WO2021166736A1 - Corps multicouche et dispositif d'affichage flexible - Google Patents

Corps multicouche et dispositif d'affichage flexible Download PDF

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Publication number
WO2021166736A1
WO2021166736A1 PCT/JP2021/004722 JP2021004722W WO2021166736A1 WO 2021166736 A1 WO2021166736 A1 WO 2021166736A1 JP 2021004722 W JP2021004722 W JP 2021004722W WO 2021166736 A1 WO2021166736 A1 WO 2021166736A1
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different
group
independently
carbon atoms
layer
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PCT/JP2021/004722
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English (en)
Japanese (ja)
Inventor
真芳 ▲徳▼田
友宏 伊藤
知典 宮本
みちる 上原
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住友化学株式会社
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Priority to KR1020227032014A priority Critical patent/KR20220140827A/ko
Priority to CN202180007445.0A priority patent/CN114868045A/zh
Publication of WO2021166736A1 publication Critical patent/WO2021166736A1/fr

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    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08L101/10—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
    • 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
    • G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements

Definitions

  • the present invention relates to a laminate and a flexible display device.
  • a fluorine-based water-repellent film represented by a film formed from a composition containing a compound having a perfluoropolyether structure has a very small surface free energy, so that it is a display device such as a touch panel display, an optical element, or a semiconductor element.
  • a display device such as a touch panel display, an optical element, or a semiconductor element.
  • Building materials, windowpanes of automobiles and buildings, etc., are used as antifouling coatings, water-repellent and oil-repellent coatings, and the like.
  • the water-repellent film is usually formed on a base material and used, and when the composition for forming a water-repellent film is applied to the base material, after another layer such as a primer layer is formed on the base material in advance. ,
  • the composition may be applied to form an antifouling coating or a water- and oil-repellent coating.
  • Patent Document 1 describes a hard coat film in which a hard coat layer (X), a primer layer (Y), and a surface layer (Z) are laminated in this order on at least one surface of a base material, and the surface layer (X).
  • a hard coat film having a water contact angle of 110 ° or more in Z) is disclosed.
  • a silane compound such as methoxysilane is preferable.
  • an object of the present invention is to provide a laminated body in which a base material, an intermediate layer, and a water-repellent layer are laminated in this order, and even if it is a thin film, it has excellent wear resistance.
  • the reflectance after deducting the loss and the back surface reflection loss is 4.5% or less.
  • the thickness of the laminated body is 500 ⁇ m or less.
  • the laminate according to [1] which satisfies the following requirement (3).
  • the surface fluorine element ratio on the water-repellent layer (r) side is 30 atomic% or more.
  • the laminate according to [1] or [2] which satisfies at least one of the following requirements (4) and (5).
  • the arithmetic mean height Sa on the water-repellent layer (r) side is 0.03 to 1.00 ⁇ m.
  • the sliding angle of water on the water-repellent layer (r) side is 25 ° or less.
  • the water-repellent layer (r) is a mixed composition (ca) of an organosilicon compound (A) represented by the following formula (a1) and an organosilicon compound (B) represented by the following formula (b1).
  • Rf a1 has a divalent perfluoropolyether structure in which both ends are oxygen atoms.
  • R 11, R 12, and R 13 are each independently an alkyl group having 1 to 20 carbon atoms, if R 11 there are a plurality may be different plural R 11 are each, R 12 is more if present may be different plurality of R 12 each may be the case where R 13 there are a plurality of different plural R 13 are each, E 1 , E 2 , E 3 , E 4 , and E 5 are independently hydrogen or fluorine atoms, respectively.
  • E 1 there are a plurality may be the different plurality of E 1, respectively, when the E 2 there are a plurality may be different plurality of E 2 are each of a plurality if E 3 there are multiple E 3 may have been different, or different plural E 4 each if E 4 there are a plurality, if E 5 there are a plurality may be different plurality of E 5, respectively,
  • G 1 and G 2 are 2- to 10-valent organosiloxane groups each independently having a siloxane bond.
  • J 1 , J 2 , and J 3 are independently hydrolyzable groups or-(CH 2 ) e6- Si (OR 14 ) 3 , e 6 is 1-5, and R 14 is a methyl group.
  • J 1 there are a plurality may be different plurality of J 1, respectively, when J 2 there are a plurality may be different plurality of J 2, respectively, J 3 is more Multiple J 3s may be different if they exist L 1 and L 2 are divalent linking groups having 1 to 12 carbon atoms which may independently contain an oxygen atom, a nitrogen atom, or a fluorine atom, and when a plurality of L 1s are present, a plurality of L 1 and L 2 are divalent linking groups.
  • L 1 It may be different for L 1, respectively, if L 2 there are a plurality may be different plurality of L 2, respectively, d11 is 1-9, d12 is 0-9, a10 and a14 are 0 to 10 independently of each other. a11 and a15 are independently 0 or 1, respectively. a12 and a16 are 0 to 9 independently of each other. a13 is 0 or 1, a21, a22, and a23 are 0 to 2 independently of each other. e1, e2, and e3 are 1 to 3 independently of each other.
  • Rf b10 is an alkyl group having 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are replaced with fluorine atoms.
  • R b11, R b12, R b13 and R b14 are each independently a hydrogen atom or a carbon atoms is an alkyl group of 1 to 4, if R b11 there are a plurality differ plurality of R b11 each may, if R b12 there are a plurality may be different plural R b12 each may be the case where R b13 there are a plurality of different plural R b13 are each if R b14 there are multiple May have different R b14s, Rf b11, Rf b12, Rf b13 and Rf b14 are each independently one or more hydrogen atoms is an alkyl group or a fluorine atom carbon number of 1 to 20 substituted by a fluorine atom, Rf b11 multiple presence
  • R is a hydrogen atom, a fluorine-containing alkyl group of the alkyl group having 1 to 4 carbon atoms having 1 to 4 carbon atoms, if a 1 there are a plurality may be different plurality of a 1, respectively,
  • a 2 is a hydrolyzable group, if A 2 there are a plurality may be different plurality of A 2, respectively, b11, b12, b13, b14 and b15 are independently integers from 0 to 100, respectively.
  • c is an integer of 1 to 3 and Rf b10 -, - Si (A 2) c (R b15) 3-c, b11 amino - ⁇ C (R b11) ( R b12) ⁇ -, b12 amino - ⁇ C (Rf b11) ( Rf b12) ⁇ -, B13- ⁇ Si (R b13 ) (R b14 ) ⁇ -, b14- ⁇ Si (Rf b13 ) (Rf b14 ) ⁇ -, b15 -A 1- are Rf b10- , Arranged in any order as long as -Si (A 2 ) c (R b15 ) 3-c is the terminal, does not form a perfluoropolyether structure, and -O- is not linked to -O- to -F.
  • the intermediate layer (c) is the cured layer of the mixed composition (cc) of the organosilicon compound (C) represented by any of the following formulas (c1) to (c3) or the organosilicon compound (C). ), which is the laminated body according to any one of [1] to [5].
  • R x11, R x12, R x13 , R x14 are each independently a hydrogen atom or a carbon atoms is an alkyl group of 1 to 4, if R x11 there are a plurality differ plurality of R x11 are each may, if R x12 there are a plurality may be different plural R x12 are each may be the case where R x13 there are a plurality of different plural R x13 are each if R x14 there are multiple May have different R x14s, Rf x11 , Rf x12 , Rf x13 , and Rf x14 are each independently an alkyl group having 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are substituted with fluorine atoms, and there are a plurality of Rf x11.
  • Rf x11 differs if the Rf x12 there are a plurality may be different plurality of Rf x12, respectively, a plurality of Rf x13 If Rf x13 is present in plural even if well, if Rf x14 there are a plurality may be different plurality of Rf x14, respectively, R x15 is an alkyl group having 1 to 20 carbon atoms, it may be the case where R x15 there are a plurality of different plural R x15 are each, X 11 is a hydrolysable group, if X 11 there are a plurality may be different plurality of X 11 are each, Y 11 is, -NH-, or -S-.
  • Z 11 is a vinyl group, an ⁇ -methylvinyl group, a styryl group, a methacryloyl group, an acryloyl group, an amino group, an isocyanate group, an isocyanurate group, an epoxy group, a ureido group, or a mercapto group.
  • p1 is an integer of 1 to 20
  • p2, p3, and p4 are independently integers of 0 to 10
  • p5 is an integer of 1 to 10.
  • p6 is an integer of 1 to 3 and If Z 11 is not an amino group, then at least one of Y 11 is -NH-, and if Y 11 is all -S-, then Z 11 is an amino group.
  • R x20 and R x21 are each independently a hydrogen atom or an alkyl group of 1 to 4 carbon atoms, if R x20 there are a plurality may be different plural R x20 are each, R x21 is When there are a plurality of R x21s, the plurality of R x21s may be different from each other, and Rf x20 and Rf x21 are each independently an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms.
  • Rf x20 there are a plurality may be different from each plurality of Rf x20, when Rf x21 there are a plurality may be different plurality of Rf x21, respectively,
  • each R x22 and R x23 is independently an alkyl group having 1 to 20 carbon atoms, may be the case where R x22 and R x23 there are a plurality of different plural R x22 and R x23 are each, X 20 and X 21 are each independently a hydrolysable group, if X 20 and X 21 there are a plurality may be different plurality of X 20 and X 21 are each,
  • p20 is an integer of 1 to 30 independently
  • p21 is an integer of 0 to 30 independently
  • at least one of the repeating units in parentheses with p20 or p21 is It has been replaced by an amine skeleton-NR 100 -where R 100 in the amine skeleton is a hydrogen atom or an al
  • p22 and p23 are independently integers of 1 to 3, respectively.
  • the p20- ⁇ C (R x20 ) (R x21 ) ⁇ -and the p21- ⁇ C (Rf x20 ) (Rf x21 ) ⁇ -do not have to be continuous p20 or p21, and are arbitrary. They are joined side by side in order, and both ends are -Si (X 20 ) p22 (R x22) 3-p22 and -Si (X 21 ) p23 (R x23 ) 3-p23 .
  • Z 31 and Z 32 are reactive functional groups other than the hydrolyzable group and the hydroxy group, respectively.
  • R x31, R x32, R x33 , R x34 are each independently a hydrogen atom or a carbon atoms is an alkyl group of 1 to 4, if R x31 there are a plurality differ plurality of R x31 are each may, if R x32 there are a plurality may be different plural R x32 are each may be the case where R x33 there are a plurality of different plural R x33 are each if R x34 there are multiple May have different R x 34s, Rf x31 , Rf x32 , Rf x33 , and Rf x34 are independently alkyl groups or fluorine atoms having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms, and there are a plurality of Rf x31.
  • Rf x31 may be different plurality of Rf x31 respectively, differ if the Rf x32 there are a plurality may be different plurality of Rf x32, respectively, a plurality of Rf x33 If Rf x33 is present in plural even if well, if Rf x34 there are a plurality may be different plurality of Rf x34, respectively, Y 31 is, -NH -, - N (CH 3) - or -O-.
  • X 31 , X 32 , X 33 , and X 34 are independently -OR c (R c is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an amino C 1-3 alkyl di C 1-3 alkoxysilyl.
  • a is a group), if X 31 there are a plurality may be different plurality of X 31 are each, if X 32 there are a plurality may be different plurality of X 32 are each, X 33 is If there are two or more may be different plurality of X 33 are each, if X 34 there are a plurality may be different plurality of X 34 are each, p31 is an integer of 0 to 20, p32, p33, and p34 are independently integers of 0 to 10, p35 is an integer of 0 to 5, and p36 is an integer of 1 to 10.
  • p37 is 0 or 1
  • the laminate of the present invention including the base material (s), the intermediate layer (c), and the water-repellent layer (r) in this order has wavelengths at an incident angle of 12 ° and a reflection angle of 12 ° measured on the surface of the water-repellent layer side. It has the requirement that the reflectance of 530 nm, which is obtained by subtracting the front surface reflectance loss and the back surface reflectance loss from the reflectance calculated by the JIS Z8701 2 degree field (C light source), is 4.5% or less. It has excellent wear resistance and also has a requirement of a thickness of 500 ⁇ m or less, so that both wear resistance and a thin film can be achieved at the same time.
  • the laminate of the present invention is a laminate having a base material (s), an intermediate layer (c), and a water-repellent layer (r) in this order, and satisfies the following requirements (1) and (2). ..
  • the reflectance after deducting the reflection loss is 4.5% or less.
  • the thickness of the laminated body is 500 ⁇ m or less.
  • the reflectance is preferably 4.3% or less, more preferably 3.5% or less, further preferably 2.5% or less, and even if it is 0.5% or more. good.
  • the thickness of the laminate of the present invention is preferably 400 ⁇ m or less, more preferably 300 ⁇ m or less, further preferably 200 ⁇ m or less, most preferably 100 ⁇ m or less, and 10 ⁇ m or more. May be good.
