TW201604005A - Complex - Google Patents

Abstract

An object of the present invention is to provide a composite which is less likely to be broken when a tensile stress is applied to a glass substrate having a micro crack on its surface. The present invention relates to a composite in which the resin of the resin layer penetrates into at least a part of the inside of the micro crack, and the ratio of the depth of the resin to the depth df of the surface of the glass substrate relative to the depth d of the micro crack, and the elongation at break of the resin layer The product of the rate TE (%) and the relief stress σS (MPa) of the above resin layer is 400 MPa‧% or more, and the tensile elastic modulus of the above resin layer is 1.0 GPa or more.

Description

Complex

The present invention relates to a composite, and more particularly to a composite in which a resin penetrates to a specific depth inside a microcrack on the surface of a glass substrate.

A composite sheet having a glass sheet and a resin layer bonded to the glass sheet is proposed as a substrate of an electronic device such as an image display panel, a solar cell, or a thin film secondary battery (see, for example, Patent Document 1). When the glass sheet contained in the composite sheet is bent and deformed by a specific radius of curvature to cause tensile stress on the main surface of the glass sheet combined with the resin layer, the tensile stress is reduced by the presence of the resin layer. small. Thereby, the breakage of the glass sheet can be suppressed.

[Previous Technical Literature] [Patent Literature]

Patent Document 1: International Publication No. 2012/166343

On the other hand, the glass substrate is usually subjected to various treatments such as a cleaning treatment, a polishing treatment, and a cutting treatment, and at this time, minute cracks are formed on the surface of the glass substrate.

The inventors of the present invention have found that a resin layer is formed on a glass substrate having micro cracks formed on the surface thereof by a specific treatment, and the characteristics of the composite are evaluated. As a result, it is found that when a tensile stress is applied to the glass substrate, There is a case where it is easy to break.

The present invention is directed to the above-mentioned actual situation, and aims to provide a presence on the surface A composite in which a glass substrate of a microcrack is less likely to be broken when a tensile stress is applied.

The inventors of the present invention have diligently studied to solve the above problems, and have completed the present invention.

That is, the first aspect of the present invention is a composite comprising a glass substrate having a micro crack on its surface and a resin layer disposed on the glass substrate, and the resin of the resin layer penetrates into at least the inside of the micro crack. a part of the ratio of the depth d _f of the resin to the depth d of the surface of the glass substrate to the depth d of the microcrack (d _f /d), the elongation at break TE (%) of the resin layer, and the fall of the resin layer the product of the stress [sigma] _S (MPa) (the ratio of (d _f / d) × elongation at break TE × yield stress σ _S) or more 400MPa‧%, the resin layer and a tensile modulus of elasticity E _resin is 1.0GPa or more.

In the first aspect, the glass substrate preferably has an average thickness of 10 to 200 μm.

In the first embodiment, the resin layer preferably has an average thickness of 10 to 100 μm.

In the first aspect, it is preferred that the resin layer contains polyimide.

According to a second aspect of the invention, there is provided an electronic device comprising the composite of the first aspect and an element formed on the glass substrate of the composite.

According to the present invention, it is possible to provide a composite which is less likely to be broken when a tensile stress is applied to a glass substrate having a micro crack on its surface.

2‧‧‧Compound

4‧‧‧ glass substrate

6‧‧‧ resin layer

8‧‧‧Small cracks

8a‧‧‧Linear cracks

8b‧‧‧ point-like tiny crack

10‧‧‧Bending test device

14‧‧‧Upper support disk

14a‧‧‧Support surface of the upper support disk

16‧‧‧Lower support disk

16a‧‧‧Support surface of the lower support disk

17‧‧‧Department

18‧‧‧Test sheet

70‧‧‧Organic EL Panel (OLED)

71‧‧‧Organic EL components

72‧‧‧pixel electrode

74‧‧‧Organic layer

76‧‧‧ opposite electrode

78‧‧‧ Sealing plate

80‧‧‧LCD panel

82‧‧‧TFT substrate

83‧‧‧TFT components

84‧‧‧CF substrate

85‧‧‧Color filter components

86‧‧‧Liquid layer

90‧‧‧Solar battery

91‧‧‧Solar battery components

92‧‧‧Transparent electrode

94‧‧‧矽

96‧‧‧Reflective electrode

98‧‧‧ Sealing plate

100‧‧‧Film secondary battery

101‧‧‧Film secondary battery components

102‧‧‧Transparent electrode

104‧‧‧ electrolyte layer

106‧‧‧ collector layer

108‧‧‧ Sealing layer

109‧‧‧ Sealing plate

110‧‧‧electronic paper

111‧‧‧Electronic paper components

112‧‧‧TFT layer

114‧‧‧ Layer containing electrical media

116‧‧‧Transparent electrode

118‧‧‧ front panel

d‧‧‧Deep crack depth

d _f ‧‧‧Deep depth of resin from the surface of the glass substrate

D‧‧‧Interval between the support surface of the upper support disk and the support surface of the lower support disk

W‧‧‧The width of tiny cracks

Fig. 1 is a cross-sectional view showing an embodiment of a composite of the present invention.

2 is a plan view of a glass substrate having minute cracks.

Fig. 3 is a cross-sectional view showing the structure of an organic EL panel according to an embodiment of the present invention.

Fig. 4 is a cross-sectional view showing the structure of a liquid crystal panel according to an embodiment of the present invention.

Fig. 5 is a cross-sectional view showing the structure of a solar cell according to an embodiment of the present invention.

Figure 6 is a cross-sectional view showing the structure of a thin film secondary battery according to an embodiment of the present invention. Figure.

Fig. 7 is a cross-sectional view showing the structure of an electronic paper according to an embodiment of the present invention.

Fig. 8 is a schematic view showing a bending test apparatus for detecting the average breaking strength of the glass substrate and the composite according to the embodiment of the present invention.

Fig. 9(A) and Fig. 9(B) are diagrams in which luciferin is adsorbed on the surface of a glass substrate having minute cracks, and the glass substrate is broken, and the broken section is observed by an optical microscope (Fig. 9(A) ) and a view obtained by observation with a fluorescence microscope (Fig. 9(B)).

The form for carrying out the invention will be described below with reference to the drawings. In the drawings, the same or corresponding components are designated by the same or corresponding reference numerals, and the description is omitted. Furthermore, the drawings in the present invention are schematic diagrams, and the relationship of the thicknesses of the layers, the positional relationship, and the like are not necessarily identical to the actual objects. Further, in the present specification, "% by weight" has the same meaning as "% by mass".

One of the characteristics of the composite of the present invention is that the properties of the resin layer (elongation at break, the stress at break, the modulus of tensile modulus) are controlled, and the resin in the resin layer penetrates into the minute crack of the glass substrate. The specific depth. It is considered that the glass substrate is easily broken due to minute cracks existing on the surface of the glass, and it is presumed that when a stress is applied to the glass, the minute crack largely extends to cause cracking. Therefore, as described above, the desired effect is obtained by the resin which exhibits a specific characteristic penetrates into the inside of the minute crack.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing an example of a composite of the present invention.

