JP2023152849A - Method for manufacturing functional thin glass - Google Patents

Abstract

To provide a method for manufacturing a functional thin glass which enables suppression of the occurrence of cracking and chipping of the functional thin glass in working of the thin glass.SOLUTION: A method for manufacturing a functional thin glass includes a step a of preparing a laminate A in which a support, a peelable pressure-sensitive adhesive tape and a thin glass having thickness of 1-200 μm are laminated in this order, a step b of working the thin glass of the laminate A thereby obtaining a laminate B having a functional thin glass, and a step c of peeling the worked functional thin glass from the peelable pressure-sensitive adhesive tape of the laminate B, wherein the peelable pressure-sensitive adhesive tape is composed of a plurality of layers having a pressure-sensitive adhesive layer (A) on the surface of the thin glass side and a pressure-sensitive adhesive layer (B) on the surface on the support side, and includes a thermally expansible microsphere in at least the one layer of the plurality of layers.SELECTED DRAWING: None

Description

The present invention relates to a method for manufacturing functional thin glass.

Cover glasses are widely used in mobile terminals such as smartphones and tablets, as well as in-vehicle displays. Cover glass is used by forming functional layers such as scratch-resistant layers, AR (anti-reflection) layers, and anti-fingerprint layers, and by applying mechanical processing such as polishing, chamfering, and cutting.

Patent Document 1 discloses that a thin glass substrate with a thickness of 10 to 150 μm is coated with a heat-expandable microsphere containing thermally expandable microspheres that start expanding and/or foaming at a temperature higher than the vacuum deposition temperature on at least one side of the base material layer. A method for manufacturing an organic electroluminescent panel is disclosed, in which an organic electroluminescent panel is temporarily fixed to a support plate via a double-sided adhesive tape having a peelable adhesive layer, and electrodes are formed on a thin glass substrate.

International Publication No. 2010/004703

However, as shown in the method for manufacturing an organic electroluminescent panel in Patent Document 1, thin glass substrates are extremely fragile, so if a single thin glass substrate is transported, the thin glass substrate may "crack" during transport. In some cases, "chips" or "chips" occur, resulting in a decrease in yield.

Furthermore, in recent years, various types of processing have been increasingly performed on the thin glass substrate in order to impart desired functions to the thin glass substrate. However, even in such processing steps, "cracks" and "chips" sometimes occur in the thin glass substrate.

An object of the present invention is to provide a method for manufacturing functional thin glass that suppresses the occurrence of cracks and chips in the thin glass when processing the thin glass.

That is, the present invention can be shown below.
[1] Step a of preparing a laminate A in which a support, a peelable adhesive tape, and a thin glass having a thickness of 1 μm to 200 μm are laminated in this order;
Processing the thin glass of the laminate A to obtain a laminate B comprising functional thin glass;
a step c of peeling the processed functional thin glass from the peelable adhesive tape of laminate B;
including;
The peelable adhesive tape is composed of multiple layers including an adhesive resin layer (A) on the thin glass side surface and an adhesive resin layer (B) on the support side surface, and at least one of the multiple layers containing thermally expandable microspheres in the layer;
Method for producing functional thin glass.
[2] The method for producing functional thin glass according to [1], wherein the processing in step b is a step of forming a functional layer on the surface of the thin glass.
[3] The functional layer is at least one selected from a hard coat layer, an antireflection layer, an antifogging layer, an antifouling layer, a water repellent layer, an ultraviolet absorbing layer, an antistatic layer, a light-shielding printed layer, and a primer layer. The method for producing a functional thin glass according to [2], which is a seed.
[4] The functional thin glass subjected to the processing treatment is composed of a plurality of sheets,
The production of functional thin glass according to any one of [1] to [3], wherein the step c is a step of peeling a plurality of sheets of the functional thin glass from the peelable adhesive tape of the laminate B. Method.
[5] Between step a and step b,
A step of cutting the entire laminate A in the lamination direction to obtain a plurality of pieces of the laminate A-1,
Step b is a step of processing at least one of the thin glasses of the plurality of singulated laminates A-1 to obtain a laminate B-1 comprising functional thin glass,
The method for manufacturing a functional thin glass according to [4], wherein the laminate B-1 has a structure in which a support, a peelable adhesive tape, and a functional thin glass are laminated in this order.
[6] Between step b and step c,
A step of cutting the entire laminate B including the functional thin glass in the lamination direction to obtain a plurality of individualized laminates B-1,
The method for manufacturing a functional thin glass according to [4], wherein the laminate B-1 has a structure in which a support, a peelable adhesive tape, and a functional thin glass are laminated in this order.
[7] Between step a and step b,
[4], including the step of cutting the thin glass of the laminate A in the lamination direction to obtain a laminate A' in which a plurality of pieces of thin glass are bonded on the peelable adhesive tape. A method for producing functional thin glass.
[8] Between step b and step c,
Cutting the functional thin glass of the laminate B in the lamination direction to obtain a laminate B' in which a plurality of individual pieces of functional thin glass are bonded on the releasable adhesive tape. 4], the method for producing functional thin glass.
[9] The thin glass is composed of a plurality of sheets,
Step a is
step a-1 of pasting the releasable adhesive tape on the support;
Step a-2 of obtaining a laminate A-2 by pasting a plurality of the thin glasses in a matrix on the peelable adhesive tape;
The method for producing functional thin glass according to [4], comprising:
[10] The method for producing functional thin glass according to [9], which includes a step of previously subjecting a plurality of sheets of the thin glass to surface polishing or edge treatment before step a-2.
[11] Step a is
a step a-1' of attaching the thin glass to one side of the peelable adhesive tape to obtain an adhesive tape with thin glass;
Step a-2' of cutting the thin glass-coated adhesive tape in the lamination direction to obtain a plurality of individualized thin glass-coated adhesive tapes;
The method according to [4], comprising step a-3' of obtaining a laminate A-3 by pasting a plurality of pieces of the thin glass-attached adhesive tape into pieces on the support in a matrix shape. Method for producing functional thin glass.
[12] The peelable adhesive tape includes a base layer, an adhesive resin layer (A) containing thermally expandable microspheres provided on one side of the base layer, and An adhesive resin layer (B) provided on the surface,
The functional thin glass is pasted on the adhesive resin layer (A),
The functional composition according to any one of [1] to [11], wherein step c is a step of peeling the functional thin glass from the peelable adhesive tape by heating the adhesive resin layer (A). Method of manufacturing thin glass.
[13] The heating temperature _TC of the adhesive resin layer (A) containing the thermally expandable microspheres in step c is higher than the heating temperature TB in the processing in step _b , according to [12]. A method for producing functional thin glass.
[14] The functional thin glass according to [13], wherein the functional layer is the light-shielding printed layer, T _B is 130° C. or more and 220° C. or less, and T _C is (T _B +5)° C. or more. manufacturing method.
[15] The production of the functional thin glass according to [13], wherein the functional layer is the primer layer, T _B is 160°C or more and 250°C or less, and T _C is (T _B +5)°C or more. Method.
[16] The peelable adhesive tape includes a base material layer, an adhesive resin layer (A) provided on one surface of the base material layer, and a thermally expandable resin layer (A) provided on the other surface of the base material layer. an adhesive resin layer (B) containing microspheres, the thin glass is pasted on the adhesive resin layer (A), and step c is heating the adhesive resin layer (B). Step c-1 of peeling the laminate of the functional thin glass and the peelable adhesive tape from the support, and peeling the functional thin glass from the adhesive resin layer (A) of the laminate. The method for producing functional thin glass according to any one of [1] to [11], comprising step c-2.
[17] The heating temperature T C-1 of the adhesive resin layer (B) containing the thermally expandable microspheres in step _c-1 is higher than the heating temperature T _B in the processing treatment of step b, [ 16], the method for producing functional thin glass.
[18] The functionality according to [17], wherein the functional layer is the light-shielding printed layer, T _B is 130° C. or more and 220° C. or less, and T _C-1 is (T _B +5)° C. or more. Method of manufacturing thin glass.
[19] The functional thin glass according to [17], wherein the functional layer is the primer layer, T _B is 160° C. or more and 250° C. or less, and T _C-1 is (T _B +5)° C. or more. manufacturing method.
[20] The method for producing functional thin glass according to any one of [12] to [19], wherein the thermally expandable microspheres include microspheres in which a substance that gasifies and expands is enclosed in a shell.
[21] A removable adhesive tape used in the method for producing functional thin glass according to any one of [1] to [20], which comprises an adhesive resin layer (A) and an adhesive resin layer (B). A peelable adhesive tape comprising thermally expandable microspheres in at least one of layer (A) and layer (B).

According to the method for manufacturing functional thin glass of the present invention, it is possible to suppress the occurrence of cracks and chips in the thin glass when processing the thin glass.

FIG. 2 is a schematic side view of a laminate in which a support, a peelable adhesive tape, and thin glass are laminated. 1 is a schematic cross-sectional view of a typical example of a peelable adhesive tape. It is a schematic process diagram showing the peeling process of functional thin glass. It is a schematic process diagram showing the peeling process of functional thin glass. It is a schematic process diagram showing the manufacturing method of the functional thin glass of 1st Embodiment by which the functional thin glass of multiple sheets is obtained. It is a schematic process diagram which shows the manufacturing method of the functional thin glass of 2nd Embodiment by which the functional thin glass of 2nd Embodiment is obtained. It is a schematic process diagram which shows the manufacturing method of the functional thin glass of 3rd Embodiment by which the functional thin glass of multiple sheets is obtained. It is a schematic process diagram which shows the manufacturing method of the functional thin glass of 4th Embodiment by which the functional thin glass of multiple sheets is obtained. It is a schematic process diagram which shows the manufacturing method of the functional thin glass of 5th Embodiment by which the functional thin glass of multiple sheets is obtained. It is a schematic process diagram which shows the manufacturing method of the functional thin glass of 6th Embodiment by which the functional thin glass of multiple sheets is obtained.

Embodiments of the present invention will be described below with reference to the drawings. Note that in all the drawings, similar components are denoted by the same reference numerals, and descriptions thereof will be omitted as appropriate. Further, for example, "1 to 10" represents "1 or more" to "10 or less" unless otherwise specified.

The method for manufacturing functional thin glass of this embodiment includes the following steps.
Step a: A laminate A is prepared in which a support, a removable adhesive tape, and thin glass having a thickness of 1 μm to 200 μm are laminated in this order.
Step b: Processing the thin glass of the laminate A to obtain a laminate B comprising functional thin glass.
Step c: The functional thin glass subjected to the processing is peeled from the peelable adhesive tape of the laminate B.

[Step a]
In this step, a laminate A is prepared in which a support 10, a peelable adhesive tape 20, and a thin glass 30 having a thickness of 1 μm to 200 μm are laminated as shown in FIG.
The peelable adhesive tape 20 is composed of multiple layers including an adhesive resin layer (A) on the thin glass side surface and an adhesive resin layer (B) on the support side surface, and at least one of the multiple layers Contains thermally expandable microspheres in two layers.

In this embodiment, the laminate A can be obtained by pasting the peelable adhesive tape 20 on the support 10 and then pasting the thin glass 30 on the other side of the peelable adhesive tape 20.

Specifically, first, the adhesive film 20 is attached onto the support 10 so that the adhesive resin layer (B) faces the support 10 side. A protective film called a separator may be attached on the adhesive resin layer (B), and the protective film can be peeled off and the exposed surface of the adhesive resin layer (B) can be attached to the surface of the support 10. can. Next, the protective film on the adhesive resin layer (A) of the adhesive film 20 can be peeled off, and the exposed surface of the adhesive resin layer (A) can be adhered to the surface of the thin glass 30.

As another embodiment, the laminate A can be obtained by laminating the peelable adhesive tape 20 and the thin glass 30 and then pasting the support 10 on the other surface of the peelable adhesive tape 20.

Specifically, first, the protective film on the adhesive resin layer (A) of the adhesive film 20 is peeled off, and the thin glass 30 is attached to the exposed surface of the adhesive resin layer (A). Next, the protective film on the adhesive resin layer (B) of the adhesive film 20 is peeled off, and the adhesive film 20 is pasted onto the support 10 with the adhesive resin layer (B) facing the support 10. wear.

