CN101965261A - Hard coat film and resin molded product - Google Patents

Hard coat film and resin molded product Download PDF

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Publication number
CN101965261A
CN101965261A CN2009801081747A CN200980108174A CN101965261A CN 101965261 A CN101965261 A CN 101965261A CN 2009801081747 A CN2009801081747 A CN 2009801081747A CN 200980108174 A CN200980108174 A CN 200980108174A CN 101965261 A CN101965261 A CN 101965261A
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hard coat
film
hard conating
coat film
resin
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CN101965261B (en
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斋藤正登
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Kimoto Co Ltd
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Kimoto Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/022—Mechanical properties
    • 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
    • B32B27/30—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
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • 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
    • B29K2715/00—Condition, form or state of preformed parts, e.g. inserts
    • B29K2715/006—Glues or adhesives, e.g. hot melts or thermofusible adhesives
    • 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
    • B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
    • B29K2995/002—Coloured
    • 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
    • B29K2995/0087—Wear resistance
    • 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
    • B29L2009/008—Layered products coated metalized, galvanized
    • 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
    • B32B2255/20—Inorganic coating
    • B32B2255/205—Metallic coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/536—Hardness

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Laminated Bodies (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)

Abstract

Disclosed is a hard coat film having satisfactory hard coat properties and crack resistance. A hard coat film (10) comprises a hard coat layer (12) stacked on one side surface of a base material film (11). The hard coat layer (12) is regulated so that the Martens hardness is not less than 250 N/mm2, the plastic hardness (Hupl) is not less than 800 N/mm2, and the elastic indentation modulus (EIT) is not more than 5000 MPa.

Description

Hard coat film and synthetic resin
Technical field
The present invention relates to hard coat film and the synthetic resin that has used this hard coat film.
Background technology
Known have face at base material film to form metal evaporation film or printed layers, form as the produced by insert molding of the hard conating of surface protection film with hard coat film (patent documentation 1 and patent documentation 2) at another face of base material film.
Patent documentation 1: TOHKEMY 2005-288720 communique
Patent documentation 2: TOHKEMY 2005-305786 communique
Summary of the invention
Usually, be the hard conating that purpose is used for surface protection with the moulding product, require to have being coated with property firmly.For example wishing to have pencil hardness is the above hardness of 300g load more than the H, in the steel wool test.For this reason, hard conating usually by electronic beam solidified resin or ultraviolet curing resin etc. firmly the gel-type resin of being coated with property excellence constitute.
But, when the hard coat film of record in patent documentation 1 and the patent documentation 2 is used for actual produced by insert molding, be easy to generate crackle or albefaction, fragmentation during moulding on the surface of hard conating.Generally speaking, the surface of moulding product is owing to be curved surface or the angle is arranged, thereby is difficult to avoid the generation of crackle etc.
At therewith, can consider in the resinous principle that constitutes hard conating, to add the flexibility that thermoplastic resin improves hard conating.But at this moment, the decline of being coated with property firmly of hard conating, existence can't be resisted the problem of the load of above-mentioned steel wool test.
The technical problem to be solved in the present invention is to provide has enough the being coated with property firmly and the hard coat film of fracture-resistant.In addition, its purpose also is to provide this hard coat film is integrated and synthetic resin that form.
The present invention is formed at least one face of base material film by suitable adjusting the being coated with property firmly of hard conating solves above-mentioned technical problem.
According to the present invention,, therefore can make and have enough the being coated with property firmly and the hard coat film of fracture-resistant because the being coated with property firmly of hard conating suitably regulated.
Description of drawings
Fig. 1 is the sectional view of the hard coat film of an expression example of the present invention.
Fig. 2 is the chart of an example of expression h-F curve.
(symbol description)
10 ... hard coat film, 11 ... base material film, 12 ... hard conating, 13 ... metal evaporation layer, 14 ... printed layers, 15 ... adhesive layer
The specific embodiment
Below, the embodiment of foregoing invention is described with reference to the accompanying drawings.
" hard coat film "
As shown in Figure 1, the hard coat film 10 of present embodiment has the hard conating 12 of a face that is laminated in base material film 11.
This routine hard conating 12, its firmly being coated with property obtained suitable adjusting.Particularly, Martens hardness (HM) and plasticity hardness (Hupl) are adjusted to greater than specific value, and impression elastic modelling quantity (being equivalent to Young's modulus) EIT is adjusted to less than specific value.
The present inventor is in order to take into account being coated with property and the opposite like this performance of fracture-resistant firmly, being conceived to the specific indexes relevant with the being coated with property firmly of hard conating 12 studies, found that: make Martens hardness and plasticity hardness greater than specific value and make the impression elastic modelling quantity by the being coated with property firmly of regulating hard conating 12, can take into account above-mentioned being coated with property firmly and fracture-resistant less than specific value.This routine hard conating 12 since its firmly being coated with property obtained suitable adjusting, thereby can have enough being coated with property firmly and fracture-resistant.
Martens hardness (HM) the expression test load when utilizing the Vickers pressure head to push hard conating 12 surperficial and the hardness (difficulty that is caved in) of the impression surface area hard conating 12 of trying to achieve are the hardness numbers on the surface of hard conating 12.
