TWI787508B - Laminated films and foldable devices - Google Patents

Abstract

The purpose of the present invention is to provide a laminated film which has high surface hardness and excellent bending durability and is suitable as a surface protection material for foldable devices. The laminated film of the present invention has a support body and a resin layer laminated on at least one side of the support body, and is characterized in that the resin layer (any resin layer in the case of a resin layer layered on both sides of the support body) ) fully satisfy the following (condition 1) and (condition 2). (Condition 1) The pencil hardness of the resin layer surface of the above laminated film in the pencil hardness test (750 g load) stipulated in JIS K5600-5-4 (1999) is F or more. (Condition 2) The bending durability (1) in the following bending durability test (1) is 50,000 times or more. Bending Durability Test (1): In the state where the self-laminated film is unfolded, it is bent 180° along the direction in which the surface of the resin layer becomes a depression with a bending radius of 2.5 mm, and the action of unfolding again is set once, and the above is performed at a speed of 30 to 60 times/min. During operation, the number of times until the resin layer of the laminated film cracks is taken as an index of bending durability (1)

Description

Laminated films and foldable devices

The present invention relates to a laminated film with high surface hardness and excellent bending durability and a foldable device with the laminated film.

In order to further improve the portability of mobile information terminals such as smart phones or tablets, the demand for foldable devices such as foldable displays and touch panels has increased. In order to improve portability, foldable devices must be bent to 180° with a small bending radius (for example, a bending radius of about 2.5 mm), which requires extremely high bendability (flexibility). In addition, a foldable device is carried in a folded state, opened during use, folded again after use, and used repeatedly. Therefore, high bending durability is also required, that is, cracks will not occur even if folded repeatedly. durability.

Highly flexible image display devices such as organic EL are used in foldable devices, but in order to impart scratch resistance so as not to cause scratches on the image display surface during use, it is usually formed by using a support film The scratch resistance of the image display surface of an image display device is improved by protecting it with a laminated film (hard coat film) with a hard coat layer (for example, Patent Document 1). [Prior Art Literature] [Patent Document]

Patent Document 1: Japanese Patent Laid-Open No. 2014-186210

[Problem to be Solved by the Invention]

However, although the conventional hard coating film has excellent surface hardness and flexibility, it has the following problems: if it is repeatedly folded, cracks will occur in the hard coating layer, and the bending durability is low, so it cannot be used as a member for protecting the surface of a foldable device.

Therefore, the object of the present invention is to provide a laminated film which has high surface hardness and excellent bending durability and is suitable as a surface protection material for foldable devices. Another object of the present invention is to provide a foldable device including the above-mentioned laminated film. [Technical means to solve the problem]

That is, the present invention provides a laminated film (1) having a support, and The resin layer laminated on at least one side of the support is characterized in that: This resin layer (any resin layer when there is a resin layer in the double-sided layer of the above-mentioned support) fully satisfies the following (Condition 1) and (Condition 2). (Condition 1) The pencil hardness of the resin layer surface of the above laminated film in the pencil hardness test (750 g load) stipulated in JIS K5600-5-4 (1999) is F or more. (Condition 2) The bending durability (1) in the following bending durability test (1) is 50,000 times or more. Bending Durability Test (1): In the state where the self-laminated film is unfolded, it is bent 180° along the direction in which the surface of the resin layer becomes a depression with a bending radius of 2.5 mm, and the action of unfolding again is set once, and the above is performed at a speed of 30 to 60 times/min. During operation, the number of times until the resin layer of the laminated film cracks is taken as an index of bending durability (1)

Also, the present invention provides a laminated film (2) having a support, and The resin layer laminated on at least one side of the support is characterized in that: This resin layer (any resin layer when there is a resin layer in the double-sided layer of the above-mentioned support) fully satisfies the following (Condition 1) and (Condition 3). (Condition 1) The pencil hardness of the resin layer surface of the above laminated film in the pencil hardness test (750 g load) stipulated in JIS K5600-5-4 (1999) is F or more. (Condition 3) The bending durability (2) in the following bending durability test (2) is 10,000 times or more. Bending durability test (2): In the state where the self-laminated film is unfolded, bend 180° in the direction in which the surface of the resin layer protrudes so that the bending radius becomes 4.0 mm, and then unfold it once again, and perform the above at a speed of 30 to 60 times/min. During operation, the number of times until the resin layer of the laminated film cracks is taken as an index of bending durability (2)

In the above-mentioned laminated films (1) and (2), it is preferable that the above-mentioned resin layer (in the case where there are resin layers on the double-layered layer of the above-mentioned support, be any one of the resin layers) further satisfies the following (condition 4) . (Condition 4) In the cylindrical mandrel test stipulated in JIS K5600-5-1 (1999) where the surface of the resin layer of the laminated film becomes convex, the bending radius is 5 mm, and there is no protrusion on the surface of the resin layer. Cracks

In the above-mentioned laminated films (1) and (2), it is preferable that the water contact angle of the surface of the above-mentioned resin layer (when there are resin layers on the double-layered layer of the above-mentioned support) is 95°. above.

In the above-mentioned laminated films (1) and (2), it is preferable that the above-mentioned resin layer (either one of the resin layers when there are resin layers on the double-layered layer of the above-mentioned support) fully satisfies the following (condition 5). (Condition 5) While applying a load of 1 kg/cm ² using #0000 steel wool, no scratches were visually observed in the steel wool resistance test in which the surface of the resin layer was rubbed back and forth 30 times.

In the above-mentioned laminated films (1) and (2), it is preferable that the haze of the above-mentioned resin layer (when there are resin layers on the double-layered layer of the above-mentioned support, either resin layer) is 1.0% or less.

In the above-mentioned laminated films (1) and (2), it is preferable that the above-mentioned resin layer is a cured product of a curable composition containing at least one curable compound, and at least one curable compound is a polyorganic compound. Semisiloxane (polyorganosilsesquioxane).

In the above-mentioned laminated films (1) and (2), it is preferable that the above-mentioned curable composition contains a compound having one or more thermally polymerizable functional groups and one or more photopolymerizable functional groups in a molecule.

In the above-mentioned laminated films (1) and (2), it is preferable that the above-mentioned curable composition further contains a curing catalyst. The aforementioned hardening catalyst may be a photocationic polymerization initiator. The aforementioned hardening catalyst may be a thermal cationic polymerization initiator.

In the above-mentioned laminated films (1) and (2), it is preferable that the above-mentioned curable composition further contains a fluorine-containing photopolymerizable resin.

In the above-mentioned laminated films (1) and (2), it is preferable that the above-mentioned support is a transparent support.

Also, the present invention provides a foldable device including the above-mentioned laminated film (1) or (2).

The above-mentioned foldable device may be an image display device. In the above-mentioned foldable device, the above-mentioned image display device may be an organic electroluminescent display device. [Effect of Invention]

The laminated film of the present invention has high surface hardness and excellent bending durability. Therefore, the laminated film of the present invention can be suitably used as a surface protection material for foldable devices such as foldable image display devices.

[laminated film] An aspect of the laminated film of the present invention (hereinafter sometimes referred to as "laminated film (1)") is one having a support and a resin layer laminated on at least one side of the support, and is characterized in that the resin layer (Any resin layer when there is a resin layer in the double-sided layer of the above-mentioned support.) The following (Condition 1) and (Condition 2) are fully satisfied. (Condition 1) The pencil hardness of the resin layer surface of the above laminated film in the pencil hardness test (750 g load) stipulated in JIS K5600-5-4 (1999) is F or more. (Condition 2) The bending durability (1) in the following bending durability test (1) is 50,000 times or more. Bending Durability Test (1): In the state where the self-laminated film is unfolded, it is bent 180° along the direction in which the surface of the resin layer becomes a depression with a bending radius of 2.5 mm, and the action of unfolding again is set once, and the above is performed at a speed of 30 to 60 times/min. During operation, the number of times until the resin layer of the laminated film cracks is taken as an index of bending durability (1)

The laminated film (1) of the present invention has extremely excellent surface hardness and bending durability, and can be suitably used as a surface protection material for foldable devices such as organic EL display devices. That is, in the laminated film (1) of this invention, the said resin layer fully satisfies the said (condition 1) and (condition 2). Furthermore, in the laminated film (1) of the present invention, when the above-mentioned resin layer is laminated on both sides of the above-mentioned support, any one of the resin layers may sufficiently satisfy (Condition 1) and (Condition 2). A resin layer may or may not fully satisfy (Condition 1) and/or (Condition 2).

The above condition 1 means that the surface of the resin layer of the laminated film (1) of the present invention has excellent surface hardness. The pencil hardness of the pencil hardness test (750 g load) stipulated in JIS K5600-5-4 (1999) on the surface of the resin layer is F or higher, preferably 1 H or higher, more preferably 2 H or higher, more preferably 3 H or more, more preferably 4 H or more, more preferably 5 H or more, more preferably 6 H or more, more preferably 7 H or more, further preferably 8 H or more, especially preferably 9 H. If the pencil hardness of the surface of the above-mentioned resin layer is less than F, the surface hardness of the laminated film (1) of the present invention becomes insufficient, and it may be difficult to use as a surface protective material for a foldable device.

The above-mentioned condition 2 means that the laminated film (1) of the present invention has excellent bending durability, that is, even if it is repeatedly folded, it is not easy to cause defects such as cracks in the resin layer. The condition of durability (hereinafter, sometimes referred to as "bending durability (1)") when the surface of the layer is folded repeatedly so that the surface becomes concave (inside).

Fig. 1 shows the self-laminated film (1) (1 of Fig. 1) in the unfolded state (Fig. 1 (1)) in the bending durability test (1) represented by the above-mentioned condition 2, so as to form a depression along the surface of the resin layer It is a schematic diagram (side view) of one movement of bending 180° such that the bending radius (R) in the (inner) direction (not shown) becomes 2.5 mm, and unfolding again. Figure 2 is an enlarged view of Figure 1 (4), where R represents the bending radius. In the bending durability test (1), a cylindrical mandrel with a radius of 2.5 mm can be wound around the bent portion of the resin layer of the laminated film (1) so that the bending radius becomes 2.5 mm. In the bending durability test (1), the number of times when the above operation is performed at a speed of 30 to 60 times within 1 minute until a crack occurs in the resin layer of the laminated film (1) is defined as the bending durability (1) The index.

The bending durability (1) in the bending durability test (1) of the laminated film (1) of the present invention is 50,000 times or more, preferably 60,000 times or more, more preferably 70,000 times or more, more preferably 8 More than 10,000 times, more preferably 90,000 times or more, more preferably 100,000 times or more, further preferably 150,000 times or more, especially preferably 200,000 times or more. If the bending durability (1) is less than 50,000 times, the bending durability (1) of the multilayer film (1) of the present invention becomes insufficient, and it is difficult to use it as a foldable device (especially a display device that bends inwards) etc.) in the case of surface protection materials.

As another aspect of the laminated film of the present invention (hereinafter sometimes referred to as "laminated film (2)"), it is also preferable that the above-mentioned resin layer (in the case where there are resin layers on the double-layered layer of the above-mentioned support) Any resin layer) fully satisfies the aspects of the above (Condition 1) and the following (Condition 3). (Condition 3) The bending durability (2) in the following bending durability test (2) is 10,000 times or more. Bending durability test (2): In the state where the self-laminated film is unfolded, bend 180° in the direction in which the surface of the resin layer protrudes so that the bending radius becomes 4.0 mm, and then unfold it once again, and perform the above at a speed of 30 to 60 times/min. During operation, the number of times until the resin layer of the laminated film cracks is taken as an index of bending durability (2)

Furthermore, in the laminated film (2) of the present invention, in the case where the above-mentioned resin layer is laminated on both sides of the above-mentioned support, it is sufficient that any one of the resin layers satisfies (Condition 1) and (Condition 3). A resin layer may or may not fully satisfy (Condition 1) and/or (Condition 3).

The measurement method of the pencil hardness test and the preferred pencil hardness in the condition 1 of the laminated film (2) of the present invention are the same as those of the above-mentioned laminated film (1).

The above condition 3 represents the durability of the laminated film (2) of the present invention when it is repeatedly folded so that the surface of the resin layer becomes a protrusion (outside) (hereinafter sometimes referred to as "bending durability"). Durability (2)") conditions. In the bending durability test (2) for bending durability (2), except that the surface of the resin layer becomes the convex (outer) direction, and the bending radius (R) is set to 4.0 mm, it can be used in the same bending durability as above The test was carried out under the same conditions as (1).

The bending durability (2) in the bending durability test (2) of the laminated film (2) of the present invention is 10,000 times or more, more preferably 20,000 times or more, more preferably 30,000 times or more, more preferably 4 times More than 10,000 times, more preferably 50,000 times, more preferably 60,000 times, more preferably 70,000 times, more preferably 80,000 times, more preferably 90,000 times, more preferably 100,000 times More than above, more preferably at least 150,000 times, especially preferably at least 200,000 times. If the bending durability (2) is less than 10,000 times, the bending durability (2) of the laminated film (2) of the present invention becomes insufficient, and it is difficult to use it as a foldable device (especially a display device that bends outwards) etc.) in the case of surface protection materials.

The laminated film (1) and laminated film (2) of the present invention (hereinafter, collectively referred to as "the laminated film of the present invention") are more preferably the above-mentioned resin layer (resin layer on the double-layered layer of the above-mentioned support) In the case of a layer, any resin layer) fully satisfies all of the above (Condition 1) to (Condition 3).

The laminated film of the present invention (including laminated film (1) and laminated film (2). The same below) is preferably the above-mentioned resin layer (any resin layer when there are resin layers on both sides of the above-mentioned support) Furthermore, the following (condition 4) is satisfied. (Condition 4) In the cylindrical mandrel test stipulated in JIS K5600-5-1 (1999) where the surface of the resin layer of the laminated film becomes convex, the bending radius is 5 mm, and there is no protrusion on the surface of the resin layer. Cracks occur (hereinafter, for example, sometimes referred to as "bending less than 5 mm")

Furthermore, in the laminated film of the present invention, when the above-mentioned resin layer is laminated on both sides of the above-mentioned support, any one resin layer may fully satisfy (Condition 4), and the other resin layer may fully satisfy (Condition 4). 4), may not be fully satisfied.

The above-mentioned condition 4 is a condition showing that the laminated film of the present invention has excellent bendability. The bendability of the laminated film of the present invention is 5 mm or less, preferably 4.5 mm or less, more preferably 4.0 mm or less, more preferably 3.5 mm or less, more preferably 3.0 mm or less, further preferably 2.5 mm or less, especially Preferably less than 2.0 mm. When the bendability exceeds 5 mm, the bendability of the laminated film of the present invention becomes insufficient, and it may be difficult to use as a surface protection material for foldable devices (especially display devices that bend outward).

The laminated film of the present invention is preferably the above-mentioned resin layer (any resin layer when there are resin layers on the double-layered layer of the above-mentioned support) and satisfies the following (condition 5). (Condition 5) While applying a load of 1 kg/cm ² using #0000 steel wool, no scratches were visually observed in the steel wool resistance test in which the surface of the above-mentioned resin layer was rubbed back and forth 30 times (hereinafter, sometimes referred to as "Scratch resistance is 30 times or more")

Furthermore, in the laminated film of the present invention, when the above-mentioned resin layer is laminated on both sides of the above-mentioned support, it is sufficient that any one resin layer satisfies (Condition 5) and the other resin layer satisfies (Condition 5). 5), may not be fully satisfied.

The above-mentioned condition 5 is a condition showing that the laminated film of the present invention has excellent scratch resistance. The scratch resistance of the laminated film of the present invention is more than 30 times, preferably more than 100 times, more preferably more than 200 times, more preferably more than 300 times, more preferably more than 500 times, more preferably more than 700 times, and further Preferably, it is 1000 times or more, especially preferably, it is 2000 times or more. When the scratch resistance is less than 30 times, the scratch resistance of the laminated film of the present invention becomes insufficient, and it may be difficult to use as a surface protective material for a foldable device.

The laminated film of the present invention may have a support, a layer other than a resin layer, such as an anchor layer, an adhesive layer, a low-reflection layer, an antifouling layer, a water-repellent layer, an oil-repellent layer, an antifog layer, a protective film layer, and a printing layer. , conductive layer, electromagnetic wave shielding layer, ultraviolet absorbing layer, infrared absorbing layer, blue light cutting layer, etc. The above-mentioned resin layer may be formed on only a part of the surface of the above-mentioned support, or may be formed on the entire surface.

The haze of the laminated film of the present invention is, for example, 7% or less, preferably 6% or less, more preferably 5% or less, more preferably 4% or less, further preferably 3% or less, especially preferably 2% or less, The best is below 1%. In addition, the lower limit of the haze is, for example, 0.1%. In particular, by setting the haze to 7% or less, it tends to be suitable for applications requiring very high transparency (for example, surface protection sheets of displays such as touch panels, etc.). The haze of the present invention can be easily controlled within the above range by using, for example, the following transparent substrate as a support. In addition, in this specification, haze can be measured based on JISK7136.

The total light transmittance of the laminated film of the present invention is, for example, above 85%, preferably above 90%. In particular, by setting the total light transmittance to 90% or more, it tends to be suitable for applications requiring very high transparency (for example, surface protection sheets of displays such as touch panels, etc.). The total light transmittance of the present invention can be easily controlled within the above range by using the following transparent substrate as a support, for example. In addition, in this specification, total light transmittance can be measured based on JISK7361-1.

The thickness of the laminated film of the present invention (the total thickness of the support body/resin layer) can be appropriately selected, for example, from the range of 1 to 10000 μm, preferably 10 to 1000 μm, more preferably 15 to 800 μm, and even more preferably 20-700 μm, preferably 30-500 μm.

In the laminated film of the present invention, the water contact angle of the surface of the resin layer (when there are resin layers on the double-sided layer of the above-mentioned support) is preferably 95° or more, more preferably 96° Above, more preferably above 97°, more preferably above 98°, more preferably above 99°, more preferably above 100°, more preferably above 101°, more preferably above 102°, more preferably above 103° , and more preferably at least 104°, especially preferably at least 105°. When the water contact angle is less than 95°, the antifouling property of the laminated film of the present invention becomes insufficient, and it may be difficult to use it as a surface protection material for a foldable device.

Furthermore, in the laminated film of the present invention, when the above-mentioned resin layer is laminated on both sides of the above-mentioned support, it is only necessary that the water contact angle of any one resin layer is 95° or more, and the water contact angle of the other resin layer The angle is not limited, and may be greater than or equal to 95°, and may be less than 95°.

The laminated film of the present invention having the above properties can be obtained by selecting the material of the support, controlling the thickness of the support, controlling the composition or thickness of the resin layer, and laminating the film on the support as follows.

(support body) As the support in the laminated film of the present invention, plastic substrates, metal substrates, ceramic substrates, semiconductor substrates, glass substrates, paper substrates, wood substrates (wooden substrates), and coated substrates can be used. Known or commonly used supports such as substrates on the surface are not particularly limited. Among them, plastic substrates are preferred. The aforementioned support may have a single-layer configuration or a multi-layer (laminated) configuration, and the configuration (structure) is not particularly limited.

The plastic material constituting the above-mentioned plastic substrate is not particularly limited, and examples include: polyesters such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN); polyimide; polycarbonate ; Polyamide; Polyacetal; Polyphenylene ether; Polyphenylene sulfide; Polyether; Polyether ether ketone; ), copolymers of norbornene and ethylene, etc., copolymers of norbornene-based monomers and olefinic monomers (cyclic olefin copolymers such as addition polymers or ring-opening polymers, etc.), derivatives thereof, etc. Cyclic polyolefins; vinyl polymers (such as acrylic resins such as polymethyl methacrylate (PMMA), polystyrene, polyvinyl chloride, acrylonitrile-styrene-butadiene resin (ABS resin), etc.); Vinylidene-based polymers (such as polyvinylidene chloride, etc.); cellulose-based resins such as triacetyl cellulose (TAC); epoxy resins; phenol resins; melamine resins; urea resins; maleimide Resin; polysiloxane and other plastic materials. Furthermore, the above-mentioned plastic base material may be composed of only one type of plastic material, or may be composed of two or more types of plastic materials.

Among them, as the above-mentioned plastic substrate, in order to obtain a laminated film with excellent transparency and bending durability, it is preferable to use a support (transparent support) with excellent transparency and bending durability, and a polyester film (especially PET, PEN), polyimide film, cyclic polyolefin film, polycarbonate film, TAC film, PMMA film, and more preferably polyester film (especially PET, PEN), polyimide film.

