TW201708318A - Resin film, laminated article, optical member, display member and front panel - Google Patents

Abstract

This invention provides a resin film 10 containing polyimides polymer, while conducting an light exposing test for exposing a predetermined light from a main surface 10a to the resin film 10, the resin film satisfies the following conditions of: (i) the resin film after light exposing test has a transparency of 85% or more to a light with a wavelength of 550 nm; and (ii) the resin film before light exposing test has a yellowness of 5 or less, and the difference of yellowness of the resin film before and after the light exposing test is less than 2.5.

Description

Resin film, laminate, optical member, display member, and front panel

The present invention relates to a resin film, a laminate, an optical member, a display member, and a front panel.

Conventionally, glass has been used as a material for a substrate, an optical member substrate, and a front panel of a display member constituting various display devices such as a solar cell or a display. However, glass has the disadvantage of being easily cracked and heavy. Moreover, in recent years, when the display is made thinner, lighter, and flexible, the glass substrate or the glass front panel does not have sufficient material properties. Therefore, an acrylic resin and a laminate having scratch resistance to a resin have been studied as a material or a substrate instead of glass. A composite material of an organic material and an inorganic material containing a mixed film of polyimide and cerium oxide has been studied (for example, refer to Patent Documents 1 and 2).

Prior technical literature Patent literature

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2008-163309

[Patent Document 2] US Patent No. 8207256

According to the findings of the inventors of the present invention, the resin film containing a polyimine-based polymer has high transparency and can achieve excellent flexibility. However, in the case of a resin film containing a polyimine-based polymer, the contrast and the hue may change during bending, and in this case, it is necessary to further improve. The resin film applied to the substrate of the display member of the flexible device, the substrate of the optical member, and/or the use of the front panel is required to have good visibility when bent.

Therefore, the main object of the present invention is to improve the visibility at the time of bending in a resin film containing a polyimine-based polymer and having high transparency.

The resin film of one aspect of the present invention contains a polyimine-based polymer. The light-receiving test was carried out by irradiating the resin film with light of 313 nm for 24 hours from one main surface side of the resin film by a light source having an output of 40 W at a distance of 5 cm from the resin film. The following conditions.

(i) the resin film after the light irradiation test has a transmittance of 85% or more for 550 nm light; and (ii) the resin film before the light irradiation test has a yellowness of 5 or less, and the resin film The difference in yellowness before and after the light irradiation test was less than 2.5.

A resin film satisfying the conditions (i) and (ii), when bent Contrast or hue is not easy to change, but can maintain good visibility.

The present invention provides a laminated body comprising the above resin film and a functional layer provided on at least one side of the resin film. The functional layer may be a layer having at least one function selected from the group consisting of ultraviolet absorption, adhesion, and high hardness on the surface.

The laminate may further have an undercoat layer provided between the resin film and the functional layer.

The substrate of the optical member or the display member and the front panel of the aspect of the invention have the resin film or the laminate. When these systems are applied to a flexible device, they can contribute to excellent visibility at the time of bending.

According to the present invention, in the case of a resin film containing a polyimine-based polymer, visibility during bending can be improved.

10‧‧‧Resin film

10a, 10b‧‧‧ main faces

20‧‧‧ functional layer

25‧‧‧Undercoat

25a‧‧‧Main face

30‧‧‧Laminated body (layered body)

50‧‧‧Organic EL device

51‧‧‧Organic EL components

52‧‧‧1st electrode

53‧‧‧2nd electrode

54‧‧‧Lighting layer

55‧‧‧1st substrate

56‧‧‧2nd substrate

59‧‧‧ Sealing material

70‧‧‧Touch sensor

71‧‧‧Touch sensor substrate

72‧‧‧Component layer

90‧‧‧ front panel

100‧‧‧ display device

Fig. 1 is a cross-sectional view showing an embodiment of a resin film.

Fig. 2 is a cross-sectional view showing an embodiment of a laminated body.

Fig. 3 is a cross-sectional view showing an embodiment of a laminated body.

Fig. 4 is a schematic cross-sectional view showing an embodiment of a display device.

(to implement the form of the invention)

Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In each figure, the same Or the corresponding elements are denoted by the same reference numerals and the repeated description is omitted.

[Resin film]

Fig. 1 is a cross-sectional view showing an embodiment of a resin film. The resin film 10 shown in Fig. 1 is a polyimine-based polymer and has a pair of main faces 10a and 10b facing each other.

A light source having an output of 40 W at a distance of 5 cm from the resin film 10 was used to irradiate the resin film 10 with light of 313 nm for 24 hours from the main surface 10a side. The resin film 10 satisfies the following conditions: (i) the resin film after the light irradiation test has a transmittance of 85% or more for 550 nm light; and (ii) the resin film before the light irradiation test has a yellowness (YI value) of 5 or less, and The difference in yellowness before and after the light irradiation test of the resin film was less than 2.5. The resin film satisfying the conditions (i) and (ii) does not easily change in contrast or hue during bending, and can maintain good visibility.

The resin film which satisfies the conditions (i) and (ii) can be easily obtained by, for example, using a polyimine-based polymer having high transparency and containing a UV absorber in the resin film. Specific examples of the polyimine-based polymer and the ultraviolet absorber having high transparency will be described later.

The transmittance of the resin film 10 after the light irradiation test to light of 550 nm is preferably 90% or more, and usually 100% or less. It is 95% or less. The haze of the resin film 10 after the light irradiation test is preferably 0.9 or less, and may be 0.1 or more. The resin film 10 before the light irradiation test may have a transmittance of 85% or more for light of 550 nm. The transmittance of the resin film to light of a predetermined wavelength means the ratio of the light intensity of the same wavelength with respect to the incident resin film and the light intensity of the same wavelength after the resin film is transmitted. The haze can be measured in accordance with JIS K 7105:1981. The detailed measurement methods of the transmittance and the haze are described in Examples to be described later.

The yellowness of the resin film 10 before the light irradiation test is preferably 4 or less, more preferably 3 or less, and may be 0.5 or more. When the yellowness before the light irradiation test is YI ₀ and the yellowness after the light irradiation is YI ₁ , the difference in yellowness ΔYI before and after the light irradiation test of the resin film is according to the formula "ΔYI=YI ₁ -YI ₀ And calculate. The ΔYI is preferably 2.3 or less, more preferably 2.0 or less, and may be 0.1 or more. The detailed measurement method of the yellowness is described in the examples described later.

The resin film 10 contains a polyimine-based polymer. In the present specification, the polyimine-based polymer means a polymer having at least one type of repeating structural unit represented by the formula (PI), the formula (a), the formula (a') or the formula (b). . From the viewpoint of the strength and transparency of the film, the main structure of the repeating structural unit represented by the formula (PI) is a polyimine-based polymer. The repeating structural unit represented by the formula (PI) is preferably 40 mol% or more, more preferably 50 mol% or more, and more preferably 70 mol%, based on the total repeating structural unit of the polyimine-based polymer. More than %, more preferably more than 90% by mole, and even more preferably 98% by mole.

