JP2009258274A - Pressure-sensitive adhesive sheet for front plate of display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thin pressure-sensitive adhesive sheet for a front plate of a display device, which is excellent in adhesion between a substrate layer and a pressure-sensitive adhesive layer, has sufficient shock absorbing property and water cut-off property, and maintains the above physical characteristics even in a high temperature environment and a temperature variable environment. <P>SOLUTION: A pressure-sensitive adhesive tape for a front plate of a display device is provided, which comprises a substrate layer and an acrylic pressure-sensitive adhesive layer laminated and integrated on at least one surface of the substrate layer and is placed between a display panel and a transparent front plate for protecting the display panel. The adhesive tape is characterized in that: the substrate layer consists of a crosslinked polyolefin resin foamed sheet having a crosslinking degree of 5 to 60 wt.% and an aspect ratio of cells ranging from 0.25 to 1; and the acrylic pressure-sensitive adhesive layer comprises an acrylic pressure-sensitive adhesive containing 1 to 30 pts.wt. of a tackifying resin having a softening point of 130°C or higher based on 100 pts.wt. of an acrylic polymer. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an adhesive sheet for a display device front plate.

Conventionally, in the assembly of a liquid crystal panel, a cushion material is used for the purpose of absorbing an impact. The liquid crystal display device described in Patent Document 1 includes a rubber cushion material between the housing and the front plate.
The liquid crystal display device described in Patent Document 2 includes a cushion material between the liquid crystal panel and the panel guide.
Detailed studies are being conducted on such cushioning materials and shock absorbing materials. For example, Patent Document 3 discloses a shock absorbing sheet having a rubber foam and a bubble-containing adhesive layer. Further, it is described that this shock absorbing sheet is interposed between the image display panel and the transparent front plate.

In recent years, with the demand for downsizing / thinning electronic devices, display panels are generally getting thinner.
In a thin display panel, the cushion material used is required to have a high impact absorbing ability while being thin. In particular, display panels used for portable electronic components and display panels used for home appliances used around water are required to be thinner and more water-tight.
However, it has been difficult to achieve both excellent impact absorbability and water stoppage while being thin.

  On the other hand, as a study of the foam sheet itself, as a foamed resin sheet having sufficient flexibility even if it is thinned, Patent Document 4 discloses that a polyolefin resin and a pyrolytic foaming agent are supplied to an extruder and melt-kneaded. A cross-linked polyolefin resin foam sheet obtained by foaming a foamable polyolefin resin sheet formed by extruding into a sheet form from an extruder, which has a specific degree of cross-linking and aspect ratio has been proposed Yes.

By the way, since the display panel generally tends to have heat on the surface or inside thereof, heat is generated while the display panel is used, and the temperature rises. After a while after use, the temperature drops to the surrounding temperature. Especially when used for display panels for portable electronic devices used externally, both when the temperature of the internal space and surface rises, and when the temperature difference from high temperature to normal temperature or low temperature is repeatedly loaded. It is required to exhibit shock absorption and water stoppage that are the same as normal temperatures.
However, in the case of the above-mentioned cross-linked polyolefin resin foamed sheet, if the temperature difference from high temperature to normal temperature or low temperature is repeatedly applied as described above, there is a risk that settling will occur, causing problems in water stoppage and shock absorption. It was.

JP 2007-047620 A JP 2005-346061 A JP 2006-110773 A WO2005 / 007731 Publication

  In view of the above circumstances, the present invention is excellent in adhesion between the base material layer and the pressure-sensitive adhesive layer, and has a sufficient impact absorbability and water-stopping property while being thin, and at high temperatures and in a temperature change environment. An object of the present invention is to provide a pressure-sensitive adhesive sheet for a display device front plate that can maintain the physical properties of the display device.

  In order to achieve the above object, as a result of intensive studies, the present inventors have used a specific resin foam sheet as a base material layer, and by using an acrylic pressure-sensitive adhesive having a specific composition for the pressure-sensitive adhesive layer, thereby reducing the thickness. Even so, it has been found that a pressure-sensitive adhesive sheet for a display device front plate can be obtained which has excellent shock absorption and water-stopping properties and does not impair their physical properties even at high temperatures, and has completed the present invention.

That is, the pressure-sensitive adhesive sheet for a display device front plate according to the present invention has an acrylic pressure-sensitive adhesive layer laminated and integrated on at least one side of a base material layer, and is between a display panel and a transparent front plate for protecting the display panel. The base material layer is a cross-linked polyolefin resin foam sheet having a cross-linking degree of 5 to 60% by weight and a bubble aspect ratio of 0.25 to 1. And the acrylic pressure-sensitive adhesive layer is characterized by comprising an acrylic pressure-sensitive adhesive containing 1 to 30 parts by weight of a tackifying resin having a softening point of 130 ° C. or higher with respect to 100 parts by weight of the acrylic polymer. .
The present invention will be described in detail below.

(Polyolefin foamed resin sheet)
The pressure-sensitive adhesive sheet for a display device front plate according to the present invention has a crosslinking degree of 5 to 60% by weight and a foamed aspect ratio (average bubble diameter of MD / average bubble diameter of CD) of 0.25 to 1. It has a base material layer which consists of a resin foam sheet.
By using such a cross-linked polyolefin-based foamed resin sheet as a base material layer, the pressure-sensitive adhesive sheet for a display device front plate of the present invention has an extremely excellent impact absorbability even when it is thin, and has a waterproof property. Will also be excellent.

  That is, if the degree of cross-linking of the crosslinked polyolefin resin foam sheet is small, bubbles in the vicinity of the surface of the foam sheet break up when the foam sheet is stretched, resulting in surface roughness and sufficient adhesion with the adhesive layer. If the foamable polyolefin resin composition is too large, the melt viscosity of the foamable polyolefin resin composition becomes too large, and the foamable polyolefin resin composition follows foaming when heat-foaming the foamable polyolefin resin composition. It becomes difficult to obtain a crosslinked polyolefin resin foamed sheet having a desired expansion ratio, and as a result, the impact absorbability is inferior. Therefore, it is limited to 5 to 60% by weight, and preferably 10 to 40% by weight.

In addition, the degree of crosslinking of the crosslinked polyolefin resin foamed sheet refers to that measured in the following manner. About 100 mg of a test piece is taken from the crosslinked polyolefin resin foam sheet, and the weight A (mg) of the test piece is precisely weighed. Next, this test piece was immersed in 30 cm ³ of xylene at 120 ° C. and allowed to stand for 24 hours, and then filtered through a 200-mesh wire mesh to collect the insoluble matter on the wire mesh, vacuum dried, and the weight of the insoluble matter. Weigh B (mg) precisely. From the obtained value, the degree of crosslinking (% by weight) is calculated by the following formula.
Crosslinking degree (% by weight) = 100 × (B / A)

Furthermore, the cross-linked polyolefin resin foam sheet has an aspect ratio of bubbles (average bubble diameter of MD / average bubble diameter of CD) of 0.25 to 1, or an aspect ratio of bubbles (average bubble of CD) Diameter / average bubble diameter of VD) is required to be 2 to 18, the aspect ratio of bubbles (average bubble diameter of MD / average bubble diameter of CD) is 0.25 to 1, and the aspect ratio of bubbles (Average bubble diameter of CD / average bubble diameter of VD) is preferably 2-18.
Specifically, when the ratio of the average bubble diameter of MD and the average bubble diameter of CD in the crosslinked polyolefin resin foam sheet, that is, the aspect ratio of the bubbles (average bubble diameter of MD / average bubble diameter of CD) is small. The foaming ratio may decrease and the flexibility may decrease or the thickness, flexibility and tensile strength of the crosslinked polyolefin resin foam sheet may vary. Therefore, it is limited to 0.25 to 1, and 0.25 to 0.60 is preferable.

