WO2012063637A1 - Film de couche dure multicouche pour moulage par injection, procédé pour produire celui-ci, et procédé pour produire un objet moulé par injection en utilisant le film de couche dure multicouche - Google Patents

Film de couche dure multicouche pour moulage par injection, procédé pour produire celui-ci, et procédé pour produire un objet moulé par injection en utilisant le film de couche dure multicouche Download PDF

Info

Publication number
WO2012063637A1
WO2012063637A1 PCT/JP2011/074504 JP2011074504W WO2012063637A1 WO 2012063637 A1 WO2012063637 A1 WO 2012063637A1 JP 2011074504 W JP2011074504 W JP 2011074504W WO 2012063637 A1 WO2012063637 A1 WO 2012063637A1
Authority
WO
WIPO (PCT)
Prior art keywords
hard coat
injection
resin
group
layer
Prior art date
Application number
PCT/JP2011/074504
Other languages
English (en)
Japanese (ja)
Inventor
裕明 山田
禎寿 後藤
敬一 林
Original Assignee
新日鐵化学株式会社
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
Priority claimed from JP2011220236A external-priority patent/JP5735394B2/ja
Priority claimed from JP2011220237A external-priority patent/JP5794883B2/ja
Application filed by 新日鐵化学株式会社 filed Critical 新日鐵化学株式会社
Priority to KR1020137014529A priority Critical patent/KR101902492B1/ko
Priority to CN201180054153.9A priority patent/CN103201080B/zh
Publication of WO2012063637A1 publication Critical patent/WO2012063637A1/fr

Links

Images

Classifications

    • 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
    • B29C45/14778—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 the article consisting of a material with particular properties, e.g. porous, brittle
    • B29C45/14811—Multilayered 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
    • B32B27/06—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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2633/00—Use of polymers of unsaturated acids or derivatives thereof for preformed parts, e.g. for inserts
    • B29K2633/04—Polymers of esters
    • B29K2633/12—Polymers of methacrylic acid esters, e.g. PMMA, i.e. polymethylmethacrylate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2667/00—Use of polyesters or derivatives thereof for preformed parts, e.g. for inserts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2669/00—Use of PC, i.e. polycarbonates or derivatives thereof for preformed parts, e.g. for inserts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/007—Hardness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2009/00—Layered products
    • B29L2009/005—Layered products coated
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating

Definitions

  • the present invention relates to a hard coat film laminate for injection molding, a method for producing the same, and a method for producing an injection molded article using the hard coat film laminate, for example, windows for automobiles, aircraft, buildings, schools, shops, etc.
  • a hard coat film laminate for injection molding necessary for the production of a molded article of PET (polyethylene terephthalate) resin, a method for producing the same, and a method for producing an injection molded article using the same.
  • thermoplastic resins such as polycarbonate have been widely used as alternative materials because of their lighter weight than glass or metal.
  • polycarbonate resin has a lower surface hardness than glass and is easily scratched. To prevent this, the surface is protected by applying paint or pasting a curable film on it. Yes.
  • Patent Document 1 discloses a base material layer made of a mixed resin composition containing a polycarbonate resin and a polyester resin, and an ultraviolet curable resin composition containing an acrylic polymer.
  • An invention relating to a hard coat film for injection molding provided with a hard coat layer made of a cured product is described.
  • Patent Document 2 discloses that a curable coating agent is applied to a resin film, the coating agent is semi-cured, and then mounted in a mold to obtain a polycarbonate resin.
  • Patent Document 2 An invention relating to a method for producing a polycarbonate resin molded article obtained by injection molding, peeling off a resin film, and further curing the coating agent to cure the surface is described.
  • a silicone coating agent obtained by adding colloidal silica to an organosilane having a structure of R n Si (OH) 4-n and an acrylic coating agent are mentioned as preferable ones.
  • acrylic and silicone coating agents that have been used mainly as hard coats to protect the surface of injection-molded resin until now are not sufficient in terms of scratch resistance.
  • the surface hardness can be fully expressed, but the adhesiveness to injection molded products is excellent, and at the same time, the ability to follow the mold is satisfied. There is a further need for such a hard coat film laminate.
  • the present invention has been made in order to solve the above-described problems, and has a very high surface hardness as a hard coat of a molded article of polycarbonate resin, PMMA resin, or PET resin.
  • An object of the present invention is to provide a hard coat film laminate for injection molding that is excellent in followability.
  • an object of this invention is to provide the method of manufacturing such a hard coat film laminated body for injection molding.
  • this invention aims at providing the manufacturing method of the injection molded object using this hard coat film laminated body.
  • a photocurable resin composition containing a photocurable siliceous silsesquioxane resin is cured to form a hard coat layer.
  • a base material layer containing at least one of polycarbonate, polymethyl methacrylate, or polyethylene terephthalate By stacking and integrating with a base material layer containing at least one of polycarbonate, polymethyl methacrylate, or polyethylene terephthalate, and mounting it in a mold, a molded product of polycarbonate resin, PMMA resin, or PET resin It has been found that a hard coat having a high surface hardness can be formed on the surface with a good adhesion through a base material layer, and that the following property to the mold can be satisfied, and the present invention has been completed.
  • the gist of the present invention is as follows.
  • a single layer of a resin selected from the group consisting of polycarbonate, polymethyl methacrylate, and polyethylene terephthalate, or a base layer composed of two or more layers, and a single layer laminated on one side of the base layer A hard coat film laminate for injection molding comprising a hard coat layer, wherein the hard coat layer comprises a photocurable resin composition containing a photo-curing cage silsesquioxane resin.
  • a hard coat film laminate for injection molding characterized by being cured and having a thickness of 20 ⁇ m or more, a transmittance at a wavelength of 550 nm of 90% or more, and a glass transition temperature of 230 ° C. or more.
  • the cage silsesquioxane resin has the following general formula (1): RSix 3 (1)
  • R shows the organic functional group or vinyl group which has a (meth) acryloyl group
  • X shows the hydrolysis group chosen from an alkoxy group or an acetoxy group.
  • the silicon compound is hydrolyzed and partially condensed, and the obtained hydrolysis product is further recondensed in the presence of a nonpolar solvent and a basic catalyst.
  • the cage silsesquioxane resin is represented by the following general formula (2): [RSiO 3/2 ] n (2) [In Formula (2), R shows the organic functional group or vinyl group which has a (meth) acryloyl group, and n shows 8, 10, 12, or 14.
  • R shows the organic functional group or vinyl group which has a (meth) acryloyl group
  • n shows 8, 10, 12, or 14.
  • R is the following general formula (3): [In the formula (3), R 1 represents a hydrogen atom or a methyl group, and m represents an integer of 1 to 3.
  • R 1 represents a hydrogen atom or a methyl group
  • m represents an integer of 1 to 3.
  • a single layer of one type of resin selected from the group consisting of polycarbonate, polymethyl methacrylate, and polyethylene terephthalate, or a base layer composed of two or more types and a hard coat layer were laminated and integrated.
  • a method for producing a hard coat film laminate for injection molding wherein a photocurable resin composition containing a photocurable siliceous silsesquioxane resin is applied to one side of a base material layer and cured.
  • a hard coat film for injection molding characterized by forming a hard coat layer having a thickness of 20 ⁇ m or more, a transmittance of 90% or more at a wavelength of 550 nm, and a glass transition temperature of 230 ° C. or more A manufacturing method of a layered product.
  • the hard coat film laminate for injection molding provided with the hard coat layer formed is placed in an injection mold, and in that state, one of polycarbonate, polymethyl methacrylate, or polyethylene terephthalate is injected into the mold
  • the hard coat layer is formed by curing a photocurable resin composition containing a photocurable siliceous silsesquioxane resin and has a thickness of 20 ⁇ m or more, and has a transmittance of 90% at a wavelength of 550 nm.
  • the cage silsesquioxane resin has the following general formula (1): RSix 3 (1)
