Transfer sheet and manufacturing method thereof, manufacturing method of molded article using said transfer sheet, molded article, and front panel and image display device using said molded article

Abstract

Provided is a manufacturing method for a transfer sheet capable of imparting a sufficient function to an adherend. The transfer-sheet manufacturing method includes the following steps (1) to (2) that are performed in order. (1) A step for applying a transfer-layer-formation application liquid to a release base material 1, to form a transfer layer containing at least one functional layer. (2) A step for laminating a release base material 2 on the transfer layer to obtain a transfer sheet A that has the release base material 1, the transfer layer, and the release base material 2, in this order, and in which peel strength 2 between the release base material 2 and the transfer layer is stronger than peel strength 1 between the release base material 1 and the transfer layer.

Description

[Technical Field]

[0001] The present invention relates to a transfer sheet and a method for producing the same, a method for producing a molded article using the transfer sheet, the molded article, and a front panel and an image display device using the molded article. [Background technology]

[0002] 2. Description of the Related Art There are cases where it is required to impart predetermined functions such as anti-reflection and anti-fouling properties to the surface of an arbitrary adherend. In such cases, insert molding, for example, is carried out. Insert molding is a method of obtaining a molded body by placing a functional film having a functional layer on a support inside an injection molding mold, pouring an injection resin into the support side, and integrating the support side of the functional film with the injected resin as the adherend.

[0003] However, in the case of insert molding, a relatively thick support exists between the adherend and the functional layer, which causes problems such as an increase in the overall thickness of the molded body and a loss of the texture of the adherend.

[0004] On the other hand, a method of imparting a predetermined function to the surface of an adherend by directly applying a functional coating material to the surface of the adherend using a spray or the like has also been used. This method can solve the above-mentioned problems. However, when applying coating directly to the surface of the adherend, there is a problem that unevenness in the coating can cause unevenness in the function. In particular, when the surface of the adherend has an uneven shape, the problem of uneven coating is likely to be significant.

[0005] Furthermore, as a means other than insert molding and direct coating, a means has been proposed in which a functional layer is formed on an adherend by transfer using a transfer sheet (Patent Documents 1 to 4). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2014-130298 [Patent Document 2] Japanese Patent Application Laid-Open No. 2009-072954 [Patent Document 3] Japanese Patent Application Laid-Open No. 2009-056674 [Patent Document 4] Japanese Patent Application Laid-Open No. 2008-151930 Summary of the Invention [Problem to be solved by the invention]

[0007] However, when a functional layer is transferred onto an adherend using the transfer sheets disclosed in Patent Documents 1 to 4, there have been many cases where the transferred functional layer is unable to fully function compared to insert molding or direct coating.

[0008] The present invention aims to provide a transfer sheet manufacturing method and a transfer sheet that can impart sufficient functionality to an adherend. The present invention also aims to provide a molded article to which sufficient functionality has been imparted by a transfer layer, a manufacturing method for the molded article, and a front panel and an image display device that use the molded article. [Means for solving the problem]

[0009] The present invention, which solves the above problems, provides the following [1] to [6]. [1] A method for producing a transfer sheet, which comprises the following steps (1) to (2) in order: (1) A step of applying a coating liquid for forming a transfer layer onto a release substrate 1 to form a transfer layer including at least one functional layer. (2) A step of laminating a release substrate 2 on the transfer layer to obtain a transfer sheet A having the release substrate 1, the transfer layer, and the release substrate 2 in this order, wherein the peel strength 2 between the release substrate 2 and the transfer layer is greater than the peel strength 1 between the release substrate 1 and the transfer layer. [2] The method for producing a transfer sheet according to the above [1], further comprising the step (3) below: (3) A step of peeling off the release substrate 1 from the transfer sheet A to obtain a transfer sheet B having the transfer layer on the release substrate 2. [3] A method for producing a molded body, comprising the steps of (4) and (5) below in order: (4) A step of obtaining a laminate C by closely adhering the surface of the transfer layer side of the transfer sheet B described in [2] above to an adherend. (5) A step of peeling off the release substrate 2 from the laminate C to obtain a molded article having a transfer layer on an adherend. [4] A transfer sheet A, comprising a release substrate 1, a transfer layer, and a release substrate 2 in this order, wherein the peel strength 2 between the release substrate 2 and the transfer layer is greater than the peel strength 1 between the release substrate 1 and the transfer layer, the transfer layer includes at least one functional layer, and at least one of the functional layers has a function that is unevenly distributed toward the release substrate 2 side. [5] Transfer sheet B, which has a transfer layer on a release substrate 2, the transfer layer including at least one functional layer, and at least one of the functional layers has a function that is unevenly distributed on the release substrate 2 side. [6] A molded article having a transfer layer on an adherend, the transfer layer having at least one functional layer, at least one of the functional layers having a function unevenly distributed on the side opposite to the adherend. [Effects of the Invention]

[0010] According to the method for producing a transfer sheet of the present invention, a transfer sheet capable of imparting sufficient functionality to an adherend can be easily produced. Furthermore, according to the transfer sheet of the present invention, sufficient functionality can be imparted to an adherend. Furthermore, according to the method for producing a molded article of the present invention, a molded article having sufficient functionality due to the transfer layer can be easily produced. Furthermore, according to the molded article of the present invention and the front panel and image display device using the same, the molded article having a transfer layer and the like can have sufficient functionality. [Brief explanation of the drawings]

[0011] [Figure 1] FIG. 1 is a cross-sectional view showing one embodiment of a work-in-progress of the release sheet A of the present invention. [Figure 2] FIG. 1 is a cross-sectional view showing one embodiment of a release sheet A of the present invention. [Figure 3] FIG. 1 is a cross-sectional view showing one embodiment of a release sheet B of the present invention. [Figure 4] 1A to 1C are cross-sectional views illustrating steps in a method for producing a molded article according to an embodiment of the present invention. [Figure 5] 1A and 1B are cross-sectional views showing an example of a conventional transfer sheet and an example of a method for producing a molded article using the transfer sheet. [Figure 6] 1 is a cross-sectional photograph of an example of a low refractive index layer in which hollow particles and non-hollow particles are uniformly dispersed. [Figure 7] 1 is a cross-sectional photograph of an example of a low refractive index layer in which hollow particles and non-hollow particles are not uniformly dispersed. DETAILED DESCRIPTION OF THE INVENTION

[0012] [Transfer sheet manufacturing method] The method for producing the transfer sheet of the present invention involves carrying out the following steps (1) and (2) in order. (1) A step of applying a coating liquid for forming a transfer layer onto a release substrate 1 to form a transfer layer including at least one functional layer. (2) A step of laminating a release substrate 2 on the transfer layer to obtain a transfer sheet A having the release substrate 1, the transfer layer, and the release substrate 2 in this order, wherein the peel strength 2 between the release substrate 2 and the transfer layer is greater than the peel strength 1 between the release substrate 1 and the transfer layer.

[0013] Fig. 1 is a cross-sectional view showing one embodiment of the laminate at the stage after step 1. The laminate in Fig. 1 has a transfer layer 30 on a release substrate 1 (10). Fig. 2 is a cross-sectional view showing one embodiment of transfer sheet A (100) obtained through steps (1) and (2). Transfer sheet A (100) in Fig. 2 has a transfer layer 30 and a release substrate 2 (20) on a release substrate 1 (10). 1 and 2, the transfer layer 30 includes two functional layers (functional layer 1 (31) and functional layer 2 (32)). Also, in FIGS. 1 and 2, the gradation of functional layer 2 (32) indicates the degree of uneven distribution of the functional component in functional layer 2 (32) (the darker the color, the higher the density of the functional component).

[0014] <Process (1)> Step 1 is a step of applying a transfer layer forming coating liquid onto a release substrate 1 to form a transfer layer including at least one functional layer.

[0015] Examples of a means for applying the coating liquid for forming a transfer layer onto the release substrate 1 include general-purpose coating means such as gravure coating, die coating, and bar coating. When the transfer layer has two or more functional layers, the functional layers may be formed sequentially or simultaneously using coating equipment capable of simultaneous multi-layer coating. After the transfer layer-forming coating liquid is applied, it is preferable to dry it and / or irradiate it with ultraviolet light, if necessary, to volatilize the solvent and harden the resin composition.

[0016] <<Release base material 1>> The release substrate 1 can be any substrate that can be peeled off from the transfer layer without any particular limitation, and a plastic film is preferably used. Examples of plastic films that can be used as the release substrate 1 include plastic films formed from one or more of polyolefin resins such as polyethylene and polypropylene, vinyl resins such as polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer and ethylene-vinyl alcohol copolymer, polyester resins such as polyethylene terephthalate, polyethylene naphthalate and polybutylene terephthalate, acrylic resins such as polymethyl (meth)acrylate and polyethyl (meth)acrylate, styrene resins such as polystyrene, polyamide resins such as nylon 6 or nylon 66, cellulose resins such as triacetyl cellulose, polycarbonate resins and polyimide resins.

[0017] The release substrate 1 is preferably one whose surface has been subjected to a release treatment with a release agent such as a fluorine-based release agent and a silicone-based release agent from the viewpoints of improving the releasability from the transfer layer and making the release strength 2 greater than the release strength 1. Also, from the above two viewpoints, the surface shape of the release substrate 1 is preferably substantially smooth. Specifically, the surface of the release substrate 1 on the side where the transfer layer is formed preferably has an arithmetic mean roughness Ra of 0.04 μm or less according to JIS B0601:1994 at a cut-off value of 0.25 mm. The Ra of the release substrate 1 can be measured under the following measurement conditions by preparing an evaluation sample in which a black acrylic plate (manufactured by Kuraray, trade name "Comoglass 502K") is bonded via a transparent adhesive (manufactured by Hitachi Chemical Co., Ltd., trade name "DA-1000") to the surface of the release substrate 1 on the side where the transfer layer is not laminated, after cutting the release substrate 1 into 100 mm × 100 mm, placing the sample on a horizontal plane. <Measurement conditions for Ra> · Reference length (cut-off value λc of roughness curve): 0.25 mm · Evaluation length (reference length (cut-off value λc) × 5): 1.25 mm · Feed speed of stylus: 0.1 mm / s · Vertical magnification: 100000 times · Horizontal magnification: 50 times · Skid: Not used (no contact with measurement surface) · Cut-off filter type: Gaussian · JIS mode: JIS1994

[0018] Also, the release substrate 1 may have an antistatic layer from the viewpoint of suppressing release electrification.

[0019] The thickness of the release substrate 1 is not particularly limited, but from the viewpoint of handleability, it is preferably 10 to 500 μm, more preferably 20 to 400 μm, and even more preferably 30 to 300 μm. Also, from the viewpoint of making the entire transfer sheet A flexible and improving handleability, the upper limit value of the thickness of the release substrate 1 is more preferably 90 μm or less, and most preferably 45 μm or less. When the thickness of release substrate 1 is T1 and the thickness of release substrate 2 is T2, T2 / T1 is preferably greater than 1.00, more preferably 1.10 or greater, and even more preferably 1.20 or greater, from the viewpoint of ease of handling after peeling off release substrate 1. Furthermore, from the viewpoint of suppressing curling of the transfer sheet, T2 / T1 is preferably 2.00 or less, more preferably 1.80 or less, and even more preferably 1.60 or less.

[0020] <<Transfer layer>> The transfer layer is a layer that is transferred onto an adherend, and has the role of imparting a predetermined function to the adherend. The transfer layer includes at least one functional layer. The number of functional layers included in the transfer layer may be only one, two as shown in Figures 1 and 2, or even three or more.

[0021] Examples of the functional layer include a hard coat layer, a low refractive index layer, a high refractive index layer, an antiglare layer, an antifouling layer, a stress relaxation layer, an antistatic layer, a gas barrier layer, an ultraviolet absorbing layer, a colored layer, a specific wavelength absorbing layer, an antifogging layer, and a transparent conductive layer. The functional layer may also have a combination of two or more of the above-mentioned functions. In other words, in this specification, the term "hard coat layer," "low refractive index layer," "high refractive index layer," "antiglare layer," "antifouling layer," "stress relaxation layer," "antistatic layer," "gas barrier layer," "ultraviolet absorbing layer," "colored layer," "specific wavelength absorbing layer," "antifogging layer," and "transparent conductive layer" refers not only to a functional layer having a single function, but also to a functional layer having a combination of functions. For example, the term "hard coat layer" includes an antifouling hard coat layer, an antiglare hard coat layer, and a high refractive index hard coat layer. The term "antifouling layer" includes an antiglare antifouling layer and a low refractive index antifouling layer.

[0022] In addition to the functional layer, the transfer layer may have other layers such as an adhesive layer and an anchor layer that do not impart any special function to the adherend.

[0023] The adhesive layer has the role of increasing the interlayer adhesion of the functional layers when placed between the functional layers, or increasing the adhesion between the transfer layer and the adherend when positioned on the farthest side of the release substrate 2. The adhesive layer can be formed from an adhesive layer-forming coating liquid containing a general-purpose resin component that exhibits adhesive properties. In addition, if the functional layer has adhesive properties and has good adhesion between the functional layer and the substrate, or if a double-sided adhesive sheet is used to adhere the transfer layer to the substrate, it is not necessary to provide an adhesive layer on the farthest side of the release substrate 2.

[0024] The adhesive layer may be a pressure-sensitive adhesive layer (a so-called pressure-sensitive adhesive layer) or an adhesive layer having heat-sealing properties. Furthermore, when the adhesive layer is disposed at the position farthest from the release substrate 2 (the position in contact with the release substrate 1), the adhesive layer is preferably an adhesive layer having heat-sealing properties. An adhesive layer having heat-sealing properties has almost no tackiness at room temperature, and therefore can be wound into a roll in the state of transfer sheet B obtained by peeling release substrate 1 from transfer sheet A, making it easy to handle. Furthermore, by making the adhesive layer have heat-sealing properties, peel strength 2 can be made greater than peel strength 1.

[0025] The thickness of the adhesive layer is preferably 0.5 to 50 μm, more preferably 1 to 30 μm, and even more preferably 2 to 20 μm.

[0026] The anchor layer has the role of protecting the functional layer from the heat of the injected resin when performing the in-mold molding described below, for example, by forming the anchor layer on the release substrate 1 side rather than the functional layer (the side farther from the release substrate 2 than the functional layer).

[0027] The anchor layer preferably contains a cured product of a curable resin composition. The curable resin composition may be a thermosetting resin composition or an ionizing radiation curable resin composition. The resin composition may be one type or a mixture of two or more types. The embodiment of the ionizing radiation curable resin composition for the anchor layer is the same as the embodiment of the ionizing radiation curable resin composition for the hard coat layer, which will be described later. The thermosetting resin composition of the anchor layer is a composition containing at least a thermosetting resin, and is a resin composition that hardens when heated. Examples of the thermosetting resin include acrylic resin, urethane resin, phenolic resin, urea melamine resin, epoxy resin, unsaturated polyester resin, and silicone resin. In the thermosetting resin composition, a curing agent is added to the hardenable resin as needed. The thickness of the anchor layer is preferably 0.1 to 6 μm, and more preferably 0.5 to 5 μm.

[0028] Specific examples of functional layers included in the transfer layer include the following (1) to (9). In the following (1) to (9), " / " indicates the interface of each functional layer, with the right side indicating the release substrate 2 side. In the following (1) to (9), the antifouling layer, hard coat layer, high refractive index layer, low refractive index layer, and antiglare layer may be composite functional layers having other functions. For example, the antifouling layer (1), the antiglare layer (5), and the antiglare layer (6) preferably have hard coat properties. (1) Antifouling layer (2) Hard coat layer / anti-fouling layer (3) Hard coat layer / high refractive index layer / anti-fouling low refractive index layer (4) High refractive index hard coat layer / anti-fouling low refractive index layer (5) Anti-glare layer (6) Anti-glare layer / low refractive index layer (7) Hard coat layer / anti-glare layer (8) Hard coat layer / anti-glare layer / anti-fouling low refractive index layer (9) Anti-glare layer / hard coat layer / anti-fouling low refractive index layer

[0029] Typical examples of the functional layer will be specifically described below, including a hard coat layer, a low refractive index layer, a high refractive index layer, an antiglare layer, and an antifouling layer.

[0030] -Hard coat layer- The hard coat layer, which is an example of a functional layer, preferably contains a cured product of a curable resin composition such as a thermosetting resin composition or an ionizing radiation-curable resin composition, more preferably a cured product of an ionizing radiation-curable resin composition, from the viewpoint of scratch resistance. The resin composition may be one type or a mixture of multiple types.

[0031] A thermosetting resin composition is a composition containing at least a thermosetting resin, and is a resin composition that cures when heated. Examples of thermosetting resins include acrylic resins, urethane resins, phenolic resins, urea-melamine resins, epoxy resins, unsaturated polyester resins, and silicone resins. In a thermosetting resin composition, a curing agent is added to the curable resin as needed.

[0032] 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 ethylenically unsaturated bond groups such as (meth)acryloyl groups, vinyl groups, and allyl groups, as well as epoxy groups and oxetanyl groups. As the ionizing radiation-curable compound, a compound having an ethylenically unsaturated bond group is preferred, and a compound having two or more ethylenically unsaturated bond groups is more preferred, and among these, a (meth)acrylate-based compound having two or more ethylenically unsaturated bond groups is even more preferred. As the (meth)acrylate-based compound having two or more ethylenically unsaturated bond groups, either a monomer or an oligomer can be used. Ionizing radiation refers to electromagnetic waves or charged particle beams that have an energy quantum capable of polymerizing or crosslinking molecules. Usually, ultraviolet (UV) rays or electron beams (EB) are used, but other types of radiation such as electromagnetic waves (X-rays and gamma rays), alpha rays, and charged particle beams (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.

[0033] From the viewpoint of scratch resistance, the thickness of the hard coat layer is preferably 0.1 μm or more, more preferably 0.5 μm or more, even more preferably 1.0 μm or more, and even more preferably 2.0 μm or more. Also, from the viewpoint of easily suppressing the occurrence of cracks in the transfer layer during transfer, the thickness of the hard coat layer is preferably 100 μm or less, more preferably 50 μm or less, more preferably 30 μm or less, more preferably 20 μm or less, more preferably 15 μm or less, and more preferably 10 μm or less.

