CN101248150A - Pressure-sensitive adhesive sheet - Google Patents
Pressure-sensitive adhesive sheet Download PDFInfo
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- CN101248150A CN101248150A CNA200680030868XA CN200680030868A CN101248150A CN 101248150 A CN101248150 A CN 101248150A CN A200680030868X A CNA200680030868X A CN A200680030868XA CN 200680030868 A CN200680030868 A CN 200680030868A CN 101248150 A CN101248150 A CN 101248150A
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- sensitive adhesive
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- adhesive sheets
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Abstract
In a pressure-sensitive adhesive sheet 1 that comprises a base material 11 and a pressure-sensitive adhesive layer 12, and has formed therein by thermal processing a plurality of through holes 2 passing through one surface to the other surface of the pressure-sensitive adhesive sheet 1, as the base material 11, one is used for which, upon heating at a heating rate of 20 DEG C/min under a nitrogen atmosphere, the temperature at a thermal decomposition peak where the mass reduction is greatest is not more than 450 DEG C, or the difference between the temperature at the thermal decomposition peak and the temperature at a melting peak is not more than 250 DEG C. According to this pressure-sensitive adhesive sheet 1, the appearance of the pressure-sensitive adhesive sheet 1 is not marred by the through holes 2 formed by the thermal processing.
Description
Technical field
The present invention relates to pressure-sensitive adhesive sheets, utilize it can prevent or eliminate the delay and the foaming of air.
Background technology
When adhering to pressure-sensitive adhesive sheets on the adherend, between adherend and pressure sensitive adhesive surface, air entrapment can occur, thereby make the outward appearance of pressure-sensitive adhesive sheets destroy with hand.Have at pressure-sensitive adhesive sheets under the situation of big area, the delay of this air especially is easy to take place.
In addition, the resin material such as acrylic resin, ABS resin, polystyrene resin or polycarbonate resin when heating or even the situation that not have to heat under can discharge gas; When pressure-sensitive adhesive sheets being adhered on the adherend of making by this resin material, can on pressure-sensitive adhesive sheets, occur bubbling, this is because discharge gas from adherend.
In order to address this problem, open among the No.2004/061031 the international patent application spy, pressure-sensitive adhesive sheets has been proposed, wherein forming void density is 30-50,000/100cm
2The through hole of diameter 0.1-300 micron.According to this pressure-sensitive adhesive sheets, air on the pressure sensitive adhesive face side or gas can escape into the pressure-sensitive adhesive sheets face side from this through hole, and and then can prevent the air trapping or the foaming of pressure-sensitive adhesive sheets.
Disclosure of the Invention
The problem to be solved in the present invention
In above-mentioned pressure-sensitive adhesive sheets, can use the working method of laser punching, form through hole.In the working method of laser punching, the carbon dioxide laser processing method is and abrasion processing method opposite so-called LASER HEAT processing method, and this method is wherein by by heating, and the method for decomposing material is carried out method for processing.Under the situation that base mateiral is made by olefinic material, can enlarge the internal diameter of through hole by this hot-work method.If enlarge the internal diameter of through hole in such a way, but then, the around openings of each through hole causes the outward appearance of deterioration pressure-sensitive adhesive sheets because of caving inward, with after adhering to pressure-sensitive adhesive sheets on the adherend, under the liquid such as water or gasoline is attached to situation on the gained pressure-sensitive adhesive sheets, this liquid can enter in the through hole, thereby cause throughhole portions (part around through hole) swelling etc., the result destroys the outward appearance of pressure-sensitive adhesive sheets.
Situation design the present invention in view of the above; The purpose of this invention is to provide the pressure-sensitive adhesive sheets that forms through hole by the hot-work method within it, utilize it can prevent or eliminate the delay and the foaming of air, and do not have destruction the pressure-sensitive adhesive sheets outward appearance.
The mode of dealing with problems
To achieve these goals, at first, the invention provides a kind of pressure-sensitive adhesive sheets, it comprises base mateiral and pressure-sensitive adhesive layer, wherein form pressure-sensitive adhesive sheets within it by the hot-work method, the surface that a plurality of through holes pass pressure-sensitive adhesive sheets arrives another surface, and this pressure-sensitive adhesive sheets is characterised in that: in case heat base mateiral under the rate of heating of 20 ℃/min under nitrogen atmosphere, the thermolysis peak temperature when downgrade is maximum is not more than 450 ℃ (inventions 1).
Second, the invention provides a kind of pressure-sensitive adhesive sheets, it comprises base mateiral and pressure-sensitive adhesive layer, wherein form pressure-sensitive adhesive sheets within it by the hot-work method, the surface that a plurality of through holes pass pressure-sensitive adhesive sheets arrives another surface, this pressure-sensitive adhesive sheets is characterised in that: in case heat base mateiral under the rate of heating of 20 ℃/min under nitrogen atmosphere, the thermolysis peak temperature when downgrade is maximum and the difference of melting peak temperature are not more than 250 ℃ (inventions 2).
The 3rd, the invention provides a kind of pressure-sensitive adhesive sheets, it comprises base mateiral and pressure-sensitive adhesive layer, wherein form pressure-sensitive adhesive sheets within it by the hot-work method, the surface that a plurality of through holes pass pressure-sensitive adhesive sheets arrives another surface, this pressure-sensitive adhesive sheets is characterised in that: in case heat base mateiral under the rate of heating of 20 ℃/min under nitrogen atmosphere, thermolysis peak temperature when downgrade is maximum is not more than 450 ℃, with exist under the situation of melting peak, the difference of thermolysis peak temperature and fusion peak temperature is not more than 250 ℃ (inventions 3).
