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WO2013115191A1 - Agent pour la prévention de l'accumulation d'empreintes, son procédé de production, composition pour revêtements durs, base comprenant une couche de revêtement dur et panneau tactile - Google Patents

Agent pour la prévention de l'accumulation d'empreintes, son procédé de production, composition pour revêtements durs, base comprenant une couche de revêtement dur et panneau tactile Download PDF

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Publication number
WO2013115191A1
WO2013115191A1 PCT/JP2013/051923 JP2013051923W WO2013115191A1 WO 2013115191 A1 WO2013115191 A1 WO 2013115191A1 JP 2013051923 W JP2013051923 W JP 2013051923W WO 2013115191 A1 WO2013115191 A1 WO 2013115191A1
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WO
WIPO (PCT)
Prior art keywords
group
hard coat
carbon atoms
silane compound
hydrolyzable silane
Prior art date
Application number
PCT/JP2013/051923
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English (en)
Japanese (ja)
Inventor
光太郎 山田
高橋　秀幸
古川　豊
Original Assignee
旭硝子株式会社
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Filing date
Publication date
Application filed by 旭硝子株式会社 filed Critical 旭硝子株式会社
Priority to JP2013556418A priority Critical patent/JP6206188B2/ja
Priority to CN201380007252.0A priority patent/CN104080877B/zh
Priority to KR1020147019644A priority patent/KR101969192B1/ko
Publication of WO2013115191A1 publication Critical patent/WO2013115191A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/08—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • 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
    • 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

Definitions

  • the present invention relates to an anti-fingerprint agent and a method for producing the same, a composition for hard coat, a substrate having a hard coat layer, and a touch panel.
  • Touch panels used for smartphones, tablet PCs, etc. are easily touched by human fingers during use, so that oily dirt due to fingerprints, sebum, sweat, etc. is likely to adhere.
  • oily dirt adheres it is difficult to be removed, and it is conspicuous depending on the amount of light and the like.
  • similar problems have been pointed out in display glasses, optical elements, sanitary equipment, and the like.
  • an active energy ray-curable polymerizable monomer containing a polyfunctional polymerizable monomer component having two or more (meth) acryloyl groups.
  • a water- and oil-repellency-imparting agent including an active energy ray-curable functional group, a water- and oil-repellent expression site, and a specific divalent hydrocarbon group in the molecular structure, and an active energy ray polymerization initiator
  • a technique is described in which a composition is applied to a substrate and cured to form a hard coat layer having excellent wear resistance and antifouling properties such as fingerprint adhesion prevention.
  • Patent Document 2 describes a method for producing a fluoroorganopolysiloxane resin having a perfluoroalkyl group or a perfluoropolyether group used in a film-forming composition.
  • a hydrolyzable silane compound having a perfluoroalkyl group, or a mixture of this with a hydrolyzable silane compound having an organic group (having no fluorine atom) is hydrolyzed under specific conditions to produce a fluoroorgano Obtained polysiloxane resin.
  • the film formed using this resin is excellent in adhesiveness, abrasion resistance, light resistance, antifouling property, water repellency, antireflection property, low refractive index and transparency.
  • the hard coat layer obtained by using the composition described in Patent Document 1 sometimes has insufficient light resistance for antifouling properties.
  • the fluoroorganopolysiloxane resin described in Patent Document 2 uses a hydrolyzable silane compound having a perfluoroalkyl group having 8 carbon atoms as a raw material, the environmental load is high.
  • the film obtained from the resin may not have sufficient hardness.
  • the present invention has been made in view of the above circumstances, and by adding it to a photocurable hard coat resin, the surface of the resulting hard coat layer has sufficient hardness, antifouling property, particularly fingerprint adhesion.
  • Providing a partially hydrolyzed condensate that can provide a protective property, can sufficiently secure the appearance and antifouling property of the hard coat layer, in particular, the light resistance of the anti-fingerprint property, and has a low environmental impact, and a method for producing the same With the goal.
  • the present invention also includes a hard coat composition capable of forming a hard coat layer having sufficient hardness, antifouling property, particularly anti-fingerprint property and light resistance, and appearance, which contains the partial hydrolysis condensate.
  • An object and a substrate having a hard coat layer using the same, and a touch panel using the substrate having the hard coat layer are provided.
  • the present invention provides a fingerprint adhesion preventive agent having the following constitutions [1] to [14], a method for producing the same, a hard coat composition, a substrate having a hard coat layer, and a touch panel.
  • An anti-fingerprint agent comprising Symbols in the formulas (a-1), (a-2) and (a-3) are as follows.
  • R f a perfluoroalkyl group having 1 to 6 carbon atoms or a monovalent group having 2 to 100 carbon atoms represented by R f1 OR f2 — (R f1 is a perfluoroalkyl having 1 to 6 carbon atoms) Group R f2 is a perfluoroalkylene group which may have an etheric oxygen atom between carbon-carbon atoms).
  • Q 1 a divalent organic group not containing a fluorine atom having 1 to 10 carbon atoms
  • Y a group having an ethylenic double bond
  • Q 2 a divalent organic group not containing a fluorine atom having 1 to 6 carbon atoms
  • R H1 , R H2 a hydrocarbon group having 1 to 6 carbon atoms
  • X 1 , X 2 , X 3 hydrolyzable group
  • p an integer from 0 to 3
  • r a number that is 0 or 1 and q + r is 1 or 2.
  • X 1 in formula (a-1), and X 2 , X 3 , R H1 , YQ 2 in the case where a plurality of X 1 exist in formula (a-2) or formula (a-3) May be different from each other or the same.
  • the partial hydrolysis-condensation product has a fluorine atom content of 20 to 40% by mass, and R f in the formula (a-1) is a perfluoroalkyl group having 1 to 6 carbon atoms, or R a monovalent group having 2 to 40 carbon atoms represented by f1 OR f2 — (R f1 is a perfluoroalkyl group having 1 to 6 carbon atoms, and R f2 has an etheric oxygen atom between the carbon-carbon atoms. Or a perfluoroalkylene group that may be present.) [1].
  • [3] A method for producing the fingerprint adhesion preventive agent of [1] or [2], wherein the hydrolyzable silane compound (a-1) represented by (a-1) 1 to 23,000 mol of the hydrolyzable silane compound (a-2) represented by (a-2), and the hydrolyzable silane compound (a-3) represented by (a-3).
  • a hydrolyzable silane compound mixture containing 20 to 11,500 moles is hydrolyzed and partially condensed in the presence of water, an organic solvent and an acid, and a fluorine atom content is 2.5 to 40% by weight.
  • a method for producing an anti-fingerprint agent comprising producing a hydrolyzed condensate.
  • the hydrolyzable silane compound (a-2) is added in an amount of 1 to 800 mol of the hydrolyzable silane compound (a-1) with respect to 100 mol of the hydrolyzable silane compound (a-1).
  • the anti-fingerprint agent according to [3] which is a partially hydrolyzed condensate produced by hydrolyzing and partially condensing a hydrolyzable silane compound mixture containing the silane compound (a-3) in a molar ratio of 20 to 300 mol. Manufacturing method.
  • the method for producing a fingerprint adhesion preventive agent according to [3] or [4], wherein the amount of water added is 5 to 100 parts by mass with respect to 100 parts by mass of the hydrolyzable silane compound mixture.
  • R f a perfluoroalkyl group having 1 to 6 carbon atoms or a monovalent group having 2 to 100 carbon atoms represented by R f1 OR f2 — (R f1 is a perfluoroalkyl having 1 to 6 carbon atoms) Group R f2 is a perfluoroalkylene group which may have an etheric oxygen atom between carbon-carbon atoms).
  • Q 1 a divalent organic group not containing a fluorine atom having 1 to 10 carbon atoms
  • Y a group having an ethylenic double bond
  • Q 2 a divalent organic group not containing a fluorine atom having 1 to 6 carbon atoms
  • R H1 , R H2 a hydrocarbon group having 1 to 6 carbon atoms
  • X 1 , X 2 , X 3 hydrolyzable group
  • p an integer from 0 to 3
  • r a number that is 0 or 1 and q + r is 1 or 2.
  • X 1 in formula (a-1), and X 2 , X 3 , R H1 , YQ 2 in the case where a plurality of X 1 exist in formula (a-2) or formula (a-3) May be different from each other or the same.
  • the partial hydrolysis-condensation product has a fluorine atom content of 20 to 40% by mass, and R f in the formula (a-1) is a perfluoroalkyl group having 1 to 6 carbon atoms, or R a monovalent group having 2 to 40 carbon atoms represented by f1 OR f2 — (R f1 is a perfluoroalkyl group having 1 to 6 carbon atoms, and R f2 has an etheric oxygen atom between the carbon-carbon atoms.
  • the composition for hard coat according to [9] which may be a perfluoroalkylene group.
  • a touch panel comprising a substrate having the hard coat layer of [13].
  • the surface of the resulting hard coat layer can be provided with sufficient hardness and anti-fingerprint adhesion. Moreover, the light resistance of these characteristics is excellent and the environmental load is small.
  • the method for producing an anti-fingerprint agent of the present invention can be used by adding to a photocurable hard coat resin to provide sufficient hardness and anti-fingerprint adhesion to the surface of the resulting hard coat layer. The agent can be manufactured.
  • the hard coat composition of the present invention can form a hard coat layer having good appearance, sufficient hardness, antifouling property, and fingerprint adhesion preventing property on a substrate.
  • the substrate having the hard coat layer of the present invention and the touch panel using the substrate having the hard coat layer have a good appearance of the hard coat layer, and are excellent in sufficient hardness, antifouling property, and fingerprint adhesion preventing property, and Excellent light resistance.
  • “fingerprint” means that when the surface of an article is touched with a fingertip, sweat and sebum components adhering to the fingertip adhere to the surface of the article in a form in which the pattern of the fingertip is transferred.
  • the “total solid content” in the present specification means a hard coat layer forming component among the components contained in the hard coat composition, and the solvent was removed by heating the hard coat composition at 140 ° C. for 24 hours. Refers to the remaining residue. Specifically, all components other than the volatile components that volatilize by heating or the like in the process of forming a hard coat layer such as a solvent are shown. The total solid content can also be calculated from the charged amount.
