WO2015152365A1 - Feuille adhésive et procédé de production de feuille adhésive - Google Patents

Feuille adhésive et procédé de production de feuille adhésive Download PDF

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Publication number
WO2015152365A1
WO2015152365A1 PCT/JP2015/060445 JP2015060445W WO2015152365A1 WO 2015152365 A1 WO2015152365 A1 WO 2015152365A1 JP 2015060445 W JP2015060445 W JP 2015060445W WO 2015152365 A1 WO2015152365 A1 WO 2015152365A1
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WO
WIPO (PCT)
Prior art keywords
resin
resin layer
adhesive sheet
release material
sensitive adhesive
Prior art date
Application number
PCT/JP2015/060445
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English (en)
Japanese (ja)
Inventor
和恵 上村
揮一郎 加藤
由美子 網野
慈 齋藤
Original Assignee
リンテック株式会社
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Priority to JP2015563014A priority Critical patent/JP5990658B2/ja
Publication of WO2015152365A1 publication Critical patent/WO2015152365A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09J201/06—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • C09J201/08—Carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/51—Elastic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/20—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself
    • C09J2301/204—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself the adhesive coating being discontinuous
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer

Definitions

  • the present invention relates to a pressure-sensitive adhesive sheet and a method for producing a pressure-sensitive adhesive sheet.
  • a general pressure-sensitive adhesive sheet is composed of a base material, a pressure-sensitive adhesive layer formed on the base material, and a release material provided on the pressure-sensitive adhesive layer as necessary.
  • the release material is peeled off, and the pressure-sensitive adhesive layer is stuck to the adherend and attached.
  • a pressure-sensitive adhesive sheet having a large application area used for identification / decoration, coating masking, surface protection of a metal plate, etc. is applied to an adherend with an adhesive layer and an adherend.
  • air pockets are easily generated between them, and the portion becomes “bulging”, making it difficult to adhere the adhesive sheet to the adherend.
  • Patent Document 1 a release material having a fine emboss pattern is brought into contact with the surface of the pressure-sensitive adhesive layer, and a groove having a specific shape is formed on the surface of the pressure-sensitive adhesive layer.
  • a pressure-sensitive adhesive sheet that is artificially arranged in a predetermined pattern is disclosed. By using such an adhesive sheet, it is said that “air pockets” generated when sticking to an adherend can be released to the outside through a groove artificially formed on the surface of the adhesive layer. ing.
  • the pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer in which grooves having a specific shape are arranged in a predetermined pattern is difficult to remove air when the groove width is narrow, and the groove width is wide. There is a problem that not only the surface substrate is recessed and the appearance is inferior, but also the adhesive strength is lowered.
  • the adhesive sheet since the adhesive sheet has the grooves arranged in a predetermined pattern, the adhesive strength of the place where the grooves are arranged is locally inferior, and when the adhesive sheet is attached to the adherend, the adhesive sheet does not peel off from the place. May occur.
  • the pressure-sensitive adhesive sheet when the pressure-sensitive adhesive sheet is peeled off after being adhered to the adherend, the pressure-sensitive adhesive properties of the pressure-sensitive adhesive sheet are locally different. Therefore, depending on the direction in which the pressure-sensitive adhesive sheet is peeled off, there is a possibility that adhesive residue may occur on the adherend. For example, in the case of a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer in which grooves are arranged in a lattice shape, adhesive residue may occur on the adherend when peeled in an oblique direction. Further, when the punching process is performed on the pressure-sensitive adhesive sheet, the groove arrangement pattern and the punching pattern may overlap. In that case, there is a problem that the cutting depth varies, and the cutting cannot be appropriately formed in the adhesive sheet.
  • Patent Document 1 in order to form a fine structure in the pressure-sensitive adhesive layer, a method of laminating the pressure-sensitive adhesive layer and the base material after the pressure-sensitive adhesive is once applied to the emboss liner to form the pressure-sensitive adhesive layer ( The so-called transfer coating method is employed.
  • a base material having a low polarity surface such as a polyolefin base material
  • sufficient adhesion cannot be obtained at the interface between the base material and the pressure-sensitive adhesive layer.
  • a release material made of paper a release material made of a resin film makes it difficult to form a fine emboss pattern on the adhesive layer.
  • the pressure-sensitive adhesive sheet described in Patent Document 1 is inferior in blister resistance, there is a problem that blisters are likely to occur when used at high temperatures.
  • the present invention provides a pressure-sensitive adhesive sheet that has excellent air bleedability capable of easily removing air pockets that may be generated when affixed to an adherend, and also has good blister resistance and adhesive properties. For the purpose.
  • the present inventor has a resin layer including a resin portion containing a resin as a main component and a particle portion made of fine particles, and in each of predetermined regions on two surfaces of the resin layer, A pressure-sensitive adhesive sheet having a plurality of concave portions having a maximum height difference of a specific value or more and having a plurality of concave portions having a predetermined ratio or more different from each other has been found to solve the above-mentioned problems. Completed.
  • the present invention provides the following [1] to [21].
  • a resin layer containing a resin part (X) containing a resin as a main component and a particle part (Y) made of fine particles, and a substrate or a release material ( R2) and at least the surface (1) of the resin layer on the side provided with the release material (R1) is an adhesive sheet having adhesiveness, The elastic modulus at 23 ° C.
  • a maximum height difference of 100 nm or more in a region (P1) surrounded by a 5 mm square arbitrarily selected on the surface (1) of the exposed resin layer A plurality of recesses (Z1) having a shape, and 95% or more of the plurality of recesses (Z1) appearing in the region (P1) have shapes different from each other, In a region (P2) surrounded by a square with a side of 5 mm arbitrarily selected on the surface (2) of the resin layer on the side where the substrate or release material (R2) is provided, 0.5 ⁇ m or more
  • a plurality of recesses (Z2) having a maximum height difference, and 95% or more of the plurality of recesses (Z2) present in the region (P2) have shapes different from each other (hereinafter referred to as “first” Also called "adhesive sheet”.
  • a resin layer containing a resin part (X) containing a resin as a main component and a particle part (Y) made of fine particles on the release material (R1), and a substrate or release material ( R2) and at least the surface (1) of the resin layer on the side provided with the release material (R1) is an adhesive sheet having adhesiveness, The elastic modulus at 23 ° C.
  • There are a plurality of (Z1), and 95% or more of the plurality of recesses (Z1) present in the region (P1) have shapes different from each other
  • There are a plurality of recesses (Z2) having a maximum height difference, and 95% or more of the plurality of recesses (Z2) present in the region (P2) have shapes different from each other (hereinafter referred to as “second” Also called "adhesive sheet”.
  • One or more of the recesses (Z1) appearing or existing in the region (P1) on the surface (1) are surrounded by a square having a side of 5 mm adjacent to the region (P1).
  • the pressure-sensitive adhesive sheet according to the above [11] or [12], wherein the resin portion (X) further contains one or more selected from a metal chelate crosslinking agent and an epoxy crosslinking agent.
  • the resin layer includes, from the release material (R1) side, a layer (X1) mainly including the resin portion (X), a layer (Y1) including 15% by mass or more of the particle portion (Y), and mainly a resin.
  • the layer (X1) is a layer formed from a composition containing a resin as a main component
  • the layer (Y1) is a layer formed from a composition containing 15% by mass or more of fine particles
  • the pressure-sensitive adhesive sheet according to the above [20] wherein the layer (X2) is a layer formed from a composition containing a resin as a main component.
  • Step (1) On the release material (R1), a coating film (x ′) composed of a composition (x) containing a resin as a main component, and a coating composition (y) comprising 15% by mass or more of the fine particles.
  • the pressure-sensitive adhesive sheet of the present invention has excellent air bleedability that can easily remove air pockets that can be generated when it is attached to an adherend, and also has good blister resistance and pressure-sensitive adhesive properties.
  • the adhesive sheet produced in Example 1 it is an image at the time of observing with a scanning electron microscope after removing release agent (R1), Comprising: (a) is the surface (from the side surface side of the resin layer of the said adhesive sheet) The perspective image of 1) and (b) are the enlarged images of (a). It is an image at the time of observing the adhesive sheet produced in Example 1 with the scanning electron microscope, (a) is a cross-sectional image of the surface (2) side vicinity of the resin layer of the said adhesive sheet, (b) is the said adhesive FIG. 8 is a perspective image of the surface (2) of the resin layer of the sheet (note that the image in FIG.
  • Example 8 is based on the surface (2) of the resin layer in order to confirm the presence of a recess on the surface (2) of the resin layer. It was taken and photographed before laminating the material (before the backside treatment).
  • the description of “YY including XX component as main component” and “YY mainly composed of XX component” is “the component having the highest content among components included in YY is XX component”. It means that there is.
  • the specific content of the XX component in the description is usually 50% by mass or more with respect to the total amount of YY (100% by mass), but the content of the XX component is preferably It is 65 to 100% by mass, more preferably 75 to 100% by mass, and still more preferably 85 to 100% by mass.
  • “(meth) acrylic acid” indicates both “acrylic acid” and “methacrylic acid”, and the same applies to other similar terms.
  • the lower limit value and the upper limit value described in a stepwise manner can be independently combined for a preferable numerical range (for example, a range such as content).
  • a preferable numerical range for example, a range such as content.
  • a preferable numerical range for example, a range such as content.
  • the pressure-sensitive adhesive sheet of the present invention comprises a resin layer (X) containing a resin as a main component on a release material (R1) and a particle part (Y) comprising fine particles, and a substrate on the resin layer. Or if it has a peeling material (R2), it will not restrict
  • the surface (1) of the resin layer on the side on which the release material (R1) is provided has adhesiveness. .
  • the surface (2) of the resin layer on the side provided with the base material or the release material (R2) (hereinafter, also simply referred to as “the surface (2) of the resin layer”). ) May also have adhesiveness.
  • the pressure-sensitive adhesive sheet in which the surface (2) of the resin layer has adhesiveness and the release material (R2) is laminated on the surface (2) can be an adhesive sheet having adhesiveness on both surfaces.
  • the pressure-sensitive adhesive sheet according to the present invention is determined depending on whether or not a recess (Z1) having a maximum height difference of 100 nm or more exists on the surface (1) of the resin layer.
  • a "first pressure-sensitive adhesive sheet” having a structure such as the pressure-sensitive adhesive sheets 1a and 1b shown in 1 (a) and (b) and a structure like the pressure-sensitive adhesive sheets 2a and 2b shown in FIGS. 2 (a) and 2 (b) And can be divided into “second pressure-sensitive adhesive sheet”.
  • the length of the recess (Z1) when the recess (Z1) that appears or exists on the surface (1) is viewed in plan is not particularly limited. That is, the recess (Z1) includes a relatively long groove shape and a relatively short recess shape. Further, the recess (Z2) existing on the surface (2) described later includes a relatively long groove shape and a relatively short recess shape, similarly to the recess (Z1).
  • the structure of the 1st adhesive sheet and 2nd adhesive sheet of this invention is demonstrated.
  • the first pressure-sensitive adhesive sheet of the present invention and “the second pressure-sensitive adhesive sheet of the present invention” are collectively referred to as “the pressure-sensitive adhesive sheet of the present invention”.
  • the first pressure-sensitive adhesive sheet of the present invention has a maximum height of 0.5 ⁇ m or more on the surface (2) 122 of the resin layer 12 as the pressure-sensitive adhesive sheets 1a and 1b shown in FIGS. 1 (a) and 1 (b). There are a plurality of recesses (Z2) 22 having a difference.
  • the first pressure-sensitive adhesive sheet of the present invention the presence of the recess (Z1) on the surface (1) 121 of the resin layer 12 is not confirmed before the release material (R1) 11 is removed. When the R1) 11 is removed, a plurality of concave portions (Z1) having a maximum height difference of 100 nm or more appear on the surface (1) 121 of the exposed resin layer 12.
  • the release material (R1) 11 is bonded to the second pressure-sensitive adhesive sheet of the present invention such as the pressure-sensitive adhesive sheets 2a and 2b shown in FIGS. 2 (a) and 2 (b).
  • the first pressure-sensitive adhesive sheet of one embodiment of the present invention for example, a resin layer 12 and a base material 13 are placed in this order on a release material (R1) 11 as shown in FIG.
  • the pressure-sensitive adhesive sheet 1a having a structure laminated with the above is mentioned.
  • stacked the resin layer 12 and the peeling material (R2) 14 in this order on the peeling material (R1) 11 as shown in FIG.1 (b) may be sufficient.
  • the surface (1) 121 of the resin layer 12 has adhesiveness, but the surface (2) 122 of the resin layer 12 may also have adhesiveness. If the surface (2) also has adhesiveness, the adhesive sheet 1a shown in FIG. 1 (a) has good adhesion between the resin layer 12 and the substrate 13, and the adhesive sheet shown in FIG. 1 (b). If it is 1b, it can be set as a double-sided adhesive sheet.
  • the second pressure-sensitive adhesive sheet of the present invention has a maximum height of 0.5 ⁇ m or more on the surface (2) 122 of the resin layer 12 as the pressure-sensitive adhesive sheets 2a and 2b shown in FIGS.
  • the second pressure-sensitive adhesive sheet of one embodiment of the present invention for example, a resin layer 12 and a base material 13 are provided on a release material (R1) 11 as shown in FIG.
  • stacked in order is mentioned.
  • stacked the resin layer 12 and the peeling material (R2) 14 in this order on the peeling material (R1) 11 as shown in FIG.2 (b) may be sufficient.
  • the surface (2) 122 of the resin layer 12 may also have adhesiveness. If the surface (2) also has adhesiveness, the adhesive sheet 2a shown in FIG. 2 (a) has good adhesion between the resin layer 12 and the substrate 13, and the adhesive sheet shown in FIG. 2 (b). If it is 2b, it can be set as a double-sided adhesive sheet.
  • the resin layer 12 included in the pressure-sensitive adhesive sheet of the present invention is a layer including a resin part (X) containing a resin as a main component and a particle part (Y) made of fine particles.
  • a resin part (X) containing a resin as a main component and a particle part (Y) made of fine particles.
  • the configuration of the distribution of the resin portion (X) and the particle portion (Y) in the resin layer 12 may be a configuration in which the resin portion (X) and the particle portion (Y) are substantially evenly distributed. In particular, it may be configured to be divided into a part mainly composed of the resin part (X) and a part mainly composed of the particle part (Y).
  • a portion where the recess (Z2) 22 is formed on the surface (2) in the resin layer 12, a portion where the recess (Z2) 22 is formed on the surface (2).
  • the distribution may be such that the proportion of the particle portion (Y) is smaller than the others, or the particle portion (Y) may not be partially present.
  • the recess (Z2) on the surface (2) of the resin layer of the pressure-sensitive adhesive sheet of the present invention is formed by, for example, forming an emboss pattern by pressing a release material having an emboss pattern on the surface of the resin layer. It is different from a groove having a pre-designed shape as formed by The concave portion (Z2) is preferably formed by self-forming of the resin layer.
