JP2011006644A - Removable re-adhesion type self-adhesive sheet to be stuck to structure surface such as floor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a removable re-adhesion type self-adhesive sheet to be stuck to a structure surface such as a floor, the sheet having excellent re-adhesion property after removed.SOLUTION: The removable re-adhesion type self-adhesive sheet comprises a sheet body 11 and a removable re-adhesion type self-adhesive layer 5 provided on the back face of the sheet body 11. The removable re-adhesion type self-adhesive layer 5 comprises 100 parts by mass of a cured product of a specified polymer having a terminal silyl group, which includes a urethane bond and/or a urea bond in the main chain or a side chain and containing a hydrolyzable silyl group at a terminal, and 10 to 35 parts by mass of a tackifier resin. The removable re-adhesion type self-adhesive sheet is obtained by applying a removable re-adhesion type self-adhesive precursor prepared by uniformly mixing 100 parts by mass of a specified polymer having a terminal silyl group, 10 to 35 parts by mass of a tackifier resin, and a curing catalyst of the specified polymer having a terminal silyl group, on the back face of the sheet body 11 and curing the specified polymer having a terminal silyl group.

Description

  The present invention relates to a pressure-sensitive adhesive sheet that is used after being stuck to a construction surface such as a floor surface, a wall surface, or a window surface, and relates to a re-peelable and re-adhesive pressure-sensitive adhesive sheet that can be peeled and reused.

  Conventionally, a pressure-sensitive adhesive sheet has been attached to a construction surface such as a floor surface to prevent slipping (Patent Document 1). The pressure-sensitive adhesive sheet described in Patent Document 1 is for sticking to a floor surface, and is provided with a pressure-sensitive adhesive layer on the back surface of a synthetic resin sheet with irregularities (see Patent Document 1). Figure 2). However, once this adhesive sheet was stuck on the floor, it could not be peeled off and stuck on the floor again. That is, when the synthetic resin sheet as the main body is damaged when peeling or the synthetic resin sheet is not damaged, the pressure-sensitive adhesive layer cannot exhibit the adhesive force that can be adhered to the floor surface again, and the re-peeling and re-bonding type It wasn't.

  In order to realize a re-peeling / re-bonding type for such a pressure-sensitive adhesive sheet, it is considered that a pressure-sensitive adhesive layer having a re-peeling / re-bonding property may be adopted. However, various pressure-sensitive adhesives having re-peeling properties that give a re-peelable mold to the pressure-sensitive adhesive sheet are known (Patent Documents 2 and 3), but pressure-sensitive adhesives having re-peelable and re-adhesive properties are not well known. Here, the re-peelable pressure-sensitive adhesive sheet and the re-peelable re-adhesive pressure-sensitive adhesive sheet are different in that they can be bonded again to the adherend after peeling. That is, the former is a pressure-sensitive adhesive sheet that can be easily peeled off without any adhesive residue, and is not used again after being peeled to adhere to the adherend. On the other hand, the latter is easy to peel off without adherent residue on the adherend, and is used again after peeling to adhere to the adherend.

  As a re-peeling / re-adhesive type pressure-sensitive adhesive sheet, one in which a re-peeling / re-adhesive pressure-sensitive adhesive layer made of a siloxane-modified polyurethane resin is provided on one side of a substrate film is known (Patent Document 4). However, this re-peelable and re-adhesive pressure-sensitive adhesive sheet can be applied to an adherend having a smooth surface, and cannot be applied to an adherend having a relatively rough surface such as a floor as a structure. It was. That is, the re-removable / re-adhesive pressure-sensitive adhesive layer made of a siloxane-modified polyurethane resin has insufficient re-removability and re-adhesive property and cannot be applied to an adherend having a rough surface.

JP 2007-47511 A JP-A-10-158595 JP 2006-241419 A Japanese Patent Laid-Open No. 11-80678

  By using a special re-peeling / re-adhesive pressure-sensitive adhesive, the present invention can be applied to a construction surface having a relatively rough surface such as a floor surface with high strength, and an adhesive residue on the construction surface. It is an object of the present invention to provide a re-peeling / re-bonding type pressure-sensitive adhesive sheet that can be peeled off without being used and can be used again after peeling.

