CN101941353B - Manufacture method of light-cured composite film - Google Patents
Manufacture method of light-cured composite film Download PDFInfo
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- CN101941353B CN101941353B CN 200910158497 CN200910158497A CN101941353B CN 101941353 B CN101941353 B CN 101941353B CN 200910158497 CN200910158497 CN 200910158497 CN 200910158497 A CN200910158497 A CN 200910158497A CN 101941353 B CN101941353 B CN 101941353B
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Abstract
The invention discloses a manufacture method of a light-cured composite resin film, comprising the following steps of: (1) providing a plastic substrate, light-cured composite resin, a printing ink layer and plastic, wherein the plastic substrate is provided with an upper surface and a lower surface; (2) coating the upper surface of the plastic substrate with the light-cured composite resin; (3) impressing and solidifying the light-cured composite resin to form a plurality of patterns; (4) forming the plastic substrate and the plurality of patterns; (5) coating the printing ink layer on the lower surface of the plastic substrate; and (6) ejecting and attaching the plastic on the printing ink layer.
Description
Technical field
The present invention relates to a kind of diaphragm production method of light-cured composite, relate in particular to a kind of diaphragm production method that cure step is carried out the light-cured composite of forming step again that carries out first.
Background technology
Tradition promotes the manufacturing method thereof of plastic product surface character and surcharge, nothing more than fitting in plastic basis material with metal film layer or artificial leather, or with spray, the mode of spraying paint is as the surface-coated layer.Yet; the applying of metal film layer or artificial leather need be considered the tackability of above-mentioned adhesion coating and plastic basis material; its property followed directly affects the durability degree that product uses; the product surface of making does not in this way have the diaphragm effect; and the appearance colour variability can't be made lines lines or the 3D special-effect graph of colorful complexity with selectively also comparatively dull.As want after above-mentioned applying step, to promote surperficial special grains feel, and need again the spraying coating process of many one coating, so, not only cause easily the coating layer thickness skewness, the surface also has orange peel phenomenon to occur easily; Moreover conventional spray paint technique causes paint loss because easily forming the spittle, and the finished product corner also has buildup and produces, cause the bad of outward appearance, virtually raise the cost, and sprayed coating often contains the heavy metal composition, do not meet RoHS environmental protection standard and make it environment is caused burden.
Film interior trim forming technique IMD (In Mold Decoration/Forming) has then realized injection mo(u)lding, decoration integrated, can make again various special picture and text effect, has ornamental and functional.For improving IMD plastic sheeting surface physical characteristic and ornamental, as promote film surface hardness, abrasion performance characteristic and give the appearance effect such as the special picture and text of film surface, structure, in IMD plastic sheeting surface-coated specific functionality coating, just become an important topic of IMD industry.What industry was commonly used at present is with the film of Dualcure process application in IMD, its program comprises the coating of plastic material upper surface coating specific functionality, and make it reach dry tack free sclerosis in the thermmohardening mode, printing and IMF (In Mold Forming) moulding in order to follow-up lower surface, and carry out plastic injection in internal layer and make final products, carry out again at last the ultraviolet light photopolymerization step, make product surface reach the demand of high rigidity and high abrasion consumption.Yet the shortcoming of Dual cure technique is and must through the twice hardening process, will expends more time cost and fixed cost; And its plastic sheeting is before UV cured face coat, and its surperficial scratch resistance, abrasion performance characteristic are very poor, causes the impaired bad order that causes of face because of process equipment and manually-operated easily, produces yield and significantly reduces; The step of last sclerosis is after the final products forming step on the other hand, also be that downstream application end (such as shell manufactory) must be after the shape of shell molds, carry out again the step of hardening of resin, so the downstream client must have ultraviolet light photopolymerization equipment, thereby cause the cost of downstream manufacturers to increase, and also can cause the process costs of outer casing forming factory to rise at last.
For example there is again R﹠D team that cure step is moved to before the forming step; but it still uses the not ductile resin of tool; with the mode coating resin of discontinuous shape, but this practice also causes the complicated of technique, and the resin molding of discontinuity is so that the defencive function of appearance is not good yet simultaneously.
