WO2020153259A1 - Cover member - Google Patents

Abstract

Provided is a cover member which combines the properties of glass, flexibility and ease of handling.　This cover member has a configuration comprising a glass plate having a thickness not exceeding 500 μm and a resin film, laminated together with an adhesive layer interposed therebetween.　This cover member preferably has a shock resistance of at least 4 cm when subjected to the following testing. Shock resistance testing: the cover member is positioned on a flat surface with the glass plate-side surface facing upward, a ball-point pen having a ball diameter of 0.7 mm and a weight of 5.7 g is made to drop naturally onto the surface of the cover member with the pen tip first, and the dropping height (in cm) at which a crack occurs in the glass plate is taken as an indicator of shock resistance.

Description

Cover member

The present invention relates to a cover member composed of a laminated body including a glass plate. This application claims the priority of Japanese Patent Application No. 2019-010836 filed in Japan on January 25, 2019, and the content thereof is incorporated herein.

In recent years, glass is often used as a cover member for displays of mobile devices such as mobile phones, personal digital assistants, and tablet PCs. This is because glass is excellent in transparency, gas barrier property, chemical stability, surface smoothness, and the like, and the texture of glass is preferred.

However, the problems with glass are that it lacks flexibility and that it is easily broken and difficult to handle. Patent Document 1 describes a thinned glass plate, and it is described that the thinned glass plate has flexibility and can be bent slowly.

JP, 2010-105900, A

However, there was a problem with the thin glass plate that it was difficult to handle.

Therefore, an object of the present invention is to provide a cover member which has the characteristics of glass, flexibility and good handleability.
Another object of the present invention is to provide a cover member that has the characteristics of glass, flexibility, impact resistance, and good handleability.
Another object of the present invention is to provide a cover member that has the characteristics of glass, flexibility, impact resistance, bending durability, and good handleability.
Another object of the present invention is to provide a touch panel display, a flexible display, and a fingerprint authentication sensor including the cover member.
Another object of the present invention is to provide an organic electroluminescent device or an organic thin film solar cell including the cover member.
Another object of the present invention is to provide an electronic device including the display or the fingerprint authentication sensor.

As a result of intensive studies by the present inventors in order to solve the above problems, a cover member obtained by joining a glass plate and a resin film via an adhesive layer has the characteristics of glass, and has flexibility and impact resistance. It has been found that the cover member is excellent and easy to handle, and that the cover member is suitable as a cover glass for a display, a protective film for a fingerprint authentication sensor, a substrate for an organic electroluminescent device or an organic thin film solar cell, or a sealing member. The present invention has been completed based on these findings.

That is, the present invention provides a cover member having a structure in which a glass plate having a thickness of 500 μm or less and a resin film are laminated via an adhesive layer.

The present invention also provides the cover member according to the following test, which has an impact resistance of 4 cm or more.
Impact resistance test:
The cover member is placed on a flat surface with the glass plate side surface facing upward, and a ballpoint pen having a ball diameter of 0.7 mm and a weight of 5.7 g is naturally dropped from the pen tip toward the surface of the cover member to form a glass plate. The drop height (cm) before cracking is used as an index of impact resistance

The present invention also provides the cover member having a minimum bending radius of 250 mm or less.

The present invention also provides the cover member having a total thickness of 1000 μm or less.

The present invention also provides the cover member, wherein the adhesive layer is a cured product of the following adhesive (1).
Adhesive (1): containing a cationically polymerizable monomer and a curing catalyst, and as the cationically polymerizable monomer, at least one cationically polymerizable group selected from a vinyl ether group, an epoxy group, and an oxetanyl group in one molecule. And 10% by weight or more of the compound having at least one hydroxyl group based on the total amount of the cationically polymerizable monomer,

(In the formula, R is an s-valent linear or branched saturated aliphatic hydrocarbon group, or two or more linear or branched saturated aliphatic hydrocarbon groups bonded via an ether bond. s represents a valent group, and s represents an integer of 2 or more)
The compound represented by 5 wt% or more of the total amount of the cationically polymerizable monomer is contained.

In the present invention, the adhesive (1) further comprises the following formula (b′) as a cationically polymerizable monomer.

(In the formula, X represents a single bond or a linking group)
The cover member comprises the compound represented by 10% by weight or more of the total amount of the cationically polymerizable monomer.

The present invention also provides the cover member, wherein the adhesive layer is a cured product of an acrylic urethane adhesive (2) containing urethane (meth)acrylate or a polymer thereof.

The present invention also provides the cover member, wherein the adhesive layer is a cured product of a vinyl acetate adhesive (3) containing a vinyl acetate polymer.

The present invention also provides the cover member, wherein the resin film is laminated so that the MD direction is along the bending direction of the cover member.

The present invention also provides the cover member for a touch panel display.

The present invention also provides the cover member for a flexible display.

The present invention also provides the cover member for a fingerprint authentication sensor.

The present invention also provides a touch panel display including the cover member.

The present invention also provides a flexible display including the cover member.

The present invention also provides an electronic device including the display.

The present invention also provides an organic electroluminescent device including the cover member.

The present invention also provides an organic thin film solar cell including the cover member.

The present invention also provides a fingerprint authentication sensor including the cover member.

The present invention also provides an electronic device with a personal authentication function that includes the fingerprint authentication sensor.

The cover member of the present invention has the characteristics of glass. That is, transparency, gas barrier property, water vapor barrier property, chemical stability, thermal stability, electrical insulation property, surface smoothness, high hardness, resistance to twisting (or curl resistance), etc., and good texture (Appearance and touch). In addition to the characteristics of the glass, it also has flexibility and impact resistance. Furthermore, when it has a specific adhesive layer, it also has bending durability and cracks do not occur even if it is repeatedly bent.

Since the cover member of the present invention has the above-mentioned characteristics, it is used for a display (especially, as a member for covering the surface of a touch panel display or a flexible display, or as an electrode protective film of a plasma display), and for protecting a fingerprint authentication sensor. It can be suitably used for applications as a membrane.

The touch panel display equipped with the cover member of the present invention has characteristics derived from glass, is easy to handle, and has excellent impact resistance. Further, the touch panel display of the present invention is superior in touch detection sensitivity to a conventional display having a plastic film as a cover member.

The flexible display equipped with the cover member of the present invention has characteristics derived from glass, is easy to handle, and has excellent impact resistance.

The plasma display equipped with the cover member of the present invention has excellent chemical stability due to the characteristics derived from glass, so that it is possible to stably maintain the low voltage characteristics, which contributes to power saving.

-Electronic devices equipped with the above display have high performance, are easy to handle, and have excellent impact resistance. Therefore, the electronic device including the display contributes to power saving.

The cover member of the present invention has the above-mentioned characteristics, and in particular, since it has the gas barrier property and the water vapor barrier property, it is a substrate member in an organic electroluminescence device (hereinafter sometimes referred to as “organic EL device”) or an organic thin film solar cell. And/or can be preferably used as a sealing member. The organic EL device and the organic thin-film solar cell provided with the cover member of the present invention can be thin, lightweight, flexible, and have a long life.

The fingerprint authentication sensor equipped with the cover member of the present invention has characteristics derived from glass, is easy to handle, and has excellent impact resistance. Further, the fingerprint authentication sensor of the present invention has higher sensitivity than a conventional fingerprint authentication sensor having a plastic film as a cover member.

ㆍThe electronic device with a personal authentication function equipped with the fingerprint authentication sensor has high performance, is easy to handle, and has excellent impact resistance.

It is a schematic diagram which shows the measuring method of the floating amount of a test piece at the time of evaluating curl resistance. FIG. 2 is a schematic diagram (side view) showing a bending durability test method (R bending method) (one set of bending and stretching operations of the cover member at a bending radius (R) of 180° in a direction in which the surface of the glass plate is concave) is there. It is the figure which expanded and showed (4) of FIG. FIG. 3 is a schematic cross-sectional view showing an example of the cover member (1) of the present invention, in which the orientation of the resin film (6) is adjusted so that the MD direction of the resin film (6) is parallel to the bending direction of the cover member. FIG. 3 is a view of the glass plate (4) being bonded via an adhesive layer (5).

[Cover member]
The cover member of the present invention is a laminate having a structure in which a glass plate having a thickness of 500 μm or less and a resin film are laminated via an adhesive layer. The width and length of the cover member can be appropriately adjusted according to the application.

The cover member of the present invention has at least a three-layer laminated structure of glass plate/adhesive layer/resin film. The cover member of the present invention may have other layers in addition to the above three layers. For example, various functional films (for example, antireflection film, antiglare film, antifouling film, ITO film) are formed on the surface of the glass plate. Etc.) may be provided.

The total thickness of the cover member of the present invention is, for example, 1000 μm or less, and in view of excellent flexibility and bending durability, it is preferably 300 μm or less, more preferably 250 μm or less, particularly preferably 200 μm or less, most preferably 150 μm or less. Is. The lower limit of the total thickness is, for example, 50 μm, preferably 75 μm, and particularly preferably 100 μm.

The cover member of the present invention has excellent impact resistance, and the impact resistance according to the following test method (details will be described in Examples) is, for example, 4 cm or more, preferably 5 cm or more, and particularly preferably 6 cm or more.
Impact resistance test:
The cover member is placed on a flat surface with the glass plate side surface facing upward, and a ballpoint pen having a ball diameter of 0.7 mm and a weight of 5.7 g is naturally dropped from the pen tip toward the surface of the cover member to form a glass plate. The drop height (cm) before cracking is used as an index of impact resistance

The cover member of the present invention has flexibility, and its minimum bending radius changes depending on the thickness of the glass plate. For example, when the glass thickness is 50 μm or less, the minimum bending radius of the cover member is, for example, 3 mm or less. (That is, it can be bent at least once until the bending radius becomes 3 mm or less).
When the glass thickness exceeds 50 μm and is 100 μm or less, the minimum bending radius of the cover member is, for example, 20 mm or less (for example, 10 to 20 mm).
When the glass thickness exceeds 100 μm and 150 μm or less, the minimum bending radius of the cover member is, for example, 40 mm or less (for example, 25 to 40 mm).
When the glass thickness exceeds 150 μm and is 250 μm or less, the minimum bending radius of the cover member is, for example, 100 mm or less (for example, 45 to 100 mm).
When the glass thickness exceeds 250 μm and is 500 μm or less, the minimum bending radius of the cover member is, for example, 250 mm or less (for example, 110 to 250 mm).
The minimum bending radius of the cover member can be measured by the method described in the examples.

Further, the cover member of the present invention (particularly, the cover member having an adhesive layer made of a cured product of the adhesive (1) described later) is excellent in that the stress load on the glass plate during bending is relaxed by the adhesive layer. It can exhibit excellent bending durability. That is, it is possible to suppress the occurrence of cracks in the glass plate even after repeated bending and extension. The bending durability according to the following test is, for example, 10 or more, preferably 100 or more, particularly preferably 1000 or more, further preferably 2000 or more, most preferably 10000 or more.
Bending durability test:
From the stretched state of the cut piece (size: 1 cm×7 cm) of the cover member, in the direction in which the surface of the glass plate becomes concave (preferably, the surface of the glass plate becomes concave and the direction along the MD direction of the resin film). The number of sets until a crack is generated in the cut piece when the above-mentioned operation is performed at a speed of 43 sets per minute, with an operation of bending 180° and re-extending at a bending radius (R) below as one set. Is used as an index of bending durability

The bending radius (R) is preferably changed according to the thickness of the glass plate as described below.
When the glass thickness is 50 μm or less, the bending radius is, for example, 3 mm.
When the glass thickness exceeds 50 μm and is 100 μm or less, the bending radius is, for example, 20 mm or less (preferably 10 to 20 mm).
When the glass thickness exceeds 100 μm and 150 μm or less, the bending radius is, for example, 40 mm or less (preferably 25 to 40 mm).
When the glass thickness exceeds 150 μm and is 250 μm or less, the bending radius is, for example, 100 mm or less (for example, 45 to 100 mm).
When the glass thickness exceeds 250 μm and is 500 μm or less, the bending radius is, for example, 250 mm or less (for example, 110 to 250 mm).

