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WO2015029623A1 - Article stratifié avec revêtement dur et son procédé de fabrication - Google Patents

Article stratifié avec revêtement dur et son procédé de fabrication Download PDF

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Publication number
WO2015029623A1
WO2015029623A1 PCT/JP2014/068809 JP2014068809W WO2015029623A1 WO 2015029623 A1 WO2015029623 A1 WO 2015029623A1 JP 2014068809 W JP2014068809 W JP 2014068809W WO 2015029623 A1 WO2015029623 A1 WO 2015029623A1
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WIPO (PCT)
Prior art keywords
hard coat
coat layer
layer
base sheet
composition
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Ceased
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PCT/JP2014/068809
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English (en)
Japanese (ja)
Inventor
伊藤　雅春
瑛 高橋
拓己 古屋
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Lintec Corp
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Lintec Corp
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Priority to JP2015534075A priority Critical patent/JP6453755B2/ja
Publication of WO2015029623A1 publication Critical patent/WO2015029623A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • G02B1/105—
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/111—Anti-reflection coatings using layers comprising organic materials
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings

Definitions

  • the present invention relates to a hard coat laminate including a base sheet and a hard coat layer, and a method for producing the same.
  • LCD liquid crystal display
  • PDP plasma display
  • OELD organic EL display
  • touch panel a touch panel
  • LCD liquid crystal display
  • PDP plasma display
  • OELD organic EL display
  • touch panel a touch panel
  • a hard coat film having a hard coat layer is often provided on the surface of these various displays.
  • a low refractive index layer may be provided in order to prevent the reflection of the screen resulting from reflection by sunlight, light from an electric lamp, or the like.
  • the hard coat layer and the low refractive index layer are provided separately, the number of layers and the number of production steps increase, and the production of the hard coat film becomes complicated.
  • Patent Document 1 is a laminate including a transparent base material and a refractive layer in order to prevent light reflection and reflection on the screen as described above, and the refractive layer has a low refractive index in the layer.
  • a structure in which an inclined structure layer having a high refractive index and a high refractive index is formed is proposed.
  • This refractive layer is composed of a fluorine compound such as fluorosilsesquioxane and a resin having a higher refractive index than the fluorine compound, and the concentration of the fluorine compound in the refractive layer is higher than that of the substrate side. It is higher on the other side. Thereby, the refractive index gradient structure as described above is formed.
  • the refractive layer in the laminate of Patent Document 1 is not intended for hard coat properties, a separate hard coat layer is provided between the transparent substrate and the refractive layer. If it does so, the number of layers and the number of manufacturing processes will also increase, and manufacturing will become complicated.
  • the thickness of the refractive layer in the laminate of Patent Document 1 is 0.1 to 20 ⁇ m, and high hardness cannot be expected depending on the thickness.
  • the present invention has been made in view of such a situation, and provides a hard coat laminate including a hard coat layer having a high surface hardness and capable of suppressing light reflection with a single layer, and a method for manufacturing the same.
  • the purpose is to provide.
  • the present invention is a hard coat laminate comprising a base sheet and a hard coat layer laminated on at least one main surface side of the base sheet,
  • the thickness of the hard coat layer is 25 to 80 ⁇ m, and the refractive index of the hard coat layer on the base sheet side is less than the refractive index of the hard coat layer on the side opposite to the base sheet side.
  • a hard coat laminate characterized by being higher than 005 (Invention 1).
  • the thickness of a hard-coat layer is 25 micrometers or more and the refractive index of a hard-coat layer inclines in the thickness direction with said refractive index difference, Both reflection of light at the interface with the substrate sheet and reflection of light at the interface with the air of the hard coat layer (the surface of the hard coat layer) are suppressed, and the total light transmittance of the hard coat laminate is improved. .
  • the thickness of the hard coat layer is 25 ⁇ m or more, the two types of reflected light hardly interfere with each other, and the occurrence of uneven interference on the surface of the hard coat layer is suppressed.
  • the thickness of the hard coat layer is 25 ⁇ m or more, the surface hardness of the hard coat layer, and hence the hard coat laminate, becomes high.
  • the refractive index of the hard coat layer is preferably in the range of 1.35 to 1.7 (Invention 2).
  • the hard coat layer is preferably made of a material obtained by curing a composition containing an ultraviolet curable component and a photopolymerization initiator (Invention 3).
  • the composition preferably contains a phosphorus-based photopolymerization initiator as the photopolymerization initiator (Invention 4).
  • the hard coat layer preferably contains a fluorine-based additive and / or a silicone-based additive (Invention 5).
  • the hard coat layer preferably contains an inorganic filler (Invention 6).
  • the inorganic filler is preferably a silica filler (Invention 7).
  • the thickness of the substrate sheet is preferably 50 to 250 ⁇ m (Invention 8).
  • the hard coat layer is laminated on one main surface side of the base sheet, and an adhesive layer is laminated on the other main surface side of the base sheet. (Invention 9).
  • this invention is a method of manufacturing the said hard-coat laminated body (invention 3), Comprising: The layer which consists of the said composition is laminated
  • a method for producing a hard coat laminate is provided (Invention 10).
  • the hard coat laminate according to the present invention has a high surface hardness and can suppress light reflection by a single hard coat layer. Moreover, according to the manufacturing method of the hard-coat laminated body which concerns on this invention, such a hard-coat laminated body can be manufactured easily.
  • FIG. 1 is a cross-sectional view of a hard coat laminate according to an embodiment of the present invention.
