WO2012105297A1 - Procédé de fabrication d'une solution de silice colloïdale fonctionnelle, composition de résine durcissable sous l'action d'ultraviolets pour des revêtements durs l'utilisant et produit durci à base de celle-ci - Google Patents

Procédé de fabrication d'une solution de silice colloïdale fonctionnelle, composition de résine durcissable sous l'action d'ultraviolets pour des revêtements durs l'utilisant et produit durci à base de celle-ci Download PDF

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WO2012105297A1
WO2012105297A1 PCT/JP2012/050661 JP2012050661W WO2012105297A1 WO 2012105297 A1 WO2012105297 A1 WO 2012105297A1 JP 2012050661 W JP2012050661 W JP 2012050661W WO 2012105297 A1 WO2012105297 A1 WO 2012105297A1
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colloidal silica
parts
hard coat
weight
resin composition
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Japanese (ja)
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大和俊夫
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Momentive Performance Materials Japan LLC
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Momentive Performance Materials Japan LLC
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3081—Treatment with organo-silicon compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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

Definitions

  • the present invention relates to a functional colloidal silica solution used for forming a protective film excellent in pencil hardness, abrasion resistance, low curling property, adhesion and economy on the surface of optical films such as polycarbonate and plastic parts.
  • the present invention relates to a production method, an ultraviolet curable hard coat resin composition, and a cured product thereof. Background art
  • Optical film and plastic parts such as polycarbonate, polymethylmethacrylate, polystyrene, polyester, triacetylcellulose, etc. are used to prevent the surface from being scratched by handling during production and to prevent scratches caused by user use.
  • a protective hard coat layer is provided on one side or both sides.
  • This hard coat layer generally has a film thickness of 1 to 20 ⁇ m, and various active energy ray curable resins and thermosetting resins are used. However, when a hard coat layer is provided, there are insufficient pencil hardness, poor adhesion, and film curling, and improvements have been desired.
  • Patent Document 1 JP-A-57-13214 (Patent Document 1) and JP-A-2009-102503 (Patent Document 2), a composition of particles and an acrylate obtained by treating the surface of water-dispersible colloidal silica with methacryloxysilane is disclosed. And use as a photo-curing coating agent.
  • This coating agent is characterized in that the performance of the coating agent is improved by treating the surface of the silica particles with a specific organosilane and a specific condition.
  • such a coating agent is not always satisfactory.
  • it is necessary to increase the crosslink density of the film after curing.
  • the hardness of the film is increased, warpage and curl due to curing shrinkage increase, and the hardness and low curling property are increased. There was a problem that it was difficult to balance.
  • Patent Document 3 the surface of a water-dispersible colloidal silica is treated with methacryloxysilane and the main component is silica and pentaerythritol triacrylate, so that the hardness and low curling property of the film are reduced. Although some improvement was seen, further improvement was desired.
  • Patent Document 4 Japanese Patent Application Laid-Open No. 7-109355
  • the hardness of the film is improved by using as a main component silica and an acrylate monomer whose surface is treated with methacryloxysilane on the surface of solvent-dispersible colloidal silica.
  • the expensive solvent-dispersible colloidal silica is used as a starting material, the final product obtained is also expensive, which is disadvantageous in terms of economy.
  • the surface hardness was increased by using many polyfunctional acrylate monomers or adding colloidal silica whose surface was treated with a specific organosilane, but when using many polyfunctional acrylate monomers.
  • problems often occur in curing shrinkage.
  • the hard coating agent for surface protection was not suitable.
  • the present invention has been made in view of the above problems, and its purpose is to form a pencil hardness, scratch resistance, film curling, adhesion, economy when a hard coat layer is formed on the surface of an optical film or plastic part.
  • the present invention provides a method for producing a functional colloidal silica solution used in a hard coat resin composition with improved properties, and a hard coat resin composition using the functional colloidal silica solution obtained by the method. .
  • the present inventor has solved the above-mentioned problems of the prior art and provides a functional colloidal silica to provide an ultraviolet curable hard coat agent which has both hardness and low curing shrinkage and is excellent in scratch resistance, adhesion and economy.
  • a functional colloidal silica to provide an ultraviolet curable hard coat agent which has both hardness and low curing shrinkage and is excellent in scratch resistance, adhesion and economy.
