WO2020175337A1 - Corps stratifié, article ayant un corps stratifié, et dispositif d'affichage d'image - Google Patents

Corps stratifié, article ayant un corps stratifié, et dispositif d'affichage d'image Download PDF

Info

Publication number
WO2020175337A1
WO2020175337A1 PCT/JP2020/006912 JP2020006912W WO2020175337A1 WO 2020175337 A1 WO2020175337 A1 WO 2020175337A1 JP 2020006912 W JP2020006912 W JP 2020006912W WO 2020175337 A1 WO2020175337 A1 WO 2020175337A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
polymer
general formula
hard coat
coat layer
Prior art date
Application number
PCT/JP2020/006912
Other languages
English (en)
Japanese (ja)
Inventor
暢之 芥川
顕夫 田村
北村　哲
裕三 永田
Original Assignee
富士フイルム株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Priority to JP2021502154A priority Critical patent/JP7064650B2/ja
Priority to KR1020217019637A priority patent/KR102602546B1/ko
Publication of WO2020175337A1 publication Critical patent/WO2020175337A1/fr
Priority to JP2022071039A priority patent/JP2022115881A/ja

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino carboxylic acids or of polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • the present invention relates to a laminate, an article including the laminate, and an image display device.
  • CRT cathode ray tube
  • PDP plasma display
  • Image display devices such as, electroluminescent displays (ELDs), fluorescent display (VFDs), field emission displays (FEDs), and liquid crystal displays (LCDs) are designed to prevent scratches on the display surface. It is preferable to provide a laminate having a hard coat layer (hard coat film) on the substrate.
  • ELDs electroluminescent displays
  • VFDs fluorescent display
  • FEDs field emission displays
  • LCDs liquid crystal displays
  • Patent Document 1 describes a hard coat film having a hard coat layer made of a cured product of a curable composition containing a cationic curable silicone resin and a leveling agent on a substrate. There is.
  • Patent Document 1 Japanese Patent Laid-Open No. 2 0 1 8-8 3 9 15
  • An object of the present invention is to provide a laminate having excellent scratch resistance and resistance to repeated bending, and suppressing whitening, an article including the laminate, and an image display device.
  • the hard coat layer-forming composition comprising a polymer _ (3) having a group containing a fluorine atom, a cationically polymerizable group, and a radically polymerizable group is contained, and the scratch resistant layer is a radically polymerizable group.
  • the scratch resistant layer is a radically polymerizable group.
  • the polymer _ (3) has a structural unit represented by the following general formula (3_1), a structural unit represented by the following general formula (3_2), and a structural unit represented by the following general formula (3_3).
  • 1_ 2 represents a single bond or a divalent linking group, 0 2 denotes the Kachio down polymerizable group.
  • 1_ 3 represents a single bond or a divalent linking group
  • 0 3 represents the radical Le polymerizable group
  • the composition for forming a hard coat layer contains the polymer (3) in an amount of 0.001 to 5% by mass based on the total solid content of the composition for forming a hard coat layer, ⁇ 1> to ⁇
  • An image display device comprising the laminate according to any one of ⁇ 1> to ⁇ 9> as a surface protection film.
  • the present invention it is possible to provide a laminate having excellent scratch resistance and repeated bending resistance, and suppressing whitening, an article including the laminate, and an image display device.
  • the laminate of the present invention is a laminate of the present invention.
  • the bonded _ DoCoMo _ Bokuso is,
  • the hard coat layer-forming composition comprising a polymer _ (3) having a group containing a fluorine atom, a cationically polymerizable group, and a radically polymerizable group is contained, and the scratch resistant layer is a radically polymerizable group.
  • the scratch resistant layer is a radically polymerizable group.
  • Polyorganosilsesquioxane having a cationically polymerizable group (3 1) is a material capable of imparting hardness and flex resistance to the hard coat layer, but polyorganosilsesquioxane having a cationically polymerizable group (3 1)
  • the hard coating layer is Since it is a cationic polymerization system and the scratch-resistant layer is a radical polymerization system, the polymerization systems of both layers are different, and it is considered that the adhesion between the layers was weak and the improvement in scratch resistance was low.
  • the polymer (3) by adding a polymer (3) having a group containing a fluorine atom, a cationically polymerizable group, and a radically polymerizable group to the composition for forming a hard coat layer, the polymer (3) can be It is believed that the film functions as an interlayer adhesive, strengthening the adhesiveness between the layers and providing excellent scratch resistance.
  • the polymer (3) has a group containing a fluorine atom, ⁇ 2020/175 337 6 ⁇ (: 171-1? 2020/006912
  • the polymer (3) When the composition for forming a hard coat layer is applied, the polymer (3) is unevenly distributed on the surface of the hard coat layer (surface on the air interface side), and the layers can be adhered efficiently. Further, the action of the group containing a fluorine atom lowers the surface tension of the coating liquid, and suppresses Marangoni convection, wind drying unevenness, and the like, so that it is considered that whitening due to surface scattering can be suppressed.
  • the polymer (3) Since the polymer (3) has a cationically polymerizable group, it can be bonded to the polyorganosilsesquioxane (3 1) having a cationically polymerizable group, which is a material of the hard coat layer, by a polymerization reaction.
  • the polymer (3) since the polymer (3) has a radically polymerizable group, it can be bonded to the radically polymerizable compound ( ⁇ 1) which is a material of the scratch resistant layer by a polymerization reaction.
  • the polymer (3) can be bonded to both the material of the hard coat layer and the material of the scratch resistant layer, the adhesion between the layers can be enhanced, and thus the scratch resistance can be improved. it is conceivable that.
  • the laminate of the present invention includes a base material.
  • the substrate preferably has a transmittance in the visible light region of 70% or more, more preferably 80% or more, and further preferably 90% or more.
  • the substrate preferably comprises a polymer.
  • the polymer a polymer having excellent optical transparency, mechanical strength, thermal stability and the like is preferable.
  • polystyrene-based polymers examples include polycarbonate-based polymers, polyethylene terephthalate (Mitsuingo), polyethylene naphthalate (Mitsumi 1 ⁇ 1) and other polyester-based polymers, polystyrene, acrylonitrile-styrene copolymers (83 resin), and the like.
  • polyolefins such as polyethylene and polypropylene, norbornene-based resins, polyolefin-based polymers such as ethylene-propylene copolymers, polymethylmethacrylate, etc.
  • (meth) acrylic polymer such as rate, (meth) acrylic polymer, vinyl chloride polymer, nylon, amide polymer such as aromatic polyamide, imide polymer, sulfone polymer, Polyether sulfone-based polymer, polyether ether ketone-based polymer, polyphenylene sulfide-based polymer, vinylidene chloride-based polymer, vinyl alcohol-based polymer, vinyl butyral-based polymer, aryl-based polymer, polyoxymethylene-based polymer, epoxy
  • the polymer also include cellulosic polymers, cellulosic polymers typified by triacetyl cellulose, copolymers of the above polymers, and polymers obtained by mixing the above polymers.
  • amide-based polymers and imide-based polymers such as aromatic polyamides are
  • I 3 Japanese Industrial Standards 8 1 15 (2 0 0 1)
  • the number of breaks and bends measured with an IV! I Ding tester is large, and the hardness is relatively high, so it is preferably used as a substrate.
  • an aromatic polyamide as shown in Example 1 of Japanese Patent No. 5 6 9 9 4 5 4, Japanese Patent Publication No. 2 0 1 5 — 5 0 8 3 4 5 and Japanese Patent Publication No. 2 0 1 6-5
  • the polyimides described in JP-A Nos. 2 1 2 1 6 and 0 2 0 1 7/0 1 4 2 8 7 can be preferably used as a base material.
  • the amide-based polymer aromatic polyamide (aramid-based polymer) is preferable.
  • the substrate preferably contains at least one polymer selected from imide-based polymers and aramid-based polymers.
  • the base material can also be formed as a cured layer of an acrylic, urethane, acrylic urethane, epoxy, silicone or other UV curable or thermosetting resin.
  • the base material may contain a material that further softens the above-mentioned polymer.
  • the softening material refers to a compound that improves the number of times of bending at break.
  • a rubber elastic body, a brittleness improving agent, a plasticizer, a sliding ring polymer, etc. can be used as the softening material.
  • the softening material described in paragraph numbers [0 0 5 1] to [0 1 1 4] can be preferably used.
  • the softening material may be mixed alone with the polymer, or a plurality of softening materials may be appropriately used in combination, and the softening material alone or in plural without mixing with the polymer. It may be used together as a base material.
  • the amount of these softening materials to be mixed is not particularly limited, and a polymer having a sufficient number of times of breaking and folding may be used alone as a base material of the film, or a softening material may be mixed. Good, all of them may be made of flexible material (100%) and have a sufficient number of breaks and bends.
  • additives for example, an ultraviolet absorber, a matting agent, an antioxidant, a peeling accelerator, a retardation (optical anisotropy) regulator, etc.
  • They may be solid or oily. That is, its melting point or boiling point is not particularly limited.
  • the time of adding the additive may be added at any time in the step of producing the base material, or the step of adding and preparing the additive in the material preparation step may be added.
  • the addition amount of each material is not particularly limited as long as the function is exhibited.
  • the additives described in the step numbers [0 1 1 7] to [0 1 2 2] in JP-A No. 2 016 -1 6 7 0 4 3 are preferably used. it can.
  • One kind of the above additives may be used alone, or two or more kinds may be used in combination.
  • ultraviolet absorbers examples include benzotriazole compounds, triazine compounds, and benzoxazine compounds.
  • the benzotriazole compound is a compound having a benzotriazole ring, and specific examples thereof include various compounds described in paragraph 0 0 3 3 of JP-A No. 20 1 3 — 1 1 1 8 3 5
  • a benzotriazole type ultraviolet absorber can be mentioned. All ⁇ 2020/175 337 9 ⁇ (:171? 2020 /006912
  • the lyazine compound is a compound having a triazine ring, and specific examples thereof include various triazine-based UV absorbers described in paragraph 0033 of JP-A-2013-1111835.
  • benzoxazine compound for example, those described in JP-A-2014-209162, paragraph 0031 can be used.
  • the content of the ultraviolet absorber in the base material is, for example, about 0.1 to 10 parts by mass with respect to 100 parts by mass of the polymer contained in the base material, but is not particularly limited. Further, with respect to the ultraviolet absorber, reference can be made to JP-A No. 2013-111835, paragraph 0032.
  • an ultraviolet absorber having high heat resistance and low volatility is preferable. Examples of such UV absorbers include 11 3 0 [3 ⁇ 4mi 101 (manufactured by FUJIFILM Fine Chemicals Co., Ltd.), 1-111 111-360, 1-111 1
  • the base material has a small difference in refractive index between the flexible material and various additives used for the base material and the polymer.
  • the base material a base material containing an imide polymer can be preferably used.
  • the imide-based polymer means a polymer containing at least one repeating structural unit represented by the following formulas: (3), (3') and (3).
  • the repeating structural unit represented by the formula () is the main structural unit of the imido polymer.
  • the repeating structural unit represented by the formula () is preferably 40 mol% or more, more preferably 50 mol% or more, further preferably 50 mol% or more, based on all repeating structural units of the imide polymer 1. It is 70 mol% or more, particularly preferably 90 mol% or more, and most preferably 98 mol% or more.
  • ⁇ 3 represents a tetravalent organic group
  • 3 represents a divalent organic group.
  • Each of 0 4 and 4 in the formula (10) represents a divalent organic group.
  • the organic group of the tetravalent organic group represented by ⁇ (hereinafter, may be referred to as the organic group of ⁇ ) is an acyclic aliphatic group or a cyclic aliphatic group. And a group selected from the group consisting of aromatic groups. From the viewpoint of transparency and flexibility of the base material containing the imide polymer, the organic group of ⁇ is preferably a tetravalent cycloaliphatic group or a tetravalent aromatic group.
  • the aromatic group includes a monocyclic aromatic group, a condensed polycyclic aromatic group, and a non-condensed polycyclic aromatic group having two or more aromatic rings, which are directly or linked to each other by a bonding group.
  • the organic group of ⁇ is a cycloaliphatic group, a cycloaliphatic group having a fluorine-containing substituent, or a monocyclic aromatic group having a fluorine-containing substituent.
  • the fluorine-based substituent means a group containing a fluorine atom.
  • the fluorine-based substituent is preferably a fluoro group (fluorine atom, _) and a perfluoroalkyl group, and more preferably a fluoro group and a trifluoromethyl group.
  • the organic group represented by: is, for example, a saturated or unsaturated cycloalkyl group, a saturated or unsaturated heterocycloalkyl group, an aryl group, a heteroaryl group, an arylalkyl group, an alkylaryl group, And a heteroalkylaryl group, and any two groups (may be the same) of these groups, which are directly or linked to each other by a bonding group.
