WO2014083644A1 - Composition de résine durcissable par des rayons à énergie active - Google Patents

Composition de résine durcissable par des rayons à énergie active Download PDF

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WO2014083644A1
WO2014083644A1 PCT/JP2012/080777 JP2012080777W WO2014083644A1 WO 2014083644 A1 WO2014083644 A1 WO 2014083644A1 JP 2012080777 W JP2012080777 W JP 2012080777W WO 2014083644 A1 WO2014083644 A1 WO 2014083644A1
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component
mass
meth
parts
film
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PCT/JP2012/080777
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English (en)
Japanese (ja)
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清水　基弘
耕平 中島
茂一 伊藤
仁美 猪俣
智志 塩田
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リケンテクノス株式会社
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Priority to PCT/JP2012/080777 priority Critical patent/WO2014083644A1/fr
Priority to TW102142457A priority patent/TWI577733B/zh
Publication of WO2014083644A1 publication Critical patent/WO2014083644A1/fr

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    • 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
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/285—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyethers
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • 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
    • C09D133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/554—Wear resistance
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/584—Scratch resistance
    • 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
    • B32B2451/00—Decorative or ornamental articles
    • 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
    • B32B2471/00—Floor coverings
    • 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
    • B32B2479/00—Furniture
    • 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
    • B32B2509/00—Household appliances
    • B32B2509/10—Refrigerators or refrigerating equipment
    • 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
    • B32B2607/00—Walls, panels

Definitions

  • the present invention relates to an active energy ray-curable resin composition, and more specifically, has a high curing rate, excellent scratch resistance, abrasion resistance, stain resistance, bending resistance, workability, transparency, and hardness.
  • the present invention relates to an active energy ray-curable resin composition that provides a high coating film.
  • base materials made of woody materials such as wood, plywood, laminated timber, particle board, hardboard, as building materials such as flooring and wall materials, or as cabinets for household appliances such as furniture, kitchen products, refrigerators, etc.
  • a decorative sheet made by pasting a decorative sheet on the surface or the surface of a base material made of a metal material such as iron or aluminum is used.
  • Such a decorative sheet is required to have a good balance of not only decorativeness but also scratch resistance, abrasion resistance, stain resistance, transparency and the like at a high level.
  • a paint containing an active energy ray-curable resin composition containing a polyfunctional acrylate such as dipentaerythritol hexaacrylate or pentaerythritol tetraacrylate and / or a polyfunctional urethane acrylate and a polyisocyanate is often used (for example, Patent Document 2)
  • a coating film made of the above-mentioned paint has a poor balance between bending resistance and scratch resistance and wear resistance, and if the bending resistance is improved, scratch resistance and abrasion resistance are not sufficient. .
  • the said coating material has a slow curing speed, Therefore When manufacturing the decorative sheet
  • the UV curability is poor, there is a method of increasing the UV illuminance, but there is a problem that the film is deformed by the radiant heat of the UV lamp.
  • a curable coating that gives a coating film with improved scratch resistance and abrasion resistance
  • a composition containing a polymer having a siloxane bond and an acrylic polyol resin for example, Patent Document 3
  • Patent Document 4 a composition containing a copolymer having a polymer chain moiety
  • these paints have a slow curing rate, and the resulting coating film has insufficient stain resistance.
  • the object of the present invention is an active energy ray curing that has a high curing rate, excellent scratch resistance, abrasion resistance, stain resistance, bending resistance, workability, transparency, and can obtain a coating film with high hardness. It is providing a functional resin composition.
  • the present inventors have found that a resin composition in which a polyether (meth) acrylate modified with ethanolamine and having a specific number of (meth) acryloyloxy groups is combined with a polyisocyanate can achieve the above object. Further, it has been found that when finer particles are added to the resin composition, the hardness of the coating film is further increased.
  • R1 and R2 are each a polyether (meth) acrylate residue having one or more (meth) acryloyloxy groups, and the number of (meth) acryloyloxy groups in R1 and (meth) acryloyloxy in R2 Ethanolamine-modified polyether (meth) acrylate having a total number of groups of 3 or more, (B) a polyisocyanate having two or more isocyanate groups in one molecule, and (C) a photopolymerization initiator, the number of hydroxyl groups (a) in component (A) and the number of isocyanate groups in component (B) ( An active energy ray-curable resin composition having a ratio (a / b) to b) in the range of 0.5 to 1.2.
  • the resin composition of the present invention has a high curing speed. Therefore, when a laminate is produced by applying this composition to a thermoplastic resin film as a base material and curing it, the speed of the production line can be increased. This leads to a reduction in manufacturing costs. Moreover, the coating film obtained from the composition of this invention is excellent in scratch resistance, abrasion resistance, stain resistance, bending resistance, workability, and transparency. In addition, when finer particles are added to the resin composition, the hardness of the coating film is further increased. Therefore, the laminated body having this coating film is used for surface protection and decoration of building materials such as floor materials and wall materials, home appliances such as refrigerators, exterior parts such as automobile door sashes, and interior parts such as instrument panels. Can be suitably used as a decorative sheet.
  • Ethanolamine-modified polyether (meth) acrylate Component (A) in the composition of the present invention is an ethanolamine-modified polyether (meth) acrylate having the following formula (1).
  • R1 and R2 are each a polyether (meth) acrylate residue having one or more (meth) acryloyloxy groups, and the number of (meth) acryloyloxy groups in R1 and (meth) acryloyloxy in R2 The total number of groups is 3 or more, preferably 3 to 9, and more preferably 4.
  • R1 and R2 may be the same or different from each other, but R1 and R2 are preferably the same.
  • Component (A) functions to capture oxygen radicals.
  • the radical polymerizable compound is susceptible to polymerization inhibition by oxygen radicals in the air, and particularly on the surface of the coating film, a curing reaction is caused by oxygen radicals. Become slow. If the irradiation time of the active energy rays is increased so that the surface is sufficiently cured, the speed of the production line is reduced, and the influence of oxygen radicals is relatively small inside the coating film. Becomes fragile, and therefore has poor bending resistance. Since the component (A) has the specific structure of the above formula (1), the composition of the present invention is not inhibited by oxygen radicals.
  • Component (A) has an ethanolamine residue, a hydrogen is generated by extracting hydrogen of a methylene group adjacent to the nitrogen atom in the ethanolamine residue, and an oxygen radical is bound and trapped there. It is done.
  • Component (A) can be produced, for example, by reacting a compound represented by the following formula (3) and a compound represented by the following formula (4) with ethanolamine at room temperature. This reaction is highly active at room temperature and does not require a catalyst. In order to prevent gelation, it is preferable to add a solvent or the like to lower the apparent concentration.
  • R1 and R2 are as defined above.
  • TPGDA tripropylene glycol diacrylate
  • OTA 480 trade name
  • dipentaerythritol hexaacrylate manufactured by Nippon Kayaku Co., Ltd. may be mentioned.
  • the OTA480 is a compound having the following formula (5).
  • component (A) is a compound having the following formula (2).
  • the resulting composition has good storage stability, and the resulting coating film has bending resistance, workability, transparency, and three-dimensional formability. The balance of scratch resistance, abrasion resistance and stain resistance is very good.
  • a separator is placed on a coating film in order to prevent the laminates from blocking each other when the laminate is wound around a roll.
  • the curing reaction is very fast, so there is an advantage that it is not necessary to use a separator.
