WO2013021937A1 - Adhesive tape or sheet - Google Patents

Abstract

This adhesive tape or sheet has an adhesive layer on one surface of a base and is characterized in that the base is a silicone resin sheet which has a tensile stress at a strain of 10% at 100˚C of 0.1-3 MPa. The silicone resin sheet may be an inorganic oxide particle-containing silicone resin sheet which is formed from a silicone resin composition that contains a crosslinked structure wherein a polysiloxane resin and inorganic oxide particles dispersed in the polysiloxane resin are crosslinked by chemical bonds. This adhesive tape or sheet is capable of providing a combustible object with incombustibility merely by being bonded thereto, thereby significantly improving the fire resistance of the object to which the adhesive tape or sheet is bonded.

Description

Adhesive tape or sheet

The present invention relates to a pressure-sensitive adhesive tape or sheet, more specifically, a pressure-sensitive adhesive tape that can be applied to a flammable adherend to prevent surface ignition and carbonization during flame contact and to improve the fire resistance of the adherend. Or it relates to a sheet.

Conventionally, as a method for improving the fire resistance of a combustible member such as a wall material, floor material, ceiling material such as a building or public facility, a method of impregnating wood with a non-combustible component, a method of coating an inorganic substance on the surface, etc. It has been known.

For example, in Patent Document 1, a metal alkoxide solution is impregnated into wood, and then hydrolyzed or thermally decomposed to convert the metal alkoxide into a non-combustible metal oxide in wood, thereby making the wood flame-retardant. A method for manufacturing wood is disclosed. However, in this method, the object is impregnated with a substance that becomes a precursor of the incombustible component, and thus the weight increases. Also, the operation is complicated. Moreover, there is a problem that wood containing such nonflammable metal oxides is difficult to process.

Patent Document 2 discloses a flame retarding treatment method for a base sheet in which a flame retarding treatment layer made of an inorganic film is formed on at least one surface of the base sheet. However, since the flame retardant layer is hard and brittle, the thickness of the layer cannot be increased. Therefore, the incombustibility level is low. Moreover, since the flame retardant treatment layer is thin, heat is easily transmitted to the base sheet, and the base sheet is easily ignited.

JP-A-5-278008 JP 2003-33986 A

An object of the present invention is to provide a pressure-sensitive adhesive tape or sheet that can impart incombustibility to a flammable adherend simply by sticking, and can greatly improve the fire resistance of the adherend.
In addition to the above properties, another object is to provide a pressure-sensitive adhesive tape or sheet that is excellent in transparency and does not hinder the design of the adherend.

As a result of intensive studies to achieve the above object, the present inventors have used a silicone resin sheet having specific physical properties as an adhesive tape or a base material of the sheet, and the adherend is simply attached to the adherend. It was found that nonflammability can be imparted to the substrate, and that the fire resistance of the adherend can be greatly improved, and the present invention has been completed.

That is, the present invention is a pressure-sensitive adhesive tape or sheet having a pressure-sensitive adhesive layer on one side of a base material, wherein the base material has a tensile stress of 0.1 to 3 MPa at 10% strain at 100 ° C. A pressure-sensitive adhesive tape or sheet is provided.

The silicone resin sheet comprises inorganic oxide particles dispersed in a polysiloxane resin, and a silicone resin sheet containing inorganic oxide particles formed from a silicone resin composition containing a crosslinked structure in which the polysiloxane resin is crosslinked by a chemical bond. It may be.

In the inorganic oxide particle-containing silicone resin sheet, as the polysiloxane resin, a condensation-reactive group-containing polysilsesquioxane whose basic structural unit is a T unit, and a condensation reactivity whose basic structural unit is a D unit and a T unit. A group-containing polysiloxane is preferably used.

Further, in the inorganic oxide particle-containing silicone resin sheet, a condensation-reactive group-containing polysilsesquioxane whose basic structural unit is a T unit is bonded to the inorganic oxide particle by a chemical bond, and further, the basic structural unit It is preferable that a condensation-reactive group-containing polysilsesquioxane in which T is a T unit is bonded to a condensation-reactive group-containing polysiloxane whose basic structural unit is a D unit and a T unit to form a crosslinked structure. .

The total light transmittance of the substrate may be 80% or more. Further, the total light transmittance of the pressure-sensitive adhesive layer may be 80% or more. Further, the total light transmittance of the adhesive tape or sheet may be 80% or more.

The present invention also provides a fire-resistant member in which the above-mentioned adhesive tape or sheet is attached to an adherend.

In this specification, in addition to the above-described invention, the following adhesive tape or sheet and fire-resistant member will be described.

[1] An adhesive tape or sheet having an adhesive layer on one side of a substrate, wherein the substrate is a silicone resin sheet having a tensile stress of 0.1 to 3 MPa at 10% strain at 100 ° C. Adjacent to the base material, whether the layer A has a peel strength of 0.001 to 1 N / 10 mm at a temperature of at least 80 ° C. or more, and the layer A is an adhesive layer Alternatively, a pressure-sensitive adhesive tape or sheet provided with a pressure-sensitive adhesive layer through the layer A (hereinafter sometimes referred to as “pressure-sensitive adhesive tape or sheet A”).
[2] Containing inorganic oxide particles formed from a silicone resin composition in which the silicone resin sheet includes a crosslinked structure in which inorganic oxide particles dispersed in a polysiloxane resin and the polysiloxane resin are crosslinked by a chemical bond The adhesive tape or sheet according to [1], which is a silicone resin sheet.
[3] In the inorganic oxide particle-containing silicone resin sheet, as the polysiloxane resin, a condensation-reactive group-containing polysilsesquioxane whose basic structural unit is T unit, and the basic structural unit are D unit and T unit. The pressure-sensitive adhesive tape or sheet according to the above [2], wherein the condensation-reactive group-containing polysiloxane is used.
[4] In the inorganic oxide particle-containing silicone resin sheet, a condensation-reactive group-containing polysilsesquioxane whose basic structural unit is a T unit is bonded to the inorganic oxide particle by a chemical bond. The condensed reactive group-containing polysilsesquioxane whose unit is T unit is bonded to the condensed reactive group-containing polysiloxane whose basic structural unit is D unit and T unit to form a crosslinked structure [ [2] or [3].
[5] The pressure-sensitive adhesive tape or sheet according to any one of [1] to [4], wherein the peel strength of the layer A from the substrate at 23 ° C. is 0.001 to 3 N / 10 mm.
[6] The pressure-sensitive adhesive tape or sheet according to any one of [1] to [5], wherein the substrate has a total light transmittance of 80% or more.
[7] The adhesive tape or sheet according to any one of [1] to [6], wherein the total light transmittance of the adhesive layer is 80% or more.
[8] The pressure-sensitive adhesive tape or sheet according to any one of [1] to [7], wherein the total light transmittance of the pressure-sensitive adhesive tape or sheet is 80% or more.
[9] A fire-resistant member in which the adhesive tape or sheet according to any one of [1] to [8] is adhered to an adherend.

The pressure-sensitive adhesive tape or sheet A is the pressure-sensitive adhesive tape or sheet of the present invention, wherein (i) the pressure-sensitive adhesive layer is adjacent to the base material, and the pressure-sensitive adhesive layer is at least at a temperature of 80 ° C. or higher. A pressure-sensitive adhesive tape or sheet having a property of 0.001 to 1 N / 10 mm, or (ii) adjacent to the substrate, the peel force to the substrate at a temperature of at least 80 ° C. is 0. It corresponds to an adhesive tape or sheet having a layer having a characteristic of 001 to 1 N / 10 mm and having an adhesive layer provided through the layer.

In the pressure-sensitive adhesive tape or sheet of the present invention, since a silicone resin sheet having specific physical properties is used as a substrate, the substrate has appropriate toughness and flexibility. Also, the organic group content in the substrate is very low. Furthermore, the base material is supported by the pressure-sensitive adhesive layer, the strength is reinforced, and the strength is further increased by sticking to the adherend (attachment). Further, since the film thickness can be increased, heat conduction to the adherend can be suppressed during flame contact. Furthermore, since the base material has appropriate flexibility, even if the pressure-sensitive adhesive layer expands during flame contact, it is difficult to break. For this reason, non-flammability can be given to this adherend only by sticking this adhesive tape or sheet on a combustible adherend. That is, the pressure-sensitive adhesive tape or sheet of the present invention significantly improves the fire resistance of the adherend, and can reliably prevent carbonization and ignition of the adherend (a protective sheet that imparts nonflammability to the adherend). Available as
Further, since the transparency of the substrate can be increased, the design properties (wood grain, texture, etc.) of the adherend are not hindered. Furthermore, since it has a softness | flexibility, it is excellent in the followable | trackability to a curved surface, can be used also to the adherend which has a curved surface, and an uneven | corrugated adherend, and can be used as a roll-shaped adhesive tape or sheet | seat.

In particular, according to the pressure-sensitive adhesive tape or sheet A, the layer A has a layer A having a very small peeling force with respect to the base material at a high temperature adjacent to the base material. Since the silicone resin sheet layer swells, and the layer A, the pressure-sensitive adhesive layer (which may also serve as the layer A) and an air insulating layer floating from the adherend are formed, the fire resistance is further improved, the adherend, The pressure-sensitive adhesive is less likely to be carbonized.

FIG. 1 is a schematic sectional view showing an example of the pressure-sensitive adhesive tape or sheet of the present invention. FIG. 2 is a schematic cross-sectional view showing another example of the pressure-sensitive adhesive tape or sheet of the present invention. FIG. 3 is a schematic cross-sectional view showing still another example of the pressure-sensitive adhesive tape or sheet of the present invention. FIG. 4 is a perspective view of a flammability test apparatus used in the ignition and carbonization tests in Examples.

The pressure-sensitive adhesive tape or sheet of the present invention is a pressure-sensitive adhesive tape or sheet having a pressure-sensitive adhesive layer on one side of the substrate, and the substrate has a tensile stress of 0.1 to 3 MPa at 10% strain at 100 ° C. It is a silicone resin sheet. If the tensile stress at 10% strain at 100 ° C. of the base material is less than 0.1 MPa, the toughness is insufficient, the base material is cracked at the time of flame contact, and the adherend is ignited. In addition, when the tensile stress at 10% strain at 100 ° C. of the base material exceeds 3 MPa, and when the base material does not extend to 10%, the shrinkage of the adherend or the pressure-sensitive adhesive layer during flame contact, It cannot withstand deformation such as expansion, cracks, and ignites the adherend. Moreover, since a base material is too hard, a base material cracks at the time of affixing. The lower limit of the tensile stress at 10% strain of the substrate at 100 ° C. is preferably 0.2 MPa, more preferably 0.25 MPa, and the upper limit is preferably 2.5 MPa, more preferably 2 MPa.