  • a film coated with the hard coat composition is referred to as a “coating film”, a dried state thereof is referred to as a “film”, and a film obtained by curing it is referred to as a “cured film”.
  • the hard coat layer formed using the hard coat composition refers to the “cured film”.
  • the term “(meth) acryloyloxy...” such as a (meth) acryloyloxy group means both “acryloyloxy...” and “methacryloyloxy...”.
  • the term “(meth) acrylic” described later means both “acrylic” and “methacrylic”.
  • the compound represented by formula (a-1) in this specification is referred to as compound (a-1). The same applies to other compounds.
  • the partial hydrolysis condensate in the present invention is hereinafter referred to as “partial condensate (A)”.
  • the “photopolymerizable compound” in the present invention is also referred to as “photopolymerizable compound (B)”, and the “photopolymerization initiator” is also referred to as “photopolymerization initiator (C)”.
  • the fingerprint adhesion preventing property in the present specification refers to a property having both the water and oil repellency that prevents the fingerprint from adhering and the removability of the adhered fingerprint. Fingerprint adhesion prevention and antifouling properties are evaluated by numerical values of water contact angle and oleic acid contact angle. In addition, unless otherwise indicated in this specification,% represents the mass%.
  • the anti-fingerprint agent of the present invention is a partial condensate (A), that is, a hydrolyzable silane compound (a-1) represented by the following formula (a-1) and represented by the following formula (a-2)
  • R f a perfluoroalkyl group having 1 to 6 carbon atoms or a monovalent group having 2 to 100 carbon atoms represented by R f1 OR f2 — (R f1 is a perfluoroalkyl having 1 to 6 carbon atoms) Group R f2 is a perfluoroalkylene group which may have an etheric oxygen atom between carbon-carbon atoms).
  • Q 1 a divalent organic group not containing a fluorine atom having 1 to 10 carbon atoms
  • Y a group having an ethylenic double bond
  • Q 2 a divalent organic group not containing a fluorine atom having 1 to 6 carbon atoms
  • R H1 , R H2 a hydrocarbon group having 1 to 6 carbon atoms
  • X 1 , X 2 , X 3 hydrolyzable group
  • p an integer from 0 to 3
  • r a number that is 0 or 1 and q + r is 1 or 2.
  • X 1 in formula (a-1), and X 2 , X 3 , R H1 , YQ 2 in the case where a plurality of X 1 exist in formula (a-2) or formula (a-3) May be different from each other or the same.
  • the partial condensate (A) in the present invention is formed using a hard coat composition containing a fluorine atom derived from the hydrolyzable silane compound (a-1) in the above-mentioned range.
  • Excellent water and oil repellency can be imparted to the surface of the hard coat layer. Since the surface of the hard coat layer has water and oil repellency, it is considered that moisture and sebum components transferred from the fingertip to the surface are not in close contact with the surface of the hard coat layer. The sebum component in such a state can be easily wiped off. In other words, it can be said that the use of the partial condensate (A) can impart excellent fingerprint adhesion prevention to the hard coat layer.
  • the fluorine atom content in the partial condensate (A) is 2.5 to 40% by mass, more preferably 3 to 40% by mass, further preferably 20 to 40% by mass, and particularly preferably 25 to 40% by mass. 30 to 40% by mass is most preferable.
  • a fluorine atom content rate is the ratio of the fluorine atom mass per unit mass of a partial condensate (A), and can be calculated
  • the partial condensate (A) in the present invention contains a unit derived from the hydrolyzable silane compound (a-2), the solubility of the partial condensate (A) in the hydrocarbon solvent and the film-forming property are obtained. Excellent.
  • the partial condensate (A) in the present invention can be radically polymerized by containing a group having an ethylenic double bond derived from the hydrolyzable silane compound (a-3). It has excellent bondability with a group having an ethylenic double bond, which is included in the photopolymerizable compound (B) described later, which is the main component of the hard coat composition containing this, and is a partial condensate (A ) Bleeding out.
  • the partial condensate (A) in the present invention preferably has a silanol group.
  • the number of silanol groups is preferably 0.2 to 3.5, more preferably 0.2 to 2.0, and particularly preferably 0.5 to 1.5 per silicon atom.
  • the partial condensate (A) is less likely to evaporate from the surface of the substrate.
  • the hard coat composition containing the partial condensate (A) is less likely to agglomerate between the partial condensates (A) and has good storage stability.
  • the number of silanol groups in the partial condensate (A) is calculated from the ratio of peak areas of Si groups having silanol groups and Si groups having no silanol groups, as measured by 29 Si-NMR.
  • the partial condensate (A) constituting the fingerprint adhesion preventing agent of the present invention is a mixture of hydrolyzable silane compounds containing hydrolyzable silane compounds (a-1) to (a-3) (hereinafter referred to as “hydrolyzable”). It is also referred to as “silane compound mixture”).
  • hydrolyzable silane compounds containing hydrolyzable silane compounds (a-1) to (a-3) (hereinafter referred to as “hydrolyzable”). It is also referred to as “silane compound mixture”).
  • silane compound mixture hydrolyzable silane compound
  • the hydrolyzable silane compound (a-1) is a fluorine-containing hydrolyzable silane compound represented by the following formula (a-1).
  • R f -Q 1 -SiX 1 3 (a-1)
  • R f represents a perfluoroalkyl group having 1 to 6 carbon atoms, or a monovalent group having 2 to 100 carbon atoms represented by R f1 OR f2 —
  • R f1 represents carbon A perfluoroalkyl group having 1 to 6 atoms
  • R f2 is a perfluoroalkylene group which may have an etheric oxygen atom between carbon-carbon atoms
  • Q 1 is fluorine having 1 to 10 carbon atoms
  • It is a divalent organic group containing no atoms
  • X 1 is a hydrolyzable group.
  • the three X 1 may be different from each other or the same.
  • the hard coat layer formed from the hard coat composition containing the partial condensate (A) exhibits excellent fingerprint adhesion prevention properties. Since the compound (a-1) has R f , when the hard coat composition containing the partial condensate (A) is applied to the substrate, the R f group is opposite to the substrate of the coating film (that is, It tends to be unevenly distributed on the air side. That is, the partial condensate (A) tends to be unevenly distributed on the side opposite to the substrate.
  • R f does not contain a perfluoroalkyl group having 7 or more carbon atoms from the viewpoint of environmental burden and excellent solubility in a general-purpose solvent. Examples of the structure of R f include a linear structure, a branched structure, a ring structure, or a structure having a partial ring, and a linear structure is preferable.
  • R f is a perfluoroalkyl group having 1 to 6 carbon atoms
  • R f is a perfluoroalkyl group having 1 to 6 carbon atoms
  • R f is a monovalent group having 2 to 100 carbon atoms represented by R f1 OR f2 — (R f1 is a perfluoroalkyl group having 1 to 6 carbon atoms, and R f2 is an etheric group between carbon-carbon atoms. From the viewpoint of compatibility with other hydrolyzable silane compounds, the number of carbon atoms is more preferably 2 to 80, and particularly preferably 2 to 40. preferable.
  • R f2 is preferably (R f3 O) x (wherein R f3 is a perfluoroalkylene group having 1 to 10 carbon atoms, and x is an integer of 1 to 99).
  • R f3 may be linear or branched. The number of carbon atoms of R f3 is particularly preferably 1 to 5 for ease of synthesis.
  • Specific examples of (R f3 O) include the following. (CF 2 O), (CF 2 CF 2 O), (CF 2 CF 2 CF 2 O), (CF (CF 3 ) CF 2 O), (CF 2 CF 2 CF 2 CF 2 O), and the like.
  • the (R f3 O) unit may be one type or two or more types, and the bonding order is not limited. You may arrange
  • R f is a monovalent group having 2 to 100 carbon atoms represented by R f1 OR f2 —
  • R f1 OR f2 — include the following groups. CF 3 OCF 3 CF 2 CF 2 —, CF 3 OCF (CF 3 ) CF 2 —, CF 3 OCF (CF 3 ) CF 2 OCF (CF 3 ) —.
  • Q 1 in the compound (a-1) is a divalent organic group containing no fluorine atom having 1 to 10 carbon atoms, and connects R f and a hydrolyzable silyl group (—SiX 1 3 ). Valent organic group.
  • Q 1 is represented as Si bonded to the right bond and R f bonded to the left bond, specifically, — (CH 2 ) i1 — (i1 is an integer of 1 to 5.
  • Q 1 is more preferably — (CH 2 ) 2 —, — (CH 2 ) 3 — and — (CH 2 ) 2 —OC ( ⁇ O) — (CH 2 ) 2 —S— (CH 2 ) 3 —.
  • — (CH 2 ) 2 — and — (CH 2 ) 2 —OC ( ⁇ O) — (CH 2 ) 2 —S— (CH 2 ) 3 — are particularly preferred.
  • the above Q 1 includes — (CH 2 ) i1 — (wherein i1 is the same as above), — (CH 2 ) i5 —OC ( ⁇ O) — (CH 2 )
  • a group represented by i6 —S— (CH 2 ) i7 — (i5, i6 and i7 are as defined above) is preferred.
  • i1 is preferably an integer of 2 to 4, particularly preferably 2.
  • i5, i6 and i7 are each independently preferably an integer of 2 to 4, particularly preferably 2 or 3.
  • Q 1 includes — (CH 2 ) i1 —, —CH 2 O (CH 2 ) i2 —, —SO 2 NR 1 — ( A group represented by CH 2 ) i3 —, — (C ⁇ O) —NR 1 — (CH 2 ) i4 — (i1 to 4 and R 1 are the same as described above) is preferable.
  • i1 is preferably an integer of 2 to 4, particularly preferably 2.
  • X 1 represents a hydrolyzable group bonded to a silicon atom.
  • X 1 include an alkoxy group, an aryloxy group, a halogen atom, an acyloxy group, an amino group, and a group in which hydrogen of the amino group is substituted with an alkyl group.
  • X 1 is preferably an alkoxy group having 1 to 4 carbon atoms or a halogen atom, and particularly preferably a methoxy group, an ethoxy group, or a chlorine atom.