  • R shows the organic functional group or vinyl group which has a (meth) acryloyl group
  • X shows the hydrolysis group chosen from an alkoxy group or an acetoxy group.
  • the silicon compound is hydrolyzed and partially condensed, and the obtained hydrolysis product is further recondensed in the presence of a nonpolar solvent and a basic catalyst.
  • the method for producing an injection-molded article according to [9] which is obtained.
  • the cage silsesquioxane resin is represented by the following general formula (2): [RSiO 3/2 ] n (2)
  • R shows the organic functional group or vinyl group which has a (meth) acryloyl group
  • n shows 8, 10, 12, or 14.
  • R is the following general formula (3): [In the formula (3), R 1 represents a hydrogen atom or a methyl group, and m represents an integer of 1 to 3. The method for producing an injection-molded article according to [10] or [11], wherein the organic functional group is represented by the formula:
  • the hard coat film laminate for injection molding of the present invention forms a hard coat layer from a photocurable resin composition containing a photocurable siliceous silsesquioxane resin.
  • the hard coat layer is formed on the surface of the injection molded product through the base material layer containing one or more of polycarbonate, polymethyl methacrylate, or polyethylene terephthalate, the hard coat layer has excellent adhesion. It is possible to prevent peeling.
  • a hard coat film laminate for injection molding comprising a base material layer containing one or more of polycarbonate, polymethyl methacrylate, or polyethylene terephthalate and a hard coat layer is placed in an injection mold, In this state, by injecting polycarbonate resin, PMMA resin, or PET resin into the mold, resin molding is performed, and at the same time, the hard coat film laminate is integrated with the surface of the resin molded body, so that glass or metal is formed. It is possible to obtain an injection molded body that can be used as an alternative material.
  • a predetermined hard coat layer with a photocurable resin composition containing a photocurable siliceous silsesquioxane resin, it is possible to follow the mold while maintaining sufficient surface hardness. In addition, it is possible to impart high surface hardness to the surface of the injection molded product.
  • the hard coat layer since the hard coat layer is formed on the surface of the injection molded product through the base material layer containing one or more of polycarbonate, polymethyl methacrylate, or polyethylene terephthalate, the hard coat layer has excellent adhesion. While being able to prevent peeling, it is possible to integrate at the same time as the molding at the time of injection molding, and it is excellent in productivity.
  • FIG. 1 is a schematic cross-sectional view showing a hard coat film laminate of the present invention.
  • FIG. 2 is a schematic cross-sectional view showing the state of insert molding using the hard coat film laminate of the present invention.
  • FIG. 3 is a schematic cross-sectional view showing an injection molded body obtained by insert molding.
  • FIG. 4 is a schematic view showing an example of an injection molding machine used in the method for producing an injection molded body of the present invention.
  • FIG. 5 shows the light transmittance of only the hard coat layer in the hard coat film laminate of the present invention.
  • FIG. 6 shows the measurement results of the glass transition temperature of only the hard coat layer in the hard coat film laminate of the present invention.
  • the hard coat film laminate 1 includes a hard coat layer 2 on one side of a single layer of a single resin selected from the group consisting of polycarbonate, PMMA, and PET, or a base layer 4 composed of two or more layers.
  • the cover layer 3 of the plastic film is formed by laminating and integrating.
  • the resin for forming the base material layer is preferably a film-like resin, and preferably one resin film selected from the group consisting of polycarbonate, PMMA, and PET may be used alone as the base material layer.
  • a plurality of layers in which two or more kinds of resin films are laminated may be used as the base material layer.
  • a base material layer composed of a single layer of a polycarbonate film, a PMMA film, or a PET film, or a base material layer in which two polycarbonate films and a PMMA film are bonded together is more preferable.
  • the thickness of the base material layer is preferably in the range of 30 to 300 ⁇ m including the case of a single layer and the case of a plurality of layers. If it is smaller than 30 ⁇ m, the strength as a base material layer is insufficient and there is a risk of breakage. On the contrary, if it is larger than 300 ⁇ m, the followability to the mold shape is deteriorated at the time of injection molding. Further, for each resin of polycarbonate, PMMA, and PET used in the present invention, an ultraviolet absorber, a plasticizer, a pigment, or the like may be used as an additive. In the present invention, the entire thickness of the hard coat film laminate for injection molding is not particularly limited, and preferably has a suitable thickness range described for each layer.
  • the hard coat layer 2 preferably has a thickness of 20 ⁇ m or more by curing a photocurable resin composition containing a photocurable siliceous silsesquioxane resin, and has a glass transition temperature. Is made of a transparent resin layer having a transmittance of not less than 230 ° C. and a transmittance of 90% or more at a wavelength of 550 nm.
  • the thickness of the preferred hard coat layer is 20 ⁇ m or more, preferably in the range of 20 to 400 ⁇ m, and more preferably in the range of 50 to 80 ⁇ m.
  • the thickness is less than 20 ⁇ m, sufficient surface hardness cannot be obtained.
  • the thickness exceeds 400 ⁇ m, flexibility is impaired, and for example, it may be difficult to obtain a molded product having a curved surface. is there.
  • the hard coat film laminate of the present invention is used for window glass of automobiles and aircraft, the surface becomes high temperature by direct sunlight. Further, when used as a housing for a personal computer or a portable electronic device, heat is generated inside the device. Therefore, the hard coat layer needs to have heat resistance to prevent deformation due to heat, and the resin forming the hard coat layer has a glass transition temperature of 230 ° C. or higher, preferably 250 ° C. or higher.
  • the transmittance at a wavelength of 550 nm is preferably 90% or more in a liquid crystal display portion of a window glass of an automobile or an aircraft, a personal computer, or a portable electronic device.
