WO2020209212A1 - Method for producing adhesive tape - Google Patents

Method for producing adhesive tape Download PDF

Info

Publication number
WO2020209212A1
WO2020209212A1 PCT/JP2020/015459 JP2020015459W WO2020209212A1 WO 2020209212 A1 WO2020209212 A1 WO 2020209212A1 JP 2020015459 W JP2020015459 W JP 2020015459W WO 2020209212 A1 WO2020209212 A1 WO 2020209212A1
Authority
WO
WIPO (PCT)
Prior art keywords
adhesive tape
adhesive
coating liquid
producing
base material
Prior art date
Application number
PCT/JP2020/015459
Other languages
French (fr)
Japanese (ja)
Inventor
晃純 木村
洋亮 楯
大輔 吉村
Original Assignee
デンカ株式会社
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.)
Filing date
Publication date
Application filed by デンカ株式会社 filed Critical デンカ株式会社
Priority to JP2021513619A priority Critical patent/JP7368459B2/en
Publication of WO2020209212A1 publication Critical patent/WO2020209212A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/21—Paper; Textile fabrics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]

Definitions

  • the present invention relates to a method for manufacturing an adhesive tape.
  • the non-woven fabric is a porous body, it has sound deadening properties, is excellent in mechanical strength typified by tensile strength, and is inexpensive, so that it is widely used as a base material for adhesive tapes.
  • a method for producing an adhesive tape for example, there is a method of applying a coating liquid containing an adhesive on the surface of a base material to form an adhesive layer.
  • a coating liquid containing a solvent such as water or a solvent, a non-solvent-based coating liquid containing no solvent, or the like is known.
  • Patent Document 1 describes an aqueous solution containing a polycarboxylic acid-based copolymer having a specific molecular weight on paper.
  • a method for producing coated paper for printing which includes a step of coating the surface of a base material by applying a curtain, is described.
  • the manufacturing method is a method used for coating on printing paper, and in manufacturing an adhesive tape, it is necessary to increase the thickness of the coating film (that is, the adhesive layer), so that the drying speed becomes slow. , There is a problem that strike-through of the coating liquid occurs.
  • a coating liquid is once applied onto another sheet such as a release paper using a high-viscosity hot melt. After that, the coating is generally performed by transfer coating, which is transferred onto the substrate.
  • the transfer coating using a release paper has a problem that the adhesion to the non-woven fabric of the base material is low (that is, the holding power is low) and it is not suitable for manufacturing an adhesive tape in a field where re-peelability is required. is there.
  • Another problem is that the adhesive layer formed by hot melt has low heat resistance. Therefore, there is a demand for a method for producing an adhesive tape, which can suppress strike-through from the base material during production and can provide an adhesive tape having high heat resistance and removability.
  • the present invention is a method for manufacturing an adhesive tape in which a water-based coating liquid is directly applied to a base material made of a non-woven fabric to form an adhesive layer, which can prevent strike-through during manufacturing, and has high heat resistance and removability. It is an object of the present invention to provide a method for producing an adhesive tape for obtaining an adhesive tape having the above.
  • the inventors of the present application have used a pressure-sensitive adhesive coating solution containing an aqueous emulsion and a polycarboxylic acid-based polymer having a specific molecular weight and having a specific viscosity.
  • a manufacturing method having a step of forming an adhesive layer on a non-woven fabric by roll coating, and have completed the present invention. That is, the present invention has the following aspects.
  • Method of manufacturing adhesive tape including.
  • the present invention is a method for manufacturing an adhesive tape in which a water-based coating liquid is directly applied to a base material made of a non-woven fabric to form an adhesive layer. It is possible to provide a method for producing an adhesive tape, which can obtain an adhesive tape having peelability.
  • the present invention is a method for producing an adhesive tape having a base material made of a non-woven fabric and an adhesive layer, which comprises an aqueous emulsion and a polycarboxylic acid polymer having a weight average molecular weight of 4 to 30 million.
  • a step of forming an adhesive layer by applying a pressure-sensitive adhesive coating liquid having a viscosity of 6000 to 20000 mPa ⁇ s / 23 ° C. measured at 60 rpm using a mold viscometer on the substrate by roll coating. It is characterized by including.
  • water system means that an oil component is dispersed in water. Further, an appropriately selected tackifier or plasticizer may be uniformly dispersed in the "aqueous emulsion”.
  • the adhesive layer of the present invention contains an aqueous emulsion and a polycarboxylic acid-based polymer having a weight average molecular weight of 4 to 30 million, and has a viscosity of 6000 to 20000 mPa ⁇ s / measured at 60 rpm using a B-type viscometer.
  • a pressure-sensitive adhesive coating liquid at 23 ° C. is applied onto the substrate by roll coating to form the substrate.
  • the pressure-sensitive adhesive coating liquid contains an aqueous emulsion and a polycarboxylic acid-based polymer having a weight average molecular weight of 4 to 30 million.
  • the viscosity of the pressure-sensitive adhesive coating solution measured at 60 rpm using a B-type viscometer is 6000 to 20000 mPa ⁇ s / 23 ° C.
  • the aqueous emulsion of the present invention is one in which rubber particles are dispersed in water as a dispersion medium (so-called latex), one in which thermoplastic elastomer particles are dispersed in water as a dispersion medium, or a dispersion medium. It means that the acrylic polymer is dispersed in water. That is, the aqueous emulsion of the present invention also contains latex.
  • the latex may be a natural rubber latex or a synthetic rubber latex.
  • the solid content in the latex is, for example, preferably 50 to 99% by mass, more preferably 60 to 90% by mass. As such a latex, a commercially available latex may be used.
  • a natural latex a product name "EXCELTEX-HLX LA-TZ” manufactured by KUALA LUMPUR KEPONG BERHAD, a product manufactured by Regitex Co., Ltd.
  • examples include the name "TRH-70”.
  • examples of the synthetic latex include a trade name "MG30” manufactured by Musashino Chemical Co., Ltd., a trade name "Nipol (registered trademark) LX430” manufactured by Nippon Zeon Corporation, and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the acrylic polymer for example, a polymer obtained by polymerizing a monomer such as butyl acrylate, 2-ethylhexyl acrylate, or acrylic acid at an arbitrary ratio can be used.
  • thermoplastic elastomer emulsion examples include the trade name "JSR DYNARON (registered trademark) 1321P" manufactured by JSR Corporation.
  • the aqueous emulsion is preferably latex, more preferably a mixture of natural latex and synthetic latex.
  • the blending ratio (natural latex / synthetic latex) is preferably 3/7 to 7/3. By using the mixture, it becomes easy to obtain a balance between the strength of the adhesive layer and the adhesive strength.
  • the viscosity of the aqueous emulsion is preferably 10 to 300 mPa ⁇ s / 23 ° C., more preferably 50 to 200 mPa ⁇ s / 23 ° C., as measured with a B-type viscometer.
  • the proportion of the water-based emulsion in the pressure-sensitive adhesive coating liquid is preferably 5 to 70% by mass, more preferably 15 to 50% by mass, based on the total mass of the pressure-sensitive adhesive coating liquid.
  • the ratio of the water-based emulsion in the pressure-sensitive adhesive coating liquid is within the above range, there is no problem of surface skinning during coating, and it becomes easy to adjust the drying time to an appropriate range.
  • the polycarboxylic acid-based polymer is a monomer (A) containing a carboxy group (hereinafter, may be simply referred to as "monomer (A)”) or a derivative (I) of the monomer (A). ) (Hereinafter, it may be simply referred to as “derivative (I)”) to mean a polymer obtained by polymerizing. Further, in one aspect of the present invention, the polycarboxylic acid-based polymer polymerizes a monomer (X) containing at least one selected from the group consisting of the monomer (A) and the derivative (I). It may be the obtained copolymer.
  • Examples of the monomer (A) include acrylic acid, maleic acid, and methacrylic acid. Of these, from the viewpoint of solubility, the monomer (A) is preferably acrylic acid or methacrylic acid, and more preferably acrylic acid.
  • examples of the derivative (I) include mono or dialkali earth metal salts, mono or diesters, amides, imides, and anhydrides of the monomer (A). Of these, from the viewpoint of imparting water solubility, the derivative (I) is preferably a monomer or a dialkalis earth metal of the monomer (A), or an amide of the monomer (A), and the amide of the monomer (A) is preferable. More preferred.
  • the polycarboxylic acid-based polymer is preferably a polymer of a derivative (I) of a monomer (A) containing a carboxy group.
  • the derivative (I) is particularly preferably sodium acrylate or acrylamide. Since it is a polymer of the derivative (I), the effect of preventing strike-through can be easily obtained.
  • the weight average molecular weight of the polycarboxylic acid-based polymer of the present invention is 4 million to 30 million, more preferably 5 million to 20 million. When the weight average molecular weight of the polycarboxylic acid-based polymer is within the above range, the effect of preventing strike-through can be obtained.
  • the weight average molecular weight refers to a value measured by gel permeation chromatography (GPC). Specifically, GPC measurement is performed, the molecular weight at each elution time is calculated from the elution curve of monodisperse polystyrene under the following conditions, and the molecular weight is calculated as polystyrene-equivalent molecular weight.
  • the ratio of the polycarboxylic acid-based polymer in the pressure-sensitive adhesive coating liquid is preferably 0.1 to 3 parts by mass with respect to the total amount (100 parts by mass) of the aqueous emulsion. More preferably 0.5 to 2 parts by mass. Further, in one aspect of the present invention, the ratio of the polycarboxylic acid-based polymer in the pressure-sensitive adhesive coating liquid is preferably 5% by mass or less, preferably 1% by mass, based on the total mass of the pressure-sensitive adhesive coating liquid. % Or less is more preferable. When the ratio of the polycarboxylic acid-based polymer in the pressure-sensitive adhesive coating liquid is within the above range, the effect of preventing strike-through can be easily obtained and the pressure-sensitive adhesive strength can be easily improved.
  • the pressure-sensitive adhesive coating liquid may contain a pressure-sensitive adhesive as long as the effects of the present invention are not impaired.
  • the tackifier include petroleum resins such as aliphatic copolymers, aromatic copolymers, aliphatic / aromatic copolymers and alicyclic copolymers, and kumaron-inden resins. , Terpene-based resin, terpene-phenol-based resin, rosin-based resin such as polymerized rosin, (alkyl) phenol-based resin, xylene-based resin, and hydrogenated products thereof. These may be used individually by 1 type, and may be used in combination of 2 or more type.
  • tackifier a terpene phenol resin or a petroleum resin (C5 to C9 petroleum resin or C5 petroleum resin) is preferable from the viewpoint of cost and low coloring. Further, these tackifiers may be emulsions.
  • the proportion of the tackifier in the pressure-sensitive adhesive coating liquid is preferably 20 to 80% by mass, more preferably 20 to 50% by mass, based on the total mass of the pressure-sensitive adhesive coating liquid. When the ratio of the tackifier is within the above range, the effect of imparting tackiness can be easily obtained.
  • the pressure-sensitive adhesive coating liquid may contain a surfactant as long as the effects of the present invention are not impaired.
  • the surfactant include anionic surfactants, cationic surfactants, nonionic surfactants and the like.
  • an anionic surfactant is preferable because it has high solubility and few coating defects (such as repellent) during drying.
  • the anionic surfactant include sulfonic acid-based surfactants, sulfate ester-based surfactants, carboxylic acid-based surfactants, and the like. Of these, a sulfonic acid-based surfactant is more preferable from the viewpoint of solubility.
  • the proportion of the surfactant in the pressure-sensitive adhesive coating liquid is preferably 4% by mass or less, more preferably 1% by mass or less, based on the total mass of the pressure-sensitive adhesive coating liquid, from the viewpoint of not reducing the adhesive strength. ..
  • the pressure-sensitive adhesive coating liquid of the present invention may contain other additives as long as the effects of the present invention are not impaired.
  • Other additives include, for example, thickeners, softeners, surface lubricants, leveling agents, antioxidants, corrosion inhibitors, light stabilizers, UV absorbers, heat stabilizers, polymerization inhibitors, silanelinger.
  • Examples include lubricants, lubricants, inorganic or organic fillers, metal powders, pigments and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the thickener examples include a water-soluble polymer thickener, an association type thickener, and the like. Of these, a water-soluble polymer thickener is preferable from the viewpoint of the stability of the viscosity of the pressure-sensitive adhesive coating liquid.
  • the blending amount thereof is preferably 0.1 to 4% by mass with respect to the total mass of the pressure-sensitive adhesive coating liquid.
  • the total blending amount of the other additives is preferably 0.1 to 10% by mass, preferably 0, based on the total mass of the pressure-sensitive adhesive coating liquid. .5 to 8% by mass is more preferable.
  • the pressure-sensitive adhesive coating liquid of the present invention preferably contains water. Water is added to adjust the viscosity of the adhesive coating solution. Therefore, the proportion of water in the pressure-sensitive adhesive coating liquid is appropriately adjusted so that the viscosity of the pressure-sensitive adhesive coating liquid is within the above range. Pure water is preferable as water.
  • the pressure-sensitive adhesive coating liquid of the present invention has a viscosity of 6000 to 20000 mPa ⁇ s / 23 ° C., preferably 8000 to 14000 mPa ⁇ s / 23 ° C., measured under the condition of 60 rpm using a B-type viscometer. ..
  • a viscosity of the pressure-sensitive adhesive coating liquid at 23 ° C. is measured at a rotation speed of 60 rpm using a B-type viscometer. Further, as the B-type viscometer, a rotor of LV-3 manufactured by BROOKFIELD is used.
  • the thickness of the adhesive layer is preferably 15 ⁇ m or more, more preferably 30 ⁇ m or more.
  • the thickness of the adhesive layer is 15 ⁇ m or more, it becomes easy to develop sufficient adhesive force as an adhesive tape.
  • the base material of the present invention is made of a non-woven fabric. That is, the "base material made of non-woven fabric” means a sheet-like base material in which fibers constituting the non-woven fabric are combined without weaving.
  • the non-woven fabric for example, a non-woven fabric produced by the spunbond method, a non-woven fabric produced by the spunlace method, a non-woven fabric produced by the melt blow method, or the like can be used.
  • the non-woven fabric may be a single layer or a laminated non-woven fabric composed of a plurality of layers. Further, in the case of a laminated non-woven fabric, the non-woven fabrics produced by a plurality of methods may be laminated.
  • a non-woven fabric spun-bonded non-woven fabric prepared by the spunbond method.
  • a base material made of a spunbonded non-woven fabric it becomes easy to obtain a tape having high protection of the adherend.
  • the basis weight of the non-woven fabric is preferably 50 to 150 g / m 2 , and more preferably 70 to 120 g / m 2 .
  • the porosity is preferably 30 to 90%.
  • the fibers constituting the non-woven fabric are not particularly limited as long as they have the effects of the present invention, and examples thereof include aramid fibers, glass fibers, cellulose fibers, nylon fibers, vinylon fibers, polyester fibers, polyolefin fibers, rayon fibers and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type. Of these, polyester fiber is preferable from the viewpoint of heat resistance and durability.
  • the fiber diameter of the fibers constituting the non-woven fabric is preferably 3 to 50 ⁇ m, more preferably 4 to 30 ⁇ m, from the viewpoint of the strength of the base material.
  • the fiber diameter of the non-woven fabric is within the above range, the sound deadening effect can be easily obtained.
  • the thickness of the base material is preferably 200 to 700 ⁇ m, more preferably 250 to 350 ⁇ m from the viewpoint of its handling.
  • the method for producing an adhesive tape of the present invention is a step of forming an adhesive layer by applying the above-mentioned adhesive coating liquid on the base material by roll coating, preferably comma reverse coating (hereinafter, "" It may also be described as “adhesive layer forming step”).
  • the coating conditions it is preferable to coat one surface of the base material made of a non-woven fabric with the adhesive coating liquid at 30 m / sec and a drying condition of 130 ° C.
  • the pressure-sensitive adhesive layer forming step it is preferable to use a pressure-adjusted pressure-sensitive adhesive coating liquid at 20 to 30 ° C.
  • the pressure-sensitive adhesive layer forming step is preferably a step of applying the pressure-sensitive adhesive coating liquid on the base material by roll coating to form a pressure-sensitive adhesive layer having a thickness of 15 ⁇ m or more.
  • the adhesive layer may be a single layer or a multi-layer.
  • the pressure-sensitive adhesive coating liquid is applied onto the substrate by roll coating, preferably comma reverse coating, and has a thickness of 15 ⁇ m or more. It is more preferable that the step is to form the adhesive layer as a single layer.
  • the pressure-sensitive adhesive coating liquid of the present invention contains an aqueous emulsion and a polycarboxylic acid-based polymer having a specific molecular weight, and has a specific viscosity, so that it has a thickness of 15 ⁇ m or more. Even if the adhesive layer is formed in one step, strike-through is unlikely to occur.
  • the step of preparing the pressure-sensitive adhesive coating liquid may be included before the step of forming the pressure-sensitive adhesive layer.
  • the step of preparing the pressure-sensitive adhesive coating liquid include the aqueous emulsion and the polycarboxylic acid polymer, as well as a tackifier and a surfactant.
  • examples thereof include a step of appropriately selecting, blending and mixing an activator, other additives and the like, and then adding pure water to prepare an adhesive coating liquid so as to be within the above-mentioned viscosity range.
  • the blending order of each main component is arbitrary.
  • the method for producing an adhesive tape of the present invention can prevent strike-through from the base material when the adhesive layer is formed.
  • the presence or absence of strike-through from the base material can be evaluated according to the procedure shown below.
  • the prepared adhesive tape is immersed in liquid nitrogen for 1 minute to infiltrate. After that, the adhesive tape is cut vertically. Observe the cross section of the adhesive tape with a laser microscope to see if the adhesive has penetrated to the back of the substrate.
  • the adhesive tape obtained by the present production method is also excellent in heat resistance.
  • the heat resistance of the adhesive tape can be evaluated, for example, according to the procedure shown below.
  • a wire binding product (sample) of adhesive tape is prepared according to SAE J2192. Place 20 samples in a hot air circulation furnace that can switch air 8 to 20 times per hour. The sample is exposed at 105 ° C. for 3000 hours.
  • SAE J2192 For the test procedure, see Sections 7.3.3 and 7.3.4 of SAE J2192, except for the work of taking out 5 samples every 500 hours and every 1000 hours for up to 3000 hours. .. After 3000 hours have passed, wrap the wire binding product (sample) around a 40 mm mandrel and check if the tape is peeled off.
  • the adhesive tape produced by the method for producing an adhesive tape of the present invention exhibits high removability.
  • Adhesive strength evaluation The adhesive strength of the adhesive tape obtained by the method for producing an adhesive tape of the present invention can be evaluated according to JIS Z0237.
  • the adhesive tape obtained by the production method of the present invention can be used in fields where heat resistance is required, such as a car engine room. Can be suitably used as an adhesive tape of.
  • the pressure-sensitive adhesive coating liquid of the present invention has a high holding power to the base material, the obtained pressure-sensitive adhesive tape also has removability. Therefore, it can be suitably used in fields where removability is required, for example, as an adhesive tape such as an insulating tape.
  • Example 1 ⁇ Preparation of adhesive coating solution> As an aqueous emulsion, 50 parts by mass (solid content) of natural latex (manufactured by KUALA LUMPUR KEPONG BERHAD, trade name "EXCELTEX-HLX LA-TZ”), synthetic latex (manufactured by Musashino Chemical Co., Ltd., trade name "MG30") 50 Using parts by mass (solid content), as a tackifier, terpenphenol resin emulsion (manufactured by Arakawa Chemical Industry Co., Ltd., trade name "E-200”) 30 parts by mass (solid content), petroleum resin emulsion (Arakawa Chemical Industry Co., Ltd.) 70 parts by mass (solid content) of (trade name "AP-1100-NT”) manufactured by Co., Ltd.
  • natural latex manufactured by KUALA LUMPUR KEPONG BERHAD, trade name "EXCELTEX-HLX LA-TZ”
  • synthetic latex manufactured by Musashino Chemical Co
  • the heat resistance of the obtained adhesive tape was evaluated according to the following evaluation method.
  • An electric wire bundled product (sample) of an adhesive tape was prepared according to SAE J2192. Twenty samples were placed in a hot air circulation furnace capable of switching air 8 to 20 times per hour, and the samples were exposed at 105 ° C. for 3000 hours. For the test procedure, see Sections 7.3.3 and 7.3.4 of SAE J2192, except for the work of taking out 5 samples every 500 hours and every 1000 hours for up to 3000 hours. After the lapse of 3000 hours, a wire binding product (sample) was wound around a 40 mm mandrel, and it was confirmed whether the tape was peeled off. Twenty samples were evaluated according to the following evaluation criteria. The A evaluation was passed (high heat resistance). (Evaluation criteria) A: There was no peeling of the tape in all the samples. B: Tape peeling occurred in a part of the sample C: Tape peeling occurred in all the samples.
  • Adhesive strength evaluation The adhesive strength of the obtained adhesive tape was evaluated according to the method described in JIS Z0237. In addition, the obtained adhesive strength was evaluated according to the following evaluation criteria. In addition, B evaluation or higher was regarded as passing (excellent in adhesive strength). (Evaluation criteria) A: Adhesive strength is 4N / 20mm or more. B: Adhesive strength is 1N / 20mm or more and less than 4N / 20mm. C: Adhesive strength is less than 1N / 20mm.
  • Examples 2 to 4 and Comparative Examples 1 to 4 An adhesive tape was prepared in the same manner as in Example 1 except that the type of the non-woven fabric and the composition of the adhesive coating liquid were as shown in Table 1.
  • the adhesive tapes of each of the obtained examples were evaluated for strike-through, heat resistance, removability, and adhesive strength by the same method as in Example 1. The results are shown in Table 1.
  • Aqueous emulsion 1 Natural rubber latex (manufactured by KUALA LUMPURU KEPONG BERHAD, trade name "EXCELTEX-HLX LA-TZ", solid content 50% by mass).
  • Aqueous emulsion 2 Synthetic rubber latex (manufactured by Musashino Chemical Co., Ltd., trade name "MG30”, solid content 50% by mass).
  • Polycarboxylic acid polymer 1 Polyacrylamide (manufactured by SOMAR Corporation, trade name "Somalex (registered trademark) 530", weight average molecular weight 20 million).
  • Polycarboxylic acid polymer 2 Sodium polyacrylate (manufactured by Toa Synthetic Co., Ltd., trade name "Aron (registered trademark) A-20P", weight average molecular weight 5 million).
  • Polycarboxylic acid-based polymer 3 Polyacrylic acid (manufactured by Toa Synthetic Co., Ltd., trade name "Julimer (registered trademark) AC-10SHP", weight average molecular weight 1 million).
  • Adhesive imparting agent 1 Terpene phenol resin emulsion (manufactured by Arakawa Chemical Industry Co., Ltd., trade name "E-200", solid content 50% by mass).
  • Adhesive imparting agent 2 Petroleum resin emulsion (manufactured by Arakawa Chemical Industry Co., Ltd., trade name "AP-1100-NT", solid content 50% by mass).
  • Surfactant Anionic surfactant (manufactured by Kao Corporation, trade name “Neoperex G-25")
  • Thickener Water-based polymer thickener (manufactured by San Nopco Co., Ltd., trade name "Sickener SN-812").
  • Spun-bonded non-woven fabric polyester fiber, basis weight 80 g / m 2 .
  • Spunlace non-woven fabric polyester fiber, basis weight 80 g / m 2 .
  • Stitch bond non-woven fabric polyester fiber, basis weight 80 g / m 2 , 22F.
  • the weight average molecular weight of the polycarboxylic acid polymer was measured by GPC, and the molecular weight at each elution time was calculated from the elution curve of monodisperse polystyrene under the following conditions, and the molecular weight was calculated as polystyrene-equivalent molecular weight.
  • the adhesive tape obtained by the production method of the present invention did not cause strike-through during coating, and was excellent in heat resistance and removability. It also had sufficient adhesive strength to be used as an adhesive tape.
  • the adhesive tapes of Comparative Examples 1 to 4 produced by the production method not satisfying the constitution of the present invention strike-through occurred at the time of coating.
  • the obtained adhesive tape had low adhesive strength. From the above results, it was confirmed that the method for producing an adhesive tape of the present invention can prevent strike-through from the base material during production, and the obtained adhesive tape is excellent in heat resistance and removability.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesive Tapes (AREA)

Abstract

[Problem] To provide a method for producing an adhesive tape, which forms an adhesive layer by directly applying an aqueous coating liquid onto a base material that is composed of a nonwoven fabric, and which is capable of preventing strike-through during the production and enables the achievement of an adhesive tape that has high heat resistance and releasability. [Solution] A method for producing an adhesive tape having an adhesive layer and a base material that is composed of a nonwoven fabric, which comprises a step for forming the adhesive layer by applying an adhesive coating liquid that contains an aqueous emulsion and a polycarboxylic acid polymer having a weight average molecular weight of from 4,000,000 to 30,000,000, said adhesive coating liquid having a viscosity of 6,000 to 20,000 mPa∙s/23°C as measured using a B-type viscometer at 60 rpm, onto the base material by means of roll coating.