The composite 2 has a glass substrate 4 and a resin layer 6 disposed on the glass substrate 4. A micro crack 8 is present on the surface of the glass substrate 4 on the resin layer 6 side, and the resin in the resin layer 6 penetrates at least a part of the inside of the micro crack 8.

The composite 2 may be used as a substrate for an electronic device such as an image display panel, a solar cell, or a thin film secondary battery, or may be used to form various components. The composite 2 may be wound on a core or may be a manufacturer of an electronic device for use in a roll-to-roll process.

In addition, in FIG. 1, the resin layer 6 is provided only on one side of the glass substrate 4, and it may be interposed. The resin substrate 6 is provided on both sides of the glass substrate 4, respectively. The two resin layers 6 disposed through the glass substrate 4 may have the same thickness or different thicknesses, and may have the same physical properties (tensile elastic modulus, thermal expansion coefficient, etc.) or different physical properties.

First, the glass substrate 4 and the resin layer 6 which comprise the composite 2 are demonstrated in detail below.

<glass substrate>

The glass of the glass substrate 4 can be various, and examples thereof include soda lime glass and alkali-free glass.

The average thickness of the glass substrate 4 is not particularly limited, but is preferably 200 μm or less. When the average thickness of the glass substrate 4 is 200 μm or less, the glass substrate 4 can be wound into a spiral shape to form a glass roll.

The average thickness of the glass substrate 4 is preferably 150 μm or less, more preferably 100 μm or less, still more preferably 50 μm or less. Further, the average thickness of the glass substrate 4 is preferably 0.1 μm or more, more preferably 1 μm or more, still more preferably 5 μm or more, and still more preferably 10 μm or more.

Further, the average thickness is a value obtained by measuring the thickness of the glass substrate 4 of any ten or more points and arithmetically averaging them.

The thickness deviation in the width direction of the glass substrate 4 is preferably 5 μm or less. The term "thickness deviation" means the deviation from the average thickness. When the thickness deviation in the width direction of the glass substrate 4 is 5 μm or less, the composite 2 is equal to the stress generated on the glass substrate 4 when it is bent and deformed, and the damage of the glass substrate 4 can be reduced. Further, the thickness variation in the longitudinal direction of the glass substrate 4 is generally smaller than the thickness deviation in the width direction of the glass substrate 4. The thickness deviation in the width direction of the glass substrate 4 is more preferably 3 μm or less, further preferably 1 μm or less, and particularly preferably 0.5 μm or less. The thickness deviation in the width direction of the glass substrate 4 was determined by measuring the uneven shape of the front and back surfaces of the glass substrate 4 by a laser displacement meter.

The glass substrate 4 may have a strip shape, and the glass substrate 4 may have a width of 100 mm or more. When the width of the glass substrate 4 is 100 mm or more, the electronic loading by the roll-to-roll method In the manufacturing step, there is a case where the tensile force applied to the composite 2 becomes uneven in the width direction, and there is a case where the tensile stress concentrates on one portion of the glass substrate 4. In the above case, the effect of the present embodiment (the effect of reducing the damage of the glass substrate 4) is remarkably exhibited.

The method for producing the glass substrate 4 may be any of a floating method, a melting method, and a re-drawing method. In the case of the floating method, the molten glass is flowed on the molten tin in the bath to form a strip shape, and after the formed glass is slowly cooled, the cooled glass is cut into a desired size. In the case of the melting method, the molten glass overflowing from the groove-like member is merged at the lower end of the groove-like member to be formed into a strip shape, and after the formed glass is slowly cooled, the cooled glass is cut into a desired size. . In the case of the re-drawing method, the glass substrate is softened by heat, stretched to a desired thickness, and the stretched glass substrate is cured.

There are minute cracks 8 on the surface of the glass substrate 4. The microcracks 8 are generated when various processes (cleaning process, polishing process, cutting process, etc.) are performed when a glass substrate is manufactured, or when a glass substrate or the like is handled. The shape of the microcracks 8 is not particularly limited. For example, as shown in FIG. 2, which is a plan view of the glass substrate 4 having minute cracks, for example, a shape 8a in which the groove-like recesses extend in a line shape or a dot-shaped recess shape 8b is exemplified. .

The so-called micro cracks 8 mainly refer to cracks (damages) of a size below a minor size.

The size of the depth d of the microcracks 8 is not particularly limited, and may be 0.1 μm or more, and more preferably 1.0 μm or more, as measured by an electron microscope or the like. Further, the upper limit is not particularly limited, and is usually 30 μm or less, and more often 15 μm or less.

The size of the width W of the microcracks 8 is not particularly limited, and may be 1 nm or more in the range detected by an electron microscope or the like, and more preferably 10 nm or more. Further, the upper limit is not particularly limited, and is usually 100 μm or less, and more often 10 μm or less.

As a method of measuring the depth d and the width W of the microcrack 8, the method of cutting the composite 2 and observing the cut surface by an electron microscope is exemplified.

<Resin layer>

The resin layer 6 is a layer disposed on the glass substrate 4, and functions as a reinforcing layer that reinforces the rupturability of the glass substrate 4.

The relationship between the resin layer 6 and the glass substrate 4 described below satisfies the following formula (1).

Formula (1) :( ratio _{(d f / d)) ×} ( breaking elongation of the resin layer TE) × (yield stress of the resin layer σ _S) ≧ 400MPa‧%

Hereinafter, each item in the formula will be described in detail first.

As shown in FIG. 1, the resin in the resin layer 6 penetrates (fills) a portion of the inside of the minute crack 8. The ratio of the depth d _f (filling depth) of the resin to the depth d of the micro crack (d _f /d) of the surface of the glass substrate 4 (the embedding ratio of the resin in the depth direction of the micro crack) is as long as the above formula is satisfied ( 1) The relationship is not particularly limited, and it is preferably 0.01 or more, and more preferably 0.05 or more, in terms of the fact that the composite is less likely to be broken (hereinafter also referred to as "the aspect of the present invention is more excellent"). It is preferably 0.1 or more. The upper limit is not particularly limited, and since the depth d _{f is} not larger than the depth d of the minute crack, it is 1 or less. The depth d _f described above indicates the deepest position of the resin deep inside the micro crack based on the surface of the glass substrate 4.

The above ratio (d _f /d) is an average value, that is, 10 or more micro cracks are observed, the depth d of each micro crack and the depth d _{f are} measured, and the ratio of each micro crack (d _f /d) is calculated, and The ratio of the calculated micro cracks (d _f /d) is arithmetically averaged.

The depth d and the depth d _f are obtained by directly observing the fracture origin by an optical microscope after performing a failure test of the composite. Further, according to the basic formula of the failure mechanics ("ceramic destruction" P68), the theoretical value can be obtained from the failure stress and the stress intensity factor, and the correctness of the above value can be confirmed. Further, regarding the depth _df , the dye is dispersed in the resin to be coated in advance, whereby the origin of destruction after the breaking test can be observed by a fluorescence microscope, and the size thereof is measured and compared with the depth d. Here, the dye is not particularly limited, and is preferably luciferin or a derivative thereof.

