CN104057680A - Resin laminate and molding method using the same - Google Patents
Resin laminate and molding method using the same Download PDFInfo
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- CN104057680A CN104057680A CN201410101404.XA CN201410101404A CN104057680A CN 104057680 A CN104057680 A CN 104057680A CN 201410101404 A CN201410101404 A CN 201410101404A CN 104057680 A CN104057680 A CN 104057680A
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- Prior art keywords
- methyl
- resin layer
- hard resin
- acrylate
- hard
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Classifications
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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
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
-
- 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
Abstract
The invention provides a resin laminate with high surface hardness and high transparency and a molding method using the same. The resin laminate comprises at least more than a layer of a hard resin layer and a thermoplastic resin layer, the hard resin layer is formed by the curing of three-dimensional cross-linking hard resin combinations containing polyfunctional methyl acryloyl monomers with cage type silsesquioxane structures, the vitrification transition temperature is above 200 DEG C, the thermoplastic resin layer is arranged on at least one surface of the hard resin layer, the ratio of the modulus of elasticity at room temperature to the modulus of elasticity at 150 DEG C is 1-500, the single tensile modulus of elasticity of the hard resin layer is 2000-4000 MPa, the total light transmittance is above 90%, the pencil hardness of the resin laminate is above 6H, and the ratio of the total thickness of the thermoplastic resin layer to the thickness of the hard resin layer is 0.25-10. Besides, the above molding method includes filling the resin laminate in the mold and forming the thermoplastic resin by injection molding.
Description
Technical field
The present invention relates to the plastic laminated resin body with hard coat film and the forming method that has used this laminated resin body, relate to the glass pane that mainly can be widely used as such as automobile, airborne vehicle, building, school, each shop etc., the lampshade of automobile, airborne vehicle etc., dome skylight, and housing, the various parts of personal computer, portable electric appts etc., wherein, be preferred for display pannel, and there is the laminated resin body and the forming method that has used this duplexer of the state of transparent multilaminar sheet.
Background technology
For example; in the electronic equipments such as digital camera, mobile phone; substrate as 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 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.Yet the thermoplastic resins and glassy phase ratio such as acrylic acid, Merlon, PETG, have case hardness, mar proof, marresistance poor, easily scratches such shortcoming.
In order to eliminate this shortcoming, carried out the research about the surface modification of laminated resin body since in the past.For example, extensively implemented resin-coated in the method for substrate surface by thermosetting resin, ultraviolet hardening.At these, implemented, 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, the case hardnesses such as pencil hardness to be low, in practicality, had very large problem.
As for transparent plastic material further being improved to the coating technique of case hardness, for example, carried out improving by hard conating being sneaked into the filler of high rigidity the trial (with reference to patent documentation 1, patent documentation 2, patent documentation 3) of case hardness.In addition, as similar method, in order to increase the thickness of hard painting, the stress that mitigation produces, studied and sneaked into inorganic and/or organic crosslinked particle, or on the surface of this particle, import functional group, make the method (with reference to patent documentation 4, patent documentation 5) of so-called hybrid inorganic-organic of the resin partial cross-linking of itself and hard conating.In addition, also carried out by making hard conating multiple stratification, the thickness that increases coating integral body obtains the trial (with reference to patent documentation 6) of higher case hardness.
Yet, as the concrete example of these methods and the example illustrating, use compare with polycarbonate resin original pencil hardness with regard to high PETG film, tri cellulose acetate membrane as base material, thereby make pencil hardness reach 6H from 4H, although confirmed this effect, but during only for thin hard conating, cannot realize pencil hardness, therefore hard basalis, the miscellaneous function of inorganic material are 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 carried out following trial,, be used as the polycarbonate resin of the resin that pencil hardness is low, on polycarbonate resin base material, with specific thickness, form 2 coating films, this is filmed and contains two sense urethane acrylates, multifunctional oligomer, polyfunctional monomer, monofunctional monomer, and consists of the ultraviolet curing resin with specific functional group number, but pencil hardness is 4H to the maximum, and insufficient (with reference to patent documentation 7).
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: Japanese Patent: No. 4626463 communique
Summary of the invention
The present invention carries out in view of above-mentioned problem, and object is to provide a kind of high surface hardness that has, and has the laminated resin body of high transparent, and the forming method that has used this laminated resin body.
The present inventor etc. are in order to obtain case hardness excellence, and the laminated resin body with high transparent conducts in-depth research, found that the laminated resin body that possesses the thermoplasticity resin layer of the hard resin layer that formed by the three-dimensional cross-linked type hard resin composition of stipulating and regulation by formation, can realize these objects simultaneously, thereby complete the present invention.
That is, the present invention is a kind of laminated resin body, it is characterized in that, has at least 1 layer of above hard resin layer and thermoplastic resin; Above-mentioned hard resin layer is curing the forming of three-dimensional cross-linked type hard resin composition that makes to contain multifunctional (methyl) acryloyl monomer with cage silsesquioxane structure, and glass transition temperature is more than 200 ℃; Above-mentioned thermoplastic resin is at least one side of this hard resin layer, and the elastic modulus E of room temperature
1elastic modulus E with 150 ℃
2ratio (E
1/ E
2) be 1～500; The single tensile modulus of elasticity of hard resin layer is 2000～4000 MPas, and total light transmittance is more than 90%; In addition, the pencil hardness of laminated resin body is more than 6H, the total thickness t of thermoplastic resin
1thickness t with hard resin layer
2ratio (t
1/ t
2) be 0.25～10.Should illustrate, here, " (methyl) acryloyl " has " methacryl " and " acryloyl " this two aspect and contains, below also identical.
Here, (methyl) acryloyl group molal quantity of the every 100g resin solid composition preferably containing in above-mentioned three-dimensional cross-linked type hard oil/fat composition is 0.6～0.9, and in addition, the thickness of gained hard resin layer is 50 μ m～250 μ m.
