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
  • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
  • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
  • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
  • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
• • 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
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/42—Gloss-reducing agents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0025—Crosslinking or vulcanising agents; including accelerators

Definitions

• Liquid curable resin composition Liquid curable resin composition, cured film and laminate
• the present invention relates to a liquid curable resin composition, and particularly has high transparency and a low refractive index.
• the present invention relates to a liquid curable resin composition capable of forming a cured film having good scratch resistance, a cured film comprising the same, and a laminate including the cured film.
• an antireflection film made of a low refractive index material is coated on a substrate of the display device.
• a method of forming a film for example, a method of forming a thin film of a fluorine compound by an evaporation method is known.
• a technique capable of forming an antireflection film on a large-capacity display device at low cost mainly for a liquid crystal display device.
• the evaporation method it is difficult to form a uniform antireflection film with high efficiency on a large-area substrate, and the cost is low because a vacuum device is required. Is difficult to do.
• a method of forming a liquid composition by dissolving a fluoropolymer having a low refractive index in an organic solvent and applying the composition to the surface of the substrate to form an antireflection film is preferred.
• the law is being considered.
• it has been proposed to apply a fluorinated alkylsilane to the surface of a substrate for example, see Patent Documents 1 and 2).
• a method of applying a fluoropolymer having a specific structure has been proposed (for example, see Patent Document 3).
• Patent Document 1 Japanese Patent Application Laid-Open No. 61-40845
• Patent Document 2 Japanese Patent Publication No. 6-98703
• Patent Document 3 Japanese Patent Application Laid-Open No. 6-115023
• the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a liquid curable resin composition capable of efficiently producing any two or more layers. Another object of the present invention is to provide a cured film having high transparency, high adhesion to a substrate, and excellent scratch resistance (steel wool resistance).
• the present inventors have intensively studied and studied a liquid containing a fluorine-containing polymer having a specific structure, silicon dioxide particles, and a solvent having a sp value in a specific range.
• the curable resin composition By using the curable resin composition, the cured film obtained by curing the resin composition is substantially free of a layer in which silicon dioxide particles are present at a high density and substantially no silicon dioxide particles.
• the inventors have found that the layers are separated into layers and that the obtained two-layer film is excellent in abrasion resistance, thereby completing the present invention.
• the present invention provides a liquid curable resin composition, a cured film obtained by curing the same, and a laminate.
• a liquid curable resin composition comprising:
• a method for producing a cured film comprising a step of curing the liquid curable resin composition according to the above [1] by heating or irradiating radiation.
• the other layer is a hard coat layer, a layer having a refractive index of 1.5-1.7, and a layer having a refractive index of 1.3-1.5 and a layer having a refractive index of 1.6-2.2.
• the above-mentioned base material is made of triacetyl cellulose, polyethylene terephthalate resin, polycarbonate resin, acrylic resin, acrylic Z styrene copolymer resin, polyolefin resin, norbornene resin, or glass resin.
• the liquid curable resin composition of the present invention can be advantageously used particularly for forming optical materials such as an antireflection film and an optical fiber sheath material, and has a high fluorine content. It can be suitably used as a coating material, a weather-resistant film material, a coating material, and the like for a substrate requiring weather resistance.
• the cured film has excellent adhesion to the substrate, has high scratch resistance, and provides a good antireflection effect. Therefore, the cured film is extremely useful as an antireflection film and can be applied to various display devices. By doing so, the visibility can be improved.
• FIG. 1 is an electron micrograph showing a typical two-layer separation state.
• FIG. 2 is an electron micrograph showing a uniform state without layer separation.
• the liquid curable resin composition of the present invention contains the following components (A) to (E).
• At least one kind of fluorine-containing polymer selected from the group consisting of a fluorine-containing polymer having a hydroxyl group in a molecule and a fluorine-containing polymer having an ethylenically unsaturated group
• the fluorine-containing polymer is a polymer having a carbon-fluorine bond in a molecule, and in the present invention, a fluorine-containing polymer having a hydroxyl group in a molecule (hereinafter, referred to as a “hydroxyl-containing fluorine-containing polymer”) ) And at least one fluorine-containing polymer selected from the group consisting of ethylenically unsaturated group-containing fluorine-containing polymers.
• a hydroxyl group-containing fluoropolymer is used because a hydroxyl group is required as a reaction site with the component (B).
• a fluorine-containing polymer containing an ethylenically unsaturated group is used. It is also possible to use a hydroxyl group-containing fluoropolymer and an ethylenically unsaturated group-containing fluoropolymer in combination.
• hydroxyl group-containing fluoropolymer examples include those having 10 to 50 mol% of structural units derived from a monomer having a hydroxyl group and having a polysiloxane segment in the main chain.
• the fluorine content is a value measured by the arizarin complexon method, and the number average molecular weight is This is the value when tetrahydrofuran is used.
• the hydroxyl group-containing fluoropolymer is an olefin polymer having a polysiloxane segment represented by the following general formula (1) in the main chain, and the ratio of the polysiloxane segment in the fluoropolymer is usually 0.1-20 mol 0 /. It is said.
• R 1 and R 2 represent a hydrogen atom, an alkyl group, a halogenated alkyl group or an aryl group which may be the same or different.
• the above-mentioned hydroxyl-containing fluorine-containing polymer includes (a) a fluorine-containing olefin compound (hereinafter referred to as “component (a)”), and (b) a simple polymer containing a hydroxyl group copolymerizable with this component (a). And (c) an azo group-containing polysiloxane conjugate (hereinafter, referred to as “component (c)”), and necessary components. (D) a reactive emulsifier (hereinafter referred to as “component (d)”) and Z or (e) a monomer compound other than component (b) copolymerizable with component (a). Can be obtained.
• component (a) a fluorine-containing olefin compound
• component (c) an azo group-containing polysiloxane conjugate
• component (d) a reactive emulsifier
• Z a monomer compound other than component (b) copolymerizable with component (
• Examples of the fluorine-containing organic conjugate as the component (a) include compounds having at least one polymerizable unsaturated double bond and at least one fluorine atom.
• Examples thereof include: (1) fluoroolefins such as tetrafluoroethylene, hexafluoropropylene and 3,3,3-trifluoropropylene; (2) perfluoro (alkylbutyl ether) s or perfluoro (alkoxyalkylbutylether) ) Class; (3) perfluoro (methinorebi-noreeteneole), nofluoro (etinorebi-noreatenore), nofluoro (propinole vinylinorethene), nofluoro (butinorebininoreetenore), nofluoro (isobutinorebi) (4) Perfluoro (Professional) Perfluoro (alkoxyalkyl butyl ether) such as oxypropy
• hydroxyl group-containing monomer conjugate as the component (b) examples include (1) 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl butyl ether, and 4-hydroxypropyl ether.
