TWI789506B - Curable adhesive composition, adhesive sheet using the composition, laminate containing the adhesive sheet, and manufacturing method thereof - Google Patents

Abstract

The problem to be solved by the present invention is to provide a hardening adhesive composition, which can complete the construction and join even in a short time and at low temperature, and even if it does not transmit more than two active energy rays, it has Adhered bodies with deflection and unevenness can still be bonded ideally, and an adhesive sheet using the composition, a laminate containing the adhesive sheet, and a manufacturing method thereof are provided. The present invention relates to a curable adhesive composition, which is used for bonding two or more adherends having surfaces that do not transmit active energy rays, and contains a photocurable resin (A), a thermoplastic The resin (B) and the photopolymerization initiator, and the above-mentioned photocurable resin (A) and the above-mentioned thermoplastic resin (B) have polymerizable functional groups other than polymerizable unsaturated double bonds, and the adhesive using this composition sheet, a laminate containing the adhesive sheet, and a manufacturing method thereof.

Description

Curable adhesive composition, adhesive sheet using the composition, laminate containing the adhesive sheet, and manufacturing method thereof

The present invention relates to a curable adhesive composition that can be used for lamination of adherends that are difficult to transmit active energy rays, an adhesive sheet using the composition, a laminate containing the adhesive sheet, and a manufacturing method thereof .

In recent years, liquid crystal display devices have been widely used as display devices for televisions, smartphones, personal assistant devices (PADs), tablet computers, car navigation systems, and the like. The above-mentioned liquid crystal display device is generally known to have a structure in which the following members are stacked: a liquid crystal display panel, a planar lighting device (backlight device) for illuminating the liquid crystal display panel arranged on the backside of the liquid crystal display panel, Circuit boards (substrates), or chassis with other electronic components installed, heat sinks that dissipate heat generated by components, etc.

In order to laminate the components of the above-mentioned liquid crystal display device, for example, the following method is commonly used: when the surface of the components to be laminated has deflection or unevenness, an adhesive is applied and the adhesive is attached to the deflection. , After unevenness, in order to remove the uneven thickness of the coated surface, scrape off the coated adhesive to smooth the surface coated with the adhesive, and then laminate the components on the other side (for example, refer to patent documents 1). Also, in the method of joining the above-mentioned members, for example, there is a step of: when the surface of the members to be laminated has flexures or irregularities, an adhesive is applied and the adhesive is attached to the flexures or irregularities, In order to remove the uneven thickness of the coated surface, the coated adhesive is scraped to smooth the surface coated with the adhesive, and then the members on the other side are laminated (for example, refer to Patent Document 2).

In current manufacturing, in order to ensure the construction time required for the aforementioned lamination steps, it is necessary to use an adhesive with a long hardening time. As a result, the adhesive after the aforementioned lamination step needs to be matured for a long time until sufficient bonding strength is developed. Regarding the method of accelerating the hardening of the adhesive after the aforementioned lamination step, heat hardening of the adhesive under high-temperature conditions has been considered, but there is a concern that the heat during hardening may cause damage to the components of the liquid crystal display device. . In addition, due to the difference in thermal expansion of each member, the strain between the members during cooling causes deformation of the members, or cracks and peeling between the joining material and the members, and there are problems in the joining method using adhesives. topic.

In addition, in order to shorten the aforementioned hardening time, if an adhesive with excellent curability at room temperature is used, the construction time required for the aforementioned lamination step cannot be ensured, and the hardening has already been carried out before lamination, so when laminating There may be cases where sufficient joint strength cannot be expressed. In addition, as for the method of completing hardening at low temperature and in a short time, although a bonding method using light irradiation has been studied, it cannot be used in members that cannot transmit light, and the applicable members are limited, making it difficult to put it into practical use.

Considering the above background, there is a strong demand for a new bonding material, which can be completed in a short time and at low temperature, and can be ideally bonded even to materials that do not transmit light. [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Unexamined Patent Publication No. 2010-181432 [Patent Document 2] Japanese Patent Laid-Open No. 2003-136677

[Problem to be Solved by the Invention]

The problem to be solved by the present invention is to provide a hardening adhesive composition, which can complete the construction and join even in a short time and at low temperature, and has flexibility on the surface of the member even if it cannot transmit more than two active energy rays. Curved, concave-convex adherends can still be bonded ideally. Furthermore, there is provided a curable adhesive composition which, when an adhesive layer is formed using the curable adhesive composition and an adhesive sheet having the adhesive layer is produced, even when the adhesive sheet is wound The adhesive layer can still be prevented from being extruded from the end of the roll when it is stored on a roll, and an adhesive sheet using the composition, a laminate containing the adhesive sheet, and a manufacturing method thereof are provided . [Means to solve the problem]

The inventors of the present case found that by using a curable adhesive composition, which contains a photocurable resin (A), a thermoplastic resin (B) and a photopolymerization initiator, and the aforementioned photocurable resin (A) and the aforementioned The thermoplastic resin (B) has a polymerizable functional group other than a polymerizable unsaturated double bond, so that the aforementioned problems can be solved, leading to the completion of the present invention. [Effect of Invention]

The curable adhesive composition of the present invention does not undergo a rapid and violent hardening reaction even after being irradiated with active energy rays, and has the flexibility required for bonding, so the adhesive composition can be released after an external stimulus is applied. Stacking with components. The curable adhesive composition of the present invention can be bonded even to members that cannot transmit light, for example. The hardening adhesive composition of the present invention can also be heated according to need when hardening, but since the hardening has already started due to the irradiation of active energy rays, it is not necessary to perform the hardening step at a high temperature, and it can be heated even at a low temperature. Hardening is sufficiently advanced, and members can be firmly joined to each other in a short time.

The curable adhesive composition of the present invention contains a photocurable resin (A), a thermoplastic resin (B) and a photopolymerization initiator, and the photocurable resin (A) and the thermoplastic resin (B) are polymerizable Polymerizable functional group other than unsaturated double bonds, so it can form a dense crosslinked structure after hardening, and fully bond the adherend, so it can be specially used to firmly bond various components used in image display devices to each other Materials for joining. Regarding the curable adhesive composition of the present invention, when the adhesive layer is formed using the curable adhesive composition and an adhesive sheet having the adhesive layer is produced, even when the adhesive Even when the sheet is wound on a roll or the like and stored, the adhesive layer can be prevented from being extruded from the end of the roll.

The curable adhesive composition of the present invention is used for laminating two or more adherends having surfaces that do not transmit active energy rays, and contains photocurable resin (A), thermoplastic The resin (B) and the photopolymerization initiator, and the aforementioned photocurable resin (A) and the aforementioned thermoplastic resin (B) have a polymerizable functional group other than a polymerizable unsaturated double bond.

The curable adhesive composition of the present invention adheres to the adherend after applying an external stimulus and activating the polymerizable functional group of the curable adhesive composition, so it can be Hardening is performed in a state where the reactivity of the adhesive composition is improved. Thereby, hardening can be performed at a low temperature and in a short time compared with the state without activation.

The aforementioned external stimuli include heat, light (active energy ray), water (moisture) and the like, but are not limited thereto. Heat and light are preferred, and light is more preferred. If the curable adhesive composition activated by light is not irradiated with light, it will not harden regardless of the storage temperature, the storage stability is good, and the reactive part can be activated even without heating, so it can Hardening takes place at low temperature. Also, one type of external stimulus may be used alone, or multiple types may be used in combination.

For example, in terms of the aforementioned external stimuli, when heat is used in addition to the aforementioned light, since the reaction caused by the aforementioned light has already started, the heat is at best used to promote the hardening reaction, and it is not necessary to heat at a high temperature, even at a low temperature. A good hardening reaction can still be obtained with a short and short reaction time.

The photocurable resin (A) and thermoplastic resin (B) contained in the curable adhesive composition of the present invention have polymerizable functional groups other than polymerizable unsaturated double bonds. This suppresses the rapid hardening reaction after the external stimulus is applied, and slows down the hardening reaction, so that the flexibility required for bonding can be maintained even after the external stimulus is applied. As a result, the adhesive composition and the member can be laminated upon application of an external stimulus.

In the case of the aforementioned curable adhesive composition, for example, after light irradiation, hardening proceeds slowly, so after light irradiation, it still has the flexibility required for bonding, and it can be used even in adherends that cannot transmit light. to join.

As for the aforementioned curable adhesive composition, it is preferable to use a preformed sheet-like composition in consideration of excellent workability before hardening and easy adjustment of thickness.

As for the aforementioned sheet-like bonding material, it is preferable to use a thickness in the range of 50-2000 μm, more preferably in the range of 100-1500 μm, and to use a thickness in the range of 200-1000 μm, which has excellent workability before hardening , and for example, it is ideal for those with unevenness, deflection, etc. on the surface of the adherend, which can still be attached.

As for the aforementioned curable adhesive composition, if its loss tangent (tanδ ₄₀ ) at 40°C is less than 1.5 when measured at a frequency of 1 Hz, it is ideal to obtain the following curable adhesive composition: Excellent workability before hardening. For example, even when an adhesive sheet having an adhesive layer formed using a curable adhesive composition is wound on a roll and stored, the adhesive layer can still be prevented from falling from the roll. The end part of is extruded, and the accompanying property of the deflection of the member and the height difference of the surface is improved; it is better to fall in the range of 0.01 or more and 1.0 or less; use the range of 0.1 or more and 0.8 or less In the latter case, it is more preferable in terms of a curable adhesive composition that has better operability before curing, for example, even if an adhesive sheet having an adhesive layer formed using a curable adhesive composition is wound on a roll When waiting and storing it, it is still possible to further prevent the adhesive layer from being extruded from the end of the roll.

Regarding the aforementioned curable adhesive composition, if the loss tangent (tanδ ₆₀ ) at 60°C is measured at a frequency of 1 Hz and is 1.5 or higher, it is more ideal to obtain the following curable adhesive composition: Excellent workability before hardening. For example, even when an adhesive sheet having an adhesive layer formed using a curable adhesive composition is wound on a roll and stored, the adhesive layer can still be prevented from falling from the roll. The ends are extruded, and the compliance with the deflection of the member and the height difference of the surface is improved. It is better to use 2.0 or more, and it is even better to use 5.0 or more. If you use 10.0 or more, in It is more desirable to obtain a curable adhesive composition that further improves the compliance with the deflection of the member and the surface level difference.

In addition, the above-mentioned loss tangent (tanδ ₄₀ ) at 40°C and loss tangent (tanδ ₆₀ ) at 60°C were obtained by using a dynamic viscoelasticity testing machine (manufactured by Rheometrics, trade name: ARES 2KSTD), and the test piece was clamped in the system. The storage elastic modulus (G') and loss elastic modulus (G") are measured at a temperature of 40°C or 60°C and a frequency of 1Hz between the parallel disks of the measuring part of the testing machine. The loss tangent (tanδ) is expressed as The value (G"/G') obtained by dividing the aforementioned loss elastic modulus (G") by the aforementioned storage elastic modulus (G'). In addition, for the test piece used for the above measurement, the above-mentioned The adhesive layer formed of the curable adhesive composition was cut into a circular shape having a thickness of 1 mm and a diameter of 8 mm.

In addition, the loss tangent (tanδ ₄₀ ) at 40°C and the loss tangent (tanδ ₆₀ ) at 60°C of the aforementioned curable adhesive composition can be determined by appropriately selecting the aforementioned photocurable resin (A), the aforementioned thermoplastic resin ( B) According to the composition or number average molecular weight of other components, etc. as required, it is set within the aforementioned predetermined range.

Also, as for the aforementioned hardening adhesive composition, it is preferable to use one having a melting point in the range of 30°C to 120°C, more preferably one having a melting point in the range of 35°C to 90°C, and one having a melting point in the range of 40°C to 90°C. Those having a melting point within the range of 60°C are ideal for obtaining a curable adhesive composition that has excellent workability before hardening, for example, even if an adhesive layer formed using a curable adhesive composition is used. When the adhesive sheet is wound on a roll or the like and stored, the adhesive layer can still be prevented from being extruded from the end of the roll, and the attachment to the deflection of the member and the level difference of the surface can be obtained. improve.

In addition, the above-mentioned melting point refers to the use of differential scanning calorimetry (DSC method), the temperature is raised from 20°C to 150°C at a heating rate of 10°C/min, and after holding for 1 minute, it is temporarily heated at a temperature of 10°C/min. After cooling to -10°C and keeping it for 10 minutes, the temperature of the maximum exothermic peak (exothermic peak top) observed when the temperature is raised again at 10°C/min is measured.

The curable adhesive composition of the present invention contains a photocurable resin (A), and the photocurable resin (A) has a polymerizable functional group other than a polymerizable unsaturated double bond.