As a method for pasting the thin glass 30 on the surface of the adhesive resin layer (A), for example, the thin glass 30 is unrolled one after another and placed on the surface of the adhesive resin layer (A). Examples include a method of fixing.

As a method for attaching a plurality of individual pieces of thin glass to the surface of the adhesive resin layer 14, for example, a laminated body in which a plurality of individual pieces of thin glass are attached to a protective film is rolled up. A method of sequentially unrolling the laminate from the roll, placing it on the surface of the adhesive resin layer (A), then peeling off the protective film and temporarily fixing it all at once, starting from the thin glass roll. Examples include a method of unrolling the glass, placing it on the surface of the adhesive resin layer 14, and then cutting the glass into individual pieces.

As the support 10, for example, a quartz substrate, a glass substrate, a SUS substrate, etc. can be used.
The thin glass 30 usually has a thickness of 1 μm to 200 μm. It is suitably used for thin glass preferably having a thickness of 1 μm to 150 μm, more preferably 1 μm to 100 μm, particularly 1 μm to 80 μm.

The peelable adhesive tape 20 includes a base material layer, an adhesive resin layer (A) containing thermally expandable microspheres provided on one surface of the base material layer, and an adhesive resin layer (A) provided on the other surface of the base material layer. The adhesive resin layer (B) is preferably provided.
As another embodiment, an adhesive resin layer (A) provided on one surface, an adhesive resin layer (B) provided on the other surface, an adhesive resin layer (A) and an adhesive resin layer ( It is also possible to provide an intermediate layer between B), the intermediate layer comprising thermally expandable microspheres. Such an intermediate layer is preferably formed by curing a photocurable resin, and can be deformed when the thermally expandable microspheres expand when softened at a temperature at which the thermally expandable microspheres are expanded and peeled off.

In still another embodiment, the adhesive resin layer (A) and the adhesive resin layer (B), both of which contain microspheres, are directly laminated by dry lamination or the like, and the adhesive resin layer (A) and the adhesive resin layer A peelable adhesive tape having a two-layer structure containing microspheres in any one of (B) can also be used.

The peelable adhesive tape 20 can specifically adopt the following layer structure. The peelable adhesive tape 20 is attached onto the support 10 via the adhesive resin layer (B), and the thin glass 30 is laminated on the adhesive resin layer (A).
(1) Adhesive resin layer (A)/adhesive resin layer (B) containing thermally expandable microspheres
(2) Adhesive resin layer (A)/adhesive resin layer containing thermally expandable microspheres (B)
(3) Adhesive resin layer containing thermally expandable microspheres (A)/base layer/adhesive resin layer (B)
(4) Adhesive resin layer (A)/base layer/adhesive resin layer containing thermally expandable microspheres (B)
(5) Adhesive resin layer (A)/intermediate layer containing thermally expandable microspheres/adhesive resin layer (B)
(6) Adhesive resin layer containing thermally expandable microspheres (A)/intermediate layer/base layer/adhesive resin layer (B)
(7) Adhesive resin layer containing thermally expandable microspheres (A)/base layer/intermediate layer/adhesive resin layer (B)
(8) Adhesive resin layer (A)/intermediate layer/base layer/adhesive resin layer containing thermally expandable microspheres (B)
(9) Adhesive resin layer (A)/base layer/intermediate layer/adhesive resin layer containing thermally expandable microspheres (B)

FIG. 2 shows the layer structures (6) and (7), which are typical layer structures of the peelable adhesive tape 20.
As shown in FIG. 2, the layer structure (6) includes a base material layer 22 and an adhesive resin layer (A) containing thermally expandable microspheres a provided on the first surface 22a side of the base material layer 22. , an adhesive resin layer (B) provided on the second surface 22b side of the base material layer 22, and an intermediate layer 28 provided between the adhesive resin layer (B) and the base material layer 22. Be prepared.
As shown in FIG. 2, the layer structure (7) includes the base material layer 22, the adhesive resin layer (A) provided on the first surface 22a side of the base material layer 22, and the An adhesive resin layer (B) containing thermally expandable microspheres a provided on the second surface 22b side, and an intermediate layer 28 provided between the adhesive resin layer (B) and the base material layer 22. prepare

Each layer constituting the peelable adhesive tape 20 and the thermally expandable microspheres a will be described later.

[Step b]
In step b, the thin glass of the laminate A obtained in step a is processed to obtain a laminate B comprising functional thin glass. In this embodiment, it is preferable that the processing treatment is a step of forming a functional layer on the surface of the thin glass.

Examples of the functional layer include a hard coat layer, an antireflection layer, an antifogging layer, an antifouling layer, a water repellent layer, an ultraviolet absorbing layer, an antistatic layer, a light-shielding printing layer, and a primer layer. It can be formed from a single layer or multiple layers.

These functional layers can be coated by a spin coating method, a spray coating method, a bar coating method, a metal vapor deposition method, a CVD method, a vacuum vapor deposition method, a printing method, or the like. Alternatively, a product may be formed by reacting a precursor on a glass film.

The hard coat layer is a coating layer intended to provide functions such as scratch resistance, abrasion resistance, moisture resistance, hot water resistance, heat resistance, and weather resistance to the thin glass surface.
The hard coat layer is generally made of a curable organosilicon compound and an element selected from the group of Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, In, and Ti. A hard coat composition containing one or more types of oxide fine particles and/or one or more types of fine particles composed of a composite oxide of two or more elements selected from these element groups is used.

In addition to the above components, the hard coat composition also contains at least one of amines, amino acids, metal acetylacetonate complexes, organic acid metal salts, perchloric acids, salts of perchloric acids, acids, metal chlorides, and polyfunctional epoxy compounds. It is preferable to include either one. A suitable solvent that does not affect thin glass may be used in the hard coat composition, or it may be used without a solvent.

The hard coat layer is usually formed by applying a hard coat composition using a known coating method such as spin coating or dip coating, and then curing the composition. Examples of the curing method include thermosetting and curing methods using energy ray irradiation such as ultraviolet rays and visible light.
The thickness of the hard coat layer can be 0.1 μm to 50 μm.

The antireflection layer is a coating layer intended to suppress reflection of light on the surface of thin glass. Examples of the antireflection layer include layers made of metal oxides such as silicon oxide and zirconium oxide. The layer can be formed by metal vapor deposition or the like.
The layer thickness of the antireflection layer can be 50 nm to 5 μm.

The antifogging layer is a coating layer intended to suppress fogging of the thin glass surface due to water vapor or the like. The antifogging layer is formed, for example, by applying an aqueous coating solution containing an antifogging agent and drying it. A known method can be applied to apply the aqueous coating liquid.
The antifogging agent consists of an inorganic colloidal sol and a binder. Examples of inorganic colloidal sol include aqueous sol in which inorganic aqueous colloid particles such as silica, alumina, water-insoluble lithium silicate, iron hydroxide, tin hydroxide, titanium oxide, barium sulfate, etc. are dispersed in water or an aqueous medium. .
The thickness of the antifogging layer can be 0.1 μm to 5 μm.

The anti-fouling layer is a coating layer intended to suppress the adhesion of various stains such as fingerprints on the surface of thin glass. The antifouling layer can contain a resin with low surface energy. For example, silicone resins are preferred, and those containing methylpolysiloxane or phenylmethylpolysiloxane as a main component are particularly preferred. The anti-fouling layer includes an anti-fingerprint layer and the like.
The thickness of the antifouling layer can be 5 nm to 100 nm.

The water-repellent layer is a coating layer intended to suppress the adhesion of water droplets to the surface of thin glass. The water-repellent layer preferably contains a fluorine-containing silane compound or the like. More preferably, the water-repellent layer contains a hydrolyzed condensate of a fluorine-containing alkoxysilane.
The layer thickness of the water-repellent layer can be 5 nm to 100 nm.

The ultraviolet absorbing layer is a coating layer intended to absorb ultraviolet rays and suppress the effects of ultraviolet rays on devices in which functional thin glass is mounted. The ultraviolet absorbing layer includes, for example, an ultraviolet absorber, an adhesive, and the like.
Examples of the ultraviolet absorber include benzophenone compounds, benzotriazole compounds, triazine compounds, cyanoacrylates, and salicylic acid esters. Examples of the adhesive include acrylic adhesives, silicone adhesives, urethane adhesives, rubber adhesives, and the like.
The thickness of the ultraviolet absorbing layer can be 1 μm to 20 μm.

The antistatic layer is a coating layer intended to suppress charging such as static electricity on thin glass. The antistatic layer can be formed by applying and drying an aqueous coating solution containing an antistatic agent. A known method can be applied to apply the aqueous coating liquid.
Examples of antistatic agents include anionic, cationic, nonionic, betaine, and ionically conductive agents such as acrylic polymers having a quaternary ammonium base, ionene polymers, phosphate compounds, and phosphate ester compounds. , metal oxides such as tin oxide and antimony oxide, metal alkoxides and derivatives thereof such as alkoxysilane, alkoxytitanium, and alkoxyzirconium, coated carbon, coated silica, etc., or a combination of two or more can be used.
The layer thickness of the antistatic layer can be 1 nm to 10 μm.

The light-shielding printed layer is a coating layer that absorbs light of a specific wavelength and is intended to suppress the influence of light of a specific wavelength on devices in which functional thin glass is mounted. In this embodiment, the light-shielding printed layer does not include an ultraviolet absorbing layer.
The light blocking printing layer contains light blocking inks such as black, white, gray, orange, red, yellow, silver and brown. The color of the light-shielding ink can be a color that absorbs light of the wavelength to be light-shielded. The light-shielding printed layer is preferably provided within a range that does not affect the transparency of the thin glass.

Examples of the light-shielding pigment contained in the light-shielding ink include carbon black, acetylene black, lamp black, black smoke, iron black, aniline black, titanium oxide, and zinc oxide.
The light-shielding ink may further contain a solvent, a dispersant, and the like. The solvent contained in the light-shielding ink is not particularly limited, and conventionally known solvents can be used. The boiling point of the solvent contained in the light-shielding ink is, for example, less than 150°C. The dispersant contained in the light-shielding ink is not particularly limited, and conventionally known dispersants can be used.
As a commercially available light-shielding ink, for example, "Photo Black" manufactured by Toray Industries, Inc. can be mentioned.
The light-shielding printed layer may have a multilayer structure.
The light-shielding printed layer can be formed by a conventionally known printing method such as an offset printing method or a flexographic printing method. The heating temperature during printing is preferably 130°C or higher, more preferably 140°C or higher, and even more preferably 150°C or higher, from the viewpoint of sufficiently volatilizing the solvent in the ink or promoting thermal curing of the printed layer. The temperature is more preferably 160°C or higher, and from the viewpoint of preventing the peelable adhesive tape from being peeled off in step b, the temperature is preferably 220°C or lower, more preferably 200°C or lower, and still more preferably 180°C or lower.
The layer thickness of the light-shielding printed layer can be 0.1 μm to 10 μm.

The primer layer is a layer formed to improve the adhesion between thin glass and other layers, and is usually used together with other layers.
Any material can be used for the primer layer as long as it has high adhesion to thin glass, but primer compositions mainly composed of urethane resin, epoxy resin, polyester resin, or acrylic resin are usually used. Ru. For the purpose of adjusting the viscosity of the primer composition, a suitable solvent that does not affect the thin glass may be used, or the primer composition may be used without a solvent. When using a solvent, it is preferable to use a solvent with a boiling point of 150° C. or more and 250° C. or less and a solvent with a boiling point of less than 150° C. at atmospheric pressure in combination. As a result, the organic solvent evaporates appropriately during coating, and the drying of the coating film progresses, so that coating unevenness can be suppressed and film thickness uniformity can be improved.

The primer layer can be formed by either a coating method or a dry method.
When a coating method is used, a primer layer is formed by applying a primer composition to a lens using a known coating method such as spin coating or dip coating, and then solidifying the primer composition. The heating temperature during solidification is determined from the viewpoint of sufficiently volatilizing the solvent in the ink, especially from the viewpoint of sufficiently volatilizing the solvent with a boiling point of 150°C or more and 250°C or less under atmospheric pressure, or promoting thermal curing of the primer layer. In terms of temperature, the temperature is preferably 160°C or higher, more preferably 180°C or higher, even more preferably 200°C or higher, even more preferably 220°C or higher, even more preferably 230°C or higher, and the peelable adhesive tape is removed in step b. From the viewpoint of preventing peeling, the temperature is preferably 250°C or lower, more preferably 240°C or lower.
If a dry method is used, it is formed by a known dry method such as a CVD method or a vacuum evaporation method.
The layer thickness of the primer layer can be 0.5 μm to 20 μm.