  • the laminate of the present invention satisfies the above requirements (1) and (2) and further satisfies at least one of the following requirements (3) to (5).
  • the surface fluorine element ratio on the water-repellent layer (r) side is 30 atomic% or more. By satisfying the requirement (3) above, better water repellency can be realized.
  • the surface fluorine element ratio is more preferably 40 atomic% or more, still more preferably 50 atomic% or more.
  • the upper limit of the surface fluorine element ratio is not particularly limited, but is, for example, 80 atomic%.
  • the surface fluorine element ratio can be measured by the method described in Examples described later.
  • the arithmetic mean height Sa on the water-repellent layer (r) side is 0.03 to 1.00 ⁇ m. By providing the requirement (4) above, the wear resistance can be further improved. The requirement (4) is also effective in achieving better water repellency and / or slipperiness.
  • the surface height Sa on the water-repellent layer (r) side is more preferably 0.70 ⁇ m or less, further preferably 0.50 ⁇ m or less, and even more preferably 0.30 ⁇ m or less. Further, the surface height Sa may be 0.04 ⁇ m or more, or may be 0.05 ⁇ m or more.
  • the arithmetic mean height Sa is calculated in accordance with ISO 25178.
  • the sliding angle of water on the water-repellent layer (r) side is 25 ° or less.
  • the sliding angle of water is more preferably 20 ° or less, further preferably 15 ° or less, and even more preferably 10 ° or less.
  • the lower limit of the sliding angle of water is not particularly limited, but is, for example, 1 °.
  • the water-repellent layer (r) is preferably a cured layer of a mixed composition (ca) of the organosilicon compound (A) and the organosilicon compound (B).
  • Organosilicon compound (A) In the organosilicon compound (A), a monovalent group having a perfluoropolyether structure is bonded to a silicon atom, and a hydrolyzable group is bonded to the silicon atom via a linking group or not via a linking group. It is a compound that is used.
  • the water-repellent layer (r) is preferably obtained by applying the composition (ca) and curing it, and has a structure derived from the organosilicon compound (A). As described above, the organosilicon compound (A) has a hydrolyzable group bonded to a silicon atom (may be bonded via a linking group), and the organosilicon compound (A) produced by hydrolysis is produced.
  • -SiOH groups Si and OH may be bonded via a linking group
  • the water-repellent layer (r) usually has a condensed structure derived from the organosilicon compound (A).
  • the hydrolyzable group include an alkoxy group, a halogen atom, a cyano group, an acetoxy group, an isocyanate group and the like.
  • the perfluoropolyether structure can also be referred to as a perfluorooxyalkylene group.
  • the perfluoropolyether structure has liquid repellency such as water repellency or oil repellency.
  • the number of carbon atoms contained in the longest linear portion of the perfluoropolyether structure is, for example, preferably 5 or more, more preferably 10 or more, and even more preferably 20 or more.
  • the upper limit of the number of carbon atoms is not particularly limited, and may be, for example, about 200.
  • the monovalent group having a perfluoropolyether structure of the organosilicon compound (A) preferably further has a perfluoroalkyl group at the free end.
  • the water-repellent layer (r) can also be shown as a layer having a perfluoropolyether structure and a polysiloxane skeleton, and preferably further has a perfluoroalkyl group.
  • the water-repellent layer (r) has a structure in which a monovalent group having a perfluoroalkyl structure and a perfluoroalkyl group at the free end is bonded to a part of the silicon atom of the polysiloxane skeleton. Is preferable.
  • the presence of the perfluoroalkyl group on the free end side improves water repellency.
  • the carbon number of the perfluoroalkyl group (particularly the carbon number of the longest straight chain portion) is preferably, for example, 3 or more, more preferably 5 or more, and even more preferably 7 or more.
  • the upper limit of the number of carbon atoms is not particularly limited, and even if it is, for example, about 20, it exhibits excellent water repellency.
  • the perfluoroalkyl group may form a fluorine-containing group such as a fluoroalkyl group by bonding with a group in which at least a part of the hydrogen atom of the hydrocarbon group and / or the hydrocarbon group is substituted with a fluorine atom.
  • CF 3 (CF 2) m - (CH 2) n -, CF 3 (CF 2) m -C 6 H 4 - (m is 1 to 10 both are preferably the 3 ⁇ 7, n Is 1 to 5, preferably 2 to 4), and CF 3 (CF 2 ) m- (CH 2 ) n- (m is 1 to 10, preferably 3 to 4). 7 and n are all 1 to 5, preferably 2 to 4). It is more preferable that the perfluoroalkyl group is directly bonded to the perfluoropolyether structure.
  • a monovalent group having a perfluoropolyether structure and a silicon atom may be bonded via an appropriate linking group, and the perfluoropolyether may be bonded without the linking group.
  • the monovalent group having may be directly bonded to the silicon atom.
  • the linking group include a hydrocarbon group such as an alkylene group and an aromatic hydrocarbon group, a (poly) alkylene glycol group, a group in which a part of these hydrogen atoms is substituted with a fluorine atom or a substituent, and these. Examples thereof include groups in which are appropriately linked.
  • the carbon number of the linking group is, for example, 1 or more and 20 or less, preferably 2 or more and 15 or less.
  • the hydrolyzable group has an action of binding the organosilicon compounds (A) to each other or the organosilicon compound (A) and active hydrogen (hydroxyl group or the like) on the surface of the base material through a hydrolysis / dehydration condensation reaction.
  • a hydrolyzable group include an alkoxy group (particularly an alkoxy group having 1 to 4 carbon atoms), a hydroxy group, an acetoxy group, and a halogen atom (particularly a chlorine atom).
  • Preferred hydrolyzable groups are an alkoxy group and a halogen atom, and a methoxy group, an ethoxy group and a chlorine atom are particularly preferable.
  • the hydrolyzable group may be bonded to a silicon atom via a linking group, or may be directly bonded to a silicon atom without a linking group.
  • the number of hydrolyzable groups bonded to the silicon atom may be one or more and may be 2 or 3, but is preferably 2 or 3, and particularly preferably 3.
  • different hydrolyzable groups may be bonded to the silicon atom, but the same hydrolyzable group is bonded to the silicon atom.
  • the total number of fluorine-containing groups and hydrolyzable groups bonded to the silicon atom is usually 4, but may be 2 or 3 (particularly 3).
  • a monovalent group other than the hydrolyzable group may be bonded to the remaining bond, for example, an alkyl group (particularly an alkyl group having 1 to 4 carbon atoms), H, NCO. Etc. can be combined.
  • the monovalent group having a perfluoropolyether structure of the organosilicon compound (A) may be linear or may have a side chain, and is preferably linear.
  • the organosilicon compound (A) can be represented by, for example, the following formula (a).
  • D 1 represents a monovalent group having a perfluoropolyether structure
  • the ends of the side that bind to D 2 in D 1 is -CF 2 -O - *, - CFD 9 - * at Yes (* is the bond on the D 2 side)
  • D 2 is a single bond or a divalent hydrocarbon group not substituted with a fluorine atom
  • D 3 is a trivalent hydrocarbon group not substituted with a fluorine atom.
  • a part of the methylene group of the hydrocarbon group may be replaced with an oxygen atom
  • D 4 is a hydrogen atom or a fluorine atom
  • D 5 is a single bond or a divalent hydrocarbon group
  • D 6 is a monovalent group other than a hydrolyzable group
  • D 7 is a divalent group or a single bond
  • D 8 is a hydrolyzable group
  • D 9 is a hydrogen atom, a fluorine atom, or a hydrocarbon. It is a group, n1 is 1 to 30, and n2 is 1 to 3. Examples of the hydrolyzable group of D 8 include those mentioned above.
  • the organosilicon compound (A) is preferably represented by the following formula (a1).
  • Rf a1 has a divalent perfluoropolyether structure in which both ends are oxygen atoms.
  • R 11 , R 12 , and R 13 are independent alkyl groups having 1 to 20 carbon atoms (that is, R 11 and R 12 and R 13 may be the same or different from each other).
  • R 11 there are a plurality may be different plurality of R 11 each may be the case where R 12 there are a plurality of different plural R 12 are each, if R 13 there are a plurality of May have different R 13s, E 1, E 2, E 3 , E 4, and E 5 is, independently represents a hydrogen atom or a fluorine atom, if E 1 there are a plurality may be different plurality of E 1, respectively, E 2 may be the case where there are plural different multiple E 2 respectively, when the E 3 there are a plurality may be different plurality of E 3 respectively, the plurality of E if E 4 there are a plurality of 4 may be different from each, if E 5 there are a plurality may be different plurality of E 5, respectively, G 1 and G 2 are 2- to 10-valent organosiloxane groups each independently having a siloxane bond.
  • J 1 , J 2 , and J 3 are independently hydrolyzable groups or-(CH 2 ) e6- Si (OR 14 ) 3 , e 6 is 1-5, and R 14 is a methyl group. or an ethyl group, if J 1 there are a plurality may be different plurality of J 1, respectively, when J 2 there are a plurality may be different plurality of J 2, respectively, J 3 is more Multiple J 3s may be different if they exist L 1 and L 2 are divalent linking groups having 1 to 12 carbon atoms which may independently contain an oxygen atom, a nitrogen atom, or a fluorine atom, and when a plurality of L 1s are present, a plurality of L 1 and L 2 are divalent linking groups.
  • L 1 It may be different for L 1, respectively, if L 2 there are a plurality may be different plurality of L 2, respectively, d11 is 1-9, d12 is 0-9, a10 and a14 are 0 to 10 independently of each other. a11 and a15 are independently 0 or 1, respectively. a12 and a16 are 0 to 9 independently of each other. a13 is 0 or 1, a21, a22, and a23 are 0 to 2 independently of each other. e1, e2, and e3 are 1 to 3 independently of each other.
  • the organosilicon compound (A) has a perfluoropolyether structure represented by Rf a1 and a hydrolyzable group represented by J 2 or-(CH 2). ) E6- Si (OR 14 ) 3 (where R 14 has a methyl group or an ethyl group).
  • the perfluoropolyether structure is a structure in which all hydrogen atoms of the polyoxyalkylene group are replaced with fluorine atoms, and can be said to be a perfluorooxyalkylene group, which can impart water repellency to the obtained film. Further, it is a compound that can be a matrix of a film obtained by bonding the organosilicon compounds (A) with each other or with other monomers through a polymerization reaction (particularly a polycondensation reaction) by J 2.
  • Rf a1 is preferably -O- (CF 2 CF 2 O) e4- or -O- (CF 2 CF 2 CF 2 O) e5- . Both e4 and e5 are 15 to 80.
  • R 11 , R 12 , and R 13 are each independently preferably an alkyl group having 1 to 10 carbon atoms.
  • L 1 and L 2 are each independently preferably a divalent linking group having 1 to 5 carbon atoms containing a fluorine atom.
  • G 1 and G 2 are preferably divalent to pentavalent organosiloxane groups having a siloxane bond, respectively.
  • J 1 , J 2 , and J 3 are each independently preferably a methoxy group, an ethoxy group, or-(CH 2 ) e6- Si (OR 14 ) 3 .
  • a10 is preferably 0 to 5 (more preferably 0 to 3), a11 is preferably 0, a12 is preferably 0 to 7 (more preferably 0 to 5), and a14 is preferably 1 to 6 (more preferably 1).
  • a15 is preferably 0, a16 is preferably 0 to 6, a21 to a23 are all preferably 0 or 1 (more preferably all 0), and d11 is preferably 1 to 5 (more preferably 1).
  • d12 is preferably 0 to 3 (more preferably 0 or 1), and e1 to e3 are all preferably 3.
  • a13 is preferably 1.
  • Rf a1 of the above formula (a1) is -O- (CF 2 CF 2 CF 2 O) e5- , e5 is 35 to 50, and L 1 and L 2 are. All are perfluoroalkylene groups having 1 to 3 carbon atoms, E 1 , E 2 , and E 3 are all hydrogen atoms, E 4 and E 5 are hydrogen atoms or fluorine atoms, and J 1 , J 2 and J 3 are both methoxy groups or ethoxy groups (particularly methoxy groups), a10 is 1 to 3, a11 is 0, a12 is 0 to 5, and a13 is 1.
  • a14 is 2 to 5, a15 is 0, a16 is 0 to 6, a21 to a23 are independently 0 or 1 (more preferably, a21 to a23 are all 0), and d11. It is preferable to use a compound in which 1 is 1, d12 is 0 or 1, and e1 to e3 are all 3.
