JP2014114331A - Adhesive sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive sheet having uniform air permeability, in which the air permeability is hard to change even after a lapse of time.SOLUTION: The adhesive sheet includes a fibrous adhesive layer formed by spray coating, at least on one surface of a base material including a nonwoven fabric and/or a porous film, a hot-melt ultraviolet-curable acrylic adhesive or a hot-melt ultraviolet curable urethane adhesive, and thereafter by applying ultraviolet irradiation. The fibrous adhesive layer has gel fraction of 35-90%.

Description

  The present invention relates to an adhesive sheet. More specifically, the present invention relates to an adhesive sheet using a breathable substrate.

  Breathable pressure-sensitive adhesive sheets are widely used as medical and sanitary material pressure-sensitive adhesive sheets (see, for example, Patent Document 1).

  Examples of the breathable pressure-sensitive adhesive sheet include a breathable pressure-sensitive adhesive sheet in which a vent is formed by machining on a pressure-sensitive adhesive sheet made of a plastic film made of polypropylene or soft polyvinyl chloride, or a breathable material such as cloth or nonwoven fabric. A breathable pressure-sensitive adhesive sheet having a relatively large vent, such as a breathable pressure-sensitive adhesive sheet in which a pressure-sensitive adhesive is applied to a substrate in a stripe shape, is known. Since the pressure-sensitive adhesive is easy to flow at a small pressure, the pressure-sensitive adhesive may flow and flow into the vent hole over time. These breathable pressure-sensitive adhesive sheets can ensure a certain level of breathability even when some of the vent holes are blocked, but the breathability may be uneven.

  On the other hand, in recent years, pressure-sensitive adhesive tapes having more uniform air permeability have been required in various fields such as automobiles, architecture, and household appliances.

  As a breathable pressure-sensitive adhesive sheet having more uniform breathability, a breathable pressure-sensitive adhesive sheet in which a hot-melt pressure-sensitive adhesive is spray-coated on a breathable base material has been proposed. However, even with the breathable pressure-sensitive adhesive sheet, even if the breathability is uniform immediately after production, the pressure-sensitive adhesive may flow over time to block some of the vents, and the breathability may change. In terms of uniform air permeability after the passage, it was still insufficient. In particular, when stored at a high temperature (for example, 40 ° C. or higher) or when pressure is applied, the air permeability is likely to change.

JP 2006-326327 A

  Accordingly, an object of the present invention is to provide a pressure-sensitive adhesive sheet that is less likely to change air permeability even with time and has uniform air permeability. In particular, an object of the present invention is to provide a pressure-sensitive adhesive sheet having a uniform air permeability even when stored at a high temperature or when pressure is applied. In the present specification, “breathability” refers to a property of passing a gas such as air, moisture, a minute substance, or the like.

  As a result of intensive studies to achieve the above object, the present inventor was formed by spraying a specific hot melt pressure-sensitive adhesive on at least one surface of a substrate including a nonwoven fabric and / or a porous film. It has been found that by having a fibrous pressure-sensitive adhesive layer, an air-permeable pressure-sensitive adhesive sheet can be obtained that is less likely to change over time, and the present invention has been completed.

  That is, the present invention is a method in which a hot-melt ultraviolet curable acrylic pressure-sensitive adhesive or a hot-melt ultraviolet curable urethane pressure-sensitive adhesive is spray-coated on at least one surface of a substrate including a nonwoven fabric and / or a porous film. Provided is a pressure-sensitive adhesive sheet having a fibrous pressure-sensitive adhesive layer formed by ultraviolet irradiation and having a gel fraction of 35 to 90%.

  The present invention also provides a solid tackifier at a temperature of 23 ° C. with respect to 100 parts by weight of a styrene-isoprene-styrene block copolymer on at least one surface of a substrate including a nonwoven fabric and / or a porous film. It has a fibrous pressure-sensitive adhesive layer formed by spray-coating a hot-melt styrene-isoprene-styrene pressure-sensitive adhesive containing 20 to 150 parts by weight of a liquid tackifier at a temperature of 23 ° C. and 20 to 90 parts by weight. A pressure-sensitive adhesive sheet is provided.

Further, the present invention has a fibrous pressure-sensitive adhesive layer formed by spray-coating a hot-melt pressure-sensitive adhesive on at least one surface of a base material including a nonwoven fabric and / or a porous film. The pressure-sensitive adhesive sheet is characterized in that the distance of the pressure-sensitive adhesive sheet to be measured is less than 0.1 mm.
Test: Bonded to the lower end of one surface of the stainless steel plate so that the adhesive area between the fibrous pressure-sensitive adhesive layer of the adhesive sheet and the stainless steel plate is 200 mm ² (length 20 mm × width 10 mm). Reciprocate and crimp. Then, it is left at 50 ° C. for 0.5 hours, and the pressure-sensitive adhesive sheet and the stainless steel plate are installed so that the adhesive surface of the pressure-sensitive adhesive sheet and the stainless steel plate is in the vertical direction, and the weight of the pressure-sensitive adhesive sheet is reduced. A weight of 100 g is hung so as to hang down in the vertical direction, and after standing at a temperature of 50 ° C. for 120 minutes, the distance by which the pressure-sensitive adhesive sheet is displaced is measured.

  Since the pressure-sensitive adhesive sheet of the present invention has the above-described configuration, the air permeability is not easily changed over time, and the air permeability is uniform.

[Adhesive sheet]
The pressure-sensitive adhesive sheet of the present invention is a fibrous pressure-sensitive adhesive formed by spray-coating a hot-melt type UV-curable acrylic pressure-sensitive adhesive on at least one surface of a substrate including a nonwoven fabric and / or a porous film and then irradiating with ultraviolet rays. Fibrous adhesive formed by spraying a hot-melt ultraviolet curable urethane-based adhesive on at least one surface of a base material including a pressure-sensitive adhesive sheet, a nonwoven fabric and / or a porous film, and then irradiating with ultraviolet rays The temperature is 23 with respect to 100 parts by weight of a styrene-isoprene-styrene block copolymer (SIS block copolymer) on at least one surface of a base material including a pressure-sensitive adhesive sheet, a nonwoven fabric and / or a porous film. Hot melt containing 20 to 150 parts by weight of a solid tackifier at 20 ° C. and 20 to 90 parts by weight of a liquid tackifier at a temperature of 23 ° C. At least one of a pressure-sensitive adhesive sheet having a fibrous pressure-sensitive adhesive layer formed by spray-coating a styrene-isoprene-styrene-based pressure-sensitive adhesive (SIS pressure-sensitive adhesive) and / or a substrate including a nonwoven fabric and / or a porous film A pressure-sensitive adhesive sheet having a fibrous pressure-sensitive adhesive layer formed by spray-coating a hot-melt pressure-sensitive adhesive on the surface, and having a distance shifted by a pressure-sensitive adhesive sheet measured in the following <Test> of less than 0.1 mm is there.

  In the present specification, a fibrous pressure-sensitive adhesive layer formed by spraying a hot-melt type ultraviolet curable acrylic pressure-sensitive adhesive on at least one surface of a substrate including a nonwoven fabric and / or a porous film and then irradiating with ultraviolet rays The pressure-sensitive adhesive sheet having the above may be referred to as “the acrylic pressure-sensitive adhesive sheet of the present invention”. The fibrous pressure-sensitive adhesive layer in the acrylic pressure-sensitive adhesive sheet of the present invention may be referred to as “fibrous pressure-sensitive adhesive layer A”, and the base material in the acrylic pressure-sensitive adhesive sheet of the present invention may be referred to as “base material A”. A pressure-sensitive adhesive sheet having a fibrous pressure-sensitive adhesive layer formed by spraying a hot-melt type ultraviolet curable urethane-based pressure-sensitive adhesive on at least one surface of a substrate including a nonwoven fabric and / or a porous film and then irradiating with ultraviolet rays , Sometimes referred to as “the urethane-based pressure-sensitive adhesive sheet of the present invention”. The fibrous pressure-sensitive adhesive layer in the urethane-based pressure-sensitive adhesive sheet of the present invention may be referred to as “fibrous pressure-sensitive adhesive layer B”, and the substrate in the urethane-based pressure-sensitive adhesive sheet of the present invention may be referred to as “base material B”. 20 to 150 parts by weight of a solid tackifier at a temperature of 23 ° C. and at a temperature of 23 ° C. with respect to 100 parts by weight of the SIS block copolymer on at least one surface of a substrate including a nonwoven fabric and / or a porous film. When the pressure-sensitive adhesive sheet having a fibrous pressure-sensitive adhesive layer formed by spraying a hot melt type SIS pressure-sensitive adhesive containing 20 to 90 parts by weight of a liquid tackifier is referred to as “the SIS pressure-sensitive adhesive sheet of the present invention” There is. The fibrous pressure-sensitive adhesive layer in the SIS pressure-sensitive adhesive sheet of the present invention may be referred to as “fibrous pressure-sensitive adhesive layer C”, and the base material in the SIS-based pressure-sensitive adhesive sheet of the present invention may be referred to as “base material C”. In the present specification, the term “adhesive sheet” includes a tape-shaped material, that is, “adhesive tape”.

[Acrylic pressure-sensitive adhesive sheet of the present invention]
The acrylic pressure-sensitive adhesive sheet of the present invention is formed by spraying a hot-melt ultraviolet curable acrylic pressure-sensitive adhesive on at least one surface of the substrate A including a nonwoven fabric and / or a porous film and then irradiating with ultraviolet rays. A fibrous pressure-sensitive adhesive layer (fibrous pressure-sensitive adhesive layer A).

(Fibrous pressure-sensitive adhesive layer A)
The hot-melt type ultraviolet curable acrylic pressure-sensitive adhesive (heat-melting type ultraviolet curable acrylic pressure-sensitive adhesive) is a hot-melt type acrylic pressure-sensitive adhesive that is cured by ultraviolet irradiation. That is, the hot-melt type ultraviolet curable acrylic pressure-sensitive adhesive is a hot-melt type pressure-sensitive adhesive that contains an acrylic polymer and is cured by ultraviolet irradiation. The hot-melt ultraviolet curable acrylic pressure-sensitive adhesive may further contain a photopolymerization initiator, a crosslinking agent, and an additive as necessary. The said acrylic polymer can be used individually or in combination of 2 or more types.

  Although it does not specifically limit as said acrylic polymer, For example, the polymer comprised from the monomer component containing (meth) acrylic acid ester is mentioned. Although it does not specifically limit as said (meth) acrylic acid ester, For example, linear or branched, such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and isobutyl (meth) acrylate (Meth) acrylic acid alkyl ester having a chain alkyl group [preferably a (meth) acrylic acid alkyl ester having a linear or branched alkyl group having 1 to 20 carbon atoms] and the like.

  The monomer component is not particularly limited, and, for example, further, a carboxyl group-containing monomer such as (meth) acrylic acid or itaconic acid; an acid anhydride (acid anhydride group-containing monomer) of the carboxyl group-containing monomer; Hydroxyl group (hydroxyl group) -containing monomers such as 2-hydroxyethyl acrylate; Amide group-containing monomers such as (meth) acrylamide; Amino group-containing monomers; Epoxy group-containing monomers; Cyano group-containing monomers; Group-containing monomer; imide group-containing monomer; isocyanate group-containing monomer; hexanediol di (meth) acrylate, allyl (meth) acrylate, vinyl (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, urethane (meth) A Relate, polyfunctional monomer (polyfunctional monomer) such as a monomer having two or more unsaturated double bonds may contain like. The said monomer component can be used individually or in combination of 2 or more.

  Note that “(meth) acryl” means “acryl” and / or “methacryl” (one or both of “acryl” and “methacryl”). The “alkyl group” means a linear or branched alkyl group unless otherwise specified.

  The content of the acrylic polymer in the hot-melt ultraviolet curable acrylic pressure-sensitive adhesive is not particularly limited. For example, it is 40% with respect to the total amount (100% by weight) of the hot-melt ultraviolet curable acrylic pressure-sensitive adhesive. -99 weight% is preferable, More preferably, it is 60-99 weight%, More preferably, it is 70-99 weight%. By setting the content of the acrylic polymer to 40% by weight or more, it is possible to suppress fluidity (property that the adhesive flows) after spray coating and before ultraviolet irradiation, and coatability is improved. By setting the content of the acrylic polymer to 99% by weight or less, the tackiness can be expressed.

  The weight average molecular weight (Mw) of the acrylic polymer is not particularly limited, but the coating property of the pressure-sensitive adhesive increases, the applied pressure-sensitive adhesive becomes more difficult to flow, and the strength of the formed fibrous pressure-sensitive adhesive layer is improved. From the viewpoint, for example, 100,000 to 300,000 is preferable. The weight-average molecular weight of the acrylic polymer can be controlled by the monomer concentration, the monomer dropping rate, the type of polymerization initiator and the amount used, in addition to the temperature and time during polymerization.

