JP6360737B2 - Laminated member, method for producing the laminated member, and image display device - Google Patents

Description

  The present invention relates to a laminated member and a method for producing the laminated member.

  A transparent substrate used as a protective member on the display side of an image display device such as a display, a touch panel, or a mobile phone has been conventionally made of glass, but can be easily formed into a shape having a curved surface. Since it is excellent in flexibility and preferable from the viewpoint of weight reduction, the use of a plastic film as a transparent substrate has been studied.

  A transparent substrate made of a plastic film has the above-mentioned advantages, but a glass substrate is made of an inorganic material, whereas a plastic film contains an organic material, so that a conventional glass is used. It is not easy to impart a heat resistance equivalent to that of the substrate, in particular, to a transparent substrate made of a plastic film to reduce dimensional change due to heating.

  As a means to impart excellent heat resistance to a transparent substrate made of a plastic film, polymerization within a coating film made of a composition containing a material having an energy polymerizable functional group that undergoes a polymerization reaction by heat or energy rays For example, a relatively hard layer obtained by advancing the reaction may be formed on a base film to form a laminated member. Even if it is a case where a dimensional change is likely to be caused by heating with a base film alone, the use of a laminated member can make it difficult for the dimensional change to occur even by heating.

  Although the purpose is not to impart heat resistance, for example, Patent Document 1 discloses a fingerprint-resistant film in which a fingerprint-resistant layer is formed on a transparent substrate. Thus, a hard layer may be formed on a base film for the purpose of imparting a function to form a laminated member.

JP 2012-166480 A

  Although the laminated member in which the relatively hard layer is formed on the base film is preferable because various functions are given as compared with the case of the base film alone as described above, the shape of the laminated layer (particularly the thickness) ) And physical properties (especially hardness), the bending resistance of the laminated member is lowered, and the advantage that the base film is excellent in flexibility may not be fully utilized. In particular, in order to impart excellent heat resistance to the laminated member, it may be preferable to increase the thickness of the layer formed on the base film, and in this case, the bending resistance is likely to be significantly reduced. It was.

  An object of this invention is to provide the laminated member which has the outstanding heat resistance, and is excellent also in bending resistance, and the manufacturing method of this laminated member.

The present invention provided to achieve the above object is as follows.
(1) A first resin material layer, a base film laminated on one surface side of the first resin material layer, and a second material laminated on the other surface side of the first resin material layer. The first resin material layer has a glass transition point of −90 ° C. or higher and 20 ° C. or lower, and the second resin material layer has an energy polymerizable functional group. The laminated member has a total light transmittance of 85% or more measured in the thickness direction according to JIS K7361-1, and is JIS K7133. In accordance with JIS K5600-5-1, the average of the vertical dimensional change rate and the horizontal dimensional change rate measured by the heating dimensional change measuring method with heating conditions of 150 ° C. for 1 hour is 0.5% or less. In the bending resistance test by the modified cylindrical mandrel method , Lamination member, wherein the diameter of the smallest diameter of the mandrel of the mandrel does not occur cracks is 25mm or less.

(2) The laminated member according to (1), wherein a plurality of the second resin-based material layers are provided, and an outermost layer of the laminated member is composed of the second resin-based material layer.

(3) The laminated member according to (1) or (2), including a plurality of the first resin material layers and a plurality of the second resin material layers.

(4) The laminated member according to any one of (1) to (3), wherein the surface of the second resin material layer is an exposed surface or a surface in contact with the first resin material layer.

(5) The laminated member according to any one of (1) to (4), wherein at least one of the first resin material layers has a thickness of 0.5 μm to 10 μm.

(6) The laminated member according to any one of (1) to (5), wherein at least one of the second resin material layers has a thickness of 3 μm to 100 μm.

(7) The lamination according to any one of (1) to (6), wherein a ratio of a total thickness of the second resin material layers to a thickness of the laminated member is 30% or more and 80% or less. Element.

(8) The laminated member according to any one of (1) to (7), wherein at least one of the second resin material layers contains an inorganic filler at a content rate of 10% by volume to 85% by volume. .

(9) The laminated member according to any one of (1) to (8), wherein at least one of the first resin-based material layers is formed from a pressure-sensitive adhesive composition.

(10) The laminated member according to any one of (1) to (9), wherein at least one of the base films has a thickness of 2 μm to 100 μm.

(11) The laminated member according to any one of (1) to (10), wherein the laminated member has a total thickness of 200 μm or less.

(12) The method for producing a laminated member according to any one of (1) to (11), wherein the first resin material layer is formed on at least one surface of the base film. In order to form the second resin material layer, a first lamination step of forming a first laminate including the base film and the first resin material layer, including applying an adhesive composition A second laminate comprising the process film and a coating film of the coating liquid formed on one surface of the process film, including applying the coating liquid on the release surface of the process film. The second lamination step to be formed, the surface of the first resin material layer of the first laminate and the surface of the coating film of the second laminate are bonded together, and the base film and the first resin 3rd lamination | stacking which obtains 3rd laminated body provided with a system material layer, the said coating film, and the said process film And a polymerization step of forming a second resin-based material layer from the coating film by advancing a polymerization reaction of the polymerizable compound contained in the coating film included in the third laminate. The manufacturing method of a laminated member.

  According to the present invention, a laminated member having excellent heat resistance and excellent bending resistance is provided. Moreover, according to this invention, the manufacturing method of a laminated member provided with this outstanding characteristic is also provided.

It is a schematic sectional drawing of the laminated member which concerns on one Embodiment of this invention. It is a schematic sectional drawing of the laminated member which concerns on an example (4 layer structure) of other one Embodiment of this invention. It is a schematic sectional drawing of the laminated member which concerns on another example (5 layer structure) of other one Embodiment of this invention. It is a schematic sectional drawing of the laminated member which concerns on another example (9 layer structure) of other one Embodiment of this invention.

Hereinafter, embodiments of the present invention will be described.
1. Laminated Member As shown in FIG. 1, a laminated member 10 according to an embodiment of the present invention includes a first resin material layer 3 and a substrate laminated on one surface side of the first resin material layer 3. A material film 1 and a second resin material layer 2 laminated on the other surface side of the first resin material layer 3 are provided.

(1) Base Film The specific characteristics of the base film 1 included in the laminated member 10 according to the present embodiment are not particularly limited as long as the laminated member 10 can satisfy the regulations described later. The base film 1 according to one embodiment is made of a transparent plastic film. Examples of the transparent plastic film include polyolefin resins such as polyethylene, polypropylene, poly-4-methylpentene-1, and polybutene-1, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polycarbonate resins, and polyvinyl chloride resins. Film made of cellulose resin such as polyphenylene sulfide resin, polyether sulfone resin, polyethylene sulfide resin, polyphenylene ether resin, styrene resin, acrylic resin, polyamide resin, polyimide resin, cellulose acetate Or these laminated | multilayer films are mentioned. Among these, a polyethylene terephthalate film is particularly preferable.

