JP5760376B2 - SUPPORT, GLASS SUBSTRATE LAMINATE, PANEL FOR DISPLAY DEVICE WITH SUPPORT, ORGANOPOLYSILOXANE COMPOSITION, AND PROCESS FOR PRODUCING DISPLAY DEVICE PANEL - Google Patents

Description

  The present invention relates to a support, a glass substrate laminate, a panel for a display device with a support, an organopolysiloxane composition, and a method for producing a panel for a display device.

In the field of liquid crystal display devices (LCD), organic EL display devices (OLED), especially portable display devices such as digital cameras and mobile phones, weight reduction and thinning of display devices are important issues.
In order to cope with this problem, it is desired to further reduce the thickness of the glass substrate used in the display device. As a general method for reducing the thickness of the glass substrate, the glass substrate is etched using chemical etching before or after the display device member is formed on the surface of the glass substrate, and further if necessary. A method of thinning by physical polishing is performed.

However, if the thickness of the glass substrate is reduced by performing an etching process or the like before forming the display device member on the surface of the glass substrate, the strength of the glass substrate is lowered and the amount of deflection is increased. Therefore, there arises a problem that it becomes difficult to perform processing in the existing display device panel production line.
In addition, if the thickness of the glass substrate is reduced by performing an etching process after forming the display device member on the surface of the glass substrate, it is formed on the surface of the glass substrate in the process of forming the display device member on the surface of the glass substrate. There arises a problem that the formed fine scratches are manifested, that is, a problem of generation of etch pits.

Therefore, for the purpose of solving such problems, a predetermined process for manufacturing a display device in that state by laminating a thin glass substrate and a supporting substrate together through a resin layer. After that, a method of peeling the glass substrate surface and the peelable surface of the resin layer has been proposed.
For example, Patent Document 1 discloses a glass substrate laminate obtained by laminating a glass substrate and a support substrate, and the glass substrate and the support substrate have a peelable surface and are non-adhesive. A glass substrate laminate is described which is laminated via a silicone resin layer shown.
On the other hand, as a technology related to the silicone resin layer, for example, Patent Document 2 proposes an organopolysiloxane composition for forming a cured film having excellent peeling characteristics and little silicone migration to the back surface of the film. Has been.

International Publication No. 2007/018028 JP 2009-114285 A

In recent years, a manufacturing process in a high temperature environment of about 450 ° C. has been performed for manufacturing a member for a display device such as a TFT array. Therefore, in order to apply the glass substrate laminate as described in Patent Document 1 to the process, a resin layer exhibiting excellent heat resistance that does not decompose even under such a high temperature condition is required.
When the present inventors examined the heat resistance under high temperature conditions using the silicone resin layer specifically described in Patent Document 1, the heat resistance of the silicone resin layer is a practical viewpoint. Was not always satisfactory, and further improvements were needed.
Moreover, when the present inventors also examined the heat resistance of a cured product obtained by using the organopolysiloxane composition specifically described in Patent Document 2, the heat resistance of the cured product was also It was not always enough.

In order to solve the above problems, the present invention is excellent in heat resistance, can be peeled off in a short time without destroying the laminated glass substrate, and can be applied to a manufacturing process under a high temperature condition such as manufacturing a TFT array. An object of the present invention is to provide a support for supporting a glass substrate that can be applied.
Another object of the present invention is to provide an organopolysiloxane composition, a glass substrate laminate, a display device panel with a support, and a method for producing a display device panel.

As a result of intensive studies on the prior art, the present inventors have found that the decomposition of the cured silicone resin layer is suppressed when the amount of the platinum-based catalyst in the resin layer is a predetermined amount.
Based on the above findings, the present inventors have found that the above object can be achieved by the following means.

That is, in order to achieve the above object, the first aspect of the present invention provides:
A support for laminating a glass substrate on the surface of a cured silicone resin layer, comprising a support substrate and a cured silicone resin layer having a peelable surface provided on one side of the support substrate,
The cured silicone resin layer contains at least (A) a linear organopolysiloxane having an alkenyl group, (B) an organopolysiloxane having a hydrogen atom bonded to a silicon atom, and (C) a platinum-based catalyst, The organopolysiloxane composition cured by an addition reaction in which the content of the component (C) is 900 to 3000 mass ppm in terms of platinum with respect to the total amount of the components (A) and (B) The present invention provides a support characterized in that it is a cured silicone resin layer formed by curing.
In the first aspect, the thickness of the cured silicone resin layer is preferably 5 to 50 μm.

The second aspect of the present invention is a glass substrate laminate having a support substrate, a glass substrate, and a cured silicone resin layer present between them.
The cured silicone resin layer contains at least (A) a linear organopolysiloxane having an alkenyl group, (B) an organopolysiloxane having a hydrogen atom bonded to a silicon atom, and (C) a platinum-based catalyst, The content of the component (C) is a cured product of an organopolysiloxane composition that cures by an addition reaction, which is 900 to 3000 ppm by mass in terms of platinum with respect to the total amount of the components (A) and (B),
The present invention provides a glass substrate laminate, wherein the peel strength between the glass substrate and the cured silicone resin layer is lower than the peel strength between the support substrate and the cured silicone resin layer.
In the second aspect of the present invention, the organopolysiloxane composition is cured by curing the organopolysiloxane composition in a state where the cured silicone resin layer is in contact with the support substrate surface and not in contact with the glass substrate surface. It is preferable that the layer is formed by contacting the glass substrate surface later.
In the 2nd aspect of this invention, it is preferable to use for the use exposed to the temperature of 400 degreeC or more for 10 minutes or more.

  According to a third aspect of the present invention, there is provided a display device with a support for manufacturing a display device panel, wherein at least a part of the constituent members of the display device panel is formed on the glass substrate surface of the second aspect. A panel is provided.

  In the fourth aspect of the present invention, at least a part of the constituent members of the display device panel is formed on the glass substrate surface of the glass substrate laminate of the second aspect, and then the glass substrate and the support with the cured silicone resin layer are supported. The present invention provides a method for manufacturing a panel for a display device having a glass substrate, wherein the substrate is separated from the substrate.

5th aspect of this invention is an organopolysiloxane composition used for the use which forms the peelable resin layer with respect to a glass substrate,
(A) a linear organopolysiloxane having an alkenyl group, (B) an organopolysiloxane having a hydrogen atom bonded to a silicon atom, and (C) a platinum-based catalyst. The present invention provides an organopolysiloxane composition curable by addition reaction, characterized in that the amount is 900 to 3000 ppm by mass in terms of platinum with respect to the total amount of the component (A) and the component (B).

  In the 5th aspect of this invention, it is preferable to use for the use to which a hardened | cured material is exposed to the temperature of 400 degreeC or more for 10 minutes or more. Moreover, in the 5th aspect of this invention, it is also preferable to use for the use to which the hardened | cured material is exposed to the temperature of 400 degreeC or more for 10 minutes or more in the state sealed with the gas-impermeable face material.

According to the present invention, a glass substrate that has excellent heat resistance, can be peeled off in a short time without breaking the laminated glass substrate, and can be applied to a manufacturing process under a high temperature condition such as manufacturing a TFT array is supported. A support can be provided.
Furthermore, according to this invention, the manufacturing method of the organopolysiloxane composition, the glass substrate laminated body, the panel for display apparatuses with a support body, and the panel for display apparatuses can also be provided.

It is typical sectional drawing of one Embodiment of the panel for display apparatuses with a support which concerns on this invention.

Hereinafter, the organopolysiloxane composition, the support, the glass substrate laminate, and the display-equipped panel for the support according to the present invention will be described in detail.
First, the organopolysiloxane composition (components, etc.) will be described in detail below.
A characteristic of the composition includes the amount of a platinum-based catalyst. In other words, in the present invention, by using a larger amount of platinum-based catalyst than in the prior art, radicals (for example, .O-Si) generated with the decomposition of the resin under high temperature conditions are captured by the platinum-based catalyst. (Trap). As a result, the decomposition of the chained resin by the generated radicals is suppressed, and the heat resistance of the cured silicone resin layer is improved. In addition, the above effects are more prominent in a sealed state in which the resin layer is sandwiched between the support substrate and the glass substrate.

<Organopolysiloxane composition>
The organopolysiloxane composition according to the present invention contains the following three components.
Component (A): Linear organopolysiloxane having an alkenyl group (hereinafter also referred to as organoalkenyl polysiloxane)
Component (B): organopolysiloxane having a hydrogen atom bonded to a silicon atom (hereinafter also referred to as organohydrogenpolysiloxane)
Component (C): Platinum-based catalyst The content of the component (C) is 900 to 3000 ppm in terms of platinum with respect to the total amount of the component (A) and the component (B).
Moreover, (D) component: addition reaction inhibitor may contain in the composition as needed.
Below, each component is explained in full detail.