In this embodiment, before step b, the surface of the thin glass may be subjected to surface treatment in order to improve the adhesion between the surface of the thin glass and the functional layer. Specifically, corona treatment, plasma treatment, undercoat treatment, etc. may be performed.

[Step c]
In this step, the processed functional thin glass of the laminate B obtained in step b is peeled from the peelable adhesive tape of the laminate B.
The peelable adhesive tape is composed of multiple layers including an adhesive resin layer (A) on the thin glass side surface and an adhesive resin layer (B) on the support side surface, and at least one of the multiple layers Since the layer contains thermally expandable microspheres a, the functional thin glass can be easily peeled off from the peelable adhesive tape. From this point of view, it is preferable that the adhesive resin layer (A) or the adhesive resin layer (B) contain thermally expandable microspheres a.

Specifically, when the peelable adhesive tape 20 has the layer configuration (6) in FIG. When the adhesive resin layer (A) containing the spheres a and the adhesive resin layer (B) provided on the other surface of the base layer 22 are provided, the step c is as shown in FIGS. ), the functional thin glass 30' can be peeled off from the peelable adhesive tape 20 by heating the adhesive resin layer (A). The functional thin glass 30' may have a functional layer (not shown) provided on the thin glass.
In this embodiment, since the adhesive resin layer (A) containing thermally expandable microspheres a is attached to the functional thin glass, the adhesive film can be easily peeled off from the functional thin glass. .
The heating temperature T _C of the adhesive resin layer (A) containing the thermally expandable microspheres in step c is higher than the heating temperature T _B in the processing treatment of step b. Thereby, the thin glass does not peel off during processing in step b, and processing can proceed.
T _B is preferably 130°C or higher, more preferably 140°C or higher, even more preferably 150°C or higher, even more preferably 160°C or higher, and preferably 250°C or lower, more preferably 240°C or lower.
T _C is preferably at least (T _B +5)°C, more preferably at least (T _B +10)°C, and even more preferably (T _B +15)°C or higher.

When the functional layer is the light-shielding printed layer, T _B is preferably 130° C. or higher, more preferably 140° C. from the viewpoint of sufficiently volatilizing the solvent in the ink or thermosetting the functional layer. Above, the temperature is more preferably 150°C or higher, still more preferably 160°C or higher, and from the viewpoint of preventing the peelable adhesive tape from peeling off in step b, it is preferably 220°C or lower, more preferably 200°C or lower, and even more preferably 180°C. ℃ or less, and T _C is preferably (T _B +5) C or higher, more preferably (T B +10) C or higher, from the viewpoint of peeling the peelable adhesive tape in step c without peeling in step b, and more preferably (T _B +10) C or higher. More preferably, the temperature is (T _B +15)°C or higher.

When the functional layer is the primer layer, T _B is selected from the viewpoint of sufficiently volatilizing the solvent in the ink, particularly from the viewpoint of sufficiently volatilizing the solvent with a boiling point of 150° C. or higher and 250° C. or lower at atmospheric pressure, or From the viewpoint of thermosetting the functional layer, the temperature is preferably 160°C or higher, more preferably 180°C or higher, even more preferably 200°C or higher, even more preferably 220°C or higher, even more preferably 230°C or higher, and a peelable adhesive. The temperature is preferably 250° C. or lower, more preferably 240° C. or lower, from the viewpoint of not peeling the tape in step b, and T _C is preferably from the viewpoint of peeling the peelable adhesive tape in step c without peeling it in step b. is (T _B +5)°C or higher, more preferably (T _B +10)°C or higher, even more preferably (T _B +15)°C or higher.

Moreover, when the peelable adhesive tape 20 has the layer structure (7) in FIG. , an adhesive resin layer (B) containing thermally expandable microspheres a provided on the other surface of the base material layer 22, step c is heating the adhesive resin layer (B). Step c-1 (FIGS. 4(a) and 4(b)) of peeling off the laminate of the functional thin glass 30' and the peelable adhesive tape 20 from the support 10, and the adhesive resin layer of the laminate ( The step c-2 (FIG. 4(c)) of peeling off the functional thin glass 30' from A) can be included.

In this embodiment, since the adhesive resin layer (B) containing the thermally expandable microspheres a is pasted on the support 10, the adhesive film with thin glass can be easily peeled off from the support 10. I can do it.
The heating temperature T C-1 of the adhesive resin layer (B) containing the thermally expandable microspheres a in step _c-1 is higher than the heating temperature T _B in the processing of step b. Thereby, the thin glass does not peel off during processing in step b, and processing can proceed.
T _B is preferably 130°C or higher, more preferably 140°C or higher, even more preferably 150°C or higher, even more preferably 160°C or higher, and preferably 250°C or lower, more preferably 240°C or lower.
T _C-1 is preferably (T _B +5) °C or higher, more preferably (T B +10) °C or higher, and more preferably (T _B +10) °C or higher, from the viewpoint of peeling the peelable adhesive tape in step c-1 without peeling it in step b. Preferably it is (T _B +15)°C or higher.

When the functional layer is the light-shielding printed layer, T _B is preferably 130° C. or higher, more preferably 140° C. from the viewpoint of sufficiently volatilizing the solvent in the ink or thermosetting the functional layer. Above, the temperature is more preferably 150°C or higher, still more preferably 160°C or higher, and from the viewpoint of preventing the peelable adhesive tape from peeling off in step b, it is preferably 220°C or lower, more preferably 200°C or lower, and even more preferably 180°C. ℃ or less, and T _C-1 is preferably (T _B +5) C or more, more preferably (T _B +10 )°C or higher, more preferably (T _B +15)°C or higher.

When the functional layer is the primer layer, T _B is selected from the viewpoint of sufficiently volatilizing the solvent in the ink, particularly from the viewpoint of sufficiently volatilizing the solvent with a boiling point of 150° C. or higher and 250° C. or lower at atmospheric pressure, or From the viewpoint of thermosetting the functional layer, the temperature is preferably 160°C or higher, more preferably 180°C or higher, even more preferably 200°C or higher, even more preferably 220°C or higher, even more preferably 230°C or higher, and a peelable adhesive. From the viewpoint of not peeling the tape in step b, the temperature is preferably 250° C. or lower, more preferably 240° C. or lower, and T _C-1 is such that the peelable adhesive tape is not peeled in step b but peeled in step c-1. From this point of view, the temperature is preferably (T _B +5)°C or higher, more preferably (T _B +10)°C or higher, and even more preferably (T _B +15)°C or higher.

In the method for manufacturing functional thin glass of the present embodiment, it is preferable that the functional thin glass subjected to the processing treatment is composed of a plurality of sheets, and the step c includes a plurality of sheets of the functional thin glass. It is preferable to include a step of peeling off the adhesive tape from the peelable adhesive tape of the laminate B.
Hereinafter, modes in which thin glass or functional thin glass is composed of a plurality of sheets will be explained using first to sixth embodiments. Note that descriptions of steps similar to the above steps will be omitted.

[First embodiment]
The method for manufacturing functional thin glass of this embodiment includes the following steps.
Step a: Prepare a laminate A in which a support 10, a peelable adhesive tape 20, and a thin glass 30 having a thickness of 1 μm to 200 μm are laminated.
Step a': The entire laminate A is cut in the stacking direction to obtain a plurality of pieces of the laminate A-1 (FIG. 5(a)).
Step b: Processing the thin glass of the laminate A-1 to obtain a laminate B-1 comprising functional thin glass (FIG. 5(b)).
Step c: The functional thin glass subjected to the processing is peeled off from the peelable adhesive tape of the laminate B-1.

In step a', as shown in FIG. 5(a), the entire laminate A is cut in the stacking direction. For cutting, a cutting means such as a diamond cutter can be used.
By this cutting, a plurality of individualized laminates A-1 are obtained. The shape of the laminate A-1 may be strip-shaped, square, rectangular, etc. when viewed from above, and can be determined depending on the application.

Next, in the same manner as in step b described above, as shown in FIG. A laminate B-1 comprising thin glass 30a) is obtained. The plurality of laminates B-1 have a structure in which a support 10a, a peelable adhesive tape 20a, a thin glass 30a, and a functional layer 40a are laminated.
Then, in the same manner as in step c described above, the functional thin glass can be peeled off from the peelable adhesive tape 20a of the laminate B-1 to obtain a functional thin glass.

[Second embodiment]
The method for manufacturing functional thin glass of this embodiment includes the following steps.
Step a: Prepare a laminate A in which a support 10, a peelable adhesive tape 20, and a thin glass 30 having a thickness of 1 μm to 200 μm are laminated.
Step b: Processing the thin glass 30 of the laminate A to obtain a laminate B including functional thin glass.
Step b': The entire laminate B including the functional thin glass is cut in the lamination direction to obtain a plurality of individual laminates B-1 (FIG. 6(a)).
Step c: The functional thin glass subjected to the processing is peeled off from the peelable adhesive tape of the laminate B-1 (FIG. 6(b)).

In step b, the functional layer 40 is formed on the thin glasses 30 of the plurality of laminates A in the same manner as in the above-described step b, thereby producing a laminate including functional thin glass (thin glass 30 with functional layer 40). get B.
In step b', as shown in FIG. 6(a), the entire laminate B including the functional thin glass (thin glass 30 with functional layer 40) obtained in steps a and b is cut in the lamination direction. , a plurality of laminates B-1 are obtained. For cutting, a cutting means such as a diamond cutter can be used.

By this cutting, a plurality of individualized laminates B-1 are obtained. The shape of the laminate B-1 may be strip-shaped, square, rectangular, etc. when viewed from above, and can be determined depending on the application.
The plurality of singulated laminates B-1 obtained in step b' have a structure in which a support 10a, a peelable adhesive tape 20a, a thin glass 30a, and a functional layer 40a are laminated. Be prepared.
Then, in the same manner as in step c described above, the functional thin glass can be peeled off from the peelable adhesive tape 20a of the laminate B-1 to obtain a functional thin glass.

[Third embodiment]
The method for manufacturing functional thin glass of this embodiment includes the following steps.
Step a: Prepare a laminate A in which a support 10, a peelable adhesive tape 20, and a thin glass 30 having a thickness of 1 μm to 200 μm are laminated.
Step a': The thin glass 30 of the laminate A is cut in the lamination direction to obtain a laminate A' in which a plurality of pieces of thin glass 30a are bonded to the peelable adhesive tape 20 (FIG. 7). (a)).
Step b: Processing the thin glass 30a of the laminate A' to obtain a laminate B' comprising functional thin glass (FIG. 7(b)).
Step c: The functional thin glass 30a subjected to the processing is peeled off from the peelable adhesive tape 20 of the laminate B'.

In step a', before processing the thin glass 30, the thin glass 30 of the laminate A prepared in step a is cut in the lamination direction, and a plurality of individual pieces are placed on the peelable adhesive tape 20. A laminate A' including three pieces of thin glass 30a is obtained (FIG. 7(a)). To cut the thin glass 30, a cutting means such as a diamond cutter can be used. By the cutting, a plurality of pieces of thin glass 30a are obtained on the peelable adhesive tape 20. The shape of the plurality of thin glasses 30a may be a strip, square, rectangle, etc. when viewed from above, and can be determined depending on the purpose.

Next, in the same manner as in step b described above, a functional layer 40 is formed on the thin glass 30a of the laminate A', as shown in FIG. 30a) is obtained. The laminate B' has a structure in which a support 10, a peelable adhesive tape 20, a plurality of individual pieces of thin glass 30a, and a functional layer 40 are laminated. The functional layer 40 can be cut as appropriate so as to cover the surface of the thin glass 30a.

In step c, the processed functional thin glass is peeled off from the peelable adhesive tape 20 of the laminate B' and transported to the next step. At this time, the conveyance can be carried out using a known method such as vacuum suction or a jig.