Summary of the invention
Main purpose of the present invention is to provide a kind of diaphragm production method of light-cured composite, this manufacture method can provide a resin bed with deep drawing quality, make above-mentioned in-mold decoration forming technique can carry out first the hardening of resin step, carry out again a forming step, and after the moulding not like Dual cure material, need not apply again after-hardening technique behind the film forming, so have the technique of simplification, cost-effective effect; And its finished surface has special gloss, special picture and text and lines feel and height abrasionproof scratch resistance characteristic concurrently, is the diaphragm of effect more than.
In order to realize above-mentioned purpose, the invention provides a kind of diaphragm production method of light-cured composite, it is characterized in that step is as follows: provide a plastic basis material, a photocuring plyability resin, an ink lay and plastics, and this plastic basis material has a upper surface and a lower surface; Be coated with this photocuring plyability resin in the upper surface of this plastic basis material; And impression and this photocuring plyability resin of curing, to form a plurality of patterns; This plastic basis material of moulding and these a plurality of patterns; This ink lay of coating is in the lower surface of this plastic basis material; And penetrate these plastics with this ink lay of fitting, this pattern can comprise 2D/3D pattern and various stereochemical structures etc., this photocuring plyability resin comprises any one or more of a pure acrylic resin, a polyesters acrylic resin, an epoxies acrylic resin, a polyurethanes acrylic resin, and to account for this photocuring plyability resinous principle ratio be 5% to 95%.
The present invention has following benefit: the IMD technique that the present invention proposes is saved one moulding after heat hardening process or ultraviolet light photopolymerization program, also namely only need one cure step, more having improved Dual cure technique needs carry out in client the shortcoming of follow-up hardening process, and because plastic sheeting upper surface polymer coating has passed through the ultraviolet light photopolymerization program, its surperficial scratch resistance and abrasion performance characteristic are excellent, can avoid the cosmetic damage that causes because of equipment and manually-operated, save the also yield of improving product, significantly the improving product market acceptance of expending of client fixed cost.
For enabling further to understand feature of the present invention and technology contents, see also following about detailed description of the present invention and accompanying drawing, yet appended accompanying drawing only provide with reference to and explanation usefulness, be not to the present invention's limitr in addition.
Describe the present invention below in conjunction with the drawings and specific embodiments, but not as a limitation of the invention.
Description of drawings
Fig. 1 is the flow chart of the diaphragm production method of light-cured composite of the present invention;
Fig. 2 A to Fig. 2 D is the schematic diagram of the diaphragm production method of light-cured composite of the present invention.
Wherein, Reference numeral:
1: plastic sheeting
10: plastic basis material
11: pattern
12: ink lay
13: plastics
The specific embodiment
See also Fig. 1, the invention provides a kind of diaphragm production method of light-cured composite, the photocuring plyability resin that this manufacture method can be used deep drawing quality is coated in the upper surface of plastic basis material 10 to form a pattern that is ductile 11, and this plastic basis material 10 and this pattern 11 are can be simultaneously when moulding moulding and form a predetermined outward appearance, and its manufacture method comprises the steps:
Step 1 a: plastic basis material 10 is provided, this plastic basis material 10 can be polyethylene terephthalate (Polyethylene Terephthalate, PET), Merlon (Polycarbonate, PC), Triafol T (Tri-acetyl Cellulose, TAC), polymethyl methacrylate (Polymethylmethacrylate, PMMA), copolymer of methyl methacrylatestyrene (Methylmethacrylate styrene) or cyclenes copolymer (Cyclic Olefin Copolymer, the material such as COC), but be not limited with above-mentioned.In specific embodiment, the thickness of this plastic basis material 10 is 10 to 1000 microns (μ m) in addition, but above-mentioned thickness can be adjusted according to different application.
Step 2: a kind of photocuring plyability resin is provided, and this photocuring plyability is resin-coated in the upper surface of this plastic basis material 10.In this step, this photocuring plyability resin is the upper surface of coating this plastic basis material 10 with suitable method, carries out such as modes such as utilizing screen painting, roller coating, die head coating.
