阅读说明：本技术 硬涂膜及其制造方法、具备硬涂膜的物品及图像显示装置 (Hard coat film, method for producing same, article provided with hard coat film, and image display device ) 是由 福岛悠太 松本彩子 芥川畅之 于 2020-04-03 设计创作，主要内容包括：根据本发明,提供一种硬涂膜、具备硬涂膜的物品及图像显示装置,所述硬涂膜依次具有基材、粘接剂层及硬涂层,基材是含有选自由聚酰亚胺树脂、聚酰胺酰亚胺树脂及芳纶树脂组成的组中的至少一个的薄膜,在粘接剂层与基材之间具有由粘接剂层的成分和基材的成分混合而成的混合层。(According to the present invention, there are provided a hard coat film, an article provided with the hard coat film, and an image display device, the hard coat film comprising a base material, an adhesive layer, and a hard coat layer in this order, the base material being a thin film comprising at least one selected from the group consisting of a polyimide resin, a polyamideimide resin, and an aramid resin, and a mixed layer comprising a mixture of a component of the adhesive layer and a component of the base material being provided between the adhesive layer and the base material.)

1. A hard coat film comprising a base material, an adhesive layer and a hard coat layer in this order,

the base material is a film containing at least one selected from the group consisting of polyimide resins, polyamideimide resins, and aramid resins, and a mixed layer in which the components of the adhesive layer and the components of the base material are mixed is provided between the adhesive layer and the base material.

2. The hard coating film according to claim 1, wherein,

the thickness of the mixed layer is 0.1-10 μm.

3. The hard coating film according to claim 1 or2, wherein,

the hard coat layer has a scratch-resistant layer on the side opposite to the adhesive layer.

4. The hard coating film according to any one of claims 1 to 3,

the hard coat layer contains a cured product of a curable resin having a number average molecular weight of 1500 or more.

5. The hard coating film according to claim 4, wherein,

the curable resin contains a polyorganosilsesquioxane (X) having a polymerizable group.

6. The hard coating film according to any one of claims 1 to 5,

the adhesive layer contains an ultraviolet absorber.

7. An article provided with the hard coat film according to any one of claims 1 to 6.

8. An image display device comprising the hard coat film according to any one of claims 1 to 6.

9. A method for producing a hard coat film, comprising:

a step (1) of applying a hard coat layer-forming composition to a dummy support, drying the composition, and curing the composition to form at least 1 hard coat layer;

a step (2) of laminating a film base material containing at least one selected from the group consisting of polyimide resins, polyamideimide resins, and aramid resins on the side of the hard coat layer opposite to the dummy support by means of an adhesive;

a step (3) of impregnating the film base with a part of the adhesive;

a step (4) of bonding the hard coat layer to the film base material by heating or irradiating with an active energy ray; and

and (5) peeling the dummy support from the hard coat layer.

10. A method for producing a hard coat film, comprising:

a step (1') of applying a hard coat layer-forming composition to a dummy substrate, drying the composition, and curing the dried composition to form at least 1 hard coat layer;

a step (A) of bonding a protective film to the hard coat layer on the side opposite to the dummy support;

a step (B) of peeling the dummy support from the hard coat layer;

a step (2') of laminating a film base material containing at least one selected from the group consisting of polyimide resins, polyamide-imide resins, and aramid resins on the side of the hard coat layer opposite to the protective film with an adhesive;

a step (3') of impregnating the film base with a part of the adhesive; and

and a step (4') of bonding the hard coat layer to the film base material by heating or irradiating with active energy rays.

11. The method for producing a hard coat film according to claim 10, comprising:

and (5') peeling the protective film from the hard coat layer.

Technical Field

The present invention relates to a hard coat film and a method for producing the same, an article provided with the hard coat film, and an image display device.

Background

In image display devices such as Plasma Displays (PDPs), electroluminescent displays (ELDs), fluorescent displays (VFDs), Field Emission Displays (FEDs), and Liquid Crystal Displays (LCDs), it is preferable to provide an optical film (hard coat film) having a hard coat layer on a substrate in order to prevent damage to the display surface.

In recent years, for example, in smart phones and the like, there has been an increasing demand for flexible displays, and along with this, there has been a demand for optical films (flexible hard coat films) that are less likely to break even when repeatedly bent (have excellent resistance to repeated bending).

For example, patent document 1 describes a laminate for a touch panel having repeated bending resistance, which has a resin cured layer on a polyimide film or aramid film substrate.

Further, patent document 2 describes a transparent flexible hard coat film having a hard coat layer obtained by polymerizing a composition comprising a polyorganosiloxane having an alicyclic epoxy group and a reactive diluent.

Prior art documents

Patent document

Patent document 1: japanese patent laid-open publication No. 2017-33033

Patent document 2: japanese patent No. 6476134

Disclosure of Invention

Technical problem to be solved by the invention

As a base material of a flexible hard coat film, a polyimide film, a polyamideimide film, an aramid film, and the like described in patent document 1 have attracted attention because they are excellent in hardness and repeated bending resistance. The present inventors have studied the problems of the above-mentioned base materials, and as a result, they have found that there is a problem of light resistance due to decomposition of aromatic rings in the molecule when ultraviolet light is irradiated. Specifically, there are coloring of the base material by ultraviolet irradiation (light-resistant coloring) and poor adhesion between the base material and the hard coat layer (light-resistant adhesion). As a result of studies, the inventors have found that, particularly with respect to light-resistant adhesion, improvement can be achieved by forming a mixed layer in which the components of the hard coat layer and the base material are mixed between the hard coat layer and the base material.

However, when a mixed layer is formed between the hard coat layer and the substrate, in the coating/drying step of the composition for forming a hard coat layer, the surface of the substrate needs to be swollen or dissolved, and the surface hardness of the substrate may be greatly reduced, or the substrate component may be eluted in the entire hard coat layer to reduce the hardness of the hard coat layer. In particular, it is found that the hardness is remarkably decreased when a cured component having a large molecular weight is used as a material of a hard coat layer expected as a flexible hard coat film exemplified by polyorganosiloxane having an alicyclic epoxy group described in patent document 2.

In view of the above circumstances, an object of the present invention is to provide a hard coat film having high hardness, excellent light-resistant adhesion, and excellent repeated bending resistance, a method for producing the hard coat film, an article provided with the hard coat film, and an image display device.

Means for solving the technical problem

As a result of intensive studies, the present inventors have found that the above problems can be solved by the following methods.

<1>

A hard coat film comprising a base material, an adhesive layer and a hard coat layer in this order, wherein the base material is a film containing at least one selected from the group consisting of polyimide resins, polyamideimide resins and aramid resins, and a mixed layer comprising a mixture of the components of the adhesive layer and the components of the base material is provided between the adhesive layer and the base material.

<2>

The hard coat film according to <1>, wherein the thickness of the mixed layer is 0.1 to 10 μm.

<3>

The hard coat film according to <1> or <2>, which has a scratch resistant layer on a side of the hard coat layer opposite to the adhesive layer.

<4>

The hard coat film according to any one of <1> to <3>, wherein the hard coat layer contains a cured product of a curable resin having a number average molecular weight of 1500 or more.

<5>

The hard coat film according to <4>, wherein the curable resin contains a polyorganosilsesquioxane (X) having a polymerizable group.

<6>

The hard coat film according to any one of <1> to <5>, wherein the adhesive layer contains an ultraviolet absorber.

<7>

An article having the hard coat film described in any one of <1> to <6 >.

<8>

An image display device comprising the hard coat film according to any one of <1> to <6 >.

<9>

A method for producing a hard coat film, comprising:

a step (1) of applying a hard coat layer-forming composition to a dummy support, drying the composition, and curing the composition to form at least 1 hard coat layer;

a step (2) of laminating a film base material containing at least one selected from the group consisting of polyimide resins, polyamideimide resins, and aramid resins on the side of the hard coat layer opposite to the dummy support by means of an adhesive;

a step (3) of impregnating the film base with a part of the adhesive;

a step (4) of bonding the hard coat layer to the film base material by heating or irradiating with an active energy ray; and

and (5) peeling the dummy support from the hard coat layer.

<10>

A method for producing a hard coat film, comprising:

a step (1') of applying a hard coat layer-forming composition to a dummy substrate, drying the composition, and curing the dried composition to form at least 1 hard coat layer;

a step (A) of bonding a protective film to the hard coat layer on the side opposite to the dummy support;

a step (B) of peeling the dummy support from the hard coat layer;

a step (2') of laminating a film base material containing at least one selected from the group consisting of polyimide resins, polyamide-imide resins, and aramid resins on the side of the hard coat layer opposite to the protective film with an adhesive;

a step (3') of impregnating the film base material with a part of the adhesive; and

and (4') bonding the hard coat layer to the film base material by heating or irradiating with an active energy ray.

<11>

The method of producing a hard coat film according to <10>, comprising a step (5') of peeling the protective film from the hard coat layer.

Effects of the invention

According to the present invention, a hard coat film having high hardness, excellent light-resistant adhesion, and excellent repeated bending resistance, a method for producing the hard coat film, an article provided with the hard coat film, and an image display device can be provided.

Drawings

Fig. 1 is a schematic view showing an example of a hard coat film.

Fig. 2 is a schematic view showing an example of a hard coat film.

Fig. 3 is a schematic view showing an example of a method for producing a hard coat film.

Fig. 4 is a schematic view showing an example of a method for producing a hard coat film.

Fig. 5 is a schematic view showing an example of a method for producing a hard coat film.

Fig. 6 is a schematic view showing an example of a method for producing a hard coat film.

Detailed Description

Hereinafter, embodiments for carrying out the present invention will be described in detail, but the present invention is not limited to these embodiments. In the present specification, the expression "(numerical value 1) to" (numerical value 2) "means" (numerical value 1) or more and (numerical value 2) or less "when numerical values indicate physical property values, characteristic values, and the like. In the present specification, the expression "(meth) acrylate" means "at least one of acrylate and methacrylate". The same applies to "(meth) acrylic acid", "(meth) acryloyl", and the like.

[ hard coating film ]

The hard coat film of the present invention is a hard coat film comprising a base material, an adhesive layer and a hard coat layer in this order, wherein the base material is a film comprising at least one selected from the group consisting of polyimide resins, polyamideimide resins and aramid resins, and a mixed layer comprising a mixture of the components of the base material and the components of the adhesive layer is provided between the adhesive layer and the base material.

Fig. 1 and 2 are schematic views (cross-sectional views) showing an example of a hard coat film of the present invention. The hard coat film 10 in fig. 1 includes a base material 1, a mixed layer 2, an adhesive layer 3, and a hard coat layer 4 in this order. The hard coat film 11 in fig. 2 includes a substrate 1, a mixed layer 2, an adhesive layer 3, a hard coat layer 4, and a scratch-resistant layer 5 in this order.

