer having one polymerizable ethylenically unsaturated group in the molecule and two polymerizable ethylenically unsaturated groups in the molecule. Bifunctional vinyl monomers or polyfunctional vinyl monomers having at least three polymerizable ethylenically unsaturated groups in the molecule can be mentioned.

Examples of the monofunctional vinyl monomer having one polymerizable ethylenically unsaturated group in the molecule include those exemplified as monomers used for the synthesis of a copolymer which is a preferred example of the component (A). Can be mentioned.

Examples of the bifunctional vinyl monomer having two polymerizable ethylenically unsaturated groups in the molecule include polyethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, polypropylene glycol di (meth) acrylate, 2, Examples thereof include 2-bis (4- (meth) acryloxypolyethoxypolypropoxyphenyl) propane, bisphenol A diglycidyl ether di (meth) acrylate, and tricyclodecane dimethanol dimethacrylate.
Among the compounds exemplified above, tricyclodecane dimethanol dimethacrylate is preferably used from the viewpoint of improving developability.

As the polyfunctional vinyl monomer having at least three polymerizable ethylenically unsaturated groups in the molecule, conventionally known ones can be used without particular limitation. (Meth) acrylate compounds having a skeleton derived from trimethylolpropane, such as trimethylolpropane tri (meth) acrylate, from the viewpoint of corrosion inhibition of metal wiring and transparent electrode and developability; tetramethylolmethane tri (meth) acrylate, tetramethylol (Meth) acrylate compounds having a skeleton derived from tetramethylolmethane such as methanetetra (meth) acrylate; (meth) acrylates having a skeleton derived from pentaerythritol such as pentaerythritol tri (meth) acrylate and pentaerythritol tetra (meth) acrylate Compound: (Meth) acrylate compound having a skeleton derived from dipentaerythritol such as dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate ; It is preferably used or having a skeleton derived from diglycerol (meth) acrylate compound; which ditrimethylol having propane tetra (meth) ditrimethylolpropane derived skeleton such as acrylates (meth) acrylate compound.

The content of the component (A) and the component (B) is preferably 35 to 85 parts by mass of the component (A) with respect to 100 parts by mass of the total amount of the components (A) and (B). The amount is more preferably 80 parts by mass, further preferably 50 to 70 parts by mass, and particularly preferably 55 to 65 parts by mass. In particular, the point that the (A) component is 35 parts by mass or more with respect to 100 parts by mass of the total amount of the (A) component and the (B) component in that the pattern forming property and the rust prevention property of the cured film are maintained. The amount is preferably 40 parts by mass or more, more preferably 50 parts by mass or more, and particularly preferably 55 parts by mass or more.

(Photopolymerization initiator)
As the component (C), as long as it is a photopolymerization initiator, a conventionally known one can be used without particular limitation, but it is preferable to include an oxime ester compound. By using such a photopolymerization initiator, a cured film pattern can be formed with sufficient resolution even if the thickness of the first resin layer is a thin film of 10 μm or less. The cured film pattern is sufficiently excellent in transparency.

The oxime ester compound is preferably a compound represented by the following formula (3), a compound represented by the following formula (4), or a compound represented by the following formula (5).

In the formula (3), R ₁₁ and R ₁₂ each independently represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group, or a tolyl group. Preferred are an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 6 carbon atoms, a phenyl group or a tolyl group, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 4 to 6 carbon atoms, phenyl It is more preferably a group or a tolyl group, and further preferably a methyl group, a cyclopentyl group, a phenyl group or a tolyl group. R ₁₃ represents —H, —OH, —COOH, —O (CH ₂ ) OH, —O (CH ₂ ) ₂ OH, —COO (CH ₂ ) OH or —COO (CH ₂ ) ₂ OH. It is preferably —H, —O (CH ₂ ) OH, —O (CH ₂ ) ₂ OH, —COO (CH ₂ ) OH, or —COO (CH ₂ ) ₂ OH, —H, —O (CH ₂ ) ₂ OH or —COO (CH ₂ ) ₂ OH is more preferable.

In the formula (4), each R ₁₄ represents an alkyl group having 1 to 6 carbon atoms, and is preferably a propyl group. The plurality of R ₁₄ may be the same or different. R ₁₅ represents NO ₂ or ArCO (wherein Ar represents a substituted or unsubstituted aryl group), and Ar is preferably a tolyl group. Examples of the substituent in the case of having a substituent include an alkyl group having 1 to 6 carbon atoms. R ₁₆ and R ₁₇ each independently represent an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a tolyl group, and is preferably a methyl group, a phenyl group, or a tolyl group.

In the formula (5), R ₁₈ represents an alkyl group having 1 to 6 carbon atoms, and is preferably an ethyl group. R ₁₉ is an organic group having an acetal bond, and is preferably a substituent corresponding to R ₁₉ in a compound represented by the formula (5-1) described later. R ₂₀ and R ₂₁ each independently represents an alkyl group having 1 to 12 carbon atoms, a phenyl group or a tolyl group, preferably a methyl group, a phenyl group or a tolyl group, and more preferably a methyl group. R ₂₂ represents an alkyl group having 1 to 6 carbon atoms. n represents an integer of 0 to 4.

Examples of the compound represented by the above formula (3) include a compound represented by the following formula (3-1) and a compound represented by the following formula (3-2). A compound represented by the following formula (3-1) is available as IRGACURE OXE-01 (product name, manufactured by BASF Corporation).

Examples of the compound represented by the above formula (4) include a compound represented by the following formula (4-1). A compound represented by the following formula (4-1) is available as DFI-091 (product name, manufactured by Daito Chemix Co., Ltd.).

Examples of the compound represented by the above formula (5) include a compound represented by the following formula (5-1). A compound represented by the following formula (5-1) is available as Adekaoptomer N-1919 (manufactured by ADEKA, product name).

As other oxime ester compounds, it is preferable to use a compound represented by the following formula (6), a compound represented by the following formula (7), or the like.

Among the above, the compound represented by the above formula (3-1) is very preferable. Whether the compound represented by the above formula (3-1) is contained in the cured film can be confirmed by pyrolysis gas chromatograph mass spectrometry of the cured film described in International Publication No. 2013/084875.

