KR20070035503A - Pressure-sensitive adhesive sheet and method for production thereof - Google Patents

Abstract

The laser ablation process is given to the adhesive sheet provided with the base material 11 and the adhesive layer 12 at least, and the hole diameter in the base material 11 and the adhesive layer 12 is 0.1-120 micrometers, and the base material 11 The through-holes 2 with a hole diameter of 0.1-40 micrometers in the surface of are formed by the hole density of 30-50,000 piece / 100 cm <2>. In such a pressure-sensitive adhesive sheet, air sticking and bubbles can be prevented or removed by the through holes 2, but the appearance is inferior to that without the through holes.

Adhesive sheet

Description

Adhesive sheet and its manufacturing method {PRESSURE-SENSITIVE ADHESIVE SHEET AND METHOD FOR PRODUCTION THEREOF}

The present invention relates to a pressure-sensitive adhesive sheet capable of preventing or removing air clots or bubbles and a method of manufacturing the same.

When affixing an adhesive sheet to a to-be-adhered body manually, air may accumulate between a to-be-adhered body and an adhesive surface, and may damage the external appearance of an adhesive sheet. Such air pooling tends to occur especially when the area of the adhesive sheet is large.

In order to solve the poor appearance of the adhesive sheet due to the air trapping, it is necessary to replace the adhesive sheet with another adhesive sheet, to remove the adhesive sheet once and fix it, or to form a hole with a needle in the raised part of the adhesive sheet. Pulling out is being done. However, in the case of replacing the adhesive sheet, it not only requires labor, but also causes an increase in cost, and in the case of correcting the adhesive sheet, the adhesive sheet may be broken, wrinkles may appear on the surface, or the adhesiveness may be reduced. There are many problems that occur. On the other hand, the method of punching a hole with a needle may damage the external appearance of an adhesive sheet.

In order to prevent the formation of air trapping, there is a method of attaching the adherend or adhesive surface with water soaking in advance.However, a large adhesive sheet such as a glass scattering film, a decorative film, a marking film, etc., attached to the window may be used. In case of sticking, it takes a lot of time and effort. Moreover, although there exists a method of preventing air pooling by sticking using a machine rather than manual labor, mechanical adhesion may not be applicable depending on the use of an adhesive sheet, or the site | part and shape of a to-be-adhered body.

On the other hand, resin materials such as acrylic resins, ABS resins, polystyrene resins, and polycarbonate resins may generate gas even by heating or not by heating, but the adhesive sheet is attached to an adherend made of such a resin material. In this case, bubbles (bulged material) are generated in the adhesive sheet by the gas generated from the adherend.

In addition, when an adhesive sheet is affixed to the to-be-adhered body which consists of resin which gas is easy to permeate | transmit, the permeated gas may accumulate between the to-be-adhered body and an adhesive sheet, and swelling and peeling may arise in an adhesive sheet. For example, when a marking sheet is attached to a gasoline tank made of polyethylene resin of a motorcycle, vapor in the gasoline tank passes through the polyethylene resin layer of the gasoline tank and volatilizes, thereby causing swelling and peeling of the marking sheet, thereby damaging the appearance. It may cause undesirable accidents, such as causing.

In order to solve the problem mentioned above, in the adhesive sheet of patent document 1, punching process is performed in a blade shape and a hole shape with respect to a base material and an adhesive layer, the through-hole of diameter 0.2-1.0 mm is formed, and a patent document In the pressure sensitive adhesive sheet described in 2, the substrate and the pressure sensitive adhesive layer are subjected to perforation using a heating needle to form through holes having a diameter of 0.05 to 0.15 mm, and to draw air or gas out of these through holes to the outside. To prevent air trapping or air bubbles.

Patent Document 1: Japanese Patent Laid-Open No. 2-107682

Patent Document 2: Publication No. Hei 4-100235

However, in the said adhesive sheet, since a through hole is visually seen, the external appearance of an adhesive sheet is not necessarily favorable. In particular, in the case where the through hole is formed using a heating needle like the PSA sheet described in Patent Document 2, the portion where the base material is melted and swollen damages the appearance of the PSA sheet.

In addition, in the said adhesive sheet, when a liquid, such as water or gasoline, adheres to a to-be-adhered body, when a liquid, such as water or gasoline, adheres to an adhesive sheet, these liquids will go into a through hole, and a through-hole part (peripheral part of a through hole) will swell, etc. There was a problem damaging it.

