[go: up one dir, main page]

WO2018038101A1 - Composition de résine, couche de résine non durcie, film de résine et son procédé de production, et procédé de production de stratifié - Google Patents

Composition de résine, couche de résine non durcie, film de résine et son procédé de production, et procédé de production de stratifié Download PDF

Info

Publication number
WO2018038101A1
WO2018038101A1 PCT/JP2017/029932 JP2017029932W WO2018038101A1 WO 2018038101 A1 WO2018038101 A1 WO 2018038101A1 JP 2017029932 W JP2017029932 W JP 2017029932W WO 2018038101 A1 WO2018038101 A1 WO 2018038101A1
Authority
WO
WIPO (PCT)
Prior art keywords
meth
acrylate
resin layer
resin
dendrimer
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2017/029932
Other languages
English (en)
Japanese (ja)
Inventor
矢嶋英一
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Panac Co Ltd
Original Assignee
Panac Co Ltd
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 Panac Co Ltd filed Critical Panac Co Ltd
Priority to JP2018535695A priority Critical patent/JPWO2018038101A1/ja
Publication of WO2018038101A1 publication Critical patent/WO2018038101A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
    • B29C41/08—Coating a former, core or other substrate by spraying or fluidisation, e.g. spraying powder
    • B29C41/10—Coating a former, core or other substrate by spraying or fluidisation, e.g. spraying powder by fluidisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/12—Polymers provided for in subclasses C08C or C08F
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • 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
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • 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
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00

