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
  • 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 thread-like adhesive.
• a thread-like adhesive having a core material and an adhesive is generally made by coating the adhesive around a core material, and is a thin adhesive that can conform to complex shapes.
• it can be wound into a cylindrical shape using a bobbin as necessary, and since no release liner is required, it can contribute to reducing waste during the process.
• the thread-like adhesive material described in Patent Document 1 has excellent adhesive strength, and the thread-like adhesive material described in Patent Document 2 has excellent impact resistance.
• the thread-like adhesive bodies stored and transported as a roll have a problem of adhesion between the thread-like adhesive bodies. This problem is also called self-adhesion, and causes the thread-like adhesive bodies to be difficult to handle when used.
• Patent Documents 1 and 2 sufficient studies aimed at solving the problem of self-adhesion were not conducted.
• the present invention has been made in consideration of the above-mentioned conventional situation, and aims to provide a thread-like adhesive body that maintains excellent adhesive strength and suppresses self-adhesion even when wound into a roll.
• a thread-like adhesive body having a core material and an adhesive The cross section of the thread-like adhesive body has an area ratio calculated by the following formula (1) of 0.2 to 1.0.
• (Area ratio) (Area of adhesive)/(Area of core material) (1)
• the thread-like adhesive of the present invention maintains excellent adhesive strength and is able to suppress self-adhesion even when rolled up.
• a thread-like adhesive material wound into a cylindrical shape optionally using a cylindrical body such as a bobbin, is referred to as a wound body.
• the wound body may or may not include a cylindrical body such as a bobbin.
• the thread-like adhesive body of the present embodiment has a core material and an adhesive.
• thread-like refers to a shape in which the length in the longitudinal direction is sufficiently longer than the length in the transverse direction, the ratio of the length of the long axis to the length of the short axis in the cross-sectional shape (long axis/short axis) is, for example, 200 or less, and which can be bent in various directions and at various angles like a thread.
• a cross section refers to a surface obtained by cutting an object perpendicularly to the longitudinal direction.
• a cross-sectional shape refers to the shape of the cross section.
• the minor axis refers to the shortest axis passing through the center of gravity of the cross-sectional shape.
• the major axis refers to the longest axis passing through the center of gravity of the cross-sectional shape.
• the major axis/minor axis ratio is preferably 100 or less, more preferably 50 or less, even more preferably 10 or less, particularly preferably 5 or less, and most preferably 3 or less.
• the thread-like adhesive of this embodiment can be bent in a variety of directions and angles, so it can be bent to match the shape of the bonding area, and can accommodate a variety of shapes of bonding areas.
• the thread-like adhesive body of the present embodiment has a core material.
• the core material is preferably thread-like.
• the core material is a multifilament yarn that has multiple filaments and is made by doubling or twisting the multiple filaments.
• the core material is a multifilament yarn, sufficient strength and stable physical properties can be obtained. As a result, a thread-like adhesive can be obtained that has low quality variation, excellent strength, and excellent adhesive power.
• the number of filaments contained in the core material is preferably 4 or more, more preferably 10 or more, and particularly preferably 20 or more.
• the number of filaments is preferably 2000 or less, more preferably 1500 or less, and especially preferably 1000 or less.
• the type of resin used for the filament there are no particular limitations on the type of resin used for the filament, and it may be selected appropriately depending on the required properties such as strength, mass, and hardness. Examples include materials containing polymeric materials such as thermoplastic polymers, thermosetting polymers, and rubber.
• materials that can be used include polymeric materials such as rayon, cupra, acetate, promix, nylon, aramid, vinylon, vinylidene, polyvinyl chloride, acrylic, polyolefins (polyethylene, polypropylene, ethylene-propylene copolymers, ethylene-vinyl acetate copolymers, etc.), polyester resins (polyethylene terephthalate, etc.), vinyl chloride resins, vinyl acetate resins, polyimide resins, polyamide resins, fluororesins, polyurethane, polychlar, and polylactic acid; rubbers such as synthetic rubbers (natural rubber, polyurethane, etc.); and foams such as polyurethane foam and polychloroprene rubber foam.