  • content of the said cage silsesquioxane resin in a photocurable resin composition is 3 mass% with respect to the mass of a photocurable resin composition.
  • the amount is preferably in the above range, and more preferably in the range of 5 to 70% by mass.
  • the content is less than 3% by mass, the glass transition temperature of the transparent resin layer tends to be low in the hard coat film laminate for injection molding, and the heat resistance at the mold temperature at the time of injection molding may be insufficient. is there.
  • the content exceeds 70% by mass the toughness of the hard coat layer is impaired, and there is a possibility that appearance defects such as cracks are generated on the surface by handling.
  • the glass transition temperature of the hard coat layer can be adjusted, for example, even when the content of the cage silsesquioxane resin is the same.
  • the glass transition temperature of the transparent resin layer is appropriately adjusted by adjusting the content of the cage silsesquioxane resin, because it varies depending on the glass transition temperature of other resins used in combination with the cage silsesquioxane resin. Can be adjusted.
  • the upper limit of the glass transition temperature of the hard coat layer is about 450 ° C. in consideration of containing an organic substance.
  • the vertical silsesquioxane resin that forms a preferred hard coat layer in the present invention is a vertical silsesquioxane resin having photocurability.
  • cage-type silsesquioxane resins include the following general formula (1): RSix 3 (1)
  • the silicon compound represented by the formula is hydrolyzed in the presence of an organic polar solvent and a basic catalyst and partially condensed, and the resulting hydrolysis product is further recondensed in the presence of a nonpolar solvent and a basic catalyst. Things.
  • R represents an organic functional group having a (meth) acryloyl group or a vinyl group
  • X represents a hydrolysis group such as an alkoxy group or an acetoxy group.
  • such a cage silsesquioxane resin is represented by the following general formula (2): [RSiO 3/2 ] n (2) It is preferable that it is a cage-type silsesquioxane resin represented by these.
  • R represents an organic functional group having a (meth) acryloyl group or a vinyl group
  • n represents 8, 10, 12 or 14.
  • the R is represented by the general formula (3): It is preferable that it is an organic functional group represented by these.
  • R 1 represents a hydrogen atom or a methyl group.
  • m represents an integer of 1 to 3.
  • Such a cage silsesquioxane resin has a reactive functional group composed of an organic functional group having a (meth) acryloyl group on all silicon atoms in the resin, and has a controlled molecular weight distribution and molecular structure.
  • a cage silsesquioxane resin is preferred.
  • the molecular structure of such a cage silsesquioxane resin may not be a completely closed polyhedron, and may be a structure in which a part is cleaved, for example.
  • the average molecular weight of such cage-type silsesquioxane resin is not particularly limited, and such cage-type silsesquioxane resin may be an oligomer.
  • the photocurable resin composition referred to in the present invention is not particularly limited as long as it is a resin composition that can be cured by irradiation with active energy rays.
  • a photocurable resin composition may contain other resins in addition to the cage silsesquioxane.
  • the other resin that can be used by mixing with the cage silsesquioxane resin in this way is not particularly limited as long as the resin has compatibility and reactivity with the cage silsesquioxane resin.
  • (Meth) acrylic acid, methyl (meth) acrylate, and the like are mentioned as the resin having a (meth) acrylic group, and it is not directly reactive with the cage silsesquioxane, but can be used in combination.
  • such a photocurable resin composition may further contain a filler-based additive as long as it does not inhibit photocurability.
  • a filler-based additive include fine particle fillers such as silica, alumina and titanium oxide, glass fiber short fibers or long fibers, and plastic fibers such as styrene and polyester.
  • Such a photocurable resin composition usually further contains a photopolymerization initiator.
  • photopolymerization initiators include alkynephenone-based, acylphosphine oxide-based, and titanium cene-based photopolymerization initiators.
  • photopolymerization initiators include ⁇ -hydroxyalkylphenone, biacetylacetophenone, benzophenone, benzyl, benzoylisobutyl ether, benzyldimethyl ketal, (1-hydroxycyclohexyl) phenylketone, (1-hydroxy-1 -Methylethyl) phenyl ketone, ( ⁇ -hydroxyisopropyl) (p-isopropylphenyl) ketone, diethylthioxanthone, ethyl anthraquinone, bis (diethylamino) benzophenone and the like.
  • a photocurable resin composition what contains a well-known solvent as a diluent may be used for viscosity adjustment etc., but time is considered when the devolatilization removal process of a solvent is considered. Therefore, from the viewpoint that the production efficiency is reduced, and from the viewpoint that residual solvent exists in the cured film and leads to deterioration of the properties of the molded film, it is preferable to use a solvent having a content of 5% or less. It is more preferable to use those not containing.
  • the hard coat film laminate for injection molding of the present invention is prepared, for example, when a polycarbonate film is used alone as a base material layer, and the photocurable resin composition is prepared on the surface of the polycarbonate film layer in advance. It can be manufactured by curing after forming the transparent resin layer.
  • the method for applying the photocurable resin composition in this way is not particularly limited, and a known method can be adopted as appropriate.
  • a known coating device can be adopted.
  • a coating method known methods such as gravure coating, roll coating, reverse coating, knife coating, die coating, lip coating, doctor coating, extrusion coating, slide coating, wire bar coating, curtain coating, extrusion coating, spinner coating, etc.
  • a coating method can be adopted.
  • an ultraviolet irradiation method in which ultraviolet rays are generated and irradiated on the photocurable resin composition after application to be photocured is adopted.
  • the ultraviolet lamp used in such a method include a metal halide lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a pulse type xenon lamp, a xenon / mercury mixed lamp, a low-pressure sterilization lamp, and an electrodeless lamp.