FIG. 1 is a schematic sectional view showing an example of the pressure-sensitive adhesive tape or sheet of the present invention. In this example, the pressure-sensitive adhesive tape or sheet 3 has a pressure-sensitive adhesive layer 2 on one side of the substrate 1.

[Silicone resin sheet (base material)]
The silicone resin sheet used as the substrate 1 is not particularly limited as long as it is a silicone resin sheet having the above-mentioned characteristics, but the crosslinked inorganic oxide particles dispersed in the polysiloxane resin and the polysiloxane resin are cross-linked by a chemical bond. An inorganic oxide particle-containing silicone resin sheet formed from a silicone resin composition containing a structure can be suitably used. Such an inorganic oxide particle-containing silicone resin sheet has a good balance between toughness and flexibility. It is also excellent in transparency. Furthermore, since the organic group content is small, it has the property that it itself is difficult to burn. Hereinafter, the inorganic oxide particle-containing silicone resin sheet will be described.

The inorganic oxide particles may be inorganic oxide particles having a reactive functional group on the particle surface. For example, silica (SiO ₂ or SiO), alumina (Al ₂ O ₃ ), antimony-doped tin oxide (ATO) ), Titanium oxide (titania, TiO ₂ ), zirconia (ZrO ₂ ), and the like. Among these, silica is particularly preferable. An inorganic oxide particle may be used independently and may use 2 or more types together.

Examples of the reactive functional group include a hydroxyl group, an isocyanate group, a carboxyl group, an epoxy group, an amino group, a mercapto group, a vinyl type unsaturated group, a halogen atom, and an isocyanurate group. Among these, a hydroxyl group is preferable. Hydroxyl groups on the surface of silica particles exist as silanol groups.

As the average particle diameter (primary particle diameter) of the inorganic oxide particles, the upper limit is, for example, 1000 nm, preferably 500 nm, more preferably 200 nm, particularly preferably 100 nm, and the lower limit is, for example, 1 nm. The average particle diameter can be measured by a dynamic light scattering method or the like.

It is desirable that the particle size distribution of the inorganic oxide particles is narrow, and it is desirable that the inorganic oxide particles be in a monodispersed state in which the primary particle size is dispersed. Furthermore, the surface potential of the inorganic oxide particles is preferably in the acidic region (for example, pH 2 to 5, preferably pH 2 to 4). What is necessary is just to have such a surface potential at the time of reaction with polysiloxane resin.

As the inorganic oxide particles, it is preferable to use colloidal inorganic oxide particles. Examples of the colloidal inorganic oxide particles include colloidal silica (colloidal silica), colloidal alumina (alumina sol), colloidal tin oxide (tin oxide aqueous dispersion), colloidal titanium oxide (titania sol), and the like. .

Examples of colloidal silica include fine particles of silicon dioxide (anhydrous silicic acid) as described in, for example, JP-A Nos. 53-111272, 57-9051, and 57-51653. Examples thereof include colloids having an average particle size of 5 to 1000 nm, preferably 10 to 100 nm.

Further, the colloidal silica can contain, for example, alumina, sodium aluminate, etc., if necessary, and if necessary, an inorganic base (eg, sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia, etc.) Alternatively, a stabilizer such as an organic base (for example, tetramethylammonium) can be contained.

Such colloidal silica is not particularly limited and may be a known sol-gel method or the like, specifically, for example, Werner Stover et al; Colloid and Interface Sci. , 26, 62-69 (1968), Rickey D. It can be produced by the sol-gel method described in Badley et al; Langmuir 6, 792-801 (1990), Color Material Association Journal, 61 [9] 488-493 (1988).

The colloidal silica is preferably in a bare state that has not been surface-treated. In colloidal silica, a silanol group exists as a surface functional group.

As such colloidal silica, commercially available products can be used. Specifically, for example, trade names “Snowtex-XL”, “Snowtex-YL”, “Snowtex-ZL”, “PST” can be used. -2 "," Snowtex-20 "," Snowtex-30 "," Snowtex-C "," Snowtex-O "," Snowtex-OS "," Snowtex-OL "," Snowtex- " 50 ”(manufactured by Nissan Chemical Industries, Ltd.), trade names“ Adelite AT-30 ”,“ Adelite AT-40 ”,“ Adelite AT-50 ”(manufactured by Nippon Aerosil Co., Ltd.), and the like. Among these, trade names “Snowtex-O”, “Snowtex-OS”, “Snowtex-OL” and the like are particularly preferable.

In addition, as the colloidal inorganic particles other than the colloidal silica, commercially available products can be used. Specifically, for example, trade names “Alumina Sol 100”, “Alumina Sol 200”, “Alumina Sol 520” (above, Alumina sol (hydrosol) such as Nissan Chemical Industries), for example, titania sol (hydrosol) such as trade name “TTO-W-5” (produced by Ishihara Sangyo Co., Ltd.) and trade name “TS-020” (produced by Teika), for example And tin oxide aqueous dispersions such as “SN-100D” and “SN-100S” (above, manufactured by Ishihara Sangyo Co., Ltd.).

In the present invention, the inorganic oxide particles are colloidal silica whose primary particle diameter is in the range of 1 to 100 nm and whose surface potential is in the range of pH 2 to 5, and the silanol group on the surface of the colloidal silica is polysiloxane. It is preferable that the polysiloxane resin is crosslinked by chemical bonding with the resin.

The polysiloxane resin (polysiloxane resin used for reaction with inorganic oxide particles) is not particularly limited as long as it is a polysiloxane compound having reactivity with the functional group on the surface of the inorganic oxide particles. As the polysiloxane compound, a condensation-reactive silicone resin is particularly preferable. Examples of the condensation-reactive silicone resin include condensation-reactive group-containing polysiloxanes whose basic structural units are D units and T units (hereinafter, sometimes referred to as “D / T unit condensation-reactive group-containing polysiloxanes”). And a condensation-reactive group-containing polysilsesquioxane whose basic structural unit is a T unit (hereinafter sometimes referred to as “condensation-reactive group-containing polysilsesquioxane”). These may be used alone or in combination of two or more.

Among the condensation-reactive silicone resins, a combination of a DT unit condensation-reactive group-containing polysiloxane and a condensation-reactive group-containing polysilsesquioxane is particularly preferable. By combining the D / T unit condensation-reactive group-containing polysiloxane and the condensation-reactive group-containing polysilsesquioxane, a sheet having a particularly good balance between toughness and flexibility can be formed.

Examples of the condensation reactive group include silanol group, alkoxysilyl group (eg, C _1-6 alkoxysilyl group), cycloalkyloxysilyl group (eg, C _3-6 cycloalkyloxysilyl group), aryloxysilyl Group (for example, C _6-10 aryloxysilyl group and the like) and the like. Among these, a silanol group, an alkoxysilyl group, a cycloalkyloxysilyl group, and an aryloxysilyl group are preferable, and a silanol group and an alkoxysilyl group are particularly preferable.

Specifically, the D / T unit condensation-reactive group-containing polysiloxane contains, as basic structural units, a D unit represented by the following formula (1) and a T unit represented by the following formula (2). To do.

In the above formula (1), R ¹ is the same or different and represents a monovalent hydrocarbon group selected from a saturated hydrocarbon group and an aromatic hydrocarbon group. In formula (2), R ² represents a monovalent hydrocarbon group selected from a saturated hydrocarbon group and an aromatic hydrocarbon group.

Examples of the saturated hydrocarbon group for R ¹ and R ² include linear or branched alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl groups, etc. A cycloalkyl group having 3 to 6 carbon atoms such as cyclopentyl and cyclohexyl group; Examples of the aromatic hydrocarbon group for R ¹ and R ² include aryl groups having 6 to 10 carbon atoms such as phenyl and naphthyl groups.

R ¹ and R ² are preferably an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 10 carbon atoms, and more preferably a methyl group.

The D units represented by the formula (1) may be the same or different in the DT unit condensation-reactive group-containing polysiloxane, but are preferably the same. The T units represented by the formula (2) may be the same or different in the DT unit condensation-reactive group-containing polysiloxane, but are preferably the same.

In addition, the D / T unit condensation-reactive group-containing polysiloxane is a partial condensate of a corresponding silicone monomer [for example, a bifunctional silicone monomer such as a dialkyl (or aryl) dialkoxysilane and an alkyl ( Or a partial condensate with a trifunctional silicone monomer such as aryl) trialkoxysilane], in which D unit, T unit, and the following formula (3)
-OR ³ (3)
The group represented by these is contained. The group represented by the formula (3) is bonded to a silicon atom and exists at the molecular end.

R ³ represents a monovalent hydrocarbon group selected from a saturated hydrocarbon group and an aromatic hydrocarbon group. Examples of the saturated hydrocarbon group and aromatic hydrocarbon group include those similar to the saturated hydrocarbon group and aromatic hydrocarbon group in R ¹ in the above formula (1). R ³ is preferably a saturated hydrocarbon group, more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group or an ethyl group.

Examples of such a D / T unit condensation-reactive group-containing polysiloxane include an alkoxysilyl group (eg, C _1-6 alkoxysilyl group) -containing polymethylsiloxane and an alkoxysilyl group (eg, C _1-6 alkoxysilyl). Group) -containing polymethylphenylsiloxane, alkoxysilyl group (for example, C _1-6 alkoxysilyl group) -containing polyphenylsiloxane, and the like. These DT unit alkoxysilyl group-containing polysiloxanes may be used alone or in combination of two or more.

Among the D / T unit condensation-reactive group-containing polysiloxane, preferably a C _1-6 alkoxysilyl group-containing polysiloxane, more preferably a methoxysilyl group-containing polysiloxane or an ethoxysilyl group-containing polysiloxane, Particularly preferred is methoxysilyl group-containing polymethylsiloxane or ethoxysilyl group-containing polymethylsiloxane.

As the content of the condensation reactive group (for example, alkoxysilyl group) of such a DT unit condensation reactive group-containing polysiloxane, the upper limit is, for example, 30% by weight, preferably 25% by weight, and the lower limit is For example, 8% by weight, preferably 10% by weight, more preferably 12% by weight. The content of the condensation-reactive group (for example, alkoxysilyl group) can be determined from the rate of weight reduction when the temperature is raised from room temperature to 300 ° C. with a TGA (differential weight loss measurement device).