• polyester resins are preferred, and polyethylene terephthalate is more preferred.
• the content of the filaments in the core material is preferably 10 to 100% by mass, more preferably 50 to 100% by mass, and particularly preferably 80 to 100% by mass, from the viewpoint of preventing the adhesive from penetrating into the core material.
• the core material may contain various additives such as fillers (inorganic fillers, organic fillers, etc.), anti-aging agents, antioxidants, UV absorbers, antistatic agents, lubricants, plasticizers, colorants (pigments, dyes, etc.), etc., as necessary.
• the surface of the core material may be subjected to a known or conventional surface treatment, such as a corona discharge treatment, a plasma treatment, or application of a primer.
• the shape of the core material is not particularly limited, and may be appropriately adjusted depending on the required properties such as strength, mass, hardness, etc.
• the cross-sectional shape of the core material is typically circular, but may be various other shapes such as elliptical or polygonal.
• the core material may have multiple filaments, and may be a yarn that combines filaments with spun yarn, textured yarn, hollow yarn, etc. by twisting them together.
• textured yarn include textured yarn, bulky yarn, and stretch yarn, which have been subjected to shrink processing, bulking processing, etc.
• the thickness of the core material is not particularly limited, and can be adjusted as appropriate to ensure that the thickness of the thread-like adhesive is appropriate for the application.
• the number of twists in the core material is preferably 1 turn/m or more. If the number of twists is 1 turn/m or more, it becomes easier to form the voids described below, and the impact resistance of the thread-like adhesive body is improved.
• the number of twists in the core material is more preferably 20 turns/m or more, and even more preferably 50 turns/m or more.
• the twist of the core material is not too strong. Therefore, the number of twists of the core material is preferably 500 times/m or less, more preferably 300 times/m or less, and even more preferably 100 times/m or less.
• twist factor K is an index for discussing the influence of twisting (the influence on the core material's cohesion, ease of deformation, amount of adhesive attached, etc.) regardless of the thickness of the core material.
• the influence of the number of twists on the core material differs depending on the thickness of the core material, but if the twist factor K is the same, it indicates that the influence of twisting on the core material is the same regardless of the thickness of the core material.
• the twist coefficient K is preferably 0 or more, and more preferably greater than 0.
• the twist coefficient K is 200 or less, the flexibility of the core material, and therefore the thread-like adhesive, is improved, making it easier to apply to narrow areas and complex shapes such as curved sections, bent sections, and uneven sections. Therefore, the twist coefficient K is preferably 200 or less, more preferably 100 or less, and even more preferably less than 50.
• K is the twist coefficient
• T is the number of twists (turns/m)
• D is the fineness (dtex).
• the thread-like adhesive body of the present embodiment has an adhesive that coats the core material and is impregnated with the adhesive.
• the adhesive preferably covers the entire circumference of the surface of the core material in the longitudinal direction.
• the entire circumference of the surface of the core material refers to the entire periphery of the core material, and means the entire 360° circumference of the surface of the core material, centered on the center line of the core material in the longitudinal direction.
• the end faces of the core material may or may not be covered with adhesive.
• the end faces of the core material may not be covered with adhesive.
• the coverage of the core material with the adhesive is preferably 50 area% or more, more preferably 80 area% or more, even more preferably 90 area% or more, and particularly preferably 95 area% or more. If the coverage of the core material is 50 area% or more, it is possible to prevent breakage of the core material and to form a thread-like adhesive body with excellent strength.
