JP2020160157A - Glass transfer antireflection film - Google Patents

Abstract

To provide a glass transfer antireflection film excellent in transferability to glass, adhesion, surface hardness and visibility.SOLUTION: A glass transfer antireflection film is formed by laminating an antireflection layer, a transfer hard coat layer formed of the photo cured product of a transfer hard coat resin composition (HAD) and a release film 2 in this order on a release film 1. The transfer hard coat resin composition (HAD) includes the following (a)-(c) components; and when using the total amount of (a)-(c) components as 100 mass%, the content of the (a) component is 1-12 mass%, the content of the (b) component is 15-48 mass%, and the content of the (c) component is 48-81 mass%, where (a) is a polyfunctional thiol compound, (b) is an active energy beam curable resin and (c) is a polyfunctional epoxy compound.SELECTED DRAWING: None

Description

The present invention relates to an antireflection film for glass transfer, which is applied to a glass substrate for a display and has excellent adhesion, surface hardness, and visibility.

Display (display device) is used under various situations and has various uses. In the automobile field, displays are used for car navigation systems, center information displays, instrument panels, etc., and various information can be provided. Further, with the recent spread of capacitive touch panels and the like, displays can be operated by touching to select information, and not only appearance but also characteristics such as operability and touch comfort are required.
Conventionally, a method of applying antireflection processing to the display surface by various methods has been used to deal with the deterioration of visibility due to the reflection of external light. Such a method is, for example, a bonding method in which an antireflection-treated film is bonded to glass via an adhesive layer, a dip method in which an antireflection layer is formed by a liquid film treatment on a glass substrate, and the like. However, when the bonding method is applied, there arises a problem that distortion due to the adhesive layer occurs and the excellent visibility, which is a characteristic of glass, is deteriorated. In the case of the dip method, there is a problem that the productivity deteriorates because it is necessary to prepare the dip method.

In order to solve these problems, a transfer method has been proposed in which a functional layer previously laminated and formed on a release film is transferred to impart an antireflection function. For example, Patent Document 1 discloses an antireflection film for glass transfer in which a thermoplastic resin and an ethylenically unsaturated compound are used in combination for a transfer layer, so that both a hard coat function and transferability can be achieved. There is. However, although the transfer layer by this technique has excellent surface hardness, it has poor tackiness, so that it does not follow the transfer base material, and air bubbles enter at the interface between the transfer base material and the transfer base material, and transfer defects are likely to occur. In addition, the adhesiveness with glass was insufficient.

Further, Patent Document 2 discloses a technique of blending an acrylic polymer with an ultraviolet curable epoxy resin in order to provide a glass transfer layer on a hard coat layer and improve adhesiveness in the glass transfer layer. However, the compounding of the acrylic polymer alone impairs the holding performance as a coating film, and when it is rolled, it tends to cause an adverse effect such as the adhesive layer protruding due to its own weight, and cannot be applied to roll-to-roll processing. Further, since the acrylic polymer flows at a temperature of Tg or more of the acrylic polymer, there is a problem that it is not suitable for storage in a high temperature environment.

In this way, the transfer method using an antireflection film for glass transfer should be an epoch-making method that originally imparts an antireflection function to a glass substrate while increasing productivity, but transferability to glass, adhesion, and surface surface Hardness and visibility could not be satisfied at the same time, and practical application was not advanced.

Japanese Unexamined Patent Publication No. 2004-042607 Japanese Unexamined Patent Publication No. 2003-154622

As described above, an object of the present invention is to provide an antireflection film for glass transfer, which is excellent in transferability, adhesion, surface hardness, visibility and productivity to glass.

As a result of intensive research to solve the above problems, the present inventors have selected a polyfunctional thiol compound, an active energy ray-curable resin, and a polyfunctional epoxy compound in the antireflection film for glass transfer used in the transfer method. It was found that the above-mentioned problems can be solved by forming a layer of a photocured material of a resin composition used in combination at a specific content as a transfer hard coat layer having both a transfer function and a hard coat function. We have found and completed the present invention.
That is, the present invention is the following [1] and [2].

[1] An antireflection layer, a transfer hard coat layer, and a release film 2 are laminated in this order on the release film 1.
The transfer hard coat layer is an antireflection film for glass transfer, which is a layer made of a photocured product of a transfer hard coat resin composition (HAD).
The transposed hard coat resin composition (HAD) contains the following components (a) to (c), and the content of the component (a) is 100% by mass as a total of the components (a) to (c). An antireflection film for glass transfer, which has 1 to 12% by mass, the content of the component (b) is 15 to 48% by mass, and the content of the component (c) is 48 to 81% by mass.
(A) Polyfunctional thiol compound (b) Active energy ray-curable resin (c) Polyfunctional epoxy compound [2] Release film 1 of the antireflection film for glass transfer according to the above [1] on the glass surface. A glass transfer molded product having a layer of a heat molded product composed of the peeled product and 2.

In addition, the description of "○○ to △△" in this specification means a numerical range including an upper limit and a lower limit unless otherwise described. That is, "○○ to △△" means "more than ○○, less than or equal to △△".

The antireflection film for glass transfer of the present invention can transfer to glass without bubbles. INDUSTRIAL APPLICABILITY The present invention provides an antireflection film for glass transfer, which is excellent in transferability, adhesion, surface hardness, and visibility to glass.

The antireflection film for glass transfer of the present invention has a structure in which an antireflection layer, a transfer hard coat layer, and a release film 2 are laminated in this order on a release film 1. The components of this antireflection film for glass transfer will be described in order below.

<Release film>
The constituent materials of the release films 1 and 2 are not particularly limited, but for example, polypropylene resin, polyethylene resin, polyamide resin, polyester resin, polycarbonate resin, acrylic resin, polyvinyl chloride resin, acetic acid. Resin sheets such as cellulose-based resin and fluorine-based resin can be used.

