CN104129129A - Resin laminate - Google Patents
Resin laminate Download PDFInfo
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- CN104129129A CN104129129A CN201410174664.XA CN201410174664A CN104129129A CN 104129129 A CN104129129 A CN 104129129A CN 201410174664 A CN201410174664 A CN 201410174664A CN 104129129 A CN104129129 A CN 104129129A
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- Prior art keywords
- methyl
- layer
- resin
- acrylate
- resin layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- 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
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/584—Scratch resistance
Landscapes
- Laminated Bodies (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
本发明提供具有高的表面硬度且具有高透明性的树脂层叠体。一种树脂层叠体，具备硬质树脂层和基材层，所述硬质树脂层由以多官能(甲基)丙烯酰基单体为必要成分的固化型树脂组合物形成，具有三维交联结构且具有25μm～250μm的厚度，所述基材层由单层或2层以上的多层的热塑性树脂构成，上述硬质树脂层独自的拉伸弹性模量为2000～4000兆帕，并且全光线透射率为90％以上，另外，基材层的总厚度t1与硬质树脂层的厚度t2之比(t1/t2)为0.25～10，树脂层叠体的划痕硬度为40g以上。
The present invention provides a resin laminate having high surface hardness and high transparency. A resin laminate comprising a hard resin layer and a substrate layer, the hard resin layer is formed of a curable resin composition containing a polyfunctional (meth)acryloyl monomer as an essential component and has a three-dimensional crosslinked structure and have a thickness of 25 μm to 250 μm, the base material layer is composed of a single layer or two or more layers of thermoplastic resin, the tensile elastic modulus of the above-mentioned hard resin layer alone is 2000 to 4000 MPa, and all light The transmittance is 90% or more, and the ratio (t 1 /t 2 ) of the total thickness t 1 of the base material layer to the thickness t 2 of the hard resin layer is 0.25 to 10, and the scratch hardness of the resin laminate is 40 g or more .
Description
Technical field
The present invention relates to have the laminated resin body of excellent case hardness, the transparency and processing and forming, be particularly applicable to the laminated resin body of display pannel as transparent multilaminar sheet.
Background technology
In the electronic equipment such as digital camera, mobile phone; as the substrate of liquid crystal display etc.; or as the surface for the protection of liquid crystal display etc. be not scratched, the baffle of pollution etc. etc., use the duplexer of being made by thermoplastic resins such as acrylic acid, Merlon, PETGs.These resins that form duplexers are because optical characteristics is excellent and have with glassy phase than being difficult for such characteristic of breaking, so using the field of glass also to start to be widely used in recent years in the past.But, the thermoplastic resins and glassy phase ratio such as acrylic acid, Merlon, PETG, case hardness, mar proof, marresistance are poor, have the such shortcoming of easy scuffing.
In order to eliminate this shortcoming, all the time in the research of carrying out about the surface modification of laminated resin body.For example, extensively implemented resin-coated in the method for substrate surface by thermosetting resin, ultraviolet hardening.Implement, in the laminated resin body of coating, aspect mar proof, marresistance, can see improvement to a certain extent, but about case hardness insufficient, with glassy phase ratio, case hardness to be low at these, in practicality, had very large problem.
As the coating technique for transparent plastic material further being improved to case hardness, for example, carry out the trial (with reference to patent documentation 1, patent documentation 2, patent documentation 3) that the filler by hard conating being sneaked into high rigidity improves case hardness.In addition, as similar method, study the thickness that increases hard conating, sneaked into inorganic and/or organic crosslinked particle or imported functional group on the surface of this particle for relaxing the stress producing the method (with reference to patent documentation 4, patent documentation 5) that makes the partial cross-linked so-called hybrid inorganic-organic of the resin of itself and hard conating.In addition, also carried out by making hard conating multiple stratification, the thickness that increases coating entirety obtains the trial (with reference to patent documentation 6) of higher case hardness.
But, as the concrete example of these methods and the example illustrating, make pencil hardness reach 6H from 4H with regard to high PETG film, tri cellulose acetate membrane as base material with original pencil hardness compared with polycarbonate resin, although confirmed this effect, if but could realize pencil hardness during only for thin hard conating, therefore the miscellaneous function of hard basalis, inorganic material would be essential.Therefore, these basalises, inorganic material become the transparent key factor of obstruction, are not suitable for the such display unit of liquid crystal display.
In addition, also carry out following trial,, be used as the polycarbonate resin of the resin that pencil hardness is low, on polycarbonate resin base material, form 2 coating films with specific thickness, this film is made up of the ultraviolet curing resin that contains two sense urethane acrylates, multifunctional oligomer, polyfunctional monomer, monofunctional monomer and have a specific functional group number, but pencil hardness is 4H to the maximum in this technology, and insufficient (with reference to patent documentation 7).
In addition, above-mentioned patent documentation 7 is evaluated the scratch hardness of utilizing pencil method to measure based on JIS K5600-5-4, the material of stacked hard conating, hard resin layer on thermoplastic resin, be subject to the impact as the thermoplastic resin of lower floor according to character, the thickness of thermoplastic resin and hard resin layer, produce the plastic deformation, the strain that cause because of depression, be at first sight difficult to distinguish that surface is is only depression or the scar being caused by cut.In addition, according to the material difference of hard resin layer, sometimes break because the distortion due to original unexpected depression produces, only utilizing in the mensuration of pencil hardness, be difficult to measure correct case hardness.In addition; during as described above for purposes such as the baffles of liquid crystal display etc.; need in daily life consideration protection to avoid the cut being caused by firmer metal, mineral etc.; therefore with metal, mineral facies than in the judgement of being undertaken by soft pencil method, probably with actual daily life in mar proof, marresistance have difference.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2002-107503 communique
Patent documentation 2: TOHKEMY 2002-060526 communique
Patent documentation 3:WO2010/035764 brochure
Patent documentation 4: TOHKEMY 2000-112379 communique
Patent documentation 5: TOHKEMY 2000-103887 communique
Patent documentation 6: TOHKEMY 2000-052472 communique
Patent documentation 7: No. 4626463 communique of Japan Patent
Summary of the invention
The present invention completes in view of the problem of above-mentioned prior art, and its object is to provide the laminated resin body that has high surface hardness and have high transparent.