  In addition, when the ratio of the average bubble diameter of CD and the average bubble diameter of VD, that is, the aspect ratio of bubbles (average bubble diameter of CD / average bubble diameter of VD) in the crosslinked polyolefin resin foamed sheet is small, While the flexibility of the polyolefin resin foam sheet decreases, if it is large, the expansion ratio decreases and the flexibility decreases, or the thickness, flexibility and tensile strength of the crosslinked polyolefin resin foam sheet vary. Therefore, 2-18 are preferable and 2.5-15 are more preferable.

  The MD (machine direction) of the cross-linked polyolefin resin foam sheet refers to the extrusion direction, and the CD (crossing direction) of the cross-linked polyolefin resin foam sheet is orthogonal to the MD (machine direction) and cross-linked polyolefin resin foam. The direction along the surface of the sheet 1 is referred to, and the VD (vertical (thickness) direction) of the crosslinked polyolefin resin foamed sheet 1 refers to a direction orthogonal to the surface of the crosslinked polyolefin resin foamed sheet.

Next, the average cell diameter of MD of the cross-linked polyolefin resin foamed sheet is measured in the following manner. That is, the cross-linked polyolefin resin foam sheet is cut over the entire length in a plane parallel to VD at a substantially central portion of the CD.
Thereafter, the cross section of the cross-linked polyolefin resin foam sheet is magnified 60 times using a scanning electron microscope (SEM), and a photograph is taken so that the full length of the VD of the cross-linked polyolefin resin foam sheet is accommodated.

In the obtained photograph, a straight line having a length of 15 cm on the photograph (actual length of 2500 μm before enlargement) corresponding to the central portion of the VD of the crosslinked polyolefin resin foamed sheet is obtained by foaming the crosslinked polyolefin resin foam. Draw to be parallel to the sheet surface.
Next, the number of bubbles located on the straight line is visually counted, and the average bubble diameter of bubbles MD is calculated based on the following formula.
Average bubble diameter of MD (μm) = 2500 (μm) / number of bubbles (pieces)

Moreover, the average cell diameter of VD of a crosslinked polyolefin-type resin foam sheet means what was measured in the following way. That is, photography is performed in the same manner as the procedure for calculating the average cell diameter of MD of the crosslinked polyolefin resin foam sheet.
In the obtained photograph, three straight lines that divide the cut surface of the photographed crosslinked polyolefin resin foam sheet into four parts in MD are foamed in a direction (VD) perpendicular to the surface of the crosslinked polyolefin resin foam sheet. Draw over the entire length of the sheet.
Thereafter, the length of each straight line is measured and the number of bubbles located on each straight line is visually counted, and the average bubble diameter of bubbles VD is calculated for each straight line based on the following formula, and the arithmetic mean of these is calculated. Is the average bubble diameter of the VD of the bubbles.
Average bubble diameter of VD (μm) = length of straight line on photo (μm)
/ (60 x number of bubbles (pieces))

Next, the average cell diameter of CD of the cross-linked polyolefin resin foam sheet is measured in the following manner. That is, the cross-linked polyolefin resin foam sheet is cut over the entire length in the thickness direction on a plane parallel to the CD and parallel to the direction (VD) perpendicular to the surface of the cross-linked polyolefin resin foam sheet.
Thereafter, the cross section of the cross-linked polyolefin resin foam sheet is magnified 60 times using a scanning electron microscope (SEM), and a photograph is taken so that the total length in the thickness direction of the cross-linked polyolefin resin foam sheet is accommodated.
Then, based on the obtained photograph, the average cell diameter of CD is calculated in the same manner as when the average cell diameter of MD of the crosslinked polyolefin resin foamed sheet is measured.

In the above-described procedure for measuring the average bubble diameter, when counting the number of bubbles located on a straight line, the bubble diameter is determined based only on the bubble cross section appearing on the photograph.
That is, even if the bubbles seem to be completely separated from each other by the cell wall on the cut surface of the cross-linked polyolefin resin foam sheet, they communicate with each other at a portion other than the cut surface of the cross-linked polyolefin resin foam sheet. However, in the present invention, the cross-linked polyolefin resin foam sheet is not considered whether or not it is in communication with each other in the portion other than the cut surface, and based only on the cross section of the bubble film shown on the photograph. The bubble form is judged, and one void portion completely surrounded by the bubble film cross section appearing on the photograph is judged as one bubble.

Positioning on a straight line means that the straight line completely penetrates the bubble at any part of the bubble, and the straight line does not completely penetrate the bubble at both ends of the straight line. In the case where the end portion of the bubble is located in the bubble, the bubble was counted as 0.5.
When taking a photograph of the cut surface of the cross-linked polyolefin resin foam sheet, coloring the cut surface of the cross-linked polyolefin resin foam sheet facilitates the discrimination of air bubbles and enlarges the 2500 μm scale together to take a photo. This makes it easier to specify the straight line length on the photograph.

The polyolefin resin constituting the crosslinked polyolefin resin foamed sheet preferably contains 40% by weight or more of a polyethylene resin obtained using a metallocene compound containing a tetravalent transition metal as a polymerization catalyst.
Therefore, by using a polyolefin-based resin containing 40% by weight or more of a polyethylene-based resin obtained by using the above metallocene compound, the polyolefin-based resin is given flexibility without increasing the adhesiveness, and is crosslinked. The aspect ratio of the bubbles in the polyolefin resin foam sheet is within a predetermined range to improve mechanical strength and to have excellent flexibility.

In addition, the polyethylene resin obtained using the metallocene compound has a narrow molecular weight distribution, and in the case of a copolymer, the copolymer component is introduced into each molecular weight component at an approximately equal ratio. Therefore, the foamed sheet can be uniformly crosslinked. And since the foamed sheet is uniformly crosslinked, the foamed sheet can be uniformly stretched, and the thickness of the resulting crosslinked polyolefin resin foamed sheet can be made uniform as a whole.
In the polyolefin resin, the content of the polyethylene resin obtained by using the metallocene compound containing a tetravalent transition metal as a polymerization catalyst is limited to 40% by weight or more, preferably 50% by weight or more, % By weight or more is more preferable, and 100% by weight is particularly preferable. The content of the polyethylene resin obtained using the metallocene compound of 100% by weight means that only the polyethylene resin obtained using the metallocene compound is used as the polyolefin resin.

  As will be described later, the crosslinked polyolefin resin foam sheet is produced by stretching the foam sheet in a predetermined direction while foaming or heating. When the foam sheet is stretched, the foam sheet is expanded in the stretching direction so that the cell walls are close to each other. Therefore, a resin having adhesiveness to the polyolefin resin (for example, ethylene-vinyl acetate copolymer) When coalescing is used, the bubble walls are tightly integrated with each other, and the aspect ratio of the bubbles in the desired range cannot be obtained. On the other hand, the crosslinked polyolefin resin foam sheet of the present invention is required to have flexibility.

