JP2015218326A - Pressure sensitive adhesive sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pressure sensitive adhesive sheet capable of avoiding layer separation even after a heat treatment (specifically, a heat pressure treatment).SOLUTION: A pressure sensitive adhesive sheet includes an irregularity layer, a base material and an adhesive layer. The irregularity layer is disposed on one surface side of the base material. The adhesive layer is disposed on the other surface side of the base material. The irregularity layer has arithmetic average roughness (Ra) of 0.1 μm or more on a surface thereof. Glass-transition temperature of the irregularity layer is preferably 20°C or higher.

Description

  The present invention relates to an adhesive sheet.

  In product manufacturing including the process of transporting products (including raw materials, semi-finished products, and work-in-progress products) on a transport jig, barcodes etc. were printed from the viewpoint of product management during manufacturing and product traceability after manufacturing. The product may be managed by attaching an adhesive sheet (adhesive label) to the product. As such an adhesive label, an adhesive label having heat resistance (Patent Document 1) is known.

Japanese Patent Laid-Open No. 62-198490

  However, when such an adhesive label is used, the surface layer (barcode printing layer etc.) of the adhesive label may adhere to the conveying jig and the surface layer of the adhesive label may be peeled off.

Examples of the product manufacturing including the step of transporting the product on the transport jig include the manufacture of an electronic circuit board. An electronic circuit board is manufactured through the following processes, for example (FIG. 1).
i) A pressure-sensitive adhesive label 15 for product management (for example, pressure-sensitive adhesive layer 11, base material 12, print receiving layer 13, pressure-sensitive adhesive label 15 having print layer 14, etc.), pressure-sensitive adhesive layer 11 of pressure-sensitive adhesive label 15 and substrate 16 Affix it so that it touches. (FIG. 1 (a)).
ii) The substrate 16 is placed on the transport jig 17 so that the printed layer 14 of the adhesive label 15 and the transport jig 17 used for manufacturing the electronic circuit board are in contact with each other (FIG. 1A).
iii) The substrate 16 is transported to the flux spraying device, the flux is sprayed on the substrate 16, and the flux layer 18 is provided (FIG. 1B).
iv) The substrate 16 is transported to a soldering apparatus and soldered to the flux layer 18 (FIG. 1 (c)).
v) The substrate 16 is transported to a heating device, and the solder 19 is fixed by heating (for example, heating at 260 ° C. for 1 minute) (FIG. 1D).
vi) The substrate 16 is lowered from the transfer jig 17 (FIG. 1 (e)).

  When a conventional adhesive sheet (adhesive label) is used in the electronic circuit board manufacturing process described above, when the substrate is unloaded from the transport jig, a part or all of the printed layer and the print receiving layer of the adhesive label are placed on the transport jig. Productivity may decrease due to the remaining (peeling) (sometimes referred to as “layer peeling”), disappearance of the label pattern of the pressure-sensitive adhesive label, contamination of the conveying jig, and the like.

  There are various processes in manufacturing a product including a process of placing a product on a transport jig and transporting the product. The inventors of the present invention have studied the cause of delamination, and as a result, even if momentary force is applied, delamination does not occur, but when a load is applied continuously (for example, when left on a weight) It was found that slight peeling occurred. As a result of further investigation, it was found that delamination occurred significantly by applying a continuous load under heating conditions.

  Through such a detailed study, the present inventors have found that a problem of layer peeling occurs in a product manufactured through a process including heat treatment, in particular, a product manufactured through a process of heating under a certain pressure. It was found that layer peeling occurred remarkably.

  The peel-off of the adhesive label is not limited to the production of an electronic circuit board, but is observed during the production of a product produced through a process including heat treatment.

  Accordingly, an object of the present invention is to provide a pressure-sensitive adhesive sheet that hardly undergoes layer peeling even after being subjected to heat treatment (particularly heat-pressing treatment).

  Therefore, as a result of intensive studies by the present inventors, in order to solve the above problems, the layer peeling is performed for the purpose of improving the heat resistance of the layer causing the layer peeling and improving the adhesion between the layer causing the layer peeling and the substrate. It has been found that it is particularly effective to reduce the contact area of the layer causing the layer peeling to the conveying jig rather than changing the composition of the layer causing the layer peeling. And it discovered that the said problem could be solved by using the adhesive sheet which has a specific structure and arithmetic mean roughness (Ra) of at least one surface is 0.1 micrometer or more, and completed this invention.

  That is, the present invention is a pressure-sensitive adhesive sheet having a concavo-convex layer, a base material, and a pressure-sensitive adhesive layer, wherein the concavo-convex layer is provided on one surface side of the base material, and the pressure-sensitive adhesive layer is the other side of the base material. The pressure-sensitive adhesive sheet is characterized in that the average roughness (Ra) of the surface of the concavo-convex layer is 0.1 μm or more.

  The concavo-convex layer preferably has a glass transition temperature of 20 ° C. or higher.

  It is preferable that the water contact angle on the surface of the uneven layer is 85 ° or less.

  It is preferable that the uneven layer contains at least one binder resin selected from the group consisting of polyester resins, acrylic urethane resins, acrylic resins, and aramids.

  The glass transition temperature of the substrate is preferably 20 ° C. or higher.

  The water contact angle on the substrate surface is preferably 85 ° or less.

  The substrate is preferably a polyethylene terephthalate film, a polyethylene naphthalate film, or a polyimide film.

  It is preferable that inorganic particles are contained in the uneven layer.

  The average particle diameter of the inorganic particles is preferably 0.05 μm or more.

The curl in the following test is preferably 30 mm or less.
(test)
The pressure-sensitive adhesive layer surface of the pressure-sensitive adhesive sheet piece (length 100 mm, width 100 mm) is subjected to powder treatment to eliminate stickiness, and the pressure-sensitive adhesive layer surface of the pressure-sensitive adhesive sheet piece and the surface of the slide glass are in contact with each other. Is placed on a glass slide to prepare a sample.
In the above sample, the distance between the apex (4 apexes) of the pressure-sensitive adhesive layer surface of the pressure-sensitive adhesive sheet piece and the slide glass surface is measured, and the average of the four values is defined as “curl before heating” (mm). After that, the sample is put in a hot air dryer and heated at a temperature of 260 ° C. for 3 minutes, and the heated sample is also measured for the distance between the apex (4 apexes) of the adhesive layer surface of the adhesive sheet piece and the slide glass surface. The average value of the four values is defined as “curl after heating” (mm). Then, “curl” (mm) is calculated from the following calculation formula.
{Curl (mm)} = {Curl after heating (mm)}-{Curl before heating (mm)}

  The pressure-sensitive adhesive sheet of the present invention is preferably a pressure-sensitive adhesive sheet for printing used by being attached to an electronic circuit board.

  Furthermore, the present invention provides a pressure-sensitive adhesive label comprising the pressure-sensitive adhesive sheet, and having a printed layer on at least a part of a surface having an arithmetic average roughness (Ra) of the concavo-convex layer of 0.1 μm or more. .

  Since the pressure-sensitive adhesive sheet of the present invention has the above-described configuration, even if it undergoes heat treatment (particularly heat-pressure treatment), layer peeling is unlikely to occur.

FIG. 1 is a schematic cross-sectional view showing an example of a manufacturing process of an electronic circuit board. FIG. 2 is an explanatory view (cross-sectional view) for evaluating the curling property.

[Adhesive sheet]
The pressure-sensitive adhesive sheet of the present invention has at least an uneven layer, a substrate, and a pressure-sensitive adhesive layer. In the pressure-sensitive adhesive sheet of the present invention, the uneven layer is provided on one surface side of the substrate, and the pressure-sensitive adhesive is provided on the other surface side of the substrate (the surface side opposite to the surface on which the uneven layer is provided). It is a single-sided pressure-sensitive adhesive sheet in which a layer is provided and the concavo-convex layer and the pressure-sensitive adhesive layer are used as surface layers. The pressure-sensitive adhesive layer surface may be protected by a separator (release liner). In addition, another layer (for example, an undercoat layer) may be provided between the uneven layer and the base material and between the base material and the pressure-sensitive adhesive layer as long as the effects of the present invention are not impaired.

Examples of the pressure-sensitive adhesive sheet of the present invention include a concavo-convex layer / base material / pressure-sensitive adhesive layer (a pressure-sensitive adhesive sheet comprising three layers of a concavo-convex layer, a base material and a pressure-sensitive adhesive layer), and a concavo-convex layer / base material / pressure-sensitive adhesive layer / separator ( Examples of the pressure-sensitive adhesive sheet include a concave-convex layer, a base material, a pressure-sensitive adhesive layer, and a pressure-sensitive adhesive sheet composed only of a separator.
In this specification, “adhesive sheet” includes the meaning of “adhesive tape”. That is, the pressure-sensitive adhesive sheet of the present invention may be a pressure-sensitive adhesive tape having a tape-like form.
Moreover, in addition to reducing the contact area between the adherend and one surface of the pressure-sensitive adhesive sheet, the pressure-sensitive adhesive sheet of the present invention is less prone to peeling off by changing the composition of each layer of the pressure-sensitive adhesive sheet.

