WO2010018651A1 - Protected panel for display and method of forming the protected panel - Google Patents

Abstract

A protected panel for displays is provided which is obtained by adhering a protective layer to an adherend without causing air inclusion.  Even when the protective layer is applied to a light-shielding film or the like disposed on a display panel, the application does not result in inclusion of air bubbles or voids.  The protective layer can be repositioned by reapplication, and can be recycled after stripping.  Also provided is a method of forming the protected panel. A stress-relaxing layer constituted of a pressure-sensitive adhesive elastomer which comprises an acrylic or urethane resin as a major component and has a thickness of 10-3,000 µm and an elongation of 50-350% is disposed on an adherend surface of a display panel and/or a material protecting the display panel.  A protective layer constituted of a glass or resin plate having a thickness of 0.1-7 mm is adhered to the adherend surface through a hydrophobic liquid layer having a nonvolatile viscosity of 2,000 cps or lower and a thickness of 1-500 µm, the liquid layer being disposed on at least one side of the stress-relaxing layer.

Description

Protective body of display device and method of forming the protective body

The present invention relates to a protective body for a display device and a method for forming the protective body. More specifically, for example, a transparent protective layer made of glass or a resin plate is provided on a surface to be adhered (including a polarizing plate) of the display device. When affixing on a display body, it can be reattached, there is no void mixed with bubbles, it can be adhered without impairing transparency, and an effect of reducing light reflection can be obtained. Even when a printed or light shielding film is applied to a part of the surface of the display body, air bubbles and cavities do not occur, and stress relaxation of the display body and the protective layer and scattering of the display body and the protective layer occur. The present invention relates to a protective body for a display body of a display device capable of obtaining a prevention effect and a method for forming the protective body.

Display devices of display devices such as liquid crystal (LCD), PDP (plasma display panel), and organic EL (including polarizing plates; the same applies hereinafter), which are display devices (displays) of display devices such as televisions, billboards, and mobile phones An acrylic resin plate, tempered glass, or the like is used as a protective layer for protecting the film. Between this kind of display body and the protective layer, an impact buffering space is provided to protect the display body. On the other hand, the difference in the optical refractive index of the glass plate with respect to the optical refractive index of this space increases the reflective interface between the incident light from the outside and the outgoing light on the display side, and the reflectance increases by 2-3% at one interface. The reflectance increases at 4 to 6% at the interface between the space and the glass plate, and as a result, the luminance is hindered by about 12%.

As a solution for preventing light reflection with respect to the display body of the display device, a single layer or a multilayer of inorganic particles, metal oxides or the like having a nano particle diameter of about 300 nm smaller than the wavelength of light on the surface, the protective layer surface or both surfaces of the display body It has been proposed that an antireflection film is formed by sputtering, vapor deposition, coating, etching, or the like and adhered to a display body.
However, forming a thin film consisting of nano-particles while maintaining transparency is difficult to achieve reproducibility as well as forming a constant thickness, and requires a large amount of load because it requires vacuum forming and multilayer forming. It becomes expensive.

On the other hand, it has been proposed to form the thin film by liquid thermosetting adhesion, encapsulating UV (ultraviolet ray) cross-linked syrup, or forming by silicon gel, urethane gel, acrylic adhesive layer, or the like. Liquid-encapsulated acrylic syrup, urethane syrup and other UV (ultraviolet) post-crosslinks, but with thermosetting materials, it is difficult for air to escape when the liquid is injected, and distortion occurs during curing shrinkage and spacers for process jigs. The design / adjustment of (thickness of coating and prevention of liquid leakage) and liquid dripping at the time of encapsulation occur, making the film forming process complicated. The same applies to adhesion using a thermosetting adhesive.

Assuming a photovoltaic power generation glass plate (solar panel) for solar power generation as a display body of a display device, a thermoplastic EVA film (ethylene vinyl acetate) equivalent to a thickness of 300 μm is used as a laminated adhesive film as a protective layer of the display body. However, when laminating the glass plate and the light receiving element plate of these display bodies, as a countermeasure against defoaming, a fine unevenness treatment of about 2 to 10 μm is applied to the EVA film, and EVA is applied by an autoclave method or the like. Pressurized and heated for 30 minutes to 3 hours near the melting point of the film. However, disordered optical birefringence occurs in the EVA molecular orientation, making it unsuitable for display-optical components.

In addition, it is extremely difficult to attach the display body and a glass plate or an acrylic plate using an adhesive sheet, a gel sheet or the like while letting air escape. These cannot be solved even by heating and pressurizing for a long time.

On the other hand, means for sucking the air in the internal gap and bringing it into close contact under reduced pressure is proposed in JP-A-2005-319752.

Also, today, mobile phones have moved from the call function to the one-seg, game, and other directions to enjoy more images, and touch panels have been developed mainly for mobile phones. However, the power source for brightening the image is limited for viewing, unlike home televisions and personal computers, and reflection by light such as sunlight cannot be avoided when viewing outdoors even if the light source is strong. .

Home TVs and personal computer displays are also becoming more touchscreen-oriented. The problem with the above-mentioned touch panel of a mobile phone is that the display body such as an LCD must be protected from being pressed by a finger. Conventionally, as a cushioning material on the four side edges (window frame) of the display body, the thickness; 0.2 There has been proposed an arrangement in which a cushioning body made of a foamed material such as urethane type or olefin type of up to 0.6 mm is arranged. However, if it becomes a touch panel, this four side end (window frame) alone cannot cope with stress buffer over time, including buffer measures at the center of the display body.

In order to improve the brightness of the displayed image and reduce the surface reflection from the protective layer, in order to reduce the dependence on the reflectance and the incident angle and expand the wavelength range, a process that requires a multilayer coating film has been conventionally used. A complex anti-reflection coating method is used.

The prior art document information of this invention includes the following.

JP 2005-319752 A

However, the conventional protector and the forming means by sticking the protector have the following problems.

(1) The method of injecting the adhesive is difficult to remove bubbles, and the spacer (application jig) for controlling the application thickness is poorly controlled, and a gap due to distortion due to shrinkage with time is likely to occur.

(2) When a glass plate having a transparent adhesive film and a plate such as a glass plate are adhered to each other, air is inevitable only in a vacuum atmosphere, and a clear light-transmitting display is obtained by bubbles. I can't.

(3) The means for adhering smooth glass plates to each other in a vacuum atmosphere is a batch type, and repeats the normal pressure and vacuum drawing, resulting in the disadvantage of low productivity and excessive equipment costs. The same applies to the continuous vacuum method.

(4) Although there is a method of sticking plates such as a smooth glass plate and a smooth glass plate through an adhesive by an autoclave method (continuous pressure heating method), the effect of defoaming is not sufficient.

(5) In the method of applying moisture, alcohol, etc. to the smooth glass plate in advance to avoid air contamination, initial apparent deaeration is possible, but over time, the surface distortion of the glass plate can no longer be absorbed. The strain is hollowed out, and the gas is further gasified in the vicinity of a temperature of about 50 to 120 ° C. to easily generate bubbles. The same applies to the adhesive film and gel sheet.

(6) As disclosed in the above-mentioned patent document, there may be a method of venting air with an embossed transfer film or engraving roll in advance or immediately before bonding to an adhesive or gel sheet, to give a residue mark, but transparent Such a pressure-sensitive adhesive molecule is subjected to orientation strain, resulting in optical strain including Newton's ring (light interference pattern), which is not suitable for optical use.

Furthermore, extremely strict process specifications are required for crossing the surface of the adhesive and the glass plate, and adjusting the crossing of the pressure surface and the pressure gradient, which is difficult to reproduce.

(7) Also, the conventional adhesive cannot be re-applied when the positioning is misidentified, so the member has to be discarded.

(8) Further, black printing (thickness: 1 to 4 μm) and black PET film t (thickness: 10 to 12 μm, including adhesive 25 to 30 μm) are formed in a window frame shape to prevent light leakage on the protective layer. However, when an adhesive film or adhesive is applied to the entire surface of the protective layer including this part, and it is attached to one plate, the adhesive layer at the stepped part due to the thickness of the black print and the thickness of the black PET with respect to the time passes. It will not be relieved and will eventually rise and become a hollow.

(9) In addition, in order to make the adhesive film and adhesive slightly harder due to enhanced toughness in film formation, die-cutting workability, and prevention of cold flow and stress relaxation, the molecular weight is (600,000 to 1,200,000 for acrylic). On the other hand, if the polymer is made high in this way, it becomes difficult to absorb the step of the above-described (6) printing and PET film. Inevitably, the escape of bubbles becomes even more difficult.

(10) Resin systems such as acrylic resin and polycarbonate resin have residual strain due to linear expansion and molecular orientation, and the strain between the protective layer and the protective layer is larger than that of the glass plate that is the display body. Since this strain is absorbed, it is easy to cavitate.

(11) Lamination and defoaming can be performed near the melting point of 100 to 150 ° C using thermoplastic EVA (ethylene vinyl acetate) film, etc., but LCDs, organic EL, etc. of display bodies have molecular characteristics, thermal sublimation, etc. If it is easy to be damaged by heat and pressurizes, the display characteristics will be fatal damage.

The distortion of the glass plate is difficult to absorb the strain due to the fluidity when the viscosity of the adhesive is 20,000 cps or more in the region where the surface crossing is within ± 0.1 to 500 μm. Even when degassing, it can easily be reversible over time or near 80 ° C., and as a result, can become a cavity.