The mechanism of the hard coat film of the present invention that is excellent in light-resistant adhesion, high in hardness, and excellent in repeated bending resistance is not clear, but the present inventors presume as follows.

The hard coat film of the present invention is characterized by having a mixed layer formed by mixing a base material component and an adhesive component between the adhesive layer and the base material. The mixed layer can reduce the content of a base material component which is easily deteriorated by ultraviolet rays compared to a base material alone, and therefore deterioration by ultraviolet rays is less likely to occur. Since deterioration by ultraviolet rays progresses from the surface of the base material to the inside of the base material, it is considered that the hard coat film has good light-resistant adhesion by having a mixed layer having a specific thickness or more on the surface of the base material.

In the present invention, the mixed layer can be controlled by the components of the binder and the bonding process, and the composition/composition ratio and the coating/drying process of the composition for forming a hard coat layer are not limited. Therefore, it is considered that the decrease in hardness occurring when the mixed layer is formed can be prevented, and both the light-resistant adhesion and the hardness can be achieved.

< substrate >)

The base material of the hard coat film of the present invention is a film containing at least one selected from the group consisting of polyimide resins, polyamideimide resins, and aramid resins. The transmittance of the substrate in the visible light region is preferably 70% or more, more preferably 80% or more, and further preferably 90% or more.

The thin film containing the above resin is preferably used as a substrate because the number of breaking and bending times measured by an MIT tester is large and the hardness is relatively high in accordance with JIS (japanese industrial standards) P8115 (2001). For example, aramid fibers as described in example 1 of Japanese patent No. 5699454, and polyimides described in Japanese patent laid-open Nos. 2015-508345, 2016-521216, and WO2017/014287 can be preferably used as the base material.

(thickness of substrate)

The thickness of the substrate is more preferably 100 μm or less, still more preferably 80 μm or less, and most preferably 50 μm or less. When the thickness of the base material is reduced, the difference in curvature between the front surface and the back surface at the time of bending is reduced, cracks are less likely to occur, and the base material is not broken even when the base material is bent many times. On the other hand, the thickness of the substrate is preferably 3 μm or more, more preferably 5 μm or more, and most preferably 15 μm or more, from the viewpoint of easy handling of the substrate.

(method of producing substrate)

The substrate may be formed into a film by heat-melting a thermoplastic polymer, or may be formed into a film by solution casting (solution casting) using a solution in which a polymer is uniformly dissolved. In the case of film formation by heat fusion, the flexible material and various additives can be added during heat fusion. On the other hand, when the base material is produced by the solution film-forming method, the flexible material and various additives can be added to a polymer solution (hereinafter, also referred to as dope) in each production step. The timing of the addition may be arbitrarily added in the dope solution preparation step, but may be performed by adding an additive in the final preparation step of the dope solution preparation step.

To dry and/or bake the coating film, the coating film may be heated. The heating temperature of the coating film is usually 50 to 350 ℃. The heating of the coating film may be performed under an inert atmosphere or under reduced pressure. By heating the coating film, the solvent can be evaporated and removed. The resin film may be formed by a method including a step of drying the coating film at 50 to 150 ℃ and a step of baking the dried coating film at 180 to 350 ℃.

At least one main surface of the substrate may be subjected to a surface treatment.

< adhesive layer >

The adhesive layer is a layer provided for forming a hard coat layer on the surface of the base material and for adhering the hard coat layer to the base material.

As the adhesive constituting the adhesive layer, any appropriate form of adhesive can be used. Specific examples thereof include water-based adhesives, solvent-based adhesives, emulsion-based adhesives, solventless adhesives, active energy ray-curable adhesives, and thermosetting adhesives. Examples of the active energy ray-curable adhesive include an electron ray-curable adhesive, an ultraviolet ray-curable adhesive, and a visible ray-curable adhesive. A water-based adhesive, an active energy ray-curable adhesive, and a thermosetting adhesive can be preferably used. Specific examples of the aqueous adhesive include an isocyanate adhesive, a polyvinyl alcohol adhesive (PVA adhesive), a gelatin adhesive, a vinyl latex, an aqueous polyurethane, and an aqueous polyester. Specific examples of the active energy ray-curable adhesive include (meth) acrylate adhesives. Examples of the curable component in the (meth) acrylate adhesive include a compound having a (meth) acryloyl group and a compound having a vinyl group. Further, as the cationic polymerization curing adhesive, a compound having an epoxy group or an oxetane group can be used. The compound having an epoxy group is not particularly limited as long as it has at least 2 epoxy groups in the molecule, and various known curable epoxy compounds can be used. Examples of the preferable epoxy compound include a compound having at least 2 epoxy groups and at least 1 aromatic ring in a molecule (aromatic epoxy compound), a compound having at least 2 epoxy groups in a molecule and at least 1 of which is formed between adjacent 2 carbon atoms constituting an alicyclic ring (alicyclic epoxy compound), and the like. Specific examples of the thermosetting adhesive include phenol resins, epoxy resins, urethane curable resins, urea resins, melamine resins, acrylic reactive resins, and the like. Specifically, bisphenol F type epoxy compounds are exemplified. The binder is preferably different in composition from the hard coat layer.

In one embodiment, a PVA adhesive may be used as the adhesive constituting the adhesive layer. By using the PVA-based adhesive, even when a material which does not transmit active energy rays is used, the materials can be bonded to each other. In another embodiment, an active energy ray-curable adhesive can be used as the adhesive constituting the adhesive layer. When an active energy ray-curable adhesive is used, a sufficient interlayer peeling force can be obtained even with a material whose surface is hydrophobic and cannot be bonded with a PVA adhesive.

Specific examples of the adhesive include an adhesive containing an epoxy compound not containing an aromatic ring in the molecule and cured by heating or irradiation of an active energy ray as described in jp 2004-24925 a, a (meth) acrylic compound containing at least 2 (meth) acryloyl groups in the molecule and containing 100 parts by mass of the total amount of the (meth) acrylic compound as described in jp 2008-174667 a, (b) a (meth) acrylic compound having a hydroxyl group in the molecule and having only 1 polymerizable double bond, and an active energy ray-curable adhesive containing a phenol ethylene oxide-modified acrylate or a nonylphenol ethylene oxide-modified acrylate.

The storage modulus of elasticity of the adhesive layer is preferably 1.0X 10 in a region of 70 ℃ or less⁶Pa or more, more preferably 1.0X 10⁷Pa or above. The upper limit of the storage modulus of elasticity of the adhesive layer is, for example, 1.0X 10¹⁰Pa。

The thickness of the adhesive layer is preferably 0.01 to 7 μm, and more preferably 0.01 to 5 μm.

The adhesive layer in the present invention is located between the hard coat layer and the base material, and therefore has a large influence on hardness. Therefore, when an adhesive is used instead of the adhesive layer of the present invention, the hardness may be greatly reduced. From the viewpoint of hardness, the adhesive layer is preferably thin and has a high storage modulus.

In the active energy ray-curable adhesive, the selection of the initiator and the photosensitizer is also important, and as a specific example, a (meth) acrylate-based adhesive is described in examples of jp 2018-017996 a, and as a cationic polymerization-curable adhesive, it can be produced by referring to the descriptions of jp 2018-035361 a and jp 2018-041079 a.

The PVA adhesive preferably contains an additive for improving adhesion to a substrate or a hard coat layer. The type of the additive is not particularly limited, and a compound containing boric acid or the like is preferably used.

From the viewpoint of suppressing interference fringes, the difference in refractive index between the adhesive layer and the hard coat layer is preferably 0.05 or less, and more preferably 0.02 or less. The method for adjusting the refractive index of the adhesive layer is not particularly limited, and it is preferable to add hollow particles when the refractive index is to be lowered, and particles such as zirconium when the refractive index is to be raised. As a more specific example, Japanese patent application laid-open No. 2018-017996 discloses a specific example of an adhesive having a refractive index of 1.52-1.64.

From the viewpoint of light-resistant coloring, the adhesive layer preferably contains an ultraviolet absorber. When an ultraviolet absorber is added to the adhesive layer, it is preferably added to a thermosetting adhesive in view of bleeding and suppression of curing.

(ultraviolet absorber)

Examples of the ultraviolet absorber include benzotriazole compounds, triazine compounds, and benzoxazine compounds. The benzotriazole compound is a compound having a benzotriazole ring, and specific examples thereof include various benzotriazole-based ultraviolet absorbers described in paragraph 0033 of Japanese patent laid-open publication No. 2013-111835. The triazine compound is a compound having a triazine ring, and specific examples thereof include various triazine-based ultraviolet absorbers described in jp 2013-111835 a 0033. As the benzoxazine compound, for example, the benzoxazine compound described in paragraph 0031 of japanese patent application laid-open No. 2014-209162 can be used. For example, the content of the ultraviolet absorber in the adhesive layer is about 0.1 to 10 parts by mass with respect to 100 parts by mass of the polymer contained in the adhesive layer, but is not particularly limited. Further, as for the ultraviolet absorber, reference can also be made to paragraph 0032 of Japanese patent laid-open publication No. 2013-111835. In the present invention, an ultraviolet absorber having high heat resistance and low volatility is preferable. Examples of the ultraviolet absorber include UVSORB101 (manufactured by FUJIFILM Wako Pure Chemical Co corporation), TINUVIN 360, TINUVIN 460, TINUVIN 1577 (manufactured by BASF corporation), LA-F70, LA-31, and LA-46 (manufactured by ADEKA corporation).

The binder in the present invention preferably contains a compound having a molecular weight of 500 or less, more preferably 300 or less, from the viewpoint of forming a mixed layer described later. From the same viewpoint, it is preferable that the composition contains a component having an SP value of 21 to 26. In the present invention, the SP value (solubility parameter) is a value calculated by the Hoy method described in polymehrandbookfurthelium.

In addition, from the viewpoint of forming a mixed layer described later, the adhesive in the present invention is preferably high in affinity with the base material. The affinity between the base material and the adhesive can be confirmed by observing the change in the base material when the base material is immersed in the adhesive. The use of an adhesive in which the substrate is cloudy or dissolved when immersed in the adhesive is preferable because a mixed layer to be described later can be efficiently formed.

< Mixed layer >

The hard coat film of the present invention has a mixed layer formed by mixing the components of the adhesive layer and the components of the base material, between the adhesive layer and the base material layer.

The mixed layer is a region where the distribution of the compound (the composition of the adhesive layer and the composition of the base material) gradually changes from the adhesive layer side to the base material layer side between the adhesive layer and the base material. In this case, the adhesive layer refers to a portion that contains a component of the adhesive layer but does not contain a component of the base material, and the base material refers to a portion that contains a component of the base material but does not contain a component of the adhesive layer. When the film is cut with a microtome and the cross section is analyzed by a time-of-flight secondary ion mass spectrometer (TOF-SIMS), the mixed layer can be measured as a portion in which the components of the base material and all or a part of the components contained in the adhesive layer are simultaneously detected, and the film thickness in this region can be measured from the cross section information of the TOF-SIMS as well.