As a polyethylene resin obtained by using a metallocene compound containing a tetravalent transition metal as the polymerization catalyst, using a metallocene compound containing a tetravalent transition metal as a polymerization catalyst, ethylene and a small amount of an α-olefin are obtained. A linear low density polyethylene obtained by copolymerization is preferred.
Examples of the α-olefin include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene and 1-octene.
The metallocene compound generally refers to a compound having a structure in which a transition metal is sandwiched between π-electron unsaturated compounds, and a bis (cyclopentadienyl) metal complex is typical.

As the metallocene compound containing a tetravalent transition metal in the present invention, specifically, a tetravalent transition metal such as titanium, zirconium, nickel, palladium, hafnium, platinum or the like is added to one or more cyclopentadidienes. Examples thereof include compounds in which an enyl ring or an analog thereof is present as a ligand (ligand).
Examples of such metallocene compounds containing tetravalent transition metals include cyclopentadienyl titanium tris (dimethylamide), methylcyclopentadienyl titanium tris (dimethylamide), bis (cyclopentadienyl) titanium dichloride, Dimethylsilyltetramethylcyclopentadienyl-t-butylamidozirconium dichloride, dimethylsilyltetramethylcyclopentadienyl-t-butylamidohafnium dichloride, dimethylsilyltetramethylcyclopentadienyl-pn-butylphenylamidozirconium chloride , Methylphenylsilyltetramethylcyclopentadienyl-t-butylamido hafnium dichloride, indenyl titanium tris (dimethylamide), indenyl titanium tri (Diethylamide), indenyl titanium tris (di -n- propyl amide), indenyl titanium bis (di -n- butylamide) (di -n- propyl amide) and the like.

The metallocene compound exhibits an action as a catalyst in the polymerization of various olefins by changing the kind of metal and the structure of the ligand and combining with a specific cocatalyst (co-catalyst).
Specifically, the polymerization is usually performed in a catalyst system in which methylaluminoxane (MAO), a boron-based compound or the like is added to these metallocene compounds as a cocatalyst. In addition, the use ratio of the cocatalyst with respect to the metallocene compound is preferably 10 to 1,000,000 mole times, and more preferably 50 to 5,000 mole times.
The method for polymerizing the polyethylene resin is not particularly limited, and examples thereof include a solution polymerization method using an inert medium, a bulk polymerization method substantially free of an inert medium, and a gas phase polymerization method. The polymerization temperature is usually from −100 ° C. to 300 ° C., and the polymerization pressure is usually from normal pressure to 100 kg / cm ² .

Since the metallocene compound has uniform properties of active sites and each active site has the same activity, the uniformity of the molecular weight, molecular weight distribution, composition, composition distribution, etc. of the polymer to be synthesized is increased. Therefore, the polyolefin resin polymerized using these metallocene compounds as a polymerization catalyst has a narrow molecular weight distribution, and in the case of a copolymer, the copolymer component is introduced in almost equal proportion to any molecular weight component. Have
Furthermore, examples of polyolefin resins other than polyethylene resins obtained using a metallocene compound containing a tetravalent transition metal as a polymerization catalyst include polyethylene resins and polypropylene resins.

  The polyethylene resin is not particularly limited as long as it is other than a polyethylene resin obtained by using a metallocene compound containing a tetravalent transition metal as a polymerization catalyst. For example, linear low density polyethylene, low density Examples thereof include polyethylene, medium density polyethylene, high density polyethylene, ethylene-α-olefin copolymer containing 50% by weight or more of ethylene, ethylene-vinyl acetate copolymer containing 50% by weight or more of ethylene, and the like. Or two or more of them may be used in combination. Examples of the α-olefin constituting the ethylene-α-olefin copolymer include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene and 1-octene. Can be mentioned.

  Examples of the polypropylene resin include polypropylene and propylene-α-olefin copolymers containing 50% by weight or more of propylene, and these may be used alone or in combination of two or more. Good. Examples of the α-olefin constituting the propylene-α-olefin copolymer include ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene and 1-octene. Can be mentioned.

In addition, when the 25% compressive strength of the crosslinked polyolefin resin foamed sheet in accordance with JIS K6767 is large, the impact absorbability may be lowered. Therefore, 4.9 × 10 ⁴ Pa or less is preferable. Since the thickness uniformity may be inferior at the stage, 2 × 10 ⁴ to 4 × 10 ⁴ Pa is more preferable.
Furthermore, if the tensile strength at 23 ° C. in at least one direction of MD or CD in the cross-linked polyolefin resin foam sheet is small, the cross-linked polyolefin resin foam sheet may be cut during the bonding operation. × 10 ⁶ Pa or more is preferable, and if it is too large, the handleability may deteriorate when the crosslinked polyolefin-based resin foam sheet is used as the base material layer of the pressure-sensitive adhesive sheet for the display device front plate. 10 ^{6 to} 8.0 × 10 ⁶ Pa is more preferable.
In addition, the tensile strength in 23 degreeC in MD or CD of a crosslinked polyolefin-type resin foam sheet says what was measured based on JISK6767.

  Next, a method for producing a crosslinked polyolefin resin foam sheet will be described. The method for producing the crosslinked polyolefin resin foam sheet is not particularly limited. For example, a polyolefin resin containing 40% by weight or more of a polyethylene resin obtained using a metallocene compound containing a tetravalent transition metal as a polymerization catalyst. Supplying a resin and a pyrolytic foaming agent to an extruder, melt-kneading, and extruding the foamable polyolefin resin sheet into a sheet from the extruder; A step of crosslinking to a crosslinking degree of 60% by weight, and the obtained foamed resin sheet is melted or softened, and stretched in either or both directions of MD or CD to stretch the foam sheet bubbles. The aspect ratio (MD average bubble diameter / CD average bubble diameter) is 0.25 to 1 (preferably the bubble aspect ratio (CD The average cell diameter of average cell diameter / VD) can be mentioned a method containing a step of producing a crosslinked polyolefin-based resin foam sheet is 2 to 18).

  And as a method of crosslinking the expandable polyolefin resin sheet, for example, a method of irradiating the expandable polyolefin resin sheet with ionizing radiation such as electron beam, α ray, β ray, γ ray, or the like, expandable polyolefin resin Examples include a method in which an organic peroxide is blended in advance in the composition, and the resulting foamable polyolefin resin sheet is heated to decompose the organic peroxide. These methods may be used in combination.

  The amount of the thermally decomposable foaming agent in the foamable polyolefin resin composition may be appropriately determined according to the expansion ratio of the cross-linked polyolefin resin foam sheet. On the other hand, it may not be possible to obtain a crosslinked polyolefin resin foam sheet having a desired expansion ratio. On the other hand, if it is large, the tensile strength and compression recovery of the resulting crosslinked polyolefin resin foam sheet may be reduced. The amount is preferably 1 to 40 parts by weight, more preferably 1 to 30 parts by weight, based on 100 parts by weight of the polyolefin resin.

  The foamable polyolefin-based resin composition includes, as necessary, an antioxidant, a foaming aid such as zinc oxide, a cell core modifier, a heat stabilizer, a colorant, a flame retardant, an antistatic agent, and a filler. Etc. may be added within a range not impairing the physical properties of the crosslinked polyolefin resin foam sheet.