  • an ultraviolet curable hard coating agent using a functional colloidal silica solution having a particle size in a certain range synthesized by the following composition and process is extremely effective and completes the present invention. It came to.
  • the present invention (A) Water-dispersible colloidal silica having an average particle diameter of 1 to 30 nm and a hydrogen ion concentration (pH) of 6 or less; 100 parts by weight as silica content (B) Methacrylic group-containing alkoxysilane; 20 to 30 parts by weight (C) a polar solvent having a dielectric constant of 10 or more; 50 to 500 parts by weight (D) radical polymerization inhibitor; after the hydrolysis reaction in the presence of 0.001 to 1 part by weight, (E) Obtained by azeotropic dehydration using 1-methoxy-2-propanol and solvent substitution, the average particle size is 1 to 30 nm, and the difference in the average particle size of silica before and after the hydrolysis reaction is 1 A method for producing a functional colloidal silica solution within 5 times, And the functional colloidal silica solution, an acrylate resin and / or a urethane acrylate resin, and a photopolymerization initiator, an ultraviolet cur
  • the component (A) used in the present invention is water-dispersible colloidal silica having an average particle size of 1 to 30 nm and a hydrogen ion concentration (pH) of 6 or less.
  • colloidal silica fine particles are obtained by dispersing ultrafine particles of silicic anhydride having an average particle size of 1 to 200 ⁇ m in water or an organic solvent.
  • Dispersion media used for colloidal silica include alcohol solvents such as water, methanol, ethanol, isopropanol, n-propanol, isobutanol and n-butanol, polyhydric alcohol solvents such as ethylene glycol, ethyl cellosolve, butyl cellosolve, etc.
  • ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and diacetone alcohol
  • monomers such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate and tetrahydrofurfuryl acrylate.
  • water-dispersible colloidal silica having a hydrogen ion concentration (pH) of 6 or less is particularly preferable.
  • colloidal silicas are produced by a known method, and those having a concentration of about 5 to 40% mainly as a silica content are preferable.
  • the average particle size is 1 to 30 nm, preferably 10 to 30 nm, more preferably 15 to 30 nm, and still more preferably 18 to 25 nm.
  • Those having a particle diameter of less than 1 nm are expensive, and gelation tends to occur in the reaction process.
  • the thing with a particle diameter exceeding 30 nm reduces the transparency of a cured film.
  • Colloidal silica can remarkably improve the scratch resistance of the cured film and is effective in imparting anti-curl properties.
  • the silica concentration in the colloidal silica is high from the economical aspect, and the concentration can be increased.
  • An average particle size of about 18 to 25 nm is optimal. In the present invention, those having an average particle diameter in the range of 18 to 25 nm and silica in the range of 30 to 40% are preferable.
  • the component (B) By blending a certain amount of the component (B) with respect to the effective amount of the colloidal silica, it can be chemically bonded to the colloidal silica by hydrolysis under an acidic aqueous solution, and the scratch resistance of the cured film can be remarkably improved.
  • silanes 3-methacryloxypropyltrimethoxysilane, 2-methacryloxyethyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 2-methacryloxyethyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane
  • 3-methacryloxypropyltrimethoxysilane is preferred because of its availability.
  • the blending amount must be 20 to 30 parts by weight with respect to 100 parts by weight of the effective component (silica content) of component (A). If the amount is less than 20 parts by weight, the surface treatment of the colloidal silica is not sufficiently performed, and as a result, sufficient wear resistance cannot be obtained. Further, the colloidal silica particles may aggregate in the dehydration step after hydrolysis. When the amount is more than 30 parts by weight, the change in the particle size of the functional colloidal silica solution obtained becomes large, and sufficient hardness and scratch resistance are not exhibited when the ultraviolet curable hard coat composition is prepared. In addition, an excessive component (B) forms an oligomer during hydrolysis, which affects pencil hardness and wear resistance. Furthermore, the curl becomes large when applied to a film substrate.
  • Component (C) is blended in order to improve compatibility when the components (A) and (B) are hydrolyzed.
  • polar solvents having a dielectric constant of 10 or more include 1-butanol, 2-butanol, methanol, ethanol, cellosolve, etc., but compatibility between components (A) and (B) before and after the hydrolysis reaction, colloidal silica Isopropyl alcohol and / or 1-methoxy-2-propanol are preferred from the standpoints of influence on particle size and efficiency of azeotropic dehydration.