  • the polyisocyanate component (B) is a compound having two or more isocyanate groups (—N ⁇ C ⁇ O) in one molecule. Specifically, methylene bis-4-cyclohexyl isocyanate, trimethylol propane adduct of tolylene diisocyanate, trimethylol propane adduct of hexamethylene diisocyanate, trimethylol propane adduct of isophorone diisocyanate, isocyanurate of tolylene diisocyanate, hexa Examples thereof include polyisocyanates such as isocyanurate of methylene diisocyanate, isocyanurate of isophorone diisocyanate and biuret of hexamethylene diisocyanate, and urethane crosslinking agents such as block type isocyanates of the above polyisocyanate. Further, at the time of crosslinking, a catalyst such as dibutyltin dilaurate and dibutyltin dieth
  • those having three or more isocyanate groups in one molecule are preferable from the viewpoint of the bending resistance and three-dimensional formability of the coating film and the storage stability of the paint, and particularly represented by the following formula (6).
  • These have a structural feature that isocyanate groups are present at positions away from each other at the end of the hexamethylene chain, and thus the resulting coating film is elastic and excellent in scratch resistance and abrasion resistance.
  • the resin composition of the present invention is cured by the reaction between the hydroxyl group in component (A) and the isocyanate group in component (B).
  • the resin composition of the present invention has a ratio (a / b) of the number of hydroxyl groups (a) in component (A) to the number of isocyanate groups (b) in component (B) (a / b) so that curing can occur sufficiently. It is in the range of 5 to 1.2, preferably 0.7 to 1.1. When the ratio is less than the lower limit, the resulting coating film is inferior in bending resistance and three-dimensional formability. When the ratio is larger than the above upper limit, the resulting coating film is poor in stain resistance against aqueous contaminants such as aqueous magic.
  • the resin composition of the present invention comprises a (meth) acrylate compound (A ′) other than the component (A). May further be included.
  • the properties of the coating film can be appropriately adjusted according to the use of the laminate.
  • the ratio ((a + a ′) / b) to the number (b) of is in the range of 0.5 to 1.2, preferably 0.7 to 1.1.
  • the resulting coating film When the ratio is less than the lower limit, the resulting coating film is inferior in bending resistance and three-dimensional formability. When the ratio is larger than the above upper limit, the resulting coating film is poor in stain resistance against aqueous contaminants such as aqueous magic.
  • the component (A ′) may or may not have a hydroxyl group. The compounding ratio of the component (A) and the component (A ′) can be appropriately determined according to the use of the laminate.
  • the component (A) When the sum of the amount of the component (A) and the amount of the component (A ′) is 100% by mass, the component (A) is usually 10 to 100% by mass and the component (A ′) is 90 to 0% by mass, The component (A) is preferably 50 to 100% by mass and the component (A ′) is preferably 50 to 0% by mass.
  • Examples of the (meth) acrylate compound (A ′) include polyurethane (meth) acrylate, polyester (meth) acrylate, polyacryl (meth) acrylate, epoxy (meth) acrylate, polyalkylene glycol poly (meth) acrylate and (Meth) acryloyloxy group-containing prepolymer or oligomer such as polyether (meth) acrylate; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl ( (Meth) acrylate, lauryl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, phenyl (meth) Acrylate, phenyl cellosolve (meth
  • each hydroxyl group of component (A) and component (A ′) was acetylated with an acetylating reagent (acetic anhydride in pyridine), then excess acetylating reagent is hydrolyzed with water, and the resulting acetic acid is converted into Kyoto.
  • the above number was determined by titration with an ethanol solution of potassium hydroxide using a potentiometric automatic titrator AT-610, manufactured by Denki Kogyo Co., Ltd.
  • the number of isocyanate groups per unit amount of component (B) was determined based on JIS-K-7301: 1995. That is, by reacting the isocyanate group of component (B) with dinormal butylamine, and then titrating excess dinormal butylamine with an aqueous hydrochloric acid solution using an automatic potentiometric titrator AT-610 type manufactured by Kyoto Electronics Industry Co., Ltd. The above number was determined.
  • the photopolymerization initiator component (C) is a radical polymerization type photopolymerization initiator, and known ones can be used. For example, triazine compounds, acetophenone compounds, biimidazole compounds, benzoin compounds, benzophenone compounds, thioxanthone compounds, anthracene compounds, alkylphenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds And photopolymerization initiators such as oxime phenylacetate compounds, hydroxyketone compounds and aminobenzoate compounds. These can be used alone or in combination of two or more. Among these, benzophenone compounds are preferable because the reaction mechanism is a radical generation type by hydrogen abstraction.
  • the compounding quantity of a component (C) can be suitably selected with the kind of other component, and desired coating-film thickness, Generally, with respect to 100 mass parts of component (A), or a component (A ') When present, the amount is about 0.5 to 10 parts by mass with respect to 100 parts by mass in total of component (A) and component (A ′).
  • the coating thickness is 0.5 to When the thickness is 30 ⁇ m, the amount of the component (C) is 4 to 10 parts by mass with respect to 100 parts by mass of the component (A), and when the coating thickness is 30 to 500 ⁇ m, the component (A) 100 0.5 to 8 parts by mass with respect to parts by mass.
  • the reason why the amount of the component (C) is generally larger when the thickness of the coating film is thinner is that the thinner the film, the more easily the influence of curing inhibition by oxygen radicals occurs.
  • the resin composition of the present invention comprises fine particles having a particle size of 1 nm to 300 nm based on 100 parts by mass of component (A), or component (A) and component (A ′) when component (A ′) is present. It is preferably contained in an amount of 1 to 50 parts by mass with respect to 100 parts by mass in total of A ′).
  • Component (F) serves to increase the hardness of the coating film obtained from the resin composition of the present invention.
  • both inorganic fine particles and organic fine particles can be used.
  • the inorganic fine particles include silica (silicon dioxide); metal oxide fine particles such as aluminum oxide, zirconia, titania, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide, antimony oxide, and cerium oxide; Metal fluoride fine particles such as magnesium fluoride and sodium fluoride; metal fine particles; metal sulfide fine particles; metal nitride fine particles; Examples of the organic fine particles include resin beads such as a styrene resin, an acrylic resin, a polycarbonate resin, an ethylene resin, and a cured resin of an amino compound and formaldehyde. These can be used alone or in combination of two or more.
  • the surface of the fine particles is treated with a silane coupling agent such as vinylsilane or aminosilane; a titanate coupling agent; Coupling agent; Organic compound having an ethylenically unsaturated bond group such as (meth) acryloyl group, vinyl group and allyl group and reactive functional group such as epoxy group; Surface treatment agent such as fatty acid and fatty acid metal salt You may use what was processed.
  • silica and aluminum oxide fine particles are preferable, and silica fine particles are more preferable in order to obtain a coating film with higher hardness.
  • Examples of commercially available silica fine particles include Snowtex (trade name) manufactured by Nissan Chemical Industries, Ltd., Quartron (trade name) manufactured by Fuso Chemical Industries, Ltd., and the like.
  • the particle diameter of the component (F) needs to be 300 nm or less in order to impart transparency of the resulting coating film. Moreover, when the particle diameter is coarse, the hardness of the obtained coating film tends to be insufficient. Preferably it is 200 nm or less, More preferably, it is 120 nm or less. On the other hand, there is no particular lower limit of the particle diameter, but normally available particles are at most about 1 nm even if they are fine.
  • the particle diameter of the fine particles is a cumulative particle diameter distribution curve of 50 measured using a laser diffraction / scattering particle size analyzer MT3200II (trade name) manufactured by Nikkiso Co., Ltd.
  • the particle diameter is mass%.
  • the compounding quantity of a component (F) is with respect to 100 mass parts of components (A), or when a component (A ') exists, with respect to a total of 100 mass parts of a component (A) and a component (A'). 1 to 50 parts by mass. If it is 1 part by mass or less, the effect of improving the hardness of the coating film cannot be obtained. If it is 50 parts by mass or more, the bending resistance is lowered. The amount is preferably 3 to 25 parts by mass.