  • self-forming means a phenomenon that creates a disordered shape naturally in an autonomous formation process of a resin layer, and more specifically, formed from a composition that is a material for forming a resin layer. It means a phenomenon that naturally forms a disordered shape in the autonomous formation process of the resin layer by drying the coated film.
  • the recess (Z2) formed by the self-formation of the resin layer is formed in the drying process of the coating film made of the composition that is the material for forming the resin layer.
  • the shape of the recess (Z2) formed by self-forming the resin layer in this way is adjusted to some extent by adjusting the drying conditions and the type and content of the components in the composition that is the resin layer forming material.
  • the said recessed part (Z2) is not formed in a predetermined position like the groove
  • the process of forming the recesses (Z2) on the surface (2) of the resin layer of the pressure-sensitive adhesive sheet of the present invention is considered as follows. First, at the time of forming a coating film made of a composition containing fine particles as a material for forming the particle portion (Y), fine particles are present randomly in the coating film. Here, in the step of drying the coating film, shrinkage stress is generated inside the coating film, and cracks are generated in the coating film at a portion where the binding force of the resin, which seems to be caused by the presence of fine particles, is weakened. And it is thought that resin (Z2) is formed on the surface (2) of a resin layer because resin around this crack part flows into the space temporarily generated by the crack. In addition, in the drying process of the coating film, when cracks occur in the coating film, the fine particles that were originally present are pushed away to other parts, so the particle part (Y2) where the recess (Z2) is formed ) May be less than others.
  • the first pressure-sensitive adhesive sheet of the present invention has a surface (1) due to the presence of a plurality of recesses (Z2) formed on the surface (2) of the resin layer and the uneven distribution of fine particles in the resin layer. ) Is considered to have a partially non-uniform distribution. Therefore, it is considered that the recess (Z1) appears on the surface (1) of the resin layer when the release material (R1) is removed from the first pressure-sensitive adhesive sheet of the present invention. Therefore, the recess (Z1) that appears or exists on the surface (1) of the resin layer included in the first and second pressure-sensitive adhesive sheets of the present invention is, for example, a release material having an embossed pattern on the surface of the resin layer.
  • the shape of the recess (Z1) is different from the groove formed by the transfer of the embossed pattern, as in the case of the recess (Z2).
  • the said recessed part (Z1) is not formed in a predetermined position like the groove
  • the concave portion (Z2) separately forms, for example, a coating film made of a composition having a large amount of fine particles and a small resin content, and a coating film made of a composition containing a resin as a main component, It is easy to form by drying these two coating films simultaneously.
  • the recess (Z2) the recess (Z1) is likely to appear on the surface (1) when the release material (R1) is removed.
  • the two-layer coating films are dried at the same time, resulting in a shrinkage stress difference inside the coating film and causing cracks in the coating film. It will be easier.
  • each item for facilitating the formation of the recess (Z2) and the appearance of the recess (Z1) on the surface (1) are as described in the corresponding item described later. -The type of resin, constituent monomer, molecular weight, and content contained in the composition that is the coating film forming material.
  • composition which is a film-forming material The kind of crosslinking agent and the kind of solvent which are contained in the composition which is a film-forming material.
  • the above items are often set appropriately for the purpose of forming a pressure-sensitive adhesive layer having a flat surface.
  • the concave portion (Z2) when the concave portion (Z2) is intentionally formed and the release material (R1) is removed, the concave portion (Z1) that can contribute to the improvement of the air release property of the pressure-sensitive adhesive sheet on the surface (1).
  • the above-mentioned matters are set so as to appear, and this is completely different from a general method for designing an adhesive layer of an adhesive sheet.
  • the above items are preferably set as appropriate in consideration of the fluidity of fine particles and resin contained in the coating film to be formed. For example, by adjusting the viscosity of a coating film made of a composition containing a large amount of fine particles to an appropriate range, while maintaining the predetermined fluidity of the fine particles in the coating film, other coating films (containing a large amount of resin) The mixing with the coating film) can be moderately suppressed. By adjusting in this way, in the coating film containing a lot of resin, cracks are generated in the horizontal direction, and the recesses (Z2) tend to be easily formed.
  • the ratio of the formed recesses (Z2) on the surface (2) can be increased, the ratio of the recesses (Z2) connected to each other can be increased, and the release material (R1) is removed.
  • the recess (Z1) is likely to appear on the surface (1).
  • the type, constituent monomer, molecular weight, and resin content of the resin so that the resin contained in the coating film containing a large amount of resin has appropriate viscoelasticity.
  • the hardness of the coating film hardness determined by factors such as the viscoelasticity of the resin and the viscosity of the coating solution
  • the shrinkage stress of the resin portion (X) is increased, and the recess (Z2) is formed. It becomes easy to form.
  • the hardness of the coating film becomes harder, the shrinkage stress becomes stronger and the concave portion (Z2) is more likely to be generated.
  • the adhesive strength of the resin layer formed from the coating film tends to decrease.
  • the degree of swelling of the resin layer thickness by the fine particles and the self-forming force of the recesses (Z2) are adjusted, As a result, it is considered that the recess (Z2) can be easily formed on the surface (2) and can be adjusted.
  • the crosslinking rate of the formed coating film (or composition that is a forming material). That is, when the crosslinking speed of the coating film is too high, the coating film may be cured before the recess (Z2) is formed. It also affects the size of cracks in the coating.
  • the crosslinking rate of the coating film can be adjusted by appropriately setting the type of the crosslinking agent and the solvent in the composition as the forming material, the drying time and the drying temperature of the coating film.
  • the first and second pressure-sensitive adhesive sheets of the present invention preferably further satisfy one or more of the following requirements (IIIa), requirements (IVa), and requirements (Va), and satisfy all requirements: Is more preferable.
  • Requirement (Va) The shape of the pasting surface on the exposed surface (1) of the resin layer is indefinite. The requirements (Ia) to (Va) will be described in detail below.
  • FIG. 3 is a schematic cross-sectional view of the resin layer showing an example of the shape on the surface (1) side of the resin layer of the pressure-sensitive adhesive sheet of the present invention.
  • a plurality of concave portions (Z1) 21 appear or exist as shown in FIG.
  • the shape of the normal concave portion (Z1) includes two peak portions (M 1 ), (M 2 ), a valley portion (N), and Have
  • the “maximum height difference” of the recess (Z1) is the highest position (m) of the two peak portions (M 1 ) and (M 2 ) with respect to the thickness direction of the resin layer 12 (FIG. 3 (a), the length of the difference (H 1 ) between the peak portion (M 1 ) maximum point and the lowest position (n) (the minimum point of the valley portion (N) in FIG. 3 (a)). means. In the case as shown in FIG.
  • a recess (Z1) 211 having two peak portions (M 11 ) and (M 12 ) and a valley portion (N 1 ), and two peak portions (M 12 ) and (M 13 ), and a recess (Z1) 212 having a valley portion (N 2 ).
  • the length of the difference (H 11 ) between the maximum point of the peak portion (M 11 ) and the minimum point of the valley portion (N 1 ) represents the maximum height difference of the concave portion (Z 1) 211, and the peak portion (M 13 )
  • the minimum point of the valley portion (N 2 ) (H 12 ) represents the maximum height difference of the recess (Z 1) 212.
  • the “recess (Z1)” that appears or exists on the surface (1) refers to a recess having a maximum height difference of 100 nm or more.
  • the “concave portion (Z1)” defined in the present invention it is sufficient that a portion having a maximum height difference of 100 nm or more is included in any portion of the concave portion (Z1), and covers the entire region of the concave portion (Z1). It is not necessary to have a height difference of the maximum height difference value.
  • the maximum height difference of the single concave portion (Z1) is 100 nm or more.
  • the thickness is preferably 200 nm or more and less than the thickness of the resin layer, more preferably 300 nm and less than the thickness of the resin layer, and still more preferably 500 nm or more and less than the thickness of the resin layer.
  • the ratio of the maximum value of the maximum height difference values of the plurality of recesses (Z1) appearing or existing in the region (P1) to the thickness of the resin layer [maximum value of the maximum height difference / thickness of the resin layer. ] Is preferably 0.1 / 100 to 100/100, more preferably 0.8 / 100 to 50/100, still more preferably 1.2 / 100 to 30/100, still more preferably 2.0 / 100. 100 to 20/100.
  • the average width of the concave portion (Z1) is preferably 1 to 2000 ⁇ m, more preferably 3 from the viewpoint of improving the air release property of the pressure-sensitive adhesive sheet and improving the pressure-sensitive adhesive property of the pressure-sensitive adhesive sheet. It is ⁇ 1500 ⁇ m, more preferably 5 to 1000 ⁇ m.
  • the width of the concave portion (Z1) means the distance between the maximum points of the two peak portions. In the concave portion (Z1) 21 shown in FIG. It refers to the distance L 1 between M 1 ) and the mountain portion (M 2 ). Further, in the recess (Z1) 211 shown in FIG.
  • Ratio of the maximum height difference and the average width of the single recess (Z1) [maximum height difference / average width] (in the recess (Z1) 21 shown in FIG. 3A, “H 1 / L 1 ”) is preferably from 1 / 3,000,000 to 1,500 / 1, more preferably from 1 / 50,000 from the viewpoint of improving the air release property of the pressure-sensitive adhesive sheet and improving the pressure-sensitive adhesive property of the pressure-sensitive adhesive sheet. It is ⁇ 500 / 1, more preferably 1/15000 to 150/1.
  • the concave portion (Z1) that appears or exists on the surface (1) of the resin layer of the pressure-sensitive adhesive sheet of the present invention is for releasing the “air pocket” that occurs when the pressure-sensitive adhesive sheet of the present invention is stuck to the adherend to the outside. It plays a role as an air discharge passage. Normally, the recess (Z1) having a relatively small maximum height difference as described above is difficult to play a role as an air discharge passage for escaping the “air reservoir” to the outside. However, in the pressure-sensitive adhesive sheet of the present invention, the resin layer is easily deformed because a plurality of predetermined recesses (Z2) are also present on the surface (2) of the resin layer of the pressure-sensitive adhesive sheet.
  • the concave portion (Z1) on the surface (1) can escape the air pool to the outside by the pressure of the air pool. Deforms to a certain size and functions as an air discharge passage.
  • the pressure-sensitive adhesive sheet of the present invention has a shape in which 95% or more of the plurality of concave portions (Z1) appearing or existing in the region (P1) on the surface (1) are different from each other as described in the requirement (IIa).
  • FIG. 4 shows an example of a schematic plan view of the surface (1) of the resin layer of the pressure-sensitive adhesive sheet of the present invention. As shown in FIG. 4, 95% or more of the plurality of recesses (Z1) 21 that appear or exist on the surface (1) 121 of the resin layer 12 of the pressure-sensitive adhesive sheet of the present invention have different shapes.
  • the plurality of concave portions (Z1) having different shapes that appear or exist in the region (P1) on the surface (1) of the resin layer have air release properties, appearance, pressure-sensitive adhesive properties, Also, the degree of contribution to the improvement of the punching processability is different. Therefore, by forming a plurality of recesses having different degrees of contribution to various characteristics, it is possible to obtain an adhesive sheet that improves these characteristics in a well-balanced manner.
  • the ratio of the plurality of concave portions (Z1) having different shapes that appear or exist in the region (P1) on the surface (1) of the resin layer is the region (P1). ) Is preferably 98% or more, and more preferably 100%, with respect to the total number of recesses (100%).
  • whether or not the above requirement (IIa) is satisfied is determined by arbitrarily selecting a region (P1) surrounded by a square of 5 mm on each side on the surface (1) of the resin layer of the target adhesive sheet. )
  • the observation of the shape of the plurality of recesses (Z1) described above may be a method of directly observing with an electron microscope at the above magnification, and an image is acquired using the electron microscope at the above magnification and is shown in the image.
  • a method of visually observing the shape of the plurality of recesses may be used. More specifically, the determination is made based on the method described in the examples.
  • “the number of recesses (Z1) having different shapes is 100%” means “all of the plurality of recesses (Z1) observed in the region (P1) have different shapes. "Means.
  • a recess continuously connected without interruption in a selected region is counted as “one recess”. For example, even if two concave portions existing in the selected region are combined in another region adjacent to the region and formed as one concave portion, the two in the selected region
  • the individual recesses are counted as independent ones. For example, in a region (P1) surrounded by a square 50 having a side of 5 mm arbitrarily selected on the surface (1) 121 of the resin layer 12 shown in FIG. (Z1) 21 and 210 exist.
  • the number of the concave portions (Z1) appearing or existing in a region (P1) surrounded by a square of 5 mm on each side arbitrarily selected on the surface (1) of the resin layer is 2 or more. However, it is preferably 3 or more, more preferably 4 or more, from the viewpoint of improving the air release property of the pressure-sensitive adhesive sheet, and preferably 20,000 from the viewpoint of maintaining good appearance and adhesive properties. Below, more preferably 10,000 or less.
  • a region surrounded by an arbitrarily selected square 50 having a side of 5 mm on the surface (1) 121 of the resin layer 12 It is preferable that one or more of the recesses (Z1) 21 and 210 appearing or existing in (P1) extend to any side of the square 50 having a side of 5 mm, which is a boundary line of the region (P1).
  • the recesses (Z1) 21 and 210 extend to form a square 50 having a side of 5 mm, which is a boundary line of the region (P1).
  • intersections 21a there are 20 intersections 21a in total with any side.
  • the number of intersections between any side of a square having a side of 5 mm that is the boundary line between the recess (Z1) and the region (P1) is preferably 1 or more, more preferably 2 or more, More preferably, the number is 3 or more.
  • a concave portion (Z1) that appears or exists in the region (P1) on the surface (1) of the resin layer of the pressure-sensitive adhesive sheet of one embodiment of the present invention It is preferable that one or more of these have a shape extending continuously into one or more other regions (P1 ′) surrounded by a square with a side of 5 mm adjacent to the region (P1). More preferably, the shape extends continuously into the region (P1 ′), and more preferably the shape extends continuously into the other region (P1 ′). For example, in FIG.
  • the “recess (Z1) 210” is surrounded by a square 50 having a side of 5 mm.
  • the recess (Z1) appearing or existing in the region (P1) on the surface (1) of the resin layer is not only one or more other regions (P1 ′) adjacent to the region (P1), but also other It is preferable that the shape further extends continuously to the region (P1 ′′) other than the region (P1 ′) adjacent to the region (P1 ′).
  • the “concave portion 210” shown in FIG. 4B is not only the region (P1′-2) adjacent to the region (P1) but also the region (P1′ ⁇ ) adjacent to the region (P1′-2). 5) also has a continuous extended shape.
  • the pressure-sensitive adhesive sheet according to one embodiment of the present invention has a surface (1) when the surface (1) of the resin layer and the smooth surface of the translucent adherend having a smooth surface are attached as described in the requirement (IIIa). ) In 60 to 99.999% of the area where the light-transmitting adherend is adhered to the smooth surface (hereinafter also simply referred to as “applied part” or “applied part on the surface (1)”). Is preferred.
