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WO2006057297A1 - Composition de resine durcissable et film antireflet - Google Patents

Composition de resine durcissable et film antireflet Download PDF

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Publication number
WO2006057297A1
WO2006057297A1 PCT/JP2005/021577 JP2005021577W WO2006057297A1 WO 2006057297 A1 WO2006057297 A1 WO 2006057297A1 JP 2005021577 W JP2005021577 W JP 2005021577W WO 2006057297 A1 WO2006057297 A1 WO 2006057297A1
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WO
WIPO (PCT)
Prior art keywords
group
meth
refractive index
compound
acrylate
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/JP2005/021577
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English (en)
Japanese (ja)
Inventor
Takaro Yashiro
Takahiro Kawai
Tetsuya Yamamura
Hideaki Takase
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JSR Corp
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JSR Corp
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Publication of WO2006057297A1 publication Critical patent/WO2006057297A1/fr
Anticipated expiration legal-status Critical
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    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/12—Polymers provided for in subclasses C08C or C08F
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • 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
    • 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
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00

Definitions

  • the present invention relates to a curable resin composition and an antireflection film. More specifically, a curable resin composition containing an ethylenically unsaturated group-containing fluorine-containing polymer, which, when cured, provides a cured product having excellent scratch resistance, coating properties, and durability. And an antireflection film comprising a low refractive index layer made of such a cured product.
  • an antireflection film including a low refractive index layer made of a cured product excellent in workability and durability.
  • These display panels are also required to have excellent coating properties without coating defects such as coating unevenness and repellency.
  • the coating properties of the antireflection film are an important factor that affects the appearance of the final product display.
  • a fluorine-based resin coating containing a hydroxyl group-containing fluoropolymer is known (eg, Patent Documents 1 to 3).
  • the obtained coating film had excellent weather resistance, but was poor in scratch resistance and durability!
  • an isocyanate group-containing unsaturated compound having at least one isocyanate group and at least one addition-polymerizable unsaturated group, and a hydroxyl group-containing fluorine-containing polymer.
  • the ratio of the number of isocyanate groups to the number of Z hydroxyl groups is from 0.01 to 1.0.
  • a coating composition containing an unsaturated group-containing fluorine-containing vinyl polymer obtained by reacting at a ratio for example, Patent Document 4).
  • a coating composition containing such a polymer can be cured at a low temperature in a short time, but is further cured using a curing agent such as melamine resin to react with the remaining hydroxyl groups. It was necessary to let them. Furthermore, the coating film obtained in the above publication has a problem that it is sufficient in terms of coatability and scratch resistance.
  • a material for a low refractive index film having a lower refractive index than before is desired! Therefore, by utilizing the fact that the refractive index of air is lower than that of a cocoon resin component such as acrylic, particles having voids inside the particles such as porous particles and hollow particles (hereinafter collectively referred to as hollow particles) are used.
  • the technique used is known (for example, Patent Documents 7 to 9).
  • Patent Document 1 Japanese Patent Application Laid-Open No. 57-34107
  • Patent Document 2 JP-A-59-189108
  • Patent Document 3 JP-A-60-67518
  • Patent Document 4 Japanese Patent Application Laid-Open No. 61-296073
  • Patent Document 5 JP-A-2002-265866
  • Patent Document 6 Japanese Patent Laid-Open No. 10-316860
  • Patent Document 7 Japanese Patent Laid-Open No. 2003-139906
  • Patent Document 8 Japanese Patent Laid-Open No. 2002-317152
  • Patent Document 9 Japanese Patent Laid-Open No. 10-142402
  • the present invention provides a curable resin composition, a cured film, and an antireflection film including the same, which provide a cured film having excellent coatability, a low refractive index and excellent scratch resistance. With the goal.
  • the following curable resin composition, a cured film comprising the same, and an antireflection film are provided.
  • the organic solvent contains the following organic solvents (C1) and (C2), and
  • a curable resin composition that gives a cured product having a refractive index of 1.50 or less.
  • a cured film obtained by heating the curable resin composition according to any one of [1] to [3] above and curing it by irradiation with Z or radiation.
  • the curable resin composition of the present invention has a good coatability and is cured to produce a cured product (cured film) having a low refractive index and excellent scratch resistance. be able to.
  • the cured film of the present invention has a low refractive index and excellent scratch resistance!
  • the antireflection film of the present invention includes the cured film of the present invention having a low refractive index and scratch resistance, and has good antireflection characteristics and scratch resistance.
  • FIG. 1 is a cross-sectional view of an antireflection film according to an embodiment of the present invention.
  • the curable resin composition of the present invention may contain the following components (A) to (F).
  • the refractive index of the cured product obtained by curing the curable resin composition of the present invention with respect to light having a wavelength of 589 nm needs to be 1.50 or less. When the refractive index is within this range, the cured film obtained by curing the curable resin composition of the present invention is suitable as a low refractive index film constituting the antireflection film.
  • the ethylenically unsaturated group-containing fluoropolymer (A) is a fluoroolefin polymer.
  • the composition of the present invention exhibits basic performance as a low refractive index material for an antireflection film such as low refractive index, antifouling property, chemical resistance, and water resistance.
  • the component (A) has a side chain hydroxyl group modified with a (meth) acrylic compound. More preferably, it is modified with a (meth) acrylic compound having an isocyanate group. Such modification enables co-crosslinking with the radically polymerizable (meth) acrylic compound and improves the scratch resistance.
  • the ethylenically unsaturated group-containing fluorine-containing polymer is obtained by combining a compound containing one isocyanate group, at least one ethylenically unsaturated group, and a hydroxyl group-containing fluorine-containing polymer with an isocyanate group Z. It is obtained by reacting at a molar ratio of hydroxyl group of 1.1 to 1.9.
  • the compound containing one isocyanate group and at least one ethylenically unsaturated group contains one isocyanate group and at least one ethylenically unsaturated group in the molecule. If it is a compound, it is not particularly limited.
  • gelling may occur when reacting with a hydroxyl group-containing fluoropolymer.
  • a curable rosin composition to be described later can be hardened more easily, and therefore a compound having a (meth) atallyloyl group is more preferable.
  • examples of such a compound include 2- (meth) atalylooxychetyl isocyanate and 2- (meth) atalylooxypropylisocyanate alone or in combination of two or more.
  • such a compound can be synthesized by reacting diisocyanate and a hydroxyl group-containing (meth) acrylate.
  • diisocyanates examples include 2,4-tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, methylene bis (4-cyclohexylenoisocyanate).
  • Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate.
  • Pentaerythritol tri (meth) acrylate is preferred.
  • hydroxyl group-containing polyfunctional (meth) atalylate examples include, for example, Osaka Organic Chemical Co., Ltd., trade name HEA, Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA, PET-30, Toagosei ( Product name Alonics M-215, M-233, M-305, M-400, etc.
  • the hydroxyl group-containing fluoropolymer preferably contains the following structural units (a), (b) and (c): It becomes.
  • R 1 represents a fluorine atom, a fluoroalkyl group or a group represented by OR 2 (R 2 represents an alkyl group or a fluoroalkyl group)]
  • R 3 represents a hydrogen atom or a methyl group
  • R 4 represents an alkyl group, — (CH 2) OR 5 or
  • R 5 represents an alkyl group or a glycidyl group, X represents a number of 0 or 1), a carboxyl group or an alkoxycarbo group
  • R 6 represents a hydrogen atom or a methyl group
  • R 7 represents a hydrogen atom or a hydroxyalkyl group
  • V represents a number of 0 or 1
  • the fluoroalkyl group of R 1 and R 2 includes a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, and a perfluorohexyl.
  • Group, perfluorocyclohexyl group, etc. having 1 to 6 carbon atoms examples include an alkyl group.