（式中、Ｘはヒドロキシ基又はアルコキシ基を表し、Ｒは炭素数１〜２０のアルキル基を表し、ｎは０、１又は２を表す。） That is, in the present invention, a re-peeling / re-adhesive pressure-sensitive adhesive layer is provided on the back surface of the sheet body, and the re-peeling / re-adhesive pressure-sensitive adhesive layer has a urethane bond and / or a urea bond on the main chain or side chain. It has 100 parts by mass of a cured product of a terminal silyl group polymer containing a hydrolyzable silyl group represented by the following general formula (1) at the end, and 10 to 35 parts by mass of a tackifier resin. The present invention relates to a re-removable / re-adhesive pressure-sensitive adhesive sheet that is applied to a construction surface such as a floor surface.

(In the formula, X represents a hydroxy group or an alkoxy group, R represents an alkyl group having 1 to 20 carbon atoms, and n represents 0, 1 or 2.)

  The sheet body 11 is obtained by removing the re-peeling / re-adhesive pressure-sensitive adhesive layer 5 from the pressure-sensitive adhesive sheet. Therefore, any material can be used as the sheet body 11 as long as it can be a base material sheet of an adhesive sheet. Since the pressure-sensitive adhesive sheet according to the present invention is affixed to a construction surface such as a floor surface, it is preferable to use a material that is not easily damaged or deformed even if it is stepped on or rubbed. Specifically, the sheet body 11 shown in FIG. The sheet body 11 is formed by laminating and integrating a hard overcoat layer 6, a urethane resin sheet 1, a primer layer 2, an adhesive layer 3 and a support 4 in order from the surface. The hard overcoat layer 6 is provided to prevent the adhesive sheet from being damaged when stepped on. Therefore, this layer 6 can also be omitted when there is little risk of trampling and damage. The urethane resin sheet 1 is a kind of synthetic resin sheet, and is necessary for providing cushioning properties when the urethane resin sheet 1 is stuck on a floor surface. When cushioning properties and the like are not necessary, other synthetic resin sheets may be used, and sheets other than synthetic resin sheets such as metal foil and cloth may be used. The primer layer 2 is used to improve the adhesive force between the urethane resin sheet 1 and the adhesive layer 3. Therefore, if there is sufficient adhesive force between the urethane resin sheet 1 and the adhesive layer 3, it is not necessary to use it. The adhesive layer 3 integrates the support 4 and the urethane resin sheet 1, and the support 4 is used to improve the dimensional stability of the pressure-sensitive adhesive sheet. Therefore, if the urethane resin sheet 1 has sufficient dimensional stability depending on the application to be used, the adhesive layer 3 and the support 4 may be omitted.

  From the above description, it is understood that various types of the sheet body 11 can be used. For example, those composed only of synthetic resin sheets, laminates of overcoat layers / synthetic resin sheets, laminates of synthetic resin sheets / adhesive layers / supports, overcoat layers / synthetic resin sheets / adhesive layers / supports Examples include laminates. Moreover, it can replace with a synthetic resin sheet and can also be set as the sheet | seat main body 11 using metal foil, cloth, etc.

  It is preferable to provide unevenness on the surface of the sheet body 11. Since the pressure-sensitive adhesive sheet according to the present invention is often used on a floor surface, the unevenness imparts a non-slip function. The unevenness is provided on the synthetic resin sheet, particularly the urethane resin sheet. Of course, when the overcoat layer 6 exists, the overcoat layer 6 is provided with unevenness together with the synthetic resin sheet. Such unevenness can be easily imparted by performing conventionally known embossing.

  A re-peeling / re-adhesive pressure-sensitive adhesive layer 5 is provided on the back surface of the sheet body 11. The re-peeling / re-adhesive pressure-sensitive adhesive layer 5 has a terminal silyl group having a urethane bond and / or a urea bond in the main chain or side chain and containing a hydrolyzable silyl group represented by the general formula (1) at the terminal. 100 mass parts of hardened | cured material of a polymer and 10-35 mass parts of tackifying resin are contained.

  The terminal silyl group polymer (hereinafter referred to as “specific terminal silyl group polymer”) used in the present invention is a known one, and is disclosed in Japanese Patent No. 3317353, Japanese Patent No. 3030020, Japanese Patent No. 3343604, Special Table. It is described in 2004-518801 gazette, special table 2004-536957 gazette, and special table 2005-501146 gazette. Since the specific terminal silyl group polymer has a urethane bond and / or a urea bond introduced in the main chain or side chain, the adhesive layer 5 is sufficiently cured and has a tight three-dimensional network structure. Therefore, it is preferable that the pressure-sensitive adhesive layer 5 does not flow easily and the pressure-sensitive adhesive layer 5 hardly flows down or falls off even if it is peeled again and re-adhesion is repeated. In addition, the active hydrogen in the urethane bond and / or urea bond introduced into the main chain or the side chain may be substituted with an organic group. Therefore, allophanate bonds also belong to the urethane bond category, and burette bonds also belong to the urea bond category.