  • a hard coat laminate 1 according to this embodiment includes a base sheet 2 and a hard coat layer 3 stacked on one main surface side (upper side in FIG. 1) of the base sheet.
  • the thickness of the hard coat layer 3 is 25 to 80 ⁇ m, and the hard coat layer 3 is on the base sheet 2 side (interface side with the base sheet 2).
  • the refractive index is 0.005 or more higher than the refractive index on the side opposite to the base sheet 2 side of the hard coat layer 3 (the surface side of the hard coat layer 3). Therefore, the refractive index of the hard coat layer 3 is increased in the thickness direction. It is inclined.
  • the refractive index on the base sheet 2 side of the hard coat layer 3 is 0.005 or more higher than the refractive index on the side opposite to the base sheet 2 side of the hard coat layer 3, and thus the refractive index of the hard coat layer 3 is When inclined in the thickness direction, the refractive index on the base sheet 2 side of the hard coat layer 3 becomes close to the refractive index of the base sheet 2, and light at the interface between the hard coat layer 3 and the base sheet 2.
  • the refractive index on the surface side of the hard coat layer 3 is close to the refractive index of air, and the reflection of light at the interface between the hard coat layer 3 and the air (the surface of the hard coat layer 3) is suppressed. Is done. That is, according to the hard coat laminated body 1 which concerns on this embodiment, reflection of light can be suppressed by the single-layer hard coat layer 3.
  • the refractive index on the base sheet 2 side of the hard coat layer 3 in this specification refers to the measured value of the refractive index on the base sheet 2 side surface (interface with the base sheet 2) of the hard coat layer 3.
  • the refractive index of the hard coat layer 3 on the side opposite to the substrate sheet 2 side is the refractive index of the surface of the hard coat layer 3 opposite to the substrate sheet 2 side (the surface of the hard coat layer 3; the interface with air).
  • the measurement wavelength of the refractive index is 405 nm, and the measurement temperature is 25 ° C. Details of the method of measuring the refractive index are as shown in the test examples described later.
  • the refractive index of the hard coat layer 3 on the base sheet 2 side is preferably 0.006 or higher than the refractive index of the hard coat layer 3 on the side opposite to the base sheet 2 side. In particular, it is preferably higher than 0.007. In addition, the upper limit of this refractive index difference is usually about 0.1, preferably about 0.01.
  • the refractive index of the hard coat layer 3 is preferably in the range of 1.35 to 1.7, particularly preferably in the range of 1.35 to 1.65, and more preferably 1.35 to 1. Is preferably in the range of .6.
  • the refractive index of the hard coat layer 3 is within the above range, reflection of light can be more effectively suppressed.
  • the thickness of the hard coat layer 3 is 25 ⁇ m or more, it is possible to suppress the gradient of the refractive index as described above, and consequently the reflection of light. Moreover, when the thickness of the hard coat layer 3 is 25 ⁇ m or more, the surface hardness of the hard coat layer 3 becomes high. Further, when the thickness of the hard coat layer 3 is 25 ⁇ m or more, interference unevenness occurs due to interference between reflected light at the interface of the hard coat layer 3 with the base material sheet 2 and reflected light at the surface of the hard coat layer 3. Is suppressed, and the hard coat laminate 1 is excellent in light transmittance and aesthetics. This is because when the thickness of the hard coat layer 3 is large, the probability that the two types of reflected light waves overlap with each other is reduced, and light interference is less likely to occur.
  • the hard coat laminate 1 is excellent in bending resistance and easy to handle, and the hard coat laminate 1 becomes unnecessarily thick, and the manufacturing cost is reduced. It is possible to prevent the increase.
  • the thickness of the hard coat layer 3 is preferably 30 to 80 ⁇ m, and particularly preferably 35 to 80 ⁇ m.
  • the hard coat laminate 1 according to this embodiment can suppress light reflection as described above. Accordingly, the total light transmittance of the hard coat laminate 1 is preferably 80 to 96%, particularly preferably 85 to 94%, and further preferably 86 to 94%, which is excellent for optical applications. In addition, the total light transmittance in this specification says the value measured based on JISJK 7361.
  • the base sheet 2 of the hard coat laminate 1 according to this embodiment may be appropriately selected according to the use of the hard coat laminate 1, but has good affinity with the hard coat layer 3. It is preferable to use a simple resin film.
  • the hard coat laminate 1 according to the present embodiment has excellent bending resistance, and is transported and stored in the state of the wound body, or is fed from the wound body. It becomes easy to handle the hard coat laminate 1 such as all processes (for example, roll-to-roll process).
  • the hard coat laminate 1 according to the present embodiment can be used for optical applications, which is particularly preferable.
  • Such a resin film examples include polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, polyolefin films such as polyethylene film and polypropylene film, cellophane, diacetyl cellulose film, triacetyl cellulose film, acetyl cellulose butyrate film, Polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polycarbonate film, polymethylpentene film, polysulfone film, polyether ether ketone film, polyether sulfone film, poly Ether imide film, fluororesin film, poly Amide film, polyimide film, polyamideimide film, acrylic resin film, polyurethane resin film, norbornene polymer film, cyclic olefin polymer film, cyclic conjugated diene polymer film, vinyl alicyclic hydro
  • a resin film or a laminated film thereof may be mentioned.
  • a polyethylene terephthalate film, a polyethylene naphthalate film, a triacetyl cellulose film, a polyether sulfone film, a polyamide film, a polyamideimide film are particularly preferable. Etc. are preferred.