[0034] -Low refractive index layer- A low refractive index layer, which is an example of a functional layer, serves to enhance the antireflection properties of the adherend. When the transfer layer has two or more functional layers, the low refractive index layer is preferably formed on the side farthest from the release substrate 1. The low refractive index layer also preferably has antifouling properties. In other words, the low refractive index layer is preferably an antifouling low refractive index layer. In addition, by forming a high refractive index layer (described later) adjacent to the low refractive index layer on the release substrate 1 side of the low refractive index layer, the antireflection properties can be further improved.

[0035] The refractive index of the low refractive index layer is preferably 1.10 to 1.48, more preferably 1.20 to 1.45, more preferably 1.26 to 1.40, more preferably 1.28 to 1.38, and more preferably 1.30 to 1.32. In this specification, the refractive indexes of the low refractive index layer and the high refractive index layer refer to the refractive index at a wavelength of 589.3 nm. The thickness of the low refractive index layer is preferably 80 to 120 nm, more preferably 85 to 110 nm, and even more preferably 90 to 105 nm. The thickness of the low refractive index layer is preferably larger than the average particle size of the low refractive index particles such as hollow particles.

[0036] The methods for forming a low refractive index layer can be roughly divided into wet methods and dry methods. Wet methods include a method of forming a low refractive index layer by a sol-gel method using metal alkoxide or the like, a method of forming a layer by coating a low refractive index resin such as fluororesin, and a method of forming a layer by coating a low refractive index layer-forming coating liquid in which low refractive index particles are contained in a resin composition. Dry methods include a method of forming a low refractive index layer by physical vapor deposition or chemical vapor deposition, and examples of materials include SiO2, SiO x (x=1~2), MgF2, etc. The wet method is superior to the dry method in terms of production efficiency, suppression of oblique reflection hue, and chemical resistance. In the present invention, among the wet methods, from the viewpoints of adhesion, water resistance, scratch resistance, and low refractive index, it is preferable to form the low refractive index layer using a coating liquid for forming the low refractive index layer, in which low refractive index particles are contained in a binder resin composition. As the binder resin composition, for example, the curable resin composition exemplified for the hard coat layer can be used, but the curable resin composition described below is preferred.

[0037] The low refractive index layer is usually located on the outermost surface of a molded article obtained by transferring a transfer layer to an adherend. Therefore, the low refractive index layer is required to have good scratch resistance. The scratch resistance of the low refractive index layer tends to be better as the surface shape is smoother. In the conventional transfer method, the surface shape of the low refractive index layer was approximately smooth. This is thought to be because, in the conventional transfer method, a resin coating substantially free of low refractive index particles was present near the interface where the low refractive index layer contacts the release substrate, and after transfer, the resin coating was located on the outermost surface of the molded product, and the surface of the resin coating was smooth, reflecting the surface shape of the release substrate. On the other hand, when the transfer sheet A of the present invention is used, the surface of the low refractive index layer at the outermost surface of the molded product is prone to minute irregularities due to the low refractive index particles. Furthermore, in recent years, hollow particles with large particle diameters have been used as low refractive index particles to reduce the refractive index of the low refractive index layer. The inventors have discovered a problem: even if the surface of such a low refractive index layer is rubbed with an object with only fine solid matter (e.g., sand) or only oil, no visible scratches are visible, it is still scratched when rubbed with an object with both solid matter and oil (hereinafter, this problem may be referred to as "oil dust resistance"). The action of rubbing with an object with solid matter and oil corresponds to, for example, the action of a user operating a touch panel type image display device with a finger that is covered with oil contained in cosmetics, food, etc. and sand contained in the air.

[0038] Through investigations, the inventors have found that the above-mentioned scratches are primarily caused by chipping of portions of hollow particles contained in the low-refractive index layer or the detachment of hollow particles. The inventors believe that this is due to the large unevenness caused by hollow particles formed on the surface of the low-refractive index layer. Specifically, when the surface of the low-refractive index layer is rubbed with a finger having solid and oily particles attached, the oil acts as a binder, causing the solid particles to adhere to the finger as the finger moves across the surface of the low-refractive index layer. This increases the likelihood of a portion of the solid object (e.g., a sharp point of sand) getting into a depression on the surface of the low-refractive index layer, or of the solid object moving through the depression with the finger and over the protruding portion (hollow particle). This exerts a large force on the protruding portion (hollow particle), potentially damaging or causing the hollow particle to detach. Furthermore, the resin itself located in the depression is also scratched by friction with the solid object, making the hollow particle more susceptible to detachment due to the damage to the resin. The inventors conducted extensive research and found that, in order to impart oil dust resistance, it is effective to use a combination of hollow and solid particles as low-refractive-index particles and to uniformly disperse the hollow and solid particles. Fig. 6 shows a cross-sectional photograph of a low-refractive-index layer in which hollow and solid particles are uniformly dispersed, and Fig. 7 shows a cross-sectional photograph of a low-refractive-index layer in which hollow and solid particles are not uniformly dispersed. The cross-sectional photographs in Figs. 6 and 7 were obtained by observation using an electron microscope H-7650 manufactured by Hitachi High-Technologies Corporation under conditions of an emission current of 10 μA, an acceleration voltage of 100 keV, and a filament voltage of 20 V.

[0039] In order to lower the refractive index of the low refractive index layer and improve the oil dust resistance, the low refractive index particles preferably include hollow particles and non-hollow particles. The material of the hollow particles and non-hollow particles may be either an inorganic compound such as silica or magnesium fluoride, or an organic compound, but silica is preferred from the viewpoint of low refractive index and strength. The following description will focus on hollow silica particles and non-hollow silica particles.

[0040] Hollow silica particles refer to particles that have an outer shell layer made of silica, and the particle interior surrounded by the outer shell layer is hollow, and the hollow interior contains air. Hollow silica particles are particles whose refractive index decreases in proportion to the occupancy rate of gas compared to the inherent refractive index of silica due to the inclusion of air. Non-hollow silica particles are particles that do not have a hollow interior like hollow silica particles. Non-hollow silica particles are, for example, solid silica particles. The shape of the hollow silica particles and non-hollow silica particles is not particularly limited, and may be a perfect sphere, a spheroid, a nearly spherical shape such as a polyhedron that can approximate a sphere, etc. Among these, in consideration of scratch resistance, a perfect sphere, a spheroid, or a nearly spherical shape is preferred.

[0041] Since hollow silica particles contain air inside, they serve to lower the refractive index of the entire low refractive index layer. By using hollow silica particles with a large particle size and a high air content, the refractive index of the low refractive index layer can be further lowered. However, hollow silica particles tend to have poor mechanical strength. In particular, when hollow silica particles with a large particle size and a high air content are used, the scratch resistance of the low refractive index layer tends to be reduced. The non-hollow silica particles, when dispersed in the binder resin, play a role in improving the scratch resistance of the low refractive index layer.

[0042] To incorporate hollow silica particles and non-hollow silica particles into a binder resin at a high concentration and to uniformly disperse the particles in the resin in the film thickness direction, 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 hollow silica particles are close to each other and the non-hollow particles can be inserted between the hollow silica particles. 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 non-hollow silica particles / average particle size of hollow silica particles) is preferably 0.29 or less, more preferably 0.20 or less. Furthermore, the average particle size ratio is preferably 0.05 or more. In consideration of optical properties and mechanical strength, the average particle size of the hollow silica particles is preferably 50 nm or more and 100 nm or less, more preferably 60 nm or more and 80 nm or less. In addition, in consideration of dispersibility while preventing aggregation 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.

[0043] The surfaces of the hollow silica particles and non-hollow silica particles are preferably coated with a silane coupling agent, and it is more preferable to use a silane coupling agent having a (meth)acryloyl group or an epoxy group. By treating the silica particles with a silane coupling agent, the affinity between the silica particles and the binder resin is improved, making the silica particles less likely to aggregate, and therefore making it easier for the silica particles to be dispersed uniformly.

[0044] Examples of silane coupling agents include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and 3-triethoxysilyl-N-(1,3-dimethoxysilane). methyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1,6-bis(trimethoxysilyl)hexane, trifluoropropyltrimethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane. In particular, it is preferable to use one or more selected from 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane.

[0045] The higher the content of hollow silica particles, the higher the filling rate of hollow silica particles in the binder resin, and the lower the refractive index of the low refractive index layer. Therefore, the content of hollow silica particles is preferably 100 parts by mass or more, more preferably 150 parts by mass or more, per 100 parts by mass of binder resin. On the other hand, if the content of hollow silica particles relative to the binder resin is too high, the number of hollow silica particles exposed from the binder resin increases, and the amount of binder resin bonding the particles decreases. As a result, the hollow silica particles tend to be easily damaged or fall off, which tends to reduce the mechanical strength of the low refractive index layer, such as scratch resistance. Furthermore, if the content of hollow silica particles is too high, transferability tends to be impaired. For this reason, the content of hollow silica particles is preferably 400 parts by mass or less, more preferably 300 parts by mass or less, relative to 100 parts by mass of binder resin.

[0046] If the content of solid silica particles is low, the presence of solid silica particles on the surface of the low refractive index layer may not affect the increase in hardness. Furthermore, if a large amount of solid silica particles is contained, the effect of uneven shrinkage due to polymerization of the binder resin can be reduced, and the unevenness that occurs on the surface of the low refractive index layer after the resin is cured can be reduced. Reducing the unevenness on the surface of the low refractive index layer is preferable because it can improve oil dust resistance and antifouling properties. Therefore, the content of solid silica particles is preferably 90 parts by mass or more, more preferably 100 parts by mass or more, per 100 parts by mass of the binder resin. On the other hand, if the content of the non-hollow silica particles is too high, the non-hollow silica particles tend to aggregate, causing uneven shrinkage of the binder resin and increasing surface irregularities. Furthermore, if the content of the non-hollow silica particles is too high, transferability tends to be impaired. Therefore, the content of the non-hollow silica particles is preferably 200 parts by mass or less, more preferably 150 parts by mass or less, per 100 parts by mass of the binder resin.

[0047] By incorporating hollow silica particles and non-hollow silica particles in the binder resin in the above ratio, the barrier properties of the low refractive index layer can be improved, presumably because the silica particles are uniformly dispersed at a high filling rate, thereby inhibiting the permeation of gases and the like. Furthermore, various cosmetics such as sunscreens and hand creams may contain low-volatility low-molecular-weight polymers. By improving the barrier properties of the low-refractive index layer, it is possible to prevent the low-molecular-weight polymer from penetrating into the coating film of the low-refractive index layer, and to prevent problems (such as abnormal appearance) caused by the low-molecular-weight polymer remaining in the coating film for a long period of time.

[0048] The binder resin of the low refractive index layer preferably contains a cured product of an ionizing radiation curable resin composition. The ionizing radiation curable compound contained in the ionizing radiation curable resin composition is preferably a compound having an ethylenically unsaturated bond group. Among these, a (meth)acrylate compound having a (meth)acryloyl group is more preferred. Hereinafter, a (meth)acrylate compound having four or more ethylenically unsaturated bond groups will be referred to as a "polyfunctional (meth)acrylate compound," and a (meth)acrylate compound having two to three ethylenically unsaturated bond groups will be referred to as a "low-functional (meth)acrylate compound."

[0049] As the (meth)acrylate-based compound, either a monomer or an oligomer can be used. In particular, from the viewpoint of suppressing uneven shrinkage during curing and facilitating smoothing of the uneven shape on the surface of the low refractive index layer, it is more preferable that the ionizing radiation-curable compound contains a low-functional (meth)acrylate-based compound. This is preferable in that smoothing of the uneven shape on the surface of the low refractive index layer can improve oil dust resistance and antifouling properties. The use of a low-functional (meth)acrylate-based compound is also preferable in that it improves the transferability of the transfer layer. The proportion of the low-functional (meth)acrylate compound in the ionizing radiation-curable compound is preferably 60% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, and most preferably 100% by mass. Furthermore, from the viewpoint of suppressing the uneven shrinkage during curing and facilitating smoothing of the irregularities on the surface of the low refractive index layer, it is preferable that the low-functional (meth)acrylate compound is a bifunctional (meth)acrylate compound having two ethylenically unsaturated bond groups.

[0050] Among the (meth)acrylate compounds, examples of bifunctional (meth)acrylate compounds include isocyanuric acid di(meth)acrylate, polyalkylene glycol di(meth)acrylates such as ethylene glycol di(meth)acrylate, polyethylene glycol diacrylate, and polybutylene glycol di(meth)acrylate, bisphenol A tetraethoxydiacrylate, bisphenol A tetrapropoxydiacrylate, and 1,6-hexanediol diacrylate. Examples of trifunctional (meth)acrylate compounds include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and isocyanuric acid-modified tri(meth)acrylate. Examples of the tetrafunctional or higher polyfunctional (meth)acrylate compounds include pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and dipentaerythritol tetra(meth)acrylate. These (meth)acrylate compounds may be modified as described below.

[0051] Examples of the (meth)acrylate oligomer include acrylate polymers such as urethane (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, and polyether (meth)acrylate. Urethane (meth)acrylates can be obtained, for example, by reacting a polyhydric alcohol and an organic diisocyanate with a hydroxy (meth)acrylate. In addition, preferred epoxy (meth)acrylates are (meth)acrylates obtained by reacting a tri- or higher functional aromatic epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, or the like with (meth)acrylic acid; (meth)acrylates obtained by reacting a di- or higher functional aromatic epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, or the like with a polybasic acid and (meth)acrylic acid; and (meth)acrylates obtained by reacting a di- or higher functional aromatic epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, or the like with a phenol and (meth)acrylic acid.

[0052] The (meth)acrylate compound may have a partially modified molecular skeleton to suppress shrinkage unevenness due to crosslinking and enhance surface smoothness. This is preferable because smoothing the unevenness of the low refractive index layer surface can improve oil dust resistance and stain resistance. For example, (meth)acrylate compounds modified with ethylene oxide, propylene oxide, caprolactone, isocyanuric acid, alkyl, cyclic alkyl, aromatic, bisphenol, etc. can be used. In particular, from the viewpoint of increasing affinity with low refractive index particles (including silica particles) and suppressing aggregation of the low refractive index particles, the (meth)acrylate compound is preferably modified with an alkylene oxide such as ethylene oxide or propylene oxide. The proportion of the alkylene oxide-modified (meth)acrylate compound in the ionizing radiation-curable compound is preferably 60% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, and most preferably 100% by mass. The alkylene oxide-modified (meth)acrylate compound is preferably a low-functionality (meth)acrylate compound, and more preferably a (meth)acrylate compound having two ethylenically unsaturated bond groups.

[0053] Examples of alkylene oxide-modified (meth)acrylate compounds having two ethylenically unsaturated bond groups include bisphenol F alkylene oxide-modified di(meth)acrylate, bisphenol A alkylene oxide-modified di(meth)acrylate, isocyanuric acid alkylene oxide-modified di(meth)acrylate, and polyalkylene glycol di(meth)acrylate, of which polyalkylene glycol di(meth)acrylate is preferred. The average repeating unit of the alkylene glycol contained in the polyalkylene glycol di(meth)acrylate is preferably 3 to 5. Furthermore, the alkylene glycol contained in the polyalkylene glycol di(meth)acrylate is preferably ethylene glycol and / or polyethylene glycol. Examples of alkylene oxide-modified (meth)acrylate compounds having three ethylenically unsaturated bond groups include trimethylolpropane alkylene oxide-modified tri(meth)acrylate and isocyanuric acid alkylene oxide-modified tri(meth)acrylate. The above ionizing radiation curable resins can be used alone or in combination of two or more.

[0054] (Elemental analysis of the surface region of the low refractive index layer) The low refractive index layer preferably contains a binder resin and silica particles, and the proportion of Si element attributable to the silica particles, as determined by analyzing the surface region of the low refractive index layer by X-ray photoelectron spectroscopy, is 10.0 atomic % or more and 18.0 atomic % or less, and the proportion of C element, when the proportion of Si element is converted to 100 atomic %, is 180 atomic % or more and 500 atomic % or less. In this configuration, the low refractive index layer is more preferably an antifouling low refractive index layer. Also, in this configuration, the silica particles preferably include hollow silica particles and non-hollow silica particles.

[0055] When the surface of the low refractive index layer is analyzed by X-ray photoelectron spectroscopy (hereinafter simply referred to as "XPS"), at least the elements C, O, and Si are detected. The element Si originates from silica particles (inorganic component) and organic components such as silane coupling agents and leveling agents. The element C originates from the binder resin, the surface treatment agent for the silica particles (silane coupling agent), and additives. However, considering the content in the low refractive index layer, the element C can be considered to be substantially derived from the binder resin.

[0056] The surface region of the low refractive index layer analyzed by XPS shows that the ratio of Si element belonging to silica particles is 10.0 atomic % or more and 18.0 atomic % or less, and when the ratio of Si element is converted to 100 atomic %, the ratio of C element is 180 atomic % or more and 500 atomic % or less. In this specification, the "surface region" is within the range of the detection area by X-ray photoelectron spectroscopy, and refers to the region of the low refractive index layer from the surface on the release substrate 2 side to a depth of 10 nm (the region of the low refractive index layer from the surface opposite the adherend to a depth of 10 nm). The "ratio of C element when the ratio of Si element is converted to 100 atomic %" can be calculated by "C / Si × 100(%)". Hereinafter, the "ratio of C element when the ratio of Si element is converted to 100 atomic %" may be abbreviated as "C / Si". Furthermore, since the Si discussed in this specification is inorganic Si element belonging to silica particles, Si means inorganic Si element unless otherwise specified.