As the number average molecular weight of the D / T unit condensation reactive group-containing polysiloxane (standard polystyrene conversion by GPC measurement), the upper limit is, for example, 6000, preferably 5500, more preferably 5300, and the lower limit is, for example, 800, preferably Is 1000, more preferably 1200.

Commercially available products (D · T unit alkoxysilyl) such as “X-40-9246” and “X-40-9250” (manufactured by Shin-Etsu Chemical Co., Ltd.) as polysiloxanes containing DT unit condensation reactive groups Group-containing polysiloxane) can also be used.

Specifically, the condensation-reactive group-containing polysilsesquioxane contains a T unit represented by the formula (2) as a basic structural unit. The T units represented by the formula (2) may be the same or different in the condensation reactive group-containing polysilsesquioxane, but are preferably the same.

The condensation-reactive group-containing polysilsesquioxane is a partial condensate of a corresponding silicone monomer [for example, a partial condensate of a trifunctional silicone monomer such as alkyl (or aryl) trialkoxysilane]. In the structural unit, T unit and the following formula (4)
-OR ⁴ (4)
The group represented by these is contained. The group represented by the formula (4) is bonded to a silicon atom and exists at the molecular end.

R ⁴ represents a monovalent hydrocarbon group selected from a saturated hydrocarbon group and an aromatic hydrocarbon group. Examples of the saturated hydrocarbon group and aromatic hydrocarbon group include those similar to the saturated hydrocarbon group and aromatic hydrocarbon group in R ¹ in the above formula (1). R ⁴ is preferably a saturated hydrocarbon group, more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group or an ethyl group.

The condensation-reactive group-containing polysilsesquioxane may be any of a random type, a ladder type, and a cage type, but the random type is most preferable from the viewpoint of flexibility. These condensation-reactive group-containing polysilsesquioxanes may be used alone or in combination of two or more.

Among the condensation-reactive group-containing polysilsesquioxanes, preferably C _1-6 alkoxysilyl group-containing polysilsesquioxanes, more preferably methoxysilyl group-containing polysilsesquioxanes or ethoxysilyl groups Polysilsesquioxane, particularly preferably methoxysilyl group-containing polymethylsilsesquioxane or ethoxysilyl group-containing polymethylsilsesquioxane.

The upper limit of the content of the condensation-reactive group (for example, alkoxysilyl group) of such a condensation-reactive group-containing polysilsesquioxane is, for example, 50% by weight, preferably 48% by weight, more preferably 46% by weight. The lower limit is, for example, 10% by weight, preferably 15% by weight, and more preferably 20% by weight. The content of the condensation-reactive group (for example, alkoxysilyl group) can be determined from the rate of weight reduction when the temperature is raised from room temperature to 300 ° C. with a TGA (differential weight loss measurement device).

As the number average molecular weight (conversion to standard polystyrene by GPC measurement) of the polysilsesquioxane containing a condensation reactive group, the upper limit is, for example, 6000, preferably 3500, more preferably 3000, and the lower limit is, for example, 200, preferably 300, more preferably 400.

Commercially available products (alkoxy) such as trade names “KC-89”, trade names “KR-500”, “X-40-9225” (manufactured by Shin-Etsu Chemical Co., Ltd.) as polysilsesquioxanes containing condensation reactive groups Silyl group-containing polysilsesquioxane) can also be used.

In addition, as polysiloxane compounds having reactive silanol groups in the molecule (terminal), commercial names such as “X-21-3153” and “X-21-5841” (manufactured by Shin-Etsu Chemical Co., Ltd.) are available. Goods can also be used.

The proportion of the total amount of the D / T unit condensation-reactive group-containing polysiloxane and the condensation-reactive group-containing polysilsesquioxane in the entire polysiloxane compound is preferably 50% by weight or more, more preferably 70% by weight or more. Particularly preferably, it is 90% by weight or more.

In the present invention, as described above, in order to provide the sheet with a good balance between toughness and flexibility, the condensation reactive group-containing polysilsesquioxane and the D / T unit condensation reactive group-containing polysiloxane are used in combination. Is preferred. In this case, the upper limit of the ratio [the former / the latter (weight ratio)] is preferably 4.9, more preferably 4, particularly preferably 3, and the lower limit is preferably 0.2, more preferably. Is 0.5, particularly preferably 1. If the ratio of the condensation-reactive group-containing polysilsesquioxane is too high, the flexibility of the sheet is lowered, and when the adhesive tape or sheet based on the sheet is attached to the adherend, the substrate Becomes easy to break. Moreover, since the organic group content in a sheet | seat will increase when the ratio of DT unit condensation reactive group containing polysiloxane becomes too high, it will become easy to ignite. Moreover, the toughness of a sheet | seat falls, and when an adhesive sheet or tape which uses this sheet | seat as a base material is affixed on a to-be-adhered body, a base material cracks at the time of flame contact, and it becomes easy to ignite an to-be-adhered body.

In the inorganic oxide particle-containing silicone resin sheet, the upper limit of the content of inorganic oxide particles is, for example, 19% by weight, preferably 17% by weight, more preferably 15% by weight, and the lower limit is, for example, 2% by weight. %, Preferably 3% by weight, more preferably 4% by weight. If the content of inorganic oxide particles is too small, the mechanical strength tends to decrease, and if the content of inorganic oxide particles is too large, the sheet tends to be brittle.

In the present invention, the tensile stress at 10% strain at 100 ° C. of the substrate is 0.1 to 3 MPa as described above. The upper limit of the tensile stress at 10% strain at 100 ° C. of the substrate is preferably 2 MPa, more preferably 1.5 MPa, and the lower limit is preferably 0.2 MPa, more preferably 0.25 MPa. The tensile stress at 10% strain at 100 ° C. of the inorganic oxide particle-containing silicone resin sheet is determined by the content of inorganic oxide particles, the type of polysiloxane resin, the polysilsesquioxane containing condensation reactive groups, and DT. It can be adjusted by the blending ratio or the like in the case where the unit condensation reactive group-containing polysiloxane is used in combination.

The total light transmittance (for example, thickness of 100 μm) of the inorganic oxide particle-containing silicone resin sheet can be appropriately selected depending on the use, but is preferably 80% or more from the viewpoint of not impairing the design of the adherend. In particular, 85% or more is preferable. The total light transmittance of the inorganic oxide particle-containing silicone resin sheet can be adjusted by, for example, the type of inorganic oxide particles, the average primary particle diameter of the inorganic oxide particles, and the like. By reducing the average primary particle diameter of the inorganic oxide particles, the total light transmittance of the sheet can be increased.

Next, a method for producing the inorganic oxide particle-containing silicone resin sheet will be described.

The inorganic oxide particle-containing silicone resin sheet includes, for example, the inorganic oxide particles and a polysiloxane resin (preferably, a DT unit condensation-reactive group-containing polysiloxane and / or a condensation-reactive group-containing polysilsesquioxane. ) In a solvent, preferably in the presence of an acid.

Examples of the solvent include water; alcohols such as methanol, ethanol, 2-propanol, and 2-methoxyethanol; and mixtures thereof. Among these, a mixed solvent of water and alcohol is preferable, and a mixed solvent of water and 2-propanol, and a mixed solvent of water, 2-propanol and 2-methoxyethanol are more preferable.

Examples of the acid include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid; organic acids such as acetic acid and p-toluenesulfonic acid. Among these, inorganic acids are preferable, and nitric acid is particularly preferable. These acids can be used as aqueous solutions. The amount of the acid used may be an amount that can adjust the pH of the reaction system to about 2 to 5 (preferably 2 to 4).

The reaction method is not particularly limited. For example, (i) a method of adding a mixed liquid of a polysiloxane resin and a solvent to a mixed liquid of inorganic oxide particles and a solvent, and (ii) a polysiloxane resin and a solvent A method of adding a mixed liquid of inorganic oxide particles and a solvent to the mixed liquid of (iii), and (iii) a mixed liquid of inorganic oxide particles and a solvent and a mixed liquid of polysiloxane resin and a solvent together in the solvent Any of the method of adding etc. may be sufficient.

As the reaction temperature, the upper limit is, for example, 150 ° C., preferably 130 ° C., and the lower limit is, for example, 40 ° C., preferably 50 ° C. Moreover, as reaction time, an upper limit is 24 hours, for example, Preferably it is 12 hours, and a minimum is 0.3 hours, for example, Preferably it is 0.5 hours.

In addition, when the polysiloxane resin is used in combination with a D / T unit condensation-reactive group-containing polysiloxane and a condensation-reactive group-containing polysilsesquioxane, the inorganic oxide particles and the D / T unit condensation reactivity are used. The group-containing polysiloxane may be reacted with a mixture of the condensation-reactive group-containing polysilsesquioxane, and the inorganic oxide particles are first reacted with the DT unit condensation-reactive group-containing polysiloxane. Then, the condensation-reactive group-containing polysilsesquioxane may be reacted. Further, the inorganic oxide particles are first reacted with the condensation-reactive group-containing polysilsesquioxane, and then D · T unit condensation-reactive group-containing polysiloxane may be reacted.

Among these, when a method in which the inorganic oxide particles are first reacted with a polysilsesquioxane containing a condensation reactive group silyl group and then reacted with a polysiloxane containing a DT unit condensation reactive group, the toughness is obtained. It is possible to obtain a sheet having a good balance between flexibility and flexibility. Hereinafter, this method will be described.

That is, a preferable production method of the inorganic oxide particle-containing silicone resin sheet includes a first reaction step of reacting the inorganic oxide particles and the condensation reactive group-containing polysilsesquioxane whose basic structural unit is a T unit; A second reaction step in which the reaction product obtained in the first reaction step is further reacted with a condensation-reactive group-containing polysiloxane whose basic structural units are D units and T units; and the second reaction And a step of forming a film of the reaction product obtained in the step.

First, the first reaction process will be described. In the first reaction step, the inorganic oxide particles are reacted with a condensation reactive group-containing polysilsesquioxane whose basic structural unit is a T unit.

The reaction is carried out in a solvent, preferably in the presence of an acid. As the solvent, the above-mentioned solvents can be used. As the acid, the aforementioned acids can be used. The amount of the acid used may be an amount that can adjust the pH of the reaction system to about 2 to 5 (preferably 2 to 4). The reaction method is not particularly limited, and the above methods (i) to (iii) can be employed.

The upper limit of the reaction temperature in the first reaction step is, for example, 150 ° C., preferably 100 ° C., and the lower limit is, for example, 40 ° C., preferably 50 ° C. Moreover, as reaction time, an upper limit is 8 hours, for example, Preferably it is 6 hours, and a minimum is 0.3 hours, for example, Preferably it is 0.5 hours.