Description

粘着テープの製造方法Adhesive tape manufacturing method
　本発明は、粘着テープの製造方法に関する。 The present invention relates to a method for manufacturing an adhesive tape.
　不織布は、多孔質体であることから消音性を有し、引張強度に代表される機械的強度に優れ、かつ安価であることから、粘着テープ用基材として広く用いられている。
　粘着テープの製造方法としては、例えば、基材の表面に、粘着剤を含む塗工液を塗工して粘着層を形成する方法がある。前記塗工液としては、例えば、水や溶剤等の溶媒を含む塗工液、又は前記溶媒を含まない非溶媒系の塗工液等が知られている。しかしながら、不織布からなる基材上に、溶媒を含む塗工液を塗工して粘着層を形成する場合、不織布は多孔質体であることから、塗工液が浸透して基材の裏側から染み出る、「裏抜け」という現象が生じることがある。近年、環境意識への高まりを受けて、水を溶媒として含む水系塗工液への要望が高まりつつあるが、上述の裏抜けの問題から、水系塗工液の不織布上への直接塗布は難しいとされている。 Since the non-woven fabric is a porous body, it has sound deadening properties, is excellent in mechanical strength typified by tensile strength, and is inexpensive, so that it is widely used as a base material for adhesive tapes.
As a method for producing an adhesive tape, for example, there is a method of applying a coating liquid containing an adhesive on the surface of a base material to form an adhesive layer. As the coating liquid, for example, a coating liquid containing a solvent such as water or a solvent, a non-solvent-based coating liquid containing no solvent, or the like is known. However, when a coating liquid containing a solvent is applied onto a base material made of a non-woven fabric to form an adhesive layer, since the non-woven fabric is a porous body, the coating liquid permeates from the back side of the base material. A phenomenon called "through-through" that exudes may occur. In recent years, there has been an increasing demand for water-based coating liquids containing water as a solvent in response to increasing environmental awareness, but it is difficult to directly apply the water-based coating liquid onto a non-woven fabric due to the above-mentioned strike-through problem. It is said that.
　多孔質体の表面に水系塗工液を直接塗布して塗工層を形成する方法として、例えば、特許文献１には、特定の分子量を有するポリカルボン酸系共重合体を含む水溶液を、紙基材の表面にカーテン塗布にて塗工する工程を含む、印刷用塗工紙の製造方法が記載されている。しかしながら、前記製造方法は印刷用紙への塗工に用いられる方法であり、粘着テープの製造においては、塗工膜（すなわち、粘着層）の厚みを大きくする必要があるため、乾燥速度が遅くなり、塗工液の裏抜けが発生するという問題がある。 As a method for forming a coating layer by directly applying a water-based coating liquid to the surface of a porous body, for example, Patent Document 1 describes an aqueous solution containing a polycarboxylic acid-based copolymer having a specific molecular weight on paper. A method for producing coated paper for printing, which includes a step of coating the surface of a base material by applying a curtain, is described. However, the manufacturing method is a method used for coating on printing paper, and in manufacturing an adhesive tape, it is necessary to increase the thickness of the coating film (that is, the adhesive layer), so that the drying speed becomes slow. , There is a problem that strike-through of the coating liquid occurs.
　不織布からなる基材上に粘着層を形成する方法としては、前述の裏抜けを防止する観点から、高粘度ホットメルトを用いて、剥離紙等の別のシート上に塗工液を一旦塗布し、その後基材上に転写する、転写塗布での塗工が一般的に行われている。しかしながら、剥離紙を用いた転写塗工は基材の不織布との密着性が低く（すなわち、保持力が低い）、再剥離性を要求される分野の粘着テープの製造には適さないという問題がある。また、ホットメルトで形成された粘着層は耐熱性が低いという問題もある。そのため、製造時に基材からの裏抜けを抑制でき、高い耐熱性及び再剥離性を有する粘着テープを提供できる、粘着テープの製造方法が求められている。 As a method of forming an adhesive layer on a base material made of a non-woven fabric, from the viewpoint of preventing strike-through described above, a coating liquid is once applied onto another sheet such as a release paper using a high-viscosity hot melt. After that, the coating is generally performed by transfer coating, which is transferred onto the substrate. However, the transfer coating using a release paper has a problem that the adhesion to the non-woven fabric of the base material is low (that is, the holding power is low) and it is not suitable for manufacturing an adhesive tape in a field where re-peelability is required. is there. Another problem is that the adhesive layer formed by hot melt has low heat resistance. Therefore, there is a demand for a method for producing an adhesive tape, which can suppress strike-through from the base material during production and can provide an adhesive tape having high heat resistance and removability.
国際公開第２０１１／１１５１６７号公報International Publication No. 2011/115167
　本発明は、不織布からなる基材に水系塗工液を直接塗布して粘着層を形成する、粘着テープの製造方法であって、製造時の裏抜けを防止でき、高い耐熱性及び再剥離性を有する粘着テープが得られる粘着テープの製造方法を提供することを目的とする。 The present invention is a method for manufacturing an adhesive tape in which a water-based coating liquid is directly applied to a base material made of a non-woven fabric to form an adhesive layer, which can prevent strike-through during manufacturing, and has high heat resistance and removability. It is an object of the present invention to provide a method for producing an adhesive tape for obtaining an adhesive tape having the above.
　上記課題に対して、本願発明者らは鋭意検討した結果、水系エマルジョンと、特定の分子量を有するポリカルボン酸系重合体とを含み、かつ特定の粘度を有する粘着剤塗工液を用いて、ロール塗工にて不織布上に粘着層を形成する工程を有する製造方法にて、前記課題を解決できることを見出し、本発明を完成させるに至った。
　すなわち、本発明は、以下の態様を有する。
［１］不織布からなる基材と、粘着層とを有する粘着テープの製造方法であって、水系エマルジョンと、重量平均分子量が４００万～３０００万のポリカルボン酸系重合体とを含み、Ｂ型粘度計を用いて６０ｒｐｍで測定した粘度が６０００～２００００ｍＰａ・ｓ／２３℃である粘着剤塗工液を、前記基材上にロール塗工にて塗工して前記粘着層を形成する工程を含む、粘着テープの製造方法。
［２］前記粘着剤塗工液を調製する工程をさらに含む、［１］に記載の粘着テープの製造方法。
［３］前記粘着剤塗工液が水を含む、［１］又は［２］に記載の粘着テープの製造方法。
［４］前記粘着層の厚みが１５μｍ以上である、［１］から［３］のいずれか一項に記載の粘着テープの製造方法。
［５］前記ポリカルボン酸系重合体が、カルボキシ基を含有するモノマーの誘導体の重合体である、［１］から［４］のいずれか一項に記載の粘着テープの製造方法。
［６］前記カルボキシ基を含有するモノマーの誘導体が、アクリルアミドである、［５］に記載の粘着テープの製造方法。
［７］前記不織布が、スパンボンド不織布である、［１］から［６］のいずれか一項に記載の粘着テープの製造方法。 As a result of diligent studies on the above problems, the inventors of the present application have used a pressure-sensitive adhesive coating solution containing an aqueous emulsion and a polycarboxylic acid-based polymer having a specific molecular weight and having a specific viscosity. We have found that the above problems can be solved by a manufacturing method having a step of forming an adhesive layer on a non-woven fabric by roll coating, and have completed the present invention.
That is, the present invention has the following aspects.
[1] A method for producing an adhesive tape having a base material made of a non-woven fabric and an adhesive layer, which comprises an aqueous emulsion and a polycarboxylic acid polymer having a weight average molecular weight of 4 to 30 million, and is of type B. A step of forming the adhesive layer by applying a pressure-sensitive adhesive coating liquid having a viscosity of 6000 to 20000 mPa · s / 23 ° C. measured at 60 rpm using a viscometer on the substrate by roll coating. Method of manufacturing adhesive tape, including.
[2] The method for producing an adhesive tape according to [1], further comprising a step of preparing the pressure-sensitive adhesive coating liquid.
[3] The method for producing an adhesive tape according to [1] or [2], wherein the adhesive coating liquid contains water.
[4] The method for producing an adhesive tape according to any one of [1] to [3], wherein the thickness of the adhesive layer is 15 μm or more.
[5] The method for producing an adhesive tape according to any one of [1] to [4], wherein the polycarboxylic acid-based polymer is a polymer of a derivative of a monomer containing a carboxy group.
[6] The method for producing an adhesive tape according to [5], wherein the derivative of the monomer containing a carboxy group is acrylamide.
[7] The method for producing an adhesive tape according to any one of [1] to [6], wherein the nonwoven fabric is a spunbonded nonwoven fabric.
　本発明によれば、不織布からなる基材に水系塗工液を直接塗布して粘着層を形成する、粘着テープの製造方法であって、製造時の裏抜けを防止でき、高い耐熱性及び再剥離性を有する粘着テープが得られる粘着テープの製造方法を提供できる。 According to the present invention, it is a method for manufacturing an adhesive tape in which a water-based coating liquid is directly applied to a base material made of a non-woven fabric to form an adhesive layer. It is possible to provide a method for producing an adhesive tape, which can obtain an adhesive tape having peelability.
　以下、本発明を詳細に説明するが、本発明は以下の態様に限定されるものではない。
［粘着テープの製造方法］
　本発明は、不織布からなる基材と、粘着層とを有する粘着テープの製造方法であって、水系エマルジョンと、重量平均分子量が４００万～３０００万のポリカルボン酸系重合体とを含み、Ｂ型粘度計を用いて６０ｒｐｍで測定した粘度が６０００～２００００ｍＰａ・ｓ／２３℃である粘着剤塗工液を、前記基材上にロール塗工にて塗工して粘着層を形成する工程を含むことを特徴とする。
　なお、本明細書において、「水系」とは、水中に油状成分が分散していることを意味する。また、「水系エマルジョン」には、適切に選択された粘着付与剤や可塑剤が均一に分散していてもよい。 Hereinafter, the present invention will be described in detail, but the present invention is not limited to the following aspects.
[Manufacturing method of adhesive tape]
The present invention is a method for producing an adhesive tape having a base material made of a non-woven fabric and an adhesive layer, which comprises an aqueous emulsion and a polycarboxylic acid polymer having a weight average molecular weight of 4 to 30 million. A step of forming an adhesive layer by applying a pressure-sensitive adhesive coating liquid having a viscosity of 6000 to 20000 mPa · s / 23 ° C. measured at 60 rpm using a mold viscometer on the substrate by roll coating. It is characterized by including.
In addition, in this specification, "water system" means that an oil component is dispersed in water. Further, an appropriately selected tackifier or plasticizer may be uniformly dispersed in the "aqueous emulsion".
＜粘着層＞
　本発明の粘着層は、水系エマルジョンと、重量平均分子量が４００万～３０００万のポリカルボン酸系重合体とを含み、Ｂ型粘度計を用いて６０ｒｐｍで測定した粘度が６０００～２００００ｍＰａ・ｓ／２３℃である粘着剤塗工液を、前記基材上にロール塗工にて塗工して形成される。 <Adhesive layer>
The adhesive layer of the present invention contains an aqueous emulsion and a polycarboxylic acid-based polymer having a weight average molecular weight of 4 to 30 million, and has a viscosity of 6000 to 20000 mPa · s / measured at 60 rpm using a B-type viscometer. A pressure-sensitive adhesive coating liquid at 23 ° C. is applied onto the substrate by roll coating to form the substrate.