<(A) component: Organoalkenyl polysiloxane>
The organoalkenyl polysiloxane as component (A) is a linear organopolysiloxane having an alkenyl group in one molecule.

Although it does not specifically limit as an alkenyl group, For example, a vinyl group (ethenyl group), an allyl group (2-propenyl group), a butenyl group, a pentenyl group, a hexynyl group etc. are mentioned, Among these, since it is excellent in heat resistance, a vinyl group Is preferred.
The number of alkenyl groups contained in one molecule is preferably 2 or more.
Further, the content of the alkenyl group in the organoalkenyl polysiloxane is not particularly limited, but is preferably 0.03 to 10 mol%, more preferably 0.05 to 5 mol%, in terms of excellent heat resistance of the resulting resin layer. 0.1 to 3 mol% is particularly preferable. If the alkenyl group content is too high, handling may be difficult due to an increase in viscosity.

  The viscosity at 25 ° C. of the organoalkenylpolysiloxane is not particularly limited, but is preferably 40 to 10000 cP, more preferably 40 to 5000 cP, from the viewpoints of handleability and the heat resistance of the resulting cured silicone resin layer.

In general, monofunctional units at both ends of a linear organopolysiloxane are called M units, and bifunctional units other than both ends are called D units, and linear organopolysiloxanes having n D units are used. The structure of polysiloxane is represented by M (D) _n M. Moreover, when expressing the average composition of each unit, it may be represented by M ₂ (D) _n .

  In the organoalkenyl polysiloxane, the alkenyl group is present in the M unit or D unit, and may be present in both the M unit and D unit. From the viewpoint of curing speed, it is preferably present at least in M units, and preferably present in both two M units. In addition, organoalkenylpolysiloxanes having alkenyl groups only in M units have a lower heat resistance because the higher the molecular weight, the lower the alkenyl group concentration per molecule and the lower the crosslinking density of the cured silicone resin layer. Since there exists a possibility, it is preferable to have an alkenyl group in a part of D unit with M unit.

As the organoalkenylpolysiloxane, a linear organopolysiloxane having an average composition represented by the following formula (1) is preferable.
(M ¹ ) _a (M ² ) _b (D ¹ ) _c (D ² ) _d (1)
Where M ¹ is an M unit having no alkenyl group, M ² is an M unit having an alkenyl group, D ¹ is a D unit having no alkenyl group, and D ² is a D unit having an alkenyl group, and a is 0 The number of ˜2, b is a number of 0 to 2, a + b = 2, c is a number of 0 or more, d is a number of 0 or more, and c + d = n (where b + d is 2 or more). In addition, n is preferably 1 to 1500.
In the more preferred organoalkenylpolysiloxane represented by the formula (1), a is a number of 0 or more and less than 1, b is a number of 1 or more and 2 or less, c is a number of 1 or more, and d is a number of 1 or more.

The M ² unit may have two or three alkenyl groups, but preferably has one. The D ² unit may have two alkenyl groups, but preferably has one. The alkenyl group is preferably a vinyl group. The M ¹ unit, D ¹ unit, M ² unit, and D ² unit are preferably those represented by the following formulae. R ^{1 to} R ⁵ each independently represents an alkyl group or fluoroalkyl group having 4 or less carbon atoms, or a phenyl group. R ^{1 to} R ⁵ are preferably all methyl groups.

Formula (1) shows the average composition of the organosiloxane units in the organoalkenyl polysiloxane, and each molecule of the organoalkenyl polysiloxane is an integer where a is an integer from 0 to 2, and b is an integer from 0 to 2. And a + b = 2 is satisfied, c is an integer of 0 or more, and d is an integer of 0 or more. Since the organoalkenyl polysiloxane has two or more alkenyl groups per molecule, b + d is 2 or more.
The organoalkenylpolysiloxane which is a compound having a linear structure may be a mixture with another organopolysiloxane having an alkenyl group (such as a branched organopolysiloxane). Only used. However, the organoalkenyl polysiloxane may be a mixture of two or more organoalkenyl polysiloxanes. In addition, when two types of organoalkenylpolysiloxanes having different La values are used in combination, a more advantageous effect can be obtained. The La value will be described later.
In addition, when there are a large number of D ¹ and D ² in the organoalkenyl polysiloxane represented by the formula (1), the arrangement of D ¹ and D ² is a block copolymer chain structure even if it is a random copolymer chain structure. There may be.
As the organoalkenyl polysiloxane, organoalkenyl polysiloxanes represented by the following formulas (A) and (B) described in International Publication No. 2007/018028 can be used. In the following formulas (A) and (B), p represents an integer of 1 to 1500, and q represents an integer of 1 to 1500. p + q = n.

  The equivalent number La of alkenyl groups per 100 grams of the organoalkenyl polysiloxane is preferably in the range of 0.001 ≦ La ≦ 30. More preferable La is 0.0015 ≦ La ≦ 20, and further preferably 0.002 ≦ La ≦ 15. By setting La within this range, the heat resistance of the cured silicone resin is improved, and the temporal stability of the peel strength between the cured silicone resin layer and the glass substrate is improved.

<(B) component: organohydrogenpolysiloxane>
The (B) component organohydrogenpolysiloxane is an organopolysiloxane having a hydrogen atom bonded to a silicon atom.
The number of hydrogen atoms bonded to silicon atoms in the organohydrogenpolysiloxane is preferably 2 or more, more preferably 2 to 200, from the viewpoint of good heat resistance of the resulting cured silicone resin layer. 6 to 100 are particularly preferred.

  The viscosity of the organohydrogenpolysiloxane at 25 ° C. is not particularly limited, but is preferably 1 to 1000 cP, more preferably 5 to 800 cP, from the viewpoints of handleability and the heat resistance of the resulting cured silicone resin layer.

The organohydrogenpolysiloxane may be linear or branched, and is preferably linear from the viewpoint of the heat resistance of the resulting cured silicone resin layer.
In the case of a straight chain, the hydrogen atom is present in the M unit or D unit, and may be present in both the M unit and D unit. From the viewpoint of curing speed, it is preferably present at least in M units, and preferably present in both two M units.

As the organohydrogenpolysiloxane, a linear organohydrogenpolysiloxane having an average composition represented by the following formula (2) is preferable.
(M ³ ) _α (M ⁴ ) _β (D ³ ) _γ (D ⁴ ) _δ (2)
Where M ³ is an M unit in which no hydrogen atom bonded to a silicon atom is present, M ⁴ is an M unit in which a hydrogen atom bonded to a silicon atom is present, D ³ is a D unit in which no hydrogen atom bonded to a silicon atom is present, And D ⁴ represents a D unit in which a hydrogen atom bonded to a silicon atom is present, α is a number of 0 or more and less than 2, β is a number of 2 or less that is not 0, α + β = 2, γ is a number exceeding 0, and δ is A number greater than or equal to 0 is γ + δ = m. In addition, m is preferably 1 to 150.
More preferable organohydrogenpolysiloxanes are such that α is a number of 0 or more and less than 1, β is a number of 1 or more and 2 or less, γ is a number of 1 or more, and δ is a number of 1 or more.

The M ⁴ unit may have two or three hydrogen atoms bonded to a silicon atom, but preferably has one. The D ⁴ unit may have two hydrogen atoms bonded to a silicon atom, but preferably has one. The M ³ unit, D ³ unit, M ⁴ unit, and D ⁴ unit are preferably those represented by the following formulae. R ^{1 to} R ⁵ each independently represents an alkyl group or fluoroalkyl group having 4 or less carbon atoms, or a phenyl group. R ^{1 to} R ⁵ are preferably all methyl groups.

When D ⁴ units are present (when δ is not 0), γ / δ, which is the abundance ratio between D ³ and D ⁴ , is an index representing the density of hydrogen atoms bonded to silicon atoms in the molecule. The abundance ratio (γ / δ) is preferably 0.2 to 30, and particularly preferably 0.5 to 20. If this abundance ratio is too small, the residual amount of hydrogen atoms bonded to unreacted silicon atoms in the cured silicone resin increases, so that the change in peel strength of the cured silicone resin with respect to the glass substrate increases with time, and heat resistance is increased. There is a risk of deteriorating sex. On the other hand, if the abundance ratio is too large, the crosslink density of the cured silicone resin decreases, which may cause a decrease in heat resistance.

