WO2015163281A1 - 複合体及びその製造方法 - Google Patents
複合体及びその製造方法 Download PDFInfo
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- WO2015163281A1 WO2015163281A1 PCT/JP2015/061981 JP2015061981W WO2015163281A1 WO 2015163281 A1 WO2015163281 A1 WO 2015163281A1 JP 2015061981 W JP2015061981 W JP 2015061981W WO 2015163281 A1 WO2015163281 A1 WO 2015163281A1
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Definitions
- the present invention provides a composite having a curable resin layer or a film layer on one or both sides of a sheet layer containing fine fibers as a main component, or a single or both sides of a sheet layer (nonwoven fabric layer) containing fine fibers as a main component.
- a composite (nonwoven fabric resin composite) in which a curable resin layer or a film layer is laminated through a layer (easy-adhesive layer) hereinafter referred to as “composite”
- composite a sheet mainly composed of fine fibers
- the present invention relates to a composite in which a coating layer is laminated on one side or both sides of a layer (hereinafter referred to as “bonding sheet”) and a method for producing the same.
- the present invention further relates to an illumination device, a projection device, a signboard or image display device, a touch panel, or a solar cell including the above complex.
- cellulose fibers particularly wood-derived cellulose fibers (pulp) are widely used mainly as paper products.
- the width of the cellulose fibers used in the paper is in most cases 10-50 ⁇ m.
- Paper (sheet) obtained from such cellulose fibers is opaque and is widely used as printing paper.
- the cellulose fiber is treated (beating, pulverizing) with a refiner, kneader, sand grinder or the like, and the cellulose fiber is refined (microfibril), a transparent paper (glassine paper or the like) is obtained.
- nonwoven fabrics composed of cellulose fibers have been used as printing paper, books, and the like as paper by adding a sizing agent, a paper strength enhancer, and the like. Furthermore, the use of nonwoven fabrics made of cellulose fibers by utilizing permeability to gases and liquids has been studied for use in filters, power storage elements, batteries or capacitor separators.
- Patent Document 1 includes a nonwoven fabric (a) containing cellulose and a resin (b) other than cellulose, wherein (a) component is 0.1 wt% or more and 99 wt% or less, and (b) component is 1 A composite is described which is characterized in that it is not less than 9% by weight and not more than 99.9% by weight.
- pores of a nonwoven fabric (a) containing cellulose are filled with a resin (b) other than cellulose.
- Patent Document 2 describes a plastic film with a hard coat layer in which a primer layer and a hard coat layer are laminated on a transparent plastic film.
- the resin constituting the hard coat layer is a cured product of a resin composition containing pentafunctional or higher functional (meth) acrylate, monofunctional (meth) acrylate and a photopolymerization initiator as essential components.
- the transparent plastic used in Patent Document 2 is a polyester film, particularly a PET film.
- Patent Document 3 describes a non-woven fabric obtained by papermaking cellulose fibers having an average fiber diameter of 0.1 to 20 ⁇ m and cellulose nanofibers having an average fiber diameter of less than 100 nm, and a separator for a storage battery element composed of the non-woven fabric.
- JP 2006-316253 A Japanese Patent Laid-Open No. 9-300549 JP 2012-36517 A
- This invention made it the subject which should be solved to provide the composite_body
- the present invention also provides a composite having high strength and high transparency, a composite having high adhesion between a sheet (sheet layer) mainly composed of fine cellulose fibers and a curable resin layer or a film layer, and fine cellulose. It was set as the problem which should be solved to provide the sheet
- the present inventors diligently studied to solve the above problems. As a result, by laminating a resin layer on one or both sides of a nonwoven fabric layer containing fine fibers having an average fiber width of 2 to 1000 nm via an easy-adhesive layer, the adhesion of the resin layer is high and highly transparent.
- the present inventors have found that a non-woven resin composite can be provided, and have completed the present invention. Specifically, the present inventors have intensively studied to solve the above problems. As a result, 1) a composite in which a curable resin layer or a film layer is laminated on one side or both sides of a sheet (hereinafter referred to as “sheet layer”) mainly composed of fine fibers having an average fiber width of 2 to 1000 nm is high.
- the composite according to any one of (1) to (4), wherein the fine fibers are fibers containing cellulose fibers.
- the coating layer is a hybrid material of an organic component and an inorganic component.
- the hybrid material of the organic component and the inorganic component is composed of an organic component having a silicon skeleton and an inorganic component.
- the organic component is a component containing at least one selected from a methyl group, a mercapto group, a methacryl group, an acryloyl group, a vinyl group, and an amino group.
- the coating layer is at least one selected from a thermosetting resin, a thermoplastic resin, and a photocurable resin.
- the sheet according to (16), wherein the coating layer is a hybrid material of an organic component and an inorganic component.
- a step of providing a coating layer on one or both sides of a sheet layer containing fine fibers having an average fiber width of 2 to 1000 nm as a main component; and curable on the surface of the coating layer opposite to the sheet layer A process for providing a resin layer or a film layer.
- a resin layer is laminated on one side or both sides of a nonwoven fabric layer containing fine fibers having an average fiber width of 2 to 1000 nm obtained by chemical treatment and defibration treatment of a fiber raw material via an easily adhesive layer.
- a non-woven resin composite [2] The nonwoven fabric resin composite according to [1], wherein the fine fibers have an average fiber width of 2 to 100 nm. [3] The nonwoven fabric resin composite according to [1] or [2], wherein the density of the nonwoven fabric layer is 0.90 g / cm 3 or more.
- the thickness of the nonwoven fabric layer is 2 to 150 ⁇ m, the thickness of the easy-adhesive layer is 0.1 to 30 ⁇ m, and the thickness of the resin layer is 0.2 to 50 ⁇ m.
- a composite of a nonwoven fabric and a resin in which the resin layer has high adhesion and is highly transparent. More specifically, according to the present invention, 1) a composite having high strength and high transparency, 2) a composite having high adhesion and high strength and high transparency between the sheet layer and the curable resin layer or film layer. Body, 3) A bonding sheet having high adhesion and high transparency between the sheet layer and the coating layer is provided.
- FIG. 1 shows a composite in which a curable resin layer or a film layer is laminated on one side of a sheet layer via a coating layer.
- FIG. 2 shows a composite in which a curable resin layer or a film layer is laminated on both sides of a sheet layer via a coating layer.
- the nonwoven fabric resin composite of the present invention has an easy-adhesion layer on one or both sides of a nonwoven fabric layer containing fine fibers having an average fiber width of 2 to 1000 nm obtained by chemical treatment and defibration treatment of a fiber raw material.
- the resin layer is laminated. That is, the nonwoven fabric resin composite of the present invention is a laminate including at least a nonwoven fabric layer, an easily adhesive layer, and a resin layer.
- the composite of the present invention is 1) a composite in which a curable resin layer or a film layer is laminated on one or both sides of a sheet layer mainly composed of fine fibers having an average fiber width of 2 to 1000 nm, 2) A composite in which a curable resin layer or a film layer is laminated on one or both sides of a sheet layer mainly composed of fine fibers having an average fiber width of 2 to 1000 nm via a coating layer, and 3) an average fiber width of 2 to It is a bonding sheet in which a coating layer is laminated on one side or both sides of a sheet layer mainly composed of 1000 nm fine fibers.
- the composite of the present invention is composed of 1) a composite composed of two layers of a sheet layer and a curable resin layer or a film layer, 2) a sheet layer, a coating layer, and a curable resin layer or a film layer.
- FIG. 1 shows a case where a curable resin layer or a film layer is laminated on one side of a sheet layer via a coating layer.
- FIG. 2 shows a case where a curable resin layer or a film layer is laminated on both surfaces of a sheet layer via a coating layer.
- the sheet layer in the present invention is mainly composed of fine fibers having an average fiber width of 2 to 1000 nm.
- the fine fiber is not particularly limited as long as it has a mean fiber width of 2 to 1000 nm, and may be fine cellulose fiber or fine fiber other than fine cellulose fiber. Fine cellulose fiber and fine cellulose fiber It may be a mixture with other fine fibers.
- the fine fiber is a cellulose fiber.
- fibers other than fine cellulose fibers include, but are not limited to, semi-synthetic fibers and regenerated fibers such as inorganic fibers, organic fibers, and synthetic fibers.
- inorganic fibers include, but are not limited to, glass fibers, rock fibers, and metal fibers.
- organic fibers include, but are not limited to, fibers derived from natural products such as carbon fibers, chitin, and chitosan.
- synthetic fibers include, but are not limited to, nylon, pinilone, vinylidene, polyester, polyolefin (eg, polyethylene, polypropylene, etc.), polyurethane, acrylic, polyvinyl chloride, aramid, and the like.
- Semi-synthetic fibers include but are not limited to acetate, triacetate, promix and the like.
- the regenerated fiber include, but are not limited to, rayon, cupra, polynosic rayon, lyocell, and tencel.
- Fine fibers other than fine cellulose fibers can be mixed with fine cellulose fibers and then subjected to treatments such as chemical treatment and fibrillation treatment. Chemical treatments and fibrillation treatments can be applied to fine fibers other than fine cellulose fibers. It can also be mixed with fine cellulose fibers after the above treatment.
- the amount of fine fibers other than fine cellulose fibers in the total amount of fine cellulose fibers and fine cellulose fibers other than fine cellulose fibers is not particularly limited, but is preferably 50% by mass or less. is there.
- the addition amount of fine fibers other than the fine cellulose fibers is more preferably 40% by mass or less, further preferably 30% by mass or less, and particularly preferably 20% by mass or less.
- fine cellulose fibers obtained by subjecting a cellulose raw material to chemical treatment and defibration treatment may be used as fine fibers.
- the cellulose raw material include paper pulp, cotton pulp such as cotton linter and cotton lint, non-wood pulp such as hemp, straw, and pagas, cellulose isolated from sea squirts and seaweed, etc., but are not particularly limited. .