The cover member of the present invention has high transparency, and the total light transmittance is, for example, 80% or more, preferably 85% or more, particularly preferably 88% or more, and most preferably 90% or more.

Further, the surface hardness of the cover member of the present invention (particularly the surface hardness of the glass plate side surface) is, for example, H or higher, preferably 2H or higher, especially pencil hardness (JIS K5600-5-4 (ISO/DIN15184)). It is preferably 3H or more, and most preferably 5H or more, and the cover member of the present invention can maintain high surface hardness (particularly the surface hardness of the bent portion) as described above even after continuous bending.

The cover member of the present invention can be wound into a roll to form a wound body. In addition, the wound body thus obtained is easy to convey and easy to store.

Further, since the cover member of the present invention has the above-mentioned characteristics, it can be suitably used as a cover member for a display (in particular, a flexible display). More specifically, the cover member of the present invention can be suitably used as a cover member for a touch panel display or a cover member for a flexible display.

In addition, the cover member of the present invention has high gas barrier property and water vapor barrier property derived from glass, and also has flexibility, so that it is used as a substrate member and/or a sealing member in an organic EL device or an organic thin film solar cell. It can be used preferably.

In addition, if the surface of the cover member of the present invention is provided with a conductor wiring, it can be used as a printed circuit board (particularly, a flexible printed circuit board). For example, a flexible display, a flexible solar cell, a flexible touch panel electrode substrate, a flexible illumination, a flexible It can be suitably used as a substrate in a flexible device such as a battery.

The cover member of the present invention can also be used as a semiconductor insulating film, a liquid crystal display insulating film, an electrode protective film, and the like.

(Glass plate)
The thickness of the glass plate constituting the cover member of the present invention is 500 μm or less, and in terms of excellent flexibility, preferably 250 μm, more preferably 150 μm or less, further preferably 100 μm or less, particularly preferably 75 μm or less, most preferably Is 50 μm or less. Further, in terms of extremely excellent bending durability, it is preferably 10 μm or more, more preferably 20 μm or more, and particularly preferably 30 μm or more.

The minimum bending radius of the glass plate changes according to the thickness of the glass plate, but using a glass plate having a minimum bending radius within the following range is effective in improving the bending durability of the cover member. preferable.
When the glass thickness is 50 μm or less, the minimum bending radius is, for example, 3 mm or less (that is, it can be bent at least once until the bending radius becomes 3 mm or less).
When the glass thickness exceeds 50 μm and is 100 μm or less, the minimum bending radius is, for example, 20 mm or less (for example, 10 to 20 mm).
When the glass thickness exceeds 100 μm and is 150 μm or less, the minimum bending radius is, for example, 40 mm or less (for example, 25 to 40 mm).
When the glass thickness exceeds 150 μm and is 250 μm or less, the minimum bending radius is, for example, 100 mm or less (for example, 45 to 100 mm).
When the glass thickness is more than 250 μm and 500 μm or less, the minimum bending radius is, for example, 250 mm or less (for example, 110 to 250 mm).

(Resin film)
As the resin film forming the cover member of the present invention, it is preferable to use a plastic film having excellent transparency (total light transmittance is 80% or more).

As the material of the plastic film, there are thermoplastic plastics and thermosetting plastics. Examples of the thermoplastic include polyethylene, polypropylene, polyethylene terephthalate (PET), polyvinyl chloride, acrylonitrile butadiene styrene (ABS), polyvinylidene chloride, cellulose acetate (eg, triacetyl cellulose (TAC)), polyethylene. General-purpose plastics such as naphthalate (PEN); engineering plastics such as polyamide, polycarbonate, polyvinylidene fluoride; polysulfone, polyether sulfone, polyphenylene sulfide, polyamide imide (PAI), polyimide (PI), polyether ether ketone (PEEK), etc. Super engineering plastics, etc. are included. The thermosetting plastics include, for example, phenol resin, melamine resin, polyurethane, silicone resin and the like.

As the resin film, a plastic film made of at least one material selected from PET, PAI, PI, cellulose acetate (in particular, TAC), and PEN is preferable because of its extremely excellent bending durability. , PET or PI plastic films are preferred.

The thickness of the resin film is, for example, 500 μm or less, and in terms of excellent flexibility, it is preferably 250 μm, more preferably 150 μm or less, further preferably 140 μm or less, particularly preferably 120 μm or less, most preferably 100 μm or less, further preferably Is 80 μm or less, particularly preferably 70 μm or less. Further, it is preferably 10 μm or more, more preferably 20 μm or more, and particularly preferably 30 μm or more from the viewpoint of extremely excellent bending durability.

(Adhesive layer)
The thickness of the adhesive layer constituting the cover member of the present invention is, for example, 100 μm or less, preferably 80 μm or less, particularly preferably 50 μm or less, and most preferably 30 μm or less. The lower limit of the thickness is, for example, 1 μm, preferably 5 μm. When the adhesive layer is in the above range, the adhesiveness and bending durability as well as the transparency (the total light transmittance is, for example, 80% or more) are preferable, which is preferable. When the thickness of the adhesive layer is excessive, the adhesiveness is improved, but the bending durability and the transparency tend to be lowered.

It is preferable that the adhesive layer has excellent adhesion to a glass plate or a resin film. The adhesion of the adhesive layer (particularly, the adhesive layer made of a cured product of the adhesive (1) described later) to the glass plate and/or the resin film is determined by the cross-cut method (based on JIS K 5600-5-6). In the 6-step classification test, for example, classification 0 to 2.

In addition, in terms of imparting excellent bending durability to the cover member of the present invention, the elastic modulus of the adhesive layer (particularly, the adhesive layer made of a cured product of the adhesive (1) described later) (for example, 25° C.). Young's modulus) is, for example, preferably 0.01 MPa to 1000 GPa, particularly preferably 1 MPa to 100 GPa, most preferably 5 MPa to 50 GPa, and particularly preferably 5 MPa to 10 GPa.

Further, the adhesive layer preferably has excellent heat resistance in that the bending durability of the cover member of the present invention can be kept high even in a high temperature environment, and the glass transition temperature (Tg) or melting point (Tm) of the adhesive layer is preferable. ) Is preferably in the following range.

The glass transition temperature (Tg) or melting point (Tm) of the adhesive layer made of a cured product of the adhesive (1) described below is preferably 70° C. or higher, particularly preferably 80° C. or higher. The upper limit is, for example, 150°C. The glass transition temperature (Tg) or melting point (Tm) of the adhesive (1) can be measured by thermal analysis such as DSC or TGA or dynamic viscoelasticity measurement.

The glass transition temperature (Tg) of the adhesive layer made of a cured product of the acrylic urethane adhesive (2) described below is preferably 0 to 100°C, more preferably 0 to 70°C, and particularly preferably 0 to 30°C. ..

The glass transition temperature (Tg) of the adhesive layer made of a cured product of the vinyl acetate adhesive (3) described below is preferably 5° C. or lower, more preferably less than −5° C., and particularly preferably −10° C. or lower. The lower limit of the glass transition temperature is, for example, −30° C., preferably −20° C.

The glass transition temperatures of the adhesives (2) and (3) are measured, for example, by a method based on JIS K7244-4, more specifically, by dynamic viscoelasticity measurement (for example, heating rate: 5° C./min, measurement It can be determined as the temperature of the peak top of tan δ (loss tangent) measured in the temperature: 20 to 350° C., deformation mode: dynamic viscoelasticity measurement under the conditions of tensile mode).

Further, from the viewpoint that excellent bending durability can be imparted to the cover member of the present invention, the storage elastic modulus at 20° C. of the adhesive layer is preferably in the following range. The storage elastic modulus in the present specification is a value measured using a dynamic viscoelasticity measuring device.

The storage elastic modulus at 20° C. of the adhesive layer made of a cured product of the acrylic urethane adhesive (2) described below is preferably 10 MPa or more, more preferably 50 MPa or more, particularly preferably 80 MPa or more, and most preferably 120 MPa or more. is there.

The storage elastic modulus at 20° C. of the adhesive layer made of a cured product of the vinyl acetate adhesive (3) described later is preferably 10 to 200 MPa, more preferably 30 to 150 MPa, and particularly preferably 30 to 100 MPa.

(adhesive)
The adhesive layer is made of a cured product of an adhesive. Examples of the adhesive for forming the adhesive layer include an ultraviolet curable adhesive, a thermosetting adhesive, and a thermoplastic adhesive. Among the above-mentioned curable adhesives, the ultraviolet curable adhesives are preferable because they are excellent in quick-curing properties and can be used for resin films having low heat resistance. In the present specification, "curing" includes curing of the radical-curable or cationic-curable adhesive described below accompanied by polymerization of monomers, and curing by cooling a heated and softened thermoplastic adhesive (or , Solidification).

UV curable adhesives include radical curable and cationic curable adhesives. Radical curable adhesives are excellent in that they have fast curability and that they have a wide variety of monomers. On the other hand, the cation-curable adhesive is excellent in that it is less susceptible to curing inhibition by oxygen and is rapidly cured even in the presence of oxygen. Further, since the curing shrinkage is small, it has excellent dimensional stability. When the resin film and the glass plate are bonded to each other using an adhesive having a large curing shrinkage, curling is likely to occur in the obtained cover member due to the curing shrinkage of the adhesive.

(Cationic curable adhesive)
The cationically curable adhesive contains a cationically polymerizable monomer and a curing catalyst. Examples of the cationically polymerizable monomer include compounds containing at least one cationically polymerizable group selected from a vinyl ether group, an epoxy group, and an oxetanyl group.

Among them, the cation-curable adhesive has, as a cation-polymerizable monomer, at least one cation-polymerizable group selected from a vinyl ether group, an epoxy group, and an oxetanyl group and at least one hydroxyl group in one molecule. A compound (hereinafter sometimes referred to as "compound (I)") in an amount of 10% by weight or more based on the total amount of the cationically polymerizable monomer,

(In the formula, R is an s-valent linear or branched saturated aliphatic hydrocarbon group, or two or more linear or branched saturated aliphatic hydrocarbon groups bonded via an ether bond. s represents a valent group, and s represents an integer of 2 or more)
An adhesive containing a compound represented by (hereinafter sometimes referred to as "compound (b)") in an amount of 5% by weight or more based on the total amount of the cationically polymerizable monomer (hereinafter sometimes referred to as "adhesive (1)"). ) Is preferred.

The adhesive (1) has excellent adhesion to a glass plate and has an extremely excellent adhesive force even if the glass plate surface is not pretreated (for example, primer treatment, plasma treatment, corona treatment, etc.). The film can be glued. Also, since it has excellent adhesive strength, it can bond the glass plate and the resin film with a very small amount of use, and when the glass plate and the resin film are transparent, they can bond without impairing their transparency. It is possible to form a cover member having excellent transparency (total light transmittance is, for example, 80% or more). Furthermore, the cured product of the adhesive (1) is suppressed in brittleness to an extremely low level and has excellent toughness.

(Compound (I))
The compound (I) is a compound having at least two kinds of functional groups in one molecule. Specifically, it is a compound having at least one cationically polymerizable group selected from a vinyl ether group, an epoxy group, and an oxetanyl group and at least one hydroxyl group in one molecule. The cured product obtained by curing the adhesive containing the compound (I) has high hardness because the two types of functional groups are polymerized to form a highly crosslinked structure.