[Fourth embodiment]
The method for manufacturing functional thin glass of this embodiment includes the following steps.
Step a: Prepare a laminate A in which a support 10, a peelable adhesive tape 20, and a thin glass 30 having a thickness of 1 μm to 200 μm are laminated.
Step b: Processing the thin glass 30 of the laminate A to obtain a laminate B including functional thin glass.
Step b': Cut the functional thin glass of the laminate B in the lamination direction to obtain a laminate B' in which a plurality of individual pieces of functional thin glass are bonded on the peelable adhesive tape 20 ( Figure 8(a)).
Step c: The functional thin glass subjected to the processing is peeled off from the peelable adhesive tape 20 of the laminate B' (FIG. 8(b)).

Unlike the third embodiment, in step b', the functional thin glass (thin glass 30 with functional layer 40) of the laminate B obtained in steps a and b is placed on the peelable adhesive tape 20 in the laminating direction. A plurality of pieces of functional thin glass are placed on the peelable adhesive tape 20 (FIG. 8(a)).
For cutting, a cutting means such as a diamond cutter can be used.
By the cutting, a plurality of individual pieces of functional thin glass (thin glass 30a with functional layer 40a) are obtained. The shape of the functional thin glass may be a strip, a square, a rectangle, etc. when viewed from above, and can be determined depending on the intended use.

Next, in step c, a plurality of pieces of functional thin glass (thin glass 30a with functional layer 40a) are peeled off from the peelable adhesive tape of laminate B' and transported to the next step. At this time, the conveyance can be carried out using a known method such as vacuum suction or a jig.

[Fifth embodiment]
The method for manufacturing functional thin glass of this embodiment includes the following steps.
Step a-1: The peelable adhesive tape 20 is attached onto the support 10.
Step a-2: A plurality of thin glasses 30a are pasted in a matrix on the peelable adhesive tape 20 to obtain a laminate A-2 (FIG. 9(a)).
Step b: Processing is performed on the plurality of thin glasses 30a of the laminate A-2 to obtain a laminate B-2 comprising functional thin glass (FIG. 9(b)).
Step c: The functional thin glass subjected to the processing is peeled off from the peelable adhesive tape 20 of the laminate B-2 (FIG. 9(c)).

In step a-1, a removable adhesive tape 20 is attached onto the support 10 as described in step a above.

Specifically, in step a-2, a plurality of pieces of thin glass 30a are sequentially unwound from a roll of thin glass with a resin film to which a plurality of pieces of thin glass 30a are pasted to form the adhesive resin layer (A). A method of placing thin glass 30a on the surface so as to face each other, then peeling off the resin film from the resin film-coated thin glass, and pasting a plurality of thin glasses 30a on the peelable adhesive tape 20 in a matrix shape. Alternatively, a method of sequentially placing a plurality of individual pieces of thin glass 30a may be mentioned. The shape of the thin glass 30a cut into a plurality of pieces may be a strip, a square, a rectangle, etc. when viewed from above, and can be determined depending on the purpose.
It is also preferable to include a step of previously subjecting the plurality of thin glasses 30a to surface polishing or edge treatment before step a-2.

Next, in the same manner as in step b described above, as shown in FIG. A laminate B-2 comprising thin glass 30a) is obtained. The laminate B-2 has a structure in which a support 10, a peelable adhesive tape 20, a plurality of individual pieces of thin glass 30a, and a functional layer 40a are laminated.

Next, in step c, a plurality of pieces of functional thin glass (thin glass 30a with functional layer 40a) are peeled off from the peelable adhesive tape 20 of laminate B-2 (FIG. 9(c)). ) and transported to the next process. At this time, the conveyance can be carried out using a known method such as vacuum suction or a jig.

[Sixth embodiment]
The method for manufacturing functional thin glass of this embodiment includes the following steps.
Step a-1': The thin glass 30 is attached to one side of the peelable adhesive tape 20 to obtain an adhesive tape with thin glass.
Step a-2': Cutting the adhesive tape 20 with thin glass 30 in the lamination direction to obtain a plurality of pieces of adhesive tape 20a with thin glass 30a,
Step a-3': A plurality of pieces of the adhesive tape 20a with the thin glasses 30a that have been cut into pieces are pasted in a matrix shape on the support 10 to obtain a laminate A-3 (FIG. 10(a) ).
Step b: Processing the thin glass 30a of the laminate A-3 to obtain a laminate B-3 comprising functional thin glass (FIG. 10(b)).
Step c: The functional thin glass subjected to the processing is peeled off from the peelable adhesive tape 20a of the laminate B-3 (FIG. 10(c)).

In step a-1', as described in step a above, the thin glass 30 is attached to one surface of the removable adhesive tape 20 to obtain an adhesive tape with thin glass.

In step a-2', the thin glass-coated adhesive tape obtained in step a-1' is temporarily fixed by pasting the thin glass side onto a resin film, and the thin glass-coated adhesive tape is applied from the adhesive tape side. Can be cut in the stacking direction. This makes it possible to obtain a laminate in which a plurality of pieces of adhesive tape with thin glass are attached to a resin film.
For cutting, a cutting means such as a diamond cutter can be used.
By the cutting, a plurality of individual pieces of adhesive tape with thin glass are obtained. The shape of the adhesive tape with thin glass may be strip-shaped, square, rectangular, etc. when viewed from above, and can be determined depending on the application.

In step a-3', a plurality of individual thin glass-attached 30a adhesive tapes 20a are adhered to a support in a matrix shape to obtain a laminate A-3 (FIG. 10(a)).
Specifically, the adhesive tape 20a with thin glass 30a is sequentially unwound from a roll of resin film to which the adhesive tape 20a with thin glass 30a, which has been cut into a plurality of pieces, is affixed, and the adhesive tape 20a with thin glass 30a is applied to the surface of the support 10. , and then peeling off the resin film from the adhesive tape 20a with thin glass 30a, and pasting a plurality of adhesive tapes 20a with thin glass 30a on the base material 10 in a matrix shape, or singulation. An example of this method is to sequentially place a plurality of thin glass-covered 30a adhesive tapes 20a.

Next, in the same manner as in step b described above, as shown in FIG. 10(b), a functional layer 40a is formed on the plurality of thin glasses 30a of the laminate A-3, and a functional layer 40a is formed on the adhesive tape 20a. A laminate B-3 including thin glass (thin glass 30a with functional layer 40a) is obtained. The laminate B-2 has a structure in which a support 10, a peelable adhesive tape 20a, a plurality of individual pieces of thin glass 30a, and a functional layer 40a are laminated.

Next, in step c, a plurality of functional thin glasses (thin glass 30a with functional layer 40a) are peeled off from the peelable adhesive tape 20a of the laminate B-3 (FIG. 10(c)), and then subjected to the next step. transported. At this time, the conveyance can be carried out using a known method such as vacuum suction or a jig.

The layers constituting the peelable adhesive tape 20 and the thermally expandable microspheres a will be explained below.

(Base material layer 22)
The base material layer 22 constituting the peelable adhesive tape 20 is a layer provided for the purpose of improving the handling properties, mechanical properties, heat resistance, and other characteristics of the peelable adhesive tape 20.
Although the base material layer 22 is not particularly limited, for example, a resin film may be used.

Examples of the resin constituting the resin film include known thermoplastic resins. For example, polyolefins such as polyethylene, polypropylene, poly(4-methyl-1-pentene), and poly(1-butene); polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; Polyamide such as meta-xylene adipamide; polyacrylate; polymethacrylate; polyvinyl chloride; polyvinylidene chloride; polyimide; polyetherimide; ethylene/vinyl acetate copolymer; polyacrylonitrile; polycarbonate; polystyrene; ionomer; polysulfone; One or more types selected from ether sulfone; polyphenylene ether, etc. can be mentioned.

Among these, from the viewpoint of excellent balance of transparency, mechanical strength, price, etc., one or more selected from polypropylene, polyethylene terephthalate, polyethylene naphthalate, polyamide, and polyimide are preferred, and polyethylene terephthalate and polyethylene naphthalate are preferred. At least one selected from the following is more preferred.

The base material layer 22 may be a single layer or may be a layer of two or more types.
Further, the form of the resin film used to form the base material layer 22 may be a stretched film or a film stretched in a uniaxial direction or biaxial direction. From the viewpoint of improving the mechanical strength of the film, it is preferable that the film be uniaxially or biaxially stretched.

From the viewpoint of obtaining good film properties, the thickness of the base layer 22 is preferably 1 μm or more and 500 μm or less, more preferably 5 μm or more and 300 μm or less, and even more preferably 10 μm or more and 250 μm or less.
The base layer 22 may be surface-treated to improve adhesion with other layers. Specifically, corona treatment, plasma treatment, undercoat treatment, primer coat treatment, etc. may be performed.

[Thermally expandable microspheres a]
The adhesive resin layer (A), the adhesive resin layer (B), or the intermediate layer 28 is a heat-peelable adhesive resin layer that can contain thermally expandable microspheres a. Thereby, the thin glass 30 or the support 10 can be easily peeled off from the peelable adhesive tape 20 by heating.

As the thermally expandable microspheres a, for example, a microencapsulated foaming agent can be used. Examples of such thermally expandable microspheres include microspheres in which a substance that easily gasifies and expands upon heating, such as isobutane, propane, and pentane, is enclosed within an elastic shell. Examples of the material constituting the shell include vinylidene chloride-acrylonitrile copolymer, polyvinyl alcohol, polyvinyl butyral, polymethyl methacrylate, polyacrylonitrile, polyvinylidene chloride, polysulfone, and the like. Thermally expandable microspheres can be produced, for example, by a coacervation method, an interfacial polymerization method, or the like.

The content of the thermally expandable microspheres a can be appropriately set depending on the expansion magnification of the adhesive resin layer (A), the adhesive resin layer (B), or the intermediate layer 28, the tendency to reduce adhesive strength, etc. Although not particularly limited, for example, 1 part by mass or more and 150 parts by mass or less, preferably 10 parts by mass or more and 130 parts by mass or less, more preferably 12 parts by mass or more and 100 parts by mass, based on 100 parts by mass of the resin constituting these layers. It is as follows.
The temperature at which gas is generated from the thermally expandable microspheres or the temperature at which the thermally expandable microspheres thermally expand is preferably higher than 150°C, more preferably higher than 170°C, still more preferably higher than 190°C, even more preferably 210°C. It is preferable to design the temperature to be higher than 230°C, more preferably higher than 235°C, even more preferably higher than 240°C, even more preferably higher than 245°C.
Further, the temperature at which gas is generated from the thermally expandable microspheres or the temperature at which the thermally expandable microspheres thermally expand is preferably (T _B +5)°C or higher with respect to the heating temperature T _B in step b, It is preferable to design the temperature so that the temperature is more preferably (T _B +10)°C or higher, and even more preferably (T _B +15)°C or higher.
As mentioned above, when the functional layer is a light-shielding printed layer, T _B is preferably 160°C or higher, so the temperature at which gas is generated from the thermally expandable microspheres or the temperature at which the thermally expandable microspheres thermally expand The temperature is preferably 165°C or higher, more preferably 170°C or higher, even more preferably 175°C or higher. As a commercially available thermally expandable microsphere that expands in such a temperature range, there can be mentioned a high temperature expandable grade of "Matsumoto Microsphere (registered trademark) F, FN series" manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd.
As mentioned above, when the functional layer is a primer layer, T _B is preferably 230°C or higher, so the temperature at which gas is generated from the thermally expandable microspheres or the temperature at which the thermally expandable microspheres thermally expand. is preferably 235°C or higher, more preferably 240°C or higher, even more preferably 245°C or higher. Commercially available thermally expandable microspheres that expand in such a temperature range include the ultra-high temperature expandable grade of "Matsumoto Microsphere (registered trademark) F, FN series" manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd. .

The average particle diameter D ₅₀ of the thermally expandable microspheres a is, for example, preferably 1 μm or more and 47 μm or less, more preferably 5 μm or more and 27 μm or less. Furthermore, the particle diameter D _99.9 of the thermally expandable microspheres a is preferably 20 μm or more and 300 μm or less, more preferably 30 μm or more and 180 μm or less.
The average particle diameter of the thermally expandable microspheres a can be measured with a general particle shape/particle size analyzer, such as Microtrac MT3000II, FPIA-3000, Mastersizer 3000E, etc.