- paper pulp is preferable in terms of availability, but is not particularly limited.
- Examples of papermaking pulp include, but are not limited to, chemical pulp, semi-chemical pulp, mechanical pulp, non-wood pulp, and deinked pulp.
- Examples of the chemical pulp include hardwood kraft pulp, softwood kraft pulp, sulfite pulp (SP), and soda pulp (AP).
- examples of the hardwood kraft pulp include bleached kraft pulp (LBKP), unbleached kraft pulp (LUKP), and oxygen bleached kraft pulp (LOKP).
- examples of softwood kraft pulp include bleached kraft pulp (NBKP), unbleached kraft pulp (NUKP), and oxygen bleached kraft pulp (NOKP).
- Semi-chemical pulp includes semi-chemical pulp (SCP), chemiground wood pulp (CGP), and the like.
- Examples of the mechanical pulp include groundwood pulp (GP) and thermomechanical pulp (TMP, BCTMP).
- non-wood pulp examples include non-wood pulp made from straw, cocoon, hemp, kenaf and the like.
- deinked pulp examples include deinked pulp made from waste paper. Among these, kraft pulp, deinked pulp, and sulfite pulp are preferable because they are more easily available, but are not particularly limited.
- a cellulose raw material may be used individually by 1 type, and may be used in mixture of 2 or more types.
- the (number average) fiber width of the fine cellulose fibers is 2 to 1000 nm, more preferably the number average fiber width is 2 to 100 nm.
- the fine cellulose fibers may be cellulose fibers or rod-like particles that are much thinner than the pulp fibers normally used in papermaking applications.
- the fine cellulose fiber is an aggregate of cellulose molecules including a crystal part, and its crystal structure is type I (parallel chain).
- the number average fiber width of the fine cellulose fibers can be measured by observing with an electron microscope. When the average fiber width of the fine cellulose fiber is less than 2 nm, the physical properties (strength, rigidity, dimensional stability) as the fine cellulose fiber are not exhibited because the cellulose molecule is dissolved in water.
- the measurement of the fiber width by electron microscope observation of a fine cellulose fiber is performed as follows. An aqueous suspension of fine cellulose fibers having a concentration of 0.05 to 0.1% by mass is prepared, and the suspension is cast on a carbon film-coated grid subjected to a hydrophilic treatment to obtain a sample for TEM observation.
- an SEM image of the surface cast on glass may be observed. Observation with an electron microscope image is performed at a magnification of 1000 times, 5000 times, 10000 times, or 50000 times depending on the width of the constituent fibers. However, the sample, observation conditions, and magnification are adjusted to satisfy the following conditions.
- One straight line X is drawn at an arbitrary location in the observation image, and 20 or more fibers intersect the straight line X.
- a straight line Y perpendicular to the straight line is drawn in the same image, and 20 or more fibers intersect the straight line Y.
- the average fiber width of fine cellulose fibers is the average value of the fiber widths read in this way.
- the fiber length of the fine cellulose fiber is not particularly limited, but is preferably 1 to 1000 ⁇ m, more preferably 5 to 800 ⁇ m, and particularly preferably 10 to 600 ⁇ m.
- the fiber length can be obtained by image analysis using TEM, SEM, or AFM.
- the method of chemical treatment of cellulose raw materials or other fiber raw materials is not particularly limited as long as it is a method capable of obtaining fine fibers.
- the treatment method include, but are not limited to, ozone treatment, TEMPO oxidation treatment, enzyme treatment, or treatment with a compound capable of forming a covalent bond with a functional group in cellulose or a fiber raw material.
- a method described in JP 2010-254726 A can be exemplified, but it is not particularly limited. Specifically, after the fiber is treated with ozone, it is dispersed in water, and the resulting aqueous dispersion of the fiber is pulverized.
- the method described in International Publication WO2013 / 176033 can be mentioned, but is not particularly limited.
- the fiber raw material is treated with an enzyme at least under a condition where the ratio of the enzyme EG activity to the CBHI activity is 0.06 or more.
- the treatment with a compound having a quaternary ammonium group described in JP 2011-162608 A is a method of reacting a hydroxyl group in a fiber with a cationizing agent having a quaternary ammonium group to cation-modify the fiber. It is.
- the method using a carboxylic acid compound described in JP2013-136659A can be performed as follows.
- a fiber raw material is treated with at least one carboxylic acid compound selected from the group consisting of a compound having two or more carboxy groups, an acid anhydride of a compound having two or more carboxy groups, and a derivative thereof.
- the fiber raw material into which the carboxy group has been introduced is treated with an alkaline solution.
- the following method can be used. That is, a method of mixing a powder or an aqueous solution of Compound A with a fiber raw material, a method of adding an aqueous solution of Compound A to a fiber raw material slurry, or the like.
- Compound A includes, but is not limited to, phosphoric acid, polyphosphoric acid, phosphorous acid, phosphonic acid, polyphosphonic acid or esters thereof. These may also be in the form of salts.
- Examples of the compound having a phosphoric acid group include, but are not limited to, phosphoric acid, sodium salt of phosphoric acid, potassium salt of phosphoric acid, and ammonium salt of phosphoric acid.
- Examples of the sodium salt of phosphoric acid include sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, sodium pyrophosphate and sodium metaphosphate.
- Examples of the potassium salt of phosphoric acid include potassium dihydrogen phosphate, dipotassium hydrogen phosphate, tripotassium phosphate, potassium pyrophosphate and potassium metaphosphate.
- Examples of the ammonium salt of phosphoric acid include ammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, ammonium pyrophosphate, and ammonium metaphosphate.
- ⁇ Defibration processing> Cellulose raw materials or other fiber raw materials (inorganic fibers, organic fibers, synthetic fibers, semi-synthetic fibers, regenerated fibers, etc.) are refined by subjecting them to a defibrating treatment, and the number average fiber width is 2 to 1000 nm. Can be obtained.
- the raw material obtained by the chemical treatment can be defibrated using a defibrating apparatus to obtain a fine fiber dispersion.
- an apparatus for wet pulverization can be used as appropriate.
- grinder stone mill type grinder
- high pressure homogenizer ultra high pressure homogenizer
- high pressure collision type grinder ball mill
- disk type refiner conical refiner
- biaxial kneader vibration mill
- homomixer under high speed rotation ultrasonic dispersion Machine, beater, etc.
- the defibrating apparatus is not limited to the above.
- the sheet layer of the present invention is mainly composed of fine fibers.
- seat layer a nonwoven fabric, a woven fabric, paper, a film, etc. can be used without limitation in particular.
- the content of fine fibers contained in the sheet layer is preferably 50% by mass or more, more preferably 60% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more based on the dry weight of the sheet layer. . The higher the content of fine fibers in the sheet layer, the higher the strength of the sheet.
- the density of the sheet layer in the present invention is not particularly limited, is preferably 0.90 g / cm 3 or more, more preferably 1.00 g / cm 3 or more, more preferably 1.10 g / cm 3 or more is there.
- the upper limit of the density of the sheet layer is not particularly limited, but is generally 1.60 g / cm 3 or less.
- the thickness of the sheet layer in the present invention is not particularly limited, and is generally about 1 to 300 ⁇ m, preferably 2 to 150 ⁇ m, more preferably 5 to 100 ⁇ m, and further preferably 5 to 50 ⁇ m.
- the sheet layer may be a laminate of a plurality of sheet layers depending on the purpose. In the case of using a plurality of sheet layers, the total thickness and the total density of the plurality of sheet layers are preferably within the above-described range.
- a suspension containing fine fibers is prepared.
- a hydrophilic polymer may be added to this suspension.
- hydrophilic polymers include polyethylene glycol, cellulose derivatives (hydroxyethyl cellulose, carboxyethyl cellulose, carboxymethyl cellulose, etc.), casein, dextrin, starch, modified starch, polyvinyl alcohol, modified polyvinyl alcohol (acetoacetylated polyvinyl alcohol, etc.), Polyethylene oxide, polyvinyl pyrrolidone, polyvinyl methyl ether, polyacrylic acid salts, polyacrylamide, acrylic acid alkyl ester copolymer, urethane copolymer and the like can be mentioned, but are not particularly limited.
- hydrophilic low molecular weight compound can be used instead of the hydrophilic polymer.
- hydrophilic low molecular weight compounds include, but are not limited to, glycerin, erythritol, xylitol, sorbitol, galactitol, mannitol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, and butylene glycol.
- the addition amount in the case of adding a hydrophilic polymer or a hydrophilic low molecular weight compound is preferably 1 to 200 parts by mass, more preferably 1 to 150 parts by mass, further preferably 100 parts by mass of the solid content of the fine fiber. Is 2 to 120 parts by mass, particularly preferably 3 to 100 parts by mass, but is not particularly limited.
- the suspension containing fine fibers to be applied to the base material is a liquid containing fine fibers and a dispersion medium.
- a dispersion medium water or an organic solvent can be used, but from the viewpoint of handleability and cost, only water is preferable, but it is not particularly limited. Even when an organic solvent is used, it is preferably used in combination with water, but is not particularly limited.
- the organic solvent used in combination with water is preferably a polar solvent such as an alcohol solvent, a ketone solvent, an ether solvent, or an acetate solvent, but is not particularly limited thereto.
- the alcohol solvent include methanol, ethanol, propanol, butanol and the like.
- ketone solvents include acetone and methyl ethyl ketone.
- ether solvents include diethyl ether, ethylene glycol dimethyl ether, and tetrahydrofuran.
- the acetate solvent include ethyl acetate.
- the solid content concentration of the fine fibers contained in the suspension is not particularly limited, but is preferably 0.1 to 20% by mass, more preferably 0.1 to 10% by mass, and further preferably 0.5 to 10% by mass. . If the solid content concentration after dilution is equal to or higher than the lower limit, the efficiency of the defibrating treatment is improved, and if it is equal to or lower than the upper limit, blockage in the defibrating apparatus can be prevented.
