WO2023136171A1 - Single-sided adhesive tape - Google Patents

Single-sided adhesive tape Download PDF

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Publication number
WO2023136171A1
WO2023136171A1 PCT/JP2022/048577 JP2022048577W WO2023136171A1 WO 2023136171 A1 WO2023136171 A1 WO 2023136171A1 JP 2022048577 W JP2022048577 W JP 2022048577W WO 2023136171 A1 WO2023136171 A1 WO 2023136171A1
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WO
WIPO (PCT)
Prior art keywords
sensitive adhesive
adhesive layer
adhesive tape
heat
sided
Prior art date
Application number
PCT/JP2022/048577
Other languages
French (fr)
Japanese (ja)
Inventor
徳之 内田
Original Assignee
積水化学工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by 積水化学工業株式会社 filed Critical 積水化学工業株式会社
Priority to CN202280055522.4A priority Critical patent/CN117813359A/en
Publication of WO2023136171A1 publication Critical patent/WO2023136171A1/en

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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/06Non-macromolecular additives organic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00Adhesives based on unspecified macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/20Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22Plastics; Metallised plastics
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/20Adhesives in the form of films or foils characterised by their carriers
    • C09J7/28Metal sheet
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38Pressure-sensitive adhesives [PSA]

Definitions

  • the present invention relates to single-sided adhesive tapes.
  • Adhesive tapes have been widely used to fix components in electronic devices.
  • Adhesive tape is also used as a processing material in the manufacturing process of electronic devices. used.
  • these adhesives and adhesive tapes are required to have functions such as heat resistance, thermal conductivity, and impact resistance depending on the environment in which they are used (for example, Patent Documents 1 to 3 ).
  • substrates such as printed wiring boards used in electronic devices are manufactured by forming a circuit on a copper foil portion of a copper clad laminate (CCL) in which a copper foil and a resin layer are laminated.
  • CCL copper clad laminate
  • substrates such as printed wiring boards have become thinner. There is a problem that the edges of the copper clad laminate are damaged during the process.
  • the present inventors have studied protecting the ends of the copper-clad laminate by attaching an adhesive tape.
  • the copper-clad laminate is thin as described above, the copper-clad laminate bends or warps when the adhesive tape is attached to the edge of the copper-clad laminate. It has been found that the adhesive tape comes into contact with the adhesive tape and sticks to it, causing the adhesive tape to wrinkle.
  • a strong alkaline solution is used as the processing liquid. For this reason, when exposed to a strong alkaline solution, the adhesive tape peels off, resulting in insufficient protection of the edges of the copper-clad laminate and corrosion of the copper on the surface of the copper-clad laminate.
  • An object of the present invention is to provide a single-sided pressure-sensitive adhesive tape that does not wrinkle easily even when applied to a thin adherend and has excellent resistance to strong alkaline solutions.
  • the present disclosure 1 is a single-sided adhesive tape having a substrate and a heat-sensitive adhesive layer laminated on one surface of the substrate, wherein the substrate is at least on the side opposite to the heat-sensitive adhesive layer.
  • the present disclosure 2 is the single-sided adhesive tape of the present disclosure 1, wherein the metal layer is made of copper.
  • Present Disclosure 3 is the single-sided pressure-sensitive adhesive tape according to Present Disclosure 1 or 2, wherein the substrate is a metal substrate.
  • Present Disclosure 4 is the single-sided pressure-sensitive adhesive tape according to Present Disclosure 3, wherein the metal substrate is a copper foil.
  • This disclosure 5 is the single-sided adhesive tape of this disclosure 1, 2, 3 or 4, further comprising a pressure sensitive adhesive layer between said substrate and said heat sensitive adhesive layer.
  • the heat-sensitive adhesive layer has a storage modulus G' of 5 MPa or more at 23°C and a storage modulus G' of 0.2 MPa or less at 100°C. 5 or 6 single-sided adhesive tape.
  • the present disclosure 8 is the single-sided adhesive tape according to the present disclosure 1, 2, 3, 4, 5, 6 or 7, wherein the heat-sensitive adhesive layer has a gel fraction of 50% by weight or more.
  • the present disclosure 9 is the single-sided adhesive tape of the present disclosure 1, 2, 3, 4, 5, 6, 7, or 8, wherein the heat-sensitive adhesive layer has a surface roughness Ra of 0.01 ⁇ m or more and 0.8 ⁇ m or less. is.
  • the present disclosure 10 is the single-sided adhesive tape according to the present disclosure 1, 2, 3, 4, 5, 6, 7, 8 or 9, wherein the heat-sensitive adhesive layer contains an acrylic polymer.
  • Present Disclosure 11 is the single-sided adhesive tape of Present Disclosure 10, wherein the heat-sensitive adhesive layer further contains a tackifying resin.
  • the present disclosure 12 is the single-sided adhesive tape of the present disclosure 11, wherein the tackifying resin has a softening point of 100° C. or higher.
  • Present Disclosure 13 is the single-sided pressure-sensitive adhesive tape according to Present Disclosure 11 or 12, wherein the tackifying resin has a hydroxyl value of 25 mgKOH/g or more.
  • Present Disclosure 14 is the single-sided pressure-sensitive adhesive tape according to Present Disclosure 11, 12 or 13, wherein the content of the tackifier resin is 5 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the acrylic polymer.
  • the present disclosure 15 is the single-sided adhesive tape according to the present disclosure 10, 11, 12, 13 or 14, wherein the heat-sensitive adhesive layer contains an epoxy-based cross-linking agent.
  • the present disclosure 16 is the single-sided adhesive tape of the present disclosure 5, wherein the pressure-sensitive adhesive layer has a gel fraction of 50% by weight or more.
  • the present disclosure 17 is the single-sided adhesive tape of the present disclosure 5, wherein the pressure-sensitive adhesive layer contains an epoxy-based cross-linking agent.
  • the present disclosure 18 is a single-sided adhesive tape having a base material and a heat-sensitive adhesive layer laminated on one side of the base material, wherein the base material is at least on the side opposite to the heat-sensitive adhesive layer. It has a metal layer on the surface, and the heat-sensitive adhesive layer contains an acrylic polymer and a tackifying resin, and the tackifying resin has a softening point of 100° C.
  • the present disclosure 19 is an etching process, a desmear process, or an electroless plating process, the present disclosures 1 and 2, which are used to protect the edges of the metal-clad laminate by attaching them to the edges of the metal-clad laminate. , 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 or 18 single-sided adhesive tape.
  • the present disclosure 20 is a single-sided adhesive tape having a metal layer on one side and a heat-sensitive adhesive layer on the other side, wherein the heat-sensitive adhesive layer has a coefficient of static friction against SUS of 5 or less. It is a single-sided adhesive tape.
  • the present disclosure 21 is the single-sided adhesive tape of the present disclosure 21, wherein the metal layer is made of copper. Disclosure 22 is the single-sided adhesive tape of Disclosures 20 or 21, further comprising a pressure sensitive adhesive layer between said substrate and said heat sensitive adhesive layer.
  • the present disclosure 23 is the single-sided adhesive tape of the present disclosure 20, 21 or 22, wherein the heat-sensitive adhesive layer has a loss tangent peak temperature of 40 ° C. or higher measured at a measurement frequency of 1 Hz using a dynamic viscoelasticity measuring device. is.
  • the heat-sensitive adhesive layer has a storage elastic modulus G' of 5 MPa or more at 23°C and a storage elastic modulus G' of 0.2 MPa or less at 100°C. It is a single-sided adhesive tape.
  • the present disclosure 25 is the single-sided adhesive tape according to the present disclosure 20, 21, 22, 23 or 24, wherein the heat-sensitive adhesive layer has a gel fraction of 50% by weight or more.
  • 26 of the present disclosure is the single-sided adhesive tape according to 20, 21, 22, 23, 24 or 25, wherein the heat-sensitive adhesive layer has a surface roughness Ra of 0.01 ⁇ m or more and 0.8 ⁇ m or less.
  • the present disclosure 27 is the single-sided adhesive tape of the present disclosure 20, 21, 22, 23, 24, 25 or 26, wherein the heat-sensitive adhesive layer contains an acrylic polymer.
  • This disclosure 28 is the single-sided adhesive tape of this disclosure 27, wherein said thermal adhesive layer further contains a tackifying resin.
  • This disclosure 29 is the single-sided adhesive tape of this disclosure 28, wherein the tackifying resin has a softening point of 100° C. or higher.
  • This disclosure 30 is the single-sided adhesive tape of this disclosure 28 or 29, wherein the tackifying resin has a hydroxyl value of 25 mgKOH/g or more.
  • Present Disclosure 31 is the single-sided adhesive tape according to Present Disclosures 28, 29, or 30, wherein the content of said tackifying resin relative to 100 parts by weight of said acrylic polymer is 5 parts by weight or more and 50 parts by weight or less.
  • 32 of the present disclosure is the single-sided adhesive tape according to 27, 28, 29, 30 or 31 of the present disclosure, wherein the heat-sensitive adhesive layer contains an epoxy-based cross-linking agent.
  • This disclosure 33 is the single-sided adhesive tape of this disclosure 22, wherein the pressure-sensitive adhesive layer has a gel fraction of 50% by weight or more.
  • This disclosure 34 is the single-sided adhesive tape of this disclosure 22, wherein the pressure-sensitive adhesive layer contains an epoxy-based cross-linking agent.
  • the present disclosure 35 is used to protect the edges of the metal-clad laminate by attaching to the edges of the metal-clad laminate in the etching process, the desmear process, or the electroless plating process. , 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33 or 34.
  • the present invention will be described in detail below.
  • the present inventors have found that in a single-sided adhesive tape having a substrate and a heat-sensitive adhesive layer laminated on one side of the substrate, the substrate is placed on at least the surface opposite to the heat-sensitive adhesive layer, It has been considered to have a metal layer and to adjust the coefficient of static friction of the heat-sensitive adhesive layer against SUS to a certain value or less.
  • the present inventors have found that such a single-sided pressure-sensitive adhesive tape is less likely to wrinkle when attached to a thin adherend and has excellent resistance to strong alkaline solutions, and has developed the present invention. I came to complete it.
  • the single-sided adhesive tape has a substrate and a heat-sensitive adhesive layer laminated on one side of the substrate.
  • the base material refers to the entire portion of the single-sided pressure-sensitive adhesive tape excluding the pressure-sensitive adhesive layer, and is a member that supports the pressure-sensitive adhesive layer.
  • the adhesive layer includes the heat-sensitive adhesive layer positioned on the outermost surface of the single-sided adhesive tape, and another adhesive layer (for example, a pressure-sensitive adhesive layer) having a composition different from that of the heat-sensitive adhesive layer. may contain.
  • the heat-sensitive adhesive layer laminated on one side of the base material means that the heat-sensitive adhesive layer is disposed on one side of the base material, and the base material and the heat-sensitive adhesive layer are directly attached to each other. Or means that it is indirectly bonded, specifically, in the single-sided adhesive tape, the base material and the heat-sensitive adhesive layer are in direct contact, and It includes the case of having the above-mentioned other pressure-sensitive adhesive layer between the substrate and the above-mentioned substrate.
  • the heat-sensitive adhesive layer is a layer containing an adhesive that exhibits almost no adhesiveness at room temperature (23° C.) and exhibits adhesiveness when heated to a temperature equal to or higher than the glass transition point of the adhesive layer.
  • the pressure-sensitive adhesive layer is a layer containing an adhesive that exhibits adhesiveness at room temperature (23°C).
  • the substrate has a metal layer at least on the surface opposite to the heat-sensitive adhesive layer. That is, in the single-sided adhesive tape of the present invention, one outermost surface is the metal layer forming the base material, and the other outermost surface is the heat-sensitive adhesive layer.
  • the metal layer is exposed on the outermost surface when the single-sided adhesive tape is attached to the edge of the metal-clad laminate. . This makes it difficult for the single-sided adhesive tape to come off even when exposed to a strong alkaline solution.
  • a metal plating treatment such as electroless plating is performed, the metal plating layer deposited on the surface of the metal layer is difficult to separate from the metal layer. Therefore, even if the metal-clad laminate is plated with a single-sided adhesive tape, it is possible to prevent the metal-plated layer from peeling off from the single-sided adhesive tape in a later step. .
  • the metal forming the metal layer is not particularly limited, and examples thereof include copper, aluminum, nickel, and titanium. Moreover, alloys, such as stainless steel and Monel, are mentioned as a metal which comprises the said metal layer. Above all, it is preferable that the metal layer is made of copper, because the restoring force after folding is small and the single-sided pressure-sensitive adhesive tape can be easily handled because it is hard to break.
  • the substrate is not particularly limited as long as it has the metal layer on at least the surface opposite to the heat-sensitive adhesive layer, and may be composed of a single layer or multiple layers.
  • the base material consists of a single layer
  • the base material is composed only of the metal layer.
  • the said base material comprised only by the said metal layer is also called a metal base material.
  • the above metal base refers to all bases composed only of metal layers, and includes not only bases composed of a single metal layer but also bases composed of a plurality of metal layers.
  • the layer constituting the surface opposite to the heat-sensitive adhesive layer is the metal layer, and other layers are not limited.
  • the base material for example, the base material itself may be a metal base material, or a laminated base material having a resin base material and the metal layer laminated on the surface of the resin base material, good too.
  • the base material is the metal base material
  • the single-sided adhesive tape is folded back (bent) so as to extend from the front surface to the back surface of the metal-clad laminate and is attached to the edge of the metal-clad laminate.
  • the metal base retains its shape, it is possible to suppress the restoring force due to the bending of the metal base. As a result, gaps are less likely to occur between the ends of the metal-clad laminate and the heat-sensitive adhesive layer, and peeling is less likely to occur.
  • the metal constituting the metal substrate is not particularly limited, and includes the metals constituting the metal layer as described above. Above all, it is preferable that the metal substrate is a copper foil, since the restoring force after folding is small and the single-sided pressure-sensitive adhesive tape can be easily handled because it is hard to break.
  • the resin substrate is not particularly limited.
  • a resin film and a polyurethane-based resin film can be mentioned.
  • the resin substrate include polyolefin foam sheets such as polyethylene foam sheets and polypropylene foam sheets, and polyurethane foam sheets.
  • a PET film is preferable.
  • the thickness of the substrate is not particularly limited, but a preferable lower limit is 2 ⁇ m and a preferable upper limit is 30 ⁇ m. When the thickness of the base material is within the above range, peeling is less likely to occur even when the single-sided adhesive tape is folded back (bent) and attached to the edge of the metal-clad laminate. A more preferable lower limit of the thickness of the substrate is 4 ⁇ m, and a more preferable upper limit thereof is 20 ⁇ m.
  • the thickness of the metal layer in the substrate is not particularly limited, but the preferable lower limit of the ratio of the thickness of the metal layer to the thickness of the entire substrate is 0.1%.
  • the thickness ratio of the metal layer is 0.1% or more, the resistance of the single-sided pressure-sensitive adhesive tape to strong alkaline solutions is further enhanced.
  • a more preferable lower limit of the thickness ratio of the metal layer is 1%.
  • the upper limit of the thickness ratio of the metal layer is not particularly limited, and when the substrate is the metal substrate, the thickness ratio of the metal layer is 100%.
  • the upper limit of the coefficient of static friction of the heat-sensitive adhesive layer to SUS is 5. Since the heat-sensitive adhesive layer exhibits almost no adhesiveness at room temperature, when a part of the metal-clad laminate comes into contact with the heat-sensitive adhesive layer when the single-sided adhesive tape is attached to the edge of the metal-clad laminate, The heat-sensitive adhesive layer does not stick to the surface, and wrinkles are less likely to occur. Furthermore, since the coefficient of static friction with respect to SUS is 5 or less, the heat-sensitive adhesive layer can slide on the metal-clad laminate, so that the single-sided adhesive tape is attached to the edge of the metal-clad laminate.
  • a preferable upper limit of the coefficient of static friction for SUS is 3, and a more preferable upper limit is 2.
  • the lower limit of the coefficient of static friction with respect to SUS is not particularly limited, the practical lower limit is about 0.1.
  • the coefficient of static friction against SUS was measured using SUS304 (size 63 mm x 63 mm, weight 200 g) as a sliding piece, and at a tensile speed of 100 mm/min in accordance with JIS K7125 at room temperature (23°C) and humidity of 50%. can be measured at When measuring, put the single-sided adhesive tape as a sample on the other material, put the sliding piece as a weight on the single-sided adhesive tape, and pull the single-sided adhesive tape with a string to measure the resistance generated at that time. Measure the force (frictional force). As the mating material, SUS304 (size: 250 mm x 150 mm x thickness: 1.5 mm) can be used like the sliding piece.
  • the method for adjusting the coefficient of static friction within the above range is not particularly limited.
  • a method of adjusting the elastic modulus G', the gel fraction, the surface roughness Ra, etc. within appropriate ranges can be mentioned. More specifically, for example, as a method for adjusting the peak temperature of the loss tangent of the heat-sensitive adhesive layer, the storage elastic modulus G′ at 23° C., the gel fraction, etc., the base polymer contained in the heat-sensitive adhesive layer
  • a method of adjusting the type, molecular weight and molecular weight distribution, the type and content of the tackifying resin, the type and content of the cross-linking agent, and the like can be mentioned.
  • a film for example, release-treated PET
  • a method of appropriately adjusting the surface roughness of the film Since the surface roughness of the film used at this time is transferred to the surface of the heat-sensitive adhesive layer, the surface roughness of the heat-sensitive adhesive layer can be improved by appropriately adjusting the surface roughness of the film. Ra can be adjusted.
  • the heat-sensitive adhesive layer has a peak temperature of loss tangent (hereinafter also referred to as tan ⁇ or simply loss tangent) measured at a measurement frequency of 1 Hz using a dynamic viscoelasticity measuring device, although the peak temperature is not particularly limited.
  • tan ⁇ or simply loss tangent a peak temperature of loss tangent measured at a measurement frequency of 1 Hz using a dynamic viscoelasticity measuring device.
  • the peak temperature of the loss tangent is more preferably 42° C. or higher, even more preferably 45° C. or higher.
  • the peak temperature of the loss tangent is preferably 100° C.
  • the loss tangent is measured using a dynamic viscoelasticity measuring device (DVA-200, manufactured by IT Keisoku Co., Ltd., or equivalent) under the conditions of 5 ° C./min and 1 Hz in a low-speed heating shear deformation mode. It can be obtained by measuring dynamic viscoelasticity spectrum from -40°C to 140°C.
  • DVA-200 manufactured by IT Keisoku Co., Ltd., or equivalent
  • the storage elastic modulus G' of the heat-sensitive adhesive layer is not particularly limited, but the preferred lower limit of the storage elastic modulus G' at 23°C is 5 MPa, and the preferred upper limit of the storage elastic modulus G' at 100°C is 0.2 MPa. . If the storage elastic modulus G′ at 23° C. is 5 MPa or more, the heat-sensitive adhesive layer exhibits almost no adhesiveness at room temperature. can be further suppressed. A more preferable lower limit of the storage elastic modulus G' at 23°C is 8 MPa, and a more preferable lower limit is 10 MPa. Although the upper limit of the storage elastic modulus G' at 23°C is not particularly limited, the upper limit is preferably 10000 MPa, more preferably 1000 MPa, from the viewpoint that the single-sided adhesive tape can be easily rolled.
  • the heat-sensitive adhesive layer exhibits sufficient adhesiveness by heating, so that the single-sided adhesive tape is brought into contact with the edge of the metal-clad laminate.
  • the single-sided adhesive tape can be attached to the edge of the metal-clad laminate by adjusting the position and the like so that the single-sided adhesive tape does not wrinkle or float, and then heat-pressing it.
  • a more preferable upper limit of the storage elastic modulus G' at 100°C is 0.1 MPa, and a further preferable upper limit is 0.08 MPa.
  • the storage modulus G′ at 23° C. or 100° C. is measured using a dynamic viscoelasticity measuring device (for example, “DVA-200” manufactured by IT Instrument Control Co., Ltd., “ARES” manufactured by Rheometrics Co., Ltd.). It can be obtained by measuring from ⁇ 40° C. to 140° C. under the conditions of shear mode of physical viscoelasticity measurement, angular frequency of 1 Hz, and speed of 5° C./min.
  • a dynamic viscoelasticity measuring device for example, “DVA-200” manufactured by IT Instrument Control Co., Ltd., “ARES” manufactured by Rheometrics Co., Ltd.
  • the gel fraction of the heat-sensitive adhesive layer is not particularly limited, but the preferred lower limit is 50% by weight.
  • the gel fraction is 50% by weight or more, the heat-sensitive adhesive layer is prevented from being swelled by the strong alkaline solution, and the resistance of the single-sided adhesive tape to the strong alkaline solution becomes higher.
  • the gel fraction is 50% by weight or more, it becomes easier to adjust the coefficient of static friction to the SUS within the above range, and wrinkles are further suppressed when the single-sided adhesive tape is attached to the edge of the metal-clad laminate. can do.
  • a more preferable lower limit of the gel fraction is 60% by weight.
  • the upper limit of the gel fraction is not particularly limited, the upper limit is preferably 90% by weight, and the upper limit is more preferably 80% by weight, since the heat-sensitive adhesive layer tends to exhibit sufficient adhesiveness when heated.
  • the gel fraction can be measured by the following method. 0.1 g of only the heat-sensitive adhesive layer (adhesive composition) is taken out from the single-sided adhesive tape, immersed in 50 mL of ethyl acetate, and shaken with a shaker at a temperature of 23°C and 200 rpm for 24 hours. After shaking, a metal mesh (#200 mesh) is used to separate the ethyl acetate and the pressure-sensitive adhesive composition that has absorbed and swollen the ethyl acetate.
  • the adhesive composition after separation is dried at 110° C. for 1 hour.
  • the weight of the pressure-sensitive adhesive composition containing the metal mesh after drying is measured, and the gel fraction is calculated using the following formula.
  • Gel fraction (% by weight) 100 x (W 1 - W 2 )/W 0 (W 0 : initial weight of adhesive composition, W 1 : weight of adhesive composition containing metal mesh after drying, W 2 : initial weight of metal mesh)
  • the surface roughness Ra of the heat-sensitive adhesive layer is not particularly limited, but the preferred lower limit is 0.01 ⁇ m and the preferred upper limit is 0.8 ⁇ m. If the surface roughness Ra is within the above range, it becomes easier to adjust the static friction coefficient to the above SUS within the above range, and wrinkles are further suppressed when the single-sided adhesive tape is attached to the edge of the metal-clad laminate. can be done.
  • a more preferable lower limit of the surface roughness Ra is 0.02 ⁇ m, and a more preferable upper limit thereof is 0.1 ⁇ m.
  • the surface roughness Ra means arithmetic mean roughness defined in JIS B 0601-2001.
  • the heat-sensitive adhesive layer is not particularly limited, and for example, rubber-based, styrene-based, polyester-based, acrylic-based heat-sensitive adhesive layers can be used. Since it can be adhered to various adherends by thermocompression, it preferably contains an acrylic polymer.
  • the acrylic polymer contained in the heat-sensitive adhesive layer (hereinafter also referred to as the acrylic polymer for the heat-sensitive adhesive layer) is not particularly limited, but preferably has a structural unit derived from a monomer having a crosslinkable functional group.
  • the acrylic polymer for the heat-sensitive adhesive layer can be cross-linked when a cross-linking agent is used in combination.
  • the degree of crosslinking at that time the storage elastic modulus G' of the heat-sensitive adhesive layer can be easily adjusted within the above range, and the coefficient of static friction against SUS can be easily adjusted within the above range.
  • Examples of the crosslinkable functional group include a hydroxyl group, a carboxyl group, a glycidyl group, an amino group, an amide group, and a nitrile group. Among them, a hydroxyl group or a carboxyl group is preferable because the storage elastic modulus G′ of the heat-sensitive adhesive layer can be easily adjusted.
  • Examples of the monomer having a hydroxyl group include (meth)acrylic acid esters having a hydroxyl group such as 4-hydroxybutyl (meth)acrylate and 2-hydroxyethyl (meth)acrylate.
  • Examples of the monomer having a carboxyl group include (meth)acrylic acid.
  • Examples of the monomer having a glycidyl group include glycidyl (meth)acrylate.
  • examples of the amide group-containing monomer include hydroxyethylacrylamide, isopropylacrylamide, and dimethylaminopropylacrylamide.
  • examples of the nitrile group-containing monomer include acrylonitrile.
  • These monomers having a crosslinkable functional group may be used alone or in combination of two or more.
  • (meth)acrylate means acrylate or methacrylate
  • (meth)acryl means acrylic or methacrylic.
  • the acrylic polymer may be a methacrylic polymer.
  • the content of the structural unit derived from the monomer having a crosslinkable functional group in the acrylic polymer for the heat-sensitive adhesive layer is not particularly limited, but the preferred lower limit is 0.1% by weight and the preferred upper limit is 5% by weight. Further, when a monomer having a carboxyl group is used as the monomer having a crosslinkable functional group, the resistance of the single-sided adhesive tape to a strong alkaline solution is further increased. A more preferable upper limit of the content is 3% by weight, and a further preferable upper limit is 0.5% by weight.
  • the acrylic polymer for the heat-sensitive adhesive layer preferably has a structural unit derived from (meth)acrylate having an alkyl group having 1 to 4 carbon atoms, and has an alkyl group having 1 to 4 carbon atoms. It is more preferable to have structural units derived from methacrylate. Moreover, the acrylic polymer for the heat-sensitive adhesive layer preferably has a structural unit derived from (meth)acrylate having an alkyl group having a cyclic structure.
  • the acrylic polymer for the heat-sensitive adhesive layer has these structural units, it becomes easier to adjust the peak temperature of the loss tangent of the heat-sensitive adhesive layer and the storage elastic modulus G' within the above range, and the static friction against the SUS Since it becomes easier to adjust the coefficient within the above range, wrinkles can be further suppressed when the single-sided adhesive tape is attached to the edge of the metal-clad laminate.
  • the acrylic polymer for the heat-sensitive adhesive layer is selected from the group consisting of a structural unit derived from a methacrylate having an alkyl group having 1 to 4 carbon atoms and a structural unit derived from a methacrylate having an alkyl group having a cyclic structure. It is more preferable to have at least one selected.
  • the (meth)acrylate having an alkyl group having 1 to 4 carbon atoms is not particularly limited, and examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and the like. mentioned.
  • the (meth)acrylate having an alkyl group having a cyclic structure is not particularly limited, and examples thereof include cyclohexyl (meth)acrylate and isobornyl (meth)acrylate. These (meth)acrylates may be used alone or in combination of two or more.
  • the preferable lower limit is 50% by weight and the preferable upper limit is 98% by weight. If the total content of the structural units is within the above range, the peak temperature of the loss tangent and the storage elastic modulus G′ of the heat-sensitive adhesive layer can be easily adjusted within the above range, and the static friction coefficient for the SUS is within the above range. Therefore, wrinkles can be further suppressed when the single-sided adhesive tape is attached to the edge of the metal-clad laminate.
  • a more preferable lower limit of the total content of the structural units is 60% by weight, a more preferable lower limit is 70% by weight, a more preferable upper limit is 95% by weight, a still more preferable upper limit is 90% by weight, and a still more preferable upper limit is 80% by weight.
  • the total content is a structural unit derived from a (meth)acrylate having an alkyl group having 1 to 4 carbon atoms, and a structural unit derived from a (meth)acrylate having an alkyl group having a cyclic structure.
  • the acrylic polymer for the heat-sensitive adhesive layer may contain either one or both of them.
  • the preferred lower limit is 50% by weight and the preferred upper limit is 90% by weight.
  • a more preferable lower limit of the above total content is 60% by weight, and a more preferable upper limit is 80% by weight.
  • the acrylic polymer for the heat-sensitive adhesive layer may further have structural units derived from other monomers as long as the effects of the present invention are not impaired.
  • the other monomers include n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, Lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, ethyl carbitol (meth)acrylate, vinyl acetate, fluorine-containing (meth)acrylate, etc.
  • the acrylic polymer for the heat-sensitive adhesive layer is prepared by an ultraviolet polymerization method, it preferably further contains structural units derived from polyfunctional monomers such as divinylbenzene and trimethylolpropane tri(meth)acrylate. .
  • the solubility parameter (SP value) of the acrylic polymer for the heat-sensitive adhesive layer is not particularly limited, but the preferred lower limit is 9.2 and the preferred upper limit is 10.5.
  • SP value is within the above range, the heat-sensitive adhesive layer is prevented from being swelled by a strong alkaline solution, and the resistance of the single-sided adhesive tape to a strong alkaline solution is increased. Further, when the SP value is within the above range, the adhesion of the heat-sensitive adhesive layer to the metal-clad laminate is increased, and the metal-clad laminate can be sufficiently protected.
  • the SP value has a more preferable lower limit of 9.5, a more preferable upper limit of 10.2, a still more preferable lower limit of 9.6, and a still more preferable upper limit of 10.
  • the solubility parameter (SP value) means the solubility parameter (SP value) ((cal/cm 3 ) 0.5 ) according to the Fedors method, and is calculated according to the Fedors method (RF Fedors, Polym. Eng. Sci. , 14(2), 147-154 (1974)) and is an index capable of expressing the ease of dissolution.
  • the weight average molecular weight (Mw) of the acrylic polymer for the heat-sensitive adhesive layer is not particularly limited, but the preferred lower limit is 250,000, the preferred upper limit is 2,000,000, the more preferred lower limit is 300,000, and the further preferred lower limit is 400,000. and a more preferable upper limit is 1,500,000.
  • the weight-average molecular weight (Mw) can be adjusted by polymerization conditions (eg, type or amount of polymerization initiator, polymerization temperature, monomer concentration, etc.). Moreover, the weight average molecular weight (Mw) can be measured by the following method.