The thickness of the mixed layer is preferably 0.1 to 10.0 μm, more preferably 1.0 to 6.0 μm. The thickness of the mixed layer is preferably set to 0.1 μm or more because an effect of improving the light-resistant adhesion can be obtained, and 1.0 μm or more because the light-resistant adhesion can be improved even when ultraviolet rays are irradiated for a long time. On the other hand, the hardness is improved by making the thickness of the mixed layer 10 μm or less, and the hardness can be further kept favorable by making the thickness of the mixed layer 6.0 μm or less, which is preferable.

< hard coating layer >

The hard coat layer of the hard coat film of the present invention will be explained. The hard coat layer of the present invention is preferably a cured product containing a curing component of the composition for forming a hard coat layer. The curing component of the composition for forming a hard coat layer in the present invention is not particularly limited, but is preferably a curable resin having a number average molecular weight of 1500 or more, and more preferably contains a polyorganosilsesquioxane (X) having a polymerizable group. The number average molecular weight is preferably 1500 or more, because the hardness of the composition for forming a hard coat layer when it is impregnated into the base material without interposing an adhesive layer therebetween is remarkably reduced, and the effect of the present invention is remarkable. Further, the use of the polyorganosilsesquioxane (X) having a polymerizable group is preferable because a hard coating film having excellent hardness and repeated bending resistance can be provided.

The cured product of the polyorganosilsesquioxane (X) having a polymerizable group is preferably a product obtained by curing a curable composition containing the polyorganosilsesquioxane (X) having a polymerizable group by heating and/or irradiation with ionizing radiation.

(polyorganosilsesquioxane (X) having polymerizable group)

The polymerizable group in the polyorganosilsesquioxane (X) having a polymerizable group is not particularly limited, and a polymerizable group capable of radical polymerization or cationic polymerization is preferable. As the radical polymerizable group, a generally known radical polymerizable group can be used, and a preferred group is a (meth) acryloyl group. As the cationically polymerizable group, a known cationically polymerizable group can be used, and specific examples thereof include an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiroorthoester group, and a vinyloxy group. Among them, an alicyclic ether group and an ethyleneoxy group are preferable, an epoxy group, an oxetane group and an ethyleneoxy group are particularly preferable, and an epoxy group is most preferably used.

The polyorganosilsesquioxane having a polymerizable group (also referred to as "polyorganosilsesquioxane (X)") has at least a siloxane structural unit having a polymerizable group, and is preferably a polyorganosilsesquioxane represented by the following general formula (1).

[ chemical formula 1]

In the general formula (1), Rb may include a (meth) acryloyl group, an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiroorthoester group, an ethyleneoxy group, and the like. Among them, preferred are alicyclic ether groups and ethyleneoxy groups, which represent groups containing an epoxy group, an oxetanyl group and an ethyleneoxy group, and Rc represents a 1-valent group. q and r represent the ratio of Rb and Rc in the general formula (1), q + r is 100, q is greater than 0, and r is 0 or more. When a plurality of Rb and Rc exist in the general formula (1), the plurality of Rb and Rc may be the same or different. In the case where a plurality of Rc exist in the general formula (1), the plurality of Rc may form a bond with each other.

[ SiO ] in the general formula (1)_1.5]Represents a structural portion composed of a siloxane bond (Si-O-Si) in the polyorganosilsesquioxane.

The polyorganosilsesquioxane is a network polymer or a polyhedral atom cluster having a siloxane structural unit derived from a hydrolyzable trifunctional silane compound, and can form a random structure, a ladder structure, a cage structure, or the like from siloxane bonds. In bookIn the invention, [ SiO ]_1.5]The structural portion shown may be any of those described above, but preferably contains a large number of trapezoidal structures. By forming the trapezoidal structure, the deformation recovery property of the hard coat film can be favorably maintained. Regarding the formation of the ladder structure, it is possible to determine the FT-IR (Fourier Transform Infrared Spectroscopy) at 1020-1050cm^-1Qualitative confirmation was made by passive self-characterized Si-O-Si stretching absorption in the nearby ladder structures.

In the general formula (1), Rb may include a (meth) acryloyl group, an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiroorthoester group, an ethyleneoxy group, and the like.

Rb in the general formula (1) is derived from a group (a group other than an alkoxy group and a halogen atom; for example, Rb in a hydrolyzable silane compound represented by the following formula (B)) bonded to a silicon atom in a hydrolyzable trifunctional silane compound used as a raw material of a polyorganosilsesquioxane.

In the general formula (1), Rc represents a 1-valent group.

As the 1-valent group represented by Rc, a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group may be mentioned.

Examples of the alkyl group represented by Rc include alkyl groups having 1 to 10 carbon atoms, and examples thereof include straight-chain or branched alkyl groups such as methyl, ethyl, propyl, n-butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, and isopentyl groups.

Examples of the cycloalkyl group represented by Rc include cycloalkyl groups having 3 to 15 carbon atoms, for example, cyclobutyl, cyclopentyl, cyclohexyl, and the like.

Examples of the alkenyl group represented by Rc include alkenyl groups having 2 to 10 carbon atoms, and examples thereof include linear or branched alkenyl groups such as vinyl, allyl, and isopropenyl groups.

Examples of the aryl group represented by Rc include aryl groups having 6 to 15 carbon atoms, and examples thereof include phenyl, tolyl, naphthyl and the like.

Examples of the aralkyl group represented by Rc include aralkyl groups having 7 to 20 carbon atoms, and examples thereof include benzyl groups, phenethyl groups, and the like.

Examples of the substituted alkyl group, substituted cycloalkyl group, substituted alkenyl group, substituted aryl group, and substituted aralkyl group include those in which a hydrogen atom or a part or all of the main chain skeleton of each of the alkyl group, cycloalkyl group, alkenyl group, aryl group, and aralkyl group is substituted with at least 1 member selected from the group consisting of an ether group, an ester group, a carbonyl group, a halogen atom (fluorine atom, etc.), an acryloyl group, a methacryloyl group, a mercapto group, and a hydroxyl group (hydroxyl group), and the like.

Rc is preferably a substituted or unsubstituted alkyl group, and more preferably an unsubstituted alkyl group having 1 to 10 carbon atoms.

In the case where a plurality of Rc exist in the general formula (1), the plurality of Rc may form a bond with each other. Preferably 2 or 3 Rc form bonds with each other, more preferably 2 Rc form bonds with each other.

As a group formed by bonding 2 Rc to each other (Rc)₂) The alkylene group is preferably one in which a substituted or unsubstituted alkyl group represented by Rc is bonded.

As Rc₂Examples of the alkylene group include a linear or branched alkylene group such as a methylene group, an ethylene group, a propylene group, an isopropylene group, an n-butylene group, an isobutylene group, a sec-butylene group, a tert-butylene group, an n-pentylene group, an isopentylene group, a sec-pentylene group, a tert-pentylene group, an n-hexylene group, an isohexylene group, a sec-hexylene group, a tert-hexylene group, an n-heptylene group, an isoheptylene group, a sec-heptylene group, a tert-heptylene group, an n-octylene group, an isooctylene group, a sec-octylene group, and a tert-octylene group.

As Rc₂The alkylene group is preferably an unsubstituted alkylene group having 2 to 20 carbon atoms, more preferably an unsubstituted alkylene group having 2 to 20 carbon atoms, still more preferably an unsubstituted alkylene group having 2 to 8 carbon atoms, and particularly preferably an n-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group, or an n-octylene group.

A group formed by bonding 3 Rc to each other: (Rc₃) Preferably in the above Rc₂The alkylene group is a 3-valent group in which any hydrogen atom in the alkylene group is reduced.

The Rc in the general formula (1) is derived from a group (a group other than an alkoxy group and a halogen atom; for example, Rc in hydrolyzable silane compounds represented by the following formulas (C1) to (C3) bonded to a silicon atom in hydrolyzable silane compounds used as raw materials of polyorganosilsesquioxane₁～Rc₃Etc.).

In the general formula (1), q is greater than 0 and r is 0 or greater.

Preferably, q/(q + r) is 0.5 to 1.0. By setting the total amount of the group represented by Rb to the total amount of the groups represented by Rb or Rc contained in the polyorganosilsesquioxane (X) to be at least half, a network made of an organic crosslinking group is sufficiently formed, and thus various performances such as hardness and repeated bending resistance can be satisfactorily maintained.

q/(q + r) is more preferably 0.7 to 1.0, still more preferably 0.9 to 1.0, and particularly preferably 0.95 to 1.0.

In the general formula (1), it is also preferable that a plurality of Rc exist and form a bond with each other. In this case, r/(q + r) is preferably 0.005 to 0.20.

r/(q + r) is more preferably 0.005 to 0.10, still more preferably 0.005 to 0.05, and particularly preferably 0.005 to 0.025.

The number average molecular weight (Mn) of the polyorganosilsesquioxane (X) in terms of standard polystyrene by Gel Permeation Chromatography (GPC) is preferably 1500 to 80000, more preferably 2000 to 50000.

The molecular weight dispersity (Mw/Mn) of the polyorganosilsesquioxane (X) in terms of standard polystyrene based on GPC is, for example, 1.0 to 20.0, preferably 1.0 to 10.0.

The number average molecular weight, weight average molecular weight, and molecular weight dispersion degree of the polyorganosilsesquioxane (X) were measured by the following apparatus and conditions.

A measuring device: trade name "LC-20 AD" (manufactured by SHIMADZU CORPORATION)

Column: shodex KF-801X 2, KF-802 and KF-803 (manufactured by SHOWA DENKO K.K.)

Measuring temperature: 40 deg.C

Eluent: tetrahydrofuran (THF), sample concentration 0.1-0.2 mass%

Flow rate: 1 mL/min

A detector: UV-VIS detector (trade name "SPD-20A", manufactured by SHIMADZU CORPORATION N)

Molecular weight: conversion to standard polystyrene

< method for producing polyorganosiloxane (X) >

The polyorganosilsesquioxane (X) can be produced by a known production method, and is not particularly limited, and can be produced by a method of hydrolyzing and condensing 1 or2 or more kinds of hydrolyzable silane compounds. As the hydrolyzable silane compound, a hydrolyzable trifunctional silane compound (a compound represented by the following formula (B)) for forming an epoxy group-containing siloxane structural unit is preferably used as the hydrolyzable silane compound.

When r in the general formula (1) is greater than 0, it is preferable to use a compound represented by the following formula (C1), (C2) or (C3) together as the hydrolyzable silane compound.

[ chemical formula 2]

Rb-Si(X²)₃ (B)

Rb in the formula (B) has the same meaning as Rb in the above general formula (1), and preferable examples thereof are also the same.