Attention is in specification sheets of the present invention, and " sheet material " is regarded as comprising the notion of film, and " film " is regarded as comprising the notion of sheet material.
For the base mateiral that satisfies the above condition, when forming through hole, there is cause thermal damage seldom by the hot-work method, therefore do not enlarge the internal diameter of through hole.That is to say,, prevented that the through hole internal diameter from enlarging the appearance degradation of the pressure-sensitive adhesive sheets that causes according to foregoing invention (invention 1-3).
Under the situation of foregoing invention (invention 1-3), the preferred LASER HEAT processing method of hot-work (invention 4).Yet, under the situation of foregoing invention (invention 4), employed laser apparatus carbon dioxide laser (invention 5) preferably in LASER HEAT processing.
Under the situation of foregoing invention (invention 1-5), at the diameter of base mateiral surface through hole preferably less than the through-hole diameter (invention 6) of pressure sensitive adhesive surface in pressure-sensitive adhesive layer.By changing the diameter of through hole in such a way, become so unobvious at base mateiral surface through hole, so the outward appearance of pressure-sensitive adhesive sheets becomes better.
The invention effect
According to the present invention, obtain to form the pressure-sensitive adhesive sheets of through hole within it by the hot-work method, utilize it can prevent or eliminate the delay and the foaming of air, and do not have destruction the pressure-sensitive adhesive sheets outward appearance.
The accompanying drawing summary
Fig. 1 is the cross sectional view of pressure-sensitive adhesive sheets according to an embodiment of the invention;
Fig. 2 is the amplification cross sectional view of pressure-sensitive adhesive sheets part, and it shows the through hole with enlarged inner diameter;
Fig. 3 is made up of following cross sectional view, and described cross sectional view shows according to one embodiment of the invention, makes an example of the method for pressure-sensitive adhesive sheets;
Fig. 4 is the TG/DTA chart of measuring result simultaneously that shows the base mateiral of embodiment 1;
Fig. 5 is the TG/DTA chart of measuring result simultaneously that shows the base mateiral of embodiment 2;
Fig. 6 is the TG/DTA chart of measuring result simultaneously that shows the base mateiral of embodiment 3;
Fig. 7 is the TG/DTA chart of measuring result simultaneously that shows the base mateiral of embodiment 4;
Fig. 8 is the TG/DTA chart of measuring result simultaneously that shows the base mateiral of embodiment 5;
Fig. 9 is the TG/DTA chart of measuring result simultaneously that shows the base mateiral of embodiment 6; With
Figure 10 is the TG/DTA chart of measuring result simultaneously that shows the base mateiral of Comparative Examples 1 and 2.
The explanation of reference marker
1: pressure-sensitive adhesive sheets
11: base mateiral
12: pressure-sensitive adhesive layer
13: release liner
1A: base mateiral surface
1B: pressure sensitive adhesive surface
2: through hole
Implement optimal mode of the present invention
It below is the explanation of embodiment of the present invention.
[pressure-sensitive adhesive sheets]
Fig. 1 is the cross sectional view of pressure-sensitive adhesive sheets according to an embodiment of the invention.
As shown in Figure 1, pressure-sensitive adhesive sheets 1 comprises that base mateiral 11, pressure-sensitive adhesive layer 12 and release liner 13 and are laminated on another layer according to embodiments of the present invention.Yet, note when using pressure-sensitive adhesive sheets 1, peeling off release liner 13.
Form a plurality of through holes 2 in pressure-sensitive adhesive sheets 1, described a plurality of through holes 2 penetrate base mateiral 11 and pressure-sensitive adhesive layer 12 also and then from base mateiral surface 1A passes through to arrive pressure sensitive adhesive surface 1B.When using pressure-sensitive adhesive sheets 1, air between the 1B of the pressure sensitive adhesive surface of adherend and pressure-sensitive adhesive layer 12 and the gas that discharges from adherend escape into from these through holes 2 on the outside of base mateiral surface 1A, therefore as described below, can prevent or eliminate air trapping and foaming.
In case under nitrogen atmosphere, when heating under the rate of heating of 20 ℃/min, base mateiral 11 must satisfy one of the following:
Thermolysis peak temperature when (a) downgrade is maximum is not more than 450 ℃;
Thermolysis peak temperature when (b) downgrade is maximum and the difference of melting peak temperature are not more than 250 ℃; Or
Thermolysis peak temperature when (c) downgrade is maximum is not more than 450 ℃ and exist under the situation of melting peak, and the difference of thermolysis peak temperature and fusion peak temperature is not more than 250 ℃.
For base mateiral 11, poor by aforesaid low heat decomposition temperature and/or little heat decomposition temperature and melt temperature, when by the hot-work method, especially LASER HEAT processing method, when more specifically the carbon dioxide laser processing method forms through hole 2, to the cause thermal damage that base mateiral 11 exists seldom, therefore do not enlarge the internal diameter of through hole 2.The problem that does not have appearance to cause by the internal diameter that enlarges through hole 2, i.e. following problems for example: because of the cave inward appearance degradation of the pressure-sensitive adhesive sheets 1 that causes of the around openings of each through hole 2, with after adhering to pressure-sensitive adhesive sheets 1 on the adherend, under the liquid such as water or gasoline is attached to situation on the pressure-sensitive adhesive sheets 1, this liquid enters in the through hole 2, thereby cause throughhole portions (part around through hole) swelling etc., the result destroys the outward appearance of pressure-sensitive adhesive sheets.