  • the area ratio of the said sticking part is 60% or more, the adhesive surface of the surface (1) of a resin layer and a to-be-adhered body can be ensured, and an adhesive characteristic can be made favorable.
  • the pressure-sensitive adhesive sheet can be made excellent in air-releasing properties, and air pockets that can be generated when the adhesive sheet is affixed to an adherend are easy. Can be removed.
  • the ratio of the area to be adhered to the adherend is preferably 70 to 99.999%, more preferably 80 to 99.996%, still more preferably 85 to 99.9999%, and still more preferably. 90 to 99.990%.
  • the “translucent adherend having a smooth surface” described in the requirement (IIIa) is an adherend used in the measurement of the area ratio of the affixed portion on the surface (1) specified by the requirement. It merely defines the adherend to which the pressure-sensitive adhesive sheet of the present invention is to be attached.
  • the adherend to which the pressure-sensitive adhesive sheet of the present invention is applied is not particularly limited as to whether it has a smooth surface or translucency. For example, it may be a non-transparent adherend comprising a curved surface. Good.
  • the “smooth surface” described in the requirement (IIIa) means that the center line average roughness (Ra 75 ) defined by JIS B0601: 2001 is less than 0.1 ⁇ m (preferably 0.02 ⁇ m or less, more preferably 0.01 ⁇ m). Means the following):
  • the “translucency” described in the requirement (IIIa) means a characteristic that the total light transmittance measured in accordance with JIS K7105 is 70% or more.
  • the material for forming the light-transmitting adherend described in requirement (IIIa) is not particularly limited, but glass is preferable from the viewpoint that it is easy to obtain a light-transmitting adherend having a smooth surface as defined above.
  • the area ratio values of the pasted portions in each region are as follows:
  • the average value of the area ratio of the applied part obtained by the operations (i) to (iii) can be regarded as the “area ratio of the applied part on the surface (1)” of the pressure-sensitive adhesive sheet to be measured.
  • the average value of the area ratio of the applied part calculated by the method described in the examples is regarded as “the area ratio of the applied part on the surface (1)” of the pressure-sensitive adhesive sheet to be measured. You can also.
  • the digital microscope for example, “Digital Microscope VHX-1000” or “Digital Microscope VHX-5000” manufactured by Keyence Corporation can be used. Further, the area to be observed may be increased according to the measurable magnification of the digital microscope, and the area ratio (%) of the affixed portion per 1 mm 2 may be calculated.
  • FIG. 5A the surface (1) of a region (P1) surrounded by a square 50 having a side of 5 mm on the surface (1) 121 of the resin layer shown in FIG. ) 121 and the smooth surface 101a of the translucent adherend 101 are affixed and viewed in a plan view from the W direction on the translucent adherend 101 side in the region (P1) of FIG.
  • FIG. 5B is a diagram schematically showing an example of the shape of the pasted portion in the selected region (P1). Comparing the translucent adherend shown in FIG.
  • FIG. 5 (b) with the schematic diagram in the region (P1) after application and the schematic diagram in the region (P1) shown in FIG. 4 (a), FIG.
  • the non-sticking part 51 with the translucent to-be-adhered body in 5 (b) may become smaller than the part which the recessed part (Z1) 21 in the area
  • the non-sticking part 51 with the smooth surface of a translucent to-be-adhered body is a location where a height difference is large also in the structure of the recessed part (Z1) 21. Therefore, it can be said that the greater the proportion of the non-sticking portion 51, the higher the effect of air release that allows the “air pocket” to escape to the outside.
  • the surface (1) of the resin layer and the smooth surface of the translucent adherend having a smooth surface are pasted.
  • the shape of the affixed portion 52 with the smooth surface of the translucent adherend on the surface (1) of the resin layer (hereinafter also simply referred to as “the affixed portion shape”) is the translucent adherend side. It is preferable that it can be visually recognized. Note that whether or not the shape of the pasted portion can be visually confirmed is determined by visually observing the laminated body 100 of FIG. 5A obtained from the above-described operation (i) from the W direction. It can be judged by whether or not can be confirmed.
  • the surface (1) of the resin layer and When the smooth surface of the translucent adherend having a smooth surface is affixed, the shape of the affixed portion of the surface (1) of the resin layer with the smooth surface of the adherend may be indefinite.
  • “the shape of the affixed portion is indefinite” means that the shape of the affixed portion when the shape of the affixed portion is viewed in plan is surrounded by only a circle or a straight line ( This means a shape that does not have a specific shape such as a triangle, a quadrangle, etc., has no regularity in shape, and does not show similarities in the shapes of individual pasted portions. That is, the shape of the sticking surface formed by transferring the emboss pattern such as pressing the release material having the emboss pattern against the surface of the resin layer cannot be said to be “indeterminate”.
  • the “adhesion of the adhesive sheet” It can also be considered that the shape of the portion is indefinite.
  • recessed part (Z1) appears irregularly or exists on the surface (1) of a resin layer as said requirement (IVa).
  • a plurality of recesses (Z1) appear or exist irregularly on the surface (1) of the resin layer means that a plurality of recesses (Z1 appearing or existing on the surface (1) of the resin layer.
  • Position does not have the same repeating pattern and is irregular (random) (a state in which a plurality of concave portions (Z1) appear or have no periodicity at a position).
  • the “arrangement” Is different from the state of When the plurality of concave portions (Z1) appear or exist irregularly on the surface (1) of the resin layer, it is possible to provide a pressure-sensitive adhesive sheet in which various properties such as air leakage and pressure-sensitive adhesive properties are improved in a well-balanced manner.
  • a plurality of recesses (Z1) appear or appear irregularly on the surface (1) of the resin layer is determined on the surface (1) of the resin layer of the target adhesive sheet.
  • the position of the plurality of concave portions (Z1) present is determined by visual observation or observation with a digital microscope or an electron microscope (magnification: 30 to 100 times).
  • an arbitrarily selected area on the surface (1) surrounded by a square having a side of 1 to 10 mm is selected and appears in the area.
  • the positions of a plurality of existing recesses (Z1) may be determined by observing with a digital microscope or an electron microscope (magnification: 30 to 100 times). In other words, if there is no regularity in the “positions of the plurality of recesses (Z1)” that appear or exist in the selected area, the target adhesive sheet is considered to satisfy the requirement (IV). Can do.
  • the observation of the positions of the plurality of concave portions (Z1) may be a method of directly observing with a digital microscope or an electron microscope at the above magnification, and acquiring an image using the digital microscope or the electron microscope at the above magnification, A method of visually observing the positions of the plurality of recesses (Z1) shown in the image may be used.
  • the shape of the sticking surface on the surface (1) which the resin layer exposed is an indefinite shape as the said requirement (Va).
  • the shape of the sticking surface on the exposed surface (1) means that the release material (R1) is removed, and a plurality of appearing or existing on the exposed surface (1) of the resin layer. It is the surface except the range which a recessed part (Z1) occupies.
  • the “sticking surface” refers to a shaded portion of the surface (1) 121 of the resin layer excluding a plurality of recesses (Z1).
  • the shape of the affixed surface is indefinite means that the affixed surface shape is only a circle or a straight line like the shape of the shaded portion of the surface (1) 121 of the resin layer shown in FIG. It means that the shape does not have a specific shape such as an enclosed shape (triangle, square, etc.) and does not have a predetermined repetitive pattern. That is, the shape of the pasting surface formed by transferring the emboss pattern such as pressing the release material having the emboss pattern against the surface of the resin layer is excluded.
  • the shape of the sticking surface on the surface (1) of the resin layer is considered to be indefinite. Since the shape of the sticking surface on the surface (1) where the resin layer is exposed is indeterminate, it is possible to obtain a pressure-sensitive adhesive sheet in which various properties such as air release and pressure-sensitive adhesive properties are improved in a well-balanced manner.
  • the shape of the sticking surface on the surface (1) is indefinite” is determined by visually or digitally examining the shape of the sticking surface on the surface (1) of the resin layer of the target adhesive sheet. In principle, it is determined by observation with an electron microscope (magnification: 30 to 100 times). However, an arbitrarily selected area on the surface (1) surrounded by a square having a side of 1 to 10 mm (preferably, an area (P1) surrounded by a square having a side of 5 mm) is present in the area.
  • the shape of the applied surface to be determined may be determined by observing with a digital microscope or an electron microscope (magnification: 30 to 100 times).
  • the target adhesive sheet when it is determined that the “shape of the pasting surface” in the selected region is indefinite, the target adhesive sheet can be regarded as satisfying the requirement (V).
  • the observation of the shape of the affixed surface may be a method of directly observing with a digital microscope or an electron microscope at the above magnification, and an image is obtained using the digital microscope or the electron microscope at the above magnification and shown in the image. A method of visually observing the shape of the applied surface is also possible.
  • the recess (Z2) present on the surface (2) of the resin layer satisfies the following requirements (Ib) and (IIb).
  • the first and second pressure-sensitive adhesive sheets of the present invention further satisfy one or more of the following requirements (IIIb), requirements (IVb), and requirements (Vb), and satisfy all the requirements. Is more preferable.
  • Requirement (IIIb) One or more recesses (Z2) exist in a region (Q2) surrounded by a square of 1 mm on an arbitrarily selected side on the surface (2).
  • Requirement (IVb) A plurality of concave portions (Z2) are irregularly present on the surface (2) of the resin layer.
  • FIG. 6 is a schematic cross-sectional view of the resin layer showing an example of the shape on the surface (2) side of the resin layer of the pressure-sensitive adhesive sheet of the present invention.
  • the shape of the normal concave portion (Z2) includes two peak portions (M 1 ), (M 2 ), a valley portion (N), and Have
  • the “maximum height difference” of the recess (Z2) is the highest position (m) of the two peak portions (M 1 ) and (M 2 ) with respect to the thickness direction of the resin layer 12 (FIG. 6 (a), the length of the difference (H 2 ) between the peak portion (M 1 ) maximum point and the lowest position (n) (the minimum point of the valley portion (N) in FIG. 6 (a)). means.
  • FIG. 1 the maximum height difference
  • a recess (Z2) 221 having two peak portions (M 11 ) and (M 12 ) and a valley portion (N 1 ), and two peak portions (M 12 ), (M 13 ), and a recess (Z2) 222 having a valley portion (N 2 ).
  • the length of the difference (H 21 ) between the maximum point of the peak portion (M 11 ) and the minimum point of the valley portion (N 1 ) represents the maximum height difference of the recess (Z 2) 221, and the peak portion (M 13 ) And the minimum point of the valley portion (N 2 ) (H 22 ) represent the maximum height difference of the recess (Z 2) 222.
  • the “recess (Z2)” present on the surface (2) refers to a recess having a maximum height difference of 0.5 ⁇ m or more.
  • a portion having a maximum height difference of 0.5 ⁇ m or more may be included in any portion of the concave portion (Z2). It is not necessary to have a height difference of the maximum height difference value over the region.
  • the determination of whether or not there are a plurality of recesses (Z2) that satisfy the requirement (Ib) is based on a region (5 mm) of an arbitrarily selected one side on the surface (2) of the resin layer of the pressure-sensitive adhesive sheet ( The determination is made by observing the inside of P2) with an electron microscope. More specifically, the determination is made by the method described in the examples.
  • the maximum height difference of the single concave portion (Z2) is 0.5 ⁇ m or more.
  • the thickness is preferably 1.0 ⁇ m or more and less than the thickness of the resin layer, more preferably 3.0 ⁇ m or more and the thickness of the resin layer or less, and further preferably 5.0 ⁇ m or more and the thickness of the resin layer or less. .
  • the ratio of the maximum value of the maximum height difference values of the plurality of recesses (Z2) existing in the region (P2) to the thickness of the resin layer [maximum value of maximum height difference / thickness of the resin layer] Is preferably 1/100 to 100/100, more preferably 5/100 to 99/100, still more preferably 10/100 to 96/100, and even more preferably 15/100 to 90/100.
  • the average value of the width of the concave portion (Z2) is preferably 1 to 500 ⁇ m, more preferably 3 to 400 ⁇ m, and still more preferably 5 to 300 ⁇ m.
  • the width of the concave portion (Z2) means the distance between the maximum points of the two peak portions. In the concave portion (Z2) 22 shown in FIG. It refers to the distance L 2 between M 1 ) and the mountain portion (M 2 ). Further, in the recess (Z2) 221 shown in FIG.
  • Ratio of the maximum height difference and the average width of the single recess (Z2) [maximum height difference / average width] (in the recess (Z2) 22 shown in FIG. 5A, “H 2 / L 2 ”) is preferably 1/500 to 100/1, more preferably 3/400 to 70/3, still more preferably 1/60 to 10/1.
  • the plurality of recesses (Z2) on the surface (2) of the resin layer play an auxiliary role of deforming the resin layer when the surface (1) of the resin layer is pressed against the adherend. That is, by having a plurality of recesses (Z2) on the surface (2) of the resin layer, when the surface (1) of the resin layer of the pressure-sensitive adhesive sheet of the present invention is attached to the adherend, the recesses on the surface (1) (Z1) can be deformed to such an extent that it can serve as an air discharge passage that can release an air pocket generated during sticking to the adherend to the outside.
  • region (P2) on the surface (2) has a mutually different shape as said requirement (IIb).
  • the plurality of recesses (Z2) are not formed using a release material or the like on which an emboss pattern is applied.
  • 95% or more of the plurality of recesses (Z2) existing on the surface (2) of the resin layer have shapes different from each other, which improves the mobility of the resin layer. This contributes to improved air bleedability in conjunction with a plurality of recesses (Z1) that appear or exist on the surface (1) of the resin layer.
  • the ratio of the plurality of recesses (Z2) having different shapes existing in the region (P2) on the surface (2) of the resin layer is the region (P2) Is preferably 98% or more, and more preferably 100%, with respect to the total number (100%) of the recesses present in.
  • the determination as to whether or not the requirement (IIb) is satisfied is the same as the description of the requirement (IIa) regarding the recess (Z1).
  • the pressure-sensitive adhesive sheet of one embodiment of the present invention has one concave portion (Z2) in a region (Q2) surrounded by a square with a side of 1 mm arbitrarily selected on the surface (2) as required (IIIb). It is preferable to exist above. When one or more recesses (Z2) are present in the region (Q2), it is possible to further improve the mobility of the resin layer. From the above viewpoint, the number of the concave portions (Z2) present in the region (Q2) is preferably 2 or more, more preferably 3 or more, and further preferably 4 or more. On the other hand, the appearance and the adhesive properties are good. From the standpoint of maintaining the thickness, it is preferably 1000 or less, more preferably 500 or less.
  • the surface (2) of the resin layer of the adhesive sheet of this invention has adhesiveness
  • the plurality of recesses (Z2) on the surface (2) serve as an air discharge passage for escaping an “air pool” generated when the pressure-sensitive adhesive sheet is attached to the adherend.
  • one or more of the recesses (Z2) existing in () extend to any side of a square with a side of 1 mm, which is the boundary line of the region (Q2).
  • the number of intersections between any one side of a square having a side of 1 mm that is the boundary line between the recess (Z2) and the region (Q2) is preferably 1 or more, more preferably 2 or more, More preferably, the number is 3 or more.
