JP2007262320A - Double-sided pressure sensitive adhesive sheet or tape for glass - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a double-sided pressure sensitive adhesive tape which is used as a double sided pressure sensitive adhesive sheet or tape by adhering at least one adhesive face on a glass plate, sustaining fixing strength even if a comparatively large load is applied, hardly shifting between both adherents. <P>SOLUTION: The invention relates to the double sided pressure sensitive adhesive sheet or tape comprising a support body comprising a sheet shaped foam or a tape shaped foam or a support body obtained by laminating a rigid resin film onto at least one side of a sheet shaped or tape shaped foam, the pressure sensitive adhesive layers formed on both sides of the support body, and a releasing layer adhered at least one side opposite to the supporting body of the pressure sensitive adhesive layer, wherein the sheet is used by adhering at least one side of the pressure sensitive adhesive layer onto the glass plate, the pressure sensitive adhesive sheet or tape has ≤2.5mm of tensile shear displacement at the peak of the tensile shearing strength of adhesion at room temperature in measuring the tensile shearing strength of adhesion of the double sided pressure sensitive adhesive sheet or tape without the releasing layer, according to JIS K 6850 using a glass plate as an adherent. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a double-sided pressure-sensitive adhesive sheet or tape for fixing various members to a glass member.

As a mounting structure for attaching a window glass to an opening of a vehicle, there is known a temporary fixing member that temporarily holds the glass against the opening by a fastener until the adhesive applied to the glass is cured. (See Patent Document 1). The temporary fixing member is a member that is attached in advance to a window glass with a fastener provided with a leg having a claw portion, and the claw portion is locked to an attachment hole formed in an opening of a vehicle body. . This temporary fixing member is usually attached to the window glass with a double-sided adhesive tape. As the double-sided pressure-sensitive adhesive tape, a double-sided pressure-sensitive adhesive tape in which an acrylic resin-based pressure-sensitive adhesive layer is formed on a base material made of acrylic foam is widely used.
JP-A-8-310233

  In recent years, windshields for vehicles tend to be larger due to design requirements. When attaching such a large glass to the opening of the vehicle, there is a problem that the window glass is displaced from the position temporarily held in the direction parallel to the glass surface by its own weight while the adhesive is cured. In addition, due to the design requirement to create a sense of unity as a vehicle (called a flash surface), a configuration in which the distance between the end portion of the wind glass and the body is narrow is preferred. In this case, since the reaction force applied to a part called a molding lip disposed between the window glass and the body increases, there is a problem that the window glass is displaced from the temporarily held position.

  The present invention solves the above-described problems and provides the following inventions.

  [1] A support made of a sheet-like or tape-like foam or a support made by laminating a hard resin film on at least one side of a sheet-like or tape-like foam, and an adhesive layer formed on both sides of the support, A double-sided pressure-sensitive adhesive sheet or tape that is used by adhering at least one pressure-sensitive adhesive surface to a glass plate, comprising a release layer attached to at least one surface of the pressure-sensitive adhesive layer opposite to the support, In the tensile shear bond strength test of the double-sided pressure-sensitive adhesive sheet or tape from which the release layer according to JIS K 6850 is removed using a glass plate as the adherend, the tensile shear displacement amount at the peak value of the tensile shear bond strength at room temperature is A double-sided pressure-sensitive adhesive sheet for glass or tape that is 2.5 mm or less.

  [2] The test according to [1], wherein the tensile shear displacement at the peak value of the tensile shear adhesive strength at room temperature is 2.0 mm or less in the test using the glass plate not subjected to the primer treatment as an adherend. Double-sided adhesive sheet or tape for glass.

  [3] A support made of a sheet-like or tape-like foam or a support made by laminating a hard resin film on at least one side of a sheet-like or tape-like foam, and an adhesive layer formed on both sides of the support, In the double-sided pressure-sensitive adhesive sheet or tape used by adhering at least one pressure-sensitive adhesive surface having a release layer attached to at least one surface of the pressure-sensitive adhesive layer opposite to the support to a glass plate, the pressure-sensitive adhesive A layer is a urethane resin obtained by reacting a chain extender with an isocyanate group-terminated prepolymer obtained by reacting a polyol and a polyisocyanate compound in an excess ratio of an isocyanate group, or a terminal terminator further added to the urethane resin. A double-sided pressure-sensitive adhesive sheet for glass, which is formed of a urethane resin obtained by reacting Over-flops.

  [4] The double-sided pressure-sensitive adhesive sheet for glass according to [3], wherein the pressure-sensitive adhesive layer is formed of a crosslinked polyurethane resin obtained by further reacting the urethane resin with a second polyisocyanate compound as a crosslinking agent. tape.

[5] The double-sided pressure-sensitive adhesive sheet or tape for glass according to [3] or [4], wherein at least a part of the chain extender is a compound selected from the following (a) and (b).
(A) having three or more functional groups capable of reacting with an isocyanate group, and two of these functional groups are one or two selected from a primary amino group, a secondary amino group, and a primary hydroxyl group A compound which is a functional group and the remaining functional group is at least one functional group selected from a secondary hydroxyl group, a tertiary hydroxyl group and a carboxyl group.
(B) having three or more functional groups capable of reacting with an isocyanate group, two of which are one or two functional groups selected from a primary amino group and a secondary amino group A compound in which the remaining functional group is a primary hydroxyl group.

  [6] At least a part of the chain extender is (1) a compound having one primary amino group, one primary hydroxyl group and at least one secondary hydroxyl group, and (2) one secondary amino group and 1 The compound according to [5], which is a compound having one primary hydroxyl group and at least one secondary hydroxyl group, or (3) a compound having two primary hydroxyl groups and at least one secondary hydroxyl group or tertiary hydroxyl group. Double-sided adhesive sheet or tape for glass.

  [7] Both surfaces for glass according to any one of [3] to [6], wherein the polyol is a polyoxyalkylene polyol having an average hydroxyl value of 2 or more and a hydroxyl value of 5.6 to 600 mgKOH / m. Adhesive sheet or tape.

  [8] The double-sided pressure-sensitive adhesive sheet or tape for glass according to any one of [3] to [7], wherein the sheet-like or tape-like foam is a polyurethane foam.

[9] The sheet-like or tape-like foam according to any one of [3] to [8], wherein the thickness is 0.05 to 3.0 mm and the density is 100 to 800 kg / m ^3. Double-sided adhesive sheet or tape for glass.

  [10] The double-sided pressure-sensitive adhesive sheet for glass or tape according to any one of [3] to [9], wherein the hard resin film has a thickness of 10 to 50 μm and is made of polypropylene or polyethylene terephthalate.

  [11] The double-sided adhesive for glass according to any one of [3] to [9], wherein the support is made of polyurethane foam having a thickness of 0.05 to 3.0 mm and a density of 100 to 800 kg / m. Sheet or tape.

[12] Any of [3] to [10], wherein the support has a thickness of 0.05 to 3.0 mm and a polyurethane foam and a hard resin film having a density of 100 to 800 kg / m ³ are laminated. The double-sided pressure-sensitive adhesive sheet for glass or tape according to any one of the above.

  [13] A bottom surface fixed to the inner surface of the vehicle window glass plate via a double-sided adhesive sheet or tape, a temporary fixing main body portion inserted into an engagement hole provided in a body flange of the vehicle, and the bottom surface A temporary fixing member with an adhesive layer for temporarily fixing a glass plate for a vehicle window, having the double-sided adhesive sheet for glass or tape according to any one of [1] to [12] attached thereto.

  [14] A glass plate for a vehicle window, a bottom surface fixed to the inner side surface of the glass plate via a double-sided adhesive sheet or tape, and a temporary fixing main body portion inserted into an engagement hole provided in a body flange of the vehicle And the double-sided pressure-sensitive adhesive sheet for glass or tape according to any one of [1] to [12], from which a release layer interposed between the glass plate and the temporary fixing member is removed. Glass plate for automobile window with temporary fixing member.