Definitions

  • the present invention relates to a resin composition, an uncured resin layer, a resin film, a manufacturing method thereof, and a manufacturing method of a laminate.
  • a method of producing a plastic molded product by providing a hard coat layer on the surface there are insert molding and vacuum molding.
  • insert molding a film with a hard coat layer is loaded into a mold, molten resin is injected into a cavity, the film and resin are integrated, and a plastic with a hard coat layer provided on the surface A molded product is obtained.
  • vacuum forming heat is applied to the film on which the hard coat layer is formed to soften it, and then the film is pressed against the mold of the desired shape, and the film is brought into close contact by sucking out the air between the film and the mold.
  • This is a molding method for producing a film having a desired shape.
  • the hard coat layer has been changed from a thermosetting type to an ultraviolet curing type.
  • molding is an uncured state which can be ultraviolet-cured, and the after-curing type which UV-irradiates after shaping
  • a hard coat layer having a specific function is provided.
  • the after cure type is advantageous for stretchability because it is molded before UV irradiation, and a hard coat layer having a high hardness inherent to the hard coat can be obtained after UV irradiation.
  • Patent Document 1 proposes an insert molding film having a hard coat layer formed of an active energy ray-curable resin composition containing a polyfunctional oligomer having a dendrimer structure at a specific ratio.
  • Patent Document 2 proposes a decorative sheet having a hard coat layer formed from an ink composition containing a specific acrylic polymer, an acrylic monomer, and reactive inorganic particles.
  • Patent Document 1 does not specifically evaluate the tack-free property.
  • Patent Document 2 a specific acrylic monomer is used in the ink composition for forming the hard coat layer.
  • the ratio of the acrylic monomer is large, there is a concern that the curing shrinkage is increased during after-curing. .
  • problems such as cracking are likely to occur.
  • the present invention has been made in view of the above, and is an uncured resin layer that has no stickiness on the surface before curing and is excellent in blocking resistance and stretchability, and has surface hardness and scratch resistance after curing. It aims at providing the uncured resin layer which can be set as the cured resin layer with favorable property. Moreover, it aims at providing the manufacturing method of the resin film which has the said unhardened resin layer, its manufacturing method, and a laminated body. Furthermore, it aims at providing the resin composition which can form the above uncured resin layers.
  • a resin composition comprising a dendrimer-type polyfunctional (meth) acrylate having a dendrimer structure, a reactive (meth) acrylate having a weight average molecular weight of 1,000 to 120,000, and surface-modified inorganic particles.
  • An uncured resin layer comprising a dendrimer-type polyfunctional (meth) acrylate having a dendrimer structure, a reactive (meth) acrylate having a weight average molecular weight of 1,000 to 120,000, and surface-modified inorganic particles.
  • a coating film comprising a dendrimer-type polyfunctional (meth) acrylate having a dendrimer structure, a reactive (meth) acrylate having a weight average molecular weight of 1,000 to 120,000, and surface-modified inorganic particles is formed on a plastic substrate.
  • a resin film comprising: a coating film forming step to be formed on the substrate; and a non-cured resin layer forming step in which the coating film on the plastic substrate is subjected to a drying treatment at a room temperature to 150 ° C. to form an uncured resin layer.
  • a transfer molding step in which the resin film according to [3] is heated and softened, is brought into close contact with a predetermined shape mold, and the shape of the predetermined shape mold is transferred onto the surface of the resin film,
  • An active energy ray curing step for sequentially curing the resin film after the transfer molding treatment by irradiating active energy rays.
  • an uncured resin layer having no surface stickiness before curing, excellent blocking resistance and stretchability, and after curing, a cured resin layer having good surface hardness and scratch resistance is an uncured resin layer that can be provided.
  • An uncured resin layer that can be provided can be provided.
  • the resin film which has the said uncured resin layer, its manufacturing method, and the manufacturing method of a laminated body can be provided.
  • the resin composition which can form the above uncured resin layers can be provided.
  • (meth) acryl includes both “methacryl” and “acryl”. Furthermore, “(meth) acrylate” includes both “methacrylate” and “acrylate”.
  • Resin Composition One aspect of the resin composition of the present invention includes a dendrimer-type polyfunctional (meth) acrylate having a dendrimer structure, a reactive (meth) acrylate having a weight average molecular weight of 1,000 to 120,000, and Contains surface-modified inorganic particles.
  • the dendrimer type polyfunctional (meth) acrylate can achieve both good surface hardness and crack resistance. Moreover, tack-free property and blocking resistance can be mainly imparted by reactive (meth) acrylate. Furthermore, the surface-modified inorganic particles can mainly improve tack-free properties and surface hardness. In one embodiment of the present invention, the mixing of three components of dendrimer-type polyfunctional (meth) acrylate, reactive (meth) acrylate, and surface-modified inorganic particles exhibits different effects and synergistic effects from the case where each is independent. To do.
  • Dendrimer-type polyfunctional (meth) acrylate having a dendrimer structure Dendrimer-type polyfunctional (meth) acrylate is a resin in which an acrylic group is arranged on a branch part (branch molecule) of a dendrimer (including a hyperbranched polymer).
  • the density of the acrylic group is high, the curing rate can be improved.
  • the Van del Waals distance between the branch molecules is shorter than that of a normal molecule, the gap between the (meth) acrylic distance before curing and the bonding distance after curing is reduced, and the curing shrinkage unique to (meth) acrylic Can be reduced.
  • the dendrimer type polyfunctional (meth) acrylate is preferably represented by the following formula (1).
  • R a is a hydrogen atom, an acryloyl group, or a methacryloyl group
  • R c is either a structure represented by the following formula (1-1) or the following formula (1-2). Not all R a are hydrogen atoms.
  • R a has the same meaning as R a in formula (1), R d represents a structure represented by formula (1-1).
  • the weight average molecular weight of the dendrimer type polyfunctional (meth) acrylate is preferably 1,000 to 100,000, more preferably 10,000 to 30,000, and 16,000 to 20,000. More preferably.
  • the weight average molecular weight is 1,000 to 100,000, the surface hardness and the crack resistance can be more balanced.