Β / δ representing the abundance ratio of M ⁴ units to D ⁴ units is preferably 15 ≦ (β / δ) × 1000 ≦ 1500. More preferably, 15 ≦ (β / δ) × 1000 ≦ 1000, and particularly preferably 15 ≦ (β / δ) × 1000 ≦ 500. If (β / δ) × 1000 is 15 or more, the molecular weight and the crosslinking density are not excessively high, and the reactivity is good. Therefore, the peel strength due to unreacted groups is less changed with time, and the peel strength is stable. is there. On the other hand, if (β / δ) × 1000 is 1500 or less, the molecular weight and the crosslink density are appropriate, so that physical properties such as strength are good.

  An organohydrogenpolysiloxane represented by the following formula (C) described in International Publication No. 2007/018028 can also be used as the organohydrogenpolysiloxane (corresponding to a compound with β = 0). In the following formula (C), x represents an integer of 0 to 150, and y represents an integer of 1 to 150. x + y = m.

  The content ratio of the organoalkenylpolysiloxane and the organohydrogenpolysiloxane in the organopolysiloxane composition is not particularly limited. And the molar ratio (hydrogen atom / alkenyl group) is preferably adjusted to 0.7 to 1.05. Especially, it is preferable to adjust a content ratio so that it may become 0.8-1.0. When the molar ratio between the hydrogen atom bonded to the silicon atom and the alkenyl group exceeds 1.05, the peel strength of the cured silicone resin after standing for a long time may increase. In addition, when the molar ratio of the hydrogen atom bonded to the silicon atom and the alkenyl group is less than 0.7, the crosslink density of the cured silicone resin is lowered, which may cause a problem in chemical resistance.

<(C) component: platinum-based catalyst>
Component (C) is a platinum-based catalyst that promotes the reaction between the alkenyl group in component (A) and the hydrogen atom bonded to the silicon atom in component (B).
A known catalyst can be used as the platinum-based catalyst. Specifically, platinum fine powder, platinum black, chloroplatinic acid such as chloroplatinic acid, dichloroplatinic acid, platinum tetrachloride, alcohol compound or aldehyde compound of chloroplatinic acid, platinum olefin complex, alkenylsiloxane And a complex or a carbonyl complex. More specifically, commercially available products such as platinum alkenylsiloxane complex (for example, CAT-PL-56 manufactured by Shin-Etsu Silicone Co., Ltd.) can be used.

The content of the platinum-based catalyst in the organopolysiloxane composition is 900 to 3000 mass ppm in terms of platinum with respect to the total amount of the component (A) and the component (B). Especially, 1100-3000 mass ppm is preferable and 1500-3000 mass ppm is more preferable at the point of the heat resistance of the cured silicone resin layer obtained, and the applicability | paintability (storage stability of a liquid) of an organopolysiloxane composition. The heat resistance of the obtained cured silicone resin layer is favorable in it being 900 mass ppm or more. When it is 3000 ppm by mass or less, the coating property (storage stability of the liquid) of the composition is good.
Good heat resistance means that the weight loss of the cured silicone resin layer is small under the conditions (temperature / time) for producing a liquid crystal display member or the like. Specifically, it is preferable that 50% by weight or more of the initial resin weight of the cured silicone resin layer in the glass laminate remains in one heating, and more than 70% by weight remains. preferable.
Specifically, the coating property (storage stability of the liquid) means that the increase in viscosity is small during storage at room temperature, and a coating film having a good surface condition can be obtained when it is applied. Regarding the degree of thickening, when the composition is stored for 1 month at room temperature, the viscosity of the composition is preferably within 1.1 times the initial viscosity.

<(D) component: addition reaction inhibitor>
Component (D) is an addition reaction inhibitor and is a compound used for the purpose of controlling the reaction by the platinum-based catalyst. In addition, (D) component is arbitrary components and is used as needed.
Known addition reaction inhibitors can be used. Specifically, benzotriazole compounds (Japanese Patent Publication No. 40-25069), acetylene alcohol compounds (Japanese Patent Publication No. 44-31476), vinyl group-containing polysiloxane compounds (Japanese Patent Publication No. 48-10947), hydro Examples thereof include peroxides (Japanese Patent Publication No. 57-20340) and amine compounds (Japanese Patent Laid-Open No. 63-56563). Preferably, it can be selected from acetylene or acetylene alcohol-containing compounds. More specifically, 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, ethynylcyclohexanol, 3,5-dimethyl-1-hexyn-3-ol, etc. Can do.

  The content of the addition reaction inhibitor in the organopolysiloxane composition is not particularly limited, but is preferably 0.1 to 15% by mass with respect to the total amount of the composition in terms of controlling the curing reaction of the composition, 10 mass% is more preferable.

(Other additives)
Various additives may be contained in the organopolysiloxane composition according to the present invention as long as the effects of the present invention are not impaired. For example, you may contain inorganic fillers, such as various silicas, calcium carbonate, and iron oxide.
In addition, organic solvents such as hexane, heptane, octane, toluene and xylene, and dispersion media such as water are components that do not constitute the cured silicone resin layer, but include improved workability for application of the organopolysiloxane composition. Can be used for purposes.

The organopolysiloxane composition can be used for various applications, and is preferably used for forming a resin layer having a peelable surface (peelable resin layer). Especially, it is preferable to use in order to form the resin layer which shows peelability with respect to a glass substrate. That is, it is preferably a composition for forming a peelable resin layer on a glass substrate.
The organopolysiloxane composition is also preferably used for applications in which a cured silicone resin, which is a cured product thereof, is exposed to a temperature of 400 ° C. or higher for 10 minutes or longer.
Furthermore, the organopolysiloxane composition should be used in applications where the cured silicone resin, which is the cured product, is exposed to a temperature of 400 ° C. or more for 10 minutes or more in a state of being sealed with a gas-impermeable face material. Is also preferable. In addition, as a gas impermeable face material, a glass substrate etc. are mentioned, for example.

<Support, glass substrate laminate, panel for display with support>
FIG. 1 is a schematic cross-sectional view of an embodiment of a display panel with a support according to the present invention.
A display device panel 10 with a support shown in FIG. 1 includes a support 20 according to the present invention, and includes a support substrate 12, a resin layer (cured silicone resin layer) 14, a glass substrate 16, and a display device panel. The constituent members 18 are stacked in this order. Note that the thickness of each layer is not limited by the drawing.
The support substrate 12 and the resin layer 14 constitute the support 20 according to the present invention, the support 20 and the glass substrate 16 constitute the glass substrate laminate 30 according to the present invention, and the glass substrate 16 and the display device. The panel structural member 18 constitutes a display device panel 40 (without the support 20).
Below, each layer which comprises the support body 20, the glass substrate laminated body 30, the display apparatus panel 40, and the display apparatus panel 10 with a support body which concern on this invention is demonstrated.

<Support substrate>
The support substrate 12 used in the present invention is not particularly limited as long as it supports the glass substrate 16 through a resin layer 14 described later and reinforces the strength of the glass substrate 16.
Although it does not restrict | limit especially as a material of the support substrate 12, Glass, a silicon | silicone, a synthetic resin, a metal, etc. are illustrated as a suitable example from a viewpoint of industrial availability. Among these, the support substrate 12 is preferably a glass plate, a silicon wafer, a synthetic resin plate, or a metal plate.

When glass is employed as the material of the support substrate 12, glass having various compositions such as glass containing alkali metal oxide (such as soda lime glass) and non-alkali glass can be used. Among these, alkali-free glass is preferable because of its low thermal shrinkage rate.
The difference in coefficient of linear expansion between the glass substrate 16 and the glass used for the support substrate 12 is preferably 150 × 10 ⁻⁷ / ° C. or less, more preferably 100 × 10 ⁻⁷ / ° C. or less, and 50 × More preferably, it is 10 ⁻⁷ / ° C. or less. The glass of the glass substrate 16 and the glass of the support substrate 12 may be made of the same material. In this case, the difference between the linear expansion coefficients of both glasses is zero.

  When plastic (synthetic resin) is adopted as the material of the support substrate 12, the type is not particularly limited. For example, polyethylene terephthalate resin, polycarbonate resin, polyimide resin, fluorine resin, polyamide resin, polyaramid resin, polyethersulfone resin, Examples include polyether ketone resins, polyether ether ketone resins, polyethylene naphthalate resins, polyacrylic resins, various liquid crystal polymer resins, and silicone resins.

  When a metal is adopted as the material of the support substrate 12, the type is not particularly limited, and examples thereof include stainless steel and copper.

