WO2017014279A1 - 樹脂フィルム、積層体、光学部材、表示部材及び前面板 - Google Patents
樹脂フィルム、積層体、光学部材、表示部材及び前面板 Download PDFInfo
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- WO2017014279A1 WO2017014279A1 PCT/JP2016/071440 JP2016071440W WO2017014279A1 WO 2017014279 A1 WO2017014279 A1 WO 2017014279A1 JP 2016071440 W JP2016071440 W JP 2016071440W WO 2017014279 A1 WO2017014279 A1 WO 2017014279A1
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- layer
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- laminate
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- MGNZXYYWBUKAII-UHFFFAOYSA-N C1C=CC=CC1 Chemical compound C1C=CC=CC1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 9
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Definitions
- the present invention relates to a resin film, a laminate, an optical member, a display member, and a front plate.
- glass has been used as a base material for display members, a base material for optical members, and a material for a front plate constituting various display devices such as solar cells or displays.
- glass has the disadvantage of being easily broken and heavy.
- the glass substrate or the glass front plate has not had sufficient material properties. Therefore, an acrylic resin and a laminate obtained by imparting scratch resistance to the resin have been studied as a material or a substrate that can replace glass.
- a composite material of an organic material and an inorganic material such as a hybrid film containing polyimide and silica has also been studied (see, for example, Patent Documents 1 and 2).
- a resin film containing a polyimide polymer can achieve excellent flexibility while having high transparency.
- a resin film containing a polyimide-based polymer may cause changes in contrast and hue when bent, and further improvement is necessary in this respect.
- the resin film applied to the base material of the display member of the flexible device, the base material of the optical member and / or the front plate is required to have good visibility when bent.
- a main object of the present invention is to improve visibility at the time of bending with respect to a resin film containing a polyimide polymer and having high transparency.
- the resin film according to one embodiment of the present invention contains a polyimide polymer.
- the resin The film satisfies the following conditions.
- the resin film after the light irradiation test has a transmittance of 85% or more for light of 550 nm; and
- the resin film before the light irradiation test has a yellowness of 5 or less, and the difference in yellowness before and after the light irradiation test of the resin film is less than 2.5.
- This invention provides the laminated body which has the said resin film and the functional layer provided in the at least one surface side of this resin film.
- the functional layer may be a layer having at least one function selected from the group consisting of ultraviolet absorption, adhesiveness, and a function of developing high hardness on the surface.
- the laminate may further include a primer layer provided between the resin film and the functional layer.
- the substrate of the optical member or display member according to one embodiment of the present invention and the front plate have the resin film or laminate. These can contribute to excellent visibility when bent when applied to a flexible device.
- the visibility at the time of bending can be improved with respect to the transparent resin film containing the polyimide polymer.
- FIG. 1 is a cross-sectional view showing an embodiment of a resin film.
- a resin film 10 shown in FIG. 1 contains a polyimide-based polymer and has a pair of opposing main surfaces 10a and 10b.
- a light irradiation test for irradiating the resin film 10 with light of 313 nm from the main surface 10a side for 24 hours with a light source with an output of 40 W provided at a distance of 5 cm from the resin film 10 is as follows. : (I) The resin film after the light irradiation test has a transmittance of 85% or more for light of 550 nm, 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 is less than 2.5. Meet. A resin film satisfying these conditions (i) and (ii) is unlikely to cause a change in contrast or hue when bent, and can maintain good visibility.
- a resin film satisfying the conditions (i) and (ii) can be easily obtained by using, for example, a polyimide polymer having high transparency and including an ultraviolet absorber in the resin film.
- a polyimide polymer having high transparency and the ultraviolet absorber will be described later.
- the transmittance for light at 550 nm of the resin film 10 after the light irradiation test is preferably 90% or more, usually 100% or less, and may be 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 with respect to light of 550 nm.
- the transmittance of the resin film with respect to light having a predetermined wavelength means the ratio of the intensity of light having the same wavelength transmitted through the resin film to the intensity of light having the predetermined wavelength incident on the resin film. Haze can be measured according to JIS K 7105: 1981. Details of the transmittance and haze measurement method will be described in Examples 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.
- ⁇ YI is preferably 2.3 or less, more preferably 2.0 or less, and may be 0.1 or more. Details of the yellowness measurement method will be described in the examples described later.
- Resin film 10 contains a polyimide polymer.
- the polyimide polymer means a polymer having at least one repeating structural unit represented by the formula (PI), the formula (a), the formula (a ′) or the formula (b). . It is preferable from the viewpoint of the strength and transparency of the film that the repeating structural unit represented by the formula (PI) is the main structural unit of the polyimide polymer.
- the repeating structural unit represented by the formula (PI) is preferably 40 mol% or more, more preferably 50 mol% or more, further preferably 70 mol%, based on all repeating structural units of the polyimide-based polymer. More preferably, it is 90 mol% or more, and still more preferably 98 mol%.
- the organic group of the tetravalent organic group represented by G includes an acyclic aliphatic group, a cyclic aliphatic group, and an aromatic group. And a group selected from the group consisting of:
- the organic group of G is preferably a tetravalent cyclic aliphatic group or a tetravalent aromatic group from the viewpoint of transparency and flexibility of the resin film 10.
- the aromatic group include a monocyclic aromatic group, a condensed polycyclic aromatic group, and a non-condensed polycyclic aromatic group having two or more aromatic rings and connected to each other directly or by a bonding group. Etc.
- the organic group of G is a cyclic aliphatic group, a cyclic aliphatic group having a fluorine-based substituent, a monocyclic aromatic group having a fluorine-based substituent, A condensed polycyclic aromatic group having a fluorine-based substituent or a non-condensed polycyclic aromatic group having a fluorine-based substituent is preferable.
- the fluorine-based substituent means a group containing a fluorine atom.
- the fluorine-based substituent is preferably a fluoro group (fluorine atom, -F) and a perfluoroalkyl group, more preferably a fluoro group and a trifluoromethyl group.
- the organic group of G is, for example, 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 heteroalkylaryl.