In addition, preferred above-mentioned hard resin layer and thermoplastic resin are situated between and by adhesive linkage, are undertaken stackedly, for this adhesive linkage, are preferably any in caking property bonding agent, pressure-sensitive bonding agent, Photocurable adhesive agent, heat-curable adhesive or hot-melt adhesive.Or above-mentioned hard resin layer and thermoplastic resin also can be situated between and be undertaken stacked by easy adhesive linkage.
And, for above-mentioned multifunctional (methyl) acryloyl monomer with cage silsesquioxane structure, be preferably the compound being represented by following formula (1).
（R
1SiO
3/2）
n（R
2R
3SiO
2/2）
m（R
4R
5R
6SiO
1/2）
l（1）
(R in formula
1～R
6it is the group of the alkyl with carbon number 1～6, phenyl, (methyl) acryloyl group, (methyl) acryloxyalkyl, vinyl, oxirane ring; the group that can be respectively identical also can contain different groups; 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, the number that l is 0～4, and meet m≤1.）
In addition, the present invention is a kind of forming method of laminated resin body, it is characterized in that, by above-mentioned laminated resin body is carried out to the shape that regulation is given in thermoforming.And the present invention is a kind of forming method, it is characterized in that, by the laminated resin body of the regulation shape obtaining is thus filled in mould, by thermoplastic injection moulding, thereby it is integrated to make to have laminated resin body and the thermoplastic resin of hard resin layer.
According to the present invention, can be formed in and under the state that remains transparent, there is high case hardness, and impact, bending 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.
Accompanying drawing explanation
Fig. 1 is the key diagram that schematically shows the laminated resin body that the 1st mode of the present invention invents.
Fig. 2 is the key diagram that schematically shows the laminated resin body that the 2nd mode of the present invention invents.
Fig. 3 is the key diagram that schematically shows the laminated resin body that the 3rd mode of the present invention invents.
Fig. 4 means the side view of the injection (mo(u)lding) machine using in the embodiment of the present invention.
Fig. 5 is the sectional view of the laminated resin body after moulding.
Symbol description
1: hard resin layer
2: adhesive phase
3,3b: thermoplastic resin
4: printed layers
5; Pressure-sensitive bond layer
6: screening glass
The specific embodiment
Below, the present invention is described in detail
< hard resin layer >
Hard fat layer in laminated resin body of the present invention is solidified and is formed by the three-dimensional cross-linked type hard resin composition that makes to contain multifunctional (methyl) acryloyl monomer with cage silsesquioxane structure, and its glass transition temperature is more than 200 ℃.
Wherein, multifunctional (methyl) acryloyl monomer that has an above-mentioned curability cage silsesquioxane structure is preferably the compound 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
6it is the group of the alkyl with carbon number 1～6, phenyl, (methyl) acryloyl group, (methyl) acryloxyalkyl, vinyl, oxirane ring; the group that can be respectively identical also can contain different groups; 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, the number that l is 0～4, and meet m≤1.）
; above-mentioned multifunctional (methyl) acryloyl monomer with cage silsesquioxane structure is preferably the silicon atom that forms cage and all contains the reactive functional groups that has the organo-functional group of (methyl) acryloyl group or consist of (methyl) acryloxyalkyl and the controlled monomer of molecular weight distribution and structure; but part functional group also can be replaced as alkyl, phenyl etc.; in addition; can not totally enclosed polyhedral structure, but the structure of part cracking.During for the structure of part cracking, on the organosilicon chain connecting, can there is (methyl) acryloyl group.
The three-dimensional cross-linked type hard resin composition of the hard resin layer 1 using in the present invention in addition, can will have (methyl) acrylate of 2 above ethene unsaturated bonds and use in molecule.As above-mentioned multifunctional (methyl) acrylate, can enumerate two senses (methyl) acrylate and (methyl) acrylate more than trifunctional.
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 chlorinated isocyanurates, 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) chlorinated isocyanurates, 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.
Should illustrate, multi-functional (methyl) acrylate with cage silsesquioxane structure can be used separately wherein a kind, also can combine two or more use.
The scope that the molal quantity of (methyl) acryloyl group of every 100g solid constituent of the hard resin layer consisting of the three-dimensional cross-linked type hard resin composition 1 preferred three-dimensional cross-linking type hard resin composition in the present invention is 0.6～0.9; in addition, its thickness is preferably 50 μ m～250 μ m.If the molal quantity of (methyl) acryloyl group of every 100g is less than 0.6, cannot obtain sufficient pencil hardness, if more than 0.9, flexibility disappears, and it is difficult that moulding becomes, and in addition, resistance to impact reduces, and it is difficult that the machinings such as cutting, perforation become.In addition, if thickness is less than 50 μ m, cannot obtain sufficient pencil hardness, if thickness surpasses 250 μ m, total light transmittance reduces, and has the required such problems of the transparency such as display that can not get.
The molal quantity of (methyl) acryloyl group of every 100g solid constituent of three-dimensional cross-linked type hard resin composition goes out with following formula grate.
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) acryloyl monomer as three-dimensional cross-linked type hard resin composition; average (methyl) acryloyl radix that use is calculated according to mixing ratio; while being combined with the fillers such as silica, also comprise its weight, calculate on this basis the mean value of the molal quantity of (methyl) acryloyl group.That is, with the solid constituent of three-dimensional cross-linked type hard resin composition in (methyl) acryloyl group of existing per unit mass molar concentration (mole/100g) quite.
The hard resin layer 1 consisting of the three-dimensional cross-linked type hard resin composition that forms hard resin layer, can not depart from the molal quantity of (methyl) acryloyl group of every 100g solid constituent of three-dimensional cross-linked type hard resin composition in 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, therefore the trend that has case hardness to reduce, when coordinate for objects such as adjusting viscosity, be preferably limited to bottom line, with respect to three-dimensional cross-linked type hard resin composition, be preferably below 30 % by weight.
As simple function (methyl) acrylate, for example, can enumerate methyl acrylate, 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 compounds such as acrylate based compound addition 6-caprolactone of above-mentioned hydroxyl are 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, acrylic acid (2-Ethyl-2-Methyl-1,3-dioxa penta ring-4-yl) methyl esters, acrylic acid (2-isobutyl group-2-methyl isophthalic acid, 3-dioxa penta ring-4-yl) methyl esters etc.