  • Rf a1 of the above formula (a1) is ⁇ O ⁇ (CF 2 CF 2 CF 2 O) e5- , e5 is 25 to 40, L 1 is a fluorine atom and It is a divalent linking group having 3 to 6 carbon atoms containing an oxygen atom, L 2 is a perfluoroalkylene group having 1 to 3 carbon atoms, E 2 and E 3 are both hydrogen atoms, and E 5 is a hydrogen atom. It is a fluorine atom, J 2 is-(CH 2 ) e6- Si (OCH 3 ) 3 , e6 is 2 to 4, a10 is 1 to 3, a11 is 0, and a12 is 0.
  • a13 is 0, a14 is 2-5, a15 is 0, a16 is 0, and a21-a23 are independently 0 or 1 (more preferably a21-a23). Is all 0), d11 is 1, d12 is 0, and e2 is 3. It is also preferable to use a compound.
  • organosilicon compound (A) is a compound represented by the following formula (a2-1).
  • Rf a21 is an alkyl group having 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are replaced with fluorine atoms.
  • Rf a22 , Rf a23 , Rf a24 , and Rf a25 are independently alkyl groups or fluorine atoms having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms, and there are a plurality of Rf a22.
  • Rf a22 if present may be different plurality of Rf a22 respectively, if Rf a23 there are a plurality may be different plurality of Rf a23, respectively, a plurality of Rf a24 If Rf a24 are present in plural It may be different, if Rf a25 there are a plurality may be different plurality of Rf a25 respectively, R 20, R 21, R 22, and R 23 are each independently hydrogen atom or an alkyl group having 1 to 4 carbon atoms, if R 20 there are a plurality differ plurality of R 20 each may, if R 21 there are a plurality may be different plurality of R 21 each may be the case where R 22 there are a plurality of different plural R 22 are each, if R 23 there are a plurality of It may be a different multiple of R 23, respectively, R 24 is an alkyl group having 1 to 20 carbon atoms, it may be the case where R 24 there are a plurality of different plural R 24 are each, M 1 is
  • f16 is an integer from 1 to 20 and f17 is an integer of 0 to 2 and g1 is an integer of 1 to 3 and Rf a21- , M 2- , f11- ⁇ C (R 20 ) (R 21 ) ⁇ -, f12- ⁇ C (Rf a22 ) (Rf a23 ) ⁇ -, f13- ⁇ Si (R) 22 ) (R 23 ) ⁇ -, f14- ⁇ Si (Rf a24 ) (Rf a25 ) ⁇ -, f15 -M 3- , and f16- [CH 2 C (M 1 ) ⁇ (CH 2 ) f17-Si (M 4 ) g1 (R 24 ) 3-g1 ⁇ ]- ends at Rf a21- and M 2- , in the order of forming a perfluoropolyether structure at least in part.
  • Rf a21 is preferably an alkyl group having 1 to 10 carbon atoms substituted with one or more fluorine atoms, more preferably a perfluoroalkyl group having 1 to 10 carbon atoms, and further preferably 1 to 10 carbon atoms. It is a perfluoroalkyl group of 5.
  • Rf a22 , Rf a23 , Rf a24 , and Rf a25 are preferably independently each of a fluorine atom or an alkyl group having 1 to 2 carbon atoms in which one or more hydrogen atoms are substituted with a fluorine atom. Preferably all are fluorine atoms.
  • R 20 , R 21 , R 22 and R 23 are preferably independent hydrogen atoms or alkyl groups having 1 to 2 carbon atoms, and more preferably all hydrogen atoms.
  • R 24 is preferably an alkyl group having 1 to 5 carbon atoms.
  • M 1 is preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms independently of each other, and more preferably all hydrogen atoms.
  • M 2 is preferably a hydrogen atom.
  • M 4 is preferably an alkoxy group or a halogen atom, and more preferably a methoxy group, an ethoxy group or a chlorine atom.
  • f11, f13, and f14 are each 1/2 or less of f12, more preferably 1/4 or less, still more preferably f13 or f14 being 0, and particularly preferably f13 and f14 being 0. Is.
  • F15 is preferably 1/5 or more of the total value of f11, f12, f13, and f14, and is less than or equal to the total value of f11, f12, f13, and f14.
  • the f12 is preferably 20 to 600, more preferably 20 to 200, still more preferably 50 to 200 (more preferably 30 to 150, particularly preferably 50 to 150, most preferably 80 to 140).
  • the f15 is preferably 4 to 600, more preferably 4 to 200, still more preferably 10 to 200 (more preferably 30 to 60).
  • the total value of f11, f12, f13, f14, and f15 is preferably 20 to 600, more preferably 20 to 200, and even more preferably 50 to 200.
  • F16 is preferably 1 to 18. More preferably, it is 1 to 15. More preferably, it is 1 to 10.
  • F17 is preferably 0 to 1.
  • G1 is preferably 2 to 3, more preferably 3.
  • the repeating unit (ie- ⁇ C (Rf a22) (Rf a23 ) ⁇ -) enclosed in parentheses with f12 on the most fixed end side (the side that bonds to the silicon atom) is optional, but preferably.
  • the repeating units ie- ⁇ C (Rf a22) (Rf a23 ) ⁇ -and- ⁇ Si (Rf a24 ) (Rf a25 ) ⁇ -) with the sides f12 and f14 in parentheses are Repeat units with f11 and f13 on the most free end side and enclosed in parentheses (ie- ⁇ C (R 20 ) (R 21 ) ⁇ -and- ⁇ Si (R 22 ) (R 23 ) ⁇ - ) Is located on the free end side.
  • Rf a21 is a perfluoroalkyl group having 1 to 5 carbon atoms
  • Rf a22 , Rf a23 , Rf a24 , and Rf a25 are all fluorine atoms
  • M 3 is all -O-.
  • M 4 is all a methoxy group, an ethoxy group or a chlorine atom (particularly a methoxy group or an ethoxy group)
  • M 1 and M 2 are both hydrogen atoms
  • f11 is 0, and f12 is 30 to 150 (from). It is preferable that 80 to 140), f15 is 30 to 60, f13 and f14 are 0, f17 is 0 to 1 (particularly 0), g1 is 3, and f16 is 1 to 10.
  • organosilicon compound (A) is a compound represented by the following formula (a2-2).
  • Rf a26 , Rf a27 , Rf a28 , and Rf a29 are independently alkyl groups or fluorine atoms having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms, and there are a plurality of Rf a26.
  • Rf a26 if present may be different plurality of Rf a26 respectively, if Rf a27 there are a plurality may be different plurality of Rf a27, respectively, a plurality of Rf a28 If Rf a28 are present in plural It may be different, if Rf a29 there are a plurality may be different plurality of Rf a29 respectively, R 25, R 26, R 27, and R 28 are each independently hydrogen atom or an alkyl group having 1 to 4 carbon atoms, if R 25 there are a plurality differ plurality of R 25 each may, if R 26 there are a plurality may be different plurality of R 26 each may be the case where R 27 there are a plurality of different plural R 27 are each, if R 28 there are a plurality of It may be a different multiple of R 28, respectively, R 29, and R 30 are each independently an alkyl group having 1 to 20 carbon atoms, if R 29 there are a plurality may be different plural R 29 are each, R 30
  • R is a hydrogen atom, a fluorine-containing alkyl group of the alkyl group having 1 to 4 carbon atoms having 1 to 4 carbon atoms, if M 7 there are a plurality may be different plurality of M 7, respectively, M 5, M 9 are each independently hydrogen atom or an alkyl group having 1 to 4 carbon atoms, if M 5 there are a plurality may be different plurality of M 5, respectively, M 9 are multiple if present may be different plurality of M 9, respectively, M 6 and M 10 are independently hydrogen or halogen atoms, respectively.
  • M 8, and M 11 are each independently a hydrolysable group, if M 8 there are a plurality may be different plurality of M 8, respectively, of a plurality if M 11 there are a plurality of M 11 may be different, f21, f22, f23, f24, and f25 are independently integers from 0 to 600, and the total value of f21, f22, f23, f24, and f25 is 13 or more.
  • f26 and f28 are each independently an integer of 1 to 20.
  • f27 and f29 are independently integers of 0 to 2, respectively.
  • g2 and g3 are independently integers of 1 to 3, respectively.
  • M 10- , M 6- , f21- ⁇ C (R 25 ) (R 26 ) ⁇ -, f22- ⁇ C (Rf a26 ) (Rf a27 ) ⁇ -, f23- ⁇ Si (R) 27) (R 28) ⁇ - , f24 amino - ⁇ Si (Rf a28) ( Rf a29) ⁇ -, f25 amino -M 7 -, f26 amino - [CH 2 C (M 5 ) ⁇ (CH 2 ) F27-Si (M 8 ) g2 (R 29 ) 3-g2 ⁇ ], and f28- [CH 2 C (M 9 ) ⁇ (CH 2 ) f29-Si (M 11 ) g3 (R 30 ) 3 -g3 ⁇ ] are arranged in the order of forming a perfluoropolyether structure at least in part, with M 10- and M 6- at the ends, and in any order unless -O- is
  • Rf a26 , Rf a27 , Rf a28 , and Rf a29 are all fluorine atoms
  • M 7 is all -O-
  • M 8 and M 11 are all methoxy and ethoxy groups.
  • it is a chlorine atom (particularly a methoxy group or an ethoxy group)
  • M 5 , M 6 , M 9 , and M 10 are all hydrogen atoms
  • f21 is 0, and f22 is 30 to 150 (more preferably 80 to 140).
  • F25 is 30 to 60
  • f23 and f24 are 0, f27 and f29 are 0 to 1 (particularly preferably 0)
  • g2 and g3 are 3, and f26 and f28 are 1 to 10.
  • the organosilicon compound (A) includes a compound of the following formula (a3).
  • R 30 is a perfluoroalkyl group having 2 to 6 carbon atoms
  • R 31 and R 32 are independently perfluoroalkylene groups having 2 to 6 carbon atoms
  • R 33 is a trivalent saturated hydrocarbon group having 2 to 6 carbon atoms
  • R 34 is an alkyl group having 1 to 3 carbon atoms.
  • the carbon numbers of R 30 , R 31 , R 32 , and R 33 are preferably 2 to 4 independently, and more preferably 2 to 3.
  • h1 is 5 to 70
  • h2 is 1 to 5
  • h3 is 1 to 10.
  • h1 is preferably 10 to 60, 20 to 50 is more preferable
  • h2 is 1 to 4
  • 1 to 3 is more preferable
  • h3 is 1 to 8 is preferable
  • 1 to 6 is more preferable.
  • organosilicon compound (A) a compound represented by the following formula (a4) can also be mentioned.
  • R 40 is a perfluoroalkyl group having 2 to 5 carbon atoms
  • R 41 is a perfluoroalkylene group having 2 to 5 carbon atoms
  • R 42 is a perfluoroalkylene group having 2 to 5 carbon atoms.
  • a part of the hydrogen atom of the alkylene group is a fluoroalkylene group substituted with fluorine
  • R 43 and R 44 are independently alkylene groups having 2 to 5 carbon atoms
  • R 45 is a methyl group or an ethyl group.
  • k1, k2, and k3 are independently integers of 1 to 5.
  • the number average molecular weight of the organosilicon compound (A) is preferably 2,000 or more, more preferably 4,000 or more, still more preferably 6,000 or more, particularly preferably 7,000 or more, and 40. It is preferably 000 or less, more preferably 20,000 or less, and even more preferably 15,000 or less.
  • organosilicon compound (A) examples include a compound represented by the following formula (1) or a compound having a structure similar to the compound, and examples thereof include Optool (registered trademark) UF503 manufactured by Daikin Industries, Ltd. ..
  • Examples of the compound represented by the above formula (1) include those synthesized by the methods described in Synthesis Examples 1 and 2 of JP-A-2014-15609, where r is 43 and s is an integer of 1 to 6. , The number average molecular weight is about 8000.
  • Examples of the similar structure include a structure in which the number of carbon atoms of the hydrocarbon group of the above formula (1) or the number of carbon atoms of the hydrocarbon group substituted with a fluorine atom is different, a perfluoropolyether structure and a silicon atom without a linking group.
  • Other hydrocarbon groups (including hydrocarbon groups in which at least some hydrogen atoms are replaced with fluorine atoms) are located at any position of the linking group between the bonded structure, the perfluoropolyether structure and the silicon atom. Examples thereof include a structure in which a silicon atom and a hydrolyzable group are bonded via a linking group, a structure in which the values of r and s are different, and the like, but the structure is not limited to these structures.
  • Organosilicon compound (B) As will be described later, the organosilicon compound (B) represented by the following formula (b1) has a hydrolyzable group represented by A 2 , and is usually produced by hydrolysis of the organosilicon compound (B). -SiOH group is dehydrated and condensed with the -SiOH group of the organosilicon compound (A) generated by hydrolysis and / or the -SiOH group of the organosilicon compound (B) generated by hydrolysis.
  • the water-repellent layer (r) which is a cured layer of the mixed composition (ca), has a condensed structure derived from the organosilicon compound (A) and a condensed structure derived from the organosilicon compound (B).