The G system in the formula (PI) represents a tetravalent organic group, and the A system represents a divalent organic group. The G ² in the formula (a) represents a trivalent organic group, and the A ² represents a divalent organic group. The G ³ in the formula (a') represents a tetravalent organic group, and the A ³ represents a divalent organic group. The G ⁴ and A ⁴ systems in the formula (b) each represent a divalent organic group.

In the formula (PI), organic as a tetravalent organic group represented by G The group (hereinafter referred to as an organic group called G) may be a group selected from the group consisting of an acyclic aliphatic group, a cyclic aliphatic group, and an aromatic group. From the viewpoint of transparency and flexibility of the resin film 10, the organic group of G is preferably a tetravalent cyclic aliphatic group or a tetravalent aromatic group. Examples of the aromatic group include a monocyclic aromatic group, a condensed polycyclic aromatic group, and a non-condensed one having two or more aromatic rings which are bonded directly or via a bonding group. Polycyclic aromatic groups and the like. The organic group of G is a cyclic aliphatic group, a cyclic aliphatic group having a fluorine-based substituent, and a monocyclic aromatic group having a fluorine-based substituent from the viewpoints of transparency of the resin film and suppression of coloring. A condensed polycyclic aromatic group having a fluorine-based substituent or a non-condensed polycyclic aromatic group having a fluorine-based substituent is preferred. The fluorine-based substituent in the present specification means a group containing a fluorine atom. The fluorine-based substituent is preferably a fluorine group (a fluorine atom, -F) or a perfluoroalkyl group, more preferably a fluorine group or a trifluoromethyl group.

More specifically, the organic group of G, for example, can be selected from a saturated or unsaturated cycloalkyl group, a saturated or unsaturated heterocycloalkyl group, an aryl group, a heteroaryl group, an arylalkyl group, an alkylaryl group, a heteroalkyl group. a aryl group and a group having any two of these groups (which may be the same) and which are bonded to each other directly or via a bonding group. Examples of the bonding group include -O-, an alkylene group having 1 to 10 carbon atoms, -SO ₂ -, -CO- or -CO-NR- (R represents a methyl group, an ethyl group, a propyl group or the like). An alkyl group having 1 to 3 carbon atoms or a hydrogen atom).

G represents a carbon number of the tetravalent organic group, usually 2 to 32, preferably 4 to 15, more preferably 5 to 10, still more preferably 6 to 8. When the organic group of G is a cyclic aliphatic group or an aromatic group, the carbon atoms constituting the groups At least one of them may be substituted by a hetero atom. Examples of the hetero atom include O, N or S.

Specific examples of G include the groups represented by the following formula (20), formula (21), formula (22), formula (23), formula (24), formula (25) or formula (26). The * in the formula indicates a dangling key. Z in the formula (26) represents a single bond, -O-, -CH ₂ -, -C(CH ₃ ) ₂ -, -Ar-O-Ar-, -Ar-CH ₂ -Ar-, -Ar -C(CH ₃ ) ₂ -Ar- or -Ar-SO ₂ -Ar-. The Ar system represents an aryl group having 6 to 20 carbon atoms, and may be, for example, an alkylene group. At least one of the hydrogen atoms of the groups may be substituted with a fluorine-based substituent.

In the formula (PI), the organic group of the divalent organic group represented by A (hereinafter, sometimes referred to as an organic group of A) may be selected from the group consisting of an acyclic aliphatic group, a cyclic aliphatic group, and an aromatic group. The basis of the group. The divalent organic group represented by A is preferably selected from the group consisting of a divalent cyclic aliphatic group and a divalent aromatic group. Examples of the aromatic group include a monocyclic aromatic group, a condensed polycyclic aromatic group, and two or more aromatic rings, and these are straight. A non-condensed polycyclic aromatic group which is bonded to each other by a bonding group. From the viewpoint of transparency of the resin film and suppression of coloration, it is preferred that the organic group of A is introduced with a fluorine-based substituent.

More specifically, the organic group of A is, for example, selected from a saturated or unsaturated cycloalkyl group, a saturated or unsaturated heterocycloalkyl group, an aryl group, a heteroaryl group, an arylalkyl group, an alkylaryl group, a heteroalkyl group. An aryl group and a group having any two of these groups (which may be the same) and which are bonded to each other directly or via a bonding group. Examples of the hetero atom include O, N or S, and examples of the bonding group include -O-, an alkylene group having 1 to 10 carbon atoms, -SO ₂ -, -CO- or -CO-NR- ( R is an alkyl group having 1 to 3 carbon atoms or a hydrogen atom such as a methyl group, an ethyl group or a propyl group.

A represents a carbon number of the divalent organic group, usually 2 to 40, preferably 5 to 32, more preferably 12 to 28, still more preferably 24 to 27.

Specific examples of A include the groups represented by the following formula (30), formula (31), formula (32), formula (33) or formula (34). The * in the formula indicates a dangling key. Z ¹ to Z ³ are each independently and represent a single bond, -O-, -CH ₂ -, -C(CH ₃ ) ₂ -, -SO ₂ -, -CO- or -CO-NR- (R is a methyl group An alkyl group having 1 to 3 carbon atoms such as an ethyl group or a propyl group or a hydrogen atom). In the following groups, Z ¹ and Z ² , and Z ² and Z ³ are preferably each a meta or a para position for each ring. The single bond of Z ¹ and the terminal, the single bond of Z ² and the terminal, and the single bond of Z ³ and the terminal are preferably each a meta or a para position. In one example of A, Z ¹ and Z ³ are -O-, and Z ² is -CH ₂ -, -C(CH ₃ ) ₂ - or -SO ₂ -. One or two or more hydrogen atoms of the groups may be substituted with a fluorine-based substituent.

At least one hydrogen atom among the hydrogen atoms constituting at least one of A and G may be selected from the group consisting of a fluorine-based substituent, a hydroxyl group, a sulfonic acid group, and an alkyl group having 1 to 10 carbon atoms. At least one functional group is substituted. When the organic group of the above A and the organic group of G are each a cyclic aliphatic group or an aromatic group, it is preferred that at least one of A and G has a fluorine-based substituent, and both of A and G have a fluorine-based substitution. The base is preferred.

G ² in the formula (a) is a trivalent organic group. The organic group may be selected from the same groups as the organic group of G in the formula (PI), except for the point of the trivalent group. Examples of G ² include a group in which four of the four dangling bonds represented by the formulae (20) to (26), which are specific examples of G, are replaced with a hydrogen atom. The A ² system in the formula (a) can be selected from the same groups as those in the formula (PI).

G ³ in the formula (a') can be selected from the same groups as the organic group of G in the formula (PI). The A ³ system in the formula (a') can be selected from the same groups as those in the formula (PI).

G ⁴ in the formula (b) is a divalent organic group. The organic group can be selected from the same groups as the organic group of G in the formula (PI), except for the point of the divalent group. Examples of G ⁴ include a group in which four of the four dangling bonds represented by the formulae (20) to (26), which are specific examples of G, are replaced with a hydrogen atom. The A ⁴ system in the formula (b) can be selected from the same groups as those in the formula (PI).