And this photocuring plyability resin can be divided into a ultraviolet light photopolymerization resin or a thermosetting resin according to its sclerosis mode, wherein this ultraviolet light photopolymerization resin comprises pure acrylic acid fat (Full acrylate resin), polyesters acrylate oligomer (Polyester acrylate oligomer), epoxies acrylate oligomer (Epoxy acrylate oligomer), polyurethane kind acrylate oligomer (Polyurethaneacrylate oligomer) any one or more, and account for this photocuring plyability resinous principle ratio and be roughly 5% to 95%; Also this ultraviolet light photopolymerization resin can be dispersed in the suitable diluent, above-mentioned various resins can be classified and diluting monomer that diluent comprises also can comprise any one or more of monofunctional reaction monomers, difunctionality radical reaction monomer, trifunctional radical reaction monomer and multiple functional radical reaction monomers according to its functional group's number again, and account for this photocuring plyability resinous principle ratio and be roughly 5% to 95%; For example, the monofunctional reaction monomers can be PHEA (2-phenoxy ethyl acrylate-2-phenoxyethyl acrylate), PH3EOA (Ethoxylated Phenoxyl Acrylate-ethoxyquin phenoxy group ethene acid esters), CTFA (Cyclic Trimethylol-propane Formal Acrylate-ring trimethylolpropane dimethoxym ethane acrylate), BA (Benzyl Acrylate-phenyl acrylate), LA (Lauryl Acrylate-laurate acrylate), LMA (Lauryl Methacrylate-laurate methacrylate), SA (Stearyl Acrylate-stearic acid acrylate), SMA (StearylMethacrylate stearic acid methacrylate), ISODA (Isodecyl Acrylate isodecyl acrylate), ODA (C8-C10 Acrylate-C8-C10 acrylate), IBOA (IsobornylAcrylate-iso-bornyl acrylate), IBOMA (Isobornyl Methacrylate-isobornyl methacrylate), EOEOEA (2-(2-Ethoxyethoxy) Ethyl Acrylate-ethoxy ethoxy ethyl propylene acid esters) etc., chemical formula as follows: Mono (meth) acrylate (wherein, R1=H, CH3; R2 can be Alkyl alkyl, Carboxyl group carboxyl, Phenol ethoxylate ethoxyquin phenolic group etc.)
Difunctionality radical reaction monomer can be HPHPDA (Hydroxypivalyl HydroxypivalateDiacrylate-3-hydroxyl-2,2-dimethyl propyl-3-hydroxyl-2,2--dimethyl propyl ester diacrylate), DCPDA (dicyclopentadiene acrylate-tristane dimethanol diacrylate), HDDA (1,6-hexanediol diacrylate-1, the 6--hexanediyl ester), (Ethoxylated 1 for HD2EODA, 6-Hexanediol Diacrylate-ethoxyquin 1, the 6--hexanediyl ester), DPGDA (Dipropylene Glycol Diacrylate-propylene glycol diacrylate), TPGDA (Tripropylene Glycol Diacrylate-tripropylene glycol diacrylate), PEGDA (Polyethylene Glycol Diacrylate-polyethyleneglycol diacrylate), NPGDA (Neopentyl Glycol Diacrylate-neopentylglycol diacrylate), NPG2PODA (Propoxylated Neopentyl Glycol Diacrylate-the third oxidation neopentylglycol diacrylate), BEPDDA (2-Butyl-2-Ethyl-1,3-Propanediol Diacrylate-2-butyl-2-ethyl-1, the ammediol diacrylate), BPA4EODA (Ethoxylated Bisphenol-ADiacrylate-Yi Yangization Twin phenol A diacrylate), BPA1OEODA (EthoxylatedBisphenol-A Diacrylate-Yi Yangization Twin phenol A diacrylate), MPDDA (2-Methyl-1,3-Propanediol Diacrylate-2-methyl isophthalic acid, the ammediol diacrylate), MPD2EODA (Ethoxylated2 2-Methyl-1,3-Propanediol-ethoxyquin-2-methyl isophthalic acid, the ammediol diacrylate), EGDMA (Ethylene Glycol Dimethacrylate-ethylene glycol dimethacrylate), PEGDMA (Polyethylene Glycol Dimethacrylate-polyethylene glycol dimethacrylate), BPA2EODMA (Ethoxylated Bisphenol-A Dimethacrylate-ethoxyquin bisphenol a dimethacrylate), BPA4EODMA (Ethoxylated Bisphenol-ADimethacrylate-ethoxyquin bisphenol a dimethacrylate), BPA10EODMA (EthoxylatedBisphenol-A Dimethacrylate-ethoxyquin bisphenol a dimethacrylate), 3EGDMA (Triethylene Glycol Dimethacrylate-TEGDMA), DEGDMA (Diethylene Glycol Dimethacrylate-diethylene glycol dimethylacrylate), HEMAP (2-Hydroxyethyl methacrylate phosphate-2-HEMA phosphate) etc., please refer to following chemical formula: Di (meth) acrylate (R1=H, CH3, wherein R2 can be the Alkylene vinyl, Bisphenol A ethoxylate ethoxyquin bisphenol-A, Hydroxy group alkyl etc.).