- Examples of the bonding group include —O—, an alkylene group having 1 to 10 carbon atoms, —SO 2 —, —CO— or —CO—NR— (where R represents a methyl group, an ethyl group, a propyl group, etc. 3 represents an alkyl group or a hydrogen atom).
- the carbon number of the tetravalent organic group represented by G is usually 2 to 32, preferably 4 to 15, more preferably 5 to 10, and further preferably 6 to 8.
- the organic group of G is a cycloaliphatic group or an aromatic group, at least one of the carbon atoms constituting these groups may be replaced with a heteroatom.
- Heteroatoms include O, N, or S.
- G examples include groups represented by the following formula (20), formula (21), formula (22), formula (23), formula (24), formula (25), or formula (26). It is done. * In the formula indicates a bond.
- 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— is represented.
- Ar represents an aryl group having 6 to 20 carbon atoms, and may be, for example, a phenylene group. At least one of the hydrogen atoms of these groups may be substituted with a fluorine-based substituent.
- the organic group of the divalent organic group represented by A includes an acyclic aliphatic group, a cyclic aliphatic group, and an aromatic group.
- the divalent organic group represented by A is preferably selected from a divalent cycloaliphatic group and a divalent aromatic group.
- the aromatic group includes a monocyclic aromatic group, a condensed polycyclic aromatic group, and a non-condensed polycyclic aromatic group having two or more aromatic rings, which are connected to each other directly or by a bonding group. Groups. From the viewpoint of transparency of the resin film and suppression of coloring, it is preferable that a fluorine-based substituent is introduced into the organic group of A.
- the organic group of A is, for example, 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 heteroalkylaryl.
- the hetero atom include O, N, or S.
- Examples of the bonding group include —O—, an alkylene group having 1 to 10 carbon atoms, —SO 2 —, —CO—, or —CO—NR— (R represents methyl Group, an alkyl group having 1 to 3 carbon atoms such as an ethyl group or a propyl group, or a hydrogen atom).
- the carbon number of the divalent organic group represented by A is usually 2 to 40, preferably 5 to 32, more preferably 12 to 28, and further preferably 24 to 27.
- A include groups represented by the following formula (30), formula (31), formula (32), formula (33), or formula (34).
- * In the formula indicates a bond.
- Z 1 ⁇ Z 3 are each independently a single bond, -O -, - CH 2 - , - C (CH 3) 2 -, - SO 2 -, - CO- or -CO-NR- (R is Represents a C 1-3 alkyl group such as a methyl group, an ethyl group, or a propyl group, or a hydrogen atom.
- Z 1 and Z 2 , and Z 2 and Z 3 are each preferably in the meta position or the para position with respect to each ring.
- Z 1 and the single bond at the terminal, Z 2 and the single bond at the terminal, and Z 3 and the single bond at the terminal are preferably in the meta position or the para position, respectively.
- 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 these groups may be substituted with a fluorine-based substituent.
- At least one hydrogen atom constituting at least one of A and G is at least one selected from the group consisting of a fluorine-based substituent, a hydroxyl group, a sulfone group, and an alkyl group having 1 to 10 carbon atoms. It may be substituted with a functional group.
- the organic group of A and the organic group of G are each a cyclic aliphatic group or an aromatic group, it is preferable that at least one of A and G has a fluorine-based substituent, and both A and G are fluorine. It is more preferable to have a system substituent.
- G 2 in the formula (a) is a trivalent organic group.
- This organic group can be selected from the same groups as the organic group of G in formula (PI) except that it is a trivalent group.
- Examples of G 2 include groups in which any one of the four bonds of the groups represented by formulas (20) to (26) listed as specific examples of G is replaced with a hydrogen atom. Can do.
- a 2 in formula (a) can be selected from the same groups as A in formula (PI).
- G 4 in the formula (b) is a divalent organic group.
- This organic group can be selected from the same groups as the organic group of G in formula (PI) except that it is a divalent group.
- Examples of G 4 include groups in which any two of the four bonds of the groups represented by formulas (20) to (26) listed as specific examples of G are replaced with hydrogen atoms. Can do.
- a 4 in formula (b) can be selected from the same groups as A in formula (PI).
- 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 diamines and tricarboxylic acid compounds.
- the repeating structural unit represented by the formula (b) is usually derived from diamines and dicarboxylic acid compounds.
- tetracarboxylic acid compounds include aromatic tetracarboxylic acid compounds, alicyclic tetracarboxylic acid compounds, and acyclic aliphatic tetracarboxylic acid compounds. Two or more of these may be used in combination.
- the tetracarboxylic acid compound is preferably a tetracarboxylic dianhydride, and examples of the tetracarboxylic dianhydride include aromatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, and acyclic fatty acids.
- Group tetracarboxylic dianhydride examples include aromatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, and acyclic fatty acids.
- the tricarboxylic acid compound examples include aromatic tricarboxylic acid, alicyclic tricarboxylic acid, acyclic aliphatic tricarboxylic acid and related acid chloride compounds, acid anhydrides and the like.
- the tricarboxylic acid compound is preferably selected from aromatic tricarboxylic acids, alicyclic tricarboxylic acids, acyclic aliphatic tricarboxylic acids, and related acid chloride compounds. Two or more tricarboxylic acid compounds may be used in combination.
- the tricarboxylic acid compound may be selected from an alicyclic tricarboxylic acid compound and an aromatic tricarboxylic acid compound. preferable. From the viewpoint of transparency of the resin film and suppression of coloring, the tricarboxylic acid compound is preferably selected from an alicyclic tricarboxylic acid compound having a fluorine-based substituent and an aromatic tricarboxylic acid compound having a fluorine-based substituent.
- dicarboxylic acid compound examples include aromatic dicarboxylic acid, alicyclic dicarboxylic acid, acyclic aliphatic dicarboxylic acid and related acid chloride compounds, acid anhydrides and the like.
- the dicarboxylic acid compound is preferably selected from aromatic dicarboxylic acids, alicyclic dicarboxylic acids, acyclic aliphatic dicarboxylic acids and related acid chloride compounds. Two or more dicarboxylic acid compounds may be used in combination.