The content of the component (C) is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B) in terms of excellent photosensitivity and resolution. It is more preferably from 5 to 5 parts by mass, further preferably from 1 to 3 parts by mass, and particularly preferably from 1 to 2 parts by mass.

(Additive)
The resin composition forming the first resin layer according to this embodiment is a triazole compound having a mercapto group, a tetrazole compound having a mercapto group, and a thiadiazole having a mercapto group from the viewpoint of further improving the rust prevention property of the cured film. It is preferable to further contain a compound, a triazole compound having an amino group, or a tetrazole compound having an amino group (hereinafter also referred to as component (D)). Examples of the triazole compound having a mercapto group include 3-mercapto-triazole (manufactured by Wako Pure Chemical Industries, Ltd., product name: 3MT). Examples of the thiadiazole compound having a mercapto group include 2-amino-5-mercapto-1,3,4-thiadiazole (manufactured by Wako Pure Chemical Industries, Ltd., product name: ATT).

Examples of the triazole compound having an amino group include benzotriazole, 1H-benzotriazole-1-acetonitrile, benzotriazole-5-carboxylic acid, 1H-benzotriazole-1-methanol, carboxybenzotriazole, etc. , 3-mercaptotriazole, 5-mercaptotriazole, and other triazole compounds containing a mercapto group are substituted with amino groups.

Examples of the tetrazole compounds having an amino group include 5-amino-1H-tetrazole, 1-methyl-5-amino-tetrazole, 1-methyl-5-mercapto-1H-tetrazole, and 1-carboxymethyl-5-amino-tetrazole. Etc. These tetrazole compounds may be water-soluble salts thereof. Specific examples include alkali metal salts of 1-methyl-5-amino-tetrazole such as sodium, potassium and lithium.

When the component (D) is contained, the content thereof is preferably 0.05 to 5.0 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B), and 0.1 to 2. 0 part by mass is more preferable, 0.2 to 1.0 part by mass is further preferable, and 0.3 to 0.8 part by mass is particularly preferable.

The resin composition forming the first resin layer according to the present embodiment is a phosphate ester having an ethylenically unsaturated group (hereinafter referred to as “adhesiveness” to the substrate with an ITO electrode pattern and preventing the development residue). , (Also referred to as component (E)). The phosphate ester having an ethylenically unsaturated group may overlap with the component (B), but in this specification, it is not included in the component (B).

(E) As a phosphoric acid ester having an ethylenically unsaturated group as a component, while ensuring sufficient rust prevention of the cured film to be formed, the adhesion to the substrate with the ITO electrode pattern and developability are at a high level. From the standpoint of compatibility, the Phosmer series (Phosmer-M, Phosmer-CL, Phosmer-PE, Phosmer-MH, Phosmer-PP, etc.) manufactured by Unichemical Co., Ltd. -2 etc.) is preferred.

In the resin composition forming the first resin layer according to the present embodiment, as other additives, an adhesiveness imparting agent such as a silane coupling agent, a rust preventive agent, a leveling agent, and a plasticizer, as necessary. , Fillers, antifoaming agents, flame retardants, stabilizers, antioxidants, fragrances, thermal cross-linking agents, polymerization inhibitors, etc. with respect to 100 parts by mass of the total amount of component (A) and component (B), About 01 to 20 parts by mass can be contained. These can be used alone or in combination of two or more. In addition, said "resin composition which forms the 1st resin layer" means the composition of the state which does not contain the solvent mentioned later, and content of each component is content with respect to component whole quantity other than the solvent mentioned later It is.

The refractive index of the first resin layer at a wavelength of 633 nm is usually 1.40 to 1.49.

The thickness of the first resin layer is preferably 15 μm or less in terms of the thickness after drying in order to sufficiently exhibit the effect as a protective film and sufficiently bury the step on the surface of the substrate with the transparent electrode pattern. The thickness is more preferably 10 μm, and further preferably 3 to 8 μm.

<Second resin layer>
The second resin layer contains a polymer having an acid value of 150 mgKOH / g or more and metal oxide particles. The refractive index of the second resin layer is higher than that of the first resin layer.

(A polymer with an acid value of 150 mgKOH / g or more)
The second resin layer contains a polymer having an acid value of 150 mgKOH / g or more.

As the polymer, compounds exemplified in the component (A) used for the first resin layer can be preferably used.

The acid value of the polymer is 150 mgKOH / g or more from the viewpoint of improving alkali developability when bonded to the first resin layer. Further, from the viewpoint of achieving both controllability of the cured film shape and rust prevention of the cured film, it is preferably 150 to 200 mgKOH / g, more preferably 150 to 175 mgKOH / g, and 150 to 160 mgKOH. More preferably, it is / g. As a method for improving the acid value of a polymer, a carboxyl group is imparted to the side chain of the polymer. The acid value of the polymer can be measured in the same manner as the acid value of the binder polymer.

The weight average molecular weight of the polymer having an acid value of 150 mgKOH / g or more is preferably 10,000 to 200,000, more preferably 10,000 to 150,000 from the viewpoint of resolution, and 10,000 to It is more preferably 10,000, particularly preferably 10,000 to 85,000, and most preferably 10,000 to 70,000. In addition, a weight average molecular weight can be measured similarly to the weight average molecular weight measurement of a binder polymer.

<Metal oxide particles>
The composition forming the second resin layer 30 contains metal oxide particles (hereinafter also referred to as the component (F)). In particular, it is preferable to contain metal oxide particles having a refractive index of 1.5 or more at a wavelength of 633 nm.

Thereby, when the photosensitive refractive index adjusting film is prepared, the transparency of the second resin layer and the refractive index at a wavelength of 633 nm can be improved. Moreover, developability can be improved, suppressing adsorption | suction to a base material. The metal oxide particles preferably contain, for example, zirconium oxide or titanium oxide particles from the viewpoint of suppressing the bone-visible phenomenon.

As the zirconium oxide particles, when the material of the transparent electrode is ITO, it is preferable to use zirconium oxide nanoparticles from the viewpoint of improving the refractive index and adhesion between the ITO and the transparent substrate. Among the zirconium oxide nanoparticles, the particle size distribution Dmax is preferably 40 nm or less.