  • the bonding group one hundred and one, alkylene group of from 1 to 1 0 carbon atoms, _ 3_Rei 2 -, _ ⁇ _ ⁇ one or _ ⁇ _ ⁇ _ ([3 ⁇ 4 is a methyl group, an ethyl group, and propyl group having a carbon Which represents an alkyl group of the formula 1 to 3 or a hydrogen atom).
  • the tetravalent organic group represented by ⁇ usually has 2 to 32 carbon atoms, preferably 4 to 15 carbon atoms, more preferably 5 to 10 carbon atoms, and further preferably 6 to 8 carbon atoms. Is.
  • the organic group of ⁇ is a cycloaliphatic group or an aromatic group, at least one of the carbon atoms constituting these groups may be replaced with a hetero atom. Examples of the hetero atom include O, 1 ⁇ ] or 3.
  • an acyclic aliphatic group, a cyclic aliphatic group and an aromatic group are included. Examples include groups selected from the group consisting of group groups.
  • the divalent organic group represented by is preferably selected from a divalent cycloaliphatic group and a divalent aromatic group.
  • the aromatic group includes a monocyclic aromatic group, a condensed polycyclic aromatic group, and a non-condensed polycyclic aromatic group having two or more aromatic rings, which are directly or linked to each other by a bonding group. Groups. From the viewpoints of transparency of the base material and suppression of coloring, it is preferable that a fluorine-based substituent is introduced into the organic group.
  • the eight organic groups include, for example, a saturated or unsaturated cycloalkyl group, a saturated or unsaturated heterocycloalkyl group, an aryl group, a heteroaryl group, an arylalkyl group, an alkylaryl group, A heteroalkylaryl group, and any two of these groups (which may be the same), which are linked to each other directly or by a linking group.
  • the hetero atom, ⁇ include 1 ⁇ 1 or 3, as the bonding group, one hundred and one from 1 to 1 0 alkylene group carbon number one 3_Rei 2 -, one hundred one or one hundred one ([Including an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, a propyl group or a hydrogen atom]).
  • the carbon number of the divalent organic group represented by 8 is usually 2 to 40, and preferably
  • 1 and 3 are one hundred and one, and 2 _ ⁇ _1 ⁇ 1 2 -, _ ⁇ (Rei_1 ⁇ 1 3) 2 - or _ 3_Rei 2 -.
  • One or more hydrogen atoms of these groups may be substituted with a fluorine-based substituent.
  • At least one hydrogen atom of hydrogen atoms constituting at least one of 8 and ⁇ is selected from the group consisting of a fluorine-based substituent, a hydroxyl group, a sulfone group, and an alkyl group having 1 to 10 carbon atoms. May be substituted with at least one functional group.
  • the organic group of and the organic group of is respectively a cycloaliphatic group or an aromatic group, it is preferable that at least one of and has a fluorine-based substituent, and both of and are fluorine-based. It is more preferable to have a substituent.
  • ⁇ 2 in the formula (3) is a trivalent organic group.
  • This organic group is a trivalent group ⁇ 2020/175 337 14 ⁇ (:171? 2020 /006912
  • Expression (3' It can be selected from the same groups as ⁇ in formula (I). Eight- three in formula (3') can be selected from the same groups as eight in formula (I).
  • ⁇ 4 is a divalent organic group.
  • This organic group can be selected from the same groups as the organic group of ⁇ in the formula (), except that it is a divalent group.
  • a group in which any two of the four bonds of the groups represented by formula (20) to formula (26) given as specific examples of You can Eight four in formula (I) can be selected from the same groups as eight in formula (I).
  • the imide-based polymer contained in the base material containing the imide-based polymer includes a diamine, a tetracarboxylic acid compound (an acid chloride compound, and a tetracarboxylic acid compound analog such as tetracarboxylic dianhydride Or a tricarboxylic acid compound (including an acid chloride compound and a tricarboxylic acid compound analog such as a tricarboxylic acid anhydride), may be a condensation polymer obtained by polycondensation. Further, a dicarboxylic acid compound (including an analog such as an acid chloride compound) may be polycondensed.
  • the repeating structural unit represented by the formula () or the formula (3') is usually derived from a diamine and a tetracarboxylic acid compound.
  • the repeating structural unit represented by the formula (3) is usually derived from a diamine and a tricarboxylic acid compound.
  • the repeating structural unit represented by the formula ( ⁇ ) is usually derived from diamines and dicarboxylic acid compounds.
  • tetracarboxylic acid compound examples include aromatic tetracarboxylic acid compounds, alicyclic tetracarboxylic acid compounds, and acyclic aliphatic tetracarboxylic acid compounds. ⁇ 2020/175 337 15 ⁇ (:171? 2020 /006912
  • the tetracarboxylic acid compound is preferably tetracarboxylic dianhydride.
  • tetracarboxylic acid dianhydride examples include aromatic tetracarboxylic acid dianhydride, alicyclic tetracarboxylic acid dianhydride, and acyclic aliphatic tetracarboxylic acid dianhydride.
  • the tetracarboxylic acid compound is an alicyclic tetracarbone compound or an aromatic tetracarboxylic acid compound. Etc. are preferred.
  • a tetracarboxylic acid compound is an alicyclic tetracarboxylic acid compound having a fluorine-based substituent and an aromatic tetracarboxylic acid compound having a fluorine-based substituent. It is preferably selected from carboxylic acid compounds, and more preferably an alicyclic tetracarboxylic acid compound having a fluorine-based substituent.
  • Examples of the tricarboxylic acid compound include aromatic tricarboxylic acids, alicyclic tricarboxylic acids, acyclic aliphatic tricarboxylic acids and their related acid chloride compounds, and acid anhydrides.
  • the tricarboxylic acid compound is preferably selected from aromatic tricarboxylic acid, alicyclic tricarboxylic acid, acyclic aliphatic tricarboxylic acid and their related acid chloride compounds. Two or more tricarboxylic acid compounds may be used in combination.
  • the tricarboxylic acid compound is an alicyclic tricarboxylic acid compound or an aromatic compound. It is preferably a tricarboxylic acid compound.
  • the tricarboxylic acid compound is an alicyclic tricarboxylic acid compound having a fluorine-based substituent or an aromatic tricarboxylic acid compound having a fluorine-based substituent. More preferably.
  • dicarboxylic acid compound examples include aromatic dicarboxylic acids, alicyclic dicarboxylic acids, acyclic aliphatic dicarboxylic acids and their related acid chloride compounds, and acid anhydrides.
  • the dicarboxylic acid compound is preferably an aromatic dicarboxylic acid. It is selected from acids, alicyclic dicarboxylic acids, acyclic aliphatic dicarboxylic acids and their related acid chloride compounds. Two or more dicarboxylic acid compounds may be used in combination.
  • the dicarboxylic acid compound is an alicyclic dicarboxylic acid compound or an aromatic compound. It is preferably a dicarboxylic acid compound.
  • the dicarboxylic acid compound is an alicyclic dicarboxylic acid compound having a fluorine-based substituent or an aromatic dicarboxylic acid compound having a fluorine-based substituent from the viewpoint of transparency and suppression of coloration of a substrate containing an imide-based polymer. Is more preferable.
  • diamines examples include aromatic diamines, alicyclic diamines, and aliphatic diamines, and two or more of them may be used in combination.
  • diamines are alicyclic diamines and aromatic compounds having a fluorine-based substituent. It is preferably selected from diamines.
  • the use of such an imide-based polymer has particularly excellent flexibility and a high light transmittance (for example, 85% or more, preferably 88% or more with respect to light of 550 nm), It is easy to obtain a substrate having low yellowness (Y value, 5 or less, preferably 3 or less), and low haze (1.5% or less, preferably 1.0% or less).
  • the imide-based polymer may be a copolymer containing a plurality of different types of repeating structural units described above.
  • the weight average molecular weight of the polyimide-based polymer is usually 100,000 to 500,000.
  • the weight average molecular weight of the imide-based polymer is preferably 50,000 to 500,000, more preferably 70,000 to 400,000.
  • the weight average molecular weight is a standard polystyrene equivalent molecular weight measured by gel permeation chromatography (GPC). If the weight average molecular weight of the imido polymer is large, it tends to be easy to obtain high flexibility. ⁇ 2020/175 337 17 ⁇ (:171? 2020 /006912
  • the imide-based polymer may contain a halogen atom such as a fluorine atom that can be introduced by the above-mentioned fluorine-based substituent or the like.
  • a halogen atom such as a fluorine atom that can be introduced by the above-mentioned fluorine-based substituent or the like.
  • the halogen atom is preferably a fluorine atom.
  • the content of halogen atoms in the polyimide-based polymer is preferably 1 to 40 mass% based on the mass of the polyimide-based polymer,
  • the substrate containing the imide-based polymer may contain one kind or two or more kinds of ultraviolet absorbers.
  • the ultraviolet absorber can be appropriately selected from those commonly used as an ultraviolet absorber in the field of resin materials. UV absorbers
  • the ultraviolet absorber that can be appropriately combined with the imide-based polymer includes, for example, at least one compound selected from the group consisting of benzophenone-based compounds, salicylate-based compounds, benzotriazole-based compounds, and triazine-based compounds.
  • system compound refers to a derivative of the compound to which the “system compound” is attached.
  • benzophenone-based compound refers to a compound having benzophenone as a base skeleton and a substituent bonded to benzophenone.
  • the content of the ultraviolet absorber is usually 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, usually 10% with respect to the total mass of the substrate. It is not more than 8% by mass, preferably not more than 8% by mass, more preferably not more than 6% by mass.
  • the weather resistance of the base material can be enhanced. ⁇ 2020/175 337 18 ⁇ (:171? 2020 /006912
  • the substrate containing the imide-based polymer may further contain an inorganic material such as inorganic particles.
  • the inorganic material is preferably a silicon material containing silicon atoms. Since the base material containing the imide-based polymer contains an inorganic material such as a silicon material, the tensile elastic modulus of the base material containing the imide-based polymer can be easily increased to 4.003 or more. However, the method of controlling the tensile elastic modulus of the base material containing the imide polymer is not limited to the compounding of the inorganic material.
  • Examples of the silicon material containing a silicon atom include silica particles, quaternary alkoxysilanes such as tetraethyl orthosilicate (Chomi 03), and silicon compounds such as silsesquioxane derivatives.
  • silicon materials silica particles are preferable from the viewpoint of transparency and flexibility of the substrate containing the imide polymer.
  • the average primary particle diameter of silica particles is usually 100 n It is the following. When the average primary particle size of silica particles is 100 n or less, transparency tends to improve.
  • the average primary particle diameter of silica particles in a substrate containing an imide-based polymer can be determined by observation with a transmission electron microscope (Cingemi IV!).
  • the primary particle size of the silica particles can be a unidirectional diameter measured by a transmission electron microscope (Dingmi IV!).
  • the average primary particle diameter can be obtained as an average value of 10 points of the primary particle diameter measured by observing D.
  • the particle distribution of silica particles before forming a base material containing an imide-based polymer can be obtained by a commercially available laser diffraction particle size distribution analyzer.
  • the mixing ratio of the imide-based polymer and the inorganic material is 1:9 to 10:0 in terms of mass ratio with the total of both being 10.
  • it is more preferably 3:7 to 10:0, and 3:7 to 8:
  • the ratio of the inorganic material to the total mass of the imido polymer and the inorganic material is usually 20% by mass or more, preferably 30% by mass or more, usually 90% by mass or less, and preferably 70% by mass. % Or less.
  • the imido polymer is ⁇ 2020/175 337 19 ⁇ (:171? 2020/006912
  • the transparency and mechanical strength of the substrate containing the limmer tend to be improved.
  • the tensile elastic modulus of the substrate containing the imide-based polymer can be easily increased to 4.03 or more.
  • the base material containing the imide-based polymer may further contain components other than the imide-based polymer and the inorganic material, as long as transparency and flexibility are not significantly impaired.
  • components other than the imide polymer and the inorganic material include antioxidants, release agents, stabilizers, coloring agents such as bluing agents, flame retardants, lubricants, thickeners and leveling agents.
  • the ratio of components other than imide-based polymers and inorganic materials is preferably more than 0% and 20% by mass or less, more preferably more than 0% and 10% by mass with respect to the mass of the base material. % Or less.
  • the substrate containing the imide-based polymer contains the imide-based polymer and the silicon material
  • the ratio of the number of silicon atoms to the number of nitrogen atoms on at least one surface of 3 / 1 ⁇ ! The above is preferable.
  • This atomic number ratio of 3 / / is X-ray photoelectron spectroscopy 1-101: 06 1 601:
  • the composition of the base material containing the imide-based polymer was evaluated by “0
  • 3 / 1 ⁇ 1 is more preferably 9 or more, further preferably 10 or more, preferably 50 or less, and more preferably 40 or less. ..
  • the base material is preferably in the form of a film.