Trifunctional radical reaction monomer can be THEICTA (tris (2-hydroxyethyl)-isocyanuratetriacrylate-three (2-ethoxy) isocyanic acid triacrylate), TMPTA (trimethylol propanetriacrylate-trimethylolpropane triacrylate), PET3A (PentaerythritolTriacrylate-pentaerythritol triacrylate), TMP3EOTA (EthoxylatedTrimethylolpropane Triacrylate-ethoxyquin trimethylolpropane triacrylate), TMP3POTA (trimethylolpropane-3PO-triacrylate-the third oxidation trimethylolpropane triacrylate), TMP9EOTA (Ethoxylated (9) trimethylolpropane triacrylate-ethoxyquin trimethylolpropane triacrylate), TMPl5EOTA (EthoxylatedTrimethylolpropane Triacrylate-ethoxyquin trimethylolpropane triacrylate), G3POTA (Propoxylated Glyceryl Triacrylate-glycerol propoxylate triacrylate), TMPTMA (Trimethylolpropane trimethylacrylate-trimethylol-propane trimethacrylate), TMP3EOTMA (Ethoxylated Trimethylolpropane Trimethacrylate-ethoxyquin trimethylol-propane trimethacrylate) etc., chemical formula as follows: Tri (meth) acrylate and Multi-functional (meth) acrylate (R1=H, CH3, wherein R2 can be Trimethylolpropane three hydrocarbon methyl-prop alkyl, Pentaerythritol pentaerythrite base, Propoxylated Glyceryl glycerol propoxylate base)
N 〉=3 wherein; And the multiple functional radical reaction monomers is DPHA (DipentaerythritolHexaacrylate-dipentaerythritol acrylate), PET4A (Pentaerythritoltetraacrylate-tetramethylol methane tetraacrylate), PET5EO4A (PentaerythritolTetraacrylate Omnimer-ethoxyquin tetramethylol methane tetraacrylate), DiTMP4A (Ditrimethylolpropane Tetraacrylate-couple-trimethylolpropane tetra-acrylate), PET5PO4A (Propoxylated Pentaerythritol Tetraacrylate-the third oxidation tetramethylol methane tetraacrylate) etc., except above-mentioned composition, also can add other composition among this ultraviolet light photopolymerization resin, (for example: inorganic nano material such as nanometer SiO2 (silica) for example add organic inorganic hybrid, nano-ZnO (zinc oxide), nanometer Al2O3 (aluminium oxide), nano Ce O2 (cerium oxide) is made in above-mentioned monomer or the macromolecule oligomer with grafting or dispersing mode), the light initiator (for example: commercial product:CIBA 184, CIBA 369, CIBA 173, CIBA 819, CIBA TPO etc.), levelling or froth breaking auxiliary agent, lubrication prescription (for example: polyester resin change properties of organic silicon, organic silicon modified by polyether, the alkyl-modified organosilicon of aromatic alkyl, fluorin modified crylic acid EVA and above-mentioned derivative) any one or more, and account for this photocuring plyability resin ratio and be roughly 0.1% to 20%.On the other hand, comprise acrylic polyol resin, PEPA and other additive (the same organic inorganic hybridization thing, light initiator, levelling or defoamer, the lubrication prescription etc. that are set forth in the ultraviolet light photopolymerization resin) in this thermosetting resin, but be not limited with above-mentioned.
Step 3: press firmly, solidify this photocuring plyability resin to form a pattern that is ductile 11 in the upper surface (such as Fig. 2 A) of this plastic basis material 10.The photocuring plyability resin that then is coated with according to step 2 in this step carries out different hardening processes, for example, ultraviolet light photopolymerization technique: with this coating of ultraviolet light energy exposure of 50-3000mj/cm2, or thermmohardening technique: waited in 1 to 100 minute with 60-200 ℃ of baking coating to be hardened and to form a pattern 11 with high ductibility, and in the process of above-mentioned coating sclerosis, simultaneously in the forming step of this pattern 11, roller or the mould that can use the surface to be provided with structure carry out in the mode of prolonging pressure, this pattern 11 can be cuboid, cone, polygonal cylinder, the structures such as 2D/3D figure or lines lines, but be not limited with above-mentioned.