  • composition of the present invention may contain a solvent as needed for dilution.
  • the solvent is compatible with components (A), (A ′), (B), (C) and (E), and components (A), (A ′), (B), (C), ( There is no particular limitation as long as it does not react with E) and (F) or catalyze the self-reaction of these components.
  • known compounds such as 1-methoxy-2-propanol, n-butyl acetate, toluene and methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, diacetone alcohol and the like can be used.
  • a solvent containing 40% by mass or more, more preferably 80% by mass or more of 1-methoxy-2-propanol is preferable, and the thermoplastic resin film (3) described below is coated with the above composition.
  • a resin film having low solvent resistance such as a stretched polyester resin film.
  • unstretched polyester-based resin films are widely used as base films for decorative films because they are excellent in three-dimensional formability and bending resistance and surface gloss, but are poor in solvent resistance. Therefore, when a composition containing a solvent is applied to an unstretched polyester resin film as a base film, the surface gloss of the resulting decorative film is lost, or in some cases the base film swells and a decorative film is obtained. There is a problem of disappearing. If the solvent contains 40% by mass or more of 1-methoxy-2-propanol, the above problem does not occur.
  • the amount of the solvent can be appropriately adjusted so as to have a suitable viscosity according to the coating apparatus and the thickness of the coating film.
  • the composition of the present invention is a UV-reactive fluorine-based surface modifier for preventing paint repellency and for preventing fingerprint resistance, stain resistance and blocking of the coating film.
  • Agent (E) may further be included.
  • the ultraviolet-reactive fluorine-based surface modifier (E) is preferably a compound having a fluorine-containing group, a hydrophilic group, a lipophilic group, and an ultraviolet-reactive group. Mega-Face RS-75 (trade name) is available.
  • the amount of component (E) is based on 100 parts by weight of component (A) or, if component (A ′) is present, based on a total of 100 parts by weight of component (A) and component (A ′),
  • the amount is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 2.0 parts by mass. If the amount is more than 5 parts by mass, the surface hardness may decrease.
  • the resin composition of the present invention is an antioxidant, a weather resistance stabilizer, a light resistance stabilizer, an ultraviolet absorber, a heat stabilizer, an antistatic agent, a surfactant, within a range not impairing the effects of the present invention.
  • One type or two or more types of additives such as a colorant, an infrared shielding agent, a leveling agent, a thixotropic agent, and a filler may be included.
  • the resin composition of the present invention can be obtained by mixing and stirring the above components (A), (B), (C) and preferably (F), and other optional components.
  • the resin composition thus obtained is active energy ray-curable, and this is applied to the surface of the thermoplastic resin film (3) as a base material and irradiated with active energy rays such as ultraviolet rays, visible rays, and electron beams.
  • active energy rays such as ultraviolet rays, visible rays, and electron beams.
  • a laminate having a coating film (1) excellent in scratch resistance, abrasion resistance, contamination resistance and bending resistance is obtained.
  • thermal lamination is performed after the coating composition (1) is formed by applying, drying and curing the above composition to a substrate having excellent solvent resistance, for example, a biaxially stretched polyethylene terephthalate film having a release treatment applied to the surface.
  • the resin composition of the present invention has a fast curing reaction, it is possible to increase the line speed when the composition is applied to a substrate to produce a laminate, and thus the manufacturing cost can be reduced. .
  • the thickness of the coating film (1) is preferably 0.5 ⁇ m or more. If it is thinner than this, scratch resistance may be insufficient. On the other hand, there is no upper limit on the thickness of the coating film. However, since an unnecessarily thick coating film only increases the cost, the thickness is 60 ⁇ m at most.
  • thermoplastic resin film (3) Any thermoplastic resin film can be used as the thermoplastic resin film (3) where the coating film (1) made of the resin composition is laminated to form a laminate.
  • thermoplastic resin film (3) polyvinyl chloride resin, non-crystalline, low crystalline or crystalline polyester, polypropylene, polyolefin such as polyethylene, acrylonitrile / butadiene / styrene copolymer resin (ABS resin), styrene / ethylene / butadiene / styrene copolymer Styrene resin such as hydrogenated styrene / ethylene / butadiene / styrene copolymer, unstretched film of thermoplastic resin such as polyamide, acrylic, polycarbonate, polyurethane, uniaxially stretched film and biaxially stretched film it can.
  • ABS resin acrylonitrile / butadiene / styrene copolymer resin
  • Styrene resin such as hydrogen
  • a non-stretched film of a polyvinyl chloride resin or an amorphous polyester resin or a stretched crystalline polyester film is used.
  • a thermoplastic resin film (3) itself has high surface glossiness, and it is preferable that it is transparent.
  • a non-stretched film of an amorphous polyester resin and a stretched polyester film are preferable.
  • Polyester resins such as polyethylene terephthalate, glycol copolymerized polyethylene terephthalate, acid copolymerized polyethylene terephthalate, and polyethylene naphthalate, or these resins
  • a biaxially stretched polyester film comprising any combination is particularly preferred.
  • non-stretched film of the non-crystalline polyester resin examples include SET329 FZ26401 ⁇ trade name, cyclohexanedimethanol copolymerized polyethylene terephthalate (PETG resin) film ⁇ manufactured by Riken Technos Co., Ltd. Mention of Lumirror (trade name) of Co., Ltd., Emblet S25 (trade name) of Unitika Co., Ltd., Melinex (705) # 75 (trade name) of Teijin Ltd. and A4300 (trade name) of Toyobo Co., Ltd. it can.
  • the thickness of the thermoplastic resin film (3) is usually 10 ⁇ m to 100 ⁇ m, preferably 15 to 50 ⁇ m. If it is thinner than the above lower limit, wrinkles may enter the laminated body. If it is thicker than the above upper limit, the laminated body will be bounced during lapping molding, and the processing speed of coating and laminating must be kept low. It may disappear.
  • Lamination of the coating film (1) composed of the above composition onto the thermoplastic resin film (3) is applied directly to the thermoplastic resin film (3) or via an anchor coat (2) layer described later.
  • a coating film (1) by applying, drying and curing the above composition to a substrate excellent in solvent resistance, for example, a biaxially stretched polyethylene terephthalate film having a release treatment applied to the surface by drying and curing ) Can be performed by bonding directly to the thermoplastic resin film (3) or via the anchor coat (2) layer by a method such as thermal lamination or dry lamination.
  • Anchor coat (2) The laminate may have an anchor coat (2) between the coating film (1) and the thermoplastic resin film (3). By providing the anchor coat (2), the adhesive strength between the coating film (1) and the thermoplastic resin film (3) can be increased.
  • an anchor coating agent for forming the anchor coat (2) As an anchor coating agent for forming the anchor coat (2), it is well soluble in known solvents such as 1-methoxy-2-propanol, n-butyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, acetone and the like. As long as a sufficient anchor effect can be obtained, there is no particular limitation, and conventional ones such as polyester, acrylic, polyurethane, acrylic urethane, and polyester urethane can be used. Commercially available examples include Byron 24SS (trade name) manufactured by Toyobo Co., Ltd., AU2141NT manufactured by Tokushi Co., Ltd., and the like.
  • the anchor coat (2) is formed on one surface of the thermoplastic resin film (3) by applying an anchor coat agent by a conventional method.
  • the anchor coat (2) A coating film (1) comprising the above composition can be laminated on the substrate.
  • the thickness of the anchor coat (2) is usually about 0.1 to 5 ⁇ m, preferably 0.5 to 2 ⁇ m.
  • the method for applying the resin composition or the anchor coating agent to the thermoplastic resin film (3) is not particularly limited, and a known web application method can be used. Specific examples include roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and die coating.