[0057] The C / Si ratio in the surface region of the low refractive index layer reflects the distribution state of the solid silica particles and hollow silica particles in the thickness direction of the low refractive index layer. When silica particles are unevenly distributed on the side opposite the surface of the low-refractive-index layer, the proportion of Si element attributed to the silica particles in the surface region is low, and the proportion of C element is relatively high. A similar trend occurs when the silica particles are buried in the binder resin and barely present on the surface of the low-refractive-index layer. On the other hand, when silica particles (especially hollow silica particles) are not coated with binder resin and are exposed on the surface of the low-refractive-index layer, or when the coating of binder resin is very thin and they are nearly exposed, the proportion of Si element attributed to the silica particles is high, and the proportion of C element is relatively low.

[0058] The ratio of the Si element attributable to the silica particles in the surface region of the low refractive index layer reflects the state of existence of the solid silica particles and hollow silica particles in the surface region. Even if a large amount of hollow silica is present in the surface region of the low refractive index layer, it does not significantly contribute to an increase in the ratio of Si element attributable to silica particles because it is hollow. However, if a large amount of non-hollow silica is present in the surface region, the ratio of Si element attributable to silica particles will be increased. When a sufficient amount of silica particles is present in the surface region of the low refractive index layer, the ratio of Si element attributable to silica particles in the surface region of the low refractive index layer will be 10.0 atomic % or more. In particular, when the ratio of Si element attributable to silica particles is 13.0 atomic % or more, a high concentration of non-hollow silica particles will be present on the surface side, which is preferable because it improves scratch resistance. On the other hand, when the ratio of Si element attributable to silica particles exceeds 18.0 atomic %, not only non-hollow silica but also hollow silica particles will be present in the surface region, and the silica particles will be exposed or nearly exposed to the surface, which tends to reduce scratch resistance as described below. Furthermore, a sufficient amount of silica particles is present in the surface region of the low refractive index layer, so that the C / Si ratio satisfies 500 atomic % or less. If the C / Si ratio exceeds 500 atomic %, the silica particles are embedded in the binder resin, resulting in an excess of binder resin in the surface region, which tends to reduce scratch resistance. On the other hand, if the C / Si ratio is less than 180 atomic %, the amount of silica particles present on the surface increases, and in particular, hollow silica particles not coated with binder resin or hollow silica particles with a very thin coating of binder resin are exposed or nearly exposed on the surface, which tends to reduce scratch resistance. Considering scratch resistance and sufficient coverage, the C / Si ratio is preferably 200 atomic % or more, more preferably 250 atomic % or more. Furthermore, the C / Si ratio is preferably 400 atomic % or less, more preferably 350 atomic % or less.

[0059] By setting the C element ratio and Si element ratio in the surface region of the low refractive index layer within the above ranges, the hollow silica particles can be coated with an appropriate amount of binder resin, and a sufficient amount of solid silica particles can be present in the gaps between the hollow silica particles, which makes it easier to achieve a smoother surface of the low refractive index layer, low reflectance, and excellent surface durability such as high scratch resistance.

[0060] Even if the coating liquid for forming the low refractive index layer does not contain a fluorine-containing compound such as a fluorine-based leveling agent, fluorine may be detected on the surface of the formed low refractive index layer in some cases. For example, this may be the case when another functional layer adjacent to the low refractive index layer contains a fluorine-based leveling agent, and the leveling agent of the other functional layer migrates to the surface of the low refractive index layer. In this embodiment, the F element may be detected by XPS as long as it does not impair the effects of the present invention, but it is preferable that the F element is not detected by XPS. In other words, it is preferable that the surface region of the low refractive index layer does not substantially contain fluorine atoms. Since the fluorine-containing compound itself tends to be relatively soft, by making the surface region of the low refractive index layer substantially free of fluorine atoms, it is possible to easily improve scratch resistance. Even if another functional layer adjacent to the low refractive index layer contains a fluorine-based leveling agent, if the low refractive index layer exhibits the above element ratio and contains silica particles at a high concentration relative to the binder resin, diffusion of the fluorine-containing compound in the other functional layer can be suppressed, making it easier to make the surface region of the low refractive index layer substantially free of F atoms. In this specification, "substantially not containing fluorine atoms" means that the ratio of F elements in the surface region is 0.5 atomic % or less, more preferably 0.1 atomic % or less.

[0061] It is also preferable that the surface region of the low refractive index layer has the above element ratios in that high gas barrier properties (water vapor permeability, oxygen gas permeability) can be imparted.

[0062] In order to achieve the above-mentioned element ratio, it is preferable that the hollow silica particles and non-hollow silica particles are uniformly dispersed in the low refractive index layer. In this specification, "uniformly dispersed" means that the hollow silica particles and non-hollow silica particles are not only uniformly dispersed in the surface region of the low refractive index layer, but also uniformly dispersed in the thickness direction of the low refractive index layer when viewed in cross section. That is, when XPS analysis is performed in the thickness direction of the low refractive index layer, it is preferable that the ratio of Si element belonging to the silica particles and C / Si satisfy the above-mentioned ranges at different locations in the thickness direction. For example, when the thickness of the low refractive index layer is divided into three equal parts and defined as a first region, a second region, and a third region in order from the transparent substrate side, it is preferable that the ratio of Si element belonging to the silica particles and C / Si satisfy the above-mentioned ranges at any location in the first region and any location in the second region. FIG. 6 shows a low refractive index layer in which hollow particles and non-hollow particles are uniformly dispersed, and FIG. 7 shows a cross-sectional photograph of a low refractive index layer in which hollow particles and non-hollow particles are not uniformly dispersed. The surface of the low refractive index layer in which hollow silica particles and non-hollow silica particles are uniformly dispersed is also preferred in that it is easy to improve the antifouling properties.

[0063] (Leveling agent) The low refractive index layer preferably contains a leveling agent from the viewpoint of antifouling properties and surface smoothness. The leveling agent preferably has a reactive group such as a (meth)acryloyl group and is capable of reacting with the binder resin. The leveling agent may be a fluorine-based or silicone-based agent, with a silicone-based agent being preferred. The inclusion of a silicone-based leveling agent can further smoothen the surface of the low refractive index layer. Furthermore, compared with a fluorine-based agent, a silicone-based agent can more easily improve the slipperiness and antifouling properties (ease of wiping off fingerprints, large contact angles with pure water and hexadecane) of the surface of the low refractive index layer. Furthermore, compared with a fluorine-based agent, a silicone-based agent is preferred because it is less likely to impair the hardness of the low refractive index layer.

[0064] The content of the leveling agent is preferably 1 to 25 parts by mass, more preferably 2 to 20 parts by mass, and even more preferably 5 to 18 parts by mass, relative to 100 parts by mass of the binder resin. By setting the content of the leveling agent to 1 part by mass or more, it is possible to easily impart various properties such as antifouling properties, and by setting the content of the leveling agent to 25 parts by mass or less, it is possible to suppress a decrease in scratch resistance.

[0065] The low refractive index layer preferably has a smooth surface to obtain excellent surface durability. The maximum height roughness Rz is sufficient as long as it is 110 nm or less, preferably 100 nm or less, and more preferably 90 nm or less. Furthermore, since a smoother surface can obtain even better surface durability, Rz is preferably 70 nm or less, more preferably 60 nm or less, and even more preferably 55 nm or less. Furthermore, Rz / Ra (Ra is the arithmetic mean roughness) is preferably 22.0 or less, more preferably 18.0 or less, more preferably 16.0 or less, more preferably 12.0 or less, more preferably 10.0 or less, and more preferably 9.0 or less. In this specification, Ra and Rz are two-dimensional roughness parameters described in the Scanning Probe Microscope SPM-9600 Upgrade Kit Instruction Manual (SPM-9600, February 2016, pp. 194-195) that have been expanded to three dimensions. Ra and Rz are defined as follows: (arithmetic mean roughness Ra) When a reference length (L) is cut out from the roughness curve in the direction of the average line, and the X axis is taken in the direction of the average line of this cut-out portion and the Y axis is taken in the direction of the vertical magnification, and the roughness curve is expressed as y = f(x), the following formula can be used.

number

[0066] A small Rz means that the convex portions caused by the hollow silica particles in the micro-region are small. Also, a small Rz / Ra means that the irregularities caused by the silica particles in the micro-region are uniform and do not have protruding irregularities relative to the average elevation difference of the irregularities. The value of Ra is not particularly limited, but is preferably 15 nm or less, more preferably 12 nm or less, even more preferably 10 nm or less, and even more preferably 6.5 nm or less. By uniformly dispersing the low refractive index particles in the low refractive index layer and suppressing uneven shrinkage of the low refractive index layer, it becomes easier to satisfy the above-mentioned ranges of Rz and Rz / Ra. Furthermore, by having the low refractive index layer exhibit the above-mentioned element ratio, it becomes easier to satisfy the above-mentioned ranges of Rz and Rz / Ra. The Rz of the surface of the low refractive index layer may become as large as about 90 to 110 nm depending on the processing conditions of the low refractive index layer. In such a case, if Rz / Ra is in the above range, it is easy to obtain favorable surface resistance.

[0067] By ensuring that the Rz and Rz / Ra of the low refractive index layer surface are within the above ranges, the resistance when solid matter moves over the convex portions (caused by hollow silica particles present near the surface) on the low refractive index layer surface can be reduced. Therefore, even when rubbed with oily sand under a load, solid matter is believed to move smoothly over the low refractive index layer surface. It is also believed that the hardness of the concave portions themselves is increased. As a result, it can be assumed that breakage and shedding of the hollow silica particles are prevented, and damage to the binder resin itself is also prevented. Furthermore, by setting Rz and Rz / Ra within the above ranges, it becomes easier to achieve good antifouling properties.

[0068] On the other hand, if the Rz and Rz / Ra of the low refractive index layer surface are too small, blocking may occur during the manufacturing process. Therefore, Rz is preferably 30 nm or more, more preferably 70 nm or more. Furthermore, Rz / Ra is preferably 3.0 or more, more preferably 5.0 or more.

[0069] In this specification, various parameters such as surface roughness such as Rz and Ra, optical properties such as reflectance Y value, and element ratios refer to the average values ​​of measurements taken at 14 points excluding the minimum and maximum values ​​of the 16 measurement points, unless otherwise specified. In this specification, the 16 measurement points are preferably determined by drawing a margin of 0.5 cm from the outer edge of the measurement sample and dividing the area inside the margin into five equal parts vertically and horizontally, with the measurement centers being the 16 intersections. For example, if the measurement sample is rectangular, it is preferable to leave a margin of 0.5 cm from the outer edge of the rectangle and perform measurements at 16 intersections of dotted lines dividing the area inside the margin into five equal parts vertically and horizontally, and calculate the parameters as the average values. Note that if the measurement sample has a shape other than a rectangle, such as a circle, ellipse, triangle, or pentagon, it is preferable to draw a rectangle inscribed in the shape and perform measurements at 16 points on the rectangle using the above method. Unless otherwise specified, the surface roughness and other parameters are measured at a temperature of 23°C ± 5°C and a relative humidity of 40 to 65%.Unless otherwise specified, the sample is exposed to the above atmosphere for at least 30 minutes before each measurement and then measured and evaluated.

[0070] The low refractive index layer can be formed by applying and drying a coating liquid for forming a low refractive index layer, in which each component constituting the low refractive index layer is dissolved or dispersed. Usually, a solvent is used in the coating liquid to adjust the viscosity or to make each component soluble or dispersible. Examples of the solvent include ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), ethers (dioxane, tetrahydrofuran, etc.), aliphatic hydrocarbons (hexane, etc.), alicyclic hydrocarbons (cyclohexane, etc.), aromatic hydrocarbons (toluene, xylene, etc.), halogenated carbons (dichloromethane, dichloroethane, etc.), esters (methyl acetate, ethyl acetate, butyl acetate, etc.), alcohols (butanol, cyclohexanol, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, etc.), cellosolve acetates, sulfoxides (dimethyl sulfoxide, etc.), glycol ethers (1-methoxy-2-propyl acetate, etc.), amides (dimethylformamide, dimethylacetamide, etc.), and mixtures thereof may also be used.

[0071] If the solvent evaporates too quickly, the solvent will convect violently when the coating liquid for forming the low refractive index layer dries. Therefore, even if the silica particles in the coating liquid are uniformly dispersed, the state of uniform dispersion is likely to be disrupted by the violent convection of the solvent during drying. For this reason, it is preferable to include a solvent with a slow evaporation rate. Specifically, it is preferable to include a solvent with a relative evaporation rate (relative evaporation rate when the evaporation rate of n-butyl acetate is set to 100) of 70 or less, and more preferably a solvent with a relative evaporation rate of 30 to 60. Furthermore, the solvent with a relative evaporation rate of 70 or less preferably accounts for 10 to 50% by mass, and more preferably 20 to 40% by mass, of the total solvent. Examples of relative evaporation rates for slow-evaporating solvents are isobutyl alcohol (64), 1-butanol (47), 1-methoxy-2-propyl acetate (44), ethyl cellosolve (38), and cyclohexanone (32). The remaining solvent (solvent other than the solvent with a slow evaporation rate) is preferably one that has excellent resin solubility. The remaining solvent preferably has a relative evaporation rate of 100 or more.

[0072] In addition, in order to suppress convection of the solvent during drying and improve the dispersibility of the silica particles, it is preferable that the drying temperature during the formation of the low refractive index layer is as low as possible. The drying temperature can be appropriately set in consideration of the type of solvent, the dispersibility of the silica particles, the production rate, etc. As described above, controlling the relative evaporation rate and drying temperature of the solvent is preferable because it also leads to smoothing of the surface of the low refractive index layer.

[0073] -High refractive index layer- The high refractive index layer, which is an example of a functional layer, preferably has a refractive index of 1.53 to 1.85, more preferably 1.54 to 1.80, more preferably 1.55 to 1.75, and even more preferably 1.56 to 1.70. The thickness of the high refractive index layer is preferably 200 nm or less, more preferably 50 to 180 nm, and even more preferably 70 to 150 nm. When a high refractive index hard coat layer is used, the thickness is preferably similar to that of the hard coat layer.

[0074] The high refractive index layer can be formed from a coating liquid for forming a high refractive index layer, which contains a binder resin composition and high refractive index particles. As the binder resin composition, for example, the curable resin composition exemplified for the hard coat layer can be used.

[0075] Examples of high refractive index particles include antimony pentoxide (1.79), zinc oxide (1.90), titanium oxide (2.3 to 2.7), cerium oxide (1.95), tin-doped indium oxide (1.95 to 2.00), antimony-doped tin oxide (1.75 to 1.85), yttrium oxide (1.87), and zirconium oxide (2.10).

[0076] 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. From the viewpoint of whitening suppression and transparency, 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, more preferably 60 nm or less, and more preferably 30 nm or less. The smaller the average particle size of the high refractive index particles, the better the transparency, and by making it 60 nm or less, the transparency can be made extremely good.

[0077] The average particle size of the high refractive index particles or the low refractive index particles can be calculated by the following steps (y1) to (y3). (y1) A cross section of the high refractive index layer or low refractive index layer is imaged by TEM or STEM. The acceleration voltage of the TEM or STEM is preferably 10 kV to 30 kV, and the magnification is preferably 50,000 to 300,000 times. (y2) Randomly extract 10 particles from the observed image and calculate the particle diameter of each particle. The particle diameter is measured as the distance between two parallel lines that maximize the distance between the two lines when the cross section of the particle is sandwiched between the two lines. If the particles are aggregated, the aggregated particles are considered to be a single particle and are measured. (y3) The same procedure is carried out five times on a separate observation image of the same sample, and the value obtained from the number average of the particle diameters of a total of 50 particles is taken as the average particle diameter of the high refractive index particles or low refractive index particles.

[0078] -Anti-glare layer- An antiglare layer, which is an example of a functional layer, has the role of enhancing the antiglare properties of an adherend. The antiglare layer can be formed, for example, from a coating liquid for forming an antiglare layer containing a binder resin composition and particles. Alternatively, the antiglare layer can be formed by utilizing phase separation of the resin composition, or by incorporating particles into a resin composition utilizing such phase separation. For example, the curable resin composition exemplified for the hard coat layer can be used as the binder resin composition.

[0079] The particles may be either organic or inorganic. Examples of organic particles include particles made of polymethyl methacrylate, polyacrylic-styrene copolymer, melamine resin, polycarbonate, polystyrene, polyvinyl chloride, benzoguanamine-melamine-formaldehyde condensate, silicone, fluorine-based resin, and polyester-based resin. Examples of inorganic particles include particles made of silica, alumina, antimony, zirconia, and titania.

[0080] The average particle size of the particles in the antiglare layer cannot be generalized as it differs depending on the thickness of the antiglare layer, but is preferably 1.0 to 10.0 μm, more preferably 2.0 to 8.0 μm, and even more preferably 3.0 to 6.0 μm.

[0081] The average particle size of the particles in the antiglare layer can be calculated by the following steps (z1) to (z3). (z1) A transmission observation image of the cross section of the antiglare layer is taken using an optical microscope. The magnification is preferably 500 to 2000 times. (z2) Randomly extract 10 particles from the observed image and calculate the particle diameter of each particle. The particle diameter is measured as the distance between two parallel lines that maximizes the distance between the two lines when the cross section of the particle is sandwiched between the two lines. (z3) The same procedure is repeated five times on a separate observation image of the same sample, and the value obtained from the number average of the particle diameters of a total of 50 particles is regarded as the average particle diameter of the particles in the antiglare layer.

[0082] The content of particles in the antiglare layer cannot be generalized because it varies depending on the desired level of antiglare properties, but it is preferably 1 to 100 parts by mass, more preferably 5 to 50 parts by mass, and even more preferably 10 to 30 parts by mass, per 100 parts by mass of the resin component. The antiglare layer may contain fine particles having an average particle size of less than 500 nm in order to impart antistatic properties, control the refractive index, and adjust the shrinkage of the antiglare layer due to curing of the curable resin composition.

[0083] The thickness of the antiglare layer is preferably 0.5 μm or more, more preferably 1.0 μm or more, and even more preferably 2.0 μm or more. The thickness of the antiglare layer is preferably 50 μm or less, more preferably 30 μm or more, more preferably 20 μm or less, more preferably 15 μm or less, and even more preferably 10 μm or less.

