WO2010103944A1 - Composition de résine pour la formation de couche de revêtement transparente, et stratifié - Google Patents

Composition de résine pour la formation de couche de revêtement transparente, et stratifié Download PDF

Info

Publication number
WO2010103944A1
WO2010103944A1 PCT/JP2010/053197 JP2010053197W WO2010103944A1 WO 2010103944 A1 WO2010103944 A1 WO 2010103944A1 JP 2010053197 W JP2010053197 W JP 2010053197W WO 2010103944 A1 WO2010103944 A1 WO 2010103944A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
transparent
transparent coating
transparent film
resin composition
Prior art date
Application number
PCT/JP2010/053197
Other languages
English (en)
Japanese (ja)
Inventor
長川敬一
川▲崎▼徳明
苅田和紗
松川公洋
Original Assignee
堺化学工業株式会社
地方独立行政法人 大阪市立工業研究所
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 堺化学工業株式会社, 地方独立行政法人 大阪市立工業研究所 filed Critical 堺化学工業株式会社
Priority to JP2011503769A priority Critical patent/JPWO2010103944A1/ja
Priority to KR1020117021133A priority patent/KR20120013304A/ko
Priority to CN2010800064874A priority patent/CN102307953A/zh
Publication of WO2010103944A1 publication Critical patent/WO2010103944A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • 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
    • C09D181/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Coating compositions based on polysulfones; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • 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
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond

Definitions

  • the present invention relates to a resin composition for forming a transparent coating layer, a laminate, and a method for producing a transparent coating.
  • a resistive film type touch panel generally has a touch-side plastic substrate in which a transparent conductive thin film such as a tin-doped indium oxide (ITO) film is laminated on one side of a transparent plastic substrate, and an ITO film on one side of a transparent substrate such as glass.
  • the transparent conductive thin film is laminated with a transparent substrate on the display side through an insulating spacer so that the transparent conductive thin films face each other.
  • the input is performed by pressing the touch input surface of the touch side plastic substrate with a pen or a finger (referring to the surface opposite to the transparent conductive thin film), and the transparent conductive thin film on the touch side plastic substrate and the display side transparent substrate The transparent conductive thin film is contacted.
  • an acrylic or methacrylic resin or the like has been often used (for example, Patent Document 1, Patent Document 2 and the like), but a hard coat layer formed from an acrylic or methacrylic resin.
  • a hard coat layer formed from an acrylic or methacrylic resin.
  • flexibility was inferior. Therefore, when molding the touch panel surface, there is a problem with the transferability of the mold surface due to lack of flexibility, there is a problem that cracks occur, and the hard coat layer may fall off from the base material. There was a problem that the moldability was limited.
  • the present invention relates to a surface material such as a plastic substrate, and has a scratch resistance and an abrasion resistance without using a lubricant, has excellent flexibility, and has a sufficient hardness.
  • An object of the present invention is to provide a resin composition for forming a transparent coating layer for forming a film, and a laminate using the composition.
  • the present inventors have obtained a transparent coating film having a specific composition, specifically, a composition containing an organosilicon compound and a polythiol compound, which has an excellent balance between flexibility and hardness. As a result, the present invention was completed.
  • the first aspect of the present invention relates to a resin composition for forming a transparent coating layer, wherein the resin composition for forming a transparent coating layer includes the following components (A) and (B): (A) an organosilicon compound having a reactive functional group, and (B) Polythiol compound.
  • the composition is preferably one having a curable under irradiation with ultraviolet rays of 500 mJ / cm 2 or more 2,000 mJ / cm 2 or less of the total irradiation amount.
  • the resin composition for forming a transparent coating layer of the present invention further contains (C) a photoacid generator.
  • the composition preferably has curability under irradiation of ultraviolet rays with an integrated dose of 100 mJ / cm 2 or more and less than 500 mJ / cm 2. is there.
  • the organosilicon compound (A) preferably contains at least part of a compound having one or more carbon-carbon unsaturated bonds in one molecule.
  • the organosilicon compound is preferably vinyltriacetoxysilane.
  • the second aspect of the present invention is: A plastic substrate; A laminate having a transparent coating layer formed from the resin composition for forming a transparent coating layer, The transparent coating layer is provided on at least one side of the surface of the base material, The transparent coating layer also relates to a laminate having a pencil hardness of 2H or more and a minimum mandrel diameter of 5 mm or less that does not cause cracks in the mandrel test.
  • the third aspect of the present invention is: (A) coating a resin composition containing an organosilicon compound having a reactive functional group and (B) a polythiol compound on a substrate; Curing the composition to obtain a transparent coating, In the step of obtaining the transparent film, comprising irradiating the composition with ultraviolet rays,
  • the present invention relates to a method for producing a transparent coating.
  • integrated irradiation dose of ultraviolet rays to the composition is 500 mJ / cm 2 or more 2,000 mJ / cm 2 or less.
  • the resin composition further contains (C) a photoacid generator,
  • the cumulative amount of ultraviolet rays applied to the composition is 100 mJ / cm 2 or more and less than 500 mJ / cm 2 .
  • the transparent film formed from the resin composition for forming a transparent film layer of the present invention is excellent in flexibility, hardness, scratch resistance and abrasion resistance. Therefore, it is a material suitable for use as a hard coat layer.
  • the resin composition for forming a transparent coating layer of the present invention has the following components: (A) an organosilicon compound having a reactive functional group, and (B) A composition containing a polythiol compound.
  • organosilicon compound having a reactive functional group as component (A) will be described.
  • the organosilicon compound functions as a hard segment of the transparent film. Although it does not restrict
  • the “reactive functional group” of the organosilicon compound specifically means a mercapto reactive group, that is, a functional group that undergoes an addition reaction with a mercapto (—SH) group.
  • reactive functional groups are not particularly limited, but include groups having carbon-carbon unsaturated bonds such as vinyl groups, allyl groups, and alkenyl groups, and epoxy groups, styryl groups, acryloxy groups, methacryloxy groups, and isocyanate groups. Etc. are mentioned as preferable examples. Of these, a group having a carbon-carbon unsaturated bond is particularly preferred.
  • the organosilicon compound (A) may be one kind or a mixture of two or more kinds, but the organosilicon compound (A) has one carbon-carbon unsaturated bond as described above in one molecule. It is preferable to include at least a part of the compound having the above.
  • organosilicon compound (A) which has a reactive functional group
  • organosilicon compound represented by a following formula and its hydrolyzate are mentioned.
  • R 1 is unsubstituted or substituted with a reactive functional group selected from the group consisting of a vinyl group, an epoxy group, a styryl group, an acryloxy group, a methacryloxy group, and an isocyanate group.
  • R 2 is an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 2 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or 6 to 6 carbon atoms.
  • component (A) represented by the above formula examples include tetraalkoxysilanes such as tetraethoxysilane; alkylalkoxysilanes such as methyltrimethoxysilane; vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltriacetoxy.