It is preferable to use a photocationically polymerizable compound and/or a photoanionically polymerizable compound for the said photocurable resin (A). By using the aforementioned photocationically polymerizable compound and/or photoanionically polymerizable compound, it is not hindered by oxygen during curing, and the reaction can still continue after irradiation, and since it will be laminated with the member after irradiation with light, Even components that do not transmit light can still be laminated. In particular, the use of a cationically polymerizable compound is preferable since it is excellent in reactivity after irradiation with light, and it is easy to obtain high adhesiveness after curing. The aforementioned photopolymerizable compounds may be used alone or in combination.

The aforementioned photocationically polymerizable compound is not particularly limited as long as it has one or more photocationically polymerizable functional groups in one molecule. For photocationically polymerizable compounds, it is preferable to have one or more epoxy groups, oxetanyl groups, hydroxyl groups, vinyl ether groups, episulfide groups, ethyleneimine groups, and oxazole groups in one molecule. Photocationically polymerizable functional groups such as linyl groups. Among them, in terms of obtaining high curability and bondability after curing, it is more preferable that the aforementioned photocationically polymerizable compound has an epoxy group or an oxetanyl group.

The compound which has one or more epoxy groups in 1 molecule can be used for the said photocationically polymerizable compound which has an epoxy group. Specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, polyhydroxynaphthalene type epoxy resin, isocyanate modified Reactive epoxy resin, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide modified epoxy resin, phenol novolak type Epoxy resin, cresol novolak type epoxy resin, hexanediol type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type cyclopentadiene Oxygen resin, phenol aralkyl type epoxy resin, naphthol novolak type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensation novolak type epoxy resin, naphthol-cresol co-condensation Polycondensation novolak type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenolic resin type epoxy resin, biphenyl modified novolac type epoxy resin, trimethylolpropane type epoxy resin, alicyclic epoxy resin, Acrylic resin with epoxy group, polyurethane resin with epoxy group, polyester resin with epoxy group, flexible epoxy resin, etc.

Among them, as for the above-mentioned epoxy resin, it is preferable to use an alicyclic epoxy resin or a multifunctional aliphatic epoxy resin. If an alicyclic epoxy resin is used, since the above-mentioned photocationic polymerizability is excellent, it is possible to obtain curability. Excellent bonding material, so ideal.

In addition, other resin components can also be mixed with them, or other resin components can be added to improve flexibility, or to improve adhesion and bending strength. For such modified products, CTBN can be used (butadiene-acrylonitrile rubber with carboxyl group at the end) modified epoxy resin; epoxy resin obtained by dispersing various rubbers such as acrylic rubber, NBR, SBR, butyl rubber or isoprene rubber in the resin; Epoxy resin modified by liquid rubber as mentioned above; epoxy resin added with various resins such as acrylic resin, urethane resin, urea resin, polyester resin, and styrene resin; Chelating modified epoxy resin; polyol modified epoxy resin, etc.

Examples of the aforementioned photocationically polymerizable compound having an oxetanyl group include: 1,4-bis((3-ethyl-3-oxetanylmethoxy)methyl)benzene, 1,4-bis((3-methyl-3-oxetanylmethoxy)methyl)benzene, 3-methyl-3-epoxypropyloxetane, 3-ethyl -3-epoxypropyl oxetane, 3-methyl-3-hydroxymethyl oxetane, 3-ethyl-3-hydroxymethyl oxetane, two (1-ethyl Oxetane compounds such as (3-oxetanyl)methyl) ether.

The aforementioned photocurable resin (A) is preferably used in the range of 10% by mass to 50% by mass relative to the total amount of the curable adhesive composition, and if used in the range of 20% by mass to 40% by mass, the It is more desirable to obtain an adhesive composition that does not lower the bondability after curing and, for example, even when an adhesive sheet composed of a curable adhesive composition is wound on a roll or the like and stored, It is still possible to further prevent the adhesive layer from being extruded from the end of the roller, and the compliance with the deflection of the member and the unevenness of the surface is further improved.

Moreover, the curable adhesive composition of this invention contains a thermoplastic resin (B). The aforementioned thermoplastic resin (B) has a polymerizable functional group other than a polymerizable unsaturated double bond. By using the thermoplastic resin (B) having a polymerizable functional group other than the polymerizable unsaturated double bond, it can interact with the aforementioned polymerizable compound (A), and can suppress the rapid hardening reaction after external stimulus is applied, And the hardening reaction proceeds slowly, so it can still have the flexibility required for bonding after external stimulation is applied. As a result, the adhesive composition and the member can be laminated upon application of an external stimulus.

The polymerizable functional group contained in the thermoplastic resin (B) preferably has at least one or more selected from the group consisting of an isocyanate group, a hydroxyl group, an oxetanyl group, and an epoxy group. By using the aforementioned thermoplastic resin (B) having at least one or more selected from the group consisting of isocyanate group, hydroxyl group, oxetanyl group, and epoxy group, it is possible to combine with the aforementioned polymerizable compound (A) They react with each other, and can suppress the rapid hardening reaction after the external stimulus is applied, and make the hardening reaction proceed slowly, so it can still have the flexibility required for bonding after the external stimulus is applied. As a result, the adhesive composition and the member can be laminated upon application of an external stimulus.

As for the aforementioned thermoplastic resin (B), if its loss tangent (tanδ ₄₀ ) at 40°C is less than 1.5 when measured at a frequency of 1 Hz, it is ideal for obtaining the following curable adhesive composition: before hardening The workability is excellent, for example, even when the adhesive sheet having the adhesive layer formed by using the curable adhesive composition containing the aforementioned thermoplastic resin (B) is wound on a roll or the like and stored, the The adhesive layer is extruded from the end of the roller, and the attachment to the deflection of the member and the height difference of the surface is improved; it is better to fall in the range of 0.01 or more to 1.0 or less; use 0.1 If the range is more than 0.8, it is more preferable in the following aspects: the workability before curing is excellent, for example, even if the adhesive layer is formed using the curable adhesive composition containing the aforementioned thermoplastic resin (B). When the tab is wound on a roll or the like and stored, the adhesive layer can be further prevented from being extruded from the end of the roll.

As for the aforementioned thermoplastic resin (B), if the loss tangent (tanδ ₆₀ ) at 60°C is measured at a frequency of 1 Hz and is 1.5 or higher, it is preferable to obtain a curable adhesive composition as follows: The workability is excellent, for example, even when the adhesive sheet having the adhesive layer formed by using the curable adhesive composition containing the aforementioned thermoplastic resin (B) is wound on a roll or the like and stored, the The adhesive layer is extruded from the end of the roller, and the compliance with the deflection of the member and the unevenness of the surface is improved. It is better to use 5.0 or more. It is more ideal in terms of a hardening adhesive composition that can further improve the adherence to the deflection of the member and the unevenness of the surface.

In addition, the above-mentioned loss tangent (tanδ ₄₀ ) at 40°C and loss tangent (tanδ ₆₀ ) at 60°C were obtained by using a dynamic viscoelasticity testing machine (manufactured by Rheometrics Co., Ltd., trade name: ARES 2KSTD), and the test piece was clamped in the system. The storage elastic modulus (G') and loss elastic modulus (G") are measured at a temperature of 40°C or 60°C and a frequency of 1Hz between the parallel disks of the measuring part of the testing machine. The loss tangent (tanδ) is expressed as The value (G"/G') obtained by dividing the aforementioned loss elastic modulus (G") by the aforementioned storage elastic modulus (G'). In addition, for the test piece used for the above measurement, the above-mentioned The adhesive layer formed of the curable adhesive composition was cut into a circular shape having a thickness of 1 mm and a diameter of 8 mm.

In addition, the loss tangent (tanδ ₄₀ ) at 40°C and the loss tangent (tanδ ₆₀ ) at 60°C of the above-mentioned thermoplastic resin (B), for example, when using a urethane-based resin, can be properly selected to form urethane The composition of the polyol and polyisocyanate of the ester resin or the number average molecular weight thereof is set within the aforementioned predetermined range.

Also, for the aforementioned thermoplastic resin (B), it is preferable to use one having a melting point in the range of 30°C to 120°C, more preferably one having a melting point in the range of 35°C to 100°C, and one having a melting point in the range of 40°C to 80°C. Those having a melting point within the above range are ideal for obtaining a curable adhesive composition that is excellent in workability before hardening, for example, even if a curable adhesive composition containing the aforementioned thermoplastic resin (B) is formed When the adhesive sheet of the adhesive layer is wound on a roll or the like and stored, the adhesive layer can still be prevented from being extruded from the end of the roll, and it is attached to the deflection of the component and the level difference of the surface The attachment of parts has been improved.

In addition, the above-mentioned melting point refers to the use of differential scanning calorimetry (DSC method), the temperature is raised from 20°C to 150°C at a heating rate of 10°C/min, and after holding for 1 minute, it is temporarily heated at a temperature of 10°C/min. After cooling to -10°C and keeping it for 10 minutes, the temperature of the maximum exothermic peak (exothermic peak top) observed when the temperature is raised again at 10°C/min is measured.

In addition, as the aforementioned thermoplastic resin (B), it is preferable to use an adhesive resin having a weight-average molecular weight in the range of 2,000 to 2,000,000 in order to obtain an adhesive composition that has excellent workability before hardening, and For example, even when an adhesive sheet having an adhesive layer formed using the curable adhesive composition described above is wound up on a roll or the like and stored, the adhesive layer can be further prevented from being drawn from the end of the roll. Extrusion, and the compliance with the deflection of the member and the unevenness of the surface are further improved. A more ideal range of weight average molecular weight is 5,000-1,000,000, and an even more ideal range of weight average molecular weight is 5,000-800,000. If the weight average molecular weight is too small, the cohesive force of the curable adhesive composition before curing is insufficient, and the curable adhesive composition oozes out over time, resulting in a decrease in workability. Moreover, when a weight average molecular weight is too large, compatibility with the said photocurable resin (A) may fall.

Examples of the thermoplastic resin (B) include polyester resins, urethane resins, acrylic resins, and polyvinyl acetal resins. These adhesive resins may be homopolymers or copolymers. In addition, these adhesive resins may be used alone or in combination of two or more.

For the aforementioned thermoplastic resin (B), it is preferable to use a urethane-based resin or an acrylic resin in order to obtain an adhesive composition that is excellent in workability before hardening and, for example, even if it is used When the adhesive sheet of the adhesive layer formed by the curable adhesive composition is wound on a roll and stored, the adhesive layer can still be further prevented from being extruded from the end of the roll, and the accompanying It is more preferable to use a urethane-based resin (B') to further improve the conformability to the flexure of the member and the uneven portion of the surface.

The aforementioned urethane resin (B') preferably has a polymerizable functional group other than a polymerizable unsaturated double bond. By using the urethane-based resin (B') having a polymerizable functional group other than a polymerizable unsaturated double bond, it is possible to suppress a rapid response to external stimuli to the aforementioned adhesive composition, so it is possible to The members are joined to each other after an external stimulus is applied.

As for the aforementioned external stimulus, light is preferably used. When the polymerization reaction is advanced to form a cured product, by using the above-mentioned urethane resin (B') having a polymerizable functional group other than the polymerizable unsaturated double bond, not only polymerization can be performed by irradiation with light, but also Polymerization is carried out by means of a dark reaction, so that, for example, members that cannot transmit light can be joined to each other.

As for the aforementioned external stimulus, in addition to the aforementioned light, heat may also be used in combination if necessary. At this time, since the aforementioned light-induced reaction has already started, the heat is used to promote the hardening reaction at best. It is not necessary to heat at a high temperature, and a good hardening reaction can be obtained even at a low temperature and for a short time.

The polymerizable functional group other than the aforementioned polymerizable unsaturated double bond preferably has at least one or more selected from the group consisting of an isocyanate group, a hydroxyl group, an oxetanyl group, and an epoxy group. As the urethane resin (B') having the aforementioned isocyanate group, for example, a polyisocyanate group-containing polyol (b'1) obtained by reacting a polyisocyanate (b'2) can be used. Carbamate (B'1).

As the urethane-based resin (B') having the aforementioned hydroxyl group, for example, polyurethane having a hydroxyl group obtained by reacting a polyol (b'1) with a polyisocyanate (b'2) can be used. Ester (B'2).

As for the urethane resin (B') having the aforementioned oxetanyl group or epoxy group, for example, a polyurethane (B'1) having the aforementioned isocyanate group can be used A functional group (b"1) that can react with the aforementioned isocyanate group and has an oxetanyl group or an epoxy group and has at least one polymerizable functional group (b"2) other than an unsaturated double bond. Polyurethane (B'3) obtained by reacting body (B"). As the functional group (b"1) capable of reacting with the aforementioned isocyanate group, for example: hydroxyl group, amino group, carboxyl group, mercapto group, etc. can be used, preferably: hydroxyl group, amino group.