  • a metal halide lamp or a high-pressure mercury lamp it is preferable to use a metal halide lamp or a high-pressure mercury lamp.
  • irradiation exposure may be in the range of 20 ⁇ 10000mJ / cm 2, it is preferably in the range of at 100 ⁇ 10000mJ / cm 2. Further, from the viewpoint of effective use of light energy, it is preferable to attach an elliptical, parabolic, or diffusive reflector to the ultraviolet lamp, and a heat cut filter or the like may be attached as a cooling measure.
  • a cooling device to the irradiated part of the ultraviolet lamp.
  • a cooling device By such a cooling device, it is possible to suppress thermal deformation of the hard coat film laminate for injection molding induced by heat generated from the ultraviolet lamp.
  • a cooling method of such a cooling device a known method such as an air cooling method or a water cooling method can be employed.
  • the ultraviolet curing reaction is a radical reaction
  • the reaction inhibition by oxygen is received. Therefore, from the viewpoint of suppressing reaction inhibition by oxygen in the curing reaction of the photocurable resin composition, it is preferable to cover the surface with a cover layer made of a transparent plastic film after applying the photocurable resin composition.
  • the oxygen concentration on the surface of the photocurable resin composition is preferably 1% or less, and preferably 0.1% or less. preferable. In order to reduce the oxygen concentration in this way, it is preferable to employ a transparent plastic film having no voids on the surface and low oxygen permeability.
  • film materials include PET (polyethylene terephthalate), PEN (polyethylene naphthalate), PBT (polybutylene phthalate), PC (polycarbonate), polypropylene, polyethylene, acetate resin, acrylic resin, and vinyl fluoride.
  • Plastics such as resin, polyamide, polyarylate, cellophane, polyethersulfone and norbornene resin. These plastics can be used alone or in combination of two or more. Since such a plastic film must be able to be peeled off from the cured photocurable resin composition (hard coat layer), the surface of the plastic film is subjected to easy peeling treatment such as silicon coating or fluorine coating. It is preferable to use what is.
  • the hard coat layer 2 and the plastic film are formed on one surface of a single layer of a single resin selected from the group consisting of polycarbonate, polymethyl methacrylate, and polyethylene terephthalate, or a base layer 4 composed of two or more types.
  • the hard coat film laminate in which the cover layer 3 is laminated and integrated is placed in an injection mold.
  • the hard coat film laminate 1 is arranged in a flat shape in the cavity of the first injection mold 5.
  • the cover layer 3 of the plastic film of the hard coat film laminate 1 is disposed so as to contact the cavity wall surface of the first injection mold 5.
  • the second injection mold 6 is overlaid on the first injection mold 5 and closed, and in this state, the cavities in the molds 5 and 6 are inserted through the injection gate.
  • a thermoplastic resin is injected into the container.
  • injection molding of a thermoplastic resin is performed to form a resin molded body, and at the same time, the hard coat film laminate is integrally formed on the surface of the resin molded body.
  • the plastic film cover layer 3 on the surface of FIG. 3 is peeled off to obtain an injection molded body 8 having a hard coat portion on the surface.
  • FIG. 4 is a schematic view showing the entire injection molding machine equipped with a mechanism for continuously supplying the hard coat film laminate 1.
  • the second injection molding 6 in FIG. 2 is arranged on the fixed side platen 11
  • the first injection mold 5 is arranged on the movable side platen 9, and harder than the film loading machine 13 along the movable side platen 9.
  • the first injection mold 5 is overlapped with the second injection mold 6 and closed, and then from the nozzle 12.
  • the injection molded body 8 is obtained by injecting the thermoplastic resin.
  • the hard coat film laminated body 1 for obtaining the next injection molding body can be supplied by operating a film loading machine.
  • the film loading machine only needs to have a mechanism for continuously unwinding from the supply side, and does not necessarily have a mechanism for winding.
  • the base material layer (base material layer containing at least one of polycarbonate, polymethyl methacrylate, or polyethylene terephthalate) 4
  • the resin is not particularly limited as long as it is a thermoplastic resin that can be melted and integrated with each other, and is preferably a polycarbonate resin, a PMMA resin, or a PET resin.
  • the injection molding resin may contain various additives such as an antioxidant, a light stabilizer, an ultraviolet absorber, a lubricant, and a plasticizer inhibitor.
  • a planar mold and a mold having a curvature can be used as the shape of the injection mold.
  • a mold having a curvature is preferably set so that the elongation is 0.1% to 10%, the length to the end, and the amount of sagging.
  • Example 1 The following structural formula (4) 25 parts of silsesquioxane, 65 parts of dipentaerythritol (manufactured by Nippon Kayaku Co., Ltd., trade name “KAYARAD DPHA”), dimethylol tricyclodecane diacrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name “light acrylate DCP— A ”) 10 parts and 2.5 parts of hydroxycyclohexyl phenyl ketone (Ciba Specialty Chemicals, trade name” IRGACURE 184 ”) are stirred and mixed uniformly, and then defoamed to obtain a liquid photocurable resin composition. Got.
  • a polycarbonate film (manufactured by Sumitomo Chemical Co., Ltd., trade name “Technoloy”) obtained by surface-treating the obtained liquid photocurable resin composition with a silane coupling agent (trade name “KBE-903”, manufactured by Shin-Etsu Chemical Co., Ltd.) in advance. C000 ”) so that the thickness after curing was 0.05 mm.
  • a transparent cover film material: polyethylene terephthalate, light transmittance of 90% or more at a wavelength of 550 nm
  • ultraviolet rays are emitted from a metal halide lamp at 6400 mJ / cm 2.
  • the hard coating layer is cured by irradiating with an irradiation exposure amount of 1 to 3, whereby a hard layer for injection molding having a three-layer structure of a base material layer 4-hard coat layer 2-cover layer 3 made of polycarbonate resin as shown in FIG. Coated film laminate 1 was obtained.
  • FIG. 2A a part of the cover layer 3 remains on the cavity wall surface of the first injection mold while the hard coat film laminate 1 is kept flat in the first injection mold 5.