Moreover, in the case of a resin liquid in which the dispersibility of the pigment is poor, the viscosity can be used uniformly. The water-soluble resin is used as an observation resin. By making the viscosity of the composition for forming a resin layer which is actually used for forming the resin layer coincide with the viscosity of the composition for evaluation including the observation resin and the dye, the composition for evaluation is invaded into the inside of the micro crack of the depth d. The degree is the same as that in the case of using the composition for forming a resin layer. Here, the water-soluble resin means polyvinyl alcohol (PVA), hydroxy cellulose (HEC), or the like. Further, the depth d can be obtained by adsorbing the dye on the inner surface of the microcrack and observing the origin of destruction after the breaking test by a fluorescence microscope.

Further, as an example, as shown in FIG. 9(A) and FIG. 9(B), the use of the fracture surface near the fracture starting point of the glass substrate after the luciferin is adsorbed on the surface of the glass substrate having the micro cracks is examined. Photographs were observed with an optical microscope and a fluorescent microscope. Fig. 9(A) is an observation view under an optical microscope, and Fig. 9(B) is an observation view under a fluorescence microscope. The arrow in the figure means the thickness direction of the glass substrate. If the two are compared, the fluorescein derived from the inside of the microcrack can be confirmed on the surface of one of FIG. 9(B) (the surface on the lower side of the glass substrate in the drawing), and the distance glass is The depth d can be calculated from the depth of the fluorescent region on the surface of the substrate. Further, as described above, a pigment (for example, luciferin) may be dispersed in the resin to be coated, and the cross section of the glass substrate after the breaking test may be observed in the same manner as in the above-described FIG. 9(B), thereby observing the above-mentioned depth. d _f .

The breaking elongation TE (%) of the resin layer 6 is not particularly limited as long as it satisfies the relationship of the above formula (1), and is preferably 20% or more, and more preferably in terms of the effect of the present invention. 40% or more.

The elongation at break TE (%) is determined in accordance with ASTM D882-12.

The magnitude of the stress σ _S (MPa) of the resin layer 6 is not particularly limited as long as it satisfies the relationship of the above formula (1), and is preferably 50 MPa or more, more preferably 100 MPa, in terms of the effect of the present invention being more excellent. the above.

The method for determining the stress σ _S is based on JIS-C-2151:2006.

The above formula (1) means that the product of the above ratio (d _f /d), the elongation at break TE of the resin layer 6, and the relief stress σ _S of the resin layer 6 is 400 MPa‧% (N/mm ² ‧%) or more . In the aspect of the present invention, the left side of the formula (1) ((r _f / d)) × (elongation at break TE of the resin layer) × (the stress of the resin layer σ _S) )) is preferably 450 MPa‧% or more, more preferably 500 MPa‧% or more. The upper limit is not particularly limited, and is usually 8,000 MPa ‧ % or less, and more often 2,000 MPa ‧ %

As described above, the reason why the glass substrate 4 is broken is mainly because stress concentrates on the micro cracks 8 existing on the surface of the glass substrate 4, and the glass substrate 4 is easily broken. The present inventors have found that by making the resin which can form the resin layer 6 exhibiting the specific elongation at break TE and the stress σ _S into a certain depth inside the minute crack 8, that is, by satisfying the relationship of the formula (1) The stress in the direction in which the rupture of the microcrack 8 is further extended as shown by the hollow arrow in Fig. 1 can be suppressed.

More specifically, as described above, the reason why the glass substrate is broken is that stress concentrates on minute cracks, but when the resin penetrates into (inserted into) the micro cracks, the energy applied to the micro cracks is distributed according to the depth to which it is deepened. To the resin. At this time, the amount of work performed by the resin is represented by the following formula (X).

In the formula (X), W' represents the amount of work performed by the resin embedded in the microcrack, α represents the embedding rate of the resin in the depth direction of the microcrack, d represents the depth of the microcrack, and σ represents the lodging of the resin. The stress, ε, represents the elongation at break of the resin.

Among the above variables, d (the depth of the microcrack) corresponds to the deepest microcrack corresponding to the lowest strength of the glass passing through a certain step, and if it is the same batch of the glass substrate, there is no large change, and therefore it can be regarded as a substantially constant. Thus, the amount of work W' depends on α, σ and ε. The inventors of the present invention have found that if the product of the three parameters is a specific value, the glass substrate is less likely to be cracked.

In particular, the larger the elongation at break TE of the resin layer 6, the wider the allowable stress of the resin inside the microcrack until the fracture. Further, the larger the relief stress σ _{S of} the resin layer 6 is, the wider the allowable stress of the resin inside the microcrack is up to the undulation.

The tensile elastic modulus E _resin of the resin layer 6 is 1.0 GPa or more, and is preferably 1.5 GPa or more, and more preferably 2.0 GPa or more, in terms of the effect of the present invention being more excellent. The upper limit is not particularly limited, and is usually 15 GPa or less, and more often 10 GPa or less.

The method for measuring the tensile elastic modulus E _resin is based on JIS-C-2151 (2006).

The average thickness of the resin layer 6 is not particularly limited, but is preferably 100 μm or less. When the average thickness of the resin layer 6 is 100 μm or less, the flexibility of the composite 2 can be sufficiently ensured. Moreover, when the average thickness of the resin layer 6 is 100 μm or less, warpage due to a difference in thermal expansion coefficient between the resin and the glass can be suppressed. The average thickness of the resin layer 6 is preferably 90 μm or less, more preferably 75 μm or less. Further, the average thickness of the resin layer 6 is preferably 0.5 μm or more, more preferably 1 μm or more, and still more preferably 10 μm or more from the viewpoint of the effect of the present invention being more excellent.

Further, the average thickness is a value obtained by measuring the thickness of the resin layer 6 of any ten or more points and arithmetically averaging these.

The resin layer 6 can be formed, for example, only of a resin. Further, the resin layer 6 may be formed of a material containing a resin, and may be formed, for example, of a resin or a filler.

Examples of the filler include a fibrous form, a non-fibrous filler cross section such as a plate shape, a scaly shape, a granular shape, an indefinite shape, and a crushed product. Specific examples thereof include glass fiber and PAN (Polyacrylonitrile). Metal fiber such as carbon fiber, stainless steel fiber, aluminum fiber or brass fiber, organic fiber such as aromatic polyamide fiber, gypsum fiber, ceramic fiber, asbestos fiber, zirconia fiber, alumina fiber, cerium oxide Fiber, titanium oxide fiber, tantalum carbide fiber, rock wool, potassium titanate whisker, barium titanate Whiskers, aluminum borate whiskers, tantalum nitride whiskers, mica, talc, kaolin, ceria, calcium carbonate, glass beads, glass flakes, glass microspheres, clay, molybdenum disulfide, apatite, titanium oxide, Zinc oxide, calcium polyphosphate, metal powder, metal flakes, metal strips, metal oxides, carbon powder, graphite, carbon black, scaly carbon, carbon nanotubes, and the like. Specific examples of the metal powder of the metal powder, the metal foil, and the metal strip include silver, nickel, copper, zinc, aluminum, stainless steel, iron, brass, chromium, tin, and the like. The type of the glass fiber or the carbon fiber is not particularly limited as long as it is generally used for resin reinforcement. For example, it can be selected from a long fiber type or a short fiber type woven fiber or a ground fiber. Further, the resin layer 6 may be composed of a woven fabric impregnated with a resin, a nonwoven fabric or the like.