• Hydroxyl-containing butyl ethers such as hydroxybutyl butyl ether, 3-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether, and 6-hydroxyhexyl vinyl ether; (2) 2-hydroxyethyl yl ether; Hydroxy group-containing aryl ethers such as hydroxybutylaryl ether and glycerol monoallyl ether; (3) aryl alcohol; (4) hydroxyethyl (meth) acrylate; and others. These compounds can be used alone or in combination of two or more. Preferred are hydroxyl group-containing alkylbutyl ethers.
• Preferred combinations of the above components (a), (b) and (c) are, for example, (1) fluororefin / hydroxyl-containing alkylbutyl ether / polydimethylsiloxane unit, (2) fluororefin Z perfluoro ( (Alkyl alkyl ether) Z hydroxyl-containing alkyl vinyl ether Z polydimethylsiloxane unit, (3) Fluororefin Z perfluoro (alkoxyalkylbutyl ether) / hydroxyl-containing alkyl vinyl ether / polydimethylsiloxane unit, (4) Fluororefin Z perfluoro (alkyl (Butyl ether) Z Hydroxyl group-containing alkylbutyl ether / polydimethylsiloxane unit, (5) Fluororefin Z Perfluoro (alkoxyalkylbutyl ether) Z Hydroxyl group-containing alkylbutyl Ether Z is a poly
• the proportion of the structural unit derived from the component (a) exceeds 70 mol%, the solubility of the obtained hydroxyl group-containing fluoropolymer in an organic solvent is significantly reduced, and the obtained liquid curable resin is reduced.
• the composition has low transparency and low adhesion to the substrate.
• the structural unit derived from the component (b) is preferably 10 to 50 mol%. More preferably, the lower limit is 13 mol% or more, more preferably more than 20 mol%, and 21 mol% or more, and preferably the upper limit is 45 mol% or less, further preferably 35 mol% or less. It is.
• the cured product has good two-layer separation, abrasion resistance and dust. Wipeability can be realized.
• the proportion of the structural unit derived from the component (b) is less than 10 mol%, the solubility of the hydroxyl group-containing fluoropolymer in an organic solvent becomes poor.
• the cured product of the resin composition has deteriorated optical properties of transparency and low reflectance.
• the azo group-containing polysiloxane conjugate of the component (c) is itself a thermal radical generator, and is a polymerization initiator in a polymerization reaction for obtaining a hydroxyl group-containing fluoropolymer.
• other radical initiators can be used in combination.
• a polysiloxane segment represented by the general formula (1) is preferably 0. 1 20 mol 0/0, more preferably 0 The proportion is 1 to 15 mol%, particularly preferably 0.1 to 10 mol%, and particularly preferably 0.1 to 5 mol%.
• a reactive emulsifier is preferably used as a monomer component as the component (d).
• the component (d) when the hydroxyl group-containing fluoropolymer is used as a coating agent, good coating properties and leveling properties can be obtained.
• this reactive emulsifier it is particularly preferable to use a nonionic reactive emulsifier.
• the non-ionic reactive emulsifier include, for example, compounds represented by the following general formula (3) or (4).
• R 3 is an alkyl group which may be linear or branched, and is preferably an alkyl group having 140 carbon atoms.
• the amount of the structural unit derived from the component is rather preferably is 0 to 10 mol 0/0, more preferably 0.5 1 5 mole 0/0, Particularly preferably, it is 0.1-1 mol%. If this proportion exceeds 10 mol%, the resulting liquid curable resin composition becomes sticky, which makes it difficult to handle and reduces the moisture resistance when used as a coating agent.
• the monomer compound (e) other than the component (b) copolymerizable with the component (a) includes (1) methylinolebininoleatenole, ethinolebininoleatenole, n-- Propinolebininoleatenore, isopropyl vinyl ether, n- butylvinylether, isobutylvinylether, tert-butinolebininoleatenole, n-pentinolebininoleatenole, n-hexinolebininoleatenole, n-octylbi- Alkyl ethers or cycloalkyl vinyl ethers such as butyl ether, n-dodecyl butyl ether, 2-ethylhexyl butyl ether and cyclohexyl butyl ether; (2) vinyl acetate, vinyl propionate, vinyl butyrate, Carboxy
• the proportion of the structural unit derived from component (e), preferably rather is 0 70 mole 0/0, more preferably from 5 to 35 mol 0/0.
• this proportion exceeds 70 mol%, the resulting liquid curable resin composition becomes tacky, and thus it becomes difficult to handle, and when used as a coating agent, the moisture resistance decreases.
• component (d) When component (d) is contained, preferred combinations of component (a), component (b), component (c), component (d) and component (e) are as follows.
• Fluororefin / hydroxyl-containing butyl ether / polydimethylsiloxane unit / nonionic reactive emulsifier Z-alkyl butyl ether (2) Fluororefin Z-perfluoro mouth (alkyl butyl ether) / hydroxyl-containing butyl ether / polydimethylsiloxane Unit Z-Non-active reactive emulsifier Z-alkyl butyl ether, (3) Fluororefin / Perfluoro (alkoxyalkyl butyl ether) / hydroxyl-containing butyl ether / polydimethylsiloxane unit / Non-active reactive emulsifier / alkyl butyl ether, ( 4) Fluororefin z Perfluoro (alkyl alkyl ether) Z hydroxyl-containing butyl ether Z polydimethylsiloxane unit Z non-ionic reactive emulsifier Z-
• radical polymerization initiator examples include (1) disilver oxides such as acetyl peroxide and benzoyl peroxide; and (2) methylethyl ketone peroxide. Ketones such as oxides and cyclohexanone peroxide Oxides; (3) hydride peroxides such as hydrogen peroxide, tert-butyl peroxide and cumene hydroperoxide; (4) dialkyls such as di-tert-butyl peroxide, ditamyl peroxide and dilauroyl peroxide Peroxides; (5) peroxyesters such as tert-butylperoxyacetate and tert-butylperoxybivalate; (6) azo-based compounds such as azobisisobutyro-tolyl and azobisisovalero-tolyl; (7) Persulfates such as ammonium persulfate, sodium persulfate and potassium per
• radical polymerization initiator examples include, for example, perfluoroethyl iodide, perfluoropropyl iodide, perfluorobutyl iodide, (perfluorobutyl) ethyl iodide, perfluorohexyl iodide , 2- (perfluorohexyl) ethyl iodide, perfluoroheptyl iodide, perfluorooctyl iodide, 2- (perfluorooctyl) ethyl iodide, perfluorodecyl iodide, 2— (par Fluorodecyl) ethyl iodide, heptafluoro-1-odopropane, monofluoro-3-methylbutyl iodide, perfluoro5-methylhexyl iodide, 2- (perfluoroe
• any of an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method, and a solution polymerization method using a radical polymerization initiator can be used.