Zirconium oxide nanoparticles are OZ-S30K (product name, manufactured by Nissan Chemical Industries, Ltd.), OZ-S40K-AC (product name, manufactured by Nissan Chemical Industries, Ltd.), SZR-K (dispersion of zirconium oxide methyl ethyl ketone, Sakai Chemical). Kogyo Co., Ltd., product name) and SZR-M (zirconium oxide methanol dispersion, Sakai Chemical Industry Co., Ltd., product name) are commercially available.

In the composition forming the second resin layer 30, titanium oxide nanoparticles can be used as the component (F). Of the titanium oxide nanoparticles, the particle size distribution Dmax is preferably 50 nm or less, more preferably 10 to 50 nm.

As the component (F), in addition to the metal oxide particles, oxide particles or sulfide particles containing atoms such as Mg, Al, Si, Ca, Cr, Cu, Zn, and Ba can be used. These can be used alone or in combination of two or more.

In addition to the metal oxide particles, organic compounds such as a compound having a triazine ring, a compound having an isocyanuric acid skeleton, and a compound having a fluorene skeleton can also be used. Thereby, the refractive index in wavelength 633nm can be improved.

The content of the metal oxide particles is preferably 20 to 85 parts by mass with respect to 100 parts by mass of the composition forming the second resin layer, from the viewpoint of improving the refractive index and developability of the second resin layer. 35 to 85 parts by mass, more preferably 50 to 85 parts by mass, and most preferably 70 to 85 parts by mass.

In the composition forming the second resin layer, the components (B) to (E) and other additives used for the first resin layer can be preferably used.

The composition forming the second resin layer is not necessarily required to contain a photopolymerization component such as a photopolymerizable compound or a photopolymerization initiator, but utilizes a photopolymerization component that migrates from an adjacent resin layer by layer formation. The second resin layer can be photocured.

In addition, said "composition which forms the 2nd resin layer" means the composition of the state which does not contain the solvent mentioned later, and content of each component is content with respect to component whole quantity other than the solvent mentioned later. .

The polymer content of the composition forming the second resin layer is preferably 40 to 80 parts by mass, and 50 to 80 parts by mass with respect to 100 parts by mass of the total amount of the polymer and the component (B). More preferred is 60 to 80 parts by mass. By making polymer content into the said range, pattern formation property and the rust prevention property of a cured film can be improved.

The second resin layer preferably has a refractive index of 1.5 to 1.9 at a wavelength of 633 nm. More specifically, it is preferably 1.50 to 1.90, more preferably 1.53 to 1.85, and still more preferably 1.55 to 1.75. When the refractive index at the wavelength of 633 nm of the second resin layer is within the above range, when the transparent laminate 100 shown in FIG. 2 is formed, the transparent electrode pattern 50a such as ITO and the cured film 22 of the first resin layer are formed. It becomes an intermediate value of the refractive index of various members (for example, a transparent adhesive film (OCA, Optical Clear Adhesive) for bonding a cover glass used for modularization and a transparent electrode pattern), such as ITO. The color difference due to optical reflection between the portion where the transparent electrode pattern is formed and the portion where the transparent electrode pattern is not formed can be reduced, and the bone appearance phenomenon can be suppressed. Moreover, it becomes possible to reduce the reflected light intensity of the whole screen, and to suppress the transmittance | permeability fall on a screen. The refractive index can be measured with reference to the examples in the present specification.

The refractive index of a transparent electrode such as ITO is preferably 1.80 to 2.10, more preferably 1.85 to 2.05, and even more preferably 1.90 to 2.00. . Further, the refractive index of a member such as OCA is preferably 1.45 to 1.55, more preferably 1.47 to 1.53, and further preferably 1.48 to 1.51. .

The thickness of the second resin layer is preferably 40 to 500 nm after drying, more preferably 40 to 100 nm, further preferably 40 to 80 nm, and more preferably 40 to 60 nm. Is particularly preferred. When the thickness is 40 to 500 nm, the reflected light intensity of the entire screen can be further reduced.

<Other layers>
The photosensitive refractive index adjusting film of the present invention may be provided with other appropriately selected layers as long as the effects of the present invention are obtained. There is no restriction | limiting in particular as said other layer, According to the objective, it can select suitably, For example, a cushion layer, an oxygen shielding layer, a peeling layer, an adhesive layer etc. are mentioned. The said photosensitive refractive index adjustment film may have these layers individually by 1 type, and may have 2 or more types. Moreover, you may have 2 or more of the same kind of layers.

<Protective film>
Examples of the protective film 40 include polyethylene, polypropylene, polyethylene terephthalate, polycarbonate, a polyethylene-vinyl acetate copolymer, a polyethylene-vinyl acetate copolymer film, and a laminated film of these films and polyethylene.

The thickness of the protective film 40 is preferably 5 to 100 μm, but from the viewpoint of storing in a roll, it is preferably 70 μm or less, more preferably 60 μm or less, and even more preferably 50 μm or less. It is especially preferable that it is 40 micrometers or less.

[Method for producing photosensitive refractive index adjusting film]
The first resin layer 20 and the second resin layer 30 of the photosensitive refractive index adjusting film are, for example, a coating liquid containing a resin composition that forms the first resin layer, and a composition that forms the second resin layer. It can form by preparing the coating liquid containing a thing, respectively apply | coating this on the support film 10 and the protective film 40, drying, and bonding together. Or the coating liquid containing the resin composition which forms the 1st resin layer on the support film 10 is applied and dried, and then the 2nd resin layer is formed on the 1st resin layer 20 It can also form by apply | coating and drying the coating liquid containing this, and affixing the protective film 40 as needed.

The coating solution is obtained by uniformly dissolving or dispersing each component constituting the resin composition forming the first resin layer and the resin composition forming the second resin layer according to this embodiment described above in a solvent. Obtainable.

The solvent used as the coating solution is not particularly limited, and known ones can be used. Solvents used as coating solutions are, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, methanol, ethanol, propanol, butanol, methylene glycol, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol Examples include ethyl methyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, chloroform, and methylene chloride.

