Release laminate, transfer sheet, process sheet, and article using the same

Abstract

Provided is a releasable laminate that has a predetermined adhesive strength to a pressure-sensitive adhesive while allowing the pressure-sensitive adhesive to be easily peeled off. [Solution] A laminate having a release layer on a transparent plastic film, the release layer being located on the outermost surface of the laminate, and satisfying the following conditions: <Condition> Prepare adhesive tape A having a peel strength of PA (N / 10 mm) according to Method 1 of JIS Z0237:2009 (180° peeling from a stainless steel test plate). Apply adhesive tape A to the surface of the release layer side of a release laminate. Use a dropper to drip water onto the surface of the release layer side of the release laminate so that at least the area where adhesive tape A is applied and an area 1 cm outward from the outer edge of adhesive tape A are covered with water. Five minutes after the water dripping is complete, adhesive tape A is peeled according to Method 1 of JIS Z0237:2009, except that the test plate is a release laminate instead of stainless steel. When the peel strength is P2 (N / 10 mm), P2 / PA is 0.2 or less.

Description

Technical Field

[0001] The present invention relates to a release laminate, a transfer sheet, a process sheet, and an article using the same.

Background Art

[0002] In recent years, due to the miniaturization of electronic device components, in the manufacturing thereof, a method of manufacturing components is carried out in which various electronic device components are adhesively fixed on a film, and after the completion of processes such as cutting and punching, each component is peeled off from the film and used. Such a film is called a "process film" and is mainly used in the manufacture of ceramic green sheets.

[0003] As such a process film, for example, those such as Patent Document 1 have been proposed.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] The process film of Patent Document 1 imparts initial adhesiveness with an adhesive layer formed on the film, while after the completion of the process, the adhesive layer is cured by irradiating with ionizing radiation to reduce the adhesiveness, and further heated to thermally shrink the film, so that components and the like can be easily peeled off from the adhesive layer. However, the process film of Patent Document 1 requires irradiation with ionizing radiation and heating, the process is complicated, two facilities (ionizing radiation irradiation facility, heating facility) are required, and the economic efficiency is not good. Also, a process film that enables peeling of components and the like with only irradiation with ionizing radiation or heating after the completion of the process has been proposed, but it is still necessary to have an ionizing radiation irradiation facility or a heating facility.

[0006] As described above, the conventional process film had problems such as work efficiency when peeling off components or the like adhered to the film after the process was completed. Moreover, not limited to the process film, a member having a predetermined adhesive strength with respect to the adhesive and being easily peelable has not been proposed.

[0007] The present invention has been made in view of such circumstances, and an object thereof is to provide a release laminate having a predetermined adhesive strength with respect to an adhesive and being easily peelable, a transfer sheet, a process sheet, and an article using the same.

Means for Solving the Problems

[0008] In order to solve the above problems, the present invention provides the following [1] to [4]. [1] A laminate having a release layer on a transparent plastic film, wherein the release layer is located on the outermost surface of the laminate and satisfies the following Conditions 1 and 2, a release laminate. <Condition 1> Prepare an adhesive tape A having a peel strength of PA (N / 10 mm) by Method 1 (180° peel with respect to a stainless steel test plate) of JIS Z0237:2009. When the adhesive tape A is bonded to the surface on the release layer side of the release laminate and the peel strength when the adhesive tape A is peeled off in accordance with Method 1 of JIS Z0237:2009 except that the test plate is not stainless steel but the release laminate is defined as P1 (N / 10 mm), P1 / PA shows 0.75 or more. <Condition 2> Bond the adhesive tape A to the surface on the release layer side of the release laminate. Drop water with a dropper so that at least the region where the adhesive tape A is bonded and the region 1 cm outside the outer edge of the adhesive tape A on the surface on the release layer side of the release laminate are covered with water. When the peel strength when the adhesive tape A is peeled off in accordance with Method 1 of JIS Z0237:2009 except that the test plate is not stainless steel but the release laminate is defined as P2 (N / 10 mm) after 5 minutes have elapsed since the water dropping was completed, P2 / PA shows 0.2 or less. [2] A transfer sheet having a transfer layer on the release layer of the release laminate described in [1] above. [3] A process sheet having the release layer of the release laminate described in [1] above on the outermost surface. [4] An article in which the release layer of the release laminate described in [1] above is arranged to face the surface. [Advantages of the Invention]

[0009] According to the present invention, there can be provided a release laminate having a predetermined adhesive force with respect to an adhesive and capable of easily peeling an adherend by a simple process of dropping water, and a transfer sheet, a process sheet, and an article using the same. [Brief Description of the Drawings]

[0010]

Figure 1

Figure 2

[0011] [Release Laminate] The release laminate of the present invention is a laminate having a release layer on a transparent plastic film, the release layer is located on the outermost surface of the laminate, and satisfies the following conditions 1 to 2. [Condition 1] Prepare an adhesive tape A with a peel strength of PA (N / 10 mm) by the method 1 (180° peel from a stainless steel test plate) of JIS Z0237:2009. When the adhesive tape A is bonded to the surface on the release layer side of the release laminate and the peel strength when the adhesive tape A is peeled in accordance with the method 1 of JIS Z0237:2009 except that the test plate is the release laminate instead of stainless steel is defined as P1 (N / 10 mm), P1 / PA shows 0.75 or more. [Condition 2] Attach the adhesive tape A to the surface on the release layer side of the release laminate. Using a dropper, drip water so that at least the area where the adhesive tape A is attached and the area 1 cm outside the outer edge of the adhesive tape A on the surface on the release layer side of the release laminate are covered with water. When the peeling strength when peeling the adhesive tape A in accordance with Method 1 of JIS Z0237:2009, except that the test plate is the release laminate instead of stainless steel, is defined as P2 (N / 10 mm) after 5 minutes have elapsed since the dripping of water is completed, P2 / PA shows 0.2 or less.

[0012] Figures 1 and 2 are cross-sectional views showing an embodiment of the release laminate of the present invention. The release laminate 100 in Figures 1 and 2 has, in this order, a hard coat layer 20, a layer 30 containing an inorganic compound, and a release layer 40 on a transparent plastic film 10. Further, the release laminate 100 in Figure 2 has a hard coat layer 20, a layer 30 containing an inorganic compound, and a release layer 40 on both sides of the transparent plastic film 10. Note that the release laminate of the present invention is not limited to the embodiments in Figures 1 and 2. For example, between the transparent plastic film 10 and the release layer 40, there may be no layer 30 containing an inorganic compound and / or hard coat layer 20. Further, the release layer 40 does not need to be formed on the entire surface of the transparent plastic film 10 and may be provided on at least a part of the transparent plastic film 10. Further, the release laminate may have other layers (not shown).

[0013] The release laminate of the present invention needs to satisfy the following Condition 1. <Condition 1> Prepare an adhesive tape A with a peeling strength of PA (N / 10 mm) according to Method 1 of JIS Z0237:2009 (180° peeling with respect to a stainless steel test plate). Attach the adhesive tape A to the surface on the release layer side of the release laminate, and when the peeling strength when peeling the adhesive tape A in accordance with Method 1 of JIS Z0237:2009, except that the test plate is the release laminate instead of stainless steel, is defined as P1 (N / 10 mm), P1 / PA shows 0.75 or more.

[0014] Satisfying Condition 1 indicates that the adhesive tape adheres sufficiently to the surface on the release layer side of the release laminate. Moreover, satisfying Condition 1 and the subsequently described Condition 2 indicates that, in the initial stage, while the adhesive tape adheres sufficiently, it can be easily peeled off by a simple operation such as dropping water.

[0015] As the adhesive tape A used in Conditions 1 to 4, it is preferable that the peel strength in accordance with Method 1 (180° peel from a stainless steel test plate) of JIS Z0237:2009 is 3 to 7 (N / 10 mm). In addition, the adhesives of the adhesive tape A used in Conditions 1 to 4 include rubber-based adhesives, acrylic adhesives, urethane adhesives, and silicone adhesives. Also, it is preferable that the base material of the adhesive tape A is a film.

[0016] In order to easily satisfy Condition 1, it is preferable to form the release layer from the materials described later, set the thickness of the release layer within the range described later, and improve the adhesion between the release layer and the layer in contact with the release layer.

