TWI834718B - Glass laminated body - Google Patents

Abstract

The subject of the present invention is to provide a glass laminate that can suppress the generation of curling and the damage of the glass substrate. The glass laminate 1 of the present invention has a carrier film 2 and a glass substrate 3 disposed on the upper side thereof and having a thickness of less than 150 μm, and the carrier film 2 has a plastic substrate 4 having a thickness of less than 100 μm and an adhesive layer 5 disposed on the upper side thereof. When the glass laminate 1 is heated at 140°C for 60 minutes, the peeling force between the carrier film 2 and the glass substrate 3 is greater than 0.1 N/50 mm and less than 2.0 N/50 mm.

Description

Glass laminated body

The present invention relates to a glass laminated body. Specifically, the present invention relates to a glass laminated body suitable for optical applications.

In recent years, thin glass substrates have been used as flexible substrates for optical films included in image display devices such as liquid crystal displays and organic EL (Electroluminescence) displays from the viewpoint of heat resistance. Specifically, a transparent conductive film formed by forming a transparent conductive layer such as indium tin oxide (ITO) on a thin glass substrate is used as a touch panel film.

In order to mass-produce this optical film, a roll-to-roll method is used. That is, a long thin glass substrate is prepared, functional layers such as a transparent conductive layer are sequentially formed on the thin glass substrate, and finally the thin glass substrate is rolled into a roll shape.

However, when an optical film having a thin glass base material is wound, the thin glass base material is damaged due to the stress between the thin glass base materials stacked in the thickness direction. Therefore, a glass laminated body with a resin layer in which an adhesive layer and a resin layer are laminated on a thin glass base material has been proposed (see Patent Document 1). [Prior technical literature] [Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2017-39227

[The problem that the invention aims to solve]

However, in Patent Document 1, since the resin layer is laminated on the thin glass base material via the adhesive layer, the resin layer cannot be peeled off from the thin glass base material. Therefore, since the resin layer remains as a final product (optical film), thinning of the optical film cannot be achieved, and the optical properties (light transmittance or color tone) may be reduced.

Therefore, a method of laminating a carrier film including an adhesive layer and a plastic film on a thin glass substrate of an optical film was studied. The carrier film is laminated on a thin glass substrate through an adhesive layer. Therefore, after the optical film is produced and before it is assembled into an image display device, the adhesive layer can be used as a boundary and can be easily removed (peeled off).

In addition, depending on the type of optical film, heat treatment may be performed during production of the optical film. For example, in an optical film in which a transparent conductive layer such as ITO is formed on a thin glass substrate, heat treatment is performed in order to crystallize (lower resistance).

In this way, curling occurs due to the difference in thermal expansion coefficients between the thin glass substrate and the carrier film. Therefore, studies have also been conducted on making the carrier film thinner and reducing curling.

However, if the laminate of the thin film carrier film and the thin glass substrate is heated, when the carrier film is removed, the carrier film cannot be smoothly peeled off from the thin glass substrate, resulting in the defect that the thin glass substrate is damaged.

The present invention provides a glass laminated body that can suppress the occurrence of curling and suppress damage to a glass substrate. [Technical means to solve problems]

The present invention [1] includes a glass laminate having a carrier film and a glass base material disposed on one side in the thickness direction of the carrier film and having a thickness of 150 μm or less, and the carrier film has a thickness of 100 μm or less. When the above-mentioned glass laminate is heated at 140°C for 60 minutes, the peeling force between the above-mentioned carrier film and the above-mentioned glass substrate is 0.1 N. / 2.0 N above 50 mm / below 50 mm.

The present invention [2] includes the glass laminated body according to [1], which further includes a transparent conductive layer arranged on one side in the thickness direction of the glass substrate.

The present invention [3] includes the glass laminated body according to [1] or [2], which is wound into a roll shape. [Effects of the invention]

The glass laminated body of the present invention has a glass base material with a thickness of 150 μm or less, so it can be formed into a roll shape, and industrial production (mass production) using the roll-to-roll method can be realized.

Furthermore, since the glass laminated body of the present invention includes a carrier film and a glass base material, when the glass laminated body is formed into a drum shape, damage to the glass base material can be suppressed.

In addition, the carrier film has a plastic base material and an adhesive layer with a thickness of less than 100 μm, so it can suppress curling during heat treatment.

In addition, when the glass laminated body of the present invention is heated at 140°C for 60 minutes, the peeling force between the carrier film and the glass substrate is 0.1 N/50 mm or more and 2.0 N/50 mm or less. Therefore, even after heating, the peeling force can be The carrier film peels off smoothly from the glass substrate. Therefore, when the carrier film is peeled off, damage to the glass substrate can be suppressed.

＜One embodiment＞ A glass laminated body 1 as one embodiment of the present invention will be described with reference to FIGS. 1 to 4 .

In FIG. 1 , the upper and lower directions on the paper are the up and down directions (thickness direction), the upper side of the paper is the upper side (one side in the thickness direction), and the lower side of the paper is the lower side (the other side in the thickness direction). In addition, in FIG. 1 , the left-right direction and the depth direction of the paper surface are plane directions orthogonal to the up-down direction. Specifically, follow the directional arrows in each figure.

1. Glass laminated body As shown in FIG. 1 , the glass laminated body 1 is flexible and has a film shape (including a sheet shape) with a specific thickness. The glass laminated body 1 extends in a plane direction orthogonal to the up-down direction (thickness direction) and has a flat upper surface (surface on one side in the thickness direction) and a flat lower surface (surface on the other side in the thickness direction). The glass laminated body 1 is, for example, a component used to produce a base material for a touch panel included in an image display device, that is, it is not an image display device. That is, the glass laminated body 1 is a device that does not include an image display element such as an LCD (Liquid Crystal Display, liquid crystal display device) module and is distributed as a single part and can be used industrially.

