JP2021133680A - Transfer sheet and laminate, method for manufacturing laminate, and image display device - Google Patents

Abstract

To provide a transfer sheet and a laminate which can keep texture of an adherend good, have high surface hardness of a laminate, and can suppress occurrence of scratches.MEANS FOR SOLVING THE PROBLEM: A transfer sheet has a transfer layer on a peeling base material A, in which the transfer layer has an antireflection layer, a hard coat layer and an adhesive layer in this order form the side of the peeling base material A, and the adhesive layer contains a thermoplastic resin and an ionizing radiation curable resin composition.SELECTED DRAWING: Figure 1

Description

The present invention relates to a transfer sheet and a laminate, a method for manufacturing the laminate, and an image display device.

It may be required to impart predetermined functions such as antireflection, antiglare, and antifouling properties to the surface of an arbitrary adherend. Further, when the adherend is glass, it is required that the texture such as hardness and coldness that the glass has when touched by hand, that is, so-called cold touch, can be obtained even after the surface is given a predetermined function. .. In such a case, for example, there is a method of imparting a predetermined function to the surface of the adherend by directly applying a functional paint to the surface of the adherend by spraying or the like.

However, when the functional paint is directly applied to the surface of the adherend, there is a problem that the function becomes uneven due to the uneven coating.

In order to solve the above-mentioned problem of direct coating, a functional film having a functional layer on a support and an adherend are integrated to give a predetermined function to the surface of the adherend. The body is proposed. For example, Patent Document 1 states that a hard coat layer, a high refractive index layer, and a low refractive index layer are laminated in this order on one surface of a thermoplastic transparent base film to prevent fingerprint resistance for insert molding. A resin molded body having a film on the surface has been proposed.

Japanese Unexamined Patent Publication No. 2016-020049 Japanese Unexamined Patent Publication No. 2003-103680

However, although the resin molded product disclosed in Patent Document 1 has good antireflection property, it is adhered because a relatively thick layer such as a thermoplastic transparent base film is present on the adherend. The texture of the body could not be reflected on the surface of the molded product, and a cold touch could not be obtained.

In order not to impair the texture of the adherend, a means using an antireflection transfer film as in Patent Document 2 can be considered.

However, in the laminated body obtained by transferring the antireflection layer to the adherend using the antireflection transfer film as in Patent Document 2, there are many problems that the antireflection layer is scratched and the generated scratches are conspicuous. ..

The present invention has been made in view of such circumstances, and the transfer sheet and the laminate which can maintain a good texture of the adherend, have a high surface hardness of the laminate, and can suppress the occurrence of scratches. The challenge is to provide the body. Another object of the present invention is to provide a method for producing the laminated body. Another object of the present invention is to provide an image display device having the laminated body.

As a result of diligent research, the present inventor has found that scratches on the laminate formed by transferring the transfer layer to the adherend using the transfer film are likely to occur when the hardness of the adhesive layer is low, and the transfer layer is reflected. It has been found that when the protective layer is provided, the scratches generated become more noticeable. As a result of further research, the above-mentioned problems have been solved by including the thermoplastic resin and the ionizing radiation curable resin in the adhesive layer of the transfer sheet having the antireflection layer as the transfer layer.

That is, the present invention provides the following [1] to [7].
[1] A transfer sheet having a transfer layer on the release base material A, wherein the transfer layer has an antireflection layer, a hard coat layer, and an adhesive layer in this order from the release base material A side, and the adhesive layer. Is a transfer sheet containing a thermoplastic resin and an ionizing radiation curable resin composition.
[2] The mass ratio _M B / _{M A} of the mass _{M B} of the mass _{M A} and the ionizing radiation curable resin composition of the thermoplastic resin of the adhesive layer is 0.10 or more 1.30 or less, [1 ] The transfer sheet described in.
[3] A laminate in which an adhesive layer, a hard coat layer, and an antireflection layer are contained in this order on a glass substrate, and the adhesive layer contains a thermoplastic resin and an ionizing radiation curable resin composition.
[4] The mass ratio _M B / _{M A} of the mass _{M B} of the mass _{M A} and the ionizing radiation curable resin composition of the thermosetting resin of the adhesive layer is 0.10 or more 1.30 or less, [ 3].
[5] JIS K 5600-5-6: 1999 under the condition that the number of cuts in each direction of the lattice pattern is 11 and the cut interval is 1 mm between the glass base material and the adhesive layer. The laminate according to [3] or [4], wherein the evaluation result of the adhesiveness carried out by the cross-cut method shows that the cross-cut portion where peeling can be confirmed in the lattice pattern is less than 5%.
[6] A method for producing a laminate having the following steps (1) to (4).
(1) A step of superimposing the transfer sheet according to [1] or [2] on a glass base material in contact with the surface of the transfer sheet on the adhesive layer side.
(2) A step of heating and pressurizing from the peeling base material A side of the transfer sheet to bring the glass base material and the adhesive layer of the transfer sheet into close contact with each other.
(3) A step of peeling and removing the peeling base material A of the transfer sheet from the glass base material and the transfer sheet that are in close contact with each other.
(4) A step of irradiating ionizing radiation from the antireflection layer side of the transfer layer to promote curing of the transfer layer.
[7] An image display device having the laminate according to any one of [3] to [5] on the display element.

According to the present invention, it is possible to provide a transfer sheet, a laminate, and an image display device that can maintain a good texture of an adherend, have a high surface hardness of the laminate, and can suppress the occurrence of scratches. .. Further, according to the present invention, the laminated body can be easily manufactured.

It is sectional drawing which shows one Embodiment of the transfer sheet of this invention. It is sectional drawing which shows one Embodiment of the laminated body of this invention.

[Transfer sheet]
The transfer sheet of the present invention is a transfer sheet having a transfer layer on the release base material A, and the transfer layer has an antireflection layer, a hard coat layer and an adhesive layer in this order from the release base material A side. The adhesive layer is characterized by containing an ionizing radiation curable resin composition and a thermoplastic resin.

The ionizing radioactive resin composition contained in the adhesive layer of the transfer sheet of the present invention refers to a cured product of the ionizing radiation curable resin composition and an uncured product of the ionizing radiation curable resin composition.
In the ionizing radiation curable resin composition contained in the adhesive layer of the transfer sheet of the present invention, the ratio of the cured product of the ionizing radiation curable resin composition is preferably 50% by mass or more, more preferably 70% by mass or more, and 90% by mass or more. More preferably by mass% or more.

By having the above characteristics, the laminate using the transfer sheet of the present invention maintains a good texture of the adherend, and further, the surface hardness of the laminate is high, and the laminate can suppress the occurrence of scratches. Become.

FIG. 1 is a cross-sectional view showing an embodiment of the transfer sheet of the present invention. The transfer sheet 1 of FIG. 1 has a transfer layer 100 on the release base material A10, and the transfer layer 100 has an antireflection layer 20, a hard coat layer 30, and an adhesive layer 40 in this order from the side in contact with the release base material A10. Have.
Although not shown, the transfer sheet 1 of FIG. 1 may have an anchor layer between the layers in order to improve the adhesion of each layer constituting the transfer sheet 1. Further, although not shown, the transfer sheet 1 of FIG. 1 may further have a release base material B on a surface opposite to the release base material A of the adhesive layer.

[Release base material A]
The release base material A is a layer that is releasably laminated with the transfer layer in the layer constituting the transfer sheet.
The release base material A is preferably a plastic film that can be peelably laminated with the transfer layer and has heat resistance in order to improve processability in the transfer step.
Examples of the plastic film used as the release base material A include polyester resins such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate, polyamide resins such as nylon 6 or nylon 66, polyimide resins, and olefin resins. It is preferable to use polyester resin, and it is particularly preferable to use polyethylene terephthalate.

The plastic film used for the release base material A has a heat shrinkage rate of 100 ° C. for 30 minutes measured in accordance with JIS C 2318: 1997 5.3.4 (dimensional change) in order to improve workability. It is preferably within ± 1.5%, more preferably within ± 1.0%, and even more preferably within ± 0.5%. The heat shrinkage rate of the plastic film is preferably in the above range in all directions.
When the heat shrinkage rate of the plastic film is within the above range, it is possible to easily suppress the deformation of the release base material A when heated in the step of transferring the transfer layer to the adherend, and the transfer layer (particularly, the inorganic film) can be easily suppressed. It becomes easier to prevent cracks from occurring in the antireflection layer).
The heat shrinkage rate is determined by marking the test piece in accordance with JIS C 2318: 1997 5.3.4 (dimensional change), and at the mark interval (A) before heating and at 100 ° C. for 30 minutes. The mark interval (B) after the heat treatment is measured and calculated by the following formula.
Heat shrinkage rate (%) = (AB) / A × 100

The thickness of the release base material A is not particularly limited, but in order to improve handleability, it is preferably 10 μm or more and 200 μm or less, more preferably 20 μm or more and 150 μm or less, and further preferably 30 μm or more and 100 μm or less. ..

The peeling base material A needs to have an adhesive layer on the surface in contact with the transfer layer because the peeling base material A needs not to be peeled off from the transfer layer before the peeling base material A is peeled off from the transfer layer through the transfer step. Is preferable. The adhesive layer is not particularly limited as long as it can be detachably laminated with the transfer layer, and a known adhesive can be used.

As the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer of the release base material A, an acrylic-based, urethane-based, silicone-based, rubber-based, or other pressure-sensitive adhesive can be appropriately selected and used. The pressure-sensitive adhesive is preferably an acrylic type or a silicone type in order to improve heat resistance.

The thickness of the adhesive layer of the release base material A is not particularly limited, but in order to improve the balance between the peelability and the adhesiveness with the transfer layer, it is preferably 1 μm or more and 30 μm or less, more preferably 3 μm or more and 20 μm or less, and 5 μm or more and 15 μm or less. Is even more preferable.

The peel strength between the release base material A and the transfer layer is preferably 100 mN / 25 mm or more and 600 mN / 25 mm or less, more preferably 120 mN / 25 mm or more and 500 mN / 25 mm or less, and further preferably 140 mN / 25 mm or more and 400 mN / 25 mm or less.
By setting the peel strength between the peeling base material A and the transfer layer to 100 mN / 25 mm or more, it becomes easy to prevent the peeling base material A from being unintentionally peeled off before the peeling base material A is peeled off from the transfer layer. .. Further, by setting the peel strength between the release base material A and the transfer layer to 400 mN / 25 mm or less, when the release base material A is peeled from the transfer layer, the transfer layer and the adhesive layer undergo cohesive failure and interfacial peeling. It becomes easier to deter.