• an appropriate operation can be selected from a batch operation, a semi-continuous operation, a continuous operation, or the like.
• the polymerization reaction for obtaining the hydroxyl group-containing fluoropolymer is performed in a solvent system using a solvent.
• a solvent preferably, butyl acetate, isopropyl acetate, isobutyl acetate, and cellosolve acetate; (2) esters, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexane.
• Ketones such as xanone; (3) cyclic ethers such as tetrahydrofuran and dioxane; (4) amides such as N, N-dimethylformamide and N, N-dimethylacetoamide; (5) toluene, xylene and the like Aromatic hydrocarbons; and others. Further, if necessary, alcohols, aliphatic hydrocarbons and the like can be mixed and used.
• the hydroxyl group-containing fluoropolymer obtained as described above may be capable of directly using the reaction solution obtained by the polymerization reaction as a liquid curable resin composition in some cases. It is also possible to perform appropriate post-processing on As the post-treatment, for example, a general purification method represented by a purification method in which a polymerization reaction solution is added dropwise to an insolubilizing solvent for the hydroxyl group-containing fluoropolymer made of alcohol or the like to coagulate the hydroxyl group-containing fluoropolymer. A reprecipitation treatment can be performed, and then a solution of the hydroxyl group-containing fluoropolymer can be prepared by dissolving the obtained solid copolymer in a solvent. In addition, the polymerization reaction solution from which residual monomers have been removed can be used as it is as a solution of a hydroxyl group-containing fluoropolymer.
• the ethylenically unsaturated group-containing fluoropolymer used in the present invention includes a compound containing one isocyanate group and at least one ethylenically unsaturated group, and the above-mentioned (1) hydroxyl group-containing fluoropolymer. And are obtained by reacting Those obtained by reacting at a molar ratio of isocyanate groups Z hydroxyl groups of 1.1 to 1.9 are preferred.
• a compound containing one isocyanate group and at least one ethylenically unsaturated group a compound containing one isocyanate group and at least one ethylenically unsaturated group in a molecule If so, there is no particular limitation. When two or more isocyanate groups are contained, gelation may occur when the above-mentioned (1) hydroxy group-containing fluoropolymer is reacted. Further, as the above-mentioned ethylenically unsaturated group, a (meth) atalyloyl group is preferable because the liquid curable resin composition of the present invention can be more easily cured. Is more preferable. Examples of such a compound include 2- (meth) atalyloyloxyshethyl isocyanate and 2- (meth) atalyloyloxypropyl isocyanate, either alone or in combination of two or more.
• Such a compound can also be synthesized by reacting diisocyanate and a (meth) acrylate having a hydroxyl group.
• diisocyanates include 2,4 tolylene diisocyanate, 2,6 tolylene diisocyanate, 1,3 xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5 naphthalenediisonate.
• 2,4-tolylene diisocyanate isophorone diisocyanate, xylylene diisocyanate, methylene bis (4-cyclohexyl isocyanate), and 1,3-bis (isosinate methyl) cyclohexane Particularly preferred.
• Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) atalyle hydraprolatone (meth) atalylate, polypropylene glycol (meth) atalylate, dipentaerythritol penta (meth) acrylate. And pentaerythritol tri (meth) atalylate, pentaerythritol di (meth) atalylate monostearate, isocyanuric acid EO-modified di (meth) atalylate, and the like, alone or in combination of two or more.
• 2-hydroxyethyl (meth) acrylate and pentaerythritol tri (meth) acrylate are particularly preferred.
• Commercially available hydroxyl-containing polyfunctional (meth) acrylates include, for example, those manufactured by Osaka Organic Chemical Co., Ltd. Trade name HEA, Nippon Kayaku Co., Ltd. trade name KAYARAD DPHA, PET-30, Toagosei Co., Ltd. trade name Aronix M-215, M-233, M-305, M-400 etc. it can.
• the amount of the hydroxyl group-containing polyfunctional (meth) atalylate to be added should be 1.1 to 1.2 mol per 1 mol of the diisocyanate. preferable.
• the ethylenically unsaturated group-containing fluoropolymer used in the present invention includes the above-mentioned compound containing one isocyanate group and at least one ethylenically unsaturated group, and a hydroxyl group-containing fluoropolymer. And is preferably reacted at a molar ratio of isocyanate group Z hydroxyl group of 1.1 to 1.9.
• the reason for this is that if the molar ratio is less than 1.1, the scratch resistance and durability may decrease, while if the molar ratio exceeds 1.9, the ultraviolet-curable resin composition may be reduced. This is because the abrasion resistance of the coating film after dipping in an aqueous alkali solution may decrease.
• the molar ratio of the isocyanate group to the hydroxyl group is preferably 1.1 to 1.5, more preferably 1.2 to 1.5.
• the content of one kind of fluoropolymer is preferably 3-95% by mass based on 100% by mass of the total composition excluding the organic solvent. The reason for this is that if the content is less than 3% by mass, the refractive index of the cured coating film of the ultraviolet-curable resin composition may increase, and a sufficient antireflection effect may not be obtained.
• the addition amount of the component (A) is more preferably 5 to 90% by mass, and more preferably 10 to 80% by mass.
• the curable compound of the component (B) is not particularly limited, but is a compound having a thermosetting or radiation-curable polymerizable group, and has at least two polymerizable groups as part or all of the component (B). It is necessary to include the compound having the above. This compound is suitably used for enhancing the film forming property of the composition.
• the curable conjugate may be simply mixed and included with the fluorine-containing polymer of the component (A), or cured with the fluorine-containing polymer of the component (A). Reaction products obtained by reacting all of the compounds with the active compound or those obtained by reacting only some of them.
• thermosetting curable compound examples include various amino compounds, various hydroxyl group-containing compounds such as pentaerythritol, polyphenol, and glycol, and the like.
• the amino compound used as the curable compound is an amino group capable of reacting with a hydroxyl group present in a hydroxyl group-containing fluoropolymer, for example, one or both of a hydroxyalkylamino group and an alkoxyalkylamino group.