The polyimine-based polymer contained in the resin film 10 may be a dicarboxylic acid compound or a tetracarboxylic acid compound (a tetracarboxylic acid compound analog such as a ruthenium chloride compound or a tetracarboxylic dianhydride). Or a condensed polymer obtained by polycondensing at least one type of a tricarboxylic acid compound (including a tricarboxylic acid compound analog such as a ruthenium chloride compound or a tricarboxylic acid anhydride). Further, a dicarboxylic acid compound (an analog containing a ruthenium chloride compound or the like) may be subjected to polycondensation. The repeating structural unit represented by the formula (PI) or the formula (a') is usually derived from a diamine and a tetracarboxylic acid compound. The repeating structural unit represented by the formula (a) is usually derived from a diamine and a tricarboxylic acid compound. The repeating structural unit represented by the formula (b) is usually derived from a diamine and a dicarboxylic acid compound.

Examples of the tetracarboxylic acid compound include an aromatic tetracarboxylic acid compound, an alicyclic tetracarboxylic acid compound, and an acyclic aliphatic tetracarboxylic acid compound. These may also be used in combination of 2 or more types. The tetracarboxylic acid compound is preferably a tetracarboxylic dianhydride, and examples of the tetracarboxylic dianhydride include an aromatic tetracarboxylic dianhydride, an alicyclic tetracarboxylic dianhydride, and an acyclic aliphatic tetracarboxylic acid. anhydride.

The tetracarboxylic acid compound is selected from the group consisting of an alicyclic tetracarboxylic acid compound and an aromatic four from the viewpoints of the solubility of the polyimine-based polymer in a solvent and the transparency and flexibility after forming the resin film 10 . Carboxylic acid Things are better. The tetracarboxylic acid compound is preferably selected from the group consisting of an alicyclic tetracarboxylic acid compound having a fluorine-based substituent and an aromatic tetracarboxylic acid compound having a fluorine-based substituent, from the viewpoints of transparency of the resin film and coloring inhibition. Further, an alicyclic tetracarboxylic acid compound having a fluorine-based substituent is more preferable.

Examples of the tricarboxylic acid compound include an aromatic tricarboxylic acid, an alicyclic tricarboxylic acid, an acyclic aliphatic tricarboxylic acid, and the like, a similar chlorochemical compound, an acid anhydride, and the like. The tricarboxylic acid compound is preferably an aromatic tricarboxylic acid, an alicyclic tricarboxylic acid, an acyclic aliphatic tricarboxylic acid, and the like. Two or more kinds of tricarboxylic acid compounds may be used in combination.

The tricarboxylic acid compound is selected from the group consisting of an alicyclic tricarboxylic acid compound and an aromatic tricarboxylic acid from the viewpoints of solubility of a polyimine-based polymer to a solvent and transparency and flexibility after forming the resin film 10 . Acid compounds are preferred. The tricarboxylic acid compound is preferably selected from the group consisting of an alicyclic tricarboxylic acid compound having a fluorine-based substituent and an aromatic tricarboxylic acid compound having a fluorine-based substituent, from the viewpoints of transparency of the resin film and suppression of coloring. .

Examples of the dicarboxylic acid compound include an aromatic dicarboxylic acid, an alicyclic dicarboxylic acid, an acyclic aliphatic dicarboxylic acid, and the like, a similar chlorochemical compound, an acid anhydride, and the like. The dicarboxylic acid compound is preferably selected from the group consisting of an aromatic dicarboxylic acid, an alicyclic dicarboxylic acid, an acyclic aliphatic dicarboxylic acid, and the like. Two or more types of dicarboxylic acid compounds may be used in combination.

The dicarboxylic acid compound is selected from the group consisting of an alicyclic dicarboxylic acid compound and an aromatic diene from the viewpoints of the solubility of the polyimine-based polymer to the solvent and the transparency and flexibility after the resin film 10 is formed. A carboxylic acid compound is preferred. From the viewpoint of transparency of the resin film and suppression of coloring, The carboxylic acid compound is preferably an alicyclic dicarboxylic acid compound having a fluorine-based substituent and an aromatic dicarboxylic acid compound having a fluorine-based substituent.

Examples of the diamines include aromatic diamines, alicyclic diamines, and aliphatic diamines. These may also be used in combination of 2 or more types. The diamine is selected from the group consisting of having an alicyclic diamine and having a fluorine-based substituent from the viewpoints of solubility of a polyimine-based polymer to a solvent and transparency and flexibility after forming the resin film 10 . Aromatic diamines are preferred.

When such a polyimide-based polymer is used, it is possible to easily obtain particularly excellent flexibility and have high light transmittance (for example, light light of 550 nm is 85% or more, preferably 88% or more), and low yellow color. A resin film having a degree of YI (for example, 5 or less, preferably 3 or less) and a low haze (for example, 1.5% or less, preferably 1.0% or less).

The polyimine-based polymer may contain a plurality of different types of copolymers containing the above-mentioned repeating structural unit. The polyamidene-based polymer has a weight average molecular weight of usually 10,000 to 500,000. The polyamidene-based polymer preferably has a weight average molecular weight of 50,000 to 500,000, preferably 70,000 to 400,000. The weight average molecular weight is a standard polystyrene-converted molecular weight measured by gel permeation chromatography (GPC). When the weight average molecular weight of the polyimine-based polymer is large, the flexibility tends to be high, and when the weight average molecular weight of the polyimine-based polymer is too large, the viscosity of the varnish becomes high and the processing is high. The tendency to be depressed.

The polyimine-based polymer may contain a halogen atom such as a fluorine atom which can be introduced by the fluorine-based substituent or the like described above. The elastic modulus of the resin film can be obtained by the polyimine-based polymer containing a halogen atom Lift and lower the yellowness. Thereby, damage, wrinkles, and the like which are generated in the resin film can be suppressed, and the transparency of the resin film can be improved. The halogen atom is preferably a fluorine atom. The content of the halogen atom in the polyimine-based polymer is preferably from 1 to 40% by mass, preferably from 1 to 30% by mass, based on the mass of the polyamidene-based polymer.

The resin film 10 may contain one or more types of ultraviolet absorbers. The ultraviolet absorber can be suitably selected from those generally used as a UV absorber in the field of resin materials. The ultraviolet absorber may also contain a compound that absorbs light having a wavelength of 400 nm or less. Examples of the ultraviolet absorber which can be appropriately combined with the polyimine-based polymer include, for example, a diphenylketone-based compound, a salicylate-based compound, a benzotriazole-based compound, and three. At least one compound of the group consisting of compounds.

In the present specification, the term "systemic compound" means a derivative of a compound to which the "system compound" is added. For example, the "diphenylketone-based compound" means a compound having a diphenyl ketone as a matrix of a parent and a substituent bonded to a diphenyl ketone.