In the present specification, the peel strength can be measured according to the 180 degree peel test of JIS Z 0237: 2009. The atmosphere for measuring the peel strength is preferably 23 ° C. and a humidity of 40% or more and 65% or less. Further, it is preferable to allow the sample to acclimatize to the atmosphere for 30 minutes before measuring the peel strength. The measurement is carried out three times per sample, and the average value is taken as the peel strength.

[Transfer layer]
The transfer layer is a layer that is transferred to the adherend, and has a role of imparting a predetermined function to the surface of the adherend.
The transfer layer of the transfer sheet of the present invention includes at least an antireflection layer, a hard coat layer, and an adhesive layer in this order.

The transfer layer may further have another functional layer. Examples of other functional layers include an antiglare layer, an antifouling layer, a stress relaxation layer, an antistatic layer, a gas barrier layer, an antifog layer, a transparent conductive layer and the like.

Further, the antireflection layer, the hard coat layer, the adhesive layer and the other functional layer included in the transfer layer may be a composite of two or more of the above-mentioned functions.

The transfer layer may further have an anchor layer or the like between the layers constituting the transfer layer in order to improve the adhesion between the layers constituting the transfer layer.

The total thickness of the transfer layer is preferably 3 μm or more and 30 μm or less, more preferably 5 μm or more and 21 μm or less, and further preferably 7 μm or more and 15 μm or less. When the total thickness of the transfer layer is 3 μm or more, a predetermined thickness of the adhesive layer, the hard coat layer and the antireflection layer can be secured. By setting the total thickness of the transfer layer to 30 μm or less, it is possible to easily maintain the texture of the adherend when the transfer layer is touched by hand in the laminated body after transfer.

(Anti-reflective layer)
The antireflection layer has a function of imparting an antireflection function to the surface of the adherend in the layer constituting the transfer layer of the transfer sheet.

The antireflection layer includes at least one or more low refractive index layers. By including the low refractive index layer in the antireflection layer, the transfer sheet of the present invention can impart an antireflection function to the surface of the laminated body.

The antireflection layer preferably further contains one or more high refractive index layers. When the antireflection layer includes a high refractive index layer, it is preferable that the low refractive index layer and the high refractive index layer are alternately laminated. By alternately stacking the low refractive index layer and the high refractive index layer, the antireflection effect is further enhanced.
When the low refractive index layer and the high refractive index layer are alternately laminated, it is preferable to arrange the low refractive index layer on the side closest to the peeling base material A of the transfer sheet in the antireflection layer. By arranging the low refractive index layer on the side closest to the release base material A, the low refractive index layer can be formed on the outermost surface of the laminated body at the time of forming the laminated body, so that the refractive index between the surface of the laminated body and air The difference can be reduced, and the antireflection effect of the laminated body can be easily enhanced.

The antireflection layer is preferably a total of two or more layers consisting of one or more low refractive index layers and one or more high refractive index layers, and is preferably two or more low refractive index layers and two or more high refractive index layers. A total of four or more layers composed of rate layers is more preferable, and a total of five layers including three low refractive index layers and two high refractive index layers is particularly preferable.
When the antireflection layer is formed by a wet method such as coating described later, the antireflection layer is a single layer composed of one low refractive index layer, or one low refractive index layer and one high refractive index layer. It is preferably composed of a total of two layers. Further, when the antireflection layer is formed by a dry method such as sputtering described later, it is preferable that the antireflection layer is a total of five layers including three low refractive index layers and two high refractive index layers.
By forming the antireflection layer into a multi-layer composed of one or more low refractive index layers and one or more high refractive index layers, the antireflection effect is further enhanced.

The total thickness of the antireflection layer varies depending on the number of layers of the antireflection layer and cannot be unequivocally determined. The following are particularly preferred.
By setting the total thickness of the antireflection layer in the above range, the antireflection function can be suitably imparted to the surface of the laminated body.

-Low refractive index layer-
The refractive index of the low refractive index layer is preferably 1.10 or more and 1.48 or less, more preferably 1.20 or more and 1.45 or less, more preferably 1.26 or more and 1.40 or less, and 1.28 or more and 1. 38 or less is more preferable, and 1.30 or more and 1.32 or less are more preferable.
The thickness of the low refractive index layer is preferably 8 nm or more and 120 nm or less, more preferably 15 nm or more and 110 nm or less, and more preferably 20 nm or more and 105 nm or less.

The method for forming the low refractive index layer can be roughly divided into a wet method and a dry method. As the wet method, a method of forming by a sol-gel method using a metal alkoxide or the like, a method of forming by coating a resin having a low refractive index such as a fluororesin, or a low refractive index particles contained in a resin composition. A method of forming by applying a coating liquid for forming a refractive index layer can be mentioned. Examples of the dry method include a method of selecting particles having a desired refractive index from low refractive index particles, which will be described later, and forming them by a physical vapor deposition method, a chemical vapor deposition method, or sputtering.
The wet method is superior to the dry method in terms of production efficiency, suppression of obliquely reflected hue, and chemical resistance. In the present invention, even in the wet method, a low refractive index in which low refractive index particles are contained in a binder resin composition in order to improve adhesion, water resistance and scratch resistance, and to reduce the refractive index. It is preferably formed with a layer-forming coating liquid. As the binder resin composition of the low refractive index layer, for example, a curable resin composition can be used, and it is preferable to use the ionizing radiation curable resin composition exemplified by the adhesive layer described later.

The low refractive index layer preferably contains hollow particles in order to lower the refractive index of the low refractive index layer and bring it within the above refractive index range. Further, in order to increase the surface hardness of the laminate and improve the scratch resistance, it is preferable to contain non-hollow particles.
The material of the hollow particles and the non-hollow particles may be any of an inorganic compound such as silica and magnesium fluoride, and an organic compound, but silica is preferable in order to lower the refractive index and improve the strength. Hereinafter, the center of hollow silica particles and non-hollow silica particles will be described.

Hollow silica particles refer to particles having an outer shell layer made of silica, the inside of the particles surrounded by the outer shell layer is a cavity, and the inside of the cavity contains air. Hollow silica particles are particles whose refractive index decreases in proportion to the gas occupancy rate as compared with the original refractive index of silica due to the inclusion of air. Non-hollow silica particles are particles that are not hollow inside, such as hollow silica particles. The non-hollow silica particles are, for example, solid silica particles.
The shapes of the hollow silica particles and the non-hollow silica particles are not particularly limited, and may be a spherical shape, a spheroidal shape, or a substantially spherical shape such as a polyhedral shape that can be approximated to a sphere. Among them, in consideration of scratch resistance, it is preferably a true sphere, a spheroid, or a substantially sphere.

Since the hollow silica particles contain air inside, they play a role of lowering the refractive index of the entire low refractive index layer. By using hollow silica particles having a large particle size with an increased proportion of air, the refractive index of the low refractive index layer can be further reduced. On the other hand, hollow silica particles tend to be inferior in mechanical strength. In particular, when hollow silica particles having a large particle size with an increased proportion of air are used, the scratch resistance of the low refractive index layer tends to be lowered.
The non-hollow silica particles play a role of improving the scratch resistance of the low refractive index layer by dispersing in the binder resin.

In order to contain the hollow silica particles and the non-hollow silica particles in the binder resin at a high concentration and uniformly disperse the particles in the resin in the film thickness direction, the hollow silica particles are close to each other, and the hollow silica particles are further arranged. It is preferable to set the average particle size of the hollow silica particles and the average particle size of the non-hollow silica particles so that the non-hollow particles can be inserted between the two. Specifically, the ratio of the average particle size of the non-hollow silica particles to the average particle size of the hollow silica particles (average particle size of the non-hollow silica particles / average particle size of the hollow silica particles) is 0.29 or less. It is preferably 0.20 or less, and more preferably 0.20 or less. Moreover, the ratio of the average particle diameter is preferably 0.05 or more. Considering the optical characteristics and the mechanical strength, the average particle size of the hollow silica particles is preferably 30 nm or more and 100 nm or less, and more preferably 50 nm or more and 80 nm or less. Further, considering the dispersibility while preventing the agglomeration of the non-hollow silica particles, the average particle size of the non-hollow silica particles is preferably 5 nm or more and 20 nm or less, and more preferably 10 nm or more and 15 nm or less.

The surfaces of the hollow silica particles and the non-hollow silica particles are preferably coated with a silane coupling agent. It is more preferable to use a silane coupling agent having a (meth) acryloyl group or an epoxy group.
By subjecting the silica particles to a surface treatment with a silane coupling agent, the affinity between the silica particles and the binder resin is improved, and the aggregation of the silica particles is less likely to occur. Therefore, the dispersion of silica particles tends to be uniform.

Examples of the silane coupling agent include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltri. Methoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3 -Glysidoxypropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane , 3-Aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, Tris- (trimethoxysilylpropyl) isocia Nurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanuppropyltriethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, Phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1,6-bis (trimethoxysilyl) hexane , Trifluoropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane and the like. In particular, one or more selected from 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane may be used. preferable.

As the content of the hollow silica particles increases, the filling rate of the hollow silica particles in the binder resin increases, and the refractive index of the low refractive index layer decreases. Therefore, the content of the hollow silica particles is preferably 100 parts by mass or more, and more preferably 150 parts by mass or more with respect to 100 parts by mass of the binder resin.
On the other hand, if the content of the hollow silica particles with respect to the binder resin is too large, the number of hollow silica particles exposed from the binder resin increases and the amount of the binder resin bonded between the particles decreases. For this reason, the hollow silica particles tend to be easily damaged or fall off, and the mechanical strength such as scratch resistance of the low refractive index layer tends to decrease. Further, if the content of the hollow silica particles is too large, the transferability tends to be impaired. Therefore, the content of the hollow silica particles is preferably 300 parts by mass or less, and more preferably 200 parts by mass or less with respect to 100 parts by mass of the binder resin.

