WO2006134834A1 - Composition liquide durcissable, film durci et stratifié antistatique - Google Patents

Composition liquide durcissable, film durci et stratifié antistatique Download PDF

Info

Publication number
WO2006134834A1
WO2006134834A1 PCT/JP2006/311599 JP2006311599W WO2006134834A1 WO 2006134834 A1 WO2006134834 A1 WO 2006134834A1 JP 2006311599 W JP2006311599 W JP 2006311599W WO 2006134834 A1 WO2006134834 A1 WO 2006134834A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
formula
meth
compound represented
particles
Prior art date
Application number
PCT/JP2006/311599
Other languages
English (en)
Japanese (ja)
Inventor
Shingo Itai
Noriyasu Shinohara
Takayoshi Tanabe
Hiroomi Shimomura
Takaro Yashiro
Tetsuya Yamamura
Ryoji Tatara
Shin Hatori
Original Assignee
Jsr Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2005172278A external-priority patent/JP2006348069A/ja
Application filed by Jsr Corporation filed Critical Jsr Corporation
Publication of WO2006134834A1 publication Critical patent/WO2006134834A1/fr

Links

Classifications

    • 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
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black

Definitions

  • the present invention relates to a liquid curable composition, a cured film thereof, and an antistatic laminate. More specifically, it has excellent curability and various substrates such as plastics (polycarbonate, polymethylmetatalylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cell mouthwater resin, ABS, etc. Coatings with excellent antistatic properties, hardness, scratch resistance, and transparency on the surfaces of resin, AS resin, norbornene resin, etc., metal, wood, paper, glass, ceramics, slate, etc.
  • the present invention relates to an antistatic laminate comprising a liquid curable composition capable of forming (A) and a cured film layer obtained by curing the composition.
  • a radiation-curable composition has been used on the surface of the equipment to provide a scratch-resistant and adhesive coating (hard coat) and an antistatic function.
  • a coating film antistatic film
  • a multilayer structure (antireflection film) of a low refractive index layer and a high refractive index layer is formed on the surface of the optical article.
  • optical articles such as plastic lenses are required to prevent dust from being attached due to static electricity, and to improve the reduction in transmittance due to reflection. Therefore, prevention of dust adhesion due to static electricity and prevention of reflection on the screen has been demanded.
  • Patent Document 1 a composition containing a sulfonic acid and a phosphoric acid monomer as an ion conductive component
  • Patent Document 2 a composition containing a chain metal powder
  • Patent Document 3 a composition mainly composed of a copolymer of methyl methacrylate and polyether acrylate
  • Patent Document 3 a conductive material containing a pigment coated with a conductive polymer.
  • Optical disk material (Patent Document 5), Silane coupler containing coating composition (Patent Document 4), trifunctional acrylic ester, monofunctional ethylenically unsaturated group-containing compound, photopolymerization initiator, and conductive powder
  • Conductive paint containing hydrolyzate of antimony-doped tin oxide particles and tetraalkoxysilane, photosensitizer, and organic solvent dispersed in (Patent Document 6), and polymerizable unsaturated group in the molecule
  • Liquid curable resin composition containing a reaction product of an alkoxysilane and metal oxide particles, a trifunctional acrylic compound, and a radiation polymerization initiator
  • primary particles A conductive oxide fine powder having a diameter of ⁇ m or less, an easily dispersible low boiling solvent of the conductive oxide fine powder, a hardly dispersible low boiling solvent of the conductive oxide fine powder, and a binder resin Examples thereof include a coating material for forming a transparent conductive film (Pa
  • These display panels are required to have scratch resistance that is often wiped with gauze impregnated with ethanol or the like in order to remove attached fingerprints, dust, and the like. There is also a demand for contamination resistance that can easily wipe off attached fingerprints and dust.
  • the antireflection film is provided on the liquid crystal unit in a state of being bonded to a polarizing plate.
  • the base material for example, triacetyl cellulose is used, but in the antireflection film using such a base material, in order to increase the adhesion when bonded to the polarizing plate, In general, it is necessary to carry out the quenching with an aqueous alkaline solution. Therefore, in applications of liquid crystal display panels, there is a demand for an antireflection film excellent in alkali resistance, particularly in durability.
  • a fluorine-based resin coating containing a hydroxyl group-containing fluoropolymer is known (for example, Patent Documents 9 to 11).
  • a hydroxyl group-containing coating is used to cure the coating film. It is necessary to heat and crosslink the fluoropolymer and a curing agent such as melamine resin under an acid catalyst. Depending on the heating conditions, the curing time becomes excessively long, and the types of substrates that can be used are limited. There was a problem of being.
  • 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 weight There has been proposed a coating composition containing an unsaturated group-containing fluorinated vinyl polymer obtained by reacting a polymer with an isocyanate group at a ratio of the number of isocyanate groups to the number of Z hydroxyl groups of 0.01 to 1.0. (For example, Patent Document 12).
  • a coating composition containing such a polymer can be cured at a low temperature in a short time, but a curing agent such as melamine resin is further used to react the remaining hydroxyl groups. Needed to be cured. Furthermore, the coating film obtained in the above publication has a problem that it is sufficient in terms of coatability and scratch resistance.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 47-34539
  • Patent Document 2 JP-A-55-78070
  • Patent Document 3 JP-A-60-60166
  • Patent Document 4 Japanese Patent Laid-Open No. 2-194071
  • Patent Document 5 Japanese Patent Laid-Open No. 4-172634
  • Patent Document 6 JP-A-6-2644009
  • Patent Document 7 Japanese Unexamined Patent Publication No. 2000-143924
  • Patent Document 8 Japanese Patent Laid-Open No. 2001-131485
  • Patent Document 9 Japanese Patent Laid-Open No. 57-34107
  • Patent Document 10 Japanese Patent Application Laid-Open No. 59-189108
  • Patent Document 11 Japanese Patent Laid-Open No. 60-67518
  • Patent Document 12 JP-A 61-296073
  • Patent Document 1 uses an ion conductive material, but its performance fluctuates due to drying when the antistatic performance is not sufficient. Since the composition described in Patent Document 2 disperses a chain-like metal powder having a large particle size, transparency is lowered. Since the composition described in Patent Document 3 contains a large amount of a non-curable dispersant, the strength of the cured film decreases. Since the material described in Patent Document 5 contains high-concentration chargeable inorganic particles, transparency is lowered. The paint described in Patent Document 6 has insufficient long-term storage stability. Patent Document 7 does not disclose any method for producing a composition having antistatic performance. When a transparent conductive film is formed by applying and drying the paint described in Patent Document 8, the organic matrix having a binder compounding power is not provided with a cross-linked structure, so that the organic solvent resistance is not sufficient.
  • the present invention has been made in view of the above-described problems, and is a coating film excellent in curability and excellent in antistatic property, hardness, scratch resistance, and transparency on the surface of various base materials. It is an object of the present invention to provide a liquid curable composition capable of forming a coating) and a cured film thereof.
  • the present invention can also exhibit sufficient antistatic performance even when the amount of the conductive particles is small, is excellent in curability, and has antistatic properties on the surface of various substrates.
  • the present inventor has found that a tin-containing indium oxide particle having a specific particle size, a compound having two or more polymerizable unsaturated groups in the molecule, and photopolymerization initiation
  • a composition containing an agent and a solvent the antistatic performance is exhibited even when the amount of the conductive particles is small compared to the conventional one, and the transparency is not impaired! /, And a cured film can be obtained.
  • the present invention has been completed by finding out what can be done.
  • the inventor has also found that the above object can be achieved by a laminate having a cured film layer obtained by curing the composition, and has completed the present invention.
  • this cured film layer is combined with a low refractive index film obtained by curing a specific ethylenically unsaturated group-containing fluoropolymer and a curable resin composition containing silica particles, thereby providing an antireflection laminate.
  • the present invention was completed by finding that the abrasion resistance and contamination resistance of the body were improved.
  • the present invention provides the following liquid curable composition, cured film, method for producing the cured film, laminate, and method for producing the laminate.
  • A Particles mainly composed of tin-containing indium oxide (ITO) having a primary particle size of 20 nm or less and a secondary particle size of 50 nm or less
  • the component (A) is tin-containing indium oxide (ITO) surface-treated with a surface treatment agent. 3.
  • X represents NH, 0 (oxygen atom) or S (ion atom), and Y represents O or S.
  • a cured film obtained by curing the liquid curable composition according to any one of 1 to 4 above.
  • a method for producing a cured film which comprises a step of irradiating the liquid curable composition according to any one of 1 to 4 above with radiation to cure the composition.
  • a laminate comprising: a cured film layer obtained by curing the liquid curable composition according to any one of 1 to 4 above.
  • the laminated body is an antireflection film in which at least an antistatic layer and a low refractive index layer are laminated on a base material in this order in the order of V and side force,
  • the low refractive index layer is
  • R 11 represents a fluorine atom, a fluoroalkyl group or a group represented by —OR ”(R represents an alkyl group or a fluoroalkyl group)]
  • R 13 is a hydrogen atom or a methyl group
  • R 14 is an alkyl group,-(CH) —OR 15
  • R 15 represents an alkyl group or a glycidyl group, c represents a number of 0 or 1), a carboxyl group or an alkoxycarbo group] [Chemical 3]
  • R 16 represents a hydrogen atom or a methyl group
  • R 17 represents a hydrogen atom or a hydroxyalkyl group
  • V represents a number of 0 or 1
  • the hydroxyl group-containing fluoropolymer is further added to the following structural units (d) derived from an azo group-containing polysiloxane compound with respect to a total of 100 mole parts of the structural units (a) to (c).
  • R 18 and R 19 may be the same or different and each represents a hydrogen atom, an alkyl group, a halogenialkyl group or an aryl group]
  • X each independently represents an alkoxy group having 1 to 4 carbon atoms, a halogeno group, an isocyanate group, an alkyloxycarbon group having 2 to 4 carbon atoms, or an alkylamino group having 1 to 4 carbon atoms.
  • R 29 Is an alkenyl group having 2 to 8 carbon atoms, an talyloxyalkyl group having 4 to 8 carbon atoms, or A methacryloxyalkyl group having 5 to 8 carbon atoms, j represents an integer of 1 to 3; X in formula (22) and X in formula (23) may be the same or different.
  • X each independently represents an alkoxy group having 1 to 4 carbon atoms, a halogeno group, an isocyanate group, an alkyloxycarbon group having 2 to 4 carbon atoms, or an alkylamino group having 1 to 4 carbon atoms.
  • R 29 Is an alkenyl group having 2 to 8 carbon atoms, an attaryloxyalkyl group having 4 to 8 carbon atoms, or a methacryloxyalkyl group having 5 to 8 carbon atoms
  • j is an integer of 1 to 3.
  • R 3 is 1 carbon number -12 fluorine-substituted alkyl group
  • k represents an integer of 1 to 3.
  • X in formula (22), X in formula (23) and X in formula (24) may be the same or different. May be.
  • the hydrolysis And Z or a hydrolysis-condensation product have a reactant power of 67 to 99 mol% of the key compound represented by the formula (22) and 33 to 1 mol% of the key compound represented by the formula (23).
  • liquid curing that can form a coating film (coating) having excellent curability and excellent antistatic properties, hardness, scratch resistance, and transparency on the surface of various substrates.
  • Composition and a cured film thereof can be provided.
  • liquid curable composition of the present invention a cured film having both antistatic properties and transparency requirements can be obtained.
  • an antistatic laminate having a cured film obtained by curing the liquid curable composition.
  • the laminate of the present invention is an optical component having an antistatic function, particularly an antistatic device. It is useful as an antireflection film having a function.
  • FIG. 1 is a schematic diagram showing a basic configuration of a laminate according to the present invention.
  • FIG. 2A is a schematic view showing a first form of an antireflection film with an antistatic function of the present invention.
  • FIG. 2B is a schematic diagram showing another form of the first form of the antireflection film with an antistatic function of the present invention.
  • FIG. 2C is a schematic view showing a second embodiment of the antireflection film with an antistatic function of the present invention.