SUMMARY OF THE INVENTION The present invention has been made in view of such a situation, and although it is possible to prevent or remove air trappings and bubbles by the through holes, the present invention provides a pressure-sensitive adhesive sheet and a method of manufacturing the same in comparison with those without a through hole. The purpose.

In order to achieve the said objective, 1st this invention is an adhesive sheet which has at least a base material and an adhesive layer, and is provided with the some through-hole which penetrates from one surface to the other surface, The said base material and the said adhesive layer The hole diameter of the through hole is 0.1 to 120 μm, the diameter of the through hole on the surface of the substrate is 0.1 to 40 μm, and the hole density of the through hole is 30 to 50,000 holes / 100 cm 2, and the through hole is It provides the adhesive sheet formed and formed by the laser ablation process (Invention 1).

In addition, in this specification, the concept of a film is included in the "sheet", and the concept of a sheet is included in the "film".

In the pressure-sensitive adhesive sheet (Invention 1) according to the present invention, since the air between the adherend and the pressure-sensitive adhesive sticks out from the through hole to the outside of the pressure-sensitive adhesive sheet surface, air does not roll up when the adhesive is stuck to the adherend, and the air may be stuck. Can be prevented. Although the air may be rolled up and the air may be clogged, by recompressing the air pool or the air pool periphery including the air pool, the air escapes from the through hole to the outside of the adhesive sheet surface, and the air pool is lost. In addition, even if gas is generated from the adherend after adhering to the adherend, the gas escapes from the through-hole to the outside of the adhesive sheet surface, whereby bubbles can be prevented from occurring.

In addition, the through-hole formed by the laser ablation process is in shape because the melt called so-called dross adheres to the circumferential edge thereof, or heat deformation does not occur on the adhesive sheet surface or inside, and the shape of the through-hole is When the hole diameter is 40 µm or less, the through hole is not visible to the naked eye on the surface of the substrate, and the appearance is the same as that of the pressure-sensitive adhesive sheet without the through hole. This is not influenced by the nature of the substrate, and even through a high gloss substrate, a substrate having a low concealment rate, or a high brightness substrate, through holes are usually easily seen, the through holes are not visible to the naked eye on the surface of the substrate.

Moreover, in the said adhesive sheet, even if liquid, such as water or gasoline, adheres to a to-be-adhered body, even if a liquid, such as water or gasoline, adheres to these adhesive sheets, these liquids will go into a through hole and swelling of a through hole part (periphery of a through hole) etc. will be prevented. Therefore, the external appearance of an adhesive sheet is maintained favorable.

In the said invention (invention 1), it is preferable that the hole diameter of the said through hole becomes small gradually from the adhesive sheet back surface to the adhesive sheet surface (invention 2). As the hole diameter of the through hole is changed in this manner, the through hole is hardly seen on the surface of the pressure sensitive adhesive sheet, and the appearance of the pressure sensitive adhesive sheet is better.

Secondly, in the present invention, laser ablation is applied to an adhesive sheet having at least a substrate and an adhesive layer, the pore diameter in the substrate and the adhesive layer is 0.1 to 120 µm, and the pore diameter on the surface of the substrate is Provided is a pressure-sensitive adhesive sheet manufacturing method characterized by forming a through hole having a diameter of 0.1 to 40 µm at a hole density of 30 to 50,000 particles / 100 cm 2 (Invention 3).

According to the above invention (Invention 3), there is no adherence or thermal deformation of the dross, and the through hole can be formed in an orderly shape. Therefore, the formed through hole is not visible to the naked eye on the surface of the substrate, and as a result, An adhesive sheet such as an adhesive sheet without a through hole is obtained. Moreover, in the obtained adhesive sheet, even if liquid, such as water or gasoline, adheres to an adherend, even if liquid, such as water or gasoline, adheres, these liquids will go into a through hole and swelling of a through hole part (periphery of a through hole) etc. will be prevented. Therefore, the external appearance of an adhesive sheet is maintained favorable.

In the said invention (invention 3), the said laser ablation process is the laser light (invention 4) or excimer laser (invention 5) whose wavelength is 150-352 nm, pulse width is 2-300 ns, or wavelength is 150-900. Nm and a pulse width of 10 to 900 fs, or a femtosecond laser (invention 7).

In the said invention (invention 3-7), it is preferable to perform the said laser ablation process from the adhesive sheet back surface side (invention 8). Here, "adhesive sheet back surface" means the surface opposite to the surface of an adhesive sheet, and when a peeling material exists in a lowermost layer, when the lower surface of a peeling material and a peeling material do not exist and an adhesive layer is exposed, The adhesive side is applicable.