- the sheet layer can be prepared by coating a suspension containing fine fibers on a substrate.
- a film, a woven fabric, a sheet-like material represented by a nonwoven fabric, a plate or a cylindrical body can be used, but it is not particularly limited thereto.
- the material of the base material for example, resin, metal, paper, or the like is used, and resin or paper is preferable in that a fine fiber-containing sheet can be more easily manufactured.
- the material is not particularly limited thereto.
- the resin include, but are not limited to, polytetrafluoroethylene, polyethylene, polypropylene, polyethylene terephthalate, polyvinyl chloride, polyvinylidene chloride, polystyrene, and acrylic resin.
- Examples of the metal include aluminum, stainless steel, zinc, iron, and brass, but are not particularly limited.
- Examples of the paper base material include paper base materials such as glossy paper, high-quality paper, medium-quality paper, copy paper, art paper, coated paper, craft paper, paperboard, white paperboard, newsprint, and renewal paper. There is no particular limitation.
- a coating machine for coating a suspension containing fine fibers for example, a roll coater, a gravure coater, a die coater, a curtain coater, an air doctor coater, or the like can be used, but it is not particularly limited.
- a die coater, a curtain coater, and a spray coater are preferable because the thickness can be made more uniform, and a die coater is more preferable, but it is not particularly limited thereto.
- the coating temperature is not particularly limited, but is preferably 10 to 80 ° C, and more preferably 10 to 60 ° C. If the coating temperature is equal to or higher than the lower limit, the fine fiber-containing suspension can be easily applied, and if it is equal to or lower than the upper limit, volatilization of the dispersion medium during the coating can be suppressed.
- the non-woven fabric layer is formed by drying the suspension containing fine fibers coated on the substrate.
- a drying method Either a non-contact drying method or the method of drying while restraining a sheet
- the non-contact drying method is not particularly limited, but a method of drying by heating with hot air, infrared rays, far infrared rays or near infrared rays (heating drying method) or a method of drying in vacuum (vacuum drying method) is applied. Can do. Although the heat drying method and the vacuum drying method may be combined, the heat drying method is usually applied. Although drying by infrared rays, far infrared rays, or near infrared rays can be performed using an infrared device, a far infrared device, or a near infrared device, it is not particularly limited.
- the heating temperature in the heat drying method is not particularly limited, but is preferably 40 to 120 ° C, more preferably 40 to 105 ° C. If the heating temperature is at least the lower limit value, the dispersion medium can be volatilized quickly, and if it is at most the upper limit value, the cost required for heating and the discoloration due to the heat of the fine fibers can be suppressed.
- the component which comprises a coating layer is not specifically limited,
- the hybrid material of an inorganic component and an organic component, a thermosetting resin, a photocurable resin, a thermoplastic resin etc. can be used.
- the resin include polyester resins, urethane resins, acrylic resins, olefin resins, fluorine resins, vinyl chloride resins, styrene resins, epoxy resins, and silicone resins.
- the component constituting the coating layer it is preferable to use a hybrid material of an inorganic component and an organic component.
- the above-mentioned hybrid material or resin of an inorganic component and an organic component may be used alone or in combination of two or more.
- a hybrid material of an inorganic component and an organic component and a resin can be used in combination.
- an adhesive, an adhesive sheet, etc. can also be used as a coating layer.
- hybrid material of an inorganic component and an organic component for example, a composite of an organic component and an inorganic component whose coating layer has a silicon skeleton can be given.
- examples of the hybrid material of an organic component and an inorganic component having a silicon skeleton include silsesquioxane.
- Silsesquioxane is a network polymer or polyhedral cluster having a structure represented by (RSiO 3/2 ) n (wherein R represents an organic group). If a reactive substituent is introduced into R, a cured product of a hybrid material of an organic component and an inorganic component can be produced using this reactive substituent.
- R represents an organic group
- a reactive substituent is introduced into R, a cured product of a hybrid material of an organic component and an inorganic component can be produced using this reactive substituent.
- As the structure of silsesquioxane a random structure, a complete cage structure, an incomplete cage structure, a ladder structure, and the like are known.
- silsesquioxane Aposagawa Chemical Co., Ltd.
- organic component constituting the hybrid material of inorganic component and organic component examples include components having a methyl group, a mercapto group, a methacryl group, an acryloyl group, a vinyl group, and an amino group, and include at least one component.
- organic components include amines.
- a composite having high adhesion between the sheet layer and the curable resin layer or film layer (1: sheet layer and curable resin layer, 2: sheet layer and film layer). Can be manufactured.
- the organic component contained in the hybrid material of the inorganic component and the organic component is easy to adhere to the curable resin layer or the film layer, while the inorganic component contained in the hybrid material is easy to adhere to the sheet layer.
- the adhesiveness of the curable resin layer or the film layer becomes good.
- the method for adhering the sheet layer and the coating layer is not particularly limited, and examples thereof include application and bonding methods.
- the coating layer can be formed by applying a solution containing the components constituting the coating layer to the sheet layer and curing it as necessary.
- the curing method include, but are not limited to, a method of curing by heat and a method of curing by irradiation with radiation.
- radiation include, but are not limited to, infrared light, visible light, and ultraviolet light.
- a thermal polymerization initiator may be used, and any method that can be cured can be used without particular limitation.
- pressure-sensitive adhesive pressure-sensitive adhesive composed of pressure-sensitive adhesive and release sheet (Peel off the release sheet that covers the pressure-sensitive adhesive when in use, and use pressure-sensitive adhesive.
- Product name non-carrier tape
- the sheet layer and the coating layer can also be bonded together.
- the thickness of the coating layer in the present invention is not particularly limited, and is generally about 0.1 to 50 ⁇ m, preferably 0.1 to 30 ⁇ m, more preferably 0.2 to 20 ⁇ m, still more preferably. 0.5 to 10 ⁇ m.
- a coating layer can also be made into two or more layers. When setting it as a some coating layer, it is preferable that the total thickness of a some coating layer exists in said range.
- thermoplastic resin a thermosetting resin, a photocurable resin etc.
- a component constituting the curable resin layer or the film layer it is desirable to use a component having a barrier ability against humidity, water, heat, gas and the like. At least two or more curable resin layers or film layers can be laminated.
- thermoplastic resins styrene resins, acrylic resins, aromatic polycarbonate resins, aliphatic polycarbonate resins, aromatic polyester resins, aliphatic polyester resins, aliphatic polyolefin resins, cyclic olefin resins, polyamides
- resins include, but are not particularly limited to, resins based on polyphenylene ether, resins based on thermoplastic polyimide, polyacetal based resins, polysulfone based resins and amorphous fluorine based resins.
- thermosetting resins examples include epoxy resins, acrylic resins, oxetane resins, phenol resins, urea resins, melamine resins, unsaturated polyester resins, silicon resins, polyurethane resins, allyl ester resins, diallyl phthalate resins, etc. Not.
- photocurable resin examples include precursors such as an epoxy resin, an acrylic resin, and an oxetane resin, but are not limited thereto.
- the resin may be used alone, or two or more different resins may be used.
- thermoplastic resins thermosetting resins, and photocurable resins, photocurable resins are most preferable.
- thermosetting resin examples include, but are not limited to, polyfunctional amines, polyamides, acid anhydrides, phenol resins, and the like.
- curing catalyst for the thermosetting resin examples include imidazole and the like, but are not particularly limited thereto.
- curing agent and a curing catalyst can also be used independently, and can also use 2 or more types.
- the method for adhering the sheet layer and the curable resin layer or film layer, and the method for adhering the sheet layer and the curable resin layer or film layer through the coating layer are not particularly limited, but methods such as coating and bonding Can be mentioned.
- a solution containing a resin precursor and a curing agent is applied to the sheet layer and cured to form a curable resin layer or a film layer.
- the curing method include, but are not limited to, a method of curing by heat and a method of curing by irradiation with radiation.
- radiation include, but are not limited to, infrared light, visible light, and ultraviolet light.
- a thermal polymerization initiator may be used, and any method that can be cured can be used without particular limitation.
- the coating layer is applied to the sheet layer, and then the curable resin layer or film is applied to the coating layer by the same method as described above.
- a layer can be formed.
- a pressure-sensitive adhesive As the coating layer, a pressure-sensitive adhesive, a pressure-sensitive adhesive composed of a pressure-sensitive adhesive and a release sheet (the pressure-sensitive adhesive is used by peeling off the release sheet covering the pressure-sensitive adhesive at the time of use) (example: non-carrier tape), pressure-sensitive adhesive
- a sheet layer and a curable resin layer or a film layer can also be bonded together using a sheet or the like.
- the thickness of the curable resin layer or film layer in the present invention is not particularly limited, and is generally about 0.1 to 100 ⁇ m, preferably 0.2 to 50 ⁇ m, more preferably 0.5 to 20 ⁇ m. More preferably, it is 1 to 10 ⁇ m.
- the curable resin layer or film layer may be a laminate of a plurality of curable resin layers or film layers depending on the purpose. When a plurality of curable resin layers or film layers are used, the total thickness of the plurality of curable resin layers or film layers is preferably within the above range.
- the barrier ability against water of the sheet layer can be improved.
- a composite in which a curable resin layer or a film layer is laminated on a sheet layer (2 layers), 2) a sheet layer, and a curable resin layer or a film layer are interposed via a coating layer.
- a laminated composite (3 layers), 3) a laminating sheet (2 layers) in which a coating layer is laminated on a sheet layer.
- a composite (two layers) in which a curable resin layer or a film layer is laminated on a sheet layer is characterized by high strength and high transparency.
- a composite in which a sheet layer and a curable resin layer or a film layer are laminated via a coating layer is high in strength and highly transparent, and the sheet layer and the curable resin layer or film layer. It has the characteristic that adhesiveness of is high.