If the content of the non-hollow silica particles is low, even if the non-hollow silica particles are present on the surface of the low refractive index layer, they may not affect the increase in hardness. Further, when a large amount of non-hollow silica particles are contained, the influence of shrinkage unevenness due to the polymerization of the binder resin can be reduced, and the unevenness generated on the surface of the low refractive index layer after the resin is cured can be reduced. Therefore, the content of the non-hollow silica particles is preferably 90 parts by mass or more, and more preferably 100 parts by mass or more with respect to 100 parts by mass of the binder resin.
On the other hand, if the content of the non-hollow silica particles is too large, the non-hollow silica tends to aggregate, causing uneven shrinkage of the binder resin and increasing surface irregularities. Further, if the content of the non-hollow silica particles is too large, the transferability tends to be impaired. Therefore, the content of the non-hollow silica particles is preferably 200 parts by mass or less, and more preferably 150 parts by mass or less with respect to 100 parts by mass of the binder resin.

The binder resin composition of the low refractive index layer preferably contains a curable resin composition, and more preferably contains an ionizing radiation curable resin composition. As the ionizing radiation curable resin composition contained in the binder resin composition of the low refractive index layer, for example, the ionizing radiation curable resin composition exemplified in the adhesive layer described later can be used.

The low refractive index layer preferably contains a leveling agent in order to improve antifouling property and surface smoothness.
Examples of the leveling agent include fluorine-based and silicone-based, but fluorine-based agents are preferable. By including a fluorine-based leveling agent, the surface of the low refractive index layer can be made smoother. Further, the slipperiness and antifouling property (fingerprint wiping property, large contact angle with pure water and hexadecane) of the surface of the low refractive index layer can be improved.

The content of the leveling agent is preferably 0.15 parts by mass or more and 35.0 parts by mass or less, and 0.20 parts by mass or more and 30 parts by mass with respect to 100 parts by mass of the curable resin contained in the low refractive index layer. It is more preferably 0 parts by mass or less, and further preferably 0.25 parts by mass or more and 25.0 parts by mass or less. By setting the content of the leveling agent to 0.15 parts by mass or more, the surface of the hard coat layer can be easily smoothed, and the slipperiness and antifouling property can be improved. Further, by setting the content of the leveling agent to 35.0 parts by mass or less, it is possible to suppress a decrease in the hardness of the low refractive index layer.

-High refractive index layer-
The refractive index of the high refractive index layer is preferably 1.53 or more and 2.50 or less, more preferably 1.54 or more and 2.40 or less, further preferably 1.55 or more and 2.30 or less, and 1.56 or more and 2. 25 or less is particularly preferable.
The thickness of the high refractive index layer is preferably 200 nm or less, more preferably 10 nm or more and 180 nm or less, and further preferably 20 nm or more and 150 nm or less.

The method for forming the high refractive index layer can be roughly divided into a wet method and a dry method. As the wet method, a method of forming by a sol-gel method using a metal alkoxide or the like, a method of forming by coating a resin having a high refractive index, and a method for forming a high refractive index layer in which high refractive index particles are contained in a resin composition. A method of forming by applying a coating liquid can be mentioned. Examples of the dry method include a method of selecting particles having a desired refractive index from the high-refractive index particles described later, and forming them by a physical vapor deposition method, a chemical vapor deposition method, or sputtering. The wet method is superior to the dry method in terms of production efficiency, suppression of obliquely reflected hue, and chemical resistance. In the present invention, among the wet methods, a high refractive index layer in which a binder resin composition contains high refractive index particles in order to improve adhesion, water resistance and scratch resistance, and to increase the refractive index. It is preferably formed with a coating liquid for forming. As the binder resin composition of the high refractive index layer, for example, a curable resin composition can be used, and it is preferable to use the ionizing radiation curable resin composition exemplified by the adhesive layer described later.

Examples of the inorganic compound forming the high refractive index layer include antimony pentoxide (1.79), zinc oxide (1.90), titanium oxide (2.3 or more and 2.7 or less), cerium oxide (1.95), and the like. Tin-doped indium oxide (1.95 or more and 2.00 or less), antimony-doped tin oxide (1.75 or more and 1.85 or less), yttrium oxide (1.87), zirconium oxide (2.10) and niobium pentoxide (2) .33) and the like. The numerical value in parentheses means the refractive index.

The average particle size of the high-refractive index particles is preferably 2 nm or more, more preferably 5 nm or more, and even more preferably 10 nm or more. The average particle size of the high-refractive index particles is preferably 200 nm or less, more preferably 100 nm or less, more preferably 80 nm or less, and more preferably 60 nm or less in order to easily suppress whitening and improve transparency. , 30 nm or less is more preferable. The smaller the average particle size of the high-refractive index particles, the better the transparency. In particular, when the average particle size is 60 nm or less, the transparency can be extremely improved.

In the present invention, the average particle size of the particles in the antireflection layer and the hard coat layer described later is measured by measuring the particles in the solution by a dynamic light scattering method, and the particle size distribution is represented by the cumulative distribution of volumes. The particle size is 50% (d50: median size), and can be measured using a Microtrac particle size analyzer (manufactured by Nikkiso Co., Ltd.). The average particle size of the fine particles described later can be measured by the same method.

(Adhesive layer)
The adhesive layer is a layer that is in contact with the adherend in the layer constituting the transfer layer of the transfer sheet, and is formed, for example, to improve the adhesion to the adherend.

In the present invention, the adhesive layer is required to contain an ionizing radiation curable resin composition and a thermoplastic resin. If the adhesive layer does not contain a thermoplastic resin, the adhesiveness between the adhesive layer and the adherend such as glass is lowered, and a predetermined function is not imparted to the surface of the laminate. Further, if the adhesive layer does not contain the ionizing radiation curable resin composition, the hardness of the transfer layer becomes low, and the surface hardness of the laminated body cannot be increased.

The ionizing radiation curable resin composition of the adhesive layer may contain an uncured product, but it is preferable that the cured product is the main component. In the ionizing radiation curable resin composition contained in the adhesive layer, the ratio of the cured product of the ionizing radiation curable resin composition is preferably 50% by mass or more, more preferably 70% by mass or more, and further 90% by mass or more. preferable.

Wherein contained in the adhesive layer, the mass ratio _M B / _{M A} of the mass _{M B} of the mass _{M A} and the ionizing radiation curable resin composition of the thermoplastic resin is preferably 0.10 or more, 0.15 The above is more preferable, 0.20 or more is further preferable, and 0.40 or more is particularly preferable. M B _/ M _A that is 0.10 or more, it is possible to increase the hardness of the adhesive layer, the hardness of the adherend is not impaired by the adhesive layer, it tends to reflect the surface hardness of the laminate. Therefore, particularly when the adherend is a hard material such as glass, the surface hardness of the laminated body can be increased, and scratches on the surface of the laminated body can be prevented.
Further it, the mass ratio _M B / _{M A,} preferably 1.30 or less, more preferably 1.20 or less, further preferably 1.00 or less, 0.80 or less Is particularly preferable. By M B _/ M _A is 1.30 or less, it is possible to include a large amount of thermoplastic resin in the adhesive layer, can improve the workability at the time of thermal transfer of the transfer layer to the adherend. Further, since the curing shrinkage when the ionizing radiation curable resin composition is cured can be suppressed, the distortion of the adhesive layer can be reduced. Therefore, the interlayer strength between the adhesive layer and other layers constituting the transfer layer can be improved, and it is possible to easily prevent the transfer layer from being delaminated due to rubbing or the like. Further, since it is possible to prevent the adhesion between the adhesive layer and the adherend from being lowered due to the distortion of the adhesive layer, it is possible to prevent the transfer layer from peeling off from the adherend.

The adhesive layer preferably has no tack in order to improve reworkability when the transfer sheet is placed on an adherend such as a glass base material.
In the present specification, in the tilted ball tack test of JIS Z 0237: 2009, an adhesive layer in which the ball does not stop in the measuring section for 5 seconds or more under the conditions of "ball number: No. 1" and "tilt angle: 20 °". Is regarded as an "adhesive layer without tack". The temperature and relative humidity conditions at the time of the test are the general conditions specified in JIS Z 0237: 2009 (temperature: 23 ± 1 ° C., relative humidity: 50 ± 5%).

As the thermoplastic resin contained in the adhesive layer of the present invention, a thermoplastic resin which is a transparent resin and exhibits adhesiveness by heating is preferable. For example, polyvinyl butyral (PVB) and ethylene-vinyl acetate copolymer (EVA) are preferable. ), Polyester, polyurethane, polyester urethane, acrylic, olefin and the like. Among these, in order to improve the adhesion between the adhesive layer and the adherend such as a glass base material, it is preferable to use one selected from polyvinyl butyral, ethylene-vinyl acetate copolymer and polyester urethane. It is more preferable to use polyvinyl butyral or polyester urethane.
When polyvinyl butyral is used as the thermoplastic resin, the glass transition temperature of polyvinyl butyral is preferably 55 ° C. or higher and 90 ° C. or lower, more preferably 60 ° C. or higher and 80 ° C. or lower.
When the glass transition temperature is 55 ° C. or higher, the hardness of the adhesive layer is less likely to be lowered, and the surface hardness of the laminated body is likely to be increased.
Further, when the glass transition temperature is 90 ° C. or lower, the processability by thermal transfer can be improved and the adhesion between the adhesive layer and the adherend can be improved, so that the transfer layer can be prevented from falling off from the adherend. It becomes easier to suppress.
The glass transition temperature can be determined based on the measurement of the change in calorific value (DSC method) by DSC (differential scanning calorimetry).

When an ethylene-vinyl acetate copolymer is used as the thermoplastic resin, the vinyl acetate content defined in JIS K 6924-1: 1997 is preferably 25% or more and 50% or less, and more preferably 30% or more and 45% or less. preferable. When the vinyl acetate content is 25% or more, a large amount of polar groups can be contained in the adhesive layer, so that the adhesion between the adhesive layer and the adherend such as glass can be improved, and the transfer layer can be separated from the adherend. It becomes easier to prevent it from falling off. Further, when the vinyl acetate content is 50% or less, the hardness of the adhesive layer is less likely to be lowered, and the surface hardness of the laminated body is easily increased.