Attention provision " downgrade maximum " is intended being defined under the situation that has a plurality of thermolysis peak values (referring to Fig. 4-10), corresponding to the temperature of maximum heat decomposition temperature.In addition, exist under the situation of a plurality of melting peaks, utilizing the melting peak when minimum temperature.This is because at first begin fusion under this melting peak temperature.
Herein, the expansion of the internal diameter of through hole 2 is meant as shown in Figure 2 basically, the maximum diameter d of through hole 2 in base mateiral 11
2Greater than diameter d at 1A place, base mateiral surface through hole 2
1, and the remarkable in addition diameter d greater than the through hole at the interface 2 between base mateiral 11 and pressure-sensitive adhesive layer 12
3, but not necessarily be limited to corresponding above-mentioned condition, think any variation that comprises through hole 2 diameters that wherein produce above-described problem.If the internal diameter of through hole 2 enlarges, then with the diameter d of through hole 2
2Consistently, the around openings of through hole 2 tend to cave inward (referring to Fig. 2).
Under the thermolysis peak value, the preferred 300-440 of the said temperature of base mateiral 11 ℃, and the difference of thermolysis peak temperature and fusion peak temperature preferably is not more than 235 ℃.
As the material of base mateiral 11, the material with above-described Thermal Decomposition Characteristics is preferably selected from material known; The example of this material is film or the foam films that is formed from a resin, the example of resin has polyester, the polyester thermoplastic elastomer, urethane, the polyurethanes thermoplastic elastomer, polystyrene, polystyrene-type thermoplastic elastomers, any various modification, for example epoxidised thermoplastic elastomer, polyvinyl chloride, acrylate copolymer, vinylformic acid-urethane copolymers, vinylformic acid-carboxylamine ester graft copolymer, or acroleic acid polyurethane, the blend of acrylic resin and urethane resin for example, or the resin of above-mentioned laminated film and so on, the perhaps resin molding such as composed paper.On the other hand, for by polyolefine, for example polyethylene or polypropylene, or the resin molding made of polyolefins thermoplastic elastomer, in a single day heat decomposition temperature is high and melt temperature is low, therefore uses laser beam irradiation, then material fusion before experience thermolysis and dispersion, so the internal diameter of through hole enlarges.
As the material in the base mateiral 11, in the middle of above-mentioned resin molding, consider from environmental, the resin molding of making by not chloride bond thing in its main chain, especially by polyester, the polyester thermoplastic elastomer, urethane, the polyurethanes thermoplastic elastomer, polystyrene, polystyrene-type thermoplastic elastomers, any various modification, for example epoxidised thermoplastic elastomer, acrylate copolymer, vinylformic acid-urethane copolymers, vinylformic acid-carboxylamine ester graft copolymer, or acroleic acid polyurethane, for example the resin molding made of the blend of acrylic resin and urethane resin is more preferred.
In addition, material as base mateiral 11, for above-mentioned resin molding, modulus in tension (Young's modulus) is the resin molding of 100-2500MPa, particularly by polybutylene terephthalate, the polyester thermoplastic elastomer, urethane, the polyurethanes thermoplastic elastomer, polystyrene, polystyrene-type thermoplastic elastomers, any various modification, for example epoxidised thermoplastic elastomer, polyvinyl chloride, acrylate copolymer, vinylformic acid-urethane copolymers, vinylformic acid-carboxylamine ester graft copolymer, or acroleic acid polyurethane, the resin molding made of the blend of acrylic resin and urethane resin for example, the resin molding of modulus in tension in above-mentioned scope is preferred.Modulus in tension is easy to handle for the resin molding of 100MPa at least, and modulus in tension is not more than the resin molding of 2500MPa and has high ability and follow curvilinear surface, therefore is suitable for going up and using having the adherend of curvilinear surface (adherend).
That is to say, as the material in the base mateiral 11, by polybutylene terephthalate, polyester thermoplastic elastomer, urethane, polyurethanes thermoplastic elastomer, polystyrene, polystyrene-type thermoplastic elastomers, any various modifications, for example epoxidised thermoplastic elastomer, acrylate copolymer, vinylformic acid-urethane copolymers, vinylformic acid-carboxylamine ester graft copolymer, or acroleic acid polyurethane, for example the resin molding made of the blend of acrylic resin and urethane resin is preferred especially.
Notice that above-mentioned resin molding can contain any various additive, for example mineral filler, organic filler and uv-absorbing agent.In addition, resin molding can be to use process materials, by the resin molding of casting method or similar approach formation.In addition, as long as the shape to through hole 2 does not have negative impact, then the surface of resin molding can have the ornament layer that forms by the method such as printing, japanning, transfer on the transfer sheet, vapour deposition or sputter thereon, the adhesion promotion coating that perhaps can have formation thereon is for forming this ornament layer, the perhaps coating such as gloss is regulated coating, perhaps can have thereon the coating that forms, for example hard coat, anti-pollution coating, surfaceness/specular gloss coating of regulating coating or giving anti-Weather.In addition, can on whole material, perhaps can on the only part of material, form this ornament layer or coating.
The thickness of base mateiral 11 is generally about 1-500 micron, preferred 3-300 micron, but can optionally change according to the purposes of pressure-sensitive adhesive sheets 1.