（粘着剤塗工液）
　本発明において、粘着剤塗工液は、水系エマルジョンと、重量平均分子量が４００万～３０００万のポリカルボン酸系重合体とを含むものである。また、前記粘着剤塗工液のＢ型粘度計を用いて６０ｒｐｍの条件で測定した粘度は、６０００～２００００ｍＰａ・ｓ／２３℃である。このような粘着剤塗工液を用いることで、塗工液が基材の裏側から染み出る、裏抜けの現象を防止することができる。また、前記粘着剤塗工液は耐熱性が高いため、本発明の製造方法で得られる粘着テープは高い耐熱性を有する。さらに、前記粘着剤塗工液は基材に対する保持力も高いため、得られる粘着テープは再剥離性も有している。 (Adhesive coating liquid)
In the present invention, the pressure-sensitive adhesive coating liquid contains an aqueous emulsion and a polycarboxylic acid-based polymer having a weight average molecular weight of 4 to 30 million. The viscosity of the pressure-sensitive adhesive coating solution measured at 60 rpm using a B-type viscometer is 6000 to 20000 mPa · s / 23 ° C. By using such an adhesive coating liquid, it is possible to prevent the phenomenon of strike-through in which the coating liquid seeps out from the back side of the base material. Further, since the pressure-sensitive adhesive coating liquid has high heat resistance, the pressure-sensitive adhesive tape obtained by the production method of the present invention has high heat resistance. Further, since the pressure-sensitive adhesive coating liquid has a high holding power against the base material, the obtained pressure-sensitive adhesive tape also has removability.
　（水系エマルジョン）
　本発明の水系エマルジョンとは、分散媒である水中にゴム粒子が分散しているもの（いわゆる、ラテックス）、分散媒である水中に熱可塑性エラストマー粒子が分散しているもの、又は分散媒である水中にアクリル系ポリマーが分散しているものを意味している。すなわち、本発明の水系エマルジョンには、ラテックスも含まれる。
　ラテックスは、天然ゴムラテックスであってもよく、合成ゴムラテックスであってもよい。また、ラテックス中の固形分は、例えば、５０～９９質量％が好ましく、６０～９０質量％がより好ましい。
　このようなラテックスとしては、市販されているものを用いてもよく、例えば、天然ラテックスとしては、ＫＵＡＬＡ　ＬＵＭＰＵＲ　ＫＥＰＯＮＧ　ＢＥＲＨＡＤ製の商品名「ＥＸＣＥＬＴＥＸ－ＨＬＸ　ＬＡ－ＴＺ」、（株）レジテックス製の商品名「ＴＲＨ－７０」等が挙げられる。また、合成ラテックスとしては、ムサシノケミカル（株）製の商品名「ＭＧ３０」、日本ゼオン（株）製の商品名「Ｎｉｐｏｌ（登録商標）　ＬＸ４３０」等が挙げられる。これらは１種単独で用いてもよく、２種以上を組み合わせて用いてもよい。
　さらに、アクリル系ポリマーとしては、例えば、ブチルアクリレート、２－エチルヘキシルアクリレート、アクリル酸等のモノマーを任意の割合で重合したポリマーを使用することができる。
　また、熱可塑性エラストマーのエマルジョンとしては、例えば、ＪＳＲ（株）製の商品名「ＪＳＲ　ＤＹＮＡＲＯＮ（登録商標）１３２１Ｐ」等が挙げられる。
　本発明の１つの態様において、水系エマルジョンは、ラテックスであることが好ましく、天然ラテックスと合成ラテックスとの混合物であることがより好ましい。また、その配合比（天然ラテックス／合成ラテックス）は、３／７～７／３が好ましい。前記混合物を用いることで粘着層の強度と粘着力のバランスを得られやすくなる。
　また、水系エマルジョンの粘度は、Ｂ型粘度計を用いて測定した値が、１０～３００ｍＰａ・ｓ／２３℃であることが好ましく、５０～２００ｍＰａ・ｓ／２３℃であることがより好ましい。 (Aqueous emulsion)
The aqueous emulsion of the present invention is one in which rubber particles are dispersed in water as a dispersion medium (so-called latex), one in which thermoplastic elastomer particles are dispersed in water as a dispersion medium, or a dispersion medium. It means that the acrylic polymer is dispersed in water. That is, the aqueous emulsion of the present invention also contains latex.
The latex may be a natural rubber latex or a synthetic rubber latex. The solid content in the latex is, for example, preferably 50 to 99% by mass, more preferably 60 to 90% by mass.
As such a latex, a commercially available latex may be used. For example, as a natural latex, a product name "EXCELTEX-HLX LA-TZ" manufactured by KUALA LUMPUR KEPONG BERHAD, a product manufactured by Regitex Co., Ltd. Examples include the name "TRH-70". Examples of the synthetic latex include a trade name "MG30" manufactured by Musashino Chemical Co., Ltd., a trade name "Nipol (registered trademark) LX430" manufactured by Nippon Zeon Corporation, and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.
Further, as the acrylic polymer, for example, a polymer obtained by polymerizing a monomer such as butyl acrylate, 2-ethylhexyl acrylate, or acrylic acid at an arbitrary ratio can be used.
Examples of the thermoplastic elastomer emulsion include the trade name "JSR DYNARON (registered trademark) 1321P" manufactured by JSR Corporation.
In one embodiment of the invention, the aqueous emulsion is preferably latex, more preferably a mixture of natural latex and synthetic latex. The blending ratio (natural latex / synthetic latex) is preferably 3/7 to 7/3. By using the mixture, it becomes easy to obtain a balance between the strength of the adhesive layer and the adhesive strength.
The viscosity of the aqueous emulsion is preferably 10 to 300 mPa · s / 23 ° C., more preferably 50 to 200 mPa · s / 23 ° C., as measured with a B-type viscometer.
　本発明の１つの態様において、粘着剤塗工液中の水系エマルジョンの割合は、粘着剤塗工液の総質量に対して、５～７０量％が好ましく、１５～５０質量％がより好ましい。粘着剤塗工液中の水系エマルジョンの割合が前記範囲内であれば、塗布時に表面の皮張りの問題がなく、かつ乾燥時間を適切な範囲に調整しやすくなる。 In one aspect of the present invention, the proportion of the water-based emulsion in the pressure-sensitive adhesive coating liquid is preferably 5 to 70% by mass, more preferably 15 to 50% by mass, based on the total mass of the pressure-sensitive adhesive coating liquid. When the ratio of the water-based emulsion in the pressure-sensitive adhesive coating liquid is within the above range, there is no problem of surface skinning during coating, and it becomes easy to adjust the drying time to an appropriate range.
　（ポリカルボン酸系重合体）
　本発明において、ポリカルボン酸系重合体とは、カルボキシ基を含有するモノマー（Ａ）（以下、単に「モノマー（Ａ）」と記載することもある）、又は前記モノマー（Ａ）の誘導体（Ｉ）（以下、単に「誘導体（Ｉ）」と記載することもある）を重合して得られる重合体を意味する。また、本発明の１つの態様においては、ポリカルボン酸系重合体は、前記モノマー（Ａ）及び前記誘導体（Ｉ）からなる群より選択される少なくとも１つを含むモノマー（Ｘ）を重合して得られる共重合体であってもよい。
　モノマー（Ａ）としては、例えば、アクリル酸、マレイン酸、及びメタクリル酸等が挙げられる。このうち、溶解性の観点から、前記モノマー（Ａ）としては、アクリル酸、メタクリル酸が好ましく、アクリル酸がより好ましい。
　また、誘導体（Ｉ）としては、例えば、前記モノマー（Ａ）の、モノ又はジアルカリ土類金属塩、モノ又はジエステル、アミド、イミド、及び無水物等が挙げられる。このうち、水溶性付与の観点から、前記誘導体（Ｉ）としては、前記モノマー（Ａ）のモノ又はジアルカリ土類金属、又は前記モノマー（Ａ）のアミドが好ましく、前記モノマー（Ａ）のアミドがより好ましい。
　本発明の１つ態様において、ポリカルボン酸系重合体は、カルボキシ基を含有するモノマー（Ａ）の誘導体（Ｉ）の重合体であることが好ましい。また、前記誘導体（Ｉ）としては、アクリル酸ナトリウム、又はアクリルアミドであることが特に好ましい。誘導体（Ｉ）の重合体であることにより、裏抜け防止の効果が得られやすくなる。 (Polycarboxylic acid polymer)
In the present invention, the polycarboxylic acid-based polymer is a monomer (A) containing a carboxy group (hereinafter, may be simply referred to as "monomer (A)") or a derivative (I) of the monomer (A). ) (Hereinafter, it may be simply referred to as “derivative (I)”) to mean a polymer obtained by polymerizing. Further, in one aspect of the present invention, the polycarboxylic acid-based polymer polymerizes a monomer (X) containing at least one selected from the group consisting of the monomer (A) and the derivative (I). It may be the obtained copolymer.
Examples of the monomer (A) include acrylic acid, maleic acid, and methacrylic acid. Of these, from the viewpoint of solubility, the monomer (A) is preferably acrylic acid or methacrylic acid, and more preferably acrylic acid.
In addition, examples of the derivative (I) include mono or dialkali earth metal salts, mono or diesters, amides, imides, and anhydrides of the monomer (A). Of these, from the viewpoint of imparting water solubility, the derivative (I) is preferably a monomer or a dialkalis earth metal of the monomer (A), or an amide of the monomer (A), and the amide of the monomer (A) is preferable. More preferred.
In one aspect of the present invention, the polycarboxylic acid-based polymer is preferably a polymer of a derivative (I) of a monomer (A) containing a carboxy group. Further, the derivative (I) is particularly preferably sodium acrylate or acrylamide. Since it is a polymer of the derivative (I), the effect of preventing strike-through can be easily obtained.
　本発明のポリカルボン酸系重合体の重量平均分子量は、４００万～３０００万であり、５００万～２０００万であることがより好ましい。ポリカルボン酸系重合体の重量平均分子量が前記範囲内であれば、裏抜け防止の効果が得られる。なお、前記重量平均分子量は、ゲルパーミエーションクロマトグラフィ（ＧＰＣ）を用いて測定した値のことを指す。具体的には、ＧＰＣ測定を行い、以下の条件にて単分散ポリスチレンの溶出曲線より各溶出時間における分子量を算出し、ポリスチレン換算の分子量として算出する。
＜測定条件＞
　機種：昭和電工株式会社製　商品名：「Ｓｈｏｄｅｘ　ＧＰＣ－１０１」
　カラム：ポリマーラボラトリーズ社製　ＰＬｇｅｌ　１０μｍ　ＭＩＸＥＤ－Ａ
　移動相：テトラヒドロフラン
　試料濃度：０．２質量％
　温度：オーブン４０℃、注入口３５℃、検出器３５℃
　検出器：示差屈折計 The weight average molecular weight of the polycarboxylic acid-based polymer of the present invention is 4 million to 30 million, more preferably 5 million to 20 million. When the weight average molecular weight of the polycarboxylic acid-based polymer is within the above range, the effect of preventing strike-through can be obtained. The weight average molecular weight refers to a value measured by gel permeation chromatography (GPC). Specifically, GPC measurement is performed, the molecular weight at each elution time is calculated from the elution curve of monodisperse polystyrene under the following conditions, and the molecular weight is calculated as polystyrene-equivalent molecular weight.
<Measurement conditions>
Model: Showa Denko KK Product name: "Shodex GPC-101"
Column: Polymer Laboratories PLgel 10 μm MIXED-A
Mobile phase: tetrahydrofuran Sample concentration: 0.2% by mass
Temperature: Oven 40 ° C, inlet 35 ° C, detector 35 ° C
Detector: Differential refractometer
　本発明の１つの態様において、粘着剤塗工液中のポリカルボン酸系重合体の割合は、前記水系エマルジョンの合計量（１００質量部）に対して、０．１～３質量部が好ましく、０．５～２質量部がより好ましい。
　また、本発明の１つの態様においては、粘着剤塗工液中の前記ポリカルボン酸系重合体の割合は、粘着剤塗工液の総質量に対して、５質量％以下が好ましく、１質量％以下がより好ましい。
　粘着剤塗工液中のポリカルボン酸系重合体の割合が前記範囲内であれば、裏抜け防止の効果が得られやすくなり、粘着強度が向上しやすい。 In one aspect of the present invention, the ratio of the polycarboxylic acid-based polymer in the pressure-sensitive adhesive coating liquid is preferably 0.1 to 3 parts by mass with respect to the total amount (100 parts by mass) of the aqueous emulsion. More preferably 0.5 to 2 parts by mass.
Further, in one aspect of the present invention, the ratio of the polycarboxylic acid-based polymer in the pressure-sensitive adhesive coating liquid is preferably 5% by mass or less, preferably 1% by mass, based on the total mass of the pressure-sensitive adhesive coating liquid. % Or less is more preferable.
When the ratio of the polycarboxylic acid-based polymer in the pressure-sensitive adhesive coating liquid is within the above range, the effect of preventing strike-through can be easily obtained and the pressure-sensitive adhesive strength can be easily improved.