In the case of forming the through hole by laser ablation, since the tapered tape is formed in the through hole in many cases, the hole diameter of the through hole is determined by performing the laser ablation from the adhesive sheet back side. The direction on the adhesive sheet surface side becomes smaller than the side, and therefore, the through hole is hardly seen on the adhesive sheet surface, and the appearance of the adhesive sheet is better.

According to this invention, although the air hole and a bubble can be prevented or removed by a through hole, the adhesive sheet which a through hole is not visually seen on the surface of a base material is provided. This adhesive sheet does not depend on the property of a base material, and it seems that an external appearance does not have a through hole, and has an extremely favorable external appearance. Moreover, after sticking this adhesive sheet, it can maintain a favorable appearance also in the environment to which a liquid adheres.

1 is a cross-sectional view of an adhesive sheet according to an embodiment of the present invention.

2 is a partially enlarged cross-sectional view of an adhesive sheet according to one embodiment of the present invention.

3 is a cross-sectional view showing an example of a pressure-sensitive adhesive sheet manufacturing method according to an embodiment of the present invention.

* Code Description

1: adhesive sheet

11: description

12: pressure-sensitive adhesive layer

13: release material

1A: Adhesive sheet surface

1B: Adhesive surface

2: through hole

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described.

[Adhesive sheet]

1 is a cross-sectional view of an adhesive sheet according to an embodiment of the present invention.

As shown in FIG. 1, the adhesive sheet 1 which concerns on this embodiment consists of laminating | stacking the base material 11, the adhesive layer 12, and the peeling material 13. As shown in FIG. However, the peeling material 13 peels at the time of use of the adhesive sheet 1.

In this adhesive sheet 1, the penetration hole 2 which penetrates the base material 11 and the adhesive layer 12 from the adhesive sheet surface 1A to the adhesion surface 1B is formed in multiple numbers, and this through hole (2) is formed by laser ablation processing. The detailed description of laser ablation processing is mentioned later.

The material of the base material 11 is not particularly limited as long as it is a material in which the through hole 2 can be formed by the laser ablation process. For example, a resin film, a metal film, a resin film on which metal is deposited, paper, and lamination thereof Sieves and the like. These materials may contain various additives, such as an inorganic filler, an organic filler, and a ultraviolet absorber.

On the other hand, a decorative layer may be formed on the surface of the material, for example, by printing, printing, coating of paint, transfer from a transfer sheet, vapor deposition, sputtering, or the like. An undercoat layer such as a gross adjustment coat may be formed, or a top coat layer such as a hard coat, an antifouling coat, a surface roughness and a mirror surface glossiness adjustment coat may be formed. In addition, these decorative layers, an undercoat layer, or a top coat layer may be formed in the whole surface of the said material, and may be formed partially.

Examples of the resin film include polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyvinyl chloride, polystyrene, polyurethane, polycarbonate, polyamide, polyimide and polymethacrylic acid. Methyl, polybutene, polybutadiene, polymethylpentene, ethylene vinyl acetate copolymer, ethylene (meth) acrylic acid copolymer, ethylene (meth) acrylic acid ester copolymer, ABS resin, ionomer resin; Films made of resins such as thermoplastic elastomers containing components such as polyolefins, polyurethanes, polystyrenes, polyvinyl chlorides, polyesters, foamed films, laminated films thereof and the like can be used. A commercially available thing may be used for a resin film, and what was formed by the casting method etc. using a process material may be used. As the paper, for example, good quality paper, glassine paper, coated paper, laminated paper or the like can be used.

It does not specifically limit as said process material, For example, peeling process of various papers or resin films, such as polyethylene terephthalate, polypropylene, polyethylene, with a peeling agent or synthetic resins, such as a silicone type, polyester type, acrylic type, alkyd type, urethane type, etc. You can use one. The thickness of a process material is about 10-200 micrometers normally, Preferably it is about 25-150 micrometers.

The degree of gloss (surface roughness), concealment rate, and brightness of the base material 11 in the present embodiment is not particularly limited, and through holes are easily visible, and high gloss (for example, surface roughness Ra) is 0.15. Less than μm, or having a mirror glossiness Gs (60 °) of 80% or more), a low hiding rate (eg less than 90%), or a high brightness (eg, L * a * b * colorimetric system When the saturation C * is 60 or less, the brightness L * exceeds 60, and when the saturation C * exceeds 60, the brightness L * exceeds 85.