  • the second injection mold was overlaid on the first injection mold, and in this state, it was dried in advance at 120 ° C. for 24 hours from the injection gate into the cavity in the mold.
  • a polycarbonate resin trade name “Taflon 1900” manufactured by Idemitsu Co., Ltd.
  • FIG. An injection molded body 8 having a hard coat portion made of the hard coat film laminate 1 on the surface of a resin molded body 7 made of a polycarbonate resin having a thickness of 3 mm as shown in FIG.
  • ⁇ Surface hardness evaluation method> The molded body provided with the hard coat portion was subjected to scratch hardness (pencil method) according to JIS K5600-5-4. A steel wool test was also conducted. The steel wool test was performed using an eraser testing machine (manufactured by Honko Seisakusho Co., Ltd.) using steel wool # 0000, and the steel wool was reciprocated with a load of 500 g.
  • ⁇ Strength evaluation method> A bending test was performed on a molded body having a hard coat portion.
  • a test piece of 120 mm ⁇ 30 mm is placed on a base having an opening at the center (opening: 80 mm ⁇ 50 mm), and from the upper side, a push core tip R: SR5, speed: 5 mm / cm, indentation
  • the bending stress when pressed down to a depth of 40 mm and the surface state of the hard coat layer were observed.
  • Example 2 The liquid photocurable resin composition was applied so that the thickness after curing was 0.025 mm, and after obtaining an injection molded body 8 provided with a hard coat portion in the same manner as in Example 1, Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.
  • Example 3 The polycarbonate film side of the polycarbonate PMMA film (manufactured by Sumitomo Chemical Co., Ltd., trade name “Technoloy C001”) in which the polycarbonate film and the PMMA film are bonded together is previously a silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBE-903”). Surface treatment with.
  • An injection-molded article provided with the above-mentioned liquid photocurable resin composition on the surface-treated polycarbonate film side so that the thickness after curing is 0.07 mm, and having a hard coat portion in the same manner as in Example 1. After obtaining 8, evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.
  • Comparative Example 2 As a comparative example, the product name Iupilon sheet MR58 (thickness: 0.65 mm) manufactured by Mitsubishi Gas Chemical Co., Ltd., which had an acrylic hard coat applied to the surface of a polycarbonate sheet, was attached and evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 4 The liquid photocurable resin composition described above was applied to a PMMA film (manufactured by Sumitomo Chemical Co., Ltd., trade name “Technoloy S001G”) which was previously surface-treated with a silane coupling agent (trade name “KBE-903” manufactured by Shin-Etsu Chemical Co., Ltd.). It applied so that the thickness after hardening might be set to 0.1 mm, and the hard coat film laminated body 1 for injection molding was obtained by the method similar to Example 1.
  • a PMMA film manufactured by Sumitomo Chemical Co., Ltd., trade name “Technoloy S001G”
  • a silane coupling agent trade name “KBE-903” manufactured by Shin-Etsu Chemical Co., Ltd.
  • the injection resin was changed to PMMA resin (manufactured by Sumitomo Chemical Co., Ltd., trade name “Sumipex HT55X”) in the same manner as in Example 1, resin temperature 250 ° C., mold temperature 80 ° C., set injection pressure 129 MPa, injection time 6 seconds.
  • the injection molded body 8 provided with the hard coat portion made of the hard coat film laminate 1 on the surface of the resin molded body 7 made of 1.6 mm thick PMMA resin as shown in FIG. It was. Table 1 shows the results of evaluation in the same manner as in Example 1.
  • Example 5 15 parts of silsesquioxane represented by the above structural formula (4), 55 parts of dipentaerythritol (manufactured by Nippon Kayaku Co., Ltd., trade name “KAYARAD DPHA”), dimethylol tricyclodecane diacrylate (manufactured by Kyoeisha Chemical Co., Ltd., product) 30 parts of the name “light acrylate DCP-A”) and 2.5 parts of hydroxycyclohexyl phenyl ketone (manufactured by Ciba Specialty Chemicals, trade name “IRGACURE 184”) are stirred and mixed uniformly, and then defoamed and liquidized. A photocurable resin composition was obtained.
  • dipentaerythritol manufactured by Nippon Kayaku Co., Ltd., trade name “KAYARAD DPHA”
  • dimethylol tricyclodecane diacrylate manufactured by Kyoeisha Chemical Co., Ltd., product
  • Example 1 shows the results of evaluation in the same manner as in Example 1.
  • Example 6 70 parts of silsesquioxane represented by the structural formula (4), 20 parts of dipentaerythritol (manufactured by Nippon Kayaku Co., Ltd., trade name “KAYARAD DPHA”), dimethylol tricyclodecane diacrylate (manufactured by Kyoeisha Chemical Co., Ltd., product) 10 parts of the name “light acrylate DCP-A”) and 2.5 parts of hydroxycyclohexyl phenyl ketone (Ciba Specialty Chemicals, trade name “IRGACURE 184”) are uniformly stirred and mixed, and then defoamed to form a liquid. A photocurable resin composition was obtained.
  • dipentaerythritol manufactured by Nippon Kayaku Co., Ltd., trade name “KAYARAD DPHA”
  • dimethylol tricyclodecane diacrylate manufactured by Kyoeisha Chemical Co., Ltd., product
  • Example 1 shows the results of evaluation in the same manner as in Example 1.
  • the liquid photocurable resin composition used in Example 1 above was applied on PET for the base layer so that the thickness after curing was 0.050 mm, and another cover layer PET was then applied thereon. After pressure-bonding to the coated photocurable resin, the hard coat layer was cured by irradiating ultraviolet rays with an ultra-high pressure mercury lamp at an irradiation exposure amount of 6400 mJ / cm 2 . After curing, the PET for the base layer and the cover layer were peeled off to obtain a film having only the hard coat layer.
  • ⁇ Dynamic viscoelasticity measurement> The glass transition temperature of only the hard coat layer was measured with a dynamic viscoelasticity measuring device (DVE-V4 Rheospectr manufactured by UBM Co., Ltd.). The results are as shown in FIG. 6, and the glass transition temperature represented by tan ⁇ was not observed in the measurement up to 230 ° C.
  • E ′ represents the storage elastic modulus
  • E ′′ represents the loss elastic modulus
  • tan ⁇ E ′′ / E ′.
  • Hard coat film laminate 2 for injection molding 2 Hard coat layer 3: Cover layer 4: Base material layer 5: First injection mold 6: Second injection mold 7: Resin molded body 8: Injection molded body 9: Movable side platen 10: Tie bar 11: Fixed side platen 12: Nozzle 13: Film loading machine