  According to the double-sided pressure-sensitive adhesive sheet or tape for glass of the present invention, the adhesive force between the glass plate and the member fixed thereto is strong, and the load is applied in a direction parallel to the surface of the pressure-sensitive adhesive layer. Even if it is done, a fixed position can be held. Therefore, when the window glass is attached to the opening of the vehicle, it is possible to reduce the deviation of the window glass from the temporarily held position until the adhesive is cured.

  The double-sided pressure-sensitive adhesive sheet or tape for glass of the present invention comprises a support comprising a sheet-like or tape-like foam or a support comprising a hard resin film laminated on at least one side of the sheet-like or tape-like foam, and both sides of this support. A pressure-sensitive adhesive layer formed on the substrate and a release layer attached to at least one surface of the pressure-sensitive adhesive layer opposite to the support are adhered to a glass plate for use. It is a double-sided adhesive sheet or tape. Hereinafter, “double-sided pressure-sensitive adhesive sheet or tape” is referred to as “double-sided pressure-sensitive adhesive tape” unless otherwise specified. This double-sided pressure-sensitive adhesive tape has a release layer on both sides, but it is naturally used after removing the release layer when it is made to adhere to the adherend surface. Release layers such as those with one or both sides of the release layer removed to adhere to the adherend surface, or those with one or both sides attached to the adherend surface after removal of one or both sides of the release layer What is naturally assumed to be absent is sometimes referred to as a double-sided adhesive tape.

  The double-sided pressure-sensitive adhesive tape of the present invention has a tensile shear displacement amount of 2.5 mm or less at the peak value of the tensile shear bond strength at room temperature in a tensile shear bond strength test according to JIS K 6850 using a glass plate as the adherend. This is a double-sided adhesive tape. The other adherend in the tensile shear bond strength test according to JIS K 6850 is preferably an adherend made of the same material as the surface in contact with the adhesive layer of the member fixed to the glass plate via the double-sided adhesive tape. . When the materials are not the same, it is preferable that the test is performed with an adherend having a substantially same adhesion force as the surface of the member to be fixed that is in contact with the adhesive layer. The material of the surface in contact with the adhesive layer of the member to be fixed is such that the tensile shear adhesive strength in the tensile shear adhesive strength test according to JIS K 6850 using a glass plate and the other adherend is 0.1 MPa or more. The other adherend is preferably made of a material. A more preferable material is a material having a surface with a tensile shear bond strength of 0.4 MPa or more.

  The material of the surface in contact with the adhesive layer of the member to be fixed is not limited to the material of the member itself, but may be a surface material modified by surface treatment or the like. In that case, it is preferable that the surface of the adherend in the above test is similarly modified. The modification of the surface may be performed on one surface of the glass plate and the other adherend, or may be performed only on the other surface. A typical surface modification is primer treatment, but is not limited thereto.

  The feature of the double-sided pressure-sensitive adhesive tape of the present invention is that there is little displacement with respect to a load in a direction parallel to the surface of the pressure-sensitive adhesive layer. That is, the tensile shear displacement test at the peak value of the tensile shear bond strength at room temperature is 2.5 mm or less in the tensile shear bond strength test according to JIS K 6850. The tensile shear displacement of an adherend having a primed surface is usually greater than the tensile shear displacement of an unprimed adherend. This is because when the peak value of the tensile shear bond strength is increased by the primer treatment, the tensile shear displacement amount apparently increases, but the shear displacement amount when compared with the same load is usually reduced by the primer treatment. At the same time, since the tensile shear bond strength is usually increased by the primer treatment, the surface contacting the adhesive layer of the glass plate or the member to be fixed is treated to increase the peak value of the tensile shear bond strength as in the primer treatment. Is preferred.

  In the test using the glass plate not subjected to the primer treatment as an adherend, the tensile shear displacement amount at the peak value of the tensile shear adhesive strength at room temperature is preferably 2.0 mm or less. In this test, an adherend that has not been primed is also used as the other adherend. In the case of double-sided adhesive tape, if this test is performed without performing primer treatment on both of the adherends, the peak value of the tensile shear adhesive strength decreases (that is, the adhesive layer and the adherend are easily peeled off), thereby causing the above-mentioned tension. The shear displacement also decreases (that is, peeling occurs with a small shear displacement). This phenomenon occurs similarly in the double-sided pressure-sensitive adhesive tape of the present invention and the conventional double-sided pressure-sensitive adhesive tape. Therefore, the shear displacement amount in the test of the double-sided pressure-sensitive adhesive tape of the present invention using the primer-treated adherence material and the shear displacement amount in the conventional double-sided pressure-sensitive adhesive tape test using the non-primer-treated adherend material Is a close value. In order to compare these two double-sided adhesive tapes, it is necessary to measure under the same test conditions. The shear displacement of the conventional double-sided pressure-sensitive adhesive tape using a non-primed adherend may be a value close to 2.5 mm, but the shear of the double-sided pressure-sensitive adhesive tape of the present invention measured under the same conditions The amount of displacement is preferably 2.0 mm or less.

  The double-sided pressure-sensitive adhesive tape of the present invention is used for fixing a glass plate and members made of various materials as described above. As the material of the glass plate, various glasses can be used, and examples thereof include soda lime silica glass, glass containing a coloring component such as iron ion in soda lime silica glass (glass having heat ray absorption ability), and the like. The shape of the glass plate may be a flat plate or may have a curvature. Furthermore, the glass plate may be either a single glass plate or a laminated glass in which a plurality of single glass plates are laminated via an intermediate film. Further, these glass plates may be tempered.

  The use of the glass plate having the member fixed by the double-sided pressure-sensitive adhesive tape of the present invention is not particularly limited, and examples thereof include automobile window glass and architectural glass, and those used for automobile window glass are preferable.

  The place where various members are fixed to the glass plate may be the glass surface, the peripheral edge, or the edge. Moreover, the surface on which various members are fixed in the glass plate may be the surface of the glass plate itself, or may be the surface on which the dark ceramic paste fired body is formed. Since the dark-colored ceramic pace fired body is usually formed by applying a composition containing glass frit and dark pigment on the glass surface and firing it, in the present invention, the properties relating to adhesion are the same as those on the glass surface. It is thought that it has. Further, a surface treatment such as a heat ray shielding coating (for example, a film made of a metal oxide or the like) may be applied.

  As various members to be fixed to the glass plate, resin members are preferable. Examples of the resin member include a temporary fixing member for temporarily holding the window glass in the opening of the vehicle; a member called a molding or a mold for closing the gap between the opening of the vehicle and the window glass; It is done. Examples of the material of the temporary fixing member include high-strength resins such as polybutylene terephthalate (PBT) and polyacetal (POM) that have a low mechanical deformation and a high mechanical strength. Examples of the molding material include soft vinyl chloride resin-based thermoplastic elastomers, olefin-based thermoplastic elastomers, and olefin-based thermoplastic rubbers.

  The member fixed to the glass plate is not limited to a resin member, and may be a metal member such as an aluminum die cast member or a member made of a steel plate subjected to various surface treatments. Examples of such a member include a bracket for fixing sensors such as a rain sensor to the surface of the window glass. Furthermore, it is also preferable to use the double-sided pressure-sensitive adhesive tape of the present invention for fixing between glass plates or a crow plate and other glass members.

  Specifically, the glass plate and various members can be bonded to the glass glass by fixing the temporary fixing member to the place where the dark ceramic paste fired body is formed, and fixing the molding to the periphery of the window glass. And the use of fixing the bracket to the surface of the window glass. Here, the shape and size of the members such as the temporary fixing member, the molding, and the bracket are not particularly limited, and various shapes and sizes can be used.

  It is preferable that the bonding surface of the glass plate and a member such as a resin member or a metal member is subjected to a polishing treatment with an abrasive or a cleaning treatment with a solvent. Each member may be subjected only to polishing treatment or cleaning treatment, but may be subjected to primer treatment as necessary. Various primers such as a urethane primer, an acrylic primer, and a silane coupling agent can be used as the primer, and the primer can be appropriately selected from those having good compatibility with the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer. In the present invention, since a urethane-based adhesive is preferable as the adhesive as described later, a urethane-based primer is preferable as the primer. As the urethane-based primer, “N-200; trade name” manufactured by Sumitomo 3M Ltd. can be preferably used. The treatment with the primer may be performed only on the adhesion surface of one adherend, or may be performed on the adhesion surfaces of both adherends.