- the dicarboxylic acid compound may be selected from alicyclic dicarboxylic acid compounds and aromatic dicarboxylic acid compounds. preferable. From the viewpoint of transparency of the resin film and suppression of coloring, the dicarboxylic acid compound is preferably selected from an alicyclic dicarboxylic acid compound having a fluorine-based substituent and an aromatic dicarboxylic acid compound having a fluorine-based substituent.
- diamines examples include aromatic diamines, alicyclic diamines, and aliphatic diamines. Two or more of these may be used in combination. From the viewpoint of the solubility of the polyimide polymer in the solvent, and the transparency and flexibility when the resin film 10 is formed, the diamine is selected from an alicyclic diamine and an aromatic diamine having a fluorine substituent. Is preferred.
- the polyimide polymer may be a copolymer containing a plurality of different types of repeating structural units.
- the weight average molecular weight of the polyimide polymer is usually 10,000 to 500,000.
- the weight average molecular weight of the polyimide polymer is preferably 50,000 to 500,000, more preferably 70,000 to 400,000.
- the weight average molecular weight is a standard polystyrene equivalent molecular weight measured by gel permeation chromatography (GPC). If the weight average molecular weight of the polyimide polymer is large, high flexibility tends to be obtained, but if the weight average molecular weight of the polyimide polymer is too large, the viscosity of the varnish tends to increase and the workability tends to decrease. is there.
- the polyimide-based polymer may contain a halogen atom such as a fluorine atom that can be introduced by the above-described fluorine-based substituent.
- a halogen atom such as a fluorine atom that can be introduced by the above-described fluorine-based substituent.
- the halogen atom is preferably a fluorine atom.
- the content of halogen atoms in the polyimide polymer is preferably 1 to 40% by mass, more preferably 1 to 30% by mass based on the mass of the polyimide polymer.
- the resin film 10 may contain 1 type, or 2 or more types of ultraviolet absorbers.
- the ultraviolet absorber can be appropriately selected from those usually used as an ultraviolet absorber in the field of resin materials.
- the ultraviolet absorber may contain a compound that absorbs light having a wavelength of 400 nm or less.
- Examples of the ultraviolet absorber that can be appropriately combined with the polyimide polymer include at least one compound selected from the group consisting of benzophenone compounds, salicylate compounds, benzotriazole compounds, and triazine compounds.
- the “system compound” refers to a derivative of the compound to which the “system compound” is attached.
- a “benzophenone compound” refers to a compound having benzophenone as a host skeleton and a substituent bonded to benzophenone.
- the blending amount of the ultraviolet absorber may be an amount such that the resin film 10 satisfies the above conditions (i) and (ii).
- the amount of the ultraviolet absorber is usually 1% by mass or more, preferably 2% by mass or more, and preferably 3% by mass or more, based on the total mass of the resin film. It is 10 mass% or less, it is preferable that it is 8 mass% or less, and it is preferable that it is 6 mass% or less.
- the resin film 10 may further contain an inorganic material such as inorganic particles.
- the inorganic material is preferably a silicon material containing a silicon atom.
- the resin film 10 contains an inorganic material such as a silicon material, a particularly excellent effect can be obtained in terms of flexibility.
- silicon materials containing silicon atoms include silica particles, quaternary alkoxysilanes such as tetraethyl orthosilicate (TEOS), and silicon compounds such as silsesquioxane derivatives.
- TEOS tetraethyl orthosilicate
- silicon compounds such as silsesquioxane derivatives.
- silica particles are preferable from the viewpoint of the transparency and flexibility of the resin film 10.
- the average primary particle diameter of the silica particles is usually 100 nm or less. When the average primary particle diameter of the silica particles is 100 nm or less, the transparency tends to be improved.
- the average primary particle diameter of the silica particles in the resin film can be determined by observation with a transmission electron microscope (TEM).
- the primary particle diameter of the silica particles can be a constant direction diameter measured by a transmission electron microscope (TEM).
- the average primary particle diameter can be obtained as an average value of ten primary particle diameters measured by TEM observation.
- the particle distribution of the silica particles before forming the resin film can be determined by a commercially available laser diffraction particle size distribution meter.
- the blending ratio of the polyimide-based polymer and the inorganic material is preferably 1: 9 to 10: 0 in terms of mass ratio, with the sum of both being 10 and 3: 7 to 10: 0. More preferably, it is more preferably 3: 7 to 8: 2, and still more preferably 3: 7 to 7: 3.
- the ratio of the inorganic material to the total mass of the polyimide-based polymer and the inorganic material is usually 20% by mass or more, preferably 30% by mass or more, usually 90% by mass or less, and 70% by mass or less. Is preferred. There exists a tendency for the transparency and mechanical strength of a resin film to improve that the compounding ratio of a polyimide-type polymer and an inorganic material exists in said range.
- the resin film 10 may further contain other components as long as the transparency and flexibility are not significantly impaired.
- other components include colorants such as antioxidants, mold release agents, stabilizers, and bluing agents, flame retardants, lubricants, and leveling agents.
- the proportion of components other than the polyimide-based polymer and the inorganic material is preferably more than 0% and not more than 20% by mass, more preferably more than 0% and not more than 10% by mass with respect to the mass of the resin film 10. It is.
- Si / N which is the atomic ratio of silicon atoms to nitrogen atoms, is 8 or more on at least one main surface 10a.
- This atomic ratio Si / N is determined by evaluating the composition of the main surface 10a by X-ray photoelectron spectroscopy (XPS) and calculating the amount of silicon atoms and the amount of nitrogen atoms present. This is a calculated value.
- XPS X-ray photoelectron spectroscopy
- Si / N in the main surface 10a of the resin film 10 is 8 or more, sufficient adhesion with the functional layer 20 described later is obtained.
- Si / N is more preferably 9 or more, further preferably 10 or more, preferably 50 or less, and more preferably 40 or less.