  • Examples of the alkyl group for R 2 include alkyl groups having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a cyclohexyl group.
  • the structural unit (a) can be introduced by using a fluorine-containing vinyl monomer as a polymerization component.
  • a fluorine-containing butyl monomer is not particularly limited as long as it is a compound having at least one polymerizable unsaturated double bond and at least one fluorine atom. Examples of this include fluoroolefins such as tetrafluoroethylene, hexafluoropropylene, 3, 3, 3-trifluoropropylene; alkyl perfluoro oral ether or alkoxyalkyl perfluorobule.
  • Ethers Perfluoro (alkyl butyl ether) such as perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), (propyl vinyl ether), perfluoro (butinolevino reetenole), perfluoro (isobutino vinyl ether), etc.
  • a single perfluoro (alkoxyalkyl butyl ether) such as perfluoro (propoxypropyl butyl ether) or a combination of two or more thereof.
  • hexafluoropropylene and perfluoro (alkyl butyl ether) or perfluoro (alkoxy alkyl butyl ether) are more preferred and used in combination!
  • the content of the structural unit (a) is 20 to 70 mol% when the total amount of the hydroxyl group-containing fluoropolymer is 100 mol%. This is because when the content is less than 20 mol%, it may be difficult to develop a low refractive index, which is an optically characteristic of the fluorine-containing material as intended by the present invention. This is because if the content exceeds 70 mol%, the solubility of the hydroxyl-containing fluoropolymer in an organic solvent, transparency, or adhesion to a substrate may be lowered.
  • the content of the structural unit (a) is preferably 25 to 65 mol%, more preferably 30 to 60 mol%, based on the total amount of the hydroxyl group-containing fluoropolymer. Power S is more preferable.
  • alkyl group for R 4 or R 5 a methyl group, an ethyl group, a propyl group C 1-12 alkyl groups such as hexyl group, cyclohexyl group, lauryl group and the like, and alkoxycarbonyl groups include methoxycarbonyl group, ethoxycarbonyl group and the like.
  • the structural unit (b) can be introduced by using the above-mentioned butyl monomer having a substituent as a polymerization component.
  • bur monomers include methyl vinyl ethere, ethino levinino le ethere, n- propino levinino ethere, isopropino levinino ether, n-butyl vinyl ether, isobutyl vinyl ether, tert -Butyl vinyl etherenole, n-pentinolevinoreethenole, n-hexenolevinoreethenore, n-year-old cubinorebi-noreethenore, n-dodecinolevinorethenore, 2-ethinorehexinolevinoreteol, cyclohexyl vinyl ether Alkyl butyl ethers or cycloalkyl alkyl ethers such as: ethyl
  • the content of the structural unit (b) is 10 to 70 mol% when the total amount of the hydroxyl group-containing fluoropolymer is 100 mol%.
  • the reason for this is that when the content is less than 10 mol%, the solubility of the hydroxyl group-containing fluoropolymer in the organic solvent may be reduced.
  • the content exceeds 70 mol%, This is because the optical properties such as transparency and low reflectivity of the hydroxyl group-containing fluoropolymer may be deteriorated.
  • the content of the structural unit (b) is preferably 20 to 60 mol%, more preferably 20 to 60 mol%, based on the total amount of the hydroxyl group-containing fluoropolymer. Power S is more preferable.
  • the hydroxyalkyl group for R 7 includes a 2-hydroxyethyl group, 2-hydroxy group Examples include droxypropyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 3-hydroxybutyl group, 5-hydroxypentyl group, and 6-hydroxyhexyl group.
  • the structural unit (c) can be introduced by using a hydroxyl group-containing vinyl monomer as a polymerization component.
  • hydroxyl-containing butyl monomers include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 5-hydroxypentyl.
  • Hydroxyl-containing butyl ethers such as vinyl ether, 6-hydroxyhexyl vinyl ether, hydroxyl-containing butyl ethers such as 2-hydroxyethyl allyl ether, 4-hydroxy butyl allyl ether, glycerol monoallyl ether, allyl alcohol, etc. Can be mentioned.
  • hydroxyl group-containing vinyl monomers include 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and force prolatatone ( (Meth) acrylate, polypropylene glycol (meth) atrelate, etc. can be used.
  • the content of the structural unit (c) is preferably 5 to 70 mol% when the total amount of the hydroxyl group-containing fluoropolymer is 100 mol%. This is because when the content is less than 5 mol%, the solubility of the hydroxyl group-containing fluoropolymer in the organic solvent may be reduced. On the other hand, when the content exceeds 70 mol%, This is because the optical properties such as transparency and low reflectivity of the hydroxyl group-containing fluoropolymer may be deteriorated.
  • the content of the structural unit (c) is 5 to 40 mol% with respect to the total amount of the hydroxyl group-containing fluoropolymer. It is more preferable to do this.
  • the hydroxyl group-containing fluoropolymer preferably further comprises the following structural unit (d).
  • R 8 and R 9 may be the same or different and each represents a hydrogen atom, an alkyl group, a halogenated alkyl group or an aryl group]
  • the alkyl group of R 8 or R 9 is an alkyl group having 1 to 3 carbon atoms, such as a methyl group, an ethyl group, or a propyl group.
  • a fluoroalkyl group having 1 to 4 carbon atoms such as a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, or the like is a phenyl group or a benzyl group.
  • a naphthyl group and the like is a phenyl group or a benzyl group.
  • the structural unit (d) can be introduced by using an azo group-containing polysiloxane compound having a polysiloxane segment represented by the above formula (4).
  • an azo group-containing polysiloxane compound having a polysiloxane segment represented by the above formula (4).
  • Examples of such an azo group-containing polysiloxane compound include compounds represented by the following formula (5).
  • R 1Q to R 13 represent the same or different hydrogen atom, alkyl group or cyan group, and R ′′ to R 17 may be the same or different.
  • the structural unit (d) is included in the hydroxyl group-containing fluoropolymer as a part of the structural unit (e).
  • R 1U to R ′′, R 14 to R ′′, p, q, s, t and y are the same as those in the above formula (5).
  • the alkyl groups represented by R 1Q to R 13 include carbon atoms such as a methyl group, an ethyl group, a propyl group, a hexyl group, and a cyclohexyl group. 1-12 alkyl groups are mentioned, R
  • the alkyl group represented by “ ⁇ R 17 ” includes an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, and a propyl group.
  • the azo group-containing polysiloxane compound represented by the above formula (5) is particularly preferably a compound represented by the following formula (7).
  • the content of the structural unit (d) is preferably 0.1 to 10 mol% when the total amount of the hydroxyl group-containing fluoropolymer is 100 mol%.
  • the reason for this is that when the content is less than 0.1 mol%, the surface slipperiness of the coated film after curing may be lowered, and the scratch resistance of the coated film may be lowered. If it exceeds 10 mol%, the transparency of the hydroxyl group-containing fluorine-containing polymer is inferior, and when used as a coating material, repelling or the like may easily occur during coating.
  • the content of the structural unit (e) should be determined so that the content of the structural unit (d) contained therein falls within the above range.
  • the hydroxyl group-containing fluoropolymer preferably further comprises the following structural unit (f).
  • R 18 represents a group having an emulsifying action
  • the group having an emulsifying action of R 18 has both a hydrophobic group and a hydrophilic group, and the hydrophilic group is a polyether structure such as polyethylene oxide or polypropylene oxide. The group is preferred.
  • Examples of the group having an emulsifying action include a group represented by the following formula (9).
  • n is a number from 1 to 20
  • m is a number from 0 to 4
  • u is a number from 3 to 50
  • the structural unit (f) can be introduced by using a reactive emulsifier as a polymerization component.