On the other hand, if the pressure-sensitive adhesive is implemented with low cross-linking and low molecular weight, it will protrude and shift between the laminates, and the required quality will not be satisfied.

Although it can be said that the above-mentioned Japanese Patent Application Laid-Open No. 2005-314595 presents the problems of stress air absorption and removability, these are conventional joining methods that facilitate easy deaeration between a plate and a film, and are more difficult to display. There is no problem of laminating and sticking the protective layer and degassing after sticking.

The present invention solves the above-mentioned problems or problems. As a result of many years of research, a hydrophobic liquid layer is used for an adhesive elastic body, and the adhesive elastic body and a liquid forming the hydrophobic liquid layer are used in combination. It can be easily adhered and reattached, and it can be degassed while flowing and diffusing, and the liquid can be covalently bonded or chemically equilibrated over time. This is based on the knowledge that the desired performance can be obtained in terms of absorption and adhesion of polymer strain, etc. due to its low properties, low sacrificing light transmittance, low light reflectance, and Newton's ring.

The present invention employs the hydrophobic liquid layer having the above-described degassing and initial adhesion mitigating functions, thereby adhering without adhering air between the display body as the adherend and the protective layer and applying it to the display body. The printed mark and the light shielding film are free of bubbles and cavities, can be repositioned by reattachment and can be regenerated by peeling, and the required quality of adhesiveness is not sacrificed. Newton's ring is also achieved by obtaining stress relief by elasticity, high light transmittance, and low light reflectance effect, and by making the refractive index of the adhesive elastic body and hydrophobic liquid layer close to the light refractive index of 1.4% of the display body. It is an object of the present invention to provide a protective body that can be lowered and that can be prevented from being scattered when the glass is broken.

In addition, a further object of the present invention is that a highly difficult antireflection treatment such as a multilayer coating or multilayer vacuum sputtering made of an optical antireflection agent (ITO, ZnO, tin oxide) having a nano particle size is unnecessary, and the brightness of the display image is reduced. It is an object of the present invention to provide a method for forming the protective layer which can be improved without any air in the display / optical component adhering / fixing, which can improve the efficiency easily and can also prevent scattering.

In order to achieve the above object, the protective body of the display device of the present invention has a display body 40 of the display device and a thickness mainly composed of an acrylic or urethane resin disposed between the display body and the protective layer 10; At least one stress relaxation layer 20 made of an adhesive elastic body having an elongation of 50 to 350%, and a non-volatile component viscosity of 2000 cps or less formed on at least one surface of the stress relaxation layer; a hydrophobic liquid layer of 1 to 500 μm 30 (claim 1). The protective layer 10 can be formed from a resin plate made of glass or acrylic having a thickness of 0.1 to 7 mm.

Furthermore, the protective body of the display device according to the present invention is arranged such that the stress relaxation layer 20 is disposed on the display body 40 serving as the adherend surface and / or on the protection layer 10, so that both the stress relaxation layer 20 and the hydrophobic property are provided. The protective layer and the display body can be adhered via the liquid layer 30 (claim 2).

In order to achieve the above object, a method for forming a protective body for a display device according to the present invention includes an elongation ratio of 50 to 50 on the display body 40 of the display device and / or the protective layer 10 of the display body, which is an adherend surface. A stress relaxation layer 20 made of an adhesive elastic body mainly composed of 350% acrylic or urethane resin is formed to a thickness of 10 to 3000 μm, and a hydrophobic component having a nonvolatile component viscosity of 2000 cps or less is formed on at least one surface of the stress relaxation layer. The liquid layer 30 is formed to a thickness of 1 to 500 μm, and the protective layer 10 having a thickness of 0.1 to 7 mm and the display body 40 of the display device are pasted through the hydrophobic liquid layer 30. (Claim 9).

The protective body of the display device of the present invention has a thickness of 1.5 to 200 μm, light transmittance of 60%, preferably 85% or more between one surface of the stress relaxation layer 20 or between the stress relaxation layers 20 and 20. A base material 70 made of a polyester (PET) film is disposed to have a total thickness in the range of 10 to 3000 μm, and the protective layer 10 and the display body 40 are disposed on the other surface of the stress relaxation layer 20 via the hydrophobic liquid layer. If they are laminated, it is preferable that the protective layer 10 is prevented from scattering when the display device is dropped (claims 7 and 8).

The stress relaxation layer is made of an adhesive elastic body of a three-dimensional crosslinked polymer adhesive gel, and the hydrophobic liquid layer 30 is formed on at least one surface of the stress relaxation layer 20 to a thickness of 1 to 500 μm, and the hydrophobic liquid layer The layer 30 forms a secondary gelation or chemical equilibrium with the stress relaxation layer 20 over time, so that the strain of the protective layer 10 is absorbed and the protective layer is adhered to the adherend surface. It is characterized (claim 10).

The adhesive strength of the adhesive elastic body is preferably 2 to 40 N / 25 mm width (JIS-Z-0237) (Claim 3).

The boiling point of the hydrophobic liquid layer is preferably 60 to 400 ° C., a viscosity of 1 to 500 cps, and a solid content thickness of 1 to 500 μm (Claim 4).

The light refraction index of the stress relaxation layer and the hydrophobic liquid layer is preferably in the range of ± 0.1 to 0.2 with respect to the refraction index of the display body and the protective layer, and the light transmittance of 80 to 99. % (Claim 5).

The acrylic adhesive elastic body has a functional group and has acrylic acid, ethyl acrylate, methyl acrylate, 2-ethylhexyl acrylate, butyl acrylate, isobutyl acrylate, isononyl acrylate, dimethylaminoethyl acrylate, acrylic Methoxyethyl acid, stearyl acrylate, isooctyl acrylate, N-octyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, methyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, methacryl It can be selected from cyclohexyl acid, trimethylolpropane trimethacrylate, tertiary butyl methacrylate, maleic anhydride, itaconic anhydride, and citraconic anhydride. Section 6).

The hydrophobic liquid material forming the hydrophobic liquid layer is a monomer or oligomer having a hydrophobic molecular weight of 1000 g / mol or less and a non-volatile viscosity of 2000 cps or less, such as acrylic acid, fatty acid, expensive alcohol, phthalate ester, and carboxylic acid ester. (Claim 11).

As a gelling agent in the hydrophobic liquid layer, dioctyl phthalate, dibutyl phthalate (DBP), diisonyl phthalate (DINP), diidecyl phthalate (DIDP) and the like, phthalate esters, polyesters, polyethers, adipine At least one selected from the group consisting of acid ester, citrate ester, maleate ester, benzoate ester, sepacate ester, phosphate ester, oleic acid, vegetable oil, epoxidized plant An additive may be included (claim 12).

The additive is at least one selected from the group consisting of the gelling agents, and preferably has a light transmittance of 80% or more due to compatibility and transparency (claim 13).

The additive contains a solvent in the gelling agent, and can be applied and dried to adhere the protective layer to the adherend surface (claim 14).

The present invention solves the above-mentioned problems and problems, achieves the above-mentioned object, and has the following effects.

The reason why the cavity is formed when the display body and the protective layer are laminated by the adhesive elastic body is that either the adherend surface or the adhesive elastic body cannot absorb one surface smooth strain, but the hydrophobic liquid layer of the present invention. Due to the property of absorbing the strain while flowing and diffusing due to “wetting”, the hydrophobic liquid layer of the present invention and the pressure-sensitive adhesive can be bonded to each other without inhibiting the independent functions of each.

In addition, the hydrophobic liquid layer of the present invention having a viscosity of 1 to 2000 cps (at 22 ° C. atmosphere) is applied to glass or an adhesive film or an adhesive elastic body in advance with a thickness of 1 to 500 μm, preferably 5 to 40 μm. It was able to adhere well while releasing air. It can also be easily corrected if it is stuck in the wrong position.

This is because the low-viscosity monomer or oligomer flows and diffuses while leveling the glass plate surface of the adherend while promoting degassing by the self-adhesion pressure and pressure of the display and protective layer. It is a structure in which, without breaking the three-dimensional cross-linked structure of the body, it will eventually undergo chemical gelation or chemical equilibrium and living polymerization to complete the adhesion.

施工 Workability is also better than processes that require adhesive application amount, application thickness, and curing control. In addition, adhesive strength, thickness, etc. according to other applications such as protection of display bodies such as LCD (liquid crystal television), advertisement display bodies, PDP (plasma television), vehicle damping plate bonding, etc. The material can be designed freely, and the application range of the adhesive film or gel sheet can be expanded.

Furthermore, an adhesive elastic body is disposed on both the display body such as an LCD and a protective layer, and a hydrophobic liquid material is dropped or applied in the middle, and the both are laminated to form a display board or resin board having a large surface distortion. It can be adapted and, of course, can be corrected by mispositioning.

In addition, we were able to meet high demands including those for airplanes without degrading outdoor visibility by light reflection.

In addition, it is possible to reduce the surface reflection of the glass surface that causes flare and ghost without using anti-reflection coating, suppress the dependence of reflectance and incident angle, or rare metals such as ITO The wavelength range could be expanded without the need for a very multilayer coating film using multi-layer sputtering or metal oxide.

Also, the sticking process is simplified, and an inexpensive product can be obtained.