If suppose the glass pane as automobile, airborne vehicle by laminated resin body of the present invention, due to direct sunlight, surface becomes high temperature.In addition, while being used as the housing of personal computer, portable electric appts etc., device interior produces heat.Therefore, in order to prevent that hard resin layer is out of shape because of heat, need heat resistance, glass transition temperature need to be for more than 200 ℃.Should illustrate, consider and contain organic matter, can cause organic decomposition etc., thus the glass transition temperature of hard resin layer on be limited to 450 ℃.
In addition, the single tensile modulus of elasticity of hard resin layer using in the present invention is 2000～4000 MPas.If tensile modulus of elasticity is less than 2000 MPas, the pencil hardness of laminated resin body, lower than 6H, if surpass 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 total light transmittance need to be for more than 90%.
For the three-dimensional cross-linked type hard resin composition using in the present invention, can be by it being carried out to free-radical polymerized obtaining (methyl) acrylate copolymer.For the physical property of improving (methyl) acrylic resin copolymer, or promote the objects such as free-radical polymerized, can in three-dimensional cross-linked type hard resin composition of the present invention, coordinate various additives.As the additive that promotes reaction, can illustration thermal polymerization, thermal polymerization promoter, Photoepolymerizationinitiater initiater, light-initiated auxiliary agent, sensitizer etc.While coordinating Photoepolymerizationinitiater initiater and thermal polymerization, with respect to total 100 weight portions of three-dimensional cross-linked type hard resin composition, its addition is preferably the scope of 0.1～5 weight portion, more preferably the scope of 0.1～3 weight portion.If this addition less than 0.1 weight portion, solidifies and become insufficient, the intensity of gained hard resin layer, rigidity step-down, on the other hand, if surpass 5 weight portions, may produce the problem such as painted of hard resin layer.Should illustrate, in total 100 weight portions of said three-dimensional cross-linked type hard resin composition, not comprise the fillers such as silica here.
The Photoepolymerizationinitiater initiater using when making three-dimensional cross-linked type hard resin composition be Photocurable composition, can preferably be used the compounds such as acetophenone system, benzoin system, benzophenone series, thioxanthones (チ オ キ サ Application ソ Application) are, acylphosphine oxide system.More specifically, can enumerate 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, 1,2-octane diketone, 1-[4-(phenyl sulfenyl)-, 2-(O-benzoyl oxime)] (1.2-オ Network タ Application ジ オ Application, 1-[4-(Off ェ ニ Le チ オ)-, 2-(O-ベ Application ゾ イ Le オ キ シ system)]), 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 a kind of, also can be by two kinds of above and use.
The three-dimensional cross-linked type hard 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 arbitrary shapes such as plane, curved surfaces.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 ℃ left and right.Now, by make its polymerizing curable in mould, on steel band, thereby can access the hard resin layer of desirable shape.
In addition, while utilizing irradiation to manufacture hard resin layer, can obtain by the ultraviolet ray of illumination wavelength 10～400nm, the luminous ray of wavelength 400～700nm.The light wavelength of using is not particularly limited, but particularly preferably uses the near ultraviolet ray of wavelength 200～400nm.As the lamp in ultraviolet generation source, can illustration low pressure mercury lamp 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. (power output:.Because there is feature each comfortable its light splitting distribution aspect of these ultraviolet lamps, so select according to the kind of the light trigger using.
Method as the hard resin layer of the arbitrary shape that utilizes irradiation to obtain using in the present invention, such as enumerating following method: inject three-dimensional cross-linked hard resin composition in the mould that there is chamber shape arbitrarily and formed by transparent raw material such as quartz glass, with above-mentioned ultraviolet lamp irradiation ultraviolet radiation, carry out polymerizing curable, make it from mold releasability, manufacture thus the formed body (hard resin layer) of desirable shape.In the situation that not using mould, such as can the following method of illustration etc.: on mobile steel band, the coating machine coating three-dimensional cross-linked type hard resin composition of the present invention that uses scraper, roller shape, makes its polymerizing curable with above-mentioned ultraviolet lamp, manufactures thus the formed body of sheet.
Should illustrate, while utilizing like this ultraviolet irradiation that three-dimensional cross-linked type hard resin composition is solidified, because ultraviolet curing reaction is radical reaction, so the reaction that can be subject to being caused by oxygen hinders.Therefore, from suppressing the reaction being caused by oxygen the curing reaction of three-dimensional cross-linked type hard resin composition, hinder such viewpoint and consider, preferably, after coat three-dimensional cross-linking type hard resin composition, use the overcoat being formed by transparent plastic foil to cover its surface.In addition, by making the surperficial oxygen concentration of three-dimensional cross-linked type hard oil/fat composition with the surface that overcoat covers three-dimensional cross-linked tree type hard resin composition like this, be preferably below 1%, more preferably below 0.1%.In order to reduce like this oxygen concentration, preferably adopt surface there is no hole and the low transparent plastic foil of oxygen permeability.As the material of such film, such as enumerating PET(PETG), PEN(PEN), PBT(polybutylene terephthalate (PBT)), PC(Merlon), polypropylene, polyethylene, acetate resins, acrylic resin, PVF be the plastics such as resin, polyamide, polyarylate, glassine paper, polyether sulfone, norbornene resin.These plastics can be used singly or in combination of two or more thereof.
Because above-mentioned plastic foil must be peeled off with the hard resin layer and the thermoplastic resin that consist of three-dimensional cross-linked type hard resin composition, so preferably use, the easily plastic foil of lift-off processing such as silicon coating, fluorine coating has been implemented in the surface of plastic foil.
In addition, above-mentioned plastic foil can be used as screening glass 6.During as screening glass 6, from the viewpoint of heat resistance, the transparency, weatherability, solvent resistance, rigidity, cost, consider, preferably use PETG film or polycarbonate membrane.
< thermoplasticity resin layer >
As the thermoplastic resin 3(3b using in the present invention), preferably clear is excellent, 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, hardness, mouldability, rigidity, the viewpoint of cost is considered, preferably use PETG, polymethyl methacrylate, or Merlon.These films can be used without the film stretching, and also can use the film of having implemented stretch process.