Landscapes

  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne : un film de couche dure multicouche pour moulage par injection qui, en tant que couche dure pour des articles en résine moulés, a une dureté superficielle extrêmement élevée, une excellente adhésion, et une excellente conformabilité à des moules ; un procédé pour produire le film de couche dure multicouche ; et un procédé pour produire un objet moulé par injection utilisant le film de couche dure multicouche. Une couche dure qui a une épaisseur de 20 µm ou plus, une transmittance mesurée à une longueur d'onde de 550 nm de 90 % ou plus, et une température de transition vitreuse de 230 ºC ou plus est formée par application d'une composition de résine photodurcissable contenant une résine de silsesquioxane à structure de cage qui est photodurcissable sur une surface d'un film de couche de base constitué de, par exemple, une résine polycarbonate et durcissement de la composition. Ainsi, un film de couche dure multicouche pour moulage par injection est obtenu. Ce film de couche dure multicouche est placé dans un moule pour moulage par injection, et une résine est moulée. Simultanément à cela, le film de couche dure multicouche est intégré avec la surface de l'objet en résine moulé.
PCT/JP2011/074504 2010-11-10 2011-10-25 Film de couche dure multicouche pour moulage par injection, procédé pour produire celui-ci, et procédé pour produire un objet moulé par injection en utilisant le film de couche dure multicouche WO2012063637A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1020137014529A KR101902492B1 (ko) 2010-11-10 2011-10-25 사출 성형용 하드코트 필름 적층체, 그 제조방법, 및 그 하드코트 필름 적층체를 이용한 사출 성형체의 제조방법
CN201180054153.9A CN103201080B (zh) 2010-11-10 2011-10-25 注射成型用硬涂膜层叠体、其制造方法和利用了该硬涂膜层叠体的注射成型体的制造方法

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
JP2010-251693 2010-11-10
JP2010251693 2010-11-10
JP2011-032006 2011-02-17
JP2011032006 2011-02-17
JP2011220236A JP5735394B2 (ja) 2011-02-17 2011-10-04 射出成形用ハードコートフィルム積層体を利用した射出成形体の製造方法
JP2011-220236 2011-10-04
JP2011-220237 2011-10-04
JP2011220237A JP5794883B2 (ja) 2010-11-10 2011-10-04 射出成形用ハードコートフィルム積層体及びその製造方法並びに射出成形体