  • the amount is preferably 50 to 500 parts by weight, particularly preferably 70 to 150 parts by weight from the viewpoints of compatibility and the solvent distillation efficiency after the hydrolysis reaction.
  • the (D) component can suppress the polymerization of methacrylic groups and improve the yield by allowing it to coexist during the hydrolysis reaction of the (A) component and the (B) component.
  • the radical polymerization inhibitor is not particularly limited, and any radical polymerization inhibitor can be used as long as it is generally used as a radical polymerization inhibitor.
  • quinone polymerization inhibitors such as hydroquinone, methoxyhydroquinone, benzoquinone and p-tert-butylcatechol; 2,6-di-tert-butylphenol, 2,4-di-tert-butylphenol, 2-tert- Alkylphenol polymerization inhibitors such as butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol; alkylated diphenylamine, N, N '-Diphenyl-p-phenylenediamine, phenothiazine, 4-hydroxy-2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 1,4-dihydroxy- 2,2,6,6-
  • radical polymerization inhibitors include quinone polymerization inhibitors, amine polymerization inhibitors, copper dithiocarbamate polymerization inhibitors, and 1-oxyl polymerization inhibitors.
  • Particularly preferred radical polymerization inhibitors include hydroquinone, methoxyhydroquinone, benzoquinone, p-tert-butylcatechol, phenothiazine, alkylated diphenylamine, copper dibutyldithiocarbamate, 2,2,6,6-tetramethylpiperidine-1-oxyl, 4 Examples include -hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, esters of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, and the like.
  • the blending amount is preferably 0.001 to 1 part by weight from the viewpoint of the effect of suppressing the radical polymerization reaction during the hydrolysis reaction and the reactivity of the hard coat composition with respect to ultraviolet rays when prepared into a hard coat composition. 01 to 0.1 parts by weight are preferred.
  • the component (E) is used when water or by-products are distilled off from the system after the hydrolysis reaction.
  • acrylates with low viscosity such as 1,6-hexanediol diacrylate and tripropylene glycol diacrylate are blended to remove water and by-products by distillation, isobutanol, toluene, IPA (isopropanol) Dehydration or azeotropic dehydration was performed using a solvent such as DMF (dimethylformamide).
  • the silica particle diameter in the finally obtained functional colloidal silica solution becomes large, and as a result, when prepared into a resin composition for hard coat, pencil hardness, There was an effect on wear and low curl properties.
  • the obtained functional colloidal silica already contains a specific acrylate, so the properties of the hard coat composition to be finally prepared are limited. Therefore, since it cannot be treated as a versatile masterbatch-like functional colloidal silica, its value is limited.
  • any acrylate having such a low viscosity is bifunctional, and a composition containing this acrylate is not suitable for the present invention aiming at high hardness and scratch resistance.
  • 1-methoxy-2-propanol is suitable for hard coat resin compositions for films and various plastics because it does not affect plastic substrates that are easily affected by organic solvents such as polycarbonate.
  • the blending amount is not particularly limited as long as it is necessary for azeotropic dehydration and there is an amount capable of stably dispersing the obtained functional colloidal silica.
  • the components (A) to (C) are hydrolyzed in the presence of the component (D) in the first step.
  • the conditions at this time are not particularly limited, but generally 70 to 120 ° C., more preferably 2 hours or more at the reflux temperature is appropriate.
  • azeotropic dehydration is performed using the component (E) to obtain a functional colloidal silica solution.
  • the conditions for azeotropic dehydration are not particularly limited, but azeotropic dehydration is preferably performed under reduced pressure so that the solution temperature does not become 50 ° C. or higher.
  • additives such as a silane coupling agent, a leveling agent, an acrylate, a urethane acrylate, and a diluting solvent can be blended within a range not impairing the characteristics of the present invention.
  • the average amount of silica particles before and after the hydrolysis reaction is controlled by controlling the blending amount of the methacryl group-containing alkoxysilane and selectively using 1-methoxy-2-propanol for azeotropic dehydration.
  • a functional colloidal silica solution having a diameter difference of 1.5 times or less can be produced.
  • an acrylate resin or a urethane acrylate resin is blended as a binder component, a photopolymerization initiator, a diluting solvent if necessary, and leveling. It can be obtained by blending agents, but in order to obtain a UV-hardening hard coat resin composition with essentially high hardness, a trifunctional or higher polyfunctional type acrylate or urethane acrylate is mainly used as a binder component. It is preferable to do.