When polyester urethane is used as the thermoplastic resin, the glass transition temperature of the polyester urethane is preferably 55 ° C. or higher and 90 ° C. or lower, and more preferably 60 ° C. or higher and 80 ° C. or lower.
When the glass transition temperature is 55 ° C. or higher, the hardness of the adhesive layer is less likely to be lowered, and the surface hardness of the laminated body is likely to be increased. Further, when the glass transition temperature is 90 ° C. or lower, the processability by thermal transfer can be improved and the adhesion between the adhesive layer and the adherend can be improved, so that the transfer layer can be prevented from falling off from the adherend. It becomes easier to suppress.
The weight average molecular weight of the polyester urethane is preferably 15,000 or more and 45,000 or less, and more preferably 25,000 or more and 35,000 or less.
When the weight average molecular weight is 15,000 or more, the adhesion between the adhesive layer and the adherend can be easily improved. Further, when the weight average molecular weight is 35,000 or less, the viscosity of the coating liquid for forming the adhesive can be in an appropriate range, so that a uniform adhesive layer can be formed, and the transfer sheet and the laminate having a good appearance can be formed. Can be obtained.
The weight average molecular weight in the present specification is an average molecular weight measured by GPC analysis and converted into standard polystyrene.

The ionizing radiation curable resin composition is a composition containing a compound having an ionizing radiation curable functional group (hereinafter, also referred to as “ionizing radiation curable compound”). Examples of the ionizing radiation curable functional group include an ethylenically unsaturated group such as a (meth) acroyl group, a vinyl group and an allyl group, and an oxetanyl group.
As the ionizing radiation curable compound contained in the ionizing radiation curable resin composition of the adhesive layer, a compound having an ethylenically unsaturated bond group is preferable. Further, in order to prevent the transfer layer from being damaged in the process of producing the transfer sheet, as the ionizing radiation curable compound, a compound having two or more ethylenically unsaturated bonding groups is more preferable, and among them, the ethylenically unsaturated compound is preferable. A polyfunctional (meth) acrylate compound having two or more binding groups is more preferable. As the polyfunctional (meth) acrylate compound, either a monomer or an oligomer can be used.

The ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or cross-linking a molecule, and usually, an ultraviolet ray (UV) or an electron beam (EB) is used. Electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion-rays can also be used.
The ionizing radiation curable resin composition contained in the adhesive layer is preferably an electron beam curable resin composition or an ultraviolet curable resin composition, and more preferably an ultraviolet curable resin composition.
By using an ultraviolet curable resin composition for the adhesive layer, when the layer in contact with the adhesive layer also contains the ultraviolet curable resin composition, the ultraviolet curable resin compositions contained in each layer are chemically bonded to each other. Therefore, the interlayer strength between the adhesive layer and the layer in contact with the adhesive layer can be improved. Therefore, delamination can be less likely to occur in the transfer layer, and the scratch resistance of the surface of the laminate can be easily improved. Further, by increasing the adhesion between the respective layers of the transfer layer, the entire transfer layer is integrated, and the generated scratches become less noticeable.

Among the polyfunctional (meth) acrylate-based compounds, the bifunctional (meth) acrylate-based monomers include ethylene glycol di (meth) acrylate, bisphenol A tetraethoxydiacrylate, bisphenol A tetrapropoxydiacrylate, and 1,6-hexane. Examples thereof include diol diacrylate.
Examples of the trifunctional or higher functional (meth) acrylate-based monomer include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and di. Examples thereof include pentaerythritol tetra (meth) acrylate and isocyanuric acid-modified tri (meth) acrylate.
Further, the (meth) acrylate-based monomer may be one in which a part of the molecular skeleton is modified, and is modified with ethylene oxide, propylene oxide, caprolactone, isocyanuric acid, alkyl, cyclic alkyl, aromatic, bisphenol and the like. Can also be used.

Examples of the polyfunctional (meth) acrylate-based oligomer include acrylate-based polymers such as urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, and polyether (meth) acrylate.
Urethane (meth) acrylate is obtained, for example, by reacting a polyhydric alcohol or an organic diisocyanate with a hydroxy (meth) acrylate.
Further, the preferable epoxy (meth) acrylate is a (meth) acrylate obtained by reacting a (meth) acrylic acid with a trifunctional or higher functional aromatic epoxy resin, an alicyclic epoxy resin, an aliphatic epoxy resin or the like, and a bifunctional epoxy resin. (Meta) acrylate obtained by reacting the above aromatic epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, etc. with polybasic acid and (meth) acrylic acid, and bifunctional or higher functional aromatic epoxy resin, It is a (meth) acrylate obtained by reacting an alicyclic epoxy resin, an aliphatic epoxy resin or the like with phenols and (meth) acrylic acid.
The ionizing radiation curable resin may be used alone or in combination of two or more.

Further, among the ionizing radiation curable resin compositions exemplified above, the (meth) acrylate-based compound modifies a part of the molecular skeleton in order to suppress shrinkage unevenness due to cross-linking and enhance surface smoothness. It may be the one that is. For example, those modified with ethylene oxide, propylene oxide, caprolactone, isocyanuric acid, alkyl, cyclic alkyl, aromatic, bisphenol and the like can also be used.
In particular, the above (meth) acrylate-based compound may be prepared with tris (2-acroxyethyl) isocyanurate, ε-caprolactone-modified tris- (2-acroxyethyl) isocyanurate, etc. in order to improve the moist heat resistance of the adhesive layer. Those modified with isocyanuric acid (having an isocyanurate structure) are preferable. As the (meth) acrylate having an isocyanurate structure in the skeleton, those further modified with caprolactone are particularly preferable. Since the (meth) acrylate having an isocyanurate structure in the skeleton is further caprolactone-modified, it becomes easier to alleviate the strain of the adhesive layer. Therefore, when the laminated body is used as a part of the product, the distortion of the adhesive layer caused by changes in temperature and humidity can be further relaxed, so that the adhesion between the adhesive layer and the adherend is less likely to decrease. With the passage of time, it becomes easy to prevent the transfer layer from peeling off from the adherend and falling off.

When the ionizing radiation curable resin composition contained in the adhesive layer is an ultraviolet curable resin composition, it contains a photopolymerization initiator.
Examples of the photopolymerization initiator include one or more selected from acetophenone, benzophenone, α-hydroxyalkylphenone, Michler ketone, benzoin, benzyl dimethyl ketal, benzoyl benzoate, α-acyl oxime ester, thioxanthones and the like.
When the layer in contact with the adhesive layer contains an ultraviolet curable resin composition, the photopolymerization initiator contained in the adhesive layer initiates photopolymerization different from that of the photopolymerization initiator contained in other layers constituting the transfer layer. It may be an agent, or it may be the same photopolymerization initiator.

When the layer in contact with the adhesive layer contains an ultraviolet curable resin composition, the photopolymerization initiator contained in the adhesive layer is different from the photopolymerization initiator contained in the layer in contact with the adhesive layer. Since it becomes easy to control the curing timing and the degree of curing of the ultraviolet curable resin composition in the process of forming the transfer layer and the process of forming the laminate, the strain of each layer can be reduced and the strength between the layers can be increased. This makes it easier to prevent delamination of the transfer layer.

When the layer in contact with the adhesive layer contains an ultraviolet curable resin composition, the photopolymerization initiator contained in the adhesive layer is the same photopolymerization initiator as the photopolymerization initiator contained in the layer in contact with the adhesive layer. As a result, the adhesive layer and the layer in contact with the adhesive layer are likely to be chemically bonded, and the interlayer strength is likely to be increased. Therefore, delamination can be less likely to occur in the transfer layer, and the scratch resistance of the surface of the laminate can be easily improved. Further, by increasing the adhesion between the layers, the entire transfer layer is integrated, and the scratches generated are less noticeable.

When the ionizing radiation curable resin composition contained in the adhesive layer is an ultraviolet curable resin composition, the content of the photopolymerization initiator shall be 1 part by mass or more with respect to 100 parts by mass of the ultraviolet curable resin composition. Is preferable, and it is more preferably 2 parts by mass or more, and further preferably 3 parts by mass or more.
By adding 1 part by mass or more of the photopolymerization initiator to 100 parts by mass of the ultraviolet curable resin composition, it becomes easy for the photopolymerization initiator to remain near the surface of the adhesive layer when the adhesive layer is formed, and the adhesive layer is formed. The layer in contact with the UV curable resin composition can be easily chemically bonded.
If the content of the photopolymerization initiator is excessive, the above-mentioned effect is not improved, but the physical properties of the resin layer are deteriorated. Therefore, the content of the photopolymerization initiator in the resin layer forming ink is determined. It is preferably 10 parts by mass or less with respect to 100 parts by mass of the ultraviolet curable resin composition.

When the ionizing radiation curable resin composition contained in the adhesive layer is an ultraviolet curable resin composition, it is preferable to further contain a photopolymerization accelerator.
The photopolymerization accelerator can reduce the polymerization inhibition by air at the time of curing and accelerate the curing rate, and is selected from, for example, p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid ethyl ester and the like. One or more types can be mentioned.

The adhesive layer of the present invention may contain various additives as long as the effects of the present invention are not impaired. For example, an antioxidant, a pigment, a silane coupling agent, a light stabilizer, and an ultraviolet absorber. Etc. can be blended.

(Hard coat layer)
The hard coat layer is formed in the layer constituting the transfer layer of the transfer sheet, for example, in order to give the transfer layer a predetermined surface hardness and scratch resistance.

The hard coat layer preferably contains a curable resin composition such as a thermosetting resin composition or an ionizing radiation curable resin composition in order to give the transfer layer a predetermined surface hardness, and is preferably an ionizing radiation curable resin. More preferably, it contains a composition.
Here, the curable resin composition refers to a cured product of the curable resin composition and an uncured product of the curable resin composition. The ratio of the cured product of the curable resin composition contained in the curable resin composition of the hard coat layer is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more.