The above-mentioned supports (especially plastic substrates) may also contain antioxidants, ultraviolet absorbers, light-resistant stabilizers, heat stabilizers, crystal nucleating agents, flame retardants, flame retardant additives, fillers, and plasticizers if necessary , Impact resistance modifier, reinforcing agent, dispersant, antistatic agent, foaming agent, antibacterial agent and other additives. In addition, an additive may be used individually by 1 type, and may use it in combination of 2 or more types.

Roughening treatment, easy-adhesive treatment, antistatic treatment, sandblasting treatment (sand roughening treatment), corona discharge treatment, plasma treatment, chemical Etching treatment, water roughening treatment, flame treatment, acid treatment, alkali treatment, oxidation treatment, ultraviolet irradiation treatment, silane coupling agent treatment and other known or customary surface treatments. Furthermore, the above-mentioned plastic substrate can be an unstretched film or a stretched film (uniaxially stretched film, biaxially stretched film, etc.). In addition, as a support body, a commercial item can be used.

The thickness of the above-mentioned support is, for example, about 1-1000 μm, preferably 5-500 μm, more preferably 10-400 μm, more preferably 15-400 μm, further preferably 20-300 μm, especially preferably 25 μm. ~200 μm.

The haze of the support of the present invention is, for example, 7% or less, preferably 6% or less, more preferably 5% or less, more preferably 4% or less, further preferably 3% or less, especially preferably 2% or less, The best is below 1%. In addition, the lower limit of the haze is, for example, 0.1%. In particular, by setting the haze to 7% or less, it tends to be suitable for applications requiring very high transparency (for example, surface protection sheets of displays such as touch panels, etc.).

The total light transmittance of the support of the present invention is, for example, above 85%, preferably above 90%. In particular, by setting the total light transmittance to 90% or more, it tends to be suitable for applications requiring very high transparency (for example, surface protection sheets of displays such as touch panels, etc.).

(resin layer) In the present invention, the above-mentioned resin layer is formed using a cured product of the following curable composition. That is, the resin layer is a layer composed of a cured product formed from the curable composition, and satisfies the above-mentioned (Condition 1) and (Condition 2) or (Condition 3) sufficiently, preferably satisfies the above-mentioned (Condition 4) and/or (Condition 5) layers. In addition, the above-mentioned resin layer can be produced using a curable composition by the production method of the laminated film described below.

The thickness of the resin layer is, for example, 1 to 100 μm, preferably 2 to 80 μm, more preferably 3 to 60 μm, and still more preferably 5 to 50 μm from the viewpoint of surface hardness and scratch resistance. , the best is 10~40 μm. When the thickness of the resin layer is thinner than 1 μm, high surface hardness may not be maintained. In addition, when the thickness of the resin layer is thicker than 100 μm, problems such as large curls tend to occur.

The haze of the resin layer is, for example, 1.0% or less, preferably 0.5% or less, more preferably 0.1% or less. Furthermore, the lower limit of the haze of the resin layer is, for example, 0.1%. In particular, by setting the haze of the resin layer to 1.0% or less, it tends to be suitable for applications requiring very high transparency (for example, surface protection sheets for displays such as touch panels). The haze of the resin layer can be obtained from the difference obtained by subtracting the haze of the support from the haze of the above laminated film (support/resin layer).

The total light transmittance of the resin layer is, for example, above 85%, preferably above 90%. By making the total light transmittance 85% or more, for example, it tends to be suitable for applications requiring very high transparency (for example, surface protection sheets of displays such as touch panels). The total light transmittance of the resin layer can be obtained, for example, by applying the above curable composition to the release mold so that the thickness after curing becomes the same as the resin layer of the laminated film of the present invention. The substrate was cured, and after the cured film was peeled off, it was measured in accordance with JIS K7361-1.

The smoothness of the surface of the above-mentioned resin layer is also excellent, and the arithmetic average roughness _Ra is, for example, 0.1-20 nm, preferably 0.1-10 nm, more preferably 0.1-5 nm in the method based on JIS B0601.

The above-mentioned resin layer may be laminated on only one surface of the above-mentioned support, or may be laminated on both surfaces. In the case of resin laminated layers on both sides of the support, the same resin layer may be used, or different resin layers may be used. Also, in the case where the resin layer is laminated on both sides of the support, one resin layer satisfies the above (Condition 1) and (Condition 2) or (Condition 3), preferably fully satisfies the above (Condition 4) and/or Or (Condition 5) may be sufficient, and the other resin layer may fully satisfy any one or more of (Conditions 1 to 5), or may not fully satisfy.

(hardening composition) The curable composition used to form the resin layer in the laminated film of the present invention is not particularly limited, and it can be used in the hard coat layer of known hard coat films without particular limitation. Specifically, it can be used containing It is formed by hardening the hardening composition of one or more hardening compounds.

As the curable compound constituting the above-mentioned curable composition, components of a hard coat layer for forming a known hard coat film can be used without particular limitation, for example, (meth)acrylate compounds, cationic curable polymer Silicone resin, epoxy resin, melamine resin, vinyl ether resin, oxetane resin, etc. In order to fully satisfy the above-mentioned performances (Conditions 1 to 5) of the laminated film of the present invention, a cation-curable polysiloxane resin is preferred.

[式（1）中，R¹ 表示含有陽離子聚合性官能基之基]The above-mentioned cation-curable polysiloxane resin is preferably in the form of containing polyorganosilsesquioxane, specifically, it is preferable to use a polyorganosilsesquioxane containing "having a constituent unit represented by the following formula (1) Silicone (hereinafter, sometimes referred to as "polyorganosilsesquioxane of the present invention")" (hereinafter, sometimes referred to as "curable composition of the present invention")" is formed.

[In formula (1), R ¹ represents a group containing a cationic polymerizable functional group]

The curable composition of the present invention is a curable composition (curable resin composition) containing the polyorganosilsesquioxane of the present invention as an essential component, and is used to form the resin layer in the laminated film of the present invention. sclerosing composition. As described below, the hardening composition of the present invention may further contain a hardening catalyst (especially a photocationic polymerization initiator, a radical polymerization initiator), or have one or more thermally polymerizable functional groups and Compounds with one or more photopolymerizable functional groups, fluorine-containing photopolymerizable resins, surface regulators or surface modifiers, and other components.

(Polyorganosilsesquioxane) The polyorganosilsesquioxane of the present invention is characterized by having a structural unit represented by the above formula (1). In addition, the polyorganosilsesquioxane of the present invention preferably has a structural unit represented by the following formula (1) (sometimes referred to as "T3 body") and a structural unit represented by the following formula (II) (Sometimes called "T2 body"). Furthermore, it is preferable that the polyorganosilsesquioxane of this invention has the structural unit represented by following formula (4).

The structural unit represented by the above formula (1) is usually a silsesquioxane structural unit (so-called T unit) represented by [RSiO _3/2 ]. In addition, R in the said formula represents a hydrogen atom or a monovalent organic group, and it is the same below. The structural unit represented by said formula (1) is formed by the hydrolysis and condensation reaction of the corresponding hydrolyzable trifunctional silane compound (specifically, the compound represented by following formula (a), for example).

R ¹ in formula (1) represents a group (monovalent group) containing a cationically polymerizable functional group. That is, the polyorganosilsesquioxane-based compound of the present invention is a cation-curable compound (cationically polymerizable compound) having at least a cationically polymerizable functional group in its molecule.

The "cationically polymerizable functional group" in the group containing the above-mentioned cationically polymerizable functional group is not particularly limited as long as it is cationic polymerizable, and examples thereof include epoxy groups, oxetanyl groups, and vinyl ether groups. base, vinyl phenyl, etc. As a cationic polymerizable functional group, an epoxy group is especially preferable from a viewpoint of the surface hardness (for example, F or more) of a resin layer.

Examples of the above-mentioned group containing a cationic polymerizable functional group include known or commonly used groups having an oxirane ring, and are not particularly limited. In terms of the curability of the curable composition, the surface hardness of the cured product (resin layer) or From the viewpoint of heat resistance, a group represented by the following formula (1a), a group represented by the following formula (1b), a group represented by the following formula (1c), and a group represented by the following formula (1d) are preferable. The group represented is more preferably a group represented by the following formula (1a), a group represented by the following formula (1c), and still more preferably a group represented by the following formula (1a).

In the above formula (1a), R ^1a represents a linear or branched alkylene group. Examples of linear or branched alkylene groups include methylene, methylmethylene, dimethylmethylene, ethylene, propylene, trimethylene, tetramethylene, Straight-chain or branched alkylene groups having 1 to 10 carbon atoms such as pentamethylene, hexamethylene, and decamethylene. Among them, R ^1a is preferably a linear alkylene group having 1 to 4 carbon atoms, or a branched chain having 3 or 4 carbon atoms, from the viewpoint of the surface hardness or curability of the cured product (resin layer). The alkylene group is more preferably an ethylidene group, a trimethylene group, and a propylidene group, and further preferably an ethylidene group or a trimethylene group.

In the above formula (1b), R ^1b represents a straight-chain or branched alkylene group, and the same groups as R ^1a can be exemplified. Among them, R ^1b is preferably a straight-chain alkylene group having 1 to 4 carbons or a branched chain having 3 or 4 carbons from the viewpoint of the surface hardness or curability of the cured product (resin layer). The alkylene group is more preferably an ethylidene group, a trimethylene group, and a propylidene group, and further preferably an ethylidene group or a trimethylene group.

In the above formula (1c), R ^1c represents a linear or branched alkylene group, and the same groups as R ^1a can be exemplified. Among them, R ^1c is preferably a straight-chain alkylene group having 1 to 4 carbons or a branched chain having 3 or 4 carbons from the viewpoint of the surface hardness or curability of the cured product (resin layer). The alkylene group is more preferably an ethylidene group, a trimethylene group, and a propylidene group, and further preferably an ethylidene group or a trimethylene group.

In the above formula (1d), R ^1d represents a straight-chain or branched alkylene group, and the same groups as R ^1a can be exemplified. Among them, R ^1d is preferably a straight-chain alkylene group having 1 to 4 carbons or a branched chain having 3 or 4 carbons from the viewpoint of the surface hardness or curability of the cured product (resin layer). The alkylene group is more preferably an ethylidene group, a trimethylene group, and a propylidene group, and further preferably an ethylidene group or a trimethylene group.

As R ¹ in the formula (1), the following group is particularly preferable: the group represented by the above formula (1a), and R ^1a is an ethylidene group [especially, 2-(3',4'-epoxy cyclohexyl) ethyl].

As the group containing the above-mentioned oxetane group, known or customary groups having an oxetane ring can be mentioned, without particular limitation, for example, oxetanyl itself, an oxetanyl-substituted A group (preferably an alkyl group having 1 to 10 carbons, more preferably an alkyl group having 1 to 5 carbons) containing hydrogen atoms (usually 1 or more, and preferably 1 hydrogen atom). From the viewpoint of the curability of the curable composition and the heat resistance of the cured product (resin layer), 3-oxocyclobutyl, oxetan-3-ylmethyl, 3-ethyloxetane Butane-3-ylmethyl, 2-(oxobutane-3-yl)ethyl, 2-(3-ethyloxybutane-3-yl)ethyl, 3-(oxobutane -3-ylmethoxy)propyl, 3-(3-ethyloxycyclobutan-3-ylmethoxy)propyl and the like.

As the group containing the above-mentioned vinyl ether group, known or conventional groups having a vinyl ether group can be mentioned, without particular limitation, for example, a vinyl ether group itself, a vinyl ether group substituted with an alkyl group (preferably a carbon number of 1 ~10, more preferably an alkyl group having 1 to 5 carbon atoms) hydrogen atoms (usually 1 or more, and preferably 1 hydrogen atom) are formed. From the viewpoint of the curability of the curable composition and the heat resistance of the cured product (resin layer), vinyloxymethyl, 2-(ethyleneoxy)ethyl, 3-(ethyleneoxy)propyl are preferred. Base etc.

As the group containing the above-mentioned vinylphenyl group, known or customary groups having vinylphenyl groups can be mentioned, without particular limitation, for example, vinylphenyl itself, vinylphenyl substituted alkyl (preferably carbon number 1 ~10, more preferably an alkyl group having 1 to 5 carbon atoms) hydrogen atoms (usually 1 or more, and preferably 1 hydrogen atom) are formed. From the viewpoint of the curability of the curable composition and the heat resistance of the cured product (resin layer), 4-vinylphenyl, 3-vinylphenyl, 2-vinylphenyl and the like are preferable.

The polyorganosilsesquioxane of the present invention may have only one structural unit represented by the above formula (1), or may have two or more structural units represented by the above formula (1).

Regarding the polyorganosilsesquioxane of the present invention, as the silsesquioxane structural unit [RSiO _3/2 ], in addition to the structural unit represented by the above formula (1), it may also have the following formula (2 ) represents the constituent unit.

The structural unit represented by the above formula (2) is usually a silsesquioxane structural unit (T unit) represented by [RSiO _3/2 ]. That is, the structural unit represented by said formula (2) is formed by the hydrolysis and condensation reaction of the corresponding hydrolyzable trifunctional silane compound (specifically, the compound represented by following formula (b), for example).

R in the above formula ( ² ) represents substituted or unsubstituted aryl, substituted or unsubstituted aralkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkane group, or substituted or unsubstituted alkenyl group. As said aryl group, a phenyl group, a tolyl group, a naphthyl group etc. are mentioned, for example. As said aralkyl group, a benzyl group, a phenethyl group, etc. are mentioned, for example. As said cycloalkyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group etc. are mentioned, for example. Examples of the above-mentioned alkyl group include linear or branched groups such as methyl, ethyl, propyl, n-butyl, isopropyl, isobutyl, second-butyl, third-butyl, and isopentyl. The alkyl group. As said alkenyl group, linear or branched alkenyl groups, such as vinyl group, allyl group, and isopropenyl group, are mentioned, for example.

Examples of the above-mentioned substituted aryl group, substituted aralkyl group, substituted cycloalkyl group, substituted alkyl group, and substituted alkenyl group include hydrogen in each of the above-mentioned aryl group, aralkyl group, cycloalkyl group, alkyl group, and alkenyl group. A part or all of the atoms or main chain skeleton are selected from ether group, ester group, carbonyl group, siloxane group, halogen atom (fluorine atom, etc.), acrylic group, methacrylic group, mercapto group, amino group and hydroxyl group (hydroxyl) At least one substituent group in the group formed.

Among them, R ² is preferably substituted or unsubstituted aryl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, more preferably substituted or unsubstituted aryl group, more preferably phenyl group.

The ratio of each of the above-mentioned silsesquioxane constituent units (the constituent units represented by the formula (1), the constituent units represented by the formula (2)) in the polyorganosilsesquioxane of the present invention can be determined according to the ratio used to form the The composition of the raw material (hydrolyzable trifunctional silane) of the constituent units can be adjusted appropriately.

In addition to the structural units represented by the above formula (1) and the structural units represented by the formula (2), the polyorganosilsesquioxane of the present invention may further have a structural unit selected from the above formula (1) And the structural unit represented by the silsesquioxane structural unit [RSiO _3/2 ], [R ₃ SO _1/2 ] other than the structural unit represented by formula (2) (so-called M unit), [R ₂ SiO ₂ At least one siloxane structural unit in the group consisting of a structural unit represented by [SiO _4/2 ] (so-called D unit) and a structural unit represented by [SiO _4/2] (so-called Q unit). In addition, as a silsesquioxane structural unit other than the structural unit represented by said formula (1) and the structural unit represented by formula (2), the structural unit etc. which are represented by following formula (3) are mentioned, for example.

When the polyorganosilsesquioxane of the present invention has the structural unit (T3 body) represented by the above formula (I) and the structural unit (T2 body) represented by the above formula (II), the ratio [T3 body/T2 body] is not particularly limited, for example, can be appropriately selected from the range of 5 or more (for example, 5 or more and 500 or less). The lower limit of the ratio [T3 body/T2 body] of an aspect of the polyorganosilsesquioxane of the present invention is preferably 5, more preferably 6, further preferably 7, and the upper limit is preferably It is less than 20, more preferably 18, more preferably 16, still more preferably 14. There exists a tendency for the surface hardness of a resin layer to improve by making the said ratio [T3 body/T2 body] 5 or more. By setting the above ratio [T3 body/T2 body] to less than 20 (preferably 18 or less), the compatibility with other components in the curable composition is improved, and the viscosity is also suppressed, so it is easy to use and easy to apply apply.

In another aspect of the polyorganosilsesquioxane of the present invention, the lower limit of the ratio [T3 body/T2 body] is preferably 20, more preferably 21, more preferably 23, and still more preferably 25, And the upper limit is preferably 500, more preferably 100, more preferably 50, and still more preferably 40. By setting the above ratio [T3 body/T2 body] to 20 or more, in addition to improving the surface hardness and adhesion, the surface is easy to become non-adhesive when it is made into an unhardened or semi-hardened resin layer, and the blocking resistance Raised while easily coiled into rolls. On the other hand, by setting the above-mentioned ratio [T3 body/T2 body] to 500 or less, the compatibility with other components in the curable composition is improved, and the viscosity is also suppressed, so it is easy to handle and easy to apply.

In addition, when the structural unit represented by said formula (I) is described in more detail, it is represented by following formula (I'). Moreover, when the structural unit represented by said formula (II) is described in more detail, it is represented by following formula (II'). In the structure represented by the following formula (I'), the three oxygen atoms bonded to silicon atoms are respectively bonded to other silicon atoms (silicon atoms not represented in formula (I')). On the other hand, in the structure represented by the following formula (II'), the two oxygen atoms located above and below the silicon atom are respectively bonded to other silicon atoms (silicon atoms not represented in the formula (II') Knot. That is, both the above-mentioned T3 body and T2 body are structural units (T units) formed by hydrolysis and condensation reactions of the corresponding hydrolyzable trifunctional silane compounds.

R a in the above formula (I) (the R ^a in the formula (I') is also the same) and R ^b in the formula (II) ⁽ the R ^b in the formula (II') is also the same) respectively represent cationic polymerizable Functional group, substituted or unsubstituted aryl, substituted or unsubstituted aralkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkyl, substituted or Unsubstituted alkenyl, or a hydrogen atom. Specific examples of R ^a and R ^b include the same ones as R ¹ in the above formula (1) and R ² in the above formula (2). Furthermore, R a in formula (I) and R ^b in formula (II ⁾ are respectively derived from the silicon atom bond in the hydrolyzable trifunctional silane compound used as the raw material of the polyorganosilsesquioxane of the present invention. Groups (groups other than alkoxy groups and halogen atoms; for example, R ¹ , R ² , hydrogen atoms, etc. in the following formulas (a) to (c)).

R ^c in the above formula (II) (the same is true for R ^c in the formula (II')) represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include linear or branched chain alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, and isobutyl. The alkyl group in ^R in the formula (II) is usually derived from the alkoxy group in the hydrolyzable silane compound used as the raw material of the polyorganosilsesquioxane of the present invention (for example, as the following X ¹ to X ³ Alkoxy, etc.) of the alkyl group.

The ratio [T3 body/T2 body] of the polyorganosilsesquioxane of the present invention can be obtained, for example, by ²⁹ Si-NMR spectrum measurement. In the ²⁹ Si-NMR spectrum, the silicon atom in the constituent unit (T3 body) represented by the above formula (I) and the silicon atom in the constituent unit (T2 body) represented by the above formula (II) are in different positions ( Chemical shift) shows the signal (peak), so by calculating the integral ratio of these peaks, the above-mentioned ratio [T3 body/T2 body] can be obtained. Specifically, for example, the polyorganosilsesquioxane in the present invention is represented by the above-mentioned formula (1), and has the composition that R ¹ is 2-(3',4'-epoxycyclohexyl)ethyl In the case of the unit, the signal of the silicon atom in the structure (T3 body) represented by the above formula (I) appears at -64~-70 ppm, and the signal of the silicon atom in the structure (T2 body) represented by the above formula (II) The atomic signal appears at -54~-60 ppm. Therefore, in this case, by calculating the integral ratio of the signal of -64~-70 ppm (T3 body) and the signal of -54~-60 ppm (T2 body), the above ratio [T3 body/T2 body] can be obtained ]. When R ¹ is a group containing a cationically polymerizable functional group other than 2-(3',4'-epoxycyclohexyl)ethyl, [T3 body/T2 body] can be obtained in the same manner.