  The hydrolyzable silyl group constituting the terminal of the specific terminal silyl group polymer preferably has n of 1 in the general formula (1). That is, it preferably has two hydrolyzable groups at the terminal. Those having n of 0 have three hydrolyzable groups at the end, but such a specific terminal silyl group polymer has a dense three-dimensional network structure after curing, compared with those having n of 1. The pressure-sensitive adhesive layer 5 becomes too hard, and tends to be inferior in followability to bending of the tape base material or the sheet base material. In addition, since n having 2 has only one hydrolyzable group at the end, the three-dimensional network structure after curing becomes insufficient, the pressure-sensitive adhesive layer 5 becomes too soft, and it tends to flow off or fall off. May be easier. Further, as can be seen from this, in order to achieve the desired hardness and softness in the pressure-sensitive adhesive layer 5, those having n of 0, 1, or 2 may be mixed and adjusted at a predetermined ratio. A urethane bond and / or a urea bond are introduced into the main chain of the specific terminal silyl group polymer, and the main chain is preferably a polyoxyalkylene such as polyoxypropylene or polyoxyethylene. This is because when the main chain is mainly polyoxyalkylene, the resulting pressure-sensitive adhesive layer 5 can easily exhibit appropriate softness.

  In the present invention, the specific terminal silyl group polymer and another terminal silyl group polymer may be mixed. For example, a specific terminal silyl group polymer may be mixed with a terminal silyl group polymer in which no urethane bond and / or urea bond is introduced into the main chain and side chain. The latter terminal silyl group polymer is harder to cure than the specific terminal silyl group polymer, but the degree of curing can be increased by mixing with the specific terminal silyl group polymer.

  As tackifying resin used by this invention, well-known tackifying resin used when obtaining an adhesive is used. For example, rosin resins such as rosin, polymerized rosin, hydrogenated rosin, rosin ester; terpene resins such as terpene phenol resin, aromatic modified terpene resin, hydrogenated terpene resin, rosin phenol resin; aliphatic petroleum resin; aromatic Various petroleum resins; various hydrogenated petroleum resins such as aromatic hydrogenated petroleum resins, dicyclopentadiene hydrogenated petroleum resins, aliphatic hydrogenated petroleum resins; coumarone indene resins; styrene resins; maleic acid resins; An alkylphenol resin; a xylene resin or the like can be used. In particular, in the present invention, it is preferable to use a styrene resin or a terpene resin.

  The compounding quantity of tackifying resin is mix | blended 10-35 mass parts with respect to 100 mass parts of hardened | cured materials of a specific terminal silyl group polymer. When the blending amount of the tackifying resin is less than 10 parts by mass, the initial adhesive force becomes insufficient, and it is not suitable for sticking to the construction surface of the floor surface. Moreover, when the compounding quantity of tackifying resin exceeds 35 mass parts, since the adhesive force when it peels and re-adheres falls, it is unpreferable. That is, if the compounding amount of the tackifying resin is adjusted to 10 to 35 parts by mass, even if it is re-peeled about 5 times and re-adhered, there is little decrease in adhesive force during re-adhesion.

  The re-peeling / re-adhesive pressure-sensitive adhesive sheet according to the present invention can be produced, for example, by the following method. First, the above-mentioned specific terminal silyl group polymer, its curing catalyst and tackifying resin are uniformly mixed to obtain a pressure-sensitive adhesive precursor. In general, the pressure-sensitive adhesive precursor is obtained by uniformly mixing a specific terminal silyl group polymer and a tackifying resin to obtain a mixture, and then adding and mixing a curing catalyst and stirring to obtain a uniform mixture. Is preferred. That is, it is preferable to finally add and mix the curing catalyst to obtain the pressure-sensitive adhesive precursor. This is because the curing catalyst has a catalytic action on the specific terminal silyl group polymer, and therefore, when mixed from the beginning, the adhesive precursor may be cured before being applied to the back surface of the sheet body. In addition, when mixing a specific terminal silyl group polymer and tackifying resin uniformly, when both compatibility is inadequate, you may use an organic solvent. As the organic solvent, alcohols such as ethanol, ethyl acetate, toluene, methylcyclohexane and the like are used. Further, when the compatibility between the specific terminal silyl group polymer and the tackifier resin is good, the organic solvent may not be used.