  • FIG. 2D is a schematic diagram showing another form of the second form of the antireflection film with an antistatic function of the present invention.
  • FIG. 2E is a schematic view showing a third embodiment of the antireflection film with an antistatic function of the present invention.
  • FIG. 2F is a schematic view showing another form of the third form of the antireflection film with an antistatic function of the present invention.
  • FIG. 3 is an electron micrograph of a cross section of the cured film of the present invention showing a typical state in which ITO particles of component (A) are unevenly distributed on the substrate side.
  • the laminate of the present invention has at least a substrate and a cured film layer obtained by curing a liquid curable composition containing the following components (A) to (D).
  • A Particles mainly composed of tin-containing indium oxide (ITO) having a primary particle size of 20 nm or less and a secondary particle size of 50 nm or less
  • the antireflection film which is a preferred embodiment of the laminate of the present invention, is such that the antistatic layer and the low refractive index layer comprising at least the cured film layer are close to the base material on the base material.
  • the side force is also an antireflection film laminated in this order, and the low refractive index layer is a cured product of a curable resin composition containing the following components (G) and (H).
  • the laminate 1 of the present invention has a base film 10 and a cured film layer 12 formed by curing the liquid curable composition.
  • the laminate of the present invention only needs to have at least the substrate 10 and the cured film layer 12. Depending on the, various layers may be provided. The layer provided according to the purpose will be described later.
  • the laminate 1 of the present invention has the cured film layer 12 having excellent scratch resistance and adhesion, it is particularly useful as a hard coat.
  • the laminate 1 of the present invention has an antistatic laminate by disposing a cured film layer 12 having an excellent antistatic function on a substrate of various shapes such as a film, a plate, or a lens. Useful as a body.
  • an antireflection film having an antistatic function for various display panels such as a CRT, a liquid crystal display panel, a plasma display panel, an electret luminescence display panel (hereinafter referred to as “antireflection film”)
  • an antireflection film with an antistatic function such as a plastic lens, a polarizing film, and a solar battery panel.
  • the cured film layer provided on the substrate of the laminate of the present invention comprises the following liquid curable composition (hereinafter, simply “composition” or “antistatic layer forming composition”). It is obtained by curing, and the laminate can be given a function as a conductive film and a function as Z or a hard coat.
  • composition liquid curable composition
  • antistatic layer forming composition antistatic layer forming composition
  • liquid curable composition used in the present invention will be specifically described.
  • Component (A) used in the present invention is tin-containing indium oxide (hereinafter, also simply referred to as “ITO”) particles.
  • the component ( ⁇ ) is an essential component for imparting conductivity (antistatic property) to the cured film obtained by curing the composition of the present invention.
  • the primary particle size of the soot particles is 20 nm or less, and the secondary particle size is 50 nm or less.
  • the primary particle size of the ITO particles is preferably 15 nm or less, and the secondary particle size is preferably 40 ⁇ . m or less.
  • the primary particle size of the ITO particles of component (A) is a value measured with a transmission electron microscope when the shape is spherical, regardless of the presence or absence of the surface treatment described later, and the shape is needle-like.
  • the value obtained as the number average particle size by observing the short axis with a transmission electron microscope is a value measured with a transmission electron microscope.
  • the secondary particle size of the soot particles of the component ( ⁇ ) is a value obtained by a dynamic light scattering type particle size distribution measuring device regardless of the presence or absence of surface treatment described later.
  • soot powders of soot particles include a trade name: soot powder manufactured by Fuji Chemical Co., Ltd.
  • the soot particles used as the component ( ⁇ ) can be used in a state of being dispersed in a powder or a solvent. However, since uniform dispersibility is easily obtained, it is preferable to use in a state of being dispersed in a solvent. Yes.
  • soot particles used as the component (soot) are dispersed in a solvent
  • the soot particles used as the component (soot) may be soot particles surface-treated with a surface treatment agent or the like in order to improve dispersibility in a solvent.
  • examples of the surface treatment agent include alkoxysilane compounds, tetrabutoxysilane, tetrabutoxyzirconium, tetraisopropoxyaluminum, and the like. These can be used alone or in combination of two or more.
  • alkoxysilane compound examples include a group of compounds having an unsaturated double bond in the molecule, such as ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -acryloxypropyltrimethoxysilane, and burtrimethoxysilane.
  • ⁇ -methacryloxypropyltrimethoxysilane ⁇ -acryloxypropyltrimethoxysilane
  • burtrimethoxysilane ⁇ -glycidoxypropyltriethoxysilane
  • ⁇ -glycidoxypropyltrimethoxysilane and other compounds having an epoxy group in the molecule, ⁇ -aminopropyltriethoxysilane, y-amaminopropyltrimethoxysilane, etc.
  • Compound group having an amino group in the molecule compound group having a mercapto group in the molecule such as ⁇ -mercaptopropyltrimethoxysilane, ⁇ -mercaptopropyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, Alkyl silanes such as phenyltrimethoxysilane Etc. can be mentioned.
  • Surface treatment ⁇ Preferable in terms of dispersion stability of particles.
  • a reactive surface treatment agent having a functional group that is copolymerized or cross-linked with an organic resin is also preferable.
  • a surface treatment agent include a compound group having an unsaturated double bond in the molecule, two or more polymerizable unsaturated groups, a group represented by the following formula (1), and a silanol group or hydrolysis.
  • a compound having a group that forms a silanol group is preferred.
  • X represents NH, 0 (oxygen atom) or S (ion atom), and Y represents O or S.
  • Examples thereof include alkoxysilane compounds having an unsaturated group.
  • a compound represented by the following formula (2) can be exemplified.
  • R 1 is a methyl group
  • R 2 is an alkyl group having 1 to 6 carbon atoms
  • R 3 is a hydrogen atom or a methyl group
  • m is 1 or 2
  • n is an integer of 1 to 5
  • X is 1 to 5 carbon atoms 6 divalent alkylene group
  • Y is a chain, cyclic or branched divalent hydrocarbon group having 3 to 14 carbon atoms
  • Z is an (n + 1) valent chain, cyclic or branched Is a divalent hydrocarbon group having 2 to 14 carbon atoms. In Z, It may contain a single bond.
  • the compound represented by the formula (2) can be produced by reacting mercaptoalkoxysilanes, diisocyanates, and hydroxyl group-containing polyfunctional (meth) acrylates.
  • an intermediate bonded with a thiourethane bond by reaction of mercaptoalkoxysilanes and diisocyanates is prepared, and then the remaining isocyanate is reacted with a hydroxyl group-containing polyfunctional (meth) acrylate.
  • a method for producing a product bonded with a urethane bond can be mentioned.
  • an intermediate bonded with a urethane bond is first produced by a reaction between a diisocyanate and a hydroxyl group-containing polyfunctional (meth) acrylate, and then the remaining isocyanate is reacted with a mercaptoalkoxysilane. Even if the same product is obtained, the addition reaction between the mercaptoalkoxysilanes and the (meth) acrylic group occurs simultaneously, so that the purity is lowered and a gel-like product may be formed.
  • Examples of mercaptoalkoxysilanes used in the production of the compound represented by formula (2) include ⁇ -mercaptopropyltrimethoxysilane, ⁇ -mercaptopropyltriethoxysilane, ⁇ -mercaptopropyltributoxysilane, ⁇ -mercaptopropyldimethylmethoxysilane, ⁇ -mercaptopropylmethyldimethoxysilane and the like can be mentioned. Of these, ⁇ -mercaptopropyltrimethoxysilane and ⁇ -mercaptopropylmethyldimethoxysilane are preferable.
  • Examples of commercially available mercaptoalkoxysilanes include trade name: SH6062 manufactured by Toray Dow Co., Ltd.
  • the diisocyanates include, for example, 1,4-butylene diisocyanate, 1,6 monohexylene diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated bisphenolate.
  • 2,4-toluene diisocyanate, isophorone diisocyanate, and hydrogenated xylylene diisocyanate are preferable.
  • polyisocyanate compounds include, for example, product names manufactured by Mitsui Nisso Urethane Co., Ltd .: TDI—80Z20, TDI—100, MDI—CR100, MDI—CR300, MDI—PH, NDI, manufactured by Nippon Polyurethane Industry Co., Ltd. Trade name: Coronate T, Millionate ⁇ , Millionone MR, HDI, Takeda Pharmaceutical Co., Ltd. Product name: Takenate 600, etc.
  • Examples of the hydroxyl group-containing polyfunctional (meth) atalylates include, for example, trimethylolpropandi (meth) atalylate, tris (2-hydroxyethyl) isocyanurate di (meth) atalylate, pentaerythritol. Examples thereof include tri (meth) acrylate and dipentaerythritol penta (meth) acrylate. Of these, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate are preferred. These form two or more polymerizable unsaturated groups in the compound represented by the formula (2).
  • These mercaptoalkoxysilanes, diisocyanates, and hydroxyl group-containing polyfunctional (meth) acrylates may be used alone or in combination of two or more.
  • the compounding ratio of mercaptoalkoxysilanes, di-socyanates, and hydroxyl group-containing polyfunctional (meth) acrylates is mercaptoalkoxysilanes.
  • the molar specific force S of the diisocyanates with respect to is preferably 0.8 to 1.5, more preferably 1.0 to 1.2. When this molar ratio is less than 0.8, the storage stability of the composition may be lowered, and when it exceeds 1.5, the dispersibility may be lowered.
  • the molar ratio of the hydroxyl group-containing (meth) acrylates to the diisocyanates is preferably from 1.0 to 1.5, more preferably from 1.0 to 1.2. If this mono ktt force is less than S1.0, gelation may occur, and if it exceeds 1.5, the antistatic property may deteriorate.
  • the compound represented by formula (2) is usually preferably produced in dry air in order to prevent anaerobic polymerization of acrylic groups and to prevent hydrolysis of alkoxysilanes.
  • the reaction temperature is preferably 0 ° C to 100 ° C, more preferably 20 ° C to 80 ° C.
  • a known catalyst may be added in the urethane reaction for the purpose of shortening the production time.
  • the catalyst include dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin di (2-ethylhexanoate), and octyltin triacetate.
  • the amount of the catalyst added is from 0.01 to 1% by weight based on the total amount with the diisocyanates.
  • thermal polymerization inhibitor for the purpose of preventing thermal polymerization of the compound represented by the formula (2), a thermal polymerization inhibitor is added during the production. It may be added.
  • the thermal polymerization inhibitor include P-methoxyphenol and hydrated quinone.
  • the addition amount of the thermal polymerization inhibitor is preferably 0.01% by weight to 1% by weight with respect to the total of the hydroxyl group-containing polyfunctional (meth) acrylates.
  • the compound represented by formula (2) can also be produced in a solvent.
  • a solvent for example, a solvent having a boiling point of 200 ° C. or lower that does not react with mercaptoalkoxysilanes, diisocyanates, and hydroxyl group-containing polyfunctional (meth) acrylates can be appropriately selected.
  • Specific examples of such solvents include ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, esters such as ethyl acetate, butyl acetate and amyl acetate, and hydrocarbons such as toluene and xylene. Can be mentioned.
  • the surface-treated ITO particles can be produced by hydrolyzing the surface treatment agent in the presence of the ITO particles.
  • the preferred manufacturing method is (A) IT
  • water is added to a mixture of O particles, a surface treatment agent, and an organic solvent, followed by hydrolysis.
  • the alkoxy group is temporarily converted into a silanol group (Si—OH) by hydrolysis of the surface treatment agent, and this silanol group reacts with the metal hydroxide (M—OH) on the ITO particles. Then, it is presumed that the surface treatment agent is fixed on the ITO particles by forming a metalloxane bond (M—O—Si).
  • the compounding amount of the surface treatment agent is preferably 0.1 to 50 parts by weight, more preferably 1 to 35 parts by weight with respect to 100 parts by weight of the (A) ITO particles. If the surface treatment agent is less than 0.1 part by weight, the cured film may have insufficient wear resistance, and if it exceeds 50 parts by weight, the antistatic performance may be insufficient.
  • the amount of water is preferably 0.5 to 1.5 equivalents relative to the total alkoxy equivalent in the surface treatment agent, and 0.5 to 5 with respect to 100 parts by weight of the surface treatment agent. It is preferable to add 0 part by weight.
  • the water used is preferably ion exchange water or distilled water.
  • the hydrolysis reaction can be carried out in the presence of an organic solvent by heating and stirring at a temperature of 0 ° C to the boiling point of the component, usually 30 to 100 ° C, for 1 to 24 hours.
  • an organic solvent when (A) ITO particles dispersed in an organic solvent in advance are used, it can be carried out as they are, but an organic solvent may be added separately.
  • an acid or a base may be added as a catalyst in order to promote the reaction during the hydrolysis.
