TW201509242A - Transparent-circuit-board manufacturing method - Google Patents

Abstract

This invention provides a transparent-circuit-board manufacturing method that makes it possible to perform desired patterning in a clean fashion while reducing outgassing due to a temporary affixing material even if a high-temperature treatment with a temperature of 200 DEG C or more, for example, is performed. This invention is a transparent-circuit-board manufacturing method that includes the following steps: a laminate-preparation step in which a laminate comprising a transparent workpiece temporarily affixed to a support with a temporary affixing material interposed therebetween is prepared; a patterning step in which patterning that includes a heat treatment using a temperature of 200 DEG C or more is used to form a pattern on the transparent workpiece, yielding a transparent circuit board; and a separation step in which the transparent circuit board is separated from the temporary affixing material. If the temporary affixing material is subjected to simultaneous differential thermal and thermogravimetric measurement with the temperature raised to 400 DEG C at a rate of 5 DEG C/min, said temporary affixing material exhibits a weight decrease percentage of less than 1% at temperatures less than or equal to 200 DEG C.

Description

Transparent circuit substrate manufacturing method

The present invention relates to a method of manufacturing a transparent circuit substrate.

In recent years, as a member of an electronic device or a display, for example, a glass substrate which is lightweight, has impact resistance, and is thin, such as a circuit board of a TFT (drive circuit), a color filter, and a touch panel, has been developed.

However, as the thickness of the glass substrate is reduced, the strength of the glass sheet to be processed is lowered or bent, which makes it difficult to operate during the manufacturing process or the work efficiency is lowered. As a method for producing a glass substrate to cope with the above, a technique is disclosed in which a thin glass substrate is fixed to a support substrate as a reinforcing material via an adhesive, and a transparent electrode film is formed on the surface of the thin glass substrate ( Patent Document 1).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-285324

In the above technique, the thin-walled glass substrate, the adhesive as the temporary fixing material, and the support substrate are integrally patterned, and therefore the adhesive is also affected by the heat treatment at this time. Although the adhesive has heat resistance, it is not sufficient. If the influence of the heat treatment cannot be ignored, the outgas of the adhesive may be contaminated to contaminate the glass substrate or the desired pattern may not be formed.

The present invention has been made in view of the above problems found in the production of a transparent circuit board, and an object of the invention is to provide a method for reducing the generation of outgassing from a temporary fixing material even when subjected to a high temperature treatment of, for example, 200 ° C or higher. A method of manufacturing a transparent circuit substrate that requires pattern processing.

As a result of intensive studies, the inventors of the present invention have found that the above object can be attained by the following constitution, and the present invention has been completed.

The present invention relates to a method of manufacturing a transparent circuit substrate, comprising: a laminate preparation step of preparing a laminated body in which a transparent workpiece is temporarily fixed to a support via a temporary fixing member, and a processing step is included Forming a pattern of heat treatment at 200° C. or higher to form a transparent circuit substrate on the transparent workpiece, and a peeling step of peeling off the transparent circuit substrate from the temporary fixing material; and raising temperature of the temporary fixing member by 5 When the temperature was raised to 400 ° C and the differential thermal-thermal weight simultaneous measurement was carried out, the weight reduction rate of the temporary fixing material at 200 ° C was less than 1%.

In this manufacturing method, since a transparent workpiece is fixed by using a temporary fixing material having a high heat resistance of less than 1% at a high temperature of 200 ° C or lower, even if pattern processing including heat treatment at 200 ° C or higher is performed, The generation of outgas from the temporary fixing material can be sufficiently suppressed, and as a result, pattern processing can be performed in a clean state, and a desired pattern can be formed. Further, the method for measuring the weight reduction rate is based on the description of the examples.

In the manufacturing method, the temporary fixing member preferably includes a high-adhesion layer having an adhesion force of 0.05 N/20 mm or more and 10 N/20 mm or less to the glass plate, and a low adhesion layer having 0 N/for the glass plate. Adhesive force of 20mm or more and less than 0.05N/20mm. According to this configuration, the removability at the time of processing of the transparent workpiece and the peelability after the processing can be simultaneously achieved with high efficiency.

In the plan view of the laminated body after the pattern formation, the outer periphery of the pattern processing region on the transparent workpiece is preferably located on the inner side of the outer periphery of the lower adhesive layer. Thereby, even when the peripheral portion of the transparent circuit substrate is cut out, or when the transparent circuit substrate is singulated one by one, the low-adhesive layer can be distributed to the cut-out transparent circuit. The substrate can be easily peeled off from the support. Furthermore, the number of pattern processing regions corresponding to one low adhesion layer may be one or plural. When a plurality of pattern processing regions are allocated to one low-adhesion layer, the outer periphery of the pattern processing region at the outermost periphery may be located inside the outer periphery of the low-adhesion layer.

In the above laminated body, the low-adhesion layer is preferably disposed between the transparent workpiece and the support, and the high-adhesion layer is preferably connected to the outer peripheral side surface of the transparent circuit substrate and the outer peripheral side surface of the support. Mode configuration. Thereby, the high adhesive layer is not attached to the processing region of the transparent workpiece, so that the transparent workpiece can be processed in a clean state. Further, when the transparent workpiece is peeled off from the support, only a portion of the high-adhesion layer located on the outer periphery can be peeled off or cut off, so that the production efficiency can be improved.

In the case where the high-adhesion layer is disposed on the outer peripheral side of the laminated body, the height of the high-adhesion layer is preferably 50% or more and less than 100% of the height of the laminated body in the side view of the laminated body. Thereby, the transparent workpiece can be firmly fixed to the support, and the high adhesive layer can be prevented from being folded into the processing surface of the transparent workpiece, and the transparent workpiece can be cleanly processed.

10, 40‧‧‧ layered body

11, 21, 31, 41‧‧‧ temporary fixtures

11a, 21a, 31a, 41a‧‧‧ high adhesion layer

11b, 21b, 31b, 41b‧‧‧ low adhesion layer

11C, 21C‧‧‧ the central part of temporary fixtures

11P, 21P‧‧‧ Peripheral parts of temporary fixtures

12. 42‧‧‧ Support

13, 43‧‧‧ transparent workpiece

14, 44‧‧‧ patterns

15, 45‧‧‧ Transparent circuit substrate

H‧‧‧ Height of high adhesion layer

H‧‧‧ height of laminated body

Fig. 1A is a partial perspective plan view of a temporary fixing member according to an embodiment of the present invention.

Fig. 1B is a cross-sectional view taken along line X-X of Fig. 1.

Fig. 2A is a schematic cross-sectional view showing a method of manufacturing a transparent circuit board according to an embodiment of the present invention.

Fig. 2B is a schematic cross-sectional view showing a method of manufacturing a transparent circuit board according to an embodiment of the present invention.

2C is a view for explaining the manufacture of a transparent circuit substrate according to an embodiment of the present invention; Sectional pattern diagram of the law.

2D is a schematic cross-sectional view for explaining a method of manufacturing a transparent circuit substrate according to an embodiment of the present invention.

Fig. 3 is a cross-sectional schematic view showing a temporary fixing member according to another embodiment of the present invention.

Fig. 4 is a cross-sectional schematic view showing a temporary fixing member according to still another embodiment of the present invention.

Fig. 5 is a cross-sectional schematic view showing a temporary fixing member according to still another embodiment of the present invention.