Schematic of the experimental method which shows the effect of the hydrophobic liquid layer of this invention. Schematic of the process which shows conveyance of the hydrophobic liquid body of this invention, and formation of the hydrophobic liquid layer by application | coating. 1 shows an embodiment in which a stress relaxation layer made of an adhesive elastic body is formed on a display surface of a display device according to the present invention and a protective surface of the display body, and FIG. The figure (B) is the schematic which shows the time of sticking. The schematic diagram which shows the experimental example of the raising of the level | step-difference part of this film and a protective layer, or hollowing (bubble generation) with respect to the display body window frame (it substitutes with a light leakage prevention film | membrane or a film) of an adhesive elastic body. Schematic which shows the other Example 10 which arrange | positions the PET film as a base material between stress relaxation layers.

Adhesive elastic body The adhesive elastic body provided in the present invention is a UV-crosslinked acrylic resin material mainly composed of a urethane-based heat-crosslinking type and a monomer and / or oligomer of acrylic acid, and is crosslinked by irradiating with ultraviolet rays. It is a composition having adhesiveness and elasticity obtained by being crosslinked by heat.

The adhesive elastic body thus obtained has high transparency and high viscoelasticity, so that it has good adhesion to the adherend surface and has affinity for the hydrophobic liquid layer. Adhesive elastic body is partially cross-linked and plasticized and does not flow cold, has high followability to the surface shape of the adherend surface, high transparency and reduced reflection, stress relaxation, scattering prevention effect, Airtightness and the like can be realized. In addition, it can be wound into a roll due to its flexibility, and can be continuously processed in a long state, resulting in high productivity and high yield.

The adhesive elastic body is composed of a rubber having a hardness of 20 to 90 degrees with respect to a thickness of 6 mm and an elongation of 2 to 15 times, preferably 2 to 4 times in the vertical and horizontal directions. be able to.

The adhesive strength of the adhesive elastic body has a thickness of 45 to 2000 μm and a range of 2 to 40 N / 25 mm width (JIS-Z-0273).

As the main component of the composition adhesive elastic body, as the monomer and / or oligomer of the acrylic acid as the main component, for example, the following can be used.

Examples of monomers having a functional group include acrylic acid, methacrylic acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornene dicarboxylic acid, bicyclo [2,2,1] hept-2-ene- And unsaturated carboxylic acids such as 5,6-dicarboxylic acid,
These derivatives include maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic anhydride, , Aminoethyl (meth) acrylate, propylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, aminopropyl (meth) acrylate, phenylaminoethyl (meth) acrylate, cyclohexyl (meth) acrylate Alkyl ester derivatives of (meth) acrylic acid such as aminoethyl, vinylamine derivatives such as N-vinyldiethylamine and N-acetylvinylamine, allylamine derivatives such as allylamine, methacrylamine and N-methylacrylamine, N , N-dimethylacrylamide, N, N Acrylamide derivatives such as dimethylaminopropylacrylamide, acrylamide, N-methylacrylamide, aminostyrenes such as p-aminostyrene, amino group-containing ethylenic monomers such as 6-aminohexyl succinimide, 2-aminoethyl succinimide, etc. A monomer having a saturated bond can be suitably used as appropriate.

In addition to these, ethyl acrylate, methyl acrylate, 2-ethylhexyl acrylate, butyl acrylate, isobutyl acrylate, isononyl acrylate, dimethylaminoethyl acrylate, methoxyethyl acrylate, stearyl acrylate, isooctyl acrylate, N-octyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, methyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, cyclohexyl methacrylate, trimethylolpropane trimethacrylate, tartar methacrylate Libutyl etc. can be used.

These main ingredients may be used in combination of two or more.

In order to form a crosslinked structure with respect to the above-described monomer or oligomer, a polyfunctional monomer having two or more functions can be suitably used.

As the polyfunctional monomer, for example, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, Neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, 1,1,1-trishydroxymethylethane diacrylate, 1,1,1-trishydroxymethylethanetri Acrylate, 1,1,1-trishydroxymethylpropane triacrylate, N-methylol acrylate, etc. can be used as appropriate.

Auxiliary materials In addition to the above-mentioned acrylic acid monomers and / or oligomers, which are the main components, the photopolymerization initiator, UV crosslinking accelerator (increase) are included in the UV crosslinkable acrylic resin material that becomes the above-mentioned adhesive elastic body by UV irradiation. Sensitizers) are blended.

Other auxiliary materials may include fillers, such as inorganic metal fillers as antireflective agents, vinyl acetate, styrene for the purpose of modifying hardness and adhesion, A tackifier (tackifier) may be blended. However, the addition of an inorganic metal filler, vinyl acetate, styrene, and tackifier causes optical birefringence in the Z direction (thickness direction) of the adhesive elastic body, thereby reducing the transparency, and in particular the thickness of the adhesive elastic body is 10%. In the present invention formed with a thickness of ˜3000 μm, the transparency is remarkably deteriorated. Therefore, when obtaining an adhesive film or sheet used in applications requiring transparency, these additives are not added, or a relatively small amount is added. It is preferable to stop. Alternatively, the cast process film is preferably a stretched PET film rich in smoothness because of improved light transmittance.

In the case of an ultraviolet crosslinking type instead of a thermosetting type, the acrylic resin material is coated on both sides with a nitrogen purge or a gas barrier film.

This gas barrier film has an oxygen permeability of 10,000 cc / cm ² . 24 h 20 ° C. Any material such as olefin film such as PE and PP, PET film, paper-resin laminate film or coated paper may be used as long as it is 90% RH “JIS-K-7126” or less. However, it is preferable to use a stretched PET film because it corresponds to the heat rays of an ultraviolet lamp, has reaction heat resistance, requires gas barrier properties, and has a smooth finished surface.

Of the gas barrier films, those to be peeled here are preferably coated with a release agent such as silicone on the application surface of the acrylic resin material.

The ratio of the adhesive elastic body to the hydrophobic liquid layer is in the range of 5 to 10 parts by weight of the hydrophobic liquid layer with respect to 100 parts by weight of the adhesive elastic body. Preferably, the amount of the hydrophobic liquid layer is 10 to 35 parts by weight with respect to 100 parts by weight of the adhesive elastic body in order to maintain the hardness of the adhesive elastic body.

The coating and sheeting methods for adhesive elastics use a comma knife coater, die coater, revers coater, etc. for both solution-type and solvent-free types. A die coater is preferable from the viewpoint of preventing the above.

Hydrophobic liquid layer Hydrophobic liquid layer forming the hydrophobic liquid layer is hydrophobic such as acrylic acid, fatty acid, expensive alcohol, phthalic acid ester, carboxylic acid ester, etc. with a molecular weight of 1000 g / mol or less and a non-volatile viscosity of 2000 cps or less. is there. As the monomer or oligomer, those similar to the adhesive elastic body can be used.

Examples of the phthalic acid ester type include DOP (dioctyl phthalate), DBP (dibutyl phthalate), DINP (diisonyl phthalate), DIDP (diidecyl phthalate), polyester type, and polyether type.

Also, there are adipic acid ester type, citric acid ester type, maleic acid ester type, benzoic acid ester type, sepacic acid ester type, phosphoric acid ester type, oleic acid, vegetable oil type, and epoxidized plant type.

Details are as follows.
Examples of carboxylic acid esters include ethyl acetoacetate, propyl acetoacetate, butyl acetoacetate, t-butyl acetoacetate, ethyl benzoyl acetate, and examples of o-carbonylphenol include 2-hydroxy-benzaldehyde, 2′-hydroxy. -Acetophenone, methyl-2-hydroxybenzoate, phenyl-2-hydroxybenzoate benzoic acid, o-toluic acid, m-toluic acid, p-toluic acid, 4-tert-butylbenzoic acid, 1-naphthoic acid, or 2 -Naphthoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, arachidic acid, or behenic acid, 2-hydroxycaproic acid, 2-hydroxy-3,3-dimethylγ-butyrolactone, 2-hydroxyisocaprone Acid, β Propiolactone, .delta.-valerolactone, .epsilon.-caprolactone, 4-methyl-caprolactone, 3,5,5-trimethyl-caprolactone, 3,3,5-trimethyl-caprolactone.