[0084] -Anti-fouling layer- An antifouling layer, which is an example of a functional layer, has the role of enhancing the antifouling properties of an adherend. When the transfer layer has two or more functional layers, it is preferable that the antifouling layer is formed on the side farthest from the release substrate 1. The antifouling layer can be formed from a coating liquid for forming an antifouling layer, which contains, for example, a binder resin composition and an antifouling agent. As the binder resin composition, for example, the curable resin composition exemplified for the hard coat layer can be used.

[0085] Examples of the antifouling agent include fluorine-based resins, silicone-based resins, and fluorine-silicone copolymer resins. The antifouling agent preferably has a reactive group capable of reacting with the binder resin composition in order to prevent bleeding out from the antifouling layer, i.e., the antifouling agent is preferably immobilized to the binder resin composition in the antifouling layer. Furthermore, from the viewpoint of suppressing bleeding out from the stain-resistant layer, a self-crosslinkable stain-resistant agent is also preferred. In other words, the stain-resistant agent in the stain-resistant layer is preferably self-crosslinked.

[0086] The content of the antifouling agent in the antifouling layer is preferably 5 to 30 mass %, more preferably 7 to 20 mass %, of the total solid content of the antifouling layer.

[0087] The thickness of the antifouling layer is not particularly limited. For example, when it is an antifouling hard coat layer, it is preferably based on the thickness of the hard coat layer. Furthermore, when it is an antifouling low refractive index layer, it is preferably based on the thickness of the low refractive index layer.

[0088] The degree of antifouling property of the antifouling layer varies depending on the required antifouling property and therefore cannot be generally defined, but it is preferable that the contact angle with pure water is 80 degrees or more, more preferably 85 degrees or more, and even more preferably 90 degrees or more. If the contact angle of pure water on the antifouling layer becomes too large, the content of the antifouling agent in the antifouling layer increases relatively, which may result in a deterioration in the physical properties (scratch resistance, etc.) of the antifouling layer. Therefore, the contact angle of pure water on the antifouling layer is preferably 120 degrees or less, more preferably 110 degrees or less, even more preferably 100 degrees or less, and even more preferably 95 degrees or less. When other functional layers such as a low refractive index layer have antifouling properties, the contact angle of pure water is preferably within the above range. In this specification, the contact angle is measured by the θ / 2 method.

[0089] -Layer located farthest from the release substrate 2- When the adherend is glass, the layer that is located farthest from the release substrate 2 among the layers constituting the transfer layer preferably contains a resin having one or more functional groups selected from a carboxyl group and a methoxy group. When this layer contains a resin having one or more functional groups selected from a carboxyl group and a methoxy group, it is possible to easily improve adhesion to glass. The proportion of resins having one or more functional groups selected from carboxyl groups and methoxy groups in the total resin components of the layer is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, and most preferably 100% by mass.

[0090] <Process (2)> Step (2) is a step of laminating a release substrate 2 on the transfer layer formed in step (1) to obtain a transfer sheet A having a release substrate 1, a transfer layer, and a release substrate 2 in this order, and in which the peel strength 2 between the release substrate 2 and the transfer layer is greater than the peel strength 1 between the release substrate 1 and the transfer layer.

[0091] In the step (2), there is no particular limitation on the means for laminating the release substrate 2 on the transfer layer. For example, the release substrate 2 can be laminated on the transfer layer by dry lamination. When the release substrate 2 has an adhesive layer, the adhesive force of the adhesive layer can be utilized to dry laminate the release substrate 2 onto the transfer layer. Furthermore, when the functional layer farthest from the release substrate 1 among the functional layers constituting the transfer layer has tack at the time of step (2), the tack of the functional layer can be utilized to dry laminate the release substrate 2 onto the transfer layer.

[0092] Of the two release substrates included in transfer sheet A, release substrate 1 is peeled off before transfer and does not remain at the time of transfer, but release substrate 2 remains at the time of transfer. To enable only release substrate 1 to be peeled off before transfer, in step (2), it is necessary to make peel strength 2 between release substrate 2 and the transfer layer greater than peel strength 1 between release substrate 1 and the transfer layer. As shown in Comparative Example 4-1, if an opportunity for peeling is provided by creating a notch or the like and the transfer sheet is pressed from both sides, it is possible to peel off the release substrate 1 first even if the relationship "peel strength 2 < peel strength 1" is satisfied. However, if the relationship is "peel strength 2 < peel strength 1", the transfer process becomes significantly more complicated and a load is applied to the transfer layer during transfer, impairing the function of the transfer layer, which is not preferable.

[0093] The difference between peel strength 2 and peel strength 1 (peel strength 2 - peel strength 1) is preferably 15 mN / 25 mm or more, more preferably 40 mN / 25 mm or more, and even more preferably 100 mN / 25 mm or more, from the viewpoint of facilitating peeling of only release substrate 1 before transfer. If the difference is too large, it may be difficult to peel release substrate 2 after transfer, so the difference is preferably 450 mN / 25 mm or less, more preferably 350 mN / 25 mm or less, even more preferably 300 mN / 25 mm or less, and even more preferably 200 mN / 25 mm or less. From the viewpoint of preventing the release substrate 1 from falling off, the peel strength 1 is preferably 10 mN / 25 mm or more, more preferably 20 mN / 25 mm or more, even more preferably 40 mN / 25 mm or more, and even more preferably 50 mN / 25 mm or more. From the viewpoint of easily differentiating the peel strength 1 from the peel strength 2, the peel strength 1 is preferably 90 mN / 25 mm or less, and more preferably 70 mN / 25 mm or less. From the viewpoint of easily differentiating peel strength 2 from peel strength 1, peel strength 2 is preferably 100 mN / 25 mm or more, more preferably 120 mN / 25 mm or more, and even more preferably 140 mN / 25 mm or more. Furthermore, from the viewpoint of suppressing cohesive failure of the adhesive layer and transfer layer on the release substrate 2 side when peeling off the release substrate 2, peel strength 2 is preferably 600 mN / 25 mm or less, more preferably 500 mN / 25 mm or less, even more preferably 400 mN / 25 mm or less, and even more preferably 300 mN / 25 mm or less. In this specification, peel strength can be measured in accordance with the 180-degree peel test of JIS Z0237:2009. The atmosphere in which peel strength is measured is preferably 23°C and humidity is 40 to 65%. Furthermore, before measuring the peel strength, it is preferable to allow the sample to acclimate to the above atmosphere for 30 minutes. Measurement is performed three times for each sample, and the average value is taken as the peel strength.

[0094] <<Release base material 2>> The release substrate 2 can be any substrate that can be peeled off from the transfer layer without any particular limitation, and a plastic film is preferably used. As the plastic film used as the release substrate 2, the same plastic films as those exemplified as the release substrate 1 can be used.

[0095] The surface of the transfer layer side of the release substrate 2 preferably has an arithmetic mean roughness Ra of 0.04 μm or less at a cutoff value of 0.25 mm according to JIS B0601:1994. Ra of the release substrate 2 can be measured by the same method as Ra of the release substrate 1.

[0096] Note that release substrate 1 is peeled off before transfer and does not remain at the time of transfer, but release substrate 2 remains at the time of transfer. For this reason, it is preferable that release substrate 2 has good conformability to the shape of the adherend. Specifically, release substrate 2 preferably has an elongation at break of 70% or more, more preferably 80% or more, in a tensile property test in accordance with JIS K7127:1999. Note that if release substrate 2 is stretchable, a shrinking force is generated in release substrate 2 after laminating release substrate 2 on the transfer layer, making release substrate 1 more likely to peel from the transfer layer. For this reason, when a stretchable release substrate 2 is used, it is preferable to increase peel strength 1 (preferably 40 mN / 25 mm or more, more preferably 50 mN / 25 mm or more).

[0097] From the viewpoint of making the peel strength 2 greater than the peel strength 1 and enabling the release substrate 2 to be peeled from the transfer layer, it is preferable that the release substrate 2 has an adhesive layer with weak adhesive strength on its surface. The adhesive contained in the adhesive layer on the surface of the release substrate 2 is preferably an adhesive with a weak adhesive strength so that the peel strength 2 falls within the above range.

[0098] The release substrate 2 may have an antistatic layer from the viewpoint of suppressing peeling electrification. The thickness of the release substrate 2 is not particularly limited, but from the viewpoints of ease of handling after peeling off the release substrate 1 and ability to conform to the shape of the adherend, it is preferably 5 to 100 μm, more preferably 10 to 80 μm, and even more preferably 20 to 70 μm. Furthermore, since the entire transfer sheet B becomes flexible and can be easily used for transferring to a 3D shape, the upper limit is more preferably 60 μm or less, and most preferably 45 μm or less.

[0099] The effects of the transfer sheet A obtained by the transfer sheet manufacturing method of the present invention will be described below. Transfer sheet A is used as follows. First, before transfer, release substrate 1 is peeled off from transfer sheet A to obtain transfer sheet B (200) shown in Fig. 3. Then, as shown in Fig. 4(a), laminate C (400) is obtained by closely adhering the transfer layer side of transfer sheet B to the adherend, and then, as shown in Fig. 4(b), release substrate 2 is peeled off from laminate C to obtain molded body 800 in which the transfer layer is transferred onto the adherend. The thickness direction of the functional layer 1 (31) and the functional layer 2 (32) in Figure 4(b) is the same as the thickness direction of the functional layer 1 (31) and the functional layer 2 (32) of the transfer layer in Figure 1. In other words, the upper side in the thickness direction of the functional layer 1 (31) and the functional layer 2 (32) in Figure 4(b) is the same as the upper side in the thickness direction of the functional layer 1 (31) and the functional layer 2 (32) in Figure 1. When a functional layer is formed on a substrate, the function may be uniform across the thickness of the functional layer, but in many cases, the function is unevenly distributed across the thickness of the functional layer. In other words, the surface side of the functional layer often has different functions than the substrate side. Furthermore, typical functional paints are designed to fully function on the surface side of the functional layer. Therefore, the fact that the upper thickness sides of functional layer 1 (31) and functional layer 2 (32) in Figure 4(b) are aligned with the upper thickness sides of functional layer 1 (31) and functional layer 2 (32) in Figure 1 means that the molded product in Figure 4(b) is likely to fully function in the functional layer. For example, in both Figures 1 and 4(b), the functional component is unevenly distributed on the surface side (the upper side in Figures 1 and 4(b)) (the darker the color of functional layer 2 (32), the higher the density of the functional component, indicating the uneven distribution of the functional component). This allows functional layer 2 (32) to fully function.

[0100] On the other hand, a conventional transfer sheet has a cross-sectional configuration as shown in Fig. 5(a), for example. The conventional transfer sheet in Fig. 5(a) has a transfer layer 30 on a release substrate 13, and the transfer layer 30 has a functional layer 2 (32) and a functional layer 1 (31) from the release substrate side. In the case of a conventional transfer sheet, a laminate is obtained by closely adhering the transfer layer side of the transfer sheet to the adherend, as shown in Figure 5(b), and then the release substrate 13 is peeled off from the laminate, as shown in Figure 5(c), to obtain a molded body 800 in which the transfer layer is transferred onto the adherend. The thickness direction orientation of functional layer 1 (31) and functional layer 2 (32) in Fig. 5(c) is different from the thickness direction orientation of functional layer 1 (31) and functional layer 2 (32) of the transfer layer in Fig. 5(a). In other words, the upper side in the thickness direction of functional layer 1 (31) and functional layer 2 (32) in Fig. 5(c) corresponds to the lower side in the thickness direction of functional layer 1 (31) and functional layer 2 (32) in Fig. 5(a). In this way, in the case of transfer using a conventional transfer sheet, the thickness direction of the functional layer formed on the releasable substrate is reversed from the thickness direction of the functional layer transferred to the adherend, making it difficult for the functional layer to fully function. For example, in the molded body 800 of Figure 5(c), the functional component of functional layer 2 (32) is unevenly distributed on the opposite side from the surface (the lower side of Figure 5(c)), so functional layer 2 (32) cannot fully function.

[0101] As described above, the transfer sheet A obtained by the method for producing a transfer sheet of the present invention can impart sufficient functionality to a molded article.

[0102] The uneven distribution of functions described above is particularly pronounced when the functional layer is an antiglare layer or an antifouling layer. Therefore, the method for producing a transfer sheet of the present invention is suitable when at least one of the functional layers is an antiglare layer or an antifouling layer, as it is more likely to exhibit its effects. In particular, it is preferred that at least one of the functional layers is an antifouling low refractive index layer. On the other hand, in the case of conventional transfer sheets, even if they contain an antiglare layer and an antifouling layer as transfer layers, they are unable to impart sufficient antiglare and antifouling properties to the adherend for the following reasons. First, when a conventional transfer sheet includes an antiglare layer as a transfer layer, the surface shape of the antiglare layer transferred to the adherend has a shape that is approximately complementary to the surface shape of the release sheet. Furthermore, the surface shape of the release sheet is usually smoothed to facilitate releasability from the transfer layer, so the surface shape of the antiglare layer transferred to the adherend does not have an uneven shape and does not provide sufficient antiglare properties. For example, if functional layer 2 (32) in Figure 5(a) is the antiglare layer and functional layer 1 (31) is the adhesive layer, the surface shape of functional layer 2 (32, antiglare layer) in Figure 5(c) will be complementary to the surface shape of the release substrate 13, making it difficult to provide antiglare properties due to surface unevenness. Furthermore, when an antifouling layer containing an antifouling agent is formed on a substrate, the antifouling agent tends to gather at the air interface, which has low surface energy. For example, if Functional Layer 2 (32) in Figure 5(a) is the antifouling layer and Functional Layer 1 (31) is the adhesive layer, the proportion of the functional component (antifouling agent) on the surface side of Functional Layer 2 (32, antifouling layer) in Figure 5(c) is low, and sufficient antifouling properties cannot be achieved.

[0103] <Process (3)> In the method for producing a transfer sheet of the present invention, it is preferable to further carry out the following step (3). (3) A step of peeling off the release substrate 1 from the transfer sheet A to obtain a transfer sheet B having the transfer layer on the release substrate 2.

[0104] In step (3), the release substrate 1 is peeled off from the transfer sheet A obtained in step (2). The release substrate 1 also serves to protect the transfer layer when the transfer sheet is cut or transported, but is not necessary during transfer. For this reason, it is preferable to peel off the release substrate 1 before transfer, as shown in step (3).

[0105] [Method of manufacturing molded body] The method for producing a molded article of the present invention involves sequentially carrying out the following steps (4) and (5). (4) A step of obtaining a laminate C by closely adhering the surface of the transfer sheet B on the side of the transfer layer to an adherend. (5) A step of peeling off the release substrate 2 from the laminate C to obtain a molded article having a transfer layer on an adherend.

[0106] Step (4) is a step of obtaining a laminate C (400) in which the transfer layer side of the transfer sheet B is adhered to an adherend (FIG. 4(a)). In step (4), the means for adhering the transfer layer side of the transfer sheet B to the adherend is not particularly limited. For example, if the layer furthest from the release substrate 2 among the layers constituting the transfer layer exhibits adhesiveness (preferably heat-sensitive adhesiveness), the adhesiveness of this layer can be utilized to adhere the transfer layer to the adherend. In addition, in the case of in-mold molding, the transfer layer and the adherend can be adhered to each other by using a resin that has high adhesiveness to the transfer layer as the injected resin (≒adherend). Alternatively, the transfer layer and the adherend may be adhered to each other via a double-sided adhesive sheet.

[0107] <Adherend> The material of the adherend is not particularly limited, and examples thereof include one selected from inorganic materials such as glass and ceramic, and resins, or a mixture thereof.

[0108] When in-mold molding is performed, it is preferable to use an injection-moldable thermoplastic resin or thermosetting resin as the adherend, and among these, a thermoplastic resin is more preferable. Examples of thermoplastic resins include polystyrene-based resins, polyolefin-based resins, ABS resins (including heat-resistant ABS resins), AS resins, AN resins, polyphenylene oxide-based resins, polycarbonate-based resins, polyacetal-based resins, acrylic-based resins, polyethylene terephthalate-based resins, polybutylene terephthalate-based resins, polysulfone-based resins, and polyphenylene sulfide-based resins.

[0109] The shape of the adherend is not particularly limited, and may be a flat plate or may have a three-dimensional shape. The thickness of the adherend is also not particularly limited. The adherend may be one that has been molded in advance, or one that is molded during step (4) such as in-mold molding.

[0110] Step (5) is a step of peeling off the release substrate 2 (20) from the laminate C (400) to obtain a molded article having the transfer layer 30 on the adherend 300 (FIG. 4(b)).

[0111] In steps (4) and (5), known transfer methods can be used. Examples include (i) a method of producing a laminate C by adhering the transfer layer side of transfer sheet B to a pre-formed adherend, and then peeling off the release substrate 2 from the laminate C, (ii) a method of producing a laminate C by adhering the transfer layer side of transfer sheet B to a flat adherend, and then peeling off the release substrate 2 from the laminate C, and (iii) a method of producing a laminate C by integrating (adhering) the transfer layer side of transfer sheet B with the adherend during injection molding, and then peeling off the release substrate 2 from the laminate C (in-mold molding (injection molding simultaneous transfer decoration method)).

[0112] One embodiment of in-mold molding includes the following steps (a) to (d). (a) A step of placing the transfer layer side of the transfer sheet B facing the inside of the in-mold forming die. (b) A step of injecting resin into the in-mold molding die. (c) A step of obtaining a laminate C by integrating (adhering) the transfer layer side of the transfer sheet B with the resin. (d) A step of removing the release substrate 2 from the laminate C after removing the laminate C from the mold.

[0113] [Transfer sheet A] The transfer sheet A of the present invention comprises a release substrate 1, a transfer layer, and a release substrate 2 in this order, wherein the peel strength 2 between the release substrate 2 and the transfer layer is greater than the peel strength 1 between the release substrate 1 and the transfer layer, the transfer layer includes at least one functional layer, and at least one of the functional layers has its function concentrated toward the release substrate 2 side.