The hot castable resin layer using in the present invention is at the elastic modulus E of room temperature
1elastic modulus E with 150 ℃
2ratio (E
1/ E
2) be 1～500 scope.Mould while supposing moulding described later or the normal temperature of injection-molded resin are 150 ℃, if the elastic modelling quantity under room temperature is higher than the elastic modelling quantity at this temperature, the shape becoming cannot maintain moulding time due to the sprung back who causes because of hard resin layer.Therefore, the elastic modelling quantity of room temperature is larger with the ratio of the elastic modelling quantity of 150 ℃, easier moulding under forming temperature, and at room temperature shape more easily keeps.Therefore,, if modular ratio surpasses 500, the shape of the pencil hardness that has a laminated resin body during lower than 6H, thermoforming controlled the problem that becomes difficult such.Should illustrate, in the mensuration of modular ratio, thermoplasticity resin layer is heated to 230 ℃ with the programming rate of 5 ℃/min from room temperature and carry out Measurement of Dynamic Viscoelasticity, obtain the ratio of the storage elastic modulus (E ') of room temperature and 150 ℃.Should illustrate, in the present invention, said room temperature refers to the temperature of about 23～27 ℃, take 25 ℃ as benchmark in elastic modulus detection.
The gross thickness of the thermoplastic resin using in the present invention is 0.25～10 with the ratio (thermoplastic resin/hard tree resin layer) of the thickness of hard resin layer.If the ratio of thickness is less than 0.25, exist the processabilities such as moulding, cutting, perforation to become difficult such problem, if surpass 10, exist pencil hardness lower than the such problem of 6H.Should illustrate, the thickness of thermoplastic resin (being its total during multilayer) is preferably 30 μ m～1000 μ m.If be less than 30 μ m, the problem that while there is injection moulding, the generation of hard resin layer broken, crackle is such, on the other hand, if surpass 1000 μ m, exists pencil hardness to become difficult such problem lower than 6H, processing.
That the hard tree resin layer 1 of the laminated resin body the present invention relates to and thermoplastic resin 3 can utilize is membranaceous, the arbitrary adhesive phase 2 in sheet is stacked.As this adhesive phase 2, its thickness is preferably 0.01～30 μ m, more 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, cannot fully obtain the pencil hardness of laminated resin body if.Should illustrate, adhesive phase 2 herein can be any in following adhesive linkage or easy adhesive linkage.
< adhesive linkage >
As the layer that forms adhesive phase 2, can enumerate and use caking property bonding agent, pressure-sensitive bonding agent, Photocurable adhesive agent, the adhesive linkage of 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, is just not particularly limited.
The easy adhesive linkage > of <
In addition, as other layer that forms adhesive phase 2, can enumerate easy adhesive linkage.Easily adhesive linkage be carried out to the surface of the tree resin layer of difficult cementability carried out imposing chemical easy-adhesion energy or physics easy-adhesion can the layer of processing.Chemistry easy-adhesion can refer to by form the thin layer of the resin with functional group on substrate layer, form chemical bond with hard resin layer, thereby obtain the performance of closing force, 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 the performance with the closing force of hard tree resin layer.As the material with chemical easy-adhesion energy, can enumerate multifunctional (methyl) esters of acrylic acid, epoxies, contain the compound of sulfydryl etc., as the material with physics easy-adhesion energy, can enumerate SiO
2, SiN, SiC etc. vapor-deposited film etc.
In Fig. 1, show the 1st embodiment as an example of the embodiment of the laminated resin body the present invention relates to.As shown in Figure 1; this laminated resin body is as described below: on the two sides of thermoplasticity resin layer 3, be situated between and at upper and lower surface, form hard tree resin layer 1 by adhesive phase 2; and the lower surface at a side hard resin layer 1 has the structure that possesses printed layers 4, and the most surface at these surperficial back sides is formed with screening glass 6.Wherein, each adhesive phase 2 is as being used for making hard resin layer 1 and the integrated adhesive linkage performance of thermoplastic resin 3 function.
As shown in Figure 1, by the lower surface formation printed layers 4 of the laminated resin body the present invention relates to, thereby can form figure, Wen Yu etc.As the printing decorative pattern of printed layers 4, can enumerate the patterns such as wood grain, bag, woven design, sand streak, geometric figure, Wen Yu, whole solid (ベ タ comprehensively), metal, can set arbitrarily.
Preferably in printed layers 4, coordinating the resinous principle good with the compatibility of hard resin layer, thermoplasticity resin layer, is that resin, polyester urethane are that resin, cellulose esters are resin, alkyd resins, chlorinated polyolefin resin etc. such as polyethylene base system resin, polyamide-based resin, polyester based resin, acrylic resin, polyurethane series resin, polyvinyl acetals such as can enumerating vinyl chloride/vinyl acetate copolymer.By coordinating such resinous principle, thereby can suppress peeling off, coming off of printing.In addition, while forming 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, such as enumerating 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.In addition, as the thickness of printed layers 4, in this laminates, this film-stack products formed or the stacked products formed of this laminates, to obtain the mode of desirable appearance, suitably select thickness, be conventionally preferably 0.5～30 μ m left and right.
For laminated resin body of the present invention, as the 2nd, the 3rd embodiment, can illustration example structure as shown in Figure 2 and Figure 3.
Wherein, in the mat woven of fine bamboo strips 2 embodiments shown in Fig. 2; upper surface at thermoplastic resin 3 is formed with printed layers 4; at these printed layers 4 upper lateral parts and the side that do not form printed layers 4, clamped respectively pressure-sensitive bond layer 5; in printed layers 4 sides, be formed with hard tree resin layer 1; in a side that does not form printed layers 4, be formed with thermoplastic resin 3b in addition, on its two sides, be formed with screening glass 6.
In this Fig. 2, as used thermoplastic resin 3, as long as there is the transparency, be just not particularly limited, but preferred polymethyl methacrylate (PMMA).If thermoplastic resin 3 is PMMA, compare with PC, in the situation that thermoplastic resin is thick, even if hard resin layer is the thickness that approaches lower limit, also can form high pencil hardness.