• the coverage of the core material can be calculated, for example, using an X-ray CT scanner (Xradia 520 Versa, Zeiss, tube voltage 60 kV, tube current 83 ⁇ A, pixel size 1.5 ⁇ m/pixel). Specifically, 1601 continuous transmission images are taken around the entire circumference of the thread-like adhesive from 0° to 360°. The obtained images are three-dimensionally reconstructed using image analysis software [ImageJ, AVIZO (Thermo Fisher Scientific)], and the core material, adhesive, and air are identified by performing ternary quantization and noise removal based on the brightness.
• image analysis software image analysis software
• This identification is performed by checking the brightness of the air and adhesive, respectively, setting a first threshold value at the intermediate value, and further checking the brightness of the adhesive and core material, respectively, and setting a second threshold value at the intermediate value.
• the interface 1 does not include the interface between the core material and the voids in the thread-like adhesive body of the present embodiment.
• the interface 1 does not include the interface between the core material and the voids inside the filament.
• the interface 2 is intended to be the interface between the adhesive and air.
• the interface 2 does not include the interface between the adhesive and the voids in the thread-like adhesive body of the present embodiment.
• the interface 2 does not include the interface between the adhesive and the voids inside the filament.
• the adhesive is impregnated into the core material
• the adhesive is present between multiple filaments in the core material.
• the adhesive and the core material maintain adhesion, making them less likely to peel off, and improving the strength of the thread-like adhesive.
• the adhesive is not particularly limited, and known adhesives can be used. Examples include acrylic adhesives, rubber adhesives, vinyl alkyl ether adhesives, silicone adhesives, polyester adhesives, polyamide adhesives, urethane adhesives, fluorine adhesives, and epoxy adhesives. Among them, from the viewpoint of adhesion, acrylic adhesives, urethane adhesives, silicone adhesives, rubber adhesives, and polyester adhesives are preferred, and acrylic adhesives are particularly preferred because the adhesion is easy to control. Note that only one type of adhesive may be used alone, or two or more types may be used in combination.
• the adhesive in this embodiment is preferably a pressure-sensitive adhesive that has adhesion at room temperature and can attach an adherend to its surface by the pressure generated when the surface of the adhesive and the surface of the adherend come into contact with each other. If it is a pressure-sensitive adhesive, it does not require heating and can be applied to adherends that are sensitive to heat.
• Both solvent-based and water-dispersed adhesives can be used as the adhesive, and it is preferable to use an adhesive in which crosslinking progresses as the adhesive composition dries (solvent evaporation, heating) and the crosslinking is completed quickly after drying. This is because new crosslinking is not increased after the adhesive surfaces come into contact with each other.
• water-dispersed adhesives are preferred because they can be applied at high speed, are environmentally friendly, and have little effect (swelling, dissolution) on the substrate and core material due to the solvent, and water-dispersed acrylic adhesives are more preferred.
• acrylic adhesive refers to an adhesive that uses an acrylic polymer as the base polymer (the main component of the polymer components, i.e., a component that accounts for 50% or more by mass).
• Acrylic polymer refers to a polymer that uses a monomer having at least one (meth)acryloyl group in one molecule (hereinafter, this may be referred to as "acrylic monomer”) as the main constituent monomer component (the main component of the monomer, i.e., a component that accounts for more than 50% by mass of the total amount of monomers that make up the acrylic polymer).
• acrylic monomer refers to acryloyl and methacryloyl in a comprehensive sense.
• (meth)acrylic acid ester refers to acrylic acid ester and methacrylic acid ester
• (meth)acrylic refers to acrylic and methacrylic in a comprehensive sense.
• the acrylic polymer is preferably, for example, a polymer of a monomer raw material that contains an alkyl (meth)acrylate ester as the main monomer and may further contain a sub-monomer that is copolymerizable with the main monomer.
• the main monomer refers to a component that accounts for more than 50% by mass of the monomer composition in the monomer raw material.
• R1 represents a hydrogen atom or a methyl group
• R2 represents an alkyl group having 2 to 14 carbon atoms.
• Examples of the compound include compounds represented by the following formula:
• R2 examples include an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an isoamyl group, a hexyl group, a heptyl group, a 2-ethylhexyl group, an isooctyl group, an isononyl group, and an isodecyl group.