Type to the pressure-sensitive adhesive sheets that constitutes pressure-sensitive adhesive layer 12 is not particularly limited, as long as this pressure sensitive adhesive is the pressure sensitive adhesive that through hole 2 can form within it; This pressure sensitive adhesive can be any acrylic-type, polyester type, urethane type, rubber type, siloxanes type or analogue.In addition, pressure sensitive adhesive can be the type of any emulsion type, type of solvent or less solvent and can be or crosslink type or non-crosslinked type.
The thickness of pressure-sensitive adhesive layer 12 is generally the 1-300 micron, preferred 5-100 micron, but can optionally change according to the purposes of pressure-sensitive adhesive sheets 1.
Material to release liner 13 is not particularly limited, but can use by the resin such as polyethylene terephthalate, polypropylene or polyethylene, perhaps use stripper, for example the stripper of the stripper of siloxanes type, fluorine type or the carbamate that contains chain alkyl carry out film or the foam films that the paper such as glassine paper, enamelled paper or laminated paper that lift-off processing crosses is made.
The thickness of release liner 13 is generally about 10-250 micron, preferably about 20-200 micron.In addition, the thickness of the stripper in release liner 13 is generally the 0.05-5 micron, preferred 0.1-3 micron.
Hot-work method by the following stated forms the through hole 2 that penetrates base mateiral 11 and pressure-sensitive adhesive layer 12.
Diameter at base mateiral 11 and pressure-sensitive adhesive layer 12 inner via holes 2 is preferably the 0.1-300 micron, especially preferred 0.5-150 micron.The diameter of the through hole 2 by satisfying these conditions, air or gas can easily be escaped from through hole 2, but with the naked eye are not easy to find out through hole 2 on the 1A of base mateiral surface, so this pressure-sensitive adhesive sheets 1 has good outward appearance.
The diameter of through hole 2 can be constant on the thickness direction of pressure-sensitive adhesive sheets 1, perhaps on the thickness direction of pressure-sensitive adhesive sheets 1, can change, but under the situation of the vary in diameter of through hole 2 on the thickness direction of pressure-sensitive adhesive sheets 1, the diameter of the through hole 2 preferably positive 1A from the back 1B of pressure-sensitive adhesive sheets to pressure-sensitive adhesive sheets reduces gradually.By changing the diameter of through hole 2 in such a way, at the positive 1A of pressure-sensitive adhesive sheets place, through hole 2 is so not remarkable, so the outward appearance of pressure-sensitive adhesive sheets 1 is better.
The preferred 30-50 of hole density of through hole 2,000/100cm
2, especially preferred 100-10,000/100cm
2If the hole density of through hole 2 is less than 30/100cm
2, then air may be difficult to escape, and if the hole density of through hole 2 greater than 50,000/100cm
2, then the physical strength of pressure-sensitive adhesive sheets 1 may descend.
Only penetrate base mateiral 11 and pressure-sensitive adhesive layer 12 at pressure-sensitive adhesive sheets 1 inner via hole 2 according to embodiments of the present invention, but the also penetrable release liner 13 of taking off of through hole 2.
In addition, pressure-sensitive adhesive sheets 1 has release liner 13 according to embodiments of the present invention, but the present invention to it without limits; Pressure-sensitive adhesive sheets 1 can not have release liner 13.In addition, the size of pressure-sensitive adhesive sheets 1 according to embodiments of the present invention, shape or the like are not particularly limited.For example, pressure-sensitive adhesive sheets 1 can be only to contain the adhesive tape (pressure sensitive adhesive tape) of base mateiral 11 and pressure-sensitive adhesive layer 12 and also can twine rolling.
[manufacturing pressure-sensitive adhesive sheets]
With reference to figure 3 (a)-(f), the example of manufacturing according to the method for the pressure-sensitive adhesive sheets 1 of above-mentioned embodiment described.
In manufacture method of the present invention, at first,, on the surface that the lift-off processing of release liner 13 is crossed, form pressure-sensitive adhesive layer 12 as Fig. 3 (a) with (b).Can contain the pressure sensitive adhesive (it constitutes pressure-sensitive adhesive layer 12) and the coating agent of solvent optionally by preparation, use spreader, for example roller coat device, cutter are coated with machine, the roller cutter is coated with machine (roll knife coater), air-blade type coating machine, die coater, scraping strip coating machine, grooved roll coating machine or curtain coater, on the surface that the lift-off processing of release liner 13 is crossed, apply the coating agent, and dry, form pressure-sensitive adhesive layer 12.
Next, shown in Fig. 3 (c), base mateiral 11 is superimposed upon on pressure-sensitive adhesive layer 12 surfaces, and then obtains to contain the layered product of base mateiral 11, pressure-sensitive adhesive layer 12 and release liner 13.Then, shown in Fig. 3 (d), peel off release liner 13 from pressure-sensitive adhesive layer 12, then shown in Fig. 3 (e), form through hole 2 in the layered product that contains base mateiral 11 and pressure-sensitive adhesive layer 12, shown in Fig. 3 (f), release liner 13 once more superposes on pressure-sensitive adhesive layer 12 then.
Carry out the formation of through hole 2 by the hot-work method.As the type of this hot-work method, have LASER HEAT processing method, the hot skill of handling needles, fusion perforation method or the like, but in the middle of these, preferred LASER HEAT processing method is because can easily form the fine through hole with good air escape capability under required hole density.The example of employed laser type comprises carbonic acid gas (CO in the LASER HEAT processing method
2) laser apparatus, TEA-CO
2Laser apparatus, YAG laser apparatus, UV-YAG laser apparatus, YVO
4Laser apparatus and YLF Lasers device, but in the middle of these, consider the preferably carbon dioxide laser apparatus in equal angles such as production efficiency, costs.
