WO2016027580A1 - Actinic-ray-curable resin composition, optical member, pressure-sensitive adhesive sheet, laminate for touch panel, and capacitive touch panel - Google Patents

Abstract

The purpose of the present invention is to provide: an actinic-ray-curable resin composition that gives a pressure-sensitive adhesive sheet which has a reduced residual-monomer content and is excellent in terms of adhesion and conformability to level differences and which, when used in capacitive touch panels, can inhibit the occurrence of malfunctions in a wide ambient temperature range from low to high temperatures; an optical member and a pressure-sensitive adhesive sheet each obtained by curing the actinic-ray-curable resin composition; and a laminate for touch panels and a capacitive touch panel which both include the pressure-sensitive adhesive sheet. This actinic-ray-curable resin composition comprises a polymerizable compound (A) selected from the group consisting of polymerizable compounds (a1) and (a2) represented by specific formulae, a polymerizable compound (B) selected from the group consisting of the diesters and diamides of one or more dicarboxylic acids selected from the group consisting of maleic acid, fumaric acid, and citraconic acid, and a photopolymerization initiator (C).

Description

Active energy ray-curable resin composition, optical member, pressure-sensitive adhesive sheet, laminate for touch panel, and capacitive touch panel

The present invention relates to an active energy ray-curable resin composition, an optical member, an adhesive sheet (particularly an adhesive sheet for a touch panel), a laminate for a touch panel, and a capacitive touch panel.

In recent years, the rate of mounting touch panels on mobile phones, portable game devices, and the like has increased, and for example, capacitive touch panels capable of detecting multiple points (hereinafter simply referred to as touch panels) are attracting attention.
Usually, when manufacturing a touch panel, a composition that cures with active energy rays (active energy ray-curable composition) or the like is used in order to bring each member such as a display device or a touch panel sensor into close contact. In addition, the said composition is often shape | molded and used for a sheet form.

For example, Patent Document 1 discloses an active energy ray-curable adhesive composition containing a (meth) acrylate monomer and a photopolymerization initiator, and describes that it can be suitably used for a touch panel. (Claims, Examples, Paragraph [0021]).

JP 2013-144749 A

On the other hand, the adhesive sheet is required to have various characteristics when used for a touch panel. For example, excellent adhesion is required from the viewpoint of durability of the touch panel. Further, from the viewpoint of the adhesiveness of the pressure-sensitive adhesive sheet and the durability of the pressure-sensitive adhesive sheet itself, a low monomer residual ratio is required. Moreover, when bonding to the transparent panel which has the level | step difference by a decoration part, it is calculated | required that there are few bubble generation | occurrence | production in a level | step-difference part. That is, it is required to have excellent step following ability. Furthermore, from the viewpoint of environmental adaptability of the touch panel, it is required that malfunctions are unlikely to occur in various usage environments such as cold regions and warm regions. That is, a low malfunction occurrence rate is required.

Under these circumstances, the present inventor made a pressure-sensitive adhesive sheet using a composition containing a (meth) acrylate monomer and a photopolymerization initiator with reference to Patent Document 1, and found the above characteristics (monomer residual ratio, adhesion). It has become clear that at least one of the following characteristics, step following ability and malfunction occurrence rate does not meet the level required recently.

Therefore, in view of the above circumstances, the present invention has a low monomer residual rate when made into a pressure-sensitive adhesive sheet, excellent adhesion and step followability, and low temperature when used as a pressure-sensitive adhesive sheet as a pressure-sensitive adhesive sheet. Active energy ray-curable resin composition capable of suppressing the occurrence of malfunction under a wide temperature environment from high to high temperature, an optical member and an adhesive sheet obtained by curing the active energy ray-curable resin composition And it aims at providing the laminated body for touch panels provided with the said adhesive sheet, and a capacitive touch panel.

As a result of intensive studies on the above problems, the present inventors have found that the above problems can be solved by using two kinds of specific polymerizable compounds (monomers), and have reached the present invention.
That is, the present inventor has found that the above problem can be solved by the following configuration.

(1) a polymerizable compound A1 selected from the group consisting of a polymerizable compound a1 represented by formula (I) described later and a polymerizable compound a2 represented by formula (II) described later;
A polymerizable compound B selected from the group consisting of diesters and diamides of dicarboxylic acids selected from the group consisting of maleic acid, fumaric acid and citraconic acid;
An active energy ray-curable resin composition containing a photopolymerization initiator C.
(2) The active energy ray-curable resin composition according to (1), wherein the ratio of the number of moles of the polymerizable compound A to the number of moles of the polymerizable compound B is 0.6 to 4.
(3) The active energy ray-curable resin composition according to (1) or (2), further including a crosslinking agent.
(4) The Tg of the homopolymer of the polymerizable compound A is 50 ° C. or higher, and the Tg of the homopolymer of the polymerizable compound B is 0 ° C. or lower.
Alternatively, any one of the above (1) to (3), wherein the Tg of the homopolymer of the polymerizable compound A is 0 ° C. or lower and the Tg of the homopolymer of the polymerizable compound B is 50 ° C. or higher. The active energy ray-curable resin composition described.
(5) An optical member obtained by curing the active energy ray-curable resin composition according to any one of (1) to (4) above.
(6) A pressure-sensitive adhesive sheet obtained by curing the active energy ray-curable resin composition according to any one of (1) to (4) above.
(7) The adhesive sheet according to (6), which is an adhesive sheet for a touch panel.
(8) A laminate for a touch panel comprising the pressure-sensitive adhesive sheet according to (7) and a capacitive touch panel sensor.
(9) Further, a protective substrate is provided,
The laminated body for touchscreens as described in said (8) provided with the said protective substrate, the said adhesive sheet, and the said capacitive touch panel sensor in this order.
(10) A capacitive touch panel comprising the capacitive touch panel sensor, the adhesive sheet according to (7), and a display device in this order.

As shown below, according to the present invention, when a pressure-sensitive adhesive sheet is used, the monomer residual ratio is low, the adhesion and the step following ability are excellent, and when used as a pressure-sensitive adhesive sheet for a capacitive touch panel, the temperature is low. Active energy ray-curable resin composition capable of suppressing the occurrence of malfunction under a wide temperature environment from high to high temperature, an optical member and an adhesive sheet obtained by curing the active energy ray-curable resin composition And the laminated body for touchscreens and an electrostatic capacitance type touch panel provided with the said adhesive sheet can be provided.
Hereinafter, “the occurrence of malfunctions in a wide range of temperature environments from low to high temperatures when used in a capacitive touch panel” is also simply referred to as “excellent low malfunction”.

It is sectional drawing of the one aspect | mode of the laminated body for touchscreens of this invention. It is sectional drawing of another aspect of the laminated body for touchscreens of this invention. It is sectional drawing of the electrostatic capacitance type touch panel of this invention. It is a top view of one embodiment of a capacitive touch panel sensor. FIG. 5 is a cross-sectional view taken along a cutting line AA shown in FIG. It is an enlarged plan view of a 1st detection electrode. It is a partial cross section of other embodiment of an electrostatic capacitance type touch panel sensor. It is a partial cross section of other embodiment of an electrostatic capacitance type touch panel sensor. It is a partial top view of one Embodiment of other embodiment of an electrostatic capacitance type touch panel sensor. FIG. 10 is a cross-sectional view taken along a cutting line AA shown in FIG.

Below, the active energy ray-curable resin composition of the present invention, an optical member and an adhesive sheet obtained by curing the active energy ray-curable resin composition, and a laminate for a touch panel comprising the adhesive sheet, A capacitive touch panel will be described.
In this specification, (meth) acryl represents acryl or methacryl, (meth) acrylate represents acrylate or methacrylate, (meth) acryloyl represents acryloyl or methacryloyl, and (meth) acryl Represents acrylic or methacrylic.
In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
Moreover, in this specification, when a component contains 2 or more types of compounds, content of the said component refers to total content.

[Active energy ray-curable resin composition]
The active energy ray-curable resin composition of the present invention (hereinafter, “active energy ray-curable resin composition” is also simply referred to as “composition”) includes a polymerizable compound a1 represented by the formula (I) described below, And a diester of a polymerizable compound A selected from the group consisting of a polymerizable compound a2 represented by formula (II) and a dicarboxylic acid selected from the group consisting of maleic acid, fumaric acid and citraconic acid, and A polymerizable compound B selected from the group consisting of diamide and a photopolymerization initiator C are contained.
Since the composition of this invention takes such a structure, it is thought that a desired effect is acquired. The reason is not clear, but it is presumed that it is as follows.

As described above, the composition of the present invention contains the polymerizable compound A and the polymerizable compound B.
Here, the unsaturated bond part of the polymerizable compound A has a relatively high electron density, and the unsaturated bond part of the polymerizable compound B has a relatively low electron density. Therefore, the radicals emitted from both are highly reactive with each other, and the monomer is rapidly consumed during curing. That is, the pressure-sensitive adhesive sheet obtained from the composition of the present invention (the pressure-sensitive adhesive sheet of the present invention) has a low monomer residual ratio. In addition, when a monomer remains in an adhesive sheet, it will lead to the fall of adhesiveness and durability.
Furthermore, the polymer chain formed by curing has a structure having a side chain for each carbon, such as maleic acid and fumaric acid, and the structure is greatly different from a general acrylic polymer having a side chain for every two carbons. Therefore, it is expected that the repulsion between the side chains is large, and the aggregation between the polymer chains is moderately suppressed. As a result, the pressure-sensitive adhesive sheet of the present invention is highly flexible.
As described above, the pressure-sensitive adhesive sheet of the present invention is considered to exhibit excellent adhesion as a result because of a small amount of residual monomer and high flexibility.
Moreover, since the adhesive sheet of this invention is high in flexibility as above-mentioned, it is thought that it is excellent also in level | step difference followability. Furthermore, as described above, since the pressure-sensitive adhesive sheet of the present invention has a small amount of residual monomer, it is considered that there are few residual double bonds, resulting in a low dielectric constant and excellent low malfunction.

Hereinafter, each component contained in the composition of the present invention will be described in detail.

[Polymerizable compound A]
The polymerizable compound A (hereinafter also referred to as monomer A) is selected from the group consisting of a polymerizable compound a1 represented by the following formula (I) and a polymerizable compound a2 represented by the following formula (II). It is a polymerizable compound. The polymerizable compound A may contain both the polymerizable compound a1 and the polymerizable compound a2.

In the above formulas (I) and (II), R ₁ to R ₃ each independently represents a hydrogen atom or an alkyl group (preferably a substituent W described later) (preferably a substituent W described later). An alkyl group having 1 to 10 carbon atoms), an alkoxy group (—OR: R represents an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms)), an alkylthio group (—SR: R represents an alkyl group (preferably Or an alkylamino group (—NR ₂ : R represents a hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms). They may be the same or different, but one of the two R's represents an alkyl group).