Fatty acid esters include wheat germ oil, sunflower oil, rapeseed oil, sesame oil, corn oil, apricot oil, castor oil, karate butter, avocado oil, olive oil, soybean oil, sweet almond oil, coconut oil, rapeseed oil, cottonseed oil, hazelnut oil , Macadamia oil, jojoba oil, alfalfa oil, poppy oil, pumpkin oil, bone marrow oil, black currant seed oil, evening primrose oil, millet oil, barley oil, quinoa oil, rye oil, safflower oil, candle nut oil, passiflora oil and musk rose Oil, perserine oil (cetostearyl octanoate), isopropyl myristate, isopropyl palmitate, C12-C15 alkylbenzoate, hexyl laurate, diisopropyl adipate, isononyl isononanoate, 2-ethylhexyl palmitate, Decanoates or ricinolates such as sostearyl isostearate, alkyl or polyalkyl octanoates, propylene glycol dioctanoate; hydroxylated esters such as isostearyl lactate and diisostearyl malate; and pentaerythritol esters, di (2 -Ethylhexyl) adipate, diisononyl adipate, di (2-ethylhexyl) sebacate, di (2-ethylhexyl) azelate, diisononylcyclohexane-1,2-dicarboxylate, oleic acid, linolenic acid or linolenic acid, tri (2-ethylhexyl) Phosphate, diphenyl 2-ethylhexyl phosphate, diphenyl cresyl phosphate, or tricresyl phosphate, di-1-butyl adipate, adipic acid -n- octyl, sebacate -n- butyl, aliphatic, such as di-2-ethylhexyl azelate dibasic acid ester, diphenyl phosphate, 2-ethylhexyl phosphoric acid ester, such as phosphoric acid diphenyl octyl,
Hydroxy polyvalent carboxylic acid ester systems such as tributyl acetyl citrate, tri-2-ethylhexyl acetyl citrate, tributyl citrate,
Fatty acid esters such as methyl acetylricinoleate and amyl stearate,
Polyhydric alcohol esters such as glycerin triacetate and triethylene glycol dicaprylate,
Epoxy plasticizers such as epoxidized soybean oil, epoxidized linseed fatty acid butyl ester, octyl epoxy stearate, polypropylene glycol sebacate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, methacrylic acid n-butyl, isobutyl methacrylate, n-pentyl methacrylate, n-hexyl methacrylate, n-heptyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, meta Methacrylic acid aliphatic hydrocarbon (eg, alkyl having 1 to 18 carbon atoms) esters such as decyl acrylate, dodecyl methacrylate, stearyl methacrylate, etc .; methacrylic acid such as cyclohexyl methacrylate and isobornyl methacrylate Aliphatic alicyclic hydrocarbon esters; Aralkyl esters of methacrylic acid such as benzyl methacrylate; Aromatic hydrocarbon esters of methacrylic acid such as phenyl methacrylate and toluyl methacrylate; 2-methoxyethyl methacrylate; Esters of methacrylic acid such as 3-methoxybutyl acrylate and functional group-containing alcohols having etheric oxygen; trifluoromethyl methacrylate, trifluoromethyl methyl methacrylate, 2-trifluoromethyl ethyl methacrylate, 2-trifluoroethyl methacrylate, 2-perfluoroethyl ethyl methacrylate, 2-perfluoroethyl 2-perfluorobutyl ethyl methacrylate, 2-perfluoroethyl methacrylate, perfluoromethyl methacrylate , Taacryl, diperfluoromethyl methyl acid, 2-perfluoromethyl-2-perfluoroethyl methyl methacrylate, 2-perfluorohexyl ethyl methacrylate, 2-perfluorodecyl ethyl methacrylate, 2-methacrylic acid 2- And methacrylic acid fluorinated alkyl esters such as perfluorohexadecylethyl.

Examples of phthalic acid esters include phthalic acid compounds such as DOP (dioctyl phthalate) and DINP (diisononyl phthalate), aromatic polybasic acid esters such as trioctyl trimellitate, DOA (dioctyl adipate), DINA (diisononyl adipate), Di (2-ethylhexyl) phthalate, diisononyl phthalate, diisodecyl phthalate, benzyl butyl phthalate, benzyl isooctyl phthalate, benzyl isononyl phthalate, diethyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, dimethyl phthalate, diethyl phthalate, phthalic acid Di-n-butyl, di- (2-ethylhexyl) phthalate, diheptyl phthalate, diisodecyl phthalate, di-n-octyl phthalate, diisononyl phthalate, Phthalic acid derivatives such as ditridecyl lurate, octyldecyl phthalate, butylbenzyl phthalate, dicyclohexyl phthalate; isophthalic acid derivatives such as dimethyl isophthalate; tetrahydrophthalic acid derivatives such as di- (2-ethylhexyl) tetrahydrophthalic acid Adipic acid derivatives such as dimethyl adipate, dibutyl adipate, di-n-hexyl adipate, di- (2-ethylhexyl) adipate, isononyl adipate, diisodecyl adipate, dibutyl diglycol adipate; Azelaic acid derivatives such as 2-ethylhexyl; sebacic acid derivatives such as dibutyl sebacate; dodecane-2-acid derivatives; maleic acid derivatives such as dibutyl maleate and di-2-ethylhexyl maleate; fumes such as dibutyl fumarate; Trimellitic acid derivatives; trimellitic acid derivatives such as tris-2-ethylhexyl trimellitic acid; pyromellitic acid derivatives; citric acid derivatives such as acetyltributyl citrate; itaconic acid derivatives; oleic acid derivatives; ricinoleic acid derivatives; stearic acid derivatives; Sulfonic acid derivatives; phosphoric acid derivatives; glutaric acid derivatives; polyester plasticizers that are polymers of dibasic acids such as adipic acid, azelaic acid, and phthalic acid and glycols and monohydric alcohols, glycol derivatives, glycerin derivatives, chlorine Paraffin derivatives such as chlorinated paraffins, epoxy derivatives polyester polymerization plasticizers, polyether polymerization plasticizers, carbonate derivatives such as ethylene carbonate and propylene carbonate, succinic acid, adipic acid, azelaic acid, sebacine Acid, dodecanedioic acid, maleic acid, and malic acid, tartaric acid and citric acid are also used as long as the performance of the present invention is not impaired.

These components may be a combination of two or more components having a light transmittance of 80% or more due to compatibility and transparency. Moreover, in order to reduce the viscosity in order to apply thinly, it is also optional to apply in combination with a solvent. However, when laminating, it is preferable to dry with hot air or the like so that there is no residual solvent. If this remains, it tends to cause outgas (bubbles).

The viscosity of the non-volatile component is 2000 cps or less, preferably 500 cps or less, and 50 cps or less is more preferable in order to facilitate flowability, diffusibility, and reattachment.

For defoaming and reattachment, the hydrophobic liquid layer preferably has an SP value (solubility index) in the range of 8 to 14 and 5, and the SP value is preferably in the range of 8 to 10 due to compatibility with acrylic resin and urethane resin. When the SP value differs from 2 to 5 with respect to the SP value of the adhesive elastic body, it is difficult to obtain living polymerization and gelation (migration) of the hydrophobic liquid layer to the adhesive elastic body.

When the hydrophobic liquid layer is converted into a coating amount, it is dropped or applied to the surface of the adhesive elastic body so that the average thickness is 5 to 400 μm / m ² . Although the amount of dripping depends on the strain of the protective plate, the amount equivalent to 20 to 60μm / m ² is suitable from the viewpoint of stability over time. Excessive degassing is good, but dripping occurs and adhesion is not performed completely. Sometimes.

In order to prevent optical birefringence and Newton's ring, it is preferable that the optical refractive index of the viscoelastic body layer and the hydrophobic liquid layer is the same as that of the display body or the protective body. Alternatively, the refractive index of the acrylic plate is in the range of 1.3 to 1.57%.

The optical refractive index is preferably the same as that of the protective plate or display plate glass or acrylic plate, and the optical refractive index is in the vicinity of 1.4%. In the range of 0.2, a difference of 0.01% in the light refractive index can be a factor of polarization birefringence and Newton ring.

Here, the refractive index of the acrylic plate as the protective plate is 1.5%, and the refractive index of the adhesive elastic body is 1.47%. The refractive index of the adhesive elastic body is preferably 1.47 to 1.53. Incidentally, the refractive index of water is 1.33%.

The difference between the refractive index of 0.01%, the birefringence, and the generation of Newton rings are related to the thickness. The difference in refractive index does not immediately become a Newton ring, and the incident angle is changed when light passes through the object. Therefore, the reflection angle varies depending on the thickness, and the Newton ring (light interference pattern) cannot be visually recognized. This is because the reflection due to the difference in refractive index is amplified and the image is not deflected.

Additives Additives or gelling agents that can be used as phthalate esters include, for example, DOP (dioctyl phthalate), DBP (dibutyl phthalate), DINP (diisonyl phthalate), DIDP (diidecyl phthalate) , Polyester and polyether.

Also, there are adipic acid ester type, citric acid ester type, maleic acid ester type, benzoic acid ester type, sepacic acid ester type, phosphoric acid ester type, oleic acid, vegetable oil type, and epoxidized plant type. And it is at least 1 sort (s) selected from the group which consists of these gelatinizers, Preferably, it is a thing with 80% or more of light transmittance from compatibility and transparency.

Example 1
Adhesive elastic body production and formulation example 1
Photopolymerization initiator Irgacure 184 manufactured by Nippon Ciba Geigy Co., Ltd. manufactured by Ciba Special Chemical Co., Ltd.) with respect to 100 parts by weight of 2-ethylhexyl acrylate and 30 parts by weight of acrylic syrup with butyl acrylate .2 parts by weight and 0.5 part by weight of an ultraviolet crosslinking accelerator (M-5A: manufactured by Soken Chemical Co., Ltd.) are gradually added and stirred.

The film is formed by extruding an acrylic adhesive elastic body with a die coater, casting it on a PET 50 μm film (pet-a) silicon-treated product, and using a PET 38 μm silicon release film (pet-b) as a gas barrier film. The coating was anaerobically coated and cross-linked with ultraviolet rays (UV irradiation below) (not shown, the symbols pet-a and pet-b were given for convenience of understanding).

In the ultraviolet crosslinking method, irradiation was performed with a UV irradiation apparatus (black light FL40SBL: NEC 40W × 2 lamp, wavelength range 200 to 280 nm / UV irradiation 500 mW / cm ² wavelength 365 nm with a mercury lamp 2 to 3 min).