The thermosetting resin composition is a composition containing at least a thermosetting resin, and is a resin composition that is cured by heating. Examples of the thermosetting resin include acrylic resin, urethane resin, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, and silicone resin. In the thermosetting resin composition, a curing agent is added to these curable resins as needed.
When the curable resin composition of the hard coat layer contains the thermosetting resin composition, the preferable ratio of the cured product of the thermosetting resin composition contained in the thermosetting resin composition is described above. This is the same as the preferable ratio of the cured product of the curable resin composition contained in the curable resin composition of the hard coat layer.

As the ionizing radiation curable resin composition contained in the hard coat layer, for example, the ionizing radiation curable resin composition exemplified in the above-mentioned adhesive layer can be used.
When the curable resin composition of the hard coat layer contains the ionizing radiation curable resin composition, the preferable ratio of the cured product of the ionizing radiation curable resin composition contained in the ionizing radiation curable resin composition is , The same as the preferable ratio of the cured product contained in the curable resin composition of the hard coat layer described above.

The hard coat layer may further contain particles in order to impart antiglare properties to the transfer layer.

When imparting antiglare property to the hard coat layer, either organic particles or inorganic particles can be used as the particles. Examples of the organic particles include particles composed of polymethylmethacrylate, polyacrylic-styrene copolymer, melamine resin, polycarbonate, polystyrene, polyvinyl chloride, benzoguanamine-melamine-formaldehyde condensate, silicone, fluororesin, polyester resin and the like. Can be mentioned. Examples of the inorganic particles include particles made of silica, alumina, antimony, zirconia, titania and the like.

The average particle size of the particles in the hard coat layer varies depending on the thickness of the hard coat layer and cannot be unequivocally determined, but is preferably 1.0 μm or more and 10.0 μm or less, and is preferably 2.0 μm or more and 8.0 μm or less. More preferably, it is 3.0 μm or more and 6.0 μm or less.

The content of particles in the hard coat layer varies depending on the desired degree of antiglare, so it cannot be said unconditionally, but it may be 1 part by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the resin component. It is preferably 5 parts by mass or more and 50 parts by mass or less, and more preferably 10 parts by mass or more and 30 parts by mass or less.

The hard coat layer improves the surface hardness of the transfer layer, imparts antistatic properties, controls the refractive index, and adjusts the shrinkage of the hard coat layer due to curing of the curable resin composition. Therefore, fine particles having an average particle diameter of less than 500 nm may be contained.
When improving the surface hardness of the transfer layer, the fine particles are preferably inorganic oxides such as silica, alumina, antimony, zirconia and titania.

It is preferable that the hard coat layer further contains a leveling agent in order to improve the surface smoothness. Examples of the leveling agent include fluorine-based and silicone-based.

The content of the leveling agent is preferably 0.15 parts by mass or more and 2.5 parts by mass or less, and 0.20 parts by mass or more and 2.0 parts by mass with respect to 100 parts by mass of the curable resin contained in the hard coat layer. It is more preferably parts by mass or less, and further preferably 0.25 parts by mass or more and 1.0 parts by mass or less. By setting the content of the leveling agent to 0.15 parts by mass or more, the surface of the hard coat layer can be easily smoothed. Further, by setting the content of the leveling agent to 2.5 parts by mass or less, the adhesion between the hard coat layer and the antireflection layer is improved.

As a method for forming the hard coat layer, various known methods such as roll coat, gravure coat, air knife coat, comma coat, die coat and the like are used, and gravure coat and roll coat are preferably used from the viewpoint of productivity.

The thickness of the hard coat layer is preferably 1 μm or more, more preferably 2 μm or more, and even more preferably 3 μm or more. When the hard coat layer is 1 μm or more, the surface hardness of the laminate to which the transfer layer is transferred can be increased. The thickness of the hard coat layer is preferably 10 μm or less, more preferably 7 μm or less, and even more preferably 5 μm or less. By setting the thickness of the hard coat layer to 10 μm or less, the transfer layer does not become thicker than necessary, and cracks are less likely to occur in the transfer layer when the transfer layer is transferred to the laminate.

(Anchor layer)
The anchor layer is preferably formed between the layers of the transfer layer in order to improve the adhesion between the layers of the transfer layer. By having the anchor layer, it is possible to prevent the strain of each layer, which occurs during the production of the transfer sheet or the transfer process of the transfer layer, from propagating to other layers, and it becomes easy to prevent the strain and cracks of the transfer layer from occurring. .. For example, due to the presence of the anchor layer, the strain when the adhesive layer is softened by heating is relaxed by the anchor layer, the strain is suppressed from propagating to other layers (particularly the antireflection layer), and the other layers (especially the antireflection layer) are suppressed. It is possible to easily suppress the occurrence of cracks in the antireflection layer).
Further, it is particularly preferable that the anchor layer is formed between the hard coat layer and the adhesive layer.

The anchor layer preferably contains a curable resin composition such as an ionizing radiation curable resin composition or a thermosetting resin composition in order to improve the adhesion between the layers of the transfer layer, and the ionizing radiation curable resin composition. It is more preferable to include a substance.
Here, the curable resin composition refers to a cured product of the curable resin composition and an uncured product of the curable resin composition. The ratio of the cured product of the curable resin composition contained in the curable resin composition of the anchor layer is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more.

As the thermosetting resin composition contained in the anchor layer, for example, the thermosetting resin composition exemplified in the above-mentioned hard coat layer can be used. When the curable resin composition of the anchor layer contains the thermosetting resin composition, the preferable ratio of the cured product of the thermosetting resin composition contained in the thermosetting resin composition is the above-mentioned anchor. It is the same as the preferable ratio of the cured product of the curable resin composition contained in the curable resin composition of the layer.
Further, as the ionizing radiation curable resin composition contained in the anchor layer, for example, the ionizing radiation curable resin composition exemplified in the above-mentioned adhesive layer can be used. When the curable resin composition of the anchor layer contains the ionizing radiation curable resin composition, the preferable ratio of the cured product of the ionizing radiation curable resin composition contained in the ionizing radiation curable resin composition is It is the same as the preferable ratio of the cured product of the curable resin composition contained in the curable resin composition of the anchor layer described above.

The thickness of the anchor layer is preferably 1 μm or more, more preferably 2 μm or more, and even more preferably 3 μm or more. By setting the thickness of the anchor layer to 1 μm or more, it becomes easy to improve the adhesion between the anchor layer and the layer in contact with the anchor layer, and further, the distortion of each layer that occurs during the production of the transfer sheet or the transfer process of the transfer layer. Is prevented from propagating to other layers, and it becomes easy to prevent distortion and cracks from occurring in the transfer layer.
The thickness of the anchor layer is preferably 10 μm or less, more preferably 7 μm or less, and even more preferably 5 μm or less. By setting the thickness of the anchor layer to 10 μm or less, it becomes easier to utilize the texture of the adherend when the laminate is formed and then touched by hand, and especially when the adherend is glass, the hardness of the glass is increased. It is easy to reflect on the surface of the laminate, and it is easy to increase the surface hardness. Further, by setting the thickness of the anchor layer to 10 μm or less, it becomes difficult to prevent the heat applied from the release base material A side from propagating to the adhesive layer during the transfer step of the transfer layer, and the adhesive layer can be heated efficiently. Therefore, it becomes easy to suppress cracks in the transfer layer due to overheating.

If the anchor layer is formed between the hard coat layer and the adhesive layer, the ratio T _{A /} T _B of the thickness of the anchor layer and the (T _A) and the thickness of the adhesive layer (T _B) is 0.3 or more It is preferably 0.5 or more, more preferably 0.7 or more. By T A _/ T _B is 0.3 or more, when heated in the transfer process, distortion of the adhesive layer softened by heating, hardly propagated to other layers (particularly antireflective layer), another layer (Especially the antireflection layer) is less likely to crack.
_The upper limit is preferably 5.0 or less of the T A / _{T B,} more preferably 3.0 or less, more preferably 2.0 or less. By T A _/ T _B is 5.0 or less, during the transfer step of the transfer layer, heat applied from the release substrate A side becomes difficult to inhibit the propagating in the adhesive layer, the adhesive layer efficiently heated Therefore, it becomes easy to suppress cracks in the transfer layer due to overheating.

If the anchor layer is formed between the hard coat layer and the adhesive layer, the ratio T _{A /} T _C of the thickness (T _C) of the thickness of the anchor layer and the (T _A) Hard coat layer 0.3 Is more preferable, 0.5 or more is more preferable, and 0.7 or more is further preferable. By T A _/ T _C is 0.3 or more, the influence of the curing shrinkage that occurs upon curing the hard coat layer is not easily propagated to the adhesive layer, prevents distortion or wrinkles occur in the adhesive layer By making it easier, the adhesive strength between the peeling base material B and the adhesive layer, which will be described later, is lowered, and it is possible to easily prevent unintentional peeling.
_The upper limit of T A / _{T C} is preferably 5.0 or less, more preferably 3.0 or less, more preferably 2.0 or less. By T A _/ T _C is 5.0 or less, during the transfer step of the transfer layer, heat applied from the release substrate A side becomes difficult to inhibit the propagating in the adhesive layer, the adhesive layer efficiently heated Therefore, it becomes easy to suppress distortion and cracks in the transfer layer due to overheating.

(Surface shape of transfer layer)
In the transfer sheet of the present invention, the surface shape of the transfer layer on the release base material A side is preferably substantially smooth. Specifically, the surface shape of the antireflection layer on the peeling base material A side is preferably such that the arithmetic average roughness Ra of JIS B 0601: 1994 at a cutoff value of 0.25 mm is 0.04 μm or less. Since the surface shape of the antireflection layer on the peeling base material A side is substantially smooth, it becomes easy to utilize the texture of the adherend when touched by hand.

Ra on the surface of the transfer base A side of the release base material is, for example, a transfer layer cut from a transfer sheet cut to 100 mm × 100 mm onto a glass base material (manufactured by AGC, trade name “Dragonrail”) having a thickness of 0.7 mm. An evaluation sample transferred according to the method to the examples described later is prepared, the sample is placed on a horizontal plane, JIS B 0601: 1994 is compliant, and the measurement can be performed under the following measurement conditions.
<Measurement conditions for Ra>
-Reference length (cutoff value of roughness curve λc): 0.25 mm
-Evaluation length (reference length (cutoff value λc) x 5): 1.25 mm
・ Feeding speed of stylus: 0.1 mm / s
・ Vertical magnification: 100,000 times ・ Horizontal magnification: 50 times ・ Skid: Not used (no contact with the measurement surface)
-Cut-off filter type: Gaussian-JIS mode: JIS1994

[Peeling base material B]
The transfer sheet may have the release base material B on the surface of the adhesive layer opposite to the release base material A in order to improve the handleability.