  The double-sided pressure-sensitive adhesive tape of the present invention has a tensile shear bond strength at room temperature in a tensile shear bond strength test of the double-sided pressure-sensitive adhesive sheet or tape having a glass plate as an adherend and a release layer according to JIS K 6850 removed. The double-sided pressure-sensitive adhesive tape has a tensile shear displacement at a peak value of 2.5 mm or less. In the present invention, “room temperature” when performing a tensile shear bond strength test refers to a temperature range of 20 to 25 ° C.

  In the present invention, the “peak value of tensile shear bond strength” is a test piece when the crosshead moving speed is 10 mm / min at room temperature according to JIS K 6850 (tensile shear bond strength test method). This is the value of the tensile shear bond strength when ruptures. In addition, the adhesion | attachment conditions and test conditions of a test body are explained in full detail in an Example.

  That is, the tensile shear adhesive strength in the present invention is not the shear tensile shear adhesive strength of the double-sided pressure-sensitive adhesive tape itself, but the tensile shear adhesive strength of bonded materials.

  The peak value of the shear tensile shear bond strength is preferably 0.4 MPa or more, more preferably 0.6 MPa or more, and particularly preferably 1.0 MPa or more from the viewpoint of being effective for holding the fixed position. The upper limit of the peak value of the tensile shear bond strength is not particularly limited, but is generally about 1.5 to 1.7 MPa.

  In the present invention, the tensile shear displacement amount is a tensile shear bond in which a test piece breaks when tested at room temperature with a crosshead moving speed of 10 mm / min in accordance with JIS K 6850 (tensile shear bond strength test method). It shows the amount of movement of the crosshead when the strength is obtained (when the peak value of the tensile shear bond strength is obtained).

  In the present invention, the amount of tensile shear displacement is 2.5 mm or less, and preferably 2.0 mm or less when an adherend not subjected to primer treatment is used. When the tensile shear displacement is 2.5 mm or less, it is effective for maintaining the bonding position. The lower limit of the tensile shear displacement amount is not particularly limited, but if the difference in the thermal expansion coefficient of the adherend is large, peeling may occur at the interface between the adherend and the double-sided adhesive tape, or the glass plate may be broken. There is. Moreover, when a glass plate is a member used for transportation equipment such as a glass plate for an automobile window, if the amount of tensile shear displacement is extremely small, the glass plate may break due to vibration during use. Therefore, in such a case, it is preferable to have some amount of tensile shear displacement. In this case, the lower limit value of the tensile shear displacement amount is preferably 0.5 mm. Therefore, the tensile shear displacement is 2.5 mm or less, preferably 0.5 to 2.5 mm.

  As the double-sided pressure-sensitive adhesive tape of the present invention, various double-sided pressure-sensitive adhesive tapes can be used as long as they have the values of the tensile shear displacement and the tensile shear bond strength. Among these, in the present invention, a support formed of a sheet-like or tape-like foam or a support obtained by laminating a hard resin film on at least one side of a sheet-like or tape-like foam, and formed on both sides of this support In a double-sided pressure-sensitive adhesive tape comprising a pressure-sensitive adhesive layer and a release layer attached to at least one surface of the pressure-sensitive adhesive layer opposite to the support, the pressure-sensitive adhesive layer converts a polyol and a polyisocyanate compound to isocyanate. Formed with a urethane resin obtained by reacting a chain extender with an isocyanate group-terminated prepolymer obtained by reacting at an excessive ratio of the group, or a urethane resin obtained by further reacting a terminal stopper with the urethane resin. A double-sided adhesive tape is preferred.

  The double-sided pressure-sensitive adhesive tape comprises a support made of a sheet-like or tape-like foam or a support made by laminating a hard resin film on at least one side of a sheet-like or tape-like foam, and an adhesive formed on both sides of the support And a release layer attached to at least one surface of the pressure-sensitive adhesive layer opposite to the support.

[Support]
In the present invention, the foam is preferably made of a polyacrylic foam, a polyethylene foam, or a polyurethane foam. Polyurethane foam is particularly preferred.

The density of the polyurethane foam is preferably 100~800kg / ^{m 3,} more preferably 200 to 600 kg / ^{m 3.} When the density is less than 100 kg / m ³ , the strength as a support tends to be insufficient. On the other hand, if it exceeds 800 kg / m ³ , the tensile shear bond strength tends to be insufficient.

  Moreover, it is preferable that the thickness of the said polyurethane foam is 0.05-3.0 mm, and 0.1-2.0 mm is more preferable. If the thickness of the polyurethane foam is less than 0.05 mm, the tensile shear bond strength tends to be insufficient. On the other hand, if it exceeds 3.0 mm, the tensile shear displacement amount tends to increase.

  In the double-sided pressure-sensitive adhesive tape of the present invention, the support may consist only of the sheet-like or tape-like foam, and a hard resin film may be attached thereto. Among them, a hard resin film is affixed to at least one surface of a sheet-like or tape-like foam because it can provide a double-sided pressure-sensitive adhesive tape with high flexibility while having flexibility. Is preferred. And it is preferable that the foam and the hard resin film are affixed by reactive adhesion.

  The hard resin film has a thickness of 10 to 50 μm and is preferably made of polypropylene or polyethylene terephthalate.

  As the reactive bonding method between the sheet-like or tape-like foam and the hard resin film, for example, the foam raw material is predetermined on the surface of the hard resin film using a known spray coater such as a knife coater or a roll coater. A method in which foaming is completed at room temperature to 90 ° C. after coating, and curing is performed at 120 ° C. or lower in an oven at room temperature or high temperature.

  As a material (hereinafter referred to as “foam substrate”) in which a hard resin film is integrated by reactive adhesion on the surface of a sheet-like or tape-like foam, a commercially available one may be used. And “Nipplay MCS; trade name” commercially available from Nihon Hojo Co., Ltd.

[Adhesive layer]
In the double-sided pressure-sensitive adhesive tape of the present invention, the pressure-sensitive adhesive layer is obtained by reacting a chain extender with an isocyanate group-terminated prepolymer obtained by reacting a polyol and a polyisocyanate compound in an excess ratio of isocyanate groups. Or a pressure-sensitive adhesive made of a urethane resin mainly composed of a product obtained by reacting a terminal terminator, and mainly composed of a crosslinked polyurethane resin obtained by further reacting the urethane resin with a polyisocyanate compound. It is preferable to be formed with an adhesive.

  Hereinafter, the adhesive layer will be described in more detail.

(Polyol)
As a polyol used as a raw material for the isocyanate group-terminated prepolymer, for example, polyoxyalkylene polyol and polyester polyol are preferable, and polyoxyalkylene polyol is particularly preferable.

  The polyoxyalkylene polyol can be produced by ring-opening addition of alkylene oxide in the presence of a ring-opening polymerization catalyst and a polyvalent initiator.

  The alkylene oxide is preferably an alkylene oxide having 2 to 6 carbon atoms, and specific examples thereof include ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide and the like. Among these, ethylene oxide, propylene oxide, and combinations thereof are particularly preferable.

  Examples of the ring-opening polymerization catalyst include general-purpose alkali metal compound catalysts such as potassium hydroxide (KOH) and sodium hydroxide; cesium metal compound catalysts such as cesium hydroxide; double metal cyanide complex catalysts such as zinc hexacyanocobaltate complex A phosphazene catalyst and the like.

  The polyvalent initiator is a compound having two or more active hydrogen atoms with which an alkylene oxide can react, and examples thereof include polyhydric alcohols, polyhydric phenols, polyamines, and alkanolamines. The valence is preferably 2 to 6, more preferably 2 to 3, and most preferably 2. Specifically, for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, bisphenol A, glycerin, trimethylolpropane or a small amount thereof. Examples include relatively low molecular weight polyoxyalkylene polyols to which alkylene oxide is added. When using a double metal cyanide complex catalyst, it is preferable to use a polyoxyalkylene polyol having a molecular weight per hydroxyl group of 200 to 500 as a polyvalent initiator. These may use only 1 type and may use 2 or more types together.