[0017] The release laminate of the present invention needs to satisfy the following Condition 2. <Condition 2> The adhesive tape A is bonded to the surface on the release layer side of the release laminate. Water is dropped with a dropper so that at least the region where the adhesive tape A is bonded and the region 1 cm outside the outer edge of the adhesive tape A on the surface on the release layer side of the release laminate are covered with water. After 5 minutes have elapsed since the dropping of water is completed, when the peel strength when peeling the adhesive tape A in accordance with Method 1 of JIS Z0237:2009 except that the test plate is the release laminate instead of stainless steel is taken as P2 (N / 10 mm), P2 / PA shows 0.2 or less.

[0018] Satisfying Condition 2 means that, by extremely simple steps such as dropping water and short-time waiting, the peel strength of the adhered object such as the adhesive tape decreases, and the adhered object such as the adhesive tape can be easily peeled off. In addition, in Condition 2 and Conditions 3 and 4 described later, the water to be dropped is preferably ion-exchanged water.

[0019] The release base material of the transfer sheet is required to have a property of good adhesiveness with the transfer layer formed on the release base material, and after the transfer layer is transferred to the adherend, it is required to have a property of being easily peeled off from the transfer layer. In addition, the process sheet is required to have a property of being able to adhere and fix electronic components etc. via an adhesive etc., and after the process is completed, it is required to have a property of being able to easily peel off the electronic components etc. from the surface of the process sheet. In addition, in showcases, show windows and windows, it is required to have a property of fixing display items such as advertisements with an adhesive tape, and when changing the display item, it is required to have a property of being able to easily peel off the adhesive tape. Therefore, the release laminate of the present invention that satisfies Condition 1 and Condition 2 is useful for the release base material of the transfer sheet and the process sheet. It is also useful to apply the release laminate of the present invention to the surfaces of showcases, show windows and windows.

[0020] In order to easily satisfy Condition 2, it is preferable to form the release layer from the materials described later and to set the thickness of the release layer within the range described later.

[0021] The release laminate of the present invention preferably further satisfies the following Condition 3. <Condition 3> Using a cotton 300-thread count flannel cloth, the surface of the release layer of the release laminate is rubbed 1000 times back and forth with a load of 500 g / cm 2 to obtain a friction laminate 1. Adhesive tape A is bonded to the surface of the friction laminate 1 on the release layer side. Using a dropper, water is dropped so that at least the area where the adhesive tape A is bonded and the area 1 cm outside the outer edge of the adhesive tape A on the surface of the release layer side of the friction laminate 1 are covered with water. After 5 minutes have elapsed since the dropping of the water was completed, except that the test plate is the friction laminate 1 instead of stainless steel, when the peel strength when peeling off the adhesive tape A in accordance with Method 1 of JIS Z0237:2009 is taken as P3 (N / 10 mm), P3 / PA shows 0.2 or less.

[0022] Condition 3 indicates that even if the surface of the release layer is rubbed many times with a flannel cloth, the characteristics of Condition 2 are maintained. In other words, satisfying Condition 3 means that the property that the adhesive strength of an adherend such as an adhesive tape decreases when water is dropped can be sustained over a long period.

[0023] The release base material of the transfer sheet and the process sheet are usually discarded after being used once. However, when Condition 3 is satisfied, since the property of reducing the adhesive strength of the adherend does not decrease due to friction, it is preferable in that the release base material of the transfer sheet and the process sheet can be used repeatedly. In addition, in showcases, show windows, and windows, the surface is cleaned daily, but by satisfying Condition 3, it becomes possible to maintain the property of reducing the adhesive strength of the adherend even by repeated cleaning. Therefore, by satisfying Condition 3, the configuration in which the release laminate of the present invention is applied to the surfaces of showcases, show windows, and windows can be made more useful, which is preferable. In this specification, "showcase" means a box whose interior can be visually recognized in a normal state, and is a concept including refrigerators and freezers.

[0024] In order to easily satisfy Condition 3, it is preferable to increase the scratch resistance of the surface of the release laminate (release layer surface). Specifically, it is preferable to dispose a layer containing an inorganic compound between the transparent plastic film and the release layer. Further, the layer containing the inorganic compound preferably further contains a binder resin. Furthermore, it is preferable to perform the treatment described later on the surface of the layer containing the inorganic compound.

[0025] The release laminate of the present invention preferably further satisfies the following Condition 4. <Condition 4> The surface of the release layer of the release laminate is rubbed with a 300-thread flannel cloth under a load of 500 g / cm 2The one that has been rubbed 5,000 times back and forth is defined as the friction laminate 2. The adhesive tape A is bonded to the surface on the release layer side of the friction laminate 2. Using a dropper, water is dropped so that at least the area where the adhesive tape A is bonded and the area 1 cm outside the outer edge of the adhesive tape A on the surface on the release layer side of the friction laminate 2 are covered with water. After 5 minutes have elapsed since the dropping of water is completed, when the peeling strength when peeling the adhesive tape A in accordance with Method 1 of JIS Z0237:2009 except that the test plate is the friction laminate 2 instead of stainless steel is defined as P4 (N / 10 mm), P4 / PA shows 0.2 or less.

[0026] <Transparent plastic film> The transparent plastic film can be formed from resins such as polyester, triacetyl cellulose (TAC), cellulose diacetate, cellulose acetate butyrate, polyamide, polyimide, polyethersulfone, polysulfone, polypropylene, polymethylpentene, polyvinyl chloride, polyvinyl acetal, polyether ketone, polymethyl methacrylate, polycarbonate, polyurethane, and amorphous olefin (Cyclo-Olefin-Polymer: COP). Among these transparent plastic films, from the viewpoints of mechanical strength and dimensional stability, a stretched film, particularly a biaxially stretched polyester film, is preferable. Among polyester films, polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) are preferable.

[0027] The thickness of the transparent plastic film is preferably 5 to 500 μm, and more preferably 10 to 200 μm. Also, the total light transmittance of the transparent plastic film in accordance with JIS K7361-1:1997 is preferably 80% or more, more preferably 90% or more, and even more preferably 95% or more.

[0028] From the perspective of improving the adhesion to the layer formed on the film, one-sided or both-sided easy adhesion treatment such as physical or chemical surface treatment such as oxidation method or unevenness method may be performed on the transparent plastic film. Also, from the same perspective, it is preferable to form an easy adhesion layer on the transparent plastic film.

[0029] <Layer containing an inorganic compound> The release laminate preferably has a layer containing an inorganic compound between the transparent plastic film and the release layer. By adopting such a configuration, the adhesion between the transparent plastic film and the release layer becomes good, and it becomes easy to satisfy Conditions 1 to 4.

[0030] The layer containing an inorganic compound can be roughly classified into those formed by the wet method and those formed by the dry method. Examples of the wet method include a method of forming by the sol-gel method using a metal alkoxide or the like, and a method of forming by applying a coating liquid containing inorganic particles in a binder resin composition. Examples of the dry method include a physical vapor deposition method or a chemical vapor deposition method using inorganic particles as a raw material. The wet method is excellent in terms of production efficiency. In addition, the layer containing an inorganic compound formed by the wet method is suitable in that it has excellent coating suitability for the release layer. Furthermore, the layer containing an inorganic compound formed by the wet method is suitable in that it easily improves the adhesion to the layer directly below (for example, a transparent plastic film, a hard coat layer). Also, among the wet methods, a method of applying and drying a coating liquid containing inorganic particles as an inorganic compound and a binder resin composition is preferable. That is, the layer containing an inorganic compound preferably contains inorganic particles as an inorganic compound and a binder resin.

[0031] The particle diameter of the inorganic particles is not particularly limited, but from the viewpoints of transparency and suppression of particle dropout, etc., the average primary particle diameter is preferably 5 to 200 nm, and more preferably 10 to 150 nm.

[0032] The average primary particle diameter of the inorganic particles can be calculated by the following operations (1) to (3). (1) Image the cross-section of the mold-releasing laminate with TEM or STEM. The acceleration voltage of TEM or STEM is preferably 10 kV to 30 kV, and the magnification is preferably 50,000 to 300,000 times. (2) Extract any 10 primary particles from the observation image and calculate the particle diameter of each primary particle. The particle diameter is measured as the distance between two straight lines in a combination of two straight lines such that the distance between the two straight lines is maximized when the cross-section of the primary particle is sandwiched by any two parallel straight lines. (3) Perform the same operation 5 times on the observation images of different screens of the same sample, and take the value obtained from the number average of a total of 50 as the average particle diameter of the primary particles.