(Adhesive resin layer (A))
The present adhesive resin layer (A) is a layer for temporarily fixing the thin glass 30 by contacting the surface of the thin glass 30 during the processing process of the thin glass 30, for example.

Examples of the adhesive resin (A1) constituting the adhesive resin layer (A) include (meth)acrylic resin (a), urethane resin, silicone resin, polyolefin resin, polyester resin, and polyamide resin. , fluororesins, styrene-diene block copolymer resins, and the like. Among these, (meth)acrylic resin (a) is preferred.

The (meth)acrylic adhesive resin (a) used in the adhesive resin layer (A) includes, for example, a resin having a functional group that can react with the (meth)acrylic acid alkyl ester monomer unit (a1) and the crosslinking agent. A copolymer containing the monomer unit (a2) can be mentioned.
In the present embodiment, the (meth)acrylic acid alkyl ester means an acrylic acid alkyl ester, a methacrylic acid alkyl ester, or a mixture thereof.

The (meth)acrylic adhesive resin (a) according to the present embodiment is, for example, a monomer mixture containing a (meth)acrylic acid alkyl ester monomer (a1) and a monomer (a2) having a functional group capable of reacting with a crosslinking agent. It can be obtained by copolymerizing.

Examples of the monomer (a1) forming the (meth)acrylic acid alkyl ester monomer unit (a1) include (meth)acrylic acid alkyl esters having an alkyl group having about 1 to 12 carbon atoms. Preferred is a (meth)acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms. Specific examples include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, and 2-ethylhexyl methacrylate. These may be used alone or in combination of two or more.

In the (meth)acrylic adhesive resin (a) according to the present embodiment, the content of the (meth)acrylic acid alkyl ester monomer unit (a1) is the total monomer content in the (meth)acrylic adhesive resin (a). When the total of units is 100 mass%, it is preferably 10 mass% or more and 98.9 mass% or less, more preferably 50 mass% or more and 97 mass% or less, and 85 mass% or more and 95 mass% or less. It is more preferable that

Examples of the monomer (a2) forming the monomer (a2) having a functional group capable of reacting with a crosslinking agent include acrylic acid, methacrylic acid, itaconic acid, mesaconic acid, citraconic acid, fumaric acid, maleic acid, and itaconic acid monoalkyl ester. , mesaconic acid monoalkyl ester, citraconic acid monoalkyl ester, fumaric acid monoalkyl ester, maleic acid monoalkyl ester, glycidyl acrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, acrylamide , methacrylamide, tertiary-butylaminoethyl acrylate, tertiary-butylaminoethyl methacrylate, and the like. Preferred are acrylic acid, methacrylic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, acrylamide, methacrylamide, and the like. These may be used alone or in combination of two or more.
In the (meth)acrylic adhesive resin (a) according to the present embodiment, the content of monomer units (a2) is 100% by mass of the total of all monomer units in the (meth)acrylic adhesive resin (a). The content is preferably 1% by mass or more and 40% by mass or less, more preferably 1% by mass or more and 20% by mass or less, and even more preferably 1% by mass or more and 10% by mass or less.

The (meth)acrylic adhesive resin (a) according to the present embodiment includes, in addition to monomer units (a1) and monomer units (a2), a bifunctional monomer unit (a3) and a specific compound having properties as a surfactant. It may further contain a comonomer unit (hereinafter referred to as a polymerizable surfactant).
The polymerizable surfactant has a property of copolymerizing with monomer (a1), monomer (a2), and monomer (a3), and also acts as an emulsifier when emulsion polymerization is performed.

Monomers (a3) forming the bifunctional monomer unit (a3) include allyl methacrylate, allyl acrylate, divinylbenzene, vinyl methacrylate, vinyl acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri( meth)acrylate, dipentaerythritol hexa(meth)acrylate, tetraethylene glycol di(meth)acrylate, and, for example, diacrylate or dimethacrylate at both ends and propylene glycol type main chain structure (for example, NOF Corporation) (manufactured by NOF Corporation; product names: PDP-200, PDP-400, ADP-200, ADP-400), tetramethylene glycol type (for example, manufactured by NOF Corporation; product names: ADT-250, ADT-850) ) and mixed types thereof (for example, manufactured by NOF Corporation; trade names: ADET-1800 and ADET-4000).

In the (meth)acrylic adhesive resin (a) according to the present embodiment, the content of monomer units (a3) is 100% by mass of the total of all monomer units in the (meth)acrylic adhesive resin (a). It is preferably 0.1% by mass or more and 30% by mass or less, more preferably 0.1% by mass or more and 15% by mass or less, and 0.1% by mass or more and 20% by mass or less. is more preferable, and particularly preferably 0.1% by mass or more and 5% by mass or less.

Examples of polymerizable surfactants include those obtained by introducing a polymerizable 1-propenyl group into the benzene ring of polyoxyethylene nonylphenyl ether (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.; trade name: Aqualon RN-10). , RN-20, RN-30, RN-50, etc.), polyoxyethylene nonylphenyl ether sulfate ester ammonium salt with a polymerizable 1-propenyl group introduced into the benzene ring (Daiichi Kogyo Seiyaku) Aqualon HS-10, Aqualon HS-20, Aqualon HS-1025, etc.), and sulfosuccinic acid diester type (manufactured by Kao Corporation; product name) that has a polymerizable double bond in the molecule. : Latemul S-120A, Latemul S-180A, etc.).

In the (meth)acrylic adhesive resin (a) according to the present embodiment, the content of the polymerizable surfactant is 100% by mass of the total of all monomer units in the (meth)acrylic adhesive resin (a). It is preferably 0.1% by mass or more and 30% by mass or less, more preferably 0.1% by mass or more and 20% by mass or less, and 0.1% by mass or more and 15% by mass or less. is more preferable, and particularly preferably 0.1% by mass or more and 5% by mass or less.

The (meth)acrylic adhesive resin (a) according to the present embodiment further contains a monomer unit formed from a monomer having a polymerizable double bond such as vinyl acetate, acrylonitrile, or styrene, if necessary. You can.

Examples of the polymerization reaction mechanism of the (meth)acrylic adhesive resin (a) according to this embodiment include radical polymerization, anionic polymerization, and cationic polymerization. Considering the manufacturing cost of the (meth)acrylic adhesive resin (a), the influence of the functional groups of the monomers, the influence of ions on the surface of electronic parts, etc., it is preferable to carry out polymerization by radical polymerization.
When polymerizing by radical polymerization reaction, benzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, 3,3,5-trimethylhexanoyl peroxide, di-2-ethylhexyl peroxide is used as a radical polymerization initiator. Dicarbonate, methyl ethyl ketone peroxide, t-butyl peroxyphthalate, t-butyl peroxybenzoate, di-t-butyl peroxy acetate, t-butyl peroxyisobutyrate, t-butyl peroxy-2-hexanoate, t -Butylperoxy-2-ethylhexanoate, t-butylperoxy-3,5,5-trimethylhexanoate, acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, t-butyl peroxide, di -Organic peroxides such as t-amyl peroxide; Inorganic peroxides such as ammonium persulfate, potassium persulfate, and sodium persulfate; 2,2'-azobisisobutyronitrile, 2,2'-azobis-2 Examples include azo compounds such as -methylbutyronitrile and 4,4'-azobis-4-cyanovaleric acid.

In the case of polymerization by emulsion polymerization, among these radical polymerization initiators, water-soluble inorganic peroxides such as ammonium persulfate, potassium persulfate, and sodium persulfate, and also water-soluble 4,4'-azobis Azo compounds having a carboxyl group in the molecule, such as -4-cyanovaleric acid, are preferred. Considering the influence of ions on the surface of electronic parts, azo compounds having a carboxyl group in the molecule such as ammonium persulfate and 4,4'-azobis-4-cyanovaleric acid are more preferred; Particularly preferred are azo compounds having a carboxyl group in the molecule, such as -4-cyanovaleric acid.

In addition to the adhesive resin (A1), the adhesive resin layer (A) according to the present embodiment preferably further includes a crosslinking agent (A2) having two or more crosslinkable functional groups in one molecule.
The crosslinking agent (A2) having two or more crosslinkable functional groups in one molecule is used to react with the functional groups of the adhesive resin (A1) to adjust the adhesive force and cohesive force.
Such crosslinking agents (A2) include sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, glycerol polyglycidyl ether, neopentyl glycol diglycidyl ether, resorcin diglycidyl Epoxy compounds such as ether; Isocyanate compounds such as tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate 3-adduct of trimethylolpropane, polyisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate; trimethylolpropane-tri-β-aziridine lupropionate, tetramethylolmethane-tri-β-aziridinylpropionate, N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxamide), N,N'-hexamethylene-1 , 6-bis(1-aziridinecarboxamide), N,N'-toluene-2,4-bis(1-aziridinecarboxamide), trimethylolpropane-tri-β-(2-methylaziridine)propionate, etc. system compounds; tetrafunctional epoxy compounds such as N,N,N',N'-tetraglycidyl-m-xylene diamine, 1,3-bis(N,N'-diglycidylaminomethyl)cyclohexane; hexamethoxymethylol Examples include melamine-based compounds such as melamine. These may be used alone or in combination of two or more.
Among these, it is preferable to include one or more selected from epoxy compounds, isocyanate compounds, and aziridine compounds.

The content of the crosslinking agent (A2) is usually preferably within a range such that the number of functional groups in the crosslinking agent (A2) does not exceed the number of functional groups in the adhesive resin (A1). However, it may be contained in excess if necessary, such as when new functional groups are generated in the crosslinking reaction or when the crosslinking reaction is slow.
The content of the crosslinking agent (A2) in the adhesive resin layer (A) is preferably 0.1 parts by mass or more and 10 parts by mass or less, and 0.5 parts by mass or less, based on 100 parts by mass of the adhesive resin (A1). More preferably, it is at least 5 parts by mass and at most 5 parts by mass.

The adhesive resin layer (A) according to the present embodiment preferably contains a tackifier resin in addition to the adhesive resin (A1) from the viewpoint of improving adhesion to the support substrate. It is preferable to include a tackifying resin in the adhesive resin layer (A) because it becomes easy to adjust the adhesion with the supporting substrate at around room temperature. The tackifier resin preferably has a softening point of 100°C or higher. Specific examples of tackifying resins include rosin-based resins such as rosin-based derivatives treated with esterification; terpene-based resins such as α-pinene, β-pinene, dipentene, and terpene phenol; gum-based, Natural rosins such as wood-based and tall oil-based rosins; examples of these natural rosins include hydrogenated, disproportionated, polymerized, maleated, petroleum resins; coumaron-indene resins.

Among these, those with a softening point in the range of 100 to 160°C are more preferred, and those with a softening point in the range of 120 to 150°C are particularly preferred. When a tackifying resin having a softening point within the above range is used, not only is there less contamination and adhesive residue on the supporting substrate, but also it is possible to further improve the adhesion to the supporting substrate in a working environment. Furthermore, when a polymerized rosin ester-based tackifying resin is used as the tackifying resin, not only is there less contamination and adhesive residue on the supporting substrate, but also the adhesion to the supporting substrate is improved in an environment of 80 to 130°C. In the case of a heat-expandable adhesive containing heat-expandable microspheres, after the heat-expandable microspheres a are expanded, they can be more easily peeled off from the support substrate.

The blending ratio of the tackifying resin may be appropriately selected so that the modulus of elasticity of the adhesive resin layer (A) can be adjusted within a desired predetermined numerical range, and is not particularly limited. However, in view of the elastic modulus and initial peeling force of the adhesive resin layer (A), it is preferable to use 1 to 100 parts by mass based on 100 parts by mass of the adhesive resin (A1). When the blending ratio of the tackifier resin is equal to or higher than the above lower limit based on 100 parts by mass of the tackifying resin (A1), the adhesion to the support substrate during operation tends to be good. On the other hand, if it is below the above upper limit, the adhesion to the support substrate at room temperature tends to be good. In terms of adhesion to the supporting substrate and stickability at room temperature, it is more preferable that the blending ratio of the tackifying resin is 2 to 50 parts by mass based on 100 parts by mass of the adhesive resin (A1). Further, the acid value of the tackifying resin is preferably 30 or less. When the acid value of the tackifying resin is below the above upper limit, adhesive residue tends to be less likely to be left on the supporting substrate upon peeling.