　（粘着付与剤）
　本発明の１つの態様において、粘着剤塗工液中には、本発明の効果を損なわない範囲で、粘着付与剤が含まれていてもよい。粘着付与剤としては、例えば、脂肪族系共重合体、芳香族系共重合体、脂肪族・芳香族系共重合体系や脂環式系共重合体等の石油系樹脂、クマロン－インデン系樹脂、テルペン系樹脂、テルペンフェノール系樹脂、重合ロジン等のロジン系樹脂、（アルキル）フェノール系樹脂、キシレン系樹脂又はこれらの水添物等が挙げられる。これらは１種単独で用いてもよく、２種以上を組み合わせて用いてもよい。
　粘着付与剤としては、コスト、着色低の観点から、テルペンフェノール樹脂、石油樹脂（Ｃ５～Ｃ９系石油樹脂、又はＣ５系石油樹脂）が好ましい。また、これら粘着付与剤は、エマルジョンであってもよい。
　また、粘着剤塗工液中の粘着付与剤の割合は、粘着剤塗工液の総質量に対して、２０～８０質量％が好ましく、２０～５０質量％がより好ましい。粘着付与剤の割合が前記範囲内であれば、粘着性付与の効果が得られやすくなる。 (Adhesive agent)
In one aspect of the present invention, the pressure-sensitive adhesive coating liquid may contain a pressure-sensitive adhesive as long as the effects of the present invention are not impaired. Examples of the tackifier include petroleum resins such as aliphatic copolymers, aromatic copolymers, aliphatic / aromatic copolymers and alicyclic copolymers, and kumaron-inden resins. , Terpene-based resin, terpene-phenol-based resin, rosin-based resin such as polymerized rosin, (alkyl) phenol-based resin, xylene-based resin, and hydrogenated products thereof. These may be used individually by 1 type, and may be used in combination of 2 or more type.
As the tackifier, a terpene phenol resin or a petroleum resin (C5 to C9 petroleum resin or C5 petroleum resin) is preferable from the viewpoint of cost and low coloring. Further, these tackifiers may be emulsions.
The proportion of the tackifier in the pressure-sensitive adhesive coating liquid is preferably 20 to 80% by mass, more preferably 20 to 50% by mass, based on the total mass of the pressure-sensitive adhesive coating liquid. When the ratio of the tackifier is within the above range, the effect of imparting tackiness can be easily obtained.
　（界面活性剤）
　本発明の１つの態様において、粘着剤塗工液中には、本発明の効果を損なわない範囲で、界面活性剤が含まれていてもよい。
　界面活性剤としては、例えば、アニオン性界面活性剤、カチオン性界面活性剤、ノニオン性界面活性剤等が挙げられる。本発明においては、溶解性が高く、乾燥時の塗布不良（ハジキ等）が少ないことから、アニオン性界面活性剤であることが好ましい。アニオン性界面活性剤としては、例えば、スルホン酸系界面活性剤、硫酸エステル系界面活性剤、カルボン酸系界面活性剤等が挙げられる。このうち、溶解性の観点から、スルホン酸系界面活性剤がより好ましい。
　また、粘着剤塗工液中の界面活性剤の割合は、粘着力を低下させない観点から、粘着剤塗工液の総質量に対して、４質量％以下が好ましく、１質量％以下がより好ましい。 (Surfactant)
In one aspect of the present invention, the pressure-sensitive adhesive coating liquid may contain a surfactant as long as the effects of the present invention are not impaired.
Examples of the surfactant include anionic surfactants, cationic surfactants, nonionic surfactants and the like. In the present invention, an anionic surfactant is preferable because it has high solubility and few coating defects (such as repellent) during drying. Examples of the anionic surfactant include sulfonic acid-based surfactants, sulfate ester-based surfactants, carboxylic acid-based surfactants, and the like. Of these, a sulfonic acid-based surfactant is more preferable from the viewpoint of solubility.
The proportion of the surfactant in the pressure-sensitive adhesive coating liquid is preferably 4% by mass or less, more preferably 1% by mass or less, based on the total mass of the pressure-sensitive adhesive coating liquid, from the viewpoint of not reducing the adhesive strength. ..
　（その他の添加剤）
　本発明の粘着剤塗工液には、本発明の効果を損なわない範囲において、その他の添加剤が含まれていてもよい。その他の添加剤としては、例えば、増粘剤、軟化剤、表面潤滑剤、レベリング剤、酸化防止剤、腐食防止剤、光安定剤、紫外線吸収剤、耐熱安定剤、重合禁止剤、シランカップリンング剤、滑剤、無機又は有機の充填剤、金属粉、顔料等が挙げられる。これらは１種単独で用いてもよく、２種以上を組み合わせて用いてもよい。 (Other additives)
The pressure-sensitive adhesive coating liquid of the present invention may contain other additives as long as the effects of the present invention are not impaired. Other additives include, for example, thickeners, softeners, surface lubricants, leveling agents, antioxidants, corrosion inhibitors, light stabilizers, UV absorbers, heat stabilizers, polymerization inhibitors, silane cuprins. Examples include lubricants, lubricants, inorganic or organic fillers, metal powders, pigments and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.
　増粘剤としては、例えば、水溶性高分子増粘剤、会合型増粘剤等が挙げられる。このうち、粘着剤塗工液の粘度の安定性の観点から、水溶性高分子増粘剤が好ましい。また、粘着剤塗工液が増粘剤を含む場合、その配合量は、粘着剤塗工液の総質量に対して、０．１～４質量％が好ましい。 Examples of the thickener include a water-soluble polymer thickener, an association type thickener, and the like. Of these, a water-soluble polymer thickener is preferable from the viewpoint of the stability of the viscosity of the pressure-sensitive adhesive coating liquid. When the pressure-sensitive adhesive coating liquid contains a thickener, the blending amount thereof is preferably 0.1 to 4% by mass with respect to the total mass of the pressure-sensitive adhesive coating liquid.
　粘着剤塗工液が前記のその他の添加剤を含む場合、その他の添加剤の合計の配合量は、粘着剤塗工液の総質量に対して、０．１～１０質量％が好ましく、０．５～８質量％がより好ましい。 When the pressure-sensitive adhesive coating liquid contains the above-mentioned other additives, the total blending amount of the other additives is preferably 0.1 to 10% by mass, preferably 0, based on the total mass of the pressure-sensitive adhesive coating liquid. .5 to 8% by mass is more preferable.
　（溶剤）
　本発明の粘着剤塗工液は、水を含むことが好ましい。水は、粘着剤塗工液の粘度を調整するために配合される。従って、粘着剤塗工液中の水の割合は、粘着剤塗工液の粘度が、前述の範囲内となるように適宜調整される。水としては、純水が好ましい。 (solvent)
The pressure-sensitive adhesive coating liquid of the present invention preferably contains water. Water is added to adjust the viscosity of the adhesive coating solution. Therefore, the proportion of water in the pressure-sensitive adhesive coating liquid is appropriately adjusted so that the viscosity of the pressure-sensitive adhesive coating liquid is within the above range. Pure water is preferable as water.
　本発明の粘着剤塗工液は、Ｂ型粘度計を用いて６０ｒｐｍの条件で測定した粘度が、６０００～２００００ｍＰａ・ｓ／２３℃であり、８０００～１４０００ｍＰａ・ｓ／２３℃であることが好ましい。粘着剤塗工液の粘度を前記範囲内とすることで、基材からの裏抜けを防止することができる。
　粘着剤塗工液の２３℃における粘度は、Ｂ型粘度計を用いて、６０ｒｐｍの回転速度で測定される。また、Ｂ型粘度計としては、ＢＲＯＯＫＦＩＥＬＤ製のＬＶ－３のローターを用いる。 The pressure-sensitive adhesive coating liquid of the present invention has a viscosity of 6000 to 20000 mPa · s / 23 ° C., preferably 8000 to 14000 mPa · s / 23 ° C., measured under the condition of 60 rpm using a B-type viscometer. .. By setting the viscosity of the pressure-sensitive adhesive coating liquid within the above range, strike-through from the base material can be prevented.
The viscosity of the pressure-sensitive adhesive coating liquid at 23 ° C. is measured at a rotation speed of 60 rpm using a B-type viscometer. Further, as the B-type viscometer, a rotor of LV-3 manufactured by BROOKFIELD is used.
　本発明の１つの態様においては、粘着層の厚みは、１５μｍ以上であることが好ましく、３０μｍ以上であることがより好ましい。粘着層の厚みが１５μｍ以上であれば、粘着テープとして十分な粘着力を発現しやすくなる。 In one aspect of the present invention, the thickness of the adhesive layer is preferably 15 μm or more, more preferably 30 μm or more. When the thickness of the adhesive layer is 15 μm or more, it becomes easy to develop sufficient adhesive force as an adhesive tape.
＜基材＞
　本発明の基材は、不織布からなる。すなわち、「不織布からなる基材」とは、不織布を構成する繊維を織らずに組み合わせたシート状の基材のことを意味する。
　前記不織布としては、例えば、スパンボンド法で作成された不織布、スパンレース法で作成された不織布、メルトブロー法で作成された不織布等を用いることができる。また、不織布は単層であってもよく、複数の層からなる積層不織布であってもよい。また積層不織布の場合、複数の方法で作成された不織布を積層させたものであってもよい。このうち、基材の強度の観点から、スパンボンド法で作成された不織布（スパンボンド不織布）を用いることが好ましい。スパンボンド不織布からなる基材を用いることで、被着体の保護性が高いテープが得られやすくなる。 <Base material>
The base material of the present invention is made of a non-woven fabric. That is, the "base material made of non-woven fabric" means a sheet-like base material in which fibers constituting the non-woven fabric are combined without weaving.
As the non-woven fabric, for example, a non-woven fabric produced by the spunbond method, a non-woven fabric produced by the spunlace method, a non-woven fabric produced by the melt blow method, or the like can be used. Further, the non-woven fabric may be a single layer or a laminated non-woven fabric composed of a plurality of layers. Further, in the case of a laminated non-woven fabric, the non-woven fabrics produced by a plurality of methods may be laminated. Of these, from the viewpoint of the strength of the base material, it is preferable to use a non-woven fabric (spun-bonded non-woven fabric) prepared by the spunbond method. By using a base material made of a spunbonded non-woven fabric, it becomes easy to obtain a tape having high protection of the adherend.
　不織布の目付は、５０～１５０ｇ／ｍ２であるものが好ましく、７０～１２０ｇ／ｍ２であるものがより好ましい。また、その空隙率としては、３０～９０％が好ましい。
　不織布を構成する繊維としては、本発明の効果を有する限り特に限定されず、例えば、アラミド繊維、ガラス繊維、セルロース繊維、ナイロン繊維、ビニロン繊維、ポリエステル繊維、ポリオレフィン繊維、レーヨン繊維等が挙げられる。これらは１種単独で用いられてもよく、２種以上を組み合わせて用いてもよい。このうち、耐熱性、耐久性の観点から、ポリエステル繊維が好ましい。
　不織布を構成する繊維の繊維径は、基材の強度の観点から、３～５０μｍが好ましく、４～３０μｍがより好ましい。不織布の繊維径が前記範囲内であれば、消音の効果が得られやすくなる。 The basis weight of the non-woven fabric is preferably 50 to 150 g / m 2 , and more preferably 70 to 120 g / m 2 . The porosity is preferably 30 to 90%.
The fibers constituting the non-woven fabric are not particularly limited as long as they have the effects of the present invention, and examples thereof include aramid fibers, glass fibers, cellulose fibers, nylon fibers, vinylon fibers, polyester fibers, polyolefin fibers, rayon fibers and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type. Of these, polyester fiber is preferable from the viewpoint of heat resistance and durability.
The fiber diameter of the fibers constituting the non-woven fabric is preferably 3 to 50 μm, more preferably 4 to 30 μm, from the viewpoint of the strength of the base material. When the fiber diameter of the non-woven fabric is within the above range, the sound deadening effect can be easily obtained.
　基材の厚みは、その取り扱いの観点から、２００～７００μｍであることが好ましく、２５０～３５０μｍであることがより好ましい。 The thickness of the base material is preferably 200 to 700 μm, more preferably 250 to 350 μm from the viewpoint of its handling.