  • the intermolecular distance of the cross-linked portion is small and the curing shrinkage is small, so that cracks are unlikely to occur.
  • the (meth) acryl equivalent of the dendrimer type polyfunctional (meth) acrylate is preferably 80 to 250 g / eq, more preferably 100 to 200 g / eq. By being 80 to 250 g / eq, good tack-free properties and reactivity can be maintained.
  • the compounds having the structure of the formula (1) are trade names of Biscote # 1000 (Osaka Organic Chemical Co., Ltd.), SIRIUS-501 (Osaka Organic Chemical Co., Ltd.), A-HBR-5 (Shin Nakamura). Chemical Co., Ltd.), New Frontier R-1150 (Daiichi Kogyo Seiyaku Co., Ltd.), SN-2301 (Sartomer Co., Ltd.) and the like.
  • SIRIUS-501 has dipentaerythritol as a core, and is mainly composed of a multi-branched (dipentaerythritol hexaacrylate (DPHA) -linked) polyacrylate having an acrylate group at the terminal.
  • DPHA dipentaerythritol hexaacrylate
  • Reactive (meth) acrylate having a weight average molecular weight of 1,000 to 120,000
  • (meth) acrylic acid ester is an essential component, and if necessary, (meth) It can be easily produced by copolymerizing a carboxylic acid group-containing monomer such as acrylic acid, itaconic acid or maleic anhydride, a urethane polymer or a urethane oligomer.
  • (meth) acrylic acid esters examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and tert-butyl.
  • (Meth) acrylate lauryl (meth) acrylate, stearyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cyclododecyl (meth) acrylate, isobornyl (meth) acrylate And dicyclopentanyl methacrylate.
  • a reactive thermoplastic resin is preferable.
  • organic solvents include alcohol solvents such as methanol, ethanol, isopropyl alcohol and butanol, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate and butyl acetate, methyl cellosolve and ethyl cellosolve.
  • alcohol solvents such as methanol, ethanol, isopropyl alcohol and butanol
  • ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone
  • ester solvents such as ethyl acetate and butyl acetate, methyl cellosolve and ethyl cellosolve.
  • Ether solvents such as toluene, hydrocarbon solvents such as toluene, hexane and cyclohexane, organic solvents such as tetrahydrofuran and mixed solvents thereof can be used, but in consideration of dissolution of thermoplastic resin, ketones, esters, ethers System solvents are preferred.
  • the reactive (meth) acrylate is not particularly limited as long as it is a solid tack-free and reactive (meth) acrylate resin (for example, an acrylate having a functional group reactive on the polymerized main chain in the side chain).
  • the structure includes, for example, (meth) acryl main chain and side chain with (meth) acryloyl group and / or urethane side chain such as urethane oligomer and urethane polymer, urethane main chain and side chain with urethane oligomer Or those having a (meth) acryloyl group on the urethane main chain and side chain.
  • the weight average molecular weight of the reactive (meth) acrylate is less than 1,000 and when it exceeds 120,000, good tack-free property and compatibility are hardly obtained.
  • the weight average molecular weight is preferably 2,000 to 110,000, more preferably 2,000 to 100,000, and further preferably 2,500 to 95,000.
  • a weight average molecular weight can be calculated
  • the (meth) acrylic equivalent of the reactive (meth) acrylate is preferably 200 to 2000 g / eq. By being 200 to 2000 g / eq, good tack-free properties and reactivity can be maintained.
  • “(meth) acrylic equivalent” means the molecular weight per (meth) acryloyl group in the (meth) acrylic resin.
  • the surface-modified inorganic particles have a reactive functional group on the surface of the inorganic particles.
  • the reactive functional group include ethylenically unsaturated bonds such as vinyl group, (meth) acryloyl group, and allyl group, epoxy group, silanol group, and the like.
  • High hardness and scratch resistance (scratch resistance) From the viewpoint of improving the above, a vinyl group, a (meth) acryloyl group, and an allyl group are more preferable.
  • Preferred inorganic particles include metal oxide particles such as silica particles (colloidal silica, fumed silica, precipitated silica, etc.), alumina particles, zirconia particles, titania particles, zinc oxide particles, etc., and high hardness and scratch resistance. From the viewpoint of improving the properties, silica particles and alumina particles are preferable, and silica particles are more preferable.
  • the shape of the inorganic particles examples include a sphere, an ellipsoid, a polyhedron, a scale shape, and the like, and these shapes are preferably uniform and sized.
  • the average particle diameter of the inorganic particles can be appropriately selected depending on the thickness of the layer to be formed, but is preferably 0.005 to 0.5 ⁇ m, more preferably 0.01 to 0.1 ⁇ m, and More preferably, the thickness is 01 to 0.03 ⁇ m.
  • the average particle diameter is a 50% particle diameter (d50: median diameter) when the particles in the solution are measured by a dynamic light scattering method and the particle diameter distribution is expressed as a cumulative distribution, and is laser diffraction / scattering. It can be measured using the method.
  • the surface-modified inorganic particles can be obtained, for example, by decorating the surface with a silane coupling agent.
  • a silane coupling agent examples include known silane coupling agents having a (meth) acryloyl group, an alkoxy group, an amino group, a vinyl group, an epoxy group, a mercapto group, a chloro group, and the like.
  • octenyl Trimethoxysilane glycidoxyoctyltrimethoxysilane, methacryloxyoctyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -methacryloxypropylmethyldimethoxysilane, ⁇ -methacryloxypropyl Dimethylmethoxysilane, ⁇ -methacryloxypropyltriethoxysilane, ⁇ -methacryloxypropyldimethylethoxysilane, ⁇ -acryloxypropyltrimethoxysilane, ⁇ -acryloxypropylmethyldimethoxysilane, ⁇ -a Liloxypropyldimethylmethoxysilane, ⁇ -acryloxypropyltriethoxysilane, ⁇ -acryloxypropylmethyldiethoxysilane, ⁇ -acryloxypropy
  • the method of decorating the surface of the inorganic particles with the silane coupling agent is not particularly limited and may be any known method, such as a dry method of spraying the silane coupling agent or silane coupling after dispersing the inorganic particles in a solvent. Examples thereof include a wet method in which an agent is added and reacted. And among the above-mentioned, as a surface modification inorganic particle, it is preferable that it is a surface modification silica particle from a practical viewpoint.
  • the surface-modified inorganic particles are preferably contained in an amount of 50 to 350 parts by mass with respect to 100 parts by mass in total of the dendrimer type polyfunctional (meth) acrylate (solid content) and the reactive (meth) acrylate (solid content). 100 to 350 parts by mass is more preferable, and 180 to 320 parts by mass is further preferable. By containing 50 to 350 parts by mass, tack-free properties and surface hardness can be further improved.