  • the said base material sheet 2 in order to improve adhesiveness with the layers (The hard-coat layer 3, the curl suppression layer mentioned later, an adhesive layer, etc.) provided in the surface, it is desired on one side or both sides as desired.
  • Surface treatment can be performed by a primer treatment, an oxidation method, an unevenness method, or the like.
  • the oxidation method include corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, ozone / ultraviolet treatment
  • the unevenness method include a sand blast method and a solvent treatment method.
  • These surface treatment methods are appropriately selected according to the type of the substrate sheet 2.
  • a resin film, particularly a polyethylene terephthalate film, on which an easy-adhesion layer is formed by primer treatment is preferably used.
  • the thickness of the substrate sheet 2 is usually preferably about 50 to 300 ⁇ m.
  • the hard coat laminate 1 may be curled due to curing shrinkage of the hard coat layer 3.
  • the thickness of the base sheet 2 is preferably 50 ⁇ m or more, particularly preferably 75 ⁇ m or more, and more preferably 100 ⁇ m or more. It is preferable that Moreover, the effect that the surface hardness of the hard-coat laminated body 1 improves is also acquired by thickening the thickness of the base material sheet 2 in this way.
  • the thickness of the base sheet 2 is too thick, the bending resistance of the hard coat laminate 1 is lowered, and handling as a winding body may be difficult.
  • 300 ⁇ m or less more preferably 250 ⁇ m or less, particularly preferably 215 ⁇ m or less, and further preferably 200 ⁇ m or less.
  • the hard coat layer 3 of the hard coat laminate 1 according to this embodiment is laminated on one main surface side (upper side in FIG. 1) of the base sheet 2 and is higher than the hard coat laminate 1. Gives surface hardness.
  • the hard coat layer 3 of the hard coat laminate 1 cures a composition containing an ultraviolet curable component and a photopolymerization initiator (hereinafter also referred to as “hard coat layer composition”).
  • a composition containing an ultraviolet curable component and a photopolymerization initiator (hereinafter also referred to as “hard coat layer composition”).
  • it is made of a material.
  • the composition layer side with respect to the laminated body of the layer of the composition for hard-coat layers containing a ultraviolet curable component and a photoinitiator (henceforth "composition layer") and the base material sheet 2.
  • the photopolymerization initiator is consumed on the side close to the light source in the composition layer, and the photopolymerization initiator on the opposite side of the base sheet 2 in the hard coat layer 3 where the composition layer is cured.
  • the remaining amount is reduced, the consumption of the photopolymerization initiator is small on the side far from the light source in the composition layer, and the residual amount of the photopolymerization initiator on the base sheet 2 side in the hard coat layer 3 where the composition layer is cured. Will increase. Since the refractive index of the photopolymerization initiator is generally higher than the refractive index of the ultraviolet curable component, the refractive index is low on the side close to the light source of the hard coat layer 3, and the refractive index is high on the side far from the light source. . Thus, the refractive index of the hard coat layer 3 can be inclined in the thickness direction by curing the hard coat layer composition with ultraviolet rays.
  • the ultraviolet curable component is one that can be cured by irradiation with ultraviolet rays to exhibit a desired hardness and achieve the above-described gradient refractive index in relation to the photopolymerization initiator. If it does not specifically limit.
  • the ultraviolet curable component examples include a polyfunctional (meth) acrylate monomer, a (meth) acrylate prepolymer, and an ultraviolet curable polymer.
  • the polyfunctional (meth) acrylate monomer and the (meth) acrylate prepolymer may be used alone or in combination.
  • (meth) acrylate means both acrylate and methacrylate. The same applies to other similar terms.
  • multifunctional (meth) acrylate monomers examples include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and polyethylene glycol diene.
  • examples of the (meth) acrylate-based prepolymer include polyester acrylate-based, epoxy acrylate-based, urethane acrylate-based, polyol acrylate-based prepolymers, and the like.
  • polyester acrylate-based prepolymer examples include esterification of a hydroxyl group of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol with (meth) acrylic acid, It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding alkylene oxide to carboxylic acid with (meth) acrylic acid.
  • the epoxy acrylate prepolymer can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin and esterifying it.
  • the urethane acrylate prepolymer can be obtained, for example, by esterifying a polyurethane oligomer obtained by a reaction of polyether polyol or polyester polyol and polyisocyanate with (meth) acrylic acid.
  • the polyol acrylate prepolymer can be obtained, for example, by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid.
  • the above prepolymers may be used alone or in combination of two or more.
  • the ultraviolet curable polymer for example, a (meth) acrylic acid ester copolymer having an ultraviolet curable group in the side chain (hereinafter referred to as “ultraviolet curable (meth) acrylic acid ester copolymer (A)”).
  • the ultraviolet curable (meth) acrylic acid ester copolymer (A) includes an acrylic copolymer (a1) having a functional group-containing monomer unit, and an unsaturated group-containing compound having a substituent bonded to the functional group ( Those obtained by reacting with a2) are preferred.
  • the acrylic copolymer (a1) contains a structural unit derived from a functional group-containing monomer and a structural unit derived from a (meth) acrylate monomer or a derivative thereof.
  • the functional group-containing monomer contained in the acrylic copolymer (a1) as a structural unit is a molecule containing a polymerizable double bond and a functional group such as a hydroxyl group, a carboxyl group, an amino group, a substituted amino group, or an epoxy group.
  • the monomer contained therein preferably a hydroxyl group-containing unsaturated compound or a carboxyl group-containing unsaturated compound.
  • Such functional group-containing monomers include hydroxyl group-containing compounds such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, and 4-hydroxybutyl acrylate.