A method for producing a transparent circuit board according to the present invention includes a laminate preparation step of preparing a laminate in which a transparent workpiece is temporarily fixed to a support via a temporary fixing member, and a processing step of including a temperature of 200 ° C or higher Forming a pattern of the heat treatment to form a transparent circuit substrate on the transparent workpiece; and a peeling step of peeling the transparent circuit substrate from the temporary fixing material, and heating the substrate at a temperature increase rate of 5 ° C/min When the temperature was raised to 400 ° C and the differential thermal-thermal weight synchronization measurement was performed, the weight reduction rate of the temporary fixing material at 200 ° C was less than 1%.

First, a method of manufacturing a transparent circuit substrate according to an embodiment of the present invention will be described below with reference to the drawings. In addition, in the drawings, portions that are not described are omitted, and portions that are enlarged or reduced for convenience of explanation are shown. In addition, the terms "upper surface" and "lower surface" used in the present specification are used to indicate the positional relationship of each constituent member in the drawing for convenience of explanation, and are not limited to temporary fixing materials or semiconductors. The actual state or positional relationship of the device.

<First embodiment>

[Layer preparation step]

In the laminate preparation step, the transparent workpiece is temporarily fixed by the temporary fixing material. A layered body that is set on the support. Hereinafter, each member will be described, and the formation of the laminated body will be described.

(temporary fixing material)

Fig. 1A is a partial perspective plan view of a temporary fixing member according to an embodiment of the present invention, and Fig. 1B is a cross-sectional view taken along line X-X. As shown in Fig. 1B, in the temporary fixing member 11, the peripheral portion 11P is formed of the high-adhesion layer 11a, and the central portion 11C on the inner side of the peripheral portion 11P is made of the high-adhesion layer 11a and the adhesive force is lower than that of the high-adhesion layer 11a. The adhesive layer 11b is formed by lamination. That is, the temporary fixing member 11 has a low-adhesion layer 11b and a high-adhesion layer 11a which is laminated on the low-adhesion layer 11b so as to cover the upper surface and the side surface of the low-adhesion layer 11b. The adhesion of the low adhesion layer 11b is lower than the adhesion of the high adhesion layer 11a. When the temporary fixing material 11 is bonded to the support, the temporary fixing material 11 is bonded to the support by the surface on the exposed side of the low-adhesion layer 11b as a bonding surface (see FIG. 2A).

In the temporary fixing member 11, the high adhesive layer 11a having an adhesive force higher than that of the low-adhesion layer 11b exists in the peripheral portion, so that the portion can be firmly adhered to the support. Further, it is not only the high-adhesion layer 11a but also the low-adhesion layer 11b having a lower adhesive force than the high-adhesion layer 11a. Therefore, in the peeling step described below, the support and the transparent circuit substrate can be easily moved up and down by an external force. Separation.

Further, in the temporary fixing member 11, the transparent workpiece placed on the temporary fixing member 11 can be more firmly fixed to the surface on which only the high-adhesion layer 11a is exposed. Further, the central portion 11C is formed by laminating a high adhesion layer 11a and a low adhesion layer 11b. Therefore, the central portion 11C formed by laminating the high-adhesion layer 11a and the low-adhesion layer 11b has a relatively low adhesive force as compared with the peripheral portion 11P formed only of the high-adhesion layer 11a. Thereby, the support can be easily separated from the transparent circuit substrate by applying an external force. Further, since the low-adhesion layer 11b is also connected to the support, the temporary fixing member 11 is easily peeled off from the support after the peeling step. Therefore, it is easy to reuse the support. Further, since the high-adhesion layer 11a is formed on the peripheral edge portion 11P of the temporary fixing member 11, the high-adhesion layer 11a is dissolved by a solvent in the peeling step described below, or a cutter or a laser is used. Further, the slit is physically cut, whereby the adhesion of the peripheral portion 11P to the central portion 11C can be blocked, and the temporary fixing member 11 can be more easily peeled off from the support 12.

The temporary fixing material 11 is subjected to differential thermal-thermal weight synchronous measurement at a temperature increase rate of 5 ° C/min to 400 ° C. At this time, the weight reduction rate of the temporary fixing material 11 at 200 ° C is preferably less than 1%. Preferably, it is 0.8% or less, and further preferably 0.6% or less. The lower limit of the weight reduction rate is preferably as low as possible, and is preferably 0% or more, but may be 0.01% or more. When the weight reduction rate is within the above range, the generation of outgas from the temporary fixing material can be sufficiently suppressed, and the pattern can be processed in a clean state to form a desired pattern.

The thickness of the temporary fixing member 11 is not particularly limited, and the lower limit thereof is, for example, 5 μm or more, and preferably 10 μm or more. When the thickness is 5 μm or more, the surface of the support or the surface of the transparent workpiece can follow the irregularities, and the support and the transparent workpiece can be filled with the temporary fixing material without a gap. Further, the upper limit of the thickness of the temporary fixing member 11 is, for example, 500 μm or less, preferably 200 μm or less. When it is 500 μm or less, thickness unevenness or shrinkage and expansion at the time of heating can be suppressed.

The thickness of the high-adhesion layer 11a in the central portion 11C can be appropriately set, and the lower limit thereof is preferably 0.1 μm or more, more preferably 0.5 μm or more, and still more preferably 1 μm or more. Further, the upper limit of the thickness is preferably 300 μm or less, more preferably 200 μm or less. Further, the thickness of the low-adhesion layer 11b in the central portion 11C can be appropriately set to the same thickness as that of the high-adhesion layer 11a.

As shown in FIG. 1A, the temporary fixing member 11 has a rectangular shape in plan view. The plan view size of the temporary fixing member 11 is not particularly limited, and may be appropriately set depending on the size of the processed transparent workpiece. For example, the length of one side of the temporary fixing member 11 is preferably +1.0 to -1.0 mm with respect to the length of the corresponding side in the support.

Further, when the temporary fixing member 11 is viewed in plan, the shape of the low-adhesion layer 11b is rectangular. The area of the low-adhesion layer 11b when the temporary fixing member 11 is viewed from above is preferably 10% or more, more preferably 20% or more, and still more preferably 50% or more with respect to the area of the temporary fixing member 11 when the temporary fixing member 11 is viewed from above. . When it is 10% or more, it is easy to separate a transparent circuit board and a support. Further, the area of the low-adhesion layer 11b is preferably 99.95% or less, more preferably 99.9% or less. If it is 99.95% or less, the transparent workpiece can be firmly fixed to the support.

(high adhesion layer)

Regarding the adhesion of the high-adhesion layer 11a, for example, at a temperature of 23±2° C. and a peeling speed of 300 mm/min, the 90° peeling force to the glass plate is preferably 0.05 N/20 mm or more, and more preferably 0.10 N/20 mm or more. . When it is 0.05 N/20 mm or more, the support and the temporary fixing material 11 can be fixed more firmly. Further, the upper limit of the 90° peeling force is not particularly limited, and is preferably as large as possible, but is, for example, 10 N/20 mm or less, preferably 5 N/20 mm or less.

The adhesive composition constituting the high-adhesion layer 11a is not particularly limited, and a structural unit having a fluorenylene group and at least a part having a diamine derived from an alkyl ether structure or a linear alkyl group can be preferably used. A polyimine resin or a polyamidoximine resin of a structural unit of a diamine. Further, a polyoxynoxy resin can also be preferably used. Among them, the above polyimine resin is preferred in terms of heat resistance, chemical resistance, and paste residue.