The heat resistance of the support substrate 12 is not particularly limited. However, when a glass substrate 16 is laminated on the support substrate 12 and a TFT array of a display device member is formed, the heat resistance is preferably high. Specifically, the temperature at which the weight loss when the material sample is heated at 10 ° C./min in an air atmosphere exceeds 5% of the sample weight is defined as the 5% heating weight loss temperature. The temperature is preferably 300 ° C. or higher. Furthermore, it is more preferable that it is 350 degreeC or more.
In this case, any of the above glasses is applicable in terms of heat resistance.
Preferred plastic materials from the viewpoint of heat resistance include polyimide resins, fluororesins, polyamide resins, polyaramid resins, polyethersulfone resins, polyetherketone resins, polyetheretherketone resins, polyethylene naphthalate resins, and various liquid crystal polymer resins. Illustrated.

Although the thickness of the support substrate 12 is not specifically limited, It is preferable that it is the thickness which can process the glass substrate laminated body 30 of this invention with the manufacturing line of the present panel for display apparatuses. For example, the thickness of a glass substrate currently used in a liquid crystal display device is mainly in the range of 0.5 to 1.2 mm, and particularly 0.7 mm. In the present invention, it is mainly assumed that a thinner glass substrate is used. At this time, if the thickness of the glass substrate laminate 30 is about the same as the current glass substrate, it can be easily adapted to the current production line.
For example, when the current production line is designed to process a glass substrate having a thickness of 0.5 mm and the thickness of the glass substrate 16 is 0.1 mm, the thickness of the support substrate 12 and the resin layer The sum of the thickness of 14 is 0.4 mm. In addition, the current production line is most commonly designed to process a glass substrate having a thickness of 0.7 mm. For example, if the thickness of the glass substrate 16 is 0.4 mm, it is supported. The sum of the thickness of the substrate 12 and the thickness of the resin layer 14 is set to 0.3 mm.

  The glass substrate 16 in the present invention is not limited to the liquid crystal display device, and the present invention is not intended only to adapt the glass substrate laminate 30 to the current production line for the display device panel 40. . Therefore, the thickness of the support substrate 12 is not limited, but is preferably 0.1 to 1.1 mm. Further, the thickness of the support substrate 12 is preferably thicker than the glass substrate 16. Moreover, when the support substrate 12 is a glass plate, it is preferable that it is especially 0.3 mm or more. When the support substrate 12 is a glass plate, the thickness is more preferably 0.3 to 0.8 mm, and further preferably 0.4 to 0.7 mm.

  When the glass substrate is adopted as the support substrate 12, the surface of the support substrate 12 composed of the various materials described above may be a polished surface that is polished or a non-etched surface (fabric surface) that is not polished. There may be. From the viewpoint of productivity and cost, a non-etched surface (fabric surface) is preferable.

The support substrate 12 has a first main surface and a second main surface, and the shape thereof is not limited, but is preferably rectangular. Here, the rectangle is substantially a rectangle and includes a shape obtained by cutting off the corners of the peripheral portion (corner cut).
Although the magnitude | size of the support substrate 12 is not limited, For example, in the case of a rectangle, it may be 100-2000 mm x 100-2000 mm, and it is preferable that it is 500-1000 mm x 500-1000 mm.

<Resin layer (cured silicone resin layer)>
The resin layer 14 is fixed on the first main surface of the support substrate 12 described above, and in the glass substrate laminate 30 in which the glass substrate 16 is laminated, the glass substrate 16 having the first main surface and the second main surface. The first main surface is in close contact. The peel strength between the first main surface of the glass substrate 16 and the resin layer 14 needs to be lower than the peel strength between the first main surface of the support substrate 12 and the resin layer 14. That is, when separating the glass substrate 16 and the support substrate 12, the glass substrate 16 is peeled off at the interface between the first main surface of the glass substrate 16 and the resin layer 14, and the first main surface of the support substrate 12 and the resin layer 14 are separated. It must be difficult to peel off at the interface. For this reason, although the resin layer 14 adheres to the 1st main surface of the glass substrate 16, it has the surface characteristic which can peel the glass substrate 16 easily. That is, the resin layer 14 is bonded to the first main surface of the glass substrate 16 with a certain bonding force to prevent the glass substrate 16 from being displaced, and at the same time, when the glass substrate 16 is peeled off. The glass substrate 16 is bonded with a bonding force that can be easily peeled without breaking the glass substrate 16. In this invention, the property which can peel this resin layer 14 surface easily is called peelability. On the other hand, the first main surface of the support substrate 12 and the resin layer 14 are bonded with a bonding force that is relatively difficult to peel.

In the glass substrate laminate 30 of the present invention, the resin layer 14 and the glass substrate 16 are not attached by the adhesive force that the adhesive has, and the force caused by the van der Waals force between the solid molecules, that is, the adhesion It is preferable that it is attached by force.
On the other hand, the bonding force of the resin layer 14 to the first main surface of the support substrate 12 is relatively higher than the bonding force of the glass substrate 16 to the first main surface. In the present invention, the bonding of the glass substrate 16 to the first main surface is referred to as adhesion, and the bonding of the support substrate 12 to the first main surface is referred to as fixing.
Further, since the resin layer 14 is highly flexible, even if foreign matter such as bubbles or dust is mixed between the glass substrate 16 and the resin layer 14, it is possible to suppress the occurrence of distortion defects in the glass substrate 16. .

  In order to relatively lower the peel strength of the resin layer 14 with respect to the first main surface of the glass substrate 16 and to relatively increase the peel strength of the resin layer 14 with respect to the first main surface of the support substrate 12, A siloxane composition is cured on the first main surface of the support substrate 12 to form a resin layer 14 made of a cured silicone resin, and then a glass substrate 16 is laminated and adhered to the resin layer 14 made of a cured silicone resin. Is preferred. The cured silicone resin in the present invention is the same resin as the non-adhesive cured silicone resin used for release paper and the like, and even if it is in close contact with the glass substrate 16, the peel strength is low. However, when the organopolysiloxane composition to be a cured silicone resin is cured on the surface of the support substrate 12, it adheres by interaction with the surface of the support substrate 12 during the curing reaction, and the cured resin layer 14 and the surface of the support substrate 12 It is considered that the peel strength of the is increased. Therefore, even if the glass substrate 16 and the support substrate 12 are made of the same material, a difference can be provided in the peeling strength between the resin layer 14 and both.

The formation of the resin layer 14 with a difference between the peel strength with respect to the first main surface of the glass substrate 16 and the peel strength with respect to the first main surface of the support substrate 12 is not limited to the above method. For example, when the support substrate 12 made of a material having higher adhesion to the surface of the resin layer 14 than the glass substrate 16 is used, the glass substrate 16 and the support substrate 12 are interposed with a film-like resin layer 14 (cured silicone resin film) interposed therebetween. Can be laminated simultaneously.
Further, when the adhesion of the organopolysiloxane composition by curing to the glass substrate 16 is sufficiently low and the adhesion to the support substrate 12 is sufficiently high, the organopolysiloxane is interposed between the glass substrate 16 and the support substrate 12. The resin layer 14 can be formed by curing the composition.
Even when the support substrate 12 is made of the same glass material as that of the glass substrate 16, it is possible to increase the peel strength with respect to the resin layer 14 by performing a process for improving the adhesion of the surface of the support substrate 12. For example, the surface of the support substrate 12 made of a glass material can be treated to increase the concentration of silanol groups to increase the bonding force with the resin layer 14.

<Formation of resin layer>
As described above, it is preferable to cure the organopolysiloxane composition on the first main surface of the support substrate 12 to form the resin layer 14 made of a cured silicone resin. For this purpose, the organopolysiloxane composition is applied to one side of the support substrate 12 to form a layer of the organopolysiloxane composition, and then the organopolysiloxane composition is cured to form a cured silicone resin layer.
When the organopolysiloxane composition is a fluid composition, the organopolysiloxane composition is formed as it is, and the organopolysiloxane composition is applied as it is, and the organopolysiloxane composition is a composition with low fluidity or non-fluidity. Is applied by blending an organic solvent. Also, an emulsion or dispersion of an organopolysiloxane composition can be used. The coating film containing a volatile component such as an organic solvent is then evaporated to remove the volatile component to form a layer of an organopolysiloxane composition. Curing of the organopolysiloxane composition can be performed continuously with the removal of volatile components by evaporation.

  Curing of the organopolysiloxane composition is not limited to the above method. For example, the organopolysiloxane composition can be cured on some peelable surface to produce a cured silicone resin film, and this film can be laminated to the support substrate 12 to produce the support 20. When the organopolysiloxane composition does not contain a volatile component, it can be cured by being sandwiched between the glass substrate 16 and the support substrate 12 as described above.