(Uneven layer)
The concavo-convex layer is a layer having an arithmetic average roughness (Ra) of at least one surface of 0.1 μm or more. The pressure-sensitive adhesive sheet of the present invention is a pressure-sensitive adhesive sheet having a surface on which the arithmetic average roughness (Ra) of the uneven layer is 0.1 μm or more as one surface.

  Although the said uneven | corrugated layer is not specifically limited, For example, it is preferable that binder resin is included. The uneven layer may further contain inorganic particles, a curing agent, a crosslinking agent, and other additives.

The binder resin in the uneven layer is not particularly limited. For example, polyimide, polyether ether ketone, polyether sulfone, polyether imide, polysulfone, polyphenylene sulfide, polyamide imide, polyester imide, non-aromatic polyamide, paraban acid Resin, fluorine resin, epoxy resin, polyester resin, acrylic resin, acrylic urethane resin, aramid, hydrocarbon resin, vinyl resin, acetal resin, styrene resin, polyurethane resin, rubber resin , Alkyd resins, fiber-based resins, and the like. Among them, a group consisting of polyester resins, acrylic resins, acrylic urethane resins, and aramids from the viewpoint of being familiar with the base material (especially polyimide film), less likely to be peeled off, and easy to provide a printing layer such as a barcode. At least one resin selected from the above is preferred. In particular, a polyester resin is preferable from the viewpoint of printability and the adhesiveness to the polyimide film. From the viewpoint of excellent heat resistance and solvent resistance, aramid (particularly, meta-aramid obtained by cocondensation polymerization from m-phenylenediamine and isophthalic acid chloride) is preferable. The binder resin may be used alone or in combination of two or more.
Polyethylene resins are not preferred because they may cause layer peeling even if the arithmetic average roughness (Ra) of the surface is 0.1 μm or more.

The glass transition temperature (Tg) of the binder resin in the concavo-convex layer is not particularly limited, but the concavo-convex shape of the concavo-convex layer is not limited even after heating (for example, after heating at a temperature of 230 to 350 ° C. for a time of 0.1 to 30 minutes). From the viewpoint of being easily maintained, for example, 10 ° C or higher is preferable, more preferably 20 ° C or higher, and further preferably 50 ° C or higher. Although the upper limit of the glass transition temperature (Tg) of the binder resin in the uneven layer is not particularly limited, for example, 300 ° C is preferable, more preferably 250 ° C, still more preferably 200 ° C, and particularly preferably 100 ° C. In addition, the glass transition temperature in this specification means the glass transition temperature measured with the following measuring methods.
(Measurement method of glass transition temperature)
About 1 to 2 mg of a sample (for example, binder resin) is weighed in an open cell made of aluminum, and 50 ml / min using a temperature-modulated DSC (trade name “Q-2000”, manufactured by TA Instruments Inc.). Under a nitrogen atmosphere, a reversing heat flow (specific heat component) behavior of a sample (for example, a binder resin) is obtained at a temperature rising rate of 10 ° C./min. Referring to JIS-K-7121, the low temperature side baseline of the obtained Reversing Heat Flow and the straight line that is equidistant from the straight line extending the high temperature side base line, and the stepwise change of the glass transition The temperature at the point where the curve of the part intersects is defined as the glass transition temperature (Tg) of the sample (for example, binder resin). In addition, when a sample decomposes | disassembles before glass transition, let the decomposed temperature be a glass transition temperature.

  Examples of the polyester resin include trade name “Byron 29SS” (manufactured by Toyobo Co., Ltd.), trade name “S-140” (manufactured by Takamatsu Yushi Co., Ltd.), trade name “TP-220” (Nippon Synthetic Chemical). Kogyo Co., Ltd.). Examples of the acrylic resin include a trade name “A-817” (manufactured by DIC Corporation), a trade name “A-814” (manufactured by DIC Corporation), and a trade name “A-829” (DIC Corporation). Manufactured). Examples of the acrylic urethane-based resin include trade name “UV-3610ID80” (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), trade name “HY-364” (manufactured by DIC Corporation), and the like. Examples of the aramid include a trade name “Conex” (manufactured by Teijin Ltd.), a trade name “255-A” (manufactured by T & K TOKA Corp.), and the like.

  The content of the binder resin in the concavo-convex layer is not particularly limited. For example, the content is 50% by weight with respect to the entire concavo-convex layer (or the total coating liquid used when forming the concavo-convex layer) (100% by weight). The above is preferable, more preferably 70% by weight or more, and still more preferably 75% by weight or more. When content of binder resin is the said range, it is excellent in heat resistance and it becomes easy to maintain the uneven | corrugated shape on the uneven | corrugated layer surface.

The inorganic particles in the concavo-convex layer are not particularly limited. For example, ceramic powder such as titania, silicon carbide, silicon nitride, boron nitride, alumina, zirconia, silicon oxide, barium titanate; calcium carbonate, talc, CoO.Al ₂ O ₃ , NiO ₂ · CrO ₃ , CoO · MnO ₂ · CrO · Fe ₂ O ₃ , pigments such as MnO ₂ · Cr ₂ O ₃ ; aluminum powder, stainless steel powder, iron powder, nickel powder, chromium powder, silver powder, Examples thereof include metal powder such as gold powder. Among these, from the viewpoint of easy control of the particle size (particle size), easy reading of the printed layer provided on the surface of the concavo-convex layer, cost, and viewpoint that inorganic particles are easily dispersed in the binder resin. Therefore, titania is preferable. Moreover, you may use a metal powder from a viewpoint of avoiding peeling electrification. One kind of the inorganic particles may be used, or two or more kinds may be used in combination.

Although the average particle diameter of the inorganic particles is not particularly limited, for example, 0.05 μm or more (for example, 0.05 to 5.00 μm or the like) is preferable, 0.05 to 4.00 μm is more preferable, and 0 is more preferable. 0.05 to 3.00 μm. When the average particle size is 5 μm or less, the display of the print layer becomes clear and information reading of the print layer becomes easy. When the average particle size is 0.05 μm or more, the uneven shape of the uneven layer is easily maintained.
In this specification, the average particle diameter of inorganic particles is a value measured by the following method.
The cross section of the concavo-convex layer containing inorganic particles is observed with a scanning electron microscope (SEM, trade name “S-4800”, manufactured by Hitachi High-Technologies Corporation, observed at 30000 times), and the particle size of any 15 inorganic particles is measured. The average value is determined as the average particle size.

  The content of the inorganic particles in the concavo-convex layer is not particularly limited, but is preferably 10 to 2000 parts by weight, more preferably 10 to 1000 parts by weight, and further preferably 10 to 10 parts by weight with respect to 100 parts by weight of the binder resin. 500 parts by weight, more preferably 15 to 100 parts by weight, particularly preferably 20 to 50 parts by weight. When the content of the inorganic particles is 10 parts by weight or more, the uneven shape on the surface of the uneven layer is easily maintained. When the content of the inorganic particles is 2000 parts by weight or less, the inorganic particles are easily dispersed in the uneven layer.

  Although it does not specifically limit as the hardening | curing agent in the said uneven | corrugated layer, From a viewpoint that an uneven | corrugated layer becomes stronger further and an uneven | corrugated shape becomes easy to maintain, for example, an isocyanate type hardening | curing agent, a melamine type hardening | curing agent, an epoxy-type hardening | curing agent, etc. Can be mentioned.

  Although it does not specifically limit as a crosslinking agent in the said uneven | corrugated layer, For example, an isocyanate type crosslinking agent, a melamine type crosslinking agent, and an epoxy type crosslinking agent are mentioned.

  Although it does not specifically limit as another additive in the said uneven | corrugated layer, For example, antioxidant, antioxidant, an ultraviolet absorber etc. are mentioned.

  Although the thickness of the said uneven | corrugated layer is not specifically limited, For example, 1-500 micrometers is preferable, More preferably, it is 3-300 micrometers, Especially preferably, it is 5-100 micrometers.

  The concavo-convex layer may have a single layer structure or a laminated structure. Note that the concavo-convex layer having a laminated structure may be such that at least one of at least one surface of the outermost layer has an arithmetic average roughness (Ra) of 0.1 μm or more. The arithmetic average roughness (Ra) of the surface may be 0.1 μm or more, or only one of the outermost surface layers may have an arithmetic average roughness (Ra) of 0.1 μm or more. When the concavo-convex layer has a laminated structure, each layer may have the same composition or a different composition. As the concavo-convex layer of the laminated structure, for example, the outermost layer serving as an interface with air (one surface of the pressure-sensitive adhesive sheet) is a layer that easily maintains the concavo-convex shape, and the surface in contact with the base material is adhesive to the base material. And a laminated structure that is an excellent layer.