In addition, in order to improve the releasability of the release films 1 and 2, a release material is usually applied to the release surface (the joint surface with the antireflection layer or the transfer hard coat layer). Examples of the mold release material include an epoxy resin-based mold release agent, an epoxy melamine resin-based mold release agent, a melamine resin-based mold release agent, an aminoalkido resin-based mold release agent, a silicone resin-based mold release agent, and a fluorine resin-based mold release agent. One or more kinds of agents, cellulose derivative type release agents, urea resin type release agents, polyolefin resin type release agents, paraffin type release agents and the like can be used. A commercially available product on which the release material is previously applied and formed can be used. For example, Toyobo Co., Ltd., peeling film, E7002, E7006, E7007, K1504, K1571, TN100, TN200, Mitsubishi Chemical Holdings Group Co., Ltd. Diafoil, MR-, MRA, MRA (AA2), MRF, MRV38 (V04), film binar HTA, KF, BD, DG-2, etc. manufactured by Fujimori Kogyo Co., Ltd. can be mentioned.
The constituent materials and the release materials of the release films 1 and 2 may be the same as or different from each other.

The thickness of the release films 1 and 2 is preferably 20 to 200 μm. If the thickness of the release film is within this range, the strength of the release film is sufficiently maintained, so that there is no risk of the release film being torn when the release film is peeled off after transfer, and the release property should be sufficiently maintained. Can be done.
The thicknesses of the release films 1 and 2 may be the same or different from each other.

<Anti-reflective layer>
The antireflection layer is a layer for imparting an antireflection function for the purpose of improving visibility. The antireflection layer may be a single layer or a multilayer, but is preferably a single layer composed of a low refractive index layer or a multilayer including a high refractive index layer and a low refractive index layer, and particularly from the viewpoint of lowering the minimum reflectance. It is more preferable that the two layers are composed of a high refractive index layer and a low refractive index layer. When a two-layer structure consisting of a high refractive index layer and a low refractive index layer is used as the antireflection layer, the low refractive index layer, the high refractive index layer, the transfer hard coat layer, and the release mold are placed on the release film 1. It is preferable that the film 2 is a glass transfer antireflection film laminated in this order.
The antireflection layer can be designed in a timely manner based on the desired visibility, physical properties and cost. Further, the interfacial adhesion with the transfer hard coat layer is important, and it is necessary to design the composition so as to adhere to the transfer hard coat layer.

<Low refractive index layer>
The low refractive index layer is a layer for imparting an antireflection function, and when the antireflection layer is formed by the low refractive index layer alone, it is a layer that requires an adhesion function with a transfer hard coat layer and is low. It is formed by drying and curing the resin composition (L) for a refractive index layer. The film thickness of the low refractive index layer after curing is set so that the minimum reflectance in the target wavelength region is minimized in the range of 50 to 150 nm. When the thickness of the low refractive index layer is within the above range, the minimum reflectance does not become too high and it can be preferably used.

The resin composition (L) for a low refractive index layer is a resin composition containing an active energy ray-curable resin (Lb), low refractive index fine particles, and a photoinitiator. The blending amount of each component in the above composition is 100% by mass in total of the active energy ray-curable resin (Lb), the low refractive index fine particles, and the photoinitiator, of which 30 is usually the active energy ray-curable resin. It is a composition containing ~ 74% by mass, 25 to 65% by mass of low refractive index fine particles, and 1 to 10% by mass of a photoinitiator.
Other components can be blended in the resin composition (L) for a low refractive index layer. As other components, metal oxides, photosensitizers, stabilizers, ultraviolet absorbers, infrared absorbers, antioxidants, leveling agents, adhesion improvers, antifouling agents and the like are used.
The low refractive index layer is preferably adjusted so that the refractive index is 1.3 to 1.45 depending on the relative relationship between the active energy ray-curable resin (Lb) and the low refractive index fine particles. The refractive index in the present specification can be measured by an Abbe refractive index meter.

The resin composition (L) for a low refractive index layer contains an active energy ray-curable resin (Lb). In the present specification, the active energy ray-curable resin refers to a resin that is cured through a cross-linking reaction or the like when irradiated with ultraviolet rays, electron beams, or the like. Examples of the active energy ray-curable resin include monomers, oligomers, and polymers having an ethylenically unsaturated double bond such as a vinyl group and a (meth) acryloyl group.
Examples of the active energy ray-curable resin (Lb) used in the resin composition for a low refractive index layer (L) include acrylate compounds, urethane acrylate compounds, epoxy acrylate compounds, and monofunctional compounds and polyfunctional compounds in a timely manner. Selected and used. In particular, from the viewpoint of low refractive index, fluorine-containing acrylate compounds, urethane acrylate compounds, epoxy acrylate compounds and the like are preferable.
In the resin composition for a low refractive index layer (L), the active energy ray-curable resin (Lb), the low refractive index fine particles, and the photoinitiator total 100% by mass of the active energy ray-curable resin (Lb). The blending amount is usually 30 to 74% by mass, preferably 30 to 45% by mass. When the content of the active energy ray-curable resin (Lb) is within this range, the coating strength is kept good, and the content of the low refractive index fine particles is set within the range described later, so that the low refractive index is low. The refractive index of the layer is also lowered and the antireflection function is improved.

The low refractive index fine particles used in the low refractive index layer are preferably fine particles having a refractive index of 1.2 to 1.45, and examples thereof include hollow silica fine particles, magnesium fluoride fine particles, calcium fluoride fine particles, and the like. Hollow silica fine particles are particularly preferable from the viewpoint of low refractive index. The refractive index of the hollow silica fine particles is preferably 1.2 to 1.4.
The blending amount of the hollow silica fine particles is usually 100% by mass of the total of the active energy ray-curable resin (Lb), the low refractive index fine particles, and the photoinitiator in the low refractive index layer resin composition (L). It is 25 to 65% by mass, preferably 50 to 65% by mass. When the blending amount is within this range, the refractive index of the low refractive index layer becomes low, a good antireflection function can be obtained, and the amount of the active energy ray-curable resin (Lb) is set within the above range. The strength of the coating film can also be maintained.