  • the hydrolyzable group include an alkoxy group, a halogen atom, a cyano group, an acetoxy group, an isocyanate group and the like.
  • Rf b10 is an alkyl group having 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are replaced with fluorine atoms.
  • R b11, R b12, R b13 , R b14 are each independently a hydrogen atom or a carbon atoms is an alkyl group of 1 to 4, if R b11 there are a plurality differ plurality of R b11 each may, if R b12 there are a plurality may be different plural R b12 each may be the case where R b13 there are a plurality of different plural R b13 are each if R b14 there are multiple May have different R b14s, Rf b11, Rf b12, Rf b13 , Rf b14 are each independently one or more hydrogen atoms is an alkyl group or a fluorine atom carbon number of 1 to 20 substituted by a fluorine atom, Rf b11
  • R is a hydrogen atom, a fluorine-containing alkyl group of the alkyl group having 1 to 4 carbon atoms having 1 to 4 carbon atoms, if a 1 there are a plurality may be different plurality of a 1, respectively,
  • a 2 is a hydrolyzable group, if A 2 there are a plurality may be different plurality of A 2, respectively, b11, b12, b13, b14, and b15 are independently integers from 0 to 100, respectively.
  • c is an integer of 1 to 3 and Rf b10 -, - Si (A 2) c (R b15) 3-c, b11 amino - ⁇ C (R b11) ( R b12) ⁇ -, b12 amino - ⁇ C (Rf b11) ( Rf b12) ⁇ -, B13- ⁇ Si (R b13 ) (R b14 ) ⁇ -, b14- ⁇ Si (Rf b13 ) (Rf b14 ) ⁇ -, b15 -A 1- are Rf b10- , Arranged in any order as long as -Si (A 2 ) c (R b15 ) 3-c is the terminal, does not form a perfluoropolyether structure, and -O- is not linked to -O- to -F. Join.
  • Rf b10 is preferably a fluorine atom or a perfluoroalkyl group having 1 to 10 carbon atoms (more preferably 1 to 5 carbon atoms) independently of each other.
  • R b11, R b12, R b13 , and R b14 is preferably a hydrogen atom.
  • R b15 is preferably an alkyl group having 1 to 5 carbon atoms.
  • a 2 is preferably an alkoxy group having 1 to 4 carbon atoms or a halogen atom, and more preferably a methoxy group, an ethoxy group or a chlorine atom.
  • B11 is preferably 1 to 30, more preferably 1 to 25, further preferably 1 to 10, particularly preferably 1 to 5, and most preferably 1 to 2.
  • B12 is preferably 0 to 15, more preferably 0 to 10.
  • B13 is preferably 0 to 5, more preferably 0 to 2.
  • B14 is preferably 0 to 4, more preferably 0 to 2.
  • B15 is preferably 0 to 4, more preferably 0 to 2.
  • C is preferably 2 to 3, more preferably 3.
  • the total value of b11, b12, b13, b14, and b15 is preferably 3 or more, preferably 5 or more, preferably 80 or less, more preferably 50 or less, and further preferably 20 or less.
  • Rf b10 is a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms
  • R b11 and R b12 are both hydrogen atoms
  • a 2 is a methoxy group or an ethoxy group
  • b11 is 1 to 1 to 1. It is preferable that 5, b12 is 0 to 5, b13, b14, and b15 are all 0, and c is 3.
  • Specific examples of the compound represented by the above formula (b1) include CF 3- Si- (OCH 3 ) 3 , C j F 2j + 1- Si- (OC 2 H 5 ) 3 (j is 1 to 12). Of these, C 4 F 9- Si- (OC 2 H 5 ) 3 , C 6 F 13- Si- (OC 2 H 5 ) 3 , C 7 F 15- Si- (OC) 2 H 5 ) 3 and C 8 F 17- Si- (OC 2 H 5 ) 3 are preferable.
  • CF 3 (CF 2 ) m- (CH 2 ) n SiCl 3 CF 3 (CF 2 ) m- (CH 2 ) n Si (OCH 3 ) 3
  • CF 3 (CF 2 ) m- (CH 2 ) n Si (OC 2 H 5 ) 3 can also be mentioned (m is 1 to 10, preferably 3 to 7, and n is 1 to 5, preferably 2 to 4).
  • the compound represented by the following formula (b2) is preferable.
  • R 60 is a perfluoroalkyl group having 3 to 8 carbon atoms
  • R 61 is an alkylene group having 1 to 5 carbon atoms
  • R 62 is an alkyl group having 1 to 3 carbon atoms. ..
  • the mixed composition (ca) is a composition in which the organosilicon compound (A) and the organosilicon compound (B) are mixed, and the organosilicon compound (A) and the organosilicon compound (B) are mixed. Is obtained by mixing, and when a component other than the organosilicon compound (A) and the organosilicon compound (B) is mixed, the organosilicon compound (A) and the organosilicon compound (B) are mixed. It is obtained by mixing and other components.
  • the mixed composition (ca) also includes those whose reaction has proceeded after mixing, for example, during storage.
  • the mixed composition (ca) is usually mixed with a solvent (D).
  • a solvent (D) it is preferable to use a fluorine-based solvent, for example, a fluorinated ether solvent, a fluorinated amine solvent, a fluorinated hydrocarbon solvent and the like can be used, and the boiling point is particularly 100 ° C. or higher. Is preferable.
  • hydrofluoro ethers such as fluoroalkyl (particularly perfluoroalkyl group having 2 to 6 carbon atoms) -alkyl (particularly methyl group or ethyl group) ether are preferable, and for example, ethyl nona fluorobutyl ether or ethyl nona. Fluoroisobutyl ether can be mentioned. Examples of the ethyl nonafluorobutyl ether or ethyl nonafluoroisobutyl ether include Novec® 7200 (manufactured by 3M, molecular weight of about 264).
  • the fluorinated amine-based solvent is preferably an amine in which at least one hydrogen atom of ammonia is substituted with a fluoroalkyl group, and a third in which all hydrogen atoms of ammonia are substituted with a fluoroalkyl group (particularly a perfluoroalkyl group).
  • Primary amines are preferred, and specific examples thereof include tris (heptafluoropropyl) amines, such as Florinate (registered trademark) FC-3283 (manufactured by 3M, molecular weight: about 521).
  • fluorinated hydrocarbon solvent examples include a fluorinated aliphatic hydrocarbon solvent such as 1,1,1,3,3-pentafluorobutane, and a fluorinated aromatic solvent such as 1,3-bis (trifluoromethylbenzene). Hydrocarbon-based solvents can be mentioned.
  • 1,1,1,3,3-pentafluorobutane examples include Solve 55 (manufactured by Solvex).
  • hydrochlorofluorocarbons such as Asahiclean (registered trademark) AK225 (manufactured by AGC) and hydrofluorocarbons such as Asahiclean (registered trademark) AC2000 (manufactured by Asahi Glass Co., Ltd.) may be used. Can be done.
  • the solvent (D) it is preferable to use at least a fluorinated amine solvent as the solvent (D). Further, as the solvent (D), it is preferable to use two or more kinds of fluorine-based solvents, and it is preferable to use a fluorinated amine-based solvent and a fluorinated hydrocarbon-based solvent (particularly, a fluorinated aliphatic hydrocarbon-based solvent).
  • the amount of the organosilicon compound (A) in the mixed composition (ca) is, for example, 0.01% by mass or more, preferably 0.03% by mass or more, based on 100% by mass of the entire composition. It is more preferably 0.05% by mass or more, preferably 1.0% by mass or less, more preferably 0.5% by mass or less, still more preferably 0.3% by mass or less. Yes, and it is particularly preferable that it is 0.1% by mass or less.
  • the amount of the organosilicon compound (B) in the mixed composition (ca) is, for example, 0.01% by mass or more, preferably 0.03% by mass or more, based on 100% by mass of the entire composition. It is preferably 0.3% by mass or less, and more preferably 0.2% by mass or less.
  • the mass ratio of the organosilicon compound (B) to the organosilicon compound (A) is preferably 0.01 or more, more preferably 0.1 or more, still more preferably 0.3 or more, and 2. It is preferably 0 or less, more preferably 1.5 or less, and even more preferably 1.0 or less.
  • the amounts of the above-mentioned organosilicon compounds (A) and (B) can be adjusted at the time of preparing the composition.
  • the amounts of the organosilicon compounds (A) and (B) may be calculated from the analysis result of the composition.
  • the mixed composition (ca) for forming the water-repellent layer (r) is a silanol condensation catalyst, an antioxidant, a rust preventive, an ultraviolet absorber, a light stabilizer, and a fungicide, as long as the effect of the present invention is not impaired.
  • Various additives such as fungicides, antibacterial agents, bioadhesion inhibitors, deodorants, pigments, flame retardants, and antistatic agents may be mixed.
  • the thickness of the water-repellent layer (r) is, for example, about 1 to 1000 nm.
  • the intermediate layer (c) is a mixed composition (cc) of an organosilicon compound (C) having a silicon atom and an amino group or an amine skeleton (-NR 100- , and R 100 is a hydrogen atom or an alkyl group).
  • the cured layer of the above or a vapor-deposited layer of the organosilicon compound (C), and the intermediate layer (c) has an amino group or an amine skeleton.
  • the silicon atom of the organic silicon compound (C) has a hydrolyzable group or a hydroxy group bonded thereto, and the organic silicon compound (C) has a hydrolyzable group bonded to a Si—OH group or a silicon atom.
  • the intermediate layer (c) preferably has a condensed structure derived from the organic silicon compound (C).
  • the intermediate layer (c) can function as a primer layer for the water-repellent layer (r).
  • the hydrolyzable group bonded to the silicon atom of the organic silicon compound (C) include an alkoxy group, a halogen atom, a cyano group, an acetoxy group and an isocyanate group. It is preferable that an alkoxy group or a hydroxy group having 1 to 4 carbon atoms is bonded to the silicon atom of the organosilicon compound (C).
  • the organosilicon compound (C) is preferably a compound represented by any of the following formulas (c1) to (c3).
  • Organosilicon compound (C) represented by the following formula (c1) (hereinafter, organosilicon compound (C1))
  • R x11, R x12, R x13 , R x14 are each independently a hydrogen atom or a carbon atoms is an alkyl group of 1 to 4, if R x11 there are a plurality differ plurality of R x11 are each may, if R x12 there are a plurality may be different plural R x12 are each may be the case where R x13 there are a plurality of different plural R x13 are each if R x14 there are multiple May have different R x14s, Rf x11 , Rf x12 , Rf x13 , and Rf x14 are each independently an alkyl group having 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are substituted with fluorine atoms, and there are a plurality of Rf x11.
  • Rf x11 differs if the Rf x12 there are a plurality may be different plurality of Rf x12, respectively, a plurality of Rf x13 If Rf x13 is present in plural even if well, if Rf x14 there are a plurality may be different plurality of Rf x14, respectively, R x15 is an alkyl group having 1 to 20 carbon atoms, it may be the case where R x15 there are a plurality of different plural R x15 are each, X 11 is a hydrolysable group, if X 11 there are a plurality may be different plurality of X 11 are each, Y 11 is, -NH-, or -S-.
  • Z 11 is a vinyl group, an ⁇ -methylvinyl group, a styryl group, a methacryloyl group, an acryloyl group, an amino group, an isocyanate group, an isocyanurate group, an epoxy group, a ureido group, or a mercapto group.
  • p1 is an integer of 1 to 20
  • p2, p3, and p4 are independently integers of 0 to 10
  • p5 is an integer of 1 to 10.
  • p6 is an integer of 1 to 3 and If Z 11 is not an amino group, then at least one of Y 11 is -NH-, and if Y 11 is all -S-, then Z 11 is an amino group.
  • R x11 , R x12 , R x13 , and R x14 are preferably hydrogen atoms.
  • Rf x11 , Rf x12 , Rf x13 , and Rf x14 are each independently an alkyl group having 1 to 10 carbon atoms or a fluorine atom in which one or more hydrogen atoms are substituted with fluorine atoms.
  • R x15 is preferably an alkyl group having 1 to 5 carbon atoms.
  • X 11 is preferably an alkoxy group, a halogen atom, a cyano group, or an isocyanate group, more preferably an alkoxy group, and even more preferably a methoxy group or an ethoxy group.
  • Y 11 is preferably ⁇ NH ⁇ .
  • Z 11 is preferably a methacryloyl group, an acryloyl group, a mercapto group or an amino group, more preferably a mercapto group or an amino group, and even more preferably an amino group.
  • P1 is preferably 1 to 15, more preferably 2 to 10.
  • p2, p3 and p4 are preferably 0 to 5, more preferably all 0 to 2.
  • p5 is preferably 1 to 5, more preferably 1 to 3.
  • the p6 is preferably 2 to 3, more preferably 3.