  Curing catalysts include titanium chloride, tin chloride, zirconium chloride, aluminum chloride, iron chloride, zinc chloride, zinc bromide, copper chloride, antimony chloride and other metal halides, and boron trifluoride, boron trichloride, etc. A boron halide compound or the like is used. In addition, amine complexes, alcohol complexes, ether complexes and the like of the above compounds are also used. In the present invention, particularly preferred are titanium (IV) chloride, tin (IV) chloride, zirconium (IV) chloride, aluminum (III) chloride, boron trifluoride amine complexes and alcohol complexes.

  For the reasons described above, the tackifier resin is blended in an amount of 10 to 35 parts by mass with respect to 100 parts by mass of the specific terminal silyl group polymer. Moreover, it is preferable to mix | blend 0.001-10 mass parts of curing catalysts with respect to 100 mass parts of specific terminal silyl group polymers. When the blending amount of the curing catalyst is less than 0.001 part by mass, the catalytic action becomes insufficient, and it tends to be difficult to form an adhesive layer having a close three-dimensional network structure. Moreover, when the compounding quantity of a curing catalyst exceeds 10 mass parts, there exists a possibility that it may harden | cure when obtaining a pressure-sensitive adhesive precursor because the catalytic action becomes excessive.

  In addition, the following compounds or substances may be added to and mixed with the pressure-sensitive adhesive precursor. For example, silane coupling agents, anti-aging agents, dehydrating agents such as vinyl silane compounds and calcium oxide, fillers, plasticizers, thixotropic agents such as anhydrous silica and amide wax, diluents such as isoparaffin, aluminum hydroxide, halogen-based Add flame retardants such as flame retardants, phosphorus flame retardants, silicone flame retardants, functional oligomers such as silicone alkoxy oligomers and acrylic oligomers, pigments, titanate coupling agents, aluminum coupling agents, drying oils, etc. May be.

  Optional dehydrating agents include calcium oxide, magnesium oxide, zinc oxide, calcium chloride, orthosilicate ester, vinyl silane compounds such as vinyltrimethoxysilane, silicate compounds such as methyl silicate and ethyl silicate, activated carbon, zeolite, etc. Can be mentioned

  Anti-aging agents that are optional additives include radical chain initiation inhibitors (hydrazide, amide, etc.), UV absorbers (benzotriazole, triazine, benzophenone, etc.), quenchers (organic nickel, etc.) , HALS (hindered amines, etc.) as radical scavengers, phenolic antioxidants (hindered phenols, semihindered phenols, etc.), and phosphorus antioxidants (phosphites, phosphonites, etc.) as peroxide decomposers ), Sulfur type antioxidants (thioether type, etc.) are used. Commercially available anti-aging agents include: Adeka Stub series manufactured by Asahi Denka Kogyo; Hostanox series, Hostabin series, Sanduboa series, Hostastat series manufactured by Clariant Japan; Sanol series manufactured by Sankyo Lifetech; The Chinubin series, Irgafos series, Irganox series, Kimasorb series, etc. manufactured by Ciba Specialty Chemicals are used.

  After obtaining the pressure-sensitive adhesive precursor as described above, this is applied to the back surface of the sheet body 11. As a method for applying the pressure-sensitive adhesive precursor, a conventionally known method can be employed, for example, a knife coater method, a roll coater method, or the like. Furthermore, the coating thickness of the pressure-sensitive adhesive precursor is the same as the conventional one, and is about 50 to 100 μm.

  After apply | coating an adhesive precursor to the back surface of the sheet | seat main body 11, the specific terminal silyl group polymer contained in the adhesive precursor is hardened. Since the specific terminal silyl group polymers condense in the presence of moisture to form a three-dimensional network structure and cure, the adhesive precursor after coating may be placed in the presence of moisture such as water vapor. Specifically, when placed in the atmosphere, it is placed in the presence of water vapor. Moreover, since an organic solvent etc. may be contained in an adhesive precursor, in order to evaporate these, it is common to heat to the temperature of 80 degreeC or more. Therefore, in general, the re-removable / re-adhesive pressure-sensitive adhesive layer 5 can be formed by applying the pressure-sensitive adhesive precursor to the back surface of the sheet main body 11 and then heating in the air. An adhesive sheet is obtained.