In the above formulas (I) and (II), R ₄ to R ₇ may each independently have a hydrogen atom, —CO—R _A , or a substituent (for example, substituent W described later). Represents an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms), an aryl group, or a heteroaryl group.
The aryl group is preferably an aryl group having 6 to 18 carbon atoms. Specific examples of the ring constituting the aryl group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring, a triphenylene ring, a naphthacene ring, and a biphenyl ring. And a terphenyl ring (the three benzene rings may be connected in any connection manner).
The heteroaryl group is preferably a heteroaryl group comprising a 5-membered, 6-membered or 7-membered ring or a condensed ring thereof. Examples of the hetero atom contained in the heteroaryl group include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the ring constituting the heteroaryl group include furan ring, thiophene ring, pyrrole ring, oxazole ring, isoxazole ring, oxadiazole ring, thiazole ring, isothiazole ring, thiadiazole ring, imidazole ring, pyrazole ring, Triazole ring, furazane ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, tetrazine ring, benzofuran ring, isobenzofuran ring, benzothiophene ring, indole ring, indoline ring, isoindole ring, benzoxazole Ring, benzothiazole ring, indazole ring, benzimidazole ring, quinoline ring, isoquinoline ring, cinnoline ring, phthalazine ring, quinazoline ring, quinoxaline ring, dibenzofuran ring, dibenzothiophene ring, carbazole ring, Kurijin ring, phenanthridine ring, phenanthroline ring, phenazine ring, naphthyridine ring, purine ring and pteridine ring.
R _A represents a hydrogen atom or an alkyl group, an aryl group, or a heteroaryl group which may have a substituent (for example, a substituent W described later). Specific examples and preferred embodiments of the alkyl group, aryl group, and heteroaryl group are as described above.

In the above formulas (I) and (II), R ₁ to R ₇ may be bonded to each other to form a ring.
Here, “to form a ring by bonding to each other” means that two or more groups are bonded through a single bond with a hydrogen atom as a bond at an arbitrary hydrogen atom position to form a ring. Intended.
For example, VC (vinylene carbonate) used in the examples described later is such that R ₆ in the above formula (II) is —CO—H (formyl group), R ₇ is a hydrogen atom, R ₆ formyl This corresponds to an embodiment in which a hydrogen atom in the group and a hydrogen atom of R ₇ are bonded via a single bond using a hydrogen atom as a bond to form a ring.
In the above formula (I), R ₄ and R ₅ are preferably bonded to each other to form a ring.
In the above formula (II), R ₆ and R ₇ are preferably bonded to each other to form a ring.

A preferred embodiment of the polymerizable compound a1 represented by the above formula (I) is, for example, a polymerizable compound a11 represented by the following formula (I-1). The polymerizable compound a11 corresponds to an embodiment in which R ₄ and R ₅ in the above formula (I) are bonded to each other to form a ring.

Definition of _R 1 ~ _{R 3} in the above formula (I-1), specific examples and preferred embodiments are the same as _R 1 ~ _{R 3} in formula (I) as defined above.

In the above formula (I-1), R ₄₁ and R ₅₁ are each independently —CO—R _A1 — or an alkylene group (which may have a substituent W described later) ( Preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 2 to 8 carbon atoms, still more preferably an alkylene group having 3 to 6 carbon atoms, an arylene group or a heteroarylene group.
The arylene group is preferably an arylene group having 6 to 18 carbon atoms. Specific examples of the ring constituting the arylene group are the same as R ₄ to R _{7 in} the above formulas (I) and (II).
The heteroarylene group is preferably a heteroarylene group comprising a 5-membered, 6-membered or 7-membered ring or a condensed ring thereof. Examples of the hetero atom contained in the heteroarylene group include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the ring constituting the heteroarylene group are the same as R ₄ to R _{7 in} the above formulas (I) and (II).
R _A1 represents a single bond or an alkylene group, an arylene group, or a heteroarylene group, which may have a substituent (for example, a substituent W described later). Specific examples and preferred embodiments of the alkylene group, arylene group, and heteroarylene group are as described above.

A preferred embodiment of the polymerizable compound a11 represented by the above formula (I-1) is, for example, a polymerizable compound a12 represented by the following formula (I-2).

Definition of _R 1 ~ _{R 3} in the above formula (I-2), specific examples and preferred embodiments are the same as _R 1 ~ _{R 3} in formula (I) as defined above.
Definition of _{R 41} and _{R 51} in the above formula (I-2), specific examples and preferred embodiments are the same as _{R 41} and _{R 51} in the above formula (I-1).

In the above formula (I-2), R _X and R _Y represent a hydrogen atom or a substituent (for example, substituent W described later). When n is an integer of 2 or more, a plurality of R _X may be the same or different.

In the above formula (I-2), n represents an integer of 1 or more. n is preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and still more preferably 1.
For example, when n is 1, R ₄₁ is —CO—R _A1 — (R _A1 : single bond), and R ₅₁ is a methylene group, the nitrogen atom in the above formula (I-2) is substituted. When the ring to be included is a 5-membered ring, n is 3, R ₄₁ is —CO—R _A1 — (R _A1 : single bond), and R ₅₁ is a methylene group, the above formula (I-2) The ring containing a nitrogen atom is a 7-membered ring.

Specific examples of the polymerizable compound a12 include N-vinylpyrrolidone and N-vinylcaprolactam.

A preferred embodiment of the polymerizable compound a2 represented by the above formula (II) is, for example, a polymerizable compound a21 represented by the following formula (II-1). The polymerizable compound a21 corresponds to an embodiment in which R ₆ and R ₇ in the above formula (II) are bonded to each other to form a ring.

The formula (II-1) Definition of _R 1 ~ _{R 2} in, specific examples and preferred embodiments are the same as _R 1 ~ _{R 2} in the above-mentioned formula (I).

In the above formula (II-1), R ₆₁ and R ₇₁ may each independently have a single bond, —CO—R _A1 —, or a substituent (for example, substituent W described later). An alkylene group (preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 2 to 8 carbon atoms, and still more preferably an alkylene group having 3 to 6 carbon atoms), an arylene group, or a heteroarylene group is represented.
The arylene group is preferably an arylene group having 6 to 18 carbon atoms. Specific examples of the ring constituting the arylene group are the same as R ₄ to R _{7 in} the above formulas (I) and (II).
The heteroarylene group is preferably a heteroarylene group comprising a 5-membered, 6-membered or 7-membered ring or a condensed ring thereof. Examples of the hetero atom contained in the heteroarylene group include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the ring constituting the heteroarylene group are the same as R ₄ to R _{7 in} the above formulas (I) and (II).
R _A1 represents a single bond or an alkylene group, an arylene group, or a heteroarylene group, which may have a substituent (for example, a substituent W described later). Specific examples and preferred embodiments of the alkylene group, arylene group, and heteroarylene group are as described above.
When one of R ₆₁ and R ₇₁ is a single bond, the other is preferably not a single bond.

Specific examples of the polymerizable compound a21 include vinylene carbonate.

In the composition of the present invention, the content of the polymerizable compound A is not particularly limited, but is preferably 0.1 to 30% by mass, more preferably 1 to 15% by mass with respect to the total amount of the composition. preferable.
In addition, in this specification, when the composition of this invention contains a solvent, a composition whole quantity means the sum total of components other than a solvent.

[Polymerizable compound B]
The polymerizable compound B (hereinafter also referred to as monomer B) is a polymerizable compound selected from the group consisting of diesters and diamides of dicarboxylic acids selected from the group consisting of maleic acid, fumaric acid and citraconic acid.
That is, the polymerizable compound B is maleic acid diester, maleic acid diamide, fumaric acid diester, fumaric acid diamide, citraconic acid diester, or citraconic acid diamide. The polymerizable compound B may contain two or more of these.
The diester is preferably a diester of the dicarboxylic acid and R _B OH (preferably an alcohol) (where R _B represents a hydrocarbon group). Among these, a diester of dicarboxylic acid selected from the group consisting of maleic acid and fumaric acid and R _B OH is preferable, and a diester of fumaric acid and R _B OH is more preferable.
Examples of R _B (hydrocarbon group) include an aliphatic hydrocarbon group and an aromatic hydrocarbon group.
The aliphatic hydrocarbon group may be linear, branched or cyclic. Specific examples of the aliphatic hydrocarbon group include a linear or branched alkyl group (particularly 1 to 20 carbon atoms), a linear or branched alkenyl group (particularly 2 to 20 carbon atoms), Examples thereof include a linear or branched alkynyl group (particularly, having 2 to 20 carbon atoms). The aliphatic hydrocarbon group is preferably a linear or branched alkyl group.
Examples of the aromatic hydrocarbon group include an aryl group and a naphthyl group. Examples of the aryl group include aryl groups having 6 to 18 carbon atoms such as a phenyl group, a tolyl group, and a xylyl group.

The polymerizable compound B is preferably a maleic acid diester, a fumaric acid diester, or a citraconic acid diester, more preferably a maleic acid diester or a fumaric acid diester, and even more preferably a fumaric acid diester.

A preferred embodiment of the maleic acid diester includes, for example, a compound represented by the following formula (B1).

In the above formula (B1), the definition, specific examples and preferred embodiments of R _B1 are the same as those of the above R _B. Two R _B1 may be the same or different.

As a preferable embodiment of the above fumaric acid diester, for example, a compound represented by the following formula (B2) can be mentioned.

In the above formula (B2), the definition, specific examples and preferred embodiments of R _B2 are the same as those of R _B. Two R _B2 may be the same or different.

In the composition of the present invention, the content of the polymerizable compound B is not particularly limited, but is preferably 1 to 70% by mass, and more preferably 10 to 30% by mass with respect to the total amount of the composition.

The ratio (A / B) of the number of moles (A) of the polymerizable compound A to the number of moles (B) of the polymerizable compound B is not particularly limited, but is preferably 0.25 to 4, preferably 0.6 to 2. 0.0 is more preferable.

The Tg when the polymerizable compound A is a homopolymer and the Tg when the polymerizable compound B is a homopolymer are not particularly limited, but preferably satisfy the following (i) or (ii). (I) The Tg of the homopolymer of the polymerizable compound A is 50 ° C. or more (preferably 50 to 100 ° C.), and the Tg of the homopolymer of the polymerizable compound B is 0 ° C. or less (preferably −50 to 0 ° C.).
(Ii) The Tg of the homopolymer of the polymerizable compound A is 0 ° C. or less (preferably −50 to 0 ° C.), and the Tg of the homopolymer of the polymerizable compound B is 50 ° C. or more (preferably 50 to 100 ° C.).
Here, the homopolymer means a homopolymer having a degree of polymerization of 100.
Moreover, Tg (glass transition temperature) is measured by DSC (differential scanning calorimetry).