＜製造工程＞
　本発明の粘着テープの製造方法は、前述の粘着剤塗工液を、前記基材上にロール塗工、好ましくはコンマリバース塗工にて塗工して粘着層を形成する工程（以下、「粘着層形成工程」と記載することもある）を含む。塗工条件としては、不織布からなる基材の一方の表面に、前記粘着剤塗工液を３０ｍ／ｓｅｃ、乾燥条件１３０℃で塗工することが好ましい。
　粘着層形成工程において、粘着剤塗工液は、２０～３０℃に温調されたものを用いることが好ましい。 <Manufacturing process>
The method for producing an adhesive tape of the present invention is a step of forming an adhesive layer by applying the above-mentioned adhesive coating liquid on the base material by roll coating, preferably comma reverse coating (hereinafter, "" It may also be described as "adhesive layer forming step"). As the coating conditions, it is preferable to coat one surface of the base material made of a non-woven fabric with the adhesive coating liquid at 30 m / sec and a drying condition of 130 ° C.
In the pressure-sensitive adhesive layer forming step, it is preferable to use a pressure-adjusted pressure-sensitive adhesive coating liquid at 20 to 30 ° C.
　また、前記粘着層形成工程は、前記粘着剤塗工液を、前記基材上にロール塗工にて塗工し、厚みが１５μｍ以上の粘着層を形成する工程であることが好ましい。前記粘着層は、単層であってもよく、多層であってもよい。本発明の１つの態様においては、前記粘着層形成工程は、前記粘着剤塗工液を、前記基材上にロール塗工、好ましくはコンマリバース塗工にて塗工し、厚みが１５μｍ以上の粘着層を単層で形成する工程であることがより好ましい。本発明の粘着剤塗工液は、前述の通り、水系エマルジョンと、特定の分子量を有するポリカルボン酸系重合体とを含み、かつ特定の粘度を有しているため、１５μｍ以上の厚みを有する粘着層を１段階で形成しても、裏抜けが生じにくい。 Further, the pressure-sensitive adhesive layer forming step is preferably a step of applying the pressure-sensitive adhesive coating liquid on the base material by roll coating to form a pressure-sensitive adhesive layer having a thickness of 15 μm or more. The adhesive layer may be a single layer or a multi-layer. In one aspect of the present invention, in the pressure-sensitive adhesive layer forming step, the pressure-sensitive adhesive coating liquid is applied onto the substrate by roll coating, preferably comma reverse coating, and has a thickness of 15 μm or more. It is more preferable that the step is to form the adhesive layer as a single layer. As described above, the pressure-sensitive adhesive coating liquid of the present invention contains an aqueous emulsion and a polycarboxylic acid-based polymer having a specific molecular weight, and has a specific viscosity, so that it has a thickness of 15 μm or more. Even if the adhesive layer is formed in one step, strike-through is unlikely to occur.
　また、本発明の１つの態様においては、前記粘着層形成工程の前に、前記粘着剤塗工液を調製する工程を含んでいてもよい。
　粘着剤塗工液を調製する工程（以下、「塗工液調製工程」と記載することもある）としては、例えば、前記水系エマルジョン及び前記ポリカルボン酸系重合体の他、粘着付与剤、界面活性剤、及びその他の添加剤等を適宜選択して配合して混合した後、純水を添加して、前述の粘度範囲内となるように粘着剤塗工液を調製する工程が挙げられる。また、各主成分の配合順序は任意である。 Further, in one aspect of the present invention, the step of preparing the pressure-sensitive adhesive coating liquid may be included before the step of forming the pressure-sensitive adhesive layer.
Examples of the step of preparing the pressure-sensitive adhesive coating liquid (hereinafter, also referred to as “coating liquid preparation step”) include the aqueous emulsion and the polycarboxylic acid polymer, as well as a tackifier and a surfactant. Examples thereof include a step of appropriately selecting, blending and mixing an activator, other additives and the like, and then adding pure water to prepare an adhesive coating liquid so as to be within the above-mentioned viscosity range. In addition, the blending order of each main component is arbitrary.
＜評価方法＞
（基材からの裏抜け評価）
　本発明の粘着テープの製造方法は、粘着層形成時の基材からの裏抜けを防止できる。
　基材からの裏抜けの有無については、以下に示す手順に従って評価することができる。
　作製した粘着テープを液体窒素中に１分間浸漬させて浸潤させる。その後、粘着テープを垂直にカットする。粘着テープの断面をレーザー顕微鏡で観察し、粘着剤が基材の背面まで浸潤していないかどうかを確認する。 <Evaluation method>
(Evaluation of strike-through from the base material)
The method for producing an adhesive tape of the present invention can prevent strike-through from the base material when the adhesive layer is formed.
The presence or absence of strike-through from the base material can be evaluated according to the procedure shown below.
The prepared adhesive tape is immersed in liquid nitrogen for 1 minute to infiltrate. After that, the adhesive tape is cut vertically. Observe the cross section of the adhesive tape with a laser microscope to see if the adhesive has penetrated to the back of the substrate.
（耐熱性評価）
　本発明の粘着テープの製造方法は、耐熱性の高い粘着剤塗工液を用いているため、本製造方法で得られる粘着テープは耐熱性にも優れている。
　粘着テープの耐熱性は、例えば、以下に示す手順に従って評価することができる。
　ＳＡＥ　Ｊ２１９２に従って粘着テープの電線結束品（試料）を作成する。１時間に８～２０回のエア切替えが可能な熱風循環炉に試料２０本を入れる。１０５℃で試料を３０００時間暴露させる。試験手順については、ＳＡＥ　Ｊ２１９２の第７．３．３節、第７．３．４節を参照することができるが、５００時間毎、１０００時間毎に３０００時間まで試料５本を取り出す作業は除く。３０００時間経過後に４０ｍｍのマンドレルに電線結束品（試料）を巻きつけ、テープの剥れがないか確認する。 (Heat resistance evaluation)
Since the method for producing the adhesive tape of the present invention uses an adhesive coating liquid having high heat resistance, the adhesive tape obtained by the present production method is also excellent in heat resistance.
The heat resistance of the adhesive tape can be evaluated, for example, according to the procedure shown below.
A wire binding product (sample) of adhesive tape is prepared according to SAE J2192. Place 20 samples in a hot air circulation furnace that can switch air 8 to 20 times per hour. The sample is exposed at 105 ° C. for 3000 hours. For the test procedure, see Sections 7.3.3 and 7.3.4 of SAE J2192, except for the work of taking out 5 samples every 500 hours and every 1000 hours for up to 3000 hours. .. After 3000 hours have passed, wrap the wire binding product (sample) around a 40 mm mandrel and check if the tape is peeled off.
（再剥離性評価）
　本発明の粘着テープの製造方法により製造された粘着テープは、高い再剥離性を示す。粘着テープの再剥離性は、以下の通りの測定法で評価することができる。
　作製した粘着テープをステンレス板（ＳＵＳ３０４）に貼着した後、２３℃、６５％ＲＨの条件下で２４時間放置する。その後、ステンレス板から剥離し、下記式に従って再剥離性（％）を評価する。
　再剥離性（％）＝（粘着剤残りのない面積）／（貼り付けた全体の面積）×１００
　上記式において、再剥離性の値が高い（粘着剤残りのない面積が広い）ほど、再剥離性に優れる。 (Removability evaluation)
The adhesive tape produced by the method for producing an adhesive tape of the present invention exhibits high removability. The removability of the adhesive tape can be evaluated by the following measurement method.
After the prepared adhesive tape is attached to a stainless steel plate (SUS304), it is left to stand for 24 hours under the conditions of 23 ° C. and 65% RH. Then, it is peeled off from the stainless steel plate, and the re-peelability (%) is evaluated according to the following formula.
Removability (%) = (area without adhesive residue) / (total area pasted) x 100
In the above formula, the higher the removability value (the larger the area where there is no adhesive residue), the better the removability.
（粘着力評価）
　本発明の粘着テープの製造方法により得られる粘着テープの粘着力は、ＪＩＳ　Ｚ０２３７に従って評価することができる。 (Adhesive strength evaluation)
The adhesive strength of the adhesive tape obtained by the method for producing an adhesive tape of the present invention can be evaluated according to JIS Z0237.
［用途］
　前述の通り、本発明の粘着テープの製造方法によれば、不織布からなる基材に水系塗工液を直接塗布して粘着層を形成しても、基材からの裏抜けが生じない。また、耐熱性の高い粘着剤塗工液を用いて粘着層を形成しているため、本発明の製造方法により得られる粘着テープは、耐熱性が要求される分野、例えば、車のエンジンルーム等の粘着テープとして、好適に用いることができる。また、本発明の粘着剤塗工液は基材に対する保持力も高いため、得られる粘着テープは再剥離性も備えている。そのため、再剥離性が求められる分野、例えば、絶縁テープ等の粘着テープとしても、好適に用いることができる。 [Use]
As described above, according to the method for producing an adhesive tape of the present invention, even if a water-based coating liquid is directly applied to a base material made of a non-woven fabric to form an adhesive layer, strike-through from the base material does not occur. Further, since the adhesive layer is formed by using an adhesive coating liquid having high heat resistance, the adhesive tape obtained by the production method of the present invention can be used in fields where heat resistance is required, such as a car engine room. Can be suitably used as an adhesive tape of. Further, since the pressure-sensitive adhesive coating liquid of the present invention has a high holding power to the base material, the obtained pressure-sensitive adhesive tape also has removability. Therefore, it can be suitably used in fields where removability is required, for example, as an adhesive tape such as an insulating tape.
　以下、実施例を示して本発明を詳細に説明するが、本発明は以下の記載によって限定されるものではない。 Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following description.
［実施例１］
＜粘着剤塗工液の調製＞
　水系エマルジョンとして、天然ラテックス（ＫＵＡＬＡ　ＬＵＭＰＵＲ　ＫＥＰＯＮＧ　ＢＥＲＨＡＤ社製、商品名「ＥＸＣＥＬＴＥＸ－ＨＬＸ　ＬＡ－ＴＺ」）５０質量部（固形分）、合成ラテックス（ムサシノケミカル（株）製、商品名「ＭＧ３０」）５０質量部（固形分）を用い、粘着付与剤として、テルペンフェノール樹脂エマルジョン（荒川化学工業（株）製、商品名「Ｅ－２００」）３０質量部（固形分）、石油樹脂エマルジョン（荒川化学工業（株）製、商品名「ＡＰ－１１００－ＮＴ」）７０質量部（固形分）をそれぞれ添加して混合し、エマルジョン混合物を調製した。前記エマルジョン混合物に、アニオン系界面活性剤（花王（株）製、商品名「ネオペレックス（登録商法）Ｇ－２５」）２質量部（固形分）、水溶性高分子増粘剤（サンノプコ（株）製、商品名「シックナーＳＮ－８１２」）０．２質量部（固形分）、ポリカルボン酸系重合体（ポリアクリルアミド）（ソマール（株）製、商品名「ソマレックス（登録商標）５３０」、重量平均分子量２０００万）２質量部をそれぞれ添加し、純水で粘度を調整して粘着剤塗工液を得た。得られた粘着剤塗工液の粘度（Ｂ型粘度計、回転速度６０ｒｐｍ）は、１２０００ｍＰａ・ｓ／２３℃であった。粘着剤塗工液の組成を表１に示す。 [Example 1]
<Preparation of adhesive coating solution>
As an aqueous emulsion, 50 parts by mass (solid content) of natural latex (manufactured by KUALA LUMPUR KEPONG BERHAD, trade name "EXCELTEX-HLX LA-TZ"), synthetic latex (manufactured by Musashino Chemical Co., Ltd., trade name "MG30") 50 Using parts by mass (solid content), as a tackifier, terpenphenol resin emulsion (manufactured by Arakawa Chemical Industry Co., Ltd., trade name "E-200") 30 parts by mass (solid content), petroleum resin emulsion (Arakawa Chemical Industry Co., Ltd.) 70 parts by mass (solid content) of (trade name "AP-1100-NT") manufactured by Co., Ltd. was added and mixed to prepare an emulsion mixture. To the emulsion mixture, 2 parts by mass (solid content) of an anionic surfactant (manufactured by Kao Co., Ltd., trade name "Neoperex (registered commercial method) G-25"), water-soluble polymer thickener (Sannopco Co., Ltd.) ), Product name "Thickener SN-812") 0.2 parts by mass (solid content), polycarboxylic acid polymer (polyacrylamide) (manufactured by Somar Co., Ltd., product name "Somalex (registered trademark) 530", Weight average molecular weight 20 million) 2 parts by mass were added respectively, and the viscosity was adjusted with pure water to obtain a pressure-sensitive adhesive coating liquid. The viscosity of the obtained adhesive coating liquid (B-type viscometer, rotation speed 60 rpm) was 12000 mPa · s / 23 ° C. The composition of the pressure-sensitive adhesive coating liquid is shown in Table 1.