• an alkyl group having 2 to 10 carbon atoms such as a butyl group or a 2-ethylhexyl group, is preferred as R2 .
• the above (meth)acrylic acid alkyl esters can be used alone or in combination of two or more kinds.
• the ratio of the (meth)acrylic acid alkyl ester [for example, the above-mentioned (meth)acrylic acid C2-14 alkyl ester] in a monomer mixture containing the (meth)acrylic acid alkyl ester as a main component is generally 80 mass % or more (for example, about 80 to 99.8 mass %), preferably 85 mass % or more (for example, about 85 to 99.5 mass %), and more preferably 90 mass % or more (for example, about 90 to 99 mass %).
• the monomer mixture usually contains a functional group-containing monomer (thermally crosslinkable functional group-containing monomer) to introduce crosslinking points for thermal crosslinking.
• a functional group-containing monomer thermalally crosslinkable functional group-containing monomer
• the adhesive strength to the adherend is also improved.
• Examples of the functional group-containing monomer include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, crotonic acid, and maleic anhydride, or their acid anhydrides; hydroxyl group-containing monomers such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate; amide group-containing monomers such as (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N-methylol (meth)acrylamide, N-methoxymethyl (meth)acrylamide, and N-butoxymethyl (meth)acrylamide; amino group-containing monomers such as dimethylaminoethyl (meth)acrylate and t-butylaminoethyl (meth)acrylate; glycidyl group-containing monomers such as glycidyl (meth)acrylate; (meth)acrylonitrile, N
• the amount of the functional group-containing monomer used is, for example, about 0.5 to 12 parts by mass, and preferably about 1 to 8 parts by mass, per 100 parts by mass of the (meth)acrylic acid alkyl ester.
• the monomer mixture may contain other copolymerizable monomers as necessary to enhance properties such as cohesive strength.
• copolymerizable monomers include vinyl esters such as methyl (meth)acrylate and vinyl acetate; aromatic vinyl compounds such as styrene and vinyl toluene; (meth)acrylic acid esters of cyclic alcohols such as cyclopentyl di(meth)acrylate and isobornyl (meth)acrylate; and (meth)acrylic acid esters of polyhydric alcohols such as neopentyl glycol di(meth)acrylate, hexanediol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. These copolymerizable monomers may be used alone or in combination.
• the crosslinking agent used in the acrylic adhesives may be any commonly used crosslinking agent, such as silane-based crosslinking agents, organic peroxides, epoxy-based compounds, amino group-containing compounds, organic metal salts, metal alcoholates, metal chelates, hydrazide-based crosslinking agents, carbodiimide-based crosslinking agents, isocyanate-based crosslinking agents, and silanol-based crosslinking agents.
• organic metal salts, metal chelates, hydrazide-based crosslinking agents, and silane-based crosslinking agents are preferred because crosslinking is completed quickly after drying of the adhesive composition.
• crosslinking agent may be either oil-soluble or water-soluble, and may be used alone or in combination of two or more types.
• silane crosslinking agent it is preferable to use a silane monomer that is copolymerizable with the (meth)acrylic acid alkyl ester.
• the silane monomer is not particularly limited as long as it is a polymerizable compound having a silicon atom, but a silane compound having a (meth)acryloyl group such as a (meth)acryloyloxyalkylsilane derivative is preferable because it has excellent copolymerizability with the (meth)acrylic acid alkyl ester.
• silane monomer examples include ⁇ -methacryloxypropyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-acryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, and 3-acryloyloxypropylmethyldiethoxysilane. These silane monomers can be used alone or in combination of two or more.