[Photopolymerization initiator C]
The photopolymerization initiator C (hereinafter also referred to as initiator C) is not particularly limited, and a known photopolymerization initiator can be used. For example, alkynephenone photopolymerization initiator, methoxyketone photopolymerization initiator, acylphosphine oxide photopolymerization initiator, hydroxyketone photopolymerization initiator (eg, IRGACURE184; 1,2-α-hydroxyalkylphenone) Aminoketone photopolymerization initiators (for example, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one (IRGACURE® 907), oxime photopolymerization initiators, Can be mentioned.

Among these, the photopolymerization initiator preferably includes at least one selected from the group consisting of monoacylphosphine oxide (A1) and bisacylphosphine oxide (A2).
The monoacylphosphine oxide (A1) is not particularly limited, and a known monoacylphosphine oxide can be used. As a suitable aspect of monoacylphosphine oxide (A1), the monoacylphosphine oxide represented by a following formula (A1) is mentioned, for example.

In the above formula (A1), R ^A11 represents a hydrocarbon group which may have a substituent. Although it does not restrict | limit especially as a hydrocarbon group, As an example, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, etc. are mentioned, Especially, it is preferable that it is an aromatic hydrocarbon group.
The aliphatic hydrocarbon group may be linear, branched or cyclic. Specific examples of the aliphatic hydrocarbon group include a linear or branched alkyl group (particularly 1 to 20 carbon atoms), a linear or branched alkenyl group (particularly 2 to 20 carbon atoms), Examples thereof include a linear or branched alkynyl group (particularly, having 2 to 20 carbon atoms). The aliphatic hydrocarbon group is preferably a linear or branched alkyl group.
Examples of the aromatic hydrocarbon group include an aryl group and a naphthyl group. Examples of the aryl group include aryl groups having 6 to 18 carbon atoms such as a phenyl group, a tolyl group, and a xylyl group.
The substituent that the hydrocarbon group may have is not particularly limited, but specific examples include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, etc.) and the like. Can be mentioned. Specific examples and preferred embodiments of the aliphatic hydrocarbon group and the aromatic hydrocarbon group are as described above. The substituent is preferably an aliphatic hydrocarbon group.

In the formula (A1), R ^A12 and R ^A13 each independently represent a hydrocarbon group or a hydrocarbon oxy group (—OR: where R represents a hydrocarbon group) which may have a substituent. . Specific examples of the hydrocarbon group of the hydrocarbon group which may have a substituent and the hydrocarbon group (R) of the hydrocarbon oxy group are the same as the hydrocarbon group described above. Moreover, the specific example and suitable aspect of a substituent which a hydrocarbon group or a hydrocarbon oxy group may have are the same as the substituent mentioned above.
One of R ^A12 and R ^A13 is preferably an aromatic hydrocarbon group which may have a substituent. When one of R ^A12 and R ^{A13 is} an aromatic hydrocarbon group which may have a substituent, the other may have a phenyl group (particularly having 6 to 18 carbon atoms) or an alkoxy group (which may have a substituent) Particularly preferred are those having 1 to 5 carbon atoms, and more preferred are phenyl groups (particularly 6 to 18 carbon atoms) which may have a substituent.

Specific examples of the monoacylphosphine oxide (A1) include benzoyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyl-diphenylphosphine oxide, 3, Examples include 4-dimethylbenzoyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoyl-phenylethoxyphosphine oxide, and the like.

The bisacylphosphine oxide (A2) is not particularly limited, and a known bisacylphosphine oxide can be used. As a suitable aspect of bisacylphosphine oxide (A2), the bisacylphosphine oxide represented by a following formula (A2) is mentioned, for example.

In the formula (A2), R ^A21 to R ^A23 each independently represent a hydrocarbon group that may have a substituent. Specific examples and preferred embodiments of the hydrocarbon group and the substituent are the same as those of R ^A11 described above.

Specific examples of bisacylphosphine oxide (A2) include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide. And bis (2,6-dimethylbenzoyl) -ethylphosphine oxide.

In the composition of the present invention, the content of the photopolymerization initiator C is not particularly limited, but is preferably 0.1 to 10% by mass, and preferably 1 to 5% by mass with respect to the total amount of the composition. More preferred.

[Optional ingredients]
The composition of this invention may contain components other than the component mentioned above as needed.
Examples of such components include polymerizable compounds other than the polymerizable compounds A and B, a crosslinking agent, a tackifier, a plasticizer, a polymerization inhibition inhibitor, a chain transfer agent, a solvent, and a sensitizing dye.

<Polymerizable compounds other than polymerizable compounds A and B>
A polymerizable compound (monomer) other than the polymerizable compounds A and B is not particularly limited, and specific examples include (meth) acrylic monomers.

The (meth) acrylic monomer is not particularly limited. For example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) ) Acrylate, tetrahydrofurfuryl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, isononyl (meth) acrylate, isodecinyl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) Acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, isobornyl (meth) acrylate, butoxydiethylene glycol (meth) acrylate Rate, benzyl (meth) acrylate, dicyclohexyl (meth) acrylate, 2-dicyclohexyloxyethyl (meth) acrylate, morpholino (meth) acrylamide, phenoxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, ethylene glycol di (meth) ) Acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, nonanediol di ( (Meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, 2-morpholinoethyl (meth) acrylate, 9-anthryl (meth) acrylate, 2,2-bi (4- (meth) acryloyloxyphenyl) propane, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trans-1,4-cyclohexanediol di (meth) acrylate, dicyclopentenyloxyethyl (meth) ) Acrylate, methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, polyethylene glycol (meth) Acrylate, polypropylene glycol (meth) acrylate, poly (ethylene glycol-tetramethylene glycol) (meth) acrylate, poly Examples include ri (propylene glycol-tetramethylene glycol) (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, glycidyl (meth) acrylate, and the like.

In the composition of the present invention, the total content of the polymerizable compounds (the total of the polymerizable compound A, the polymerizable compound B, and the polymerizable compounds other than the polymerizable compounds A and B) is not particularly limited, The amount is preferably 1 to 80% by mass, more preferably 10 to 40% by mass, based on the total amount of the product.

<Crosslinking agent>
The composition of the present invention preferably contains a crosslinking agent.
Although the said crosslinking agent is not restrict | limited in particular, As a specific example, the compound (henceforth the crosslinking agent D) etc. which have several (2 or more) radically polymerizable group are mentioned.
The cross-linking agent D only needs to have a plurality of radically polymerizable groups, but preferably has 2 to 6, more preferably 2 to 3.
The kind of the radical polymerizable group is not particularly limited, and examples thereof include (meth) acryloyl group, acrylamide group, vinyl group, styryl group, and allyl group. Among these, a methacryloyl group is preferable in that the effect of the present invention is more excellent.

The type of skeleton in the cross-linking agent is not particularly limited, but is preferably one selected from the group consisting of polybutadiene, polyisoprene, hydrogenated polybutadiene, and hydrogenated polyisoprene. That is, the cross-linking agent is preferably one type selected from the group consisting of polybutadiene, polyisoprene, hydrogenated polybutadiene, and hydrogenated polyisoprene having a methacryloyl group.

In the composition of the present invention, the content of the crosslinking agent is not particularly limited, but is preferably 10 to 30% by mass, and more preferably 15 to 25% by mass with respect to the total amount of the composition.
In view of more excellent effects of the present invention, the content of the crosslinking agent is preferably 50 to 100% by mass and more preferably 70 to 90% by mass with respect to the total of the polymerizable compounds. preferable.

<Tackifier>
As the tackifier, those known in the field of patch or patch preparation may be appropriately selected and used. Examples of tackifiers include tackifier resins, such as rosin resins such as rosin esters, hydrogenated rosin esters, disproportionated rosin esters, and polymerized rosin esters; coumarone indene resins, hydrogenated coumarone indene resins, Coumarone indene resins such as phenol-modified coumarone indene resin and epoxy-modified coumarone indene resin; α-pinene resin, β-pinene resin; polyterpene resin, hydrogenated terpene resin, aromatic modified terpene resin, terpene phenol resin, etc. Terpene-based resins; petroleum-based resins such as aliphatic petroleum resins, aromatic petroleum resins, and aromatic-modified aliphatic petroleum resins. These can be used alone or in combination of two or more, and rosin resins, terpene resins and coumarone indene resins are particularly preferable.

In the composition of the present invention, the content of the tackifier is not particularly limited, but is preferably 10 to 70% by mass, and more preferably 30 to 50% by mass with respect to the total amount of the composition.

<Plasticizer>
The plasticizer is not particularly limited, but for example, natural rubber, polyisobutylene, polybutene, polyisoprene, polybutadiene, hydrogenated polyisoprene, hydrogenated polybutadiene, styrene butadiene rubber, or a co-polymer of any combination selected from these groups. Examples include coalescence.
In addition, it is preferable that a radically polymerizable group is not contained in a plasticizer.

In the composition of the present invention, the content of the plasticizer is not particularly limited, but is preferably 5 to 25% by mass, more preferably 8 to 16% by mass with respect to the entire composition.

<Polymerization inhibitor>
The polymerization inhibition inhibitor has a function of suppressing polymerization inhibition by oxygen. Polymerization inhibition suppression is not particularly limited, and examples thereof include phosphites (for example, triphenyl phosphite), amines (for example, aniline, hindered amine, DBU (diazabicycloundecene)), thiols (for example, dodecane). Thiol, pentaerythritol tetra (3-mercaptopropionate) and the like. The composition of the present invention may contain two or more polymerization inhibition inhibitors.
It is preferable that the composition of the present invention does not contain a polymerization inhibitor (especially dodecanethiol).

<Solvent>
The composition of the present invention may contain a solvent. Examples of the solvent used include water, organic solvents (for example, alcohols such as methanol, ketones such as acetone, amides such as formamide, sulfoxides such as dimethyl sulfoxide, esters such as ethyl acetate, ethers, and the like. Etc.), or a mixed solvent thereof.

In addition to the above, the composition of the present invention is filled with a surface lubricant, leveling agent, antioxidant, corrosion inhibitor, light stabilizer, ultraviolet absorber, polymerization inhibitor, silane coupling agent, inorganic or organic filling. Depending on the use for which various conventionally known additives such as powders such as agents, metal powders and pigments, particles and foils are used, they can be added as appropriate.

[Substituent W]
Hereinafter, the substituent W in this specification will be described.
Examples of the substituent W include a hydrogen atom, a halogen atom, an alkyl group (including a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group), an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), an alkynyl group, An aryl group, a heterocyclic group (also referred to as a heterocyclic group), a cyano group, a hydroxy group, an alkylenehydroxy group (—R—OH: R is an alkylene group), a nitro group, a carboxy group, an alkylenecarboxy group (—R -COOH: R is an alkylene group), alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including anilino group) , Ammonio group, acylamino group, aminocarbonyl Mino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or aryl Sulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl or heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino Groups, phosphono groups, silyl groups, hydrazino groups, ureido groups, boronic acid groups (—B (OH) ₂ ), phosphato groups (—OPO (OH) ₂ ), sulfato groups (—OSO ₃ H), and other known groups Such as substituents That.