  • a methoxy group and an ethoxy group are converted into a hydroxyl group (silanol group) by hydrolysis reaction, and a reaction for forming a Si—O—Si bond by condensation reaction between molecules tends to proceed smoothly.
  • compound (a-1) include the following compounds. F (CF 2 ) 4 CH 2 CH 2 Si (OCH 3 ) 3 , F (CF 2 ) 4 CH 2 CH 2 Si (OCH 2 CH 3 ) 3 , F (CF 2 ) 4 CH 2 CH 2 SiCl 3 , F (CF 2) 6 CH 2 CH 2 Si (OCH 3) 3, F (CF 2) 6 CH 2 CH 2 Si (OCH 2 CH 3) 3, F (CF 2) 6 CH 2 CH 2 SiCl 3.
  • the hydrolyzable silane compound that is a raw material of the partial condensate (A) in the present invention the compound (a-1) can be used alone or in combination of two or more.
  • the content of the compound (a-1) in the hydrolyzable silane compound mixture is the fluorine atom content in the partial condensate (A) obtained from the mixture.
  • the amount is in the range.
  • the hydrolyzable silane compound (a-2) is used together with the above compound (a-1) as a hydrolyzable silane compound that is a raw material of the partial condensate (A) in the present invention. It is a compound represented by these.
  • R H1 p —SiX 2 (4-p) (a-2) In the formula (a-2), R H1 is a hydrocarbon group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms or a phenyl group, more preferably a methyl group or an ethyl group, The group is particularly preferred.
  • X 2 is a hydrolyzable group, and the same as X 1 in the above formula (a-1) including preferred embodiments can be adopted.
  • p is an integer of 0 to 3. However, when p is 2 or 3, two or three R H1 and (4-p) X 2 may be different from each other or the same.
  • Compound (a-2) is preferably a tetrafunctional compound in which p is 0, or a trifunctional compound in which p is 1, and particularly preferably a tetrafunctional compound.
  • the compound (a-2) one type may be used alone, or two or more types may be used in combination. When using 2 or more types together, a bifunctional compound and / or a monofunctional compound can also be used together with a tetrafunctional compound and / or a trifunctional compound.
  • the partial condensate (A) water and oil repellency is exhibited by R f in the unit derived from the compound (a-1). Further, in the unit derived from the compound (a-2), when p is 0, there is an advantage that the film forming property in the partial condensate (A) is excellent. In the unit derived from the compound (a-2), when p is 1, 2 or 3 (that is, when R H1 is present), the presence of R H1 to some extent allows the partial condensate (A) to be hydrocarbon-based. Thus, there is an advantage that a relatively inexpensive solvent can be selected when a coating film of the composition for hard coat is formed on the surface of the substrate.
  • the compound (a-2) include the following compounds. Further, as the compound (a-2), a partial hydrolysis-condensation product of the compound (a-2) obtained by partial hydrolysis-condensation of a plurality of them in advance may be used as necessary. In addition, you may use the partial hydrolysis condensate similarly about another hydrolysable silane compound.
  • Si (OCH 3 ) 4 Si (OCH 2 CH 3 ) 4 , CH 3 Si (OCH 3 ) 3 , CH 3 Si (OCH 2 CH 3 ) 3 , CH 3 CH 2 Si (OCH 3 ) 3 , CH 3 CH 2 Si (OCH 2 CH 3 ) 3 , (CH 3 ) 2 Si (OCH 3 ) 2 , (CH 3 ) 2 Si (OCH 2 CH 3 ) 2 , A partially hydrolyzed condensate of Si (OCH 3 ) 4 (for example, methyl silicate 51 (trade name) manufactured by Colcoat Co.), Partially hydrolyzed condensate of Si (OCH 2 CH 3 ) 4 (for example, ethyl silicate 40 and ethyl silicate 48 manufactured by Colcoat Co., Ltd., and silicate 45 manufactured by Tama Chemical Industry Co., Ltd. (both are trade names)).
  • Si (OCH 3 ) 4 for example, methyl silicate 51 (trade name) manufactured by Colcoat Co.
  • compound (a-2) can be used alone or in combination of two or more.
  • the content of the hydrolyzable silane compound (a-2) in the hydrolyzable silane compound mixture is 100 mol of the hydrolyzable silane compound (a-1) with respect to 100 mol of the hydrolyzable silane compound (a-1). 1) to 23,000 moles of 2) are preferred, 1 to 15,000 moles are more preferred, 1 to 3,000 moles are more preferred, 1 to 800 moles are particularly preferred, and 1 to 400 moles are most preferred.
  • hydrolyzable silane compound (a-3) is a hydrolyzable silane compound containing a group having an ethylenic double bond represented by the following formula (a-3), and the compound (a-1), the compound Along with (a-2), it is used as a raw material for the partial condensate (A) in the present invention.
  • X 3 representing a hydrolyzable group can be the same as X 1 in the above formula (a-1) including preferred embodiments.
  • R H2 can be employed the same ones as including the preferred embodiments and R H1 in the above formula (a-2).
  • Y in the formula (a-3) is a group having an ethylenic double bond, and Q 2 is a divalent organic group containing no fluorine atom having 1 to 6 carbon atoms.
  • q is 1 or 2
  • r is 0 or 1
  • q + r is a number that becomes 1 or 2.
  • a plurality of YQ 2 and X 3 are present in the hydrolyzable silane compound, these may be different from each other or the same.
  • compound (a-3) Since compound (a-3) has Y, when the film of the hard coat composition film containing the resulting partial condensate (A) is photocured, it is partially condensed via the group on the surface of the film.
  • the products (A) or the partial condensate (A) and the group having an ethylenic double bond of the photopolymerizable compound (B) contained in the hard coat composition can be polymerized. Therefore, it has the effect of making the partial condensate (A) easy to be unevenly distributed on the surface of the hard coat layer, particularly after photocuring, and keeps the surface of the hard coat layer water and oil repellency and prevents fingerprint adhesion even after long-term use. The effect of sustaining can be given.
  • Y in the formula (a-3) is preferably a (meth) acryloyloxy group, a vinylphenyl group or the like, and a (meth) acryloyloxy group is particularly preferable.
  • Q 2 in the formula (a-3) is a linking group that bonds a hydrolyzable silyl group (—SiX 3 (4-qr) (R H2 ) r ) and Y, specifically, Examples thereof include an alkylene group having 2 to 6 carbon atoms and a phenylene group. Of these, — (CH 2 ) 3 — is preferable.
  • the hydrolyzable silane compound which is a raw material of the partial condensate (A) in the present invention can be used alone or in combination of two or more.
  • the content of the hydrolyzable silane compound (a-3) in the hydrolyzable silane compound mixture is preferably 20 to 11,500 with respect to 100 mol of the hydrolyzable silane compound (a-1). 20 to 8,000 mol is more preferable, 20 to 2,000 is more preferable, 20 to 300 mol is particularly preferable, and 50 to 200 mol is most preferable.
  • the hydrolyzable silane compound mixture that is a raw material of the partial condensate (A) in the present invention is added to the compound (a-1), the compound (a-2) and the compound (a-3) as necessary.
  • hydrolyzable silane compounds other than these compounds may be included for the purpose of improving the compatibility of the obtained partial condensate (A) with the hard coat composition and controlling the reactivity.
  • the content of the other hydrolyzable silane compound in the hydrolyzable silane compound mixture is within the range where the fluorine atom content in the resulting partial condensate (A) is 2.5 to 40% by mass. ), 100 to 100 mol of the total amount of compound (a-2) and compound (a-3), it is preferably 1 to 100 mol.
  • the partial condensate (A) in the present invention includes a hydrolyzable silane compound (a-1), a hydrolyzable silane compound (a-2), a hydrolyzable silane compound (a-3), and, if necessary, It consists of the partial hydrolysis-condensation product of the hydrolysable silane compound mixture which consists of another hydrolysable silane compound mix
  • the partial condensate (A) in the present invention comprises a hydrolyzable silane compound (a-1), a hydrolyzable silane compound (a-2), and a hydrolyzable silane compound (a-3).
  • the partial condensate (A) obtained by partial hydrolysis condensation of the mixture is preferred.
  • the hydrolyzable silane compound (a-1), hydrolyzable silane compound (a-2), and hydrolyzable silane compound (a-3) content in the hydrolyzable silane compound mixture are as follows:
  • the content of fluorine atom in the partial condensate (A) to be obtained is not particularly limited as long as the content is 2.5 to 40% by mass.
  • 100 mol of the hydrolyzable silane compound (a-1) On the other hand, the content is preferably 1 to 23,000 mol of the hydrolyzable silane compound (a-2) and 20 to 11,500 mol of the hydrolyzable silane compound (a-3).
  • 1 to 800 moles of the hydrolyzable silane compound (a-2) and 20 to 300 moles of the hydrolyzable silane compound (a-3) are particularly preferred.
  • the partial condensate (A) in the present invention is a partial hydrolysis condensate of the raw material hydrolyzable silane compound mixture, and is usually a mixture composed of a plurality of condensates having different degrees of polymerization. That is, the partial condensate (A) is converted into a hydrolyzable silane compound (a-1), hydrolyzable silane compound (a-2), hydrolyzable silane compound (a) as a raw material hydrolyzable silane compound, for example. When it is produced using a mixture comprising a-3), it becomes a condensate having a structure of an average composition formula represented by the following formula (1).
  • the partial condensate (A) is a product (partially hydrolyzed condensate) in which a hydrolyzable group or silanol group remains, it is difficult to express this product by a chemical formula.
  • the average composition formula represented is a chemical formula when it is assumed that all of the hydrolyzable groups or silanol groups are siloxane bonds in the partially hydrolyzed condensate produced as described above.
  • R f , Q 1 , R H1 , Y, Q 2 , R H2 and preferred ranges of p, q, r are the same as described above.
  • s, t, and u are the average number of units present in a plurality of fluorine-containing silane compound mixtures having different degrees of polymerization.
  • the partial condensate (A) in the present invention is represented by the formula (1), the main chain is composed of a polysiloxane bond having a large bond energy, and therefore has good light resistance.