The present inventor etc. are excellent and have a laminated resin body of high transparent in order to obtain case hardness, conduct in-depth research, found that the laminated resin body that possesses the hard resin layer being formed by the hardening resin composition specifying and the substrate layer being formed by thermoplastic resin by formation, can realize these objects simultaneously, thereby complete the present invention.
; the present invention is a kind of laminated resin body; it is characterized in that; possess hard resin layer and substrate layer; described hard resin layer is by forming taking multifunctional (methyl) acryl monomer as the curable resin composition of neccessary composition; there is three-dimensional crosslinking structure and there is the thickness of 25 μ m～250 μ m; described substrate layer is made up of the thermoplastic resin of individual layer or 2 layers of above multilayer; above-mentioned hard resin layer tensile modulus of elasticity is alone 2000～4000 MPas; and full light transmittance is more than 90%; in addition, the total thickness t of substrate layer
1thickness t with hard resin layer
2ratio (t
1/ t
2) be 0.25～10, the scratch hardness of laminated resin body is more than 40g.
Here for the evaluation of the hardness of the laminated resin body in the present invention, be the scratch hardness of utilizing the evaluation method based on ISO1518-2 to obtain.The method is the evaluation method of having utilized fluctuating load method, and therefore the character of the hard resin layer on upper strata and the thermoplastic resin entirety of lower floor is not subject to the impact of thickness, can be not as the deviation of the evaluation of duplexer carry out the evaluation of hardness.
In the present invention, the functional group's number that is preferably formed (methyl) acryl monomer in the hardening resin composition of hard resin layer is that taking the solid constituent 100g with respect to hardening resin composition, the ratio more than 40g contains 4 above monomers.
In addition, in the present invention, preferably hard resin layer and substrate layer Jie are undertaken stacked by adhesive linkage.For this adhesive linkage, be preferably be selected from caking property bonding agent, pressure-sensitive bonding agent, Photocurable adhesive agent, heat-curable adhesive or hot-melt adhesive appoint one kind or two or more.In addition, hard resin layer and thermoplastic resin also can be situated between and be undertaken stacked by easy adhesive linkage.In addition,, in the present invention, can possess hard resin layer on the table back of the body two sides of substrate layer.
In addition, in the present invention, contained multifunctional (methyl) acryl monomer of curable resin composition that forms hard resin layer preferably has cage silsesquioxane structure.Multifunctional (methyl) acryl monomer more preferably with cage silsesquioxane structure is the compound that following formula (1) represents,
(R
1SiO
3/2)
n(R
2R
3SiO
2/2)
m(R
4R
5R
6SiO
1/2)
l (1)
(R in formula
1～R
6alkyl, phenyl, (methyl) acryloyl group, (methyl) acryloxyalkyl, vinyl of carbon number 1～6 or the group with oxirane ring; can also can contain different groups for identical group separately; but in formula, at least there are 2 (methyl) acryloyl groups; n, m, l are mean value; n is 6～14 number; m is 0～4 number, and l represents 0～4 number, and meets m≤l).
Laminated resin body of the present invention, can have high case hardness maintaining under transparent state.And, can form impact, bending and have the laminated resin body of enough patience, therefore, the excellent in workability such as moulding, cutting, perforation, can be used as the housing of display pannel, design excellence etc.
Brief description of the drawings
Fig. 1 is the key diagram that schematically shows the duplexer that the 1st mode of the present invention invents.
Fig. 2 is the key diagram that schematically shows the duplexer that the 2nd mode of the present invention invents.
Fig. 3 is the key diagram that schematically shows the duplexer that the 3rd mode of the present invention invents.
Symbol description
1: hard resin layer
2: adhesive layer
3: substrate layer
3b: substrate layer
4: printed layers
5: pressure-sensitive bond layer
Detailed description of the invention
Below, the present invention is described in detail.
< hard resin layer >
As long as the curable resin composition of the formation hard resin layer in laminated resin body of the present invention contains multifunctional (methyl) acrylate in molecule with more than 2 ethylenic unsaturated bond, be not particularly limited.,, as above-mentioned multifunctional (methyl) acrylate, can enumerate two senses (methyl) acrylate or (methyl) acrylate more than trifunctional.
Wherein, as two senses (methyl) acrylate, for example, can enumerate ethylene glycol bisthioglycolate (methyl) acrylate, diethylene glycol two (methyl) acrylate, hexylene glycol (methyl) acrylate, long-chain fat family two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, 3-hydroxypivalic acid neopentyl glycol two (methyl) acrylate, stearic acid modified pentaerythrite two (methyl) acrylate, propylidene two (methyl) acrylate, glycerine (methyl) acrylate, triethylene glycol two (methyl) acrylate, TEG two (methyl) acrylate, tetramethylene glycol two (methyl) acrylate, butanediol two (methyl) acrylate, two cyclopenta two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, polytrimethylene two (methyl) acrylate, triglycerin two (methyl) acrylate, neopentyl glycol modification trimethylolpropane two (methyl) acrylate, allylation cyclohexyl two (methyl) acrylate, methoxylation cyclohexyl two (methyl) acrylate, propylene acidylate isocyanuric acid ester, two (acryloxy neopentyl glycol) adipate ester, bisphenol-A two (methyl) acrylate, tetrabromobisphenol A two (methyl) acrylate, bisphenol S two (methyl) acrylate, butanediol two (methyl) acrylate, phthalic acid two (methyl) acrylate, di(2-ethylhexyl)phosphate (methyl) acrylate, two (methyl) zinc acrylate resin etc.