The ²⁹ Si-NMR spectrum of the polyorganosilsesquioxane of the present invention can be measured, for example, by the following equipment and conditions. Measuring device: Trade name "JNM-ECA500NMR" (manufactured by JEOL Ltd.) Solvent: Deuterium chloroform Cumulative number of times: 1800 Measurement temperature: 25°C

When the ratio [T3 body/T2 body] of the polyorganosilsesquioxane of the present invention is within the above range (for example, 5 to 500), it means that in the polyorganosilsesquioxane of the present invention There is a certain amount of T2 bodies relative to T3 bodies. As such a T2 body, the structural unit represented by following formula (4), the structural unit represented by following formula (5), the structural unit represented by following formula (6), etc. are mentioned, for example. R ¹ in the following formula (4) and R ² in the following formula (5) are the same as R ¹ in the above formula (1) and R ² in the above formula (2), respectively. R ^c in the following formulas (4) to (6) is the same as R ^c in formula (II), and represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

The polyorganosilsesquioxane of the present invention may have any one of the cage-type, incomplete cage-type, ladder-type, and random-type silsesquioxane structures, and may also be combined with these silsesquioxane structures. 2 or more.

When the polyorganosilsesquioxane of the present invention has the structural unit represented by the above formula (4), the structural unit represented by the above formula (1) and the structural unit represented by the above formula (4) are relatively The ratio (total amount) of the total amount of oxane constituent units [all siloxane constituent units; the total amount of M units, D units, T units, and Q units] (100 mole %) is not particularly limited, and is preferably 55～100 mol%, more preferably 65～100 mol%, and then preferably 80～99 mol%. By setting the above ratio to 55 mol % or more, the curability of the curable composition is improved, and the surface hardness and adhesiveness of the cured product (resin layer) are significantly increased. In addition, the ratio of each silsesquioxane structural unit in the polyorganosilsesquioxane of this invention can be calculated from the composition of a raw material, NMR spectrum measurement, etc., for example.

The structural unit represented by the above formula (2) and the structural unit represented by the above formula (5) in the polyorganosilsesquioxane of the present invention are relative to the total amount of the siloxane structural units [all siloxane structural units The ratio (total amount) of the total amount of M unit, D unit, T unit and Q unit] (100 mol%) is not particularly limited, is preferably 0～70 mol%, is more preferably 0～60 mol mol%, and then preferably 0 ~ 40 mol%, especially preferably 1 ~ 15 mol%. By setting the above-mentioned ratio to 70 mol% or less, the ratio of the structural unit represented by the formula (1) and the structural unit represented by the formula (4) can be relatively increased, so the curability of the curable composition is improved, The surface hardness or adhesiveness of the cured product (resin layer) tends to increase further. On the other hand, there exists a tendency for the gas barrier property of a hardened|cured material (resin layer) to improve by making the said ratio into 1 mol% or more.

The structural unit represented by the above formula (1), the structural unit represented by the above formula (2), the structural unit represented by the above formula (4), and the above formula (5) in the polyorganosilsesquioxane of the present invention The ratio (total amount) of the indicated constituent units to the total amount of siloxane constituent units [all siloxane constituent units; the total amount of M units, D units, T units, and Q units] (100 mole%) It is not particularly limited, but it is preferably 60-100 mol%, more preferably 70-100 mol%, and more preferably 80-100 mol%. There exists a tendency for the surface hardness and adhesiveness of a hardened|cured material (resin layer) to further increase by making the said ratio into 60 mol% or more.

The polyorganosilsesquioxane of the present invention has a standard polystyrene-equivalent number average molecular weight (Mn) by gel permeation chromatography, which is not particularly limited, and can be appropriately selected from, for example, a range of 1,000 to 50,000. The lower limit of the number average molecular weight of one aspect of the polyorganosilsesquioxane of the present invention is preferably 1000, more preferably 1100, and the upper limit is preferably 3000, more preferably 2800, and more preferably 2600. By setting the number average molecular weight to 1000 or more, the heat resistance, scratch resistance, and adhesiveness of the cured product (resin layer) tend to be further improved. By setting the number average molecular weight to 3000 or less, the compatibility with other components in the curable composition is improved, and the heat resistance of the cured product (resin layer) tends to be further improved.

The lower limit of the number average molecular weight of another aspect of the polyorganosilsesquioxane of the present invention is preferably 2500, more preferably 2800, further preferably 3000, and the upper limit is preferably 50000, more preferably 10000, and more preferably 8000. By setting the number average molecular weight to 2500 or more, in addition to improving the heat resistance, scratch resistance, and adhesiveness of the cured product (resin layer), the surface becomes less sticky when it is made into an uncured or semi-hardened resin layer , the resistance to adhesion is improved, and it is easy to be wound into a roll. By setting the number average molecular weight to 50,000 or less, the compatibility with other components in the curable composition improves, and the heat resistance of the cured product (resin layer) tends to further improve.

The molecular weight dispersion (Mw/Mn) of the polyorganosilsesquioxane of the present invention in terms of standard polystyrene by gel permeation chromatography is not particularly limited, and can be appropriately selected from the range of 1.0 to 4.0. The lower limit of the molecular weight dispersion is preferably 1.0, more preferably 1.1, still more preferably 1.2. By making the molecular weight dispersity 1.1 or more, it tends to become liquid easily and usability improves. On the other hand, the upper limit of the molecular weight dispersion is preferably 4.0, more preferably 3.0, still more preferably 2.5 (for example, preferably 3.0, more preferably 2.0, still more preferably 1.9). By making the molecular weight dispersion degree 4.0 or less (for example, 3.0 or less), there exists a tendency for the surface hardness and adhesiveness of a hardened|cured material (resin layer) to further increase.

Furthermore, the number average molecular weight and molecular weight dispersion of the polyorganosilsesquioxane of the present invention can be measured by the following devices and conditions. Measuring device: Trade name "LC-20AD" (manufactured by Shimadzu Corporation) String: Shodex KF-801×2, KF-802 and KF-803 (manufactured by Showa Denko Co., Ltd.) Measuring temperature: 40°C Eluent: THF, sample concentration 0.1~0.2% by weight Flow rate: 1 mL/min Detector: UV-VIS detector (trade name "SPD-20A", manufactured by Shimadzu Corporation) Molecular weight: Standard polystyrene conversion

The 5% weight loss temperature (T _d5 ) of the polyorganosilsesquioxane of the present invention in air environment is not particularly limited, preferably above 330°C (for example, 330~450°C), more preferably above 340°C, More preferably, it is 350° C. or higher. When the 5% weight loss temperature is 330° C. or higher, the heat resistance of the cured product (resin layer) tends to be further improved. In particular, the ratio [T3 body/T2 body] of the polyorganosilsesquioxane of the present invention is 5 to 500, the number average molecular weight is 1,000 to 50,000, and the molecular weight dispersion is 1.0 to 4.0. 5% weight reduction temperature is controlled above 330°C. Furthermore, the 5% weight loss temperature is the temperature at the time point when the weight before heating is reduced by 5% when heating at a constant heating rate, and becomes an index of heat resistance. The above-mentioned 5% weight loss temperature can be measured by TGA (thermogravimetric analysis) in an air environment at a heating rate of 5° C./min.

The polyorganosilsesquioxane of the present invention can be produced by known or customary polysiloxane production methods without particular limitation, for example, by hydrolyzing one or more hydrolyzable silane compounds and condensation methods. Among them, as the above-mentioned hydrolyzable silane compound, a hydrolyzable trifunctional silane compound (compound represented by the following formula (a)) for forming the structural unit represented by the above-mentioned formula (1) must be used as an essential hydrolyzable silane compound .

More specifically, for example, represented by the following formula (a) as a hydrolyzable silane compound used to form the silsesquioxane constituent unit (T unit) in the polyorganosilsesquioxane of the present invention The polyorganosilsesquioxane of the present invention can be produced by hydrolyzing and condensing the compound represented by the following formula (b) and the compound represented by the following formula (c) if necessary.

The compound represented by the said formula (a) is a compound which forms the structural unit represented by the formula (1) in the polyorganosilsesquioxane of this invention. R ¹ in the formula (a) is the same as R ¹ in the above formula (1), and represents a group containing a cationically polymerizable functional group. That is, as R ¹ in the formula (a), it is preferably a group represented by the above formula (1a), a group represented by the above formula (1b), a group represented by the above formula (1c), a group represented by the above formula ( The base represented by 1d) is more preferably the base represented by the above formula (1a), the base represented by the above formula (1c), and more preferably the base represented by the above formula (1a), especially the above formula ( 1a), and R ^1a is an ethylenyl group [especially, 2-(3',4'-epoxycyclohexyl)ethyl].

X ¹ in the above formula (a) represents an alkoxy group or a halogen atom. Examples of the alkoxy group in X include: alkoxy groups having ¹ to 4 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, and isobutoxy. Moreover, examples of the halogen atom in X1 include ^a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among them, X ¹ is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group. In addition, three X ¹ may be respectively the same or different.

The compound represented by the said formula (b) is a compound which forms the structural unit represented by the formula (2) in the polyorganosilsesquioxane of this invention. R ² in the formula (b) is the same as R ² in the above formula (2), and represents a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted ring Alkyl, substituted or unsubstituted alkyl, or substituted or unsubstituted alkenyl. That is, R ² in formula (b) is preferably substituted or unsubstituted aryl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, more preferably substituted or an unsubstituted aryl group, more preferably a phenyl group.

X ² in the above formula (b) represents an alkoxy group or a halogen atom. Specific examples ^{of X2} include those exemplified as X1. Among them, X ² is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group. Furthermore, the three X ^2s may be the same or different.

The compound represented by the said formula (c) is a compound which forms the structural unit represented by the formula (3) in the polyorganosilsesquioxane of this invention. X ³ in the above formula (c) represents an alkoxy group or a halogen atom. Specific examples ^{of X3} include those exemplified as X1. Among them, X ³ is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group. Furthermore, the three X ³ may be the same or different.

As the hydrolyzable silane compound, a hydrolyzable silane compound other than the compounds represented by the above formulas (a) to (c) may be used in combination. Examples include: hydrolyzable trifunctional silane compounds other than the compounds represented by the above formulas (a) to (c), hydrolyzable monofunctional silane compounds forming M units, hydrolyzable bifunctional silane compounds forming D units, and hydrolyzable bifunctional silane compounds forming Q units. Unit hydrolyzable tetrafunctional silane compounds, etc.

The amount or composition of the above-mentioned hydrolyzable silane compound can be appropriately adjusted according to the desired structure of the polyorganosilsesquioxane of the present invention. For example, the amount of the compound represented by the above formula (a) is not particularly limited, but it is preferably 55 to 100 mol %, more preferably It is 65～100 mol%, and more preferably 80～99 mol%.

Also, the amount of the compound represented by the above formula (b) is not particularly limited, but it is preferably 0 to 70 mole %, more preferably 0 to 60 mol%, more preferably 0 to 40 mol%, especially preferably 1 to 15 mol%.

Furthermore, the ratio (total ratio) of the compound represented by the formula (a) to the compound represented by the formula (b) to the total amount (100 mol%) of the hydrolyzable silane compound used is not particularly limited. It is preferably 60-100 mol%, more preferably 70-100 mol%, and more preferably 80-100 mol%.

Moreover, when using 2 or more types together as said hydrolyzable silane compound, the hydrolysis and condensation reaction of these hydrolyzable silane compounds may be performed simultaneously, and may be performed sequentially. When performing the above reactions sequentially, the order of performing the reactions is not particularly limited.

The hydrolysis and condensation reaction of the said hydrolyzable silane compound may be performed in 1 stage, and may be divided into 2 or more stages and may be performed. For example, in order to efficiently produce the polyorganosilsesquioxane (hereinafter sometimes referred to as "low molecular weight polysilsesquioxane") of the present invention having the ratio [T3 body/T2 body] of less than 20 and/or a number average molecular weight of less than 2500, Organosilsesquioxane"), it is preferable to carry out the hydrolysis and condensation reaction in one stage. In addition, in order to efficiently produce the polyorganosilsesquioxane (hereinafter, sometimes referred to as "high molecular weight poly Organosilsesquioxane"), it is preferable to carry out the hydrolysis and condensation reaction in two or more stages (preferably two stages), that is, the above-mentioned low molecular weight polyorganosilsesquioxane is used as a raw material, and then carried out more than once hydrolysis and condensation reactions. In the following, low molecular weight polyorganosilsesquioxane obtained by performing hydrolysis and condensation reaction of hydrolyzable silane compound in one stage, and further hydrolysis and condensation reaction of low molecular weight polyorganosilsesquioxane are obtained to obtain high Although the aspect of the molecular weight polyorganosilsesquioxane is demonstrated, the manufacturing method of the polyorganosilsesquioxane of this invention is not limited to this.

In the case of carrying out the hydrolysis and condensation reaction of the present invention in two stages, it is preferable to obtain the ratio [T3 body/T2 body] of 5 or more and less than 20 in the hydrolysis and condensation reaction of the first stage. A low-molecular-weight polyorganosilsesquioxane having an average molecular weight of not less than 1,000 and not more than 2,500, and in the second stage, the above-mentioned A high molecular weight polyorganosilsesquioxane having a ratio [T3 body/T2 body] of 20 to 500 and a number average molecular weight of 2,500 to 50,000.

The hydrolysis and condensation reactions in the first stage may be performed in the presence or non-existence of a solvent. Among them, it is preferably carried out in the presence of a solvent. Examples of the solvent include: aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran, and dioxane; acetone, methyl ethyl ketone, methyl Ketones such as isobutyl ketone; methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate and other esters; N,N-dimethylformamide, N,N-dimethylacetamide and other amides Amines; Nitriles such as acetonitrile, propionitrile, and benzonitrile; Alcohols such as methanol, ethanol, isopropanol, butanol, etc. Among these solvents, ketones and ethers are preferred. In addition, a solvent may be used individually by 1 type, and may use it in combination of 2 or more types.

The usage amount of the solvent in the hydrolysis and condensation reaction in the first stage is not particularly limited, and it can be in the range of 0 to 2000 parts by weight relative to the total amount of 100 parts by weight of the hydrolyzable silane compound, depending on the required reaction time, etc. Make appropriate adjustments.

The hydrolysis and condensation reactions in the first stage are preferably carried out in the presence of a catalyst and water. The above-mentioned catalyst may be an acidic catalyst or an alkaline catalyst, and is preferably an alkaline catalyst in order to suppress the decomposition of cationic polymerizable functional groups such as epoxy groups. Examples of the acidic catalyst include: inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and boric acid; phosphates; carboxylic acids such as acetic acid, formic acid, and trifluoroacetic acid; methanesulfonic acid, trifluoromethanesulfonic acid, and p-toluenesulfonic acid Sulfonic acid such as acid; Solid acid such as activated clay; Lewis acid such as ferric chloride, etc. Examples of the alkaline catalyst include: hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide; hydrogens of alkaline earth metals such as magnesium hydroxide, calcium hydroxide, and barium hydroxide; Oxides; carbonates of alkali metals such as lithium carbonate, sodium carbonate, potassium carbonate, and cesium carbonate; carbonates of alkaline earth metals such as magnesium carbonate; lithium bicarbonate, sodium bicarbonate, sodium bicarbonate, potassium bicarbonate, cesium bicarbonate, etc. Bicarbonates of alkali metals; organic acid salts of alkali metals such as lithium acetate, sodium acetate, potassium acetate, and cesium acetate (e.g. acetate); organic acid salts of alkaline earth metals such as magnesium acetate (e.g. acetate); lithium methoxide, methanol Alkoxides of alkali metals such as sodium, sodium ethoxide, sodium isopropoxide, potassium ethoxide, and potassium tert-butoxide; phenates of alkali metals such as sodium phenoxide; triethylamine, N-methylpiperidine, 1,8 -Diacridine bicyclo[5.4.0]undec-7-ene, 1,5-diacribicyclo[4.3.0]non-5-ene and other amines (tertiary amines, etc.); pyridine, 2,2'- Nitrogen-containing aromatic heterocyclic compounds such as bipyridyl, 1,10-phenanthroline, etc. In addition, a catalyst may be used individually by 1 type, and may use it in combination of 2 or more types. In addition, the catalyst can also be used in a state of being dissolved or dispersed in water, a solvent, or the like.

The amount of the catalyst used in the hydrolysis and condensation reaction in the first stage is not particularly limited, and can be appropriately adjusted within the range of 0.002 to 0.200 mol relative to 1 mol of the total amount of the hydrolyzable silane compound.

The amount of water used in the hydrolysis and condensation reactions in the first stage is not particularly limited, and can be appropriately adjusted within the range of 0.5 to 20 moles relative to 1 mole of the total amount of the hydrolyzable silane compound.

The method of adding the above-mentioned water in the hydrolysis and condensation reaction in the first stage is not particularly limited, and the total amount of water used (the total amount used) may be added at one time, or may be added successively. When adding one by one, it may be added continuously or may be added intermittently.

As the reaction conditions for the hydrolysis and condensation reactions in the first stage, it is particularly important to select such reaction conditions that the above-mentioned ratio [T3 body/T2 body] of the low molecular weight polyorganosilsesquioxane becomes 5 or more and less than 20. The reaction temperature of the hydrolysis and condensation reaction in the first stage is not particularly limited, but is preferably 40-100°C, more preferably 45-80°C. By controlling the reaction temperature in the above-mentioned range, the above-mentioned ratio [T3 body/T2 body] tends to be more efficiently controlled to 5 or more and less than 20. Also, the reaction time of the hydrolysis and condensation reaction in the first stage is not particularly limited, but is preferably 0.1 to 10 hours, more preferably 1.5 to 8 hours. In addition, the hydrolysis and condensation reactions in the first stage may be performed under normal pressure, or may be performed under increased pressure or reduced pressure. Moreover, the environment during the hydrolysis and condensation reaction in the first stage is not particularly limited, for example, it can be any one of inert gas environments such as nitrogen atmosphere and argon atmosphere, and the presence of oxygen such as air, etc., preferably In an inert gas environment.

Low molecular weight polyorganosilsesquioxane can be obtained through the hydrolysis and condensation reaction in the first stage above. After completion of the hydrolysis and condensation reactions in the first stage, it is preferable to neutralize the catalyst in order to suppress the decomposition of cationic polymerizable functional groups such as ring-opening of epoxy groups. In addition, for example, it can be separated by washing with water, washing with acid, washing with alkali, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, etc., or a combination of these separation means. Separation and purification of molecular weight polyorganosilsesquioxane.

A high molecular weight polyorganosilsesquioxane can be produced by subjecting the low molecular weight polyorganosilsesquioxane obtained by the first stage hydrolysis and condensation reaction to the second stage hydrolysis and condensation reaction. The hydrolysis and condensation reactions in the second stage may be performed in the presence or non-existence of a solvent. When the second-stage hydrolysis and condensation reaction is performed in the presence of a solvent, the solvents listed for the first-stage hydrolysis and condensation reaction can be used. As the solvent for the hydrolysis and condensation reaction in the second stage, low-molecular-weight polyorganosilsesquioxane containing the reaction solvent and extraction solvent for the hydrolysis and condensation reaction in the first stage can be used as it is, or a part obtained by distillation. In addition, a solvent may be used individually by 1 type, and may use it in combination of 2 or more types.

When the solvent is used in the hydrolysis and condensation reaction of the second stage, its usage amount is not particularly limited, and it can be in the range of 0 to 2000 parts by weight relative to 100 parts by weight of low molecular weight polyorganosilsesquioxane , according to the required response time, etc. to be adjusted appropriately.

The hydrolysis and condensation reactions in the second stage are preferably carried out in the presence of a catalyst and water. The above-mentioned catalyst can use the catalyst listed in the hydrolysis and condensation reaction of the first stage. In order to suppress the decomposition of cationic polymerizable functional groups such as epoxy groups, it is preferably an alkaline catalyst, and more preferably sodium hydroxide, Hydroxides of alkali metals such as potassium hydroxide and cesium hydroxide; carbonates of alkali metals such as lithium carbonate, sodium carbonate, potassium carbonate, and cesium carbonate. In addition, a catalyst may be used individually by 1 type, and may use it in combination of 2 or more types. In addition, the catalyst can also be used in a state of being dissolved or dispersed in water, a solvent, or the like.

The amount of the above-mentioned catalyst used in the hydrolysis and condensation reaction in the second stage is not particularly limited, and it can be preferably 0.01 to 10,000 ppm, more preferably Adjust appropriately within the range of 0.1~1000 ppm.