  • s: t is preferably within the range described above as the content ratio of the compound (a-2) to the compound (a-1) in the hydrolyzable silane compound mixture.
  • s: u is preferably within the above-mentioned range as the content ratio of the compound (a-3) to the compound (a-1) in the mixture. Expressing this as s: t: u, it is preferably in the relationship of 100: 1 to 23,000: 20 to 11,500 (molar ratio), and 100: 1 to 800: 20 to 300 (molar ratio). Is particularly preferred.
  • the number average molecular weight (Mn) of the partial condensate (A) in the present invention is preferably 500 or more and less than 10,000, more preferably 500 or more and less than 5,000, and particularly preferably 500 or more and less than 3,000.
  • the number average molecular weight (Mn) is equal to or more than the above lower limit, when the hard coat layer is formed using the hard coat composition, the surface migration of the partial condensate (A) is high, and a small amount of addition is good. Therefore, the hardness of the cured film is improved.
  • the number average molecular weight (Mn) is less than the above upper limit, the partial condensate (A) is excellent in compatibility with the solvent and other components in the hard coat composition. Further, the phase separation is difficult, and the storage stability of the hard coat composition is improved.
  • the number average molecular weight (Mn) of the partial condensate (A) can be adjusted by selecting reaction conditions and the like.
  • the partial condensate (A) having a fluorine atom content of 2.5 to 40% by mass constituting the fingerprint adhesion preventive agent of the present invention includes the hydrolyzable silane compound (a-1) and hydrolyzable silane compound described above. (A-2), a hydrolyzable silane compound (a-3) containing the hydrolyzable silane compound (a-3) in a content such that the fluorine atom content in the resulting partial condensate (A) is 2.5 to 40% by mass
  • the mixture can be produced by hydrolysis and partial condensation.
  • reaction step (I) 1 to 23,000 mol of hydrolyzable silane compound (a-2) and hydrolyzable silane compound (a-) with respect to 100 mol of hydrolyzable silane compound (a-1) 3) a step of hydrolyzing and partially condensing the hydrolyzable silane compound mixture containing 20 to 11,500 mole ratio of 3) in the presence of water, an organic solvent and an acid.
  • the hydrolysis and partial condensation reaction is a reaction in which a silanol group is generated by a hydrolysis reaction of a hydrolyzable group and a siloxane bond is generated by a dehydration condensation reaction between silanol groups.
  • the fluorine atom content is 20 to 40% by mass
  • R f in the hydrolyzable silane compound (a-1) is a perfluoroalkyl having 1 to 6 carbon atoms.
  • R f1 OR f2 — R f1 is a perfluoroalkyl group having 1 to 6 carbon atoms
  • R f2 is an ether between carbon-carbon atoms.
  • the reaction step (I) is carried out with respect to 100 mol of the hydrolyzable silane compound (a-1) with respect to 100 mol of the hydrolyzable silane compound (a-1).
  • reaction step (Ia) A hydrolyzable silane compound mixture containing 1 to 800 mol of compound (a-2) and 20 to 300 mol of hydrolyzable silane compound (a-3) in the presence of water, an organic solvent and an acid, Hydrolyzed and partially condensed (Hereinafter, also referred to as reaction step (Ia)).
  • reaction step (Ia) the various conditions in the reaction step (I) include the conditions in the reaction step (Ia). Among these, the reaction step (Ia) will be further described when there are particularly preferable conditions for the reaction step (Ia).
  • the amount of water used in the reaction step (I) is preferably 5 to 100 parts by mass and particularly preferably 5 to 80 parts by mass with respect to 100 parts by mass of the hydrolyzable silane compound mixture.
  • the amount of water to be used is preferably 5 to 40 parts by mass, particularly preferably 5 to 25 parts by mass with respect to 100 parts by mass of the hydrolyzable silane compound mixture.
  • the acid acts as a catalyst for hydrolyzing and partially condensing the hydrolyzable silane compound.
  • the acid include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, and organic acids such as acetic acid, oxalic acid, and maleic acid. Of these, nitric acid is preferable.
  • the amount of the acid is preferably 0.01 to 10 parts by weight, particularly preferably 0.01 to 1 part by weight, based on 100 parts by weight of the hydrolyzable silane compound mixture.
  • organic solvent used in the reaction step (I) examples include organic solvents usually used when hydrolyzing and condensing a hydrolyzable silane compound.
  • organic solvents such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, ethylene glycol, glycerin and propylene glycol; ketones such as acetone, methyl isobutyl ketone and cyclohexanone
  • Cellsolves such as 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol; 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol, 2- (2-butoxyethoxy) ethanol
  • Carbitols such as methyl acetate, ethyl acetate, n-butyl acetate, ethyl lactate, n-butyl lactate, ethylene glycol monomethyl ether acetate, ethylene glycol mono
  • the partial condensate (A) to be obtained preferably has a silanol group as described above. Moreover, the partial condensate (A) obtained is often blended into the hard coat composition together with the organic solvent used in the reaction step (I). Accordingly, it is preferable to use an organic solvent that stabilizes the silanol group as the organic solvent used in the reaction step (I).
  • the organic solvent that stabilizes the silanol group include compounds having a hydroxyl group and a relative dielectric constant ( ⁇ ) in the range of 5 to 20 at 25 ° C.
  • glycol monoalkyl ether acetate solvents having 2 to 8 carbon atoms examples include glycol monoalkyl ether acetate solvents having 2 to 8 carbon atoms, glycol monoalkyl ether solvents, glyme solvents, hydrocarbon alcohols having 2 to 4 carbon atoms, and the like.
  • propylene glycol monomethyl ether acetate ⁇ : 8.3 as a glycol-based monoalkyl ether acetate solvent
  • propylene glycol monomethyl ether ( ⁇ : 12.3) as a glycol-based monoalkyl ether solvent
  • hydrogen alcohol examples include 2-propanol ( ⁇ : 19.92).
  • propylene glycol monomethyl ether which is a protic polar solvent capable of hydrogen bonding, is preferable because of its high silanol group stabilizing effect.
  • the organic solvent is preferably composed only of a compound having a hydroxyl group and a relative dielectric constant ( ⁇ ) in the range of 5 to 20 at 25 ° C. from the viewpoint of sufficiently stabilizing the silanol group.
  • the organic solvent may contain a compound other than the compound, if necessary.
  • the organic solvent has a hydroxyl group and a relative dielectric constant ( ⁇ ) at 25 ° C. in the range of 5 to 20 with respect to the total amount of the organic solvent. Is preferably contained in the range of 10 to 100% by mass from the viewpoint of the silanol group stabilizing effect, and particularly preferably in the range of 20 to 100% by mass.
  • the reaction step (I) is preferably performed at a reaction temperature from room temperature to the boiling point of the solvent under suitable stirring conditions.
  • the reaction time depends on the amount of raw material components to be used, reaction temperature, stirring conditions and the like, but is preferably 0.5 to 24 hours, particularly preferably 1 to 18 hours.
  • the obtained partial condensate (A) can be contained in the hard coat composition of the present invention without removing the organic solvent. After removing the organic solvent by a usual method, the partial condensate (A) may be isolated and then contained in the hard coat composition.
  • composition for hard coats of the present invention contains the partial condensate (A) and a photopolymerizable component, and the content of the partial condensate (A) is 0. 0 relative to the total solid content of the composition.
  • a hard coat composition having a content of 01 to 20% by mass.
  • the photopolymerizable component contains a photopolymerizable compound (B), and preferably further contains a photopolymerization initiator (C).
  • the composition for hard coats of the present invention may further contain an organic solvent (D), silica fine particles (E) and other additives as required.
  • a cured film which is a film obtained by curing the composition, is at least transparent to visible light.
  • the cured film is preferably a colorless transparent film, but may be a colored transparent film.
  • the hard coat composition contains an additive that inhibits the transparency of the cured film.
  • a powder made of a transparent material having a refractive index substantially equal to that of the cured film, such as silica fine particles (E), is a composition for hard coat as an additive for improving the abrasion resistance of the cured film without reducing the transparency. Can be blended into products.
  • the composition for hard coats of the present invention contains the partial condensate (A).
  • the content of the partial condensate (A) in the hard coat composition of the present invention is 0.01 to 20% by mass, preferably 0.1 to 10% by mass, based on the total solid content in the hard coat composition. 0.1 to 5% by mass is particularly preferable.
  • content of a partial condensate (A) into the said range the storage stability of the composition for hard-coats becomes favorable.
  • the surface of the hard coat layer obtained from the hard coat composition has good antifouling properties and fingerprint adhesion prevention properties, and a hard coat layer having a surface with a good appearance can be obtained.
  • the photopolymerizable compound (B) in the hard coat composition of the present invention is a compound that starts polymerization reaction by irradiating light in the presence of a photopolymerization initiator (C) described later, and cures by polymerization. It is a generic name. Depending on conditions and types, photopolymerization may be carried out only with the photopolymerizable compound (B), but it is usually used together with a photopolymerization initiator (C).
  • the photopolymerizable compound (B) contains a polyfunctional monomer having two or more ethylenic double bonds in one molecule (hereinafter also referred to as “monomer (b-1)”). It is preferable to do.
  • the photopolymerizable compound (B) is cured by irradiation with light, specifically, ultraviolet rays, electron beams, X-rays, radiation, high-frequency rays, or the like.
  • the partial condensate (A) is a compound having an ethylenic double bond, but the photopolymerizable compound (B) does not include a compound corresponding to the partial condensate (A).
  • the monomer (b-1) is not particularly limited as long as it is a compound having a group having two or more ethylenic double bonds (hereinafter also referred to as “polymerizable functional group”) in one molecule.
  • the polymerizable functional group is preferably an ⁇ , ⁇ -unsaturated group such as a (meth) acryloyl group, a vinyl group, or an allyl group, and a (meth) acryloyl group is particularly preferable. Among them, an acryloyl group that is more easily polymerized by ultraviolet rays is preferable.
  • the monomer (b-1) may be a compound having a total of two or more polymerizable functional groups in one molecule, or a compound having a total of two or more of the same polymerizable functional groups. There may be.