  • thermoplastic resin film (5) In the laminate, the thermoplastic resin film (5) is further laminated via an adhesive layer (4) on the surface opposite to the surface on which the coating film (1) of the thermoplastic resin film (3) is laminated. (Refer to FIG. 1), and an adhesive layer (6) may be further provided thereon.
  • an adherend for example, a particle board
  • the irregularities are laminated when the laminate further has a thermoplastic resin film (5). It is preferable that it can be prevented from reaching the surface of the film, and therefore, vividness can be maintained.
  • the lamination of the thermoplastic resin film (5) is performed, for example, by applying an adhesive on the surface opposite to the surface on which the coating film (1) of the thermoplastic resin film (3) is laminated, and then applying the adhesive layer (4).
  • the thermoplastic resin film (5) can be formed thereon by using a metal roll-rubber roll heat laminating apparatus. At this time, the metal roll side is brought into contact with the coating film (1).
  • the surface temperature of the metal roll is preferably 120 ° C. or higher, more preferably 160 ° C. or higher.
  • the upper limit of the surface temperature is about 250 ° C. in consideration of the heat resistance of the thermoplastic resin film (3).
  • the thickness of the thermoplastic resin film (5) is not particularly limited, but is usually 20 to 1000 ⁇ m, preferably 100 to 500 ⁇ m. If it is too thin, when the laminate is affixed to the adherend, the irregularities on the surface of the adherend may reach the surface of the laminate, and may not provide sharpness. If it is too thick, Bonding workability to the adherend tends to be lowered.
  • thermoplastic resin film (5) those mentioned for the thermoplastic resin film (3) can be used.
  • the thermoplastic resin film (5) is preferably 60 to 130 ° C.
  • the thermoplastic resin film having such a glass transition temperature include films of acrylic resin, polyvinyl chloride resin, polyester resin, and acrylonitrile / butadiene / styrene copolymer resin.
  • the thermoplastic resin film (5) has the following resins ( ⁇ -1) and ( ⁇ -2): ( ⁇ -1) Amorphous polyethylene terephthalate in which the dicarboxylic acid component is terephthalic acid, and the glycol component is composed of 60 mol% or more and less than 90 mol% of ethylene glycol and 10 mol% or more and less than 40 mol% of 1,4-cyclohexanedimethanol.
  • the aromatic polyester resin composition further comprises a polybutylene terephthalate resin, a polytrimethylene terephthalate resin, a polytrimethylene terephthalate resin, a polybutylene terephthalate copolymer in which the dicarboxylic acid component is terephthalic acid and isophthalic acid, and the glycol component is tetramethylene glycol.
  • Other polyester resins such as resins may be included.
  • a further resin other than the above is added in an amount of 0.1 to 10 parts by mass. It may be included in the range.
  • the further resin examples include methacrylic acid ester-styrene / butadiene rubber graft copolymer, acrylonitrile-styrene / butadiene rubber graft copolymer, acrylonitrile-styrene / ethylene-propylene rubber graft copolymer, acrylonitrile-styrene / Mention may be made of elastomer resins such as acrylic ester graft copolymers, methacrylic ester / acrylic ester rubber graft copolymers, methacrylic ester-acrylonitrile / acrylic ester rubber graft copolymers and thermoplastic polyester elastomers.
  • elastomer resins such as acrylic ester graft copolymers, methacrylic ester / acrylic ester rubber graft copolymers, methacrylic ester-acrylonitrile / acrylic ester rubber graft copolymers and thermoplastic polyester elasto
  • the aromatic polyester resin composition further contains 0.1 to 5 mass of additives such as a lubricant, an antioxidant, a weather resistance stabilizer, a heat stabilizer, a release agent, an antistatic agent and a surfactant. It may be included in the range of parts.
  • additives such as a lubricant, an antioxidant, a weather resistance stabilizer, a heat stabilizer, a release agent, an antistatic agent and a surfactant. It may be included in the range of parts.
  • the lubricant include hydrocarbon waxes such as paraffin wax, polyethylene wax, and polypropylene wax, fatty acid waxes such as stearic acid, hydroxystearic acid, composite stearic acid, and oleic acid, stearamide, and oxystearic acid.
  • Aliphatic amide waxes such as amide, oleic acid amide, erucyl amide, ricinoleic acid amide, behenic acid amide, methylene bis stearic acid amide, ethylene bis stearic acid amide, aliphatic esters such as stearic acid n-butyl and montanic acid ester wax And waxes, aliphatic metal soap waxes, urea-formaldehyde waxes and the like.
  • a pigment and an inorganic filler can be further contained. There is no restriction
  • the inorganic filler include light calcium carbonate, heavy calcium carbonate, hydrous magnesium silicate, and talc.
  • the film comprising the aromatic polyester resin composition can be produced by any method, for example, can be formed using a calendar processing machine, or can be formed using an extruder and a T die. You can also Any calendar processing machine can be used, and examples thereof include an upright three roll, an upright four roll, an L four roll, an inverted L four roll, and a Z roll. Any extruder can be used, and examples thereof include a single-screw extruder, a same-direction rotating twin-screw extruder, and a different-direction rotating twin-screw extruder. Any T die can be used, and examples thereof include a manifold die, a fishtail die, and a coat hanger die.
  • thermoplastic resin film (3) is a biaxially stretched polyester film
  • thermoplastic resin film (5) is a film of the above aromatic polyester resin composition. is there.
  • the adhesive for forming the adhesive layer (4) and the adhesive layer (6) is not particularly limited as long as sufficient adhesive strength can be obtained.
  • Conventional adhesives such as vinyl, polyester, polyurethane, epoxy resin, chloroprene rubber and styrene butadiene rubber can be used.
  • the method in particular of providing an adhesive bond layer is not restrict
  • any diluent solvent such as 1-methoxy-2-propanol, nbutyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, and acetone can be used as necessary.
  • Synthesis example 1 Daicel Cytec Co., Ltd. OTA480 (product name, glycerin propoxytriacrylate of formula (5) above) and 2-aminoethanol were charged into a glass beaker in an amount of 1 mol of the latter to 2 mol of the former, The reaction was carried out at a temperature of 23 ° C. for 72 hours to obtain an ethanolamine-modified polyether acrylate (A-1) having four acryloyloxy groups having the structure of the above formula (2). The number of hydroxyl groups per unit amount of component (A-1) was 1.09 mol / kg as measured by the method described above.
  • Synthesis example 2 In Synthesis Example 1, two samples were used in the same manner as in Synthesis Example 1 except that tripropylene glycol diacrylate (manufactured by Daicel-Cytec) was used instead of OTA480 (manufactured by Daicel-Cytec).
  • An ethanolamine-modified polyether acrylate (A-2) having an acryloyloxy group was synthesized.
  • the number of hydroxyl groups per unit amount of component (A-2) was 1.51 mol / kg.
  • Example 1 100 parts by mass of component (A-1) as component (A), Coronate HX (trade name, polyisocyanate of formula (6) above) (B-1) 25 manufactured by Nippon Polyurethane Industry Co., Ltd. as component (B) Anti-repellent agent (Kyoeisha Co., Ltd.) as other optional components of 10 parts by mass, 7 parts by mass of benzophenone (C-1) as component (C), and 200 parts by mass of 1-methoxy-2-propanol as component (D)
  • An active energy ray-curable resin composition was obtained by mixing and stirring together with 0.3 part by mass of manufactured Polyflow 75 (trade name).
  • Unitika's biaxially stretched polyester film “Unitika S” (trade name, thickness 50 ⁇ m) is used as the thermoplastic resin film (3), and an anchor coating agent (Toyobo Co., Ltd. Byron 24SS (trade name)) is used on one side.
  • An anchor coating agent (Toyobo Co., Ltd. Byron 24SS (trade name)) is used on one side.