The above-mentioned polymerizable functional group (b"2) other than the unsaturated double bond refers to those other than the so-called functional groups having radical polymerizability, such as functional groups having cationic polymerizability and anionic polymerizable functional groups. functional group. In addition, as for the polymerizable functional group (b"2) other than the above-mentioned unsaturated double bond, for example: epoxy group, oxetanyl group, epithiol group, etc. can be used, and oxetane group is preferably used. alkyl.

Regarding the aforementioned monomer (B"), if it has a functional group (b"1) capable of reacting with the aforementioned isocyanate group and an oxetanyl group or an epoxy group, and has polymerizability other than the aforementioned unsaturated double bond The functional group (b"2) is not particularly limited, and examples include: 3-ethyl-3-(4-hydroxybutyl)oxymethyl-oxetane, 3-hydroxymethyl-3- Ethyl oxetane, 2-hydroxymethyl oxetane, 3-hydroxy oxetane, etc.

The above-mentioned monomer (B") is preferably used within the range of 5 parts by mass to 20 parts by mass, and 5 parts by mass to 15 parts by mass relative to 100 parts by mass of the above-mentioned urethane resin (B'). It is better to use within the range.

More specifically, the aforementioned monomer (B") is preferably used to supply more than 50 mol% and 100 mol% of the isocyanate group moles of the aforementioned urethane resin (B'). The amount of the following functional groups that can react with the aforementioned isocyanate groups is better to use the amount of functional groups that can supply 60 mol% to 100 mol% of the energy to react with the aforementioned isocyanate groups, and use 80 mol% to 100 mol% The amount of the functional group that can react with the above-mentioned isocyanate group is even better. Thereby, appropriate flexibility, rapid hardening, shape retention, mechanical strength, and durability after being applied to the substrate can be obtained (especially hydrolysis resistance), the above-mentioned thermoplastic resin (B) excellent in adhesiveness to a base material, etc.

When reacting the aforementioned urethane-based resin (B') with the aforementioned monomer (B"), a urethane-forming catalyst can be used as needed. The aforementioned urethane-forming catalyst can be added to the aforementioned urethane Add appropriately at any stage of the urethanization reaction. The above-mentioned urethanization reaction is preferably carried out until the isocyanate group content (%) becomes a substantially constant value.

啉等含氮化合物；乙酸鉀、硬脂酸鋅、辛酸錫(II)等有機金屬鹽；二月桂酸二丁基錫等有機金屬化合物等。As for the aforementioned urethanization catalyst, for example, triethylamine, triethylenediamine, N-methyl

Nitrogen-containing compounds such as morphine; organometallic salts such as potassium acetate, zinc stearate, and tin(II) octoate; organometallic compounds such as dibutyltin dilaurate, etc.

In addition, as the aforementioned polyol (b'1) that can be used in the production of the aforementioned urethane resin (B'), it is possible to use polyols selected from polycarbonate polyols, polyester polyols, and polyether polyols. One or more types of the group consisting of polyols, etc. Among them, for the aforementioned polyol (b'1), it is preferable to use polycarbonate polyol and polyester polyol alone, or to use two or more of them in combination. When polycarbonate polyol and polyester polyol are used in combination, It is preferable to obtain a curable adhesive composition that is excellent in workability before curing and, for example, can be an adhesive sheet containing the curable adhesive composition of the above-mentioned urethane resin (B'). When it is wound on a roll and stored, the adhesive layer can still be further prevented from being extruded from the end of the roll, and the attachment to the deflection of the member and the level difference of the surface can be further improved. Improved.

As the above-mentioned polycarbonate polyol, for example, one obtained by reacting carbonate and/or phosgene with a low-molecular-weight polyol described later can be used. As the aforementioned carbonate, for example, methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate and the like can be used.

Also, as for the aforementioned low-molecular-weight polyols capable of reacting with carbonate and phosgene, for example, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, and 1,2-propanediol can be used. , 1,3-propanediol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol , 1,5-pentanediol, 1,5-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,7-heptanediol, 1,8- Octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 2-methyl-1, 3-propanediol, neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1, 3-hexanediol, 2-methyl-1,8-octanediol, 1,4-cyclohexanedimethanol, hydroquinone, resorcinol, bisphenol A, bisphenol F, 4 , 4'-biphenol and so on.

As the aforementioned polycarbonate polyol, aliphatic polycarbonate polyol or alicyclic polycarbonate polyol is preferably used.

For the aliphatic polycarbonate polyol, it is preferable to use it in imparting adhesiveness to the curable adhesive composition containing the above-mentioned urethane resin (B'), for example, at a level that can be attached at room temperature. Dialkyl carbonate is selected from 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol and 1,6-hexanediol It is obtained by reacting one or more polyhydric alcohols in the group consisting of alcohols.

In the alicyclic polycarbonate polyol, the adhesiveness of the adhesive sheet of the curable adhesive composition containing the above-mentioned urethane-based resin (B') can be attached at room temperature, for example. , and in terms of imparting excellent initial cohesion, it is preferable to use, for example, one obtained by reacting dialkyl carbonate with one or more polyhydric alcohols selected from the group consisting of cyclohexanedimethanol and its derivatives .

Regarding the aforementioned polycarbonate polyols, it is preferable to use those having a number average molecular weight in the range of 500 to 5,000, more preferably those having a number average molecular weight in the range of 800 to 3,000, in order to obtain the following adhesive sheet: Urethane resins with a loss tangent (tanδ ₄₀ and tanδ ₆₀ ) within the aforementioned predetermined range are excellent in workability before curing, and even if curable adhesives containing the aforementioned urethane resin (B') are bonded When the adhesive sheet of the adhesive composition is wound on a roll and stored, it can further prevent the adhesive layer from being extruded from the end of the roll, and it will be attached to the deflection of the component and the level difference of the surface The attachment of parts has been further improved.

The aforementioned polycarbonate polyol should be used in the range of 20% by mass to 80% by mass relative to the total amount of the aforementioned polyol (b'1), more preferably in the range of 30% by mass to 70% by mass, and at 40% by mass If it is used in the range of mass % to 50 mass %, it is ideal to obtain an adhesive sheet that maintains the adhesiveness of the level that can be attached under light and normal temperature, and even if it will use the above-mentioned urethane When the adhesive sheet of the adhesive layer of the curable adhesive composition based on resin (B') is wound up on a roll or the like and stored, the adhesive layer can be further prevented from being drawn from the end of the roll. Extrusion, and the compliance with the deflection of the member and the unevenness of the surface are further improved.

As the polyester polyol that can be used for the polyol (b'1), for example, those obtained by esterifying a low-molecular-weight polyol with a polycarboxylic acid, ε-caprolactone, etc. Polyesters obtained by ring-opening polymerization of cyclic ester compounds, their copolymerized polyesters, etc.

For the aforementioned low molecular weight polyols, for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol with a molecular weight of approximately 50-300 can be used , neopentyl glycol, 1,3-butanediol and other aliphatic alkylene glycols; or cyclohexanedimethanol, etc.

Also, as the aforementioned polycarboxylic acid that can be used in the manufacture of the aforementioned polyester polyol, for example, aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and dodecanedicarboxylic acid can be used; or Aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, and naphthalene dicarboxylic acid; and their anhydrides or esters, etc.

As far as the aforementioned polyester polyols are concerned, it is preferable to use aliphatic polyester polyols, and it is more preferable to use straight-chain aliphatic polyester polyols in order to obtain the following adhesive sheet: to form a loss tangent (tanδ) within the aforementioned predetermined range. ₄₀ and tanδ ₆₀ ) urethane-based resins have excellent workability before hardening, and for example, even with adhesives formed using a curable adhesive composition containing the above-mentioned urethane-based resin (B') When the adhesive sheet of the agent layer is wound on a roll and stored, it can still further prevent the adhesive layer from being extruded from the end of the roll, and it is attached to the deflection of the component and the level difference of the surface The accompanying property is further improved. The aforementioned linear aliphatic polyester polyol refers to a polyester polyol having no alkyl group in its side chain.

The polyester polyols mentioned above include those obtained by reacting the aforementioned aliphatic alkylene glycols with aliphatic dicarboxylic acids, preferably by esterifying 1,6-hexanediol with adipic acid. Aliphatic polyester polyol obtained by reaction.

As for the aforementioned polyester polyol, it is preferable to use one having a number average molecular weight in the range of 1000 to 5000 in order to obtain the following adhesive sheet: form an amine having a loss tangent (tanδ ₄₀ and tanδ ₆₀ ) within the aforementioned predetermined range The formate-based resin has excellent workability before hardening, and for example, even if an adhesive sheet having an adhesive layer formed using a curable adhesive composition containing the above-mentioned urethane-based resin (B') is rolled When it is wound on a roll or the like and stored, the adhesive layer can still be further prevented from being extruded from the end of the roll, and the compliance with the deflection of the member and the level difference of the surface can be further improved. improve.

In particular, when a polyester polyol obtained by reacting an aliphatic diol such as 1,2-ethanediol or 1,4-butanediol with adipic acid is used as the aforementioned polyester polyol, The number average molecular weight in the range of 1100~2900 should be used; when using polyester polyol obtained by reacting 1,6-hexanediol with adipic acid, the number average molecular weight in the range of 1100~5000 should be used. Molecular weight; when using polyester polyol obtained by reacting 1,6-hexanediol and sebacic acid, it is preferable to use one having a number average molecular weight in the range of 1,000 to 5,000.

The aforementioned polyester polyol is preferably used in the range of 10% by mass to 50% by mass relative to the total amount of the aforementioned polyol (b'1), and if it is used in the range of 20% by mass to 40% by mass, the following The adhesive sheet is more ideal: it maintains the level of adhesiveness that can be attached at room temperature, and even if it will have the adhesive formed by using the curable adhesive composition containing the aforementioned urethane resin (B'). When the adhesive sheet of the adhesive layer is wound on a roll and stored, it can still further prevent the adhesive layer from being extruded from the end of the roll, and it will be attached to the deflection of the component and the level difference of the surface. The attachment of parts has been further improved.

As the aforementioned polyol (b'1), it is preferable to use the aforementioned polycarbonate polyol and the aforementioned polyester polyol in combination.

The aforementioned polycarbonate polyol and the aforementioned polyester polyol are preferably used to contain a total of 20 parts by mass or more with respect to 100 parts by mass of the aforementioned polyol (b'1). When using 50 parts by mass or more, the following viscosity is obtained Ideal for tabs: maintaining adhesiveness at a level that can be attached at room temperature, and even with an adhesive formed using a curable adhesive composition containing the aforementioned urethane resin (B') When the adhesive sheet of the double layer is wound on a roll and stored, it can further prevent the adhesive layer from being extruded from the end of the roll, and it is attached to the deflection of the component and the height difference of the surface. Attachment is further improved.

When using the above-mentioned polycarbonate polyol and the above-mentioned polyester polyol in combination, [polycarbonate polyol/polyester polyol] (mass ratio) should fall within the range of 0.4~7.0, fall within the range of 1.0~2.0 If this is the case, it is more ideal to obtain an adhesive sheet that has a loss tangent (tanδ ₄₀ and tanδ ₆₀ ) within the aforementioned predetermined range of the urethane-based resin, and as a result can be maintained at a level that can be attached at room temperature. Adhesiveness, and for example, even when an adhesive sheet having an adhesive layer formed using a curable adhesive composition containing the aforementioned urethane resin (B') is wound on a roll or the like and stored , can still further prevent the adhesive layer from being extruded from the end of the roller, and the compliance with the deflection of the member and the height difference of the surface is further improved.

In addition, polyether polyols can also be used as the aforementioned polyol (b'1). As the aforementioned polyether polyol, for example, one obtained by addition-polymerizing alkylene oxide using one or more compounds having two or more active hydrogen atoms as an initiator can be used.

As the aforementioned initiator, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, Alcohol, 1,6-hexanediol, bisphenol A, glycerin, trimethylolethane, trimethylolpropane, etc.

As the aforementioned alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide, phenyloxirane, epichlorohydrin, tetrahydrofuran and the like can be used. As the aforementioned polyether polyols, aliphatic polyether polyols and polyether polyols having an alicyclic structure are preferably used.

As the aforementioned polyether polyol, polytetramethylene glycol obtained by ring-opening polymerization of tetrahydrofuran and polytetramethylene glycol obtained by reacting tetrahydrofuran with alkyl-substituted tetrahydrofuran can be used in particular. derivatives, polytetramethylene glycol derivatives obtained by copolymerizing neopentyl glycol and tetrahydrofuran, and the like. Among them, the above-mentioned polyether polyol maintains the adhesion of the adhesive sheet containing the above-mentioned curable adhesive composition at room temperature, and improves excellent flexibility and durability ( In particular, hydrolysis resistance) and the like, polytetramethylene glycol (PTMG) and polytetramethylene glycol derivatives (PTXG) are preferably used. Also, as the aforementioned polyol (b'1), other polyols may be used in addition to the aforementioned ones. As said other polyol, acrylic polyol etc. are mentioned, for example.