  • the region (Q2) has a shape extending continuously into one or more other regions (Q2 ′) surrounded by a 1 mm square adjacent to the region (Q2), and two or more other regions (Q2 ′).
  • the recess (Z2) present in the region (Q2) on the surface (2) of the resin layer is not only one or more other regions (Q2 ′) adjacent to the region (Q2) but also other regions. It is preferable that the shape further extends continuously to the region (Q2 ′′) other than the region (Q2 ′) adjacent to (Q2 ′).
  • the adhesive sheet of 1 aspect of this invention it is preferable that a several recessed part (Z2) exists irregularly on the surface (2) of a resin layer as said requirement (IVa).
  • the definition that “the plurality of recesses (Z2) are irregularly present” is irregular (random) where the positions of the plurality of recesses (Z2) do not have the same repeating pattern. This means a state (a state in which a plurality of recesses (Z1) appear or has no periodicity at positions where it exists), and is the same as the requirement (IV) of the above-described recess (Z1).
  • the pressure-sensitive adhesive sheet can be further improved in air bleeding.
  • the determination as to whether or not the requirement (IVb) is satisfied is the same as the description of the requirement (IVa) regarding the recess (Z1).
  • the surface shape except a some recessed part (Z2) is indeterminate in the surface (2) of a resin layer as the said requirement (Vb).
  • the surface (2) has adhesiveness and the pressure-sensitive adhesive sheet is used as a double-sided pressure-sensitive adhesive sheet, the surface is a “sticking surface” to the adherend.
  • the meaning of the word “the shape of the surface is indefinite” and the determination method of “whether the shape of the surface is indeterminate” are based on the requirement (Va) for the recess (Z1). Same as described.
  • the substrate used in one embodiment of the present invention is not particularly limited, and examples thereof include a paper substrate, a resin film or sheet, a substrate obtained by laminating a paper substrate with a resin, and the like. It can select suitably according to the use of a sheet
  • the paper constituting the paper substrate include thin paper, medium quality paper, high quality paper, impregnated paper, coated paper, art paper, sulfuric acid paper, glassine paper and the like.
  • Examples of the resin constituting the resin film or sheet include polyolefin resins such as polyethylene and polypropylene; vinyl such as polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, and ethylene-vinyl alcohol copolymer.
  • polyolefin resins such as polyethylene and polypropylene
  • vinyl such as polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, and ethylene-vinyl alcohol copolymer.
  • Polyester resin such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate; polystyrene; acrylonitrile-butadiene-styrene copolymer; cellulose triacetate; polycarbonate; urethane resin such as polyurethane and acrylic-modified polyurethane; polymethylpentene; Polysulfone; Polyetheretherketone; Polyethersulfone; Polyphenylene sulfide; Polyimide resins such as polyetherimide and polyimide; Polyamide resins, acrylic resins, fluorine-based resins.
  • the base material obtained by laminating a paper base material with a resin include laminated paper obtained by laminating the paper base material with a thermoplastic resin such as polyethylene.
  • a resin film or sheet is preferable, a film or sheet made of a polyester resin is more preferable, and a film or sheet made of polyethylene terephthalate (PET) is still more preferable.
  • PET polyethylene terephthalate
  • a film or sheet composed of a resin selected from polyethylene naphthalate and a polyimide resin is preferable, and an application requiring weather resistance.
  • a film or sheet composed of a resin selected from polyvinyl chloride, polyvinylidene chloride, acrylic resin, and fluororesin is preferable.
  • the thickness of the substrate is appropriately set according to the use of the pressure-sensitive adhesive sheet of the present invention, but is preferably 5 to 1000 ⁇ m, more preferably 10 to 500 ⁇ m, and still more preferably 12 to 12 from the viewpoint of handleability and economy.
  • the thickness is 250 ⁇ m, more preferably 15 to 150 ⁇ m.
  • the base material may further contain various additives such as an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a slip agent, an antiblocking agent, and a colorant.
  • the base material used in one embodiment of the present invention is preferably a non-breathable base material from the viewpoint of improving the blister resistance of the obtained pressure-sensitive adhesive sheet, and specifically, the surface of the above-described resin film or sheet.
  • a substrate having a metal layer thereon is preferred.
  • the metal formed by the metal layer include metals having metallic luster such as aluminum, tin, chromium, and titanium.
  • a method for forming the metal layer for example, a method of depositing the metal by a PVD method such as vacuum deposition, sputtering, or ion plating, or a metal foil made of the metal is attached using a general adhesive. The method etc. are mentioned, The method of vapor-depositing the said metal by PVD method is preferable.
  • the surface of the resin film or sheet is oxidized or uneven.
  • Surface treatment by a method or the like, or primer treatment may be performed.
  • the oxidation method include corona discharge treatment, plasma discharge treatment, chromic acid treatment (wet), hot air treatment, ozone, and ultraviolet irradiation treatment.
  • the unevenness method include sand blast method and solvent treatment method. Etc.
  • release material (R1), (R2) As the release material (R1) and the release material (R2) used in one embodiment of the present invention, a release sheet subjected to a double-sided release process, a release sheet subjected to a single-sided release process, or the like is used. And the like coated with a release agent.
  • the said peeling process surface does not have uneven
  • the surface of the release material (R1) that is in contact with the surface (1) of the resin layer is a release treatment surface on which an uneven shape is not formed.
  • the surface is a release treatment surface that is not provided with an emboss pattern.
  • the base material for the release material include the above-described paper base material, resin film or sheet used as the base material included in the pressure-sensitive adhesive sheet of one embodiment of the present invention, and a base material obtained by laminating a paper base material with a resin. It is done.
  • the release agent include rubber elastomers such as silicone resins, olefin resins, isoprene resins, and butadiene resins, long chain alkyl resins, alkyd resins, and fluorine resins.
  • the thickness of the release material is not particularly limited, but is preferably 10 to 200 ⁇ m, more preferably 25 to 150 ⁇ m, and still more preferably 35 to 80 ⁇ m.
  • the resin layer of the pressure-sensitive adhesive sheet of the present invention includes a resin part (X) containing a resin as a main component and a particle part (Y) made of fine particles.
  • a resin part (X) containing a resin as a main component and a particle part (Y) made of fine particles.
  • the surface (1) of the said resin layer in the side in which the peeling material (R1) was provided has adhesiveness
  • the adhesive sheet of this invention was provided with the base material or the peeling material (R2).
  • the surface (2) of the resin layer on the side may also have adhesiveness.
  • a configuration of a layer formed by forming a multilayer structure in which (Y1) and a layer (X2) mainly including the resin portion (X) are laminated in this order can be given.
  • the structure of the multilayer structure described above is a mixed structure in which the boundary between the layer (X1) and the layer (Y1) and / or the boundary between the layer (Y1) and the layer (X2) cannot be determined. There may be.
  • the layer (X1) and the layer (X2) are layers mainly including the resin portion (X), but may include a particle portion (Y).
  • the content of the particle part (Y) in the layer (X1) and the layer (X2) is each independently 15 masses with respect to the total mass (100 mass%) of the layer (X1) or the layer (X2). % And less than the content of the resin constituting the resin part (X).
  • the layer (X1) and the layer (X2) may further have a void portion (Z) described later in addition to the resin portion (X) and the particle portion (Y).
  • the content of the resin in the layer (X1) and the layer (X2) it is usually 50 to 100% by mass with respect to the total mass (100% by mass) of the layer (X1) or the layer (X2), It is preferably 65 to 100% by mass, more preferably 75 to 100% by mass, still more preferably 85 to 100% by mass, and still more preferably 90 to 100% by mass.
  • the “content of the resin in the layer (X1) and the layer (X2)” is the total amount (100% by mass (100% by mass)) of the resin composition that is a material for forming the layer (X1) or the layer (X2). However, it can be regarded as the content of the resin in a)) except for the dilution solvent.
  • grain part (Y) in a layer (X1) and a layer (X2) it is respectively independently in the total mass (100 mass%) of a layer (X1) or a layer (X2). On the other hand, it is less than 15% by mass, preferably 0 to 13% by mass, more preferably 0 to 10% by mass, still more preferably 0 to 5% by mass, and still more preferably 0% by mass.
  • the content of fine particles in the layer (X1) and the layer (X2) refers to the total amount (100% by mass (100% by mass (%) of the resin composition that is a forming material of the layer (X1) or the layer (X2) However, it can also be regarded as the content of fine particles in a)) excluding a diluting solvent.
  • the layer (X1) and the layer (X2) are preferably formed from compositions (x1) and (x2) containing a resin as a main component described later.
  • the layer (Y1) containing 15% by mass or more of the particle part (Y) may be a layer composed only of the particle part (Y), or may be a layer containing the resin part (X) together with the particle part (Y). Moreover, you may have the space
  • the content of the fine particles constituting the particle portion (Y) in the layer (Y1) is 15% by mass or more with respect to the total mass (100% by mass) of the layer (Y1), but preferably 20 to 100%.
  • the amount is by mass, more preferably from 25 to 90% by mass, still more preferably from 30 to 85% by mass, still more preferably from 35 to 80% by mass.
  • the content of the fine particles in the layer (Y1) means the fine particles in the total amount (100% by mass (excluding the diluting solvent)) of the composition that is a forming material of the layer (Y1). It can also be regarded as the content of.
  • the content of the resin in the layer (Y1) is usually 1 to 85% by mass, preferably 5 to 80% by mass, more preferably 10%, based on the total mass (100% by mass) of the layer (Y1). It is ⁇ 75% by mass, more preferably 20 to 70% by mass, and still more preferably 25 to 65% by mass.
  • “content of the resin in a layer (Y1)” is resin in the whole quantity (100 mass% (however, except a dilution solvent)) of the composition which is the formation material of the said layer (Y1). It can also be regarded as the content of.
  • the said layer (Y1) is a layer formed from the composition (y) which contains the below-mentioned microparticles
  • the resin layer which the adhesive sheet of 1 aspect of this invention has has a space
  • the void portion (Z) includes voids that exist between the fine particles, and voids that exist in the secondary particles when the fine particles are secondary particles.
  • the resin portion (X) flows into the void portion (Z) even if the void portion (Z) exists immediately after the formation of the resin layer or immediately after the formation. In some cases, the voids disappear and the resin layer has no void portion (Z).
  • the resin layer included in the pressure-sensitive adhesive sheet according to one embodiment of the present invention has a concave portion on the surface (1). Therefore, it can be excellent in air bleeding and blister resistance.
  • the shear storage elastic modulus at 100 ° C. of the resin layer included in the pressure-sensitive adhesive sheet of one embodiment of the present invention is preferably 9.0 ⁇ 10 3 Pa or more from the viewpoint of improving the air release property and blister resistance of the pressure-sensitive adhesive sheet. More preferably, it is 1.0 ⁇ 10 4 Pa or more, and further preferably 2.0 ⁇ 10 4 Pa or more.
  • the shear storage modulus at 100 ° C. of the resin layer is measured by measuring at a frequency of 1 Hz using a viscoelasticity measuring device (for example, device name “DYNAMIC ANALYZER RDA II” manufactured by Rheometrics). Means the value.
  • the thickness of the resin layer is preferably 1 to 300 ⁇ m, more preferably 5 to 150 ⁇ m, and still more preferably 10 to 75 ⁇ m.
  • the adhesive force on the surface (1) of the resin layer of the pressure-sensitive adhesive sheet of one embodiment of the present invention is preferably 0.5 N / 25 mm or more, more preferably 2.0 N / 25 mm or more, more preferably 3.0 N / 25 mm or more. More preferably, it is 4.0 N / 25mm or more, More preferably, it is 7.0 N / 25mm or more.
  • the surface (2) of the resin layer also has adhesiveness, it is preferable that the adhesive force in the surface (2) also belongs to said range.
  • the value of the said adhesive force of an adhesive sheet means the value measured by the method as described in an Example.
  • the resin part (X) constituting the resin layer contains a resin as a main component.
  • the resin portion (X) is a portion containing components other than the fine particles contained in the resin layer, and is distinguished from the particle portion (Y) in that respect.
  • the resin part (X) contains a resin as a main component and may contain a crosslinking agent or a general-purpose additive in addition to the resin.
  • the elastic modulus at 23 ° C. of the resin portion (X) on the surface (1) is 1.0 ⁇ 10 3 to 8.0 ⁇ 10 8 Pa, preferably 1.0 ⁇ 10 6. 4 to 1.0 ⁇ 10 8 Pa, more preferably 5.0 ⁇ 10 4 to 1.0 ⁇ 10 7 Pa, still more preferably 1.0 ⁇ 10 5 to 1.0 ⁇ 10 6 Pa.
  • the elastic modulus of the resin portion (X) on the surface (1) is within the above range, the recess (Z1) is likely to appear when the release material (R1) is removed.
  • the resin portion (X) in the vicinity of the surface (1) is easily deformed moderately, an air pocket generated between the surface (1) and the adherend when the surface (1) is attached to the adherend. Due to this pressure, the recess (Z1) is easily deformed. As a result, the air reservoir can be removed to the outside through the recess (Z1) despite the relatively shallow recess (Z1).
  • the said elasticity modulus is less than 1.0 * 10 ⁇ 3 > Pa, when removing a peeling material (R1), it will become difficult to make a recessed part (Z1) appear.
  • the shape maintenance property of a recessed part (Z1) is inferior, it is difficult to remove an air pocket outside through a recessed part (Z1), and the air bleeding property of an adhesive sheet falls.
  • the elastic modulus exceeds 8.0 ⁇ 10 8 Pa, it is difficult to cause the recess (Z1) to appear when the release material (R1) is removed. Further, the recess (Z1) is not easily deformed to such an extent that the air pocket can be removed to the outside, and the air release property of the adhesive sheet is lowered.
  • the value of the elastic modulus at 23 ° C. of the resin portion (X) on the surface (1) is “J.Vac.Soc.Jpn. Vol.56, No.7, 2013 p258, Ken Nakajima It is a value measured according to the elastic modulus measurement method described in ⁇ Development of a method for quantitative evaluation of elastic modulus of soft materials using a force microscope '' and specifically means a value measured by the method described in the examples. To do.
  • the resin content in the resin part (X) is usually 40% by mass or more, preferably 50% by mass or more, more preferably 65% by mass or more, based on the total amount (100% by mass) of the resin part (X). More preferably, it is 75 mass% or more, More preferably, it is 85 mass% or more, More preferably, it is 90 mass% or more, Preferably it is 100 mass% or less, More preferably, it is 99.9 mass% or less.
  • the value of the content of the resin in the resin composition that is the material for forming the resin portion (X) can also be regarded as the “content of the resin in the resin portion (X)”.
  • the resin contained in the resin part (X) preferably contains a tacky resin from the viewpoint of developing tackiness on the surface (1) of the formed resin layer.
  • the resin layer is a multilayer in which the layer (X1), the layer (Y1), and the layer (X2) are laminated in this order from the release material (R1) side.
  • at least the layer (X1) preferably contains an adhesive resin.