  • the number of polymerizable functional groups in one molecule of the monomer (b-1) is 2 or more, and 3 or more is particularly preferable.
  • the upper limit of the number of polymerizable functional groups possessed by one molecule of the monomer (b-1) is not particularly limited, and is usually about 50, preferably 30.
  • the monomer (b-1) has three or more polymerizable functional groups in one molecule from the viewpoint of developing a high level of wear resistance, and the molecular weight per functional group is 120 or less. Certain compounds are preferred. Examples of the monomer (b-1) satisfying such conditions include the following compounds.
  • Polyfunctional compound which is a polyester which is a reaction product of pentaerythritol or polypentaerythritol and (meth) acrylic acid, and has 3 or more, more preferably 4 to 20 (meth) acryloyl groups.
  • trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like are preferable.
  • a (meth) acryloyl group-containing compound having a urethane bond in the molecule acts as a pseudo-crosslinking point due to the action of the hydrogen bond of the urethane bond per functional group. Even if the molecular weight is not as small as described above, a sufficiently high wear resistance can be expressed, which is preferable.
  • the monomer (b-1) satisfying such conditions the following compounds are preferred.
  • Multifunctional compound It is an acrylic urethane that is a reaction product of a hydroxyl group-containing poly (meth) acrylate of pentaerythritol or polypentaerythritol and a polyisocyanate, and has 3 or more, more preferably 4 to 20 (meth) acryloyl groups. Multifunctional compound.
  • the monomer (b-1) one type may be used alone, or two or more types may be used in combination.
  • the monomer (b-2) is not particularly limited as long as it is a compound having one polymerizable functional group in one molecule.
  • the polymerizable functional group possessed by the monomer (b-2) is preferably a (meth) acryloyl group.
  • C z H 2z + 1 may be a straight chain structure or a branched structure.
  • the content of the monomer (b-1) in the photopolymerizable compound (B) is preferably 20 to 100% by mass with respect to the total amount of the photopolymerizable compound (B).
  • the proportion of the monomer (b-1) in the photopolymerizable compound (B) is in the above range, the wear resistance of the hard coat layer comprising the cured film of the hard coat composition is excellent.
  • the proportion of the monomer (b-1) is more preferably 50 to 100% by mass, and particularly preferably 70 to 100% by mass.
  • the content of the monomer (b-2) in the photopolymerizable compound (B) is preferably 0 to 80% by mass with respect to the total amount of the photopolymerizable compound (B).
  • the cured film has good hardness and has an appropriate film shrinkage ratio, and therefore has a hard coat layer.
  • the substrate does not warp.
  • the proportion of the monomer (b-2) is more preferably 0 to 50% by mass, and particularly preferably 0 to 30% by mass.
  • the monomer (b-1) and the monomer (b-2) may be a plurality of monomers (b-1) or a monomer (b-1)
  • a plurality of bodies (b-2) may be used in the form of a (co) oligomer or pre (co) polymer obtained by (co) polymerization in advance.
  • the content of the (co) oligomer or pre (co) polymer in the photopolymerizable compound (B) is such that the content of the repeating unit derived from the monomer (b-1) is the photopolymerizable compound.
  • the content of the repeating unit derived from the monomer (b-2) is 0 to 80% by mass based on the total amount of the photopolymerizable compound (B).
  • the ratio of the repeating unit derived from the monomer (b-1) is more preferably 50 to 100% by mass, and particularly preferably 70 to 100% by mass.
  • the ratio of the repeating unit derived from the monomer (b-2) is more preferably 0 to 50% by mass, and particularly preferably 0 to 30% by mass.
  • the content of the photopolymerizable compound (B) in the total solid content in the hard coat composition is preferably 40 to 99.99% by mass, more preferably 50 to 95% by mass, and particularly preferably 55 to 90% by mass. .
  • the photopolymerization initiator (C) used in the hard coat composition of the present invention is not particularly limited as long as it is a compound having a function as a photopolymerization initiator, but is preferably a compound that generates radicals by light.
  • the photopolymerization initiator (C) include aryl ketone photopolymerization initiators (for example, acetophenones, benzophenones, alkylaminobenzophenones, benzyls, benzoins, benzoin ethers, benzyldimethylketals, Benzoylbenzoates, ⁇ -acyloxime esters, etc.), sulfur-containing photopolymerization initiators (eg sulfides, thioxanthones, etc.), acylphosphine oxides (eg acyl diarylphosphine oxide, etc.), other photopolymerization initiation Agents.
  • aryl ketone photopolymerization initiators for example, acetophenones, benzophenones, alkylaminobenzophenones, benzyls, benzoins, benzoin ethers, benzyldimethylketals, Benzoylbenzoates, ⁇ -acylox
  • a photoinitiator (C) may be used individually by 1 type, and may use 2 or more types together. Moreover, you may use a photoinitiator (C) in combination with photosensitizers, such as amines. Examples of the photopolymerization initiator include the following compounds.
  • the content of the photopolymerization initiator (C) in the total solid content in the hard coat composition is preferably 1 to 15% by mass, more preferably 3 to 15% by mass, and particularly preferably 3 to 10% by mass. Within the above range, the compatibility with the photopolymerizable compound (B) in the hard coat composition and the curability are good, and the hardness of the cured film to be formed is good.
  • the composition for hard coats of the present invention may contain an organic solvent (D).
  • an organic solvent (D) By containing an organic solvent (D), the coating property to the base material of this composition can be improved.
  • a partial condensate (A) can be made to exist stably in the composition for hard-coats.
  • the silica fine particles (E) and other additives are uniformly dissolved or dispersed and are not particularly limited as long as they do not have reactivity with each component contained in the hard coat composition.
  • An organic solvent (D) may be used individually by 1 type, and may use 2 or more types together.
  • the amount of the organic solvent (D) used is preferably 10,000 parts by mass or less, particularly preferably 5,000 parts by mass or less, based on 100 parts by mass of the photopolymerizable compound (B).
  • Examples of the organic solvent (D) include lower alcohols such as ethyl alcohol, butyl alcohol and isopropyl alcohol, ketones such as methyl isobutyl ketone, methyl ethyl ketone and acetone, ethers such as dioxane, diethylene glycol dimethyl ether, tetrahydrofuran and methyl t-butyl ether.
  • Organic solvents such as methyl ethers such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether are preferred.
  • esters such as n-butyl acetate, isoamyl acetate, diethylene glycol monoacetate, propylene glycol monomethyl ether acetate, etc., carbon atoms of 5 to 12 such as polyfluorohexane, polyfluoromethylcyclohexane, polyfluoro-1,3-dimethylcyclohexane, etc.
  • Polyfluoroaliphatic hydrocarbons, polyfluorinated aromatic hydrocarbons such as bis (trifluoromethyl) benzene, halogenated hydrocarbons such as polyfluorinated aliphatic hydrocarbons, hydrocarbons such as toluene, xylene and hexane Etc. can be used.
  • n-butyl acetate which has an appropriate solubility and evaporation rate for the photopolymerizable compound (B), is particularly preferred.
  • the partial condensate (A) in the composition for hard coat, from the viewpoint that the partial condensate (A) can be stably present, it has a hydroxyl group and has a relative dielectric constant ( ⁇ ) of 5 at 25 ° C.
  • Compounds in the range of ⁇ 20 are preferred.
  • propylene glycol monomethyl ether which is a protic polar solvent capable of hydrogen bonding, is preferable because of its high silanol group stabilizing effect.
  • it contains 10 to 100% by mass of a compound having a hydroxyl group and a relative dielectric constant ( ⁇ ) at 25 ° C. in the range of 5 to 20 with respect to the total amount of the organic solvent.
  • the content is preferably 20 to 100% by mass.
  • organic solvent (D) When the organic solvent (D) is contained in the hard coat composition, it is preferable to select an appropriate organic solvent (D) according to the type of substrate on which the hard coat layer is formed.
  • the substrate is an aromatic polycarbonate resin having low solvent resistance
  • an organic solvent (D) having low solubility in the aromatic polycarbonate resin Lower alcohols, glycol ethers, esters, ethers And mixtures thereof are suitable.
  • composition for hard coats of the present invention may contain silica fine particles (E) as necessary. By containing the silica fine particles (E), the wear resistance of the hard coat layer can be improved.
  • colloidal silica is silicic acid ultrafine particles dispersed colloidally in a dispersion medium, and the dispersion medium is not particularly limited, but water, lower alcohols, cellosolves and the like are preferable.
  • Specific dispersion media include water, methanol, ethanol, isopropyl alcohol, n-butanol, ethylene glycol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether acetate, dimethylacetamide, toluene, xylene, methyl acetate, and ethyl acetate. , Pentyl acetate, acetone and the like.
  • the average particle diameter of the silica fine particles (E) is not particularly limited, but is preferably 1 to 1,000 nm, more preferably 1 to 200 nm, in order to exhibit high transparency of the cured film, that is, the hard coat layer after curing. 1 to 50 nm is particularly preferable.
  • the surface of the fine particles can be modified with a hydrolyzate of a hydrolyzable silane compound.
  • the surface is modified with a hydrolyzate means that the hydrolyzate of the hydrolyzable silane compound is physically or chemically bonded to a part or all of the silanol groups on the surface of the silica fine particles (E). Which means that the surface properties are modified.
  • silica fine particles to which a partial condensate of a hydrolyzate is bonded are also included.
  • the surface modification may be performed, for example, by hydrolyzing part or all of the hydrolyzable group of the hydrolyzable silane compound in the presence of silica fine particles, or causing hydrolysis and condensation reaction.
  • hydrolyzable silane compound an organic group having a functional group such as a (meth) acryloyl group, an amino group, an epoxy group or a mercapto group and a hydrolyzable group such as an alkoxy group or a hydroxyl group are bonded to a silicon atom.
  • a functional group such as a (meth) acryloyl group, an amino group, an epoxy group or a mercapto group and a hydrolyzable group such as an alkoxy group or a hydroxyl group.
  • the content thereof is preferably 0.1 to 500 parts by mass, more preferably 1 to 300 parts by mass with respect to 100 parts by mass of the photopolymerizable compound (B). Particularly preferred is ⁇ 200 parts by weight.
