CN1318462C - Acrylic resin, resin boards, transparent electrode boards for touch panels, touch panels, and processes for production of them - Google Patents
Acrylic resin, resin boards, transparent electrode boards for touch panels, touch panels, and processes for production of them Download PDFInfo
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- CN1318462C CN1318462C CNB2003801029789A CN200380102978A CN1318462C CN 1318462 C CN1318462 C CN 1318462C CN B2003801029789 A CNB2003801029789 A CN B2003801029789A CN 200380102978 A CN200380102978 A CN 200380102978A CN 1318462 C CN1318462 C CN 1318462C
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Abstract
A process for the production of acrylic resin boards by polymerizing and curing a polymerizable mixture which comprises 100 parts by mass of a mixture comprising an alkyl methacrylate wherein the alkyl has 1 to 4 carbon atoms and a polyfunctional (meth)acrylate, 0.001 to 1 part by mass of a polymerization initiator having a ten-hour half-life temperature of 80 DEG C or above, and 0.015 to 0.2 part by mass of cyclohexadiene or a terpenoid; an acrylic resin comprising 3 to 30 % by mass of alkyl methacrylate units wherein the alkyl has 8 to 20 carbon atoms, 2 to 35 % by mass of monoethylenically unsaturated monomer units comprising alkyl methacrylate units wherein the alkyl has 1 to 4 carbon atoms, and 35 to 95 % by mass of polyfunctional (meth)acrylate units; resin boards made from this resin and a process for the production thereof; and transparent electrode boards for touch panels and touch panels, made by using the above resin boards.
Description
Technical field
The touch panel of the resin board that the present invention relates to the good acrylic resin of thermotolerance, outward appearance, shape stability, is made of this acrylic resin, the transparency carrier with thermotolerance, the transparency, conducting film sticking power excellence is with transparent electrode plate and have the touch panel of this transparent electrode plate and their manufacture method.
Background technology
＜acrylic acid resin plate 〉
Acrylic acid resin plate is owing to its excellent optical is applied to lens, auto parts, illuminace component, various electronic consoles etc.But under the situation of at high temperature acrylic acid resin plate being carried out heat treated processing, there is the not enough shortcoming of thermotolerance in it.
As the stable on heating technology of improving acrylic acid resin plate, the method that imports crosslinking structure when methyl methacrylate polymerization by the interpolation polyfunctional monomer is arranged.For example, following method has been proposed: for example, mainly in order to improve thermotolerance and shock resistance, add polyfunctional group (methyl) acrylate of alkylene glycol and carry out cast polymerized method (for example, with reference to special fair 4-75241 communique) to the composition of forming by methyl methacrylate list aggressiveness and methyl methacrylate.But,, can not obtain enough thermotolerances usually by this method.In order to obtain enough thermotolerances by this method, need heavy addition polyfunctional group (methyl) acrylate, there is the trend of the degraded appearance of gained resin molded item this moment.
In addition, in order to improve thermotolerance and outward appearance, following method has been proposed: add at least a in cyclohexadiene and derivative and class terpenoid and the derivative thereof and carry out cast poymerization (for example, opening the 2002-265538 communique) with reference to the spy to methyl methacrylate and polyfunctional group (methyl) acrylate.But,, can not obtain enough thermotolerances usually by this method.In addition, the gained resin board is the resin board of easy moisture absorption.
In addition, in order to improve thermotolerance and outward appearance, following method has been proposed also: the composition that is made of alkylmethacrylate class slurry and linking agent is carried out cast poymerization, wherein alkylmethacrylate class slurry is a wherein part and form (for example, opening clear 63-30510 communique with reference to the spy) of mixed alkyl acrylate monomer and (methyl) acrylic ester cross-linking agent and polymerization.But this method causes gelation easily when preparing slurry at mixed cross-linker.
In order to improve outward appearance, the ratio appointment method (for example, opening clear 61-225207 communique with reference to the spy) within the specific limits with linking agent and alkylmethacrylate base polymer has been proposed also in addition.But, not put down in writing polyfunctional monomer at this and surpass 20% embodiment, this method can not obtain enough thermotolerances usually.In addition, in order to obtain the resin board of thermotolerance height and outward appearance excellence, need on forming, limit the obstacle when this will become industrialization.
The manufacture method of following acrylic acid resin plate has also been proposed in addition: use at least 2 kinds of radical polymerization initiators, monomer and allyl group (methyl) acrylate based on the methyl methacrylic acid ester are carried out cast poymerization, to be the high value of boundary with difference than low value differ by more than equals 5 ℃ (for example, opening flat 9-25305 communique with reference to the spy) with 75 ℃ for 10 hours half life temperatures in the described radical polymerization initiator.But this method exists allylic polymerizability poor, and can not obtain abundant stable on heating trend.
The manufacture method (for example, with reference to special fair 4-30410 communique) of following optical material is proposed in addition: carry out radical polymerization as main component with polyfunctional group (methyl) acrylate with alkene group.(for example, with reference to special fair 4-30410 communique).But there are the following problems for this method: in the stripping process during fabrication, if at high temperature do not peel off, plate will take place split.
＜touch panel transparent electrode plate and touch panel 〉
Display unit such as liquid crystal or cathode-ray picture tube is provided with the one-piece type input unit of display unit of transparent touch panel, by input pen or its display image of finger contact, touch panel plays the effect of input unit and can carry out input operation easily.Particularly the simulation touch panel of resistive film mode can be handled all operations image, therefore, has obtained using especially widely.
The simulation touch panel of resistive film mode generally has upper transparent electrode plate and lower transparent electrode plate, and top and lower transparent electrode plate are to have transparency carrier and the transparent electrode plate that is formed at the nesa coating on this transparency carrier, and have top and lower transparent electrode plate and be configured to each other the opposed structure of nesa coating with being spaced distance.
If have the upper transparent electrode plate of the touch panel of this structure with input pen or finger presses, then the upper transparent electrode plate bends, and on this press points, the nesa coating of top and lower transparent electrode plate is in contact with one another.So, detect the coordinate of this point of contact by measuring resistance, thereby read input information.
Transparent electrode plate as such touch panel, the general use: for the upper transparent electrode plate as lower electrode plate, use resin board as transparency carrier, for the lower transparent electrode plate, use sheet glass or resin board as transparency carrier, and utilize Vacuum Coating method, sputtering method, CVD (chemical vapordeposition) method, ion plating method equal vacuum to become embrane method, on the surface of these transparency carriers, form nesa coating.
Yet, use the lower electrode plate of sheet glass as transparency carrier, when pushing when the assembling of touch panel and carrying or with pen or hand, existence is broken easily, is difficult to problems such as slimming, lightweight.
On the other hand, if use resin board, can easily solve in breakage, slimming and the light-weighted problem of using the substrate that produces under the situation of sheet glass as transparency carrier as transparency carrier.In fact also to using resin board to carry out various researchs (for example, open 2000-276301 communique, spy are opened the 2001-14951 communique, the spy opens the 2001-34418 communique) with reference to the spy as the top of transparency carrier and lower electrode plate.Yet, use the transparency carrier of resin board such as in these patent documentations disclosed polyethylene terephthalate resin, its transparency is not enough.In addition, because the thermotolerance deficiency, therefore, when on transparency carrier, forming nesa coating, easy thermal distortion, because the sticking power of nesa coating is low, therefore durability not insufficient, exists problems such as needing further to process the transparency carrier surface.
In addition, disclose with methyl methacrylate with as the neopentylglycol dimethacrylate of polyfunctional group (methyl) acrylate and carried out polymerization as monomer and the methacrylic resin moulding material that obtains (for example, with reference to special fair 5-6570 communique).But not having to disclose this methacrylic resin moulding material herein fully can not point out fully that the substrate how to form is suitable for as the touch panel transparent electrode plate as the transparency carrier of touch panel with transparent electrode plate yet.In addition, the methacrylic resin moulding material of putting down in writing in this patent documentation because percent polymerization is low to 4～62 quality %, therefore, when this moulding material is made product, needs further to improve percent polymerization by operations such as compressed moulding, extrusion mouldings.Therefore, deform, and be not suitable for touch panel.
The touch panel that uses transparency carrier is disclosed, described transparency carrier is to make by following operation: add mercaptan and obtain Photocurable composition in the monomer mixture that contains more than or equal to specified two (methyl) acrylate of 90 quality %, in cell (cell) that its formation is tabular again, and make its photocuring and obtain transparency carrier (for example, opening flat 10-105335 number) with reference to the spy.But there are the following problems for this transparency carrier: behind polymerizing curable from the operation that cell is peeled off, plate takes place easily to break.
Summary of the invention
The object of the present invention is to provide the break manufacture method of acrylic acid resin plate of the good and excellent heat resistance of preventing property of plate in the stripping process during fabrication.In addition, the acrylic acid resin plate that the object of the present invention is to provide the good acrylic resin of thermotolerance, outward appearance, shape stability, constitutes by this resin.In addition, the object of the present invention is to provide and have thermotolerance, the touch panel of the resin substrate of the transparency, adhesive force excellence is with transparent electrode plate and has the touch panel of this transparent electrode plate and their manufacture method.
The present invention is the manufacture method with acrylic acid resin plate of following operation: the mixture that is made of single ethylene unsaturated monomer 5～65 quality % and polyfunctional group (methyl) acrylate 35～95 quality % of per 100 mass parts, make its 10 hours half life temperatures that contain 0.001～1 mass parts form polyblend at least a compound that is selected from the group that cyclohexadiene and derivative thereof and class terpenoid and derivative thereof form more than or equal to 80 ℃ polymerization starter and 0.015～0.2 mass parts, and this polyblend is carried out the operation of polymerizing curable, above-mentioned single ethylene unsaturated monomer is the material that comprises the alkyl methacrylate of the alkyl with carbonatoms 1～4, described polyfunctional group (methyl) acrylate is the compound of following general formula (1) expression
In the formula, R
1Expression H or CH
3
In addition; the present invention is the manufacture method with acrylic acid resin plate of following operation; the mixture that polyfunctional group (methyl) acrylate with (methyl) acryl more than 2 or 2 by the slurry of 5～65 mass parts and 35～95 mass parts of per 100 mass parts constitutes; make its 10 hours half life temperatures that contain 0.001～1 mass parts form polyblend at least a compound that is selected from the group that cyclohexadiene and derivative thereof and class terpenoid and derivative thereof form more than or equal to 80 ℃ polymerization starter and 0.015～0.2 mass parts; and this polyblend carried out the operation of polymerizing curable, above-mentioned slurry is formed by single ethylene unsaturated monomer 70～99 quality % of the alkyl methacrylate that comprises the alkyl with carbonatoms 1～4 with by (being total to) polymkeric substance 1～30 quality % that single ethylene unsaturated monomer unit of the alkyl methacrylate that comprises the alkyl with carbonatoms 1～4 constitutes.