Application methods include, for example, doctor blade coating method, Meyer bar coating method, roll coating method, screen coating method, spinner coating method, inkjet coating method, spray coating method, dip coating method, gravure coating method, curtain coating method, die coating method. Law.

The drying conditions are not particularly limited, but the drying temperature is preferably 60 to 130 ° C., and the drying time is preferably 0.5 to 30 minutes.

The thickness of the laminate including the first resin layer and the second resin layer is preferably 30 μm or less, more preferably 20 μm or less, and more preferably 10 μm or less from the viewpoint of improving the followability during lamination. More preferably. Furthermore, from the viewpoint of rust prevention, taking into account the possibility of pinholes due to protrusions on the base material, it is preferably 1 μm or more, preferably 2 μm or more, and more preferably 2 μm or more. . If it is 3 micrometers or more, it will become possible to suppress the influence by the protrusion of a base material, and to maintain rust prevention property.

The minimum value of the transmittance at a wavelength of 400 to 700 nm of the laminate comprising the first resin layer and the second resin layer is preferably 90% or more. More specifically, it is preferably 90.00% or more, more preferably 90.50% or more, and further preferably 90.70% or more. If the transmittance at a wavelength of 400 to 700 nm, which is a general visible light wavelength range, is 90% or more, the image display quality, color tone, and luminance in the sensing area are reduced when the transparent electrode in the sensing area of the touch panel is protected. Can be sufficiently suppressed. The maximum value of the transmittance is usually 100% or less. The visible light transmittance can be measured with reference to the examples in the present specification.

[Method of forming cured film pattern]
Next, a method for forming a cured film pattern using the photosensitive refractive index adjusting film will be described.

(Base material)
Examples of the substrate 50 (substrate with a transparent electrode pattern) include glass, plastic, ceramic, resin-made substrates used for touch panels, and the like. Examples of the resin base material include a polyester resin, a polystyrene resin, an olefin resin, a polybutylene terephthalate resin, a polycarbonate resin, and an acrylic resin base material. These substrates are preferably transparent.

(Transparent electrode and metal wiring)
On the base material, a transparent electrode and a metal wiring, which are targets for forming a cured film, are provided.
The transparent electrode can be formed using a conductive metal oxide film such as ITO and IZO (Indium Zinc Oxide). The transparent electrode can also be formed using a photosensitive film having a photocurable resin layer using conductive fibers such as silver fibers and carbon nanotubes.
The metal wiring can be formed by a method such as screen printing or vapor deposition using a conductive material such as Au, Ag, Cu, Al, Mo, and C, for example. Further, for example, a refractive index adjusting layer, an insulating layer, or the like may be provided between the base material and the transparent electrode and the metal wiring.

-Lamination process-
First, after removing the protective film 40 which exists as needed of the photosensitive refractive index adjusting film 1, the second resin is applied to the surface of the substrate 50 (substrate with a transparent electrode pattern). Lamination is performed by pressing from the support film side so that the layer 30 is in close contact. Examples of the pressing means include a pressing roll. The pressure roll may be provided with a heating means so that it can be heat-pressure bonded.

The heating temperature for thermocompression bonding is such that the adhesiveness between the second resin layer 30 and the substrate 50 and the constituent components of the first resin layer and the second resin layer are not easily cured or thermally decomposed. From the viewpoint, it is preferably 25 to 160 ° C., more preferably 25 to 150 ° C., and further preferably 30 to 150 ° C.

In addition, the pressure at the time of thermocompression bonding is 50 to 1 × 10 ^{5 in} terms of linear pressure from the viewpoint of suppressing deformation of the base material 50 while ensuring sufficient adhesion between the second resin layer 30 and the base material 50. N / m is preferable, 2.5 × 10 ² to 5 × 10 ⁴ N / m is more preferable, and 5 × 10 ² to 4 × 10 ⁴ N / m is further preferable.

If the photosensitive refractive index adjusting film is thermocompression bonded as described above, the pre-heat treatment of the base material is not necessarily required, but from the point of further improving the adhesion between the second resin layer 30 and the base material 50, The material 50 may be preheated. The treatment temperature at this time is preferably 30 to 150 ° C.

-Exposure process-
Next, actinic rays are radiated in a pattern to the predetermined portions of the second resin layer and the first resin layer after transfer, for example, via a photomask. When irradiating actinic light, if the support film 10 on the first resin layer is transparent, the actinic light can be irradiated as it is. If it is opaque, the actinic light is irradiated after removal. A known active light source can be used as the active light source. The pattern in this specification is not limited to the shape of the fine wiring that forms the circuit, but also includes the shape in which only the connection portion with the other base material is removed in a rectangular shape and the shape in which only the frame portion of the base material is removed. It is.

The irradiation amount of actinic rays is 1 × 10 ² to 1 × 10 ⁴ J / m ² , and heating can be accompanied during irradiation. If the irradiation amount of this actinic ray is 1 × 10 ² J / m ² or more, photocuring can sufficiently proceed, and if it is 1 × 10 ⁴ J / m ² or less, the first resin There is a tendency that discoloration of the layer and the second resin layer can be suppressed.

-Development process-
Subsequently, the unexposed portions of the first resin layer and the second resin layer after irradiation with actinic rays are removed with a developer to form a cured film pattern that covers part or all of the transparent electrode. In addition, after irradiation of actinic light, when the support film 10 is laminated | stacked on the 1st resin layer, after developing it, the image development process is performed.

The development step is preferably performed by a known method such as spraying, showering, rocking dipping, brushing, or scrubbing using an aqueous alkaline solution as a developing solution. Of these, spray development is preferably performed using an alkaline aqueous solution from the viewpoint of environment and safety. The development temperature and time can be adjusted within a conventionally known range.

The present inventors consider the reason why the poor connection between circuits of the touch panel can be suppressed by the photosensitive refractive index adjusting film of the present invention as follows. The second resin layer containing a polymer having an acid value of 150 mgKOH / g or more and metal oxide particles has good developability with respect to an alkaline developer in an unexposed part because the acid value is in the above range, and the unexposed part has an unexposed part. Dissolves quickly.