  There is no restriction | limiting in particular as thickness of the base film 1 with which the laminated member 10 which concerns on this embodiment is provided, It selects suitably according to the intended purpose of the laminated member 10, and is 0.1-500 micrometers normally. From the viewpoint of improving the handleability and realizing weight reduction, the thickness of the base film 1 is preferably 200 μm or less, and more preferably 100 μm or less. The lower limit of the thickness of the base film 1 is not limited. From the viewpoint of improving the handleability, the thickness of the base film 1 is preferably 1 μm or more, and more preferably 2 μm or more.

  The base film 1 included in the laminated member 10 according to this embodiment may include a weathering agent such as an antioxidant, an ultraviolet absorber, and a light stabilizer.

  As shown in FIG. 1, the base film 1 included in the laminated member 10 according to the embodiment of the present invention has a metallic film formed by a technique such as vapor deposition and sputtering as desired on the side opposite to the one surface 1 </ b> A. You may have on the surface.

  The base film 1 included in the laminated member 10 according to the present embodiment includes elements (second resin material layer 2 and first resin material layer 3) laminated on at least one of the surfaces thereof. For example, a surface treatment by an oxidation method or a concavo-convex method may be performed for the purpose of increasing the peel strength. Examples of the oxidation method include corona discharge treatment, plasma treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, and the like. Examples include solvent processing methods. These surface treatment methods are appropriately selected depending on the type of the base film 1, but in general, the corona discharge treatment method is preferably used from the viewpoints of effects and operability. Further, a primer layer made of a silane coupling agent or the like may be provided.

(2) Second resin-based material layer The second resin-based material layer 2 provided in the laminated member 10 according to this embodiment is a compound having an energy polymerizable functional group (also referred to as “polymerizable compound” in the present specification). ). This coating liquid can cause the polymerization reaction of the polymerizable compound to proceed by irradiation of the coating liquid of the coating liquid with ultraviolet rays, electron beams, or X-rays or by applying heat to the coating film.

  As shown in FIG. 1, at least one second resin material layer 2 included in the laminated member 10 according to this embodiment has the first resin material layer 3 on one surface of the base film 1. Laminated. As will be described later, the first resin material layer 3 is made of a relatively soft material by controlling the glass transition point. Such a relatively soft layer is located between the base film 1 and the relatively hard second resin material layer 2, thereby making it possible to improve the bending resistance of the laminated member 10. Become.

Hereinafter, the composition of the coating solution will be described.
(2-1) Polymerizable compound As long as the polymerizable compound which the coating liquid which concerns on one Embodiment of this invention contains has an energy polymerizable functional group, a specific structure and composition are not limited. However, a filler having an energy polymerizable functional group, which will be described later, is treated as a filler and is distinguished from a polymerizable compound.

  Examples of the energy polymerizable functional group possessed by the polymerizable compound include ethylenically unsaturated groups such as (meth) acryloyl group, vinyl group, allyl group and styryl group. Among these, the energy polymerizable functional group is preferably a (meth) acryloyl group because of its high reactivity. Hereinafter, the case where the energy polymerizable functional group is a (meth) acryloyl group will be described as a specific example. In the present specification, the “(meth) acryloyl group” means at least one of an acryloyl group and a methacryloyl group. The same applies to other similar words.

  The polymerizable compound may be composed of one type of compound or may be composed of a plurality of types of compounds. The polymerizable compound may contain a monomer or a polymer. When the polymerizable compound contains a polymer, the polymer may be an oligomer or a polymer.

  In the case where the polymerizable compound contains a monomer, examples of such a monomer include pentafunctional or higher polyfunctional acrylate monomers. Examples of pentafunctional or higher polyfunctional acrylate monomers include dipentaerythritol pentaacrylate, propionic acid modified dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, caprolactone modified dipentaerythritol hexaacrylate, dipentaerythritol pentamethacrylate, propionic acid. Examples thereof include modified dipentaerythritol pentamethacrylate, dipentaerythritol hexamethacrylate, and caprolactone-modified dipentaerythritol hexamethacrylate. Of these, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate are preferred.

  Examples of the monomer that the polymerizable compound may contain include a tetrafunctional or lower energy ray polymerizable monomer. Specific examples include monofunctional acrylates such as cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and isobonyl (meth) acrylate; 1,4-butanediol di ( (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, neopentyl glycol adipate di (meth) acrylate, hydroxypivalate neopentyl glycol di (Meth) acrylate, dicyclopentanyl di (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, caprolactone-modified dicyclopentenyl di (meth) acrylate , Ethylene oxide modified di (meth) acrylate phosphate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid Modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, dipentaerythritol hexa (meth) acrylate, pentaerythritol Examples thereof include ethoxytetraacrylate, ditrimethylolpropane tetraacrylate, and pentaerythritol tetraacrylate.

  In the case where the polymerizable compound includes an oligomer, examples of the oligomer include a polyester acrylate oligomer, an epoxy acrylate oligomer, a urethane acrylate oligomer, and a polyol acrylate oligomer.

  As a specific example of the polymerizable compound, there may be mentioned a case where the above-mentioned pentafunctional or higher polyfunctional acrylate monomer is used. Another specific example of the polymerizable compound includes a mixture of a polyfunctional acrylate monomer having 5 or more functional groups and an energy beam polymerizable oligomer and / or an energy beam polymerizable monomer having 4 or less functional groups.

  The content of the polymerizable compound in the coating liquid according to this embodiment is not limited. The second resin material layer 2 can be appropriately formed, and the viscosity of the coating liquid may be set to be appropriate. The mass ratio of the polymerizable compound in all components other than the solvent in the coating liquid is preferably 20% by mass or more and 95% by mass or less, and more preferably 30% by mass or more and 90% by mass or less.

(2-2) Filler The coating liquid which concerns on one Embodiment of this invention may contain a filler. The type, shape, and content of the filler are not limited as long as the second resin-based material layer 2 has appropriate optical characteristics, that is, satisfies the rules regarding the total light transmittance described later. When the coating liquid contains the filler, it becomes easy to improve the heat resistance of the laminated member 10 including the second resin material layer 2 formed from the coating liquid. When the coating liquid which concerns on this embodiment contains a filler, the filler contained in a coating liquid may be comprised from 1 type, and may be comprised from 2 or more types.

  The filler may contain an inorganic material or an organic material, but the filler contains an inorganic material from the viewpoint of easily improving the heat resistance of the laminated member 10. Preferably, it is more preferably composed of an inorganic material.

  Examples of materials that give inorganic fillers include metal oxides such as silica, aluminum oxide, zirconia, titania, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), antimony oxide, and cerium oxide; And metal fluorides such as magnesium fluoride and sodium fluoride. Metal, metal sulfide, metal nitride, or the like may be used as long as the laminated member 10 satisfies the provisions relating to the total light transmittance.

  Among these, silica and aluminum oxide are preferable as materials for providing the inorganic filler because it is easier to increase the heat resistance of the laminated member 10 and it is easily available. From the viewpoint of increasing the refractive index of the second resin material layer 2, the coating liquid may contain a filler made of zirconia, titania, antimony oxide, or the like. Conversely, from the viewpoint of reducing the refractive index of the second resin-based material layer 2, the coating liquid may contain a filler made of a fluoride such as magnesium fluoride and sodium fluoride, a hollow silica filler, and the like. From the viewpoint of imparting antistatic properties and electrical conductivity to the second resin material layer 2, the coating solution may contain a filler made of indium tin oxide (ITO), tin oxide, or the like.