In addition, as (methyl) acrylate more than trifunctional, for example, can enumerate trimethylolpropane tris (methyl) acrylate, trimethylolethane trimethacrylate (methyl) acrylate, glycerine three (methyl) acrylate, pentaerythrite two (methyl) acrylate, pentaerythrite three (methyl) acrylate, alkyl-modified dipentaerythritol three (methyl) acrylate, tricresyl phosphate (methyl) acrylate, three (acryloxy ethyl) isocyanuric acid ester, three (methacryloxyethyl) isocyanuric acid ester, pentaerythrite four (methyl) acrylate, dipentaerythritol four (methyl) acrylate, two (trimethylolpropane) tetraacrylate, alkyl-modified dipentaerythritol four (methyl) acrylate, dipentaerythritol monohydroxy five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, dipentaerythritol five (methyl) acrylate, alkyl-modified dipentaerythritol five (methyl) acrylate, carboxyl acid modified dipentaerythritol five (methyl) acrylate, carbamate three (methyl) acrylate, ester three (methyl) acrylate, carbamate six (methyl) acrylate, ester six (methyl) acrylate etc.
These multi-functional (methyl) acrylate can use separately a kind also can combine two or more use.
In addition, for curable resin composition, as multifunctional (methyl) acryl monomer, preferably contain the compound with curability cage silsesquioxane structure.
In addition, the above-mentioned compound with curability cage silsesquioxane structure more preferably contains the cage-type silsesquioxane resin that following general formula (1) represents.
(R
1SiO
3/2)
n(R
2R
3SiO
2/2)
m(R
4R
5R
6SiO
1/2)
l (1)
(R in formula
1～R
6be carbon number 1～6 alkyl, phenyl, (methyl) acryloyl group, (methyl) acryloxyalkyl, vinyl, there is the group of oxirane ring; can also can contain different groups for identical group separately; but in formula (1), at least there are 2 (methyl) acryloyl groups; n, m, l are mean value; n is 6～14 number; m is 0～4 number, and l represents 0～4 number, and meets m≤l)
Whole silicon atoms that above-mentioned cage-type silsesquioxane resin is preferably formation cage contain the controlled cage-type silsesquioxane resin of molecular weight distribution and structure by having the organo-functional group of (methyl) acryloyl group or the reactive functional groups of (methyl) acryloxyalkyl formation; but part also can be replaced as alkyl, phenyl etc.; in addition; can not be totally enclosed polyhedral structure, can be also the structure of part cracking.During for the structure of part cracking, on the organosilicon chain connecting, can there is (methyl) acryloyl group.
The hard resin layer being made up of curable resin composition using in the present invention, thickness need to be 25 μ m～250 μ m.If thickness is less than 25 μ m, cannot obtain sufficient scratch hardness, if thickness exceedes 250 μ m, full light transmittance reduces, and has the required such problems of the transparency such as display that can not get.
In addition, the hard resin layer using in the present invention tensile modulus of elasticity is alone 2000～4000 MPas.If tensile modulus of elasticity is less than 2000 MPas, the scratch hardness of laminated resin body is less than 40g, if exceed 4000 MPas, has the processabilities such as moulding, cutting, perforation to become difficult such problem.And, because the hard resin layer using in the present invention is applicable to display pannel etc., so its full light transmittance need to be more than 90%.
In addition, the functional group's number that forms (methyl) acryl monomer in the hardening resin composition of above-mentioned hard resin layer is that preferably taking the solid constituent 100g with respect to hardening resin composition, the ratio more than 40g contains 4 above monomers.(methyl) is less than 40g if functional group's number of acryl monomer is 4 above monomers, is more than 25 μ m even if there is thickness, also cannot obtain the such problem of sufficient scratch hardness.
In addition; for curable resin composition; from obtaining sufficient scratch hardness as laminated resin body when; the machining such as cutting, perforation becomes good etc. viewpoint sets out, the scope that the molal quantity of (methyl) acryloyl group of every 100g solid constituent of preferred consolidation resin combination is 0.6～0.9.Herein, the molal quantity of (methyl) acryloyl group of every 100g solid constituent of hardening resin composition calculates by following formula.
The quantity of (methyl) acryloyl group in (molal quantity of (methyl) acryloyl group of every 100g)=(100/ molecular weight) × 1 molecule
Should illustrate; while using multiple multifunctional (methyl) acryl monomer as curable resin composition; use average (methyl) acryloyl group molal quantity calculating according to mixing ratio; in the time coordinating the fillers such as silica, on the basis that comprises its weight, calculate the mean value of the molal quantity of (methyl) acryloyl group.
In addition; the stereoplasm resin bed being made up of curable resin composition, can be within the molal quantity of (methyl) acryloyl group of every 100g solid constituent of hardening resin composition depart from the scope of 0.6～0.9 scope and the combination of simple function (methyl) acrylate.But, if coordinate a certain amount of above simple function (methyl) acrylate, the trend that has case hardness to reduce, when therefore cooperation for objects such as adjusting viscosity, be preferably limited to bottom line, be preferably below 30 % by weight with respect to curable resin composition.