As the compound (I), a cationic polymerization selected from a vinyl ether group, an epoxy group, and an oxetanyl group in one molecule, from the viewpoint of increasing the hardness, reducing the curing shrinkage, and improving the adhesiveness, of the resulting cured product. The compound (i) having one functional group and one hydroxyl group is preferable.

The compound (i) includes the following three types of compounds.
i-1: a compound having one vinyl ether group and one hydroxyl group, i-2: one compound having an epoxy group and one hydroxyl group, i-3: having one oxetanyl group and one hydroxyl group Compound

The compound (i) is represented by the following formula, for example.
HO-R ^a -Y (i)
(In the formula, R ^a represents a divalent hydrocarbon group, a divalent heterocyclic group, or a divalent group in which these are bonded via a single bond or a linking group. Y is a vinyl ether group, an epoxy group, And a cationically polymerizable group selected from oxetanyl groups)

The above-mentioned hydrocarbon group includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.

Examples of the divalent aliphatic hydrocarbon group include a linear or branched alkylene group having 1 to 18 carbon atoms such as methylene group, methylmethylene group, dimethylmethylene group, ethylene group, propylene group and trimethylene group. A linear or branched alkenylene group having 2 to 18 carbon atoms such as vinylene, 1-methylvinylene, propenylene, 1-butenylene, 2-butenylene, 1-pentenylene or 2-pentenylene group; ethynylene, propynylene, 3- Examples thereof include linear or branched alkynylene groups having 2 to 18 carbon atoms such as methyl-1-propynylene, butynylene, and 1,3-butadiynylene groups.

The alicyclic ring that constitutes the divalent alicyclic hydrocarbon group includes a monocyclic hydrocarbon ring and a polycyclic hydrocarbon ring, and the polycyclic hydrocarbon ring includes a spiro hydrocarbon ring and a ring. It includes an aggregated hydrocarbon ring, a bridged cyclic hydrocarbon ring, a condensed cyclic hydrocarbon ring, and a bridged condensed cyclic hydrocarbon ring. Examples of the divalent alicyclic hydrocarbon group include groups obtained by removing two hydrogen atoms from the structural formula of the alicycle.

Examples of the monocyclic hydrocarbon ring include C _3-12 cycloalkane rings such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane and cyclooctane; C _3-12 cycloalkene rings such as cyclopentene and cyclohexene. Are listed.

Examples of the spiro hydrocarbon ring include C _5-16 spiro hydrocarbon rings such as spiro[4.4]nonane, spiro[4.5]decane, and spirobicyclohexane.

Examples of the ring-assembled hydrocarbon ring include a ring-assembled hydrocarbon ring containing two or more C _5-12 cycloalkane rings such as _{bicyclohexane} .

Examples of the bridged cyclic hydrocarbon ring include pinane, bornane, norpinane, norbornane, norbornene, bicycloheptane, bicycloheptene, bicyclooctane (bicyclo[2.2.2]octane, bicyclo[3.2.1]octane, etc. ) Etc.; bicyclic hydrocarbon rings; tricyclic hydrocarbons such as homobredan, adamantane, tricyclo[5.2.1.0 ^2,6 ]decane, tricyclo[4.3.1.1 ^2,5 ]undecane Ring; tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodecane, perhydro-1,4-methano-5,8-methanonaphthalene, and other tetracyclic hydrocarbon rings.

Examples of the condensed cyclic hydrocarbon ring include a plurality of 5- to 8-membered cycloalkane rings such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, and perhydroindene. Examples include fused rings that are individually condensed.

Examples of the above-mentioned bridged condensed cyclic hydrocarbon ring include diene dimers (for example, cycloalkadiene dimers such as cyclopentadiene, cyclohexadiene, and cycloheptadiene) and hydrogenated products thereof.

Examples of the divalent aromatic hydrocarbon group include arylene groups having 6 to 18 carbon atoms such as phenylene group, biphenylene group and naphthylene group.

The hydrocarbon group may be various substituents [eg, halogen atom, oxo group, substituted oxy group (eg, alkoxy group, aryloxy group, aralkyloxy group, acyloxy group, etc.), carboxyl group, substituted oxycarbonyl group (alkoxy group). Carbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, etc.), substituted or unsubstituted carbamoyl group, cyano group, nitro group, substituted or unsubstituted amino group, sulfo group, heterocyclic group, etc.] Good. The carboxyl group may be protected by a protecting group commonly used in the field of organic synthesis. Further, a heterocyclic ring having an aromatic or non-aromatic attribute may be condensed with the ring forming the alicyclic hydrocarbon group or the aromatic hydrocarbon group.

Examples of the linking group include a carbonyl group (—CO—), an ether bond (—O—), a thioether bond (—S—), an ester bond (—COO—), an amide bond (—CONH—), and a carbonate bond. (-OCOO-) and the like.

Examples of the heterocycle forming the divalent heterocyclic group include a heterocycle containing an oxygen atom as a hetero atom (for example, a 4-membered ring such as an oxetane ring; a furan ring, a tetrahydrofuran ring, an oxazole ring, an isoxazole ring, 5-membered ring such as γ-butyrolactone ring; 6-membered ring such as 4-oxo-4H-pyran ring, tetrahydropyran ring and morpholine ring; benzofuran ring, isobenzofuran ring, 4-oxo-4H-chromene ring, chroman ring, Fused rings such as isochroman ring; 3-oxatricyclo[4.3.1.1 ^4,8 ]undecan-2-one ring, 3-oxatricyclo[4.2.1.0 ^4,8 ]nonane- A bridge ring such as a 2-one ring), a heterocycle containing a sulfur atom as a hetero atom (for example, a 5-membered ring such as a thiophene ring, a thiazole ring, an isothiazole ring, a thiadiazole ring; a 4-oxo-4H-thiopyran ring, etc. A condensed ring such as a benzothiophene ring), a heterocycle containing a nitrogen atom as a hetero atom (for example, a 5-membered ring such as a pyrrole ring, a pyrrolidine ring, a pyrazole ring, an imidazole ring, a triazole ring; a pyridine ring, 6-membered ring such as pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring; condensed ring such as indole ring, indoline ring, quinoline ring, acridine ring, naphthyridine ring, quinazoline ring and purine ring) .. The heterocyclic group includes, in addition to the substituents that the hydrocarbon group may have, an alkyl group (for example, a C _1-4 alkyl group such as a methyl group and an ethyl group), a cycloalkyl group, an aryl group. (For example, a phenyl group, a naphthyl group, etc.) may be included. Examples of the divalent heterocyclic group include groups obtained by removing two hydrogen atoms from the above structural formula of the heterocycle.

Above all, R ^a is preferably ^a divalent hydrocarbon group or a divalent group in which two or more hydrocarbon groups are bonded via a linking group, particularly preferably a divalent aliphatic hydrocarbon group, Alternatively, a divalent group in which two or more aliphatic hydrocarbon groups are bonded via a linking group, most preferably a linear or branched alkylene group having 1 to 18 carbon atoms, or a divalent group having 1 to 18 carbon atoms A group in which two or more linear or branched alkylene groups are bonded via a linking group, particularly preferably a linear or branched alkylene group having 1 to 6 carbon atoms, or 1 to 6 carbon atoms. Two or more of the straight-chain or branched-chain alkylene groups are bound to each other via a linking group. Moreover, as the linking group, an ether bond is preferable.

The compound (i) contains a compound (i-1) having one vinyl ether group and one hydroxyl group and/or a compound (i-3) having one oxetanyl group and one hydroxyl group, It is preferable in that a cured product having higher hardness can be obtained, and it is particularly preferable to contain at least the compound (i-3).

The compound (i) preferably contains at least one selected from the compounds represented by the following formulas (i-1-1) to (i-1-3) (i-3-1), Especially, it is preferable to contain at least a compound represented by the following formula (i-3-1).

(Compound (b))
The compound (b) is a compound represented by the following formula (b).

(In the formula, R is an s-valent linear or branched saturated aliphatic hydrocarbon group, or two or more linear or branched saturated aliphatic hydrocarbon groups bonded via an ether bond. s represents a valent group, and s represents an integer of 2 or more)

S in the formula represents an integer of 2 or more, for example, an integer of 2 to 6, preferably an integer of 2 to 4, particularly preferably an integer of 2 to 3, and particularly preferably 2.

Among the s-valent linear or branched saturated aliphatic hydrocarbon groups for R, examples of the divalent linear or branched saturated aliphatic hydrocarbon group include, for example, methylene group, methylmethylene group, and dimethyl group. Straight-chain or branched alkylene having 1 to 18 carbon atoms (preferably 1 to 10 carbon atoms, particularly preferably 3 to 6 carbon atoms) such as methylene group, ethylene group, propylene group, trimethylene group, tetramethylene group, etc. Groups. The trivalent or higher valent linear or branched saturated aliphatic hydrocarbon group is further defined as (s-2) hydrogens from the structural formula of the divalent linear or branched saturated aliphatic hydrocarbon group. Groups excluding.

The total number of carbon atoms of the group represented by R is, for example, 1 to 20, preferably 2 to 15, particularly preferably 2 to 10, and most preferably 3 to 8.

Examples of the compound (b) include compounds represented by the following formulas (b-1) to (b-5), trimethylolethane triglycidyl ether, pentaerythritol tetraglycidyl ether, glycerin triglycidyl ether, and dipenta. At least one selected from erythritol hexaglycidyl ether is preferable, and particularly at least selected from compounds represented by the following formulas (b-1) to (b-5) in view of low viscosity and excellent coatability. It is one kind, and most preferably at least one kind selected from the compounds represented by the following formulas (b-1) to (b-4).

(Vinyl ether compound (A))
The adhesive (1) has, as a cationically polymerizable monomer, a compound having at least one vinyl ether group in one molecule and having no hydroxyl group (in the present specification, other than the compound (I) described above). 1 type, or 2 or more types may be contained. The vinyl ether compound (A) may have another cationically polymerizable group (for example, an epoxy group, an oxetanyl group, etc.) in addition to the vinyl ether group.

Examples of the vinyl ether compound (A) include compounds represented by the following formula (a).
R ^c -(O-CH=CH ₂ ) _t (a)
(In the formula, R ^c represents a t-valent hydrocarbon group, a t-valent heterocyclic group, or a t-valent group in which these are bonded via a single bond or a linking group, and t is an integer of 1 or more. Show)

The t is an integer of 1 or more, for example, an integer of 1 to 10, preferably an integer of 1 to 5, particularly preferably an integer of 2 to 5.

As the t-valent hydrocarbon group and t-valent heterocyclic group in R ^c, include t-valent group corresponding to the divalent hydrocarbon group and divalent heterocyclic group in R ^a. Further, the t-valent hydrocarbon group and the t-valent heterocyclic group may have a substituent, and as the substituent, the divalent hydrocarbon group and the divalent heterocyclic group in R ^{a can be used} . And a group containing an epoxy group or an oxetanyl group. Further, examples of the linking group include the same examples as the linking group for R ^a . Above all, R ^c is preferably a t-valent group having an alicyclic or heterocyclic skeleton.

Examples of the vinyl ether compound (A) include compounds represented by the following formulas (a-1) to (a-2), cyclohexyl dimethanol monovinyl ether, cyclohexyl vinyl ether, cyclohexyl methyl vinyl ether, cyclohexyl ethyl vinyl ether, menthyl vinyl ether, and tetrahydrofuran. Furyl vinyl ether, norbornenyl vinyl ether, 1-adamantyl vinyl ether, 2-adamantyl vinyl ether, 1,4-cyclohexanediol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether and the like are preferable.

(Epoxy compound (B))
The adhesive (1) has, as a cationically polymerizable monomer, a compound having at least one epoxy group in a molecule and not having a hydroxyl group (in addition to the compound (I) and the compound (b) described above. Except for compounds having a vinyl ether group; in the present specification, it may be referred to as “epoxy compound (B)”) may be contained in one kind or two or more kinds. The epoxy compound (B) may have another cationically polymerizable group (eg, oxetanyl group) in addition to the epoxy group.