  • Examples include carboxyl group-containing compounds such as acrylate, acrylic acid, methacrylic acid, and itaconic acid, and these are used alone or in combination of two or more.
  • Examples of the (meth) acrylic acid ester monomer contained in the acrylic copolymer (a1) as a structural unit include cycloalkyl (meth) acrylate, benzyl (meth) acrylate, and an alkyl group having 1 to 18 carbon atoms (meta ) Acrylic acid alkyl esters are used. Among these, particularly preferred are (meth) acrylic acid alkyl esters having an alkyl group having 1 to 18 carbon atoms, such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate. 2-ethylhexyl (meth) acrylate or the like is used.
  • the acrylic copolymer (a1) contains the structural unit derived from the functional group-containing monomer in an amount of usually 3 to 100% by mass, preferably 5 to 40% by mass, particularly preferably 10 to 30% by mass, A structural unit derived from a (meth) acrylic acid ester monomer or a derivative thereof is usually contained in a proportion of 0 to 97% by mass, preferably 60 to 95% by mass, particularly preferably 70 to 90% by mass.
  • the acrylic copolymer (a1) can be obtained by copolymerizing a functional group-containing monomer as described above with a (meth) acrylic acid ester monomer or a derivative thereof in a conventional manner.
  • Vinyl formate, vinyl acetate, styrene and the like may be copolymerized in a small amount (for example, 10% by mass or less, preferably 5% by mass or less).
  • the substituent of the unsaturated group-containing compound (a2) can be appropriately selected according to the type of functional group of the functional group-containing monomer unit of the acrylic copolymer (a1).
  • the substituent is preferably an isocyanate group or an epoxy group.
  • the functional group is a carboxyl group
  • the substituent is an aziridinyl group, an epoxy group or an oxazoline group.
  • the functional group is an epoxy group
  • the substituent is preferably an amino group, a carboxyl group or an aziridinyl group.
  • One such substituent is included in each molecule of the unsaturated group-containing compound (a2).
  • the unsaturated group-containing compound (a2) contains 1 to 5, preferably 1 to 2, UV curable unsaturated groups (carbon-carbon double bonds) per molecule.
  • Specific examples of such unsaturated group-containing compound (a2) include, for example, acryloyloxyethyl isocyanate, methacryloyloxyethyl isocyanate, meta-isopropenyl- ⁇ , ⁇ -dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate;
  • an acryloyl monoisocyanate compound obtained by reacting a polyisocyanate compound with hydroxyethyl (meth) acrylate; an acryloyl monoisocyanate obtained by reacting a diisocyanate compound or polyisocyanate compound with a polyol compound and hydroxyethyl (meth) acrylate Compound; Glycidyl (meth) acrylate; (Meth) acrylic acid, 2- (1-azi
  • the unsaturated group-containing compound (a2) is usually 20 to 100 equivalents, preferably 40 to 100 equivalents, particularly preferably 60 to 100 equivalents per 100 equivalents of the functional group-containing monomer of the acrylic copolymer (a1). Used in
  • the ultraviolet curable (meth) acrylic acid ester copolymer (A) is obtained by reacting an acrylic copolymer (a1) and an unsaturated group-containing compound (a2) in an organic solvent in a conventional manner. can get.
  • the weight average molecular weight (Mw) of the ultraviolet curable (meth) acrylic acid ester copolymer (A) is preferably 10,000 to 100,000, particularly preferably 20,000 to 80,000. Further, it is preferably 30,000 to 60,000.
  • the weight average molecular weight (Mw) in this specification is the value of polystyrene conversion measured by the gel permeation chromatography (GPC) method.
  • the ultraviolet curable component constituting the hard coat layer 3 of the present embodiment preferably has a glass transition point after curing of 130 ° C. or higher, more preferably 150 ° C. or higher, and no glass transition point is observed. It is particularly preferred that In the manufacture of a touch panel or the like, a process in which the hard coat laminate 1 is heated may be included. In this case, thermal shrinkage of the hard coat laminate 1 becomes a problem. By using the curable component, the hard coat layer 3 becomes excellent in heat resistance, and excellent heat resistance can be imparted to the hard coat laminate 1.
  • the hard coat layer 3 having an inclined refractive index can be easily formed without requiring particularly precise control with respect to the conditions for forming the hard coat layer 3.
  • the photopolymerization initiator is not particularly limited as long as it functions as a photopolymerization initiator of the ultraviolet curable component to be used and can achieve the above-described gradient refractive index. It is preferable to use a phosphorus photopolymerization initiator. According to the phosphorous photopolymerization initiator, a refractive index difference in the hard coat layer 3 is likely to occur. That is, the difference between the refractive index on the base sheet 2 side of the hard coat layer 3 and the refractive index on the side opposite to the base sheet 2 side of the hard coat layer 3 can be 0.005 or more.
  • the phosphorus photopolymerization initiator is a compound containing phosphorus in the molecule, and generates a radical having a polymerization initiating ability when exposed to ultraviolet rays.
  • an acylphosphine oxide compound is preferable, and a compound having a CO—PO bond in the molecule is more preferable.
  • the molecular weight of the phosphorus photopolymerization initiator is preferably 100 to 2000, particularly preferably 200 to 1000.
  • a compound represented by the following general formula (I) is particularly preferably used.
  • R 1 is an aromatic group which may have a substituent, and is preferably dimethylphenyl, trimethylphenyl, trimethoxyphenyl, dimethoxyphenyl, phenyl or the like.