  The surface of the filler may be chemically modified. The specific structure of chemical modification is not limited. As an example, it has an energy polymerizable functional group like a polymerizable compound through a silane coupling agent or the like. In this case, it is difficult to cause peeling between the filler and the polymerizable compound, the heat resistance of the laminated member 10 is increased, and a favorable tendency that the laminated member 10 easily satisfies the provisions relating to the total light transmittance is observed. It becomes easy. In the present specification, silica having an energy polymerizable functional group is referred to as reactive silica, and silica having no energy polymerizable functional group is referred to as non-reactive silica.

  The filler may be spherical or non-spherical. When it is non-spherical, it may be indefinite, or may have a shape with a high aspect ratio such as a needle shape or a scale shape. Since it becomes easy for the laminated member 10 to satisfy the provisions regarding the total light transmittance, it may be preferable that the filler is spherical.

  The size of the filler is not limited. The average particle diameter of the filler is usually from about 5 nm to about 2 μm, and the laminated member 10 is likely to satisfy the provisions relating to the total light transmittance. Therefore, the average particle diameter of the filler is preferably from 5 nm to 100 nm. In some cases. In addition, let the average particle diameter below 1 micrometer of the filler in this specification be the value measured by the dynamic light-scattering method using the particle size distribution measuring apparatus (The Nikkiso Co., Ltd. make, Nanotrack Wave-UT151). The average particle size of 1 μm or more of the filler is a value measured by a laser diffraction / scattering method using a particle size distribution measuring device (manufactured by Nikkiso Co., Ltd., Microtrac MT3000II).

  When the coating liquid which concerns on this embodiment contains a filler, content of the filler in a coating liquid is not limited. Set appropriately so that the heat resistance of the laminated member 10, the degree of shrinkage when the second resin material layer 2 is formed from the coating film, and the provisions relating to the total light transmittance of the laminated member 10 can be set within a desired range. do it. Illustratively showing specific numerical ranges, the volume content in the second resin material layer 2 may be about 2% to 95% by volume, and preferably 5% to 80% by volume. Yes, 10% by volume or more and 70% by volume or less may be more preferable.

(2-3) Polymerization initiator The coating liquid which concerns on this embodiment may contain a polymerization initiator. When the coating liquid which concerns on this embodiment contains a polymerization initiator, the kind of polymerization initiator contained in a coating liquid is not limited. The polymerization initiator may be either a photopolymerization initiator or a thermal polymerization initiator, and both may be contained in the coating liquid. By containing a polymerization initiator, it is possible to advance the polymerization reaction of the polymerizable compounds in the coating film by irradiating the coating film of the coating liquid with ultraviolet rays or applying heat to the coating film. It becomes.

  Examples of the photopolymerization initiator include acylphosphine oxide, acetophenone, benzophenone, benzoin, thioxanthone, and imidazole photopolymerization initiators.

  Examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like.

  Examples of the acetophenone photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, diethoxyacetophenone, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2-methylpropan-1-one, 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) Phenyl] -1-butanone, benzyldimethyl ketal, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] pheni } -2-methylpropan-1-one, and 2,2-dimethoxy-1,2-and the like.

  Examples of the benzophenone photopolymerization initiator include benzophenone, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, 4,4′-bis-dimethylaminobenzophenone and the like can be mentioned.

  Examples of the benzoin photopolymerization initiator include benzoin compounds such as benzoin, methylbenzoin, and ethylbenzoin, and benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, and benzoin phenyl ether.

  Examples of the thioxanthone photopolymerization initiator include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 1-chloro-4-propoxythioxanthone, 2,4-dichlorothioxanthone, and the like.

  Examples of the imidazole photopolymerization initiator include 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbisimidazolyl, 2,2′-bis (o-chlorophenyl)- 4,4 ′, 5,5′-tetra- (p-methoxyphenyl) bisimidazolyl, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2 ′ -Hexaarylbisimidazole compounds such as biimidazole.

  These photopolymerization initiators may be used alone or in combination of two or more.

  Examples of the thermal polymerization initiator include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, and di (2-ethoxyethyl). Peroxydicarbonate, t-butylperoxyneodecanoate, t-butylperoxybivalate, t-hexylperoxypivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, lauroyl Organic peroxides such as peroxide and diacetyl peroxide; 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane- 1-carbonyl), 2,2′-azobis (2,4-dimethyl) Valeronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate), 4,4′-azobis (4-cyano) Valeric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), 2,2′-azobis [2- (2-imidazolin-2-yl) propane] and the like. .

  These thermal polymerization initiators may be used alone or in combination of two or more.

  Among these polymerization initiators, a photopolymerization initiator is preferable from the viewpoint of reactivity. Among the photopolymerization initiators, acyl phosphine oxide photopolymerization initiators such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and acetophenone photopolymerization initiators such as 1-hydroxy-cyclohexyl phenyl ketone are preferable.

  The amount of the polymerization initiator used is not particularly limited. Illustratively, a specific numerical value range may be 1 to 15 parts by mass with respect to 100 parts by mass of the polymerizable compound, and a range of 2 to 10 parts by mass is exemplified as a preferred range.

  When the polymerization initiator contained in the coating liquid according to the present embodiment is a photopolymerization initiator, the coating liquid according to the present embodiment, together with the photopolymerization initiator, is ethyl N, N-dimethylaminobenzoate. Photosensitizers such as tertiary amines such as esters, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, and triethanolamine may be used in combination. These photosensitizers can be used alone or in admixture of two or more.

(2-4) Other components In addition to the polymerizable compound, the coating liquid according to the present embodiment, if necessary, the above-described filler, polymerization initiator, and various additional components such as a leveling agent and an antioxidant. Agents, ultraviolet absorbers, infrared absorbers, antistatic agents, light stabilizers, antifoaming agents, and the like. In addition to these active ingredients, the coating liquid according to the present embodiment preferably contains a solvent as necessary, and is adjusted to a concentration and viscosity suitable for coating.

  Examples of the solvent used in this case include aliphatic hydrocarbons such as hexane, heptane, and cyclohexane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as methylene chloride and ethylene chloride; methanol, ethanol, propanol, butanol, Examples include alcohols such as 1-methoxy-2-propanol; ketones such as acetone, methyl ethyl ketone, 2-pentanone, methyl isobutyl ketone, and isophorone; esters such as ethyl acetate and butyl acetate; and cellosolv solvents such as ethyl cellosolve.

(2-5) Thickness The thickness of the second resin material layer 2 is not particularly limited. As an example, it is 1 μm or more and 200 μm or less, more preferably 3 μm or more and 100 μm or less, and particularly preferably 5 μm or more and 50 μm or less. Since the second resin-based material layer 2 is a layer made of a relatively hard material, the total thickness of the second resin-based material layers 2 (as will be described later, the laminated member according to the present embodiment is a second resin). The ratio of the thickness of the laminated member 10 to the thickness of the laminated member 10 may be preferably 30% or more and 80% or less, and more preferably 34% or more and 70% or less. There is a case.