  • the adhesive resin examples include acrylic resins, rubber resins, urethane resins, and silicone resins.
  • these adhesive resins the adhesive properties and weather resistance are good, and when the release material (R1) is removed, the surface (1) of the resin layer satisfies the above requirements (Ia) to (IIa).
  • the content of the adhesive resin selected from the acrylic resin and the rubber resin is preferably 25 to 100% by mass, more preferably relative to the total amount (100% by mass) of the resin contained in the resin portion (X). It is 50 to 100% by mass, more preferably 70 to 100% by mass, still more preferably 80 to 100% by mass, and still more preferably 100% by mass.
  • the resin portion (X) contains a resin having a functional group, It is more preferable to include an acrylic resin having a functional group.
  • the resin layer is a multilayer in which the layer (X1), the layer (Y1), and the layer (X2) are laminated in this order from the release material (R1) side.
  • at least the layer (Y1) preferably contains a resin having a functional group.
  • the functional group is a group that is a starting point of crosslinking with a crosslinking agent, and examples thereof include a hydroxy group, a carboxy group, an epoxy group, an amino group, a cyano group, a keto group, and an alkoxysilyl group. preferable.
  • resin part (X) contains a crosslinking agent further with resin which has the said functional group.
  • at least the layer (Y1) preferably contains a crosslinking agent together with the resin having the functional group.
  • the crosslinking agent include an isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent, and a metal chelate crosslinking agent.
  • isocyanate-based crosslinking agent examples include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate; alicyclic polyisocyanates such as isophorone diisocyanate and hydrogenated diphenylmethane diisocyanate;
  • epoxy-based crosslinking agent examples include ethylene glycol glycidyl ether, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, Examples include 1,6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, diglycidyl aniline, diglycidyl amine and the like.
  • aziridine-based crosslinking agent examples include diphenylmethane-4,4′-bis (1-aziridinecarboxamide), trimethylolpropane tri- ⁇ -aziridinylpropionate, tetramethylolmethanetri- ⁇ -aziridinyl.
  • Examples of the metal chelate crosslinking agent include chelate compounds whose metal atoms are aluminum, zirconium, titanium, zinc, iron, tin, and the like, and an aluminum chelate crosslinking agent is preferable.
  • Examples of the aluminum chelate-based crosslinking agent include diisopropoxy aluminum monooleyl acetoacetate, monoisopropoxy aluminum bis oleyl acetoacetate, monoisopropoxy aluminum monooleate monoethyl acetoacetate, diisopropoxy aluminum monolauryl acetoacetate, Examples include isopropoxyaluminum monostearyl acetoacetate and diisopropoxyaluminum monoisostearyl acetoacetate.
  • the resin portion (X) is composed of a metal chelate crosslinking agent and an epoxy crosslinking. It is preferable to include one or more selected from agents, more preferably to include a metal chelate crosslinking agent, and even more preferably to include an aluminum chelate crosslinking agent.
  • the content of the crosslinking agent is preferably 0.01 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, and still more preferably 0.3 to 7.0 parts with respect to 100 parts by mass of the resin having a functional group. Part by mass.
  • the resin portion (X) contains a metal chelate crosslinking agent and It is preferable that an epoxy type crosslinking agent is included together.
  • the content ratio of the metal chelate crosslinking agent and the epoxy crosslinking agent in the resin part (X) is preferably 10/90 to 99.5 / 0.5, more preferably 50/50 to 99.0 / 1.0, and still more preferably 65/35 by mass ratio. To 98.5 / 1.5, more preferably 75/25 to 98.0 / 2.0.
  • the resin part (X) may contain a general-purpose additive.
  • the general-purpose additive include tackifiers, antioxidants, softeners (plasticizers), rust inhibitors, pigments, dyes, retarders, reaction accelerators, ultraviolet absorbers, and the like. These general-purpose additives may be used alone or in combination of two or more.
  • the content of each general-purpose additive is preferably 0.0001 to 60 parts by mass, more preferably 0.001 to 100 parts by mass of the resin. 001 to 50 parts by mass.
  • the said resin contained in resin part (X) may be only 1 type, and may be used in combination of 2 or more type.
  • the material for forming the resin portion (X) of the resin layer of the pressure-sensitive adhesive sheet of the present invention is preferably a pressure-sensitive adhesive including a pressure-sensitive adhesive resin having a functional group, and an acrylic pressure-sensitive adhesive including an acrylic resin having a functional group. More preferably, it is a rubber-based pressure-sensitive adhesive containing an agent or a rubber-based resin.
  • an acrylic pressure-sensitive adhesive and a rubber-based pressure-sensitive adhesive that are suitable as the forming material of the resin portion (X) will be described.
  • the acrylic pressure-sensitive adhesive that is the material for forming the resin portion (X) may be either a solvent type or an emulsion type.
  • the acrylic pressure-sensitive adhesive preferably contains an acrylic resin (A) having a functional group (hereinafter also simply referred to as “acrylic resin (A)”) and a crosslinking agent (B).
  • acrylic resin (A) contained in the acrylic pressure-sensitive adhesive include a polymer having a structural unit derived from an alkyl (meth) acrylate having a linear or branched alkyl group and a cyclic structure ( Examples thereof include a polymer having a structural unit derived from (meth) acrylate.
  • the mass average molecular weight (Mw) of the acrylic resin (A) is preferably 50,000 to 1,500,000, more preferably 150,000 to 1,300,000, still more preferably 250,000 to 1,100,000, still more preferably 350,000 to 90,000. Ten thousand.
  • the acrylic resin (A) a structural unit (a1) derived from an alkyl (meth) acrylate (a1 ′) having an alkyl group having 1 to 18 carbon atoms (hereinafter also referred to as “monomer (a1 ′)”), And an acrylic copolymer (A1) having a structural unit (a2) derived from the functional group-containing monomer (a2 ′) (hereinafter also referred to as “monomer (a2 ′)”). More preferably, it is a combination (A1).
  • the content of the acrylic copolymer (A1) is preferably 50 to 100% by mass, more preferably 70 to 100%, based on the total amount (100% by mass) of the acrylic resin (A) in the acrylic adhesive.
  • the form of copolymerization of the acrylic copolymer (A1) is not particularly limited, and may be any of a block copolymer, a random copolymer, and a graft copolymer.
  • the number of carbon atoms of the alkyl group contained in the monomer (a1 ′) is more preferably 4 to 12, further preferably 4 to 8, and still more preferably 4 to 6, from the viewpoint of improving the adhesive property.
  • the monomer (a1 ′) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tridecyl ( Examples include meth) acrylate and stearyl (meth) acrylate. Among these, butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are preferable, and butyl (meth) acrylate is more preferable.
  • the content of the structural unit (a1) is preferably 50 to 99.5% by weight, more preferably 60 to 99% by weight, based on all the structural units (100% by weight) of the acrylic copolymer (A1). More preferably, it is 70 to 95% by mass, and still more preferably 80 to 93% by mass.
  • Examples of the monomer (a2 ′) include a hydroxy group-containing monomer, a carboxy group-containing monomer, an epoxy group-containing monomer, an amino group-containing monomer, a cyano group-containing monomer, a keto group-containing monomer, and an alkoxysilyl group-containing monomer. .
  • a carboxy group-containing monomer is more preferable.
  • Examples of the carboxy group-containing monomer include (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, and (meth) acrylic acid is preferred.
  • the content of the structural unit (a2) is preferably 0.5 to 50% by weight, more preferably 1 to 40% by weight, based on all the structural units (100% by weight) of the acrylic copolymer (A1). More preferably, it is 5 to 30% by mass, and still more preferably 7 to 20% by mass.
  • the acrylic copolymer (A1) may have a structural unit (a3) derived from another monomer (a3 ′) other than the monomers (a1 ′) and (a2 ′).
  • the other monomer (a3 ′) include cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and dicyclopentenyl.
  • Examples thereof include (meth) acrylate having a cyclic structure such as oxyethyl (meth) acrylate and imide (meth) acrylate, vinyl acetate, acrylonitrile, and styrene.
  • the content of the structural unit (a3) is preferably 0 to 30% by weight, more preferably 0 to 20% by weight, still more preferably based on the total structural unit (100% by weight) of the acrylic copolymer (A1). Is 0 to 10% by mass, more preferably 0 to 5% by mass.
  • the above monomers (a1 ′) to (a3 ′) may be used alone or in combination of two or more.
  • the method for synthesizing the acrylic copolymer (A1) component is not particularly limited.
  • the raw material monomer is dissolved in a solvent and solution polymerization is performed in the presence of a polymerization initiator, a chain transfer agent, or the like.
  • a polymerization initiator e.g., ethylene glycol dimethacrylate
  • a chain transfer agent e.g., ethylene glycol dimethacrylate
  • a dispersant emulsion polymerization in an aqueous system using raw material monomers.
  • crosslinking agent (B) contained in the acrylic pressure-sensitive adhesive examples include those described above. From the viewpoint of improving the pressure-sensitive adhesive properties, the surface of the resin layer (1) when the release material (R1) is removed. ) To make a plurality of recesses (Z1) satisfying the above requirements (Ia) to (IIa) easily appear, and a plurality of the resin layer surface (2) satisfying the above requirements (Ib) to (IIb) From the viewpoint of facilitating the formation of the recess (Z2), it is preferable to include one or more selected from a metal chelate crosslinking agent and an epoxy crosslinking agent, more preferably a metal chelate crosslinking agent, and an aluminum chelate system. More preferably, it contains a crosslinking agent.
  • the crosslinker (B) may be a metal chelate crosslinker. And an epoxy-based crosslinking agent are preferably included.
  • the content of the crosslinking agent (B) is preferably 0.01 to 15 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the acrylic resin (A) in the acrylic adhesive. More preferably, it is 0.3 to 7.0 parts by mass.
  • the content ratio of the metal chelate crosslinking agent and the epoxy crosslinking agent is preferably a mass ratio, preferably 10/90 to 99.5 / 0.5, more preferably 50/50 to 99.0 / 1.0, still more preferably 65/35 to 98.5 / 1.5, still more preferably 75/25 to 98.0 / 2.0.
  • the acrylic pressure-sensitive adhesive used in one embodiment of the present invention may contain a general-purpose additive as long as the effects of the present invention are not impaired.
  • Examples of the general-purpose additive include those described above, and the content of the general-purpose additive is also as described above.
  • a pressure-sensitive resin other than the acrylic resin (A) (for example, urethane-based resin, rubber-based resin, silicone-based resin, etc.) within a range that does not impair the effects of the present invention. ) May be contained.
  • the content of the acrylic resin (A) in the acrylic pressure-sensitive adhesive is preferably 50 to 100% by mass, more preferably 70%, based on the total amount (100% by mass) of the adhesive resin contained in the acrylic pressure-sensitive adhesive. To 100% by mass, more preferably 80 to 100% by mass, and still more preferably 100% by mass.
  • Rubber adhesive As a material for forming the resin part (X) of the present invention, a rubber-based pressure-sensitive adhesive containing a rubber-based resin may be used.
  • the rubber-based pressure-sensitive adhesive is suitable as a material for forming the resin portion (X) on the surface (1) side from the viewpoint of adjusting the elastic modulus of the resin portion (X) on the surface (1) of the resin layer to the above range. is there.
  • the rubber resin for example, synthetic rubber such as polyisobutylene resin and polybutene resin, or natural rubber can be used.
  • the weight average molecular weight of the rubber-based resin is preferably 20,000 or more, more preferably 30,000 to 1,000,000, and still more preferably, from the viewpoint of improving the adhesive strength and the wettability with respect to the adherend and the solubility with respect to the solvent. It is 50,000 to 800,000, more preferably 70,000 to 600,000.
  • the content of the rubber-based resin with respect to the total amount (100% by mass) of the rubber-based adhesive is preferably 30 to 100% by mass, more preferably 40 to 90% by mass, and still more preferably 45 from the viewpoint of improving the adhesive strength. It is ⁇ 80 mass%, more preferably 50 to 70 mass%.
  • the rubber-based adhesive may contain a tackifier resin and general-purpose additives (light stabilizer, antioxidant, ultraviolet absorber, resin stabilizer, pigment, extender, softener, etc.) together with the rubber resin. Good.
  • polyisobutylene resins are preferable.
  • the structure of the polyisobutylene resin is a resin having a polyisobutylene skeleton in the main chain or side chain, and specifically, a resin having the following structural unit (a).
  • polyisobutylene-based resin examples include polyisobutylene, which is a homopolymer of isobutylene, a copolymer of isobutylene and isoprene, a copolymer of isobutylene and n-butene, a copolymer of isobutylene and butadiene, and these copolymers And halogenated butyl rubber obtained by bromination or chlorination.
  • polyisobutylene resin is a copolymer
  • the structural unit derived from isobutylene shall be contained most among all the structural units.
  • the content of the structural unit derived from isobutylene in the polyisobutylene resin is preferably 80 to 100% by mass, more preferably 90 to 100% by mass with respect to all the structural units (100% by mass) of the polyisobutylene resin. %, More preferably 95 to 100% by mass, and still more preferably 100% by mass.
  • These polyisobutylene resins may be used alone or in combination of two or more.
  • the polyisobutylene resin used in one embodiment of the present invention includes a polyisobutylene resin ( ⁇ ) having a mass average molecular weight of 2.7 to 1,200,000 and a polyisobutylene resin ( ⁇ ) having a mass average molecular weight of 50,000 to 250,000. It is preferable to include both.
  • a high molecular weight polyisobutylene resin ( ⁇ ) in the rubber-based adhesive the durability and weather resistance of the resin layer formed from the rubber-based adhesive can be improved and the adhesive strength can be improved. it can.
  • the low molecular weight polyisobutylene resin ( ⁇ ) is well compatible with the PIB resin ( ⁇ ) in the rubber-based pressure-sensitive adhesive and plays a role in appropriately plasticizing the PIB resin ( ⁇ ).
  • the wettability with respect to the to-be-adhered body of the resin layer formed is improved, an adhesive physical property, a softness
  • Ruko you may use said polyisobutylene-type resin ((alpha)) and ((beta)) individually or in combination of 2 or more types, respectively.
  • the mass average molecular weight of the polyisobutylene resin ( ⁇ ) is preferably 270,000 to 1,200,000, more preferably 290,000 to 1,000,000, still more preferably 31 to 800,000, still more preferably 320,000 to 40,000. Ten thousand. If the mass average molecular weight is 270,000 or more, the cohesive force of the prepared pressure-sensitive adhesive can be sufficiently improved, and the concern about contamination of the adherend can be eliminated. On the other hand, if the mass average molecular weight is 1,200,000 or less, the cohesive force of the prepared pressure-sensitive adhesive becomes too high, and thus the adverse effect of flexibility and fluidity can be avoided, and a resin formed from the pressure-sensitive adhesive The wetting of the layer with the adherend can be improved. Moreover, when preparing an adhesive, the solubility with respect to a solvent can also be made favorable.