And by above-mentioned manufacture method, can make a plastic sheeting 1 that is construed as by this pattern 11 and this plastic basis material 10, because this pattern 11 all has high ductibility with this plastic basis material 10, so this plastic sheeting 1 is when being subjected to external force to produce deformation, this pattern 11 still can fit tightly each other with this plastic basis material 10 and the phenomenon that this pattern 11 cracked (cracking) can not occur or peel off (peeling).Moreover, this pattern 11 on this plastic sheeting 1 has the characteristic of high rigidity, and this pattern 11 can represent different special gloss, such as metallic luster, special graph or literal or special grains feel, such as leather hand feeling etc., also namely this plastic sheeting 1 for having the multilayer film of above-mentioned multiple different functionalities.
On the other hand, also comprise that one adds and be scattered in the step of this photocuring plyability resin with the organic or inorganic particulate before the step 2, for example will (particle diameter be between 1～100nm) for micro mist with nanometer grade silica (Silica dioxide) for micron order polyurethane (PU) powder (particle diameter is between 1～100 μ m), be dispersed to evenly with suitable mixing plant, so as to above-mentioned powder particle being scattered in equably among this photocuring plyability resin; This organic or inorganic particulate kind is any one or more of polymethyl methacrylate (PMMA), silica (Silica dioxide), ceria (Cerium dioxide), aluminium oxide (Aluminumtrioxide), zinc oxide (Zinc oxide), sodium oxide molybdena (Sodium oxide), and this particulate adds and is roughly approximately 0.1% to 60%.
Also comprise any one or more of an organic hybrid thing or an inorganic hybrid in the photocuring plyability resin, and account for this photocuring plyability resin ratio and be roughly 0.1% to 50%.
Next, step 4 please refer to Fig. 2 B: the plastic sheeting 1 of this tool ductility is shaped to a predetermined face shaping.The shape that this plastic sheeting 1 is shaped to needed final products in this step, such as utilizing the techniques such as high pressure, high temperature or vacuum forming that this plastic sheeting that is ductile 1 is shaped to the hull shape that phone housing etc. has predefined external appearance.And in technique proposed by the invention, carry out again the outward appearance forming step although first photocuring plyability hardening of resin is formed pattern 11, but because this pattern 11 is ductile, so when being subjected to external force to produce distortion, this pattern 11 still can be attached on the plastic basis material 10 by the extension ability, and can chipping grade cause the situation of structural deterioration
Step 5 please refer to Fig. 2 C: coating one ink lay 12 is in the lower surface of this plastic basis material 10.This ink lay 12 is colorful or 3D printing ink to be coated in the lower surface of this plastic basis material 10 by mode of printing, and 12 of this ink laies can show colorful lines lines or 3D picture and text special efficacy etc., but are not limited with above-mentioned.
Follow step 6, please refer to Fig. 2 D: moulding and molding inject plastics 13 in the lower surface of this plastic basis material 10.In this step be first will be in step 5 the plastic basis material after the moulding 10, pattern 11 and ink lay 12 place in the mould of being scheduled to, the mode that recycling penetrates penetrates the below that plastics 13 fit in this ink lay 12, can be Merlon (PC) with these plastics 13 of shell that form product, polypropylene (Polypropylene, PP), styrene (Polystyrene, PS), polymethyl methacrylate (PMMA), copolymer of methyl methacrylatestyrene (Methylmethacrylate styrene), acrylonitrile-butadiene-styrene copolymer (ABS), polyethylene terephthalate (PET), polyformaldehyde (Polyoxymethylene, POM), the materials such as nylon (Nylon).Plastic basis material 10 after this moulding and pattern 11 can be coated in the outside of these plastics 13 whereby, have special gloss to provide, an adventitia of special picture and text or lines feel, and the protective layer of the better anti-scratching wearproof of these plastics 13 and this ink lay 12 more can be provided.