The adhesive resin layer (A) may contain additives such as plasticizers as other components. The total content of the adhesive resin (A1), crosslinking agent (A2), and tackifier resin in the adhesive resin layer (A) is preferably 100% by mass when the entire adhesive resin layer (A) is 100% by mass. The content is 50% by mass or more, more preferably 70% by mass or more, even more preferably 90% by mass or more, particularly preferably 95% by mass or more. Further, when the adhesive resin layer (A) is composed of a heat-expandable adhesive, the adhesive resin (A1), the crosslinking agent (A2), the tackifier resin, and the gas generation in the adhesive resin layer (A) The total content of the components and thermally expandable microspheres is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably It is 90% by mass or more, particularly preferably 95% by mass or more.

The adhesive resin layer (A) may be a single layer or a multilayer. For example, by laminating two or more layers with different degrees of expansion upon heating to form the adhesive resin layer (A), one surface and the other surface of the adhesive resin layer (A) can be It is also possible to change the releasability.
The thickness of the adhesive resin layer (A) is, for example, preferably 5 μm or more and 300 μm or less, more preferably 20 μm or more and 150 μm or less.

The adhesive resin layer (A) may be composed of one layer of the adhesive resin layer (A1) containing thermally expandable microspheres a, as shown in the layer structure (6) in FIG. As in configuration (7), it may be composed of a single adhesive resin layer (A2) having the same composition as layer (A1) except that it does not contain thermally expandable microspheres a. Alternatively, the adhesive resin layer (A) may be composed of multiple layers including an adhesive resin layer (A1) and an adhesive resin layer (A2).

The adhesive resin layer (A) can be formed, for example, by applying an adhesive coating liquid onto the base layer 22 or the intermediate layer 28, or by applying the adhesive resin layer (A) formed on the separator to the base layer 22 or the intermediate layer. It can be formed by a method of transferring onto the layer 28 or the like.
As a method for applying the adhesive coating liquid, conventionally known coating methods such as a roll coater method, a reverse roll coater method, a gravure roll method, a bar coat method, a comma coater method, a die coater method, etc. can be employed. There are no particular restrictions on the drying conditions for the applied adhesive, but it is generally preferable to dry it at a temperature in the range of 80 to 200°C for 10 seconds to 10 minutes. More preferably, drying is performed at 80 to 170°C for 15 seconds to 5 minutes. In order to sufficiently promote the crosslinking reaction between the crosslinking agent and the adhesive, after the adhesive coating liquid has been dried, it may be heated at 40 to 80°C for about 5 to 300 hours.

Further, the base material layer 22 and the adhesive resin layer (A) may be formed by co-extrusion molding, or the film-like base material layer 22 and the film-like adhesive resin layer (A) may be laminated (laminated). ) may be formed.
The base material layer 22, the intermediate layer 28, and the adhesive resin layer (A) may be formed by coextrusion molding, or the base material layer 22 in the form of a film, the intermediate layer 28 in the form of a film, and the adhesive resin layer in the form of a film may be formed by coextrusion molding. (A) may be laminated (stacked).

(Adhesive resin layer (B))
The adhesive resin layer (B) is a layer for temporarily fixing the "peelable adhesive tape with thin glass" by contacting the surface of the support 10, for example, in the method for producing functional thin glass.

The adhesive resin layer (B) usually contains adhesive resin (B1).
Examples of the adhesive resin (B1) include (meth)acrylic adhesive resin (b), silicone adhesive resin, urethane adhesive resin, olefin adhesive resin, styrene adhesive resin, etc. .
Among these, (meth)acrylic adhesive resin (b) is preferred from the viewpoint of facilitating adjustment of adhesive strength.

The adhesive resin layer (B) can also be a radiation-crosslinked adhesive resin layer whose adhesive strength can be reduced by radiation. When the radiation-crosslinkable adhesive resin layer is irradiated with radiation, it crosslinks and its adhesive strength is significantly reduced, making it easier to peel off the releasable adhesive tape from thin glass. Examples of radiation include ultraviolet rays, electron beams, and infrared rays.
As the radiation crosslinkable adhesive resin layer, an ultraviolet crosslinkable adhesive resin layer is preferable.

The (meth)acrylic adhesive resin (b) used in the adhesive resin layer (B) includes, for example, a resin having a functional group that can react with the (meth)acrylic acid alkyl ester monomer unit (b1) and the crosslinking agent. A copolymer containing the monomer unit (b2) can be mentioned.
In the present embodiment, the (meth)acrylic acid alkyl ester means an acrylic acid alkyl ester, a methacrylic acid alkyl ester, or a mixture thereof.

The (meth)acrylic adhesive resin (b) according to the present embodiment is, for example, a monomer mixture containing a (meth)acrylic acid alkyl ester monomer (b1) and a monomer (b2) having a functional group that can react with a crosslinking agent. It can be obtained by copolymerizing.

Examples of the monomer (b1) forming the (meth)acrylic acid alkyl ester monomer unit (b1) include (meth)acrylic acid alkyl esters having an alkyl group having about 1 to 12 carbon atoms. Preferred is a (meth)acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms. Specific examples include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, and 2-ethylhexyl methacrylate. These may be used alone or in combination of two or more.

In the (meth)acrylic adhesive resin (b) according to the present embodiment, the content of the (meth)acrylic acid alkyl ester monomer unit (b1) is the total monomer content in the (meth)acrylic adhesive resin (b). When the total of units is 100 mass%, it is preferably 10 mass% or more and 98.9 mass% or less, more preferably 50 mass% or more and 97 mass% or less, and 85 mass% or more and 95 mass% or less. It is more preferable that

Examples of the monomer (b2) forming the monomer (b2) having a functional group capable of reacting with a crosslinking agent include acrylic acid, methacrylic acid, itaconic acid, mesaconic acid, citraconic acid, fumaric acid, maleic acid, and itaconic acid monoalkyl ester. , mesaconic acid monoalkyl ester, citraconic acid monoalkyl ester, fumaric acid monoalkyl ester, maleic acid monoalkyl ester, glycidyl acrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, acrylamide , methacrylamide, tertiary-butylaminoethyl acrylate, tertiary-butylaminoethyl methacrylate, and the like. Preferred are acrylic acid, methacrylic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, acrylamide, methacrylamide, and the like. These may be used alone or in combination of two or more.
In the (meth)acrylic adhesive resin (b) according to the present embodiment, the content of monomer units (b2) is 100% by mass of the total of all monomer units in the (meth)acrylic adhesive resin (b). The content is preferably 1% by mass or more and 40% by mass or less, more preferably 1% by mass or more and 20% by mass or less, and even more preferably 1% by mass or more and 10% by mass or less.

The (meth)acrylic adhesive resin (b) according to the present embodiment includes, in addition to the monomer unit (b1) and the monomer unit (b2), a bifunctional monomer unit (b3) and a specific compound having properties as a surfactant. It may further contain a comonomer unit (hereinafter referred to as a polymerizable surfactant).
The polymerizable surfactant has a property of copolymerizing with monomer (b1), monomer (b2), and monomer (b3), and also acts as an emulsifier when emulsion polymerization is performed.

The monomer (b3) forming the bifunctional monomer unit (b3) includes allyl methacrylate, allyl acrylate, divinylbenzene, vinyl methacrylate, vinyl acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri( meth)acrylate, dipentaerythritol hexa(meth)acrylate, tetraethylene glycol di(meth)acrylate, and, for example, diacrylate or dimethacrylate at both ends and propylene glycol type main chain structure (for example, NOF Corporation) (manufactured by NOF Corporation, product names: PDP-200, PDP-400, ADP-200, ADP-400), tetramethylene glycol type (for example, manufactured by NOF Corporation, product names: ADT-250, ADT-850) ) and mixtures thereof (eg, manufactured by NOF Corporation, product names: ADET-1800 and ADET-4000).

In the (meth)acrylic adhesive resin (b) according to the present embodiment, the content of monomer units (b3) is 100% by mass of the total of all monomer units in the (meth)acrylic adhesive resin (b). 0.1% by mass or more and 30% by mass or less, more preferably 0.1% by mass or more and 15% by mass or less, even more preferably 0.1% by mass or more and 20% by mass or less, and 0.1% by mass. The content is particularly preferably 5% by mass or less.

Examples of polymerizable surfactants include those obtained by introducing a polymerizable 1-propenyl group into the benzene ring of polyoxyethylene nonylphenyl ether (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.; trade name: Aqualon RN-10). , RN-20, RN-30, RN-50, etc.), polyoxyethylene nonylphenyl ether sulfate ester ammonium salt with a polymerizable 1-propenyl group introduced into the benzene ring (Daiichi Kogyo Seiyaku) Aqualon HS-10, Aqualon HS-20, Aqualon HS-1025, etc.), and sulfosuccinic acid diester type (manufactured by Kao Corporation; product name) that has a polymerizable double bond in the molecule. : Latemul S-120A, Latemul S-180A, etc.).
In the (meth)acrylic adhesive resin (b) according to the present embodiment, the content of the polymerizable surfactant is 100% by mass of the total of all monomer units in the (meth)acrylic adhesive resin (b). 0.1% by mass or more and 30% by mass or less, more preferably 0.1% by mass or more and 15% by mass or less, even more preferably 0.1% by mass or more and 20% by mass or less, and 0.1% by mass. The content is particularly preferably 5% by mass or less.

The (meth)acrylic adhesive resin (b) according to the present embodiment further contains a monomer unit formed from a monomer having a polymerizable double bond such as vinyl acetate, acrylonitrile, or styrene, if necessary. You can.

Examples of the polymerization reaction mechanism of the (meth)acrylic adhesive resin (b) according to this embodiment include radical polymerization, anionic polymerization, and cationic polymerization. Considering the manufacturing cost of the (meth)acrylic adhesive resin (b), the influence of the functional groups of the monomers, the influence of ions on the surface of electronic parts, etc., it is preferable to carry out polymerization by radical polymerization.
When polymerizing by radical polymerization reaction, benzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, 3,3,5-trimethylhexanoyl peroxide, di-2-ethylhexyl peroxide is used as a radical polymerization initiator. Dicarbonate, methyl ethyl ketone peroxide, t-butyl peroxyphthalate, t-butyl peroxybenzoate, di-t-butyl peroxy acetate, t-butyl peroxyisobutyrate, t-butyl peroxy-2-hexanoate, t -Butylperoxy-2-ethylhexanoate, t-butylperoxy-3,5,5-trimethylhexanoate, acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, t-butyl peroxide, di -Organic peroxides such as t-amyl peroxide; Inorganic peroxides such as ammonium persulfate, potassium persulfate, and sodium persulfate; 2,2'-azobisisobutyronitrile, 2,2'-azobis-2 Examples include azo compounds such as -methylbutyronitrile and 4,4'-azobis-4-cyanovaleric acid.

In the case of polymerization by emulsion polymerization, among these radical polymerization initiators, water-soluble inorganic peroxides such as ammonium persulfate, potassium persulfate, and sodium persulfate, and also water-soluble 4,4'-azobis Azo compounds having a carboxyl group in the molecule, such as -4-cyanovaleric acid, are preferred. Considering the influence of ions on the surface of electronic parts, azo compounds having a carboxyl group in the molecule such as ammonium persulfate and 4,4'-azobis-4-cyanovaleric acid are more preferred; Particularly preferred are azo compounds having a carboxyl group in the molecule, such as -4-cyanovaleric acid.

In addition to the adhesive resin (B1), the adhesive resin layer (B) according to the present embodiment preferably further includes a crosslinking agent (B2) having two or more crosslinkable functional groups in one molecule.