Specifically, the glass laminated body 1 is provided with the carrier film 2 and the glass base material 3 arrange|positioned on the upper surface. That is, the glass laminated body 1 includes the carrier film 2 and the glass base material 3 in this order from the bottom. It is preferable that the glass laminated body 1 contains the carrier film 2 and the glass base material 3. Each component is described in detail below.

2. Carrier film The carrier film 2 is a protective member provided on the lower surface of the glass base material 3 in order to prevent damage to the glass base material 3 when the glass base material 3 or transparent conductive glass 6 described below is transported, heated and/or stored. The carrier film 2 supports the glass substrate 3 from the lower side.

The carrier film 2 has a film shape with a specific thickness, extends in the plane direction, and has a flat upper surface and a flat lower surface. The carrier film 2 is disposed on the lower side of the glass laminated body 1. Specifically, it is disposed on the entire lower surface of the glass base material 3 so as to be in contact with the lower surface of the glass base material 3.

Specifically, the carrier film 2 includes a plastic base material 4 and an adhesive layer 5 disposed on the upper surface of the plastic base material 4 . That is, the carrier film 2 has a plastic base material 4 and an adhesive layer 5 in order from the bottom. Preferably, the carrier film 2 includes a plastic base material 4 and an adhesive layer 5 .

(Plastic base material) The plastic substrate 4 is a support substrate used to ensure the mechanical strength of the carrier film 2 and protect the glass substrate 3 from damage during transportation, heating, and/or storage.

The plastic base material 4 has a film shape and is provided on the lowermost layer of the glass laminated body 1 .

The plastic base material 4 is, for example, a flexible polymer film. Examples of the material of the plastic base 4 include polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate; for example, polymethacrylic acid. (Meth)acrylic resins such as esters (acrylic resins and/or methacrylic resins); for example, olefin resins such as polyethylene, polypropylene, cyclic olefin polymers (such as nordecene series, cyclopentadiene series) ; For example, polycarbonate resin, polyether resin, polyarylate resin, melamine resin, polyamide resin, polyimide resin, cellulose resin, polystyrene resin, etc. These materials can be used individually or in combination of 2 or more types.

From the viewpoints of transparency, heat resistance, mechanical strength, etc., polyester resin is preferred, and PET is more preferred.

The thickness of the plastic substrate 4 is less than 100 μm, preferably less than 60 μm, more preferably less than 35 μm. Moreover, for example, it is 5 micrometers or more, Preferably it is 10 micrometers or more. As long as the thickness of the plastic base material 4 is below the above-mentioned upper limit, the occurrence of curling can be suppressed when the glass laminated body 1 is heated. On the other hand, as long as the thickness of the plastic base material 4 is not less than the above-mentioned lower limit, the mechanical strength is excellent and damage to the glass base material 3 can be suppressed.

The thickness of the plastic base material 4 can be measured using a dial gauge (“DG-205” manufactured by PEACOCK).

(adhesive layer) The adhesive layer 5 is a layer (pressure-sensitive adhesive layer) used to bond the plastic substrate 4 to the glass substrate 3. It is also a layer that is easy to peel off from the glass substrate 3 after bonding (easy peeling). layer).

The adhesive layer 5 has a film shape and is disposed on the entire upper surface of the plastic base material 4 in contact with the upper surface of the plastic base material 4 . Specifically, the adhesive layer 5 is disposed between the plastic substrate 4 and the glass substrate 3 in such a manner that it is in contact with the upper surface of the plastic substrate 4 and the lower surface of the glass substrate 3 . Specifically, the adhesive layer 5 is pressure-sensitively bonded to the lower surface of the glass substrate 3 .

The adhesive layer 5 is formed of an adhesive composition.

Examples of the adhesive composition include an acrylic adhesive composition, a rubber adhesive composition, a silicone adhesive composition, a polyester adhesive composition, and a polyurethane adhesive composition. Compositions, polyamide-based adhesive compositions, epoxy-based adhesive compositions, vinyl alkyl ether-based adhesive compositions, fluorine-based adhesive compositions, etc. These adhesive compositions can be used individually or in combination of 2 or more types.

From the viewpoints of adhesion before heating and peelability after heating, the adhesive composition is preferably an acrylic adhesive composition.

The acrylic adhesive composition contains, as a polymer component, an acrylic polymer obtained by polymerizing a monomer component containing an alkyl (meth)acrylate, for example.

The (meth)acrylic acid alkyl ester is an acrylic acid alkyl ester and/or a methacrylic acid alkyl ester. Specific examples thereof include: (meth)butyl acrylate, (meth)isobutyl acrylate, (meth)acrylic acid isobutyl ester, (meth)acrylic acid alkyl ester, Second butyl acrylate, third butyl (meth)acrylate, amyl (meth)acrylate, neopentyl (meth)acrylate, isopentyl (meth)acrylate, hexyl (meth)acrylate Ester, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, Alkyl (meth)acrylates having a linear or branched alkyl moiety having 4 to 14 carbon atoms, such as tetradecyl (meth)acrylate. The alkyl (meth)acrylate can be used alone or in combination of two or more kinds.

As the (meth)acrylic acid alkyl ester, a (meth)acrylic acid alkyl ester having an alkyl moiety having 4 to 12 carbon atoms is preferred, and an alkyl (meth)acrylic acid ester having an alkyl moiety having a carbon number of 6 to 10 is more preferred. As the (meth)acrylic acid alkyl ester, more preferably, 2-ethylhexyl (meth)acrylate can be used.

The compounding ratio of the alkyl (meth)acrylate is, for example, 90 parts by mass or more, preferably 95 parts by mass or more, and, for example, 99 parts by mass or less, preferably 100 parts by mass or less of the total amount of the monomer components. Preferably, it is 98 parts by mass or less. By adjusting the blending ratio of alkyl (meth)acrylate, the peeling force of the adhesive layer 5 can be adjusted.