In addition, surface roughness (Ra: arithmetic mean roughness) is based on JISB0601. The mirror glossiness Gs (60 °) is based on JIS Z8741. L *, a *, b *, and C * are based on JIS Z8729, and the relationship of C * and a * and b * is represented by C * = (a * ² + b * ² ) ^1/2 . The hiding rate is based on JIS K5400.

Although the thickness of the base material 11 is 1-500 micrometers normally, Preferably it is about 3-300 micrometers, It can change suitably according to the use of the adhesive sheet 1.

The type of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer 12 is not particularly limited as long as the material can form the through holes 2 by laser ablation, but is not limited to acrylic, polyester, polyurethane, rubber, and silicone. Any of these may be sufficient. In addition, an adhesive may be any of emulsion type, a solvent type, or a non-solvent type, and may be any of a crosslinking type or a non-crosslinking type.

Although the thickness of the adhesive layer 12 is 1-300 micrometers normally, Preferably it is about 5-100 micrometers, According to the use of the adhesive sheet 1, it can change suitably.

The material of the release material 13 is not particularly limited, and for example, a film made of a resin such as polyethylene terephthalate, polypropylene, polyethylene or foamed film thereof, or paper such as glassine, coated paper, laminated paper, etc. The thing which peeled off by peeling agents, such as a fluorine type and a long chain alkyl group containing carbamate, can be used.

The thickness of the peeling material 13 is about 10-250 micrometers normally, Preferably it is about 20-200 micrometers. Moreover, the thickness of the peeling agent in the peeling material 13 is 0.05-5 micrometers normally, Preferably it is 0.1-3 micrometers.

In this embodiment, the hole diameter in the base material 11 and the adhesive layer 12 of the through-hole 2 is 0.1-120 micrometers, Preferably it is 1-100 micrometers, and the hole in the surface of the base material 11 The diameter is 0.1-40 탆, preferably 1-38 탆.

When the hole diameter of the through hole 2 satisfies the above condition, air or gas is easily released from the through hole 2, and the through hole 2 is not visible to the naked eye on the adhesive sheet surface 1A. In particular, the through hole 2 is formed by laser ablation, so that a melt called so-called dross adheres to the peripheral edge of the through hole 2, or thermal deformation occurs on the surface or inside of the adhesive sheet 1. Since or not, the shape of the through hole 2 is trimmed, even if the base material 11 is of high gloss, a high hiding rate, or a high brightness, the hole diameter of the through hole 2 is the above condition. If it satisfies, the through hole 2 is not visible to the naked eye.

Although the hole diameter of the through-hole 2 may be constant in the thickness direction of the adhesive sheet 1, and may change in the thickness direction of the adhesive sheet 1, the hole diameter of the through-hole 2 is the adhesive sheet 1 When it changes in the thickness direction of, as shown in FIG. 2, it is preferable that the hole diameter of the through hole 2 becomes gradually smaller from the adhesion surface 1B to the adhesion sheet surface 1A. As the hole diameter of the through hole 2 changes in this manner, the through hole 2 is hardly visible on the adhesive sheet surface 1A.

The hole density of the through hole 2 is 30-50,000 piece / 100 cm <2>, Preferably it is 100-10,000 piece / 100 cm <2>. If the hole density of the through hole 2 is less than 30/100 cm 2, air or gas is hard to escape, and if the hole density of the through hole 2 exceeds 50,000 / 100 cm 2, the mechanical strength of the pressure sensitive adhesive sheet 1 is reduced. Is lowered.

In addition, although the through hole 2 in the adhesive sheet 1 which concerns on this embodiment penetrates only the base material 11 and the adhesive layer 12, you may penetrate the peeling material 13. As shown in FIG.

In addition, although the adhesive sheet 1 which concerns on this embodiment is equipped with the peeling material 13, this invention is not limited to this, The peeling material 13 may not be required. In addition, the size, shape, etc. of the adhesive sheet 1 which concerns on this embodiment are not specifically limited. For example, the adhesive sheet 1 is a tape-shaped thing (adhesive tape) which consists only of the base material 11 and the adhesive layer 12, and may be what consists of a winding body wound by roll shape.

[Production of Adhesive Sheet]

An example of the manufacturing method of the adhesive sheet 1 which concerns on the said embodiment is demonstrated with reference to FIG.3 (a)-(d).