  • acids include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, methanesulfonic acid, toluene sulfonic acid, phthalic acid, malic acid, tartaric acid, malonic acid, formic acid, oxalic acid, methacrylic acid, acrylic acid,
  • organic acids such as itaconic acid, and ammonium salts such as tetramethylammonium hydrochloride and tetrabutylammonium hydrochloride.
  • Examples of the base include amines such as aqueous ammonia, triethylamine, tributylamine, and triethanolamine.
  • a preferable catalyst is an acid, and an organic acid is more preferable. The amount of these catalysts added is preferably 0.001 to 1 part by weight, more preferably 0.01 to 0.1 part by weight, based on 100 parts by weight of the alkoxysilane compound.
  • Examples of the dehydrating agent are organic carboxylic acid orthoesters and ketals. Specifically, for example, orthoformate methyl ester, orthoformate ethyl ester, orthoacetic acid methyl ester, orthoacetic acid ethyl ester, etc., acetone dimethyl ketal, jetyl ketone dimethyl ketal, Examples include cetophenone dimethyl ketal, cyclohexanone dimethyl ketal, cyclohexanone jetyl ketal, and benzophenone dimethyl ketal. Among them, preferred are organic carboxylic acid orthoesters, and more preferred are orthoformate methyl ester and orthoformate ethyl ester.
  • These dehydrating agents can be added in an amount of not less than 10 moles and not more than 10 moles, preferably not less than 3 moles and not more than the amount of water contained in the composition. If it is less than the equivalent mole, the storage stability may not be sufficiently improved. These dehydrating agents are preferably added after the preparation of the composition. This promotes the storage stability of the composition and the formation of chemical bonds between the silanol groups in the hydrolyzate of the surface treatment agent and (A) ITO particles.
  • the surface treatment agent is mediated by a siloxy group (Si—O—). It is presumed that (A) it is fixed on the surface of ITO particles by chemical bonding.
  • the (A) ITO particles surface-treated with a reactive surface treatment agent are particularly referred to as reactive particles (RA).
  • the blending amount of component (A) is not particularly limited, but is preferably 5 to 40% by weight, more preferably 7 to 35% by weight in 100% by weight of the total solid content of the composition of the present invention. The same applies when component (A) is surface treated. If the blending amount is less than 5% by weight, the antistatic property may be inferior, and if it exceeds 40 parts by weight, the film forming property of the coating film may be inferior.
  • the blending amount of component (A) refers to the blending amount as a solid content, and does not include a dispersion medium.
  • Component (B) used in the present invention is a compound having two or more polymerizable unsaturated groups in the molecule.
  • the cured film obtained by curing the composition of the present invention has film-forming properties and transparency. It is an ingredient to be given.
  • a cured product having excellent scratch resistance and organic solvent resistance can be obtained.
  • component (B) include (meth) acrylic esters and vinyl compounds.
  • (Meth) acrylic esters include trimethylol propane tri (meth) acrylate, ditrimethylol propane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipenta Erythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethylene phthalate (meta ) Atalylate, 1,3-Butanedioldi (meth) atarylate, 1,4-Butanedioldi (meth) atalylate, 1,6-Hexanedioldi (meth) atalylate, Neopentylglycoldi (meth) Atalylate, diethyleneda
  • vinyl compounds include dibutene benzene, ethylene glycol dibutyl ether, diethylene glycol divinino ether, triethylene glycol divinino etherate and the like.
  • These (B) components may be used individually by 1 type, and may use 2 or
  • the amount of component) is preferably 55 to 94% by weight, more preferably 60 to 92% by weight, based on 100% by weight of the total solid content of the composition of the present invention. If the blending amount of component (B) is less than 55% by weight, the resulting cured product may have poor transparency, and if it exceeds 94% by weight, the antistatic property may be inferior.
  • Component is a photopolymerization initiator and is added to increase the curing rate when the composition of the present invention is cured by irradiation with radiation.
  • radiation means visible light, ultraviolet light, far ultraviolet light, X-rays, electron beams, ⁇ rays, j8 rays, ⁇ rays, and the like.
  • the blending amount of component (C) is preferably 0.1 to 15% by weight, more preferably 0.5 to LO weight, based on 100% by weight of the total solid content of the composition of the present invention. %.
  • Component (C) can be used alone or in combination of two or more.
  • Examples of the component (C) include 1-hydroxycyclohexyl phenol ketone, 2,2 dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole , 3-methylacetophenone, 4-clobenbenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, Michler's ketone, benzoin propyl ether, benzoin ether, benzil dimethyl ketal, 1 Mono (4 isopropyl phenol) 2 hydroxy 2 methyl Propane 1-one, 2-Hydroxy-1-2-Methyl-1-Fane Propane 1-one, Thioxanthone, Jetylthioxanthone, 2-Isopropylthixanthone, 2-Chlorothioxanthone, 2-Methyl-11 )
  • Component (D) used in the present invention is a solvent, and is a component for adjusting the fluidity of the composition of the present invention.
  • the solvent as the component (D) in the composition of the present invention has a concentration of the total solid content of the composition of 0.
  • the amount of the solvent added is preferably within the range of 33.3 to 19,900 parts by weight when the total solid content of the composition of the present invention is 100 parts by weight.
  • the reason for this is that (D) when the amount of the solvent added is less than 33.3 parts by weight, the viscosity of the composition may increase and the coatability may decrease, whereas when the amount exceeds 19,900 parts by weight. In other words, the resulting cured product is too thin and may not exhibit sufficient hardness.
  • the type of the solvent is not particularly limited, but usually a solvent having a boiling point of 200 ° C or lower at normal pressure is preferred. Specifically, water, alcohols, ketones, ethers, esters, hydrocarbons, amides and the like are used. These can be used alone or in combination of two or more.
  • Examples of alcohols include methanol, ethanol, isopropyl alcohol, isobutanol, n-butanol, tert-butanol, ethoxyethanol, butoxhetano monoole, diethyleneglycolenomonoethinoreethenole, benzenoreanoreconole, Examples include phenolic alcohol.
  • Examples of the ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
  • Examples of ethers include dibutyl ether, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether (PGME), and the like.
  • Esters include, for example, ethyl acetate, butyl acetate, ethyl lactate, methyl acetate And ethyl acetate.
  • hydrocarbons include toluene and xylene.
  • amides include N, N dimethylformamide, N, N dimethylacetamide, N-methylpyrrolidone and the like.
  • the dispersion medium is different from the dispersion medium that may be used as the solvent of component (D) as it is. It is possible to use only a solvent, or a combination of a dispersion medium and another solvent can be used as a solvent for component (D)!
  • component (E) in the composition of the present invention, as a component other than components (A) to (D), other compounds having a polymerizable unsaturated group (component (E)) can be blended as necessary.
  • the component is a compound having one polymerizable unsaturated group in the molecule.
  • component (E) examples include, for example, N-bulupyrrolidone, N-vinylcaprolactam-containing burata-containing ratata, isobornyl (meth) acrylate, boryl (meth) acrylate, tricyclodehydrate. Containing alicyclic structures such as force (meth) acrylate, dicyclopental (meth) acrylate, dicyclopentale (meth) acrylate, cyclohexyl (meth) acrylate, etc.
  • (meth) acrylate benzyl (Meth) Atalylate, 4-Butylcyclohexyl (Meth) Atalylate, Ataliloylmorpholine, Bulimidazole, Bulpyridine, 2-Hydroxychetyl (Meth) Atalylate, 2-Hydroxypropyl (Meth) Atalylate, 2-Hydroxybutyl (Meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, Propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) Atalylate, isoamyl (meth) atarylate, hexyl (meth) atarylate, heptyl (
  • R 4 represents a hydrogen atom or a methyl group
  • R 5 represents an alkylene group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms
  • R 6 represents a hydrogen atom or 1 to 12 carbon atoms, preferably 1 to 9 alkyl group
  • Ph represents a fullerene group
  • p represents a number of 0 to 12, preferably 1 to 8.
  • E Commercially available components (E) include: ALONIX M-101, M-102, M-111, M-113, M-114, M-117 (above, manufactured by Toa Gosei Co., Ltd.); LA, STA, IBXA, 2 — MTA, # 192, # 193 (Osaka Organic Chemical Co., Ltd.); 3 ⁇ 4: Esters AMP—10G, A MP—20G, AMP—60G (above, Shin-Nakamura Chemical Co., Ltd.); Light Atylate L—A, S—A, IB—XA, PO—A, PO—200A NP-4EA, NP-8EA (manufactured by Kyoeisha Chemical Co., Ltd.); FA-511, FA-512A, FA-513A (manufactured by Hitachi Chemical Co., Ltd.).
  • the liquid curable composition is obtained by reacting non-conductive particles or non-conductive particles with an alkoxysilane compound in an organic solvent within a range that does not cause problems such as separation and gelling. You can use the resulting particles together!
  • the antistatic function that is, the surface resistance when a cured film is maintained while maintaining a value of 10 13 ⁇ or lower, Abrasion resistance can be improved.
  • non-conductive particles specifically, silicon oxide, acid aluminum, acid Oxide particles such as zirconium oxide, titanium oxide, cerium oxide, etc., or oxides containing two or more elements selected from group forces consisting of silicon, aluminum, zirconium, titanium, and cerium Particles can be mentioned.
  • the primary particle diameter of the non-conductive particles is preferably 0.1 m or less, more preferably 0.001 to 0.05 ⁇ m, as a value obtained by observation with a transmission electron microscope. It is. If it exceeds 0.1 m, sedimentation may occur in the composition or the smoothness of the coating film may be lowered.
  • the non-conductive particles and the alkoxysilane compound may be hydrolyzed in an organic solvent and then mixed. This treatment improves the dispersion stability of the nonconductive particles.
  • the hydrolysis treatment of the non-conductive particles and the alkoxysilane compound in an organic solvent can be performed in the same manner as the method for treating the oxide particles as the component (A) described above.
  • non-conductive particles include, for example, acid silica particles (for example, silica particles), colloidal silica, manufactured by Nissan Chemical Industries, Ltd., trade names: methanol silica sol, IPA- ST, MEK—ST, NBA-ST, XBA—ST, DMAC—ST, ST—UP, ST—OUP ⁇ ST—20, ST—40, ST—C, ST—N, ST—0, ST—50, ST—OL can be listed.
  • powder silica is manufactured by Nippon Aerosil Co., Ltd. Product name: Aerosil 130, Aerosil 300, Aerosil 380, Aerosil TT600, Aerosil 0X50, Asahi Glass Co., Ltd.
  • the blending ratio of the non-conductive particles is preferably 0.1 to 35% by weight, more preferably 1 to 30% by weight in 100% by weight of the total solid content of the composition of the present invention. [0078] 7. Additives
  • an antioxidant an ultraviolet absorber, a photostabilizer, a thermal polymerization inhibitor, a leveling agent, a surfactant, a lubricant and the like are blended as necessary. can do.
  • Anti-oxidation agent manufactured by Chino Specialty Chemicals Co., Ltd. Trade name: Ilganox 1010, 1035, 1076, 1222, etc.
  • Ultraviolet absorbers manufactured by Ciba Specialty Chemicals Co., Ltd.
  • Product name Tinuvin P234, 320 , 326, 327, 328, 213, 329, manufactured by Sipro Kasei Co., Ltd.
  • Product name Seasorb 102, 103, 501, 202, 712, etc.
  • the viscosity of the composition of the present invention thus obtained is usually 1 to 20, 0 OOmPa's, preferably 1 to 1, OOOmPa's at 25 ° C.
  • the solid content excluding the solvent (D) of the composition of the present invention is preferably in the range of 0.5 to 75% by weight. If the solid content is less than 0.5% by weight, the resulting cured product may be too thin and may not exhibit sufficient hardness. If it exceeds 75% by weight, the viscosity of the composition will increase. As a result, applicability may decrease.
  • the liquid curable composition of the present invention comprises the above components (A) to (D) and, if necessary, the above-mentioned compounds having other polymerizable unsaturated groups, non-conductive particles, and other additives. In addition, it is obtained by mixing.
  • the cured film layer of the laminate of the present invention can be obtained by coating the antistatic layer-forming composition described above on the substrate, drying it, and then irradiating it with radiation to cure the composition. .
  • the surface resistance of the obtained cured film layer is 1 X 10 13 ⁇ or less, sufficient antistatic performance can be exhibited, usually 1 to 10 12 ⁇ or less, preferably 1 to 10 1 () ⁇ In the following, it is more preferably 1 to 10 8 ⁇ . If the surface resistance exceeds 1 ⁇ 10 12 ⁇ well, the antistatic performance is sufficient and the dust is not easily attached or the attached dust cannot be removed easily. There is a case.
  • the surface resistance of the laminate (antireflection film with an antistatic function) of the present invention when a low refractive index layer or the like described later is formed on a cured film layer having a surface resistance value in the above range is usually normal. 1 ⁇ 10 13 ⁇ / mouth or less, preferably ⁇ ⁇ ⁇ ⁇ ⁇ / mouth or less, more preferably 1 ⁇ 10 8 ⁇ / mouth or less.
  • the method for applying the composition for forming an antistatic layer is not particularly limited! /, But for example, a known method such as roll coating, spray coating, flow coating, diving, screen printing, ink jet printing or the like is applied. be able to.