The monomer component may contain functional group-containing monomers in addition to alkyl (meth)acrylate.

Examples of functional group-containing monomers include, for example, carboxyl group-containing monomers such as acrylic acid and methacrylic acid; and hydroxyl group-containing monomers such as 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate. The functional group-containing monomer may be used alone or in combination of two or more types.

From the viewpoints of adhesion before heating and peelability after heating, the functional group-containing monomer is preferably a hydroxyl group-containing monomer, and more preferably, 2-hydroxyethyl acrylate is used.

The blending ratio of the functional group-containing monomer is, for example, 1 part by mass or more, preferably 2 parts by mass or more, and, for example, 10 parts by mass or less, preferably 100 parts by mass or less of the total amount of the monomer components. 5 parts by mass or less.

The weight average molecular weight of the acrylic polymer is, for example, 100,000 or more, preferably 300,000 or more, and, for example, 2 million or less, preferably 1 million or less. The weight average molecular weight can be measured by gel permeation chromatography based on standard polystyrene conversion values.

The acrylic adhesive composition can be obtained by known methods such as solution polymerization, block polymerization, and photopolymerization.

The adhesive composition preferably contains a cross-linking agent. Examples of the cross-linking agent include isocyanate-based cross-linking agents, epoxy-based cross-linking agents, melamine-based resins, aziridine derivatives, metal chelate compounds, and the like. These cross-linking agents can be used alone or in combination of two or more types.

Preferable examples of the cross-linking agent include isocyanate-based cross-linking agents and epoxy-based cross-linking agents, and more preferred examples include isocyanate-based cross-linking agents.

Examples of isocyanate-based crosslinking agents include aromatic isocyanates such as toluene diisocyanate and xylene diisocyanate; alicyclic isocyanates such as cyclopentyl diisocyanate and cyclohexane diisocyanate; and examples such as butyl diisocyanate and hexamethylene aliphatic isocyanates such as trimethylolpropane/toluene diisocyanate trimer adduct, trimethylolpropane/hexamethylene diisocyanate trimer adduct, hexamethylene diisocyanate Isocyanate adducts such as isocyanurate bodies; such as polyether polyisocyanates, polyester polyisocyanates and other polyol adducts; such as isocyanurate bodies, biuret bodies, allophanate bodies, etc. .

Preferred examples of the epoxy cross-linking agent include polyfunctional epoxy compounds. Specific examples include: N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1 , 3-bis(N,N-diglycidylaminemethyl)cyclohexane (trade name "Tetrad C", manufactured by MITSUBISHI GAS Chemical Co., Ltd.), etc.

The blending ratio of the crosslinking agent is, for example, 1 part by mass or more, preferably 2 parts by mass or more, and, for example, 15 parts by mass or less, preferably 5 parts by mass or less, based on 100 parts by mass of the polymer component. The peeling force of the adhesive layer 5 can be adjusted by adjusting the blending ratio of the cross-linking agent.

In the case of containing a cross-linking agent, it is better to include a cross-linking catalyst. Examples of cross-linking catalysts include tin-based catalysts such as tin octoate, dioctyltin dilaurate, dibutyltin bis(acetylpyruvate), and tin-based chelate compounds; for example, tris(acetylpyruvate) Iron-based catalysts such as iron, iron trimethylate, iron triisopropoxide, ferric chloride, etc. These cross-linking catalysts can be used alone or in combination of two or more types. Preferred examples include tin-based catalysts.

The mixing ratio of the cross-linking catalyst is, for example, 0.1 parts by mass or more, preferably 0.2 parts by mass or more, and, for example, 5 parts by mass or less, preferably 3 parts by mass or less, based on 100 parts by mass of the cross-linking agent. The peeling force of the adhesive layer 5 can be adjusted by adjusting the blending ratio of the cross-linking catalyst.

The adhesive composition may further appropriately contain known additives such as adhesive resin, processing aids, pigments, flame retardants, fillers, softeners, and anti-aging agents.

The thickness of the adhesive layer 5 is, for example, 5 μm or more, preferably 10 μm or more, and, for example, 100 μm or less, preferably 50 μm or less.

The thickness of the adhesive layer 5 can be measured using a dial gauge (“DG-205” manufactured by PEACOCK).

The thickness of the carrier film 2 is, for example, 10 μm or more, preferably 20 μm or more, and, for example, 100 μm or less, preferably 75 μm or less, more preferably 50 μm or less, further preferably 25 μm or less. As long as the thickness of the carrier film 2 is equal to or less than the above upper limit, the occurrence of curling when the glass laminated body 1 is heated can be suppressed. On the other hand, as long as the thickness of the carrier film 2 is not less than the above-mentioned lower limit, the mechanical strength is excellent and damage to the glass base material 3 can be suppressed.

3. Glass substrate The glass base material 3 is a support member that ensures the mechanical strength of optical components such as transparent conductive glass (described below) and supports functional layers such as transparent conductive layers (described below).

The glass substrate 3 has a film shape and is disposed on the entire upper surface of the carrier film 2 in contact with the upper surface of the carrier film 2 . Specifically, the glass substrate 3 is pressure-sensitively bonded to the upper surface of the adhesive layer 5 .

The glass substrate 3 is flexible and made of transparent glass.

Examples of glass include alkali-free glass, soda glass, borosilicate glass, aluminosilicate glass, and the like.

Known base treatment (primer treatment) can also be performed on the upper surface or lower surface of the glass substrate 3 . That is, the glass base material 3 may have a primer layer on its upper surface or lower surface.