[0033] Examples of the inorganic particles include silica, magnesium fluoride, alumina, zirconia, and titania. Among these, from the viewpoint of reducing the reflectance, low refractive index inorganic particles such as silica and magnesium fluoride are preferable. When the reflectance is lowered, it can be suitably used for applications where visibility is important, such as showcases, show windows, and windows. In addition, from the viewpoint of reducing the reflectance, the low refractive index inorganic particles preferably have voids. The inorganic particles having voids have fine voids inside and contain air in the voids, so they have a low refractive index. Examples of the inorganic particles having voids include porous inorganic particles and hollow inorganic particles, and among them, hollow inorganic particles are preferable. Among the hollow inorganic particles, hollow silica is preferable.

[0034] The hollow inorganic particles refer to particles having an outer shell layer made of an inorganic compound, with a cavity inside the particle surrounded by the outer shell layer and containing air inside the particle. The shape of the hollow inorganic particles may be any of substantially spherical shapes such as true spherical, ellipsoidal of revolution, and polyhedral shapes approximating a sphere, chain-like, needle-like, plate-like, flake-like, rod-like, fiber-like, etc. Among them, it is preferably true spherical or substantially spherical, and more preferably ellipsoidal of revolution or true spherical.

[0035] While hollow inorganic particles can reduce the refractive index, they tend to be inferior in water resistance and scratch resistance compared to other low-refractive-index inorganic particles. In particular, when using hollow particles with a large particle diameter and a high air ratio, the water resistance and scratch resistance of the layer containing the inorganic compound are likely to decrease. However, in the case where the release laminate of the present invention contains hollow inorganic particles in the layer containing the inorganic compound, the weakness of the hollow inorganic particles (decrease in water resistance and scratch resistance) can be compensated by the release layer located on the layer containing the inorganic compound. Further, when the layer containing the inorganic compound contains hollow inorganic particles, by performing the treatment described later on the surface of the layer containing the inorganic compound, the adhesion between the layer containing the inorganic compound and the release layer becomes good, and it is preferable in that the weakness of the hollow inorganic particles (decrease in water resistance and scratch resistance) can be further compensated.

[0036] The low-refractive-index inorganic particles may be surface-treated, but from the viewpoint of enhancing the adhesion between the layer containing the inorganic compound and the release layer, those without surface treatment are preferable.

[0037] The content of the inorganic particles is preferably 20 to 250 parts by mass, more preferably 30 to 230 parts by mass, and even more preferably 40 to 200 parts by mass with respect to 100 parts by mass of the binder resin of the layer containing the inorganic compound. By setting the content of the inorganic particles to 20 parts by mass or more, it is easy to improve the adhesion between the layer containing the inorganic compound and the release layer. Also, when the inorganic particles are low-refractive-index inorganic particles, by setting the content of the inorganic particles to 20 parts by mass or more, the antireflection property can be improved. Also, by setting the content of the inorganic particles to 250 parts by mass or less, it is easy to suppress a decrease in the coating film strength of the layer containing the inorganic compound, and thus to suppress a decrease in the scratch resistance of the release laminate. Also, it is possible to use the low-refractive-index inorganic particles in combination with hollow inorganic particles and other low-refractive-index inorganic particles. In this case, the ratio of the hollow inorganic particles to the total amount of the low-refractive-index inorganic particles is preferably 50% by mass or more, more preferably 60% by mass or more and 95% by mass or less, and even more preferably 70% by mass or more and 90% by mass or less.

[0038] As the binder resin of the layer containing an inorganic compound, it is preferable to contain a cured product of a curable resin composition such as a thermosetting resin composition or an ionizing radiation curable resin composition. From the viewpoint of improving scratch resistance, it is more preferable to contain a cured product of an ionizing radiation curable resin composition.

[0039] The binder resin of the layer containing an inorganic compound preferably does not substantially contain a fluorine component from the viewpoints of adhesion to the release layer and coatability of the release layer coating liquid. Not substantially containing means that the content in terms of fluorine atoms of the fluorine component with respect to the total amount of the binder resin of the layer containing an inorganic compound is 1% by mass or less, preferably 0.1% by mass or less, more preferably 0.01% by mass or less, and still more preferably 0% by mass.

[0040] A thermosetting resin composition is a composition containing at least a thermosetting resin and is a resin composition that cures by heating. Examples of the thermosetting resin include acrylic resin, urethane resin, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, silicone resin, etc. A curing agent is added to these curable resins in the thermosetting resin composition as necessary.

[0041] An 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 ethylenically unsaturated bond groups such as (meth)acryloyl group, vinyl group, allyl group, and epoxy group, oxetanyl group, etc. As the ionizing radiation curable compound, a compound having an ethylenically unsaturated bond group is preferable, a compound having two or more ethylenically unsaturated bond groups is more preferable, and among them, a polyfunctional (meth)acrylate-based compound having two or more ethylenically unsaturated bond groups is still more preferable. As the polyfunctional (meth)acrylate-based compound, either a monomer or an oligomer can be used. Note that ionizing radiation means electromagnetic waves or charged particle beams that have energy quanta capable of polymerizing or crosslinking molecules. Usually, ultraviolet rays (UV) or electron beams (EB) are used, but other electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion beams can also be used. In this specification, "(meth)acrylate" means acrylate or methacrylate, "(meth)acrylic acid" means acrylic acid or methacrylic acid, and "(meth)acryloyl group" means acryloyl group or methacryloyl group.

[0042] Among the polyfunctional (meth)acrylate compounds, examples of the bifunctional (meth)acrylate monomers include ethylene glycol di(meth)acrylate, bisphenol A tetraethoxydiacrylate, bisphenol A tetrapropoxydiacrylate, 1,6-hexanediol diacrylate, and the like. Examples of the trifunctional or higher (meth)acrylate monomers include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol tetra(meth)acrylate, isocyanuric acid-modified tri(meth)acrylate, and the like. In addition, the above (meth)acrylate monomers may be those in which a part of the molecular skeleton is modified, and those modified with ethylene oxide, propylene oxide, caprolactone, isocyanuric acid, alkyl, cyclic alkyl, aromatic, bisphenol, etc. can also be used.

[0043] Examples of the polyfunctional (meth)acrylate oligomers include acrylate-based polymers such as urethane (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, and polyether (meth)acrylate. Urethane (meth)acrylate can be obtained, for example, by the reaction of a polyhydric alcohol and an organic diisocyanate with hydroxy (meth)acrylate. Also, preferred epoxy (meth)acrylates are (meth)acrylates obtained by reacting trifunctional or higher functional aromatic epoxy resins, alicyclic epoxy resins, aliphatic epoxy resins, etc. with (meth)acrylic acid, (meth)acrylates obtained by reacting bifunctional or higher functional aromatic epoxy resins, alicyclic epoxy resins, aliphatic epoxy resins, etc. with polybasic acids and (meth)acrylic acid, and (meth)acrylates obtained by reacting bifunctional or higher functional aromatic epoxy resins, alicyclic epoxy resins, aliphatic epoxy resins, etc. with phenols and (meth)acrylic acid. The above-mentioned radiation curable compound can be used alone or in combination of two or more.

[0044] When the radiation curable compound is an ultraviolet curable compound, the radiation curable composition preferably contains additives such as a photopolymerization initiator and a photopolymerization accelerator. Examples of the photopolymerization initiator include one or more selected from acetophenone, benzophenone, α-hydroxyalkylphenone, Michler's ketone, benzoin, benzyldimethylketal, benzoyl benzoate, α-acyl oxime ester, thioxanthones, etc. In addition, the photopolymerization accelerator can reduce the polymerization inhibition by air during curing and increase the curing rate. Examples thereof include one or more selected from isoamyl p-dimethylaminobenzoate, ethyl p-dimethylaminobenzoate, etc.

[0045] When the layer containing an inorganic compound contains inorganic particles as the inorganic compound and a binder resin, it is preferable that the inorganic particles are exposed at least partially on the surface of the layer containing an inorganic compound (the surface on the release layer side of the layer containing an inorganic compound). Since the inorganic particles are exposed from the surface of the layer containing an inorganic compound, the adhesion between the layer containing an inorganic compound and the release layer can be easily improved. In order to expose inorganic particles from the surface of the layer containing an inorganic compound, after forming the layer containing an inorganic compound, it is preferable to subject the surface of the layer containing an inorganic compound to corona discharge treatment or saponification treatment. When forming a layer containing inorganic particles and a binder resin, the surface of the inorganic particles is covered with the binder resin. Here, the thickness of the binder resin covering the surface of the inorganic particles varies from place to place, with some thick and some thin. And in the areas where the surface of the inorganic particles is thinly covered with the binder resin, the thin film of the binder resin is removed by the above-mentioned corona discharge treatment or saponification treatment, and the inorganic particles are exposed.