  • the radiation source used for curing the composition for forming an antistatic layer is not particularly limited as long as it can be cured in a short time after the composition is applied.
  • Examples of the visible ray source include direct sunlight, lamps, fluorescent lamps, and lasers.
  • Examples of the ultraviolet ray source include mercury lamps, halide lamps, and lasers, and electron beam source.
  • a method using a thermoelectron generated from a commercially available tungsten filament a cold cathode method in which a metal is generated through a high voltage pulse, and a collision between an ionized gaseous molecule and a metal electrode 2
  • Examples include secondary electron systems that use secondary electrons.
  • Examples of the source of ⁇ rays, j8 rays, and ⁇ rays include fission materials such as 6 ° Co.
  • fission materials such as 6 ° Co.
  • vacuum tubes that collide accelerated electrons with the anode can be used. .
  • These radiations may be irradiated alone or in combination of two or more kinds. Alternatively, one or more kinds of radiation may be irradiated for a certain period.
  • the thickness of the cured film layer is preferably 0.05-30 ⁇ m! /.
  • the thickness is relatively thick, preferably 2 to 15 m.
  • 0.05 to L0 m is preferable.
  • the total light transmittance is preferably 85% or more.
  • Base materials used in the laminate of the present invention are metal, ceramics, glass, plastic, wood
  • the material, slate, etc. are not particularly limited and may be appropriately selected depending on the purpose of use.However, as a material capable of exhibiting high productivity and industrial utility such as radiation curability, for example, a film or a fiber-like substrate. Preferably applied. Particularly preferred materials are plastic film and plastic plate.
  • plastics include polycarbonate, polymethyl methacrylate, polystyrene Z polymethyl methacrylate copolymer, polystyrene, polyester, polyolefin, triacetyl cellulose resin, and diethylene glycol diaryl. Examples include carbonate (CR-39), ABS resin, AS resin, polyamide, epoxy resin, melamine resin, cyclized polyolefin resin (for example, norbornene-based resin).
  • the base material to be used is preferably a base material such as polyester or polyethylene terephthalate (PET) in which the surface to which the composition for forming an antistatic layer is applied is subjected to an easy adhesion treatment.
  • Examples of such easy adhesion treatment include corona discharge treatment and easy adhesion layer coating treatment.
  • a preferred example of a commercially available base material subjected to easy adhesion treatment is polyester film A4300 (manufactured by Toyobo Co., Ltd.).
  • the thickness of the substrate should be appropriately set according to the purpose and is not particularly limited.
  • a method of forming a low refractive index layer or a multilayer structure of a low refractive index layer and a high refractive index layer is formed on a base material or a hard-coated base material. It is known that the method to do is effective.
  • FIG. 2A shows a first embodiment in which the laminate of the present invention is used as an antireflection film with an antistatic function.
  • the antireflection film 2 with an antistatic function is formed by forming an antistatic layer 12 which is a cured film layer obtained by curing the liquid curable composition on a base material 10, and further thereon.
  • a low refractive index layer 18 is formed.
  • the antistatic layer 12 has both an antistatic function and a function as a hard coat layer.
  • the refractive index of the antistatic layer 12 needs to be higher than the refractive index of the low refractive index layer 18.
  • the antistatic layer 12 of the antireflection film 2 of the present invention can also function as a hard coat layer, but a hard coat layer can also be provided separately.
  • the hard coat layer n is provided between the antistatic layer 12 and the low refractive index layer 18.
  • the refractive index of the hard coat layer 11 must be higher than the refractive index of the low refractive index layer 18.
  • FIG. 2D shows a second embodiment in which the laminate of the present invention is used as an antireflection film with an antistatic function.
  • the antireflection film 2 with an antistatic function is obtained by forming an antistatic layer 12 which is a cured film layer obtained by curing the liquid curable composition on a base material 10, and further thereon.
  • the high refractive index layer 16 and the low refractive index layer 18 are formed in this order.
  • the antistatic layer 12 may have both an antistatic function, a function as a coating, and a function as a medium refractive index layer.
  • the refractive index of the antistatic layer 12 is lower than the refractive index of the high refractive index layer 16. It must be higher than the refractive index.
  • a mode in which a hard coat layer is separately provided is also possible as in the first mode.
  • the hard coat layer 11 can be provided between the antistatic layer 12 and the high refractive index layer 16. These configurations are shown in Figure 2F.
  • FIG. 2G shows a third embodiment in which the laminate of the present invention is used as an antireflection film with an antistatic function.
  • the antireflection film 2 with an antistatic function is obtained by forming an antistatic layer 12 which is a cured film layer obtained by curing the liquid curable composition on a base material 10, and further thereon.
  • the middle refractive index layer 14, the high refractive index layer 16, and the low refractive index layer 18 are formed in this order.
  • the antistatic layer 12 has both an antistatic function and a function as a hard coat.
  • the third embodiment it is also possible to provide a hard coat layer separately as in the first embodiment.
  • the hard coat layer 11 can be provided between the antistatic layer 12 and the medium refractive index layer 14. These forms are shown in FIG.
  • the layers other than the antistatic layer and the substrate provided in the first to third embodiments of the antireflection film with an antistatic function will be described.
  • the low refractive index layer is a layer having a thickness of 0.05 to 0.20 m and a refractive index of 1.30 to L45.
  • the refractive index in the present invention means a refractive index of 589 nm at 25 ° C.
  • the material used for the low refractive index layer is not particularly limited as long as the desired properties are obtained.
  • a curable composition containing an fluorinated polymer, an acrylic monomer, and a fluorinated acrylic monomer. And cured products such as epoxy group-containing compounds and fluorine-containing epoxy group-containing compounds.
  • silica fine particles and the like can be blended.
  • a low refractive index layer is formed using a curable resin composition containing components (E) and (F) described later.
  • the high refractive index layer has a thickness in the range of 0.05 to 0.20 m and a refractive index in the range of 1.55 to 2.20.
  • high refractive index inorganic particles such as metal oxide particles can be mixed.
  • metal oxide particles include antimony-containing tin oxide (ATO) particles, tin-containing indium oxide (ITO) particles, oxide-zinc (ZnO) particles, antimony-containing ZnO, and Al-containing Z ⁇ . Particles ZrO particles, TiO particles, silica-coated TiO particles, Al 2 O 3 / ZrO-coated TiO particles,
  • Examples include CeO particles.
  • antimony-containing tin oxide (ATO) particles are preferred.
  • ITO indium oxide
  • PTO phosphorus-containing tin oxide
  • A1-containing ZnO particles Al 2 O 3 / ZrO-coated TiO particles.
  • metal oxide particles are one kind alone or
  • the high refractive index layer can have a function of a hard coat layer.
  • the refractive index is 1.50 ⁇ : L 90 Therefore, a layer having a refractive index higher than that of the low refractive index layer and lower than that of the high refractive index layer is referred to as a middle refractive index layer.
  • the refractive index of the middle refractive index layer is preferably 1.50 to L80, more preferably 1.50 to L75.
  • the middle refractive index layer has a thickness in the range of 0.05 to 0.20 / zm.
  • high refractive index inorganic particles such as metal oxide particles can be combined.
  • metal oxide particles include antimony-containing tin oxide (ATO) particles, tin-containing indium oxide (ITO) particles, ZnO particles, antimony-containing ZnO, A1-containing ZnO particles, ZrO particles, TiO Particles, silica-coated TiO particles, Al 2 O 3 / ZrO-coated TiO particles, CeO particles
  • antimony-containing tin oxide (ATO) particles tin-containing indium oxide (ITO) particles, phosphorus-containing tin oxide (PTO) particles, A1-containing ZnO particles, ZrO particles
  • metal oxide particles can be used singly or in combination of two or more.
  • the reflectance can be lowered by combining the low refractive index layer and the high refractive index layer, and the reflectance can be reduced by combining the low refractive index layer, the high refractive index layer, and the middle refractive index layer. Can be reduced and the glare can be reduced.
  • hard coat layer examples include SiO, epoxy resin, acrylic resin, melamine
  • silica particles may be blended with these rosins.
  • the hard coat layer has the effect of increasing the mechanical strength of the laminate.
  • the thickness of the hard coat layer is
  • the refractive index of the coated layer is usually in the range of 1.45 to 1.70, preferably 1.45 to L60.
  • the material of the substrate when the laminate of the present invention is used as an antireflection film must be transparent.
  • resin AS resin, polyamide, epoxy resin, melamine resin and cyclized polyolefin resin (for example, norbornene-based resin).
  • the base subjected to the easy adhesion treatment is used.
  • Material is preferred. Examples of such easy adhesion treatment include corona discharge treatment and easy adhesion layer coating treatment.
  • a preferred example of a commercially available base material subjected to easy adhesion treatment is polyester film A4300 (manufactured by Toyobo Co., Ltd.).
  • Polyester film A4300 (manufactured by Toyobo Co., Ltd.) subjected to easy adhesion treatment is coated with the liquid curable composition of the present invention and cured to form the ITO particles of component (A).
  • Fig. 3 shows an electron micrograph of a cured film cross section showing a typical state of uneven distribution on the material side. In FIG. 3, the lower part is the substrate side, the upper part is the air side, and it can be seen that the ITO particles are unevenly distributed on the substrate side.
  • the thickness of the substrate is not particularly limited, but is usually in the range of 30 to 300 ⁇ m, preferably 50 to 200 ⁇ m.
  • the laminate of the present invention has scratches on, for example, plastic optical components, touch panels, film-type liquid crystal elements, plastic casings, plastic containers, flooring materials for building interior materials, wall materials, artificial stones, etc. It can be suitably used as a hard coating material for preventing (scratching) and preventing contamination; an adhesive for various base materials, a sealing material; a binder material for printing ink, and the like.
  • the film thickness of the low, medium and high refractive index layers is usually 60 to 150 nm
  • the film thickness of the hard coat layer is usually 1 to 20 111
  • the film thickness of the antistatic layer is usually 0.05 to 30 / ⁇ ⁇ . It is.
  • the layer can be produced by a known method such as coating and curing, vapor deposition, or sputtering.
  • the low refractive index layer formed in the laminate of the present invention comprises (G) a curable polymer containing an ethylenically unsaturated group and (i) a curable resin composition containing silica particles (hereinafter referred to as “low refractive index”).
  • the cured product is preferably composed of a composition for forming a rate layer “t”.
  • the ethylenically unsaturated group-containing fluoropolymer (G) used for the composition for forming a low refractive index layer is composed of a compound containing one isocyanate group and at least one ethylenically unsaturated group, and a hydroxyl group-containing polymer. It can be obtained by reacting with a fluoropolymer.
  • 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.
  • diisocyanates examples include 2,4-tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, methylene bis (4-cyclohexenoylisocyanate), 1,3-bis (isocyanate) Methyl) cyclohexane is preferred.
  • hydroxyl group-containing (meth) acrylate 2-hydroxyethyl (meth) acrylate and pentaerythritol tri (meth) acrylate are preferable.
  • 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. can be obtained.
  • the hydroxyl group-containing fluoropolymer preferably comprises the following structural units (a), (b) and (c).
  • R 11 represents a fluorine atom, a fluoroalkyl group or a group represented by —OR ”(R represents an alkyl group or a fluoroalkyl group)]
  • R 13 is a hydrogen atom or a methyl group
  • R 14 is an alkyl group,-(CH) —OR 15
  • R 15 represents an alkyl group or a glycidyl group, c represents a number of 0 or 1), a carboxyl group or an alkoxycarbo group
  • R 16 represents a hydrogen atom or a methyl group
  • R 17 represents a hydrogen atom or a hydroxyalkyl group
  • V represents a number of 0 or 1
  • the fluoroalkyl group of R 11 and R 12 includes a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a no-fluorine hexyl group. And a fluoroalkyl group having 1 to 6 carbon atoms such as perfluorocyclohexyl group.
  • the alkyl group for R 12 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.
  • Perfluoro (alkyl vinyl ether) such as perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), perfluoro (propyl vinyl ether), perfluoro (butyl vinyl ether), perfluoro (isobutyl vinyl ether), etc .