  In the uneven layer, only one surface (one surface) may have an arithmetic average roughness (Ra) of 0.1 μm or more, and both surfaces (both surfaces) have an arithmetic average roughness (Ra) of 0.1 μm. It may be the above. That is, the uneven layer, which is the surface layer of the pressure-sensitive adhesive sheet of the present invention, may have an arithmetic average roughness (Ra) of 0.1 μm or more only at the interface with air, The interface with the layer may have an arithmetic average roughness (Ra) of 0.1 μm or more. In particular, the uneven layer has an arithmetic average roughness (Ra) of one surface of 0.1 μm or more and the other surface is flat (for example, an arithmetic average roughness (Ra) of 0.05 μm or less). Is preferred. When both surfaces have an arithmetic average roughness (Ra) of 0.1 μm or more, the arithmetic average roughness of each surface may be the same or different.

The arithmetic average roughness (Ra) of the surface of the concavo-convex layer is 0.1 μm or more (for example, 0.1 to 7.0 μm) from the viewpoint that layer peeling hardly occurs. Among these, from the viewpoint that layer peeling is less likely to occur and a printing layer is easily provided, 0.5 to 5.0 μm is preferable, and 0.6 to 4.5 μm is more preferable. In particular, 0.8 to 4.0 μm is preferable, 1 to 3.5 μm is more preferable, and 2 to 3 μm is more preferable from the viewpoint that the display of the printed layer becomes clear and layer peeling is less likely to occur. When both surfaces of the uneven layer are uneven, the arithmetic average roughness (Ra) of both surfaces may be the same or different.
The arithmetic average roughness (Ra) in the present specification specifically refers to a value measured by the method described in “(arithmetic average roughness (Ra))” in (Evaluation) described later.
The arithmetic average roughness of the surface of the concavo-convex layer is, for example, the type and particle size of inorganic particles, the type of Meyer bar, the plate used for gravure printing, the post-treatment after forming the concavo-convex layer (corona treatment (voltage during corona treatment) And sand blasting).

  Although the glass transition temperature (Tg) of the said uneven | corrugated layer is not specifically limited, For example, 20 degreeC or more (for example, 20-300 degreeC) is preferable, More preferably, it is 50-300 degreeC, More preferably, it is 60-300 degreeC, Especially preferably Is 70-300 ° C. When the glass transition temperature of the uneven layer is in the above range, the heat resistance of the uneven layer is improved and the uneven shape is easily maintained.

The water contact angle on the surface of the concavo-convex layer (the water contact angle on the surface having an arithmetic average roughness (Ra) of the concavo-convex layer of 0.1 μm or more) is not particularly limited. 85 ° or less), preferably 65 ° or less, more preferably 64 ° or less, and particularly preferably 60 ° or less. When the water contact angle of the concavo-convex layer is in the above range, it becomes easy to provide a print layer, and a clearer print layer can be formed.
The water contact angle in the present specification specifically refers to a value measured by the method described in “(Water contact angle)” in (Evaluation) described later.

(Base material)
The substrate is not particularly limited. For example, polyimide, polyether ether ketone, polyether sulfone, polyether imide, polysulfone, polyphenylene sulfide, polyamide imide, polyester imide, non-aromatic polyamide, paravanic acid resin, Fluorine resin, epoxy resin, hydrocarbon resin, vinyl resin, acetal resin, acrylic resin, styrene resin, polyester resin, polyurethane resin, rubber resin, alkyd resin, fiber resin, The film which consists of etc. is preferable. The base material may be a film made of one kind of resin or a film made of two or more kinds of resins. Among them, polyester resin (polyester film), polyimide (polyimide film), hydrocarbon resin (hydrocarbon resin film, particularly polyolefin film), polyurethane resin (polyurethane film), polyetherimide (polyether) Imide film) and styrene resin (polystyrene film), more preferably polyethylene terephthalate film, polyethylene naphthalate film, polyimide film, polybutylene terephthalate film, polypropylene film, polyurethane film, polyetherimide film, polystyrene film. More preferably, it is a polyethylene terephthalate film, a polyethylene naphthalate film, or a polyimide film. In particular, a polyimide film is preferable from the viewpoint of excellent heat resistance and excellent anchoring property with the binder resin in the uneven layer. The substrate may be a single layer or a multilayer.

  Examples of the polyester film include trade name “Lumirror S10” (manufactured by Toray Industries, Inc., polyethylene terephthalate film), trade name “Teonex film” (manufactured by Teijin DuPont Films, Ltd., polyethylene naphthalate film), product The name “G2” (manufactured by Teijin DuPont Films Co., Ltd.) can be mentioned. As a polyimide film, for example, a brand name “100H” (manufactured by Toray Industries, Inc.), a brand name “Kapton H type” (manufactured by Toray DuPont), and a brand name “Apical type” (manufactured by Kaneka Corporation). Etc.

  The base material may be subjected to surface treatment, for example. The surface treatment is not particularly limited. For example, corona discharge treatment, plasma treatment, sand mat processing treatment, ozone exposure, flame exposure, high-voltage impact exposure, ionizing radiation treatment, etc., chemical treatment such as chromic acid treatment. And easy adhesion treatment (coating treatment) with a coating agent (priming agent).

The substrate is preferably a substrate excellent in heat resistance. Especially, although melting | fusing point of the said base material is not specifically limited, For example, it is preferable that it is 150 degreeC or more.
(Measuring method of melting point)
The melting point is a temperature measured using a trade name “Q-2000” (manufactured by TA Instruments Inc.) under a nitrogen atmosphere of 50 ml / min and a temperature increase rate of 10 ° C./min. If thermal decomposition occurs before the melting point appears, the decomposition temperature is taken as the melting point.

The substrate is preferably a substrate having good thermal dimensional stability. Among them, the heat shrinkage rate of the substrate is not particularly limited, but is preferably 5% or less, and more preferably 3% or less, for example.
(Measurement method of thermal shrinkage)
The thermal shrinkage rate is the rate of change in the dimensions (the rate of shrinkage due to heating) obtained from the following conditions and formula using a TMA device (trade name “TMA / SS7100”, manufactured by Hitachi High-Tech Science Co., Ltd.). .
Measurement mode: Tensile method Measurement load: 19.6 mN
Rate of temperature increase: 5 ° C./min Heat shrinkage rate = {(Dimension at 23 ° C. (mm)) − (Dimension at 260 ° C. (mm))} / (Dimension at 23 ° C. (mm)) × 100

The coefficient of thermal expansion of the substrate is not particularly limited, but is preferably, for example, less than 3%, more preferably less than 1.5%, and particularly preferably less than 1%.
(Measurement method of thermal expansion coefficient)
The coefficient of thermal expansion is a value measured under the following conditions using a TMA apparatus (trade name “TMA / SS7100”, manufactured by Hitachi High-Tech Science Co., Ltd.).
Measurement mode: Compression-expansion method Measurement load: 50 mN
Probe diameter: 3.5mmΦ
Temperature increase rate: 5 ° C / min

The base material is preferably a flexible base material. Although the elasticity modulus of the said base material is not specifically limited, For example, it is preferable that it is 5000 MPa or less, More preferably, it is 4000 MPa or less.
(Measurement method of elastic modulus)
The elastic modulus is a value measured under the following conditions using a viscoelasticity measuring device (DMS) (trade name “DMS6100”, manufactured by Hitachi High-Tech Science Co., Ltd.).
Measurement mode: Tensile chuck spacing: 20 mm
Temperature increase rate: 2 ° C / min

  Although the thickness of the said base material is not specifically limited, For example, 500 micrometers or less (for example, 1-500 micrometers) are preferable, More preferably, it is 5-200 micrometers, Especially preferably, it is 5-150 micrometers, Especially preferably, it is 5-100 micrometers.

  Although the glass transition temperature (Tg) of the said base material is not specifically limited, For example, 20 degreeC or more (for example, 20-350 degreeC) is preferable, More preferably, it is 60-350 degreeC, More preferably, it is 70-350 degreeC, More preferably Is 80 to 350 ° C, more preferably 100 to 350 ° C, still more preferably 120 to 350 ° C, and particularly preferably 170 to 350 ° C. When the glass transition temperature of the base material is in the above range, the heat resistance of the base material is improved, and an increase in the contact area between the uneven layer surface and the adherend caused by the softening of the base material by heat can be suppressed.

  The water contact angle on the surface of the substrate is not particularly limited, but is preferably 85 ° or less (greater than 0 ° and 85 ° or less), more preferably 80 ° or less, and even more preferably 75 ° or less. When the water contact angle of the substrate is within the above range, it becomes easy to provide a layer such as an uneven layer and an adhesive layer that are excellent in adhesion to the substrate.