[0046] From the viewpoint of further improving the adhesion to the release layer and maintaining the release property of the adhesive over a longer period due to water dripping, the layer containing an inorganic compound preferably contains a silane coupling agent. Examples of the silane coupling agent include alkoxysilanes such as tetraethoxysilane and methyltriethoxysilane; vinyl-based silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane; (meth)acryloyl group-containing silane coupling agents such as 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltriethoxysilane; epoxy-based silane coupling agents; amino-based silane coupling agents, etc. Among these, from the viewpoint of scratch resistance, (meth)acryloyl group-containing silane coupling agents are preferable.

[0047] The content of the silane coupling agent is preferably 5 to 60% by mass, more preferably 7 to 45% by mass, and even more preferably 10 to 30% by mass of the total solid content of the layer containing an inorganic compound.

[0048] The thickness of the layer containing an inorganic compound is not particularly limited, but when using low refractive index particles as the inorganic compound, from the viewpoint of suppressing reflectivity, it is preferably 70 to 120 nm, more preferably 80 to 110 nm, and even more preferably 85 to 105 nm. The thickness of the layer containing the inorganic compound can be calculated from the average value of the thicknesses at 20 locations measured from an image of a cross-section taken using, for example, a scanning transmission electron microscope (STEM). The thicknesses of the release layer, hard coat layer, and high refractive index layer, which will be described later, can also be calculated in the same manner.

[0049] When low refractive index particles are used as the inorganic compound, the refractive index of the layer containing the inorganic compound (low refractive index layer) is preferably 1.26 to 1.37, more preferably 1.28 to 1.35, and even more preferably 1.30 to 1.33. In this specification, the refractive index can be calculated, for example, by fitting the reflection spectrum measured by a reflection photometer and the reflection spectrum calculated from an optical model of a multilayer thin film using the Fresnel coefficient.

[0050] <Release layer> The release layer is formed on the outermost surface of the release laminate. The release layer is required not to swell or dissolve when water is dropped under Conditions 2 to 4.

[0051] The release layer is preferably a cured product of a release layer forming composition containing an organosol-dispersed silica sol. An organosol-dispersed silica sol is a colloidal solution in which colloidal silica with a particle size on the nano order is dispersed in an organic solvent. By applying a release layer forming composition containing an organosol-dispersed silica sol and heating or the like to cause dehydration condensation of the silica sol, a cured product of the release layer forming composition containing an organosol-dispersed silica sol can be obtained. Examples of the organic solvent of the organosol-dispersed silica sol include alcohols, glycols, esters, ketones, ethers, saturated hydrocarbons, unsaturated hydrocarbons, and the like. From the viewpoint of making the particle size of the silica sol within the range of the thickness of the release layer described later, the particle size of the silica sol is preferably 1 to 20 nm.

[0052] Specific examples of the organic solvent-dispersed silica sol include IPA-ST (particle size: approximately 12 nm), IPA-ST-UP (particle size: approximately 9 to 15 nm), MIBK-ST (particle size: approximately 12 nm), PMA-ST (particle size: approximately 12 nm), PGM-ST (particle size: approximately 12 nm), and MIBK-SD (particle size: approximately 12 nm) manufactured by Nissan Chemical Industries, Ltd.; PL-1-IPA (10 to 15 nm), PL-1-TOL (10 to 15 nm), PL-1-PGME (10 to 15 nm), and PL-1-MEK (10 to 15 nm) manufactured by Fuso Chemical Industry Co., Ltd.; and Sururia, etc. manufactured by JGC Catalysts and Chemicals Ltd.

[0053] Further, the release layer is preferably a cured product of a release layer-forming composition containing a modified product of an organic solvent-dispersed silica sol. Examples of the modified product of the organic solvent-dispersed silica sol include those obtained by reacting the silanol of the silica sol with a silane coupling agent represented by the following formula (I). The cured product of the composition containing the modified product (obtained by reacting the silanol of the silica sol with the silane coupling agent represented by the following formula (I)) has a high level of hydrophilicity, and due to the presence of the organic group, it has adhesiveness to the adhesive tape, so it can easily satisfy Condition 1. In addition, the cured product of the composition containing the modified product has a high level of hydrophilicity, water enters between the adhesive tape attached to the release layer and the surface of the release layer, weakening the adhesive force of the adhesive tape, and it can easily satisfy Condition 2. Further, the cured product of the composition containing the modified product has excellent adhesion to the layer containing the inorganic compound and can improve the scratch resistance of the release laminate, so it can easily satisfy Condition 3. Furthermore, since the cured product of the composition containing the modified product has a low refractive index of about 1.4, it can easily lower the reflectance. The above-described actions are considered to be caused by "the cured product of the composition containing the modified product having minute hydrophilic domains and hydrophobic domains on its surface" and "the relationship that the coordination energy of water to the hydrophilic domain > the binding force between the hydrophobic domain and the components of the pen holds". Also, the reason why the release layer does not peel off when water is dropped is considered to be that the modified product and the inorganic compound in the layer containing the inorganic compound are chemically bonded.

[0054] (W) 3-k (R) k Si-R 1 -(X-R 2 ) m -N + (R 3 )(R 4 )-R 5 -Y (I) [In formula (I), W represents an alkoxy group having 1 to 3 carbon atoms, R represents an alkyl group having 1 to 3 carbon atoms, k represents 0 or 1, and R 1 represents an alkylene group having 1 to 5 carbon atoms, X represents -NHCOO-, -NHCONH- or -S-, m represents 0 or 1, and R 2 represents an alkylene group having 1 to 10 carbon atoms which may contain an ether bond, an ester bond or an amide bond, or -CH2CH2N + (CH3){(CH2) n Y)}CH2CH2OCH2CH2-, R 3 and R 4 may be the same or different and each represents an alkyl group having 1 to 3 carbon atoms, R 5 represents a methylene group, an ethylene group, a propylene group or a methylenephenylene group, and Y represents -COO - or -SO3 - .]

[0055] Examples of the R (alkyl group having 1 to 3 carbon atoms) in the above formula (I) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, etc. Among these, a methyl group is preferred. Examples of the R 1 (alkylene group having 1 to 5 carbon atoms) in the above formula (I) include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group. Among these, a trimethylene group is preferred. Examples of the R 2 in the above formula (I) preferably include an ethylene group, a trimethylene group, an ethyleneoxyethylene group and -CH2CH2N + (CH3){(CH2) n Y)}CH2CH2OCH2CH2-. Examples of the R 3 and R 4Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group and an ethyl group, and among these, a methyl group is preferred.

[0056] Specific examples of the silane coupling agent of the above formula (I) include the following compounds. (CH3O)3SiCH2CH2CH2N + (CH3)2CH2COO - (C2H5O)3SiCH2CH2CH2NHCOOCH2CH2N + (CH3)2CH2COO - (C2H5O)3SiCH2CH2CH2NHCOOCH2CH2CH2N + (CH3)2CH2COO - (C2H5O)3SiCH2CH2CH2NHCOOCH2CH2CH2CH2N + (CH3)2CH2COO - (C2H5O)3SiCH2CH2CH2NHCOOCH2CH2OCH2CH2N + (CH3)2CH2COO - (C2H5O)3SiCH2CH2CH2NHCOOCH2CH2N + (CH3)(CH2COO - )CH2CH2OCH2CH2N + (CH3)2CH2COO - (C2H5O)3SiCH2CH2CH2NHCONHCH2CH2N + (CH3)2CH2COO - (C2H5O)3SiCH2CH2CH2NHCONHCH2CH2CH2N + (CH3)2CH2COO - (CH3O)3SiCH2CH2CH2SCH2CH2CH2N + (CH3)2CH2COO - (CH3O)3SiCH2CH2CH2SCH2CH2COOCH2CH2N + (CH3)2CH2COO- (CH3O)3SiCH2CH2CH2N + (CH3)2CH2CH2COO - (CH3O)3SiCH2CH2CH2N + (CH3)2CH2C6H4COO - (C2H5O)2Si(CH3)CH2CH2CH2N + (CH3)2CH2COO - (CH3O)3SiCH2CH2CH2N + (CH3)2CH2CH2CH2SO3 - (C2H5O)3SiCH2CH2CH2NHCOOCH2CH2N + (CH3)2CH2CH2CH2SO3 - (C2H5O)3SiCH2CH2CH2NHCOOCH2CH2CH2N + (CH3)2CH2CH2CH2SO3 - (C2H5O)3SiCH2CH2CH2NHCOOCH2CH2CH2CH2N + (CH3)2CCH2CH2CH2SO3 - (C2H5O)3SiCH2CH2CH2NHCOOCH2CH2OCH2CH2N + (CH3)2CH2CH2CH2SO3 - (C2H5O)3SiCH2CH2CH2NHCOOCH2CH2N + (CH3)(SO3 - )CH2CH2OCH2CH2N + (CH3)2CH2CH2CH2SO3 - (C2H5O)3SiCH2CH2CH2NHCONHCH2CH2N + (CH3)2CH2CH2CH2SO3 - (C2H5O)3SiCH2CH2CH2NHCONHCH2CH2CH2N + (CH3)2CH2CH2CH2SO3 - (CH3O)3SiCH2CH2CH2SCH2CH2CH2N + (CH3)2CH2CH2CH2SO3 - (CH3O)3SiCH2CH2CH2SCH2CH2COOCH2CH2N + (CH3)2CH2CH2CH2SO3 - (C2H5O)2Si(CH3)CH2CH2CH2N + (CH3)2CH2CH2CH2SO3 -