  Examples of the organic peroxide include 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis. (T-butylperoxy) octane, n-butyl-4,4-bis (t-butylperoxy) valerate, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, α, α '-Bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t- Butylperoxy) hexyne-3, benzoyl peroxide, cumylperoxyneodecanate, t-butylperoxybenzoate, 2,5-dimethyl-2,5-di ( Benzoylperoxy) hexane, t-butylperoxyisopropyl carbonate, t-butylperoxyallyl carbonate and the like may be mentioned, and these may be used alone or in combination of two or more.

  When the amount of the organic peroxide added is small, the foamable polyolefin resin sheet may be insufficiently cross-linked. On the other hand, when the amount is large, the organic peroxide decomposition residue in the resulting cross-linked polyolefin resin foam sheet. May remain, so 0.01 to 5 parts by weight is preferable and 0.1 to 3 parts by weight is more preferable with respect to 100 parts by weight of the polyolefin resin.

  Further, the method for foaming the foamable polyolefin resin sheet is not particularly limited, and examples thereof include a method of heating with hot air, a method of heating with infrared rays, a method using a salt bath, and a method using an oil bath. May be used in combination.

  The stretching of the foamed sheet may be performed after foaming the foamable polyolefin resin sheet to obtain the foamed sheet, or may be performed while foaming the foamable polyolefin resin sheet. In addition, after foaming a foamable polyolefin resin sheet to obtain a foamed sheet, when the foamed sheet is stretched, the foamed sheet is continuously stretched while the foamed sheet is maintained in a molten state without being cooled. Alternatively, after the foam sheet is cooled, the foam sheet may be heated again to be in a molten or softened state and then stretched.

Here, the molten state of the foamed sheet refers to a state in which the temperature of both surfaces of the foamed sheet is heated to the melting point of the polyolefin resin constituting the foamed sheet.
By stretching the foamed sheet, it is possible to produce a crosslinked polyolefin resin foamed sheet in which the foam sheet has an aspect ratio within a predetermined range by stretching and deforming the foamed cells in a predetermined direction.

  Furthermore, in the extending | stretching direction of a foam sheet, it is extended toward MD or CD of a long-shaped expandable polyolefin resin sheet, or toward MD and CD. In addition, when extending | stretching a foamable polyolefin resin sheet toward MD and CD, you may extend | stretch a foam sheet simultaneously toward MD and CD, and may extend | stretch separately for every one direction.

  As a method of stretching the foam sheet into MD, for example, while cooling the long foam sheet after foaming, rather than the speed (supply speed) at which the long foamable polyolefin resin sheet is supplied to the foaming process. The method of extending the foamed sheet to MD by increasing the winding speed (winding speed), and the speed of winding the foamed sheet (winding speed) rather than the speed of supplying the foamed sheet to the stretching process (supplying speed) Examples thereof include a method of stretching the foam sheet into MD by increasing the speed).

  In the former method, the expandable polyolefin resin sheet expands to MD by its own expansion. Therefore, when the foam sheet is stretched to MD, expansion to MD by expansion of the expandable polyolefin resin sheet. In consideration of the amount, it is necessary to adjust the sheet supply speed and the winding speed so that the foamed sheet is stretched to MD more than the expansion amount.

  Further, as a method of extending the foam sheet into the CD, the both ends of the CD of the foam sheet are gripped by a pair of grip members, and the foam sheet is moved by gradually moving the pair of grip members in directions away from each other. A method of stretching to CD is preferred. In addition, since the expandable polyolefin resin sheet expands to CD due to its own foaming, when the expanded sheet is stretched to CD, the expansion to CD due to expansion of the expandable polyolefin resin sheet is taken into consideration. Therefore, it is necessary to adjust so that the foamed sheet is stretched to the CD more than the expansion amount.

  Here, if the draw ratio in MD of the cross-linked polyolefin resin foam sheet is small, the flexibility and tensile strength of the cross-linked polyolefin resin foam sheet may be reduced, while if large, the foam sheet is cut during the stretch. Or the foaming gas escapes from the foaming sheet being foamed, the expansion ratio of the resulting crosslinked polyolefin resin foam sheet is significantly reduced, and the flexibility and tensile strength of the crosslinked polyolefin resin foam sheet are reduced. Since it may become non-uniform | heterogenous, 1.1-2.0 times are preferable and 1.2-1.5 times are more preferable.

In addition, the draw ratio in MD of a crosslinked polyolefin-type resin foam sheet is computed in the following way. That is, while obtaining the third root F of the expansion ratio of the crosslinked polyolefin resin foam sheet, the ratio (winding speed / supply speed) V between the winding speed and the supply speed is determined, and the crosslinked polyolefin resin foam is calculated based on the following formula. The draw ratio in the MD of the sheet can be calculated. However, the expansion ratio of the cross-linked polyolefin resin foam sheet is obtained by dividing the specific gravity of the expandable polyolefin resin sheet by the specific gravity of the cross-linked polyolefin resin foam sheet.
Stretch ratio (times) in MD of foam sheet = V / F

  Also, if the draw ratio of the crosslinked polyolefin resin foamed sheet in the CD is small, the flexibility and tensile strength of the crosslinked polyolefin resin foam sheet may be reduced. On the other hand, if the stretch ratio is large, the foamed sheet may be cut during stretching. Alternatively, the foaming gas escapes from the foam sheet being foamed, the foaming ratio of the resulting crosslinked polyolefin resin foam sheet is remarkably reduced, and the flexibility and tensile strength of the crosslinked polyolefin resin foam sheet are reduced, resulting in poor quality. Since it may become uniform, 1.2 to 4.5 times are preferable, and 1.5 to 3.5 times are more preferable.

In addition, the draw ratio of CD in the crosslinked polyolefin resin foamed sheet is the length of CD of the crosslinked polyolefin resin foamed sheet obtained by heating and foaming the expandable polyolefin resin sheet without stretching the MD and CD. The length of CD of the crosslinked polyolefin-based resin foam sheet stretched to CD is W2, and can be calculated based on the following formula.
Stretch ratio (times) of CD of foam sheet = W2 / W1

(Thickness)
The thickness of the base material layer made of the crosslinked polyolefin resin foam sheet is not particularly limited, but if it is thin, the flexibility, tensile strength, etc. of the crosslinked polyolefin resin foam sheet are reduced, and the display device obtained While the impact absorption, texture, mechanical strength, etc. of the pressure-sensitive adhesive sheet for the front plate are reduced, the improvement of the performance of the pressure-sensitive adhesive sheet for the front plate of the display device cannot be expected even if the thickness is increased. 1-3 mm is preferable.

(Acrylic adhesive layer)
The pressure-sensitive adhesive sheet for a display device front plate of the present invention is an acrylic pressure-sensitive adhesive layer containing 1 to 30 parts by weight of a tackifying resin having a softening point of 130 ° C. or higher with respect to 100 parts by weight of the acrylic pressure-sensitive adhesive layer. It is necessary to consist of an agent. That is, when a tackifying resin having a softening point of less than 130 ° C. is blended, the heat resistance of the pressure-sensitive adhesive layer is inferior. For example, when a temperature cycle test is performed, the pressure-sensitive adhesive force is insufficient or the pressure-sensitive adhesive layer is There is a case where it accumulates. If the adhesive force is insufficient or the adhesive layer sags, a gap may be formed between the adherends. As a result, shock absorption may be significantly deteriorated when the temperature cycle is applied. Aqueous properties may be significantly reduced. The softening point is preferably 135 to 150 ° C.
In addition, the softening point of tackifying resin means what was measured based on the ring and ball method of JISK2871.