The thickness of the glass substrate 3 is 150 μm or less, preferably 120 μm or less, more preferably 100 μm or less. Moreover, for example, it is 10 micrometers or more, Preferably it is 50 micrometers or more. As long as the thickness of the glass base material 3 is not more than the above upper limit, the flexibility is excellent and the glass base material 3 can be wound into a roll shape. In addition, as long as the thickness of the glass base material 3 is equal to or greater than the above-mentioned lower limit, the mechanical strength is excellent and damage during transportation can be suppressed.

The thickness of the glass base material 3 can be measured using a dial gauge ("DG-205" manufactured by PEACOCK Corporation).

4. Manufacturing method of glass laminated body The method of manufacturing the glass laminated body 1 is demonstrated. The manufacturing method of the glass laminated body 1 includes, for example, a preparation step and a bonding step in this order. The glass laminated body 1 is manufactured by a roll-to-roll method, for example.

(preparatory steps) In the preparation step, the carrier film 2 is prepared.

The carrier film 2 can be obtained by applying the dilution obtained by diluting the adhesive composition with a solvent onto the upper surface of the long plastic substrate 4 and drying it.

Examples of the solvent include organic solvents, aqueous solvents (specifically, water), and the like. Preferably, organic solvents are used. Examples of the organic solvent include alcohol compounds such as methanol, ethanol, and isopropyl alcohol; ketone compounds such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; and ester compounds such as ethyl acetate and butyl acetate. Ether compounds such as propylene glycol monomethyl ether; such as toluene, xylene and other aromatic compounds. These solvents can be used individually or in combination of 2 or more types. Preferred examples include ester compounds.

The solid content concentration in the diluent is, for example, 1 mass% or more, preferably 10 mass% or more, and, for example, 40 mass% or less, preferably 30 mass% or less.

The coating method can be appropriately selected depending on the coating liquid and the plastic base material 4 . Examples include: dip coating method, air knife coating method, curtain coating method, roller coating method, wire bar coating method, gravure coating method, inkjet method, etc.

The drying temperature is, for example, 50°C or higher, preferably 100°C or higher, and is, for example, 200°C or lower, preferably 150°C or lower.

The drying time is, for example, 0.5 minutes or more, preferably 1 minute or more, and, for example, 30 minutes or less, preferably 10 minutes or less.

(fitting step) In the bonding step, the carrier film 2 is bonded to the glass substrate 3 .

Specifically, the lower surface of the long glass substrate 3 is brought into contact with the adhesive layer 5 of the carrier film 2 .

As the glass base material 3, a publicly known or commercially available one can be used. The long glass base material 3 usually has a glass base material 3 and a spacer (spacer paper, etc.) arranged on one side of the glass base material 3, and the glass base material 3 is wound into a roll shape. The spacer is removed from the glass substrate 3 before the bonding step.

Furthermore, from the viewpoint of the adhesion between the glass substrate 3 and the transparent conductive layer (described below), the lower surface or the upper surface of the glass substrate 3 may be subjected to sputtering, corona discharge, flame, or ultraviolet irradiation if necessary. , electron beam irradiation, chemical treatment, oxidation and other etching treatments. In addition, the glass base material 3 can be dust-removed and purified by solvent cleaning, ultrasonic cleaning, or the like.

Thereby, the glass laminated body 1 provided with the carrier film 2 and the glass base material 3 arrange|positioned on the upper surface is obtained.

The thickness of the glass laminated body 1 is, for example, 50 μm or more, preferably 100 μm or more, and, for example, 300 μm or less, preferably 200 μm or less.

In the glass laminated body 1 before heating, that is, in the initial glass laminated body 1, the peeling force between the carrier film 2 and the glass substrate 3 is, for example, 0.05 N/50 mm or more, preferably 0.1 N/50 mm or more. , and, for example, it is 1.5 N/50 mm or less, preferably 1.0 N/50 mm or less, more preferably 0.5 N/50 mm or less. As long as the peeling force is equal to or higher than the lower limit, peeling or detachment of the carrier film 2 and the glass substrate 3 during transportation can be suppressed. Furthermore, as long as the peeling force is equal to or less than the upper limit, when the glass laminated body 1 is heated, the peeling force can be suppressed from rising excessively, and the carrier film 2 can be smoothly removed from the glass laminated body 1 .

In the heated glass laminated body 1, specifically, in the glass laminated body 1 heated at 140°C for 60 minutes, the peeling force between the carrier film 2 and the glass substrate 3 is 0.1 N/50 mm or more and 2.0 N /50 mm or less. It is preferably 0.5 N/50 mm or more, more preferably 1.0 N/50 mm or more, and more preferably 1.8 N/50 mm or less. That is, when the glass laminated body 1 is heated at 140° C. for 60 minutes, the peeling force between the carrier film 2 and the glass base material 3 falls within the above range. As long as the peeling force is equal to or higher than the lower limit, the generation of bubbles between the carrier film 2 and the glass laminated body 1 can be suppressed. Moreover, as long as the said peeling force is below the said upper limit, the carrier film 2 can be smoothly removed from the glass laminated body 1, and the damage of the glass base material 3 can be suppressed.

These peeling forces can be measured using a sample cut into a 50 mm wide glass laminate 1 under the conditions of a stretching speed of 300 mm/min and a peeling angle of 180°. More specifically, it will be described in detail in Examples.

5.Use of glass laminate The glass laminated body 1 can be used, for example, in a manufacturing method of an optical member. Hereinafter, as one embodiment of the manufacturing method of an optical member, a method of manufacturing the transparent conductive glass 6 shown in FIG. 2 using the glass laminated body 1 will be described.

The manufacturing method of the transparent conductive glass 6 includes, for example, a conductive layer arrangement step and a heating step in sequence. The transparent conductive glass 6 is produced by a roll-to-roll method, for example.

(Conductive layer configuration steps) In the conductive layer arrangement step, the transparent conductive layer 7 is arranged on the upper surface of the glass laminate 1 .