  When the organopolysiloxane composition is applied to one side of the support substrate 12 to form a layer of the organopolysiloxane composition, the application method is not particularly limited, and a conventionally known method can be used. Known methods include spray coating, die coating, spin coating, dip coating, roll coating, bar coating, screen printing, and gravure coating. From such a method, it can select suitably according to the kind of composition. For example, when a volatile component is not blended in the organopolysiloxane composition, a die coating method, a spin coating method, or a screen printing method is preferable. In the case of a composition containing a volatile component such as a solvent, the composition is cured after removing the volatile component by heating or the like before curing.

  The conditions for curing the organopolysiloxane composition vary depending on the type of organopolysiloxane used, and the optimum conditions are appropriately selected. Usually, the heating temperature is preferably 50 to 300 ° C, more preferably 100 ° C to 270 ° C, and the treatment time is preferably 5 to 300 minutes, more preferably 5 to 180 minutes.

If the resin layer 14 has low silicone migration, when the glass substrate 16 is peeled off, the components in the resin layer 14 are difficult to migrate to the glass substrate. Silicone transferability refers to a phenomenon in which a relatively low molecular weight silicone component in a silicone resin moves from the surface of the silicone resin to the surface of another material in contact with the silicone resin. In the present invention, unreacted organopolysiloxane, decomposed product of organopolysiloxane, decomposed product of cured silicone resin, etc. present in the cured silicone resin of the resin layer 14 are silicone components that easily migrate.
In order to obtain the resin layer 14 having low silicone migration, it is preferable to proceed the curing reaction as much as possible so that an unreacted organopolysiloxane component does not remain in the resin layer 14. The reaction temperature and reaction time as described above are preferable because substantially no unreacted organopolysiloxane component remains in the resin layer 14. If the reaction time is too long or the reaction temperature is too high, the organopolysiloxane component and the cured silicone resin are simultaneously oxidized and decomposed to produce a low molecular weight organopolysiloxane component, resulting in silicone migration. May increase. It is preferable to allow the curing reaction to proceed as much as possible so that an unreacted organopolysiloxane component does not remain in the resin layer 14 in order to improve the peelability after the heat treatment.

  In addition, in order to provide a high fixing force (high peel strength) between the resin layer 14 and the support substrate 12, surface modification treatment (priming treatment) may be performed on the surface of the support substrate 12. For example, a chemical method (primer treatment) that improves the fixing force chemically such as a silane coupling agent, a physical method that increases surface active groups such as a flame (flame) treatment, or a surface such as a sandblast treatment Examples of such a mechanical processing method increase the catch by increasing the roughness of the material.

The thickness of the resin layer 14 made of the cured silicone resin is not particularly limited, and an optimal thickness is appropriately selected depending on the type of the glass substrate 16 and the like. Especially, it is preferable that it is 5-50 micrometers, It is more preferable that it is 5-30 micrometers, It is further more preferable that it is 7-30 micrometers. When the thickness of the resin layer 14 is within such a range, the adhesion between the surface of the glass substrate 16 and the resin layer 14 becomes better. Moreover, even if air bubbles or foreign substances are present, the occurrence of distortion defects in the glass substrate 16 can be further suppressed. In addition, if the thickness of the resin layer 14 is too thick, it takes time and materials to form the resin layer 14 and is not economical.
The resin layer 14 may be composed of two or more layers. In this case, “the thickness of the resin layer” means the total thickness of all the layers.
Moreover, when the resin layer 14 consists of two or more layers, the kind of resin which forms each layer may differ.

The resin layer 14 preferably has a peelable surface tension of 30 mN / m or less, more preferably 25 mN / m or less, and even more preferably 22 mN / m or less. Although there is no limitation in particular about a minimum, it is preferred that it is 15mN / m or more.
With such surface tension, it can be more easily peeled off from the surface of the glass substrate 16, and at the same time, adhesion to the surface of the glass substrate 16 is sufficient.

  The resin layer 14 is preferably made of a material having a glass transition point lower than room temperature (about 25 ° C.) or having no glass transition point. If the glass transition point is as described above, it can have moderate elasticity while maintaining non-adhesiveness, and can be more easily peeled off from the surface of the glass substrate 16, and at the same time adheres to the surface of the glass substrate 16. It will be enough.

Moreover, it is preferable that the resin layer 14 has the outstanding heat resistance. For example, when forming the structural member 18 of the panel for display devices on the 2nd main surface of the glass substrate 16, the glass substrate laminated body 30 of this invention can be used for the heat processing on high temperature conditions. The cured silicone resin in the present invention has sufficient heat resistance to withstand this heat treatment.
More specifically, the thermal decomposition start temperature of the resin layer 14 made of the cured silicone resin in the present invention can be 400 ° C. or higher in the glass substrate laminated state. The heat resistant temperature is more preferably 420 ° C. or higher, and particularly preferably 430 ° C. to 450 ° C. If it is in the said range, decomposition | disassembly of the resin layer 14 will be suppressed also under high temperature conditions (about 400 degreeC or more), such as a manufacturing process of a TFT array, and generation | occurrence | production of the foam in the glass substrate laminated body 30 will be suppressed more.

The thermal decomposition start temperature is expressed by the following measurement method.
A resin layer (thickness = about 15-20 μm) is formed on a 50 mm square support substrate (thickness = about 0.4-0.6 mm), and a 50 mm square glass substrate (thickness = about 0.1-0.1 mm). An evaluation sample is obtained by further stacking 0.4 mm). Then, the sample is placed on a hot plate heated to 300 ° C., heated at a heating rate of 10 ° C. per minute, and the temperature at which the foaming phenomenon is confirmed in the sample is defined as the thermal decomposition start temperature.

<Support>
In the illustrated example, the support 20 according to the present invention includes the support substrate 12 and the resin layer 14 described above. Since the surface of the resin layer 14 exhibits good peeling performance, it can be peeled without destroying the laminated glass substrate 16 thereon. Therefore, it can be suitably used as a support for supporting the glass substrate. Moreover, as another use, the support body of the glass substrate for organic EL lighting, etc. are mentioned.
In addition, as above-mentioned, it is preferable that it is a support body provided with the resin layer 14 formed by hardening the said organopolysiloxane composition on the support substrate surface.

<Glass substrate>
The glass substrate 16 is a glass substrate for producing a display device panel by forming a constituent member 18 of the display device panel, which will be described later, on the glass substrate 16.
The manufacturing method of the glass substrate 16 used by this invention is not specifically limited, It can manufacture by a conventionally well-known method. For example, it can be obtained by melting a conventionally known glass raw material into a molten glass and then forming it into a plate shape by a float method, a fusion method, a slot down draw method, a redraw method, a pulling method or the like. Commercial products can also be used.

  The thickness, shape, size, physical properties (heat shrinkage rate, surface shape, chemical resistance, etc.), composition, etc. of the glass substrate 16 are not particularly limited. For example, a glass substrate for a display device such as a conventional LCD or OLED It may be the same.

  The thickness of the glass substrate 16 is not particularly limited, but is preferably less than 0.7 mm, more preferably 0.5 mm or less, and even more preferably 0.4 mm or less. Further, it is preferably 0.05 mm or more, more preferably 0.07 mm or more, and further preferably 0.1 mm or more.

  The glass substrate 16 has the 1st main surface and the 2nd main surface, Although the shape is not limited, It is preferable that it is a rectangle. Here, the rectangle is substantially a rectangle and includes a shape obtained by cutting off the corners of the peripheral portion (corner cut).

  Although the magnitude | size of the glass substrate 16 is not limited, For example, in the case of a rectangle, it may be 100-2000 mm x 100-2000 mm, and it is preferable that it is 500-1000 mm x 500-1000 mm.

  With such a preferable thickness and preferable size, the glass substrate laminate 30 of the present invention can easily peel the glass substrate 16 and the support 20 from each other.

Properties of the glass substrate 16 such as heat shrinkage, surface shape, chemical resistance, etc. are not particularly limited, and vary depending on the type of display device panel to be manufactured.
However, the thermal contraction rate of the glass substrate 16 is preferably small. Specifically, the linear expansion coefficient, which is an index of the thermal shrinkage rate, is preferably 150 × 10 ⁻⁷ / ° C. or less, more preferably 100 × 10 ⁻⁷ / ° C. or less, and 45 × 10 ⁻⁷ / ° C. More preferably, it is not higher than ° C. This is because it is difficult to produce a high-definition display device when the thermal shrinkage rate is large.
In addition, in this invention, a linear expansion coefficient means a thing prescribed | regulated to JISR3102 (1995).
The glass substrate 16 is made of, for example, alkali glass or non-alkali glass. Among these, alkali-free glass is preferable because of its low thermal shrinkage rate.