(Adhesive layer)
The pressure-sensitive adhesive layer is a layer formed of a pressure-sensitive adhesive containing a base polymer as a pressure-sensitive adhesive component. The pressure-sensitive adhesive further includes a crosslinking agent, a tackifier resin, a crosslinking accelerator, an anti-aging agent, a filler, a colorant (pigment, dye, etc.), an ultraviolet absorber, a chain transfer agent, a plasticizer, a softener, and a surfactant. Further, it may contain an antistatic agent or the like.

Although it does not specifically limit as said base polymer, From a viewpoint of initial stage adhesiveness, heat resistance, and solvent resistance, a (meth) acrylic-type polymer, a silicone type polymer, an epoxy-type polymer etc. are preferable, for example. Among these, a (meth) acrylic polymer is preferable from the viewpoint of excellent adhesiveness.
The (meth) acrylic polymer is a (meth) acrylic polymer configured with a (meth) acrylic acid alkyl ester having a linear or branched alkyl group as an essential monomer component (monomer component). It is preferable. The monomer component constituting the (meth) acrylic polymer further includes a copolymerizable monomer such as a polar group-containing monomer, a polyfunctional monomer, and other copolymerizable monomers. May be included. By using these copolymerization monomer components, for example, the adhesion to the adherend can be improved, or the cohesive force of the pressure-sensitive adhesive layer can be increased. In addition, said "(meth) acryl" represents "acryl" and / or "methacryl" (any one or both of "acryl" and "methacryl"), and others are also the same.

  Examples of the (meth) acrylic acid alkyl ester having a linear or branched alkyl group (hereinafter sometimes simply referred to as “(meth) acrylic acid alkyl ester”) include, for example, methyl (meth) acrylate , Ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, (meth) T-butyl acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, (Meth) acrylic acid decyl, (meth) acrylic acid isodecyl, (meth) acrylic acid undecyl, (meth) acrylic acid dodecyl, (meth) acrylic acid tridecyl, (meth) acrylic acid tetradecyl, (meth) acrylic acid pentadecyl, (meta ) Alkyl (meth) acrylates having 1 to 20 carbon atoms in the alkyl group such as hexadecyl acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate Examples include esters. Among them, (meth) acrylic acid alkyl esters having 2 to 10 carbon atoms in the alkyl group are preferable, (meth) acrylic acid alkyl esters having 4 to 8 carbon atoms in the alkyl group are more preferable, and acrylic acid 2- Ethylhexyl (2EHA). The said (meth) acrylic-acid alkylester can be used individually or in combination of 2 or more types.

  Although content of the said (meth) acrylic-acid alkylester is not specifically limited, 50 weight% or more (for example, 50-99 weight) with respect to the monomer component whole quantity (100 weight%) which comprises a (meth) acrylic-type polymer. %), More preferably 80 to 98% by weight, still more preferably 85 to 95% by weight. By setting the content to 50% by weight or more, characteristics (such as adhesiveness) as a (meth) acrylic polymer can be exhibited.

  Examples of the polar group-containing monomer include carboxyl group-containing monomers such as (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid (such as maleic anhydride and itaconic anhydride). (Including acid anhydride group-containing monomers); 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxy (meth) acrylate (Meth) acrylic acid hydroxyalkyl such as hexyl; hydroxyl group (hydroxyl group) -containing monomers such as vinyl alcohol and allyl alcohol; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) Amyl group-containing monomers such as clinamide and N-hydroxyethylacrylamide; amino group-containing monomers such as aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, and t-butylaminoethyl (meth) acrylate Glycidyl group-containing monomers such as glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate; cyano group-containing monomers such as acrylonitrile and methacrylonitrile; N-vinyl-2-pyrrolidone, (meth) In addition to acryloylmorpholine, vinyl-containing monomers such as vinylpyridine, N-vinylpiperidone, vinylpyrimidine, N-vinylpiperazine, N-vinylpyrrole, N-vinylimidazole, vinyloxazole; methoxyethyl (meth) acrylate , (Meth) acrylic acid ethoxye (Meth) acrylic acid alkoxyalkyl monomers such as sodium; sulfonic acid group-containing monomers such as sodium vinyl sulfonate; phosphate group-containing monomers such as 2-hydroxyethylacryloyl phosphate; cyclohexylmaleimide and isopropyl Examples thereof include imide group-containing monomers such as maleimide; isocyanate group-containing monomers such as 2-methacryloyloxyethyl isocyanate. Among these, a carboxyl group-containing monomer is preferable, and acrylic acid (AA) is more preferable. The said polar group containing monomer can be used individually or in combination of 2 or more types.

  The content of the polar group-containing monomer is not particularly limited, but from the viewpoint of adhesiveness and cohesiveness, for example, 1 to 1% of the total amount of monomer components (100% by weight) constituting the (meth) acrylic polymer. 50 weight% is preferable, More preferably, it is 2-20 weight%, More preferably, it is 5-15 weight%. Moreover, the ratio of the polar group-containing monomer is not particularly limited, but from the viewpoint of adhesiveness and cohesiveness, for example, 5 to 20 parts by weight with respect to 100 parts by weight of the (meth) acrylic acid alkyl ester is Preferably, it is 10 to 15 parts by weight.

  The polyfunctional monomer is a monomer having two or more ethylenically unsaturated groups (an organic group containing a carbon-carbon double bond) in the molecule (in one molecule). Although it does not specifically limit as said ethylenically unsaturated group, For example, (meth) acryloyl group, alkenyl group (vinyl group (ethenyl group), allyl group (2-propenyl group), butenyl group, pentenyl group, hexenyl group, etc. ) And the like. Specific examples of the polyfunctional monomer include hexanediol di (meth) acrylate, butanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, and (poly) propylene glycol di (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, allyl ( Examples thereof include (meth) acrylate, vinyl (meth) acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, and urethane acrylate. The said polyfunctional monomer can be used individually or in combination of 2 or more types.

  The content of the polyfunctional monomer is not particularly limited, but from the viewpoint of adhesiveness and cohesiveness, 0.5% with respect to the total amount of monomer components (100% by weight) constituting the (meth) acrylic polymer. % By weight or less (for example, more than 0% by weight and 0.5% by weight or less) is preferable, and more preferably more than 0% by weight and 0.3% by weight or less.

  Examples of other copolymerizable monomers other than the polar group-containing monomer and the polyfunctional monomer include cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and the like. (Meth) acrylic acid ester having an alicyclic hydrocarbon group; (meth) acrylic acid aryl ester such as phenyl (meth) acrylate; vinyl esters such as vinyl acetate and vinyl propionate; aroma such as styrene and vinyltoluene Olefins or dienes such as ethylene, butadiene, isoprene and isobutylene; vinyl ethers such as vinyl alkyl ether; vinyl chloride and the like.

  The (meth) acrylic polymer can be prepared by polymerizing the above monomer components by a known or conventional polymerization method. Examples of the polymerization method of the (meth) acrylic polymer include a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, and a polymerization method by active energy ray irradiation (active energy ray polymerization method). Among these, the solution polymerization method and the active energy ray polymerization method are preferable in terms of transparency, water resistance, cost, and the like, and the solution polymerization method is more preferable.

  Although it does not specifically limit as a solvent used for said solution polymerization, For example, Esters, such as ethyl acetate and n-butyl acetate; Aromatic hydrocarbons, such as toluene and benzene; Fats, such as n-hexane and n-heptane Organic solvents such as aliphatic hydrocarbons; cycloaliphatic hydrocarbons such as cyclohexane and methylcyclohexane; ketones such as methyl ethyl ketone and methyl isobutyl ketone. The said solvent can be used individually or in combination of 2 or more types.

  The polymerization initiator used for the polymerization of the (meth) acrylic polymer is not particularly limited. For example, 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2, 4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbohydrate) Nitrile), 2,2′-azobis (2,4,4-trimethylpentane), dimethyl-2,2′-azobis (2-methylpropionate) and the like; benzoyl peroxide, t- Butyl hydroperoxide, di-t-butyl peroxide, t-butyl peroxybenzoate, dicumyl peroxide, 1,1-bis (t-butylperoxide Carboxymethyl) -3,3,5-trimethylcyclohexane, oil-soluble polymerization initiators such as 1,1-bis (t-butylperoxy) peroxide polymerization initiators cyclododecane like are preferably exemplified. The said polymerization initiator can be used individually or in combination of 2 or more types.

  Although content of the said polymerization initiator is not specifically limited, From the viewpoint of adhesiveness and cohesiveness, for example, it is 0.1 with respect to the monomer component whole quantity (100 weight part) which comprises the said (meth) acrylic-type polymer. Is preferably 10 to 10 parts by weight, and more preferably 0.4 to 2 parts by weight.