The amount of the ultraviolet absorber to be formulated may be any amount as long as the resin film 10 can satisfy the above conditions (i) and (ii). Specifically, the amount of the ultraviolet absorber is usually 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, usually 10% by mass or less, and 8% by mass based on the total mass of the resin film. The following is preferred, and 6 mass% or less is preferred.

The resin film 10 may further contain an inorganic material such as inorganic particles. The inorganic material is preferably a ruthenium material containing a ruthenium atom. The resin film 10 contains an inorganic material such as a ruthenium material, and in terms of flexibility, it is capable of Very good results are obtained.

Examples of the ruthenium-containing ruthenium-containing material include ruthenium oxide particles, a ruthenium compound such as a 4-stage alkoxy decane or a sesquioxane derivative such as tetraethyl orthophthalate (TEOS). Among these ruthenium materials, ruthenium oxide particles are preferred from the viewpoint of transparency and flexibility of the resin film 10.

The average primary particle diameter of the cerium oxide particles is usually 100 nm or less. When the average primary particle diameter of the cerium oxide particles is 100 nm or less, the transparency tends to be improved.

The average primary particle diameter of the cerium oxide particles in the resin film can be obtained by observation by a transmission electron microscope (TEM). The primary particle diameter of the cerium oxide particles can be set to a directional diameter by a transmission electron microscope (TEM). The average primary particle diameter can be determined by TEM observation to determine the primary particle diameter of 10 points and to obtain the average value. The particle distribution of the cerium oxide particles before the formation of the resin film can be obtained by using a commercially available laser diffraction type particle size distribution meter.

In the resin film 10, the mixing ratio of the polyimine-based polymer to the inorganic material is set to 10 in total, and preferably 1:9 to 10:0 in terms of mass ratio, and 3:7 to 10:0 is preferred, preferably 3:7 to 8:2, and more preferably 3:7 to 7:3. The ratio of the inorganic material is usually 20% by mass or more, preferably 30% by mass or more, and usually 90% by mass or less, and preferably 70% by mass or less, based on the total mass of the polyimine-based polymer and the inorganic material. When the blending ratio of the polyimine-based polymer to the inorganic material is within the above range, the transparency and mechanical strength of the resin film are improved. tendency.

The resin film 10 further contains other components in a range that does not significantly impair transparency and flexibility. Examples of other components include coloring agents such as antioxidants, release agents, stabilizers, and blueing agents, flame retardants, slip agents, and leveling agents. The ratio of the components other than the polyimine-based polymer and the inorganic material is preferably more than 0% and 20% by mass or less, more preferably more than 0% and not more than 10% by mass, based on the mass of the resin film 10.

When the resin film 10 contains a polyimine-based polymer and a ruthenium material, the atomic ratio of the ruthenium atom to the nitrogen atom at at least one main surface 10a, that is, Si/N is preferably 8 or more. This atomic ratio is a value calculated by evaluating the composition of the principal surface 10a by X-ray photoelectron spectroscopy (XPS) by X-ray photoelectron spectroscopy (XPS), and the amount of ruthenium atoms present and the amount of nitrogen atoms present.

When the Si/N of the main surface 10a of the resin film 10 is 8 or more, sufficient adhesion can be obtained with the functional layer 20 described later. From the viewpoint of adhesion, the Si/N system is preferably 9 or more, more preferably 10 or more, more preferably 50 or less, and still more preferably 40 or less.

The thickness of the resin film 10 can be appropriately adjusted in accordance with the flexible device to which the laminated body 30 is applied, preferably 10 to 500 μm, more preferably 15 to 200 μm, still more preferably 20 to 100 μm. The resin film 10 having such a configuration has particularly excellent bendability.

Next, an example of a method of producing the resin film 10 of the present embodiment will be described. High polyimine used in the manufacture of resin films The molecular varnish is prepared by dissolving a polyimine polymer which can be dissolved in a solvent by a synthetic method using a conventional polyimine-based polymer and dissolved in a solvent. The solvent may be a solvent which can dissolve the polyimine-based polymer, and examples thereof include dimethylacetamide (DMAC), dimethylformamide (DMF), dimethylammonium (DMSO), and γ. - Butyrolactone (GBL), and a mixed solvent of these.

When a resin film containing an inorganic material is produced, an inorganic material is added to the polyimine-based polymer varnish, and the mixture is stirred and mixed by a conventional stirring method to prepare a dispersion in which the inorganic material is uniformly dispersed. When a UV absorber is formulated, an ultraviolet absorber can be added to the dispersion.

The polyimine-based polymer varnish or dispersion may further contain an additive. Examples of the additive include a coloring agent such as an antioxidant, a releasing agent, a stabilizer, and a bluing agent, a flame retardant, a slip agent, a tackifier, and a leveling agent. The polyimine-based polymer varnish or dispersion may further contain a compound such as an alkoxy decane having one or two or more alkoxylated metal groups which contributes to bonding between inorganic particles. An example of such a compound is an alkoxydecane having an amine group. By using a polyimine-based polymer varnish or dispersion containing such a compound, it is possible to increase the mixing ratio of the inorganic particles while maintaining optical properties such as transparency of the resin film. .

The polyimine-based polymer varnish or dispersion may further contain water. The content of water is usually 0.1 to 10% by mass based on the mass of the polyimine-based polymer varnish or dispersion.

The resin film can be produced by a suitable conventional method. As an example of a manufacturing method, the following methods are mentioned. The above polyimine-based polymer varnish or dispersion is applied to a substrate by a conventional winding type and batch method to form a coating film. The coating film was dried to form a film. Subsequently, the resin film 10 is obtained by peeling the film from the substrate. Examples of the substrate include a polyethylene terephthalate (PET) substrate, a stainless steel (SUS) belt, and a glass substrate.

The coating film may also be heated for drying, and/or baking of the coating film. The heating temperature of the coating film is usually 50 to 350 °C. The heating of the coating film can also be carried out under an inert atmosphere or under reduced pressure. The solvent can be evaporated and removed by heating of the coating film. The resin film can be formed by a method comprising the steps of: drying the coating film at 50 to 150 ° C; and baking the dried coating film at 180 to 350 ° C.

Next, a surface treatment may be applied to at least one main surface of the resin film. The surface treatment is preferably UV ozone treatment. By UV ozone treatment, Si/N can be easily made 8 or more. However, the method of setting Si/N to 8 or more is not limited by UV ozone treatment. On the main faces 10a and/or 10b of the resin film 10, a surface treatment such as plasma treatment or corona discharge treatment may be performed to enhance adhesion to a functional layer to be described later.

The UV ozone treatment is capable of using a conventional ultraviolet light source containing a wavelength of 200 nm or less. As an example of the ultraviolet light source, a low pressure mercury lamp can be cited. As the ultraviolet light source, various commercially available devices having an ultraviolet light source can also be used. The commercially available device is, for example, an ultraviolet (UV) ozone cleaning device UV-208 manufactured by TECHNOVISION.