  • both R x11 and R x12 are hydrogen atoms
  • Y 11 is -NH-
  • X 11 is an alkoxy group (particularly a methoxy group or an ethoxy group).
  • Z 11 is an amino group or a mercapto group
  • p1 is 1 to 10
  • p2, p3 and p4 are all
  • p5 is 1 to 5 (particularly 1 to 3)
  • p6 It is preferable to use a compound having a value of 3.
  • the organosilicon compound (C1) is preferably represented by the following formula (c1-2).
  • X 12 is a hydrolysable group, if X 12 there are a plurality may be different plurality of X 12 are each, Y 12 is -NH- Z 12 is an amino group or a mercapto group, R x16 is an alkyl group having 1 to 20 carbon atoms, it may be the case where R x16 there are a plurality of different plural R x16 are each, p is an integer of 1 to 3, q is an integer of 2 to 5, and r is an integer of 0 to 5.
  • X 12 is preferably an alkoxy group, a halogen atom, a cyano group, or an isocyanate group, more preferably an alkoxy group, and even more preferably an alkoxy group having 1 to 4 carbon atoms.
  • Z 12 is preferably an amino group.
  • R x16 is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms.
  • P is preferably an integer of 2 to 3, and more preferably 3.
  • Q is preferably an integer of 2 to 3
  • r is preferably an integer of 2 to 4.
  • Organosilicon compound (C) represented by the following formula (c2) (hereinafter, organosilicon compound (C2))
  • R x20 and R x21 are each independently a hydrogen atom or an alkyl group of 1 to 4 carbon atoms, if R x20 there are a plurality may be different plural R x20 are each, R x21 is If there are multiple R x21s, multiple R x21s may be different.
  • Rf x20 and Rf x21 are each independently an alkyl group having 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are substituted with fluorine atoms, and when a plurality of Rf x20 are present, a plurality of Rfs are present.
  • each R x22 and R x23 is independently an alkyl group having 1 to 20 carbon atoms, may be the case where R x22 and R x23 there are a plurality of different plural R x22 and R x23 are each, X 20 and X 21 are each independently a hydrolysable group, if X 20 and X 21 there are a plurality may be different plurality of X 20 and X 21 are each, p20 is an integer from 1 to 30, p21 is an integer from 0 to 30, and at least one of the repeating units in parentheses with p20 or p21 is replaced by the amine backbone-NR 100-.
  • R 100 in the amine skeleton is a hydrogen atom or an alkyl group.
  • p22 and p23 are independently integers of 1 to 3, respectively.
  • the p20- ⁇ C (R x20 ) (R x21 ) ⁇ -and the p21- ⁇ C (Rf x20 ) (Rf x21 ) ⁇ -do not have to be consecutive p20 or p21, and are in any order. Both ends are -Si (X 20 ) p22 (R x22 ) 3-p22 and -Si (X 21 ) p23 (R x23 ) 3-p23 .
  • R x20 and Rx21 are preferably hydrogen atoms.
  • Rf x20 and Rf x21 are preferably alkyl groups or fluorine atoms having 1 to 10 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms, respectively.
  • R x22 and R x23 are preferably a carbon number of alkyl group of 1 to 5.
  • X 20 and X 21 are preferably an alkoxy group, a halogen atom, a cyano group, or an isocyanate group, more preferably an alkoxy group, and even more preferably a methoxy group or an ethoxy group.
  • At least one amine skeleton-NR 100 - may be present in the molecule as described above, and any of the repeating units in parentheses with p20 or p21 may be replaced by the amine skeleton.
  • a plurality of the amine skeletons may be present, and in that case, the number of amine skeletons is preferably 1 to 10, more preferably 1 to 5, and even more preferably 2 to 5. Further, in this case, it is preferable to have an alkylene group between adjacent amine skeletons, and the carbon number of the alkylene group is preferably 1 to 10, and more preferably 1 to 5. The carbon number of the alkylene group between adjacent amine backbones is included in the total number of p20 or p21.
  • the number of carbon atoms is preferably 5 or less, and more preferably 3 or less.
  • the amine skeleton -NR 100- is preferably -NH- (R 100 is a hydrogen atom).
  • P20 is preferably 1 to 15, more preferably 1 to 10, excluding the number of repeating units replaced by the amine skeleton.
  • P21 is preferably 0 to 5, more preferably all 0 to 2, except for the number of repeating units replaced by the amine skeleton.
  • P22 and p23 are preferably 2 to 3, more preferably 3.
  • the organosilicon compound (C2) in the formula (c2), an R x20 and R x21 are both hydrogen atom, X 20 and X 21 is an alkoxy group (particularly methoxy group or ethoxy group), a p20
  • the repeating units in parentheses are replaced with at least one amine skeleton-NR 100- , where R 100 is a hydrogen atom and p20 is 1-10 (but replaced by an amine skeleton). (Excluding the number of repeating units), it is preferable to use a compound in which p21 is 0 and p22 and p23 are 3.
  • Product name; X-12-5263HP, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) is represented by the above formula (c2).
  • R x20 and R x21 are both hydrogen atoms, p20 is 8, p21 is 0, and amine skeleton is 2.
  • the organosilicon compound (C2) is preferably a compound represented by the following formula (c2-2).
  • X 22 and X 23 are each independently a hydrolyzable group, when X 22 and X 23 there are a plurality may be different plurality of X 22 and X 23 are each, R x24 and R x25 are each independently alkyl groups having 1 to 20 carbons, may be the case where R x24 and R x25 there are a plurality of different plural R x24 and R x25 are each, -C w H 2w -has at least one of its methylene groups replaced by an amine skeleton -NR 100- , where R 100 is a hydrogen atom or an alkyl group.
  • w is an integer from 1 to 30 (excluding the number of methylene groups replaced by the amine backbone).
  • p24 and p25 are each independently an integer of 1 to 3.
  • X 22 and X 23 are preferably an alkoxy group, a halogen atom, a cyano group, or an isocyanate group, more preferably an alkoxy group, and an alkoxy group having 1 to 4 carbon atoms (particularly a methoxy group or an ethoxy group). Is more preferable.
  • a plurality of amine skeletons ⁇ NR 100 ⁇ may be present, and in that case, the number of amine skeletons is preferably 1 to 10, more preferably 1 to 5, and preferably 2 to 5. More preferred. Further, in this case, it is preferable to have an alkylene group between adjacent amine skeletons.
  • the alkylene group preferably has 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms. The number of carbon atoms of the alkylene group between adjacent amine skeletons is included in the total number of w.
  • the number of carbon atoms is preferably 5 or less, and more preferably 3 or less.
  • the amine skeleton -NR 100- is preferably -NH- (R 100 is a hydrogen atom).
  • R x24 and R x25 are preferably alkyl groups having 1 to 10 carbon atoms, and more preferably alkyl groups having 1 to 5 carbon atoms.
  • P24 and p25 are preferably integers of 2 to 3, and more preferably 3.
  • W is preferably 1 or more, more preferably 2 or more, preferably 20 or less, and more preferably 10 or less.
  • Organosilicon compound (C) represented by the following formula (c3) (hereinafter, organosilicon compound (C3))
  • Z 31 and Z 32 are reactive functional groups other than the hydrolyzable group and the hydroxy group, respectively.
  • the reactive functional group include a vinyl group, an ⁇ -methylvinyl group, a styryl group, a methacryloyl group, an acryloyl group, an amino group, an epoxy group, a ureido group, or a mercapto group.
  • Z 31 and Z 32 an amino group, a mercapto group, or a methacryloyl group is preferable, and an amino group is particularly preferable.
  • R x31, R x32, R x33 , R x34 are each independently a hydrogen atom or a carbon atoms is an alkyl group of 1 to 4, if R x31 there are a plurality differ plurality of R x31 are each may, if R x32 there are a plurality may be different plural R x32 are each may be the case where R x33 there are a plurality of different plural R x33 are each if R x34 there are multiple May have different R x 34s.
  • R x31 , R x32 , R x33 , and R x34 are preferably hydrogen atoms or alkyl groups having 1 to 2 carbon atoms, and more preferably hydrogen atoms.
  • Rf x31 , Rf x32 , Rf x33 , and Rf x34 are independently alkyl groups or fluorine atoms having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms, and there are a plurality of Rf x31. If you may be different plurality of Rf x31 respectively, differ if the Rf x32 there are a plurality may be different plurality of Rf x32, respectively, a plurality of Rf x33 If Rf x33 is present in plural even if well, a plurality of Rf x34 If Rf x34 there are a plurality may be different from each other.
  • Rf x31 , Rf x32 , Rf x33 , and Rf x34 are preferably alkyl groups or fluorine atoms having 1 to 10 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms.
  • Y 31 is, -NH -, - N (CH 3) - or -O-. And, in the case where the Y 31 there are a plurality may be different plurality of Y 31, respectively.
  • Y 31 is preferably ⁇ NH ⁇ .
  • X 31 , X 32 , X 33 , and X 34 are independently -OR c (R c is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an amino C 1-3 alkyl di C 1-3 alkoxysilyl. a is a group), if X 31 there are a plurality may be different plurality of X 31 are each, if X 32 there are a plurality may be different plurality of X 32 are each, X 33 is If there are two or more may be multiple X 33 are different each, a plurality of X 34 may be different from each if X 34 there are a plurality.
  • R c is preferably a hydrogen atom or ⁇ OR c , which is an alkyl group having 1 to 2 carbon atoms, and R c is more preferably a hydrogen atom.
  • p31 is an integer of 0 to 20
  • p32, p33, and p34 are independently integers of 0 to 10
  • p35 is an integer of 0 to 5
  • p36 is an integer of 1 to 10.
  • p37 is 0 or 1.
  • p31 is preferably 1 to 15, more preferably 3 to 13, and even more preferably 5 to 10.
  • P32, p33 and p34 are each independently preferably 0 to 5, more preferably all 0 to 2.
  • the p35 is preferably 1 to 5, more preferably 1 to 3.
  • p36 is preferably 1 to 5, more preferably 1 to 3.
  • P37 is preferably 1.
  • the organosilicon compound (C3) satisfies the condition that at least one of Z 31 and Z 32 is an amino group, or at least one of Y 31 is -NH- or -N (CH 3)-and is terminal.
  • p31 amino - ⁇ C (R x31) ( R x32) ⁇ - is, - ⁇ C (R x31) ( R x32) ⁇ - It is not necessary for bonded continuously, through the other units in the middle It may be combined with each other, and a total of p31 may be used. The same applies to the units enclosed by p32 to p37.
  • the organosilicon compound (C3), Z 31 and Z 32 is amino group, R x31 and R x32 are each a hydrogen atom, p31 is 3 to 13 (preferably 5 ⁇ 10), R x33 and R x34 is a hydrogen atom, Rf x31 to Rf x34 are all alkyl groups or fluorine atoms having 1 to 10 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms, and p32 to p34 are all. 0 to 5, Y 31 is -NH-, p35 is 0 to 5 (preferably 0 to 3), X 31 to X 34 are all -OH, and p36 is 1 to 5 (preferably). 1 to 3), and a compound having p37 of 1 is preferable.
  • the organosilicon compound (C3) is preferably represented by the following formula (c3-2).
  • Z 31 , Z 32 , X 31 , X 32 , X 33 , X 34 , and Y 31 are synonymous with these in the formula (c3), and p41 to p44 are independent of each other. Is an integer of 1 to 6, and p45 and 46 are independently 0 or 1, respectively.
  • Z 31 and Z 32 are preferably an amino group, a mercapto group, or a methacryloyl group, and particularly preferably an amino group.
  • X 31, X 32, X 33 , X 34, is more it is preferred that R c is -OR c is an alkyl group of a hydrogen atom, or C 1 ⁇ 2, R c is a hydrogen atom preferable.
  • Y 31 is preferably ⁇ NH ⁇ .
  • P41 to p44 are preferably 2 or more, preferably 5 or less, and more preferably 4 or less. It is preferable that both p45 and p46 are 0.
  • the mixed composition (cc) is a composition in which the organosilicon compound (C) is mixed, and the organosilicon compound (C) may be one kind or two or more kinds.
  • the mixed composition (cc) is obtained by mixing the organosilicon compound (C), and when a component other than the organosilicon compound (C) is mixed, the organosilicon compound (C) and other components are mixed. Is obtained by mixing.
  • the mixed composition (cc) also includes those whose reaction has proceeded after mixing, for example, during storage.
  • the mixed composition (cc) contains a condensate of the organosilicon compound (C), and more specifically, the above. It can be mentioned that the mixed composition (cc) contains an organosilicon compound (C3') in which the organosilicon compound (C3) is condensed and bonded at at least one of the above X 31 to X 34.
  • the organosilicon compound (C3') has two or more structures (c31-1) represented by the following formula (c31-1), and the structures (c31-1) have the following * 3 or * 4. It is a chain-like or cyclically bonded compound, and the bond at the following * 3 or * 4 is due to the condensation of the X 31 or X 32 of two or more of the organosilicon compounds (C3).