[Method for preparing active energy ray-curable resin composition]
The preparation method in particular of the composition of this invention is not restrict | limited, A well-known method is employable. For example, after mixing each said component, it can prepare by stirring by a well-known means.

[Adhesive sheet]
The pressure-sensitive adhesive sheet of the present invention is a pressure-sensitive adhesive sheet obtained by curing the above-described composition of the present invention.
The thickness of the pressure-sensitive adhesive sheet is not particularly limited, but is preferably 5 to 2500 μm, more preferably 50 to 500 μm, and still more preferably 100 to 250 μm.
The pressure-sensitive adhesive sheet is preferably optically transparent. That is, it is preferably a transparent adhesive sheet. Optically transparent means that the total light transmittance is 85% or more, preferably 90% or more, and more preferably 95% or more.

<Method for producing adhesive sheet>
The manufacturing method in particular of an adhesive sheet is not restrict | limited, It can manufacture from a well-known method. For example, the composition of the present invention described above is applied on a predetermined substrate (for example, a release sheet such as release PET) and cured by irradiating with active energy rays (ultraviolet rays, visible rays, X-rays, etc.). The method of letting it be mentioned.
Examples of the method for applying the composition include a gravure coater, a comma coater, a bar coater, a knife coater, a die coater, and a roll coater.
Examples of the method of irradiating the active energy ray include a method using a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, a Deep-UV light, a xenon lamp, a chemical lamp, a carbon arc lamp, and the like. The energy of irradiation with the active energy ray is not particularly limited, but is preferably 1 to 10 J / cm ² .
After forming the pressure-sensitive adhesive sheet, if necessary, a release sheet such as release PET may be laminated on the exposed surface of the formed pressure-sensitive adhesive sheet.

In addition, even if the adhesive sheet is a type that does not have a base material (base material-less adhesive sheet), it has a base material in which an adhesive layer is disposed on at least one main surface of the base material (adhesive sheet with a base material) For example, a double-sided pressure-sensitive adhesive sheet with a base material having a pressure-sensitive adhesive layer on both sides of the base material, or a single-sided pressure-sensitive adhesive sheet with a base material having a pressure-sensitive adhesive layer only on one side of the base material) may be used.

[Laminate for touch panel, capacitive touch panel]
The laminated body for touchscreens of this invention is equipped with the adhesive sheet of this invention mentioned above, and a capacitive touch panel sensor.
One embodiment of the laminate for a touch panel of the present invention will be described with reference to the drawings.
FIG. 1 is a cross-sectional view schematically showing one embodiment of the laminate for a touch panel of the present invention. In FIG. 1, the laminated body 100 for a touch panel includes an adhesive sheet 12 and a capacitive touch panel sensor 18.
Moreover, FIG. 2 is sectional drawing which represents typically another aspect of the laminated body for touchscreens of this invention. In FIG. 2, the laminate for touch panel 200 includes a protective substrate 20, an adhesive sheet 12, and a capacitive touch panel sensor 18.

Moreover, the capacitive touch panel of this invention is equipped with a capacitive touch panel sensor, the adhesive sheet of this invention mentioned above, and a display apparatus in this order.
One embodiment of the capacitive touch panel of the present invention will be described with reference to the drawings.
FIG. 3A is a cross-sectional view schematically illustrating one embodiment of the capacitive touch panel of the present invention. In FIG. 3A, the capacitive touch panel 300 includes a capacitive touch panel sensor 18, an adhesive sheet 12, and a display device 50.
FIG. 3B is a cross-sectional view schematically showing another aspect of the capacitive touch panel of the present invention. In FIG. 3B, the capacitive touch panel 400 includes the protective substrate 20, the adhesive sheet 12, the capacitive touch panel sensor 18, the adhesive sheet 12, and the display device 50.
FIG. 3C is a cross-sectional view schematically showing still another aspect of the capacitive touch panel of the present invention. In FIG. 3C, the capacitive touch panel 500 includes a protective substrate integrated capacitive touch panel sensor 60, an adhesive sheet 12, and a display device 50. Here, the protective substrate integrated capacitive touch panel sensor 60 is a member in which a protective substrate and a capacitive touch panel sensor are integrated, as will be described later. There is no adhesive sheet in between. Therefore, the capacitive touch panel 500 including the protective substrate integrated capacitive touch panel sensor 60 is thinner than the capacitive touch panel 400 described above.
Hereinafter, various members used in the laminate for a touch panel and the capacitive touch panel will be described in detail.

[Capacitive touch panel sensor]
The capacitive touch panel sensor 18 is arranged on the display device (operator side) and uses a change in capacitance that occurs when an external conductor such as a human finger comes into contact (approaching). This is a sensor that detects the position of an external conductor such as a finger.
The configuration of the capacitive touch panel sensor 18 is not particularly limited, but usually has a detection electrode (especially, a detection electrode extending in the X direction and a detection electrode extending in the Y direction), and the static electricity of the detection electrode in contact with or close to the finger. The coordinates of the finger are specified by detecting the change in capacitance.

The suitable aspect of the electrostatic capacitance type touch panel sensor 18 is explained in full detail using FIG.
FIG. 4 shows a plan view of the capacitive touch panel sensor 180. FIG. 5 is a cross-sectional view taken along the cutting line AA in FIG. The capacitive touch panel sensor 180 includes a substrate 22, a first detection electrode 24 disposed on one main surface (surface) of the substrate 22, a first lead-out wiring 26, and the other main surface of the substrate 22. A second detection electrode 28, a second lead-out wiring 30, and a flexible printed wiring board 32 are provided on the upper side (on the back surface). The region where the first detection electrode 24 and the second detection electrode 28 are provided constitutes an input region E _I (an input region (sensing unit) capable of detecting the contact of an object) that can be input by the user, and input. A first lead wiring 26, a second lead wiring 30 and a flexible printed wiring board 32 are arranged in the outer region E _O located outside the region E _I.
Below, the said structure is explained in full detail.

The substrate 22 plays a role of supporting the first detection electrode 24 and the second detection electrode 28 in the input region E _I and plays a role of supporting the first lead wiring 26 and the second lead wiring 30 in the outer region E _O. It is a member.
The substrate 22 preferably transmits light appropriately. Specifically, the total light transmittance of the substrate 22 is preferably 85 to 100%.
The substrate 22 preferably has an insulating property (is an insulating substrate). That is, the substrate 22 is a layer for ensuring insulation between the first detection electrode 24 and the second detection electrode 28.

The substrate 22 is preferably a transparent substrate (particularly a transparent insulating substrate). Specific examples thereof include an insulating resin substrate, a ceramic substrate, and a glass substrate. Among these, an insulating resin substrate is preferable because of its excellent toughness.
More specifically, the material constituting the insulating resin substrate is polyethylene terephthalate, polyethersulfone, polyacrylic resin, polyurethane resin, polyester, polycarbonate, polysulfone, polyamide, polyarylate, polyolefin, cellulose resin, poly Examples include vinyl chloride and cycloolefin resins. Among these, polyethylene terephthalate, cycloolefin resin, polycarbonate, and triacetyl cellulose resin are preferable because of excellent transparency.

In FIG. 4, the substrate 22 is a single layer, but may be a multilayer of two or more layers.
The thickness of the substrate 22 (when the substrate 22 is a multilayer of two or more layers, the total thickness thereof) is not particularly limited, but is preferably 5 to 350 μm, more preferably 30 to 150 μm. Within the above range, desired visible light transmittance can be obtained, and handling is easy.
Moreover, in FIG. 4, the planar view shape of the board | substrate 22 is substantially rectangular shape, However, It is not restricted to this. For example, it may be circular or polygonal.

The first detection electrode 24 and the second detection electrode 28 are sensing electrodes that sense a change in capacitance, and constitute a sensing unit (sensor unit). That is, when the fingertip is brought into contact with the touch panel, the mutual capacitance between the first detection electrode 24 and the second detection electrode 28 changes, and the position of the fingertip is calculated by the IC circuit based on the change amount.
First detection electrode 24, which has a role to detect the input position in the X direction of the finger of the user in proximity to the input region E _I, has the function of generating an electrostatic capacitance between the finger ing. The first detection electrodes 24 are electrodes that extend in a first direction (X direction) and are arranged at a predetermined interval in a second direction (Y direction) orthogonal to the first direction. Includes patterns.
The second detection electrode 28 has a role of detecting the input position in the Y direction of the user's finger approaching the input area E _I and has a function of generating a capacitance between the second detection electrode 28 and the finger. ing. The second detection electrodes 28 are electrodes that extend in the second direction (Y direction) and are arranged at a predetermined interval in the first direction (X direction), and include a predetermined pattern as will be described later. In FIG. 4, five first detection electrodes 24 and five second detection electrodes 28 are provided, but the number is not particularly limited and may be plural.

In FIG. 4, the first detection electrode 24 and the second detection electrode 28 are composed of conductive thin wires. FIG. 6 shows an enlarged plan view of a part of the first detection electrode 24. As shown in FIG. 6, the first detection electrode 24 is composed of conductive thin wires 34, and includes a plurality of gratings 36 formed of intersecting conductive thin wires 34. Note that, similarly to the first detection electrode 24, the second detection electrode 28 also includes a plurality of lattices 36 formed by intersecting conductive thin wires 34.

Examples of the material of the conductive thin wire 34 include metals and alloys such as gold (Au), silver (Ag), copper (Cu), and aluminum (Al), ITO, tin oxide, zinc oxide, cadmium oxide, gallium oxide, Examples thereof include metal oxides such as titanium oxide. Among these, silver is preferable because the conductivity of the conductive thin wire 34 is excellent.

The conductive fine wire 34 preferably contains a binder from the viewpoint of adhesion between the conductive fine wire 34 and the substrate 22.
The binder is preferably a water-soluble polymer because the adhesion between the conductive thin wire 34 and the substrate 22 is more excellent. Examples of binders include gelatin, carrageenan, polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), starch and other polysaccharides, cellulose and its derivatives, polyethylene oxide, polysaccharides, polyvinylamine, chitosan, polylysine, and polyacryl. Examples include acid, polyalginic acid, polyhyaluronic acid, carboxycellulose, gum arabic, and sodium alginate. Among these, gelatin is preferable because the adhesion between the conductive thin wire 34 and the substrate 22 is more excellent.
In addition to lime-processed gelatin, acid-processed gelatin may be used as gelatin, and gelatin hydrolyzate, gelatin enzyme decomposition product, and other gelatins modified with amino groups and carboxyl groups (phthalated gelatin, acetylated gelatin) Can be used.