  Although it does not specifically limit as said crosslinking agent, From a viewpoint that the base polymer (for example, (meth) acrylic polymer) which comprises an adhesive layer is bridge | crosslinked and the cohesion force of an adhesive layer can be enlarged further, For example, a polyfunctional melamine compound (melamine type crosslinking agent), a polyfunctional epoxy compound (epoxy type crosslinking agent), a polyfunctional isocyanate compound (isocyanate type crosslinking agent), etc. are mentioned. Among these, from the viewpoint of reactivity, an isocyanate-based crosslinking agent and an epoxy-based crosslinking agent are preferable, and an isocyanate-based crosslinking agent is more preferable. The said crosslinking agent can be used individually or in mixture of 2 or more types.

  Examples of the isocyanate-based crosslinking agent include lower aliphatic polyisocyanates such as 1,2-ethylene diisocyanate, 1,4-butylene diisocyanate, and 1,6-hexamethylene diisocyanate; cyclopentylene diisocyanate, cyclohexylene diisocyanate, and isophorone. Alicyclic polyisocyanates such as diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate; 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, etc. Aromatic polyisocyanates; trimethylolpropane / tolylene diisocyanate adduct [manufactured by Nippon Polyurethane Industry Co., Ltd., trade name “Coronate L”] Trimethylolpropane / hexamethylene diisocyanate adduct [Nippon Polyurethane Industry Co., Ltd. under the trade name "Coronate HL"], and the like.

  Examples of the epoxy crosslinking agent include N, N, N ′, N′-tetraglycidyl-m-xylenediamine, diglycidylaniline, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, 1 , 6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, Pentaerythritol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitan polyglycidyl ether, trimethylolpropane polyglycid Diethyl ether, adipic acid diglycidyl ester, o-phthalic acid diglycidyl ester, triglycidyl-tris (2-hydroxyethyl) isocyanurate, resorcin diglycidyl ether, bisphenol-S-diglycidyl ether, and epoxy group in the molecule And an epoxy resin having two or more. As a commercial item, a brand name "Tetrad C" (Mitsubishi Gas Chemical Co., Ltd. product) can be used, for example.

  The content of the crosslinking agent is not particularly limited, but from the viewpoint that the pressure-sensitive adhesive layer does not become too hard and is excellent in cohesiveness, it is 0.1 to 5% by weight with respect to the total amount of the pressure-sensitive adhesive (100% by weight). Is more preferable, and 0.3 to 1% by weight is more preferable. Further, the ratio of the cross-linking agent is not particularly limited, but from the viewpoint that the pressure-sensitive adhesive layer does not become too hard and has excellent cohesiveness, for example, 100 parts by weight of the base polymer (for example, (meth) acrylic polymer). On the other hand, 0.1-5 weight part is preferable, More preferably, it is 0.3-1 weight part.

  Although it does not specifically limit as said tackifying resin, From a viewpoint of an adhesive improvement, a terpene type tackifying resin, a phenol type tackifying resin, a rosin type tackifying resin, a petroleum type tackifying resin etc. are mentioned, for example. The said tackifying resin can be used individually or in combination of 2 or more types.

  Although the thickness of the said adhesive layer is not specifically limited, 5-200 micrometers is preferable, More preferably, it is 3-100 micrometers, More preferably, it is 5-50 micrometers, Most preferably, it is 10-40 micrometers.

(Separator)
The separator is not particularly limited. For example, a base material having a release layer such as a plastic film or paper surface-treated with a release agent such as silicone-based, long-chain alkyl-based, fluorine-based, or molybdenum sulfide; polytetrafluoro A low-adhesive substrate made of a fluoropolymer such as ethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene / hexafluoropropylene copolymer, chlorofluoroethylene / vinylidene fluoride copolymer; And a low-adhesive substrate made of a nonpolar polymer such as an olefin resin (for example, polyethylene, polypropylene, etc.). In addition, a separator peels off when using an adhesive sheet (for example, when affixing on a to-be-adhered body).

  Although the manufacturing method of the adhesive sheet of this invention is not specifically limited, For example, the manufacturing method including the process of forming an uneven | corrugated layer and the process of forming an adhesive layer is mentioned.

Although it does not specifically limit as a process of forming the said uneven | corrugated layer, For example, the coating liquid containing binder resin is used using a fountain coater, a reverse roll coater, a comma coater, a gravure coater, a Mayer bar coater (rod coater) etc. Examples include a coating process. However, when the desired unevenness cannot be obtained by these methods, a method of further increasing the unevenness may be used in combination.
As a method of increasing the unevenness, for example, a method of applying the coating liquid uniformly to the surface, such as a phantom coater, reverse roll coater, or comma coater, the coating liquid is applied and dried. There is a method of sandblasting the work surface. In coating methods such as gravure coater and Mayer bar coater (rod coater) where the coater has a coating liquid coating part and a non-coating part, a gravure plate (ink reservoir, also called a cup) is used to obtain sufficient unevenness. And a method of increasing the diameter and winding period (pitch) of the wire wound around the bar in the Mayer bar coater. Further, if the substrate line speed at the time of printing is reduced, the coating amount at an arbitrary location increases, so that the unevenness can be made larger.
Further, regardless of the coater method, when the solvent volatilization rate is increased, the resin is solidified before the coated surface is smoothed by the leveling effect, so that the unevenness increases. Examples of the method for increasing the volatilization rate include various methods such as increasing the drying temperature, increasing the amount of drying air, and decreasing the line speed in the drying tower. Any one or more of the methods for increasing the volatilization rate can be used, and can be determined in consideration of the viscosity of the binder resin, the solvent boiling point, and the like.

  Although the depth of the plate of the plate used in the gravure printing is not particularly limited, for example, 0.05 to 1000 μm is preferable, and 0.1 to 100 μm is more preferable. The shape of the plate is not particularly limited, and examples thereof include oblique lines, turtle shells, pyramids, and trapezoids.

  Although it does not specifically limit as drying conditions in the process of forming the said uneven | corrugated layer, The temperature of 70-150 degreeC and the drying for 0.1 to 100 minutes are mentioned.

  Although the process of forming the said adhesive layer is not specifically limited, For example, the said adhesive mixed uniformly is used using a fountain coater, a reverse roll coater, a comma coater, a gravure coater, a Mayer bar coater (rod coater) etc. The method of forming by coating and drying is mentioned. The pressure-sensitive adhesive may be applied to the surface of the substrate surface that is not provided with the uneven layer, or the surface of the substrate surface that is not provided with the uneven layer after the adhesive is applied and dried on the separator. It may be pasted together.

  Although it does not specifically limit as drying conditions in the process of forming the said adhesive layer, For example, temperature 100-170 degreeC and time 0.1-100 minutes are mentioned.

The pressure-sensitive adhesive sheet of the present invention is not easily bent by heating (for example, a temperature of 230 to 350 ° C., for a period of 0.1 to 30 minutes) (for example, the end portion is not easily lifted from a state of being attached to an adherend). Is preferred. Specifically, the pressure-sensitive adhesive sheet of the present invention is not particularly limited, but the curl is preferably 50 mm or less (for example, 1 to 50 mm), more preferably 30 mm or less, still more preferably 20 mm or less, and particularly preferably 10 mm. It is as follows.
The curl is a value measured by a method described in “(Curlability)” in (Evaluation) described later.

In the pressure-sensitive adhesive sheet of the present invention, when the coefficient of thermal expansion is different between the uneven layer and the substrate, the pressure-sensitive adhesive sheet is easily bent by heating. From the viewpoint that it is difficult to bend by heating, the difference between the thermal expansion coefficient of the concavo-convex layer and the thermal expansion coefficient of the substrate is preferably 5% or less, more preferably 2% or less, and even more preferably 1% or less. . The coefficient of thermal expansion refers to a value measured by the following method.
(Measurement method of thermal expansion coefficient)
The coefficient of thermal expansion is a value measured under the following conditions using a TMA apparatus (trade name “TMA / SS7100”, manufactured by Hitachi High-Tech Science Co., Ltd.).
Measurement mode: Compression-expansion method Measurement load: 50 mN
Probe diameter: 3.5mmΦ
Temperature increase rate: 5 ° C / min

  The pressure-sensitive adhesive sheet of the present invention is not particularly limited, but, for example, the layer peeling measured by the method described in (Evaluation), “(Layer peeling)” is preferably 30% or less, and preferably 20% or less. Is more preferable, 10% or less is further preferable, and 0% is particularly preferable. When the layer peeling is in the above range, it becomes difficult to cause the disappearance of the label pattern, the contamination of the conveying jig, and the like, and the productivity is improved.