The epoxy group includes two adjacent carbon atoms forming an alicyclic ring (for example, a 3- to 8-membered alicyclic ring) such as a cyclohexene oxide group represented by the following formula (e-1), and an oxygen atom. And a group composed of and (hereinafter sometimes referred to as “alicyclic epoxy group”) and an ethylene oxide group represented by the following formula (e-2). In the following formula, R ¹ represents a hydrogen atom or a C _1-3 alkyl group.

As the epoxy compound (B), a compound having two or more epoxy groups in one molecule is preferable because of its excellent curability, and particularly, a compound having two or more alicyclic epoxy groups in one molecule, ethylene oxide. At least one selected from a compound having two or more groups in one molecule and a compound having one or more alicyclic epoxy groups and one or more ethylene oxide groups in one molecule is preferable.

As the compound having two or more alicyclic epoxy groups in one molecule, a compound represented by the following formula (b′) is preferable.

In the above formula (b'), X represents a single bond or a linking group. Examples of the linking group include a divalent hydrocarbon group, an alkenylene group in which part or all of carbon-carbon double bonds are epoxidized, a carbonyl group (—CO—), an ether bond (—O—), Examples thereof include an ester bond (-COO-), a carbonate bond (-O-CO-O-), an amide bond (-CONH-), and a group in which a plurality of these are linked.

Examples of the divalent hydrocarbon group include a linear or branched alkylene group having 1 to 18 carbon atoms and a divalent alicyclic hydrocarbon group having 3 to 18 carbon atoms. Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include methylene group, methylmethylene group, dimethylmethylene group, ethylene group, propylene group, trimethylene group and the like. Examples of the divalent alicyclic hydrocarbon group having 3 to 18 carbon atoms include 1,2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group and 1,2-cyclohexylene group. And cycloalkylene groups (including cycloalkylidene group) such as 1,3-cyclohexylene group, 1,4-cyclohexylene group, and cyclohexylidene group.

Examples of the alkenylene group in the alkenylene group in which some or all of the carbon-carbon double bonds are epoxidized (sometimes referred to as “epoxidized alkenylene group”) include, for example, vinylene group, propenylene group, 1-butenylene group. Examples thereof include linear or branched alkenylene groups having 2 to 8 carbon atoms such as 2-butenylene group, butadienylene group, pentenylene group, hexenylene group, heptenylene group and octenylene group. In particular, the epoxidized alkenylene group is preferably an alkenylene group in which all carbon-carbon double bonds are epoxidized, and more preferably an alkenylene group having 2 to 4 carbon atoms in which all carbon-carbon double bonds are epoxidized. It is an alkenylene group.

A substituent may be bonded to the cyclohexene oxide group in the above formula (b′), and examples of the substituent include a halogen atom, a C _1-10 alkyl group, a C _1-10 alkoxy group, C _2-10 alkenyloxy group, C _6-14 aryloxy group, C _7-18 aralkyloxy group, C _1-10 acyloxy group, C _1-10 alkoxycarbonyl group, C _6-14 aryloxycarbonyl group, C _{7- 18} aralkyloxycarbonyl group, epoxy group-containing group, oxetanyl group-containing group, C _1-10 acyl group, isocyanate group, sulfo group, carbamoyl group, oxo group and the like.

Typical examples of the compound represented by the above formula (b') include (3,4,3',4'-diepoxy)bicyclohexyl, bis(3,4-epoxycyclohexylmethyl)ether, 1,2. -Epoxy-1,2-bis(3,4-epoxycyclohexan-1-yl)ethane, 2,2-bis(3,4-epoxycyclohexan-1-yl)propane, 1,2-bis(3,4) —Epoxycyclohexan-1-yl)ethane, compounds represented by the following formulas (b′-1) to (b′-8) and the like can be mentioned. In the formula (b'-5), L is an alkylene group having 1 to 8 carbon atoms (for example, a straight chain or branched chain having 1 to 3 carbon atoms such as methylene group, ethylene group, propylene group, isopropylene group). A chain-like alkylene group) is shown. In addition, n ¹ and n ² in the following formulas (b′-5) and (b′-7) each represent an integer of 1 to 30.

The compounds having two or more alicyclic epoxy groups in one molecule further include compounds represented by the following formulas (b'-9) (b'-10). N ³ to n ⁸ in the following formulas (b′-9) and (b′-10) are the same or different and each represents an integer of 1 to 30.

Examples of the compound having two or more ethylene oxide groups in one molecule include hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated biphenol diglycidyl ether, and hydrogenated phenol novolac diglycidyl. Alicyclic glycidyl ethers such as ethers and hydrogenated cresol novolac diglycidyl ethers; bisphenol A diglycidyl ethers, bisphenol F diglycidyl ethers, biphenol diglycidyl ethers, phenol novolac diglycidyl ethers, cresol novolac diglycidyl ethers Aromatic glycidyl ethers such as ethers; compounds represented by the following formula (b″) and the like can be mentioned.

In the formula (b"), R" is a group (p-valent organic group) obtained by removing p hydroxyl groups (-OH) from the structural formula of p-valent alcohol, and p and n ⁹ each represent a natural number. .. Examples of the p-valent alcohol [R″(OH) _p ] include polyhydric alcohols such as 2,2-bis(hydroxymethyl)-1-butanol (polyhydric alcohols having 1 to 15 carbon atoms) and the like. p is preferably 1 to 6, n ⁹ is 1 to case 30 is preferably .p is 2 or more, n ⁹ in groups in each [] (outside the square brackets) may be different may be the same Specific examples of the compound represented by the above formula (b″) include a 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol. [For example, a trade name "EHPE3150" (manufactured by Daicel Corporation) and the like can be mentioned.

Examples of the compound having at least one alicyclic epoxy group and at least one ethylene oxide group in one molecule include 1,2:8,9-diepoxylimonene.

As the epoxy compound (B), containing a compound having two or more alicyclic epoxy groups in one molecule (particularly, a compound represented by the formula (b′)) has fast curing property, It is preferable in that a cured product with high hardness can be obtained.

(Oxetane compound (C))
The adhesive (1) has, as a cationically polymerizable monomer, a compound having at least one oxetanyl group in one molecule other than the compound (I) and having no hydroxyl group (vinyl ether group and/or Except for compounds having an epoxy group; in the present specification, it may be referred to as "oxetane compound (C)"), and may contain one or more kinds.

The oxetane compound (C) is represented by, for example, the following formula (c).

(In the formula, R ^a represents a monovalent organic group, R ^b represents a hydrogen atom or an ethyl group, and m represents an integer of 0 or more.)

The monovalent organic group for R ^a is a monovalent hydrocarbon group, a monovalent heterocyclic group, a substituted oxycarbonyl group (alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, cycloalkyloxycarbonyl group. Etc.), substituted carbamoyl groups (N-alkylcarbamoyl groups, N-arylcarbamoyl groups, etc.), acyl groups (aliphatic acyl groups such as acetyl groups; aromatic acyl groups such as benzoyl groups), and two or more of these. Include a monovalent group bonded through a single bond or a linking group.

Examples of the monovalent hydrocarbon group and the monovalent heterocyclic group include monovalent groups corresponding to the divalent hydrocarbon group and the divalent heterocyclic group in R ^a above. Examples of the linking group include the same examples as the linking group for R ^a . These groups may have a substituent, and examples of the substituent include the same examples as the substituent which the hydrocarbon group for R ^a may have.

The above-mentioned m represents an integer of 0 or more, and is, for example, an integer of 0 to 20, preferably an integer of 0 to 1.

As the oxetane compound (C), it is preferable to use, among others, a compound having two or more oxetanyl groups in one molecule from the viewpoint of having a fast curing property and a cured product having a high hardness. A compound represented by the following formula (c-1), a compound represented by the following formula (c-2), and the like are preferable. In the present invention, commercially available products such as "Aron oxetane OXT-221" and "Aron oxetane OXT-121" (all manufactured by Toagosei Co., Ltd.) can be used.

The adhesive (1) contains, for example, 50 to 99.9% by weight (preferably 70 to 98% by weight) of the cationically polymerizable monomer, based on the total amount (100% by weight) of the adhesive. The adhesive (1) contains at least the compound (I) and the compound (b) as a cationically polymerizable monomer, and further, the vinyl ether compound (A), the epoxy compound (B), and the oxetane compound (C). You may contain 1 type(s) or 2 or more types selected from.

The content of the compound (I) is preferably 10% by weight or more (for example, 10 to 65% by weight) of the total amount of the cationically polymerizable monomer contained in the adhesive (1), and a cured product having particularly excellent adhesion to a resin film. The lower limit is preferably 25% by weight, more preferably 30% by weight, particularly preferably 33% by weight, and most preferably 35% by weight. In addition, the upper limit is preferably 55% by weight, particularly preferably 50% by weight, and most preferably 45% by weight from the viewpoint of obtaining a cured product having particularly high hardness. If the content of the compound (I) is less than the above range, the adhesion to glass tends to decrease.

The content of the compound (i-1-1) having at least one vinyl ether group and at least one hydroxyl group and the compound (i-3-1) having at least one oxetanyl group and at least one hydroxyl group is an adhesive agent. It is 25% by weight or more (for example, 25 to 65% by weight) based on the total amount of the cationically polymerizable monomer contained in (1), because a cured product having excellent adhesion to a resin film and high hardness can be obtained. From the standpoint of excellent curability, it is preferably 25% by weight or more and less than 60% by weight, most preferably 25 to 55% by weight, and particularly preferably 25 to 45% by weight.

The content of the compound (i-1-1) having one vinyl ether group and one hydroxyl group is, for example, 30% by weight or less, preferably 25% by weight or less of the total amount of the cationically polymerizable monomer contained in the adhesive (1). And particularly preferably 18% by weight or less.

The content of the compound (i-3-1) having one oxetanyl group and one hydroxyl group is excellent in adhesiveness to a resin film, and a cured product having high hardness is obtained, and thus the adhesive (1) The amount is preferably 15% by weight or more, more preferably 20% by weight or more, and particularly preferably 25% by weight or more based on the total amount of the cationically polymerizable monomer contained in. From the viewpoint of curability, the upper limit of the content is, for example, 55% by weight, preferably 45% by weight, and particularly preferably 40% by weight.

The content of the compound (b) is preferably 5% by weight or more based on the total amount of the cationically polymerizable monomer contained in the adhesive (1), has fast curing property, and has high hardness with excellent adhesion to glass. From the viewpoint of obtaining a cured product of, the content is more preferably 5 to 45% by weight, particularly preferably 12 to 40% by weight, and most preferably 18 to 30% by weight. When the content of the compound (b) is less than the above range, the obtained cured product tends to have low crack resistance and become brittle.

The compound (I)/compound (b) weight ratio is, for example, 0.5 or more, preferably 1.0 or more, and particularly preferably 1 from the viewpoint of obtaining a cured product having excellent adhesion to glass. 0.1 or more, and most preferably 1.3 or more. The upper limit of the weight ratio is, for example, 6.5, preferably 5.5, particularly preferably 3.0, most preferably 2.5, and particularly preferably 2.0.

The content of the compound other than the compound (I) and the compound (b), which has two or more cationically polymerizable groups selected from a vinyl ether group, an epoxy group, and an oxetanyl group in one molecule, is From the viewpoint of curability, for example, 15% by weight or more, preferably 20% by weight or more, particularly preferably 25% by weight or more, and most preferably 30% by weight or more of the total amount of the cationically polymerizable monomer contained in the adhesive (1). is there. The upper limit of the content is, for example, 55% by weight, preferably 50% by weight, from the viewpoint of obtaining a cured product having high hardness and excellent adhesion to glass.