On the other hand; in the 3rd embodiment shown in Fig. 3; upper surface clamping adhesive 2 at thermoplastic resin 3 forms hard resin layer 1; in addition; lower surface at thermoplastic resin 3 is formed with printed layers 4; at the lower surface that is formed with the thermoplastic resin 3 of printed layers 4, be situated between and form thermoplastic resin 3b by adhesive phase 2 or pressure-sensitive bond layer 5, on its two sides, be formed with screening glass 6.Laminated resin body in the 3rd embodiment is like this applicable to the processing of the shape that for example radius of curvature r is less.
The pressure-sensitive bond layer 5 using in the embodiment of Fig. 2 and Fig. 3 can be used known pressure-sensitive bonding agent.Particularly, such as using natural rubber, be that resin, synthetic rubber are that resin, silicon-type resin, acrylic resin, vinyl acetate are that resin, carbamate are the binding agents such as resin.As long as these bonding agents can access the just not restriction of required transmitance, caking property, weatherability.In addition, according to layer structure, in order to prevent the deteriorated of pigment, preferably in binding agent, 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 the concavo-convex of printed layers and the effect of its planarization is also reduced.In addition, more than 30 μ m, cannot fully obtain the pencil hardness of duplexer if.
In embodiments of the present invention Fig. 2,3, can under the state of laminated resin body, by thermoforming, give 3D shape.Thermoplastic resin 3 in Fig. 2,3 and 3b 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 phase 2 so can follow the shape of thermoplastic resin.As thermoforming, can enumerate vacuum forming, press empty moulding, extrusion forming etc.
In addition, during for layer structure as the laminated resin body shown in embodiments of the present invention Fig. 2, can use the A part, the B part that are shaped to respectively in advance regulation shape, be situated between and fitted by pressure-sensitive adhesive linkage 5.That is, can make to possess screening glass 6, the A part of hard resin layer 1, pressure-sensitive bond layer 5, printed layers 4 and thermoplastic resin 3, be partly situated between by 5 laminatings of pressure-sensitive bond layer and obtain with the B being formed by thermoplastic resin 3b and screening glass 6.
In addition; for the laminated resin body shown in embodiments of the present invention Fig. 3; can in the mould of desirable shape, load C part (screening glass 6, hard resin layer 1, adhesive phase 2, thermoplastic resin 3, printed layers 4 and adhesive phase 2(or pressure-sensitive bond layer 5)); and utilize injection moulding to inject thermoplastic resin 3b; and then screening glass 6 is set, form B part (thermoplasticity resin layer 3b and screening glass 6).
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, at interlayer arbitrarily, with printing process arbitrarily, form.
As shown in Figure 3, in the present invention, will carry out thermoforming as required and the laminated resin body that forms regulation shape fills in mould, by thermoplastic injection moulding, can make thus itself and thermoplastic resin integrated.Injection molding like this thermoplastic resin preferably has 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, polymethyl methacrylate, or carbonic ester, from the viewpoint of resistance to impact, consider, Merlon particularly preferably.
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) pencil hardness hardness: the JIS K5600 of take measures as benchmark.
2) total light transmittance: the JIS K7361-1 of take measures as benchmark.
3) thickness: the ID-SX processed of Mitutoyo Co., Ltd. measures.
4) tensile modulus of elasticity: the JIS K7127 of take measures as benchmark.
5) processability: at matching plane (ル ー タ ー) matching plane cutter (interior mountain sword thing system is installed in 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 section is observed to damaged (chip) for *, unobserved average evaluation is zero.
6) mouldability: observe to implement the formed body that obtains after the empty moulding of following Vacuum Pressure or injection moulding, by observing, break, in crackle, fracture, albefaction any average evaluation for *, will be zero for the average evaluation of kilter.
[synthesis example 1]
In possessing 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 Co., Ltd.) 126.9g, stirring reaction container on one side, on one side in room temperature the IPA solution with 30 minutes dropping MTMS.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 to and is after neutrality, with anhydrous magnesium sulfate, dewater.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 1]
(making of hard resin layer)
Mix in above-mentioned synthesis example, obtain on whole silicon atoms, there is the cage-type silsesquioxane compound of methacryl: 23 weight portions, dipentaerythritol acrylate: 39 weight portions, two cyclopenta diacrylates: 32 weight portions, urethane acrylate oligomer 1:6 weight portion, as the 1-hydroxycyclohexylphenylketone of Photoepolymerizationinitiater initiater: 2.5 weight portions, obtain transparent three-dimensional cross-linked type hard resin composition.Three-dimensional cross-linked type hard resin composition to gained, is used the formula of above-mentioned explanation to obtain (methyl) acryloyl group molal quantity of the every 100g resin solid composition containing in three-dimensional cross-linked type hard resin composition, and result is 0.76.The composition of this three-dimensional cross-linked type hard resin composition has been shown in table 1.
Should illustrate, the abbreviation in table 1 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 LightEster TMP processed of Kyoeisha Chemical Co., Ltd.)
D: pentaerythritol triacrylate (the Light AcrylatePE-3A processed of Kyoeisha Chemical Co., Ltd.)
E: the KAYARAD DPCA-20 processed of caprolactone modification dipentaerythritol acrylate 1(Nippon Kayaku K. K)
F: the KAYARAD DPCA-30 processed of caprolactone modification dipentaerythritol acrylate 2(Nippon Kayaku K. K)
G: two cyclopenta diacrylates (dihydroxymethyl tristane diacrylate) (the Light Acrylate processed DCP-A of Kyoeisha Chemical Co., Ltd.)
H: two cyclopenta dimethylacrylates (the NK EsterDCP processed of Xin Zhong village KCC)
I: polymethyl methacrylate (the PMMA) (KURARAY of Co., Ltd. ParapetLW processed: weight average molecular weight approximately 34000)
J: the UF-503 processed of urethane acrylate oligomer 1(Kyoeisha Chemical Co., Ltd.: number-average molecular weight approximately 8800)
K: the NK OligoUA-122P processed of urethane acrylate oligomer 2(Xin Zhong village KCC: number-average molecular weight approximately 1100)
L:1-hydroxycyclohexylphenylketone (polymerization initiator, the IRGACURE184 processed of BASF Japan Co., Ltd.)