Acrylic gel (adhesive elastic body) thickness obtained as described above: 100 μm, light transmittance of 100 μm in total thickness; 90% or more, adhesive peel strength; 2 rolls of acrylic adhesive elastic body having a performance of 25 N / 25 mm A PET (38 μm) release film on one side was sandwiched between rolls (rubber roll and metal roll), and a smooth glass plate as the display body 40, thickness: 1.8 mm × 50 mm × 70 mm was bonded to this surface. Peel off the other PET 50 μm release film (pet-a) of the bonded acrylic adhesive elastic body, and use an oleic acid plant-based hydrophobic liquid material with a viscosity of 3 cps on the upper surface of the acrylic adhesive elastic body. .25 g, 0.22 g, 0.19 g, 0.13 g, and 0.12 g were added dropwise and immediately under an irregular shape (average 18 mm diameter), a smooth glass plate as a protective layer 10 (g10) 5 levels were obtained. The pressing force was 50 mm × 70 mm and was carried out at about 5 kg for 5 seconds.

At the time of bonding, the adhesive strength of the acrylic adhesive elastic body of Example 1 (Formulation Example 1) was not expressed, and the surface was liquefied, and the position could be easily corrected. Visual observation showed no bubbles.

As for the peeling value, the coating resistance of the hydrophobic liquid material is 0.12 g, 0.13 g, 0.19 g, 0.22 g, and 0.25 g, and the peeling resistance cannot be measured until 5 minutes, and after 15 minutes. , Adhesive strength was obtained at coating amounts of 0.12 g, 0.13 g, and 0.19 g.

In the coating amounts of 0.22 g and 0.25 g, it takes 30 minutes to 60 minutes to develop the adhesive force because of the large amount of hydrophobic liquid applied.

Hydrophobic liquids with coating amounts of 0.12 g, 0.13 g, 0.19 g, 0.22 g, and 0.25 g have a thickness corresponding to about 34 to 71 μm in terms of coating thickness, and the total amount of all of these However, it is not permanently opposed to the surface of the adhesive elastic body, and is pushed out to the side end (outer periphery) with time so that the deaeration function at the time of bonding is achieved. It seems to be the effect of chemical gelation or living polymerization being absorbed. Therefore, the coating amounts of 0.22 g and 0.25 g are so large that the adhesive force cannot be expressed in the initial stage. However, the self weight of the display body and the pressure of gel expansion due to the hydrophobic liquid material also contribute to the hydrophobicity. By extruding a part of the ionic liquid to the outside, the effect after 15 minutes of application amounts of 0.12 g and 0.13 g approaches.

Correlation between Adhesive Strength of Formulation Example 1 and Hydrophobic Liquid Layer 100 parts by weight of phthalic acid ester is added to 100 parts by weight of oleic acid in the hydrophobic liquid material constituting the plant-based hydrophobic liquid layer, and the viscosity is 3 cps. 1. Adhesive elastic body 20 according to formulation example 1 of 1; thickness; upper surface of this adhesive elastic body 20 bonded to a glass plate 50 mm × 70 mm rectangle by peeling off a single-sided PET release film (50 μm) as a process paper of 100 μm product 0.25g, 0.22g, 0.19g, 0.13g, and 0.12g were added dropwise to the center of each, and the PET film thickness; Measurement was performed (the viscoelastic body was sandwiched between a glass plate and a PET film together with a hydrophobic liquid layer).

The coating amount of the hydrophobic liquid layer includes dripping on the glass plate side end other than the measurement surface.

As shown in Table 3 below, re-peeling is possible within 5 minutes. There is no significant correlation between the coating amount of the hydrophobic liquid layer and the adhesive strength.

The amount of the hydrophobic liquid was changed as shown in Tables 4 and 5 below, and the deaeration effect and the ratio of the hydrophobic liquid to the adhesive elastic body 100 were examined and the bonding state was evaluated.
Evaluation of bubbles by visual observation at the initial stage and after 15 minutes: Room temperature at 24 ° C. Observation observation for presence of voids with the naked eye: Good. ○ Slightly good Evaluation method of bonding state: Possibility of peeling with fingers.

Evaluation of Deaeration and Bonding When bonding, the adhesive strength of the acrylic adhesive elastic body of Example 1 (Formulation Example 1) was not expressed, and the surface was liquefied and the position could be easily corrected. Visual observation of the bubbles confirmed that degassing was carried out so that it would flow to the side edge during lamination [1], [2], [3]. In [4] and [5], it is not clear whether the glass surface distortion or the gel distortion, but a slight cavity remained at the end. The pressure increased to 10 kg and disappeared when observed after 15 minutes. This is the result of the hydrophobic liquid layer exhibiting flow and diffusion effects. Regarding the expression of the adhesive strength, the specimens of [3] and [4] did not peel off after 15 minutes and no deviation occurred. The specimens [1] and [2] (4 minutes after bonding) were put into an 80 ° C. oven for 15 minutes. As a result, there was no foaming and the two laminated glasses were bonded without any deviation. Attempts were made to peel off the metal plate, but the glass plate was only damaged. This is the result of gelation of the hydrophobic liquid layer on the adhesive elastic body.

All the 5 standard products were put in an 80 ° C. oven for 24 hours, but no foaming was observed. There are some fluid residue traces at the side edges, but they are not bubbles and the required quality is met.

Example 2
The composition of the adhesive elastic body is the same as in Example 1 (Composition Example 1). Acrylic gel total thickness of the resulting adhesive elastic body; light transmittance of 100 μm; 90% or more, adhesive peel strength; smooth glass plate thickness of acrylic adhesive elastic body having the performance of 25 N / 25 mm; 1.8 mm × The oleic acid viscosity is 2 cps, which is a hydrophobic liquid material forming a hydrophobic liquid layer, on the upper surface of this acrylic adhesive elastic body, and is placed at 0.20 g, 0.15 g,. 11 g, 0.6 g, and 0.5 g were dropped and smooth glass was immediately bonded to the upper surface under an irregular shape with a diameter of about 18 mm to obtain five levels. The pressing force was 50 mm × 70 mm and was carried out at about 5 kg for 5 seconds.

Effect of hydrophobic liquid layer In addition to the degassing effect and the ratio of hydrophobic liquid to adhesive elastic body 100, the bonding state was evaluated.
Evaluation of bubbles by visual observation at the initial stage and after 15 minutes: Room temperature at 24 ° C. Observation observation for presence of voids with the naked eye: Good. ○ Slightly good.
Bonding state evaluation method: Possibility of peeling with fingers.

The time of pasting was the same as in Example 1. There was no air bubble, and the glass plate was damaged when it was peeled off with a metal fitting.

Example 3
The composition of the adhesive elastic body is the same as in Example 1. The obtained adhesive elastic body has an acrylic gel with a total light transmittance of 100 μm; 90% or more, adhesive peel strength; smooth glass plate made of acrylic adhesive elastic body having a performance of 25 N / 25 mm; thickness: 1.8 mm × Attached to 50 mm × 70 mm, an additional 20 parts by weight of phthalic acid ester is mixed with 100 parts by weight of the oleic acid of Example 2 which is a hydrophobic liquid on the upper surface of the acrylic adhesive elastic body. 0.20g, 0.15g, 0.11g, 0.6g, and 0.5g were dropped on each part, and smooth glass was immediately bonded to the upper surface under an irregular shape with a diameter of about 18mm to obtain 5 levels. It was. The pressing force was 50 mm × 70 mm and was carried out at about 5 kg for 5 seconds.

Effect of hydrophobic liquid layer In addition to the degassing effect and the ratio of hydrophobic liquid to adhesive elastic body 100, the bonding state was evaluated.
Evaluation of bubbles by visual observation at the initial stage and after 15 minutes: Room temperature at 24 ° C. Observation observation for presence of voids with the naked eye: Good. ○ Slightly good.
Bonding state evaluation method: Possibility of peeling with fingers.

The time of pasting was the same as in Examples 1 and 2 above. There was no air bubble, and the glass plate was bonded to the glass plate when it was peeled off with a metal fitting. The difference from Examples 1 and 2 is satisfactory, with no superiority or inferiority, both during and after bonding.

Example 4
Formulation example 2 of solid elastic 50μm thick adhesive elastic material with acrylic as main component
2-ethylhexyl acrylate weight average molecular weight 900,000, OH functional group 6.5 (trade name: Vanlon S-2012 manufactured by Negami Kogyo) 100 parts by weight (solid content 35%) butyl acrylate weight average molecular weight 800, 000, OH functional group 8.5 (trade name SN-50 manufactured by Negami Kogyo Co., Ltd.) 50 parts by weight (solid content 20%), methyl methacrylate average molecular weight 600,000 No functional group (Precoat 200DR, manufactured by Negami Kogyo Co., Ltd.) 20 Add 0.5 parts by weight of coronate L75 (manufactured by Nippon Polyurethane Industry) as a cross-linking agent and stir. The acrylic solution was formed by applying a comma coater on stretched PET 50 μm / silicone release film, drying at 120 ° C., and protecting the surface with stretched PET 25 μm thick silicone release film.