  • the mass ratio (A: B) of the dendrimer type polyfunctional (meth) acrylate (solid content: A) and the reactive (meth) acrylate (solid content: B) is 1: 7 to 7: 1. Is preferable, and 1: 4 to 3.5: 1 is more preferable. When the ratio is 1: 7 to 7: 1, the surface hardness can be improved without causing curing shrinkage.
  • a hydrogen abstraction type photopolymerization initiator and a cleavage type photopolymerization initiator are used. Although it does not specifically limit as a kind of hydrogen abstraction type photoinitiator, Any one of a benzophenone type compound, a thioxanthone type compound, etc., or these 2 or more types of combinations can be mentioned. Although it does not specifically limit as a kind of cleavage type photoinitiator, Any one of a benzoin ether type compound, a benzyl ketal type compound, an acetophenone type compound, etc., or these 2 or more types of combinations can be mentioned.
  • a photoinitiator is not specifically limited, For example, with respect to a total of 100 mass parts of a dendrimer type polyfunctional (meth) acrylate (solid content) and a reactive (meth) acrylate (solid content), it is 0.00. It is preferable to contain 5 to 10 parts by mass.
  • Leveling agent examples include acrylic leveling agents, silicon leveling agents, fluorine leveling agents, silicon / acrylic copolymer leveling agents, fluorine-modified acrylic leveling agents, fluorine-modified silicon leveling agents, And leveling agents in which functional groups (for example, alkoxy groups such as methoxy group and ethoxy group, acyloxy groups, halogen groups, amino groups, vinyl groups, epoxy groups, methacryloxy groups, acryloxy groups, and isocyanate groups) are introduced. Can be mentioned.
  • the leveling agent is preferably contained in an amount of 0.5 to 6 parts by mass with respect to 100 parts by mass in total of the dendrimer type polyfunctional (meth) acrylate (solid content) and the reactive (meth) acrylate (solid content).
  • an active energy ray-curable monomer and urethane acrylate are added as necessary to provide various functions within the scope of the present invention.
  • Active energy ray curable oligomers such as polyester acrylate and epoxy acrylate
  • active energy ray curable polymers such as acrylic acrylate, antistatic agents, colorants, silicones, plasticizers, antifoaming agents, antioxidants, UV absorbers, Examples thereof include light stabilizers, coupling agents, organic solvents and chelating agents, inorganic fillers and organic fillers for adjusting the refractive index and preventing crosslinking shrinkage, and tack-free resins having no unsaturated double bonds.
  • Uncured resin layer One embodiment of the uncured resin layer of the present invention is a dendrimer-type polyfunctional (meth) acrylate having a dendrimer structure and a reactivity (meth) having a weight average molecular weight of 1,000 to 120,000. Contains acrylate and surface-modified inorganic particles. That is, the uncured resin layer is a dry coating film formed by applying the resin composition according to one embodiment of the present invention to a plastic substrate or the like and drying it.
  • each component contained in the uncured resin layer is, for example, in the case of “dendrimer type polyfunctional (meth) acrylate”, in addition to the dendrimer type polyfunctional (meth) acrylate itself, the dendrimer type polyfunctional (meth) acrylate is It has a dendrimer type polyfunctional (meth) acrylate residue, such as a partially reacted reactant, a reaction product of a dendrimer type polyfunctional (meth) acrylate and another resin (for example, reactive (meth) acrylate). Also included. The same applies to “reactive (meth) acrylate” and includes those having the reactive (meth) acrylate residue in addition to the reactive (meth) acrylate itself.
  • the stretchability can be made mainly good, but the “uncured” in the present invention is a range in which there is no crosslink structure between the respective components or the stretchability is good.
  • a so-called B-stage state is also included.
  • surface hardness for example, pencil hardness
  • active energy rays such as ultraviolet rays or electron beams
  • an uncured state can be obtained by performing a drying treatment at room temperature to 120 ° C. without irradiation with active energy rays.
  • Resin film and production method thereof (1) Resin film One embodiment of the resin film of the present invention has the uncured resin layer described above on a plastic substrate.
  • the thickness of the uncured resin layer is preferably 0.5 to 100 ⁇ m, and more preferably 1 to 20 ⁇ m.
  • plastic base materials include polyolefin resins such as polyethylene and polypropylene; vinyl resins such as polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene / vinyl acetate copolymer, and ethylene / vinyl alcohol copolymer; polyethylene terephthalate, polybutylene Polyester resins such as terephthalate; Acrylic resins such as poly (meth) methyl acrylate and poly (meth) ethyl acrylate; Styrene resins such as polystyrene, acrylonitrile / butadiene / styrene copolymers, cellulose triacetate, cellophane, polycarbonate, Examples include polyurethane-based elastomeric resins; allyl resins such as diethylene glycol bisallyl carbonate, and polysulfide resins.
  • the thickness of the plastic substrate is preferably 25 to 2000 ⁇ m, more preferably 50 to 300 ⁇ m, from the viewpoint of moldability and handleability.
  • mode which concerns on the manufacturing method of the resin film of this invention includes the following process one by one.
  • a coating film comprising a dendrimer-type polyfunctional (meth) acrylate having a dendrimer structure, a reactive (meth) acrylate having a weight average molecular weight of 1,000 to 200,000, and surface-modified inorganic particles is formed on a plastic substrate.
  • Drying is performed at room temperature (for example, 5 to 35 ° C., more specifically about 25 ° C. The same applies to “room temperature” below) to 150 ° C., and the coating film on the plastic substrate is not yet formed.
  • each said process is demonstrated.
  • Coating film forming step A coating film containing a dendrimer type polyfunctional (meth) acrylate, a reactive (meth) acrylate, and surface-modified inorganic particles is first mixed while stirring these three components, and further a photoinitiator, a leveling agent, etc.
  • a resin composition for forming an uncured resin layer is prepared by mixing with an additive.
  • dendrimer type polyfunctional (meth) acrylate, reactive (meth) acrylate, and surface-modified inorganic particles are as described above.
  • an uncured resin layer forming composition is applied onto a plastic substrate to form a coating film.
  • the coating method is not particularly limited, and methods such as dipping, spin coating, bar coating, gravure coating, roll coating, comma coating, die coating, gravure printing, and screen printing can be applied.