• a compound containing two or more in total and specific examples include melamine-based compounds, urea-based compounds, benzoguanamine-based conjugates, and glycolperyl-based compounds.
• Melamine-based compounds are generally known as compounds having a skeleton in which a nitrogen atom is bonded to a triazine ring, and specific examples thereof include melamine, alkylated melamine, methylol melamine, and alkoxylated methyl melamine. It is preferable that one molecule has at least one or both of a methylol group and an alkoxylated methyl group in one molecule. Specifically, methylolated melamine, alkoxylated methylmelamine, or a derivative thereof obtained by reacting melamine and formaldehyde under basic conditions are preferable, especially in liquid curable resin compositions, which have good storage stability.
• Alkoxylated methylmelamine is preferred in terms of obtaining good reactivity and good reactivity.
• the methylolated melamine and alkosylated methylmelamine used as the curable compound There are no particular restrictions on the methylolated melamine and alkosylated methylmelamine used as the curable compound.
• the method described in the literature “Plastic Materials Course [8] Urea 'Melamine Resin” (Nikkan Kogyo Shimbun) It is also possible to use various fatty substances obtained in the above.
• the urea-based compound include, in addition to urea, polymethylolidine urea, alkoxylated methylurea which is a derivative thereof, methylolylanilide having a perone ring, and alkoxylated methylperone.
• compounds such as urea derivatives various fats and oils described in the above-mentioned documents can be used.
• thermosetting curable compound Commercially available products of such a thermosetting curable compound include Cymel series manufactured by Mitsui Cytec Corporation.
• the radiation-curable curable compound needs to have two or more polymerizable unsaturated groups, and examples thereof include melamine acrylates, (meth) acrylic esters, and vinyl compounds. . Among them, (meth) acrylic esters having two or more (meth) atalyloyl groups (hereinafter, referred to as polyfunctional (meth) acrylic conjugates) are preferable.
• polyfunctional (meth) acrylic conjugate examples include trimethylolpropanetri (meth) acrylate, ditrimethylolpropanetetra (meth) atalylate, pentaerythritol tri (meth) atalylate, and pentane.
• dipentaerythritol hexa (meth) acrylate dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, and ditrimethylolpropane tetra (meth) acrylate are preferred.
• vinyl compounds include dibutylbenzene, ethylene glycol divinyl ether, diethylene glycol divinylinoleether, and triethylene glycol divinylinoleatenole.
• the content of the curable compound (B) in the liquid curable resin composition of the present invention is 3 to 95% by mass based on 100% by mass of the total composition excluding the organic solvent. It is preferred that The reason for this is that if the amount of addition is less than 3% by mass, the cured coating film of the curable resin composition may not be able to obtain the scratch resistance, while if the amount exceeds 95% by mass. This is because the refractive index of the cured coating film of the curable resin composition becomes high, and a sufficient antireflection effect may not be obtained. For this reason, it is more preferable that the amount of the component (B) is 5 to 90% by mass, and it is more preferable that the amount of the component (B) be in the range of 10 to 80% by mass. Yes.
• Examples of the curing catalyst used in the present invention include a thermal acid generator and a photoradical generator that is a photopolymerization initiator.
• the thermal acid generator is a substance capable of accelerating the curing reaction when the liquid curable resin composition coating film is heated and cured, and the heating conditions are made milder. It is a substance that can be improved.
• various acids and salts thereof used as a curing agent for general urea fat, melamine resin and the like can be used. Specific examples include, for example, various aliphatic sulfonic acids and salts thereof, various aliphatic carboxylic acids and salts thereof such as citric acid, acetic acid and maleic acid, and various aromatic carboxylic acids and salts thereof such as benzoic acid and phthalic acid. And alkylbenzenesulfonic acids and their ammonium salts, various metal salts, phosphoric acid and phosphoric acid esters of organic acids, and the like.
• photopolymerization initiators include, for example, acetophenone, acetophenone benzyl ketal, anthraquinone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane 1-on, carbazole, xanthone, 4-cyclobenzophenone, 4 , 4 'diamino benzophenone, 1, 1 dimethoxy deoxy benzoin, 3, 3' dimethyl 4-methoxy benzophenone, thioxanthone, 2, 2-dimethoxy 2- phenyl-phenacetophenone, 1- (4-dodecylphen) -Le) -2-hydroxy-2-methylpropane-1-one, 2-methyl-11- [4- (methylthio) phenyl] -2-morpholinopropane-1one, triphenylamine, 2,4,6-trimethyl Benzyldiphenylphosphine oxide, 1-hydroxycyclohexylphenol-ketone, 2-hydroxy-2- Chill
• the amount of the (C) curing catalyst used in the liquid curable resin composition of the present invention may be 0.1 to 20% by mass relative to 100% by mass of the total composition excluding the organic solvent. More preferably, the content is 0.1 to 10% by mass, and still more preferably, 11 to 10% by mass. (C) Curing If the amount of the catalyst used is too small, it is not preferable because sufficient mechanical strength cannot be obtained. If this ratio is too large, the storage stability of the liquid curable resin composition is poor, or the catalyst acts as a plasticizer in the cured film, so that sufficient mechanical strength cannot be obtained. Absent.
• an ultraviolet irradiation device metal halide lamp, high-pressure mercury lamp, etc.
• a light irradiation condition of 0.001 to lOjZcm 2.
• 0.01—5 jZcm 2 is more preferred
• 0.1—3 JZC m 2 is even more preferred.
• the component (D), iodine-containing silicon particles, refers to particles mainly composed of diacid-containing silicon (also referred to as silica).
• the number average particle size is measured by a dynamic light scattering method.
• Known particles can be used as the particles containing silica as a main component.
• the shape of the particles is not limited to ordinary colloidal silica as long as they are substantially spherical, and hollow particles, porous particles, and core particles can be used. • It may be a shell type particle or the like. In addition, it is not limited to spherical, Is also good.
• the number average particle size of 1 one 100nm determined by dynamic light scattering method, solids 10 40 Weight 0/0, pH is 2. 0-6. 5 colloidal silica is preferred.
• the dispersion medium of silica is water!
• the organic solvent include alcohols such as methanol, isopropinoleanol, ethylene glycol, butanol, and ethylene glycol monopropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; and aromatics such as toluene and xylene.
• organic solvents such as ethers such as tetrahydrofuran and 1,4-dioxane.
• amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone
• esters such as ethyl acetate, butyl acetate, and y-butyrolataton
• 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 as a mixture of two or more kinds as a dispersion medium.