The average particle size of the hollow silica fine particles preferably does not greatly exceed the thickness of the low refractive index layer, and specifically, the average particle size of the hollow silica fine particles is preferably 0.1 μm or less. This is to avoid light scattering that results in a cloudy appearance and reduces visibility. The average particle size of the hollow silica fine particles is usually 0.03 μm or more.

Further, it is preferable that the surface of the hollow silica fine particles is modified with a silane coupling agent having a (meth) acryloyl group or the like. By modifying the surface of the hollow silica fine particles with a silane coupling agent having a (meth) acryloyl group or the like, a covalent bond with the active energy ray-curable resin is formed, and the coating film strength tends to be increased. Further, when a large amount of hollow silica fine particles are blended, the interface between the low refractive index layer and the transferred hard coat layer made of the transferred hard coat resin composition (HAD) formed in contact with the low refractive index layer, or low. At the interface between the refractive index layer and the high refractive index layer made of the resin composition (H) for a high refractive index layer formed in contact with the refractive index layer, the surface of the hollow silica fine particles contained in each layer is modified. A covalent bond is formed between the (meth) acryloyl group and the active energy ray-curable resin, and the interfacial adhesion tends to be stronger.

Examples of the photoinitiator used in the low refractive index layer include a photoradical polymerization initiator. The photoradical polymerization initiator can shorten the reaction time as compared with the photocationic polymerization initiator and the photoanionic polymerization initiator, and is suitable for roll-to-roll production. In the resin composition for a low refractive index layer (L), the blending amount of the photoinitiator is usually 1 with respect to a total of 100% by mass of the active energy ray-curable resin (Lb), the low refractive index fine particles, and the photoinitiator. It is 10% by mass, preferably 2-8% by mass. When the blending amount is within this range, the low refractive index layer can be suitably used without being poorly cured or having an excessively high refractive index.
Examples of the photoradical polymerization initiator include benzoin or benzoin alkyl ether such as benzoin and benzoin methyl ether; aromatic ketones such as benzophenone and benzoylbenzoic acid; benzyl ketal such as benzyl dimethyl ketal and benzyl diethyl ketal; 1-hydroxycyclohexyl. Acetophenone such as phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propane-1-one; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) Examples thereof include acylphosphine oxides such as phenylphosphine oxide.

The resin composition for a low refractive index layer may be diluted with an organic solvent and used in order to make the system uniform and facilitate coating. Examples of such an organic solvent include alcohol-based solvents, aromatic hydrocarbon-based solvents, ether-based solvents, ester-based solvents, ether ester-based solvents, ketone-based solvents, and phosphoric acid ester-based solvents.

<High refractive index layer>
The high refractive index layer is a layer that is provided with an antireflection function and needs to have an adhesion function with a transfer hard coat layer, and is formed by drying and curing the resin composition (H) for a high refractive index layer. .. The cured film thickness of the high refractive index layer is set so that the minimum reflectance in the target wavelength region is minimized in the range of 50 to 150 nm. When the thickness of the high refractive index layer is within the above range, the minimum reflectance does not become too high and it can be preferably used.
The resin composition (H) for a high refractive index layer is a resin composition containing an active energy ray-curable resin (Hb), high refractive index fine particles, and a photoinitiator. The blending amount of each component of each of the above compositions is usually 100% by mass of the total of the active energy ray-curable resin (Hb), the high refractive index fine particles, and the photoinitiator, among which the active energy ray-curable resin (Hb) is used. ) Is 19 to 79% by mass, high refractive index fine particles are 20 to 80% by mass, and the photoinitiator is 1 to 10% by mass.

Other components can be blended in the resin composition (H) for a high refractive index layer. As other components, metal oxides, photosensitizers, stabilizers, ultraviolet absorbers, infrared absorbers, antioxidants, leveling agents, adhesion improvers and the like are used.
The refractive index of the high refractive index layer is not particularly limited as long as it is higher than the refractive index of the low refractive index layer described above, but is usually 1.5 to 1.8.
As the active energy ray-curable resin (Hb) used in the high refractive index layer, the low refractive index layer or the transferred hard coat layer is used in order to improve the adhesion to the low refractive index layer or the transferred hard coat layer. Compounds similar to the active energy ray-curable resin used in the above are preferable, and examples thereof include acrylate compounds, urethane acrylate compounds, and epoxy acrylate compounds, and monofunctional compounds and polyfunctional compounds are selected and used in a timely manner.

In the resin composition for a high refractive index layer (H), the active energy ray-curable resin (Hb), the high refractive index fine particles, and the photoinitiator are 100% by mass in total, and the active energy ray-curable resin (Hb) is used. The blending amount is usually 19 to 79% by mass, preferably 30 to 60% by mass. When the blending amount is within this range, the adhesion to the transferred hard coat layer and the low refractive index layer is improved, and the high refractive index fine particles are adjusted to the content described later to refract the high refractive index layer. The rate is increased, and the antireflection function can be satisfactorily exhibited.

Examples of the high refractive index fine particles used in the high refractive index layer include fine particles such as tin oxide, zinc oxide, titanium oxide, zirconium oxide, ITO, ATO, and zinc antimonate. The refractive index of the high refractive index fine particles is higher than that of the low refractive index fine particles described above, and specifically, it is in the range of 1.5 to 2.1.
In the resin composition for a high refractive index layer (H), the blending amount of the high refractive index fine particles is usually 100% by mass with respect to the total of 100% by mass of the active energy ray-curable resin (Hb), the high refractive index fine particles, and the photoinitiator. It is 20 to 80% by mass, preferably 30 to 60% by mass. When the blending amount is within this range, the refractive index of the high refractive index layer is increased, the antireflection function can be satisfactorily exhibited, and the amount of the active energy ray-curable resin is set within the above range. The strength as a coating film is also sufficiently high.

The average particle size of the high refractive index fine particles does not greatly exceed the thickness of the high refractive index layer, and specifically, the average particle size of the high refractive index fine particles is preferably 0.1 μm or less. This is to avoid light scattering that results in a cloudy appearance and reduces visibility. The average particle size of the highly refracted fine particles is usually 0.01 μm or more.