  • the mass average molecular weight of the polyisobutylene resin ( ⁇ ) is preferably 50,000 to 250,000, more preferably 80,000 to 230,000, still more preferably 140,000 to 220,000, and even more preferably 180,000 to 21. It is ten thousand. If the mass average molecular weight is 50,000 or more, the polyisobutylene resin ( ⁇ ) in the resin layer to be formed is separated as a low molecular component and can be prevented from being transferred to the adherend and contaminated. it can. Moreover, the outgas generation amount under high temperature can be reduced. On the other hand, when the mass average molecular weight is 250,000 or less, the polyisobutylene resin ( ⁇ ) can be sufficiently plasticized, and the wettability of the surface of the formed resin layer can be improved.
  • the content ratio of the polyisobutylene resin ( ⁇ ) to 100 parts by mass of the polyisobutylene resin ( ⁇ ) is preferably 5 to 55 parts by mass, more preferably 6 to 40 parts by mass, still more preferably 7 to 30 parts by mass, More preferably, it is 8 to 20 parts by mass.
  • the content of the polyisobutylene resin with respect to the total amount (100% by mass) of the rubber-based adhesive is preferably 30 to 90% by mass, more preferably 40 to 85% by mass, and still more preferably from the viewpoint of improving the adhesive strength. It is 45 to 80% by mass, and more preferably 50 to 70% by mass.
  • the rubber-based pressure-sensitive adhesive used in the present invention preferably further contains a tackifier resin from the viewpoint of improving the tackiness.
  • the tackifying resin can be mixed with a rubber-based resin, and has a function of improving the adhesive performance of the rubber-based resin, and has a mass average molecular weight of less than 20,000 (preferably 100 to 10,000). In the oligomer region.
  • tackifier resins include rosin resins, rosin phenol resins, and ester compounds thereof; hydrogenated rosin resins obtained by hydrogenating these rosin resins; terpene resins, terpene phenol resins, aromatic modified terpenes Terpene resins such as pentene resins; hydrogenated terpene resins obtained by hydrogenating these terpene resins; copolymerizing C5 fractions such as pentene, isoprene, piperine, and 1.3-pentadiene produced by thermal decomposition of petroleum naphtha.
  • C5 petroleum resin obtained and hydrogenated petroleum resin of this C5 petroleum resin C9 fractions such as indene, vinyltoluene, ⁇ -methylstyrene, ⁇ -methylstyrene, etc. produced by thermal decomposition of petroleum naphtha are copolymerized
  • a C9 petroleum resin obtained by hydrogenation and a hydrogenated petroleum resin of the C9 petroleum resin At least one selected from rosin resins, hydrogenated rosin resins, terpene resins, hydrogenated terpene resins, and hydrogenated petroleum resins is preferable, from the viewpoint of high compatibility with polyisobutylene resins, Hydrogenated petroleum resin is more preferable.
  • the softening point of the tackifying resin is preferably 60 to 170 ° C., more preferably 75 to 150 ° C., still more preferably 85 to 140 ° C., and still more preferably 90 to 130 ° C., from the viewpoint of improving the tackiness.
  • the value of the softening point of the tackifier resin is a value measured in accordance with JIS K2531.
  • the content of the tackifying resin is preferably 5 to 60% by mass, more preferably 10 to 50% by mass with respect to the total amount (100% by mass) of the rubber-based adhesive.
  • the particle portion (Y) constituting the resin layer is made of fine particles.
  • As the average particle size of the fine particles a plurality of materials satisfying the above requirements (Ia) to (IIa) on the surface (1) of the resin layer to be formed from the viewpoint of improving the air bleeding property and blister resistance of the pressure-sensitive adhesive sheet.
  • the thickness is 0.01 to 100 ⁇ m, more preferably 0.05 to 25 ⁇ m, still more preferably 0.1 to 10 ⁇ m.
  • the fine particles used in one embodiment of the present invention are not particularly limited, and include inorganic particles such as silica particles, metal oxide particles, barium sulfate, calcium carbonate, magnesium carbonate, glass beads, smectite, and organic particles such as acrylic beads. Can be mentioned. Among these fine particles, one or more selected from silica particles, metal oxide particles, and smectites are preferable, and silica particles are more preferable.
  • the silica particles used in one embodiment of the present invention may be either dry silica or wet silica.
  • the silica particles used in one embodiment of the present invention include organic modified silica surface-modified with an organic compound having a reactive functional group, inorganic modified silica surface-treated with an inorganic compound such as sodium aluminate or sodium hydroxide
  • organic-inorganic modified silica surface-treated with these organic compounds and inorganic compounds, organic-inorganic modified silica surface-treated with an organic-inorganic hybrid material such as a silane coupling agent, and the like may be used.
  • the mixture which consists of 2 or more types may be sufficient as these silica particles.
  • the mass concentration of silica in the silica particles is preferably 70 to 100% by mass, more preferably 85 to 100% by mass, and still more preferably 90 to 100% by mass with respect to the total amount (100% by mass) of the silica particles. .
  • the volume average secondary particle diameter of the silica particles used in one embodiment of the present invention is the above-mentioned on the surface (1) of the resin layer to be formed, from the viewpoint of improving the air bleeding property and blister resistance of the pressure-sensitive adhesive sheet.
  • the thickness is preferably 0.5 to 10 ⁇ m, more preferably 1 to 8 ⁇ m, and still more preferably 1.5 to 5 ⁇ m.
  • the value of the volume average secondary particle diameter of the silica particles is a value obtained by measuring the particle size distribution by a Coulter counter method using a multisizer three machine or the like.
  • metal oxide particles examples include particles made of metal oxide selected from titanium oxide, alumina, boehmite, chromium oxide, nickel oxide, copper oxide, titanium oxide, zirconium oxide, indium oxide, zinc oxide, and composite oxides thereof.
  • grains which consist of these metal oxides are also included.
  • smectite examples include montmorillonite, beidellite, hectorite, saponite, stevensite, nontronite, and soconite.
  • the mass retention after the resin layer of the pressure-sensitive adhesive sheet of one embodiment of the present invention is heated at 800 ° C. for 30 minutes is preferably 3 to 90% by mass, more preferably 5 to 80% by mass, and still more preferably 7 to 70%. % By mass, more preferably 9 to 60% by mass.
  • the mass retention rate can be regarded as indicating the content (% by mass) of fine particles contained in the resin layer. If the said mass retention is 3 mass% or more, it can become an adhesive sheet excellent in air bleeding property and blister resistance. Further, during the production of the pressure-sensitive adhesive sheet of the present invention, a plurality of recesses (Z1) satisfying the above requirements (Ia) to (IIa) are likely to appear or be formed on the surface (1) of the formed resin layer.
  • the resin layer has high film strength and can be a pressure-sensitive adhesive sheet having excellent water resistance and chemical resistance.
  • the method for producing the pressure-sensitive adhesive sheet of the present invention is not particularly limited, but a plurality of materials satisfying the above requirements (Ia) to (IIa) on the viewpoint of productivity and on the surface (1) of the resin layer to be formed. From the viewpoint of facilitating the appearance or formation of the recesses (Z1) and the formation of a plurality of recesses (Z2) satisfying the above requirements (Ib) to (IIb) on the surface (2). A method having the following steps (1) and (2) is preferred.
  • Step (1) On the release material (R1), a coating film (x ′) composed of a composition (x) containing a resin as a main component, and a coating composition (y) comprising 15% by mass or more of the fine particles.
  • Step of forming film (y ′) Step (2): Step of simultaneously drying coating film (x ′) and coating film (y ′) formed in step (1)
  • Step (1) comprises a coating film (x ′) comprising a composition (x) containing a resin as a main component on the release material (R1), and a composition (y) comprising 15% by mass or more of the fine particles.
  • This is a step of forming a coating film (y ′).
  • the composition (x) is a material for forming the resin part (X), and preferably contains a crosslinking agent together with the above-mentioned resin, and may further contain the above-mentioned general-purpose additives.
  • the composition (y) is a material for forming the particle portion (Y), but may further contain a resin, a crosslinking agent, and the above-mentioned general-purpose additives.
  • the composition (y) containing components such as these resins also serves as a material for forming the resin portion (X).
  • composition (x) examples of the resin contained in the composition (x) include resins constituting the above-described resin portion (X). Adhesive resins and resins having functional groups are preferable, and acrylic resins having the above-described functional groups ( One or more types selected from A) and rubber-based resins are more preferable, and one or more types selected from the above-mentioned acrylic copolymers (A1) and polyisobutylene-based resins are more preferable.
  • the content of the resin in the composition (x) is usually 40% by mass or more, preferably 50% by mass or more, based on the total amount of the composition (x) (100% by mass (excluding the dilution solvent)), More preferably 65% by mass or more, more preferably 75% by mass or more, further preferably 85% by mass or more, still more preferably 90% by mass or more, and preferably 100% by mass or less, more preferably 95% by mass. It is as follows.
  • a crosslinking agent contained in a composition (x) although the crosslinking agent contained in the above-mentioned resin part (X) is mentioned, a composition (x) is a metal chelate type crosslinking agent and an epoxy type crosslinking
  • the content ratio of the metal chelate crosslinking agent and the epoxy crosslinking agent in the composition (x) is preferably 10/90 to 99.5 / 0.5, more preferably 50/50 to 99.0 / 1.0, and still more preferably 65/35 to 98.5 by mass ratio. /1.5, more preferably 75/25 to 98.0 / 2.0.
  • the content of the crosslinking agent is preferably 0.01 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, and still more preferably 0.1 to 100 parts by mass of the resin contained in the composition (x). 3 to 7.0 parts by mass.
  • the composition (x) may be an acrylic pressure-sensitive adhesive containing the above-mentioned functional group-containing acrylic resin (A) and a crosslinking agent (B), or a rubber-based pressure-sensitive adhesive containing the above-mentioned rubber-based resin.
  • it is an acrylic pressure-sensitive adhesive containing the above-mentioned acrylic copolymer (A1) and a crosslinking agent (B), or a rubber-based pressure-sensitive adhesive containing the above-mentioned polyisobutylene resin.
  • the details of the acrylic pressure-sensitive adhesive and the rubber-based pressure-sensitive adhesive are as described above.
  • the composition (x) may contain the above-mentioned fine particles, but the content of the fine particles is less than 15% by mass and more than the content of the resin contained in the composition (x). Few.
  • the specific fine particle content is less than 15% by mass, preferably 0 to 13% by mass, based on the total amount of the composition (x) (100% by mass (excluding the dilution solvent)). More preferably, it is 0 to 10% by mass, still more preferably 0 to 5% by mass, and still more preferably 0% by mass.
  • composition (y) is a material for forming the particle portion (Y), and contains at least 15% by mass of the above-mentioned fine particles. From the viewpoint of fine particle dispersibility, the composition (y) preferably contains a resin together with the fine particles. It is more preferable to contain a crosslinking agent together with the resin. Moreover, the composition (y) may contain a general purpose additive. In addition, these resin, a crosslinking agent, and a general purpose additive become a forming material of resin part (X).
  • Examples of the fine particles contained in the composition (y) include those described above. From the viewpoint of forming a void portion (Z) in the resin layer and improving the blister resistance, silica particles are used. One or more selected from metal oxide particles and smectite are preferred.
  • the content of the fine particles in the composition (y) is such that the composition (y) is formed on the surface ( ⁇ ) of the resin layer from the viewpoint of facilitating the formation of an irregular recess formed by self-formation of the resin layer. Is 15% by mass or more, preferably 20 to 100% by mass, more preferably 25 to 90% by mass, and still more preferably 30 to 85%. The mass is more preferably 35 to 80% by mass.
  • composition (y) As resin contained in a composition (y), the same thing as resin contained in the above-mentioned composition (x) is mentioned, It is preferable that the same resin as composition (x) is included. In addition, you may use these resin individually or in combination of 2 or more types. Further, as a more specific resin contained in the composition (y), a resin having a functional group is preferable, an acrylic resin (A) having the above-described functional group is more preferable, and the above-mentioned acrylic copolymer (A1) is more preferable.
  • the content of the resin in the composition (y) is usually 1 to 85% by mass, preferably 5 to 80% by mass with respect to the total amount of the composition (y) (100% by mass (excluding the diluting solvent)). %, More preferably 10 to 75% by mass, still more preferably 20 to 70% by mass, and still more preferably 25 to 65% by mass.
  • a crosslinking agent contained in a composition (y) although the crosslinking agent contained in the above-mentioned resin part (X) is mentioned, a composition (y) is a metal chelate type crosslinking agent and an epoxy-type crosslinking. It is preferable that 1 or more types chosen from an agent are included, and it is more preferable that a metal chelate type crosslinking agent is included. Furthermore, the composition (y) preferably contains both a metal chelate crosslinking agent and an epoxy crosslinking agent.
  • composition (y) contains both a metal chelate type crosslinking agent and an epoxy type crosslinking agent
  • suitable content ratio (mass ratio) of the metal chelate type crosslinking agent and epoxy type crosslinking agent in composition (y) Is the same as that of the above-mentioned composition (x).
  • the content of the cross-linking agent is preferably 0.01 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, and still more preferably 0.1 to 100 parts by mass of the resin contained in the composition (y). 3 to 7.0 parts by mass.
  • organic solvent examples include toluene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, isopropyl alcohol, t-butanol, s-butanol, acetylacetone, cyclohexanone, n-hexane, and cyclohexane. . These solvents may be used alone or in combination of two or more.
  • the order of laminating the coating films (x ′) and (y ′) formed on the release material (R1) in this step is not particularly limited, but the coating film (y ′) and the coating film are applied on the release material (R1).
  • the film (x ′) is preferably formed so as to be laminated in this order.
  • the coating film (x ′) may be sequentially formed on the coating film (y ′). Further, from the viewpoint of productivity, a method of simultaneously forming the coating film (y ′) and the coating film (x ′) with a multilayer coater may be used.
  • Examples of the coater used for sequential formation include spin coater, spray coater, bar coater, knife coater, roll coater, knife roll coater, blade coater, gravure coater, curtain coater, and die coater.
  • Examples of the coater used for simultaneous application with a multilayer coater include a curtain coater and a die coater. Among these, a die coater is preferable from the viewpoint of operability.
  • the coating film You may perform the predrying process of the grade which does not advance hardening reaction.
  • the drying temperature at the time of performing the pre-drying treatment is usually appropriately set within a temperature range in which the formed coating film does not proceed, but preferably in step (2). Is lower than the drying temperature.
  • the specific drying temperature indicated by the phrase “below the drying temperature in step (2)” is preferably 10 to 45 ° C., more preferably 10 to 34 ° C., and further preferably 15 to 30 ° C.
  • Step (2) is a step of simultaneously drying the coating film (x ′) and the coating film (y ′) formed on the release material (R1) in the step (1).
  • Step (2) by simultaneously drying the formed coating film (x ′) and coating film (y ′), a resin layer containing the resin part (X) and the particle part (Y) is formed, and A plurality of recesses (Z2) are formed on the surface (2) of the resin layer.
  • the plurality of recesses (Z2) are formed, the plurality of recesses (Z1) are likely to appear on the surface (1) of the resin layer when the release material (R1) is removed.