The above polyimine resin can be usually obtained by imidization (dehydration condensation) of polyphosphonium amide as its precursor. As a method of imidizing polyphosphonium amide, for example, a conventionally known heating hydrazine imidation method, azeotropic dehydration method, chemical hydrazine imidation method, or the like can be employed. Among them, a heated hydrazine imidation method is preferred. In the case of using the heated hydrazine imidation method, in order to prevent deterioration of the polyimide resin by oxidation, it is preferred to carry out heat treatment in an inert gas atmosphere under a nitrogen atmosphere or a vacuum.

The above polylysine may be an acid anhydride and a diamine (including a diamine having an alkyl ether structure and a linear alkylenediamine) in a solvent selected as appropriate (also referred to as "specific diamine" And any one of these diamines (hereinafter also referred to as "other diamines") is added in such a manner as to be substantially equal to the molar ratio, and these reactions are obtained.

The diamine having an alkyl ether structure is not particularly limited as long as it has a compound having an alkyl ether structure and having at least two terminals having an amine structure. For example, a diamine having a methylene skeleton and an ether group bonded thereto may be mentioned.

The diamine having a methylene skeleton and an ether group bonded thereto may, for example, be a diamine having a polypropylene glycol structure and having one amine group at both ends, and having a polyethylene glycol structure and A diamine having an amine group and a diamine having a polybutylene glycol structure and having one amine group at both ends. Further, a diamine having a plurality of such methylene skeletons and an ether group bonded thereto and having one amine group at both ends may be mentioned.

The molecular weight of the above diamine having an ether structure is preferably in the range of from 100 to 5,000, more preferably from 150 to 4,800. When the molecular weight of the diamine having an ether structure is in the range of 100 to 5,000, it is easy to obtain a high-adhesion layer 11a having high adhesion and light peeling property.

The linear alkylenediamine may be a diamine having a linear alkylene group structure and having one amine group at each terminal. Examples of the linear alkylene diamine include ethylenediamine, hexamethylenediamine, 1,8-octanediamine, 1,10-decanediamine, 1,12-dodecanediamine, and 1, 14-tetradecanediamine, 1,16-hexadecyldiamine, 1,20-eicosanediamine, and the like. The linear alkylene diamine has a molecular weight of usually from 50 to 1,000,000, preferably from 100 to 30,000.

In the formation of the above polyimine resin, a diamine other than a specific diamine may be used in combination. As another diamine, an aromatic diamine is mentioned. By using other diamines in combination, the adhesion to the adherend can be controlled.

Examples of the aromatic diamine include 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, and m-phenylenediamine. , p-phenylenediamine, 4,4'-diaminodiphenylpropane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 3,3'- Diaminodiphenyl sulfide, 4,4'-diaminodiphenylanthracene, 3,3'-diaminodiphenylanthracene, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)-2,2 - dimethylpropane, 4,4'-diaminobenzophenone, and the like. The molecular weight of the above aromatic diamine is usually from 50 to 1,000, preferably from 100 to 500. In the present specification, the molecular weight of the diamine means a value (weight average molecular weight) measured by GPC (gel permeation chromatography) and calculated from polystyrene.

When a diamine having an alkyl ether structure and other diamines are used in combination, the blending ratio of the two is preferably in the range of 50:50 to 20:80, more preferably 20:80 to 50 in terms of molar ratio. : 50, further preferably 25:75 to 45:55. When the ratio of the specific diamine to the other diamine is in the above range, both heat resistance and peelability are more excellent.

Further, when a linear alkyl diamine and other diamines are used in combination, the ratio of the two is preferably in the range of 100:0 to 20:80, more preferably 95:5. 40:60, and further preferably 90:10 to 50:50. When the ratio of the specific diamine to the other diamine is in the above range, both heat resistance and peelability are more excellent.

Examples of the acid anhydride include 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, and 3,3',4. , 4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2, 2-bis(2,3-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA), double (2,3-di) Carboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)ruthenic anhydride, bis(3,4-dicarboxyphenyl)anthracene Di-anhydride, pyromellitic dianhydride, ethylene glycol trimellitic acid dianhydride, and the like. These may be used alone or in combination of two or more.

Examples of the solvent for reacting the above acid anhydride with the above diamine include N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N,N-dimethylformamide, and a ring. Pentanone and the like. These may be used singly or in combination of plural kinds. Further, in order to adjust the solubility of the raw material or the resin, a nonpolar solvent such as toluene or xylene may be appropriately mixed and used.

Examples of the polyoxyxylene resin include a peroxide cross-linking type polyoxynoxy adhesive, an addition reaction type polyoxynoxy adhesive, a dehydrogenation type polyoxynoxy adhesive, and a moisture curing type. Polyoxygenated adhesives, etc. The above polysiloxane resin may be used singly or in combination of two or more. When the above polyoxyxylene resin is used, the heat resistance becomes high, and the storage modulus or adhesion at a high temperature can be an appropriate value. Among the above polyoxyxylene resins, an addition reaction type polyoxo-based adhesive is preferred in terms of less impurities.

The adhesive composition constituting the high-adhesion layer 11a may also contain other additives. As this Examples of other additives include a flame retardant, a decane coupling agent, and an ion scavenger. Examples of the flame retardant include antimony trioxide, antimony pentoxide, and brominated epoxy resin. Examples of the decane coupling agent include β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, γ-glycidoxypropyltrimethoxydecane, and γ-glycidoxypropyl group. Diethoxy decane and the like. Examples of the ion scavenger include hydrotalcites and barium hydroxide. The other additives may be used alone or in combination of two or more.

(low adhesion layer)

The adhesive composition constituting the low-adhesion layer 11b is not particularly limited, and a polyimide having a quinone imine group and having at least a part of a structural unit derived from the other diamine described above can be preferably used. By using only the above-mentioned other diamine without using the above specific diamine, the adhesion can be appropriately lowered. Regarding the composition or formation method of the low-adhesion layer 11b, the same composition and formation method as the high-adhesion layer can be employed except that the above-mentioned specific diamine in the above-mentioned high-adhesion layer is not used and only the other diamine is used as the diamine.

Further, as the other diamine, a fluorine-containing aromatic diamine such as 2,2'-bis(trifluoromethyl)benzidine or 1,1'-bis(trifluoromethyl)benzidine can be preferably used. .

The low-adhesive layer 11b is not particularly limited as long as it is a layer having a high adhesive force of the adhesive layer 11a and a heat-resistant layer, in addition to the layer formed of the above-mentioned resin. Examples of such a layer include a metal such as aluminum, a film of an inorganic material such as ceramics, and a film of another heat-resistant organic material such as polyimide or polyetheretherketone. Examples of the method for forming the film of the inorganic material include a vapor deposition method, a sputtering method, a chemical vapor deposition method, and a sol-gel method.

The adhesion of the low adhesion layer 11b is lower than the adhesion of the high adhesion layer 11a. Regarding the adhesion of the low-adhesion layer 11b, for example, at a temperature of 23±2° C. and a peeling speed of 300 mm/min, the 90° peeling force to the glass plate is preferably less than 0.05 N/20 mm, more preferably 0.01 N/20 mm. the following. If it is less than 0.05 N/20 mm, the low-adhesion layer 11b can be easily peeled off. The lower limit of the 90° peeling force is preferably as low as possible, preferably 0 N/20 mm or more, more preferably 0.001 N/20 mm. Further, it is preferably 0.0015 N/20 mm or more.