Examples of the photoinitiator used in the high refractive index layer include a photoradical polymerization initiator. The photoradical polymerization initiator is preferably used to shorten the reaction time, and the photocationic polymerization initiator and the photoanionic polymerization initiator require a long reaction time, so that they should be prepared by roll-to-roll. Is not preferable. In the resin composition for a high refractive index layer (H), the blending amount of the photoinitiator is usually 1 with respect to a total of 100% by mass of the active energy ray-curable resin (Hb), high refractive index fine particles, and the photoinitiator. It is 10% by mass, preferably 2-8% by mass. When the blending amount is within this range, the curability of the high refractive index layer is good, and the refractive index of the high refractive index layer can be kept high. Specific examples of the photoradical polymerization initiator include the same photoradical polymerization initiator contained in the resin composition (L) for a low refractive index layer described above.

The resin composition for a high refractive index layer may be diluted with an organic solvent and used in order to make the system uniform and facilitate coating. Examples of such an organic solvent include alcohol-based solvents, aromatic hydrocarbon-based solvents, ether-based solvents, ester-based solvents, ether ester-based solvents, ketone-based solvents, and phosphoric acid ester-based solvents.

<Transfer hard coat layer>
The transfer hard coat layer is a layer for imparting hard coat property and adhesiveness to glass, and is formed by drying and photocuring the transfer hard coat resin composition (HAD). The translocation hard coat resin composition (HAD) used in the present invention contains a polyfunctional thiol compound (a), an active energy ray-curable resin (b) and a polyfunctional epoxy compound (c) as essential components, and if necessary. , Photoinitiator, epoxy curing catalyst.

The translocation hard coat layer used in the present invention is translocated because an optimum network structure is formed in the layer by the photocuring reaction of the polyfunctional thiol compound (a) and the active energy ray-curable resin (b). The hard coat layer itself can maintain the strength as a coating film. Further, by containing the polyfunctional epoxy compound (c), it has an appropriate tack property and is excellent in adhesiveness to glass. The hardness of the adhesive layer itself and the adhesiveness to the glass are imparted by a thermosetting reaction composed of the polyfunctional thiol compound (a) and the polyfunctional epoxy compound (c) by thermosetting after bonding to the glass. Is possible.

In the translocation hard coat resin composition (HAD), the total of the polyfunctional thiol compound (a), the active energy ray-curable resin (b), and the polyfunctional epoxy compound (c) is 100% by mass (hereinafter, simply (a). ) To (c), which is usually 1 to 12% by mass of the polyfunctional thiol compound (a) and 15 to 48% by mass of the active energy ray-curable resin (b). It is a composition containing 48 to 81% by mass of the functional epoxy compound (c).

The polyfunctional thiol compound (a) contained in the translocation hard coat resin composition (HAD) is a compound having two or more mercapto groups (thiol groups) in the molecule, and has 2 to 6 mercapto groups in the molecule. It is preferably a compound having an individual. From the viewpoint of forming an optimum network structure in the layer and imparting adhesion to glass, the polyfunctional thiol compound (a) is preferably a compound having 3 to 6 mercapto groups in the molecule, more preferably. It is preferably a compound having 4 to 6 mercapto groups in the molecule.
Specific examples of the polyfunctional thiol compound (a) include trimethylolpropanthris (3-mercaptopropionate), tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate, and pentaerythritol tetrakis (3-mercaptopropionate). Mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate) and the like. The blending amount of the polyfunctional thiol compound (a) with respect to the total 100% by mass of (a) to (c) in the translocation hard coat resin composition (HAD) is 1 to 12% by mass. When it is less than 1% by mass, the optimum network structure in the layer is not formed due to the photocuring reaction of the polyfunctional thiol compound (a) and the active energy ray-curable resin, and the coating film tends not to be retained as an adhesive layer. It is not preferable. On the other hand, if it is more than 12% by mass, the hardness of the coating film tends to be weak, which is not suitable. The blending amount of the polyfunctional thiol compound (a) with respect to the total 100% by mass of (a) to (c) is preferably 1 to 10% by mass, and more preferably 2 to 6% by mass.

The active energy ray-curable resin (b) contained in the translocation hard coat resin composition (HAD) is used to improve the adhesion to the low refractive index layer or the high refractive index layer, and is simply used. Functional compounds and polyfunctional compounds are selected and used in a timely manner. Examples of the active energy ray-curable resin (b) include (meth) acrylate compounds such as polyol (meth) acrylate, urethane (meth) acrylate compound, and epoxy (meth) acrylate compound, which have a (meth) acryloyl group. The number of functional groups is preferably bifunctional or higher, and more preferably 2 to 6 functional. For the purpose of improving the surface hardness, it is preferable to select polyol (meth) acrylate as a main component, and for the purpose of improving transferability to glass, it is preferable to select a urethane (meth) acrylate compound as a main component. For the purpose of improving the adhesion to glass, it is preferable to select an epoxy (meth) acrylate compound as a main component.
The blending amount of the active energy ray-curable resin (b) is 15 to 48% by mass, preferably 16 to 45% by mass, more preferably, based on 100% by mass of the total of (a) to (c). Is 18-40% by mass. If the amount is too small, the optimum network structure in the layer is not formed by the photocuring reaction of the polyfunctional thiol compound (a) and the active energy ray-curable resin (b), and the coating film is formed as a transfer hard coat layer. Not retained. On the other hand, if the amount is too large, the adhesiveness with the glass is deteriorated.

The polyfunctional epoxy compound (c) contained in the translocation hard coat resin composition (HAD) is an organic compound having two or more epoxy groups (oxylan rings). The molecular weight of the polyfunctional epoxy resin is 200 to 50,000, preferably 200 to 48,000, and more preferably 200 to 46,000. When the molecular weight is within this range, the volatility of the polyfunctional epoxy resin does not increase and the odor does not become strong, and the solubility in other components and the adhesion to glass are good.