  • Vinyl alkoxysilanes such as silane; ⁇ -methacryloxyalkyl-alkoxysilanes such as ⁇ -methacryloxypropyltrimethoxysilane and ⁇ -methacryloxypropyltriethoxysilane; halogen-containing silanes such as trimethylchlorosilane; ⁇ -glycidoxymethyltri Methoxysilane, ⁇ -glycidoxymethyltriethoxysilane, ⁇ -glycidoxyethyltrimethoxysilane, ⁇ -glycidoxyethyltriethoxysilane, ⁇ -glycidoxyethyltrimethoxysilane, ⁇ -glycidoxy Tiltlyethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycidoxypropylmethyldimethoxysilane, ⁇ -g
  • the component (A) preferably contains at least a part of a compound having one or more carbon-carbon unsaturated bonds in one molecule. Since the carbon-carbon unsaturated bond can be a reaction point when the polythiol compound described later undergoes a crosslinking reaction, the component (A) preferably has one or more carbon-carbon unsaturated bonds in one molecule.
  • the polythiol compound used in the present invention is not particularly limited as long as it has two or more mercapto (-SH) groups in one molecule.
  • a polyol such as ethylene glycol dimercaptopropionate and a mercapto organic acid (for example, thioglycolic acid, 3-mercaptopropionic acid, thioacetic acid, thiolactic acid, thiomalic acid, thiosalicylic acid, etc.
  • the thiol compound obtained by esterification reaction of a polyol and a mercapto organic acid is preferable, and especially the thiol compound which has three or more mercapto groups in 1 molecule is preferable.
  • the content of the component (B) is not particularly limited, but when the component (A) is 100 parts by weight, it is usually 20 to 130 parts by weight, preferably 30 to 100 parts by weight, more preferably 40 to 80 parts by weight. is there. When the component (B) is too small, the flexibility of the produced transparent film tends to be insufficient, and when it is too much, the hardness of the produced transparent film tends to be insufficient.
  • photoacid generator In one preferred embodiment of the resin composition for forming a transparent coating layer of the present invention, in addition to the above (A) and (B), (C) a photoacid generator may further be contained.
  • the photoacid generator of component (C) used in the present invention is not particularly limited, and examples thereof include those that generate a Bronsted acid or Lewis acid starting species by light irradiation such as diphenyliodonium salt and triphenylsulfonium salt. .
  • the amount is not particularly limited, but when the component (A) is 100 parts by weight, it is preferably 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, The amount is preferably 0.5 to 3 parts by weight.
  • the component (C) is too small, the curing reaction for producing the transparent film does not proceed sufficiently, the hardness of the produced transparent film tends to be insufficient, and when it is too much, the light transmittance of the produced transparent film tends to decrease. There is.
  • the resin composition for forming a transparent coating layer of the present invention may optionally contain additives such as stabilizers, and may be diluted with a solvent for the purpose of adjusting the viscosity.
  • a solvent used for dilution Ketones, ester, ethers, alcohol, etc. are mentioned, Other well-known solvents can also be used. Particularly preferred are methyl ethyl ketone, ethyl acetate, methoxypropyl acetate, xylene and dimethylformamide. These solvents may be used alone or as a mixed solution of two or more.
  • paintability may be included.
  • the amount of the solvent is preferably 0 to 100 parts by weight, more preferably 20 to 50 parts by weight when the weight of the solid content is 100 parts by weight. is there.
  • the content thereof is preferably 0.01 to 10 parts by weight, more preferably 0.01 when the solid content is 100 parts by weight. ⁇ 5 parts by weight.
  • the resin composition for forming a transparent coating layer of the present invention may contain a sol of inorganic fine particles in order to change the refractive index of the transparent coating layer.
  • sols include zinc oxide, silicon dioxide, aluminum oxide, titanium oxide, zirconium oxide, tin oxide, beryllium oxide, antimony oxide, tungsten oxide, cerium oxide, zinc stannate dispersed in an organic solvent.
  • sols of zinc antimonate, tantalum oxide, iron oxide, lead oxide and the like sols of zinc antimonate, tantalum oxide, iron oxide, lead oxide and the like. These may be used singly or in combination of two or more.
  • a composite oxide of a plurality of sols may also be used.
  • a mixture with a complex oxide may be used.
  • the content is not particularly limited, but the content is preferably 0 to 400 parts by weight, more preferably 30 to 200 parts by weight when the component (A) is 100 parts by weight. is there.
  • the present invention also relates to a laminate having a plastic substrate and a transparent coating layer formed from the above composition.
  • the transparent coating layer is provided on at least one side of the surface of the plastic substrate, the pencil hardness is 2H or more, and the minimum diameter of the mandrel that does not crack in the mandrel test Is 5 mm or less.
  • the plastic substrate is not particularly limited, but is a thermoplastic resin such as cellulose triacetate, polyester, polyamide, polyimide, polypropylene, polystyrene, polymethylpentene, polyvinyl chloride, polyvinyl acetal, methyl polymethacrylate, polycarbonate, polyurethane.
  • a stretched or unstretched film or a multilayer sheet obtained by laminating these in two to five layers can be used.
  • the multilayer sheet can be obtained by coextrusion molding or lamination through an adhesive.
  • the thickness of the plastic substrate is determined depending on the material, composition or use, but a film of 25 ⁇ m to 250 ⁇ m is preferable, and a stretched polyester (particularly polyethylene terephthalate) film of 75 to 180 ⁇ m is more preferable.
  • the method for producing the transparent coating layer is not particularly limited, but in general, a resin composition containing (A) an organosilicon compound having a reactive functional group and (B) a polythiol compound is coated on a substrate. And a step of curing the composition to obtain a transparent film, and in the step of obtaining the transparent film, a transparent film is produced by a method comprising irradiating the composition with ultraviolet rays.
  • the method for applying the resin composition for forming a transparent coating layer is not particularly limited, such as a roll coating method, a gravure coating method, a bar coating method, a spin coating method, or a dipping method.
  • the thermosetting by heating, the photocuring by irradiation of light, such as an ultraviolet-ray and visible light, etc. are mentioned.