X in the formula (B)²Represents an alkoxy group or a halogen atom.

As X²Examples of the alkoxy group in (3) include alkoxy groups having 1 to 4 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy and isobutoxy groups.

As X²Examples of the halogen atom in (b) include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

As X²Alkoxy is preferred, and methoxy and ethoxy are more preferred. In addition, 3X²The same or different.

The compound represented by the above formula (B) is a compound forming a siloxane structural unit having Rb.

[ chemical formula 3]

Rc₁-Si(X³)₃ (C1)

[ chemical formula 4]

(X³)₃Si-Rc₂-Si(X³)₃ (C2)

[ chemical formula 5]

Rc in formula (C1)₁The meaning of (2) is the same as that of Rc in the above general formula (1), and the preferable examples are also the same.

Rc in formula (C2)₂And a group (Rc) formed by bonding 2 Rc's in the above formula (1) to each other₂) The same applies to the preferred examples.

Rc in formula (C3)₃And a group (Rc) formed by bonding 3 Rc's in the above general formula (1) to each other₃) The same applies to the preferred examples.

X in the above formulae (C1) to (C3)³Has the same meaning as X in the above formula (B)²The same applies to the preferred examples. Multiple X³The same or different.

As the hydrolyzable silane compound, hydrolyzable silane compounds other than the compounds represented by the formulae (B), (C1) to (C3) may be used together. Examples thereof include hydrolyzable trifunctional silane compounds, hydrolyzable monofunctional silane compounds, and hydrolyzable difunctional silane compounds other than the compounds represented by the above formulas (B), (C1) to (C3).

Rc is derived from Rc in the hydrolyzable silane compounds represented by the formulas (C1) to (C3)₁～Rc₃In the case of (2), the mixing ratio (molar ratio) of the compounds represented by the above formulae (B), (C1) to (C3) may be adjusted so as to adjust q/(q + r) in the general formula (1).

Specifically, for example, the compound can be produced by a method in which q/(q + r) is 0.5 to 1.0, the value represented by (Z2) below is 0.5 to 1.0, and these compounds are hydrolyzed and condensed.

(Z2) ═ compound (molar amount) represented by formula (B)/{ compound (molar amount) represented by formula (B) + compound (molar amount) represented by formula (C1) + compound (molar amount) x 2 represented by formula (C2) + compound (molar amount) x 3 represented by formula (C3) }

The amount and composition of the hydrolyzable silane compound can be appropriately adjusted according to the structure of the desired polyorganosilsesquioxane (X).

The hydrolysis and condensation reaction of the hydrolyzable silane compound may be performed simultaneously or sequentially. When the above reaction is carried out successively, the order of carrying out the reaction is not particularly limited.

In the hard coat layer of the hard coat film of the present invention, the condensation rate of the polyorganosilsesquioxane (X) is preferably 80% or more from the viewpoint of the hardness of the film. The condensation rate is more preferably 90% or more, and still more preferably 95% or more.

The condensation rate can be determined by subjecting a hard coating film sample having a hard coating layer comprising a cured product of a polyorganosilsesquioxane (X)²⁹Si NMR (nuclear magnetic resonance) spectrometry and calculation using the measurement result.

The cured product of the polyorganosilsesquioxane (X) is preferably polymerized by the polymerizable group.

The reaction rate of the above polymerization reaction can be calculated as follows: FT-IR (Fourier Transform Infrared Spectroscopy) single Reflection ATR (Attenuated Total Reflection) measurements were carried out on samples before and after complete curing and heat treatment of the composition for forming a hard coat layer containing the polyorganosiloxane (X), and calculated from the change in the height of the peak derived from the polymerizable group.

The polyorganosilsesquioxane (X) may be used alone or in combination of two or more different structures.

The content of the cured product of the polyorganosilsesquioxane (X) is preferably 50% by mass or more and 100% by mass or less, more preferably 70% by mass or more and 100% by mass or less, and still more preferably 80% by mass or more and 100% by mass or less, based on the total mass of the hard coat layer.

(other additives)

The hard coat layer may contain components other than those described above, and may contain, for example, a dispersant, a leveling agent, an antifouling agent, an antistatic agent, an ultraviolet absorber, and the like.

(film thickness)

The film thickness of the hard coat layer is not particularly limited, but is preferably 1 to 100 μm, more preferably 1 to 50 μm, and still more preferably 3 to 20 μm.

The thickness of the hard coat layer was calculated by observing the cross section of the hard coat film with an optical microscope. The cross-sectional sample can be produced by a slicing method using a microtome, a cross-sectional processing method using a Focused Ion Beam (FIB) apparatus, or the like.

< other layer >

The hard coat film of the present invention may have other layers in addition to the hard coat layer. For example, a hard coat layer may be provided with a low refractive index layer for imparting antireflection properties and a scratch resistant layer for imparting scratch resistance, and a plurality of these layers may be provided.

The hard coat film of the present invention preferably has a scratch resistant layer on the surface of the hard coat layer opposite to the substrate, whereby scratch resistance can be further improved.

(scratch-resistant layer)

The scratch-resistant layer is preferably a cured product containing a compound having 2 or more (meth) acryloyl groups in 1 molecule (also referred to as "polyfunctional (meth) acrylate compound").

The polyfunctional (meth) acrylate compound is preferably a compound having 3 or more (meth) acryloyl groups in 1 molecule.

The polyfunctional (meth) acrylate compound may be a crosslinkable monomer, a crosslinkable oligomer, or a crosslinkable polymer.

Examples of the polyfunctional (meth) acrylate compound include esters of a polyol and (meth) acrylic acid. Specific examples thereof include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, bis-trimethylolpropane tetra (meth) acrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexane acrylate, pentaerythritol hexane (meth) acrylate, and the like, but pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and mixtures thereof are preferable from the viewpoint of high crosslinking.

The polyfunctional (meth) acrylate compound may be used alone or in combination of two or more different structures.

The content of the cured product of the polyfunctional (meth) acrylate compound is preferably 80% by mass or more, more preferably 85% by mass or more, and still more preferably 90% by mass or more, based on the total mass of the scratch-resistant layer.

(other additives)

The scratch-resistant layer may contain components other than those described above, and may contain, for example, inorganic particles, a leveling agent, an antifouling agent, an antistatic agent, an interlayer sealing agent, a lubricant, and the like. The interlayer sealing agent is a component for bonding the hard coat layer and the scratch-resistant layer when the scratch-resistant layer and the hard coat layer are laminated. The interlayer adhesive preferably contains a crosslinking group of the curing components of both the hard coat layer and the scratch-resistant layer. The lubricant preferably contains the following fluorine-containing compound.

(fluorine-containing Compound)

The fluorine-containing compound may be any of a monomer, an oligomer, and a polymer. The fluorine-containing compound preferably has a substituent that contributes to formation of a bond or compatibility with the polyfunctional (meth) acrylate compound in the scratch-resistant layer. The substituents may be the same or different, and preferably a plurality of such substituents are present.

The substituent is preferably a polymerizable group, and may be a polymerizable reactive group showing any of radical polymerizability, cationic polymerizability, anionic polymerizability, condensation polymerizability, and addition polymerizability, and examples of the preferable substituent include an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, a cinnamoyl group, an epoxy group, an oxetanyl group, a hydroxyl group, a polyoxyalkylene group, a carboxyl group, and an amino group. Among them, radical polymerizable groups are preferable, and among them, acryloyl and methacryloyl are particularly preferable.

The fluorine-containing compound may be a polymer or an oligomer of a compound containing no fluorine atom.

Examples of preferred fluorine-containing compounds include, but are not limited to, R-2020, M-2020, R-3833 and M-3833 manufactured by DAIKIN INDUSTRIES, LTD, OPTOOL DAC (trade name), MEGAFACE F-171, F-172, F-179A, RS-78, RS-90, DEFENSA MCF-300 and MCF-323 (trade name), manufactured by DIC Corporation.

(amount of fluorine-containing Compound added)

The amount of the fluorine-containing compound added is preferably 0.01 to 5% by mass, more preferably 0.1 to 5% by mass, even more preferably 0.5 to 5% by mass, and particularly preferably 0.5 to 2% by mass, based on the total mass of the scratch-resistant layer.

The thickness of the scratch-resistant layer is preferably 0.1 to 4 μm, more preferably 0.1 to 2 μm, and particularly preferably 0.1 to 1 μm.

The present invention also relates to an article having the hard coat film of the present invention and an image display device having the hard coat film of the present invention. The hard coat film of the present invention is particularly preferably applied to a flexible display in a smart phone or the like.

< method for producing hard coating film >

The method for producing the hard coat film of the present invention is not particularly limited, and one of preferable embodiments includes a method (embodiment a) in which after at least 1 hard coat layer is formed on a dummy support, the hard coat layer is transferred from the dummy support to a base material via an adhesive layer. Another preferred embodiment is a method (embodiment B) in which after at least 1 hard coat layer is formed on a dummy support, the hard coat layer is transferred from the dummy support to a protective film, and then the hard coat layer is transferred from the protective film to a base material via an adhesive layer.

The above-described mode a will be described in detail below. Specifically, the embodiment a is a production method including the following steps (1) to (5).

Step (1): a step of applying a composition for forming a hard coat layer on a dummy support, drying the composition, and curing the dried composition to form at least 1 hard coat layer

Step (2): laminating a film base material containing at least one selected from the group consisting of polyimide resins, polyamideimide resins and aramid resins on the side of the hard coat layer opposite to the dummy support by means of an adhesive

Step (3): a step of allowing a part of the adhesive to penetrate into the base material

Step (4): a step (5) of bonding the hard coat layer to the base material by heating or irradiation with active energy rays: a step of peeling the dummy support from the hard coat layer

Fig. 3 and 4 are schematic diagrams for explaining the method for producing a hard coat film according to embodiment a.

In fig. 3, (a) shows a state where the hard coat layer 4 is formed on the dummy support 6 by performing the step (1). (B) The above-described step (2) is performed, and the base material 1 is laminated on the side of the hard coat layer 4 opposite to the dummy support 6 via the adhesive layer 3. (C) The step (3) is performed to form the mixed layer 2 by allowing a part of the adhesive to penetrate into the base material 1. (D) As an example of the step (4), a state in which ultraviolet rays (UV) are irradiated from the dummy support 6 side is shown. (E) The step (5) is performed to peel off the dummy substrate 6 to obtain the hard coat film 10.

Fig. 4 is a view schematically showing a method for producing the hard coating film 11 having the abrasion resistant layer in the embodiment a, and is the same as fig. 3 except that the abrasion resistant layer 5 is added.

< step (1) >

The step (1) is a step of applying a composition for forming a hard coat layer on a dummy support, drying the composition, and curing the composition to form at least 1 hard coat layer.