  • Uncured resin layer forming step There are no particular restrictions on the drying conditions of the uncured resin layer. After forming a coating film from the viewpoint of the type of substrate film and productivity, for example, a drying process is performed at room temperature to 150 ° C. (preferably 50 to 100 ° C.) in a hot air drying furnace equipped with a rotating fan inside the apparatus. Apply. Thereby, the coating film on the plastic substrate becomes an uncured resin layer.
  • the resin film which concerns on 1 aspect of this invention is manufactured through the above processes.
  • (I) Injection molding process Specifically, the resin film is fed into an injection mold composed of a movable mold and a fixed mold so that the plastic substrate is on the fixed mold side. At this time, the resin films may be fed one by one, or necessary portions of the long resin film may be intermittently fed.
  • the resin film can be heated and softened, preformed so that the resin film follows the shape in the mold, and clamped to adhere to the inner surface of the mold, and then placed.
  • the heating temperature in (ii) is preferably in the range of not less than the glass transition temperature of the plastic substrate and less than the melting temperature (or melting point), and is usually performed at a temperature in the vicinity of the glass transition temperature. In addition, said glass transition temperature vicinity is the range of about glass transition temperature +/- 5 degreeC.
  • vacuum suction may be performed when the resin film is heated and softened with a hot plate for the purpose of bringing the resin film into close contact with the molding die surface.
  • a molding resin (molten resin) is injected into the cavity, cooled and solidified, and the molding resin and the resin film are laminated and integrated.
  • the molding resin to be injected is a thermoplastic resin, it is made into a fluid state by heating and melting, and when it is a thermosetting resin, the uncured liquid composition is appropriately heated and injected in a fluid state, and then cooled. And solidify. Thereby, the resin film is laminated and integrated with the formed resin molded body.
  • the heating temperature of the molding resin is generally about 180 to 280 ° C. depending on the type of the resin.
  • the injection molding resin may be any injection-moldable thermoplastic resin or thermosetting resin (including a two-component curable resin), and various resins can be used.
  • thermoplastic resin materials include polystyrene resins, polyolefin resins, acrylonitrile / butadiene / styrene resins (ABS resins) resins (including heat-resistant ABS resins), acrylonitrile / styrene resins (AS resins), acrylonitrile resins ( AN resin), polyphenylene oxide resins, polycarbonate resins, polyacetal resins, acrylic resins, polyethylene terephthalate resins, polybutylene terephthalate resins, polysulfone resins, polyphenylene sulfide resins, and the like.
  • the thermosetting resin include a two-component reaction curable polyurethane resin and an epoxy resin. These resins may be used alone or in combination of two or more.
  • Active energy ray curing process After the lamination and integration, the molded body is taken out from the mold and subjected to a curing process using an active energy ray (such as an electron beam and an ultraviolet ray). That is, the uncured resin layer is cured with active energy rays to form a laminate in which a cured resin layer is formed.
  • an active energy ray such as an electron beam and an ultraviolet ray
  • the acceleration voltage can be appropriately selected according to the type and thickness of the resin to be used, but usually about 70 to 300 kV is preferable.
  • the irradiation dose is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad).
  • the electron beam source is not particularly limited, and various electron beam accelerators such as a cockroft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, a high frequency type, etc. Can be used.
  • ultraviolet rays When ultraviolet rays are used as the active energy rays, those containing ultraviolet rays having a wavelength of 190 to 380 nm are emitted, and the irradiation dose is about 200 to 1500 mJ / cm 2 .
  • an ultraviolet-ray source For example, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a carbon arc lamp, etc. are used.
  • mode which concerns on the manufacturing method of the laminated body of this invention includes the following process one by one.
  • the heating temperature for heating the resin film is preferably in the range of near or above the glass transition temperature of the plastic substrate and less than the melting temperature (or melting point). Perform at a temperature near the temperature.
  • said glass transition temperature vicinity is the range of about glass transition temperature +/- 5 degreeC.
  • a vacuum molding process for bringing the resin film and the mold into a vacuum state and bringing the resin film into close contact with the mold, and the resin film with the force of compressed air.
  • An example is a compressed air molding process for tightly contacting the mold.
  • the step (ii) is the same as the active energy ray curing step of the above-described “one aspect according to the method for producing a laminate of the present invention”.
  • the pencil hardness of the cured resin layer after curing is preferably F or more, although it varies depending on the material used. More preferably.
  • Laminates manufactured as described above take advantage of their superior properties to make the casing of PCs and home appliances, car interiors, car navigation panels, computer peripherals exteriors, cosmetic and pharmaceutical containers, suitcases It can be used for a wide variety of applications such as housings and plastic lenses.
  • Various functional layers such as an antireflection layer and an antiglare layer can also be provided.
  • Example 1 Preparation of composition for forming uncured resin layer Dendrimer polyfunctional (meth) acrylate (SIRIUS-501, manufactured by Osaka Organic Chemical Industry Co., Ltd., weight average molecular weight: 18,700) in a glass container equipped with a magnetic stirrer.
  • SIRIUS-501 Dendrimer polyfunctional (meth) acrylate
  • the outline of the composition of the composition is shown in Table 1 below.
  • the “ratio of inorganic particles” in Table 1 is the ratio (parts by mass) of (surface modification) inorganic particles to 100 parts by mass in total of dendrimer type polyfunctional (meth) acrylate and reactive (meth) acrylate. The same applies to Tables 2 to 4.
  • Measuring device Orientec Co., Ltd. film strength automatic elongation measuring device
  • Example 2 Except that the ratio of the surface-modified inorganic particles was changed to 44.55 parts by mass in terms of solid content, the formation of the uncured resin layer and its evaluation, and the formation and evaluation of the cured resin layer were conducted in the same manner as in Example 1. went.
  • the composition is shown in Table 1 below, and the evaluation results are shown in Table 5 below.
  • Example 3 Except that the ratio of the surface-modified inorganic particles was changed to 22.5 parts by mass in terms of solid content, the formation of the uncured resin layer and its evaluation, and the formation of the cured resin layer and its evaluation were carried out in the same manner as in Example 1. went.