In addition, the present invention is the acrylic resin laminated body manufacturing method that forms nesa coating at least one surface of the acrylic acid resin plate that these manufacture method make.
In addition, the present invention has the manufacture method of the touch panel of the operation that forms nesa coating at least one surface of the acrylic acid resin plate that these manufacture method make with transparent electrode plate.
In addition, the present invention is a kind of manufacture method of touch panel, it is to have upper transparent electrode plate and lower transparent electrode plate, this upper transparent electrode plate and lower transparent electrode plate are the transparent electrode plates that has transparency carrier and be formed at least one lip-deep nesa coating of this transparency carrier, make the manufacture method of the touch panel of each other nesa coating opposed and partition distance ground this upper transparent electrode plate of configuration and this lower transparent electrode plate, wherein, at least one of this upper transparent electrode plate and lower transparent electrode plate is the touch panel transparent electrode plate that makes by above-mentioned manufacture method.
In addition, the present invention is the acrylic resin that contains polyfunctional group (methyl) acrylic ester unit with (methyl) acryl more than 2 or 2 of single ethylene unsaturated monomer unit of the alkyl methacrylate that comprises the alkyl with carbonatoms 1～4 of the alkyl methacrylate unit of the alkyl with carbonatoms 8～20 of 3～30 quality % and 2～35 quality % and 35～95 quality %.
In addition; the present invention has the manufacture method of acrylic acid resin plate of polyblend being carried out the operation of polymerizing curable, and described polyblend contains the single ethylene unsaturated monomers of alkyl methacrylate of the alkyl with carbonatoms 1～4 of the alkyl methacrylate of the alkyl with carbonatoms 8～20 of 3～30 quality % and 2～35 quality % and polyfunctional group (methyl) acrylate with (methyl) acryl more than 2 or 2 of 35～95 quality %.
In addition, the present invention forms nesa coating and the acrylic resin layered product that forms at least one surface of this acrylic acid resin plate.
In addition, the present invention is the touch panel transparent electrode plate with this acrylic resin layered product.
In addition, the present invention is a kind of touch panel, it is to have upper transparent electrode plate and lower transparent electrode plate, this upper transparent electrode plate and lower transparent electrode plate are the transparent electrode plates that has transparency carrier and be formed at least one lip-deep nesa coating of this transparency carrier, make the opposed and touch panel of partition distance ground this upper transparent electrode plate of configuration and this lower transparent electrode plate of each other nesa coating, and at least one of this upper transparent electrode plate and lower transparent electrode plate is above-mentioned touch panel transparent electrode plate.
In the manufacture method of acrylic acid resin plate of the present invention, by adopting specified composition, thereby can keep the optical property of the excellence of acrylic resin, and can significantly improve plate in thermotolerance, outward appearance, the stripping process during fabrication the preventing property of breaking.
In addition, with regard to the acrylic acid resin plate of forming with regard to acrylic resin of the present invention, by this resin, by adopting specified composition, thereby the excellent optical property that can keep acrylic resin itself to have, and can significantly improve thermotolerance, outward appearance, shape stability.In addition, forming nesa coating such as ITO film and the acrylic resin layered product that forms on this acrylic acid resin plate, is very useful as the touch panel transparent electrode plate.
Touch panel of the present invention with transparent electrode plate owing to kept the optical property of the excellence that acrylic resin had originally, and has a thermotolerance of the thermofixation operation of the film formation process that can tolerate inorganic thin film, electrode, and adhesive force is very excellent, therefore, need not to carry out the surface treatment of resin substrate.In addition, resin board can be used in the substrate of touch panel with transparent electrode plate, therefore, can be easy to prevent breakage, realization lightweight, the thin layerization of touch panel, can be applicable to purposes, the shape that can not obtain in the use of former sheet glass.
Description of drawings
Fig. 1 is the mode sectional drawing of expression touch panel of the present invention with an example of transparent electrode plate.
Fig. 2 is that expression touch panel of the present invention cuts open with the pattern of an example of transparent electrode plate and schemes.
Fig. 3 is that the transparent electrode plate represented among Fig. 1 and Fig. 2 mode sectional drawing as an example of the touch panel of lower transparent electrode plate is used in expression.
Embodiment
＜acrylic resin and resin board 〉
At the manufacture method of acrylic acid resin plate of the present invention, at first, just use the situation of the mixture of forming by single ethylene unsaturated monomers and polyfunctional group (methyl) acrylate to describe.
Mixture under this situation is the material by polyfunctional group (methyl) the acrylate formation with (methyl) acryl more than 2 or 2 of single ethylene unsaturated monomer of the alkyl methacrylate of the alkyl that has carbonatoms 1～4 comprising of 5～65 quality % and 35～95 quality %.
The content of single ethylene unsaturated monomer that comprises the alkyl methacrylate of the alkyl with carbonatoms 1～4 is 5～65 quality % in mixture.Have following trend: if this content more than or equal to 5 quality %, then outward appearance improves, if this content smaller or equal to 65 quality %, then thermotolerance improves.In addition, this content is preferably 10～55 quality %, more preferably 15～50 quality %.When the total amount of single ethylene unsaturated monomer of the alkyl methacrylate that comprises the alkyl with carbonatoms 1～4 is made as 100 mass parts, under the situation of giving the resin board high transparent, the ratio of alkyl methacrylate with alkyl of carbonatoms 1～4 is preferably greater than and equals 50 mass parts, in addition under the situation, the ratio of single ethylene unsaturated monomer is preferably smaller or equal to 50 mass parts.In case form such ratio, the tendency that exists the transparency to improve, and also thermotolerance improves more.
As the alkyl methacrylate of alkyl, can enumerate for example methyl methacrylate, Jia Jibingxisuanyizhi, n propyl methacrylate, isopropyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, methacrylic tert-butyl acrylate etc. with carbonatoms 1～4.Can also and use these esters.Wherein, special preferable methyl methyl acrylate.
As the single ethylene unsaturated monomers beyond the alkyl methacrylate of alkyl, can enumerate for example vinylbenzene with carbonatoms 1～4, alpha-methyl styrene, vinyl cyanide, vinylformic acid, methacrylic acid, methyl acrylate, ethyl propenoate, n-butyl acrylate, ethyl acrylate, lauryl methacrylate(LMA), tridecyl methacrylate(TD-, methacrylic acid stearyl ester, methacrylic acid isostearoyl ester, cyclohexyl methacrylate, benzyl methacrylate, the methacrylic acid Isobornyl, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, methacrylic acid-2-hydroxy methacrylate, methacrylic acid hydroxyl propyl ester, methacrylic acid methoxy base ethyl ester, methacrylic acid ethoxy ethyl ester etc.Can also and use these esters.In order to reduce the levels of residual monomers of gained resin board, preferably use methyl acrylate, ethyl propenoate etc. to have the alkyl acrylate of the alkyl of carbonatoms 1～4.
Content with polyfunctional group (methyl) acrylate of (methyl) acryl more than 2 or 2 is 35～95 quality % in mixing.Have following trend: if this content more than or equal to 35 quality %, then thermotolerance improves, if smaller or equal to 95 quality %, then outward appearance is good.This content is preferably 45～90 quality %, more preferably 50～85 quality %.
What is called has polyfunctional group (methyl) acrylate of (methyl) acryl more than 2 or 2, is meant the multi-functional acrylate with the acryl more than 2 or 2 or has the polyfunctional group methacrylic ester of the methacryloyl more than 2 or 2.Can also and use these.As this polyfunctional group (methyl) acrylate, can enumerate the compound shown in the following general formula (1),
(in the formula, R
1Expression hydrogen or methyl)
Compound shown in the following general formula (2),
(in the formula, R
2And R
3Expression hydrogen or methyl, R
4And R
5Expression hydrogen or carbonatoms are smaller or equal to 3 alkyl, and n represents 0～4 integer.) and
Trimethylolpropane trimethacrylate, Viscoat 295, tetramethylolmethane tetramethyl-acrylate, tetramethylol methane tetraacrylate, two (TriMethylolPropane(TMP)) hexamethyl acrylate, two (TriMethylolPropane(TMP)s), six acrylate, Dipentaerythritol hexamethyl acrylate, dipentaerythritol acrylate etc.Can also and use these compounds.
Wherein, the compound of preferably representing by general formula (1) or general formula (2).
As compound, can enumerate for example two (oxygen methyl) three rings [5,2,1,0 by general formula (1) expression
2.6] decane diacrylate, two (oxygen methyl) three rings [5,2,1,0
2.6] the decane dimethacrylate etc.Can also and use these compounds.By using these compounds, can reduce the water absorbability of gained resin.
As compound by general formula (2) expression, for example, can enumerate alkylene glycol dimethacrylate, alkylene glycol diacrylate, 1, ammediol dimethacrylate, 1, ammediol diacrylate, 1,4-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, 2-methyl isophthalic acid, ammediol dimethacrylate, neopentylglycol dimethacrylate, neopentylglycol diacrylate, 2,2 '-dimethyl-1,4-butylene glycol dimethacrylate etc.Consider from the angle that improves the transparency, in compound by general formula (2) expression, neopentylglycol dimethacrylate most preferably.Can also and use these compounds.In general formula (2), n is more than or equal under 1 the situation, and outward appearance is good, and n is smaller or equal under 4 the situation, and thermotolerance improves.In addition, with the compound comparison of general formula (1), if use the compound of general formula (2), then owing to there is the big trend of polymerization shrinkage, therefore, its content is preferably 35～70 quality % in mixture.If compound is more than or equal to 35 quality %, then thermotolerance improves, if smaller or equal to 70 quality %, then outward appearance is good.In addition, its content is preferably greater than and equals 45 quality %.In addition, when using the compound of general formula (2), the content of single ethylene unsaturated monomer that comprises the alkyl methacrylate of the alkyl with carbonatoms 1～4 is preferably 30～65 quality % in mixture.If content is more than or equal to 30 quality %, then outward appearance improves, if content smaller or equal to 65 quality %, then thermotolerance improves.In addition, its content is preferably smaller or equal to 55 quality %.