＜粘着テープの作成＞
　目付けが８０ｇ／ｍ２のスパンボンド不織布からなる基材上にコンマリバースコーターを用いて粘着剤塗工液を塗布し、１３０℃で乾燥を行った。結果、厚みが３５μｍとなるように前記粘着剤塗工液を塗工して、粘着層を形成することができた。得られた粘着テープの各種物性を以下の評価方法に従って評価した。結果を表１に示す。 <Creation of adhesive tape>
An adhesive coating liquid was applied to a substrate made of a spunbonded non-woven fabric having a basis weight of 80 g / m 2 using a comma reverse coater, and dried at 130 ° C. As a result, the pressure-sensitive adhesive coating liquid could be applied so as to have a thickness of 35 μm to form an pressure-sensitive adhesive layer. Various physical properties of the obtained adhesive tape were evaluated according to the following evaluation methods. The results are shown in Table 1.
（裏抜け評価）
　以下の評価方法に従って評価した。
　作製した粘着テープを液体窒素中に１分間浸漬させて浸潤させた。その後、粘着テープを垂直にカットした。粘着テープの断面をレーザー顕微鏡で観察し、粘着剤が基材の背面まで浸潤していないかどうかを確認した。 (Striking evaluation)
Evaluation was performed according to the following evaluation method.
The prepared adhesive tape was immersed in liquid nitrogen for 1 minute to infiltrate. Then, the adhesive tape was cut vertically. The cross section of the adhesive tape was observed with a laser microscope to confirm whether the adhesive had infiltrated the back surface of the substrate.
（耐熱性評価）
　得られた粘着テープについて、以下の評価方法に従って耐熱性を評価した。
　ＳＡＥ　Ｊ２１９２に従って粘着テープの電線結束品（試料）を作成した。１時間に８～２０回のエア切替えが可能な熱風循環炉に試料２０本を入れ、１０５℃で試料を３０００時間暴露させた。試験手順については、ＳＡＥ　Ｊ２１９２の第７．３．３節、第７．３．４節を参照したが、５００時間毎、１０００時間毎に３０００時間まで試料５本を取り出す作業は除いた。３０００時間経過後に４０ｍｍのマンドレルに電線結束品（試料）を巻きつけ、テープの剥れがないか確認した。２０試料について、以下の評価基準に従って評価した。なお、Ａ評価を合格（耐熱性が高い）とした。
　（評価基準）
　Ａ：全ての試料でテープに剥がれが生じていなかった。
　Ｂ：試料の一部にテープ剥がれが生じていた
　Ｃ：全ての試料でテープ剥がれが生じていた。 (Heat resistance evaluation)
The heat resistance of the obtained adhesive tape was evaluated according to the following evaluation method.
An electric wire bundled product (sample) of an adhesive tape was prepared according to SAE J2192. Twenty samples were placed in a hot air circulation furnace capable of switching air 8 to 20 times per hour, and the samples were exposed at 105 ° C. for 3000 hours. For the test procedure, see Sections 7.3.3 and 7.3.4 of SAE J2192, except for the work of taking out 5 samples every 500 hours and every 1000 hours for up to 3000 hours. After the lapse of 3000 hours, a wire binding product (sample) was wound around a 40 mm mandrel, and it was confirmed whether the tape was peeled off. Twenty samples were evaluated according to the following evaluation criteria. The A evaluation was passed (high heat resistance).
(Evaluation criteria)
A: There was no peeling of the tape in all the samples.
B: Tape peeling occurred in a part of the sample C: Tape peeling occurred in all the samples.
（再剥離性評価）
　作製した粘着テープをステンレス板（ＳＵＳ３０４）に貼着した後、２３℃、６５％ＲＨの条件下で２４時間放置した。その後、ステンレス板から剥離し、下記式に従って再剥離性（％）を評価した。
　再剥離性（％）＝（粘着剤残りのない面積）／（貼り付けた全体の面積）×１００
　上記式において、再剥離性の値が高い（粘着剤残りのない面積が広い）ほど、再剥離性に優れるとして評価した。 (Removability evaluation)
The produced adhesive tape was attached to a stainless steel plate (SUS304) and then left to stand for 24 hours under the conditions of 23 ° C. and 65% RH. Then, it was peeled off from the stainless steel plate, and the re-peelability (%) was evaluated according to the following formula.
Removability (%) = (area without adhesive residue) / (total area pasted) x 100
In the above formula, it was evaluated that the higher the removability value (the larger the area without the adhesive residue), the better the removability.
（粘着力評価）
　得られた粘着テープの粘着力を、ＪＩＳ　Ｚ０２３７に記載の方法に従って評価した。また、得られた粘着力について、以下の評価基準に従って評価した。なお、Ｂ評価以上を合格（粘着力に優れる）とした。
　（評価基準）
　Ａ：粘着力が４Ｎ／２０ｍｍ以上。
　Ｂ：粘着力が１Ｎ／２０ｍｍ以上４Ｎ／２０ｍｍ未満。
　Ｃ：粘着力が１Ｎ／２０ｍｍ未満。 (Adhesive strength evaluation)
The adhesive strength of the obtained adhesive tape was evaluated according to the method described in JIS Z0237. In addition, the obtained adhesive strength was evaluated according to the following evaluation criteria. In addition, B evaluation or higher was regarded as passing (excellent in adhesive strength).
(Evaluation criteria)
A: Adhesive strength is 4N / 20mm or more.
B: Adhesive strength is 1N / 20mm or more and less than 4N / 20mm.
C: Adhesive strength is less than 1N / 20mm.
［実施例２～４、及び比較例１～４］
　不織布の種類、及び粘着剤塗工液の組成を表１に示す通りとした以外は、実施例１と同様の方法にて、粘着テープを作成した。得られた各例の粘着テープについて、実施例１と同様の方法にて、裏抜け、耐熱性、再剥離性、及び粘着力を評価した。結果を表１に示す。 [Examples 2 to 4 and Comparative Examples 1 to 4]
An adhesive tape was prepared in the same manner as in Example 1 except that the type of the non-woven fabric and the composition of the adhesive coating liquid were as shown in Table 1. The adhesive tapes of each of the obtained examples were evaluated for strike-through, heat resistance, removability, and adhesive strength by the same method as in Example 1. The results are shown in Table 1.
　表１中の各成分の詳細は以下のとおりである。
　水系エマルジョン１：天然ゴムラテックス（ＫＵＡＬＡ　ＬＵＭＰＵＲ　ＫＥＰＯＮＧ　ＢＥＲＨＡＤ社製、商品名「ＥＸＣＥＬＴＥＸ－ＨＬＸ　ＬＡ－ＴＺ」、固形分５０質量％）。
　水系エマルジョン２：合成ゴムラテックス（ムサシノケミカル（株）製、商品名「ＭＧ３０」、固形分５０質量％）。
　ポリカルボン酸系重合体１：ポリアクリルアミド（ソマール（株）製、商品名「ソマレックス（登録商標）５３０」、重量平均分子量２０００万）。
　ポリカルボン酸系重合体２：ポリアクリル酸ナトリウム（東亜合成（株）製、商品名「アロン（登録商標）　Ａ－２０Ｐ」、重量平均分子量５００万）。
　ポリカルボン酸系重合体３：ポリアクリル酸（東亜合成（株）製、商品名「ジュリマー（登録商標）ＡＣ－１０ＳＨＰ」、重量平均分子量１００万）。
　粘着付与剤１：テルペンフェノール樹脂エマルジョン（荒川化学工業（株）製、商品名「Ｅ－２００」、固形分５０質量％）。
　粘着付与剤２：石油樹脂エマルジョン（荒川化学工業（株）製、商品名「ＡＰ－１１００－ＮＴ」、固形分５０質量％）。
　界面活性剤：アニオン系界面活性剤（花王（株）製、商品名「ネオペレックス　Ｇ－２５」）
　増粘剤：水系高分子増粘剤（サンノプコ（株）製、商品名「シックナーＳＮ－８１２」）。
　スパンボンド不織布：ポリエステル繊維、目付け８０ｇ／ｍ２。
　スパンレース不織布：ポリエステル繊維、目付け８０ｇ／ｍ２。
　ステッチボンド不織布：ポリエステル繊維、目付け８０ｇ／ｍ２、２２Ｆ。
　なお、ポリカルボン酸系重合体の重量平均分子量は、ＧＰＣ測定を行い、以下の条件にて単分散ポリスチレンの溶出曲線より各溶出時間における分子量を算出し、ポリスチレン換算の分子量として算出した。
＜測定条件＞
　機種：昭和電工株式会社製　商品名：「Ｓｈｏｄｅｘ　ＧＰＣ－１０１」
　カラム：ポリマーラボラトリーズ社製　ＰＬｇｅｌ　１０μｍ　ＭＩＸＥＤ－Ａ
　移動相：テトラヒドロフラン
　試料濃度：０．２質量％
　温度：オーブン４０℃、注入口３５℃、検出器３５℃ Details of each component in Table 1 are as follows.
Aqueous emulsion 1: Natural rubber latex (manufactured by KUALA LUMPURU KEPONG BERHAD, trade name "EXCELTEX-HLX LA-TZ", solid content 50% by mass).
Aqueous emulsion 2: Synthetic rubber latex (manufactured by Musashino Chemical Co., Ltd., trade name "MG30", solid content 50% by mass).
Polycarboxylic acid polymer 1: Polyacrylamide (manufactured by SOMAR Corporation, trade name "Somalex (registered trademark) 530", weight average molecular weight 20 million).
Polycarboxylic acid polymer 2: Sodium polyacrylate (manufactured by Toa Synthetic Co., Ltd., trade name "Aron (registered trademark) A-20P", weight average molecular weight 5 million).
Polycarboxylic acid-based polymer 3: Polyacrylic acid (manufactured by Toa Synthetic Co., Ltd., trade name "Julimer (registered trademark) AC-10SHP", weight average molecular weight 1 million).
Adhesive imparting agent 1: Terpene phenol resin emulsion (manufactured by Arakawa Chemical Industry Co., Ltd., trade name "E-200", solid content 50% by mass).
Adhesive imparting agent 2: Petroleum resin emulsion (manufactured by Arakawa Chemical Industry Co., Ltd., trade name "AP-1100-NT", solid content 50% by mass).
Surfactant: Anionic surfactant (manufactured by Kao Corporation, trade name "Neoperex G-25")
Thickener: Water-based polymer thickener (manufactured by San Nopco Co., Ltd., trade name "Sickener SN-812").
Spun-bonded non-woven fabric: polyester fiber, basis weight 80 g / m 2 .
Spunlace non-woven fabric: polyester fiber, basis weight 80 g / m 2 .
Stitch bond non-woven fabric: polyester fiber, basis weight 80 g / m 2 , 22F.
The weight average molecular weight of the polycarboxylic acid polymer was measured by GPC, and the molecular weight at each elution time was calculated from the elution curve of monodisperse polystyrene under the following conditions, and the molecular weight was calculated as polystyrene-equivalent molecular weight.
<Measurement conditions>
Model: Showa Denko KK Product name: "Shodex GPC-101"
Column: Polymer Laboratories PLgel 10 μm MIXED-A
Mobile phase: tetrahydrofuran Sample concentration: 0.2% by mass
Temperature: Oven 40 ° C, inlet 35 ° C, detector 35 ° C
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１に示す通り、本発明の製造方法で得られた粘着テープは、塗工時の裏抜けが生じず、かつ耐熱性、再剥離性に優れていた。また、粘着テープとして使用するために十分な粘着力も有していた。一方、本発明の構成を満たさない製造方法にて製造した比較例１～４の粘着テープでは、塗工時に裏抜けが生じた。また、得られた粘着テープは、粘着力が低かった。以上の結果から、本発明の粘着テープの製造方法は、製造時の基材からの裏抜けを防止でき、かつ得られた粘着テープは、耐熱性及び再剥離性に優れることが確認された。 As shown in Table 1, the adhesive tape obtained by the production method of the present invention did not cause strike-through during coating, and was excellent in heat resistance and removability. It also had sufficient adhesive strength to be used as an adhesive tape. On the other hand, in the adhesive tapes of Comparative Examples 1 to 4 produced by the production method not satisfying the constitution of the present invention, strike-through occurred at the time of coating. In addition, the obtained adhesive tape had low adhesive strength. From the above results, it was confirmed that the method for producing an adhesive tape of the present invention can prevent strike-through from the base material during production, and the obtained adhesive tape is excellent in heat resistance and removability.