  • the resin composition for transparent film layer formation of this invention has photocurability, especially ultraviolet-curing property. Is not particularly limited, when not containing a photo acid generator of the component (C) is preferably irradiated with ultraviolet light of 500 mJ / cm 2 or more 2,000 mJ / cm 2 or less of the total irradiation amount.
  • the photoacid generator of component (C) is not contained, if the cumulative irradiation amount of ultraviolet rays at the time of curing is 500 mJ / cm 2 or less, curing is insufficient, and as a result, sufficient hardness (approximately pencil hardness) However, there is a risk that a transparent film having a hardness higher than H, preferably a hardness higher than 2H may not be obtained.
  • the cumulative irradiation amount of ultraviolet rays at the time of curing is not particularly limited, but is typically 100 mJ / cm 2 or more, and 100 mJ A transparent film with sufficient hardness can be obtained even with an integrated irradiation dose of / cm 2 or more and less than 500 mJ / cm 2 .
  • the component (C) photoacid generator when irradiated with ultraviolet rays of 500 mJ / cm 2 or more 2,000 mJ / cm 2 or less of the total irradiation amount, sufficient hardness transparent A coating can be obtained.
  • the initiation of Bronsted acid or Lewis acid is generated from the (C) component photoacid generator by ultraviolet irradiation, and the reaction of the (A) component
  • the organosilicon compound having a functional functional group and the polythiol compound (B) react simultaneously, curing proceeds and a transparent film is formed. Moreover, heating etc. can also be performed as needed.
  • the average thickness of the transparent coating layer is not particularly limited, but is preferably 0.5 to 30 ⁇ m, more preferably 1 to 10 ⁇ m.
  • the surface of the plastic substrate is preferably subjected to pretreatment such as alkali treatment, plasma treatment, and ultraviolet treatment as necessary.
  • the transparent film formed by the above method has a pencil hardness of 2H or higher.
  • pencil hardness refers to a value measured according to JIS K5600-5-4.
  • the value of pencil hardness is JIS K5600-5-4, preferably H or higher, more preferably 2H or higher.
  • the transparent coating has a minimum mandrel diameter of 5 mm or less that does not cause cracks in the mandrel test.
  • the “mandrel test” refers to a test performed in accordance with JIS K5600-5-1.
  • the minimum diameter value of the mandrel that does not crack is preferably 10 mm or less, more preferably 5 mm or less.
  • the pencil hardness was specified according to JIS K5600-5-4.
  • the mandrel test was conducted based on JIS K5600-5-1.
  • Example 1 ⁇ Relationship between UV irradiation and properties of transparent film> (Example 1)
  • a transparent coating layer forming resin composition 1 having the following composition was applied by a spin coating method.
  • Ultraviolet rays were irradiated using a metal halide lamp UVL3000M2O type lamp manufactured by Co., Ltd.
  • the amount of irradiation at this time was 600 mJ / cm 2 when measured with an ultraviolet illuminance meter UVP365-01 manufactured by Iwasaki Electric Co., Ltd.
  • the laminate was heated and dried at 120 ° C.
  • the transparent film thus obtained had an average thickness of 5 ⁇ m.
  • the transparent film had a pencil hardness of 2H.
  • the laminate having the transparent film has flexibility in a mandrel test so as not to crack even when the curvature is 2 mm (that is, the minimum diameter of the mandrel that does not cause cracking is 2 mm or less). there were. The results are also shown in Table 1.
  • Example 2 Except having changed the polythiol compound into 77 parts of tris (mercaptopropionyloxyethyl) isocyanurate, the same operation as Example 1 was performed and the laminated body provided with the transparent film was obtained. While measuring the average film thickness and pencil hardness of the obtained transparent film, a mandrel test was performed. The results are shown in Table 1.
  • Example 3 Except having changed the polythiol compound into 53 parts of pentaerythritol tetrakis (mercaptopropionate), the same operation as Example 1 was performed and the laminated body provided with the transparent film was obtained. While measuring the average film thickness and pencil hardness of the obtained transparent film, a mandrel test was performed. The results are shown in Table 1.
  • Example 4 On one surface of a 125 ⁇ m thick polyester film A-4100 (plastic substrate, manufactured by Toyobo Co., Ltd.), a transparent coating layer forming resin composition having the following composition was applied by spin coating, and ultraviolet rays were applied at 200 mJ / After irradiation with cm 2 , the laminate having a transparent film was prepared by heating and drying at 120 ° C. for 20 minutes. The transparent film thus obtained had a thickness of 5 ⁇ m. The pencil hardness of this transparent film was 2H.
  • the laminate having the transparent coating does not crack even when it has a curvature of 2 mm in the mandrel test (JIS K5600-5-1) (that is, the minimum diameter of the mandrel that does not cause cracking is 2 mm or less). ) It was flexible. The results are also shown in Table 1.
  • Example 5 The same operation as in Example 4 was performed except that the polythiol compound was changed to 77 parts of tris (mercaptopropionyloxyethyl) isocyanurate to obtain a laminate having a transparent film. While measuring the average film thickness and pencil hardness of the obtained transparent film, a mandrel test was performed. The results are shown in Table 1.
  • Example 6 The same operation as in Example 4 was performed except that the polythiol compound was changed to 53 parts of pentaerythritol tetrakis (mercaptopropionate) to obtain a laminate having a transparent film. While measuring the average film thickness and pencil hardness of the obtained transparent film, a mandrel test was performed. The results are shown in Table 1.
  • Example 7 Except not adding a photo-acid generator, operation similar to Example 4 was performed and the laminated body provided with the transparent film was obtained. While measuring the average film thickness and pencil hardness of the obtained transparent film, a mandrel test was performed. The results are shown in Table 1.
  • Example 8 Except not adding a photo-acid generator, operation similar to Example 5 was performed and the laminated body provided with the transparent film was obtained. While measuring the average film thickness and pencil hardness of the obtained transparent film, a mandrel test was performed. The results are shown in Table 1.