Then, the situation of using the mixture that the slurry be made up of single ethylene unsaturated monomer and (being total to) polymkeric substance and polyfunctional group (methyl) acrylate form is described.
The mixture of this situation is that polyfunctional group (methyl) acrylate with (methyl) acryl more than 2 or 2 by the slurry of 5～65 mass parts and 35～95 mass parts constitutes; wherein, described slurry is had (being total to) polymkeric substance that the single ethylene unsaturated monomer unit by the alkyl methacrylate that comprises the alkyl with carbonatoms 1～4 of single ethylene unsaturated monomer of alkyl methacrylate of alkyl of carbonatoms 1～4 and 1～30 quality % constitutes and forms by comprising of 70～99 quality %.The content of the slurry in the 100 mass parts mixtures is preferably 10～55 mass parts, more preferably 15～50 mass parts.(methyl) acrylate content in the mixture of 100 mass parts is preferably 45～90 mass parts, more preferably 50～85 mass parts.
In slurry, the content of single ethylene unsaturated monomer of the alkyl methacrylate that comprises the alkyl with carbonatoms 1～4 of formation slurry is 70～99 quality %.If this monomer is more than or equal to 70 quality %, then thermotolerance improves, if smaller or equal to 99 quality %, then outward appearance improves.
As the object lesson of the alkyl methacrylate of the alkyl that constitutes slurry, other the object lesson of single ethylene unsaturated monomer and both suitable ratio of componentss, can enumerate situation same as described above with carbonatoms 1～4.
(being total to) polymkeric substance that constitutes slurry is that the single ethylene unsaturated monomer unit by the alkyl methacrylate that comprises the alkyl with carbonatoms 1～4 constitutes.Be the alkyl with carbonatoms 1～4 alkyl methacrylate single aggressiveness or have carbonatoms 1～4 alkyl alkyl methacrylate and with can with the multipolymer of single ethylene unsaturated monomer of these copolymerizations.Below, this polymkeric substance or multipolymer are suitably called " (being total to) polymkeric substance ".
In slurry, the content that is somebody's turn to do (being total to) polymkeric substance is 1～30 quality %.Have following trend: if the content of (being total to) polymkeric substance more than or equal to 1 quality %, then outward appearance improves, if smaller or equal to 30 quality %, then thermotolerance improves.
As the object lesson of the alkyl methacrylate of the alkyl that constitutes (being total to) polymkeric substance, other the object lesson of single ethylene unsaturated monomer and the ratio of components that both are suitable, can enumerate situation same as described above with carbonatoms 1～4.
As constituting polyfunctional group (methyl) acrylate with (methyl) acryl more than 2 or 2 of mixture jointly, can enumerate situation same as described above with slurry.In 100 mass parts and mixture slurry, the content of this polyfunctional group (methyl) acrylate is 35～95 mass parts.Have following trend: if this content more than or equal to 35 mass parts, then thermotolerance improves, if this content smaller or equal to 95 mass parts, then outward appearance is good.In addition, this content is preferably 45～90 mass parts, more preferably 50～85 mass parts.In addition, when using compound by general formula (2) expression as functional group's (methyl) acrylate, with mixture 100 mass parts of slurry in, the content of this compound is preferably 35～70 mass parts.Have following trend: if content more than or equal to 35 mass parts, then thermotolerance improves, if content smaller or equal to 70 mass parts, then outward appearance is good.In addition, the content of this compound is preferably greater than and equals 45 mass parts.
In the present invention, use any in 2 kinds of mixtures of above explanation, 10 hours half life temperatures that this mixture of per 100 mass parts adds 0.001～1 mass parts are modulated polyblend more than or equal to 80 ℃ the polymerization starter and at least a compound that is selected from cyclohexadiene and derivative and class terpenoid and derivative thereof of 0.015～0.2 mass parts.
As 10 hours half life temperatures polymerization starter more than or equal to 80 ℃, for example, can enumerate 1, two (hexanaphthene-1-nitrile) (half life temperature was 88 ℃ in 10 hours) of 1 '-azo, 2,2 '-azo two (2,4, the 4-2,4,4-Trimethyl-1-pentene) (half life temperature was 110 ℃ in 10 hours), 2-cyano group-2-propyl group azoformamide (2-cyano-2-propylazoformamide) (half life temperature was 104 ℃ in 10 hours), dicumyl peroxide (half life temperature was 117 ℃ in 10 hours), tert-butyl peroxide isopropyl benzene (half life temperature was 121 ℃ in 10 hours), di-t-butyl peroxide (half life temperature was 126 ℃ in 10 hours), tert-butyl peroxide-3,3,5-tri-methyl hexanoic acid ester (half life temperature was 100 ℃ in 10 hours), tert-butyl peroxide laurate (half life temperature was 95 ℃ in 10 hours), peroxide tert-butyl acetate (half life temperature was 103 ℃ in 10 hours), the diperoxy tertiary butyl six hydrogen terephthalates (half life temperature was 83 ℃ in 10 hours), diperoxy tertiary butyl azelate (half life temperature was 99 ℃ in 10 hours), tert-butyl peroxide allyl carbonate (half life temperature was 94 ℃ in 10 hours), tert-butyl peroxide sec.-propyl carbonic ether (half life temperature was 97 ℃ in 10 hours), 1,1-diperoxy tertiary butyl hexanaphthene (half life temperature was 97 ℃ in 10 hours), peroxidation uncle hexyl sec.-propyl monocarbonate (half life temperature was 95 ℃ in 10 hours), 1, the 1-diperoxy tertiary butyl-3,3,5-trimethyl-cyclohexane (half life temperature was 95 ℃ in 10 hours), 1,1-diperoxy uncle hexyl-3,3,5-trimethyl-cyclohexane (half life temperature was 87 ℃ in 10 hours) etc.Can also and use these compounds.The upper limit of 10 hours half life temperatures is preferably 130 ℃.
In per 100 mass parts mixtures, 10 hours half life temperatures are 0.001～1 mass parts more than or equal to the addition of 80 ℃ polymerization starter.If more than or equal to 0.001 mass parts, even add cyclohexadiene, class terpenoid and derivative thereof, also there is the trend of thermotolerance raising in this addition.In addition, residual initiator reduces, the trend of good thermal stability if addition smaller or equal to 1 mass parts, exists.And then this addition is preferably 0.005～0.5 mass parts.
In addition, can also be with such polymerization starter and with the polymerization starter of 80 ℃ of 10 hours half rate phases temperature less thaies.Polymerization starter as 80 ℃ of 10 hours half life temperature less thaies, for example can enumerate isobutyryl peroxide tert-butyl ester (half life temperature was 77 ℃ in 10 hours), tert-butyl peroxide-2-ethylhexanoate (half life temperature was 72 ℃ in 10 hours), tert-butyl peroxide pivalate (half life temperature was 55 ℃ in 10 hours), peroxidation uncle hexyl pivalate (half life temperature was 53 ℃ in 10 hours), tert-butyl peroxide new decanoate ester (half life temperature was 47 ℃ in 10 hours), 2,2 '-azobis isobutyronitrile (half life temperature was 65 ℃ in 10 hours), 2,2 '-azo two (2, the 4-methyl pentane nitrile) (half life temperature was 51 ℃ in 10 hours), 2,2 '-azo two (2,4-dimethyl-4-methoxyl group valeric acid nitrile) (half life temperature was 30 ℃ in 10 hours) etc.Can also and use these compounds.
At least a compound that is selected from cyclohexadiene and derivative thereof and class terpenoid and derivative thereof is the composition that plays the polymerization regulator function.Below be referred to as " compound (a) ".As this compound (a), for example, can enumerate 1,1-methyl isophthalic acid, 4-cyclohexadiene, α-terpinene, β-terpinene, γ-terpinene, terpinolene, limonene, myrcene, α-Pai Xi, beta-pinene, terpinol etc.Preferred especially terpinolene.
The mixture of per 100 mass parts, the addition of compound (a) is 0.015～0.2 mass parts.Have following trend: if this addition more than or equal to 0.015 mass parts, then in the stripping process during fabrication, is difficult for taking place plate and splits, if this addition smaller or equal to 0.2 mass parts, then residual monomer reduces, good thermal stability.Stripping process during so-called here the manufacturing is meant from polymerizing curable and finishes the back up to the operation of peeling off acrylic acid resin plate from mold.In addition, this addition is preferably 0.02～0.15 mass parts.
By polymerizing curable polyblend described above, can make acrylic acid resin plate.As the polymerizing curable method of polyblend, known the whole bag of tricks before can using.Especially preferably inject polyblend and carry out polymerizing curable to mold, and the so-called cast poymerization method of peeling off from mold.
Below illustrate the cast polymerized method of methyl methacrylate of using as the alkyl methacrylate of alkyl with carbonatoms 1～4.But the present invention is not limited to this method.At first, contain methyl methacrylate, polyfunctional group (methyl) acrylate to the suction lottle adding, add (be total to) polymkeric substance contain methyl methacrylate units as required, so add as required can copolymerization other single ethylene unsaturated monomers, stir and the formation mixture.Add polymerization starter, polymerization regulator " compound (a) " to this mixture, carry out vacuum outgas, form polyblend.Inject this polyblend in the mold that between by a pair of strengthening glass sheets, sandwiches packing ring and constitute, put into process furnace, under 40～70 ℃, carry out 2～5 hours polymerizing curable, under 100～150 ℃, carry out 1～6 hour polymerizing curable, and product is peeled off, thereby can make acrylic acid resin plate from mold.
Can also use for example minute surface SUS plate, surface to have the minute surface SUS system endless belt that trickle concavo-convex peel plate, subtend move and substitute this strengthening glass sheets as mold.In addition, can also be according to suitably selective polymerization temperature of hope, time.
The thickness of acrylic acid resin plate is preferably 0.5～5mm.If thickness more than or equal to 0.5mm, is then made utilizing bulk polymerization under the situation of resin board, having when mold is peeled off acrylic acid resin plate breaks produces the tendency that becomes difficult.In addition, if thickness, then has the difficult tendency of plate fission during polymerization smaller or equal to 5mm.
Polyblend is to contain the mixture of above-mentioned various composition as main component, but, as required, can also add tinting material, releasing agent, antioxidant, stablizer, static inhibitor, antiseptic-germicide, fire retardant, anti-impact modifier, photostabilizer, UV light absorber, light scattering agent, polymerization retarder, chain-transfer agent etc.In order further to reduce the levels of residual monomers of gained resin board, preferably add chain-transfer agents such as mercaptan.