  • * 1 and * 2 of the following formula (c31-1) have at least the units enclosed by p31, p32, p33, p34, p35, (p36) -1, and p37 of the following formula (c31-2), respectively.
  • One type is bonded in any order and groups having a Z-terminal are bonded, and the groups that are bonded to * 1 and * 2 may be different for each of the plurality of structures (c31-1).
  • * 3 at the end is a hydrogen atom
  • * 4 is a hydroxy group.
  • Z is a reactive functional group other than the hydrolyzable group and the hydroxy group.
  • R x31 , R x32 , R x33 , R x34 , Rf x31 , Rf x32 , Rf x33 , Rf 34 , Y 31 , X 31 , X 32 , X 33 , X 34 , p31 to p37 are included in the above equation (c3). It is synonymous with these codes of.
  • organosilicon compound (C3) is a compound represented by the above formula (c3-2), as the organosilicon compound (C3'), for example, the structure represented by the following formula (c31-3) is described below * 3.
  • the structure represented by the following formula (c31-3) is bonded in a chain, the terminal * 3 is a hydrogen atom and the terminal * 4 is a hydroxy group.
  • the organosilicon compound (C3') is preferably a compound in which the structure represented by the above formula (c31-3) is bonded by 2 to 10 (preferably 3 to 8).
  • the mixed composition (cc) is preferably mixed with the solvent (E).
  • the solvent (E) is not particularly limited, and for example, water, an alcohol solvent, a ketone solvent, an ether solvent, a hydrocarbon solvent, an ester solvent, or the like can be used, and in particular, water, an alcohol solvent, or a ketone solvent can be used. , A hydrocarbon solvent is preferable.
  • Examples of the alcohol solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol and the like.
  • Examples of the ketone solvent include acetone, methyl ethyl ketone, and methyl isobutyl ketone.
  • Examples of the ether solvent include diethyl ether, dipropyl ether, tetrahydrofuran, 1,4-dioxane and the like.
  • Examples of the hydrocarbon solvent include an aliphatic hydrocarbon solvent such as pentane and hexane, an alicyclic hydrocarbon solvent such as cyclohexane, and an aromatic hydrocarbon solvent such as benzene, toluene and xylene.
  • Examples of the ester solvent include ethyl acetate, propyl acetate, butyl acetate and the like.
  • the total amount of the composition (cc) is 100% by mass
  • the total amount of the organosilicon compound (C) is preferably 0.005% by mass or more, more preferably 0.01% by mass or more. It is more preferably 0.02% by mass or more, further preferably 0.1% by mass or more, still preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 2% by mass or less. be.
  • the amount of the above-mentioned organosilicon compound (C) can be adjusted at the time of preparation of the composition.
  • the amount of the organosilicon compound (C) may be calculated from the analysis result of the composition.
  • the base material (s) is preferably a layer having a function of preventing reflection of incident light on the surface on the intermediate layer (c) side, specifically, in a visible light region of 380 to 780 nm.
  • the surface on the intermediate layer (c) side is preferably a layer exhibiting a reflection characteristic in which the reflectance is reduced to about 5.0% or less, more preferably 4.80% or less, still more preferably 4. It is less than 5.5%.
  • the reflectance may be evaluated by the spectral reflectance at a wavelength of 530 nm.
  • the base material (s) preferably has a surface Si ratio of 1 atomic% or more in at least the outermost layer on the intermediate layer (c) side, and the base material (s) is preferably an organic material or an inorganic material.
  • the surface Si ratio is at least a predetermined value, the surface of the base material (s) and the components constituting the intermediate layer (c) or the water-repellent layer (r) are likely to be bonded to each other, and the laminate of the present invention is water-repellent.
  • the wear resistance of the surface on the layer (r) side is further improved.
  • the surface Si ratio is more preferably 5 atomic% or more, further preferably 10 atomic% or more, still more preferably 20 atomic% or more, and may be 40 atomic% or less.
  • the base material (s) may be composed of one kind of material or two or more kinds of materials.
  • the material constituting the base material (s) include acrylic resin, polycarbonate resin, polyester resin (polyethylene terephthalate, etc.), styrene resin, acrylic-styrene copolymer resin, cellulose resin, polyolefin resin, and vinyl resin (polyethylene, Thermoplastic resins such as polyvinyl chloride, polystyrene, vinylbenzyl chloride resin, polyvinyl alcohol, etc .; or thermosetting resins such as phenol resin, urea resin, melamine resin, epoxy resin, unsaturated polyester, silicone resin, urethane resin, etc.
  • resin materials such as engineering plastics such as polyamide resins, polyimide resins and polyamideimide resins, or metal oxides such as titanium, zirconium, aluminum, niobium, tantalum, lanthanum or silicon can be mentioned.
  • the base material (s) when the base material (s) is composed of one kind of material, it may be a resin layer having a surface Si ratio of 1 atomic% or more, or even a metal oxide layer such as silica. good.
  • a protective layer provided on the resin layer to protect the article from scratches in applications requiring abrasion resistance such as displays of electronic devices.
  • a hard coat layer it may be referred to as a hard coat layer.
  • the layer is provided.
  • the above-mentioned thermosetting resin, thermoplastic resin, or engineering plastic can be used, and polyester resin is particularly preferable.
  • the above-mentioned hard coat layer is a layer having a surface hardness, and the hardness is, for example, a pencil hardness of 2H or more.
  • the hard coat layer may have a single layer structure or a multi-layer structure.
  • the hard coat layer contains a hard coat layer resin
  • the hard coat layer resin include acrylic resin, epoxy resin, urethane resin, vinylbenzyl chloride resin, vinyl resin, silicone resin, and these.
  • examples thereof include ultraviolet curable type, electron beam curable type, and heat curable type resins such as mixed resins, and as described above, it is preferable that the surface Si ratio of the resin forming the hard coat layer is 1 atomic% or more. ..
  • the hard coat layer preferably contains an acrylic resin and has a surface Si ratio of 1 atomic% or more in order to exhibit high hardness. It is also preferable to include an epoxy resin because the adhesion to the water-repellent layer (r) via the intermediate layer (c) tends to be good.
  • the hard coat layer may further contain an ultraviolet absorber, a metal oxide such as silica or alumina, or an inorganic filler such as polyorganosiloxane.
  • an ultraviolet absorber such as silica or alumina
  • an inorganic filler such as polyorganosiloxane.
  • an antireflection layer may be provided on the resin layer, or a hard coat layer provided on the resin layer. It is also preferable that an antireflection layer is further provided on the top, and in this case, the resin layer, the hard coat layer, the antireflection layer, the intermediate layer (c), and the water repellent layer (r) are laminated in this order. ..
  • the material constituting the resin layer the above-mentioned thermosetting resin, thermoplastic resin, or engineering plastic can be used.
  • the antireflection layer is a layer having a function of preventing the reflection of incident light, and is a layer exhibiting a reflection characteristic in which the reflectance is reduced to about 5% or less in the visible light region of 380 to 780 nm.
  • the structure of the antireflection layer is not particularly limited, and may be a single-layer structure or a multi-layer structure. In the case of a multi-layer structure, a structure in which low refractive index layers and high refractive index layers are alternately laminated is preferable, and the total number of layers is preferably 2 to 20.
  • the material constituting the high refractive index layer examples include oxides of titanium, zirconium, aluminum, niobium, tantalum and lanthanum, and examples of the material constituting the low refractive index layer include oxides of silicon (that is, silica).
  • the antireflection layer having a multi-layer structure a structure in which SiO 2 and ZrO 2 or SiO 2 and Nb 2 O 5 are alternately laminated and the outermost layer on the opposite side to the base material (s) is SiO 2 is preferable. ..
  • the antireflection layer can be formed, for example, by a vapor deposition method.
  • the reflection characteristics and / or the material may be satisfied in at least the outermost layer on the intermediate layer (c) side of the base material (s), and preferably the base material (s).
  • s) may be filled with a thickness of 10% or more (thickness of the base material (s)) from the outermost surface layer on the intermediate layer (c) side, and more preferably 40% or more. It is more preferable that the entire base material (s) is filled.
  • the thickness of the base material (s) is, for example, 1 to 498 ⁇ m, preferably 1 to 300 ⁇ m, more preferably 1 to 100 ⁇ m, still more preferably 10 to 95 ⁇ m, and particularly preferably 30 to 90 ⁇ m.
  • the water contact angle (initial contact angle) when the laminate of the present invention is evaluated according to the method described in Examples described later is, for example, 105 ° or more, more preferably 110 ° or more, and for example 125 °. It is as follows.
  • the first method for producing the laminate of the present invention includes (i) a step of applying the mixed composition (cc) on the base material (s) and (ii) a coated surface of the mixed composition (cc). Including a step of applying the mixed composition (ca) to, and (iii) a step of curing the mixed composition (cc) and the mixed composition (ca), and applying the mixed composition (cc).
  • the intermediate layer (c) is formed from the layer, and the water-repellent layer (r) is formed from the coating layer of the mixed composition (ca).
  • a known method can be used, but a spin coating method or a dip coating method is preferable.
  • the mixed composition (ca) for forming the water-repellent layer (r) is applied to the coated surface of the mixed composition (cc) and dried to obtain the mixed composition (cc) from the coated layer.
  • the intermediate layer (c) can be formed, and the water-repellent layer (r) can be formed from the coating layer of the mixed composition (ca).
  • the intermediate layer (c) may be formed during or after the application of the mixed composition (cc), and the intermediate layer (c) and the water-repellent layer (r) may be formed. May proceed at the same time.
  • Examples of the method for applying the composition for forming the water-repellent layer (r) include a dip coating method, a roll coating method, a bar coating method, a spin coating method, a spray coating method, a die coating method, and a gravure coating method. ..
  • the laminate of the present invention can be produced by allowing it to stand at room temperature in the air for, for example, 1 hour or more (usually 24 hours or less).
  • room temperature is 5 to 60 ° C, preferably 15 to 40 ° C.
  • the humidity condition when the product is allowed to stand at room temperature may be 50 to 90% RH.
  • the organosilicon compound (C) is vapor-deposited on the base material (s) to form the intermediate layer (c), and the intermediate layer (c) is formed.
  • the mixed composition (ca) is applied onto the coating layer and cured to form the water-repellent layer (r) from the coating layer of the mixed composition (ca).
  • the organosilicon compound (C) alone may be vapor-deposited on the base material (s), or the organosilicon compound (c) may be vapor-deposited.
  • a solid substance that is, the organosilicon compound (C) obtained by removing the solvent from the mixed composition of C) and the solvent may be vapor-deposited on the base material (s). After applying the composition for forming the water-repellent layer (r), the same procedure as in the first method may be applied.
  • the base material (s) is hydrophilized before the composition (cc) is applied or before the organosilicon compound (C) is vapor-deposited.
  • the hydrophilic treatment include hydrophilization treatments such as corona treatment, plasma treatment, ultraviolet treatment, and ion cleaning treatment, and plasma treatment and ion cleaning treatment are more preferable.
  • hydrophilization treatment such as plasma treatment
  • functional groups such as OH groups and COOH groups can be formed on the surface of the base material, especially when such functional groups are formed on the surface of the base material.
  • the adhesion between the intermediate layer (c) and the base material (s) can be further improved.
  • the present invention also provides a flexible display device comprising the optical laminate of the present invention.
  • the laminate of the present invention can preferably be used as a front plate in a flexible display device, and the front plate may be referred to as a window film.
  • the flexible display device is preferably composed of a laminated body for a flexible display device and an organic EL display panel, and the laminated body for the flexible display device is arranged on the visual side with respect to the organic EL display panel and is configured to be bendable. ing.
  • the laminated body for a flexible display device may further contain a polarizing plate (preferably a circular polarizing plate), a touch sensor, and the like, and the stacking order thereof is arbitrary, but the window film (that is, the present invention) is viewed from the visual side. It is preferable that the laminated body), the polarizing plate, and the touch sensor are laminated in this order, or the window film, the touch sensor, and the polarizing plate are laminated in this order. If a polarizing plate is present on the visual side of the touch sensor, the pattern of the touch sensor is less likely to be visually recognized and the visibility of the displayed image is improved, which is preferable. Each member can be laminated using an adhesive, an adhesive, or the like. Further, the flexible display device can be provided with a light-shielding pattern formed on at least one surface of any of the layers of the window film, the polarizing plate, and the touch sensor.
  • the flexible display device of the present invention preferably includes a polarizing plate, particularly a circular polarizing plate.
  • the circular polarizing plate is a functional layer having a function of transmitting only a right or left circularly polarized light component by laminating a ⁇ / 4 retardation plate on a linear polarizing plate.