  • the acrylic polymer solution is filtered through a filter (material: polytetrafluoroethylene, pore diameter: 0.2 ⁇ m).
  • the obtained filtrate is supplied to a gel permeation chromatograph (e.g., Waters, 2690 Separations Model), and GPC measurement is performed under the conditions of a sample flow rate of 1 ml/min and a column temperature of 40 ° C., and the acrylic polymer is converted to polystyrene.
  • the molecular weight is measured to determine the weight average molecular weight (Mw).
  • Mw weight average molecular weight
  • GPC KF-806L or GPC LF-804 manufactured by Showa Denko KK
  • a differential refractometer is used as the detector.
  • the method for preparing the acrylic polymer for the heat-sensitive adhesive layer is not particularly limited, and examples thereof include a method of radically reacting the monomers from which the structural units are derived in the presence of a polymerization initiator.
  • the polymerization method is not particularly limited, and conventionally known methods can be used. Examples thereof include solution polymerization (boiling point polymerization or constant temperature polymerization), emulsion polymerization, suspension polymerization, bulk polymerization and the like. Among them, solution polymerization is preferable from the viewpoint of ease of synthesis and water resistance.
  • reaction solvents include ethyl acetate, toluene, methyl ethyl ketone, methyl sulfoxide, ethanol, acetone, and diethyl ether. These reaction solvents may be used alone or in combination of two or more.
  • the polymerization initiator is not particularly limited, and examples thereof include organic peroxides and azo compounds.
  • organic peroxide include 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane, t-hexylperoxypivalate, t-butylperoxypivalate, 2,5 -dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxy isobutyrate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate and the like.
  • the azo compound include azobisisobutyronitrile and azobiscyclohexanecarbonitrile.
  • the heat-sensitive adhesive layer preferably further contains a tackifying resin.
  • a tackifying resin By containing the tackifying resin in the heat-sensitive adhesive layer, the interfacial adhesion is improved when the single-sided adhesive tape is heat-pressed, and the resistance of the single-sided adhesive tape to strong alkaline solutions is further increased.
  • the tackifying resin is not particularly limited, and examples thereof include coumarone resins, terpene resins, terpene phenol resins, rosin resins, rosin derivative resins, petroleum resins, alkylphenol resins, and hydrides thereof. These tackifying resins may be used alone or in combination of two or more.
  • the terpene phenolic resin means a polymer containing terpene residues and phenol residues.
  • terpene phenol resins include copolymers of terpene and phenol compounds (terpene-phenol copolymer resins), and homopolymers or copolymers of terpene (terpene resins, typically unmodified terpene resins). is a concept including phenol-modified terpene resins modified with phenol, and resins obtained by hydrogenating the terpene sites in these resins.
  • the terpene constituting the terpene phenol resin is not particularly limited, but monoterpenes such as ⁇ -pinene, ⁇ -pinene, limonene and camphene are preferable.
  • Limonene includes d-form, l-form and d/l-form (dipentene).
  • the rosin resin include unmodified rosins (fresh rosins) such as gum rosin, wood rosin and tall oil rosin, modified rosins obtained by modifying these unmodified rosins, and the like. Modification of the modified rosin includes, for example, hydrogenation, disproportionation, and polymerization. More specific examples of the modified rosin include hydrogenated rosin, disproportionated rosin, polymerized rosin, and other chemically modified rosins.
  • unmodified rosins fresh rosins
  • modified rosins obtained by modifying these unmodified rosins
  • Modification of the modified rosin includes, for example, hydrogenation, disproportionation, and polymerization. More specific examples of the modified rosin include hydrogenated rosin, disproportionated rosin, polymerized rosin, and other chemically modified rosins.
  • a rosin ester resin obtained by esterifying the rosin resin with an alcohol an unsaturated fatty acid-modified rosin resin obtained by modifying the rosin resin with an unsaturated fatty acid, and an unsaturated rosin ester resin.
  • Unsaturated fatty acid-modified rosin ester resin modified with saturated fatty acid and the like can be mentioned.
  • the rosin derivative resin include rosin alcohol resin obtained by reducing the carboxyl group in the unsaturated fatty acid-modified rosin resin or unsaturated fatty acid-modified rosin ester resin.
  • examples of the rosin derivative resins include metal salts of the rosin resins or rosin derivative resins (particularly, rosin ester resins), rosin phenol resins, and the like.
  • the rosin phenol resin can be obtained by adding phenol to the above rosin resin or rosin derivative resin under an acid catalyst, followed by thermal polymerization.
  • the petroleum resins include aliphatic (C5) petroleum resins, aromatic (C9) petroleum resins, C5/C9 copolymer petroleum resins, alicyclic petroleum resins, and Hydrogenated products thereof and the like are included.
  • the tackifier resin preferably has a softening point of 100° C. or higher and a hydroxyl value of 25 mgKOH/g or higher.
  • the tackifying resin more preferably contains a hydrogenated rosin ester resin having a hydroxyl value of 40 mgKOH/g or more.
  • the upper limit of the hydroxyl value of the hydrogenated rosin ester resin having a hydroxyl value of 40 mgKOH/g or more is not particularly limited, it is usually about 80 mgKOH/g, preferably 50 mgKOH/g or less.
  • the content of the tackifying resin is not particularly limited, but the preferred lower limit is 5 parts by weight, the preferred upper limit is 50 parts by weight, and the more preferred lower limit is 10 parts by weight, with respect to 100 parts by weight of the acrylic polymer for the heat-sensitive adhesive layer. A more preferable upper limit is 35 parts by weight.
  • the content of the tackifying resin is within the above range, the interfacial adhesion is improved when the single-sided adhesive tape is heat-pressed, and the resistance of the single-sided adhesive tape to strong alkaline solutions is further enhanced.
  • the heat-sensitive adhesive layer may contain a silane coupling agent.
  • a silane coupling agent in the heat-sensitive adhesive layer, the interfacial adhesion is improved when the single-sided adhesive tape is heat-pressed, and the resistance of the single-sided adhesive tape to strong alkaline solutions is further increased.
  • the silane coupling agent is not particularly limited, and examples include vinyltrimethoxysilane, vinyltriethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -methacryloxypropylmethyldimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane.
  • ⁇ -glycidoxypropylmethyldimethoxysilane ⁇ -glycidoxypropylmethyldiethoxysilane
  • ⁇ -glycidoxypropyltriethoxysilane 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane
  • ⁇ -amino Propyltrimethoxysilane ⁇ -aminopropyltriethoxysilane
  • ⁇ -aminopropyltrimethylmethoxysilane N-(2-aminoethyl)3-aminopropyltriethoxysilane, N-(2-aminoethyl)3-aminopropylmethyl dimethoxysilane
  • ⁇ -mercaptopropyltrimethoxysilane ⁇ -mercaptopropyltriethoxysilane, mercaptobutyltrimethoxysilane, ⁇ -mercaptopropylmethyldimethoxys
  • the content of the silane coupling agent is not particularly limited, but the preferred lower limit is 0.1 parts by weight and the preferred upper limit is 5 parts by weight with respect to 100 parts by weight of the acrylic polymer for the heat-sensitive adhesive layer.
  • the content of the silane coupling agent is within this range, the interfacial adhesion is improved when the single-sided pressure-sensitive adhesive tape is heat-pressed, and the resistance of the single-sided pressure-sensitive adhesive tape to strong alkaline solutions is further increased.
  • a more preferable lower limit to the content of the silane coupling agent is 0.5 parts by weight, and a more preferable upper limit is 3 parts by weight.
  • the heat-sensitive adhesive layer may further contain a cross-linking agent.
  • the acrylic polymer for the heat-sensitive adhesive layer contains a structural unit derived from a monomer having a cross-linkable functional group. It is possible to crosslink between the system polymers.
  • the cross-linking agent is not particularly limited, and examples thereof include isocyanate-based cross-linking agents, aziridine-based cross-linking agents, epoxy-based cross-linking agents, and metal chelate-type cross-linking agents. Among them, an isocyanate-based cross-linking agent and an epoxy-based cross-linking agent are preferable.
  • the content of the crosslinking agent is not particularly limited, but the preferred lower limit is 0.01 parts by weight, the preferred upper limit is 10 parts by weight, and the more preferred lower limit is 0.1 parts by weight, per 100 parts by weight of the acrylic polymer for the heat-sensitive adhesive layer. Parts by weight, a more preferred upper limit is 5 parts by weight.
  • the heat-sensitive adhesive layer may contain additives such as plasticizers, emulsifiers, softeners, fillers, pigments and dyes, and other resins, if necessary.
  • the thickness of the heat-sensitive adhesive layer is not particularly limited, but the preferred lower limit is 5 ⁇ m and the preferred upper limit is 100 ⁇ m. When the thickness is within the above range, the single-sided adhesive tape can be satisfactorily heat-pressed, wrinkles at that time can be further suppressed, and the single-sided adhesive tape has a higher resistance to strong alkaline solutions.
  • a more preferable lower limit of the thickness is 10 ⁇ m, a more preferable upper limit is 50 ⁇ m, a still more preferable lower limit is 20 ⁇ m, and a further preferable upper limit is 40 ⁇ m.
  • the thickness of the heat-sensitive adhesive layer is preferably thicker than 1/2 of the thickness of the metal-clad laminate used as the adherend.
  • the edge of the metal-clad laminate and the heat-sensitive adhesive A gap is less likely to occur with the agent layer, and peeling is less likely to occur. More preferably, the thickness of the heat-sensitive adhesive layer is thicker than 2/3 of the thickness of the metal-clad laminate.
  • the single-sided adhesive tape preferably further has a pressure-sensitive adhesive layer between the substrate and the heat-sensitive adhesive layer.
  • the anchoring property between the substrate and the heat-sensitive adhesive layer is increased, so that the resistance of the single-sided pressure-sensitive adhesive tape to strong alkaline solutions is increased.
  • the storage elastic modulus G' of the pressure-sensitive adhesive layer is not particularly limited, but the preferred upper limit of the storage elastic modulus G' at 23°C is 0.2 MPa. When the storage elastic modulus G′ at 23° C. is 0.2 MPa or less, the anchoring property between the substrate and the heat-sensitive adhesive layer is further improved. A more preferable upper limit of the storage modulus G' at 23°C is 0.15 MPa.
  • the lower limit of the storage elastic modulus G' at 23°C is not particularly limited, but from the viewpoint of maintaining the cohesive strength of the pressure-sensitive adhesive layer, the preferred lower limit is 0.01 MPa, and the more preferred lower limit is 0.03 MPa.
  • a dynamic viscoelasticity measuring device for example, "DVA-200” manufactured by IT Instrument Control Co., Ltd., “ARES” manufactured by Rheometrics, etc.
  • DVA-200 manufactured by IT Instrument Control Co., Ltd.
  • ARES manufactured by Rheometrics, etc.
  • the storage elastic modulus G′ at 23° C. can be adjusted by the type, molecular weight and molecular weight distribution of the base polymer contained in the pressure-sensitive adhesive layer, the type and content of the tackifying resin, the type and content of the cross-linking agent, and the like. .
  • the pressure-sensitive adhesive layer is not particularly limited, and for example, rubber-based, styrene-based, polyester-based, acrylic-based pressure-sensitive adhesive layers can be used. and exhibits adhesiveness at room temperature and can be adhered to various adherends, and therefore, it preferably contains an acrylic polymer.
  • the acrylic polymer contained in the pressure-sensitive adhesive layer (hereinafter also referred to as acrylic polymer for pressure-sensitive adhesive layer) is not particularly limited.
  • the acrylic polymer for the pressure-sensitive adhesive layer contains an acrylic acid alkyl ester and/or methacrylic acid alkyl ester having an alkyl group having a carbon number of 1 to 18 as a main monomer, and if necessary, a crosslinkable functional It is preferably a (meth)acrylic acid ester copolymer obtained by copolymerizing a monomer having a group by a conventional method. In addition, other copolymerizable modifying monomers may be copolymerized.
  • the acrylic polymer for the pressure-sensitive adhesive layer preferably has structural units derived from a monomer having a crosslinkable functional group. By having such a structural unit, the acrylic polymer for the pressure-sensitive adhesive layer can be cross-linked when a cross-linking agent is used in combination. By adjusting the degree of crosslinking at that time, the storage elastic modulus G' of the pressure-sensitive adhesive layer can be adjusted.
  • Examples of the crosslinkable functional group include a hydroxyl group, a carboxyl group, a glycidyl group, an amino group, an amide group, and a nitrile group. Among them, a hydroxyl group or a carboxyl group is preferable because the storage elastic modulus G′ of the pressure-sensitive adhesive layer can be easily adjusted.
  • Examples of the monomer having a hydroxyl group include (meth)acrylic acid esters having a hydroxyl group such as 4-hydroxybutyl (meth)acrylate and 2-hydroxyethyl (meth)acrylate.
  • Examples of the monomer having a carboxyl group include (meth)acrylic acid.
  • Examples of the monomer having a glycidyl group include glycidyl (meth)acrylate.
  • Examples of the amide group-containing monomer include hydroxyethylacrylamide, isopropylacrylamide, and dimethylaminopropylacrylamide.
  • Examples of the nitrile group-containing monomer include acrylonitrile. These monomers having a crosslinkable functional group may be used alone or in combination of two or more.
  • the content of the structural unit derived from the monomer having a crosslinkable functional group in the acrylic polymer for the pressure-sensitive adhesive layer is not particularly limited, but the preferred lower limit is 0.1% by weight and the preferred upper limit is 5% by weight. . Further, when a monomer having a carboxyl group is used as the monomer having a crosslinkable functional group, the resistance of the single-sided adhesive tape to a strong alkaline solution is further increased. A more preferable upper limit of the content is 3% by weight, and a further preferable upper limit is 0.5% by weight.
  • the acrylic polymer for the pressure-sensitive adhesive layer preferably has a structural unit derived from (meth)acrylate having an alkyl group with 8 or more carbon atoms.
  • a structural unit derived from (meth)acrylate having an alkyl group with 8 or more carbon atoms By having such a structural unit, the hydrophobicity of the acrylic polymer for the pressure-sensitive adhesive layer is increased, and the infiltration of a strong alkaline solution into the molecular chain is further suppressed. is more resistant to
  • Examples of the (meth)acrylate having an alkyl group having 8 or more carbon atoms include n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl ( meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, isobornyl (meth)acrylate and the like.
  • These (meth)acrylates having an alkyl group with 8 or more carbon atoms may be used alone or in combination of two or more.
  • 2-ethylhexyl acrylate, lauryl acrylate, and lauryl methacrylate are preferably used because the pressure-sensitive adhesive layer does not become too hard and sufficient tackiness can be maintained.
  • the content of the structural unit derived from the (meth)acrylate having an alkyl group having 8 or more carbon atoms in the acrylic polymer for the pressure-sensitive adhesive layer is not particularly limited, but the preferred lower limit is 15% by weight, and the preferred upper limit is 99% by weight.
  • the content of the (meth)acrylate having an alkyl group having 8 or more carbon atoms is within the above range, the hydrophobicity of the acrylic polymer for the pressure-sensitive adhesive layer is increased, and a strong alkaline solution enters the molecular chain. is further suppressed, the resistance of the single-sided adhesive tape to strong alkaline solutions is further increased.
  • a more preferable lower limit to the content of the structural unit derived from the (meth)acrylate having an alkyl group having 8 or more carbon atoms is 20% by weight, and a more preferable upper limit is 30% by weight.
  • the above acrylic polymer for the pressure-sensitive adhesive layer may further have structural units derived from other monomers to the extent that the effects of the present invention are not impaired.
  • examples of the above other monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, ethyl carbitol (meth) ) acrylate, vinyl acetate, fluorine-containing (meth)acrylate, and the like.
  • the acrylic polymer for the pressure-sensitive adhesive layer is prepared by an ultraviolet polymerization method, it may further contain structural units derived from polyfunctional monomers such as divinylbenzene and trimethylolpropane tri(meth)acrylate. preferable.
  • the solubility parameter (SP value) of the acrylic polymer for the pressure-sensitive adhesive layer is not particularly limited, and is the same as the solubility parameter (SP value) of the acrylic polymer for the heat-sensitive adhesive layer. you can
  • the weight-average molecular weight (Mw) of the acrylic polymer for the pressure-sensitive adhesive layer is not particularly limited, and may be the same weight-average molecular weight (Mw) as the weight-average molecular weight (Mw) of the acrylic polymer for the heat-sensitive adhesive layer. you can
  • the method for preparing the acrylic polymer for the pressure-sensitive adhesive layer is not particularly limited, and in the same manner as in the case of the acrylic polymer for the heat-sensitive adhesive layer, for example, a monomer from which the structural unit is derived may be added as a polymerization initiator. and a method of radical reaction in the presence of.
  • the pressure-sensitive adhesive layer preferably further contains a tackifying resin.
  • the tackifying resin is not particularly limited, and the same tackifying resin as that used in the heat-sensitive adhesive layer can be used.
  • the content of the tackifying resin is not particularly limited, but the preferred lower limit is 3 parts by weight, the preferred upper limit is 50 parts by weight, and the more preferred lower limit is 10 parts by weight, relative to 100 parts by weight of the acrylic polymer for the pressure-sensitive adhesive layer. , and a more preferred upper limit is 35 parts by weight. When the content of the tackifier resin is within the above range, the adhesive strength of the pressure-sensitive adhesive layer is improved.
  • the pressure-sensitive adhesive layer may contain a silane coupling agent.
  • the silane coupling agent is not particularly limited, and the same silane coupling agent as the silane coupling agent used in the heat-sensitive adhesive layer can be used.
  • the content of the silane coupling agent is also not particularly limited, and the same content as the content in the heat-sensitive adhesive layer can be employed.
  • the pressure-sensitive adhesive layer may further contain a cross-linking agent.
  • the pressure-sensitive adhesive layer contains the cross-linking agent
  • the acrylic polymer for the pressure-sensitive adhesive layer contains a structural unit derived from the monomer having the crosslinkable functional group
  • the pressure-sensitive adhesive Cross-linking can be performed between the layer acrylic polymers.
  • the cross-linking agent is not particularly limited, and the same cross-linking agent as that used in the heat-sensitive adhesive layer can be used, and an epoxy-based cross-linking agent is more preferable.
  • the content of the cross-linking agent is also not particularly limited, and the same content as the content in the heat-sensitive adhesive layer can be adopted.
  • the pressure-sensitive adhesive layer may contain additives such as plasticizers, emulsifiers, softeners, fillers, pigments and dyes, and other resins, if necessary.
  • the gel fraction of the pressure-sensitive adhesive layer is not particularly limited, and may be the same as that of the heat-sensitive adhesive layer, preferably 50% by weight or more.
  • the thickness of the pressure-sensitive adhesive layer is not particularly limited, but the preferred lower limit is 0.1 ⁇ m and the preferred upper limit is 30 ⁇ m. When the thickness of the pressure-sensitive adhesive layer is within the above range, the anchoring property between the substrate and the heat-sensitive adhesive layer is further improved.
  • a more preferable lower limit of the thickness of the pressure-sensitive adhesive layer is 5 ⁇ m, and a more preferable upper limit thereof is 20 ⁇ m.
  • a base material and a heat-sensitive adhesive layer laminated on one surface of the base material are provided, and the base material has at least the surface opposite to the heat-sensitive adhesive layer.
  • a single-sided pressure-sensitive adhesive tape having a metal layer was described, but based on the relationship between the heat-sensitive adhesive layer and the metal layer instead of the relationship between the substrate, the heat-sensitive adhesive layer, and the metal layer, in the present invention, It can be said that the single-sided pressure-sensitive adhesive tape may have the above-mentioned metal layer as a member constituting the above-mentioned base material disposed on the surface opposite to the above-mentioned heat-sensitive adhesive layer.
  • a single-sided adhesive tape having a metal layer on one side and a heat-sensitive adhesive layer on the other side, wherein the heat-sensitive adhesive layer has a static friction coefficient of 5 against SUS.
  • the following are single-sided adhesive tapes. Even in such a different embodiment, it is possible to realize a single-sided pressure-sensitive adhesive tape that is less likely to wrinkle when attached to a thin adherend and has excellent resistance to strong alkaline solutions.
  • the method for producing the single-sided pressure-sensitive adhesive tape of the present invention is not particularly limited. After coating on a release-treated PET film, it is dried to form a heat-sensitive adhesive layer, and the heat-sensitive adhesive layer is transferred to a base material.
  • the use of the single-sided adhesive tape of the present invention is not particularly limited, but it is less likely to wrinkle when attached to a thin adherend and has excellent resistance to strong alkaline solutions. It can be preferably used in some cases.
  • the single-sided pressure-sensitive adhesive tape of the present invention is particularly suitable for attaching to the edge of the metal-clad laminate to protect the edge of the metal-clad laminate in the etching process, the desmear process, or the electroless plating process.
  • the single-sided adhesive tape of the present invention is a metal-clad laminate, especially a thin one (specifically, a thickness of 100 ⁇ m or less, preferably around 20 to 50 ⁇ m, especially around 30 to 40 ⁇ m).
  • the edge of the metal-clad laminate can be attached to the edge of the metal-clad laminate.
  • the region protected by the single-sided adhesive tape can be separated (removed) by trimming the region of the metal-clad laminate protected by the single-sided adhesive tape.
  • the method of protecting the edges of the metal-clad laminate by attaching the single-sided adhesive tape of the present invention to the edges of the metal-clad laminate is not particularly limited. and a method of thermocompression bonding to the end of the .
  • a temperature of 80 to 120° C., a pressure of 0.1 to 5 MPa, and a time of 30 to 300 seconds can be used.
  • the single-sided adhesive tapes When the single-sided adhesive tapes are attached to the squares of the metal-clad laminate, the single-sided adhesive tapes may be attached overlappingly or may be attached so as not to overlap.
  • FIGS. 1 to 8 are cross-sectional views schematically showing an example of a state in which the edge of a metal-clad laminate is protected using the single-sided pressure-sensitive adhesive tape of the present invention.
  • a single-sided adhesive tape 30 having a substrate 31 and a heat-sensitive adhesive layer 32 is used.
  • the single-sided adhesive tape 30 is folded back (bent) and attached to the end portion of the metal-clad laminate 2 so as to extend from the front surface to the back surface of the metal-clad laminate 2.
  • FIGS. Furthermore, in FIG. 4 , the entire back surface of the metal-clad laminate 2 is covered with a single-sided adhesive tape 30 .
  • Adhesive tape 30' is used in the edge-protected metal-clad laminate 1 shown in FIGS.
  • Adhesive tape 30' is used in the edge-protected metal-clad laminate 1 shown in FIGS.
  • a single-sided adhesive tape 30'' having a substrate 31'' and a heat-sensitive adhesive layer 32'' are used.
  • 3a indicates the interface between the heat-sensitive adhesive layers, and by minimizing the gap at this interface 3a, damage to the edges of the metal-clad laminate 2 can be further suppressed. It is possible to further suppress the infiltration of the solution into the end portion even when exposed to a strong alkaline solution.
  • FIG. 1 is a cross-sectional view schematically showing an example of a state in which the edge of a metal-clad laminate is protected using the single-sided pressure-sensitive adhesive tape of the present invention
  • BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view schematically showing an example of a state in which the edge of a metal-clad laminate is protected using the single-sided pressure-sensitive adhesive tape of the present invention
  • FIG. 1 is a cross-sectional view schematically showing an example of a state in which the edge of a metal-clad laminate is protected using the single-sided pressure-sensitive adhesive tape of the present invention
  • FIG. 1 is a cross-sectional view schematically showing an example of a state in which the edge of a metal-clad laminate is protected using the single-sided pressure-sensitive adhesive tape of the present invention
  • FIG. 1 is a cross-sectional view schematically showing an example of a state in which the edge of a metal-clad laminate is protected using the single-sided pressure-sensitive adhesive tape of the present invention
  • FIG. 1 is a cross-sectional view schematically showing an example of a state in which the edge of a metal-clad laminate is protected using the single-sided pressure-sensitive adhesive tape of the present invention
  • FIG. 1 is a cross-sectional view schematically showing an example of a state in which the edge of a metal-clad laminate is protected using the single-sided pressure-sensitive adhesive tape of the present invention
  • FIG. 1 is a cross-sectional view schematically showing an example of a state in which the edge of a metal-clad laminate is protected using the single-sided pressure-sensitive adhesive tape of the present invention
  • Example 1 Preparation of acrylic polymer Ethyl acetate was added as a polymerization solvent into a reaction vessel, and nitrogen was bubbled through the reaction vessel. Subsequently, a polymerization initiator solution obtained by diluting 0.3 parts by weight of azobisisobutyronitrile 10 times with ethyl acetate as a polymerization initiator was charged into the reaction vessel, and a total of 100 parts by weight of monomers having the composition shown in Table 1 was added. was added dropwise over 2 hours.
  • a polymerization initiator solution obtained by diluting 0.3 parts by weight of azobisisobutyronitrile 10 times with ethyl acetate as a polymerization initiator was put into the reaction vessel again, and the polymerization reaction was performed for 4 hours to obtain an acrylic polymer.
  • a containing solution was obtained.
  • a solubility parameter (SP value) was determined for the obtained acrylic polymer.
  • the weight average molecular weight (Mw) in terms of polystyrene was determined for the obtained acrylic polymer by gel permeation chromatography using GPC LF-804 (manufactured by Showa Denko KK) as a column.
  • the obtained adhesive solution was coated on a release-treated PET film (manufactured by Toyo Cloth Co., Ltd., SP3000-75) with a thickness of 75 ⁇ m so that the thickness of the heat-sensitive adhesive layer after drying would be the thickness shown in Table 1. After that, it was dried at 110° C. for 5 minutes to form a heat-sensitive adhesive layer.
  • This heat-sensitive adhesive layer was transferred to an electrolytic copper foil (thickness 18 ⁇ m, manufactured by Fukuda Metal Foil Powder Industry Co., Ltd.) as a base material at 100 ° C. and cured at 40 ° C. for 48 hours. , and the release-treated PET film were laminated in this order to obtain a single-sided adhesive tape.
  • a measurement sample consisting of only a heat-sensitive adhesive layer of 10 mm ⁇ 6 mm and 1 mm in thickness was prepared in the same manner as in the Examples.
  • the resulting measurement sample was measured using a dynamic viscoelasticity measuring device (DVA-200, manufactured by IT Keisoku Co., Ltd.) under the conditions of shear mode for dynamic viscoelasticity measurement, angular frequency of 1 Hz, and speed of 5 ° C./min.
  • Dynamic viscoelasticity measurement was performed from -40°C to 140°C, and the storage elastic modulus G' at 23°C and 100°C was measured.
  • Examples 2-3 Comparative Example 1
  • a single-sided adhesive tape was obtained in the same manner as in Example 1, except for the changes shown in the table.
  • Example 4 Preparation of acrylic polymer
  • a solution containing the acrylic polymer used for the heat-sensitive adhesive layer (acrylic polymer for the heat-sensitive adhesive layer) and the acrylic polymer used for the pressure-sensitive adhesive layer were prepared.
  • (acrylic polymer for pressure-sensitive adhesive layer) was prepared.
  • a polymerized rosin ester resin manufactured by Arakawa Chemical Industries, Ltd., D-135, softening point 135° C., hydroxyl value 45 mg KOH /g
  • a cross-linking agent epoxy-based cross-linking agent, Tetrad C, manufactured by Mitsubishi Gas Chemical Co., Ltd.
  • Table 1 shows the thickness of the pressure-sensitive adhesive layer after drying on a release-treated PET film (manufactured by Toyo Cloth Co., Ltd., SP3000-75) of the obtained pressure-sensitive adhesive layer adhesive solution. After coating so as to have a thickness, it was dried at 110° C. for 5 minutes to form a pressure-sensitive adhesive layer. This pressure-sensitive adhesive layer was transferred to an electrolytic copper foil (thickness: 18 ⁇ m, manufactured by Fukuda Metal Foil Powder Co., Ltd.) as a base material, and the release-treated PET film was peeled off.
  • the adhesive solution for the heat-sensitive adhesive layer is applied onto a 75 ⁇ m-thick release-treated PET film (manufactured by Toyo Cloth Co., Ltd., SP3000-75), and the thickness of the heat-sensitive adhesive layer after drying becomes the thickness shown in Table 1. and dried at 110° C. for 5 minutes to form a heat-sensitive adhesive layer.
  • This heat-sensitive adhesive layer was transferred to the pressure-sensitive adhesive layer at 23° C. and cured at 40° C. for 48 hours to obtain the substrate, pressure-sensitive adhesive layer, heat-sensitive adhesive layer, and release-treated PET film. A single-sided adhesive tape laminated in this order was obtained.
  • Example 5-14 Comparative Examples 2-3
  • a single-sided adhesive tape was obtained in the same manner as in Example 1, except for the changes shown in the table.
  • the PET film manufactured by Toyo Cloth Co., Ltd., type 10
  • the release-treated PET film on which the adhesive solution for the heat-sensitive adhesive layer was applied. Changed Ra.
  • the obtained single-sided adhesive tape was cut into 7 mm ⁇ 80 mm, and the edge of a copper clad laminate (CCL) (manufactured by Panasonic, R1515E, resin layer thickness 40 ⁇ m, copper foil thickness 2 ⁇ m) pasted on the part. More specifically, a single-sided pressure-sensitive adhesive tape was attached so as to form the covering form shown in FIG. First, a single-sided adhesive tape was placed on one side of one side of the copper-clad laminate so that the end of the long side of the single-sided adhesive tape was positioned 3.5 mm from the edge of the copper-clad laminate. It was heat-pressed for 30 seconds at a pressure of 0.3 MPa.
  • the single-sided adhesive tape is bent toward the other side of the copper-clad laminate so as not to create a gap, and the copper-clad laminate is attached. It was brought into contact with the other surface and heat-pressed under the condition of 100° C. and the pressure of 0.3 MPa for 30 seconds. The attached single-sided adhesive tape was visually observed to confirm the occurrence of wrinkles. The case where there was no wrinkle was evaluated as ⁇ , and the case where there was wrinkle was evaluated as X.
  • BA butyl acrylate 2-EHA: 2-ethylhexyl acrylate MMA: methyl methacrylate BMA: butyl methacrylate IBOA: isobornyl acrylate IBOMA: isobornyl methacrylate AAc: acrylic acid HEA: 2-hydroxyethyl acrylate