(3) First resin-based material layer As described above, the first resin-based material layer 3 included in the laminated member 10 according to the present embodiment has the base film 1 laminated on one surface and the second surface on the other surface. A resin material layer 2 is laminated. Since the glass transition point of the first resin material layer 3 is −90 ° C. or more and 20 ° C. or less, the first resin material layer 3 is preferentially applied when a bending force is applied to the laminated member 10. It is possible to reduce the deformation amount of the second resin material layer 2 which is deformed and constitutes the laminated member, in particular, the second resin material layer 2 having relatively high brittleness because it is relatively hard. For this reason, it is possible to improve the bending resistance as the laminated member 10.

  From the viewpoint of further improving the shape stability of the laminated member 10 according to the present embodiment, the glass transition point of the first resin material layer 3 is preferably −80 ° C. or higher, and more preferably −70 ° C. or higher. preferable. From the viewpoint of more stably increasing the bending resistance of the laminated member 10 according to the present embodiment, the glass transition point of the first resin material layer 3 is preferably 10 ° C. or less, and preferably 0 ° C. or less. More preferably, it is -10 degrees C or less, Most preferably, it is -30 degrees C or less.

  The material which comprises the 1st resin material layer 3 with which the laminated member 10 which concerns on this embodiment is provided is not limited as long as the 1st resin material layer 3 satisfy | fills the conditions regarding said glass transition point. As an example that is not limited, the first resin material layer 3 is made of an adhesive layer. The pressure-sensitive adhesive layer is a layer formed from a pressure-sensitive adhesive composition. The composition of the pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer is not particularly limited. Examples of the pressure-sensitive adhesive that is the main component include rubber-based, acrylic-based, silicone-based, and urethane-based pressure-sensitive adhesives. One type of these may be used, or two or more types may be used. The pressure-sensitive adhesive layer may have a laminated structure.

  The acrylic pressure-sensitive adhesive among the above will be described in more detail. The main component is an acrylic copolymer obtained by copolymerizing a functional group-containing monomer and another monomer such as an acrylic ester or methacrylic ester. And The pressure-sensitive adhesive composition may further contain a cross-linking agent, a tackifier, a filler, an antioxidant, an antistatic agent, an ultraviolet absorber and the like as necessary.

  Examples of the functional group-containing monomer include carboxyl group-containing monomers such as acrylic acid and methacrylic acid, and hydroxyl group-containing monomers such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and 4-hydroxybutyl acrylate. . The functional group-containing monomer preferably includes 0.3 to 5.0% by mass as a monomer unit based on the whole monomer constituting the acrylic copolymer (100% by mass). When the acrylic copolymer contains a functional group, the cohesive force can be adjusted by reaction with the crosslinking agent, and the adhesive force and heat resistance can be improved.

  There is no restriction | limiting in particular as a crosslinking agent used for the 1st resin type material layer 3, It uses suitably selecting from what is conventionally used in the adhesive composition which has an acrylic material as a main component, for example, , Polyisocyanate compounds, epoxy resins, melamine resins, urea resins, dialdehydes, methylol polymers, aziridine compounds, metal chelate compounds, metal alkoxides, metal salts, and the like, preferably polyisocyanate compounds are used.

  The thickness of the pressure-sensitive adhesive layer is not particularly limited. It should be appropriately set according to the application, and is usually about 0.1 μm to 500 μm, preferably about 0.2 μm to 100 μm, and preferably about 0.5 μm to 10 μm. It may be more preferable.

(4) Physical Properties, etc. (4-1) Total Light Transmittance The laminated member 10 according to this embodiment has a total light transmittance (hereinafter referred to as “total light transmission”) measured in the thickness direction in accordance with JIS K7361-1. Abbreviated as “rate”) is 85% or more. When the total light transmittance is 85% or more, it can be preferably used as a transparent substrate used as a protective member on the display side of the image display device. From the viewpoint of improving applicability to the protective member, the total light transmittance is preferably 90% or more. In addition, the thickness of the laminated member 10 at the time of measuring this total light transmittance is not specified.

(4-2) Dimensional Change Rate The laminated member 10 according to the present embodiment is based on JIS K7133, and the vertical dimensional change rate and the horizontal dimensional change measured by a heating dimensional change measurement method with heating conditions of 150 ° C. for 1 hour. The average rate (hereinafter abbreviated as “dimensional change rate”) is 0.5% or less. When the dimensional change rate is 0.5% or less, it becomes possible to have heat resistance equivalent to that of a glass substrate that has been conventionally used as a transparent substrate. From the viewpoint of facilitating that the laminated member 10 according to the present embodiment has excellent heat resistance, the dimensional change rate is preferably 0.4% or less, and more preferably 0.35% or less. Is particularly preferably 0.3% or less.

  Note that “vertical” and “horizontal” in the vertical dimension change rate and the horizontal dimension change rate described above are directions parallel to the major axis of a member formed by cutting the laminated member 10 according to the present embodiment as a transparent substrate. Is defined as “vertical”, and the direction perpendicular thereto is defined as “horizontal”. In order for the transparent substrate formed from the laminated member 10 according to the present embodiment to impart appropriate optical characteristics, the vertical or horizontal direction may be parallel or perpendicular to the major axis direction (MD direction) in the original fabric of the laminated member 10. It may not be defined.

(4-3) Bending Resistance The laminated member 10 according to the present embodiment has the smallest diameter among the mandrels in which cracks did not occur in the bending resistance test by the cylindrical mandrel method according to JIS K5600-5-1. The diameter of the mandrel (hereinafter also referred to as “minimum mandrel diameter”) is 25 mm or less. Such excellent bending resistance is considered to be due to the fact that the laminated member 10 includes the first resin material layer 3 whose glass transition point is controlled within a predetermined range as described above. From the viewpoint of providing superior bending resistance, the laminated member 10 according to this embodiment preferably has a minimum mandrel diameter of 20 mm or less, more preferably 12 mm or less, and particularly preferably 8 mm or less. preferable.

(4-4) Thickness The thickness of the laminated member 10 according to the present embodiment is not limited. It should be set appropriately according to the application. In addition, although the thickness of the laminated member 10 which concerns on this embodiment is not limited, the laminated member 10 of the thickness satisfy | fills that the total light transmittance is 85% or more as mentioned above. In consideration of applicability as a protective member, the thickness of the laminated member 10 according to the present embodiment is preferably 1 μm or more and 500 μm or less, and more preferably 5 μm or more and 200 μm or less.

(5) Other Elements in Laminated Member The laminated member 10 according to the present embodiment may include components other than the base film 1, the second resin material layer 2, the first resin material layer 3, and the like. . Specific examples of such elements include a pressure-sensitive adhesive layer and a release sheet.

(5-1) Adhesive Layer The laminated member 10 according to an embodiment of the present invention shown in FIG. 1 includes an adhesive layer on the surface opposite to the one surface 1A of the base film 1. May be. Since the details regarding the pressure-sensitive adhesive layer are the same as those of the pressure-sensitive adhesive layer according to the first resin material layer 3, description thereof is omitted.