  • a reactive emulsifier examples include compounds represented by the following formula (10).
  • the content of the structural unit (f) is preferably 0.1 to 5 mol% when the total amount of the hydroxyl group-containing fluoropolymer is 100 mol%.
  • the reason for this is that when the content ratio is 0.1 mol% or more, the solubility of the hydroxyl group-containing fluoropolymer in the solvent is improved. If the proportion is within 5 mol%, the tackiness of the curable resin composition will not increase excessively, it will be easy to handle, and even if it is used as a coating material, the moisture resistance will not decrease. Because.
  • the hydroxyl group-containing fluoropolymer preferably has a polystyrene equivalent number average molecular weight of 5,000 to 500,000 as measured by gel permeation chromatography using tetrahydrofuran as a solvent.
  • the reason for this is that when the number average molecular weight is less than 5,000, the mechanical strength of the hydroxyl group-containing fluoropolymer may be reduced.
  • the number average molecular weight exceeds 500,000, it will be described later. This is because the viscosity of the curable resin composition becomes high and thin film coating may be difficult.
  • the hydroxyl group-containing fluoropolymer has a polystyrene-reduced number average molecular weight of preferably 10,000 to 300,000, more preferably 10,000 to 100,000.
  • the ethylenically unsaturated group-containing fluorine-containing polymer comprises the above-mentioned compound containing one isocyanate group, at least one ethylenically unsaturated group, and a hydroxyl group-containing fluorine-containing polymer. It is obtained by reacting at a molar ratio of hydroxyl group of 1.1 to 1.9. The reason for this is that if the molar ratio is less than 1.1, the scratch resistance and durability may be reduced. On the other hand, if the molar ratio exceeds 1.9, the application of the curable resin composition is not possible. This is because the scratch resistance of the membrane after immersion in an alkaline solution may be lowered.
  • the molar ratio of the isocyanate group Z hydroxyl group is preferably 1.1 to 1.5, more preferably 1.2 to 1.5.
  • the amount of component (A) to be added is not particularly limited, but is usually 10 to 90% by weight based on the total amount of the composition other than the organic solvent. The reason for this is that when the amount added is less than 10% by weight, the refractive index of the cured coating film of the curable resin composition becomes high, and a sufficient antireflection effect may not be obtained. When the added amount exceeds 90% by weight, it is curable This is because the scratch resistance of the cured coating film of the resin composition may not be obtained.
  • (A) rather more preferably that a 15 to 90% by weight ⁇ components, further preferably a value within the range of 20 to 85 weight 0/0 .
  • the (meth) acrylate compound is used for enhancing the scratch resistance of a cured product obtained by curing a curable resin composition and an antireflection film using the cured product.
  • the compound is not particularly limited as long as it is a compound containing at least one (meth) attaroyl group in the molecule.
  • Monomers having one (meth) atallyloyl group include, for example, acrylamide, (meth) acryloylmorpholine, 7-amino-3,7-dimethyloctyl (meth) acrylate, isobutoxymethyl (meth) acrylamide, isobornyloxetyl ( (Meth) Atarylate, Isovolyl (Meth) Atylate, 2-Ethylhexyl (Meth) Atylate, Ethyl Jetylene Glycol (Meth) Atylate, t-Octyl (Meth) acrylamide, Diacetone (Meth) Acrylate Mido, dimethylaminoethyl (meth) acrylate, jetylaminoethyl (meth) acrylate, lauryl (meth) acrylate, dicyclopentagen (meth) acrylate, dicyclopente-roxetyl (meth) acrylate, dicyclopentale (Meta
  • examples of the monomer having two or more (meth) atalyloyl groups include ethylene glycol di (meth) acrylate, dicyclopentadidi (meth) acrylate, triethylene glycol dialate, tetraethylene glycol diacrylate.
  • composition of the present invention preferably contains a compound containing at least two (meth) atalyloyl groups in the molecule. More preferably, a compound containing at least 3 or more (meth) atalyloyl groups in the molecule is particularly preferable.
  • Such three or more compounds include the tri (meth) atareto toy compounds exemplified above, tetra (meth) atta relay toy compounds, penta (meth) atalyto toy compounds, hexa ( It is possible to select from among the meta) talate toy compounds, among which trimethylol propane tri (meth) acrylate, EO-modified trimethylol propane tri (meth) acrylate, dipentaerythritol Sa (meth) acrylate, dipentaerythritol penta (meth) acrylate, and ditrimethylol propanetetra (meth) acrylate are particularly preferred.
  • trimethylol propane tri (meth) acrylate EO-modified trimethylol propane tri (meth) acrylate
  • dipentaerythritol Sa (meth) acrylate dipentaerythritol penta (meth) acrylate
  • the (meth) atalytoy compound may contain fluorine.
  • fluorine examples include perfluorooctylethyl (meth) acrylate, octafluoropentyl (meth) acrylate, trifluoroethyl (meth) acrylate, and the like alone or in combination The combination of the above is mentioned.
  • the amount of component (B) to be added is not particularly limited, but is usually 1 to 88% by weight based on the total amount of the composition other than the organic solvent. The reason for this is that if the addition amount is less than 1% by weight, the scratch resistance of the cured coating film of the curable resin composition may not be obtained, while the addition amount exceeds 88% by weight. This is because the refractive index of the cured coating film of the curable resin composition becomes high and a sufficient antireflection effect may not be obtained.
  • the addition amount of the component (B) is more preferably 1 to 60% by weight, and further preferably 1 to 40% by weight.
  • the curable composition of the present invention needs to contain the following organic solvents (C1) and (C2). By containing these organic solvents, the coating properties of the curable composition can be improved.
  • the organic solvent (C2) An organic solvent having a boiling point of 130 ° C or higher and 200 ° C or lower at 25 ° C1 atm.
  • the organic solvent (C1) reduces the surface tension of the curable resin composition of the present invention, Improve sex.
  • Specific examples of the organic solvent (C1) include n-pentane, 2-methylbutane, n-hexane, 2-methylpentane, 2,2 dimethylbutane, 2,3 dimethylbutane, n-heptane, isooctane, and cyclopentane.
  • Aliphatic hydrocarbons such as methylcyclopentane and cyclohexane, methyl chloride, acetyl chloride, chloropropyl chloride, isopropyl chloride, chlorobutyl chloride, isobutyl chloride, t-butyl chloride, sec butyl chloride, 1, Halogens such as 1-diclonal ethane, hexafluorobenzene, 1, 1, 2-trichloroeuro- 1, 2, 2, — trifluoroethane, 1, 1, 2, 2-tetrachloro-1, 2-difluoroethane Hydrocarbons, methyl ethyl ketone (MEK), ketones such as acetone, methanol, ethanol, 1 propanol , Isopropyl alcohol (IPA), 1-butanol, 2-butanol, t-butanol, alcohols such as 2, 2, 2-trifluoroethanol, jetyl ether, dipropyl ether, diiso
  • MEK surface tension 2. 4 X 10 _4 NZcm
  • ketones such as acetone
  • IPA surface tension 2. 2 X 10 _4 NZcm
  • t chromatography butanol surface tension 1. 9 X 10 _4 NZcm
  • t-butanol is more preferable.
  • the surface tension of the organic solvent (C1) must be less than 2.5 X 10 _4 NZcm at 25 ° C and 1 atm, and preferably less than 2.1 X 10 _4 NZcm.
  • the surface tension is measured by the wall Helmi (plate) method.
  • the organic solvent (C2) prevents whitening of the coating film in the step of removing the organic solvent after applying the curable resin composition of the present invention.