A compound other than the compound (b), which has two or more epoxy groups in one molecule and has no hydroxyl group (preferably a compound having two or more alicyclic epoxy groups in one molecule). , Particularly preferably the content of the compound represented by the formula (b′)) is a cationically polymerizable monomer contained in the adhesive (1) in that it has fast curing property and a cured product with high hardness is obtained. The total amount is preferably 10% by weight or more, more preferably 20% by weight or more, and particularly preferably 25% by weight or more. The upper limit of the content is, for example, 50% by weight, preferably 45% by weight, and particularly preferably 43% by weight from the viewpoint of obtaining a cured product having high hardness and excellent adhesion to glass.

The content of the compound having two or more vinyl ether groups in one molecule and having no hydroxyl group is, for example, 20% by weight or less of the total amount of the cationically polymerizable monomers contained in the adhesive (1), and preferably It is 15% by weight or less.

The content of the compound having two or more oxetanyl groups in one molecule and having no hydroxyl group is, for example, 20% by weight or less of the total amount of the cationically polymerizable monomer contained in the adhesive (1), and preferably It is 15% by weight or less.

The content of the compound having one cationically polymerizable group selected from a vinyl ether group, an epoxy group, and an oxetanyl group in one molecule and having no hydroxyl group is, from the viewpoint of curability, an adhesive (1 Is less than 30% by weight, more preferably 20% by weight or less, particularly preferably 10% by weight or less, most preferably 5% by weight or less, particularly preferably 1% by weight. It is as follows.

(Curing catalyst)
The curing catalyst includes known or conventional photocationic polymerization initiators and photoradical polymerization initiators. It is preferable that the cationically curable adhesive contains at least a photocationic polymerization initiator as a curing catalyst, and in particular, it is preferable that both the cationic photopolymerization initiator and the photoradical polymerization initiator are contained so that the curing reaction of the adhesive may be further improved. It is preferable in that it can be efficiently progressed, and a cured product having particularly high hardness can be obtained.

The cationically curable adhesive preferably uses a photocationic polymerization initiator as a curing catalyst, and the amount thereof is, for example, 0.1 to 20 parts by weight, preferably 0 based on 100 parts by weight of the cationically polymerizable monomer. 0.5 to 20 parts by weight, particularly preferably 1 to 10 parts by weight.

When a photoradical polymerization initiator is used as a curing catalyst together with a photocationic polymerization initiator, the amount of the photoradical polymerization initiator used is 0.1 to 5 parts by weight based on 100 parts by weight of the cationically polymerizable monomer. It is particularly preferably 0.5 to 3 parts by weight, most preferably 0.5 to 2 parts by weight.

Examples of the cationic photopolymerization initiator include diazonium salt compounds, iodonium salt compounds, sulfonium salt compounds, phosphonium salt compounds, selenium salt compounds, oxonium salt compounds, ammonium salt compounds, bromine salt compounds. Etc. In the present invention, for example, product names “CPI-101A”, “CPI-100P”, “CPI-110P” (above, manufactured by San Apro Co., Ltd.), product names “CYRACURE UVI-6990”, “CYRACURE UVI-6992”. "(Above, Dow Chemical Co.), trade name "UVACURE1590" (manufactured by Daicel Ornex Co., Ltd.), trade names "CD-1010", "CD-1011", "CD-1012" (above US Sartomer Product name: “Irgacure-264” (manufactured by BASF), product name “CIT-1682” (manufactured by Nippon Soda Co., Ltd.), product name “PHOTOINITIATOR 2074” (manufactured by Rhodia Japan Co., Ltd.), etc. Can be preferably used. These can be used alone or in combination of two or more.

Examples of the photoradical polymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, diethoxyacetophenone, 1-(4-isopropylphenyl)-2- Hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2- Propyl)ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoinphenyl Ether, benzyl dimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone-4-methoxybenzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone , Isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, methylphenylglyoxylate , Benzyl, camphorquinone and the like. In the present invention, for example, trade names “Irgacure-184”, “Irgacure-127”, “Irgacure-149”, “Irgacure-261”, “Irgacure-369”, “Irgacure-500”, “Irgacure-651” , "Irgacure-754", "Irgacure-784", "Irgacure-819", "Irgacure-907", "Irgacure-1116", "Irgacure-1173", "Irgacure-1664", "Irgacure-1700", "Irgacure-1704" Commercially available products such as "Irgacure-1800", "Irgacure-1850", "Irgacure-2959", "Irgacure-4043", "Darocure-1173" and "Darocure-MBF" (manufactured by BASF) can be preferably used. .. These can be used alone or in combination of two or more.

(Radical curable adhesive)
Examples of the radical-curable adhesive include acrylic adhesives. The acrylic adhesive contains a (meth)acrylic copolymer and a crosslinking agent.

The (meth)acrylic copolymer can be produced, for example, by reacting one or more acrylic monomers in the presence of a photo or thermal radical polymerization initiator.

The weight average molecular weight (converted to standard polystyrene) of the (meth)acrylic copolymer is, for example, about 100,000 to 5,000,000.

Examples of the acrylic monomer include ethyl acrylate, butyl acrylate, isobutyl acrylate, t-butyl acrylate, and acrylic acid C _1-10 alkyl esters such as 2-ethylhexyl acrylate, and the like. Examples thereof include (meth)acrylic acid esters such as methacrylic acid esters. These can be used individually by 1 type or in combination of 2 or more types.

Further, as the acrylic monomer, other radical polymerizable monomers copolymerizable with the (meth)acrylic acid ester can be used in addition to the (meth)acrylic acid ester. Other radically polymerizable monomers include carboxyl group-containing monomers and hydroxyl group-containing monomers. These can be used individually by 1 type or in combination of 2 or more types.

Examples of the carboxyl group-containing monomer include monocarboxylic acids such as (meth)acrylic acid, crotonic acid and isocrotonic acid; polyvalent carboxylic acids such as itaconic acid, maleic acid and fumaric acid; maleic anhydride and itaconic anhydride. An anhydride of polyvalent carboxylic acid; a monoalkyl ester of the polyvalent carboxylic acid (for example, a C _1-16 alkyl ester such as methyl ester, ethyl ester, propyl ester, butyl ester, hexyl ester, octyl ester, lauryl ester, etc.) Are listed.

Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, Examples thereof include vinyl alcohol and allyl alcohol.

In addition to the above, other radically polymerizable monomers include olefins [eg chain olefins such as ethylene, propylene, 1-butene and butadiene (especially C _2-12 alkenes); cyclopentene, cyclohexene, cycloheptene, norbornene, Cyclic olefins such as 5-methyl-2-norbornene and tetracyclododecene], aromatic vinyl compounds (eg, styrene, vinyltoluene, α-methylstyrene, 1-propenylbenzene, 1-vinylnaphthalene, 2-vinylnaphthalene, C _6-14 aromatic vinyl compounds such as 3-vinylpyridine, 3-vinylfuran, 3-vinylthiophene and 3-vinylquinoline; urethane (meth)acrylates (eg 2,4-tolylene diisocyanate, 1,3 -Xylylene diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, 2,2,4-trimethylhexamethylene Polyisocyanate compound such as diisocyanate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, ethylene glycol mono(meth)acrylate, propylene glycol mono(meth)acrylate, 2-hydroxy-3-methoxypropyl (Meth)acrylate, pentaerythritol tri(meth)acrylate, N-methylol(meth)acrylamide, N-hydroxy(meth)acrylamide, etc. (reaction product with (meth)acrylic monomer having active hydrogen); vinyl ester (eg, , C _1-16 fatty acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl caprylate, and vinyl caproate), maleic acid esters or fumaric acid esters (eg, diethyl maleate, dibutyl maleate, dioctyl maleate, maleic acid) Maleic acid di-C _1-10 alkyl esters such as acid di(2-ethylhexyl), and fumaric acid diesters corresponding thereto, and indenes (eg, indene, methyl indene, ethyl indene, dimethyl indene, etc.) Indene; halogenated indene such as chloroindene and bromoindene) and the like.

Examples of the cross-linking agent include isocyanate cross-linking agents and epoxy cross-linking agents. Examples of the isocyanate-based cross-linking agent include aliphatic polyisocyanates such as 1,6-hexamethylene diisocyanate; cycloaliphatic polyisocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate; toluene diisocyanate and xylylene diisocyanate. And other aromatic polyisocyanate compounds; Examples of the epoxy cross-linking agent include 1,3-bis(N,N'-diglycidylaminomethyl)cyclohexane and resorcin diglycidyl ether. These can be used individually by 1 type or in combination of 2 or more types.

The content of the cross-linking agent is, for example, 0.001 to 10 parts by weight with respect to 100 parts by weight of the (meth)acrylic copolymer.

(Thermoplastic adhesive)
The thermoplastic adhesive contains at least one thermoplastic resin.

Examples of the thermoplastic resin include (meth)acrylic acid ester homopolymers or copolymers, (meth)acrylic/urethane copolymers (particularly, (meth)acrylic/urethane graft copolymers), styrene-(meth) ) Acrylic ester copolymer, vinyl acetate-(meth)acrylic acid ester copolymer, ethylene-(meth)acrylic acid ester copolymer, ethylene-(meth)acrylic acid copolymer, (meth)acrylic acid ester -(Meth)acrylic acid copolymer, styrene-acrylonitrile-(meth)acrylic acid ester copolymer, styrene-(meth)acrylic acid ester-(meth)acrylic acid copolymer, styrene-acrylonitrile-(meth)acrylic Acid ester-(meth)acrylic acid copolymer, ethylene-vinyl acetate-(meth)acrylic acid ester copolymer, vinylpyrrolidone-(meth)acrylic acid ester copolymer, styrene-butadiene-(meth)acrylic acid copolymer Acrylic polymer containing (meth)acrylic acid or its ester as a monomer such as polymer; Vinyl acetate polymer containing vinyl acetate as a monomer such as vinyl acetate resin and ethylene-vinyl acetate copolymer; Synthetic rubbers such as styrene-butadiene copolymer, isobutylene resin, isobutylene-isoprene copolymer, butadiene resin, styrene-isoprene copolymer, acrylonitrile-butadiene copolymer; natural rubber; ethylene-vinyl chloride copolymer, chloride Examples thereof include vinyl-vinylidene chloride copolymer, vinylpyrrolidone-styrene copolymer, chlorinated propylene resin, urethane resin and ethyl cellulose.

As the thermoplastic adhesive, an acrylic urethane adhesive (2) containing a (meth)acrylic/urethane copolymer or a vinyl acetate adhesive (3) containing a vinyl acetate polymer (especially ethylene-vinyl acetate (Copolymer) is preferable in that a cover member having excellent bending durability can be obtained.

The adhesive may further contain a solvent, but if it is solvent-free, that is, if it does not contain a solvent, the drying property can be improved, and it can be applied to a resin film that is easily deteriorated by the solvent. Is preferable, and the generation of odor due to volatilization of the solvent can be prevented. The content of the solvent is, for example, 10% by weight or less, preferably 5% by weight or less of the total amount of the adhesive (100% by weight). It is particularly preferably 1% by weight or less.

If necessary, additives such as an antioxidant, a defoaming agent, a leveling agent, a silane coupling agent, a filler, a flame retardant, and a stabilizer (for example, amines) may be added to the adhesive. You can

When the adhesive is a cation-curable adhesive, a well-known and commonly used sensitizer (for example, acridine compound, benzoflavins, perylenes, anthracenes, thioxanthone compounds, laser dyes, etc.) A sensitizer or the like can be added. In particular, when the adhesive is used for the purpose of curing by irradiating UV-LED, the inclusion of a sensitizer improves the ultraviolet light absorption of the curing catalyst and improves the curability. The content of the sensitizer (the total amount of two or more kinds) is, for example, 0.05 to 10 parts by weight, preferably 0.1 to 5 parts by weight, relative to 100 parts by weight of the monomer. Is.