(5-2) Release sheet When the laminated member 10 according to this embodiment includes the above-mentioned pressure-sensitive adhesive layer, for the purpose of protecting the surface opposite to the side facing the base film 1 until use, The release surface of the release sheet may be affixed to the surface. As this release sheet, for example, a release treatment comprising applying a release agent to one surface of a plastic film such as a polyester film such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, or a polyolefin film such as polypropylene or polyethylene. What was given. As the release agent, silicone-based, fluorine-based, long-chain alkyl-based, and the like can be used, and among these, a silicone-based material that is inexpensive and provides stable performance is preferable. The thickness of the release sheet is not particularly limited.

  The thickness of the release sheet is not limited. Usually, it is about 20-250 micrometers.

2. Other Embodiments of Laminated Member In the laminated member 10 according to the embodiment shown in FIG. 1, the second resin material layer 2, the first resin material layer 3, and the base film 1 are arranged in this order. Although having a structure, the laminated member according to the present invention may have a structure other than the structure shown in FIG. 1 as described below. These laminated members include a plurality of second resin-based material layers, and the outermost layers of the laminated members may be each composed of a second resin-based material layer. Moreover, a plurality of first resin material layers may be provided and a plurality of second resin material layers may be provided. Alternatively, the surface of the second resin material layer may be an exposed surface or a surface in contact with the first resin material layer.

(1) Four-layer structure As shown in FIG. 2, a laminated member 101 according to another embodiment of the present invention includes two second resin-based material layers (second resin-based material layers 21a and 21b). The outermost layers of the laminated member 101 are each composed of a second resin material layer (one is the second resin material layer 21a and the other is the second resin material layer 21b).

  The laminated member 101 shown in FIG. 2 includes one first resin-based material layer 31, and one surface of the first resin-based material layer 31 is in contact with the surface of the second resin-based material layer 21a. The surface is in contact with the substrate film 11. Therefore, one surface of the base film 11 is in contact with the surface of the second resin material layer 21b.

  Since the laminated member 101 having such a structure includes two second resin material layers, it can have more excellent heat resistance. Further, when a bending force is applied to the laminated member 101, the first resin material layer 31 is preferentially deformed, so that excellent bending resistance can be obtained.

(2) Five-layer structure As shown in FIG. 3, a laminated member 102 according to another embodiment of the present invention includes a second resin material layer 22a, a first resin material layer 32a, a base film 12, The first resin material layer 32b and the second resin material layer 22b have a structure arranged in this order.

  That is, the laminated member 102 according to another embodiment of the present invention includes two second resin-based material layers (second resin-based material layers 22a and 22b) and two first resin-based material layers ( The first resin material layers 32a and 32b) and the outermost layer of the laminated member 102 are both composed of a second resin material layer (one is the second resin material layer 22a and the other is the second resin material layer 22b). The surfaces of the two second resin material layers 22a and 22b are surfaces that contact either the exposed surface or the first resin material layers 32a and 32b.

  Since the laminated member 102 having a five-layer structure as shown in FIG. 3 includes two second resin material layers, it is possible to have more excellent heat resistance. In addition, since the second resin material layers 22a and 22b are both in contact with the first resin material layers 32a and 32b, when the bending force is applied to the laminated member 102, the first resin material material 22a and 22b are in contact with the first resin material layers 32a and 32b. By the preferential deformation of the layers 32a and 32b, the deformation amount of the second resin material layers 22a and 22b can be suppressed. Therefore, the laminated member 102 can have excellent bending resistance.

(3) Nine-layer structure As shown in FIG. 4, the laminated member 103 according to another embodiment of the present invention includes a second resin material layer 23a, a first resin material layer 33a, a base film 13a, The first resin material layer 33b, the second resin material layer 23b, the first resin material layer 33c, the base film 13b, the first resin material layer 33d, and the second resin material layer 23c are arranged in this order. The structure is provided.

  That is, the laminated member 103 according to another embodiment of the present invention includes three second resin material layers (second resin material layers 23a, 23b, and 23c), and four first resin material layers. Provided (first resin material layers 33a, 33b, 33c, 33d) and two base films (base films 13a, 13b). The outermost layers of the laminated member 103 are each composed of a second resin material layer (one is the second resin material layer 23a and the other is the second resin material layer 23c). The surfaces of the three second resin material layers 23a, 23b, and 23c are exposed surfaces or surfaces that are in contact with any of the first resin material layers 33a, 33b, 33c, and 33d.

  Since the laminated member 103 having a nine-layer structure as shown in FIG. 4 includes three second resin-based material layers, the laminated member 103 can have particularly excellent heat resistance. Moreover, since the second resin material layers 23a, 23b, and 23c are all in contact with at least one of the first resin material layers 33a, 33b, and 33c, a bending force is applied to the laminated member 102. Furthermore, the deformation amount of the second resin material layers 23a, 23b, and 23c can be suppressed by preferential deformation of the first resin material layers 33a, 33b, and 33c. Therefore, the laminated member 103 can have excellent bending resistance.

3. Manufacturing method of laminated member The manufacturing method of the laminated members 10, 101, 102, 103 according to the present embodiment is not limited. According to the manufacturing method described below, the laminated members 10, 101, 102, and 103 shown in FIG. 1 can be efficiently manufactured below. In this manufacturing method, a process film (a film used in the manufacturing process) is used. In the following manufacturing method, for ease of explanation, each of the steps included in the manufacturing method will be described by taking the case of manufacturing the laminated member 10 as a specific example, and then the other laminated members 101, 102, A manufacturing method 103 will be described.

(1) First laminating step First, as a first laminating step, including applying a pressure-sensitive adhesive composition for forming the first resin-based material layer 3 on one surface 1A of the base film 1, A 1st laminated body provided with the base film 1 and the 1st resin material layer 3 is formed. The application amount of the pressure-sensitive adhesive composition is not limited. It sets suitably according to the thickness of the 1st resin type material layer 3 formed from the coating film obtained by application | coating in a 1st lamination process. The application method is not particularly limited. Examples thereof include a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, and a gravure coating method. If necessary, the coating film formed on one surface 1A of the base film 1 is dried, and the first resin material layer 3 is removed by removing volatile components, particularly the solvent, contained in the coating film. You may get The conditions for drying are arbitrary, and include, for example, drying at 80 to 140 ° C. for several minutes to several tens of minutes.

(2) Second Laminating Step Next, as a second laminating step, a coating liquid for forming the second resin assembly material layer 2 is applied on the release surface of the step film, A 2nd laminated body provided with the coating film of the coating liquid formed on one side of a process film is formed. The application amount of the coating liquid is not limited. It sets suitably according to the thickness of the 2nd resin material layer 2 formed from the coating film obtained by application in the 2nd lamination process. The application method is not particularly limited. Examples thereof include a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, and a gravure coating method. If necessary, the coating film formed on the release surface of the process film may be dried to remove volatile components, particularly the solvent, contained in the coating film. The conditions for drying are arbitrary, and include, for example, drying at 80 to 140 ° C. for several minutes to several tens of minutes.