Examples of the polyfunctional epoxy compound (c) include oxidation obtained by oxidizing the double bond of a glycidyl ether type epoxy resin, a glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin, or a double bond-containing compound with a peroxide. Examples include type epoxy resins. Among these, glycidyl ether type epoxy resin and glycidyl ester type epoxy resin are preferable because the reactivity at room temperature is slow and the usable time is long. As the polyfunctional epoxy resin, only one type may be used alone, or two or more types may be mixed and used. The blending amount of the polyfunctional epoxy compound (c) is 48 to 81% by mass with respect to the total of 100% by mass of (a) to (c). If it is less than 48% by mass, it is not suitable because it causes a decrease in adhesiveness with glass. On the other hand, when it is more than 81% by mass, the amount of the polyfunctional thiol compound (a) or the active energy ray-curable resin (b) is small, and the coating film tends not to be retained as an adhesive layer, which is not preferable. The blending amount of the polyfunctional epoxy compound (c) with respect to the total 100% by mass of (a) to (c) is preferably 50 to 80% by mass, and more preferably 55 to 79% by mass.

As the photoinitiator contained in the translocation hard coat resin composition (HAD) as required, a photoradical polymerization initiator is preferable. The photoradical polymerization initiator is preferably used when shortening the reaction time, and the photocationic polymerization initiator and the photoanionic polymerization initiator require a long reaction time, so that the preparation by roll-to-roll is considered. Is not preferable. Specific examples of the photoradical polymerization initiator include the same photoradical polymerization initiator contained in the resin composition (L) for a low refractive index layer described above.
The blending amount of the photoinitiator with respect to the total 100% by mass of (a) to (c) is 1 to 10% by mass. If it is more than 10% by mass, the adhesion to the glass tends to decrease, which is not preferable. The blending amount of the photoinitiator with respect to the total 100% by mass of (a) to (c) is preferably 1 to 5% by mass.

An amine compound or the like is used as the epoxy curing catalyst contained in the translocation hard coat resin composition (HAD) as needed. The epoxy curing catalyst is added to accelerate (catalyst) the reaction between the thiol group and the epoxy group. Examples of the amine compound include monofunctional amines having a molecular weight of 90 to 700, preferably 100 to 690, and more preferably 110 to 680, and polyamines having a plurality of amino groups. Moreover, the amine compound may form a salt with an organic acid in advance in order to adjust the catalytic activity. Organic acids to be reacted with the amine compound in advance include aliphatic carboxylic acids such as stearic acid and 2-ethylhexanoic acid having 1 to 5 carbon atoms and 1 to 5 carboxyl groups in the molecule, and carboxyls having 1 to 20 carbon atoms. Examples thereof include aromatic carboxylic acids such as pyromellitic acid, trimellitic acid and benzoic acid having 1 to 10 groups in the molecule, or isocyanuric acid.
The content of the epoxy curing catalyst in the translocation hard coat resin composition (HAD) is preferably 0.1 to 10 parts by mass, more preferably 1 part by mass with respect to 100 parts by mass of the polyfunctional epoxy compound (c). ~ 5 parts by mass.

The film thickness of the transferred hard coat layer after curing is set within the range of 1 to 50 μm, preferably 1 to 15 μm. If the film thickness is thinner than 1 μm, air bubbles will be caught when the film is transferred to the glass, which is a drawback and is not preferable. On the other hand, when the film thickness is thicker than 50 μm, the hard coat function tends to deteriorate, which is not preferable.

The translocation hard coat resin composition (HAD) may be used diluted with an organic solvent in order to make the system uniform and facilitate coating. Examples of such an organic solvent include alcohol-based solvents, aromatic hydrocarbon-based solvents, ether-based solvents, ester-based solvents, ether ester-based solvents, ketone-based solvents, and phosphoric acid ester-based solvents.

<Formation of antireflection film for glass transfer>
The antireflection layer is preferably formed of a single layer composed of a low refractive index layer or two layers composed of a low refractive index layer and a high refractive index layer.
When the antireflection layer is formed of a low refractive index layer, the antireflection layer is formed by applying a resin composition for a low refractive index layer onto the release film 1, drying it if necessary, and then using active energy rays. It is formed by curing by irradiation, thereby obtaining a laminated body X1 in which an antireflection layer composed of a single layer having a low refractive index is laminated on the release film 1. A release material may be applied to the release surface of the release film 1 in order to improve the release property.
When the antireflection layer is formed of two layers consisting of a low refractive index layer and a high refractive index layer, the antireflection layer is obtained by applying a resin composition for a high refractive index layer on the low refractive index layer. It is formed by drying, if necessary, and then curing by irradiation with active energy rays. As a result, the laminated body X2 in which the antireflection layer is laminated on the release film 1 is obtained. The laminate X2 is a laminate X2 in which a release film 1, a low refractive index layer, and a high refractive index layer are laminated in this order.

The transfer hard coat layer is formed by applying a transfer hard coat resin composition on the antireflection layer of the laminate X1 or X2, drying it if necessary, and then curing it by irradiation with active energy rays. To. As a result, the laminated body Y in which the transfer hard coat layer is formed on the antireflection layer of the laminated body X1 or X2 is obtained.
Next, as a final step, the release film 2 is bonded onto the transfer hard coat layer of the laminated body Y to obtain an antireflection film for glass transfer.

When transferring the antireflection film for glass transfer to glass, the release film 2 is peeled off, and then the transfer hard coat layer surface is bonded to the glass. After that, heat treatment is performed to peel off the release film 1, so that various functions can be transferred onto the glass. Therefore, when the peeling force at the interface between the release film 1 and the low refractive index layer is R1 and the peeling force at the interface between the release film 2 and the transfer hard coat layer is R2, it is preferable that the relationship is R1> R2.

Further, when the release film 2 is peeled off, if the intra-layer network of the transfer hard coat layer is insufficient, the transfer hard coat layer component may remain on the release film 2, so that the transfer hard coat resin The composition needs to be properly designed.