  The thickness (μm) of the uneven layer (the thickness of the uneven layer / the thickness of the substrate) relative to the thickness (μm) of the substrate in the pressure-sensitive adhesive sheet of the present invention is not particularly limited. From the viewpoint of easy sticking to an adherend and less layer peeling, for example, 0.1 to 1 is preferable, more preferably 0.15 to 0.5, and particularly preferably 0.2 to 0.3. It is.

  When the pressure-sensitive adhesive sheet of the present invention is used for production management of a product (for example, an electronic circuit board), a manufacturing process (for example, a heating process, a chemical process, a cleaning process) for about 30 minutes after the pressure-sensitive adhesive sheet is attached to an adherend. Etc.), the product is often completed. Therefore, it is preferable that the pressure-sensitive adhesive sheet of the present invention is excellent in adhesiveness even 30 minutes after being attached to the adherend. Specifically, a pressure sensitive adhesive sheet piece having a width of 10 mm and a length of 100 mm is made of a slide glass (trade name “Micro Slide Glass” manufactured by Matsunami Glass Industry Co., Ltd., length 76 mm, width 26 mm, thickness 1.2 to 1.5 mm. ) Under the conditions of 2 kg roller 1 reciprocation, and 180 ° peel adhesion after leaving for 30 minutes in an atmosphere of 23 ° C. and 50% RH (peeling conditions: temperature 23 ° C., 50% RH, tensile speed 5 m) / Min, peeling angle 180 °) is preferably 1 N / 10 mm or more.

  It is preferable that the adhesive sheet of this invention can be used also for manufacture management of the product (for example, electronic circuit board etc.) manufactured through the process including the heat processing of the temperature of 50-300 degreeC. For example, it is preferable that no sticking out of the pressure-sensitive adhesive layer or peeling of the pressure-sensitive adhesive sheet occurs after the heat treatment at a temperature of 50 to 300 ° C. Specifically, a pressure sensitive adhesive sheet piece having a width of 10 mm and a length of 100 mm is made of a slide glass (trade name “Micro Slide Glass” manufactured by Matsunami Glass Industry Co., Ltd., length 76 mm, width 26 mm, thickness 1.2 to 1.5 mm. ) Under the conditions of 1 kg of 2 kg roller, and left for 30 minutes in an atmosphere of a temperature of 23 ° C. and 50% RH, and then the adhesive layer protrudes after heating at a temperature of 300 ° C. for 5 minutes. It is preferably 0.3 mm or less from the edge, and the pressure-sensitive adhesive sheet piece is not peeled off from the slide glass after heating. In addition, peeling from the slide glass of an adhesive sheet piece can be confirmed visually.

  It is preferable that the pressure-sensitive adhesive sheet of the present invention can be used for production management of a product (for example, an electronic circuit board or the like) including a cleaning step during and / or after the production of the product. For example, the pressure-sensitive adhesive sheet of the present invention is preferably difficult to peel off from the adherend even after being washed with a solvent (for example, isopropanol). Specifically, a pressure sensitive adhesive sheet piece having a width of 10 mm and a length of 100 mm is made of a slide glass (trade name “Micro Slide Glass” manufactured by Matsunami Glass Industry Co., Ltd., length 76 mm, width 26 mm, thickness 1.2 to 1.5 mm. ) Under the conditions of 1 kg of 2 kg rollers, and left for 30 minutes in an atmosphere at a temperature of 23 ° C. and 50% RH. Then, the surface of the adhesive sheet piece is covered with a cotton cloth soaked with isopropanol while applying a load of 300 gf. It is preferable that the adhesive sheet piece does not peel off from the slide glass after 100 reciprocations. In addition, peeling from the slide glass of an adhesive sheet piece can be confirmed visually.

  The pressure-sensitive adhesive sheet of the present invention can be used, for example, as a pressure-sensitive adhesive sheet for printing information such as a barcode (particularly a pressure-sensitive adhesive sheet for barcode printing). Specifically, a product manufactured through a process including heat treatment (for example, temperature 230 to 350 ° C., 0.1 to 30 minutes) (particularly pressure heat treatment (for example, temperature 230 to 350 ° C., pressure 0). .1-10 Pa, product manufactured through a process including a time of 0.1 to 30 minutes) (for example, management at the time of manufacture, traceability after manufacture, etc.) The adhesive sheet for printing used for management of a circuit board is preferable.

  Examples of products manufactured through a process including heat treatment include mounting of electronic circuit boards (such as HDD boards) and electronic components. The pressure-sensitive adhesive sheet of the present invention is preferably, for example, a pressure-sensitive adhesive sheet for printing used by being attached to an electronic circuit board.

  As a conveyance jig (conveyance jig which touches the uneven | corrugated layer of the adhesive sheet of this invention) used when manufacturing through the process including heat processing, a glass plate, a stainless steel plate (SUS), epoxy resin and glass on wood, for example The member etc. which coated etc. are mentioned.

  Examples of the heating in the process including the heat treatment include a temperature of 230 to 350 ° C. (preferably 250 to 340 ° C.) and a time of 0.1 to 30 minutes (preferably 1 to 20 minutes). Moreover, as a pressure, 0.1-10 Pa (preferably 0.1-5 Pa) is mentioned, for example.

[Adhesive label]
The pressure-sensitive adhesive label of the present invention is a pressure-sensitive adhesive label having the pressure-sensitive adhesive sheet of the present invention. The pressure-sensitive adhesive label of the present invention has a printed layer on at least a part of the surface of the pressure-sensitive adhesive sheet of the present invention, wherein the arithmetic average roughness (Ra) of the concavo-convex layer is 0.1 μm or more. Examples of the pressure-sensitive adhesive label of the present invention include pressure-sensitive adhesive labels having a configuration of printing layer / concave layer / base material / adhesive layer, print layer / concave layer / base material / pressure-sensitive adhesive layer / separator, and the like.

(Print layer)
Although the said printing layer is not specifically limited, For example, it is preferable to form from the ink containing resin and a coloring agent.

  The resin contained in the ink is not particularly limited, and examples thereof include polyester resins, polyamide resins, acrylic resins, acrylic urethane resins, polycarbonate resins, phenol resins, polyolefin resins, and aramids. . Among these, polyester resins are preferable from the viewpoint of cost and easy application of ink to the surface of the uneven layer. The said resin can be used individually or in combination of 2 or more types.

  When the binder resin contained in the concavo-convex layer and the resin contained in the ink forming the print layer are the same type, when the print layer is formed by thermal transfer, the respective resins are melted and pressure-bonded. In some cases, the uneven layer and the printed layer are more firmly bonded. Therefore, the binder resin contained in the concavo-convex layer and the resin contained in the ink forming the printing layer are the same type of resin (for example, resins having the same type of main skeleton such as polyester resin and polyester resin). It is preferable.

  Although content of the said resin is not specifically limited, For example, 5-95 weight% is preferable with respect to the ink whole quantity (100 weight%).

  The colorant contained in the ink is not particularly limited, and examples thereof include organic or inorganic pigments, carbon, and metal powder. The organic pigment is not particularly limited, and examples thereof include azo pigments, phthalocyanine pigments, triphenylmethane pigments, metal complex pigments, vat dye pigments, quinacridone pigments, and isoindolinone pigments. . Although it does not specifically limit as said inorganic pigment, For example, black things, such as chromium oxide, cobalt oxide, iron oxide, manganese oxide, chromate, permanganate; Manganese oxide, alumina, chromium oxide, tin oxide, Red materials such as iron oxide, cadmium sulfide, selenium sulfide; blue materials such as cobalt oxide, zirconia, vanadium oxide, chromium oxide, divanadium pentoxide; zirconium, silicon, praseodymium, vanadium, tin, chromium, titanium, antimony, etc. Yellow matter; Green color such as chromium oxide, cobalt / chromium, alumina / chromium; Pink color such as aluminum / manganese, iron / silicon / zirconium; White color such as silica, titania, alumina, zinc white, zirconia, calcium oxide, mica Thing, etc. The colorants can be used alone or in combination of two or more.

  Although content of the said coloring agent is not specifically limited, For example, 1 to 90 weight% is preferable with respect to ink whole quantity (100 weight%). When the ink and the colorant are contained in the ink, the content of the colorant is not particularly limited, but is preferably 50 to 500 parts by weight with respect to 100 parts by weight of the resin, for example.

  The ink may further contain a solvent, an organic solvent, alcohol, or the like as necessary.

  Although the shape (pattern, pattern) in planar view of the said printing layer is not specifically limited, For example, shapes, such as printing, a pattern, and a barcode, are mentioned. Among these, a barcode is preferable from the viewpoint of a large amount of information and ease of information management.

  Although the thickness of the said printing layer is not specifically limited from an adhesive viewpoint with an uneven | corrugated layer, For example, 0.1-15 micrometers is preferable, More preferably, it is 0.4-12 micrometers, More preferably, it is 0.7 micrometers-10 micrometers. is there. In addition, although a detailed cause is unknown, a surface uneven | corrugated shape may be maintained even when the thickness of a printing layer is thicker than the arithmetic mean roughness (Ra) of an uneven | corrugated layer.