  • the process of applying the resin composition obtained above on the anchor coat (2), drying, irradiating with ultraviolet rays, and winding the obtained laminate on a roll is a series of production lines, 50 m / min line Performed continuously at speed. The roll could be wound well without using a separator.
  • the resin composition was applied using a film Mayer bar type coating apparatus so that the coating thickness after drying was 11 ⁇ m.
  • the line speed in an Example and a comparative example is the fastest speed which can manufacture a laminated body stably in a production line.
  • the obtained laminates were subjected to the following tests (1) to (7). The results are shown in Table 1.
  • Example 2 As a component (B), Sumidur HT of Sumika Bayer Urethane Co., Ltd. (trade name, polyisocyanate of the above formula (7), number of isocyanate groups per unit amount: 3.10 mol / kg) (B-2) was used in the same manner as in Example 1 except that 42 was used in an amount of 42 parts by mass. The results are shown in Table 1.
  • Examples 3 to 6 and Comparative Examples 1 and 2 A laminate was produced in the same manner as in Example 1 except that the amount of component (B) in Example 1 was changed as shown in Table 1. The results are shown in Table 1.
  • Example 6 a laminate was produced in the same manner as in Example 6 except that the component (A-2) obtained in Synthesis Example 2 was used in place of the component (A-1). The line speed at this time was 50 m / min as in Example 6, but a separator was required for winding onto the roll. The results are shown in Table 1.
  • Example 4 In Example 1, instead of component (A-1), tripropylene glycol diacrylate (manufactured by Daicel Cytec Co., Ltd., number of hydroxyl groups per unit amount: 0 mol / kg) (A-3) was used.
  • (C) is an alkylphenone photopolymerization initiator (Darocur 1173 (trade name), 2-hydroxy-2-methyl-1-phenyl-propan-1-one) (C-2) from Ciba Japan Co., Ltd.
  • a laminate was produced in the same manner as in Example 1 except that it was used in an amount of 5 parts by mass. The line speed at this time was 30 m / min.
  • Example 5 dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., number of hydroxyl groups per unit amount: 0.63 mol / kg) (A-4) was used instead of component (A-1).
  • a laminate was manufactured in the same manner as in Example 1 except that the amount of the component (B) was changed so that the ratio (a / b) was 0.85.
  • the results are shown in Table 1.
  • the above (A-4) does not have a hydroxyl group in structure, but a hydroxyl group exists because it contains a component in which a part of the acryloyloxy group is hydrolyzed.
  • Example 6 In Example 1, instead of component (A-1), ditrimethylolpropane tetraacrylate (manufactured by Nippon Kayaku Co., Ltd., number of hydroxyl groups per unit amount: 0.35 mol / kg) (A-5) was used. In addition, a laminate was manufactured in the same manner as in Example 1 except that the amount of the component (B) was changed so that the ratio (a / b) was 0.85. The results are shown in Table 1.
  • Comparative Example 7 In Example 1, “self-healing paint No. 100” (trade name, polydimethylsiloxane graft acrylate-based paint) manufactured by NATCO Co., Ltd. was used as the resin composition, and the dry film thickness was 20 ⁇ m. A laminate was obtained in the same manner as in Example 1. The line speed at this time was 10 m / min, and a separator was required for winding onto a roll. The results are shown in Table 1. The film thickness in Comparative Example 7 was made thicker than the thickness in Example 1 (11 ⁇ m) because the results of scratch resistance-1 and 2 corresponding to the most important characteristics of the self-healing paint were This is for comparison with the example. The scratch resistance is better when the coating thickness is thicker.
  • Example 7 In Example 1, a laminate was produced in the same manner as in Example 1 except that the coating thickness was 2 ⁇ m. The line speed at this time was 40 m / min. The reason why the line speed is slower than that of Example 1 is that when the coating film is thin, the influence of oxygen radicals reaches the inside of the coating film, and as a result, the curing speed of the entire coating film becomes slow. The results are shown in Table 1.
  • Example 8 In Example 1, a laminate was produced in the same manner as in Example 1 except that the coating thickness was 50 ⁇ m. The line speed at this time was 50 m / min. The results are shown in Table 1.
  • Example 9 In Example 1, a laminate was produced in the same manner as in Example 1 except that methyl ethyl ketone was used as the component (D). The line speed at this time was 50 m / min. The results are shown in Table 1.
  • Pencil Hardness According to JIS K 5600-5-4, the hardness of the coating film surface was evaluated using a pencil ⁇ "Uni" (trade name) of Mitsubishi Pencil Co., Ltd. ⁇ under a 200 g load condition.
  • the composition of the present invention can produce a laminate having a coating film comprising the composition at a high line speed, and the coating film has scratch resistance and stain resistance. Excellent bending resistance and appearance.
  • the compositions of Comparative Examples 1 and 2 having a ratio (a / b) outside the scope of the present invention are inferior in any of scratch resistance, stain resistance and bending resistance of the resulting coating film.
  • the composition of Comparative Example 3 using a component (A) having a smaller number of (meth) acryloyloxy groups than the range of the present invention is inferior in scratch resistance and stain resistance of the resulting coating film.
  • compositions of Comparative Examples 4 to 6 using the component (A) having no ethanolamine residue had a slow curing speed and therefore a slow line speed. Further, the obtained coating film was inferior in any of scratch resistance, stain resistance, bending resistance and appearance.
  • Comparative Example 7 in which a polydimethylsiloxane graft acrylate paint, which is a self-healing paint, was used as the resin composition, the coating film was poor in stain resistance. Further, as is clear from the comparison between Example 7 and Example 8, the thicker coating film can increase the line speed, but in Comparative Example 7, the coating film thickness is higher than that of Example 1. Despite the increase in thickness, the cure rate was slow and therefore the line speed was slow.
  • Example 10 In Example 1, as the thermoplastic resin film (3), SET329 FZ26401 (trade name, cyclohexanedimethanol copolymerized polyethylene terephthalate (PETG resin) film manufactured by Riken Technos Co., Ltd., thickness 100 ⁇ m, conforming to JIS-7105-1981 on the surface. A laminate was produced in the same manner as in Example 1 except that the 60 ° gloss (90%) measured in this manner was used and no anchor coat agent was used. The line speed at this time was 50 m / min. The obtained laminates were subjected to the tests (1) to (7). Further, the 60 ° gloss of the surface of the coating film (1) was measured according to JIS-7105-1981. The results are shown in Table 2.
  • PETG resin cyclohexanedimethanol copolymerized polyethylene terephthalate
  • Example 10 a laminate was produced in the same manner as in Example 10 except that methyl ethyl ketone was used as component (D). However, the thermoplastic resin film (3) as a base material swelled, and the laminate was produced. Can not get.
  • thermoplastic resin film (3) as the substrate is an unstretched polyester film
  • methyl ethyl ketone is used as the solvent (D)
  • the substrate film swells to obtain a laminate.
  • D-2 a solvent containing 1% by mass of 1-methoxy-2-propanol
  • the base film does not swell and the gloss of the base film is not lowered.
  • a laminate was obtained (Examples 10 and 11).
  • Example 12 A biaxially stretched polyester film “E5101 (trade name)” (thickness 25 ⁇ m) of Toyobo Co., Ltd. is used as the thermoplastic resin film (3), and an anchor coating agent “Byron 24SS (trade name) of Toyobo Co., Ltd. is used on one side thereof.
  • An anchor coating agent “Byron 24SS (trade name) of Toyobo Co., Ltd. was used on one side thereof.
  • the line was run continuously at a line speed of 50 m / min.
  • the roll could be wound well without using a separator.