For the processing of laser apparatus pore-forming, exist to excite (burst) processing method (excitation mode), wherein use position of laser beam continuous irradiation, up to forming a through hole 2; With cyclic process method (circulation pattern), wherein with laser beam a plurality of positions of irradiation according to the order of sequence, so that be formed uniformly a plurality of through holes 2.The former is to reduce the influence of heating to goods to be processed at the superiority superior and latter aspect thermo-efficiency.Can use any of these pattern to carry out the LASER HEAT processing method.
When carrying out the LASER HEAT processing method, preferably with laser beam directly from pressure-sensitive adhesive layer 12 side irradiation pressure-sensitive adhesive layers 12.By in such a way, carry out LASER HEAT processing from pressure-sensitive adhesive layer 12, even through hole 2 becomes cone, the diameter that can make through hole 2 on base mateiral 11 sides less than pressure-sensitive adhesive layer 12 sides.In addition, by peel off release liner 13 and with the direct irradiation pressure-sensitive adhesive layer 12 of laser beam temporarily, the opening of each through hole 2 does not have to cause broadening because of the hot-melt substance from release liner 13 in pressure-sensitive adhesive layer 12, so precision height of diameter and hole density, with therefore can form the through hole 2 that water or analogue are not easy to enter, entering of they can have negative impact to pressure-sensitive adhesive sheets 1.In addition, when with laser beam irradiation pressure-sensitive adhesive layer 12, do not exist therebetween, can shorten the laser beam irradiation time, perhaps can reduce laser output energy by making release liner 13.If laser output energy decreases then can reduce the negative impact to pressure-sensitive adhesive layer 12 and base mateiral 11, and can form and have seldom melt substance (burr) and the thermal distortion through hole 2 of the uniform shapes of (they cause because of the heat from laser beam) partly seldom.
Using process materials to be used as under the situation of base mateiral 11, can be laminated at this process materials and carry out LASER HEAT processing under the base mateiral 11 lip-deep states by the base mateiral 11 that casting method or similar approach form.In addition, before carrying out the LASER HEAT processing method, can in the required stage, strippable protection sheet material be laminated on the surface of base mateiral 11 (not having the laminating technology material thereon).As the protection sheet material, the known resin molding or the analogue of removable pressure-sensitive adhesive layer that for example can use thereon lamination.
Forming by the LASER HEAT processing method under the situation of through hole 2; melt substance can be attached to the around openings of through hole 2; but by being present in base mateiral 11 lip-deep process materials or protection sheet material; melt substance will be attached on process materials or the protection sheet material; rather than on the base mateiral 11, therefore can keep the outward appearance of pressure-sensitive adhesive sheets 1 preferably.
Attention is in above-mentioned manufacture method, on release liner 13, form pressure-sensitive adhesive layer 12, then base mateiral 11 is superimposed upon on the formed pressure-sensitive adhesive layer 12, but in the present invention without limits, for example can directly on base mateiral 11, forms pressure-sensitive adhesive layer 12 it.In addition, LASER HEAT processing can be under the laminated state of release liner 13, carried out thereon, in addition, the irradiation of laser beam can be adopted from base mateiral 11 sides.
[purposes of pressure-sensitive adhesive sheets]
When adhering to pressure-sensitive adhesive sheets on the adherend, at first peel off release liner 13 from pressure-sensitive adhesive layer 12.
Next, the pressure sensitive adhesive surface 1B in the pressure-sensitive adhesive layer 12 of exposure is closely contacted with adherend, on adherend, push pressure-sensitive adhesive sheets 1 then.This moment, escape into the outside of base mateiral surface 1A the through hole 2 that air between the pressure sensitive adhesive surface 1B in adherend and pressure-sensitive adhesive layer 12 forms in pressure-sensitive adhesive sheets 1, therefore air tends to not be captured between adherend and the pressure sensitive adhesive surface 1B, has promptly prevented the air trapping generation.Even air is hunted down, air trapping has taken place in the result, then part by pushing air trapping again or encirclement contain the air entrapment part of peripheral part of air trapping part, can make air escape into the outside of base mateiral surface 1A from through hole 2, thereby eliminate air entrapment.Even after adhering on pressure-sensitive adhesive sheets 1, after the long-time section of past, the elimination of this air entrapment also is possible.
In addition, even after adhering to pressure-sensitive adhesive sheets 1 on the adherend, when gas discharged from adherend, the through hole 2 that this gas will form in pressure-sensitive adhesive sheets 1 escaped into the outside of base mateiral surface 1A, thereby prevented that pressure-sensitive adhesive sheets 1 from bubbling.
Adopt above-mentioned pressure-sensitive adhesive sheets 1, there is not the expansion of the internal diameter of through hole 2, with the appearance degradation that does not therefore have opening because of each through hole 2 to change to cave inward the pressure-sensitive adhesive sheets 1 that causes, this is external adhere to pressure-sensitive adhesive sheets 1 on the adherend after, under the liquid such as water or gasoline is attached to situation on the gained pressure-sensitive adhesive sheets 1, this liquid does not enter in the through hole 2, therefore there is not swelling in throughhole portions (surrounding through hole part on every side), therefore can keep pressure-sensitive adhesive sheets 1 good surface appearance.
Embodiment
Below be to more detailed description of the present invention by embodiment etc.; Yet scope of the present invention is not limited to these embodiment or the like.