  • the thickness of the base material is more preferably 100 or less, further preferably 80 or less, and most preferably 50 or less.
  • the thickness of the base material is thin, the difference in curvature between the front surface and the back surface during bending is small, cracks are less likely to occur, and breakage of the base material does not occur even if the base material is bent multiple times.
  • the thickness of the base material is preferably 3 or more, more preferably 5 or more, and most preferably 15 or more.
  • the base material may be formed by heat-melting a thermoplastic polymer, or may be formed by solution casting (solvent casting method) from a solution in which the polymer is uniformly dissolved.
  • solvent casting method solution casting method
  • the above-mentioned softening material and various additives can be added during heat melting.
  • the substrate is produced by the solution casting method
  • the above-mentioned softening material and various additives can be added to the polymer solution (hereinafter also referred to as a dope) in each preparation step.
  • the addition may be performed at any time in the dope preparation process, but may be carried out by adding the additive to the final preparation process of the dope preparation process.
  • the coating film may be heated for drying and/or baking the coating film.
  • the heating temperature of the coating film is usually 50 to 350 ° .
  • the coating film may be heated under an inert atmosphere or under reduced pressure.
  • the solvent can be evaporated and removed by heating the coating film.
  • the substrate, the method comprising the steps of drying the coating film at 5 0 ⁇ 1 5 0 ° ⁇ , and a step of 1 8 0 ⁇ 3 5 0 ° ⁇ Debe Kingu the coating film after drying, are formed Good.
  • At least one surface of the base material may be surface-treated.
  • the laminate of the present invention includes a hard coat layer.
  • the hard coat layer is formed on at least the _ side of the substrate.
  • the laminate of the present invention has at least one hard coat layer between the base material and the scratch resistant layer.
  • the hard coat layer of the laminate of the present invention comprises a polyorganosilsesquioxane (3 1) having a cation-polymerizable group, and a group containing a fluorine atom, a cation-polymerizable group and a radical-polymerizable group. It includes a cured product of the hard coat layer-forming composition containing the polymer (3). ⁇ 2020/175 337 21 ⁇ (: 171? 2020/006912
  • Polyorganosilsesquioxane having a cationically polymerizable group (3 1) Polyorganosilsesquioxane having a cationically polymerizable group (3 1) (“Polyorganosilsesquioxane (3 1)”
  • the cationically polymerizable group in the polyorganosilsesquioxane (31) is not particularly limited, and a generally known cationically polymerizable group can be used. Examples thereof include an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiro orthoester group, and a vinyloxy group.
  • an alicyclic ether group and a vinyloxy group are preferable, an epoxy group, an oxetanyl group and a vinyloxy group are particularly preferable, and an epoxy group is most preferable.
  • the epoxy group may be an alicyclic epoxy group (a group having a condensed ring structure of an epoxy group and an alicyclic group).
  • the polyorganosilsesquioxane (31) is preferably a polyorganosilsesquioxane represented by the following general formula (1).
  • [?] represents a group containing a cationically polymerizable group
  • Represents a monovalent group. And “represent the ratio of 13 and ⁇ in the general formula (1), +“ 100, is greater than 0, and is “0 or more.
  • a plurality of swallows and ⁇ may be the same or different, and when there are plural 80 in general formula (1), plural may form a bond with each other. ..
  • Polyorganosilsesquioxane is a network having a siloxane constitutional unit (silsesquioxane unit) derived from a hydrolyzable trifunctional silane compound. — A hexagonal polymer or a polyhedral cluster, which can form a random structure, a ladder structure, a cage structure, etc. by a siloxane bond.
  • siloxane constitutional unit siloxane constitutional unit derived from a hydrolyzable trifunctional silane compound.
  • a hexagonal polymer or a polyhedral cluster which can form a random structure, a ladder structure, a cage structure, etc. by a siloxane bond.
  • [S i ⁇ !. 5] structure represents portion may have any structure described above, but preferably contains a large amount of ladder structure. By forming the ladder structure, it is possible to maintain good deformation recovery of the laminate. Ladder structure shape
  • R b represents a group containing a cationically polymerizable group, and preferably a group containing an epoxy group.
  • Examples of the group containing an epoxy group include known groups having an oxirane ring.
  • R b is preferably a group represented by the following formulas (1 b) to (4 b).
  • ** represents a connecting portion with 3 m in the general formula (1), and is represented by [3 ⁇ 4 11 ⁇ [3 ⁇ 4 21 ⁇ Represents a single bond or a divalent linking group. [[ 3] and [[] are preferably substituted or unsubstituted alkylene groups.
  • alkylene group represented by [3 ⁇ 4 3 and [3 ⁇ 4 a linear or branched alkylene group having 1 to 10 carbon atoms is preferable, and examples thereof include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, and examples thereof include a propylene group, a propylene group, a butyl-butylene group, an n-pentylene group, a hexylene group, and an n-decylene group. ⁇ 2020/175 337 24 ⁇ (: 171?
  • the alkylene group represented by 3 and 4 I has a substituent, the substituent is a hydroxyl group, a carboxyl group, an alkoxy group, an aryl group, a heteroaryl group, a halogen atom, a nitro group, a cyano group, a silyl group, or the like.
  • the substituent is a hydroxyl group, a carboxyl group, an alkoxy group, an aryl group, a heteroaryl group, a halogen atom, a nitro group, a cyano group, a silyl group, or the like.
  • an unsubstituted straight-chain alkylene group having 1 to 4 carbon atoms and an unsubstituted branched alkylene group having 3 or 4 carbon atoms are preferable, ethylene group, n-propylene More preferably, it is an ethylene group or a closed-propylene group.
  • the polyorganosilsesquioxane (31) preferably has an alicyclic epoxy group (a group having a condensed ring structure of an epoxy group and an alicyclic group).
  • an alicyclic epoxy group a group having a condensed ring structure of an epoxy group and an alicyclic group.
  • the general formula (1) is preferably a group having an alicyclic epoxy group, more preferably a group having an epoxycyclohexyl group, and a group represented by the above formula (1 13) Is more preferable.
  • the general formula (1) Is a group bonded to a silicon atom in the hydrolyzable trifunctional silane compound used as a raw material for the polyorganosilsesquioxane (a group other than an alkoxy group and a halogen atom; for example, represented by the formula (M) below. 13) in hydrolyzable silane compounds).
  • the monovalent group represented by ⁇ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted An unsubstituted aralkyl group may be mentioned.
  • Examples of the alkyl group represented by ⁇ include an alkyl group having 1 to 10 carbon atoms.
  • Examples thereof include straight-chain or branched-chain alkyl groups such as a methyl group, an ethyl group, a propyl group, a _butyl group, an isopropyl group, an isoptyl group, a 3_butyl group, a 1_butyl group, and an isopentyl group.
  • Examples of the cycloalkyl group represented by ⁇ include a cycloalkyl group having 3 to 15 carbon atoms, and examples thereof include a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
  • Examples of the alkenyl group represented by ⁇ include an alkenyl group having 2 to 10 carbon atoms, and examples thereof include a linear or branched alkenyl group such as a vinyl group, an allyl group and an isopropenyl group.
  • Examples of the aryl group represented by ⁇ include aryl groups having 6 to 15 carbon atoms, and examples thereof include a phenyl group, a tolyl group, and a naphthyl group.
  • the aralkyl group represented by ⁇ includes an aralkyl group having 7 to 20 carbon atoms, and examples thereof include a benzyl group and a phenethyl group.
  • the above-mentioned substituted alkyl group, substituted cycloalkyl group, substituted alkenyl group, substituted aryl group, and substituted aralkyl group include hydrogen atoms in each of the above-mentioned alkyl group, cycloalkyl group, alkenyl group, aryl group, and aralkyl group.
  • Part or all of the child or main chain skeleton is from the group consisting of ether group, ester group, carbonyl group, halogen atom (fluorine atom, etc.), acryl group, methacryl group, mercapto group, and hydroxy group (hydroxyl group) Examples include groups substituted with at least one selected.
  • ⁇ is preferably a substituted or unsubstituted alkyl group and has an unsubstituted carbon number of 1 to 1
  • the plurality of O may form a bond with each other. It is preferable that two or three O's form a bond with each other, and it is more preferable that two O's form a bond with each other.
  • a group formed by bonding two ⁇ to each other Is preferably an alkylene group formed by combining the substituted or unsubstituted alkyl groups represented by the above.
  • An unsubstituted alkylene group having 2 to 20 carbon atoms is preferable, more preferably an unsubstituted alkylene group having 2 to 20 carbon atoms, and further preferably an unsubstituted alkylene group having 2 to 8 carbon atoms, Especially preferably! ...!—Putylene group, Pentylene group, Hexylene group, 1-1-heptylene group, 1-1-octylene group.
  • the alkylene group represented by 2 is preferably a trivalent group in which any hydrogen atom in the alkylene group is reduced by one.
  • the general formula (1) Is a group bonded to a silicon atom in a hydrolyzable silane compound used as a raw material of polyorganosilsesquioxane (a group other than an alkoxy group and a halogen atom; In the hydrolyzable silane compound represented ⁇ 3 etc.).
  • (+ “) is preferably from 0.5 to 1.0.
  • the total amount of the group represented by the swallow or ⁇ contained in the polyorganosilsesquioxane (3 1) Since the network formed by the organic cross-linking group is sufficiently formed, it is possible to maintain good hardness and repeated bending resistance.
  • 4 + 0 is more preferably 0.7 to 1.0, further preferably 0.9 to 1.0, and particularly preferably 0.95 to 1.0.
  • 4+0 is more preferably 0.005 to 0.01, more preferably 0.005 to 0.05, and particularly preferably 0.005 to 0.025.
  • the molecular weight dispersity (Mw/Mn) of polyorganosilsesquioxane (3 1) in terms of standard polystyrene by ⁇ is, for example, 1.0 to 4.0, preferably 1.1. To 3.7, more preferably 1.2 to 3.0, and further preferably 1.3 to 2.5. IV! represents the weight average molecular weight, and IV! n represents the number average molecular weight.
  • the weight average molecular weight and molecular weight dispersity of the polyorganosilsesquioxane (31) are measured by the following apparatus and conditions.
  • Measuring device Product name "!_ (3-20 8 0" (manufactured by Shimadzu Corporation) Column: 3 0 6 fathers [ ⁇ 801 x 2 pcs, [ ⁇ 1802, and ⁇ - 803 (Showa Denko KK ) Made)
  • Detector 11 _ ⁇ 3 detectors (brand name "30 _ 20 8", manufactured by Shimadzu Corporation)
  • the polyorganosilsesquioxane (31) can be produced by a known production method, and is not particularly limited, but it is produced by a method of hydrolyzing and condensing one or more hydrolyzable silan compounds. it can.
  • a hydrolyzable silane compound a hydrolyzable trifunctional silane compound (a compound represented by the following formula (M)) for forming a siloxane constitutional unit containing an epoxy group is used as the hydrolyzable silane compound.
  • M hydrolyzable trifunctional silane compound
  • X 2 in the formula (Mi) represents an alkoxy group or a halogen atom.
  • alkoxy group for X 2 examples include an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, a butoxy group and an isoptyloxy group.
  • halogen atom for X 2 examples include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
  • an alkoxy group is preferable, and a methoxy group and an ethoxy group are more preferable.
  • the three X 2 may be the same or different. ⁇ 2020/175 337 30 ⁇ (:171? 2020 /006912
  • the compound represented by the above formula (M) is a compound forming a siloxane constitutional unit having a gap.
  • X 3 in the above formulas ( ⁇ 1) to ( ⁇ 3) has the same meaning as X 2 in the above formula (M), and the preferred examples are also the same.
  • a plurality of X 3's may be the same or different.
  • hydrolyzable silane compound a hydrolyzable silane compound other than the compounds represented by the formulas (M) and ( ⁇ 31) to (03) may be used in combination.
  • Examples thereof include trifunctional silane compounds, hydrolyzable monofunctional silane compounds, and hydrolyzable bifunctional silane compounds.
  • [0107] is a hydrolyzable silane compound represented by the above formulas ( ⁇ 31) to (03).
  • / (+ ⁇ ) in the general formula (1) it suffices to adjust the compounding ratio (molar ratio) of the compounds represented by the above formulas (M) and ( ⁇ 3 1) to (0 3). ..
  • the value represented by the following (2) should be 0.5 to 1.0, and these compounds should be produced by hydrolysis and condensation. ..
  • the amount and composition of the above hydrolyzable silane compound can be appropriately adjusted according to the desired structure of the polyorganosilsesquioxane (31).
  • hydrolysis and condensation reaction of the hydrolyzable silane compound can be performed simultaneously or sequentially.
  • the order of performing the reactions is not particularly limited.
  • the hydrolysis and condensation reaction of the hydrolyzable silane compound can be carried out in the presence or absence of a solvent, and is preferably carried out in the presence of a solvent.
  • the solvent examples include aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran and dioxane; ketones such as acetone, methyl ethyl ketone and methyl isoptyl ketone; acetic acid.
  • aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene
  • ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran and dioxane
  • ketones such as acetone, methyl ethyl ketone and methyl isoptyl ketone
  • acetic acid examples include aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; ethers such as diethyl ether, dim
  • Esters such as methyl, ethyl acetate, isopropyl acetate, and butyl acetate; 1 ⁇ 1, 1 ⁇ 1-dimethylformamide, 1 ⁇ 1, 1 ⁇ 1-amide such as dimethylacetamide; acetonitrile, propionitrile , Nitrile such as benzonitrile; methanol, ethanol, isopropyl alcohol ⁇ 2020/175 337 32 ⁇ (: 171? 2020 /006912
  • the solvent is preferably ketone or ether.
  • the solvent may be used alone or in combination of two or more.
  • the amount of the solvent used is not particularly limited, and within a range of 0 to 200 parts by mass with respect to the total amount of the hydrolyzable silane compound of 100 parts by mass, a desired reaction time, etc. It can be adjusted accordingly.
  • the hydrolysis and condensation reactions of the hydrolyzable silane compound are preferably allowed to proceed in the presence of a catalyst and water.
  • the catalyst may be an acid catalyst or an alkali catalyst.
  • Examples of the above-mentioned acid catalyst include mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and boric acid; phosphoric acid esters; carboxylic acids such as acetic acid, sacrificial acid and trifluoroacetic acid; methansulfonic acid, trifluoromethanesulfonic acid, Examples thereof include sulfonic acids such as toluenesulfonic acid; solid acids such as activated clay; Lewis acids such as iron chloride.
  • alkali catalyst examples include hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide, potassium hydroxide and cesium hydroxide; alkaline earth metals such as magnesium hydroxide, calcium hydroxide and barium hydroxide.
  • nitrogen-containing aromatic heterocyclic compounds such as 2,2′-bibilidyl and 1,10-phenanthroline.
  • the catalyst may be used alone or in combination of two or more.
  • the catalyst can also be used in a state of being dissolved or dispersed in water, an organic solvent or the like.
  • the catalyst is preferably a base catalyst.
  • a base catalyst By using a base catalyst, the condensation rate of polyorganosilsesquioxane can be increased, and the deformation recovery rate upon curing can be kept good.
  • the amount of the catalyst used is not particularly limited, and may be appropriately adjusted within the range of 0.002 to 0.200 mol based on 1 mol of the total amount of the hydrolyzable silane compound. You can
  • the amount of water used in the hydrolysis and condensation reaction is not particularly limited, and may be appropriately in the range of 0.5 to 20 mol with respect to 1 mol of the total amount of the hydrolyzable silane compound. Can be adjusted.
  • the method for adding the water is not particularly limited, and the total amount of water used (total amount used) may be added all at once or sequentially. When they are added sequentially, they may be added continuously or intermittently.
  • the reaction conditions for carrying out the hydrolysis and condensation reaction of the above-mentioned hydrolyzable silane compound are, in particular, a reaction such that the condensation rate of the polyorganosilsesquioxane (31) is 80% or more. It is important to choose the conditions.
  • the reaction temperature of the hydrolysis and condensation reaction is, for example, 40 to 100 ° , preferably 45 to 80 ° . By controlling the reaction temperature within the above range, the condensation rate tends to be controlled to 80% or more.
  • the reaction time of the hydrolysis and condensation reactions is, for example, 0.1 to 10 hours, preferably 1.5 to 8 hours.
  • the above hydrolysis and condensation reaction can be carried out under normal pressure, or under pressure or under reduced pressure.
  • the atmosphere during the hydrolysis and condensation reaction may be, for example, an atmosphere of an inert gas such as a nitrogen atmosphere or an argon atmosphere, or the presence of oxygen such as an air. atmosphere Lower is preferred.
  • the polyorganosilsesquioxane (a 1) is obtained by the hydrolysis and condensation reaction of the hydrolyzable silane compound. After completion of the hydrolysis and condensation reactions, it is preferable to neutralize the catalyst in order to suppress ring opening of the epoxy group.
  • polyorganosilsesquioxane (a 1) can be separated by, for example, washing with water, washing with acid, washing with alkali, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or a combination thereof. It may be separated and purified by a separation means or the like.
  • the polyorganosilsesquioxane (a 1) condensation rate is preferably 80% or more from the viewpoint of film hardness.
  • the condensation rate is more preferably 90% or more, further preferably 95% or more.
  • the condensation rate is calculated using 29 Si NMR (nuclear magnetic resonance) spectrum measurement on a sample having a hard coat layer containing a cured product of polyorganosilsesquioxane (a 1) and using the measurement result. It is possible to calculate 29 Si NMR (nuclear magnetic resonance) spectrum measurement on a sample having a hard coat layer containing a cured product of polyorganosilsesquioxane (a 1) and using the measurement result. It is possible to
  • the epoxy group is preferably ring-opened by a polymerization reaction.
  • the epoxy group ring-opening rate of the cured product of the polyorganosilsesquioxane (a 1) having an epoxy group is preferably 40% or more from the viewpoint of the hardness of the film.
  • the ring opening rate is more preferably 50% or more, further preferably 60% or more.
  • the ring-opening rate is F T-IR (Fourier I ransrorm Infrared Spectroscopy) of the sample before and after the complete curing and heat treatment of the composition for forming a hard core layer containing polyorganosilsesquioxane (a 1).
  • F T-IR Fastier I ransrorm Infrared Spectroscopy
  • ATR Average Total Reef Iection
  • the polyorganosilsesquioxane (31) may be used alone or in combination of two or more having different structures.
  • the content of 3 1) is preferably 50% by mass or more, and more preferably 70% by mass or more, based on the total solid content of the composition for forming a hard coat layer. More preferably, it is at least mass %.
  • the upper limit of the content of polyorganosilsesquioxane (81) in the hard coat layer-forming composition is 99.9% by mass or less based on the total solid content of the hard coat layer-forming composition.
  • the amount is preferably 98% by mass or less, more preferably 97% by mass or less.
  • the total solid content refers to all components other than the solvent.
  • the polymer (3) As described above for the polymer (3) having a group containing a fluorine atom, a cationically polymerizable group, and a radically polymerizable group (also referred to as “polymer (3) ”), the polymer (3) is a hard resin. It can function as an interlayer adhesive that enhances the adhesion between the coat layer and the scratch resistant layer.
  • the group containing a fluorine atom in the polymer (3) is a group containing at least one fluorine atom, and includes, for example, a fluorine atom and an organic group having at least one fluorine atom.
  • examples include groups.
  • the organic group include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, an aryl group, and a group formed by combining at least two of these, and an alkyl group is preferable. preferable.
  • alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, cycloalkynyl group and aryl group may further have a substituent in addition to the fluorine atom. ⁇ 2020/175 337 36 ⁇ (:171? 2020 /006912
  • the fluorine-containing group is preferably a fluoroalkyl group having 1 to 20 carbon atoms, more preferably a fluoroalkyl group having 2 to 15 carbon atoms, and a fluoroalkyl group having 4 to 10 carbon atoms. It is more preferable that the fluoroalkyl group is a fluoroalkyl group having 4 to 8 carbon atoms.
  • the number of fluorine atoms in one fluorine-containing group is preferably 3 or more, more preferably 5 or more, and further preferably 9 or more.
  • the number of fluorine atoms in one fluorine-containing group is preferably 17 or less, and more preferably 13 or less.
  • the fluorine-containing group is preferably a group represented by the following general formula (Chi...!).
  • 91 is preferably an integer of 1 to 7, more preferably an integer of 1 to 5, and even more preferably 1 or 2.
  • 92 is preferably an integer of 2 to 8, more preferably an integer of 4 to 8, and even more preferably an integer of 4 to 6.
  • the cation-polymerizable group in the polymer (3) is not particularly limited, and a generally known cation-polymerizable group can be used. Specifically, an alicyclic ether group, a cyclic acetal group, a cyclic lactone group can be used. , A cyclic thioether group, a spiro orthoester group, a vinyloxy group and the like. As the cationic polymerizable group, an alicyclic ether group and a vinyloxy group are preferable, an epoxy group, an oxetanyl group and a vinyloxy group are particularly preferable, and an epoxy group is most preferable. ⁇ 0 2020/175 337 37 ⁇ (: 17 2020 /006912
  • the epoxy group may be an alicyclic epoxy group (a group having a condensed ring structure of an epoxy group and an alicyclic group).
  • each of the above groups may have a substituent.
  • the cationically polymerizable group is a group represented by the following formula (6-1), a group represented by the following general formula (6-2), or a group represented by the following general formula (6-3). It is preferable to have.
  • alkyl group having 1 to 6 carbon atoms examples include a methyl group, an ethyl group, a 11-propyl group, a __propyl group, a s-butyl group, a s-hexyl group and the like.
  • alkyl group has a substituent
  • substituents include a hydroxyl group, a carboxyl group, an alkoxy group, an aryl group, a heteroaryl group, a halogen atom, a nitro group, a cyano group and a silyl group.
  • 8 13 is preferably an unsubstituted linear alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group or an ethyl group.
  • alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a 11-propyl group, a __propyl group, a door-butyl group, a door-hexyl group and the like.
  • examples of the substituent include a hydroxyl group, a carboxyl group, an alkoxy group, an aryl group, a heteroaryl group, a halogen atom, a nitro group, a cyano group and a silyl group.
  • 93 represents an integer of 0 to 2, preferably 0 or 1, and more preferably 0.
  • the radically polymerizable group in the polymer (3) is not particularly limited, and a generally known radically polymerizable group can be used.
  • the radically polymerizable group include a polymerizable unsaturated group, specifically, a (meth)acryloyl group, a vinyl group, an allyl group and the like, and a (meth)acryloyl group is preferable.
  • Each of the above groups may have a substituent.
  • the content molar ratio of the structural unit having a fluorine atom is preferably more than 1 mol% and less than 70 mol% with respect to all the structural units,
  • the molar ratio of the constituent units having a fluorine atom is more than 1 mol% and less than 50 mol% with respect to all the constituent units, whereby the radical polymerizable group in the polymer (3) is A radical contained in the composition for forming a scratch resistant layer ⁇ 2020/175 337 39 ⁇ (:171? 2020 /006912
  • the polymerization reaction of the polymerizable compound (O 1) with the radically polymerizable group is not easily inhibited, the adhesion between the hard coat layer and the scratch resistant layer is increased, and the scratch resistance is easily improved, which is preferable.
  • the molar ratio of the constituent units having a cationically polymerizable group in the polymer (3) is more than 25 mol% and not more than 85 mol% with respect to all the constituent units. Is preferable, 30 mol% or more and 85 mol% or less is more preferable, and 30 mol% or more and 60 mol% or less is further preferable.
  • the content molar ratio of the structural unit having a radically polymerizable group in the polymer _) is preferably more than 1 mol% with respect to all the structural units. It is more preferably at least 90 mol% and more preferably at least 30 mol% and not more than 60 mol%.
  • the weight average molecular weight (IV!) of the polymer (3) is preferably 500 to 500.
  • 00 more preferably 1 000 to 30000, further preferably 1 500 to 1 2000, even more preferably 1 500 to 1 0000, particularly preferably 1 500 to 6000, and most preferably 1 500 to 4500.
  • Molecular weight dispersity of polymer (3) Is, for example, 1.00 to 4.
  • N represents the weight average molecular weight
  • IV! n represents the number average molecular weight
  • the weight average molecular weight and the molecular weight dispersity of the polymer _ (3) are measured values of OO (in terms of polystyrene).
  • the weight average molecular weight, specifically prepared 1-1! _ As a device (3_8220 (manufactured by Tosoh Corporation), with tetrahydrofuran as the eluent, Ding 3 ⁇ 9 6 I (registered trademark) ⁇ as column 30001 ⁇ 1 ⁇ 1 _ + Ding 3 [ ⁇ 96 I (registered trademark) ⁇ 20001 ⁇ 1 ⁇ 1 _, temperature 23°0, flow rate 1 / n , differential refractive index ([3 ⁇ 4 ⁇ ) detection Measure with a measuring instrument.
  • the polymer (3) may be used alone or in combination of two or more having different structures. ⁇ 2020/175 337 40 ⁇ (:171? 2020 /006912
  • the content of the polymer (3) in the composition for forming a hard coat layer in the present invention is, based on the total solid content of the composition for forming a hard coat layer, from the viewpoint of scratch resistance and suppression of whitening. 0.01 to 5 mass% is preferable, 0.01 to 3 mass% is more preferable, and 0.01 to 2 mass% is even more preferable, and 0.01 to It is particularly preferably 1% by mass.
  • the structure of the polymer (3) is not particularly limited, but it is preferably polyorganosilsesquioxane or (meth)acrylic polymer, and more preferably polyorganosilsesquioxane.
  • the polymer (3) is polyorganosilsesquioxane, whitening is particularly reduced in the laminate of the present invention, which is preferable.