  Moreover, in this invention, after obtaining a double-sided adhesive tape with the following methods, a re-peeling re-adhesion type adhesive sheet can also be obtained. That is, a double-sided pressure-sensitive adhesive tape in which the adhesive layer 3 is provided on one side of the support 4 and the re-peeling / re-adhesive pressure-sensitive adhesive layer 5 is provided on the other side is obtained. The re-peeling / re-adhesive pressure-sensitive adhesive layer 5 is provided by applying the above-mentioned pressure-sensitive adhesive precursor to the other surface of the support 4 or by applying it to the surface of the release paper 7 and then transferring it to the support 4. do it. If the adhesive layer 3 of the double-sided pressure-sensitive adhesive tape obtained by such a method is adhered to the back surface of the synthetic resin sheet 1 directly or via the primer layer 2, the re-peelable / re-adhesive pressure-sensitive adhesive sheet according to the present invention can be obtained. Obtainable.

  The re-peeling / re-adhesive pressure-sensitive adhesive sheet according to the present invention can be used as a non-slip sheet by sticking to a floor surface of a building such as a station, a store or a living room, a floor surface of a bathtub, or a floor surface of a bathroom. . It can also be used to prevent damage to the walls and windows by sticking to the walls and windows of buildings such as stations, shops or living rooms. That is, it is used by sticking to various structural surfaces for various purposes. And after peeling, the re-peeling / re-adhesive pressure-sensitive adhesive sheet is peeled off, and the dust adhering to the re-peeling / re-adhesive pressure-sensitive adhesive layer is washed away with water. Specifically, using a urethane sponge impregnated with water, a wiping cloth, or the like, the re-peeling / re-adhesive pressure-sensitive adhesive layer surface is rubbed to remove dust. And it sticks to a floor surface etc. again and uses it. The re-peeling / re-adhesive pressure-sensitive adhesive sheet according to the present invention can be used by repeating such peeling and sticking several times.

  The re-removable / re-adhesive pressure-sensitive adhesive sheet according to the present invention contains a specific amount of tackifying resin in a cured product in which the re-removable / re-adhesive pressure-sensitive adhesive layer has a three-dimensional network structure of a specific terminal silyl group polymer. Therefore, after sticking on the floor surface or the like, it can be peeled off and pasted again on the floor surface or the like. And when sticking on a floor surface etc. again, there exists an effect that the adhesive force hardly declines.

1 is a schematic cross-sectional view of a re-peeling / re-bonding pressure-sensitive adhesive sheet attached to a construction surface such as a floor according to an example of the present invention.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to an Example. The present invention should be construed as being based on the knowledge that a pressure-sensitive adhesive layer comprising a cured product of a specific terminal silyl group polymer and a specific amount of tackifying resin is excellent in re-removability and re-adhesion. .

Example 1
[Synthesis of specific terminal silyl group polymer]
In a reaction vessel, 206 parts by mass of N-aminoethyl-γ-aminopropylmethyldimethoxysilane and 172 parts by mass of methyl acrylate were charged and reacted at 80 ° C. for 10 hours while stirring and mixing in a nitrogen atmosphere. A silane compound serving as a silylating agent was obtained.
On the other hand, PML S4015 (polyoxypropylene diol, molecular weight 15000: manufactured by Asahi Glass Co., Ltd.) 1000 parts by mass, isophorone diisocyanate 24.6 parts by mass (NCO / OH ratio = 1.7) and dibutyltin dilaurate 0.05 parts by mass in another reaction vessel. The mixture was reacted at 85 ° C. for 7 hours with stirring and mixing under a nitrogen atmosphere to obtain a urethane prepolymer in which the main chain was mainly polyoxypropylene and urethane bonds were introduced into the main chain.
The specific terminal silyl group polymer was obtained by adding 42.1 mass parts of said silane compounds to 1000 mass parts of this urethane prepolymer, and making it react at 80 degreeC for 1 hour, stirring and mixing in nitrogen atmosphere. Progress of the reaction was confirmed by disappearance of isocyanate group absorption (2265 cm ⁻¹ ) by IR.
This specific terminal silyl group polymer has two methoxy groups as hydrolyzable silyl groups represented by the general formula (1), the main chain is mainly polyoxypropylene, and urethane bonds are introduced into the main chain. It will be.