  • the UV curable type is such that the solid content (active ingredient) based on the functional colloidal silica solution is 50% or more of the total solid content (active ingredient). It is necessary to prepare a resin composition for hard coat, and it is particularly preferably 60% or more.
  • composition satisfies the above conditions, the effect of the present invention can be obtained.
  • a functional colloidal silica solution As a specific composition, a functional colloidal silica solution; an acrylate resin and / or urethane with respect to 100 parts by weight as a silica component A suitable amount is 40 to 100 parts by weight of an acrylate resin, 4 to 16 parts by weight of a photopolymerization initiator, and 200 to 1000 parts by weight as the total solvent content.
  • the acrylate resin, urethane acrylate resin, photopolymerization initiator, and diluting solvent used in the present invention are not particularly limited as long as they are conventionally used in ultraviolet curable hard coat resin compositions. Dipentaerythritol hexaacrylate, pentaerythritol pentaacrylate, dipentaerythritol pentaacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate and the like.
  • Urethane acrylate resins include urethane acrylates “purple light UV-1700B”, “purple light UV-6300B”, “purple light UV-7640B” manufactured by JSR Corporation, Ebecryl® 1290 manufactured by Daicel-Cytec, and “UA-306H” manufactured by Kyoeisha Chemical. Or the like.
  • any known and generally available ones can be used, but those having a maximum wavelength peak of UV absorption of 400 nm or less are particularly desirable in order to ensure transparency in the visible region.
  • the diluting solvent known solvents such as alcohol solvents such as 1-methoxy-2-propanol, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, and ester solvents such as ethyl acetate and butyl acetate can be used. It can be used alone or in a mixed solvent system.
  • the resin composition for hard coat be filtered before use.
  • the filter material is preferably PTFE, polypropylene, or the like that is not easily eroded by an acrylic compound, and the filter diameter during filtration is preferably about 0.2 to 10 microns because it is easily available.
  • the filter diameter is divided into two stages, with the passage of 2 to 10 microns in the early stage and 0.2 to 1 micron in the latter stage, so that colloidal silica agglomerates, gels derived from acrylic resin, and dust mixed in from the air are more efficient. It can be removed well and the final appearance of the film can be kept good.
  • the UV curable hard coat composition described above is applied to the surface of an optical film or plastic part substrate by roll, wire bar, doctor blade, flow, spray, brushing, etc. It can be cured by irradiating with ultraviolet rays.
  • the ultraviolet light source any light source that generates ultraviolet light can be used without limitation.
  • a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a fusion lamp, or the like can be used.
  • Irradiation conditions vary depending on each lamp, but in the case of a fusion lamp (H bulb), the amount of irradiation light is preferably about 50 to 1000 mJ / cm 2 in the ultraviolet UV-B wavelength region.
  • the ultraviolet curable hard coat composition is preferably irradiated with ultraviolet rays during or after coating and drying, and the irradiation time is preferably 0.5 seconds to 5 minutes. From the viewpoint of curing efficiency or work efficiency of the ultraviolet curable resin, 3 More preferred is seconds to 2 minutes.
  • the formation thickness of the ultraviolet curable hard coat agent is 1 to 20 ⁇ m, preferably 5 to 15 ⁇ m.
  • the film thickness decreases, the influence of polymerization inhibition by oxygen during photocuring increases, and a curing system under an inert gas such as nitrogen is required. Further, when the film thickness becomes extremely large, there is a problem that the deformation of the base material during curing shrinkage becomes large.
  • the evaluation method is as follows. (Average particle size) The measurement was performed with a submicron particle size distribution analyzer Coulter N4 Plus manufactured by Beckman Coulter. (Pencil hardness) The test was conducted on the film surface on which the cured film was formed according to the test method of JIS K 5600-5-4. However, after conditioning for 16 hours or more under the conditions of 23 ° C. and 50% RH, the load is 1 kg, the test is performed five times with a pencil of the same hardness scale, the type of indentation is visually examined, and the plasticity for each hardness scale Evaluation was performed by the number of times without deformation or cohesive failure / number of tests.