- a lamination sheet two layers in which a coating layer is laminated on a sheet layer is characterized by high strength and high transparency, and high adhesion between the sheet layer and the coating layer.
- the adhesion between the layers of the composite and the laminating sheet is preferably 10 or less, more preferably 10 or less in 100 squares in a cross-cut test according to JIS standard K5400 described in the following experimental examples. Is 5 or less, more preferably 3 or less.
- the composite of the present invention and the lamination sheet are characterized by high transparency.
- the total light transmittance of the composite of the present invention is preferably 70% or more, more preferably 80% or more, still more preferably 85% or more, and further preferably 90% or more.
- the upper limit of the total light transmittance is not particularly limited, and may be 100% or 99% or less.
- the haze of the composite of the present invention is preferably 10% or less, more preferably 5% or less, and further preferably 3% or less.
- the composite and the sheet for bonding of the present invention can be used for image display devices such as a liquid crystal display, a plasma display, an organic EL display, a field emission display, and a rear projection television. Furthermore, the composite of the present invention can also be used for an illumination device and a projection device. Furthermore, the composite and the sheet for lamination of the present invention can be used for a wiring board, a front plate, a color filter substrate and the like of a touch panel and a solar cell (such as a silicon-based solar cell and a dye-sensitized solar cell). For use as a substrate, it may be laminated with a barrier film, ITO, TFT or the like.
- Example 1 Film formation of sheet layer (A) (also referred to as non-woven fabric layer (A)) Using a non-woven fabric as a sheet, a sheet layer (non-woven fabric layer) was prepared by the following method. 265 g of sodium dihydrogen phosphate dihydrate and 197 g of disodium hydrogen phosphate were dissolved in 538 g of water to obtain an aqueous solution of a phosphoric acid compound (hereinafter referred to as “phosphorylation reagent”).
- phosphorylation reagent a phosphoric acid compound
- Softwood bleached kraft pulp (manufactured by Oji Paper Co., Ltd., moisture 50 mass%, Canadian standard freeness (CSF) 700 ml measured according to JIS P8121) is diluted with ion-exchanged water so that the moisture content is 80 mass%.
- a pulp suspension was obtained.
- 210 g of the phosphorylating reagent was added to 500 g of this pulp suspension, and the mixture was dried until the mass became constant while being kneaded occasionally with a blow dryer at 105 ° C. Subsequently, it heat-processed for 1 hour, kneading occasionally with a 150 degreeC ventilation dryer, and introduce
- Ion exchange water was added to the pulp obtained after washing and dewatering to make a 1.0 mass% pulp suspension.
- This pulp suspension was passed five times with a high-pressure homogenizer (“Panda Plus 2000” manufactured by NiroSoavi) at an operating pressure of 1200 bar to obtain a fine fibrous cellulose suspension (1). Furthermore, it was passed 5 times at a pressure of 245 MPa with a wet atomizer (“Ultimizer” manufactured by Sugino Machine Co., Ltd.) to obtain a fine fibrous cellulose suspension (2).
- the average fiber width of the fine fibrous cellulose was 4.2 nm.
- Polyethylene glycol manufactured by Wako Pure Chemical Industries, Ltd .: molecular weight 4000000 was added to the fine fibrous cellulose suspension (2) so as to be 15 parts by mass with respect to 100 parts by mass of the fine fibrous cellulose.
- the concentration was adjusted so that the solid content concentration was 0.5% by mass.
- the suspension was weighed so that the finished basis weight of the nonwoven fabric was 37.5 g / m 2 , developed on a commercially available acrylic plate, and dried in an oven at 50 ° C.
- the board for a dam was arrange
- the nonwoven fabric layer (A) was obtained (the content of fine fibrous cellulose contained in the nonwoven fabric layer was 86.9% by mass).
- the resulting nonwoven fabric layer (A) had a thickness of 25 ⁇ m and a density of 1.49 g / cm 3 .
- coating layer (B) 76 parts by weight of UV coat anchor agent (Arakawa Chemical Industries, Ltd. Aracoat AP2510, solid content 30% by mass), which is a polyester resin, curing agent (Arakawa Chemical Industry Aracoat CL2502, Solid content 20% by mass) 10 parts by weight and 14 parts by weight of methyl ethyl ketone were mixed to obtain an easily adhesive coating solution. Next, an easy-adhesive coating solution was applied to one side of the nonwoven fabric layer (A) using a Mayer bar. Then, it dried at 100 degreeC for 3 minute (s), the easy-adhesion coating liquid was hardened, and the coating layer (B) with a thickness of 1 micrometer was formed into a film. By the above procedure, a composite composed of the nonwoven fabric layer (A) and the coating layer (B) was obtained.
- UV coat anchor agent Arakawa Chemical Industries, Ltd. Aracoat AP2510, solid content 30% by mass
- curing agent Arakawa Chemical Industry Aracoat CL2502
- Example 2 (1) Formation of coating layer (B) In (2) of Experimental Example 1, after the coating layer (B) was formed on one side of the nonwoven fabric layer (A), the thickness on the opposite side was increased in the same procedure. A coating layer (B) having a thickness of 1.0 ⁇ m was formed to obtain a composite composed of the nonwoven fabric layer (A) and the coating layer (B).
- Example 3 50 parts by weight of a urethane acrylate resin composition (“Beam Set 575CB” manufactured by Arakawa Chemical Industries) and 50 parts by weight of methyl ethyl ketone were mixed to obtain a curable resin precursor solution.
- the curable resin precursor solution was applied to one side of the composite composed of the nonwoven fabric layer (A) and the coating layer (B) obtained in (1) of Experimental Example 2 using a Mayer bar.
- UV light of 300 mJ / cm 2 was irradiated using a UV conveyor device (“ECS-4011GX” manufactured by Eye Graphics Co., Ltd.) to cure the curable resin precursor solution.
- a resin layer (C) having a thickness of 2.5 ⁇ m was formed. Further, a resin layer (C) having a thickness of 2.5 ⁇ m was formed on the opposite surface in the same procedure.
- the composite body in which the resin layer (C) was laminated on both surfaces of the nonwoven fabric layer (A) via the coating layer (B) was obtained.
- Example 4 40 parts by weight of an acrylic resin composition (“Adekaoptomer HC500-60” manufactured by Adeka) and 60 parts by weight of methyl ethyl ketone were mixed to obtain a curable resin precursor solution.
- the curable resin precursor solution was applied to one side of the composite composed of the nonwoven fabric layer (A) and the coating layer (B) obtained in Example 2 (1) using a Mayer bar.
- the UV curable resin precursor solution was cured by irradiating with 300 mJ / cm 2 of UV using a UV conveyor device (“ECS-4011GX” manufactured by Eye Graphics).
- a resin layer (C) having a thickness of 2.5 ⁇ m was formed.
- a resin layer (C) having a thickness of 2.5 ⁇ m was formed on the opposite surface in the same procedure.
- the composite body in which the resin layer (C) was laminated on both surfaces of the nonwoven fabric layer (A) via the coating layer (B) was obtained.
- Example 5 In Experimental Example 4, the thickness of the nonwoven fabric layer (A) was 50 ⁇ m (density 1.47 g / cm 3 ). Except for the above, a composite in which the resin layer (C) was laminated on both surfaces of the nonwoven fabric layer (A) via the coating layer (B) was obtained in the same procedure as in Experimental Example 4.
- Example 6 In Experimental Example 4, the thickness of the nonwoven fabric layer (A) was 75 ⁇ m (density 1.46 g / cm 3 ). Except for the above, a composite in which the resin layer (C) was laminated on both surfaces of the nonwoven fabric layer (A) via the coating layer (B) was obtained in the same procedure as in Experimental Example 4.
- Example 7 In Experimental Example 6, the thickness of the resin layer (C) formed on both surfaces of the composite composed of the nonwoven fabric layer (A) and the coating layer (B) was 10 ⁇ m. Except for the above, a composite in which the resin layer (C) was laminated on both surfaces of the nonwoven fabric layer (A) via the coating layer (B) was obtained in the same procedure as in Experimental Example 6.
- Example 8 In Experimental Example 6, the thickness of the resin layer (C) formed on both surfaces of the composite composed of the nonwoven fabric layer (A) and the coating layer (B) was 20 ⁇ m. Except for the above, a composite in which the resin layer (C) was laminated on both surfaces of the nonwoven fabric layer (A) via the coating layer (B) was obtained in the same procedure as in Experimental Example 6.
- Example 9 Film formation of coating layer (B) Silsesquioxane ("Composeran SQ107” manufactured by Arakawa Chemical Industries, Ltd.) 26 parts by weight, curing agent ("HBSQ201” manufactured by Arakawa Chemical Industries, Ltd.) 14 parts by weight, isopropyl alcohol 60 parts by weight The parts were mixed to obtain an adhesive coating solution. Next, an adhesive coating solution was applied to one side of the nonwoven fabric layer (A) obtained in (1) of Experimental Example 1 using a Mayer bar. Then, after drying at 100 ° C. for 3 minutes, UV adhesive of 300 mJ / cm 2 was irradiated using a UV conveyor device (“ECS-4011GX” manufactured by iGraphics) to cure the adhesive coating solution.
- a UV conveyor device (“ECS-4011GX” manufactured by iGraphics)
- a coating layer (B) having a thickness of 2.5 ⁇ m was formed. Further, a coating layer having a thickness of 2.5 ⁇ m was formed on the opposite surface in the same procedure. By the above procedure, a composite composed of the nonwoven fabric layer (A) and the coating layer (B) was obtained.
- a resin layer (C) having a thickness of 2.5 ⁇ m was formed on the opposite surface in the same procedure.
- the composite body in which the resin layer (C) was laminated on both surfaces of the nonwoven fabric layer (A) via the coating layer (B) was obtained.