Next, the second reaction process will be described. In the second reaction step, the reaction product obtained in the first reaction step is further reacted (condensed) with a condensation-reactive group-containing polysiloxane whose basic structural units are D units and T units. The reaction solution itself obtained in the first reaction step may be subjected to the second reaction step, but after the reaction solution is subjected to appropriate treatments such as liquidity adjustment, concentration, dilution, solvent exchange, etc. It can also be used for the second reaction step. In this step, the condensation reactive group possessed by the condensation reactive group-containing polysilsesquioxane in which the basic structural unit reacted with the inorganic oxide particles in the first reaction step is a T unit, and the basic structural unit is D. The condensation reactive group of the condensation reactive group-containing polysiloxane which is a unit and a T unit is reacted.

The reaction is performed in a solvent. As the solvent, the above-mentioned solvents can be used. The reaction is preferably performed under acidic conditions. The pH of the reaction system is, for example, 2 to 5, preferably 2 to 4. The reaction method is not particularly limited, and a condensation-reactive group-containing polysiloxane having a basic structural unit of D units and T units and a solvent in a liquid containing the reaction product obtained in the first reaction step. And a reaction product obtained in the first reaction step in a mixture of a condensation-reactive group-containing polysiloxane whose basic structural units are D units and T units and a solvent. Any of a method of adding a liquid to be contained may be used.

As the reaction temperature in the second reaction step, the upper limit is, for example, 150 ° C., preferably 130 ° C., and the lower limit is, for example, 50 ° C., preferably 60 ° C. Moreover, as reaction time, an upper limit is 8 hours, for example, Preferably it is 6 hours, and a minimum is 0.3 hours, for example, Preferably it is 0.5 hours.

According to this preferred method, high heat resistance and strength can be maintained by firmly bonding inorganic oxide particles having strength with polysilsesquioxane comprising T units capable of imparting hardness, and then flexible. Since the DT resin having D units is bonded, toughness and flexibility can be provided in a balanced manner. In addition, since the inorganic oxide particles are reacted with the condensation reactive group-containing polysilsesquioxane whose basic structural unit is a T unit in the first stage, the DT resin is bonded to the inorganic oxide particles. Compared to the case where DT resin is bound first, a flexible amount of DT resin can be obtained. Therefore, an inorganic oxide particle-containing silicone resin sheet that is remarkably excellent in flexibility can be obtained.

In the film forming step, the reaction product obtained in the second reaction step is formed into a film. The reaction solution obtained in the second reaction step may be used for film formation as it is, but after the reaction solution has been subjected to appropriate treatments such as liquidity adjustment, concentration, dilution, solvent exchange, washing, etc., It can also use for a film-forming process. Moreover, after adding a curing catalyst, it can also be attached to film formation.

The film forming method is not particularly limited, and a known or commonly used film forming method can be employed. A solution or dispersion liquid (inorganic oxide particle-containing silicone resin composition) containing a reaction product is placed on a transfer substrate. A method of forming a film by coating and drying and, if necessary, heat curing to complete the reaction is preferably used. The drying temperature is, for example, about 50 to 150 ° C. The temperature at the time of heat curing is, for example, about 40 to 250 ° C. The film forming process is not limited to the above two-step reaction method, and can be applied to the general production of inorganic oxide particle-containing silicone resin sheets.

As the transfer substrate, a substrate whose surface has been subjected to a peeling treatment can be used. The material of the transfer substrate is not particularly limited, and examples thereof include thermoplastic resins such as polyester, thermosetting resins, metals, and glass.

Thus, an inorganic oxide particle-containing silicone resin sheet having a good balance between toughness and flexibility can be obtained, and can be suitably used as a base material for the pressure-sensitive adhesive tape or sheet of the present invention.

In the present invention, the thickness of the substrate is usually 10 μm or more (for example, 10 to 10,000 μm), preferably 20 μm or more (for example, from the viewpoint of imparting toughness and preventing heat conduction to the adherend. 20 to 5000 μm), more preferably 30 μm or more (for example, 30 to 1000 μm).

In the base material, a colorant such as a pigment may be added as necessary, and the base material may be colored or designed.

The total light transmittance (thickness: 100 μm, for example) of the substrate can be appropriately selected depending on the application and the like, but is preferably 80% or more, particularly 85% or more from the viewpoint of not impairing the design properties of the adherend. preferable.

[Adhesive layer]
The pressure-sensitive adhesive tape or sheet 3 of the present invention has a pressure-sensitive adhesive layer 2 on one side of the substrate 1. Since the strength is low only in the base material (silicone resin sheet), it is easy to break due to deformation etc. when the adherend is in contact with flame, but by providing an adhesive layer and sticking to the adherend through the adhesive layer, The entire sheet is reinforced, the fire resistance of the adherend can be greatly improved, ignition and carbonization can be prevented, and incombustibility can be achieved.

It does not specifically limit as an adhesive which comprises the adhesive layer 2, For example, a rubber adhesive, an acrylic adhesive, a vinyl alkyl ether adhesive, a silicone adhesive, a polyester adhesive, a polyamide adhesive Known adhesives such as urethane adhesives, styrene-diene block copolymer adhesives, and adhesives with improved creep characteristics in which a hot-melt resin having a melting point of about 200 ° C. or less is blended with these adhesives. One type or a combination of two or more types can be used. The pressure-sensitive adhesive may be any known pressure-sensitive adhesive such as a solvent type, an emulsion type, a hot melt type, and a UV curable type.

In general, as the pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive using natural rubber or various synthetic rubbers as a base polymer; an acrylic polymer using one or more (meth) acrylic acid alkyl esters as monomer components An acrylic pressure-sensitive adhesive having a base polymer (homopolymer or copolymer) is used. In the present invention, an acrylic adhesive having an acrylic polymer as a base polymer is particularly preferably used.

If an acrylic adhesive, etc., whose expansion coefficient is significantly different from that of the silicone resin that constitutes the base material is used as the adhesive, the base material will stick to the flame contact due to the difference in expansion coefficient between the adhesive layer and the base material. In some cases, it floats from the agent layer to form a heat insulating layer of air, and the adherend is less likely to be carbonized.

Examples of the (meth) acrylic acid alkyl ester used as the monomer component of the acrylic polymer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and (meth) acrylic acid. Isopropyl, butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, (meth ) Heptyl acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, ( Pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, ( Data) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl and the like (meth) (meth) acrylic acid C _1-20 alkyl esters such as eicosyl acrylate.

The acrylic polymer is a unit corresponding to another monomer component copolymerizable with the (meth) acrylic acid alkyl ester, if necessary, for the purpose of modifying cohesive strength, heat resistance, crosslinkability and the like. May be included. Examples of such a monomer component include an aliphatic cyclic skeleton such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, and bornyl (meth) acrylate (meta ) Acrylic acid ester; (meth) acrylic acid ester having an aromatic carbon ring such as phenyl (meth) acrylate and benzyl (meth) acrylate; acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, Carboxylic group-containing monomers such as maleic acid, fumaric acid and crotonic acid; Acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, (meth) Acrylic acid hydroxybuty Hydroxyl group-containing monomers such as hydroxyhexyl (meth) acrylate, hydroxyoctyl (meth) acrylate, hydroxydecyl (meth) acrylate, hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl methacrylate; Contains sulfonic acid groups such as sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, (meth) acrylamide propane sulfonic acid, sulfopropyl (meth) acrylate, (meth) acryloyloxynaphthalene sulfonic acid Monomer: (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methylolpropane (meth) a (N-substituted) amide-containing monomers such as rilamide; (meth) acrylic such as aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, and t-butylaminoethyl (meth) acrylate Acid aminoalkyl monomers; (meth) acrylic acid alkoxyalkyl monomers such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate; N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N- Maleimide monomers such as phenylmaleimide; N-methylitaconimide, N-ethylitaconimide, N-butylitaconimide, N-octylitaconimide, N-2-ethylhexylitaconimide, N-cyclohexylitaconimide, N-laurylitaconimide Itaconimide monomers such as conimide; succinimide monomers such as N- (meth) acryloyloxymethylene succinimide, N- (meth) acryloyl-6-oxyhexamethylene succinimide, N- (meth) acryloyl-8-oxyoctamethylene succinimide; Vinyl acetate, vinyl propionate, N-vinyl pyrrolidone, methyl vinyl pyrrolidone, vinyl pyridine, vinyl piperidone, vinyl pyrimidine, vinyl piperazine, vinyl pyrazine, vinyl pyrrole, vinyl imidazole, vinyl oxazole, vinyl morpholine, N-vinyl carboxylic acid amides, Vinyl monomers such as styrene, α-methylstyrene, N-vinylcaprolactam; cyano group-containing monomers such as acrylonitrile and methacrylonitrile Epoxy group-containing acrylic monomers such as glycidyl (meth) acrylate; polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, etc. Glycol acrylic ester monomer; N- (meth) acryloylmorpholine, tetrahydrofurfuryl (meth) acrylate, fluorine (meth) acrylate, silicone (meth) acrylate and other heterocyclic rings, halogen atoms, silicon atoms, etc. Monomers: hexanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl Recall di (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, epoxy acrylate, polyester acrylate, urethane acrylate, etc. Polyfunctional monomers; Olefin monomers such as isoprene, butadiene, and isobutylene; Vinyl ether monomers such as vinyl ether. These monomer components can be used alone or in combination of two or more.

The acrylic polymer can be produced by a known radical polymerization method such as solution polymerization, bulk polymerization, and emulsion polymerization. The acrylic polymer may be any of a random copolymer, a block copolymer, a graft polymer, and the like. In polymerization, a commonly used polymerization initiator or chain transfer agent can be used.

The weight average molecular weight of the base polymer constituting the pressure-sensitive adhesive is, for example, 10,000 to 2,000,000, preferably 300,000 to 1,500,000. When the weight average molecular weight of the base polymer is too low, although excellent in the followability with the adherend, for example, when peeling is necessary, the adherend tends to be contaminated with adhesive residue or the like. On the other hand, if the weight average molecular weight of the base polymer is too high, the followability to the adherend tends to decrease.