The photosensitive refractive index adjusting film of the present invention is laminated so that the second resin layer is in close contact with the substrate. Therefore, when the second resin layer in close contact with the substrate is developed, the first resin layer on the surface of the second resin layer on the side opposite to the substrate follows and peels off. As a result, the inventor speculates that the generation of development residue is suppressed, and poor circuit connection between touch panels can be suppressed.

<Curing film>
The cured film of the present invention is a cured film obtained by curing the first resin layer and the second resin layer of the photosensitive refractive index adjusting film of the present invention. The cured film of the present invention can be used as, for example, an electrode protective film for a touch panel, a planarizing film and interlayer insulating film for display elements such as liquid crystal and organic EL, a protective film for a color filter, a solder resist film for a printed wiring board, and the like. Is possible.

For example, when most of the second resin layer is covered with the first resin layer and is not exposed, the second resin layer does not necessarily need to be cured. The cured film of the present invention includes the case where such a first resin layer is cured and the second resin layer is not cured.
The cured film of the present invention is preferably formed in a pattern.

The moisture permeability of the cured film formed by curing the first resin layer and the second resin layer is preferably 350 g / m ² · 24 h or less from the viewpoint of suppressing corrosion of the metal wiring and the transparent electrode, more preferably m is ² · 24h or less, more preferably at most 250 g ^/ m 2 · 24h, even more preferably at most 200g ^/ m 2 · 24h. The moisture permeability can be measured with reference to the examples in the present specification.

<Electronic parts>
The electronic component according to the present embodiment includes a cured film formed using a photosensitive refractive index adjusting film. This cured film is preferably formed in a pattern. Examples of the electronic component include a touch panel, a liquid crystal display, an organic electroluminescence, a solar cell module, a printed wiring board, and electronic paper.

FIG. 3 is a schematic top view showing an example of a capacitive touch panel. The touch panel shown in FIG. 3 has a sensing area 102 for detecting a touch position coordinate on one side of a transparent substrate 101, and the transparent electrode 103 and the transparent electrode 104 for detecting a capacitance change in this area are based on the sensing area 102. It is provided on the material 101.

The transparent electrode 103 and the transparent electrode 104 detect the X position coordinate and the Y position coordinate of the touch position, respectively.

On the transparent substrate 101, a metal wiring 105 for transmitting a touch position detection signal from the transparent electrode 103 and the transparent electrode 104 to an external circuit is provided. Further, the metal wiring 105 and the transparent electrode 103 and the transparent electrode 104 are connected by a connection electrode 106 provided on the transparent electrode 103 and the transparent electrode 104. In addition, a connection terminal 107 for connection to an external circuit is provided at the end of the metal wiring 105 opposite to the connection portion between the transparent electrode 103 and the transparent electrode 104.

As shown in FIG. 3, by forming the cured film pattern 123, the transparent electrode 103, the transparent electrode 104, the metal wiring 105, the connection electrode 106, the function of the protective film of the connection terminal 107, and the transparent electrode pattern are formed. The function of adjusting the refractive index of the sensing region 102 is performed simultaneously.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

<Preparation of binder polymer solution (A1)>
A flask equipped with a stirrer, reflux condenser, inert gas inlet and thermometer was charged with (1) shown in Table 1, heated to 80 ° C. in a nitrogen gas atmosphere, and the reaction temperature was 80 ° C. ± 2 While maintaining the temperature, (2) shown in Table 1 was added dropwise uniformly over 4 hours. After dropwise addition of (2), stirring was continued at 80 ° C. ± 2 ° C. for 6 hours. A binder polymer solution (solid content 45 mass%) having a weight average molecular weight of 65,000 and an acid value of 78 mgKOH / g, (A1) was obtained. In Table 1, the unit of the amount of each component is part by mass.

<Preparation of binder polymer solution (A2)>
A binder polymer solution (solid content 57 mass%) having a weight average molecular weight of 18,000 and an acid value of 156.6 mgKOH / g, except that the blending amount was changed as shown in Table 1. Some (A2) was obtained.

[Preparation of Binder Polymer Solution (A3)>
A binder polymer solution (solid content 50 mass%) having a weight average molecular weight of 30,000 and an acid value of 156.6 mgKOH / g, except that the blending amount was changed as shown in Table 1. Some (A3) was obtained.

[Method for measuring weight average molecular weight]
The weight average molecular weight (Mw) was measured by gel permeation chromatography (GPC), and was derived by conversion using a standard polystyrene calibration curve. The GPC conditions are shown below.
<GPC conditions>
Pump: L-6000 (product name, manufactured by Hitachi, Ltd.)
Column: Gelpack GL-R420, Gelpack GL-R430, Gelpack GL-R440 (product name, manufactured by Hitachi Chemical Co., Ltd.)
Eluent: Tetrahydrofuran Measurement temperature: 40 ° C
Flow rate: 2.05 mL / min Detector: L-3300 (RI detector, manufactured by Hitachi, Ltd., product name)

[Measurement method of acid value]
The acid value was measured by a neutralization titration method based on JIS K0070 as shown below.

First, the binder polymer solution was heated at 130 ° C. for 1 hour to remove volatile matter, thereby obtaining a solid content. Then, after accurately weighing 1 g of the solid binder polymer, 30 g of acetone was added to the binder polymer, and this was uniformly dissolved to obtain a resin solution. Next, an appropriate amount of an indicator, phenolphthalein, was added to the resin solution, and neutralization titration was performed using a 0.1 mol / L potassium hydroxide aqueous solution. And the acid value was computed by following Formula.
Acid value = 0.1 × V × f ₁ × 56.1 / (Wp × I / 100)
In the formula, V is a titration amount (mL) of 0.1 mol / L potassium hydroxide aqueous solution used for titration, f ₁ is a factor (concentration conversion factor) of 0.1 mol / L potassium hydroxide aqueous solution, and Wp is a measured resin. The mass (g) and I of the solution indicate the proportion (mass%) of the non-volatile content in the measured resin solution.