  • a viewpoint of easily forming a plurality of recesses (Z2) satisfying the above requirements (Ib) to (IIb) on the surface (2) of the resin layer to be formed, and a release material From the viewpoint of facilitating the appearance of a plurality of recesses (Z1) on the surface (1) of the resin layer when R1) is removed, it is preferably 35 to 200 ° C, more preferably 60 to 180 ° C, still more preferably It is 70 to 160 ° C., more preferably 80 to 140 ° C. When the drying temperature is 35 ° C. or higher, a plurality of recesses (Z2) are easily formed on the surface (2).
  • the release material (R1) when the release material (R1) is removed, the surface (1) of the resin layer is removed. In addition, a plurality of recesses (Z1) are likely to appear.
  • the said drying temperature is 200 degrees C or less, the malfunction that the base material and peeling material which an adhesive sheet has shrink
  • a void portion (Z) can be formed around the particle portion (Y) of the resin layer formed by this step.
  • the void portion (Z) can be easily formed by using at least one selected from silica particles, metal oxide particles, and smectite as the fine particles contained in the composition (y).
  • the first of the present invention as shown in FIG. 1 (a) or (b) is obtained.
  • An adhesive sheet is obtained.
  • the release material (R1) of the first pressure-sensitive adhesive sheet of the present invention is removed, a plurality of the above-described recesses (Z1) appear on the surface (1) of the resin layer. Therefore, by removing the release material (R1) of the first pressure-sensitive adhesive sheet of the present invention and causing a plurality of recesses (Z1) to appear, by laminating the release material on the surface (1) of the resin layer again, The 2nd adhesive sheet of this invention as shown in Drawing 2 (a) or (b) can be manufactured.
  • the removed release material may be used again, or a separate release material may be used.
  • the following first and second modes are used.
  • a production method is preferred.
  • composition (x1) or (x2) containing a resin as a main component is the same as the above-described composition (x), and the composition The details of each component contained in the product (x1) or (x2) (type of component, suitable component, component content, etc.) are also the same.
  • composition (y) containing 15% by mass or more of fine particles is also as described above.
  • the manufacturing method of the first aspect includes at least the following steps (1A) and (2A).
  • the composition (x1), the composition (y), and the composition (x2) are mixed with the above-described solvent to form a solution of the composition and then applied.
  • the composition (x) that is a forming material on the surface (1) side of the resin layer is It is preferable to use a rubber-based adhesive containing a rubber-based resin.
  • a coating film (x1 '), a coating film (y'), and a coating film (x2 ') after forming a coating film (x1') on a peeling material (R1), a coating film (x1 A method of sequentially forming using the above coater, such as forming a coating film (y ') on the coating film (y) and forming a coating film (x2') on the coating film (y '), may be used.
  • the film (x1 ′), the coating film (y ′), and the coating film (x2 ′) may be formed by simultaneous application using the multilayer coater described above.
  • step (1A) after forming one or more coating films (x1 ′), coating film (y ′), and coating film (x2 ′), before moving to step (2A), You may perform the predrying process of the grade which the hardening reaction of the said coating film does not advance. For example, after each of the coating film (x1 ′), the coating film (y ′), and the coating film (x2 ′) is formed, the above pre-drying treatment may be performed each time. ) And the coating film (y ′), and after the above pre-drying treatment, the coating film (x2 ′) may be formed.
  • the drying temperature at the time of performing the pre-drying treatment is usually appropriately set in a temperature range in which the formed coating film does not cure, but preferably in step (2A). Is lower than the drying temperature.
  • the specific drying temperature indicated by the phrase “below the drying temperature in step (2A)” is preferably 10 to 45 ° C., more preferably 10 to 34 ° C., and further preferably 15 to 30 ° C.
  • the step (2A) is a step of simultaneously drying the coating film (x1 ′), the coating film (y ′), and the coating film (x2 ′) formed in the step (1A).
  • the range is the same as in step (2) above.
  • a resin layer including the resin portion (X) and the particle portion (Y) is formed.
  • a 1st adhesive sheet is obtained. Moreover, after removing the release material (R1) of the first pressure-sensitive adhesive sheet of the present invention and causing a plurality of recesses (Z1) to appear, by laminating the release material on the surface (1) of the resin layer again, The 2nd adhesive sheet of this invention as shown in Drawing 2 (a) or (b) can be manufactured.
  • Step (1B) A coating film comprising a composition (y) containing 15% by mass or more of the fine particles on a layer (X1) mainly containing the resin portion (X) provided on the release material (R1).
  • the “layer (X1) mainly including the resin portion (X)” is formed by drying the coating film (x1 ′) made of the composition (x1) including the resin as the main component. be able to. Since the layer (X1) is formed from the composition (x1), the layer (X1) may contain a crosslinking agent, a general-purpose additive and the like in addition to the resin. The content of the resin portion (X) in the layer (X1) is as described above.
  • the composition (x) that is a forming material on the surface (1) side of the resin layer is It is preferable to use a rubber-based adhesive containing a rubber-based resin.
  • a coating film (x1 ′) made of a composition (x1) containing a resin as a main component is formed on the release material (R1), and the coating film (x1 ′) is dried.
  • the drying temperature at this time is not particularly limited, and is preferably 35 to 200 ° C, more preferably 60 to 180 ° C, still more preferably 70 to 160 ° C, and still more preferably 80 to 140 ° C.
  • the coating film (y ′) and the coating film (x2 ′) are formed in this order on the layer (X1) obtained after drying, not on the coating film (x1 ′). This is different from the first aspect described above. Also in the step (1B), it is preferable that the composition (y) and the composition (x2) are mixed with the above-mentioned solvent to form a solution of the composition and then applied.
  • the coating film (y ′) and the coating film (x2 ′) after forming the coating film (y ′) on the layer (X1), the coating film (x2 ′) is formed on the coating film (y ′).
  • the drying temperature at the time of performing the pre-drying treatment is usually appropriately set within a temperature range in which the formed coating film does not cure, but preferably in step (2B). Is lower than the drying temperature.
  • the specific drying temperature indicated by the phrase “below the drying temperature in step (2B)” is preferably 10 to 45 ° C., more preferably 10 to 34 ° C., and further preferably 15 to 30 ° C.
  • the step (2B) is a step of simultaneously drying the coating film (y ′) and the coating film (x2 ′) formed in the step (1B).
  • the preferred range of the drying temperature in this step is the above-described step (2). ).
  • a resin layer including the resin portion (X) and the particle portion (Y) is formed.
  • a 1st adhesive sheet is obtained. Moreover, after removing the release material (R1) of the first pressure-sensitive adhesive sheet of the present invention and causing a plurality of recesses (Z1) to appear, by laminating the release material on the surface (1) of the resin layer again, The 2nd adhesive sheet of this invention as shown in Drawing 2 (a) or (b) can be manufactured.
  • a resin layer containing a resin part (X) containing a resin as a main component and a particle part (Y) made of fine particles, and a substrate or a release material ( R2) and at least the surface (1) of the resin layer on the side provided with the release material (R1) is an adhesive sheet having adhesiveness
  • a maximum height difference of 100 nm or more in a region (P1) surrounded by a 5 mm square arbitrarily selected on the surface (1) of the exposed resin layer A plurality of recesses (Z1) having In a region (P2) surrounded by a square with a side of 5 mm arbitrarily selected on the surface (2) of the resin layer on the side where the substrate or release material (R2) is provided, 0.5 ⁇ m or more
  • a resin layer containing a resin part (X) containing a resin as a main component and a particle part (Y) made of fine particles on a release material (R1), and a substrate or a release material ( R2) and at least the surface (1) of the resin layer on the side provided with the release material (R1) is an adhesive sheet having adhesiveness, The elastic modulus at 23 ° C.
  • a maximum height difference of 100 nm or more in a region (P1) surrounded by a 5 mm square arbitrarily selected on the surface (1) of the exposed resin layer A plurality of recesses (Z1) having In a region (P2) surrounded by a square with a side of 5 mm arbitrarily selected on the surface (2) of the resin layer on the side where the substrate or release material (R2) is provided, 0.5 ⁇ m or more
  • a resin layer (X) containing a resin as a main component and a particle portion (Y) made of fine particles, and a base material or release material ( R2) and at least the surface (1) of the resin layer on the side provided with the release material (R1) is an adhesive sheet having adhesiveness, The elastic modulus at 23 ° C.
  • a resin layer (X) containing a resin as a main component and a particle portion (Y) made of fine particles, and a base material or release material ( R2) and at least the surface (1) of the resin layer on the side provided with the release material (R1) is an adhesive sheet having adhesiveness, The elastic modulus at 23 ° C.
  • a maximum height difference of 100 nm or more in a region (P1) surrounded by a 5 mm square arbitrarily selected on the surface (1) of the exposed resin layer A plurality of recesses (Z1) having a shape, the shape of the pasting surface on the surface (1) exposed of the resin layer is indefinite, In a region (P2) surrounded by a square with a side of 5 mm arbitrarily selected on the surface (2) of the resin layer on the side where the substrate or release material (R2) is provided, 0.5 ⁇ m or more
  • a pressure-sensitive adhesive sheet (4A) having a plurality of concave portions (Z2) having a maximum height difference In a region (P2) surrounded by a square with a side of 5 mm arbitrarily selected on the surface (2) of the resin layer on the side where the substrate or release material (R2) is provided, 0.5 ⁇ m or more
  • a pressure-sensitive adhesive sheet (4A) having a plurality of concave portions (Z2) having a maximum height difference When the release material (R1) is removed
  • a resin layer (X) containing a resin as a main component and a particle portion (Y) made of fine particles, and a base material or release material ( R2) and at least the surface (1) of the resin layer on the side provided with the release material (R1) is an adhesive sheet having adhesiveness, The elastic modulus at 23 ° C.
  • a plurality of recesses (Z1) having a length of one or more of the recesses (Z1) appearing in the region (P1) extend to any side of a square having a side of 5 mm, which is a boundary line of the region (P1).
  • Examples of another embodiment of the second pressure-sensitive adhesive sheet of the present invention include pressure-sensitive adhesive sheets (1B) to (5B) shown in the following [1B] to [5B]. Details of the constituent elements of the pressure-sensitive adhesive sheets (1B) to (5B) are as described above.
  • a resin layer containing a resin part (X) containing a resin as a main component and a particle part (Y) made of fine particles on a release material (R1), and a substrate or a release material ( R2) and at least the surface (1) of the resin layer on the side provided with the release material (R1) is an adhesive sheet having adhesiveness
  • a resin layer containing a resin part (X) containing a resin as a main component and a particle part (Y) made of fine particles on the release material (R1), and a substrate or release material ( R2) and at least the surface (1) of the resin layer on the side provided with the release material (R1) is an adhesive sheet having adhesiveness, The elastic modulus at 23 ° C.
  • a resin layer containing a resin part (X) containing a resin as a main component and a particle part (Y) made of fine particles on a release material (R1), and a substrate or a release material ( R2) and at least the surface (1) of the resin layer on the side provided with the release material (R1) is an adhesive sheet having adhesiveness, The elastic modulus at 23 ° C.
  • a resin layer (X) containing a resin as a main component and a particle portion (Y) made of fine particles, and a substrate or release material ( R2) and at least the surface (1) of the resin layer on the side provided with the release material (R1) is an adhesive sheet having adhesiveness, The elastic modulus at 23 ° C.
  • There are a plurality of (Z1) and the shape of the sticking surface on the exposed surface (1) of the resin layer is indefinite,
  • a region (P2) surrounded by a square with a side of 5 mm arbitrarily selected on the surface (2) of the resin layer on the side where the substrate or release material (R2) is provided 0.5 ⁇ m or more
  • a resin layer (X) containing a resin as a main component and a particle portion (Y) made of fine particles, and a substrate or release material ( R2) and at least the surface (1) of the resin layer on the side provided with the release material (R1) is an adhesive sheet having adhesiveness, The elastic modulus at 23 ° C.
  • volume average secondary particle diameter of silica particles was determined by measuring the particle size distribution by a Coulter counter method using a multisizer three machine (manufactured by Beckman Coulter, Inc.).
  • the thickness of the resin layer was measured by observing the cross section of the resin layer of the target pressure-sensitive adhesive sheet using a scanning electron microscope (manufactured by Hitachi, Ltd., product name “S-4700”).
  • Production Example y-1 ⁇ 2 (Preparation of coating solutions (y-1) to (y-2) for forming a coating film (y ′))
  • the fine particle dispersion (y-0) prepared in Production Example y-0 in the blending amount (solid content) shown in Table 1, the above-mentioned acrylic resin (i) solution, and an aluminum chelate-based crosslinking agent (product name “M” ⁇ 5A ”, manufactured by Soken Chemical Co., Ltd., solid content concentration: 4.95% by mass), and a dilution solvent of the type shown in Table 1 is added, and the solid content concentration and fine particle concentration shown in Table 1 are added.
  • Coating solutions (y-1) to (y-2) for forming a film (y ′) were prepared.
  • IPA isopropyl alcohol
  • CHN cyclohexanone
  • Examples 1 to 5 Formation of coating film As release material (R1), a release film (product name “SP-PET381031” manufactured by Lintec Corporation, thickness 38 ⁇ m, a silicone release agent layer provided on one side of a polyethylene terephthalate (PET) film) was used. On the release agent layer of the release film, using an applicator, the resin composition solution (x-1) or (x-2) prepared in Production Example x-1 or x-2 of the type shown in Table 2 is used. Then, the coating film (x1 ′) was formed by coating so that the thickness of the coating film after coating (thickness of the coating film in a non-dried state) was the thickness shown in Table 2.
  • a release film product name “SP-PET381031” manufactured by Lintec Corporation, thickness 38 ⁇ m, a silicone release agent layer provided on one side of a polyethylene terephthalate (PET) film
  • PET polyethylene terephthalate
  • the coating solution (y-1) for forming the coating film (y ′) prepared in Production Example y-1 is overcoated.
  • the film (x1 ′) and the coating film (y ′) were applied so that the total thickness of the two layers (the total thickness of the two layers in the non-dried state) was the thickness shown in Table 2, and the coating film (y ') Formed.
  • the resin composition solution (x-1) prepared in Production Example x-1 was overcoated with the coating film (x1 ′)
  • the coating film (y ′) and the coating film (x2 ′) were applied so that the total thickness of the three layers (the total thickness of the three layers in the non-dried state) was the thickness shown in Table 2.
  • x2 ′) was formed.
  • (2) Drying treatment Thereafter, the three-layer coating film (x1 ′), coating film (y ′), and coating film (x2 ′) were simultaneously dried at a drying temperature of 100 ° C.
  • Example 6 Formation of layer (X1) As a release material (R1), a release film (product name “SP-PET381031” manufactured by Lintec Corporation, thickness 38 ⁇ m, with a silicone release agent layer on one side of a PET film) ) was used. The thickness of the coating film after application of the resin composition solution (x-1) prepared in Production Example x-1 using an applicator on the release agent layer of the release film (the coating film in a non-dried state) The film was applied so that the thickness was 25 ⁇ m, and a coating film (x1 ′) was formed. And it was made to dry for 2 minutes at the drying temperature of 100 degreeC, and the layer (X1) containing the resin part (X) was formed.