The resin of the resin layer 6 can be various, and for example, it can be any of a thermoplastic resin and a thermosetting resin.

As the thermosetting resin, for example, polyimide (PI), epoxy resin (EP), or the like can be used. As the thermoplastic resin, for example, polyamine (PA), polyamidoximine (PAI), polyetheretherketone (PEEK), polybenzimidazole (PBI), liquid crystal polymer (LCP), polyparaphenylene can be used. Ethylene dicarboxylate (PET), polyethylene naphthalate (PEN), polyether oxime (PES), cyclic polyolefin (COP), polycarbonate (PC), polyvinyl chloride (PVC), poly Ethylene (PE), polypropylene (PP), acrylic resin (PMMA (PolymethylMethacrylate)), urethane (PU), and the like.

Further, the resin layer 6 may be formed of a photocurable resin, or may be a copolymer or a mixture. The manufacturing step of the electronic device by the roll-to-roll method sometimes includes a step accompanied by heat treatment, and the heat-resistant temperature (temperature at which continuous use) of the resin is preferably 100 ° C or higher. Examples of the resin having a heat resistance temperature of 100 ° C or higher include polyimine (PI), epoxy resin (EP), polyamine (PA), polyamidimide (PAI), and polyether ether ketone. (PEEK), polybenzimidazole (PBI), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyether oxime (PES), cyclic polyolefin (COP), Polycarbonate (PC), polyvinyl chloride (PVC), acrylic resin (PMMA), urethane (PU), and the like.

Among them, the resin in the resin layer 6 is preferably a polyimide or an epoxy resin, and more preferably a polyimide.

The structure of the polyimine is not particularly limited, and is preferably a repeating unit containing a residue (X) having a tetracarboxylic acid represented by the following formula (I) and a residue (A) of a diamine. Further, the polyimine preferably contains a repeating unit represented by the formula (I) as a main component (preferably 95 mol% or more with respect to all repeating units), and may contain other repeating units other than For example, a repeating unit represented by the following formula (2-1) or (2-2).

Further, the residue (X) of the tetracarboxylic acid means a tetracarboxylic acid residue obtained by removing a carboxyl group from a tetracarboxylic acid, and the residue (A) of a so-called diamine means that the amine group is removed from the diamine. Diamine residue.

In the formula (I), X represents a tetracarboxylic acid residue obtained by removing a carboxyl group from a tetracarboxylic acid, and A represents a diamine residue obtained by removing an amine group from a diamine.

In the formula (I), X represents a tetracarboxylic acid residue obtained by removing a carboxyl group from a tetracarboxylic acid, and preferably contains at least one selected from the group consisting of groups represented by the following formulas (X1) to (X4). Kind of base. In particular, in terms of the effect of the present invention being more excellent, more preferably 50% by mole or more (preferably 80 to 100% by mole) of the total number of Xs is selected from the following formulas (X1) to (X4) At least one of the groups consisting of the indicated groups. Further preferably, substantially all of the total number of X (100 mol%) comprises a group selected from the group consisting of the following formulas (X1) to (X4). At least one base in the group.

Further, A represents a diamine residue obtained by removing an amine group from a diamine, and preferably contains at least one group selected from the group consisting of groups represented by the following formulas (A1) to (A8). In particular, in terms of the effect of the present invention being more excellent, more preferably 50 mol% or more (preferably 80 to 100 mol%) of the total number of A is selected from the following formulas (A1) to (A8) At least one of the groups consisting of the indicated groups. Further, it is preferable that substantially all of the total number of A (100 mol%) includes at least one group selected from the group consisting of the groups represented by the following formulas (A1) to (A8).

Further, in terms of the effect of the present invention being more excellent, it is preferable that 80 to 100 mol% of the total number of Xs is selected from the group consisting of the groups represented by the following formulas (X1) to (X4). At least one of the groups, and 80 to 100 mol% of the total number of A includes at least one group selected from the group consisting of the groups represented by the following formulas (A1) to (A8), and more preferably X The substantial total number (100 mol%) of the total number includes at least one group selected from the group consisting of the groups represented by the following formulas (X1) to (X4), and the substantial total number of A (100 mo The ear %) contains at least one group selected from the group consisting of the groups represented by the following formulas (A1) to (A8).

In particular, in view of the fact that the effect of the present invention is more excellent, X is preferably a group represented by the formula (X1) and a group represented by the formula (X4), and more preferably a group represented by the formula (X1).

Further, in view of the fact that the effect of the present invention is more excellent, A is preferably a group represented by the formula (A1) and a group represented by the formula (A6), and more preferably a group represented by the formula (A1).

As the polyimine which comprises a preferred combination of the group represented by the formula (X1) to (X4) and the group represented by the formula (A1) to (A8), X is preferably a formula (X1). Polyimine 1 in which A is a group represented by the formula (A1), and X is a group represented by the formula (X4), and A is a polyimine 2 represented by the formula (A6). In the case of polyimine 1, heat resistance is more excellent. Further, in the case of polyimine 2, colorless transparency is preferred.

The number of repetitions (n) of the repeating unit represented by the above formula (I) in the polyimine is not particularly limited, and is preferably an integer of 2 or more. In terms of the effect of the present invention being more excellent, it is preferably 10~10000, more preferably 15~1000.

The polyimine may further contain, as a tetracarboxylic acid residue (X), one or more selected from the group consisting of the groups exemplified below in the range of non-destructive heat resistance. Further, two or more kinds of the groups exemplified below may be included.

[Chemical 3]

Further, the polyimine may further contain, as a diamine residue (A), one or more selected from the group consisting of the groups exemplified below in the range of non-deterioration heat resistance. Further, two or more kinds of the groups exemplified below may be included.

[Chemical 4]

The resin layer 6 may cover the portion where the glass substrate 4 is to be broken, and may cover at least a part of one of the main faces of the resin layer 6. The resin layer 6 preferably covers the entire main surface of one of the glass substrates 4. Further, the resin layer 6 may also protrude from one main surface of the glass substrate 4.

The method for producing the resin layer 6 is not particularly limited, and the optimum conditions are appropriately selected depending on the materials to be used. In view of the fact that the effects of the present invention are more excellent, a liquid resin composition can be applied to the glass substrate 4. A method of forming the resin layer 6 by curing it.

In addition, the production method in the case of producing the resin layer (polyimine resin layer) containing the above polyimine is not particularly limited, and it is preferred to use the polycarbonate represented by the above formula (I) by thermal curing. The form of the curable resin of the imide resin.