  The polyoxyalkylene polyol preferably has an average number of hydroxyl groups of 2 or more, more preferably 2 to 6, particularly preferably 2 to 3, and most preferably 2. The number of hydroxyl groups per molecule of the polyoxyalkylene polyol matches the number of active hydrogen atoms of the polyvalent initiator used for production.

  The polyoxyalkylene polyol preferably has a hydroxyl value of 5.6 to 600 mgKOH / g. When the hydroxyl value is less than 5.6 mg KOH / g, the molecular weight is large, so that it is difficult to react with the polyisocyanate compound, and the obtained prepolymer tends to be difficult to react with the chain extender. On the other hand, when it exceeds 600 mgKOH / g, the ratio of the isocyanate compound in the obtained prepolymer becomes relatively high, and gelation is likely to occur when the isocyanate group-terminated prepolymer is reacted with a chain extender.

  The hydroxyl value of the polyoxyalkylene polyol is preferably 5.6 to 280 mgKOH / g, more preferably 11 to 112 mgKOH / g, and most preferably 18 to 75 mgKOH / g.

  The polyoxyalkylene polyol may be a mixture of two or more, and even in that case, the average degree of unsaturation and the hydroxyl value are preferably within the above ranges.

  A known polyester polyol can be used as the polyester polyol. For example, a polyester polyol obtained by condensation reaction of a low molecular weight diol component and a dibasic acid component can be mentioned. Examples of the low molecular weight diol include ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, and 3,3′-diene. Methylol heptane, polyoxyethylene glycol, polyoxypropylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, octanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, Examples include cyclohexanediol and bisphenol A. Further, glycerin, trimethylolpropane, pentaerythritol and the like may be used in combination with a low molecular weight diol. Examples of the dibasic acid component include terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid, trimellitic acid, and other aliphatic dibasic acids or aromatic dibasic acids. Polyester polyols obtained by ring-opening polymerization of cyclic ester compounds such as lactones such as poly (ε-caprolactone), poly (β-methyl-γ-valerolactone), and polyvalerolactone can also be used.

  The polyester polyol preferably has a hydroxyl value of 20 to 600 mgKOH / g, and more preferably 30 to 300 mgKOH / g.

  The polyester polyol may be a mixture of two or more, and in that case, the average hydroxyl value is preferably within the above range.

  As the polyol, a polyoxyalkylene polyol and a polyester polyol may be used in combination, but they are different in reactivity, and are easily gelled or turbid in the reaction solution. It is preferable to set it as mass% or less, and it is more preferable to set it as 5 mass% or less. In addition, it is more preferable not to use polyoxyalkylene polyol and polyester polyol together. If the reaction solution becomes turbid, a colorless and transparent urethane resin cannot be obtained.

(Polyisocyanate compound)
As the polyisocyanate compound used as the raw material for the isocyanate group-terminated prepolymer, known aromatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, and the like can be used.

  Examples of the aromatic polyisocyanate include a polyisocyanate having an aromatic ring and having an isocyanate group directly bonded to the aromatic ring, and a polyisocyanate having an aromatic ring and an isocyanate group not directly bonded to the aromatic ring. Can be mentioned. Specifically, examples of the polyisocyanate having an aromatic ring and having an isocyanate group directly bonded to the aromatic ring include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, and 4,4′-diphenylmethane diisocyanate. (Hereinafter referred to as “MDI”), 2,4-tolylene diisocyanate (hereinafter referred to as “2,4-TDI”), 2,6-tolylene diisocyanate (hereinafter referred to as “2,6-TDI”) 4,4′-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4′-diphenyl ether diisocyanate, 4,4 ′, 4 "-triphenylmethane triisocyanate, etc. Has an aromatic ring, as the polyisocyanate having an isocyanate group is not directly bonded to the aromatic ring, for example, p- tetramethylxylylene diisocyanate, m- tetramethylxylylene diisocyanate, and the like.

  Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (hereinafter referred to as “HDI”), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate and the like can be mentioned.

  Examples of the alicyclic polyisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (hereinafter referred to as “IPDI”), 1,3-cyclopentane diisocyanate, and 1,3-cyclohexane diisocyanate. 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanatomethyl) cyclohexane, 1, 4-bis (isocyanatomethyl) cyclohexane and the like can be mentioned.

  Further, it may be a trimethylolpropane adduct type modified product of the polyisocyanate compound described above, a burette type modified product reacted with water, or an isocyanurate type modified product containing an isocyanurate ring.

  Among the polyisocyanate compounds described above, one or more selected from HDI, IPDI, MDI, 2,4-TDI, 2,6-TDI, and modified products thereof are preferable. When importance is attached to weather resistance, one or more selected from HDI, IPDI and their modified products are particularly preferred.

(Isocyanate group-terminated prepolymer)
The said polyol and polyisocyanate compound are made to react and an isocyanate group terminal prepolymer is obtained. The production reaction of the isocyanate group-terminated prepolymer is not particularly limited, and examples thereof include a method in which a polyol, a polyisocyanate compound, and, if necessary, a urethanization catalyst and a solvent are charged in a reactor.

  The mixing ratio of the polyol and the polyisocyanate compound is such that the index [(number of moles of NCO / number of moles of OH) × 100] is 110 to 300 in order to leave an isocyanate group at the terminal. Preferably, the reaction is more preferably 130 to 250. If the index is less than 110, gelation tends to increase the viscosity, and if it exceeds 300, the concentration of unreacted isocyanate compound in the prepolymer becomes too high and the chain extension reaction in the next step tends to be difficult.

  The isocyanate group content of the isocyanate group-terminated prepolymer (hereinafter referred to as “NCO%”) is 0.5 to 0.5, although it varies depending on the reactivity of the polyol and polyisocyanate compound used and the blending amount of the chain extender. 12 mass% is preferable and 1-4 mass% is more preferable. If the NCO% is less than 0.5% by mass, a sufficient amount of chain extender cannot be reacted, and if it exceeds 12% by mass, the chain extension reaction tends to be difficult to control.

  Examples of the urethanization catalyst used in the prepolymer formation reaction include known ones such as tertiary amine compounds and organometallic compounds.

  Examples of the tertiary amine compound include triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) and the like.

  Examples of organometallic compounds include tin compounds and non-tin compounds. Examples of tin compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (hereinafter referred to as “DBTDL”), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide. , Tributyltin oxide, tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, tin 2-ethylhexanoate and the like. Examples of non-tin compounds include titanium compounds such as dibutyltitanium dichloride, tetrabutyltitanate, butoxytitanium trichloride, lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate. Iron compounds such as iron 2-ethylhexanoate and iron acetylacetonate, cobalt compounds such as cobalt benzoate and cobalt 2-ethylhexanoate, zinc compounds such as zinc naphthenate and zinc 2-ethylhexanoate, Examples thereof include zirconium naphthenate.

  Among the urethanization catalysts described above, DBTDL, 2-ethylhexanoic acid tin and the like are preferable. Moreover, the urethanization catalyst mentioned above may be used independently, and may be used together.

  Examples of the solvent include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, esters such as ethyl acetate and butyl acetate, and ketones such as methyl ethyl ketone (hereinafter referred to as “MEK”). , Dimethylformamide, cyclohexanone, and the like. These may be used alone or in combination of two or more.

  The reaction temperature is preferably 120 ° C. or lower, more preferably 70 to 100 ° C. When the reaction temperature exceeds 120 ° C., the allophanate reaction proceeds to make it difficult to synthesize an isocyanate group-terminated prepolymer having a predetermined molecular weight and structure, and it becomes difficult to control the reaction rate. When the reaction temperature is 70 to 100 ° C., the reaction time is preferably 2 to 20 hours.

(Chain extender)
At least a part of the chain extender is preferably a compound selected from the following (a) and (b).