[Measurement method of hydroxyl value]
The hydroxyl value was measured by a neutralization titration method based on JIS K0070 as shown below. First, the binder polymer solution was heated at 130 ° C. for 1 hour to remove volatile matter, thereby obtaining a solid content. Then, after accurately weighing 1 g of the above-mentioned solid binder polymer, the binder polymer was put into an Erlenmeyer flask, 10 mL of 10 mass% acetic anhydride pyridine solution was added to uniformly dissolve the binder polymer, and heated at 100 ° C. for 1 hour. . After heating, 10 mL of water and 10 mL of pyridine were added and heated at 100 ° C. for 10 minutes. Then, using an automatic titrator (product name: COM-1700, manufactured by Hiranuma Sangyo Co., Ltd.), 0.5 mol / L of potassium hydroxide was added. Neutralization titration was performed with an ethanol solution. And the hydroxyl value was computed by following Formula.
Hydroxyl value = (AB) × f ₂ × 28.05 / S + D
In the formula, A is the amount (mL) of 0.5 mol / L potassium hydroxide ethanol solution used for the blank test, B is the amount (mL) of 0.5 mol / L potassium hydroxide ethanol solution used for titration, f ₂ Is a factor (concentration conversion factor) of 0.5 mol / L potassium hydroxide ethanol solution, S is the mass (g) of the binder polymer, and D is the acid value.
In the blank test, the above process is performed without adding a binder polymer.

<Preparation of coating solution for forming first resin layer>
The components shown in Table 2 were mixed with a stirrer for 15 minutes to prepare coating solutions 1 to 5 for forming the first resin layer. In Table 2, the unit of the amount of each component is part by mass.

The symbols of the components in Table 2 have the following meanings.

(A) Component (A1): Propylene glycol monomethyl ether / toluene solution of copolymer having a monomer blending ratio (methacrylic acid / methyl methacrylate / ethyl acrylate = 12/58/30 (mass ratio)), weight average molecular weight 65,000, acid value 78 mgKOH / g, hydroxyl value 2 mgKOH / g, glass transition temperature 60 ° C.

(B) Component A-DCP: Tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name)
DCP: Tricyclodecane dimethanol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name)
T-1420 (T): Ditrimethylolpropane tetraacrylate (manufactured by Nippon Kayaku Co., Ltd., product name)

(C) Component IRGACURE OXE 01: 1,2-octanedione, 1-[(4-phenylthio) phenyl-, 2- (O-benzoyloxime)] (product name, manufactured by BASF Corporation)

(D) Component HAT: 5-amino-1H-tetrazole (product name, manufactured by Toyobo Co., Ltd.)

(E) Component PM-21: Phosphoric ester having a photopolymerizable unsaturated group (manufactured by Nippon Kayaku Co., Ltd., product name)

Other components Antage W-500 (AW-500): 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (product name, manufactured by Kawaguchi Chemical Co., Ltd.)

<Preparation of coating solution for forming second resin layer>
Components shown in Table 3 to be described later were mixed for 15 minutes using a stirrer to prepare coating solutions IM-1 to IM-4 for forming a second resin layer. In Table 3, the unit of the amount of each component is part by mass.

The symbols of the components in Table 3 have the following meanings.

Polymer (A1): Propylene glycol monomethyl ether / toluene solution of copolymer having a monomer blending ratio (methacrylic acid / methyl methacrylate / ethyl acrylate = 12/58/30 (mass ratio)), weight average molecular weight 65,000 , Acid value 78 mgKOH / g, hydroxyl value 2 mgKOH / g, glass transition temperature 60 ° C.
(A2): propylene glycol monomethyl of a copolymer having a monomer blending ratio (methacrylic acid / methyl methacrylate / butyl acrylate / butyl methacrylate = 24 / 43.5 / 15.2 / 17.3 (mass ratio)) Ether solution, weight average molecular weight 18,000, acid value 156.6 mg KOH / g.
(A3): propylene glycol monomethyl of a copolymer having a monomer blending ratio (methacrylic acid / methyl methacrylate / butyl acrylate / butyl methacrylate = 24 / 43.5 / 15.2 / 17.3 (mass ratio)) Ether solution, weight average molecular weight 30,000, acid value 156.6 mg KOH / g.

(B) Component BPE-1300: Ethoxylated bisphenol A dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name)

(D) Component B-6030: 5-amino-1H tetrazole (product name, manufactured by Chiyoda Chemical Co., Ltd.)

(E) Component PM-21: Phosphoric ester having a photopolymerizable unsaturated group (manufactured by Nippon Kayaku Co., Ltd., product name)

(F) Component OZ-S30K: Zirconia dispersion (manufactured by Nissan Chemical Industries, Ltd., product name: Nanouse OZ-S30K)

Other components L-7001: Octamethylcyclotetrasiloxane (product name, manufactured by Toray Dow Corning Co., Ltd.)

[Measurement of refractive index]
A coating solution for forming the second resin layer is uniformly applied on a glass substrate having a thickness of 0.7 mm, a length of 10 cm and a width of 10 cm by a spin coater, and dried for 3 minutes by a hot air dwelling dryer at 100 ° C. Then, the solvent was removed and a second resin layer was formed.

Next, the second resin layer obtained above was allowed to stand for 30 minutes in a box-type dryer (model number: NV50-CA, manufactured by Mitsubishi Electric Corporation) heated to 140 ° C., and the second resin layer was A sample for refractive index measurement was obtained. In addition, in the form of the photosensitive refractive index adjusting film, it is difficult to measure the refractive index of the second resin layer single layer, so it can be estimated from the value of the outermost surface layer on the protective film side of the second resin layer. it can.

Subsequently, the refractive index at a wavelength of 633 nm was measured for the obtained sample for refractive index measurement with ETA-TCM (product name, manufactured by AudioDev GmbH).

[Preparation of photosensitive film provided with first resin layer]
On a polyethylene terephthalate film having a thickness of 16 μm (support film, manufactured by Toray Industries, Inc., product name: FB40), a coating solution for forming the first resin layer shown in Tables 4 and 5 was applied, The solvent was removed by drying at 100 ° C. for 3 minutes to form a first resin layer. The amount of the coating solution was adjusted so that the thickness after drying was 8 μm.