  • Abrasion resistance Using the Taber abrasion test described in JIS K 7204 and JIS K 7105 using two wheels with a wear wheel CS10F and a load of 250 g on one wheel, and subtracting the haze (haze) at the time of 500 rotations from the initial haze, Abrasion was evaluated. The lower the value, the better the wear resistance. (Curl property) The sample was cut out with a size of 100 mm ⁇ 100 mm square, and conditioned for 16 hours or more under the conditions of 23 ° C. and 50% RH, and then the lifted distances at the four corners of the sample were measured to obtain an average value.
  • Adhesion A lattice-shaped crosscut was prepared on the surface of the film on which the cured film was formed according to the test method of JIS K 5600-5-6, and a cellophane tape peeling test with a width of 25 mm was performed. The evaluation of adhesion was shown by the number of remaining eyes / total number of eyes.
  • Synthesis example 1 430 parts of isopropyl alcohol (IPA), Snowtex O-40 manufactured by Nissan Chemical Industries, Ltd. (water-dispersible colloidal silica; silica content 40%, pH of about 3, particle size 16.7 nm), 1340 parts, Momentive Performance Material A mixture of 140 parts TSL8370 (3-methacryloxypropyltrimethoxysilane) and 0.35 parts 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxy free radical manufactured by The mixture was refluxed with stirring at about 82 ° C. for 3 hours.
  • IPA isopropyl alcohol
  • Snowtex O-40 Snowtex O-40 manufactured by Nissan Chemical Industries, Ltd.
  • Momentive Performance Material A mixture of 140 parts TSL8370 (3-methacryloxypropyltrimethoxysilane) and 0.35 parts 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxy free radical manufactured by The mixture was refluxed with stirring at about 82 ° C. for 3 hours.
  • Synthesis example 2 430 parts of isopropyl alcohol used in Synthesis Example 1 were replaced with 830 parts of 1-methoxy-2-propanol, and the total amount of 1-methoxy-2-propanol used for distillation under reduced pressure was changed from 1350 parts to 620 parts (methanol). The ratio used for the vacuum distillation of the water and the like by azeotropic distillation is the same as in Synthesis Example 1. The same applies hereinafter.
  • a 1-methoxy-2-propanol solution (FCS-2) of functional colloidal silica having a content of 60% was prepared.
  • Synthesis example 3 After cooling, 500 parts of 1-methoxy-2-propanol was added together with 275 parts of pentaerythritol triacrylate, and the total amount of 1-methoxy-2-propanol used for distillation under reduced pressure was increased from 1350 parts. Substituting 1530 parts, a 1-methoxy-2-propanol solution (FCS-3) of functional colloidal silica having a nonvolatile content of 60% was finally prepared in the same procedure as in Synthesis Example 1.
  • Synthesis example 4 430 parts of isopropyl alcohol, Snowtex O-40 manufactured by Nissan Chemical Industries, Ltd. (water-dispersible colloidal silica; silica content 40%, pH about 3, particle size 16.7 nm), 1340 parts, Momentive Performance Materials Japan
  • FCS-4 internal functional silica content of about 60%
  • Synthesis example 5 430 parts of isopropyl alcohol, Snowtex O-40 manufactured by Nissan Chemical Industries, Ltd. (water-dispersible colloidal silica; silica content 40%, pH about 3, particle size 16.7 nm), 1340 parts, Momentive Performance Materials Japan
  • isobutanol (IBA) was added, and isopropyl alcohol and by-product methanol were distilled off under reduced pressure. Further, 1720 parts of isobutanol was added in several portions, and finally an isobutanol solution (FCS-5) of functional colloidal silica having a nonvolatile content of 60% was prepared.
  • Synthesis Example 6 The amount of TSL8370 was increased from 140 parts to 240 parts, and finally a 1-methoxy-2-propanol solution (FCS-6) of functional colloidal silica having a nonvolatile content of 60% was synthesized by the same synthesis procedure as in Synthesis Example 1. ) was produced.
  • Examples 1 to 4 The functional colloidal silica solutions obtained in Synthesis Examples 1 to 3, the pentaerythritol triacrylate (PETA), and the urethane acrylate (UA; manufactured by JSR Corporation) so that the ultraviolet curable hard coat composition described in Table 1 is obtained.
  • UV-7640B the pentaerythritol triacrylate
  • U urethane acrylate
  • UV-7640B Irgacure 184 (photopolymerization initiator) manufactured by BASF Japan Ltd., 1-methoxy-2-propanol and the like were prepared, followed by pressure filtration to obtain a hard coat solution.
  • the unit in the table is part by weight.