As simple function (methyl) acrylate, for example, can enumerate methyl acrylate herein, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, acrylic acid pentyl ester, acrylic acid peopentyl ester, acrylic acid isopentyl ester, Hexyl 2-propenoate, acrylic acid heptyl ester, 2-ethyl hexyl acrylate, 2-EHA, acrylic acid n-octyl, Isooctyl acrylate monomer, acrylic acid ester in the ninth of the ten Heavenly Stems, acrylic acid ester in the different ninth of the ten Heavenly Stems, decyl acrylate, isodecyl acrylate, acrylic acid undecyl ester, dodecylacrylate, tridecyl acrylate, acrylic acid myristyl ester, acrylic acid pentadecyl ester, the different myristyl ester of acrylic acid, aliphatic acrylate, acrylic acid heptadecyl ester, acrylic acid stearyl, acrylic acid nonadecyl ester, acrylic acid eicosyl ester, the positive Lauryl Ester of acrylic acid, the alkyl-acrylates such as stearyl acrylate base ester, acryloyl morpholine, cyclohexyl acrylate, acrylic acid double cyclopentenyl ester, acrylic acid double cyclopentenyl oxygen base ethyl ester, acrylic acid two cyclopentyl esters, phenyl acrylate, benzyl acrylate, acrylic acid 2-hydroxy methacrylate, acrylic acid 2-hydroxy propyl ester, acrylic acid 2-hydroxyl butyl ester, acrylic acid 2-hydroxyl-3-phenyl oxygen base propyl ester, BDO mono acrylic ester, 2-hydroxy alkyl acryloyl phosphate, acrylic acid 4-hydroxyl cyclohexyl, 1,6-hexanediol monoacrylate, neopentyl glycol mono acrylic ester, the compound that the cyclic ester compound addition such as acrylate based compound and 6-caprolactone of above-mentioned hydroxyl is formed, by alkyl glycidyl ether, allyl glycidyl ether, glycidyl acrylates etc. are containing the compound of glycidyl and the compound that acrylic acid addition reaction obtains, polyethylene glycol monoacrylate, polypropylene glycol mono acrylic ester, acrylic acid tetrahydro furfuryl ester, isobornyl acrylate, (2-Ethyl-2-Methyl-1,3-dioxa penta encircle-4-yl) methacrylate, (2-isobutyl group-2-methyl isophthalic acid, 3-dioxa penta encircle-4-yl) methacrylate etc.
The curable resin composition using in the present invention is by carrying out free-radical polymerized obtaining (methyl) acrylic resin copolymer to it.For the physical property of improving (methyl) acrylic resin copolymer, or promote the objects such as free-radical polymerized, can in curable resin composition of the present invention, coordinate various additives.As the additive that promotes reaction, can illustrate thermal polymerization, thermal polymerization promoter, Photoepolymerizationinitiater initiater, light-initiated auxiliary agent, sensitizer etc.While coordinating Photoepolymerizationinitiater initiater and thermal polymerization, its addition is preferably the scope of 0.1～5 weight portion, the more preferably scope of 0.1～3 weight portion with respect to total 100 weight portions of curable resin composition.If this addition less than 0.1 weight portion solidifies and becomes insufficient, the intensity of gained hard resin layer, rigidity step-down, on the other hand, if exceed 5 weight portions, may produce the problem such as painted of hard resin layer.
The Photoepolymerizationinitiater initiater using when curable resin composition is formed to Photocurable composition, can preferably use the compounds such as acetophenone system, benzoin system, benzophenone series, thioxanthones system, acylphosphine oxide system.More specifically, can illustrate 2,2-dimethoxy-1,2-diphenylethane-1-ketone, 1-hydroxyl-cyclohexyl-phenyl-one, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-[4-(2-hydroxyl-oxethyl)-phenyl]-2-hydroxy-2-methyl-1-propane-1-ketone, 2-hydroxyl-1-[4-[4-(2-hydroxy-2-methyl-propiono)-benzyl] phenyl]-2-methyl-propane-1-ketone, phenyl glyoxalic acid methylester, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, two (2,4,6-trimethylbenzoyl)-phenyl phosphine oxide, 1-[4-(thiophenyl)]-1,2-octane diketone-2-(O-benzoyl oxime), 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-ethyl ketone-1-(O-acetyl oxime), TMDPO, 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino propane-1-ketone, 1-hydroxyl-cyclohexyl-phenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone-1-ketone, two-2,6-dimethoxy benzoyl-2,4,4-tri-methyl-amyl phosphine oxide, benzophenone, thioxanthones, CTX, 2,4-diethyl thioxanthone, isopropyl thioxanthone, the chloro-4-propoxyl group of 1-thioxanthones, these can use separately one, also can be by two kinds of above and use.
The curable resin composition using in the present invention, by coordinating radical polymerization initiator, utilizes heating or irradiation that it is solidified, thereby can manufacture hard resin layer with the arbitrary shape such as plane, curved surface.While utilizing heating to manufacture the hard resin layer of arbitrary shape, its forming temperature can, according to the selection of thermal polymerization and promoter, be selected from the wide region of room temperature to 200 DEG C left and right.Now, by make its polymerizing curable in mould, on steel band, thereby can obtain the hard resin layer of desirable shape.
In addition, while utilizing irradiation to manufacture hard resin layer, can obtain by the luminous ray of the ultraviolet ray of illumination wavelength 10～400nm, wavelength 400～700nm.The light wavelength using is not particularly limited, but particularly preferably uses the near ultraviolet ray of wavelength 200～400nm.As the lamp as ultraviolet generation source, can illustrate low pressure mercury lamp (power output: 0.4～4W/cm), high-pressure sodium lamp (40～160W/cm), ultrahigh pressure mercury lamp (173～435W/cm), metal halide lamp (80～160W/cm), xenon flash lamp (80～120W/cm), electrodeless discharge lamp (80～120W/cm) etc.Because there is feature its light splitting distribution aspect of the each leisure of these ultraviolet lamps, so select according to the kind of the light trigger using.
As the method for the hard resin layer of the arbitrary shape that utilizes irradiation to obtain using in the present invention, for example can illustrate following method: in the mould that there is chamber shape arbitrarily, formed by transparent materials such as quartz glass, inject hardening resin composition, carry out polymerizing curable with above-mentioned ultraviolet lamp irradiation ultraviolet radiation, make it from mold releasability, manufacture thus the method for the hard resin layer of desirable shape; In the situation that not using mould, for example can illustrate following method etc.: on mobile steel band, use the coating machine of scraper, roller shape to be coated with curable resin composition of the present invention, make its polymerizing curable with above-mentioned ultraviolet lamp, manufacture thus the hard resin layer of sheet.