In this manufacturing method, as shown to FIG. 3 (a)-(b), the adhesive layer 12 is formed in the peeling process surface of the peeling material 13 first. In forming the pressure-sensitive adhesive layer 12, a pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer 12 and a coating agent further containing a solvent, if desired, are prepared, and a roll coater, knife coater, roll knife coater, air knife coater, die coater, What is necessary is just to apply | coat and dry to the peeling process surface of the peeling material 13 with coating machines, such as a bar coater, a gravure coater, and a curtain coater.

Next, as shown in FIG.3 (c), the base material 11 is crimped | bonded to the surface of the adhesive layer 12, and it is a laminated body which consists of the base material 11, the adhesive layer 12, and the peeling material 13. do. And as shown in FIG.3 (d), after peeling the peeling material 13 from the adhesive layer 12, as shown in FIG.3 (e), the base material 11 and the adhesive layer 12 are carried out. The laser ablation process is performed to the laminated body which forms, and the through hole 2 is formed. Finally, as shown in FIG.3 (f), the peeling material 13 is stuck to the adhesive layer 12 again.

Among laser processing, to form a hole in the carbon dioxide (C0 ₂₎ laser, a laser processing or the like by the YAG laser, a so-called laser heat process, the work by converting light energy into heat energy. Therefore, when such laser thermal processing is performed on the adhesive sheet, dross may adhere to the peripheral edge of the through hole 2, or heat deformation may occur on the surface or inside of the adhesive sheet. Or its periphery looks easy.

On the other hand, laser ablation processing sublimates the workpiece | work material which does not go through a liquid state, when the absorption wavelength of a material matches the wavelength of a laser, and forms a hole in a workpiece | work. Since an ordinary organic substance has a strong absorption wavelength in the ultraviolet region, when a laser having a wavelength corresponding to the absorption wavelength is irradiated to a workpiece made of an organic material, a chemical bond in the constituent molecules of the organic material is instantly detected in the laser irradiation portion. This breaks, the part disassembles and scatters, and a hole is formed in the workpiece.

Therefore, according to the laser ablation process, dross is not attached to the peripheral edge of the through hole 2, or thermal deformation does not occur in the surface or inside of the adhesive sheet 1, and the shape of the through hole 2 is kept in order. Although the base material 11 is high gloss, low hiding rate, or high brightness, the through hole 2 is not visible to the naked eye.

Laser ablation processing is preferably performed using an excimer laser or femtosecond laser. On the other hand, the excimer laser also includes an ultraviolet femtosecond laser. Specifically, laser ablation processing is performed using laser light having a wavelength of 150 to 352 nm and a pulse width of 2 to 300 ns, or laser light having a wavelength of 150 to 900 nm and a pulse width of 10 to 900 fs. It is desirable to.

Examples of the excimer laser include an XeCl excimer laser having an oscillation wavelength of 308 nm and a KrF excimer laser having an oscillation wavelength of 248 nm. Examples of a femtosecond laser include a Ti: Sapphire laser that oscillates at a center wavelength of about 800 nm. have.

In this manufacturing method, a laser is irradiated directly to the adhesive layer 12 from the adhesive layer 12 side. By performing laser ablation from the pressure-sensitive adhesive layer 12 in this way, even if a taper is formed in the through hole 2 as shown in FIG. 2, the hole diameter of the through hole 2 is equal to the release material 13 side. The direction on the substrate 11 side becomes smaller than that, and the hole diameter on the surface of the substrate 11 of the through hole 2 can be easily controlled within the above range (0.1 to 40 µm).

In addition, by peeling the peeling material 13 once and irradiating a laser directly to the adhesive layer 12 without interposing the peeling material 13, it is possible to shorten the laser irradiation time or reduce the output energy of the laser. It is possible to form the through hole 2 with high efficiency.

In this manufacturing method, what was formed by the casting method etc. using the process material as the base material 11 may be used, In this case, the process material is laminated | stacked on the surface of the base material 11. In addition, in this manufacturing method, the peelable protective sheet may be laminated | stacked on the surface of the base material (base material on which the process material is not laminated | stacked) 11 in arbitrary steps, before performing a laser ablation process. As a protective sheet, the well-known adhesive protective sheet etc. which consist of a base material and a re peelable adhesive layer can be used, for example.

In addition, in this manufacturing method, although the adhesive layer 12 is formed on the peeling material 13 and the adhesive layer 12 and the base material 11 which were formed are matched and pasted, this invention is not limited to this, The adhesive layer You may form (12) directly on the base material 11. Moreover, you may perform laser ablation process from the base material 11, the said process material, or the protective sheet side.