Hereinafter, a preferred embodiment of the method for producing a polyimide resin layer will be described in detail. Bright. The manufacturing method preferably has the following steps (1) and (2).

Step (1): a step of applying a curable resin which is a polyimine resin represented by the above formula (I) to a glass substrate 4 by thermal curing to obtain a coating film

Step (2): a step of subjecting the coating film to heat treatment to form a polyimide layer

The procedure of each step will be described in detail below.

(Step (1): Coating film forming step)

The step (1) is a step of applying a curable resin which is a polyimine resin having a repeating unit represented by the above formula (I) to a glass substrate 4 by thermal curing to obtain a coating film.

Further, the curable resin preferably contains a polyamic acid obtained by reacting a tetracarboxylic dianhydride with a diamine, and at least a part of the tetracarboxylic dianhydride is selected from the following formulas (Y1) to (Y4). At least one tetracarboxylic dianhydride in the group consisting of the compounds represented, and at least a part of the diamines is at least one selected from the group consisting of compounds represented by the following formulas (B1) to (B8) One type of diamine.

Further, the polyamic acid is usually represented by a structural formula including a repeating unit represented by the following formula (2-1) and/or formula (2-2). Further, in the formulas (2-1) and (2-2), the definitions of X and A are the same as the definitions of X and A in the formula (I), respectively.

The reaction conditions of the tetracarboxylic dianhydride and the diamine are not particularly limited, and in terms of efficiently synthesizing the polyamic acid, it is preferably from -30 to 70 ° C (preferably from -20 to 40 ° C). The reaction is carried out under .

The mixing ratio of the tetracarboxylic dianhydride to the diamine is not particularly limited, and is preferably from 0.66 to 1.5 mol, more preferably from 0.9 to 1.1 mol, based on 1 mol of the diamine. It is preferably reacted with 0.97~1.03 mole of tetracarboxylic dianhydride.

An organic solvent may also be used as needed in the reaction of the tetracarboxylic dianhydride with the diamine. The type of the organic solvent to be used is not particularly limited, and for example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-diethylacetamide, N, can be used. N-dimethylformamide, N,N-diethylformamide, N-methylcaprolactam, hexamethylphosphoniumamine, tetramethylene hydrazine, dimethyl hydrazine, m. Phenol, phenol, p-chlorophenol, 2-chloro-4-hydroxytoluene, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, two Alkane, γ-butyrolactone, dioxolane, cyclohexanone, cyclopentanone or the like may be used in combination of two or more kinds.

In the above reaction, other tetracarboxylic dianhydrides other than the tetracarboxylic dianhydride selected from the group consisting of the compounds represented by the above formulas (Y1) to (Y4) may be used in combination.

Further, in the above reaction, other diamines other than the diamines selected from the group consisting of the compounds represented by the above formulas (B1) to (B8) may be used in combination.

Further, as the curable resin used in the present step, a tetracarboxylic dianhydride which can be reacted with polyglycine can be added in addition to the polyamic acid obtained by reacting the above tetracarboxylic dianhydride with a diamine. Or diamines. When tetracarboxylic dianhydride or diamine is added in addition to poly-proline, two or more poly-lysines having a repeating unit represented by formula (2-1) or formula (2-2) can be obtained. The molecule is bonded via a tetracarboxylic dianhydride or a diamine.

In the case where the polyamine has an amine group at the terminal, a tetracarboxylic dianhydride may be added, and the carboxyl group may be added in a manner of 0.9 to 1.1 moles per mole of the polyglycolic acid. In the case where the polyglycolic acid has a carboxyl group at the terminal, a diamine may be added, and the amine group may be added in an amount of 0.9 to 1.1 moles per mole of the polyglycolic acid. Further, in the case where the polyglycolic acid has a carboxyl group at the terminal, the acid terminal may be obtained by adding water or an arbitrary alcohol to ring-open the acid anhydride group at the terminal.

The tetracarboxylic dianhydride to be added later is more preferably a compound represented by the formula (Y1) to (Y4). The diamine to be added later is preferably a diamine having an aromatic ring, more preferably a compound represented by the formula (B1) to (B8).

In the case where a tetracarboxylic dianhydride or a diamine is added in the subsequent manner, the degree of polymerization (n) of the polyamic acid having a repeating unit represented by the formula (2-1) or the formula (2-2) is preferably 1~20. If aggregated When the degree (n) is in this range, the concentration of the polyamic acid in the curable resin solution is 30% by mass or more, and the solution of the curable resin can be made to have a low viscosity state.

A component other than the curable resin can also be used in this step.

For example, a solvent can be used. More specifically, the curable resin can be dissolved in a solvent and used as a solution of a curable resin (curable resin solution). As the solvent, an organic solvent is preferred in terms of solubility of the polyamic acid. The organic solvent to be used in the above reaction can be mentioned as the organic solvent to be used.

In the case where the organic solvent is contained in the curable resin solution, the content of the organic solvent is not particularly limited as long as the coating film thickness can be adjusted and the coating property is good, and generally, it is hardened. The total mass of the resin solution is preferably from 5 to 95% by mass, more preferably from 10 to 90% by mass.

Further, a dehydrating agent or a dehydration ring-closing catalyst which is intended to promote the dehydration ring closure of polyamic acid may be used in combination. For example, as the dehydrating agent, for example, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used. Further, as the dehydration ring-closing catalyst, for example, a tertiary amine such as pyridine, trimethylpyridine, lutidine or triethylamine can be used.

A method of applying a curable resin (or a curable resin solution) to the surface of the glass substrate is not particularly limited, and a known method can be used. For example, a spray coating method, a die coating method, a spin coating method, a dip coating method, a roll coating method, a bar coating method, a screen printing method, a gravure coating method, and the like can be given.

The thickness of the coating film obtained by the above treatment is not particularly limited, and the polyimide layer of the desired thickness can be appropriately adjusted.

(Step (2): Heat treatment step)

The step (2) is a step of subjecting the coating film to heat treatment to form a polyimide film. By carrying out this step, for example, the polyamic acid contained in the curable resin is subjected to a ring closure reaction to form a desired resin layer.

The method of heat treatment is not particularly limited, and a known method is suitably used (for example, attached) The support substrate of the coating film is placed in a heating oven for heating).

The heating temperature is not particularly limited, and is preferably from 300 to 500 ° C, and more preferably from 350 to 450 ° C in terms of a lower residual solvent ratio and a further increase in the sulfhydrylation ratio and more excellent effects of the present invention. The ring closure reaction of polyglycolic acid is mainly carried out at the above heating temperature. Therefore, the above temperature is also referred to as the hydrazine imidization temperature. Further, as described later, in terms of the effect of the present invention being more excellent, it is preferred to gradually increase the heating temperature to the hydrazine imidization temperature.