Specifically, the transparent conductive layer 7 is formed on the upper surface of the glass substrate 3 by, for example, a dry method.

Examples of dry methods include vacuum evaporation, sputtering, and ion plating. Preferable ones include sputtering. By this method, the transparent conductive layer 7 can be formed, which is a thin film and has a uniform thickness.

When a sputtering method is used, examples of the target material include the following metal oxides constituting the transparent conductive layer 7, and a preferred example is ITO. From the viewpoint of durability, crystallization, etc. of the ITO layer, the tin oxide concentration of ITO is, for example, 0.5 mass% or more, preferably 3 mass% or more, and, for example, 15 mass% or less, preferably 13 mass% or less. .

Examples of the gas include inert gases such as Ar. Moreover, a reactive gas such as oxygen may be used together as necessary. When a reactive gas is used together, the flow rate ratio (sccm) of the reactive gas is not particularly limited, but it is, for example, 0.1 flow % or more and 5 flow % or less relative to the total flow rate of the sputtering gas and the reactive gas.

From the viewpoint of suppressing a decrease in the sputtering rate, discharge stability, etc., the air pressure during sputtering is, for example, 1 Pa or less, preferably 0.1 Pa or more and 0.7 Pa or less.

The power supply may be, for example, any one of a DC (Direct Current) power supply, an AC (Alternating Current) power supply, an MF (Middle Frequency) power supply, and an RF (Radio Frequency) power supply, or it may be A combination of these.

Thereby, as shown in FIG. 2, the transparent conductive glass laminated body 8 which has the carrier film 2 and the transparent conductive glass 6 arrange|positioned on the upper surface is obtained.

The peeling force between the carrier film 2 and the transparent conductive glass 6 at this time is substantially the same as the peeling force between the carrier film 2 and the glass substrate 3 in the initial stage.

(heating step) In the heating step, the transparent conductive glass laminated body 8 is heated.

The heat treatment can be performed using, for example, an infrared heater, an oven, or the like.

The heating atmosphere may be either under air or under vacuum, but from the viewpoint of crystallization, under air is preferred.

The heating temperature is, for example, 100°C or higher, preferably 120°C or higher, and, for example, it is 200°C or lower, preferably 160°C or lower. As long as the heating temperature is within the above range, thermal damage to the plastic base material 4 and impurities generated therefrom can be suppressed, and crystallization transformation can be reliably performed.

The heating time is appropriately determined depending on the heating temperature, and is, for example, 10 minutes or more, preferably 30 minutes or more, and, for example, 5 hours or less, preferably 2 hours or less.

Thereby, when the transparent conductive layer 7 is made of ITO or the like, the transparent conductive layer 7 is crystallized, and the conductivity of the transparent conductive layer 7 is improved. Specifically, a transparent conductive glass laminated body 8 including the glass base material 3 and the heated transparent conductive layer 7 arranged on the upper surface is obtained.

The peeling force between the carrier film 2 and the transparent conductive glass 6 in the heated transparent conductive glass laminate 8 is substantially the same as the peeling force between the carrier film 2 and the glass substrate 3 in the heated glass laminate 1. .

Next, roll it into a drum shape. Thereby, the long transparent conductive glass laminated body 8 is obtained in the form of the drum body 9 rolled into a drum shape as shown in FIG. 3 .

If necessary, the transparent conductive layer 7 is subsequently patterned by known etching. Etching can be performed before winding up the transparent conductive glass laminated body 8 into the drum body 9 . Alternatively, the transparent conductive glass laminated body 8 may be rolled out from the drum 9 in a roll-to-roll manner, etched, and then rolled into a drum shape again.

The pattern of the transparent conductive layer 7 is appropriately determined depending on the application to which the transparent conductive glass 6 is applied. Examples thereof include striped electrode patterns or wiring patterns.

6.Transparent conductive glass laminate The transparent conductive glass laminated body 8 includes the carrier film 2 and the transparent conductive glass 6 arranged on its upper surface. The transparent conductive glass 6 includes a glass base material 3 and a transparent conductive layer 7 arranged on its upper surface. In other words, the transparent conductive glass laminated body 8 includes the glass laminated body 1 and the transparent conductive layer 7 arranged on the upper surface.

(transparent conductive layer) The transparent conductive layer 7 is a conductive layer used to form a required transparent pattern such as an electrode pattern or a wiring pattern.

The transparent conductive layer 7 is the uppermost layer of the transparent conductive glass laminate 8 and has a film shape. The transparent conductive layer 7 is disposed on the entire upper surface of the glass substrate 3 in contact with the upper surface of the glass substrate 3 .

Examples of the material of the transparent conductive layer 7 include at least one selected from the group consisting of In, Sn, Zn, Ga, Sb, Ti, Si, Zr, Mg, Al, Au, Ag, Cu, Pd, and W. A metal oxide of a metal. The metal oxide may also be further doped with metal atoms shown in the above group if necessary.

Specific examples of the transparent conductive layer 7 include indium-containing oxides such as indium-tin composite oxide (ITO), and examples include antimony-containing oxides such as antimony-tin composite oxide (ATO). Preferably, Examples thereof include indium-containing oxides, and more preferably, ITO is included.

When the transparent conductive layer 7 contains ITO, the tin oxide (SnO ₂ ) content relative to the total amount of tin oxide and indium oxide (In ₂ O ₃ ) is, for example, 0.5 mass% or more, preferably 3 mass% or more. Moreover, for example, it is 15 mass % or less, Preferably it is 13 mass % or less. As long as the content of tin oxide is equal to or higher than the above-mentioned lower limit, the durability of the transparent conductive layer 7 can be further improved. In addition, as long as the content of tin oxide is below the above upper limit, the crystallization transformation of the transparent conductive layer 7 can be facilitated, thereby improving the stability of the transparency or specific resistance.