  • the resin composition was applied using a film Mayer bar type coating
  • thermoplastic resin film (3) of the laminate obtained above a polyester hot melt adhesive “AD-170-20 (trade name)” manufactured by Tokushi Co., Ltd. has a thickness of 2.5 ⁇ m after drying. Then, the thermoplastic resin film (5) obtained as described below is bonded using a mirror metal roll-rubber roll thermal laminator to obtain a laminate having the structure shown in FIG. It was. At this time, the metal roll side was in contact with the coating film (1), and the surface temperature of the metal roll was set to 190 ° C. For the laminate thus obtained, the above test (1 ) To (7) and the following tests (8) to (10) were conducted. Further, the 60 ° gloss of the surface of the coating film (1) was measured according to JIS-7105-1981. The results are shown in Table 3.
  • thermoplastic resin film (5) 44 parts by mass of PETG resin “Cadence GS1 (trade name)” of Eastman Chemical Company, Inc.
  • Crystalline polyethylene terephthalate resin “WK-801 (trade name)” (Dicarboxylic acid component: mixture of terephthalic acid 90 mol% or more and less than 99 mol% and isophthalic acid 1 mol% or more and less than 10 mol%; glycol component: ethylene glycol) 41 parts by mass, polybutylene terephthalate resin “Toraycon 1200M” manufactured by Toray Industries, Inc. (Trade name) ”15 parts by weight, Kaneka Co., Ltd.
  • thermoplastic resin film (5) was obtained by being cooled and solidified by being sandwiched between a mirror cooling roll made of rubber and a cooling roll made of rubber.
  • Example 13 As a component (B), Sumidur HT of Sumika Bayer Urethane Co., Ltd. (trade name, polyisocyanate of the above formula (7), number of isocyanate groups per unit amount: 3.10 mol / kg) (B-2) was used in the same manner as in Example 12 except that 42 was used in an amount of 42 parts by mass. The results are shown in Table 3.
  • Examples 14 to 17 and Comparative Examples 8 to 9 A laminate was produced in the same manner as in Example 12 except that the amount of component (B) in Example 12 was changed as shown in Table 3. The results are shown in Table 3.
  • Comparative Example 10 A laminate was produced in the same manner as in Example 17 except that the component (A-2) obtained in Synthesis Example 2 was used in place of the component (A-1). The line speed at this time was 50 m / min as in Example 17, but a separator was required for winding on the roll. The results are shown in Table 3.
  • Example 12 instead of component (A-1), tripropylene glycol diacrylate (manufactured by Daicel Cytec Co., Ltd., number of hydroxyl groups per unit amount: 0 mol / kg) (A-3) was used.
  • C is an alkylphenone photopolymerization initiator (Darocur 1173 (trade name), 2-hydroxy-2-methyl-1-phenyl-propan-1-one) (C-2) from Ciba Japan Co., Ltd.
  • a laminate was produced in the same manner as in Example 12 except that it was used in an amount of 5 parts by mass. The line speed at this time was 30 m / min.
  • Example 12 dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., number of hydroxyl groups per unit amount: 0.63 mol / kg) (A-4) was used instead of component (A-1). Further, a laminate was produced in the same manner as in Example 12 except that the amount of component (B) was changed so that the ratio (a / b) was 0.85. The results are shown in Table 3. The above (A-4) does not have a hydroxyl group in structure, but a hydroxyl group exists because it contains a component in which a part of the acryloyloxy group is hydrolyzed. The same applies to (A-5) in Comparative Example 13 below.
  • Example 12 instead of component (A-1), ditrimethylolpropane tetraacrylate (manufactured by Nippon Kayaku Co., Ltd., number of hydroxyl groups per unit amount: 0.35 mol / kg) (A-5) was used. Further, a laminate was produced in the same manner as in Example 12 except that the amount of component (B) was changed so that the ratio (a / b) was 0.85. The results are shown in Table 3.
  • Example 18 In Example 12, a laminate was produced in the same manner as in Example 12 except that the thickness of the coating film was 2 ⁇ m. The line speed at this time was 40 m / min. The reason why the line speed is slower than in Example 12 is that when the coating film is thin, the influence of oxygen radicals reaches the inside of the coating film, and as a result, the curing speed of the entire coating film becomes slow. The results are shown in Table 3.
  • Example 19 In Example 12, a laminate was produced in the same manner as in Example 12 except that the thickness of the coating film was 50 ⁇ m. The line speed at this time was 50 m / min. The results are shown in Table 3.
  • Example 20 In Example 12, a laminate was produced in the same manner as in Example 12 except that methyl ethyl ketone was used as the component (D). The line speed at this time was 50 m / min. The results are shown in Table 3.
  • Example 21 component (A ′) was added in addition to component (A).
  • component (A) 50 parts by mass of component (A-1) was used, and as component (A ′), 50 parts by mass of component (A-4) was used.
  • a laminate was produced in the same manner as in Example 12 except that the active energy ray-curable resin composition was obtained using the components (B) to (E) shown in Table 3. The results are shown in Table 3.
  • Example 22 A laminate was produced in the same manner as in Example 21 except that the amount of component (E) was 2.0 parts by mass. The results are shown in Table 3.
  • Test method Solvent rubbing test The laminate obtained above was cut into a size of 100 mm ⁇ 100 mm, and the surface of the coating film (1) was scrubbed using Kimwipe (trade name) sufficiently containing methyl ethyl ketone. The presence or absence of a change in gloss or sharpness of the portion after 10 reciprocating wipes was visually observed and evaluated according to the following criteria. ⁇ : No change in surface gloss or sharpness ⁇ : Change in surface gloss or sharpness
  • the laminate having the coating film (1) made of the active energy ray-curable resin composition of the present invention has high gloss and has scratch resistance, stain resistance, and bending resistance. Moreover, characteristics such as appearance are also good.
  • the laminate of Comparative Example 10 in which the number of (meth) acryloyloxy groups is less than the range of the present invention is inferior to scratch resistance, solvent rubbing test and glycerin test.
  • the curing rate of the resin composition was slow, and therefore the line speed was slow.
  • the obtained laminate was inferior to any of scratch resistance, stain resistance, bending resistance, appearance, solvent rubbing test, glycerin test, and scratch resistance test.
  • Example 23 In Example 12, as a thermoplastic resin film (3), SET329 FZ26401 (trade name, cyclohexanedimethanol copolymerized polyethylene terephthalate (PETG resin) film manufactured by Riken Technos Co., Ltd., thickness 100 ⁇ m, surface JIS-7105-1981 A laminate was manufactured and evaluated in the same manner as in Example 12 except that a 60 ° gloss (measured in accordance with 90%) and not subjected to anchor coating treatment was used. The results are shown in Table 4.
  • PETG resin cyclohexanedimethanol copolymerized polyethylene terephthalate
  • Reference example 2 A laminate was produced in the same manner as in Example 23 except that methyl ethyl ketone was used as the component (D). However, the thermoplastic resin film (3) swelled and a laminate could not be obtained.
  • thermoplastic resin film (3) is an unstretched polyester film
  • methyl ethyl ketone is used as the solvent (D)
  • the thermoplastic resin film (3) swells to obtain a laminate.
  • D methyl ethyl ketone
  • the thermoplastic resin film (3) does not swell and the thermoplastic resin film (3 It was possible to obtain a laminate without reducing the gloss of *
  • Example 25 70 parts by weight of component (A-1) as component (A) 30 parts by mass of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., number of hydroxyl groups per unit amount: 0.63 mol / kg) (A-4) as component (A ′) Coronate HX (trade name, polyisocyanate of the above formula (6)) (B-1) 22 parts by mass as a component (B) manufactured by Nippon Polyurethane Industry Co., Ltd. 5 parts by mass of benzophenone (C-1) as component (C) Ciba Japan Co., Ltd.