[0057] The silane coupling agent of formula (I) can be obtained by reacting a silicon compound containing a dialkylamino group (for example, a silicon compound containing a dimethylamino group) with a haloacetic acid compound, a sultone ring compound or a lactone ring compound.

[0058] The temperature at which the silane coupling agent of formula (I) is added is not limited, but it is preferably between about 20 °C and the boiling point of the solvent. The reaction temperature is also not limited, but it is preferably between about 20 °C and the boiling point of the solvent. The reaction time is also not limited, but it is preferably from 10 minutes to 48 hours, more preferably from 6 hours to 24 hours.

[0059] Examples of the solvent used in the reaction for obtaining the silane coupling agent of formula (I) include ester solvents such as methyl acetate, ethyl acetate and butyl acetate, alcohol solvents such as methanol, ethanol, isopropanol, n-butanol, tert-butanol, pentanol, ethylene glycol, propylene glycol, propylene glycol monomethyl ether and 1,4-butanediol, ether solvents such as diethyl ether, tetrahydrofuran and dioxane, ketone solvents such as acetone and methyl ethyl ketone, aprotic solvents such as dimethyl sulfoxide and N,N-dimethylformamide, aromatic hydrocarbon solvents such as toluene and xylene, and mixed solvents thereof.

[0060] When obtaining the silane coupling agent of formula (I), the reaction temperature is preferably the boiling point of the solvent used or higher, and the reaction may be carried out under pressure to reach a temperature above the boiling point. The reaction time is usually from 6 hours to 36 hours, preferably from 8 hours to 36 hours, and more preferably from 8 hours to 24 hours.

[0061] As the silicon compound containing a dimethylamino group which is a raw material of the silane coupling agent of formula (I), commercially available products can be used as they are. Alternatively, a commercially available alcohol containing a dimethylamino group (for example, 2-dimethylaminoethanol, 3-dimethylaminopropanol, 4-dimethylaminobutanol, 2-dimethylaminoethoxyethanol, N,N,N'-trimethyl-N'-(2-hydroxyethyl)-bis(2-aminoethyl ether, etc.) is reacted with a silane coupling agent having an isocyanate group (for example, 3-isocyanatopropyltriethoxysilane, etc.) to obtain a compound having a -NHCOO- group, or a commercially available amine containing a dimethylamino group (for example, N,N-dimethylethylenediamine, N,N-dimethyl-1,3-propanediamine, etc.) is reacted with a silane coupling agent having an isocyanate group (for example, 3-isocyanatopropyltriethoxysilane, etc.) to obtain a compound having a -NHCONH- group and use it. Also, a thiol group-containing silicon compound (for example, 3-mercaptopropyltrimethoxy, 3-mercaptopropylmethyldimethoxysilane, etc.) is reacted with dimethylallylamine, 2-(dimethylamino)ethyl acrylate, 2-(dimethylamino)ethyl methacrylate, N-[3-(dimethylamino)propyl]acrylamide, N-[3-(dimethylamino)propyl]methacrylamide, etc. to obtain a thioether group-containing silicon compound and use it.

[0062] As the solvent when reacting the silanol of the silica sol with the silane coupling agent of formula (I), there may be mentioned alcohol solvents: methanol, ethanol, isopropanol, n-butanol, t-butanol, pentanol, ethylene glycol, propylene glycol, 1,4-butanediol, etc.; ether solvents: diethyl ether, tetrahydrofuran, dioxane, etc.; ketone solvents: acetone, methyl ethyl ketone, etc.; aprotic solvents: dimethyl sulfoxide, N,N-dimethylformamide, etc.; water; and mixed solvents thereof. Among these, preferred are alcohol solvents and water, and these solvents can be used singly or in combination of two or more.

[0063] The amount of the raw material silica sol with respect to 100 parts by mass of the solvent is preferably 1 to 50 parts by weight, more preferably 1 to 30 parts by weight.

[0064] The amount of the silane coupling agent of formula (I) with respect to the silica sol is preferably 0.1 to 10.0 mmol, more preferably 0.5 to 5.5 mmol, per 1 g of the silica sol. By setting it to 0.1 mmol or more, it becomes easier to improve the hydrophilicity of the cured product. By setting it to 10.0 mmol or less, self-condensation of the silane coupling agents can be suppressed, and it is possible to suppress a decrease in the hardness of the cured product due to a shortage of the silanol groups of the silica sol and a decrease in the scratch resistance of the release layer.

[0065] The modified product of the above-mentioned organosol-dispersed silica sol (obtained by reacting the silanol of the silica sol with the silane coupling agent of formula (I)) is modified with a functional group represented by the following formula (II). (-O-) 3-k (R) k Si-R 1 -(X-R 2 ) m -N + (R 3 )(R 4 )-R 5 -Y (II) Embodiments of each symbol (k, R, Y, etc.) in formula (II) are the same as those of each symbol in the above formula (I).

[0066] In addition, examples of the modified product of the organic solvent-dispersed silica sol include those obtained by reacting the silanol of the silica sol with a silane coupling agent containing a (meth)acryloyl group. Examples of such a silane coupling agent containing a (meth)acryloyl group include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltriethoxysilane, and the like.

[0067] The release layer-forming composition containing the modified product of the organic solvent-dispersed silica sol may further contain other curing components such as a normal organic solvent-dispersed silica sol and a curable resin composition. As the curable resin composition contained in the release layer-forming composition, the same one as the curable resin composition exemplified in the layer containing an inorganic compound can be used. By including a curable resin composition in the release layer-forming composition, the adhesion to the layer containing an inorganic compound can be further enhanced. From the viewpoint of the balance between the hydrophilicity of the release layer and the adhesion to the layer containing an inorganic compound, the content of the curable resin composition is preferably 5 to 30 parts by mass with respect to 100 parts by mass of the active ingredient of the silica sol.

[0068] The release layer-forming composition can be applied, for example, on a plastic film or a layer containing an inorganic compound, dried, and then the silica sol can be dehydrated and condensed to cure. The dehydration condensation of the silica sol proceeds even by heat treatment, but in order to accelerate the dehydration condensation, it is preferable to use a catalyst such as a base and an acid. The catalyst may be added to the release layer-forming composition, or the release layer may be exposed to a catalyst atmosphere after the formation of the release layer. The temperature conditions for the dehydration condensation of the silica sol are not particularly limited and may be appropriately determined within the range of 20 to 250°C. When the release layer forming composition contains a curable resin composition, the curing of the silica sol and the curing of the curable resin composition may be carried out simultaneously, or either one may be carried out first.

[0069] The thickness of the release layer is preferably 1 to 25 nm, more preferably 3 to 20 nm, and even more preferably 5 to 15 nm. By setting the thickness of the release layer to 1 nm or more, it is easy to improve the scratch resistance of the release layer. Further, by setting the thickness of the release layer to 25 nm or less, it is possible to suppress a decrease in the antireflection performance. Furthermore, by setting the thickness of the release layer to 25 nm or less, the molecules constituting the release layer are arranged in an orderly manner and have a high degree of hydrophilicity, and it is considered that it becomes easy to satisfy Condition 2.

[0070] The refractive index of the release layer is preferably 1.49 or less, and more preferably 1.46 or less. By setting the refractive index of the release layer to 1.49 or less, it is possible to further suppress a decrease in the antireflection performance when the layer containing the inorganic compound is made to have a low refractive index. Note that the lower limit of the refractive index of the release layer is about 1.30.