  • the external light is converted to right-handed circularly polarized light and reflected by the organic EL panel to block the left-handed circularly polarized light, and only the light emitting component of the organic EL is transmitted to suppress the influence of the reflected light. It is used to make it easier to see.
  • the absorption axis of the linear polarizing plate and the slow axis of the ⁇ / 4 retardation plate need to be theoretically 45 degrees, but practically, they are 45 ⁇ 10 degrees.
  • the linear polarizing plate and the ⁇ / 4 retardation plate do not necessarily have to be laminated adjacent to each other, and the relationship between the absorption axis and the slow phase axis may satisfy the above range. It is preferable to achieve perfect circularly polarized light at all wavelengths, but it is not always necessary in practical use. Therefore, the circularly polarizing plate in the present invention also includes an elliptical polarizing plate. It is also preferable to further laminate a ⁇ / 4 retardation film on the visible side of the linear polarizing plate to convert the emitted light into circularly polarized light to improve the visibility when wearing polarized sunglasses.
  • the linear polarizing plate is a functional layer that allows light vibrating in the transmission axis direction to pass through, but has the function of blocking the polarization of vibration components perpendicular to it.
  • the linear polarizing plate may be configured to include a linear polarizing element alone or a linear polarizing element and a protective film attached to at least one surface thereof.
  • the thickness of the linear polarizing plate may be 200 ⁇ m or less, preferably 0.5 to 100 ⁇ m. When the thickness of the linear polarizing plate is within the above range, the flexibility of the linear polarizing plate tends to be difficult to decrease.
  • the linear polarizer may be a film-type polarizer produced by dyeing and stretching a polyvinyl alcohol (hereinafter, may be abbreviated as PVA) -based film.
  • a dichroic dye such as iodine is adsorbed on the PVA-based film oriented by stretching, or the dichroic dye is oriented in a state of being adsorbed on the PVA to exhibit polarization performance.
  • other steps such as swelling, cross-linking with boric acid, washing with an aqueous solution, and drying may be included.
  • the stretching and dyeing steps may be performed on the PVA-based film alone, or may be performed in a state of being laminated with another film such as polyethylene terephthalate.
  • the thickness of the PVA-based film used is preferably 10 to 100 ⁇ m, and the draw ratio is preferably 2 to 10 times.
  • a liquid crystal coating type polarizer formed by coating a liquid crystal polarizing composition can be mentioned.
  • the liquid crystal polarizing composition may contain a liquid crystal compound and a dichroic dye compound.
  • the liquid crystal compound may have a property of exhibiting a liquid crystal state, and is particularly preferable when it has a higher-order orientation state such as a smectic phase because it can exhibit high polarization performance.
  • the liquid crystal compound preferably has a polymerizable functional group.
  • the dichroic dye compound is a dye that is oriented together with the liquid crystal compound and exhibits dichroism, and may have a polymerizable functional group, and the dichroic dye itself has liquid crystallinity. You may be doing it. Any of the compounds contained in the liquid crystal polarizing composition has a polymerizable functional group.
  • the liquid crystal polarizing composition can further contain an initiator, a solvent, a dispersant, a leveling agent, a stabilizer, a surfactant, a cross-linking agent, a silane coupling agent and the like.
  • the liquid crystal polarizing layer is manufactured by applying a liquid crystal polarizing composition on an alignment film to form a liquid crystal polarizing layer.
  • the liquid crystal polarizing layer can be formed to be thinner than the film-type polarizing element, and the thickness is preferably 0.5 to 10 ⁇ m, more preferably 1 to 5 ⁇ m.
  • the alignment film is produced, for example, by applying an alignment film forming composition on a substrate and imparting orientation by rubbing, polarized light irradiation, or the like.
  • the alignment film forming composition contains an alignment agent, and may further contain a solvent, a cross-linking agent, an initiator, a dispersant, a leveling agent, a silane coupling agent, and the like.
  • the alignment agent include polyvinyl alcohols, polyacrylates, polyamic acids, and polyimides.
  • an orientation agent that imparts orientation by polarization irradiation it is preferable to use an orientation agent containing a synnamate group.
  • the weight average molecular weight of the polymer used as the alignment agent is, for example, about 10,000 to 1,000,000.
  • the thickness of the alignment film is preferably 5 to 10,000 nm, and more preferably 10 to 500 nm in that the alignment regulating force is sufficiently exhibited.
  • the liquid crystal polarizing layer can be peeled off from the base material, transferred and laminated, or the base material can be laminated as it is. It is also preferable that the base material serves as a transparent base material for a protective film, a retardation plate, and a window film.
  • any transparent polymer film may be used, and the same materials and additives used for the transparent base material of the window film can be used. Further, it may be a coating type protective film obtained by applying a cationic curing composition such as an epoxy resin or a radical curing composition such as acrylate and curing the film.
  • the protective film may be a plasticizer, an ultraviolet absorber, an infrared absorber, a colorant such as a pigment or a dye, a fluorescent whitening agent, a dispersant, a heat stabilizer, a light stabilizer, an antioxidant, an antioxidant, if necessary. , Lubricants, solvents and the like may be contained.
  • the thickness of the protective film is preferably 200 ⁇ m or less, more preferably 1 to 100 ⁇ m. When the thickness of the protective film is within the above range, the flexibility of the film tends to be difficult to decrease.
  • the ⁇ / 4 retardation plate is a film that gives a retardation of ⁇ / 4 in a direction orthogonal to the traveling direction of incident light (in-plane direction of the film).
  • the ⁇ / 4 retardation plate may be a stretch-type retardation plate manufactured by stretching a polymer film such as a cellulose-based film, an olefin-based film, or a polycarbonate-based film.
  • the ⁇ / 4 retardation plate may be used as a retardation adjuster, a plastic agent, an ultraviolet absorber, an infrared absorber, a colorant such as a pigment or a dye, a fluorescent whitening agent, a dispersant, a heat stabilizer, and a light stabilizer.
  • the thickness of the stretched retardation plate is preferably 200 ⁇ m or less, more preferably 1 to 100 ⁇ m.
  • the thickness of the stretchable retardation plate is within the above range, the flexibility of the stretchable retardation plate tends to be difficult to decrease.
  • the ⁇ / 4 retardation plate there is a liquid crystal coating type retardation plate formed by coating a liquid crystal composition.
  • the liquid crystal composition contains a liquid crystal compound exhibiting a liquid crystal state such as nematic, cholesteric, and smectic.
  • the liquid crystal compound has a polymerizable functional group.
  • the liquid crystal composition can further contain an initiator, a solvent, a dispersant, a leveling agent, a stabilizer, a surfactant, a cross-linking agent, a silane coupling agent, and the like.
  • the liquid crystal coating type retardation plate can be manufactured by applying a liquid crystal composition on a substrate and curing the liquid crystal composition to form a liquid crystal retardation layer, similarly to the liquid crystal polarizing layer.
  • the liquid crystal coating type retardation plate can be formed to be thinner than the stretch type retardation plate.
  • the thickness of the liquid crystal polarizing layer is preferably 0.5 to 10 ⁇ m, more preferably 1 to 5 ⁇ m.
  • the liquid crystal coating type retardation plate can be peeled off from the base material, transferred and laminated, or the base material can be laminated as it is. It is also preferable that the base material serves as a transparent base material for a protective film, a retardation plate, and a window film.
  • the in-plane phase difference is preferably 100 to 4 so that it becomes ⁇ / 4 with respect to the vicinity of 560 nm, which has high luminosity factor. It is designed to be 180 nm, more preferably 130-150 nm.
  • a reverse dispersion ⁇ / 4 retardation plate using a material having a birefringence wavelength dispersion characteristic opposite to the usual one is preferable in that visibility is good.
  • a stretchable retardation plate can be used as described in JP-A-2007-232873, and a liquid crystal coating type retardation plate can be used as described in JP-A-2010-30979. ..
  • a technique for obtaining a wideband ⁇ / 4 retardation plate by combining with a ⁇ / 2 retardation plate is also known (for example, Japanese Patent Application Laid-Open No. 10-90521).
  • the ⁇ / 2 retardation plate is also manufactured by the same material method as the ⁇ / 4 retardation plate.
  • the combination of the stretchable retardation plate and the liquid crystal coating type retardation plate is arbitrary, but the thickness can be reduced by using the liquid crystal coating type retardation plate in both cases.
  • a method of laminating a positive C plate on the circularly polarizing plate in order to improve visibility in an oblique direction is known (for example, Japanese Patent Application Laid-Open No. 2014-224738).
  • the positive C plate may be a liquid crystal coating type retardation plate or a stretched retardation plate.
  • the phase difference in the thickness direction of the retardation plate is preferably ⁇ 200 to ⁇ 20 nm, more preferably ⁇ 140 to ⁇ 40 nm.
  • the flexible display device of the present invention preferably includes a touch sensor.
  • the touch sensor is used as an input means.
  • Examples of the touch sensor include various types such as a resistive film method, a surface acoustic wave method, an infrared method, an electromagnetic induction method, and a capacitance method, and a capacitance method is preferable.
  • the capacitive touch sensor is divided into an active region and an inactive region located outside the active region.
  • the active area is an area corresponding to the area where the screen is displayed on the display panel (display unit), the area where the user's touch is sensed, and the inactive area is the area where the screen is not displayed on the display device (non-active area). This is the area corresponding to the display unit).
  • the touch sensor is formed in a substrate having flexible characteristics, a sensing pattern formed in an active region of the substrate, and an inactive region of the substrate, and is connected to an external drive circuit via the sensing pattern and a pad portion.
  • Each sensing line for can be included.
  • the substrate having flexible characteristics the same material as the transparent substrate of the window film can be used.
  • the sensing pattern can include a first pattern formed in the first direction and a second pattern formed in the second direction.
  • the first pattern and the second pattern are arranged in different directions from each other.
  • the first pattern and the second pattern are formed in the same layer, and each pattern must be electrically connected in order to sense the touched point.
  • the first pattern is a form in which a plurality of unit patterns are connected to each other via a joint, but the second pattern has a structure in which a plurality of unit patterns are separated from each other in an island form, so that the second pattern is electrically operated.
  • a separate bridge electrode is required for the connection.
  • a well-known transparent electrode can be applied to the electrode for connecting the second pattern.
  • Examples of the material of the transparent electrode include indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), indium zinc oxide oxide (IZTO), and indium gallium zinc oxide (IGZO). , Cadmium tin oxide (CTO), PEDOT (poly (3,4-ethylenedioxythiophene)), carbon nanotubes (CNT), graphene, metal wire and the like, and ITO is preferable. These can be used alone or in combination of two or more.
  • the metal used for the metal wire is not particularly limited, and examples thereof include silver, gold, aluminum, copper, iron, nickel, titanium, telenium, chromium, etc., and these may be used alone or in combination of two or more. Can be done.
  • the bridge electrode can be formed on the upper part of the insulating layer via the insulating layer on the upper part of the sensing pattern, the bridge electrode is formed on the substrate, and the insulating layer and the sensing pattern can be formed on the bridge electrode.
  • the bridge electrode can be made of the same material as the sensing pattern, or it can be made of molybdenum, silver, aluminum, copper, palladium, gold, platinum, zinc, tin, titanium or two or more alloys of these. can. Since the first pattern and the second pattern must be electrically insulated, an insulating layer is formed between the sensing pattern and the bridge electrode.
  • the insulating layer may be formed only between the joint of the first pattern and the bridge electrode, or may be formed as a layer covering the entire sensing pattern. In the case of a layer covering the entire sensing pattern, the bridge electrode can connect the second pattern through a contact hole formed in the insulating layer.
  • the touch sensor is induced by a difference in transmittance between a pattern region in which a sensing pattern is formed and a non-pattern region in which a sensing pattern is not formed, specifically, a difference in refractive index in these regions.
  • An optical adjustment layer may be further included between the substrate and the electrode as a means for appropriately compensating for the difference in light transmittance.
  • the optical control layer may contain an inorganic insulating material or an organic insulating material.
  • the optical control layer can be formed by coating a photocurable composition containing a photocurable organic binder and a solvent on a substrate.
  • the photocurable composition may further contain inorganic particles.
  • the refractive index of the optical control layer can be increased by the inorganic particles.
  • the photocurable organic binder contains a copolymer of each monomer such as an acrylate-based monomer, a styrene-based monomer, and a carboxylic acid-based monomer, as long as the effects of the present invention are not impaired. be able to.
  • the photocurable organic binder may be, for example, a copolymer containing different repeating units such as an epoxy group-containing repeating unit, an acrylate repeating unit, and a carboxylic acid repeating unit. Examples of the inorganic particles include zirconia particles, titania particles, alumina particles and the like.
  • the photocuring composition may further contain additives such as a photopolymerization initiator, a polymerizable monomer, and a curing aid.