Next, a 30 μm-thick polypropylene film (protective film, product name E-201F, manufactured by Oji F-Tex Co., Ltd.) is laminated on the obtained first resin layer to produce photosensitive films of Comparative Examples 1 to 4. did.

[Production of Photosensitive Refractive Index Adjusting Film Having First Resin Layer and Second Resin Layer]
On a 16 μm thick polyethylene terephthalate film (support film, manufactured by Toray Industries, Inc., product name: FB40), a coating solution for forming the first resin layer shown in Tables 4 and 5 was applied. The solvent was removed by drying at 100 ° C. for 3 minutes to form a first resin layer. The amount of the coating solution was adjusted so that the thickness after drying was 8 μm.

On a 30 μm-thick polypropylene film (protective film, manufactured by Oji F-Tex Co., Ltd.), a coating solution for forming the second resin layer shown in Tables 4 and 5 was applied and dried at 100 ° C. for 3 minutes. The solvent was removed to form a second resin layer. The amount of the coating solution was adjusted so that the thickness after drying was 70 nm.

Next, the obtained protective film having the second resin layer and the support film having the first resin layer were laminated with a second resin layer using a laminator (product name: HLM-3000, manufactured by Hitachi Chemical Co., Ltd.). The films were laminated at 23 ° C. so that the first resin layer and the first resin layer were in close contact with each other to obtain photosensitive refractive index adjusting films of Examples 1 to 6 and Comparative Examples 5 to 9.

[Measurement of resin layer thickness]
The thickness of the 2nd resin layer was measured by measuring the 2nd resin layer (single layer) produced above by F20 (FILMETRICS Co., Ltd. product name). Further, the thickness of the first resin layer was measured by measuring the first resin layer (single layer) produced above with a digital thickness gauge (manufactured by Nikon Corporation, product name: DIGIMICROSTAND MS-5C).

The following evaluation was performed about the produced photosensitive film and the photosensitive refractive index adjustment film.

[Measurement of transmittance of cured film]
The protective film of the photosensitive refractive index adjusting film prepared above is peeled off, and a laminator (Hitachi Chemical Co., Ltd.) is attached so that the second resin layer adheres onto a glass substrate having a thickness of 0.7 mm and a length of 10 cm × width of 10 cm. Product name: HLM-3000 type), roll temperature 120 ° C., substrate feed speed 1 m / min, pressure (cylinder pressure) 4 × 10 ⁵ Pa (thickness 0.7 mm, length 10 cm × width 10 cm) Therefore, the glass substrate, the second resin layer, the first resin layer, and the support film are laminated with a linear pressure of 9.8 × 10 ³ N / m). A laminated body was produced. Also for the photosensitive film, lamination was performed in the same procedure to produce a laminate in which the glass substrate, the first resin layer, and the support film were laminated.

Next, the obtained laminate was subjected to an exposure amount of 5 × 10 ² J / m ² (measured value at a wavelength of 365 nm) from above the photosensitive resin layer side using a parallel beam exposure machine (EXM1201 manufactured by Oak Manufacturing Co., Ltd.). ) After irradiating with ultraviolet rays, the support film is removed, and the sample is left for 30 minutes in a box dryer (model number: NV50-CA, manufactured by Mitsubishi Electric Corporation) heated to 140 ° C. Got.

Next, the transmittance of the obtained transmittance measurement sample was measured in a measurement wavelength range of 400 to 700 nm using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., product name: NDH 7000).

[Moisture permeability evaluation test of cured film]
The protective film of the obtained photosensitive film is peeled off, and this is applied to a filter paper (Advantech, No. 5C, φ90 mm circle, 130 μm thickness) with a roll temperature of 100 ° C., a substrate feed speed of 0.6 m / min, and pressure bonding. Lamination was performed under conditions of pressure (cylinder pressure) of 0.5 MPa. The support film was peeled off. A protective film of a new photosensitive film was peeled off and laminated on the first resin layer laminated on the filter paper. By repeating this operation, a laminate in which a first resin layer having a thickness of 40 μm (that is, five first resin layers) and a support film were laminated on a filter paper was produced. Also for the photosensitive refractive index adjusting film, a laminate in which the first resin layer, the second resin layer and the support film having a thickness of 40 μm were laminated on the filter paper was prepared by including the above procedure.

The laminated body was irradiated with ultraviolet rays at an exposure amount of 0.6 J / m ² from above the support film surface perpendicularly using a parallel light exposure machine (EXM1201 manufactured by Oak Manufacturing Co., Ltd.).

Next, the support film of the laminate irradiated with the ultraviolet rays was peeled and removed, and further, the laminate was irradiated with ultraviolet rays at an exposure amount of 1 × 10 ⁴ J / m ² from above. A moisture permeability measurement sample having a cured film formed on the filter paper was obtained.

Next, moisture permeability measurement was performed with reference to JIS standards (Z0208, cup method). A hygroscopic material (20 g of calcium chloride (anhydrous)) was placed in a measuring cup (φ 60 mm, depth 15 mm, Morai Moto Seisakusho Co., Ltd.). The measuring cup was covered with a circular sample piece cut with scissors to a diameter of 70 mm from the moisture permeability measurement sample. The sample was left in a constant temperature and humidity chamber at 60 ° C. and 90% RH for 24 hours. The moisture permeability was calculated from the change in the total mass of the measurement cup, the hygroscopic agent, and the circular sample piece before and after standing, and the moisture permeability was evaluated according to the following ratings.
A: Moisture permeability ≦ 300 (g / m ² · 24 h).
B: 300 <moisture permeability ≦ 400 (g / m ² · 24 h).
C: 400 <moisture permeability (g / m ² · 24 h).

[Developability evaluation test]
The protective film of the obtained photosensitive film and the photosensitive refractive index adjusting film was peeled off, and a laminator (Hitachi Chemical Co., Ltd., product name HLM-3000 type) was used on a copper substrate (vertical 12 cm × horizontal 5 cm). And laminating under the conditions of a roll temperature of 100 ° C., a substrate feed speed of 0.6 m / min, and a pressure bonding pressure (cylinder pressure) of 0.5 MPa, a copper substrate, a first resin layer and a support film, and a copper substrate, A sample for developability evaluation test in which the second resin layer, the first resin layer, and the support film were laminated was prepared.