In this example, the value of the HM of hard conating 12 preferably is adjusted to 250N/mm 2More than, 280N/mm more preferably 2More than, 300N/mm more preferably 2More than.Be adjusted to more than the setting by HM, can prevent from effectively on hard conating 12, to produce scar hard conating 12.On the other hand, if the HM of hard conating 12 is excessive, then produce bad phenomenon such as film warpage sometimes.Therefore, in this example, preferably the HM with hard conating 12 is adjusted to 500N/mm 2Below, 400N/mm more preferably 2Below.
The value of the HM that this is routine is the value that records by the following method: under the atmosphere gas of temperature 20 degree and relative humidity 60%, utilize ultra micro hardness test device (Fischer Instruments company, trade name: FISCHERSCOPEHM2000), employing is according to the method for ISO-14577-1, measure the case hardness of hard conating 12, the value that records is the value of HM.Wherein, be maximum test load: the value that records under the 1mN.
The hardness (difficulty of impression) of the hard conating 12 that plasticity hardness (Hupl) expression is tried to achieve by the depth of cup after the off-load of Vickers pressure head is indexs of the hardness of hard conating 12.
In this example, the value of the Hupl of hard conating 12 preferably is adjusted to 800N/mm 2More than, 900N/mm more preferably 2More than, 1000N/mm more preferably 2More than.Be adjusted to more than the setting by Hupl, can prevent from effectively on hard conating 12, to produce scar hard conating 12.On the other hand, if the Hupl of hard conating 12 is excessive, then produce bad phenomenon such as film warpage sometimes.Therefore, in this example, preferably the Hupl with hard conating 12 is adjusted to 3000N/mm 2Below, 2000N/mm more preferably 2Below.
Illustrated that the value of Hupl can adopt according to the method for ISO-14577-1 and measure, calculated with following formula (3).In following formula, provide calculating formula (1), (2) of Hupl and omnipotent hardness (Hu) in the lump.
[several 1] Hu=F/ (A (h))=F/ (26.43 * h 2) ... (1)
[several 2] A (h)=[(4 * sin (a/2))/(cos 2(a/2))] * h 2(2)
[several 3] Hupl=(F Max/ (26.43 * hr 2)) ... (3)
Here, in formula (1)～formula (3), " F " be test load (unit: N), " F Max" be that (unit: maximum N), " A (h) " is the surface area (unit: mm that pressure head contacts with determinand to test load 2).
A (h) is calculated by the shape and the depth of cup of pressure head, when pressure head is the Vickers pressure head, according to the angle a (136 °) of the opposite face of the insertion body of pyramid, by (26.43 * h 2) calculate.In addition, " h " be the test load depth of cup of doing the time spent (unit: mm), " h Max" be that (unit: maximum mm), " hr " is (h of h-F curve to the test load depth of cup of doing the time spent Max, F Max) the h coordinate figure (unit: mm) of h axle intersection point of tangent line of point.
Above-mentioned h-F curve for example as shown in Figure 2.(1) among Fig. 2 is that load increases to F from 0 MaxThe time the h-F curve, (2) are that load is then from F MaxReduce to 0 o'clock h-F curve, (3) are (h of h-F curve Max, F Max) point tangent line.
Illustrated that the value of the Hupl that this is routine is the following value that records: use the device identical with the situation of above-mentioned HM, under condition determination described later, adopt the method according to ISO-14577-1, measure the case hardness of hard conating 12, the value that obtains is the value of Hupl.
About condition determination, indenter shape for example: Vickers pressure head (a=136 °), measure environment: 20 ℃ of relative humidity 60% of temperature, maximum test load: 1mN, load speed: 1mN/20 second, the maximum load creep time: 5 seconds, off-load speed: 1mN/20 second.About measuring, each sample all on 5 points of direction of principal axis equal intervals, circumferencial direction equal angular 3 amount at 15 and measure, with its mean value as this routine plasticity hardness (Hupl).
Impression elastic modelling quantity (Young's modulus) EIT represents the crooked easiness (flexibility) of hard conating 12, is the index of the fragility of hard conating 12.
In this example, the EIT of hard conating 12 preferably is adjusted to below the 5000MPa, more preferably below the 4900MPa.Be adjusted to below the setting by the EIT with hard conating 12, hard conating 12 is flexible, helps the raising of fracture-resistant.On the other hand, if the EIT of hard conating 12 is too small, then there is the tendency of being coated with property decline firmly.Therefore, in this example, preferably the EIT with hard conating 12 is adjusted to more than the 4000MPa, more preferably more than the 4300MPa.
Illustrated, the value that is equivalent to Young's modulus that the value of EIT is to use the device identical with the situation of above-mentioned HM and Hupl, records according to ISO-14577-1, be on corrosion resistant plate, to form hard conating 12, and the value of using the hard conating 12 obtain to record, that is to say the Young's modulus of the hard conating that under the situation of the influence of the spring rate that is not subjected to base material film 11, records 12 self.Wherein, same with HM and Hupl, be maximum test load: the value that records under the 1mN.
The value of the anti-bend test of this routine hard coat film 10 preferably is adjusted to below the 5mm, more preferably below the 4mm because of the kind of the thickness of hard conating 12, base material film 11 is different with thickness.Be adjusted to below the setting by value, can improve the fracture-resistant of hard conating 12 anti-bend test.In addition, the value of anti-bend test is a value of using the cylindrical shape axle method according to JIS-K5600-5-1 (1999) to record.
This routine hard conating 12 preferably is adjusted to when making reciprocal 10 times of steel wool #0000 under the load of 300g can not produce scar.By adjusting like this, can guarantee necessary being coated with property firmly.