< substrate layer >
As the substrate layer in the present invention, preferably clear excellence, can preferably be used PETG (PET), triacetyl cellulose (TAC), PEN (PEN), polymethyl methacrylate (PMMA), Merlon (PC), polyimides (PI), polyethylene (PE), polypropylene (PP), polyvinyl alcohol (PVA), polyvinyl chloride (PVC), cyclic olefine copolymer (COC), contain the various resin moldings such as norbornene resin, polyether sulfone, glassine paper, aromatic polyamide.These films can use without the film stretching, also can use the film of having implemented stretch process, but in them, from the viewpoint of heat resistance, the transparency, weatherability, solvent resistance, resistance to impact, processability, cost, particularly preferably PETG (PET), polymethyl methacrylate (PMMA), Merlon (PC).
Substrate layer is given rigidity to laminated resin body of the present invention, and enough patience is given in impact, bending.For example; if the hard resin layer in the present invention is formed by the curable resin composition that contains multifunctional (methyl) acryl monomer with cage silsesquioxane structure; can suitably possess cut intensity is high case hardness more than 40g; but in order to ensure the transparency; the thickness of hard resin layer is 250 μ m when following, and resistance to impact becomes insufficient.Therefore,, in the present invention, possesses the enough patience of impact, bending etc. by substrate layer.For this substrate layer, its gross thickness is 0.5～2000 μ m, is preferably 10～1000 μ m.If be less than 0.5 μ m, cannot obtain sufficient rigidity, if exceed 2000 μ m, be difficult to carry out the processing such as moulding, cutting, perforation.In addition, in the present invention, the total thickness t of substrate layer
1thickness t with hard resin layer
2ratio (t
1/ t
2) be 0.25～10.If the ratio of this thickness is less than 0.25, there are the processabilities such as moulding, cutting, perforation to become the problem of difficulty and so on, if exceed 10, there is scratch hardness to be less than this problem of 40g.
< adhesive linkage >
Laminated resin body of the present invention can utilize any the stacked hard resin layer of adhesive layer (adhesive linkage) and substrate layer of film, sheet.
As adhesive layer, its thickness is 0.01～30 μ m, is preferably 0.1～10 μ m.If be less than 0.01 μ m, be difficult to obtain sufficient adhesive effect, more than 30 μ m, possibly cannot fully obtain the scratch hardness of duplexer if.
In addition, as the material forming as the adhesive layer of adhesive linkage, can use caking property bonding agent, pressure-sensitive bonding agent, Photocurable adhesive agent, heat-curable adhesive and hot-melt adhesive.As such bonding agent, can enumerate acrylic adhesive, carbamate bonding agent, epoxy adhesive, polyester adhesive, polyvinyl alcohol bonding agent, Polyofefine adhesive agent, improved polyalkene bonding agent, polyvinyl alkyl ether bonding agent, rubber adhesive, trichloroactic acid vinyl acetate bonding agent, styrene butadiene styrene copolymer (SBS copolymer) bonding agent, its hydride (SEBS copolymer) bonding agent, vinyl-vinyl acetate copolymer, the ethylene adhesives such as ethylene-styrene copolymer, ethylene methacrylic acid methyl terpolymer, ethylene methyl acrylate copolymer, ethylene methacrylic acid ethyl ester copolymer, the acrylate adhesive such as ethylene ethyl acrylate copolymer etc., as long as cementability, the transparency, processability is good, just be not particularly limited.
The easy adhesive linkage > of <
In addition, as other layer that forms adhesive layer, can enumerate easy adhesive linkage.Easily adhesive linkage be the surface of having carried out the tree resin layer to difficult cementability impose chemical easy-adhesion energy or physics easy-adhesion can the layer of processing.Wherein, chemistry easy-adhesion can be specifically the thin layer by form the resin with functional group on substrate layer, form chemical bond with hard resin layer, thereby obtain the performance of closing force, the opposing party's physics easy-adhesion can refer to by form the irregular resin thin film layer of tool or inorganic thin film layer on base material, thereby utilizes anchoring effect to obtain and the performance of the closing force of hard tree resin layer.As have chemical easy-adhesion can material, can enumerate multifunctional (methyl) esters of acrylic acid, epoxies, containing the compound of mercapto etc., as have physics easy-adhesion can material, can enumerate SiO
2, SiN, SiC etc. vapor-deposited film etc.
In Fig. 1, show the 1st mode of the laminated resin body in the present invention.Laminated resin body shown in Fig. 1 descends the stacked hard resin layer 1 in two sides thereon at the two sides of the substrate layer 3 being made up of thermoplastic resin clamping adhesive layer 2.In addition, in the laminated resin body relating in the 1st mode, there is the structure that is formed with printed layers 4 at one-sided hard resin layer 1.Here, adhesive layer 2 is as being used for making hard resin layer 1 and the integrated adhesive linkage performance of substrate layer 3 function.In addition, form printed layers 4 by the lower surface at laminated resin body of the present invention, thereby can form figure, word etc.As the printing style of printed layers 4, can select arbitrarily, for example can enumerate the patterns such as wood grain, bag, woven design, sand streak, geometric figure, word, whole are solid, metal.Should illustrate, the adhesive layer 2 here can be above-mentioned adhesive linkage or easily in adhesive linkage any.
Preferably in printed layers 4, coordinate the resinous principle good with the compatibility of hard resin layer, substrate layer, for example can enumerate polyethylene base system resin, polyamide-based resin, polyester based resin, acrylic resin, polyurethane series resin, the Pioloform, polyvinyl acetals such as vinyl chloride/vinyl acetate copolymer is that resin, polyester urethane are that resin, cellulose esters are resin, alkyd resins and chlorinated polyolefin resin etc.By coordinating such resinous principle, thereby can suppress peeling off, coming off of printing.
In addition, form when printed layers 4, can use the pigment that contains appropriate color or the colouring agent of dyestuff.
As the formation method of printed layers 4, for example, can enumerate the print processes such as hectographic printing method, woodburytype, screen painting method, the rubbing methods such as rolling method, spraying process, and flexographic printing method.
As the thickness of printed layers 4, in laminated resin body, suitably select thickness in the mode that obtains desirable appearance, be conventionally preferably 0.5～30 μ m left and right.