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  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)

Abstract

The purpose of the present invention is to provide a single-sided adhesive tape that does not tend to wrinkle even when affixed to a thin adherend and that has exceptional resistance to strong alkaline solutions. The present invention is a single-sided adhesive tape having a base material and a heat-sensitive adhesive layer laminated on one side of the base material, wherein the base material has a metal layer at least on the surface opposite the heat-sensitive adhesive layer, and the heat-sensitive adhesive layer has a static friction coefficient against SUS of 5 or less.

Description

片面粘着テープsingle sided adhesive tape
本発明は、片面粘着テープに関する。 The present invention relates to single-sided adhesive tapes.
従来から、電子機器において部品を固定する際に、粘着剤や粘着テープが広く用いられている。また、粘着テープは、電子機器の製造工程における工程材としても用いられており、例えば、電子機器の製造工程において薄い部材を加工する際、取扱いを容易にし、破損を防止するために粘着テープが用いられている。これらの粘着剤や粘着テープには、高い粘着性に加え、使用される環境に応じて、耐熱性、熱伝導性、耐衝撃性等の機能が要求されている(例えば、特許文献1~3)。 2. Description of the Related Art Conventionally, adhesives and adhesive tapes have been widely used to fix components in electronic devices. Adhesive tape is also used as a processing material in the manufacturing process of electronic devices. used. In addition to high adhesiveness, these adhesives and adhesive tapes are required to have functions such as heat resistance, thermal conductivity, and impact resistance depending on the environment in which they are used (for example, Patent Documents 1 to 3 ).
特開2015-052050号公報JP 2015-052050 A 特開2015-021067号公報JP 2015-021067 A 特開2015-120876号公報JP 2015-120876 A
一方、電子機器に使用されるプリント配線基板等の基板は、銅箔と樹脂層とが積層された銅張積層板(CCL)の銅箔部分に回路を形成することで製造されている。
近年、プリント配線基板等の基板は薄化が進んでおり、例えば銅張積層板の厚みが100μm以下、なかでも30~40μm付近の場合、銅張積層板から基板を製造する工程においては、製造工程中に銅張積層板の端部が破損する問題が生じている。
On the other hand, substrates such as printed wiring boards used in electronic devices are manufactured by forming a circuit on a copper foil portion of a copper clad laminate (CCL) in which a copper foil and a resin layer are laminated.
In recent years, substrates such as printed wiring boards have become thinner. There is a problem that the edges of the copper clad laminate are damaged during the process.
本発明者らは、銅張積層板の端部の破損を防ぐため、銅張積層板の端部に粘着テープを貼り付けて保護することを検討した。
しかしながら、銅張積層板は上述したように厚みが薄いことから、銅張積層板の端部に粘着テープを貼り付ける際に銅張積層板にたわみ、反り等が生じ、銅張積層板の一部が粘着テープに接触して貼り付いてしまい、そこが起点となって粘着テープがシワになる問題が生じることがわかった。また、基板の製造工程で行われるエッチング処理、デスミア処理等においては、処理液として強アルカリ性の溶液が使用されている。このため、強アルカリ性溶液に晒されると粘着テープに剥がれが生じ、銅張積層板の端部を充分に保護できなかったり、銅張積層板の表面の銅が腐食されたりする問題も生じる。
In order to prevent damage to the ends of the copper-clad laminate, the present inventors have studied protecting the ends of the copper-clad laminate by attaching an adhesive tape.
However, since the copper-clad laminate is thin as described above, the copper-clad laminate bends or warps when the adhesive tape is attached to the edge of the copper-clad laminate. It has been found that the adhesive tape comes into contact with the adhesive tape and sticks to it, causing the adhesive tape to wrinkle. Further, in the etching process, the desmear process, etc., which are performed in the substrate manufacturing process, a strong alkaline solution is used as the processing liquid. For this reason, when exposed to a strong alkaline solution, the adhesive tape peels off, resulting in insufficient protection of the edges of the copper-clad laminate and corrosion of the copper on the surface of the copper-clad laminate.
本発明は、厚みが薄い被着体に貼り付ける際にもシワを生じにくく、かつ、強アルカリ性溶液への耐性に優れた片面粘着テープを提供することを目的とする。 SUMMARY OF THE INVENTION An object of the present invention is to provide a single-sided pressure-sensitive adhesive tape that does not wrinkle easily even when applied to a thin adherend and has excellent resistance to strong alkaline solutions.
本開示1は、基材と、前記基材の一方の面に積層された感熱粘着剤層とを有する片面粘着テープであって、前記基材は、少なくとも前記感熱粘着剤層とは反対側の表面に、金属層を有し、前記感熱粘着剤層は、SUSに対する静止摩擦係数が5以下である片面粘着テープである。
本開示2は、前記金属層は、銅からなる、本開示1の片面粘着テープである。
本開示3は、前記基材は、金属基材である、本開示1又は2の片面粘着テープである。
本開示4は、前記金属基材は、銅箔である、本開示3の片面粘着テープである。
本開示5は、前記基材と前記感熱粘着剤層との間に更に感圧粘着剤層を有する、本開示1、2、3又は4の片面粘着テープである。
本開示6は、前記感熱粘着剤層は、動的粘弾性測定装置を用いて測定周波数1Hzで測定した損失正接のピーク温度が40℃以上である、本開示1、2、3、4又は5の片面粘着テープである。
本開示7は、前記感熱粘着剤層は、23℃における貯蔵弾性率G’が5MPa以上、100℃における貯蔵弾性率G’が0.2MPa以下である、本開示1、2、3、4、5又は6の片面粘着テープである。
本開示8は、前記感熱粘着剤層は、ゲル分率が50重量%以上である、本開示1、2、3、4、5、6又は7の片面粘着テープである。
本開示9は、前記感熱粘着剤層は、表面粗さRaが0.01μm以上、0.8μm以下である、本開示1、2、3、4、5、6、7又は8の片面粘着テープである。
本開示10は、前記感熱粘着剤層は、アクリル系ポリマーを含有する、本開示1、2、3、4、5、6、7、8又は9の片面粘着テープである。
本開示11は、前記感熱粘着剤層は、更に、粘着付与樹脂を含有する、本開示10の片面粘着テープである。
本開示12は、前記粘着付与樹脂は、軟化点が100℃以上である、本開示11の片面粘着テープである。
本開示13は、前記粘着付与樹脂は、水酸基価が25mgKOH/g以上である、本開示11又は12の片面粘着テープである。
本開示14は、前記アクリル系ポリマー100重量部に対する前記粘着付与樹脂の含有量が5重量部以上、50重量部以下である、本開示11、12又は13の片面粘着テープである。
本開示15は、前記感熱粘着剤層は、エポキシ系架橋剤を含有する、本開示10、11、12、13又は14の片面粘着テープである。
本開示16は、前記感圧粘着剤層は、ゲル分率が50重量%以上である、本開示5の片面粘着テープである。
本開示17は、前記感圧粘着剤層は、エポキシ系架橋剤を含有する、本開示5の片面粘着テープである。
本開示18は、基材と、前記基材の一方の面に積層された感熱粘着剤層とを有する片面粘着テープであって、前記基材は、少なくとも前記感熱粘着剤層とは反対側の表面に、金属層を有し、前記感熱粘着剤層は、アクリル系ポリマー、及び、粘着付与樹脂を含有し、前記粘着付与樹脂は、軟化点が100℃以上であり、かつ水酸基価が25mgKOH/g以上であり、前記アクリル系ポリマー100重量部に対する前記粘着付与樹脂の含有量が5重量部以上、50重量部以下であり、前記感熱粘着剤層は、SUSに対する静止摩擦係数が5以下である、片面粘着テープである。
本開示19は、エッチング工程、デスミア工程、又は、無電解メッキ工程において、金属張積層板の端部に貼り付けて金属張積層板の端部を保護するために用いられる、本開示1、2、3、4、5、6、7、8、9、10、11、12、13、14、15、16、17又は18の片面粘着テープである。
本開示20は、一方の面に金属層を有し、他方の面に感熱粘着剤層を有する片面粘着テープであって、前記感熱粘着剤層は、SUSに対する静止摩擦係数が5以下である、片面粘着テープである。
本開示21は、前記金属層は、銅からなる、本開示21の片面粘着テープである。
本開示22は、前記基材と前記感熱粘着剤層との間に更に感圧粘着剤層を有する、本開示20又は21の片面粘着テープである。
本開示23は、前記感熱粘着剤層は、動的粘弾性測定装置を用いて測定周波数1Hzで測定した損失正接のピーク温度が40℃以上である、本開示20、21又は22の片面粘着テープである。
本開示24は、前記感熱粘着剤層は、23℃における貯蔵弾性率G’が5MPa以上、100℃における貯蔵弾性率G’が0.2MPa以下である、本開示20、21、22又は23の片面粘着テープである。
本開示25は、前記感熱粘着剤層は、ゲル分率が50重量%以上である、本開示20、21、22、23又は24の片面粘着テープである。
本開示26は、前記感熱粘着剤層は、表面粗さRaが0.01μm以上、0.8μm以下である、本開示20、21、22、23、24又は25の片面粘着テープである。
本開示27は、前記感熱粘着剤層は、アクリル系ポリマーを含有する、本開示20、21、22、23、24、25又は26の片面粘着テープである。
本開示28は、前記感熱粘着剤層は、更に、粘着付与樹脂を含有する、本開示27の片面粘着テープである。
本開示29は、前記粘着付与樹脂は、軟化点が100℃以上である、本開示28の片面粘着テープである。
本開示30は、前記粘着付与樹脂は、水酸基価が25mgKOH/g以上である、本開示28又は29の片面粘着テープである。
本開示31は、前記アクリル系ポリマー100重量部に対する前記粘着付与樹脂の含有量が5重量部以上、50重量部以下である、本開示28、29又は30の片面粘着テープである。
本開示32は、前記感熱粘着剤層は、エポキシ系架橋剤を含有する、本開示27、28、29、30又は31の片面粘着テープである。
本開示33は、前記感圧粘着剤層は、ゲル分率が50重量%以上である、本開示22の片面粘着テープである。
本開示34は、前記感圧粘着剤層は、エポキシ系架橋剤を含有する、本開示22の片面粘着テープである。
本開示35は、エッチング工程、デスミア工程、又は、無電解メッキ工程において、金属張積層板の端部に貼り付けて金属張積層板の端部を保護するために用いられる、本開示20、21、22、23、24、25、26、27、28、29、30、31、32、33又は34の片面粘着テープである。
以下に本発明を詳述する。
The present disclosure 1 is a single-sided adhesive tape having a substrate and a heat-sensitive adhesive layer laminated on one surface of the substrate, wherein the substrate is at least on the side opposite to the heat-sensitive adhesive layer. A single-sided adhesive tape having a metal layer on the surface and the heat-sensitive adhesive layer having a static friction coefficient of 5 or less against SUS.
The present disclosure 2 is the single-sided adhesive tape of the present disclosure 1, wherein the metal layer is made of copper.
Present Disclosure 3 is the single-sided pressure-sensitive adhesive tape according to Present Disclosure 1 or 2, wherein the substrate is a metal substrate.
Present Disclosure 4 is the single-sided pressure-sensitive adhesive tape according to Present Disclosure 3, wherein the metal substrate is a copper foil.
This disclosure 5 is the single-sided adhesive tape of this disclosure 1, 2, 3 or 4, further comprising a pressure sensitive adhesive layer between said substrate and said heat sensitive adhesive layer.
The present disclosure 1, 2, 3, 4 or 5, wherein the heat-sensitive adhesive layer has a loss tangent peak temperature of 40 ° C. or higher measured at a measurement frequency of 1 Hz using a dynamic viscoelasticity measuring device. is a single-sided adhesive tape.
According to the present disclosure 7, the heat-sensitive adhesive layer has a storage modulus G' of 5 MPa or more at 23°C and a storage modulus G' of 0.2 MPa or less at 100°C. 5 or 6 single-sided adhesive tape.
The present disclosure 8 is the single-sided adhesive tape according to the present disclosure 1, 2, 3, 4, 5, 6 or 7, wherein the heat-sensitive adhesive layer has a gel fraction of 50% by weight or more.
The present disclosure 9 is the single-sided adhesive tape of the present disclosure 1, 2, 3, 4, 5, 6, 7, or 8, wherein the heat-sensitive adhesive layer has a surface roughness Ra of 0.01 μm or more and 0.8 μm or less. is.
The present disclosure 10 is the single-sided adhesive tape according to the present disclosure 1, 2, 3, 4, 5, 6, 7, 8 or 9, wherein the heat-sensitive adhesive layer contains an acrylic polymer.
Present Disclosure 11 is the single-sided adhesive tape of Present Disclosure 10, wherein the heat-sensitive adhesive layer further contains a tackifying resin.
The present disclosure 12 is the single-sided adhesive tape of the present disclosure 11, wherein the tackifying resin has a softening point of 100° C. or higher.
Present Disclosure 13 is the single-sided pressure-sensitive adhesive tape according to Present Disclosure 11 or 12, wherein the tackifying resin has a hydroxyl value of 25 mgKOH/g or more.
Present Disclosure 14 is the single-sided pressure-sensitive adhesive tape according to Present Disclosure 11, 12 or 13, wherein the content of the tackifier resin is 5 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the acrylic polymer.
The present disclosure 15 is the single-sided adhesive tape according to the present disclosure 10, 11, 12, 13 or 14, wherein the heat-sensitive adhesive layer contains an epoxy-based cross-linking agent.
The present disclosure 16 is the single-sided adhesive tape of the present disclosure 5, wherein the pressure-sensitive adhesive layer has a gel fraction of 50% by weight or more.
The present disclosure 17 is the single-sided adhesive tape of the present disclosure 5, wherein the pressure-sensitive adhesive layer contains an epoxy-based cross-linking agent.
The present disclosure 18 is a single-sided adhesive tape having a base material and a heat-sensitive adhesive layer laminated on one side of the base material, wherein the base material is at least on the side opposite to the heat-sensitive adhesive layer. It has a metal layer on the surface, and the heat-sensitive adhesive layer contains an acrylic polymer and a tackifying resin, and the tackifying resin has a softening point of 100° C. or higher and a hydroxyl value of 25 mgKOH/ g or more, the content of the tackifying resin with respect to 100 parts by weight of the acrylic polymer is 5 parts by weight or more and 50 parts by weight or less, and the heat-sensitive adhesive layer has a coefficient of static friction against SUS of 5 or less. , is a single-sided adhesive tape.
The present disclosure 19 is an etching process, a desmear process, or an electroless plating process, the present disclosures 1 and 2, which are used to protect the edges of the metal-clad laminate by attaching them to the edges of the metal-clad laminate. , 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 or 18 single-sided adhesive tape.
The present disclosure 20 is a single-sided adhesive tape having a metal layer on one side and a heat-sensitive adhesive layer on the other side, wherein the heat-sensitive adhesive layer has a coefficient of static friction against SUS of 5 or less. It is a single-sided adhesive tape.
The present disclosure 21 is the single-sided adhesive tape of the present disclosure 21, wherein the metal layer is made of copper.
Disclosure 22 is the single-sided adhesive tape of Disclosures 20 or 21, further comprising a pressure sensitive adhesive layer between said substrate and said heat sensitive adhesive layer.
The present disclosure 23 is the single-sided adhesive tape of the present disclosure 20, 21 or 22, wherein the heat-sensitive adhesive layer has a loss tangent peak temperature of 40 ° C. or higher measured at a measurement frequency of 1 Hz using a dynamic viscoelasticity measuring device. is.
24 of the present disclosure 20, 21, 22, or 23, wherein the heat-sensitive adhesive layer has a storage elastic modulus G' of 5 MPa or more at 23°C and a storage elastic modulus G' of 0.2 MPa or less at 100°C. It is a single-sided adhesive tape.
The present disclosure 25 is the single-sided adhesive tape according to the present disclosure 20, 21, 22, 23 or 24, wherein the heat-sensitive adhesive layer has a gel fraction of 50% by weight or more.
26 of the present disclosure is the single-sided adhesive tape according to 20, 21, 22, 23, 24 or 25, wherein the heat-sensitive adhesive layer has a surface roughness Ra of 0.01 μm or more and 0.8 μm or less.
The present disclosure 27 is the single-sided adhesive tape of the present disclosure 20, 21, 22, 23, 24, 25 or 26, wherein the heat-sensitive adhesive layer contains an acrylic polymer.
This disclosure 28 is the single-sided adhesive tape of this disclosure 27, wherein said thermal adhesive layer further contains a tackifying resin.
This disclosure 29 is the single-sided adhesive tape of this disclosure 28, wherein the tackifying resin has a softening point of 100° C. or higher.
This disclosure 30 is the single-sided adhesive tape of this disclosure 28 or 29, wherein the tackifying resin has a hydroxyl value of 25 mgKOH/g or more.
Present Disclosure 31 is the single-sided adhesive tape according to Present Disclosures 28, 29, or 30, wherein the content of said tackifying resin relative to 100 parts by weight of said acrylic polymer is 5 parts by weight or more and 50 parts by weight or less.
32 of the present disclosure is the single-sided adhesive tape according to 27, 28, 29, 30 or 31 of the present disclosure, wherein the heat-sensitive adhesive layer contains an epoxy-based cross-linking agent.
This disclosure 33 is the single-sided adhesive tape of this disclosure 22, wherein the pressure-sensitive adhesive layer has a gel fraction of 50% by weight or more.
This disclosure 34 is the single-sided adhesive tape of this disclosure 22, wherein the pressure-sensitive adhesive layer contains an epoxy-based cross-linking agent.
The present disclosure 35 is used to protect the edges of the metal-clad laminate by attaching to the edges of the metal-clad laminate in the etching process, the desmear process, or the electroless plating process. , 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33 or 34.
The present invention will be described in detail below.
本発明者らは、基材と、該基材の一方の面に積層された感熱粘着剤層とを有する片面粘着テープにおいて、基材を、少なくとも感熱粘着剤層とは反対側の表面に、金属層を有するものとし、かつ、感熱粘着剤層のSUSに対する静止摩擦係数を一定値以下に調整することを検討した。本発明者らは、このような片面粘着テープであれば、厚みが薄い被着体に貼り付ける際にもシワを生じにくく、かつ、強アルカリ性溶液への耐性に優れることを見出し、本発明を完成させるに至った。 The present inventors have found that in a single-sided adhesive tape having a substrate and a heat-sensitive adhesive layer laminated on one side of the substrate, the substrate is placed on at least the surface opposite to the heat-sensitive adhesive layer, It has been considered to have a metal layer and to adjust the coefficient of static friction of the heat-sensitive adhesive layer against SUS to a certain value or less. The present inventors have found that such a single-sided pressure-sensitive adhesive tape is less likely to wrinkle when attached to a thin adherend and has excellent resistance to strong alkaline solutions, and has developed the present invention. I came to complete it.
本発明の一態様では、片面粘着テープは、基材と、上記基材の一方の面に積層された感熱粘着剤層とを有する。上記基材とは、上記片面粘着テープのうち粘着剤層を除く部分全体を指し、上記粘着剤層を支持する部材である。上記粘着剤層は、上記片面粘着テープの最表面に位置する上記感熱粘着剤層の他、上記感熱粘着剤層とは異なる組成を有する他の粘着剤層(例えば、感圧粘着剤層)を含んでいてもよい。すなわち、「上記基材の一方の面に積層された感熱粘着剤層」とは、上記基材の一方の側に感熱粘着剤層が配置され、かつ上記基材と感熱粘着剤層とが直接又は間接的に結合していることを意味し、具体的には、上記片面粘着テープには、上記基材と上記感熱粘着剤層とが直に接している場合と、上記感熱粘着剤層と上記基材との間に上記他の粘着剤層を有する場合とが含まれる。また、上記感熱粘着剤層は、常温(23℃)ではほとんど粘着性を示さず、粘着剤層のガラス転移点以上に加熱することで粘着性を発現する粘着剤を含有する層であり、上記感圧粘着剤層は、常温(23℃)で粘着性を示す粘着剤を含有する層である。 In one aspect of the present invention, the single-sided adhesive tape has a substrate and a heat-sensitive adhesive layer laminated on one side of the substrate. The base material refers to the entire portion of the single-sided pressure-sensitive adhesive tape excluding the pressure-sensitive adhesive layer, and is a member that supports the pressure-sensitive adhesive layer. The adhesive layer includes the heat-sensitive adhesive layer positioned on the outermost surface of the single-sided adhesive tape, and another adhesive layer (for example, a pressure-sensitive adhesive layer) having a composition different from that of the heat-sensitive adhesive layer. may contain. That is, "the heat-sensitive adhesive layer laminated on one side of the base material" means that the heat-sensitive adhesive layer is disposed on one side of the base material, and the base material and the heat-sensitive adhesive layer are directly attached to each other. Or means that it is indirectly bonded, specifically, in the single-sided adhesive tape, the base material and the heat-sensitive adhesive layer are in direct contact, and It includes the case of having the above-mentioned other pressure-sensitive adhesive layer between the substrate and the above-mentioned substrate. Further, the heat-sensitive adhesive layer is a layer containing an adhesive that exhibits almost no adhesiveness at room temperature (23° C.) and exhibits adhesiveness when heated to a temperature equal to or higher than the glass transition point of the adhesive layer. The pressure-sensitive adhesive layer is a layer containing an adhesive that exhibits adhesiveness at room temperature (23°C).
上記基材は、少なくとも上記感熱粘着剤層とは反対側の表面に、金属層を有する。すなわち、本発明の片面粘着テープは、一方の最表面が基材を構成する金属層であり、他方の最表面が感熱粘着剤層である。
上記金属層が、上記基材の少なくとも上記表面に配置されることで、片面粘着テープを金属張積層板の端部に貼り付けた場合には、上記金属層が最表面に露出することになる。これにより、強アルカリ性溶液に晒された場合にも片面粘着テープが剥がれにくくなる。また、無電解メッキ等の金属メッキ処理を施した場合、上記金属層の表面に析出する金属メッキ層は金属層から剥離しにくい。したがって、片面粘着テープを貼り付けた状態で金属張積層板に金属メッキ処理を施したとしても、後の工程において金属メッキ層が片面粘着テープ上から剥離して不具合を起こすことを防ぐことができる。
The substrate has a metal layer at least on the surface opposite to the heat-sensitive adhesive layer. That is, in the single-sided adhesive tape of the present invention, one outermost surface is the metal layer forming the base material, and the other outermost surface is the heat-sensitive adhesive layer.
By disposing the metal layer on at least the surface of the base material, the metal layer is exposed on the outermost surface when the single-sided adhesive tape is attached to the edge of the metal-clad laminate. . This makes it difficult for the single-sided adhesive tape to come off even when exposed to a strong alkaline solution. Further, when a metal plating treatment such as electroless plating is performed, the metal plating layer deposited on the surface of the metal layer is difficult to separate from the metal layer. Therefore, even if the metal-clad laminate is plated with a single-sided adhesive tape, it is possible to prevent the metal-plated layer from peeling off from the single-sided adhesive tape in a later step. .
上記金属層を構成する金属は特に限定されず、例えば、銅、アルミニウム、ニッケル、チタン等が挙げられる。また、上記金属層を構成する金属としては、ステンレス、モネル等の合金も挙げられる。なかでも、折り返した後の復元力が小さく、かつ、破れにくいため片面粘着テープの取り扱い性がより良好となることから、上記金属層が銅からなることが好ましい。 The metal forming the metal layer is not particularly limited, and examples thereof include copper, aluminum, nickel, and titanium. Moreover, alloys, such as stainless steel and Monel, are mentioned as a metal which comprises the said metal layer. Above all, it is preferable that the metal layer is made of copper, because the restoring force after folding is small and the single-sided pressure-sensitive adhesive tape can be easily handled because it is hard to break.
上記基材は、少なくとも上記感熱粘着剤層とは反対側の表面に、上記金属層を有していれば特に限定されず、単層からなるものであってもよいし、複数層からなるものであってもよい。
上記基材が単層からなる場合、上記基材は上記金属層のみで構成される。以下では、上記金属層のみで構成される上記基材を金属基材ともいう。なお、上記金属基材は、金属層のみで構成されている基材全般を指し、単層の金属層からなる基材だけでなく、複数の金属層からなる基材も含む。
上記基材が複数層からなる場合、上記感熱粘着剤層とは反対側の表面を構成する層が上記金属層であり、他の層は限定されない。
上記基材としては、例えば、上記基材自体が金属基材であってもよいし、樹脂基材と、該樹脂基材の表面に積層された上記金属層とを有する積層基材であってもよい。
なかでも、上記基材が上記金属基材であることにより、金属張積層板の表面から裏面にまでまたがるように片面粘着テープを折り返して(折り曲げて)金属張積層板の端部に貼り付けた場合であっても、上記金属基材が形状を保持することから、上記金属基材を折り返したことによる復元力を抑制することができる。これにより、金属張積層板の端部と上記感熱粘着剤層との間に隙間が生じにくくなり、剥がれがより生じにくくなる。
The substrate is not particularly limited as long as it has the metal layer on at least the surface opposite to the heat-sensitive adhesive layer, and may be composed of a single layer or multiple layers. may be
When the base material consists of a single layer, the base material is composed only of the metal layer. Below, the said base material comprised only by the said metal layer is also called a metal base material. In addition, the above metal base refers to all bases composed only of metal layers, and includes not only bases composed of a single metal layer but also bases composed of a plurality of metal layers.
When the substrate is composed of a plurality of layers, the layer constituting the surface opposite to the heat-sensitive adhesive layer is the metal layer, and other layers are not limited.
As the base material, for example, the base material itself may be a metal base material, or a laminated base material having a resin base material and the metal layer laminated on the surface of the resin base material, good too.
Among them, since the base material is the metal base material, the single-sided adhesive tape is folded back (bent) so as to extend from the front surface to the back surface of the metal-clad laminate and is attached to the edge of the metal-clad laminate. Even in such a case, since the metal base retains its shape, it is possible to suppress the restoring force due to the bending of the metal base. As a result, gaps are less likely to occur between the ends of the metal-clad laminate and the heat-sensitive adhesive layer, and peeling is less likely to occur.