For the aforementioned polyol (b'1), it is preferable to use one having a number average molecular weight in the range of 500 to 5,000, and to use a polyol having a number average molecular weight in the range of 1,000 to 3,000 is more effective in obtaining shape retention and coating workability. , initial cohesion and other excellent hardening adhesive composition is ideal. In addition, the said number average molecular weight is the value measured by the following conditions.

[Determination method of number average molecular weight] The measurement of the number average molecular weight described in the present invention is a value obtained by measuring the polystyrene-equivalent gel permeation chromatography (GPC) under the following conditions.

Resin sample solution: 0.4% by mass tetrahydrofuran (THF) solution Measuring device model: HLC-8220GPC (manufactured by Tosoh Co., Ltd.) String: TSKgel (manufactured by Tosoh Co., Ltd.) Eluent: Tetrahydrofuran (THF)

As the polyisocyanate (b'2) that can be used in the production of the above-mentioned urethane resin (B'), alicyclic polyisocyanate, aliphatic polyisocyanate, aromatic polyisocyanate, etc. can be used, and aliphatic polyisocyanate is preferably used. Cyclic polyisocyanate.

As the aforementioned alicyclic polyisocyanate, for example, isophorone diisocyanate, 1,3-bis(isocyanoxymethyl)cyclohexane, 4,4'-dicyclohexylmethane diisocyanate can be used alone , 2,4- and/or 2,6-methylcyclohexane diisocyanate, cyclohexylene diisocyanate, methyl cyclohexylene diisocyanate, bis(2-isocyanoxyethyl)-4-cyclohexane Hexyl-1,2-dicarboxylate, 2,5- and/or 2,6-norbornane diisocyanate, dimer acid diisocyanate, biscycloheptane triisocyanate, etc., or a combination of two or more thereof are used.

Of the aforementioned alicyclic polyisocyanates, among the aforementioned, it is preferable to use 4,4'-dicyclohexylmethane diisocyanate (HMDI), isophorone diisocyanate (IPDI), 1,3-bis(isocyanoxymethyl)cyclohexane (BICH).

As the method of making the aforementioned polyol (b'1) react with the aforementioned polyisocyanate (b'2) to produce the urethane resin (B') having an isocyanate group, for example, by making A method in which the aforementioned polyol (b'1) fed into the reaction vessel is heated under normal pressure or reduced pressure to remove moisture, and then the aforementioned polyisocyanate (b'2) is supplied in one batch or in batches and allowed to react .

The reaction between the polyol (b'1) and the polyisocyanate (b'2) is preferably at an equivalent ratio of the isocyanate group contained in the polyisocyanate (b'2) to the hydroxyl group contained in the polyol (b'1). (hereinafter referred to as [NCO/OH equivalent ratio]) is implemented within the range of 1.1~20.0, better within the range of 1.1~13.0, even better within the range of 1.1~5.0, and within the range of 1.5~3.0 Excellent implementation.

The reaction conditions (temperature, time, etc.) of the aforementioned polyol (b'1) and the aforementioned polyisocyanate (b'2) are not particularly limited as long as they are appropriately set in consideration of various conditions such as safety, quality, and cost. The temperature should fall within the range of 70~120°C, and the reaction time should fall within the range of 30 minutes~5 hours.

When the aforementioned polyol (b'1) is reacted with the aforementioned polyisocyanate (b'2), for example, a tertiary amine catalyst, an organometallic catalyst, or the like can be used as a catalyst if necessary. In addition, the aforementioned reaction may be carried out in a solvent-free environment, or may be carried out in the presence of an organic solvent.

For the aforementioned organic solvents, for example, ester solvents such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate can be used alone; ketone solvents such as acetone, methyl ethyl ketone, methyl butyl ketone, and cyclohexanone; Ether ester solvents such as methyl celluloid acetate and butyl celluloid acetate; aromatic hydrocarbon solvents such as toluene and xylene; amides such as dimethylformamide and dimethylacetamide A solvent or the like may be used in combination of two or more. The organic solvent may be removed by an appropriate method such as heating under reduced pressure or normal pressure drying during or after the production of the urethane resin (B').

The curable adhesive composition of the present invention contains a photopolymerization initiator in order to promote reactivity to external stimuli and obtain high adhesiveness after curing. In addition, the aforementioned polymerization initiators include, for example, photopolymerization initiators and thermal polymerization initiators, but by using a photopolymerization initiator whose reaction is carried out by light, it is possible to obtain a low-temperature reaction and good hardening reaction. Thereby, high bondability can be obtained without causing damage to the laminated members, deformation of the members due to strain generated between the members, or generation of cracks between the bonding material and the members. Appropriate light such as ultraviolet light or visible light can be used for the aforementioned light, and light having a wavelength of 300 nm to 420 nm is preferably used.

As far as the photopolymerization initiator is concerned, it is sufficient if it is activated by light, for example: photoradical polymerization initiator, photocation polymerization initiator, photoanion polymerization initiator, preferably using photocation As a polymerization initiator and a photoanionic polymerization initiator, it is preferable to use a photocationic polymerization initiator because the polymerization by dark reaction can be properly adjusted.

As far as the above-mentioned photocationic polymerization initiator is concerned, as long as the ring-opening reaction of the cationic polymerizable functional group is induced by the light energy of the wavelength used, it is not particularly limited, but it is preferable to use the light of the wavelength of 300~370nm to induce The ring-opening reaction of the cationic polymerizable functional group, and the compound is inactive in the wavelength region exceeding 370nm. Examples of such compounds include: onium salts such as aromatic diazonium salts, aromatic iodonium salts, and aromatic permeate salts. salt.

Specific examples of such onium salts include, for example: OPTOMA SP-150, OPTOMA SP-170, OPTOMA SP-171 (all manufactured by ADEKA); UVE-1014 (manufactured by General Electronics); OMNICAT250, OMNICAT270 (all made by IGM Resin); IRGACURE290 (made by BASF); SAN-AID SI-60L, SAN-AID SI-80L, SAN-AID SI-100L (all made by Sanshin Chemical Industry); CPI- 100P, CPI-101A, CPI-200K (all manufactured by San-Apro), etc.

系等增感劑。Moreover, the said photocationic polymerization initiator may be used individually, and may use it in combination of 2 or more types. Moreover, it is also possible to perform two-stage hardening using several photocationic polymerization initiators which differ in effective active wavelength. The aforementioned photocationic polymerization initiators can also be used in combination with anthracene series, 9-oxothio

Department of sensitizers.

In terms of the blending ratio of the aforementioned photocationic polymerization initiator, relative to 100 parts by mass of the adhesive composition, it is preferable to use it in the range of 0.001 to 30 parts by mass, and to use it in the range of 0.01 to 20 parts by mass. More preferably, it is even better to use within the range of 0.1 parts by mass to 10 parts by mass. If the blending ratio of the above-mentioned photocationic polymerization initiator is too small, the hardening required to exhibit high bonding properties will become insufficient, and if too large, the hardening properties will be improved, but the hardening after irradiation with light proceeds quickly, and the member that cannot transmit light Engaging with each other can become difficult.

The curable adhesive composition of the present invention may contain other components as needed in addition to the aforementioned photocurable resin (A), aforementioned thermoplastic resin (B), and aforementioned photopolymerization initiator. .

For the curable adhesive composition of the present invention, for example, in order to obtain the following adhesive sheet, an adhesive resin having a weight average molecular weight of 2,000 to 2,000,000 can be used: even if a curable adhesive composition is used When the adhesive sheet of the formed adhesive layer is wound up on a roll and stored, the adhesive layer can be further prevented from being extruded from the end of the roll, and it can be pasted at room temperature. Excellent adhesion. The ideal weight average molecular weight is in the range of 5,000 to 1,000,000, and the more ideal weight average molecular weight is in the range of 5,000 to 800,000.

Examples of the aforementioned adhesive resin include polyester, polyurethane, poly(meth)acrylate, polyvinyl acetal, and the like. These adhesive resins may be homopolymers or copolymers. In addition, these adhesive resins may be used alone or in combination of two or more.

If the above-mentioned adhesive resin has adhesiveness at normal temperature, the adhesiveness when laminating an adhesive sheet having an adhesive layer formed using the above-mentioned curable adhesive composition on an adherend will decrease. To be improved, it is more ideal. In order to impart adhesiveness to the aforementioned adhesive resin, the glass transition temperature of the aforementioned adhesive resin should preferably fall within the range of -30~20°C, more preferably within the range of -25~10°C. With the glass transition temperature within the above range, it is possible to impart adhesiveness and high modulus of elasticity to the aforementioned curable joining material composition, and to improve the joint strength of the aforementioned joining material.

In addition, the glass transition temperature of the aforementioned adhesive resin can be obtained, for example, by using a dynamic viscoelasticity tester (manufactured by Rheometrics Co., Ltd., trade name: ARES 2KSTD). Measure the storage elastic modulus (G') and loss elastic modulus (G") at a frequency of 1.0Hz, and calculate the temperature at which the loss tangent (tanδ) becomes the maximum value. The amount (G") was calculated by dividing the value (G"/G') obtained by the said storage elastic modulus (G').

The aforementioned adhesive resin may also be cross-linked, so functional groups capable of reacting with the functional groups contained in the cross-linking agent and the aforementioned curable adhesive composition may also be introduced. Examples of the above-mentioned functional groups include hydroxyl groups, carboxyl groups, epoxy groups, amino groups, etc., and should be appropriately selected within the range that does not interfere with the polymerization of the aforementioned curable adhesive composition.

The above-mentioned adhesive resin is preferably used in the range of 0.1 to 100 parts by mass, more preferably in the range of 1 to 50 parts by mass, and in the range of 5 to 5 parts by mass relative to 100 parts by mass of the aforementioned hardening adhesive composition. It is even better to use within the range of 30 parts by mass. By setting the blending ratio of the above-mentioned adhesive resin within the above-mentioned range, an adhesive sheet can be obtained that does not decrease in adhesiveness after hardening, and even when the adhesive sheet is wound up on a roll or the like and stored , can still further prevent the adhesive layer from being extruded from the end of the roller, and has excellent adhesion at room temperature.

The aforementioned curable adhesive composition may contain other additives as needed. As for the aforementioned additives, fillers such as aluminum hydroxide, aluminum oxide, aluminum nitride, magnesium hydroxide, magnesium oxide, mica, talc, boron nitride, and glass flakes can be used; silane coupling agents, phosphoric acid additives, acrylic acid Ester additives, tackifiers, etc. In particular, if a silane coupling agent with high reactivity with glass is used, an adhesive sheet with excellent adhesion to members composed of glass and the like can be obtained, so it is ideal to use a composition that can be combined with the above-mentioned hardening adhesive Reaction light hardening silane coupling agent is better.

Also, in terms of additives, in addition to the aforementioned ones, within the scope of not impairing the effects of the present invention, those containing the following additives can also be used, for example: softeners, stabilizers, adhesion promoters, leveling agents , defoaming agent, plasticizer, tackifying resin, fiber, antioxidant, antihydrolysis agent, tackifier, pigment and other colorants, fillers, etc.

As for the aforementioned curable adhesive composition, it is suitable to be used as an adhesive sheet by forming it into an arbitrary shape such as a sheet in advance, as mentioned above, and it may have the aforementioned adhesive on both sides of the sheet-like substrate. Layers may also be formed without the above-mentioned sheet-shaped substrate, but by using the above-mentioned adhesive layer, that is, the so-called substrate-free adhesive sheet. The above-mentioned adhesive sheet may be formed using a single adhesive layer, or may be formed by laminating two or more types of the same or different adhesive layers.

As for the manufacturing method of the above-mentioned adhesive sheet, for example, it can be manufactured by coating the above-mentioned adhesive composition on both sides of the base material, and drying as necessary to form an adhesive layer. When producing a laminate of two or more adhesive layers of the same or different composition as the aforementioned adhesive sheet, for example, by applying the adhesive composition 1 to both sides of a sheet-like substrate, The adhesive layer 1 is formed by drying as needed, and then another adhesive composition 2 is applied on the surface of the adhesive layer 1 and dried as needed to form the adhesive layer 2 .

For the aforementioned adhesive sheet, for example, the adhesive layer 1 can be formed by applying the aforementioned adhesive composition 1 on the surface of the release sheet and drying as needed, and then another adhesive composition The object 2 is coated on the surface of the aforementioned adhesive layer 1 and dried as needed to form the adhesive layer 2 . As for the adhesive sheet, it is preferable to use a composition containing a solvent in addition to a polymerizable compound and a polymerization initiator in order to improve work efficiency when forming into the sheet shape. For the aforementioned solvents, for example, ester-based solvents such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate; acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, and cyclohexanone can be used. Ketone solvents such as ketones; aromatic hydrocarbon solvents such as toluene and xylene, etc.