  • the hard coat solution thus obtained was applied to a 188 ⁇ -thick easy-adhesive PET film (Lumilar U34 manufactured by Toray Industries Inc.) with a bar coater so as to have a coating thickness of 10 ⁇ m, and after curing at 90 ° C. for 1 minute.
  • a hard coat film was formed by irradiation four times under an ultraviolet irradiation condition of 200 mJ / cm 2 (as UV-A).
  • the evaluation results are shown in Table 1.
  • Comparative Examples 1 to 4 In the same manner as in Examples 1 to 4, the functional colloidal silica solution, pentaerythritol triacrylate obtained in Synthesis Examples 4 to 6 so as to be the ultraviolet curable hard coat composition described in Table 1, manufactured by JSR Corporation Urethane acrylate (purple UV-7640B), Irgacure 184 (photopolymerization initiator) manufactured by BASF Japan Ltd., 1-methoxy-2-propanol and the like were prepared.
  • FCS-1 was added to prepare the composition shown in Table 1.
  • a hard coat film was formed in the same manner as in Experimental Examples 1 to 4. The evaluation results are shown in Table 1.

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Abstract

La présente invention concerne un procédé de fabrication d'une silice colloïdale fonctionnelle capable de fournir une matière de revêtement dur durcissable sous l'action d'ultraviolets, qui combine une dureté et un faible retrait au durcissement et qui assure une excellente résistance aux rayures, une adhérence étroite et un rendement économique. L'invention concerne également un procédé de fabrication d'une solution de silice colloïdale fonctionnelle qui est obtenue en soumettant (A) 100 parties en poids (en termes de silice) d'une silice colloïdale dispersible dans l'eau qui présente un diamètre moyen de particule de 1 à 30 nm et une concentration en ion hydrogène (pH) de 6 ou moins, (B) de 20 à 30 parties en poids d'un alcoxysilane à teneur en méthacryloxy et (C) de 50 à 500 parties en poids d'un solvant polaire ayant une constante diélectrique de 10 ou plus à une hydrolyse en présence de (D) 0,001 à 1 partie en poids de (D) un inhibiteur de polymérisation radicalaire, puis en soumettant le système résultant à une déshydratation azéotropique/déplacement de solvant à l'aide de (E) 1-méthoxy-2-propanol et qui présente un diamètre moyen de particule de 1 à 30 nm et une différence d'au plus 1,5 fois dans le diamètre moyen de particule de la silice entre avant et après l'hydrolyse.
PCT/JP2012/050661 2011-01-31 2012-01-16 Procédé de fabrication d'une solution de silice colloïdale fonctionnelle, composition de résine durcissable sous l'action d'ultraviolets pour des revêtements durs l'utilisant et produit durci à base de celle-ci Ceased WO2012105297A1 (fr)

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WO2013146477A1 (fr) * 2012-03-30 2013-10-03 新日鉄住金化学株式会社 Composition de résine de revêtement contenant de la silice et corps stratifié
CN106433254A (zh) * 2015-08-13 2017-02-22 株式会社Kcc 汽车零部件用紫外线固化型涂料组合物
WO2017141906A1 (fr) * 2016-02-16 2017-08-24 株式会社トッパンＴｏｍｏｅｇａｗａオプティカルフィルム Film de revêtement dur, plaque polarisante l'utilisant, produit traité de film de revêtement dur et élément d'affichage
CN113583284A (zh) * 2021-07-27 2021-11-02 宁波惠之星新材料科技有限公司 一种光学硬涂膜的制备方法

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WO2013146477A1 (fr) * 2012-03-30 2013-10-03 新日鉄住金化学株式会社 Composition de résine de revêtement contenant de la silice et corps stratifié
CN106433254A (zh) * 2015-08-13 2017-02-22 株式会社Kcc 汽车零部件用紫外线固化型涂料组合物
CN106433254B (zh) * 2015-08-13 2020-02-25 株式会社Kcc 汽车零部件用紫外线固化型涂料组合物
WO2017141906A1 (fr) * 2016-02-16 2017-08-24 株式会社トッパンＴｏｍｏｅｇａｗａオプティカルフィルム Film de revêtement dur, plaque polarisante l'utilisant, produit traité de film de revêtement dur et élément d'affichage
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CN113583284A (zh) * 2021-07-27 2021-11-02 宁波惠之星新材料科技有限公司 一种光学硬涂膜的制备方法

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