  • Darocur 1173 (trade name, alkylphenone photopolymerization initiator, 2-hydroxy-2-methyl-1-phenyl-propan-1-one) (C-2) 2 parts by mass, 8 parts by mass of high-purity colloidal silica (F-1) having an average particle diameter of 80 nm as component (F) and 200 parts by mass of 1-methoxy-2-propanol (D-1) as component (D) were stirred.
  • F-1 high-purity colloidal silica
  • D-1 1-methoxy-2-propanol
  • the number of isocyanate groups per unit amount of component (B-1) was 5.12 mol / kg as measured by the method described above.
  • thermoplastic resin film (3) A biaxially stretched polyester film “Embret S25” (trade name, thickness 25 ⁇ m) manufactured by Unitika Ltd. is used as the thermoplastic resin film (3), and an anchor coating agent (byron 24SS (trade name) manufactured by Toyobo Co., Ltd.) is used on one side thereof. ) was applied to a dry film thickness of 1 ⁇ m to obtain a thermoplastic resin film (3) having an anchor coat (2) on one side.
  • the process of applying the resin composition obtained above on the anchor coat (2), drying, irradiating with ultraviolet rays, and winding the obtained laminate on a roll is a series of production lines, 50 m / min line Performed continuously at speed. The roll could be wound well without using a separator.
  • the resin composition was applied using a film Mayer bar type coating apparatus so that the coating thickness after drying was 11 ⁇ m.
  • the line speed in an Example and a comparative example is the fastest speed which can manufacture a laminated body stably in a production line.
  • the obtained laminates were subjected to the above tests (1) to (7) and the following test (11). The results are shown in Table 5.
  • Example 26 As a component (B), Sumidur HT of Sumika Bayer Urethane Co., Ltd. (trade name, polyisocyanate of the above formula (7), number of isocyanate groups per unit amount: 3.10 mol / kg) (B-2) was used in the same manner as in Example 25 except that 36 was used in an amount of 36 parts by mass. The results are shown in Table 5.
  • Examples 27-30 and Comparative Examples 14-15 A laminate was produced in the same manner as in Example 25 except that the amount of component (B) in Example 25 was changed as shown in Table 5. The results are shown in Table 5.
  • Example 31 In Example 25, 100 parts by mass of the component (A-1) as the component (A), 25 parts by mass of the component (B-1) as the component (B), and 7 parts by mass of the component (C-1) as the component (C). A laminate was produced in the same manner as in Example 25 except that it was used. The results are shown in Table 6.
  • Example 31 except that 100 parts by mass of the component (A-2) obtained in Synthesis Example 2 was used instead of the component (A-1), and 35 parts by mass of the component (B-1) was used as the component (B).
  • a laminate was manufactured in the same manner as in Example 31.
  • the line speed at this time was 50 m / min as in Example 31, but a separator was required for winding on the roll. The results are shown in Table 6.
  • Example 31 instead of component (A-1), tripropylene glycol diacrylate (manufactured by Daicel-Cytec, number of hydroxyl groups per unit amount: 0 mol / kg) (A-3) was used.
  • C is an alkylphenone photopolymerization initiator (Darocur 1173 (trade name), 2-hydroxy-2-methyl-1-phenyl-propan-1-one) (C-2) from Ciba Japan Co., Ltd.
  • a laminate was produced in the same manner as in Example 31 except that it was used in an amount of 5 parts by mass. The line speed at this time was 30 m / min.
  • Example 31 instead of component (A-1), dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., number of hydroxyl groups per unit amount: 0.63 mol / kg) (A-4) was used. In addition, a laminate was manufactured in the same manner as in Example 31 except that the amount of the component (B) was changed so that the ratio (a / b) was 0.85. The results are shown in Table 6. The above (A-4) does not have a hydroxyl group in structure, but a hydroxyl group exists because it contains a component in which a part of the acryloyloxy group is hydrolyzed. The same applies to (A-5) in Comparative Example 19 below.
  • Example 31 instead of component (A-1), ditrimethylolpropane tetraacrylate (manufactured by Nippon Kayaku Co., Ltd., number of hydroxyl groups per unit amount: 0.35 mol / kg) (A-5) was used. In addition, a laminate was manufactured in the same manner as in Example 31 except that the amount of the component (B) was changed so that the ratio (a / b) was 0.85. The results are shown in Table 6.
  • Example 32 In Example 31, a laminate was produced in the same manner as in Example 31 except that the thickness of the coating film was 2 ⁇ m. The line speed at this time was 40 m / min. The reason why the line speed is slower than in Example 31 is that when the coating film is thin, the influence of oxygen radicals reaches the inside of the coating film, and as a result, the curing speed of the entire coating film becomes slow. The results are shown in Table 6.
  • Example 33 In Example 31, a laminate was produced in the same manner as in Example 31 except that the coating thickness was 50 ⁇ m. The line speed at this time was 50 m / min. The results are shown in Table 6.
  • Example 34 A laminate was produced in the same manner as in Example 31 except that methyl ethyl ketone (D-2) was used as the component (D) in Example 31. The results are shown in Table 6.
  • Example 38 A laminate was produced in the same manner as in Example 36 except that high-purity colloidal silica (F-2) having an average particle diameter of 20 nm was used as the component (F). The results are shown in Table 7.
  • Example 39 A laminate was produced in the same manner as in Example 36, except that high-purity colloidal silica (F-3) having an average particle diameter of 150 nm was used as the component (F). The results are shown in Table 7.
  • Example 40 A laminate was produced in the same manner as in Example 36 except that high-purity colloidal silica (F-4) having an average particle diameter of 250 nm was used as the component (F). The results are shown in Table 7.
  • Reference Example 5 A laminate was produced in the same manner as in Example 36 except that high-purity colloidal silica (F-5) having an average particle diameter of 400 nm was used as the component (F). The results are shown in Table 7.
  • Example 41 a laminate was produced in the same manner except that the amounts of component (A) and component (B) were changed to the amounts shown in Table 8.
  • the line speed at this time was 50 m / min. The results are shown in Table 8.
  • Example 43 A laminate was produced in the same manner as in Example 42 except that 0.5 part by mass of MegaFac RS-75 (trade name) (E-1) manufactured by DIC Corporation was used as the component (E). The line speed at this time was 50 m / min. The results are shown in Table 8.
  • Example 44 A laminate was produced in the same manner as in Example 43, except that the amount of component (E-1) was changed to 2.0 parts by mass. The line speed at this time was 50 m / min. The results are shown in Table 8.
  • Test method (11) Haze According to JIS K 7105, the coating film (1) side of the laminate was measured as the incident surface.
  • the composition of the present invention can produce a laminate having a coating film comprising the composition at a high line speed, and the coating film has scratch resistance, Excellent contamination, bending resistance, appearance and transparency.
  • the compositions of Comparative Examples 14 and 15 whose ratio (a / b) is outside the scope of the present invention are inferior in any of the scratch resistance, stain resistance and bending resistance of the resulting coating film.
  • the composition of Comparative Example 16 using a component (A) having a smaller number of (meth) acryloyloxy groups than the range of the present invention is inferior in scratch resistance and stain resistance of the resulting coating film.
  • compositions of Comparative Examples 17 to 19 using only those having no ethanolamine residue as the component (A) had a slow curing speed and therefore a slow line speed. Further, the obtained coating film was inferior in any of scratch resistance, stain resistance, bending resistance and appearance.
  • the pencil hardness is insufficient.
  • Reference Example 4 in which the amount of component (F) is greater than the preferred range of the present invention is inferior in bending resistance.
  • Reference Example 5 in which the particle diameter of the component (F) is larger than the preferred range of the present invention is inferior in transparency (haze).