  • Example 9 Except not adding a photo-acid generator, operation similar to Example 6 was performed and the laminated body provided with the transparent film was obtained. While measuring the average film thickness and pencil hardness of the obtained transparent film, a mandrel test was performed. The results are shown in Table 1.
  • Example 1 On one surface of the polyester film used in Example 1, a transparent film layer-forming resin composition having the following composition was applied by spin coating, and irradiated with ultraviolet rays at 300 mJ / cm 2 and then heated at 120 ° C. for 20 minutes. A laminate having a transparent coating was prepared by drying. The transparent film thus obtained had a thickness of 5 ⁇ m. The pencil hardness of the transparent film was 2H, but the laminate having the transparent film was cracked with a curvature of 10 mm in the mandrel test (that is, the minimum diameter of the mandrel without cracks exceeded 5 mm). The flexibility was not satisfactory.
  • Example 2 On one surface of the polyester film used in Example 1, a transparent film layer-forming resin composition having the following composition was applied by spin coating, and irradiated with ultraviolet rays at 300 mJ / cm 2 and then heated at 120 ° C. for 20 minutes. Although dried, the curing reaction did not proceed and a transparent film could not be obtained.
  • Example 3 On one surface of the polyester film used in Example 1, a transparent film layer-forming resin composition having the following composition was applied by spin coating, and irradiated with ultraviolet rays at 300 mJ / cm 2 and then heated at 120 ° C. for 20 minutes. A laminate having a transparent coating was prepared by drying. The transparent film thus obtained had a thickness of 5 ⁇ m. The pencil hardness of this transparent film was 2H, but the laminate having the transparent film was satisfactory in terms of flexibility because a crack occurred at a curvature of 10 mm in the mandrel test (JIS K5600-5-1). It wasn't possible.
  • Example 4 On one surface of the polyester film used in Example 1, a transparent film layer-forming resin composition having the following composition was applied by spin coating, and irradiated with ultraviolet rays at 300 mJ / cm 2 and then heated at 120 ° C. for 20 minutes. A laminate having a transparent coating was prepared by drying. The transparent film thus obtained had a thickness of 5 ⁇ m. In the mandrel test (JIS K5600-5-1), this transparent film was flexible with no curvature at a curvature of 3 mm, but the pencil hardness was 3B, which is not satisfactory in terms of hardness. There wasn't.
  • the transparent film layer-forming resin composition of the present invention can provide a transparent film excellent in flexibility without cracks even in the mandrel test. Furthermore, it was found that a transparent film having a high pencil hardness of 2H can be obtained by irradiating with an ultraviolet ray having an accumulated irradiation amount of 600 mJ / cm 2 . Even when the cumulative amount of UV irradiation is relatively low at 200 mJ / cm 2 , a transparent film having sufficient hardness and excellent flexibility can be obtained by blending the photoacid generator (C). I understood that.
  • the transparent film obtained from the resin composition for forming a transparent film layer of the present invention has physical properties required as a hard coat layer. It is clear that it is sufficiently equipped.
  • the laminate having the transparent coating does not crack even when it has a curvature of 2 mm in the mandrel test (JIS K5600-5-1) (that is, the minimum diameter of the mandrel that does not cause cracking is 2 mm or less). ) It was flexible. The results are also shown in Table 3.
  • Example 11 A transparent film was obtained in the same manner as in Example 10, except that 17 parts of tetraethoxysilane (TEOS) was further added to the transparent film layer forming resin composition used in Example 1. While measuring the average film thickness and pencil hardness of the obtained transparent film, a mandrel test was performed. The results are shown in Table 3.
  • TEOS tetraethoxysilane
  • Example 12 A transparent film was obtained in the same manner as in Example 10 except that the polythiol compound was changed to 77 parts of tris (mercaptopropionyloxyethyl) isocyanurate. While measuring the average film thickness and pencil hardness of the obtained transparent film, a mandrel test was performed. The results are shown in Table 3. (Example 13)
  • Example 14 A transparent film was obtained in the same manner as in Example 10 except that the polythiol compound was changed to 53 parts of pentaerythritol tetrakis (mercaptopropionate). While measuring the average film thickness and pencil hardness of the obtained transparent film, a mandrel test was performed. The results are shown in Table 3. (Example 14)
  • a transparent film was obtained in the same manner as in Example 10 except that the polythiol compound was changed to 56 parts of dipentaerythritol hexa (mercaptopropionate). While measuring the average film thickness and pencil hardness of the obtained transparent film, a mandrel test was performed. The results are shown in Table 3.
  • Example 15 The same operation as in Example 1 was performed except that 0.2 part of a surface conditioning agent BYK333 manufactured by Big Chemie Japan Co., Ltd. was further added to the resin composition for forming a transparent film layer used in Example 10, and a transparent film was formed. Obtained. While measuring the average film thickness and pencil hardness of the obtained transparent film, a mandrel test was performed. The results are shown in Table 3.
  • Example 16 A transparent film was obtained in the same manner as in Example 1 except that the organosilicon compound was changed to 100 parts of vinyltrimethoxysilane and the polythiol compound was changed to 90 parts of trimethylolpropane tris (mercaptopropionate). While measuring the average film thickness and pencil hardness of the obtained transparent film, a mandrel test was performed. The results are shown in Table 3.
  • B Polythiol compound B1: Trimethylolpropane tris (mercaptopropionate) B2: Tris (mercaptopropionyloxyethyl) isocyanurate B3: Pentaerythritol tetrakis (mercaptopropionate) B4: Dipentaerythritol hexa (mercaptopropionate)
  • TEOS Tetraethoxysilane BYK333: Surface conditioner (manufactured by Big Chemie Japan Co., Ltd.)
  • the pencil hardness is H or higher, and generally has a high hardness of 2H or higher in the presence of the photoacid generator under the condition that the cumulative irradiation amount is 300 mJ / cm 2.
  • the transparent film obtained from the resin composition for forming a transparent film layer of the present invention has physical properties required as a hard coat layer. It is clear that it is sufficiently equipped.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)