  • Perfluoro (alkoxyalkyl butyl ether) s such as propoxypropyl butyl ether may be used alone or in combination of two or more.
  • hexafluoropropylene and perfluoro (alkyl buulete) ) Or perfluoro (alkoxyalkyl butyl ether) is more preferred, and it is further preferred to use a combination of these! /.
  • the content of the structural unit (a), the sum of the structural units (a) ⁇ (c) is 100 mol%, 20 to 70 mole 0/0. This is because if the content is less than 20 mole 0/0, which is characteristic of the optically fluorine-containing material where the application is intended, it may be a case where the expression of the low refractive index becomes difficult, whereas This is because if the content exceeds 70 mol%, the solubility of the hydroxyl group-containing fluorine-containing polymer in an organic solvent, transparency, or adhesion to a substrate may be lowered.
  • the content of the structural unit (a) is more preferably 25 to 65 mol%, and further preferably 30 to 60 mol%! /.
  • examples of the alkyl group of R 13 or R 14 include alkyl groups having 1 to 12 carbon atoms such as a methyl group, an ethyl group, a propyl group, a hexyl group, a cyclohexyl group, and a lauryl group.
  • examples of the alkoxycarbonyl group represented by R 15 include a methoxycarbonyl group and an ethoxycarbonyl group.
  • 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 ethereol, 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: ethino levin
  • the content of the structural unit (b) is 10 to 70 mol% when the total of the structural units (a) to (c) 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. On the other hand, 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 more preferably 20 to 60 mol%, and even more preferably 30 to 60 mol%! /.
  • 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, etc.
  • hydroxyl-containing butyl ethers such as 2-hydroxyethyl allyl ether, 4-hydroxybutyl 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 of the structural units (a) to (c) is 100 mol%. This is because when the content is less than 5 mol%, the solubility of the hydroxyl group-containing fluoropolymer in an organic solvent may decrease. On the other hand, if the content exceeds 70 mol%, 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 more preferably 5 to 40 mol%, and even more preferably 5 to 30 mol%.
  • the hydroxyl group-containing fluoropolymer preferably further comprises the following structural unit (d).
  • R 18 and R 19 may be the same or different and each represents a hydrogen atom, an alkyl group, a halogenialkyl group or an aryl group]
  • the alkyl group represented by R 18 or R 19 is an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, or a propyl group.
  • the halogenoalkyl group is a trifluoromethyl group, C1-C4 fluoroalkyl group, such as perfluoroethyl group, perfluoropropyl group, perfluorobutyl group, etc.
  • aryl groups include a phenyl group, a benzyl group, and a naphthyl group. It is done.
  • the structural unit (d) can be introduced by using an azo group-containing polysiloxane compound having a polysiloxane segment represented by the formula (14).
  • an azo group-containing polysiloxane compound having a polysiloxane segment represented by the formula (14).
  • Examples of such an azo group-containing polysiloxane compound include compounds represented by the following formula (15).
  • alkyl group or cyan R 24 to R 27 represent a hydrogen atom or an alkyl group which may be the same or different, d and e are numbers 1 to 6, s and t are numbers 0 to 6, and y is A number from 1 to 200, z represents a number from 1 to 20. [0131] When the compound represented by the formula (15) is used, the structural unit (d) is included in the hydroxyl group-containing fluoropolymer as a part of the structural unit (e).
  • R 2 to R 23 , R 24 to R 27 , d, e, s, t, and y are the same as those in the above formula (15).
  • the alkyl group represented by R 2 to R 23 is a C 1 to C group such as a methyl group, an ethyl group, a propyl group, a hexyl group, or a cyclohexyl group.
  • 12 alkyl groups, and R 24 to R 27 alkyl groups include methyl groups, ethyl groups, propyl groups, etc.
  • a compound represented by the following formula (17) is particularly preferable.
  • the content of the structural unit (d) is preferably 0.1 to 10 mole parts with respect to 100 mole parts in total of the structural units (a) to (c).
  • the reason for this is that when the content is less than 0.1 mol part, the surface slipperiness of the coated film after curing may be lowered, and the scratch resistance of the coated film may be lowered.
  • the ratio exceeds 10 parts by mole the transparency of the hydroxyl group-containing fluoropolymer is inferior, and when used as a coating material, repelling and the like may easily occur during coating.
  • the content of the structural unit (d) is more preferably 0.1 to 5 mol parts, and even more preferably 0.1 to 3 mol parts.
  • it is desirable that the content of the structural unit (e) is 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).
  • the group having an emulsifying action of R 25 has both a hydrophobic group and a hydrophilic group, and the hydrophilic group has a polyether structure such as polyethylene oxide and polypropylene oxide. Some groups are preferred.
  • Examples of such an emulsifying group include a group represented by the following formula (19).
  • the structural unit (f) can be introduced by using a reactive emulsifier as a polymerization component.
  • reactive emulsifiers include compounds represented by the following formula (20).
  • the content of the structural unit (f) is preferably 0.1 to 5 mol parts with respect to a total of 100 mol parts of the structural units (a) to (c).
  • the reason for this is that when the content is 0.1 mol part or more, the solubility of the hydroxyl group-containing fluoropolymer in the solvent is improved. This is because the tackiness of the resin composition does not increase excessively, handling becomes easy, and moisture resistance does not decrease even when used as a coating material.
  • the content of the structural unit (f) is more preferably 0.1 to 3 mol parts, and even more preferably 0.2 to 3 mol parts.
  • 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 is obtained by reacting the above-described compound containing one isocyanate group and at least one ethylenically unsaturated group with a hydroxyl group-containing fluorine-containing polymer. Obtained.
  • a compound containing one isocyanate group and at least one ethylenically unsaturated group, and a hydroxyl group-containing fluoropolymer are an isocyanate group Z It is preferable to carry out the reaction at a hydroxyl group molar ratio 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 coating film of the curable resin composition may be used. This is because the scratch resistance after immersion in an aqueous alkali solution may be reduced.
  • 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 addition amount of the component (G) in the curable resin composition is not particularly limited, but is usually 1 to 95% by weight based on the total amount of the composition other than the organic solvent. The reason for this is that when the addition amount is less than 1% by weight, the refractive index of the cured coating film of the curable resin composition increases, and a sufficient antireflection effect may not be obtained. If the added amount exceeds 95% by weight, the scratch resistance of the cured coating film of the curable resin composition cannot be obtained! This is because there are cases.
  • the addition amount of the component (G) is more preferably 2 to 90% by weight, and further preferably 3 to 85% by weight.
  • particles containing silica as a main component can be blended, and the scratch resistance of the cured product of the composition for forming a low refractive index layer, particularly steel wool resistance. Can be improved.
  • particles having silica as a main component particles having silica having a number average particle diameter of 1 to lOOnm as a main component are preferable.
  • the particle size is measured with a transmission electron microscope.
  • the particle size of the component (H) is preferably 5 to 80 nm, more preferably 10 to 60 nm.
  • known particles can be used, and the shape is not particularly limited.
  • colloidal silica As long as it is spherical, it is not limited to ordinary colloidal silica, and may be hollow particles, porous particles, core-shell type particles, or the like. Further, it is not limited to a spherical shape, and may be an amorphous 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.
  • the organic solvent include alcohols such as methanol, isopropyl alcohol, ethylene glycolate, butanol, ethylene glycol monopolypropyl ether; methyl ethyl ketone, methyl isobutyl ketone, etc. Ketones; Aromatic hydrocarbons such as toluene and xylene; Amides such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; Esters such as ethyl acetate, butyl acetate, and ⁇ -butalate ratatones; Tetrahydrofuran, 1,4 dioxane, etc. In particular, alcohols and ketones are preferred. These organic solvents can be used alone or in admixture of two or more as a dispersion medium.
  • Examples of commercially available silica-based particles include colloidal silica manufactured by Nissan Chemical Industries, Ltd.
  • Product names: methanol silica sol, IPA-ST, MEK-ST, MEK-S T-S, ⁇ — ST— L, IPA— ZL, NBA— ST, XBA— ST, DMAC— ST, ST— UP ⁇ ST— OUP ⁇ ST— 20, ST— 40, ST— C, ST— N, ST— 0, ST-50, ST-OL, etc. can be mentioned.
  • the surface of the colloidal silica subjected to surface treatment such as chemical modification can be used.
  • it contains a hydrolyzable silicon 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-
  • a thiocyanate group such as 3-thiocyanatepropyltrimethoxysilane, which has an epoxy group (3-glycidoxypropyl) trimethoxysilane, 2- (3,4-epoxyhexoxyl) ethyltrimethoxysilane, and the like having a thiol group such as 3-mercaptopropyltrimethoxysilane Can be mentioned.
  • a preferred compound is 3-mercaptopropyltrimethoxysilane.
  • the silica particles used in the present invention preferably have an ethylenically unsaturated group (hereinafter referred to as “reactive silica particles”).
  • the method for producing reactive silica particles is not particularly limited.
  • the reactive silica particles can be obtained by reacting the silica particles having a number average particle size of 10 to LOONm and a reactive surface treatment agent. .
  • examples of the surface treating agent include alkoxysilane compounds, tetrabutoxysilane, tetrabutoxyzirconium, tetraisopropoxyaluminum, and the like. These can be used alone or in combination of two or more.
  • Specific examples of the surface treatment agent include compounds having an unsaturated double bond in the molecule such as y-methacryloxypropyltrimethoxysilane, ⁇ -acryloxypropyltrimethoxysilane, vinyltrimethoxysilane, Examples include compounds represented by the following general formula (21).
  • R. I a methyl group
  • R is an alkyl group having 1 to 6 carbon atoms, is a hydrogen atom or a methyl group, a is 1 or 2, b is an integer of 1 to 5, and A is a divalent alkylene group having 1 to 6 carbon atoms , B is a chain, cyclic or branched divalent hydrocarbon group having 3 to 14 carbon atoms, Z is a (b + 1) valent chain number, cyclic or branched carbon number 2 to 14 This is a divalent hydrocarbon group. Z may contain an ether bond.
  • silica particles have an ethylenically unsaturated group, they can be co-crosslinked with a UV curable acrylic monomer, and scratch resistance is improved. [0154] (3) Preferred embodiment (porous silica particles)
  • porous silica particles are preferred.
  • the first porous silica particles (HI) are obtained by hydrolysis and Z or hydrolysis condensation of a key compound represented by the following formula (22) and a key compound represented by the following formula (23). . That is, it is obtained by hydrolyzing and Z or hydrolytically condensing the silicon compound represented by the formula (22), and subjecting the keen compound represented by the formula (23) to hydrohydrolysis and Z or hydrolytic condensation. It is done.
  • the key compound represented by the formula (22) and the key compound represented by the formula (23) may be mixed and subjected to hydrolysis and Z or hydrolytic condensation at the same time.
  • the second porous silica particles (H2) are a key compound represented by the following formula (22), a key compound represented by the following formula (23), and a key compound represented by the following formula (24). Obtained by hydrolysis of Z and Z or hydrolytic condensation. That is, hydrolysis and Z or hydrolysis condensation of the key compound represented by the formula (22), and hydrolysis and Z or hydrolysis condensation of the key compound represented by the formula (23), and It is obtained by hydrolyzing and Z or hydrolytically condensing the silicon compound represented by the formula (24).
  • the key compound represented by the formula (22), the key compound represented by the formula (23), and the key compound represented by the formula (24) are mixed and simultaneously hydrolyzed and Z or hydrolyzed.
  • the key compound represented by formula (22) is hydrolyzed and Z or hydrolyzed, and then the key compound represented by formula (23) and formula (24) are used.
  • hydrolysis and Z or hydrolysis condensation may be carried out by adding the above-mentioned key compound.
  • each X independently represents an alkoxy group having 1 to 4 carbon atoms, a halogeno group, an isocyanate group, a carboxyl group, or an alkyloxy group having 2 to 4 carbon atoms. Carbo Or an alkylamino group having 1 to 4 carbon atoms, preferably an alkoxy group or a halogeno group, and more preferably an alkoxy group.
  • Xs may be the same or different.
  • Examples of the compound represented by the formula (22) include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, and tetrachlorosilane.
  • R 29 is an alkyl group having 2 to 8 carbon atoms, an allyloxyalkyl group having 4 to 8 carbon atoms or a methacryloxyalkyl group having 5 to 8 carbon atoms, preferably These are a bur group, an aryl group, an attaryloxychetyl group, an attaryloxypropyl group, an attaryloxybutyl group, a methacryloxycetyl group, a methacryloxypropyl group, and a methacryloxybutyl group.