上記金属基材を構成する金属は特に限定されず、上述したような金属層を構成する金属が挙げられる。なかでも、折り返した後の復元力が小さく、かつ、破れにくいため片面粘着テープの取り扱い性がより良好となることから、上記金属基材が銅箔であることが好ましい。 The metal constituting the metal substrate is not particularly limited, and includes the metals constituting the metal layer as described above. Above all, it is preferable that the metal substrate is a copper foil, since the restoring force after folding is small and the single-sided pressure-sensitive adhesive tape can be easily handled because it is hard to break.
上記樹脂基材は特に限定されず、例えば、ポリエチレンフィルム、ポリプロピレンフィルム等のポリオレフィン系樹脂フィルム、ポリエチレンテレフタレート(PET)フィルム等のポリエステル系樹脂フィルム、エチレン-酢酸ビニル共重合体フィルム、ポリ塩化ビニル系樹脂フィルム、ポリウレタン系樹脂フィルムが挙げられる。また、上記樹脂基材として、ポリエチレン発泡体シート、ポリプロピレン発泡体シート等のポリオレフィン発泡体シート、ポリウレタン発泡体シート等も挙げられる。なかでも、PETフィルムが好ましい。 The resin substrate is not particularly limited. A resin film and a polyurethane-based resin film can be mentioned. Examples of the resin substrate include polyolefin foam sheets such as polyethylene foam sheets and polypropylene foam sheets, and polyurethane foam sheets. Among them, a PET film is preferable.
上記基材の厚み(上記金属層を含めた上記基材全体の厚み)は特に限定されないが、好ましい下限は2μm、好ましい上限は30μmである。上記基材の厚みが上記範囲内であれば、片面粘着テープを折り返して(折り曲げて)金属張積層板の端部に貼り付けた場合であっても剥がれがより生じにくくなる。上記基材の厚みのより好ましい下限は4μm、より好ましい上限は20μmである。
また、上記基材における上記金属層の厚みは特に限定されないが、上記基材全体の厚みに占める上記金属層の厚みの比率の好ましい下限は0.1%である。上記金属層の厚みの比率が0.1%以上であれば、片面粘着テープの強アルカリ性溶液への耐性がより高くなる。上記金属層の厚みの比率のより好ましい下限は1%である。上記金属層の厚みの比率の上限は特に限定されず、上記基材が上記金属基材である場合は上記金属層の厚みの比率は100%となる。
The thickness of the substrate (thickness of the entire substrate including the metal layer) is not particularly limited, but a preferable lower limit is 2 μm and a preferable upper limit is 30 μm. When the thickness of the base material is within the above range, peeling is less likely to occur even when the single-sided adhesive tape is folded back (bent) and attached to the edge of the metal-clad laminate. A more preferable lower limit of the thickness of the substrate is 4 μm, and a more preferable upper limit thereof is 20 μm.
The thickness of the metal layer in the substrate is not particularly limited, but the preferable lower limit of the ratio of the thickness of the metal layer to the thickness of the entire substrate is 0.1%. When the thickness ratio of the metal layer is 0.1% or more, the resistance of the single-sided pressure-sensitive adhesive tape to strong alkaline solutions is further enhanced. A more preferable lower limit of the thickness ratio of the metal layer is 1%. The upper limit of the thickness ratio of the metal layer is not particularly limited, and when the substrate is the metal substrate, the thickness ratio of the metal layer is 100%.
上記感熱粘着剤層は、SUS(ステンレス鋼)に対する静止摩擦係数の上限が5である。
上記感熱粘着剤層は常温ではほとんど粘着性を示さないことから、片面粘着テープを金属張積層板の端部に貼り付ける際に金属張積層板の一部が上記感熱粘着剤層に接触した場合にも上記感熱粘着剤層が貼り付かず、シワを生じにくい。更に、上記SUSに対する静止摩擦係数が5以下であることで、上記感熱粘着剤層が金属張積層板に対して滑ることが可能なため、片面粘着テープを金属張積層板の端部に貼り付ける際に金属張積層板の一部が上記感熱粘着剤層に接触した状態であっても、接触した箇所が滑ることで貼り付け応力を均一化できる。これにより、上記基材に負荷がかからず、シワを生じにくい。上記SUSに対する静止摩擦係数の好ましい上限は3、より好ましい上限は2である。上記SUSに対する静止摩擦係数の下限は特に限定されないが、実質的には0.1程度が下限である。
なお、SUSに対する静止摩擦係数は、滑り片としてSUS304(サイズ63mm×63mm、重さ200g)を用い、引張速度100mm/minの条件でJIS K7125に準拠して、常温(23℃)、湿度50%にて測定することができる。測定の際は、相手材の上に試料である片面粘着テープを置き、片面粘着テープの上に重りである滑り片を置いた状態で、片面粘着テープを紐で引張り、その際に発生する抵抗力(摩擦力)を計測する。相手材としては、滑り片同様にSUS304(サイズ250mm×150mm×厚み1.5mm)を用いることができる。
The upper limit of the coefficient of static friction of the heat-sensitive adhesive layer to SUS (stainless steel) is 5.
Since the heat-sensitive adhesive layer exhibits almost no adhesiveness at room temperature, when a part of the metal-clad laminate comes into contact with the heat-sensitive adhesive layer when the single-sided adhesive tape is attached to the edge of the metal-clad laminate, The heat-sensitive adhesive layer does not stick to the surface, and wrinkles are less likely to occur. Furthermore, since the coefficient of static friction with respect to SUS is 5 or less, the heat-sensitive adhesive layer can slide on the metal-clad laminate, so that the single-sided adhesive tape is attached to the edge of the metal-clad laminate. Even if a portion of the metal-clad laminate is in contact with the heat-sensitive adhesive layer, the contacting portion slides, making it possible to equalize the attaching stress. As a result, no load is applied to the base material, and wrinkles are less likely to occur. A preferable upper limit of the coefficient of static friction for SUS is 3, and a more preferable upper limit is 2. Although the lower limit of the coefficient of static friction with respect to SUS is not particularly limited, the practical lower limit is about 0.1.
The coefficient of static friction against SUS was measured using SUS304 (size 63 mm x 63 mm, weight 200 g) as a sliding piece, and at a tensile speed of 100 mm/min in accordance with JIS K7125 at room temperature (23°C) and humidity of 50%. can be measured at When measuring, put the single-sided adhesive tape as a sample on the other material, put the sliding piece as a weight on the single-sided adhesive tape, and pull the single-sided adhesive tape with a string to measure the resistance generated at that time. Measure the force (frictional force). As the mating material, SUS304 (size: 250 mm x 150 mm x thickness: 1.5 mm) can be used like the sliding piece.
上記静止摩擦係数を上記範囲に調整する方法は特に限定されず、例えば、上記感熱粘着剤層の動的粘弾性測定装置を用いて測定周波数1Hzで測定した損失正接のピーク温度、23℃における貯蔵弾性率G’、ゲル分率、表面粗さRa等を適切な範囲に調整する方法が挙げられる。
より具体的には例えば、上記感熱粘着剤層の損失正接のピーク温度、23℃における貯蔵弾性率G’、ゲル分率等を調整する方法としては、上記感熱粘着剤層に含まれるベースポリマーの種類、分子量及び分子量分布、粘着付与樹脂の種類及び含有量、架橋剤の種類及び含有量等を調整する方法が挙げられる。また、上記表面粗さRaを調整する方法としては、上記感熱粘着剤層を形成する際、上記感熱粘着剤層を形成するための粘着剤溶液を塗工するフィルム(例えば、離型処理したPETフィルム)の表面粗さを適切に調整する方法が挙げられる。なお、上記感熱粘着剤層の表面には、このとき使用するフィルムの表面粗さが転写されるため、該フィルムの表面粗さを適切に調整することで、上記感熱粘着剤層の表面粗さRaを調整することができる。
The method for adjusting the coefficient of static friction within the above range is not particularly limited. A method of adjusting the elastic modulus G', the gel fraction, the surface roughness Ra, etc. within appropriate ranges can be mentioned.
More specifically, for example, as a method for adjusting the peak temperature of the loss tangent of the heat-sensitive adhesive layer, the storage elastic modulus G′ at 23° C., the gel fraction, etc., the base polymer contained in the heat-sensitive adhesive layer A method of adjusting the type, molecular weight and molecular weight distribution, the type and content of the tackifying resin, the type and content of the cross-linking agent, and the like can be mentioned. Further, as a method for adjusting the surface roughness Ra, when forming the heat-sensitive adhesive layer, a film (for example, release-treated PET) for coating the adhesive solution for forming the heat-sensitive adhesive layer a method of appropriately adjusting the surface roughness of the film). Since the surface roughness of the film used at this time is transferred to the surface of the heat-sensitive adhesive layer, the surface roughness of the heat-sensitive adhesive layer can be improved by appropriately adjusting the surface roughness of the film. Ra can be adjusted.
上記感熱粘着剤層は、動的粘弾性測定装置を用いて測定周波数1Hzで測定した損失正接(以下、tanδ、又は、単に損失正接ともいう)のピーク温度は特に限定されないが、40℃以上であることが好ましい。
上記損失正接のピーク温度が40℃以上であることで、上記SUSに対する静止摩擦係数を上記範囲に調整しやすくなり、片面粘着テープを金属張積層板の端部に貼り付ける際にシワをより抑制することができる。上記損失正接のピーク温度は42℃以上であることがより好ましく、45℃以上であることが更に好ましい。また、上記損失正接のピーク温度は100℃以下であることが好ましく、90℃以下であることがより好ましく、80℃以下であることが更に好ましい。
なお、上記損失正接は、動的粘弾性測定装置(アイティー計測制御社製、DVA-200、又はその同等品)を用い、低速昇温せん断変形モードの5℃/分、1Hzの条件で、-40℃~140℃の動的粘弾性スペクトルを測定することで得ることができる。
The heat-sensitive adhesive layer has a peak temperature of loss tangent (hereinafter also referred to as tan δ or simply loss tangent) measured at a measurement frequency of 1 Hz using a dynamic viscoelasticity measuring device, although the peak temperature is not particularly limited. Preferably.
When the peak temperature of the loss tangent is 40 ° C. or higher, it becomes easier to adjust the static friction coefficient to the SUS within the above range, and wrinkles are further suppressed when the single-sided adhesive tape is attached to the edge of the metal-clad laminate. can do. The peak temperature of the loss tangent is more preferably 42° C. or higher, even more preferably 45° C. or higher. The peak temperature of the loss tangent is preferably 100° C. or lower, more preferably 90° C. or lower, and even more preferably 80° C. or lower.
The loss tangent is measured using a dynamic viscoelasticity measuring device (DVA-200, manufactured by IT Keisoku Co., Ltd., or equivalent) under the conditions of 5 ° C./min and 1 Hz in a low-speed heating shear deformation mode. It can be obtained by measuring dynamic viscoelasticity spectrum from -40°C to 140°C.
上記感熱粘着剤層の貯蔵弾性率G’は特に限定されないが、23℃における貯蔵弾性率G’の好ましい下限が5MPaであり、100℃における貯蔵弾性率G’の好ましい上限が0.2MPaである。
上記23℃における貯蔵弾性率G’が5MPa以上であれば、上記感熱粘着剤層が常温ではほとんど粘着性を示さないことから、片面粘着テープを金属張積層板の端部に貼り付ける際にシワをより抑制することができる。上記23℃における貯蔵弾性率G’のより好ましい下限は8MPa、更に好ましい下限は10MPaである。上記23℃における貯蔵弾性率G’の上限は特に限定されないが、片面粘着テープを容易にロール形状にできる観点から、好ましい上限は10000MPa、より好ましい上限は1000MPaである。
The storage elastic modulus G' of the heat-sensitive adhesive layer is not particularly limited, but the preferred lower limit of the storage elastic modulus G' at 23°C is 5 MPa, and the preferred upper limit of the storage elastic modulus G' at 100°C is 0.2 MPa. .
If the storage elastic modulus G′ at 23° C. is 5 MPa or more, the heat-sensitive adhesive layer exhibits almost no adhesiveness at room temperature. can be further suppressed. A more preferable lower limit of the storage elastic modulus G' at 23°C is 8 MPa, and a more preferable lower limit is 10 MPa. Although the upper limit of the storage elastic modulus G' at 23°C is not particularly limited, the upper limit is preferably 10000 MPa, more preferably 1000 MPa, from the viewpoint that the single-sided adhesive tape can be easily rolled.
上記100℃における貯蔵弾性率G’が0.2MPa以下であれば、上記感熱粘着剤層が加熱により充分な粘着性を発現することから、片面粘着テープを金属張積層板の端部に接触させた状態で片面粘着テープにシワ及び浮きが生じないように位置等を調整した後に加熱圧着することで、片面粘着テープを金属張積層板の端部に貼り付けることができる。上記100℃における貯蔵弾性率G’のより好ましい上限は0.1MPa、更に好ましい上限は0.08MPaである。上記100℃における貯蔵弾性率G’の下限は特に限定されないが、加熱圧着時に上記感熱粘着剤層の変形による染み出しを抑制する観点から、好ましい下限は0.01MPa、より好ましい下限は0.05MPaである。
なお、23℃又は100℃における貯蔵弾性率G’は、動的粘弾性測定装置(例えば、アイティー計測制御社製「DVA-200」、レオメトリックス社製「ARES」等)を用いて、動的粘弾性測定のせん断モード、角周波数1Hz、速度5℃/minの条件で-40℃から140℃まで測定を行うことで得ることができる。
If the storage elastic modulus G′ at 100° C. is 0.2 MPa or less, the heat-sensitive adhesive layer exhibits sufficient adhesiveness by heating, so that the single-sided adhesive tape is brought into contact with the edge of the metal-clad laminate. The single-sided adhesive tape can be attached to the edge of the metal-clad laminate by adjusting the position and the like so that the single-sided adhesive tape does not wrinkle or float, and then heat-pressing it. A more preferable upper limit of the storage elastic modulus G' at 100°C is 0.1 MPa, and a further preferable upper limit is 0.08 MPa. The lower limit of the storage elastic modulus G′ at 100° C. is not particularly limited, but from the viewpoint of suppressing exudation due to deformation of the heat-sensitive adhesive layer during thermocompression bonding, a preferable lower limit is 0.01 MPa, and a more preferable lower limit is 0.05 MPa. is.
The storage modulus G′ at 23° C. or 100° C. is measured using a dynamic viscoelasticity measuring device (for example, “DVA-200” manufactured by IT Instrument Control Co., Ltd., “ARES” manufactured by Rheometrics Co., Ltd.). It can be obtained by measuring from −40° C. to 140° C. under the conditions of shear mode of physical viscoelasticity measurement, angular frequency of 1 Hz, and speed of 5° C./min.
上記感熱粘着剤層のゲル分率は特に限定されないが、好ましい下限は50重量%である。上記ゲル分率が50重量%以上であれば、上記感熱粘着剤層への強アルカリ性溶液の膨潤が抑えられ、片面粘着テープの強アルカリ性溶液への耐性がより高くなる。また、上記ゲル分率が50重量%以上であれば、上記SUSに対する静止摩擦係数を上記範囲に調整しやすくなり、片面粘着テープを金属張積層板の端部に貼り付ける際にシワをより抑制することができる。上記ゲル分率のより好ましい下限は60重量%である。上記ゲル分率の上限は特に限定されないが、上記感熱粘着剤層が加熱により充分な粘着性を発現しやすいことから、好ましい上限は90重量%、より好ましい上限は80重量%である。
なお、ゲル分率は、以下の方法により測定することができる。
片面粘着テープから感熱粘着剤層(粘着剤組成物)のみを0.1g取り出し、酢酸エチル50mL中に浸漬し、振とう機で温度23度、200rpmの条件で24時間振とうする。振とう後、金属メッシュ(目開き#200メッシュ)を用いて、酢酸エチルと酢酸エチルを吸収し膨潤した粘着剤組成物を分離する。分離後の粘着剤組成物を110℃の条件下で1時間乾燥させる。乾燥後の金属メッシュを含む粘着剤組成物の重量を測定し、下記式を用いてゲル分率を算出する。
ゲル分率(重量%)=100×(W-W)/W
(W:初期粘着剤組成物重量、W:乾燥後の金属メッシュを含む粘着剤組成物重量、W:金属メッシュの初期重量)
The gel fraction of the heat-sensitive adhesive layer is not particularly limited, but the preferred lower limit is 50% by weight. When the gel fraction is 50% by weight or more, the heat-sensitive adhesive layer is prevented from being swelled by the strong alkaline solution, and the resistance of the single-sided adhesive tape to the strong alkaline solution becomes higher. In addition, if the gel fraction is 50% by weight or more, it becomes easier to adjust the coefficient of static friction to the SUS within the above range, and wrinkles are further suppressed when the single-sided adhesive tape is attached to the edge of the metal-clad laminate. can do. A more preferable lower limit of the gel fraction is 60% by weight. Although the upper limit of the gel fraction is not particularly limited, the upper limit is preferably 90% by weight, and the upper limit is more preferably 80% by weight, since the heat-sensitive adhesive layer tends to exhibit sufficient adhesiveness when heated.
In addition, the gel fraction can be measured by the following method.
0.1 g of only the heat-sensitive adhesive layer (adhesive composition) is taken out from the single-sided adhesive tape, immersed in 50 mL of ethyl acetate, and shaken with a shaker at a temperature of 23°C and 200 rpm for 24 hours. After shaking, a metal mesh (#200 mesh) is used to separate the ethyl acetate and the pressure-sensitive adhesive composition that has absorbed and swollen the ethyl acetate. The adhesive composition after separation is dried at 110° C. for 1 hour. The weight of the pressure-sensitive adhesive composition containing the metal mesh after drying is measured, and the gel fraction is calculated using the following formula.
Gel fraction (% by weight) = 100 x (W 1 - W 2 )/W 0
(W 0 : initial weight of adhesive composition, W 1 : weight of adhesive composition containing metal mesh after drying, W 2 : initial weight of metal mesh)
上記感熱粘着剤層の表面粗さRaは特に限定されないが、好ましい下限が0.01μm、好ましい上限が0.8μmである。上記表面粗さRaが上記範囲内であれば、上記SUSに対する静止摩擦係数を上記範囲に調整しやすくなり、片面粘着テープを金属張積層板の端部に貼り付ける際にシワをより抑制することができる。上記表面粗さRaのより好ましい下限は0.02μm、より好ましい上限は0.1μmである。
なお、表面粗さRaとは、JIS B 0601-2001に規定される算術平均粗さを意味する。
The surface roughness Ra of the heat-sensitive adhesive layer is not particularly limited, but the preferred lower limit is 0.01 μm and the preferred upper limit is 0.8 μm. If the surface roughness Ra is within the above range, it becomes easier to adjust the static friction coefficient to the above SUS within the above range, and wrinkles are further suppressed when the single-sided adhesive tape is attached to the edge of the metal-clad laminate. can be done. A more preferable lower limit of the surface roughness Ra is 0.02 μm, and a more preferable upper limit thereof is 0.1 μm.
The surface roughness Ra means arithmetic mean roughness defined in JIS B 0601-2001.
上記感熱粘着剤層は特に限定されず、例えば、ゴム系、スチレン系、ポリエステル系、アクリル系等の感熱粘着剤層を用いることができるが、光、熱、水分等に対し比較的安定であり、加熱圧着により種々の被着体に接着が可能であることから、アクリル系ポリマーを含有することが好ましい。 The heat-sensitive adhesive layer is not particularly limited, and for example, rubber-based, styrene-based, polyester-based, acrylic-based heat-sensitive adhesive layers can be used. Since it can be adhered to various adherends by thermocompression, it preferably contains an acrylic polymer.
上記感熱粘着剤層に含まれるアクリル系ポリマー(以下、感熱粘着剤層用アクリル系ポリマーともいう)は特に限定されないが、架橋性官能基を有するモノマーに由来する構成単位を有することが好ましい。このような構成単位を有することで、架橋剤を併用したときに上記感熱粘着剤層用アクリル系ポリマー間を架橋させることができる。その際の架橋度を調整することで、上記感熱粘着剤層の貯蔵弾性率G’を上記範囲に調整しやすくなり、上記SUSに対する静止摩擦係数を上記範囲に調整しやすくなる。 The acrylic polymer contained in the heat-sensitive adhesive layer (hereinafter also referred to as the acrylic polymer for the heat-sensitive adhesive layer) is not particularly limited, but preferably has a structural unit derived from a monomer having a crosslinkable functional group. By having such a structural unit, the acrylic polymer for the heat-sensitive adhesive layer can be cross-linked when a cross-linking agent is used in combination. By adjusting the degree of crosslinking at that time, the storage elastic modulus G' of the heat-sensitive adhesive layer can be easily adjusted within the above range, and the coefficient of static friction against SUS can be easily adjusted within the above range.
上記架橋性官能基としては、例えば、水酸基、カルボキシル基、グリシジル基、アミノ基、アミド基、ニトリル基等が挙げられる。なかでも、上記感熱粘着剤層の貯蔵弾性率G’の調整が容易であることから、水酸基又はカルボキシル基が好ましい。
上記水酸基を有するモノマーとしては、例えば、4-ヒドロキシブチル(メタ)アクリレート、2-ヒドロキシエチル(メタ)アクリレート等の水酸基を有する(メタ)アクリル酸エステルが挙げられる。上記カルボキシル基を有するモノマーとしては、例えば、(メタ)アクリル酸等が挙げられる。上記グリシジル基を有するモノマーとしては、例えば、グリシジル(メタ)アクリレート等が挙げられる。上記アミド基を有するモノマーとしては、例えば、ヒドロキシエチルアクリルアミド、イソプロピルアクリルアミド、ジメチルアミノプロピルアクリルアミド等が挙げられる。上記ニトリル基を有するモノマーとしては、例えば、アクリロニトリル等が挙げられる。これらの架橋性官能基を有するモノマーは、単独で用いてもよく、2種以上を併用してもよい。
なお、本明細書中において(メタ)アクリレートとは、アクリレート又はメタクリレートを意味し、(メタ)アクリルとは、アクリル又はメタクリルを意味する。アクリル系ポリマーは、メタクリル系ポリマーであってもよい。
Examples of the crosslinkable functional group include a hydroxyl group, a carboxyl group, a glycidyl group, an amino group, an amide group, and a nitrile group. Among them, a hydroxyl group or a carboxyl group is preferable because the storage elastic modulus G′ of the heat-sensitive adhesive layer can be easily adjusted.
Examples of the monomer having a hydroxyl group include (meth)acrylic acid esters having a hydroxyl group such as 4-hydroxybutyl (meth)acrylate and 2-hydroxyethyl (meth)acrylate. Examples of the monomer having a carboxyl group include (meth)acrylic acid. Examples of the monomer having a glycidyl group include glycidyl (meth)acrylate. Examples of the amide group-containing monomer include hydroxyethylacrylamide, isopropylacrylamide, and dimethylaminopropylacrylamide. Examples of the nitrile group-containing monomer include acrylonitrile. These monomers having a crosslinkable functional group may be used alone or in combination of two or more.
In this specification, (meth)acrylate means acrylate or methacrylate, and (meth)acryl means acrylic or methacrylic. The acrylic polymer may be a methacrylic polymer.
上記感熱粘着剤層用アクリル系ポリマーにおける上記架橋性官能基を有するモノマーに由来する構成単位の含有量は特に限定されないが、好ましい下限が0.1重量%、好ましい上限が5重量%である。
また、上記架橋性官能基を有するモノマーとして上記カルボキシル基を有するモノマーを用いる場合、片面粘着テープの強アルカリ性溶液への耐性が更に高くなることから、上記カルボキシル基を有するモノマーに由来する構成単位の含有量のより好ましい上限は3重量%、更に好ましい上限は0.5重量%である。
The content of the structural unit derived from the monomer having a crosslinkable functional group in the acrylic polymer for the heat-sensitive adhesive layer is not particularly limited, but the preferred lower limit is 0.1% by weight and the preferred upper limit is 5% by weight.
Further, when a monomer having a carboxyl group is used as the monomer having a crosslinkable functional group, the resistance of the single-sided adhesive tape to a strong alkaline solution is further increased. A more preferable upper limit of the content is 3% by weight, and a further preferable upper limit is 0.5% by weight.
上記感熱粘着剤層用アクリル系ポリマーは、炭素数が1以上4以下のアルキル基を有する(メタ)アクリレートに由来する構成単位を有することが好ましく、炭素数が1以上4以下のアルキル基を有するメタクリレートに由来する構成単位を有することがより好ましい。また、上記感熱粘着剤層用アクリル系ポリマーは、環状構造を有するアルキル基を有する(メタ)アクリレートに由来する構成単位を有することも好ましい。
上記感熱粘着剤層用アクリル系ポリマーがこれらの構成単位を有することで、上記感熱粘着剤層の損失正接のピーク温度及び貯蔵弾性率G’を上記範囲に調整しやすくなり、上記SUSに対する静止摩擦係数を上記範囲に調整しやすくなるため、片面粘着テープを金属張積層板の端部に貼り付ける際にシワをより抑制することができる。上記感熱粘着剤層用アクリル系ポリマーは、炭素数が1以上4以下のアルキル基を有するメタクリレートに由来する構成単位、及び、環状構造を有するアルキル基を有するメタクリレートに由来する構成単位からなる群より選択される少なくとも1つを有することがより好ましい。
The acrylic polymer for the heat-sensitive adhesive layer preferably has a structural unit derived from (meth)acrylate having an alkyl group having 1 to 4 carbon atoms, and has an alkyl group having 1 to 4 carbon atoms. It is more preferable to have structural units derived from methacrylate. Moreover, the acrylic polymer for the heat-sensitive adhesive layer preferably has a structural unit derived from (meth)acrylate having an alkyl group having a cyclic structure.
When the acrylic polymer for the heat-sensitive adhesive layer has these structural units, it becomes easier to adjust the peak temperature of the loss tangent of the heat-sensitive adhesive layer and the storage elastic modulus G' within the above range, and the static friction against the SUS Since it becomes easier to adjust the coefficient within the above range, wrinkles can be further suppressed when the single-sided adhesive tape is attached to the edge of the metal-clad laminate. The acrylic polymer for the heat-sensitive adhesive layer is selected from the group consisting of a structural unit derived from a methacrylate having an alkyl group having 1 to 4 carbon atoms and a structural unit derived from a methacrylate having an alkyl group having a cyclic structure. It is more preferable to have at least one selected.
上記炭素数が1以上4以下のアルキル基を有する(メタ)アクリレートは特に限定されず、例えば、メチル(メタ)アクリレート、エチル(メタ)アクリレート、プロピル(メタ)アクリレート、ブチル(メタ)アクリレート等が挙げられる。上記環状構造を有するアルキル基を有する(メタ)アクリレートは特に限定されず、例えば、シクロヘキシル(メタ)アクリレート、イソボルニル(メタ)アクリレート等が挙げられる。これらの(メタ)アクリレートは、単独で用いてもよく、2種以上を併用してもよい。なかでも、上記感熱粘着剤層の損失正接のピーク温度及び貯蔵弾性率G’をより好ましい範囲に調整しやすいことから、メチルメタクリレート、ブチルアクリレート、ブチルメタクリレート及びイソボルニルメタクリレートからなる群より選択される少なくとも1つを用いることが好ましい。 The (meth)acrylate having an alkyl group having 1 to 4 carbon atoms is not particularly limited, and examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and the like. mentioned. The (meth)acrylate having an alkyl group having a cyclic structure is not particularly limited, and examples thereof include cyclohexyl (meth)acrylate and isobornyl (meth)acrylate. These (meth)acrylates may be used alone or in combination of two or more. Among them, it is selected from the group consisting of methyl methacrylate, butyl acrylate, butyl methacrylate and isobornyl methacrylate, since the peak temperature of the loss tangent and the storage elastic modulus G′ of the heat-sensitive adhesive layer can be easily adjusted to more preferable ranges. It is preferable to use at least one of