[Use of adhesive sheet]

When the adhesive sheet 1 is attached to the adherend, the release material 13 is peeled off from the adhesive layer 12, and the adhesive face 1B of the exposed adhesive layer 12 is brought into close contact with the adherend, thereby adhering. The sheet 1 is pressed against the adherend. At this time, the air between the adherend and the adhesive face 1B of the pressure-sensitive adhesive layer 12 escapes from the through hole 2 formed in the adhesive sheet 1 to the outside of the adhesive sheet surface 1A. Air does not roll in between the adhesive surfaces 1B, and it is prevented that air may accumulate. Although the air is curled up and the air is clogged, by recompressing the air pool or the air pool periphery including the air pool, the air escapes from the through hole 2 to the outside of the adhesive sheet surface 1A, whereby air The wages are lost. Such removal of air trapping is possible even after elapse of a long time from the sticking of the adhesive sheet 1.

After the adhesive sheet 1 is adhered to the adherend, even if gas is generated from the adherend or if the gas permeates the adherend, the gas is adhered to the surface of the adhesive sheet from the through hole 2 formed in the adhesive sheet 1. Since it escapes to the outside of 1A, air bubbles are prevented from occurring in the adhesive sheet 1.

As described above, in the pressure-sensitive adhesive sheet 1, the air holes and bubbles can be prevented or removed by the through-holes 2, but since the through-holes 2 are not visible to the naked eye, the appearance of the pressure-sensitive adhesive sheet 1 The silver does not differ significantly from that without the through hole 2 and is extremely good.

In addition, in the said adhesive sheet 1, even if a liquid adheres to the adhesive sheet 1 adhering to a to-be-adhered body, there is no adverse effect by the through-hole 2, and the external appearance of the adhesive sheet 1 is maintained favorable. .

EXAMPLE

Hereinafter, although an Example etc. demonstrate this invention further more concretely, the scope of the present invention is not limited to these Examples.

Example 1

Both sides of the quality paper were laminated with a polyethylene resin, and an acrylic solvent-type adhesive (manufactured by Lintec, PK) was applied to the peeling treatment surface of a release material (manufactured by Lintec, FPM-11, thickness: 175 µm), on which one side was coated with a silicone release agent. ) Was applied with a knife coater so that the thickness after drying was 30 μm, and dried at 90 ° C. for 1 minute. The pressure-sensitive adhesive layer thus formed had a surface roughness (Ra) of 0.266 µm, a mirror glossiness Gs (60 °) of 37.2%, and a saturation (C *) of the L * a * b * color system of 0.34 and lightness ( L *) was 26.56 and the black opaque base material (thickness: 100 micrometers) which consists of polyvinyl chloride resin of 99.9% of hiding rate was crimped | bonded and the laminated body of 3 layer structure was obtained.

In addition, the measurement of surface roughness Ra conformed to JISB0601, cut-off value (lambda) c = 0.8 mm, evaluation length ln = 10mm, and was performed using Mitsutoyo SV-3000S4 as a measuring apparatus. The mirror glossiness Gs (60 °) was in accordance with JIS Z8741, and was performed using a glossmeter VG2000 manufactured by Nippon Denshoku Industries Co., Ltd. as a measuring device. The measurement of chroma (C *) and brightness (L *) follows JIS Z8729, and is a simultaneous measurement method spectroscopic color difference meter (SQ-2000, manufactured by Nippon Denshoku Industries Co., Ltd.) as a measuring device, and a white plate (L). * = 92.47, a * = 0.61, b * = 2.90), using a C light source 2 ° field of view (C / 2) as a light source, it was carried out by reflection measurement. The hiding rate was in accordance with JIS K5400, and was performed using a SPEC TRAFLASH SF600 PLUS CTC (spectrophotometer) manufactured by datacolor international (DCI) as a measuring device. These measuring methods are the same below.

The peeling material is peeled off from the laminate, and a laser ablation process is performed on the laminate from the pressure-sensitive adhesive layer side by an excimer laser under the following conditions, and the hole diameter on the surface of the substrate is about 30 µm and the hole diameter on the adhesive surface is about. A through hole of 60 mu m (the hole diameter at the adhesive face was the maximum diameter) was formed at a hole density of 2,500 / 100 cm &lt; 2 &gt;. And the said peeling material was crimped | bonded to the adhesive layer again, and this was made into the adhesive sheet.