  • ⁇ Adhesive layer> Each layer (window film, circularly polarizing plate, touch sensor) forming the laminate for the flexible image display device and the film member (straight polarizing plate, ⁇ / 4 retardation plate, etc.) constituting each layer are joined by an adhesive.
  • the adhesive include water-based adhesives, organic solvent-based adhesives, solvent-free adhesives, solid adhesives, solvent volatilization adhesives, moisture-curable adhesives, heat-curable adhesives, anaerobic curable adhesives, and active energy ray-curable adhesives.
  • adhesives such as mold adhesives, hardener mixed adhesives, heat-melt adhesives, pressure-sensitive adhesives (adhesives), and re-wet adhesives can be used, preferably aqueous solvent volatilization. Mold adhesives, active energy ray-curable adhesives, and adhesives can be used.
  • the thickness of the adhesive layer can be appropriately adjusted according to the required adhesive force and the like, and is preferably 0.01 to 500 ⁇ m, more preferably 0.1 to 300 ⁇ m.
  • the laminated body for a flexible image display device has a plurality of adhesive layers, and the thickness and type of each may be the same or different.
  • a polyvinyl alcohol-based polymer a water-soluble polymer such as starch, an ethylene-vinyl acetate emulsion, a styrene-butadiene emulsion, or the like in an aqueous-dispersed state can be used as the main polymer.
  • a cross-linking agent a silane compound, an ionic compound, a cross-linking catalyst, an antioxidant, a dye, a pigment, an inorganic filler, an organic solvent and the like may be blended.
  • the water-based solvent volatilization type adhesive When adhering with the water-based solvent volatilization type adhesive, the water-based solvent volatilization type adhesive can be injected between the layers to be adhered, the adherend layers are bonded, and then dried to impart adhesiveness.
  • the thickness of the adhesive layer is preferably 0.01 to 10 ⁇ m, more preferably 0.1 to 1 ⁇ m.
  • the thickness and type of each layer may be the same or different.
  • the active energy ray-curable adhesive can be formed by curing an active energy ray-curable composition containing a reactive material that is irradiated with active energy rays to form an adhesive layer.
  • the active energy ray-curable composition can contain at least one polymer of a radical-polymerizable compound and a cationically polymerizable compound similar to those contained in the hard coat composition.
  • the radically polymerizable compound the same compound as the radically polymerizable compound in the hard coat composition can be used.
  • the cationically polymerizable compound the same compound as the cationically polymerizable compound in the hard coat composition can be used.
  • an epoxy compound is particularly preferable. It is also preferable to include a monofunctional compound as a reactive diluent in order to reduce the viscosity of the adhesive composition.
  • the active energy ray composition can contain a monofunctional compound in order to reduce the viscosity.
  • the monofunctional compound include an acrylate-based monomer having one (meth) acryloyl group in one molecule and a compound having one epoxy group or oxetanyl group in one molecule, for example, glycidyl (meth). ) Examples include acrylate.
  • the active energy ray composition can further contain a polymerization initiator. Examples of the polymerization initiator include radical polymerization initiators, cationic polymerization initiators, radicals and cationic polymerization initiators, and these are appropriately selected and used.
  • These polymerization initiators are decomposed by at least one of activation energy ray irradiation and heating to generate radicals or cations to promote radical polymerization and cation polymerization.
  • an initiator that can initiate at least one of radical polymerization or cationic polymerization by irradiation with active energy rays can be used.
  • the active energy ray-curable composition further comprises an ion trapping agent, an antioxidant, a chain transfer agent, an adhesion imparting agent, a thermoplastic resin, a filler, a fluid viscosity modifier, a plasticizer, a defoaming agent solvent, an additive, and a solvent. Can be included.
  • the active energy ray-curable composition is applied to either or both of the layers to be adhered, and then bonded to each layer. Alternatively, both layers to be adhered can be adhered by irradiating them with active energy rays and curing them.
  • the thickness of the adhesive layer is preferably 0.01 to 20 ⁇ m, more preferably 0.1 to 10 ⁇ m.
  • the thickness and type of the respective layers may be the same or different.
  • the pressure-sensitive adhesive is classified into an acrylic pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, and the like according to the main polymer, and any of them can be used.
  • the pressure-sensitive adhesive may contain a cross-linking agent, a silane compound, an ionic compound, a cross-linking catalyst, an antioxidant, a tackifier, a plasticizer, a dye, a pigment, an inorganic filler and the like.
  • a pressure-sensitive adhesive layer is formed by dissolving and dispersing each component constituting the pressure-sensitive adhesive in a solvent to obtain a pressure-sensitive adhesive composition, applying the pressure-sensitive adhesive composition onto a substrate, and then drying the mixture.
  • the adhesive layer may be directly formed, or a separately formed base material may be transferred. It is also preferable to use a release film to cover the adhesive surface before bonding.
  • the thickness of the adhesive layer is preferably 0.1 to 500 ⁇ m, more preferably 1 to 300 ⁇ m.
  • the thickness and type of the respective layers may be the same or different.
  • the shading pattern can be applied as at least a part of the bezel or housing of the flexible image display device.
  • the light-shielding pattern hides the wiring arranged at the edge of the flexible image display device to make it difficult to see, thereby improving the visibility of the image.
  • the shading pattern may be in the form of a single layer or multiple layers.
  • the color of the light-shielding pattern is not particularly limited, and may be various colors such as black, white, and metallic.
  • the light-shielding pattern can be formed of a pigment for embodying color and a polymer such as an acrylic resin, an ester resin, an epoxy resin, polyurethane, or silicone. They can also be used alone or in mixtures of two or more.
  • the shading pattern can be formed by various methods such as printing, lithography, and inkjet.
  • the thickness of the shading pattern is preferably 1 to 100 ⁇ m, more preferably 2 to 50 ⁇ m. It is also preferable to give a shape such as an inclination in the thickness direction of the light-shielding pattern.
  • Abrasion resistance test Using a steel wool testing machine (manufactured by Daiei Seiki Co., Ltd.) equipped with steel wool # 0000 (manufactured by Bonster), the load is applied with the steel wool in contact with the surface of the laminate (water repellent layer (r)).
  • a wear test was carried out by applying 1000 g, and the test was repeated until peeling / scratches were confirmed visually, and the wear resistance was evaluated by the number of tests when peeling / scratches were confirmed. The presence or absence of peeling and scratches was confirmed at an illuminance of 1000 lux.
  • Thickness measurement The thickness of the base material (s) was measured using DIGIMICRO (model number: MFC-101A) manufactured by Nikon Corporation. In each of the examples and comparative examples, the thickness of the water-repellent layer (r) was several nm, and the thickness of the intermediate layer (c) was about 5 to 30 nm.
  • Example 1 A reaction product of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane and chloropropyltrimethoxysilane (trade name) described in JP2012-197330A, which is represented by the following formula as an organic silicon compound (C).
  • a solution prepared by mixing 0.25% by mass of X-12-5263HP (manufactured by Shin-Etsu Chemical Industry Co., Ltd.) and 99.75% by mass of hexane as the solvent (E) is stirred at room temperature for forming the intermediate layer (c). A solution was obtained.
  • an AR film having a thickness of 84 ⁇ m was prepared as the base material (s).
  • the AR film is a film in which SiO 2 and a metal oxide (however, other than SiO 2 ) are alternately laminated on a resin layer by a vacuum vapor deposition method to make the outermost surface SiO 2 .
  • Substrate (s) measured by the above method The surface Si ratio of was 31.5 atomic%.
  • the surface of the AR film is activated by atmospheric pressure plasma treatment, and the intermediate layer (c) forming solution is applied to the activated surface using OPTICOAT MS-A100 (spin coater) manufactured by MIKASA Co., Ltd.
  • An intermediate layer (c) was obtained by coating under the conditions of a coating liquid volume of 200 ⁇ l, a rotation speed of 2000 rpm, and a rotation speed of 20 seconds.
  • organosilicon compound (A) Optool (registered trademark) UF503 manufactured by Daikin Industries, Ltd. (containing 20% by mass of the organosilicon compound (A) and 80% by mass of Novec7200 as the solvent), and the organosilicon compound ( FAS13E (C 6 F 13- C 2 H 4- Si (OC 2 H 5 ) 3 , manufactured by Tokyo Kasei Kogyo Co., Ltd.) as B), FC-3283 (C 9 F 21 N, Florinate, 3M) as solvent (D)
  • the water-repellent layer (r) is mixed and stirred at room temperature for a predetermined time. A forming solution was obtained.
  • Optool (registered trademark) UF503 is an organosilicon compound in which a monovalent group having a perfluoropolyether structure and a hydrolyzable group are each bonded to a silicon atom.
  • the proportion (solid content) of the organosilicon compound (A) in 100% by mass of the water-repellent layer (r) forming solution is 0.085% by mass, and the proportion of the organosilicon compound (B) is 0.05% by mass. Met.
  • the water-repellent layer (r) forming solution was applied onto the intermediate layer (c) using a spray coater manufactured by Apiros Co., Ltd.
  • the conditions for spray coating are scan speed: 600 mm / sec, pitch: 5 mm, liquid volume: 6 cc / min, atomizing air: 350 kPa, and gap: 70 mm. Then, it was fired at 80 ° C. for 30 minutes to obtain a laminate containing the base material (s), the intermediate layer (c), and the water-repellent layer (r) in this order.
  • Example 2 The base material (s), the intermediate layer (c), and the water-repellent layer (s) are the same as in Example 1 except that the base material (s) is changed to an AR film having a surface Si ratio of 31.3 atomic%. A laminate containing r) in this order was obtained.
  • Example 3 A laminate containing the base material (s), the intermediate layer (c), and the water-repellent layer (r) in this order was obtained in the same manner as in Example 2 except that butyl acetate was used as the solvent (E). ..
  • Example 4 The base material (s), the intermediate layer (c), and the water-repellent layer (r) are arranged in this order in the same manner as in Example 1 except that the base material (s) is changed to a hard coat film having a thickness of 45 ⁇ m. A laminate containing the mixture was obtained.
  • the hard coat film is a film in which an acrylic hard coat layer having a surface Si ratio of 1.8 atomic% is laminated on a resin layer composed of polyethylene terephthalate, and is subjected to atmospheric pressure plasma treatment similar to that in Example 1. The surface of the acrylic hard coat layer was subjected to the activation treatment according to the above.
  • Example 5 The substrate (s) was the same as in Example 1 except that the organosilicon compound (C) was changed to KBM-903 (manufactured by Shin-Etsu Chemical Co., Ltd.) and butyl acetate was used as the solvent (E). ), The intermediate layer (c), and the water-repellent layer (r) were obtained in this order.
  • Comparative Example 1 The base material (s) and the intermediate layer (c) are the same as in Example 1 except that the base material (s) is changed to an acrylic hard coat layer having a thickness of 60 ⁇ m and a surface Si ratio of 0 atomic%. ), A laminate containing the water-repellent layer (r) in this order was obtained.
  • Comparative Example 2 A laminate containing the base material (s), the intermediate layer (c), and the water-repellent layer (r) in this order was obtained in the same manner as in Comparative Example 1 except that the solvent (E) was changed to methyl ethyl ketone.
  • Table 1 shows the results of evaluating the laminates obtained in Examples and Comparative Examples by the above method.
  • the laminate of the present invention includes display devices such as touch panel displays, optical elements, semiconductor elements, building materials, nanoimprint technology, solar cells, windowpanes of automobiles and buildings, metal products such as cooking utensils, ceramic products such as tableware, and plastics. It can be suitably formed on automobile parts and the like, and is industrially useful. It is also preferably used for kitchens, bathrooms, wash basins, mirrors, articles of various members around toilets, and the like.

Abstract

L'invention concerne un corps multicouche qui est pourvu de manière séquentielle d'un matériau de base (s), d'une couche intermédiaire (c) et d'une couche hydrofuge (r) dans cet ordre, et qui est caractérisé en ce qu'elle satisfait aux exigences (1) et (2) décrites ci-après. (1) La réflectance, qui est obtenue par soustraction de la perte de réflexion de surface avant et de la perte de réflexion de surface arrière à partir de la réflectance qui est calculée, avec un champ de vision de 2 degrés (source de lumière C) de JIS Z8701, à partir de la réflectance spectrale à la longueur d'onde de 530 nm telle que mesurée sur la couche hydrofuge surface latérale (r) à l'angle d'incidence de 12° et à l'angle de réflexion de 12°, est de 4,5 % ou moins. (2) L'épaisseur du corps multicouche est inférieure ou égale à 500 µm.
PCT/JP2021/004722 2020-02-17 2021-02-09 Corps multicouche et dispositif d'affichage flexible WO2021166736A1 (fr)

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WO2024009914A1 (fr) * 2022-07-08 2024-01-11 ダイキン工業株式会社 Stratifié

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JP2023121714A (ja) * 2022-02-21 2023-08-31 住友化学株式会社 積層体、ウインドウフィルム及びタッチパネル
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