上記感熱粘着剤層用アクリル系ポリマーにおける上記炭素数が1以上4以下のアルキル基を有する(メタ)アクリレートに由来する構成単位、及び、上記環状構造を有するアルキル基を有する(メタ)アクリレートに由来する構成単位の合計含有量は特に限定されないが、好ましい下限が50重量%、好ましい上限が98重量%である。上記構成単位の合計含有量が上記範囲内であれば、上記感熱粘着剤層の損失正接のピーク温度及び貯蔵弾性率G’を上記範囲に調整しやすくなり、上記SUSに対する静止摩擦係数を上記範囲に調整しやすくなるため、片面粘着テープを金属張積層板の端部に貼り付ける際にシワをより抑制することができる。上記構成単位の合計含有量のより好ましい下限は60重量%、更に好ましい下限は70重量%であり、より好ましい上限は95重量%、更に好ましい上限は90重量%、更により好ましい上限は80重量%である。
なお、上記合計含有量は上記炭素数が1以上4以下のアルキル基を有する(メタ)アクリレートに由来する構成単位、及び、上記環状構造を有するアルキル基を有する(メタ)アクリレートに由来する構成単位の合計含有量を表すが、上記感熱粘着剤層用アクリル系ポリマーはどちらか一方のみを含有しても、両方を含有してもよい。
Structural units derived from the (meth)acrylate having an alkyl group having 1 to 4 carbon atoms in the acrylic polymer for the heat-sensitive adhesive layer, and derived from the (meth)acrylate having an alkyl group having a cyclic structure Although the total content of the constituent units is not particularly limited, the preferable lower limit is 50% by weight and the preferable upper limit is 98% by weight. If the total content of the structural units is within the above range, the peak temperature of the loss tangent and the storage elastic modulus G′ of the heat-sensitive adhesive layer can be easily adjusted within the above range, and the static friction coefficient for the SUS is within the above range. Therefore, wrinkles can be further suppressed when the single-sided adhesive tape is attached to the edge of the metal-clad laminate. A more preferable lower limit of the total content of the structural units is 60% by weight, a more preferable lower limit is 70% by weight, a more preferable upper limit is 95% by weight, a still more preferable upper limit is 90% by weight, and a still more preferable upper limit is 80% by weight. is.
In addition, the total content is a structural unit derived from a (meth)acrylate having an alkyl group having 1 to 4 carbon atoms, and a structural unit derived from a (meth)acrylate having an alkyl group having a cyclic structure. The acrylic polymer for the heat-sensitive adhesive layer may contain either one or both of them.
また、上記感熱粘着剤層用アクリル系ポリマーにおける上記炭素数が1以上4以下のアルキル基を有するメタクリレートに由来する構成単位及び上記環状構造を有するアルキル基を有するメタクリレートに由来する構成単位の合計含有量は、同様の観点から、好ましい下限が50重量%、好ましい上限が90重量%である。上記合計含有量のより好ましい下限は60重量%、より好ましい上限は80重量%である。 Further, the total content of the structural units derived from the methacrylate having an alkyl group having 1 to 4 carbon atoms and the structural unit derived from the methacrylate having an alkyl group having a cyclic structure in the acrylic polymer for the heat-sensitive adhesive layer From the same point of view, the preferred lower limit is 50% by weight and the preferred upper limit is 90% by weight. A more preferable lower limit of the above total content is 60% by weight, and a more preferable upper limit is 80% by weight.
上記感熱粘着剤層用アクリル系ポリマーは、本発明の効果を阻害しない範囲で、更に、他のモノマーに由来する構成単位を有していてもよい。上記他のモノマーとして、例えば、n-オクチル(メタ)アクリレート、イソオクチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、n-ノニル(メタ)アクリレート、イソノニル(メタ)アクリレート、デシル(メタ)アクリレート、ラウリル(メタ)アクリレート、ステアリル(メタ)アクリレート、イソステアリル(メタ)アクリレート、ベンジル(メタ)アクリレート、フェノキシエチル(メタ)アクリレート、エチルカルビトール(メタ)アクリレート、酢酸ビニル、フッ素含有(メタ)アクリレート等が挙げられる。
また、上記感熱粘着剤層用アクリル系ポリマーを紫外線重合法により調製する場合には、更に、ジビニルベンゼン、トリメチロールプロパントリ(メタ)アクリレート等の多官能モノマーに由来する構成単位を有することが好ましい。
The acrylic polymer for the heat-sensitive adhesive layer may further have structural units derived from other monomers as long as the effects of the present invention are not impaired. Examples of the other monomers include n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, Lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, ethyl carbitol (meth)acrylate, vinyl acetate, fluorine-containing (meth)acrylate, etc. is mentioned.
In addition, when the acrylic polymer for the heat-sensitive adhesive layer is prepared by an ultraviolet polymerization method, it preferably further contains structural units derived from polyfunctional monomers such as divinylbenzene and trimethylolpropane tri(meth)acrylate. .
上記感熱粘着剤層用アクリル系ポリマーの溶解度パラメーター(SP値)は特に限定されないが、好ましい下限は9.2、好ましい上限は10.5である。上記SP値が上記範囲内であれば、上記感熱粘着剤層への強アルカリ性溶液の膨潤が抑えられ、片面粘着テープの強アルカリ性溶液への耐性がより高くなる。また、上記SP値が上記範囲内であれば、上記感熱粘着剤層の金属張積層板への密着力が高くなり、金属張積層板を充分に保護することができる。上記SP値のより好ましい下限は9.5、より好ましい上限は10.2であり、更に好ましい下限は9.6、更に好ましい上限は10である。
なお、溶解度パラメーター(SP値)とは、Fedors法による溶解度パラメーター(SP値)((cal/cm0.5)を意味し、Fedors法(R.F.Fedors,Polym.Eng.Sci.,14(2),147-154(1974))を用いて算出された、溶解のしやすさを表すことのできる指標である。
The solubility parameter (SP value) of the acrylic polymer for the heat-sensitive adhesive layer is not particularly limited, but the preferred lower limit is 9.2 and the preferred upper limit is 10.5. When the SP value is within the above range, the heat-sensitive adhesive layer is prevented from being swelled by a strong alkaline solution, and the resistance of the single-sided adhesive tape to a strong alkaline solution is increased. Further, when the SP value is within the above range, the adhesion of the heat-sensitive adhesive layer to the metal-clad laminate is increased, and the metal-clad laminate can be sufficiently protected. The SP value has a more preferable lower limit of 9.5, a more preferable upper limit of 10.2, a still more preferable lower limit of 9.6, and a still more preferable upper limit of 10.
The solubility parameter (SP value) means the solubility parameter (SP value) ((cal/cm 3 ) 0.5 ) according to the Fedors method, and is calculated according to the Fedors method (RF Fedors, Polym. Eng. Sci. , 14(2), 147-154 (1974)) and is an index capable of expressing the ease of dissolution.
上記感熱粘着剤層用アクリル系ポリマーの重量平均分子量(Mw)は特に限定されないが、好ましい下限は25万、好ましい上限は200万であり、より好ましい下限は30万、更に好ましい下限は40万であり、より好ましい上限は150万である。
なお、重量平均分子量(Mw)は、重合条件(例えば、重合開始剤の種類又は量、重合温度、モノマー濃度等)によって調整できる。また、重量平均分子量(Mw)は、以下の方法により測定できる。
アクリル系ポリマー溶液をフィルター(材質:ポリテトラフルオロエチレン、ポア径:0.2μm)で濾過する。得られた濾液をゲル浸透クロマトグラフ(例えば、Waters社製、2690 Separations Model)に供給して、サンプル流量1ミリリットル/min、カラム温度40℃の条件でGPC測定を行い、アクリル系ポリマーのポリスチレン換算分子量を測定して、重量平均分子量(Mw)を求める。カラムとしては、例えば、GPC KF-806LやGPC LF-804(昭和電工社製)を用い、検出器としては、示差屈折計を用いる。
The weight average molecular weight (Mw) of the acrylic polymer for the heat-sensitive adhesive layer is not particularly limited, but the preferred lower limit is 250,000, the preferred upper limit is 2,000,000, the more preferred lower limit is 300,000, and the further preferred lower limit is 400,000. and a more preferable upper limit is 1,500,000.
The weight-average molecular weight (Mw) can be adjusted by polymerization conditions (eg, type or amount of polymerization initiator, polymerization temperature, monomer concentration, etc.). Moreover, the weight average molecular weight (Mw) can be measured by the following method.
The acrylic polymer solution is filtered through a filter (material: polytetrafluoroethylene, pore diameter: 0.2 μm). The obtained filtrate is supplied to a gel permeation chromatograph (e.g., Waters, 2690 Separations Model), and GPC measurement is performed under the conditions of a sample flow rate of 1 ml/min and a column temperature of 40 ° C., and the acrylic polymer is converted to polystyrene. The molecular weight is measured to determine the weight average molecular weight (Mw). As the column, for example, GPC KF-806L or GPC LF-804 (manufactured by Showa Denko KK) is used, and as the detector, a differential refractometer is used.
上記感熱粘着剤層用アクリル系ポリマーを調製する方法は特に限定されず、上記構成単位の由来となるモノマーを、重合開始剤の存在下にてラジカル反応させる方法等が挙げられる。重合方法は特に限定されず、従来公知の方法を用いることができる。例えば、溶液重合(沸点重合又は定温重合)、エマルジョン重合、懸濁重合、塊状重合等が挙げられる。なかでも、合成が簡便であること及び耐水性の観点から、溶液重合が好ましい。 The method for preparing the acrylic polymer for the heat-sensitive adhesive layer is not particularly limited, and examples thereof include a method of radically reacting the monomers from which the structural units are derived in the presence of a polymerization initiator. The polymerization method is not particularly limited, and conventionally known methods can be used. Examples thereof include solution polymerization (boiling point polymerization or constant temperature polymerization), emulsion polymerization, suspension polymerization, bulk polymerization and the like. Among them, solution polymerization is preferable from the viewpoint of ease of synthesis and water resistance.
重合方法として溶液重合を用いる場合、反応溶剤として、例えば、酢酸エチル、トルエン、メチルエチルケトン、メチルスルホキシド、エタノール、アセトン、ジエチルエーテル等が挙げられる。これらの反応溶剤は、単独で用いてもよく、2種以上を併用してもよい。 When solution polymerization is used as the polymerization method, examples of reaction solvents include ethyl acetate, toluene, methyl ethyl ketone, methyl sulfoxide, ethanol, acetone, and diethyl ether. These reaction solvents may be used alone or in combination of two or more.
上記重合開始剤は特に限定されず、例えば、有機過酸化物、アゾ化合物等が挙げられる。上記有機過酸化物として、例えば、1,1-ビス(t-ヘキシルパーオキシ)-3,3,5-トリメチルシクロヘキサン、t-ヘキシルパーオキシピバレート、t-ブチルパーオキシピバレート、2,5-ジメチル-2,5-ビス(2-エチルヘキサノイルパーオキシ)ヘキサン、t-ヘキシルパーオキシ-2-エチルヘキサノエート、t-ブチルパーオキシ-2-エチルヘキサノエート、t-ブチルパーオキシイソブチレート、t-ブチルパーオキシ-3,5,5-トリメチルヘキサノエート、t-ブチルパーオキシラウレート等が挙げられる。上記アゾ化合物として、例えば、アゾビスイソブチロニトリル、アゾビスシクロヘキサンカルボニトリル等が挙げられる。これらの重合開始剤は、単独で用いてもよく、2種以上を併用してもよい。 The polymerization initiator is not particularly limited, and examples thereof include organic peroxides and azo compounds. Examples of the organic peroxide include 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane, t-hexylperoxypivalate, t-butylperoxypivalate, 2,5 -dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxy isobutyrate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate and the like. Examples of the azo compound include azobisisobutyronitrile and azobiscyclohexanecarbonitrile. These polymerization initiators may be used alone or in combination of two or more.
上記感熱粘着剤層は、更に、粘着付与樹脂を含有することが好ましい。
上記感熱粘着剤層が上記粘着付与樹脂を含有することにより、片面粘着テープを加熱圧着した際の界面密着性が向上するとともに、片面粘着テープの強アルカリ性溶液への耐性が更に高くなる。
上記粘着付与樹脂は特に限定されず、例えば、クマロン樹脂、テルペン樹脂、テルペンフェノール樹脂、ロジン樹脂、ロジン誘導体樹脂、石油樹脂、アルキルフェノール樹脂、これらの水素化物等が挙げられる。これらの粘着付与樹脂は、単独で用いてもよく、2種以上を併用してもよい。
The heat-sensitive adhesive layer preferably further contains a tackifying resin.
By containing the tackifying resin in the heat-sensitive adhesive layer, the interfacial adhesion is improved when the single-sided adhesive tape is heat-pressed, and the resistance of the single-sided adhesive tape to strong alkaline solutions is further increased.
The tackifying resin is not particularly limited, and examples thereof include coumarone resins, terpene resins, terpene phenol resins, rosin resins, rosin derivative resins, petroleum resins, alkylphenol resins, and hydrides thereof. These tackifying resins may be used alone or in combination of two or more.
上記テルペンフェノール樹脂とは、テルペン残基及びフェノール残基を含むポリマーを意味する。また、テルペンフェノール樹脂とは、テルペンとフェノール化合物との共重合体(テルペン-フェノール共重合体樹脂)と、テルペンの単独重合体又は共重合体(テルペン樹脂、典型的には未変性テルペン樹脂)をフェノール変性したフェノール変性テルペン樹脂と、更にはこれらの樹脂におけるテルペン部位を水素添加した樹脂とを包含する概念である。 The terpene phenolic resin means a polymer containing terpene residues and phenol residues. In addition, terpene phenol resins include copolymers of terpene and phenol compounds (terpene-phenol copolymer resins), and homopolymers or copolymers of terpene (terpene resins, typically unmodified terpene resins). is a concept including phenol-modified terpene resins modified with phenol, and resins obtained by hydrogenating the terpene sites in these resins.
上記テルペンフェノール樹脂を構成するテルペンは特に限定されないが、α-ピネン、β-ピネン、リモネン、カンフェン等のモノテルペンが好ましい。なお、リモネンには、d体、l体及びd/l体(ジペンテン)が含まれる。 The terpene constituting the terpene phenol resin is not particularly limited, but monoterpenes such as α-pinene, β-pinene, limonene and camphene are preferable. Limonene includes d-form, l-form and d/l-form (dipentene).
上記ロジン樹脂として、より具体的には例えば、ガムロジン、ウッドロジン、トール油ロジン等の未変性ロジン(生ロジン)、これら未変性ロジンを変性した変性ロジン等が挙げられる。上記変性ロジンにおける変性としては、例えば、水添化、不均化、重合等が挙げられる。上記変性ロジンとして、より具体的には例えば、水添ロジン、不均化ロジン、重合ロジン、その他の化学的に修飾されたロジン等が挙げられる。 More specific examples of the rosin resin include unmodified rosins (fresh rosins) such as gum rosin, wood rosin and tall oil rosin, modified rosins obtained by modifying these unmodified rosins, and the like. Modification of the modified rosin includes, for example, hydrogenation, disproportionation, and polymerization. More specific examples of the modified rosin include hydrogenated rosin, disproportionated rosin, polymerized rosin, and other chemically modified rosins.
上記ロジン誘導体樹脂として、より具体的には例えば、上記ロジン樹脂をアルコール類によりエステル化したロジンエステル樹脂、上記ロジン樹脂を不飽和脂肪酸で変性した不飽和脂肪酸変性ロジン樹脂、上記ロジンエステル樹脂を不飽和脂肪酸で変性した不飽和脂肪酸変性ロジンエステル樹脂等が挙げられる。また、上記ロジン誘導体樹脂としては、例えば、上記不飽和脂肪酸変性ロジン樹脂又は不飽和脂肪酸変性ロジンエステル樹脂におけるカルボキシル基を還元処理したロジンアルコール樹脂等も挙げられる。
更に、上記ロジン誘導体樹脂としては、上記ロジン樹脂又はロジン誘導体樹脂(特に、ロジンエステル樹脂)の金属塩又はロジンフェノール樹脂等も挙げられる。なお、ロジンフェノール樹脂は、上記ロジン樹脂又はロジン誘導体樹脂に酸触媒下でフェノールを付加させ熱重合することにより得られる。
As the rosin derivative resin, more specifically, for example, a rosin ester resin obtained by esterifying the rosin resin with an alcohol, an unsaturated fatty acid-modified rosin resin obtained by modifying the rosin resin with an unsaturated fatty acid, and an unsaturated rosin ester resin. Unsaturated fatty acid-modified rosin ester resin modified with saturated fatty acid and the like can be mentioned. Examples of the rosin derivative resin include rosin alcohol resin obtained by reducing the carboxyl group in the unsaturated fatty acid-modified rosin resin or unsaturated fatty acid-modified rosin ester resin.
Further, examples of the rosin derivative resins include metal salts of the rosin resins or rosin derivative resins (particularly, rosin ester resins), rosin phenol resins, and the like. The rosin phenol resin can be obtained by adding phenol to the above rosin resin or rosin derivative resin under an acid catalyst, followed by thermal polymerization.
上記石油樹脂として、より具体的には例えば、脂肪族系(C5系)石油樹脂、芳香族系(C9系)石油樹脂、C5/C9共重合系石油樹脂、脂環族系石油樹脂、及び、これらの水添化物等が挙げられる。 More specifically, the petroleum resins include aliphatic (C5) petroleum resins, aromatic (C9) petroleum resins, C5/C9 copolymer petroleum resins, alicyclic petroleum resins, and Hydrogenated products thereof and the like are included.
なかでも、上記粘着付与樹脂は、軟化点が100℃以上、水酸基価が25mgKOH/g以上であることが好ましい。上記感熱粘着剤層がこのような粘着付与樹脂を含有することにより、片面粘着テープを加熱圧着した際の界面密着性が向上するとともに、片面粘着テープの強アルカリ性溶液への耐性が更に高くなる。更に、上記粘着付与樹脂は、水酸基価が40mgKOH/g以上の水添ロジンエステル樹脂を含有することがより好ましい。上記水酸基価が40mgKOH/g以上の水添ロジンエステル樹脂の水酸基価の上限は特に限定されないが、通常80mgKOH/g程度であり、好ましくは50mgKOH/g以下である。 In particular, the tackifier resin preferably has a softening point of 100° C. or higher and a hydroxyl value of 25 mgKOH/g or higher. By containing such a tackifying resin in the heat-sensitive adhesive layer, the interfacial adhesion is improved when the single-sided adhesive tape is heat-pressed, and the resistance of the single-sided adhesive tape to strong alkaline solutions is further increased. Furthermore, the tackifying resin more preferably contains a hydrogenated rosin ester resin having a hydroxyl value of 40 mgKOH/g or more. Although the upper limit of the hydroxyl value of the hydrogenated rosin ester resin having a hydroxyl value of 40 mgKOH/g or more is not particularly limited, it is usually about 80 mgKOH/g, preferably 50 mgKOH/g or less.
上記粘着付与樹脂の含有量は特に限定されないが、上記感熱粘着剤層用アクリル系ポリマー100重量部に対する好ましい下限は5重量部、好ましい上限は50重量部であり、より好ましい下限は10重量部、より好ましい上限は35重量部である。上記粘着付与樹脂の含有量が上記範囲内であれば、片面粘着テープを加熱圧着した際の界面密着性が向上するとともに、片面粘着テープの強アルカリ性溶液への耐性が更に高くなる。 The content of the tackifying resin is not particularly limited, but the preferred lower limit is 5 parts by weight, the preferred upper limit is 50 parts by weight, and the more preferred lower limit is 10 parts by weight, with respect to 100 parts by weight of the acrylic polymer for the heat-sensitive adhesive layer. A more preferable upper limit is 35 parts by weight. When the content of the tackifying resin is within the above range, the interfacial adhesion is improved when the single-sided adhesive tape is heat-pressed, and the resistance of the single-sided adhesive tape to strong alkaline solutions is further enhanced.
上記感熱粘着剤層は、シランカップリング剤を含有してもよい。
上記感熱粘着剤層が上記シランカップリング剤を含有することにより、片面粘着テープを加熱圧着した際の界面密着性が向上するとともに、片面粘着テープの強アルカリ性溶液への耐性が更に高くなる。
The heat-sensitive adhesive layer may contain a silane coupling agent.
By containing the silane coupling agent in the heat-sensitive adhesive layer, the interfacial adhesion is improved when the single-sided adhesive tape is heat-pressed, and the resistance of the single-sided adhesive tape to strong alkaline solutions is further increased.
上記シランカップリング剤は特に限定されず、例えば、ビニルトリメトキシシラン、ビニルトリエトキシシラン、γ-メタクリロキシプロピルトリメトキシシラン、γ-メタクリロキシプロピルメチルジメトキシシラン、γ-グリシドキシプロピルトリメトキシシラン、γ-グリシドキシプロピルメチルジメトキシシラン、γ-グリシドキシプロピルメチルジエトキシシラン、γ-グリシドキシプロピルトリエトキシシラン、2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン、γ-アミノプロピルトリメトキシシラン、γ-アミノプロピルトリエトキシシラン、γ-アミノプロピルトリメチルメトキシシラン、N-(2-アミノエチル)3-アミノプロピルトリエトキシシラン、N-(2-アミノエチル)3-アミノプロピルメチルジメトキシシラン、γ-メルカプトプロピルトリメトキシシラン、γ-メルカプトプロピルトリエトキシシラン、メルカプトブチルトリメトキシシラン、γ-メルカプトプロピルメチルジメトキシシラン等が挙げられる。なかでも、γ-グリシドキシプロピルトリエトキシシラン、γ-メルカプトプロピルトリメトキシシランが好ましい。 The silane coupling agent is not particularly limited, and examples include vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane. , γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-amino Propyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethylmethoxysilane, N-(2-aminoethyl)3-aminopropyltriethoxysilane, N-(2-aminoethyl)3-aminopropylmethyl dimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, mercaptobutyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane and the like. Among them, γ-glycidoxypropyltriethoxysilane and γ-mercaptopropyltrimethoxysilane are preferred.
上記シランカップリング剤の含有量は特に限定されないが、上記感熱粘着剤層用アクリル系ポリマー100重量部に対する好ましい下限が0.1重量部、好ましい上限が5重量部である。上記シランカップリング剤の含有量がこの範囲内であることにより、片面粘着テープを加熱圧着した際の界面密着性が向上するとともに、片面粘着テープの強アルカリ性溶液への耐性が更に高くなる。上記シランカップリング剤の含有量のより好ましい下限は0.5重量部、より好ましい上限は3重量部である。 The content of the silane coupling agent is not particularly limited, but the preferred lower limit is 0.1 parts by weight and the preferred upper limit is 5 parts by weight with respect to 100 parts by weight of the acrylic polymer for the heat-sensitive adhesive layer. When the content of the silane coupling agent is within this range, the interfacial adhesion is improved when the single-sided pressure-sensitive adhesive tape is heat-pressed, and the resistance of the single-sided pressure-sensitive adhesive tape to strong alkaline solutions is further increased. A more preferable lower limit to the content of the silane coupling agent is 0.5 parts by weight, and a more preferable upper limit is 3 parts by weight.
上記感熱粘着剤層は、更に、架橋剤を含有してもよい。
上記感熱粘着剤層が上記架橋剤を含有することで、上記感熱粘着剤層用アクリル系ポリマーが上記架橋性官能基を有するモノマーに由来する構成単位を含有する場合に上記感熱粘着剤層用アクリル系ポリマー間を架橋させることができる。
上記架橋剤は特に限定されず、例えば、イソシアネート系架橋剤、アジリジン系架橋剤、エポキシ系架橋剤、金属キレート型架橋剤等が挙げられる。なかでも、イソシアネート系架橋剤及びエポキシ系架橋剤が好ましい。更に、上記架橋性官能基を有するモノマーに由来する構成単位と反応することで加水分解しにくいエステル結合を形成するため、片面粘着テープの強アルカリ性溶液への耐性が更に高くなることから、エポキシ系架橋剤がより好ましい。
The heat-sensitive adhesive layer may further contain a cross-linking agent.
When the heat-sensitive adhesive layer contains the cross-linking agent, the acrylic polymer for the heat-sensitive adhesive layer contains a structural unit derived from a monomer having a cross-linkable functional group. It is possible to crosslink between the system polymers.
The cross-linking agent is not particularly limited, and examples thereof include isocyanate-based cross-linking agents, aziridine-based cross-linking agents, epoxy-based cross-linking agents, and metal chelate-type cross-linking agents. Among them, an isocyanate-based cross-linking agent and an epoxy-based cross-linking agent are preferable. Furthermore, by reacting with the constituent units derived from the monomer having the crosslinkable functional group, an ester bond that is difficult to hydrolyze is formed, so that the resistance of the single-sided adhesive tape to strong alkaline solutions is further increased. A cross-linking agent is more preferred.
上記架橋剤の含有量は特に限定されないが、上記感熱粘着剤層用アクリル系ポリマー100重量部に対する好ましい下限は0.01重量部、好ましい上限は10重量部であり、より好ましい下限は0.1重量部、より好ましい上限は5重量部である。 The content of the crosslinking agent is not particularly limited, but the preferred lower limit is 0.01 parts by weight, the preferred upper limit is 10 parts by weight, and the more preferred lower limit is 0.1 parts by weight, per 100 parts by weight of the acrylic polymer for the heat-sensitive adhesive layer. Parts by weight, a more preferred upper limit is 5 parts by weight.
上記感熱粘着剤層は、必要に応じて、可塑剤、乳化剤、軟化剤、充填剤、顔料、染料等の添加剤、その他の樹脂等を含有していてもよい。 The heat-sensitive adhesive layer may contain additives such as plasticizers, emulsifiers, softeners, fillers, pigments and dyes, and other resins, if necessary.
上記感熱粘着剤層の厚みは特に限定されないが、好ましい下限が5μm、好ましい上限が100μmである。上記厚みが上記範囲内であれば、片面粘着テープを良好に加熱圧着することができ、その際のシワをより抑制することができ、片面粘着テープの強アルカリ性溶液への耐性がより高くなる。上記厚みのより好ましい下限は10μm、より好ましい上限は50μmであり、更に好ましい下限は20μm、更に好ましい上限は40μmである。
また、上記感熱粘着剤層の厚みは、被着体として用いる金属張積層板の厚みの1/2よりも厚いことが好ましい。このような場合、金属張積層板の表面から裏面にまでまたがるように片面粘着テープを金属張積層板の端部に貼り付けた場合であっても、金属張積層板の端部と上記感熱粘着剤層との間に隙間が生じにくくなり、剥がれが生じにくくなる。上記感熱粘着剤層の厚みは、金属張積層板の厚みの2/3よりも厚いことがより好ましい。
The thickness of the heat-sensitive adhesive layer is not particularly limited, but the preferred lower limit is 5 µm and the preferred upper limit is 100 µm. When the thickness is within the above range, the single-sided adhesive tape can be satisfactorily heat-pressed, wrinkles at that time can be further suppressed, and the single-sided adhesive tape has a higher resistance to strong alkaline solutions. A more preferable lower limit of the thickness is 10 μm, a more preferable upper limit is 50 μm, a still more preferable lower limit is 20 μm, and a further preferable upper limit is 40 μm.
Moreover, the thickness of the heat-sensitive adhesive layer is preferably thicker than 1/2 of the thickness of the metal-clad laminate used as the adherend. In such a case, even if a single-sided adhesive tape is attached to the edge of the metal-clad laminate so as to extend from the front surface to the back surface of the metal-clad laminate, the edge of the metal-clad laminate and the heat-sensitive adhesive A gap is less likely to occur with the agent layer, and peeling is less likely to occur. More preferably, the thickness of the heat-sensitive adhesive layer is thicker than 2/3 of the thickness of the metal-clad laminate.