  • the cured film after curing that is, the hard coat layer, has sufficient wear resistance, easily maintains high transparency, and does not easily cause cracks due to external force.
  • an ultraviolet absorber In the composition for hard coat of the present invention, as an additive other than the above, an ultraviolet absorber, a light stabilizer, an antioxidant, a thermal polymerization inhibitor, if necessary, within a range not impairing the effects of the present invention, Leveling agent, antifoaming agent, thickener, anti-settling agent, pigment (organic coloring pigment, inorganic pigment), coloring dye, infrared absorber, fluorescent whitening agent, dispersant, conductive fine particle, antistatic agent, antifogging
  • One or more additives selected from the group consisting of an agent and a coupling agent may be blended.
  • a partial condensate (A) is added to a photocurable resin composition (hereinafter also referred to as “resin composition (Y)”) commercially available for forming a hard coat. ) May be contained in a proportion of 0.01 to 20% by mass with respect to the total mass of the total solid content of the resin composition (Y) and the partial condensate (A).
  • the commercially available resin composition (Y) for forming a hard coat usually contains a photopolymerizable compound (B) as a photopolymerizable component, and more often contains a photopolymerization initiator (C). If necessary, it contains various components as described above.
  • Y a commercially available resin composition for forming a hard coat
  • Y a commercially available resin composition for forming a hard coat
  • hard coat HC162 (trade name, manufactured by Yokohama Rubber Co., Ltd.), hard coat beam set 575 (CB) (trade name, Arakawa Chemical Industries). Etc.).
  • the base material having the hard coat layer of the present invention has a base material and a hard coat layer made of a cured film formed from the hard coat composition of the present invention on at least a part of the surface of the base material.
  • the base material on which the hard coat layer is formed is not particularly limited as long as it is made of a material that is generally required to form a hard coat layer having antifouling property, particularly fingerprint adhesion prevention property, metal, glass,
  • a substrate made of resin, ceramic, or a combination thereof is preferably used.
  • a transparent substrate such as glass or resin is preferable.
  • the glass include ordinary soda lime glass, borosilicate glass, alkali-free glass, and quartz glass.
  • the base material on which the hard coat layer is formed is a transparent resin, and when using a resin base material that is required to have antifouling properties, in particular, fingerprint adhesion prevention and abrasion resistance. In particular, a remarkable effect can be exhibited, which is preferable.
  • resins include aromatic polycarbonate resins, polymethyl methacrylate resins, polymethacrylimide resins, polystyrene resins, polyvinyl chloride resins, unsaturated polyester resins, polyolefin resins, ABS resins, MS (methyl methacrylate ⁇ Styrene) resin and the like.
  • the shape of the substrate and the surface on which the hard coat layer is formed are not particularly limited and are appropriately selected depending on the application.
  • the substrate When the substrate is plate-shaped, it may be a flat plate, or the entire surface or a part thereof may have a curvature.
  • the thickness of the substrate can be appropriately selected depending on the use of the substrate having a hard coat layer, but is generally preferably 0.5 to 10 mm.
  • the surface may be subjected to acid treatment (treatment using diluted hydrofluoric acid, sulfuric acid, hydrochloric acid, etc.), alkali treatment (treatment using an aqueous sodium hydroxide solution) or discharge.
  • acid treatment treatment using diluted hydrofluoric acid, sulfuric acid, hydrochloric acid, etc.
  • alkali treatment treatment using an aqueous sodium hydroxide solution
  • discharge treatment using an aqueous sodium hydroxide solution
  • Those subjected to treatment plasma irradiation, corona irradiation, electron beam irradiation, etc.
  • the method for forming the hard coat layer on the surface of the substrate is usually the same as the method for forming the hard coat layer on the substrate using the hard coat composition mainly composed of the photopolymerizable compound (B).
  • the method is applicable. Specifically, (1) a coating film forming step in which a hard coat composition is applied to a predetermined surface of a substrate to form a coating film (provided that the hard coat composition contains no solvent) (2) A solvent removal step of removing the solvent from the coating film on the base material as necessary to form a film, and (3) on the base material. It can be manufactured by a method having a photocuring step of irradiating the film with light to form a hard coat layer as a cured film.
  • the method for applying the hard coat composition to the surface of the substrate is not particularly limited, and conventionally known methods can be applied. Specific examples include a dipping method, a spin coating method, a flow coating method, a spray method, a bar coating method, a gravure coating method, a roll coating method, a blade coating method, and an air knife coating method.
  • the thickness of the coating film or film is adjusted so that the cured film after photocuring, that is, the thickness of the hard coat layer, becomes the thickness described later.
  • solvent removal step When a coating film containing a solvent is formed on the substrate, drying for solvent removal is usually performed.
  • the drying conditions depend on the hard coat composition to be used, but treatment at 40 to 120 ° C. for about 0.5 to 5 minutes is common.
  • the film on the substrate is irradiated with light, and the photocuring component in the film is reacted and cured to form a cured film, thereby forming a hard coat layer.
  • light used for light irradiation ultraviolet rays, electron beams, X-rays, radiation, high-frequency rays and the like are preferable, and ultraviolet rays having a wavelength of 180 to 500 nm are particularly preferable economically.
  • xenon lamps low-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, carbon arc lamps, tungsten lamps and other ultraviolet irradiation devices, electron beam irradiation devices, X-ray irradiation devices, high-frequency generators and the like can be used.
  • the light irradiation conditions can be appropriately changed depending on the type of the photopolymerizable compound (B), the type of the photopolymerization initiator (C), the thickness of the film, the type of the light source, and the like. Normally, preferably 100 ⁇ 5,000mJ / cm 2 as a condition of exposure to the membrane, particularly preferably 100 ⁇ 1,000mJ / cm 2.
  • the exposure time is preferably 0.1 to 60 seconds, particularly preferably 0.5 to 30 seconds. Further, for the purpose of completing the curing reaction, heat treatment can be performed after the light irradiation.
  • the thickness of the hard coat layer is preferably 0.1 to 50 ⁇ m, more preferably 0.2 to 20 ⁇ m, and particularly preferably 0.3 to 10 ⁇ m. It is preferable for the thickness of the hard coat layer to be in the above-mentioned range since the wear resistance is sufficient and the hard coat layer is sufficiently hardened.
  • the hard coat layer thus formed on the surface of the substrate has good transparency, the surface has sufficient hardness, excellent water and oil repellency, and excellent fingerprint adhesion over a long period of time. Preventive properties can be expressed.
  • the property related to the water / oil repellency on the surface of the hard coat layer of the substrate having the hard coat layer of the present invention depends on the function of the partial condensate (A) contained in the hard coat composition.
  • the partial condensate (A) is blended in the hard coat composition and binds to the photopolymerizable compound (B), which is the main component of the hard coat layer, when the hard coat layer is formed by the above method.
  • the hard coat layer exhibits excellent water and oil repellency due to the fluorine-containing organic group of the partial condensate (A), particularly on the surface.
  • the partial condensate (A) is bonded to the photopolymerizable compound (B), it hardly bleeds out from the hard coat layer and can exhibit excellent water and oil repellency over a long period of time. .
  • the surface of the hard coat layer of the substrate having the hard coat layer of the present invention is excellent in antifouling properties against oily dirt such as sebum, sweat, cosmetics, etc., particularly fingerprint adhesion prevention, and the oily dirt adheres. It is difficult to wipe off even if it adheres.
  • the base material having the hard coat layer of the present invention has the above-mentioned characteristics, it is difficult to apply oily dirt, particularly fingerprint attachment, in appearance, touch panels, display glasses, optical elements used for smartphones, tablet PCs, and the like. It is useful as a member for sanitary equipment. In particular, a remarkable effect is obtained when used for a touch panel.
  • the touch panel of the present invention has a substrate having the hard coat layer of the present invention.
  • the touch panel can be designed in the same manner as a normal touch panel except that a base material having a hard coat layer is disposed so that the hard coat layer is exposed on the touch surface.
  • Examples 1 to 3, 9 to 11, 18, 19, 21 to 24, and 26 are examples, examples 4 to 8, 12 to 16, 20, and 25 are comparative examples, and example 17 is a reference example.
  • the number average molecular weight (Mn) of the sample was determined by computer analysis of the GPC spectrum of the sample using the calibration curve.
  • the fluorine atom content was determined by 19 F NMR measurement using 1,4-ditrifluoromethylbenzene as a standard substance.
  • the ink repellency was evaluated at the initial stage and after the following light resistance test.
  • the ink repellency was evaluated by drawing a line on the surface of the obtained cured film with a felt pen (manufactured by Zebra Co., Ltd., product name: Mackie extra fine black) and visually observing the adhesion state of the ink.
  • the evaluation criteria are as follows. ⁇ (excellent): The ink repellent property is good and the ink is repelled. ⁇ (good): The ink is not repelled, and a linear repelling occurs (the line width is less than 50% of the width of the tip of the felt pen).
  • ⁇ (possible): A linear repelling of the ink occurs, and the line width is 50% or more and less than 100% of the width of the pen tip of the felt pen.
  • X (defect): A line can be drawn cleanly on the surface without repelling ink at all.
  • Example 1 Production of partial condensate (A1) and partial condensate liquid (A1-1)]
  • a-1) CF 3 (CF 2 ) 5 CH 2 CH 2 Si (OCH 3 ) 3 (Asahi Glass Co., Ltd.) 12.45 g of Si (OC 2 H 5 ) 4 (manufactured by Colcoat Co.) which is a-2), CH 2 ⁇ CHCOO (CH 2 ) 3 Si (OCH 3 ) 3 which is the above compound (a-3) (Tokyo) 40.8 g of Kasei Kogyo Co., Ltd. was added.
  • 607 g of PGME and 12.02 g of water were added to obtain a mixture.
  • the obtained PGME solution containing 10% by mass of the partial condensate (A1) was used as the partial condensate liquid (A1-1).
  • the fluorine-containing atom content rate of the partial condensate (A1) was 34.3 mass%, and the number average molecular weight (Mn) was 740.