Further, when a compound represented by the following formula (d-1) and a compound represented by the following formula (d-2) are used together as a sensitizer, the coloration of the obtained cured product can be suppressed to an extremely low level. It is preferable from the viewpoint that it can be used, and the combined ratio of these compounds [the compound represented by the formula (d-1)/the compound represented by the formula (d-2); the weight ratio] is, for example, 0.01 to 1.0, It is preferably 0.1 to 0.5, particularly preferably 0.2 to 0.5. As the compound represented by the following formula (d-1), for example, a trade name "ANTRACURE UVS-1331" (manufactured by Kawasaki Kasei Co., Ltd.) can be used. Further, as the compound represented by the following formula (d-2), for example, a trade name “ANTRACURE UVS-581” (manufactured by Kawasaki Kasei Co., Ltd.) can be used.

The surface tension (at 30° C. and 1 atmospheric pressure) of the adhesive is preferably 10 to 50 mN/m, for example. The viscosity of the adhesive [at 25° C. and a shear rate of 100 (1/s)] is 1 to 1000 mPa·s because it has excellent fluidity and excellent dischargeability when applied using an inkjet printing machine or the like. s is preferable, more preferably 5 to 500 mPa·s, particularly preferably 10 to 100 mPa·s, most preferably 10 to 50 mPa·s, and particularly preferably 10 to 30 mPa·s.
The surface tension of the adhesive can be measured by the Wilhelmy method (plate method) using, for example, a high precision surface tensiometer “DY-700” (manufactured by Kyowa Interface Science Co., Ltd.).

The cover member of the present invention can be manufactured, for example, by bonding the above-mentioned glass plate and resin film with an adhesive, and then curing the adhesive.

In the manufacturing process of the cover member (specifically, a cover member having a bending function), when the resin film is laminated on the glass plate, the MD direction of the resin film is the bending direction of the cover member (or , Along the bending direction showing excellent bending durability) or substantially parallel to the bending direction of the cover member (the crossing angle between the MD direction of the resin film and the bending direction of the cover member is, for example, 30° or less, preferably 20). 0° or less, particularly preferably 10° or less, most preferably 5° or less), or the MD direction of the resin film is substantially perpendicular to the fold line generated when the cover member is bent in the bending direction (MD direction of the resin film). The laminating direction is adjusted so that the crossing angle of the fold line and the fold line intersects, for example, 60 to 120°, preferably 70 to 110°, particularly preferably 80 to 100°, and most preferably 85 to 95°. Is preferable in that a cover member having particularly excellent bending durability can be obtained (see FIG. 4 ). The MD direction is the direction in which the molten resin flows when the resin film is manufactured by injection molding, and tends to have better mechanical strength than the TD direction. The MD direction and the TD direction of the resin film can be confirmed by the birefringence orientation direction measured using, for example, a two-dimensional birefringence device (PA-100, manufactured by Photonic Lattice Co., Ltd.).

The method of applying the adhesive to the glass plate and/or the resin film is not particularly limited, and may be, for example, a printing method, a coating method, or the like. Specifically, screen printing, mask printing, offset printing, inkjet printing, flexo printing, gravure printing, squeegee printing, silk screen printing, stamping, dispensing, spraying, brushing, etc. ..

Curing of the adhesive can be performed by a method according to the type of adhesive. For example, when using an ultraviolet curable adhesive as the adhesive, it can be cured by irradiating it with ultraviolet rays, and when using a thermoplastic adhesive as the adhesive, cool the adhesive softened by heating. Can be cured (or solidified).

Examples of the ultraviolet light source include a UV-LED, a mercury lamp such as a low, medium or high pressure mercury lamp, a mercury xenon lamp, a metal halide lamp, a tungsten lamp, an arc lamp, an excimer lamp, an excimer laser, a semiconductor laser, and a YAG. A laser, a laser system in which a laser and a nonlinear optical crystal are combined, a high frequency induced ultraviolet ray generator, or the like can be used. The ultraviolet irradiation amount (integrated light amount) is, for example, 10 to 5000 mJ/cm ² .

Also, heat treatment may be applied in addition to UV irradiation. By performing the heat treatment, the degree of curing can be further improved. When the heat treatment is performed, the heating temperature is about 40 to 200° C., and the heating time is about 1 minute to 15 hours. Further, the curing degree can be improved by leaving still for 1 to 48 hours at room temperature (20° C.) after irradiation with ultraviolet rays.

[display]
The display of the present invention includes the cover member. The display includes a liquid crystal display and a plasma display. Further, the display includes a touch panel display, a flexible display and the like.

A liquid crystal display, for example, as the display of the present invention includes the cover member as a member for covering the panel surface. Further, for example, a plasma display as a display of the present invention includes the cover member as an electrode protective film.

Since the display of the present invention includes the above-mentioned cover member, it has characteristics derived from glass (fine texture, transparency, smoothness, thermal stability, electrical insulation, chemical stability, high hardness, resistance to twisting, etc.). ), and also has flexibility and impact resistance. Furthermore, when the cover member has a specific adhesive layer (preferably an adhesive layer made of a cured product of the adhesive (1) described above), cracks do not occur even when repeatedly bent.

A touch panel display (for example, a capacitance type or a resistance film type touch panel display) provided with the cover member has a high-quality touch derived from glass. Further, since glass has a higher relative permittivity than plastic, a touch panel display including the cover member is superior in touch detection sensitivity to a conventional touch panel display formed of a plastic film. Further, even though the cover member of the present invention is thin, it has high hardness and excellent impact resistance, so that the cover member can be made into a thin film, whereby the charge amount can be increased and the touch detection sensitivity can be further improved. Can be increased. Furthermore, since the hardness is high and the impact resistance is excellent as described above, even if an impact is applied to the display surface, cracks hardly occur and the handling is easy. Further, since it has excellent chemical stability, the surface of the display does not become white and turbid even when it is wiped with a detergent or the like.

The flexible display provided with the cover member (preferably, the cover member having the adhesive layer made of the cured product of the adhesive (1)) is excellent in flexibility and does not crack even when repeatedly bent, The display surface does not turn white. In addition, it has a good texture derived from glass. Further, since the hardness is high and the shock resistance is excellent, even if an impact is applied to the display surface, cracks are less likely to occur and the handling is easy. Furthermore, since it has excellent chemical stability, the surface of the display does not become cloudy even when it is wiped with a detergent or the like.

Plasma displays have a structure in which two glass substrates, a front substrate and a rear substrate, are bonded together. Display electrodes, a dielectric layer, a protective layer, and the like are formed on the front substrate, and address electrodes, barriers, phosphor layers, and the like are formed on the rear substrate. The electrode protection film is a member that covers the dielectric surface of the front substrate and serves as an electron emission source of the plasma display. In the plasma display including the cover member as an electrode protective film, since the cover member has excellent chemical stability due to the characteristics derived from glass, low voltage characteristics can be stably maintained, which contributes to power saving. ..

[Electronics]
An electronic device of the present invention includes the above display. More specifically, the display includes a display in which the cover member covers the panel surface. Alternatively, it includes a display having the cover member as an electrode protective film.

Since the electronic device of the present invention has the above-mentioned constitution, it has characteristics derived from glass (fine texture, transparency, smoothness, thermal stability, electrical insulation, chemical stability, high hardness, and resistance to twisting, etc.). ), and also has flexibility and impact resistance. Furthermore, when the display includes a cover member having an adhesive layer made of the cured product of the adhesive (1), it has excellent bending durability and does not crack even when repeatedly bent. Therefore, the electronic device of the present invention has high performance, is easy to handle, and has excellent impact resistance.

[Organic electroluminescence device]
The organic EL device of the present invention includes the cover member. More specifically, the cover member is provided as a substrate member and/or a sealing member.

Although the organic materials and electrodes used for organic EL devices are deteriorated by a very small amount of water and oxygen, the cover member has a high gas barrier property derived from glass and a high water vapor barrier property (water vapor permeation at 23° C. and 50% RH). Since the rate is, for example, 10 ⁻⁵ g/m ² /day or less), it is possible to prevent the organic material and the electrode from being deteriorated by moisture or oxygen. Further, the cover member also has flexibility.

Therefore, according to the organic EL device of the present invention, a thin and lightweight flexible organic EL device can be realized. In addition, it is possible to prevent deterioration of the organic EL element and realize a long life. The organic EL device includes an organic EL display and an organic EL lighting.

[Organic thin film solar cell]
The organic thin film solar cell of the present invention includes the cover member. More specifically, the cover member is provided as a substrate member and/or a sealing member.

The element (surface electrode/hole transport layer/photoelectric conversion layer/back electrode) constituting the organic thin-film solar cell is deteriorated by a very small amount of water or oxygen, but the cover member has a high gas barrier property derived from glass. Since it has a high water vapor barrier property (the water vapor transmission rate at 23° C. and 50% RH is, for example, 10 ⁻⁵ g/m ² /day or less), it is possible to prevent the element from being deteriorated by moisture or oxygen. .. Further, the cover member also has flexibility.

Therefore, according to the organic thin film solar cell of the present invention, a thin and lightweight flexible organic thin film solar cell can be realized. In addition, deterioration of the element can be prevented and a long life can be realized.

The organic thin film solar cell of the present invention can be suitably used for mobile charging devices and the like.

[Fingerprint authentication sensor]
The fingerprint authentication sensor of the present invention includes the cover member as a protective film that covers the surface of the fingerprint authentication sensor. INDUSTRIAL APPLICABILITY The fingerprint authentication sensor of the present invention can be used for electronic devices (including IC cards) desired to have a personal authentication function such as a touch panel, a display, a card key, and a credit card.

The fingerprint authentication sensor has a structure in which an electrode is formed on the first substrate and the second substrate is stacked on it. The fingerprint authentication sensor of the present invention includes the cover member as the first substrate and/or the second substrate.

Since the fingerprint authentication sensor of the present invention has the above-mentioned configuration, it has a high-quality touch derived from glass. Further, glass has a higher relative dielectric constant than plastic. Therefore, the fingerprint authentication sensor can have a larger capacitance and higher sensitivity than a conventional product using a plastic film as a substrate. Further, since the hardness is high and the impact resistance is excellent, even if an impact is applied to the surface, cracks are less likely to occur and the handling is easy. Further, since it has excellent chemical stability, the surface of the display does not become white and turbid even when it is wiped with a detergent or the like.

[Electronic devices with personal authentication function]
An electronic device with a personal authentication function of the present invention is an electronic device (including an IC card) provided with the fingerprint authentication sensor, and includes, for example, a touch panel with a personal authentication function, a display with a personal authentication function, a card key with a personal authentication function, and an individual. Examples include credit cards with an authentication function.

Since the electronic device with a personal authentication function of the present invention includes the fingerprint authentication sensor including the cover member, it has high sensitivity and high quality. Furthermore, it is easy to handle.

Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to these Examples.

Preparation Example 1 (Preparation of adhesive)
Each component was mixed according to the formulation shown in Table 1 (unit is parts by weight) to obtain an adhesive. The viscosity of the obtained adhesive at 25° C. and a shear rate of 100 (1/s) was measured using an E-type viscometer (trade name “VISCOMETER TV-25”, manufactured by Toki Sangyo Co., Ltd.), It was 22.6 mPa·s.

Preparation Examples 2 to 31, Comparative Preparation Examples 1 to 3 (preparation of adhesive)
An adhesive was obtained in the same manner as in Preparation Example 1 except that the formulation was changed as shown in Table 1 (unit is parts by weight).