Then, use roll coater, the mode that becomes 0.15mm with thickness is by three-dimensional cross-linked type hard resin composition cast on the PET that has carried out lift-off processing (curtain coating), the pet layer that other has been carried out to lift-off processing is pressed on after the three-dimensional cross-linked type hard resin composition of casting, use the high-pressure sodium lamp of 30W/cm, with 4000mJ/cm
2cumulative exposure amount it is solidified, the PET that has carried out lift-off processing is all peeled off and is removed, obtain thus becoming the hard resin layer of the sheet of specific thickness (150 μ m).Gained hard resin layer is measured to glass transition temperature, and result is until do not observe glass transition temperature in the mensuration of 300 ℃.In addition, measure tensile modulus of elasticity and total light transmittance of this hard resin layer.Show the result in table 1.
(making of laminated resin body)
By cation, be Photocurable adhesive agent (vertical chemical industry society of association system) in the mode of thickness that becomes 5 μ m to the Merlon (PC-1151 processed of Di Ren society, 200mm * 200mm * thickness 0.5mm) be coated with after curtain coating, the hard resin layer obtaining in above-mentioned is fitted in to whole of the one side side of Merlon, after crimping, use metal halide lamp with 500mJ/cm
2ratio from two sides irradiation ultraviolet radiation, to hard tree resin layer, give screening glass, obtain thus laminated resin body (A part).Should illustrate, here for as the Merlon of thermoplastic resin, with the programming rate of 5 ℃/min, from room temperature (25 ℃), be heated to 230 ℃, measure dynamic viscoelastic (DMA), by the storage elastic modulus E under room temperature
1with 150 ℃ at storage elastic modulus E
2obtain modular ratio (E
1/ E
2), result is 1.35.
(the empty moulding embodiment of Vacuum Pressure)
With silicon rubber (thickness 0.8mm) from clamping up and down the laminated resin body (A part) obtaining above-mentioned, pressing delay till laminated resin body (A part) being pressed to sky at 150 ℃～250 ℃, empty 5 atmospheric pressure, upper and lower mold temperature, be that 10 seconds, pressure hold time are 30 seconds, thus laminated resin body (A part) be shaped to 4 limits and there is curved surface (radius of curvature a:8mm), have the curve form (height b:7mm) of the cross sectional shape shown in Fig. 5.The surperficial pencil hardness of the formed body of gained laminated resin body being measured to hard resin layer, result is 8H.In addition, carry out the evaluation of processability and the mouldability of above-mentioned laminated resin body.Table 2 will be shown in result set.
[embodiment 2]
(making of hard resin layer)
Mix in above-mentioned synthesis example, obtain on whole silicon atoms, there is the cage-type silsesquioxane compound of methacryl: 23 weight portions, dipentaerythritol acrylate: 39 weight portions, two cyclopenta diacrylates: 32 weight portions, urethane acrylate oligomer 1:6 weight portion, as the 1-hydroxycyclohexylphenylketone of Photoepolymerizationinitiater initiater: 2.5 weight portions, obtain having the composition shown in table 1 and transparent three-dimensional cross-linked type hard resin composition.
Next; use roll coater; the mode that becomes 0.1mm with thickness is cast three-dimensional cross-linked type hard resin composition in (curtain coating) on the PET of 200mm * 200mm * thickness 100 μ m that has carried out easy bonding processing; the PET of same size that other has been carried out to lift-off processing is after screening glass is laminated to the three-dimensional cross-linked type hard resin composition that has carried out casting; use the high-pressure sodium lamp of 30W/cm, with 4000mJ/cm
2cumulative exposure amount it is solidified, obtain thering is the sheet as the PET of thermoplastic resin on the two sides, the surperficial back side of hard resin layer (100 μ m).The carrying out of gained the face contrary with easy bonding plane of thermoplastic resin of easy bonding processing printed layers, adhesive phase are set, obtain laminated resin body (C part).Should illustrate, until do not observe the glass transition temperature of the hard resin layer in this C part in the mensuration of 300 ℃, single tensile modulus of elasticity and total light transmittance are as shown in table 1.In addition, for the modular ratio (E that is used as the PET of thermoplastic resin
1/ E
2) also concentrate and be shown in table 1.
(the empty moulding embodiment of Vacuum Pressure)
With silicon rubber (thickness 0.8mm) from clamping up and down gained laminated resin body (C part), pressing delay till laminated resin body (C part) being pressed to sky at 150 ℃～250 ℃, empty 5 atmospheric pressure, upper and lower mold temperature, be that 10 seconds, pressure hold time are 30 seconds, be shaped to thus the curve form identical with embodiment 1.The pencil hardness of the formed body of gained laminated resin body being measured to hard tree resin layer, result is 7H.In addition, carry out the evaluation of processability and the mouldability of above-mentioned laminated resin body.Table 2 will be shown in result set.
(injection moulding embodiment)
Next, after laminated resin body through curved surface forming (C part) being filled in the 1st injecting molding die of Fig. 4, the 2nd injecting molding die is overlapped on the 1st injecting molding die, under this state, at 320 ℃ of resin temperatures, 90 ℃～120 ℃ of mold temperatures, mould inner pressure 300-500kg/cm
2, 5 seconds inject time condition under, chamber injection in from from injection gate to mould is in advance 120 ℃ of polycarbonate resin (SABIC company systems that have been dried 24 hours, trade name " HFD1810 "), obtain thus the laminated resin body that makes to have hard tree resin layer (C part) and the integrated injection molded article of thermoplastic resin (B part) 500 μ m as shown in Figure 3.
[comparative example 1]
By dipentaerythritol acrylate: 85 weight portions, PMMA:15 weight portion add hot milling to 110 ℃, thereafter, mix the 1-hydroxycyclohexylphenylketone as Photoepolymerizationinitiater initiater: 2.5 weight portions, obtain three-dimensional cross-linked type hard resin composition.