(3) Third Laminating Step Subsequently, as the third laminating step, the surface of the first resin material layer 3 of the first laminated body and the surface of the coating film of the second laminated body are bonded together, and the substrate A 3rd laminated body provided with the film 1, the 1st resin material layer 3, the coating film of a 2nd laminated body, and a process film is obtained. The bonding method of a 1st laminated body and a 2nd laminated body is not limited. As an example, the first laminated body is formed as a long body, and the first laminated body is fed out from a roll obtained by winding the first laminated body, and the second laminated body is formed as a long body and wound up. Bonding with the 2nd laminated body drawn | fed out from the rolled roll is mentioned.

(4) Polymerization step In the polymerization step, the polymerization reaction of the polymerizable compound contained in the coating film of the second laminate provided in the third laminate obtained as described above is advanced to apply the second laminate. The second resin material layer 2 is formed from the film. Thus, a laminated structure having a basic structure of a laminated member 10 in which the base film 1 is laminated on one surface of the first resin material layer 1 and the second resin material layer 2 is laminated on the other surface. The body is obtained. By peeling the process film from the laminated structure, the laminated member 10 can be obtained. The polymerization method in the polymerization step is not limited. The polymerization method is appropriately set according to the type of the polymerizable compound and, when the coating film of the second laminate contains a polymerization initiator, the type of the polymerization initiator.

  Examples of the energy for advancing the polymerization reaction of the polymerizable compound include heat and energy rays. Examples of the energy rays include ionizing radiation, that is, X-rays, ultraviolet rays, and electron beams. Among these, ultraviolet rays that are relatively easy to introduce irradiation equipment are preferable.

When ultraviolet rays are used as the ionizing radiation, near ultraviolet rays including ultraviolet rays having a wavelength of about 200 to 380 nm may be used for ease of handling. The amount of ultraviolet rays may be appropriately selected depending on the polymerizable compound type and thickness of the second resin-based material layer 2 is usually 50~700mJ / cm ² or so, preferably 200 to 600 mJ / cm ^2, 200 to 500 mJ / cm ² is more preferable. Moreover, ultraviolet illuminance is about 50-500 mW / cm < ² > normally, 100-450 mW / cm < ² > is preferable and 200-400 mW / cm < ² > is more preferable. There is no restriction | limiting in particular as an ultraviolet-ray source, For example, a high pressure mercury lamp, a metal halide lamp, the light emitting diode (UV-LED) of an ultraviolet region, etc. are used.

(5) Manufacturing method of laminated member according to another embodiment The laminated member 101 shown in FIG. 2 can be produced by the following production method. First, the coating liquid for forming a 2nd resin material layer is apply | coated on the surface of the base film of said 3rd laminated body, and a coating film is formed. Laminating the peeled surface of the process film on the exposed surface (the surface opposite to the side facing the base film) of the obtained coating film, and comprising the third laminate, the coating film and the process film Get the body. By carrying out the polymerization process for proceeding the polymerization reaction of the polymerizable compound contained in the two coating films provided in the laminate thus obtained, the laminated member 101 shown in FIG. It can be obtained in the affixed state. The manufacturing method of the laminated member 101 shown in FIG. 2 is not limited to the above manufacturing method.

  The laminated member 102 shown in FIG. 3 can be manufactured by the following manufacturing method. First, in said 1st lamination | stacking process, the process including apply | coating an adhesive composition on both surfaces of a base film is implemented, and a 1st resin-type material layer is provided on a base film and both surfaces. One laminate is obtained. Next, the surface of the coating film of a 2nd laminated body is affixed on each surface (surface of a 1st resin type material layer) of the obtained 1st laminated body. By carrying out the polymerization step of proceeding the polymerization reaction of the polymerizable compound contained in the two coating films provided in the laminate comprising the second laminate, the first laminate and the second laminate obtained in this way, The laminated member 102 shown in FIG. 3 can be obtained in a state where the process film is stuck on both surfaces. The manufacturing method of the laminated member 102 shown in FIG. 3 is not limited to the above manufacturing method.

  The laminated member 103 shown in FIG. 4 can be manufactured by the following manufacturing method. First, the second laminate, the first laminate and the second laminate obtained in the process of manufacturing the laminate member 102 shown in FIG. 3 are laminated in this order (hereinafter, this laminate is referred to as “fourth”. Also referred to as a “laminated body”. Moreover, the 1st laminated body (it is equipped with an adhesive layer in the both surfaces of a base film) and the 2nd laminated body of the structure similar to what was manufactured when manufacturing the laminated member 102 is prepared. The process film which comprises one surface of a 4th laminated body is peeled, and the surface of a base film is exposed. One surface (the surface of the first resin-based material layer) of the first laminated body is attached to the surface of the exposed base film. Subsequently, the surface of the second resin material layer of the second laminate is attached to the other surface (surface of the first resin material layer) of the first laminate. The polymerizable compound contained in the three coating films provided in the laminate comprising the second laminate, the first laminate, and the fourth laminate (where one process film is peeled off) thus obtained. By carrying out the polymerization process for advancing the polymerization reaction, the laminated member 103 shown in FIG. 4 can be obtained in a state where the process film is stuck on both surfaces. The manufacturing method of the laminated member 103 shown in FIG. 4 is not limited to the above manufacturing method.

  The embodiment described above is described for facilitating understanding of the present invention, and is not described for limiting the present invention. Therefore, each element disclosed in the above embodiment is intended to include all design changes and equivalents belonging to the technical scope of the present invention.

  For example, in the method of manufacturing the laminated member 101 shown in FIG. 2 or the laminated member 102 shown in FIG. 3, the polymerization of each coating film is performed by performing a single polymerization process on two coating films. Although the reaction is proceeding, a plurality of polymerization steps may be performed so that the polymerization reaction of each coating film proceeds.

  EXAMPLES Hereinafter, although an Example etc. demonstrate this invention further more concretely, the scope of the present invention is not limited to these Examples etc.

[Example 1]
(1) Preparation of coating solution A coating solution having the following composition was prepared.
i) 40 parts by mass of dipentaerythritol hexaacrylate (DPHA) as an ultraviolet curable acrylate resin of a polymerizable compound;
ii) 60 parts by weight of reactive silica (average particle size of 10 to 15 nm) as a filler,
iii) 1 part by mass of 2,4,6-trimethylbenzoyldiphenylphosphine oxide (“Irgacure (registered trademark) TPO” manufactured by BASF) as a photopolymerization initiator, and iv) 50 parts by mass of methyl isobutyl ketone (MIBK) as a solvent Department.

(2) Preparation of pressure-sensitive adhesive composition A pressure-sensitive adhesive composition having the following composition was prepared.
i) 100 parts by mass of an acrylic adhesive main agent,
ii) 1 part by mass of a tolylene diisocyanate derivative-based curing agent,
iii) 35 parts by mass of toluene as a solvent.

(3) Production of first laminate On one side of a 75 μm-thick polyethylene terephthalate base film, the pressure-sensitive adhesive composition is formed with a Meyer bar as a first resin material layer. An amount of 2 μm was applied and dried in a drying oven at 100 ° C. for 2 minutes to obtain a first laminate composed of a base film and a first resin material layer.