(pseudo support)

The dummy support is not particularly limited as long as it has a smooth surface. The dummy support has surface flatness with a surface roughness of 30nm or less, and it is preferable that the dummy support does not interfere with the application of the hard coat layer forming composition, and dummy supports formed of various materials can be used, but for example, a polyethylene terephthalate (PET) film, a cycloolefin resin film, a triacetyl cellulose (TAC) film, or the like can be preferably used.

In the present invention, SPA-400 (manufactured by Hitachi High-Tech Science Corporation) was used in a measurement range of 5. mu. m.times.5. mu.m, measurement mode: DFM, measurement frequency: the surface roughness was measured under the measurement condition of 2 Hz.

(composition for Forming hard coat layer)

The composition for forming a hard coat layer is a composition for forming the hard coat layer.

The hard coat layer-forming composition is usually in a liquid form. The composition for forming a hard coat layer is preferably prepared by dissolving or dispersing the curable resin, and if necessary, various additives and a polymerization initiator in an appropriate solvent. In this case, the concentration of the solid content is usually about 10 to 90 mass%, preferably about 20to 80 mass%, and particularly preferably about 40 to 70 mass%.

(polymerization initiator)

The curable resin preferably contains a cationic photopolymerization initiator or a radical photopolymerization initiator depending on the type of polymerizable group contained. In addition, only one initiator may be used, or two or more initiators having different structures may be used simultaneously.

(cationic photopolymerization initiator)

As the cationic photopolymerization initiator, any known cationic photopolymerization initiator can be used without any limitation as long as it can generate cations as active species by light irradiation. Specific examples thereof include known sulfonium salts, ammonium salts, iodonium salts (for example, diaryliodonium salts), triarylsulfonium salts, diazonium salts, and iminium salts. More specifically, examples thereof include cationic photopolymerization initiators represented by the formulae (25) to (28) shown in Japanese patent application laid-open Nos. H8-143806 and 0053, and cationic polymerization catalysts exemplified in Japanese patent application laid-open No. H8-283320 and 0020. The cationic photopolymerization initiator can be synthesized by a known method, and can also be obtained as a commercially available product. Examples of commercially available products include NIPPON SODA CO., LTD products CI-1370, CI-2064, CI-2397, CI-2624, CI-2639, CI-2734, CI-2758, CI-2823, CI-2855, and CI-5102; PHOTOOINIATOR 2047 manufactured by Rhodia, Inc.; UVI-6974 and UVI-6990 manufactured by Union Carbide Corporation; San-Apro Ltd, manufactured as CPI-10P, and the like.

The cationic photopolymerization initiator is preferably a diazonium salt, an iodonium salt, a sulfonium salt or an iminium salt, in view of sensitivity of the photopolymerization initiator to light, stability of the compound, and the like. Further, from the viewpoint of light resistance, an iodide salt is most preferable.

Specific commercially available products of iodonium-based cationic photopolymerization initiators include B2380 manufactured by Tokyo Chemical Co., Ltd, Midori Kagaku Co., Ltd, BBI-102 manufactured by Ltd, WakoPure Chemical industries, WPI-113 manufactured by Ltd, WakoPure Chemical industries, WPI-124 manufactured by Ltd, WakoPure Chemical industries, WPI-169 manufactured by Ltd, WakoPure Chemical industries, WPI-170 manufactured by Ltd, Toyo Gosei Co., Ltd, and DTBPI-PFBS manufactured by Ltd.

Further, as specific examples of the iodine salt compound which can be used as the cationic photopolymerization initiator, the following compounds FK-1 and FK-2 can be mentioned.

[ chemical formula 6]

[ chemical formula 7]

The content of the polymerization initiator in the composition for forming a hard coat layer is not particularly limited as long as it is appropriately adjusted within a range in which the polymerization reaction (cationic polymerization) of the curable resin is favorably progressed. The amount of the curing resin is, for example, in the range of 0.1 to 200 parts by mass, preferably 1 to 20 parts by mass, and more preferably 1 to 5 parts by mass, based on 100 parts by mass of the curing resin. (radical photopolymerization initiator)

As the radical photopolymerization initiator, any known radical photopolymerization initiator can be used without any limitation as long as it can generate radicals as active species by light irradiation. Specific examples thereof include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-2-morpholinyl (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] propanone oligomer, and 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl ] -1-one Acetophenone such as phenyl } -2-methyl-propan-1-one; oxime esters such as 1, 2-octanedione, 1- [4- (phenylthio) -, 2- (O-benzoyloxime) ], ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -, 1- (0-acetyloxime) and the like; benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenones such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4 ' -methyl-diphenylsulfide, 3 ', 4, 4 ' -tetrakis (t-butylperoxycarbonyl) benzophenone, 2, 4, 6-trimethylbenzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl ] phenylmethanesulfonium bromide, and (4-benzoylbenzyl) trimethylammonium chloride; thioxanthones such as 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and 2- (3-dimethylamino-2-hydroxy) -3, 4-dimethyl-9H-thioxanthone-9-one methochloride; acylphosphine oxides such as 2, 4, 6-trimethylbenzoyl-diphenylphosphine oxide, bis (2, 6-dimethoxybenzoyl) -2, 4, 4-trimethyl-pentylphosphine oxide, and bis (2, 4, 6-trimethylbenzoyl) -phenylphosphine oxide; and the like. Further, as an auxiliary agent for the radical photopolymerization initiator, triethanolamine, triisopropanolamine, 4 ' -dimethylaminobenzophenone (Michler's ketone), 4 ' -diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, ethyl 4-dimethylaminobenzoate, ethyl (n-butoxy) 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2, 4-diethylthioxanthone, 2, 4-diisopropylthioxanthone, and the like can be used in combination.

The radical photopolymerization initiator and the auxiliary can be synthesized by a known method or can be commercially available.

The content of the radical photopolymerization initiator in the composition for forming a mixed layer is not particularly limited, and may be appropriately adjusted within a range in which the polymerization reaction (radical polymerization) of the radical polymerizable compound is favorably carried out. The amount of the curing resin is, for example, in the range of 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass, and more preferably 1 to 10 parts by mass, based on 100 parts by mass of the curing resin.

(optional Components)

The composition for forming a hard coat layer may contain one or more optional components in addition to the curable resin and the polymerization initiator. Specific examples of the optional component include a solvent and various additives.

(solvent)

The solvent that can be contained as an arbitrary component is preferably an organic solvent, and one or two or more organic solvents can be mixed and used at an arbitrary ratio. Specific examples of the organic solvent include alcohols such as methanol, ethanol, propanol, n-butanol, and isobutanol; ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone, and cyclohexanone; cellosolves such as ethyl cellosolve; aromatic compounds such as toluene and xylene; glycol ethers such as propylene glycol monomethyl ether; acetates such as methyl acetate, ethyl acetate, and butyl acetate; diacetone alcohol, and the like. The amount of the solvent in the composition can be appropriately adjusted within a range in which the coating suitability of the composition can be ensured. For example, the amount of the polyorganosiloxane (a1) and the polymerization initiator can be 50 to 500 parts by mass, and preferably 80 to 200 parts by mass, based on 100 parts by mass of the total amount of the polyorganosiloxane and the polymerization initiator.

(additives)

The composition may optionally contain one or more known additives as needed. Examples of such additives include a dispersant, a leveling agent, an antifouling agent, an antistatic agent, and an ultraviolet absorber. For details of these, for example, refer to paragraphs 0032 to 0034 of Japanese patent application laid-open No. 2012 and 229412. However, it is not limited to these, and various additives generally used for polymerizable compositions can be used. The amount of the additive to be added to the composition may be appropriately adjusted, and is not particularly limited.

< method for producing composition >

The composition for forming a hard coat layer used in the present invention can be prepared by mixing the above-described respective components simultaneously or sequentially in any order. The preparation method is not particularly limited, and a known stirrer or the like can be used for the preparation.

The method of applying the composition for forming a hard coat layer is not particularly limited, and a known method can be used. Examples thereof include a dip coating method, an air knife coating method, a curtain coating method, a roll coating method, a bar coating method, a gravure coating method, and a die coating method. (curing of hard coat layer)

The kind of the ionizing radiation used in curing the hard coat layer is not particularly limited, and X-rays, electron beams, ultraviolet rays, visible light, infrared rays, and the like can be mentioned, but ultraviolet rays can be preferably used. As the irradiation amount of the ionizing radiation, for example, when the coating film is ultraviolet-curable, it is preferable to irradiate it with an ultraviolet lamp at 10mJ/cm²～6000mJ/cm²The curable compound is cured by the ultraviolet ray of (3). More preferably 50mJ/cm²～6000mJ/cm²More preferably 100mJ/cm²～6000mJ/cm². In order to accelerate curing of the coating film, it is preferable to combine heating during irradiation with ionizing radiation. The heating temperature is preferably 40 ℃ to 140 ℃, and more preferably 60 ℃ to 140 ℃. Further, it is also preferable to irradiate ionizing radiation a plurality of times.

The oxygen concentration during curing is preferably 0to 1.0 vol%, more preferably 0to 0.1 vol%, and most preferably 0to 0.05 vol%. When the oxygen concentration during curing is less than 1.0 vol%, the film is less susceptible to inhibition of curing by oxygen, and thus a strong film is obtained.

The specific structure when the hard coat film contains two or more hard coat layers or contains the other layers other than the hard coat layer is not particularly limited, but a layer directly coated on the dummy support (i.e., a layer to be the outermost surface of the hard coat film) is preferable because the scratch resistance is good in a structure of a scratch resistant layer. When the hard coat film contains two or more hard coat layers or contains the other layers in addition to the hard coat layer, it is preferable to design each layer so that the adhesion between the layers becomes good. Specifically, there may be mentioned a method of using a reactive group of the curable resin of the adjacent layers as a reactive group capable of bonding to each other, a method of using the above interlayer-sealing agent, and the like. From the same viewpoint, it is preferable that the layers formed first are cured by semi-curing and then stacked.

As the conditions for semi-curing, for example, when the coating film is ultraviolet-curable, it is preferable to irradiate it with an ultraviolet lamp at 2mJ/cm²～1000mJ/cm²The curable compound is cured by the ultraviolet ray of (3). More preferably 2mJ/cm²～100mJ/cm²More preferably 5mJ/cm²～50mJ/cm². As the kind of the ultraviolet lamp, a metal halide lamp, a high-pressure mercury lamp, or the like can be preferably used.

The oxygen concentration during curing is not particularly limited, and when a component (a compound having a (meth) acryloyl group) which is easily inhibited from curing is contained, the oxygen concentration is preferably adjusted to 0.1 to 2.0 vol%, since a semi-cured state with residual surface functions can be formed.

When the hard coat film contains two or more hard coat layers or contains the other layers in addition to the hard coat layer, it is preferable to further include a step of accelerating the curing of all the layers during or after curing the hard coat layer directly in contact with the adhesive layer. By accelerating the curing of all layers, the hardness can be improved. The method of accelerating the curing is the same method as the curing of the hard coat layer described above.