上記片面粘着テープは、上記基材と上記感熱粘着剤層との間に更に感圧粘着剤層を有することが好ましい。これにより、上記基材と上記感熱粘着剤層との間のアンカー性が増すことから、片面粘着テープの強アルカリ性溶液への耐性がより高くなる。 The single-sided adhesive tape preferably further has a pressure-sensitive adhesive layer between the substrate and the heat-sensitive adhesive layer. As a result, the anchoring property between the substrate and the heat-sensitive adhesive layer is increased, so that the resistance of the single-sided pressure-sensitive adhesive tape to strong alkaline solutions is increased.
上記感圧粘着剤層の貯蔵弾性率G’は特に限定されないが、23℃における貯蔵弾性率G’の好ましい上限が0.2MPaである。上記23℃における貯蔵弾性率G’が0.2MPa以下であれば、上記基材と上記感熱粘着剤層との間のアンカー性がより向上する。上記23℃における貯蔵弾性率G’のより好ましい上限は0.15MPaである。上記23℃における貯蔵弾性率G’の下限は特に限定されないが、上記感圧粘着剤層の凝集力を維持する観点から、好ましい下限は0.01MPa、より好ましい下限は0.03MPaである。
なお、23℃における貯蔵弾性率は、動的粘弾性測定装置(例えば、アイティー計測制御社製「DVA-200」、レオメトリックス社製「ARES」等)を用いて、動的粘弾性測定のせん断モード、角周波数1Hz、速度5℃/minの条件で-40℃から140℃まで測定を行うことで得ることができる。
The storage elastic modulus G' of the pressure-sensitive adhesive layer is not particularly limited, but the preferred upper limit of the storage elastic modulus G' at 23°C is 0.2 MPa. When the storage elastic modulus G′ at 23° C. is 0.2 MPa or less, the anchoring property between the substrate and the heat-sensitive adhesive layer is further improved. A more preferable upper limit of the storage modulus G' at 23°C is 0.15 MPa. The lower limit of the storage elastic modulus G' at 23°C is not particularly limited, but from the viewpoint of maintaining the cohesive strength of the pressure-sensitive adhesive layer, the preferred lower limit is 0.01 MPa, and the more preferred lower limit is 0.03 MPa.
The storage modulus at 23 ° C. is measured using a dynamic viscoelasticity measuring device (for example, "DVA-200" manufactured by IT Instrument Control Co., Ltd., "ARES" manufactured by Rheometrics, etc.). It can be obtained by measuring from −40° C. to 140° C. under the conditions of shear mode, angular frequency of 1 Hz, and speed of 5° C./min.
上記23℃における貯蔵弾性率G’は、上記感圧粘着剤層に含まれるベースポリマーの種類、分子量及び分子量分布、粘着付与樹脂の種類及び含有量、架橋剤の種類及び含有量等によって調整できる。 The storage elastic modulus G′ at 23° C. can be adjusted by the type, molecular weight and molecular weight distribution of the base polymer contained in the pressure-sensitive adhesive layer, the type and content of the tackifying resin, the type and content of the cross-linking agent, and the like. .
上記感圧粘着剤層は特に限定されず、例えば、ゴム系、スチレン系、ポリエステル系、アクリル系等の感圧粘着剤層を用いることができるが、光、熱、水分等に対し比較的安定であり、常温で粘着性を示し、種々の被着体に接着が可能であることから、アクリル系ポリマーを含有することが好ましい。 The pressure-sensitive adhesive layer is not particularly limited, and for example, rubber-based, styrene-based, polyester-based, acrylic-based pressure-sensitive adhesive layers can be used. and exhibits adhesiveness at room temperature and can be adhered to various adherends, and therefore, it preferably contains an acrylic polymer.
上記感圧粘着剤層に含まれるアクリル系ポリマー(以下、感圧粘着剤層用アクリル系ポリマーともいう)は特に限定されない。上記感圧粘着剤層用アクリル系ポリマーは、アルキル基の炭素数が1~18の範囲にあるアクリル酸アルキルエステル及び/又はメタクリル酸アルキルエステルを主モノマーとし、これと必要に応じて架橋性官能基を有するモノマーとを常法により共重合させることにより得られる(メタ)アクリル酸エステル共重合体であることが好ましい。更に、共重合可能な他の改質用モノマーを共重合させてもよい。 The acrylic polymer contained in the pressure-sensitive adhesive layer (hereinafter also referred to as acrylic polymer for pressure-sensitive adhesive layer) is not particularly limited. The acrylic polymer for the pressure-sensitive adhesive layer contains an acrylic acid alkyl ester and/or methacrylic acid alkyl ester having an alkyl group having a carbon number of 1 to 18 as a main monomer, and if necessary, a crosslinkable functional It is preferably a (meth)acrylic acid ester copolymer obtained by copolymerizing a monomer having a group by a conventional method. In addition, other copolymerizable modifying monomers may be copolymerized.
上記感圧粘着剤層用アクリル系ポリマーは、架橋性官能基を有するモノマーに由来する構成単位を有することが好ましい。このような構成単位を有することで、架橋剤を併用したときに上記感圧粘着剤層用アクリル系ポリマー間を架橋させることができる。その際の架橋度を調整することで、上記感圧粘着剤層の貯蔵弾性率G’を調整することができる。 The acrylic polymer for the pressure-sensitive adhesive layer preferably has structural units derived from a monomer having a crosslinkable functional group. By having such a structural unit, the acrylic polymer for the pressure-sensitive adhesive layer can be cross-linked when a cross-linking agent is used in combination. By adjusting the degree of crosslinking at that time, the storage elastic modulus G' of the pressure-sensitive adhesive layer can be adjusted.
上記架橋性官能基としては、例えば、水酸基、カルボキシル基、グリシジル基、アミノ基、アミド基、ニトリル基等が挙げられる。なかでも、上記感圧粘着剤層の貯蔵弾性率G’の調整が容易であることから、水酸基又はカルボキシル基が好ましい。
上記水酸基を有するモノマーとしては、例えば、4-ヒドロキシブチル(メタ)アクリレート、2-ヒドロキシエチル(メタ)アクリレート等の水酸基を有する(メタ)アクリル酸エステルが挙げられる。上記カルボキシル基を有するモノマーとしては、例えば、(メタ)アクリル酸等が挙げられる。上記グリシジル基を有するモノマーとしては、例えば、グリシジル(メタ)アクリレート等が挙げられる。上記アミド基を有するモノマーとしては、例えば、ヒドロキシエチルアクリルアミド、イソプロピルアクリルアミド、ジメチルアミノプロピルアクリルアミド等が挙げられる。上記ニトリル基を有するモノマーとしては、例えば、アクリロニトリル等が挙げられる。これらの架橋性官能基を有するモノマーは、単独で用いてもよく、2種以上を併用してもよい。
Examples of the crosslinkable functional group include a hydroxyl group, a carboxyl group, a glycidyl group, an amino group, an amide group, and a nitrile group. Among them, a hydroxyl group or a carboxyl group is preferable because the storage elastic modulus G′ of the pressure-sensitive adhesive layer can be easily adjusted.
Examples of the monomer having a hydroxyl group include (meth)acrylic acid esters having a hydroxyl group such as 4-hydroxybutyl (meth)acrylate and 2-hydroxyethyl (meth)acrylate. Examples of the monomer having a carboxyl group include (meth)acrylic acid. Examples of the monomer having a glycidyl group include glycidyl (meth)acrylate. Examples of the amide group-containing monomer include hydroxyethylacrylamide, isopropylacrylamide, and dimethylaminopropylacrylamide. Examples of the nitrile group-containing monomer include acrylonitrile. These monomers having a crosslinkable functional group may be used alone or in combination of two or more.
上記感圧粘着剤層用アクリル系ポリマーにおける上記架橋性官能基を有するモノマーに由来する構成単位の含有量は特に限定されないが、好ましい下限が0.1重量%、好ましい上限が5重量%である。
また、上記架橋性官能基を有するモノマーとして上記カルボキシル基を有するモノマーを用いる場合、片面粘着テープの強アルカリ性溶液への耐性が更に高くなることから、上記カルボキシル基を有するモノマーに由来する構成単位の含有量のより好ましい上限は3重量%、更に好ましい上限は0.5重量%である。
The content of the structural unit derived from the monomer having a crosslinkable functional group in the acrylic polymer for the pressure-sensitive adhesive layer is not particularly limited, but the preferred lower limit is 0.1% by weight and the preferred upper limit is 5% by weight. .
Further, when a monomer having a carboxyl group is used as the monomer having a crosslinkable functional group, the resistance of the single-sided adhesive tape to a strong alkaline solution is further increased. A more preferable upper limit of the content is 3% by weight, and a further preferable upper limit is 0.5% by weight.
上記感圧粘着剤層用アクリル系ポリマーは、炭素数が8以上のアルキル基を有する(メタ)アクリレートに由来する構成単位を有することが好ましい。このような構成単位を有することで、上記感圧粘着剤層用アクリル系ポリマーの疎水性が上がり、分子鎖内への強アルカリ性溶液の浸入がより抑えられるため、片面粘着テープの強アルカリ性溶液への耐性が更に高くなる。 The acrylic polymer for the pressure-sensitive adhesive layer preferably has a structural unit derived from (meth)acrylate having an alkyl group with 8 or more carbon atoms. By having such a structural unit, the hydrophobicity of the acrylic polymer for the pressure-sensitive adhesive layer is increased, and the infiltration of a strong alkaline solution into the molecular chain is further suppressed. is more resistant to
上記炭素数が8以上のアルキル基を有する(メタ)アクリレートとしては、n-オクチル(メタ)アクリレート、イソオクチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、n-ノニル(メタ)アクリレート、イソノニル(メタ)アクリレート、デシル(メタ)アクリレート、ラウリル(メタ)アクリレート、ステアリル(メタ)アクリレート、イソステアリル(メタ)アクリレート、イソボルニル(メタ)アクリレート等が挙げられる。これらの炭素数が8以上のアルキル基を有する(メタ)アクリレートは、単独で用いてもよく、2種以上を併用してもよい。なかでも、上記感圧粘着剤層が硬くなりすぎず、充分なタック性を維持できることから、2-エチルヘキシルアクリレート、ラウリルアクリレート、ラウリルメタクリレートを用いることが好ましい。 Examples of the (meth)acrylate having an alkyl group having 8 or more carbon atoms include n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl ( meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, isobornyl (meth)acrylate and the like. These (meth)acrylates having an alkyl group with 8 or more carbon atoms may be used alone or in combination of two or more. Among them, 2-ethylhexyl acrylate, lauryl acrylate, and lauryl methacrylate are preferably used because the pressure-sensitive adhesive layer does not become too hard and sufficient tackiness can be maintained.
上記感圧粘着剤層用アクリル系ポリマーにおける上記炭素数が8以上のアルキル基を有する(メタ)アクリレートに由来する構成単位の含有量は特に限定されないが、好ましい下限が15重量%、好ましい上限が99重量%である。上記炭素数が8以上のアルキル基を有する(メタ)アクリレートの含有量が上記範囲内であれば、上記感圧粘着剤層用アクリル系ポリマーの疎水性が上がり、分子鎖内への強アルカリ性溶液の浸入がより抑えられるため、片面粘着テープの強アルカリ性溶液への耐性が更に高くなる。上記炭素数が8以上のアルキル基を有する(メタ)アクリレートに由来する構成単位の含有量のより好ましい下限は20重量%、より好ましい上限は30重量%である。 The content of the structural unit derived from the (meth)acrylate having an alkyl group having 8 or more carbon atoms in the acrylic polymer for the pressure-sensitive adhesive layer is not particularly limited, but the preferred lower limit is 15% by weight, and the preferred upper limit is 99% by weight. When the content of the (meth)acrylate having an alkyl group having 8 or more carbon atoms is within the above range, the hydrophobicity of the acrylic polymer for the pressure-sensitive adhesive layer is increased, and a strong alkaline solution enters the molecular chain. is further suppressed, the resistance of the single-sided adhesive tape to strong alkaline solutions is further increased. A more preferable lower limit to the content of the structural unit derived from the (meth)acrylate having an alkyl group having 8 or more carbon atoms is 20% by weight, and a more preferable upper limit is 30% by weight.
上記感圧粘着剤層用アクリル系ポリマーは、本発明の効果を阻害しない範囲で、更に、他のモノマーに由来する構成単位を有していてもよい。上記他のモノマーとして、例えば、メチル(メタ)アクリレート、エチル(メタ)アクリレート、プロピル(メタ)アクリレート、ブチル(メタ)アクリレート、ベンジル(メタ)アクリレート、フェノキシエチル(メタ)アクリレート、エチルカルビトール(メタ)アクリレート、酢酸ビニル、フッ素含有(メタ)アクリレート等が挙げられる。
また、上記感圧粘着剤層用アクリル系ポリマーを紫外線重合法により調製する場合には、更に、ジビニルベンゼン、トリメチロールプロパントリ(メタ)アクリレート等の多官能モノマーに由来する構成単位を有することが好ましい。
The above acrylic polymer for the pressure-sensitive adhesive layer may further have structural units derived from other monomers to the extent that the effects of the present invention are not impaired. Examples of the above other monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, ethyl carbitol (meth) ) acrylate, vinyl acetate, fluorine-containing (meth)acrylate, and the like.
When the acrylic polymer for the pressure-sensitive adhesive layer is prepared by an ultraviolet polymerization method, it may further contain structural units derived from polyfunctional monomers such as divinylbenzene and trimethylolpropane tri(meth)acrylate. preferable.
上記感圧粘着剤層用アクリル系ポリマーの溶解度パラメーター(SP値)は特に限定されず、上記感熱粘着剤層用アクリル系ポリマーの溶解度パラメーター(SP値)と同様の溶解度パラメーター(SP値)であってよい。 The solubility parameter (SP value) of the acrylic polymer for the pressure-sensitive adhesive layer is not particularly limited, and is the same as the solubility parameter (SP value) of the acrylic polymer for the heat-sensitive adhesive layer. you can
上記感圧粘着剤層用アクリル系ポリマーの重量平均分子量(Mw)は特に限定されず、上記感熱粘着剤層用アクリル系ポリマーの重量平均分子量(Mw)と同様の重量平均分子量(Mw)であってよい。 The weight-average molecular weight (Mw) of the acrylic polymer for the pressure-sensitive adhesive layer is not particularly limited, and may be the same weight-average molecular weight (Mw) as the weight-average molecular weight (Mw) of the acrylic polymer for the heat-sensitive adhesive layer. you can
上記感圧粘着剤層用アクリル系ポリマーを調製する方法は特に限定されず、上記感熱粘着剤層用アクリル系ポリマーの場合と同様に、例えば、上記構成単位の由来となるモノマーを、重合開始剤の存在下にてラジカル反応させる方法等が挙げられる。 The method for preparing the acrylic polymer for the pressure-sensitive adhesive layer is not particularly limited, and in the same manner as in the case of the acrylic polymer for the heat-sensitive adhesive layer, for example, a monomer from which the structural unit is derived may be added as a polymerization initiator. and a method of radical reaction in the presence of.
上記感圧粘着剤層は、更に、粘着付与樹脂を含有することが好ましい。
上記感圧粘着剤層が上記粘着付与樹脂を含有することにより、上記感圧粘着剤層の粘着力が向上する。上記粘着付与樹脂は特に限定されず、上記感熱粘着剤層に用いられる粘着付与樹脂と同様の粘着付与樹脂を用いることができる。
上記粘着付与樹脂の含有量は特に限定されないが、上記感圧粘着剤層用アクリル系ポリマー100重量部に対する好ましい下限は3重量部、好ましい上限は50重量部であり、より好ましい下限は10重量部、より好ましい上限は35重量部である。上記粘着付与樹脂の含有量が上記範囲内であれば、上記感圧粘着剤層の粘着力が向上する。
The pressure-sensitive adhesive layer preferably further contains a tackifying resin.
By containing the tackifying resin in the pressure-sensitive adhesive layer, the adhesive strength of the pressure-sensitive adhesive layer is improved. The tackifying resin is not particularly limited, and the same tackifying resin as that used in the heat-sensitive adhesive layer can be used.
The content of the tackifying resin is not particularly limited, but the preferred lower limit is 3 parts by weight, the preferred upper limit is 50 parts by weight, and the more preferred lower limit is 10 parts by weight, relative to 100 parts by weight of the acrylic polymer for the pressure-sensitive adhesive layer. , and a more preferred upper limit is 35 parts by weight. When the content of the tackifier resin is within the above range, the adhesive strength of the pressure-sensitive adhesive layer is improved.
上記感圧粘着剤層は、シランカップリング剤を含有してもよい。
上記シランカップリング剤は特に限定されず、上記感熱粘着剤層に用いられるシランカップリング剤と同様のシランカップリング剤を用いることができる。上記シランカップリング剤の含有量も特に限定されず、上記感熱粘着剤層における含有量と同様の含有量を採用することができる。
The pressure-sensitive adhesive layer may contain a silane coupling agent.
The silane coupling agent is not particularly limited, and the same silane coupling agent as the silane coupling agent used in the heat-sensitive adhesive layer can be used. The content of the silane coupling agent is also not particularly limited, and the same content as the content in the heat-sensitive adhesive layer can be employed.
上記感圧粘着剤層は、更に、架橋剤を含有してもよい。
上記感圧粘着剤層が上記架橋剤を含有することで、上記感圧粘着剤層用アクリル系ポリマーが上記架橋性官能基を有するモノマーに由来する構成単位を含有する場合に上記感圧粘着剤層用アクリル系ポリマー間を架橋させることができる。
上記架橋剤は特に限定されず、上記感熱粘着剤層に用いられる架橋剤と同様の架橋剤を用いることができ、エポキシ系架橋剤がより好ましい。上記架橋剤の含有量も特に限定されず、上記感熱粘着剤層における含有量と同様の含有量を採用することができる。
The pressure-sensitive adhesive layer may further contain a cross-linking agent.
When the pressure-sensitive adhesive layer contains the cross-linking agent, and the acrylic polymer for the pressure-sensitive adhesive layer contains a structural unit derived from the monomer having the crosslinkable functional group, the pressure-sensitive adhesive Cross-linking can be performed between the layer acrylic polymers.
The cross-linking agent is not particularly limited, and the same cross-linking agent as that used in the heat-sensitive adhesive layer can be used, and an epoxy-based cross-linking agent is more preferable. The content of the cross-linking agent is also not particularly limited, and the same content as the content in the heat-sensitive adhesive layer can be adopted.
上記感圧粘着剤層は、必要に応じて、可塑剤、乳化剤、軟化剤、充填剤、顔料、染料等の添加剤、その他の樹脂等を含有していてもよい。  The pressure-sensitive adhesive layer may contain additives such as plasticizers, emulsifiers, softeners, fillers, pigments and dyes, and other resins, if necessary. 
上記感圧粘着剤層のゲル分率は特に限定されず、上記感熱粘着剤層と同様であってよく、50重量%以上が好ましい。
上記感圧粘着剤層の厚みは特に限定されないが、好ましい下限は0.1μm、好ましい上限は30μmである。上記感圧粘着剤層の厚みが上記範囲内であれば、上記基材と上記感熱粘着剤層との間のアンカー性がより向上する。上記感圧粘着剤層の厚みのより好ましい下限は5μm、より好ましい上限は20μmである。
The gel fraction of the pressure-sensitive adhesive layer is not particularly limited, and may be the same as that of the heat-sensitive adhesive layer, preferably 50% by weight or more.
The thickness of the pressure-sensitive adhesive layer is not particularly limited, but the preferred lower limit is 0.1 μm and the preferred upper limit is 30 μm. When the thickness of the pressure-sensitive adhesive layer is within the above range, the anchoring property between the substrate and the heat-sensitive adhesive layer is further improved. A more preferable lower limit of the thickness of the pressure-sensitive adhesive layer is 5 μm, and a more preferable upper limit thereof is 20 μm.
以上、本発明の一態様として、基材と、上記基材の一方の面に積層された感熱粘着剤層とを有し、上記基材が、少なくとも上記感熱粘着剤層とは反対側の表面に、金属層を有する片面粘着テープについて説明したが、上記基材、上記感熱粘着剤層及び上記金属層の関係に代えて上記感熱粘着剤層及び上記金属層の関係に基づけば、本発明において、片面粘着テープは、上記感熱粘着剤層とは反対側の表面に、上記基材を構成する部材としての上記金属層が配置されているものであればよいと言える。すなわち、本発明の別態様として、一方の面に金属層を有し、他方の面に感熱粘着剤層を有する片面粘着テープであって、上記感熱粘着剤層は、SUSに対する静止摩擦係数が5以下である、片面粘着テープが挙げられる。このような別態様であっても、厚みが薄い被着体に貼り付ける際にもシワを生じにくく、かつ、強アルカリ性溶液への耐性に優れた片面粘着テープを実現することができる。 As described above, as one aspect of the present invention, a base material and a heat-sensitive adhesive layer laminated on one surface of the base material are provided, and the base material has at least the surface opposite to the heat-sensitive adhesive layer. , a single-sided pressure-sensitive adhesive tape having a metal layer was described, but based on the relationship between the heat-sensitive adhesive layer and the metal layer instead of the relationship between the substrate, the heat-sensitive adhesive layer, and the metal layer, in the present invention, It can be said that the single-sided pressure-sensitive adhesive tape may have the above-mentioned metal layer as a member constituting the above-mentioned base material disposed on the surface opposite to the above-mentioned heat-sensitive adhesive layer. That is, as another aspect of the present invention, there is provided a single-sided adhesive tape having a metal layer on one side and a heat-sensitive adhesive layer on the other side, wherein the heat-sensitive adhesive layer has a static friction coefficient of 5 against SUS. The following are single-sided adhesive tapes. Even in such a different embodiment, it is possible to realize a single-sided pressure-sensitive adhesive tape that is less likely to wrinkle when attached to a thin adherend and has excellent resistance to strong alkaline solutions.
本発明の片面粘着テープを製造する方法は特に限定されず、例えば、アクリル系ポリマー、粘着付与樹脂、シランカップリング剤、架橋剤等を配合して粘着剤溶液を調製し、この粘着剤溶液を離型処理したPETフィルム上に塗工した後、乾燥させて感熱粘着剤層を形成させ、この感熱粘着剤層を基材に転着させる方法等が挙げられる。 The method for producing the single-sided pressure-sensitive adhesive tape of the present invention is not particularly limited. After coating on a release-treated PET film, it is dried to form a heat-sensitive adhesive layer, and the heat-sensitive adhesive layer is transferred to a base material.
本発明の片面粘着テープの用途は特に限定されないが、厚みが薄い被着体に貼り付ける際にもシワを生じにくく、かつ、強アルカリ性溶液への耐性に優れることから、プリント配線基板を製造する際に好適に用いることができる。なかでも、本発明の片面粘着テープは、エッチング工程、デスミア工程、又は、無電解メッキ工程において、金属張積層板の端部に貼り付けて金属張積層板の端部を保護するために特に好適に用いることができる。
より具体的には、本発明の片面粘着テープは、金属張積層板、なかでも厚みが薄い(具体的には、厚みが100μm以下、好ましくは20~50μm付近、なかでも30~40μm付近の)金属張積層板の端部に貼り付けて金属張積層板の端部を保護するために用いることができる。
なお、工程終了後には、金属張積層板における片面粘着テープで保護された領域をトリミングすることで、片面粘着テープで保護された領域を分離する(取り除く)ことができる。
The use of the single-sided adhesive tape of the present invention is not particularly limited, but it is less likely to wrinkle when attached to a thin adherend and has excellent resistance to strong alkaline solutions. It can be preferably used in some cases. Among them, the single-sided pressure-sensitive adhesive tape of the present invention is particularly suitable for attaching to the edge of the metal-clad laminate to protect the edge of the metal-clad laminate in the etching process, the desmear process, or the electroless plating process. can be used for
More specifically, the single-sided adhesive tape of the present invention is a metal-clad laminate, especially a thin one (specifically, a thickness of 100 μm or less, preferably around 20 to 50 μm, especially around 30 to 40 μm). It can be used to protect the edge of the metal-clad laminate by attaching it to the edge of the metal-clad laminate.
After completion of the process, the region protected by the single-sided adhesive tape can be separated (removed) by trimming the region of the metal-clad laminate protected by the single-sided adhesive tape.
本発明の片面粘着テープを金属張積層板の端部に貼り付けて金属張積層板の端部を保護する方法は特に限定されず、例えば、プレス機を用いて片面粘着テープを金属張積層板の端部に加熱圧着する方法等が挙げられる。加熱圧着時の条件としては、例えば、温度80~120℃、圧力0.1~5MPa、時間30~300秒間を用いることができる。なお、金属張積層板の四角に片面粘着テープを貼り付ける場合には、片面粘着テープを重複して貼り付けてもよく、重複しないように貼り付けてもよい。 The method of protecting the edges of the metal-clad laminate by attaching the single-sided adhesive tape of the present invention to the edges of the metal-clad laminate is not particularly limited. and a method of thermocompression bonding to the end of the . As conditions for thermocompression bonding, for example, a temperature of 80 to 120° C., a pressure of 0.1 to 5 MPa, and a time of 30 to 300 seconds can be used. When the single-sided adhesive tapes are attached to the squares of the metal-clad laminate, the single-sided adhesive tapes may be attached overlappingly or may be attached so as not to overlap.
図1~8に、本発明の片面粘着テープを用いて金属張積層板の端部を保護した状態の一例を模式的に示す断面図を示す。
図1~4に示す端部保護された金属張積層板1においては、基材31及び感熱粘着剤層32を有する片面粘着テープ30が使用されている。図1~4においては、金属張積層板2の表面から裏面にまでまたがるように片面粘着テープ30を折り返して(折り曲げて)金属張積層板2の端部に貼り付けている。更に、図4においては、金属張積層板2の裏面の全体が片面粘着テープ30で覆われている。
図5~7に示す端部保護された金属張積層板1においては、基材31及び感熱粘着剤層32を有する片面粘着テープ30と、基材31’及び感熱粘着剤層32’を有する片面粘着テープ30’とが使用されている。
図8に示す端部保護された金属張積層板1においては、基材31及び感熱粘着剤層32を有する片面粘着テープ30と、基材31’及び感熱粘着剤層32’を有する片面粘着テープ30’と、基材31’’及び感熱粘着剤層32’’を有する片面粘着テープ30’’とが使用されている。
1 to 8 are cross-sectional views schematically showing an example of a state in which the edge of a metal-clad laminate is protected using the single-sided pressure-sensitive adhesive tape of the present invention.
In the edge-protected metal-clad laminate 1 shown in FIGS. 1-4, a single-sided adhesive tape 30 having a substrate 31 and a heat-sensitive adhesive layer 32 is used. 1 to 4, the single-sided adhesive tape 30 is folded back (bent) and attached to the end portion of the metal-clad laminate 2 so as to extend from the front surface to the back surface of the metal-clad laminate 2. In FIGS. Furthermore, in FIG. 4 , the entire back surface of the metal-clad laminate 2 is covered with a single-sided adhesive tape 30 .
In the edge-protected metal-clad laminate 1 shown in FIGS. Adhesive tape 30' is used.
In the edge-protected metal-clad laminate 1 shown in FIG. 30' and a single-sided adhesive tape 30'' having a substrate 31'' and a heat-sensitive adhesive layer 32'' are used.