The coating method of the resin composition for a low refractive index layer, the resin composition for a high refractive index layer, and the transfer hard coat resin composition is not particularly limited, and for example, a roll coating method, a spin coating method, a dip coating method, etc. Any known coating method such as a spray coating method, a bar coating method, a knife coating method, a die coating method, an inkjet method, and a gravure coating method can be adopted.

As a method of laminating the release film 2 on the transfer hard coat layer, there is no problem in using a known technique, but a method of laminating by pressing a roller is particularly preferable. If the intra-layer network of the transfer hard coat layer is insufficient, the adhesive layer may protrude when bonded or stored as a roll-to-roll shape. Therefore, the transfer hard coat resin composition Things need to be designed properly.

Examples of the active energy ray include UV (ultraviolet ray) and EB (electron beam). Light irradiation amount is required about 150~1000mJ / cm ^2, in a nitrogen atmosphere, the light irradiation amount, it is possible to reduce to about 100 mJ / cm ^2.

Each step of producing the antireflection film for glass transfer of the present invention is preferably a roll-to-roll method in which productivity is significantly improved. The roll-to-roll method does not use individually separated supports as in the single-wafer method, but applies, dries, cures, and bonds while feeding out a long film support wound in a roll shape. A transport method in which the film is continuously wound up on a roll. All the processes may be connected, but if the processing time for each process is different, it is more productive to unwind and wind each process as needed.

The glass transfer molded product of the present invention has a layer of a heat-molded product made of a release product of the release films 1 and 2 on the glass surface of the glass base material. The heat-molded product is a heated laminate composed of an antireflection layer and a transfer hard coat layer. Specifically, as a method for obtaining the glass transfer molded product of the present invention, the release film 2 is peeled from the antireflection film for glass transfer of the present invention, and then the release film 2 is peeled off from the antireflection film for glass transfer. Is transferred to the glass surface with the transferred hard coat layer and the glass surface facing each other, and the release film 1 which is the base film is peeled off. As the transfer method, for example, a hot press can be used. More specifically, the surface of the transferred hard coat layer is brought into contact with the glass surface of the glass base material and heated to adhere to the glass base material. After that, the release film 1 is peeled off. The device used for the hot press may be either a continuous type or a single-wafer type, but in order to avoid a decrease in yield due to air bubble mixing, it is preferable to use a single-wafer type vacuum heat press machine to improve productivity. A roll laminator under atmospheric pressure can be used for.

The heating temperature is preferably 100 ° C. to 180 ° C. Within this temperature range, the polyfunctional thiol compound and the polyfunctional epoxy compound are well bonded, and the softening of the release film does not matter. Further, when heating is required, it is also possible to peel off the release film 1 and then heat it again. The heating temperature at that time is preferably 100 ° C. to 250 ° C.
Examples of the glass substrate as the adherend include alkaline glass, non-alkali glass, heat-tempered glass, and chemically tempered glass, and chemically strengthened glass, which is widely used as a cover glass for a touch panel, is preferable. Here, the chemically strengthened glass refers to glass whose mechanical properties such as hardness are improved by replacing sodium ions on the glass surface with potassium ions by chemical treatment.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.
[Preparation of resin composition for low refractive index layer]
A resin composition for a low refractive index layer (L-1 to L-5) was obtained by mixing each component of the type and amount shown in Table 1. Next, MEK (methyl ethyl ketone) was mixed with each composition so that the solid content concentration was 5% by mass to obtain a coating liquid for a low refractive index layer. The types of each component shown in Table 1 are as follows.

(Active energy ray-curable resin (Lb))
α-1: Dipentaerythritol hexaacrylate α-2: Urethane acrylate compound, "UV-7630B" (trade name) manufactured by Nippon Synthetic Chemical Industry Co., Ltd., molecular weight (Mw) 2200, number of functional groups 6,
α-3: Fluorine-containing acrylate compound, "LINK-162A" (trade name) manufactured by Kyoeisha Chemical Co., Ltd., number of functional groups 2,
α-4: Epoxy acrylate compound, "Epoxy ester 200PA" (trade name) manufactured by Kyoeisha Chemical Co., Ltd., number of functional groups 2,
(Hollow fine particles)
β-1: Hollow silica fine particles with a particle diameter of 60 nm and silane coupling treatment, "Thruria 4320" (trade name) manufactured by Nikki Catalyst Kasei Co., Ltd., refractive index 1.25
β-2: Silane-coupled hollow silica fine particles with a particle diameter of 70 nm, "Thruria 5320" (trade name) manufactured by Nikki Catalyst Kasei Co., Ltd., refractive index 1.20
(Light initiator)
γ-1: 1-Hydroxycyclohexyl-phenylketone, "IRGACURE184" manufactured by Ciba Specialty Chemicals Co., Ltd. (trade name)

[Preparation of resin composition for high refractive index layer]
A resin composition for a high refractive index layer (H-1, H-2) was obtained by mixing each component of the type and amount shown in Table 2. Next, MEK was mixed with each composition so that the solid content concentration was 5% by mass to obtain a coating liquid for a high refractive index layer. The specific materials shown in Table 2 are as follows.
(Active energy ray-curable resin (Hb))
α-1: Dipentaerythritol hexaacrylate α-2: Urethane acrylate, "UV-7630B" manufactured by Nippon Synthetic Chemical Industry Co., Ltd., molecular weight (Mw) 2200, number of functional groups 6
(High refractive index fine particles)
ε-1: ITO fine particles, refractive index 1.8 (average particle diameter: 0.06 μm)
(Light initiator)
γ-1: 1-Hydroxycyclohexyl-phenylketone, "IRGACURE184" manufactured by Ciba Specialty Chemicals Co., Ltd. (trade name)

[Preparation of Transfer Hard Coat Resin Composition]
A translocation hard coat resin composition (HAD-1 to HAD-9, HAD'-1 to HAD'-8) was obtained by mixing the components of the types and amounts shown in Tables 3 and 4. Next, methyl isobutyl ketone (MIBK) was mixed with each composition so that the solid content concentration was 20% by mass to obtain a coating liquid for a transfer hard coat layer. The specific materials shown in Tables 3 and 4 are as follows.
(Polyfunctional thiol compound (a))
a-1: Dipentaerythritol hexakis (3-mercaptopropionate)
a-2: Trimethylolpropane tris (3-mercaptopropionate)
a-3: Tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate

(Active energy ray-curable resin (b))
b-1: Dipentaerythritol hexaacrylate, number of functional groups 6
b-2: Urethane acrylate, "UV-7630B" (trade name) manufactured by Nippon Synthetic Chemical Industry Co., Ltd., molecular weight (Mw) 2200, number of functional groups 6
b-3: Acrylic acid-modified tripropylene glycol diglycidyl ether, "Epoxy ester 200PA" (trade name) manufactured by Kyoeisha Chemical Co., Ltd., number of functional groups 2
b-4: Diethylene glycol dimethacrylate, "Light Ester 2EG" (trade name) manufactured by Kyoeisha Chemical Co., Ltd., number of functional groups 2
(Resin other than active energy ray-curable resin)
b'-1: Styrene / methacrylic polymer, "Dianal BR-50" (trade name) manufactured by Mitsubishi Rayon Co., Ltd., weight average molecular weight 65,000
(Polyfunctional epoxy compound (c))
c-1: Phosphoric acid-modified bisphenol A type epoxy resin, "ADEKA RESIN EP-49-10N" (trade name) manufactured by ADEKA Corporation, epoxy equivalent 220 g / eq
c-2: Bisphenol A type liquid epoxy resin, "jER 828EL" (trade name) manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 190 g / eq
(Light initiator)
d-1: 1-Hydroxycyclohexylphenylketone, "IRGACURE184" manufactured by Ciba Specialty Chemicals Co., Ltd. (trade name)
(Epoxy curing catalyst)
e-1: Imidazole / alkylurea modified product, "ADEKA Hardener EH-3366S" manufactured by ADEKA Corporation (trade name)

<Manufacturing of antireflection film for glass transfer>
(Example 1)

On the release layer surface of the release film 1 (PET1) [trade name: E7002, film thickness: 50 μm, manufactured by Toyo Boseki Co., Ltd.], 5 mass of the resin composition for low refractive index (L-1) was added to the solvent (methyl ethyl ketone). A coating liquid for a low refractive index layer diluted to% is applied with a bar coater so that the film thickness after curing is 90 nm, and the release film 1 is cured by irradiating with ultraviolet rays of 50 mJ with a 120 W high-pressure mercury lamp. A laminate X1 having an antireflection layer (low refractive index layer) formed on it was obtained.

Subsequently, a transfer hard coat resin composition (HAD-1) diluted to 20% by mass with a solvent (methyl isobutyl ketone) on the antireflection layer (low refractive index layer) of the laminate X1. The layer coating liquid is applied with a bar coater so that the film thickness after curing is 5 μm, and is cured by irradiating 400 mJ of ultraviolet rays with a 120 W high-pressure mercury lamp, and then transferred onto the antireflection layer of the laminate X1. A laminate Y on which a wearing hard coat layer was formed was obtained. Then, the release layer surface of the release film 2 [trade name: E7002, film thickness: 50 μm, manufactured by Toyobo Co., Ltd.] is bonded so as to face the transfer hard coat layer surface for glass transfer of Example 1. An antireflection film was prepared.

(Examples 2-9, Comparative Examples 1-8)
For glass transfer in the same manner as in Example 1 except that the types of the resin composition for low refractive index and the transfer hard coat resin composition and the film thickness of each layer are the materials and film thicknesses shown in Tables 5 and 6. An antireflection film was prepared.

(Example 10)
The low refractive index was placed on the release film 1 in the same manner as in Example 1 except that the film thickness after curing was adjusted to 100 nm using the resin composition for a low refractive index layer (L-1). A laminated body X1 having an antireflection layer composed of layers was obtained. Next, a coating liquid for a high refractive index layer obtained by diluting the resin composition for a high refractive index layer (H-1) with a solvent (methyl ethyl ketone) to 5% by mass on the low refractive index layer of the laminate X1 was cured with a bar coater. A high refractive index layer is prepared by applying the film so that the subsequent film thickness is 90 nm and irradiating with an ultraviolet ray of 50 mJ with a 120 W high-pressure mercury lamp to cure the film, and the low refractive index layer and the high refractive index layer are formed on the release film 1. A laminated body X2 having an antireflection layer composed of a refractive index layer was obtained.

Subsequently, on the antireflection layer of the laminate X2, a coating liquid for a transfer hard coat layer obtained by diluting the transfer hard coat resin composition (HAD-1) with a solvent (methyl isobutyl ketone) to 20% by mass is applied. It is applied with a coater so that the film thickness after curing is 1 μm, and is cured by irradiating 400 mJ of ultraviolet rays with a 120 W high-pressure mercury lamp to form a transfer hard coat layer on the antireflection layer of the laminate X2. The laminated body Y was obtained. Then, the release layer surface of the release film 2 [trade name: E7002, film thickness: 50 μm, manufactured by Toyobo Co., Ltd.] is bonded so as to face the transfer hard coat layer surface for glass transfer of Example 10. An antireflection film was prepared.

(Example 11)
Example 10 except that the types of the resin composition for a low refractive index layer, the resin composition for a high refractive index layer, and the transposed hard coat resin composition, and the film thickness of each layer are the materials and film thicknesses shown in Table 5. In the same manner as above, an antireflection film for glass transfer was produced.

The antireflection film for glass transfer of each of the examples and the comparative examples obtained as described above was evaluated for peelability and transfer hard coat layer protrusion by the following method.