The crosslinking agent (B2) having two or more crosslinkable functional groups in one molecule can be reacted with the functional groups of the adhesive resin (B1) to adjust the adhesive force and cohesive force.
Such crosslinking agents (B2) include sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, glycerol polyglycidyl ether, neopentyl glycol diglycidyl ether, resorcin diglycidyl Epoxy compounds such as ether; Isocyanate compounds such as tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate 3-adduct of trimethylolpropane, polyisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate; trimethylolpropane-tri-β-aziridine lupropionate, tetramethylolmethane-tri-β-aziridinylpropionate, N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxamide), N,N'-hexamethylene-1 , 6-bis(1-aziridinecarboxamide), N,N'-toluene-2,4-bis(1-aziridinecarboxamide), trimethylolpropane-tri-β-(2-methylaziridine)propionate, etc. system compounds; tetrafunctional epoxy compounds such as N,N,N',N'-tetraglycidyl-m-xylene diamine, 1,3-bis(N,N'-diglycidylaminomethyl)cyclohexane; hexamethoxymethylol Examples include melamine-based compounds such as melamine. These may be used alone or in combination of two or more.
Among these, it is preferable to include one or more selected from epoxy compounds, isocyanate compounds, and aziridine compounds.

The content of the crosslinking agent (B2) is usually preferably within a range such that the number of functional groups in the crosslinking agent (B2) does not exceed the number of functional groups in the adhesive resin (B1). However, it may be contained in excess if necessary, such as when new functional groups are generated in the crosslinking reaction or when the crosslinking reaction is slow.
The content of the crosslinking agent (B2) in the adhesive resin layer (B) is 100 parts by mass of the adhesive resin (B1) from the viewpoint of improving the balance between the heat resistance and adhesion of the adhesive resin layer (B). The amount is preferably 0.1 parts by mass or more and 15 parts by mass or less.

The adhesive resin layer (B) may contain additives such as a plasticizer and a tackifier resin as other components. When the adhesive resin layer (B) is a radiation crosslinkable adhesive resin layer, it may contain various additives for radiation crosslinking. The total content of the adhesive resin (B1) and crosslinking agent (B2) in the adhesive resin layer (B) is preferably 50% by mass when the entire adhesive resin layer (B) is 100% by mass. The content is more preferably 70% by mass or more, further preferably 90% by mass or more, particularly preferably 95% by mass or more. Thereby, it is possible to further suppress adhesive residue on the support side when the peelable adhesive tape is peeled from the support.

The adhesive resin layer (B) may be composed of one layer of the adhesive resin layer (B1) containing thermally expandable microspheres a, as shown in layer structure (7) in FIG. As shown in layer structure (6), it may be composed of a single adhesive resin layer (B2) having the same composition as layer (B1) except that it does not contain thermally expandable microspheres a. Alternatively, the adhesive resin layer (B) may be composed of multiple layers including an adhesive resin layer (B1) and an adhesive resin layer (B2).
The thickness of the adhesive resin layer (B) is not particularly limited, but is preferably, for example, 1 μm or more and 100 μm or less, more preferably 3 μm or more and 50 μm or less.

The adhesive resin layer (B) can be formed, for example, by applying an adhesive onto the base layer 22 or the intermediate layer 28. The adhesive may be dissolved in a solvent and applied as a coating liquid, it may be applied as an aqueous emulsion, or the liquid adhesive may be applied directly.
Among these, water-based emulsion coating liquids are preferred. As the water-based emulsion coating liquid, for example, (meth)acrylic adhesive resin (b), silicone adhesive resin, urethane adhesive resin, olefin adhesive resin, styrene adhesive resin, etc. are dispersed in water. Examples include coating liquids.

An adhesive coating solution dissolved in an organic solvent may also be used. The organic solvent is not particularly limited, and may be appropriately selected from known organic solvents in view of solubility and drying time. Examples of organic solvents include ester systems such as ethyl acetate and methyl acetate; ketone systems such as acetone and MEK; aromatic systems such as benzene, toluene, and ethylbenzene; linear or cycloaliphatic systems such as heptane, hexane, and cyclohexane; isopropanol. Examples include alcohols such as , butanol and the like. Ethyl acetate and toluene are preferred as organic solvents. These solvents may be used alone or in combination of two or more.

As a method for applying the adhesive coating liquid, conventionally known coating methods such as a roll coater method, a reverse roll coater method, a gravure roll method, a bar coat method, a comma coater method, a die coater method, etc. can be employed. There are no particular restrictions on the drying conditions for the applied adhesive, but it is generally preferable to dry it at a temperature in the range of 80 to 200°C for 10 seconds to 10 minutes. More preferably, drying is performed at 80 to 170°C for 15 seconds to 5 minutes. In order to sufficiently promote the crosslinking reaction between the crosslinking agent and the adhesive, after the adhesive coating liquid has been dried, it may be heated at 40 to 80°C for about 5 to 300 hours.

Further, the base material layer 22, the adhesive resin layer (A) and the intermediate layer 28 may be formed by co-extrusion molding, or the film-like base material layer 22 and the film-like adhesive resin layer (A) may be formed by co-extrusion molding. It may be formed by laminating (layering). In the examples described below, first, an adhesive resin layer (A) is formed on the surface of a separator (release film), and then the adhesive resin layer (A) is bonded to another layer to perform peeling. The molded adhesive tape 20 is manufactured.

(Middle layer 28)
The intermediate layer 28 absorbs irregularities on the surface of the adhesive resin layer caused by the thermally expandable microspheres a, and can suppress the formation of void walls between the support and the thin glass 30. The thin glass 30 can be uniformly temporarily fixed during processing, and furthermore, the thin glass 30 can be prevented from being contaminated. Furthermore, the presence of the intermediate layer 28 allows the thin glass 30 to be positioned with respect to the support 10, and the processability of the thin glass 30 is excellent.
Furthermore, the elastic modulus of the intermediate layer 28 can be increased by crosslinking and hardening the intermediate layer 28 by external stimulation. Thereby, in processing the thin glass 30, the thin glass 30 can be positioned more accurately with respect to the support 10, and the processability of the thin glass 30 is further improved.
External stimuli include, for example, heat or light.
The intermediate layer 28 can also be described as an uneven absorbing resin layer due to its function.

The resin constituting the intermediate layer 28 is not particularly limited as long as it exhibits unevenness absorption properties, and is preferably a thermoplastic resin, for example. Specifically, one or more types selected from the group consisting of polyolefin resins, polystyrene resins, and (meth)acrylic resins are more preferable. As another aspect, a resin having a Shore D hardness according to ASTM D-2240 Shore D is preferably 50 or less, more preferably 40 or less.
Even when the resin constituting the intermediate layer 28 is not a thermoplastic resin, it is preferable that it has the same unevenness absorption properties as above.

Intermediate layer 28 preferably includes a resin, a crosslinking agent, and an initiator that generates active chemical species upon external stimulation. When the intermediate layer 28 contains these components, the intermediate layer 28 can be crosslinked more effectively by external stimulation, and the elastic modulus of the intermediate layer 28 can be further improved. This can prevent the intermediate layer 28 from softening due to heat during the process of sealing electronic components with the sealant, and as a result, prevent the electronic components from sinking into the peelable adhesive tape due to the pressure of the sealant. This can be further suppressed.
Note that depending on the chemical structure and reactivity of the resin and crosslinking agent, the intermediate layer 28 may be crosslinked (cured) by external stimulation even if it does not necessarily contain an initiator.

The resin that can be used to form the intermediate layer 28 is not particularly limited, but for example, the resin described as the adhesive resin (A1) in the adhesive resin layer described above can be preferably mentioned.

Other resins that can be used to form the intermediate layer 28 are not particularly limited, and include, for example, ethylene/α-olefin copolymers containing ethylene and α-olefins having 3 to 20 carbon atoms, high-density ethylene resins, Low density ethylene resin, medium density ethylene resin, ultra low density ethylene resin, linear low density polyethylene (LLDPE) resin, propylene (co)polymer, 1-butene (co)polymer, 4-methyl Pentene-1 (co)polymer, ethylene/cyclic olefin copolymer, ethylene/α-olefin/cyclic olefin copolymer, ethylene/α-olefin/non-conjugated polyene copolymer, ethylene/α-olefin/conjugated polyene Olefin resins such as copolymers, ethylene/aromatic vinyl copolymers, ethylene/α-olefin/aromatic vinyl copolymers; ethylene/unsaturated carboxylic anhydride copolymers, ethylene/α-olefin/unsaturated Ethylene/carboxylic anhydride copolymers such as carboxylic anhydride copolymers; ethylene/epoxy copolymers such as ethylene/epoxy-containing unsaturated compound copolymers and ethylene/α-olefin/epoxy-containing unsaturated compound copolymers Polymer: Ethylene/ethyl (meth)acrylate copolymer, ethylene/methyl (meth)acrylate copolymer, ethylene/propyl (meth)acrylate copolymer, ethylene/butyl (meth)acrylate copolymer , ethylene/hexyl (meth)acrylate copolymer, ethylene/2-hydroxyethyl (meth)acrylate copolymer, ethylene/2-hydroxypropyl (meth)acrylate copolymer, ethylene/(meth)acrylate copolymer Ethylene/(meth)acrylic acid ester copolymers such as glycidyl acrylate copolymers; ethylene/(meth)acrylic acid copolymers, ethylene/maleic acid copolymers, ethylene/fumaric acid copolymers, ethylene/croton Ethylene/ethylenic unsaturated acid copolymers such as acid copolymers; ethylene/vinyl acetate copolymer, ethylene/vinyl propionate copolymer, ethylene/vinyl butyrate copolymer, ethylene/vinyl stearate copolymer Ethylene/vinyl ester copolymers such as; ethylene/styrene copolymers, etc.; unsaturated carboxylic acid ester (co)polymers such as (meth)acrylic acid ester (co)polymers; ethylene/acrylic acid metal salt copolymers Ionomer resins such as ethylene/methacrylic acid metal salt copolymers; urethane resins; silicone resins; acrylic acid resins; methacrylic acid resins; cyclic olefin (co)polymers; α-olefins/aromatics Vinyl compound/aromatic polyene copolymer; ethylene/α-olefin/aromatic vinyl compound; aromatic polyene copolymer; ethylene/aromatic vinyl compound/aromatic polyene copolymer; styrene resin; acrylonitrile/butadiene/ Styrene copolymer; Styrene/conjugated diene copolymer; Acrylonitrile/styrene copolymer; Acrylonitrile/ethylene/α-olefin/non-conjugated polyene/styrene copolymer; Acrylonitrile/ethylene/α-olefin/conjugated polyene/styrene copolymer Polymer; methacrylic acid/styrene copolymer; ethylene terephthalate resin; fluororesin; polyester carbonate; polyvinyl chloride; polyvinylidene chloride; polyolefin thermoplastic elastomer; polystyrene thermoplastic elastomer; polyurethane thermoplastic elastomer; 1, One or more selected from 2-polybutadiene thermoplastic elastomer; trans polyisoprene thermoplastic elastomer; chlorinated polyethylene thermoplastic elastomer; liquid crystalline polyester; polylactic acid, etc. can be used.
The intermediate layer 28 may contain only one resin, or may contain two or more resins.

As the crosslinking agent that can be included in the intermediate layer 28, there may be mentioned without particular limitation those that undergo a crosslinking reaction with chemical species generated from an initiator.
Preferred crosslinking agents include polyfunctional (meth)acrylate compounds. More specifically, urethane (meth)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylolmethanetetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol Examples include stall monohydroxypenta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and 1,4-butanediol di(meth)acrylate.

Further, examples of the crosslinking agent include various monomers or oligomers such as urethane-based, polyether-based, polyester-based, polycarbonate-based, and polybutadiene-based.
The amount of the crosslinking agent is, for example, 5 parts by mass or more and 500 parts by mass or less, preferably 40 parts by mass or more and 150 parts by mass or less, based on 100 parts by mass of the resin (base polymer) such as a (meth)acrylic polymer.

As another aspect, the intermediate layer 28 may contain one or more crosslinking agents (A2) that can be contained in the adhesive resin layer (A) described above. Specifically, the intermediate layer 28 may contain an isocyanate-based compound. When such a crosslinking material is used, the amount thereof is, for example, 0.01 parts by mass or more and 5 parts by mass or less, preferably 0.01 parts by mass or more and 3 parts by mass or less, per 100 parts by mass of the resin (base polymer). be.