For adhesives, in addition to the base polymer, if necessary, crosslinking agents (epoxy crosslinking agents, isocyanate crosslinking agents, melamine crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, metal chelate compounds, etc.), crosslinking Accelerator (crosslinking catalyst), tackifier (for example, rosin derivative resin, polyterpene resin, petroleum resin, oil-soluble phenol resin, etc.), thickener, plasticizer, filler, foaming agent, anti-aging agent, antioxidant And an appropriate additive such as an ultraviolet absorber, an antistatic agent, a surfactant, a leveling agent, a colorant, a flame retardant, and a silane coupling agent. As said flame retardant, the inorganic flame retardant etc. which are used for the heat insulation layer mentioned later can be used. By adding a flame retardant to the adhesive, the fire resistance of the adherend can be further improved.

The formation of the pressure-sensitive adhesive layer can be performed by a known or conventional method. For example, a method of applying the pressure-sensitive adhesive composition onto a base material [when an intermediate layer (for example, layer A described later) is present on the base material, the intermediate layer], a method for applying the pressure-sensitive adhesive composition to an appropriate transfer After forming the pressure-sensitive adhesive layer on the base material, the pressure-sensitive adhesive layer is placed on the base material [if the intermediate layer (for example, layer A described later) exists on the base material, the intermediate layer] And a method of simultaneously coating the base material and the pressure-sensitive adhesive composition on a suitable substrate. The application and coating can be performed by a coater, an extruder, a printing machine or the like generally used for forming the pressure-sensitive adhesive layer.

The thickness of the pressure-sensitive adhesive layer can be appropriately selected depending on the application and the like, and the upper limit is, for example, 3000 μm, preferably 500 μm, and the lower limit is, for example, 5 μm, preferably 10 μm.

The total light transmittance (for example, thickness 20 μm) of the pressure-sensitive adhesive layer can be appropriately selected depending on the use, but is preferably 80% or more, particularly 85% or more from the viewpoint of not deteriorating the design of the adherend. preferable.

The pressure-sensitive adhesive tape or sheet of the present invention has another layer (intermediate layer; for example, a printed layer, a heat insulating layer, an elastic layer, a rigid layer, etc.) between the substrate and the pressure-sensitive adhesive layer as necessary. May be.

Design property can be imparted to the pressure-sensitive adhesive tape or sheet by providing a printing layer between the substrate and the pressure-sensitive adhesive layer.

In addition, by providing a heat insulating layer between the base material and the pressure-sensitive adhesive layer, heat conduction to the adherend can be further suppressed, the fire resistance of the adherend can be further improved, and the adherend Carbonization and ignition can be prevented more reliably.

The heat insulating layer can be formed of a flame retardant composition containing a flame retardant such as an inorganic flame retardant, for example. Examples of the inorganic flame retardant include, for example, sodium silicate (water glass) and sodium polyborate, which are foamed when heated and can form a heat insulating layer due to low thermal conductivity of bubbles; Examples thereof include aluminum hydroxide and magnesium hydroxide, which can be insulated by generating water.

In order to impart flexibility to the heat insulating layer, it is preferable to add an organic polymer to the flame retardant composition. The organic polymer is not particularly limited as long as it can contain a flame retardant such as the above inorganic flame retardant, and examples thereof include polymers shown as the base polymer of the pressure-sensitive adhesive.

As the flame retardant composition, a composition in which a sodium silicate aqueous solution and a water-dispersed polymer (for example, a water-dispersed acrylic polymer) are mixed is particularly preferable in that flexibility and transparency can be imparted to the heat insulating layer. preferable.

As content (in solid content conversion) of the inorganic flame retardant in a heat insulation layer, an upper limit is 70 weight%, for example, Preferably it is 40 weight%, and a minimum is 1 weight%, for example, Preferably, it is 5 weight%. . The upper limit of the thickness of the heat insulating layer is, for example, 3000 μm, preferably 500 μm, and the lower limit is, for example, 5 μm, preferably 10 μm.

There is no restriction | limiting in particular as a formation method of a heat insulation layer, For example, it can form by the method similar to the said adhesive layer.

In the pressure-sensitive adhesive tape or sheet of the present invention, a separator for protecting the pressure-sensitive adhesive layer may be provided on the pressure-sensitive adhesive layer until the pressure-sensitive adhesive tape or sheet is used.

The total light transmittance (for example, thickness 120 μm) of the pressure-sensitive adhesive tape or sheet of the present invention can be appropriately selected depending on the application, but is preferably 80% or more from the viewpoint of not impairing the design properties of the adherend. 85% or more is preferable.

The method for attaching the adhesive tape or sheet of the present invention to the adherend is not particularly limited, and the adhesive layer may be attached to the adherend with the base material (silicone resin sheet) facing outside. In addition, a peelable film (peelable film) is laminated on the surface of the substrate opposite to the pressure-sensitive adhesive layer, and affixed to the adherend in the form of a peelable film / substrate / pressure-sensitive adhesive layer. Then, the peelable film may be peeled off. As the peelable film, for example, a low polarity film (polyolefin film or the like) can be used. When the base material is soft and has no waist, the handleability and the pasting workability are improved by laminating the peelable film in this way. In addition, when functioning as a protective sheet for imparting fire resistance to the adherend, it is ignited if there is a flammable film on the outermost surface in a state of being attached to the adherend, so that the outside of the base material (silicone resin sheet) It is important not to use a flammable film laminated on the surface.

According to the pressure-sensitive adhesive tape or sheet of the present invention, since a silicone resin sheet having specific physical properties is used as a base material, it is possible to greatly improve the fire resistance of an adherend (adherent) simply by sticking. Incombustibility can be imparted to the flammable adherend. Moreover, the abrasion resistance (including scratch resistance) of the adherend can be improved by sticking to the adherend. For example, in the pencil hardness evaluation method defined in JIS K5400, the hardness of the surface of the adherend to which the pressure-sensitive adhesive tape or sheet of the present invention is affixed can be “H” or higher. Therefore, for example, a hard coat effect can be given to wood by sticking the pressure-sensitive adhesive tape or sheet of the present invention to wood. Furthermore, even if a poster or the like is attached to the surface of the adherend to which the adhesive tape or sheet of the present invention has been attached, the substrate is composed of a silicone resin with few polar groups, There is no increase in the thickness, and when peeling, it can be peeled without any adhesive residue. That is, tape peelability can be imparted to the adherend.

Further, when the pressure-sensitive adhesive tape or sheet of the present invention is affixed to an adherend, the irregularities on the surface of the adherend are filled with the pressure-sensitive adhesive of the pressure-sensitive adhesive tape or sheet of the present invention, the outermost surface is smoothed, Gloss can be given to the body. For example, the glossiness (glossiness at 60 ° -60 ° reflection) measured with a gloss meter can be, for example, 60% or more, preferably 70% or more, more preferably 75% or more. Gloss can be given to the surface of the body.

Furthermore, when the adhesive tape or sheet of the present invention is applied to an adherend, the water resistance is improved. For example, an adherend (10 cm long × 10 cm wide sample piece) to which the pressure-sensitive adhesive tape or sheet of the present invention is applied is placed horizontally, and 5 g of water at a water temperature of 23 ° C. is placed on the surface (the surface of the pressure-sensitive adhesive tape or sheet affixed). The sample piece is left to stand for 24 hours, and then the sample piece is made vertical, the water that has not been absorbed is dropped, the weight of the sample piece is measured, and the water absorption obtained by the following formula is, for example, 1% or less, preferably 0 .1% or less, or 0%. Therefore, the effect of the drug added to the adherend is maintained and the appearance is good.
Water absorption (%) = {(sample weight after test−sample weight before test) / (sample weight before test)} × 100

Also, the pressure-sensitive adhesive tape or sheet of the present invention is excellent in weather resistance because the substrate is composed of a silicone resin sheet. When a light stabilizer is added to the pressure-sensitive adhesive layer (or pressure-sensitive adhesive layer and substrate) of the pressure-sensitive adhesive tape or sheet of the present invention, the pressure-sensitive adhesive tape or sheet of the present invention is affixed to the adherend, The weather resistance can be further improved, and the adherend can be prevented from being burned, yellowed or cracked.

Furthermore, by sticking the pressure-sensitive adhesive tape or sheet of the present invention to the adherend, bleeding to the surface such as spears, drugs and low molecular weight components contained in the adherend can be prevented, and the design inherently possessed by the adherend Can be maintained for a long time. This is probably because the adhesive tape or sheet of the present invention does not allow water to pass through, so that the drug or the like hardly aggregates.

Further, by sticking the adhesive tape or sheet of the present invention to the adherend, since external water does not enter the adherend, corrosion of the adherend can be prevented.

Furthermore, after sticking the adhesive tape or sheet of the present invention to the adherend and after completing a predetermined role, the adherend can be incinerated and discarded by peeling off the adhesive tape or sheet. That is, the pressure-sensitive adhesive tape or sheet of the present invention is excellent in adherend disposal.

Moreover, even if the pressure-sensitive adhesive tape or sheet of the present invention is applied to an adherend, the adherend processability is good. That is, the conventional flame-retardant wood is hard and heavy and has poor workability, whereas the adherend (wood etc.) to which the adhesive tape or sheet of the present invention is applied does not impair the original physical properties of the adherend. , Possesses good workability (nail driveability, nail pullability, etc.).

Furthermore, the pressure-sensitive adhesive tape or sheet of the present invention can impart antibacterial, antifungal, solvent resistance, chemical resistance and acid resistance to the adherend.

In the pressure-sensitive adhesive tape or sheet of the present invention, various properties can be imparted by adding appropriate additives in the silicone resin base material layer and / or the pressure-sensitive adhesive layer, or by providing appropriate layers. For example, the contamination resistance of the adherend can be improved by providing a hydrophilic layer (a layer containing sol-gel, titanium oxide, or the like). In the pressure-sensitive adhesive tape or sheet of the present invention, an insecticidal (termite) component or an antibacterial component is added to the silicone resin substrate layer and / or the adhesive layer, or a layer containing an insecticidal (termite) component or an antibacterial component is added. By providing it separately, high adherence (termite) and antibacterial properties can be imparted to the adherend. Furthermore, the antireflection property can be imparted to the adherend by adding particles to at least the surface layer portion of the base material of the pressure-sensitive adhesive tape or sheet of the present invention, or by imparting irregularities to the surface of the base material by transfer.

[Adhesive tape or sheet A]
The pressure-sensitive adhesive tape or sheet A is a pressure-sensitive adhesive tape or sheet having a pressure-sensitive adhesive layer on one side of a base material, and the base material has a tensile stress of 0.1 to 3 MPa at 10% strain at 100 ° C. A resin sheet, having a layer A adjacent to the substrate and having a peel strength of 0.001 to 1 N / 10 mm to the substrate at a temperature of at least 80 ° C., the layer A being an adhesive It is a layer or the adhesive layer is provided through the said layer A, It is characterized by the above-mentioned.