  • the organic solvent (C2) include aliphatic hydrocarbons such as nonane, decane, dodecane, ethylcyclohexane, p-menthane, o-xylene, m-xylene, p-xylene, ethylbenzene, tamen, mesitylene, n— Aromatic hydrocarbons such as butylbenzene, sec butylbenzene, tert-butylenebenzene, p-cymene, o-jetylbenzene, m-jetylbenzene, p-decylbenzene, n-pentylbenzene, 1, 1, 2, 2-tetrachloroethane, pentachloroethane, hexachloroethane, 1, 2, 3 trichloroprone,
  • Halogenated charcoal hydrogen 1-pentanol, 2-methoxyethanol, 2-ethoxyethanol, 1- Xyl-2-propanol, isopentyl alcohol, 1-hexanol, 2-methyl-1 pentanol, 4-methyl-2 pentanol, 2 ethyl 1-butanol, 1 heptanol, 2 heptanol, 3 heptanol, 1-octanol, 2— Octanol, 2 Ethyl 1 Hexanol, 3, 5, 5 Trimethylhexanol, Cyclohexano 1-methylcyclohexanol, 2-methylenohexanol, 3-methinohexanol, 4 methylhexanol, 1,2 ethanediol, 1,2 propanediol, 1,2 butanediol, 2-methyl-2, 4 Pentanediol, phenol, o-cresol, 2-ethoxyethanol, 2- (methoxyethoxy)
  • ethers such as bis (2 chloroethyl) ether, 2 heptanone (MAK), 4 1-Heptanone, Diisoptyl ketone, Acetonylacetone, Cyclohexanone, Methyl ketone Hexanone and other ketones, pentyl formate, pentyl acetate, isopentyl acetate, 3-methoxybutyl acetate, sec Hexyl, 2-ethylbutyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, butyl propionate, isopentyl propionate, butyl butyrate, isobenzyl
  • MA 4 monoheptanone, diisobutylketone, acetonylacetone, cyclohexanone, methylcyclohexanone and other ketons, lactic acid ethyl, butyl lactate, 2-ethoxyethyl acetate, 2-methoxyethylyl Esters such as cetate, 2-butoxychetyl acetate, methyl acetoacetate, ethyl acetoacetate, propylene glycol monomethyl ether acetate (PGMEA) are preferred, more preferably MA :, cyclohexanone, ethyl lactate, PGMEA It is.
  • the curable resin composition of the present invention has a boiling point at 25 ° C1 atm of 100 ° C or more and less than 130 ° C, in addition to the organic solvents (C1) and (C2), if necessary.
  • the curable composition after coating can be quickly dried.
  • organic solvent (C3) examples include aliphatic hydrocarbons such as octane, 2, 2, 3 trimethylpentane, 2, 2, 5 trimethylhexane and methylcyclohexane, aromatic hydrocarbons such as toluene, 1, Halogenated hydrocarbons such as 1,2-trichlorodiethane, 1,1,1,1,2-tetrachlorodiethane, 1-cyclopentane, benzotrifluoride, 1-bromo-2-chloroethane, 2 pentanone, 3 pentanone, 2 Ketones such as xanone, methyl isobutyl ketone (MIBK), 1-butanol, isobutyl alcohol, 2 pentanol, 3 pentanol, t-pentyl alcohol, 2-methyl-1-butanol, 3-methyl-2-butanol, neopentyl alcohol, 4-Methyl-2-pentanol, 2-methoxyethanol, 1-methoxy 2-propan
  • ketones such as 2 pentanone, 3 pentanone, 2-hexanone, methyl isobutyl ketone (MIBK), butyrate formate, propyl acetate, butyl acetate, isobutyl acetate, sec butyl acetate, methyl butyrate, ethyl butyrate, More preferred are esters such as jetyl carbonate and pentyl lactate. Is butyl acetate, MIBK.
  • MIBK methyl isobutyl ketone
  • the blending amount (total amount) of the (C) organic solvent in the curable resin composition of the present invention is not particularly limited, but all components other than the (C) organic solvent in the composition 100
  • the amount is usually 100 to 100,000 parts by weight, preferably 300 to 20000 parts by weight, and more preferably 1000 to 10,000 parts by weight with respect to parts by weight.
  • the amount of (C 1) component, (C2) component and (C3) component contained in 100% by weight of all (C) component is 10-99.5% by weight, 0.5-90% by weight and 0 to 89.5 percent by weight, good Mashiku is 20 to 98.5 wt 0/0, a 0.5 to 80 weight 0/0 and 1 to 79.5 wt 0/0, more preferably 30 to 80% by weight, 1 to 60% by weight and 1 to 69% by weight.
  • (D) particles containing silica as a main component can be blended.
  • the particle size is measured with a transmission electron microscope.
  • the scratch resistance of the cured product of the curable resin composition of the present invention can be improved.
  • these particles containing silica as a main component known particles can be used. If the shape of the particles is spherical, not only ordinary colloidal silica but also hollow particles, porous particles, core-shell type particles are used. And so on. However, it is particularly preferable that a part or all of the component (D) preferred by the hollow particles and the porous particles is hollow particles to reduce the refractive index of the obtained cured product. Moreover, it is not limited to a spherical shape, and may be an irregularly shaped particle. Colloidal silica having a solid content of 10 to 40% by weight is preferred.
  • the dispersion medium is water! /
  • an organic solvent is preferred.
  • organic solvents include alcohols such as methanol, isopropyl alcohol, ethylene glycolol, butanol, ethylene glycol monopolypropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic carbonization such as toluene and xylene.
  • Hydrogens Amides such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; Esters such as ethyl acetate, butyl acetate, and ⁇ -butalate Rataton; Organic solvents such as ethers such as tetrahydrofuran and 1,4 dioxane Of these, alcohols and ketones are preferred. These organic solvents can be used alone or in combination as a dispersion medium.
  • Amides such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone
  • Esters such as ethyl acetate, butyl acetate, and ⁇ -butalate Rataton
  • Organic solvents such as ethers such as tetrahydrofuran and 1,4 dioxane Of these, alcohols and ketones are preferred. These organic solvents can be used alone or in combination as a dispersion medium.
  • particles mainly composed of silica include, for example, colloidal silica manufactured by Nissan Chemical Industries, Ltd.
  • the surface of the colloidal silica that has been subjected to a surface treatment such as chemical modification can be used.
  • it contains a hydrolyzable key compound having one or more alkyl groups in the molecule or a hydrolyzate thereof.
  • hydrolyzable silicon compounds include trimethylmethoxysilane, tryptylmethoxysilane, dimethyldimethoxysilane, dibutinoresimethoxysilane, methyltrimethoxysilane, butinoretrimethoxysilane, octyltrimethoxysilane, dodecyltrimethoxy.
  • it has one or more reactive groups in the molecule.
  • Use hydrolyzable key compounds Also.
  • Molecular hydrolyzable Kei-containing compound having one or more reactive groups in the as having ⁇ group as the reactive group In example embodiment, urea propyltrimethoxysilane, Nyu-
  • Examples of those having a thiol group, such as ethyltrimethoxysilane include 3-mercaptopropyltrimethoxysilane.
  • a preferred compound is 3-mercaptopropyltrimethoxysilane.
  • Particles (D) containing silica as a main component are organic compounds containing polymerizable unsaturated groups (hereinafter referred to as "special Sometimes referred to as “constant organic compound”. It is preferable that the surface treatment is performed by (). Powerful surface treatment enables co-crosslinking with UV curable acrylic monomers, improving scratch resistance.
  • the specific organic compound used in the present invention is a polymerizable compound containing a polymerizable unsaturated group in the molecule.
  • This compound is preferably a compound further containing a group represented by the following formula (11) in the molecule, and a compound having a silanol group in the molecule or a compound that generates a silanol group by hydrolysis.