Below, the present invention will carry out for the photocuring plyability resin of heterogeneity ratio above-mentioned in-mold decoration forming technique and make 13 groups of enforcement aspects, the go forward side by side characteristic test of line correlation: at first allocate special ultraviolet light photopolymerization resin compounded prescription, this ultraviolet light photopolymerization resinous principle ratio is 20% to 80%, the best is 40% to 60%, wherein the ultraviolet light photopolymerization resin comprises two or more functional groups' acrylic resin, the organic inorganic hybridization thing, diluting monomer (comprises monofunctional, the difunctionality base, the any one or more combination of trifunctional base and multiple functional radical reaction monomers) etc., need add the light inlet initiator in addition, levelling or froth breaking auxiliary agent, lubrication prescription etc., after uniform stirring mixes, can be added into again moistening micron or nano particle in above-mentioned prescription, its extra percentage by weight that adds is about 5 to 60%, add two kinds of fine particles at those embodiment and be respectively micron-level poly (methyl methacrylate) (PMMA) powder (particle diameter is between 1 to 100 μ m) and nanometer grade silica (Silica dioxide) micro mist (particle diameter between 1 to 100nm), with homogenizer dispersed with stirring 20 minutes, again with nano-milled dispersion machine, and cooperate ultrasonic vibrating after one hour, the colloid prescription of above-mentioned ultraviolet light photopolymerization resin is coated Merlon (PC) membrane surface (being the surface of plastic basis material 10) of 200 μ m, the unhardened resinous coat that is about 20 μ m to form coating thickness, re-use the structure roller and make the solid geometry structure to prolong the pressure mode on unhardened plastic film surface, art picture and text or lines lines etc., and carry out simultaneously ultraviolet light photopolymerization program (the UV irradiation energy is about 1000mj/cm2) with unhardened resinous coat sclerosis formation pattern 11.Carry out afterwards release demoulding and shaping structures and get final product to get the scratch-resistant protective film layer of special gloss, special picture and text and lines feel, again can be with plastic basis material 10, pattern 11 common moulding to obtain the outside embryo of phone housing protective layer in the present embodiment through high pressure or vacuum forming; Then can carry out colorful in the lower surface of plastic basis material 10 or the 3D ink printing to form an ink lay 12; Again the diaphragm after the above-mentioned moulding is inserted in the jetting mold, then carry out ABS ejection formation step in the lower surface of plastic basis material 10 and finish that above-mentioned mould is in-built to be set to the finished product that type technique is produced.Table one is the proportion of composing of respectively organizing different embodiments.
The sample information of table one ultraviolet light photopolymerization resin formula and adding proportion
A: deep drawing quality oligomer (resin)
B: monofunctional reaction monomers
C: difunctionality radical reaction monomer
D: trifunctional radical reaction monomer
E: multiple functional radical reaction monomers
F: organic inorganic hybridization thing
G: additive
H: the organic-inorganic charges (wherein, inorganic filler: SiO2 (silica) particulate, ZnO (zinc oxide) particulate, Al2O3 (aluminium oxide) particulate, CeO2 (cerium oxide) particulate etc., organic filler: PMMA (polymethacrylates) particulate, PU (polyurethane) particulate etc.)
Analyze one: table two is the specificity analysises that sample 1～5 carried out aforementioned rete according to the interpolation of differential responses monomer.Wherein abrasion resistance test is that steel wool with 100 g of loadings rubs 100 times back and forth, and detects its haze change amount to penetrate haze meter.Height 10mm is used in the extensibility test, and the mould of R value 0.4mm is tested its moulding extensibility with the IMD forming machine.The result who is detected by table two shows: use the monofunctional monomer as diluent, have the most excellent IMD mouldability, but hardness and abrasion performance effect are general; And with the monomer more than the difunctionality base as diluent, can promote hardness and abrasion performance characteristic, and not affect then, but its IMD moulding result also is general.
The detection that table two differential responses monomer adds relatively
Analyze two: table three is the specificity analysises that sample 6～8 carried out aforementioned rete according to the adding proportion of different trifunctional monomers.The result who is detected by table three shows: use 20% above trifunctional reaction monomers as diluent, can promote case hardness and abrasion performance effect, yet but make as a result variation of IMD moulding, the beginning has better molding effect below 10% and the addition of trifunctional reaction monomers is down to.
The detection of table three trifunctional monomer adding proportion relatively
Analyze three: table four is the specificity analysises that sample 9～11 carried out aforementioned rete according to the adding proportion of different organic inorganic hybridization things.The result who is detected by table four shows: add 20% above organic inorganic hybridization thing in prescription, mainly can promote the abrasion performance effect and slightly promote case hardness, and IMD moulding result's performance presents general effect, and the beginning has better molding effect below 10% and addition is down to.