[0114] The embodiments of the release substrates 1 and 2, and the peel strengths 1 and 2 of the transfer sheet A of the present invention are the same as those of the release substrates 1 and 2, and the peel strengths 1 and 2 used in the transfer sheet manufacturing method of the present invention described above. For example, the difference between peel strength 2 and peel strength 1 (peel strength 2 - peel strength 1) is preferably 15 mN / 25 mm or more, more preferably 40 mN / 25 mm or more, and even more preferably 100 mN / 25 mm or more. Furthermore, the difference is preferably 450 mN / 25 mm or less, more preferably 350 mN / 25 mm or less, even more preferably 300 mN / 25 mm or less, and even more preferably 200 mN / 25 mm or less. The embodiment of the transfer layer of the transfer sheet A of the present invention is the same as the embodiment of the transfer layer of the above-mentioned method for producing a transfer sheet of the present invention, but the uneven distribution of functions will be further explained below.

[0115] The transfer layer of the transfer sheet A of the present invention includes at least one functional layer, and at least one of the functional layers has a function unevenly distributed on the release substrate 2 side. Since at least one functional layer included in the transfer layer has a function unevenly distributed on the release substrate 2 side, the molded article obtained by peeling off the release substrate 1 to obtain transfer sheet B and transferring the transfer layer of transfer sheet B to an adherend can fully exhibit the function of the functional layer whose function is unevenly distributed on the release substrate 2 side. When the functional layer is a single layer, it is sufficient that the function is unevenly distributed on the release substrate 2 side within the single layer. Note that when the transfer layer has two or more functional layers, it is preferable that the function of the functional layer located closest to the release substrate 2 is unevenly distributed. As described above, it is difficult to ensure that the functions of the antiglare layer and the antifouling layer are fully exhibited in conventional transfer sheets. For this reason, the transfer sheet A of the present invention is suitable in that it is more likely to exhibit its effects when the functional layer whose function is unevenly distributed on the release substrate 2 side is an antiglare layer or an antifouling layer. In particular, it is preferable that at least one of the functional layers is an antifouling low refractive index layer.

[0116] The uneven distribution of the function in the functional layer can be evaluated by the concentration and cross-sectional shape of the functional component. For example, the uneven distribution of the function can be evaluated by comparing the concentration (X2) of the functional component contained in the functional layer at the interface with release substrate 2 with the concentration (X1) of the functional component contained in the functional layer on the surface opposite to release substrate 2 (the interface with release substrate 1). In this case, for example, an X2 / X1 ratio of 10 or more (preferably X2 / X1 is 20 or more, and more preferably X2 / X1 is 50 or more) can be used as a criterion for indicating that the function is unevenly distributed. More specifically, when the functional layer is an antifouling layer and the functional component that exhibits antifouling properties is a fluorine component, the uneven distribution of the function (antifouling properties) can be confirmed by quantitatively analyzing the proportion of fluorine atoms in the functional layer at the interface with release substrate 2 and the proportion of fluorine atoms in the functional layer at the interface with release substrate 1 using X-ray photoelectron spectroscopy (XPS). Furthermore, on the assumption that the formulation of the transfer layer is the same, the uneven distribution of the functional component can be evaluated by comparing the physical properties of a molded product obtained by the molded product manufacturing method of the present invention (for example, a molded product obtained by the steps in Fig. 4) with those of a molded product obtained by a conventional molded product manufacturing method (for example, a molded product obtained by the steps in Fig. 5). Examples of physical properties to be compared include water contact angle, pencil hardness, and reflectance.

[0117] Regarding the cross-sectional shape, for example, a cross section of the functional layer cut vertically can be imaged using a scanning transmission electron microscope (STEM), and the length (L2) of the ridge line on the surface of the functional layer on the release substrate 2 side can be compared with the length (L1) of the ridge line on the surface of the functional layer on the opposite side of the release substrate 2 (the release substrate 1 side) to evaluate the uneven distribution of function. For example, if the functional layer is an antiglare layer, the longer the ridge line, the more irregular the surface of the functional layer and the more effectively the function (antiglare property) is exerted. Therefore, a longer L2 than L1 can be used as a criterion for indicating uneven distribution of function (antiglare property). The ratio L2 / L1 varies depending on the strength of the antiglare property to be imparted, so it is not possible to generalize, but it is preferably 1.001 or greater, and more preferably 1.002 or greater. When the average inclination angle on the L2 side is 3 degrees and the average inclination angle on the L1 side is 0 degrees, L2 / L1 is 1.00137, and when the average inclination angle on the L2 side is 5 degrees and the average inclination angle on the L1 side is 0 degrees, L2 / L1 is 1.00382. If the functional layer closest to the release substrate 2 is an antiglare layer, the uneven distribution of function (antiglare properties) can also be confirmed by measuring the surface shape of the antiglare layer after transfer to the adherend. Specifically, if the arithmetic mean roughness Ra of the antiglare layer surface at a cutoff value of 0.25 mm according to JIS B0601:1994 is 0.05 μm or more, it can be said that the function of the antiglare layer is uneven. Furthermore, if the release substrate 2 remains and the Ra on the transfer layer side can be measured, it can be said that the function of the antiglare layer is uneven if the relationship Ra of the release substrate 2 < Ra of the antiglare layer surface holds. Antiglare layers include a type in which surface roughness is imparted by particles and a type in which surface roughness is imparted by resin phase separation. In this embodiment, both types can easily achieve L2 / L1 within the above range.

[0118] Transfer sheet A may be in the form of sheets cut to a predetermined size, or in the form of a roll obtained by winding a long sheet into a roll. The size of the sheets is not particularly limited, but the maximum diameter is approximately 2 to 500 inches. The "maximum diameter" refers to the maximum length when any two points on transfer sheet A are connected. For example, if transfer sheet A is rectangular, the diagonal line of the area is the maximum diameter. If transfer sheet A is circular, the diameter is the maximum diameter. The width and length of the roll are not particularly limited, but generally the width is about 200 to 3000 mm and the length is about 100 to 5000 m. The transfer sheet A in roll form can be cut into sheets according to the size of the adherend. When cutting, it is preferable to remove the end of the roll, which has unstable physical properties. The shape of the sheets is not particularly limited either, and may be, for example, polygonal (triangle, square, pentagon, etc.) or circular, or may be a random, indeterminate shape.

[0119] [Transfer sheet B] The transfer sheet B of the present invention has a transfer layer on a release substrate 2, the transfer layer including at least one functional layer, and at least one of the functional layers has a function that is concentrated on the release substrate 2 side.

[0120] As described above, it is difficult to ensure that the functions of the antiglare layer and the antifouling layer are fully exhibited in conventional transfer sheets. For this reason, the transfer sheet B of the present invention is suitable in that it is more likely to exhibit its effects when the functional layer whose function is unevenly distributed on the release substrate 2 side is an antiglare layer or an antifouling layer. In particular, it is preferable that at least one of the functional layers is an antifouling low refractive index layer.

[0121] The transfer sheet B of the present invention can be obtained by peeling off the release substrate 1 from the transfer sheet A of the present invention described above.

[0122] [Molded body] The molded article of the present invention has a transfer layer on an adherend, the transfer layer having at least one functional layer, and at least one of the functional layers has a function unevenly distributed on the side opposite to the adherend.

[0123] The embodiment of the adherend constituting the molded article of the present invention is the same as the embodiment of the adherend used in the above-mentioned method for producing a molded article of the present invention. For example, the adherend may be one selected from glass, ceramics, and resin, or a mixture thereof. The molded article of the present invention is preferable in that it easily imparts the luxurious feel and cool texture of glass to glass-like substrates. This effect can be more easily achieved when the functional layer, in which the function is unevenly distributed on the side opposite the substrate, is a low refractive index layer. Furthermore, this effect can be more easily achieved by satisfying either (a) the Si element ratio and C / Si of the low refractive index layer being within the above-described ranges, or (b) the low refractive index layer being antifouling and having a pure water contact angle within the above-described ranges. This effect can be even more easily achieved by satisfying both (a) and (b). In recent years, the luxurious feel and texture of glass have become important for image display devices due to their larger size, narrow bezel designs, and 3D shapes (particularly in automotive applications). Therefore, the molded article of the present invention is useful. The embodiment of the transfer layer constituting the molded product of the present invention is the same as the embodiment of the transfer layer used in the above-described method for producing a transfer sheet of the present invention. The transfer layer constituting the molded article of the present invention has at least one functional layer, and at least one of the functional layers has a function unevenly distributed on the side opposite to the adherend. The uneven distribution of function is as described for the transfer sheet A of the present invention. For example, the functional layer having a function unevenly distributed on the side opposite to the adherend is preferably an antiglare layer, an antifouling layer, or an antifouling low refractive index layer. The antifouling low refractive index layer preferably contains a binder resin and silica particles, and the proportion of Si element attributable to the silica particles, as determined by X-ray photoelectron spectroscopy, is preferably 10.0 atomic % or more and 18.0 atomic % or less, and the proportion of C element, when the proportion of Si element is converted to 100 atomic %, is preferably 180 atomic % or more and 500 atomic % or less.

[0124] As described above, molded articles produced using conventional transfer sheets have difficulty in fully exhibiting their antiglare and antifouling functions due to the antiglare layer and antifouling layer contained in the transfer layer. Therefore, the molded article of the present invention is preferable in that it is more likely to exhibit its effects when the functional layer, whose function is unevenly distributed on the side opposite to the adherend, is an antiglare layer or an antifouling layer. In particular, it is preferable that at least one of the functional layers is an antifouling low refractive index layer.

[0125] In the molded article of the present invention, from the viewpoint of adhesion between the adherend and the transfer layer, it is preferable that the layer constituting the transfer layer that is located closest to the adherend is an adhesive layer. The embodiment of the adhesive layer is the same as the embodiment of the adhesive layer exemplified in the above-mentioned method for producing a transfer sheet of the present invention.

[0126] In addition, in the molded article of the present invention, the adherend is preferably glass, and the layer of the transfer layer that is closest to the adherend preferably contains a resin having one or more functional groups selected from a carboxyl group and a methoxy group. This configuration makes it easier to improve the adhesion between the glass adherend and the transfer layer. The proportion of resins having one or more functional groups selected from carboxyl groups and methoxy groups in the total resin components of the layer located closest to the adherend is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, and most preferably 100% by mass.

[0127] Furthermore, when the material of the adherend is an acrylic resin, it is preferable that the layer constituting the transfer layer that is closest to the adherend contains an acrylic resin. Furthermore, when the material of the adherend is selected from modified polyphenylene oxide, polycarbonate resin, and styrene resin, it is preferable that the layer constituting the transfer layer that is closest to the adherend contains one or more selected from acrylic resin, polystyrene resin, polyamide resin, and polyester resin. Furthermore, when the material of the adherend is polypropylene resin, it is preferable that the layer constituting the transfer layer that is closest to the adherend contains one or more selected from chlorinated polyolefin resin, chlorinated ethylene-vinyl acetate copolymer resin, cyclized rubber, and coumarone-indene resin.

[0128] When the transfer layer transferred to the adherend includes a low refractive index layer, the luminous reflectance Y value measured at a light incident angle of 5 degrees from the side of the molded body having the low refractive index layer is preferably 2.0% or less, more preferably 1.0% or less, more preferably 0.5% or less, and even more preferably 0.2% or less. In this specification, the luminous reflectance Y value refers to the luminous reflectance Y value of the CIE 1931 standard color system. The luminous reflectance Y value can be calculated using a spectrophotometer (for example, Shimadzu Corporation, product name "UV-2450"). In addition, when the adherend is light-transmitting, it is preferable to prepare a sample by attaching a light-shielding black plate to the back surface of the adherend via a pressure-sensitive adhesive layer, and measure the luminous reflectance Y value of the sample.

[0129] [Front panel for image display device] The front panel for an image display device of the present invention is made of the above-mentioned molded article of the present invention. The front plate of the present invention is preferably used so that the surface on the transfer layer side faces the front surface of the image display device.

[0130] The front panel is preferably in the form of a sheet cut to a predetermined size. The size of the sheet is not particularly limited, but the maximum diameter is approximately 2 to 500 inches. The "maximum diameter" refers to the maximum length when any two points on the front panel are connected. For example, if the front panel is rectangular, the diagonal line of the area is the maximum diameter. Also, if the front panel is circular, the diameter is the maximum diameter. The shape of the sheets is not particularly limited, and may be, for example, polygonal (triangle, square, pentagon, etc.) or circular, or may be a random, irregular shape.

[0131] [Image display device] The image display device of the present invention is an image display device having a front panel on a display element, and the front panel is the above-mentioned molded article of the present invention.

[0132] Examples of the display element include a liquid crystal display element, an EL display element (an organic EL display element, an inorganic EL display element), a plasma display element, and further, an LED display element such as a micro LED display element. These display elements may have a touch panel function inside the display element. The liquid crystal display modes of the liquid crystal display element include IPS mode, VA mode, multi-domain mode, OCB mode, STN mode, TSTN mode, etc. When the display element is a liquid crystal display element, a backlight is required. The backlight is placed on the side opposite to the side having the molded body of the liquid crystal display element. The image display device may be an image display device with a touch panel. The front plate is preferably disposed so that the surface on the transfer layer side faces away from the display element.

[0133] The size of the image display device is not particularly limited, but the maximum diameter is about 2 to 500 inches. The "maximum diameter" refers to the maximum length when any two points on the image display device are connected. For example, if the image display device is rectangular, the diagonal line of the area is the maximum diameter. Also, if the image display device is circular, the diameter is the maximum diameter. The shape of the image display device is not particularly limited, and may be, for example, polygonal (triangle, square, pentagon, etc.), circular, or may be a random, indeterminate shape. [Example]

[0134] EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited to the embodiments described in the Examples.

[0135] 1. Evaluation and measurement of uneven distribution of functions The molded articles obtained in Examples 1-1 to 1-3 and Comparative Examples 1-1 to 1-3 were subjected to the following measurements and evaluations. The results are shown in Table 1. Note that the sizes of the molded articles used in the following measurements and evaluations are examples only, and are not intended to be limiting. The temperature and humidity of the atmosphere during each measurement and evaluation were 23°C ± 5°C and 40 to 65%, respectively. Before each measurement and evaluation, the molded body was exposed to the above atmosphere for 30 minutes or more.

[0136] 1-1. Antifouling properties (water contact angle) A glass plate with double-sided tape (751B, manufactured by Teraoka Seisakusho) was prepared by adhering double-sided tape to a 10 × 10 cm soda glass. Transfer sheet B was prepared by peeling off release substrate 1 from transfer sheet A of Examples 1-1 to 1-3, and the adhesive layer side of transfer sheet B was adhered to the surface of the glass plate with the double-sided tape, yielding a 10 × 10 cm laminate. Release substrate 2 was peeled off from the laminate, and 1.0 μL of pure water was dropped onto the surface of the transfer layer (the surface of the antifouling low refractive index layer) using a contact angle meter (DM-300, manufactured by Kyowa Interface Science). The static contact angle 10 seconds after the drop was applied was measured according to the θ / 2 method. Three measurements were taken, and the average value was used as the water contact angle for Examples 1-1 to 1-3. The results are shown in Table 1. Furthermore, laminates were obtained by laminating the adhesive layer side of the transfer sheet of Comparative Examples 1-1 to 1-3 to the surface of a glass plate to which double-sided tape had been attached. The release substrate was peeled off from the laminate, and 1.0 μL of pure water was dropped onto the surface of the transfer layer (the surface of the antifouling low refractive index layer) using a contact angle meter (DM-300, manufactured by Kyowa Interface Science). The static contact angle 10 seconds after the drop was applied was measured according to the θ / 2 method. Three measurements were taken, and the average value was used as the water contact angle for Comparative Examples 1-1 to 1-3. The results are shown in Table 1.

[0137] 1-2. Stain resistance (writing and erasability of oil-based marker) An A4 white mount was placed on a flat table, and the 10 x 10 cm laminate prepared in 1-1 above was fixed to the mount with mending tape (3M, product name "810-3-18") on all four sides so that the stain-resistant low refractive index layer surface was facing up. Next, three lines, 5 mm or more wide and 5 cm long, were written on the surface of the stain-resistant low refractive index layer using the bold side of a black oil-based marker (Zebra, product name "Hi-Macchie," MO-150-MC) at 2 cm intervals, and then erased. The writability and erasability were evaluated according to the following criteria. Furthermore, the stain resistance was evaluated according to the following criteria as a comprehensive evaluation of the writability and erasability. The stain resistance evaluation results are shown in Table 1. <Writability> Thirty seconds after writing, the three lines were visually observed to see if they had bounced. If two or more of the three lines had bounced, it was evaluated as if the marker had bounced. If the line shape was not maintained and it had deformed, or if the line width or length had shrunk, it was also considered as if the marker had bounced. <Erasability> Ten seconds after visually evaluating the writability, the three lines were wiped with a cloth (product name "Kimwipe", manufactured by Nippon Paper Crecia Co., Ltd., product number: S-200), and the number of times it took for the black ink of the marker to become invisible after wiping was evaluated. <<Stain resistance>> A: The magic marker repels the stain and can be wiped off in one wipe. B: It doesn't repel magic marker, but it can be wiped off in 2 to 5 wipes. C: The magic marker does not repel and cannot be wiped off even after five tries.