  • X represents NH, 0 (oxygen atom) or S (ion atom), Y represents O or S o)
  • the polymerizable unsaturated group contained in the specific organic compound is not particularly limited.
  • the polymerizable unsaturated group includes, but is not limited to, atalyloyl group, methacryloyl group, vinyl group, probe group, butagel group, styryl group, ethynyl group, cinnamoyl group, Maleate groups and acrylamide groups can be mentioned as preferred examples.
  • This polymerizable unsaturated group is a structural unit that undergoes addition polymerization with active radical species.
  • the specific organic compound preferably further contains a group represented by the formula (11) in the molecule.
  • These groups can be used alone or in combination of two or more.
  • the specific organic compound is a compound having a silanol group in the molecule (hereinafter referred to as “silanol group-containing compound” t) or a compound that generates a silanol group by hydrolysis (hereinafter referred to as “silanol group-generating compound”). Is preferred).
  • silanol group-generating compound include compounds having an alkoxy group, an aryloxy group, a acetoxy group, an amino group, a halogen atom, etc. on the silicon atom.
  • An alkoxy group or an aryloxy group is formed on the silicon atom.
  • a compound containing the compound, that is, an alkoxysilyl group-containing compound or an aryloxysilyl group-containing compound is preferable.
  • the silanol group-generating site of the silanol group or silanol group-generating compound is a structural unit that binds to particles containing silica as a main component by a condensation reaction that occurs following a condensation reaction or hydrolysis.
  • the specific organic compound include, for example, a compound represented by the following formula (12).
  • R 1 and R 2U are the same or different hydrogen atoms, alkyl groups having 1 to 8 carbon atoms, or aryl groups, and a represents a number of 1, 2 or 3.
  • R 19 and R 2 ° examples include methyl, ethyl, propyl, butyl, octyl, phenol, xylyl group and the like.
  • Examples of the group represented by [(R 19 0) R 20 Si—] include, for example, a trimethoxysilyl group, a triethoxy group, and the like.
  • a 3 ⁇ a examples thereof include a silyl group, a triphenoxysilyl group, a methyldimethoxysilyl group, and a dimethylmethoxysilyl group. Of these groups, a trimethoxysilyl group or a triethoxysilyl group is preferable.
  • R 21 is a divalent organic group having an aliphatic or aromatic structure having 1 to 12 carbon atoms, and may contain a chain, branched or cyclic structure.
  • examples of such an organic group include methylene, ethylene, propylene, butylene, hexamethylene, cyclohexylene, phenylene, xylylene, and dodecamethylene.
  • preferred examples are methylene, propylene, cyclohexylene, and phenylene.
  • R 22 is a divalent organic group, and usually a molecular weight of 14 to 10,000, preferably a molecular force of 76 or 500, and the medium force of a divalent organic group is selected.
  • chain polyalkylene groups such as hexamethylene, otatamethylene, dodecamethylene, etc .
  • alicyclic or polycyclic divalent organic groups such as cyclohexylene, norvolylene, etc .
  • phenylene, naphthylene, biphenylene, And divalent aromatic groups such as polyphenylene, and these alkyl group-substituted and aryl-substituted groups.
  • these divalent organic groups may include a polyether bond, a polyester bond, a polyamide bond, a polycarbonate bond, which may contain an atomic group containing an element other than carbon and hydrogen atoms, and further in the above formula (11). Indicating groups can also be included.
  • R 23 is (b + 1) -valent organic group, preferably a linear, branched or cyclic saturated hydrocarbon group, selected from unsaturated hydrocarbon group.
  • Z represents a monovalent organic group having a polymerizable unsaturated group in the molecule that undergoes an intermolecular crosslinking reaction in the presence of an active radical species.
  • an active radical species for example, ataryloyl (oxy) group, meta-atallyloyl (oxy) group, bur (oxy) group, probe (oxy) group, butagel (oxy) group, styryl (oxy) group, ethur ( Oxy) group, cinnamoyl (oxy) group, maleate group, allylamido group, methacrylamide group and the like.
  • an allyloyl (oxy) group and a methacryloyl (oxy) group are preferable.
  • b is preferably a positive integer of 1 to 20, more preferably 1 to 10, particularly preferably 1 to 5.
  • a method described in JP-A-9-100111 can be used. That is, (i) an addition reaction between a mercaptoalkoxysilane, a polyisocyanate compound, and an active hydrogen group-containing polymerizable unsaturated compound. More can be done. Alternatively, the reaction can be carried out by a direct reaction between a compound having an alkoxysilyl group and an isocyanate group in the molecule and an active hydrogen-containing polymerizable unsaturated compound. Furthermore, (c) it can be synthesized directly by addition reaction of a compound having a polymerizable unsaturated group and isocyanate group in the molecule with mercaptoalkoxysilane or aminosilane.
  • (i) is preferably used to synthesize the compound represented by the formula (12). More specifically, for example,
  • mercaptoalkoxysilanes include mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, mercaptopropylmethyldiethoxysilane, mercaptopropyldimethoxymethylsilane, mercaptopropylmethoxydimethylsilane, mercaptopropyltriphenoxysilane, mercapto And propyltributoxysilane.
  • mercaptopropyltrimethoxysilane and mercaptopropyltriethoxysilane are preferable.
  • a product of addition of an amino-substituted alkoxy silane and an epoxy group-substituted mercaptan, an epoxy silane and ⁇ , ⁇ -dimethyl An addition product with a Lukaptoi compound can also be used.
  • the polyisocyanate compound used in the synthesis of the specific organic compound can be selected from the polyisocyanate compounds composed of chain saturated hydrocarbons, cyclic saturated hydrocarbons, and aromatic hydrocarbons.
  • polyisocyanate compounds include, for example, 2,4 tolylene diisocyanate, 2,6 tolylene diisocyanate, 1,3 xylylene diisocyanate, 1,4-xylylene Range isocyanate, 1,5 Naphthalene diisocyanate, m-Phenol-diisocyanate, p-Phenol-diisocyanate, 3,3, -dimethinoleol 4,4, -diphenylmethane diisocyanate, 4,4'-diphenyl- L-methane diisocyanate, 3,3, -dimethylphenol diisocyanate, 4,4, -biphenol-diisocyanate, 1,6 hexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclo Hexinoreisocyanate), 2,2,4 Trimethylhexamethylene diisocyanate, bis (2-isocyanateethyl) fuma
  • 2,4 tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, methylene bis (4-cyclohexylenoisocyanate), 1, 3 bis (isocyanate) Nate methyl) cyclohexane, etc. are preferred. These can be used alone or in combination of two or more.
  • Examples of these active hydrogen-containing polymerizable unsaturated compounds include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2 Hydroxy 1 3 Phenyloxypropyl (meth) acrylate, 1,4 —Butanediol mono (meth) acrylate, 2-hydroxyalkyl (meth) attaylyl phosphate, 4-hydroxycyclohexyl (meth) acrylate, 1,6-hexane monomono (meth) acrylate , Neopentyl alcohol mono (meth) attairelate, trimethylol propanedi (meth) atelier, trimethy mouth-lugetane (meth) atelate, pentaerythritol tri (meth) attalierate, dipentaerythritol penta (Meta) Attalinate etc.
  • glycidyl group-containing compounds such as alkyl glycidyl ether, allyl glycidyl ether, glycidyl (meth) acrylate, and (meth) acrylic acid can be used.
  • glycidyl group-containing compounds such as alkyl glycidyl ether, allyl glycidyl ether, glycidyl (meth) acrylate, and (meth) acrylic acid
  • 2-hydroxyxetyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and pentaerythritol (meth) acrylate are preferred.