  • the composition is shown in Table 1 below, and the evaluation results are shown in Table 5 below.
  • Example 4 Except for changing the proportion of the surface-modified inorganic particles to 117.45 parts by mass in terms of solid content, in the same manner as in Example 1, the formation and evaluation of the uncured resin layer and the formation and evaluation of the cured resin layer went.
  • the composition is shown in Table 2 below, and the evaluation results are shown in Table 5 below.
  • Example 5 Formation of an uncured resin layer and its evaluation, in the same manner as in Example 1, except that the reactive (meth) acrylate was changed to 50 parts by mass and the ratio of the surface-modified inorganic particles was changed to 141.75 parts by mass in terms of solid content.
  • the cured resin layer was formed and evaluated.
  • the composition is shown in Table 2 below, and the evaluation results are shown in Table 5 below.
  • Example 6 Reactive (meth) acrylate 50 parts by weight, except that the proportion of the surface-modified inorganic particles was changed to 75.33 parts by weight in terms of solid content, in the same manner as in Example 1, formation of an uncured resin layer and its evaluation, and The cured resin layer was formed and evaluated.
  • the composition is shown in Table 2 below, and the evaluation results are shown in Table 5 below.
  • Example 7 Example 1 except that the reactive (meth) acrylate was changed to Art Resin H-108SC (urethane acrylate, manufactured by Negami Kogyo Co., Ltd., molecular weight: 2800, solid content: 50 mass%, solvent: ethyl acetate).
  • Art Resin H-108SC urethane acrylate, manufactured by Negami Kogyo Co., Ltd., molecular weight: 2800, solid content: 50 mass%, solvent: ethyl acetate.
  • the composition is shown in Table 2 below, and the evaluation results are shown in Table 5 below.
  • Comparative Example 1 Except not adding a dendrimer type polyfunctional (meth) acrylate, it carried out similarly to Example 1, and formed and evaluated the uncured resin layer, and formed and evaluated the cured resin layer.
  • the composition is shown in Table 3 below, and the evaluation results are shown in Table 5 below.
  • Comparative Example 2 Except not adding reactive (meth) acrylate, it carried out similarly to Example 1, and formed and evaluated the uncured resin layer, and formed and evaluated the cured resin layer.
  • the composition is shown in Table 3 below, and the evaluation results are shown in Table 5 below.
  • Example 3 (Comparative Example 3) Except that the surface-modified inorganic particles were not added, the uncured resin layer was formed and evaluated in the same manner as in Example 1, and the cured resin layer was formed and evaluated.
  • the composition is shown in Table 3 below, and the evaluation results are shown in Table 5 below.
  • Comparative Example 5 243 parts by mass of surface-modified inorganic particles, simple silica particles that have not been surface-modified (PGM-ST, Nissan Chemical Industries, Ltd., average particle size: 10-15 nm, solid content: 30% by mass, dispersion medium: PGME) Except having used, it carried out similarly to Example 1, and formed and evaluated the uncured resin layer, and formed and evaluated the cured resin layer.
  • the composition is shown in Table 3 below, and the evaluation results are shown in Table 5 below.
  • Example 8 Example 6 except that the reactive (meth) acrylate was changed to PA-341 (urethane acrylate, manufactured by Negami Kogyo Co., Ltd., weight average molecular weight: 6,480, solid content: 50 mass%, solvent: methyl ethyl ketone) Similarly, formation and evaluation of an uncured resin layer and formation and evaluation of a cured resin layer were performed. The composition is shown in Table 4 below, and the evaluation results are shown in Table 6 below.
  • PA-341 urethane acrylate, manufactured by Negami Kogyo Co., Ltd., weight average molecular weight: 6,480, solid content: 50 mass%, solvent: methyl ethyl ketone
  • Example 9 Example 6 except that the reactive (meth) acrylate was changed to PA-359 (urethane acrylate, manufactured by Negami Kogyo Co., Ltd., weight average molecular weight: 8,304, solid content: 50 mass%, solvent: methyl ethyl ketone). Similarly, formation and evaluation of an uncured resin layer and formation and evaluation of a cured resin layer were performed. The composition is shown in Table 4 below, and the evaluation results are shown in Table 6 below.
  • PA-359 urethane acrylate, manufactured by Negami Kogyo Co., Ltd., weight average molecular weight: 8,304, solid content: 50 mass%, solvent: methyl ethyl ketone
  • Example 10 Example except that reactive (meth) acrylate was changed to 8BR-600 (urethane acrylate, manufactured by Taisei Fine Chemical Co., Ltd., weight average molecular weight: 91,000, solid content: 39% by mass, solvent: methyl isobutyl ketone)
  • 8BR-600 urethane acrylate, manufactured by Taisei Fine Chemical Co., Ltd., weight average molecular weight: 91,000, solid content: 39% by mass, solvent: methyl isobutyl ketone
  • Example 11 The reactive (meth) acrylate was changed to 8BR-930MB (urethane acrylate, manufactured by Taisei Fine Chemical Co., Ltd., weight average molecular weight: 15,000, solid content: 52 mass%, solvent: methyl isobutyl ketone and methyl ethyl ketone)
  • 8BR-930MB urethane acrylate, manufactured by Taisei Fine Chemical Co., Ltd., weight average molecular weight: 15,000, solid content: 52 mass%, solvent: methyl isobutyl ketone and methyl ethyl ketone
  • the uncured resin layers of Examples 1 to 11 according to the present invention all have good tackiness, blocking resistance, and stretchability, and the cured resin layer obtained by curing this also has surface hardness, scratch resistance, Both adhesion and cracking were good.
  • Comparative Examples 1 to 5 it was not possible to satisfy all the evaluation items in the uncured resin layer and the cured resin layer. Moreover, in the comparative example 5, the external appearance of the coating liquid became cloudy white, and it was expected that defects were likely to occur in applications where transparency was required.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Laminated Bodies (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Moulding By Coating Moulds (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne une composition de résine ou équivalents qui comprend un (méth)acrylate multifonctionnel de type dendrimère ayant une structure dendrimère, un (méth)acrylate réactif ayant un poids moléculaire moyen en poids de 1 000 à 120 000, et des particules inorganiques à surface modifiée.
PCT/JP2017/029932 2016-08-24 2017-08-22 Composition de résine, couche de résine non durcie, film de résine et son procédé de production, et procédé de production de stratifié Ceased WO2018038101A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2018535695A JPWO2018038101A1 (ja) 2016-08-24 2017-08-22 樹脂組成物、未硬化樹脂層、樹脂フィルム及びその製造方法、積層体の製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016-163276 2016-08-24
JP2016163276 2016-08-24