- Example 10 In Experimental Example 9, the thickness of the coating layer (B) formed on both sides of the nonwoven fabric layer (A) is 5.0 ⁇ m, and both sides of the composite composed of the nonwoven fabric layer (A) and the coating layer (B) The thickness of the resin layer (C) formed on the substrate was 10 ⁇ m. Except for the above, a composite in which the resin layer (C) was laminated on both surfaces of the nonwoven fabric layer (A) via the coating layer (B) was obtained in the same procedure as in Experimental Example 9.
- Example 11 In Experimental Example 10, the thickness of the nonwoven fabric layer (A) was 130 ⁇ m (density 1.42 g / cm 3 ). Except for the above, a composite in which the resin layer (C) was laminated on both surfaces of the nonwoven fabric layer (A) via the coating layer (B) was obtained in the same procedure as in Experimental Example 10.
- Example 12 In Experimental Example 11, the thickness of the resin layer (C) formed on both surfaces of the composite composed of the nonwoven fabric layer (A) and the coating layer (B) was 40 ⁇ m. In the film formation of the resin layer (C), coating was performed using a film applicator in order to increase the coating amount of the curable resin precursor solution to obtain a predetermined film thickness. Except for the above, a composite in which the resin layer (C) was laminated on both surfaces of the nonwoven fabric layer (A) via the coating layer (B) was obtained in the same procedure as in Experimental Example 11.
- Example 13 In Experimental Example 12, the thickness of the coating layer (B) formed on both surfaces of the nonwoven fabric layer (A) was 25 ⁇ m.
- Coating was performed using an applicator. Except for the above, a composite in which the resin layer (C) was laminated on both surfaces of the nonwoven fabric layer (A) via the coating layer (B) was obtained in the same procedure as in Experimental Example 12.
- Example 14 A 2.5 ⁇ m resin layer (C) was formed on one side of the nonwoven fabric layer (A) obtained in (1) of Experimental Example 1 by the same procedure as in (3) of Experimental Example 1. Further, a resin layer (C) having a thickness of 2.5 ⁇ m was formed on the opposite surface in the same procedure. By the above procedure, the composite body in which the resin layer (C) was directly laminated on both surfaces of the nonwoven fabric layer (A) was obtained.
- Example 15 On one side of the nonwoven fabric layer (A) obtained in (1) of Experimental Example 1, 40 parts by weight of an acrylic resin composition (“ADEKA OPTMER HC500-60” manufactured by Adeka) and 60 parts by weight of methyl ethyl ketone were mixed. The obtained curable resin precursor solution was applied using a Mayer bar. Next, after drying at 100 ° C. for 2 minutes, the UV curable resin precursor solution was cured by irradiating with 300 mJ / cm 2 of UV using a UV conveyor device (“ECS-4011GX” manufactured by Eye Graphics). A resin layer (C) having a thickness of 2.5 ⁇ m was formed.
- an acrylic resin composition (“ADEKA OPTMER HC500-60” manufactured by Adeka)
- methyl ethyl ketone 60 parts by weight of methyl ethyl ketone were mixed.
- the obtained curable resin precursor solution was applied using a Mayer bar. Next, after drying at 100 ° C. for 2 minutes, the UV curable resin precursor solution was
- a resin layer (C) having a thickness of 2.5 ⁇ m was formed on the opposite surface in the same procedure.
- the composite body in which the resin layer (C) was directly laminated on both surfaces of the nonwoven fabric layer (A) was obtained.
- Example 16 (1) of Experimental Example 1 except that polyethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd .: molecular weight 4000000) was added so as to be 150 parts by mass with respect to 100 parts by mass of fine fibrous cellulose.
- the nonwoven fabric layer (A) was obtained in the same manner as described above (the content of fine fibrous cellulose contained in the nonwoven fabric layer was 40% by mass).
- a resin layer (C) having a thickness of 2.5 ⁇ m was formed in the same procedure as (3) of Experimental Example 1. Further, a resin layer (C) having a thickness of 2.5 ⁇ m was formed on the opposite surface in the same procedure.
- the composite body in which the resin layer (C) was directly laminated on both surfaces of the nonwoven fabric layer (A) was obtained.
- Example 17 In Experimental Example 1, a coating layer (B) was formed on the nonwoven fabric layer (A), and a composite without forming the resin layer (C) was produced. That is, a lamination sheet (composite) composed of two layers of a nonwoven fabric layer (A) and a coating layer (B) was produced. The adhesion between the nonwoven fabric layer (A) and the coating layer (B) was evaluated. All other tests were performed in the same manner as in Experimental Example 1. The results are shown in Table 2.
- the lamination sheets (Experimental Examples 17 and 18) in which the coating layer was laminated on the nonwoven fabric layer (sheet layer) had high adhesion between the nonwoven fabric layer and the coating layer and were highly transparent.