As the binder, a polymer different from the above gelatin (hereinafter also simply referred to as a polymer) may be used together with gelatin.
The type of polymer used is not particularly limited as long as it is different from gelatin. For example, acrylic resin, styrene resin, vinyl resin, polyolefin resin, polyester resin, polyurethane resin, polyamide resin, polycarbonate resin , A polydiene resin, an epoxy resin, a silicone resin, a cellulose polymer, and a chitosan polymer, or at least one resin selected from the group consisting of: Examples include coalescence.

The volume ratio of metal to binder (metal volume / binder volume) in the conductive thin wire 34 is preferably 1.0 or more, and more preferably 1.5 or more. By setting the volume ratio of the metal and the binder to 1.0 or more, the conductivity of the conductive thin wire 34 can be further increased. The upper limit is not particularly limited, but is preferably 6.0 or less, more preferably 4.0 or less, and even more preferably 2.5 or less from the viewpoint of productivity.
The volume ratio of the metal and the binder can be calculated from the density of the metal and the binder contained in the conductive thin wire 34. For example, when the metal is silver, the density of silver is 10.5 g / cm ³ , and when the binder is gelatin, the density of gelatin is 1.34 g / cm ³ .

Although the line width of the conductive thin wire 34 is not particularly limited, it is preferably 30 μm or less, more preferably 15 μm or less, further preferably 10 μm or less, and particularly preferably 9 μm or less, from the viewpoint that a low resistance electrode can be formed relatively easily. 7 μm or less is most preferable, 0.5 μm or more is preferable, and 1.0 μm or more is more preferable.
The thickness of the conductive thin wire 34 is not particularly limited, but can be selected from 0.00001 mm to 0.2 mm from the viewpoint of conductivity and visibility, but is preferably 30 μm or less, more preferably 20 μm or less, and 0.01 Is more preferably from 9 to 9 μm, most preferably from 0.05 to 5 μm.

The lattice 36 includes an opening region surrounded by the thin conductive wires 34. The length W of one side of the grating 36 is preferably 800 μm or less, more preferably 600 μm or less, and preferably 400 μm or more.
In the first detection electrode 24 and the second detection electrode 28, the aperture ratio is preferably 85% or more, more preferably 90% or more, and most preferably 95% or more in terms of visible light transmittance. preferable. The aperture ratio corresponds to the ratio of the transmissive portion excluding the conductive thin wires 34 in the first detection electrode 24 or the second detection electrode 28 in the predetermined region.

The lattice 36 has a substantially rhombus shape. However, other polygonal shapes (for example, a triangle, a quadrangle, and a hexagon) may be used. Further, the shape of one side may be a curved shape or a circular arc shape in addition to a linear shape. In the case of the arc shape, for example, the two opposing sides may have an outwardly convex arc shape, and the other two opposing sides may have an inwardly convex arc shape. The shape of each side may be a wavy shape in which an outwardly convex arc and an inwardly convex arc are continuous. Of course, the shape of each side may be a sine curve.
In FIG. 6, the conductive thin wire 34 is formed as a mesh pattern, but is not limited to this mode, and may be a stripe pattern.

The first lead wiring 26 and the second lead wiring 30 are members that play a role in applying a voltage to the first detection electrode 24 and the second detection electrode 28, respectively.
The first lead wiring 26 is disposed on the substrate 22 in the outer region E _O , one end of which is electrically connected to the corresponding first detection electrode 24, and the other end is electrically connected to the flexible printed wiring board 32. The
The second lead wiring 30 is disposed on the substrate 22 in the outer region E _O , one end of which is electrically connected to the corresponding second detection electrode 28, and the other end is electrically connected to the flexible printed wiring board 32. The
In FIG. 4, five first extraction wirings 26 and five second extraction wirings 30 are illustrated, but the number is not particularly limited, and a plurality of the first extraction wirings are usually arranged according to the number of detection electrodes. The

Examples of the material constituting the first lead wiring 26 and the second lead wiring 30 include metals such as gold (Au), silver (Ag), and copper (Cu), tin oxide, zinc oxide, cadmium oxide, and gallium oxide. And metal oxides such as titanium oxide. Among these, silver is preferable because of its excellent conductivity. Moreover, you may be comprised with metal pastes, such as a silver paste and a copper paste, metals, such as aluminum (Al) and molybdenum (Mo), and an alloy thin film. In the case of a metal paste, a screen printing or ink jet printing method is used, and in the case of a metal or alloy thin film, a patterning method such as a photolithography method is suitably used for the sputtered film.
In addition, it is preferable that the binder is contained in the 1st extraction wiring 26 and the 2nd extraction wiring 30 from the point which adhesiveness with the board | substrate 22 is more excellent. The kind of binder is as above-mentioned.

The flexible printed wiring board 32 is a board in which a plurality of wirings and terminals are provided on a substrate, and is connected to each other end of the first lead wiring 26 and each other end of the second lead wiring 30 to electrostatically It plays a role of connecting the capacitive touch panel sensor 180 and an external device (for example, a display device).

[Manufacturing method of capacitive touch panel sensor]
The manufacturing method of the capacitive touch panel sensor 180 is not particularly limited, and a known method can be adopted. For example, there is a method in which a photoresist film on the metal foil formed on both main surfaces of the substrate 22 is exposed and developed to form a resist pattern, and the metal foil exposed from the resist pattern is etched. Further, there is a method in which a paste containing metal fine particles or metal nanowires is printed on both main surfaces of the substrate 22 and metal plating is performed on the paste. Moreover, the method of printing and forming on the board | substrate 22 with a screen printing plate or a gravure printing plate, or the method of forming by an inkjet is also mentioned.

Furthermore, in addition to the above method, a method using silver halide can be mentioned. More specifically, the step (1) of forming a silver halide emulsion layer (hereinafter also referred to simply as a photosensitive layer) containing silver halide and a binder on both surfaces of the substrate 22, respectively, exposing the photosensitive layer. Then, the method which has the process (2) which carries out image development processing is mentioned.
Below, each process is demonstrated.

<Step (1): Photosensitive layer forming step>
Step (1) is a step of forming a photosensitive layer containing silver halide and a binder on both surfaces of the substrate 22.
The method for forming the photosensitive layer is not particularly limited, but from the viewpoint of productivity, the photosensitive layer forming composition containing silver halide and a binder is brought into contact with the substrate 22, and the photosensitive layer is formed on both surfaces of the substrate 22. The method of forming is preferred.
Below, after explaining in full detail the aspect of the composition for photosensitive layer formation used with the said method, the procedure of a process is explained in full detail.

The photosensitive layer forming composition contains a silver halide and a binder.
The halogen element contained in the silver halide may be any of chlorine, bromine, iodine and fluorine, or a combination thereof. As the silver halide, for example, silver halides mainly composed of silver chloride, silver bromide and silver iodide are preferably used, and silver halides mainly composed of silver bromide and silver chloride are preferably used.
The kind of binder used is as above-mentioned. Moreover, the binder may be contained in the composition for photosensitive layer formation in the form of latex.
The volume ratio of the silver halide and the binder contained in the composition for forming the photosensitive layer is not particularly limited, and is appropriately adjusted so as to be within a preferable volume ratio range of the metal and the binder in the conductive thin wire 34 described above. Is done.

The composition for forming a photosensitive layer contains a solvent, if necessary.
Examples of the solvent used include water, organic solvents (for example, alcohols such as methanol, ketones such as acetone, amides such as formamide, sulfoxides such as dimethyl sulfoxide, esters such as ethyl acetate, ethers, and the like. Etc.), ionic liquids, or mixed solvents thereof.
The content of the solvent to be used is not particularly limited, but is preferably in the range of 30 to 90% by mass, and more preferably in the range of 50 to 80% by mass with respect to the total mass of silver halide and binder.

(Process procedure)
The method for bringing the composition for forming a photosensitive layer and the substrate 22 into contact with each other is not particularly limited, and a known method can be adopted. For example, the method of apply | coating the composition for photosensitive layer formation to the board | substrate 22, the method of immersing the board | substrate 22 in the composition for photosensitive layer formation, etc. are mentioned.
The content of the binder in the formed photosensitive layer is not particularly limited but is preferably 0.3 ~ 5.0g / m ^2, more preferably 0.5 ~ 2.0g / m ^2.
Further, the content of the silver halide in the photosensitive layer is not particularly limited, but is preferably 1.0 to 20.0 g / m ^{2 in} terms of silver from the viewpoint that the conductive properties of the conductive fine wire 34 are more excellent. 0 to 15.0 g / m ² is more preferable.

In addition, you may further provide the protective layer which consists of a binder on a photosensitive layer as needed. By providing the protective layer, scratches can be prevented and mechanical properties can be improved.

<Process (2): Exposure development process>
In the step (2), the photosensitive layer obtained in the above step (1) is subjected to pattern exposure and then developed to thereby perform the first detection electrode 24 and the first lead wiring 26, and the second detection electrode 28 and the second detection electrode 28. This is a step of forming two lead-out wirings 30.
First, the pattern exposure process will be described in detail below, and then the development process will be described in detail.

(Pattern exposure)
By subjecting the photosensitive layer to pattern exposure, the silver halide in the photosensitive layer in the exposed region forms a latent image. In the area where the latent image is formed, conductive thin lines are formed by a development process described later. On the other hand, in an unexposed area that has not been exposed, the silver halide dissolves and flows out of the photosensitive layer during the fixing process described later, and a transparent film is obtained.
The light source used in the exposure is not particularly limited, and examples thereof include light such as visible light and ultraviolet light, and radiation such as X-rays.
The method for performing pattern exposure is not particularly limited. For example, surface exposure using a photomask may be performed, or scanning exposure using a laser beam may be performed. The shape of the pattern is not particularly limited, and is appropriately adjusted according to the pattern of the conductive fine wire to be formed.

(Development processing)
The development processing method is not particularly limited, and a known method can be employed. For example, a usual development processing technique used for silver salt photographic film, photographic paper, film for printing plate making, emulsion mask for photomask, and the like can be used.
The type of the developer used in the development process is not particularly limited. For example, PQ developer, MQ developer, MAA developer and the like can be used. Commercially available products include, for example, CN-16, CR-56, CP45X, FD-3, Papitol, C-41, E-6, RA-4, D-19, D-72 prescribed by KODAK. Or a developer contained in a kit thereof can be used. A lith developer can also be used.
The development process can include a fixing process performed for the purpose of removing and stabilizing the silver salt in the unexposed part. For the fixing process, a technique of fixing process used for silver salt photographic film, photographic paper, film for printing plate making, emulsion mask for photomask, and the like can be used.
The fixing temperature in the fixing step is preferably about 20 ° C. to about 50 ° C., more preferably 25 to 45 ° C. The fixing time is preferably 5 seconds to 1 minute, more preferably 7 seconds to 50 seconds.
The mass of the metallic silver contained in the exposed portion (conductive thin wire) after the development treatment is preferably a content of 50% by mass or more with respect to the mass of silver contained in the exposed portion before the exposure, More preferably, it is at least mass%. If the mass of silver contained in the exposed portion is 50% by mass or more based on the mass of silver contained in the exposed portion before exposure, it is preferable because high conductivity can be obtained.