The amount of water used in the hydrolysis and condensation reactions in the second stage is not particularly limited, but it can be preferably 10 to 100,000 ppm, more preferably 100 to Adjust appropriately within the range of 20000 ppm. If the amount of water used exceeds 100,000 ppm, the ratio [T3 body/T2 body] or the number average molecular weight of high molecular weight polyorganosilsesquioxane tends to be difficult to control within a specific range.

The method of adding the above-mentioned water in the hydrolysis and condensation reaction in the second stage is not particularly limited, and the total amount of water used (total usage amount) may be added at one time, or may be added successively. When adding one by one, it may be added continuously or may be added intermittently.

As the reaction conditions for the hydrolysis and condensation reactions in the second stage, it is particularly important to select such that the ratio [T3 body/T2 body] of the high molecular weight polyorganosilsesquioxane is 20 or more and 500 or less, and the number average molecular weight becomes 2500~50000 reaction conditions. The reaction temperature of the hydrolysis and condensation reaction in the second stage varies depending on the catalyst used and is not particularly limited, but is preferably 5 to 200°C, more preferably 30 to 100°C. By controlling the reaction temperature to the above-mentioned range, the above-mentioned ratio [T3 body/T2 body] and the number average molecular weight tend to be more efficiently controlled to a desired range. Also, the reaction time of the hydrolysis and condensation reaction in the second stage is not particularly limited, but is preferably 0.5 to 1000 hours, more preferably 1 to 500 hours. Also, by carrying out the hydrolysis and condensation reactions within the range of the above-mentioned reaction temperature, taking samples in due course, and monitoring the above-mentioned ratio [T3 body/T2 body] and the number average molecular weight while carrying out the reaction, it is also possible to obtain the desired product. The ratio [T3 body/T2 body], high molecular weight polyorganosilsesquioxane with number average molecular weight.

The hydrolysis and condensation reactions in the second stage can be performed under normal pressure, or under increased or reduced pressure. Moreover, the environment during the hydrolysis and condensation reaction in the second stage is not particularly limited, for example, it can be any one of inert gas environments such as nitrogen atmosphere and argon atmosphere, and the presence of oxygen such as air, etc., preferably In an inert gas environment.

High molecular weight polyorganosilsesquioxane can be obtained through the hydrolysis and condensation reaction in the second stage above. After completion of the hydrolysis and condensation reactions in the second stage, it is preferable to neutralize the catalyst in order to suppress the decomposition of cationic polymerizable functional groups such as ring-opening of epoxy groups. Further, for example, high concentration can be separated by washing with water, washing with acid, washing with alkali, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, etc., or a combination of these separation means. Separation and purification of molecular weight polyorganosilsesquioxane.

Since the polyorganosilsesquioxane of the present invention has the above-mentioned constitution, the resin layer obtained by curing the curable composition containing the polyorganosilsesquioxane as an essential component is endowed with high surface hardness and excellent properties. Bending durability, easy to form a resin layer that fully satisfies the above (conditions 1 to 5).

In the curable composition of the present invention, the polyorganosilsesquioxane of the present invention may be used alone or in combination of two or more.

The content (blending amount) of the polyorganosilsesquioxane of the present invention in the curable composition of the present invention is not particularly limited, but relative to the total amount (100% by weight) of the curable composition excluding the solvent, It is preferably at least 50% by weight and less than 100% by weight, more preferably 60 to 99% by weight, and still more preferably 70 to 95% by weight. By making content of the polyorganosilsesquioxane of this invention 50 weight% or more, there exists a tendency for the surface hardness and adhesiveness of a hardened|cured material (resin layer) to improve further. On the other hand, by setting the content of the polyorganosilsesquioxane of the present invention to less than 100% by weight (for example, 95% by weight or less), it is possible to contain a hardening catalyst, and to have one or more heat molecules in the following molecules: Compounds of polymerizable functional groups and one or more photopolymerizable functional groups, epoxy compounds, or fluorine-containing photopolymerizable resins, etc., can more efficiently harden the curable composition, and the surface hardness・Tendency to improve bending durability.

The ratio of the polyorganosilsesquioxane of the present invention to the total amount (100% by weight) of the cation-curable compound contained in the curable composition of the present invention is not particularly limited, but is preferably 60 to 99% by weight , more preferably 65 to 98% by weight, and more preferably 70 to 95% by weight. By making content of the polyorganosilsesquioxane of this invention 60 weight% or more, there exists a tendency for the surface hardness and adhesiveness of a hardened|cured material (resin layer) to improve further. On the other hand, by setting the content of the polyorganosilsesquioxane of the present invention to 99% by weight or less, it is possible to contain the following molecules having one or more thermally polymerizable functional groups and one or more photopolymerizable functional groups: Functional group compounds or epoxy compounds tend to improve surface hardness and bending durability.

(hardening catalyst) The curable composition of the present invention preferably further contains a curing catalyst. Among these, it is particularly preferable to contain a cationic polymerization initiator or a radical polymerization initiator as a curing catalyst, since the curing time until the stickiness can be further shortened.

The aforementioned cationic polymerization initiator is a compound capable of starting or accelerating the cationic polymerization reaction of the cation-curing compound such as the polyorganosilsesquioxane of the present invention. It does not specifically limit as said cationic polymerization initiator, For example, a photocationic polymerization initiator (photoacid generator), a thermal cationic polymerization initiator (thermal acid generator), etc. are mentioned.

As the above-mentioned photocationic polymerization initiator, well-known or commonly used photocationic polymerization initiators can be used, for example, cite salt (a salt of a ions and anions), a salt of iodonium (a salt of ions and anions), selenium salts (salt of selenium ion and anion), ammonium salt (salt of ammonium ion and anion), phosphonium salt (salt of phosphonium ion and anion), salt of transition metal complex ion and anion, etc. These can be used individually by 1 type or in combination of 2 or more types.

Examples of the above-mentioned permeate salts include [4-(4-biphenylsulfanyl)phenyl]-4-biphenylphenyl permetrix tris(pentafluoroethyl)trifluorophosphate, triphenyl permeate, Tri-p-tolyl permeate, tri-o-tolyl permeate, tris(4-methoxyphenyl) permeate, 1-naphthyl diphenyl permeate, 2-naphthyl diphenyl permeate, three (4 -Fluorophenyl) percited salt, tri-1-naphthyl percited salt, tris-2-naphthyl percited salt, tris(4-hydroxyphenyl) percited salt, diphenyl[4-(phenylthio)phenyl ] percited salt, 4-(p-tolylthio)phenyl bis(p-phenyl) percited salt and other triaryl percited salts; diphenylbenzoylmethyl percited salt, diphenyl 4-nitrobenzoylform Diaryl permeate salts such as base permeate, diphenylbenzyl permeate, diphenylmethyl permeate, etc.; phenylmethyl benzyl permeate, 4-hydroxyphenylmethyl benzyl permeate, Monoaryl permeicium salts such as oxyphenylmethyl benzyl permeicium salt; Dimethylbenzoyl methyl permeic acid salt, phenacyl tetrahydrothiophenium (phenacyl tetrahydrothiophenium) salt, dimethylbenzyl permeic acid salt And other trialkyl cobalt salts, etc.

As the above-mentioned diphenyl[4-(phenylthio)phenyl]conium salt, for example, diphenyl[4-(phenylthio)phenyl]percite hexafluoroantimonate, diphenyl[4-( Phenylthio)phenyl]perzium hexafluorophosphate, etc.

Examples of the above-mentioned iodonium salts include: trade name "UV9380C" (manufactured by Momentive Performance Materials Japan LLC, bis(4-dodecylphenyl)iodonium=hexafluoroantimonate 45% alkyl glycidyl ether solution), Product name "RHODORSIL PHOTOINITIATOR 2074" (manufactured by Rhodia Japan Co., Ltd., Tetrakis(pentafluorophenyl)borate=[(1-methylethyl)phenyl](methylphenyl)io), product name "WPI -124" (manufactured by Wako Pure Chemical Industries, Ltd.), diphenyliodonium salt, di-p-tolyliodonium salt, bis(4-dodecylphenyl)iodonium salt, bis(4-methoxybenzene) base) salt, etc.

Examples of the above-mentioned selenium salts include: triphenylselenium salt, tri-p-tolylselenium salt, tri-o-tolylselenium salt, tris(4-methoxyphenyl)selenium salt, 1-naphthyldiphenylselenide Salt and other triaryl selenide salts; Aryl selenium salts; trialkyl selenium salts such as dimethyl benzoyl methyl selenium salts, etc.

Examples of the above-mentioned ammonium salts include tetramethylammonium salts, ethyltrimethylammonium salts, diethyldimethylammonium salts, triethylmethylammonium salts, tetraethylammonium salts, trimethyl- Tetraalkylammonium salts such as n-propylammonium salts and trimethyl-n-butylammonium salts; pyrrolidinium salts such as N,N-dimethylpyrrolidinium salts and N-ethyl-N-methylpyrrolidinium salts Onium (pyrrolidinium) salt; imidazolinium (imidazolinium) salt such as N,N'-dimethylimidazolinium salt, N,N'-diethylimidazolinium salt; N,N'-dimethyltetrahydro Pyrimidinium salts, N,N'-diethyltetrahydropyrimidinium salts and other tetrahydropyrimidinium salts; N,N-dimethylmorpholinium salts, N,N-diethylmorpholine Onium salts and other morpholinium (morpholinium) salts; N,N-dimethylpiperidinium salts, N,N-diethylpiperidinium salts and other piperidinium (piperidinium) salts; N-methylpyridinium salt, N-ethylpyridinium salt and other pyridinium salts; N,N'-dimethylimidazolium salt and other imidazolium salts; N-methylquinolinium salt and other quinolinium (quinolium) salts ) salts; isoquinolinium salts such as N-methylisoquinolinium salts; thiazonium salts such as benzylbenzothiazolium salts; acridinium salts such as benzylacridinium salts, etc.

Examples of the above-mentioned phosphonium salts include: tetraarylphosphonium salts such as tetraphenylphosphonium salts, tetra-p-tolylphosphonium salts, and tetrakis(2-methoxyphenyl)phosphonium salts; triarylphosphonium salts such as triphenylbenzylphosphonium salts; phosphonium salts; tetraalkylphosphonium salts such as triethylbenzylphosphonium salts, tributylbenzylphosphonium salts, tetraethylphosphonium salts, tetrabutylphosphonium salts, triethylbenzoylmethylphosphonium salts, etc.

Examples of salts of transition metal complex ions include: (η5-cyclopentadienyl)(η6-toluene)Cr ⁺ , (η5-cyclopentadienyl)(η6-xylene)Cr ⁺ , etc. Salts of chromium complex cations; salts of iron complex cations such as (η5-cyclopentadienyl)(η6-toluene)Fe ⁺ , (η5-cyclopentadienyl)(η6-xylene)Fe ⁺ Wait.

Examples of anions constituting the above-mentioned salts include: SbF ₆ ^- , PF ₆ ^- , BF ₄ ^- , (CF ₃ CF ₂ ) ₃ PF ₃ ^- , (CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ^- , (C ₆ F ₅ ) ₄ B ^- , (C ₆ F ₅ ) ₄ Ga ^- , sulfonate anion (trifluoromethanesulfonate anion, pentafluoroethanesulfonate anion, nonafluorobutanesulfonate anion, methanesulfonate anion, benzenesulfonate anion anion, p-toluenesulfonate anion, etc.), (CF ₃ SO ₂ ) ₃ C ^- , (CF ₃ SO ₂ ) ₂ N ^- , perhalogenate ion, halogenated sulfonate ion, sulfate ion, carbonate ion, aluminate ion ions, hexafluorobismuthate ions, carboxylate ions, aryl borate ions, thiocyanate ions, nitrate ions, etc.

Examples of the aforementioned thermal cationic polymerization initiators include: aryl percite salts, aryl peroxide salts, allene-ion complexes, quaternary ammonium salts, aluminum chelate compounds, and boron trifluoride amine complexes. Wait.

As said aryl permeic acid salt, hexafluoroantimonate etc. are mentioned, for example. In the curable composition of the present invention, for example, trade names "SP-66", "SP-77" (the above are manufactured by ADEKA Co., Ltd.); trade names "San-Aid SI-60L", "San- Commercially available products such as "Aid SI-80L", "San-Aid SI-100L", and "San-Aid SI-150L" (the above are manufactured by Sanshin Chemical Industry Co., Ltd.). Examples of the aluminum chelate compound include ethylaluminum diisopropyl acetoacetate, aluminum tris(ethylacetoacetate), and the like. Moreover, examples of the boron trifluoride amine complex include boron trifluoride monoethylamine complex, boron trifluoride imidazole complex, boron trifluoride piperidine complex, and the like.

Furthermore, in the curable composition of the present invention, the curing catalyst may be used alone or in combination of two or more.

The content (blending amount) of the above-mentioned curing catalyst in the curable composition of the present invention is not particularly limited, but is preferably 0.01 to 3.0 parts by weight relative to 100 parts by weight of the polyorganosilsesquioxane of the present invention, More preferably 0.05 to 3.0 parts by weight, further preferably 0.1 to 1.0 parts by weight (for example, 0.3 to 1.0 parts by weight). By making the content of the curing catalyst 0.01 parts by weight or more, the curing reaction can be efficiently and sufficiently advanced, and the surface hardness and adhesiveness of the cured product (resin layer) tend to be further improved. On the other hand, by making content of a hardening catalyst 3.0 weight part or less, there exists a tendency for the storage stability of a curable composition to improve more, or to suppress the coloring of a hardened|cured material (resin layer).

(Compounds with one or more thermally polymerizable functional groups and one or more photopolymerizable functional groups in the molecule) The curable composition of the present invention preferably contains a compound having one or more thermally polymerizable functional groups and one or more photopolymerizable functional groups in the molecule (hereinafter, sometimes referred to as "compound A"). By containing the polyorganosilsesquioxane and compound A of the present invention in the curable composition of the present invention, the crosslinking density of the cured product can be effectively increased, and it is easy to give the cured product (resin layer) a higher surface Hardness and excellent bending durability.

The "thermally polymerizable functional group" of compound A is not particularly limited as long as it is a functional group that imparts polymerizability to compound A by heat. Examples include: hydroxyl group, epoxy group, oxetanyl group, vinyl ether The group etc. are preferably a hydroxyl group and an epoxy group from the viewpoint of the surface hardness and bending durability of the resin layer of the present invention. Furthermore, when the compound A has two or more thermally polymerizable functional groups, these thermally polymerizable functional groups may be respectively the same or different.

The "photopolymerizable functional group" of compound A is not particularly limited as long as it is a functional group that imparts polymerizability to compound A by light (such as ultraviolet light). Examples include (meth)acryl, vinyl, etc. Among them, a (meth)acryl group is preferable from the viewpoint of the surface hardness and bending durability of the resin layer of the present invention. Furthermore, when compound A has two or more photopolymerizable functional groups, these photopolymerizable functional groups may be respectively the same or different.

As long as the number of thermally polymerizable functional groups in one molecule of Compound A is 1 or more, it is not particularly limited, for example, it is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 or 2. Also, as long as the number of photopolymerizable functional groups in one molecule of compound A is one or more, it is not particularly limited, for example, it is preferably 1 to 5, more preferably 1 to 3, and even more preferably Preferably 1 or 2.

The functional group equivalent weight of the thermopolymerizable functional group of Compound A is not particularly limited, but is preferably 50-500, more preferably 80-480, and still more preferably 120-450. When the said functional group equivalent is less than 50, the bending durability of hardened|cured material (resin layer) may become inadequate. On the other hand, when the said functional group equivalent exceeds 500, the surface hardness of hardened|cured material (resin layer) may fall. In addition, the functional group equivalent of the thermopolymerizable functional group of compound A can be computed by the following formula. [The functional group equivalent weight of the thermally polymerizable functional group]=[the molecular weight of the compound A]/[the number of the thermally polymerizable functional groups possessed by the compound A]

The functional group equivalent weight of the photopolymerizable functional group of Compound A is not particularly limited, but is preferably 50-500, more preferably 80-480, and still more preferably 120-450. When the said functional group equivalent is less than 50, the bending durability of hardened|cured material (resin layer) may become inadequate. On the other hand, when the said functional group equivalent exceeds 500, the surface hardness of hardened|cured material (resin layer) may fall. In addition, the functional group equivalent of the photopolymerizable functional group of compound A can be computed by the following formula. [The functional group equivalent weight of the photopolymerizable functional group]=[the molecular weight of the compound A]/[the number of the photopolymerizable functional group that the compound A has]

Specific examples of compound A include: 3,4-epoxycyclohexylmethyl (meth)acrylate, glycidyl (meth)acrylate, tripropylene glycol diglycidyl ether di(meth)acrylate (a compound obtained by reacting (meth)acrylic acid with two epoxy groups of tripropylene glycol diglycidyl ether), tripropylene glycol diglycidyl ether half (meth)acrylate (by making (meth)acrylic acid and tripropylene glycol A compound obtained by reacting one epoxy group of diglycidyl ether), bisphenol A epoxy di(meth)acrylate (reacting (meth)acrylic acid and two epoxy groups of bisphenol A diglycidyl ether The compound obtained), bisphenol A epoxy half (meth) acrylate (the compound obtained by reacting (meth)acrylic acid or its derivatives with an epoxy group of bisphenol A diglycidyl ether), bisphenol A diglycidyl ether Phenol F Epoxy Di(meth)acrylate, Bisphenol F Epoxy Hemi(meth)acrylate, Bisphenol S Epoxy Di(meth)acrylate, Bisphenol S Epoxy Hemi(meth)acrylate Compounds with epoxy group and/or hydroxyl group and (meth)acryl group in one molecule; 3-oxocyclobutyl methyl (meth)acrylate, 3-methyl-3-oxocyclobutylmethyl (meth)acrylate ester, 3-ethyl-3-oxocyclobutylmethyl (meth)acrylate, 3-butyl-3-oxocyclobutylmethyl (meth)acrylate, 3-hexyl-3-oxocyclobutylmethyl (meth)acrylate Compounds with oxocyclobutyl and (meth)acryl groups in one molecule, such as esters; 2-vinyloxyethyl (meth)acrylate, 3-vinyloxypropyl (meth)acrylate, (meth)acrylate ) 1-methyl-2-vinyloxyethyl acrylate, 2-vinyloxypropyl (meth)acrylate, 4-vinyloxybutyl (meth)acrylate, 1-methyl (meth)acrylate -3-vinyloxypropyl ester, 1-vinyloxymethylpropyl (meth)acrylate, 2-methyl-3-vinyloxypropyl (meth)acrylate, 1,1 (meth)acrylate -Dimethyl-2-vinyloxyethyl ester, 3-vinyloxybutyl (meth)acrylate, 1-methyl-2-vinyloxypropyl (meth)acrylate, (meth)acrylic acid 2 - Vinyloxybutyl, 4-vinyloxycyclohexyl (meth)acrylate, 6-vinyloxyhexyl (meth)acrylate, 4-vinyloxymethylcyclohexylmethyl (meth)acrylate , 3-vinyloxymethylcyclohexylmethyl (meth)acrylate, 2-vinyloxycyclohexylmethyl (meth)acrylate, p-vinyloxymethylphenylmethyl (meth)acrylate, ( m-vinyloxymethylphenylmethyl methacrylate, o-vinyloxymethylphenylmethyl (meth)acrylate, 2-(ethyleneoxyethoxy)ethyl (meth)acrylate, ( 2-(ethyleneoxyisopropoxy)ethyl (meth)acrylate, 2-(ethyleneoxyethoxy)propyl (meth)acrylate, 2-(ethyleneoxyethoxy)(meth)acrylate ) isopropyl ester, 2-(ethyleneoxyisopropoxy)propyl (meth)acrylate, 2-(vinyloxyisopropoxy)isopropyl (meth)acrylate, (meth)acrylic acid 2 -(ethyleneoxyethoxy Ethoxy)ethyl ester, 2-(ethyleneoxyethoxyisopropoxy)ethyl (meth)acrylate, 2-(ethyleneoxyisopropoxyethoxy)ethyl (meth)acrylate , 2-(vinyloxyisopropoxyisopropoxy)ethyl (meth)acrylate, 2-(ethyleneoxyethoxyethoxy)propyl (meth)acrylate, (meth)acrylic acid 2-(vinyloxyethoxyisopropoxy)propyl, 2-(vinyloxyisopropoxyethoxy)propyl (meth)acrylate, 2-(ethyleneoxy)(meth)acrylate Isopropoxyisopropoxy)propyl, 2-(ethyleneoxyethoxyethoxy)isopropyl (meth)acrylate, 2-(ethyleneoxyethoxyisopropyl)(meth)acrylate oxy)isopropyl ester, 2-(vinyloxyisopropoxyethoxy)isopropyl (meth)acrylate, 2-(vinyloxyisopropoxyisopropoxy)(meth)acrylate Isopropyl ester, 2-(vinyloxyethoxyethoxyethoxy)ethyl (meth)acrylate, 2-(vinyloxyethoxyethoxyethoxyethoxyethoxy)(meth)acrylate base) ethyl ester, 2-(isopropenyloxyethoxy)ethyl (meth)acrylate, 2-(isopropenyloxyethoxyethoxy)ethyl (meth)acrylate, (methyl) 2-(isopropenyloxyethoxyethoxyethoxyethoxy)ethyl acrylate, 2-(isopropenyloxyethoxyethoxyethoxyethoxyethoxy)ethyl (meth)acrylate, ( Compounds having vinyl ether groups and (meth)acryl groups in one molecule, such as polyethylene glycol monovinyl methacrylate and polypropylene glycol monovinyl (meth)acrylate, etc.