  • a release film product name “SP-PET381031” manufactured by Lintec Corporation, thickness 38 ⁇ m, with a silicone release agent layer on one side of a PET film
  • the resin composition solution (x-1) prepared in Production Example x-1 is applied onto the formed coating film (y ′) using the coating film (x1 ′) and the coating film before drying.
  • (Y ′) and the coating film (x2 ′) were applied so that the total thickness (total thickness of the three layers in the non-dried state) of the three layers was the thickness shown in Table 2, and the coating film (x2 ′ ) Was formed.
  • (3) Drying treatment Thereafter, the two-layer coating films (y ′) and (x2 ′) are simultaneously dried at a drying temperature of 100 ° C. for 2 minutes to obtain a resin part (X) and a particle part (Y).
  • Example 1 Comparative Example 1 In Example 1, the coating film (y ′) and the coating film (x2 ′) were not formed, and a knife coater was used on the release agent layer of the above-described release film used as the release material (R1). The solution (x-1) of the resin composition prepared in -1 was applied so that the film thickness after drying was 25 ⁇ m, and a coating film (x1 ′) was formed in the same manner as in Example 1. Then, a pressure-sensitive adhesive sheet with a base material having a resin layer having a thickness of 25 ⁇ m and consisting only of the resin portion (X) was produced.
  • Comparative Example 2 (1) Formation of a resin layer As a release material (R1), a release film (product name “SP-PET381031” manufactured by Lintec Corporation, thickness 38 ⁇ m, a silicone release agent layer is provided on one side of a polyethylene terephthalate (PET) film) was used. On the release agent layer of the release film, using an applicator, the resin composition solution (x-1) prepared in Production Example x-1 was applied to form a coating film (x1 ′). And dried for 2 minutes to form a layer (X1) having a thickness of 5 ⁇ m including the resin portion (X).
  • a release material a release film (product name “SP-PET381031” manufactured by Lintec Corporation, thickness 38 ⁇ m, a silicone release agent layer is provided on one side of a polyethylene terephthalate (PET) film) was used.
  • the resin composition solution (x-1) prepared in Production Example x-1 was applied to form a coating film (x1 ′). And dried for 2 minutes to form
  • the coating solution (y-1) for forming the coating film (y ′) prepared in Production Example y-1 was applied onto the release agent layer of the same type of release film as described above using an applicator. After forming the coating film (y ′), it was dried at 100 ° C. for 2 minutes to form a layer (Y1) having a thickness of 15 ⁇ m including the resin part (X) and the particle part (Y). Further, separately from the above, the resin composition solution (x-1) prepared in Production Example x-1 was applied onto the release agent layer of the same type of release film as described above by using an applicator. After forming x2 ′), the film was dried at 100 ° C.
  • a layer (X2) having a thickness of 5 ⁇ m including the resin portion (X) is laminated so that the surface of the layer (X1) formed on the peeling material (R1) and the surface which the layer (Y1) formed as mentioned above exposed may be bonded.
  • the release film on the layer (Y1) was removed, and the surface of the exposed layer (Y1) was laminated to the exposed surface of the layer (X2) formed as described above.
  • the layer (X1), the layer (Y1), and the layer (X2) are laminated in this order on the release material (R1), and the resin part (X) and the particle part (Y) are included.
  • a resin layer having a thickness of 25 ⁇ m was formed.
  • Examples 7-8 Formation of a coating film As a release material (R1), a release film (product name “SP-PET 381031”, thickness 38 ⁇ m, provided with a silicone release agent layer on one side of a PET film) manufactured by Lintec Corporation) Using. On the release agent layer of the release film, the resin composition solution (x-3) prepared in Production Example x-3 and the coating solution (y ′) forming coating solution (y) prepared in Production Example y-2 -2) and the resin composition solution (x-3) prepared in Production Example x-3 at the same time using a multilayer die coater (width: 250 mm) in this order at the flow rates and coating speeds shown in Table 3.
  • Example 9 Formation of layer (X1) As a release material (R1), a release film (product name “SP-PET381031” manufactured by Lintec Corporation, thickness 38 ⁇ m, with a silicone release agent layer on one side of a PET film) ) was used. On the release agent layer of the release film, the resin composition solution (x-1) prepared in Production Example x-1 was applied using an applicator to form a coating film (x1 ′). And it was made to dry for 2 minutes at the drying temperature of 100 degreeC, and the 8 micrometer-thick layer (X1) containing the resin part (X) was formed.
  • a release film product name “SP-PET381031” manufactured by Lintec Corporation, thickness 38 ⁇ m, with a silicone release agent layer on one side of a PET film
  • the coating film (y ') prepared in Production Example y-1 was formed on the surface of the layer (X1) exposed by peeling off the release film previously laminated of the above laminate.
  • the coating solution (y-1) for coating and the solution (x-1) of the resin composition prepared in Production Example x-1 were formed in this order at the flow rate and coating speed shown in Table 3 in this order.
  • a scanning probe microscope manufactured by Shimadzu Corporation, product name “SPM-9700”
  • a cantilever manufactured by TEAM NANOTEC, product name “LRCH 250”, spring constant: 0.3 N / m, thermal fluctuation
  • Measured value by the method 0.24 N / m, probe tip radius 300 nm
  • the force curve measurement the relationship between the amount of warpage of the cantilever and the amount of displacement of the piezo scanner when the cantilever is pushed into the resin portion (X) and when it is pulled away can be obtained.
  • the obtained force curve is converted into the relationship between the load (F) and the sample deformation amount ( ⁇ ) as an F- ⁇ curve, and this F- ⁇ curve is the Johnson-Kendall-Roberts (JKR) two-point method.
  • JKR Johnson-Kendall-Roberts
  • the elastic modulus E of the sample can be obtained by the following equation from two points of an equilibrium point (point A) and an adhesion point (point B) in the separation process. If the coordinates of A and B are defined as A ( ⁇ 0 , 0) and B ( ⁇ 1 , F 1 ), respectively, the elastic modulus E can be calculated from the following equation.
  • ⁇ is the Poisson's ratio of the sample, and is 0.5 in this embodiment.
  • R is the radius of curvature of the tip of the cantilever probe, and is 300 nm in this embodiment.
  • Requirement (Ib) There are a plurality of concave portions (Z2) having a maximum height difference of 0.5 ⁇ m or more in a region (P2) surrounded by a square of 5 mm on an arbitrarily selected side on the surface (2).
  • the number of recesses (Z2) having different shapes is 95% or more (100%) with respect to the total number (100%), that is, all the recesses (Z2) in the region (P2) have different shapes.
  • B Although the shape of the sticking part with the smooth surface of the translucent adherend on the surface (1) can be visually confirmed, the shape of the sticking part is not indefinite.
  • C The shape of the pasting part with the smooth surface of the translucent adherend on the surface (1) cannot be visually confirmed.
  • Air escape characteristics> A pressure-sensitive adhesive sheet with a base material having a size of 50 mm long ⁇ 50 mm wide was affixed to a melamine coating plate as an adherend so that air retention occurred. And the presence or absence of the air pocket after crimping
  • Adhesive sheet with base material measuring 50 mm long ⁇ 50 mm wide is affixed to a polymethyl methacrylate plate (product name “Acrylite L001”, manufactured by Mitsubishi Rayon Co., Ltd.) 70 mm long ⁇ 150 mm wide ⁇ 2 mm thick.
  • a test sample was prepared by pressure bonding using This test sample was allowed to stand at 23 ° C. for 12 hours, then left in an 80 ° C. hot air dryer for 1.5 hours, and further left in a 90 ° C. hot air dryer for 1.5 hours, after heating was promoted.
  • the blister generation state was visually observed, and the blister resistance of each pressure-sensitive adhesive sheet was evaluated according to the following criteria.
  • B A blister was partially confirmed.
  • C Blister was confirmed on the entire surface.
  • the pressure-sensitive adhesive sheets produced in Examples 1 to 9 had a plurality of recesses (Z1) satisfying the requirements (Ia) to (IIa) on the surface (1), and the surface (2 It was confirmed that there were a plurality of recesses (Z2) satisfying the above requirements (Ib) to (IIIb), and all of air bleedability, blister resistance and adhesive strength were good.
  • the release material (R1) was removed, and the region (P1) on the surface (1) of the exposed resin layer was subjected to the above scanning electron microscope ( When observed with a magnification of 30 times, it was confirmed that a plurality of recesses (Z1) appeared irregularly and existed, and the shape of the pasting surface in the region (P1) on the surface (1) was It was irregular.
  • the release material (R1) was removed, and the recesses (Z1 that appeared in the region (P1) on the surface (1) of the exposed resin layer ) Extend to one side of a 5 mm square that is the boundary line of the region (P1), and is surrounded by a 5 mm square adjacent to the region (P1). It was confirmed to have a shape extending continuously into the region (P1 ′).
  • FIG. 7 and 8 are images when observed with a scanning electron microscope after removing the release material (R1) of the pressure-sensitive adhesive sheet produced in Example 1.
  • FIG. FIG. 7A is a cross-sectional image near the surface (1) side of the resin layer of the pressure-sensitive adhesive sheet
  • FIG. 7B is a perspective image of the surface (1) of the resin layer of the pressure-sensitive adhesive sheet.
  • Fig.8 (a) is a perspective image of the surface (1) seen from the side surface side of the resin layer of the said adhesive sheet
  • FIG.8 (b) is an enlarged image of Fig.8 (a).
  • FIG. 9A is a cross-sectional image in the vicinity of the surface (2) side of the resin layer of the pressure-sensitive adhesive sheet produced in Example 1
  • FIG. 9B is the surface (2) of the resin layer of the pressure-sensitive adhesive sheet.
  • the length of 20.0 ⁇ m is shown for the 10 scales shown in the lower right of the image
  • the length of FIG. 9B is shown in the lower right of the image.
  • the length of 500 ⁇ m is indicated by 10 divisions.
  • a plurality of concave portions are formed on the surface (2) of the resin layer of the pressure-sensitive adhesive sheet produced in Example 1.
  • the image in FIG. 9 is obtained by photographing before laminating the base material on the surface (2) of the resin layer (before the back surface treatment) in order to confirm the presence of the recess on the surface (2) of the resin layer. It is a thing.
  • FIG. 10 is an image of the pressure-sensitive adhesive sheet produced in Example 8 when observed with a scanning electron microscope after removing the release agent (R1)
  • FIG. 10 (a) is a resin layer of the pressure-sensitive adhesive sheet
  • FIG. 10B is a perspective image of the surface (2) of the resin layer of the pressure-sensitive adhesive sheet.
  • the length of 1.00 mm is shown for the 10 scales described in the lower right in the said image.
  • a plurality of recesses appeared and existed. It can be seen that a plurality of recesses are also formed on the surface (2).
  • FIG. 10B in order to confirm the presence of the concave portion on the surface (2) of the resin layer, before laminating the base material on the surface (2) of the resin layer (before the back surface treatment). It was obtained by shooting.
  • FIG. 11 is an image when the pressure-sensitive adhesive sheet produced in Comparative Example 1 is observed with a scanning electron microscope, where (a) is a cross-sectional image of the pressure-sensitive adhesive sheet, and (b) is the surface of the resin layer of the pressure-sensitive adhesive sheet. It is a perspective image of (1). In the image of FIG. 11 (a), the length of 20.0 ⁇ m is shown on the 10 scales shown in the lower right in the image, and in the image of FIG.
  • the pressure-sensitive adhesive sheet of one embodiment of the present invention is useful as a pressure-sensitive adhesive sheet having a large affixing area used for identification or decoration, for coating masking, for surface protection of metal plates and the like.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne une feuille adhésive qui a, sur un matériau détachable (R1), une couche de résine qui comprend une partie résine (X) et une partie particules (Y) et qui a un substrat ou un matériau détachable (R2). Au moins une surface (1) de la couche de résine qui est du côté pourvu du matériau détachable (R1) a des propriétés adhésives. Le module élastique de la partie résine (X) de la surface (1) à 23 °C est dans une plage prescrite. Lorsque le matériau détachable (R1) est retiré, la surface exposée (1) de la couche de résine a une différence de hauteur maximale supérieure ou égale à 100 nm à l'intérieur d'une région donnée arbitrairement choisie, sur 95 % ou plus de laquelle apparaissent une pluralité de parties en creux (Z1) qui ont des formes différentes les une des autres. Une surface (2) de la couche de résine qui est du côté pourvu du substrat ou du matériau détachable (R2) a une différence de hauteur maximale supérieure ou égale à 0,5 μm à l'intérieur d'une région donnée arbitrairement choisie, sur 95 % de laquelle sont présentes une pluralité de parties en creux (Z2) qui ont des formes différentes les unes des autres. La feuille adhésive a d'excellentes propriétés de libération d'air et a des caractéristiques adhésives et une résistance au cloquage avantageuses.
PCT/JP2015/060445 2014-04-02 2015-04-02 Feuille adhésive et procédé de production de feuille adhésive WO2015152365A1 (fr)

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JP2017119396A (ja) * 2015-12-28 2017-07-06 住友化学株式会社 樹脂フィルム付光学部材の製造方法
WO2018101335A1 (fr) * 2016-11-30 2018-06-07 リンテック株式会社 Feuille adhésive double face et procédé de production de feuille adhésive double face
JP2020142530A (ja) * 2020-05-15 2020-09-10 住友化学株式会社 樹脂フィルム付光学部材の製造方法

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JP2008150431A (ja) * 2006-12-14 2008-07-03 Lintec Corp 粘着シート及び粘着シートの製造方法
WO2009048176A1 (fr) * 2007-10-12 2009-04-16 Lintec Corporation Feuille adhésive sensible à la pression et son procédé de production
WO2009116522A1 (fr) * 2008-03-18 2009-09-24 リンテック株式会社 Feuille adhésive facile à coller
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JP2008150431A (ja) * 2006-12-14 2008-07-03 Lintec Corp 粘着シート及び粘着シートの製造方法
WO2008075767A1 (fr) * 2006-12-21 2008-06-26 Lintec Corporation Feuille adhésive sensible à la pression et procédé pour sa production
WO2009048176A1 (fr) * 2007-10-12 2009-04-16 Lintec Corporation Feuille adhésive sensible à la pression et son procédé de production
WO2009116522A1 (fr) * 2008-03-18 2009-09-24 リンテック株式会社 Feuille adhésive facile à coller
JP2012197332A (ja) * 2011-03-18 2012-10-18 Lintec Corp 粘着シート

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017119396A (ja) * 2015-12-28 2017-07-06 住友化学株式会社 樹脂フィルム付光学部材の製造方法
WO2018101335A1 (fr) * 2016-11-30 2018-06-07 リンテック株式会社 Feuille adhésive double face et procédé de production de feuille adhésive double face
JP2020142530A (ja) * 2020-05-15 2020-09-10 住友化学株式会社 樹脂フィルム付光学部材の製造方法

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