"ITO" in this specification only needs to be a composite oxide containing at least indium (In) and tin (Sn), and may contain additional components other than these. Examples of additional components include metal elements other than In and Sn. Specifically, Zn, Ga, Sb, Ti, Si, Zr, Mg, Al, Au, Ag, Cu, Pd, W, Fe, Pb, Ni, Nb, Cr, Ga, etc.

The specific resistance of the transparent conductive layer 7 is, for example, 5.0×10 ^-4 Ω·cm or less, preferably 2.0×10 ^-4 Ω·cm or less. Specific resistance can be measured by the four-terminal method.

The thickness of the transparent conductive layer 7 is, for example, 10 nm or more, preferably 30 nm or more, and, for example, 300 nm or less, preferably 100 nm or less. As long as the thickness of the transparent conductive layer 7 is not less than the above-mentioned lower limit, the conductivity will be excellent. On the other hand, as long as the thickness of the transparent conductive layer 7 is equal to or less than the upper limit, the transparent conductive glass 6 can be thinned. The thickness of the transparent conductive layer 7 can be measured using a scanning fluorescence X-ray analysis device.

The transparent conductive layer 7 may be either amorphous or crystalline, but when performing the heating step, it is preferably crystalline. As long as the transparent conductive layer 7 is crystalline, the conductivity is excellent.

Whether the transparent conductive layer is amorphous or crystalline can be determined by the following method: For example, when the transparent conductive layer is an ITO layer, immerse it in hydrochloric acid (concentration 5 mass%) at 20°C for 15 minutes, and then wash with water. , dry, and measure the resistance between terminals about 15 mm apart. In this specification, when the resistance between terminals of 15 mm exceeds 10 kΩ after being immersed in hydrochloric acid (20°C, concentration 5% by mass), washed with water, and dried, the ITO layer is considered amorphous. When the inter-terminal resistance between mm is 10 kΩ or less, the ITO layer is considered crystalline.

The transparent conductive glass laminated body 8 is used in optical devices such as image display devices, for example. More specifically, the carrier film 2 is removed (peeled off) from the transparent conductive glass laminated body 8 and the transparent conductive glass 6 is used as a member of an image display device.

Specifically, when an image display device (for example, an image display device having an image display element such as an LCD module or an organic EL module) is provided with the transparent conductive glass 6 , the transparent conductive glass 6 is used, for example, as a touch panel. Use base material. As the form of the touch panel, there are various methods such as optical method, ultrasonic method, electrostatic capacitive method, resistive film method, etc., and it is especially suitable for the electrostatic capacitive method touch panel.

In addition, the transparent conductive glass 6 is, for example, a component of a base material for a touch panel included in an image display device, that is, it is not an image display device. That is, the transparent conductive glass 6 is used to make parts for image display devices, etc., and does not include image display elements such as LCD modules, but includes the glass base material 3 and the transparent conductive layer 7. It is distributed as a single part in the industry. Available devices.

Moreover, the glass laminated body 1 and the transparent conductive glass laminated body 8 include the carrier film 2 and the glass base material 3 with a thickness of 150 μm or less. Therefore, the roller body 9 can be formed, and industrial production using the roll-to-roll method can be realized. .

In addition, the carrier film 2 has a plastic base material 4 and an adhesive layer 5 with a thickness of 100 μm or less. Therefore, when the roll-to-roll method is used for winding, the mutually laminated glass base materials 3 can be relaxed in the drum body 9 stress, and suppress the damage caused by the stress.

In addition, the carrier film 2 has a plastic base material 4 and an adhesive layer 5 with a thickness of 100 μm or less, so the thermal shrinkage of the plastic base material 4 can be reduced and curling after heating can be suppressed. Therefore, the heated glass laminated body 1 can be easily formed into a drum shape.

Furthermore, when the glass laminated body 1 or the transparent conductive glass laminated body 8 is heated at 140°C for 60 minutes, the peeling force between the carrier film 2 and the glass substrate 3 (even the transparent conductive glass 6) is 0.1 N/50 mm or more 2.0 N/50 mm or less, therefore even after heating, the carrier film 2 can be smoothly peeled off from the glass substrate 3 (or transparent conductive glass 6). Therefore, when the carrier film 2 is peeled off, damage to the glass substrate 3 can be suppressed.

In particular, the present invention achieves mass production of optical components (for example, transparent conductive glass 6) using a roll-to-roll method using the flexible glass substrate 3 as a supporting substrate.

Specifically, when the flexible glass substrate 3 is used and the optical film is manufactured by the roll-to-roll method, in the drum-shaped optical film, the stress on the glass substrates 3 that are laminated on each other causes the glass substrate 3 to Cause damage.

Therefore, in order to prevent damage to the glass substrate 3, if the carrier film 2 is disposed on the lower surface of the glass substrate 3, a large thermal expansion coefficient difference will occur between the carrier film 2 and the glass substrate 3 during heating. Curling makes it difficult to roll into a roll.

Therefore, it is clear that in order to suppress curling, if the thickness of the plastic substrate 4 of the carrier film 2 is set to 100 μm or less, the carrier film 2 cannot be smoothly peeled off from the glass substrate 3 and the glass substrate 3 may be damaged. This aspect was further studied, and it was found that the peeling force based on the adhesive layer 5 increased significantly as the plastic substrate 4 became thinner.

Based on this knowledge, the present inventors focused on the peeling force based on the heated adhesive layer 5. As a result, in addition to the structure of the carrier film, the heated carrier film 2 and the glass substrate 3 were peeled off. The above problems are solved by setting the force within a specific range. That is, the occurrence of curling due to heating, damage to the glass base material 3 during winding, and damage to the glass base material 3 when the carrier film is peeled off are solved. Therefore, actual mass production using the roll-to-roll method can be achieved.