  • the composition for forming a hard coat layer in the present invention contains the above-mentioned polyorganosylsesquioxane (31), the polymer (3) is a polyorganosil. It is considered that this is because sesquioxane has high compatibility with polyorganosylsesquioxane (31) and therefore has high homogeneity in the vicinity of the surface of the hard coat layer (not like microphase separation).
  • polymer (3) is polyorganosilsesquioxane
  • polymer (3) is also referred to as polyorganosilsesquioxane (33).
  • polyorganosilsesquioxane (33) is not particularly limited, and may have a structure that can be adopted as polyorganosilsesquioxane, such as a random structure, a ladder structure, or a cage structure. I like to be there.
  • Polyorganosilsesquioxane (3 3) is a silsesquioxane unit having a group containing a fluorine atom, a silsesquioxane unit having a cationically polymerizable group, and a silsesquioxane unit having a radically polymerizable group. It is preferable to have
  • Polyorganosilsesquioxane (33) is represented by the following general formula (3-1). ⁇ 0 2020/175 337 41 ⁇ (: 17 2020 /006912
  • 1_ 2 represents a single bond or a divalent linking group, 0 2 denotes the Kachio down polymerizable group.
  • 1_ 3 represents a single bond or a divalent linking group
  • 0 3 represents the radical Le polymerizable group
  • the molar ratio of the constituent units represented by the general formula (3-1) is more than 1 mol% and not more than 70 mol% based on all constituent units. Is more preferable, 3 mol% or more and 50 mol% or less is more preferable, and 5 mol% or more and 20 mol% or less is further preferable.
  • the content molar ratio of the structural unit represented by the general formula (3-2) is 15% or more and 85 5% or less based on all the structural units. Is more preferable, 30 mol% or more and 80 mol% or less is more preferable, 30 mol% or more and 70 mol% or less is further preferable, and 30 mol% or more and 60 mol% or more is preferable. % Or less is particularly preferable.
  • the content molar ratio of the structural unit represented by the general formula (3-3) is more than 1 mol% based on all the structural units. ⁇ 2020/175 337 42 ⁇ (: 171? 2020 /006912
  • an organic linking group having 1 to 20 carbon atoms eg, an alkylene group which may have a substituent, a cycloalkylene group which may have a substituent, and a substituent
  • an arylene group e.g., an organic linking group having 1 to 20 carbon atoms (eg, an alkylene group which may have a substituent, a cycloalkylene group which may have a substituent, and a substituent) Or an arylene group), or a linking group formed by combining two or more of these.
  • the above represents a hydrogen atom or a substituent.
  • _ general formula (3_ 1) a structural unit represented by the following _ general formula - is preferably a structural unit table in (3_ 1 ⁇ ).
  • 9 1 represents an integer from 0 to 12
  • 92 represents an integer from 1 to 8
  • 1_ 2 represents a single bond or a divalent linking group.
  • 1_ 2 is bivalent ⁇ 02020/175 337 43 ⁇ (: 17 2020 /006912
  • an alkylene group of 0 good carbon atoms 1-1 may have a substituent, one hundred and one, one thousand and one, ten thousand and one one OO 1, 1, 3 -, or a linking group formed by combining two or more of these is preferable, an alkylene group having 1 to 5 carbon atoms which may have a substituent, _ ⁇ 1, _ ⁇ ⁇ one,
  • 301 is a linking group formed by combining two or more of these, and an alkylene group having 1 to 5 carbon atoms which may have a substituent, or a substituted group.
  • a linking group formed by combining a C1-5 alkylene group which may have a group and 101 is more preferable.
  • 0 2 represents a cation polymerizable group.
  • the cationically polymerizable group is the same as described above.
  • structural units represented by the general formula (3_2), structural units represented by the following general formula (3_2_ 6 1), the structural unit represented by the following general formula (3_2_ 6 2), or the following general formula is preferably a structural unit represented by (3_2_ 6 3).
  • 1_ 2 represents a single bond or a divalent linking group.
  • Or 1 or 2 represents a single bond or a divalent linking group.
  • 1_ 2 represents a single bond or a divalent linking group.
  • 1 2 is the same as 1_ 2 in the above general formula (3-2).
  • 1-3 represents a single bond or a divalent linking group.
  • Specific examples and preferred ranges in the case where 1_ 3 represents a divalent linking group are the same as those in the above 1_ 2 .
  • 0 3 represents a radical polymerizable group.
  • the radical polymerizable group is the same as described above.
  • the constitutional unit represented by the general formula (3_3) may be a constitutional unit represented by the following general formula (3_3_ "1") or a constitutional unit represented by the following general formula (3_3_ "2). Preferred.
  • Formula (3_3_ "1), 1_ 3 represents a single bond or a divalent linking group, Represents a hydrogen atom or a methyl group.
  • 1_ 3 represents a single bond or a divalent linking group.
  • the method for producing the polyorganosilsesquioxane (33) is not particularly limited. ⁇ 2020/175 337 49 2020/006912
  • hydrolyzable silane compound a hydrolyzable trifunctional silane compound having a group containing a fluorine atom (preferably represented by the following general formula (3 _ 1) represented by the formula), a hydrolyzable trifunctional silane compound having a cationically polymerizable group (preferably a compound represented by the following general formula (30 1 _2)), and a radically polymerizable group. It is preferable to use a hydrolyzable trifunctional silane compound (preferably a compound represented by the following general formula (3_3)).
  • X 4 ⁇ X 6 each independently represent an alkoxy group or a halogen atom
  • l 1 represents a single bond or a divalent linking group
  • X 7 ⁇ X 9 each independently represent an alkoxy group or a halogen atom
  • 1_ 2 represents a single bond or a divalent linking group
  • 0 2 represents a cation polymerizable group.
  • X 1 ⁇ to X 12 are each independently an alkoxy group or halogen. ⁇ 2020/175 337 50 ⁇ (:171? 2020 /006912
  • X 4 - X 12 represents an alkoxy group or a halogen atom independently.
  • alkoxy group examples include methoxy group, ethoxy group, propoxy group, isopropyloxy group, butoxy group, isoptyloxy group, and other alkoxy groups having 1 to 4 carbon atoms.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
  • X 4 to X 12 an alkoxy group is preferable, and a methoxy group and an ethoxy group are more preferable.
  • X 4 to X 12 may be the same or different.
  • the amount and composition of the hydrolyzable silane compound can be appropriately adjusted according to the desired structure of the polyorganosilsesquioxane (33).
  • hydrolysis and condensation reactions of the hydrolyzable silane compound can be performed simultaneously or sequentially.
  • the order of performing the reactions is not particularly limited.
  • hydrolysis and condensation reactions of the hydrolyzable silane compound can be carried out in the presence or absence of a solvent, and are preferably carried out in the presence of a solvent.
  • solvent examples include aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; diethyl ether, dimethyethane, and tetrahydine. ⁇ 2020/175 337 51 ⁇ (:171? 2020 /006912
  • Ethers such as drofuran and dioxane; ketones such as acetone, methyl ethyl ketone, methyl isopropyl ethyl ketone; esters such as methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate; 1 ⁇ 1, 1 ⁇ 1-dimethylformamide, 1 ⁇ 1, 1 ⁇ 1 - amino-de-such as dimethyl acetamidine de; acetonitrile, propionitrile, nitrile such as base Nzonitoriru; methanol, ethanol, isopropyl alcohol _ le, alkoxyalkyl _ le such as butanol _ le and the like .
  • the solvent is preferably ketone or ether.
  • the solvent may be used alone or in combination of two or more.
  • the amount of the solvent used is not particularly limited, and is usually the total amount of the hydrolyzable silane compound.
  • the hydrolysis and condensation reactions of the hydrolyzable silane compound are preferably allowed to proceed in the presence of a catalyst and water.
  • the catalyst may be an acid catalyst or an alkali catalyst.
  • the acid catalyst is not particularly limited, and examples thereof include mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and boric acid; phosphoric acid esters; carboxylic acids such as acetic acid, sacrificial acid and trifluoroacetic acid; methanesulfonic acid, Trifluoromethanesulfonic acid, Examples thereof include sulfonic acids such as toluene sulfonic acid; solid acids such as activated clay; Lewis acids such as iron chloride.
  • the alkali catalyst is not particularly limited, and examples thereof include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide; magnesium hydroxide, calcium hydroxide, barium hydroxide, and the like.
  • Alkaline earth metal hydroxides lithium carbonates, sodium carbonates, potassium carbonates, cesium carbonates and other alkali metal carbonates; magnesium carbonates and other alkaline earth metal carbonates; lithium hydrogen carbonate, sodium hydrogen carbonate, carbonic acid
  • Alkali metal hydrogencarbonates such as potassium hydrogen and cesium hydrogen carbonate
  • Organic acid salts of alkali metals such as lithium acetate, sodium acetate, potassium acetate and cesium acetate (eg acetate);
  • Alkaline earths such as magnesium acetate Metal organic acid salt (eg ⁇ 2020/175337 52 ⁇ (:171? 2020/006912
  • the catalyst may be used alone or in combination of two or more.
  • the catalyst can also be used in a state of being dissolved or dispersed in water, a solvent or the like.
  • the amount of the catalyst used is not particularly limited, and is usually adjusted appropriately within the range of 0.002 to 0.20.2 mol with respect to 1 mol of the total amount of the hydrolyzable silane compound. You can
  • the amount of water used in the hydrolysis and condensation reactions is not particularly limited, and is usually within a range of 0.5 to 40 mols based on 1 mol of the total amount of the hydrolyzable silane compound, It can be adjusted appropriately.
  • the method for adding the water is not particularly limited, and the total amount of water used (total amount used) may be added all at once or sequentially. When they are added sequentially, they may be added continuously or intermittently.
  • reaction temperature of the hydrolysis and condensation reaction is not particularly limited, and may be, for example, 40 to
  • the reaction time of the hydrolysis and condensation reaction is not particularly limited and is, for example, 0.1 to 15 hours, and preferably 1.5 to 10 hours. Further, the hydrolysis and condensation reactions can be carried out under normal pressure, or under pressure or under reduced pressure.
  • the atmosphere for the hydrolysis and condensation reaction may be, for example, an atmosphere of an inert gas such as a nitrogen atmosphere or an argon atmosphere, or the presence of oxygen such as an air. A gas atmosphere is preferable. ⁇ 0 2020/175 337 53 ⁇ (: 17 2020 /006912
  • the polyorganosilsesquioxane (33) can be obtained by the hydrolysis and condensation reaction of the hydrolyzable silane compound. After completion of the hydrolysis and condensation reactions, the catalyst may be neutralized.
  • polyorganosilsesquioxane (33) can be separated by, for example, washing with water, washing with acid, washing with alkali, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, and other separation means. It may be separated and purified by a combination of separating means.
  • the polymer (3) is an acrylic polymer
  • the polymer (3) is also called (medium) acrylic polymer (38).
  • the (meth)acrylic polymer (38) may have a group containing a fluorine atom in its side chain, and may not have a fluorine atom in its main chain, from the viewpoint of adhesion to the scratch resistant layer. preferable.
  • the (meth) acrylic polymer (38) is a structural unit represented by the following general formula (1), a structural unit represented by the following general formula (_2), and a general formula (_3) below. It is preferable to have a structural unit represented by
  • IV 2 represents a hydrogen atom or a methyl group
  • 1_ 5 represents a single bond or a divalent linking group
  • ⁇ 5 represents a cation polymerizable group.
  • IV! 3 represents a hydrogen atom or a methyl group
  • 1_ ⁇ is a single bond or ⁇ 2020/175 337 54 ⁇ (: 171? 2020 /006912
  • 1_ 4 represents a single bond or a divalent linking group
  • 1_ 4 represents a divalent linking group
  • the specific examples are as follows.
  • 0 4 represents a group containing a fluorine atom.
  • the group containing a fluorine atom is the same as described above.
  • _ general formula structural units represented by (_ 1) is preferably a structural unit table below _ general formula (an "! One-! 1).
  • 0 2 represents a cation polymerizable group.
  • the cationically polymerizable group is the same as described above.
  • structural units represented by the general formula (_2), structural units represented by the following general formula (_2_ 6 1), the structural unit represented by the following general formula (_2_ 6 2), or the following general formula is preferably a structural unit represented by (_2_ 6 3). ⁇ 2020/175 337 55
  • IV! 2 represents a hydrogen atom or a methyl group
  • 1-5 represents a single bond or a divalent linking group.
  • IV! 2 represents a hydrogen atom or a methyl group, It represents an elementary atom or a substituted or unsubstituted alkyl group, and 1-5 represents a single bond or a divalent linking group.
  • IV! 2 represents a hydrogen atom or a methyl group, It represents a substituted or unsubstituted alkyl group. 3 represents an integer from 0 to 2. When there are two or more, they may be the same as or different from each other. 1_ 5 represents a single bond or a divalent linking group.
  • 1_ 6 represents a single bond or a divalent linking group.
  • Specific examples and preferred range when 1_ 6 represents a divalent linking group are the same as 1_ 3 in the aforementioned general formula (3_3).
  • the structural unit represented by general formula (_3) is a structural unit represented by the following general formula (_3_ “1”) or a structural unit represented by the following general formula (_3_ “2) Is preferred.