  The photopolymerization initiator in the hot melt ultraviolet curable acrylic pressure-sensitive adhesive is not particularly limited, but can be appropriately selected and used from known or commonly used ones. For example, a benzoin ether photopolymerization initiator, Acetophenone photopolymerization initiator, α-ketol photopolymerization initiator, aromatic sulfonyl chloride photopolymerization initiator, photoactive oxime photopolymerization initiator, benzoin photopolymerization initiator, benzyl photopolymerization initiator, benzophenone And photopolymerization initiators such as photopolymerization initiators, ketal photopolymerization initiators, and thioxanthone photopolymerization initiators. The said photoinitiator can be used individually or in combination of 2 or more types.

  Although the usage-amount of the said photoinitiator is not specifically limited, For example, 0.1-5 weight part is preferable with respect to 100 weight part of said acrylic polymers, More preferably, it is 0.1-3 weight part. .

  The cross-linking agent in the hot-melt ultraviolet curable acrylic pressure-sensitive adhesive is not particularly limited. For example, an isocyanate cross-linking agent, an epoxy cross-linking agent, a melamine cross-linking agent, a peroxide cross-linking agent, and a urea cross-linking agent. Agents, metal alkoxide crosslinking agents, metal chelate crosslinking agents, metal salt crosslinking agents, carbodiimide crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, amine crosslinking agents and the like. The said crosslinking agent can be used individually or in combination of 2 or more types.

  Although the usage-amount of the said crosslinking agent is not specifically limited, For example, 0.01-10 weight part is preferable with respect to 100 weight part of said acrylic polymers, More preferably, it is 0.1-5 weight part.

  The additive in the hot-melt ultraviolet curable acrylic pressure-sensitive adhesive is not particularly limited. For example, a plasticizer, a filler (filler), an anti-aging agent, an antioxidant, a colorant (a pigment such as carbon black) And dyes), crosslinking accelerators (crosslinking aids), ultraviolet absorbers, softeners, surfactants, antistatic agents, and the like.

  The hot melt ultraviolet curable acrylic pressure-sensitive adhesive can be prepared, for example, by mixing the acrylic polymer, the photopolymerization initiator added as necessary, the crosslinking agent, the additive, and the like.

  The hot-melt ultraviolet curable acrylic pressure-sensitive adhesive has ultraviolet curable properties, so that it can undergo a curing reaction (for example, a polymerization reaction or a crosslinking reaction) before spray coating and after spray coating. Therefore, before spray coating, the viscosity can be adjusted so that the applied adhesive is easy to spray and the applied adhesive is difficult to flow, and the coating property is excellent. Moreover, after spray-coating, the adhesive force of an adhesive layer can be made suitable for a use by controlling hardening reaction.

  Note that a moisture-curing pressure-sensitive adhesive (moisture-curable pressure-sensitive adhesive) that is cured by moisture takes a long time to cure, and the pressure-sensitive adhesive (pressure-sensitive adhesive layer) may flow during the curing reaction to block the air holes. Therefore, it is not preferable. Moreover, since the adhesive (electron beam curable adhesive) which has an electron beam sclerosis | hardenability hardened | cured by an electron beam requires strong irradiation energy with respect to hardening reaction, members (for example, base materials) other than a fibrous adhesive layer Etc.) may change in quality.

  Since the hot-melt ultraviolet curable acrylic pressure-sensitive adhesive can be heated and melted, a fibrous pressure-sensitive adhesive layer having excellent breathability can be formed by spray coating or the like. Moreover, since it does not contain a solvent, it is excellent in safety and productivity, and the applied adhesive is difficult to flow.

  As the hot-melt ultraviolet curable acrylic pressure-sensitive adhesive, for example, a commercial product such as “Acrymelt G-7048” (manufactured by No-Tape Kogyo Co., Ltd.) is used from the viewpoint of adhesive properties at high temperatures and the degree of crosslinking. be able to.

  The fibrous pressure-sensitive adhesive layer A is formed by spraying the hot-melt ultraviolet curable acrylic pressure-sensitive adhesive and then irradiating with ultraviolet rays. That is, the method of providing the fibrous pressure-sensitive adhesive layer A is a method of spraying the hot-melt ultraviolet curable acrylic pressure-sensitive adhesive and then irradiating with ultraviolet rays. Although it does not specifically limit as the method of the said spray application, For example, the method of spraying and apply | coating the adhesive which was heat-melted by the curtain spray system through a hot air etc. is mentioned.

  The temperature at which the hot melt ultraviolet curable acrylic pressure-sensitive adhesive (melting temperature) is melted during spray coating is not particularly limited, but is preferably 100 to 200 ° C or more, more preferably 120 to 170 ° C, and still more preferably. 120-150 ° C. When the heating and melting temperature is less than 100 ° C., the pressure-sensitive adhesive may flow after application and block the vent hole. When the heating and melting temperature exceeds 200 ° C., the adhesive is easily deteriorated due to thermal deterioration. Although it does not specifically limit as a viscosity (melt viscosity) after the fusion | melting of the said hot-melt type ultraviolet curable acrylic adhesive, For example, 6000-100000 mPa * s is preferable, More preferably, it is 8000-15000 mPa * s. By setting the viscosity after melting within the above range, a fibrous pressure-sensitive adhesive layer having an appropriate average fiber diameter can be formed. The viscosity after melting can be measured by the method described in “(1) Viscosity” in (Evaluation) described later.

  Although the air flow rate at the time of spray coating by the curtain spray method is not particularly limited, 500 to 1500 L / min is preferable, and 800 to 1200 L / min is more preferable. Moreover, although air temperature is not specifically limited, 150-250 degreeC is preferable, More preferably, it is 170-200 degreeC.

5-100 g / cm < ² > is preferable and, as for the application quantity of the hot-melt type ultraviolet curable acrylic adhesive at the time of spray application, More preferably, it is 10-50 g / cm < ² >. By setting the coating amount to 5 g / cm ² or more, the coating unevenness is reduced and the adhesion to the adherend is excellent. By setting the coating amount to 100 g / cm ² or less, the air permeability is excellent.

Although it does not specifically limit as irradiation conditions at the time of ultraviolet irradiation after spray-applying the said hot-melt type ultraviolet curable acrylic adhesive, For example, illumination intensity 120-240 mW / cm < ² > (More preferably, 200-240 mW / cm ² ) and a light amount of 50 to 1000 mJ / cm ² (more preferably, 300 to 500 mJ / cm ² ). By irradiating with ultraviolet rays under the above conditions, the gel fraction of the fibrous pressure-sensitive adhesive layer can be controlled, and the fibrous pressure-sensitive adhesive layer becomes more difficult to flow even when stored at a high temperature or when pressure is applied.

  5-100 micrometers is preferable and, as for the average fiber diameter of the said fibrous adhesive layer A, More preferably, it is 10-60 micrometers. When the average fiber diameter is 5 μm or more, the adhesive strength is improved. In addition, the adhesive is less likely to scatter around when spraying, and the productivity is excellent. When the average fiber diameter is 100 μm or less, there is little air permeability unevenness. Further, when spraying the pressure-sensitive adhesive, the temperature of the pressure-sensitive adhesive is not easily transmitted to the base material, and the base material is hardly damaged. The average fiber diameter can be controlled by the melt viscosity of the pressure-sensitive adhesive, the air flow rate during spray coating (hot air flow rate), the height of the curtain spray die, the spray temperature (spray die temperature), and the like.

  The thickness of the fibrous pressure-sensitive adhesive layer A is preferably 10 to 300 μm, more preferably 30 to 200 μm, and still more preferably 50 to 100 μm, from the viewpoint of tape smoothness.

  The gel fraction of the fibrous pressure-sensitive adhesive layer A is 35 to 90%, preferably 40 to 80%, more preferably 40 to 70%. By setting the gel fraction to 35% or more, the fibrous pressure-sensitive adhesive layer becomes difficult to flow, and the air permeability hardly changes over time, and the air permeability is uniform. In addition, even after storage at a high temperature or when pressure is applied, the pressure-sensitive adhesive layer hardly flows and the air permeability hardly changes. By setting the gel fraction to 90% or less, the adhesive strength is improved. The gel fraction can be controlled by the type of pressure-sensitive adhesive, spray coating conditions, curing conditions, and the like.

Specifically, the gel fraction (ratio of toluene insoluble matter) can be measured and calculated, for example, by the following <Method for measuring gel fraction>.
<Method for measuring gel fraction>
About 0.1 g of a fibrous pressure-sensitive adhesive layer is collected from the pressure-sensitive adhesive sheet to obtain a fibrous pressure-sensitive adhesive layer for gel fraction measurement. After wrapping the fibrous pressure-sensitive adhesive layer for measuring the gel fraction in a porous tetrafluoroethylene sheet (trade name “NTF1122”, manufactured by Nitto Denko Corporation) having pores having an average pore diameter of 0.2 μm, silk thread The weight at that time is measured, and this weight is defined as the weight before immersion. The weight before immersion is the total weight of the fibrous pressure-sensitive adhesive layer, the tetrafluoroethylene sheet, and the kite string. Further, the total weight of the tetrafluoroethylene sheet and the kite string is also measured, and this weight is defined as the wrapping weight.
Next, the above fibrous pressure-sensitive adhesive layer wrapped with a tetrafluoroethylene sheet and bound with a kite string (referred to as “sample”) is placed in a 50 mL container filled with toluene and allowed to stand at 70 ° C. for 24 hours. . Thereafter, a sample (after toluene treatment) is taken out from the container, transferred to an aluminum cup, dried in a dryer at 130 ° C. for 2 hours to remove toluene, and then the weight is measured. And
Then, the gel fraction is calculated from the following formula.
Gel fraction (% by weight) = (A−B) / (C−B) × 100
(In the above formula, A is the weight after immersion, B is the weight of the bag, and C is the weight before immersion.)

(Substrate A)
The base material A includes at least one of a nonwoven fabric (nonwoven fabric A) and a porous film (porous film A). The base material A may be, for example, a single-layer base material made only of the non-woven fabric A or the porous film A, a laminated base material containing the non-woven fabric A, a laminated base material containing the porous film A, or the non-woven fabric A. And the laminated base material containing the porous film A may be sufficient. In the case where the substrate A is a laminated substrate, in addition to the nonwoven fabric A and the porous film A, air permeable members such as paper and woven fabric may be included.

  The nonwoven fabric A is not particularly limited. For example, polyamide nonwoven fabric (nylon nonwoven fabric, etc.), polyester nonwoven fabric, polyolefin nonwoven fabric (polypropylene nonwoven fabric, polyethylene nonwoven fabric, polypropylene / polyethylene mixed nonwoven fabric, etc.), rayon nonwoven fabric, etc. And other known or conventional non-woven fabrics (non-woven fabrics made of natural fibers, non-woven fabrics made of synthetic fibers, etc.). Among these, polyester nonwoven fabrics are preferable from the viewpoint of texture and breathability. The said nonwoven fabric A may be comprised from 1 type of fiber, and may be comprised combining multiple types of fiber.

Although the manufacturing method of the said nonwoven fabric A is not specifically limited, For example, a spun bond system, a spunlace system, etc. are mentioned. Among these, a nonwoven fabric (spunbond nonwoven fabric) manufactured by a spunbond method is preferable from the viewpoint of strength. In addition, the said nonwoven fabric A may have any form of a single layer and a multilayer. In the nonwoven fabric A, the fiber diameter (average fiber diameter), fiber length, basis weight, and the like are not particularly limited. For example, the basis weight is preferably ²⁰ to 100 g / m ² , more preferably from the viewpoint of processability and cost. 20 to 80 g / m ² .

  Although it does not specifically limit as said porous film A, For example, the porous film etc. which are comprised from polyolefin resin, polyester resin, polystyrene resin, etc. are mentioned. Among these, a porous film composed of a polyolefin-based resin is preferable from the viewpoint of price and flexibility.

  Although it does not specifically limit as said polyolefin resin, For example, a polyethylene-type resin, a polypropylene-type resin, an ethylene-alpha-olefin copolymer etc. are mentioned. The said polyolefin resin may be used independently, and 2 or more types may be mixed and used for it.

  Although resin (for example, polyolefin resin) which constitutes the porous film A is not particularly limited, for example, inorganic particles may be included. The inorganic particles play a role of making the film porous by generating voids (pores) around the inorganic particles by stretching. The inorganic particles can be appropriately selected from known or commonly used particles, and examples thereof include metal carbonates such as calcium carbonate and magnesium carbonate; and metal salts of sulfuric acid such as magnesium sulfate. The shape of the inorganic particles is not particularly limited, and a flat plate shape, a granular shape, or the like can be used. The said inorganic particle may be used independently and may mix and use 2 or more types.