Below acrylic resin of the present invention is described.
Acrylic resin of the present invention is the resin that contains polyfunctional group (methyl) acrylic ester unit with (methyl) acryl more than 2 or 2 of the alkyl methacrylate that comprises the alkyl with carbonatoms 1～4 unitary single ethylene unsaturated monomer unit of the alkyl methacrylate unit of the alkyl with carbonatoms 8～20 of 3～30 quality % and 2～35 quality % and 35～95 quality %.
Each unitary content is the value of ratio of whole monomeric units of the expression polymkeric substance more than a kind or 2 kinds or 2 kinds that constitutes resin at this.Promptly, acrylic resin of the present invention can also be the resin that the polymkeric substance by a kind of following gained constitutes: will constitute that above-mentioned each unitary 3 monomer carry out copolymerization together and the multipolymer that obtains, in addition, can also be following gained resin: in advance at least one the monomeric part that constitutes in above-mentioned each unitary 3 monomer is formed polymkeric substance, in the presence of this polymkeric substance, the monomer that polymerization is residual and the resin that obtains.The resin of latter instance for example can carry out polymerization by the slurry that (being total to) polymkeric substance that contains alkyl methacrylate and desired monomer are constituted and make.
The unitary content of alkyl methacrylate with alkyl of carbonatoms 8～20 is 3～30 quality % in resin.Have following trend: if this content more than or equal to 3 quality %, then shape stability improves, if this content smaller or equal to 30 quality %, then thermotolerance improves.This content is 5～20 quality % more preferably.
As the alkyl methacrylate unit of alkyl, can enumerate by deutero-unit such as methacrylic acid-2-ethylhexyl, lauryl methacrylate(LMA), methacrylic acid tridecyl ester, methacrylic acid stearyl, methacrylic acid isooctadecane base esters with carbonatoms 8～20.Can also and use these unit.
The unitary content of the unitary single ethylene unsaturated monomer of alkyl methacrylate that comprises the alkyl with carbonatoms 1～4 is 2～35 quality % in resin.If this content is more than or equal to 2 quality %, then outward appearance improves, if this content smaller or equal to 35 quality %, then thermotolerance and shape stability improve.This content is 5～25 quality % more preferably.When the unitary total amount of the unitary single ethylene unsaturated monomer of the alkyl methacrylate that comprises the alkyl with carbonatoms 1～4 is 100 mass parts, the unitary ratio of alkyl methacrylate with alkyl of carbonatoms 1～4 is preferably greater than and equals 50 mass parts, and other the unitary ratio of single ethylene unsaturated monomer is preferably smaller or equal to 50 mass parts.If form such ratio, then the transparency has the trend of raising, and in addition, thermotolerance has the trend of further raising.
As the unitary object lesson of the alkyl methacrylate of alkyl, can enumerate the alkyl methacrylate deutero-unit of object lesson of the alkyl methacrylate of the alkyl that uses in the manufacture method by the acrylic acid resin plate of above explanation with carbonatoms 1～4 with carbonatoms 1～4.
In addition, as the single ethylene unsaturated monomer unit beyond the alkyl methacrylate unit of alkyl, can enumerate the various unit in addition, alkyl methacrylate unit of alkyl with carbonatoms 8～20 with carbonatoms 1～4.As its object lesson, can enumerate the unit of deriving and obtaining by the material suitable in the object lesson of the single ethylene unsaturated monomer that in the manufacture method of the acrylic acid resin plate of above explanation, uses with it.
Content with polyfunctional group (methyl) acrylic ester unit of (methyl) acryl more than 2 or 2 is 35～95 quality % in resin.Have following trend: if this content more than or equal to 35 quality %, then thermotolerance improves, if this content smaller or equal to 95 quality %, then outward appearance is good.This content is preferably 45～90 quality %, more preferably 50～85 quality %.
As the object lesson of polyfunctional group (methyl) acrylate, can enumerate the identical material of object lesson with polyfunctional group (methyl) acrylate that in the manufacture method of the acrylic acid resin plate of above explanation, uses with (methyl) acryl more than 2 or 2.Wherein, the compound of preferably representing by general formula (1).
Acrylic resin of the present invention is the resin that contains as the primary structure unit with each monomeric unit described above.This resin preferably uses as acrylic acid resin plate.
The method of making the resin board that is made of acrylic resin of the present invention has following operation: to the alkyl methacrylate of the alkyl with carbonatoms 8～20 that contains 3～30 quality % and single ethylene unsaturated monomer of the alkyl methacrylate that comprises the alkyl with carbonatoms 1～4 and the having more than 2 or 2 of 35～95 quality % of 2～35 quality %; the polyfunctional group of (methyl) acryl; the polyblend of (methyl) acrylate carries out the operation of polymerizing curable.Each monomeric object lesson etc. as mentioned above as used herein.
As the polymerizing curable method of polyblend, known the whole bag of tricks before can using.Especially preferably inject polyblend, carry out polymerizing curable to mold, and the so-called cast poymerization method of peeling off from mold.
For polyblend is carried out polymerization, known various radical initiators before can using.Object lesson as radical initiator, can enumerate tert-butyl peroxide pivalate, peroxidation uncle hexyl pivalate, tert-butyl peroxide new decanoate ester, peroxidation uncle hexyl neodecanoic acid ester, tert-butyl peroxide sec.-propyl carbonic ether, peroxidation uncle hexyl sec.-propyl monocarbonate, 2, two (the 4-methoxyl groups-2 of 2 '-azo, the 4-methyl pentane nitrile), 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2,2 '-azobis isobutyronitrile etc.As polymerization starter, preferably use 10 hours half life temperatures more than or equal to 80 ℃ polymerization starter.Per 100 mass parts mixtures, its content is preferably 0.001～1 mass parts.10 hours half life temperatures more than or equal to object lesson of 80 ℃ polymerization starter etc. as mentioned above.
Below, illustrate use methacrylic acid isooctadecane base ester as alkyl methacrylate with alkyl of carbonatoms 8～20, use the cast polymerized method of methyl methacrylate as the alkyl methacrylate of alkyl with carbonatoms 1～4.But the present invention is not limited to this method.
At first, contain methacrylic acid isooctadecane base ester, methyl methacrylate, polyfunctional group (methyl) acrylate to the suction lottle adding, add (being total to) polymkeric substance that contains methyl methacrylate units as required, and then add as required can copolymerization other single ethylene unsaturated monomers, stir and form mixture.Add radical polymerization initiator to this mixture, carry out vacuum outgas.Inject this polyblend in the mold that between a pair of strengthening glass sheets, sandwiches packing ring and constitute, put into process furnace, under 40～70 ℃, carry out 2～5 hours polymerizing curable, under 100～150 ℃, carry out 1～6 hour polymerizing curable, and product is peeled off, thereby can make acrylic acid resin plate from mold.
Can also use for example minute surface SUS plate, surface to have the minute surface SUS endless belt that trickle concavo-convex sheet glass, subtend move and substitute this strengthening glass sheets as mold.In addition, can also be according to suitably selective polymerization temperature of hope, time.
The thickness of acrylic acid resin plate of the present invention is preferably 0.5～5mm.If thickness more than or equal to 0.5mm, is made when utilizing bulk polymerization under the situation of resin board, having when mold is peeled off acrylic acid resin plate breaks produces the tendency that becomes difficult.In addition, if smaller or equal to 5mm, having plate to split during polymerization, thickness produces the tendency that becomes difficult.
Polyblend is to contain the mixture of above-mentioned various composition as main component, but, as required, can also add tinting material, releasing agent, antioxidant, stablizer, static inhibitor, antiseptic-germicide, fire retardant, anti-impact modifier, photostabilizer, UV light absorber, light scattering agent, polymerization retarder, polymerization regulator, chain-transfer agent etc.As polymerization regulator, the preferred at least a compound that is selected from cyclohexadiene and derivative and class terpenoid and the derivative thereof that uses.The mixture of per 100 mass parts, its content is preferably 0.015～0.2 mass parts.Its object lessons etc. as mentioned above.In addition, in order further to reduce the levels of residual monomers of gained resin board, preferably add chain-transfer agents such as mercaptan.
Acrylic acid resin plate of the present invention still keeps the optical property of the excellence of acrylic resin, and the plate in the thermotolerance, outward appearance, stripping process during fabrication splits preventing property and is greatly improved.
Such acrylic acid resin plate can be applied to the periphery material of heating light sources such as for example incandescent lampshade, halogen lampshade; The parts of heating such as suit dried machine, microwave oven, baking box household electrical appliance; Optical lenses such as glasses lens, sunglasses eyeglass, camera lens, video recorder lens, eye shield lens, contact lens; The survey meter watch glasses is waited for bus and is carried parts, vehicle-mounted audio device parts, display device for mounting on vehicle parts, the onboard navigation system parts carrier material of waiting for bus, and is applied to the front panel of various display unit such as plasma display system, liquid crystal indicator, projection display, the various display units such as photoconduction tabula rasa of liquid crystal indicator in addition.
＜nesa coating 〉
The acrylic acid resin plate that the present invention obtains can form nesa coating and become the acrylic resin layered product on its at least one surface.As this nesa coating, so long as film transparent and conduction is just passable.For example, can use inorganic thin film or organic polymer film.
As the material of inorganic thin film, for example, can enumerate stannic oxide, Indium sesquioxide, ITO transparent metal oxides such as (adding the Indium sesquioxide of tin).Wherein, preferred ITO.In addition, as the organic polymer thin-film material, can enumerate polyisothianaphthene etc.
In addition, the acrylic resin layered product that is formed with nesa coatings such as ITO at least one surface of acrylic acid resin plate can be applied to the purposes of transparent conductive material.For example, can be applied to electrical element circuit materials such as electrical condenser, resistance; Copy material such as electrofax or electrostatic recording; Liquid-crystal display becomes indicating meter with, electrochromism and signal input such as uses to use transparency electrode with, electroluminescent display with, touch panel; Photo-electric conversion element such as solar cell, image intensifer in addition, can also be applied to antistatic with various uses such as parts, electromagnetic wave shielding parts, surface heat element, transmitters.Wherein, be preferably used as the touch panel transparent electrode plate.