The heating time is not particularly limited, and the optimum time is appropriately selected depending on the structure of the curable resin to be used, and the residual solvent ratio is lowered, the ruthenium imidization ratio is further increased, and the effect of the present invention is further improved. The temperature rise time of the temperature to the imidization temperature is preferably from 30 to 180 minutes, more preferably from 60 to 120 minutes. Further, in the case of performing the drying and heat treatment described later, the temperature rise time from the temperature at the time of the heat treatment to the heat treatment temperature of the hydrazine imidization temperature may be within the above range. Further, the temperature increase rate at the time of temperature rise is not particularly limited, but it is preferred to increase the temperature at a substantially constant speed (constant temperature increase rate), and it is preferable to use a heating start temperature (dry temperature when subjected to dry heat treatment) The difference between the difference from the specific imidization temperature divided by the specific temperature rise time. Specifically, when the heating start temperature is 120 ° C, the hydrazine imidization temperature is 350 ° C, and the temperature rise time is 120 minutes, the temperature increase rate is preferably about (350-120) / 120 ≒ 1.9 ° C / min.

Further, the holding time at the hydrazine imidization temperature is preferably from 30 to 120 minutes.

The heating environment is not particularly limited, and is, for example, carried out in the atmosphere, under vacuum or under an inert gas.

Furthermore, the heat treatment can be carried out in stages at different temperatures.

Further, a drying heat treatment for removing volatile components (solvents) in the coating film may be carried out as needed before the treatment at the above heating temperature. The temperature conditions for the drying and heat treatment are not particularly limited, and in terms of the effect of the present invention being more excellent, the heat treatment at 40 to 200 ° C is preferred. Further, the drying time is not particularly limited, and the effect of the present invention is more excellent. In terms of aspect, it is preferably 15 to 120 minutes, more preferably 30 to 60 minutes. Furthermore, the drying heat treatment can be carried out in stages at different temperatures.

Therefore, as one of the preferable aspects of the step (2), a drying treatment at the above temperature may be employed, and then the heat treatment at 350 to 450 ° C may be carried out.

The polyimine resin layer containing the polyimide resin is formed by the above step (2).

The ruthenium imidation ratio of the polyimide resin is not particularly limited, and is preferably 99.0% or more, and more preferably 99.5% or more, in terms of the effect of the present invention being more excellent.

The method for measuring the yield of hydrazine is carried out by heating the curable resin at 350 ° C for 2 hours in a nitrogen atmosphere, and the yttrium imidation ratio is 100%, which is derived from the IR spectrum of the curable resin. the carbonyl peak (PEI): a peak strength of about 1780cm ^-1 to the peak intensity of the phase change before and after heat treatment (e.g., benzene ring derived peak: about 1500cm ^-1) intensity ratio is obtained.

In the above step (1), a curable resin which is a polyimine resin having a repeating unit represented by the above formula (I) by thermal curing is applied onto a glass substrate to produce a coating film, but The composition is not limited to this embodiment. For example, a composition comprising a polyimine resin represented by the above formula (I) and a solvent may be applied to form a coating film.

<Composite and electronic device>

The composite body includes a glass substrate 4 and a resin layer 6.

The light transmittance of the composite is not particularly limited, and may be 90% or less and 80% or less in the case of application to an OLED which does not require light to be transmitted to the top of the rear substrate.

Next, the electronic device will be described.

Examples of the electronic device include an image display panel, a solar cell, a thin film secondary battery, and an imaging element (CCD (Charge Coupled Device), CMOS (Complementary Metal Oxide Semiconductor)). Etc.), pressure sensors, acceleration sensors, biosensors, etc. Examples of the image display panel include a liquid crystal panel (LCD), a plasma display panel (PDP), an organic EL panel (OLED), and electronic paper. The electronic device has a composite body of the above configuration and an element formed on the composite body.

Fig. 3 is a view showing an organic EL panel (OLED) according to an embodiment of the present invention. The organic EL panel 70 is composed of, for example, a composite 2, a pixel electrode 72, an organic layer 74, a counter electrode 76, a sealing plate 78, and the like. The organic layer 74 includes at least a light-emitting layer, and optionally includes a hole injection layer, a hole transport layer, an electron transport layer, and an electron injection layer. For example, the organic layer 74 sequentially includes a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer from the anode side. The top emission type organic EL element 71 is constituted by the pixel electrode 72, the organic layer 74, the counter electrode 76, and the like. Further, the organic EL element may be of a bottom emission type.

Fig. 4 is a view showing a liquid crystal panel according to an embodiment of the present invention. The liquid crystal panel 80 is composed of a TFT substrate 82, a CF substrate 84, a liquid crystal layer 86, and the like. The TFT substrate 82 is formed by patterning a TFT element (thin film transistor element) 83 on the composite 2 (for example, the glass substrate 4 constituting the composite 2). The CF substrate 84 is formed by patterning the color filter element 85 on the other composite 2 (for example, the glass substrate 4 constituting the composite 2). The liquid crystal layer 86 is formed between the TFT substrate 82 and the CF substrate 84. The TFT substrate 82 and the CF substrate 84 correspond to the electronic device described in the patent application.

Fig. 5 is a view showing a solar cell according to an embodiment of the present invention. The solar cell 90 is composed of, for example, a composite 2, a transparent electrode 92, a ruthenium layer 94, a reflective electrode 96, a sealing plate 98, and the like. The tantalum layer is composed of, for example, a p-layer (a layer doped into a p-type), an i-layer (a light-absorbing layer), an n-layer (a layer doped into an n-type), and the like from the anode side. The prismatic solar cell element 91 is constituted by the transparent electrode 92, the ruthenium layer 94, the reflective electrode 96, and the like. Further, the solar cell element may be a compound type, a dye-sensitized type, a quantum dot type or the like.

Fig. 6 is a view showing a thin film secondary battery according to an embodiment of the present invention. The thin film secondary battery 100 is composed of, for example, a composite 2, a transparent electrode 102, an electrolyte layer 104, a collector layer 106, The sealing layer 108, the sealing plate 109, and the like are configured. The thin film secondary battery element 101 is composed of the transparent electrode 102, the electrolyte layer 104, the collector layer 106, the sealing layer 108, and the like. Further, the thin film secondary battery element 101 of the present embodiment is of a lithium ion type, and may be a nickel hydrogen type, a polymer type, a ceramic electrolyte type or the like.

Fig. 7 is a view showing an electronic paper according to an embodiment of the present invention. The electronic paper 110 is composed of, for example, a composite 2, a TFT layer 112, a layer 114 containing an electrical medium (for example, a microcapsule), a transparent electrode 116, and a front panel 118. The electronic paper element 111 is composed of a TFT layer 112, a layer 114 containing an electrical medium, a transparent electrode 116, and the like. The electronic paper element may be any of a microcapsule type, a transverse electric field type, a torsion sphere type, a particle moving type, an electron jet type, and a polymer network type.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the examples. Example 1 is an example, and Examples 2 and 3 are comparative examples.

In the following examples, a glass substrate X (having an average thickness of 100 μm, a thickness deviation of 1 μm or less in the width direction, an alkali-free glass, a thermal expansion coefficient of 4 × 10 ^-6 /° C., and a tensile modulus of elasticity of 77 GPa) was used as the glass substrate. There are a plurality of minute cracks on the surface of the glass substrate X. The width W of the micro crack is about 10 to 100 nm, and the depth d is 10 μm or less.