- the thickness of the resin film 10 is appropriately adjusted according to the flexible device to which the laminate 30 is applied, but is preferably 10 to 500 ⁇ m, more preferably 15 to 200 ⁇ m, and more preferably 20 to 100 ⁇ m. More preferably.
- the resin film 10 having such a configuration has particularly excellent flexibility.
- the polyimide polymer varnish used for the production of the resin film is prepared by dissolving a polyimide polymer soluble in a solvent polymerized by a known polyimide polymer synthesis method in a solvent.
- the solvent may be any solvent that dissolves the polyimide polymer.
- DMAC dimethylformaceamide
- DMF dimethylformamide
- DMSO dimethylsulfoxide
- GBL ⁇ -butyrolactone
- an inorganic material is added to a polyimide polymer varnish, and stirred and mixed by a known stirring method to prepare a dispersion in which the inorganic material is uniformly dispersed.
- a UV absorber is blended, the UV absorber can be added to this dispersion.
- the polyimide polymer varnish or dispersion may further contain an additive.
- additives include colorants such as antioxidants, mold release agents, stabilizers, and bluing agents, flame retardants, lubricants, thickeners, and leveling agents.
- the polyimide-based polymer varnish or the dispersion may contain a compound such as alkoxysilane having one or more metal alkoxide groups that contributes to bonding between inorganic particles.
- An example of such a compound is an alkoxysilane having an amino group.
- the polyimide polymer varnish or dispersion may further contain water.
- the water content is usually 0.1 to 10% by mass relative to the mass of the polyimide polymer varnish or dispersion.
- the resin film can be produced by an appropriate known method. The following method is mentioned as an example of a manufacturing method.
- the polyimide polymer varnish or dispersion is applied to a substrate by a known roll-to-roll or batch method to form a coating film.
- the coating is dried to form a film.
- the resin film 10 is obtained by peeling a film from a base material.
- the substrate include a polyethylene terephthalate (PET) substrate, a stainless steel (SUS) belt, or a glass substrate.
- the coating film may be heated for drying and / or baking the coating film.
- the heating temperature of the coating film is usually 50 to 350 ° C.
- the coating film may be heated under an inert atmosphere or under reduced pressure.
- the solvent can be evaporated and removed by heating the coating film.
- the resin film may be formed by a method including a step of drying the coating film at 50 to 150 ° C. and a step of baking the dried coating film at 180 to 350 ° C.
- surface treatment may be performed on at least one main surface of the resin film.
- the surface treatment is preferably UV ozone treatment.
- Si / N can be easily increased to 8 or more.
- the method of setting Si / N to 8 or more is not limited to UV ozone treatment.
- the main surface 10a and / or 10b of the resin film 10 may be subjected to a surface treatment such as a plasma treatment or a corona discharge treatment in order to improve adhesion with a functional layer described later.
- UV ozone treatment can be performed using a known ultraviolet light source including a wavelength of 200 nm or less.
- An example of an ultraviolet light source is a low-pressure mercury lamp.
- the ultraviolet light source various commercially available devices equipped with an ultraviolet light source may be used. Examples of the commercially available apparatus include an ultraviolet (UV) ozone cleaning apparatus UV-208 manufactured by Technovision.
- FIG. 2 is a cross-sectional view showing an embodiment of the laminate.
- a laminated body 30 shown in FIG. 2 is a laminated body having the resin film 10 and the functional layer 20 laminated on one main surface 10a of the resin film 10.
- the functional layer 20 may be a layer for further imparting a function (performance) to the laminate 30 when the laminate 30 is used as an optical member of a flexible device or a base material of a display member, or a front plate.
- the optical member means a sensor unit such as a touch sensor or a signal transmission unit in the display device
- the display member means an image display unit such as an organic EL device or a liquid crystal display device in the display device.
- the functional layer 20 is preferably a layer having at least one function selected from the group consisting of ultraviolet absorption, a function of developing high hardness on the surface, adhesiveness, hue adjustment, and refractive index adjustment.
- the layer having an ultraviolet absorption function is, for example, a main material selected from an ultraviolet curable transparent resin, an electron beam curable transparent resin, and a thermosetting transparent resin. And an ultraviolet absorber dispersed in the main material.
- an ultraviolet absorbing layer As the functional layer 20, it is possible to easily suppress a change in yellowness due to light irradiation.
- the ultraviolet curable, electron beam curable, or thermosetting transparent resin as the main material of the ultraviolet absorbing layer is not particularly limited, but may be, for example, poly (meth) acrylate.
- the ultraviolet absorber can be selected from the same compounds as those exemplified as the ultraviolet absorber that can be contained in the resin film 10.
- the ultraviolet absorbing layer may be a layer that absorbs 95% or more of light having a wavelength of 400 nm or less (for example, light having a wavelength of 313 nm).
- the ultraviolet absorbing layer may 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 an ultraviolet absorber having a concentration that provides such transmittance. From the viewpoint of suppressing the increase in yellowness of the laminate due to light irradiation, the content ratio of the ultraviolet absorber in the ultraviolet absorbing layer (functional layer 20) is usually 1% by mass or more based on the mass of the ultraviolet absorbing layer. Yes, preferably 3% by mass or more, usually 10% by mass or less, and preferably 8% by mass or less.
- the layer (hard coat layer) having a function of expressing high hardness on the surface as the functional layer 20 is a layer that gives the laminate a surface having a pencil hardness higher than the pencil hardness of the surface of the resin film, for example.
- the hard coat layer is not particularly limited, but includes an ultraviolet curable resin, an electron beam curable resin, or a thermosetting resin typified by poly (meth) acrylates.
- the hard coat layer may contain a photopolymerization initiator and an organic solvent.
- the poly (meth) acrylates are, for example, poly (meth) acrylates formed from one or more (meth) acrylates selected from polyurethane (meth) acrylates, epoxy (meth) acrylates, and other polyfunctional poly (meth) acrylates. (Meth) acrylate.
- the hard coat layer may contain inorganic oxides such as silica, alumina and polyorganosiloxane in addition to the above components.