The adhesive sheet of the present invention can be produced by mixing the aforementioned polymerizable compound with optional components such as the aforementioned polymerization initiator and solvent. When mixing the above-mentioned components to produce the joint material (X), you can use a dissolver (dissolver), a butterfly knife mixer, a BDM double-shaft mixer, a planetary mixer, etc. according to the need. For the mixer, when using the aforementioned conductive fillers, it is better to use a planetary mixer in order to improve their dispersibility.

In addition, the above-mentioned polymerization initiator is preferably used before curing the above-mentioned adhesive sheet or before forming the above-mentioned adhesive sheet into a sheet shape or the like. Also, the adhesive sheet can be produced, for example, by making a composition containing the polymerizable compound and optional components such as the polymerization initiator and solvent, and then coating the surface of, for example, a release liner and drying it. The aforementioned drying is preferably carried out at a temperature of 40°C to 120°C, and it is more desirable to carry out at a temperature of about 50°C to 90°C in order to suppress the progress of the hardening reaction of the sheet-like bonding material. In addition, it is preferable because it can suppress blistering on the surface of the sheet due to rapid volatilization of solvents and the like.

The above-mentioned adhesive sheet can also be pinched by the above-mentioned release liner until it is used. For the aforementioned release liner, for example, paper such as kraft paper, cellophane, and high-quality paper; resin films such as polyethylene, polypropylene (OPP, CPP), and polyethylene terephthalate; Laminated paper made of layers, one or both sides of the above-mentioned paper that is filled with clay, polyvinyl alcohol, etc., and released with silicone-based resin, etc., etc.

The temperature when storing the aforementioned adhesive sheet is preferably -10°C or higher, more preferably 5°C or higher, and if it is higher than 23°C, it can reduce the water absorption of the aforementioned adhesive sheet caused by condensation and inhibit the hardening of the aforementioned adhesive sheet Sexual reduction, so more ideal.

Ultraviolet light is preferably used as the light used for curing the adhesive sheet and bonding the members and the like. The aforementioned ultraviolet rays may be irradiated under an inert gas environment such as nitrogen gas or may be irradiated under an air environment in order to efficiently carry out the hardening reaction by ultraviolet rays. Also, if necessary, heat may be used in combination as an energy source, and heating may be performed after irradiation with light.

When ultraviolet rays are used as light, examples include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, electrodeless lamps (FUSION LAMPs), chemical lamps, black light lamps, mercury-xenon lamps, short-arc lamps, and helium-cadmium lamps. Laser, argon laser, sunlight, LED, etc. Also, a xenon flash lamp capable of flashing light is preferable because it can minimize the influence of heat on the substrate.

As the above-mentioned light irradiation device, in addition to the above-mentioned ones, germicidal lamps, carbon arcs, xenon lamps, metal halide lamps, scanning type, curtain type electron beam accelerators, etc. can also be used.

The said adhesive sheet can be made into a laminated body by sticking to a to-be-adhered body. The method for producing a laminate using the adhesive sheet of the present invention is the manufacture of a laminate in which two or more adherends having surfaces that do not transmit active energy rays are laminated via an adhesive sheet The method, which includes in order: the step [1] of bonding the adhesive layer of the adhesive sheet to the first adherend by using pressure-sensitive bonding; applying the aforementioned adhesive sheet before or after step [1] The step of irradiating the surface of the other side of the adhesive layer with active energy rays to increase the hardening rate of the adhesive layer by 0.01~30% [2]; the step of crushing the aforementioned adhesive sheet [3]; and Step [4] of further hardening the hardening rate of the aforementioned adhesive layer by 20% or more from the hardening rate of the aforementioned step [2] in the state where the aforementioned adhesive sheet is crushed.

The above-mentioned adhered system having a surface that does not transmit active energy rays refers to an adhered body whose transmittance of light with a wavelength of 200nm to 780nm is less than 30%. Examples include: aluminum, stainless steel, copper and other metals; glass epoxy Resin substrate or colored film substrate, etc.

In the aforementioned step [1], the adhesive layer of the adhesive sheet and the first adherend are not heated, but bonded by pressure-sensitive bonding. This step [1] does not require heating and other operations, and can be carried out appropriately at the temperature of the working environment, so it is easy to temporarily fix the adhesive sheet to the first adherend, and it is also easy to carry out re-bonding .

The pressure used in the pressure-sensitive bonding in the aforementioned step [1] should be 0.1~3000KPa, more preferably 0.5~1000KPa, and if it is 1.0~500KPa, it will not damage the first adherend and obtain high bonding strength. The adhesiveness necessary for strength is more ideal.

In the aforementioned step [2], the surface of the other side of the adhesive layer of the aforementioned adhesive sheet is irradiated with active energy rays before or after step [1], so that the hardening rate of the adhesive layer is increased by 0.01~30 %. In this step [2], since the adhesiveness necessary for bonding is obtained even after the active energy ray irradiation, the adherends can be laminated even after the active energy ray irradiation.

The irradiation intensity of the aforementioned active energy rays is preferably 0.1-1000 mW/cm ² , more preferably 0.5-800 mW/cm ² , and even more preferably 0.1-400 mW/cm ² . By setting to the above-mentioned predetermined intensity, the heat generated at the time of irradiating active energy rays can be reduced, so the curing rate after irradiating active energy rays can be appropriately adjusted.

As for the irradiation time of the aforementioned active energy rays, it is preferably 1 to 60 seconds, more preferably 5 to 50 seconds, and even more preferably 10 to 40 seconds. By setting to the aforementioned predetermined time, the heat generated when irradiating active energy rays can be reduced, so that the curing rate after irradiating active energy rays can be appropriately adjusted.

Regarding the irradiation time of the aforementioned active energy rays, irradiation may be performed at one time or may be performed in divided steps. When the irradiation is performed in divided steps, for example, one minute of irradiation may be divided into two times, and the irradiation may be performed twice in 30 seconds. By grading, the heat generated when irradiating active energy rays can be reduced, so the curing rate after irradiating active energy rays can be appropriately adjusted.

In the aforementioned step [2], the hardening rate of the aforementioned adhesive sheet after irradiating the aforementioned active energy rays is increased by 0.01-30%. In addition, increasing the hardening rate by 1% means that when the hardening rate in the step [1] is 1%, the increase is 2% (the same applies hereinafter). By setting the above-mentioned curing rate, the adhesive sheet has the adhesiveness necessary for bonding even after the active energy ray irradiation, so even after the active energy ray irradiation, the adherends can be laminated. In addition, by setting the aforementioned curing rate, the adhesive sheet still has the flexibility required to cope with the difference in height even after the active energy ray is irradiated, so that at least one of the adherends has a deflection In the step of laminating adherends such as unevenness and/or unevenness, the adhesive sheet can still be attached to the aforementioned flexure and/or unevenness. In the aforementioned step [2], it is preferable to increase the hardening rate by 0.1-20%, and it is more preferable to increase the hardening rate by 0.2-10%.

In addition, the above-mentioned hardening rate is expressed by gel fraction, and the gel fraction refers to the adhesive layer of the adhesive sheet of the present invention immersed in toluene adjusted to 23°C for 24 hours, and according to the undissolved in the above-mentioned The mass of the adhesive layer of the adhesive sheet remaining in the solvent after drying and the value calculated by the following formula.

Gel fraction (mass %)=[(mass of adhesive layer of adhesive sheet not dissolved in toluene)/(mass of adhesive layer of adhesive sheet before immersion in toluene)]×100

In the aforementioned step [2], the hardening reaction of the aforementioned adhesive sheet is started by irradiating active energy rays. Other methods for initiating the hardening reaction include heating, moisture absorption (water absorption), etc., but by using active energy rays, it can be applied even to components that may deteriorate due to heating, and it is not necessary to Manage moisture absorption of the adhesive sheet in the lamination step.

As the aforementioned active energy rays, ultraviolet rays are preferably used. The aforementioned ultraviolet rays may be irradiated under an inert gas environment such as nitrogen gas or may be irradiated under an air environment in order to efficiently carry out the hardening reaction by ultraviolet rays. Also, if necessary, heat may be used in combination as an energy source, and heating may be performed after irradiating active energy rays.

When ultraviolet rays are used as active energy rays, examples include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, electrodeless lamps (FUSION LAMP), chemical lamps, black light lamps, mercury-xenon lamps, short-arc lamps, helium - Cadmium laser, argon laser, sunlight, LED, etc. Also, a xenon flash lamp capable of flashing irradiating active energy rays is preferable because it can minimize the influence of heat on the substrate.

As the irradiation device of the above-mentioned active energy rays, in addition to the above-mentioned ones, germicidal lamps, carbon arcs, xenon lamps, metal halide lamps, scanning type, curtain type electron beam accelerators, etc. can also be used.

As the method of irradiating the aforementioned active energy rays, a method of directly irradiating the aforementioned adhesive sheet, or a method of irradiating active energy rays through a substrate laminated on the aforementioned adhesive sheet in advance can be mentioned. In this case, the aforementioned base material and the like must be transparent, and examples of the aforementioned base material include release liners described later.

In the aforementioned step [3], the adhesion to the adherend can be improved by crushing the aforementioned adhesive sheet. The tabs accompany this flex, bump, and allow it to bond properly.

The second adherend is bonded to the surface of the adhesive layer of the laminate consisting of the adhesive layer and the first adherend, and the bonding is at a temperature of 30 to 100°C for 10 seconds to 10 seconds. Apply a pressure of 1~500KPa every minute, so that the thickness of the aforementioned adhesive sheet is more than 10% thinner than the original thickness.

Also, in the aforementioned step [3], by properly adjusting the temperature, pressure, and time described later, for example, the thickness of the adhesive sheet can be made thinner by more than 10% than the original thickness, whereby, for example, at least one of the adherends In the step of laminating an adherend having warpage and/or unevenness, the adhesive sheet can be sufficiently attached to the warp and/or unevenness. In addition, in order to bond the adhesive sheet to the adherend with the thickness of the adhesive sheet being 10% or more thinner than the original thickness, it is necessary to set the curing rate after the active energy ray irradiation in the aforementioned step [2] to within the aforementioned predetermined range.

In the aforementioned step [3], the temperature for crushing the aforementioned adhesive sheet is necessary to make the aforementioned adhesive sheet adhere to the adherend and change the thickness. In terms of bonding, the temperature can be adjusted appropriately, but it is preferably 30 ~100°C, more preferably 40°C~90°C, more preferably 50~80°C. By setting within the aforementioned predetermined range, the shape of the sheet can be maintained in the aforementioned steps [1], [2], and it is not necessary to suppress damage to members of the liquid crystal display device due to heating, the thickness can be appropriately changed, and the use can be obtained. In order to obtain the adhesiveness necessary for high joint strength, it is more ideal.

In the aforementioned step [3], the pressure of crushing the aforementioned adhesive sheet is necessary to make the aforementioned adhesive sheet adhere to the adherend and change the thickness. In terms of bonding, the pressure can be adjusted appropriately, but it is preferably 0.1 The pressure of ~3000KPa is more preferably 0.5~1000KPa. If it is 1.0~500KPa, the components of the liquid crystal display device will not be damaged due to the pressure, and the thickness can be changed appropriately, and the necessary strength for obtaining high joint strength can be obtained. Adhesive, so more ideal.

In the aforementioned step [3], the time for crushing the aforementioned adhesive sheet is necessary to make the aforementioned adhesive sheet adhere to the adherend and change the thickness. In terms of bonding, the time can be adjusted appropriately, but it is preferably 10 Seconds to 20 minutes, preferably 30 seconds to 15 minutes, 1 to 10 minutes, the adherend will not be damaged, and the thickness can be changed appropriately, and the necessary adhesion for obtaining high joint strength can be obtained Sex, so it is more ideal.

The aforementioned step [3] should be implemented within 60 minutes after the aforementioned step [2]. It is better within 5 to 45 minutes, and it is even better to implement within 10 to 30 minutes. By setting within the aforementioned predetermined range, the preparation time for moving from the aforementioned step [2] to the aforementioned step [3] can be ensured, and the flexibility necessary for crushing the aforementioned adhesive sheet can be imparted in the aforementioned step [3].

In the aforementioned step [4], by aging at a temperature of 20-100° C. for 30 minutes to 7 days, the hardening rate of the aforementioned adhesive layer is further increased by more than 20% from the hardening rate of the aforementioned step [2]. In the production method of the present invention, the hardening reaction of the adhesive sheet will start by irradiating active energy rays, so hardening will still proceed even at normal temperature, but the hardening time can be shortened by heating as needed.

For the hardened product formed by hardening the adhesive sheet in the aforementioned step [4], it is preferable to increase the hardening rate by more than 30%. By setting to the said hardening rate, the adhesive bond layer which can join members firmly can be obtained. As far as the hardening rate of the above-mentioned adhesive sheet is concerned, it is better to set it at 40% or more, and it is even better to increase it to 50% or more, and it is best to increase it to 60% or more.