＜Example of changes＞ Hereinafter, a modification example of the embodiment shown in FIGS. 1 to 2 will be described. Furthermore, these modifications also exhibit the same functions and effects as those of the above-mentioned embodiment.

(1) In FIGS. 1 to 2 , a method for manufacturing a transparent conductive glass laminated body 8 is illustrated as the use of the glass laminated body 1 . However, the use of the glass laminated body 1 may also be an anti-reflective glass laminated body. The manufacturing method is not shown in the figure.

The anti-reflective glass laminated body includes a carrier film 2 and anti-reflective glass arranged on its upper surface. Anti-reflective glass includes a glass substrate 3 and an anti-reflective layer arranged on its upper surface. That is, the anti-reflective glass and the anti-reflective glass laminate are provided with an anti-reflective layer instead of the transparent conductive layer 7 .

The anti-reflective layer has a low refractive index layer and a high refractive index layer, and is preferably an alternating laminated body of low refractive index layers and high refractive index layers.

The refractive index of the low refractive layer is, for example, 1.35 or more and 1.55 or less. Examples of materials for the low refractive layer include silicon oxide, magnesium fluoride, and the like.

The refractive index of the high refractive index layer is, for example, 1.80 or more and 2.40 or less. Examples of materials for the high refractive layer include titanium oxide, niobium oxide, zirconium oxide, ITO, ATO, and the like.

The total thickness of the anti-reflection layer is, for example, 100 nm or more, preferably 200 nm or more, and, for example, 500 nm or less, preferably 300 nm or less.

Such an anti-reflection layer is described in Japanese Patent Application Laid-Open No. 2017-227898, for example.

The anti-reflective glass laminated body can be produced by performing the anti-reflective layer arranging step in place of the conductive layer arranging step in the manufacturing method of the transparent conductive glass laminated body 8 .

In the anti-reflective layer configuration step, an anti-reflective layer is formed on the upper surface of the glass substrate 3 by a dry method. As a dry method, the above-mentioned ones are mentioned, Preferably, a sputtering method is mentioned.

When the sputtering method is used, the material constituting the above-mentioned anti-reflection layer is used as the target material. That is, a target containing a material of a high refractive layer and a target containing a material of a low refractive layer are used.

(2) As for the use of the glass laminated body 1, for example, although not shown in the figure, functional layers other than the transparent conductive layer 7 and the anti-reflective layer can also be arranged on the glass substrate 3 of the glass laminated body 1 to produce a product with A glass laminate containing the required functional layer (such as an optical adjustment layer). [Example]

Examples and comparative examples are shown below to further explain the present invention in detail. In addition, the present invention is not limited at all by the Examples and Comparative Examples. In addition, specific numerical values such as blending ratios (content ratios), physical property values, and parameters used in the following description may be replaced by corresponding blending ratios (content ratios), physical property values, etc. described in the above "Embodiments". The upper limit value (a value defined in the form of "below" or "under") or the lower limit value (a value defined in the form of "above" or "exceed") of the corresponding record of the parameters.

Example 1 (Production of carrier film) 96.2 parts by mass of 2-ethylhexyl acrylate (2EHA) and 3.8 parts by mass of hydroxyethyl acrylate (HEA) as monomer components, and 2,2'-azobisisobutyronitrile ( AIBN) 0.2 parts by mass and 150 parts by mass of ethyl acetate were mixed together, and nitrogen gas was introduced while stirring at 23° C. to perform nitrogen replacement. Thereafter, the liquid temperature was maintained at approximately 65° C., and a polymerization reaction was performed for 6 hours to prepare a solution of acrylic polymer A (concentration 40% by mass). The weight average molecular weight of acrylic polymer A is 540,000.

Ethyl acetate was added to the solution of acrylic polymer A and diluted to a concentration of 20% by mass. To 500 parts by mass of the diluent (100 parts by mass of solid content), 4 parts by mass of toluene diisocyanate (manufactured by Tosoh, "Coronate L" (C/L)) as a cross-linking agent and laurel as a cross-linking catalyst were added 0.02 parts by mass of dibutyltin acid was added and stirred to prepare an acrylic adhesive solution.

The acrylic adhesive solution is coated on one side of a long polyester film (plastic substrate, "Polyester Film Lumirror 25R75" manufactured by Toray Company, thickness 25 μm) in a roll-to-roll method, and heated at 130°C for 2 minutes to form an adhesive layer with a thickness of 23 μm. Thereby, a carrier film is produced.

(Manufacturing of glass laminates) Prepare a long glass substrate (thickness 100 μm, "G-Leaf" manufactured by Nippon Electric Glass Co., Ltd.). The adhesive layer of the carrier film is bonded to the glass substrate in a roll-to-roll manner and then rolled into a winding drum.

Thereby, a glass laminated body which has a carrier film and a glass base material and is rolled into a drum shape is manufactured.

Examples 2-3 A glass laminated body was produced in the same manner as in Example 1, except that the thickness of the polyester film was changed to the thickness described in Table 1.

Example 4 In the preparation of the acrylic adhesive solution, 4 parts by mass of the isocyanate cross-linking agent "Coronate HX" (C-HX) was used as the cross-linking agent, and the amount of dibutyltin dilaurate was changed to 0.015 parts by mass. Moreover, the thickness of the polyester film and the adhesive layer was changed to the thickness described in Example 1. Except for the above, a glass laminated body was produced in the same manner as in Example 1.

Example 5 90 parts by mass of butyl acrylate (BA) and 10 parts by mass of acrylic acid (AA) as monomer components, 0.2 parts by mass of AIBN as a polymerization initiator, and 186 parts by mass of ethyl acetate were mixed while heating at 23°C. While stirring, nitrogen gas was introduced to perform nitrogen replacement. Thereafter, the liquid temperature was maintained at approximately 63° C., and a polymerization reaction was performed for 10 hours to prepare a solution of acrylic polymer B (concentration: 35% by mass). The weight average molecular weight of acrylic polymer B is 500,000.