- the layer having an adhesive function (adhesive layer) as the functional layer 20 has a function of bonding the laminate 30 to another member.
- the material for forming the adhesive layer include a thermosetting resin composition and a photocurable resin composition.
- the adhesive layer may be composed of a resin composition containing a component having a polymerizable functional group. In this case, strong adhesion can be realized by further polymerizing the resin composition constituting the adhesive layer after the laminate 30 is brought into close contact with another member.
- the adhesive strength between 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.
- the resin composition can be polymerized and cured by supplying energy afterwards.
- the pressure-sensitive adhesive layer may be a layer called a pressure-sensitive adhesive (Pressure Sensitive Adhesive, PSA) that is stuck to an object by pressing.
- PSA Pressure Sensitive Adhesive
- the pressure-sensitive adhesive may be a pressure-sensitive adhesive that is “a substance that is sticky at normal temperature and adheres to an adherend with light pressure” (JIS K6800). And an adhesive that can maintain stability until the coating is broken by appropriate means (pressure, heat, etc.) (JIS K6800).
- the layer having a function of adjusting the hue (hue adjusting layer) as the functional layer 20 is a layer capable of adjusting the laminate 30 to a target hue.
- the hue adjustment layer may be a layer containing a resin and a colorant, for example.
- the colorant include inorganic pigments such as titanium oxide, zinc oxide, dial, titanium oxide-based fired pigment, ultramarine blue, cobalt aluminate, and carbon black; azo-based compounds, quinacridone-based compounds, anthraquinone-based compounds, and perylene-based materials.
- Organic pigments such as compounds, isoindolinone compounds, phthalocyanine compounds, quinophthalone compounds, selenium compounds and diketopyrrolopyrrole compounds; body pigments such as barium sulfate and calcium carbonate; basic dyes, acid dyes and mordant dyes And the like.
- the layer having a function of adjusting the refractive index (refractive index adjusting layer) as the functional layer 20 is a layer having a refractive index different from that of the resin film 10 and can impart a predetermined refractive index to the laminate.
- the refractive index adjustment layer may be, for example, an appropriately selected resin, a resin layer further containing a pigment as necessary, or a metal thin film.
- Examples of the pigment for adjusting the refractive index include silicon oxide, aluminum oxide, antimony oxide, tin oxide, titanium oxide, zirconium oxide and tantalum oxide.
- the average particle diameter of the pigment is preferably 0.1 ⁇ m or less.
- metal used for the refractive index adjustment layer examples include metals such as titanium oxide, tantalum oxide, zirconium oxide, zinc oxide, tin oxide, silicon oxide, indium oxide, titanium oxynitride, titanium nitride, silicon oxynitride, and silicon nitride. Oxides or metal nitrides may be mentioned.
- the functional layer 20 preferably has a function of expressing high hardness on the surface and a function of absorbing ultraviolet rays.
- the functional layer 20 in this case includes a “single layer having a function of developing high hardness on the surface and a function of absorbing ultraviolet light”, a “multilayer including a layer having a function of developing high hardness on the surface and a layer having ultraviolet absorption” Or “a multilayer including a single layer having a function of developing high hardness on the surface and a function of absorbing ultraviolet light and a layer having a function of developing high hardness on the surface”.
- the thickness of the functional layer 20 is appropriately adjusted according to the flexible device to which the laminate 30 is applied, but is preferably 1 to 100 ⁇ m, and more preferably 2 to 80 ⁇ m.
- the functional layer 20 is typically thinner than the resin film 10.
- the ultraviolet absorbing layer as the functional layer 20 is formed by, for example, applying a dispersion liquid containing an ultraviolet absorbent and a main material such as a resin in which the ultraviolet absorbent is dispersed to the main surface 10a of the resin film 10. It can be formed by forming and drying and curing the coating.
- the pressure-sensitive adhesive layer as the functional layer 20 is formed by, for example, applying a solution containing a pressure-sensitive adhesive that forms the pressure-sensitive adhesive layer to the main surface 10a of the resin film 10 to form a coating film, and drying and curing the coating film. Can be formed.
- the hue adjustment layer as the functional layer 20 is, for example, applied to the main surface 10a of the resin film 10 with a dispersion liquid containing a pigment or the like that forms the hue adjustment layer and a main material such as a resin in which the pigment or the like is dispersed. It can be formed by forming a coating film and drying and curing the coating film.
- the refractive index adjusting layer as the functional layer 20 is a dispersion containing, for example, inorganic particles that form the refractive index adjusting layer on the main surface 10a of the resin film 10 and a main material such as a resin in which the inorganic particles are dispersed. It can form by apply
- the functional layer 20 is a single layer having a function of developing a high hardness on the surface and a function of absorbing ultraviolet rays.
- the major layer 10a of the resin film 10 is mainly composed of an ultraviolet absorbent and a resin in which the ultraviolet absorbent is dispersed. It can form by apply
- the resin that forms the main material and the resin that forms the hard coat layer may be the same.
- a multilayer functional layer including a layer having a function of developing high hardness on the surface and a layer having ultraviolet absorption can be formed by the following method. Applying a dispersion liquid containing a UV absorber and a main material such as a resin in which the UV absorber is dispersed to the main surface 10a of the resin film 10 to form a coating film, and drying and curing the coating film Thus, an ultraviolet absorbing layer is formed. Next, a hard coat layer may be formed by applying a solution containing a resin for forming a hard coat layer to the ultraviolet absorbing layer to form a coat, and drying and curing the coat. By this method, a multilayer functional layer including a layer having a function of developing high hardness on the surface and a layer having ultraviolet absorption is formed.
- a multilayer including a single layer having a function of developing high hardness on the surface and a function of absorbing ultraviolet light and a layer having a function of developing high hardness on the surface can be formed by the following method.
- a coating film is formed on the main surface 10a of the resin film 10 by applying a dispersion containing an ultraviolet absorbent, a main material such as a resin in which the ultraviolet absorbent is dispersed, and a resin that forms a hard coat layer, The coating film is dried and cured to form a single layer having a function of expressing high hardness and an ultraviolet absorption function on the surface, and further, a solution containing a resin that forms a hard coat layer on the single layer.