Thickness obtained in this way; light transmittance of 50 μm; 90% or more, adhesive peel strength; two rolls (rubber roll) of acrylic adhesive elastic body having the performance of 15 N / 25 mm (based on measurement method JIS-Z-0273) And a metal roll), a PET 38 μm release film on one side was peeled off, and a smooth glass plate thickness of 1.8 mm × 50 mm × 70 mm was bonded to this surface. One PET peeled film thickness of this bonded acrylic adhesive elastic body; 50 μm is peeled off, and the upper surface of this acrylic adhesive elastic body is oleic acid plant-based hydrophobic liquid layer, viscosity 3 cps and phthalate ester; viscosity 2 cps. The solution was dropped into 0.20 g, 0.15 g, 0.11 g, 0.06 g, and 0.05 g at the center so that there were 4 points at the center, and smooth glass was immediately bonded to the upper surface to obtain 5 levels. The pressing force was 50 mm × 70 mm and was carried out at about 5 kg for 5 seconds.

Effect of hydrophobic liquid layer Initial evaluation of cavities and bubbles by visual observation and evaluation after 15 minutes: Room temperature at 24 ° C. Observation evaluation of presence or absence of cavities with the naked eye.
○: There is a slight cavity in the periphery.
▲: Cavity occurs in about 20% region ×: Cavity occurs in the center.
● Joint state evaluation method Can be peeled off with sensory fingers. Deviation is the presence or absence of creep at 5k load.

Evaluation by continuous pressurization The above-mentioned four levels of 0.05 g and 0.06 g of the hydrophobic liquid layer were evaluated as follows for 15 minutes with a pressing force of 5 kg / glass plate 50 mm × 70 mm.

next,
Experiments were conducted on the presence or absence of bubbles and discoloration in the heat resistance test.
◎; There is no cavity.
○: There is a slight cavity in the periphery.
▲: Cavity occurs in about 20% region ×: Cavity occurs in the center.

In addition, the ratio between the coating amount of the hydrophobic liquid layer and the adhesive elastic body was considered.
Specific gravity of acrylic adhesive elastic body 1.18 Specific gravity of hydrophobic liquid layer 0.91

The specific gravity difference between oleic acid and phthalic acid is within an error range with respect to thickness.

The bonding was the same as in Examples 1 to 3. When the hydrophobic liquid layer was removed except 0.05 g and 0.06 g, cavities and bubbles were not generated without continuous load. The glass plate was damaged when the metal plate was peeled off with the metal fitting. The difference from Examples 1 to 3 is satisfactory because there is no superiority or inferiority at the time of bonding and after bonding, except that the hydrophobic liquid layer is only 0.05 g and 0.06 g. Moreover, it was proved that 0.05 g and 0.06 g drop-coated products in which the hydrophobic liquid layer was thinly fluidized and diffused could be degassed if continuous pressure was applied.

Example 5
The formulation in this example is the same as in Example 1. Light transmittance of the resulting acrylic gel with a total thickness of 100 μm; 90% or more, Adhesive peel strength; Acrylic adhesive elastic body having a performance of 25 N / 25 mm is applied to a smooth glass plate, thickness: 0.8 mm × 400 mm × 400 mm The hydrophobic liquid layer was stuck on the upper surface of this acrylic adhesive elastic body.

Oleic acid plant-based hydrophobic liquid is dropped into the central part of acrylic adhesive elastic body at 120g and 80g, respectively, and smooth glass is pasted on the upper surface under an irregular shape with a diameter of about 200mm to obtain two levels. It was. The pressing force was 400 mm × 400 mm at about 15 kg for 5 seconds and then 4 kg at room temperature for 1 hour.

[Effect of hydrophobic liquid layer]
Evaluation of bubble generation in the initial stage 60 minutes after sticking: Visual observation; Observation at room temperature of 24 ° C. Observation evaluation of presence or absence of cavities Degassing effect A: No bubbles.
○: Cavity or flow mark at the side end ×: Cavity in the central region excluding the side end part Bonding state evaluation method Sensory: Possibility of peeling with fingers.

At the time of bonding, the adhesive strength of the acrylic adhesive elastic body was not expressed, and the surface was liquefied, and the position could be easily corrected. By visual observation of the bubbles, it was confirmed that deaeration was performed so as to flow to the side edge during lamination. Regarding the expression of adhesive strength, the specimens of [1] and [2] did not peel off after 60 minutes and no deviation occurred. In addition, image distortion (thickness transfer distortion resulting from the horizontal axis shrinkage of the stretched PET film), that is, optical distortion, caused by the crossing of the thickness of the acrylic adhesive elastic body, that is, between the two glass plates together with the gelation of the hydrophobic liquid material. This is probably due to the fact that the thickness balance and molecular orientation distortion were removed, but the optical distortion was improved and the perspective image distortion was eliminated.

Although it was put into an 80 ° C. oven for 24 hours, no foaming was observed. Some of the side edges have slight flow residue marks, but the required quality (the outer periphery is decorated with black printing or black film or shielded) is satisfied rather than air bubbles.

Example 6: Adhesive elastic body mainly composed of urethane resin
In this blending example 3, 40 parts by weight of a curing agent isocyanate (trade name Vernock 980 solids manufactured by Dainippon Ink Manufacturing Co., Ltd., 75% solids) is added to 100 parts by weight of polyol (trade name Barnock 161 solids manufactured by Dainippon Ink Manufacturing Co., Ltd. 100%). The mixture was added and stirred. The obtained liquid is deposited on a PET silicon release film so as to have a thickness of 100 μm. The film formation method was a comma coater, and the drying zone was subjected to a temperature gradient and the urethane-based adhesive elastic body was finished at a speed of 3 m / min including a maximum temperature of 120 ° C.

This urethane-based adhesive elastic body was bonded to a glass plate thickness of 1.8 mm × 50 mm × 70 mm. Hydrophobic ester, a hydrophobic liquid layer, was dropped on one glass plate, using a viscosity of 2 cps, and dropped at 0.12 g, 0.15 g, and 0.19 g at the center and 4 points at the center. A smooth glass was laminated to obtain 3 levels. The pressing force was 50 mm × 70 mm and was carried out at about 5 kg for 5 seconds.

Bubble generation and peeling evaluation at the initial stage and 15 minutes after sticking (visual observation; room temperature 24 ° C. atmosphere)
Evaluation of observation of presence or absence of voids with the naked eye: ◎; Good ○; Slightly good Evaluation method of bonding state Sensory; Possibility of peeling with fingers.

When the physical properties of Formulation Example 3 were evaluated, bonding was the same as in Examples 1 to 5 described above. The hydrophobic liquid layer was effective and adhered without voids and bubbles. Even after 1 hour, the glass plate was damaged when the metal plate was peeled off. A film made of a urethane-based adhesive elastic body is more than three times that of an acrylic-based film and has a high scattering prevention effect.

Example 7
Referring to Fig. 4, the display window frame of adhesive elastic body (substitute with light leakage prevention film or film) has been demonstrated to prevent the stepped portion between this film and the protective layer from rising and becoming hollow (bubble generation). To do.

18 sheets of adhesive elastic body 20 of Example 1 (Composition Example 1) were applied while being pressed with a rubber roll so that air bubbles would not enter the glass plate, in this case, a protective layer 10 having a plane of 0.7 mm × 400 mm × 400 mm. Get the board. Further, on the surface of the adhesive elastic body 20, a PET stretched film thickness equivalent to the display window frame (light leakage prevention film); 5, 12, 24, 38, 50, 80 μm, width 25 mm, length 400 mm, respectively. The three are adhered to the surface of the glass plate with an equal width. A glass plate equivalent to the adherend surface, one of the display bodies, 0.7 mm x 400 mm x 400 mm in a hydrophobic liquid layer oleic acid: 0 g (no hydrophobic liquid), 80 g, 120 g, centered to obtain three levels The adhesive elastic body 20 and the display body 40 were bonded to each other when it was dropped onto the part and spread to a diameter of about 100 mm (see FIG. 1).

The bonded PET stretched film 50 has a thickness of 6 levels; 5, 12, 24, 38, 50, and 75 mm, and a hydrophobic liquid layer 3 level (0, 80, 120 g). It is as follows. For comparison, a blank with no hydrophobic liquid layer was added.
Evaluation of cavitation after aging: Visual evaluation display ◎: No cavity, no bubbles ○: Outside 2 mm diameter or less less than 5 ◎ ▲; Outside 3 mm diameter or less less than 5 ×: Straight, circular, bubbles

Example 8
An experiment similar to FIG. 4 was performed.
In order to verify the possibility that a stepped part floats up against the display window frame (light leakage prevention film) of the adhesive elastic body and a cavity is formed, the PET stretched film thickness of Example 6; Corresponding glass plate; dimensional thickness; 0.7 mm × width 50 mm × length 70 mm), PET stretched film, thickness: 75 μm is attached to the side edge at 5 mm width, and the presence or absence of a cavity is observed. At the same time, it is a black OPP (biaxially stretched polypropylene) film single-sided adhesive tape with a black OPP film / acrylic adhesive, thickness: 40 μm / 40 μm (trade name: multilayer tape # 40, manufactured by Kyodo Giken Chemical) A total thickness of 80 μm was used, and the same width and length were applied to one glass plate (without adhesive elastic body) for comparison.

The adhesive elastic body of Example 1 is bonded to a flat glass plate g10 having a size of 0.7 mm × 50 mm × 70 mm while being pressed with a rubber roll so as not to enter bubbles to obtain four plates. Further, a PET stretched film thickness equivalent to a display window frame (light leakage prevention film); 50, 80 μm, width 5 mm, and length 70 mm are adhered to each side edge on the surface of the adhesive elastic body.