Claims (7)

  1. 　不織布からなる基材と、粘着層とを有する粘着テープの製造方法であって、
    　水系エマルジョンと、重量平均分子量が４００万～３０００万のポリカルボン酸系重合体とを含み、Ｂ型粘度計を用いて６０ｒｐｍで測定した粘度が６０００～２００００ｍＰａ・ｓ／２３℃である粘着剤塗工液を、前記基材上にロール塗工にて塗工して前記粘着層を形成する工程を含む、粘着テープの製造方法。     A method for producing an adhesive tape having a base material made of a non-woven fabric and an adhesive layer.
    Adhesive coating containing an aqueous emulsion and a polycarboxylic acid polymer having a weight average molecular weight of 4 to 30 million and having a viscosity of 6000 to 20000 mPa · s / 23 ° C. measured at 60 rpm using a B-type viscometer. A method for producing an adhesive tape, which comprises a step of applying a working liquid onto the base material by roll coating to form the adhesive layer.
  2. 　前記粘着剤塗工液を調製する工程をさらに含む、請求項１に記載の粘着テープの製造方法。 The method for producing an adhesive tape according to claim 1, further comprising a step of preparing the adhesive coating liquid.
  3. 　前記粘着剤塗工液が水を含む、請求項１又は２に記載の粘着テープの製造方法。 The method for producing an adhesive tape according to claim 1 or 2, wherein the adhesive coating liquid contains water.
  4. 　前記粘着層の厚みが１５μｍ以上である、請求項１から３のいずれか一項に記載の粘着テープの製造方法。 The method for producing an adhesive tape according to any one of claims 1 to 3, wherein the thickness of the adhesive layer is 15 μm or more.
  5. 　前記ポリカルボン酸系重合体が、カルボキシ基を含有するモノマーの誘導体の重合体である、請求項１から４のいずれか一項に記載の粘着テープの製造方法。 The method for producing an adhesive tape according to any one of claims 1 to 4, wherein the polycarboxylic acid-based polymer is a polymer of a derivative of a monomer containing a carboxy group.
  6. 　前記カルボキシ基を含有するモノマーの誘導体が、アクリルアミドである、請求項５に記載の粘着テープの製造方法。 The method for producing an adhesive tape according to claim 5, wherein the derivative of the monomer containing a carboxy group is acrylamide.
  7. 　前記不織布が、スパンボンド不織布である、請求項１から６のいずれか一項に記載の粘着テープの製造方法。
          The method for producing an adhesive tape according to any one of claims 1 to 6, wherein the nonwoven fabric is a spunbonded nonwoven fabric.
PCT/JP2020/015459 2019-04-08 2020-04-06 Method for producing adhesive tape WO2020209212A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2021513619A JP7368459B2 (en) 2019-04-08 2020-04-06 Adhesive tape manufacturing method