Ethyl acetate was added to the solution of acrylic polymer B to dilute it to a concentration of 20% by mass. 11 parts by mass of a tetrafunctional epoxy compound ("Tetrad C" (T-C) manufactured by MITSUBISHI GAS Chemical Co., Ltd.) as a cross-linking agent was added to 500 parts by mass of the diluent (100 parts by mass of solid content), stirred, and prepared. Acrylic adhesive solution.

Coat the acrylic adhesive solution on one side of the long polyester film (same as above) using a roll-to-roll method, and heat it at 130°C for 2 minutes to form an adhesive layer with a thickness of 20 μm. Thereby, a carrier film is produced.

A glass laminated body was produced in the same manner as in Example 1 except using this carrier film.

Comparative example 1 A glass laminated body was produced in the same manner as in Example 5, except that the thickness of the polyester film was changed to the thickness described in Table 1.

Comparative example 2 A glass laminated body was produced in the same manner as in Example 5, except that the amount of the cross-linking agent in the adhesive layer was changed to the amount described in Table 1.

Comparative example 3 A glass laminated body was produced in the same manner as in Comparative Example 2, except that the thickness of the polyester film was changed to the thickness described in Table 1.

Comparative example 4 A glass laminated body was produced in the same manner as in Example 5, except that the amount of the cross-linking agent in the adhesive layer was changed to the amount described in Table 1.

Comparative example 5 A glass laminated body was produced in the same manner as in Comparative Example 4, except that the thickness of the polyester film was changed to the thickness described in Table 1.

Comparative example 6 In the adhesive layer, the amount of the monomer component and the amount of the cross-linking agent were changed to the amounts described in Table 1. Moreover, the thickness of the polyester film and the adhesive layer was changed to the amount described in Table 1. Except for the above, a glass laminated body was produced in the same manner as in Example 5.

(Thickness of each layer) The thickness of the plastic film, adhesive layer and glass substrate was measured using a dial gauge ("DG-205" manufactured by PEACOCK Company).

(Initial peeling force) The glass laminated body was cut into a width of 50 mm and a length of 200 mm, and the glass substrate 3 sides of the cut glass laminated body were fixed to a peeling force measuring device (device name "TCM-1kNB") via tape (fixing member) 12. Sample stage 11 manufactured by Minebea Mitsumi Co., Ltd. Then, one longitudinal end of the carrier film 2 in the glass laminate is held by the movable stage 13, and stretched in the longitudinal direction at a stretching speed of 300 mm/min, thereby measuring the peeling angle of 180°. Peeling force below (N/50 mm) (refer to Figure 4). The results are shown in Table 1.

(Peel strength after heating) The glass laminated body was heated at 140°C for 60 minutes. For this heated glass laminate, the peeling force (N/50 mm) at a peeling angle of 180° was measured under the condition of a stretching speed of 300 mm/min in the same manner as the above-mentioned initial peeling force test. The results are shown in Table 1.

(curl test) The glass laminated body of each Example and each Comparative Example was cut into a square shape of 20 cm×20 cm in plan view to prepare a test piece. The test piece was placed on the water platform in the oven with the polyester film on the upper side, and heated at 140°C for 60 minutes. Thereafter, it was left to cool at room temperature (23° C.) for 1 hour, and this was used as a heated test piece.

On the heated test piece, measure the average value H of the height of the four corners from the horizontal platform (see Figure 5). The results are shown in Table 1.

(Peelability) In the peeling force after heating mentioned above, the glass base material after peeling was confirmed.

The case where no damage to the glass base material is confirmed is evaluated as ○, and the case where damage such as defects is confirmed in part of the glass base material is evaluated as ×. The results are shown in Table 1.

(Confirmation of bubble) Observe with the naked eye the heated test piece in the above curl test.

The case where bubbles were not confirmed in the adhesive layer was evaluated as ○, and the case where bubbles were confirmed was evaluated as ×. The results are shown in Table 1.

[Table 1]

1: Glass laminated body 2: Carrier film 3: Glass substrate 4: Plastic base material 5: Adhesive layer 6:Transparent conductive glass 7:Transparent conductive layer 8:Transparent conductive glass laminate 9:Roller body 11: Sample table 12:Tape 13:Mobile carrier

FIG. 1 is a cross-sectional view showing an embodiment of the glass laminated body of the present invention. FIG. 2 is a cross-sectional view showing a transparent conductive glass laminated body including the glass laminated body shown in FIG. 1 . FIG. 3 is a perspective view showing the roller body of the transparent conductive glass laminated body shown in FIG. 2 . FIG. 4 is a schematic diagram showing a test for measuring the peeling force of a glass laminate in Examples. FIG. 5 is a schematic diagram showing a test for measuring the curl of a glass laminate in Examples.

1: Glass laminated body

2: Carrier film

3: Glass substrate

4: Plastic base material

5: Adhesive layer

Claims (3)

A glass laminated body, characterized in that: it is provided with a carrier film; and Disposed on one side of the thickness direction of the above-mentioned carrier film and a glass substrate with a thickness of 150 μm or less; And the above-mentioned carrier film has Plastic substrates with a thickness of less than 100 μm and The adhesive layer is arranged on one side of the thickness direction of the above-mentioned plastic substrate, When the above-mentioned glass laminate is heated at 140° C. for 60 minutes, the peeling force between the above-mentioned carrier film and the above-mentioned glass substrate is 0.1 N/50 mm or more and 2.0 N/50 mm or less. The glass laminated body of claim 1 further includes a transparent conductive layer arranged on one side in the thickness direction of the glass base material. For example, the glass laminate of claim 1 or 2 is rolled into a drum shape.