  • IV! 3 represents a hydrogen atom or a methyl group
  • 1_ 6 represents a single bond or a divalent linking group.
  • the method for producing the (meth)acrylic polymer (38) is not particularly limited, and it can be produced by a known production method.
  • a monomer having a (meth)acryloyl group is radically polymerized. It can be manufactured by the method.
  • Compound represented by the following general formula (_ 1) corresponds to a structural unit table by the general formula (_ 1), compounds represented by the following general formula (_2), the top Symbol _ general formula ( corresponding with the structural unit represented by _2), a compound represented by the following _ general formula (Rei_1 _3) corresponds to the constitutional unit represented by the general formula (_3)
  • IV! 2 represents a hydrogen atom or a methyl group
  • 1-5 represents a single bond or a divalent linking group
  • 0 5 represents a cation polymerizable group.
  • 1 ⁇ /1 3 represents a hydrogen atom or a methyl group
  • 1_ 6 is a single bond.
  • 0 6 represents a radical polymerizable group.
  • composition for forming a hard coat layer in the present invention preferably contains a cationic polymerization initiator.
  • composition for forming a hard coat layer in the present invention which contains a cationic polymerization initiator, can favorably proceed the polymerization reaction of the polyorganosilsesquioxane (3 1) and the cationically polymerizable group of the polymer (5). It is possible to combine the polyorganosilsesquioxane (81) and the polymer (3) in the hard coat layer.
  • the cationic polymerization initiator may be a photopolymerization initiator or a thermal polymerization initiator.
  • the content of the cationic polymerization initiator in the composition for forming the hard coat layer is not particularly limited, but for example, polyorganosilsesquioxane (3 1)
  • the composition for forming a hard coat layer in the present invention may contain a solvent.
  • a solvent an organic solvent is preferable, and one kind or two or more kinds of organic solvents can be mixed and used at an arbitrary ratio.
  • Specific examples of the organic solvent include, for example, methanol, ethanol, propanol, 11 _ butanol, _ _ butano. ⁇ 2020/175 337 62 ⁇ (:171? 2020/006912
  • -Alcohols such as acetone; Ketones such as acetone, methylisoptylketone, methylethylketone and cyclohexanone; Cellosolves such as ethylcellosolve; Aromatic compounds such as toluene and xylene; Propylene glycol monomethyl ether etc. Glycol ethers; acetic acid esters such as methyl acetate, ethyl acetate and butyl acetate; diacetone alcohol and the like.
  • the content of the solvent in the composition for forming a hard coat layer in the present invention can be appropriately adjusted within a range in which the suitability for coating of the composition for forming a hard coat layer can be ensured.
  • the total solid content of the hard coat layer-forming composition may be 50 to 500 parts by mass, preferably 80 to 200 parts by mass, based on 100 parts by mass. You can
  • composition for forming a hard coat layer usually takes the form of a liquid.
  • the solid content of the composition for forming a hard coat layer is usually about 10 to 90% by mass, preferably 20 to 80% by mass, and particularly preferably about 40 to 70% by mass. ..
  • the composition for forming a hard coat layer in the present invention may contain a component other than the above, and examples thereof include inorganic fine particles, a dispersant, a leveling agent, an antifouling agent, an antistatic agent, an ultraviolet absorber, It may contain an antioxidant and the like.
  • composition for forming a hard coat layer used in the present invention can be prepared by simultaneously mixing the various components described above or sequentially in an arbitrary order.
  • the preparation method is not particularly limited, and a known stirrer or the like can be used for the preparation.
  • the hard coat layer of the laminate of the present invention contains a cured product of the composition for forming a hard coat layer containing polyorganosilsesquioxane (31) and polymer (3), and preferably polyorganosyl. It includes a cured product of a composition for forming a hard coat layer, which contains sesquioxane (31), polymer _ (3), and a cationic polymerization initiator. ⁇ 2020/175 337 63 ⁇ (:171? 2020 /006912
  • the hardened product of the composition for forming a hard coat layer is at least a hardened product obtained by bonding a cationically polymerizable group of polyorganosylsesquioxane (3 1) and a cationically polymerizable group of the polymer (3) by a polymerization reaction. It is preferable to include.
  • the content of the cured product of the hard coat layer-forming composition in the hard coat layer of the laminate of the present invention is preferably 50% by mass or more, and more preferably 60% by mass or more. , 70% by mass or more is more preferable.
  • the thickness of the hard coat layer is not particularly limited, but is preferably 0.5 to 300, more preferably 1 to 25, and further preferably 2 to 20.
  • the film thickness of the hard coat layer is calculated by observing the cross section of the laminate with an optical microscope.
  • the cross-section sample can be created by a microtome method using an ultra-microtome cross-section cutting device, or a cross-section processing method using a focused ion beam (Mimi) device.
  • Mimi focused ion beam
  • the laminate of the present invention includes a scratch resistant layer.
  • the scratch resistant layer is formed on the hard coat layer.
  • the laminate of the present invention has at least one scratch resistant layer on the surface of the hard coat layer opposite to the substrate.
  • the scratch-resistant layer of the laminate of the present invention contains a cured product of the scratch-resistant layer-forming composition containing the radically polymerizable compound (O 1 ).
  • the radical-polymerizable compound ( ⁇ 1) (also referred to as “compound ( ⁇ 1)") is explained.
  • the compound ( ⁇ 1) is a compound having a radically polymerizable group.
  • the radically polymerizable group in the compound (O1) is not particularly limited, and a commonly known radical carboxylic acid polymerizable group can be used.
  • Examples of the group include a polymerizable unsaturated group, specifically, a (meth)acryloyl group, a vinyl group, an allyl group and the like, and a (meth)acryloyl group is preferable.
  • a polymerizable unsaturated group specifically, a (meth)acryloyl group, a vinyl group, an allyl group and the like, and a (meth)acryloyl group is preferable.
  • Each of the above groups may have a substituent.
  • the compound ( ⁇ 1) is preferably a compound having two or more (meth)acryloyl groups in one molecule, and a compound having three or more (meth)acryloyl groups in one molecule. Is more preferable.
  • the molecular weight of the compound (O1) is not particularly limited, and it may be a monomer, an oligomer or a polymer.
  • Examples of compounds having two (meth)acryloyl groups in one molecule include neopentyl glycol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, and Propylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, hydroxypivalate neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyl oxyacrylate
  • Preferable examples are chill (meth)acrylate, dicyclopentanyl di(meth)acrylate and the like.
  • Examples of the compound having three or more (meth)acryloyl groups in one molecule include an ester of a polyhydric alcohol and (meth)acrylic acid. Specifically, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethanetri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol.
  • Examples include tall tetra(meth)acrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol hexa(meth)acrylate, etc. ⁇ 2020/175 337 65 ⁇ (:171? 2020/006912
  • ethyl triacrylate pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, or mixtures thereof.
  • the compound (O1) may be used alone or in combination of two or more kinds having different structures.
  • the content of the compound ( ⁇ 1) in the composition for forming a scratch resistant layer is preferably 80% by mass or more based on the total solid content in the composition for forming a scratch resistant layer, 85 mass% or more is more preferable, and 90 mass% or more is further preferable.
  • composition for forming a scratch resistant layer in the present invention preferably contains a radical polymerization initiator.
  • the scratch-resistant layer forming composition of the present invention contains a radical polymerizable group of the polymer _ (3) and the compound ( ⁇ 1) contained in the above-mentioned hard coat layer forming composition by containing a radical polymerization initiator.
  • the polymer _ (3) which is capable of favorably advancing the polymerization reaction of, is unevenly distributed on the surface of the hard coat layer coating on the scratch-resistant layer coating side, and the compound ( ⁇ 1) in the scratch-resistant layer coating layer Can be combined with each other, and the adhesion between the hard coating layer and the scratch resistant layer can be enhanced.
  • radical polymerization initiator Only one radical polymerization initiator may be used, or two or more radical polymerization initiators having different structures may be used in combination.
  • the radical polymerization initiator may be a photopolymerization initiator or a thermal polymerization initiator.
  • the content of the radical polymerization initiator in the scratch-resistant layer-forming composition is not particularly limited, but may be, for example, 0.1 to 200 parts by mass relative to 100 parts by mass of the compound ( ⁇ 1). A part is preferable, and 1 to 50 parts by mass is more preferable.
  • the composition for forming a scratch resistant layer in the present invention may contain a solvent.
  • the solvent is the same as the solvent that may be contained in the composition for forming a hard coat layer.
  • the content of the solvent in the composition for forming a scratch resistant layer in the present invention is ⁇ 2020/175 337 66 ⁇ (:171? 2020 /006912
  • the composition for forming a scratch resistant layer it can be appropriately adjusted within a range that can secure the coating suitability of the composition for forming.
  • the total solid content of 100 parts by mass of the composition for forming a scratch resistant layer it can be 50 to 500 parts by mass, and preferably 80 to 200 parts by mass. You can
  • the composition for forming a scratch resistant layer usually takes the form of a liquid.
  • the solid content of the scratch-resistant layer forming composition is usually about 10 to 90% by mass, preferably 20 to 80% by mass, and particularly preferably about 40 to 70% by mass. ..
  • composition for forming a scratch resistant layer may contain components other than the above, and for example, it may contain inorganic particles, leveling agents, antifouling agents, antistatic agents, slip agents, solvents and the like. Good.
  • the fluorine-containing compound may be any of a monomer, an oligomer and a polymer.
  • the fluorine-containing compound preferably has a substituent that contributes to bond formation or compatibility with the polyfunctional (meth)acrylate compound ( ⁇ 1) in the scratch resistant layer.
  • the substituents may be the same or different, and it is preferable that there are plural substituents.
  • This substituent is preferably a polymerizable group, and may be a polymerizable reactive group exhibiting any of radically polymerizable, cationically polymerizable, anionically polymerizable, polycondensable and addition polymerizable, and examples of preferable substituents Examples thereof include an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, a cinnamoyl group, an epoxy group, an oxetanyl group, a hydroxyl group, a polyoxyalkylene group, a carboxyl group and an amino group. Of these, radically polymerizable groups are preferable, and acryloyl group and methacryloyl group are particularly preferable.
  • the fluorine-containing compound may be a polymer with a compound not containing a fluorine atom or may be a ligomer. ⁇ 2020/175 337 67 ⁇ (:171? 2020 /006912
  • the above-mentioned fluorine-containing compound is preferably a fluorine-based compound represented by the following general formula ().
  • nf represents an integer of 1 to 3.
  • 111 is an integer of 1 to 3.
  • the polymerizable unsaturated group is preferably a group having an unsaturated bond capable of causing a radical polymerization reaction by irradiation with active energy rays such as ultraviolet rays and electron beams (that is, radical polymerizable group), and (meth) Acryloyl group, (meth)acryloyloxy group, vinyl group, allyl group, etc., (meth)acryloyl group, (meth)acryloyloxy group, and any hydrogen atom in these groups is replaced by a fluorine atom.
  • the groups described above are preferably used.
  • Na represents a (per) fluoroalkyl group or a (per) fluoropolyether group.
  • the (per) fluoroalkyl group represents at least one of a fluoroalkyl group and a perfluoroalkyl group
  • the (per) fluoropolyether group represents at least one of a fluoropolyether group and a perfluoropolyether group.
  • the (per)fluoroalkyl group is preferably a group having 1 to 20 carbon atoms, and more preferably a group having 1 to 10 carbon atoms.
  • branched structure for example ten! ( ⁇ 3) 2, one Rei_1 to 1 2 ⁇ ( ⁇ 3) 2, ten 1 to 1 (Rei_1 to 1 3) ⁇ 2 ⁇ 3, one Rei_1 ⁇ 1 (Rei_1 ⁇ 1 3) ( ⁇ 2) 5 ⁇ be filed in 2 1 ⁇ 1), alicyclic structure (preferably a 5- or 6-membered ring, for example perfluoro cyclo hexyl and perfluoro Cyclopentyl groups as well as substituted with these groups ⁇ 2020/175 337 68 ⁇ (:171? 2020 /006912
  • the (per)fluoropolyether group refers to a case where the (per)fluoroalkyl group has an ether bond, and may be a monovalent group or a divalent or higher valent group.
  • Fluoropolyether groups include, for example, 2 ⁇ 3, ten H 2 CH 2 ⁇ _CH 2 C 4 F 8 H, _ ⁇ 1-1 2 ⁇ 1-1 2 hundred 1-1 2 ⁇ 1-1 2 ⁇ 8! 7 include _ ⁇ _1 ⁇ 1 2 ⁇ H 2 OC F 2 CF 2 OC F 2 CF 2 H% fluorine atom fluorocycloalkyl group with carbon number 4-2 0 having four or more like.