In addition, if the amount of tackifying resin added is large, the pressure-sensitive adhesive layer becomes hard, and the distortion caused by the difference in shrinkage between the display panel housing and the display panel itself and the front plate due to temperature change cannot be alleviated. In addition, there may be a case where the physical distortion of the casing cannot be followed, and a gap is formed between the adherends due to long-term use. If the gap is formed in this way, the shock absorption is remarkably inferior, or the water stoppage is remarkably lowered. If the amount is too small, the adhesive strength may be insufficient.
For this reason, it is 1-30 weight part with respect to 100 weight part of acrylic polymers, Preferably it is 5-30 weight part, Especially preferably, it is 10-20 weight part.

Examples of the tackifying resin include rosin ester compounds such as polymerized rosin esters, hydrogenated rosin ester resins, and disproportionated rosin ester resins, rosin resins, polymerized rosin resins, hydrogenated rosin resins, rosin-modified phenol resins, Examples include terpene phenol resins, coumarone indene resins, alkylphenol resins, and petroleum resins. Among these, rosin ester compounds, rosin resins, polymerized rosin resins, and petroleum resins are preferable because low molecular weight components can be removed, and rosin ester compounds are more preferable.
The tackifying resin preferably has a content of volatile components having a weight average molecular weight of 600 or less and 13% by weight or less. By using such a tackifying resin, it is possible to reduce the volatile components generated by the tackifying resin without impairing the physical properties of the tack, and to obtain an acrylic pressure-sensitive adhesive that improves the tack physical properties and suppresses outgas generation as much as possible. be able to. And the adhesiveness with a base material layer can be improved and, as a result, a tape with higher water stopping property can be obtained. In addition, the weight average molecular weight of the said tackifying resin and its content can be measured by GPC, and can be calculated by a polystyrene conversion value and an area ratio.

Examples of a method for removing a volatile component having a weight average molecular weight of 600 or less from the tackifying resin include a method in which the tackifying resin is heated and melted above the softening point, and a method in which water vapor is blown.

When the tackifying resin is heated and melted, it is preferably heated in an inert gas such as nitrogen or helium in order to prevent an oxidation reaction with oxygen in the air, and the heating time is the tackifying resin by heating. In order to avoid decomposition of 1 to 5 hours is preferable.

  When steam is blown, the volatile components can be effectively reduced by blowing the steam after the pressure-reducing pressure of the tackifier resin is reduced to 1 to 50 kPa. As the time for blowing water vapor, if the time is short, the volatile component may not be reduced. On the other hand, if it is long, there is no difference in the effect of reducing the volatile component.

  The acrylic polymer used for the acrylic pressure-sensitive adhesive is not particularly limited, but is a homopolymer of a (meth) acrylic acid ester monomer, a (meth) acrylic acid ester monomer, and other copolymerizable with this. A copolymer with a monomer is mentioned, and a copolymer is preferable. In addition, (meth) acrylic acid means methacrylic acid or acrylic acid.

The (meth) acrylic acid ester monomer is not particularly limited. For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylic Examples include n-butyl acid, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, and (meth) acrylic acid alkyl esters are preferred. Further, (meth) acrylic acid alkyl ester having 4 or more carbon atoms in the alkyl group is more preferable, and (meth) acrylic acid alkyl ester having 4 to 12 carbon atoms in the alkyl group is particularly preferable.
Examples of monomers copolymerizable with (meth) acrylic acid esters include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid and maleic anhydride; 2-hydroxyethyl (meth) acrylate And hydroxyl group-containing monomers such as n-methylolacrylamide; epoxy group-containing monomers such as glycidyl acrylate and allyl glycidyl ether, and acrylic acid and methacrylic acid are preferred.

  The acrylic polymer is preferably a copolymer obtained by polymerizing a monomer containing (meth) acrylic acid and a (meth) acrylic acid alkyl ester having 4 to 12 carbon atoms in the alkyl group. More preferred is a copolymer obtained by polymerizing a monomer containing 50% by weight or more of acrylic acid and (meth) acrylic acid alkyl ester having 4 to 12 carbon atoms in the alkyl group as a total amount. A copolymer obtained by polymerizing an acid and a monomer containing 50 to 100% by weight of a total amount of an alkyl (meth) acrylic acid alkyl ester having 4 to 12 carbon atoms in the alkyl group is particularly preferable.

When the weight average molecular weight of the acrylic polymer is small, the fluidity is good and the initial tack is excellent, but the cohesive force is small, the heat resistance is lowered, and adhesive residue may be generated. Although it has excellent heat resistance, the fluidity is poor and the initial tack may be small, so 300,000 to 800,000 are preferable.
In addition, the weight average molecular weight of an acrylic polymer means what was measured as a polystyrene conversion molecular weight by GPC (Gel Permeation Chromatography: Gel permeation chromatography) method.
Specifically, the weight average molecular weight of the acrylic polymer is determined by filtering a diluted solution obtained by diluting the acrylic polymer with tetrahydrofuran (THF) 50 times with a filter, and based on the obtained filtrate. It can be obtained by measuring the polystyrene equivalent molecular weight of the polymer based on gel permeation chromatography. As said gel permeation chromatograph, what is marketed with the brand name "2690 Separations Model" from Water company etc. can be used, for example.

  The acrylic polymer is produced by polymerizing a monomer in a general manner in the presence of a polymerization initiator, but such a polymerization initiator is not particularly limited, for example, peroxide polymerization. Examples thereof include an initiator and an azo polymerization initiator, and those having a 10-hour half-life temperature of 80 ° C. or less are preferred so that the polymerization initiator and its residue do not remain in the resulting acrylic pressure-sensitive adhesive. In addition, a polymerization initiator may be used independently or may use 2 or more types together.

Furthermore, in producing an acrylic polymer by polymerization, in particular, the polymerization initiator has a 10-hour half-life temperature of 80 ° C. or less so that the polymerization initiator and its residue do not remain in the reaction solution as volatile components. It is preferable to select a certain one and set the polymerization temperature to be higher than the 10-hour half-life temperature of the polymerization initiator, and to perform polymerization for as long as possible. Furthermore, in order to reduce the polymerization initiator remaining in the reaction solution after the polymerization and allow the polymerization reaction to proceed rapidly and completely, the polymerization temperature T at the end of the polymerization is adjusted to satisfy the following formula (1). The polymerization temperature T is preferably maintained for a long time.
t _1/2 + 5 ≦ T ≦ t _1/2 +25 (1)
(T _1/2 : 10-hour half-life temperature of the polymerization initiator)

  Further, it is preferable that the acrylic polymer has less residual monomer, residual polymerization initiator and other impurities, and the residual monomer, residual polymerization initiator and other impurities are removed as necessary during or after the polymerization. It is preferable to reduce.