Abstract

L'invention concerne une composition de revêtement pour former, sans utiliser aucun lubrifiant ni agent similaire, une couche de revêtement transparente qui présente une résistance à la rayure, une résistance à l'usure, une excellente flexibilité et une dureté suffisante, ainsi qu'un stratifié employant la composition. L'invention concerne une composition de résine pour la formation d'une couche de revêtement transparente, qui se caractérise en ce qu'elle contient (A) un composé d'organosilicium comprenant un groupe fonctionnel réactif et (B) un composé polythiol. L'invention concerne également un procédé de production de la composition et un stratifié.
PCT/JP2010/053197 2009-03-13 2010-03-01 Composition de résine pour la formation de couche de revêtement transparente, et stratifié WO2010103944A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2011503769A JPWO2010103944A1 (ja) 2009-03-13 2010-03-01 透明被膜層形成用樹脂組成物及び積層体
KR1020117021133A KR20120013304A (ko) 2009-03-13 2010-03-01 투명 피막층 형성용 수지 조성물 및 적층체
CN2010800064874A CN102307953A (zh) 2009-03-13 2010-03-01 透明覆膜层形成用树脂组合物和层积体

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2009061791 2009-03-13
JP2009-061791 2009-03-13

Publications (1)

Publication Number Publication Date
WO2010103944A1 true WO2010103944A1 (fr) 2010-09-16