Hydrophobic liquid layer Two levels of oleic acid 80 g and 120 g were dropped onto the center and spread to about 10 mm diameter, and the glass plate with the adhesive elastic body was bonded together.

The evaluation of cavitation of the two levels having a difference in the thickness of the stretched PET stretched film, the two levels of the hydrophobic liquid layer, and the four levels in total is as follows. For comparison, a blank with no hydrophobic liquid layer was added.
Evaluation of cavitation after aging: Visual evaluation display ◎: No void bubbles ○: Outside 2 mm diameter or less less than 5 ▲; Outside 3 mm diameter or less less than 5 ×: Linear, circular and bubbles.

In the vicinity of the dimensions of 50 mm × 70 mm corresponding to the display body of the mobile phone, the distortion was absorbed at the film step and no cavities were generated. The same was true for the OPP film with adhesive, and there was no void. In addition, in the adhesive layer of the black OPP film with adhesive, the migration (chemical equilibrium) of the hydrophobic liquid layer and the cavities and strain due to swelling were not observed.

Application and Transport of Hydrophobic Liquid Referring to FIG. 2, a method for manufacturing a protective body of the present invention or a method for forming a protective body on a display body of a display device will be described.

A polyethylene adhesive tape (LLDPE 40 μm / acrylic adhesive layer 10 μm configuration), which is a known protective adhesive tape (process paper) 50, has an adhesive strength equivalent to 0.5 N / 25 mm for application and transportation of a hydrophobic liquid.

The size of the glass plate 40, which is a display body to be adhered, is 50 mm × 70 mm (equivalent to a mobile phone display body). A slit is made with a width of 70 mm so that the width of the tape is 10 mm from both ends of the glass plate 40, and a glass plate of 50 mm × 70 mm is placed on this tape and conveyed to a conveyance / coating line composed of AC rolls. The hydrophobic liquid 30 used oleic acid.

The coating roll is applied by a bottom feed two roll type (B, C roll).

By applying the glass plate 40 to the protective adhesive tape 50, the glass plate could be applied without dropping off. Furthermore, intermittent application of the space between the glass plates can be naturally performed by the thickness of the glass plates, and no special control is required.

The amount of coating is controlled by two systems: the interval between B roll and C roll and the rotation ratio of B roll and C roll.

The glass plate was not dropped off, and the coating thickness was 10-200 μm, allowing arbitrary coating.

B roll reverse rotation (relative to C roll) was applicable.

The coating method includes extrusion casting such as a die and a nozzle, but this example shows that bottom coating is suitable for bottom coating due to the limitation of intermittent coating.

Example 9
This is an example of a display body of a display device, here, a glass plate 40 and a protective layer of the display body, here a multilayer adhesive elastic body layer in which adhesive elastic bodies 20, 20 are arranged on both acrylic resin plates 10.

The formulation example of the adhesive elastic body is the same as that of Example 1 in the previous section.
Thickness of acrylic gel obtained; light transmittance of 100 μm; 90% or more, adhesive peel strength; light transmittance of total thickness of 400 μm with different thicknesses of 25 N / 25 mm and the same composition; 90% or more, adhesive Peel force: A stress relaxation layer made of an acrylic adhesive elastic body 20 having a performance of 27 N / 25 mm is used.

One acrylic gel, with a total thickness of 100 μm, smooth transparent glass plate 40 thickness; 1.8 mm × 300 mm × 300 mm coated with a pressure rubber roll so that air does not enter, the other with a total thickness of 400 μm, light transmittance; 90% The acrylic adhesive elastic body 20 having the performance of adhesive peel strength: 27 N / 25 mm is applied to the other acrylic plate 10 having the same size and thickness: 3 mm × 300 mm × 300 mm with the same pressure rubber roll.

On the surface of the acrylic adhesive elastic body 20 of the glass plate 40 to which one acrylic adhesive elastic body is applied, the same hydrophobic liquid 30 (oleic acid, viscosity 3 cps) as in Example 1 is used as the center, and 1, 4, 5 respectively. , 6 and 10 g, after dropping to 5 levels, immediately paste the transparent acrylic resin plate 10 coated with the acrylic adhesive elastic body 20 of the other thickness so that the layer surfaces of both adhesive elastic bodies 20 are laminated. .

The pressing force was 300 mm × 300 mm and was carried out at about 5 kg for 5 minutes.
Evaluation after 15 minutes by visual observation of bubbles (at room temperature of 24 ° C)
Observed evaluation of the presence or absence of voids with the naked eye: ◎ is good, ○ is a little better Evaluation method of bonding state: Sensory test (possibility of peeling with fingers)

When sticking the display body 40 and the protective layer 10 which are both adherend surfaces, the adhesive force of the adhesive elastic body 20 does not appear, and the bubbles also move to the side edge as the hydrophobic liquid 30 flows and diffuses. It was confirmed that it was extruded.

Also, with the liquefaction of the adherend surface, the position could be easily corrected except for [1]. By visual observation of the bubbles, it was confirmed that degassing was carried out so that it would flow to the side edge when laminating [2], [3], [4], [5] except for [1]. In [1], the amount of dripping of the hydrophobic liquid is insufficient, so that it does not spread to the periphery, and both adhesive elastic bodies on the adherend surface are joined in the vicinity of the outer frame 20 mm, leaving a cavity. .

[5] The amount of dripping of the hydrophobic liquid is excessive, so there is a lot of liquid dripping after bonding and it is difficult to stop the deviation.

As a result of putting the specimens [1], [2], [3], [4], and [5] [after 4 minutes of bonding] into an 80 ° C. oven for 15 minutes, there was no new foaming. The partial cavity was reduced by 60% or more. Adhesion was stable except for [5]. [5] still had a liquid-like behavior that was dominated by hydrophobic liquids.

The glass plate display and acrylic resin plate protective layer have a size of 300 mm x 除 き 300 mm, and are almost stably laminated with no voids except for [1]. Not only the difference in thermal expansion coefficient between the two, but also the residual strain of molecular orientation and the expansion and contraction due to water absorption (water absorption rate 1.2% / relative humidity 65%) during sheet molding of acrylic resin plates are comparable to those of glass plates. It is a difference and a heterogeneity.

Compared with the glass plate display, this behavior is mainly due to the adhesive elastic body that effectively absorbs the expansion and contraction of the large acrylic resin plate, but this effect is further enhanced. Is the effect of the layer gelled by the hydrophobic liquid layer that should be called the second buffer layer formed between the two adhesive elastic layers.

Example 10
Example of interposing a PET film as a substrate The composition of the adhesive elastic body 20 is the same as in Example 1 (Formulation Example 1).

The adhesive elastic body is extruded by a die coater, formed on a stretched PET 25 μm film corona-treated product as a base material 70, anaerobically exposed to PET 38 μm silicon release film as a gas barrier film, and crosslinked with ultraviolet rays (UV irradiation below), An adhesive elastic body 20 having a thickness of 100 μm on one side is formed, and a similar adhesive elastic body 20 having a thickness of 100 μm is formed on the opposite surface of the base material 70, which is coated with a PET 38 μm silicon release film, and ultraviolet rays. Crosslinking was performed (Figure 5).

The ultraviolet crosslinking method is the same as in Example 1.

Acrylic adhesive elastic body 20 having a total thickness of acrylic gel, which is the obtained adhesive elastic body; light transmittance of 250 μm; 90% or more, adhesive peel strength; 17 N / 25 mm, is used here as display body 40. Smooth glass plate thickness: 1.8 mm × 50 mm × 70 mm, and the surface of this acrylic adhesive elastic body 20 is a hydrophobic liquid material that forms a hydrophobic liquid layer 30. 0.20 g, 0.15 g, 0.11 g, 0.6 g, and 0.5 g were added dropwise to the surface immediately under an irregular shape with a diameter of about 18 mm. Here, as a transparent protective layer 10 Smooth glass was laminated to obtain 5 levels. The pressing force was 50 mm × 70 mm and was carried out at about 5 kg for 5 seconds.

Effect of hydrophobic liquid layer Evaluation of bubbles after visual observation for 15 minutes (at room temperature of 24 ° C)
Observation evaluation of presence or absence of voids with the naked eye is good. ○ Slightly good.
Bonding state evaluation method: Possibility of peeling with fingers.

　

The pasting was the same as in Example 1. There was no generation of bubbles.
Since the stretched PET film 70 as a base material excellent in dimensional stability is interposed between the adhesive elastic body layers 20 and 20, the rigidity of the protective layer is increased and peeling is easy. This easy peelability facilitates re-correction at the time of pasting, avoids the waste of the protective layer and the display itself, and can greatly contribute to the yield and productivity in the lamination process.

Example 11
Example of Laminating PET Film on Protective Layer 10 The stretched polyester (PET) film having a light transmittance of 60% or more is coated on one side with a thickness of 15 μm on the one side of the stretched polyester (PET) film with a thickness of 15 μm. The protective body is laminated on the acrylic plate 10 which is a protective layer through the conductive liquid layer 30.

The formulation example of the adhesive elastic body is the same as in Example 1 described above.

An acrylic gel similar to that of Example 1 is formed on a stretched PET film of 150 μm in thickness on one side; 15 μm, and light transmittance: 90% or more, adhesive peel strength: 10 N / 25 mm is obtained.