  • j is an integer of 1-3, Preferably it is 1-2.
  • Examples of the compound represented by the formula (23) include vinyltrimethoxysilane, butyltrioxysilane, vinyltrichlorosilane, talyloxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, and the like.
  • the porous silica particles can contain an ethylenically unsaturated group.
  • the scratch resistance of the antireflection film of the present invention having a cured film obtained by curing the curable composition is improved.
  • R 3 is a fluorine-substituted alkyl group having 1 to 12 carbon atoms, preferably a fluorine-substituted alkyl group having 3 to 12 carbon atoms, more preferably fluorine having 3 to 10 carbon atoms. Substituted alkyl group.
  • k is an integer of 1 to 3, preferably 1 to 2.
  • Examples of the compound represented by the formula (24) include 3, 3, 3-trifluoropropyltrimethoxysilane, 2-perfluorohexylmethyltrimethoxysilane, and 2-perfluorohexoxysilyltrimethoxy.
  • the porous silica particles can contain a fluorine-containing alkyl group.
  • the stain resistance of the cured film obtained by curing the curable composition can be improved.
  • Two or more kinds of the key compound represented by the formula (22), the key compound represented by the formula (23), and the key compound represented by the formula (24) may be used.
  • the total of the key compound represented by the formula (22), the key compound represented by the formula (23) and the key compound represented by (24) is 100.
  • the key compound represented by the formula (22), the key compound represented by the formula Z (23), and the key compound represented by the formula Z (2 4) are preferably 60 to 9871. It is hydrolyzed and / or hydrolyzed and condensed at a ratio of ⁇ 301 to 20 (mol%), preferably 65 to 962 to 202 to 15 (mol%).
  • the first and second porous silica particles (HI) and (H2) used in the present invention have an average particle size force of ⁇ 50 nm, preferably 5 to 45 nm, more preferably 5 to 40 nm.
  • the average particle diameter is a number average particle diameter, and is measured with a transmission electron microscope image.
  • the term “porous” means that the specific surface area is 50 to: L000m 2 Zg, preferably 50 to 800 m 2 Zg, and more preferably 100 to 800 m 2 / g. The specific surface area is measured by the BET method.
  • the average particle size is within the above range, scattering of the obtained coating film in the visible light region can be suppressed. Moreover, due to being porous, the density is lowered and the refractive index of the film containing such porous silica particles is lowered.
  • porous silica particles (H) are obtained by the production method described below.
  • the first or second porous silica particles (HI) and (H2) are at least one selected from water, alcohols having 1 to 3 carbon atoms, basic compounds, and acid amides, diols, and semi-ethers of diols.
  • the key compound represented by the above formula (22) and the key compound represented by the formula (23), or the key compound represented by the above formula (22), the formula (23 ) And the compound represented by formula (24) are hydrolyzed and Z Or it can manufacture by hydrolytic condensation.
  • amine compounds are used, and specific examples include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, monoethanolamine, diethylanolamine, dimethylmonoethanol.
  • ammonia, ethanolamine, hydroxy-tetramethylamine or the like is used.
  • the acid amide, diol or diol half-ether is preferably compatible with water and alcohol.
  • N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, etc. are used, preferably N, N-dimethylformamide, N, N-dimethylacetamide is used.
  • the diol for example, ethylene glycol, propylene glycol, 1,2-butanediol and the like are used, and preferably ethylene glycol and propylene glycol are used.
  • ethylene glycol monomethyl ether or propylene glycol monomethyl ether is used as the half ether of the diol.
  • porous silica particles used in the present invention can be made porous by the coexistence of acid amide, diol or diol half ether during synthesis.
  • the total concentration of the key compound of formula (22) and the key compound of formula (23) or the key compound of formulas (22) to (24) in the reaction solution is usually 0 in terms of complete hydrolysis condensate. 5 to 10% by weight, preferably 1 to 8% by weight.
  • “in terms of complete hydrolyzed condensate” is a theoretical value calculated assuming that the key compound was completely hydrolyzed and condensed. This corresponds to the weight of X in the compound and the compound of (23) or the compounds of formulas (22) to (24) when X is substituted with 2 moles of oxygen atoms.
  • the compound of formula (22) and the compound of formula (23), or the compound of formula (22), the compound of formula (23) and the compound of formula (24) are mixed simultaneously.
  • Hydrolysis and Z or hydrolytic condensation may also be used. Water, alcohols having 1 to 3 carbon atoms, basic compounds, and acid amides, diols and diols and diol semi-ether forces are present.
  • the key compound represented by the formula (22) is hydrolyzed and subjected to Z or hydrolytic condensation, and then the key compound represented by the formula (23) or the formula (23), respectively.
  • hydrolysis and Z or hydrolysis condensation may be carried out by adding a key compound and a key compound represented by the formula (24).
  • the reaction temperature for hydrolysis and Z or hydrolysis-condensation can be arbitrarily determined in consideration of the boiling point and reaction time of the alcohol and acidamide to be used.
  • the reaction time is defined by the formula (22), the compound represented by formula (23), the type of formula (24), the reaction rate, the type and amount of base, etc.
  • the optimum value varies depending on the value, and is not limited.
  • the porous silica particles become organic.
  • a dispersion liquid dispersed in a solvent can be obtained.
  • the dispersion medium is water! /
  • organic solvents are 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.
  • the compounding amount of the porous silica particles (H) in the resin composition is usually 5 to 99% by weight, preferably 10 to 98% by weight, based on the total amount of the composition other than the organic solvent. More preferred is -97% by weight. If it is less than 5% by weight, the hardness of the cured film may be insufficient. If it exceeds 99% by weight, sufficient film strength may not be obtained.
  • the amount of particles means a solid content, and when the particles are used in the form of a solvent dispersion, the amount of particles does not include the amount of solvent.
  • the following components can be added to the composition for a low refractive index layer used in the present invention, if necessary.
  • the polyfunctional (meth) attareito toy compound containing at least two or more (meth) attaroyl groups and Z or at least one or more (meth) alkyls It is also possible to add a fluorine-containing (meth) attareito toy compound containing a acryloyl group.
  • the compound is not particularly limited as long as it is a compound containing at least two (meth) atallyloyl groups in the molecule.
  • examples include neopentyl glycol di (meth) acrylate, trimethylol propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylol ethane tri (meth) acrylate, penta erythritol tetra (Meth) acrylate, dipentaerythritol tetra (meth) acrylate, alkyl-modified dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl-modified dipenta erythritol penta (meth) acrylate, Dipentaerythritol hexa (meth) acrylate, force prolatatatone modified dipentaery
  • neopentyl glycol di (meth) acrylate dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and force prolatatatone.
  • Modified dipentaerythritol hexa (meth) acrylate is particularly preferred.
  • the compound is not particularly limited as long as it is a fluorine-containing (meth) ataretoy compound containing at least one or more (meth) atalyloyl groups.
  • fluorine-containing (meth) ataretoy compound containing at least one or more (meth) atalyloyl groups.
  • examples thereof include perfluorooctyl cetyl (meth) acrylate, octafluoropentyl (meth) acrylate, trifluoroethyl (meth) acrylate, and the like. These can be used alone or in combination of two or more.
  • the amount of component (I) to be added is not particularly limited, but is usually 0 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 addition amount exceeds 90% 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.
  • the amount of component (I) added is more preferably 80% by weight or less, and further preferably 60% by weight or less.
  • a compound that generates active species by irradiation of active energy rays or heat can also be added.
  • 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.
  • an active energy ray Light energy rays such as visible light, ultraviolet rays, infrared rays, X-rays, ⁇ rays, j8 rays, ⁇ rays and the like can be mentioned.
  • 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 Trimethyl benzoyl diphosphine phosphine oxide, 2-methyl- 1 1 [4 1 (methylthio) phenol] 1 2 Morpholinopropane 1 1-one, 2 (dimethylamino) 1 1 [4 (morpholol) phenol 1] -butanone and the like are more preferable, 1-hydroxycyclohexylphenylketone, 2-methyl-1-one [4 (methylthio) phenol] 2 morpholinopropane 1-o 2— (Dimethylamino) — 1— [4- (Morpholol) phenol] —2 Phenylmethyl )-1-butanone and the like.
  • the addition amount of the photopolymerization initiator is not particularly limited, but is preferably 0.01 to 20% by weight based on the total amount of the composition other than the organic solvent. This is because when the amount added is less than 0.01% 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, when the addition amount of the photopolymerization initiator exceeds 20% by weight, the refractive index of the cured film increases and the antireflection effect may be lowered.
  • the photopolymerization initiator it is more preferable to add the photopolymerization initiator to 0.05 to 15% by weight with respect to the total amount of the composition other than the organic solvent. It is more preferable to do this.
  • 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 Oral peroxide, 2,2, -azobis (2,4-dimethylvale-tolyl), 2,2, -azobis (4-methoxy-2,4-dimethylvale-tolyl), etc., alone or in combination of two or more Can be mentioned.
  • the addition amount of the thermal polymerization initiator is not particularly limited, but is preferably 0.01 to 20% by weight based on the total amount of the composition other than the organic solvent. The reason for this is that if the amount of added calories is less than 0.01% by weight, the curing reaction becomes insufficient, and the scratch resistance and the scratch resistance after immersion in an alkaline aqueous solution may decrease. On the other hand, if the amount of addition of the photopolymerization initiator exceeds S20% by weight, the refractive index of the cured film increases and the antireflection effect may decrease. For this reason, it is more preferable to add the thermal polymerization initiator to 0.05 to 15% by weight with respect to the total amount of the composition other than the organic solvent. It is more preferable that the value be within the range.
  • an organic solvent it is preferable to add an organic solvent to the curable resin composition.
  • an organic solvent an alcohol solvent having 1 to 8 carbon atoms, a ketone system having 3 to 10 carbon atoms, or an ester solvent having 3 to carbon atoms: L0 can be preferably used.
  • Ethyl ketone, methyl amyl ketone, methanol, ethanol, tert-butanol, isopropanol, propylene glycolanol monomethylol ether, propylene glycol norethyl ether, propylene glycol monopropyl ether, etc. are particularly preferred and can be mentioned as examples. .
  • These organic solvents can be used alone or in combination of two or more.
  • the addition amount of the organic solvent is not particularly limited, but is preferably 100 to 100,000 parts by weight with respect to 100 parts by weight of the composition other than the organic solvent.
  • the reason for this is that when the addition amount is less than 100 parts by weight, it may be difficult to adjust the viscosity of the curable resin composition.
  • the addition amount exceeds 100,000 parts by weight the curable resin composition is difficult to adjust. This is because the storage stability of the composition may be decreased, or the viscosity may be excessively decreased to make handling difficult.
  • 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.
  • Additives such as plasticizers, ultraviolet absorbers, antioxidants, antistatic agents, silane coupling agents, inorganic fillers other than the component (H), pigments, dyes and the like can also be contained.
  • the curable resin composition used in the present invention comprises the (G) ethylenically unsaturated group-containing fluoropolymer and the (H) component, or, if necessary, the (I) component, the ⁇ component, ( Ii) It can be prepared by adding an organic solvent and an additive, respectively, and mixing at room temperature or under heating conditions. Specifically, mixers, aders, ball mills, triple rolls, etc. It can be prepared using a mixer. However, when mixing under heating conditions
  • the temperature is not higher than the decomposition start temperature of the thermal polymerization initiator.
  • the exposure dose is within the range of 0.01 to 10 j / cm 2 .
  • the value is preferred.
  • the exposure amount it is more preferable to set the exposure amount to a value in the range of 0.1 to 5 jZcm 2 , and it is more preferable to set the exposure value to a value in the range of 0.3 to 3 jZcm 2 .
  • composition for forming a low refractive index layer is cured by heating, it is preferably heated at a temperature in the range of 30 to 200 ° C for 0.5 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.