(Other characteristics of temporary fixing materials)

The weight reduction rate of the temporary fixing material after immersion in a 3% aqueous solution of tetramethylammonium hydroxide (TMAH) at room temperature for 5 minutes is preferably less than 1% by weight, more preferably less than 0.9% by weight, and further It is preferably less than 0.8% by weight. Further, the weight reduction rate is preferably as small as possible. Therefore, the lower limit of the weight reduction rate is preferably 0% by weight or more, but may be 0.001% by weight or more. When the weight reduction rate after immersion in the TMAH aqueous solution is in the above range, the solvent resistance (especially the solvent resistance to the TMAH aqueous solution) can be improved. The above weight reduction rate of the temporary fixing material can be controlled, for example, by the composition of the diamine used (the solubility of the diamine in the TMAH aqueous solution). The method for measuring the weight reduction rate described above is based on the description of the examples.

The weight reduction rate of the temporary fixing material after immersion in a 10% sulfuric acid aqueous solution at room temperature for 5 minutes is preferably less than 1% by weight, more preferably less than 0.9% by weight, and even more preferably less than 0.8% by weight. . Further, the weight reduction rate is preferably as small as possible. Therefore, the lower limit of the weight reduction rate is preferably 0% by weight or more, but may be 0.001% by weight or more. When the weight reduction rate after immersing in the aqueous sulfuric acid solution is in the above range, the acid resistance (especially the acid resistance to the sulfuric acid aqueous solution) can be improved. The above weight reduction rate of the temporary fixing material can be controlled, for example, by using the composition of the diamine used (the solubility of the diamine in the aqueous sulfuric acid solution). The method for measuring the weight reduction rate described above is based on the description of the examples.

The weight reduction rate of the temporary fixing material after immersion in a 10% sodium hydroxide aqueous solution at room temperature for 5 minutes is preferably less than 1% by weight, more preferably less than 0.9% by weight, and even more preferably less than 0.8%. weight%. Further, the weight reduction rate is preferably as small as possible. Therefore, the lower limit of the weight reduction rate is preferably 0% by weight or more, but may be 0.001% by weight or more. When the weight reduction rate after immersing in the aqueous sodium hydroxide solution is in the above range, alkali resistance (especially alkali resistance to an aqueous sodium hydroxide solution) can be improved. The above weight reduction rate of the temporary fixing material can be controlled, for example, by the composition of the diamine used (the solubility of the diamine in the aqueous sodium hydroxide solution). The method for measuring the weight reduction rate described above is based on the description of the examples.

The weight reduction rate of the temporary fixing material after immersion in 100 mL of N-methylpyrrolidone (NMP) at room temperature for 5 minutes is preferably less than 1% by weight, more preferably less than 0.9% by weight, and further Jia is less than 0.8% by weight. Further, the weight reduction rate is preferably as small as possible. Therefore, the lower limit of the weight reduction rate is preferably 0% by weight or more, but may be 0.001% by weight or more. When the weight reduction rate after immersion in NMP is in the above range, solvent resistance (especially resistance to NMP) can be improved. The above weight reduction rate of the temporary fixing material can be controlled, for example, by the composition of the diamine used (the solubility of the diamine to NMP). The method for measuring the weight reduction rate described above can be carried out in accordance with other measurement procedures for chemical resistance evaluation.

(Method of manufacturing temporary fixing materials)

The method for producing the temporary fixing member 11 is not particularly limited. As a first method, for example, it can be produced by applying a solution containing a composition for forming the low-adhesion layer 11b to a spacer, drying it to form a coating layer, and further comprising containing it to form a high adhesion. A solution of the composition of the layer 11a is applied onto and around the low-adhesion layer 11b, and dried to form a coating layer. The spacer for protection can also be attached to the high-adhesion layer 11a. In this method, the coating layer formed around the low-adhesion layer 11b becomes the high-adhesion layer 11a of the peripheral edge portion 11P. As a second method, a procedure may be employed in which the high-adhesion layer 11a and the low-adhesion layer 11b are respectively formed on different spacers, and finally the two are bonded together. In this case, by making the planar view of the high-adhesion layer 11a larger than the plan view size of the low-adhesion layer 11b, the high-adhesion layer 11a as the peripheral edge portion 11P can be formed around the low-adhesion layer 11b. As a third method, a procedure may be employed in which the low-adhesion layer 11b formed on the spacer is bonded to the support 12, and the high-adhesion layer 11a additionally formed on the spacer is bonded thereto. In this case, the high-adhesion layer 11a as the peripheral edge portion 11P may be formed around the low-adhesion layer 11b by making the planar view of the high-adhesion layer 11a larger than the plan view size of the low-adhesion layer 11b. Further, when the inorganic thin film or another heat resistant organic thin film or the like is used as the low-adhesion layer 11b, as a fourth method, a procedure may be employed in which the low-adhesion layer 11b is formed on the support 12 by vapor deposition or bonding. And attached to it and additionally formed on the spacer The adhesive layer 11a or the fifth method may be a method in which a low-adhesion layer 11b formed of an inorganic thin film or the like is formed on the high-adhesion layer 11a by vapor deposition or bonding, and the surface of the low-adhesion layer 11b is exposed. The surface is bonded to the support 12. The viscosity or coating amount of the applied solution may be appropriately set.

(transparent workpiece)

The transparent workpiece 13 (see FIG. 2A) is not particularly limited as long as it is a material having transparency and heat resistance, and examples thereof include polyesters such as polyethylene terephthalate and polyethylene naphthalate. Polycarbonate, polyimine, polyetherimide, polyamine, polyamidimide, wholly aromatic polyamine, polyphenylene sulfide, aromatic polyamide (paper), glass, glass Cloth, fluororesin, polyoxyxylene resin, metal (foil), paper, FRP (fiber reinforced plastics, fiber reinforced plastic), ultra-thin glass, physical tempered glass, chemically strengthened glass, and the like. Among them, the transparent workpiece preferably has substantially no flexibility. The term "substantially non-flexible" means that the bending modulus is broken at 500 MPa or more in the three-point bending test according to JIS R 1601.

The thickness of the transparent workpiece 13 may be set according to the design of the device in which the transparent circuit substrate is processed. However, the upper limit of the thickness is preferably 5 mm or less, more preferably 1 mm or less. Further, the lower limit of the thickness of the transparent workpiece is preferably 0.01 mm or more, and more preferably 0.05 mm or more from the viewpoint of strength or durability.

(support)

The support 12 (see FIG. 2A) is not particularly limited, and a SUS plate, a glass plate, a plastic plate or the like can be preferably used. As a material of the plastic plate, for example, low density polyethylene, linear polyethylene, medium density polyethylene, high density polyethylene, ultra low density polyethylene, random copolymer polypropylene, block copolymer polypropylene, and both can be used. Polyolefins such as polypropylene, polybutene, polymethylpentene, ethylene-vinyl acetate copolymer, ionic polymer resin, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylate (random , alternating) copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, polyurethane, polyethylene terephthalate Polyesters such as esters, polyethylene naphthalates, polycarbonates, polyimines, polyetheretherketones, polyimines, polyetherimine, polyamines, wholly aromatic polyamines, poly Phenylene sulfide, aromatic polyamine (paper), glass, glass cloth, fluororesin, polyvinyl chloride, polyvinylidene chloride, cellulose resin, polyoxyl resin, paper, and the like.

The support 12 can be used singly or in combination of two or more. The thickness of the support is not particularly limited and is usually about 10 μm to 20 mm.