(4) Production of second laminate On the surface (release surface) on which the release agent of the process film consisting of a film made of polyethylene terephthalate having a thickness of 38 μm (applying release agent applied on one surface) is applied. The working liquid was applied with a Meyer bar in an amount such that the thickness as the second resin material layer was 30 μm, to obtain a second laminate composed of a process film and a coating film.

(5) Preparation of 3rd laminated body The surface of the 1st resin material layer of said 1st laminated body and the surface of the coating film of the 2nd laminated body were bonded together, and the 3rd laminated body was obtained.

(6) Production of Laminate Member Amount of the above-mentioned coating liquid on the surface of the obtained third laminate on the base film side with a Mayer bar, the thickness of the second resin material layer being 30 μm It was applied, and the above-mentioned process film was stuck on this coating film so that the peeled surface was in contact with the surface of the coating film. In this way, the laminated body which consists of a 3rd laminated body, a coating film, and a process film was obtained. The laminated body was subjected to a polymerization process in which light was irradiated using a high-pressure mercury lamp (Igraphics Inc., illuminance 200 mW / cm ² ) so that the irradiation amount was 500 mJ / cm ² . By this polymerization step, the two coating films included in the laminate are cured to form a second resin material layer having a thickness of 30 μm, a first resin material layer having a thickness of 2 μm, and a base having a thickness of 75 μm. A laminated member including a material film and a second resin material layer having a thickness of 30 μm was obtained in a state in which the process film was adhered to both surfaces. Table 1 shows ratios (unit:%, hereinafter, this ratio is also referred to as “second layer thickness ratio”) of the total thickness of the second resin-based material layers in the obtained laminated member to the thickness of the laminated member. Shown in

[Example 2]
In the same manner as in Example 1, a coating solution and a pressure-sensitive adhesive composition were prepared.
On both surfaces of a 75 μm-thick polyethylene terephthalate base film, the above pressure-sensitive adhesive composition is applied with a Mayer bar in an amount of 2 μm as the first resin material layer and dried. It dried on 100 degreeC 2 minute conditions in the furnace, and obtained the 1st laminated body which consists of a base film and two 1st resin type material layers.

  On the surface of the process film consisting of a film made of polyethylene terephthalate having a thickness of 38 μm (with a release agent applied on one side), the above-mentioned coating solution is applied to the second resin system on the Meyer bar. The second layered product composed of the process film and the coating film was obtained by applying an amount of 30 μm as the material layer. This process was repeated to prepare two second laminates.

  The surface of the coating film of the 2nd laminated body was stuck on both surfaces of the 1st laminated body, and the laminated body which consists of a 2nd laminated body, a 1st laminated body, and a 2nd laminated body was obtained. The laminated body was subjected to a polymerization step of irradiating light from a high-pressure mercury lamp in the same manner as in Example 1 to obtain a second resin material layer having a thickness of 30 μm and a first resin having a thickness of 2 μm. A process film is attached to both sides of a laminated member comprising a base material layer, a base film having a thickness of 75 μm, a first resin base material layer having a thickness of 2 μm, and a second resin base material layer having a thickness of 30 μm. Was obtained. Table 1 shows the second layer thickness ratio of the obtained laminated member.

Example 3
A second film having a thickness of 10 μm was used in the same manner as in Example 2 except that a film made of polyethylene terephthalate having a thickness of 25 μm was used as the base film and the thickness of the second resin material layer was 10 μm. A resin material layer, a first resin material layer having a thickness of 2 μm, a base film having a thickness of 25 μm, a first resin material layer having a thickness of 2 μm, and a second resin material layer having a thickness of 10 μm. The laminated member provided was obtained in a state where the process film was stuck on both sides. Table 1 shows the second layer thickness ratio of the obtained laminated member.

Example 4
A pressure-sensitive adhesive composition having the following composition was prepared, and a second resin-based material layer having a thickness of 30 μm and a thickness of 2 μm were obtained in the same manner as in Example 2 except that this pressure-sensitive adhesive composition was used. A laminated member comprising a first resin material layer, a base film having a thickness of 75 μm, a first resin material material layer having a thickness of 2 μm, and a second resin material layer having a thickness of 30 μm is formed on both surfaces. Obtained with the film attached. Table 1 shows the second layer thickness ratio of the obtained laminated member.
The composition of the prepared adhesive composition was as follows.
i) 100 parts by mass of an acrylic adhesive main agent,
ii) 1 part by weight of a cellulose binder,
iii) 6 parts by mass of isopropyl alcohol as a solvent.

Example 5
In the same manner as in Example 3, the second resin material layer having a thickness of 10 μm, the first resin material layer having a thickness of 2 μm, the base film having a thickness of 25 μm, and the first resin system having a thickness of 2 μm. A laminate that provides a laminate member comprising a material layer and a second resin-based material layer having a thickness of 10 μm, wherein the laminate is in a state before the polymerization step (second laminate, first laminate, and first laminate). A laminate comprising two laminates) was prepared as a fourth laminate. Moreover, the 1st laminated body (what laminated | stacked the 1st resin type material layer on both surfaces of the base film) and the 1st which has the same structure as what was manufactured in the process which manufactures the laminated member which concerns on Example 3 and 1st. Two laminated bodies (one in which the second resin material layer was laminated on one surface of the process film) were prepared.

  The process film affixed on one surface of the fourth laminate was peeled off, and the surface of the first resin material layer of the first laminate was affixed to the surface of the exposed second resin material layer. Next, the surface of the second resin material layer of the second laminate was affixed to the exposed surface of the first laminate (the surface opposite to the side facing the fourth laminate). A polymerization process similar to that of Example 3 was performed on the thus obtained fourth laminate (however, one process film was peeled off), the laminate comprising the first laminate and the second laminate. 10 μm thick second resin material layer, 2 μm thick first resin material layer, 25 μm thick substrate film, 2 μm thick first resin material layer, 10 μm thick A second resin-based material layer having a thickness, a first resin-based material layer having a thickness of 2 μm, a base film having a thickness of 25 μm, a first resin-based material layer having a thickness of 2 μm, and a second resin having a thickness of 10 μm. A laminated member provided with a resin-based material layer was obtained in a state where a process film was adhered to both surfaces. Table 1 shows the second layer thickness ratio of the obtained laminated member.

Example 6
The thickness of 10 μm was the same as in Example 5 except that the pressure-sensitive adhesive composition for forming the first resin material layer was changed to the following composition and the thickness of the base film was changed to 6 μm. 2 μm thick first resin material layer, 6 μm thick substrate film, 2 μm thick first resin material layer, 10 μm thick second resin A first resin material layer having a thickness of 2 μm, a base film having a thickness of 6 μm, a first resin material layer having a thickness of 2 μm, and a second resin material layer having a thickness of 10 μm. The laminated member was obtained with the process film attached to both sides. Table 1 shows the second layer thickness ratio of the obtained laminated member.

The composition of the prepared adhesive composition was as follows.
i) 100 parts by mass of an acrylic adhesive main agent,
ii) 1 part by mass of a tolylene diisocyanate derivative-based curing agent,
iii) 35 parts by mass of toluene as a solvent.