Publications (1)

Publication Number Publication Date
WO2018038101A1 true WO2018038101A1 (fr) 2018-03-01

Family

ID=61245024

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2017/029932 Ceased WO2018038101A1 (fr) 2016-08-24 2017-08-22 Composition de résine, couche de résine non durcie, film de résine et son procédé de production, et procédé de production de stratifié

Country Status (2)

Country Link
JP (1) JPWO2018038101A1 (fr)
WO (1) WO2018038101A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109762417A (zh) * 2019-01-04 2019-05-17 东莞市华纬涂装设备有限公司 一种汽车内饰件涂装生产工艺
WO2020031967A1 (fr) * 2018-08-08 2020-02-13 三菱瓦斯化学株式会社 Composition de revêtement dur, film stratifié et film durcissable
WO2020031968A1 (fr) * 2018-08-08 2020-02-13 三菱瓦斯化学株式会社 Stratifié pour moulage
WO2021193809A1 (fr) * 2020-03-26 2021-09-30 三菱瓦斯化学株式会社 Article obtenu par moulage d'insertion de film et procédé de fabrication d'un article moulé par insertion de film
JPWO2022168811A1 (fr) * 2021-02-04 2022-08-11
WO2022168810A1 (fr) * 2021-02-04 2022-08-11 三菱瓦斯化学株式会社 Stratifié et son procédé de production

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0248908A (ja) * 1988-05-30 1990-02-19 Tanazawa Hatsukoushiya:Kk 表面転写方法
WO2009008278A1 (fr) * 2007-07-11 2009-01-15 Kimoto Co., Ltd. Article moulé en résine utilisant un film pour le moulage d'insert
WO2010116821A1 (fr) * 2009-03-30 2010-10-14 株式会社 きもと Composition et stratifié
JP2014077121A (ja) * 2012-09-21 2014-05-01 Nippon Synthetic Chem Ind Co Ltd:The ポリビニルアルコール系フィルム及びその製造方法、並びにポリビニルアルコール系フィルムを用いた熱転写用積層体及びこれを用いた熱転写方法
JP2015071665A (ja) * 2013-10-02 2015-04-16 三菱化学株式会社 硬化性組成物
WO2015198787A1 (fr) * 2014-06-26 2015-12-30 Dic株式会社 Composition de résine durcissant à l'énergie active, matériau de revêtement, film de revêtement et film stratifié
WO2015198788A1 (fr) * 2014-06-26 2015-12-30 Dic株式会社 Composition de résine durcissable par des rayons actiniques, composition de revêtement, film de revêtement et film stratifié
WO2016031931A1 (fr) * 2014-08-29 2016-03-03 住友大阪セメント株式会社 Composition de résine, film de revêtement, film plastique avec film de revêtement, et dispositif d'affichage
WO2016072450A1 (fr) * 2014-11-05 2016-05-12 大日本印刷株式会社 Feuille de transfert et corps de revêtement dur utilisant celle-ci

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0248908A (ja) * 1988-05-30 1990-02-19 Tanazawa Hatsukoushiya:Kk 表面転写方法
WO2009008278A1 (fr) * 2007-07-11 2009-01-15 Kimoto Co., Ltd. Article moulé en résine utilisant un film pour le moulage d'insert
WO2010116821A1 (fr) * 2009-03-30 2010-10-14 株式会社 きもと Composition et stratifié
JP2014077121A (ja) * 2012-09-21 2014-05-01 Nippon Synthetic Chem Ind Co Ltd:The ポリビニルアルコール系フィルム及びその製造方法、並びにポリビニルアルコール系フィルムを用いた熱転写用積層体及びこれを用いた熱転写方法
JP2015071665A (ja) * 2013-10-02 2015-04-16 三菱化学株式会社 硬化性組成物
WO2015198787A1 (fr) * 2014-06-26 2015-12-30 Dic株式会社 Composition de résine durcissant à l'énergie active, matériau de revêtement, film de revêtement et film stratifié
WO2015198788A1 (fr) * 2014-06-26 2015-12-30 Dic株式会社 Composition de résine durcissable par des rayons actiniques, composition de revêtement, film de revêtement et film stratifié
WO2016031931A1 (fr) * 2014-08-29 2016-03-03 住友大阪セメント株式会社 Composition de résine, film de revêtement, film plastique avec film de revêtement, et dispositif d'affichage
WO2016072450A1 (fr) * 2014-11-05 2016-05-12 大日本印刷株式会社 Feuille de transfert et corps de revêtement dur utilisant celle-ci