Publications (1)

Publication Number Publication Date
WO2012063637A1 true WO2012063637A1 (fr) 2012-05-18

Family

ID=46050789

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2011/074504 WO2012063637A1 (fr) 2010-11-10 2011-10-25 Film de couche dure multicouche pour moulage par injection, procédé pour produire celui-ci, et procédé pour produire un objet moulé par injection en utilisant le film de couche dure multicouche

Country Status (1)

Country Link
WO (1) WO2012063637A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104057680A (zh) * 2013-03-19 2014-09-24 新日铁住金化学株式会社 树脂层叠体和使用了该树脂层叠体的成型方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009178904A (ja) * 2008-01-30 2009-08-13 Nippon Steel Chem Co Ltd 加飾印刷フィルム積層体
JP2009214499A (ja) * 2008-03-12 2009-09-24 Dainippon Printing Co Ltd 加飾樹脂成形品の製造方法及び加飾樹脂成形品
JP2010064384A (ja) * 2008-09-11 2010-03-25 Ono Sangyo Kk 樹脂成形品
JP2010125719A (ja) * 2008-11-28 2010-06-10 Nippon Steel Chem Co Ltd 飛散防止性能付きガラス

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009178904A (ja) * 2008-01-30 2009-08-13 Nippon Steel Chem Co Ltd 加飾印刷フィルム積層体
JP2009214499A (ja) * 2008-03-12 2009-09-24 Dainippon Printing Co Ltd 加飾樹脂成形品の製造方法及び加飾樹脂成形品
JP2010064384A (ja) * 2008-09-11 2010-03-25 Ono Sangyo Kk 樹脂成形品
JP2010125719A (ja) * 2008-11-28 2010-06-10 Nippon Steel Chem Co Ltd 飛散防止性能付きガラス

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104057680A (zh) * 2013-03-19 2014-09-24 新日铁住金化学株式会社 树脂层叠体和使用了该树脂层叠体的成型方法

Similar Documents

Publication Publication Date Title
KR101902492B1 (ko) 사출 성형용 하드코트 필름 적층체, 그 제조방법, 및 그 하드코트 필름 적층체를 이용한 사출 성형체의 제조방법
TWI760385B (zh) 具有防眩性及抗反射性之透明基板與其製造方法
KR101379491B1 (ko) 하드코팅 필름 및 이의 제조방법
KR101415840B1 (ko) 하드코팅 필름
KR101555737B1 (ko) 아크릴계 수지 시트를 연속적으로 제조하는 방법
TWI753069B (zh) 透明樹脂基板
US20130209796A1 (en) Polycarbonate with hard coat layer
TWI394660B (zh) 薄膜積層體及其製造方法
CN107531029B (zh) 活性能量线固化性树脂组合物、防雾防污层叠体、物品及其制造方法、以及防污方法
KR101578254B1 (ko) 수지 적층체의 제조방법
JPWO2020008961A1 (ja) 加飾フィルム、加飾方法、加飾成型体の製造方法、及び、加飾成型フィルム
JP5735394B2 (ja) 射出成形用ハードコートフィルム積層体を利用した射出成形体の製造方法
KR20140114795A (ko) 수지 적층체 및 이것을 사용한 성형 방법
JP5794883B2 (ja) 射出成形用ハードコートフィルム積層体及びその製造方法並びに射出成形体
JP5616036B2 (ja) 基材、中間膜及び微細凹凸構造膜を積層してなる積層体
WO2012063637A1 (fr) Film de couche dure multicouche pour moulage par injection, procédé pour produire celui-ci, et procédé pour produire un objet moulé par injection en utilisant le film de couche dure multicouche
JP7229833B2 (ja) 成型用積層フィルム
TW201800262A (zh) 聚酯膜及其製造方法、硬塗膜及其製造方法、圖像顯示裝置及觸控面板
KR20230038142A (ko) 인서트 성형용 하드 코트 필름 및 인서트 성형품의 제조방법
JP2022110332A (ja) 反射防止基板
KR20090035233A (ko) 반사외관이 우수한 디스플레이용 하드코팅필름
JP2020082439A (ja) 樹脂硬化層付き基板、化粧板、車両用窓、及び樹脂硬化層付き基板の製造方法
WO2021070632A1 (fr) Procédé de production d'élément incurvé et corps stratifié de résine de polycarbonate à revêtement dur pour flexion thermique
TWI791705B (zh) 積層體以及成形體及其製造方法
TW202311037A (zh) 抗反射膜及使用其之樹脂成形品

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: 11840674

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20137014529

Country of ref document: KR

Kind code of ref document: A

122 Ep: pct application non-entry in european phase

Ref document number: 11840674

Country of ref document: EP

Kind code of ref document: A1