When the peel strength between the peeling base material A and the transfer layer is defined as P1 and the peeling strength between the peeling base material B and the adhesive layer is defined as P2, P2 <P1 is required. When P2 <P1, the peeling base material B can be peeled off before the peeling base material A.
The difference (P1-P2) between the peel strength P1 and the peel strength P2 is preferably 15 mN / 25 mm or more, preferably 40 mN / 25 mm or more, in order to facilitate peeling of only the peel base material B before transfer. More preferably, it is 100 mN / 25 mm or more. If the difference is too large, it may be difficult to peel off the peeling base material A after transfer. Therefore, the difference is preferably 450 mN / 25 mm or less, and more preferably 350 mN / 25 mm or less. ..

The peel strength between the peeling base material B and the adhesive layer is preferably 10 mN / 25 mm or more, more preferably 20 mN / 25 mm or more, and further preferably 30 mN / 25 mm or more. When the peel strength is 10 mN / 25 mm or more, it is possible to prevent the peel base material B from peeling from the adhesive layer at an unintended timing. The peel strength between the peeling base material B and the adhesive layer is preferably 90 mN / mm or less, more preferably 80 mN / mm or less, and further preferably 70 mN / mm or less. When the peeling strength is 90 mN / mm or less, when the peeling base material B is peeled off and removed, the above-mentioned peeling base material A is suppressed from being peeled off, and only the peeling base material B can be easily peeled off.

The release base material B is not particularly limited as long as it can be separated from the transfer layer, and a plastic film is preferably used.
As the plastic film used as the peeling base material B, the same ones as those exemplified in the plastic film of the peeling base material A can be used.
Among the illustrated plastic films, polyester is preferably used as the release base material B in order to improve handleability.

The thickness of the release base material B is not particularly limited, but in order to improve handleability, it is preferably 10 μm or more and 200 μm or less, more preferably 20 μm or more and 150 μm or less, and further preferably 30 μm or more and 100 μm or less. preferable.

The thickness of each layer constituting the transfer sheet is, for example, the thickness of 20 points from the cross-sectional image taken by using a scanning electron microscope (SEM), a transmission electron microscope (TEM), or a scanning transmission electron microscope (STEM). It can be measured and calculated from the average value of 20 values. When the film thickness to be measured is on the order of μm, it is preferable to use SEM, and when the film thickness is on the order of nm, it is preferable to use TEM or STEM. In the case of SEM, the acceleration voltage is preferably 1 kV or more and 10 kV or less, and the magnification is preferably 1000 times or more and 7000 times or less. In the case of TEM or STEM, the acceleration voltage is 10 kV or more and 30 kV or less, and the magnification is 50,000 times or more and 300,000 times or less. Is preferable.

[Laminate]
The laminate of the present invention is characterized in that an adhesive layer, a hard coat layer and an antireflection layer are contained in this order on a glass base material, and the adhesive layer contains a thermoplastic resin and an ionizing radiation curable resin composition. ..

In the ionizing radiation curable resin composition in the adhesive layer of the laminate, the ratio of the cured product of the ionizing radiation curable resin composition is preferably 80% by mass or more, more preferably 90% by mass or more, and 100% by mass. Is even more preferable.
The ratio of the cured product of the ionizing radiation curable resin composition in the adhesive layer of the laminate is preferably higher than the ratio of the cured product of the ionizing radiation curable resin composition in the adhesive layer of the transfer sheet. That is, it is preferable to irradiate ionizing radiation during the production of the laminate to increase the degree of curing of the ionizing radiation curable resin composition of the adhesive layer of the laminate rather than the adhesive layer of the transfer sheet.

FIG. 2 is a cross-sectional view showing an embodiment of the laminated body of the present invention. The laminated body 2 of FIG. 2 has an adhesive layer 40, a hard coat layer 30, and an antireflection layer 20 on the adherend 50 in this order.
Although the laminated body 2 of FIG. 2 is not shown, an anchor layer may be provided between the layers in order to improve the adhesion of each layer constituting the laminated body 2.

The embodiment of the antireflection layer constituting the laminated body of the present invention is the same as the embodiment of the antireflection layer of the transfer sheet described above.

The adhesive layer of the laminate of the present invention needs to contain an ionizing radiation curable resin composition and a thermoplastic resin. If the adhesive layer does not contain a thermoplastic resin, the adhesiveness between the adhesive layer and an adherend such as glass is lowered, and a predetermined function is not imparted to the surface of the laminate. Further, if the adhesive layer does not contain an ionizing radiation curable resin, the hardness of the transfer layer becomes low, and the surface hardness of the laminated body cannot be increased.

The embodiment of the thermoplastic resin contained in the adhesive layer of the laminate is the same as the embodiment of the thermoplastic resin contained in the adhesive layer of the transfer sheet described above.
Further, the embodiment of the ionizing radiation curable resin contained in the adhesive layer of the laminated body is the same as the embodiment of the ionizing radiation curable resin contained in the adhesive layer of the transfer sheet described above. However, the preferable ratio of the cured product of the ionizing radiation curable resin contained in the ionizing radiation curable resin of the laminated body is preferably as described above.

Contained in the adhesive layer of the laminate, the weight ratio M _{B /} M _A of the mass M _B of the mass M _A of the thermoplastic resin wherein the ionizing radiation curable resin composition is preferably 0.10 or more , 0.15 or more, more preferably 0.20 or more, and particularly preferably 0.40 or more. M B _/ M _A that is 0.10 or more, it is possible to increase the hardness of the adhesive layer, the hardness of the adherend is not impaired by the adhesive layer, likely to be reflected in the surface hardness of the laminate, in particular deposition When the body is made of a hard material such as glass, the surface hardness of the laminated body can be increased, and the surface of the laminated body can be prevented from being scratched.
Further it, the mass ratio _M B / _{M A,} preferably 1.30 or less, more preferably 1.20 or less, further preferably 1.00 or less, 0.80 or less Is particularly preferable. By M A _/ M _B is 1.30 or less, improves adhesion between the adhesive layer and the adherend, possible to prevent the transfer layer is peeled off from the adherend.

The embodiment of the hard coat layer constituting the laminate of the present invention is the same as the embodiment of the hard coat layer of the transfer sheet described above. However, in the curable resin composition contained in the hard coat layer of the laminate, the ratio of the cured product of the curable resin composition contained in the cured resin composition is preferably 80% by mass or more, preferably 90% by mass or more. More preferably, it is more preferably 100% by mass.
The ratio of the cured product of the curable resin composition in the hard coat layer of the laminate is preferably higher than the ratio of the cured product of the curable resin composition in the hard coat layer of the transfer sheet. That is, during the production of the laminate, the curing of the curable resin composition is promoted by irradiation with ionizing radiation, aging, etc., and the curable resin composition of the hard coat layer of the laminate is cured rather than the hard coat layer of the transfer sheet. It is preferable to increase the degree of.

The laminate of the present invention may include an anchor layer, if necessary. The embodiment when the laminate of the present invention includes an anchor layer is the same as the embodiment of the anchor layer of the transfer sheet described above. However, in the curable resin composition contained in the anchor layer of the laminate, the ratio of the cured product of the curable resin composition contained in the cured resin composition is preferably 80% by mass or more, more preferably 90% by mass or more. It is preferably 100% by mass, and more preferably 100% by mass.
The ratio of the cured product of the curable resin composition in the anchor layer of the laminate is preferably higher than the ratio of the cured product of the curable resin composition in the anchor layer of the transfer sheet. That is, during the production of the laminate, the curing of the curable resin composition is promoted by irradiation with ionizing radiation, aging, etc., and the degree of curing of the curable resin composition of the anchor layer of the laminate is higher than that of the anchor layer of the transfer sheet. It is preferable to increase.

The laminate of the present invention has JIS K 5600-5-6 under the conditions that the number of cuts in each direction of the lattice pattern is 11 and the cut interval is 1 mm between the glass base material described later and the adhesive layer. : It is preferable that the cross-cut portion where peeling can be confirmed in the lattice pattern is less than 5% in the evaluation result of the adhesion carried out by the cross-cut method specified in 1999. When the cross-cut portion where peeling can be confirmed is less than 5%, the adhesion strength between the adherend such as a glass substrate and the adhesive layer is high, and the transfer layer is prevented from peeling off from the laminated body. can.

As for the surface hardness of the laminate of the present invention, the pencil hardness defined in JIS K 5600-5-4: 1999 scratch hardness (pencil method) is preferably H or more, and more preferably 2H or more. When the pencil hardness is H or more, the antireflection layer is less likely to be scratched, the antireflection function of the laminated body is easily improved, and the texture of the adherend is easily utilized.

[Subject]
The adherend in the laminate of the present invention is a glass base material. Examples of the glass base material include a base material made of glass such as soda-lime glass, borosilicate glass and quartz glass.
Further, the shape of the adherend is not particularly limited, and may be a flat plate shape or a three-dimensional shape.

The thickness of the adherend is preferably 0.1 mm or more and 10 mm or less, more preferably 0.5 mm or more and 8 mm or less, and further preferably 0.5 mm or more and 5 mm or less.

[Manufacturing method of transfer sheet]
The method for producing a transfer sheet of the present invention includes a step of forming an adhesive layer on the release base material B, a step of forming a hard coat layer on the adhesive layer, and a step of forming an antireflection layer on the hard coat layer. At least a step of laminating the release base material A on the antireflection layer is included.

(Adhesive layer forming process)
The step of forming the adhesive layer is a step of forming the adhesive layer on the release base material B. As a method for forming the adhesive layer, a known coating method can be used as described above, and the adhesive layer can be formed by, for example, a gravure coat.
At the time of forming the adhesive layer, the adhesive layer may or may not be irradiated with ionizing radiation.