In addition, the above-mentioned hardening rate is expressed by gel fraction, and the gel fraction refers to the adhesive layer of the adhesive sheet of the present invention immersed in toluene adjusted to 23°C for 24 hours, and according to the undissolved in the above-mentioned The mass of the adhesive layer of the adhesive sheet remaining in the solvent after drying and the value calculated by the following formula.

Gel fraction (mass %)=[(mass of adhesive layer of adhesive sheet not dissolved in toluene)/(mass of adhesive layer of adhesive sheet before immersion in toluene)]×100

As for the curing temperature in the aforementioned step [4], it is preferably 30-100°C, more preferably 40-90°C, and even more preferably 50-80°C. By setting it within the aforementioned predetermined range, it is more desirable that the thickness can be appropriately changed without suppressing damage to members of the liquid crystal display device due to heating, and that the adhesiveness necessary for obtaining high bonding strength can be obtained.

As far as the hardening time of the aforementioned step [4] is concerned, it should be matured for 10 minutes to 7 days, more preferably for 15 minutes to 1 day, and even more preferably for 20 minutes to 3 hours. If matured for 1 to 2 hours, it can be restrained at high temperature The damage of the components of the liquid crystal display device caused by the heating, and the deformation of the adherend caused by the strain between the components generated during cooling due to the thermal expansion difference of each component can be suppressed, and the bonding between the adhesive sheet and the Peeling caused by cracks between bonded bodies.

The aforementioned step [4] should be implemented within 60 minutes after the aforementioned step [2]. It is better within 5 to 45 minutes, and it is even better to implement within 10 to 30 minutes. By setting within the aforementioned predetermined range, the preparation time for moving from the aforementioned step [2] to the aforementioned step [4] can be ensured, and the necessary time for bonding the aforementioned adhesive sheet to the adherend can be given in the aforementioned step [4]. Adhesiveness and softness required.

Regarding the adhesive layer of the adhesive sheet used in the aforementioned manufacturing method, the loss tangent (tanδ ₂₃ ) of the adhesive layer before hardening at 23°C is preferably less than 1.5.

In addition, the aforementioned loss tangent (tanδ ₂₃ ) at 23°C was obtained using a dynamic viscoelasticity testing machine (manufactured by Rheometrics, trade name: ARES 2KSTD), and the test piece was sandwiched between parallel discs in the measuring section of the testing machine. , Measure the storage elastic modulus (G') and loss elastic modulus (G") at a temperature of 0~150°C and a frequency of 1 Hz, and the loss tangent (tanδ) is divided by the aforementioned loss elastic modulus (G") The value (G"/G') obtained by storing the elastic modulus (G'). In addition, for the test piece used in the above measurement, the above-mentioned adhesive layer was cut into a piece with a thickness of 1 mm and a diameter of 8 mm. The size of the circular shape.

For the adhesive layer of the above-mentioned adhesive sheet, when measuring the loss tangent (tanδ ₂₃ ) of the adhesive layer before hardening at 23°C at a frequency of 1 Hz, it should be set to less than 1.5, and set to 0.01 or more to 1.0 The following range is more preferable, and if it is set in the range of 0.1 to 0.8, it is more ideal to obtain the following manufacturing method: in the aforementioned step [1] and step [2], the thickness of the adhesive sheet is maintained constant, and Improved operability when attaching adhesive sheets.

In addition, the loss tangent (tanδ ₂₃ ) of the adhesive layer at 23°C before hardening of the above-mentioned adhesive sheet can be used in addition to the above-mentioned conditions at the time of production, and can also be used by appropriately selecting the above-mentioned photocurable resin described later. (A), the above-mentioned thermoplastic resin (B), the composition or the number average molecular weight of other components according to need, etc., are set within the above-mentioned predetermined range.

As for the adhesive layer of the aforementioned adhesive sheet, it is preferable to use one having a melting point below the implementation temperature of step [3]. Those having a melting point within the aforementioned range can appropriately reduce the thickness of the aforementioned adhesive sheet, and can obtain a manufacturing method in which compliance with deflection of the member and the compliance of the surface level difference is improved.

In addition, the above-mentioned melting point refers to the use of differential scanning calorimetry (DSC method), the temperature is raised from 20°C to 150°C at a heating rate of 10°C/min, and after holding for 1 minute, it is temporarily heated at a temperature of 10°C/min. After cooling to -10°C and keeping it for 10 minutes, the temperature of the maximum exothermic peak (exothermic peak top) observed when the temperature is raised again at 10°C/min is measured.

As for the adhesive layer of the aforementioned adhesive sheet, the storage elastic modulus (E'40) of the cured adhesive layer at 40°C is preferably 1.0×10 ⁴ Pa or more when measured at a frequency of 1.0 Hz, and The storage elastic modulus (E'60) at 60°C is preferably 1.0×10 ⁴ Pa or more when measured at a frequency of 1.0 Hz. By setting the storage elastic modulus as described above, an adhesive layer capable of firmly joining members can be obtained.

In addition, the dynamic viscoelasticity of the cured product formed by hardening the adhesive sheet (cured adhesive layer) is a value measured using a dynamic viscoelasticity measuring device (manufactured by Rheometrics, trade name: RSA-II). In addition, the above-mentioned measurement uses the following: prepare the hardened product (adhesive layer after hardening) with a thickness of 100 μm formed by hardening the above-mentioned adhesive sheet, and punch it into a test piece according to JIS K 7127 using a dumbbell-shaped cutting machine. The shape of model 5.

As for the adhesive layer of the adhesive sheet used in the aforementioned manufacturing method, it is preferable to use a thickness in the range of 50-2000 μm, more preferably 100-1500 μm, and 200-1000 μm. After obtaining the following manufacturing method The aspect is more ideal: in the aforementioned step [1] and step [2], the thickness of the adhesive sheet can be maintained at a certain level, and the operability when pasting the adhesive sheet can be improved, and in the aforementioned step [3], it can be properly implemented The thickness of the aforementioned adhesive sheet is thinned, and the compliance with the deflection of the member and the unevenness of the surface is improved.

Utilizing the above-mentioned manufacturing method of laminates, construction and bonding can be completed even in a short time and at low temperature, and even if two or more active energy rays are not transmitted, the adherend has bending and unevenness on the surface of the member It can still be joined ideally.

The laminated body of the present invention is soft before hardening, so it is excellent in adhering to members with deflection and unevenness, and can fully bond the members after hardening, so it can be used exclusively for image display devices. The joint material used for various components.

Examples of the aforementioned image display device include mobile terminals (PDA) such as personal computers, mobile phones, smart phones, and tablet computers, game consoles, televisions (TV), car navigation, touch panels, tablet computers, etc. A component of a flat-panel image display device using an image display panel equipped with LCD, PDP, EL, organic EL, micro LED, quantum dot (QD), etc. The constituent members include, for example, an image display panel, a circuit board, a back cover, a bezel, a frame, and a chassis. The adhesive sheet of the present invention can firmly join members after hardening, so it can also be used for joining members constituting large-scale image display devices used in industrial applications and advertising applications. [Example]

Hereinafter, the present invention will be more specifically described using examples and comparative examples. ＜Preparation of urethane resin (B'-1)＞ 50 parts by mass of aliphatic polycarbonate polyol with a number average molecular weight of 2000 obtained by reacting 1,5-pentanediol, 1,6-hexanediol and dialkyl carbonate in a reaction vessel , mixed with 30 parts by mass of polyester polyol with a number average molecular weight of 4500 obtained by reacting 1,6-hexanediol and adipic acid, and heated to 100°C under reduced pressure for dehydration, so that The water content was 0.05% by mass.

Then, after cooling the mixture of the above-mentioned aliphatic polycarbonate polyol and the above-mentioned polyester polyol to 70°C, and mixing it with 14.5 parts by mass of dicyclohexylmethane-4,4'-diisocyanate, the temperature was raised to 100 °C and reacted for 3 hours to obtain a urethane-based resin (B'-1). In addition, the aforementioned urethane resin (B'-1) has an isocyanate group as a polymerizable functional group.

＜Preparation of urethane resin (B'-2)＞ 40 parts by mass of aliphatic polycarbonate polyol with a number average molecular weight of 2000 obtained by reacting 1,5-pentanediol, 1,6-hexanediol and dialkyl carbonate in a reaction vessel , mixed with 40 parts by mass of polyester polyol with a number average molecular weight of 4500 obtained by reacting 1,6-hexanediol and adipic acid, and heated to 100°C under reduced pressure for dehydration, so that The water content was 0.05% by mass.

Then, after cooling the mixture of the above-mentioned aliphatic polycarbonate polyol and the above-mentioned polyester polyol to 70°C, and mixing it with 13.7 parts by mass of dicyclohexylmethane-4,4'-diisocyanate, the temperature was raised to 100 °C and reacted for 3 hours to obtain a urethane-based resin (B'-2). In addition, the aforementioned urethane resin (B'-2) has an isocyanate group as a polymerizable functional group.

＜Preparation of urethane resin (B'-3)＞ 60 parts by mass of aliphatic polycarbonate polyol with a number average molecular weight of 2000 obtained by reacting 1,5-pentanediol, 1,6-hexanediol and dialkyl carbonate in a reaction vessel , mixed with 20 parts by mass of polyester polyol with a number average molecular weight of 4500 obtained by reacting 1,6-hexanediol and adipic acid, and heated to 100°C under reduced pressure for dehydration, so that The water content was 0.05% by mass.

Then, after cooling the mixture of the above-mentioned aliphatic polycarbonate polyol and the above-mentioned polyester polyol to 70°C, and mixing it with 16.3 parts by mass of dicyclohexylmethane-4,4'-diisocyanate, the temperature was raised to 100 °C and reacted for 3 hours to obtain a urethane-based resin (B'-3). In addition, the aforementioned urethane resin (B'-3) has an isocyanate group as a polymerizable functional group.

＜Preparation of urethane resin (B'-4)＞ 60 parts by mass of aliphatic polycarbonate polyol with a number average molecular weight of 2000 obtained by reacting 1,5-pentanediol, 1,6-hexanediol and dialkyl carbonate in a reaction vessel , mixed with 20 parts by mass of polyester polyol with a number average molecular weight of 4500 obtained by reacting 1,6-hexanediol and adipic acid, and heated to 100°C under reduced pressure for dehydration, so that The water content was 0.05% by mass.

Then, after cooling the mixture of the above-mentioned aliphatic polycarbonate polyol and the above-mentioned polyester polyol to 70°C, and mixing it with 15.3 parts by mass of dicyclohexylmethane-4,4'-diisocyanate, the temperature was raised to 100 °C and reacted for 3 hours to obtain a urethane-based resin (B'-4). In addition, the aforementioned urethane resin (B'-4) has an isocyanate group as a polymerizable functional group.

＜Preparation of urethane resin (B'-5)＞ 60 parts by mass of aliphatic polycarbonate polyol with a number average molecular weight of 2000 obtained by reacting 1,5-pentanediol, 1,6-hexanediol and dialkyl carbonate in a reaction vessel , mixed with 20 parts by mass of polyester polyol with a number average molecular weight of 4500 obtained by reacting 1,6-hexanediol and adipic acid, and heated to 100°C under reduced pressure for dehydration, so that The water content was 0.05% by mass.

Then, after cooling the mixture of the above-mentioned aliphatic polycarbonate polyol and the above-mentioned polyester polyol to 70°C, and mixing it with 4.5 parts by mass of dicyclohexylmethane-4,4'-diisocyanate, the temperature was raised to 100 °C and allowed to react for 3 hours until the hydroxyl content became a constant value to obtain a urethane resin (B'-5). In addition, the aforementioned urethane resin (B'-5) has a hydroxyl group as a polymerizable functional group.

＜Preparation of urethane resin (C'-1)＞ 60 parts by mass of aliphatic polycarbonate polyol with a number average molecular weight of 2000 obtained by reacting 1,5-pentanediol, 1,6-hexanediol and dialkyl carbonate in a reaction vessel , mixed with 20 parts by mass of polyester polyol with a number average molecular weight of 1000 obtained by reacting 1,4-butanediol and adipic acid, and heated to 100°C under reduced pressure for dehydration, so that The water content was 0.05% by mass.

Then, after cooling the mixture of the aforementioned aliphatic polycarbonate polyol and the aforementioned polyester polyol to 70° C., mixing it with 20 parts by mass of dicyclohexylmethane-4,4′-diisocyanate, the temperature was raised to 100 °C and allowed to react for 3 hours to obtain a urethane-based prepolymer having an isocyanate group.

100 parts by mass of the aforementioned urethane-based prepolymer was heated and melted at 100° C., 11.4 parts by mass of 2-hydroxyethyl acrylate and 0.01 part by mass of tin (II) octoate were mixed, and the It was made to react at 100 degreeC until NCO% became a constant value, and the urethane resin (C'-1) was obtained. In addition, the urethane resin (C'-1) has a polymerizable unsaturated double bond as a polymerizable functional group.