From the viewpoint of the bending durability and surface hardness of the cured product (resin layer), it is preferable that the compound A has an epoxy group and/or a hydroxyl group as a thermally polymerizable functional group in one molecule, and an epoxy group as a photopolymerizable functional group. Compounds of (meth)acryloyl groups with sexual functional groups, specifically, 3,4-epoxycyclohexylmethyl (meth)acrylate, glycidyl (meth)acrylate, tripropylene glycol diglycidyl Glyceryl ether half (meth)acrylate, bisphenol A epoxy half (meth)acrylate, bisphenol F epoxy half (meth)acrylate, bisphenol S epoxy half (meth)acrylate, etc.

In addition, in the curable composition of this invention, compound A may be used individually by 1 type, and may use it in combination of 2 or more types. Compound A can be produced by a known method, for example, by combining a part of the thermally polymerizable functional group of a compound having two or more thermally polymerizable functional groups (such as epoxy groups, hydroxyl groups) in one molecule with It can be obtained by reacting carboxylic acid (such as acrylic acid, methacrylic acid, etc.) or its derivatives with photopolymerizable functional groups. In addition, as the above-mentioned compound A, for example, trade names "Lightester G", "Epoxy Ester 200PA", "Epoxy Ester 200PA-E5" (the above are manufactured by Kyoeisha Chemical Co., Ltd.), trade names "NK OLIGO EA1010N" can be used, for example. (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) and other commercially available products.

The content (blending amount) of the above-mentioned compound A in the curable composition of the present invention is not particularly limited, but in terms of solid content, it is preferably 1 ~100 parts by weight, more preferably 3~75 parts by weight, more preferably 5~50 parts by weight. There exists a tendency for the bending durability of a hardened|cured material (resin layer) to improve more by making content of compound A into 1 weight part or more. On the other hand, there exists a tendency for the surface hardness of hardened|cured material (resin layer) to be maintained by making content of compound A into 100 weight part or less.

(fluorine-containing photopolymerizable resin) The curable composition of the present invention preferably contains a fluorine-containing photopolymerizable resin. The fluorine-containing photopolymerizable resin is a resin (oligomer) having a fluorine-containing group such as a fluoroaliphatic hydrocarbon skeleton and a photopolymerizable functional group in the molecule. By containing the polyorganosilsesquioxane or compound A of the present invention and the fluorine-containing photopolymerizable resin in the curable composition of the present invention, the crosslinking density of the surface of the resin layer when it is made into a cured product can be effectively increased, and it has Improve the appearance of the surface of the cured product (resin layer) such as smoothness, improve the surface hardness, scratch resistance and antifouling properties. In particular, by blending the fluorine-containing photopolymerizable resin and the compound A into the curable composition of the present invention, the effect becomes remarkable.

Examples of the photopolymerizable functional group of the fluorine-containing photopolymerizable resin include the same ones as the "photopolymerizable functional group" of the above-mentioned compound A. In terms of the scratch resistance and antifouling properties of the resin layer of the present invention, From this point of view, a (meth)acryloyl group is preferable. Furthermore, when the fluorine-containing photopolymerizable resin has two or more photopolymerizable functional groups, these photopolymerizable functional groups may be respectively the same or different.

It is not particularly limited as long as the number of photopolymerizable functional groups in one molecule of the above-mentioned fluorine-containing photopolymerizable resin is one or more, for example, it is preferably 1 to 5, more preferably 1 to 3 indivual.

The "fluorine-containing group" of the fluorine-containing photopolymerizable resin is not particularly limited as long as it has a fluorine atom, and examples thereof include those having a fluoroaliphatic hydrocarbon skeleton. Examples of the fluoroaliphatic hydrocarbon skeleton include fluorocarbons such as fluoromethane, fluoroethane, fluoropropane, fluoroisopropane, fluorobutane, fluoroisobutane, fluorobutane, fluoropentane, and fluorohexane. _1-10 alkanes etc.

These fluoroaliphatic hydrocarbon skeletons only need to have at least a part of the hydrogen atoms substituted with fluorine atoms. From the viewpoint of improving the scratch resistance, sliding properties, and antifouling properties of the resin layer, it is preferred that all the hydrogen atoms be substituted with fluorine atoms. Perfluoroaliphatic hydrocarbon skeleton with fluorine atoms.

Furthermore, the fluoroaliphatic hydrocarbon skeleton can form a polyfluoroalkylene ether skeleton as a repeating unit via an ether bond. The fluoroaliphatic hydrocarbon group as a repeating unit may be at least one selected from the group consisting of fluoromethylene, fluoroethyl, fluoropropyl, fluoroisopropyl and other fluoro C _1-4 alkylene groups . The repeating number (polymerization degree) of the polyfluoroalkylene ether unit is, for example, 10-3000, preferably 30-1000, more preferably 50-500.

The above-mentioned fluorine-containing photopolymerizable resin may have a silicone-containing group in addition to the above-mentioned "photopolymerizable functional group" and "fluorine-containing group". The fluorine-containing photopolymerizable resin further has a polysiloxane-containing group, which improves the affinity with the polyorganosilsesquioxane of the present invention, thereby improving the surface hardness and scratch resistance of the cured product (resin layer) , Antifouling tendency. The polysiloxane-containing group is a group with a polyorganosiloxane skeleton, as long as it is a polyorganosiloxane formed by M units, D units, T units, and Q units. Usually, it is better to use a polyorganosiloxane composed of D units. The formation of polyorganosiloxane. As the organic group of polyorganosiloxane, C _1-4 alkyl group and aryl group are usually used, and methyl group and phenyl group (especially methyl group) are commonly used. The repeating number (polymerization degree) of the siloxane unit is, for example, 2-3000, preferably 3-2000, more preferably 5-1000.

As the above-mentioned fluorine-containing photopolymerizable resin, commercially available products can be used. E", "MEGAFAC RS-76-E", "MEGAFAC RS-76-NS", "MEGAFAC RS-78", "MEGAFAC RS-90" (the above are manufactured by DIC Co., Ltd.); trade name "Ftergent 601AD" , "Ftergent 601ADH2", "Ftergent 602A", "Ftergent 650AC", "Ftergent 681" (the above are manufactured by NEOS Co., Ltd.), etc.

These fluorine-containing photopolymerizable resins may be used alone or in combination of two or more.

The content (blending amount) of the above-mentioned fluorine-containing photopolymerizable resin in the curable composition of the present invention is not particularly limited, and it is based on solid content, relative to 100 parts by weight of the polyorganosilsesquioxane of the present invention , such as 0.01 to 15 parts by weight, preferably 0.05 to 10 parts by weight, more preferably 0.01 to 5 parts by weight, and more preferably 0.2 to 3 parts by weight. By making content of the fluorine-containing photopolymerizable resin 0.01 weight part or more, there exists a tendency for the abrasion resistance of hardened|cured material (resin layer) and antifouling property to improve further.

(epoxy compound) The above-mentioned curable composition may contain epoxy compounds other than the polyorganosilsesquioxane of the present invention (hereinafter, may be simply referred to as "epoxy compounds"). By containing an epoxy compound in addition to the polyorganosilsesquioxane of the present invention, a cured product (resin layer) having high surface hardness and excellent flexibility, flexibility and workability can be formed.

As the above-mentioned epoxy compound, a well-known and commonly used compound having one or more epoxy groups (oxirane ring) in the molecule can be used, without particular limitation, examples include: alicyclic epoxy compounds (alicyclic rings) Oxygen resin), aromatic epoxy compound (aromatic epoxy resin), aliphatic epoxy compound (aliphatic epoxy resin), etc. Among them, alicyclic epoxy compounds are preferred.

As the above-mentioned alicyclic epoxy compound, there are known and commonly used compounds having one or more alicyclic rings and one or more epoxy groups in the molecule, without particular limitation, for example: (1) having the following compounds in the molecule: The above-mentioned epoxy group (called "alicyclic epoxy group"), the epoxy group is composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring; (2) the epoxy group directly utilizes a single bond and Compounds with alicyclic bonds; (3) Compounds with alicyclic and glycidyl ether groups in the molecule (glycidyl ether type epoxy compounds), etc.

As the compound having an alicyclic epoxy group in the molecule of the above (1), any compound that is known and used can be used. Among them, the alicyclic epoxy group is preferably an epoxycyclohexyl group, and is particularly preferably a compound represented by the following formula (i).

In the above formula (i), Y represents a single bond or a linking group (a divalent group having one or more atoms). Examples of the linking group include: a divalent hydrocarbon group, an alkenylene group in which a part or all of the carbon-carbon double bond is epoxidized, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, and a plurality of such groups. The basis of the connection and so on. One or more hydrogen atoms of the cyclohexane ring in formula (i) may be substituted with a substituent such as an alkyl group having 1 to 6 carbon atoms.

Examples of the divalent hydrocarbon group include linear or branched alkylene groups having 1 to 18 carbon atoms, divalent alicyclic hydrocarbon groups, and the like. Examples of linear or branched alkylene groups having 1 to 18 carbon atoms include methylene, methylmethylene, dimethylmethylene, ethylidene, propylidene, and trimethylene Base etc. Examples of the divalent alicyclic hydrocarbon group include: 1,2-cyclopentyl, 1,3-cyclopentyl, cyclopentylene, 1,2-cyclohexyl, 1,3-cyclopentyl Divalent cycloalkylene groups (including cycloalkylene groups) such as hexyl, 1,4-cyclohexylene, and cyclohexylene.

As the alkenylene group in the above-mentioned alkenylene group in which part or all of the carbon-carbon double bond is epoxidized (sometimes referred to as "epoxyalkenyl group"), for example, vinyl group, propenyl group, 1- Butenyl, 2-butenyl, butadienyl, pentenyl, hexenyl, heptenyl, octenyl and other straight or branched chains with 2 to 8 carbon atoms Alkenyl, etc. In particular, the epoxidized alkenylene group is preferably an epoxidized alkenylene group having all carbon-carbon double bonds, more preferably an epoxidized alkenylene group having 2 to 4 carbon atoms having all carbon-carbon double bonds. base.

Representative examples of the alicyclic epoxy compounds represented by the above formula (i) include (3,4,3',4'-diepoxy)bicyclohexane, the following formula (i-1 )~(i-10) represented compounds, etc. Furthermore, l and m in the following formulas (i-5) and (i-7) represent integers of 1 to 30, respectively. R' in the following formula (i-5) is an alkylene group with 1 to 8 carbons, among which, methylene, ethylidene, propylidene, isopropylidene and other carbons with 1 to 3 straight or branched chain alkylene. n1 to n6 in the following formulas (i-9) and (i-10) represent integers of 1 to 30, respectively. In addition, examples of the alicyclic epoxy compound represented by the above formula (i) include 2,2-bis(3,4-epoxycyclohexyl)propane, 1,2-bis(3,4- Epoxycyclohexyl)ethane, 2,3-bis(3,4-epoxycyclohexyl)oxirane, bis(3,4-epoxycyclohexylmethyl)ether, etc.

As a compound which said (2) epoxy group is directly bonded to an alicyclic ring by a single bond, the compound etc. which are represented by following formula (ii) are mentioned, for example.

In formula (ii), R'' represents a group (p-valent organic group) obtained by removing p hydroxyl groups (-OH) from the structural formula of p-hydric alcohol, and p and n represent natural numbers respectively. Examples of the p-hydric alcohol [R''(OH) _p ] include polyalcohols such as 2,2-bis(hydroxymethyl)-1-butanol (alcohols having 1 to 15 carbon atoms, etc.). p is preferably 1 to 6, and n is preferably 1 to 30. When p is 2 or more, the n in the bases in each () (inside parentheses) may be the same or different. As the compound represented by the above formula (ii), specifically, 1,2-epoxy-4-(2-oxirane of 2,2-bis(hydroxymethyl)-1-butanol base) cyclohexane adduct [For example, a trade name "EHPE3150" (manufactured by Daicel Co., Ltd.) etc. can be used] and the like.

Examples of the compound having an alicyclic ring and a glycidyl ether group in the molecule (3) above include glycidyl ethers of alicyclic alcohols (especially alicyclic polyhydric alcohols). More specifically, for example, 2,2-bis[4-(2,3-epoxypropoxy)cyclohexyl]propane, 2,2-bis[3,5-dimethyl-4- (2,3-Epoxypropoxy)cyclohexyl]propane and other bisphenol A type epoxy compounds are hydrogenated (hydrogenated bisphenol A type epoxy compounds); bis[o,o-(2,3 -Glycidoxy)cyclohexyl]methane, bis[o,p-(2,3-glycidoxy)cyclohexyl]methane, bis[p,p-(2,3-glycidoxy )cyclohexyl]methane, bis[3,5-dimethyl-4-(2,3-epoxypropoxy)cyclohexyl]methane and other bisphenol F-type epoxy compounds hydrogenated (hydrogenated bisphenol F type epoxy compounds); hydrogenated biphenol type epoxy compounds; hydrogenated phenol novolac type epoxy compounds; hydrogenated cresol novolak type epoxy compounds; hydrogenated cresol novolak type epoxy compounds of bisphenol A; hydrogenated naphthalene Type epoxy compounds; hydrogenated epoxy compounds of epoxy compounds obtained from trisphenol methane; hydrogenated epoxy compounds of the following aromatic epoxy compounds, etc.

Examples of the above-mentioned aromatic epoxy compounds include those obtained by condensation reaction of bisphenols [for example, bisphenol A, bisphenol F, bisphenol S, bisphenol fennel, etc.] and epihalohydrin. Epi-Bis type glycidyl ether type epoxy resin; high-molecular weight Epi-Bis type glycidyl ether obtained by further performing addition reaction of these Epi-Bis type glycidyl ether type epoxy resins with the above-mentioned bisphenols Type epoxy resin; Formaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, willow aldehyde, etc.] polyols obtained by condensation reaction and epihalohydrin condensation reaction obtained novolak · alkyl type glycidyl ether type epoxy resin; Two phenol skeletons are bonded to the 9-position of the oxene ring, and the oxygen atoms obtained by removing hydrogen atoms from the hydroxyl groups of the phenol skeletons are respectively bonded to glycidyl groups directly or through alkyleneoxy groups. Epoxy compounds, etc.

As the above-mentioned aliphatic epoxy compounds, for example, glycidyl ethers of alcohols (q is a natural number) not having a q-valent ring structure; monobasic or polycarboxylic acids [for example, acetic acid, propionic acid, butyric acid, stearic acid glycidyl esters of adipic acid, adipic acid, sebacic acid, maleic acid, itaconic acid, etc.]; epoxy resins of oils with double bonds, such as epoxidized linseed oil, epoxidized soybean oil, epoxidized castor oil, etc. compounds; epoxides of polyolefins (including polydienes) such as epoxidized polybutadiene, etc. Furthermore, examples of alcohols that do not have a q-valent ring structure include: monohydric alcohols such as methanol, ethanol, 1-propanol, isopropanol, and 1-butanol; ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, Dihydric alcohols such as polypropylene glycol; glycerin, diglycerin, erythritol, trimethylolethane, trimethylolpropane, neopentylthritol, dipenteoerythritol, sorbitol, etc. Alcohol etc. Also, the q-hydric alcohol may be polyether polyol, polyester polyol, polycarbonate polyol, polyolefin polyol, or the like.

The said epoxy compound may be used individually by 1 type, and may use it in combination of 2 or more types. The epoxy compound is preferably an alicyclic epoxy compound from the viewpoint of the surface hardness, flexibility, and bending durability of the cured product (resin layer), and more preferably (2) an epoxy group that utilizes a single bond directly. The compound bonded to the alicyclic ring is particularly preferably a compound represented by the above formula (ii) [for example, a trade name "EHPE3150" (manufactured by Daicel Co., Ltd.) etc. can be used].

The content (blending amount) of the above-mentioned epoxy compound is, for example, 0.5 to 100 parts by weight, preferably 1 to 80 parts by weight, more preferably 100 parts by weight of the total amount of the polyorganosilsesquioxane of the present invention. Best is 5～50 parts by weight. By setting the content of the epoxy compound to 0.5 parts by weight or more, the surface hardness of the cured product (resin layer) further increases, and the softness, flexibility, workability, and bending durability tend to be more excellent. On the other hand, there exists a tendency for the abrasion resistance of hardened|cured material to improve more by making content of the said epoxy compound into 100 weight part or less.

(Silicon dioxide particles with (meth)acryl group-containing groups on the surface) The curable composition of the present invention may contain "silicon dioxide particles having a (meth)acryl group-containing group on the surface". The surface of the silicon dioxide particles having (meth)acryl group-containing groups is due to the presence of numerous hydroxyl groups (Si-OH groups) on the surface of the silicon dioxide particles, and the hydroxyl groups are combined with the above-mentioned polyorganic times of the present invention when hardened. The semisiloxane reacts to increase the crosslink density of the polyorganosilsesquioxane after hardening. In addition, the (meth)acryl groups in the plurality of silica particles are bonded to each other during curing, thereby increasing the crosslink density after curing. By increasing the crosslink density after curing in this way, the scratch resistance in the resin layer is improved. Also, if a layer (functional layer) having functions such as antifouling properties or low reflectivity is provided on the resin layer, the adhesion between the resin layer and the functional layer may be weak, and the functional layer may be peeled off, and there may be cases where it does not matter. The condition of recoatability. However, when the above-mentioned silica particles are used, recoatability can be imparted, and processability (processing suitability) when the above-mentioned functional layer is provided on the surface of the resin layer can also be improved.

Furthermore, it is considered that the above-mentioned silica particles can impart stability to the curable composition by having (meth)acryl groups on the surface. The so-called stability mentioned above means that in the preparation stage of the hardening composition before hardening, the above-mentioned silicon dioxide particles react with polyorganosilsesquioxane, and the viscosity of the hardening composition will not increase significantly (gelation) or curing. In the case of using ordinary silica particles ( _SiO2 particles) that do not have functional groups such as (meth)acryl group-containing groups on the surface, the silica particles aggregate with each other, and the curable composition gels The risk of transformation. The above-mentioned silica particles may have functional groups other than (meth)acryl groups (such as polysiloxane modification groups). In addition, (meth)acryl is a generic term for acryl (acryl) and methacryl (methacryl).

The above-mentioned silica particles can be used as a dispersion in a state of being dispersed in a known or customary general dispersion medium such as water or an organic solvent. Moreover, what made the silica particle react with the silane coupling agent which has a (meth)acryl group containing group can be used as said silica particle. As the above-mentioned silica particles, for example, trade names "BYK-LPX22699", "NANOBYK-3650", "NANOBYK-3651", and "NANOBYK-3652" (the above are manufactured by BYK-Chemie Japan Co., Ltd.) can be used.

The particle size of the above-mentioned silicon dioxide particles is, for example, 1-100 nm, preferably 3-50 nm, more preferably 5-30 nm.

When the curable composition of the present invention contains silica particles having a (meth)acryl group-containing group on the surface, the ratio is, for example, relative to 100 parts by weight of the polyorganosilsesquioxane of the present invention, 0.01 to 20 parts by weight, preferably 0.05 to 15 parts by weight, more preferably 0.01 to 10 parts by weight, and more preferably 0.2 to 5 parts by weight. By making the ratio of the said silica particle 0.01 weight part or more, the external appearance of the surface of a resin layer can be made favorable, and sufficient recoatability can be provided. Moreover, the surface hardness of a resin layer can be improved by making the ratio of a silica particle into 20 weight part or less.