This routine hard conating 12 also preferably is adjusted to pencil and draws the value of writing (pencil hardness) for more than the H.Further preferably be adjusted to more than the 2H.Be adjusted to more than the setting by pencil being drawn the value of writing, can prevent the surperficial impaired of hard conating 12 effectively.In addition, to draw the value of writing be the value of using the method according to JIS-K5400 (1990) to record to pencil.
The thickness of this routine hard conating 12 is preferably below the 10 μ m, more preferably below the 5 μ m.This is because if thickness surpasses 10 μ m, then be easy to generate crackle etc.On the other hand, if thickness is thin excessively, then can't bring into play fully being coated with property firmly sometimes.Therefore, the thickness of hard conating 12 is preferably more than the 0.5 μ m, more preferably more than the 1 μ m, more preferably more than the 2 μ m.
This routine hard conating 12 for example can be as the acquisition of getting off: preparation coating, it is coated on the base material film 11, and it is solidified obtain.
The coating that this example can be used contains resinous principle.Resinous principle comprises the ionizing radiation gel-type resin.
As the ionizing radiation gel-type resin that contains in the resinous principle, can use the optical polymerism prepolymer of crosslinking curing under the irradiation of ionizing radiation (ultraviolet ray or electron beam).In this example, can use optical polymerism prepolymer described later separately, also can be used in combination more than 2 kinds.
The optical polymerism prepolymer has cationic polymerization type and radical polymerization mould assembly.
As cationic polymerization type optical polymerism prepolymer, can enumerate epoxylite or vinyl ethers resinoid etc.As epoxylite, can enumerate for example bisphenol-type epoxy resin, phenolic resin varnish type epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin etc.
As radical polymerization mould assembly optical polymerism prepolymer,, especially preferably use the acrylic compounds prepolymer (hard prepolymer) that has 2 above acryloyl groups in 1 molecule, forms the three dimensional network structure by crosslinking curing from the viewpoint of being coated with property firmly.
As the acrylic compounds prepolymer, can enumerate urethane acrylate, polyester acrylate, epoxy acrylate, melamine acrylate, poly-fluoroalkyl acrylate, organic silicon acrylic ester etc.
Urethane acrylate class prepolymer for example can obtain by the following method: the urethane oligomer that will be obtained by the reaction of PPG or PEPA and PIC, esterification obtains urethane acrylate class prepolymer with the reaction of (methyl) acrylic acid.As polyester acrylate class prepolymer, for example can obtain by the following method: two ends that will be obtained by the condensation of polybasic carboxylic acid and polyacid alcohol have the hydroxyl of the polyester oligomer of hydroxyl, carry out esterification with (methyl) acrylic acid, perhaps will be on polybasic carboxylic acid the hydroxyl of end of addition alkylene oxide and the oligomer that obtains, carry out esterification with (methyl) acrylic acid, obtain polyester acrylate class prepolymer.Epoxy acrylate class prepolymer for example can obtain by the following method: esterification obtains epoxy acrylate class prepolymer with the reaction of (methyl) acrylic acid for the bisphenol-type epoxy resin that molecular weight is lower or the oxirane of phenolic resin varnish type epoxy resin.
The acrylic compounds prepolymer can wait suitably according to the kind of applied object (base material film 11) or purposes and select.In addition, the acrylic compounds prepolymer can use separately, but gives various performances for the raising of crosslinking curing and the adjusting of cure shrinkage etc., preferably adds photopolymerization monomer.
As photopolymerization monomer, can enumerate simple function acrylic monomers (2-EHA for example, acrylic acid 2-hydroxy methacrylate, acrylic acid 2-hydroxy propyl ester, acrylic acid butoxy ethyl ester etc.), 2 functionalized propylene's acid monomers (for example 1, the 6-hexanediyl ester, neopentylglycol diacrylate, diethylene glycol diacrylate, polyethyleneglycol diacrylate, hydroxy new pentane acid ester neopentylglycol diacrylate etc.), 3 officials can be above acrylic monomers (dipentaerythritol acrylate for example, TMPTA, pentaerythritol triacrylate etc.).In addition, " acrylate " also comprises methacrylate except as the acrylate shown in literal.These photopolymerization monomers may be used singly or in combination of two or more.
The optical polymerism prepolymer in this routine coating and the total content of photopolymerization monomer (solid state component conversion) in total resinous principle, are preferably 40～99 weight %, more preferably 60～95 weight %, more preferably 80～90 weight %.
Particularly in this example, in order to take into account the being coated with property firmly and the fracture-resistant of formed tunicle, preferably in the ionizing radiation gel-type resin, add specific optical polymerism prepolymer (A) and photopolymerization monomer (B) at least any.
As specific optical polymerism prepolymer (A), can enumerate the multifunctional oligomer that has tree in the molecule, has (methyl) acrylate-functional groups more than 3.
Tree is meant monomer generation branching and carries out the shape that polymerization, radial extension form that the multifunctional oligomer with tree is shown in general formula (1).
Figure BPA00001216318300071
In the formula, X be hydrogen, acryloyl group or
Figure BPA00001216318300072
Particularly, be to have the multifunctional oligomer that functional group, ends such as amino, hydroxyl, carboxyl, phenyl, Oxyranyle, vinyl, expoxy propane base have (methyl) acrylate-functional groups.Wherein, dissolubility from solvent or operability and when adding other ionizing radiation gel-type resins and the viewpoints such as intermiscibility of this resin preferably contain the multifunctional oligomer that Oxyranyle, end have (methyl) acrylate-functional groups.