[0138] 2. Preparation of transfer sheet and molded body [Example 1-1] Coating solution 1 for forming an adhesive layer (adhesive layer having heat sealing properties) having the following formulation was applied to a polyethylene terephthalate film (release substrate 1) having a thickness of 38 μm and a size of 200 mm × 600 mm, the surface of which had been release-treated, and dried (100°C, 60 seconds) to form an adhesive layer with a thickness of 2 μm. Next, a coating solution 1 for forming a hard coat layer having the following formulation was applied onto the adhesive layer and dried (70°C, 30 seconds) to form a coating film, and then ultraviolet light was irradiated from the hard coat layer side to cure the ionizing radiation curable composition, thereby forming a hard coat layer with a thickness of 5 μm. Next, coating liquid 1 for forming an antifouling low refractive index layer having the following formulation was applied onto the hard coat layer, dried (50°C, 60 seconds), and irradiated with ultraviolet light to form an antifouling low refractive index layer having a thickness of 100 nm and a refractive index of 1.30. Next, a release substrate 2 (manufactured by San-A Chemical Co., Ltd., product name "SAT TS1050TRL") having a pressure-sensitive adhesive layer on a 50 μm thick polyethylene terephthalate film was prepared, and the adhesive layer side of the release substrate 2 was attached to the antifouling low refractive index layer to obtain a transfer sheet A of Example 1-1. The transfer sheet A of Example 1-1 has a release substrate 1, an adhesive layer, a hard coat layer, an antifouling low refractive index layer, and a release substrate 2 in this order. Furthermore, release substrate 1 was peeled off from the obtained transfer sheet A to obtain transfer sheet B of Example 1-1. Since release substrate 1 could be peeled off from transfer sheet A while leaving release substrate 2 behind, transfer sheet A shows that peel strength 2 is greater than peel strength 1.

[0139] Next, the adhesive layer side of transfer sheet B was placed on the substrate (a polycarbonate resin plate (manufactured by Sumitomo Bakelite Co., Ltd., product name "ECK 100UU", thickness 2 mm)), and the transfer sheet was heat-transferred from the release substrate side using a roll-type hot stamping machine (manufactured by Navitas Co., Ltd., product name "RH-300") at a roll temperature of 220 to 240°C and a roll speed of 20 mm / s. Next, the release substrate 2 of the transfer sheet B was peeled off to obtain the molded article of Example 1-1. The molded article of Example 1-1 has an adherend, an adhesive layer, a hard coat layer, and an antifouling low refractive index layer in this order.

[0140] <Coating liquid 1 for forming adhesive layer> Acrylic resin 23.0 parts by mass (Mitsubishi Chemical Corporation, product name "Mytec UC026", active ingredient: 40% by mass, methyl ethyl ketone solvent) Methyl ethyl ketone 74.0 parts by mass

[0141] <Coating liquid 1 for forming hard coat layer> Photopolymerization initiator 0.5 parts by mass (Manufactured by BASF, product name "Omnirad 184") Reactive acrylic polymer 30.0 parts by mass (Active ingredient: 35% by mass, methyl ethyl ketone / 2,6-di-tert-butyl-4-cresol mixed solvent) Multifunctional urethane acrylate resin 5 parts by mass (DIC Corporation, product name: Luxidia ERS-543, active ingredient: 80% by weight, toluene solvent) Zirconium dioxide 9.0 parts by mass (Active ingredient: 70% by mass, methyl ethyl ketone solvent, average particle size 11 nm) Leveling agent 0.2 parts by mass (DIC Corporation, product name "Megafac F-560", active ingredient: 20% by mass) ·Dilution solvent 55.3 parts by mass (2:8 mixed solvent of methyl isobutyl ketone and methyl ethyl ketone)

[0142] <Coating Solution A for Forming Antifouling Low Refractive Index Layer> Photopolymerization initiator 0.1 parts by mass (Manufactured by IGM Resins, product name "Omnirad 127") ·UV curable resin 1.1 parts by mass (Tri- to tetrafunctional alkoxylated pentaerythritol acrylate, manufactured by Shin-Nakamura Chemical Co., Ltd., product name "NK Ester ATM-4PL") Hollow silica 6.3 parts by weight (active ingredient: 1.3 parts by weight) (Average particle size 60nm) Solid silica 0.9 parts by weight (active ingredient: 0.3 parts by weight) (Average particle size 12nm) Fluorine-based antifouling agent 0.1 parts by weight (active ingredient: 0.005 parts by weight) (DIC, product name "Megafac F-568") ·Dilution solvent 91.5 parts by mass (9:1 mixed solvent of methyl isobutyl ketone and propylene glycol monomethyl ether acetate)

[0143] [Example 1-2] In the anti-fouling low refractive index layer forming coating solution A of Example 1-1, 0.1 parts by mass of a fluorine-based anti-fouling agent (manufactured by DIC Corporation, product name "Megafac F-568") was replaced with a mixture of 0.005 parts by mass of a silicone-based anti-fouling agent (manufactured by BYK Japan, product name "BYK-UV3510", active ingredient: 100% by mass) and 0.095 parts by mass of methyl isobutyl ketone, to prepare an anti-fouling low refractive index layer forming coating solution B. Transfer sheets A, B and molded bodies of Example 1-2 were obtained in the same manner as in Example 1-1, except that this coating solution was used.

[0144] [Examples 1-3] In the anti-fouling low refractive index layer forming coating solution A of Example 1-1, 0.05 mass parts of the 0.1 mass parts of the fluorine-based anti-fouling agent (manufactured by DIC Corporation, product name "Megafac F-568") was replaced with a mixture of 0.0025 mass parts of a silicone-based anti-fouling agent (manufactured by BYK Japan, product name "BYK-UV3510", active ingredient: 100 mass%) and 0.0475 mass parts of methyl isobutyl ketone, to prepare an anti-fouling low refractive index layer forming coating solution C. Transfer sheets A, B and molded bodies of Example 1-3 were obtained in the same manner as in Example 1-1, except that this was used.

[0145] [Comparative Example 1-1] The coating solution A for forming an antifouling low refractive index layer having the above formulation was applied to a 100 μm thick polyethylene terephthalate film (release substrate, size 200 mm × 600 mm) whose surface had been release-treated, dried (50°C, 60 seconds), and irradiated with ultraviolet light to form an antifouling low refractive index layer having a thickness of 100 nm and a refractive index of 1.30. Next, the coating solution 1 for forming a hard coat layer having the above-described formulation was applied onto the antifouling low refractive index layer, and the coating film was formed by drying (70°C, 30 seconds). After that, ultraviolet light was irradiated from the hard coat layer side to cure the ionizing radiation curable composition, thereby forming a hard coat layer having a thickness of 5 μm. Next, coating solution 1 for forming an anchor layer having the following formulation was applied onto the hard coat layer, and dried and cured at 100° C. for 1 minute to form an anchor layer having a thickness of 2 μm. Next, the adhesive layer (heat-sealable adhesive layer) forming coating liquid 1 having the above formulation was applied onto the anchor layer, and dried and cured at 100°C for 1 minute to form a 2µm thick adhesive layer, thereby obtaining a transfer sheet of Comparative Example 1-1. The transfer sheet of Comparative Example 1-1 has, in this order, a release substrate, an antifouling low refractive index layer, a hard coat layer, an anchor layer, and an adhesive layer.

[0146] Next, the adhesive layer side of the transfer sheet was placed on the adherend (a polycarbonate resin plate (manufactured by Sumitomo Bakelite Co., Ltd., product name "ECK 100UU", thickness 2 mm)), and the transfer sheet was heat-transferred from the release substrate side using a roll-type hot stamping machine (manufactured by Navitas Co., Ltd., product name "RH-300") at a roll temperature of 220 to 240°C and a roll speed of 20 mm / s. Next, the release substrate of the transfer sheet was peeled off to obtain a molded article of Comparative Example 1-1. The molded article of Comparative Example 1-1 has an adherend, an adhesive layer, an anchor layer, a hard coat layer, and an antifouling low refractive index layer in this order.

[0147] <Coating solution 1 for forming anchor layer> Isocyanate resin 7.5 parts by mass (Active ingredient: 40%, ethyl acetate solvent) Polyester resin 46.2 parts by mass (Active ingredient: 26%, toluene / ethyl acetate / methyl ethyl ketone mixed solvent) ·Dilution solvent 46.3 parts by mass (4:6 mixed solvent of ethyl acetate and toluene)

[0148] [Comparative Example 1-2] In the anti-fouling low refractive index layer forming coating solution A of Comparative Example 1-1, 0.1 parts by mass of a fluorine-based anti-fouling agent (manufactured by DIC Corporation, product name "Megafac F-568") was replaced with a mixture of 0.005 parts by mass of a silicone-based anti-fouling agent (manufactured by BYK Japan, product name "BYK-UV3510", active ingredient: 100% by mass) and 0.095 parts by mass of methyl isobutyl ketone, to prepare an anti-fouling low refractive index layer forming coating solution B. The transfer sheet and molded body of Comparative Example 1-2 were obtained in the same manner as in Comparative Example 1-1, except that this was used.

[0149] [Comparative Example 1-3] In the anti-fouling low refractive index layer forming coating solution A of Comparative Example 1-1, 0.05 mass parts of the 0.1 mass parts of the fluorine-based anti-fouling agent (manufactured by DIC Corporation, product name "Megafac F-568") was replaced with a mixture of 0.0025 mass parts of a silicone-based anti-fouling agent (manufactured by BYK Japan, product name "BYK-UV3510", active ingredient: 100 mass%) and 0.0475 mass parts of methyl isobutyl ketone, to prepare an anti-fouling low refractive index layer forming coating solution C. The transfer sheet and molded body of Comparative Example 1-3 were obtained in the same manner as in Comparative Example 1-1, except that this was used.

[0150] [Table 1]

[0151] As is clear from the results in Table 1, the molded articles of Examples 1-1 to 1-3 have a high water contact angle and good antifouling properties. Furthermore, since the molded articles of Examples 1-1 to 1-3 and the molded articles of Comparative Examples 1-1 to 1-3 have the same functional layer formulation, the results in Table 1 support the fact that in the functional layers (antifouling low refractive index layers) of the molded articles of Examples 1-1 to 1-3, the antifouling agent component, which is a functional component, is unevenly distributed on the side opposite to the adherend.

[0152] 3. Comparison of oil dust resistance, etc. of the antifouling low refractive index layer 3-1. Preparation of transfer sheet and molded body [Example 2-1] Transfer sheet A, transfer sheet B, and a molded article of Example 2-1 were obtained in the same manner as in Example 1-1, except that the antifouling low refractive index layer-forming coating solution A of Example 1-1 was changed to the antifouling low refractive index layer-forming coating solution D of the following formulation and the drying conditions were changed to 60°C for 1 minute. The refractive index of the low refractive index layer of Example 2-1 was 1.33.

[0153] <Coating Solution D for Forming Antifouling Low Refractive Index Layer> Photopolymerization initiator 0.02 parts by mass (Manufactured by IGM Resins, product name "Omnirad 127") ·UV curable resin 0.6 parts by mass (Polyethylene glycol (n≒4) diacrylate, manufactured by Toagosei Co., Ltd., product name "M-240") Hollow silica 6.2 parts by weight (active ingredient: 1.2 parts by weight) (Hollow silica with an average particle size of 75 nm, surface-treated with a silane coupling agent containing a methacryloyl group. Dispersion containing 20% ​​by mass of active ingredient) Solid silica 1.8 parts by weight (active ingredient: 0.7 parts by weight) (Solid silica with an average particle size of 12.5 nm, surface-treated with a silane coupling agent containing a methacryloyl group. Dispersion containing 40% by mass of active ingredient) Silicone leveling agent 0.08 parts by mass (Shin-Etsu Chemical Co., Ltd., product name "KP-420") ·Dilution solvent 91.3 parts by mass (68:32 mixed solvent of methyl isobutyl ketone and 1-methoxy-2-propyl acetate)

[0154] [Example 2-2] The transfer sheet A, transfer sheet B, and molded body of Example 2-2 were obtained in the same manner as in Example 2-1, except that "0.6 parts by mass of the ultraviolet curable resin" in the coating liquid D for forming the low-refractive-index layer with low fouling property was changed to "0.6 parts by mass of an 80:20 mixture of the following ultraviolet curable resin a and ultraviolet curable resin b". The refractive index of the low-refractive-index layer in Example 2-1 was 1.33. · Ultraviolet curable resin a (polyethylene glycol (n≈4) diacrylate, manufactured by Toagosei Co., Ltd., trade name "M-240") · Ultraviolet curable resin b (pentaerythritol (tri / tetra) acrylate, manufactured by Nippon Kayaku Co., Ltd., trade name "KAYARAD PET-30")

[0155] 3-2. Surface roughness Samples were prepared by cutting the molded bodies of Examples 2-1 and 2-2 prepared in 3-1 into 5 cm × 5 cm. Using an atomic force microscope (AFM) SPM-9600 manufactured by Shimadzu Corporation, the shape of the molded body of the sample was measured in the On-Line (measurement) mode in the Soft: SPM Manager. The measurement conditions are shown below. Then, using the Off-Line (analysis) mode, tilt correction processing was performed to obtain a grayscale image when the height: 0 nm was black and the height: 100 nm or more was white. The lowest point within the measurement range was set as "height 0 nm". The obtained AFM images were analyzed to obtain the Rz (maximum height roughness) and Ra (arithmetic mean roughness) of each sample. The average values of Rz and Rz / Ra at 14 locations for each sample were evaluated. The results are shown in Table 2. <AFM measurement conditions> Measurement mode: Phase <00​​​​​​​​​​​​​​​​The molded articles of Examples 1-1 to 1-3 and 2-1 to 2-2 were cut into 5 cm x 5 cm samples. A test liquid was prepared by mixing AC dust (ISO12103-1, A2 (Fine)) and olive oil (CAS No. 8001-25-0) at a 1 / 1 (weight ratio). Eight layers of cloth (manufactured by AS ONE Corporation, product name "ASPURE PROPLEA II") were folded and firmly attached with a rubber band to the tip of a rod-shaped metal member (rod-shaped end surface shaped like a 1 cm x 1 cm square). The side of the rod-shaped metal member to which the cloth was attached was immersed in the test liquid, and 5 g of the test liquid was evenly soaked into the end surface of the cloth, thereby obtaining a rod-shaped metal member for scraping. The sample was attached to a test table with the antifouling low refractive index layer facing up. A weight was attached to the rod-shaped metal member for rubbing, and the cloth side of the rod-shaped metal member was brought into contact with the surface of the antifouling low refractive index layer. The weight was moved back and forth 10 times at a moving speed of 100 mm / sec and a moving distance of 200 mm per reciprocation (one-way moving distance 100 mm). The contact area between the cloth and the low refractive index layer was approximately 1 cm2, which was roughly equal to the area of ​​the end face of the rod-shaped metal member. 2 Unless otherwise specified, the test environment was a temperature of 23°C ± 1°C and a relative humidity of 50% ± 5%. Thereafter, the sample was observed with the naked eye from the antifouling low refractive index layer side under fluorescent light (Panasonic Corporation three-wavelength fluorescent light, model number: FHF32EX-NH, illuminance on the sample 800-1200 Lx, observation distance 30 cm) and under LED lighting (Gentos Corporation LED light, model number: TX-850Re, illuminance on the sample 4000-6000 Lx, observation distance 30 cm), and the number of scratches was evaluated. The load was the weight of the weight, and the oil dust resistance was evaluated as the maximum load per unit area (g / cm) when no scratches were observed (0 scratches) after the test. 2 The test was carried out with n=2 for each example, and the average was taken as the oil dust resistance of each example. The results are shown in Table 2.

[0157] 3-4. Anti-fouling properties (fingerprint wipe-off) The molded articles of Examples 1-1 to 1-3 and 2-1 to 2-2 were cut into 5 cm x 5 cm samples. A finger pad was pressed against the surface of the antifouling low refractive index layer of each sample to leave a fingerprint. The fingerprint was then wiped off using a nonwoven fabric (manufactured by Asahi Kasei Corporation, product name: Bencotton), and the number of times it was wiped until the fingerprint was no longer visible was evaluated. Those whose fingerprints became invisible after wiping up to three times were rated "A", those whose fingerprints became invisible after wiping four to seven times were rated "B", and those whose fingerprints remained visible even after wiping seven times were rated "C". The results are shown in Table 2.

[0158] [Table 2]

[0159] Comparing Examples 1-1 to 1-3 with Examples 2-1 to 2-2, Examples 2-1 to 2-2 have good oil dust resistance. This is thought to be because, in the low refractive index layers of Examples 2-1 to 2-2, hollow silica and solid silica are uniformly dispersed in the low refractive index layers as shown in Fig. 6 and the surface shape of the low refractive index layers is not rough, whereas in the low refractive index layers of Examples 1-1 to 1-3, hollow silica and solid silica are not uniformly dispersed in the low refractive index layers as shown in Fig. 7 and the surface shape of the low refractive index layers is rough.

[0160] 4. Evaluation and measurement of peel strength The transfer sheets obtained in Examples 3-1 to 3-5 and Comparative Example 3-1 below were subjected to the following measurements and evaluations. The results are shown in Table 3. The measurements and evaluations were carried out in an atmosphere with a temperature of 23°C ± 5°C and a humidity of 40 to 65%.

[0161] 4-1. Peel strength In accordance with the 180-degree peel test of JIS Z0237:2009, the peel strength 1 between the release substrate 1 and the transfer layer and the peel strength 2 between the release substrate 2 and the transfer layer were measured for the release sheets A obtained in Examples 3-1 to 3-5 and Comparative Example 3-1. For Examples 3-1 to 3-5 and Comparative Example 3-1, the peel strengths 1 and 2 were measured three times, and the average values ​​were used as the peel strengths 1 and 2 for Examples 3-1 to 3-5 and Comparative Example 3-1. The sample conditions and measurement conditions were set as follows:

[0162] <Sample conditions for measuring peel strength 1> A laminate is prepared by forming a transfer layer on a release substrate 1 (the laminate with release substrate 2 laminated on the transfer layer corresponds to transfer sheet A). The laminate is cut to a size of 25 mm wide x 150 mm long. A strong adhesive double-sided tape (751B, manufactured by Teraoka Seisakusho) cut to a length of 150 mm is attached to a metal ruler (straight ruler silver TSU-30N, manufactured by Trusco Nakayama; the same will be used hereinafter), to prepare a substrate with double-sided tape. The double-sided tape side of the substrate with double-sided tape faces the transfer layer side of the cut laminate, and a pressure of 2 kg / cm is applied. 2 The release substrate 1 was peeled off from the edge by 10 to 20 mm to provide a sample for measuring peel strength 1 in Examples 3-1 to 3-5 and Comparative Example 3-1. <Sample Condition 1 for Measuring Peel Strength 2 (Examples 3-1 to 3-5)> The transfer sheet A is left on a flat desk with the release substrate 2 side facing up for 24 hours (the atmosphere during leaving is a temperature of 23°C ± 5°C and a humidity of 40 to 65%). Next, the release substrate 1 is peeled off from the transfer sheet A, and then it is cut into a size of 25 mm wide x 150 mm long. The double-sided tape side of the substrate with the double-sided tape is placed opposite the transfer layer side of the cut transfer sheet, and the sheet is pressed under a pressure of 2 kg / cm. 2 The release substrate 2 was peeled off from the edge by 10 to 20 mm to provide a sample for measuring peel strength 2 in Examples 3-1 to 3-5. <Sample Condition 2 for Measuring Peel Strength 2 (Comparative Example 3-1)> The transfer sheet A is left on a flat desk with the release substrate 2 side facing up for 24 hours (the atmosphere during leaving is a temperature of 23°C ± 5°C and a humidity of 40 to 65%). Next, the transfer sheet A is cut into a size of 25 mm wide x 150 mm long. The double-sided tape side of the substrate with the double-sided tape is placed opposite the release substrate 1 side of the cut transfer sheet A, and the sheet is pressed under a pressure of 2 kg / cm. 2 The release substrate 2 was peeled off from the edge by 10 to 20 mm to obtain a sample for measuring peel strength 2 of Comparative Example 3-1.