Further, the glass substrate X is produced by a floating method. Specifically, the molten glass is formed on a molten tin to be formed into a strip shape, and after the glass to be formed is slowly cooled, the cooled glass is cut into a desired size. In the slow cooling step and the cutting step, the glass is supported by the air pressure of the compressed air so that the glass does not come into contact with the solid matter. In the cutting step, a laser cutting method as a non-contact cutting method is employed.

<Manufacturing Example 1: Production of Polyproline Solution (P1)>

P-phenylenediamine (10.8 g, 0.1 mol) was dissolved in 1-methyl-2-pyrrolidone (226.0 g), and stirred at room temperature. Add BPDA (3,3',4,4'-bisphenyltetracarboxylic dianhydride,3,3',4,4'-biphenyltetracarboxylic dianhydride) to the mixture for 1 minute (29.4 g, 0.1 mol), stirred at room temperature for 2 hours to obtain a polyglycine containing a repeating unit represented by the above formula (2-1) and/or formula (2-2) and having a solid content concentration of 20 masses % polyglycine solution (P1). The viscosity of the solution was measured and found to be 3000 cps at 20 °C.

The viscosity was obtained by using a DVL-BII type digital viscometer (B type viscometer) manufactured by Tokimec Co., Ltd., and measuring the rotational viscosity at 20 °C.

Further, X in the repeating unit represented by the formula (2-1) and/or the formula (2-2) contained in the polyamic acid is a group represented by the formula (X1), and A is a formula (A1). The basis of the representation.

<Example 1>

First, the glass substrate X is washed with pure water, and then further cleaned by UV cleaning.

Then, the polyaminic acid solution (P1) was applied onto the first main surface of the glass substrate X by a spin coater (revolution number: 2000 rpm, 15 seconds), thereby providing a polylysine on the glass substrate X. The coating film (coating amount: 100 g/m ² ).

Further, the polyamic acid is a resin obtained by reacting a compound represented by the above formula (Y1) with a compound represented by the formula (B1).

Next, it was heated in the air at 60 ° C for 30 minutes, then heated at 120 ° C for 30 minutes, and further heated to 350 ° C for 2 hours, and kept at 350 ° C for 1 hour, and the coating film was heated to form a resin layer (average thickness). : 25 μm). The formed resin layer contains a polyimine resin having a repeating unit represented by the following formula (X in the formula (I) contains a group represented by the formula (X1), and A contains a group represented by the formula (A1)) . Further, the oxime imidization ratio was 99.7%.

<Example 2>

The heating conditions of the coating film were set to 60 ° C for 30 minutes, then heated at 120 ° C for 30 minutes, and further heated in an oven at 350 ° C for 1 hour, except that the same method as in Example 1 was used. A glass composite is obtained.

<Example 3>

After forming a resin layer (polyimine film) by the same method as in Example 1, the polyimide film was temporarily peeled off and overlapped with another glass substrate X, and "HAL-TEC" manufactured by Sankyo Co., Ltd. was used. The amount of press-in was set to 1 mm, and the laminate was rolled under the atmosphere.

<Measurement of various parameters>

("d _f /d")

The depth d of the microcrack is obtained by directly performing the destruction test described later on the glass substrate X, and directly observing the fracture origin by an optical microscope.

Further, regarding the measurement of the depth d _f of the resin, first, 0.1% by mass of 3-aminopropyltriethoxydecane (KBM903) was dissolved and coated on the surface of the glass substrate X by spin coating (2000 rpm). Isopropyl alcohol solution. Then, after drying at 80 ° C for 10 minutes, a fluorescent isothiocyanate (concentration: 0.01 (mmol/l)) and a water-soluble resin (concentration) were used by a spin coater (revolution number: 2000 rpm, 15 seconds). An aqueous solution of vinyl alcohol) is applied to the first main surface of the glass substrate X. After the coating treatment, the glass substrate X was rinsed three times with pure water, dried, and then subjected to a breaking test described later, and thereafter, a fracture origin was observed using a fluorescence microscope (Olympus), and the depth d _{f was} observed. Further, the concentration of the polyvinyl alcohol in the aqueous solution is adjusted so that the viscosity of the aqueous solution is equal to the viscosity of the polyamic acid solution (P1).

Further, as described above, a method of measuring the depth d _f by a fluorescence microscope is disclosed. After the fracture test described later is performed on the obtained composite, the fracture origin is directly observed by an optical microscope, and as a result, the depth obtained by the above-mentioned fluorescence microscope is observed. The depth d _f is the same value.

In addition, when it is difficult to perform measurement by a microscope, the theoretical value is obtained from the failure stress and the stress intensity factor according to the basic formula d=(K/2σ) ² ("ceramic destruction" P68) of the failure mechanics. And use this value.

(The elongation at break of the resin layer TE)

The elongation at break TE of the resin layer (polyimine resin layer) was measured in accordance with ASTM D882-12.

(The lodging stress σ _{S of the} resin layer and the tensile elastic modulus E _resin )

The lodging stress σ _S and the tensile elastic modulus E _resin of the resin layer (polyimine resin layer) were measured in accordance with JIS-C-2151:2006.

Further, regarding the elongation at break TE of the resin layer (polyimine resin layer), the stress σ _S of the resin layer, and the tensile elastic modulus E _resin of the resin layer, after the resin layer is peeled off from the obtained composite The above measurement was carried out. When the resin layer cannot be peeled off, the glass substrate is dissolved by hydrofluoric acid to obtain a resin layer for measurement.

<Evaluation (destruction test)>

The average fracture strength of the glass substrate in the case where the resin layer was prepared in Examples 1 to 3 was measured by the bending test apparatus of Fig. 8.

Hereinafter, first, a method of measuring the average fracture strength of the glass substrate in the case where the resin layer is not present will be described with reference to FIG.

Fig. 8 is a view showing a bending test apparatus for detecting the average breaking strength of the glass substrate of the present invention. In the state shown by the solid line, when the lower support disk moves to the left in the drawing with respect to the upper support disk, the state shown by the single-dot chain line is shown.

As shown in FIG. 8, the bending test apparatus 10 includes a support disk 14 as the upper side of the first support disk and a support disk 16 as the lower support side of the second support disk, and the test sheet 18 is placed on the upper support disk 14 and the lower support disk 16 Bend between.

The test sheet 18 is at the same time as the glass substrate for which the average breaking strength is to be known. The produced glass substrate is processed and produced. Glass substrates produced at the same time (eg, glass substrates of the same batch) can be considered to have the same degree of damage to the surface. Further, the test sheet 18 can also be cut out from the glass substrate itself which is known to have an average breaking strength.

The test sheet 18 is formed in a rectangular shape in a natural state without external force. The length of the short side of the test sheet 18 was 100 mm, and the length of the long side of the test sheet 18 was 150 mm.