  • Example 45 In Example 31, as the thermoplastic resin film (3), SET329 FZ26401 (trade name, cyclohexanedimethanol copolymerized polyethylene terephthalate (PETG resin) film manufactured by Riken Technos Co., Ltd., thickness 100 ⁇ m, conforming to JIS-7105-1981 on the surface. And a laminate was produced in the same manner as in Example 31 except that the 60 ° gloss (90%) was used and no anchor coat agent was used. The line speed at this time was 50 m / min. The obtained laminates were subjected to the tests (1) to (7). Further, the 60 ° gloss of the surface of the coating film (1) was measured according to JIS-7105-1981. The results are shown in Table 9.
  • PETG resin cyclohexanedimethanol copolymerized polyethylene terephthalate
  • D-1 1-methoxy-2-propanol
  • D-2 methyl ethyl ketone
  • 50 mass ratio
  • Example 45 a laminate was produced in the same manner as in Example 45 except that methyl ethyl ketone (D-2) was used as the component (D).
  • the thermoplastic resin film (3) as a base material was produced. It swelled and a laminate could not be obtained.
  • thermoplastic resin film (3) as the base material is an unstretched amorphous polyester film
  • methyl ethyl ketone is used as the solvent (D)
  • the base film swells and is laminated. A body could not be obtained (Reference Example 6).
  • a solvent containing 1% by mass of 1-methoxy-2-propanol (D-2) is used as the solvent (D)
  • the base film does not swell and the gloss of the base film is not lowered.
  • a laminate was obtained (Examples 45 and 46).
  • Coating film 2 Anchor coat 3: Thermoplastic resin film 4: Adhesive layer 5: Thermoplastic resin film

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  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
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Abstract

La composition selon l'invention comprend (A) un méth)acrylate de polyéther modifié par une éthanolamine spécifique, (B) un polyisocyanate ayant au moins deux groupes isocyanate par molécule et (C) un amorceur de photopolymérisation, le rapport du nombre (a) de groupes hydroxy dans le composant (A) au nombre (b) de groupes isocyanate dans le composant (B) (à savoir, (a/b)) s'inscrivant dans la plage de 0,5 à 1,2.
PCT/JP2012/080777 2012-11-28 2012-11-28 Composition de résine durcissable par des rayons à énergie active WO2014083644A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018172527A (ja) * 2017-03-31 2018-11-08 日揮触媒化成株式会社 透明被膜形成用塗布液及び透明被膜付基材
EP3158008B1 (fr) 2014-06-23 2019-12-25 Arkema France Oligomères acryles multifonctionnels de structure ramifiée par polyaddition entre amines et acrylates multifonctionnels

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111533884B (zh) * 2020-05-08 2022-03-15 深圳市前海博扬研究院有限公司 一种聚氨酯改性丙烯酸酯uv树脂及其制备方法

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE804019A (fr) * 1972-09-18 1973-12-17 Desoto Inc Produits de reaction d'addition selon michael, non gelifies, durcissable par radiations
US3914165A (en) * 1972-09-18 1975-10-21 Desoto Inc Radiation curable non-gelled michael addition reaction products
US3925349A (en) * 1972-09-18 1975-12-09 Desoto Inc Radiation curable non-gelled michael addition reaction products
EP0280222A2 (fr) * 1987-02-27 1988-08-31 BASF Aktiengesellschaft Produits d'addition à partir d'acrylates et d'amines et leur utilisation dans des masses durcissables par rayons
JPH04318087A (ja) * 1991-04-15 1992-11-09 Fujikura Kasei Co Ltd 光硬化性塗料組成物
JPH0931150A (ja) * 1995-05-15 1997-02-04 Dainippon Ink & Chem Inc ウレタンプレポリマー、活性エネルギー線硬化型水性ポリウレタン樹脂組成物、及びその製造方法
JP2001040247A (ja) * 1999-07-30 2001-02-13 Kansai Paint Co Ltd 硬化性塗料組成物及び塗膜形成法
JP2001207086A (ja) * 2000-01-28 2001-07-31 Riken Vinyl Industry Co Ltd 紫外線硬化性塗料用組成物及びそれを用いた積層体の製造方法
JP2004224834A (ja) * 2003-01-20 2004-08-12 Riken Technos Corp 電離放射線感応型塗料組成物及びそれを用いた積層体

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101792500A (zh) * 2009-10-09 2010-08-04 长兴化学工业股份有限公司 可聚合组合物及包含该可聚合组合物的光学膜

Patent Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE804019A (fr) * 1972-09-18 1973-12-17 Desoto Inc Produits de reaction d'addition selon michael, non gelifies, durcissable par radiations
NL7312860A (fr) * 1972-09-18 1974-03-20
DE2346424A1 (de) * 1972-09-18 1974-04-11 Desoto Inc Strahlungshaertbare, nicht gelierte michael-additionsprodukte
FR2200297A1 (fr) * 1972-09-18 1974-04-19 Desoto Inc
JPS4994736A (fr) * 1972-09-18 1974-09-09
US3844916A (en) * 1972-09-18 1974-10-29 Desoto Inc Radiation curable non-gelled michael addition reaction products
US3914165A (en) * 1972-09-18 1975-10-21 Desoto Inc Radiation curable non-gelled michael addition reaction products
US3925349A (en) * 1972-09-18 1975-12-09 Desoto Inc Radiation curable non-gelled michael addition reaction products
GB1448737A (en) * 1972-09-18 1976-09-08 Desoto Inc Polymerizable compositions
CA1016692A (en) * 1972-09-18 1977-08-30 Desoto Radiation curable non-gelled michael addition reaction products
EP0280222A2 (fr) * 1987-02-27 1988-08-31 BASF Aktiengesellschaft Produits d'addition à partir d'acrylates et d'amines et leur utilisation dans des masses durcissables par rayons
DE3706355A1 (de) * 1987-02-27 1988-09-08 Basf Ag Additionsprodukte aus acrylaten und aminen sowie deren verwendung in strahlungshaertbaren massen
JPS63227553A (ja) * 1987-02-27 1988-09-21 ビーエーエスエフ　アクチェンゲゼルシャフト アクリラート及びアミンから形成される付加生成物ならびに照射線硬可能の材料におけるその用途
JPH04318087A (ja) * 1991-04-15 1992-11-09 Fujikura Kasei Co Ltd 光硬化性塗料組成物
JPH0931150A (ja) * 1995-05-15 1997-02-04 Dainippon Ink & Chem Inc ウレタンプレポリマー、活性エネルギー線硬化型水性ポリウレタン樹脂組成物、及びその製造方法
JP2001040247A (ja) * 1999-07-30 2001-02-13 Kansai Paint Co Ltd 硬化性塗料組成物及び塗膜形成法
JP2001207086A (ja) * 2000-01-28 2001-07-31 Riken Vinyl Industry Co Ltd 紫外線硬化性塗料用組成物及びそれを用いた積層体の製造方法
JP2004224834A (ja) * 2003-01-20 2004-08-12 Riken Technos Corp 電離放射線感応型塗料組成物及びそれを用いた積層体

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3158008B1 (fr) 2014-06-23 2019-12-25 Arkema France Oligomères acryles multifonctionnels de structure ramifiée par polyaddition entre amines et acrylates multifonctionnels
EP3158008B2 (fr) † 2014-06-23 2023-05-17 Arkema France Oligomères acryles multifonctionnels de structure ramifiée par polyaddition entre amines et acrylates multifonctionnels
JP2018172527A (ja) * 2017-03-31 2018-11-08 日揮触媒化成株式会社 透明被膜形成用塗布液及び透明被膜付基材
JP6990521B2 (ja) 2017-03-31 2022-01-12 日揮触媒化成株式会社 透明被膜形成用塗布液及び透明被膜付基材

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