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2019073290 2019-04-08
JP2019-073290 2019-04-08

Publications (1)

Publication Number Publication Date
WO2020209212A1 true WO2020209212A1 (en) 2020-10-15

Family

ID=72751670

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2020/015459 WO2020209212A1 (en) 2019-04-08 2020-04-06 Method for producing adhesive tape

Country Status (3)

Country Link
JP (1) JP7368459B2 (en)
TW (1) TW202100700A (en)
WO (1) WO2020209212A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113215833A (en) * 2021-06-18 2021-08-06 汪晓东 Moisture-keeping antirust oil sealing tape

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0987173A (en) * 1995-09-25 1997-03-31 Lion Corp Aqueous tacky adhesive composition
JPH11263944A (en) * 1998-03-17 1999-09-28 Itc:Kk Webby adhesive material
JP2008231171A (en) * 2007-03-19 2008-10-02 Ricoh Co Ltd Pressure-sensitive adhesive label for heat-sensitive recording
WO2011115167A1 (en) * 2010-03-18 2011-09-22 日本製紙株式会社 Coated paper for printing and manufacturing method for same
WO2013069784A1 (en) * 2011-11-10 2013-05-16 カモ井加工紙株式会社 Adhesive tape and masker
WO2015060210A1 (en) * 2013-10-23 2015-04-30 昭和電工株式会社 Adhesive agent composition and removable adhesive double-sided tape produced using same
WO2018088303A1 (en) * 2016-11-09 2018-05-17 株式会社クラレ Pressure-sensitive adhesive sheet, adhesive plaster, and production processes therefor

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0987173A (en) * 1995-09-25 1997-03-31 Lion Corp Aqueous tacky adhesive composition
JPH11263944A (en) * 1998-03-17 1999-09-28 Itc:Kk Webby adhesive material
JP2008231171A (en) * 2007-03-19 2008-10-02 Ricoh Co Ltd Pressure-sensitive adhesive label for heat-sensitive recording
WO2011115167A1 (en) * 2010-03-18 2011-09-22 日本製紙株式会社 Coated paper for printing and manufacturing method for same
WO2013069784A1 (en) * 2011-11-10 2013-05-16 カモ井加工紙株式会社 Adhesive tape and masker
WO2015060210A1 (en) * 2013-10-23 2015-04-30 昭和電工株式会社 Adhesive agent composition and removable adhesive double-sided tape produced using same
WO2018088303A1 (en) * 2016-11-09 2018-05-17 株式会社クラレ Pressure-sensitive adhesive sheet, adhesive plaster, and production processes therefor

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113215833A (en) * 2021-06-18 2021-08-06 汪晓东 Moisture-keeping antirust oil sealing tape

Also Published As

Publication number Publication date
TW202100700A (en) 2021-01-01
JP7368459B2 (en) 2023-10-24
JPWO2020209212A1 (en) 2020-10-15

Similar Documents

Publication Publication Date Title
US6020062A (en) Article having slippable adhesive
KR101182075B1 (en) Double-sided adhesive tape
TWI669362B (en) Pressure sensitive adhesive
WO1998020086A9 (en) Article having slippable adhesive
TW201739862A (en) Adhesive sheet
JP2015165023A (en) pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet
JP6207112B1 (en) Re-peelable aqueous pressure-sensitive adhesive composition and re-peelable pressure-sensitive adhesive sheet
JP2008143970A (en) Manufacturing method for double-coated adhesion pressure-sensitive adhesion sheet
JP5497258B2 (en) Removable adhesive sheet
JP2009173689A (en) Aqueous dispersion type adhesive composition and adhesive sheet
JP2008115315A (en) Water dispersion type acrylic pressure-sensitive adhesive, pressure-sensitive adhesive tape and method for manufacturing the same
JP2007023068A (en) Double-sided tacky tape and method for producing double-sided tacky tape
TW202122544A (en) Hot melt adhesive composition, adhesive tape, and method for producing adhesive tape
CN108138011B (en) Adhesive, in particular for a peelable adhesive tape, and use for bonding on a coated woodchip wallpaper
JP7368459B2 (en) Adhesive tape manufacturing method
US20190077998A1 (en) Self-adhesive article and use thereof for bonding on coated woodchip wallpaper
JP5286460B2 (en) Sleeve hole filling adhesive sheet
JP2008081567A (en) Emulsion of acrylic copolymer and adhesive containing the same
WO2022039108A1 (en) Adhesive tape and method for manufacturing same
JP2005194448A (en) Acrylic copolymer emulsion for pressure-sensitive adhesive, method for producing the same and pressure-sensitive adhesive sheet
JP2011225812A (en) Water dispersion type acrylic adhesive composition, and method for manufacturing adhesive layer
JPH03217478A (en) Adhesive for electrostatic flocking
JPH0812954A (en) Adhesive tape
JP6225377B2 (en) Adhesive tape and laminated adhesive tape
JP6201275B1 (en) Aqueous pressure-sensitive adhesive composition and releasable pressure-sensitive adhesive sheet

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20788250

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2021513619

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20788250

Country of ref document: EP

Kind code of ref document: A1