[0163] <Measurement conditions> Using a Tensilon universal testing machine (RTC-1310A, manufactured by Orientec Co., Ltd.), the prepared measurement sample adherend (metal ruler) was fixed to one of the chucking jigs attached to the Tensilon universal testing machine, and the peeled end of release substrate 1 or 2 was fixed to the other chucking jig, and the test was set so that it was pulled in the longitudinal direction of release substrate 1 or 2. The transfer sheet was then pulled 70 mm in a peel angle of 180° at a peel speed of 300 mm / min at room temperature (23°C), and the load required for peeling was measured. The average load over a travel distance of 10 mm to 30 mm was recorded as the peel force in one measurement, and the average value of three measurements was recorded as the peel force.

[0164] 4-2.Releasability of release substrate 1 The transfer sheet A is left on a flat desk with the release substrate 1 side facing up for 24 hours (the atmosphere during leaving is a temperature of 23°C ± 5°C and a humidity of 40 to 65%). Next, the transfer sheet A is cut into a size of 25 mm wide x 150 mm long. The double-sided tape side of the substrate with the double-sided tape is placed opposite the release substrate 2 side of the cut transfer sheet A, and the sheet is pressed under a pressure of 2 kg / cm. 2 The laminate was laminated under a load of 0.05g, and the peelability of the release substrate 1 of the laminate was evaluated according to the following criteria. AA: With a simple operation, the release substrate 1 can be stably peeled off before the release substrate 2, and no local lifting occurs at the interface between the release substrate 2 and the transfer layer. A: If the work is done carefully, release substrate 1 can be peeled off before release substrate 2, and no local lifting occurs at the interface between release substrate 2 and the transfer layer. B: If the work is done carefully, release substrate 1 can be peeled off before release substrate 2, but local lifting may occur at the interface between release substrate 2 and the transfer layer. C: Even if you try to carefully peel off only the release substrate 1, the release substrate 2 peels off first.

[0165] 5. Preparation of Release Substrate The following substrates i to vii were prepared as release substrates 1 and 2 used in Examples 3-1 to 3-5 and Comparative Example 3-1. Substrate i is a plastic film having a release layer, and substrates ii to vii have a pressure-sensitive adhesive layer with weak adhesive strength on the plastic film. Substrate i: Fujimori Kogyo Co., Ltd., product name "FILMBYNA (registered trademark)", product number: 38E-NSD, substrate thickness 38 μm Substrate ii: Sanitekt MS24, manufactured by San-A Kaken Co., Ltd., substrate thickness 40 μm Substrate iii: Sanitekt Y06F (manufactured by San-ei Kaken Co., Ltd.), substrate thickness 60 μm Substrate iv: Sanitekt Y26F (manufactured by San-A Kaken Co., Ltd.), substrate thickness 60 μm Substrate v: San-ei Kaken Co., Ltd. product name "SAT2038T-JSL", substrate thickness 60 μm Substrate vi: Toray Film Processing Co., Ltd. product name "R304A", substrate thickness 40 μm Substrate vii: Sanitect SAT 1050TRL, manufactured by San-A Chemical Co., Ltd., substrate thickness 50 μm

[0166] 6. Preparation of transfer sheet [Example 3-1] The adhesive layer-forming coating liquid 1 was applied to a release substrate 1 (substrate i above) and dried to form an adhesive layer with a thickness of 2 μm. Next, the hard coat layer-forming coating liquid 1 was applied to the adhesive layer and dried (70°C, 30 seconds) to form a coating film, and then ultraviolet light was irradiated from the hard coat layer side to cure the ionizing radiation curable composition, forming a hard coat layer with a thickness of 5 μm. Next, release substrate 2 (substrate ii above) was laminated on the hard coat layer to obtain a transfer sheet A of Example 3-1. The transfer sheet A of Example 3-1 has, in this order, a release substrate 1, an adhesive layer, a hard coat layer, and a release substrate 2.

[0167] [Examples 3-2 to 3-5], [Comparative Example 3-1] Except for changing the release substrate 2 to one shown in Table 3, the same procedures as in Example 3-1 were carried out to obtain transfer sheets A of Examples 3-2 to 3-5 and Comparative Example 3-1.

[0168] [Table 3]

[0169] As shown in Table 3, it can be confirmed that the transfer sheets A of Examples 3-1 to 3-5, in which peel strength 2 is greater than peel strength 1, can have release substrate 1 peeled off while leaving release substrate 2 to obtain transfer sheet B. The thickness direction of the functional layer of the molded article obtained by transferring the transfer layer of transfer sheet B, relative to the adherend, is the same as the thickness direction of the functional layer relative to release substrate 1 of transfer sheet A. Therefore, the transfer sheets A of Examples 3-1 to 3-5 can fully impart the functions of the functional layer, whose functions are unevenly distributed on the surface side, to the adherend. Although not shown in the table, modified examples of Examples 3-1 to 3-5 were tested in which release substrate 1 was changed to a substrate different from substrate i. As a result, it was confirmed that if peel strength 2 - peel strength 1 was 100 mN / 25 mm or more, the release property of release substrate 1 was evaluated as AA, if peel strength 2 - peel strength 1 was 40 mN / 25 mm or more, the release property of release substrate 1 was evaluated as A, and if peel strength 2 - peel strength 1 was 15 mN / 25 mm or more, the release property of release substrate 1 was evaluated as B.

[0170] 7. Performance comparison of antifouling low refractive index layers 7-1. Preparation of transfer sheet and molded body [Example 4-1] The adhesive layer-forming coating liquid 1 was applied to a release substrate 1 (the above substrate i (trade name "FILMBYNA (registered trademark)" manufactured by Fujimori Kogyo Co., Ltd., product number: 38E-NSD)) and dried to form a 2 μm-thick adhesive layer. Next, the hard coat layer-forming coating liquid 1 was applied to the adhesive layer and dried (70°C, 30 seconds) to form a coating film, and then ultraviolet light was irradiated from the hard coat layer side to cure the ionizing radiation-curable composition, forming a 5 μm-thick hard coat layer. Next, the antifouling low refractive index layer-forming coating liquid D was applied to the hard coat layer, dried (50°C, 60 seconds), and irradiated with ultraviolet light to form an antifouling low refractive index layer with a thickness of 100 nm and a refractive index of 1.33. Next, release substrate 2 (the above substrate ii, the above product name "SaniTect MS24" manufactured by San-A Kaken Co., Ltd.) was laminated on the antifouling low refractive index layer to obtain a transfer sheet A of Example 4-1. The transfer sheet A of Example 4-1 has a release substrate 1, an adhesive layer, a hard coat layer, an antifouling low refractive index layer, and a release substrate 2 in this order. Next, the release substrate 1 was peeled off from the obtained transfer sheet A to obtain a transfer sheet B of Example 4-1. Next, the adhesive layer side of transfer sheet B was placed on the substrate (a polycarbonate resin plate (manufactured by Sumitomo Bakelite Co., Ltd., product name "ECK 100UU", thickness 2 mm)), and the transfer sheet was heat-transferred from the release substrate 2 side using a roll-type hot stamping machine (manufactured by Navitas Co., Ltd., product name "RH-300") under conditions of a roll temperature of 220 to 240°C and a roll speed of 20 mm / s. Next, the release substrate 2 of the transfer sheet B was peeled off to obtain a molded article of Example 4-1. The molded article of Example 4-1 has an adherend, an adhesive layer, a hard coat layer, and an antifouling low refractive index layer in this order.

[0171] [Example 4-2] The transfer sheet A, transfer sheet B and molded body of Example 4-2 were obtained in the same manner as in Example 4-1, except that the coating liquid D for forming an antifouling low refractive index layer was changed to the coating liquid E for forming an antifouling low refractive index layer described below.

[0172] <Coating Solution E for Forming Antifouling Low Refractive Index Layer> Photopolymerization initiator 0.02 parts by mass (Manufactured by IGM Resins, product name "Omnirad 127") ·UV curable resin 0.6 parts by mass (Polyethylene glycol (n≒4) diacrylate, manufactured by Toagosei Co., Ltd., product name "M-240") Hollow silica 6.2 parts by weight (active ingredient: 1.2 parts by weight) (Hollow silica with an average particle size of 75 nm, surface-treated with a silane coupling agent containing a methacryloyl group. Dispersion containing 20% ​​by mass of active ingredient) Solid silica 1.8 parts by weight (active ingredient: 0.7 parts by weight) (Solid silica with an average particle size of 12.5 nm, surface-treated with a silane coupling agent containing a methacryloyl group. Dispersion containing 40% by mass of active ingredient) Fluorine-based leveling agent 0.08 parts by mass (Shin-Etsu Chemical Co., Ltd., product name "X-71-1203M") ·Dilution solvent 91.3 parts by mass (68:32 mixed solvent of methyl isobutyl ketone and 1-methoxy-2-propyl acetate)

[0173] [Example 4-3] The transfer sheet A, transfer sheet B and molded body of Example 4-3 were obtained in the same manner as in Example 4-1, except that the coating liquid D for forming an antifouling low refractive index layer was changed to the coating liquid F for forming an antifouling low refractive index layer described below.

[0174] <Coating Solution F for Forming Antifouling Low Refractive Index Layer> Photopolymerization initiator 0.02 parts by mass (Manufactured by IGM Resins, product name "Omnirad 127") ·Ultraviolet curable resin a 0.3 parts by mass (Pentaerythritol (tri / tetra)acrylate, manufactured by Nippon Kayaku Co., Ltd., product name "KAYARAD PET-30") ·UV curable resin b 0.3 parts by mass (Dipentaerythritol (hexa / penta)acrylate, manufactured by Nippon Kayaku Co., Ltd., product name "KAYARAD DPHA") Hollow silica 6.2 parts by weight (active ingredient: 1.2 parts by weight) (Hollow silica with an average particle size of 75 nm, surface-treated with a silane coupling agent containing a methacryloyl group. Dispersion containing 20% ​​by mass of active ingredient) Solid silica 1.8 parts by weight (active ingredient: 0.7 parts by weight) (Solid silica with an average particle size of 12.5 nm, surface-treated with a silane coupling agent containing a methacryloyl group. Dispersion containing 40% by mass of active ingredient) Fluorine-based leveling agent 0.08 parts by mass (Shin-Etsu Chemical Co., Ltd., product name "X-71-1203M") ·Dilution solvent 91.3 parts by mass (68:32 mixed solvent of methyl isobutyl ketone and 1-methoxy-2-propyl acetate)

[0175] [Example 4-4] The transfer sheet A, transfer sheet B and molded body of Example 4-4 were obtained in the same manner as in Example 4-1, except that the coating liquid D for forming an antifouling low refractive index layer was changed to the coating liquid G for forming an antifouling low refractive index layer described below.

[0176] <Coating Solution G for Forming Antifouling Low Refractive Index Layer> Photopolymerization initiator 0.02 parts by mass (Manufactured by IGM Resins, product name "Omnirad 127") ·Ultraviolet curable resin a 0.3 parts by mass (Pentaerythritol (tri / tetra)acrylate, manufactured by Nippon Kayaku Co., Ltd., product name "KAYARAD PET-30") ·UV curable resin b 0.3 parts by mass (Dipentaerythritol (hexa / penta)acrylate, manufactured by Nippon Kayaku Co., Ltd., product name "KAYARAD DPHA") Hollow silica 6.2 parts by weight (active ingredient: 1.2 parts by weight) (Hollow silica with an average particle size of 75 nm, surface-treated with a silane coupling agent containing a methacryloyl group. Dispersion containing 20% ​​by mass of active ingredient) Solid silica 1.8 parts by weight (active ingredient: 0.7 parts by weight) (Solid silica with an average particle size of 12.5 nm, surface-treated with a silane coupling agent containing a methacryloyl group. Dispersion containing 40% by mass of active ingredient) Silicone leveling agent 0.08 parts by mass (Shin-Etsu Chemical Co., Ltd., product name "KP-420") ·Dilution solvent 91.3 parts by mass (68:32 mixed solvent of methyl isobutyl ketone and 1-methoxy-2-propyl acetate)

[0177] [Examples 4-5] Transfer sheet A, transfer sheet B and a molded article of Example 4-5 were obtained in the same manner as in Example 4-1, except that coating liquid 1 for forming a hard coat layer was changed to coating liquid 2 for forming a hard coat layer described below.

[0178] <Coating liquid 2 for forming hard coat layer> ·Ultraviolet curable compound 23.7 parts by mass (Multifunctional urethane acrylate, manufactured by DIC Corporation, product name: Luxidia ERS-543) ·Ultraviolet curable compound 18.5 parts by mass (Multifunctional urethane acrylate, manufactured by DIC Corporation, product name: Luxidia EKS-796) UV absorber 0.74 parts by mass (Hydroxyphenyltriazine, manufactured by BASF Japan Ltd., product name: Tinuvin 477) ·Ultraviolet curable compound 1.85 parts by mass (Acrylic resin, manufactured by Arakawa Chemical Co., Ltd., product name DSR-1) Photopolymerization initiator 0.84 parts by mass (IGM Resins BV, product name "Omnirad 184") Acrylic resin particles 5.17 parts by mass (Average particle size 2.0μm) Acrylic resin particles 0.72 parts by mass (Fumed silica, average particle size 200nm) Silicone leveling agent 0.27 parts by mass (Momentive Performance Materials, product name: TSF4460) ·Dilution solvent 48.3 parts by mass (Toluene / IPA = 60 / 40 mixture)

[0179] [Comparative Example 4-1] Transfer sheet A, transfer sheet B and a molded body of Comparative Example 4-1 were obtained in the same manner as in Example 4-1, except that the release substrate 2 was changed to the above substrate vii (trade name "SaniTect SAT 1050TRL" manufactured by San-A Chemical Co., Ltd.). In addition, in the transfer sheet A of Comparative Example 4-1, peel strength 2 is smaller than peel strength 1, so that release substrate 1 cannot be peeled off before release substrate 2 using a normal method. For this reason, in Comparative Example 4-1, a slit was made in the release substrate 1 side of transfer sheet A to create an opportunity for peeling of release substrate 1, and release substrate 1 was peeled off little by little while pressing down on both sides of transfer sheet A to prevent release substrate 2 from peeling off, thereby obtaining transfer sheet B.

[0180] [Comparative Example 4-2] The antifouling low refractive index layer-forming coating liquid D was applied to a release substrate 1 (the above substrate i), dried (50°C, 60 seconds), and irradiated with ultraviolet light to form an antifouling low refractive index layer with a thickness of 100 nm and a refractive index of 1.33. Next, the hard coat layer-forming coating liquid 1 was applied to the antifouling low refractive index layer and dried (70°C, 30 seconds) to form a coating film, and then irradiated with ultraviolet light from the hard coat layer side to cure the ionizing radiation curable composition and form a hard coat layer with a thickness of 5 μm. Next, the adhesive layer-forming coating liquid 1 was applied to the hard coat layer and dried to form a 2 μm thick adhesive layer, thereby obtaining a transfer sheet of Comparative Example 4-2. The transfer sheet of Comparative Example 4-2 has, in this order, a release substrate 1, an antifouling low refractive index layer, a hard coat layer, and an adhesive layer. Next, the adhesive layer side of the transfer sheet was placed on the adherend (a polycarbonate resin plate (manufactured by Sumitomo Bakelite Co., Ltd., product name "ECK 100UU", thickness 2 mm)), and the transfer sheet was heat-transferred from the release substrate 1 side using a roll-type hot stamping machine (manufactured by Navitas Co., Ltd., product name "RH-300") at a roll temperature of 220 to 240°C and a roll speed of 20 mm / s. Next, the release substrate 1 of the transfer sheet was peeled off to obtain a molded article of Comparative Example 4-2. The molded article of Comparative Example 4-2 has an adherend, an adhesive layer, a hard coat layer, and an antifouling low refractive index layer in this order.

[0181] [Reference example 4-1] Transfer sheet A, transfer sheet B and a molded body of Reference Example 4-1 were obtained in the same manner as in Example 4-1, except that the release substrate 2 was changed to the above substrate iv (trade name "SaniTect Y26F" manufactured by San-A Chemical Co., Ltd.).

[0182] 7-2. Measurement and evaluation The following measurements and evaluations were carried out on the molded articles of Examples 4-1 to 4-5, Comparative Examples 4-1 and 4-2, and Reference Example 4-1. The atmosphere during each measurement and evaluation was set to a temperature of 23°C ± 5°C and a humidity of 40 to 65%, unless otherwise specified. Furthermore, unless otherwise specified, the molded articles were exposed to the above atmosphere for 30 minutes or more before each measurement and evaluation. The results are shown in Table 4.