  The printed layer may be provided on the entire surface of the concavo-convex layer (the concavo-convex shape surface of the concavo-convex layer) or may be provided in part. Although the shape (pattern, pattern) in planar view of the said printing layer is not specifically limited, For example, shapes, such as printing, a pattern, and a barcode, are mentioned.

  The means for forming the printing layer is not particularly limited, and various printing means such as a thermal transfer method (thermal transfer), an ink jet method, and a gravure printing method can be employed. In addition, two printed layers (for example, two printed layers comprising a concavo-convex layer / a black printed layer / a white printed layer) are provided on the surface of the concavo-convex layer, and the surface printed layer (for example, a white printed layer) is applied by applying a laser. It is also possible to make the other print layer (for example, black print layer) visible by skipping the layer.

The pressure-sensitive adhesive label of the present invention can visually recognize a printed layer even after heating (for example, heating at 230 to 350 ° C. for 0.1 to 30 minutes). Can be read with a code reader). The pressure-sensitive adhesive label of the present invention may be readable using a barcode verification machine (for example, (trade name “AUTOSCAN”, manufactured by RJS) even after heating at a temperature of 230 to 350 ° C. for 0.1 to 30 minutes. Specifically, the PCS value after heating at a temperature of 260 ° C. for 3 minutes is preferably, for example, 70% or more, and more preferably 80% or more.
The PCS value is an index of barcode contrast, and is a value derived from the space reflectance of the barcode and the reflectance of the bar. The PCS value is a value obtained by subtracting the reflectance of the bar from the reflectance of the space and dividing it by the reflectance of the space. That is, the PCS value is a value calculated from the following equation.
PCS = {(space reflectance) − (bar reflectance)} / (space reflectance)
For example, a barcode composed of a white space and a black bar can be calculated from {(white space reflectance) − (black bar reflectance)} / (white space reflectance). Note that the closer the PCS value is to 1, the greater the separation between the reflectance of the space and the reflectance of the bar, so that the barcode has a higher contrast (easier to read).
The reflectance refers to the reflectance when, for example, red light having a wavelength of 660 nm is irradiated from a direction with an incident angle of 90 °. The reflectance can be measured using, for example, a bar code verifier (trade name “AUTOSCAN”, manufactured by RJS).

  The pressure-sensitive adhesive label of the present invention is, for example, a product manufactured through a process including heat treatment (for example, temperature 230 to 350 ° C., 0.1 to 30 minutes) (particularly pressure heat treatment (for example, temperature 230 to 350 ° C, pressure 0.1 to 10 Pa, time 0.1 to 30 minutes, etc.) (manufactured through processes including processes) (for example, management at the time of manufacturing an electronic circuit board, traceability after manufacturing, etc.) Can be used.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited at all by these.

Example 1
100 parts by weight of a polyester resin (trade name “Byron 29SS”, manufactured by Toyobo Co., Ltd.), titanium dioxide (trade name “TITONE R-42”, manufactured by Sakai Chemical Industry Co., Ltd., average particle size 0.3 μm) 30 weights Parts were mixed to prepare a coating solution. Then, a polyimide film (trade name “100H”, manufactured by Toray Industries, Inc., thickness 25 μm) is coated with a coating solution using a Mayer bar # 2 to provide a concavo-convex layer having a concavo-convex shape on the surface, It was dried under the conditions of a temperature of 100 ° C. and a time of 1 minute to form an uneven layer having a thickness of 7 μm and an arithmetic average roughness (Ra) of 0.15 μm.
In addition, acrylic polymer (2EHA / AA / Niper BW (manufactured by NOF Corporation) / ethyl acetate / toluene = 90/10 / 0.6 / 200/130 (parts by weight) polymerized by blending) 100 An adhesive was prepared by mixing 0.5 parts by weight of an isocyanate-based crosslinking agent (trade name “Coronate L”, manufactured by Nippon Polyurethane Co., Ltd.). Then, an adhesive is applied on the surface of the polyimide film opposite to the surface on which the uneven layer is formed, using an applicator, and dried at a temperature of 140 ° C. for 2 minutes. The adhesive has a thickness of 30 μm. The adhesive sheet which formed the layer and has a structure of an uneven | corrugated layer / base material / adhesive layer was produced.

(Example 2)
A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1 except that a gravure plate (depth of 2.0 μm) was used for gravure printing to provide an uneven layer. The uneven layer had a thickness of 7 μm and an arithmetic average roughness (Ra) of 0.21 μm.

(Example 3)
A pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 except that the Mayer bar # 5 was used. The uneven layer had a thickness of 7 μm and an arithmetic average roughness (Ra) of 1.01 μm.

Example 4
A pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 except that the Mayer bar # 8 was used. The uneven layer had a thickness of 7 μm and an arithmetic average roughness (Ra) of 2.35 μm.

(Example 5)
A pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 except that the Mayer bar # 11 was used. The uneven layer had a thickness of 7 μm and an arithmetic average roughness (Ra) of 3.32 μm.

(Example 6)
A pressure-sensitive adhesive sheet as in Example 1 except that a polyethylene terephthalate film (trade name “Lumirror S10”, manufactured by Toray Industries, Inc., thickness 25 μm) was used in place of the polyimide film, and Mayer Bar # 8 was used. Was made. The uneven layer had a thickness of 7 μm and an arithmetic average roughness (Ra) of 2.33 μm.

(Example 7)
As a base material, a polyethylene naphthalate film (trade name “Teonex film”, manufactured by Teijin DuPont Films, Inc., thickness 25 μm) is used instead of a polyimide film, and a Mayer bar # 8 is used. Thus, an adhesive sheet was produced. The uneven layer had a thickness of 7 μm and an arithmetic average roughness (Ra) of 2.41 μm.

(Example 8)
As a coating solution, 100 parts by weight of a polyester resin (trade name “Byron 29SS”, manufactured by Toyobo Co., Ltd.), iron oxide (trade name “AM-200”, manufactured by Titanium Industry Co., Ltd.), average particle size of 3.0 μm ) Was used, and an adhesive sheet was prepared in the same manner as in Example 1 except that Mayer Bar # 8 was used. The uneven layer had a thickness of 7 μm and an arithmetic average roughness (Ra) of 2.35 μm.

Example 9
As a coating liquid, acrylic resin (trade name “A-817”, manufactured by DIC Corporation) 100 parts by weight, titanium dioxide (trade name “TITONE R-42”, manufactured by Sakai Chemical Industry Co., Ltd., average particle diameter) 0.3 μm) A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1 except that the coating liquid mixed with 30 parts by weight was used and Mayer bar # 8 was used. The uneven layer had a thickness of 7 μm and an arithmetic average roughness (Ra) of 2.45 μm.

(Example 10)
As a coating liquid, acrylic urethane resin (trade name “UV-3610ID80”, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 100 parts by weight, titanium dioxide (trade name “TITONE R-42”, manufactured by Sakai Chemical Industry Co., Ltd.) In addition, a pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1 except that a coating solution in which 30 parts by weight of an average particle diameter of 0.3 μm) was mixed and a Mayer bar # 8 was used. The uneven layer had a thickness of 7 μm and an arithmetic average roughness (Ra) of 2.32 μm.

(Example 11)
As a coating liquid, 100 parts by weight of aramid (trade name “Conex”, manufactured by Teijin Ltd.), titanium dioxide (trade name “TITONE R-42”, manufactured by Sakai Chemical Industry Co., Ltd., average particle size: 0.3 μm) ) A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1 except that 30 parts by weight of the coating liquid was used and Mayer bar # 8 was used. The uneven layer had a thickness of 7 μm and an arithmetic average roughness (Ra) of 2.22 μm.

(Comparative Example 1)
A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1 except that the same coating liquid as in Example 1 was applied using an applicator and the uneven shape was not provided. The uneven layer had a thickness of 7 μm and an arithmetic average roughness (Ra) of 0.05 μm.

[Evaluation]
About the adhesive sheet obtained by the Example and the comparative example, it evaluated by the following measuring method or evaluation method.
The evaluation results are shown in Table 1.