The number of (methyl) acrylate-functional groups and the molecular weight of oligomer are big more, and then the hardness of the hard conating 12 that is formed by the ionizing radiation curable resin composition is high more, is difficult for more during shaping cracking.Wherein, when the number of (methyl) acrylate-functional groups was too much, the fracture-resistant during shaping can descend.In addition, if the molecular weight of oligomer is excessive, then the being coated with property firmly of hard conating 12 can descend.Therefore, the number of (methyl) acrylate-functional groups is preferably 3～10, and more preferably 5～8.In addition, molecular weight is preferably 1000～3000, and more preferably 1500～2000.
The content of the optical polymerism prepolymer (A) in this routine coating, total 100 weight portions with respect to photopolymerization monomer and other optical polymerism prepolymers, be preferably 10～160 weight portions, more preferably 20～100 weight portions, more preferably 30～70 weight portions.By the content that makes optical polymerism prepolymer (A) is more than 10 weight portions, can prevent to crack etc. in the marginal portion when pressurized when moulding.In addition, be below 160 weight portions, can keep being coated with property firmly.
As specific photopolymerization monomer (B), can be set forth in the photopolymerization monomer that has polymerism reactive group and ring structure in the molecule.
Ring structure contains at least a kind of element that is selected from carbon, nitrogen, oxygen and the silicon, is preferably five-membered ring or hexatomic ring.As ring structure, specifically can enumerate cyclenes, oxolanes, 1 such as cyclopentene, cyclohexene, 3-diox, 6-caprolactone, epsilon-caprolactams, silicon are for cyclopentene, cyclodecane, isobornyl etc.As monomer, can enumerate 6-caprolactone modification three-(2-acryloxy ethyl) isocyanuric acid ester, 6-caprolactone modification three (2-ethoxy) isocyanuric acid ester, dihydroxymethyl tristane two (methyl) acrylate, isobornyl (methyl) acrylate, oxolane (methyl) acrylate, 2-acryloxy ethyl hexahydrophthalic acid etc. with such ring structure.
The content of the photopolymerization monomer (B) in this routine coating, overall with respect to the optical polymerism prepolymer and the photopolymerization monomer that constitute the ionizing radiation gel-type resin, press solid state component and convert, be preferably 1～70 weight %, more preferably 5～50 weight %.If more than the 1 weight %, crack in the time of preventing to pressurize etc.If below the 70 weight %, then can prevent the decline of being coated with property firmly of hard conating 12.
In addition, when when containing above-mentioned optical polymerism prepolymer (A), also containing (B), (A) and total content (B), with respect to other the photopolymerization monomer and total 100 weight portions of other optical polymerism prepolymer, be preferably 20～200 weight portions, more preferably 30～160 weight portions, more preferably 40～140 weight portions.(A) with the total content of (B) according to thickness of hard conating 12 etc. and different, therefore cannot treat different things as the same, but for example when the thickness of hard conating 12 scope at 2～5 μ m, with respect to (A) and total content (B), (B) be preferably 10～90 weight %, more preferably 15～60 weight %, more preferably 20～40 weight %.By the content that makes (B) is more than the 10 weight %, more difficult crack in the marginal portion etc. when pressurized when moulding.By being below the 80 weight %, can prevent being coated with property decline firmly.
When forming this routine hard conating 12, when making it solidify the back use, preferably in this routine coating, cooperate additives such as Photoepolymerizationinitiater initiater, photopolymerization promoter, ultraviolet sensitizer by the ultraviolet ray irradiation.
As Photoepolymerizationinitiater initiater; for radical polymerization mould assembly optical polymerism prepolymer or photopolymerization monomer, for example can enumerate acetophenone, benzophenone, michaelis ketone (Michler ' s ketone), benzoin, benzyl methyl ketal, phenylamino benzoic acid carbamoyl ester, α-acyl group oxime ester, thioxanthones etc.As Photoepolymerizationinitiater initiater, for example can enumerate the compound that anion such as salt such as aromatic matte ion, aromatic series oxo sulfonium cation, aromatic series iodide ion and tetrafluoroborate, hexafluorophosphate, hexafluoro antimonate, hexafluoro arsenate form at cationic polymerization type optical polymerism prepolymer.They may be used alone, two or more kinds can also be used in combination.As photopolymerization promoter, can enumerate p-dimethylaminobenzoic acid isopentyl ester, p-dimethylaminobenzoic acid ethyl ester etc.As ultraviolet sensitizer, can enumerate n-butylamine, triethylamine, tri-n-butyl phosphine etc.
In this routine coating,, except that the ionizing radiation gel-type resin, can contain other resins such as thermoplastic resin about below the 30 weight % of the resin that constitutes hard conating 12 or thermohardening type resin as the base-material composition.In addition, according to the kind of ionizing radiation gel-type resin, the use level of other resins that can contain is different sometimes.When containing the thermohardening type resin, use separately or and with thermal polymerization monomer or prepolymer, can contain thermal polymerization as required, promptly under heating, produce the compound etc. of living radical kind.As thermal polymerization, for example can enumerate peroxide, azo-compound etc.As object lesson, can enumerate benzoyl peroxide, tert butyl peroxy benzoate, azodiisobutyronitrile etc.