  The surface of the glass substrate 16 described above may be a polished surface that has been subjected to polishing treatment, or may be a non-etched surface (fabric surface) that has not been subjected to polishing treatment. That is, a material that satisfies flatness may be selected as appropriate in accordance with the required accuracy of the display panel to be manufactured.

<Glass substrate laminate>
In the illustrated example, the glass substrate laminate 30 according to the present invention includes the support substrate 12, the resin layer 14, and the glass substrate 16 described above. It is preferable that a glass substrate laminated body is used for the use exposed to the temperature of 400 degreeC or more for 10 minutes or more. In addition, specifically as an above-mentioned use, the use etc. which manufacture the panel for display apparatuses mentioned later are mentioned.
As described above, the resin layer 14 has a peelable surface, and can easily peel off the glass substrate 16 and the display device panel 40 (the glass substrate 16 on which the constituent member 18 of the display device panel is formed). . More specifically, the peel strength between the surface of the resin layer 14 and the surface of the glass substrate 16 is preferably 8.5 N / 25 mm or less, more preferably 7.8 N / 25 mm or less, and 4.5 N / 25 mm. The following are particularly preferred: If it is in the said intensity | strength, destruction of the resin layer 14 at the time of peeling, destruction of the glass substrate 16, etc. hardly occur, and it is preferable. About a lower limit, the glass substrate 16 should just have the adhesive force of the grade which does not raise | generate a position shift on the resin layer 14, and it is preferable that it is 1.0 N / 25mm or more normally.

The peel strength between the resin layer 14 surface and the glass substrate 16 surface is represented by the following measurement method.
A resin layer (thickness = about 15 to 20 μm) is formed on the entire surface of a 25 × 50 mm square support substrate (thickness = about 0.4 to 0.6 mm), and a 25 × 75 mm square glass substrate (thickness = An evaluation sample is obtained by laminating about 0.1 to 0.4 mm). Then, after fixing the non-adsorption surface of the support substrate of the sample to the end of the table with double-sided tape, the center part of the protruding glass substrate (25 × 25 mm) is pushed up vertically using a digital force gauge and peeled off. Measure strength.

On the other hand, the peel strength between the resin layer 14 surface and the support substrate 12 surface is preferably 9.8 N / 25 mm or more, more preferably 14.7 N / 25 mm or more, and particularly preferably 19.6 N / 25 mm or more. . In the case of having the above-described peel strength, when the glass substrate 16 or the like is peeled from the resin layer 14, the support substrate 12 and the resin layer 14 are unlikely to peel off, and the glass substrate 16 or the like and the support 20 (supporting substrate 20 12 and a laminate of the resin layer 14). As described above, this peel strength can be easily achieved by curing the curable silicone resin composition on the support substrate 12. Also, if the peel strength between the surface of the resin layer 14 and the surface of the support substrate 12 is too high, when the support substrate 12 and the resin layer 14 need to be peeled for reuse of the support substrate 12, There is a possibility that the peeling becomes difficult. Therefore, the peel strength between the resin layer 14 surface and the support substrate 12 surface is preferably 29.4 N / 25 mm or less.
Further, the peel strength between the resin layer 14 surface and the support substrate 12 surface is preferably 10 N / 25 mm or more higher than the peel strength between the resin layer 14 surface and the glass substrate 16 surface, and 15 N / 25 mm or more. High is preferred.

<Method for producing glass substrate laminate>
The glass substrate laminate 30 is preferably manufactured by a method (laminate method) in which the glass substrate 16 is laminated on the surface of the resin layer 14 of the support 20. However, the manufacturing method of the glass substrate laminate 30 is not limited to this lamination method. In the laminating method, the first main surface of the glass substrate 16 and the peelable surface of the resin layer 14 are bonded together by a force caused by van der Waals force between adjacent solid molecules, that is, an adhesion force. It is considered possible. Therefore, in this case, the support substrate 12 and the glass substrate 16 can be held in a state of being laminated via the resin layer 14.
Hereinafter, the manufacturing method of the glass substrate laminated body 30 by the method of laminating | stacking the glass substrate 16 on the surface of the resin layer 14 of the support body 20 is demonstrated.

  The method for laminating the glass substrate 16 on the surface of the resin layer 14 fixed to the support substrate 12 is not particularly limited, and can be carried out using a known method. For example, after laminating the glass substrate 16 on the surface of the resin layer 14 in a normal pressure environment, a non-contact pressure bonding method using a pressure chamber, or a method of pressure bonding the resin layer 14 and the glass substrate 16 using a roll or a press. Etc. It is preferable that the resin layer 14 and the glass substrate 16 are more closely adhered to each other by pressure bonding with a pressure chamber, a roll, a press or the like. Further, it is preferable because air bubbles mixed between the resin layer 14 and the glass substrate 16 are relatively easily removed by pressurization with gas and pressure bonding with a roll or press. When pressure bonding is performed by a vacuum laminating method or a vacuum pressing method, it is more preferable because the suppression of the mixing of bubbles and the securing of good adhesion are performed better. By pressure bonding under vacuum, there is an advantage that even if minute bubbles remain, the bubbles do not grow by heating, and the glass substrate 16 is unlikely to be distorted.

  When laminating the support 20 and the glass substrate 16, it is preferable that the surface of the glass substrate 16 is sufficiently washed and laminated in an environment with a high degree of cleanliness. Even if a foreign substance is mixed between the resin layer 14 and the glass substrate 16, the resin layer 14 is deformed and thus does not affect the flatness of the surface of the glass substrate 16. Is preferable because it becomes favorable.

<Components of display panel>
In the present invention, the constituent member 18 of the display device panel refers to a member formed on the glass substrate 16 or a part thereof in a display device such as an LCD or an OLED using a glass substrate. For example, in a display device such as an LCD or OLED, various circuit patterns such as a TFT array (hereinafter simply referred to as “array”), a protective layer, a color filter, a liquid crystal, a transparent electrode made of ITO, etc. on the surface of the glass substrate 16. These members or a combination of these members is formed. Further, for example, in a display device made of OLED, a transparent electrode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and the like formed on the glass substrate 16 can be used. The display device panel 40 including the glass substrate 16 and the constituent member 18 is a glass substrate on which at least a part of the above members is formed. Therefore, for example, the display device panel 40 is a glass substrate on which an array is formed or a glass substrate on which a transparent electrode is formed.

<Panel for display with support>
In the illustrated example, the support-equipped display device panel 10 includes a support substrate 12, a resin layer 14, a glass substrate 16, and a component 18 of the display device panel.
The display device panel with support 10 includes, for example, an array formation surface of the support device display panel in which the array is formed on the second main surface of the glass substrate, and a color filter is the second main surface of the glass substrate. A form in which the color filter forming surface of the display device panel with another support formed on the surface is bonded via a sealing material or the like is also included.

Further, the display device panel 40 can be obtained from the support-equipped display device panel 10. That is, the glass substrate 16 and the resin layer 14 fixed to the support substrate 12 are peeled from the display device panel 10 with the support, and the display device panel component member 18 and the glass substrate 16 are used. A panel 40 can be obtained.
Further, a display device can be obtained from such a display device panel. Examples of the display device include an LCD and an OLED. Examples of LCD include TN type, STN type, FE type, TFT type, and MIM type.

<Method for producing panel for display device with support>
Although the manufacturing method of the panel for display apparatuses with a support mentioned above is not specifically limited, Forming at least one part of constituent member 18 of a panel for display apparatuses may be formed on the glass substrate 16 surface of glass substrate layered product 30 mentioned above. preferable.

A method for forming at least a part of the constituent member 18 of the display device panel on the surface of the glass substrate 16 of the glass substrate laminate 30 is not particularly limited, and conventionally known according to the type of the constituent member 18 of the display device panel. The method is implemented.
For example, taking the case of manufacturing an OLED as an example, in order to form an organic EL structure on the second main surface of the glass substrate 16 of the glass substrate laminate 30, it is transparent on the second main surface of the glass substrate 16. Form an electrode, deposit a hole injection layer, hole transport layer, light emitting layer, electron transport layer, etc. on the surface on which a transparent electrode is formed, form a back electrode, seal using a sealing plate, etc. Various layer formation and processing are performed. Specific examples of the layer formation and processing include film formation processing, vapor deposition processing, sealing plate adhesion processing, and the like. The formation of these constituent members may be part of the formation of all the constituent members necessary for the display device panel. In that case, after the glass substrate 16 on which some of the constituent members are formed is peeled off from the resin layer 14, the remaining constituent members are formed on the glass substrate 16 to manufacture a display device panel.