(A) having three or more functional groups capable of reacting with an isocyanate group, and two of these functional groups are one or two selected from a primary amino group, a secondary amino group, and a primary hydroxyl group A compound which is a functional group and the remaining functional group is at least one functional group selected from a secondary hydroxyl group, a tertiary hydroxyl group and a carboxyl group.
(B) having three or more functional groups capable of reacting with an isocyanate group, two of which are one or two functional groups selected from a primary amino group and a secondary amino group A compound in which the remaining functional group is a primary hydroxyl group.

  As such a chain extender, the molecular weight is preferably 500 or less.

  Examples of the chain extender include the following compounds (1) to (6).

(1) A compound having one primary amino group, one primary hydroxyl group and at least one secondary hydroxyl group.
(2) A compound having one secondary amino group, one primary hydroxyl group and at least one secondary hydroxyl group.
(3) A compound having two primary hydroxyl groups and at least one secondary hydroxyl group or tertiary hydroxyl group.
(4) A compound having two amino groups and at least one hydroxyl group.
(5) A compound having two primary hydroxyl groups and at least one carboxyl group.
(6) A compound having two amino groups and at least one carboxyl group.

  Specific examples of the compound (1) include 1-amino-2,3-propanediol (hereinafter referred to as “APD”) and the like.

  Specific examples of the compound (2) include 1-methylamino-2,3-propanediol (hereinafter referred to as “MAPD”), N- (2-hydroxypropyl) ethanolamine, and the like. .

  As a specific example, the compound of the above (3) is, for example, adding an alkylene oxide having 3 to 4 carbon atoms to one compound selected from the group consisting of diethanolamine, triethanolamine, trimethylolpropane and pentaerythritol. (C3-C4 alkylene oxide includes propylene oxide, 1,2-butylene oxide, 3,4-butylene oxide), glycerin, diglycerin, 1,2,4-butane Examples thereof include glycerin compounds such as triol and 1,2,5-pentanetriol, mannitol, maltose, sorbitol and the like.

  The amino group of the compound (4) may be either a primary amino group or a secondary amino group. Further, the hydroxyl group may be a primary, secondary or tertiary hydroxyl group. The compound (4) is, for example, a propylene oxide 1 mol adduct of metaxylylenediamine (manufactured by Aoki Yushi Co., Ltd., “MXDA-PO1; trade name”), propylene oxide 2 of metaxylylenediamine. Mole adduct (Aoki Yushi Co., Ltd., “MXDA-PO2; trade name”), metaxylylenediamine 1-mol ethylene oxide adduct (Aoki Yushi Co., Ltd., “MXDA-EO1; trade name”), metaxylylene diamine Ethylene oxide 2 mol adduct (Aoki Yushi Co., Ltd., “MXDA-EO2; trade name”), 2-hydroxyethylaminopropylamine (manufactured by Koei Chemical Co., Ltd.), aminoethylethanolamine, N- (2-hydroxyethyl) Examples include xylylenediamine.

  Examples of the compound (5) include dimethylolcarboxylic acids. Specific examples thereof include dimethylolpropionic acid (hereinafter referred to as “DMPA”) and 2,2-bis (hydroxymethyl) propionic acid). Dimethylolbutanoic acid (hereinafter referred to as “DMBA”), 2,2-bis (hydroxymethyl) butanoic acid), dimethylolpentanoic acid (2,2-bis (hydroxymethyl) pentanoic acid), dimethylolheptane Acid (2,2-bis (hydroxymethyl) heptanoic acid), dimethyloloctanoic acid (2,2-bis (hydroxymethyl) octanoic acid), dimethylolnonanoic acid (2,2-bis (hydroxymethyl) nonanoic acid ) And the like.

  Specific examples of the compound (6) include lysine and arginine.

  In the present invention, as a chain extender, in addition to the compounds (1) to (6), a compound having one secondary amino group and one primary hydroxyl group and one tertiary hydroxyl group, etc. Can also be used.

  And as a chain extender in this invention, the compound of said (1)-(3) is preferable, More preferably, it is a compound of said (1), (2).

The above compound has three or more functional groups, but two relatively reactive functional groups mainly react with an isocyanate group-terminated prepolymer, and the remaining relatively reactive functional groups react. Without remaining in the resin. This remaining functional group can later be used in a crosslinking reaction with a crosslinking agent. Moreover, since this chain extension reaction is easy to control the reaction, the gelation of the product can be suppressed to prevent the urethane resin from becoming highly viscous.
All of the above compounds are easily available and low in cost.

(Other chain extenders)
In the present invention, other chain extenders other than the above compounds can be used in combination. As the other chain extender, a compound having a molecular weight of 500 or less having two functional groups capable of reacting with an isocyanate group is preferable. Examples of other chain extenders include diamine compounds such as isophorone diamine, ethylene diamine and tolylene diamine, diol compounds such as 1,4-butanediol, 1,6-hexanediol and ethylene glycol, and alkanolamines such as monoethanolamine. Kind. Moreover, you may use together a small amount of triol compounds other than the above-mentioned compound. When using other chain extenders, 50 mol% or less of the total amount of chain extenders used is preferable.

  Further, in the case where a chain extender having three or more functional groups capable of reacting with the isocyanate group is combined with other chain extenders, urethanes in which the residues of these chain extenders are uniformly arranged in the molecule In order to obtain a resin, it is preferable to combine a chain extender having three or more functional groups capable of reacting with the isocyanate group, other chain extenders, and those having close reactivity with the isocyanate group. For example, when the chain extender having three or more functional groups capable of reacting with the isocyanate group has two amino groups, the other chain extender is preferably a diamine compound such as ethylenediamine or tolylenediamine. . When the chain extender having three or more functional groups capable of reacting with the isocyanate group has two primary hydroxyl groups, it is preferable to combine a diol compound such as 1,4-butanediol as the other chain extender. .

(Urethane resin)
The isocyanate group-terminated prepolymer and the chain extender are subjected to a chain extension reaction to obtain a urethane resin. The chain extension reaction is not particularly limited, and examples thereof include the following methods (A) to (C). Since the isocyanate group gradually decreases, it is easy to obtain a uniform resin. The method (C) is preferred.

(A) A method in which an isocyanate group-terminated prepolymer solution is charged into a flask and a chain extender is dropped into the flask to cause a reaction.
(B) A method in which a chain extender is charged into a flask and an isocyanate group-terminated prepolymer solution is dropped to react.
(C) A method in which the isocyanate group-terminated prepolymer solution is diluted with a solvent, and then a predetermined amount of a chain extender is added to the flask and reacted.

  The addition amount of the chain extender varies depending on the NCO% of the isocyanate group-terminated prepolymer, but is preferably an amount such that the NCO% of the isocyanate group-terminated prepolymer after chain extension is 0.01 to 1.0% by mass. More preferably, the amount is 0.05 to 0.2% by mass. When the amount of the chain extender added is such that the NCO% of the isocyanate group-terminated prepolymer is less than 0.01% by mass, the viscosity rapidly increases during the chain extension reaction, and gelation tends to occur. If the amount of NCO% of the isocyanate group-terminated prepolymer exceeds 0.4% by mass, chain extension becomes insufficient and it becomes difficult to obtain a desired molecular weight.

  The reaction temperature in the chain extension reaction is preferably 80 ° C. or lower. When the reaction temperature exceeds 80 ° C., the reaction rate becomes too fast and it becomes difficult to control the reaction, so that it tends to be difficult to obtain a urethane resin having a desired molecular weight and structure. When the chain extension reaction is carried out in the presence of a solvent, the boiling point is preferably not higher than the boiling point of the solvent, and particularly 40 to 60 ° C. is preferred in the presence of MEK and ethyl acetate.

  In the present invention, the urethane resin obtained by the chain extension reaction may be further reacted with a terminal terminator. By reacting with a terminal stopper, a highly stable urethane resin can be obtained.

  The terminal terminator is a compound having a functional group capable of reacting with an isocyanate group and having only one functional group, or a compound having a functional group capable of reacting with an isocyanate group, A compound having one or two functional groups having high reactivity and functional groups having lower reactivity than the functional group can be used.