(formation of laminated body)

Hereinafter, a case where the temporary fixing member 11 shown in FIGS. 1A and 1B is used will be described. 2A to 2D are schematic cross-sectional views for explaining a method of manufacturing a transparent circuit substrate according to an embodiment of the present invention. When the temporary fixing material 11 is produced by the above-described first or second method, the spacer is peeled off from the temporarily fixed material 11 to be produced, and the lower surface of the temporary fixing member 11 is used as a bonding surface to be bonded to the support 12 ( Refer to Figure 2A). The bonding method is not particularly limited, and a method using pressure bonding is preferred. The crimping is usually performed by pressing while being pressed by a pressing mechanism such as a crimping roller. The conditions for the pressure bonding are preferably 20 ° C to 150 ° C, 0.01 MPa to 10 MPa, and 1 mm / sec to 100 mm / sec. As described above, since the temporary fixing member 11 is exposed on the lower surface of the lower adhesive layer 11a having a higher adhesive force than the low-adhesion layer 11b, it can be firmly adhered to the support 1. In the case where the temporary fixing member 11 is produced by the above-described third to fifth methods, since the temporary fixing member 11 is produced in a state of being bonded to the support 12, it can be directly used in the next step.

Then, the laminated body 10 can be formed by bonding the transparent workpiece 13 to the temporary fixing member 11. The bonding method is not particularly limited, and is preferably pressure bonding. The crimping is usually performed by a pressing mechanism such as a crimping roller or a press machine. From the viewpoint of the unevenness of the irregularities, the thickness of the adherend, and the total thickness of the support, it is preferred to be a pressurization method. As a condition for crimping, it is preferably: temperature: 40 ° C to 200 ° C, extrusion: 0.1 kg / cm ² to 100 kg / cm ² , decompression environment: 1 to 100 torr (1.33 × 10 ² Pa ~ 1.33 × 10 ⁴ Pa), time: 60~600s.

[Processing steps]

As shown in FIG. 2B, in the processing step, the transparent circuit substrate 15 is formed by forming the pattern 14 on the transparent workpiece 13 by pattern processing including heat treatment at 200 ° C or higher.

The processing of the transparent workpiece 13 is not particularly limited, and a conventionally known process can be employed depending on the device design applied to the processed transparent circuit substrate 15, and representative examples thereof include pattern formation. Examples of the pattern 14 include a transparent substrate for use as a base substrate of a flexible circuit board (FPC) or an organic EL panel, or an electronic paper, an LCD, a display circuit using an organic EL as a display portion, and a color filter. Circuits, films, components, and the like formed on the transparent workpiece, which are necessary for applications such as a circuit board of a touch panel or a film forming process of a solar cell. The pattern may be required for the above-described use, and the shape or material of the pattern may be appropriately selected.

When a transparent circuit board is used as a member in which a circuit board such as a TFT (drive circuit) or a color filter is formed, a circuit board can be produced by a known photolithography process. As a representative photolithography step, the formation of the organic or inorganic thin film, the coating of the photoresist composition, the drying of the photoresist film, the exposure, the etching of the photoresist film, the etching of the above film, A process such as removal of the photoresist film forms a desired pattern circuit.

In the processing step, since the film formation, the drying of the photoresist film, or the cleaning and drying after the etching are performed as described above, the temporary fixing member 11 is required to have chemical resistance when the photoresist film or the plating wiring is formed. The heat resistance during film formation or drying, drying, and the vacuum resistance when forming a film (wiring) by sputtering or the like. Previously, due to the heat treatment or the vacuum treatment as described above, the outgas is generated by the temporary fixing member 11, and the interface between the temporary fixing member 11 and the transparent workpiece 13 or the interface between the temporary fixing member 11 and the support 13 generates bubbles or generates a release. The formation of a film due to gas is poor, or the temporary fixing member 11 is modified or deformed by the chemical treatment as described above, and thus the desired pattern formation may not be performed. In the present invention, the temporary fixing member 11 having heat resistance, chemical resistance, and vacuum resistance is used, so that the target pattern can be formed.

As the transparent circuit substrate, each of the transparent circuit substrates such as a single-sided circuit, a double-sided circuit, and a multilayer circuit can be formed, and not only a circuit but also a component can be mounted. Transparent workpiece When the circuit is formed on both sides, a method may be employed in which the circuit forming surface is fixed to the support via a temporary fixing member and the circuit is formed on the other surface after forming the circuit on one side.

In the case where an organic transistor is formed on a transparent workpiece, for example, a material thereof is not particularly limited, and a low molecular organic semiconductor material, a polymer organic semiconductor material, or an organic/inorganic hybrid semiconductor material can be used as the gate insulating material. An organic polymer material or an inorganic material can be used.

As a method of forming an organic transistor, a transfer method or the like can be cited, and an electrode or a wiring can be formed by directly drawing on a film. As such materials, a metal nanopaste or ink containing metal nanoparticles such as silver, or a paste or ink containing metal oxide-containing nanoparticles can be used. Further, a solution of a conductive polymer or the like can also be used. As the method of drawing the above-mentioned transistor and electrode/wiring, an inkjet method, a screen printing method, a gravure printing, a flexographic printing, or a nano printing technique can be employed. Further, a TFT circuit or the like can be formed on the film by transfer.

On the flexible circuit board manufactured as described above, a layer necessary for forming a display layer such as a liquid crystal display or an organic EL display can be further formed, and processing can be performed so as to have a layer structure corresponding to each display.

As shown in FIG. 2B, in the plan view of the laminated body 10 on which the transparent circuit substrate 15 is formed, the outer periphery of the pattern processing region on the transparent workpiece 13 (the outermost periphery of the pattern 14) is preferably located on the lower adhesive layer 11b. Outside the inner circumference. Therefore, even when the peripheral portion of the transparent circuit substrate is cut out, or when the transparent circuit substrate is diced one by one, the low-adhesion layer 11b can be distributed to the transparent portion. The circuit board can be easily peeled off from the support 12.

[Peeling step]

Then, the transparent circuit board 15 is peeled off from the temporary fixing member 11. Specifically, first, as shown in FIGS. 2C and 2D, the support 12 and the temporary fixing member 11 are peeled off with the surface of the temporary fixing member 11 on the side of the support 12 as an interface. As described above, the temporary fixing member 11 has not only the high adhesive layer 11a but also the low adhesive layer 11b having a lower adhesive force than the high adhesive layer 11a. Therefore, the support can be easily separated from the transparent circuit substrate by an external force.

Further, the central portion 11C of the temporary fixing member 11 is formed by laminating a high-adhesion layer 11a and a low-adhesion layer 11b. Therefore, the central portion 11C formed by laminating the high-adhesion layer 11a and the low-adhesion layer 11b has a relatively low adhesive force as compared with the peripheral portion 11P formed only of the high-adhesion layer 11a. Thereby, the support can be easily separated from the transparent circuit substrate by applying an external force. Further, since the high-adhesion layer 11a is formed on the peripheral edge portion 11P of the temporary fixing member 11, the high-adhesion layer 11a can be dissolved by a solvent or the slit can be physically cut by a cutter or a laser. The adhesion of the peripheral portion 11P to the central portion 11C is broken, and the temporary fixing member 11 can be more easily peeled off from the support 12. As a method of blocking the adhesion of the high-adhesion layer 11a or reducing the adhesion, a method of dissolving the high-adhesion layer 11a by a solvent to block the adhesion, and using a cutter or a laser to be equal to the high-adhesion layer 11a A method of physically cutting out a slit to block an adhesive force, a method of forming a high-adhesion layer 11a by a material whose adhesion is lowered by heating, and lowering an adhesive force by heating. In Fig. 2C, before the peeling, the slit is physically cut at a position slightly inside the outer circumference of the central portion 11C. Thereby, the adhesion of the peripheral portion 11P to the central portion 11C is blocked, and only the low-adhesion layer 11b has an adhesive force to the support in the central portion 11C, so that the separation of the central portion 11C from the support 12 can be made easier. .