- Example 23 An after-UV type adhesive (“DC011” manufactured by New Tac Kasei Co., Ltd., thickness 25 ⁇ m) was bonded as a coating layer (B) to the nonwoven fabric layer (A) obtained in Experimental Example 1. Furthermore, a PET film (“Lumirror S10” manufactured by Toray Industries Inc., thickness 25 ⁇ m) was bonded as a film layer (C) to the upper surface of the coating layer (B). Thereafter, the coating layer (B) was cured by irradiating UV rays of 250 mJ / cm 2 six times from the film layer (C) side using a UV conveyor device (“ECS-4011GX” manufactured by Eye Graphics Co., Ltd.). By the above procedure, the composite body by which the film layer (C) was laminated
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Abstract
Description
本発明はまた、高強度で透明性の高い複合体、また、微細セルロース繊維を主成分とするシート(シート層)と、硬化性樹脂層又はフィルム層との密着性の高い複合体、微細セルロース繊維を主成分とするシート(シート層)と、被覆層との密着性の高い張り合わせ用シートを提供することを解決すべき課題とした。
詳細には、本発明者らは上記の課題を解決するために鋭意検討した。その結果、1)平均繊維幅2~1000nmの微細繊維を主成分とするシート(以下、「シート層」という。)の片面又は両面に硬化性樹脂層又はフィルム層が積層された複合体は高強度で高透明であることを見出した。また、2)平均繊維幅2~1000nmの微細繊維を主成分とするシート層の片面又は両面に被覆層を介して硬化性樹脂層又はフィルム層が積層された複合体、3)平均繊維幅2~1000nmの微細繊維を主成分とするシート層の片面又は両面に被覆層が積層された張り合わせ用シートは、各層間の密着性が高く、高強度で高透明であることを見出し、本発明を完成するに至った。
(1)平均繊維幅2~1000nmの微細繊維を主成分とするシート層の片面又は両面に、硬化性樹脂層又はフィルム層を有する複合体。
(2)微細繊維の平均繊維幅が2~100nmである、(1)に記載の複合体。
(3)シート層の密度が0.90g/cm3以上である、(1)又は(2)に記載の複合体。
(4)シート層が不織布である(1)から(3)の何れか1項に記載の複合体。
(5)微細繊維が、セルロース繊維を含む繊維である、(1)から(4)の何れか1項に記載の複合体。
(6)シート層の片面又は両面に設けられた被覆層を介して、硬化性樹脂層又はフィルム層が積層された、(1)から(5)の何れか1項に記載の複合体。
(7)シート層の厚さが2~150μmであり、被覆層の厚さが0.1~30μmであり、硬化性樹脂層又はフィルム層の厚さが0.2~100μmである、(6)に記載の複合体。
(8)シート層と、硬化性樹脂層又はフィルム層の密着性が、JIS規格K5400に準拠したクロスカット試験において100マス中のはく離数が10以下である、(6)又は(7)に記載の複合体。
(9)全光線透過率が85%以上であり、ヘーズが10%以下である、(6)から(8)の何れか1項に記載の複合体。
(10)被覆層が、有機成分と無機成分のハイブリッド材である、(6)から(9)の何れか1項に記載の複合体。
(11)有機成分と無機成分のハイブリッド材が、ケイ素骨格を有する有機成分と無機成分から構成される、(10)に記載の複合体。
(12)有機成分がメチル基、メルカプト基、メタクリル基、アクリロイル基、ビニル基、及びアミノ基から選ばれる少なくとも1種を含む成分である、(10)又は(11)に記載の複合体。
(13)有機成分と無機成分のハイブリッド材が、シルセスキオキサンである、(10)から(12)の何れか1項に記載の複合体。
(14)被覆層が、熱硬化性樹脂、熱可塑性樹脂、及び光硬化性樹脂の中から選ばれる少なくとも1種である、(6)から(9)の何れか1項に記載の複合体。
(15)被覆層が粘着剤である、(6)から(9)の何れか1項に記載の複合体。
(16)平均繊維幅2~1000nmのセルロース微細繊維を主成分とするシート層の片面又は両面に、被覆層を有する貼り合わせ用シート。
(17)被覆層が、有機成分と無機成分のハイブリッド材である(16)に記載のシート。
(18)有機成分がメチル基、メルカプト基、メタクリル基、アクリロイル基、ビニル基、及びアミノ基から選ばれる少なくとも1種を含む成分である、(17)に記載のシート。
(19)有機成分と無機成分のハイブリッド材が、シルセスキオキサンである、(17)又は(18)に記載のシート。
(20)(16)~(19)のシートに、硬化性樹脂層又はフィルム層を積層した複合体。
(21)平均繊維幅2~1000nmの微細繊維を主成分とするシート層の片面又は両面に、被覆層を設ける工程;及び前記被覆層の、シート層とは反対側の表面上に、硬化性樹脂層又はフィルム層を設ける工程、を含む、複合体の製造方法。
(22)シート層と被覆層が、塗工、又は貼り合わせにより積層された、(21)に記載の複合体の製造方法。
(23)被覆層と、硬化性樹脂層又はフィルム層が、塗工、又は貼り合わせにより積層された、(21)に記載の複合体の製造方法。
(24)(1)から(20)の何れか1項に記載の複合体を含む、照明装置、投影装置、看板又は画像表示装置、タッチパネル又は太陽電池。
[2]微細繊維の平均繊維幅が2~100nmである、[1]に記載の不織布樹脂複合体。
[3]不織布層の密度が0.90g/cm3以上である、[1]又は[2]に記載の不織布樹脂複合体。
[4]不織布層の厚さが2~150μmであり、易接着性層の厚さが0.1~30μmであり、樹脂層の厚さが0.2~50μmである、[1]から[3]の何れかに記載の不織布樹脂複合体。
[5]樹脂層の密着性が、JIS規格K5400に準拠したクロスカット試験において100マス中のはく離数が10以下である、[1]から[4]の何れかに記載の不織布樹脂複合体。
[6]全光線透過率が85%以上であり、ヘーズが10%以下である[1]から[5]の何れかに記載の不織布樹脂複合体。
[7]易接着性層が、樹脂からなる、[1]から[6]の何れかに記載の不織布樹脂複合体。
[8]易接着性層が、ポリエステル樹脂又はシルセスキオキサン系樹脂からなる、[1]から[7]の何れかに記載の不織布樹脂複合体。
[9]樹脂層が、硬化性樹脂前駆体を紫外線処理又は熱処理によって硬化することにより得た樹脂層である、[1]から[8]の何れかに記載の不織布樹脂複合体。
[10]微細繊維が、セルロース繊維を含む繊維である、[1]から[9]の何れかに記載の不織布樹脂複合体。
[11]繊維原料を化学的処理及び解繊処理することにより得た平均繊維幅2~1000nmの微細繊維を含有する不織布層の片面又は両面に、易接着性層を設ける工程;及び
前記易接着性層の、不織布層とは反対側の表面上に、樹脂層を設ける工程、
を含む、[1]から[10]の何れかに記載の不織布樹脂複合体の製造方法。
[12][1]から[10]の何れかに記載の不織布樹脂複合体を含む、照明装置、投影装置、看板又は画像表示装置、タッチパネル又は太陽電池。
2 被覆層
3 硬化性樹脂層又はフィルム層
本発明におけるシート層は、平均繊維幅2~1000nmの微細繊維を主成分とする。微細繊維は、平均繊維幅が2~1000nmの微細繊維であればその種類は特に限定されず、微細セルロース繊維でもよいし、微細セルロース繊維以外の微細繊維でもよく、微細セルロース繊維と、微細セルロース繊維以外の微細繊維との混合物でもよい。好ましくは、微細繊維はセルロース繊維である。
本発明においては、微細繊維として、セルロース原料を化学的処理及び解繊処理することによって得られる微細セルロース繊維を使用してもよい。
セルロース原料としては、製紙用パルプ、コットンリンターやコットンリントなどの綿系パルプ、麻、麦わら、パガスなどの非木材系パルプ、ホヤや海草などから単離されるセルロースなどが挙げられるが、特に限定されない。これらの中でも、入手のしやすさという点で、製紙用パルプが好ましいが、特に限定されない。製紙用パルプとしては、化学パルプ、半化学パルプ、機械パルプ、非木材パルプ、及び脱墨パルプが挙げられるが、特に限定されない。化学パルプとしては、広葉樹クラフトパルプ、針葉樹クラフトパルプ、サルファイトパルプ(SP)、ソーダパルプ(AP)等を挙げることができる。ここで広葉樹クラフトパルプとしては、晒クラフトパルプ(LBKP)、未晒クラフトパルプ(LUKP)、酸素漂白クラフトパルプ(LOKP)などが挙げられる。また針葉樹クラフトパルプとしては、晒クラフトパルプ(NBKP)、未晒クラフトパルプ(NUKP)、酸素漂白クラフトパルプ(NOKP)などが挙げられる。半化学パルプとしては、セミケミカルパルプ(SCP)、ケミグラウンドウッドパルプ(CGP)等が挙げられる。機械パルプとしては、砕木パルプ(GP)、サーモメカニカルパルプ(TMP、BCTMP)等を挙げられる。非木材パルプとしては、楮、三椏、麻、ケナフ等を原料とする非木材パルプが挙げられる。脱墨パルプとしては、古紙を原料とする脱墨パルプが挙げられる。これらの中でも、より入手しやすいことから、クラフトパルプ、脱墨パルプ、サルファイトパルプが好ましいが、特に限定されない。セルロース原料は1種を単独で用いてもよいし、2種以上混合して用いてもよい。
(2)同じ画像内で該直線と垂直に交差する直線Yを引き、該直線Yに対し、20本以上の繊維が交差する。
セルロース原料又はその他の繊維原料(無機繊維、有機繊維、合成繊維等、半合成繊維、再生繊維など)の化学的処理の方法は、微細繊維を得ることができる方法である限り特に限定されない。処理の方法は、例えば、オゾン処理、TEMPO酸化処理、酵素処理、又はセルロース又は繊維原料中の官能基と共有結合を形成し得る化合物による処理などが挙げられるがこれらに限定されない。
(1)特開2011-162608に記載されている四級アンモニウム基を有する化合物による処理;
(2)特開2013-136859(特開2013-136859の内容は全て本明細書中に引用される)に記載されているカルボン酸系化合物を使用する方法;並びに
(3)国際公開WO2013/73652(WO2013/73652の内容は全て本明細書中に引用される)に記載されている「構造中にリン原子を含有するオキソ酸、ポリオキソ酸又はそれらの塩から選ばれる少なくとも1種の化合物」を使用する方法:
セルロース原料又はその他の繊維原料(無機繊維、有機繊維、合成繊維等、半合成繊維、再生繊維など)は解繊処理に供することにより微細化して、数平均繊維幅が2~1000nmである微細繊維を得ることができる。解繊処理工程では、解繊処理装置を用いて、前記の化学的処理で得られた原料を解繊処理して、微細繊維分散液を得ることができる。
本発明におけるシート層の密度は、特に限定されないが、好ましくは0.90g/cm3以上であり、より好ましくは1.00g/cm3以上であり、さらに好ましくは1.10g/cm3以上である。シート層の密度の上限は、特に限定されないが、一般的には、1.60g/cm3以下である。
なお、シート層は、目的に応じて複数のシート層を積層したものでもよい。複数のシート層を使用する場合は、複数のシート層の合計の厚み並びに合計の密度が、上記した範囲内であることが好ましい。
シート層の形成に際して、微細繊維を含む懸濁液を調製する。この懸濁液には、親水性高分子を添加してもよい。親水性高分子としては、例えば、ポリエチレングリコール、セルロース誘導体(ヒドロキシエチルセルロース,カルボキシエチルセルロース,カルボキシメチルセルロース等)、カゼイン、デキストリン、澱粉、変性澱粉、ポリビニルアルコール、変性ポリビニルアルコール(アセトアセチル化ポリビニルアルコール等)、ポリエチレンオキサイド、ポリビニルピロリドン、ポリビニルメチルエーテル、ポリアクリル酸塩類、ポリアクリルアミド、アクリル酸アルキルエステル共重合体、ウレタン系共重合体などを挙げることができるが、特に限定されない。
被覆層を構成する成分は、特に限定されず、無機成分と有機成分のハイブリッド材、熱硬化性樹脂、光硬化性樹脂、熱可塑性樹脂などを用いることができる。前記樹脂としては、ポリエステル系樹脂、ウレタン系樹脂、アクリル系樹脂、オレフィン系樹脂、フッ素系樹脂、塩化ビニル系樹脂、スチレン系樹脂、エポキシ系樹脂、シリコーン系樹脂、等が挙げられる。被覆層を構成する成分は、無機成分と有機成分のハイブリッド材を用いることが好ましい。前記、無機成分と有機成分のハイブリッド材、又は樹脂は、1種を単独で使用してもよいし、2種以上を併用してもよい。無機成分と有機成分のハイブリッド材と樹脂を併用することもできる。また、被覆層として、粘着剤、粘着シートなどを用いることもできる。
被覆層は、2層以上とすることもできる。複数の被覆層とする場合は、複数の被覆層の合計の厚みが、上記の範囲内であることが好ましい。
硬化性樹脂層又はフィルム層を構成する成分としては、特に限定されないが、熱可塑性樹脂、熱硬化性樹脂、光硬化性樹脂などを用いることができる。硬化性樹脂層又はフィルム層を構成する成分は、湿度、水、熱、ガスなどに対してバリア能を有する成分を用いることが望ましい。硬化性樹脂層又はフィルム層は、少なくとも2層以上積層することもできる。
なお、上記の熱可塑性樹脂、熱硬化性樹脂及び光硬化性樹脂のうち、光硬化性樹脂が最も好ましい。
また、塗布により被覆層を介してシート層に硬化性樹脂層又はフィルム層を接着させる場合、シート層に被覆層を塗工した後、被覆層に上記と同様の方法により硬化性樹脂層又はフィルム層を形成させることができる。
被覆層として、粘着剤、粘着剤と剥離シートから構成される粘着剤(使用時に粘着剤をカバーしている剥離シートを剥がし粘着剤を使用する。(例)商品名:ノンキャリアテープ)、粘着シートなどを用いてシート層と硬化性樹脂層又はフィルム層を貼合わせることもできる。
硬化性樹脂層又はフィルム層は、目的に応じて複数の硬化性樹脂層又はフィルム層を積層したものでもよい。複数の硬化性樹脂層又はフィルム層を使用する場合は、複数の硬化性樹脂層又はフィルム層の合計の厚みが、上記の範囲内であることが好ましい。
本発明の複合体は、1)シート層に硬化性樹脂層又はフィルム層が積層された複合体(2層)、2)シート層と、硬化性樹脂層又はフィルム層が、被覆層を介して積層された複合体(3層)、3)シート層に被覆層が積層された張り合わせ用シート(2層)である。
1)シート層に硬化性樹脂層又はフィルム層が積層された複合体(2層)は、高強度で高透明であるという特徴を有する。2)シート層と、硬化性樹脂層又はフィルム層が、被覆層を介して積層された複合体(3層)は、高強度で高透明であり、シート層と、硬化性樹脂層又はフィルム層の密着性が高いという特徴を有する。3)シート層に被覆層が積層された張り合わせ用シート(2層)は、高強度で高透明であり、シート層と被覆層の密着性が高いという特徴を有する。
前記複合体、及び張り合わせ用シートの各層間の密着性は、以下の実験例に記載したJIS規格K5400に準拠したクロスカット試験において100マス中のはく離数が10以下であることが好ましく、より好ましくは5以下であり、さらに好ましくは3以下である。
また、本発明の複合体、及び張り合わせ用シートは透明性が高いことを特徴とする。本発明の複合体の全光線透過率は、好ましくは70%以上であり、より好ましくは80%以上であり、さらに好ましくは85%以上であり、さらに好ましくは90%以上である。全光線透過率の上限は特に限定されず、100%でもよいし、99%以下でもよい。本発明の複合体のヘーズは、好ましくは10%以下であり、より好ましくは5%以下であり、さらに好ましくは3%以下である。
本発明の複合体、及び張り合わせ用シートは、液晶ディスプレイ、プラズマディスプレイ、有機ELディスプレイ、フィールドエミッションディスプレイ、リアプロジェクションテレビ等の画像表示装置等に用いることができる。さらに本発明の複合体は、照明装置、投影装置に用いることもできる。さらに本発明の複合体、及び張り合わせ用シートは、タッチパネルや太陽電池(シリコン系太陽電池、色素増感太陽電池など)の配線基板や前面板、カラーフィルター基板等に用いることができる。基板としての用途において、バリア膜、ITO、TFT等と積層してもよい。
(1)シート層(A)(不織布層(A)ということもある。)の成膜
シートとして不織布を用いて下記の方法でシート層(不織布層)を作製した。
リン酸二水素ナトリウム二水和物265g、及びリン酸水素二ナトリウム197gを538gの水に溶解させ、リン酸系化合物の水溶液(以下、「リン酸化試薬」という。)を得た。
ポリエステル系樹脂であるUVコートアンカー剤(荒川化学工業社製アラコートAP2510、固形分30質量%)76重量部、硬化剤(荒川化学工業社製アラコートCL2502、固形分20質量%)10重量部及びメチルエチルケトン14重量部を混合し、易接着性塗工液を得た。次いで、不織布層(A)の片面に易接着性塗工液をメイヤーバーを用いて塗工した。その後、100℃で3分間乾燥して易接着性塗工液を硬化し、厚さ1μmの被覆層(B)を成膜した。以上の手順により、不織布層(A)と被覆層(B)から構成される複合体を得た。
アクリル樹脂組成物(荒川化学工業社製「ビームセット381」)80重量部、及びメチルエチルケトン20重量部を混合して、硬化性樹脂前駆体溶液を得た。不織布層(A)・被覆層(B)複合体の被覆層(B)の上に上記の硬化性樹脂前駆体溶液をメイヤーバーを用いて塗工した。次いでUVコンベア装置(アイグラフィックス社製「ECS-4011GX」)を用いて300mJ/cm2の紫外線を照射して、硬化性樹脂前駆体溶液を硬化し、厚さ2.5μmの樹脂層(C)を成膜した。以上の手順により、不織布層(A)の片面に被覆層(B)を介して樹脂層(C)が積層された複合体を得た。
(1)被覆層(B)の成膜
実験例1の(2)において、不織布層(A)の片面に被覆層(B)を成膜した後、反対側の面にも同様の手順で厚さ1.0μmの被覆層(B)を成膜し、不織布層(A)と被覆層(B)から構成される複合体を得た。
不織布層(A)と被覆層(B)から構成される複合体の片面に実験例1の(3)と同様の手順で2.5μmの樹脂層(C)を成膜した。さらに、反対側の面にも同様の手順で厚さ2.5μmの樹脂層(C)を成膜した。以上の手順により、不織布層(A)の両面に被覆層(B)を介して樹脂層(C)が積層された複合体を得た。
ウレタンアクリレート樹脂組成物(荒川化学工業社製「ビームセット575CB」)50重量部、及びメチルエチルケトン50重量部を混合して、硬化性樹脂前駆体溶液を得た。 実験例2の(1)において得た不織布層(A)と被覆層(B)から構成される複合体の片面に、上記の硬化性樹脂前駆体溶液をメイヤーバーを用いて塗工した。次いで80℃で3分間乾燥した後、UVコンベア装置(アイグラフィックス社製「ECS-4011GX」)を用いて300mJ/cm2の紫外線を照射して、硬化性樹脂前駆体溶液を硬化し、厚さ2.5μmの樹脂層(C)を成膜した。さらに、反対側の面にも同様の手順で厚さ2.5μmの樹脂層(C)を成膜した。以上の手順により、不織布層(A)の両面に被覆層(B)を介して樹脂層(C)が積層された複合体を得た。
アクリル樹脂組成物(アデカ社製「アデカオプトマー HC500-60」)40重量部、及びメチルエチルケトン60重量部を混合して、硬化性樹脂前駆体溶液を得た。実施例2の(1)において得た不織布層(A)と被覆層(B)から構成される複合体の片面に、上記の硬化性樹脂前駆体溶液をメイヤーバーを用いて塗工した。次いで100℃で2分間乾燥した後、UVコンベア装置(アイグラフィックス社製「ECS-4011GX」)を用いて300mJ/cm2の紫外線を照射して、硬化性樹脂前駆体溶液を硬化し、厚さ2.5μmの樹脂層(C)を成膜した。さらに、反対側の面にも同様の手順で厚さ2.5μmの樹脂層(C)を成膜した。以上の手順により、不織布層(A)の両面に被覆層(B)を介して樹脂層(C)が積層された複合体を得た。
実験例4において、不織布層(A)の厚さを50μm(密度1.47g/cm3)とした。上記以外は実験例4と同様の手順で、不織布層(A)の両面に被覆層(B)を介して樹脂層(C)が積層された複合体を得た。
実験例4において、不織布層(A)の厚さを75μm(密度1.46g/cm3)とした。上記以外は実験例4と同様の手順で、不織布層(A)の両面に被覆層(B)を介して樹脂層(C)が積層された複合体を得た。
実験例6において、不織布層(A)と被覆層(B)から構成される複合体の両面に成膜する樹脂層(C)の厚さを10μmとした。上記以外は実験例6と同様の手順で、不織布層(A)の両面に被覆層(B)を介して樹脂層(C)が積層された複合体を得た。
実験例6において、不織布層(A)と被覆層(B)から構成される複合体の両面に成膜する樹脂層(C)の厚さを20μmとした。上記以外は実験例6と同様の手順で、不織布層(A)の両面に被覆層(B)を介して樹脂層(C)が積層された複合体を得た。
(1)被覆層(B)の成膜
シルセスキオキサン(荒川化学工業社製「コンポセランSQ107」)26重量部、硬化剤(荒川化学工業社製「HBSQ201」)14重量部、イソプロピルアルコール60重量部を混合し、接着性塗工液を得た。次いで、実験例1の(1)で得られた不織布層(A)の片面に接着性塗工液をメイヤーバーを用いて塗工した。その後、100℃で3分間乾燥した後、UVコンベア装置(アイグラフィックス社製「ECS-4011GX」)を用いて300mJ/cm2の紫外線を照射して、接着性塗工液を硬化し、厚さ2.5μmの被覆層(B)を成膜した。さらに、反対側の面にも同様の手順で厚さ2.5μmの被覆層を成膜した。以上の手順により、不織布層(A)と被覆層(B)から構成される複合体を得た。