  The porous film A may contain various additives such as a colorant, an antioxidant, an antioxidant, an ultraviolet absorber, a flame retardant, and a stabilizer.

  Although the said porous film A is not specifically limited, For example, it can be manufactured by making porous by extending | stretching an unstretched film. The porous film A can be produced by, for example, a melt film forming method (T-die method, inflation method). Specifically, for example, the polyester resin, the inorganic particles, and the like are mixed and dispersed in a biaxial kneading extruder to produce raw material pellets, and then melt-extruded in a monoaxial extruder to produce an unstretched film. The unstretched film is made porous by stretching. When a porous film is used as a laminated film, a coextrusion method can be preferably used. The porous film A may be subjected to various treatments such as back treatment and antistatic treatment as necessary.

  Although the thickness of the said base material A is not specifically limited, From a viewpoint of workability and a feel, for example, 30-200 micrometers is preferable, More preferably, it is 30-150 micrometers, More preferably, it is 30-100 micrometers.

Although the fragile air permeability of the base material A is not particularly limited, it is preferably, for example, 300 to 5000 cc / cm ² / sec, more preferably 1000 to 3000 cc / cm ² / sec from the viewpoint of air permeability. In addition, in this specification, a fragile air permeability means what was measured based on JISL1096.

  The acrylic pressure-sensitive adhesive sheet of the present invention may be a single-sided pressure-sensitive adhesive sheet having a fibrous pressure-sensitive adhesive layer A on one surface of the substrate A, or a fibrous pressure-sensitive adhesive layer on both surfaces of the substrate A. A double-sided pressure-sensitive adhesive sheet having A or a fibrous pressure-sensitive adhesive layer A other than the fibrous pressure-sensitive adhesive layer A (for example, fibrous pressure-sensitive adhesive layer) on one surface of the substrate A and the other surface. Double-sided pressure-sensitive adhesive sheet having adhesive layer B, fibrous pressure-sensitive adhesive layer C, fibrous pressure-sensitive adhesive layer B, and fibrous pressure-sensitive adhesive layer other than fibrous pressure-sensitive adhesive layer C) may be used. When the acrylic pressure-sensitive adhesive sheet of the present invention is a double-sided pressure-sensitive adhesive sheet, a double-sided pressure-sensitive adhesive sheet having the fibrous pressure-sensitive adhesive layer A on both surfaces of the substrate A is preferable from the viewpoint of productivity.

  Although the manufacturing method of the acrylic adhesive sheet of this invention can use a well-known thru | or usual manufacturing method, it does not specifically limit, For example, the fibrous adhesive layer A is provided in the at least one surface of the said base material A. The method etc. are mentioned. Examples of the method for providing the fibrous pressure-sensitive adhesive layer A include a method for providing the fibrous pressure-sensitive adhesive layer A.

More specifically, the fibrous adhesive layer A is formed by spray-coating a hot melt ultraviolet curable acrylic adhesive on at least one surface of the substrate A including the nonwoven fabric A and / or the porous film A. step, illuminance fibrous adhesive layer a 120~240mW / cm ² (preferably 200~240mW / cm ^2), the gel fraction of the fibrous pressure-sensitive adhesive layer a was irradiated with ultraviolet light quantity 300~500mJ / cm ² The manufacturing method including the process etc. which make 35-90% is mentioned. The method for producing an acrylic pressure-sensitive adhesive sheet of the present invention may include all of the above steps or a part thereof.

  Although the thickness (total thickness) of the acrylic adhesive sheet of this invention is not specifically limited, 50-200 micrometers is preferable, More preferably, it is 70-150 micrometers. When the thickness is 200 μm or less, flexibility and texture can be improved. When the thickness is 50 μm or more, wrinkles are hardly formed and the productivity is excellent. The thickness of the pressure-sensitive adhesive sheet does not include the thickness of the separator.

The fragile air permeability of the acrylic pressure-sensitive adhesive sheet of the present invention is not particularly limited, but is preferably 30 to 500 cc / cm ² / sec, and more preferably 100 to 300 cc / cm ² / sec, from the viewpoint of air permeability. .

[Urethane adhesive sheet of the present invention]
The urethane-based pressure-sensitive adhesive sheet of the present invention is formed by spraying a hot-melt type UV-curable urethane-based pressure-sensitive adhesive on at least one surface of a base material B including a nonwoven fabric and / or a porous film and then irradiating with ultraviolet rays. A fibrous pressure-sensitive adhesive layer (fibrous pressure-sensitive adhesive layer B).

(Fibrous pressure-sensitive adhesive layer B)
The hot melt ultraviolet curable urethane pressure-sensitive adhesive (heat-melting type ultraviolet curable urethane pressure-sensitive adhesive) is a hot-melt type urethane pressure-sensitive adhesive that is cured by ultraviolet irradiation. That is, the hot-melt type ultraviolet curable urethane-based pressure-sensitive adhesive is a hot-melt type pressure-sensitive adhesive that contains a urethane-based polymer and is cured by ultraviolet irradiation. The hot-melt ultraviolet curable urethane-based pressure-sensitive adhesive may further contain a photopolymerization initiator and an additive as necessary. The said urethane type polymer can be used individually or in combination of 2 or more types.

Although it does not specifically limit as said urethane type polymer, For example, the urethane type polymer represented by following formula (1) can be used suitably.
X-R-Y (1)
(In the formula (1), R is a urethane polymer chain part, X is a group having a reactive functional group, and Y is a group having a reactive functional group or a sealing group.)

  In the urethane polymer represented by the above formula (1), examples of the reactive functional group in the group having a reactive functional group as X include a vinyl group, a vinyl-alkyl group (for example, an allyl group), acryloyl, and the like. In addition to a reactive functional group containing a vinyl group such as a group or a methacryloyl group (sometimes referred to as a “vinyl group-containing functional group”), a carboxyl group, a hydroxyl group, an epoxy group, an amino group, and the like can be given. The reactive functional group is preferably a vinyl group-containing functional group (vinyl group, allyl group, acryloyl group, methacryloyl group, etc.), and among them, acryloyl group and methacryloyl group (when these are collectively referred to as “(meth) acryloyl group”) Is particularly preferred. The reactive functional group may be one type or two or more types.

  When introducing a group having a reactive functional group (such as a vinyl group-containing functional group) into the urethane polymer in the urethane polymer, together with the reactive functional group, the monomer component in the urethane polymer A compound having a reactive group (sometimes referred to as “monomer reactive group”) (sometimes referred to as “vinyl group-containing monomer reactive compound”) can be used. In such a vinyl group-containing monomer-reactive compound, examples of the monomer-reactive group include a hydroxyl group, an isocyanate group, a carboxyl group, and an amino group, and a hydroxyl group is preferable. The vinyl group-containing monomer reactive compound only needs to have at least one monomer reactive group in the molecule. In addition, the vinyl group-containing monomer reactive compound may have only one type of monomer reactive group or two or more types.

  As the vinyl group-containing monomer reactive compound, for example, a compound having a hydroxyl group together with a vinyl group-containing functional group (sometimes referred to as “vinyl group-containing hydroxy compound”) is preferably used. Examples of such a vinyl group-containing hydroxy compound include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxy. Hydroxyalkyl (meth) acrylates such as butyl (meth) acrylate; hydroxyalkyl vinyl ethers such as hydroxymethyl vinyl ether, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether; Ether, 2-hydroxyethyl allyl ether, 3-hydroxypropyl allyl ether, 2-hydroxypropyl allyl ether Such as hydroxyalkyl allyl ether and 4-hydroxybutyl allyl ether. As the vinyl group-containing hydroxy compound, hydroxyalkyl (meth) acrylate is preferable, and 2-hydroxyethyl acrylate is particularly preferable.

  Moreover, in the urethane polymer represented by the formula (1), the sealing group in the group having a sealing group as Y represents the reactivity of the terminal group (such as an isocyanate group) of the urethane polymer chain part. Introduced to seal. Examples of such a sealing group include hydrocarbon-oxy groups such as an alkoxy group, an aryloxy group, and a cycloalkyloxy group, and an alkoxy group is preferable. Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, isopropoxy group, butyloxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, Alkoxy having 1 to 30 carbon atoms such as dodecyloxy group, tridecyloxy group, tetradecyloxy group, pentadecyloxy group, hexadecyloxy group, heptadecyloxy group, octadecyloxy group, nonadecyloxy group, eicosyloxy group Group and the like. A sealing group can be used individually or in combination of 2 or more types.

  In addition, when introducing the group which has an alkoxy group into a urethane type polymer as a group which has a sealing group, monools can be used. Such monools are not particularly limited, and for example, methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, isooctanol, nonyl alcohol, decyl In addition to aliphatic monohydric alcohols such as alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, hexadecyl alcohol, heptadecyl alcohol, octadecyl alcohol, nonadecyl alcohol, eicosyl alcohol, 1-hydroxycyclohexyl phenyl ketone, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) keto And the like hydroxyl group-containing phenyl ketones such as. As monools, aliphatic monohydric alcohols are preferable, and octadecyl alcohol is particularly preferable.

  In the group having a reactive functional group as Y in the formula (1), the reactive functional group is the same reactive functional group as the reactive functional group in the group having a reactive functional group as X [for example, In addition to vinyl group-containing functional groups such as vinyl groups, vinyl-alkyl groups (eg, allyl groups), acryloyl groups, methacryloyl groups, etc., carboxyl groups, hydroxyl groups, epoxy groups, amino groups, and the like] can be used. Among them, Y is preferably a group having a sealing group.

  Furthermore, in the urethane polymer represented by the formula (1), the urethane polymer chain portion as R is a residue of the urethane polymer and reacts with the polyisocyanate compound and the isocyanate group. It is composed of a urethane polymer containing at least a monomer component as a compound having at least two groups having a property (sometimes referred to as “isocyanate-reactive compound”). Examples of the polyisocyanate compound include aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate, and araliphatic polyisocyanate. Polyisocyanate compounds can be used alone or in combination of two or more.

  Examples of the aliphatic polyisocyanate include 1,6-hexamethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2-methyl-1,5-pentane diisocyanate, 3-methyl-1,5-pentane diisocyanate, lysine diisocyanate, Aliphatic diisocyanates such as 2,4,4-trimethyl-1,6-hexamethylene diisocyanate and 2,2,4-trimethyl-1,6-hexamethylene diisocyanate are included.

  Examples of the alicyclic polyisocyanate include alicyclic diisocyanates such as isophorone diisocyanate, norbornane diisocyanate, cyclohexyl diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenated tetramethylxylene diisocyanate. Is included.

  Aromatic polyisocyanates include, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-diphenyl ether diisocyanate, 2 -Nitrodiphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, Aromatic diisocyanates such as m-phenylene diisocyanate, p-phenylene diisocyanate, naphthylene-1,4-diisocyanate, naphthylene-1,5-diisocyanate, 3,3′-dimethoxydiphenyl-4,4′-diisocyanate Anate etc. are included.

  Examples of the araliphatic polyisocyanate include araliphatic diisocyanates such as xylylene-1,4-diisocyanate and xylylene-1,3-diisocyanate.

  In addition, as the polyisocyanate-based compound, the above-exemplified aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate, double body or trimer by araliphatic polyisocyanate, reaction product or polymer (for example, Diphenylmethane diisocyanate duplex and trimer, reaction product of trimethylolpropane and tolylene diisocyanate, reaction product of trimethylolpropane and hexamethylene diisocyanate, polymethylene polyphenyl isocyanate, polyether polyisocyanate, polyester polyisocyanate Etc.) can also be used.

  As the polyisocyanate compound, an alicyclic polyisocyanate (particularly isophorone diisocyanate) can be suitably used.

  The isocyanate-reactive compound is not particularly limited as long as it is a compound having at least two groups having reactivity with respect to isocyanate groups in the molecule. Examples of reactive groups for isocyanate groups include hydroxyl groups and amino groups. The reactive group with respect to an isocyanate group may be single, and 2 or more types may be combined together. Examples of the isocyanate-reactive compound include a polyol compound and a polyamine compound. The isocyanate-reactive compounds can be used alone or in combination of two or more. Therefore, as the isocyanate-reactive compound, only one selected from polyol-based compounds and polyamine-based compounds may be used, or two or more selected from polyol-based compounds and polyamine-based compounds may be used in combination. .

  As the isocyanate-reactive compound, a polyol compound can be suitably used. The polyol compound is not particularly limited as long as it is a polyol compound used as a monomer component of a known urethane polymer, and may be, for example, a low molecular weight type polyol compound such as a polyhydric alcohol. High molecular weight type polyol compounds such as polyols, polyether polyols, polycarbonate polyols, polyolefin polyols, and polyacryl polyols may be used.

  Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-trimethylene glycol, 1,4-tetramethylene diol, 1,5-pentamethylene diol, neopentyl glycol, 1, In addition to diols such as 6-hexamethylenediol, 1,4-cyclohexanediol, and bisphenol A, glycerin, trimethylolpropane, trimethylolethane, sugar alcohols (such as xylitol and sorbitol), and the like can be given.

The polyester polyol is not particularly limited as long as it is a polyester polymer having at least two hydroxyl groups in the molecule (particularly at the terminal). The polyester polyol is prepared by a method of polymerizing a polyhydric alcohol and a polyvalent carboxylic acid by polycondensation, a method of ring-opening polymerization of a cyclic ester (lactone), or a method combining these methods. In addition, well-known conditions etc. can be utilized suitably for the conditions of superposition | polymerization at the time of preparing polyester polyol. The polyhydric alcohol can be appropriately selected from polyhydric alcohols exemplified as low molecular weight type polyol compounds and dimer diol. Examples of the polyvalent carboxylic acid include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, and tetradecanedioic acid. , Pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, hexatriacontanedioic acid [HOOC- (CH ₂ ) ₃₄ —COOH], aliphatic dicarboxylic acids such as dimer acid; 1,4-cyclohexanedicarboxylic acid Alicyclic dicarboxylic acid such as terephthalic acid, isophthalic acid, and aromatic dicarboxylic acid such as phthalic acid. Examples of the cyclic ester include ε-caprolactone. Specifically, as the polyester polyol, for example, a polyester polyol by dimer acid and 1,6-hexamethylene diol, a polyester polyol by hexatriacontanedioic acid and dimer diol, a polyester polyol by dimer acid and dimer diol, etc. Is mentioned.

  The polyether polyol is not particularly limited as long as it is a polyether polymer having at least two hydroxyl groups in the molecule (particularly at the terminal). The polyether polyol is prepared by a method in which alkylene glycol is polymerized by condensation, a method in which cyclic ether is ring-opened, or a method in which these methods are combined. In addition, well-known conditions etc. can be utilized suitably for the conditions of superposition | polymerization at the time of preparing polyether polyol. Examples of the alkylene glycol include ethylene glycol, propylene glycol, and tetramethylene glycol. Specifically, examples of the polyether polyol include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and poly (ethylene glycol-propylene glycol) copolymers.

  The polycarbonate polyol is not particularly limited as long as it is a polycarbonate polymer having at least two hydroxyl groups in the molecule (particularly at the terminal). As polycarbonate polyol, a method of reacting polyhydric alcohol and phosgene, a method of reacting polyhydric alcohol and diphenyl carbonate by transesterification, cyclic carbonate (ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, hexamethylene carbonate, etc.) In addition to the ring-opening polymerization of the alkylene carbonate, etc.), and a combination of these methods.

  Polyolefin polyol and polyacryl polyol are each an olefin polymer having at least two hydroxyl groups in the molecule (particularly at the terminal), or at least two hydroxyl groups in the molecule (particularly at the terminal). There is no particular limitation as long as it is an acrylic polymer. In order to introduce a hydroxyl group into an olefin polymer or acrylic polymer, olefin as a monomer main component of the olefin polymer or (meth) acrylic acid ester as a monomer main component of the acrylic polymer Α, β-unsaturated compound having a hydroxyl group as a copolymerization component [for example, (meth) acrylic acid alkyl ester such as 2-hydroxyethyl (meth) acrylate and 3-hydroxypropyl (meth) acrylate)] Is used.

  Among these, as the isocyanate-reactive compound, a polyester polyol can be preferably used. The number average molecular weight of the polyester polyol is not particularly limited, and can be selected, for example, from a range of 5,000 to 1,000,000 (preferably 10,000 to 500,000, more preferably 100,000 to 300,000).

  Further, the polyamine compound as the isocyanate-reactive compound is not particularly limited as long as it is a polyamine compound used as a monomer component of a known urethane polymer, and examples thereof include aliphatic polyamines, alicyclic polyamines, and aromatics. Polyamines, araliphatic polyamines and the like are included. Polyamine compounds can be used alone or in combination of two or more. Examples of the aliphatic polyamine include 1,3-trimethylenediamine (diaminopropane), 1,4-tetramethylenediamine (diaminobutane), 1,6-hexamethylenediamine, 1,9-nonamethylenediamine, and bisamino. Propyl ether, bisaminopropyl ethane, bisaminopropyl diethylene glycol, bisaminopropoxyneopentyl glycol and the like are included. The alicyclic polyamines include, for example, isophorone diamine and hydrogenated diphenylmethane diamine. Aromatic polyamines include, for example, 2,4-tolylenediamine, 2,6-tolylenediamine, 4,4′-diphenylmethanediamine, 2,4′-diphenylmethanediamine, and the like. Examples of the araliphatic polyamine include xylylene-1,4-diamine and xylylene-1,3-diamine.

  Thus, in the urethane polymer represented by the above formula (1), one end of the polyurethane polymer chain is a group having a reactive functional group, and the other end is a group having a reactive functional group. Or it has the structure used as the group which has a sealing group. The method for producing such a urethane polymer is not particularly limited, and for example, a method described in JP-A-10-330453 can be used. Specifically, the urethane polymer is a method of introducing a reactive functional group or a sealing group after preparing a polyurethane polymer, or a method of introducing a reactive functional group or a sealing group during preparation of a polyurethane polymer. It can prepare by.

  As the urethane polymer represented by the above formula (1), a urethane polymer having a vinyl group-containing functional group as a reactive functional group [particularly, a urethane prepolymer having a (meth) acryloyl group] is suitable. In such a reactive functional group-containing urethane prepolymer, a polyisocyanate compound and a polyol compound (particularly polyester polyol) are used as monomer components as the urethane polymer chain part constituting the main chain or skeleton. And a urethane polymer chain portion (residue of the urethane polymer) by a urethane polymer having an isocyanate group at the end is preferable.

  In addition, as a urethane type polymer represented by the said Formula (1), the urethane type polymer illustrated by Unexamined-Japanese-Patent No. 10-330453, Unexamined-Japanese-Patent No. 2005-247938, 2005-281689, for example, urethane Examples thereof include urethane polymers formed from a prepolymer.

  The content of the urethane polymer in the hot melt ultraviolet curable urethane pressure-sensitive adhesive is not particularly limited. For example, the content of the urethane polymer is 40% with respect to the total amount (100% by weight) of the hot melt ultraviolet curable urethane pressure sensitive adhesive. -99 weight% is preferable, More preferably, it is 60-99 weight%, More preferably, it is 70-99 weight%. By setting the content of the urethane polymer to 40% by weight or more, the fluidity at high temperature can be suppressed. By setting the content of the urethane polymer to 99% by weight or less, it is possible to express adhesiveness.

  The weight average molecular weight (Mw) of the urethane-based polymer is not particularly limited, but the applicability of the adhesive increases, the applied adhesive becomes difficult to flow, and the strength of the formed fibrous adhesive layer is improved. From the viewpoint, for example, 40,000 to 60,000 is preferable. The weight-average molecular weight of the urethane polymer can be controlled by the monomer concentration, the monomer dropping rate, the type of polymerization initiator, the amount used, and the like in addition to the temperature and time during polymerization.

  Although it does not specifically limit as said photoinitiator in the said hot-melt type ultraviolet curable urethane type adhesive, For example, the above-mentioned thing is mentioned. The said photoinitiator can be used individually or in combination of 2 or more types.

  Although the usage-amount of the said photoinitiator is not specifically limited, For example, 0.5-3 weight part is preferable with respect to 100 weight part of said urethane type polymers, More preferably, it is 0.5-1 weight part. .

  The additive in the hot-melt ultraviolet curable urethane pressure-sensitive adhesive is not particularly limited. For example, a crosslinking agent, a plasticizer, a filler (filler), an anti-aging agent, an antioxidant, a colorant (carbon black) Pigments and dyes), crosslinking accelerators (crosslinking aids), ultraviolet absorbers, softeners, surfactants, antistatic agents, and the like.

  The hot-melt ultraviolet curable urethane pressure-sensitive adhesive can be prepared, for example, by mixing the urethane polymer, the photopolymerization initiator added as necessary, the crosslinking agent, the additive, and the like.

  The hot-melt ultraviolet curable urethane-based pressure-sensitive adhesive has ultraviolet curable properties, and thus can undergo a curing reaction (for example, a polymerization reaction or a crosslinking reaction) before spray coating and after spray coating. Therefore, before spray coating, the viscosity can be adjusted so that the applied adhesive is easy to spray and the applied adhesive is difficult to flow, and the coating property is excellent. Moreover, after spray-coating, the adhesive force of an adhesive layer can be made suitable for a use by controlling hardening reaction.

  Note that a moisture-curing pressure-sensitive adhesive (moisture-curable pressure-sensitive adhesive) that is cured by moisture takes a long time to cure, and the pressure-sensitive adhesive (pressure-sensitive adhesive layer) may flow during the curing reaction to block the air holes. Therefore, it is not preferable. Moreover, since the adhesive (electron beam curable adhesive) which has an electron beam sclerosis | hardenability hardened | cured by an electron beam requires strong irradiation energy with respect to hardening reaction, members (for example, base materials) other than a fibrous adhesive layer Etc.) may change in quality.

  Since the hot-melt ultraviolet curable urethane-based pressure-sensitive adhesive can be melted by heating, a fibrous pressure-sensitive adhesive layer having excellent air permeability can be formed by spray coating or the like. Moreover, since it does not contain a solvent, it is excellent in safety and productivity, and the applied adhesive is difficult to flow.

  As said hot melt type ultraviolet curable urethane type adhesive, commercial items, such as a brand name "PSA-7511" (made by Kyoeisha Chemical Co., Ltd.), can be used, for example.

  The fibrous pressure-sensitive adhesive layer B is formed by spraying the hot-melt ultraviolet curable urethane pressure-sensitive adhesive and then irradiating with ultraviolet rays. That is, the method of providing the fibrous pressure-sensitive adhesive layer B is a method of spraying the hot-melt ultraviolet curable urethane-based pressure-sensitive adhesive and then irradiating with ultraviolet rays. Although it does not specifically limit as the method of the said spray application, For example, the method of spraying and apply | coating the adhesive which was heat-melted by the curtain spray system through a hot air etc. is mentioned.

  The temperature at which the hot-melt ultraviolet curable urethane-based pressure-sensitive adhesive is melted during spray coating (heat melting temperature) is not particularly limited, but is preferably 100 to 200 ° C or more, more preferably 130 to 170 ° C, and still more preferably. 130-150 ° C. When the heating and melting temperature is less than 100 ° C., the pressure-sensitive adhesive may flow after application and block the vent hole. When the heating and melting temperature exceeds 200 ° C., the adhesive is easily deteriorated due to thermal deterioration. Although it does not specifically limit as a viscosity (melt viscosity) after melting of the said hot-melt type ultraviolet curable urethane type adhesive, For example, 6000-100000 mPa * s is preferable, More preferably, it is 10000-20000 mPa * s. By setting the viscosity after melting within the above range, a fibrous pressure-sensitive adhesive layer having an appropriate average fiber diameter can be formed. The viscosity after melting can be measured by the method described in “(1) Viscosity” in (Evaluation) described later.

  Although the air flow rate at the time of spray coating by the curtain spray method is not particularly limited, 500 to 1500 L / min is preferable, and 800 to 1200 L / min is more preferable. Moreover, although air temperature is not specifically limited, 150-200 degreeC is preferable, More preferably, it is 150-170 degreeC.

5-100 g / m < ² > is preferable and, as for the application quantity of the hot-melt type ultraviolet curable urethane type adhesive at the time of spray application, More preferably, it is 10-50 g / m < ² >. By setting the coating amount to 5 g / m ² or more, the coating unevenness is reduced and the adhesion to the adherend is excellent. By setting the coating amount to 100 g / m ² or less, the air permeability is excellent.

Irradiation conditions for ultraviolet irradiation after spray application of the hot melt ultraviolet curable urethane pressure-sensitive adhesive are not particularly limited. For example, the illuminance is 120 to 240 mW / cm ² , and the light intensity is 50 to 1000 mJ / cm ² ( More preferably, the conditions which irradiate 300-500 mJ / cm < ² >) ultraviolet rays are mentioned. By irradiating with ultraviolet rays under the above conditions, the gel fraction of the fibrous pressure-sensitive adhesive layer can be controlled, and the fibrous pressure-sensitive adhesive layer becomes difficult to flow even when stored at a high temperature or when pressure is applied.

  5-100 micrometers is preferable and, as for the average fiber diameter of the said fibrous adhesive layer B, More preferably, it is 10-50 micrometers. When the average fiber diameter is 5 μm or more, the adhesive strength is improved. In addition, the adhesive is less likely to scatter around when spraying, and the productivity is excellent. When the average fiber diameter is 100 μm or less, the temperature of the pressure-sensitive adhesive is hardly transmitted to the base material when spraying the pressure-sensitive adhesive, and the base material is hardly damaged. The average fiber diameter can be controlled by the melt viscosity of the pressure-sensitive adhesive, the air flow rate during spray coating (hot air flow rate), the height of the curtain spray die, the spray temperature (spray die temperature), and the like.