Laser by excimer laser Ablation  Processing condition

Rash Medium: KrF

Oscillation Wavelength: 248nm

Pulse Width: 16ns

Frequency: 197Hz

Example 2

Using a polyethylene terephthalate film (thickness: 50 µm) obtained by peeling one surface with an alkyd release agent as a process material, the surface roughness (Ra) was 0.031 µm by the casting method, and the mirror surface glossiness Gs (60 °). Is a black opaque substrate composed of a polyurethane resin having 91.2%, a saturation (C *) of 0.21, a brightness (L *) of 24.69, and a hiding rate of 99.7% in a L * a * b * color system (thickness: 100 Μm) was formed.

On the other hand, in the same manner as in Example 1, an adhesive layer was formed on the release material, and both were pressed to obtain a laminate having a four-layer structure such that the pressure-sensitive adhesive layer and the surface other than the process material of the substrate with the process material were brought into close contact with each other.

The peeling material was peeled off from the obtained laminate, and laser ablation was performed on the laminate from the pressure-sensitive adhesive layer side in the same manner as in Example 1, and the hole diameter on the surface of the substrate was about 25 µm and the hole diameter on the adhesive surface was about 55. A through hole having a 占 퐉 (the hole diameter at the adhesive surface is the maximum diameter) was formed at a hole density of 2,500 / 100 cm 2. And the said peeling material was crimped | bonded to the adhesive layer again, and this was made into the adhesive sheet.

Example 3

As a base material, surface roughness (Ra) is 0.373 micrometers, the mirror glossiness Gs (60 degrees) is 24.8%, the saturation (C *) is 0.34 in the L * a * b * color system, and the brightness (L *) is 27.39. And a black opaque substrate (thickness: 100 µm) made of an olefinic thermoplastic elastomer having a concealment ratio of 99.3% and a colorless transparent acrylic coat (thickness: 5 µm) on the surface thereof, An adhesive sheet was produced in the same manner as in Example 1 except that the hole diameter was about 25 μm and the hole diameter on the adhesive face was about 65 μm.

Example 4

As the substrate, a colorless transparent substrate (thickness: 25 µm) made of polyethylene terephthalate having a surface roughness Ra of 0.035 µm, a mirror glossiness Gs (60 °) of 80.4%, and a hiding rate of 8.0% was used. An adhesive sheet was produced in the same manner as in Example 1 except that the hole diameter on the substrate surface of the through hole was about 15 μm and the hole diameter on the adhesive face was about 45 μm.

Example 5

The surface roughness (Ra) is 0.216 µm, the mirror glossiness Gs (60 °) is 28.5%, the saturation (C *) is 2.08, the brightness (L *) is 65.21 in the L * a * b * colorimetric system, and concealment. A gray opaque substrate (thickness: 55 µm) made of a polyvinyl chloride resin having a rate of 97.3% was formed on the process material in the same manner as in Example 2.

Using the base material with a process material obtained as mentioned above, the adhesive sheet was produced like Example 2 except having made the hole diameter in the adhesive surface of a through hole into about 60 micrometers.

Example 6

In the same manner as in Example 2, a laminate having a four-layer structure was produced, and the release material was peeled off from the laminate thus obtained. The laminate was subjected to laser ablation with a femtosecond laser under the following conditions from the pressure-sensitive adhesive layer side, The through hole (the hole diameter at the adhered surface is the maximum diameter) of about 10 mu m in the hole diameter and about 30 mu m in the adhesive surface was formed at a hole density of 2,500 / 100 cm &lt; 2 &gt;. And the said peeling material was crimped | bonded to the adhesive layer again, and this was made into the adhesive sheet.

Femtosecond  Laser by laser Ablation  Condition of processing

Rash Medium: Ti: Sapphire

Oscillation Wavelength: 800nm

Pulse Width: 150fs

Frequency: 1 kHz

Comparative Example 1

Instead of laser ablation processing with an excimer laser, laser thermal processing with a C0 ₂ laser under the following conditions is carried out so that the hole diameter on the substrate surface of the through hole is about 35 µm and the hole diameter on the adhesive surface is about 90 µm. A pressure-sensitive adhesive sheet was produced in the same manner as in Example 2 except for the above.

C0 ₂ Laser by laser Thermal processing  Condition

Rash Medium: C0 ₂

Oscillation Wavelength: 9.4㎛

Pulse width: 40㎲

Frequency: 1 kHz

Comparative Example 2

C0 ₂ instead of laser ablation processing by excimer laser The laser thermal processing (the condition is the same as that of Comparative Example 1) by laser, except that the hole diameter on the substrate surface of the through hole is about 35 μm and the hole diameter on the adhesive surface is about 85 μm. In the same manner as in 4, an adhesive sheet was produced.