In addition, in this routine coating, can suitably cooperate adding ingredient as required.As adding ingredient, for example can enumerate in order to the delustering agent of giving anti-dazzle function or colouring agent, antistatic agent, ultra-violet absorber etc.
The coating that this is routine is during as organic solvent class coating, suitably select to get final product according to the kind of resinous principle, can add additive as required with retarder thinners such as organic solvents with after (the also having adding ingredient as required) dissolving of above-mentioned resinous principle or disperseing, make this routine coating.As organic solvent, do not have particular restriction, can enumerate alcohols (methyl alcohol for example, ethanol, isopropyl alcohol, butanols, octanol etc.), ketone (acetone for example, MEK (MEK), the first isobutyl ketone, cyclohexanone etc.), ester class (ethyl acetate for example, butyl acetate, ethyl lactate, gamma-butyrolacton, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate etc.), ethers (glycol monoethyl ether for example, diethylene glycol monobutyl ether etc.), aromatic hydrocarbons (benzene for example, toluene, dimethylbenzene etc.), amide-type (dimethyl formamide for example, dimethylacetylamide, N-methyl pyrrolidone etc.).When as solvent-free class coating, in above-mentioned resinous principle, add adding ingredient as required, promptly can be made into this routine coating.
As base material film 11; the film of preferably clear, hear resistance and mechanical strength excellence specifically can be enumerated PETG, polybutylene terephthalate (PBT), PEN, Merlon, polyethylene, polypropylene, polystyrene, tri acetyl cellulose, acrylic acid, polyvinyl chloride, norbornene compound etc.Particularly, preferably use through the biaxial stretch-formed PETG film that obtains from the viewpoint good to the dimensional stability of heat.
Base material film 11 can be implemented surface treatments such as easy gluing processing for good with the adhesivity of hard conating 12 and metal evaporation layer 13 described later or printed layers 14 or adhesive layer 15.
In base material film 11, can contain with pigment or ultra-violet absorber be representative, with the identical additive of additive that can in this routine coating, contain.
The thickness of base material film 11 does not have particular restriction, but if consider operability and mechanical strength etc., is 20～200 μ m, is preferably about 50～150 μ m.
Coating composition on base material film 11 (coating) can adopt well-established law to carry out, and for example can enumerate that rod is coated with, the coating of mouthful pattern, scraper coating, rotation coating, roller coat, intaglio plate coating, flow coat, dip coated, spraying, serigraphy, bristle coating etc.
In this example, be coated with for the mode of above-mentioned thickness in drying described later, curing back by the thickness of filming after the coating.Behind this routine coating of coating on the base material film 11, preferably make after the coating film dry down about 50～120 ℃.
About the curing of coating, can filming after the coating be carried out slaking and/or shine ionizing radiation (light) carrying out by heat.
Under the situation of utilizing heat,, can enumerate for example electric heater, infrared lamp, hot blast etc. as its thermal source.
Under the situation of utilizing ionizing radiation (light), as its line source, coat filming on the base material film 11 in short time curing as long as can make, there is not particular restriction.For example, as ultrared line source, can enumerate lamp, resistance heated plate, laser etc.As the line source of luminous ray, can enumerate daylight, lamp, fluorescent lamp, laser etc.As the line source of ultraviolet ray (ionizing radiation), can enumerate ultrahigh pressure mercury lamp, high-pressure sodium lamp, low pressure mercury lamp, carbon arc, Metal halogen lamp etc.100nm～400nm that irradiation is sent from these ultraviolet line sources, the ultraviolet ray that is preferably the wavelength region may of 200nm～400nm.As the line source of electron beam (ionizing radiation), can enumerate sweep type or curtain formula electron-beam accelerator etc.The electron beam of the wavelength region may below the 100nm that irradiation is sent from these electron-beam accelerators.
The exposure of ionizing radiation is according to the kind of ionizing radiation and difference, and for example under ultraviolet situation, light quantity is preferably 100～500mJ/cm 2About, under the situation of electron beam, about preferred 10～1000krad.
The routine hard conating 12 of this of Zhi Zaoing is taken into account being coated with property (marresistance) and fracture-resistant firmly as mentioned above.The performance fracture-resistant is because when the pressure (bending power or tensile force) that applied from the outside when keeping being coated with property firmly, intramolecular tree absorption pressure, perhaps intramolecular ring structure deforms and absorption pressure, all prevents at laminar surface generation crackle.
The hard coat film 10 of this embodiment is owing to have being coated with property and fracture-resistant firmly concurrently, therefore can wait at the operating portion (keypad portion) of instruments such as the touch-screen of for example household appliances or mobile phone, game machine, sound equipment player, notebook computer, application (preferably produced by insert molding purposes) in the decoration of various moulding product (especially synthetic resin) or the surface protection.
In addition, hard coat film 10 is owing to have being coated with property and fracture-resistant firmly concurrently, one-body molded purposes when therefore not only being used for produced by insert molding, disperse purposes or the thin film switch of glass that for example prevent that can also be used in addition needs the purposes of operations such as punching processing or bending machining like that.This be because, hard coat film 10 is used for perforation adds man-hour, fragmentation, crackle etc. can not appear in the marginal portion, and when being used for bending machining, can not crack yet, albefaction, fragmentation etc.
In addition, for example without synthetic resin but hard coat film when constituting the keypad portion of mobile phone also can use hard coat film 10.Because have being coated with property and fracture-resistant firmly concurrently.