(Arithmetic mean roughness (Ra))
Using the non-contact three-dimensional surface shape roughness measurement system (type “Wyko NT9100”, manufactured by Veeco), the arithmetic average roughness (Ra) of the uneven layer surface of the pressure-sensitive adhesive sheet obtained in Examples and Comparative Examples, The measurement was performed under the following conditions using a vertical scanning interference method, and the “arithmetic surface roughness (μm) of the uneven layer surface” of each adhesive sheet was determined.
Objective lens: 2.5x FOV (Field of view): 1

(Glass transition temperature (℃))
From the pressure-sensitive adhesive sheets obtained in Examples and Comparative Examples, a sample (uneven layer or substrate) was collected, weighed about 1 to 2 mg in an aluminum open cell, and temperature-modulated DSC (trade name “Q-2000”). , Manufactured by T.A. Instruments Co., Ltd.) Reversing Heat Flow (specific heat component) of the sample (concave layer or substrate) at a heating rate of 10 ° C./min in a nitrogen atmosphere of 50 ml / min. The behavior was obtained. Referring to JIS-K-7121, the low temperature side baseline of the obtained Reversing Heat Flow and the straight line that is equidistant from the straight line extending the high temperature side base line, and the stepwise change of the glass transition The temperature at the point where the partial curve intersected was defined as the “glass transition temperature (° C.)” of each sample.
In addition, when the sample decomposed | disassembled before glass transition, the decomposed temperature was made into the glass transition temperature.

(Melting point (℃))
The melting point of the base material was measured using a trade name “Q-2000” (manufactured by T.A. Instruments Inc.) under a nitrogen atmosphere of 50 ml / min at a temperature rising rate of 10 ° C./min. When thermal decomposition occurred before the melting point appeared, the decomposition temperature was taken as the melting point.

(Water contact angle (°))
The water contact angle of the concavo-convex layer surface of the pressure-sensitive adhesive sheet obtained in Examples and Comparative Examples, and the water contact angle of the substrates used in Examples and Comparative Examples were measured by the following methods.
Using an automatic contact angle meter (model FACE CA-X type, manufactured by Kyowa Interface Chemical Co., Ltd.), the surface of the uneven layer or the surface of the substrate in an atmosphere of a temperature of 23 ° C. and a humidity of 30% RH by an appropriate method of FAMAS solution Then, 2 μL of water droplets (distilled water) was dropped, and the contact angle (angle formed by the tangent line between the surface and the end of the dropped water droplet) after 1 second from the dropping was measured to obtain “water contact angle (°)”.

(Curl property)
FIG. 2 is an explanatory view (cross-sectional view) for evaluating the curling property.
The pressure-sensitive adhesive sheets obtained in Examples and Comparative Examples were cut into a length of 100 mm and a width of 100 mm (square shape) to prepare a sheet piece 21. The sheet piece 21 was subjected to powder treatment (trade name “Siccalol High”, manufactured by Wakodo Co., Ltd.) on the surface of the pressure-sensitive adhesive layer to eliminate the stickiness. The surface of the pressure-sensitive adhesive layer of the sheet piece 21 is in contact with the surface of the slide glass 22 (trade name “Micro Slide Glass”, manufactured by Matsunami Glass Industry Co., Ltd., length 76 mm, width 26 mm, thickness 1.2 to 1.5 mm). In this way, the sheet piece 21 was placed on the slide glass 22 to prepare a sample.
In the sample, the distance 23 between the apex (4 apexes) on the surface of the pressure-sensitive adhesive layer of the sheet piece and the slide glass surface was measured, and the average of the four values was defined as “curl before heating” (mm).
Thereafter, the sample was placed in a hot air dryer and heated at a temperature of 260 ° C. for 3 minutes. The sample after heating was also measured for the distance 23 between the apex (4 apexes) on the surface of the pressure-sensitive adhesive layer of the sheet piece and the slide glass surface, and the average of the four values was defined as “curl after heating” (mm). Then, “curl” (mm) was calculated from the following calculation formula.
{Curl (mm)} = {Curl after heating (mm)}-{Curl before heating (mm)}

(Layer peeling)
The pressure-sensitive adhesive sheets obtained in Examples and Comparative Examples were cut into a length of 40 mm and a width of 20 mm, and the pressure-sensitive adhesive layer surface and a slide glass (trade name “Micro Slide Glass”, manufactured by Matsunami Glass Industrial Co., Ltd., length 76 mm, width 26 mm, thickness 1.2 to 1.5 mm) was bonded to each other under the conditions of a temperature of 23 ° C. and a reciprocating 2 kg roller, and allowed to stand at a temperature of 23 ° C. for 1 hour. Thereafter, a slide glass (trade name “Micro Slide Glass” manufactured by Matsunami Glass Industry Co., Ltd., length 76 mm, width 26 mm, thickness 1.2 to 1.5 mm) is placed on the surface of the concavo-convex layer. A 5 kg weight (length 100 mm, width 100 mm) was placed. Then, after heating at 300 ° C. for 10 minutes and cooling to room temperature, remove the slide glass placed on the surface of the concavo-convex layer from the adhesive sheet, photograph the slide glass surface, and visually check the photograph after photography, Evaluation was made according to the criteria.
Excellent (◎): No peeling of the concavo-convex layer (the concavo-convex layer did not adhere to the surface of the slide glass. Ratio of the area of the concavo-convex layer attached to the surface of the slide glass to the surface area (100%) of the concavo-convex layer of the adhesive sheet Is 0%)
Good (O): The concavo-convex layer was partially peeled (the ratio of the area of the concavo-convex layer attached to the slide glass surface to the concavo-convex layer surface area (100%) of the pressure-sensitive adhesive sheet was 30% or less)
Defect (x): The uneven layer was peeled as a whole (the ratio of the area of the uneven layer attached to the slide glass surface to the uneven layer surface area (100%) of the pressure-sensitive adhesive sheet was greater than 30%)

DESCRIPTION OF SYMBOLS 11 Adhesive layer 12 Base material 13 Print receiving layer 14 Print layer 15 Adhesive label 16 Board | substrate 17 Conveying jig | tool 18 Flux layer 19 Solder 21 Sheet piece 22 Slide glass 23 The vertex of the adhesive layer surface of a sheet piece, and the surface of a slide glass distance

Claims (12)

A pressure-sensitive adhesive sheet having an uneven layer, a substrate, and a pressure-sensitive adhesive layer,
The concavo-convex layer is provided on one surface side of the substrate;
The pressure-sensitive adhesive layer is provided on the other surface side of the substrate;
The pressure-sensitive adhesive sheet is characterized in that the arithmetic average roughness (Ra) of the surface of the uneven layer is 0.1 μm or more.   The pressure sensitive adhesive sheet according to claim 1 whose glass transition temperature of said concavo-convex layer is 20 ° C or more.   The pressure sensitive adhesive sheet according to claim 1 or 2 whose water contact angle of said uneven layer surface is 85 degrees or less.   The pressure-sensitive adhesive sheet according to any one of claims 1 to 3, wherein the uneven layer includes at least one binder resin selected from the group consisting of a polyester resin, an acrylic urethane resin, an acrylic resin, and an aramid.   The pressure-sensitive adhesive sheet according to claim 1, wherein the substrate has a glass transition temperature of 20 ° C. or higher.   The pressure-sensitive adhesive sheet according to any one of claims 1 to 5, wherein a water contact angle on the surface of the substrate is 85 ° or less.   The pressure-sensitive adhesive sheet according to any one of claims 1 to 6, wherein the substrate is a polyethylene terephthalate film, a polyethylene naphthalate film, or a polyimide film.   The pressure-sensitive adhesive sheet according to any one of claims 1 to 7, wherein the uneven layer includes inorganic particles.   The pressure-sensitive adhesive sheet according to claim 8, wherein the inorganic particles have an average particle diameter of 0.05 μm or more. The pressure-sensitive adhesive sheet according to any one of claims 1 to 9, wherein a curl in the following test is 30 mm or less.
(test)
The pressure-sensitive adhesive layer surface of the pressure-sensitive adhesive sheet piece (length 100 mm, width 100 mm) is subjected to powder treatment to eliminate stickiness, and the pressure-sensitive adhesive layer surface of the pressure-sensitive adhesive sheet piece and the surface of the slide glass are in contact with each other. Is placed on a glass slide to prepare a sample.
In the above sample, the distance between the apex (4 apexes) of the pressure-sensitive adhesive layer surface of the pressure-sensitive adhesive sheet piece and the slide glass surface is measured, and the average of the four values is defined as “curl before heating” (mm). After that, the sample is put in a hot air dryer and heated at a temperature of 260 ° C. for 3 minutes, and the heated sample is also measured for the distance between the apex (4 apexes) of the adhesive layer surface of the adhesive sheet piece and the slide glass surface. The average value of the four values is defined as “curl after heating” (mm). Then, “curl” (mm) is calculated from the following calculation formula.
{Curl (mm)} = {Curl after heating (mm)}-{Curl before heating (mm)}   The pressure-sensitive adhesive sheet according to any one of claims 1 to 10, which is a pressure-sensitive adhesive sheet for printing used by being attached to an electronic circuit board.   It has the adhesive sheet of any one of Claims 1-11, and has a printing layer in at least one part of the surface whose arithmetic mean roughness (Ra) of an uneven | corrugated layer is 0.1 micrometer or more, It is characterized by the above-mentioned. To sticky label.

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