＜touch panel transparent electrode plate 〉
Touch panel of the present invention has acrylic acid resin plate that the present invention as transparency carrier makes and the nesa coating that forms with transparent electrode plate at least one face of this acrylic acid resin plate.As the method that on acrylic acid resin plate, forms nesa coating, known various one-tenth embrane methods before can using.As the example that becomes embrane method, can enumerate vacuum vapour deposition, sputtering method, CVD method, ion plating method equal vacuum and become embrane method.Here, the film forming object lesson to the sputtering method that utilizes ito thin film is described.At first, in washing procedure, utilize pure water or alkaline water washing transparency carrier, in atmosphere, more than or equal to 120 ℃, preferably under 120～130 ℃ temperature dry 1～4 hour.Then, under vacuum,, preferably under 120～130 ℃ temperature, carry out the sputter process of ITO at 100～140 ℃.Afterwards, utilize the electrode coated and evoked electrode of silver-colored paste, 130～170 ℃, preferably under 150 ℃ temperature, solidify.
Touch panel is preferably greater than with the load-carrying deflection deformation temperature of transparent electrode plate and equals 150 ℃.If load-carrying deflection deformation temperature more than or equal to 150 ℃, then when silver-colored paste is hardened, has the resin substrate distortion to become difficult tendency.In addition, when the thickness of nesa coating smaller or equal to 1 μ m, relatively thinner situation under, the load-carrying deflection deformation temperature of transparent electrode plate is identical with the load-carrying deflection deformation temperature of the acrylic acid resin plate of formation transparent electrode plate.Therefore, can also measure the load-carrying deflection deformation temperature of acrylic acid resin plate this moment, and with its load-carrying deflection deformation temperature as transparent electrode plate.
Be applied to touch panel and be preferably 0.5～2mm, more preferably 0.5～1mm with the thickness of the acrylic acid resin plate of transparent electrode plate.In addition, the thickness of nesa coating is preferably 10～50nm, more preferably 25～40nm.If adopt the thickness in these scopes, compare with transparent electrode plate with the touch panel that uses glass substrate, can obtain lightweight, thin layerization.
Be applied to touch panel and be not preferably not dyeing with the acrylic acid resin plate of transparent electrode plate.In addition, can also form antireflection film in a side that does not have nesa coating.When touch panel was 1mm with the thickness of transparent electrode plate, its total light transmittance was based on the numerical value of the assay method of the total light transmittance shown in the JIS-K7361, is preferably more than to equal 91%.If total light transmittance more than or equal to 91%, can obtain as the enough transparency of touch panel with transparent electrode plate.
＜touch panel 〉
Touch panel of the present invention is to possess upper transparent electrode plate and lower transparent electrode plate, and this upper transparent electrode plate and lower transparent electrode plate are at least one the lip-deep nesa coatings that has transparency carrier and be formed at this transparency carrier, the touch panel of this upper transparent electrode plate and this lower transparent electrode plate is set opposite to each other across the gap, and it is characterized in that: at least one of upper transparent electrode plate and lower transparent electrode plate is touch panel transparent electrode plate of the present invention.
Below, use Fig. 1～3, to touch panel of the present invention with transparent electrode plate and use the preferred examples of the touch panel of this battery lead plate to describe.Fig. 1 is the simulated section figure of expression touch panel of the present invention with an example of transparent electrode plate, and Fig. 2 is its simulation orthographic plan.In addition, Fig. 3 is that the transparent electrode plate represented among Fig. 1 and Fig. 2 simulated section figure as an example of the touch panel of lower transparent electrode plate is used in expression.
Touch panel shown in Figure 3 has following structure: lower transparent electrode plate 1 and upper transparent electrode plate 7 are set to subtend via liner 6.As Fig. 1 and shown in Figure 2, lower transparent electrode plate 1 has the electrode 4 of transparency carrier 2 and nesa coating 3 that forms and the end on the nesa coating 3 on a surface of this transparency carrier 2, be connected with evoked electrode 5 on the electrode 4.In addition, upper transparent electrode plate 7 also has the structure identical with lower transparent electrode plate 1.That is, upper transparent electrode plate 7 similarly has transparency carrier 8, nesa coating 9, electrode 10 etc.
According to following lower transparent electrode plate 1 and the upper transparent electrode plate 7 of being provided with: with separately nesa coating 3,9 as inboard, insertion point liner (dot spacer) 11 between two transparent electrode plates 1,7, and make the direction of two electrodes 4,10 intersect, reserve certain intervals setting via liner 6.Touch panel with this structure, if push with pen or finger from the top of upper transparent electrode plate 7, upper transparent electrode plate 7 deforms, via a liner 11, upper transparent conducting film 9 contacts and conducting with bottom nesa coating 3, thereby finishes input.
Touch panel of the present invention is high with the transparency of transparent electrode plate, and the rigidity height, therefore, suits as lower transparent electrode plate 1.Fig. 1～Fig. 3 represents such example.But the present invention is not limited to these examples.For example, can also use touch panel of the present invention with transparency electrode as upper transparent electrode plate 7, can also be used for lower transparent electrode plate 1 and upper transparent electrode plate 7 both.
Further describe the present invention below by embodiment.And the following stated " portion " is benchmark with the quality.In addition, the various evaluations in the table are carried out according to following method.
(1) evaluation of acrylic acid resin plate:
(1-1) load-carrying deflection deformation temperature:
In order to estimate the thermotolerance of acrylic acid resin plate,, measure load-carrying deflection deformation temperature according to the measuring method shown in the JIS-K7207.
(1-2) turbidity:
In order to estimate the optical characteristics of acrylic acid resin plate,, measure turbidity according to the measuring method shown in the JIS-K7136.
(1-3) plate splits preventing property:
For the plate of estimating acrylic acid resin plate splits preventing property, make 10 samples, polymerizing curable after finishing is cooled to mold smaller or equal to 40 ℃, represents up to peel off acrylic acid resin plate from mold the sample number that plate splits not to take place all with n/10.
(1-4) outward appearance:
In order to estimate the outward appearance of acrylic acid resin plate, make 10 samples, with n/10 represent eyes do not observe turn white, the sample number of defective such as depression.
(1-5) levels of residual monomers:
In order to estimate the levels of residual monomers of acrylic acid resin plate, in the 20ml methylene dichloride, add 0.1g and be cut into the granulous sample with nickel, left standstill 4 days at 23 ℃, make the particle dissolving after, inject supernatant liquor to gas chromatograph, the mensuration levels of residual monomers.The condition determination of vapor-phase chromatography is as follows.
Device: Xiu Laite packard (ヒ ユ-レ Star ト パ Star カ-De) company makes HP6890
Data processing equipment: HP Kai Misitai praises (ケ ミ ス テ-シ ョ Application)
Used post: HP-50.32mm Ф * 30m * 0.25 μ m thickness
The column temperature condition: 40 ℃/1min keeps → 290 ℃/3min to keep, and 20 ℃/min heats up
INJ temperature: 280 ℃
Carrier gas (He) flow: 20.0ml/min
(2) evaluation of acrylic resin layered product:
(2-1) amount of warpage:
In order to estimate the shape stability of acrylic resin layered product, carry out the shape stability test, measure its amount of warpage.Specifically, indoor at 23 ℃, the fixed temperature and humidity of 50%RH, the sample of 190mm * 190mm * 1.0mm (thick) was placed 1 day, then, in 60 ℃, the constant temperature and humidity machine of 90%RH, with clip it is sling, placed 10 days, again 23 ℃, the indoor placement of fixed temperature and humidity of 50%RH 1 hour, then, amount of warpage is measured in cooling.In the mensuration of this amount of warpage, sample is placed on the dish of level with protuberantia state up, utilize vernier measure card and separation disc face farthest between the bottom of part apart from a (mm), the ratio of the relative specimen length of this distance as amount of warpage (%).That is,
Amount of warpage (%)=a/190 * 100
Here, when being bent into to the nesa coating collateral eminence, amount of warpage be made as on the occasion of, when being bent into when the nesa coating side caves in, amount of warpage is made as negative value.
(3) the touch panel evaluation of transparent electrode plate:
(3-1) total light transmittance:
In order to estimate the transparency of touch panel, measure total light transmittance according to the assay method shown in the JIS-K7361 with battery lead plate.
(3-2) substrate deformation:
Whether be out of shape at acrylic acid resin plate (substrate), carry out following evaluation: the drying of the substrate before nesa coating (ITO) is carried out film forming, utilize this a series of touch panel of coating curing of the silver-colored paste after sputtering method carries out film forming, film forming with in manufacturing process of transparent electrode plate then, utilize naked eyes to observe, acrylic acid resin plate does not have the average evaluation of distortion to be: " zero " (well), the average evaluation that deforms are " * " (bad).
(3-3) state of ITO:
State at nesa coating (ITO), carry out following evaluation: the silver-colored paste coating solidified successive touch panel after utilizing the film forming of sputtering method, film forming is with in the manufacturing process of transparent electrode plate, observe, do not recognize optical skew and fissured average evaluation and be " zero " (well), recognize optical skew and fissured average evaluation and be " * " (bad).
(3-4) sticking power
Use cutting knife, touch panel with the nesa coating of transparent electrode plate on 1mm at interval, be reticulation and laterally vertically respectively cut 11 times, and cutting is deep to resin substrate, the grid of 100 1 * 1mm of making.Adhesive glue adhesive tape (Nichiban (ニ チ バ Application) produce, trade(brand)name cellophane tape) securely on this grid is peeled off near own directions on one side apace along 45 ℃.At this moment, the number (n) of cutting apart that residual nesa coating is not peeled off is expressed as n/100.Specifically, the value of n be preferably greater than equal 96, more preferably 100 be appropriate.The value of n is big more, and the sticking power of nesa coating is high more, can think excellent contact panel transparent electrode plate.
The manufacturing of＜acrylic acid resin plate 〉
[embodiment 1]
At 10 parts of methacrylic acid isooctadecane base esters (Xin Zhong village chemical industry society system " NK ester S-1800M "), 10 parts of methyl methacrylates and two (oxygen methyl) three rings [5,2,1,0
2,6] in 100 parts in the mixture of 80 parts of decane dimethacrylates, mixing is as 2 of polymerization starter, 2 '-azo two (2,4-dimethyl-4-methoxyl group valeronitrile) 0.05 part, 0.05 part of tert-butyl peroxide pivalate, 0.05 part of peroxidation uncle hexyl sec.-propyl carbonic ether and as 0.03 part of the terpinolene of polymerization regulator, and with the gained mixture suction lottle of packing into, stir, vacuum outgas makes polyblend.