The detection of table four organic inorganic hybridization thing adding proportion relatively
Analyze four: table five is the specificity analysises that sample 11～13 carried out aforementioned rete according to the adding proportion of different auxiliary agents and filler.The result who is detected by table five shows: add lubrication prescription and can effectively reduce skin-friction force in prescription, and then promote the abrasion performance characteristic and slightly promote case hardness, and do not affect then and the IMD mouldability; And in prescription, add organic/inorganic filler (filler), and more can significantly promote hardness and wear characteristic, and not affect then property, do not affect the IMD molding effect yet.
The detection of table five auxiliary agent and filler adding proportion relatively
Yet from the resulting analysis data of the ultraviolet light photopolymerization resin of above-mentioned different compositing formulas, sample 12,13 composition have better diaphragm characteristics, so comprehensive sample 12,13 prescription form, the composition of preferred embodiment of the present invention and processing step are:
Step (one): the compound prescription of allocating special ultraviolet light photopolymerization resin, wherein the deep drawing quality oligomer accounts for total composition percentage by weight 50%, diluent uses difunctionality radical reaction monomer and trifunctional radical reaction monomer to account for total composition percentage by weight 30% to 40%, and collocation organic inorganic hybridization thing accounts for total composition percentage by weight 10% to 20%, and additionally add light inlet initiator, levelling or froth breaking auxiliary agent, lubrication prescription accounts for total composition percentage by weight 5% altogether, and full and uniform stirring makes its mixing and dispersion.
Step (two): be added into moistening micron or nano particle in above-mentioned prescription, percentage by weight is about 5 to 50% among its extra interpolation, wherein add two kinds of fine particles and be respectively micron-level poly (methyl methacrylate) (PMMA) powder (particle diameter is between 1 to 100 μ m) and nanometer grade silica (Silicadioxide) micro mist (particle diameter between 1 to 100nm), with homogenizer dispersed with stirring 20 minutes, again with nano-milled dispersion machine, and cooperate ultrasonic vibrating one hour.
Step (three): the colloid prescription of above-mentioned ultraviolet light photopolymerization resin is coated polycarbonate (PC) diaphragm upper surface (being plastic basis material 10 upper surfaces) of 200 μ m, be about the unhardened plastic film of 20 μ m in this polycarbonate (PC) membrane surface to form coating thickness.
Step (four): utilize the structure roller to make (being pattern 11) such as plane, solid geometry structure, artistic picture and text or lines lines to prolong the pressure mode at the lip-deep resinous coat of unhardened plastic film, and carry out simultaneously ultraviolet light photopolymerization program (the UV irradiation energy is about 1000mj/cm2) with resinous coat sclerosis formation pattern 1
1 (please refer to Fig. 2 A).
Step (five): carry out release demoulding and shaping structures.
Step (six): can be with plastic basis material 10, pattern 11 common moulding to obtain the outside embryo (please refer to Fig. 2 B) of phone housing protective layer in the present embodiment through high pressure or vacuum forming.
Step (seven): in the lower surface of plastic basis material 10 carry out colorful or the 3D ink printing to form an ink lay 12 (please refer to Fig. 2 C).
Step (eight): the diaphragm after the above-mentioned moulding is inserted in the jetting mold, then carry out ABS (being plastics 13) ejection formation one final products (please refer to Fig. 2 D) in the below of ink lay 12.
In sum, the present invention has following all advantage:
The present invention uses a pattern 11 with deep drawing quality and coats on the plastic basis material 10, and this resin before moulding namely through ultraviolet light photopolymerization, make its surperficial tool scratch resistance and abrasion performance characteristic, and hardening process that needn't be extra after the moulding, so can simplify existing in-mold decoration forming technique, can solve the problem that client must be bought more hardening equipment simultaneously.
On the other hand, the pattern 11 of the deep drawing quality that technique of the present invention is used can still adhere well to plastic basis material 10 in the process of moulding, and does not have cracked problem.
Compare with Dual Cure technique, technique of the present invention is saved thermmohardening program or the ultraviolet light photopolymerization program after one moulding, having improved Dual cure technique needs carry out in client the shortcoming of follow-up hardening process, and overcome because of Dual Cure technique because of its pattern before moulding fully the sclerosis, it is very poor to satisfy its surperficial scratch resistance, when technique and manually-operated, the appearance sensitive for damages, cause the finished product yield to descend, the present invention can save expending of client fixed cost, improving product market acceptance significantly, for client shortens the production time, promote yield etc., reaching the purpose that reduces cost, and product more meets RoHS environmental protection regulations, is a kind of Green Product that environment is not caused load.