  • R 2 and R 3 are each independently a phenyl group, alkyl group, alkoxy group or aromatic acyl group which may have a substituent.
  • Preferred examples of the phenyl group which may have a substituent include dimethylphenyl, trimethylphenyl, trimethoxyphenyl, dimethoxyphenyl and phenyl, and particularly preferred is a phenyl group.
  • the alkyl group which may have a substituent is preferably 2-methylpropyl, 2,4,6-trimethylpentyl or the like, particularly preferably a 2,4,6-trimethylpentyl group. It is done.
  • the alkoxy group which may have a substituent an ethoxy group is particularly preferable.
  • the aromatic acyl group which may have a substituent is preferably an R 1 CO— group (R 1 is the same as above).
  • ⁇ Diphenyl (2,4,6-trimethoxybenzoyl) phosphine oxide ⁇ Diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide .Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide .Bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide Etc.
  • These phosphorus photopolymerization initiators may be used alone or in combination of two or more.
  • the content of the phosphorus-based photopolymerization initiator in the hard coat layer composition is preferably 0.01 to 10 parts by mass, particularly 0.05 to 5 parts by mass with respect to 100 parts by mass of the ultraviolet curable component. Part, and more preferably 0.1 to 3 parts by weight.
  • the hard coat layer composition may contain another photopolymerization initiator in addition to the phosphorous photopolymerization initiator.
  • photopolymerization initiators include benzoin compounds, acetophenone compounds, titanocene compounds, thioxanthone compounds, peroxide compounds, and the like.
  • 1-hydroxycyclohexyl phenyl ketone 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, benzoin, benzoin
  • benzoin benzoin
  • examples include methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyldiphenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, dibenzyl, diacetyl, ⁇ -chloranthraquinone, and the like.
  • the content of the other photopolymerization initiator in the hard coat layer composition is an amount that functions as a photopolymerization initiator of the ultraviolet curable component to be used without inhibiting the action of the phosphorus photopolymerization initiator. If there is, it will not be specifically limited. Usually, the amount is preferably 0.001 to 2 parts by mass, particularly preferably 0.01 to 1.5 parts by mass with respect to 100 parts by mass of the ultraviolet curable component.
  • the hard coat layer composition constituting the hard coat layer 3 of the present embodiment preferably contains a fluorine additive and / or a silicone additive. . Reflection of light at the hard coat layer 3 is often more problematic at the interface with the air than at the interface with the substrate sheet 2. By containing a silicone-based additive, the refractive index of the hard coat layer 3 to be formed becomes lower as a whole, and the refractive index on the surface side of the hard coat layer 3 becomes closer to the refractive index of air, so that Reflection of light on the surface of the coat layer 3 is effectively suppressed.
  • fluorine-based additive a copolymer of polyoxyalkylene and fluorocarbon can be preferably used.
  • fluorine-based additives include the MEGAFAC series manufactured by DIC Corporation, the FC series manufactured by Sumitomo 3M Corporation, and the footage series manufactured by Neos Corporation.
  • silicone-based additive a copolymer of polyoxyalkylene and polydimethylsiloxane can be preferably used.
  • Commercially available silicone additives include FZ-2118, FZ-77, FZ-2161 (trade names; manufactured by Toray Dow Corning Co., Ltd.), KP321, KP323, KP324, KP326, KP340, KP341 (trade names; Manufactured by Shin-Etsu Chemical Co., Ltd.), etc.
  • the content of the fluorine-based additive and the silicone-based additive in the hard coat layer composition is preferably 0.01 to 10% by mass, particularly The amount is preferably 0.05 to 5% by mass, more preferably 0.1 to 3% by mass.
  • composition for hard-coat layers which comprises the hard-coat layer 3 of this embodiment contains an inorganic filler.
  • inorganic filler By containing the inorganic filler, high surface hardness is imparted to the hard coat layer 3 of the present embodiment.
  • Preferred inorganic fillers include powders such as silica, alumina, boehmite, talc, calcium carbonate, titanium oxide, iron oxide, silicon carbide, boron nitride, zirconium oxide, beads spheroidized from these, single crystal fibers, glass fibers, and the like. These may be used alone or in combination of two or more. Among these, silica, alumina, boehmite, titanium oxide, zirconium oxide and the like are preferable, and silica is particularly preferable from the viewpoints of hardness and light transmittance.
  • the inorganic filler is preferably surface-modified.
  • An example of such a particularly preferred inorganic filler is reactive silica.
  • “reactive silica” refers to silica fine particles whose surface is modified with an organic compound having an ultraviolet curable unsaturated group.
  • the silica fine particles (reactive silica) surface-modified with an organic compound having an ultraviolet curable unsaturated group are usually silica fine particles having an average particle size of about 0.5 to 500 nm, preferably an average particle size of 1 to 200 nm. It can be obtained by reacting a surface silanol group with an organic compound containing an ultraviolet curable unsaturated group having a (meth) acryloyl group which is a functional group capable of reacting with the silanol group.
  • Examples of the organic compound containing an ultraviolet curable unsaturated group having a functional group capable of reacting with a silanol group include, for example, the general formula (II) (Wherein R 1 is a hydrogen atom or a methyl group, R 2 is a halogen atom, It is group shown by these. ) A compound represented by the formula is preferably used.
  • Examples of such compounds include (meth) acrylic acid, (meth) acrylic acid chloride, (meth) acryloyloxyethyl isocyanate, glycidyl (meth) acrylate, 2,3-iminopropyl (meth) acrylate, (meth ) (Meth) acrylic acid derivatives such as 2-hydroxyethyl acrylate and acryloyloxypropyltrimethoxysilane can be used. These (meth) acrylic acid derivatives may be used individually by 1 type, and may be used in combination of 2 or more type.