  The thickness of the fibrous pressure-sensitive adhesive layer B is preferably 10 to 200 μm, more preferably 30 to 150 μm, and still more preferably 30 to 100 μm, from the viewpoint of tape smoothness.

  The gel fraction of the fibrous pressure-sensitive adhesive layer B is 35 to 90%, preferably 40 to 80%, more preferably 40 to 70%. By setting the gel fraction to 35% or more, the fibrous pressure-sensitive adhesive layer becomes difficult to flow, and the air permeability hardly changes over time, and the air permeability is uniform. In addition, even after storage at a high temperature or when pressure is applied, the pressure-sensitive adhesive layer hardly flows and the air permeability hardly changes. By setting the gel fraction to 90% or less, the adhesive strength is improved. The gel fraction can be controlled by the type of pressure-sensitive adhesive, spray coating conditions, curing conditions, and the like. Specifically, the gel fraction (ratio of toluene insoluble matter) can be measured and calculated, for example, by the above-described <Method for measuring gel fraction>.

(Substrate B)
The base material B includes at least one of a nonwoven fabric (nonwoven fabric B) and a porous film (porous film B). The base material B may be, for example, a single-layer base material composed of only the non-woven fabric B or the porous film B, a laminated base material including the non-woven fabric B, a laminated base material including the porous film B, or the non-woven fabric B. And the laminated base material containing the porous film B may be sufficient. When the base material B is a laminated base material, in addition to the non-woven fabric B and the porous film B, air permeable members such as paper and woven fabric may be included.

  Although it does not specifically limit as said nonwoven fabric B, For example, the above-mentioned nonwoven fabric A etc. are mentioned. Among these, polyester nonwoven fabrics are preferable from the viewpoint of texture and breathability. The said nonwoven fabric B may be comprised from 1 type of fiber, and may be comprised combining multiple types of fiber.

Although the manufacturing method of the said nonwoven fabric B is not specifically limited, For example, a spun bond system, a spunlace system, etc. are mentioned. Among these, a nonwoven fabric (spunbond nonwoven fabric) manufactured by a spunbond method is preferable from the viewpoint of strength. In addition, the said nonwoven fabric B may have any form of a single layer and a multilayer. In the non-woven fabric B, the fiber diameter (average fiber diameter), fiber length, basis weight and the like are not particularly limited. For example, the basis weight is preferably ²⁰ to 100 g / m ² and more preferably from the viewpoint of processability and cost. 20 to 80 g / m ² .

  Although it does not specifically limit as said porous film B, For example, the above-mentioned porous film A etc. are mentioned. Among these, a porous film composed of a polyolefin-based resin is preferable from the viewpoint of price and flexibility.

  Although it does not specifically limit as said polyolefin resin, For example, the above-mentioned polyester resin is mentioned. The said polyolefin resin may be used independently, and 2 or more types may be mixed and used for it.

  Although resin (for example, polyolefin resin) which constitutes the porous film B is not particularly limited, for example, inorganic particles may be included. The inorganic particles play a role of making the film porous by generating voids (pores) around the inorganic particles by stretching. As said inorganic particle, it can select suitably from well-known thru | or a usual thing, for example, the above-mentioned inorganic particle etc. are mentioned. The shape of the inorganic particles is not particularly limited, and a flat plate shape, a granular shape, or the like can be used. The said inorganic particle may be used independently and may mix and use 2 or more types.

  The porous film B may contain various additives such as a colorant, an antioxidant, an antioxidant, an ultraviolet absorber, a flame retardant, and a stabilizer.

  Although the said porous film B is not specifically limited, For example, it can be manufactured by making porous by extending | stretching an unstretched film. The porous film B can be manufactured, for example, by a melt film forming method (T-die method, inflation method). Specifically, for example, the polyester resin, the inorganic particles, and the like are mixed and dispersed in a biaxial kneading extruder to produce raw material pellets, and then melt-extruded in a monoaxial extruder to produce an unstretched film. The unstretched film is made porous by stretching. When a porous film is used as a laminated film, a coextrusion method can be preferably used. The porous film B may be subjected to various treatments such as back treatment and antistatic treatment as necessary.

  Although the thickness of the said base material B is not specifically limited, From a viewpoint of workability and a feel, for example, 30-200 micrometers is preferable, More preferably, it is 30-150 micrometers, More preferably, it is 30-100 micrometers.

Although the fragile air permeability of the base material B is not particularly limited, it is preferably, for example, 300 to 5000 cc / cm ² / sec, more preferably 1000 to 3000 cc / cm ² / sec from the viewpoint of air permeability.

  The urethane pressure-sensitive adhesive sheet of the present invention may be a single-sided pressure-sensitive adhesive sheet having a fibrous pressure-sensitive adhesive layer B on one surface of the substrate B, or a fibrous pressure-sensitive adhesive layer on both surfaces of the substrate B. A double-sided pressure-sensitive adhesive sheet having B or a fibrous pressure-sensitive adhesive layer B on one surface of the substrate B, and a fibrous pressure-sensitive adhesive layer other than the fibrous pressure-sensitive adhesive layer B (for example, fibrous pressure-sensitive adhesive layer) on the other surface Double-sided pressure-sensitive adhesive sheet having adhesive layer A, fibrous pressure-sensitive adhesive layer C, fibrous pressure-sensitive adhesive layer A, and fibrous pressure-sensitive adhesive layer other than fibrous pressure-sensitive adhesive layer C) may be used. When the urethane type adhesive sheet of this invention is a double-sided adhesive sheet, the double-sided adhesive sheet which has the fibrous adhesive layer B on both surfaces of the base material B is preferable from a viewpoint of productivity.

  Although the manufacturing method of the urethane type adhesive sheet of this invention can use a well-known thru | or usual manufacturing method, It does not specifically limit, For example, the fibrous adhesive layer B is provided in the at least one surface of the said base material B. The method etc. are mentioned. Examples of the method for providing the fibrous pressure-sensitive adhesive layer B include a method for providing the fibrous pressure-sensitive adhesive layer B.

More specifically, a hot-melt ultraviolet curable acrylic pressure-sensitive adhesive is spray-coated on at least one surface of the substrate B including the nonwoven fabric B and / or the porous film B to form the fibrous pressure-sensitive adhesive layer B. step, illuminance fibrous adhesive layer B 120~240mW / cm ² (preferably 200~240mW / cm ^2), the gel fraction of the fibrous pressure-sensitive adhesive layer B was irradiated with ultraviolet light quantity 300~500mJ / cm ² The manufacturing method including the process etc. which make 35-90% is mentioned. The manufacturing method of the urethane type adhesive sheet of this invention may include all the said processes, and may include one part.

  Although the thickness (total thickness) of the urethane type adhesive sheet of this invention is not specifically limited, 50-200 micrometers is preferable, More preferably, it is 70-150 micrometers. When the thickness is 200 μm or less, flexibility and texture can be improved. When the thickness is 50 μm or more, wrinkles are hardly formed and the productivity is excellent. The thickness of the pressure-sensitive adhesive sheet does not include the thickness of the separator.

The fragile air permeability of the urethane-based pressure-sensitive adhesive sheet of the present invention is not particularly limited, but is preferably 30 to 500 cc / cm ² / sec, more preferably 100 to 300 cc / cm ² / sec, from the viewpoint of air permeability. .

[SIS pressure-sensitive adhesive sheet of the present invention]
The SIS pressure-sensitive adhesive sheet of the present invention is a fibrous pressure-sensitive adhesive layer formed by spray-coating a hot-melt SIS pressure-sensitive adhesive on at least one surface of a substrate C including a nonwoven fabric and / or a porous film. It has a fibrous pressure-sensitive adhesive layer C).

(Fibrous pressure-sensitive adhesive layer C)
The hot-melt type SIS pressure-sensitive adhesive is composed of a SIS block copolymer, a tackifier that is solid at a temperature of 23 ° C. (sometimes referred to as a tackifier A), and a tackifier that is liquid at a temperature of 23 ° C. Sometimes referred to as Agent B). The hot melt type SIS pressure-sensitive adhesive may further contain an additive as necessary.

  The SIS block copolymer is not particularly limited. For example, a block copolymer comprising a styrene polymer block of a styrene compound such as styrene or methylstyrene and an isoprene polymer block of an isoprene compound such as isoprene. A polymer etc. are mentioned. The SIS block copolymer may contain a polymer block other than the styrene polymer block and the isoprene polymer block as necessary. The styrene polymer block contained in the SIS block copolymer may be one type or two or more types. 1 type may be sufficient as the said isoprene-type polymer block contained in the said SIS block copolymer, and 2 or more types may be sufficient as it. The SIS block copolymers can be used alone or in combination of two or more.

  The content of styrene in the monomer component constituting the SIS block copolymer is not particularly limited. For example, the content of styrene is 5 to 40 with respect to the total amount of monomer components (100% by weight) constituting the SIS block copolymer. % By weight is preferable, more preferably 10 to 30% by weight, still more preferably 15 to 25% by weight. In other words, the content of the structural unit (structural unit) derived from styrene in the SIS block copolymer (100% by weight) is not particularly limited. For example, a monomer component constituting the SIS block copolymer 5-40 weight% is preferable with respect to the whole quantity (100 weight%), More preferably, it is 10-30 weight%, More preferably, it is 15-25 weight%. By setting the styrene content to 5% by weight or more, the cohesive force of the pressure-sensitive adhesive layer becomes high, and the pressure-sensitive adhesive layer becomes more difficult to flow. By setting the styrene content to 40% by weight or less, sufficient adhesion (tackiness) can be obtained.

  The content of the SIS block copolymer in the hot melt type SIS pressure-sensitive adhesive is not particularly limited. For example, it is 20 to 99% by weight with respect to the total amount of the hot melt type SIS pressure sensitive adhesive (100% by weight). Is more preferable, more preferably 40 to 99% by weight, still more preferably 50 to 90% by weight. By setting the content of the SIS block copolymer to 20% by weight or more, the cohesive force of the pressure-sensitive adhesive can be maintained. By making the content of the SIS block copolymer 99% by weight or less, the coating property is excellent.

  The weight average molecular weight (Mw) of the SIS block copolymer is not particularly limited, but the coating property of the adhesive increases, the applied adhesive becomes more difficult to flow, and the strength of the formed fibrous adhesive layer is increased. From the viewpoint of improving, for example, 100,000 to 300,000 is preferable. The weight average molecular weight of the SIS block copolymer can be controlled by the monomer concentration and the like in addition to the temperature and time during the polymerization.

  The SIS block copolymer is not particularly limited, but from the viewpoint that the pressure-sensitive adhesive becomes more difficult to flow even when high temperature or pressure is applied, the amount of SI diblock is a monomer constituting the SIS block copolymer. It is preferable that it is 10-35 weight% with respect to the component whole quantity (100 weight%).

  Commercially available products can be used as the SIS block copolymer. For example, from the viewpoint of low melt viscosity and high cohesive force, the trade name “Quintac 3280” (manufactured by Nippon Zeon Co., Ltd.), product The name “Quintac 3450” (manufactured by Nippon Zeon Co., Ltd.) is exemplified.

  When the above-mentioned hot melt type SIS pressure-sensitive adhesive contains a tackifier A (tackifier resin A), the tackiness is improved. The tackifier A is not particularly limited. For example, among the terpene tackifier resin, phenol tackifier resin, rosin tackifier resin, petroleum tackifier resin, etc. Terpene-based tackifier resin solid at 23 ° C., phenol-based tackifier resin solid at 23 ° C., rosin-based tackifier resin solid at 23 ° C., petroleum-based tackifier resin solid at 23 ° C. . Among them, a terpene tackifying resin that is solid at a temperature of 23 ° C. is preferable from the viewpoint of excellent compatibility with the SIS block copolymer. The tackifier A can be used alone or in combination of two or more.

  The terpene-based tackifier resin in the tackifier A is not particularly limited. For example, terpene resins such as α-pinene polymer, β-pinene polymer, and dipentene polymer, and these terpene resins are modified. Modified terpene resins (for example, phenol modified, aromatic modified, hydrogenated modified, hydrocarbon modified, etc.) (for example, phenol modified terpene resin, aromatic modified terpene resin, hydrogenated modified terpene resin, hydrocarbon modified terpene resin) Resins, etc.) are solid at a temperature of 23 ° C. Among these, from the viewpoint of being hardly thermally deteriorated even in a high temperature atmosphere, a hydrogenated modified terpene resin that is solid at a temperature of 23 ° C. and an aromatic modified terpene resin that is solid at a temperature of 23 ° C. are preferable. In particular, from the viewpoint that the compatibility with the SIS block copolymer is further excellent, the viscosity can be adjusted to an appropriate range, and the low-temperature adhesiveness is excellent, a hydrogenated modified terpene resin that is solid at a temperature of 23 ° C. It is preferable to contain both the aromatic modified terpene resin that is solid at a temperature of 23 ° C.