In this embodiment; the hard coat film that for example will be used for following purposes is as " produced by insert molding film ": during the moulding product moulding that will be formed by resin etc. with mould; be disposed between resin and the mould; with resin and the whole integrated molding of hard coat film, obtain having formed the synthetic resin of pattern or sealer by moulding on the surface.
When the hard coat film 10 of this embodiment was used for the produced by insert molding purposes, its basic comprising was above-mentioned base material film 11 and hard conating 12, in addition, can also be on another face of base material film 11 the stacked decorative layer that is used for decorated molded article.
As decorative layer, for example can constitute by metal evaporation layer on another face that is formed at base material film 11 13 and the printed layers 14 that is laminated on this metal evaporation layer 13.On this decorative layer, can also laminated stickiness layer 15.
Decorative layer for example can by as inferior method form: after forming metal evaporation layer 13 on another face of base material film 11, remove the part of metal evaporation layer 13 by etching, the base material film of having removed behind the metal evaporation layer 13 11 is implemented printing, perhaps adopt known printing process, silk screening, intagliotype, ink-jet method etc. after forming required literal or pattern on the base material film 11, form metal evaporation layer 13 thereon.Sometimes save printed layers 14 and on base material film 11, directly form metal evaporation layer 13, perhaps sometimes printed layers 14 is only arranged and do not have metal evaporation layer 13.Under the situation that printed layers 14 is set, on the face that is provided with printed layers 14 of base material film 11, can be provided for taking in the layer of taking in of printer's ink liquid.
Metal evaporation layer 13 can be as the formation of getting off: adopt known method, for example vacuum vapour deposition, sputtering method, ion plating method etc., with metal or their alloy or the compound film forming of aluminium, nickel, gold, platinum, chromium, iron, copper, tin, indium, silver, titanium, lead or zinc etc.
Adhesive layer 15 is the layers that are provided with in order to the adhesivity that improves moulding product material and metal evaporation layer 13, according to the material of moulding product material, can suitably use adhesive such as polyurethanes, polyacrylic, polyesters, epoxies, polyvinyl acetate class, trichloroactic acid vinyl ester copolymers, cellulose family.
" manufacture method of synthetic resin "
Then, the hard coat film that this is routine 10 is described with the example that film carries out the method for the decoration of synthetic resin or surface protection as produced by insert molding.
At first, the hard coat film 10 that this is routine is configured in the mode that hard conating when making synthetic resin 12 is positioned at the outside, and the processing of pressurizeing, and is shaped to required shape.
Then, the mode that contacts with internal face with hard conating 12 with moulding hard coat film 10 be configured in the mould, and under this state,, form die cavity at mould inside with another mould matched moulds.
Then, in the die cavity in mould, after inflow is heated as the resin material of flow regime, resin material is solidified, obtain and hard coat film 10 incorporate synthetic resins.
The condition of moulding (temperature, clamping pressure, time) is according to the suitably selections such as shape of resin (moulding material) or moulding product.Usually, clamping pressure is calculated by moulding product projected area * mould pressure inside the resin.As an example, when injection molding resin is that (L * W * H) is 60 * 80 * 2 (mm for ABS resin and moulding product size 3) time, clamping pressure is 60t, and mold temperature is 60 ℃, and resin temperature is 250 ℃, and injection speed is 60mm/ second.About resin,, for example can adopt thermoplastic resin or heat-curing resins such as acrylic resin, polycarbonate resin, ABS resin, AS resin so long as can get final product by injection molding resin.Integrated with hard coat film 10 when making resin solidification, obtain this routine synthetic resin.
In this example; as the produced by insert molding film; use has this routine hard coat film 10 of the hard conating 12 of fracture-resistant excellence; therefore when adding man-hour and utilize mould molding, the pressurization of hard coat film 10 crackle can not take place; the synthetic resin that makes (decorate or surface protection) is attractive in appearance, and being coated with property excellence firmly.
As synthetic resin, for example can enumerate operating portion (keypad portion) of instruments such as the touch-screen of household appliances or mobile phone, game machine, sound equipment player, notebook computer etc.
[embodiment]
Then, enumerate the embodiment that the embodiment of foregoing invention is specialized more, explanation in further detail.In addition, " part ", " % " are not having to be weight basis under the prerequisite of specified otherwise.
" experimental example 1 "
At first, preparation hard conating coating fluid.
＜hard conating coating fluid 〉
8 parts of the multifunctional oligomer A1 of tree
(solid state component 100%) (Miramer SP1114:MIWON company)
12 parts of optical polymerism prepolymer/photopolymerization monomers
(solid state component 100%) (wall Mu Saite (PVC one system セ Star ト) 575: waste river chemical industrial company)
0.6 part of Photoepolymerizationinitiater initiater
(IRGACURE 651: vapour crust Japanese firm)
45 parts of propylene glycol monomethyl ethers
Then, (Cowes emits the summer (コ ス モ シ ヤ イ Application) A4300: on face Japan's textile company) at the polyester film as the thick 125 μ m of base material film 11, adopt rod to be coated with the deployed hard conating coating fluid of method coating, make its drying after, usefulness high voltage mercury lamp radiation ultraviolet ray (exposure 400mJ/cm 2), form the hard conating 12 of thick 3 μ m, obtain the film sample.