[Production of re-peeling / re-adhesive adhesive sheet]
To 100 parts by mass of the specific terminal silyl group polymer, 20 parts by mass of ethyl acetate as a solvent and 9.5 parts by mass of a styrene resin (trade name “FTR8100” manufactured by Mitsui Chemicals, Inc.) as a tackifier resin (rounded off to the nearest decimal place) 10 parts by mass) was added and mixed, and stirred uniformly to obtain a mixture.
To 130 parts by mass of this mixture, 1.0 part by mass of boron trifluoride monoethylamine complex (containing 59% by mass as boron trifluoride) as a curing catalyst, an anti-aging agent (trade name “Irganox 1010”, manufactured by Ciba). 2) parts by weight and 1 part by weight of a dehydrating agent (trade name “KBM1003”, manufactured by Shin-Etsu Chemical Co., Ltd.) were added and sufficiently stirred and mixed uniformly to obtain a pressure-sensitive adhesive precursor.
This pressure-sensitive adhesive precursor was applied to the back surface of a 25 μm-thick polyester film as a sheet body by a knife coater method so that the coating thickness was about 90 μm. Then, after heating at 120 ° C. for 5 minutes in the air, leaving at room temperature for 15 minutes and then aging at 40 ° C. for 1 week to cure the specific terminal silyl group polymer and evaporate ethyl acetate and moisture. Thus, a re-peeling / re-adhesive pressure-sensitive adhesive layer was obtained. Thereby, the re-removable / re-adhesive pressure-sensitive adhesive sheet in which the re-removable / re-adhesive pressure-sensitive adhesive layer was laminated on the back surface of the sheet main body was obtained.

Example 2
A re-peelable and re-adhesive pressure-sensitive adhesive sheet was obtained by the same method as in Example 1 except that the addition amount of the tackifying resin was changed to 20 parts by mass.

Example 3
A re-peelable and re-adhesive adhesive sheet was obtained by the same method as in Example 1 except that the addition amount of the tackifying resin was changed to 30 parts by mass and the addition amount of ethyl acetate was changed to 25 parts by mass.

Example 4
A re-peelable and re-adhesive pressure-sensitive adhesive sheet was obtained by the same method as in Example 1 except that the addition amount of the tackifying resin was changed to 35 parts by mass and the addition amount of ethyl acetate was changed to 25 parts by mass.

Example 5
Instead of adding 0.2 parts by mass of boron trifluoride aminopropyltriethoxysilane complex which is a curing catalyst, titanium diisopropoxybisacetylacetonate (manufactured by Matsumoto Trading Co., Ltd., trade name “OrgaTix TC-100” “)” Was added and mixed in an amount of 4 parts by mass to obtain a re-peelable / re-adhesive adhesive sheet by the same method as in Example 3.

Example 6
Example 3 except that a terpene-based tackifier resin (trade name “YS Polystar T145” manufactured by Yasuhara Chemical Co., Ltd.) is used in place of the styrene-based resin (trade name “FTR8100” manufactured by Mitsui Chemicals, Inc.) as the tackifier resin. A re-peeling / re-bonding type pressure-sensitive adhesive sheet was obtained by the same method as that described above.

Example 7
Example 4 except that a terpene-based tackifier resin (trade name “YS Polystar T145” manufactured by Yasuhara Chemical Co., Ltd.) is used instead of a styrene-based resin (trade name “FTR8100” manufactured by Mitsui Chemicals, Inc.) as the tackifier resin. A re-peeling / re-bonding type pressure-sensitive adhesive sheet was obtained by the same method as that described above.

Reference example 1
A re-peelable and re-adhesive pressure-sensitive adhesive sheet was obtained by the same method as in Example 1 except that no tackifying resin was used.

Reference example 2
A re-peelable and re-adhesive pressure-sensitive adhesive sheet was obtained by the same method as in Example 1 except that the addition amount of the tackifying resin was changed to 0.5 parts by mass.

Comparative Example 1
A re-peelable and re-adhesive pressure-sensitive adhesive sheet was obtained by the same method as in Example 1 except that the addition amount of the tackifying resin was changed to 40 parts by mass.

Comparative Example 2
A re-peeling / re-bonding type pressure-sensitive adhesive sheet was obtained by the same method as in Example 1 except that the addition amount of the tackifying resin was changed to 60 parts by mass.