The isocyanate group content (NCO%) of the urethane resin (C'-1) having a polymerizable unsaturated double bond obtained by the aforementioned method was 0% by mass.

＜Preparation of urethane resin (C'-2)＞ 40 parts by mass of aliphatic polycarbonate polyol with a number average molecular weight of 2000 obtained by reacting 1,5-pentanediol, 1,6-hexanediol and dialkyl carbonate in a reaction vessel , mixed with 40 parts by mass of polyester polyol with a number average molecular weight of 4500 obtained by reacting 1,6-hexanediol and adipic acid, and heated to 100°C under reduced pressure for dehydration, so that The water content was 0.05% by mass.

Then, after cooling the mixture of the above-mentioned aliphatic polycarbonate polyol and the above-mentioned polyester polyol to 70°C, and mixing it with 13.7 parts by mass of dicyclohexylmethane-4,4'-diisocyanate, the temperature was raised to 100 °C and allowed to react for 3 hours to obtain a urethane-based prepolymer having an isocyanate group.

100 parts by mass of the aforementioned urethane-based prepolymer was heated and melted at 100° C., 1.6 parts by mass of 2-hydroxyethyl acrylate and 0.01 part by mass of tin (II) octoate were mixed, and the It was made to react at 100 degreeC until NCO% became a constant value, and the urethane resin (C'-2) was obtained. In addition, the urethane resin (C'-2) has a polymerizable unsaturated double bond as a polymerizable functional group.

The isocyanate group content (NCO%) of the urethane resin (C'-2) having a polymerizable unsaturated double bond obtained by the aforementioned method was 0% by mass.

(Example 1) By adding 100 parts by mass of the aforementioned urethane resin (B'-1), 43 parts by mass of CEL-2021P (manufactured by DAICEL, cycloaliphatic epoxy resin), 43 parts by mass of CPI-100P (manufactured by San-Apro, Co. Salt system, solid content concentration 50%) 11.4 mass parts were mixed and stirred, and methyl ethyl ketone was added to adjust the non-volatile content to 75 mass % to obtain an adhesive composition (a-1). Then, the aforementioned adhesive composition (a-1) was coated on a release liner (one side of a polyethylene terephthalate film with a thickness of 50 μm was treated with a polysiloxane compound) using a rod-shaped metal utensil. ) surface so that the thickness after drying becomes 100 μm.

Then, put the aforementioned coating into a dryer at 85°C to dry for 5 minutes, and attach a release liner (one side of a polyethylene terephthalate film with a thickness of 38 μm) to one side of the dried coating. Silicone compound was subjected to peeling treatment), and an adhesive sheet (X-1) with a thickness of 100 μm was obtained.

(Example 2) Except that the aforementioned urethane resin (B'-2) was used instead of the aforementioned urethane resin (B'-1), an adhesive sheet with a thickness of 100 μm was obtained in the same manner as in Example 1 ( X-2).

(Example 3) In addition to using the aforementioned urethane resin (B'-3) instead of the aforementioned urethane resin (B'-1), an adhesive sheet with a thickness of 100 μm was obtained in the same manner as in Example 1 ( X-3).

(Example 4) Except that the aforementioned urethane resin (B'-4) was used instead of the aforementioned urethane resin (B'-1), an adhesive sheet with a thickness of 100 μm was obtained in the same manner as in Example 1 ( X-4).

(Example 5) In addition to using the aforementioned urethane resin (B'-5) instead of the aforementioned urethane resin (B'-1), and changing the amount of CPI-100P used from 11.4 parts by mass to 5.7 parts by mass In addition, an adhesive sheet (X-5) having a thickness of 100 μm was obtained in the same manner as in Example 1.

(comparative example 1) Except that the aforementioned urethane resin (C'-1) was used instead of the aforementioned urethane resin (B'-1), an adhesive sheet with a thickness of 100 μm was obtained in the same manner as in Example 1 ( X'-1).

(comparative example 2) Except that the aforementioned urethane resin (C'-2) was used instead of the aforementioned urethane resin (B'-1), an adhesive sheet with a thickness of 100 μm was obtained in the same manner as in Example 1 ( X'-2).

異三聚氰酸加成物)1.0質量份替換CPI-100P11.4質量份，除此之外，以和實施例1同樣的方法獲得厚度100μm之黏接片(X’-3)。 另外，前述黏接片(X’-3)具有熱聚合性起始劑，且能藉由加熱來進行硬化反應。(Comparative Example 3) 3 parts by mass of DICY-7 (manufactured by Mitsubishi Chemical Co., Ltd., dicyandiamide) and 2MAOK-PW (manufactured by Shikoku Chemical Industry Co., Ltd., 2,4-diamino-6- [2'-Methylimidazolyl-(1')]-ethyl-s-tri

An adhesive sheet (X'-3) with a thickness of 100 μm was obtained in the same manner as in Example 1 except that 1.0 parts by mass of isocyanuric acid adduct) was substituted for 11.4 parts by mass of CPI-100P. Moreover, the said adhesive sheet (X'-3) has a thermopolymerizable initiator, and can perform hardening reaction by heating.

[Measuring method of loss tangent (tanδ) of adhesive layer before irradiation with active energy rays] Peel off the release liner laminated on both sides of the adhesive sheet obtained in Examples and Comparative Examples, and laminate the adhesive layer to a thickness of 1 mm, then cut it into a circular shape with a diameter of 8 mm as a test piece. Using a dynamic viscoelasticity testing machine (manufactured by Rheometrics, trade name: ARES 2KSTD), the test piece is clamped between the parallel disks of the measuring part of the testing machine, and the storage at a temperature of 40 ° C and 60 ° C and a frequency of 1 Hz is measured. The elastic modulus (G') and the loss elastic modulus (G"), the loss tangent (tanδ) is the value obtained by dividing the aforementioned loss elastic modulus (G") by the aforementioned storage elastic modulus (G') (G "/G').

[Evaluation method of pressure resistance (method of evaluating whether the components contained in the adhesive layer are squeezed out when a force is applied to the adhesive sheet)] The adhesive sheets obtained in Examples and Comparative Examples were cut into 5 cm x 5 cm, and after peeling off the release liner laminated on both sides, the adhesive layer was laminated to a thickness of 0.5 mm. Afterwards, the laminated adhesive sheet with a thickness of 0.5mm was pressed and bonded to the central part 10 of the release liner cut into 7cm×7cm with a thickness of 50μm at a temperature of 23°C with a pressure of 0.05MPa. Seconds make it fit.

From the upper part of the above-mentioned pasted product, a pressure of 0.1 MPa per unit area is applied, and the temperature environment of -20°C, 5°C, and 40°C is left for 24 hours. Then, the ratio of the thickness of the adhesive sheet after placement to the thickness of the adhesive sheet before placement (0.5 mm) was evaluated using the following criteria (thickness of the adhesive sheet after placement/thickness of the adhesive sheet before placement ).

◎: The ratio of the thickness of the adhesive sheet after leaving to the thickness of the adhesive sheet before leaving was 100% or more and less than 101% (no change). ○: The ratio of the thickness of the adhesive sheet after leaving to the thickness of the adhesive sheet before leaving is 97% or more and less than 100%. △: The ratio of the thickness of the adhesive sheet after leaving to the thickness of the adhesive sheet before leaving is 93% or more and less than 97%. ×: The ratio of the thickness of the adhesive sheet after placement to the thickness of the adhesive sheet before placement is less than 93%.

[Evaluation method of softness after active energy ray irradiation (method for evaluating the flexibility of the adhesive sheet after irradiating active energy ray to the surface of the adherend, and the height difference when the force is applied to the surface of the adherend)] The adhesive sheets obtained in Examples and Comparative Examples were cut into 5 cm x 5 cm, and after peeling off the release liner laminated on both sides, the adhesive layer was laminated to a thickness of 0.5 mm. Afterwards, the laminated adhesive sheet with a thickness of 0.5mm was pressed and bonded to the central part 10 of the release liner cut into 7cm×7cm with a thickness of 50μm at a temperature of 23°C with a pressure of 0.05MPa. Seconds make it fit.

After placing the aforementioned stickers in a temperature environment of 23°C for 60 minutes, use an electrodeless lamp (FUSION LAMP H-BULB) to irradiate ultraviolet light with an intensity of 100mW/cm ² for 10 seconds.

After placing the above ultraviolet irradiated sticker in a temperature environment of 23° C. for 10 minutes, use a hot pressing device heated to 70° C., and press it at 0.5 MPa for 10 seconds. The ratio of the thickness of the adhesive sheet after hot pressing to the thickness of the adhesive sheet before hot pressing (0.5 mm) was evaluated using the following criteria (thickness of the adhesive sheet after hot pressing/adhesion before hot pressing slice thickness).

◎: The ratio of the thickness of the adhesive sheet after hot pressing to the thickness of the adhesive sheet before hot pressing is less than 50%. ○: The ratio of the thickness of the adhesive sheet after hot pressing to the thickness of the adhesive sheet before hot pressing is 50% or more and less than 80%. △: The ratio of the thickness of the adhesive sheet after hot pressing to the thickness of the adhesive sheet before hot pressing is 80% or more and less than 90%. ×: The ratio of the thickness of the adhesive sheet after hot pressing to the thickness of the adhesive sheet before hot pressing is 90% or more and less than 100% (no change).

[Evaluation method for adhesiveness of members that do not transmit light (evaluation method for shear adhesion)] What cut the adhesive sheet obtained in the Example and the comparative example into the size of 10 mm in width x 10 mm in length was used as a test sample. Remove one of the release liners of the aforementioned test samples, and press and bond it to an aluminum plate with a smooth surface of 15mm in width x 150mm in length x 0.05mm in thickness at a temperature of 23°C with a pressure of 0.05MPa for 10 seconds to make it stick combine.

After placing the aforementioned stickers in a temperature environment of 23°C for 60 minutes, use an electrodeless lamp (FUSION LAMP H-BULB) to irradiate ultraviolet light with an intensity of 100mW/cm ² for 10 seconds. At this time, the aforementioned ultraviolet irradiation was performed without removing the release liner.

Place the above-mentioned sticker after ultraviolet irradiation in a temperature environment of 23°C for 10 minutes, remove the release liner, and use a hot pressing device that has been heated to 80°C to pressurize at 0.5MPa. The surface is smoothed on an epoxy resin glass plate (manufactured by Shin-Kobe Electric Co., Ltd./KEL-GEF) with a width of 15 mm x a length of 150 mm x a thickness of 1.0 mm for 10 minutes. The above-mentioned laminated body after pressure bonding was heated and placed at 80°C for 1 hour, and then placed at 23°C for more than 30 minutes and then cooled as an evaluation sample.

In addition, the aluminum plate and epoxy glass plate used in this evaluation are materials that do not transmit light.

In the aforementioned evaluation sample, the ends of the aforementioned adherend (I) and the aforementioned adherend (II) were respectively clamped, and a tensile test was performed at a tensile speed of 10 mm/min in a direction of 180 degrees using a tensile testing machine. From this, the shear adhesion (MPa) of the aforementioned test sample was obtained.

[Evaluation method of low temperature curability (evaluation method of gel fraction before hardening)] The adhesive sheets obtained in Examples and Comparative Examples were cut into a size of 40 mm×50 mm. Then, what removed only the 38-micrometer-thick release liner attached to the said adhesive sheet was used as a test sample.

After measuring the mass of the aforementioned test sample, it was immersed in toluene adjusted to 23°C for 24 hours. After the aforementioned immersion, the test sample was taken out, and the mass obtained by drying it in a dryer at 105° C. for 1 hour was measured. Calculate the gel fraction of the adhesive layer before hardening based on the aforementioned mass and the following formula.

Gel fraction (mass %) of the adhesive layer before hardening = [(mass of the adhesive layer of the adhesive sheet that is not dissolved in toluene)/(adhesion of the aforementioned adhesive sheet before toluene immersion The mass of agent layer)]×100

The mass of the adhesive layer of the aforementioned adhesive sheet before dipping refers to the value obtained by subtracting the mass of the release liner used for its manufacture from the mass of the aforementioned test sample. Moreover, the mass of the said remaining adhesive layer means the value which subtracted the mass of the said release liner from the mass of the said residue after drying.

[Evaluation method of low-temperature curability (evaluation method of gel fraction after curing)] The adhesive sheets obtained in Examples and Comparative Examples were cut into a size of 40 mm×50 mm. Then, ultraviolet rays with an intensity of 100 mW/cm ² were irradiated for 10 seconds using an electrodeless lamp (FUSION LAMP H-BULB). At this time, ultraviolet rays were irradiated to the side of the release liner having a thickness of 50 μm. Let the above-mentioned sticker after ultraviolet irradiation be heated at 80°C for 1 hour, and then let it cool at 23°C for more than 30 minutes, and then remove only the peel-off liner with a thickness of 38 μm attached to the above-mentioned adhesive sheet. The winners were used as test samples.