なお、図2~8において、3aは感熱粘着剤層同士の界面を示しており、この界面3aにできるだけ隙間を生じさせないことにより、金属張積層板2の端部の破損をより抑制することができ、強アルカリ性溶液に晒された場合にも該溶液の端部への浸入をより抑制することができる。 In FIGS. 2 to 8, 3a indicates the interface between the heat-sensitive adhesive layers, and by minimizing the gap at this interface 3a, damage to the edges of the metal-clad laminate 2 can be further suppressed. It is possible to further suppress the infiltration of the solution into the end portion even when exposed to a strong alkaline solution.
本発明によれば、厚みが薄い被着体に貼り付ける際にもシワを生じにくく、かつ、強アルカリ性溶液への耐性に優れた片面粘着テープを提供することができる。 According to the present invention, it is possible to provide a single-sided pressure-sensitive adhesive tape that is less likely to wrinkle when attached to a thin adherend and has excellent resistance to strong alkaline solutions.
本発明の片面粘着テープを用いて金属張積層板の端部を保護した状態の一例を模式的に示す断面図である。BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view schematically showing an example of a state in which the edge of a metal-clad laminate is protected using the single-sided pressure-sensitive adhesive tape of the present invention; 本発明の片面粘着テープを用いて金属張積層板の端部を保護した状態の一例を模式的に示す断面図である。BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view schematically showing an example of a state in which the edge of a metal-clad laminate is protected using the single-sided pressure-sensitive adhesive tape of the present invention; 本発明の片面粘着テープを用いて金属張積層板の端部を保護した状態の一例を模式的に示す断面図である。BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view schematically showing an example of a state in which the edge of a metal-clad laminate is protected using the single-sided pressure-sensitive adhesive tape of the present invention; 本発明の片面粘着テープを用いて金属張積層板の端部を保護した状態の一例を模式的に示す断面図である。BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view schematically showing an example of a state in which the edge of a metal-clad laminate is protected using the single-sided pressure-sensitive adhesive tape of the present invention; 本発明の片面粘着テープを用いて金属張積層板の端部を保護した状態の一例を模式的に示す断面図である。BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view schematically showing an example of a state in which the edge of a metal-clad laminate is protected using the single-sided pressure-sensitive adhesive tape of the present invention; 本発明の片面粘着テープを用いて金属張積層板の端部を保護した状態の一例を模式的に示す断面図である。BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view schematically showing an example of a state in which the edge of a metal-clad laminate is protected using the single-sided pressure-sensitive adhesive tape of the present invention; 本発明の片面粘着テープを用いて金属張積層板の端部を保護した状態の一例を模式的に示す断面図である。BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view schematically showing an example of a state in which the edge of a metal-clad laminate is protected using the single-sided pressure-sensitive adhesive tape of the present invention; 本発明の片面粘着テープを用いて金属張積層板の端部を保護した状態の一例を模式的に示す断面図である。BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view schematically showing an example of a state in which the edge of a metal-clad laminate is protected using the single-sided pressure-sensitive adhesive tape of the present invention;
以下に実施例を掲げて本発明の態様を更に詳しく説明するが、本発明はこれら実施例のみに限定されない。 EXAMPLES The aspects of the present invention will be described in more detail with reference to Examples below, but the present invention is not limited only to these Examples.
実施例及び比較例において使用した粘着付与樹脂を以下に示す。
・水添ロジンエステル樹脂(荒川化学工業社製、KE-359、軟化点100℃、水酸基価42mgKOH/g)
・水添ロジンエステル樹脂(荒川化学工業社製、KE-311、軟化点100℃、水酸基価8mgKOH/g)
・水添ロジンエステル樹脂(荒川化学工業社製、エステルガムH、軟化点68℃、水酸基価29mgKOH/g)
・不均化ロジンエステル樹脂(荒川化学工業社製、KE-100、軟化点100℃、水酸基価6mgKOH/g)
・不均化ロジンエステル樹脂(荒川化学工業社製、A-100、軟化点100℃、水酸基価16mgKOH/g)
・重合ロジンエステル樹脂(荒川化学工業社製、D-135、軟化点135℃、水酸基価45mgKOH/g)
The tackifying resins used in Examples and Comparative Examples are shown below.
・ Hydrogenated rosin ester resin (manufactured by Arakawa Chemical Industries, Ltd., KE-359, softening point 100 ° C., hydroxyl value 42 mg KOH / g)
・Hydrogenated rosin ester resin (manufactured by Arakawa Chemical Industries, Ltd., KE-311, softening point 100 ° C., hydroxyl value 8 mg KOH / g)
・Hydrogenated rosin ester resin (manufactured by Arakawa Chemical Industries, Ltd., ester gum H, softening point 68° C., hydroxyl value 29 mgKOH/g)
・ Disproportionated rosin ester resin (manufactured by Arakawa Chemical Industries, Ltd., KE-100, softening point 100 ° C., hydroxyl value 6 mg KOH / g)
・ Disproportionated rosin ester resin (manufactured by Arakawa Chemical Industries, Ltd., A-100, softening point 100 ° C., hydroxyl value 16 mg KOH / g)
・ Polymerized rosin ester resin (manufactured by Arakawa Chemical Industries, Ltd., D-135, softening point 135 ° C., hydroxyl value 45 mg KOH / g)
(実施例1)
(1)アクリル系ポリマーの調製
反応容器内に、重合溶媒として酢酸エチルを加え、窒素でバブリングした後、窒素を流入しながら反応容器を加熱して還流を開始した。続いて、重合開始剤としてアゾビスイソブチロニトリル0.3重量部を酢酸エチルで10倍希釈した重合開始剤溶液を反応容器内に投入し、表1に示す組成のモノマーの合計100重量部を2時間かけて滴下添加した。滴下終了後、重合開始剤としてアゾビスイソブチロニトリル0.3重量部を酢酸エチルで10倍希釈した重合開始剤溶液を反応容器内に再度投入し、4時間重合反応を行い、アクリル系ポリマー含有溶液を得た。
得られたアクリル系ポリマーについて、溶解度パラメーター(SP値)を求めた。また、得られたアクリル系ポリマーについて、カラムとしてGPC LF-804(昭和電工社製)を用いたゲルパーミエーションクロマトグラフ法により、ポリスチレン換算での重量平均分子量(Mw)を求めた。
(Example 1)
(1) Preparation of acrylic polymer Ethyl acetate was added as a polymerization solvent into a reaction vessel, and nitrogen was bubbled through the reaction vessel. Subsequently, a polymerization initiator solution obtained by diluting 0.3 parts by weight of azobisisobutyronitrile 10 times with ethyl acetate as a polymerization initiator was charged into the reaction vessel, and a total of 100 parts by weight of monomers having the composition shown in Table 1 was added. was added dropwise over 2 hours. After the completion of dropping, a polymerization initiator solution obtained by diluting 0.3 parts by weight of azobisisobutyronitrile 10 times with ethyl acetate as a polymerization initiator was put into the reaction vessel again, and the polymerization reaction was performed for 4 hours to obtain an acrylic polymer. A containing solution was obtained.
A solubility parameter (SP value) was determined for the obtained acrylic polymer. Further, the weight average molecular weight (Mw) in terms of polystyrene was determined for the obtained acrylic polymer by gel permeation chromatography using GPC LF-804 (manufactured by Showa Denko KK) as a column.
(2)片面粘着テープの製造
得られたアクリル系ポリマー含有溶液に、アクリル系ポリマー100重量部に対してシランカップリング剤(信越化学工業社製、KBM803)を1重量部、架橋剤(エポキシ系架橋剤、三菱ガス化学社製、テトラッドC)を0.3重量部(固体成分比率)加え、粘着剤溶液を調製した。
得られた粘着剤溶液を厚み75μmの離型処理したPETフィルム(東洋クロス社製、SP3000-75)上に、乾燥後の感熱粘着剤層の厚みが表1に示す厚みとなるように塗工した後、110℃で5分間乾燥させて感熱粘着剤層を形成させた。この感熱粘着剤層を基材としての電解銅箔(厚み18μm、福田金属箔紛工業社製)に100℃条件下で転着させ、40℃で48時間養生し、基材、感熱粘着剤層、離型処理したPETフィルムがこの順に積層された片面粘着テープを得た。
(2) Production of Single-Sided Adhesive Tape To the obtained acrylic polymer-containing solution, 1 part by weight of a silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBM803) per 100 parts by weight of the acrylic polymer, a cross-linking agent (epoxy-based A cross-linking agent, Tetrad C, manufactured by Mitsubishi Gas Chemical Co., Ltd., was added in an amount of 0.3 parts by weight (solid component ratio) to prepare an adhesive solution.
The obtained adhesive solution was coated on a release-treated PET film (manufactured by Toyo Cloth Co., Ltd., SP3000-75) with a thickness of 75 μm so that the thickness of the heat-sensitive adhesive layer after drying would be the thickness shown in Table 1. After that, it was dried at 110° C. for 5 minutes to form a heat-sensitive adhesive layer. This heat-sensitive adhesive layer was transferred to an electrolytic copper foil (thickness 18 μm, manufactured by Fukuda Metal Foil Powder Industry Co., Ltd.) as a base material at 100 ° C. and cured at 40 ° C. for 48 hours. , and the release-treated PET film were laminated in this order to obtain a single-sided adhesive tape.
(3)ゲル分率の測定
片面粘着テープから感熱粘着剤層(粘着剤組成物)のみを0.1g取り出し、酢酸エチル50mL中に浸漬し、振とう機で温度23度、200rpmの条件で24時間振とうした。振とう後、金属メッシュ(目開き#200メッシュ)を用いて、酢酸エチルと酢酸エチルを吸収し膨潤した粘着剤組成物を分離した。分離後の粘着剤組成物を110℃の条件下で1時間乾燥させた。乾燥後の金属メッシュを含む粘着剤組成物の重量を測定し、下記式を用いてゲル分率を算出した。
ゲル分率(重量%)=100×(W-W)/W
(W:初期粘着剤組成物重量、W:乾燥後の金属メッシュを含む粘着剤組成物重量、W:金属メッシュの初期重量)
(3) Measurement of gel fraction 0.1 g of only the heat-sensitive adhesive layer (adhesive composition) was taken out from the single-sided adhesive tape, immersed in 50 mL of ethyl acetate, and shaken at 23°C and 200 rpm for 24 hours. Time was shaken. After shaking, ethyl acetate and the adhesive composition swollen by absorbing ethyl acetate were separated using a metal mesh (#200 mesh opening). The adhesive composition after separation was dried at 110° C. for 1 hour. The weight of the pressure-sensitive adhesive composition containing the metal mesh after drying was measured, and the gel fraction was calculated using the following formula.
Gel fraction (% by weight) = 100 x (W 1 - W 2 )/W 0
(W 0 : initial weight of adhesive composition, W 1 : weight of adhesive composition containing metal mesh after drying, W 2 : initial weight of metal mesh)
(4)貯蔵弾性率G’及び損失正接のピーク温度の測定
実施例と同様の方法で10mm×6mm、厚さ1mmの感熱粘着剤層のみからなる測定サンプルを作製した。
得られた測定サンプルについて、動的粘弾性測定装置(アイティー計測制御社製、DVA-200)を用いて、動的粘弾性測定のせん断モード、角周波数1Hz、速度5℃/minの条件で-40℃から140℃まで動的粘弾性測定を行い、23℃及び100℃における貯蔵弾性率G’を測定した。更に、動的粘弾性測定装置(アイティー計測制御社製、DVA-200)を用い、低速昇温せん断変形モードの5℃/分、1Hzの条件で、-40℃~140℃の動的粘弾性スペクトルを測定することで損失正接のピーク温度を測定した。
(4) Measurement of Storage Modulus G' and Peak Temperature of Loss Tangent A measurement sample consisting of only a heat-sensitive adhesive layer of 10 mm×6 mm and 1 mm in thickness was prepared in the same manner as in the Examples.
The resulting measurement sample was measured using a dynamic viscoelasticity measuring device (DVA-200, manufactured by IT Keisoku Co., Ltd.) under the conditions of shear mode for dynamic viscoelasticity measurement, angular frequency of 1 Hz, and speed of 5 ° C./min. Dynamic viscoelasticity measurement was performed from -40°C to 140°C, and the storage elastic modulus G' at 23°C and 100°C was measured. Furthermore, using a dynamic viscoelasticity measuring device (DVA-200, manufactured by IT Keisoku Co., Ltd.), the dynamic viscosity of -40 ° C to 140 ° C under the conditions of 5 ° C / min and 1 Hz in the slow heating shear deformation mode. The peak temperature of the loss tangent was measured by measuring the elastic spectrum.
(5)静止摩擦係数の測定
滑り片としてSUS304(サイズ63mm×63mm、重さ200g、ユタカパネルサービス製)を用い、引張速度100mm/minの条件でJIS K7125に準拠して、常温(23℃)、湿度50%にて片面粘着テープの静止摩擦係数を測定した。なお、測定の際の試料の相手材としては、滑り片同様にSUS304(サイズ250mm×150mm×厚み1.5mm、ユタカパネルサービス製)を用いた。
(5) Measurement of static friction coefficient SUS304 (size 63 mm x 63 mm, weight 200 g, manufactured by Yutaka Panel Service) was used as a sliding piece, and tensile speed was 100 mm / min in accordance with JIS K7125. , and a humidity of 50%. SUS304 (size 250 mm×150 mm×thickness 1.5 mm, manufactured by Yutaka Panel Service Co., Ltd.) was used as the mating material of the sample in the measurement, like the sliding piece.
(6)表面粗さRaの測定
片面粘着テープの感熱粘着剤層について、JIS B 0601-2001に規定される算術平均粗さを測定し、表面粗さRaとした。
(6) Measurement of Surface Roughness Ra With respect to the heat-sensitive adhesive layer of the single-sided adhesive tape, the arithmetic mean roughness specified in JIS B 0601-2001 was measured to obtain the surface roughness Ra.
(実施例2~3、比較例1)
表に示すように変更したこと以外は実施例1と同様にして、片面粘着テープを得た。
(Examples 2-3, Comparative Example 1)
A single-sided adhesive tape was obtained in the same manner as in Example 1, except for the changes shown in the table.
(実施例4)
(1)アクリル系ポリマーの調製
実施例1と同様にして、感熱粘着剤層に用いるアクリル系ポリマー(感熱粘着剤層用アクリル系ポリマー)の含有溶液と、感圧粘着剤層に用いるアクリル系ポリマー(感圧粘着剤層用アクリル系ポリマー)の含有溶液とをそれぞれ調製した。
(Example 4)
(1) Preparation of acrylic polymer In the same manner as in Example 1, a solution containing the acrylic polymer used for the heat-sensitive adhesive layer (acrylic polymer for the heat-sensitive adhesive layer) and the acrylic polymer used for the pressure-sensitive adhesive layer were prepared. (acrylic polymer for pressure-sensitive adhesive layer) was prepared.
(2)片面粘着テープの製造
得られた感熱粘着剤層用アクリル系ポリマー含有溶液に、アクリル系ポリマー100重量部に対して水添ロジンエステル樹脂(荒川化学工業社製、KE-359、軟化点100℃、水酸基価42mgKOH/g)を30重量部加えた。更に、シランカップリング剤(信越化学工業社製、KBM803)を1重量部、架橋剤(エポキシ系架橋剤、三菱ガス化学社製、テトラッドC)を0.3重量部(固体成分比率)加え、感熱粘着剤層用粘着剤溶液を調製した。
また、得られた感圧粘着剤層用アクリル系ポリマー含有溶液に、アクリル系ポリマー100重量部に対して重合ロジンエステル樹脂(荒川化学工業社製、D-135、軟化点135℃、水酸基価45mgKOH/g)を15重量部加えた。更に、架橋剤(エポキシ系架橋剤、三菱ガス化学社製、テトラッドC)を0.15重量部(固体成分比率)加え、感圧粘着剤層用粘着剤溶液を調製した。
(2) Production of Single-sided Adhesive Tape Into the obtained acrylic polymer-containing solution for the heat-sensitive adhesive layer, hydrogenated rosin ester resin (KE-359, manufactured by Arakawa Chemical Industries, Ltd., softening point 100° C., hydroxyl value 42 mgKOH/g) was added in 30 parts by weight. Furthermore, 1 part by weight of a silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBM803) and 0.3 parts by weight (solid component ratio) of a cross-linking agent (epoxy cross-linking agent, manufactured by Mitsubishi Gas Chemical Co., Ltd., Tetrad C) are added, An adhesive solution for a heat-sensitive adhesive layer was prepared.
In addition, a polymerized rosin ester resin (manufactured by Arakawa Chemical Industries, Ltd., D-135, softening point 135° C., hydroxyl value 45 mg KOH /g) was added in an amount of 15 parts by weight. Further, 0.15 parts by weight (solid component ratio) of a cross-linking agent (epoxy-based cross-linking agent, Tetrad C, manufactured by Mitsubishi Gas Chemical Co., Ltd.) was added to prepare an adhesive solution for a pressure-sensitive adhesive layer.
得られた感圧粘着剤層用粘着剤溶液を厚み75μmの離型処理したPETフィルム(東洋クロス社製、SP3000-75)上に、乾燥後の感圧粘着剤層の厚みが表1に示す厚みとなるように塗工した後、110℃で5分間乾燥させて感圧粘着剤層を形成させた。この感圧粘着剤層を基材としての電解銅箔(厚み18μm、福田金属箔紛工業社製)に転着させ、離型処理したPETフィルムを剥離した。その後、感熱粘着剤層用粘着剤溶液を厚み75μmの離型処理したPETフィルム(東洋クロス社製、SP3000-75)上に、乾燥後の感熱粘着剤層の厚みが表1に示す厚みとなるように塗工した後、110℃で5分間乾燥させて感熱粘着剤層を形成させた。この感熱粘着剤層を感圧粘着剤層に23℃条件下で転着させ、40℃で48時間養生し、基材、感圧粘着剤層、感熱粘着剤層、離型処理したPETフィルムがこの順に積層された片面粘着テープを得た。 Table 1 shows the thickness of the pressure-sensitive adhesive layer after drying on a release-treated PET film (manufactured by Toyo Cloth Co., Ltd., SP3000-75) of the obtained pressure-sensitive adhesive layer adhesive solution. After coating so as to have a thickness, it was dried at 110° C. for 5 minutes to form a pressure-sensitive adhesive layer. This pressure-sensitive adhesive layer was transferred to an electrolytic copper foil (thickness: 18 μm, manufactured by Fukuda Metal Foil Powder Co., Ltd.) as a base material, and the release-treated PET film was peeled off. Then, the adhesive solution for the heat-sensitive adhesive layer is applied onto a 75 μm-thick release-treated PET film (manufactured by Toyo Cloth Co., Ltd., SP3000-75), and the thickness of the heat-sensitive adhesive layer after drying becomes the thickness shown in Table 1. and dried at 110° C. for 5 minutes to form a heat-sensitive adhesive layer. This heat-sensitive adhesive layer was transferred to the pressure-sensitive adhesive layer at 23° C. and cured at 40° C. for 48 hours to obtain the substrate, pressure-sensitive adhesive layer, heat-sensitive adhesive layer, and release-treated PET film. A single-sided adhesive tape laminated in this order was obtained.
(3)ゲル分率の測定
実施例1と同様にして測定を行った。
(3) Measurement of gel fraction Measurement was carried out in the same manner as in Example 1.
(4)貯蔵弾性率G’及び損失正接のピーク温度の測定
実施例1と同様にして測定を行った。
(4) Measurement of storage elastic modulus G' and loss tangent peak temperature Measurements were carried out in the same manner as in Example 1.
(5)静止摩擦係数の測定
実施例1と同様にして測定を行った。
(5) Measurement of Static Friction Coefficient Measurement was carried out in the same manner as in Example 1.
(6)表面粗さRaの測定
実施例1と同様にして測定を行った。
(6) Measurement of surface roughness Ra Measurement was performed in the same manner as in Example 1.
(実施例5~14、比較例2~3)
表に示すように変更したこと以外は実施例1と同様にして、片面粘着テープを得た。
なお、実施例5では、感熱粘着剤層用粘着剤溶液を塗工する離型処理したPETフィルムをPETフィルム(東洋クロス社製、タイプ10)に変更することにより、感熱粘着剤層の表面粗さRaを変更した。
(Examples 5-14, Comparative Examples 2-3)
A single-sided adhesive tape was obtained in the same manner as in Example 1, except for the changes shown in the table.
In Example 5, the PET film (manufactured by Toyo Cloth Co., Ltd., type 10) was used instead of the release-treated PET film on which the adhesive solution for the heat-sensitive adhesive layer was applied. Changed Ra.
<評価>
実施例及び比較例で得られた片面粘着テープについて以下の評価を行った。結果を表1~3に示した。
<Evaluation>
The single-sided pressure-sensitive adhesive tapes obtained in Examples and Comparative Examples were evaluated as follows. The results are shown in Tables 1-3.
(1)貼り付け時のシワの評価
得られた片面粘着テープを7mm×80mmに切断し、銅張積層板(CCL)(Panasonic社製、R1515E、樹脂層厚み40μm、銅箔厚み2μm)の端部に貼り付けた。
より詳細には、図1に示す被覆形態となるように片面粘着テープを貼り付けた。まず、銅張積層板の一辺の一方の面に、銅張積層板の端部から3.5mmの位置に片面粘着テープの長辺の端部がくるように片面粘着テープを置き、100℃条件下、圧力0.3MPaで30秒間、加熱圧着した。その後、貼り付けされていない片面粘着テープの基材面をステンレス板で押さえながら、銅張積層板のもう一方の面に向かって隙間が生じないように片面粘着テープを折り曲げ、銅張積層板のもう一方の面に接触させ、100℃条件下、圧力0.3MPaで30秒間、加熱圧着した。
貼り付けた片面粘着テープを目視で観察し、シワの発生を確認した。シワがなかった場合を○、シワがあった場合を×とした。
(1) Evaluation of wrinkles during application The obtained single-sided adhesive tape was cut into 7 mm × 80 mm, and the edge of a copper clad laminate (CCL) (manufactured by Panasonic, R1515E, resin layer thickness 40 μm, copper foil thickness 2 μm) pasted on the part.
More specifically, a single-sided pressure-sensitive adhesive tape was attached so as to form the covering form shown in FIG. First, a single-sided adhesive tape was placed on one side of one side of the copper-clad laminate so that the end of the long side of the single-sided adhesive tape was positioned 3.5 mm from the edge of the copper-clad laminate. It was heat-pressed for 30 seconds at a pressure of 0.3 MPa. After that, while pressing the base surface of the single-sided adhesive tape that is not attached with a stainless steel plate, the single-sided adhesive tape is bent toward the other side of the copper-clad laminate so as not to create a gap, and the copper-clad laminate is attached. It was brought into contact with the other surface and heat-pressed under the condition of 100° C. and the pressure of 0.3 MPa for 30 seconds.
The attached single-sided adhesive tape was visually observed to confirm the occurrence of wrinkles. The case where there was no wrinkle was evaluated as ◯, and the case where there was wrinkle was evaluated as X.
(2)強アルカリ性溶液への耐性の評価
上記「(1)貼り付け時のシワの評価」と同様にして、片面粘着テープを銅張積層板の端部に貼り付けて試験片を作製し、以下の評価を行った。なお、表4に無電解メッキの条件を、表5にデスミア処理の条件を示した。
(2) Evaluation of resistance to strong alkaline solution In the same manner as in "(1) Evaluation of wrinkles during application" above, a single-sided adhesive tape was attached to the end of the copper-clad laminate to prepare a test piece, The following evaluations were performed. Table 4 shows the conditions for electroless plating, and Table 5 shows the conditions for desmear treatment.
(2-1)強アルカリ性溶液
5重量%に調整した水酸化ナトリウム水溶液を50℃に加熱し、試験片を5分間浸漬した。試験片を取り出した後、銅張積層板から片面粘着テープを剥離した。銅張積層板の片面粘着テープを貼り付けていた部分の銅の変色を確認して強アルカリ性溶液への耐性を評価した。
銅の変色がみられなかった場合を◎、片面粘着テープを貼り付けていた部分の端部から2mm以内の範囲に銅の変色がみられた場合を〇、片面粘着テープを貼り付けていた部分の端部から2mmを超える範囲で銅の変色がみられた場合を×とした。
(2-1) Strong alkaline solution A sodium hydroxide aqueous solution adjusted to 5% by weight was heated to 50° C., and the test piece was immersed for 5 minutes. After taking out the test piece, the single-sided adhesive tape was peeled off from the copper-clad laminate. The resistance to strong alkaline solutions was evaluated by confirming discoloration of the copper at the portion of the copper-clad laminate where the single-sided adhesive tape had been pasted.
◎ indicates no discoloration of the copper, ◯ indicates discoloration of the copper within 2 mm from the end of the portion where the single-sided adhesive tape was applied, and ◯ indicates the portion where the single-sided adhesive tape was applied. The case where discoloration of copper was observed in a range exceeding 2 mm from the edge of the plate was evaluated as x.
(2-2)デスミア及び無電解メッキ
試験片に対して、表5に示す条件でデスミア処理を行った後、表4に示す条件で無電解メッキを行った。試験片を取り出した後、銅張積層板から片面粘着テープを剥離した。銅張積層板の片面粘着テープを貼り付けていた部分の銅の変色を確認してデスミア及び無電解メッキへの耐性を評価した。
銅の変色がみられなかった場合を◎、片面粘着テープを貼り付けていた部分の端部から2mm以内の範囲に銅の変色がみられた場合を〇、片面粘着テープを貼り付けていた部分の端部から2mmを超える範囲で銅の変色がみられた場合を×とした。
(2-2) Desmear and Electroless Plating Test pieces were subjected to desmear treatment under the conditions shown in Table 5, and then electrolessly plated under the conditions shown in Table 4. After taking out the test piece, the single-sided adhesive tape was peeled off from the copper-clad laminate. Resistance to desmear and electroless plating was evaluated by confirming discoloration of copper in the portion of the copper-clad laminate where the single-sided adhesive tape had been pasted.
◎ indicates no discoloration of the copper, ◯ indicates discoloration of the copper within 2 mm from the end of the portion where the single-sided adhesive tape was applied, and ◯ indicates the portion where the single-sided adhesive tape was applied. The case where discoloration of copper was observed in a range exceeding 2 mm from the edge of the plate was evaluated as x.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
BA:ブチルアクリレート
2-EHA:2-エチルヘキシルアクリレート
MMA:メチルメタクリレート
BMA:ブチルメタクリレート
IBOA:イソボルニルアクリレート
IBOMA:イソボルニルメタクリレート
AAc:アクリル酸
HEA:2-ヒドロキシエチルアクリレート
BA: butyl acrylate 2-EHA: 2-ethylhexyl acrylate MMA: methyl methacrylate BMA: butyl methacrylate IBOA: isobornyl acrylate IBOMA: isobornyl methacrylate AAc: acrylic acid HEA: 2-hydroxyethyl acrylate
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
本発明によれば、厚みが薄い被着体に貼り付ける際にもシワを生じにくく、かつ、強アルカリ性溶液への耐性に優れた片面粘着テープを提供することができる。 According to the present invention, it is possible to provide a single-sided pressure-sensitive adhesive tape that is less likely to wrinkle when attached to a thin adherend and has excellent resistance to strong alkaline solutions.
1  端部保護された金属張積層板
2  金属張積層板
30,30’,30’’  片面粘着テープ
31,31’,31’’  基材
32,32’,32’’  感熱粘着剤層
3a  感熱粘着剤層同士の界面