[0071] <Hard coat layer> It is preferable to have a hard coat layer between the transparent plastic film and the release layer in order to enhance the scratch resistance. When there is a layer containing an inorganic compound between the transparent plastic film and the release layer, it is preferable to have a hard coat layer between the transparent plastic film and the layer containing the inorganic compound.

[0072] The hard coat layer preferably contains a cured product of a curable resin composition such as a thermosetting resin composition or an ionizing radiation curable resin composition, and more preferably contains a cured product of an ionizing radiation curable resin composition from the viewpoint of further improving the scratch resistance. The thermosetting resin composition and the ionizing radiation curable resin composition of the hard coat layer can be the same as those of the thermosetting resin composition and the ionizing radiation curable resin composition of the layer containing the inorganic compound described above.

[0073] The thickness of the hard coat layer is preferably from 0.1 to 100 μm, more preferably from 0.5 to 20 μm, and even more preferably from 1 to 10 μm. By setting the thickness of the hard coat layer within the above range, it is possible to improve the scratch resistance and easily suppress the occurrence of curling.

[0074] The refractive index of the hard coat layer is preferably adjusted within the range of 1.45 to 1.70. Further, when the layer containing an inorganic compound is made to have a low refractive index, if there is a high refractive index layer in contact with the transparent plastic film side of the layer containing the low refractive index inorganic compound, the refractive index of the hard coat layer is preferably lower than the refractive index of the high refractive index layer, more preferably from 1.50 to 1.65, and even more preferably from 1.55 to 1.60. If the refractive index of the hard coat layer is within such a range, the hard coat layer serves as an intermediate refractive index layer, and an interference effect by the three layers of the hard coat layer (intermediate refractive index layer), the high refractive index layer, and the low refractive index layer (the layer containing the low refractive index inorganic compound) becomes possible, so that the reflectance can be lowered.

[0075] As means for imparting the role of an intermediate refractive index layer to the hard coat layer, there may be mentioned means of blending a resin having a high refractive index into the hard coat layer coating liquid, and means of blending particles having a high refractive index. Examples of the resin having a high refractive index include those obtained by introducing a group containing sulfur, phosphorus, bromine, an aromatic ring, etc. into the above-described thermosetting resin or radiation curable compound. Examples of the particles having a high refractive index are the same as the high refractive index particles used for the high refractive index layer described later.

[0076] <High refractive index layer> When the layer containing an inorganic compound is made to have a low refractive index, from the viewpoint of further lowering the reflectance of the release laminate, it is preferable to have a high refractive index layer in contact with the transparent plastic film side of the layer containing the low refractive index inorganic compound. The high refractive index layer can be formed, for example, from a high refractive index layer coating liquid containing high refractive index particles and a binder resin composition.

[0077] Examples of the high refractive index particles include antimony pentoxide, zinc oxide, titanium oxide, cerium oxide, tin-doped indium oxide, antimony-doped tin oxide, yttrium oxide, and zirconium oxide. The average particle diameter of the primary particles of the high refractive index particles is preferably 3 to 200 nm, more preferably 5 to 100 nm, and even more preferably 7 to 50 nm.

[0078] From the viewpoint of the balance between increasing the refractive index of the coating film and the coating film strength, the content of the high refractive index particles is preferably 50 to 1000 parts by mass, more preferably 100 to 750 parts by mass, and even more preferably 200 to 500 parts by mass with respect to 100 parts by mass of the binder resin.

[0079] Examples of the binder resin of the high refractive index layer include cured products of curable resin compositions. As the curable resin composition, the same ones as those exemplified for the layer containing an inorganic compound can be used, and an ionizing radiation curable resin composition is preferable.

[0080] The refractive index of the high refractive index layer is preferably 1.55 to 1.85, more preferably 1.56 to 1.75. Further, the thickness of the high refractive index layer is preferably 200 nm or less, more preferably 50 to 180 nm.

[0081] <Other Layers> The release laminate of the present invention may have other layers. For example, an adhesive layer, an antistatic layer, a printing layer, etc. may be provided on the surface of the transparent plastic film opposite to the layer containing the inorganic compound.

[0082] <Other Physical Properties> When the release laminate is used for showcases, show windows, windows, etc., from the viewpoint of improving visibility, the haze according to JIS K7136:2000 is preferably less than 2.0%, more preferably 1.5% or less, and even more preferably 1.0% or less. Note that the light-transmissive portion is intended to exclude portions where light transmittance has decreased (portions with a total light transmittance of 50% or less), for example, by forming a printed layer on the surface opposite to the layer containing the inorganic compound of the transparent plastic film.

[0083] The surface on the release layer side of the release laminate preferably has an arithmetic mean roughness Ra (JIS B0601:1994) with a cut-off value of 0.08 mm of 0.02 μm or less, and more preferably 0.01 μm or less.

[0084] The reflectance of the surface on the release layer side of the release laminate is preferably 2.0% or less, more preferably 1.5% or less, and even more preferably 1.0% or less. By reducing the reflectance, visibility becomes good, and it can be suitably used for showcases, show windows, windows, etc.

[0085] In this specification, the reflectance refers to the visual sense reflectance Y value in the CIE1931 standard colorimetric system, and is the average value of 10 measurements. Further, in this specification, the reflectance of the surface on the release layer side of the release laminate is measured by preparing a sample in which a black plate is bonded via a transparent adhesive layer on the side opposite to the reflectance measurement surface of the release laminate, and irradiating light at an incident angle of 5° from the release layer side of the sample. The light source for measuring the reflectance is preferably D65. The refractive index difference between the member (for example, a transparent plastic film) in contact with the transparent adhesive layer of the sample and the transparent adhesive layer is preferably within 0.15, and more preferably within 0.10. The black plate preferably has a total light transmittance of 1% or less according to JIS K7361-1:1997, and more preferably 0%. The refractive index difference between the refractive index of the resin constituting the black plate and the transparent adhesive layer is preferably within 0.15, and more preferably within 0.10.

[0086] <Size, shape, etc.> The release laminate may be in a sheet form or in a roll form. In addition, the size of the single sheet is not particularly limited, but generally, the diagonal size is about 2 to 500 inches. The width and length of the roll are not particularly limited, but generally, the width is about 500 to 3000 mm and the length is about 500 to 5000 m. Also, the shape of the single sheet is not particularly limited, and for example, it may be polygonal (triangle, quadrilateral, pentagon, etc.), circular, or randomly irregular.

[0087] <Use> The above-described release laminate of the present invention is used, for example, as a release base material for a transfer sheet and a process sheet, and can also be used as a surface member for a showcase, a show window, and a window.

[0088] [Transfer Sheet] The transfer sheet of the present invention has a transfer layer on the release layer of the above-described release laminate of the present invention. That is, the transfer sheet of the present invention uses the above-described release laminate as a release base material for the transfer sheet.

[0089] In the stage before initial transfer, the transfer sheet of the present invention can sufficiently adhere the release layer to the release laminate (release base material), and after adhering the transfer layer to the adherend, the release laminate (release base material) can be easily peeled off from the transfer layer by a simple process of dropping water.

[0090] The transfer layer of the transfer sheet includes, for example, a configuration having a functional layer and an adhesive layer. In this configuration, the functional layer is disposed on the side of the release laminate (release base material). Examples of the functional layer include a hard coat layer, an antireflection layer, and an antifouling layer.

[0091] [Process Sheet] The process sheet of the present invention has the release layer of the above-described release laminate of the present invention on the outermost surface.

[0092] The process sheet of the present invention can easily peel the processed electronic components, etc. from the process sheet by a simple process of dropping water after the process while adhesively bonding the electronic components, etc. with sufficient adhesive force through an adhesive.

[0093] [Article] The article of the present invention is configured such that the release layer of the release laminate of the present invention described above faces the surface.

[0094] Examples of the article include a showcase, a show window, and a window. That is, the articles of the present invention include a showcase, a show window, and a window configured such that the release layer of the release laminate faces the surface. The article of the present invention can easily peel the display object such as an advertisement while fixing the display object such as an advertisement with sufficient adhesive force using an adhesive tape, and when changing the display object, the display object can be easily peeled by a simple process of dropping water.

Example

[0095] Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. Note that the present invention is not limited to the forms described in the Examples.

[0096] 1. Evaluation and Measurement The following measurements and evaluations were performed on the release laminates obtained in the Examples and Comparative Examples. The results are shown in Table 1.