[0183] (1)XPS analysis Measurement pieces were cut out from the molded articles of the examples. Using an X-ray photoelectron spectrometer, X-ray photoelectron spectra of the C1s orbital, O1s orbital, Si2p orbital, and F1s orbital on the surface of the low refractive index layer of each measurement piece were measured under the conditions described below. Peak separation was performed on each X-ray photoelectron spectrum to determine the ratios of C, O, F, and Si elements. Furthermore, peak separation was performed on the X-ray photoelectron spectrum of the Si2p orbital to determine the ratio of Si element attributed to the silica particles (hollow silica particles and solid silica particles) ("Inorganic Si" in the table). Measurements were performed at 14 locations for each sample, and further analysis was performed on two samples (n = 2). The average of these measurements was used as the element ratio for each example and comparative example. Furthermore, from the obtained element ratios, the ratio of C element (C / Si) was calculated when the ratio of Si element attributed to the silica particles determined above was converted to 100 atomic %. In Tables 1 and 2, elements other than the Si element (inorganic Si element), C element, and F element derived from inorganic components, such as the O element, are listed as "other elements," and the total ratio of these elements is shown. <Measurement> Equipment: Kratos AXIS-NOVA X-ray source: AlKα X-ray output: 150W Emission current: 10mA Accelerating voltage: 15 kV Measurement area: 300×700μm

[0184] (2) Surface roughness The molded article of the example was cut into a 5 cm x 5 cm measurement sample. Using the measurement sample, Rz (maximum height roughness) and Ra (arithmetic mean roughness) were measured using the same method as in 3-2 above.

[0185] (3) Reflectance (visible reflectance Y value) Samples (5 cm x 5 cm) were prepared by bonding a black plate (manufactured by Kuraray Co., Ltd., product name: COMOGLAS DFA2CG 502K (black) series, thickness 2 mm) to the adherend side of the molded article of the Examples, Comparative Examples, and Reference Examples via a 25 μm thick transparent adhesive layer (manufactured by Panac Corporation, product name: Panaclean PD-S1). When the direction perpendicular to the surface of the low refractive index layer of the sample was set to 0 degrees, light was incident on the sample from a direction of 5 degrees, and the reflectance of the sample (luminous reflectance Y value) was measured based on the specular reflection of the incident light. The reflectance was measured using a spectral reflectance meter (Shimadzu Corporation, product name: UV-2450) under conditions of a viewing angle of 2 degrees, light source C, and a wavelength range of 380 to 780 nm. The reflectance was then calculated using software (built-in UVPC color measurement version 3.12) that converts the measured value into the brightness perceived by the human eye, and the value indicating the visual reflectance was determined as the reflectance. A visual reflectance Y value of 0.2% or less is rated as "AA", 0.4% or less is rated as "A", 0.4% or more but 0.7% or less is rated as "B", and 0.7% or more but 2.0% or less is rated as "B". - "

[0186] (4) Water contact angle 1.0 μL of pure water was dropped onto the surface (surface of the antifouling low refractive index layer) of the molded article of each of the Examples, Comparative Examples, and Reference Examples, and the static contact angle was measured 10 seconds after the drop had settled according to the θ / 2 method. Three measurements were taken, and the average value was used as the water contact angle. The measurement device used was a contact angle meter (product number "DM-300" manufactured by Kyowa Interface Science Co., Ltd.

[0187] (5) Stain resistance 1 (oil-based marker writing and erasability) An A4 white mount was placed on a flat table, and a sample of the molded article cut to 10 x 10 cm in size in 7-1 above was fixed on the mount with mending tape (3M, product name "810-3-18") on all four sides so that the stain-resistant low refractive index layer surface was facing up. Next, three lines, 5 mm or more wide and 5 cm long, were written on the surface of the stain-resistant low refractive index layer using the bold side of a black oil-based marker (product name "Hi-Macchie", Zebra, product number MO-150-MC), spaced 2 cm apart, and then erased. The writability and erasability were evaluated according to the following criteria. Furthermore, as a comprehensive evaluation of the writability and erasability, the stain resistance was evaluated according to the following criteria. <Writability> Thirty seconds after writing, the three lines were visually observed to see if they had bounced. If two or more of the three lines had bounced, it was evaluated as if the marker had bounced. If the line shape was not maintained and it had deformed, or if the line width or length had shrunk, it was also considered as if the marker had bounced. <Erasability> Ten seconds after visually evaluating the writability, the three lines were wiped with a cloth (product name "Kimwipe", manufactured by Nippon Paper Crecia Co., Ltd., product number: S-200), and the number of times it took for the black ink of the marker to become invisible after wiping was evaluated. <<Stain resistance>> AA: Magic repels and can be wiped off in one wipe. A: It doesn't repel magic marker, but it can be wiped off in 2-3 wipes. B: It doesn't repel magic marker, but it can be wiped off in 4-5 wipes. C: The magic marker does not repel and cannot be wiped off even after five tries.

[0188] (6) Antifouling 2 (fingerprint wipeability) The molded articles of the Examples, Comparative Examples, and Reference Examples were cut into 5 cm x 5 cm samples. Using these measurement samples, fingerprint wiping properties were evaluated using the same method and evaluation criteria as in 3-4 above. The evaluation criteria are shown below. A: Fingerprints become invisible after wiping up to three times. B: Fingerprints become invisible after 4 to 7 wipes. C: Fingerprints are still visible even after wiping seven times.

[0189] (7) Oil dust resistance test The molded articles of the Examples, Comparative Examples, and Reference Examples were cut into 5 cm x 5 cm samples, and the oil dust resistance of the measurement samples was evaluated in the same manner as in 3-3 above.

[0190] (8) Peel strength The peel strength 1 of the transfer sheets of the Examples, Comparative Examples and Reference Examples was measured by the same method as in 4-1 above. Furthermore, the peel strength 2 of the transfer sheets of Examples 4-1 to 4-5, Comparative Example 4-1, and Reference Example 4-1 was measured using the same method as in 4-1 above. However, for Examples 4-1 to 4-5 and Reference Example 4-1, samples were prepared using the method described in "Sample condition 1 for measuring peel strength 2" in 4-1 above, and for Comparative Example 4-1, samples were prepared using the method described in "Sample condition 2 for measuring peel strength 2" in 4-1 above.

[0191] (9) Transferability The workability when producing a molded article from the transfer sheets of the Examples, Comparative Examples and Reference Examples was evaluated according to the following criteria. A: The workability when peeling off the release substrate is good, and the transfer work is also good. C1: It is difficult to peel the release substrate 1 from the transfer sheet A before peeling the release substrate 2 from the transfer sheet A in a normal operation, and the transfer workability is poor. C2: After the transfer sheet B is attached to the adherend, the peeling force when peeling off the release substrate 2 is too strong, resulting in poor transfer workability.

[0192] [Table 4]

[0193] Table 4 confirms that the molded articles of Examples 4-1 to 4-5 are able to exhibit the function of an antifouling low refractive index layer satisfactorily. In particular, it can be confirmed that the molded articles of Examples 4-1, 4-2, and 4-5, in which the Si element ratio and C / Si of the antifouling low refractive index layer are within the above ranges, have good oil dust resistance. In particular, the molded article of Example 4-1 had excellent oil dust resistance even under LED, an evaluation light source that is more stringent than fluorescent lamps, and had scratch resistance at the same level as an antireflection layer produced by a dry manufacturing method.

[0194] (10-1) Preparation of samples for evaluating the texture of glass The adhesive layer side of transfer sheet B of Examples 4-1 to 4-4 was placed on the substrate (soda glass (thickness 1.8 mm, 10 cm square) from Hiraoka Special Glass Manufacturing Co., Ltd.), and heat-transferred from the release substrate 2 side of transfer sheet B using a roll-type hot stamping machine (manufactured by Navitas, product name "RH-300") under conditions of a roll temperature of 220 to 240°C and a roll speed of 20 mm / s. Next, the release substrate 2 of the transfer sheet B was peeled off to obtain molded articles of Examples 4-1 to 4-4 in which the adherend was glass. These molded articles had an adherend (glass), an adhesive layer, a hard coat layer, and an antifouling low refractive index layer in this order. In addition, a molded article having a glass adherend of Comparative Example 4-3 was obtained by laminating a commercially available optically adhesive anti-reflection film (Panac Corporation, product name: Panaclean DSG-17 / PD-C3) onto an adherend (soda glass (thickness 1.8 mm, 10 cm square) manufactured by Hiraoka Specialty Glass Co., Ltd.). The molded article of Comparative Example 4-3 has an adherend (glass), an adhesive layer (thickness 25 μm), a substrate (a triacetyl cellulose film with a thickness of 40 μm), a hard coat layer, and an anti-reflection layer, in that order. The reflectance Y value of the molded article of Comparative Example 4-3 was 0.4% or less, which was evaluated as level A.

[0195] (10-2) Evaluation of glass texture The molded body prepared in 10-1 was subjected to the following tests to evaluate the feel and smoothness: "Lightly sliding the surface of the molded body with the pad of a finger five times" and "Lightly tapping the surface of the molded body with a fingernail to check the sound." Specifically, the soda glass was used as a standard sample, and the feel and smoothness of the molded body were evaluated to see if they were close to those of the standard sample. The glass molded adherends of Examples 4-1 to 4-4 had a texture closer to that of glass than the glass molded adherend of Comparative Example 4-3. For the glass molded articles of Examples 4-1 to 4-4, there was no difference in the sound made by fingernails among the four samples, but in terms of sliding with the pad of a finger, Examples 4-2 and 4-3 were better than Examples 4-1 and 4-4. Furthermore, the reflection Y values ​​of Examples 4-2 and 4-3 were 0.2% or less, which were particularly excellent. [Explanation of symbols]

[0196] 10: Release base material 1 13: Release base material 20: Release base material 2 30: Transfer layer 31: Functional layer 1 32: Functional layer 2 100: Transfer sheet A 200: Transfer sheet B 300: Adherent 400: Laminate C 600: Conventional transfer sheet 800: Molded body

Claims

1. A method for producing a transfer sheet A by carrying out the following steps (1) to (2) in order. (1) A step of applying a coating liquid for forming a transfer layer onto a release substrate 1 to form a transfer layer including at least one functional layer. at least one of the functional layers has a function unevenly distributed on the side opposite to the release substrate 1, and the functional layer having a function unevenly distributed on the side opposite to the release substrate 1 is an antifouling low refractive index layer having a function unevenly distributed by an antifouling agent, the antifouling low refractive index layer has a refractive index of 1.10 to 1.48, the antifouling low refractive index layer contains a binder resin, the antifouling agent, and silica particles, the binder resin contains a cured product of a (meth)acrylate compound having a (meth)acryloyl group, the antifouling agent is any one selected from a fluorine-based resin, a silicone-based resin, and a fluorine-silicone copolymer resin, and the silica particles contain hollow silica particles and non-hollow silica particles, a surface region of the antifouling low refractive index layer opposite to the release substrate 1 is analyzed by X-ray photoelectron spectroscopy, the ratio of Si element attributable to the silica particles being 10.0 atomic % or more and 18.0 atomic % or less, and a ratio of C element being 180 atomic % or more and 500 atomic % or less when the ratio of Si element is converted to 100 atomic %, When the thickness of the antifouling low refractive index layer is divided into three equal parts and defined as a first region, a second region, and a third region in that order from the release substrate 1 side, any location in the first region and any location in the second region are analyzed by X-ray photoelectron spectroscopy, the ratio of Si element belonging to the silica particles is obtained to be 10.0 atomic % or more and 18.0 atomic % or less, and the ratio of C element when the ratio of Si element is converted to 100 atomic % is 180 atomic % or more and 500 atomic % or less. (2) A step of laminating a release substrate 2 on the transfer layer to obtain a transfer sheet A having the release substrate 1, the transfer layer, and the release substrate 2 in this order, and wherein the peel strength 2 between the release substrate 2 and the transfer layer is greater than the peel strength 1 between the release substrate 1 and the transfer layer.

2. The method for producing transfer sheet B further comprises carrying out the following step (3). (3) A step of peeling off the release substrate 1 from the transfer sheet A obtained by the method for producing a transfer sheet A according to claim 1 to obtain a transfer sheet B having the transfer layer on the release substrate 2.

3. A method for producing a molded body, comprising sequentially carrying out the following steps (4) and (5): (4) A step of obtaining a laminate C by closely adhering the surface of the transfer layer side of the transfer sheet B obtained by the method for producing a transfer sheet B according to claim 2 to an adherend. (5) A step of peeling off the release substrate 2 from the laminate C to obtain a molded article having a transfer layer on an adherend.

4. a transfer sheet A comprising a release substrate 1, a transfer layer, and a release substrate 2 in this order, wherein a peel strength 2 between the release substrate 2 and the transfer layer is greater than a peel strength 1 between the release substrate 1 and the transfer layer, the transfer layer comprising at least one functional layer, at least one of which has a function unevenly distributed on the release substrate 2 side, and the functional layer unevenly distributed on the release substrate 2 side is an antifouling low refractive index layer having a function unevenly distributed due to an antifouling agent, the antifouling low refractive index layer having a refractive index of 1.10 to 1.48, the antifouling low refractive index layer comprising a binder resin, the antifouling agent, and silica particles, the binder resin comprising a cured product of a (meth)acrylate compound having a (meth)acryloyl group, the antifouling agent being any one selected from a fluorine-based resin, a silicone-based resin, and a fluorine-silicone copolymer resin, and the silica particles comprising hollow silica particles and non-hollow silica particles, a ratio of Si element attributable to the silica particles, which is obtained by analyzing a surface region of the antifouling low refractive index layer on the release substrate 2 side by X-ray photoelectron spectroscopy, is 10.0 atomic % or more and 18.0 atomic % or less, and a ratio of C element, when the ratio of Si element is converted to 100 atomic %, is 180 atomic % or more and 500 atomic % or less; Transfer sheet A, in which the thickness of the antifouling low refractive index layer is divided into three equal parts, and defined as a first region, a second region, and a third region in that order from the release substrate 1 side, and an arbitrary location within the first region and an arbitrary location within the second region are analyzed by X-ray photoelectron spectroscopy, the ratio of Si element belonging to the silica particles is obtained to be 10.0 atomic % or more and 18.0 atomic % or less, and the ratio of C element when the ratio of the Si element is converted to 100 atomic % is 180 atomic % or more and 500 atomic % or less.

5. 5. The transfer sheet A according to claim 4, wherein the difference between the peel strength 2 and the peel strength 1 is 15 mN / 25 mm or more and 450 mN / 25 mm or less.

6. a transfer sheet B, the transfer sheet B comprising a transfer layer on a release substrate 2, the transfer layer comprising at least one functional layer, at least one of the functional layers having a function unevenly distributed on the release substrate 2 side, the functional layer having a function unevenly distributed on the release substrate 2 side being an antifouling low refractive index layer having a function unevenly distributed due to an antifouling agent, the antifouling low refractive index layer having a refractive index of 1.10 to 1.48, the antifouling low refractive index layer comprising a binder resin, the antifouling agent and silica particles, the binder resin comprising a cured product of a (meth)acrylate compound having a (meth)acryloyl group, the antifouling agent being any one selected from a fluorine-based resin, a silicone-based resin and a fluorine-silicone copolymer resin, the silica particles comprising hollow silica particles and non-hollow silica particles, a ratio of Si element attributable to the silica particles, which is obtained by analyzing a surface region of the antifouling low refractive index layer on the release substrate 2 side by X-ray photoelectron spectroscopy, is 10.0 atomic % or more and 18.0 atomic % or less, and a ratio of C element, when the ratio of Si element is converted to 100 atomic %, is 180 atomic % or more and 500 atomic % or less; Transfer sheet B, in which the thickness of the antifouling low refractive index layer is divided into three equal parts, and defined as a first region, a second region, and a third region in that order from the side opposite to the release substrate 2, and the ratio of Si element attributable to the silica particles obtained by analyzing any location in the first region and any location in the second region by X-ray photoelectron spectroscopy is 10.0 atomic % or more and 18.0 atomic % or less, and the ratio of C element when the ratio of Si element is converted to 100 atomic % is 180 atomic % or more and 500 atomic % or less.

7. a transfer layer on an adherend, the transfer layer having at least one functional layer, at least one of the functional layers having a function unevenly distributed on the side opposite to the adherend, the functional layer having a function unevenly distributed on the side opposite to the adherend being an antifouling low refractive index layer having a function unevenly distributed by an antifouling agent, the antifouling low refractive index layer having a refractive index of 1.10 to 1.48, the antifouling low refractive index layer comprising a binder resin, the antifouling agent and silica particles, the binder resin comprising a cured product of a (meth)acrylate compound having a (meth)acryloyl group, the antifouling agent being any one selected from a fluorine-based resin, a silicone-based resin and a fluorine-silicone copolymer resin, the silica particles comprising hollow silica particles and non-hollow silica particles, a ratio of Si element attributable to the silica particles, which is obtained by analyzing a surface region of the antifouling low refractive index layer opposite to the adherend by X-ray photoelectron spectroscopy, is 10.0 atomic % or more and 18.0 atomic % or less, and a ratio of C element, when the ratio of Si element is converted to 100 atomic %, is 180 atomic % or more and 500 atomic % or less; A molded product in which the thickness of the antifouling low refractive index layer is divided into three equal parts, and defined as a first region, a second region, and a third region in that order from the adherend side, and an arbitrary location in the first region and an arbitrary location in the second region are analyzed by X-ray photoelectron spectroscopy, the ratio of Si element belonging to the silica particles is obtained to be 10.0 atomic % or more and 18.0 atomic % or less, and the ratio of C element when the ratio of the Si element is converted to 100 atomic % is 180 atomic % or more and 500 atomic % or less.

8. The molded article according to claim 7, wherein the adherend is one selected from glass, ceramics, and resin, or a mixture thereof.

9. 9. The molded article according to claim 7 or 8, wherein the adherend is glass, and the layer of the layers constituting the transfer layer that is located closest to the adherend contains a resin having one or more functional groups selected from a carboxyl group and a methoxy group.

10. A front panel for an image display device, comprising the molded article according to any one of claims 7 to 9.

11. An image display device having a front panel on a display element, wherein the front panel is the molded article according to any one of claims 7 to 9.

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