This polyblend is injected the mold that constitutes by inserting packing ring between a pair of chilled glass sheet of interval 1.7mm, remove bubble, put into process furnace, 55 ℃ of polymerizations 1 hour, 50 ℃ of polymerizations 1 hour, then at 135 ℃ of polyase 13s hour.Afterwards, mold is cooled to below 40 ℃, peels off,, make the acrylic acid resin plate of thickness 1mm again 130 ℃ of heating 4 hours.
Plate can not take place in the cooling of this resin board behind polymerizing curable split, plate do not occur when peeling off taking-up yet and split.In addition, this resin board has the good surface appearance that does not have albefaction and depression.In addition, turbidity is measured, the result is 0.2%, demonstrates the good transparency.Load-carrying deflection deformation temperature is above 200 ℃.In addition, two (oxygen methyl) three rings [5,2,1,0
2.6] levels of residual monomers of decane dimethacrylate is 2.34%.The main raw material of the polyblend of present embodiment is formed and evaluation result is shown in table 1.
[embodiment 2～24, comparative example 1～9]
Except adopting the raw material composition shown in table 1～6, all the other make acrylic acid resin plate similarly to Example 1.Evaluation result is shown in table 1～6.
[embodiment 25]
In embodiment 1, further add 0.05 part of n-dodecyl mercaptan as chain-transfer agent to polyblend, all the other make acrylic acid resin plate similarly to Example 1.Evaluation result is shown in table 7.And, two (oxygen methyl) three rings [5,2,1,0
2,6] levels of residual monomers of decane dimethacrylate is 2.09%.
[embodiment 26]
In embodiment 1, substitute 10 parts of methacrylic acid isooctadecane base esters, all the other manufacturing acrylic acid resin plates similarly to Example 1 with 5 parts of methacrylic acid isooctadecane base esters and 5 parts of methyl acrylates.Evaluation result is shown in table 7.And, two (oxygen methyl) three rings [5,2,1,0
2,6] levels of residual monomers of decane dimethacrylate is 2.03%.
The film forming of＜nesa coating 〉
Clean the various acrylic acid resin plates that embodiment 1～26 and comparative example 1～9 make with pure water, and put it into hot-air drying stove, with 120 ℃ warm air dryings 2 hours.Then, utilize sputtering method, on resin board, form the ITO film, make the acrylic resin layered product as nesa coating.The thickness of nesa coating is adjusted to about 30nm.In addition, in this sputter, with the In of mass ratio 95/5
2O
3/ SnO
2As target, be vented to 10
-3Pa as importing gas, carries out the RF sputter with argon gas/oxygen of volume ratio 92.5/7.5 under 120 ℃ heating.Amount of warpage after the shape stability test of each acrylic resin layered product of gained is shown in table 1～7.
＜touch panel the manufacturing of transparent electrode plate 〉
Above-mentioned each acrylic resin layered product is cut into horizontal 250mm * vertical 180mm, utilizes the pattern of regulation, silver coating paste on layered product makes it to solidify under 150 ℃, forms electrode and evoked electrode.The touch panel transparent electrode plate of shop drawings 1 and structure shown in Figure 2 respectively.The thickness of this electrode and evoked electrode is regulated into about 10 μ m.Each touch panel of gained is shown in table 1～7 with the evaluation result of transparent electrode plate.
＜touch panel 〉
Use above-mentioned each touch panel to use transparent electrode plate, make the touch panel of structure shown in Figure 3 as lower transparent electrode plate 1.Specifically, use above-mentioned each touch panel to use transparent electrode plate as lower transparent electrode plate 1.In addition, as upper transparent electrode plate 7, use as lower electrode plate: utilize the method identical, go up the battery lead plate of the ITO film that forms about 25nm at the polyethylene terephthalate film (Supreme Being people's (strain) produces, ProductName Tai Telong (テ ト ロ Application) film) of thick 188 μ m with the lower transparent electrode plate.As liner, use the double-sided belt of 100 μ m.
In addition, pattern according to the rules applies the light-cured type acrylic resin on bottom nesa coating 3, and is cured by uviolizing, and the pitch with 3mm that forms high 10 μ m, diameter 50 μ m is arranged in the some liner 11 of zigzag.In addition, on electrode 4 and electrode 10, form insulating film (not diagram).Be equivalent to 12 types by being assembled into the structure that lower transparent electrode plate 1 and upper transparent electrode plate 7 are provided with via liner 6 subtends, making, the touch panel of promptly horizontal 250mm * vertical 180mm.
Table 1
| The alkyl methacrylate that contains the C8-20 alkyl | M M A | Polyfunctional group (methyl) acrylate | Polymerization starter | Polymerization regulator TP | Acrylic acid resin plate | The acrylic resin layered product | The touch panel transparent electrode plate | |||||||||||
| Load-carrying deflection deformation temperature (℃) | Turbidity | Plate splits preventing property | Outward appearance | Amount of warpage (%) | Total light transmittance (%) | Base plate deformation | The ITO state | Sticking power | ||||||||||
| Kind | (part) | (part) | Kind | (part) | Kind | (part) | (part) | |||||||||||
| Embodiment | 1 | ISMA | 10 | 10 | TDMA | 80 | ADMVN | 0.05 | 0.03 | Surpass 200 | 0.2 | 10/10 | 10/10 | 0.2 | 92 | ○ | ○ | 100/100 |
| HPP | 0.05 | |||||||||||||||||
| HPIC | 0.05 | |||||||||||||||||
| 2 | ISMA | 5 | 15 | TDMA | 70 | ADMVN | 0.05 | 0.03 | Surpass 200 | 0.2 | 10/10 | 10/10 | 0.3 | 92 | ○ | ○ | 100/100 | |
| HPP | 0.05 | |||||||||||||||||
| HPIC | 0.05 | |||||||||||||||||
| 3 | ISMA | 10 | 20 | TDMA | 70 | ADMVN | 0.05 | 0.03 | 197 | 0.2 | 10/10 | 10/10 | 0.3 | 92 | ○ | ○ | 100/100 | |
| HPP | 0.05 | |||||||||||||||||
| HPIC | 0.05 | |||||||||||||||||
| 4 | LMA | 10 | 20 | TDMA | 70 | ADMVN | 0.05 | 0.03 | 190 | 0.2 | 10/10 | 10/10 | 0.3 | 92 | ○ | ○ | 100/100 | |
| HPP | 0.05 | |||||||||||||||||
| HPIC | 0.05 | |||||||||||||||||
| 5 | TMA | 10 | 20 | TDMA | 70 | ADMVN | 0.05 | 0.03 | 196 | 0.2 | 10/10 | 10/10 | 0.3 | 92 | ○ | ○ | 100/100 | |
| HPP | 0.05 | |||||||||||||||||
| HPIC | 0.05 | |||||||||||||||||
| 6 | SMA | 10 | 20 | TDMA | 70 | ADMVN | 0.05 | 0.03 | 200 | 0.2 | 10/10 | 10/10 | 0.3 | 92 | ○ | ○ | 100/100 | |
| HPP | 0.05 | |||||||||||||||||
| HPIC | 0.05 | |||||||||||||||||
| 7 | ISMA | 5 | 25 | TDMA | 70 | ADMVN | 0.05 | 0.03 | 198 | 0.2 | 10/10 | 10/10 | 0.4 | 92 | ○ | ○ | 100/100 | |
| HPP | 0.05 | |||||||||||||||||
| HPIC | 0.05 | |||||||||||||||||
Table 2
| The alkyl methacrylate that contains the C8-20 alkyl | M M A | Polyfunctional group (methyl) acrylate | Polymerization starter | Polymerization regulator TP | Acrylic acid resin plate | The acrylic resin layered product | The touch panel transparent electrode plate | |||||||||||
| Load-carrying deflection deformation temperature (℃) | Turbidity | Plate splits preventing property | Outward appearance | Amount of warpage (%) | Total light transmittance (%) | Base plate deformation | The ITO state | Sticking power | ||||||||||
| Kind | (part) | (part) | Kind | (part) | Kind | (part) | (part) | |||||||||||
| Embodiment | 8 | ISMA | 20 | 5 | TDMA | 75 | ADMVN | 0.05 | 0.03 | 190 | 0.2 | 10/10 | 10/10 | 0.1 | 92 | ○ | ○ | 100/100 |
| HPP | 0.05 | |||||||||||||||||
| HPIC | 0.05 | |||||||||||||||||
| 9 | ISMA | 15 | 20 | TDMA | 65 | ADMVN | 0.05 | 0.03 | 171 | 0.2 | 10/10 | 10/10 | 0.2 | 92 | ○ | ○ | 100/100 | |
| HPP | 0.05 | |||||||||||||||||
| HPIC | 0.05 | |||||||||||||||||
| 10 | ISMA | 20 | 25 | TDMA | 55 | ADMVN | 0.05 | 0.03 | Surpass 200 | 0.2 | 10/10 | 10/10 | 0.3 | 92 | ○ | ○ | 100/100 | |
| HPP | 0.05 | |||||||||||||||||
| HPIC | 0.05 | |||||||||||||||||
| 11 | - | - | 20 | TDMA | 80 | ADMVN | 0.05 | 0.03 | Surpass 200 | 0.2 | 10/10 | 10/10 | 1.0 | 92 | ○ | ○ | 100/100 | |