  • Such reactive silica sica fine particles surface-modified with an organic compound having an ultraviolet curable unsaturated group
  • the aforementioned polyfunctional (meth) acrylate monomer and / or (meth) acrylate prepolymer As the organic-inorganic hybrid material contained, for example, trade names “OPSTAR Z7530”, “OPSTAR Z7524”, “OPSTAR TU4086”, “OPSTAR Z7537” (manufactured by JSR Corporation) and the like can be used.
  • the average particle size of the inorganic filler used in the present embodiment is preferably 1 to 200 nm, particularly preferably 10 to 200 nm, and further preferably 20 to 200 nm.
  • the hard coat layer 3 obtained by curing the composition for hard coat layer has higher surface hardness.
  • the average particle size of the inorganic filler is 200 nm or less, light scattering hardly occurs in the obtained hard coat layer 3 and the transparency of the hard coat layer 3 is increased. Therefore, by using such a hard coat layer 3 together with the transparent resin film described above as the base sheet 2, the hard coat laminate 1 according to the present embodiment becomes highly transparent, particularly for optical applications. It can be used suitably.
  • the average particle diameter of an inorganic filler shall be measured by the zeta potential measuring method.
  • the content of the inorganic filler in the hard coat layer 3 of the present embodiment is preferably 0 to 85% by volume (85% by volume or less) with respect to the hard coat layer 3, and more preferably 30 to 85% by volume. It is particularly preferably 40 to 80% by volume, and more preferably 45 to 70% by volume.
  • the surface hardness provided to the hard-coat layer 3 becomes higher because the content is 30 volume% or more.
  • layer formation using the composition for hard-coat layers becomes easy because content of an inorganic filler is 85 volume% or less.
  • content of the inorganic filler in this specification shall be calculated
  • the organic component is combusted according to JIS 7250-1, the mass% of the inorganic filler is determined from the ash content obtained, and the true density of the inorganic filler is determined according to JIS Z8807. Thereafter, the density of the heat-resistant layer 3 is obtained from JIS Z8807, and the volume percentage of the inorganic filler is obtained from the measured values of mass% of the inorganic filler, the true density of the inorganic filler, and the density of the heat-resistant layer 3.
  • the hard coat layer composition constituting the hard coat layer 3 of the present embodiment may contain various additives in addition to the components described above.
  • the various additives include ultraviolet absorbers, antioxidants, light stabilizers, antistatic agents, silane coupling agents, anti-aging agents, thermal polymerization inhibitors, colorants, surfactants, storage stabilizers, plasticizers.
  • the pencil hardness of the hard coat layer 3 measured according to JIS K5600-5-4 is preferably 4H or more, particularly preferably 5H or more, and 6H More preferably, it is the above.
  • the hard coat laminate 1 satisfying the conditions required by the hard coat layer 3 has a high surface hardness and excellent scratch resistance. According to the hard coat layer 3 having a thickness of 25 ⁇ m or more, the pencil hardness can be achieved.
  • the hard coat laminated body 1 which concerns on this embodiment can be preferably manufactured with the following method.
  • a composition for a hard coat layer containing an ultraviolet curable component and a photopolymerization initiator is used.
  • composition layer made of the composition for hard coat layer is formed on one main surface of the substrate sheet 2.
  • the composition for hard coat layer may be directly applied to one main surface of the substrate sheet 2 to form a composition layer, or after the composition for hard coat layer is applied to the cover sheet, A composition layer with a cover sheet may be bonded to one main surface of the base sheet 2.
  • cover sheet those exemplified above as the resin film can be used.
  • surface or both surfaces of these resin films was peel-processed with the peeling agent can also be used.
  • the composition layer is formed by preparing a coating agent containing a composition for a hard coat layer and, if desired, further a solvent, applying this to the base sheet 2 or the cover sheet, and drying.
  • the coating agent may be applied by a conventional method, for example, a bar coating method, a knife coating method, a Mayer bar method, a roll coating method, a blade coating method, a die coating method, or a gravure coating method. Drying can be performed, for example, by heating at 80 to 150 ° C. for about 30 seconds to 5 minutes.
  • the composition layer is cured to form a hard coat layer 3 by irradiating ultraviolet rays from the side opposite to the base sheet 2.
  • the cover sheet is left as it is, and when the cover sheet is not attached to the composition layer. It is preferable that a cover sheet is newly laminated on the composition layer, or the base material sheet 2 and the laminate of the composition layer are placed in an atmosphere having a low oxygen concentration, preferably in a nitrogen atmosphere.
  • a cover sheet In making the composition layer shielded from oxygen, it is preferable to use a cover sheet from the viewpoint of ease of production, cost, and the like. That is, it is preferable to produce a laminate in which the composition layer is laminated on one main surface of the substrate sheet 2 and the cover sheet is laminated on the opposite side of the composition layer from the substrate sheet 2 side. It is preferable to apply the composition for hard coat layer to the cover sheet, and bond the composition layer with the cover sheet to one main surface of the base sheet 2. In this case, ultraviolet rays are irradiated from the cover sheet side.