  • tin-containing indium oxide dispersion In a container shielded from ultraviolet rays, tin-containing indium oxide dispersion (Fuji Chemical Co., Ltd. Houtform NID-20, dispersion solvent isopropyl alcohol, tin-containing indium oxide 20% by weight, average primary particle size 13nm
  • ITO particles—1 50 parts
  • dipentaerythritol hexaatalylate (trade name KAYA, manufactured by Nippon Gyaku Co., Ltd.) RAD DPHA
  • B-l dipentaerythritol hexaatalylate
  • each composition of Examples 2-3 and Comparative Examples 1-3 shown in Table 1 was obtained.
  • the blending amount of ITO particles and dispersant represents only the solid content in the added dispersion, and the dispersion medium is included in the blending amount of the solvent.
  • Examples 1-3 and Comparative Examples 1-3 on a polyester film A4 300 made by Toyobo Co., Ltd., film thickness 188 111
  • a wire bar coater Each of the compositions was applied and dried in an oven at 80 ° C. for 3 minutes to form a coating film.
  • the coating film was cured with ultraviolet light under a light irradiation condition of UZcm 2 using a metal nitride lamp in the atmosphere to form a cured film (hard coat layer) having a thickness of 3 ⁇ m.
  • the total cured light transmittance, haze, and surface resistance of the obtained cured film were evaluated according to the following criteria. The results obtained are shown in Table 1.
  • the total light transmittance (%) and haze (%) of the cured film were measured using a color haze meter (manufactured by Suga Test Instruments Co., Ltd.) according to JIS K7105.
  • the pencil hardness of the cured film was evaluated according to JIS K5600-5-4, and the film cured on a glass substrate was evaluated. (3) Surface resistance
  • ITO particles 1: Fuji Chemical Co., Ltd., Nutform NID-20 (—Next particle size: 13 nm, Secondary particle size: 25 nm IPA dispersion)
  • Dispersant 1 Dispersant contained in Fuji Chemical Co., Ltd.
  • Utoform NID-20 ITO particles 2 Pastoran made by Mitsui Mining Co., Ltd. (Primary particle size: 30nm, Secondary particle size: 15Onm water dispersion)
  • Dispersant 2 Dispersant contained in Pastoran (ITO particle-2) manufactured by Mitsui Mining & Smelting Co., Ltd.
  • ITO particles-3 Nanotec (primary particle size: 25nm, secondary particle size: 80 ⁇ m EtOH dispersion) manufactured by Shi Kasei Co., Ltd.
  • Dispersant 3 Dispersant included in Nanotech manufactured by Shi Kasei Co., Ltd.
  • ITO particle-4 Pastoran manufactured by Mitsui Mining Co., Ltd. (Primary particle size: 30nm, Secondary particle size: 30Onm MeOH dispersion)
  • Dispersant 4 Dispersant contained in Pastoran (ITO particles—4) manufactured by Mitsui Mining Co., Ltd.
  • Comparative Examples 1 and 3 are of the order of 10 7 ⁇ , and the surface resistance is very small, but the haze is large and the transparency is poor.
  • Comparative Example 2 on the contrary, the haze is relatively low, but the surface resistance is as large as 10 14 ⁇ , and the antistatic property is inferior.
  • the surface resistance is Both are in the order of ⁇ ⁇ , and the haze is 0.1% or 0.2%, which satisfies the requirements of both antistatic properties and transparency. Power.
  • this yarn composition contains a total of 773 parts of the compounds represented by the following formula (25) and the following formula (26), and 220 parts of pentaerythritol tetraatalylate which has not participated in the reaction. Are mixed.
  • this composition contains 75 parts of the compound (B-1) represented by the following formula (27) and 37 parts of pentaerythritol tetraatalylate which is not involved in the reaction.
  • Production Example 3 Production of reactive silica particle sol bonded with an organic compound having a polymerizable unsaturated group
  • Silica particle sol (Methyl ethyl ketone silica sol, MEK-ST — L, Nissan Chemical Industries, Ltd., number average particle size 0.05 ⁇ m, silica concentration 30%) 143 g (43 g as silica particles), Production Example 1 2.8 g of the solution containing the specific organic compound (Aa) produced in 1), 0 lg of distilled water and 0. Olg of p-hydroquinone monomethyl ether were mixed and heated and stirred at 65 ° C. Four hours later, orthoformate methyl ester 1.Og was added, and the mixture was further heated for 1 hour to obtain a reactive silica particle sol having a solid content of 31%.
  • Hexafluoropropylene 86. Og was then added and heating was started.
  • the pressure when the temperature in the autoclave reached 60 ° C was 2.9 X 10 5 Pa.
  • the reaction was continued with stirring at 70 ° C. for 20 hours.
  • the pressure dropped to 2.
  • OX 10 5 Pa the autoclave was cooled with water to stop the reaction. After reaching room temperature, the unreacted monomer was released and the autoclave was released to obtain a polymer solution having a solid content concentration of 30.0%.
  • the obtained polymer solution was poured into methanol to precipitate a polymer, which was then washed with methanol and vacuum dried at 50 ° C. to obtain 220 g of a hydroxyl group-containing fluoropolymer.
  • a 1-liter separable flask equipped with a magnetic stirrer, a glass cooling tube, and a thermometer was charged with 70.0 g of the hydroxyl group-containing fluoropolymer obtained in Production Example 4, and 2, 6-di-t as a polymerization inhibitor.
  • Olg and MIBK520g were charged and stirred at 20 ° C. until the hydroxyl group-containing fluoropolymer dissolved in MIBK and the solution became clear and uniform.
  • porous silica particle 1 powder sample 10 g was placed in an aluminum dish and dried on a hot plate at 150 ° C. for 1 hour to obtain a porous silica particle 1 powder sample.
  • the BET specific surface area of the obtained porous silica particle powder was measured using AUTOSORB-1 manufactured by Quantachrome Instruments, the specific surface area was 200 m 2 Zg.
  • Example 4 56 g of MIBK solution of the ethylenically unsaturated group-containing fluoropolymer obtained in Production Example 5 (8.5 g as an ethylenically unsaturated group-containing fluoropolymer) and the porous silica obtained in Production Example 7 1750 g of the particle dispersion (87.5 g as porous silica particles), 2-methyl-1 [4 (methylthio) phenol] 2 morpholinopropane 1-on 4 g, MIBK 700 g as a photopolymerization initiator were attached with a stirrer. The mixture was placed in a glass separable flask and stirred at 23 ° C. for 1 hour to obtain a composition 2 for forming a low refractive index layer. When the solid content was determined in the same manner as in Example 1, it was 4% by weight. [0206] Example 4
  • Example 1 The liquid curable composition obtained in Example 1 was applied to a polyester film A4300 (made by Toyobo Co., Ltd., film thickness 188 ⁇ m) subjected to surface easy adhesion treatment using a wire bar coater # 20. And dried in an oven at 80 ° C for 3 minutes. Subsequently, the coating film was UV-cured under a light irradiation condition of UZcm 2 using a methanolide lamp in the atmosphere to produce a film having an antistatic hard coat layer. When the film thickness of the antistatic hard coat layer was measured with a stylus type surface shape measuring instrument, it was 3 m.
  • the composition 1 for forming a low refractive index layer obtained in Production Example 6 was applied using a wire bar coater # 3, and the conditions of 80 ° C for 1 minute in an oven were applied. And dried. Next, using a metal nitride lamp under a nitrogen atmosphere, the coating film was UV-cured under the light irradiation conditions of UZcm 2 to form a low refractive index layer, thereby producing an antireflection laminate 1. Reflectance power of the obtained antireflection laminate 1 The film thickness of the low refractive index layer was calculated.
  • An antireflection laminate 2 was prepared in the same manner as in Example 4 except that the low refractive index layer forming composition 2 obtained in Production Example 8 was used instead of the low refractive index layer forming composition 1. .
  • the film thickness of the low refractive index layer was calculated in the same manner as in Example 1, it was 0 .: Lm.
  • An antireflection laminate 3 was produced in the same manner as in Example 4 except that the liquid curable composition obtained in Example 3 was used instead of the liquid curable composition obtained in Example 1.
  • the film thickness of the low refractive index layer was calculated in the same manner as in Example 4, it was 0 .: Lm.
  • An antireflection laminate 4 was prepared in the same manner as in Example 6 except that the low refractive index layer forming composition 2 obtained in Production Example 8 was used instead of the low refractive index layer forming composition 1. [0210] Comparative Example 4
  • Example 6 except that the liquid curable composition obtained in Comparative Example 2 was applied on the base material using a wire bar coater # 40 instead of the liquid resin composition obtained in Example 1.
  • a wire bar coater # 40 instead of the liquid resin composition obtained in Example 1.
  • an antireflection laminate 5 was produced.
  • the film thickness of the low refractive index layer was calculated in the same manner as in Example 4, it was 0.1 m.
  • An antireflection laminate 6 was prepared in the same manner as in Comparative Example 4 except that the low refractive index layer forming composition 2 obtained in Production Example 8 was used instead of the low refractive index layer forming composition 1. .
  • the film thickness of the low refractive index layer was calculated in the same manner as in Example 4, it was 0 .: Lm.
  • the total light transmittance (%) and haze (%) of the cured film were measured according to JIS K7105 using a color haze meter (manufactured by Suga Test Instruments Co., Ltd.). Table 2 shows the results obtained.
  • the surface resistance ( ⁇ / mouth) of the cured film was measured using a high resistance meter (Agilent Technologies Corp. Agilent 4339B) and a resiliency cell 16008B (Agilent Technology Co., Ltd.) The measurement was performed under an applied voltage of 100V. The results obtained are shown in Table 2.
  • the reflectance of the resulting anti-reflection laminate was measured with a spectral reflectance measuring device (instant multi-photometering system, MCPD-3000, manufactured by Otsuka Electronics Co., Ltd.).
  • the absolute reflectance was measured in the wavelength range of 400 to 800 nm. And evaluated.
  • Table 2 shows the reflectance at a wavelength of 550 nm.
  • the cloth rubbing resistance test of the antireflection laminate was carried out by the following method.
  • a non-woven fabric B EMCOT S-2, manufactured by Asahi Kasei Kogyo Co., Ltd.
  • a Gakushin type friction fastness tester AB-301, manufactured by Tester Sangyo Co., Ltd.
  • Table 2 shows the results obtained.
  • the ethanol resistance test of the cured film was performed by the following method. That is, a non-woven fabric soaked with ethanol (BEMCOT S-2, manufactured by Asahi Kasei Kogyo Co., Ltd.) is attached to a Gakushin type friction fastness tester (AB-301, manufactured by Tester Sangyo Co., Ltd.), and the surface of the cured film was repeatedly rubbed 20 times under the condition of a load of 500 g, and the presence or absence of scratches on the surface of the cured film was visually confirmed according to the following criteria. Table 2 shows the results obtained.
  • Examples 4 to 7 using particles (ITO particles 1) containing tin-containing indium oxide (ITO) as a main component are high in total light transmittance, low in haze, low in surface resistance, scratch resistance, and chemical resistance. It can be seen that it is excellent in quality.
  • a liquid curing that is excellent in curability and can form a coating film (film) excellent in antistatic properties, hardness, scratch resistance, and transparency on the surface of various substrates.
  • Composition, cured film and antistatic laminate can be provided.
  • the cured film of the present invention has excellent scratch resistance and adhesion, it is useful as a hard coat. Further, since it has an excellent antistatic function, it is useful as an antistatic film by being disposed on a substrate of various shapes such as a film, a plate, or a lens.
  • Examples of the application of the cured film of the present invention include, for example, touch panel protective films, transfer foils, optical disk hard coats, automotive window films, antistatic protective films for lenses, cosmetic containers, and the like.
  • Examples thereof include use as an anti-reflection film for antistatics for various display panels and the like, and use as an anti-reflection film for anti-statics such as plastic lenses, polarizing films and solar battery panels.
  • an antistatic laminate having an excellent curability and having a cured film having excellent antistatic properties, hardness, scratch resistance, and transparency on the surface of various substrates. it can.
  • the laminate of the present invention mainly includes, for example, a protective film for touch panels, a transfer foil, a hard coat for optical disks, a window film for automobiles, an antistatic protective film for lenses, and a surface protective film for high-design containers such as cosmetic containers.
  • Anti-static function for various display panels such as CRT, liquid crystal display panel, plasma display panel, electo-luminescence display panel, etc. as a hard coat for the purpose of preventing product surface scratches and electrostatic dust.
  • As an attached antireflection film it can be used as an antireflection film with an antistatic function for plastic lenses, polarizing films, solar battery panels and the like.
  • the laminate of the present invention can prevent scratches (scratches) on, for example, plastic optical parts, touch panels, film-type liquid crystal elements, plastic housings, plastic containers, flooring materials as building interior materials, wall materials, artificial stones, etc. It can be suitably used as a hard coating material for preventing contamination, an adhesive for various substrates, a sealing material, a binder material for printing ink, and the like.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Laminated Bodies (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