(silicon acrylate) The curable composition of the present invention may contain "silicon acrylate". Silicon acrylate (polysiloxane acrylate) is one of the additives with at least silicon atom and (meth)acryl group. The silicon acrylate mentioned above may have a functional group (such as a hydroxyl group) other than the (meth)acryl group. The aforementioned silicon acrylate may be silicon diacrylate, silicon triacrylate, silicon tetraacrylate, silicon pentaacrylate, silicon hexaacrylate, silicon heptaacrylate, or silicon octaacrylate. The above-mentioned silicone acrylate can effectively increase the cross-linking density of the resin layer surface when the resin layer is formed by using the above-mentioned polyorganosilsesquioxane together in the curable composition, and can improve the smoothness of the surface of the resin layer. It improves the appearance of hardness, scratch resistance and anti-fouling properties of the surface. In addition, (meth)acryl is a generic term for acryl (acryl) and methacryl (methacryl).

The above-mentioned silicone acrylate can be used as a dispersion in a state of being dispersed in a well-known or customary normal dispersion medium such as an organic solvent (eg, acetone, toluene, methanol, ethanol). As the silicon acrylate, for example, trade names "KRM8479", "EBECRYL 350", and "EBECRYL 1360" (manufactured by Daicel-allnex Co., Ltd.) can be used.

When the curable composition of the present invention contains the above-mentioned silicone acrylate, its ratio is, for example, 0.01 to 15 parts by weight, preferably 0.05 to 10 parts by weight, relative to 100 parts by weight of the above-mentioned polyorganosilsesquioxane, More preferably 0.01～5 parts by weight, more preferably 0.2～3 parts by weight. When the ratio of the above-mentioned silicon acrylate is 0.01 parts by weight or more, scratch resistance and antifouling property can be improved when it is made into a resin layer. Moreover, by making the ratio of silicon acrylate into 15 weight part or less, the surface hardness at the time of making it into a resin layer can be raised further.

In terms of further improving the appearance of the resin layer, increasing the surface hardness, and improving the scratch resistance, it is preferable to use both silicon acrylate and silicon dioxide particles having a (meth)acryl group-containing group on the surface. Regarding the case where both of the silicon acrylate and the above-mentioned silicon dioxide particles are contained, the ratio of the silicon acrylate to the total of the above-mentioned silicon dioxide particles is, for example, 0.01 to 100 parts by weight of the above-mentioned polyorganosilsesquioxane 20 parts by weight, preferably 0.05 to 15 parts by weight, more preferably 0.01 to 10 parts by weight, and more preferably 0.2 to 5 parts by weight. By making the said ratio into 0.01 weight part or more, the abrasion resistance at the time of making it into a resin layer can be improved. Moreover, the surface hardness at the time of making it into a resin layer can be improved more by making the said ratio into 20 weight part or less.

(leveling agent) The curable composition of the present invention may have a leveling agent. As said leveling agent, the silicone type leveling agent which has a hydroxyl group etc. are mentioned, for example. Among them, the leveling agent is set not to contain the above-mentioned fluorine-containing photopolymerizable resin.

As the silicone-based leveling agent, commercially available silicone-based leveling agents can be used, for example, the product names "BYK-300", "BYK-301/302", "BYK-306", "BYK -307", "BYK-310", "BYK-315", "BYK-313", "BYK-320", "BYK-322", "BYK-323", "BYK-325", "BYK-330 ", "BYK-331", "BYK-333", "BYK-337", "BYK-341", "BYK-344", "BYK-345/346", "BYK-347", "BYK-348 ", "BYK-349", "BYK-370", "BYK-375", "BYK-377", "BYK-378", "BYK-UV3500", "BYK-UV3510", "BYK-UV3570", "BYK-3550", "BYK-SILCLEAN3700", "BYK-SILCLEAN3720" (the above are manufactured by BYK-Chemie Japan Co., Ltd.); product names "AC FS 180", "AC FS 360", "ACS 20" (the above manufactured for Algin Chemie); trade names "Polyflow KL-400X", "Polyflow KL-400HF", "Polyflow KL-401", "Polyflow KL-402", "Polyflow KL-403", "Polyflow KL-404" ( The above are manufactured by Kyoeisha Chemical Co., Ltd.); trade names "KP-323", "KP-326", "KP-341", "KP-104", "KP-110", "KP-112" ( The above are manufactured by Shin-Etsu Chemical Co., Ltd.); trade names "LP-7001", "LP-7002", "8032 ADDITIVE", "57 ADDITIVE", "L-7604", "FZ-2110", "FZ- 2105", "67 ADDITIVE", "8618 ADDITIVE", "3 ADDITIVE", "56 ADDITIVE" (manufactured by Dow Corning Toray Co., Ltd.).

As the above-mentioned fluorine-based leveling agent, a commercially available fluorine-based leveling agent can be used, for example, the trade name "OPTOOL DSX", "OPTOOL DAC-HP" (the above are manufactured by Daikin Industries Co., Ltd.); the trade name "Surflon S-242", "Surflon S-243", "Surflon S-420", "Surflon S-611", "Surflon S-651", "Surflon S-386" (manufactured by AGC Seimi Chemical Co., Ltd.) ; Trade name "BYK-340" (manufactured by BYK-Chemie Japan Co., Ltd.); Trade name "AC110a", "AC100a" (the above are manufactured by Algin Chemie); Trade name "MEGAFAC F-114", "MEGAFAC F-410 ", "MEGAFAC F-444", "MEGAFAC EXP TP-2066", "MEGAFAC F-430", "MEGAFAC F-472SF", "MEGAFAC F-477", "MEGAFAC F-552", "MEGAFAC F-553 ", "MEGAFAC F-554", "MEGAFAC F-555", "MEGAFAC R-94", "MEGAFAC RS-72-K", "MEGAFAC RS-75", "MEGAFAC F-556", "MEGAFAC EXP TF -1367", "MEGAFAC EXP TF-1437", "MEGAFAC F-558", "MEGAFAC EXP TF-1537" (manufactured by DIC Corporation); trade names "FC-4430", "FC-4432" ( The above are manufactured by Sumitomo 3M Co., Ltd.); trade names "Ftergent 100", "Ftergent 100C", "Ftergent 110", "Ftergent 150", "Ftergent 150CH", "Ftergent A-K", "Ftergent 501", "Ftergent 250 ", "Ftergent 251", "Ftergent 222F", "Ftergent 208G", "Ftergent 300", "Ftergent 310", "Ftergent 400SW" (manufactured by NEOS Co., Ltd.); product names "PF-136A", " PF-156A", "PF-151N", "PF-636", "PF-6320", "PF-656", "PF-652 0", "PF-651", "PF-652", "PF-3320" (manufactured by Kitamura Chemical Co., Ltd.) and other commercially available products.

Examples of the above-mentioned polysiloxane-based leveling agent having a hydroxyl group include polyether-modified polyether groups introduced into the main chain or side chain of polyorganosiloxane skeleton (polydimethylsiloxane, etc.) Polyorganosiloxane, polyester-modified polyorganosiloxane with polyester group introduced into the main chain or side chain of polyorganosiloxane skeleton, polyorganosiloxane introduced into (meth)acrylic resin Alkanes polysiloxane modified (meth)acrylic resin, etc. In these leveling agents, the hydroxyl group may have a polyorganosiloxane skeleton, and may also have a polyether group or a polyester group. As a commercial item of such a leveling agent, a brand name "BYK-370", "BYK-SILCLEAN3700", "BYK-SILCLEAN3720" etc. can be used, for example.

When the curable composition of the present invention contains the aforementioned leveling agent, its ratio is, for example, 0.01 to 20 parts by weight, preferably 0.05 to 15 parts by weight, relative to 100 parts by weight of the polyorganosilsesquioxane of the present invention. part, more preferably 0.01 to 10 parts by weight, and more preferably 0.2 to 5 parts by weight. When there is too little ratio of a leveling agent, the surface smoothness of a resin layer may fall, and when too much, the surface hardness of a resin layer may fall.

The curable composition of the present invention may further contain, as other optional components, precipitated silica, wet silica, fumed silica, calcined silica, titanium oxide, aluminum oxide, Glass, quartz, aluminosilicate, iron oxide, zinc oxide, calcium carbonate, carbon black, silicon carbide, silicon nitride, boron nitride and other inorganic fillers, using organohalosilane, organoalkoxysilane, organosilazane Inorganic fillers treated with such fillers as organosilicon compounds; fine powders of organic resins such as polysiloxane resins, epoxy resins, and fluororesins; fillers such as conductive metal powders such as silver and copper, hardening aids, Solvents (organic solvents, etc.), stabilizers (antioxidants, ultraviolet absorbers, light-resistant stabilizers, heat stabilizers, heavy metal deactivators, etc.), flame retardants (phosphorus-based flame retardants, halogen-based flame retardants, inorganic-based Flame retardants, etc.), flame retardant additives, reinforcing materials (other fillers, etc.), nucleating agents, coupling agents (silane coupling agents, etc.), lubricants, waxes, plasticizers, mold release agents, impact modifiers , Hue modifiers, clearing agents, rheology modifiers (fluidity modifiers, etc.), processability modifiers, colorants (dyes, pigments, etc.), antistatic agents, dispersants, defoamers, anti-pinhole agents , surface modifier (slipping agent, etc.), matting agent, defoamer, foam suppressor, defoamer, antibacterial agent, preservative, viscosity regulator, tackifier, photosensitizer, foaming agent and other commonly used additives. These additives may be used alone or in combination of two or more.

(Manufacturing method of curable composition) The curable composition of the present invention is not particularly limited, and can be prepared by stirring and mixing the above-mentioned components while heating at room temperature or if necessary. Furthermore, the curable composition can be used as a one-liquid composition in which each component is pre-mixed as it is, for example, it can also be used as a mixture of two or more components stored in advance at a specific ratio before use. Composition of multi-liquid system (for example, 2-liquid system).

The curable composition of the present invention is not particularly limited, but is preferably liquid at room temperature (about 25°C). More specifically, the above-mentioned curable composition is measured by the viscosity at 25°C of a liquid diluted to 20% of a solvent [especially a curable composition (solution) with a ratio of 20% by weight of methyl isobutyl ketone]. It is preferably 300 to 20000 mPa·s, more preferably 500 to 10000 mPa·s, and still more preferably 1000 to 8000 mPa·s. There exists a tendency for the heat resistance of a resin layer to improve further by making the said viscosity into 300 mPa*s or more. On the other hand, by setting the above-mentioned viscosity to 20000 mPa·s or less, it tends to be easy to prepare or use the curable composition, and it tends to make it difficult for air bubbles to remain in the resin layer. Furthermore, the viscosity of the curable composition was measured using a viscometer (trade name "MCR301", manufactured by Anton Paar Co., Ltd.) under the conditions of a swing angle of 5%, a frequency of 0.1 to 100 (1/s), and a temperature of 25°C. Determination.

The resin layer in the present invention can be obtained by polymerizing the cation-curable compound (polyorganosilsesquioxane of the present invention, etc.) contained in the above-mentioned curable composition and curing it.

In order to further improve the recoatability of the resin layer, surface treatments such as corona discharge treatment, plasma discharge treatment, ozone exposure treatment, and excimer treatment can be performed on the surface of the resin layer to modify the surface by corona discharge irradiation. . Among them, corona discharge treatment is more preferable at the point that recoatability can be easily improved.

Corona discharge treatment is to process the surface of the resin layer by generating an uneven electric field around the sharper electrode (needle electrode) to generate a continuous discharge. Plasma discharge treatment is the process of processing the surface of the resin layer by discharging in the atmosphere to generate activated positive and negative charged particles. The ozone exposure treatment is, for example, a treatment of processing the surface of the resin layer by generating ozone by ultraviolet irradiation using a low-pressure mercury lamp or the like in the presence of oxygen, for example. Excimer treatment is a process of processing the surface of the resin layer by ultraviolet irradiation or laser irradiation using an excimer lamp in a vacuum state.

Examples of the functional layer that can be provided on the resin layer include layers having functions such as scratch resistance, abrasion resistance, stain resistance (stain resistance), fingerprint resistance, and antireflection (low reflection). The functional layer is a commonly known or customary functional layer that has the functions listed above and is used in the resin layer of display devices such as mobile phones or smart phones. Examples of materials constituting the functional layer include: acrylic-based materials, fluorine-based materials, and polysiloxane-based materials. As a method of providing the functional layer on the resin layer, a method using the same coating method as the laminated film described below, a method using vapor deposition or sputtering, and the like are exemplified.

(Manufacturing method of laminated film) The laminated film of the present invention can be produced according to known or customary hard coating film production methods, and the production method is not particularly limited, and can be produced by the following method: by coating the above-mentioned curable composition on at least one side of the support material to form a resin layer by curing the curable composition.

The curing method of the above-mentioned resin layer can be appropriately selected from known methods, for example, a method of irradiating and/or heating an active energy ray can be mentioned. As the above-mentioned active energy rays, for example, any one of infrared rays, visible light, ultraviolet rays, X-rays, electron beams, α rays, β rays, and γ rays may be used. Among them, ultraviolet rays are preferable in terms of excellent usability.

The hardening conditions of the above-mentioned resin layer by irradiation of active energy rays can be appropriately adjusted according to the type or energy of the irradiated active energy rays, the shape or size of the resin layer, etc., and are not particularly limited. In the case of ultraviolet ray irradiation, For example, it is preferably about 1 to 1000 mJ/cm ² . Furthermore, for the irradiation of active energy rays, for example, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, carbon arcs, metal halide lamps, sunlight, LED lamps, lasers, etc. can be used. After the irradiation of active energy rays, heat treatment (annealing, aging) may be further performed to further progress the hardening reaction.

Conditions for hardening by heating in the above-mentioned resin layer are not particularly limited, for example, preferably 30 to 200°C, more preferably 50 to 190°C. The hardening time can be appropriately set.

The laminated film of the present invention can be produced by a roll-to-roll method because it is composed of a resin layer excellent in flexibility and processability. By producing the laminated film of the present invention in a roll-to-roll manner, its productivity can be significantly improved. As a method of manufacturing the laminated film of the present invention in a roll-to-roll manner, a known or conventional manufacturing method of a roll-to-roll manner can be used, and there is no particular limitation, and the following methods can be exemplified: The step of the body (step A); by applying a curable composition to at least one surface of the unrolled support, and then, if necessary, drying the solvent to remove the curable composition to harden to form a resin layer The step (step B); and thereafter, the step of rewinding the obtained laminate into a roll (step C) is taken as a necessary step, and these steps are carried out continuously (steps A~C). Furthermore, the method may also include steps other than steps A to C.

[foldable device] Since the laminated film of the present invention has high surface hardness and excellent bending durability, it can be suitably used as a surface protection material for foldable devices that are folded and used in addition to the surface protection materials of ordinary image display devices. . Flexible devices include, for example, mobile information terminals such as smartphones, tablets, or wearable terminals. For example, the laminated film of the present invention includes displays for these flexible devices (such as touch panels, wearable Displays used in terminals, organic EL displays, etc.), protective films, barrier films, TFT substrates, etc. Since the foldable device of the present invention has the laminated film of the present invention having excellent bending durability, no cracks will occur in the resin layer even if it is repeatedly bent and stretched, and it has excellent reliability. In addition, foldable devices such as mobile information terminals provided with the above-mentioned laminated film having excellent transparency have excellent visibility. [Example]

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited by these examples. Furthermore, the determination of the molecular weight of the product was performed using Alliance HPLC System 2695 (manufactured by Waters), Refractive Index Detector 2414 (manufactured by Waters), column: Tskgel GMH _HR -M×2 (manufactured by Tosoh Co., Ltd.), guard column: Tskgel guard column H _HR L (manufactured by Tosoh Co., Ltd.), column oven: COLUMN HEATER U-620 (manufactured by Sugai), solvent: THF, and measurement conditions: 40°C. Also, the ratio [T3 body/T2 body] of the T2 body and the T3 body in the product was measured by ²⁹ Si-NMR spectrum measurement using JEOL ECA500 (500 MHz).

Production example 1: Production of low molecular weight polyorganosilsesquioxane containing epoxy groups Put it in a 1000 ml flask (reaction vessel) equipped with a thermometer, a stirring device, a reflux condenser and a nitrogen gas introduction tube, under a nitrogen stream Add 277.2 millimoles (68.30 g) of 2-(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3.0 millimoles (0.56 g) of phenyltrimethoxysilane and 275.4 g of acetone, and heat up to 50°C. After adding 7.74 g (2.8 millimoles as potassium carbonate) of 5% potassium carbonate aqueous solution to the mixture obtained above in 5 minutes, 2800.0 millimoles (50.40 g) of water were added over 20 minutes. Furthermore, no significant temperature rise occurred during the addition. Thereafter, polycondensation reaction was performed for 5 hours under a nitrogen gas flow while maintaining 50°C. Then, while cooling the reaction solution, 137.70 g of methyl isobutyl ketone and 100.60 g of 5% saline were injected. This solution was transferred to a 1 L separating funnel, and 137.70 g of methyl isobutyl ketone was added again, followed by washing with water. After liquid separation, extract the water layer, wash with water until the lower layer becomes neutral, and separate the upper layer, then distill off the solvent from the upper layer under the conditions of 1 mmHg and 50°C to obtain 75.18 g of A colorless, transparent and liquid product of 23% by weight of methyl isobutyl ketone (epoxy group-containing low molecular weight polyorganosilsesquioxane). The product was analyzed, and the number average molecular weight was 2235, and the molecular weight dispersion was 1.54. The ratio [T3 body/T2 body] of the above product calculated from the ²⁹ Si-NMR spectrum was 11.9. The ¹ H-NMR chart and the ²⁹ Si-NMR chart of the obtained epoxy group-containing low-molecular-weight polyorganosilsesquioxane obtained are shown in FIG. 3 , respectively.

Production Example 2: Production of High Molecular Weight Polyorganosilsesquioxane Containing Epoxy Groups Into a 1000 ml flask (reaction vessel) equipped with a thermometer, a stirring device, a reflux condenser and a nitrogen introduction tube, under a nitrogen stream Add the mixture (75 g) containing the epoxy-group-containing low-molecular-weight polyorganosilsesquioxane obtained in Production Example 1, relative to the substantial content of the epoxy-group-containing low-molecular-weight polyorganosilsesquioxane Add 100 ppm (5.6 mg) of potassium hydroxide and 2,000 ppm (112 mg) of water, take a sample at 80°C for 18 hours and measure the molecular weight. As a result, the number average molecular weight Mn rises to 6,000, and then cools to room temperature , add 300 mL of methyl isobutyl ketone, and add 300 mL of water, wash with water repeatedly, thereby remove the alkali component and concentrate, thus obtaining 74.5 g of a colorless, transparent and liquid product containing 25% by weight of methyl isobutyl ketone Product (high molecular weight polyorganosilsesquioxane containing epoxy group 1). The product was analyzed, and the number average molecular weight was 6176, and the molecular weight dispersion was 2.31. The ratio [T3 body/T2 body] of the above product calculated from the ²⁹ Si-NMR spectrum was 50.2. The ¹ H-NMR chart of the obtained epoxy group-containing high molecular weight polyorganosilsesquioxane 1 is shown in FIG. 5 , and the ²⁹ Si-NMR chart is shown in FIG. 6 .

Example 1: Production of hard coat film A mixed solution having a blending ratio shown in Table 1 was prepared and used as a hard coat liquid (curable composition). Using a wire bar coater #14, the hard coating solution obtained above was applied to a PEN film (trade name "Teonex Q65 HWA", Teijin Co., Ltd. After the surface was manufactured), it was placed in an oven at 150°C for 2 minutes, and then, it was irradiated with ultraviolet light at an illuminance of 600 mJ/cm ² using a high-pressure mercury lamp (manufactured by EYE GRAPHICS Co., Ltd.). Thereafter, heat treatment was performed at 150° C. for 60 minutes to harden the coating film of the hard coating liquid, thereby producing a hard coating film having a hard coating layer.

[Table 1]

Embodiment 2～5: the manufacture of hard coating film A hard coat film was produced in the same manner as in Example 1 except that the thickness of the hard coat layer was changed to 20 to 50 μm.