  As a method of reducing the residual monomer in the reaction solution at the time of polymerization, for example, a method of replacing the reflux solution of the reaction solution with a new solvent; when the polymerization rate becomes 95% or more, preferably 98% or more, vinyl acetate A method of removing a residual monomer together with a scavenger monomer by adding a relatively low boiling point scavenger monomer such as vinyl butyl ether, methyl acrylate, styrene, etc., and reacting the residual monomer with the scavenger monomer; Examples thereof include a method of washing an acrylic pressure-sensitive adhesive using a poor solvent for the pressure-sensitive adhesive, for example, a low boiling point solvent such as methanol, ethanol, n-hexane, and n-heptane.

  Furthermore, you may add additives, such as a crosslinking agent, a plasticizer, an emulsifier, a softening agent, a filler, a pigment, and dye, to an acrylic adhesive. In addition, it is preferable that these additives also remove volatile components as much as possible.

  The crosslinking agent is not particularly limited, and examples thereof include an isocyanate crosslinking agent, an aziridine crosslinking agent, an epoxy crosslinking agent, and a metal chelate crosslinking agent. Further, the acrylic pressure-sensitive adhesive may contain a heat conductive filler such as alumina, boron nitride, aluminum nitride, silicon nitride, silicon carbide, magnesium oxide, silica, magnesia, ceramic powder and the like.

  By adding a heat conductive filler in the pressure-sensitive adhesive layer, the heat conductivity of the pressure-sensitive adhesive sheet for the front panel of the display device can be improved. It can be heated efficiently.

  And if the thickness of the pressure-sensitive adhesive layer is thin, the adhesiveness of the pressure-sensitive adhesive sheet for the display device front plate may be lowered, and if it is thick, the workability of the tape may be inferior, When the closed space is formed by using the pressure-sensitive adhesive sheet for plates, outgas may be a problem, so 10 to 150 μm is preferable. More preferably, it is 20-100 micrometers, More preferably, it is 30-60 micrometers.

(Tape VOC)
When the pressure-sensitive adhesive sheet for a display device front plate of the present invention is heated at 90 ° C. for 30 minutes, the volatile component concentration calculated by the following formula (2) is preferably less than 500 ppm. That is, when the volatile component concentration is less than 500 ppm, it can be evaluated that the amount of volatile components generated from the adhesive tape is dramatically small, and adverse effects on the electronic components in the display device can be prevented. Moreover, it becomes very excellent in adhesiveness with the base material layer mentioned above.
Volatile component concentration (ppm)
= Weight of volatile component X (μg) / Adhesive sheet weight for display device front plate before heating (g) Formula (2)
(However, in Formula (2), the volatile component weight X represents the weight in terms of hexadecane.)

  The volatile component weight X is obtained by concentrating the weight of the volatile component released when the pressure-sensitive adhesive sheet for the display device front plate is heated at 90 ° C. for 30 minutes using a thermal desorption device, and using a GC-MS device. Can be measured. The volatile component concentration can be calculated by dividing the measured volatile component weight X by the weight of the pressure-sensitive adhesive sheet for the display device front plate.

Specifically, as the method for measuring the volatile component concentration, specifically, an acrylic pressure-sensitive adhesive constituting the pressure-sensitive adhesive sheet for the display device front plate is prepared, and about 20 mg of this pressure-sensitive adhesive is sample tube. (Inner diameter: about 5 mm, length: about 10 cm) Obtained by flowing helium gas into the sample tube at a flow rate of 1.5 ml / min for 30 minutes while heating and holding at 90 ° C. Volatile components are collected and concentrated in a trap tube built in the thermal desorption apparatus, and then the trap tube is heated at 280 ° C. for 10 minutes and supplied to the GC-MS apparatus.
In the GC-MS apparatus, a nonpolar capillary column (trade name “HP-1” manufactured by Agilent Technologies, 0.32 mm × 60 m × 0.25 μm) was used, and the temperature of the capillary column was 40 ° C. for 4 minutes. After the maintenance, the capillary column is heated to 100 ° C. at a heating rate of 5 ° C. per minute, and then the capillary column is heated to 320 ° C. at a heating rate of 10 ° C. per minute, and then at 320 ° C. Hold for 3 minutes. The MS measurement range is 30 to 400 amu, the helium flow rate is 1.5 ml / min, the ionization voltage is 70 eV, the ion source is 230 ° C., the interface is 250 ° C., and the transfer line is 225 ° C. The weight of the volatile component can be calculated by converting the obtained peak area by weight based on an absolute calibration curve created with n-hexadecane.

The measured weight of the volatile component is proportionally converted to the weight of the acrylic pressure-sensitive adhesive constituting the pressure-sensitive adhesive sheet for the display device front plate to be measured, and the proportionally converted volatile component weight X is displayed on the display device. The volatile component concentration can be calculated by dividing by the weight of the pressure sensitive adhesive sheet for the front plate.
The thermal desorption device is commercially available, for example, from Perkin Elmer under the trade name “ATD-400”, and the GC-MS device is commercially available, for example, from JEOL under the trade name “Automass II-15”. ing.

Furthermore, the pressure-sensitive adhesive sheet for a display device front plate of the present invention preferably has a volatile toluene concentration calculated by the following formula (3) of less than 50 ppm when heated at 90 ° C. for 30 minutes. . Thus, if the volatile toluene concentration is less than 50 ppm, the amount of toluene generated from the pressure-sensitive adhesive sheet for the display device front plate can be kept low even when the temperature becomes high, and the generation of odor can be suppressed. Can do.
Volatile toluene concentration (ppm)
= Weight of volatile toluene Y (μg) / weight of double-sided pressure-sensitive adhesive tape before heating (g) Formula (3)
(However, in formula (3), the volatile toluene weight Y represents the weight in terms of hexadecane.)
The volatile toluene concentration can be calculated by measuring the volatile toluene weight Y in the same manner as the volatile component weight X and dividing the volatile toluene weight Y by the weight of the double-sided adhesive tape.

  Such acrylic pressure-sensitive adhesives can reduce low molecular weight components such as residual monomers as much as possible, adjust the weight average molecular weight of acrylic polymers to a certain range, or adjust the softening point of the tackifying resin. Achievable.

(Manufacturing method of pressure-sensitive adhesive sheet for display device front plate)
Examples of the method for producing a pressure-sensitive adhesive sheet for a display device front plate of the present invention include a method in which a pressure-sensitive adhesive is applied to at least one surface of a base material layer made of a crosslinked polyolefin resin foamed sheet and the pressure-sensitive adhesive layers are laminated and integrated.
As a method of applying and laminating and integrating the pressure-sensitive adhesive layer, for example, a method of applying a pressure-sensitive adhesive using a coating machine such as a coater on at least one surface of the cross-linked polyolefin resin foam sheet, at least a cross-linked polyolefin resin foam sheet Examples thereof include a method of spraying and applying a pressure-sensitive adhesive using a spray on one side, a method of applying a pressure-sensitive adhesive using a brush on at least one side of a crosslinked polyolefin resin foam sheet, and the like.

  The pressure-sensitive adhesive sheet for a display device front plate of the present invention preferably has a pressure-sensitive adhesive layer only on one side of the base material layer. The above-mentioned crosslinked polyolefin resin foam sheet used as a base material layer in the pressure-sensitive adhesive sheet for a display device front plate of the present invention alone exhibits very excellent adhesion to other resin materials. For this reason, even when an adhesive layer is provided only on one side, the fixing part does not shift due to the adhesive strength of the adhesive layer and the adhesive strength of the polyolefin resin foam sheet on the other side, ensuring shock absorption and water-stopping properties. it can. In addition, since both sides are not made adhesive layers, they are not fixed too strongly, so they have excellent initial reworkability (possible to reposition), and more absorb strain caused by differences in shrinkage between the bonded members. It becomes easy.