  • the composition layer When irradiated with ultraviolet rays as described above, the composition layer is close to the light source without being inhibited by oxygen (the side opposite to the base sheet 2 in the hard coat layer 3 (the surface side of the hard coat layer 3)). ) Consumes a large amount of photopolymerization initiator, reduces the residual amount of photopolymerization initiator and lowers the refractive index, and on the side far from the light source in the composition layer (base sheet 2 side in the hard coat layer 3) The consumption amount of the photopolymerization initiator is small, the residual amount of the photopolymerization initiator is increased, the refractive index is increased, and the refractive index of the obtained hard coat layer 3 is inclined in the thickness direction.
  • UV irradiation, high-pressure mercury lamp, a fusion H lamp can be carried out by a xenon lamp or the like, the dose of ultraviolet rays, the illuminance 50 ⁇ 1000mW / cm 2, light amount 50 ⁇ 1000mJ / cm 2 is preferably about.
  • the use of the hard coat laminate 1 according to this embodiment can be preferably used for applications that require both surface hardness and light antireflection properties.
  • the hard coat laminated body 1 which concerns on this embodiment can be preferably used as a surface layer of various displays, such as a liquid crystal display (LCD), a plasma display (PDP), an organic electroluminescent display (OELD), and a touch panel, for example.
  • LCD liquid crystal display
  • PDP plasma display
  • OELD organic electroluminescent display
  • touch panel for example.
  • the curl suppressing layer 4 As the material constituting the curl suppressing layer 4, a material having a curing shrinkage comparable to that of the hard coat layer 3 is preferable.
  • the curl suppressing layer 4 is preferably made of a material obtained by curing a composition containing a curable component (hereinafter sometimes referred to as “curling suppressing layer composition”), and the hard coat layer 3 is inorganic. When it contains a filler, it is preferable that the composition for curl suppression layers also contains an inorganic filler.
  • thermosetting component As the curable component of the curl suppressing layer composition, other than those exemplified as the ultraviolet curable component of the hard coat layer composition, a thermosetting component can be used. However, from the viewpoint of simplifying the production process, it is preferable to use an ultraviolet curable component as the curable component, and from the viewpoint of curling suppression, the curability having the same degree of curing shrinkage as the hard coat layer 3 is used. It is preferred to use the components.
  • the inorganic filler used in the curl suppression layer composition those exemplified as the inorganic filler of the hard coat layer composition can be used, and the same as that used in the hard coat layer composition. preferable. Moreover, it is preferable that content of the inorganic filler in the composition for curl suppression layers is made into the same grade as the composition for hard-coat layers. As a result, the curing shrinkage of the curl suppressing layer 4 and the curing shrinkage of the hard coat layer 3 become approximately the same, and curling of the hard coat laminate 1A is more effectively suppressed.
  • the curl suppressing layer composition may contain a photopolymerization initiator, a fluorine-based additive and / or a silicone-based additive, other additives, and the like, as in the hard coat layer composition.
  • a photopolymerization initiator e.g., a fluorine-based additive and / or a silicone-based additive, other additives, and the like.
  • these components those exemplified for the hard coat layer composition described above can be used.
  • the ratio of the thickness of the curl suppressing layer 4 to the thickness of the hard coat layer 3 is preferably 0.2 to 2, particularly 0.2 to 1. Is more preferable, and 0.3 to 0.8 is more preferable.
  • the ratio of the thickness of the curl suppressing layer 4 to the thickness of the hard coat layer 3 is within the above range, curling of the hard coat laminate 1A according to the present embodiment is effectively suppressed.
  • the thickness of the curl suppressing layer 4 is preferably 4 to 100 ⁇ m, more preferably 5 to 100 ⁇ m, particularly preferably 20 to 50 ⁇ m, and further preferably 25 to 50 ⁇ m.
  • the thickness of the curl suppression layer 4 is in the above range, the ratio of the thickness of the curl suppression layer 4 to the thickness of the hard coat layer 3 easily satisfies the above-described conditions, and the hard coat laminate according to the present embodiment. Curling of 1A is more effectively suppressed.
  • the hard coat laminate 1A according to this embodiment can be manufactured basically in the same manner as the hard coat laminate 1 described above. However, the hard coat layer 3 and the curl suppression layer 4 may be cured simultaneously, or after the composition layer of the hard coat layer 3 (or the curl suppression layer 4) is formed and cured, the curl suppression layer 4 is cured. A composition layer (or hard coat layer 3) may be formed and cured.
  • a pressure-sensitive adhesive layer 5 is laminated on the other main surface side of the base sheet 2 in the hard coat laminate 1 (surface side opposite to the surface on which the hard coat layer 3 is laminated).
  • symbol of the hard-coat laminated body shown in FIG. 3 is described as "1B.”
  • a pressure-sensitive adhesive layer may be laminated on the opposite side of the curl suppression layer 4 in the hard coat laminate 1A from the base sheet 2 side.
  • the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer 5 is not particularly limited, and a known pressure-sensitive adhesive such as an acrylic pressure-sensitive adhesive, a rubber pressure-sensitive adhesive, or a silicone pressure-sensitive adhesive can be used.
  • the thickness of the pressure-sensitive adhesive layer 5 is not particularly limited, but is usually 5 to 100 ⁇ m, preferably 10 to 60 ⁇ m.
  • the hard coat laminate 1B according to this embodiment can be manufactured basically in the same manner as the hard coat laminate 1 described above. What is necessary is just to form the adhesive layer 5 by a conventional method.
  • a release sheet may be laminated on the exposed surface of the pressure-sensitive adhesive layer 5 (surface opposite to the base sheet 2 side).
  • another layer may be interposed between the base sheet 2 in the hard coat laminate 1, 1A, 1B and the hard coat layer 3, the curl suppressing layer 4 or the pressure-sensitive adhesive layer 5.