[embodiment 1]
Use cutter to be coated with machine, apply vinylformic acid solvent based pressure sensitive adhesive (by LintecCorporation, PK makes) coating, so that after drying, laminated polyethylene resin and the surface that a surface uses the lift-off processing of the release liner that the lift-off processing of type siloxane stripper obtains to cross (made by LintecCorporation on by two surfaces at no timber paper, FPM-11,175 microns of thickness) thickness on is 30 microns and carried out drying 1 minute under 90 ℃.(make by the resin molding that the polyester thermoplastic elastomer is made by Kurabo Industries Ltd.; ES9300BK; thickness: 100 microns) be superimposed upon on the pressure-sensitive adhesive layer of formation like this as base mateiral; and the protection sheet material that will have a removable pressure-sensitive adhesive layer is (by Sumiron Co.; Ltd. make; E-2035, thickness: 60 microns) stick on the surface of base mateiral, so the layered product that acquisition has four-layer structure.
Peel off release liner from this layered product, and with carbon dioxide laser (by Matsushita Industrial Equipment Co., Ltd.; Use YB-HCSO3, two-stroke excite processing, frequency 3000Hz, pulse width 50 microseconds (stroke for the first time)/40 microseconds (stroke for the second time)) at this layered product of pressure-sensitive adhesive layer side irradiation, be 2500/100cm so form hole density
2Hole.And then the release liner that on pressure-sensitive adhesive layer, superposes, and peel off the protection sheet material from the base mateiral surface, so obtain pressure-sensitive adhesive sheets.
[embodiment 2]
With the embodiment 1 the same pressure-sensitive adhesive sheets of making, the resin molding that different is is made by the blend of acrylic resin and urethane resin is (by Nippon Carbide IndustriesCo., Inc. make, B (41) C-M, thickness: 100 microns) the second stroke pulse width as base mateiral and carbon dioxide laser is 20 microseconds.
[embodiment 3]
With the embodiment 1 the same pressure-sensitive adhesive sheets of making, the resin molding that different is is made by urethane resin is (by Seikoh Chemicals Co., Ltd. make, FT80-100BK, thickness: 100 microns) the second stroke pulse width as base mateiral and carbon dioxide laser is 20 microseconds.
[embodiment 4]
With the embodiment 1 the same pressure-sensitive adhesive sheets of making, the resin molding that different is is made by polyvinyl chloride (PVC) RESINS is (by Nippon Carbide Industries Co., Inc.. make, Fuji-Paint 8344M2 (30), thickness: 100 microns) the second stroke pulse width as base mateiral and carbon dioxide laser is 50 microseconds.
[embodiment 5]
With the embodiment 1 the same pressure-sensitive adhesive sheets of making, different is that the trilaminar laminating resin film of two classes that contains acrylate resin layer (16 microns of thickness), styrene analog thermoplastic elastomer layer (68 microns of thickness) and acrylate resin layer (16 microns of thickness) (is made by Gunze Ltd., VM-52,100 microns of thickness) as base mateiral, with the second stroke pulse width of carbon dioxide laser be 50 microseconds, and the pulse width of the 3rd stroke is 20 microseconds.
[embodiment 6]
With the embodiment 1 the same pressure-sensitive adhesive sheets of making, the resin molding that different is is made by polyester is (by Toyobo Co., Ltd. make, Crisper G2311, thickness: 50 microns) as base mateiral, with the first stroke pulse width of carbon dioxide laser be that the pulse width of 25 microseconds and second stroke is 20 microseconds.
[Comparative Examples 1]
With the embodiment 1 the same pressure-sensitive adhesive sheets of making, different is (to be made by Mitsubishi Chemical MKV Company by the resin molding that polyolefins thermoplastic elastomer is made, CT-030, thickness 100 microseconds) as base mateiral, with the number of strokes quantitative change that makes carbon dioxide laser be 4 (pulse width of first to the 3rd stroke is 50 microseconds, and four-stroke pulse width is 40 microseconds).
Note working as and the embodiment 1 the same layered product of making, different is with embodiment 1 the same identical condition under, with carbon dioxide laser irradiation base mateiral, when described base mateiral is the above-mentioned resin molding of being made by polyolefins thermoplastic elastomer, do not form through hole.
[Comparative Examples 2]
With the embodiment 1 the same pressure-sensitive adhesive sheets of making, different is (to be made by Mitsubishi Chemical MKV Company by the resin molding that polyolefins thermoplastic elastomer is made, CT-030, thickness 100 microseconds) as base mateiral, with the number of strokes quantitative change that makes carbon dioxide laser be 6 (pulse width of first to the 5th stroke is 30 microseconds, and the pulse width of six-stroke is 20 microseconds).
Note when under the same identical condition with embodiment 1 with the layered product of carbon dioxide laser irradiation equally to make with embodiment 1, during different is above-mentioned resin molding that base mateiral is to be made by polyolefins thermoplastic elastomer, do not form through hole.
[test example]
(1) differential thermal/thermogravimetric is measured simultaneously
For (the example weight: 10mg), carry out TG/DTA under the following conditions and measure (differential thermal/thermogravimetric is measured simultaneously) simultaneously of employed each base mateiral in embodiment and Comparative Examples.Carry out DTA (differential thermal analysis) and carry out TG (thermogravimetry) according to JIS K7121 according to JIS K7120.
Measuring apparatus: DTG-60 differential thermal/thermogravimetric is measuring apparatus simultaneously, is made by ShimadzuCorporation
Atmosphere: nitrogen
Nitrogen purging condition: 50ml/min
Rate of heating: 20 ℃/min
Fig. 4-10 shows the chart that shows measuring result.In each chart, solid line represents that DTA and dotted line represent TGA.According to each chart, the temperature (T when measuring melting peak
1), thermolysis peak temperature (T
2), the poor (T of thermolysis peak temperature and fusion peak temperature
2-T
1) and the decline of the weight percentage meter in 40-500 ℃.The result has been shown in the table 1.