Family

ID=42728234

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2010/053197 WO2010103944A1 (fr) 2009-03-13 2010-03-01 Composition de résine pour la formation de couche de revêtement transparente, et stratifié

Country Status (5)

Country Link
JP (1) JPWO2010103944A1 (fr)
KR (1) KR20120013304A (fr)
CN (1) CN102307953A (fr)
TW (1) TW201035226A (fr)
WO (1) WO2010103944A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012046452A (ja) * 2010-08-27 2012-03-08 Nof Corp チオエーテル含有アルコキシシラン誘導体、およびその用途
JP2012057136A (ja) * 2010-09-13 2012-03-22 Sakai Chem Ind Co Ltd 透明被膜形成用樹脂組成物、積層体、及び透明被膜の製造方法
JP2012197233A (ja) * 2011-03-18 2012-10-18 Nof Corp チオエーテル含有アルコキシシラン誘導体、およびその用途
JPWO2012127608A1 (ja) * 2011-03-22 2014-07-24 富士通株式会社 塗膜及びその製造方法
WO2017150420A1 (fr) * 2016-03-02 2017-09-08 リンテック株式会社 Agent de revêtement dur et film stratifié
WO2017150422A1 (fr) * 2016-03-02 2017-09-08 リンテック株式会社 Agent de revêtement dur et film stratifié
WO2017150421A1 (fr) * 2016-03-02 2017-09-08 リンテック株式会社 Film stratifié

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109111554B (zh) * 2018-07-25 2021-02-02 浩力森涂料（上海）有限公司 一种抗磨损乙烯基硅油改性丙烯酸乳液的制备方法
JP7119861B2 (ja) * 2018-10-01 2022-08-17 日信化学工業株式会社 コーティング用組成物及び積層体

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54142299A (en) * 1978-04-28 1979-11-06 Denki Kagaku Kogyo Kk Photo-setting composition
JPS62141065A (ja) * 1985-12-17 1987-06-24 Toray Silicone Co Ltd 硬化性オルガノポリシロキサン組成物
JPS6314752B2 (fr) * 1981-02-24 1988-04-01 Nippon Ita Garasu Kk
JPS6321695B2 (fr) * 1980-11-29 1988-05-09 Dainippon Printing Co Ltd
JPH05306147A (ja) * 1992-04-16 1993-11-19 Borden Inc 光ファイバー用紫外線硬化可能なコーティングおよび該コーティングを被覆した光ファイバー
JPH05320511A (ja) * 1990-04-10 1993-12-03 Dow Corning Corp オレフィン官能性シリコーンへのチオールの付加により硬化するシリコーン有機コンフォーマルコーティング組成物
JPH08157725A (ja) * 1994-12-09 1996-06-18 Shin Etsu Chem Co Ltd 剥離性紫外線硬化シリコーン組成物及び剥離紙

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4272586A (en) * 1978-02-23 1981-06-09 Denki Kagaku Kogyo Kabushiki Kaisha Laminated glass product
JP4860129B2 (ja) * 2004-09-01 2012-01-25 日揮触媒化成株式会社 透明被膜形成用塗布液および透明被膜付基材

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54142299A (en) * 1978-04-28 1979-11-06 Denki Kagaku Kogyo Kk Photo-setting composition
JPS6321695B2 (fr) * 1980-11-29 1988-05-09 Dainippon Printing Co Ltd
JPS6314752B2 (fr) * 1981-02-24 1988-04-01 Nippon Ita Garasu Kk
JPS62141065A (ja) * 1985-12-17 1987-06-24 Toray Silicone Co Ltd 硬化性オルガノポリシロキサン組成物
JPH05320511A (ja) * 1990-04-10 1993-12-03 Dow Corning Corp オレフィン官能性シリコーンへのチオールの付加により硬化するシリコーン有機コンフォーマルコーティング組成物
JPH05306147A (ja) * 1992-04-16 1993-11-19 Borden Inc 光ファイバー用紫外線硬化可能なコーティングおよび該コーティングを被覆した光ファイバー
JPH08157725A (ja) * 1994-12-09 1996-06-18 Shin Etsu Chem Co Ltd 剥離性紫外線硬化シリコーン組成物及び剥離紙