  • a perfluoropolyether group for example, one ( ⁇ 2 0) ( ⁇ 2 0 2 20) ⁇ -
  • the above chi and chi each independently represent an integer of 0 to 20. However, dried + dried is an integer of 1 or more.
  • the total of dried fish and dried fish is preferably 1 to 83, more preferably 1 to 43, and even more preferably 5 to 23.
  • the fluorine-containing compound is one from the viewpoint of excellent scratch resistance ( ⁇ 2 ⁇ ) - ( ⁇ 2 ⁇ 2 ⁇ ) particularly preferred and this having a perfluoropolyether group represented by.
  • the fluorine-containing compound preferably has a perfluoropolyether group and a plurality of polymerizable unsaturated groups in one molecule.
  • linking group represents a linking group.
  • examples thereof include an alkylene group, an arylene group and a heteroalkylene group, and a linking group formed by combining these groups.
  • These linking groups may further have an oxy group, a carbonyl group, a carbonyloxy group, a carbonylimino group, a sulfonamide group, and the like, and a functional group in which these groups are combined.
  • It is preferably an ethylene group, and more preferably an ethylene group bonded to a carbonylimino group.
  • the fluorine atom content of the fluorine-containing compound is not particularly limited, but is preferably 20% by mass or more, more preferably 30 to 70% by mass, and further preferably 40 to 70% by mass. ⁇ 2020/175 337 69 ⁇ (:171? 2020 /006912
  • Examples of preferable fluorine-containing compounds include [3 ⁇ 4-2020, 1 ⁇ /1-2020, 6-3833, IV!-3833 and Optool 0880 (trade name) manufactured by Daikin Chemical Industries, Ltd. , ⁇ I ⁇ made by Megafaq-1 7 1,-1 72,-179 8, [3 ⁇ 43-78, [3 ⁇ 43-90, Defenser IV! ⁇ -300 and IV! ⁇ -323 (these product names) Examples include but are not limited to:
  • the product of nf and mf (nfXm) is preferably 2 or more, and more preferably 4 or more.
  • Weight average molecular weight of fluorine-containing compound having polymerizable unsaturated group can be measured using molecular exclusion chromatography, for example gel permeation chromatography ( ⁇ ).
  • fluorine-containing compound used in the present invention Is preferably 400 or more and less than 50,000, more preferably 400 or more and less than 30,000, and even more preferably 400 or more and less than 2,500.
  • the content of the fluorine-containing compound is preferably 0.01 to 5% by mass, more preferably 0.1 to 5% by mass, and more preferably 0.01 to 5% by mass based on the total solid content in the composition for forming a scratch resistant layer.
  • 5 to 5 mass% is more preferable, and 0.5 to 2 mass% is particularly preferable.
  • composition for forming a scratch resistant layer used in the present invention can be prepared by simultaneously mixing the various components described above or sequentially in an arbitrary order.
  • the preparation method is not particularly limited, and a known stirrer or the like can be used for the preparation.
  • the scratch-resistant layer of the laminate of the present invention contains a cured product of the scratch-resistant layer-forming composition containing the compound ( ⁇ 1 ), and preferably contains the compound ( ⁇ 1) and a radical polymerization initiator. It includes a cured product of the composition for forming a scratch resistant layer.
  • the cured product of the composition for forming a scratch resistant layer preferably contains at least a cured product obtained by polymerization reaction of the radically polymerizable group of the compound (O1). ⁇ 2020/175 337 70 ⁇ (:171? 2020/006912
  • the content of the cured product of the scratch-resistant layer forming composition in the scratch-resistant layer of the laminate of the present invention is preferably 60% by mass or more, and 70% by mass or more based on the total mass of the scratch-resistant layer. Is more preferable, and 80% by mass or more is further preferable.
  • the film thickness of the scratch resistant layer is preferably less than 3.0, more preferably 0.01 to 2.0, and ⁇ .
  • the laminate of the present invention has excellent resistance to repeated bending.
  • the laminate of the present invention has no scratches when the abrasion resistance layer is placed inside and a bending test of 180 ° with a radius of curvature of 2 is repeated 300,000 times.
  • the repeated bending resistance is specifically measured as follows.
  • the laminate of the present invention has excellent scratch resistance.
  • the laminate of the present invention is made of #0000 steel wool. It is preferable that the surface of the scratch-resistant layer be rubbed 100 times back and forth while applying a load of 1. No scratches are generated, and it is preferable that the scratches are not generated when rubbed 100 times back and forth.
  • the scratch resistance is specifically measured as follows.
  • the surface of the scratch resistant layer of the laminate is subjected to a rubbing test using a rubbing tester under the following conditions to give an index of scratch resistance.
  • Scrubbing material Steel wool (manufactured by Nippon Steel Wool Co., Ltd., Grade 1 ⁇ 1 ⁇ .#00000)
  • Tip contact area 20 X 01 X 201
  • the oily black ink was applied to the surface (surface of the base material) opposite to the rubbed surface (surface of the scratch resistant layer) of the laminated body, and it was visually observed by reflected light, and it was in contact with steel wool. The number of times of rubbing when a part is scratched is measured and evaluated.
  • the method for producing a laminate of the present invention is preferably a production method including the following steps (I) to (IV).
  • the step () is a polyorganosylsesquioxane (3 1) having a cationically polymerizable group on the substrate, and a polymer (3) having a fluorine atom-containing group, a cationically polymerizable group and a radically polymerizable group. Is applied to form a hard coat layer-forming composition to form a hard coat layer coating film.
  • the base material, polyorganosilsesquioxane (31), polymer (3) and composition for forming a hard coat layer are as described above.
  • the method of applying the composition for forming a hard coat layer is not particularly limited, and a known method can be used. Examples thereof include a dip coating method, an air knife coating method, a force-ten coating method, a mouth roller coating method, a wire bar coating method, a gravure coating method and a die coating method.
  • the step ( ⁇ ) is a step of forming a hard coat layer by curing the hard coat layer coating film.
  • Curing the hard coat layer coating means that at least a part of the cationically polymerizable groups of the polyorganosilsesquioxane (81) and polymer (3) contained in the hard coat layer coating is polymerized.
  • the hard coat layer coating film is preferably cured by irradiation with ionizing radiation or heating.
  • the type of ionizing radiation is not particularly limited, and examples thereof include X-rays, electron beams, ultraviolet rays, visible light, and infrared rays, and ultraviolet rays are preferably used.
  • the coating film of the hard coat layer is UV curable, it can be treated with a UV lamp to measure 10". Then, the curable compound is preferably semi-cured. 5 0_Rei_1 "/ ⁇ 111 2 to 1 8 0 0
  • a metal halide lamp, a high-pressure mercury lamp, or the like is preferably used as the UV lamp type.
  • the oxygen concentration during curing is preferably 0 to 1.0% by volume, more preferably 0 to 0. 1% by volume, and most preferably 0 to 0. 05% by volume. Good
  • the step ( ⁇ ) is a step of forming a scratch-resistant layer coating film by applying the scratch-resistant layer forming composition containing the radically polymerizable compound ( ⁇ 1) on the hard coat layer.
  • the radical polymerizable compound ( ⁇ 1) and the composition for forming a scratch resistant layer are as described above.
  • the method for applying the composition for forming a scratch resistant layer is not particularly limited, and a known method can be used.
  • a known method can be used.
  • the dip coating method, the air knife coating method, the force-ten coating method, the mouth-roller coating method, the wire bar coating method, the gravure coating method, the die coating method and the like can be mentioned.
  • step (IV)-step ( ⁇ V) forms a scratch resistant layer by curing the above scratch resistant layer coating film ⁇ 2020/175 337 74 ⁇ (:171? 2020 /006912
  • Curing of the scratch resistant layer coating is preferably performed by irradiation with ionizing radiation or heating. Irradiation and heating of ionizing radiation are the same as those described in the process ( ⁇ ).
  • the curing of the scratch resistant layer coating means a polymerization reaction of at least a part of the radical polymerizable group of the radical polymerizable compound (O 1) contained in the scratch resistant layer coating.
  • the coating film of the hard coat layer is semi-cured in the above step ( ⁇ ). That is, in the step ( ⁇ ), the hard coat layer coating film is semi-cured, and then in the step ( ⁇ ), the scratch-resistant layer forming composition is applied on the semi-cured hard coat layer. It is preferable to form a layer coating film, and then in step (IV), the scratch-resistant layer coating film is cured and the hard coat layer is completely cured.
  • the hard coat layer coating means to polymerize only part of the cationically polymerizable groups of the polyorganosilsesquioxane (81) and polymer (3) contained in the hard coat layer coating. It means to react.
  • the semi-curing of the coating film of the hard coat layer can be carried out by adjusting the irradiation dose of ionizing radiation and the heating temperature and time.
  • a drying process may be performed if necessary. Drying is performed by blowing warm air, placing in a heating furnace, transporting in a heating furnace, heating with a roller from the surface (base material surface) where the hard coat layer and scratch resistant layer are not provided. It can be carried out.
  • the heating temperature may be set to a temperature at which the solvent can be dried and removed, and is not particularly limited. Here, the heating temperature means the temperature of warm air or the ambient temperature in the heating furnace.
  • the laminate of the present invention is excellent in scratch resistance and resistance to repeated bending and has little whitening, and can be used, for example, as an optical film (preferably a hard coat film). Further, the laminate of the present invention can be used as a surface protective film of an image display device, and for example, a folderable device ⁇ 2020/175 337 75 ⁇ (:171? 2020 /006912
  • a folderable device is a device that employs a flexible display whose display screen can be deformed, and the device itself (display) can be folded using the deformability of the display screen.
  • foldable devices include organic electroluminescent devices.
  • the present invention also relates to an article provided with the laminate of the present invention, and an image display device provided with the laminate of the present invention as a surface protective film.
  • 1 0101 1 to 19 is about 133.322 Pa.
  • each polymer used as the interlayer adhesive is shown below.
  • the molecular weight (1 ⁇ /1) and dispersity (Mw/ Mn ) of each polymer are shown in Table 1 below.
  • “3 0 5 ” represents a silsesquioxane unit.
  • Interlayer adhesive (3X 1 — 1) was added to IV! I, a solution containing the above compound (8).
  • ⁇ 111 is the start of photocationic polymerization by San-Apro Co., Ltd. It is an agent (solid content concentration 50% by mass).
  • the compounds used in the composition for forming a scratch resistant layer are as follows.
  • D P l ⁇ A A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.
  • RS- 90 Lubricant, manufactured by DIC Corporation
  • the hard coat layer forming composition HC-1 was applied onto a polyimide base material S _ 1 having a thickness of 30 m using a wire par # 18 so that the film thickness after curing became 18 Mm. After coating, a hard coat layer coating film was provided on the substrate.
  • the hard coat layer coating film was dried at 120°C for 1 minute, and then the illuminance was 18 mW/ Irradiation with an ultraviolet ray having a dose of cm 2 and an irradiation dose of 19 mJ/cm 2 was performed. In this way, the hard coat layer coating film was semi-cured.
  • the scratch-resistant layer forming composition S R-1 was applied using a die coater so that the film thickness after curing would be 0.8 ⁇ m. ..
  • Example 1 hard coat film having a hard coat layer and a scratch resistant layer on a substrate.
  • Example 2 was repeated in the same manner as in Example 1 except that the type and content of the interlayer adhesive used, the film thickness of the hard coat layer, and the film thickness of the scratch resistant layer were changed as described in Table 1 below. ⁇ 10 and the laminates (hard coat films) of Comparative Examples 1 to 7 were manufactured.
  • Scrubbing material Steel wool (manufactured by Nippon Steel Wool Co., Ltd., Grade 1 ⁇ 1 ⁇ .#00000)
  • Mouth scratches when rubbed 10 times back and forth
  • the tester used was a sample film with a diameter of 4 After bending along the curved surface of (cylindrical) at a bending angle of 180° at the center in the longitudinal direction and then returning it to its original position (expanding the sample film), one test is repeated and this test is repeated. Is. When the above 180° bending test was repeated 300,000 times, the case where no crack was generated was evaluated as 8, and the case where a crack was generated was evaluated as Mami. The presence or absence of cracks was visually evaluated.
  • the whitening of the film is performed with a surface roughness non-contact 3D surface profilometer (6 "I Surface roughness measured using an (trade name), manufactured by Ryoka System Co., Ltd. ) Was evaluated.
  • the content (% by mass) of the interlayer adhesive is a value based on the total solid content of the composition for forming a hard coat layer.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Laminated Bodies (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Epoxy Resins (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Silicon Polymers (AREA)