[0097] 1-1. Confirmation of Conditions 1 to 3 (1) Adhesive tape A1 with a peel strength of 3 N / 10 mm according to Method 1 (180° peel from a stainless steel test plate) of JIS Z0237:2009 was prepared, and the peel strengths P1 (N / 10 mm), P2 (N / 10 mm), and P3 (N / 10 mm) under Conditions 1 to 3 were measured to confirm whether Conditions 1 to 3 were satisfied. Those satisfying each condition were designated as "A", and those not satisfying each condition were designated as "C". A tensilon universal testing machine manufactured by Orientec was used for the measurement of the peel strength, and the peel rate was 300 mm / min. In addition, the atmosphere when performing Conditions 1 to 3 was set to a temperature of 23°C ± 5°C and a humidity of 40 to 65%. Also, before performing Conditions 1 to 3, each sample was left in the said atmosphere for 10 minutes or more. Further, in Conditions 3 and 4, the reciprocating friction was carried out using a Kagaku-shin ken type friction tester conforming to JIS L0849:2013 at a speed of 30 mm one-way and 1 second per reciprocation. Also, in Conditions 2 and 3, ion-exchanged water was used as the water. Further, in Conditions 1 to 3, the width of the adhesive tape was 10 mm, and the length of the region of the total length of the adhesive tape that was bonded to the release laminate was 50 mm. Also, in Conditions 2 to 3, the amount of water droplet was 20 ml.

[0098] 1-2. Confirmation of Conditions 1 to 3 (2) An adhesive tape A2 with a peel strength of 7 N / 10 mm in accordance with Method 1 of JIS Z0237:2009 (180° peel from a stainless steel test plate) was prepared, and in the same manner as in 1-1 above, it was confirmed whether Conditions 1 to 3 were satisfied.

[0099] 1-3. Steel wool resistance (SW resistance) After cutting the release laminates of the examples and comparative examples into a size of 5.0 cm × 5.0 cm, a sample (5.0 cm × 5.0 cm) was prepared by laminating a transparent adhesive layer with a thickness of 25 μm (manufactured by Panac Co., Ltd., product name: Panaclean PD-S1) and a transparent glass plate with a thickness of 2 mm on the transparent plastic film side. #0000 steel wool was pressed against the surface on the release layer side of the sample, and after rubbing 10 times under a load of 500 g / cm 2 a black plate was placed on the back surface of the sample, and under the illumination of a fluorescent lamp, it was visually evaluated whether scratches could be visually recognized from the release layer side. Those with no visible scratches were rated as "A", and those with visible scratches were rated as "C". Further, for those rated as A under a load of 500 g / cm 2 when the same evaluation was carried out under a load of 700 g / cm 2 those with no visible scratches were rated as "AA".

[0100] 1-4. Reflectance (visual reflectance Y value) On the transparent plastic film side of the release laminate of the examples and comparative examples, a black plate (manufactured by Kuraray Co., Ltd., product name: Komoglas DFA2CG 502K (black) series, total light transmittance 0%, thickness 2 mm, refractive index 1.49) was bonded through a transparent adhesive layer with a thickness of 25 μm (manufactured by Panac Co., product name: Panaclean PD-S1, refractive index 1.49) to prepare a sample (5 cm × 5 cm). When the direction perpendicular to the surface of the release laminate was set to 0 degrees, light was incident on the sample from a direction of 5 degrees, and the reflectance (visual reflectance Y value) of the sample was measured based on the specularly reflected light of the incident light. The reflectance was measured using a spectrophotometric reflectometer (manufactured by Shimadzu Corporation, product name: MPC3100) in the wavelength range of 380 to 780 nm for the 5° specular reflectance, and then the value indicating the visual reflectance calculated by software (built into MPC3100) that converts it into the brightness felt by the human eye was taken as the reflectance. The reflectance at 10 locations was measured for each sample, and the average value was taken as the reflectance of each sample.

[0101] 2. Preparation of coating solution The following coating solutions were prepared. <Coating solution for hard coat layer> · Urethane acrylate (product name "UX5005", manufactured by Nippon Kayaku Co., Ltd., 9-functional) 50 parts by mass · Pentaerythritol triacrylate 25 parts by mass · Acrylate monomer (product name "R684", manufactured by Nippon Kayaku Co., Ltd., 2-functional) 25 parts by mass · Photoinitiator (product name "Irgacure 184", manufactured by BASF) 4 parts by mass · Levelling agent (product name "Megafac F477", manufactured by DIC) 0.2 parts by mass · Methyl ethyl ketone 125 parts by mass · Propylene glycol monomethyl ether acetate 25 parts by mass

[0102] <Coating solution for layer containing inorganic compound (low refractive index layer)> · Propylene oxide-modified pentaerythritol tetraacrylate (product name "ATM-4P", manufactured by Shin-Nakamura Chemical Co., Ltd., solid content 100%) 75 parts by mass · 25 parts by mass of pentaerythritol triacrylate · 800 parts by mass of a dispersion containing hollow silica fine particles (solid content: 20%, average primary particle diameter: 60 nm) · 83 parts by mass of a dispersion containing reactive silica fine particles (trade name: "MIBK-SD", manufactured by Nissan Chemical Industries, Ltd., solid content: 30%, average primary particle diameter: 12 nm) · 7 parts by mass of a photoinitiator (trade name: "Irgacure 127", manufactured by BASF) · 9300 parts by mass of methyl isobutyl ketone · 1100 parts by mass of propylene glycol monomethyl ether acetate

[0103] <Release layer coating liquid 1> · 5 parts by mass of a solution containing a modified product of the following organosol-dispersed silica sol (solid content: about 0.08% by mass) · 45 parts by mass of ion-exchanged water · 5 parts by mass of isopropyl alcohol

[0104] <Solution containing a modified product of organosol-dispersed silica sol> 4.39 g of 1,2-oxathiolane 2,2-dioxide (manufactured by Tokyo Chemical Industry Co., Ltd.) and 7.26 g of N,N-dimethyl-3-aminopropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 40 ml of ethyl dehydracetate and stirred at room temperature for 24 hours. By filtering the resulting white precipitate, 8.5 g of N-propyltrimethoxysilane-N,N-dimethyl-N-(3-sulfopropyl)ammonium betaine was obtained. Next, 4.0 g of N-propyltrimethoxysilane-N,N-dimethyl-N-(3-sulfopropyl)ammonium betaine and 13.2 g of an organosol-dispersed silica sol (manufactured by Nissan Chemical Industries, Ltd., IPA-ST (solid content: 30%)) were dissolved in a solvent (a mixed solvent of 80 ml of ethanol and 140 ml of water) and heated under reflux overnight. After cooling, 520 mg of lithium hydroxide monohydrate (manufactured by Nacalai Tesque, Inc.) was dissolved in a small amount of water and added to the reaction solution for neutralization. Water was added to the resulting reaction solution to adjust the volume to 500 g, thereby obtaining (-O-)3SiCH2CH2CH2N +500 g of a solution containing a modified product of an organosol-dispersed silica sol modified with a (CH3)2CH2CH2CH2SO3- group was obtained (solid content: approximately 1.6% by mass).

[0105] <Release layer coating liquid 2> · 4 parts by mass of the solution containing the modified product of the above organosol-dispersed silica sol (solid content: approximately 0.064 part by mass) · Si5O4(OC2H5) 12 (trade name “ethyl silicate 40”, manufactured by Colcoat Co., Ltd.) 0.02 part by mass (in terms of solid content) · 0.002 part by mass of 3-methacryloxypropyltrimethoxysilane · 45 parts by mass of ion-exchanged water · 5 parts by mass of isopropyl alcohol

[0106] 3. Preparation of the release laminate [Example 1] The coating liquid for the hard coat layer with the above formulation was applied onto a polyethylene terephthalate film with a thickness of 100 μm (refractive index 1.65), dried (at 70°C for 1 minute) and irradiated with ultraviolet rays (100 mJ / cm 2 ) to form a hard coat layer with a thickness of 10 μm. Next, the coating liquid for the layer containing the inorganic compound (low refractive index layer) with the above formulation was applied onto the hard coat layer, dried (at 90°C for 1 minute) and irradiated with ultraviolet rays (200 mJ / cm 2 ) to form a layer containing an inorganic compound with a thickness of 90 nm and a refractive index of 1.35. Next, after subjecting the surface of the layer containing the inorganic compound to corona discharge treatment, the coating liquid 1 for the release layer with the above formulation was applied, dried (at 100°C for 1 minute), and further heat-treated at 110°C for 15 minutes to cure (dehydration condensation) the silica sol and form a release layer, thereby obtaining the release laminate of Example 1. The theoretical thickness of the release layer based on the coating amount was 10 nm. In addition, when the coating liquid 1 for the release layer was formed to a thickness at which the refractive index could be measured and the refractive index was measured, it was 1.43.