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012046452A (ja) * 2010-08-27 2012-03-08 Nof Corp チオエーテル含有アルコキシシラン誘導体、およびその用途
JP2012057136A (ja) * 2010-09-13 2012-03-22 Sakai Chem Ind Co Ltd 透明被膜形成用樹脂組成物、積層体、及び透明被膜の製造方法
JP2012197233A (ja) * 2011-03-18 2012-10-18 Nof Corp チオエーテル含有アルコキシシラン誘導体、およびその用途
JPWO2012127608A1 (ja) * 2011-03-22 2014-07-24 富士通株式会社 塗膜及びその製造方法
WO2017150420A1 (fr) * 2016-03-02 2017-09-08 リンテック株式会社 Agent de revêtement dur et film stratifié
WO2017150422A1 (fr) * 2016-03-02 2017-09-08 リンテック株式会社 Agent de revêtement dur et film stratifié
WO2017150421A1 (fr) * 2016-03-02 2017-09-08 リンテック株式会社 Film stratifié
CN108699391A (zh) * 2016-03-02 2018-10-23 琳得科株式会社 硬涂剂和层叠膜
KR20180120189A (ko) 2016-03-02 2018-11-05 린텍 가부시키가이샤 적층 필름
JPWO2017150420A1 (ja) * 2016-03-02 2018-12-20 リンテック株式会社 ハードコート剤及び積層フィルム
JPWO2017150422A1 (ja) * 2016-03-02 2018-12-27 リンテック株式会社 ハードコート剤及び積層フィルム
JPWO2017150421A1 (ja) * 2016-03-02 2019-02-07 リンテック株式会社 積層フィルム
CN108699391B (zh) * 2016-03-02 2022-04-05 琳得科株式会社 硬涂剂和层叠膜

Also Published As

Publication number Publication date
JPWO2010103944A1 (ja) 2012-09-13
CN102307953A (zh) 2012-01-04
KR20120013304A (ko) 2012-02-14
TW201035226A (en) 2010-10-01

Similar Documents

Publication Publication Date Title
WO2010103944A1 (fr) Composition de résine pour la formation de couche de revêtement transparente, et stratifié
TWI465532B (zh) 透明被膜形成用塗料及附有透明被膜之基材
JP5081147B2 (ja) 反射防止コーティング組成物及びそのようなコーティングを堆積させる方法
JP4726198B2 (ja) 感光性樹脂組成物及びその硬化皮膜を有するフィルム
WO2014157334A1 (fr) Film de revêtement dur et son procédé de fabrication
KR20160057221A (ko) 하드코팅층 형성용 조성물
JP2006169328A (ja) 感光性樹脂組成物及びその硬化皮膜を有するフィルム
JPWO2005040245A1 (ja) 感光性樹脂組成物及びその硬化皮膜を有するフィルム
EP1895333B1 (fr) Composition de revêtement dur et produit optique en plastique
JP2006348061A (ja) 感光性樹脂組成物及びその硬化皮膜を有するフィルム
US20220072826A1 (en) Glass Substrate Multilayer Structure, Method of Producing the Same, and Flexible Display Panel Including the Same
TWI749213B (zh) 活性能量線硬化性組成物、及硬塗膜
JP2004017410A (ja) ハードコート被覆非晶質ポリオレフィン樹脂の製造方法及び樹脂物品
JP2005262597A (ja) ハードコートフィルム
WO2017150421A1 (fr) Film stratifié
JP2003147268A (ja) 硬化被膜が形成された透明基材及びそのための硬化性樹脂組成物
JP4736387B2 (ja) 耐擦傷性及び反射防止性を有する積層体
JP4834990B2 (ja) 防眩性積層体及び表示装置
JP2009203282A (ja) 透明帯電防止膜形成用塗料とそれを用いた透明帯電防止膜および透明帯電防止膜付き透明基材
JP2006199765A (ja) 感光性樹脂組成物及びその硬化皮膜を有するフィルム
JP6971965B2 (ja) ハードコート剤及び積層フィルム
JP2021155587A (ja) 水溶性オリゴシロキサン
JP6874312B2 (ja) ハードコート用樹脂組成物の製造方法、及びハードコート用樹脂組成物
JP5827475B2 (ja) 光学フィルム用基材及び光学フィルムの製造方法
JP2013224436A (ja) 表面処理金属酸化物粒子の製造方法、該粒子を含む透明被膜形成用塗布液および透明被膜付基材

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201080006487.4

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10750698

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2011503769

Country of ref document: JP

ENP Entry into the national phase

Ref document number: 20117021133

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 10750698

Country of ref document: EP

Kind code of ref document: A1