Smoothly transparent acrylic plate thickness: 1 mm x 300 mm x 300 mm with a hydrophobic liquid 30 (phthalate ester viscosity 3 cps) in the center, and dropped immediately to 1, 4, 5, 6, 10 g and 5 levels respectively, immediately after A stretched PET film roll-like product coated with an acrylic adhesive elastic body is stuck so that the surface of the elastic layer is laminated while pressing with a rubber roll.

The applied pressure was about 10 kg / 1 m linear pressure.
Evaluation after 15 minutes by visual observation of bubbles (at room temperature of 24 ° C)
Observed evaluation of the presence or absence of voids with the naked eye: ◎ is good, ○ is a little better Evaluation method of bonding state: Sensory test (possibility of peeling with fingers)

¡Since it is bonded with pressure rubber using a roll-shaped member that enables uniform sticking and drawing, the degassing effect is high, and air bubbles are naturally not seen.

90% light transmittance is also obtained. Within 15 minutes, the reworkability (removability) is good and a high yield is obtained. If the surface of the stretched PET film (opposite side of the viscoelastic body) is coated with a scratch-resistant hard coat 2 to 6H (pencil hardness) of 1 to 15 μm (solid content), it is more desirable for protection.

Example 12
Prevents dripping from the joining edge of the glass plate, which is a protective body after applying and laminating a hydrophobic liquid.
In order to avoid the possibility of leakage or dripping of the hydrophobic liquid after the protective body on the adhesive elastic layer corresponding to the large-diameter LCD, for example, is laminated through the hydrophobic liquid layer, A bonding liquid adsorbent is applied to seal the joint edge.

As the adsorbent, 100 parts by weight of urethane carbonate (100 parts by weight of TDI with respect to 100 parts by weight of polyol) is used as a binder with respect to 100 parts by weight of calcium carbonate (product name: PK80, particle size: 30 μm indefinite form). ) Mixing and stirring with a three-blade mixer at a blending ratio of 2 parts by weight and 30 parts by weight of IPA (isopropylene alcohol) as a dispersion gives a viscosity of 3000 cps.

The compounding of the adhesive elastic body is the same as in Example 1 (Composition Example 1). Acrylic gel total thickness of the obtained adhesive elastic body; light transmittance of 100 μm; 90% or more, adhesive peel strength; smooth glass plate thickness of acrylic adhesive elastic body having performance of 25 N / 25 mm; 1.8 mm × Attached to a 50mm x 70mm acrylic adhesive elastic body, a DIDP (diisodecyl phthalate) viscosity of 3 cps, which is a hydrophobic liquid layer forming a hydrophobic liquid layer on the upper surface, is 0.60g, 0.40g, 0.20g, dripping, respectively. Then, smooth glass 8 mm × 60 mm × 80 mm was immediately bonded to the upper surface under an irregular shape with a diameter of about 18 mm to obtain three levels. After bonding, the adsorbent of the above composition is laminated with a simple bottle with an injection nozzle so that the hydrophobic liquid does not leak out, and the outer peripheral edge of the joint is putty-like with a width of about 3 mm and a thickness of about 2 to 5 mm Sealed.

The pressing force was 50 mm × 70 mm, and was carried out at about 1 kg for 15 minutes.

The adsorption effect is manifested. Leakage or spillage and adsorption start about 1 minute after bonding, but this changes the color tone from whitening to slightly translucent due to the vaporization effect of IPA and the adsorption effect of calcium carbonate, and after 30 minutes it becomes semisolid and hardened None, liquid leakage is sealed while adsorbing liquid. As a secondary effect, adhesive fixation of the display laminate was also obtained, and it was possible to complement the prevention of misalignment due to the adhesive elastic body and hydrophobic liquid at the time of initial bonding, and both effects of leakage prevention and adhesive fixation were obtained at the same time. .

As an adsorbent for liquid leakage countermeasures, there are other methods using fiber bodies such as paper, synthetic fiber, and cotton. However, the mixture composition having the initial fluidity is used for pouring into the minute gaps of the glass laminate. Things are more effective.

10 (g10) Transparent protective layer (acrylic plate)
20 Adhesive elastic body (stress relaxation layer)
30 Hydrophobic liquid layer (hydrophobic liquid)
40 (g40) Display body (of display device) (glass plate)
50 Protective adhesive tape (process paper)
60 Light leakage prevention film (Light leakage prevention film)
70 Base material (stretched PET film)

Claims (16)

At least one stress relaxation comprising a display body of a display device and a pressure-sensitive adhesive body having an acrylic or urethane resin as a main component disposed between the display body and a protective layer; 10 to 3000 μm and elongation of 50 to 350% A protective body for a display device comprising a layer and a hydrophobic liquid layer having a non-volatile component viscosity of 2000 cps or less; 1 to 500 μm formed on at least one surface of the stress relaxation layer. The stress relaxation layer is disposed on the adherend surface and / or on the protective layer, and the protective layer and the display body are adhered to each other through the stress relaxation layers and the hydrophobic liquid layer. The protective body of the display device according to claim 1, wherein The display device protective body according to claim 1, wherein the adhesive elastic body has an adhesive strength of 2 to 40 N / 25 mm width (JIS-Z-0237). The protective body for a display device according to claim 1, wherein the hydrophobic liquid layer has a boiling point of 60 to 400 ° C or less, a viscosity of 1 to 500 cps, and a solid content thickness of 1 to 500 µm. The light refraction index of the stress relaxation layer and the hydrophobic liquid layer is within a range of ± 0.1 to 0.2 with respect to the refraction index of the display body and the protective layer, and a light transmittance of 80 to 99%. The display device protector according to claim 1, wherein: The acrylic adhesive elastic body has a functional group and has acrylic acid, ethyl acrylate, methyl acrylate, 2-ethylhexyl acrylate, butyl acrylate, isobutyl acrylate, isononyl acrylate, dimethylaminoethyl acrylate, acrylic Methoxyethyl acid, stearyl acrylate, isooctyl acrylate, N-octyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, methyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, methacryl The table according to claim 1 or 3, which is cyclohexyl acid, trimethylolpropane trimethacrylate, tertiary butyl methacrylate, maleic anhydride, itaconic anhydride, citraconic anhydride. Protection body of the device. A base material made of a stretched polyester (PET) film having a thickness of 1.5 to 200 μm and a light transmittance of 85% or more is placed on one surface of the stress relaxation layer to have a total thickness of 10 to 3000 μm. The protective body of the display device according to claim 1, wherein the protective layer is laminated on a surface via the hydrophobic liquid layer. The protective body for a display device according to claim 7, wherein a base material made of the stretched polyester (PET) film is disposed between the stress relaxation layers. A stress relaxation layer made of an adhesive elastic body mainly composed of an acrylic or urethane resin with an elongation of 50 to 350% is formed on the display surface of the display device and / or the adherend surface forming the protective layer of the display body. Formed into a thickness of 10 to 3000 μm, and a hydrophobic liquid layer having a non-volatile component viscosity of 2000 cps or less is formed on at least one surface of the stress relaxation layer; a thickness of 0.1 to 500 μm is formed through the hydrophobic liquid layer; A method for forming a protective body for a display device, comprising attaching a surface to be adhered comprising a protective layer of 1 to 7 mm and a display body of the display device. The stress relaxation layer is made of an adhesive elastic body of a three-dimensional cross-linked polymer adhesive gel, and the hydrophobic liquid layer is formed on at least one surface of the stress relaxation layer to a thickness of 1 to 500 μm, and the hydrophobic liquid layer is The stress relaxation layer forms a secondary gelation or chemical equilibrium with time to absorb strain of the adherend and the protective layer, and the protective layer is adhered to the adherend surface. A method for forming a protective body for a display device according to claim 9. The hydrophobic liquid material forming the hydrophobic liquid layer is a monomer or oligomer having a hydrophobic molecular weight of 1000 g / mol or less and a non-volatile viscosity of 2000 cps or less, such as acrylic acid, fatty acid, expensive alcohol, phthalate ester, carboxylic acid ester, etc. A method for forming a protective body for a display device according to claim 9 or 10. As a gelling agent in the hydrophobic liquid layer, dioctyl phthalate, dibutyl phthalate (DBP), diisonyl phthalate (DINP), diidecyl phthalate (DIDP) and the like, phthalate esters, polyesters, polyethers, adipine At least one selected from the group consisting of acid ester, citrate ester, maleate ester, benzoate ester, sepacate ester, phosphate ester, oleic acid, vegetable oil, epoxidized plant The method for forming a protective body of a display device according to any one of claims 9 to 11, comprising an additive. 13. The method for forming a protective body of a display device according to claim 12, wherein the additive is at least one selected from the group consisting of the gelling agents, and has a light transmittance of 80% or more due to compatibility and transparency. . 14. The method for forming a protective body of a display device according to claim 13, wherein the additive contains a solvent in the gelling agent, is applied and dried, and the protective layer is adhered to the adherend surface. 10. The method for forming a protective body for a display device according to claim 9, wherein after the protective body and the display body are joined via the hydrophobic liquid layer, the outer peripheral edge of the laminated / joined outer periphery is sealed with an adsorbent. 16. The display device according to claim 15, wherein the adsorbent has a viscosity of 3000 cps obtained by mixing 2 parts by weight of urethane resin and 30 parts by weight of IPA (isopropylene alcohol) with 100 parts by weight of calcium carbonate, and mixing and stirring the mixture. Method for forming a protector.

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