[Test Example]

With respect to the pressure-sensitive adhesive sheets obtained in Examples and Comparative Examples, an air pool disappearance test and a hole visibility test were performed as follows. The results are shown in Table 1.

Air stiffness test: cut to 50 mm x 50 mm, and with the process material, the process material is peeled off, and the adhesive sheet from which the release material is peeled off is a melamine having a partial spherical recess having a diameter of 15 mm and a maximum depth of 1 mm. It was pasted to a paint plate (there is an air pool between the recess and the adhesive sheet), and the adhesive sheet was pressed with a skid to check whether the air pool could be removed. As a result, the adhesive sheet followed the recessed part of the melamine coated plate and the air clot was removed, and the adhesive sheet did not follow the recessed part of the melamine coated plate, and the air pool was not removed (including the air pool remaining at least). ) Is indicated by ×.

Hole Visibility Test: Cut to 30 mm x 30 mm, and with the process material, peel off the process material, attach the peeled-off adhesive sheet to the white melamine paint plate, and visually penetrate from the surface of the adhesive sheet under indoor fluorescent lamps. It was examined whether the presence of holes could be recognized. On the other hand, the distance from an eye to an adhesive sheet was made into about 30 cm, and the angle which sees an adhesive sheet was often changed. As a result,? Indicates that the presence of the through hole was not recognized, and x indicates that the presence of the through hole was recognized.

TABLE 1

Air pool burnout test Hole visibility check Example 1 ○ ○ Example 2 ○ ○ Example 3 ○ ○ Example 4 ○ ○ Example 5 ○ ○ Example 6 ○ ○ Comparative Example 1 ○ × Comparative Example 2 ○ ×

In the pressure-sensitive adhesive sheets (Examples 1 to 6) in which the through holes were formed by laser ablation, there was no dross or thermal deformation, and the presence of the through holes could not be recognized, and therefore the appearance was extremely good. On the other hand, in the pressure-sensitive adhesive sheets (Comparative Examples 1 and 2) in which the through holes were formed by laser heat processing, the presence of the through holes was recognized by dross, heat deformation, and other thermal effects, and the appearance was damaged.

In general, the present invention is a case where air sticking and bubbles are likely to occur in the pressure sensitive adhesive sheet, for example, when the area of the pressure sensitive adhesive sheet is large or when gas is generated from the adherend. It can be used preferably for the adhesive sheet required.

Claims (8)

As an adhesive sheet which has at least a base material and an adhesive layer, and the through-hole which penetrates from one surface to another surface is formed in multiple numbers, The hole diameter of the said through hole in the said base material and the adhesive layer is 0.1-120 micrometers, The diameter of the through hole in the surface of the substrate is 0.1 to 40㎛, The hole density of the through hole is 30 to 50,000 pieces / 100 cm 2, The through hole is formed by a laser ablation process, characterized in that the adhesive sheet. The method of claim 1, The hole diameter of the said through hole becomes small gradually from the adhesive sheet back surface to the adhesive sheet surface, The adhesive sheet characterized by the above-mentioned. Laser ablation processing is carried out on the pressure sensitive adhesive sheet having at least the base material and the pressure sensitive adhesive layer, and the through hole having a hole diameter of 0.1 to 120 μm in the base material and the pressure sensitive adhesive layer and a hole diameter of 0.1 to 40 μm on the surface of the base material. The hole is formed by the hole density of 30-50,000 piece / 100 cm <2>, The adhesive sheet manufacturing method characterized by the above-mentioned. The method of claim 3, The wavelength of the laser beam used for the said laser ablation process is 150-352 nm, and pulse width is 2-300 ns, The adhesive sheet manufacturing method characterized by the above-mentioned. The method of claim 3, The laser ablation process is performed using an excimer laser, The adhesive sheet manufacturing method characterized by the above-mentioned. The method of claim 3, The wavelength of the laser beam used for the said laser ablation process is 150-900 nm, and pulse width is 10-900fs, The adhesive sheet manufacturing method characterized by the above-mentioned. The method of claim 3, The laser ablation process is performed using a femtosecond laser, The adhesive sheet manufacturing method characterized by the above-mentioned. The method according to any one of claims 3 to 7, The said laser ablation process is performed from the adhesive sheet back surface side, The adhesive sheet manufacturing method characterized by the above-mentioned.

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