  As the compound having only one functional group, that is, a compound having only one primary amino group, secondary amino group, tertiary amino group, primary hydroxyl group or secondary hydroxyl group can be used. Examples thereof include monoamine compounds such as diethylamine and morpholine and monool compounds such as methanol.

  As a compound having a functional group capable of reacting with an isocyanate group and having one functional group having a high reactivity and one or two functional groups having a reactivity lower than the functional group, for example, one The compound which has a 1-2 hydroxyl group with a secondary amino group or a secondary amino group is mentioned. Such a compound has two or more functional groups, but the reactivity of the functional groups is different. Therefore, after one highly functional functional group reacts, the remaining functional groups do not react. , Substantially equivalent to monofunctionality. The hydroxyl group is more preferably a secondary hydroxyl group. Specifically, monoamine compounds having a hydroxyl group such as 2-amino-2-methyl-1-propanol (hereinafter referred to as “AMP”), monoisopropanolamine, aminopropanol, and the like can be used.

  The addition amount of the terminal stopper is preferably such that the terminal stopper is 1 mole or more and 2 moles or less with respect to 1 mole of the terminal isocyanate group remaining after the chain extension reaction. If it is less than 1 mol, an isocyanate group remains after the termination reaction, and the resulting urethane resin becomes unstable. If it exceeds 2 moles, the number of low molecular weight compounds increases, which is not preferable.

  Moreover, you may add an additive as needed. Examples of the additive include fillers such as talc, calcium carbonate, and titanium oxide, tackifiers, colorants, ultraviolet absorbers, antioxidants, antifoaming agents, and light stabilizers.

  The urethane resin has a standard polystyrene equivalent molecular weight by GPC, preferably a number average molecular weight of 10,000 or more, and more preferably a number average molecular weight of 30,000 or more. If the number average molecular weight is less than 10,000, the adhesive properties, particularly the holding power, are remarkably lowered, which is not preferable. The upper limit is not particularly limited, but if the number average molecular weight exceeds 300,000, gelation may occur, which is not preferable. Therefore, the number average molecular weight is preferably 300,000 or less.

(Crosslinked polyurethane resin)
Since the urethane resin itself has adhesive performance, it can be used as it is as an adhesive layer. However, the functional group remaining in the urethane resin is further reacted with the second polyisocyanate compound as a cross-linking agent to crosslink through the functional group remaining in the urethane resin, thereby balancing the adhesion performance and strength. Becomes better. Moreover, since it uses the urethane resin mentioned above, it is low-cost. And since this urethane resin and the said crosslinked polyurethane resin do not contain an acryl-type compound, it is thought that the transferability to a to-be-adhered body and skin irritation are low. Furthermore, since this crosslinked polyurethane resin has a large molecular weight and is difficult to harden at low temperatures, it is considered that the temperature dependency of the adhesive force is low. And it seems that a low molecular weight compound does not transfer to the surface like a rubber-type adhesive.

  Examples of the polyisocyanate compound that can be used as a crosslinking agent include the polyisocyanate compounds described above and polyfunctional polyisocyanates such as trimethylolpropane adduct-type modified products, burette-type modified products, and isocyanurate-type modified products. Among these, a modified product having an average functional group number exceeding 2 is preferable. For example, “Duranate P301-75E; trade name” (manufactured by Asahi Kasei Co., Ltd., trimethylolpropane adduct type HDI, isocyanate group content: 12.9 mass%, solid content: 75 mass%), “Coronate L; trade name” (Japan) The product made from a polyurethane company, a trimethylol propane adduct type TDI, isocyanate group content: 13.5 mass%, solid content: 75 mass%), etc. can be used.

  As a use amount of the crosslinking agent, a polyisocyanate compound having an isocyanate group content (excluding a solvent in the case of a solution) of 10 to 30% by mass is reacted within a range of 20 parts by mass or less with respect to 100 parts by mass of the urethane resin. It is preferable to make it. It is more preferably 0.01 to 10 parts by mass because better removability is exhibited. On the other hand, when a polyisocyanate compound as a crosslinking agent is not used, the cohesive force is lowered and the cohesive failure is easily caused. Moreover, when it exceeds 20 mass parts, it exists in the tendency for aggregation to be too strong and for adhesive force to fall. Since the strength of the pressure-sensitive adhesive can be adjusted by adjusting the amount of the crosslinking agent used, it is possible to easily obtain a pressure-sensitive adhesive having a balance between pressure-sensitive adhesiveness and strength.

  The polyisocyanate compound as a crosslinking agent is preferably added to the urethane resin and subjected to a crosslinking reaction immediately before the pressure-sensitive adhesive layer is formed on the support.

  When the crosslinking agent and the functional group remaining in the urethane resin are reacted, a urethanization catalyst can be used. As a urethanization catalyst, the urethanization catalyst used in the isocyanate group terminal prepolymer production | generation reaction can be used.

  Moreover, you may add an additive as needed. As an additive, an isocyanate group containing silane compound etc. are mentioned, for example.

  The pressure-sensitive adhesive layer in the present invention preferably has an adhesive strength measured by the following method of 10 N / 25 mm or more. That is, a pressure-sensitive adhesive sheet is obtained by providing a pressure-sensitive adhesive layer with a thickness of 25 μm on a 25 μm PET film. This adhesive sheet cut into a 25 mm wide tape is stuck to a stainless steel plate (SUS304 (JIS)) having a thickness of 1.5 mm in an atmosphere at 23 ° C. and a relative humidity of 65%. Subsequently, pressure bonding is performed using a 2 kg rubber roll according to JIS Z 0237 (1991). This is a method of measuring adhesive strength (180 degree peel, tensile speed 300 mm / min) with a tensile tester specified in JIS B 7721 after 30 minutes.

[Peeling layer]
In the double-sided pressure-sensitive adhesive tape of the present invention, a release layer for protecting the pressure-sensitive adhesive layer of the pressure-sensitive adhesive layer is provided on at least one surface of the pressure-sensitive adhesive layer until use. For example, when the double-sided pressure-sensitive adhesive tape is in sheet form, it is preferable to have it on both surfaces of the pressure-sensitive adhesive layer opposite to the support. Moreover, when a double-sided adhesive tape is roll shape, it is preferable to have on one surface of the surface on the opposite side to the said support body of an adhesive layer.

  The release layer is not particularly defined, and can be appropriately selected from known release liner films. For example, paper, non-woven fabric, or a synthetic resin film such as polyethylene terephthalate is used as a base material, and at least one surface of the base material is a silicone release agent, a fluorine release agent, a long-chain alkyl release treatment And a treatment agent such as an agent, and a release treatment layer is provided.

[Method for producing adhesive sheet or tape]
The double-sided pressure-sensitive adhesive tape of the present invention can be produced, for example, as follows.
That is, a pressure-sensitive adhesive layer is formed by supplying a urethane resin solution or a mixture of a urethane resin solution and a cross-linking agent to the surface of the release liner film on which the release treatment layer is provided, and extending and drying it. Next, a support is laminated on the pressure-sensitive adhesive layer, and the pressure-sensitive adhesive layer is formed on the support. In addition, the same operation is performed on the other surface to form an adhesive layer on both surfaces of the support.
Then, the release liner film and the support integrated with each other through the pressure-sensitive adhesive layer are cured at room temperature for about one week. At this time, when a mixture of the urethane resin solution and the crosslinking agent is supplied, the crosslinking reaction of the urethane resin proceeds on the release liner film to form a crosslinked urethane resin. By carrying out like this, the double-sided adhesive tape protected with the liner film for peeling (peeling layer) can be manufactured. In addition, a peeling layer may be provided in both surfaces of the adhesive layer of a double-sided adhesive tape, and may be provided only in one side. Moreover, when providing a peeling layer only on the single side | surface of an adhesive layer, it is preferable that a double-sided adhesive tape is wound up in roll shape using the peeling liner film which can peel on both surfaces.
The double-sided pressure-sensitive adhesive tape thus obtained can be used in the form of a sheet or cut into a tape depending on the intended use.