Comparative Example 3
On the back side of the sheet main body used in Example 1, an acrylic solvent type adhesive (manufactured by Nippon Synthetic Chemical Co., Ltd., trade name “Coponil N-4105”) was applied with a knife coater so that the coating thickness was about 90 μm, A re-peeling / re-adhesive pressure-sensitive adhesive sheet was obtained.

The re-peeling / re-bonding properties of the re-peeling / re-bonding pressure-sensitive adhesive sheets obtained in Examples 1 to 7, Reference Examples 1 and 2 and Comparative Examples 1 to 3 were evaluated by the following methods. The results are shown in Table 1.
[Initial bond strength]
After the re-peeling / re-adhesive adhesive sheet was attached to the hard vinyl chloride plate as the adherend and cured at 23 ° C. for 3 days, JIS Z 0237 10.4 was peeled off 180 degrees except for the adherend. The initial adhesive strength (N / 20 mm) was measured according to the method described in the measurement.
[Adhesion strength after contamination]
The entire surface of the re-peeling / re-adhesive pressure-sensitive adhesive layer is coated with silitin powder [“Siritin V85” (average particle size: 3 μm) manufactured by Hoffman Mineral Co., Ltd.] and pressed by hand. To contaminate. After leaving for 5 minutes, while supplying water to the entire surface of the re-peeling / re-adhesive pressure-sensitive adhesive layer, it is rubbed with a urethane sponge to wash off the silytin powder. Thereafter, it is dried in an atmosphere of 60 ° C. for 10 minutes. And again, after sticking a re-peeling / re-adhesive adhesive sheet on the hard vinyl chloride plate which is the adherend and curing at 23 ° C. for 3 days, JIS Z 0237 10.4 180 degree peeling except for the adherend The adhesion strength (N / 20 mm) was measured according to the method described in the measurement of adhesive force. In addition, the thing which performed contamination | pollution-washing-drying once is made into the adhesive strength after contamination (one time), and the thing which performed contamination-washing-drying twice is the adhesion strength after contamination (twice). In the following, this was repeated up to 5 times. The adhesion strength after performing this contamination-washing-drying n times is to peel off the adherend n times, then wash and dry the re-peelable / re-adhesive pressure-sensitive adhesive layer, and re-adhere to the adherend. It correlates well with the adhesive strength of the case.

[Table 1]
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Bond strength after contamination
────────────────────
Initial bond strength 1 time 2 times 3 times 4 times 5 times ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━━
Example 1 4.8 5.0 5.4 5.7 6.0 5.5
Example 2 5.5 5.8 6.3 5.4 6.3 5.7
Example 3 7.1 7.4 7.6 7.7 6.8 6.5
Example 4 8.7 9.1 9.0 8.8 8.5 8.6
Example 5 7.1 7.8 7.4 7.9 7.5 7.0
Example 6 9.1 9.8 9.5 9.6 10.1 9.1
Example 7 9.7 9.8 10.2 9.3 9.5 8.8
──────────────────────────────────────
Reference Example 1 4.2 4.9 5.3 5.2 4.8 4.6
Reference Example 2 4.3 4.6 5.2 5.1 5.3 4.9
──────────────────────────────────────
Comparative Example 1 10.4 8.0 7.5 7.6 7.0 7.4
Comparative Example 2 14.0 10.2 10.0 8.2 9.7 8.5
Comparative Example 3 11.6 9.0 8.5 6.6 6.0 5.5
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  From the results shown in Table 1, the initial adhesive strength is assumed to be 100%, and the percentage of the adhesive strength after contamination relative to the initial adhesive strength is calculated as follows. That is, 104 to 125% in Example 1, 98 to 115% in Example 2, 92 to 108% in Example 3, 98 to 105% in Example 4, 99 to 111% in Example 5, and Example 6 Is 100 to 111%, and Example 7 is 91 to 105%. In Reference Example 1, it is 110 to 126%, and in Reference Example 2 is 107 to 123%. On the other hand, it is 67 to 77% in Comparative Example 1, 59 to 73% in Comparative Example 2, and 47 to 78% in Comparative Example 3. When measuring the initial adhesive strength and the adhesive strength after contamination, the fracture occurred at the interface between the adherend and the re-peeling / re-adhesive pressure-sensitive adhesive layer, and no adhesive remained on the adherend.