The uppermost support film of the sample for developability evaluation test obtained above was peeled off. Thereafter, spray development was performed at 30 ° C. for 10 seconds or 20 seconds using a 1.0 mass% sodium carbonate aqueous solution. The obtained substrate surface state was observed with the naked eye, and the development residue was evaluated according to the following viewpoints.
A: Development residue is not confirmed on the substrate surface.
B: A slight development residue is confirmed on the surface of the substrate.
C: Development residue is confirmed on the substrate surface.

<Results of moisture permeability evaluation test and developability evaluation test>

As shown in Table 4 and Table 5 below, a first resin layer containing a di (meth) acrylate compound having a dicyclopentanyl structure or a dicyclopentenyl structure was provided on the first resin layer. Examples 1 to 6 using a photosensitive refractive index adjusting film comprising a polymer having an acid value of 150 mgKOH / g or more and a second resin layer containing metal oxide particles achieve both low moisture permeability and developability. I was able to. On the other hand, Comparative Examples 1 to 4 using a photosensitive film not containing the second resin layer had a problem in developability. Further, in Comparative Examples 5 to 8 using the second resin layer containing a polymer having an acid value of 150 mgKOH / g or less, there was a problem in developability. In Comparative Example 9 using the first resin layer containing a photopolymerizable compound other than the di (meth) acrylate compound having a dicyclopentanyl structure or a dicyclopentenyl structure, there was a problem with low moisture permeability. It was.

In the case of the photosensitive refractive index adjusting film of the present invention, it was confirmed that the developability can be improved even if a material that is inferior in developability is used for the first resin layer.

DESCRIPTION OF SYMBOLS 1 ... Photosensitive refractive index adjustment film, 10 ... Support film, 20 ... 1st resin layer, 30 ... 2nd resin layer, 22 ... Cured film of 1st resin layer, 32 ... Curing of 2nd resin layer Membrane, 40 ... Protective film, 50 ... Substrate with transparent electrode pattern, 50a ... Transparent electrode pattern, 100 ... Transparent laminate, 101 ... Transparent substrate, 102 ... Sensing region, 103, 104 ... Transparent electrode, 105 ... Metal wiring 106 connection electrode 107 connection terminal 123 cured film pattern

Claims (18)

1. A support film, a first resin layer containing a di (meth) acrylate compound having a dicyclopentanyl structure or a dicyclopentenyl structure provided on the support film, and provided on the first resin layer And a second resin layer containing a polymer having an acid value of 150 mgKOH / g or more and metal oxide particles.
2. The photosensitive refractive index adjustment film of Claim 1 whose di (meth) acrylate compound which has the said dicyclopentanyl structure or dicyclopentenyl structure is a compound represented by following General formula (1).
   

   

   [In General Formula (1), R ¹ and R ² each independently represent a hydrogen atom or a methyl group, X represents a divalent group having a dicyclopentanyl structure or a dicyclopentenyl structure, and R ³ And R ⁴ each independently represents an alkylene group having 1 to 4 carbon atoms, n and m each independently represents an integer of 0 to 2, p and q each independently represents an integer of 0 or more, and p + q = 0 to 10 is selected. ]
3. The photosensitive refractive index adjusting film according to claim 1 or 2, wherein the polymer having an acid value of 150 mgKOH / g or more has a carboxyl group.
4. The polymer having an acid value of 150 mgKOH / g or more is (meth) acrylic acid, (meth) acrylic acid glycidyl ester, (meth) acrylic acid benzyl ester, styrene, (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester. A structural unit derived from at least one compound selected from the group consisting of butyl ester, (meth) acrylic acid ester, and (meth) acrylic acid-2-ethylhexyl ester. The photosensitive refractive index adjustment film of description.
5. The photosensitive refractive index adjusting film according to any one of claims 1 to 4, wherein the metal oxide particles are zirconium oxide or titanium oxide.
6. The photosensitive refractive index adjusting film according to any one of claims 1 to 5, wherein the first resin layer contains a binder polymer and a photopolymerization initiator.
7. The photosensitive refractive index adjusting film according to claim 6, wherein the photopolymerization initiator contains an oxime ester compound.
8. The photosensitive refractive index adjusting film according to claim 6 or 7, wherein the binder polymer has a carboxyl group.
9. The binder polymer is (meth) acrylic acid, (meth) acrylic acid glycidyl ester, (meth) acrylic acid benzyl ester, styrene, (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid The photosensitive refractive index according to any one of claims 6 to 8, which has a structural unit derived from at least one compound selected from the group consisting of butyl ester and (meth) acrylic acid-2-ethylhexyl ester. Adjustment film.
10. The photosensitive refractive index adjusting film according to any one of claims 1 to 9, wherein the first resin layer contains a phosphoric ester having an ethylenically unsaturated group.
11. The photosensitive refractive index adjusting film according to any one of claims 1 to 10, wherein the refractive index at a wavelength of 633 nm of the second resin layer is 1.5 to 1.9.
12. The photosensitive refractive index adjusting film according to any one of claims 1 to 11, wherein the thickness of the second resin layer is 40 nm to 500 nm.
13. The photosensitive member according to any one of claims 1 to 12, wherein the minimum value of transmittance at a wavelength of 400 to 700 nm of the laminate comprising the first resin layer and the second resin layer is 90% or more. Refractive index adjusting film.
14. The photosensitive refractive index adjusting film according to any one of claims 1 to 13, wherein the total thickness of the first resin layer and the second resin layer is 30 μm or less.
15. The first resin layer and the second resin using the photosensitive refractive index adjusting film according to any one of claims 1 to 14 so that the second resin layer is in close contact with a substrate. Laminating the layers;
    Exposing a predetermined portion of the first resin layer and the second resin layer on the substrate;
    Removing the portion other than the exposed predetermined portion;
    A method for forming a cured film pattern comprising:
16. A cured film obtained by curing the second resin layer and the first resin layer of the photosensitive refractive index adjusting film according to any one of claims 1 to 14.
17. The cured film according to claim 16, wherein the cured film is formed in a pattern.
18. An electronic component having the cured film according to claim 16 or 17.

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