- a multilayer functional layer including a layer having a function of developing high hardness on the surface and a function of absorbing ultraviolet light and a layer having a function of developing high hardness on the surface is formed.
- FIG. 3 is also a cross-sectional view showing an embodiment of the laminate.
- a laminate 30 shown in FIG. 3 further includes a primer 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 similar to the laminate of FIG. Yes.
- the primer layer 25 is laminated on one main surface 10 a of the resin film 10.
- the functional layer 20 is laminated on the main surface 25a opposite to the main surface that contacts the resin film 10 of the primer layer 25.
- the primer layer 25 is a layer formed from a primer agent, and preferably contains a material that can enhance adhesion between the resin film 10 and the functional layer 20.
- the compound contained in the primer layer 25 may be chemically bonded to the polyimide polymer or silicon material contained in the resin film 10 at the interface.
- primer agent examples include a UV-curable, thermosetting, or two-component curable epoxy compound primer agent.
- the primer agent may be a polyamic acid. These primer agents are suitable for enhancing the adhesion between the resin film 10 and the functional layer 20.
- the primer agent may contain a silane coupling agent.
- the silane coupling agent may be chemically bonded to the silicon material contained in the resin film 10 by a condensation reaction.
- the silane coupling agent can be suitably used particularly when the compounding ratio of the silicon material contained in the resin film 10 is high.
- Examples of the silane coupling agent include compounds having an alkoxysilyl group having a silicon atom and 1 to 3 alkoxy groups covalently bonded to the silicon atom.
- a compound having a structure in which two or more alkoxy groups are covalently bonded to a silicon atom is preferable, and a compound having a structure in which three alkoxy groups are covalently bonded to a silicon atom is more preferable.
- the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, an n-butoxy group, and a t-butoxy group. Among these, a methoxy group and an ethoxy group are preferable because reactivity with a silicon material can be increased.
- the thickness of the primer layer 25 is appropriately adjusted according to the functional layer 20, but is preferably 0.01 nm to 20 ⁇ m.
- the thickness of the primer layer 25 is preferably 0.01 ⁇ m to 20 ⁇ m, and more preferably 0.1 ⁇ m to 10 ⁇ m.
- the primer layer 25 preferably has a thickness of 0.1 nm to 1 ⁇ m, and more preferably 0.5 nm to 0.1 ⁇ m.
- the laminate 30 of FIG. 3 forms, for example, a coating film by applying a solution in which the primer agent is dissolved to the main surface 10a of the resin film 10, and then forming the primer layer by drying and curing the formed coating film. It can manufacture by the method including doing.
- the method for forming other members is the same as that of the laminate 30 in FIG.
- the primer layer 25 may be cured simultaneously with the functional layer 20 or may be separately cured before the functional layer 20 is formed.
- the resin film and laminate of the present embodiment have high transparency and can maintain excellent visibility when bent. Further, the resin film and the laminate can also have excellent flexibility. When a primer layer is provided between the resin film and the functional layer, the adhesion between the resin film and the functional layer is increased.
- Resin film and laminate are functionalities such as transparency, UV resistance, and high hardness on the surface required when applied to optical device or display member substrate of flexible device or front plate Can have.
- the structure of the resin film and the laminate can be modified as appropriate.
- functional layers can be provided on both sides of the resin film.
- a primer layer may be provided between each functional layer and the resin film.
- FIG. 4 is a cross-sectional view showing an embodiment of a display device.
- a display device 100 illustrated in FIG. 4 includes an organic EL device 50, a touch sensor 70, and a front plate 90. These are usually housed in a housing.
- the organic EL device 50 and the touch sensor 70 and the touch sensor 70 and the front plate 90 are bonded with, for example, an optical clear adhesive (not shown).
- the organic EL element 51 has a pair of electrodes (first electrode 52 and second electrode 53) and a 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 made of a light-transmitting conductive material.
- the second electrode 53 may also have optical transparency.
- a known material can be employed as the first electrode 52 and the second electrode 53.
- the light emitting layer 54 can be formed of a known light emitting material constituting the organic EL element.
- the light emitting material may be either a low molecular compound or a high molecular compound.
- the first substrate 55 is made of a light transmissive material.
- the second substrate 56 may be light transmissive.
- substrate 56 are bonded together by the sealing material 59 arrange
- the first substrate 55, the second substrate 56, and the sealing material 59 form a sealing structure that seals the organic EL element inside.
- the first substrate 55 and / or the second substrate 56 is often a gas barrier material.
- an inorganic material such as glass or a known transparent resin such as an acrylic resin can be used.
- a transparent resin such as an acrylic resin
- the above-described resin film or laminate according to the present embodiment can also be employed.
- the first substrate 55 and the second substrate 56 that can employ the laminate according to the present embodiment correspond to the base material or gas barrier material of the display member in the present embodiment.
- the organic EL device 50 having the first substrate 55 and the second substrate 56 employs the resin film or laminate according to the present embodiment, and thus has excellent flexibility.
- the touch sensor 70 is an optical member having a touch sensor base 71 and an element layer 72 having a detection element formed on the touch sensor base 71.
- a known detection element composed of a semiconductor element, a wiring, a resistor, and the like is formed.
- a configuration of the detection element a configuration that realizes a known detection method such as a matrix switch, a resistance film method, or a capacitance method can be adopted.
- the touch sensor substrate 71 that can employ the laminate according to the present embodiment corresponds to the optical member in the present embodiment. Since the touch sensor 70 having such a touch sensor substrate 71 employs the resin film or laminate according to the present embodiment, it has excellent flexibility.
- the front plate 90 that can employ the resin film or laminate according to the present embodiment is excellent in flexibility because it employs the resin film or laminate according to the present embodiment.
- the display device 100 When the display device 100 employs the resin film or laminate according to this embodiment as one or more constituent members selected from the organic EL device 50, the touch sensor 70, and the front plate 90, the display device 100 has excellent flexibility as a whole. be able to. That is, the display device 100 can be a flexible device.