アクリル樹脂組成物(アデカ社製「アデカオプトマー HC500-60」)40重量部、及びメチルエチルケトン60重量部を混合して、硬化性樹脂前駆体溶液を得た。不織布層(A)と被覆層(B)から構成される複合体の片面に、上記の硬化性樹脂前駆体溶液をメイヤーバーを用いて塗工した。次いで100℃で2分間乾燥した後、UVコンベア装置(アイグラフィックス社製「ECS-4011GX」)を用いて300mJ/cm2の紫外線を照射して、硬化性樹脂前駆体溶液を硬化し、厚さ2.5μmの樹脂層(C)を成膜した。さらに、反対側の面にも同様の手順で厚さ2.5μmの樹脂層(C)を成膜した。以上の手順により、不織布層(A)の両面に被覆層(B)を介して樹脂層(C)が積層された複合体を得た。
実験例9において、不織布層(A)の両面に成膜する被覆層(B)の厚さを5.0μmとし、また不織布層(A)と被覆層(B)から構成される複合体の両面に成膜する樹脂層(C)の厚さを10μmとした。上記以外は実験例9と同様の手順で、不織布層(A)の両面に被覆層(B)を介して樹脂層(C)が積層された複合体を得た。
実験例10において、不織布層(A)の厚さを130μm(密度1.42g/cm3)とした。上記以外は実験例10と同様の手順で、不織布層(A)の両面に被覆層(B)を介して樹脂層(C)が積層された複合体を得た。
実験例11において、不織布層(A)と被覆層(B)から構成される複合体の両面に成膜する樹脂層(C)の厚さを40μmとした。なお、樹脂層(C)の成膜においては、硬化性樹脂前駆体溶液の塗工量を増やし、所定の膜厚とするため、フィルムアプリケーターを用いて塗工を行った。上記以外は実験例11と同様の手順で、不織布層(A)の両面に被覆層(B)を介して樹脂層(C)が積層された複合体を得た。
実験例12において、不織布層(A)の両面に成膜する被覆層(B)の厚さ25μmとした。なお、被覆層(B)、及び樹脂層(C)の成膜においては、易接着性塗工液、及び硬化性樹脂前駆体溶液の塗工量を増やし、所定の膜厚とするため、フィルムアプリケーターを用いて塗工を行った。上記以外は実験例12と同様の手順で、不織布層(A)の両面に被覆層(B)を介して樹脂層(C)が積層された複合体を得た。
実験例1の(1)で得られた不織布層(A)の片面に、実験例1の(3)と同様の手順で2.5μmの樹脂層(C)を成膜した。さらに、反対側の面にも同様の手順で厚さ2.5μmの樹脂層(C)を成膜した。以上の手順により、不織布層(A)の両面に樹脂層(C)が直接積層された複合体を得た。
実験例1の(1)で得られた不織布層(A)の片面に、アクリル樹脂組成物(アデカ社製「アデカオプトマー HC500-60」)40重量部、及びメチルエチルケトン60重量部を混合して得た硬化性樹脂前駆体溶液をメイヤーバーを用いて塗工した。次いで100℃で2分間乾燥した後、UVコンベア装置(アイグラフィックス社製「ECS-4011GX」)を用いて300mJ/cm2の紫外線を照射して、硬化性樹脂前駆体溶液を硬化し、厚さ2.5μmの樹脂層(C)を成膜した。さらに、反対側の面にも同様の手順で厚さ2.5μmの樹脂層(C)を成膜した。以上の手順により、不織布層(A)の両面に樹脂層(C)が直接積層された複合体を得た。
実験例1の(1)において、ポリエチレングリコール(和光純薬社製:分子量4000000)を微細繊維状セルロース100質量部に対し、150質量部になるように添加した以外は実験例1の(1)と同様にして不織布層(A)を得た(不織布層に含まれる微細繊維状セルロースの含有量は、40質量%)。次いで、実験例1の(3)と同様の手順で2.5μmの樹脂層(C)を成膜した。さらに、反対側の面にも同様の手順で厚さ2.5μmの樹脂層(C)を成膜した。以上の手順により、不織布層(A)の両面に樹脂層(C)が直接積層された複合体を得た。
前記の実験例で作製した複合体について以下の評価方法に従って評価した。上記の評価結果を表1に示す。
JIS規格K5400に準拠し、複合体の面に1mm2のクロスカットを100個入れ、セロハンテープ(ニチバン社製)をその上に貼り付け、1.5kg/cm2の荷重で押し付けた後、90°方向にはく離した。はく離したマス数により、不織布層(A)と樹脂層(C)の密着性を評価した。
(2)複合体の全光線透過率
JIS規格K7105に準拠し、ヘーズメータ(スガ試験機社製「HM-150」)を用いてC光による全光線透過率を測定した。
(3)複合体のヘーズ
JIS規格K7136に準拠し、ヘーズメータ(スガ試験機社製「HM-150」)を用いてC光によるヘーズ値を測定した。
(4)引張弾性率
JIS規格P8113に準拠し、引張試験機(L&W社製「フラクチャータフネステスターSE-064」)を用いて引張弾性率を測定した。
実験例1において、不織布層(A)に被覆層(B)を成膜し、樹脂層(C)を成膜しない複合体を作製した。すなわち、不織布層(A)と被覆層(B)の2層から構成される張り合わせ用シート(複合体)を作製した。不織布層(A)と被覆層(B)の密着性について評価した。それ以外は全て実験例1と同様の方法で試験した。結果を表2に示す。
実験例17において、不織布層の片面に被覆層を成膜した後、不織布層の反対側の面にも同様の手順で厚さ1.0μmの被覆層を成膜した以外は全て実験例17と同様の方法で試験した。結果を表2に示す。
実験例1で作製した複合体の割れ易さについて下記の方法で評価した(以下、「割れ性の評価」という。)。結果を表3に示す。
複合体(縦10cm x 横10cm)を手で折り曲げ、不織布複合体に亀裂が生じるかかどうかを目視で下記の基準で評価した。
○:亀裂が生じなかった。
×:亀裂が生じた
実験例2で作製した複合体の割れ易さについて実験例19と同様の方法で評価した。結果を表3に示す。
実験例1において、被覆層としてポリエステル系樹脂の代わりにシルセスキオキサン(荒川化学工業社製「コンポセランSQ107」)を用いた以外は全て実験例1と同様の方法で試験した。作製した複合体の割れ易さについて実験例19と同様の方法で評価した。結果を表3に示す。
実験例2において、被覆層としてポリエステル系樹脂の代わりにシルセスキオキサン(荒川化学工業社製「コンポセランSQ107」)を用いた以外は全て実験例2と同様の方法で試験した。作製した複合体の割れ易さについて実験例19と同様の方法で評価した。結果を表3に示す。
実験例1で得られた不織布層(A)に対し、被覆層(B)としてアフターUV型粘着剤(新タック化成製「DC011」、厚さ25μm)を貼合した。さらに、被覆層(B)の上面にフィルム層(C)としてPETフィルム(東レ製「ルミラーS10」、厚さ25μm)を貼合した。その後、UVコンベア装置(アイグラフィックス社製「ECS-4011GX」)を用いてフィルム層(C)側から250mJ/cm2の紫外線を6回照射して、被覆層(B)を硬化させた。以上の手順により、不織布層(A)の片面に被覆層(B)を介してフィルム層(C)が積層された複合体を得た。結果を表4に示す。
実験例23において、シート層(A)の片面に被覆層(B)、及びフィルム層(C)を積層した後、反対側の面にも同様の手順で被覆層(B)、及びフィルム層(C)を積層した。以上の手順により、シート層(A)の両面に被覆層(B)を介してフィルム層(C)が積層された複合体を得た。結果を表4に示す。
Claims (24)
- 平均繊維幅2~1000nmの微細繊維を主成分とするシート層の片面又は両面に、硬化性樹脂層又はフィルム層を有する複合体。
- 微細繊維の平均繊維幅が2~100nmである、請求項1に記載の複合体。
- シート層の密度が0.90g/cm3以上である、請求項1又は2に記載の複合体。
- シート層が不織布である、請求項1から3の何れか1項に記載の複合体。
- 微細繊維が、セルロース繊維を含む繊維である、請求項1から4の何れか1項に記載の複合体。
- シート層の片面又は両面に設けられた被覆層を介して、硬化性樹脂層又はフィルム層が積層された、請求項1から5の何れか1項に記載の複合体。
- シート層の厚さが2~150μmであり、被覆層の一層当たりの厚さが0.1~30μmであり、硬化性樹脂層又はフィルム層の一層当たりの厚さが0.2~100μmである、請求項6に記載の複合体。
- シート層と、硬化性樹脂層又はフィルム層の密着性が、JIS規格K5400に準拠したクロスカット試験において100マス中のはく離数が10以下である、請求項6又は7に記載の複合体。
- 全光線透過率が85%以上であり、ヘーズが10%以下である、請求項6から8の何れか1項に記載の複合体。
- 被覆層が、有機成分と無機成分のハイブリッド材である、請求項6から9の何れか1項に記載の複合体。
- 有機成分と無機成分のハイブリッド材が、ケイ素骨格を有する有機成分と無機成分から構成される、請求項10に記載の複合体。
- 有機成分がメチル基、メルカプト基、メタクリル基、アクリロイル基、ビニル基、及びアミノ基から選ばれる少なくとも1種類を含む成分である、請求項10又は11に記載の複合体。
- 有機成分と無機成分のハイブリッド材が、シルセスキオキサンである、請求項10から12の何れか1項に記載の複合体。
- 被覆層が、熱硬化性樹脂、熱可塑性樹脂、及び光硬化性樹脂から選ばれる少なくとも1種である、請求項6から9の何れか1項に記載の複合体。
- 被覆層が粘着剤である、請求項6から9の何れか1項に記載の複合体。
- 平均繊維幅2~1000nmのセルロース微細繊維を主成分とするシート層の片面又は両面に、被覆層を有する貼り合わせ用シート。
- 被覆層が、有機成分と無機成分のハイブリッド材である、請求項16に記載のシート。
- 有機成分が、メチル基、メルカプト基、メタクリル基、アクリロイル基、ビニル基、及びアミノ基から選ばれる少なくとも1種を含む成分である、請求項17に記載のシート。
- 有機成分と無機成分のハイブリッド材が、シルセスキオキサンである、請求項17又は18に記載のシート。
- 請求項16~19のシートに、硬化性樹脂層又はフィルム層を積層した複合体。
- 平均繊維幅2~1000nmの微細繊維を主成分とするシート層の片面又は両面に、被覆層を設ける工程;及び
前記被覆層の、シート層とは反対側の表面上に、硬化性樹脂層又はフィルム層を設ける工程
を含む、複合体の製造方法。 - シート層と被覆層が、塗工、又は貼り合わせにより積層された、請求項21に記載の複合体の製造方法。
- 被覆層と、硬化性樹脂層又はフィルム層が、塗工、又は貼り合わせにより積層された、請求項21に記載の複合体の製造方法。
- 請求項1から20の何れか1項に記載の複合体を含む、照明装置、投影装置、看板又は画像表示装置、タッチパネル、又は太陽電池。
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EP3135488B1 (en) | 2023-12-06 |
JP2020104525A (ja) | 2020-07-09 |
EP3135488C0 (en) | 2023-12-06 |
JP6950778B2 (ja) | 2021-10-13 |
EP3135488A1 (en) | 2017-03-01 |
JPWO2015163281A1 (ja) | 2017-04-13 |
TW201542366A (zh) | 2015-11-16 |
CN106457798A (zh) | 2017-02-22 |
EP3135488A4 (en) | 2017-11-08 |
US20170043565A1 (en) | 2017-02-16 |
KR20160145608A (ko) | 2016-12-20 |
US10532545B2 (en) | 2020-01-14 |
JP6686880B2 (ja) | 2020-04-22 |
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