(Adhesion evaluation)
The adhesive obtained in the preparation example and the comparative preparation example was applied to a glass plate (trade name "S9112", manufactured by Matsunami Glass Industry Co., Ltd.) (coating thickness: 5 μm), and an LED irradiator as a light source under an air atmosphere. Was irradiated with light having a wavelength of 365 nm to obtain a cured product/glass plate laminate.
The obtained laminate was subjected to an adhesion test (cross-cut method; conforming to JIS K5600-5-6 (ISO2409)), and the adhesion was evaluated by a 6-step classification test.

(Curl resistance evaluation (1))
The adhesive obtained in Preparation Example and Comparative Preparation Example was applied to a PET film (size: length×width=1 cm×7 cm, thickness: 100 μm) as a resin film (coating film thickness: 10 μm), and in an air atmosphere, Light of 365 nm was irradiated using an LED irradiator until tackiness disappeared to obtain a cured product/PET laminate.
The obtained cured product/PET laminate (size: length×width=1 cm×7 cm) was used as a test piece, which was placed on a horizontal surface, and when one of the short sides of the test piece was pressed, the other short side was a horizontal surface. The amount of floating was measured and the curl resistance was evaluated according to the following criteria (FIG. 1). The smaller the floating amount, the better the curl resistance.
◎ (Very good): Lifting amount is less than 1 mm ○ (Good): Lifting amount is 1 mm or more and less than 2 mm △ (Fair): Lifting amount is 2 mm or more and less than 5 mm × (Poor): Lifting amount is 5 mm or more

The results are summarized in the table below.

The abbreviations in the table are explained below.
<Compound (I)>
HEVE: ethylene glycol monovinyl ether HBVE: 4-hydroxybutyl vinyl ether DEGMVE: diethylene glycol monovinyl ether OXT101: 3-ethyl-3-hydroxymethyl oxetane, trade name "Aron Oxetane OXT-101", manufactured by Toagosei Co., Ltd. <Compound (b )>
1,6-HDGE: 1,6-hexanediol diglycidyl ether 1,4-BDGE: 1,4-butanediol diglycidyl ether 1,2-EDGE: ethylene glycol diglycidyl ether NPGDGE: neopentyl glycol diglycidyl ether YH300 : Trimethylolpropane triglycidyl ether <Other cationically polymerizable monomers>
ISBDVE: isosorbide divinyl ether, trade name "ISB-DVE", manufactured by Daicel Corporation ONBDVE: oxanorbornene divinyl ether CHDVE: 1,4-cyclohexanediol divinyl ether 2021P: 3,4-epoxycyclohexylmethyl (3,4-epoxy) ) Cyclohexanecarboxylate, trade name "Ceroxide 2021P", manufactured by Daicel Corporation b'-1: (3,4,3',4'-diepoxy)bicyclohexyl 2-EHVE: 2-ethylhexyl vinyl ether TEGDVE: triethylene glycol Divinyl ether OXT212: 3-ethyl-3-[(2-ethylhexyloxy)methyl]oxetane, trade name "Aron Oxetane OXT-212", Toagosei Co., Ltd. OXT221: Bis[1-ethyl(3-oxetanyl)] Methyl ether, trade name "Aron Oxetane OXT-221", manufactured by Toagosei Co., Ltd. <Radical polymerizable monomer>
DCPA: tricyclodecane dimethanol diacrylate DPGDA: dipropylene glycol diacrylate VEEA: 2-(2-vinyloxyethoxy)ethyl acrylate <Curing catalyst>
CPI-110P: a mixture of diphenyl[4-(phenylthio)phenyl]sulfonium hexafluorophosphate and thiodi-p-phenylenebis(diphenylsulfonium)bis(hexafluorophosphate) (99.5/0.5), trade name "CPI-110P", Irg184: 1-hydroxy-cyclohexyl-phenyl-ketone manufactured by San-Apro Co., Ltd., trade name "Irgacure-184", manufactured by BASF <sensitizer>
UVS1331:9,10-dibutoxyanthracene, trade name "Anthracure UVS-1331", Kawasaki Kasei Co., Ltd. UVS581:9,10-di(capryloyloxy)anthracene, trade name "Anthracure UVS-581" Manufactured by Kawasaki Chemical Industry Co., Ltd.

Example 1
The adhesive obtained in Preparation Example 8 was applied onto a triacetyl cellulose film (TAC, size: length×width=1 cm×7 cm, thickness: 60 μm) so that the thickness after drying was 15 μm, and a glass plate (product After the name "G-leaf", manufactured by Nippon Electric Glass Co., Ltd., thickness 50 μm) is stuck, it is irradiated with light of 365 nm (irradiation amount: 2000 mJ/cm ² ) using an LED irradiator in an air atmosphere. A TAC/adhesive layer/G-leaf stack was obtained. The pencil hardness of the G-leaf surface of the obtained laminate was measured by the method according to JIS K5600-5-4 (ISO/DIN15184) and found to be 9H.

Example 2
PET/adhesion was performed in the same manner as in Example 1 except that a PET film (product number: A4300, manufactured by Toyobo Co., Ltd. size: length×width=1 cm×7 cm, thickness: 75 μm) was used instead of the triacetyl cellulose film. A layer/G-leaf stack was obtained. The pencil hardness of the G-leaf surface of the obtained laminate was 9H.

Example 3
A laminate was obtained in the same manner as in Example 2 except that the PET film (thickness: 75 μm) was replaced with the PET film (thickness: 38 μm).

Example 4
A laminate was obtained in the same manner as in Example 3 except that the glass plate having a thickness of 50 μm was changed to the glass plate having a thickness of 100 μm.

Example 5
A laminate was obtained in the same manner as in Example 3 except that the glass plate having a thickness of 50 μm was changed to the glass plate having a thickness of 150 μm.

Example 6
PET plate with acrylic adhesive layer (adhesive layer thickness: 25 μm, PET thickness: 50 μm, product name “ASF50 527ALF”) on a glass plate (trade name “G-leaf”, manufactured by Nippon Electric Glass Co., Ltd., thickness 50 μm) (Manufactured by Daicel Co., Ltd.) were stuck together to obtain a PET/acrylic adhesive layer/G-leaf laminate.

Example 7
A laminate was obtained in the same manner as in Example 6 except that the glass plate having a thickness of 50 μm was changed to the glass plate having a thickness of 100 μm.

Example 8
A laminate was obtained in the same manner as in Example 6 except that the glass plate having a thickness of 50 μm was changed to the glass plate having a thickness of 150 μm.

Comparative Example 1
Instead of the laminate, only G-leaf (thickness: 50 μm) was used. The pencil hardness of the G-leaf surface was 9H.

Comparative example 2
Instead of the laminate, only a glass plate with a thickness of 100 μm was used.

Comparative Example 3
Instead of the laminate, only a glass plate having a thickness of 150 μm was used.

(Total light transmittance)
The transparency of the laminate (in the comparative example, a glass plate) was evaluated by measuring the total light transmittance (in accordance with JIS-K7361).

(Flexibility evaluation)
At 25° C., the laminate (a glass plate in the comparative example) was bent so as to have a concave glass plate surface, sandwiched between the vices of a vise, and a handle was turned to gradually tighten the laminate at the time when the laminate cracked for the first time. The bending radius of the laminate was defined as the minimum bending radius (mm).

(Bending durability evaluation (1))
Using the laminate (in the comparative example, a glass plate) as a test piece, at 25° C., the test piece was placed horizontally on a flat surface and stretched. When the glass plate having a thickness of 50 μm is used in the direction in which is concave, the bending radius is 3 mm, and when the glass plate having a thickness of 100 μm is used, the glass plate having a bending radius of 15 mm and a thickness of 150 μm is used. In this case, set the bending radius to 35 mm, bend 180°, and then extend again to return it to one set, and perform the above-mentioned operation at a speed of 43 sets per minute, and set the number of sets until cracks occur in the test piece. Was used as an index of bending durability (see FIGS. 2 and 3).

(Impact resistance evaluation)
The laminated body (in the comparative example, a glass plate) was placed on a flat surface with the glass plate side surface facing upward, and a ballpoint pen having a ball diameter of 0.7 mm and a weight of 5.7 g (without ZEBRA New Crystal Care S cap) was placed. With the pen tip facing downward, the laminate is naturally dropped toward the surface of the laminate, and the lowest drop height (cm) at which a glass plate is cracked is used as an index of impact resistance. The drop height is the height of the pen tip position of the ballpoint pen. The drop height started from 1 cm and increased in 1 cm increments.

(Relative permittivity)
The relative permittivity of the laminate (a structure not including the adhesive layer) was calculated. Note that the relative permittivity of the glass plate was 5.8 (1 MHz, 20° C.), the relative permittivity of the PET film was 3.2 (1 MHz, 20° C.), and these two dielectric materials were connected in series for calculation. ..

(Curl resistance evaluation (2))
The laminate (glass plate in the comparative example) was evaluated by the same method as the above-mentioned curl resistance evaluation (1).

The results are summarized in the table below.

Examples 9 to 17 (Preparation of laminate)
The adhesive obtained in Preparation Example 8 was applied onto the resin films shown in the table below so that the thickness after drying was 15 μm, and the glass plate having the minimum bending radius shown in the table below (trade name “G- ”Leaf”, manufactured by Nippon Electric Glass Co., Ltd., thickness 50 μm), the bending direction of the laminate to be obtained is 45° with respect to the MD direction, the TD direction, or the birefringence orientation direction of the resin film. After being laminated so as to be parallel to the direction of, a light of 365 nm was irradiated (irradiation amount: 2000 mJ/cm ² ) using an LED irradiator in an air atmosphere to obtain a resin film/adhesive layer/G-leaf laminate ( A sample number of 10) was obtained for each example. The minimum bending radius was measured by the same method as the above (evaluation of flexibility).

(Flexibility durability evaluation (2))
The obtained laminate (10 samples in each example) was placed horizontally on a flat surface and stretched, and at the center thereof, the test piece was bent in a direction in which the surface of the G-leaf was concave. Bending 180° so that the radius becomes 3 mm, and then stretching again and returning it to 1 set, 1 set is performed 2000 sets at a speed of 43 sets, and from the ratio of the sample in which no crack was generated in the test piece The bending durability was evaluated.

The results are summarized in the table below.

The abbreviations in the table are explained below.
<Resin film>
PET: Biaxially stretched PET film, trade name "Cosmo Shine A4300", Toyobo Co., Ltd. TAC: Biaxially stretched triacetyl cellulose film, trade name "Fujitac TG60UL", Fuji Film Co., Ltd. PEN: Biaxially stretched polyethylene Naphthalate film, trade name "Teonex Q65HA", manufactured by Teijin Film Solutions Ltd. PAI: Biaxially oriented polyamideimide film, trade name "Taimide OT-050", manufactured by Taimide Tech. Inc.

Examples 18 to 24, Comparative Example 4 (Preparation of laminate)
The adhesive described in the following table was applied onto a PET film (biaxially stretched PET film, trade name "Cosmo Shine A4300", manufactured by Toyobo Co., Ltd.) so that the thickness after drying was as described in the following table. Then, a glass plate having a minimum bending radius of 3 mm or less (trade name “G-leaf”, manufactured by Nippon Electric Glass Co., Ltd., thickness: 50 μm) is used to obtain a laminate from which the MD direction of the PET film is to be obtained. After bonding so as to be parallel to the bending direction, the adhesive was cured by the following method to obtain a PET/adhesive layer/G-leaf laminate.
<Curing method>
Examples 18, 21, 23, 24: Cured by heating and drying a solvent Example 19: Curing by irradiating ultraviolet rays Example 20: Curing by irradiating ultraviolet rays after heating and drying a solvent Example 22: The sheet-like adhesive was sandwiched between glass and PET and then cured by vacuum pressure bonding. Comparative Example 4: Cured by standing at room temperature for 24 hours

In addition, the storage elastic modulus and Tg of the adhesive layer were measured by cutting a cured adhesive (thickness: 0.5 mm) into a width of 4 mm and a length of 3 cm, and using this as a sample for dynamic viscoelasticity measurement (DMA). , Was carried out under the following conditions.
<Measuring device and measuring conditions>
Measuring device: Solid viscoelasticity measuring device (“RSAIII”, manufactured by TA INSTRUMENTS)
Atmosphere: Nitrogen temperature range: 20~350℃
Temperature rise: 5℃/min Deformation mode: Tensile mode

The laminates obtained in Examples 18 to 24 and Comparative Example 4 were used as test pieces, and the bending durability was evaluated by the same method as the bending durability evaluation (1).