  • Table 1 shows the raw material composition of the partial condensate (A1) and the amount of each component used in the production in terms of mass (g). Further, regarding the raw material composition, the number of moles when the compound (a-1) is 100 moles is also shown. The amount of each component used in the production is shown together with parts by mass when the total amount of the compounds (a-1) to (a-3) is 100 parts by mass. The fluorine atom content and the number average molecular weight (Mn) are also shown.
  • Examples 2 to 6 Production of partial condensates (A2) to (A6) and partial condensate liquids (A2-1) to (A6-1)] Partial condensates (A2) to (A6) and partial condensate liquids (A2-1) to (A6-1) were obtained in the same manner as in Example 1 except that the ingredients were mixed as shown in Table 1.
  • Example 7 Production of partial condensate (A7)
  • the composition of the raw materials was changed as shown in Table 1. After completion of the reaction, white grease was precipitated. The white grease was filtered, washed with ion-exchanged water until the pH reached 6-7, and dried at 60 ° C. under reduced pressure for 3 hours to obtain a slightly viscous white solid resin. The obtained resin was defined as a partial condensate (A7).
  • Example 8 Production of partial condensate (A8) and partial condensate liquid (A8-1)]
  • a white wax-like compound in which ⁇ -caprolactone was ring-opened and added to one end of C 3 F 7 (OCF 2 CF 2 CF 2 ) 20 O (CF 2 ) 2 CH 2 OH was obtained.
  • the number average molecular weight (Mn) of the compound was 4,400, and the polymerization degree of caprolactone was about 3.5.
  • Example 9 Production of hard coat composition and substrate having hard coat layer
  • 10 g of the liquid (A1-1) produced in Example 1 80 g of the photopolymerizable compound (B-1), a photopolymerization initiator (C-1 4 g) and 100 g of the organic solvent (D-1) were added, and the mixture was stirred for 1 hour at room temperature and in the light-shielded state.
  • 75 g of colloidal silica (E-1) was slowly added with stirring, and the mixture was further stirred for 1 hour at room temperature and in the light-shielded state to obtain composition 1 for hard coat.
  • hard coat composition example 1 was applied to the surface of the PET substrate by bar coating and dried on a hot plate at 50 ° C. for 1 minute to form a film on the surface of the substrate. Subsequently, light irradiation was performed using a high-pressure mercury lamp (light quantity: 300 mJ / cm 2 , ultraviolet integrated energy amount having a wavelength of 365 nm). As a result, a cured film having a thickness of 5 ⁇ m was obtained on the surface of the substrate. This cured film (hard coat layer) was evaluated by the method described above. The results are shown in Table 2 together with the composition of the hard coat composition.
  • Example 10 to 17 Production of hard coat composition and substrate having hard coat layer
  • Hard coat compositions 2 to 9 were produced in the same manner as in Example 9, except that the photopolymerization initiator (C), the organic solvent (D) and the colloidal silica (E) were changed as shown in Table 2. Using each of these, a cured film (hard coat layer) was formed on a PET substrate in the same manner as in Example 9, and evaluated. The results are shown in Table 2 together with the composition of the hard coat composition.
  • Example 18 Production of partial condensate (A9) and partial condensate liquid (A9-1)]
  • the above compound (a-1) CF 3 O (CF 2 CF 2 O) 8 CF 2 C ( ⁇ O) NHCH 2 CH 2 CH 2 Si (OCH 3 ) 3 3.3 g of (produced based on Example 2 of International Publication No.
  • the obtained solution containing 5% by mass of the partial condensate (A9) was used as the partial condensate liquid (A9-1).
  • the fluorine-containing atom content of the partial condensate (A9) was 3.9% by mass, and the number average molecular weight (Mn) was 1,160.
  • Example 19 Production of partial condensate (A10) and partial condensate liquid (A10-1)]
  • a-1) KY-108 trade name, manufactured by Shin-Etsu Chemical Co., Ltd.
  • a-2) Si (OC) 60.7 g of 2 H 5 ) 4 manufactured by Colcoat Co.
  • 34.1 g of CH 2 ⁇ CHCOO (CH 2 ) 3 Si (OCH 3 ) 3 manufactured by Tokyo Chemical Industry Co., Ltd.
  • 537 g of hexafluorometaxylene and 230 g of 2-propanol were added to obtain a mixture.
  • the obtained solution containing 7% by mass of the partial condensate (A10) was used as the partial condensate liquid (A10-1).
  • the fluorine-containing atom content of the partial condensate (A10) was 7.4% by mass, and the number average molecular weight (Mn) was 1,230.
  • Example 20 Production of partial condensate (X1) and partial condensate liquid (X1-1)]
  • the above compound (a-1) CF 3 O (CF 2 CF 2 O) 8 CF 2 C ( ⁇ O) NHCH 2 CH 2 CH 2 Si (OCH 3 ) 3 1.7 g of (produced based on Example 2 of International Publication No.
  • the obtained solution containing 5% by mass of the partial condensate (X1) was used as the partial condensate liquid (X1-1).
  • the fluorine-containing atom content rate of the partial condensate (X1) was 2.1 mass%, and the number average molecular weight (Mn) was 1,150.
  • Example 21 Production of partial condensate (A11) and partial condensate liquid (A11-1)]
  • a 2 liter flask equipped with a stirrer 88.0 g of F (CF 2 ) 6 CH 2 CH 2 OC ( ⁇ O) C (CH 3 ) ⁇ CH 2 under a nitrogen atmosphere, HSCH 2 CH 2 CH 2 Si 40.0 g of (OCH 3 ) 3 and 0.33 g of 2,2′-azobisisobutyronitrile (AIBN) were added.
  • AIBN 2,2′-azobisisobutyronitrile
  • 710 g of hexafluorometaxylene and 304 g of 2-propanol were added to obtain a mixture.
  • the obtained solution containing 10% by mass of the partial condensate (A11) was used as the partial condensate liquid (A11-1).
  • the fluorine-containing atom content of the partial condensate (A11) was 12.4% by mass, and the number average molecular weight (Mn) was 990.
  • Table 3 shows the raw material compositions of the partial condensates (A9), (A10), (X1) and (A11) and the amounts of each component used in the production in terms of mass (g). Further, regarding the raw material composition, the number of moles when the compound (a-1) is 100 moles is also shown. The amount of each component used in the production is shown together with parts by mass when the total amount of the compounds (a-1) to (a-3) is 100 parts by mass. The fluorine atom content and the number average molecular weight (Mn) are also shown.
  • Examples 22 to 26 Production of hard coat composition and substrate having hard coat layer
  • Commercially available resin compositions for forming hard coats shown in Table 4 are the partial condensate liquids (A9-1), (A10-1), (X1-1) and (A11-1) obtained in Examples 18 to 21.
  • the ratios of the partial condensates (A9), (A10), (X1) and (A11) are shown in Table 4 with respect to the total solid content of the resin composition (Y) and the total mass of the partial condensates.
  • Hard coat compositions 10 to 14 were produced so as to contain the indicated ratio (mass%).
  • photocurable resin composition (Y) in each example either hard coat HC162 (trade name, manufactured by Yokohama Rubber Co., Ltd.) or hard coat beam set 575 (CB) (trade name, manufactured by Arakawa Chemical Industries, Ltd.) was used. Using each of these, a cured film (hard coat layer) was formed on a PET substrate in the same manner as in Example 11, and evaluated. The results are shown in Table 4 together with the composition of the hard coat composition.
  • the hard coat layers of Examples 9 and 10 formed by using the partial condensates (A1) and (A2) of the present invention, respectively, have fingerprint adhesion prevention, light resistance, and cured film as shown by water and oil repellency and ink repellency. Appearance and pencil hardness were good.
  • the hard coat layer of Example 11 formed using the partial condensate (A3) of the present invention had a fingerprint adhesion preventing property and a cured film appearance was good.
  • the hard coat layers of Examples 22 to 24 and 26 formed using the partial condensates (A9), (A10), and (A11) of the present invention, respectively, have fingerprint adhesion prevention properties that are indicated by water / oil repellency and ink repellency. The cured film appearance was good.
  • the hard coat layer of Example 12 using the partial condensate (A4) having a fluorine atom content of more than 40% of the partial condensate had an insufficient cured film appearance.
  • the hard coat layer of Example 13 using the partial condensate (A5) containing no compound (a-2) unit had insufficient ink repellency. Since it does not contain the unit of compound (a-2), it is presumed that the film forming property of the partially hydrolyzed condensate was impaired.
  • the hard coat layer of Example 14 using the partial condensate (A6) containing no compound (a-3) unit had insufficient ink repellency. Since it does not contain the unit of the compound (a-3), it is presumed that the partial hydrolysis-condensation product did not polymerize with the photopolymerizable compound (B), and it was hard to be unevenly distributed on the surface of the coat layer.
  • the hard coat layer of Example 15 using the partial condensate (A7) using a hydrolyzable silane compound having a perfluoroalkyl group having 8 carbon atoms has a large environmental load. Further, the appearance of the cured film was insufficient. This is presumed to be because the number average molecular weight of the partially hydrolyzed condensate is large, so that the compatibility with the photopolymerizable compound (B) was insufficient.
  • the hard coat layer of Example 16 using the partial condensate (A8) whose main chain is composed of hydrocarbons had insufficient light resistance. It is presumed that the main chain is composed of hydrocarbons, and therefore deteriorated due to ultraviolet rays.
  • Example 17 a composition for hard coat was produced using the partial hydrolysis-condensation product of Example obtained in Example 1, and a substrate having a hard coat layer was produced using the composition.
  • the hard coat composition was produced with a composition in which the content of the partially hydrolyzed condensate in the total solid content exceeded 20% by mass, the ink repellent property was insufficient in the hard coat layer of Example 17. there were.
  • the partial hydrolysis condensate having a low surface energy has a characteristic of segregating on the surface.
  • a layer in which the partially hydrolyzed condensate was concentrated was formed, and it is estimated that the partial condensate (A) and the photopolymerizable compound (B) could not be sufficiently crosslinked.
  • a suitable composition is appropriately adjusted according to the range of properties required for the composition.
  • the hard coat layer of Example 25 using the partial condensate (X1) having a fluorine atom content of less than 2.5% had insufficient ink repellency. It is presumed that the surface was not sufficiently covered with Rf .