The pressure-sensitive adhesive tape or sheet A is one embodiment of the pressure-sensitive adhesive tape or sheet of the present invention. As described above, in the pressure-sensitive adhesive tape or sheet of the present invention, (i) the pressure-sensitive adhesive layer is adjacent to the substrate. The pressure-sensitive adhesive layer has an adhesive tape or sheet having a property that the peel force to the substrate at a temperature of at least 80 ° C. is 0.001 to 1 N / 10 mm, or (ii) adjacent to the substrate. And a pressure-sensitive adhesive tape or sheet having a layer having a property of a peel strength of 0.001 to 1 N / 10 mm with respect to the substrate at a temperature of at least 80 ° C. and having a pressure-sensitive adhesive layer interposed therebetween. It is equivalent to.

Hereinafter, the adhesive tape or sheet A will be described, but the substrate and the adhesive layer are the same as described above.

In the pressure-sensitive adhesive tape or sheet A, the peeling force with respect to the substrate at a temperature of at least 80 ° C. or higher (for example, any temperature within the range of 80 to 150 ° C.) is 0.001 to 1 N / It has a layer A that is 10 mm. The layer A may be a pressure-sensitive adhesive layer in the pressure-sensitive adhesive tape or sheet of the present invention, and a pressure-sensitive adhesive layer is provided on one side of the base material via the layer A separately from the layer A. Also good. The lower limit of the peeling force for the substrate at a temperature of at least 80 ° C. of the layer A is preferably 0.005 N / 10 mm, more preferably 0.01 N / 10 mm, and the upper limit is preferably 0.85 N / 10 mm. Preferably it is 0.7N / 10mm.

FIG. 2 is a schematic sectional view showing an example of an adhesive tape or sheet A. In this example, the adhesive tape or sheet 40 has a layer A30 on one side of the substrate 10, and the layer A30 also serves as an adhesive layer of the adhesive tape or sheet. FIG. 3 is a schematic cross-sectional view showing another example of an adhesive tape or sheet A. In this example, the pressure-sensitive adhesive tape or sheet 400 is provided with the pressure-sensitive adhesive layer 20 on one side of the base material 10 via the layer A30.

[Layer A]
The pressure-sensitive adhesive tape or sheet A (40, 400) has a layer A30 adjacent to the base material 10 and having a peeling force with respect to the base material 10 at a temperature of at least 80 ° C. of 0.001 to 1 N / 10 mm. ing. Since the pressure-sensitive adhesive tape or sheet A has the layer A, the silicone resin sheet layer swells at the time of flame contact (at high temperature), and the layer A, the pressure-sensitive adhesive layer (the layer A may also serve as), and the adherend Since a heat insulating layer of air is formed by floating from above, fire resistance is further improved compared to the case where the layer A is not provided, and the adherend and the adhesive are less likely to be carbonized.

The layer A is particularly limited as long as the peeling force with respect to the substrate is in the range of 0.001 to 1 N / 10 mm at a temperature of at least 80 ° C. (for example, any temperature in the range of 80 to 200 ° C.). For example, a high-temperature fine-tack layer that is highly tacky at room temperature (for example, 23 ° C.) but has low tack at high temperature (for example, 80 ° C. or higher), room temperature (for example, 23 ° C.), and high temperature (80 ° C. or higher). In any case of higher temperature), a room-temperature micro-tack layer, an adsorbing layer and the like having low adhesiveness can be mentioned. Examples of the high-temperature fine tack layer include a warm-off pressure-sensitive adhesive layer, a heat-foaming pressure-sensitive adhesive layer (for example, a heat-expandable microsphere-containing pressure-sensitive adhesive layer), and a thermosetting pressure-sensitive adhesive layer. Moreover, as a room temperature fine tack layer, for example, a pressure-sensitive adhesive layer having low adhesiveness at room temperature (and even at a high temperature), a thermosetting pressure-sensitive adhesive layer after being thermally cured, and ultraviolet curing after being irradiated with ultraviolet rays Examples include a fine tack adhesive layer such as a mold adhesive layer; a fine tack film or sheet layer whose surface is weakly tacky (slightly tacky). Furthermore, as an absorptive layer, an absorptive film or a sheet layer such as a foam resin layer having irregularities on the surface can be cited.

In the case where the layer A is composed of a pressure-sensitive adhesive, the pressure-sensitive adhesive can be selected and used from the pressure-sensitive adhesives described in the section of the pressure-sensitive adhesive layer.

When layer A also serves as the adhesive layer of the adhesive tape or sheet, it is preferable that the peeling force of layer A on the substrate at 23 ° C. is 0.001 to 3 N / 10 mm. The upper limit of the peeling force for the substrate A at 23 ° C. is more preferably 2.7 N / 10 mm, and the lower limit is more preferably 0.005 N / 10 mm, and particularly preferably 0.01 N / 10 mm.

Formation of layer A can be performed by a known or conventional method used for forming a pressure-sensitive adhesive layer or a film layer. For example, a method of applying a composition (solution, emulsion, melt, etc.) such as a pressure-sensitive adhesive composition for forming layer A onto a substrate, a composition for forming layer A with an appropriate transfer group After forming layer A by coating on the material, the method of transferring (transferring) layer A onto the base material and the composition for forming base material and layer A on an appropriate substrate simultaneously The method of coating etc. are mentioned. Application and coating can be performed by a coater, an extruder, a printing machine, or the like generally used for forming an adhesive layer or the like. When layer A is a film or sheet, a known or conventional lamination method, extrusion method (including coextrusion method), or the like can be used.

The thickness of the layer A can be appropriately selected depending on the application. As for the thickness of the layer A, the upper limit is, for example, 3000 μm, preferably 500 μm, more preferably 100 μm, particularly preferably 60 μm, and the lower limit is, for example, 5 μm, preferably 10 μm.

The total light transmittance (for example, 20 μm in thickness) of the layer A can be appropriately selected depending on the application, but is preferably 80% or more, particularly preferably 85% or more from the viewpoint of not impairing the design properties of the adherend. .

The adhesive tape or sheet A has an adhesive layer on one side of the substrate. In the example of FIG. 3, the pressure-sensitive adhesive layer 20 is provided on one side of the substrate 10 via the layer A30. When the layer A has adhesiveness at room temperature (for example, 23 ° C.), the layer A30 may also serve as the adhesive layer as shown in FIG. 2, and it is necessary to provide an adhesive layer separately from the layer A. Absent.

The adhesive tape or sheet A has another layer (intermediate layer; for example, a printed layer, a heat insulating layer, an elastic layer, a rigid layer, etc.) between the layer A and the adhesive layer as necessary. Also good.

By providing a printing layer between the layer A and the pressure-sensitive adhesive layer, design properties can be imparted to the pressure-sensitive adhesive tape or sheet.

In addition, by providing a heat insulating layer between the layer A and the pressure-sensitive adhesive layer, heat conduction to the adherend can be further suppressed, the fire resistance of the adherend can be further improved, and the adherend Carbonization and ignition can be prevented more reliably. The heat insulating layer is the same as described above.

The method for attaching the adhesive tape or sheet A to the adherend is not particularly limited, and the adhesive layer may be attached to the adherend with the base material (silicone resin sheet) facing outside. A peelable film (peelable film) is laminated on the surface of the substrate opposite to the pressure-sensitive adhesive layer, and the peelable film / substrate / layer A / pressure-sensitive adhesive layer (layer A is the pressure-sensitive adhesive). The peelable film may be peeled off after being attached to the adherend in the form of a layer that may also serve as a layer). As the peelable film, for example, a low polarity film (polyolefin film or the like) can be used. When the base material is soft and has no waist, the handleability and the pasting workability are improved by laminating the peelable film in this way. In addition, when functioning as a protective sheet for imparting fire resistance to the adherend, it is ignited if there is a flammable film on the outermost surface in a state of being attached to the adherend, so that the outside of the base material (silicone resin sheet) It is important not to use a flammable film laminated on the surface.

[Fireproof members]
In the refractory member of the present invention, the adhesive tape or sheet (including the adhesive tape or sheet A) is attached to an adherend.

The adherend is not particularly limited as long as it is flammable and can be improved in fire resistance. Examples of the adherend include wood products, plastic products, paper products, and fabric products.

As fireproof members, for example, wooden houses such as conventional shaft construction method and frame wall construction method, reinforced concrete construction, lightweight steel construction, lightweight steel construction, lightweight steel construction, steel construction construction of heavy steel construction, prefabrication construction construction house, etc. Super high-rise condominiums, high-rise condominiums, mid- and low-rise condominiums, apartment buildings such as apartments, coffee shops, restaurants, office buildings, department stores, supermarkets, indoor parking lots, movie theaters, hotels, various sports facilities, gymnasiums, concert halls, dome-shaped baseball Large buildings such as fields, soccer fields, indoor soccer fields, indoor pools, factory buildings and public buildings, exterior wall materials, exterior wall finish materials, interior wall materials, interior wall finish materials, wall insulation materials, ceiling materials, ceiling finish materials, roofing materials , Flooring materials, flooring materials, partition materials, bathroom wall materials, floor materials and ceiling materials and finishing materials, kitchen wall materials, floor materials and ceiling materials Finishing materials, toilet wall materials, flooring materials, ceiling materials, finishing materials, pillar materials, column protection materials, interior materials and surface finishing materials of various doors such as toilets, interiors, entrances and walls, partition materials, Examples include curtains, especially kitchen wall materials and ceiling materials, and partition materials for clean rooms.

In addition, as fireproof materials, surface finish materials for fire prevention equipment such as exhaust ducts, fire doors and fire shutters, surface finish materials for furniture such as tables, anti-scattering materials and surface finish materials such as window glass, mirrors and tiles, signboards and electronic Examples include signboard surface finishing materials and roll screens.

Furthermore, as fireproof members, body protection materials for ships, airplanes, automobiles, railway vehicles, inner and outer wall materials, ceiling materials, roof materials, surface protection materials for printed materials stuck inside and outside railway vehicles, inkjet media materials Surface protection materials, solar cell external protection materials and internal protection materials, battery protection materials such as lithium ion batteries, and electrical / electronic equipment members such as partitions inside electrical equipment.

Furthermore, examples of fire-resistant members include ashtray peripherals, rubber box surface finishing materials, front panels of pachinko machines, and case protection materials.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to them. In the following description, “parts” and “%” are based on weight unless otherwise specified.