  • Example 1 Composition containing ultraviolet curable component and inorganic filler (manufactured by JSR, trade name “OPSTAR Z7530”, dipentaerythritol hexaacrylate as ultraviolet curable component, reactive silica as inorganic filler, content of inorganic filler: 49% by volume, photopolymerization initiator: 3% by mass, solid content concentration: 73% by mass, solvent: methyl ethyl ketone) 100 parts by mass (in terms of solid content; the same shall apply hereinafter) and diphenyl (2, 1,6 parts of 6,6-trimethoxybenzoyl) phosphine oxide (manufactured by BASF, trade name “Lucirin TPO”) was mixed with stirring to obtain a composition for a hard coat layer.
  • inorganic filler manufactured by JSR, trade name “OPSTAR Z7530”
  • dipentaerythritol hexaacrylate as ultraviolet curable component
  • reactive silica as inorganic filler
  • the composition for a hard coat layer is formed on a release surface of a release sheet (corresponding to a cover sheet; product name “PLR382020 *” manufactured by Lintec Corporation) in which one side of a polyethylene terephthalate (PET) film is release-treated with a silicone-based release agent.
  • PET polyethylene terephthalate
  • the composition for a hard coat layer is formed on a release surface of a release sheet (corresponding to a cover sheet; product name “PLR382020 *” manufactured by Lintec Corporation) in which one side of a polyethylene terephthalate (PET) film is release-treated with a silicone-based release agent.
  • PET polyethylene terephthalate
  • a PET film (trade name “COSMO SHINE PET50A-4100”, manufactured by Toyobo Co., Ltd., thickness: 50 ⁇ m) as a base sheet was bonded to the composition layer of the hard coat layer composition. . Then, ultraviolet rays are irradiated from the release sheet (cover sheet) side of the obtained laminate (illuminance: 300 mW / cm 2 , light amount: 1300 mJ / cm 2 ) to cure the composition layer of the hard coat layer composition. Thus, a hard coat layer (thickness: 25 ⁇ m) was formed. In this way, a laminate comprising a release sheet (cover sheet) / hard coat layer / base sheet, that is, a hard coat laminate in which the release sheet (cover sheet) was laminated on the outside of the hard coat layer was obtained. .
  • Example 2 The same as in Example 1 except that the thickness of the hard coat layer was changed to 50 ⁇ m and the base sheet was changed to a PET film (trade name “Cosmo Shine PET125A-4300”, thickness: 125 ⁇ m, manufactured by Toyobo Co., Ltd.). A hard coat laminate was produced.
  • Example 3 100 parts by mass of a mixture of urethane acrylate and polyfunctional acrylate, which are UV curable components (made by Arakawa Chemical Industry Co., Ltd., trade name “Beam Set 575CB”, containing photopolymerization initiator), and photoreactive fluorine / silicone additive 5 parts by mass (made by Neos, trade name “Futgent 601AD”) and diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide (trade name “Darocur TPO” made by BASF) which is a phosphoric photopolymerization initiator ) 1 part by mass was mixed with stirring to obtain a composition for a hard coat layer.
  • UV curable components made by Arakawa Chemical Industry Co., Ltd., trade name “Beam Set 575CB”, containing photopolymerization initiator
  • photoreactive fluorine / silicone additive 5 parts by mass
  • Neos trade name “Futgent 601AD”
  • the hard coat layer composition was used for forming the hard coat layer, the thickness of the hard coat layer was changed to 30 ⁇ m, and the base sheet was a PET film (trade name “COSMO SHINE PET188A-4300” manufactured by Toyobo Co., Ltd.) , Thickness: 188 ⁇ m), a hard coat laminate was produced in the same manner as in Example 1.
  • Example 1 A hard coat laminate was produced in the same manner as in Example 3 except that the thickness of the hard coat layer was changed to 10 ⁇ m.
  • the refractive index of the interface with the base sheet of the hard coat layer is measured, and the refractive index on the surface side of the hard coat layer is The refractive index at the interface with air was measured.
  • the refractive index on the base sheet side of the hard coat layer is 0.005 or more larger than the refractive index on the surface side of the hard coat layer, Therefore, the total light transmittance was large, no interference unevenness was generated, and the surface hardness was high.
  • the hard coat laminate of the present invention is suitably used for a surface protective sheet of various displays such as a liquid crystal display (LCD), a plasma display (PDP), an organic EL display (OELD), and a touch panel.
  • LCD liquid crystal display
  • PDP plasma display
  • OELD organic EL display
  • touch panel a touch panel

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Laminated Bodies (AREA)
  • Surface Treatment Of Optical Elements (AREA)

Abstract

　La présente invention concerne un article stratifié avec revêtement dur (1) doté d'une feuille de substrat (2) et d'une couche de revêtement dur (3) stratifiée sur au moins un des côtés de surface principale de la feuille de substrat (2), l'épaisseur de la couche de revêtement dur (3) étant comprise entre 25 et 80 µm, et l'indice de réfraction de la couche de revêtement dur (3) du côté de la feuille de substrat (2) étant supérieur de 0,005 ou plus par rapport à l'indice de réfraction de la couche de revêtement dur (3) du côté opposé à la feuille de substrat (2). La couche de revêtement dur (3) de cet article stratifié avec revêtement dur (1) offre une dureté de surface élevée et permet de supprimer les reflets de lumière en utilisant une couche simple.
PCT/JP2014/068809 2013-08-27 2014-07-15 Article stratifié avec revêtement dur et son procédé de fabrication Ceased WO2015029623A1 (fr)

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