  • the surface treatment method of the particles with the specific organic compound is not particularly limited, but it can also be produced by mixing the specific organic compound and particles, heating and stirring.
  • the reaction is preferably carried out in the presence of water in order to efficiently combine the silanol group-generating site of the specific organic compound with the particles.
  • the surface treatment can be performed by a method including an operation of mixing at least the particles and the specific organic compound.
  • the reaction amount of the particles and the specific organic compound is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, and particularly preferably, with the total of the particles and the specific organic compound being 100% by weight. Is 1% by weight or more. If it is less than 0.01% by weight, the resulting cured product may not have sufficient transparency and scratch resistance due to insufficient dispersibility of the particles in the composition.
  • the amount of water consumed by hydrolysis of the alkoxysilane compound during the surface treatment should be such that at least one alkoxy group on the silicon in one molecule is hydrolyzed. Yes.
  • the amount of water added or present during hydrolysis is at least one third of the number of moles of all alkoxy groups on the silicon, more preferably two minutes of the number of moles of all alkoxy groups. 1 to less than 3 times.
  • the product obtained by mixing the alkoxysilane compound and the particles in a completely moisture-free condition is a product in which the alkoxysilane compound is physically adsorbed on the particle surface. In the cured product of the composition containing the composed particles, the effect of developing high hardness and scratch resistance is low.
  • the alkoxysilane compound is separately subjected to hydrolysis, and then mixed with powder particles or solvent dispersion sol of particles, followed by heating and stirring.
  • a method of hydrolyzing the alkoxysilane compound in the presence of particles; or a method of surface-treating the particles in the presence of other components such as a polymerization initiator can be selected.
  • a method in which the alkoxysilane compound is hydrolyzed in the presence of particles is preferable.
  • the temperature is preferably 0 ° C or higher and 150 ° C or lower, more preferably 20 ° C or higher and 100 ° C or lower.
  • the processing time is usually in the range of 5 minutes to 24 hours.
  • an organic solvent is added for the purpose of smoothly and uniformly carrying out the reaction with the alkoxysilane compound. Also good.
  • organic solvent include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, and lactic acid.
  • Esters such as ethyl and y butyrolatatatone; Ethers such as ethylene glycol monomethyl ether and polyethylene glycol monobutyl ether; Aromatic hydrocarbons such as benzene, toluene and xylene; Dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc.
  • the amides can be mentioned. Of these, methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene and xylene are preferred.
  • the amount of these solvents added is not particularly limited as long as it meets the purpose of carrying out the reaction smoothly and uniformly.
  • a solvent-dispersed sol When a solvent-dispersed sol is used as particles, a small amount of the solvent-dispersed sol and the specific organic compound are used. It can be produced by mixing at least.
  • an organic solvent which is uniformly compatible with water may be added for the purpose of ensuring uniformity at the initial stage of the reaction and allowing the reaction to proceed smoothly.
  • an acid, salt or base may be added as a catalyst.
  • the acid examples include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid; organic acids such as methanesulfonic acid, toluenesulfonic acid, phthalic acid, malonic acid, formic acid, acetic acid, and succinic acid; methacrylic acid, acrylic acid, An unsaturated organic acid such as itaconic acid, as a salt, for example, an ammonium salt such as tetramethyl ammonium hydrochloride, tetraptyl ammonium hydrochloride, etc., and as a base, for example, Ammonia water, jetylamine, triethylamine, dibutylamine, primary amines such as cyclohexylamine, secondary or tertiary aliphatic amines, aromatic amines such as pyridine, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, Examples include quaternary ammonium hydrox
  • the organic acid, unsaturated organic acid, as the base tertiary Amin or quaternary ammonium - a Umuhidorokishido is preferably 0.001 to 1.0 parts by weight, more preferably 0.01 parts by weight and 0.1 parts by weight with respect to 100 parts by weight of the alkoxysilane compound.
  • inorganic compounds such as zeolite, anhydrous silica and anhydrous alumina, and organic compounds such as methyl orthoformate, ethyl orthoformate, tetraethoxymethane, and tetrabutoxymethane can be used.
  • orthoesters such as methyl orthoformate and ethyl orthoformate are preferred.
  • the amount of the alkoxysilane compound bound to the particles is usually 110 ° C to 800 ° C in air as a constant value of weight loss% when the dry powder is completely burned in air. It can be determined by thermogravimetric analysis.
  • the blending amount of component (D) in the resin composition is usually 0 to 40% by weight, preferably 1 to 30% by weight, based on the total amount of the composition other than the organic solvent. Weight percent is even more preferred.
  • the amount of particles means solid content, and the particles are used in the form of a solvent dispersion sol. Sometimes the amount does not include the amount of solvent.
  • a compound that generates active species upon irradiation with active energy rays or heat is used to cure the curable resin composition.
  • photopolymerization initiators examples include photoradical generators that generate radicals as active species.
  • the active energy ray is defined as an energy ray capable of decomposing a compound that generates active species to generate active species.
  • active energy rays include optical energy rays such as visible light, ultraviolet rays, infrared rays, X rays, ⁇ rays, j8 rays, and ⁇ rays.
  • ultraviolet rays it is preferable to use ultraviolet rays from the viewpoint of having a certain energy level, a high curing speed, and a relatively inexpensive irradiation apparatus, and a small size.
  • photo radical generators include, for example, acetophenone, acetophenone benzil ketal, anthraquinone, 1- (4-isopropylphenol) 2 hydroxy-1-methylpropanone 1-on, carbazole, xanthone, 4-clobenbenzophenone.
  • photopolymerization initiators 2, 2 dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2, 4, 6 Trimethylbenzoyl diphosphine phosphine oxide, 2-methyl- 1 1 [4 (methylthio) phenol] 2 Morpholinopropane 1-one, 2 (dimethylamino) 1 4 (morpholinyl) phenol] 2 methanol 1) -butanone and the like are more preferable, 1-hydroxycyclohexylphenylketone, 2-methyl-11 [4 (methylthio) phenol] 2 morpholinopropane 1-ion, 2- (dimethylamino) ) -1- [4- (morpholol) phenol] -2 phenolmethyl) -1-butanone and the like.
  • the addition amount of the photopolymerization initiator is not particularly limited, but is preferably 0.1 to 10% by weight with respect to the total amount of the composition other than the organic solvent. The reason for this is that when the amount of the additive is less than 0.1% by weight, the curing reaction becomes insufficient and the scratch resistance and the scratch resistance after immersion in an alkaline aqueous solution may be lowered. On the other hand, if the addition amount of the photopolymerization initiator exceeds 10% by weight, the refractive index of the cured product increases and the antireflection effect may decrease.
  • the addition amount of the photopolymerization initiator is 15% by weight with respect to the total amount of the composition other than the organic solvent.
  • thermal polymerization initiator examples include a thermal radical generator that generates a radical as the active species.
  • thermal radical generators examples include benzoyl peroxide, tert-butyloxybenzoate, azobisisobutyoxy-tolyl, acetylyl peroxide, lauryl peroxide, tert butyl peracetate, tamil peroxide, tert butyl peroxide, tert butyl hydride peroxide 2, 2, azobis (2, 4 dimethyl vale Mouth-tolyl), 2,2, -azobis (4-methoxy-2,4-dimethylvale mouth-tolyl) and the like may be used alone or in combination of two or more.
  • the addition amount of the thermal polymerization initiator is not particularly limited, but is preferably 0.1 to 10% by weight based on the total amount of the composition other than the organic solvent. This is because if the amount added is less than 0.1% by weight, the curing reaction becomes insufficient, and the scratch resistance and the scratch resistance after immersion in an alkaline aqueous solution may be lowered. On the other hand, if the addition amount of the photopolymerization initiator exceeds 10% by weight, the refractive index of the cured product increases and the antireflection effect may decrease.