After measuring the mass of the aforementioned test sample, it was immersed in toluene adjusted to 23°C for 24 hours. After the aforementioned immersion, the test sample was taken out, dried in a dryer at 105°C for 1 hour, and its mass was measured. Calculate the gel fraction of the hardened adhesive layer based on the aforementioned mass and the following formula.

Gel fraction (mass %) of the hardened adhesive layer=[(mass of the adhesive layer of the adhesive sheet that is not dissolved in toluene)/(adhesion of the aforementioned adhesive sheet before toluene immersion The mass of agent layer)]×100

The mass of the adhesive layer of the aforementioned adhesive sheet before dipping refers to the value obtained by subtracting the mass of the release liner used for its manufacture from the mass of the aforementioned test sample. Moreover, the mass of the said remaining adhesive layer means the value which subtracted the mass of the said release liner from the mass of the said residue after drying.

[Table 1]

[Table 2]

(Example 6) Make the aluminum plate with a smooth surface of width 15mm×length 70mm×thickness 0.3mm, degrease the aluminum plate with a spacer, arrange it in parallel at an interval of 12mm at the end of the top surface of the aluminum plate, and glue two spacers. Aluminum with spacers, and Use it as the adherend (I). In addition, the said spacer was comprised from the PET film and the adhesive sheet, and it manufactured so that the total thickness of the PET film and the adhesive sheet might become 80 micrometers. Also, a glass epoxy plate (manufactured by Shin-Kobe Electric Co., Ltd./KEL-GEF) with a width of 15 mm×length 70 mm×thickness 1.0 mm was used as an adherend (II). In addition, the aforementioned adherend (I) and the aforementioned adherend (II) are materials that do not transmit light.

Step [1-1]: Cut the aforementioned adhesive sheet (X-1) into a size of 10 mm in width and 10 mm in length as a test sample. Remove the release liner with a thickness of 38 μm from the aforementioned test sample, and place it between the two spacers of the aforementioned adherend (I), pressurize and crimp with a pressure of 0.05 MPa for 10 seconds at a temperature of 23°C to make it fit.

Step [2-1]: Then place the above-mentioned stickers in a temperature environment of 23°C for 30 minutes. Thereafter, the surface layer on the other side of the aforementioned test sample was irradiated with ultraviolet light at an intensity of about 100 mW/cm ² for 10 seconds using an electrodeless lamp (FUSION LAMP H-BULB).

Step [3-1]: After placing the above-mentioned sticker after ultraviolet irradiation at a temperature of 23°C for 20 minutes, remove the peel-off liner on the other side of the test sample, and use heat heated to 80°C The pressing device pressurizes for 10 minutes under the state of pressurizing at 0.2 MPa.

Step [4-1]: Heat the above-mentioned laminated body at 80°C for 1 hour, then let it stand at 23°C for 30 minutes and cool it down to obtain an evaluation sample (Y-1) .

The gel fraction of the aforementioned adhesive sheet (X-1) was 0.5% before being irradiated with ultraviolet rays.

In addition, in terms of the measurement method of the gel fraction, the adhesive sheet is cut into a size of 40 mm x 50 mm, and only the release liner on one side is removed as a test piece. After measuring the mass of the test piece, it was immersed in toluene adjusted to 23° C. for 24 hours. After the aforementioned immersion, the test piece was taken out, and the mass obtained by drying it in a dryer at 105° C. for 1 hour was measured. The gel fraction of the adhesive layer before irradiating active energy rays was calculated based on the aforementioned mass and the following formula.

Gel fraction (mass %) of the adhesive layer before irradiating active energy rays = [(mass of the adhesive layer of the adhesive sheet that is not dissolved in toluene)/(the aforementioned adhesive sheet before toluene immersion The mass of the adhesive layer)]×100

The mass of the adhesive layer of the adhesive sheet before immersion refers to the value obtained by subtracting the mass of the release liner used for its manufacture from the mass of the aforementioned test piece. Moreover, the mass of the said remaining adhesive layer means the value which subtracted the mass of the said release liner from the mass of the said residue after drying.

In the aforementioned step [2-1], the gel fraction of the aforementioned adhesive sheet (X-1) after irradiating ultraviolet rays was 8.5%.

In the aforementioned step [4-1], the gel fraction of the aforementioned adhesive sheet (X-1) after being placed in the aforementioned 23°C environment for 30 minutes and cooled was 71.5%.

As a result of visually confirming the above-mentioned evaluation sample (Y-1), no changes such as bending, occurrence of dents, and discoloration of the above-mentioned adherends (I) and adherends (II) were observed.

(Example 7) Use the aforementioned adhesive sheet (X-2) to replace the aforementioned adhesive sheet (X-1), except that, implement step [1-2], step [2-2], step [3-2], step [4-2], and obtain an evaluation sample (Y-2).

The gel fraction of the aforementioned adhesive sheet (X-2) was 0.2% before being irradiated with ultraviolet rays.

In the aforementioned step [2-2], the gel fraction of the aforementioned adhesive sheet (X-2) after being irradiated with ultraviolet rays was 6.1%.

In the aforementioned step [4-2], the gel fraction of the aforementioned adhesive sheet (X-2) after being placed in the aforementioned 23°C environment for 30 minutes and cooled was 68.9%.

As a result of visually confirming the above-mentioned evaluation sample (Y-2), changes such as bending, occurrence of dents, and discoloration of the above-mentioned adherends (I) and adherends (II) were not observed.

(Comparative Example 4) In the aforementioned step [2-1], irradiate ultraviolet rays with an intensity of about 100mW/cm ² for 1 minute, except that, implement step [1-1'], step [2-1'], step [3-1'], step [4-1'], and obtain the evaluation sample (Y'-1).

In the aforementioned step [2-1'], the gel fraction of the aforementioned adhesive sheet (X-1) after ultraviolet irradiation was 46.1%.

In the aforementioned step [4-1'], the gel fraction of the aforementioned adhesive sheet (X-1) after being placed in the aforementioned 23°C environment for 30 minutes and cooled was 77.8%.

As a result of visually confirming the aforementioned evaluation sample (Y'-1), it was observed that partial deflection and dents occurred in the aforementioned adherend (I).

(Comparative Example 5) In the aforementioned step [2-1], irradiate ultraviolet rays with an intensity of about 90 mW/cm ² for 1 second, except that, in the same manner as in Example 6, step [1-2'], Step [2-2'], step [3-2'], step [4-2'], and obtain an evaluation sample (Y'-2).

In the aforementioned step [2-2'], the gel fraction of the aforementioned adhesive sheet (X-1) after irradiating ultraviolet rays was 0.3%.

In the aforementioned step [4-2'], the gel fraction of the aforementioned adhesive sheet (X-1) after being placed in the aforementioned 23°C environment for 30 minutes and cooled was 10.8%.

As a result of visually confirming the aforementioned evaluation sample (Y'-2), no changes such as flexure, occurrence of dents, and discoloration of the aforementioned adherend (I) and adherend (II) were observed.

(Comparative Example 6) In the aforementioned step [2-1], irradiate ultraviolet rays with an intensity of about 90 mW/cm ² for 1 second, and in the aforementioned step [4-1], press-bond the aforementioned laminated body In addition to changing the heating and placing from 80°C to 180°C, steps [1-3'], steps [2-3'], steps [3-3'], steps [4-3'], and obtain the evaluation sample (Y'-3).

In the aforementioned step [2-3'], the gel fraction of the aforementioned adhesive sheet (X-1) after irradiating ultraviolet rays was 0.3%.

In the aforementioned step [4-3'], the gel fraction of the aforementioned adhesive sheet (X-1) after being placed in the aforementioned 23°C environment for 30 minutes and cooled was 84.1%.

As a result of visually confirming the aforementioned evaluation sample (Y'-2), the aforementioned adherend (II) deteriorated and discolored to yellow.

Moreover, the following evaluation was implemented about the evaluation sample obtained by the said Example and the comparative example.

[Evaluation of thickness change (softness)] By measuring the total thickness of the evaluation samples obtained in the aforementioned examples and comparative examples, and subtracting the thickness of the adherend (I) and the adherend (II) from it, the thickness of the aforementioned laminated adhesive sheet is calculated , and evaluated using the following criteria.

◎: The thickness of the adhesive sheet after the aforementioned lamination is 80 μm. 〇: The thickness of the adhesive sheet after the above-mentioned lamination is thicker than 80 μm and 90 μm or less. △: The thickness of the adhesive sheet after the above-mentioned lamination is thicker than 90 μm and 95 μm or less. ×: The thickness of the adhesive sheet after the above-mentioned lamination is thicker than 95 μm and 100 μm or less (no change).

[Evaluation of Shear Adhesion (Jointability)] By clamping the end of the adherend (I) and the aforementioned adherend (II) of the evaluation samples obtained in the above-mentioned examples and comparative examples, in a temperature environment of 23°C, use a tensile tester along the The tensile test was carried out at a tensile speed of 10mm/min in the direction of 180 degrees to obtain the shear adhesion of the aforementioned evaluation samples.

[table 3]

Claims (18)

A curable adhesive composition used for bonding two or more adherends with surfaces that do not transmit active energy rays; it contains a photocurable resin (A), a thermoplastic resin (B ) and a photopolymerization initiator, and the photocurable resin (A) has at least base,

Polymerizable functional groups other than one or more polymerizable unsaturated double bonds in the group consisting of oxazoline groups, the thermoplastic resin (B) has at least one group consisting of isocyanate groups, hydroxyl groups and oxetanyl groups One or more polymerizable functional groups other than polymerizable unsaturated double bonds in the group, the photocurable resin (A) is 10% by mass to the total amount of the curable adhesive composition. When used within a range of 50% by mass, the loss tangent (tanδ ₄₀ ) at 40°C is less than 1.5, and the loss tangent (tanδ ₆₀ ) at 60°C is 1.5 or more. Such as the curable adhesive composition of claim 1, wherein the thermoplastic resin (B) is a urethane resin (B'). Such as the curable adhesive composition of item 2 of the scope of the patent application, wherein the urethane resin (B') includes polycarbonate polyol, polyester polyol and polyether polyol Polyurethane resin (BA') obtained by reacting one or more polyols (b'1) and polyisocyanate (b'2) in the group consisting of alcohols. Such as the curable adhesive composition of claim 3, wherein the polyol (b'1) includes polycarbonate polyol and polyester polyol. For example, the curable adhesive composition of claim 4, wherein the polycarbonate polyol has a number-average molecular weight of 500-5000, and the polyester polyol has a number-average molecular weight of 1000-5000. The curable adhesive composition according to any one of items 1 to 5 of the patent claims, wherein the photopolymerization initiator is a photocationic polymerization initiator. For example, the curable adhesive composition of any one of items 1 to 5 of the scope of the patent application has a melting point within the range of 30°C to 120°C. An adhesive sheet has an adhesive layer formed by using the curable adhesive composition according to any one of items 1 to 7 in the scope of the patent application. A laminate obtained by attaching the adhesive sheet as described in item 8 of the patent application to the adherend. For example, the laminated body of item 9 in the scope of the patent application is used in image display devices. A method for manufacturing a laminate, comprising laminating two or more adherends with surfaces that do not transmit active energy rays through an adhesive sheet such as item 8 of the scope of the patent application; it includes sequentially : Step [1] of bonding the adhesive layer of the adhesive sheet to the first adherend by pressure-sensitive bonding; another step of bonding the adhesive layer of the adhesive sheet before or after step [1] The step of irradiating the surface of one side with active energy rays to increase the hardening rate of the adhesive layer by 0.01~30% [2]; the step of crushing the adhesive sheet [3]; and pressing the adhesive sheet In the collapsed state, the step [4] of further hardening the curing rate of the adhesive layer by 20% or more from the curing rate of the step [2]. For example, the method for manufacturing a laminated body as claimed in claim 11 of the patent application, wherein, in the step [1], the pressure for bonding is 0.1~3000KPa. Such as the manufacturing method of the laminated body of claim 11 or 12, wherein, in the step [2], the active energy ray intensity is 0.1~1000mW/cm ² , and the active energy ray is irradiated for 0.1~60 seconds. Such as the manufacturing method of the laminated body of claim 11 or 12 of the patent scope, wherein, in the step [3], the adhesive sheet is crushed by applying a pressure of 1-600KPa at a temperature of 30-100°C . Such as the manufacturing method of the laminated body of claim 11 or 12 of the patent scope, wherein, in the step [4], the adhesive sheet is matured at a temperature of 20-100°C for 10 minutes to 7 days. It hardens. The manufacturing method of the laminated body as claimed in claim 11 or 12, wherein the step [3] is implemented within 60 minutes after the end of the step [2]. The manufacturing method of the laminated body as claimed in claim 11 or 12 of the patent application, wherein the step [4] is implemented within 60 minutes after the end of the step [2]. An image display device is manufactured by using any one of the manufacturing methods in the 11th to 17th items of the patent application.