(Use)
The pressure-sensitive adhesive sheet for a display device front plate of the present invention can be used for fixing various display panels or display housings and a display device front plate. In particular, the display plate is preferably an acrylic resin plate.

Since the pressure-sensitive adhesive sheet for a display device front plate according to the present invention is configured as described above, it has a sufficient impact absorption and water-stopping property while being thin, and also has a high temperature and a temperature change environment. The physical properties of can be kept.
Therefore, a display device with excellent durability can be provided.

  In addition, if the content of a component having a weight average molecular weight of 600 or less is 13% or less as a tackifying resin, the amount of volatile component can be suppressed to a very small amount, so that the volatile component is contained in an electronic component even in a narrow internal space. Does not adversely affect

  Examples of the present invention will be described in detail below, but the present invention is not limited to the following examples.

(Example 1)
(Production of acrylic adhesive)
In a reactor equipped with a thermometer, a stirrer, a cooling tube, a dropping funnel, and a nitrogen gas introduction tube, 70 parts by weight of n-butyl acrylate, 27 parts by weight of 2-ethylhexyl acrylate, 3 parts by weight of acrylic acid, 2-hydroxyethyl methacrylate 0 A monomer mixture consisting of 0.1 part by weight and 0.05 part by weight of dodecanethiol and 80 parts by weight of ethyl acetate were supplied and stirred to dissolve the monomer mixture in ethyl acetate to prepare a monomer mixture solution.
At the reflux point, 4 mmol of lauroyl peroxide (10-hour half-life temperature: 62 ° C.) as a polymerization initiator was added to the polymerization for 4 hours to polymerize.

After 4 hours, 4 mmol of a polymerization initiator was further added over 4 to 6 hours, followed by polymerization for 10 hours. Thereafter, 5 g of vinyl acetate monomer was added to obtain an acrylic polymer.
To 100 parts by weight of the obtained acrylic polymer (solid), 1.6 parts by weight of an isocyanate-based crosslinking agent (trade name “Coronate L”, active ingredient: 55% by weight, manufactured by Nippon Polyurethane Co., Ltd.) and weight as a tackifier resin An acrylic pressure-sensitive adhesive A was obtained by adding and stirring 19 parts by weight of a rosin ester compound having a softening point of 140 ° C. from which volatile components having an average molecular weight of 600 or less were removed (content 9.6% by weight).

(Preparation of base material)
Linear low-density polyethylene obtained by using a metallocene compound containing a tetravalent transition metal as a polymerization catalyst (trade name “EXACT3027” manufactured by Exxon Chemical Co., Ltd., density: 0.900 g / cm ³ , weight average molecular weight: 2.0, melting point: 98 ° C., softening point: 85 ° C.) 100 parts by weight, azodicarbonamide 5 parts by weight, 2,6-di-t-butyl-p-cresol 0.3 part by weight and zinc oxide 1 part by weight The foamable polyolefin resin composition comprising the above was supplied to an extruder, melted and kneaded at 130 ° C., and extruded into a long foamable polyolefin resin sheet having a width of 200 mm and a thickness of 0.8 mm.

Next, the foamable polyolefin resin sheet is cross-linked by irradiating an electron beam with an acceleration voltage of 800 kV for 5 Mrad on both surfaces of the long foamable polyolefin resin sheet, and then the foamable polyolefin resin sheet is heated with hot air and infrared rays. The mixture was continuously fed into a foaming furnace maintained at 250 ° C. by a heater to be heated and foamed.
Then, after continuously feeding the obtained foam sheet from the foaming furnace, the foam sheet is stretched to the CD while maintaining the temperature of both surfaces at 200 to 250 ° C. The foamed sheet is stretched to MD by winding the foamed sheet at a winding speed faster than the feeding speed (feeding speed) of the polyolefin resin sheet to the foaming furnace, and the foamed cells are stretched to CD and MD. A base material A made of a crosslinked polyolefin resin foam sheet having a width of 1050 mm, a thickness of 0.1 mm, a crosslinking degree of 25% by weight and an expansion ratio of 4.7 times was obtained.

(Preparation of pressure-sensitive adhesive sheet for display device front plate)
The acrylic adhesive A is applied to both surfaces of the substrate A so that the thickness is 50 μm after drying, and is dried at 105 ° C. for 5 minutes. From the acrylic adhesive A to one surface of the substrate A, A pressure-sensitive adhesive sheet for a display device front plate in which a 50 μm-thick pressure-sensitive adhesive layer was laminated and integrated was produced.

(Example 2)
Substrate B was obtained in the same manner as in Example 1 except that the thickness of the crosslinked polyolefin resin foamed sheet was adjusted to 0.2 mm by adjusting the winding speed. And the adhesive sheet for display apparatus front plates was produced using this base material B and the acrylic adhesive A similarly to Example 1. FIG.

(Example 3)
An acrylic pressure-sensitive adhesive B was obtained in the same manner as in Example 1 except that the amount of the rosin ester compound used in Example 1 was 25 parts by weight. A pressure-sensitive adhesive sheet for a display device front plate was produced in the same manner as in Example 1 except that the acrylic pressure-sensitive adhesive B was used.

Example 4
An acrylic pressure-sensitive adhesive C was obtained in the same manner as in Example 1 except that 19 parts by weight of a rosin ester compound having a softening point of 140 ° C. from which volatile components were not removed was used. A display device front plate pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1 except that the acrylic pressure-sensitive adhesive C was used.
(Example 5)
An acrylic pressure-sensitive adhesive D was obtained in the same manner as in Example 1 except that 2 parts by weight of a rosin ester compound having a softening point of 140 ° C. from which volatile components were not removed was used. A pressure-sensitive adhesive sheet for a display device front plate was produced in the same manner as in Example 1 except that the acrylic pressure-sensitive adhesive D was used.

(Comparative Example 1)
A pressure-sensitive adhesive sheet for a display device front plate in the same manner as in Example 1 except that polyurethane foam (“Polon SR” manufactured by INOAC, thickness 0.2 mm) was used as the base material C instead of the crosslinked polyolefin resin foam sheet. Was made.

(Comparative Example 2)
An acrylic pressure-sensitive adhesive E was obtained in the same manner as in Example 1 except that 32 parts by weight of the same rosin ester compound used in Example 1 was blended. A pressure-sensitive adhesive sheet for a display device front plate was produced in the same manner as in Example 1 except that the acrylic pressure-sensitive adhesive E was used.

(Comparative Example 3)
Instead of the rosin ester compound used in Example 1, Example 1 except that 19 parts by weight of a tackifying resin having a softening point of 125 ° C. (knitted terpene polymer, “YS Resin PX” manufactured by Yasuhara Chemical Co., Ltd.) was blended. Similarly, an acrylic pressure-sensitive adhesive F was obtained. A pressure-sensitive adhesive sheet for a display device front plate was produced in the same manner as in Example 1 except that the acrylic pressure-sensitive adhesive F was used.