Example 6: Manufacture of a hard coat film A hard coat film was produced in the same manner as in Example 1, except that the hard coat liquid having the blending ratio shown in Table 2 was used, and the thickness of the hard coat layer was changed to 40 μm. . [Table 2]

Example 7: Manufacture of hard coat film A hard coat film was produced in the same manner as in Example 1, except that the hard coat liquid having the blending ratio shown in Table 3 was used, and the thickness of the hard coat layer was changed to 40 μm. . [table 3]

Example 8: Manufacture of a hard coat film A hard coat film was produced in the same manner as in Example 1, except that the hard coat liquid having the blending ratio shown in Table 4 was used to change the thickness of the hard coat layer to 40 μm. . [Table 4]

Comparative Examples 1 to 3: Manufacture of Hard Coating Film Using the hard coating solution of the blending ratio shown in Table 5, the thickness of the hard coating layer was changed to 40 μm, except that the hard coating film was produced in the same manner as in Example 1. coating film. [table 5]

The following evaluation was performed about the hard coat film obtained by the Example and the comparative example. The results are shown in Table 6.

＜Haze and total light transmittance＞ The haze and total light transmittance of the hard coating film obtained above were measured using the haze meter (Nippon Denshoku Industries Co., Ltd. make, NDH-5000W).

＜Surface Hardness (Pencil Hardness)＞ The pencil hardness of the hard coat surface in the hard coat film obtained above was evaluated based on JIS K5600-5-4 (750-g load).

<Scratch resistance> For the hard coat surface of the hard coat film obtained above, #0000 steel wool was reciprocated with a load of 1000 g/cm ² , and the presence or absence of scratches on the hard coat surface was confirmed. As for the surface of the hard coat layer, scratch resistance was evaluated by the number of times until scratches were confirmed. In addition, when the scar was not confirmed even after 1000 round-trips or more, it is indicated as "1 K<".

＜Bending (1) (cylindrical mandrel method)＞ Regarding the flexibility of the hard coat film obtained above, the surface of the hard coat layer becomes concave (inside), using a cylindrical mandrel, and according to JIS K5600-5-1, the surface of the hard coat layer is not Bendability (1) was evaluated by the bending radius (mm) of cracks.

＜Bending (2) (cylindrical mandrel method)＞ Regarding the flexibility of the hard coat film obtained above, the hard coat surface becomes convex (outside), using a cylindrical mandrel, and according to JIS K5600-5-1, on the surface of the hard coat Bendability (2) was evaluated by bending radius (mm) without cracks.

＜Continuous bending durability (1)＞ The continuous bending durability of the hard coat film obtained above was measured using the planar object no-load U-shaped stretch tester (made by Yuasa System Co., Ltd., Z-044). The measurement is performed with the surface of the hard coat as a depression (inside), at a bending radius of 2.5 mm, at a speed of 30 to 60 times/minute, and the number of times until the hard coat is cracked is defined as the bending durability (1) (Refer to Figures 1 and 2). In addition, when no cracks occurred even after 100,000 times or more, it was expressed as "100 K<".

＜Bending durability (2)＞ The continuous bending durability of the hard coat film obtained above was measured using the planar object no-load U-shaped stretch tester (made by Yuasa System Co., Ltd., Z-044). The measurement is performed with the surface of the hard coat as convex (outside), at a bending radius of 4.0 mm, at a speed of 30 to 60 times per minute, and the number of times until the hard coat is cracked is defined as the bending durability (2 ) (refer to Figure 1, 2). In addition, when no cracks occurred even after 100,000 times or more, it was expressed as "100 K<".

＜Water contact angle＞ The water contact angle (°) of the surface of the hard coat film obtained above (surface of the hard coat layer) was measured by a droplet method.

[Table 6]

Components used in Examples and Comparative Examples are as follows. [resin] Production Example 1: Epoxy-group-containing low-molecular-weight polyorganosilsesquioxane obtained in Production Example 1 (polyorganosilsesquioxane of the present invention) 200PA-E5: Trade name "Epoxy Ester200PA-E5", tripropylene glycol diglycidyl ether hemi(meth)acrylate (a combination of more than one thermally polymerizable functional group and more than one photopolymerizable functional group in the molecule) Compounds), manufactured by Kyorongsha Chemical Co., Ltd. Lightester G: Trade name "Lightester G", glycidyl methacrylate (a compound having one or more thermally polymerizable functional groups and one or more photopolymerizable functional groups in the molecule), Kyoeisha Chemical Co., Ltd. manufacture EA-1010N: trade name "NK OLIGO EA1010N", bisphenol A epoxy hemiacrylate (compound with more than one thermally polymerizable functional group and more than one photopolymerizable functional group in the molecule), Shin Nakamura Chemical Manufacturing Co., Ltd. EHPE3150, trade name "EHPE3150" (a compound in which the epoxy group is directly bonded to an alicyclic ring using a single bond), manufactured by Daicel Co., Ltd. Celloxide 2021P: Trade name "Celloxide 2021P", 3,4-epoxycyclohexylmethyl(3,4-epoxy)cyclohexanecarboxylate, manufactured by Daicel Co., Ltd. [polymerization initiator] CPI-310PG: Trade name "CPI-310PG", photocationic polymerization initiator, manufactured by San-Apro Co., Ltd. CPI-210S: Trade name "CPI-210S", photocationic polymerization initiator, manufactured by San-Apro Co., Ltd. [Fluorine-containing photopolymerizable resin] FT601ADH2: Trade name "Ftergent 601ADH2", manufactured by NEOS Co., Ltd. RS-76-E: Trade name "MEGAFAC RS-76-E", manufactured by DIC Co., Ltd. [Surface conditioner] Surflon S243: Trade name "Surflon S243" (fluorine-based leveling agent), manufactured by AGC Seimi Chemical Co., Ltd. [solvent] MIBK: methyl isobutyl ketone MEK: methyl ethyl ketone

Variations of the present invention described above are described below. [1] A laminated film comprising a support and a resin layer laminated on at least one side of the support, characterized in that: the resin layer (in the case of the resin layer being layered on both sides of the above-mentioned support is optional) A resin layer) fully satisfies the following (Condition 1) and (Condition 2). (Condition 1) The pencil hardness of the resin layer surface of the above laminated film in the pencil hardness test (750 g load) stipulated in JIS K5600-5-4 (1999) is F or more. (Condition 2) The bending durability (1) in the following bending durability test (1) is 50,000 times or more. Bending durability test (1): In the state where the self-laminated film is unfolded, it is bent 180° along the direction in which the surface of the resin layer becomes concave with a bending radius of 2.5 mm, and the action of unfolding it again is set once, and the time is 30~ When the above-mentioned operation is performed at a speed of 60 times/minute, the number of times until the resin layer of the laminated film is cracked is used as an index of bending durability (1) [2] The laminated film described in the above [1], Wherein, the above-mentioned pencil hardness is more than 1H (preferably more than 2H, more preferably more than 3H, more preferably more than 4H, more preferably more than 5H, more preferably more than 6H, more preferably 7H above, more preferably above 8 H, especially preferably above 9 H). [3] The laminated film described in [1] or [2] above, wherein the bending durability (1) is 60,000 or more (preferably 70,000 or more, more preferably 80,000 or more, More preferably, it is at least 90,000 times, more preferably at least 100,000 times, further preferably at least 150,000 times, especially preferably at least 200,000 times). [4] A laminated film comprising a support, and a resin layer laminated on at least one side of the support, characterized in that: the resin layer (in the case of the resin layer being layered on both sides of the above-mentioned support is optional) - resin layer) sufficiently satisfy the following (Condition 1) and (Condition 3). (Condition 1) The pencil hardness of the resin layer surface of the above laminated film in the pencil hardness test (750 g load) stipulated in JIS K5600-5-4 (1999) is F or more. (Condition 3) The bending durability (2) in the following bending durability test (2) is 10,000 times or more. Bending durability test (2): In the state where the self-laminated film is unfolded, it is bent 180° along the convex direction of the surface of the resin layer with a bending radius of 4.0 mm, and the action of unfolding it again is set once, and the time is 30~ When the above-mentioned operation is performed at a speed of 60 times/minute, the number of times until the resin layer of the laminated film is cracked is used as an index of bending durability (2) [5] The laminated film described in the above [4], Wherein, the above-mentioned pencil hardness is more than 1H (preferably more than 2H, more preferably more than 3H, more preferably more than 4H, more preferably more than 5H, more preferably more than 6H, more preferably 7H above, more preferably above 8 H, especially preferably above 9 H). [6] The laminated film described in [4] or [5] above, wherein the bending durability (2) is 20,000 or more (preferably 30,000 or more, more preferably 40,000 or more, More preferably at least 50,000 times, more preferably at least 60,000 times, more preferably at least 70,000 times, more preferably at least 80,000 times, more preferably at least 90,000 times, more preferably at least 100,000 times, and even more preferably The best is more than 150,000 times, and the best is more than 200,000 times). [7] The laminated film according to any one of the above [1] to [6], wherein the resin layer (any resin layer when there are resin layers on the double-sided layer of the support) is further The following (condition 4) is fully satisfied. (Condition 4) In the cylindrical mandrel test specified in JIS K5600-5-1 (1999) where the surface of the resin layer of the laminated film becomes convex, the bending radius is 5 mm (preferably 4.5 mm, more Preferably 4.0 mm, more preferably 3.5 mm, more preferably 3.0 mm, more preferably 2.5 mm, especially 2.0 mm), and no cracks occur on the surface of the resin layer [8] as above [1] to The laminated film according to any one of [7], wherein the water contact angle of the surface of the above-mentioned resin layer (when there are resin layers on both sides of the above-mentioned support) is 95° or more (preferably more than 96°, more preferably more than 97°, more preferably more than 98°, more preferably more than 99°, more preferably more than 100°, more preferably more than 101°, more preferably more than 102°, More preferably, it is 103° or more, further preferably, it is 104° or more, and most preferably, it is 105° or more). [9] The laminated film according to any one of the above [1] to [8], wherein the above-mentioned resin layer (any resin layer when there are resin layers on the double-layered layer of the above-mentioned support) is further The following (condition 5) is fully satisfied. (Condition 5) While using #0000 steel wool to apply a load of 1 kg/cm ² , rub the surface of the above resin layer back and forth 30 times (preferably 100 times, more preferably 200 times, more preferably 300 times) , more preferably 500 times, more preferably 700 times, further preferably 1000 times, especially preferably 2000 times) in the steel wool resistance test, no scratches were visually observed. [10] The laminated film according to any one of the above [1] to [9], wherein the above-mentioned resin layer (any resin layer when there is a resin layer on the double-layered layer of the above-mentioned support) The haze is 1.0% or less (preferably 0.5% or less, more preferably 0.1% or less).

[11] The laminated film described in any one of [1] to [10] above, which has a haze of 7% or less (preferably 6% or less, more preferably 5% or less, more preferably 4% or less , and more preferably 3% or less, especially preferably 2% or less, most preferably 1% or less). [12] The laminated film according to any one of [1] to [11] above, which has a total light transmittance of 85% or more (preferably 90% or more). [13] The laminated film described in any one of the above [1] to [12], which has a thickness (total thickness of the support/resin layer) of 1 to 10000 (preferably 10 to 1000 μm, more preferably 15 to 800 μm, more preferably 20 to 700 μm, especially preferably 30 to 500 μm).

[14] The laminated film according to any one of the above [1] to [13], wherein the support is a polyester film (especially PET, PEN), a polyimide film, a cyclic polyolefin film , polycarbonate film, TAC film, or PMMA film (preferably polyester film (especially PET, PEN), or polyimide film). [15] The laminated film according to any one of the above [1] to [14], wherein the support has a thickness of 1 to 1000 μm (preferably 5 to 500 μm, more preferably 10 to 400 μm) , more preferably 15-400 μm, further preferably 20-300 μm, especially preferably 25-200 μm). [16] The laminated film according to any one of [1] to [15] above, wherein the support has a haze of 7% or less (preferably 6% or less, more preferably 5% or less, more preferably Preferably it is 4% or less, more preferably 3% or less, especially preferably 2% or less, most preferably 1% or less). [17] The laminated film according to any one of [1] to [16] above, wherein the total light transmittance of the support is 85% or more (preferably 90% or more).

[18] The laminated film according to any one of the above [1] to [17], wherein the resin layer has a thickness of 1 to 100 μm (preferably 2 to 80 μm, more preferably 3 to 60 μm) , and more preferably 5~50 μm, most preferably 10~40 μm). [19] The laminated film according to any one of [1] to [18] above, wherein the resin layer has a total light transmittance of 85% or more (preferably 90% or more). [20] The laminated film described in any one of the above [1] to [19], wherein the arithmetic average roughness R _a of the resin layer is 0.1 to 20 nm (preferably 0.1~10 nm, more preferably 0.1~5 nm).

[式（1）中，R¹ 表示含有陽離子聚合性官能基之基] [23]如上述[22]中所記載之積層膜，其中，上述陽離子聚合性官能基係選自由環氧基、氧環丁烷基、乙烯醚基及乙烯苯基所組成之群中之至少1種（較佳為環氧基）。 [24]如上述[22]或[23]中所記載之積層膜，其中，上述含有陽離子聚合性官能基之基係選自由下述式（1a）所表示之基、下述式（1b）所表示之基、下述式（1c）所表示之基及下述式（1d）所表示之基所組成之群中之至少1種（較佳為選自由下述式（1a）所表示之基及下述式（1c）所表示之基所組成之群中之至少1種，進而較佳為下述式（1a）所表示之基）。

[上述式（1a）中，R^1a 表示直鏈或支鏈狀之伸烷基]

[上述式（1b）中，R^1b 表示直鏈或支鏈狀之伸烷基]

[上述式（1c）中，R^1c 表示直鏈或支鏈狀之伸烷基]

[上述式（1d）中，R^1d 表示直鏈或支鏈狀之伸烷基] [25]如上述[22]至[24]中任一項所記載之積層膜，其中，R¹ 為下述基：上述式（1a）所表示之基，且R^1a 為伸乙基[其中尤其為，2-(3',4'-環氧環己基)乙基]。[21] The laminated film according to any one of the above [1] to [20], wherein the resin layer is a cured product of a curable composition containing one or more curable compounds, and the curable compound At least one kind is polyorganosilsesquioxane. [22] The laminated film according to the above [21], wherein the curable composition contains a polyorganosilsesquioxane having a structural unit represented by the following formula (1).

[In the formula (1), R ¹ represents a group containing a cationic polymerizable functional group] [23] The laminated film described in the above [22], wherein the above cationic polymerizable functional group is selected from epoxy groups, oxygen At least one type (preferably epoxy group) selected from the group consisting of cyclobutanyl group, vinyl ether group and vinylphenyl group. [24] The laminated film as described in [22] or [23] above, wherein the group containing a cationically polymerizable functional group is selected from the group represented by the following formula (1a), the following formula (1b) At least one of the groups represented by the group represented by, the group represented by the following formula (1c) and the group represented by the following formula (1d) (preferably selected from the group represented by the following formula (1a) group and at least one of the groups represented by the following formula (1c), more preferably a group represented by the following formula (1a)).

[In the above formula (1a), R ^1a represents a linear or branched alkylene group]

[In the above formula (1b), R ^1b represents a linear or branched alkylene group]

[In the above formula (1c), R ^1c represents a linear or branched alkylene group]

[In the above formula (1d), R ^1d represents a linear or branched alkylene group] [25] The laminated film as described in any one of the above [22] to [24], wherein R ¹ is the following The group: a group represented by the above formula (1a), and R ^1a is an ethylidene group [especially, 2-(3',4'-epoxycyclohexyl)ethyl].

[上述式（2）中，R² 表示經取代或未經取代之芳基、經取代或未經取代之芳烷基、經取代或未經取代之環烷基、經取代或未經取代之烷基、或經取代或未經取代之烯基] [27]如上述[26]中所記載之積層膜，其中，上述R² 為經取代或未經取代之芳基、經取代或未經取代之烷基、或經取代或未經取代之烯基（較佳為經取代或未經取代之芳基，更佳為苯基）。 [28]如上述[22]至[27]中任一項所記載之積層膜，其中，上述聚有機倍半矽氧烷具有下述式（I）所表示之構成單元（有時稱為「T3體」）、與下述式（II）所表示之構成單元（有時稱為「T2體」）。

[上述式（I）中之R^a 及式（II）中之R^b 分別表示含有陽離子聚合性官能基之基、經取代或未經取代之芳基、經取代或未經取代之芳烷基、經取代或未經取代之環烷基、經取代或未經取代之烷基、經取代或未經取代之烯基、或氫原子。上述式（II）中之R^c 表示氫原子或碳數1〜4之烷基] [29]如上述[28]中所記載之積層膜，其中，上述式（I）所表示之構成單元（T3體）與上述式（II）所表示之構成單元（T2體）之比率[T3體/T2體]為5以上（例如5以上且500以下）。 [30]如上述[29]中所記載之積層膜，其中，上述比率[T3體/T2體]之下限值為5（較佳為6，進而較佳為7），且上限值未達20（較佳為18，更佳為16，進而較佳為14）。 [31]如上述[29]中所記載之積層膜，其中，上述比率[T3體/T2體]之下限值為20（較佳為21，更佳為23，進而較佳為25），且上限值為500（較佳為100，更佳為50，進而較佳為40）。 [32]如上述[22]至[31]中任一項所記載之積層膜，其中，上述聚有機倍半矽氧烷具有下述式（4）所表示之構成單元。

[式（4）中，R¹ 係與式（1）中者相同。R^c 係與式（II）中者相同] [33]如上述[32]中所記載之積層膜，其中，上述聚有機倍半矽氧烷中之上述式（1）所表示之構成單元及上述式（4）所表示之構成單元相對於矽氧烷構成單元之總量（100莫耳%）之比率（總量）為55〜100莫耳%（較佳為65〜100莫耳%，進而較佳為80〜99莫耳%）。 [34]如上述[22]至[33]中任一項所記載之積層膜，其中，上述聚有機倍半矽氧烷具有下述式（5）所表示之構成單元。

[式（5）中，R² 係與式（2）中者相同。R^c 係與式（II）中者相同] [35]如上述[34]中所記載之積層膜，其中，上述聚有機倍半矽氧烷中之上述式（2）所表示之構成單元及上述式（5）所表示之構成單元相對於矽氧烷構成單元之總量（100莫耳%）之比率（總量）為0〜70莫耳%（較佳為0〜60莫耳%，更佳為0〜40莫耳%，尤佳為1〜15莫耳%）。 [36]如上述[32]至[35]中任一項所記載之積層膜，其中，上述聚有機倍半矽氧烷中之上述式（1）所表示之構成單元、上述式（2）所表示之構成單元、上述式（4）所表示之構成單元及上述式（5）所表示之構成單元相對於矽氧烷構成單元之總量（100莫耳%）之比率（總量）為60〜100莫耳%（較佳為70〜100莫耳%，更佳為80〜100莫耳%）。 [37]如上述[21]至[36]中任一項所記載之積層膜，其中，上述聚有機倍半矽氧烷之數量平均分子量之下限值為1000（較佳為1100），且上限值為3000（較佳為2800，更佳為2600）。 [38]如上述[21]至[36]中任一項所記載之積層膜，其中，上述聚有機倍半矽氧烷之數量平均分子量之下限值為2500（較佳為2800，更佳為3000），且上限值為50000（較佳為10000，更佳為8000）。 [39]如上述[21]至[38]中任一項所記載之積層膜，其中，上述聚有機倍半矽氧烷之分子量分散度之下限值為1.0（較佳為1.1，更佳為1.2）。 [40]如上述[21]至[39]中任一項所記載之積層膜，其中，上述聚有機倍半矽氧烷之分子量分散度之上限值為3.0（較佳為2.0，更佳為1.9）。 [41]如上述[21]至[39]中任一項所記載之積層膜，其中，上述聚有機倍半矽氧烷之分子量分散度之上限值為4.0（較佳為3.0，更佳為2.5）。 [42]如上述[21]至[41]中任一項所記載之積層膜，其中，上述聚有機倍半矽氧烷於空氣環境下之5%重量減少溫度（T_d5 ）為330℃以上（例如330〜450℃，較佳為340℃以上，更佳為350℃以上）。 [43]如上述[21]至[42]中任一項所記載之積層膜，其中，上述硬化性組成物中之上述聚有機倍半矽氧烷之含量（摻合量）相對於除溶劑以外之硬化性組成物之總量（100重量%）為50重量%以上且未達100重量%（較佳為60〜99重量%，更佳為70〜95重量%）。 [44]如上述[21]至[43]中任一項所記載之積層膜，其中，上述聚有機倍半矽氧烷相對於上述硬化性組成物中所含之陽離子硬化性化合物之總量（100重量%）之比率為60〜99重量%（較佳為65〜98重量%，更佳為70〜95重量%）。[26] The laminated film according to any one of the above [22] to [25], wherein the polyorganosilsesquioxane further has a structural unit represented by the following formula (2).