La présente invention concerne un stratifié comprenant au moins un matériau de base et une couche de film durci obtenue en durcissant une composition liquide durcissable contenant les composants suivants : (A) des particules composées principalement d’oxyde d’indium contenant de l’étain (ITO), le diamètre des particules principales de celles-ci étant de 20 nm ou moins et le diamètre des particules secondaires de 50 nm ou moins, (B) un composé comportant deux ou plusieurs groupes insaturés polymérisables dans chaque molécule, (C) un initiateur de photopolymérisation et (D) un solvant.
PCT/JP2006/311599 2005-06-13 2006-06-09 Composition liquide durcissable, film durci et stratifié antistatique WO2006134834A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2005-172279 2005-06-13
JP2005172278A JP2006348069A (ja) 2005-06-13 2005-06-13 液状硬化性組成物及びその硬化膜
JP2005-172278 2005-06-13
JP2005172279 2005-06-13

Publications (1)

Publication Number Publication Date
WO2006134834A1 true WO2006134834A1 (fr) 2006-12-21

Family

ID=37532197

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2006/311599 WO2006134834A1 (fr) 2005-06-13 2006-06-09 Composition liquide durcissable, film durci et stratifié antistatique

Country Status (2)

Country Link
TW (1) TW200712113A (fr)
WO (1) WO2006134834A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104945977A (zh) * 2015-06-18 2015-09-30 成都纳硕科技有限公司 一种外墙用水性紫外光低温固化涂料

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115073129A (zh) * 2022-06-17 2022-09-20 广东盈浩工艺制品有限公司 一种防静电陶瓷及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09108621A (ja) * 1995-10-17 1997-04-28 Nippon Kayaku Co Ltd 紫外線硬化型熱線遮断性樹脂組成物及びそれをコーティングしたフィルム
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
JP2004176006A (ja) * 2002-11-29 2004-06-24 Sumitomo Seika Chem Co Ltd 光硬化性組成物
JP2004307735A (ja) * 2003-04-10 2004-11-04 Jsr Corp 液状硬化性組成物、硬化膜及び帯電防止用積層体

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09108621A (ja) * 1995-10-17 1997-04-28 Nippon Kayaku Co Ltd 紫外線硬化型熱線遮断性樹脂組成物及びそれをコーティングしたフィルム
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
JP2004176006A (ja) * 2002-11-29 2004-06-24 Sumitomo Seika Chem Co Ltd 光硬化性組成物
JP2004307735A (ja) * 2003-04-10 2004-11-04 Jsr Corp 液状硬化性組成物、硬化膜及び帯電防止用積層体

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104945977A (zh) * 2015-06-18 2015-09-30 成都纳硕科技有限公司 一种外墙用水性紫外光低温固化涂料

Also Published As

Publication number Publication date
TW200712113A (en) 2007-04-01

Similar Documents

Publication Publication Date Title
KR100917528B1 (ko) 경화성 액체 조성물, 경화 필름 및 대전방지성 라미네이트
JP5092744B2 (ja) 反射防止積層体
CN109312038B (zh) 活化能射线固化性树脂组合物、树脂成型品以及树脂成型品的制造方法
JP5477299B2 (ja) マレイミド基で表面修飾した無機酸化物微粒子を含む硬化型組成物
KR101268700B1 (ko) 액상 경화성 조성물, 경화막 및 대전 방지용 적층체
US20090191404A1 (en) Curable liquid composition, cured film, and antistatic laminate
JP2005089536A (ja) 硬化性樹脂組成物及び反射防止膜
WO2006109496A1 (fr) Composition de résine durcissable par irradiation et revêtement antireflet
JP2006306008A (ja) 帯電防止用積層体
JP4144477B2 (ja) 液状硬化性組成物、硬化膜及び帯電防止用積層体
JP4899545B2 (ja) 硬化性樹脂組成物及びそれからなる硬化膜
JP4872142B2 (ja) 帯電防止用硬化性組成物、硬化膜及び帯電防止性反射防止積層体
JPWO2006070707A1 (ja) 反射防止膜
WO2006070710A1 (fr) Film antireflet
JP2007229999A (ja) 反射防止積層体
KR101220567B1 (ko) 경화성 수지 조성물 및 이를 포함하는 경화막 및 적층체
JP2007022071A (ja) 帯電防止用積層体
WO2006051835A1 (fr) Composition de résine durcissable, film durci formé à partir de celle-ci et corps multicouche
WO2006134834A1 (fr) Composition liquide durcissable, film durci et stratifié antistatique
JP2008137190A (ja) 反射防止積層体
WO2007004447A1 (fr) Composition durcissable antistatique, film durci de celle-ci et corps multicouche antistatique
JP2006348069A (ja) 液状硬化性組成物及びその硬化膜
JP5339320B2 (ja) 硬化性組成物及び反射防止膜
JP4618018B2 (ja) 帯電防止用積層体
JP2007007984A (ja) 帯電防止用積層体

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 06757222

Country of ref document: EP

Kind code of ref document: A1