• particles containing silica as a main component include, for example, Snowtex 0 (manufactured by Nissan Chemical Industries, Ltd.) (number-average particle diameter of 7 nm determined by dynamic light scattering method, solid content of 20% by mass). , pH 2 7), the number average particle size determined by SNOWTEX OL (dynamic light scattering method:. 15 nm, solid content:. 20 weight 0/0, pH2 5), and the like.
• particles containing silica as a main component particles obtained by performing a surface treatment such as chemical modification on the surface of colloidal silica can be used.
• the chemical modification include an organic compound (Ab) having a polymerizable unsaturated group described below, a hydrolyzable silicon compound having one or more alkyl groups in a molecule or a compound containing a hydrolyzate thereof (hereinafter, referred to as And an organic compound (Ac).
• the reaction referred to here includes not only covalent bonds but also non-covalent bonds such as physical adsorption.
• the silicon dioxide particles that are not bonded to the organic compound (Ab) (hereinafter, referred to as dioxygenated silicon particles (Aa)) and the organic compound (Ab) or (Ac) are bonded.
• the particles are reactive particles (Dab) or (Dac) t.
• the silicon dioxide particles (Aa) are combined with the organic compound (Ab) or (Ac) having a polymerizable unsaturated group to form reactive particles (Dab) or (Dac). Accordingly, (D) the silicon dioxide particle component has a polymerizable unsaturated group, and can form a strong covalent bond with other polymerizable components, thereby improving the scratch resistance of the cured film obtained. be able to.
• the organic compound (Ab) is preferably a compound having a silanol group in the molecule or a compound that generates a silanol group by hydrolysis.
• the polymerizable unsaturated group contained in the organic compound (Ab) is not particularly limited, and examples thereof include an atalyloyl group, a methacryloyl group, a vinyl group, a probel group, a butagel group, a styryl group, an ethynyl group, and cinnamoyl.
• Groups, maleate groups and acrylamide groups are mentioned as preferred examples.
• This polymerizable unsaturated group is a structural unit that undergoes addition polymerization using an active radical species.
• These groups can be used alone or in combination of two or more.
• the organic compound (Ab) is preferably a compound having a silanol group in the molecule or a compound which generates a silanol group by hydrolysis.
• the compound that generates such a silanol group include a conjugated compound in which an alkoxy group, an aryloxy group, an acetyloxy group, an amino group, a halogen atom, and the like are bonded to a silicon atom.
• a compound to which an alkoxy group or an aryloxy group is bonded, that is, an alkoxysilyl group-containing compound or an aryloxysilyl group-containing compound is preferred.
• the silanol group or the silanol group-generating site of the compound that forms a silanol group is a structural unit that bonds to the silicon dioxide particles (D) by a condensation reaction or a condensation reaction that occurs after hydrolysis.
• Preferred specific examples of the organic compound (Ab) include, for example, a compound represented by the following formula (A-2).
• R 24 and R 25 are a hydrogen atom or an alkyl group or an aryl group having 18 carbon atoms, which may be the same or different, such as methyl, ethyl, propyl, butyl, octyl, and phenyl. And xylyl groups. Here, it is an integer of 1 to 3.
• Examples of the group represented by [(R 24 0) R 25 Si—] include, for example, a trimethoxysilyl group and a triethoxy group.
• Examples thereof include a silyl group, a triphenoxysilyl group, a methyldimethoxysilyl group, and a dimethylmethoxysilyl group.
• a trimethoxysilyl group or a triethoxysilyl group is preferred.
• R 26 is a divalent organic group having an aliphatic or aromatic structure 1 one 12 carbon atoms, linear, it may contain a branched or cyclic structure. Specific examples include methylene, ethylene, propylene, butylene, hexamethylene, cyclohexylene, phenylene, xylylene, dodecamethylene and the like.
• R 27 is a divalent organic radical, usually, the molecular weight 14 from 10,000, preferably, molecular weight 76 5 Medium strength of divalent organic group of 00 is selected.
• Specific examples include chain polyalkylene groups such as hexamethylene, otatamethylene, and dodecamethylene; alicyclic or polycyclic divalent organic groups such as cyclohexylene and norborene; phenylene, naphthylene, and biphenyl- Divalent aromatic groups such as benzene and polyphenylene; and alkyl-substituted and aryl-substituted products thereof.
• these divalent organic groups may include a polyether bond, a polyester bond, a polyamide bond, and a polycarbonate bond, which may include an atomic group containing an element other than carbon and hydrogen atoms.
• R 28 is (k + 1) -valent organic group, preferably a linear, branched or cyclic saturated hydrocarbon group, selected from unsaturated hydrocarbon group.
• Z represents a monovalent organic group having in its molecule a polymerizable unsaturated group that undergoes an intermolecular cross-linking reaction in the presence of an active radical species.
• k is preferably an integer of 110, more preferably an integer of 110, and particularly preferably an integer of 115.
• mercaptopropyltrimethoxysilane and isophorone diisocyanate are mixed in the presence of dibutyltin dilaurate, reacted at about 60 to 70 ° C for about several hours, and then added with pentaerythritol triatalylate. — Manufactured by reacting at 70 ° C for several hours.
• An organic compound (Ab) having a silanol group or a group capable of forming a silanol group by hydrolysis is mixed with the silicon dioxide particles (Aa), and the mixture is hydrolyzed to bond the two. Obtained
• the proportion of the organic polymer component in the reactive particles (Dab), ie, the hydrolyzate and condensate of the hydrolyzable silane, is usually the percentage of mass loss when the dry powder is completely burned in air.
• the room temperature force in air can also be determined by thermal mass spectrometry usually up to 800 ° C.
• the amount of the organic compound (Ab) bound to the dioxygenated silicon particles (Aa) is determined by the sum of the reactive particles (Dab) (the diacidic silicon particles (Aa) and the organic compound (Ab)). ) As 100% by mass, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and particularly preferably 1% by mass or more.
• the amount of the organic compound (Ab) bonded to the silicon dioxide particles (Aa) is less than 0.01% by mass, the dispersibility of the reactive particles (Dab) in the composition is insufficient. The transparency and abrasion resistance of the resulting cured product may not be sufficient.
• the compounding ratio of the silicon dioxide particles (Aa) in the raw material during the production of the reactive particles (Dab) is preferably from 5 to 99% by mass, and more preferably from 10 to 98% by mass. is there.
• Examples of the compound containing a hydrolyzable silicon compound having one or more alkyl groups in the molecule or a hydrolyzate thereof include trimethylmethoxysilane, tributylmethoxysilane, dimethylmethysilane, and the like.