  The softening temperature (softening point) of the terpene tackifying resin that is solid at a temperature of 23 ° C. in the tackifier A is not particularly limited, but is preferably 80 to 130 ° C., and more preferably 90 to 120 ° C., for example. When the softening temperature is 80 ° C. or higher, the pressure-sensitive adhesive becomes more difficult to flow. When the softening temperature is 130 ° C. or lower, the coating property is excellent. In addition, the said softening temperature means the Vicat softening point measured based on JISK7206.

  The terpene-based tackifying resin that is solid at a temperature of 23 ° C. in the tackifier A is not particularly limited, but from the viewpoint that the pressure-sensitive adhesive hardly flows even when a high temperature or pressure is applied, for example, the softening point is 80. It is preferable that the temperature is at least ° C.

  Examples of the phenolic tackifier resin in the tackifier A include condensates of various phenols (eg, phenol, m-cresol, 3,5-xylenol, p-alkylphenol, resorcin, etc.) and formaldehyde (eg, alkylphenol type). Resin, xylene formaldehyde resin, etc.), resole obtained by addition reaction of the above phenols and formaldehyde with an alkali catalyst, novolak obtained by condensation reaction of the above phenols with formaldehyde with an acid catalyst, and rosins (not yet used). Among rosin-modified phenolic resins obtained by adding phenol to an acid catalyst and heat-polymerizing a modified rosin, modified rosin, various rosin derivatives, etc.), those solid at 23 ° C. are exemplified.

  Examples of the rosin-based tackifying resin in the tackifier A include, for example, unmodified rosin (raw rosin) such as gum rosin, wood rosin, tall oil rosin, and hydrogenation, disproportionation, polymerization, etc. of these unmodified rosins. Modified rosins modified by the above (hydrogenated rosin, disproportionated rosin, polymerized rosin, other chemically modified rosins, etc.) and various rosin derivatives, etc., which are solid at a temperature of 23 ° C. Can be mentioned.

  Examples of the petroleum-based tackifier resin in the tackifier A include, for example, aromatic petroleum resins, aliphatic petroleum resins, alicyclic petroleum resins (aliphatic cyclic petroleum resins), and aliphatic / aromatic petroleum resins. Among known petroleum resins such as aliphatic / alicyclic petroleum resins, hydrogenated petroleum resins, coumarone resins, coumarone indene resins and the like, those that are solid at a temperature of 23 ° C. can be mentioned.

  The content of tackifier A in the hot melt type SIS adhesive is 20 to 150 parts by weight, preferably 20 to 100 parts by weight, more preferably 100 parts by weight of the SIS block copolymer. 50 to 80 parts by weight. By making the content 20 parts by weight or more, the pressure-sensitive adhesive becomes difficult to flow. By setting the content to 150 parts by weight or less, low temperature characteristics can be secured.

  Commercially available products can be used as the tackifier A. For example, from the viewpoint of reducing cohesive force at high temperatures while reducing the viscosity, the trade name “Clearon M105” (manufactured by Yasuhara Chemical Co., Ltd., Hydrogenated modified terpene resin), trade name “Clearon K4090” (manufactured by Yasuhara Chemical Co., Ltd.) and the like.

  The tackifier A is a solid at a temperature of 23 ° C. The melting point of the tackifier A is not particularly limited, but is preferably higher than 23 ° C., and more preferably 90 ° C. or higher.

  When tackifier B (tackifier resin B) is included in the hot melt type SIS adhesive, the melt viscosity decreases. The tackifier B is not particularly limited as long as it is liquid (liquid) at a temperature of 23 ° C., and examples thereof include a terpene tackifier resin, a phenol tackifier resin, a rosin tackifier resin, and a petroleum tackifier resin. Of these, liquid at a temperature of 23 ° C. (terpene tackifying resin that is liquid at a temperature of 23 ° C., phenolic tackifying resin that is liquid at a temperature of 23 ° C., rosin tackifying resin that is liquid at a temperature of 23 ° C., and at a temperature of 23 ° C. Liquid petroleum-based tackifying resins), petroleum oils such as paraffin oil, process oil, naphthenic oil, castor oil, linseed oil, soybean oil, di-2-ethylhexyl phthalate (DOP), dibutyl phthalate (DBP), Examples thereof include organic acid esters such as phosphate esters, higher fatty acid esters, and alkyl sulfonate esters. Tackifier B can be used alone or in combination of two or more.

  The content of tackifier B in the hot melt type SIS pressure-sensitive adhesive is 20 to 90 parts by weight, preferably 20 to 80 parts by weight, more preferably 100 parts by weight of the SIS block copolymer. 20 to 60 parts by weight. By making the content 20 parts by weight or more, coatability is improved. When the content is 90 parts by weight or less, the fluidity is lowered. In particular, even after storage at a high temperature or when pressure is applied, the pressure-sensitive adhesive layer is difficult to flow and the air permeability is difficult to change.

  Commercially available products can be used as the tackifier B, and examples thereof include a trade name “YS Resin TO-L” (manufactured by Yasuhara Chemical Co., Ltd., aromatic modified terpene resin).

When the hot melt type SIS pressure-sensitive adhesive contains only the tackifier A, the melt viscosity becomes high and the coatability may be deteriorated. When both tackifier A and tackifier B are included, the melt viscosity can be adjusted to an appropriate range, and the low-temperature adhesiveness is also excellent. Therefore, the hot-melt type SIS pressure-sensitive adhesive is not particularly limited, but preferably includes both the tackifier A and the tackifier B.
The total amount of tackifier A and tackifier B in the hot melt type SIS pressure-sensitive adhesive is not particularly limited. For example, 40 to 240 parts by weight is preferable with respect to 100 parts by weight of the SIS block copolymer. More preferably, it is 50-200 weight part, More preferably, it is 50-150 weight part.

  When the hot melt type SIS adhesive contains both the tackifier A and the tackifier B, the air permeability is less likely to change even after storage at a high temperature or when pressure is applied. From the viewpoint, the proportion of tackifier B is less than that of tackifier A (for example, the proportion of tackifier B in the total amount of tackifier A and tackifier B is less than 50%, preferably 40%. The following is preferable.

  The additive in the hot melt type SIS pressure-sensitive adhesive is not particularly limited. For example, an antioxidant, a crosslinking agent, a polymerization initiator, a crosslinking accelerator, an anti-aging agent, a filler, a colorant, an ultraviolet absorber, Examples include chain transfer agents, plasticizers, surfactants, and antistatic agents. Of these, antioxidants are preferred.

  When an antioxidant is contained in the hot melt type SIS adhesive, the thermal stability of the adhesive is further improved. The antioxidant is not particularly limited. For example, 4-[[4,6-bis (octylthio) -1,3,5-triazin-2-yl] amino] -2,6-di-tert- Hindered phenol antioxidants having a 2,6-alkylphenol skeleton such as butylphenol (Irganox 565) and phosphite compounds such as tris (2,4-di-t-butylphenyl) phosphite (Irgaphos 168) And a mixture thereof. The said antioxidant can be used individually or in combination of 2 or more types.

  From the viewpoint of preventing primary aging and secondary aging, the above antioxidant is a hindered phenolic antioxidant having a 2,6-alkylphenol skeleton such as Irganox B612 (a mixture of Irganox 565 and Irgaphos 168) and A mixture of phosphate ester compounds is preferred.

  The content of the antioxidant in the hot-melt type SIS pressure-sensitive adhesive is not particularly limited. For example, it is preferably 0.5 to 10 parts by weight, more preferably 100 parts by weight of the SIS block copolymer. 1 to 5 parts by weight, more preferably 1 to 3 parts by weight. Thermal stability improves by making the said content into 0.5 weight part or more. By setting the content to 10 parts by weight or less, bleeding of low molecular weight compounds in the pressure-sensitive adhesive layer can be suppressed.

  The hot-melt type SIS-based pressure-sensitive adhesive is not particularly limited, but even when stored at a high temperature or when pressure is applied, it is more difficult to flow, the melt viscosity is in an appropriate range, and the adhesive strength is excellent. From the viewpoint, for example, a mixture of a SIS block copolymer, a hydrogenated modified terpene resin, an aromatic modified terpene resin, a hindered phenol antioxidant having a 2,6-alkylphenol skeleton and a phosphite compound is included. It is preferable.

  The hot-melt type SIS pressure-sensitive adhesive may be prepared by mixing, for example, the SIS block copolymer, the tackifier A, the tackifier B, the antioxidant added as necessary. it can.

  Since the hot melt type SIS pressure-sensitive adhesive can be heated and melted, a fibrous pressure-sensitive adhesive layer having excellent air permeability can be formed by spray coating or the like. Moreover, since it does not contain a solvent, it is excellent in safety.

  The fibrous pressure-sensitive adhesive layer C is formed by spraying the hot melt type SIS pressure-sensitive adhesive. That is, the method of providing the fibrous pressure-sensitive adhesive layer C is a method of spray-coating the hot melt type SIS pressure-sensitive adhesive. Although it does not specifically limit as the method of the said spray application, For example, the method of spraying and apply | coating the adhesive which was heat-melted by the curtain spray system through a hot air etc. is mentioned.

  The temperature at which the hot melt type SIS pressure-sensitive adhesive is melted (spreading temperature) when spray coating is not particularly limited, but is preferably 100 to 200 ° C or higher, more preferably 130 to 200 ° C, and still more preferably 160 to 200. ° C. When the heating and melting temperature is less than 100 ° C., the pressure-sensitive adhesive may flow after application and block the vent hole. When the heating and melting temperature exceeds 200 ° C., the adhesive is easily deteriorated due to thermal deterioration. Although it does not specifically limit as a viscosity (melting viscosity) after the fusion | melting of the said hot-melt type SIS type adhesive, For example, 6000-100000 mPa * s is preferable, More preferably, it is 8000-15000 mPa * s. By setting the viscosity after melting within the above range, a fibrous pressure-sensitive adhesive layer having an appropriate average fiber diameter can be formed. The viscosity after melting can be measured by the method described in “(1) Viscosity” in (Evaluation) described later.

  Although the air flow rate at the time of spray coating by the curtain spray method is not particularly limited, 500 to 1500 L / min is preferable, and 800 to 1200 L / min is more preferable. Moreover, although air temperature is not specifically limited, 150-250 degreeC is preferable, More preferably, it is 170-200 degreeC.

5-100 g / m < ² > is preferable and, as for the application quantity of the hot-melt type SIS type adhesive at the time of spray coating, More preferably, it is 10-50 g / m < ² >. By setting the coating amount to 5 g / m ² or more, the coating unevenness is reduced and the adhesion to the adherend is excellent. By setting the coating amount to 100 g / m ² or less, the air permeability is excellent.

  5-100 micrometers is preferable and, as for the average fiber diameter of the said fibrous adhesive layer C, More preferably, it is 10-50 micrometers. When the average fiber diameter is 5 μm or more, the adhesive strength is improved. In addition, the adhesive is less likely to scatter around when spraying, and the productivity is excellent. When the average fiber diameter is 100 μm or less, the temperature of the pressure-sensitive adhesive is hardly transmitted to the base material when spraying the pressure-sensitive adhesive, and the base material is hardly damaged. The average fiber diameter can be controlled by the melt viscosity of the pressure-sensitive adhesive, the air flow rate during spray coating (hot air flow rate), the height of the curtain spray die, the spray temperature (spray die temperature), and the like.

  The thickness of the fibrous pressure-sensitive adhesive layer C is preferably 10 to 200 μm, more preferably 30 to 150 μm, and further preferably 30 to 100 μm, from the viewpoint of tape smoothness.

(Substrate C)
The base material C includes at least one of a nonwoven fabric (nonwoven fabric C) and a porous film (porous film C). The base material C may be, for example, a single-layer base material composed of only the nonwoven fabric C or the porous film C, a laminated base material including the nonwoven fabric C, a laminated base material including the porous film C, or the nonwoven fabric C. And the laminated base material containing the porous film C may be sufficient. When the base material C is a laminated base material, in addition to the nonwoven fabric C and the porous film C, air permeable members such as paper and woven fabric may be included.

  Although it does not specifically limit as the said nonwoven fabric C, For example, the above-mentioned nonwoven fabric A etc. are mentioned. Among these, polyester nonwoven fabrics are preferable from the viewpoint of texture and breathability. The said nonwoven fabric C may be comprised from 1 type of fiber, and may be comprised combining multiple types of fiber.