About each of the adhesive sheets for display device front plates obtained in Examples 1 to 5 and Comparative Examples 1 to 3, the aspect ratio of the crosslinked polyolefin resin foam sheet (average cell diameter of MD / average cell diameter of CD), 25% compressive strength, waterstop, impact conductivity, cold cycle resistance, VOC, and cloudiness were examined, and the results are shown in Table 1.
The aspect ratio, 25% compressive strength, waterstop, impact conductivity, cold heat cycle resistance, VOC, and cloudiness were evaluated by the following evaluation methods.

(Evaluation methods)
〔aspect ratio〕
After calculating the average cell diameter of MD and CD in the crosslinked polyolefin resin foam sheet obtained by the above-described method, it was calculated by the following formula.
Aspect ratio = MD average bubble diameter / CD average bubble diameter

[25% compressive strength]
A 25% compressive strength in accordance with JIS K6767 was determined.

[Waterproof evaluation]
Two acrylic plates of 150 mm × 150 mm × 5 mm were prepared. One acrylic plate was provided with a hole having a diameter of 7 mm.
The pressure-sensitive adhesive sheets for display device front plates obtained in Examples and Comparative Examples were cut into donut shapes having an outer diameter of 60 mm and an inner diameter of 50 mm to obtain sample pieces.
Two acrylic plates were bonded together using this donut-shaped sample piece.
After that, a hose is attached to the hole, and the cross-linked polyolefin resin foam sheet constituting the base material layer is compressed so that the compressibility is 20%, and the portion corresponding to the inner diameter of the donut is filled with water to a pressure of 10 kPa. It was. And the leakage of water was evaluated according to JISC0920 IPX7 while applying a pressure of 10 kPa.

[Shock absorption rate]
Two iron plates having a thickness of 2 mm and a size of 100 × 100 mm were prepared. An impact pickup device was attached to one iron plate and used as a lower iron plate. At the center of this lower iron plate, the adhesive sheet for the display device front plate produced in the examples and comparative examples is cut to 50 × 50 mm, and the other iron plate is placed on the adhesive sheet for the display device front plate. I put it.
Next, in a state where the cross-linked polyolefin resin foam sheet constituting the base material layer is compressed so that the compressibility is 40%, an iron ball having a weight of 15 g is vertically separated from the upper iron plate by 10 cm. The impact acceleration was measured with an impact pick-up device after naturally falling to the center, and the average of the absolute values of the positive and negative maximum values was defined as impact conductivity 1.
Moreover, the impact conductivity 2 when the iron ball was dropped only on the iron plate to which the impact pickup device was attached was measured, and the impact absorption rate when the pressure-sensitive adhesive sheet for the display device front plate was interposed was obtained by the following formula. . In addition, it means that the impact could be absorbed with the adhesive sheet for display apparatus front plates, so that an impact absorption rate was small.
Impact absorption rate = ((impact conductivity 1 / impact conductivity 2) × 100)

[Cooling and heat cycle resistance]
From the adhesive sheet for the front plate of the display device, an adhesive sheet frame piece having a rectangular shape of 80 mm × 80 mm on the outside, a rectangular shape of 50 mm × 50 mm cut from the inside, and a width of 25 mm was produced.
Two 100 × 100 mm × (thickness 5 mm) acrylic resin transparent plates and aluminum plates were prepared. The pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet piece was attached to the central portion of one plate, and the other plate was laminated on the pressure-sensitive adhesive sheet piece from the base material layer side. Then, using 12 bolts, two plates were fixed at a thickness that would result in a compression rate of the foamed substrate of 20%, to produce a test piece.
This test piece was subjected to 30 cycles with a cooling cycle tester (manufactured by ESTEC) at -20 ° C for 2 hours / 80 ° C for 2 hours as one cycle.
After 30 cycles, the test piece was immersed in an aqueous layer containing 40 ° C. water to a depth of 20 cm. The water temperature was kept at 40 ° C. and immersed for 24 hours. Thereafter, the test piece was taken out and visually confirmed whether water had entered the inside of the pressure-sensitive adhesive sheet frame piece.

(Measurement of volatile component concentration)
About the obtained adhesive sheet for display apparatus front boards, the volatile component density | concentration calculated by above-mentioned Formula (2) and the volatile toluene density | concentration calculated by Formula (3) were measured in the above-mentioned way. Measurement was performed at 90 ° C. for the purpose of promoting the volatilization of volatile components.

[Evaluation of cloudy]
About 20 g of the pressure-sensitive adhesive sheet for the display device front plate was put in a glass bottle with an internal volume of 100 ml, covered with a glass plate, heated at 120 ° C. for 24 hours, and the change of the glass plate was visually evaluated. The evaluation criteria are as follows.
○: No change.
Δ: There is a slight amount of cloudiness.
X: There is cloudiness that can be clearly confirmed.

As shown in Table 1 above, it can be seen that the pressure-sensitive adhesive sheet for a display device front plate of the present invention is excellent in water-stopping and impact resistance and also in heat resistance.
It can also be seen that the generation of VOCs can be reduced by removing volatile components having a weight average molecular weight of 600 or less in the tackifier resin as in Examples 1 to 3.

Claims (6)

An acrylic pressure-sensitive adhesive layer is laminated and integrated on at least one surface of the base material layer, and is a pressure-sensitive adhesive sheet for a display device front plate interposed between a display panel and a transparent front plate for protecting the display panel,
The base material layer is a cross-linked polyolefin resin foam sheet having a cross-linking degree of 5 to 60% by weight and a bubble aspect ratio of 0.25 to 1.
The acrylic pressure-sensitive adhesive layer is composed of an acrylic pressure-sensitive adhesive containing 1 to 30 parts by weight of a tackifier resin having a softening point of 130 ° C. or higher with respect to 100 parts by weight of the acrylic copolymer. Adhesive sheet for display device front plate.   The pressure-sensitive adhesive sheet for a display device front plate according to claim 1, wherein the tackifying resin has a content of a component having a weight average molecular weight of 600 or less of 13% or less. The pressure-sensitive adhesive sheet for a display device front plate according to claim 1 or 2, wherein the volatile component concentration calculated by the formula (1) is less than 500 ppm when heated at 90 ° C for 30 minutes.
Volatile component concentration (ppm)
= Weight of volatile component X (μg) / Adhesive sheet weight for display device front plate before heating (g) Formula (1)
(However, in formula (1), the volatile component weight X represents the weight in terms of hexadecane.)   The acrylic pressure-sensitive adhesive includes a copolymer obtained by polymerizing a monomer containing (meth) acrylic acid and a (meth) acrylic acid alkyl ester having an alkyl group having 4 to 12 carbon atoms. The pressure-sensitive adhesive sheet for a display device front plate according to any one of claims 3 to 4.   The acrylic polymer is copolymerized by selecting a polymerization initiator having a 10-hour half-life temperature of 80 ° C. or lower and a polymerization temperature higher than the 10-hour half-life temperature of the polymerization initiator. The pressure-sensitive adhesive sheet for a display device front plate according to any one of claims 1 to 4.   The display device front plate according to any one of claims 1 to 5, wherein the thickness of the crosslinked polyolefin resin foam sheet is 0.1 to 3 mm, and the thickness of the acrylic pressure-sensitive adhesive layer is 10 to 150 µm. Adhesive sheet.