In addition, for laminated resin body of the present invention, as the 2nd, the 3rd embodiment, can illustrate example structure as shown in Figure 2 and Figure 3.
In the mat woven of fine bamboo strips 2 embodiments shown in Fig. 2, upper surface at substrate layer 3b forms printed layers 4, clamp respectively pressure-sensitive bond layer 5 at these printed layers 4 upper lateral parts and the side that do not form printed layers 4, form hard tree resin layer 1 in printed layers 4 sides, form substrate layer 3 in a side that does not form printed layers 4 in addition.
In Fig. 2, as the substrate layer 3b using, be just not particularly limited as long as there is the transparency, but preferred polymethyl methacrylate (PMMA).
In addition, in the 3rd embodiment shown in Fig. 3, be situated between and form hard resin layer 1 by adhesive layer 2 at the upper surface of substrate layer 3, in addition, form printed layers 4 at the lower surface of substrate layer 3, be situated between and form the 2nd substrate layer 3 by pressure-sensitive bond layer 5 in its underpart.
The pressure-sensitive bond layer 5 using in the embodiment of Fig. 2 and Fig. 3 can use known pressure-sensitive bonding agent.Particularly, for example can use natural rubber is that resin, synthetic rubber are that resin, silicon-type resin, acrylic resin, vinyl acetate are that resin, carbamate are the adhesives such as resin.
As long as above-mentioned bonding agent can obtain required light transmission, caking property, weatherability and just be not limited to this.In addition, form according to layer, in order to prevent the deteriorated of pigment, preferably in adhesive, contain and there is the UV absorbent (BTA etc.) that absorbs ultraviolet effect.
As pressure-sensitive bond layer 5, its average thickness is 0.01～30 μ m, is preferably 0.1～10 μ m.If be less than 0.01 μ m, cannot obtain sufficient adhesive strength, and absorb printed layers concavo-convex and the effect of its planarization is also reduced.In addition, if be greater than 30 μ m, may become the key factor that the scratch hardness of duplexer is reduced.
In embodiments of the present invention Fig. 1,3, can under the state of laminated resin body, give 3D shape by thermoforming.Substrate layer 3 in Fig. 1,3 can be by warm and moulding, because hard resin layer 1 has sufficient flexibility, is situated between and forms one-body molded product by adhesive layer 2 so can follow the shape of substrate layer 3.As thermoforming, can enumerate vacuum forming, press empty moulding, extrusion forming etc.
In addition, while formation for the layer as the laminated resin body shown in embodiments of the present invention Fig. 2, can make to be shaped to respectively in advance A part (the hard resin layer 1 of regulation shape, pressure-sensitive bond layer 5, printed layers 4, substrate layer 3b) and B part (pressure-sensitive bond layer 5, substrate layer 3) be situated between and fitted by pressure-sensitive bond layer 5, in addition, for the substrate layer 3 that forms B part, can in the mould of desirable shape, load in advance A part form pressure-sensitive bond layer 5 and part, then utilize injection moulding to form with resin injection as injection moulding.
Should illustrate, in embodiment Fig. 1～3, be formed with respectively printed layers 4, but printed layers 4 also can omit, in addition, coordinate duplexer manufacturing process, form with printing process arbitrarily at interlayer arbitrarily.
When substrate layer 3 is carried out to injection moulding, the thermoplastic resin of using as injection moulding, preferably there is the transparency, can preferably use PETG (PET), triacetyl cellulose (TAC), PEN (PEN), polymethyl methacrylate (PMMA), Merlon (PC), polyimides (PI), polyethylene (PE), polypropylene (PP), polyvinyl alcohol (PVA), polyvinyl chloride (PVC), cyclic olefine copolymer (COC), containing norbornene resin, polyether sulfone, glassine paper, the various resin moldings such as aromatic polyamide, from heat resistance, the transparency, weatherability, solvent resistance, rigidity, the viewpoint of cost is considered, preferably use PETG or Merlon, consider from the viewpoint of resistance to impact, particularly preferably Merlon.
Here the evaluation method of hardness of the present invention is described.The scratch hardness assay method that utilizes front end shape to adopt the fluctuating load method of the pressure head of acute angle to carry out is disclosed in ISO1518-2.The method is following method: apply to load on pressure head is squeezed under the surperficial state of sample sample is moved, observe the scar being caused by pressure head, carry out evaluation hardness Fc (g) according to load now by the formula shown in following.
Fc＝{(100-d)/100)}×(Ff-Fi)
D: start the distance (mm) to terminal from scuffing while being 100mm from measuring starting point to the distance of terminal
Ff: in the load (g) of terminal
Fi: in the load (g) of measuring starting point
The present inventor etc. adopt the method to implement hardness evaluation to various materials, found that the scuffing difficulty that can more accurate judgement cannot judge in pencil hardness, and properties of materials is now investigated.The scratch hardness of having utilized fluctuating load method for 40g be preferred scope above.If be worth less than this scope, owing to easily scratching simply with a small amount of load, thereby not preferred.Should illustrate, be that great situation remarks additionally to the value of scratch hardness, also do not scratch even if apply large load the difficulty that namely represents processing, thereby not preferred.In addition, when hard resin layer has because of the character of load bending, the value of scratch hardness also becomes greatly sometimes, even but without scar, reduce owing to remaining dent mark or texture, thereby not preferred.Should illustrate, the load of measuring while having utilized the scratch hardness of fluctuating load method is not particularly limited, and can measure starting point with about 0～hundreds of g, measure with the scope of tens of～hundreds of g at terminal.
Embodiment
Below, use embodiment to further describe the present invention.Should illustrate, the evaluation method and the symbol that in the present invention, use are as described below.
1) scratch hardness: taking ISO1518-2 (coating and varnish-scratch resistant mensuration-part 2: variable load method) as benchmark, the sapphire pin that the R that uses front end is 0.03 ± 0.005mm, the translational speed 10mm/s of pin, in the scope of 0～200g, slowly increase load, utilize the load of microscopic examination according to can visual scar time to evaluate.