Example 1
In a container equipped with a stirrer, a reflux condenser, and a nitrogen introduction tube, 15 g of colloidal silica solution having an average particle size of 8-11 nm (trade name: Snowtex OS, Nissan Chemical Co., Ltd., solid content concentration 20%), 2-propanol 15 g and 5 g of 2-methoxyethanol were added. Concentrated nitric acid was added to adjust the acidity (pH) of the solution within the range of 2 to 4. Next, after the temperature was raised to 70 ° C., 35 g of a silsesquioxane compound having a reactive methoxysilyl group at the molecular end (trade name: X-40-9225, manufactured by Shin-Etsu Chemical Co., Ltd., methoxy content 24%) A solution dissolved in 35 g of propanol was dropped over 2 hours using a dropping funnel to react the silsesquioxane compound with the surface of the colloidal silica particles.
Subsequently, a trifunctional alkoxysilane having a reactive methoxysilyl group at the molecular end and a polysiloxane compound derived from a bifunctional alkoxysilane (trade name: X-40-9246, manufactured by Shin-Etsu Chemical Co., Ltd., methoxy content 12%) A solution prepared by dissolving 25 g in 25 g of 2-propanol was added dropwise over 1 hour to react with the silsesquioxane compound on the colloidal silica. After stirring with heating at 100 ° C. for 1 hour, the mixture was cooled to room temperature (25 ° C.), and concentrated under reduced pressure by distilling off the solvent. 0.05 g of a catalyst (trade name “CAT-AC”, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to the liquid to obtain a liquid transparent resin composition A.
A transparent resin composition A was applied to a silicone-treated surface of a silicone-treated polyethylene terephthalate (PET) film (thickness: 38 μm, trade name “MRF-38”, manufactured by Mitsubishi Plastics). Using an applicator, it was applied so that the thickness after drying was 100 μm, and then dried in a hot air circulation oven at 130 ° C. for 5 minutes to obtain a silicone resin substrate.
Polyethylene terephthalate (PET) film in which water-dispersed acrylic adhesive [base polymer: 2-ethylhexyl acrylate / butyl acrylate / acrylic acid = 30/70/3 (weight ratio), solid content 40%] is treated with silicone (Thickness: 38 μm, trade name “MRF-38”, manufactured by Mitsubishi Plastics, Inc.) Using an applicator manufactured by Tester Sangyo Co., Ltd., the thickness after drying is 20 μm. Then, it was dried in a hot air circulation oven at 130 ° C. for 5 minutes to obtain an acrylic pressure-sensitive adhesive layer.
An adhesive tape (silicone resin substrate / acrylic adhesive layer) was obtained by bonding the silicone resin substrate prepared above and the acrylic adhesive layer. When this is affixed to the adherend, the silicone resin substrate becomes the outermost surface. The total light transmittance (thickness: 100 μm) of the silicone resin substrate is 94%, the total light transmittance (thickness: 20 μm) of the adhesive layer is 90%, and the total light transmittance of the entire adhesive tape (thickness: 120 μm). Was 92%.

Example 2
Water dispersion type acrylic adhesive [base polymer: 2-ethylhexyl acrylate / butyl acrylate / acrylic acid = 30/70/3 (weight ratio), solid content 40%] to 100 parts, 25 parts of sodium silicate aqueous solution ( After adding and stirring sodium silicate 3 (manufactured by Adeka, solid content 38%), a silicone-treated polyethylene terephthalate (PET) film (thickness: 38 μm, trade name “MRF-38”, manufactured by Mitsubishi Plastics) On the silicone-treated surface, using an applicator made by Tester Sangyo Co., Ltd., the thickness after drying is applied to 100 μm, and then dried in a hot air circulating oven at 90 ° C. for 5 minutes to form a heat insulating layer. Obtained.
By adhering the silicone resin base material and acrylic pressure-sensitive adhesive layer prepared in Example 1 and the above heat-insulating layer so as to have a layer structure of silicone resin base material / heat-insulating layer / acrylic pressure-sensitive adhesive layer, I got a tape. When this is affixed to the adherend, the silicone resin substrate becomes the outermost surface. In addition, the total light transmittance (thickness: 100 μm) of the heat insulating layer was 89%, and the total light transmittance (thickness: 220 μm) of the entire adhesive tape was 89%.

Example 3
In a container equipped with a stirrer, a reflux condenser, and a nitrogen introduction tube, 15 g of colloidal silica solution having an average particle size of 8-11 nm (trade name: Snowtex OS, Nissan Chemical Co., Ltd., solid content concentration 20%), 2-propanol 15 g and 5 g of 2-methoxyethanol were added. Concentrated nitric acid was added to adjust the acidity (pH) of the solution within the range of 2 to 4. Next, after the temperature was raised to 70 ° C., 35 g of a silsesquioxane compound having a reactive methoxysilyl group at the molecular end (trade name: X-40-9225, manufactured by Shin-Etsu Chemical Co., Ltd., methoxy content 24%) A solution dissolved in 35 g of propanol was dropped over 2 hours using a dropping funnel to react the silsesquioxane compound with the surface of the colloidal silica particles.
Subsequently, a trifunctional alkoxysilane having a reactive methoxysilyl group at the molecular end and a polysiloxane compound derived from a bifunctional alkoxysilane (trade name: X-40-9246, manufactured by Shin-Etsu Chemical Co., Ltd., methoxy content 12%) A solution prepared by dissolving 25 g in 25 g of 2-propanol was added dropwise over 1 hour to react with the silsesquioxane compound on the colloidal silica. After stirring with heating at 100 ° C. for 1 hour, the mixture was cooled to room temperature (25 ° C.), and the solvent was distilled off under reduced pressure and concentrated to obtain a liquid transparent resin composition B.
A transparent resin composition B was applied to a silicone-treated surface of a silicone-treated polyethylene terephthalate (PET) film (thickness: 38 μm, trade name “MRF-38”, manufactured by Mitsubishi Plastics). Using an applicator, it was applied so that the thickness after drying was 100 μm, and then dried in a hot air circulation oven at 130 ° C. for 5 minutes to obtain a silicone resin substrate.
Water-dispersible acrylic adhesive [base polymer: 2-ethylhexyl acrylate / acrylic acid = 100/4 (weight ratio), solid content 40%] (fine tack adhesive composition) treated with silicone-treated polyethylene terephthalate (PET ) Using a tester industry applicator on the silicone-treated surface of the film (thickness: 38 μm, trade name “MRF-38”, manufactured by Mitsubishi Plastics), the thickness after drying should be 20 μm. And then dried in a hot air circulating oven at 130 ° C. for 5 minutes to obtain a fine tack adhesive layer.
Water-dispersed acrylic adhesive [base polymer: 2-ethylhexyl acrylate / butyl acrylate / acrylic acid = 30/70/3 (weight ratio), solid content 40%] (acrylic adhesive composition) treated with silicone The thickness of the polyethylene terephthalate (PET) film (thickness: 38 μm, trade name “MRF-38”, manufactured by Mitsubishi Plastics, Inc.) on the silicone-treated surface using an applicator manufactured by Tester Sangyo Co., Ltd. Was then applied in a hot air circulation oven at 130 ° C. for 5 minutes to obtain an acrylic pressure-sensitive adhesive layer.
An adhesive tape (silicone resin substrate / fine tack pressure-sensitive adhesive layer / acrylic pressure-sensitive adhesive layer) was obtained by bonding the silicone resin base material prepared above, the fine tack pressure-sensitive adhesive layer, and the acrylic pressure-sensitive adhesive layer. When this is affixed to the adherend, the silicone resin substrate becomes the outermost surface. The total light transmittance (thickness: 100 μm) of the silicone resin substrate is 94%, the total light transmittance (thickness: 20 μm) of the fine tack adhesive layer is 90%, and the total light transmittance of the acrylic pressure-sensitive adhesive layer ( (Thickness: 20 μm) was 90%, and the total light transmittance (thickness: 140 μm) of the entire adhesive tape was 91%.

Example 4
A water-dispersed acrylic pressure-sensitive adhesive [base polymer: 2-ethylhexyl acrylate / acrylic acid = 100/4 (weight ratio), solid content 40%] to a solid content of 104 parts by weight of the acrylic pressure-sensitive adhesive, A mixed liquid (fine tack adhesive composition) containing 3 parts by weight of a crosslinking agent [1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, trade name “Tetrad C”, manufactured by Mitsubishi Gas Chemical Co., Ltd.] Then, the silicone-treated polyethylene terephthalate (PET) film (thickness: 38 μm, trade name “MRF-38”, manufactured by Mitsubishi Plastics) was dried using an applicator manufactured by Tester Sangyo Co., Ltd. The coating was applied so that the subsequent thickness was 20 μm, and then dried in a hot air circulation oven at 130 ° C. for 5 minutes to obtain a fine tack adhesive layer.
Except using this fine tack adhesive layer as the fine tack adhesive layer, the same operation as in Example 3 was performed to obtain an adhesive tape (silicone resin substrate / fine tack adhesive layer / acrylic adhesive layer). It was. When this is affixed to the adherend, the silicone resin substrate becomes the outermost surface. The total light transmittance (thickness: 100 μm) of the silicone resin substrate is 94%, the total light transmittance (thickness: 20 μm) of the fine tack adhesive layer is 90%, and the total light transmittance of the acrylic pressure-sensitive adhesive layer ( (Thickness: 20 μm) was 90%, and the total light transmittance (thickness: 140 μm) of the entire adhesive tape was 91%.

Example 5
A water-dispersed acrylic pressure-sensitive adhesive [base polymer: 2-ethylhexyl acrylate / butyl acrylate / acrylic acid = 30/70/4 (weight ratio), solid content 40%] and solid content 104 of the acrylic pressure-sensitive adhesive A mixed solution containing 0.1 part by weight of a crosslinking agent [1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, trade name “Tetrad C”, manufactured by Mitsubishi Gas Chemical Co., Ltd.] with respect to parts by weight ( Tester Sangyo Co., Ltd. on a silicone-treated surface of a polyethylene-treated terephthalate (PET) film (thickness: 38 μm, trade name “MRF-38”, manufactured by Mitsubishi Plastics). Using a made applicator, apply so that the thickness after drying is 20 μm, and then dry in a hot air circulating oven at 130 ° C. for 5 minutes to form a fine tack adhesive layer Got.
Except using this fine tack adhesive layer as the fine tack adhesive layer, the same operation as in Example 3 was performed to obtain an adhesive tape (silicone resin substrate / fine tack adhesive layer / acrylic adhesive layer). It was. When this is affixed to the adherend, the silicone resin substrate becomes the outermost surface. The total light transmittance (thickness: 100 μm) of the silicone resin substrate is 94%, the total light transmittance (thickness: 20 μm) of the fine tack adhesive layer is 90%, and the total light transmittance of the acrylic pressure-sensitive adhesive layer ( (Thickness: 20 μm) was 90%, and the total light transmittance (thickness: 140 μm) of the entire adhesive tape was 91%.