The resin film 10 of the present embodiment obtained in this manner has excellent flexibility. Further, when at least one main surface 10a has a ratio of the atomic ratio of the ruthenium atom to the nitrogen atom, that is, Si/N is 8 or more, excellent adhesion can be obtained with the functional layer 20 to be described later.

[layered body]

Fig. 2 is a cross-sectional view showing an embodiment of a laminated body. The laminated body 30 shown in Fig. 2 is a laminated body of the resin film 10 and the functional layer 20, and the functional layer 20 is laminated on one main surface 10a of the resin film 10.

When the laminated body 30 is used as an optical member of a flexible device or a substrate or a front panel of a display member, the functional layer 20 can be a layer for further imparting a function (performance) to the laminated body 30. Here, in the present specification, the optical member means a sensor portion or a signal transmitting portion of a touch sensor or the like of the display device, and the display member means an organic EL device or a liquid crystal display of the display device. An image display unit such as a device.

The functional layer 20 is preferably one having at least one function selected from the group consisting of ultraviolet absorption, high surface hardness, adhesion, hue adjustment, and refractive index adjustment.

The ultraviolet absorbing layer (ultraviolet absorbing layer) as the functional layer 20 is composed of, for example, a main material and an ultraviolet absorbing agent dispersed in the main material, wherein the main material is selected from the group consisting of ultraviolet curable transparent resin and electron ray. A hardening type transparent resin and a thermosetting type transparent resin. By providing the ultraviolet absorbing layer as the functional layer 20, it is possible to easily suppress a change in yellowness caused by light irradiation.

The ultraviolet curable type, the electron beam hardening type, or the thermosetting type transparent resin which is the main material of the ultraviolet absorbing layer is not particularly limited, and may be, for example, a poly(meth)acrylate. The ultraviolet absorber can be selected from the same compounds as those exemplified as the ultraviolet absorber which can be contained in the resin film 10.

The ultraviolet absorbing layer may be a layer that absorbs light having a wavelength of 400 nm or less (for example, light having a wavelength of 313 nm) by 95% or more. In other words, the ultraviolet absorbing layer may also be a layer having a transmittance of light having a wavelength of 400 nm or less (for example, light having a wavelength of 313 nm) of less than 5%. The ultraviolet absorbing layer can contain a UV absorber having a concentration at which such transmittance can be obtained. The content ratio of the ultraviolet absorber in the ultraviolet absorbing layer (functional layer 20) is based on the mass of the ultraviolet absorbing layer, and is usually 1% by mass or more, from the viewpoint of suppressing an increase in the yellowness of the layered body due to light irradiation. It is preferably 3% by mass or more, usually 10% by mass or less, and preferably 8% by mass or less.

As the layer (hard coat layer) of the function layer 20 having a function of giving a high hardness to the surface, for example, a layer having a surface having a pencil hardness higher than the pencil hardness of the surface of the resin film is provided to the laminate. The hard coat layer is not particularly limited, and includes an ultraviolet curable type, an electron beam hardening type or a thermosetting type resin typified by poly(meth)acrylates. The hard coat layer may also contain a photopolymerization initiator and an organic solvent. The poly(meth) acrylate is, for example, one or more selected from the group consisting of polyurethane (meth) acrylate, epoxy (meth) acrylate, and other polyfunctional poly(meth) acrylates. Poly(meth)acrylate formed by (meth) acrylates. The hard coat layer may contain cerium oxide, aluminum oxide, polyorganosiloxane, etc. in addition to the above components. Inorganic oxides.

The layer (adhesive layer) having an adhesive function as the functional layer 20 has a function of causing the laminated body 30 to follow other members. The material for forming the adhesive layer may, for example, be a thermosetting resin composition or a photocurable resin composition.

The adhesive layer may also be composed of a resin composition containing a component having a polymerizable functional group. At this time, after the laminated body 30 is adhered to the other member, the resin composition constituting the adhesive layer is further polymerized, whereby a strong adhesion can be achieved. The adhesive strength of the resin film 10 and the adhesive layer is preferably 0.1 N/cm or more, and more preferably 0.5 N/cm or more.

The adhesive layer may contain a thermosetting resin composition or a photocurable resin composition as a material. At this time, by supplying energy after the event, the resin composition can be polymerized and cured.

The adhesive layer may be attached to the layer of the object by pressing, which is called Pressure Sensitive Adhesive (PSA). The pressure-sensitive adhesive may be an adhesive having "adhesiveness at normal temperature and adhering to a material to be pressed by a light pressure" (JIS K6800), or "containing a specific component in a protective film (micro A capsule-type adhesive agent (JIS K6800) which is capable of maintaining the stability inside to the capsule (JIS K6800) by a suitable means (pressure, heat, etc.).

As a layer (hue adjustment layer) having a function of hue adjustment of the functional layer 20, the layered body 30 can be adjusted to a layer of a target hue. The hue adjustment layer may be, for example, a layer containing a resin and a coloring agent. Examples of the colorant include titanium oxide, zinc oxide, iron oxide red, and titanium oxide. An inorganic pigment such as calcined pigment, ultramarine, cobalt aluminate or carbon black; an azo compound, a quinacridone compound, an anthraquinone compound, a perylene compound, an isoindolinone compound , an organic pigment such as a phthalocyanine compound, a quinophthalone compound, a threne compound, and a diketopyrrolopyrrole compound; an extender pigment such as barium sulfate or calcium carbonate; a basic dye; Dyes such as acid dyes and mordant dyes.

The layer (refractive index adjusting layer) having the refractive index adjusting function as the functional layer 20 is a layer having a refractive index different from that of the resin film 10 and capable of imparting a predetermined refractive index to the laminated body. The refractive index adjusting layer may be, for example, a resin layer containing a resin selected as appropriate, and optionally a pigment, or a metal thin film.

Examples of the pigment for adjusting the refractive index include cerium oxide, aluminum oxide, cerium oxide, tin oxide, titanium oxide, zirconium oxide, and cerium oxide. The average particle diameter of the pigment is preferably 0.1 μm or less. By setting the average particle diameter of the pigment to 0.1 μm or less, it is possible to prevent the light transmitted through the refractive index adjusting layer from being diffusely reflected and to prevent the transparency from being lowered.

Examples of the metal used in the refractive index adjusting layer include titanium oxide, cerium oxide, zirconium oxide, zinc oxide, tin oxide, antimony oxide, indium oxide, titanium oxynitride, titanium nitride, hafnium oxynitride, and nitrogen. A metal oxide or metal nitride such as ruthenium or the like.

The functional layer 20 appropriately has the above-described functions in accordance with the use of the laminated body 30. The functional layer 20 can be a single layer or a plurality of layers. Each layer can have one type of function or two or more types of functions.

The functional layer 20 is preferably provided with a function of exhibiting high hardness on the surface and an ultraviolet absorbing function. In this case, the functional layer 20 is preferably one of the following: "a single layer having a function of causing a high hardness on the surface and an ultraviolet absorbing function", "a layer having a function of causing a surface to exhibit high hardness, and having an ultraviolet absorbing property. "Multilayer of the layer" or "a multilayer comprising a layer having a function of rendering the surface high in hardness and having a function of ultraviolet absorbing function and a layer having a function of rendering the surface high in hardness".