• hydrolyzable silicon compound itself having one or more reactive groups in the molecule can also be used.
• Hydrolyzable silicon compounds having one or more reactive groups in the molecule include, for example, ureapropyl as a compound having a ⁇ group as a reactive group.
• a compound having an thiocyanate group such as lmethoxysilane
• 2- (3,4-epoxycyclohexyl) ethyl as having an epoxy group
• a compound having a thiol group such as lmethoxysilane
• 3-mercaptopropyltrimethoxysilane Preferred examples of the compound include 3-mercaptopropyltrimethoxysilane.
• the proportion of (D) silicon dioxide particles (including the case of reactive particles (Aab) or (Aac)) contained in 100% by mass of the liquid curable resin composition of the present invention was determined to be The amount is preferably 1 to 80% by mass, more preferably 10 to 60% by mass, based on 100% by mass of the total amount of the composition excluding the solvent.
• the liquid curable resin composition of the present invention two or more kinds of (D) diacid silicon particles differing in particle diameter, surface modification and the like can be blended.
• the number average particle diameter of the silicon dioxide particles is 100 nm or less. If the number average particle diameter exceeds 100 ⁇ m, it may be difficult to uniformly disperse the silicon dioxide particles. In addition, the silicon dioxide particles tend to settle out, and may lack storage stability. Furthermore, the transparency of the obtained cured film may decrease or the turbidity (Haze value) may increase.
• the number average particle diameter is more preferably from 10 to 80 nm, and even more preferably from 10 to 50 nm.
• the “number average particle size” is a primary particle size when the silicon dioxide particles are aggregated.
• the solvent of the component (E) used in the liquid curable resin composition of the present invention has an sp value of more than 8.5 and less than 12.8, preferably 8.9 or more and 10.0 or less. There is no particular limitation if it exists.
• the layer separation property means that when the composition of the present invention is applied and the solvent is removed, two or more layers, that is, at least the (D) dianilide silicon particles have a high density. And (D) a layer in which silicon dioxide particles are not substantially present. This means that two or more layers are formed separately.
• the sp value of the solvent is a solubility parameter ( ⁇ ), Is a scale representing the polarity value of.
• the sp value of the solvent is a value represented by the cohesive energy / density and the negative square root of the molecular volume, as represented by the following equation.
• solubility parameter of each component of the specific organic solvent used in the present invention is described in, for example, "Polymer Handbook (third Edition)", edited by J. BRANDRUP et al. (JOHN WILEY & SONS).
• Examples of the solvent of the preferred component (E) used in the liquid curable resin composition of the present invention include aceton, methyl ethyl ketone, methyl propyl ketone and the like.
• the solvent for the liquid curable resin composition can usually contain the solvent used for producing the fluoropolymer as it is.
• a solvent can be separately added and blended for the purpose of improving the coating properties of the liquid curable resin composition and the like, and for other purposes.
• Preferred solvents contained in the liquid curable resin composition of the present invention include ketones such as methylethyl ketone, methyl isobutyl ketone and cyclohexanone, and esters such as ethyl acetate and butyl acetate. it can.
• the solution of the liquid curable resin composition of the present invention may contain a solvent which cannot dissolve the hydroxyl group-containing fluoropolymer or the ethylenically unsaturated group-containing fluoropolymer, for example, water, alcohols and the like.
• a poor solvent such as an ether can be used in combination within a range in which the hydroxyl-containing fluoropolymer or the ethylenically unsaturated group-containing fluoropolymer does not precipitate.
• the solution containing the hydroxyl group-containing fluoropolymer or the ethylenically unsaturated group-containing fluoropolymer may have good preservability and favorable coating properties in some cases.
• Examples of such poorly soluble solvents include ethyl alcohol, isopropyl alcohol, tert-butyl alcohol, ethyl sorb and butyl sorb.
• the compounding amount of the solvent of the component (E) is based on 100 parts by mass of the solid matter excluding the organic solvent (the solvent of the component (E) and other solvents) in the liquid curable resin composition of the present invention. Is preferably 25 One 9900 parts by mass, more preferably 100-4900 parts by mass, and even more preferably 400-3300 parts by mass is used.
• the liquid curable resin composition of the present invention may have, for example, the purpose of improving the coating properties of the liquid curable resin composition and the physical properties of a thin film after curing, and imparting photosensitivity to a coating film.
• various additives having a hydroxyl group such as various polymers and monomers, coloring agents such as pigments and dyes, stabilizers such as antioxidants and ultraviolet absorbers, photosensitive acid generators, surfactants, and polymerization inhibitors.
• a photoacid generator for the purpose of improving the hardness and durability of the formed cured film, and in particular, does not reduce the transparency of the liquid curable resin composition after curing, Further, it is preferable to select and use one that is uniformly dissolved in the solution.
• Examples of the polymer having a hydroxyl group that can be blended in the liquid curable resin composition of the present invention are obtained by copolymerizing a hydroxyl-containing copolymerizable monomer such as hydroxyethyl (meth) acrylate.
• Examples include resins having a phenol skeleton known as polymers, novolak resins or resole resins.
• colorants examples include: (1) extenders such as alumina white, clay, barium carbonate, and barium sulfate; (2) zinc white, lead white, Inorganic pigments such as graphite, lead red, ultramarine, navy blue, titanium oxide, zinc chromate, red iron, carbon black, etc .; (3) Brilliant carmine 6B, permanent red 6B, permanent red R, benzidine yellow, phthalocyanine blue, phthalocyanine green, etc. Organic pigments;
• Basic dyes such as magenta and rhodamine; (5) Direct dyes such as direct scarlet and direct orange; (6) Acid dyes such as roserin and methanol yellow; and others.
• Stabilizers such as anti-aging agents and ultraviolet absorbers
• the antioxidant and the ultraviolet absorber which can be added to the liquid curable resin composition of the present invention known agents can be used.
• the anti-aging agent include, for example, di-tert-butylphenol, pyrogallol, benzoquinone, hydroquinone, methylene blue, tert-butylcatechol, monobenzyl ether, methylhydroquinone, amylquinone, amiguchixyhydroquinone, n-butylphenol , Phenol, hydroquinone monopropyl ether, 4, 4 '— [1- [4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl] ethylidene] diphenol, 1,1,3-tris ( 2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, diphenylamines, phenylenediamines, phenothiazine, mercaptobenzimid
• the ultraviolet absorber include, for example, salicylic acid-based ultraviolet absorbers typified by phenol salicylate, benzophenone-based ultraviolet absorbers such as dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone; Ultraviolet absorbers used as additives for various plastics such as benzotriazole-based ultraviolet absorbers and cyanoacrylate-based ultraviolet absorbers can be used.