[0107] [Example 2] A release laminate of Example 2 was obtained in the same manner as in Example 1, except that the thickness of the release layer was changed to 15 nm.

[0108] [Example 3] A mold release laminate of Example 3 was obtained in the same manner as in Example 1, except that the thickness of the release layer was changed to 7 nm.

[0109] [Example 4] A mold release laminate of Example 4 was obtained in the same manner as in Example 1, except that the "hollow silica fine particle-containing dispersion (solid content 20%, average primary particle diameter 60 nm)" in the coating liquid for the layer containing an inorganic compound (low refractive index layer) was changed to the "hollow silica fine particle-containing dispersion (solid content 20%, average primary particle diameter 75 nm)".

[0110] [Example 5] A mold release laminate of Example 5 was obtained in the same manner as in Example 1, except that the "hollow silica fine particle-containing dispersion (solid content 20%, average primary particle diameter 60 nm)" in the coating liquid for the layer containing an inorganic compound (low refractive index layer) was changed to the "hollow silica fine particle-containing dispersion (solid content 20%, average primary particle diameter 50 nm)".

[0111] [Example 6] A mold release laminate of Example 6 was obtained in the same manner as in Example 1, except that the "hollow silica fine particle-containing dispersion (solid content 20%, average primary particle diameter 60 nm)" in the coating liquid for the layer containing an inorganic compound (low refractive index layer) was changed to the "hollow silica fine particle-containing dispersion (solid content 20%, average primary particle diameter 100 nm)".

[0112] [Example 7] A mold release laminate of Example 7 was obtained in the same manner as in Example 1, except that a high refractive index layer (refractive index 1.65, thickness 165 nm) was formed between the hard coat layer and the layer containing an inorganic compound. Note that the high refractive index layer was formed by applying the following coating liquid for a high refractive index layer, drying (90 °C, 1 minute), and ultraviolet irradiation (200 mJ / cm 2 ). [Coating Liquid for High Refractive Index Layer] · 100 parts by mass of pentaerythritol triacrylate (trade name PET30, manufactured by Nippon Kayaku Co., Ltd., solid content 100%) · Antimony pentoxide-containing dispersion (trade name "V-4564", manufactured by Nippon Shokubai Catalysts & Chemicals Co., Ltd., solid content 40%, average primary particle diameter 20 nm) 1100 parts by mass · Fluorine-based leveling agent (trade name "Megafac F568", manufactured by DIC Corporation, solid content 5%) 300 parts by mass · Photoinitiator (trade name "Irgacure 127", manufactured by BASF) 8 parts by mass

[0113] [Example 8] A release property laminate of Example 8 was obtained in the same manner as in Example 1, except that the coating liquid for the layer containing an inorganic compound (low refractive index layer) was changed to the coating liquid for the layer containing an inorganic compound (low refractive index layer) of Example 8 below. [Coating liquid for the layer containing an inorganic compound (low refractive index layer) of Example 8] · Silane coupling agent 1 (tetraethoxysilane) 25 parts by mass · Silane coupling agent 2 (3-methacryloxypropyltrimethoxysilane) 25 parts by mass · Pentaerythritol triacrylate 50 parts by mass · Dispersion containing hollow silica fine particles (solid content 20%, average primary particle diameter 60 nm) 800 parts by mass · Photoinitiator (trade name "Irgacure 127", manufactured by BASF) 7 parts by mass · Methyl isobutyl ketone 9300 parts by mass · IPA 1100 parts by mass

[0114] [Example 9] In the same manner as in Example 1, a hard coat layer and a layer containing an inorganic compound were formed on a polyethylene terephthalate film (refractive index 1.65). Next, after subjecting the surface of the layer containing an inorganic compound to corona discharge treatment, the coating liquid 2 for the release layer of the above formulation was applied, dried (100 °C, 1 minute), heat-treated at 110 °C for 15 minutes to cure (dehydration condensation) the silica sol, and then irradiated with ultraviolet rays (200 mJ / cm 2 ) to obtain a release property laminate of Example 9. The theoretical thickness of the release layer based on the coating amount is 10 nm. In addition, when the release layer coating liquid 2 was formed to a thickness at which the refractive index could be measured and the refractive index was measured, it was 1.43.

[0115] [Comparative Example 1] A release property laminate of Comparative Example 1 was obtained in the same manner as in Example 1, except that a release layer was not formed on the layer containing the inorganic compound.

[0116] [Reference Example 1] A release property laminate of Reference Example 1 was obtained in the same manner as in Example 1, except that a layer containing an inorganic compound was not formed on the hard coat layer and a release layer was directly formed on the hard coat layer.

[0117]

Table 1

[0118] As is clear from Table 1, the release property laminates of Examples 1 to 9 have a predetermined adhesive force with respect to the adhesive, and on the other hand, the adherend can be easily peeled off by a simple process of dropping water, and it can be confirmed that the performance can be maintained over a long period. Although not evaluated in the table, the release property laminate of Example 8 satisfied the conditions 4 of the specification and could maintain the performance over an extremely long period.

Explanation of Signs

[0119] 10: Transparent plastic film 20: Hard coat layer 30: Layer containing inorganic compound 40: Release layer 100: Release property laminate

Claims

1. A laminate having a release layer on a transparent plastic film, wherein the release layer is located on the outermost surface of the laminate and satisfies the following Conditions 1 to 2, and the release layer is a cured product of a release layer-forming composition containing an organosol-dispersed silica sol modified with a silane coupling agent. A releasable laminate. <Condition 1> Prepare an adhesive tape A with a peel strength of PA (N / 10 mm) according to Method 1 (180° peel from a stainless steel test plate) of JIS Z0237:2009. The adhesive tape A is attached to the surface of the releasable laminate on the side of the release layer. When the peel strength when peeling the adhesive tape A in accordance with Method 1 of JIS Z0237:2009 except that the test plate is not stainless steel but the releasable laminate is defined as P1 (N / 10 mm), P1 / PA shows 0.75 or more. <Condition 2> Attach the adhesive tape A to the surface of the releasable laminate on the side of the release layer. Using a dropper, drip water so that at least the area where the adhesive tape A is attached and the area 1 cm outside the outer edge of the adhesive tape A on the surface of the releasable laminate on the side of the release layer are covered with water. After 5 minutes have elapsed since the dripping of water was completed, when the peel strength when peeling the adhesive tape A in accordance with Method 1 of JIS Z0237:2009 except that the test plate is not stainless steel but the releasable laminate is defined as P2 (N / 10 mm), P2 / PA shows 0.2 or less.

2. The releasable laminate according to Claim 1, further satisfying the following Condition 3. <Condition 3> The surface of the release layer of the release laminate is rubbed 1000 times back and forth under a load of 500 g / cm using a napped cloth of 300 count cotton. ２ The resulting product is defined as a friction laminate 1. An adhesive tape A is bonded to the surface on the release layer side of the friction laminate 1. Water is dripped with a dropper so that at least the region to which the adhesive tape A is bonded and the region 1 cm outside the outer edge of the adhesive tape A on the surface on the release layer side of the friction laminate 1 are covered with water. After 5 minutes have elapsed since the dripping of water was completed, when the peel strength when peeling the adhesive tape A in accordance with Method 1 of JIS Z0237:2009 except that the test plate is not stainless steel but the friction laminate 1 is defined as P3 (N / 10 mm), P3 / PA shows 0.2 or less.

3. The releasable laminate according to Claim 1 or 2, having the release layer on both surfaces of the transparent plastic film.

4. The releasable laminate according to any one of Claims 1 to 3, wherein the thickness of the release layer is 1 to 25 nm.

5. The releasable laminate according to any one of Claims 1 to 4, having a layer containing an inorganic compound between the transparent plastic film and the release layer.

6. The releasable laminate according to any one of Claims 1 to 5, having a hard coat layer between the transparent plastic film and the release layer.

7. A transfer sheet having a transfer layer on the release layer of the release laminate according to any one of claims 1 to 6.

8. A process sheet having the release layer of the release laminate according to any one of claims 1 to 6 on the outermost surface.

9. An article in which the release layer of the release laminate according to any one of claims 1 to 6 is disposed so as to face the surface.

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