| HPP | 0.05 | |||||||||||||||||
| HPIC | 0.05 | |||||||||||||||||
| 12 | - | - | 10 | TDMA | 90 | ADMVN | 0.05 | 0.03 | Surpass 200 | 0.2 | 10/10 | 10/10 | 0.7 | 92 | ○ | ○ | 100/100 | |
| HPP | 0.05 | |||||||||||||||||
| HPIC | 0.05 | |||||||||||||||||
| 13 | - | - | 50 | TDMA | 50 | ADMVN | 0.05 | 0.03 | 157 | 0.2 | 10/10 | 10/10 | 1.3 | 92 | ○ | ○ | 100/100 | |
| HPP | 0.05 | |||||||||||||||||
| HPIC | 0.05 | |||||||||||||||||
Table 3
| The alkyl methacrylate that contains the C8-20 alkyl | M M A | Polyfunctional group (methyl) acrylate | Polymerization starter | Polymerization regulator TP | Acrylic acid resin plate | The acrylic resin layered product | The touch panel transparent electrode plate | |||||||||||
| Load-carrying deflection deformation temperature (℃) | Turbidity | Plate splits preventing property | Outward appearance | Amount of warpage (%) | Total light transmittance (%) | Base plate deformation | The ITO state | Sticking power | ||||||||||
| Kind | (part) | (part) | Kind | (part) | Kind | (part) | (part) | |||||||||||
| Embodiment | 14 | - | - | 20 | TDMA | 80 | ADMVN | 0.05 | 0.05 | Surpass 200 | 0.2 | 10/10 | 10/10 | 1.0 | 92 | ○ | ○ | 100/100 |
| HPP | 0.05 | |||||||||||||||||
| HPIC | 0.05 | |||||||||||||||||
| 15 | - | - | 20 | TDMA | 80 | ADMVN | 0.05 | 0.02 | Surpass 200 | 0.2 | 10/10 | 10/10 | 1.0 | 92 | ○ | ○ | 100/100 | |
| HPP | 0.05 | |||||||||||||||||
| HPIC | 0.05 | |||||||||||||||||
| 16 | - | - | 20 | TDMA | 80 | ADMVN | 0.05 | 0.03 | Surpass 200 | 0.2 | 10/10 | 10/10 | 1.1 | 92 | ○ | ○ | 100/100 | |
| HPP | 0.05 | |||||||||||||||||
| HPIC | 0.05 | |||||||||||||||||
| 17 | - | - | 20 | TDMA | 80 | ADMVN | 0.05 | 0.03 | Surpass 200 | 0.2 | 10/10 | 10/10 | 1.0 | 92 | ○ | ○ | 100/100 | |
| HPP | 0.05 | |||||||||||||||||
| HPIC | 0.05 | |||||||||||||||||
Table 4
| The alkyl methacrylate that contains the C8-20 alkyl | M M A | Polyfunctional group (methyl) acrylate | Polymerization starter | Polymerization regulator TP | Acrylic acid resin plate | The acrylic resin layered product | The touch panel transparent electrode plate | |||||||||||
| Load-carrying deflection deformation temperature (℃) | Turbidity | Plate splits preventing property | Outward appearance | Amount of warpage (%) | Total light transmittance (%) | Base plate deformation | The ITO state | Sticking power | ||||||||||
| Mn | (part) | (part) | Kind | (part) | Kind | (part) | (part) | |||||||||||
| Embodiment | 18 | 450000 | 3.75 | 46.25 | TDMA | 50 | ADMVN | 0.05 | 0.03 | 189 | 0.2 | 10/10 | 10/10 | 1.9 | 92 | ○ | ○ | 100/100 |
| HPP | 0.05 | |||||||||||||||||
| HPIC | 0.05 | |||||||||||||||||
| 19 | 450000 | 3.75 | 46.25 | TDMA | 50 | ADMVN | 0.05 | 0.06 | 190 | 0.2 | 10/10 | 10/10 | 1.9 | 92 | ○ | ○ | 100/100 | |
| HPP | 0.05 | |||||||||||||||||
| HPIC | 0.05 | |||||||||||||||||
| 20 | 450000 | 3.75 | 46.25 | TDMA | 50 | ADMVN | 0.05 | 0.1 | 190 | 0.2 | 10/10 | 10/10 | 1.9 | 92 | ○ | ○ | 100/100 | |
| HPP | 0.05 | |||||||||||||||||
| HPIC | 0.05 | |||||||||||||||||
| 21 | 450000 | 3.75 | 46.25 | TDMA | 50 | ADMVN | 0.05 | 0.02 | 187 | 0.2 | 10/10 | 10/10 | 1.8 | 92 | ○ | ○ | 100/100 | |
| HPP | 0.05 | |||||||||||||||||
| HPIC | 0.05 | |||||||||||||||||
| 22 | 450000 | 3 | 37 | TDMA | 60 | ADMVN | 0.05 | 0.03 | Surpass 200 | 0.2 | 10/10 | 10/10 | 2.0 | 92 | ○ | ○ | 100/100 | |
| HPP | 0.05 | |||||||||||||||||
| HPIC | 0.05 | |||||||||||||||||
| 23 | 450000 | 4.13 | 50.87 | TDMA | 45 | ADMVN | 0.05 | 0.03 | 167 | 0.2 | 10/10 | 10/10 | 1.9 | 92 | ○ | ○ | 100/100 | |
| HPP | 0.05 | |||||||||||||||||
| HPIC | 0.05 | |||||||||||||||||
| 24 | - | 0 | 50 | TDMA | 50 | ADMVN | 0.05 | 0.03 | 190 | 0.2 | 10/10 | 10/10 | 1.9 | 92 | ○ | ○ | 100/100 | |
| HPP | 0.05 | |||||||||||||||||
| HPIC | 0.05 | |||||||||||||||||
Table 5
| The alkyl methacrylate that contains the C8-20 alkyl | M M A | Polyfunctional group (methyl) acrylate | Polymerization starter | Polymerization regulator TP | Acrylic acid resin plate | The acrylic resin layered product | The touch panel transparent electrode plate | |||||||||||
| Load-carrying deflection deformation temperature (℃) | Turbidity | Plate splits preventing property | Outward appearance | Amount of warpage (%) | Total light transmittance (%) | Base plate deformation | The ITO state | Sticking power | ||||||||||
| Kind | (part) | (part) | Kind | (part) | Kind | (part) | (part) | |||||||||||
| Comparative example | 1 | - | 0 | 20 | TDMA | 80 | ADMVN | 0.05 | 0 | Surpass 200 | 0.2 | 1/10 | 8/10 | 1.0 | 92 | ○ | ○ | 100/100 |
| HPP | 0.05 | |||||||||||||||||
| HPIC | 0.05 | |||||||||||||||||
| 2 | - | 0 | 20 | TDMA | 80 | ADMVN | 0.05 | 0.005 | Surpass 200 | 0.2 | 3/10 | 10/10 | 1.0 | 92 | ○ | ○ | 100/100 | |
| HPP | 0.05 | |||||||||||||||||
| HPIC | 0.05 | |||||||||||||||||
| 3 | - | 0 | 70 | TDMA | 30 | ADMVN | 0.05 | 0.03 | 120 | 0.2 | 10/10 | 10/10 | 1.7 | 92 | × | × | 70100 | |
| HPP | 0.05 | |||||||||||||||||
| HPIC | 0.05 | |||||||||||||||||
| 4 | - | 0 | 50 | TDMA | 50 | ADMVN | 0.05 | 0.03 | 140 | 0.2 | 10/10 | 10/10 | 1.3 | 92 | × | × | 82/100 | |
| HPP | 0.05 | |||||||||||||||||
| - | - | |||||||||||||||||
| 5 | |
5 | 65 | TDMA | 0 | ADMVN | 0.05 | 0.03 | 115 | 0.2 | 10/10 | 10/10 | Be out of shape during film forming | 92 | × | × | 68/100 | |
| HPP | 0.05 | |||||||||||||||||
| HPIC | 0.05 | |||||||||||||||||
Table 6
| The alkyl methacrylate that contains the C8-20 alkyl | M M A | Polyfunctional group (methyl) acrylate | Polymerization starter | Polymerization regulator TP | Acrylic acid resin plate | The acrylic resin layered product | The touch panel transparent electrode plate | |||||||||||
| Load-carrying deflection deformation temperature (℃) | Turbidity | Plate splits preventing property | Outward appearance | Amount of warpage (%) | Total light transmittance (%) | Base plate deformation | The ITO state | Sticking power | ||||||||||
| Mn | (part) | (part) | Kind | (part) | Kind | (part) | (part) | |||||||||||
| Comparative example | 6 | 450000 | 3.75 | 46.25 | NPG | 50 | ADMVN | 0.03 | 0 | 184 | 0.2 | 1/10 | 10/10 | 1.9 | 92 | ○ | ○ | 100/100 |
| HPP | 0.01 | |||||||||||||||||
| BPIC | 0.01 | |||||||||||||||||
| 7 | 450000 | 3.75 | 46.25 | NPG | 50 | ADMVN | 0.03 | 0.005 | 185 | 0.2 | 3/10 | 10/10 | 1.9 | 92 | ○ | ○ | 100/100 | |
| HPP | 0.01 | |||||||||||||||||
| BPIC | 0.01 | |||||||||||||||||
| 8 | 450000 | 5.25 | 64.75 | NPG | 30 | ADMVN | 0.03 | 0.03 | 141 | 0.2 | 10/10 | 10/10 | 1.8 | 92 | × | × | 83/100 | |
| HPP | 0.01 | |||||||||||||||||
| BPIC | 0.01 | |||||||||||||||||
| 9 | - | 0 | 50 | NPG | 50 | ADMVN | 0.03 | 0.005 | 184 | 0.2 | 0/10 | 10/10 | 1.9 | 92 | ○ | ○ | 100/100 | |
| HPP | 0.01 | |||||||||||||||||
| BPIC | 0.01 | |||||||||||||||||
Table 7
| The alkyl methacrylate that contains the C8-20 alkyl | M M A | Polyfunctional group (methyl) acrylate | Polymerization starter | Polymerization regulator TP | Acrylic acid resin plate | The acrylic resin layered product | The touch panel transparent electrode plate | |||||||||||
| Load-carrying deflection deformation temperature (℃) | Turbidity | Plate splits preventing property | Outward appearance | Amount of warpage (%) | Total light transmittance (%) | Base plate deformation | The ITO state | Sticking power | ||||||||||
| Kind | (part) | (part) | Kind | (part) | Kind | (part) | (part) | |||||||||||
| Embodiment | 25 | |
10 | 10 | TDMA | 80 | ADMVN | 0.05 | 0.03 | Surpass 200 | 0.2 | 10/10 | 10/10 | 0.2 | 92 | ○ | ○ | 100/100 |
| HPP | 0.05 | |||||||||||||||||
| HPIC | 0.05 | |||||||||||||||||
| 26 | |
5 | 10 | TDMA | 80 | ADMVN | 0.05 | 0.03 | Surpass 200 | 0.2 | 10/10 | 10/10 | 0.3 | 92 | ○ | ○ | 100/100 | |
| HPP | 0.05 | |||||||||||||||||
| HPIC | 0.05 | |||||||||||||||||
※ embodiment 25 and then contain 0.05 part of n-dodecyl mercaptan
※ embodiment 26 and then contain 5 parts of methyl acrylates
Following content is represented in abbreviation in each table.