The thickness of the functional layer 20 can be appropriately adjusted in accordance with the flexible device to which the laminated body 30 is applied, preferably from 1 to 100 μm, preferably from 2 to 80 μm. Typically, the functional layer 20 is thinner than the resin film 10.

The laminated body 30 can be obtained by forming the functional layer 20 on the main surface 10a of the resin film 10. The functional layer 20 can be formed using conventional winding and batch methods.

The ultraviolet absorbing layer of the functional layer 20 can be formed by applying a dispersion liquid containing a main component such as a UV absorber and a resin which disperses the ultraviolet absorber to the main surface 10a of the resin film 10, and the coating film can be formed. The coating film is dried and hardened to form.

The hard coat layer of the functional layer 20 can be formed, for example, by applying a solution containing a resin forming a hard coat layer to the main surface 10a of the resin film 10 to form a coating film, and drying and hardening the coating film.

The adhesive layer of the functional layer 20 can be formed, for example, by applying a solution containing an adhesive for forming an adhesive layer on the main surface 10a of the resin film 10 to form a coating film, and drying and curing the coating film.

The color adjustment layer of the functional layer 20 can be coated with a dispersion of a main material such as a pigment or the like which forms a hue adjustment layer and a resin which disperses a pigment or the like on the main surface 10a of the resin film 10, for example. The film is formed by drying and hardening the coating film.

The refractive index adjusting layer of the functional layer 20 can be applied to the main surface 10a of the resin film 10 by dispersing a main material such as an inorganic particle or the like which forms a refractive index adjusting layer, and a resin which disperses inorganic particles or the like. The coating film is formed into a liquid, and the coating film is dried and hardened to form.

The functional layer 20 has a function of exhibiting a high hardness on the surface and a single layer having an ultraviolet absorbing function, and is capable of applying a resin containing a UV absorber and a resin which disperses the ultraviolet absorber to the main surface 10a of the resin film 10 And forming a coating film by forming a dispersion of the resin of the hard coat layer, and drying and hardening the coating film to form. The resin as the main material and the resin forming the hard coat layer may be the same.

A functional layer comprising a layer having a function of exhibiting high hardness on the surface and a layer having ultraviolet absorbing layer can be formed by the following method.

On the main surface 10a of the resin film 10, a dispersion liquid of a main material containing a UV absorber and a resin which disperses the ultraviolet absorber is applied to form a coating film, and the coating film is dried and cured to form an ultraviolet absorbing layer. Next, a solution containing a resin forming a hard coat layer is applied to the ultraviolet absorbing layer to form a coating film, and the coating film is dried and cured to form a hard coat layer. With this method, it is possible to form a functional layer including a layer having a function of exhibiting a high hardness on the surface and a layer having a layer having ultraviolet absorption.

A multilayer comprising a layer having a function of exhibiting high hardness on the surface and a layer having an ultraviolet absorbing function and a layer having a function of exhibiting high hardness on the surface can be formed by the following method.

A main layer of a resin containing an ultraviolet absorber, a resin which disperses the ultraviolet absorber, and a dispersion of a resin which forms a hard coat layer may be applied to the main surface 10a of the resin film 10 to form a coating film, and the coating film may be dried. And hardening to form a single layer having a function of exhibiting high hardness on the surface and having an ultraviolet absorbing function, and applying a solution containing a resin forming a hard coat layer to the single layer to form a coating film, and drying the coating film And hardened to form a hard coat layer. According to this method, it is possible to form a functional layer including a layer having a function of exhibiting a high hardness on the surface and a layer having an ultraviolet absorbing function and a layer having a function of exhibiting a high hardness on the surface.

The layered body 30 of the present embodiment obtained in this manner has excellent flexibility. The laminated body 30 can have the functions of transparency, ultraviolet light resistance, and the function of exhibiting high hardness on the surface of the optical member of the flexible device or the substrate of the display member or the front panel. . When the Si/N of the main surface 10a of the resin film 10 is 8 or more, the adhesiveness of the resin film 10 and the functional layer 20 is also excellent.

Fig. 3 is a cross-sectional view showing an embodiment of a laminated body. The laminated body 30 shown in Fig. 3 further has an undercoat layer 25 provided between the resin film 10 and the functional layer 20 in addition to the resin film 10 and the functional layer 20 which are the same as the laminated body of Fig. 2 . The undercoat layer 25 is laminated on one main surface 10a of the resin film 10. The functional layer 20 is layered at The main surface of the undercoat layer 25 that is in contact with the resin film 10 is the main surface 25a on the opposite side.

The undercoat layer 25 is a layer made of a primer, and preferably contains a material capable of improving the adhesion to the resin film 10 and the functional layer 20. The compound contained in the undercoat layer 25 may be chemically bonded to the interface with a polyimide-based polymer or a ruthenium material contained in the resin film 10.

The primer may, for example, be a primer of an ultraviolet curable type, a thermosetting type or a two-liquid curing type epoxy compound. The primer may also be a polyamic acid. These primers are suitable because they can improve the adhesion to the resin film 10 and the functional layer 20.

The primer may also contain a decane coupling agent. The decane coupling agent can also be chemically bonded to the ruthenium material contained in the resin film 10 by a condensation reaction. In particular, the decane coupling agent can be used in a case where the blending ratio of the ruthenium material contained in the resin film 10 is high.

The decane coupling agent may, for example, be a compound having an alkoxyalkyl group having a fluorene atom and one to three alkoxy groups covalently bonded to the ruthenium atom. A compound having a structure in which two or more alkoxy groups are covalently bonded to a ruthenium atom is preferred, and a compound having a structure in which three or more alkoxy groups are covalently bonded to a ruthenium atom is preferred. Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, a n-butoxy group, and a third butoxy group. In particular, it is preferred to use a methoxy group and an ethoxy group because the reactivity with the ruthenium material can be improved.

The decane coupling agent is preferably a substituent having high affinity with the resin film 10 and the functional layer 20. From and in the resin film 10 From the viewpoint of the affinity of the polyimine-based polymer, the substituent of the decane coupling agent is preferably an epoxy group, an amine group, a urea group or an isocyanate group. When the functional layer 20 contains a (meth) acrylate, the decane coupling agent used in the undercoat layer 25 has an epoxy group, a methacryl fluorenyl group, an acryl fluorenyl group, an amine group or a benzene because the affinity is improved. Vinyl is preferred. Among these, a decane coupling agent having a substituent selected from a methacryl fluorenyl group, an acryl fluorenyl group, and an amine group has a tendency to exhibit excellent affinity with the resin film 10 and the functional layer 20, good.

The thickness of the undercoat layer 25 can be appropriately adjusted in accordance with the functional layer 20, preferably 0.01 nm to 20 μm. When a primer of an epoxy compound is used, the thickness of the undercoat layer 25 is preferably from 0.01 μm to 20 μm, more preferably from 0.1 μm to 10 μm. When the decane coupling agent is used, the thickness of the undercoat layer 25 is preferably 0.1 nm to 1 μm, more preferably 0.5 nm to 0.1 μm.