When forming an adhesive layer, the mass ratio M _{B /} M _A of the mass M _B of the mass M _A and the ionizing radiation curable resin composition of the thermoplastic resin contained in the adhesive layer is preferably 0.10 or more , 0.15 or more, more preferably 0.20 or more, and particularly preferably 0.40 or more. Further it, the mass ratio _M B / _{M A,} preferably 1.30 or less, more preferably 1.20 or less, further preferably 1.00 or less, 0.80 or less Is particularly preferable.
By M B _/ M _A is 1.30 or less, without irradiating ionizing radiation at the time of bonding layer formed, it is possible to form a tack-free adhesive layer, it is possible to quickly proceed to the next step.
Further, as described above, when the ionizing radiation curable resin composition contained in the adhesive layer is an ultraviolet curable resin and the layer formed on the adhesive layer contains an ultraviolet curable resin, the adhesive layer and the adhesive layer are formed. The interlayer strength with the layer formed on the top can be improved, and the effect of improving the scratch resistance can be exhibited. The M B _/ M _A as 1.30 or less, and, by not irradiated with ultraviolet rays when forming the adhesive layer, can be made more remarkable the effect.

Further, a step of peeling the surface of the peeling base material B may be included before the step of forming the adhesive layer. The peeling treatment can be performed by applying the above-mentioned peeling agent to the surface where the peeling base material B comes into contact with the adhesive layer in the adhesive layer forming step. A known coating method can be used for coating the above-mentioned release agent, for example, a gravure coat can be applied.

(Hard coat layer forming process)
The hard coat layer forming step is a step of forming a hard coat layer on the adhesive layer. As a method for forming the hard coat layer, a known coating method can be used as described above, and for example, it can be formed by a gravure coat.
Further, when the hard coat layer is formed, the semi-cured state can be obtained by adjusting the irradiation amount of ionizing radiation.

When the adhesive layer is not irradiated with ionizing radiation, the ionizing radiation curable resin composition of the adhesive layer can be cured by irradiating the adhesive layer with ionizing radiation at the time of forming the hard coat.

(Anti-reflection layer forming process)
The step of forming the antireflection layer is a step of laminating a low refractive index layer and a high refractive index layer on the hard coat layer as an antireflection layer. As a method for forming the low refractive index layer and the high refractive index layer as the antireflection layer, a known wet method or dry method can be used as described above. When the wet method is used, it can be formed by applying, for example, a gravure coat. When the dry method is used, it can be formed by, for example, a chemical vapor deposition method.

(Peeling base material A forming step)
The step of forming the peeling base material A is a step of forming the peeling base material A on the antireflection layer, and can be laminated by, for example, a known laminating method.

Further, a step of forming an adhesive layer on the peeling base material A may be included before the step of forming the peeling base material A. The adhesive layer can be formed on the surface where the release base material A is in contact with the antireflection layer in the release base material A forming step. A known coating method can be used as the method for forming the adhesive layer, and the adhesive layer can be formed by, for example, a gravure coat.

(Anchor layer forming process)
The transfer sheet manufacturing step may further include a step of forming an anchor layer. The process of forming the anchor layer is a step of forming an anchor layer between the layers constituting the transfer sheet. As a method for forming the anchor layer, a known coating method can be used, and for example, it can be formed by a gravure coat.

[Manufacturing method of laminated body]
The laminate of the present invention can be produced by transferring the transfer layer of the transfer sheet of the present invention onto the adherend described above.

Further, the laminate of the present invention can be produced by transferring the transfer layer from the above-mentioned transfer sheet to the adherend by the following steps (1) to (4).
(1) A step of superimposing the above-mentioned transfer sheet on a glass base material in contact with the surface of the transfer sheet on the adhesive layer side.
(2) A step of heating and pressurizing from the peeling base material A side of the transfer sheet to bring the glass base material and the adhesive layer of the transfer sheet into close contact with each other.
(3) A step of peeling and removing the peeling base material A of the transfer sheet from the glass base material and the transfer sheet that are in close contact with each other.
(4) A step of irradiating ionizing radiation from the antireflection layer side of the transfer layer to promote curing of the transfer layer.

The steps (1) and (2) can be carried out by a laminating method in which heating and pressurization are combined with a roll transfer device or the like.

In the step (2), the surface temperature of the transfer sheet on the peeling base material A side is preferably 110 ° C. or lower, more preferably 100 ° C. or lower, further preferably 90 ° C. or lower, and particularly preferably 80 ° C. or lower. By setting the surface temperature of the transfer sheet on the release base material A side of the transfer sheet to 110 ° C. or lower in the step (2), the release base material A softens and is less likely to be deformed, and it becomes easier to prevent cracks from occurring in the transfer layer. The lower limit of the surface temperature of the transfer sheet in the step (2) is not particularly limited as long as the glass substrate and the transfer sheet are in close contact with each other, but is usually 35 ° C. or higher, preferably 40 ° C. or higher, and 45 ° C. or higher. More preferred.

Further, when the above-mentioned transfer sheet has the peeling base material B on the surface opposite to the peeling base material A of the adhesive layer, the step of the following step (0) is performed before the step of the above-mentioned step (1). It is preferable to have.
(0) A step of peeling the peeling base material B from the transfer sheet to expose the adhesive layer.

[Image display device]
The image display device of the present invention has the above-mentioned laminate of the present invention on the light emitting surface side of the display element.

The laminate is preferably arranged so that the surface on the antireflection layer side faces the surface on the side opposite to the display element with reference to the glass base material.
Further, the laminated body is preferably arranged on the outermost surface of the image display device.

Examples of the display element include a liquid crystal display element, an EL display element (organic EL display element, an inorganic EL display element), a plasma display element, and the like, and further, an LED display element such as a micro LED display element can be mentioned. These display elements may have a touch panel function inside the display element.
Examples of the liquid crystal display method of the liquid crystal display element include an IPS method, a VA method, a multi-domain method, an OCB method, an STN method, and a TSTN method. When the display element is a liquid crystal display element, a backlight is required. The backlight is arranged on the side opposite to the side having the laminated body of the liquid crystal display elements.
The image display device may be an image display device with a touch panel.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. The present invention is not limited to the embodiments described in the examples.

1. 1. Evaluation and measurement Various characteristics of the laminate obtained in Examples and Comparative Examples were evaluated according to the following procedure. The results are summarized in Table 1.

1-1. Adhesion The adhesion of the transfer layer was evaluated according to the cross-cut method specified in JIS K 5600-5-6: 1999.
The sample is a grid pattern of 10 squares x 10 squares = 100 squares (number of cuts:) after the laminates prepared in Examples and Comparative Examples are stored for 24 hours in an environment of 23 ° C. and 50% relative humidity. 11 pieces were cut in each direction of the lattice pattern, and the cutting interval was 1 mm) so that the cutting edge reached from the transfer layer to the glass substrate.
Adhesive tape (manufactured by Nichiban Co., Ltd., product name "Cellotape (registered trademark)") was attached to the cross-cut surface of the above cross-cut sample to form JIS K 5600-5-6: 1999. A peeling test was conducted in accordance with the specified cross-cut method.
Based on the results of the peeling test, the adhesion was evaluated according to the following evaluation criteria.
<Evaluation criteria>
A: Less than 5% of the cross-cut parts can be confirmed to be peeled off in the grid pattern.
B: The cross-cut portion where peeling can be confirmed in the grid pattern is 5% or more and less than 15%.
C: The cross-cut part where peeling can be confirmed in the grid pattern is 15% or more.

1-2. Pencil hardness The surface hardness of the laminate was measured as the pencil hardness in accordance with JIS K 5600-5-4: 1999 scratch hardness (pencil method).
A pencil having a predetermined hardness was moved on the surface of the laminate of Examples and Comparative Examples on the antireflection layer side at an angle of 45 ° with respect to the surface of the sample at a speed of 10 mm / sec with a load of 750 g. The hardness was measured.
For each sample, the above operation was performed three times using a pencil having each hardness. At this time, among the pencils that did not have any scratches, the hardest one was defined as the pencil hardness of the sample and is shown in Table 1.

1-3. Scratch resistance Steel wool (“Bonster # 0000”, manufactured by Nippon Steel Wool Co., Ltd.) is reciprocated 100 times with a load of ^{100 g / m 2} against the surface of the laminate of Examples and Comparative Examples on the antireflection layer side. The surface condition was visually observed and evaluated according to the following criteria.
<Evaluation criteria>
A: No change in luster is confirmed.
C: Scratches were confirmed, and gloss change was confirmed.

1-4. Drying to the touch In the preparation of the transfer sheets of Examples and Comparative Examples described later, after the adhesive layer is coated and dried, the coated surface of the adhesive layer is touched with a finger, and then the surface condition is visually observed, and the following criteria are used. Evaluated in.
<Evaluation criteria>
A: No surface change is confirmed.
B: A slight change in the surface was confirmed.
C: The trace of touching with a finger was clearly confirmed.