In addition to the above steps, the following undercoat layer forming step, antihalation layer forming step, or heat treatment may be performed as necessary.
(Undercoat layer forming process)
For the reason of excellent adhesion between the substrate 22 and the silver halide emulsion layer, it is preferable to perform a step of forming an undercoat layer containing the binder on both sides of the substrate 22 before the step (1).
The binder used is as described above. The thickness of the undercoat layer is not particularly limited, but is preferably from 0.01 to 0.5 μm, more preferably from 0.01 to 0.1 μm, from the viewpoint that the adhesiveness and the rate of change in mutual capacitance can be further suppressed.
(Anti-halation layer formation process)
From the viewpoint of thinning the conductive thin wire 34, it is preferable to carry out a step of forming antihalation layers on both surfaces of the substrate 22 before the step (1).

<Process (3): Heating process>
Step (3) is a step of performing heat treatment after the development processing. By performing this step, fusion occurs between the binders, and the hardness of the conductive thin wires 34 is further increased. In particular, when polymer particles are dispersed as a binder in the composition for forming a photosensitive layer (when the binder is polymer particles in latex), by performing this step, fusion occurs between the polymer particles, Conductive thin wires 34 having a desired hardness are formed.
The conditions for the heat treatment are appropriately selected depending on the binder to be used, but it is preferably 40 ° C. or higher from the viewpoint of the film forming temperature of the polymer particles, more preferably 50 ° C. or higher, and further 60 ° C. or higher. preferable. Further, from the viewpoint of suppressing curling of the substrate and the like, 150 ° C. or lower is preferable, and 100 ° C. or lower is more preferable.
The heating time is not particularly limited, but is preferably 1 to 5 minutes and more preferably 1 to 3 minutes from the viewpoint of suppressing curling of the substrate and the like and productivity.
In addition, since this heat treatment can be combined with a drying step usually performed after exposure and development processing, it is not necessary to increase a new step for film formation of polymer particles, and productivity, cost, etc. Excellent from a viewpoint.

In addition, by performing the said process, the light transmissive part containing a binder is formed between the electroconductive thin wires 34. FIG. The transmittance in the light-transmitting portion is preferably 90% or more, more preferably 95% or more, still more preferably 97% or more, and more preferably 98% or more, as shown by the minimum transmittance in the wavelength region of 380 to 780 nm. Is particularly preferable, and 99% or more is most preferable.
The light transmissive portion may contain materials other than the binder, and examples thereof include a silver difficult solvent.

The aspect of the capacitive touch panel sensor is not limited to the aspect of FIG. 4 described above, and may be another aspect.
For example, as shown in FIG. 7, the capacitive touch panel sensor 280 is electrically connected to the first substrate 38, the second detection electrode 28 disposed on the first substrate 38, and one end of the second detection electrode 28. And electrically connected to one end of the second lead-out wiring (not shown) disposed on the first substrate 38, the adhesive sheet 40, the first detection electrode 24, and the first detection electrode 24. A first lead wire (not shown), a second substrate 42 adjacent to the first detection electrode 24 and the first lead wire, and a flexible printed wiring board (not shown).
As shown in FIG. 7, the capacitive touch panel sensor 280 has the same configuration as the capacitive touch panel sensor 180 except for the first substrate 38, the second substrate 42, and the adhesive sheet 40. Therefore, the same components are denoted by the same reference numerals, and the description thereof is omitted.
The definitions of the first substrate 38 and the second substrate 42 are the same as the definition of the substrate 22 described above.
The pressure-sensitive adhesive sheet 40 is a layer for bringing the first detection electrode 24 and the second detection electrode 28 into close contact with each other, and is preferably optically transparent (preferably a transparent pressure-sensitive adhesive sheet). A known material may be used as the material constituting the pressure-sensitive adhesive sheet 40, and the pressure-sensitive adhesive sheet 12 may be used as the pressure-sensitive adhesive sheet 40.
A plurality of the first detection electrodes 24 and the second detection electrodes 28 in FIG. 7 are used as shown in FIG. 4, and both are arranged so as to be orthogonal to each other as shown in FIG.
In addition, the capacitive touch panel sensor 280 shown in FIG. 7 is prepared by preparing two substrates with electrodes having a substrate and detection electrodes and lead wires arranged on the substrate surface, so that the electrodes face each other. Corresponds to the capacitive touch panel sensor obtained by bonding through the.

As another aspect of the capacitive touch panel sensor, an aspect shown in FIG.
The capacitive touch panel sensor 380 is electrically connected to the first substrate 38, the second detection electrode 28 disposed on the first substrate 38, and one end of the second detection electrode 28. A second lead-out wiring (not shown), an adhesive sheet 40, a second substrate 42, a first detection electrode 24 disposed on the second substrate 42, and one end of the first detection electrode 24; A first lead-out wiring (not shown) and a flexible printed wiring board (not shown) which are electrically connected and are arranged on the second substrate 42 are provided.
The capacitive touch panel sensor 380 shown in FIG. 8 has the same layers as the capacitive touch panel sensor 280 shown in FIG. 7 except that the order of the layers is different. Are denoted by the same reference numerals, and the description thereof is omitted.
Further, a plurality of the first detection electrodes 24 and the second detection electrodes 28 in FIG. 8 are used as shown in FIG. 4, and both are arranged so as to be orthogonal to each other as shown in FIG. .
In addition, the capacitive touch panel sensor 380 shown in FIG. 8 prepares two substrates with electrodes having a substrate and detection electrodes and lead wires arranged on the substrate surface, and the substrate in the substrate with one electrode It corresponds to the electrostatic capacitance type touch panel sensor obtained by bonding through an adhesive sheet so that the electrode of the other board | substrate with an electrode may face.

As another aspect of the capacitive touch panel sensor, for example, in FIG. 4, the conductive thin wires 34 of the first detection electrode 24 and the second detection electrode 28 are made of metal oxide particles, metal such as silver paste or copper paste. You may be comprised with the paste. Among these, a conductive film made of a thin silver wire and a silver nanowire conductive film are preferable in terms of excellent conductivity and transparency.
In addition, the first detection electrode 24 and the second detection electrode 28 are configured by the mesh structure of the conductive thin wires 34. However, the present invention is not limited to this mode. For example, a metal oxide thin film (transparent metal) such as ITO or ZnO is used. Oxide thin film), and a transparent conductive film in which a network is formed of metal nanowires such as silver nanowires and copper nanowires.
More specifically, as shown in FIG. 9, a capacitive touch panel sensor 180a having a first detection electrode 24a and a second detection electrode 28a made of a transparent metal oxide may be used. FIG. 9 is a partial plan view of the input area of the capacitive touch panel sensor 180a. FIG. 10 is a cross-sectional view taken along the cutting line AA in FIG. The capacitive touch panel sensor 180a is electrically connected to the first substrate 38, the second detection electrode 28a disposed on the first substrate 38, and one end of the second detection electrode 28a. A second lead-out wiring (not shown), an adhesive sheet 40, a second substrate 42, a first detection electrode 24a disposed on the second substrate 42, and one end of the first detection electrode 24a. A first lead-out wiring (not shown) and a flexible printed wiring board (not shown) which are electrically connected and are arranged on the second substrate 42 are provided.
The capacitive touch panel sensor 180a shown in FIGS. 9 and 10 has the same layer as the capacitive touch panel sensor 380 shown in FIG. 8 except for the points other than the first detection electrode 24a and the second detection electrode 28a. Therefore, the same components are denoted by the same reference numerals, and the description thereof is omitted.
The capacitive touch panel sensor 180a shown in FIG. 9 and FIG. 10 prepares two substrates with electrodes having a substrate and detection electrodes and lead wires arranged on the substrate surface, and the substrate in the substrate with one electrode This corresponds to a capacitive touch panel sensor obtained by bonding through an adhesive layer so that the electrode on the other electrode-attached substrate faces the electrode.

As described above, the first detection electrode 24a and the second detection electrode 28a are electrodes extending in the X-axis direction and the Y-axis direction, respectively, and are made of a transparent metal oxide, for example, indium tin oxide (ITO). The 9 and 10, in order to make use of the transparent electrode ITO as a sensor, the resistance of the indium tin oxide (ITO) itself is increased, the total wiring resistance is reduced by increasing the electrode area, and the thickness is further increased. It is designed to ensure the light transmittance by making it thinner and taking advantage of the characteristics of the transparent electrode.
In addition to ITO, examples of materials that can be used in the above embodiment include zinc oxide (ZnO), indium zinc oxide (IZO), gallium zinc oxide (GZO), and aluminum zinc oxide (AZO). It is done.
The patterning of the electrode parts (the first detection electrode 24a and the second detection electrode 28a) can be selected according to the material of the electrode part, and includes a photolithography method, a resist mask screen printing-etching method, an inkjet method, a printing method, and the like. It may be used.

[Protective board]
The protective substrate 20 is a substrate disposed on the adhesive sheet, and serves to protect a capacitive touch panel sensor 18 (to be described later) from the external environment, and its main surface constitutes a touch surface.
The protective substrate 20 is preferably a transparent substrate, and a plastic film, a plastic plate, a glass plate, or the like is used. It is desirable that the thickness of the substrate is appropriately selected according to each application.
Examples of the raw material for the plastic film and the plastic plate include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); polyolefins such as polyethylene (PE), polypropylene (PP), polystyrene, and EVA; Resin; In addition, polycarbonate (PC), polyamide, polyimide, acrylic resin, triacetyl cellulose (TAC), cycloolefin resin (COP), and the like can be used.
Further, as the protective substrate 20, a polarizing plate, a circular polarizing plate, or the like may be used.

[Protective substrate integrated type capacitive touch panel sensor]
The protective substrate integrated capacitive touch panel sensor 60 is a member in which a protective substrate and a capacitive touch panel sensor are integrated.
The method for manufacturing the protective substrate integrated capacitive touch panel sensor 60 is not particularly limited, and examples thereof include a method of directly forming a detection electrode on the protective substrate.

[Display device]
The display device 50 is a device having a display surface for displaying an image, and each member is arranged on the display screen side.
The type of the display device 50 is not particularly limited, and a known display device can be used. For example, cathode ray tube (CRT) display, liquid crystal display (LCD), organic light emitting diode (OLED) display, vacuum fluorescent display (VFD), plasma display panel (PDP), surface field display (SED) or field emission display (FED) or electronic paper (E-Paper).