Abstract

La présente invention concerne un corps stratifié ayant un substrat, une couche de revêtement dur et une couche résistant aux rayures, dans cet ordre, la couche de revêtement dur comprenant un produit durci d'une composition pour former une couche de revêtement dur comprenant un polyorganosilsesquioxane (a1) ayant un groupe polymérisable par voie cationique, et un polymère (S) ayant un groupe comprenant un atome de fluor, un groupe polymérisable par voie cationique et un groupe polymérisable par voie radicalaire, et la couche résistant aux rayures comprenant un produit durci d'une composition pour former une couche résistant aux rayures qui comprend un composé polymérisable par voie radicalaire (c1) ; l'invention concerne également un article et un dispositif d'affichage d'image qui comprennent le corps stratifié.
PCT/JP2020/006912 2019-02-27 2020-02-20 Corps stratifié, article ayant un corps stratifié, et dispositif d'affichage d'image WO2020175337A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2021502154A JP7064650B2 (ja) 2019-02-27 2020-02-20 積層体、積層体を備えた物品、及び画像表示装置
KR1020217019637A KR102602546B1 (ko) 2019-02-27 2020-02-20 적층체, 적층체를 구비한 물품, 및 화상 표시 장치
JP2022071039A JP2022115881A (ja) 2019-02-27 2022-04-22 積層体、積層体を備えた物品、及び画像表示装置

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2019-034955 2019-02-27
JP2019034955 2019-02-27

Publications (1)

Publication Number Publication Date
WO2020175337A1 true WO2020175337A1 (fr) 2020-09-03

Family

ID=72238467

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2020/006912 WO2020175337A1 (fr) 2019-02-27 2020-02-20 Corps stratifié, article ayant un corps stratifié, et dispositif d'affichage d'image

Country Status (3)

Country Link
JP (2) JP7064650B2 (fr)
KR (1) KR102602546B1 (fr)
WO (1) WO2020175337A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022004746A1 (fr) * 2020-06-29 2022-01-06 富士フイルム株式会社 Stratifié, procédé de production pour stratifié, film de protection de surface contenant un stratifié pour dispositif d'affichage d'image, et article et dispositif d'affichage d'image comprenant un stratifié
WO2022004747A1 (fr) * 2020-06-29 2022-01-06 富士フイルム株式会社 Composition destinée à être utilisée pour former une couche de revêtement dur, film de revêtement dur, procédé de production de film de revêtement dur, et article comprenant un film de revêtement dur
JP2022115881A (ja) * 2019-02-27 2022-08-09 富士フイルム株式会社 積層体、積層体を備えた物品、及び画像表示装置
WO2022259893A1 (fr) * 2021-06-07 2022-12-15 富士フイルム株式会社 Composition de résine durcissable, film de revêtement dur et procédé de production de film de revêtement dur
WO2023276864A1 (fr) * 2021-06-29 2023-01-05 東洋紡株式会社 Composé silsesquioxane, et procédé de fabrication de celui-ci

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW202348434A (zh) * 2022-04-14 2023-12-16 芬蘭商歐提騰有限公司 柔性多層聚矽氧烷硬塗層

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014043101A (ja) * 2012-08-03 2014-03-13 Mazda Motor Corp 透明積層体およびその製造方法
JP2015212353A (ja) * 2013-12-13 2015-11-26 株式会社ダイセル ポリオルガノシルセスキオキサン、ハードコートフィルム、接着シート、及び積層物
WO2016010041A1 (fr) * 2014-07-15 2016-01-21 Jnc株式会社 Stratifié, article protégé en surface, procédé de fabrication de stratifié
US20160046830A1 (en) * 2014-08-13 2016-02-18 Sk Innovation Co., Ltd. Composition for making hard coating layer
WO2018116598A1 (fr) * 2016-12-22 2018-06-28 富士フイルム株式会社 Film optique et procédé de fabrication d'un film optique
WO2020021931A1 (fr) * 2018-07-27 2020-01-30 富士フイルム株式会社 Film de revêtement dur, article pourvu d'un film de revêtement dur, et appareil d'affichage d'image

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6619955B2 (ja) * 2015-06-17 2019-12-11 株式会社ダイセル 傷回復フィルム
KR101889955B1 (ko) * 2016-03-14 2018-08-20 주식회사 엘지화학 반사 방지 필름
KR20180058912A (ko) * 2016-11-24 2018-06-04 삼성디스플레이 주식회사 하드 코팅 조성물 및 플렉서블 표시 장치
JP6931526B2 (ja) 2016-11-25 2021-09-08 株式会社ダイセル ハードコートフィルム
JP6850408B2 (ja) * 2017-01-10 2021-03-31 Jnc株式会社 ラジカル重合性官能基を有するシルセスキオキサン誘導体、その組成物および低硬化収縮性硬化膜
JP6842977B2 (ja) * 2017-04-12 2021-03-17 株式会社ダイセル 積層体
JP2018178003A (ja) * 2017-04-17 2018-11-15 株式会社ダイセル フッ素含有エポキシ変性シルセスキオキサン、及びそれを含む硬化性組成物
JP2018189800A (ja) * 2017-05-02 2018-11-29 株式会社ダイセル 曲面ディスプレイ用ハードコートフィルム、ハードコートフィルム付き透明基板及びディスプレイ装置
KR102412888B1 (ko) * 2017-05-12 2022-06-28 삼성디스플레이 주식회사 하드코팅용 조성물, 및 하드코팅층을 포함하는 윈도우 부재
KR101818487B1 (ko) * 2017-05-16 2018-02-22 한국생산기술연구원 하드코팅 수지 조성물
JP2019164255A (ja) * 2018-03-20 2019-09-26 株式会社ダイセル 反射防止フィルム
JP7312543B2 (ja) * 2018-11-21 2023-07-21 株式会社ダイセル ガラス代替基材用耐候性ハードコート組成物、硬化物、及び積層体
JP7064650B2 (ja) * 2019-02-27 2022-05-10 富士フイルム株式会社 積層体、積層体を備えた物品、及び画像表示装置

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014043101A (ja) * 2012-08-03 2014-03-13 Mazda Motor Corp 透明積層体およびその製造方法
JP2015212353A (ja) * 2013-12-13 2015-11-26 株式会社ダイセル ポリオルガノシルセスキオキサン、ハードコートフィルム、接着シート、及び積層物
WO2016010041A1 (fr) * 2014-07-15 2016-01-21 Jnc株式会社 Stratifié, article protégé en surface, procédé de fabrication de stratifié
US20160046830A1 (en) * 2014-08-13 2016-02-18 Sk Innovation Co., Ltd. Composition for making hard coating layer
WO2018116598A1 (fr) * 2016-12-22 2018-06-28 富士フイルム株式会社 Film optique et procédé de fabrication d'un film optique
WO2020021931A1 (fr) * 2018-07-27 2020-01-30 富士フイルム株式会社 Film de revêtement dur, article pourvu d'un film de revêtement dur, et appareil d'affichage d'image

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022115881A (ja) * 2019-02-27 2022-08-09 富士フイルム株式会社 積層体、積層体を備えた物品、及び画像表示装置
WO2022004746A1 (fr) * 2020-06-29 2022-01-06 富士フイルム株式会社 Stratifié, procédé de production pour stratifié, film de protection de surface contenant un stratifié pour dispositif d'affichage d'image, et article et dispositif d'affichage d'image comprenant un stratifié
WO2022004747A1 (fr) * 2020-06-29 2022-01-06 富士フイルム株式会社 Composition destinée à être utilisée pour former une couche de revêtement dur, film de revêtement dur, procédé de production de film de revêtement dur, et article comprenant un film de revêtement dur
JPWO2022004747A1 (fr) * 2020-06-29 2022-01-06
JP7373074B2 (ja) 2020-06-29 2023-11-01 富士フイルム株式会社 ハードコート層形成用組成物、ハードコートフィルム、ハードコートフィルムの製造方法及びハードコートフィルムを含む物品
WO2022259893A1 (fr) * 2021-06-07 2022-12-15 富士フイルム株式会社 Composition de résine durcissable, film de revêtement dur et procédé de production de film de revêtement dur
WO2023276864A1 (fr) * 2021-06-29 2023-01-05 東洋紡株式会社 Composé silsesquioxane, et procédé de fabrication de celui-ci

Also Published As

Publication number Publication date
KR102602546B1 (ko) 2023-11-16
JPWO2020175337A1 (ja) 2021-10-28
JP2022115881A (ja) 2022-08-09
JP7064650B2 (ja) 2022-05-10
KR20210095187A (ko) 2021-07-30

Similar Documents

Publication Publication Date Title
WO2020175337A1 (fr) Corps stratifié, article ayant un corps stratifié, et dispositif d'affichage d'image
JP6979517B2 (ja) ハードコートフィルム、ハードコートフィルムを備えた物品、及び画像表示装置
JP6967662B2 (ja) ハードコートフィルム、ハードコートフィルムを有する物品、画像表示装置、及びハードコートフィルムの製造方法
JP7263356B2 (ja) ハードコートフィルム、ハードコートフィルムを備えた物品、及び画像表示装置
JP6999808B2 (ja) 組成物、ハードコートフィルム、ハードコートフィルムを備えた物品、及び画像表示装置
CN113544193B (zh) 聚有机硅倍半氧烷及硬涂层形成用组合物
JPWO2019235108A1 (ja) 改質剤、組成物、ハードコートフィルム、ハードコートフィルムを備えた物品、及び画像表示装置
KR102298174B1 (ko) 광학적층체 및 이를 포함하는 플렉서블 디스플레이 패널
CN115136033B (zh) 硬涂层形成用组合物、硬涂膜、具有硬涂膜的物品、图像显示装置及硬涂膜的制造方法
CN113840854B (zh) 树脂组合物、硬涂薄膜以及聚有机硅倍半氧烷
JP7280963B2 (ja) ハードコート層形成用組成物、ハードコートフィルム、ハードコートフィルムの製造方法、及びハードコートフィルムを含む物品
JP7291150B2 (ja) ハードコート組成物、ハードコートフィルム、ハードコートフィルムを有する物品、画像表示装置、及びハードコートフィルムの製造方法
WO2022004746A1 (fr) Stratifié, procédé de production pour stratifié, film de protection de surface contenant un stratifié pour dispositif d'affichage d'image, et article et dispositif d'affichage d'image comprenant un stratifié
CN115298275B (zh) 硬涂层形成用组合物、硬涂膜、硬涂膜的制造方法及具备硬涂膜的物品
JP6945062B2 (ja) ハードコート層形成用組成物、ハードコートフィルム、ハードコートフィルムを有する物品、画像表示装置、及びハードコートフィルムの製造方法
WO2022004747A1 (fr) Composition destinée à être utilisée pour former une couche de revêtement dur, film de revêtement dur, procédé de production de film de revêtement dur, et article comprenant un film de revêtement dur
WO2020235274A1 (fr) Film de revêtement dur, article ayant un film de revêtement dur, et dispositif d'affichage d'image
KR20220165184A (ko) 경화층 형성용 조성물, 적층체, 적층체의 제조 방법, 적층체를 구비한 물품, 화상 표시 장치 및 플렉시블 디스플레이

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20762716

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2021502154

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 20217019637

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20762716

Country of ref document: EP

Kind code of ref document: A1