To the film sample that obtains, estimate the Martens hardness (HM), plasticity hardness (Hupl), impression elastic modelling quantity (Young's modulus) of hard conating 12, being coated with property (anti-steel wool (SW) property and pencil hardness), fracture-resistant and pencil hardness firmly with following method.The result is as shown in table 1.
About (1) " Martens hardness (HM) ", (2) " plasticity hardness (Hupl) " and (3) " Young's modulus ", all use ultra micro hardness test device (Fischer Instruments company, trade name: FISCHERSCOPEHM2000), employing is according to the method for ISO-14577-1, under condition determination described later, measure the case hardness or the Young's modulus of hard conating 12.
(1), the condition determination of (2) and (3) is as described below.
Indenter shape: Vickers pressure head (a=136 °),
Measure environment: 20 ℃ of relative humidity 60% of temperature,
Maximum test load: 1mN,
Load speed: 1mN/20 second,
The maximum load creep time: 5 seconds,
Off-load speed: 1mN/20 second.
About (4) " anti-SW ", at first, with the load of 300g with the surface of the reciprocal wiping hard conating 12 of steel wool #0000 10 times.Then, the surface of perusal hard conating 12 has or not scar.Consequently, do not have be evaluated as " ◎ " of scar, almost do not have be evaluated as " zero " of scar, be evaluated as " * " of obvious scar arranged.
About (5) " pencil hardness ", adopt method according to JIS-K5400 (1990), measure the pencil of film specimen surface and draw the value of writing.And then, with the measured value that obtains is being evaluated as more than the 2H " ◎ ", being evaluated as of the above not enough 2H of H " zero ", in same embodiment, make a plurality of samples, difference according to sample, the measured value that has is the situation of the not enough H of measured value that has of the above not enough 2H of H, is evaluated as " △ ", being evaluated as of the not enough H of measured value " * ".
About (6) " fracture-resistant ", according to resistance to bend(ing) (cylindrical shape axle method) based on JIS-K5600-5-1 (1999), on the iron staff of the about 5mm of diameter, be positioned at the mode film sample of reeling respectively in the outside with hard conating 12, whether perusal cracks at the hard conating 12 of its winding part.Its result does not have be evaluated as " ◎ " of crackle, does not almost have be evaluated as " zero " of crackle, and be evaluated as " △ " of some crackles arranged, and be evaluated as " * " of obvious crackle arranged.
" experimental example 2 "
Except using hard conating by following prescription preparation with the coating fluid, under the condition identical, prepare coating fluid with experimental example 1, obtain the film sample.Carry out mensuration and the evaluation identical then with experimental example 1.The result is as shown in table 1.
＜hard conating coating fluid 〉
5 parts of 6-caprolactone modification three (2-ethoxy) isocyanuric acid esters
(SR368: Saudi horse (サ one ト マ one) company) (solid state component 100%)
10 parts of optical polymerism prepolymer/photopolymerization monomers
(wall Mu Saite 575: waste river chemical industrial company) (solid state component 100%)
0.4 part of Photoepolymerizationinitiater initiater
(IRGACURE 651: vapour crust Japanese firm)
30 parts of propylene glycol monomethyl ethers
" experimental example 3 "
Except with tree multifunctional oligomer A2 (NK エ ス テ Le A-HBR5: Xin Zhong village chemical industrial company) replace the multifunctional oligomer A1 of tree, under the condition identical, prepare coating fluid, obtain the film sample with experimental example 1.Carry out mensuration and the evaluation identical then with experimental example 1.The result is as shown in table 1.
" experimental example 4 "
Except the use level that makes the multifunctional oligomer A1 of tree is 12 parts, to make the use level of optical polymerism prepolymer/photopolymerization monomer be 8 especially, under the condition identical, prepare coating fluid with experimental example 1, obtain the film sample.Carry out mensuration and the evaluation identical then with experimental example 1.The result is as shown in table 1.
" experimental example 5 "
Except the use level that makes the multifunctional oligomer A1 of tree is 4 parts, to make the use level of optical polymerism prepolymer/photopolymerization monomer be 16 especially, under the condition identical, prepare coating fluid with experimental example 1, obtain the film sample.Carry out mensuration and the evaluation identical then with experimental example 1.The result is as shown in table 1.
" experimental example 6 "
Except the use level that makes 6-caprolactone modification three (2-ethoxy) isocyanuric acid ester (hereinafter referred to as " ring structure reactive monomer ") is 1 part, to make the use level of optical polymerism prepolymer/photopolymerization monomer be 14 especially, under the condition identical, prepare coating fluid, obtain the film sample with experimental example 2.Carry out mensuration and the evaluation identical then with experimental example 2.The result is as shown in table 1.
" experimental example 7 "
Except the use level that makes the ring structure reactive monomer is 10 parts, to make the use level of optical polymerism prepolymer/photopolymerization monomer be 5 especially, under the condition identical, prepare coating fluid with experimental example 2, obtain the film sample.Carry out mensuration and the evaluation identical then with experimental example 2.The result is as shown in table 1.
" experimental example 8 "
Except mismatching the multifunctional oligomer A1 of tree (0 part), making the use level of optical polymerism prepolymer/photopolymerization monomer is 20 especially, prepares coating fluid under the condition identical with experimental example 1, obtains the film sample.Carry out mensuration and the evaluation identical then with experimental example 1.The result is as shown in table 1.