Although the manufacturing method of the said nonwoven fabric C is not specifically limited, For example, a spun bond system, a spunlace system, etc. are mentioned. Among these, a nonwoven fabric (spunbond nonwoven fabric) manufactured by a spunbond method is preferable from the viewpoint of strength. In addition, the said nonwoven fabric C may have any form of a single layer and a multilayer. In the non-woven fabric C, the fiber diameter (average fiber diameter), fiber length, basis weight, etc. are not particularly limited. For example, the basis weight is preferably ²⁰ to 100 g / m ² , more preferably from the viewpoint of processability and cost. 20 to 80 g / m ² .

  Although it does not specifically limit as said porous film C, For example, the above-mentioned porous film A etc. are mentioned. Among these, a porous film composed of a polyolefin-based resin is preferable from the viewpoint of price and flexibility.

  Although it does not specifically limit as said polyolefin resin, For example, the above-mentioned polyolefin resin is mentioned. The said polyolefin resin may be used independently, and 2 or more types may be mixed and used for it.

  Although resin (for example, polyolefin resin) which constitutes the porous film C is not particularly limited, for example, inorganic particles may be included. The inorganic particles play a role of making the film porous by generating voids (pores) around the inorganic particles by stretching. As said inorganic particle, it can select suitably from well-known thru | or a usual thing, for example, the above-mentioned inorganic particle etc. are mentioned. The shape of the inorganic particles is not particularly limited, and a flat plate shape, a granular shape, or the like can be used. The said inorganic particle may be used independently and may mix and use 2 or more types.

  The porous film C may be blended with various additives such as a colorant, an antioxidant, an antioxidant, an ultraviolet absorber, a flame retardant, and a stabilizer.

  Although the said porous film C is not specifically limited, For example, it can be manufactured by making porous by extending | stretching an unstretched film. The porous film C can be produced, for example, by a melt film forming method (T-die method, inflation method). Specifically, for example, the polyester resin, the inorganic particles, and the like are mixed and dispersed in a biaxial kneading extruder to produce raw material pellets, and then melt-extruded in a monoaxial extruder to produce an unstretched film. The unstretched film is made porous by stretching. When a porous film is used as a laminated film, a coextrusion method can be preferably used. The porous film C may be subjected to various treatments such as back treatment and antistatic treatment as necessary.

  Although the thickness of the said base material C is not specifically limited, From a viewpoint of workability or a texture, 30-200 micrometers is preferable, for example, More preferably, it is 30-150 micrometers, More preferably, it is 30-100 micrometers.

Although the fragile air permeability of the substrate C is not particularly limited, it is preferably, for example, 300 to 5000 cc / cm ² / sec, more preferably 1000 to 3000 cc / cm ² / sec from the viewpoint of air permeability.

  The SIS pressure-sensitive adhesive sheet of the present invention may be a single-sided pressure-sensitive adhesive sheet having a fibrous pressure-sensitive adhesive layer C on one surface of the substrate C, or a fibrous pressure-sensitive adhesive layer on both surfaces of the substrate C. A double-sided pressure-sensitive adhesive sheet having C or a fibrous pressure-sensitive adhesive layer C on one surface of the substrate C and a fibrous pressure-sensitive adhesive layer other than the fibrous pressure-sensitive adhesive layer C (for example, fibrous pressure-sensitive adhesive layer) on the other surface Double-sided pressure-sensitive adhesive sheet having adhesive layer A, fibrous pressure-sensitive adhesive layer B, fibrous pressure-sensitive adhesive layer A, and fibrous pressure-sensitive adhesive layer other than fibrous pressure-sensitive adhesive layer B) may be used. When the SIS pressure-sensitive adhesive sheet of the present invention is a double-sided pressure-sensitive adhesive sheet, a double-sided pressure-sensitive adhesive sheet having a fibrous pressure-sensitive adhesive layer C on both surfaces of the substrate C is preferable from the viewpoint of productivity.

  The production method of the SIS pressure-sensitive adhesive sheet of the present invention can be a known or conventional production method, and is not particularly limited. For example, the fibrous pressure-sensitive adhesive layer C is provided on at least one surface of the substrate C. The method etc. are mentioned. Examples of the method of providing the fibrous pressure-sensitive adhesive layer C include a method of providing the fibrous pressure-sensitive adhesive layer C.

  More specifically, the step of forming the fibrous pressure-sensitive adhesive layer C by spray-coating the hot melt type SIS pressure-sensitive adhesive on at least one surface of the substrate C including the nonwoven fabric C and / or the porous film C, etc. The manufacturing method containing is mentioned. The manufacturing method of the SIS pressure-sensitive adhesive sheet of the present invention may include other steps.

  The thickness (total thickness) of the SIS pressure-sensitive adhesive sheet of the present invention is not particularly limited, but is preferably 50 to 200 μm, more preferably 70 to 150 μm. When the thickness is 200 μm or less, flexibility and texture can be improved. When the thickness is 50 μm or more, wrinkles are hardly formed and the productivity is excellent. The thickness of the pressure-sensitive adhesive sheet does not include the thickness of the separator.

The fragile air permeability of the SIS pressure-sensitive adhesive sheet of the present invention is not particularly limited, but is preferably 30 to 500 cc / cm ² / sec, more preferably 100 to 300 cc / cm ² / sec from the viewpoint of air permeability. .

[Separator]
The fibrous pressure-sensitive adhesive layer (fibrous pressure-sensitive adhesive layer A, fibrous pressure-sensitive adhesive layer B, fibrous pressure-sensitive adhesive layer C, etc.) in the pressure-sensitive adhesive sheet of the present invention is protected by a separator (release liner) until use. Also good. The separator is used as a protective material for the fibrous pressure-sensitive adhesive layer, and is peeled off when the pressure-sensitive adhesive sheet of the present invention is attached to an adherend. Note that the separator is not necessarily provided.

  As the separator, a conventional release paper or the like can be used, and is not particularly limited. For example, a substrate having a release agent layer, a low adhesive substrate made of a fluorine-based polymer, or a low adhesive substrate made of a nonpolar polymer. Etc. Examples of the substrate having the release agent layer include a plastic film or paper surface-treated with a release agent such as a silicone release agent, a long-chain alkyl release agent, a fluorine release agent, and a molybdenum sulfide release agent. Can be mentioned. Examples of the fluorine polymer include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, chlorofluoroethylene-vinylidene fluoride copolymer, and the like. Is mentioned. Moreover, as said nonpolar polymer, polyolefin resin (for example, polyethylene, a polypropylene, etc.) etc. are mentioned, for example. The separator can be formed by a known or common method. Further, the thickness of the separator is not particularly limited.

  In the pressure-sensitive adhesive sheet of the present invention, from the viewpoint that the pressure-sensitive adhesive layer hardly flows even at a high temperature, it is preferable that the distance by which the pressure-sensitive adhesive sheet measured in the following <Test> is shifted is less than 0.1 mm. That is, as the pressure-sensitive adhesive sheet in which the distance measured by the pressure-sensitive adhesive sheet measured in the following <Test> is less than 0.1 mm, for example, the acrylic pressure-sensitive adhesive sheet of the present invention, the urethane pressure-sensitive adhesive sheet of the present invention, A SIS pressure sensitive adhesive sheet etc. are illustrated preferably.

<Test>
At the lower end of one side of a stainless steel plate (thickness 5 mm, size: length 150 mm × width 50 mm), the adhesive area between the fibrous adhesive layer of the adhesive sheet of the present invention and the stainless steel plate is 200 mm ² (length 20 mm × width). 10 mm), and a 2 kg roller is reciprocated once for pressure bonding. Then, the adhesive sheet of the present invention and the stainless steel plate are placed so that the adhesive surface of the adhesive sheet of the present invention and the stainless steel plate are in the vertical direction, and left at 50 ° C. for 0.5 hour. A weight having a weight of 100 g is hung on a test piece with a string so as to hang down in the vertical direction, and a load of 100 gf (0.98 N) is applied. After leaving at a temperature of 50 ° C. for 120 minutes, the distance by which the pressure-sensitive adhesive sheet of the present invention is displaced is measured.

  In addition, the distance which the adhesive sheet shifted | deviated is the distance (movement distance) which the adhesive sheet shifted | deviated in the perpendicular direction, and 120 minutes pass after the upper end of the position which bonded the stainless steel plate and the adhesive sheet at the time of a measurement start. The distance to the upper end of the position where the stainless steel plate and the adhesive sheet are bonded together.

In the pressure-sensitive adhesive sheet of the present invention, from the viewpoint that the pressure-sensitive adhesive layer becomes more difficult to flow at a high temperature, the limit holding force measured in the following <Test of limit holding force> is preferably 100 g / cm ² or more. More preferably, it is 200 g / cm ² or more. The limit holding force can be controlled by the composition and content of the pressure-sensitive adhesive, the gel fraction of the pressure-sensitive adhesive layer, the conditions of the curing reaction, and the like.

<Test of limit holding force>
At the lower end of one side of a stainless steel plate (thickness 5 mm, size: length 150 mm × width 50 mm), the adhesive area between the fibrous adhesive layer of the adhesive sheet of the present invention and the stainless steel plate is 200 mm ² (length 20 mm × width). 10 mm), and a 2 kg roller is reciprocated once for pressure bonding. Then, the adhesive sheet of the present invention and the stainless steel plate are placed so that the adhesive surface of the adhesive sheet of the present invention and the stainless steel plate are in the vertical direction, and left at 50 ° C. for 0.5 hour. A weight having a weight of 100 g is hung on a test piece with a string so as to hang down in the vertical direction, and a load of 100 gf (0.98 N) is applied. After leaving at a temperature of 50 ° C. for 120 minutes, the distance by which the pressure-sensitive adhesive sheet of the present invention is displaced is measured.
When the displaced distance is less than 0.1 mm, the weight of the weight is increased by 50 g (the load is increased by 50 gf), and further left to stand at a temperature of 50 ° C. for 120 minutes. Measure. The weight (g) of the weight when the distance that the pressure-sensitive adhesive sheet of the present invention is displaced from the position where the pressure-sensitive adhesive sheet of the present invention and the stainless steel plate are first bonded is 0.1 mm or more is expressed as the pressure-sensitive adhesive of the present invention. Dividing by the bonding area (cm ² ) between the fibrous adhesive layer of the sheet and the stainless steel plate, the limit holding force (g / cm ² ) is obtained.

  In the above <Test>, the pressure-sensitive adhesive sheet of the present invention is the acrylic pressure-sensitive adhesive sheet of the present invention, the urethane pressure-sensitive adhesive sheet of the present invention, and the It may be other than the SIS-based pressure-sensitive adhesive sheet, and a hot-melt pressure-sensitive adhesive (for example, a hot-melt-type vinyl alkyl ether-based pressure-sensitive adhesive or a hot-melt-type silicone-based pressure-sensitive adhesive is applied to at least one surface of a substrate including a nonwoven fabric and / or a porous film. Adhesive, hot-melt polyester adhesive, hot-melt polyamide adhesive, hot-melt fluorine-based adhesive, hot-melt epoxy adhesive, etc.) It may be an adhesive sheet.

  Although the adhesive sheet of this invention is not specifically limited, For example, it is used suitably for uses, such as medical care, a sanitary material, a motor vehicle, a building, and household appliances.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

Example 1
SIS block copolymer [manufactured by Nippon Zeon Co., Ltd., trade name “Quintac 3280”]: 100 parts by weight of hydrogenated terpene resin [manufactured by Yashara Chemical Co., Ltd., trade name “Clearon M105”, solid at 23 ° C. Tackifier]: 60 parts by weight, aromatic modified terpene resin [manufactured by Yashara Chemical Co., Ltd., trade name “YS Resin TO-L”, tackifier liquid at 23 ° C.], 50 parts by weight, and antioxidant [BASF Japan K.K., trade name “Irganox B612”]: 1 part by weight was added and mixed to obtain a hot-melt styrene-isoprene-styrene pressure-sensitive adhesive.
The above hot-melt styrene-isoprene-styrene pressure-sensitive adhesive is melted at 180 ° C., on one side of a polyester-based spunbond nonwoven fabric [trade name “E5025” manufactured by Asahi Kasei Fibers Co., Ltd., basis weight 25 g / m ³ ]. Then, application was carried out by spray coating at an application temperature of 180 ° C. and an application amount of 30 g / m ² to form a fibrous pressure-sensitive adhesive layer having an average fiber diameter of 50 μm, thereby preparing an adhesive sheet.