<Method for Manufacturing Display Panel>
After obtaining the above-described display device panel 10 with a support, the first main surface of the glass substrate 16 and the peelable surface of the resin layer 14 in the display device panel 40 with a support are further peeled to obtain a display device. Panel 40 can be obtained. As described above, when the constituent members on the glass substrate 16 at the time of peeling are a part of the formation of all the constituent members necessary for the display device panel, the remaining constituent members are then formed on the glass substrate 16. Thus, the display device panel 40 is manufactured.

  The method of peeling the 1st main surface of the glass substrate 16 and the peelable surface of the resin layer 14 is not specifically limited. Specifically, for example, a sharp blade-like object is inserted into the interface between the glass substrate 16 and the resin layer 14 and given a trigger for peeling, and then the peeling is performed by spraying a mixed fluid of water and compressed air. can do. Preferably, the support substrate 12 of the display device panel with support 10 is placed on the surface plate so that the support substrate 12 is on the upper side and the panel side is on the lower side, and the panel side substrate is vacuum-adsorbed on the surface plate (the support substrate is on both sides). In this state, the blade is first inserted into the glass substrate 16-resin layer 14 interface. Then, the support substrate 12 side is sucked by a plurality of vacuum suction pads, and the vacuum suction pads are raised in order from the vicinity of the place where the blade is inserted. As a result, an air layer is formed at the interface between the resin layer 14 and the panel-side glass substrate 16, and the air layer spreads over the entire interface, so that the support substrate 12 can be easily peeled off (panel 10 for display device with support). In the case where the support substrate 12 is laminated on both sides, the above peeling process is repeated one side at a time).

  Moreover, after obtaining the display device panel 40 described above, a display device can be manufactured by using the obtained display device panel 40. Here, the operation for obtaining the display device is not particularly limited. For example, the display device can be manufactured by a conventionally known method.

  For example, when manufacturing a TFT-LCD as a display device, a step of forming an array on a conventionally known glass substrate, a step of forming a color filter, a glass substrate on which an array is formed, and a glass substrate on which a color filter is formed May be the same as various steps such as a step of bonding together through a sealing material or the like (array / color filter bonding step). More specifically, examples of the processing performed in these steps include pure water cleaning, drying, film formation, resist solution application, exposure, development, etching, and resist removal. Furthermore, as a process performed after implementing an array color filter bonding process, there exists a liquid-crystal injection | pouring process and the sealing process of the injection port performed after implementation of this process, The process implemented by these processes is mentioned.

  The following items were evaluated for the glass substrate laminates produced in the following examples.

<Example 1>
Prepare a glass substrate (“AN100”, linear expansion coefficient 38 × 10 ⁻⁷ / ° C. non-alkali glass plate: manufactured by Asahi Glass Co., Ltd.) having a length of 350 mm, a width of 300 mm, and a thickness of 0.5 mm as a support substrate and washed with pure water Then, the substrate was cleaned by UV cleaning to obtain a support substrate having a cleaned surface.
Next, as a component (A), linear vinylmethylpolysiloxane (“VDT-127”, viscosity at 25 ° C. 700-800 cP (centipoise): manufactured by Azumax, mol% of vinyl group in 1 mol of organopolysiloxane: 0.325 ) And linear methylhydropolysiloxane (“HMS-301” as component (B), viscosity 25-35 cP (centipoise) at 25 ° C .: manufactured by Asmax, the number of hydrogen atoms bonded to silicon atoms in one molecule: 8) and the molar ratio of all alkenyl groups to hydrogen atoms bonded to all silicon atoms (hydrogen atom / alkenyl group) is 0.9, and the component is added to 100 parts by weight of this siloxane mixture. As (D), 0.3 part by mass of 1-ethynyl-1-cyclohexanol was added. Next, a platinum-based catalyst (CAT-PL-56 manufactured by Shin-Etsu Silicone Co., Ltd.) is added to the total amount of the component (A) and the component (B) so as to be 1100 ppm in terms of platinum, and organopolysiloxane A composition was obtained.
The obtained composition was applied onto the first main surface of the previously cleaned support substrate by a spin coater (2000 rpm, 20 seconds, coating amount 20 g / m ² ). Thereafter, the mixture coated on the support substrate is heated and cured in the atmosphere at 180 ° C. for 60 minutes to form a cured silicone resin layer having a length of 350 mm × width of 300 mm and a thickness of 30 μm on the support substrate, thereby obtaining a support A. It was. The surface tension of the cured silicone resin layer was 20.0 N / m.

On the other hand, a glass substrate having a length of 350 mm, a width of 300 mm, and a thickness of 0.2 mm (“AN100”, an alkali-free glass plate having a linear expansion coefficient of 38 × 10 ⁻⁷ / ° C .: manufactured by Asahi Glass Co., Ltd.) is washed with pure water and UV The surface of the resin substrate was cleaned.
Then, after aligning the support A and the glass substrate, using a vacuum press apparatus, the first main surface of the glass substrate and the peelable surface of the cured silicone resin layer of the support A are used at room temperature. The glass substrate laminate A was obtained by close contact.

<Example 2>
A glass substrate laminate was obtained according to the same procedure as in Example 1 except that the platinum catalyst amount was 1500 ppm in terms of platinum with respect to the total amount of the component (A) and the component (B). . The surface tension of the cured silicone resin layer was 20.2 N / m.

<Example 3>
A glass substrate laminate was obtained according to the same procedure as in Example 1, except that the platinum catalyst amount was 2000 ppm in terms of platinum with respect to the total amount of the component (A) and the component (B). . The surface tension of the cured silicone resin layer was 20.0 N / m.

  In addition, from the result of the peelability test in which peeling proceeds between a glass substrate and a cured silicone resin layer described later, the peel strength between the glass substrate and the cured silicone resin layer in Examples 1 to 3 is It was confirmed that it was lower than the peel strength between the cured silicone resin layer.

<Comparative Example 1>
A glass substrate laminate was obtained according to the same procedure as in Example 1 except that the platinum catalyst amount was 200 ppm in terms of platinum with respect to the total amount of the component (A) and the component (B). .

<Comparative Example 2>
A glass substrate laminate was obtained according to the same procedure as in Example 1, except that the amount of the platinum-based catalyst was 700 ppm in terms of platinum with respect to the total amount of the component (A) and the component (B). .

  Next, the following items were evaluated.

<Heat resistance test>
The glass substrate laminate having a size of 20 mm × 20 mm was placed in a table lamp heating device (MILA-5000 manufactured by ULVAC-RIKO) and heat-treated at a temperature of 450 ° C. for 1 hour. Then, it cooled to room temperature and confirmed the residual weight of the hardening silicone resin layer before and behind a heating. In addition, the temperature of this heat processing is substantially the same as the heating temperature in the manufacturing process of a liquid crystal panel.
Usually, in the manufacturing process of a liquid crystal panel, a heat treatment process at 450 ° C. is usually performed at least twice. Therefore, in the heat resistance test, if the remaining weight% [(weight of the resin layer after heating / weight of the resin layer before heating) × 100] is 70% by weight or more, “A”, and if it is 50% by weight or more, When “B” was 40% by weight or more, “C” was evaluated. In addition, if it is 50 weight% or more, a resin layer can remain | survive even if it passes through the said 2 times heat processing process. If it is 40 weight% or more, a glass substrate can be favorably hold | maintained on a support body even after heat processing. On the other hand, the case of less than 40% by weight was evaluated as “D”.

<Adhesion test>
The glass substrate laminate is placed on a horizontal plate so that the second main surface of the glass substrate is on the upper side, and the center of the second main surface of the glass substrate is adsorbed with an adsorption pad having a diameter of 20 mm, It was lifted at a speed of 25 mm / sec, and it was evaluated whether the glass substrate and the supporting substrate were not separated and had good adhesion.
The case where it was not separated was evaluated as adhesion “◯”, and the case where it was separated was evaluated as adhesion “x”.