  • a photosensitizer In the curable resin composition, a photosensitizer, a polymerization inhibitor, a polymerization initiation assistant, a leveling agent, a wettability improver, a surfactant, an acceptable agent are used as long as the objects and effects of the present invention are not impaired. It is also preferable to further contain additives such as plasticizers, ultraviolet absorbers, antioxidants, antistatic agents, silane coupling agents, inorganic fillers other than the components (C) and (D), pigments, and dyes.
  • additives such as plasticizers, ultraviolet absorbers, antioxidants, antistatic agents, silane coupling agents, inorganic fillers other than the components (C) and (D), pigments, and dyes.
  • the curable resin composition of the present invention comprises the above (A) ethylenically unsaturated group-containing fluoropolymer, the above (B) component and (C) component or, if necessary, the above (D) component, (E) It can be prepared by adding the components and (F) additive, respectively, and mixing at room temperature or under heating conditions. Specifically, it can be prepared using a mixer such as a mixer, a kneader, a ball mill, or a three roll. However, when mixing under heating conditions, it is preferable to carry out at or below the decomposition start temperature of the thermal polymerization initiator.
  • the exposure amount is within a range of 0.01 to 10 j / cm 2. It is preferable that
  • the exposure amount it is more preferable to set the exposure amount to a value in the range of 0.05 to 5jZcm 2 , and more preferably to a value in the range of 0.1 to 3j / cm 2 .
  • the curable resin composition When the curable resin composition is cured by heating, it is preferably heated at a temperature in the range of 30 to 200 ° C for 1 to 180 minutes. By heating in this way, an antireflection film having excellent scratch resistance can be obtained more efficiently without damaging the substrate and the like.
  • the antireflection film of the present invention includes a low refractive index layer made of a cured product obtained by curing the curable resin composition. Furthermore, the antireflection film of the present invention can contain a high refractive index layer, a hard coat layer, and z or a substrate under the low refractive index layer.
  • Figure 1 shows a powerful antireflection coating 10. As shown in FIG. 1, a hard coat layer 14 and a low refractive index layer 18 are laminated on a substrate 12.
  • a high refractive index layer 16 (not shown) may be formed between the hard coat layer 14 and the low refractive index layer 18.
  • the low refractive index layer 18 may be formed directly on the substrate 12 without providing the hard coat layer 14.
  • an intermediate refractive index layer (not shown) may be provided between the high refractive index layer 16 and the low refractive index layer 18 or between the high refractive index layer 16 and the hard coat layer 14. Good.
  • the low refractive index layer is composed of a cured product obtained by curing the curable resin composition of the present invention. Since the configuration and the like of the curable resin composition are as described above, a specific description thereof will be omitted, and the refractive index and thickness of the low refractive index layer will be described below.
  • the refractive index of the cured product obtained by curing the curable resin composition (the refractive index of Na—D line, measured Constant temperature 25 ° C.), that is, the refractive index of the low refractive index film is 1.50 or less, preferably 1.45 or less. This is because when the refractive index of the low refractive index film exceeds 1.45, the antireflection effect may be significantly reduced when combined with a high refractive index film. Therefore, it is more preferable that the refractive index of the low refractive index film is 1.44 or less.
  • the other low refractive index films exceed 1.45. It may be a value.
  • the refractive index difference from the high refractive index layer is preferably 0.05 or more.
  • the difference in refractive index between the low refractive index layer and the high refractive index layer is less than 0.05, the synergistic effect of these antireflective film layers cannot be obtained, and instead the antireflective effect. This is because there is a case where the value decreases.
  • the difference in refractive index between the low refractive index layer and the high refractive index layer is set to a value within the range of 0.1 to 0.5. More preferably, the value of
  • the thickness of the low refractive index layer is not particularly limited, but is preferably 50 to 300 nm, for example.
  • the reason for this is that when the thickness of the low refractive index layer is less than 50 nm, the adhesion to the high refractive index film as a base may decrease, whereas when the thickness exceeds 300 nm, optical interference does not occur. This is because the antireflection effect may be reduced, and therefore the thickness of the low refractive index layer is more preferably 50 to 250 nm, more preferably 60 to 200 nm.
  • the total thickness may be 50 to 300 nm.
  • a high refractive index layer may be formed between the hard coat layer and the low refractive index layer.
  • a curable composition for forming a high refractive index layer As a film formation component, epoxy-type resin, phenol-type resin, melamine-type resin It is preferable to include one kind or a combination of two or more kinds such as alkyd series resin, cyanate series resin, acrylic series resin, polyester series resin, urethane series resin and siloxane series resin. This is because such a resin can form a strong thin film as the high refractive index layer, and as a result, the scratch resistance of the antireflection film can be remarkably improved.
  • the refractive index of these resins alone is 1.45 to L62, which may not be sufficient to obtain high antireflection performance. Therefore, it is more preferable to blend high refractive index inorganic particles, for example, metal oxide particles.
  • a curable composition capable of thermosetting, ultraviolet curing, and electron beam curing can be used, but an ultraviolet curable composition having good productivity is more preferably used.
  • the thickness of the high refractive index layer is not particularly limited, but is preferably, for example, 50-30, OOOnm. The reason for this is that when the thickness of the high refractive index layer is less than 50 nm, when combined with the low refractive index layer, the antireflection effect may decrease the adhesion to the substrate, while the thickness If the thickness exceeds 30, OOOnm, optical interference may occur and the antireflection effect may be reduced.
  • the thickness of the high refractive index layer is more preferably 50 to: L, OOOnm, and more preferably 60 to 500 nm.
  • the total thickness may be 50 to 30 and OOOnm.
  • the thickness of a high refractive index layer can be 50-300 nm.
  • the constituent material of the hard coat layer used for the antireflection film of the present invention is not particularly limited.
  • siloxane resin, acrylic resin, melamine resin, epoxy resin, etc. can be used alone or in combination of two or more.
  • the thickness of the hard coat layer is not particularly limited, but is preferably 1 to 50 / ⁇ ⁇ and more preferably 5 to 10 m. The reason for this is that when the thickness of the hard coat layer is less than 1 ⁇ m, the adhesion of the antireflection film to the substrate may not be improved, whereas the thickness exceeds 50 / zm. And form uniformly This is because it may be difficult.
  • the type of substrate used in the antireflection film of the present invention is not particularly limited.
  • glass polycarbonate-based resin, polyester-based resin, acrylic-based resin, triacetylcellulose-based resin (TAC)
  • TAC triacetylcellulose-based resin
  • examples of such a base material include: By using anti-reflective coatings containing these base materials, it can be used in a wide range of applications for anti-reflective coatings such as color filters in camera lens units, television (CRT) screen display units, or liquid crystal display devices. In this case, an excellent antireflection effect can be obtained.
  • a 2.0-liter stainless steel autoclave with a magnetic stirrer was thoroughly replaced with nitrogen gas, and then 1200 g of ethyl acetate, 346 g of perfluoro (propyl butyl ether), 94 g of ethyl vinyl ether, 115 g of hydroxy ethyl vinyl ether, 4 g of lauryl oxide, 23 g of a polydimethylsiloxane containing an azo group represented by the above formula (7) (VPS 1001 (trade name), manufactured by Wako Pure Chemical Industries, Ltd.) and a nonionic reactive emulsifier (NE— 30 (trade name), manufactured by Asahi Denka Kogyo Co., Ltd.) was charged with 450 g, cooled to ⁇ 50 ° C. with dry ice-methanol, and then oxygen in the system was removed again with nitrogen gas.