[table 1]
| Weight percentage meter decline (%) | Fusion peak value temperature T 1(℃) | Thermolysis peak temperature T 2(℃) | T 2-T 1(℃) | |
| |
93.14 | 219.4 | 421.5 | 202.1 |
| |
77.27 | 191.3 | 331.7 | 140.4 |
| Embodiment 3 | 97.44 | - | 373.9 | - |
| Embodiment 4 | 77.50 | - | 328.7 | - |
| Embodiment 5 | 75.82 | - | 415.2 | - |
| Embodiment 6 | 76.32 | 262.7 | 439.8 | 177.1 |
| Comparative Examples 1 | 97.59 | 166.0 | 463.4 | 297.4 |
| Comparative Examples 2 | 97.59 | 166.0 | 463.4 | 297.4 |
(2) through-hole diameter is measured
Cut each pressure-sensitive adhesive sheets that each embodiment and Comparative Examples obtain in the through-hole section office, and use scanning electronic microscope (by Hitachi Ltd., make, model S-2360N), measurement is at the through-hole diameter of base mateiral surface, maximum diameter in base mateiral, the diameter at the interface between base mateiral and pressure-sensitive adhesive layer and at the diameter of pressure sensitive adhesive surface.Table 2 shows the result.
(3) outward appearance detects
For the pressure-sensitive adhesive sheets that obtains in embodiment and Comparative Examples, the outward appearance of carrying out as described below detects.The result has been shown in the table 2.
(size: 30mm * 30mm) adheres on the plate of trimeric cyanamide coating of white the pressure-sensitive adhesive sheets that release liner is therefrom peeled off, and with the naked eye detects the outward appearance on pressure-sensitive adhesive sheets surface under room fluorescent lights.Distance between eyes and the pressure-sensitive adhesive sheets is about 30cm, and changes the angle of observing pressure-sensitive adhesive sheets.Be not subjected to through hole destructive pressure-sensitive adhesive sheets for outward appearance, result queue is " zero " and be subjected to through hole destructive pressure-sensitive adhesive sheets for outward appearance, and result queue is " * ".Next, to adhere on the plate of trimeric cyanamide coating and each pressure-sensitive adhesive sheets that left standstill 24 hours is immersed in the hot water 168 hours or is immersed in the gasoline 0.5 hour under 40 ℃, therefrom gather then, with after 48 hours, naked eyes detect the outward appearance judge pressure-sensitive adhesive sheets and whether are subjected to swelling or the through-hole section destruction of grading.Compare before with dipping, the unconspicuous pressure-sensitive adhesive sheets of through hole is labeled as " zero " and is labeled as " * " by tangible pressure-sensitive adhesive sheets.
[table 2]
| Through-hole diameter (microsecond) | Outward appearance | ||||||
| The base mateiral surface | Maximum diameter in the base mateiral | The interface | The pressure sensitive adhesive surface | Immediately after adhering to | After the dipping | ||
| Hot | Gasoline | ||||||
| Embodiment | |||||||
| 1 | 30 | 60 | 60 | 65 | ○ | ○ | ○ |
| |
30 | 65 | 65 | 70 | ○ | ○ | ○ |
| Embodiment 3 | 20 | 50 | 55 | 60 | ○ | ○ | ○ |
| Embodiment 4 | 25 | 60 | 60 | 70 | ○ | ○ | ○ |
| Embodiment 5 | 25 | 65 | 65 | 70 | ○ | ○ | (*1) |
| Embodiment 6 | 30 | 55 | 55 | 60 | ○ | ○ | ○ |
| Comparative Examples 1 | 30 | 140 | 70 | 180 | × | × | × |
| Comparative Examples 2 | 25 | 100 | 50 | 140 | × | × | × |
* 1: the not anti-gasoline of base mateiral resin itself.
(4) air entrapment is removed test 1
For obtain each pressure-sensitive adhesive sheets in embodiment and Comparative Examples, the air entrapment that carries out as described below is removed test.The result has been shown in the table 3.
The pressure-sensitive adhesive sheets that release liner is therefrom peeled off (size: 50mm * 50mm) adhere on the plate of smooth trimeric cyanamide coating, so that the air entrapment of the about 15mm of diameter occurs, use squeegee to push this pressure-sensitive adhesive sheets then, and whether proof can eliminate air entrapment.
For the pressure-sensitive adhesive sheets of eliminating air entrapment, result queue is " zero " and the pressure-sensitive adhesive sheets of not eliminating air entrapment (comprising pressure-sensitive adhesive sheets residual even a small amount of air entrapment), and result queue is " * ".
(5) air entrapment is removed test 2
For obtain each pressure-sensitive adhesive sheets in embodiment and Comparative Examples, the air entrapment that carries out as described below is removed test.The result has been shown in the table 3.