2) full light transmittance: measure taking JIS K7361-1 as benchmark.
3) thickness: use the ID-SX processed of Mitutoyo company to measure.
4) tensile modulus of elasticity: measure taking JIS K7127 as benchmark.
5) processability: matching plane cutter (interior mountain sword thing system is installed at matching plane processing machine (MEGAROTECHNICA company system), sword footpath 2mm, straight sword), the laminated resin body obtaining in to embodiment under the processing conditions of rotating speed 20000rpm, feed speed 900mm/ minute carries out machining, carry out the microscopic examination of section, the average evaluation that to observe damaged (chip) at section for ×, unobserved average evaluation is zero.
[embodiment 1]
(making of hard resin layer)
Dipentaerythritol acrylate 85 weight portions and PMMA15 weight portion are added to hot milling to 110 DEG C, thereafter, mix 1-hydroxycyclohexylphenylketone 2.5 weight portions as Photoepolymerizationinitiater initiater, obtain hardening resin composition.
Next, use roll coater, the mode that becomes 0.15mm with thickness hardening resin composition is cast on the PET that has carried out lift-off processing (curtain coating), by other carrying out the pet layer of lift-off processing be pressed on after the hardening resin composition of having cast, use the high-pressure sodium lamp of 30W/cm with 4000mJ/cm
2cumulative exposure amount make its solidify, remove by peeling off completely the PET that has carried out lift-off processing, can obtain the hard resin layer of the sheet that forms specific thickness.The hard resin layer obtaining is measured to tensile modulus of elasticity and full light transmittance.Show the result in table 1.
(making of laminated resin body)
Be Photocurable adhesive agent (vertical chemical industry company of association system) in the mode of thickness that becomes 5 μ m at the Merlon as substrate layer (PC-1151 processed of Di Ren company, 200mm × 200mm × thickness 0.5mm (t by cation
1)) be coated with after curtain coating, hard resin layer obtained above is fitted in to whole an of side of Merlon, after crimping, with metal halide lamp with 500mJ/cm
2ratio from two sides irradiation ultraviolet radiation, obtain laminated resin body.The laminated resin body obtaining is evaluated to scratch hardness and processability.By hard resin layer thickness (t now
2), thickness ratio (t
1/ t
2) and scratch hardness the results are shown in table 1.
[embodiment 2]
Mix proportion is made as to the part by weight shown in table 1, in addition, obtains similarly to Example 1 hard resin layer and laminated resin body.The evaluation result of the formed body obtaining is shown in to table 1 in the lump.
[synthesis example 1]
Possessing in the reaction vessel of mixer, dropping funel, thermometer, pack into as 2-propyl alcohol (IPA) 400ml of solvent with as 5% tetramethylammonium hydroxide aqueous solution (the TMAH aqueous solution) of base catalyst.In dropping funel, add IPA150ml and 3-methacryloxypropyl trimethoxy silane (the MTMS:Dow Corning Toray Silicone SZ-6030 processed of company) 126.9g, stirring reaction container on one side, on one side at the IPA solution that drips MTMS for 30 minutes for room temperature.MTMS does not stir 2 hours after dripping and finishing heatedly.Stir after 2 hours under reduced pressure except desolventizing, with toluene 500ml dissolving.With saturated aqueous common salt, reaction solution is washed until be after neutrality, dewatered with anhydrous magnesium sulfate.Filtering anhydrous magnesium sulfate, concentrates, and obtains thus having on whole silicon atoms the cage-type silsesquioxane compound 86g of methacryl.This silsesquioxane is the colourless viscous liquid that dissolves in various organic solvents.
[embodiment 3]
Mix the urethane acrylate oligomer 1 of cage-type silsesquioxane compound 25 weight portions on whole silicon atoms with methacryl that obtain in above-mentioned synthesis example 1, dipentaerythritol acrylate 40 weight portions, two cyclopenta diacrylate 30 weight portions, 5 weight portions and 1-hydroxycyclohexylphenylketone 2.5 weight portions as Photoepolymerizationinitiater initiater, obtain transparent hardening resin composition.
Next, obtain similarly to Example 1, after hard resin layer, making similarly to Example 1 laminated resin body evaluation.Show the result in table 1.
[embodiment 4～9 and comparative example 1～4]
Mix proportion is made as to the part by weight shown in table 1, in addition, obtains similarly to Example 1 hard resin layer and laminated resin body.The evaluation result of the formed body obtaining is shown in to table 1 in the lump.
Abbreviation in table is as described below.
A: the compound obtaining in synthesis example 1
B: dipentaerythritol acrylate (KAYARADDPHA processed of Nippon Kayaku K. K)
C: trimethylol-propane trimethacrylate (the Light Ester processed TMP of Kyoeisha Chemical Co., Ltd.)
D: pentaerythritol triacrylate (the Light Acrylate processed PE-3A of Kyoeisha Chemical Co., Ltd.)
E: caprolactone modification dipentaerythritol acrylate 1 (the KAYARAD DPCA-20 processed of Nippon Kayaku K. K)
F: caprolactone modification dipentaerythritol acrylate 2 (the KAYARAD DPCA-30 processed of Nippon Kayaku K. K)
G: two cyclopenta diacrylates (the Light AcrylateDCP-A processed of Kyoeisha Chemical Co., Ltd.)
H: two cyclopenta dimethylacrylates (the NK EsterDCP processed of KCC of Xin Zhong village)
I:PMMA (the Parapet LW processed of KURARAY company: weight average molecular weight approximately 34000)
J: urethane acrylate oligomer 1 (UF-503 processed of Kyoeisha Chemical Co., Ltd.: number-average molecular weight approximately 8800)
K: urethane acrylate oligomer 2 (the NK Oligo processed UA-122P of KCC of Xin Zhong village: number-average molecular weight approximately 1100)
L:1-hydroxycyclohexylphenylketone (polymerization initiator, the IRGACURE184 processed of BASF Japan company)
Table 1
Claims (8)
1. a laminated resin body; it is characterized in that; possess hard resin layer and substrate layer; described hard resin layer is by forming taking multifunctional (methyl) acryl monomer as the curable resin composition of neccessary composition; there is three-dimensional crosslinking structure and there is the thickness of 25 μ m～250 μ m; described substrate layer is made up of monolayer thermoplastic resin or 2 layers of above multi-layer thermoplastic resin; described hard resin layer tensile modulus of elasticity is alone 2000～4000 MPas; and full light transmittance is more than 90%; in addition, the total thickness t of substrate layer
1thickness t with hard resin layer
2ratio t
1/ t
2be 0.25～10, the scratch hardness of laminated resin body is more than 40g.