Certainly; the present invention also can have other various embodiments; in the situation that does not deviate from spirit of the present invention and essence thereof; those of ordinary skill in the art work as can make according to the present invention various corresponding changes and distortion, but these corresponding changes and distortion all should belong to the protection domain of the appended claim of the present invention.
Claims (6)
1. the diaphragm production method of a light-cured composite is characterized in that, may further comprise the steps:
Provide a plastic basis material, a photocuring plyability resin, an ink lay and plastics, and this plastic basis material have a upper surface and a lower surface;
Be coated with this photocuring plyability resin in the upper surface of this plastic basis material;
Impression and this photocuring plyability resin of curing are to form a plurality of patterns;
This plastic basis material of moulding and these a plurality of patterns;
This ink lay of coating is in this lower surface; And
Penetrate these plastics with this ink lay of fitting, this photocuring plyability resin comprises any one or more of a pure acrylic resin, a polyesters acrylic resin, an epoxies acrylic resin, a polyurethanes acrylic resin, and to account for this photocuring plyability weight resin percentage be 5% to 95%.
2. the diaphragm production method of light-cured composite according to claim 1, it is characterized in that, this plastic basis material is a polyethylene terephthalate, a Merlon, a Triafol T, a polymethyl methacrylate, monomethyl methyl acrylate-styrol copolymer or a cyclenes copolymer material, and the thickness of this plastic basis material is 10 to 1000 microns.
3. the diaphragm production method of light-cured composite according to claim 1, it is characterized in that, this photocuring plyability resin also comprises a diluent, this diluent comprises a diluting monomer, this diluting monomer has any one or more of a monofunctional reaction monomers, a pair of functional group reaction monomers, a trifunctional radical reaction monomer, a multiple functional radical reaction monomers, and to account for this photocuring plyability weight resin percentage be 5% to 95%.
4. the diaphragm production method of light-cured composite according to claim 1, it is characterized in that, this photocuring plyability resin also comprises any one or more of a levelling agent, a defoamer or a lubrication prescription, and to account for this photocuring plyability weight resin percentage be 0.1% to 20%.
5. the diaphragm production method of light-cured composite according to claim 1, it is characterized in that, wherein photocuring plyability resin also comprises any one or more of organic hybrid or inorganic hybrid, and to account for this photocuring plyability weight resin percentage be 0.1% to 50%.
6. the diaphragm production method of light-cured composite according to claim 1, it is characterized in that, this photocuring plyability resin also comprises: an organic or inorganic particulate, its particle diameter is between 1nm to 100 μ m, this organic or inorganic particulate kind is any one or more of polymethyl methacrylate, silica, ceria, aluminium oxide, zinc oxide, sodium oxide molybdena, and it is 0.1% to 60% that this particulate adds percentage by weight, and is scattered in this photocuring plyability resin.
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| JP5706861B2 (en) * | 2011-10-21 | 2015-04-22 | キヤノン株式会社 | Detector, detection method, imprint apparatus, and article manufacturing method |
| JP6636776B2 (en) * | 2014-11-11 | 2020-01-29 | 凸版印刷株式会社 | Decorative sheet and method for manufacturing decorative sheet |
| CN104816511B (en) * | 2015-04-29 | 2017-06-13 | 深圳市华星光电技术有限公司 | Case frame and preparation method thereof |
| CN109057208A (en) * | 2018-07-27 | 2018-12-21 | 江苏贝格丽新材料科技有限公司 | A kind of corrosion-resistant, anti-pollution, mould proof fungi-proofing wall decoration film and manufacturing method |
| TWI708680B (en) * | 2019-01-08 | 2020-11-01 | 穎華科技股份有限公司 | Polymer plastic front plate and method for manufacturing the same |
| CN110515142A (en) * | 2019-08-29 | 2019-11-29 | 安徽屹珹新材料科技有限公司 | A kind of colorful optical film and its preparation method and application structure |
| TWM621890U (en) * | 2021-05-21 | 2022-01-01 | 金亞典科技有限公司 | Light-transmitting decorated molding article |
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| EP1647399A2 (en) * | 2004-10-12 | 2006-04-19 | Bayer MaterialScience AG | Deformable composite plastic film coated with a soft touch lacquer, and plastic composite structures and method of its manufacture |
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