The above-mentioned pressure-sensitive adhesive sheet of the present invention can be suitably used for the production of a capacitive touch panel. For example, between the display device and the capacitive touch panel sensor, between the capacitive touch panel sensor and a protective substrate, or on the substrate and the substrate in the capacitive touch sensor. It is used to provide an adhesive sheet that is disposed between conductive films provided with detection electrodes.
In particular, the pressure-sensitive adhesive sheet of the present invention is preferably used for providing a pressure-sensitive adhesive layer adjacent to the detection electrode in the capacitive touch panel. When used in such an aspect, it is preferable because touch malfunctions due to the influence of the above-described variation factors can be remarkably reduced.
In addition, as a case where the adhesive sheet is adjacent to the detection electrode, for example, when the capacitive touch panel sensor has a configuration in which the detection electrode is arranged on the back surface of the substrate, the detection electrode is in contact with both detection electrodes. The case where an adhesive sheet is arrange | positioned is mentioned. In another case, the capacitive touch panel sensor has two conductive films each having a substrate and a detection electrode disposed on one side of the substrate, and the two conductive films are detected when bonded. The case where an adhesive sheet is arrange | positioned so that an electrode may be touched is mentioned. More specifically, the case where it uses as an aspect of the adhesive sheet 40 of FIG. 7 and FIG. 8 is mentioned.

[Optical members]
The optical member of the present invention is an optical member obtained by curing the above-described composition of the present invention. The method of hardening is the same as that of the adhesive sheet mentioned above.
The optical member of the present invention includes, for example, a lens (glass lens, digital camera lens, Fresnel lens, prism lens, etc.), optical overcoat agent, hard coat agent, antireflection film, optical fiber, optical waveguide, LED sealing. It can be suitably used for a fixing material, a planarizing material for LED, a base material for micro OLED, a coating material for solar battery, and the like.

Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.

[Examples 1 to 21, Comparative Examples 1 to 10]
<Preparation of composition>
The components shown in Table 1 below were mixed in the blending amounts (parts by mass) shown in Table 1 below and stirred to obtain each composition.
For example, the composition of Example 1 has VC (6 parts by weight), EHM (19 parts by weight), TPO (3.0 parts by weight), UC-102 (21.8 parts by weight), P- 135 (41 parts by mass) and Polyoil 110 (9.2 parts by mass) are mixed and stirred. Details of each component are as described below.

<Production of adhesive sheet>
Each composition obtained was applied onto release PET to form a composition layer. Thereafter, the formed composition layer was irradiated with a fusion UV lamp (D bulb: illuminance 200 mW / cm ² ) under the condition of ³ J / cm ² and cured to form an adhesive sheet (thickness: 150 μm) formed on the release PET. )

[Evaluation]
<Monomer residual ratio>
The monomer residual rate was evaluated about each obtained adhesive sheet. Here, the monomer residual ratio means the residual ratio of the monomer contained in the composition in the pressure-sensitive adhesive sheet.
Specifically, the same amount (30 g) of the composition and the pressure-sensitive adhesive sheet obtained from the composition are weighed, and each is placed in a tetrahydrofuran / methanol (mass ratio: 1/1) solution (10 g) at room temperature for 24 hours. The monomer contained in each was extracted by contact, and the resulting extract was HPLC (HPLC SLI-20A manufactured by Shimadzu Corp., column: TSKgel ODS-100V, eluent: tetrahydrofuran / acetonitrile = 1/9, column The area derived from the monomer was measured over the temperature (40 ° C.), and the ratio of the area derived from the monomer extracted from the composition (S1) to the area derived from the monomer extracted from the adhesive sheet (S2) (S2 / S1) × 100 was calculated and used as the monomer residual rate (%). The results are shown in Table 1. Practically, the residual monomer ratio is preferably less than 13.0%.

<Gel fraction>
The gel fraction was evaluated about each obtained adhesive sheet.
Specifically, first, the pressure-sensitive adhesive sheet (0.2 g) was immersed in ethyl acetate (30 g) and allowed to stand for 24 hours while maintaining at 40 ° C. (By this, components other than the gel component in the pressure-sensitive adhesive sheet were ethyl acetate. To dissolve). Next, the immersed adhesive sheet was taken out, dried, and its mass was measured. And the gel fraction (mass%) in an adhesive sheet was computed from the following formula | equation. The results are shown in Table 1.
“Gel fraction” = (mass of adhesive sheet after immersion) / (mass of adhesive sheet before immersion) × 100 (%)

<Adhesion>
Each obtained pressure-sensitive adhesive sheet was cut into 2.5 cm × 5 cm, and a sample was prepared by sticking one side of the cut-out pressure-sensitive adhesive sheet to a glass substrate and the other side to a Kapton film. Subsequently, one end of the Kapton film was gripped using an autograph manufactured by Shimadzu Corporation, a 180 degree peel test (tensile speed of 300 cm / min) was performed, and an average test force value of the adhesive sheet and the glass substrate was measured. The value was defined as adhesive strength (N / mm). The results are shown in Table 1. Practically, the adhesive strength is preferably 0.50 N / mm or more.

<Step following capability>
Each obtained adhesive sheet was cut into 2.5 cm × 4 cm, one side of the cut out adhesive sheet was attached to a glass substrate wrapped with Kapton tape (5 mm width 35 μm thickness), and the other side was attached to optical PET. An attached sample was produced. Subsequently, using an autoclave, a heat press treatment was performed under the conditions of an internal temperature of 40 ° C., 5 atm, and 20 minutes to prepare a sample for a step following test.
About the produced sample, the boundary surface formed between the adhesive sheet and the Kapton tape level | step difference was observed with the Nikon optical microscope, and the boundary space | gap width was measured.
Of the measured boundary gap width, the largest value of less than 20 μm is designated as “A” as having excellent step followability, and those having 20 μm or more but less than 50 μm are designated as “B” having relatively excellent step followability, A material having a thickness of 50 μm or more and less than 100 μm is not preferable, but “C” is used as a practically usable product, and a product having a thickness of 100 μm or more is “D” because it is inferior in level-step following property and has no practicality. The results are shown in Table 1.

<Malfunction occurrence rate>
First, the manufacturing method of the touch panel used by evaluation of malfunction occurrence rate is shown below.

(Preparation of silver halide emulsion)
To the following 1 liquid maintained at 38 ° C. and pH 4.5, an amount corresponding to 90% of each of the following 2 and 3 liquids was simultaneously added over 20 minutes while stirring to form 0.16 μm core particles. Subsequently, the following 4 and 5 solutions were added over 8 minutes, and the remaining 10% of the following 2 and 3 solutions were added over 2 minutes to grow to 0.21 μm. Further, 0.15 g of potassium iodide was added and ripened for 5 minutes to complete the grain formation.

1 liquid:
750 ml of water
9g gelatin
Sodium chloride 3g
1,3-Dimethylimidazolidine-2-thione 20mg
Sodium benzenethiosulfonate 10mg
Citric acid 0.7g
Two liquids:
300 ml of water
150 g silver nitrate
3 liquids:
300 ml of water
Sodium chloride 38g
Potassium bromide 32g
Potassium hexachloroiridium (III) (0.005% KCl 20% aqueous solution) 8 ml
Ammonium hexachlororhodate (0.001% NaCl 20% aqueous solution) 10 ml
4 liquids:
100ml water
Silver nitrate 50g
5 liquids:
100ml water
Sodium chloride 13g
Potassium bromide 11g
Yellow blood salt 5mg

Then, it was washed with water by a flocculation method according to a conventional method. Specifically, the temperature was lowered to 35 ° C., and the pH was lowered using sulfuric acid until the silver halide precipitated (the pH was in the range of 3.6 ± 0.2). Next, about 3 liters of the supernatant was removed (first water washing). Further, 3 liters of distilled water was added, and sulfuric acid was added until the silver halide settled. Again, 3 liters of the supernatant was removed (second water wash). The same operation as the second water washing was further repeated once (third water washing) to complete the water washing / desalting step. The emulsion after washing with water and desalting was adjusted to pH 6.4 and pAg 7.5, and gelatin 3.9 g, sodium benzenethiosulfonate 10 mg, sodium benzenethiosulfinate 3 mg, sodium thiosulfate 15 mg and chloroauric acid 10 mg were added. Chemical sensitization to obtain optimum sensitivity at 0 ° C., 100 mg of 1,3,3a, 7-tetraazaindene as stabilizer and 100 mg of proxel (trade name, manufactured by ICI Co., Ltd.) as preservative It was. The finally obtained emulsion contains 0.08 mol% of silver iodide, and the ratio of silver chlorobromide is 70 mol% of silver chloride and 30 mol% of silver bromide. It was a silver iodochlorobromide cubic grain emulsion having a coefficient of 9%.

(Preparation of photosensitive layer forming composition)
1,3,3a, 7-tetraazaindene 1.2 × 10 ⁻⁴ mol / mol Ag, hydroquinone 1.2 × 10 ⁻² mol / mol Ag, citric acid 3.0 × 10 ⁻⁴ mol / Mole Ag and 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt (0.90 g / mole Ag) were added, and the pH of the coating solution was adjusted to 5.6 using citric acid, and photosensitivity was achieved. A composition for forming a conductive layer was obtained.

(Photosensitive layer forming step)
After subjecting a polyethylene terephthalate (PET) film having a thickness of 100 μm to corona discharge treatment, a gelatin layer having a thickness of 0.1 μm as an undercoat layer on both sides of the PET film, and an optical density of about 1.0 on the undercoat layer. And an antihalation layer containing a dye which is decolorized by alkali in the developer. On the antihalation layer, the composition for forming a photosensitive layer was applied, a gelatin layer having a thickness of 0.15 μm was further provided, and a PET film having a photosensitive layer formed on both sides was obtained. The obtained film is referred to as film A. The formed photosensitive layer had a silver amount of 6.0 g / m ² and a gelatin amount of 1.0 g / m ² .

(Exposure development process)
As shown in FIG. 4, a high voltage is applied through a photomask in which detection electrodes (first detection electrodes and second detection electrodes) and lead wires (first lead wires and second lead wires) are arranged on both surfaces of the film A. Exposure was performed using parallel light using a mercury lamp as a light source. After the exposure, development was performed with the following developer, and further development was performed using a fixer (trade name: N3X-R for CN16X, manufactured by Fuji Film). Furthermore, by rinsing with pure water and drying, a capacitive touch panel sensor A provided with detection electrodes and lead wires made of Ag fine wires on both sides was obtained.
In the obtained capacitive touch panel sensor A, the detection electrodes are composed of conductive thin wires that intersect in a mesh shape. Further, as described above, the first detection electrode is an electrode extending in the X direction, and the second detection electrode is an electrode extending in the Y direction, and each is disposed on the film at a pitch of 4.5 to 5 mm.