< step (2) >

The step (2) is a step of laminating a film base material containing at least one of a polyimide resin, a polyamideimide resin, or an aramid resin on the side of the hard coat layer opposite to the dummy support by an adhesive.

The adhesive layer used is as described above. The method for providing the adhesive layer is not particularly limited, and for example, a method of providing an adhesive layer having a uniform thickness by injecting an adhesive between the base film and the side of the hard coat layer opposite to the dummy support, a method of uniformly applying an adhesive on the side of the hard coat layer opposite to the dummy support or the base film, and bonding the adhesive to another film, or the like can be used.

(surface treatment)

Before the step (2), it is preferable to perform a surface treatment on the side of the hard coat layer opposite to the dummy support or the surface of the base material as necessary.

Examples of the surface treatment at this time include a method of modifying the surface of the film by corona discharge treatment, glow discharge treatment, ultraviolet irradiation treatment, flame treatment, ozone treatment, acid treatment, alkali treatment, and the like. Reference herein to glow discharge treatment is at 10^-3Low-temperature plasma generated under a low-pressure gas of about 20Torr is preferable, and plasma treatment under atmospheric pressure is also preferable. The plasma-excited gas is a gas in which plasma excitation occurs under the above-described conditions, and examples thereof include fluorocarbon compounds such as argon, helium, neon, krypton, xenon, nitrogen, carbon dioxide, and carbon tetrafluoride, and mixtures thereof. Details of these are described in detail on pages 30 to 32 of the invention Association public bulletin technique No. 2001-. Among these treatments, plasma treatment and corona discharge treatment are preferable.

(plasma treatment)

As the plasma treatment, there are treatments by vacuum glow discharge, atmospheric pressure glow discharge, and the like, and as other methods, there are methods such as frame plasma treatment. For example, the methods described in Japanese patent application laid-open Nos. 6-123062, 11-293011, and 11-5857 can be used.

(Corona discharge treatment)

The corona discharge treatment can be carried out by any conventionally known method, for example, methods disclosed in Japanese patent publication No. 48-5043, Japanese patent publication No. 47-51905, Japanese patent publication No. 47-28067, Japanese patent publication No. 49-83767, Japanese patent publication No. 51-41770, Japanese patent publication No. 51-131576, and Japanese patent publication No. 2001-272503.

< step (3) >

The step (3) is a step of allowing a part of the adhesive to penetrate into the base material. By penetrating a part of the adhesive layer into the base material, the hard coat film can be made to have good light-resistant adhesion. The ease of penetration of the adhesive in step (3) varies depending on the type of the substrate used, and can be appropriately adjusted depending on the composition and process of the adhesive. Examples of the method of adjusting the mixed layer by the process include the temperature and time in the step (3). The longer the time of step (3), the higher the temperature, the more the penetration of the adhesive into the substrate can be promoted. The temperature and time of the step (3) are not particularly limited, and examples of the temperature include 30 to 200 ℃ (preferably 40 to 150 ℃). The time is 30 seconds to 5 minutes (preferably 1 minute to 4 minutes).

< step (4) >

The step (4) is a step of bonding the hard coat layer to the base material by heating or irradiation with active energy rays.

The method for bonding the hard coat layer and the base material is not particularly limited, and can be appropriately changed depending on the composition of the adhesive layer used. For example, the polyvinyl alcohol-based adhesive may be removed by heating a solvent (water, alcohol, or the like), the active energy ray-curable adhesive may be irradiated with an active energy ray, and the thermosetting adhesive may be thermally cured by heating. The type of the active energy ray is not particularly limited, and X-rays, electron beams, ultraviolet rays, visible light, infrared rays, and the like can be given, and ultraviolet rays can be preferably used. The surface to which the active energy ray is irradiated in the step (4) is not particularly specified, and can be determined according to the transmittance of the active energy ray used for each member. The curing conditions for the ultraviolet curing are the same as those for the hard coat layer described above.

In addition, both heating and irradiation with active energy rays may be performed in step (4).

< step (5) >

The step (5) is a step of peeling the dummy support from the hard coat layer.

The laminate obtained in step (4) was cut into a width of 25mm, the substrate side of the laminate was fixed to a glass substrate with an adhesive, and the peeling force at the time of peeling at a speed of 300mm/min in the 90 ° direction was measured, whereby the peeling force at the time of peeling the above-mentioned dummy support from the hard coat layer in step (5) could be quantified. The peel force measured by the above method is preferably 0.1N/25mm to 10.0N/25mm, more preferably 0.2N/25mm to 8.0N/25 mm. A peel force of 0.1N/25mm or more is preferred because the hard coat layer is less likely to peel off from the dummy support in a step other than step (5). On the other hand, a peel force of 10.0N/25mm or less is preferable because a part of the hard coat layer is less likely to remain on the dummy support or the adhesive layer is less likely to peel in step (5). The peeling force between the dummy support and the hard coat layer varies depending on the type of the dummy support and the hard coat layer used, and therefore can be appropriately adjusted. Examples of the method of adjustment include a method of using a dummy support subjected to a release treatment, a method of adding a compound for promoting peeling to a composition for forming a hard coat layer, and the like. Specific examples of the compound for promoting exfoliation include a compound having a long-chain alkyl group, a fluorine-containing compound, a silicone-containing compound, and the like.

(surface treatment)

After the step (5), the surface of the hard coat layer on the side opposite to the substrate may be subjected to surface treatment. The type of surface treatment is not particularly limited, and examples thereof include treatments for imparting stain resistance, fingerprint resistance, and slidability.

In the above aspect a, since the pseudo support is present in the portion to be the outermost surface of the hard coat layer when the hard coat layer is formed, the fluorine-containing compound and the leveling agent may not be present in a sufficiently concentrated manner on the outermost surface. In this case, it is preferable to perform the above treatment because the water repellency and scratch resistance required for the hard coat surface can be imparted.

Hereinafter, the above-described mode B will be described in detail. Specifically, the mode B is a production method including the following steps (1 '), (a) to (B), (2 ') to (5 ').

Step (1'): a step of applying a composition for forming a hard coat layer on a dummy support, drying the composition, and curing the dried composition to form at least 1 hard coat layer

Step (A): bonding a protective film to the hard coat layer on the side opposite to the dummy support

A step (B): step of peeling off the dummy support from the hard coat layer

Step (2'): laminating a film base material containing at least one selected from the group consisting of polyimide resins, polyamideimide resins and aramid resins on the side of the hard coat layer opposite to the protective film with an adhesive

Step (3'): a step of penetrating a part of the adhesive layer into the base material

Step (4'): bonding the hard coat layer to the film substrate by heating or irradiating with active energy rays

Step (5'): a step of peeling the protective film from the hard coat layer

Fig. 5 and 6 are schematic diagrams for explaining the method for producing a hard coat film according to embodiment B.

In fig. 5, (a) shows a state where the hard coat layer 4 is formed on the dummy substrate 6 by performing the step (1'). (b) The process (a) is performed, and the protective film 9 is bonded to the hard coat layer 4 on the side opposite to the dummy support 6. The protective film 9 includes an adhesive layer 7 and a support 8 for the protective film. (c) The step (B) is shown in a state where the dummy support 6 is peeled off from the hard coat layer 4. (d) The step (2') is performed in a state where a film base material 1 containing at least one selected from the group consisting of polyimide resins, polyamide-imide resins, and aramid resins is laminated on the side of the hard coat layer 4 opposite to the protective film 9 with an adhesive layer 3 interposed therebetween. (e) The step (3') is shown in which a part of the adhesive layer 3 is caused to penetrate into the base material 1 to form the mixed layer 2. (f) As an example of the step (4'), a state in which Ultraviolet (UV) rays are irradiated from the protective film 9 side is shown. (g) The step (5') is performed to peel off the protective film 9 from the hard coat layer 4 to obtain a hard coat film 10.

Fig. 6 is a view schematically showing a method for producing embodiment B of hard coat film 11 having a scratch resistant layer, and is the same as in fig. 5 except that scratch resistant layer 5 is added.

< step (1') >)

The step (1') is the same as the step (1) of the embodiment a. In the step (1 '), as in the step (1), a specific structure is not particularly limited when the hard coating film includes two or more hard coating layers or includes the other layers other than the hard coating layer, and a structure in which the layer laminated last in the step (1') is a scratch resistant layer is preferable from the viewpoint of scratch resistance.

< Process (A) >

The step (a) is a step of bonding a protective film to the hard coat layer on the side opposite to the dummy support. Here, the protective film means a laminate composed of a support and an adhesive layer, and the adhesive layer side of the protective film is preferably bonded to the hard coat layer. The protective film is obtained by peeling a release film from a protective film with a release film composed of a support/an adhesive layer/a release film. As the protective film with a release film, a commercially available protective film with a release film can be preferably used. Specific examples thereof include FUJIMORI KOGYO CO., LTD. AS3-304, AS3-305, AS3-306, AS3-307, AS3-310, AS3-0421, AS3-0520, AS3-0620, LBO-307, NBO-0424, ZBO-0421, S-362 and TFB-4T3-367 AS.

< Process (B) >

The step (B) is a step of peeling the dummy support from the hard coat layer.

In order to peel the dummy support from the hard coat layer, the adhesion between the protective film and the hard coat layer needs to be higher than the peeling force between the dummy support and the hard coat layer. The method of adjusting the peeling force between the dummy support and the hard coat layer is not particularly limited, and examples thereof include a method of reducing the peeling force between the dummy support and the hard coat layer using a dummy support subjected to a mold release treatment. Further, the method of adjusting the adhesion between the protective film and the hard coat layer is not particularly limited, and for example, a method of bonding the protective film to the semi-cured hard coat layer and then curing the hard coat layer in the step (a) may be mentioned.

< step (2') >)

The step (2') is the same as the step (2) except that the dummy support is a protective film in the step (2) of the embodiment a.

< step (3') >)

The step (3') is the same as the step (3) of the embodiment a.

< step (4') >)

The step (4') is the same as the step (4) except that the dummy support is a protective film in the step (4) of the embodiment a.

< step (5') >)

The step (5') is the same as the step (5) except that the dummy support is a protective film in the step (5) of the embodiment a.

In the embodiment B, the number of steps is increased as compared with the embodiment a, and when a hard coat layer is formed, since a dummy support is not present on the outermost surface of the hard coat layer, the fluorine-containing compound and the leveling agent are easily concentrated on the outermost surface, and it is preferable when water repellency and scratch resistance are to be imparted to the hard coat surface. In the case of mode B, in order to further improve the water repellency and the abrasion resistance, the surface of the hard coat layer on the side opposite to the substrate may be subjected to the same surface treatment as in mode a after the step (5).

Examples

The present invention will be described in more detail with reference to examples, but the scope of the present invention should not be construed as being limited thereto.