Next, similarly to Example 2, obtaining making laminated resin body after hard resin layer, and evaluating.Show the result in table 2.
[embodiment 3～8 and comparative example 2～6]
Making mix proportion is the part by weight shown in table 1, in addition, in embodiment 3, embodiment 7, comparative example 2 and comparative example 4, similarly to Example 1, in embodiment 4, embodiment 5, embodiment 6, embodiment 8, comparative example 1, comparative example 3, comparative example 5 and comparative example 6, obtain similarly to Example 2 hard resin layer and laminated resin body.The evaluation result of gained formed body is shown in to table 2 in the lump.
[synthesis example 2]
By acrylic acid two cyclopentyl ester 4.0 moles (825g), 2-hydroxyethyl methacrylate 3.0 moles (390g), 1,4-butanediol diacrylate 3.0 moles (595g), 2,4-diphenyl-4-methyl-1-pentene 4.0 moles of (889g), toluene 2400ml drop in the reactor of 10.0L, at 90 ℃ of benzoyl peroxides that add 240mmol, react 6 hours.By cooling polymerisation is stopped after, at room temperature reaction mixture is dropped in a large amount of hexanes, polymer is separated out.With hexane, clean resulting polymers, filter, be dried, weigh, obtain copolymer A 615g(yield: 34%)
The Mw of gained copolymer A is that 15200, Mn is that 3900, Mw/Mn is 3.9.Copolymer A contains from the construction unit of acrylic acid two cyclopentyl esters and adds up to 37.8 % by mole, and the construction unit containing from 2-hydroxyethyl methacrylate adds up to 29.3 % by mole, contains from 32.9 % by mole of the construction units of BDO diacrylate.In addition, from 2, the end group of the structure of 4-diphenyl-4-methyl-1-pentene exists 9.8 % by mole with respect to the total amount of acrylic acid two cyclopentyl esters, 2-hydroxyethyl methacrylate, BDO diacrylate and 2,4-diphenyl-4-methyl-1-pentene.And the ratio of side chain acrylate (ペ Application ダ Application ト ア Network リ レ ー ト) is 16.5 % by mole.Mb is 0.29.Copolymer A dissolves in ethanol, 2-propyl alcohol, butanols, toluene, dimethylbenzene, THF, dichloroethanes, carrene, chloroform, and does not see the generation of gel.
[synthesis example 3]
By acrylic acid two cyclopentyl ester 0.24 mole (49.5g), dihydroxymethyl tristane diacrylate 2.6 moles (729.4g), 1,4-butanediol diacrylate 0.96 mole (190.1g), acrylic acid 2-hydroxy propyl ester 0.96 mole (124.9g), 2,4-diphenyl-4-methyl-1-pentene 0.48 mole of (113.4g), tertiary lauryl mercaptan 3.12 moles of (631.5g), toluene 700ml drop in the reactor of 3.0L, at 90 ℃ of benzoyl peroxides that add 72mmol, react 6 hours.By cooling polymerisation is stopped after, at room temperature reaction mixture is dropped in a large amount of hexanes, polymer is separated out.With hexane, clean resulting polymers, filter, be dried, weigh, obtain copolymer B696.9g(yield: 63.7 % by mole).
The Mw of gained copolymer B is that 39500, Mn is that 7240, Mw/Mn is 5.5.By carrying out
13c-NMR,
1h-NMR analyzes and elementary analysis, result is that copolymer A contains from 4.9 % by mole of the construction units of acrylic acid two cyclopentyl esters, contain from dihydroxymethyl tristane diacrylate and 1, the construction unit of 4-butanediol diacrylate adds up to 75.5 % by mole, contains from 19.6 % by mole of the construction units of acrylic acid 2-hydroxy propyl ester.In addition, from 2, the end group of the structure of 4-diphenyl-4-methyl-1-pentene is with respect to from acrylic acid two cyclopentyl esters, dihydroxymethyl tristane diacrylate, acrylic acid 2-hydroxy propyl ester, 2, the total amount of the end group of the structure of 4-diphenyl-4-methyl-1-pentene and tertiary lauryl mercaptan (total amount that is called below, total Component units) exists 3.7 % by mole.On the other hand, from the end group of the structure of tertiary lauryl mercaptan, with respect to the total amount of total Component units, there are 18.6 % by mole.And the ratio of side chain acrylate is 43.5 % by mole.
Copolymer B dissolves in toluene, dimethylbenzene, THF, dichloroethanes, carrene, chloroform, and does not see the generation of gel.
[embodiment 9～12]
Making mix proportion is the part by weight shown in table 3, in addition, obtains similarly to Example 1 hard resin layer and laminated resin body.The evaluation result of gained formed body is shown in to table 3 in the lump.
[table 3]
| Embodiment 9 | Embodiment 10 | Embodiment 11 | Embodiment 12 | |
| M | 10 | 10 | ||
| N | 20 | |||
| B | 35 | 35 | 30 | 20 |
| O | 35 | 35 | 30 | 25 |
| P | 20 | 20 | ||
| Q | 20 | |||
| G | 30 | |||
| R | 20 | |||
| J | 5 | |||
| L | 2.5 | 2.5 | 2.5 | 2.5 |
| Acryloyl group molal quantity | 0.79 | 0.73 | 0.72 | 0.81 |
| Thickness | 150 | 150 | 150 | 150 |
| Tensile modulus of elasticity | 2620 | 2250 | 2150 | 3050 |
| Transmissivity | 90.6 | 90.5 | 90.3 | 90.1 |
| A part | PC(500um) | PC(500um) | PC(500um) | PC(500um) |
| B part | ||||
| C part | ||||
| Modular ratio | 1.35 | 1.35 | 1.35 | 1.35 |
| Thickness Ratio | 3.33 | 3.33 | 3.33 | 3.33 |
| Pencil hardness | 8H | 6H | 6H | 8H |
| Processability | ○ | ○ | ○ | ○ |
| Mouldability | ○ | ○ | ○ | ○ |
Should illustrate, the abbreviation in table 3 except above-mentioned is as described below.