In the laminated body 30 of FIG. 3, for example, a coating film in which a primer is dissolved is applied to the main surface 10a of the resin film 10, and the formed coating film is dried and hardened to form an undercoat layer. Method to manufacture. The method of forming the other members is the same as that of the layered body 30 of Fig. 2 . The undercoat layer 25 and the functional layer 20 may be simultaneously hardened, or may be additionally hardened before the functional layer 20 is formed.

The resin film and the laminated system of the present embodiment have high transparency and can maintain excellent visibility at the time of bending. Further, the resin film and the laminate also have excellent flexibility. When the undercoat layer is provided between the resin film and the functional layer, the adhesion between the resin film and the functional layer is changed. high. When the resin film and the laminated system are applied to the optical member of the flexible device or the substrate of the display member or the front panel, it is possible to have desired transparency, ultraviolet resistance, and a function of exhibiting high hardness on the surface. Functionality.

The structure of the resin film and the laminate can be appropriately deformed. For example, a functional layer can be provided on each side of the resin film. At this time, an undercoat layer may be provided between the respective functional layers and the resin film.

[Display device (flexible device)]

Fig. 4 is a cross-sectional view showing an embodiment of a display device. The display device 100 shown in FIG. 4 has an organic EL device 50, a touch sensor 70, and a front panel 90. These systems are usually housed in a housing. Between the organic EL device 50 and the touch sensor 70, and between the touch sensor 70 and the front panel 90, for example, an optical adhesive (not shown) is used.

The organic EL device 50 includes a display member of the organic EL element 51, the first substrate 55, the second substrate 56, and the sealing member 59.

The organic EL element 51 includes a pair of electrodes (the first electrode 52 and the second electrode 53) and the light-emitting layer 54. The light-emitting layer 54 is disposed between the first electrode 52 and the second electrode 53.

The first electrode 52 is formed using a light-transmitting conductive material. The second electrode 53 may also have light transmittance. As the first electrode 52 and the second electrode 53, a conventional material can be used.

The light-emitting layer 54 can use the conventional structure constituting the organic EL element The luminescent material is formed. The luminescent material may be any of a low molecular compound and a high molecular compound.

When electric power is supplied between the first electrode 52 and the second electrode 53, the light-emitting layer 54 is supplied with a carrier (electrons and holes) and generates light at the light-emitting layer 54. The light generated by the light-emitting layer 54 is transmitted to the outside of the organic EL device 50 through the first electrode 52 and the first substrate 55.

The first substrate 55 is formed of a material having light transparency. The second substrate 56 may also have light transmittance. The first substrate 55 and the second substrate 56 are bonded together by a sealing material 59 that is disposed to surround the periphery of the organic EL element. The first substrate 55, the second substrate 56, and the sealing material 59 form a sealing structure in which the organic EL element is sealed inside. Most of the first substrate 55 and/or the second substrate 56 are gas barrier materials.

As a material for forming either or both of the first substrate 55 and the second substrate 56, an inorganic material such as glass or a conventional transparent resin such as an acrylic resin can be used. As such members, the resin film or laminate of the above-described embodiment can also be used.

The first substrate 55 and the second substrate 56 which can be used in the laminate of the present embodiment are the base material or the gas barrier material of the display member of the present embodiment. The organic EL device 50 having the first substrate 55 and the second substrate 56 has excellent flexibility because the resin film or the laminate of the present embodiment is used.

The touch sensor 70 is an optical member having a touch sensor substrate 71 and an element layer 72, wherein the element layer 72 has a detecting element formed on the touch sensor substrate 71.

The touch sensor substrate 71 is formed using a material having light transparency. As the touch sensor substrate 71, an inorganic material such as glass or a conventional transparent resin such as an acrylic resin can be used. As the touch sensor substrate 71, the resin film or the laminate of the above-described embodiment can also be used.

The element layer 72 is formed with a conventional detecting element composed of a semiconductor element, a wiring, a resistor, or the like. As a configuration of the detecting element, a conventional detection method can be realized by a matrix switch, a resistive film method, a capacitive type or the like.

The touch sensor substrate 71 of the laminated body of the present embodiment can be used as the optical member of the present embodiment. The touch sensor 70 having such a touch sensor substrate 71 has excellent flexibility because the resin film or the laminate of the embodiment is used.

The front panel 90 is formed of a material having light transparency. The front panel 90 is located on the outermost layer on the display screen side of the display device and functions as a protective member for protecting the display device. The front panel is also known as the window film. As the front panel 90, an inorganic material such as glass or a conventional transparent resin such as an acrylic resin can be used. As the front panel 90, the resin film or the laminate of the above-described embodiment can also be used. When a laminate is used as the front panel 90, generally, the functional layer is provided with a laminate in a direction outside the display device.

The resin film or the laminate front panel 90 of the present embodiment can be excellent in flexibility because the resin film or the laminate of the present embodiment is used.

When the resin film or the laminate of the present embodiment is used as one or more constituent members selected from the organic EL device 50, the touch sensor 70, and the front panel 90, the display device 100 can have excellent flexibility. That is, the display device 100 can be a flexible device.

The device (flexible device) to which the resin film and the laminate of the present embodiment can be applied is not limited to the above display device. For example, a solar cell having a substrate on which a photoelectric conversion element is formed and a front panel provided on the surface of the substrate can also be used. In this case, when the resin film or the laminate of the present embodiment is used as the substrate or the front panel of the solar cell, the entire solar cell can have excellent flexibility.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited to the following examples.

[Example 1]

A compound represented by the formula (1), a compound represented by the formula (2), a compound represented by the formula (3), a catalyst, and a solvent (γ-butyrolactone and dimethylacetamide) are added to the polymerization tank after the nitrogen substitution. . The amount of addition is 75.0 g of the compound represented by the formula (1), 36.5 g of the compound represented by the formula (2), 76.4 g of the compound represented by the formula (3), 1.5 g of a catalyst, 438.4 g of γ-butyrolactone, and dimethyl group. Acetamide 313.1 g. The molar ratio of the compound represented by the formula (2) to the compound represented by the formula (3) is 3:7, the total of the compound represented by the formula (2) and the compound represented by the formula (3) and the compound represented by the formula (1) The molar ratio is 1.00:1.02.

After stirring the mixture in the polymerization tank to dissolve the raw material in the solvent, the mixture was heated to 100 ° C, and then heated to 200 ° C and held for 4 hours to be polymerized into polyimine. In this heating, the water in the liquid is removed. Subsequently, polyimine is obtained by purification and drying.

Next, a γ-butyrolactone solution adjusted to a concentration of 20% by mass of polyimine, a dispersion obtained by dispersing cerium oxide particles having a solid concentration of 30% by mass in γ-butyrolactone, and an alkane having an amine group Oxyacetamide dimethylacetamide solution, three A UV absorber (TINUVIN (registered trademark) 479, manufactured by BASF Corporation), and water were mixed and stirred for 30 minutes. The agitation is carried out in accordance with the method described in U.S. Patent No. 8,207,256 B2.