• the photosensitive acid generator that can be added to the liquid curable resin composition of the present invention imparts photosensitivity to a coating film of the liquid curable resin composition and, for example, irradiates radiation such as light. It is a substance that enables the coating film to be light-cured.
• the photosensitive acid generator include (1) eodonium salts, sulfo-pam salts, phospho-pam salts, diazo-pam salts, ammopram salts, and pyridi-pam salts.
• X represents a divalent group such as an alkylene group, an arylene group, or an alkoxylen group
• R 4 represents a monovalent group such as an alkyl group, an aryl group, a halogen-substituted alkyl group, or a halogen-substituted aryl group.
• R 5 0 2 SC-S 0 2 R 6 may be the same or different and each represents an alkyl group, aryl group, halogen-substituted alkyl group, halogen-substituted aryl group, etc. Shows a valence group.
• the photosensitive acid generator can be used alone or in combination of two or more kinds, and further can be used in combination with the thermal acid generator.
• the proportion of the photosensitive acid generator used in 100 parts by mass of the solid content of the liquid curable resin composition is preferably 0 to 20 parts by mass, and more preferably 0.1 to 10 parts by mass. If this ratio is too large, the cured film will be inferior in strength and the transparency will be reduced, which is not preferable.
• the liquid curable resin composition of the present invention may contain a surfactant for the purpose of improving the applicability of the liquid curable resin composition.
• a surfactant known surfactants can be used. Specifically, for example, various ionic surfactants, ionic surfactants, and nonionic surfactants can be used.
• a cationic surfactant in order to make the cured film have excellent strength and good optical properties.
• a quaternary ammonium salt is preferred, and among them, the use of a quaternary polyether ammonium salt is particularly preferred in that the dust wiping property is further improved. .
• Cationic surfactants which are quaternary polyether ammonium salts, include Adekol CC-15, CC-36, and CC-42 manufactured by Asahi Den-Dani Kogyo Co., Ltd. Etc.
• the use ratio of the surfactant is preferably 5 parts by mass or less based on 100 parts by mass of the liquid curable resin composition.
• thermal polymerization inhibitor examples include, for example, pyrogallol, benzoquinone, hydroquinone, methylene blue, tert-butylcatechol, monobenzyl ether, methylhydroquinone, amylquinone, and amide.
• a cured film is formed from the liquid curable resin composition of the present invention, it is preferable to coat the substrate (applied member).
• a coating method a method such as a diving method, a spray method, a bar coating method, a roll coating method, a spin coating method, a curtain coating method, a gravure printing method, a silk screen method, or an inkjet method can be used. .
• two or more continuous layers that is, at least a layer in which the (D) dianilide silicon particles are present at high density And (D) a layer substantially free of silicon dioxide particles are formed separately.
• Each of these separately formed layers can be confirmed, for example, by observing the cross section of the obtained film with an electron microscope.
• the layer in which the silicon dioxide particles are present at a high density is a concept indicating a portion where the silicon dioxide particles are gathered, and is substantially composed of silicon dioxide particles as a main component. Although it is a layer, a cured product of component (A) or component (B) may coexist inside the layer.
• the layer substantially free of dioxygenated silicon particles is a concept indicating a portion in which an aggregate of dioxygenated silicon particles is not observed. Is not observed at all.
• This layer is a layer substantially composed of components other than the silicon dioxide particles such as a cured product of the components (A) and (B).
• a film obtained in the process of applying the liquid curable resin composition of the present invention and evaporating the solvent includes a layer in which the silicon dioxide particles are present at a high density and a layer in which the silicon dioxide particles are present at a high density. There are virtually no dagger particles! ⁇ has a two-layer structure in which each layer forms a continuous layer.
• PET resin including PET resin having an easy-adhesion layer
• it is usually a layer that is a substrate, a layer in which silicon dioxide particles are present at a high density, Layers substantially free of silicon particles are formed adjacent to each other in this order.
• the layer structure of two or more layers refers to "a layer in which dioxygenated silicon particles are present at high density" and "a layer in which dioxinated silicon particles are not substantially present". In some cases, it may be composed of two or more layers, each containing two or more layers. In some cases, it may be two or more layers in which only two or more “layers in which silicon dioxide particles are present at a high density” have strength.
• the layer containing the high density of dioxinated silicon particles may be used. Can be formed in two or more layers. Further, the “diacid-silicon particles” of the “layer in which the diacid-silicon particles are present at a high density” include at least one kind, ie, one or two or more kinds of Means "silicon particles". When the liquid curable resin composition contains two or more types of silicon dioxide particles, one “layer in which silicon dioxide particles are present at a high density” includes two or more types of silicon dioxide particles. The elementary particle force may be configured.
• the means for curing the liquid curable resin composition is not particularly limited, either.
• heating at 30-200 ° C for 1-180 minutes is preferred.
• a cured film having excellent antireflection properties can be obtained more efficiently without damaging the substrate and the formed cured film.
• at 50-180 ° C for 2-120 minutes, more preferably 80-150. C heat for 2-60 minutes.
• Curing can also be performed by irradiating radiation.
• the irradiation can be performed under a light irradiation condition of 0.001 to 10 JZ cm 2 using an ultraviolet irradiation device (metal halide lamp, high pressure mercury lamp, etc.), but the irradiation condition is not limited to this. . 0. 01- 5j / cm 2 is more preferable and more preferable instrument 0. 1- 3j / cm 2 is.
• the degree of curing of the cured film is determined, for example, by using (B) a melamine compound as the curable conjugate, by measuring the amount of methylol groups or alkoxylated methyl groups in the melamine conjugate by infrared spectroscopy. It can be quantitatively confirmed by analysis or by measuring the gelation ratio using a Soxhlet extractor.
• the liquid curable resin composition of the present invention can be applied to various substrates in the form of a solution, and a laminate can be obtained by curing the obtained coating film.
• a laminate can be obtained by curing the obtained coating film.
• the substrate is a transparent substrate, an excellent antireflection film can be formed.
• the specific structure of the antireflection film is generally a substrate, a high-refractive-index film, and a low-refractive-index film laminated in this order.
• the thickness of the cured film of the present invention in the antireflection film is, for example, 0.05 ⁇ m to 50 ⁇ m, but is not limited thereto.