 
1 edge-protected metal-clad laminate 2 metal-clad laminate 30, 30', 30'' single-sided adhesive tape 31, 31', 31'' substrate 32, 32', 32'' heat-sensitive adhesive layer 3a heat-sensitive Interface between adhesive layers

Claims (20)

  1. 基材と、前記基材の一方の面に積層された感熱粘着剤層とを有する片面粘着テープであって、
    前記基材は、少なくとも前記感熱粘着剤層とは反対側の表面に、金属層を有し、
    前記感熱粘着剤層は、SUSに対する静止摩擦係数が5以下である
    ことを特徴とする片面粘着テープ。
    A single-sided adhesive tape having a substrate and a heat-sensitive adhesive layer laminated on one side of the substrate,
    The base material has a metal layer at least on the surface opposite to the heat-sensitive adhesive layer,
    The single-sided adhesive tape, wherein the heat-sensitive adhesive layer has a static friction coefficient of 5 or less against SUS.
  2. 前記金属層は、銅からなることを特徴とする請求項1記載の片面粘着テープ。 2. The single-sided adhesive tape of claim 1, wherein said metal layer is made of copper.
  3. 前記基材は、金属基材であることを特徴とする請求項1又は2記載の片面粘着テープ。 3. The single-sided pressure-sensitive adhesive tape according to claim 1, wherein said base material is a metal base material.
  4. 前記金属基材は、銅箔であることを特徴とする請求項3記載の片面粘着テープ。 4. The single-sided adhesive tape according to claim 3, wherein said metal substrate is a copper foil.
  5. 前記基材と前記感熱粘着剤層との間に更に感圧粘着剤層を有することを特徴とする請求項1、2、3又は4記載の片面粘着テープ。 5. The single-sided adhesive tape according to claim 1, further comprising a pressure-sensitive adhesive layer between said substrate and said heat-sensitive adhesive layer.
  6. 前記感熱粘着剤層は、動的粘弾性測定装置を用いて測定周波数1Hzで測定した損失正接のピーク温度が40℃以上であることを特徴とする請求項1、2、3、4又は5記載の片面粘着テープ。 6. The heat-sensitive adhesive layer according to claim 1, wherein the peak temperature of loss tangent measured at a measurement frequency of 1 Hz using a dynamic viscoelasticity measuring device is 40° C. or higher. single-sided adhesive tape.
  7. 前記感熱粘着剤層は、23℃における貯蔵弾性率G’が5MPa以上、100℃における貯蔵弾性率G’が0.2MPa以下であることを特徴とする請求項1、2、3、4、5又は6記載の片面粘着テープ。 6. The heat-sensitive adhesive layer has a storage modulus G' of 5 MPa or more at 23° C. and a storage modulus G' of 0.2 MPa or less at 100° C. Or the single-sided adhesive tape according to 6.
  8. 前記感熱粘着剤層は、ゲル分率が50重量%以上であることを特徴とする請求項1、2、3、4、5、6又は7記載の片面粘着テープ。 8. The single-sided adhesive tape according to claim 1, 2, 3, 4, 5, 6 or 7, wherein said heat-sensitive adhesive layer has a gel fraction of 50% by weight or more.
  9. 前記感熱粘着剤層は、表面粗さRaが0.01μm以上、0.8μm以下であることを特徴とする請求項1、2、3、4、5、6、7又は8記載の片面粘着テープ。 9. The single-sided adhesive tape according to claim 1, wherein the heat-sensitive adhesive layer has a surface roughness Ra of 0.01 μm or more and 0.8 μm or less. .
  10. 前記感熱粘着剤層は、アクリル系ポリマーを含有することを特徴とする請求項1、2、3、4、5、6、7、8又は9記載の片面粘着テープ。 10. The single-sided pressure-sensitive adhesive tape according to claim 1, wherein said heat-sensitive pressure-sensitive adhesive layer contains an acrylic polymer.
  11. 前記感熱粘着剤層は、更に、粘着付与樹脂を含有することを特徴とする請求項10記載の片面粘着テープ。 11. The single-sided adhesive tape according to claim 10, wherein said heat-sensitive adhesive layer further contains a tackifying resin.
  12. 前記粘着付与樹脂は、軟化点が100℃以上であることを特徴とする請求項11記載の片面粘着テープ。 12. The single-sided pressure-sensitive adhesive tape according to claim 11, wherein said tackifying resin has a softening point of 100[deg.] C. or higher.
  13. 前記粘着付与樹脂は、水酸基価が25mgKOH/g以上であることを特徴とする請求項11又は12記載の片面粘着テープ。 13. The single-sided pressure-sensitive adhesive tape according to claim 11, wherein the tackifying resin has a hydroxyl value of 25 mgKOH/g or more.
  14. 前記アクリル系ポリマー100重量部に対する前記粘着付与樹脂の含有量が5重量部以上、50重量部以下であることを特徴とする請求項11、12又は13記載の片面粘着テープ。 14. The single-sided pressure-sensitive adhesive tape according to claim 11, 12 or 13, wherein the content of said tackifier resin is 5 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of said acrylic polymer.
  15. 前記感熱粘着剤層は、エポキシ系架橋剤を含有することを特徴とする請求項10、11、12、13又は14記載の片面粘着テープ。 15. The single-sided adhesive tape according to claim 10, 11, 12, 13 or 14, wherein the heat-sensitive adhesive layer contains an epoxy-based cross-linking agent.
  16. 前記感圧粘着剤層は、ゲル分率が50重量%以上であることを特徴とする請求項5記載の片面粘着テープ。 6. The single-sided adhesive tape according to claim 5, wherein the pressure-sensitive adhesive layer has a gel fraction of 50% by weight or more.
  17. 前記感圧粘着剤層は、エポキシ系架橋剤を含有することを特徴とする請求項5記載の片面粘着テープ。 6. The single-sided adhesive tape according to claim 5, wherein the pressure-sensitive adhesive layer contains an epoxy-based cross-linking agent.
  18. 基材と、前記基材の一方の面に積層された感熱粘着剤層とを有する片面粘着テープであって、
    前記基材は、少なくとも前記感熱粘着剤層とは反対側の表面に、金属層を有し、
    前記感熱粘着剤層は、アクリル系ポリマー、及び、粘着付与樹脂を含有し、
    前記粘着付与樹脂は、軟化点が100℃以上であり、かつ水酸基価が25mgKOH/g以上であり、
    前記アクリル系ポリマー100重量部に対する前記粘着付与樹脂の含有量が5重量部以上、50重量部以下であり、
    前記感熱粘着剤層は、SUSに対する静止摩擦係数が5以下である
    ことを特徴とする片面粘着テープ。
    A single-sided adhesive tape having a substrate and a heat-sensitive adhesive layer laminated on one side of the substrate,
    The base material has a metal layer at least on the surface opposite to the heat-sensitive adhesive layer,
    The heat-sensitive adhesive layer contains an acrylic polymer and a tackifying resin,
    The tackifying resin has a softening point of 100° C. or higher and a hydroxyl value of 25 mgKOH/g or higher,
    The content of the tackifying resin with respect to 100 parts by weight of the acrylic polymer is 5 parts by weight or more and 50 parts by weight or less,
    The single-sided adhesive tape, wherein the heat-sensitive adhesive layer has a static friction coefficient of 5 or less against SUS.
  19. エッチング工程、デスミア工程、又は、無電解メッキ工程において、金属張積層板の端部に貼り付けて金属張積層板の端部を保護するために用いられることを特徴とする請求項1、2、3、4、5、6、7、8、9、10、11、12、13、14、15、16、17又は18記載の片面粘着テープ。 Claims 1 and 2, characterized in that it is used to protect the edge of the metal-clad laminate by attaching it to the edge of the metal-clad laminate in the etching process, the desmear process, or the electroless plating process. 19. The single-sided adhesive tape according to 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 or 18.
  20. 一方の面に金属層を有し、他方の面に感熱粘着剤層を有する片面粘着テープであって、
    前記感熱粘着剤層は、SUSに対する静止摩擦係数が5以下である
    ことを特徴とする片面粘着テープ。
     

     
    A single-sided adhesive tape having a metal layer on one side and a heat-sensitive adhesive layer on the other side,
    The single-sided adhesive tape, wherein the heat-sensitive adhesive layer has a static friction coefficient of 5 or less against SUS.


PCT/JP2022/048577 2022-01-13 2022-12-28 Single-sided adhesive tape WO2023136171A1 (en)

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PCT/JP2022/048577 WO2023136171A1 (en) 2022-01-13 2022-12-28 Single-sided adhesive tape

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CN (1) CN117813359A (en)
TW (1) TW202334353A (en)
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58154778A (en) * 1981-12-28 1983-09-14 ミネソタ・マイニング・アンド・マニユフアクチユアリング・コンパニ− Adhesive tape and manufacture
JP2006199950A (en) * 2004-12-22 2006-08-03 Ricoh Co Ltd Heat-sensitive adhesive material
WO2022050360A1 (en) * 2020-09-03 2022-03-10 積水化学工業株式会社 Metal-clad laminate having protected edge, method for producing printed wiring board, and method for producing intermediate for printed wiring boards

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58154778A (en) * 1981-12-28 1983-09-14 ミネソタ・マイニング・アンド・マニユフアクチユアリング・コンパニ− Adhesive tape and manufacture
JP2006199950A (en) * 2004-12-22 2006-08-03 Ricoh Co Ltd Heat-sensitive adhesive material
WO2022050360A1 (en) * 2020-09-03 2022-03-10 積水化学工業株式会社 Metal-clad laminate having protected edge, method for producing printed wiring board, and method for producing intermediate for printed wiring boards

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