  • the composition for hard coat containing the partial hydrolysis-condensation product of the present invention has a hardness sufficient for the substrate and can form a hard coat layer having excellent antifouling property, particularly excellent fingerprint adhesion prevention property. Furthermore, there is little environmental impact.
  • the substrate having the hard coat layer is excellent in abrasion resistance and transparency, and the surface thereof has sufficient hardness, and is excellent in antifouling property, particularly, light resistance for preventing fingerprint adhesion. For this reason, it is useful as a member for touch panels, display glasses, optical elements, sanitary equipment, etc. used in smartphones, tablet PCs, etc., which are problematic in appearance due to the appearance of oily dirt, particularly fingerprints. It should be noted that all of the specifications, claims and abstract of Japanese Patent Application No. 2012-017605 filed on January 31, 2012 and Japanese Patent Application No. 2012-245498 filed on November 7, 2012 The contents of which are hereby incorporated herein by reference.

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Abstract

L'invention concerne un produit d'hydrolyse-condensation partielle qui est capable de conférer à la surface d'une couche de revêtement dur des propriétés de dureté et de résistance aux taches suffisantes, notamment des propriétés de prévention de l'accumulation des empreintes, lorsqu'il est ajouté à une résine photodurcissable pour revêtements durs, à partir de laquelle la couche de revêtement dur est obtenue. Le produit d'hydrolyse-condensation partielle permet à la couche de revêtement dur de présenter une apparence adéquate, tout en assurant une résistance à la lumière suffisante des propriétés de prévention de l'accumulation d'empreintes. Par ailleurs, le produit d'hydrolyse-condensation partielle a peu de retombées sur l'environnement. L'invention concerne également : un procédé de production du produit d'hydrolyse-condensation partielle ; une composition pour revêtements durs dans laquelle le produit d'hydrolyse-condensation partielle est mélangé ; une base qui comprend une couche de revêtement dur ; et un panneau tactile. L'invention concerne également un agent pour la prévention de l'accumulation d'empreintes, qui est formé à partir d'un produit d'hydrolyse-condensation partielle d'un mélange de composé de silane hydrolysable, ledit produit d'hydrolyse-condensation partielle contenant une double liaison éthylénique et contenant -CnF2n+1 (avec n ≤ 6) et ayant une teneur en atome fluor de 2,5 à 40 % en masse ; et une composition pour revêtements durs, qui contient un composant photopolymérisable et 0,01 à 20 % en masse du produit d'hydrolyse-condensation partielle par rapport à la teneur totale en solides de la composition.
PCT/JP2013/051923 2012-01-31 2013-01-29 Agent pour la prévention de l'accumulation d'empreintes, son procédé de production, composition pour revêtements durs, base comprenant une couche de revêtement dur et panneau tactile WO2013115191A1 (fr)

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JP2013556418A JP6206188B2 (ja) 2012-01-31 2013-01-29 指紋付着防止剤組成物、指紋付着防止剤の製造方法、ハードコート用組成物、ハードコート層を有する基材およびタッチパネル
CN201380007252.0A CN104080877B (zh) 2012-01-31 2013-01-29 防指纹附着剂及其制造方法、硬质涂层用组合物、具有硬质涂层的基材以及触摸屏
KR1020147019644A KR101969192B1 (ko) 2012-01-31 2013-01-29 지문 부착 방지제 및 그 제조 방법, 하드 코트용 조성물, 하드 코트층을 갖는 기재 그리고 터치 패널

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JP2012245498 2012-11-07
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018078906A1 (fr) * 2016-10-31 2018-05-03 旭硝子株式会社 Composition de fluoroéther, fluide de revêtement et article
US10675658B2 (en) 2014-03-18 2020-06-09 3M Innovative Properties Company Treated article and method of making the same
US10858540B2 (en) 2015-09-23 2020-12-08 3M Innovative Properties Company Composition including silanes and methods of making a treated article
WO2022130855A1 (fr) * 2020-12-16 2022-06-23 住友電気工業株式会社 Composition de résine, matériau de revêtement secondaire pour fibre optique, et fibre optique ainsi que procédé de fabrication de celle-ci
WO2024166724A1 (fr) * 2023-02-07 2024-08-15 信越化学工業株式会社 Agent de revêtement contenant du fluor, article, et procédé de modification de surface d'article

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106927690B (zh) * 2017-02-21 2019-06-07 陕西科技大学 一种使触摸屏玻璃表面防污防指纹的方法
KR20200070810A (ko) 2018-12-10 2020-06-18 삼성전자주식회사 조성물, 이의 경화물을 포함하는 필름, 상기 필름을 포함하는 적층체 및 디스플레이 소자
JP2020180274A (ja) * 2019-04-23 2020-11-05 住友化学株式会社 混合組成物
CN112940236A (zh) * 2021-02-01 2021-06-11 浙江巨化技术中心有限公司 一种高耐磨抗指纹剂的制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000275403A (ja) * 1999-03-19 2000-10-06 Fuji Photo Film Co Ltd 反射防止膜およびそれを配置した表示装置
WO2008032722A1 (fr) * 2006-09-14 2008-03-20 Toray Industries, Inc. Matière de revêtement, article optique utilisant celle-ci et procédé de fabrication d'un article optique
JP2008069292A (ja) * 2006-09-15 2008-03-27 Shin Etsu Chem Co Ltd 光硬化性コーティング組成物及びこの組成物の硬化被膜が形成された物品
JP2008106103A (ja) * 2006-10-24 2008-05-08 Shin Etsu Chem Co Ltd 光及び熱硬化性コーティング剤組成物及びその硬化皮膜を有する物品
JP2011187558A (ja) * 2010-03-05 2011-09-22 Adeka Corp 有機薄膜トランジスタ

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62119141A (ja) * 1985-11-19 1987-05-30 Shin Etsu Chem Co Ltd 放射線硬化性光フアイバ−用被覆剤
JP3222386B2 (ja) * 1996-07-12 2001-10-29 信越化学工業株式会社 コーティング剤組成物及びそのコーティング組成物で処理してなる物品
JP3284947B2 (ja) * 1997-10-17 2002-05-27 信越化学工業株式会社 表面処理剤
JP3876961B2 (ja) * 2000-06-29 2007-02-07 信越化学工業株式会社 表面処理剤及び撥水・撥油性物品
KR20040044062A (ko) 2002-11-20 2004-05-27 김낙주 저농도산과, 초음파를 이용한 다공성 굴패각 분말 제조방법
KR20070089718A (ko) * 2004-12-28 2007-08-31 제이에스알 가부시끼가이샤 반사 방지막
KR101268700B1 (ko) * 2005-03-31 2013-05-29 제이에스알 가부시끼가이샤 액상 경화성 조성물, 경화막 및 대전 방지용 적층체
JP4671338B2 (ja) * 2005-06-27 2011-04-13 日本化薬株式会社 フッ素含有ポリシロキサン、それを用いる感光性樹脂組成物及びその硬化物
JP4711080B2 (ja) 2006-07-25 2011-06-29 信越化学工業株式会社 被膜形成用組成物用フロロオルガノポリシロキサン樹脂の製造方法
JP2008248239A (ja) * 2007-03-08 2008-10-16 Toray Ind Inc シロキサン樹脂組成物、それを用いた硬化膜および光学デバイス
WO2010013816A1 (fr) * 2008-08-01 2010-02-04 旭硝子株式会社 Composition photosensible négative, paroi de séparation pour élément optique utilisant la composition photosensible négative, et élément optique comprenant la paroi de séparation
JP4709272B2 (ja) * 2008-12-11 2011-06-22 信越化学工業株式会社 含フッ素アクリレート
JP6036699B2 (ja) * 2011-10-21 2016-11-30 旭硝子株式会社 撥インク剤の製造方法、ネガ型感光性樹脂組成物、隔壁および光学素子

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000275403A (ja) * 1999-03-19 2000-10-06 Fuji Photo Film Co Ltd 反射防止膜およびそれを配置した表示装置
WO2008032722A1 (fr) * 2006-09-14 2008-03-20 Toray Industries, Inc. Matière de revêtement, article optique utilisant celle-ci et procédé de fabrication d'un article optique
JP2008069292A (ja) * 2006-09-15 2008-03-27 Shin Etsu Chem Co Ltd 光硬化性コーティング組成物及びこの組成物の硬化被膜が形成された物品
JP2008106103A (ja) * 2006-10-24 2008-05-08 Shin Etsu Chem Co Ltd 光及び熱硬化性コーティング剤組成物及びその硬化皮膜を有する物品
JP2011187558A (ja) * 2010-03-05 2011-09-22 Adeka Corp 有機薄膜トランジスタ

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10675658B2 (en) 2014-03-18 2020-06-09 3M Innovative Properties Company Treated article and method of making the same
US10858540B2 (en) 2015-09-23 2020-12-08 3M Innovative Properties Company Composition including silanes and methods of making a treated article
WO2018078906A1 (fr) * 2016-10-31 2018-05-03 旭硝子株式会社 Composition de fluoroéther, fluide de revêtement et article
KR20190077314A (ko) * 2016-10-31 2019-07-03 에이지씨 가부시키가이샤 함불소 에테르 조성물, 코팅액 및 물품
JPWO2018078906A1 (ja) * 2016-10-31 2019-09-26 Ａｇｃ株式会社 含フッ素エーテル組成物、コーティング液および物品
US10988575B2 (en) 2016-10-31 2021-04-27 AGC Inc. Fluoroether composition, coating fluid and article
KR102269698B1 (ko) 2016-10-31 2021-06-25 에이지씨 가부시키가이샤 함불소 에테르 조성물, 코팅액 및 물품
WO2022130855A1 (fr) * 2020-12-16 2022-06-23 住友電気工業株式会社 Composition de résine, matériau de revêtement secondaire pour fibre optique, et fibre optique ainsi que procédé de fabrication de celle-ci
WO2024166724A1 (fr) * 2023-02-07 2024-08-15 信越化学工業株式会社 Agent de revêtement contenant du fluor, article, et procédé de modification de surface d'article

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