• the transparent base material include, for example, triacetyl cellulose, polyethylene terephthalate resin (Lumirror manufactured by Toray Industries, Inc.), glass, polycarbonate resin, acrylic resin, styryl resin, arylate. Resin, norbornene-based resin CFSR Co., Ltd., etc.), methyl methacrylate / styrene copolymer resin, polyolefin resin (Zeonex, manufactured by Nippon Zeon Co., Ltd.), etc. be able to.
• triacetyl cellulose, polyethylene terephthalate resin (Lumirror manufactured by Toray Industries, Inc.), norbornene-based resin C1SR (Arton manufactured by Co., Ltd.) and the like are preferable.
• a hard coat layer for example, a hard coat layer, a medium refractive index layer (refractive index 1.5-1.7) And a layer such as a combination of a low refractive index layer (1.3-1.5) and a high refractive index layer (1.6-2.2).
• a hard coat layer for example, a hard coat layer, a medium refractive index layer (refractive index 1.5-1.7) and a layer such as a combination of a low refractive index layer (1.3-1.5) and a high refractive index layer (1.6-2.2).
• a layer such as a combination of a low refractive index layer (1.3-1.5) and a high refractive index layer (1.6-2.2).
• One of these layers may be formed, or two or more different layers may be formed.
• a heat history is particularly given by heating. Is preferred. Of course, even when left at room temperature, the curing reaction proceeds with the passage of time and the desired cured film is formed.However, in practice, heating and curing are effective in reducing the 1S required time. It is. Heating conditions for the curing reaction are appropriate. The heating temperature may be selected as appropriate, but it is necessary that the heating temperature is lower than the heat-resistant limit temperature of the substrate to be coated.
• the laminate of the present invention can be used for optical components such as a lens and a selective transmission film filter in addition to the antireflection film.
• the obtained polymer solution was poured into a mixed solvent of methanol and water to precipitate a polymer, followed by washing with methanol and vacuum drying at 50 ° C to obtain 220 g of a hydroxyl group-containing fluoropolymer. .
• the measurement of the solid content was performed as follows.
• the measurement of the solid concentration was performed in the same manner.
• Catalyst 4050 (manufactured by Mitsui Cytec Co., Ltd., aromatic sulfonic acid conjugated compound, active ingredient concentration: 32%) 0.63 g, 1.3 g of hydrophobized colloidal silica having a number average particle size of lnm is dissolved in acetone as a solvent. By dissolving in 21 lg, a liquid curable resin composition 1 was obtained. The solid content concentration in this liquid curable resin composition was 4.0% by mass.
• a liquid curable resin composition 2-5 was prepared in the same manner as in Example 1, except that the solvent was changed to that shown in Table 1.
• Table 1 shows the solid content concentration of the obtained liquid curable resin composition.
• Liquid curable resin compositions 6 and 7 were prepared in the same manner as in Example 1 except that the solvent was changed to the one shown in Table 1.However, since the hydroxyl group-containing fluoropolymer did not dissolve in the solvent, it was solid. I could't measure the partial concentration.
• Example 2 Same as Example 2 except that the methoxylated methyl melamine “Cymel 303” (manufactured by Mitsui Cytec Co., Ltd.) of the thermosetting conjugate was not added, and the amount of methyl ethyl ketone as a solvent was changed to 170 g. Thus, a liquid curable resin composition 8 was obtained.
• the solid content concentration in this liquid curable resin composition was 4.0% by mass.
• Liquid curable resin composition 10 was obtained in the same manner as in Example 2, except that hydrophobic colloidal silica having a number average particle diameter of 1 lnm was not added, and the amount of methylethyl ketone as a solvent was changed to 180 g.
• the solid content concentration in this liquid curable resin composition was 4.0% by mass.
• Examples of the production of the cured film of the present invention are shown in Examples 416, and Comparative Production Examples are shown in Comparative Examples 916.
• Example 13 The liquid curable resin compositions 1-1, 5-8, and 11 prepared in Comparative Preparation Examples 1, 2, and 5-8, respectively, were subjected to single-sided adhesive polyethylene using a wire bar coater (# 3). After coating the terephthalate film A4100 (manufactured by Toyobo Co., Ltd., film thickness 188 m) on the easily-adhesive treated surface or the untreated surface, the film thickness was increased by heating at 140 ° C for 2 minutes in an oven. A 0.1 ⁇ m cured film layer was formed.
• terephthalate film A4100 manufactured by Toyobo Co., Ltd., film thickness 188 m
• liquid curable resin compositions 6 and 7 (Comparative Examples 3 and 4) could not be applied because they contained insolubles, and could not obtain a cured film.
• the antireflection property of the obtained cured film was measured at a wavelength of 340 nm using a spectral reflectance measuring device (a self-recording spectrophotometer U-3410 incorporating a large sample chamber integrating sphere attached device 150-09090, manufactured by Hitachi, Ltd.). — Reflectance was measured and evaluated in the 700 nm range. Specifically, the reflectance of the cured film was measured using the reflectance of the deposited aluminum film as a reference (100%).
• the turbidity (Haze value) of the obtained laminate was measured using a Haze meter and evaluated according to the following criteria.
• ⁇ Haze value is 1% or less.
• ⁇ Haze value is 3% or less.
• X Haze value is 5% or more.
• the steel wool resistance test of the cured film was performed by the following method. That is, a steel wool (Bonstar No. 0000, manufactured by Nippon Steel Wool Co., Ltd.) was attached to a Gakushin-type friction fastness tester (AB-301, manufactured by Tester Sangyo Co., Ltd.), and the surface of the cured film was loaded. Rubbing was repeated 10 times under the condition 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.
• the cross section of the cured film was observed with an electron microscope to determine whether or not the cured film was separated into layers, and evaluated according to the following criteria.
• 1 and 2 show electron micrographs showing a typical layer separation state corresponding to the following evaluation criteria and a uniform state after layer separation.
• the cured film of the present invention in which two layers are separated has a high reflectivity and a good turbidity and good steel wool properties (Examples 4 to 16).
• the liquid curable resin composition of the present invention can be advantageously used particularly for forming optical materials such as an antireflection film and an optical fiber sheath material, and has a high fluorine content. It can be suitably used as a coating material, a weather-resistant film material, a coating material, and the like for a substrate requiring weather resistance. Also, the cured film obtained by curing the liquid curable resin composition of the present invention is excellent in adhesion to a substrate, has high scratch resistance, and has a good antireflection effect. It is extremely useful as an anti-reflection film, and its visibility can be improved by applying it to various display devices.

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