Example 2
SIS block copolymer [manufactured by Nippon Zeon Co., Ltd., trade name “Quintac 3280”]: 100 parts by weight of hydrogenated terpene resin [manufactured by Yashara Chemical Co., Ltd., trade name “Clearon M105”, solid at 23 ° C. Tackifier]: 70 parts by weight, aromatic modified terpene resin [manufactured by Yasuhara Chemical Co., Ltd., trade name “YS Resin TO-L”, liquid tackifier at 23 ° C.]: 40 parts by weight, and antioxidant Agent [BASF Japan Co., Ltd., trade name “Irganox B612”]: 1 part by weight was added and mixed to obtain a hot melt styrene-isoprene-styrene adhesive.
The above hot-melt styrene-isoprene-styrene pressure-sensitive adhesive is melted at 185 ° C., on one side of a polyester-based spunbonded nonwoven fabric [manufactured by Asahi Kasei Fibers Co., Ltd., trade name “E5025”, basis weight 25 g / m ³ ]. Then, coating was performed by spray coating at a coating temperature of 185 ° C. and a coating amount of 30 g / m ² to form a fibrous pressure-sensitive adhesive layer having an average fiber diameter of 50 μm, thereby preparing a pressure-sensitive adhesive sheet.

Example 3
SIS block copolymer [manufactured by Nippon Zeon Co., Ltd., trade name “Quintac 3280”]: 100 parts by weight of hydrogenated terpene resin [manufactured by Yashara Chemical Co., Ltd., trade name “Clearon M105”, solid at 23 ° C. Tackifier]: 70 parts by weight, aromatic modified terpene resin [manufactured by Yasuhara Chemical Co., Ltd., trade name “YS Resin TO-L”, liquid tackifier at 23 ° C.]: 30 parts by weight, and antioxidant Agent [BASF Japan Co., Ltd., trade name “Irganox B612”]: 1 part by weight was added and mixed to obtain a hot melt styrene-isoprene-styrene adhesive.
The above hot-melt styrene-isoprene-styrene pressure-sensitive adhesive is melted at 200 ° C., on one side of a polyester-based spunbonded nonwoven fabric [Asahi Kasei Fibers, trade name “E5025”, basis weight 25 g / m ³ ]. Then, application was performed by spray coating at an application temperature of 200 ° C. and an application amount of 30 g / m ² to form a fibrous pressure-sensitive adhesive layer having an average fiber diameter of 50 μm, thereby preparing an adhesive sheet.

Comparative Example 1
SIS block copolymer [manufactured by Nippon Zeon Co., Ltd., trade name “Quintac 3280”]: 100 parts by weight of hydrogenated terpene resin [manufactured by Yashara Chemical Co., Ltd., trade name “Clearon M105”, solid at 23 ° C. Tackifier]: 80 parts by weight, aromatic modified terpene resin [manufactured by Yashara Chemical Co., Ltd., trade name “YS Resin TO-L”, liquid tackifier at 23 ° C.]: 100 parts by weight, and antioxidant Agent [BASF Japan Co., Ltd., trade name “Irganox B612”]: 1 part by weight was added and mixed to obtain a hot melt styrene-isoprene-styrene adhesive.
The hot-melt styrene-isoprene-styrene pressure-sensitive adhesive is melted at 170 ° C., and is coated on one side of a polyester-based spunbonded nonwoven fabric [Asahi Kasei Fibers Co., Ltd., trade name “E5025”, basis weight 25 g / m ³ ]. Then, application was carried out by spray coating at an application temperature of 170 ° C. and an application amount of 30 g / m ² to form a fibrous pressure-sensitive adhesive layer having an average fiber diameter of 50 μm, thereby preparing an adhesive sheet.

Example 4
Hot melt type UV curable acrylic adhesive [trade name “Acrymelt G-7048” manufactured by Notape Industries Co., Ltd.] was melted at 150 ° C., and polyester spunbond nonwoven fabric [Asahi Kasei Fibers Co., Ltd., product name] "E5025" on a single surface with a basis weight of 25 g / m ³ ] is applied by spray coating at a coating temperature of 150 ° C. and a coating amount of 30 g / m ² , and ultraviolet rays having an illuminance of 1200 mW / cm ² and a light amount of 300 mJ / cm ² are applied. Irradiation was performed to form a fibrous pressure-sensitive adhesive layer (gel fraction: 50%) having an average fiber diameter of 50 μm, and a pressure-sensitive adhesive sheet was produced.

Example 5
Hot melt type UV curable acrylic adhesive [trade name “Acrymelt G-7048” manufactured by Notape Industries Co., Ltd.] was melted at 150 ° C., and polyester spunbond nonwoven fabric [Asahi Kasei Fibers Co., Ltd., product name] "E5025" on a single surface with a basis weight of 25 g / m ³ ] is applied by spray coating at a coating temperature of 150 ° C. and a coating amount of 30 g / m ² , and an ultraviolet ray having an illuminance of 1200 mW / cm ² and a light amount of 350 mJ / cm ² is applied. Irradiation was performed to form a fibrous pressure-sensitive adhesive layer (gel fraction: 60%) having an average fiber diameter of 50 μm, thereby preparing a pressure-sensitive adhesive sheet.

Example 6
Hot melt type UV curable acrylic adhesive [trade name “Acrymelt G-7048” manufactured by Notape Industries Co., Ltd.] was melted at 150 ° C., and polyester spunbond nonwoven fabric [Asahi Kasei Fibers Co., Ltd., product name] "E5025" on a single surface with a basis weight of 25 g / m ³ ] is applied by spray coating at a coating temperature of 150 ° C. and a coating amount of 10 g / m ² , and an ultraviolet ray having an illuminance of 1200 mW / cm ² and a light amount of 350 mJ / cm ² is applied. Irradiation was performed to form a fibrous pressure-sensitive adhesive layer (gel fraction: 60%) having an average fiber diameter of 50 μm, thereby preparing a pressure-sensitive adhesive sheet.

Comparative Example 2
Hot melt type UV curable acrylic adhesive [trade name “Acrymelt G-7048” manufactured by Notape Industries Co., Ltd.] was melted at 150 ° C., and polyester spunbond nonwoven fabric [Asahi Kasei Fibers Co., Ltd., product name] "E5025" on a single surface with a basis weight of 25 g / m ³ ] is applied by spray coating at a coating temperature of 150 ° C. and a coating amount of 30 g / m ² , and an ultraviolet ray having an illuminance of 1200 mW / cm ² and a light amount of 200 mJ / cm ² is applied. Irradiation was performed to form a fibrous pressure-sensitive adhesive layer (gel fraction: 30%) having an average fiber diameter of 50 μm, and a pressure-sensitive adhesive sheet was produced.

[Evaluation]
The following measurement or evaluation was performed about the adhesive sheet obtained by the Example and the comparative example. The evaluation results are shown in Table 1.

(1) Viscosity Viscosity (viscosity at heating and melting temperature) when the hot-melt pressure-sensitive adhesive was melted in Examples and Comparative Examples was measured. The viscosity at the heating and melting temperature was measured using a Brookfield viscometer manufactured by Brookfield as a viscosity measuring device under measurement conditions of a spindle number 28 and a rotation speed of 5 rpm. The measured viscosity at heating and melting temperature (mPa · s) is shown in the column of “viscosity at heating and melting temperature (mPa · s)” in Table 1.
In the measurement of the viscosity in Examples and Comparative Examples, the heating and melting temperature is the temperature at which the pressure-sensitive adhesive is applied (application temperature).

(2) Frazier permeability The pressure-sensitive adhesive sheets obtained in Examples and Comparative Examples were pressurized at a temperature of 60 ° C. and a pressure of 0.4 MPa for 10 seconds, or left at a temperature of 40 ° C. for 6 months. A pressure-sensitive adhesive sheet immediately after production (initial pressure-sensitive adhesive sheet), a pressure-sensitive adhesive sheet (pressure-sensitive adhesive sheet after pressurization for 10 seconds at a temperature of 60 ° C. and a pressure of 0.4 MPa), and a pressure-sensitive adhesive sheet left to stand for 6 months at a temperature of 40 ° C. About (adhesive sheet after high temperature storage), the fragile air permeability was measured according to JIS L 1096.
The fragile air permeability (cc / cm ² / sec) of the initial pressure-sensitive adhesive sheet, the pressure-sensitive adhesive sheet after pressurization, and storage at high temperature is shown in Table 1, “Fragile air permeability (cc / cm ² / sec) initial”, “Fragile The air permeability (cc / cm ² / sec) after pressurization ”and“ Fragile air permeability (cc / cm ² / sec) after high temperature storage ”are shown in the columns.
The pressure-sensitive adhesive sheet after high-temperature storage has a change width of 0 to 10 cc / cm ² / sec of the fragile air-permeability of the pressure-sensitive adhesive sheet after high-temperature storage compared to the initial fragile air-permeability (when there is no change). "Excellent (◎)" when 10 cc / cm ² / sec is exceeded and 20 cc / cm ² / sec or less is "good", and when 20 cc / cm ² / sec is exceeded, "inferior (x)""The air permeability was evaluated. The air permeability evaluation of the pressure-sensitive adhesive sheet after high-temperature storage is shown in the column of “After air permeability high-temperature storage” in Table 1.

(3) Holding power A sheet piece (20 mm × 10 mm sheet piece) having a length of 20 mm and a width of 10 mm was cut out from the pressure-sensitive adhesive sheets obtained in Examples and Comparative Examples to prepare test pieces. The test piece is attached to the lower end of one side of a stainless steel plate (thickness 1.5 mm, size: length 125 mm × width 50 mm) with a bonding area between the fibrous adhesive layer of the test piece and the stainless steel plate of 200 mm ² (long (20 mm wide × 10 mm wide) and bonded by reciprocating a 2 kg roller once. Then, it was left at 50 ° C. for 0.5 hour. After that, the test piece and the stainless steel plate are installed so that the bonding surface of the fibrous adhesive layer of the test piece and the stainless steel plate is in the vertical direction, and the weight of 100 g is tested with the string so as to hang down in the vertical direction. It hung on a piece and applied a load of 100 gf (0.98 N). After allowing to stand at a temperature of 50 ° C. for 120 minutes, the distance by which the test piece shifted was measured. In addition, the distance which the test piece shifted | deviated is the distance (movement distance) which shifted | deviated to the vertical direction of the test piece, and the stainless steel after 120 minutes passed from the upper end of the position which bonded the stainless plate and the test piece at the time of a measurement start The distance to the upper end of the position where the plate and the test piece are bonded together.
The distance of displacement of the test piece is shown in the column of “Distance in which holding force adhesive sheet is displaced (mm)” in Table 1. In addition, the adhesive sheet was evaluated for the holding power of the adhesive sheet as “excellent (◯)” when the distance of the adhesive sheet was less than 0.1 mm and “inferior (×)” when the distance shifted by 0.1 mm or more. It is shown in the column of “Retention force evaluation” in Table 1.

  As is clear from Table 1, the pressure-sensitive adhesive sheets (Examples 1 to 6) of the present invention have a uniform air permeability after pressurization and after high-temperature storage with little change in air permeability immediately after production. It was. In addition, the hot melt type SIS pressure-sensitive adhesive of Example 3 had a high viscosity at the melting temperature, and had a limit viscosity that could be applied by spraying.

Claims (3)

  It is formed by spraying a hot-melt UV curable acrylic pressure-sensitive adhesive or hot-melt UV curable urethane pressure-sensitive adhesive on at least one surface of a substrate including a nonwoven fabric and / or a porous film, and then irradiating with ultraviolet light. A pressure-sensitive adhesive sheet comprising a fibrous pressure-sensitive adhesive layer having a gel fraction of 35 to 90%.   20 to 150 parts by weight of a solid tackifier at a temperature of 23 ° C. with respect to 100 parts by weight of a styrene-isoprene-styrene block copolymer on at least one surface of a substrate including a nonwoven fabric and / or a porous film, A pressure-sensitive adhesive sheet comprising a fibrous pressure-sensitive adhesive layer formed by spraying a hot-melt styrene-isoprene-styrene pressure-sensitive adhesive containing 20 to 90 parts by weight of a liquid tackifier at a temperature of 23 ° C. A pressure-sensitive adhesive sheet having a fibrous pressure-sensitive adhesive layer formed by spray-coating a hot melt pressure-sensitive adhesive on at least one surface of a substrate including a nonwoven fabric and / or a porous film, and measured in the following test The pressure-sensitive adhesive sheet characterized in that the displaced distance is less than 0.1 mm.
Test: Bonded to the lower end of one side of the stainless steel plate so that the adhesive area between the fibrous pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet and the stainless steel plate is 200 mm ² (length 20 mm × width 10 mm). Reciprocate and crimp. Thereafter, the adhesive sheet and the stainless steel plate are placed so that the adhesive sheet and the stainless steel plate are attached in a vertical direction at 50 ° C. for 0.5 hours, and the adhesive sheet is weighted. A weight of 100 g is hung so as to hang down in the vertical direction, and after standing at a temperature of 50 ° C. for 120 minutes, the distance by which the pressure-sensitive adhesive sheet is displaced is measured.