Here, the mass ratio of cerium oxide particles to polyimine is 60:40; and the amount of alkoxy decane having an amine group is set to 1.67 with respect to 100 parts by mass of the total of cerium oxide particles and polyimine. Parts by mass; 100 parts by mass relative to the total of cerium oxide particles and polyimine, three The amount of the ultraviolet absorbing agent is 3 parts by mass, and the amount of water is 10 parts by mass based on 100 parts by mass of the total of the cerium oxide particles and the polyimide.

The mixed solution was coated on a glass substrate and heated at 50 ° C. In minutes, it was heated at 140 ° C for 10 minutes and dried. Subsequently, a resin film having a thickness of 80 μm was obtained by peeling the film from the glass substrate, mounting a metal frame, and heating at 210 ° C for 1 hour. The content of the cerium oxide particles in the resin film was 60% by mass.

[Example 2 (Laminated body)]

On one surface of the resin film produced in Example 1, a two-liquid-curing primer (trade name: ARACOAT AP2510, manufactured by Arakawa Chemical Industries Co., Ltd.) was applied to form a coating film as an undercoat layer, and the coating film was dried and hardened. An undercoat layer having a thickness of 1 μm was formed.

Next, 47.5 parts by mass of a tetrafunctional acrylate (trade name: A-TMMT, manufactured by Shin-Nakamura Chemical Co., Ltd.), a tetrafunctional acrylate (trade name: A-TMPT, manufactured by Shin-Nakamura Chemical Co., Ltd.), 47.5 parts by mass, a reactive amine Formate polymer (trade name: 8BR-600, manufactured by Daisei FINE CHEMICAL Co., Ltd., 40% by mass) 12.5 parts by mass, three 3 parts by mass of a UV absorber (TINUVIN (registered trademark) 479, manufactured by BASF), 8 parts by mass of a photopolymerization initiator (IRGACURE (registered trademark) 184, CIBA. SPECIALTY. CHEMICALS), and a leveling agent (product) A solution prepared by mixing 0.6 parts by mass of BYK-350 and BYK-Chemie Japan Co., Ltd. and 107 parts by mass of methyl ethyl ketone was applied onto the undercoat layer to form a coating film. The coating film was dried and hardened to form a functional layer having a thickness of 10 μm as a "functional layer having a function of exhibiting high hardness on the surface and a function of ultraviolet absorbing function", thereby obtaining a layered product of Example 2.

[Comparative Example 1]

Add three in addition to the mixed solution used to form the resin film A resin film having a thickness of 80 μm was obtained in the same manner as in Example 1 except for the ultraviolet absorber.

[Comparative Example 2]

Polyimine ("Neopulim" manufactured by Mitsubishi Gas Chemical Co., Ltd.) having a glass transition temperature of 390 ° C was prepared. a γ-butyrolactone solution having a polyamidene concentration of 20% by mass, a dispersion liquid obtained by dispersing cerium oxide particles having a solid concentration of 30% by mass in γ-butyrolactone, and an alkoxy decane having an amine group. The dimethylacetamide solution and water were mixed and stirred for 30 minutes to obtain a mixed solution. The mass ratio of cerium oxide particles to polyimine is 55:45 and the amount of the alkoxy decane having an amine group is 1.67 parts by mass relative to 100 parts by mass of the total of cerium oxide particles and polyimine, and is relative to oxidation. The total amount of the cerium particles and the polyimine is 100 parts by mass, and the amount of water is 10 parts by mass. Using this mixed solution, a resin film having a thickness of 80 μm was obtained in the same manner as in Example 1.

(Evaluation) 1) Optical characteristics (yellowness (YI value))

The yellowness (Yellow Index: YI value) of each of the resin films of the examples and the comparative examples was measured using an ultraviolet-visible near-infrared spectrophotometer V-670 manufactured by JASCO Corporation. After the background was measured without the sample, the resin film was attached to the sample holder and measured. For the transmittance of light from 300 nm to 800 nm, 3 stimulus values (X, Y, Z) were obtained. The YI value was calculated based on the following formula.

YI=100×(1.2769X-1.0592Z)/Y

2) Transmittance

The transmittance of light having a wavelength of 550 nm was calculated by measuring the transmittance of light of 300 nm to 800 nm using an ultraviolet-visible near-infrared spectrophotometer V-670 manufactured by JASCO Corporation.

3) Haze

The resin film of the examples and the comparative examples was attached to a sample holder using a fully automatic direct reading haze computer HGM-2DP manufactured by SUGA Testing Machine Co., Ltd., and the haze of the resin film was measured.

4) Light irradiation test

The resin films of the examples and the comparative examples were subjected to a light irradiation test using UVCON manufactured by Atras. The light source was set to UV-B 313 nm, the output power was set to 40 W, and the distance between the resin film and the light source was set to 5 cm.

The resin film was irradiated with ultraviolet rays for 24 hours. After the ultraviolet irradiation, the optical characteristics (YI value, transmittance) as described above were evaluated.

5) Visibility

The film before the light irradiation test was bent to confirm the contrast and hue at this time. The appearance state of the device is determined based on the following criteria.

A: No change in contrast and hue can be observed.

C: Appearance changes such as contrast and hue change can be observed.

The evaluation results are shown in Table 1. The resin film of the example provided with the light irradiation test satisfies the above conditions (i) and (ii), and it can be confirmed that the resin film and the laminated system having the resin film have high visibility when bent.

10‧‧‧Resin film

10a, 10b‧‧‧ main faces

Claims (12)

A resin film comprising a polyimine-based polymer film in which a resin is provided from a main surface side of the resin film by a light source having an output of 40 W at a distance of 5 cm from the resin film. After the film was irradiated with light of 313 nm for 24 hours, the resin film satisfies the following conditions: (i) the resin film after the light irradiation test has a transmittance of 85% or more for light of 550 nm; Ii) The resin film before the light irradiation test had a yellowness of 5 or less, and the difference in yellowness before and after the light irradiation test of the resin film was less than 2.5. The resin film according to claim 1, wherein the resin film after the light irradiation test has a haze of 1.0% or less. The resin film according to claim 1 or 2, wherein the resin film further contains an ultraviolet absorber. A laminate comprising the resin film according to any one of claims 1 to 3, and a functional layer provided on at least one side of the resin film. The laminate according to claim 4, wherein the functional layer has at least one functional layer selected from the group consisting of ultraviolet absorption, adhesion, and high hardness on the surface. The laminate according to claim 4 or 5, further comprising an undercoat layer provided between the resin film and the functional layer. An optical member comprising the resin film according to claim 1 or 2. An optical member comprising the laminate according to any one of claims 3 to 6. A display member comprising the resin film according to claim 1 or 2. A display member having the laminate according to any one of claims 3 to 6. A front panel having the resin film described in claim 1 or 2. A front panel having the laminate according to any one of claims 3 to 6.