  And the double-sided pressure-sensitive adhesive tape of the present invention is a tensile shear bond at room temperature in a tensile shear bond strength test of the double-sided pressure-sensitive adhesive sheet or tape from which a release layer according to JIS K 6850 is removed using a glass plate as an adherend. When the tensile shear displacement amount at the peak value of the strength is 2.5 mm or less, the resin member or the metal member is fixed to the glass plate, or between the glass plates or the crow plate and other glass members. Suitable for fixing. In particular, it is effective for the purpose of adhering a glass plate and a resin member, and the adherend can be firmly fixed even in a situation where a load is applied, and displacement can be suppressed.

  The double-sided pressure-sensitive adhesive tape of the present invention has a low skin irritation because the pressure-sensitive adhesive layer is made of a polyurethane resin and does not contain an acrylic resin. Moreover, it is excellent in reworkability and can be re-attached. Since the tensile shear bond strength is high and the tensile bond shear displacement amount can be reduced, the adherend can be firmly fixed even when a load is applied.

  Specifically, it is particularly suitable for applications in which a temporary fixing member, a resin member such as a molding, and a metal member such as a bracket are bonded to a plate glass for an automobile window.

  FIG. 6 is a diagram illustrating an example of a temporary fixing member with an adhesive layer for temporarily fixing a glass plate for an automobile window, and an automotive window glass plate with a temporary fixing member. The adhesive of the present invention is obtained by cutting the double-sided pressure-sensitive adhesive tape 18 in accordance with the shape of the bottom surface (location fixed to the glass plate) of the temporary fixing member 17, peeling off one release layer, attaching it to the bottom surface, and pressing. The temporary fixing member 15 with an agent layer is obtained. The peeling layer is peeled off from the temporary fixing member with the adhesive layer, and is attached to a predetermined position of the glass for automobile window, crimped, and cured as necessary. can get.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

[1] Production example of pressure-sensitive adhesive A pressure-sensitive adhesive was produced according to the following production example (1). In addition, the polyol (P1) shown below was used for the polyol used by each manufacture example. Moreover, the compound (C1) shown below was used for the chain extender.

[Polyol]
Polyol (P1): Polyoxypropylene diol having a hydroxyl value of 56.1 mgKOH / g, produced by reacting propylene oxide with propylene glycol as an initiator and using a KOH catalyst.
[Chain extender]
Compound (C1): N- (2-hydroxypropyl) ethanolamine [Terminator]
MIPA: Monoisopropanolamine

(Production Example 1)
215.3 g of polyol (P1), 28.1 g of 2,4-TDI (made by Nippon Polyurethane Industry Co., Ltd., trade name) in a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel Coronate T-100), DBTDL as a urethanization catalyst in an amount corresponding to 25 ppm with respect to the total amount of polyol (P1), and TDI, gradually raised to 80 ° C., and reacted for 2 hours to react with an isocyanate group A terminal prepolymer was obtained (NCO% of the obtained prepolymer is shown in the table). Then, after cooling to 60 ° C. and adding 125 g of ethyl acetate and 125 g of MEK, 5.92 g of the compound (C1) as a chain extender was added and reacted. The reaction was continued at 60 ° C., and when NCO% became 0.1% by mass or less, 0.7 g of MIPA as a terminal stopper was added to terminate the reaction, and a polyurethane solution (urethane resin A) was obtained.
The obtained polyurethane solution was colorless and transparent and had a solid content of 50% by mass. The viscosity of the polyurethane solution was measured and found to be 4,300 mPa · s / 25 ° C. The number average molecular weight of the resin in this polyurethane solution was 56,000.
The viscosity of the polyurethane solution at 25 ° C. was measured with a B-type viscometer. The number average molecular weight of the resin component in the polyurethane solution was measured in terms of polystyrene by gel permeation chromatography.
Next, Coronate L (manufactured by Nippon Polyurethane Co., Ltd., trimethylolpropane adduct type TDI, isocyanate group content: 13.5% by mass, solid content: 75% by mass) as a crosslinking agent with respect to 100 parts by mass of the obtained polyurethane solution Was added and stirred and mixed at 40 rpm for 1 minute to obtain an adhesive _AP (crosslinked polyurethane resin). The results of measurement of the adhesive strength by the above method of measuring the adhesive A _P shown in Table 1.

[2] Production example of adhesive tape (Example 1)
As shown in FIG. 1 (a), a release agent for a release liner film 1 (corresponding to the release layer of the present invention) having a thickness of 100 μm and made of a polyethylene terephthalate film coated with a silicone release agent on one side is provided. the coated surface, a pressure-sensitive adhesive a _P obtained in production example 1, the thickness after drying by coating so as to be 35μm to form an adhesive layer 2. Next, the release liner film 1 on which the pressure-sensitive adhesive layer 2 was formed was dried at 100 ° C. for 1 minute to remove the solvent. Then, a foam base material 5 (Japan) having a polyethylene terephthalate film (corresponding to the hard resin film of the present invention) 4 having a thickness of 38 μm attached to one surface of a urethane foam 3 having a thickness of 0.41 mm and a density of 350 kg / m ^3. The release liner film 1 having the pressure-sensitive adhesive layer 2 formed thereon is bonded to one surface of the product name “Nipplay MCS” 0.44 mm thickness and density 580 kg / m ³ ) via the pressure-sensitive adhesive layer 2. It was. Similarly, the release liner film 1 on which the pressure-sensitive adhesive layer 2 was formed was also bonded to the other surface of the foam substrate 5 via the pressure-sensitive adhesive layer 2. Thus, the pressure-sensitive adhesive layer 2 was formed on both surfaces of the foam substrate 5 as shown in FIG. Then, it cured for 1 week on room temperature conditions, the adhesive was hardened, and the adhesive sheet of Example 1 was obtained. The obtained adhesive sheet was cut into a tape having a width of 20 mm to obtain an adhesive tape.

(Example 2)
As a support, a foam base material 5 having a 38 μm-thick polyethylene terephthalate film 4 attached to one side of a urethane foam 3 having a thickness of 0.41 mm and a density of 350 kg / m ³ (trade name “Nippray MCS manufactured by Nippon Kajo Co., Ltd.) ”A pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that a urethane foam having a thickness of 0.40 mm and a density of 350 kg / m ³ was used instead of a thickness of 0.45 mm and a density of 580 kg / m ³ ). . The obtained pressure-sensitive adhesive sheet was cut into a tape having a width of 20 mm to obtain a pressure-sensitive adhesive tape. An acrylic resin-based pressure-sensitive adhesive layer was formed on both surfaces of a support made of acrylic foam instead of the pressure-sensitive adhesive tape of Example 1. A commercial product A ("# 4215; trade name, manufactured by Sumitomo 3M Co., Ltd., thickness 0.40 mm) cut into 20 mm width was used.

[3] Adhesive evaluation example of adhesive tape [3-1] Tensile shear adhesive strength and tensile shear displacement (Part 1)
As shown in FIG. 3, a dark ceramic paste fired body layer b was formed on one end of a glass flat plate a having a size of 150 mm × 25 mm and a thickness of 5 mm. Next, the flat c (40 mm × 20 mm, thickness 3 mm) made of polybutylene terephthalate and the adhesion surface of the dark ceramic paste fired body layer were degreased with isopropyl alcohol and air-dried. Commercially available primers (manufactured by Sumitomo 3M, product number; N-200) were applied to these substrates and dried.
The double-sided pressure-sensitive adhesive tapes of Example 1, Example 2, and Comparative Example 1 cut into 20 mm × 10 mm were attached to a polybutylene terephthalate substrate. Next, this was affixed to the edge part of a dark-colored ceramic paste fired body layer, it was made to press-fit with 100N for 10 second, and was cured for 24 hours, and the test piece was obtained. The adhesion area was 20 mm × 10 m. The obtained test piece was subjected to a tensile shear displacement amount and a tensile shear bond strength with a crosshead moving speed of 10 mm / min in accordance with a tensile shear bond strength test defined in JIS K 6850. The results are shown in Table 2 and FIG.