" experimental example 9 "
Except using hard conating by following prescription preparation with the coating fluid, under the condition identical, prepare coating fluid with experimental example 1, obtain the film sample.Carry out mensuration and the evaluation identical then with experimental example 1.The result is as shown in table 1.
＜hard conating coating fluid 〉
15 parts of thermoplastic acrylic resins (solid state component 40%)
(A Kudiku (ア Network リ デ イ Star Network) A195: big Japanese ink chemical industrial company)
14 parts of optical polymerism prepolymers/photopolymer monomer
(solid state component 100%) (wall Mu Saite 575: waste river chemical industrial company)
0.4 part of Photoepolymerizationinitiater initiater
(IRGACURE 651: vapour crust Japanese firm)
36 parts of propylene glycol monomethyl ethers
" experimental example 10 "
Except the use level that makes A Kudiku A195 is 20 parts, to make the use level of wall Mu Saite 575 be 12 parts, make the use level of propylene glycol monomethyl ether be 33 especially, under the condition identical, prepare coating fluid with experimental example 9, obtain the film sample.Carry out mensuration and the evaluation identical then with experimental example 9.The result is as shown in table 1.
" experimental example 11 "
The coating fluid of preparation experiment example 4 has obtained forming the film sample of the hard conating 12 of thick 1 μ m.Carry out mensuration and the evaluation identical then with experimental example 4.The result is as shown in table 1.
[table 1]
Figure BPA00001216318300161
Result by table 1 can confirm the following fact.
At first, about being coated with property (anti-SW and pencil hardness) firmly, when the HM of hard conating 12 or the not enough setting of Hupl (experimental example 9～11), being coated with property is tending towards descending firmly.In addition, as experimental example 9, even HM more than setting but during the not enough setting of Hupl, pencil hardness is better than experimental example 10 and experimental example 11, but is lower than experimental example 1～8, and also there is the tendency that is lower than experimental example 1～8 in anti-SW.In addition, as experimental example 11, even during the not enough setting of Hupl HM more than setting, though anti-SW is good, but because the thin thickness of hard conating 12, so pencil hardness is insufficient.Relative therewith, experimental example 1～8 all obtains enough being coated with property firmly.
Then, about fracture-resistant, when the EIT of hard conating 12 surpasses setting (experimental example 8), fracture-resistant is tending towards descending.Relative therewith, experimental example 1～7, experimental example 9～11 all obtain enough fracture-resistants.
By these results as can be known: in this experimental example, experimental example 1～7 has enough being coated with property firmly and fracture-resistant concurrently, and wherein experimental example 1～3 is excellent especially.That is, the film sample of experimental example 1～3 can be taken into account being coated with property and fracture-resistant firmly at high level.
" experimental example 12～14 "
The thickness of the hard conating that will obtain in experimental example 1, experimental example 8 and experimental example 10 is the film sample of 3 μ m, the mode that is arranged in the outside with hard conating when making synthetic resin is assembled into die for injection molding, and (phone cover is with mould, size: about 50mm * 100mm), after forming 3D shape by vacuum forming, in mould, fill the acrylic resin of fusion, with mold cools down, take out with film sample one and solidify the acrylic resin moulding product that obtain.To these synthetic resins, the marginal portion on perusal synthetic resin surface (curved surface or angle part).In addition, to the being coated with property firmly on the surface of these synthetic resins, carry out and the identical evaluation of above-mentioned film sample.
Its result has used the synthetic resin of the film sample of experimental example 1, and crackle or albefaction do not take place in the marginal portion, and being coated with property has also obtained and the same good result of above-mentioned film sample firmly.
Relative therewith, used the synthetic resin of the film sample of experimental example 8, though being coated with property has obtained good result firmly, crackle or albefaction have appearred in the marginal portion.
In addition, used the synthetic resin of the film sample of experimental example 10, though crackle or albefaction do not take place in the marginal portion, being coated with property is poorer than the synthetic resin of experimental example 1 firmly.

Claims (8)

1. a hard coat film is characterized in that, is the hard coat film that hard conating is arranged at least one mask of base material film, and wherein, the Martens hardness of described hard conating is 250N/mm 2More than, plasticity hardness is 800N/mm 2More than, the impression elastic modelling quantity is below the 5000MPa.
2. hard coat film according to claim 1 is characterized in that, the value of described Martens hardness, described plasticity hardness and described impression elastic modelling quantity all is that maximum test load is the measured value under the condition of 1mN.
3. hard coat film according to claim 1 and 2 is characterized in that, using the value of the anti-bend test that the cylindrical shape axle method according to JIS-K5600-5-1 (1999) records is below the 5mm.
4. hard coat film according to claim 3 is characterized in that, when making reciprocal 10 times of steel wool #0000 under the load of 300g, described hard conating does not produce scar.
5. according to each described hard coat film in the claim 1～4, it is characterized in that the thickness of described hard conating is 0.5～10 μ m.
6. according to each described hard coat film in the claim 1～5, it is characterized in that, be formed with one deck at least in the layer that comprises metal evaporation layer, printed layers and adhesive layer at another face of described base material film.
7. a synthetic resin is characterized in that, is that described produced by insert molding film is each described hard coat film in the claim 1～6 with moulding material and the produced by insert molding moulding product with film integrated formation by moulding.
8. synthetic resin according to claim 7 is characterized in that, described moulding material is acrylic resin or polycarbonate resin.
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CN101965261B (en) 2014-05-14
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