  From the above, it can be seen that the pressure-sensitive adhesive layer mainly composed of the cured product of the specific terminal silyl group polymer is excellent in re-peeling and re-adhesion. And even if it adds to 35 mass parts of tackifying resin with respect to 100 mass parts of said hardened | cured materials, although re-adhesiveness is favorable (Examples 1-7, Reference Examples 1 and 2), it is 40 mass parts or more. It can be seen that when added, the re-adhesiveness decreases (Comparative Examples 1 and 2). In addition, although the re-removable / re-adhesive adhesive tape according to Reference Examples 1 and 2 with a small addition amount of the tackifying resin is excellent in re-removable / re-adhesive, the initial adhesive strength is about 4 N / 20 mm, It is unsuitable for wearing on construction surfaces such as floors.

DESCRIPTION OF SYMBOLS 1 Urethane resin sheet 2 Primer layer 3 Adhesive layer 4 Support body 5 Re-peeling / Re-adhesive pressure-sensitive adhesive layer 6 Overcoat layer 7 Release paper 11 Sheet body

Claims (9)

A re-peeling / re-adhesive pressure-sensitive adhesive layer is provided on the back surface of the sheet body, and the re-peeling / re-adhesive pressure-sensitive adhesive layer has a urethane bond and / or a urea bond in the main chain or side chain, and has the following general structure at the terminal. A floor surface characterized by containing 100 parts by mass of a cured product of a terminal silyl group polymer containing a hydrolyzable silyl group represented by the target (1) and 10 to 35 parts by mass of a tackifying resin Re-peeling and re-adhesive pressure-sensitive adhesive sheet that is applied to the surface of the structure.

(In the formula, X represents a hydroxy group or an alkoxy group, R represents an alkyl group having 1 to 20 carbon atoms, and n represents 0, 1 or 2.)   The re-peelable / re-adhesive adhesive sheet for sticking to a construction surface such as a floor surface according to claim 1, wherein the sheet main body is laminated from the surface in the order of a synthetic resin sheet, an adhesive layer and a support.   The re-peelable and re-adhesive adhesive sheet for sticking to a construction surface such as a floor surface according to claim 2, wherein the synthetic resin sheet is a urethane resin sheet having irregularities on the surface and has a non-slip function.   The re-peelable / re-adhesive pressure-sensitive adhesive sheet for application to a construction surface such as a floor surface according to claim 1, wherein a terminal silyl group polymer whose main chain is composed of polyoxyalkylene is used.   The n in general formula (1) is 1, The re-peeling / re-adhesive pressure-sensitive adhesive sheet for attaching to a construction surface such as a floor surface according to claim 1.   The re-peeling / re-adhesive pressure-sensitive adhesive sheet for attaching to a construction surface such as a floor surface according to claim 1, wherein a styrene-based resin or a terpene-based resin is used as the tackifying resin. 100 parts by mass of a terminal silyl group polymer having a urethane bond and / or a urea bond in the main chain or side chain and containing a hydrolyzable silyl group represented by the following general formula (1) at the terminal, By applying the re-peeling / re-adhesive pressure-sensitive adhesive precursor, in which 35 parts by mass and the terminal silyl group polymer curing catalyst are uniformly mixed, to the back surface of the sheet body, the terminal silyl group polymer is cured, The method for producing a re-removable / re-adhesive pressure-sensitive adhesive sheet attached to a construction surface such as a floor surface according to claim 1, wherein the re-removable / re-adhesive pressure-sensitive adhesive precursor is used as a re-removable / re-adhesive pressure-sensitive adhesive layer.

(In the formula, X represents a hydroxy group or an alkoxy group, R represents an alkyl group having 1 to 20 carbon atoms, and n represents 0, 1 or 2.)   The adhesive layer of the double-sided adhesive sheet in which the adhesive layer is provided on one side of the support and the re-peeling / re-adhesive pressure-sensitive adhesive layer according to claim 1 is provided on the other side is bonded to the back side of the synthetic resin sheet. The method for producing a re-peelable / re-adhesive pressure-sensitive adhesive sheet for attaching to a construction surface such as a floor surface according to claim 2.   The re-removable / re-adhesive adhesive sheet is peeled off from a construction surface such as a floor surface to which the re-removable / re-adhesive adhesive sheet according to claim 1 is attached, A re-peeling / re-bonding method, comprising: washing off dust adhering to an adhesive pressure-sensitive adhesive layer surface with water, and then re-bonding the re-peeling / re-bonding pressure-sensitive adhesive sheet to a construction surface such as a floor surface.

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