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7501362B2 (ja) 2018-08-08 2024-06-18 三菱瓦斯化学株式会社 ハードコート組成物、積層体フィルム、及び、硬化フィルム
US20210316542A1 (en) * 2018-08-08 2021-10-14 Mitsubishi Gas Chemical Company, Inc. Laminate for molding
WO2020031968A1 (fr) * 2018-08-08 2020-02-13 三菱瓦斯化学株式会社 Stratifié pour moulage
CN112512800A (zh) * 2018-08-08 2021-03-16 三菱瓦斯化学株式会社 成型用叠层体
CN112534009A (zh) * 2018-08-08 2021-03-19 三菱瓦斯化学株式会社 硬涂层组合物、叠层体膜和固化膜
JPWO2020031968A1 (ja) * 2018-08-08 2021-08-10 三菱瓦斯化学株式会社 成形用積層体
JPWO2020031967A1 (ja) * 2018-08-08 2021-08-26 三菱瓦斯化学株式会社 ハードコート組成物、積層体フィルム、及び、硬化フィルム
CN112512800B (zh) * 2018-08-08 2023-06-09 三菱瓦斯化学株式会社 成型用叠层体
WO2020031967A1 (fr) * 2018-08-08 2020-02-13 三菱瓦斯化学株式会社 Composition de revêtement dur, film stratifié et film durcissable
US11833792B2 (en) 2018-08-08 2023-12-05 Mitsubishi Gas Chemical Company, Inc. Laminate for molding
US11976208B2 (en) 2018-08-08 2024-05-07 Mitsubishi Gas Chemical Company, Inc. Hard-coat composition, laminate film, and curable film
JP2024113051A (ja) * 2018-08-08 2024-08-21 三菱瓦斯化学株式会社 ハードコート組成物、積層体フィルム、及び、硬化フィルム
JP7347427B2 (ja) 2018-08-08 2023-09-20 三菱瓦斯化学株式会社 成形用積層体
CN109762417A (zh) * 2019-01-04 2019-05-17 东莞市华纬涂装设备有限公司 一种汽车内饰件涂装生产工艺
JPWO2021193809A1 (fr) * 2020-03-26 2021-09-30
EP4129618A4 (fr) * 2020-03-26 2023-09-20 Mitsubishi Gas Chemical Company, Inc. Article obtenu par moulage d'insertion de film et procédé de fabrication d'un article moulé par insertion de film
WO2021193809A1 (fr) * 2020-03-26 2021-09-30 三菱瓦斯化学株式会社 Article obtenu par moulage d'insertion de film et procédé de fabrication d'un article moulé par insertion de film
JPWO2022168811A1 (fr) * 2021-02-04 2022-08-11
JP7273252B2 (ja) 2021-02-04 2023-05-12 三菱瓦斯化学株式会社 積層体及びその製造方法
JP7217388B2 (ja) 2021-02-04 2023-02-02 三菱瓦斯化学株式会社 積層体及びその製造方法
JPWO2022168810A1 (fr) * 2021-02-04 2022-08-11
WO2022168811A1 (fr) * 2021-02-04 2022-08-11 三菱瓦斯化学株式会社 Corps multicouche et son procédé de production
WO2022168810A1 (fr) * 2021-02-04 2022-08-11 三菱瓦斯化学株式会社 Stratifié et son procédé de production

Also Published As

Publication number Publication date
JPWO2018038101A1 (ja) 2019-07-18

Similar Documents

Publication Publication Date Title
WO2018038101A1 (fr) Composition de résine, couche de résine non durcie, film de résine et son procédé de production, et procédé de production de stratifié
JP4952910B2 (ja) 活性エネルギー線硬化性樹脂組成物およびその用途
JP4457324B2 (ja) 成型用ハードコートフィルム
JP5455730B2 (ja) 加飾用ハードコートフィルム、加飾フィルムおよび加飾成形品
JP2019147885A (ja) 樹脂組成物、未硬化樹脂層、樹脂フィルム、樹脂フィルムの製造方法、及び積層体の製造方法
JP2010284910A (ja) 加飾用ハードコートフィルム、加飾フィルムおよび加飾成形品
JP2013173871A (ja) 組成物、帯電防止性コート剤及び帯電防止性積層体
JP4678561B2 (ja) 硬化性樹脂組成物
JP5659539B2 (ja) インキ組成物及びこれを用いた加飾シート
JP6486412B2 (ja) 転写用離型フィルム及びマット状成形体の製造方法
JP5824725B2 (ja) 活性エネルギー線硬化型樹脂組成物
JP5556211B2 (ja) 加飾成形品の製造方法
JP4293886B2 (ja) 光硬化性樹脂組成物並びにそれを用いた光硬化性シート及びそれを用いた成形品の製造方法
JP2022143895A (ja) 塗料組成物、半硬化膜、加飾成形品、及び加飾成形品の製造方法
TW201529313A (zh) 轉印用裝飾膜
KR101252340B1 (ko) 하드코팅액 조성물 및 하드 코팅 필름
JP5659538B2 (ja) インキ組成物及びこれを用いた加飾シート
JP2015038173A (ja) 光硬化性樹脂組成物、積層シート、積層成形品及び積層成形品の製造方法
JP4933801B2 (ja) 表面微細凹凸構造を有する成形品およびその製造方法
JP6233691B2 (ja) 樹脂組成物、これを含有する活性エネルギー線硬化性ハードコート剤、加飾フィルム
JP2006212987A (ja) 転写材
JP2022055398A (ja) アフターキュア型成形用反射防止ハードコートフィルム
JP7108390B2 (ja) 硬化性樹脂組成物
JP2011194756A (ja) 加飾用ハードコートフィルム、加飾フィルムおよび加飾成形品
JP2012021060A (ja) インキ組成物及びこれを用いた加飾シート

Legal Events

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

Ref document number: 17843580

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2018535695

Country of ref document: JP

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: 17843580

Country of ref document: EP

Kind code of ref document: A1