<Peelability evaluation>
Ten sets of the above glass substrate laminates were prepared, put into a constant temperature and high humidity bath of 60 ° C. and 90% RH for 24 hours, and then the glass substrate laminate was taken out from the constant temperature and high humidity bath and heated at 220 ° C. for 4 hours.
After the second main surface of the glass substrate of the heat-treated glass substrate laminate is vacuum-adsorbed on a surface plate, a thickness is formed at the interface between the glass substrate and the cured silicone resin layer at one corner of the glass substrate laminate. A stainless steel blade having a thickness of 0.1 mm was inserted to give a trigger for peeling between the first main surface of the glass substrate and the peelable surface of the cured silicone resin layer.
And after adsorb | sucking the 2nd main surface of the support substrate of a glass substrate laminated body with a several vacuum suction pad by 90 mm pitch, it raises in order from the suction pad near the corner part which gave the said peeling trigger, and thereby a glass substrate The first main surface and the peelable surface of the cured silicone resin layer were peeled off. This treatment was continuously performed 10 times for 10 sets of glass substrate laminates prepared, and it was evaluated how many sets of laminates could be peeled without breaking the glass or breaking the cured silicone resin layer.
Even in one of the 10 pairs measured, “X” was evaluated when the glass was broken or the cured silicone resin layer was broken, and “◯” was evaluated when all 10 pairs could be peeled without problems.

  Table 1 shows the results of the above evaluation using the glass substrate laminates obtained in Examples 1 to 3 and Comparative Examples 1 and 2.

From the result of the said Table 1, the cured silicone resin layer obtained using the organopolysiloxane composition of this invention showed the outstanding heat resistance, adhesiveness, and peelability.
In particular, as can be seen from the comparison with Comparative Examples 1 and 2, it has been shown that it has excellent heat resistance and can be suitably applied to a manufacturing process under high-temperature conditions such as manufacturing of a TFT array.

Example 4
In this example, an LCD is manufactured using the glass substrate laminate B obtained in Example 2.
Two glass substrate laminates B are prepared, and one is subjected to an array forming process to form an array on the second main surface of the glass substrate. The remaining one sheet is subjected to a color filter forming step to form a color filter on the second main surface of the glass substrate. The heating conditions in the array formation process of this example are 450 ° C. and 1 hour.
The support B is the outer side of the laminate B1 (display panel with support according to the present invention) in which the array is formed and the laminate B2 (display panel with support according to the present invention) in which the color filter is formed. Thus, an LCD empty cell having a laminate on both sides is obtained.

  Subsequently, the second main surface of the laminated body B1 is vacuum-adsorbed on the surface plate, and a stainless steel knife having a thickness of 0.1 mm is inserted into the interface between the glass substrate and the resin layer at the corner of the laminated body B2, and the glass substrate This provides a trigger for peeling between the first main surface and the peelable surface of the resin layer. And after adsorbing the 2nd main surface of the support substrate of layered product B2 with 24 vacuum suction pads, it raises in order from the suction pad near the corner part of layered product B2. As a result, it is possible to peel off the support substrate to which the resin layer is fixed, leaving only the LCD empty cells with the support substrate of the laminate B1 on the surface plate.

  Next, the second main surface of the glass substrate having the color filter formed on the first main surface is vacuum-adsorbed on the surface plate, and a thickness of 0. 0 is formed at the interface between the glass substrate and the resin layer at the corner portion of the laminate B1. A 1 mm stainless steel blade is inserted to give a trigger for peeling between the first main surface of the glass substrate and the peelable surface of the resin layer. And after adsorbing the 2nd main surface of the support substrate of layered product B1 with 24 vacuum suction pads, it raises in an order from the suction pad near the corner part of layered product B1. As a result, only the LCD cell is left on the surface plate, and the support substrate to which the resin layer is fixed can be peeled off. In this way, an empty cell of the LCD composed of a glass substrate having a thickness of 0.1 mm is obtained.

  Subsequently, the empty cell of the LCD is cut and divided into 168 empty cells of 51 mm long × 38 mm wide, and then a liquid crystal injection step and an injection port sealing step are performed to complete the LCD cell. A step of attaching a polarizing plate to the completed LCD cell is performed, and then a module forming step is performed to obtain an LCD. The LCD obtained in this way does not have a problem in characteristics.

  According to Examples 1 to 4, by adding a platinum catalyst in an amount of 900 ppm or more in terms of platinum, the amount of decomposition of the resin layer is significantly reduced under the condition of heating at 400 ° C. or more for 10 minutes or more as compared with the addition amount of the comparative example. can do. Furthermore, when it is 1100 ppm or more, the decomposition amount of the resin layer is less than 50%, and the same heating condition can be repeated twice.

DESCRIPTION OF SYMBOLS 10 Display device panel with support body 12 Support substrate 14 Resin layer 16 Glass substrate 18 Component member of display device panel 20 Support body 30 Glass substrate laminated body 40 Display device panel

Claims (14)

A support for laminating a glass substrate on the surface of the cured silicone resin layer, comprising a support substrate and a cured silicone resin layer having a peelable surface provided on one side of the support substrate;
The cured silicone resin layer contains at least (A) a linear organopolysiloxane having an alkenyl group, (B) an organopolysiloxane having a hydrogen atom bonded to a silicon atom, and (C) a platinum-based catalyst. The organopolysiloxane composition cured by an addition reaction in which the content of the component (C) is 900 to 3000 mass ppm in terms of platinum with respect to the total amount of the component (A) and the component (B), cured silicone resin layer der formed by curing on the support surface of the substrate is,
A support characterized in that it is used for applications exposed to a temperature of 400 ° C or higher for 10 minutes or longer .   The support according to claim 1, wherein the cured silicone resin layer has a thickness of 5 to 50 μm.   The support according to claim 1 or 2, wherein the content of the component (C) is 1500 to 3000 mass ppm in terms of platinum with respect to the total amount of the component (A) and the component (B).   The support according to any one of claims 1 to 3, wherein the organopolysiloxane composition further contains an addition reaction inhibitor. A glass substrate laminate having a supporting substrate, a glass substrate and a cured silicone resin layer present between them,
The cured silicone resin layer contains at least (A) a linear organopolysiloxane having an alkenyl group, (B) an organopolysiloxane having a hydrogen atom bonded to a silicon atom, and (C) a platinum-based catalyst. Curing of an organopolysiloxane composition cured by an addition reaction, wherein the content of the component (C) is 900 to 3000 ppm by mass in terms of platinum with respect to the total amount of the component (A) and the component (B). Made of things,
Rather lower than the peeling strength between the peeling strength between the supporting substrate and the cured silicone resin layer between the glass substrate and the cured silicone resin layer,
A glass substrate laminate, which is used for an application that is exposed to a temperature of 400 ° C. or more for 10 minutes or more .   The glass substrate laminate according to claim 5, wherein the content of the component (C) is 1500 to 3000 mass ppm in terms of platinum with respect to the total amount of the component (A) and the component (B).   The glass substrate laminate according to claim 5 or 6, wherein the organopolysiloxane composition further contains an addition reaction inhibitor.   The cured silicone resin layer cures the organopolysiloxane composition in contact with the support substrate surface and not in contact with the glass substrate surface, and contacts the glass substrate surface after the organopolysiloxane composition is cured. The glass substrate laminate according to any one of claims 5 to 7, wherein the glass substrate laminate is a layer formed as described above. A support for manufacturing a panel for a display device, wherein at least a part of constituent members of the panel for a display device is formed on the glass substrate surface of the glass substrate laminate according to any one of claims 5 to 8. Panel for display. At least a part of the constituent members of the display device panel is formed on the glass substrate surface of the glass substrate laminate according to any one of claims 5 to 8 , and then the glass substrate and the support substrate with the cured silicone resin layer A method for manufacturing a panel for a display device having a glass substrate. An organopolysiloxane composition for use in forming a peelable resin layer on a glass substrate,
(A) a linear organopolysiloxane having an alkenyl group, (B) an organopolysiloxane having a hydrogen atom bonded to a silicon atom, and (C) a platinum-based catalyst,
The content of the component (C), the total amount of the component (A) and the component (B), Ri 900-3000 ppm by mass der in terms of platinum,
An organopolysiloxane composition cured by an addition reaction, wherein the cured product is used in an application in which the cured product is exposed to a temperature of 400 ° C. or higher for 10 minutes or longer . An organopolysiloxane composition for use in forming a peelable resin layer on a glass substrate,
  (A) a linear organopolysiloxane having an alkenyl group, (B) an organopolysiloxane having a hydrogen atom bonded to a silicon atom, and (C) a platinum-based catalyst,
  The content of the component (C) is 900 to 3000 ppm by mass in terms of platinum with respect to the total amount of the component (A) and the component (B).
An organopolysiloxane composition cured by an addition reaction, wherein the cured product is used for an application in which the cured product is exposed to a temperature of 400 ° C. or more for 10 minutes or more in a state of being sealed with a gas-impermeable face material. The organopolysiloxane composition according to claim 11 or 12 , wherein the content of the component (C) is 1500 to 3000 ppm by mass in terms of platinum with respect to the total amount of the component (A) and the component (B). . The organopolysiloxane composition according to any one of claims 11 to 13 , further comprising an addition reaction inhibitor.