  As shown in Table 2 and FIG. 3, the double-sided pressure-sensitive adhesive tapes of Example 1 and Example 2 had high tensile shear adhesive strength and small tensile adhesive shear displacement.

[3-2] Tensile shear adhesive strength and tensile shear displacement (Part 2)
Using the double-sided pressure-sensitive adhesive tapes of Example 1 and Comparative Example 1, (a) Test pieces obtained without performing primer treatment on both the dark ceramic paste fired body layer of the glass plate and the base made of polybutylene terephthalate, (b ) A test piece obtained by primer-treating only a base material made of polybutylene terephthalate without subjecting the dark-colored ceramic paste fired body layer to a primer treatment, and (c) a primer for both the fired-color ceramic paste fired body layer and the base material made of polybutylene terephthalate About the test piece obtained by processing, it carried out similarly to [3-1], and performed the tensile shearing adhesive strength test. The results are shown in Table 3 and FIGS.

  As shown in Table 3 and FIGS. 4 and 5, when the adhesive tape of Example 1 was used, the peak value of the tensile shear adhesive strength at room temperature for the test piece obtained by priming the dark ceramic paste fired body layer of the glass plate It can be seen that the amount of tensile shear displacement at is 2.5 mm or less.

  The double-sided pressure-sensitive adhesive tape of the present invention is useful for applications in which various members such as resin members are fixed to a glass plate. Therefore, it can be applied to a double-sided adhesive tape or the like in a field where a glass plate is used, and can be effectively applied as a double-sided adhesive tape in the automobile industry field.

It is explanatory drawing which shows an example of the manufacturing method of the double-sided adhesive tape of this invention. It is explanatory drawing which shows the adhesive evaluation method of a double-sided adhesive tape. It is a graph which shows the relationship between the tensile adhesive shear strength of the double-sided adhesive tape of an Example and a comparative example, and the amount of tensile shear displacement. It is another chart which shows the relationship between the tensile adhesive shear strength of the adhesive tape of an Example, and the amount of tensile shear displacement. It is another chart which shows the relationship between the tension adhesive shear strength of the adhesive tape of a comparative example, and the amount of tensile shear displacement. It is explanatory drawing which shows an example of the glass plate temporary clip for vehicle windows of this invention, and a glass plate with a temporary fix member.

Explanation of symbols

1: Release liner film (release layer)
2: Adhesive layer 3: Urethane foam (foam)
4: Polyethylene terephthalate film (hard resin film)
5: Foam substrate (support)
a: Glass flat plate b: Dark ceramic paste fired body layer c: Polybutylene terephthalate flat plate d: Double-sided adhesive tape 17: Temporary fastening member 18: Double-sided 15: Temporary fastening member with adhesive layer W: Automotive glass plate 40: Temporary fastening Automotive window glass plate with components

Claims (14)

A support made of sheet-like or tape-like foam, or a support made by laminating a hard resin film on at least one side of a sheet-like or tape-like foam, an adhesive layer formed on both sides of this support, and this adhesive A double-sided pressure-sensitive adhesive sheet or tape that is used by adhering at least one pressure-sensitive adhesive surface to a glass plate, comprising a release layer attached to at least one surface of the layer opposite to the support,
In the tensile shear bond strength test of the double-sided pressure-sensitive adhesive sheet or tape from which the release layer according to JIS K 6850 is removed using a glass plate as the adherend, the tensile shear displacement amount at the peak value of the tensile shear bond strength at room temperature is A double-sided pressure-sensitive adhesive sheet for glass or tape that is 2.5 mm or less.   2. The double-sided glass according to claim 1, wherein the tensile shear displacement amount at a peak value of the tensile shear adhesive strength at room temperature is 2.0 mm or less in the test using the glass plate not subjected to primer treatment as an adherend. Adhesive sheet or tape. A support made of sheet-like or tape-like foam, or a support made by laminating a hard resin film on at least one side of a sheet-like or tape-like foam, an adhesive layer formed on both sides of this support, and this adhesive In a double-sided pressure-sensitive adhesive sheet or tape that is used by adhering at least one adhesive surface with a release layer attached to at least one surface of the layer opposite to the support to a glass plate,
The pressure-sensitive adhesive layer further includes a urethane resin obtained by reacting a chain extender with an isocyanate group-terminated prepolymer obtained by reacting a polyol and a polyisocyanate compound in an excess ratio of an isocyanate group, or the urethane resin. A double-sided pressure-sensitive adhesive sheet or tape for glass, which is formed of a urethane resin obtained by reacting a terminal stopper.   The double-sided pressure-sensitive adhesive sheet for glass or tape according to claim 3, wherein the pressure-sensitive adhesive layer is formed of a crosslinked polyurethane resin obtained by further reacting the urethane resin with a second polyisocyanate compound as a crosslinking agent. The double-sided pressure-sensitive adhesive sheet or tape for glass according to claim 3 or 4, wherein at least a part of the chain extender is a compound selected from the following (a) and (b).
(A) having three or more functional groups capable of reacting with an isocyanate group, and two of these functional groups are one or two selected from a primary amino group, a secondary amino group, and a primary hydroxyl group A compound which is a functional group and the remaining functional group is at least one functional group selected from a secondary hydroxyl group, a tertiary hydroxyl group and a carboxyl group.
(B) having three or more functional groups capable of reacting with an isocyanate group, two of which are one or two functional groups selected from a primary amino group and a secondary amino group A compound in which the remaining functional group is a primary hydroxyl group.   At least a part of the chain extender is (1) a compound having one primary amino group, one primary hydroxyl group and at least one secondary hydroxyl group, and (2) one secondary amino group and one primary group. 6. Both surfaces for glass according to claim 5, which are a compound having a hydroxyl group and at least one secondary hydroxyl group, or (3) a compound having two primary hydroxyl groups and at least one secondary hydroxyl group or tertiary hydroxyl group. Adhesive sheet or tape.   The double-sided pressure-sensitive adhesive sheet or tape for glass according to any one of claims 3 to 6, wherein the polyol is a polyoxyalkylene polyol having an average hydroxyl value of 2 or more and a hydroxyl value of 5.6 to 600 mgKOH / m.   The double-sided pressure-sensitive adhesive sheet or tape for glass according to any one of claims 3 to 7, wherein the sheet-like or tape-like foam comprises a polyurethane foam. The double-sided pressure-sensitive adhesive for glass according to any one of claims 3 to 8, wherein the sheet-like or tape-like foam has a thickness of 0.05 to 3.0 mm and a density of 100 to 800 kg / m ^3. Sheet or tape.   The double-sided pressure-sensitive adhesive sheet for glass or tape according to any one of claims 3 to 9, wherein the hard resin film has a thickness of 10 to 50 µm and is made of polypropylene or polyethylene terephthalate.   The double-sided pressure-sensitive adhesive sheet or tape for glass according to any one of claims 3 to 9, wherein the support is made of polyurethane foam having a thickness of 0.05 to 3.0 mm and a density of 100 to 800 kg / m. The said support body is 0.05-3.0 mm in thickness, and laminates | stacks the polyurethane foam and hard resin film of a density of 100-800 kg / m < ³ >, It is any one of Claims 3-10. Double-sided adhesive sheet or tape for glass.   A bottom surface fixed to the inner surface of the vehicle window glass plate via a double-sided adhesive sheet or tape, a temporary fixing main body portion inserted into an engagement hole provided in a vehicle body flange, and affixed to the bottom surface A temporary fixing member with an adhesive layer for temporarily fixing a glass plate for a vehicle window, comprising the double-sided pressure-sensitive adhesive sheet for glass or tape according to any one of claims 1 to 12.   Temporarily having a glass plate for a vehicle window, a bottom surface fixed to a vehicle inner surface of the glass plate via a double-sided adhesive sheet or tape, and a temporary fixing main body portion inserted into an engagement hole provided in a body flange of the vehicle. The automobile with a temporary fixing member having the fixing member and the double-sided pressure-sensitive adhesive sheet for glass or tape according to any one of claims 1 to 12, wherein a peeling layer interposed between the glass plate and the temporary fixing member is removed. Glass plate for windows.