Comparative Example 1
A transparent resin composition A prepared in the same manner as in Example 1 was coated with an applicator manufactured by Tester Sangyo Co., Ltd. on the surface of a polyethylene terephthalate (PET) film (thickness: 38 μm, trade name “T100N38”, manufactured by Mitsubishi Plastics). It was applied so that the thickness after drying was 100 μm, and then dried in a hot air circulation oven at 130 ° C. for 5 minutes to form a silicone resin layer on the PET substrate. An adhesive tape (PET base material / silicone resin layer / acrylic adhesive layer) was obtained by laminating an acrylic adhesive layer prepared in the same manner as in Example 1 on this silicone resin layer. When this is affixed to an adherend, the PET substrate becomes the outermost surface.

Comparative Example 2
Evaluation was carried out only with a silicone resin substrate produced in the same manner as in Example 1 (not attached to a plywood board).

Comparative Example 3
In Example 1, 10 g of a silsesquioxane compound having a reactive methoxysilyl group at the molecular terminal (trade name: X-40-9225, manufactured by Shin-Etsu Chemical Co., Ltd., methoxy content 24%), reactive at the molecular terminal Except that 50 g of a trifunctional alkoxysilane having a methoxysilyl group and a polysiloxane compound derived from a bifunctional alkoxysilane (trade name: X-40-9246, manufactured by Shin-Etsu Chemical Co., Ltd., methoxy content 12%) were used. The same operation as in Example 1 was performed to prepare a silicone resin base material, an acrylic pressure-sensitive adhesive layer, and a pressure-sensitive adhesive tape (silicone resin base material / acrylic pressure-sensitive adhesive layer).

Comparative Example 4
In Example 1, 60 g of a silsesquioxane compound having a reactive methoxysilyl group at the molecular end (trade name: X-40-9225, manufactured by Shin-Etsu Chemical Co., Ltd., methoxy content 24%) was used and reacted at the molecular end. Other than not using a trifunctional alkoxysilane having a functional methoxysilyl group and a polysiloxane compound derived from a bifunctional alkoxysilane (trade name: X-40-9246, manufactured by Shin-Etsu Chemical Co., Ltd., methoxy content 12%) Performed the same operation as Example 1, and produced the silicone resin base material, the acrylic adhesive layer, and the adhesive tape (silicone resin base material / acrylic adhesive layer).

<Evaluation>
The following evaluation was performed about the silicone resin base material, adhesive tape, etc. which were obtained by the said Example and the comparative example.

(1) Ignition and carbonization test Combustion test using the combustion test equipment shown in Fig. 4 according to the combustion test of the Japan Railway Vehicle Machinery Association (general materials; 45 ° ethyl alcohol test of non-metallic materials for railway vehicles) Went. In FIG. 4, 11 is a specimen (182 mm × 257 mm), 12 is an alcohol container (iron 17.5φ × 7.1 0.8 t), and 13 is a container cradle (cork or the like having a low thermal conductivity). The distance from the center of the lower surface of the specimen to the bottom of the container is 25.4 mm (1 inch).
The pressure-sensitive adhesive tape prepared above (with respect to Comparative Example 2 is evaluated only with a silicone resin base material (not attached to the plywood)) is applied to a plywood having a size of 182 mm × 257 mm × 2.3 mm, and the surface of the pressure-sensitive adhesive tape is the alcohol container 12 side. 4 so that the center of the bottom of the fuel container (alcohol container) 12 is located 25.4 mm vertically below the center of the lower surface of the specimen, as shown in FIG. The fuel container 12 was placed on a cork base (container cradle) 13, 0.5 cc of ethyl alcohol was added to the fuel container 12, ignited, and left until the fuel was burned out. The presence or absence of ignition and carbonization (the state after ethanol combustion) of the adhesive tape (silicone resin base material in Comparative Example 2) was visually observed and evaluated according to the following criteria.
<Ignition>
○: No ignition during ethanol combustion △: Ignites during ethanol combustion but disappears during ethanol combustion ×: Ignites during ethanol combustion and burns after ethanol combustion <Carbonization>
◎: No carbonization ○: No carbonization, yellowing over 30 mm in length ×: Carbonization to the extent that it does not reach the upper end of the specimen XX: Carbonization that reaches the upper end of the specimen

(2) Stress-strain measurement Silicone resin base materials produced in the examples and comparative examples were cut into a length of 50 mm and a width of 10 mm, and set to a length of 10 mm on the chuck of an autograph (manufactured by SHIMAZU). Then, a tensile test was performed at 100 ° C. at a speed of 50 mm / min, and the tensile stress (MPa) at 10% strain at 100 ° C. was measured.

(3) Abrasion resistance test (pencil hardness)
Pencil hardness was measured on the flame-contact surface of the sample shape subjected to the ignition and carbonization tests in accordance with a pencil hardness evaluation method defined in JIS K5400 (evaluated in a state of being attached to a plywood board).

(4) Glossiness The sample-shaped flame contact surface subjected to the ignition and carbonization tests is 60 ° -60 ° with a digital variable gloss meter (trade name “UGV-5K” manufactured by Suga Test Instruments Co., Ltd.). The glossiness (%) in reflection was measured.

(5) Water resistance (water absorption)
The sample subjected to the ignition and carbonization test cut to 10 cm × 10 cm was placed on a horizontal table with the flame contact surface facing upward, and 5 g of water at a water temperature of 23 ° C. was dropped from the sample and allowed to stand for 24 hours. After the sample piece was made vertical and water that was not absorbed was dropped, the weight of the sample piece was measured, and the water absorption rate (%) was measured by the following formula.
Water absorption (%) = {(sample weight after test−sample weight before test) / (sample weight before test)} × 100

(6) Measurement of peeling force Each transparent resin composition obtained in Examples 3 to 5 and Comparative Examples 1, 3, and 4 was dried on an acrylic plate (thickness 2 mm) using an applicator manufactured by Tester Sangyo Co., Ltd. It apply | coated so that latter thickness might be set to 50 micrometers, Then, it dried at 130 degreeC for 5 minute (s) with the hot-air circulation type oven, and each produced the silicone resin adherend.
On the corona-treated surface of a polyethylene terephthalate (PET) film (thickness: 38 μm, trade name “T100N38”, manufactured by Mitsubishi Plastics), a fine tack adhesive composition (in the comparative example, an acrylic adhesive composition) Using an applicator manufactured by Tester Sangyo Co., Ltd., the coating is applied so that the thickness after drying is 20 μm, and then dried in a hot-air circulating oven at 130 ° C. for 5 minutes to form a fine tack tape (in the comparative example, an adhesive tape) Was made.
This tape was cut into a size of 10 mm in width and 100 mm in length, and each tape was attached to the silicone surface of each silicone resin adherend by reciprocating once with a roller at 2 kg pressure. After being left for 30 minutes in an environment of measurement temperature (23 ° C., 80 ° C.), using a tensile tester, peeling was performed at a peeling speed (tensile speed) of 300 mm / min and a peeling angle of 180 °, and the peeling force was measured. This peeling force is equivalent to the peeling force with respect to a base material.

The results are shown in Table 1. In the carbonization test, no yellowing was observed in the adhesive tapes of Examples 2 to 4, but slight yellowing was observed in the adhesive tape of Example 5.

In the pressure-sensitive adhesive tape or sheet of the present invention, the base material has appropriate toughness and flexibility, the organic group content in the base material is extremely low, and the base material is supported by the pressure-sensitive adhesive layer, so that the strength is reinforced. At the same time, it can be applied to an adherend (attachment) to further increase the strength and increase the thickness of the film. Even if the adhesive layer expands during a flame, it is difficult to tear. For this reason, the adhesive tape or sheet | seat of this invention can be utilized as a nonflammable sheet | seat which can improve the fire resistance of a to-be-adhered body significantly, and can prevent carbonization and ignition of an to-be-adhered body reliably.

1 Base material (silicone resin sheet)
2 Adhesive layer 3 Adhesive tape or sheet 10 Base material (silicone resin sheet)
20 Adhesive layer 30 Layer A
40 Adhesive tape or sheet 400 Adhesive tape or sheet 11 Specimen 12 Alcohol container (fuel container)
13 Container stand

Claims (8)

1. An adhesive tape or sheet having an adhesive layer on one side of a substrate, wherein the substrate is a silicone resin sheet having a tensile stress of 0.1 to 3 MPa at 10% strain at 100 ° C. Adhesive tape or sheet.
2. Inorganic oxide particle-containing silicone resin sheet formed from a silicone resin composition in which the silicone resin sheet includes a crosslinked structure in which inorganic oxide particles dispersed in a polysiloxane resin and the polysiloxane resin are crosslinked by a chemical bond The pressure-sensitive adhesive tape or sheet according to claim 1.
3. In the inorganic oxide particle-containing silicone resin sheet, as the polysiloxane resin, a condensation-reactive group-containing polysilsesquioxane whose basic structural unit is a T unit, and a condensation reactivity whose basic structural unit is a D unit and a T unit. The pressure-sensitive adhesive tape or sheet according to claim 2, wherein the group-containing polysiloxane is used.
4. In the inorganic oxide particle-containing silicone resin sheet, a condensation-reactive group-containing polysilsesquioxane whose basic structural unit is a T unit is bonded to the inorganic oxide particle by a chemical bond, and the basic structural unit is a T The condensed reactive group-containing polysiloxane whose basic structural unit is a D unit and a T unit are bonded to the condensation reactive group-containing polysilsesquioxane as a unit to form a crosslinked structure. The adhesive tape or sheet as described.
5. The pressure-sensitive adhesive tape or sheet according to any one of claims 1 to 4, wherein the substrate has a total light transmittance of 80% or more.
6. The pressure-sensitive adhesive tape or sheet according to any one of claims 1 to 5, wherein the total light transmittance of the pressure-sensitive adhesive layer is 80% or more.
7. The pressure-sensitive adhesive tape or sheet according to any one of claims 1 to 6, wherein the total light transmittance of the pressure-sensitive adhesive tape or sheet is 80% or more.
8. A fireproof member in which the adhesive tape or sheet according to any one of claims 1 to 7 is adhered to an adherend.

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