The upper side support disk 14 supports the test sheet 18. The support surface 14a of the upper side support disk 14 is a flat surface facing downward. The support surface 14a of the upper support tray 14 is fixed to the short side portion of the test sheet 18 by, for example, an adhesive tape.

The lower support tray 16 supports the test sheet 18 in the same manner as the upper support tray 14. The support surface 16a of the lower side support tray 16 is a flat surface facing upward. The other short side portion of the rectangular test piece 18 is placed on the support surface 16a of the lower support tray 16 and fixed by static friction. In order to prevent the positional deviation of the test piece 18, the stopper portion 17 abutting against the other short side portion of the test piece 18 is provided on the support surface 16a of the lower side support disk 16.

In the bending test apparatus 10, first, the operator adjusts the interval D between the support surface 14a of the upper side support disk 14 and the support surface 16a of the lower support disk 16 so as to be on the upper support disk 14 and the lower side. The test sheet 18 bent between the side support disks 16 produces a specific tensile stress.

The tensile stress σ generated at the tip end of the bent portion of the test sheet 18 (the right end of the test sheet 18 in Fig. 8) can be calculated based on the following formula (2).

σ=A×E×t/(D-t)‧‧‧(2)

In the above formula (2), A is a constant (1.198) inherent in the test, E is a tensile elastic modulus of the test sheet 18, and t is the thickness of the test sheet 18. It is clear from the formula (2) that the narrower the interval D (D>2×t), the larger the tensile stress σ.

Then, the operator moves the position of the support tray 16 on the lower side of the upper support tray 14 in the specific direction one time while maintaining the interval D. The moving speed was 10 mm/s, the moving distance was 100 mm, and the moving direction was a direction perpendicular to the short side of the test sheet 18.

In this manner, whether or not a crack is formed on the test sheet 18 bent between the upper support tray 14 and the lower support tray 16 is checked by an operator. Whether or not the crack is formed is confirmed by an AE sensor that detects the presence or absence of an AE (Acoustic Emission) wave generated when the crack is formed.

When the crack is not formed on the test sheet 18, the operator narrows the interval D between the support surface 14a of the upper side support disk 14 and the support surface 16a of the lower support disk 16 in parallel with each other. Thereby, the test sheet 18 bent between the upper side support tray 14 and the lower side support tray 16 generates higher tensile stress than the previous one.

Then, the operator moves the position relative to the lower side support tray 16 of the upper support tray 14 while maintaining the interval D, and inspects the test sheet 18 bent between the upper support tray 14 and the lower support tray 16 Whether a crack is formed on it. The tensile stress σ applied to the test sheet 18 was stepwisely narrowed in stages, and cracks were formed on the test sheet 18, whereby the breaking strength of the test sheet 18 was known. The tensile stress σ when the test sheet 18 is broken is used as the breaking strength.

The average value of the breaking strength of the five test sheets 18 was used as the average breaking strength of the five test sheets 18.

Next, a method of measuring the average fracture strength of a composite having a resin layer will be described. In the case where the resin layer was present, the bending test apparatus shown in Fig. 8 was used in the same manner as in the absence of the resin layer, and a bending test was performed to cause tensile stress on the main surface of the glass substrate to which the resin layer was bonded. The tensile stress σ generated at the tip end of the curved portion of the main surface of the glass substrate can be calculated according to the following formula (3).

σ=A×E×t/(D'-t)‧‧‧(3)

In the above formula (3), A is a constant (1.198) inherent in the test, E is a tensile elastic modulus of the glass substrate, t is the thickness of the glass substrate, and D' is "D'=D-2×u The value calculated by the formula. u represents the thickness of the resin layer. Due to the presence of the resin layer, the distance between the upper end and the lower end of the glass substrate is shorter than the interval D by 2 x u. Further, the amount of displacement of the neutral surface of the glass substrate due to the presence of the resin layer is 5% or less of the thickness t of the glass substrate, and the influence of the calculation result of the tensile stress σ is hardly affected, so that it can be ignored. The neutral surface is a surface where neither tensile stress nor compressive stress is generated, and in the case where the resin layer is not present, it is the center plane in the thickness direction of the glass substrate. The displacement of the neutral plane can be calculated by the usual formula in material mechanics. The tensile stress σ _b when the glass substrate is broken is used as the breaking strength.

Using the above apparatus, the rate of improvement of the average fracture strength of the glass substrate achieved by the presence of the reinforcing layer (resin layer) was calculated. The increase rate is a value obtained by using the average fracture strength of the glass substrate in the absence of the reinforcing layer as a reference (100%). As the average breaking strength of the criteria in Examples 1 to 3, the average breaking strength (154 MPa) of the glass substrate X was used.

Further, the flexibility of the composite prepared in Examples 1 to 3 was evaluated by the rate of increase in the flexural rigidity of the composite. Here, the "increased rate of flexural rigidity" means the rate of increase in the flexural rigidity of the composite when the flexural rigidity of the glass substrate in the absence of the resin layer is used as a reference. The flexural stiffness can be calculated using the usual formula in structural mechanics. The lower the rate of increase in flexural rigidity, the better the flexibility.

The evaluation results are shown in Table 1.

As shown in Example 1 of Table 1, it was confirmed that the composite of the present invention exhibited the desired effect. Also, the flexural rigidity does not rise too much, so the flexibility does not decrease.

On the other hand, Examples 2 and 3 which do not satisfy the requirements of the present invention do not achieve the desired effect. fruit.

Although the embodiment of the composite or the like has been described above, the present invention is not limited to the above embodiment. The present invention can be modified or improved within the scope of the gist of the invention as set forth in the appended claims.

The present invention has been described in detail with reference to the specific embodiments thereof, and it is understood that various changes or modifications may be made without departing from the spirit and scope of the invention. The present application is based on Japanese Patent Application No. 2014-123308, filed on Jun.

2‧‧‧Compound

4‧‧‧ glass substrate

6‧‧‧ resin layer

8‧‧‧Small cracks

d‧‧‧Deep crack depth

d _f ‧‧‧Deep depth of resin from the surface of the glass substrate

W‧‧‧The width of tiny cracks

Claims (5)

A composite body comprising a glass substrate having a micro crack on its surface and a resin layer disposed on the glass substrate, wherein a resin of the resin layer penetrates at least a portion of the inside of the micro crack, and the resin is away from the surface of the glass substrate The ratio of the depth d _f to the depth d of the minute crack (d _f /d), the elongation at break TE (%) of the resin layer, and the relief stress σ _S (MPa) of the resin layer ( ratio (d _f / d) × elongation at break TE × yield stress σ _S) or more 400MPa‧%, the resin layer and a tensile modulus of elasticity E _resin is 1.0GPa or more. The composite of claim 1, wherein the glass substrate has an average thickness of 10 to 200 μm. The composite of claim 1 or 2, wherein the resin layer has an average thickness of 10 to 100 μm. The composite according to any one of claims 1 to 3, wherein the above resin layer comprises polyimine. An electronic device comprising the composite according to any one of claims 1 to 4, and an element formed on the glass substrate of the composite.