M: the copolymer A obtaining in synthesis example 2
N: the copolymer B obtaining in synthesis example 3
B ': dipentaerythritol acrylate (Daicel-Cytec Co., Ltd. system)
O: trimethylolpropane triacrylate (Kyoeisha Chemical Co., Ltd.'s system)
G: dihydroxymethyl-tristane diacrylate (two cyclopenta diacrylates) (the Light Acrylate processed DCP-A of Kyoeisha Chemical Co., Ltd.)
P:1,9-nonanediol diacrylate (Kyoeisha Chemical Co., Ltd.'s system)
Q: acrylic acid two cyclopentyl esters (Hitachi Chemical Co., Ltd.'s system)
R: tripentaerythritol eight acrylate
Claims (8)
1. a laminated resin body, is characterized in that, has at least 1 layer of above hard resin layer and thermoplastic resin; Described hard resin layer is curing the forming of three-dimensional cross-linked type hard resin composition that makes to contain multifunctional (methyl) acryloyl monomer with cage silsesquioxane structure, and glass transition temperature is more than 200 ℃; Described thermoplastic resin is at least one side of this hard resin layer, and the elastic modulus E of room temperature
1elastic modulus E with 150 ℃
2ratio E
1/ E
2be 1～500; The single tensile modulus of elasticity of hard resin layer is 2000～4000 MPas, and total light transmittance is more than 90%; In addition, the pencil hardness of laminated resin body is more than 6H, the total thickness t of thermoplastic resin
1thickness t with hard resin layer
2ratio t
1/ t
2be 0.25～10.
2. laminated resin body according to claim 1; it is characterized in that; (methyl) acryloyl group molal quantity of the every 100g resin solid composition containing in three-dimensional cross-linked type hard resin composition is 0.6～0.9, and the thickness of hard resin layer is 50 μ m～250 μ m.
3. 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 adhesive linkage.
4. laminated resin body according to claim 1 and 2, is characterized in that, adhesive linkage is any in caking property bonding agent, pressure-sensitive bonding agent, Photocurable adhesive agent, heat-curable adhesive or 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, has multifunctional (methyl) acryloyl 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）
R in formula
1～R
6it is the group of the alkyl with carbon number 1～6, phenyl, (methyl) acryloyl group, (methyl) acryloxyalkyl, vinyl, oxirane ring; the group that can be respectively identical also can contain different groups; 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, the number that l is 0～4, and meet m≤1.
7. a forming method for laminated resin body, is characterized in that, by laminated resin body claimed in claim 1 is carried out to the shape that regulation is given in thermoforming.
8. the forming method of laminated resin body according to claim 7, is characterized in that, the laminated resin body of the regulation shape that the method for utilizing described in claim 7 is obtained fills in mould, and thermoplastic injection moulding is carried out integrated.
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|---|---|---|---|
| JP2013056860 | 2013-03-19 | ||
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|---|---|
| JP (1) | JP2014205345A (en) |
| KR (1) | KR20140114795A (en) |
| CN (1) | CN104057680A (en) |
| TW (1) | TW201438909A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106085169A (en) * | 2015-05-01 | 2016-11-09 | 味之素株式会社 | Solidification compound |
| CN108699266A (en) * | 2016-02-15 | 2018-10-23 | 株式会社可乐丽 | Thermoplastic resin film and its manufacturing method and laminated body |
| CN108928075A (en) * | 2017-05-26 | 2018-12-04 | 住友化学株式会社 | Curved laminated resin body |
| CN111002667A (en) * | 2019-12-19 | 2020-04-14 | 宁波长阳科技股份有限公司 | Release film and preparation method thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102065717B1 (en) * | 2016-12-26 | 2020-01-13 | 주식회사 엘지화학 | Polarizer protecting film, polarizer plate comprising the same, liquid crystal display comprising the polarizer plate, and coating composition for polarizer protecting film |
| EP3702174B1 (en) * | 2017-10-25 | 2023-05-17 | Bridgestone Corporation | Metal resin composite member for tires, and tire |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012063637A1 (en) * | 2010-11-10 | 2012-05-18 | 新日鐵化学株式会社 | Multilayered hardcoat film for injection molding, process for producing same, and process for producing injection-molded object using the multilayered hardcoat film |
| CN104981349A (en) * | 2013-02-12 | 2015-10-14 | 新日铁住金化学株式会社 | Resin laminate |
-
2014
- 2014-03-12 TW TW103108610A patent/TW201438909A/en unknown
- 2014-03-17 JP JP2014053575A patent/JP2014205345A/en active Pending
- 2014-03-18 CN CN201410101404.XA patent/CN104057680A/en active Pending
- 2014-03-18 KR KR1020140031711A patent/KR20140114795A/en not_active Application Discontinuation
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012063637A1 (en) * | 2010-11-10 | 2012-05-18 | 新日鐵化学株式会社 | Multilayered hardcoat film for injection molding, process for producing same, and process for producing injection-molded object using the multilayered hardcoat film |
| CN104981349A (en) * | 2013-02-12 | 2015-10-14 | 新日铁住金化学株式会社 | Resin laminate |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106085169A (en) * | 2015-05-01 | 2016-11-09 | 味之素株式会社 | Solidification compound |
| CN108699266A (en) * | 2016-02-15 | 2018-10-23 | 株式会社可乐丽 | Thermoplastic resin film and its manufacturing method and laminated body |
| CN108699266B (en) * | 2016-02-15 | 2021-07-16 | 株式会社可乐丽 | Thermoplastic resin film, method for producing same, and laminate |
| CN108928075A (en) * | 2017-05-26 | 2018-12-04 | 住友化学株式会社 | Curved laminated resin body |
| CN111002667A (en) * | 2019-12-19 | 2020-04-14 | 宁波长阳科技股份有限公司 | Release film and preparation method thereof |
| CN111002667B (en) * | 2019-12-19 | 2022-03-08 | 宁波长阳科技股份有限公司 | Release film and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2014205345A (en) | 2014-10-30 |
| KR20140114795A (en) | 2014-09-29 |
| TW201438909A (en) | 2014-10-16 |
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