< preparation of base Material >

(production of polyamideimide powder)

In a 1L reactor equipped with a stirrer, a nitrogen gas injection device, a dropping funnel, a temperature regulator and a cooler, 832g of N, N-dimethylacetamide (DMAc) was charged under a nitrogen gas stream, and then the temperature of the reactor was set to 25 ℃. 64.046g (0.2mol) of bistrifluoromethylbenzidine (TFDB) was added thereto and dissolved. While maintaining the obtained solution at 25 ℃, 31.09g (0.07mol) of 2, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) and 8.83g (0.03mol) of biphenyltetracarboxylic dianhydride (BPDA) were charged and stirred for a certain period of time to effect a reaction. Then, 20.302g (0.1mol) of terephthaloyl chloride (TPC) was added to obtain a polyamic acid solution having a solid content of 13% by mass. Then, 25.6g of pyridine and 33.1g of acetic anhydride were put into the polyamic acid solution, and stirred for 30 minutes, further stirred at 70 ℃ for 1 hour, and then cooled to room temperature. 20L of methanol was added thereto, and the precipitated solid component was filtered and pulverized. Then, vacuum drying was carried out at 100 ℃ for 6 hours, whereby 111g of polyamideimide powder was obtained.

(preparation of base S-1)

100g of polyamideimide powder was dissolved in 670g of N, N-dimethylacetamide (DMAc) to obtain a 13 mass% solution. The obtained solution was cast onto a stainless steel plate and dried with hot air at 130 ℃ for 30 minutes. Then, the film was peeled off from the stainless steel plate, fixed to the frame with pins, and the frame with the film fixed thereto was put into a vacuum oven, heated for 2 hours while gradually increasing the heating temperature from 100 ℃ to 300 ℃, and then gradually cooled. After the cooled film was separated from the frame, as a final heat treatment step, heat treatment was further performed at 300 ℃ for 30 minutes, thereby obtaining a substrate S-1 made of polyamideimide and having a thickness of 30 μm.

(production of aramid solution)

674.7kg of N-methyl-2-pyrrolidone, 10.6g of anhydrous lithium bromide (manufactured by Sigma-Aldrich Japan K.K.) and 33.3g of 2, 2 '-ditrifluoromethyl-4, 4' -diaminobiphenyl (manufactured by TORAY FINE CHEMICALS CO., LTD. "TFMB") and 2.9g of 4, 4 '-diaminodiphenyl sulfone (manufactured by Wakayama Seika Co., Ltd., "44 DDS" manufactured by Ltd.) were placed in a polymerization vessel equipped with a stirrer, and 18.5g of terephthaloyl dichloride (manufactured by Tokyo Chemical Co., Ltd.) and 6.4g of 4, 4' -biphenyldicarbonyl chloride (manufactured by TORAY FINE CHEMICALS CO., LTD. "4 BPAC") were added to the vessel while stirring the vessel under a nitrogen atmosphere at 4 times and 300 minutes. After stirring for 60 minutes, hydrogen chloride generated in the reaction was neutralized with lithium carbonate to obtain an aramid solution.

(preparation of base S-2)

A part of the aramid solution (polymer solution) obtained in the above was cast on an endless belt at 120 ℃ using a T-die so that the final film thickness became 65 μm, and dried until the polymer concentration became 40 mass%, and peeled off from the endless belt. Subsequently, the film containing the solvent was stretched 1.1 times in the MD (machine direction) direction in an atmosphere of 40 ℃ and washed with water of 50 ℃ to remove the solvent. Further stretching in a drying oven at 340 ℃ in the TD (Transverse direction) direction by 1.2 times resulted in a substrate S-2 formed of aramid fiber having a thickness of 50 μm.

< Synthesis of polyorganosilsesquioxane >

(Synthesis of Compound (X))

In a 1000 ml flask (reaction vessel) equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen inlet tube, 297 mmol (73.9g) of 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 7.39g of triethylamine and 370g of MIBK (methyl isobutyl ketone) were mixed under a nitrogen stream, and 73.2g of pure water was added dropwise over 30 minutes using a dropping funnel. The reaction solution was heated to 80 ℃ and subjected to polycondensation reaction under a nitrogen gas flow for 10 hours.

Then, the reaction solution was cooled, and 300g of 5 mass% saline was added to extract an organic layer. After the organic layer was washed 2 times with 300g of 5 mass% saline solution and 300g of pure water in this order, the organic layer was concentrated under 1mmHg at 50 ℃ to obtain a colorless and transparent liquid solution of methyl isobutyl ketone (MIBK) containing compound (X) (a compound of formula (1) wherein Rb: 2- (3, 4-epoxycyclohexyl) ethyl, Rc: methyl, q: 99, and r: 1) which is a polyorganosilsesquioxane having an alicyclic epoxy group) as a colorless and transparent liquid, as a MIBK solution having a solid content of 59.8 mass%.

As a result of analysis of the product, the number average molecular weight was 2050, and the molecular weight dispersion was 1.9.

Further, 1mmHg was about 133.322 Pa.

< Synthesis of interlayer sealing agent >

(Synthesis of interlayer sealing Polymer SX1)

The interlayer adhesion polymer is a compound which is concentrated on the air interface of the hard coat layer and contributes to the adhesion to the scratch-resistant layer.

30 mmol (14.05g) of trimethoxy (1H, 1H, 2H, 2H-tridecafluoro-n-octyl) silane, 135 mmol (33.26g) of 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 135 mmol (31.63g) of propyl 3- (trimethoxysilyl) acrylate, 7.39g of triethylamine and 370g of MIBK (methyl isobutyl ketone) were mixed, and 73.9g of pure water was added dropwise over 30 minutes using a dropping funnel. The reaction solution was heated to 50 ℃ and subjected to polycondensation reaction for 10 hours.

Then, the reaction solution was cooled, and 300g of 5 mass% saline was added to extract an organic layer. The organic layer was washed 2 times with 300g of 5 mass% saline solution and 300g of pure water in this order, and then concentrated under conditions of 30mmHg and 50 ℃ to obtain a colorless and transparent liquid product, i.e., a polymer (interlayer sealing agent) represented by the following formula (SX1), as a MIBK solution having a solid content concentration of 52 mass%.

[ chemical formula 8]

< preparation of composition for Forming hard coat layer >

(composition for Forming hard coat layer HC-1)

CPI-100P, leveling agent-1, and MIBK (methyl isobutyl ketone) were added to the MIBK solution containing the compound (X), and the concentrations of the respective components were adjusted to the following concentrations, and the mixture was put into a mixing tank and stirred. The obtained composition was filtered through a polypropylene filter having a pore size of 0.4. mu.m, thereby obtaining composition HC-1 for forming a hard coat layer.

98.7 parts by mass of Compound (X)

CPI-100P 1.3 parts by mass

10.01 parts by mass of leveling agent

Methyl isobutyl ketone 100.0 parts by mass

(composition for Forming hard coat layer HC-2)

HC-2 was prepared by changing HC-1 to the following composition ratio.

98.7 parts by mass of Compound (X)

CPI-100P 1.3 parts by mass

Interlayer sealing polymer SX 10.01 parts by mass

Methyl isobutyl ketone 100.0 parts by mass

The compounds used in the composition for forming a hard coat layer are as follows.

CPI-100P: cationic photopolymerization initiator, San-Apro Ltd

Leveling agent-1: a polymer having the following structure (Mw 20000, the composition ratio of the following repeating units is a mass ratio)

[ chemical formula 9]

< preparation of scratch-resistant layer-Forming composition >

(composition SR-1 for Forming scratch-resistant layer)

Each component was put into a mixing tank with the composition described below, stirred, and filtered through a polypropylene filter having a pore size of 0.4 μm, thereby obtaining a scratch-resistant layer-forming composition SR-1.

DPHA 96.2 parts by mass

Irgacure 1272.8 parts by mass

Interlayer adhesion polymer SX 11.0 parts by mass

290.0 parts by mass of methyl ethyl ketone

Methyl isobutyl ketone 10.0 parts by mass

(composition SR-2 for Forming scratch-resistant layer)

SR-2 was prepared by changing the composition ratio from SR-1 to the following one.

DPHA 96.2 parts by mass

RS-901.0 parts by mass

Compound P2.8 parts by mass

300.0 parts by mass of methyl ethyl ketone

The compounds used in the scratch-resistant layer-forming composition are as follows.

DPHA: a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, Nippo n Kayaku Co., Ltd

RS-90: lubricant manufactured by DIC Corporation

Compound P: a photoacid generator represented by the following structural formula (manufactured by Wako Pure Chemical Industries, Ltd.)

[ chemical formula 10]

< preparation of adhesive >

(ultraviolet ray curing adhesive composition UV-1)

CEL2021P 70.0.0 parts by mass

18.0 parts by mass of 1, 4-butanediol diglycidyl ether

10.0 parts by mass of 2-ethylhexyl glycidyl ether

Irgacure 2902.0 parts by mass

The compounds used in the ultraviolet-curable adhesive composition are as follows.

CEL 2021P: the following compounds. Manufactured by Daicel Corporation

Irgacure 290: sulfonium-based photo-cation initiator manufactured by BASF corporation

[ chemical formula 11]

(ultraviolet ray curing adhesive composition UV-2)

CEL2021P 70.0.0 parts by mass

18.0 parts by mass of 1, 4-butanediol diglycidyl ether

10.0 parts by mass of 2-ethylhexyl glycidyl ether

Irgacure 2903.0 parts by mass

Ultraviolet absorber 10.5 parts by mass

The ultraviolet absorber 1 used in the curable adhesive composition is as follows.

Ultraviolet absorber 1:

[ chemical formula 12]

[ example 1]

< preparation of hard coating film >

(step (1): Forming a hard coat layer on a dummy substrate)

As the dummy support, a scratch-resistant layer-forming composition SR-1 was applied on a 100 μm polyethylene terephthalate film (FD100M, Fujifilm Corporation (manufactured)) using a die coater. After drying at 120 ℃ for 1 minute, an air-cooled mercury lamp was used at 25 ℃ with an illuminance of 18mW/cm²The dose of irradiation was 10mJ/cm²And irradiating ultraviolet rays under the condition that the oxygen concentration is 1.0%, thereby semi-curing the scratch-resistant layer. Then, the hard coat layer-forming composition HC-1 was applied to the side of the scratch-resistant layer opposite to the dummy support using a die coater. After drying at 120 ℃ for 1 minute, an air-cooled mercury lamp was used at 25 ℃ under an illuminance of 60mW/cm²The dose of irradiation was 600mJ/cm²And the oxygen concentration was 100 ppm. Further using an air-cooled mercury lamp at 100 deg.C under an illumination of 60mW/cm²The dose of irradiation was 600mJ/cm²And irradiating ultraviolet rays under the condition of oxygen concentration of 100ppm, thereby fully curing the scratch-resistant layer and the hard coating layer.