Next, using each obtained adhesive sheet, a touch panel including a liquid crystal display device, a lower adhesive layer, a capacitive touch panel sensor, an upper adhesive layer, and a glass substrate in this order was manufactured. In addition, as a capacitive touch panel sensor, the capacitive touch panel sensor A manufactured above was used.
Specifically, the adhesive sheet (having the release PET on one side) and the capacitive touch panel sensor A, the surface of the adhesive sheet opposite to the surface having the release PET and one of the capacitive touch panel A The upper adhesive layer was formed by pasting using a 2 kg heavy roller so that the surface of the upper surface would face. Furthermore, the release PET of the pressure-sensitive adhesive sheet was peeled off, and a glass substrate of the same size was bonded onto the upper pressure-sensitive adhesive layer in the same manner using a 2 kg heavy roller. Then, it was exposed to the environment of 40 degreeC and 5 atmospheres for 20 minutes in the high-pressure thermostat, and the defoaming process was performed.
Next, following the same procedure as the formation of the upper adhesive layer, an adhesive sheet (having a release PET on one side) is bonded to the surface opposite to the surface on which the upper adhesive layer of the capacitive touch panel A is formed, A lower adhesive layer was formed. Furthermore, the release PET of the pressure-sensitive adhesive sheet was peeled off, and a liquid crystal display device was attached on the lower pressure-sensitive adhesive layer. Then, it was exposed to the environment of 40 degreeC and 5 atmospheres for 20 minutes in the high-pressure thermostat, and the defoaming process was performed. Thus, the touch panel was manufactured.

The obtained touch panel was heated stepwise from −40 ° C. to 80 ° C. in steps of 20 ° C., and the malfunction occurrence rate at the time of touch at each temperature was obtained. That is, in an environment of −40 ° C., −20 ° C., 0 ° C., 20 ° C., 40 ° C., 60 ° C., and 80 ° C., an arbitrary location is touched 100 times and the touch panel The occurrence rate of malfunction (%) [(number of times of not reacting normally / 100) × 100] was determined. And it evaluated according to the following criteria. The results are shown in Table 1. Practically, it is preferably “A”, “B” or “C”, more preferably “A” or “B”, and even more preferably “A”.
“A”: Malfunction occurrence rate is less than 5% “B”: Malfunction occurrence rate is 5% or more and less than 10% “C”: Malfunction occurrence rate is 10% or more and less than 15% “D”: Malfunction occurrence rate is 15% or more Less than 20% "E": Malfunction occurrence rate is 20% or more

 

 

・ＮＶＰ：Ｎ－ビニルピロリドン

・ＮＶＣ：Ｎ－ビニルカプロラクタム

・ＥＨＭ：ビス（２－エチルヘキシル）マレート

・ＥＨＦ：ビス（２－エチルヘキシル）フマレート

・ＥＨＭＡ：２－エチルヘキシルメタクリレート
・ＩＢＸＡ：イソボルニルアクリレート
・ＦＡ－５１２Ｍ：ジシクロペンテニルオキシエチルメタクリレート（日立化成社製）
・ＦＡ－５１２ＡＳ：ジシクロペンテニルオキシエチルアクリレート（日立化成社製）
・ＥＨＡ：２－エチルヘキシルアクリレート
・Ｍ－１００：サイクロマーＭ－１００（ダイセル社製）
・ＨＢＧＡ：４－ヒドロキシブチルアクリレートグリシジルエーテル
・ＤＤＴ：ドデカンチオール
・Ｉｒｇ８１９：Ｉｒｇａｃｕｒｅ８１９（ビス（２，４，６－トリメチルベンゾイル）－フェニルホスフィンオキサイド、ＢＡＳＦ社製）
・ＴＰＯ：Ｌｕｃｉｒｉｎ　ＴＰＯ（２，４，６－トリメチルベンゾイル－ジフェニルホスフィンオキサイド、ＢＡＳＦ社製）
・ＵＣ－１０２：ＵＣ－１０２（イソプレン重合物の無水マレイン酸付加物と２－ヒドロキシエチルメタクリレートとのエステル化物、１分子当たりのメタクリロイル基数：２、重量平均分子量：１９０００、クラレ社製）
・ＥＭＡ－３０００：ＥＭＡ－３０００（末端アクリル基導入ポリブタジエン、日本曹達社製）
・ＬＢＲ－３０５：ＬＢＲ－３０５（ビニル結合および１，４－結合を有するブタジエン重合体、クラレ社製）
・Ｐ－１３５：ＣＬＥＡＲＯＮ　Ｐ－１３５（水添テルペン樹脂、ヤスハラケミカル社製）
・Ｐｏｌｙｏｉｌ　１１０：液状ポリブタジエン（日本ゼオン社製） The detail of each component of the said Table 1 is as follows.
・ VC: Vinylene carbonate

・ NVP: N-vinylpyrrolidone

NVC: N-vinylcaprolactam

EHM: bis (2-ethylhexyl) malate

EHF: bis (2-ethylhexyl) fumarate

EHMA: 2-ethylhexyl methacrylate IBXA: isobornyl acrylate FA-512M: dicyclopentenyloxyethyl methacrylate (manufactured by Hitachi Chemical Co., Ltd.)
FA-512AS: dicyclopentenyloxyethyl acrylate (manufactured by Hitachi Chemical Co., Ltd.)
EHA: 2-ethylhexyl acrylate M-100: Cyclomer M-100 (manufactured by Daicel)
HBGA: 4-hydroxybutyl acrylate glycidyl ether DDT: dodecanethiol Irg819: Irgacure 819 (bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, manufactured by BASF)
TPO: Lucirin TPO (2,4,6-trimethylbenzoyl-diphenylphosphine oxide, manufactured by BASF)
UC-102: UC-102 (esterified product of maleic anhydride adduct of isoprene polymer and 2-hydroxyethyl methacrylate, number of methacryloyl groups per molecule: 2, weight average molecular weight: 19000, manufactured by Kuraray Co., Ltd.)
EMA-3000: EMA-3000 (terminal acrylic group-introduced polybutadiene, manufactured by Nippon Soda Co., Ltd.)
LBR-305: LBR-305 (butadiene polymer having vinyl bond and 1,4-bond, manufactured by Kuraray Co., Ltd.)
・ P-135: CLEARON P-135 (hydrogenated terpene resin, manufactured by Yasuhara Chemical Co., Ltd.)
Polyoil 110: Liquid polybutadiene (manufactured by Nippon Zeon)

In addition, about said VC, NVP, NVC, EHM, and EHF, Tg when it is set as a homopolymer (degree of polymerization 100) is as follows.
・ VC: 55 ℃
・ NVP: 80 ℃
-NVC: 75 ° C
・ EHM: -20 ℃
・ EHF: -25 ℃

As can be seen from Table 1, the pressure-sensitive adhesive sheet obtained from the composition of Examples of the present application containing the polymerizable compounds A and B had a low monomer residual ratio, and exhibited excellent adhesion and step following ability. In addition, when used in a capacitive touch panel, malfunctions were suppressed in a wide temperature environment from low to high temperatures.
From the comparison between Examples 1 and 2 and the comparison between Examples 5 and 6, Examples 2 and 6 in which the polymerizable compound B is a fumaric acid diester showed better adhesion and low malfunction. .
Further, from the comparison between Examples 1 and 5 and the comparison between Examples 2 and 6, Examples 5 and 6 in which the polymerizable compound A is the polymerizable compound a1 have a lower monomer residual rate, It showed better adhesion.
Further, from the comparison between Examples 7 and 9, the polymerizable compound A is a polymerizable compound a12 represented by the above formula (I-2), and n in the above formula (I-2) is 1 to 3. In Example 7, which is an integer, the monomer residual ratio was lower and more excellent adhesion was exhibited.
Further, in comparison with Examples 6 to 7 and 11 to 13, Examples 6 to 7 and 11 to 12 in which the ratio (A / B) described above is 0.6 or more have better adhesion and low malfunction. showed that. In particular, Examples 11 to 12 having a ratio (A / B) of 1.2 or more showed better adhesion and step following ability.

On the other hand, in Comparative Examples 1 to 10 using monomers other than the polymerizable compounds A and B, at least any of the monomer residual ratio, adhesion, step following ability and low malfunction was insufficient.
As can be seen from the comparison between Comparative Examples 3 and 4, when a monomer other than the polymerizable compounds A and B was used, the adhesion was improved by adding DDT, but the occurrence rate of malfunction was increased.

12 Adhesive sheets 18, 180, 180 a, 280, 380 Capacitive touch panel sensor 20 Protective substrate 22 Substrate 24, 24 a First detection electrode 26, 26 a First extraction wiring 28, 28 a Second detection electrode 30 Second extraction wiring 32 Flexible printed wiring board 34 Conductive thin wire 36 Grid 38 First substrate 40 Adhesive sheet 42 Second substrate 50 Display device 60 Integrated protective substrate capacitive touch panel sensor 100, 200 Laminate 300, 400, 500 for touch panel Capacitance Touch panel

Claims (10)

A polymerizable compound A1 selected from the group consisting of a polymerizable compound a1 represented by the following formula (I) and a polymerizable compound a2 represented by the following formula (II);
A polymerizable compound B selected from the group consisting of diesters and diamides of dicarboxylic acids selected from the group consisting of maleic acid, fumaric acid and citraconic acid;
An active energy ray-curable resin composition containing a photopolymerization initiator C.

In formulas (I) and (II), R ₁ to R ₃ each independently represents a hydrogen atom or an optionally substituted alkyl group, alkoxy group, alkylthio group, or alkylamino group. To express. R ₄ to R ₇ each independently represents a hydrogen atom, —CO—R _A , or an alkyl group, an aryl group, or a heteroaryl group which may have a substituent. Here, R _A represents a hydrogen atom or an alkyl group, an aryl group, or a heteroaryl group which may have a substituent. R ₁ to R ₇ may be bonded to each other to form a ring. The active energy ray-curable resin composition according to claim 1, wherein a ratio of the number of moles of the polymerizable compound A to the number of moles of the polymerizable compound B is 0.6 to 4. The active energy ray-curable resin composition according to claim 1 or 2, further comprising a crosslinking agent. Tg of the homopolymer of the polymerizable compound A is 50 ° C. or higher, and Tg of the homopolymer of the polymerizable compound B is 0 ° C. or lower.
Or, the Tg of the homopolymer of the polymerizable compound A is 0 ° C. or lower, and the Tg of the homopolymer of the polymerizable compound B is 50 ° C. or higher. Active energy ray-curable resin composition. An optical member obtained by curing the active energy ray-curable resin composition according to any one of claims 1 to 4. A pressure-sensitive adhesive sheet obtained by curing the active energy ray-curable resin composition according to any one of claims 1 to 4. The pressure-sensitive adhesive sheet according to claim 6, which is a pressure-sensitive adhesive sheet for a touch panel. A laminate for a touch panel comprising the pressure-sensitive adhesive sheet according to claim 7 and a capacitive touch panel sensor. In addition, with a protective substrate,
The laminated body for touchscreens of Claim 8 provided with the said protective substrate, the said adhesive sheet, and the said capacitive touch panel sensor in this order. A capacitive touch panel comprising a capacitive touch panel sensor, the adhesive sheet according to claim 7, and a display device in this order.

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