Then, as shown in FIG. 2D, the transparent circuit substrate 15 can be recovered by peeling the transparent circuit substrate 15 together with the temporary fixing member 11 from the support 12. The transparent circuit substrate 15 including the pattern processing region in which the pattern 14 is formed is positioned above the low-adhesion layer 11b, so that the peeling of the transparent circuit substrate 15 from the support 12 can be easily performed. 2A to 2D, a state in which one transparent circuit substrate 15 is formed on the temporary fixing member 11, but the present invention is not limited thereto, and a procedure may be employed in which a plurality of temporary fixing members 11 are attached to each other. Each of the transparent workpieces is patterned to form a plurality of transparent circuit substrates, and then the adhesive force of the high-adhesion layer 11a is blocked as described above to recover the transparent circuit substrates. Alternatively, the following procedure may be employed: forming a plurality of pattern processing zones for one transparent workpiece In the field, a plurality of transparent circuit substrates are formed by patterning each of the pattern processing regions, and thereafter, the adhesion of the high-adhesion layer 11a as described above is blocked, and the respective transparent circuit substrates are recovered.

In the transparent circuit board 15 which is peeled off together with the temporary fixing material 11, the temporary fixing material 11 can be removed from the transparent circuit board 15 without being subjected to special treatment.

<Second embodiment>

The temporary fixing material of the present invention is not limited to the shape of the temporary fixing member 11. Fig. 3 is a schematic cross-sectional view showing a temporary fixing member according to a second embodiment of the present invention. As shown in FIG. 3, in the temporary fixing member 21, the peripheral edge portion 21P is formed of the high-adhesion layer 21a, and the central portion 21C on the inner side of the peripheral edge portion 21P is formed of the low-adhesion layer 21b. The adhesion of the low adhesion layer 21b is lower than the adhesion of the high adhesion layer 21a.

In the temporary fixing member 21, since the central portion 21C is formed of the low-adhesion layer 21b, the support and the transparent circuit substrate can be easily separated up and down by an external force in the peeling step.

The central portion 21C of the temporary fixing member 21 is formed of the low-adhesion layer 21b, and the low-adhesion layer 21b is also connected to the support. Therefore, in the peeling step, the temporary fixing member 21 is easily peeled off from the support. Therefore, it is easy to reuse the support. Further, since the high-adhesion layer 21a is formed on the peripheral edge portion 21P of the temporary fixing member 21, the high-adhesion layer 21a is dissolved by a solvent in the peeling step, or the slit is physically cut by a cutter or a laser. The adhesion of the high-adhesion layer 21a to the central portion 21C is blocked, and the temporary fixing member 21 can be more easily peeled off from the support.

Other matters including the composition of the temporary fixing member 21 and the like can be the same as in the first embodiment.

<Third embodiment>

The temporary fixing material of the present invention is not limited to the shape of the temporary fixing members 11, 21. Fig. 4 is a cross-sectional schematic view showing a temporary fixing member according to a third embodiment of the present invention. As shown in Fig. 4, the temporary fixing member 31 is formed by laminating a high-adhesion layer 31a and a low-adhesion layer 31b. Low viscosity The adhesion of the layer 31b is lower than the adhesion of the high adhesion layer 31a.

Since the high-adhesion layer 31a is present in the temporary fixing member 31, the transparent circuit board can be fixed to the support in the processing step or the like. Further, not only the high-adhesion layer 31a but also the low-adhesion layer 31b having a lower adhesive force than the high-adhesion layer 31a is provided. Therefore, in the peeling step, the support and the transparent circuit substrate can be easily separated from each other by an external force.

The thickness of the high-adhesion layer 31a is not particularly limited, and is, for example, 10 μm or more, and preferably 20 μm or more. When the thickness is 10 μm or more, the unevenness of the surface of the transparent workpiece can be followed, and the temporary fixing member 31 can be filled between the transparent workpiece and the support without a gap. Further, the thickness of the high-adhesion layer 31a is, for example, 100 μm or less, preferably 50 μm or less. When it is 100 μm or less, thickness unevenness or shrinkage/expansion upon heating can be suppressed or prevented.

The thickness of the low-adhesion layer 31b is not particularly limited, and is, for example, 1 μm or more, and preferably 5 μm or more. When it is 1 μm or more, the unevenness of the surface of the support can be followed, and the temporary fixing material 31 can be filled between the transparent workpiece and the support without a gap. Further, the thickness of the low-adhesion layer 31b is, for example, 50 μm or less, preferably 20 μm or less. When it is 50 μm or less, thickness unevenness or shrinkage/expansion during heating can be suppressed or prevented.

Regarding the adhesion of the low-adhesion layer 31b, for example, at a temperature of 23±2° C. and a peeling speed of 300 mm/min, the 90° peeling force to the glass plate is preferably less than 0.05 N/20 mm, more preferably 0.04 N/20 mm. the following. If it is less than 0.05 N/20 mm, the transparent circuit substrate can be easily separated from the support. On the other hand, the lower limit of the 90° peeling force is preferably 0.01 N/20 mm or more, more preferably 0.02 N/20 mm or more, and still more preferably 0.03 N/20 mm or more. When it is 0.01 N/20 mm or more, the transparent workpiece can be favorably fixed to the support, and the pattern processing can be performed favorably.

Other matters including the composition of the temporary fixing member 31 and the like can be the same as in the first embodiment.

<Fourth embodiment>

The temporary fixing material of the present invention is not limited to the shape of the temporary fixing members 11, 21, and 31. Fig. 5 is a cross-sectional schematic view showing a temporary fixing member according to a fourth embodiment of the present invention. As shown in FIG. 5, in the laminated body 40, the low-adhesion layer 41b is disposed between the transparent workpiece 43 and the support 42, and the high-adhesion layer 41a is connected to the outer peripheral side of the transparent workpiece 43 and the outer peripheral side of the support 42. The way it is configured. Thereby, the high-adhesion layer 41a is not attached to the pattern processing region in which the pattern 44 of the transparent workpiece 43 is formed, and the transparent workpiece 43 can be processed in a clean state. Further, in the peeling of the transparent workpiece 43 from the support 42, only the portion of the high-adhesion layer 41a located on the outer periphery can be peeled off or cut off, so that the production efficiency can be improved.

When the high-adhesion layer 41a is disposed on the outer peripheral side surface of the laminated body 40, the height h of the high-adhesion layer 41a is preferably 50% or more and less than 100% of the height H of the laminated body in the side view of the laminated body 40. Preferably, it is 60% or more and less than 90%. Thereby, the transparent workpiece 43 can be firmly fixed to the support body 42, and the high-adhesion layer 41a can be prevented from being folded into the machined surface of the transparent workpiece 43, and the transparent workpiece 43 can be cleanly processed.