The pressure-sensitive adhesive sheets that release liner is therefrom peeled off (size: 50mm * 50mm) adhere on the plate of the trimeric cyanamide coating that has depression (recessed portion) 70mm * 70mm within it, the part spherical surface that being shaped as of described depression has diameter 15mm and full depth 1mm (between depression and pressure-sensitive adhesive sheets, having air entrapment), use squeegee to push this pressure-sensitive adhesive sheets then, and whether proof can eliminate air entrapment.Follow the recessed portion in the plate of trimeric cyanamide coating for pressure-sensitive adhesive sheets and therefore can eliminate the pressure-sensitive adhesive sheets of air entrapment, result queue is " zero ", with the trimeric cyanamide coating of recessed portion and the pressure-sensitive adhesive sheets of therefore not eliminating air entrapment (comprising pressure-sensitive adhesive sheets residual even a small amount of air entrapment) in the plate of not following to(for) pressure-sensitive adhesive sheets, result queue is " * ".
(6) measure modulus in tension (Young's modulus)
Each pressure-sensitive adhesive sheets of embodiment and Comparative Examples acquisition is cut into width 15mm and length 150mm, peel off release liner, then pressure-sensitive adhesive sheets is attached to the tensile strength tester (Tensilon that is spaced apart 100mm, by Orientec Co., Ltd. make) on, and under 200mm/min, stretch and calculate modulus in tension (Young's modulus) according to JIS K 7161 and JIS K7127.The result has been shown in the table 3.
[table 3]
| Air entrapment is removed |
Air entrapment is removed |
Modulus in tension (Young's modulus) (MPa) | |
| |
○ | ○ | 358 |
| |
○ | ○ | 432 |
| Embodiment 3 | ○ | ○ | 184 |
| Embodiment 4 | ○ | ○ | 750 |
| Embodiment 5 | ○ | ○ | 619 |
| Embodiment 6 | ○ | (*2) | 2900 |
| Comparative Examples 1 | ○ | ○ | 450 |
| Comparative Examples 2 | ○ | ○ | 450 |
* 2: can not be in the plate of trimeric cyanamide coating followed by recess.
1-3 can find out according to table, the pressure-sensitive adhesive sheets (embodiment 1-6) that meets the base mateiral of condition of the present invention for use, the air escape capability is good, in addition, the through hole internal diameter does not enlarge, therefore initial and in warm water or gasoline the good appearance after the dipping (embodiment 5 exceptions), and follow the ability also good (embodiment 6 makes an exception) of curvilinear surface.
Industrial applicibility
Adopting pressure-sensitive adhesive sheets usually to be easy to occur in the situation of air trapping or foaming, for example, have at pressure-sensitive adhesive sheets in the situation of large area, perhaps in the situation that gas discharges from adherend, with in common environment not only, and the liquid such as water or gasoline is attached in the environment on the pressure-sensitive adhesive sheets and requires in the situation of good outward appearance therein, can advantageously use pressure-sensitive adhesive sheets of the present invention.
Claims (6)
1. pressure-sensitive adhesive sheets, it comprises base mateiral and pressure-sensitive adhesive layer, wherein form pressure-sensitive adhesive sheets within it by the hot-work method, the surface that a plurality of through holes pass pressure-sensitive adhesive sheets arrives another surface, and this pressure-sensitive adhesive sheets is characterised in that:
In case the rate of heating with 20 ℃/min under nitrogen atmosphere heats described base mateiral, the thermolysis peak temperature when downgrade is maximum is not more than 450 ℃.
2. pressure-sensitive adhesive sheets, it comprises base mateiral and pressure-sensitive adhesive layer, wherein form pressure-sensitive adhesive sheets within it by the hot-work method, the surface that a plurality of through holes pass pressure-sensitive adhesive sheets arrives another surface, and this pressure-sensitive adhesive sheets is characterised in that:
In case with the rate of heating heating base mateiral of 20 ℃/min, the thermolysis peak temperature when downgrade is maximum and the difference of melting peak temperature are not more than 250 ℃ under nitrogen atmosphere.
3. pressure-sensitive adhesive sheets, it comprises base mateiral and pressure-sensitive adhesive layer, wherein form pressure-sensitive adhesive sheets within it by the hot-work method, the surface that a plurality of through holes pass pressure-sensitive adhesive sheets arrives another surface, and this pressure-sensitive adhesive sheets is characterised in that:
In case with the rate of heating of 20 ℃/min heating base mateiral, the thermolysis peak temperature when downgrade is maximum is not more than 450 ℃ and exist under the situation of melting peak under nitrogen atmosphere, the difference of thermolysis peak temperature and fusion peak temperature is not more than 250 ℃.
4. any one pressure-sensitive adhesive sheets of claim 1-3 is characterized in that described hot-work is LASER HEAT processing.
5. the pressure-sensitive adhesive sheets of claim 4 is characterized in that employed laser apparatus is a carbon dioxide laser in described LASER HEAT processing.
6. any one pressure-sensitive adhesive sheets of claim 1-5 is characterized in that at the diameter of the described through hole in the described base mateiral surface diameter less than the described through hole in pressure sensitive adhesive surface in described pressure-sensitive adhesive layer.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP210465/2005 | 2005-07-20 | ||
| JP2005210465 | 2005-07-20 | ||
| JP101385/2006 | 2006-04-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101248150A true CN101248150A (en) | 2008-08-20 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA200680030868XA Pending CN101248150A (en) | 2005-07-20 | 2006-07-20 | Pressure-sensitive adhesive sheet |
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| Country | Link |
|---|---|
| CN (1) | CN101248150A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113631381A (en) * | 2019-03-29 | 2021-11-09 | 琳得科株式会社 | Peeling detection label |
-
2006
- 2006-07-20 CN CNA200680030868XA patent/CN101248150A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113631381A (en) * | 2019-03-29 | 2021-11-09 | 琳得科株式会社 | Peeling detection label |
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Application publication date: 20080820 |