[Evaluation of peelability]
The release film 2 was peeled off from the antireflection film for glass transfer, and the presence or absence of a transferred product of the transferred hard coat resin composition on the release surface of the release film 2 was visually evaluated.
◯: The transferred product of the transferred hard coat resin composition cannot be visually recognized.
X: The transferred product of the transferred hard coat resin composition can be visually recognized.
[Evaluation of the transfer hard coat layer protruding]
Twenty antireflection films for glass transfer cut into squares having a length of 3 cm and a width of 3 cm were stacked and installed on a glass plate. Then, a glass plate was placed on the transfer film, a load of 1 kg was placed on the glass plate, and the mixture was allowed to stand at 60 ° C. for 23 days.
◯: No protrusion of the transferred hard coat layer is observed from the end.
X: Overhang of the transferred hard coat layer is observed at the end.

<Manufacturing of glass transfer molded products>
With respect to the antireflection films for glass transfer of Examples and Comparative Examples manufactured as described above, the release film 2 was peeled off, and the transfer hard coat layer surface was bonded to the glass with a hand roller. Then, by heating at 150 ° C. for 60 minutes and peeling off the release film 1, a glass having a layer of a heat-molded product composed of peeled materials of the release films 1 and 2 of the antireflection film for glass transfer on the glass surface. A transfer molded product was produced.
In Comparative Examples 1, 2, 4, 7, and 8, the peelability was poor and a glass transfer molded product could not be produced.

(Comparative Example 9)
In this comparative example, an antireflection film with an adhesive layer was used in place of the antireflection film for glass transfer of the present invention to prepare a glass-coated synthetic type product.
A coating liquid for a low refractive index layer obtained by diluting the resin composition for a low refractive index layer (L-1) with a solvent (methyl ethyl ketone) to 5% by mass is applied as a transparent base film on a polyethylene terephthalate (PET) film having a thickness of 100 μm. A low refractive index layer was formed by applying a bar coater so that the film thickness after curing was 90 nm and irradiating with an ultraviolet ray of 500 mJ with a 120 W high-pressure mercury lamp to cure the film, thereby producing an antireflection film.
Next, an adhesive layer having a thickness of 25 μm was formed on the surface of the antireflection film opposite to the low refractive index layer, and bonded to glass via the adhesive layer to prepare a glass-bonded synthetic product.
The obtained glass transfer molded product and glass-pasted synthetic type product were evaluated for distortion, minimum reflectance, pencil hardness, adhesion, and transferability by the following methods.

[Distortion evaluation]
The glass transfer molded product and the glass-pasted synthetic type product were visually confirmed and the presence or absence of distortion was evaluated.
◯: Distortion cannot be confirmed.
×: Distortion can be confirmed.
[Minimum reflectance]
In order to prevent backside reflection of glass transfer molded products and glass-pasted synthetic products, the back side is painted with black paint and the wavelength of light is 380 nm using a spectrophotometer [manufactured by JASCO Corporation, trade name: U-best560]. 5 ° and −5 ° specular spectra at ~ 780 nm were measured. The minimum reflectance (%) was read from the obtained reflection spectrum.

[Pencil hardness]
A scratch test was conducted with a pencil in accordance with JIS K5600. The hardness of the pencil is 3H, 2H, H, F, and HB in descending order of hardness.
[Adhesion]
A grid peeling tape test was performed in accordance with JIS D0202-1998. The evaluation was based on the percentage of squares that did not peel off from the glass. For example, 100/100 means that all of the 100th squares were not peeled off, and 0/100 means that all of the 100th squares were peeled off.
[Transferability]
The glass transfer molded product was visually confirmed to confirm transfer defects and the presence or absence of air bubbles.
◯: No transfer failure or air bubbles can be confirmed.
X: Either transfer failure or air bubbles can be confirmed.

From the results in Table 5, regarding Examples 1 to 11, the transferable hard coat resin composition used in the present invention has no abnormality in peelability, and even when a load is applied, the transfer hard coat layer does not protrude. I was able to confirm. Further, the glass transfer molded product obtained by using the translocation hard coat resin composition used in the present invention was excellent in distortion, minimum reflectance, pencil hardness, adhesion and transferability.

On the other hand, from the results in Table 6, in Comparative Examples 1 and 2, the content of the polyfunctional thiol compound in the transposed hard coat resin composition was small, and the peelability and the adhesive layer were poorly evaluated. In Comparative Example 4, the content of the active energy ray-curable resin in the translocation hard coat resin composition was small, and the peelability and the adhesive layer were poorly evaluated. In Comparative Example 7, the content of the polyfunctional epoxy compound (c) in the translocated hard coat resin composition was large, and the results were poor in peelability and adhesion layer protrusion evaluation. In Comparative Example 8, as a result of using an acrylic polymer instead of the active energy ray-curable resin as the translocation hard coat resin composition, the peelability and the adhesive layer protruding were poorly evaluated.

Further, in Comparative Example 3, since the content of the polyfunctional thiol compound in the translocated hard coat resin composition was large, the pencil hardness was poor. In Comparative Example 5, the content of the active energy ray-curable resin in the translocation hard coat resin composition was high, resulting in poor adhesion to glass. In Comparative Example 6, the content of the polyfunctional epoxy compound (c) in the translocated hard coat resin composition was small, resulting in poor adhesion to glass. In Comparative Example 9, in the glass-coated synthetic type product using the antireflection film with an adhesive layer instead of the antireflection film for glass transfer of the present invention, distortion due to the adhesive layer occurs, resulting in poor visibility. became.

Claims (2)

An antireflection layer, a transfer hard coat layer, and a release film 2 are laminated in this order on the release film 1.
The transfer hard coat layer is an antireflection film for glass transfer, which is a layer made of a photocured product of a transfer hard coat resin composition (HAD).
The transposed hard coat resin composition (HAD) contains the following components (a) to (c), and the content of the component (a) is 100% by mass as a total of the components (a) to (c). An antireflection film for glass transfer, which comprises 1 to 12% by mass, the content of the component (b) is 15 to 48% by mass, and the content of the component (c) is 48 to 81% by mass.
(A) Polyfunctional thiol compound (b) Active energy ray-curable resin (c) Polyfunctional epoxy compound A glass transfer molded product having a layer of a heat-molded product composed of a release product of the release films 1 and 2 of the antireflection film for glass transfer according to claim 1 on a glass surface.