The initiator (initiator that generates active chemical species upon external stimulation) that the intermediate layer 28 may include is one that is capable of crosslinking the resin and/or crosslinking agent in the intermediate layer 28 by heat or light. If so, there are no particular limitations. The initiator must be an initiator that generates active species upon heat, taking into account that other layers may not be highly transparent and that light may be blocked by electronic components. is preferred.
The chemical species generated from the initiator may be appropriately selected based on the functional groups possessed by the resin and/or crosslinking agent. The chemical species generated from the initiator are typically radicals or cations.

Examples of initiators include aromatic ketones, onium salt compounds, organic peroxides, thio compounds, hexaarylbiimidazole compounds, ketooxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, carbon halogens. Examples include compounds having a bond, azo compounds, and the like. These may be used alone or in combination of two or more.
Among these, azo compounds or organic peroxides are preferred, and organic peroxides are more preferred, in terms of ease of availability, ease of handling, and the like.

Commercially available initiators include V-70, V-65, V-601, V-59, V-40, VF-096, V-30, VAm-110, VAm-111 (Fujifilm Wako Pure Pharmaceutical company), Niper BW, Niper BMT, Perloyl TCP, Perloyl L, Perloyl 355, Perloil SA, Perhexa HC, Perbutyl 355, Perbutyl D, Perbutyl L, Perbutyl ND, Perocta O, Perhexyl D, Perhexyl O, Perhexyl PV ( (all products manufactured by NOF), Trigonox 36-C75, Laurox, Parkadox L-W75, Parkadox CH-50L, Trigonox TMBH, Kayakumen H, Kayabutyl H-70, Parkadox BC-FF, Kayahexa AD, Parkadox 14, Kayabutyl C, Kayabutyl D, Parkadox 12-XL25, Trigonox 22-N70 (22-70E), Trigonox D-T50, Trigonox 423-C70, Kaya Ester CND-C70, Trigonox 23-C70, Trigonox 257-C70, Kaya Ester P-70, Kaya Ester TMPO-70, Trigonox 121, Kaya Ester O, Kaya Ester HTP-65W, Kaya Ester AN, Trigonox 42, Trigonox F-C50, Kayabutyl B, Kayacarbon EH, Kayacarbon I-20, Kayacarbon BIC-75 , Trigonox 117, Kayalen 6-70 (manufactured by Kayaku Akzo), etc.

When the intermediate layer 28 contains an initiator, the amount thereof is preferably 0.1 parts by mass or more, and 0.3 parts by mass or more based on 100 parts by mass of the resin (base polymer) such as a (meth)acrylic polymer. is more preferable, and 0.5 parts by mass or more is even more preferable. Further, from the viewpoint of storage stability, it is preferably 15 parts by mass or less, more preferably 5 parts by mass or less.

In the peelable adhesive tape 20 of the present embodiment, the lower limit of the storage elastic modulus E' at 60° C. of the intermediate layer 28 before crosslinking further prevents the electronic component from sinking into the adhesive film during the electronic component sealing process. From the viewpoint of being able to suppress the pressure, the pressure is preferably 1.0×10 ³ Pa or more, more preferably 5.0×10 3 Pa or more.
In addition, in the peelable adhesive tape 20 of this embodiment, the upper limit of the storage elastic modulus E' at 60° C. of the intermediate layer 28 before crosslinking is such that it can effectively absorb unevenness on the chip surface and furthermore, due to the springback of the resin, 1.0×10 ⁶ Pa or less is preferable, and 5.0×10 ⁵ Pa or less is more preferable in terms of preventing deterioration of unevenness absorption.
The storage modulus E' at 60° C. of the intermediate layer 28 before crosslinking can be controlled within the above range by, for example, controlling the type and blending ratio of each component constituting the intermediate layer 28.

In the peelable adhesive tape 20 of this embodiment, the lower limit of the storage elastic modulus E' at 125° C. of the intermediate layer 28 (C') obtained by crosslinking the intermediate layer 28 is The pressure is preferably 1.0×10 ⁶ Pa or more, and more preferably 5.0×10 ⁶ Pa or more, from the viewpoint of further suppressing sinking into the peelable adhesive tape.
In addition, in the peelable adhesive tape 20 of this embodiment, one of the intermediate layers 28 (C')
The upper limit of the storage elastic modulus E' at 25° C. is preferably 1.0×10 ⁹ Pa or less, and is preferably 1.0×10 ⁸ Pa or less, from the viewpoint of further suppressing the displacement of electronic components in the sealing process. The following are more preferred.
The storage elastic modulus E' at 125° C. of the intermediate layer 28 (C') can be controlled within the above range by, for example, controlling the type and blending ratio of each component constituting the intermediate layer 28.
Here, whether or not the crosslinking treatment of the intermediate layer 28 has been completed can be determined by determining, for example, that the point at which the storage elastic modulus E' of the intermediate layer 28 no longer increases even after the crosslinking treatment is performed is the point at which crosslinking is completed. I can do it.

In this embodiment, the intermediate layer 28 may also include thermally expandable microspheres a. Such an intermediate layer 28 is obtained by curing a photocurable resin.

The thickness of the intermediate layer 28 is not particularly limited as long as it can absorb unevenness on the surface of the adhesive resin layer, but for example, it is preferably 10 μm or more and 1000 μm or less, and 20 μm or more and 900 μm or less. It is more preferably 30 μm or more and 800 μm or less, and particularly preferably 50 μm or more and 700 μm or less.

The method for forming the intermediate layer 28 is not particularly limited, and the same method as for the adhesive resin layer (A) and the adhesive resin layer (B) can be adopted.

The releasable adhesive tape 20 of this embodiment may further include, for example, an easily bonding layer between each layer within a range that does not impair the effects of this embodiment.

Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various configurations other than those described above can be adopted within a range that does not impair the effects of the present invention.

10 Support 20 Peelable adhesive tape 30 Thin glass A Laminated body (A) Adhesive resin layer (B) Adhesive resin layer 22 Base layer 22a First surface a Thermally expandable microspheres 22b Second surface 28 Intermediate layer 30 ' Functional thin glass A-1 Laminated body 10a Support 20a Peelable adhesive tape 30a Thin glass 40a Functional layer B-1 Laminated body A' Laminated body B' Laminated body A-2 Laminated body B-2 Laminated body A-3 Laminated body B-3 Laminated body

Claims (21)

Step a of preparing a laminate A in which a support, a peelable adhesive tape, and a thin glass having a thickness of 1 μm to 200 μm are laminated in this order;
Processing the thin glass of the laminate A to obtain a laminate B comprising functional thin glass;
a step c of peeling the processed functional thin glass from the peelable adhesive tape of laminate B;
including;
The peelable adhesive tape is composed of multiple layers including an adhesive resin layer (A) on the thin glass side surface and an adhesive resin layer (B) on the support side surface, and at least one of the multiple layers containing thermally expandable microspheres in the layer;
Method for producing functional thin glass. The method for manufacturing functional thin glass according to claim 1, wherein the processing in step b is a step of forming a functional layer on the surface of the thin glass. The functional layer is at least one selected from a hard coat layer, an antireflection layer, an antifogging layer, an antifouling layer, a water repellent layer, an ultraviolet absorbing layer, an antistatic layer, a light-shielding printing layer, and a primer layer. , A method for producing functional thin glass according to claim 2. The functional thin glass subjected to the processing treatment is composed of a plurality of sheets,
The method for manufacturing functional thin glass according to claim 1, wherein the step c is a step of peeling a plurality of sheets of the functional thin glass from the peelable adhesive tape of the laminate B. Between step a and step b,
A step of cutting the entire laminate A in the lamination direction to obtain a plurality of pieces of the laminate A-1,
Step b is a step of processing at least one of the thin glasses of the plurality of singulated laminates A-1 to obtain a laminate B-1 comprising functional thin glass,
The method for producing functional thin glass according to claim 4, wherein the laminate B-1 has a structure in which a support, a peelable adhesive tape, and a functional thin glass are laminated in this order. Between step b and step c,
A step of cutting the entire laminate B including the functional thin glass in the lamination direction to obtain a plurality of individualized laminates B-1,
The method for producing functional thin glass according to claim 4, wherein the laminate B-1 has a structure in which a support, a peelable adhesive tape, and a functional thin glass are laminated in this order. Between step a and step b,
5. The method according to claim 4, further comprising the step of cutting the thin glass of the laminate A in the lamination direction to obtain a laminate A' in which a plurality of pieces of thin glass are bonded to the peelable adhesive tape. A method for producing functional thin glass. Between step b and step c,
A claim comprising the step of cutting the functional thin glass of the laminate B in the lamination direction to obtain a laminate B' in which a plurality of individual pieces of functional thin glass are bonded on the peelable adhesive tape. Item 4. The method for producing functional thin glass according to item 4. The thin glass is composed of a plurality of sheets,
Step a is
step a-1 of pasting the releasable adhesive tape on the support;
Step a-2 of obtaining a laminate A-2 by pasting a plurality of the thin glasses in a matrix on the peelable adhesive tape;
The method for producing functional thin glass according to claim 4, comprising: The method for producing functional thin glass according to claim 9, further comprising the step of subjecting a plurality of sheets of thin glass to surface polishing or edge treatment in advance, before step a-2. Step a is
a step a-1' of attaching the thin glass to one side of the peelable adhesive tape to obtain an adhesive tape with thin glass;
Step a-2' of cutting the thin glass-coated adhesive tape in the lamination direction to obtain a plurality of individualized thin glass-coated adhesive tapes;
5. A step a-3' of obtaining a laminate A-3 by pasting a plurality of pieces of the thin glass-attached adhesive tape into pieces on the support in a matrix shape. Method for producing functional thin glass. The peelable adhesive tape includes a base material layer, an adhesive resin layer (A) containing thermally expandable microspheres provided on one surface of the base material layer, and a adhesive resin layer (A) provided on the other surface of the base material layer. an adhesive resin layer (B),
The functional thin glass is pasted on the adhesive resin layer (A),
The functional thin glass according to any one of claims 1 to 11, wherein step c is a step of peeling the functional thin glass from the peelable adhesive tape by heating the adhesive resin layer (A). manufacturing method. The functionality according to claim 12, wherein the heating temperature _TC of the adhesive resin layer (A) containing the thermally expandable microspheres in step c is higher than the heating temperature _TB in the processing in the step b. Method of manufacturing thin glass. The functional layer is the light-shielding printed layer,
_TB is 130°C or more and 220°C or less,
The method for producing functional thin glass according to claim 13, wherein T _C is (T _B +5)°C or higher. the functional layer is the primer layer,
_TB is 160°C or more and 250°C or less,
The method for producing functional thin glass according to claim 13, wherein T _C is (T _B +5)°C or higher. The peelable adhesive tape includes a base material layer, an adhesive resin layer (A) provided on one surface of the base material layer, and thermally expandable microspheres provided on the other surface of the base material layer. an adhesive resin layer (B) containing;
The thin glass is pasted on the adhesive resin layer (A),
Step c is
step c-1 of peeling the laminate of the functional thin glass and the peelable adhesive tape from the support by heating the adhesive resin layer (B);
Step c-2 of peeling off the functional thin glass from the adhesive resin layer (A) of the laminate;
The method for producing functional thin glass according to any one of claims 1 to 11, comprising: According to claim 16, the heating temperature T _{C-1 of the adhesive resin layer (B) containing the thermally expandable microspheres in step c-1} is higher than the heating temperature T _B in the processing treatment of the step b. The method for manufacturing the functional thin glass described above. The functional layer is the light-shielding printed layer,
_TB is 130°C or more and 220°C or less,
The method for producing functional thin glass according to claim 17, wherein T _C-1 is (T _B +5)° C. or higher. the functional layer is the primer layer,
_TB is 160°C or more and 250°C or less,
The method for producing functional thin glass according to claim 17, wherein T _C-1 is (T _B +5)° C. or higher. 13. The method for manufacturing functional thin glass according to claim 12, wherein the thermally expandable microspheres include microspheres in which a shell encloses a substance that expands upon gasification. A peelable adhesive tape used in the method for producing functional thin glass according to any one of claims 1 to 11, comprising an adhesive resin layer (A) and an adhesive resin layer (B), and comprises at least A peelable adhesive tape containing thermally expandable microspheres in either layer (A) or layer (B).

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