ADMVN:2,2 '-azo two (2,4-dimethyl-4-methoxyl group valeronitrile) (half life temperature was 30 ℃ in 10 hours)
HPP: tert-butyl peroxide pivalate (half life temperature was 53 ℃ in 10 hours)
HPIC: tert-butyl peroxide sec.-propyl monocarbonate (half life temperature was 95 ℃ in 10 hours)
BPIC: tert-butyl peroxide sec.-propyl carbonic ether (half life temperature was 97 ℃ in 10 hours)
TDMA: two (oxygen methyl) three rings [5,2,1,0
2,6] the decane dimethacrylate
NPG: neopentylglycol dimethacrylate
ISMA: methacrylic acid isooctadecane base ester
MMA: methyl methacrylate
LMA: lauryl methacrylate(LMA)
TMA: methacrylic acid tridecyl ester
SMA: methacrylic acid stearyl
TP: terpinolene
Mn: number-average molecular weight
Shown in table 1～4 and table 7, in embodiment 1～26, split preventing property, touch panel the transparency, outward appearance, sticking power with transparent electrode plate at thermotolerance, the transparency, the plate of acrylic acid resin plate, obtain good result.In addition, touch panel also can normally be worked.In addition, in embodiment 1～10,25 and 26,, obtain good result at the shape stability of acrylic resin layered product.In addition, in embodiment 25 and 26, compare with embodiment 1, levels of residual monomers reduces.
On the other hand, shown in table 5 and 6, in comparative example 1,2,6,7 and 9, in the stripping process of acrylic acid resin plate, produce problems such as plate splits.In addition, in comparative example 3～5 and 8, the thermotolerance of acrylic acid resin plate is low, deforms when when the ITO film forming 120 ℃ heating and 150 ℃ of heating when forming electrode, is unsuitable for as touch panel.
Claims (20)
1. the manufacture method of an acrylic acid resin plate, it has operation as described below: the mixture that is made of single ethylene unsaturated monomer 5～65 quality % and polyfunctional group (methyl) acrylate 35～95 quality % of per 100 mass parts, make its 10 hours half life temperatures that contain 0.001～1 mass parts form polyblend at least a compound that is selected from the group that cyclohexadiene and derivative thereof and class terpenoid and derivative thereof form more than or equal to 80 ℃ polymerization starter and 0.015～0.2 mass parts, and this polyblend is carried out the operation of polymerizing curable, above-mentioned single ethylene unsaturated monomer is the material that comprises the alkyl methacrylate of the alkyl with carbonatoms 1～4, above-mentioned polyfunctional group (methyl) acrylate is the compound by following general formula (1) expression
In the formula, R
1Expression H or CH
3
2. the manufacture method of an acrylic acid resin plate, it has operation as described below: the slurry by 5～65 mass parts of per 100 mass parts, and the mixture that constitutes of polyfunctional group (methyl) acrylate by the compound of following general formula (1) expression of 35～95 mass parts, make its 10 hours half life temperatures that contain 0.001～1 mass parts form polyblend at least a compound that is selected from the group that cyclohexadiene and derivative thereof and class terpenoid and derivative thereof form more than or equal to 80 ℃ polymerization starter and 0.015～0.2 mass parts, and this polyblend is carried out the operation of polymerizing curable, above-mentioned slurry is formed by single ethylene unsaturated monomer 70～99 quality % of the alkyl methacrylate that comprises the alkyl with carbonatoms 1～4 with by multipolymer or homopolymer 1～30 quality % that single ethylene unsaturated monomer unit of the alkyl methacrylate that comprises the alkyl with carbonatoms 1～4 constitutes
In the formula, R
1Expression H or CH
3
3. the manufacture method of acrylic acid resin plate according to claim 1, wherein, polyfunctional group (methyl) acrylate is the compound of following general formula (2) expression,
In the formula, R
2And R
3Expression H or CH
3, R
4And R
5Expression H or carbonatoms are smaller or equal to 3 alkyl, and n represents 0～4 integer.
4. the manufacture method of acrylic acid resin plate according to claim 3, wherein mixture is the mixture that single ethylene unsaturated monomer 30～65 quality % and described polyfunctional group (methyl) acrylate 35～70 quality % by the alkyl methacrylate that comprises the alkyl with carbonatoms 1～4 constitute.
5. the manufacture method of acrylic acid resin plate according to claim 2, wherein, polyfunctional group (methyl) acrylate is the compound of following general formula (2) expression,
In the formula, R
2And R
3Expression H or CH
3, R
4And R
5Expression H or carbonatoms are smaller or equal to 3 alkyl, and n represents 0～4 integer.
6. the manufacture method of acrylic acid resin plate according to claim 5, wherein, mixture is the mixture that is made of described polyfunctional group (methyl) acrylate of the slurry of 30～60 mass parts and 35～70 mass parts, and described slurry is formed by single ethylene unsaturated monomer 70～99 quality % of the alkyl methacrylate that comprises the alkyl with carbonatoms 1～4 with by multipolymer or homopolymer 1～30 quality % that single ethylene unsaturated monomer unit of the alkyl methacrylate that comprises the alkyl with carbonatoms 1～4 constitutes.
7. the acrylic resin laminated body manufacturing method that forms nesa coating is gone up at least one surface of the acrylic acid resin plate that is made by claim 1 or 2 described manufacture method.
8. acrylic resin laminated body manufacturing method according to claim 7, wherein, nesa coating is the ITO film.
9. touch panel has following operation with the manufacture method of transparent electrode plate: the operation that forms nesa coating is gone up at least one surface of the acrylic acid resin plate that is made by claim 1 or 2 described manufacture method.
10. the touch panel according to claim 9 manufacture method of transparent electrode plate, wherein, nesa coating is the ITO film.
11. the touch panel according to claim 9 manufacture method of transparent electrode plate, wherein, the load-carrying deflection deformation temperature of transparent electrode plate is more than or equal to 150 ℃.
12. the manufacture method of a touch panel, have upper transparent electrode plate and lower transparent electrode plate, this upper transparent electrode plate and lower transparent electrode plate are the transparent electrode plates that has transparency carrier and be formed at least one lip-deep nesa coating of this transparency carrier, make the manufacture method of the touch panel of each other nesa coating opposed and partition distance ground this upper transparent electrode plate of configuration and this lower transparent electrode plate, wherein, at least one of this upper transparent electrode plate and this lower transparent electrode plate is the touch panel transparent electrode plate that makes by the described manufacture method of claim 8.
13. acrylic resin, it is characterized in that, polyfunctional group (methyl) acrylic ester unit that comprises the alkyl methacrylate that comprises the alkyl unitary single ethylene unsaturated monomer unit of the alkyl methacrylate unit of alkyl of 5～20 quality % and 2～35 quality % and 50～85 quality % by the compound of following general formula (1) expression with carbonatoms 1～4 with carbonatoms 8～20
In the formula, R
1Expression H or CH
3
14. the acrylic acid resin plate that constitutes by claim 12 or 13 described resins.
15. the manufacture method of an acrylic acid resin plate, it has operation as described below: per 100 mass parts comprise the alkyl methacrylate of the alkyl with carbonatoms 8～20 of 5～20 quality %, single ethylene unsaturated monomer with the alkyl methacrylate of 2～35 quality % with carbonatoms 1～4 alkyl, mixture with polyfunctional group (methyl) acrylate of the compound of 50～85 quality % such as following general formula (1) expression, make its 10 hours half life temperatures that contain 0.001～1 mass parts form polyblend at least a compound that is selected from the group that cyclohexadiene and derivative thereof and class terpenoid and derivative thereof form more than or equal to 80 ℃ polymerization starter and 0.015～0.2 mass parts, and polyblend is carried out the operation of polymerizing curable
In the formula, R
1Expression H or CH
3
The acrylic resin layered product that constitutes 16. at least one surface of the described acrylic acid resin plate of claim 14, form nesa coating.
17. acrylic resin layered product according to claim 16, wherein, nesa coating is the ITO film.
18. have the touch panel transparent electrode plate of the described acrylic resin layered product of claim 16.
19. touch panel transparent electrode plate according to claim 18, wherein, load-carrying deflection deformation temperature is more than or equal to 150 ℃.
20. touch panel, have upper transparent electrode plate and lower transparent electrode plate, and this upper transparent electrode plate and lower transparent electrode plate have transparency carrier and are formed at least one lip-deep nesa coating of this transparency carrier, make the opposed and touch panel of partition distance ground this upper transparent electrode plate of configuration and this lower transparent electrode plate of each other nesa coating, wherein, at least one of this upper transparent electrode plate and this lower transparent electrode plate is the described touch panel transparent electrode plate of claim 18.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP326804/2002 | 2002-11-11 | ||
| JP2002326804A JP2004161825A (en) | 2002-11-11 | 2002-11-11 | Method for producing acrylic resin plate |
| JP287820/2003 | 2003-08-06 | ||
| JP291216/2003 | 2003-08-11 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1711293A CN1711293A (en) | 2005-12-21 |
| CN1318462C true CN1318462C (en) | 2007-05-30 |
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|---|---|---|---|
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|---|---|---|---|---|
| TWI512585B (en) * | 2014-03-07 | 2015-12-11 | Elan Microelectronics Corp | Capacitive touch panel and manufacture method thereof |
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|---|---|---|---|---|
| JP5006017B2 (en) * | 2006-12-07 | 2012-08-22 | 三菱レイヨン株式会社 | Method for producing resin molded product and method for producing fiber-reinforced composite material |
| WO2010105289A1 (en) | 2009-03-16 | 2010-09-23 | Carl Zeiss Vision Australia Holdings Limited | Liquid casting compositions, production processes and photochromic optical elements |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4791184A (en) * | 1984-03-27 | 1988-12-13 | Kyowa Gas Chemical Industry Co., Ltd. | Methacrylic resin molding material and method for production thereof |
| JPS6490205A (en) * | 1987-09-30 | 1989-04-06 | Japan Synthetic Rubber Co Ltd | Acrylate polymer |
-
2002
- 2002-11-11 JP JP2002326804A patent/JP2004161825A/en active Pending
-
2003
- 2003-11-10 CN CNB2003801029789A patent/CN1318462C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4791184A (en) * | 1984-03-27 | 1988-12-13 | Kyowa Gas Chemical Industry Co., Ltd. | Methacrylic resin molding material and method for production thereof |
| JPS6490205A (en) * | 1987-09-30 | 1989-04-06 | Japan Synthetic Rubber Co Ltd | Acrylate polymer |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI512585B (en) * | 2014-03-07 | 2015-12-11 | Elan Microelectronics Corp | Capacitive touch panel and manufacture method thereof |
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| JP2004161825A (en) | 2004-06-10 |
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