The thickness of the high-adhesion layer 41a (the amount of protrusion from the outer peripheral side surface of the laminated body 40) is not particularly limited, and the upper limit thereof is preferably 500 μm or less, and more preferably 200 μm or less. Thereby, it is possible to prevent the high-adhesion layer 41a from being folded into the pattern processing region, or to prevent the high-adhesion layer 41a from adhering to the support 42 when the high-adhesion layer 41a is not attached to the support 42. Further, the lower limit of the thickness is preferably 5 μm or more, and more preferably 10 μm or more. Thereby, the fixing of the transparent workpiece 43 to the support body 42 can be made stronger.

For example, a method of forming the laminated body 40 including the temporary fixing member 41 may be performed by bonding the low-adhesion layer 41b formed on the spacer to the support member 42, and bonding the transparent workpiece 43 to the low-adhesion layer 41b. The low-adhesive laminated body is thereafter formed to be high over the outer peripheral side of the low-adhesive laminated body (that is, one portion of the outer peripheral side of the transparent workpiece 43, the outer peripheral side of the low-adhesion layer 41b, and one of the outer peripheral sides of the support 42). Adhesive layer 41a. As a method of forming the high-adhesion layer 41a toward the outer peripheral side surface of the low-adhesion layered body, a procedure may be employed in which a composition solution for forming the high-adhesion layer 41a is applied to the outer peripheral side surface.

Other matters including the composition of the temporary fixing member 41 and the like can be the same as in the first embodiment.

<Other Embodiments>

The shape of the high-adhesion layer and the low-adhesion layer when the temporary fixing material is viewed from above is not limited to a rectangular shape, and may be independently formed into other shapes such as a circle, a polygon, and an ellipse.

In the above, the method of manufacturing the transparent circuit board of the present embodiment has been described. However, the method of manufacturing the transparent circuit board of the present invention is not limited to the above examples, and can be appropriately changed within the scope of the gist of the invention.

[Examples]

Hereinafter, the embodiments of the present invention will be described in detail, and the present invention is not limited to the following embodiments as long as the present invention does not deviate from the gist of the invention.

The ingredients used in the examples are as follows.

PMDA: pyromellitic dianhydride (molecular weight: 218.1)

ELASMER1000: Diamine with alkyl ether structure manufactured by Ihara Chemical Industry Co., Ltd. (molecular weight: 1229.7)

Dymer 1075: Linear alkyl diamine manufactured by Croda Japan Co., Ltd. (molecular weight: 537.0)

TFMB: 2,2'-bis(trifluoromethyl)benzidine (molecular weight: 320.2)

DDE: 4,4'-diaminodiphenyl ether (molecular weight: 200.2)

NMP: N-methyl-2-pyrrolidone

DMAc: N,N-dimethylacetamide

Commercially available polyimine sheet: Polyethylenimine film manufactured by Toray Dupont Co., Ltd. "Kapton (registered trademark) 20EN"

(Example 1)

Under the nitrogen flow, ELASMER1000 33.95g, DDE 17.42g, and PMDA 25g were mixed in 305.5g of NMP at 80 ° C, respectively, to obtain the reaction. A polyamic acid solution A1 for a high adhesion layer is obtained. Further, according to the composition for the low-adhesion layer of Table 1, the poly-proline solution A2 was obtained by the same method as the polyamic acid solution A1. The obtained polyaminic acid solution A1 was cooled to 23 ° C, applied to a separator, and dried at 90 ° C for 3 minutes to obtain a polyacrylic acid sheet A1 having a thickness of 10 μm (high adhesion layer precursor) ). Similarly, a polyaminic acid sheet A2 (low adhesion layer precursor) having a thickness of 5 μm was obtained by using polyamic acid solution A2.

The polyamic acid sheet A2 was formed into a size of 120 mm × 120 mm, and bonded to a polylysine sheet A1 having a size of 200 mm × 200 mm at a temperature substantially coincident with each other at 90 ° C to obtain a polyfluorene sheet. Amino acid sheet A. The polyamic acid sheet A obtained is imidized under a vacuum atmosphere of 10 Pa or less at 350 ° C for 1.5 hr to obtain a polyimine sheet A1 as a high adhesion layer and as a low The laminate of the adhesive layer of the polyimide sheet A2, that is, the temporary fixing material A.

The obtained temporary fixing material A was bonded to a glass plate having a length of 150 mm × a width of 150 mm × a thickness of 1 mm at a temperature of 90 ° C at a central portion of the polyimide film A2, and cut along the outer periphery of the glass plate. The material A is temporarily fixed, and the temporary fixing material A with the glass plate is obtained.

(Example 2)

The temporary fixing material B and the temporary fixing material B with the glass plate were obtained in the same manner as in the first embodiment except that the composition and thickness of each of the high-adhesive layer and the low-adhesive layer were in accordance with Table 1.

(Example 3)

According to the composition of Table 1, a polyacetic acid sheet C1 having a thickness of 10 μm as a precursor of the high adhesion layer was obtained by the same procedure as in Example 1.

In addition, an aluminum vapor-deposited film C2 of 120 mm × 120 mm × 50 nm thick was formed on a glass plate having a length of 150 mm × a width of 150 mm × a thickness of 1 mm (a vapor deposition device: "UPC-410" manufactured by ULVAC Co., Ltd., conditions: 70 A, 10 s), and was set to Low adhesion layer.

Polyacrylic acid sheet C1 of 200 mm × 200 mm size will be formed at 90 ° C to each other The aluminum vapor deposited film C2 is bonded to the formed aluminum foil in a manner that the center of gravity is substantially uniform. Then, the laminated polylysic acid sheet C1 was imidized under vacuum at 350 ° C × 1.5 hr in a vacuum environment of 10 Pa or less to obtain a polytheneimide sheet C1 and an aluminum vapor-deposited film C2. The temporary fixing material C of the laminated body.

Finally, the temporary fixing material C was cut along the outer peripheral portion of the glass sheet to obtain a temporary fixing material C attached to the glass sheet.

(Example 4)

According to the composition of Table 1, a polyphthalic acid sheet D1 having a thickness of 20 μm as a precursor of the high adhesion layer was obtained in the same procedure as in Example 1. A commercially available polyimine sheet (Kapton (registered trademark)) D2 was formed into a size of 120 mm × 120 mm, and adhered to a size of 200 mm × 200 mm in a manner to substantially coincide with each other at 90 ° C. The amino acid sheet D1 was obtained to obtain a poly-proline sheet D. The obtained polyamic acid sheet D is imidized under a vacuum atmosphere of 10 Pa or less at 350 ° C × 1.5 hr to obtain a polyimine sheet D1 as a high adhesive layer and as a low The laminated body of the commercially available polyimine sheet D2 of the adhesive layer, that is, the temporary fixing material D.

The obtained temporary fixing material D was bonded to a glass plate having a length of 150 mm × a width of 150 mm × a thickness of 1 mm at a temperature of 150 ° C at a central portion of the commercially available polyimide film D2, along the outer periphery of the glass plate. The temporary fixing material D was cut out, and the temporary fixing material D with the glass plate was obtained.

(Comparative Example 1)

According to the composition of Table 1, a polyacrylic acid sheet E1 having a thickness of 20 μm was obtained by the same procedure as in Example 1. The obtained polyamic acid sheet E1 is imidized under a vacuum environment of 10 Pa or less under conditions of 350 ° C × 1.5 hr to obtain a temporary fixing material formed of a single-layer polyimine sheet E1. E.