- the device (flexible device) to which the resin film and the laminate according to the present embodiment can be applied is not limited to the display device.
- it is also applicable to a solar cell having a substrate on which a photoelectric conversion element is formed and a front plate provided on the substrate surface.
- the resin film or laminate according to this embodiment is employed as the substrate or front plate of the solar cell, the solar cell can have excellent flexibility as a whole.
- Example 1 A nitrogen-substituted polymerization tank was charged with a compound represented by formula (1), a compound represented by formula (2), a compound represented by formula (3), a catalyst and a solvent ( ⁇ -butyrolactone and dimethylacetamide). .
- the amount charged is 75.0 g of the compound represented by formula (1), 36.5 g of the compound represented by formula (2), 76.4 g of the compound represented by formula (3), 1.5 g of catalyst, and ⁇ -butyrolactone. 438.4 g and dimethylacetamide 313.1 g.
- the molar ratio of the compound represented by Formula (2) and the compound represented by Formula (3) is 3: 7, and the total of the compound represented by Formula (2) and the compound represented by Formula (3) is The molar ratio with the compound represented by Formula (1) was 1.00: 1.02.
- the temperature of the mixture was raised to 100 ° C., and then the temperature was raised to 200 ° C. and kept for 4 hours to polymerize the polyimide. During this heating, water in the liquid was removed. Then, the polyimide was obtained by refinement
- the mass ratio of silica particles and polyimide is 60:40
- the amount of alkoxysilane having amino groups is 1.67 parts by mass with respect to 100 parts by mass of silica particles and polyimide
- the amount of triazine-based ultraviolet absorber is 3 parts by mass with respect to 100 parts by mass in total of silica particles and polyimide
- 10 parts by mass of water with respect to 100 parts by mass in total of silica particles and polyimide is 60:40
- the amount of alkoxysilane having amino groups is 1.67 parts by mass with respect to 100 parts by mass of silica particles and polyimide
- the amount of triazine-based ultraviolet absorber is 3 parts by mass with respect to 100 parts by mass in total of silica particles and polyimide
- 10 parts by mass of water with respect to 100 parts by mass in total of silica particles and polyimide is 3 parts by mass with respect to 100 parts by mass in total of silica particles and polyimide
- the mass ratio of silica particles to polyimide is 55:45, the amount of aminosilane-containing alkoxysilane is 1.67 parts by mass with respect to the total of 100 parts by mass of silica particles and polyimide, and the amount of water is between silica particles and polyimide. It was 10 mass parts with respect to a total of 100 mass parts. Using this mixed solution, a resin film having a thickness of 80 ⁇ m was obtained in the same manner as in Example 1.
- Table 1 shows the evaluation results. It is confirmed that the resin films of the examples subjected to the light irradiation test satisfy the above-mentioned conditions (i) and (ii), and that the resin film and the laminate having the same have high visibility when bent. It was done.
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Abstract
Description
(i)光照射試験後の当該樹脂フィルムが、550nmの光に対する85%以上の透過率を有する、及び、
(ii)光照射試験前の樹脂フィルムが5以下の黄色度を有し、当該樹脂フィルムの光照射試験前後での黄色度の差が2.5未満である
図1は、樹脂フィルムの一実施形態を示す断面図である。図1に示す樹脂フィルム10は、ポリイミド系高分子を含有し、対向する一対の主面10a及び10bを有する。
(i)光照射試験後の樹脂フィルムが、550nmの光に対する85%以上の透過率を有する、及び、
(ii)光照射試験前の樹脂フィルムが5以下の黄色度(YI値)を有し、樹脂フィルムの光照射試験前後での黄色度の差が2.5未満である、