2. Preparation of transfer sheet and laminate (Example 1)
On the release base material B made of a polyethylene terephthalate film having a thickness of 38 μm and whose surface has been mold-released, the coating liquid 1 for forming an adhesive layer according to the following formulation is applied, dried (100 ° C., 60 seconds), and has a thickness of 3 μm. An adhesive layer was formed.
<Coating liquid 1 for forming an adhesive layer>
-Polyvinyl butyral (PVB): 10 parts by mass (manufactured by Sekisui Chemical Co., Ltd., trade name "Eslek BM-2" glass transition temperature: 67 ° C)
-Ionizing radiation curable resin A: 2 parts by mass (manufactured by Nippon Kayaku Co., Ltd., trade name "KAYARAD PET-30")
-Photopolymerization initiator: 0.08 parts by mass (manufactured by BASF, trade name "Ominirad 184")
-Solvent (isopropanol / methyl ethyl ketone = 1/15): Appropriate amount

Next, a coating liquid for forming a hard coat layer having the following formulation is applied onto the adhesive layer, dried (100 ° C. for 60 seconds), and then irradiated with ultraviolet rays from the hard coat layer side to cure the ionizing radiation curable resin composition. A hard coat layer having a thickness of 3 μm was formed.
<Coating liquid for forming a hard coat layer>
-Photopolymerization initiator 0.5 parts by mass (manufactured by BASF, trade name "Omnirad 184")
-Reactive acrylic polymer: 30.0 parts by mass (active ingredient: 35% by mass, methyl ethyl ketone / 2,6-ditertiary butyl-4-cresol mixed solvent)
-Urethane acrylate resin: 5 parts by mass (active ingredient: 50% by mass, 1-methoxy-2-propanol / PGM-AC / 2-hydroxypropyl acrylate / 2,6-di-terriary butyl-4-cresol mixed solvent )
-Leveling agent: 0.2 parts by mass (manufactured by DIC, trade name "Megafuck F-560", active ingredient: 20% by mass)
-Diluting solvent: 55.3 parts by mass (2: 8 mixed solvent of methyl isobutyl ketone and methyl ethyl ketone)

Next, a coating liquid for forming a low refractive index layer according to the following formulation is applied onto the hard coat layer, dried (100 ° C. for 60 seconds), and then irradiated with ultraviolet rays from the hard coat layer side to cure the ionizing radiation curable resin composition. To form an antireflection layer having a thickness of 100 nm. The refractive index of the low refractive index layer was 1.30.
<Coating liquid for forming a low refractive index layer>
-Photopolymerization initiator: 0.1 parts by mass (manufactured by IGM Resins, trade name "Omnirad 127")
-UV curable resin: 1.1 parts by mass (manufactured by Shin Nakamura Chemical Industry Co., Ltd., trade name "NK ester ATM-4PL")
-Hollow silica: 6.3 parts by mass (active ingredient: 1.3 parts by mass)
(Average particle size 60 nm)
-Solid silica: 0.9 parts by mass (active ingredient: 0.3 parts by mass)
(Average particle size 12 nm)
-Fluorine-based antifouling agent: 0.1 parts by mass (active ingredient: 0.005 parts by mass)
(Product name "Mega Fvck F-568" manufactured by DIC Corporation)
-Diluting solvent: 91.5 parts by mass (9: 1 mixed solvent of methyl isobutyl ketone and propylene glycol monomethyl ether acetate)

Next, a release base material A made of a polyethylene terephthalate film having an adhesive layer and a thickness of 38 μm was bonded onto the antireflection layer so that the antireflection layer and the adhesive layer faced each other to obtain a transfer sheet used in Example 1. ..

Next, the release base material B is peeled off from the obtained transfer sheet, the adhesive layer is exposed, and the transfer base material B is transferred to a glass base material (thickness 0.7 mm, manufactured by AGC Inc., trade name "Dragonrail") as an adherend. The adhesive layer of the sheet and the adherend were overlapped and laminated. After laminating, pressurize from the transfer sheet side with a laminator (manufactured by Aco Brands Japan, trade name "Desktop Roll Laminator B316A3") while heating at a laminator temperature of 100 ° C. and a transport speed of 0.5 m / min. The transfer layer of the transfer sheet and the adherend were brought into close contact with each other.
Next, the release base material A is peeled off from the adhered transfer sheet, and ultraviolet rays are irradiated from the antireflection layer side to advance the curing of the adhesive layer, the hard coat layer and the antireflection layer, and the laminate used in Example 1 is used. Got

(Example 2)
The transfer sheet and lamination of Example 2 were carried out in the same manner as in Example 1 except that the amount of the ionizing radiation curable resin A in the adhesive layer forming coating liquid 1 was changed to 4 parts by mass to form the adhesive layer. I got a body.

(Example 3)
The transfer sheet and lamination of Example 3 were carried out in the same manner as in Example 1 except that the amount of the ionizing radiation curable resin A in the adhesive layer forming coating liquid 1 was changed to 8 parts by mass to form the adhesive layer. I got a body.

(Example 4)
The transfer sheet and lamination of Example 4 were carried out in the same manner as in Example 1 except that the amount of the ionizing radiation curable resin A in the coating liquid 1 for forming the adhesive layer was changed to 12 parts by mass to form the adhesive layer. I got a body.

(Example 5)
The transfer sheet and laminate of Example 5 were obtained in the same manner as in Example 1 except that the adhesive layer was changed to the adhesive layer forming coating liquid 2 having the following formulation.
<Coating liquid 2 for forming an adhesive layer>
-Polyvinyl butyral (PVB): 10 parts by mass (manufactured by Sekisui Chemical Co., Ltd., trade name "Eslek BM-2" glass transition temperature: 67 ° C)
-Ionizing radiation curable resin B: 4 parts by mass (manufactured by Nippon Kayaku Co., Ltd., trade name "KAYARAD DPHA")
-Photopolymerization initiator: 0.08 parts by mass (manufactured by BASF, trade name "Ominirad 184")
-Solvent (isopropanol / methyl ethyl ketone = 1/15): Appropriate amount

(Example 6)
A transfer sheet and a laminate of Example 6 were obtained in the same manner as in Example 1 except that the adhesive layer was changed to the adhesive layer forming coating liquid 3 of the following formulation.
<Coating liquid for forming an adhesive layer 3>
-Polyvinyl butyral (PVB): 10 parts by mass (manufactured by Sekisui Chemical Co., Ltd., trade name "Eslek BM-2" glass transition temperature: 67 ° C)
-Ionizing radiation curable resin C: 4 parts by mass (manufactured by Shin Nakamura Chemical Industry Co., Ltd., trade name "NK ester A-9300-1CL")
-Photopolymerization initiator: 0.08 parts by mass (manufactured by BASF, trade name "Ominirad 184")
-Solvent (isopropanol / methyl ethyl ketone = 1/15): Appropriate amount

(Example 7)
A transfer sheet and a laminate of Example 7 were obtained in the same manner as in Example 1 except that the adhesive layer was changed to the adhesive layer forming coating liquid 4 having the following formulation.
<Coating liquid for forming an adhesive layer 4>
-Ethylene-vinyl acetate copolymer (EVA): 10 parts by mass (manufactured by Tosoh Corporation, trade name "Ultrasen 760", vinyl acetate content: 42%)
-Ionizing radiation curable resin A: 4 parts by mass (manufactured by Nippon Kayaku Co., Ltd., trade name "KAYARAD PET-30")
-Photopolymerization initiator: 0.08 parts by mass (manufactured by BASF, trade name "Ominirad 184")
-Solvent (isopropanol / methyl ethyl ketone = 1/15): Appropriate amount

(Example 8)
A transfer sheet and a laminate of Example 8 were obtained in the same manner as in Example 1 except that the adhesive layer was formed by changing the coating liquid 5 for forming an adhesive layer according to the following formulation.
-Polyester urethane resin: 10 parts by mass (Mw: 34000, Tg: 65 ° C)
-Ionizing radiation curable resin D: 5 parts by mass (polyfunctional urethane acrylate having an isophorone diisocyanate skeleton, Mw: 1000)
-Photopolymerization initiator: 0.08 parts by mass (manufactured by BASF, trade name "Ominirad 184")
-Solvent (toluene / methyl ethyl ketone = 4/1): Appropriate amount

(Comparative Example 1)
A transfer sheet and a laminate of Comparative Example 1 were obtained in the same manner as in Example 1 except that the adhesive layer was formed without blending an ionizing radiation curable resin.

(Comparative Example 2)
A transfer sheet and a laminate of Comparative Example 2 were obtained in the same manner as in Example 7 except that the adhesive layer was formed without blending an ionizing radiation curable resin.

From the results in Table 1, the transfer sheets and laminates of Examples 1 to 8 in which the adhesive layer is composed of a thermoplastic resin composition and an ionizing radiation curable resin have good adhesion between the transfer layer and the adherend, and further. It can be confirmed that the surface hardness and scratch resistance of the laminated body can be improved. Although not evaluated in Table 1, the laminates of Examples 1 to 8 do not have a thick support on the adherend, and therefore, the adherend (glass) when touched by hand. ) Was maintained and the texture was good.

According to the transfer sheet and the laminated body of the present invention, it is possible to provide the transfer sheet and the laminated body which can maintain a good texture of the adherend, have a high surface hardness of the laminated body, and can suppress the occurrence of scratches. Due to the above-mentioned characteristics, the transfer sheet and the laminate of the present invention are suitably used as members of an image display device such as a liquid crystal display and an organic EL display.

1: Transfer sheet 2: Laminated body 10: Peeling base material A
20: Antireflection layer 30: Hard coat layer 40: Adhesive layer 50: Adhesion 100: Transfer layer

Claims (7)

A transfer sheet having a transfer layer on the release base material A.
The transfer layer has an antireflection layer, a hard coat layer, and an adhesive layer in this order from the release base material A side.
A transfer sheet in which the adhesive layer contains a thermoplastic resin and an ionizing radiation curable resin composition. The mass ratio _M B / _{M A} of the mass _{M B} of the mass _{M A} and the ionizing radiation curable resin composition of the thermoplastic resin of the adhesive layer is 0.10 or more 1.30 or less, according to claim 1 Transfer sheet. A laminate in which an adhesive layer, a hard coat layer, and an antireflection layer are contained in this order on a glass base material, and the adhesive layer contains a thermoplastic resin and an ionizing radiation curable resin composition. The mass ratio _M B / _{M A} of the mass _{M B} of the mass _{M A} and the ionizing radiation curable resin composition of the thermosetting resin of the adhesive layer is 0.10 or more 1.30 or less, to claim 3 The laminate described. The cross cut specified in JIS K 5600-5-6: 1999 under the condition that the number of cuts in each direction of the lattice pattern is 11 and the cut interval is 1 mm between the glass base material and the adhesive layer. The laminate according to claim 3 or 4, wherein the evaluation result of the adhesiveness carried out by the method shows that the cross-cut portion where peeling can be confirmed in the lattice pattern is less than 5%. A method for producing a laminate having the following steps (1) to (4).
(1) A step of superimposing the transfer sheet according to claim 1 or 2 on a glass base material in contact with the surface of the transfer sheet on the adhesive layer side.
(2) A step of heating and pressurizing from the peeling base material A side of the transfer sheet to bring the glass base material and the adhesive layer of the transfer sheet into close contact with each other.
(3) A step of peeling and removing the peeling base material A of the transfer sheet from the glass base material and the transfer sheet that are in close contact with each other.
(4) A step of irradiating ionizing radiation from the antireflection layer side of the transfer layer to promote curing of the transfer layer. An image display device having the laminate according to any one of claims 3 to 5 on a display element.

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