[In the above formula (2), R ² represents substituted or unsubstituted aryl, substituted or unsubstituted aralkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted Alkyl, or substituted or unsubstituted alkenyl] [27] The laminated film as described in the above [26], wherein the above R ² is substituted or unsubstituted aryl, substituted or unsubstituted Substituted alkyl, or substituted or unsubstituted alkenyl (preferably substituted or unsubstituted aryl, more preferably phenyl). [28] The laminated film according to any one of the above [22] to [27], wherein the polyorganosilsesquioxane has a structural unit represented by the following formula (I) (sometimes referred to as " T3 body"), and a structural unit represented by the following formula (II) (sometimes referred to as "T2 body").

[Ra in the above formula (I) and R ^b in the formula (II) respectively represent ^a group containing a cationic polymerizable functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group , a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom. R ^c in the above formula (II) represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms] [29] The laminated film as described in the above [28], wherein the constituent unit represented by the above formula (I) ( The ratio [T3 body/T2 body] to the structural unit (T2 body) represented by the above formula (II) is 5 or more (for example, 5 or more and 500 or less). [30] The laminated film described in [29] above, wherein the lower limit of the ratio [T3 bulk/T2 bulk] is 5 (preferably 6, more preferably 7), and the upper limit is Up to 20 (preferably 18, more preferably 16, further preferably 14). [31] The laminated film as described in [29] above, wherein the lower limit of the ratio [T3 body/T2 body] is 20 (preferably 21, more preferably 23, still more preferably 25), And the upper limit is 500 (preferably 100, more preferably 50, further preferably 40). [32] The laminated film according to any one of the above [22] to [31], wherein the polyorganosilsesquioxane has a structural unit represented by the following formula (4).

[In formula (4), R ¹ is the same as in formula (1). R ^c is the same as in formula (II)] [33] The laminated film described in [32] above, wherein the structural unit represented by the above formula (1) in the polyorganosilsesquioxane and The ratio (total amount) of the constituent units represented by the above formula (4) relative to the total amount (100 mole %) of the siloxane constituent units is 55-100 mole % (preferably 65-100 mole %, Furthermore, it is preferably 80 to 99 mole %). [34] The laminated film according to any one of the above [22] to [33], wherein the polyorganosilsesquioxane has a structural unit represented by the following formula (5).

[In formula (5), R ² is the same as in formula (2). R ^c is the same as in the formula (II)] [35] The laminated film described in the above [34], wherein the structural unit represented by the above formula (2) in the polyorganosilsesquioxane and The ratio (total amount) of the constituent units represented by the above formula (5) to the total amount (100 mole %) of the siloxane constituent units is 0 to 70 mole % (preferably 0 to 60 mole %, More preferably 0~40 mole %, most preferably 1~15 mole %). [36] The laminated film according to any one of the above [32] to [35], wherein the structural unit represented by the above formula (1) in the above polyorganosilsesquioxane, the above formula (2) The ratio (total amount) of the structural unit represented, the structural unit represented by the above formula (4), and the structural unit represented by the above formula (5) to the total amount (100 mole %) of the siloxane structural unit is 60-100 mol% (preferably 70-100 mol%, more preferably 80-100 mol%). [37] The laminated film according to any one of [21] to [36] above, wherein the lower limit of the number average molecular weight of the polyorganosilsesquioxane is 1000 (preferably 1100), and The upper limit is 3000 (preferably 2800, more preferably 2600). [38] The laminated film according to any one of the above [21] to [36], wherein the lower limit of the number average molecular weight of the polyorganosilsesquioxane is 2500 (preferably 2800, more preferably is 3000), and the upper limit is 50000 (preferably 10000, more preferably 8000). [39] The laminated film according to any one of the above [21] to [38], wherein the lower limit of the molecular weight dispersion of the polyorganosilsesquioxane is 1.0 (preferably 1.1, more preferably is 1.2). [40] The laminated film according to any one of the above [21] to [39], wherein the upper limit of the molecular weight dispersion of the polyorganosilsesquioxane is 3.0 (preferably 2.0, more preferably is 1.9). [41] The laminated film according to any one of the above [21] to [39], wherein the upper limit of the molecular weight dispersion of the polyorganosilsesquioxane is 4.0 (preferably 3.0, more preferably is 2.5). [42] The laminated film according to any one of [21] to [41] above, wherein the 5% weight loss temperature (T _d5 ) of the polyorganosilsesquioxane in an air environment is 330°C or higher (For example, 330~450°C, preferably above 340°C, more preferably above 350°C). [43] The laminated film according to any one of the above [21] to [42], wherein the content (blend amount) of the polyorganosilsesquioxane in the curable composition is The total amount (100% by weight) of other curable compositions is at least 50% by weight and less than 100% by weight (preferably 60 to 99% by weight, more preferably 70 to 95% by weight). [44] The laminated film according to any one of [21] to [43] above, wherein the polyorganosilsesquioxane relative to the total amount of the cation-curable compound contained in the curable composition is (100% by weight) ratio is 60 to 99% by weight (preferably 65 to 98% by weight, more preferably 70 to 95% by weight).

[45] The laminated film according to any one of the above [21] to [44], wherein the curable composition further contains a curing catalyst. [46] The laminated film according to the above [45], wherein the curing catalyst is a photocationic polymerization initiator. [47] The laminated film according to the above [45], wherein the curing catalyst is a thermal cationic polymerization initiator. [48] The laminated film according to any one of [45] to [47] above, wherein the content (blend amount) of the curing catalyst is 100 parts by weight of the polyorganosilsesquioxane: 0.01~3.0 parts by weight (preferably 0.05~3.0 parts by weight, more preferably 0.1~1.0 parts by weight, more preferably 0.3~1.0 parts by weight).

[49] The laminated film according to any one of [21] to [48] above, wherein the curable composition contains one or more thermally polymerizable functional groups and one or more photopolymerizable functional groups in the molecule. A compound of a functional group (hereinafter, sometimes referred to as "compound A"). [50] The laminated film as described in the above [49], wherein the "thermally polymerizable functional group" of the above-mentioned compound A is selected from the group consisting of hydroxyl group, epoxy group, oxetanyl group and vinyl ether group. At least 1 type in the group (preferably at least 1 type selected from the group consisting of a hydroxyl group and an epoxy group). [51] The laminated film as described in [49] or [50] above, wherein the "photopolymerizable functional group" contained in the compound A is selected from the group consisting of (meth)acryl and vinyl groups. At least one of the group (preferably (meth)acryloyl). [52] The laminated film as described in any one of the above-mentioned [49] to [51], wherein the number of thermally polymerizable functional groups in one molecule of the above-mentioned compound A is 1 to 5 (preferably 1 to 3, preferably 1 or 2). [53] The laminated film according to any one of the above-mentioned [49] to [52], wherein the number of photopolymerizable functional groups contained in the compound A per molecule is 1 to 5 (preferably 1 to 3, preferably 1 or 2). [54] The laminated film described in any one of the above-mentioned [49] to [53], wherein the functional group equivalent weight of the thermopolymerizable functional group of the above-mentioned compound A is 50 to 500 (preferably 80 to 480, more preferably The best is 120~450). [55] The laminated film as described in any one of [49] to [54] above, wherein the functional group equivalent weight of the photopolymerizable functional group of the above compound A is 50 to 500 (preferably 80 to 480, more preferably The best is 120~450). [56] The laminated film according to any one of the above-mentioned [49] to [55], wherein the above-mentioned compound A has an epoxy group and/or a hydroxyl group as a thermally polymerizable functional group in one molecule, and A compound of (meth)acryl group with a photopolymerizable functional group. [57] The laminated film according to any one of the above [49] to [56], wherein the compound A is selected from the group consisting of 3,4-epoxycyclohexylmethyl (meth)acrylate, (methyl) Glycidyl acrylate, tripropylene glycol diglycidyl ether hemi(meth)acrylate, bisphenol A epoxy hemi(meth)acrylate, bisphenol F epoxy hemi(meth)acrylate and bisphenol S epoxy At least 1 sort from the group which consists of a half (meth)acrylate. [58] The laminated film according to any one of the above-mentioned [49] to [57], wherein the content (blend amount) of the above-mentioned compound A is, in terms of solid content, relative to the above-mentioned polyorganosilsesquioxane 100 parts by weight are 1 to 100 parts by weight (preferably 3 to 75 parts by weight, more preferably 5 to 50 parts by weight).

[59] The laminated film according to any one of the above [21] to [58], wherein the curable composition further contains a fluorine-containing photopolymerizable resin. [60] The laminated film described in [59] above, wherein the photopolymerizable functional group of the fluorine-containing photopolymerizable resin is selected from the group consisting of (meth)acryl and vinyl groups. At least one of them (preferably (meth)acryloyl). [61] The laminated film as described in [59] or [60] above, wherein the number of photopolymerizable functional groups in one molecule of the fluorine-containing photopolymerizable resin is 1 to 5 (compared to preferably 1 to 3). [62] The laminated film according to any one of [59] to [61] above, wherein the fluorine-containing group contained in the fluorine-containing photopolymerizable resin is a group having a fluoroaliphatic hydrocarbon skeleton. [63] The laminated film according to the above [62], wherein the fluoroaliphatic hydrocarbon skeleton forms a polyfluoroalkylene ether skeleton as a repeating unit via an ether bond. [64] The laminated film according to any one of [59] to [63] above, wherein the fluorine-containing photopolymerizable resin has a silicone-containing group. [65] The laminated film according to any one of the above [59] to [64], wherein the content (blending amount) of the above-mentioned fluorine-containing photopolymerizable resin is, in terms of solid content, relative to the above-mentioned polyorganic resin 100 parts by weight of silsesquioxane is 0.01 to 15 parts by weight (preferably 0.05 to 10 parts by weight, more preferably 0.01 to 5 parts by weight, and more preferably 0.2 to 3 parts by weight).

[上述式（i）中，Y表示單鍵或連結基（具有1個以上之原子之二價基）。式（i）中之環己烷環之氫原子之1個以上可經碳數1〜6之烷基等取代基取代] [70]如上述[69]中所記載之積層膜，其中，上述式（i）所表示之脂環式環氧化合物係選自由(3,4,3',4'-二環氧基)聯環己烷、2,2-雙(3,4-環氧環己基)丙烷、1,2-雙(3,4-環氧環己基)乙烷、2,3-雙(3,4-環氧環己基)環氧乙烷、雙(3,4-環氧環己基甲基)醚及下述式（i-1）〜（i-10）所表示之化合物所組成之群中之至少1種。

[上述式（i-5）、（i-7）中之l、m分別表示1〜30之整數。上述式（i-5）中之R'表示碳數1〜8之伸烷基。上述式（i-9）、（i-10）中之nl〜n6分別表示1〜30之整數] [71]如上述[68]至[70]中任一項所記載之積層膜，其中，上述（2）環氧基直接利用單鍵與脂環鍵結之化合物為下述式（ii）所表示之化合物。

[式（ii）中，R''表示自p元醇之結構式去除p個羥基（-OH）所得之基（p價有機基）。p、n分別表示自然數，於p為2以上之情形時，各（）內（外側之括弧內）之基中之n可相同亦可不同] [72]如上述[68]至[71]中任一項所記載之積層膜，其中，上述環氧化合物係（2）環氧基直接利用單鍵與脂環鍵結之化合物（較佳為上述式（ii）所表示之化合物）。 [73]如上述[66]至[72]中任一項所記載之積層膜，其中，上述環氧化合物之含量（摻合量）相對於上述聚有機倍半矽氧烷之總量100重量份，為0.5〜100重量份（較佳為1〜80重量份，更佳為5〜50重量份）。[66] The laminated film according to any one of the above [21] to [65], wherein the curable composition further contains an epoxy compound other than the polyorganosilsesquioxane (hereinafter sometimes referred to as as "epoxy compounds"). [67] The laminated film according to the above [66], wherein the epoxy compound is at least one selected from the group consisting of alicyclic epoxy compounds, aromatic epoxy compounds, and aliphatic epoxy compounds. species (preferably alicyclic epoxy compounds). [68] The laminated film described in the above [67], wherein the alicyclic epoxy compound is selected from (1) having the following epoxy group (referred to as "alicyclic epoxy group") in the molecule Compounds, the epoxy group is composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring; (2) compounds in which the epoxy group is directly bonded to the alicyclic ring through a single bond; and (3) have an alicyclic ring in the molecule and at least one compound of glycidyl ether group (glycidyl ether type epoxy compound). [69] The laminated film according to the above [68], wherein the compound having an alicyclic epoxy group in the molecule of the above (1) is a compound represented by the following formula (i).

[In the above formula (i), Y represents a single bond or a linking group (a divalent group having one or more atoms). One or more hydrogen atoms of the cyclohexane ring in the formula (i) may be substituted by a substituent such as an alkyl group having 1 to 6 carbon atoms] [70] The laminated film as described in the above [69], wherein the above The alicyclic epoxy compound represented by formula (i) is selected from (3,4,3',4'-diepoxy) bicyclohexane, 2,2-bis(3,4-epoxy ring Hexyl) propane, 1,2-bis(3,4-epoxycyclohexyl)ethane, 2,3-bis(3,4-epoxycyclohexyl)oxirane, bis(3,4-epoxycyclohexyl) At least one of the group consisting of cyclohexylmethyl) ether and compounds represented by the following formulas (i-1) to (i-10).

[1, m in above-mentioned formula (i-5), (i-7) represent the integer of 1～30 respectively. R' in the above formula (i-5) represents an alkylene group having 1 to 8 carbon atoms. n1 to n6 in the above formulas (i-9) and (i-10) respectively represent an integer of 1 to 30] [71] The laminated film according to any one of the above [68] to [70], wherein, The above (2) compound in which the epoxy group is directly bonded to the alicyclic ring through a single bond is a compound represented by the following formula (ii).

[In formula (ii), R'' represents a group obtained by removing p hydroxyl groups (-OH) from the structural formula of p-hydric alcohol (p-valent organic group). p and n represent natural numbers respectively. When p is 2 or more, the n in the bases inside each () (in the brackets outside) can be the same or different] [72] as above [68] to [71] The laminated film according to any one of the above, wherein the epoxy compound is (2) a compound in which an epoxy group is directly bonded to an alicyclic ring via a single bond (preferably a compound represented by the above formula (ii)). [73] The laminated film according to any one of the above [66] to [72], wherein the content (blend amount) of the epoxy compound is 100% by weight relative to the total amount of the polyorganosilsesquioxane Parts are 0.5 to 100 parts by weight (preferably 1 to 80 parts by weight, more preferably 5 to 50 parts by weight).

[74] The laminated film according to any one of [1] to [73] above, wherein the support is a transparent support. [75] A foldable device comprising the laminated film described in any one of [1] to [74]. [76] The foldable device as described in [75] above, which is an image display device. [77] The foldable device as described in [76] above, wherein the image display device is an organic electroluminescence display device. [Industrial availability]

The laminated film of the present invention is suitable as a surface protection material for foldable devices such as organic electroluminescent display devices due to its high surface hardness and excellent bending durability.

1‧‧‧Laminated film R‧‧‧bending radius

Fig. 1 shows the test method of bending durability (R bending method) in the present invention (the laminated film is bent so that the bending radius (R) becomes 2.5 mm or 4.0 mm in the direction where the surface of the resin layer becomes concave or convex. 180°, and unfold 1 action) schematic diagram (side view). Fig. 2 is an enlarged view of (4) in Fig. 1. 3 is a ¹ H-NMR chart of the epoxy group-containing low molecular weight polyorganosilsesquioxane obtained in Production Example 1. FIG. FIG. 4 is a ²⁹ Si-NMR chart of the epoxy-group-containing low-molecular-weight polyorganosilsesquioxane obtained in Production Example 1. FIG. FIG. 5 is a ¹ H-NMR chart of the epoxy group-containing high molecular weight polyorganosilsesquioxane obtained in Production Example 2. FIG. FIG. 6 is a ²⁹ Si-NMR chart of epoxy group-containing high molecular weight polyorganosilsesquioxane obtained in Production Example 2. FIG.

Claims (14)

A laminated film comprising a support and a resin layer laminated on at least one side of the support, wherein the resin layer is a cured product of a curable composition containing at least one curable compound, and the curable The composition contains polyorganosilsesquioxane (polyorganosilsesquioxane) having an epoxy group-containing group, and a compound having one or more thermally polymerizable functional groups and one or more photopolymerizable functional groups in the molecule as curable compounds. compound; the resin layer (either resin layer when there are resin layers on the double-sided layer of the above-mentioned support) fully satisfies the following (condition 1) and (condition 2), (condition 1) the resin of the above-mentioned laminated film The pencil hardness of the pencil hardness test (750g load) stipulated in JIS K5600-5-4 (1999) of the surface of the layer is F or above, (condition 2) the bending durability (1) in the following bending durability test (1) ) is more than 50,000 times. Bending durability test (1): Bending the self-laminated film 180° along the direction in which the surface of the resin layer becomes depressed with a bending radius of 2.5 mm, and unfolding it again When the above-mentioned operation is performed at a speed of 30 to 60 times/min, the number of times until a crack occurs in the resin layer of the laminated film is used as an index of bending durability (1). A laminated film comprising a support and a resin layer laminated on at least one side of the support, wherein the resin layer is a cured product of a curable composition containing at least one curable compound, and the curable The composition comprises a polyorganosilsesquioxane having epoxy-containing groups, and A compound having one or more thermally polymerizable functional groups and one or more photopolymerizable functional groups in the molecule is used as a curable compound; the resin layer (in the case of a resin layer on the double-sided layer of the above-mentioned support is optional) A resin layer) fully satisfy the following (condition 1) and (condition 3), (condition 1) the pencil hardness test (750g load) stipulated in JIS K5600-5-4 (1999) of the resin layer surface of the above-mentioned laminated film The pencil hardness is F or more, (Condition 3) The bending durability (2) in the following bending durability test (2) is more than 10,000 times, the bending durability test (2): the state where the self-laminated film is unfolded, Bending 180° along the convex direction of the surface of the resin layer so that the bending radius becomes 4.0mm, and unfolding the action once again, when the above action is performed at a speed of 30 to 60 times/minute, the laminated film will The number of times until cracks occurred in the resin layer was used as an index of bending durability (2). The laminated film according to claim 1 or 2, wherein the above-mentioned resin layer (any resin layer when there are resin layers on the double-layered layer of the above-mentioned support) further fully satisfies the following (condition 4), ( Condition 4) In the cylindrical mandrel test stipulated in JIS K5600-5-1 (1999) where the surface of the resin layer of the laminated film becomes convex, the bending radius is 5mm, and there is no turtle on the surface of the resin layer crack. The laminated film according to claim 1 or 2, wherein the water contact angle of the surface of the resin layer (or any resin layer when there are resin layers on both sides of the support) is 95° or more. The laminated film according to Claim 1 or 2, wherein the above-mentioned resin layer (any resin layer when there are resin layers on the double-layered layer of the above-mentioned support) further fully satisfies the following (Condition 5), ( Condition 5) While applying a load of 1 kg/cm ² using #0000 steel wool, no scratches were visually observed in the steel wool resistance test in which the surface of the resin layer was rubbed back and forth 30 times. The laminated film as described in claim 1 or 2, wherein the above-mentioned resin layer (in the above-mentioned support In the case where the double-layered layer of the body has a resin layer, it is either resin layer) with a haze of 1.0% or less. The laminated film according to claim 1 or 2, wherein the curable composition further contains a curing catalyst. The laminated film according to claim 7, wherein the curing catalyst is a photocationic polymerization initiator. The laminated film according to claim 7, wherein the curing catalyst is a thermal cationic polymerization initiator. The laminated film according to claim 1 or 2, wherein the curable composition further contains a fluorine-containing photopolymerizable resin. The laminated film according to claim 1 or 2, wherein the support is a transparent support. A foldable device comprising the laminated film described in claim 1 or 2. The foldable device according to Claim 12 is an image display device. The foldable device according to claim 13, wherein the image display device is an organic electroluminescent display device.

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