[Comparative Example 1]
The same 2nd laminated body as what was manufactured in Example 1 was prepared, and the surface of the coating film was affixed on one side of the 75-micrometer-thick polyethylene terephthalate base film (double-sided easy-adhesion processing completed). On the surface of the base film of the laminate composed of the obtained second laminate and the base film, the coating solution used for producing the second laminate is applied to the second resin with a Mayer bar. The thickness of the system material layer was applied in an amount of 30 μm to obtain a laminate composed of the second laminate, the base film, and the coating film. The peeled surface of the process film used to produce the second laminate was pasted on the surface of the laminate. The obtained laminate was subjected to the same process as the polymerization process performed in Example 1 to obtain a second resin material layer having a thickness of 30 μm, a base film having a thickness of 75 μm, and a thickness of 30 μm. A laminated member provided with the second resin-based material layer was obtained in a state where the process film was adhered to both surfaces. Table 1 shows the second layer thickness ratio of the obtained laminated member.

[Comparative Example 2]
A second resin material layer having a thickness of 30 μm and a thickness of 2 μm were obtained in the same manner as in Example 2 except that the composition for forming the first resin material layer was changed to an epoxy adhesive. A laminated member comprising a first resin material layer, a base film having a thickness of 75 μm, a first resin material material layer having a thickness of 2 μm, and a second resin material layer having a thickness of 30 μm is formed on both surfaces. Obtained with the film attached. Table 1 shows the second layer thickness ratio of the obtained laminated member.

[Test Example 1] <Measurement of glass transition point>
Using a composition (pressure-sensitive adhesive composition or epoxy adhesive) for forming the first resin material layer used in the process of manufacturing the laminated member according to the example and the comparative example, a test piece having a thickness of 10 μm Produced. The glass transition point (Tg) of the prepared test piece was −70 to 140 ° C. at a temperature rising / falling rate of 20 ° C./min using a differential scanning calorimeter (TAinstruments, product name “DSCQ2000”). Measured in range. The results are shown in Table 1.

[Test Example 2] <Measurement of total light transmittance>
About the laminated member manufactured in the Example and the comparative example, the total light transmittance was measured to the thickness direction based on JISK7361-1. No standardization of thickness was performed. When the measured total light transmittance was 85% or more, it was determined to be good. The results are shown in Table 1.

[Test Example 3] <Measurement of heating dimensional change>
About the laminated member manufactured in the Example and the comparative example, based on JISK7133, the vertical dimension change rate and the horizontal dimension change rate were measured with the heating dimension change measuring method which makes heating conditions 150 degreeC 1 hour. The dimensional change rate (unit:%) is represented by {| (distance between gauge points before heating) − (distance between gauge points after heating) | / (distance between gauge points before heating) × 100}. The average value of the measured vertical dimensional change rate and horizontal dimensional change rate was defined as the heating dimensional change of each laminated member, and was determined to be good when the heating dimensional change was 0.5% or less. The results are shown in Table 1.

[Test Example 4] <Flexibility test>
The laminated members manufactured in the examples and comparative examples were subjected to a bending resistance test by a cylindrical mandrel method based on JIS K5600-5-1. The diameter of the mandrel having the smallest diameter (minimum mandrel diameter) was determined among the mandrels that did not crack. It was determined that the minimum mandrel diameter was 25 mm or less. The results are shown in Table 1. In Comparative Example 2, since cracks were also observed in the maximum diameter mandrel (diameter 32 mm) used in the test, “> 32” is shown in Table 1.

  As can be seen from Table 1, the laminated member of the example satisfying the conditions of the present invention has sufficient transparency (having high total light transmittance), excellent heat resistance and flex resistance. It was excellent.

  The laminated member according to the present invention is suitably used as a transparent protective member on the display side of an image display device.

10, 101, 102, 103 ... laminated members 1, 11, 12, 13a, 13b ... base film 1A ... one surface 2, 21a, 21b, 22a, 22b, 23a, 23b, 23c ... second of base film Resin-based material layers 3, 31, 32a, 32b, 33a, 33b, 33c, 33d ... first resin-based material layer

Claims (12)

At least one first resin-based material layer, a laminated member comprising at least one substrate film, and at least one second resin-based material layer,
In each of the first resin-based material layers, at least one of the base film is laminated on one surface side, and at least one of the second resin-based material layers is laminated on the other surface side,
The first resin material layer has a glass transition point of −90 ° C. or more and 10 ° C. or less,
At least one of the first resin-based material layers has a thickness of 0.5 μm or more and 10 μm or less,
The second resin material layer is formed from a coating solution containing a compound having an energy polymerizable functional group,
The laminated member is
The total light transmittance measured in the thickness direction in accordance with JIS K7361-1 is 85% or more,
According to JIS K7133, the average of the vertical dimensional change rate and the horizontal dimensional change rate measured by the heating dimensional change measuring method with heating conditions of 150 ° C. for 1 hour is 0.5% or less,
A laminated member characterized in that, in a bending resistance test by a cylindrical mandrel method according to JIS K5600-5-1, a mandrel having the smallest diameter among mandrels that do not cause cracking has a diameter of 25 mm or less.   2. The laminated member according to claim 1, comprising a plurality of the second resin-based material layers, wherein each outermost layer of the laminated member is composed of the second resin-based material layer.   The laminated member according to claim 1 or 2, comprising a plurality of the first resin-based material layers and a plurality of the second resin-based material layers.   4. The laminated member according to claim 1, wherein the surface of the second resin material layer is an exposed surface or a surface in contact with the first resin material layer. 5. The laminated member according to any one of claims 1 to 4 , wherein at least one of the second resin-based material layers has a thickness of 3 µm to 100 µm. The laminated member according to any one of claims 1 to 5 , wherein a ratio of a total thickness of the second resin-based material layers to a thickness of the laminated member is 30% or more and 80% or less. The laminated member according to any one of claims 1 to 6 , wherein at least one of the second resin-based material layers contains an inorganic filler at a content rate of 10% by volume or more and 85% by volume or less. The laminated member according to any one of claims 1 to 7 , wherein at least one of the first resin-based material layers is formed from a pressure-sensitive adhesive composition. The laminated member according to any one of claims 1 to 8 , wherein at least one of the base films has a thickness of 2 µm or more and 100 µm or less. The laminated member according to any one of claims 1 to 9 , wherein the laminated member has a total thickness of 200 µm or less. It is a manufacturing method of the lamination member according to any one of claims 1 to 10 ,
Including applying the pressure-sensitive adhesive composition for forming the first resin-based material layer on at least one surface of the base film, and including the base film and the first resin-based material layer. A first stacking step of forming a first stack,
The coating liquid formed on one surface of the process film and the process film, including applying a coating liquid for forming the second resin-based material layer on the release surface of the process film A second lamination step of forming a second laminate comprising the coating film of
Bonding the surface of the first resin material layer of the first laminate and the surface of the coating film of the second laminate, the base film, the first resin material layer, the coating film And a third lamination step for obtaining a third laminate including the step film, and a polymerization reaction of the polymerizable compound contained in the coating film included in the third laminate, so that the second resin is formed from the coating film. The manufacturing method of a laminated member characterized by including the superposition | polymerization process which forms a system material layer. An image display device comprising the laminated member according to any one of claims 1 to 10 as a transparent protective member on a display side.

Images