The obtained temporary fixing material E was bonded to a glass plate having a length of 150 mm × a width of 150 mm × a thickness of 1 mm at 90 ° C, and the temporary fixing material E was cut out along the outer periphery of the glass plate to obtain an attached Temporary fixing material E with glass plate.

[Determination of Adhesion of High Adhesive Layer and Low Adhesive Layer]

The layer formed only of the polyamic acid sheets A1 to E1 of the respective examples and comparative examples and the layer formed only of the polyamic acid sheets A2 to B2 were respectively bonded to a glass plate to be equal to a nitrogen atmosphere. The yttrium imidization was carried out at 300 ° C for 1.5 hours to obtain a polyimide sheet attached to a glass plate as a high adhesion layer and a low adhesion layer monomer. In the third embodiment, the aluminum vapor-deposited film C2 was formed on the glass plate to form a low-adhesion layer. In the fourth embodiment, the Kapton (registered trademark) polyimide sheet D2 was directly set as a low-adhesive layer, and each was attached. Combined with a glass plate. The high-adhesive layer A1~E1 with the glass plate and the low-adhesive layer A2~D2 with the glass plate were processed into 20 mm wide and 100 mm long, respectively, using a tensile tester (manufactured by Shimadzu Corporation, Autograph AGS-H) at a temperature of 23 The 90° peel force evaluation was performed at °C and 300 mm/min. The results are shown in Table 2.

[Chemical resistance evaluation]

The measurement samples were prepared by cutting 50 mm squares near the center of the temporary fixing materials A to E of the examples and the comparative examples, and drying the samples in a desiccator controlled at 25 ° C and 20% Rh for 24 hours. The measurement was carried out and recorded as weight 1. Thereafter, the measurement sample was immersed in 100 ml of a 10% aqueous sodium hydroxide (NaOH) solution at room temperature for 5 minutes, and utilized. After the ultrapure water was sufficiently washed, it was again dried by a drier for 24 hours, and the weight 2 was measured. This weight 1 and weight 2 were substituted into the following formula 1, and the weight reduction rate was calculated, and the alkali resistance was evaluated.

Weight reduction rate (%) = {(weight 1 - weight 2) / weight 1} × 100

Similarly, each sample was immersed in 100 ml of a 10% sulfuric acid aqueous solution (room temperature) for 5 minutes to evaluate acid resistance, and each sample was immersed in 100 ml of 3% tetramethylammonium hydroxide (room temperature) for 5 minutes to evaluate. Solvent resistance. The evaluation of the alkali resistance, the acid resistance, and the solvent resistance was evaluated as "○" when the weight reduction rate was less than 1%, and "x" when the weight reduction rate was 1% or more. The results are shown in Table 2.

(Measurement of weight reduction rate by differential thermal-thermal weight simultaneous measurement)

After taking about 10 mg of each sample, a differential heat-thermal weight synchronous meter ("TMA-8310", manufactured by RIGAKU Co., Ltd.) was used in a nitrogen atmosphere (flow rate: 100 ml/min) at a temperature range of 25 to 400 ° C at 5 ° C. The sample is heated at a heating rate of /min. In this case the initial weight of the weight at ₂₀₀ ℃ 200 measured weight reduction rate (%) at the 200 ℃ based on the following formula according to.

Weight reduction rate (%) = {(initial weight - weight ₂₀₀ ) / initial weight} × 100

[Resistance evaluation]

A tempered glass of 100 mm × 60 mm ("Gorilla Glass" manufactured by Corning Co., Ltd.) was bonded to temporary fixing materials A to E with glass plates at 120 ° C, 4.5 kN, 3000 Pa, and 60 seconds. Then, it was subjected to vacuum high temperature treatment for 3 hours in an environment of 300 ° C and 5 Pa, and the peeling of the tempered glass or the peeling of the temporary fixing material from the glass plate was evaluated as "○", and the visible case was evaluated as "X". The results are shown in Table 2.

[Evaluation of the peelability of glass sheets]

In the process of evaluation of the resistance to the treatment, the inside of the outer peripheral portion of the glass plate of the temporary fixing material A to E of the glass plate to which the tempered glass is attached is placed, and the slit is cut from the directly above the temporary fixing material until it reaches the glass plate, and the visible is formed. The state of the glass plate. After cutting into the incision, The tempered glass is adsorbed upward using vacuum tweezers. The case where the tempered glass and the temporary fixing material were peeled off from the glass plate by adsorption was evaluated as "○", and the case where peeling could not be peeled off was evaluated as "x". The results are shown in Table 2.

[Evaluation of tempered glass peelability]

After the bonding of the tempered glass to the temporary fixing material A to E and the vacuum high temperature treatment, the adhesive tape (No. 315B, manufactured by Nitto Denko Corporation) is attached to the surface of the temporary fixing material, and then used. Tensile testing machine (Autograph AGS-H, manufactured by Shimadzu Corporation), using a load of 5N at a temperature of 23 ° C and 300 mm/min to peel off the temporary fixing material and the tempered glass at a peeling force of 90°, which will temporarily fix the material. The case where the tempered glass was peeled off was evaluated as "○", and the case where peeling was performed at a set temperature of 100 ° C was evaluated as "Δ", and the case where peeling could not be performed was evaluated as "x". The results are shown in Table 2.

As can be seen from Table 1, the results of the temporary fixing materials of the examples were good in the retention properties during tempered glass processing, peelability after processing, chemical resistance, and heat resistance (suppression of outgassing). Although the temporary fixing material of the comparative example has good chemical resistance, the tempered glass cannot be held, and the tempered glass cannot be processed.

11‧‧‧ Temporary fixtures

11a‧‧‧High adhesion layer

11b‧‧‧Low adhesive layer

11C‧‧‧The central part of temporary fixtures

11P‧‧‧ Peripheral parts of temporary fixtures

Claims (5)

A method for manufacturing a transparent circuit substrate, comprising: a laminate preparation step of preparing a laminate in which a transparent workpiece is temporarily fixed to a support via a temporary fixing member, and the processing step is performed by including 200 ° C or higher Forming a heat-treated pattern to form a transparent circuit substrate on the transparent workpiece, and a peeling step of peeling the transparent circuit substrate from the temporary fixing material; and heating the substrate at a temperature increase rate of 5 ° C/min When the temperature was raised to 400 ° C and the differential thermal-thermal weight synchronization measurement was performed, the weight reduction rate of the temporary fixing material at 200 ° C was less than 1%. The method of manufacturing a transparent circuit substrate according to claim 1, wherein the temporary fixing material comprises: a high-adhesion layer having an adhesion force of 0.05 N/20 mm or more and 10 N/20 mm or less to the glass plate, and a low adhesion layer to the glass The board has an adhesion of 0 N/20 mm or more and less than 0.05 N/20 mm. The method of manufacturing a transparent circuit substrate according to claim 2, wherein in the plan view of the laminated body after the pattern formation, the outer periphery of the pattern processing region on the transparent workpiece is located further inside than the outer periphery of the low adhesive layer. The method of manufacturing a transparent circuit substrate according to claim 2, wherein in the laminated body, the low adhesion layer is disposed between the transparent workpiece and the support, and the high adhesion layer is configured to support the outer peripheral side of the transparent workpiece and the support The outer side of the body is connected to the side. A method of manufacturing a transparent circuit substrate according to claim 4, wherein the side of the laminate is In view of the above, the height of the high adhesion layer is 50% or more of the height of the laminate and is less than 100%.