2. laminated resin body according to claim 1; it is characterized in that, in the hardening resin composition of formation hard resin layer, functional group's number of (methyl) acryl monomer is that taking the solid constituent 100g with respect to hardening resin composition, the ratio more than 40g is contained 4 above monomers.
3. laminated resin body according to claim 1 and 2, is characterized in that, hard resin layer and substrate layer are situated between and are undertaken stacked by adhesive linkage.
4. laminated resin body according to claim 3, is characterized in that, adhesive linkage one kind or two or morely forms by being selected from appointing in caking property bonding agent, pressure-sensitive bonding agent, Photocurable adhesive agent, heat-curable adhesive and hot-melt adhesive.
5. laminated resin body according to claim 1 and 2, is characterized in that, hard resin layer and thermoplastic resin are situated between and are undertaken stacked by easy adhesive linkage.
6. laminated resin body according to claim 1 and 2, is characterized in that, contained multifunctional (methyl) acryl monomer of curable resin composition that forms hard resin layer has cage silsesquioxane structure.
7. laminated resin body according to claim 6, is characterized in that, has multifunctional (methyl) acryl monomer of cage silsesquioxane structure by following formula (1) expression,
(R
1SiO
3/2)
n(R
2R
3SiO
2/2)
m(R
4R
5R
6SiO
1/2)
l (1)
In formula, R
1～R
6alkyl, phenyl, (methyl) acryloyl group, (methyl) acryloxyalkyl, vinyl of carbon number 1～6 or the group with oxirane ring; can also can contain different groups for identical group separately; but in formula (1), at least there are 2 (methyl) acryloyl groups; n, m, l are mean value; n is 6～14 number; m is 0～4 number, and l represents 0～4 number, and meets m≤l.
8. laminated resin body according to claim 1 and 2, is characterized in that, possesses hard resin layer on the table back of the body two sides of substrate layer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013-095489 | 2013-04-30 | ||
| JP2013095489A JP2014213596A (en) | 2013-04-30 | 2013-04-30 | Resin laminate |
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| Publication Number | Publication Date |
|---|---|
| CN104129129A true CN104129129A (en) | 2014-11-05 |
Family
ID=51802103
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410174664.XA Pending CN104129129A (en) | 2013-04-30 | 2014-04-28 | Resin laminate |
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| Country | Link |
|---|---|
| JP (1) | JP2014213596A (en) |
| KR (1) | KR20140130040A (en) |
| CN (1) | CN104129129A (en) |
| TW (1) | TW201500203A (en) |
Cited By (5)
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| CN106005748A (en) * | 2016-06-29 | 2016-10-12 | 苏州市盛百威包装设备有限公司 | Packaging box of precision part |
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| CN109795190A (en) * | 2017-11-17 | 2019-05-24 | 日本航空电子工业株式会社 | Optical component and production method of product with touch sensor, optical component |
| CN114055904A (en) * | 2020-07-30 | 2022-02-18 | 株式会社瑞延理化 | Preparation method of plastic embedded glass |
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| TWI546559B (en) | 2015-05-19 | 2016-08-21 | 長興材料工業股份有限公司 | Coating composition for enhancing light transmittance and coating layer formed therefrom |
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| WO2019044786A1 (en) * | 2017-08-29 | 2019-03-07 | 東亞合成株式会社 | Resin sheet and curable composition for producing same |
| KR102126057B1 (en) * | 2017-12-28 | 2020-06-23 | 삼성에스디아이 주식회사 | Polarizing plate and optical display device comprising the same |
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-
2013
- 2013-04-30 JP JP2013095489A patent/JP2014213596A/en active Pending
-
2014
- 2014-04-16 TW TW103113825A patent/TW201500203A/en unknown
- 2014-04-28 CN CN201410174664.XA patent/CN104129129A/en active Pending
- 2014-04-29 KR KR20140051288A patent/KR20140130040A/en not_active Withdrawn
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106005748A (en) * | 2016-06-29 | 2016-10-12 | 苏州市盛百威包装设备有限公司 | Packaging box of precision part |
| CN109461372A (en) * | 2017-09-06 | 2019-03-12 | 三星显示有限公司 | For the lid window of display device and the manufacturing method of the lid window |
| CN109461372B (en) * | 2017-09-06 | 2022-05-24 | 三星显示有限公司 | Cover window for display device and method of manufacturing the same |
| CN109795190A (en) * | 2017-11-17 | 2019-05-24 | 日本航空电子工业株式会社 | Optical component and production method of product with touch sensor, optical component |
| CN109795190B (en) * | 2017-11-17 | 2021-08-24 | 日本航空电子工业株式会社 | Optical component and production method of product with touch sensor, optical component |
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| CN114055904A (en) * | 2020-07-30 | 2022-02-18 | 株式会社瑞延理化 | Preparation method of plastic embedded glass |
| CN114055904B (en) * | 2020-07-30 | 2023-12-01 | 株式会社瑞延理化 | Preparation method of plastic embedded glass |
| CN114574117A (en) * | 2022-02-25 | 2022-06-03 | 深圳昌茂粘胶新材料有限公司 | Weather-proof medium-resistant high-temperature-resistant label tape and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2014213596A (en) | 2014-11-17 |
| KR20140130040A (en) | 2014-11-07 |
| TW201500203A (en) | 2015-01-01 |
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