Further, the impact resistance of the laminate obtained in Example 19 was evaluated by the following method.
(Impact resistance evaluation)
The laminated body (in the comparative example, a glass plate) was placed on a flat surface with the glass plate side surface facing upward, and a ballpoint pen having a ball diameter of 0.7 mm and a weight of 5.7 g (without ZEBRA New Crystal Care S cap) was used. With the pen tip facing downward, the laminate is naturally dropped toward the surface of the laminate, and the lowest drop height (cm) at which a glass plate is cracked is used as an index of impact resistance. The drop height is the height of the pen tip position of the ballpoint pen. The drop height started from 1 cm and increased in 1 cm increments.

The results are summarized in the table below.

The abbreviations in the table are explained below.
<Adhesive>
UA1: Composition containing urethane-modified acrylic polymer and solvent (ethyl acetate/isopropyl alcohol) (Brand name "Akrit 8UA-017", manufactured by Taisei Fine Chemicals Co., Ltd.)
UA2: UV-curable urethane acrylate (commercial name "Acryt 8UX-077A", manufactured by Taisei Fine Chemicals Co., Ltd.) 100 parts by weight, and 5 parts by weight of Irgacure-184 are mixed together UA3: UV-curable urethane acrylic A composition obtained by mixing 0.2 parts by weight of Irgacure-184 with 100 parts by weight of a polymer (trade name "Akrit 8BR-600", manufactured by Taisei Fine Chemical Co., Ltd.) EVA1: Vinyl acetate and ethylene-vinyl acetate co-weight Composition containing coalesce and solvent (water) (trade name "Cevian-A 56094", manufactured by Daicel Finechem Co., Ltd.)
EVA2: Sheet-like adhesive composed of modified ethylene-vinyl acetate copolymer (trade name "Mersen G", manufactured by Tosoh Nikkemi Co., Ltd.)
EVA3: A composition containing a blend of vinyl acetate, an ethylene-vinyl acetate copolymer, a vinyl acetate/alkyl acrylate copolymer, and a solvent (water/methylcyclohexanone) (trade name "Sebian-A 56148", Daicel Fine Chem Co., Ltd.)
EVA4: A composition containing vinyl acetate, an ethylene-vinyl acetate copolymer, a styrene-butadiene copolymer, and a solvent (water/methylcyclohexanone) (trade name "Sebian-A 609", manufactured by Daicel Finechem Co., Ltd.)
SL: Silicone type elastic adhesive, trade name "Cemedine Super X Hyper Wide", manufactured by Cemedine Co., Ltd.

As a summary of the above, the configuration of the present invention and its variations are additionally described below.
[1] A member having a structure in which a glass plate having a thickness of 500 μm or less and a resin film are laminated via an adhesive layer.
[2] The member according to [1], which has an impact resistance of 4 cm or more according to the following test.
Impact resistance test:
The cover member is placed on a flat surface with the glass plate side surface facing upward, and a ballpoint pen having a ball diameter of 0.7 mm and a weight of 5.7 g is naturally dropped from the pen tip toward the surface of the cover member to form a glass plate. [3] The member according to [1] or [2], which has a drop height (cm) until a crack is generated as an index of impact resistance [3] and has a minimum bending radius of 250 mm or less.
[4] The member according to any one of [1] to [3], which has a total thickness of 1000 μm or less.
[5] The member according to any one of [1] to [4], wherein the adhesive layer is a cured product of the following adhesive (1).
Adhesive (1): containing a cationically polymerizable monomer and a curing catalyst, and as the cationically polymerizable monomer, at least one cationically polymerizable group selected from a vinyl ether group, an epoxy group, and an oxetanyl group in one molecule. And 10% by weight or more of the compound having at least one hydroxyl group in the total amount of the cationically polymerizable monomer, and 5% by weight or more of the total amount of the cationically polymerizable monomer in the compound represented by the formula (b).
[6] A compound having at least one cationically polymerizable group selected from a vinyl ether group, an epoxy group, and an oxetanyl group and at least one hydroxyl group in one molecule is represented by formulas (i-1-1) to (i -1-3) The member according to [5], which is at least one selected from the compounds represented by (i-3-1).
[7] A compound having at least one cationically polymerizable group selected from a vinyl ether group, an epoxy group, and an oxetanyl group and at least one hydroxyl group in one molecule is represented by the formula (i-3-1). The member according to [5], which is a compound.
[8] The compound represented by the formula (b) is at least one compound selected from compounds represented by the formulas (b-1) to (b-5), [5] to [7] The member according to any one of 1.
[9] The compound represented by the formula (b) is at least one compound selected from compounds represented by the formulas (b-1) to (b-4), [5] to [7] The member according to any one of 1.
[10] Any of [5] to [9], wherein the adhesive (1) contains, as a cationically polymerizable monomer, a compound represented by the formula (b′) in an amount of 10% by weight or more based on the total amount of the cationically polymerizable monomer. The member according to one.
[11] The compound represented by the formula (b′) is 3,4-epoxycyclohexylmethyl(3,4-epoxy)cyclohexanecarboxylate, (3,4,3′,4′-diepoxy)bicyclohexyl, bis. (3,4-epoxycyclohexylmethyl) ether, 1,2-epoxy-1,2-bis(3,4-epoxycyclohexane-1-yl)ethane, 2,2-bis(3,4-epoxycyclohexane-1) -Yl) propane and at least one compound selected from 1,2-bis(3,4-epoxycyclohexane-1-yl)ethane.
[12] The adhesive (1) contains the compound represented by the formula (c-1) and/or the compound represented by the formula (c-2) as a cationically polymerizable monomer, [5] to [5] 11] The member according to any one of [11].
[13] The member according to any one of [1] to [4], wherein the adhesive layer is a cured product of an acrylic urethane adhesive (2) containing urethane (meth)acrylate or a polymer thereof.
[14] The member according to any one of [1] to [4], wherein the adhesive layer is a cured product of a vinyl acetate adhesive (3) containing a vinyl acetate polymer.
[15] The member according to any one of [1] to [14], wherein the resin films are laminated so that the MD direction is along the bending direction of the member.
[16] The member according to any one of [1] to [15], which is a cover member.
[17] The member according to any one of [1] to [15], which is a cover member for a touch panel display.
[18] The member according to any one of [1] to [15], which is a cover member for a flexible display.
[19] The member according to any one of [1] to [15], which is a cover member for a fingerprint authentication sensor.
[20] Use of the member according to any one of [1] to [15] as a cover member.
[21] Use of the member according to any one of [1] to [15] as a cover member for a touch panel display.
[22] Use of the member according to any one of [1] to [15] as a cover member for a flexible display.
[23] Use of the member according to any one of [1] to [15] as a cover member for a fingerprint authentication sensor.
[24] A method for manufacturing a cover member, using the member according to any one of [1] to [15] to obtain a cover member.
[25] A method for manufacturing a cover member for a touch panel display, using the member according to any one of [1] to [15] to obtain a cover member for a touch panel display.
[26] A method for manufacturing a cover member for flexible display, which comprises using the member according to any one of [1] to [15] to obtain a cover member for flexible display.
[27] A method for manufacturing a cover member for a fingerprint authentication sensor, which comprises using the member according to any one of [1] to [15] to obtain a cover member for a fingerprint authentication sensor.
[28] A touch panel display including the member according to any one of [1] to [15].
[29] A flexible display provided with the member according to any one of [1] to [15].
[30] An electronic device including the display according to [28] or [29].
[31] An organic electroluminescent device including the member according to any one of [1] to [15].
[32] An organic thin-film solar cell including the member according to any one of [1] to [15].
[33] A fingerprint authentication sensor including the member according to any one of [1] to [15].
[34] An electronic device with a personal authentication function, comprising the fingerprint authentication sensor according to [33].

The cover member of the present invention is excellent in transparency, gas barrier properties, water vapor barrier properties, chemical stability, thermal stability, electrical insulation properties, surface smoothness, high hardness, and curl resistance, and has a good texture. At the same time, it has both flexibility and impact resistance. Therefore, it can be suitably used as a cover glass for a display or a protective film for a fingerprint authentication sensor.

1 cover member 2 floating amount 3 horizontal surface 4 glass plate 5 adhesive layer 6 resin film

Claims (19)

1. A cover member having a structure in which a glass plate having a thickness of 500 μm or less and a resin film are laminated via an adhesive layer.
2. The cover member according to claim 1, which has an impact resistance of 4 cm or more according to the following test.
   Impact resistance test:
   The cover member is placed on a flat surface with the glass plate side surface facing upward, and a ballpoint pen having a ball diameter of 0.7 mm and a weight of 5.7 g is naturally dropped from the pen tip toward the surface of the cover member to form a glass plate. The drop height (cm) before cracking is used as an index of impact resistance
3. The cover member according to claim 1 or 2, which has a minimum bending radius of 250 mm or less.
4. The cover member according to any one of claims 1 to 3, having a total thickness of 1000 µm or less.
5. The cover member according to any one of claims 1 to 4, wherein the adhesive layer is a cured product of the following adhesive (1).
   Adhesive (1): containing a cationically polymerizable monomer and a curing catalyst, and as the cationically polymerizable monomer, at least one cationically polymerizable group selected from a vinyl ether group, an epoxy group, and an oxetanyl group in one molecule. And 10% by weight or more of the compound having at least one hydroxyl group based on the total amount of the cationically polymerizable monomer,
   

   

   (In the formula, R is an s-valent linear or branched saturated aliphatic hydrocarbon group, or two or more linear or branched saturated aliphatic hydrocarbon groups bonded via an ether bond. s represents a valent group, and s represents an integer of 2 or more)
   The compound represented by 5 wt% or more of the total amount of the cationically polymerizable monomer is contained.
6. The adhesive (1) further comprises the following formula (b′) as a cationically polymerizable monomer.
   

   

   (In the formula, X represents a single bond or a linking group)
   The cover member according to claim 5, which contains the compound represented by 10% by weight or more of the total amount of the cationically polymerizable monomer.
7. The cover member according to any one of claims 1 to 4, wherein the adhesive layer is a cured product of an acrylic urethane adhesive (2) containing urethane (meth)acrylate or a polymer thereof.
8. The cover member according to any one of claims 1 to 4, wherein the adhesive layer is a cured product of a vinyl acetate adhesive (3) containing a vinyl acetate polymer.
9. The cover member according to any one of claims 1 to 8, wherein the resin film is laminated so that the MD direction is along the bending direction of the cover member.
10. The cover member according to any one of claims 1 to 9 for a touch panel display.
11. The cover member according to any one of claims 1 to 9 for a flexible display.
12. The cover member according to any one of claims 1 to 9 for a fingerprint authentication sensor.
13. A touch panel display comprising the cover member according to any one of claims 1 to 9.
14. A flexible display provided with the cover member according to any one of claims 1 to 9.
15. An electronic device comprising the display according to claim 13 or 14.
16. An organic electroluminescent device comprising the cover member according to any one of claims 1 to 9.
17. An organic thin film solar cell comprising the cover member according to any one of claims 1 to 9.
18. A fingerprint authentication sensor including the cover member according to any one of claims 1 to 9.
19. An electronic device with a personal authentication function, comprising the fingerprint authentication sensor according to claim 18.

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