(step (2): formation of adhesive layer)

The surface of the hard coat layer produced in step (1) on the side opposite to the scratch-resistant layer was subjected to corona discharge treatment. The corona discharge treatment was carried out at 20 m/min using a 6KVA type (NIPPON PILLAR PACKING Co., LTD., manufactured by NIPPON PILLAR PACKING Co., Ltd.) as a solid corona discharge processorA corona discharge treatment is performed. At this time, the treatment conditions were 0.375 kV. A. min/m, depending on the read values of current/voltage²The discharge frequency during the treatment was 9.6kHz, and the gap between the electrode and the dielectric roller was 1.6 mm. An ultraviolet-curable adhesive UV-1 was injected between the corona discharge-treated surface side of the hard coat layer and the substrate S-1, and the mixture was passed through a nip roll while being superimposed thereon, thereby forming a laminate having a dummy support, a scratch-resistant layer, a hard coat layer, an adhesive layer and a substrate S-1.

(step (3): formation of Mixed layer)

The laminate produced in step (2) was heated at 80 ℃ for 1 minute to form a mixed layer in which the components of the substrate S-1 and the components of the adhesive were mixed.

(step (4): bonding)

The laminate having the mixed layer produced in step (3) was irradiated with 60mW/cm of illumination from the side opposite to the substrate using an air-cooled mercury lamp at 25 ℃²The dose of irradiation was 600mJ/cm²Thereby curing the adhesive layer and bonding the hard coat layer to the base material S-1.

(step (5): peeling off the dummy substrate)

The pseudo support was peeled from the laminate in which the hard coat layer obtained in step (4) was bonded to the substrate S-1, thereby obtaining a hard coat film 1.

[ examples 2 to 5]

Hard coat films 2 to 5 were obtained in the same manner as in example 1, except that the film thickness of the hard coat layer, the substrate, and the conditions for forming the mixed layer were changed as shown in table 1.

[ example 6]

< preparation of hard coating film >

(step (1): Forming a hard coat layer on a dummy substrate)

As a dummy support, a composition HC-1 for forming a hard coat layer was coated on a 100 μm polyethylene terephthalate film (FD100M, manufactured by Fujifilm Corporation) using a die coater. After drying at 120 ℃ for 1 minute, an air-cooled mercury lamp was used at 25 ℃ under an illuminance of 60mW/cm²The dose of irradiation was 600mJ/cm²And oxygen concentration of 100ppmUltraviolet rays are irradiated. Further using an air-cooled mercury lamp at 100 deg.C under an illumination of 60mW/cm²The dose of irradiation was 600mJ/cm²And irradiating ultraviolet rays under the condition of oxygen concentration of 100ppm, thereby fully curing the hard coating layer.

(step (2): formation of adhesive layer)

The surface of the hard coat layer produced in step (1) on the side opposite to the dummy support side was subjected to corona discharge treatment under the same conditions as in example 1. An ultraviolet-curable adhesive UV-1 was injected between the corona discharge-treated surface side of the hard coat layer and the substrate S-1, and the mixture was passed through a nip roll while being superimposed thereon, thereby forming a laminate having a dummy support, a scratch-resistant layer, a hard coat layer, an adhesive layer and a substrate S-1.

(step (3): formation of Mixed layer)

The laminate produced in step (2) was heated at 80 ℃ for 1 minute to form a mixed layer in which the components of the substrate S-1 and the components of the adhesive were mixed.

(step (4): bonding)

The laminate having the mixed layer produced in step (3) was irradiated with 60mW/cm of illumination from the side opposite to the substrate using an air-cooled mercury lamp at 25 ℃²The dose of irradiation was 600mJ/cm²Thereby curing the adhesive layer and bonding the hard coat layer to the base material S-1.

(step (5): peeling off the dummy substrate)

The dummy support was peeled from the laminate in which the hard coat layer obtained in step (4) was bonded to the substrate S-1, thereby obtaining a hard coat film 6.

[ example 7]

(step (1'): Forming a hard coat layer on a dummy substrate)

As a dummy support, a composition HC-2 for forming a hard coat layer was applied to the release-treated side of a non-silicone release film HP-a5 (manufactured by Fujico co., ltd.) using a die coater. After drying at 120 ℃ for 1 minute, an air-cooled mercury lamp was used at 25 ℃ under an illuminance of 18mW/cm²The dose of irradiation was 10mJ/cm²And an oxygen concentration of 100ppm by irradiating ultraviolet raysAnd semi-curing the hard coating. Then, the hard coat layer was coated with the scratch-resistant layer-forming composition SR-2 on the side opposite to the dummy support using a die coater. After drying at 120 ℃ for 1 minute, an air-cooled mercury lamp was used at 25 ℃ under an illuminance of 18mW/cm²The dose of irradiation was 10mJ/cm²And an oxygen concentration of 1.0% by irradiating ultraviolet rays, thereby semi-curing the hard coat layer.

(Process (A): application of hard coating protective film)

A protective film obtained by peeling the release film from the protective film with a release film (master TFB AS3-304) manufactured by FUJIMORI KOGYO co. The lamination was performed at speed 1 using a laminator Bio330 for Enterprise (manufactured by DAE-EL). Then, in order to improve the adhesion force between the protective film and the scratch-resistant layer, an illuminance of 60mW/cm was applied from the hard coat protective film side at 100 ℃ using an air-cooled mercury lamp²The dose of irradiation was 600mJ/cm²Ultraviolet rays of (1).

(step (B): peeling off the dummy substrate)

The dummy support was peeled from the laminate obtained in the step (a).

(step (2'): formation of adhesive layer)

The surface of the hard coat layer produced in step (B) on the side opposite to the scratch-resistant layer was subjected to corona discharge treatment under the same conditions as in step (2) of example 1. Subsequently, an ultraviolet-curable adhesive UV-1 was injected between the corona discharge-treated surface side of the hard coat layer and the substrate S-1, and the mixture was passed through a nip roll while being superimposed thereon, thereby forming a laminate having a protective film, a scratch-resistant layer, a hard coat layer, an adhesive layer and a substrate S-1.

(step (3'): formation of Mixed layer)

A mixed layer was formed in the same manner as in the step (3) of example 1.

(step (4'): bonding)

The bonding was performed in the same manner as in the step (4) of example 1.

(step (5'): protective film)

The protective film is peeled off from the laminate obtained in the step (4'), thereby obtaining a hard coat film 7.

Comparative example 1

In example 6, a hard coat film of comparative example 1 was obtained by the same method except that the step (3) was not performed immediately after the roll was passed through the step (2) and the adhesion by the ultraviolet irradiation in the step (4) was performed.

[ example 8]

A hard coat film 8 was obtained in the same manner as in example 1, except that the ultraviolet-curable adhesive composition was changed as shown in table 1.

[ calculation of film thickness of each layer on hard coat film ]

The film thicknesses of the hard coat layer, the scratch-resistant layer, the adhesive layer, and the mixed layer of the hard coat film thus produced were calculated by cutting the hard coat film with a microtome and analyzing the cross section with a scanning electron microscope (S-5200, manufactured by Hitachi High-Tech corporation) and a time-of-flight secondary ION mass spectrometer (TOF-SIMS V, manufactured by ION-TOF Co., Ltd.), and are shown in Table 1. In addition, the thickness of the mixed layer was calculated by detecting the components of the base material and the adhesive layer at the same time.

[ evaluation of hard coating film ]

The hard coat film produced was evaluated by the following method.

(Pencil hardness)

The hard coat layer or the scratch-resistant layer side of the hard coat film was measured in accordance with JIS K5600-5-4 (1999), and evaluated in the following 4 stages.

A: the pencil hardness is more than 6H.

B: the pencil hardness is more than 5H and less than 6H.

C: the pencil hardness is more than 4H and less than 5H.

D: the pencil hardness is less than 4H.

The pencil hardness is practically required to be A to C, preferably A to B, and more preferably A.

(lightfast seal)

The light-resistant adhesion was evaluated by the following method.

The cross-cut test was performed in accordance with JIS K5600. Specifically, 11 cuts were made in a cross-cut manner at 1mm intervals on the surface of the hard coat layer or the scratch-resistant layer side of the hard coat film to form 100 1mm square grids. A transparent pressure-sensitive adhesive tape (nicoiban co., ltd., product, CELLOTAPE (registered trademark) CT-15S) was attached thereto, and the peeled portion was rapidly peeled off and visually observed to evaluate the adhesiveness. The samples for measurement were evaluated before the adhesion evaluation, after conditioning for 2 hours in a room at a temperature of 25 ℃ and a relative humidity of 60%. Xe (xenon) is added at 150W/m²After 24 hours of irradiation, the adhesion was evaluated according to the following criteria.

Adhesion A: 0 lattice of the peeled part

Adhesion B: 1 to 10 lattices of the peeled part

Adhesion C: 11 to 49 cases of peeling part

Adhesion D: 50-99 lattices of the peeled part

Adhesion E: stripping part more than 100 grids (all parts of adhesive tape)

Further, a super xenon lamp weatherometer SX75 manufactured by Suga Test Instruments co., ltd. was used for Xe irradiation.

The light-resistant adhesion is practically required to be a to C, preferably a to B, and more preferably a.

(resistance to repeated bending)

A sample film having a width of 15mm and a length of 150mm was cut out from the hard coat films produced in the examples and comparative examples, and the film was allowed to stand at a temperature of 25 ℃ and a relative humidity of 65% for 1 hour or more. Then, a bending resistance test was repeated using an impact mechanical co., ltd, model IMC-0755, bending radius of curvature 1.0mm, so that the substrate was positioned outside. The evaluation was made according to the following criteria, depending on the number of times until the sample film had cracked or broken.

A: more than 50 ten thousand times

B: more than 10 ten thousand times, less than 50 ten thousand times

C: less than 10 ten thousand times

The evaluation results are shown in table 1 below.

As shown in table 1, the hard coat films of the examples all had excellent pencil hardness, light-resistant adhesion, and repeated bending resistance. On the other hand, the hard coating film of comparative example 1 had no mixed layer formed, and thus had good pencil hardness but poor light-resistant adhesion.

Industrial applicability

According to the present invention, a hard coat film having high hardness, excellent light-resistant adhesion, and excellent repeated bending resistance, a method for producing the hard coat film, an article provided with the hard coat film, and an image display device can be provided.

The present invention is described in detail with reference to specific embodiments, but it is apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention.

The present application is based on the japanese patent application published on 12/4/2019 (japanese patent 2019-.

Description of the symbols

1-substrate, 2-mixed layer, 3-adhesive layer, 4-hard coating, 5-scratch resistant layer, 6-pseudo support, 7-adhesive layer, 8-support of protective film, 9-protective film, 10, 11-hard coating film, UV-ultraviolet.