を満たす。これら条件(i)及び(ii)を満たす樹脂フィルムは、屈曲時にコントラスト又は色相の変化を生じ難く、良好な視認性を維持することができる。
本明細書において、「系化合物」とは、当該「系化合物」が付される化合物の誘導体を指す。例えば、「ベンゾフェノン系化合物」とは、母体骨格としてのベンゾフェノンと、ベンゾフェノンに結合している置換基とを有する化合物を指す。
図2は、積層体の一実施形態を示す断面図である。図2に示す積層体30は、樹脂フィルム10と、樹脂フィルム10の一方の主面10aに積層された機能層20とを有する積層体である。
樹脂フィルム10の主面10aに、紫外線吸収剤と、紫外線吸収剤が分散される樹脂などの主材とを含む分散液を塗布して塗膜を形成し、その塗膜を乾燥及び硬化させることにより、紫外線吸収層を形成する。次いで、その紫外線吸収層に、ハードコート層を形成する樹脂を含む溶液を塗布して塗膜を形成し、その塗膜を乾燥及び硬化させることにより、ハードコート層を形成してもよい。この方法により、表面に高硬度を発現する機能を有する層と紫外線吸収を有する層とを含む多層の機能層が形成される。
樹脂フィルム10の主面10aに、紫外線吸収剤と、紫外線吸収剤が分散される樹脂などの主材と、ハードコート層を形成する樹脂とを含む分散液を塗布して塗膜を形成し、その塗膜を乾燥及び硬化させて、表面に高硬度を発現する機能及び紫外線吸収の機能を有する単層を形成し、さらに、その単層上に、ハードコート層を形成する樹脂を含む溶液を塗布して塗膜を形成し、その塗膜を乾燥及び硬化させることにより、ハードコート層を形成してもよい。この方法により、表面に高硬度を発現する機能及び紫外線吸収の機能を有する層と表面に高硬度を発現する機能を有する層とを含む多層の機能層が形成される。
図4は、表示装置の一実施形態を示す断面図である。図4に示す表示装置100は、有機EL装置50と、タッチセンサー70と、前面板90と、を有する。これらは通常、筐体に収容されている。有機EL装置50とタッチセンサー70との間、及びタッチセンサー70と前面板90との間は、たとえば不図示の光学接着剤(Optical Clear Adhesive)で接着されている。
窒素置換した重合槽に、式(1)で表される化合物、式(2)で表される化合物、式(3)で表される化合物、触媒及び溶媒(γブチロラクトン及びジメチルアセトアミド)を仕込んだ。仕込み量は、式(1)で表される化合物75.0g、式(2)で表される化合物36.5g、式(3)で表される化合物76.4g、触媒1.5g、γブチロラクトン438.4g、ジメチルアセトアミド313.1gとした。式(2)で表される化合物と式(3)で表される化合物とのモル比は3:7、式(2)で表される化合物及び式(3)で表される化合物の合計と式(1)で表される化合物とのモル比は、1.00:1.02であった。
実施例1で作製した樹脂フィルムの一方の面に、プライマー層として、2液硬化型のプライマー(商品名:アラコートAP2510、荒川化学工業社製)を塗布して塗膜を形成し、その塗膜を乾燥及び硬化させて、厚さ1μmのプライマー層を形成した。
樹脂フィルムを形成するための混合溶液に、トリアジン系紫外線吸収剤を加えなかったこと以外は、実施例1と同様にして、厚み80μmの樹脂フィルムを得た。
390℃のガラス転移温度を有するポリイミド(三菱ガス化学社製「ネオプリム」)を準備した。このポリイミドの濃度20質量%のγブチロラクトン溶液、γブチロラクトンに固形分濃度30質量%のシリカ粒子を分散した分散液、アミノ基を有するアルコキシシランのジメチルアセトアミド溶液、及び、水を混合し、30分間攪拌して混合溶液を得た。シリカ粒子とポリイミドの質量比が55:45で、アミノ基を有するアルコキシシランの量がシリカ粒子及びポリイミドの合計100質量部に対して1.67質量部で、水の量がシリカ粒子及びポリイミドの合計100質量部に対して10質量部であった。この混合溶液を用いて、実施例1と同様にして厚み80μmの樹脂フィルムを得た。
1)光学特性(黄色度(YI値))
実施例及び比較例の樹脂フィルムのそれぞれの黄色度(Yellow Index:YI値)を、日本分光社製の紫外可視近赤外分光光度計V-670によって測定した。サンプルがない状態でバックグランド測定を行った後、樹脂フィルムをサンプルホルダーにセットして、300nm~800nmの光に対する透過率測定を行い、3刺激値(X、Y、Z)を求めた。YI値を、下記の式に基づいて算出した。
YI=100×(1.2769X-1.0592Z)/Y
日本分光社製の紫外可視近赤外分光光度計V-670を用い、300nm~800nmの光に対する透過率を測定し、550nmの波長の光に対する透過率を算出した。
スガ試験機社製の全自動直読ヘーズコンピューターHGM-2DPにより、実施例及び比較例の樹脂フィルムをサンプルホルダーにセットして、樹脂フィルムのヘイズを測定した。
実施例及び比較例の樹脂フィルムを、Atras社製のUVCONを用いた光照射試験に供した。光源はUV-B 313nm、出力は40Wであり、樹脂フィルムと光源との距離を5cmに設定した。樹脂フィルムに対して、紫外線を24時間照射した。紫外線照射後、上述のように光学特性(YI値、透過率)を評価した。
光照射試験前のフィルムを屈曲させ、そのときのコントラスト及び色相等の外観の状態を確認し、以下の基準で視認性を判定した。
A:コントラスト及び色相の変化が認められない。
C:コントラスト及び色相の変化などの外観変化が認められた。
Claims (12)
- ポリイミド系高分子を含有する樹脂フィルムであって、
当該樹脂フィルムから5cmの距離に設けられた出力40Wの光源によって、樹脂フィルムの一方の面から樹脂フィルムに313nmの光を24時間照射する光照射試験を行ったときに、当該樹脂フィルムが以下の条件:
(i)光照射試験後の当該樹脂フィルムが、550nmの光に対する85%以上の透過率を有する、及び、
(ii)光照射試験前の当該樹脂フィルムが5以下の黄色度を有し、当該樹脂フィルムの光照射試験前後での黄色度の差が2.5未満である、
を満たす樹脂フィルム。 - 光照射試験後の当該樹脂フィルムが1.0%以下のヘイズを有する請求項1に記載の樹脂フィルム。
- 当該樹脂フィルムが、紫外線吸収剤を更に含有する請求項1又は2に記載の樹脂フィルム。
- 請求項1~3のいずれか一項に記載の樹脂フィルムと、該樹脂フィルムの少なくとも一方の面側に設けられた機能層と、を有する積層体。
- 機能層が、紫外線吸収、粘着性、及び表面に高硬度を発現する機能からなる群から選択される少なくとも1種の機能を有する層である請求項4に記載の積層体。
- 前記樹脂フィルムと前記機能層との間に設けられたプライマー層を更に有する請求項4又は5に記載の積層体。
- 請求項1又は2に記載の樹脂フィルムを有する光学部材。
- 請求項3~6のいずれか一項に記載の積層体を有する光学部材。
- 請求項1又は2に記載の樹脂フィルムを有する表示部材。
- 請求項3~6のいずれか一項に記載の積層体を有する表示部材。
- 請求項1又は2に記載の樹脂フィルムを有する前面板。
- 請求項3~6のいずれか一項に記載の積層体を有する前面板。
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JP6709220B2 (ja) | 2020-06-10 |
KR20190087663A (ko) | 2019-07-24 |
JP7055166B2 (ja) | 2022-04-15 |
TW202031732A (zh) | 2020-09-01 |
JP2020149064A (ja) | 2020-09-17 |
TW201708318A (zh) | 2017-03-01 |
KR20180025964A (ko) | 2018-03-09 |
KR102276382B1 (ko) | 2021-07-13 |
JPWO2017014279A1 (ja) | 2018-05-24 |
KR102002611B1 (ko) | 2019-07-22 |
TWI694096B (zh) | 2020-05-21 |
CN107735435A (zh) | 2018-02-23 |
CN107735435B (zh) | 2021-05-25 |
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