  • VPN 1001 trade name
  • NE— 30 nonionic reactive emulsifier
  • VPS1001 is an azo group-containing polydimethylsiloxane represented by the above formula (7) having a number average molecular weight of 70 to 90,000 and a polysiloxane moiety having a molecular weight of about 10,000.
  • NE-30 is a nonionic reactive emulsifier wherein n is 9, m is 1 and u is 30 in the above formula (10).
  • Table 2 the correspondence between the monomer and the structural unit is as follows.
  • MIBK methyl isobutyl ketone
  • the obtained polymer solution was poured into methanol to precipitate a polymer, which was then washed with methanol and vacuum dried at room temperature to obtain a methacryl group-containing fluoropolymer.
  • Table 3 shows the raw material monomers used.
  • composition for hard coat layer In a container shielded from ultraviolet rays, 86 parts of MEK-dispersed nanosilica sol (MEK-ST manufactured by Nissan Chemical Industries, 30 parts as solids), 65 parts of dipentaerythritol hexaatalylate (Japan) DPHA), 2-Methyl-1 [4 (Methylthio) phenyl] 2 Morpholinopropan-1-one 5 parts (Chinoku 'Specialty' Irgacure 907), MIB K44 part at 50 ° C for 2 hours
  • MEK-dispersed nanosilica sol MEK-ST manufactured by Nissan Chemical Industries, 30 parts as solids
  • MEK-ST dipentaerythritol hexaatalylate
  • 2-Methyl-1 [4 (Methylthio) phenyl] 2 Morpholinopropan-1-one 5 parts Chinoku 'Specialty' Irgacure 907)
  • A4 size single-sided easy-adhesive polyethylene terephthalate film A4300 (manufactured by Toyobo Co., Ltd., film thickness 188 ⁇ m) is coated with the silica particle-containing hard coat layer composite material prepared in Production Example 3.
  • the film was coated with a wire bar coater to a thickness of 6 m and dried in an oven at 80 ° C for 1 minute to form a coating film.
  • ultraviolet rays were irradiated under the light irradiation condition of ljZcm 2 to prepare a substrate for coating a curable resin composition.
  • the curable resin composition obtained here was applied onto a silicon wafer with a spin coater so that the thickness after drying was about 0.1 m, and then 0.3 J using a high-pressure mercury lamp under nitrogen.
  • the UV cured by irradiation with light irradiation condition of ZCM 2.
  • the resulting cured product was measured for refractive index (n 25 ) at a wavelength of 589 nm at 25 ° C using an ellipsometer.
  • the refractive index was 1.43.
  • the film was coated on the hard coat obtained in Production Example 4 with a wire bar coater to a thickness of 0.1 m, and dried at 50 ° C for 1 minute to form a coating film.
  • an antireflection film layer was formed by irradiating ultraviolet rays under a light irradiation condition of 0.2 jZcm 2 using a high-pressure mercury lamp under a nitrogen stream.
  • the minimum reflectance was 2.5%.
  • MIBK Methyl isobutyl ketone
  • each curable resin composition was coated with a wire bar coater to a film thickness of 0.1 / xm, dried at 50 ° C for 1 minute, and then coated. Formed. Next Then, under a nitrogen stream, a low-refractive-index film layer was formed by irradiating ultraviolet rays under a light irradiation condition of 0.2 jZcm 2 using a high-pressure mercury lamp. To make it easy to see coating film defects, the back surface (base material side) of the obtained antireflection film is completely painted with black spray, and from the low refractive index film side under the three-wavelength white fluorescent lamp (Toshiba EX-N) The appearance was visually evaluated. The evaluation criteria are as follows. The results are shown in Tables 4 and 5.
  • the haze of the antireflection film obtained in Evaluation Example 2 was measured with a color haze meter.
  • the evaluation criteria are as follows. The results are shown in Tables 4 and 5.
  • Each curable resin composition was coated on the hard coat under the same conditions as in Evaluation Example 2, allowed to stand at room temperature, and the time until drying was visually evaluated.
  • the evaluation criteria are as follows. The results are shown in Table 4 and Table 5.
  • the curable resin composition of the present invention is a uniform liquid composition, and has excellent scratch resistance, antifouling properties, and coating properties, and the cured film has excellent transparency, particularly an antireflection film. Useful as.

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  • Life Sciences & Earth Sciences (AREA)
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Abstract

L'invention concerne une composition de résine durcissable contenant un polymère au fluor (A) ayant un groupe non saturé éthyléniquement, un composé de (méth)acrylate (B) et un solvant organique (C) permettant d'obtenir un produit durci ayant un faible indice de réfraction ne dépassant pas 1,50 et une excellente résistance à l'abrasion. La composition de résine durcissable contient, comme solvant organique (C), un solvant organique (C1) ayant un point d'ébullition inférieur à 100 °C et une tension superficielle de 2,1 x 10-4 N/cm à 25 °C, 1 atm (1,013 x 105 Pa) et un autre solvant organique (C2) ayant un point d'ébullition d'au moins 130 °C et au plus de 200 °C à 25 °C, 1 atm. L'invention concerne en outre un film antireflet.
PCT/JP2005/021577 2004-11-29 2005-11-24 Composition de resine durcissable et film antireflet Ceased WO2006057297A1 (fr)

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JP2008030286A (ja) * 2006-07-28 2008-02-14 Jsr Corp 積層体
JP2013064934A (ja) * 2011-09-20 2013-04-11 Nitto Denko Corp 反射防止フィルムの製造方法、反射防止フィルム、偏光板および画像表示装置

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112852265B (zh) * 2019-11-28 2022-05-13 雅图高新材料有限公司 一种高固含环保快干单组分汽车涂料，稀释剂及制备方法

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JP2002069381A (ja) * 2000-08-30 2002-03-08 Matsushita Electric Ind Co Ltd 絶縁膜形成用塗料及びそれを用いて製造されたプラズマ・ディスプレイ・パネル
JP2003183332A (ja) * 2001-12-18 2003-07-03 Nippon Kayaku Co Ltd コーティング用低屈折率樹脂組成物
JP2003183322A (ja) * 2001-12-21 2003-07-03 Jsr Corp エチレン性不飽和基含有含フッ素重合体、並びにそれを用いた硬化性樹脂組成物及び反射防止膜
JP2005290133A (ja) * 2004-03-31 2005-10-20 Jsr Corp 紫外線硬化型低屈折率材組成物及び反射防止膜

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JPH0892521A (ja) * 1994-09-20 1996-04-09 Toagosei Co Ltd 含フッ素塗料組成物
JPH09241575A (ja) * 1996-03-04 1997-09-16 Dainippon Ink & Chem Inc 塗料用樹脂組成物

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Publication number Priority date Publication date Assignee Title
JP2002069381A (ja) * 2000-08-30 2002-03-08 Matsushita Electric Ind Co Ltd 絶縁膜形成用塗料及びそれを用いて製造されたプラズマ・ディスプレイ・パネル
JP2003183332A (ja) * 2001-12-18 2003-07-03 Nippon Kayaku Co Ltd コーティング用低屈折率樹脂組成物
JP2003183322A (ja) * 2001-12-21 2003-07-03 Jsr Corp エチレン性不飽和基含有含フッ素重合体、並びにそれを用いた硬化性樹脂組成物及び反射防止膜
JP2005290133A (ja) * 2004-03-31 2005-10-20 Jsr Corp 紫外線硬化型低屈折率材組成物及び反射防止膜

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008030286A (ja) * 2006-07-28 2008-02-14 Jsr Corp 積層体
JP2013064934A (ja) * 2011-09-20 2013-04-11 Nitto Denko Corp 反射防止フィルムの製造方法、反射防止フィルム、偏光板および画像表示装置

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KR20070084591A (ko) 2007-08-24
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