• copolymerizable silane monomers examples include vinyltrimethoxysilane, vinyltriethoxysilane, 4-vinylbutyltrimethoxysilane, 4-vinylbutyltriethoxysilane, 8-vinyloctyltrimethoxysilane, 8-vinyloctyltriethoxysilane, 10-methacryloyloxydecyltrimethoxysilane, 10-acryloyloxydecyltrimethoxysilane, 10-methacryloyloxydecyltriethoxysilane, and 10-acryloyloxydecyltriethoxysilane.
• the amount of crosslinking agent used can be appropriately selected depending on the type of monomer raw material and the application of the thread-like adhesive.
• the amount of crosslinking agent per 100 parts by mass of the monomer raw material (excluding the crosslinking agent) is preferably 0.005 to 5 parts by mass, and more preferably in the range of 0.01 to 3 parts by mass.
• crosslinking agents may be used, and crosslinking using other crosslinking agents, UV crosslinking, radiation crosslinking such as electron beam crosslinking, etc. may be applied.
• other crosslinking agents commonly used crosslinking agents may be used, and examples of such agents include organic peroxides, epoxy compounds, amino group-containing compounds, organic metal salts, metal alcoholates, metal chelates, hydrazide crosslinking agents, carbodiimide crosslinking agents, isocyanate crosslinking agents, silane or silanol crosslinking agents, etc.
• the other crosslinking agents may be either oil-soluble or water-soluble.
• the pressure-sensitive adhesive can be formed using a pressure-sensitive adhesive composition, and the pressure-sensitive adhesive composition is preferably a water-dispersible pressure-sensitive adhesive composition.
• the pressure-sensitive adhesive may form a layer (pressure-sensitive adhesive layer).
• the water-dispersed PSA composition can be prepared, for example, by subjecting a monomer mixture containing the above-mentioned alkyl (meth)acrylate ester as a main component and a silane-based monomer to conventional emulsion polymerization to obtain an aqueous dispersion of a (meth)acrylic acid ester copolymer, and adding thereto, as necessary, the above-mentioned other crosslinking agent.
• the polymerization method can be a general batch polymerization, continuous dropwise polymerization, or divided dropwise polymerization, and the polymerization temperature is, for example, about 20 to 100°C.
• the polymerization initiator used in the polymerization is, for example, 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]n-hydrate, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylpropionamidine) disulfate, 2,2'-azobis(2-amidinopropane)dihydrochloride, 2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis(N,N'-dimethyl
• initiators include, but are not limited to, azo initiators such as phenylisobutylamidine; persulfates such as potassium persulfate and ammonium persulfate; peroxide initiators such as benzoyl peroxide, t-butyl hydroperoxide, and hydrogen peroxide; substituted ethane initiators such as phenyl-sub
• a chain transfer agent may also be used in the polymerization.
• the chain transfer agent include conventional chain transfer agents, such as mercaptans such as lauryl mercaptan and dodecanethiol.
• the amount of the chain transfer agent used is, for example, about 0.001 to 0.5 parts by mass per 100 parts by mass of the total amount of monomers.
• anionic emulsifiers such as sodium lauryl sulfate, polyoxyethylene sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, polyoxyethylene alkyl ether sodium sulfate, polyoxyethylene alkyl phenyl ether ammonium sulfate, and polyoxyethylene alkyl phenyl ether sodium sulfate; nonionic emulsifiers such as polyoxyethylene alkyl ether and polyoxyethylene alkyl phenyl ether may be used. These emulsifiers may be used alone or in combination of two or more. The amount of the emulsifier used is, for example, about 0.2 to 10 parts by mass, and preferably about 0.5 to 5 parts by mass, per 100 parts by mass of the total amount of monomers.
• the pressure-sensitive adhesive composition may be prepared by obtaining the (meth)acrylic acid ester copolymer by a method other than emulsion polymerization, adding the crosslinking agent as necessary, and dispersing the copolymer in water with an emulsifier.
• the adhesive composition may also contain, as necessary, a base (such as aqueous ammonia) or an acid to adjust the pH, and additives commonly used in adhesives, such as tackifier resins, thickeners, surfactants, antioxidants, fillers, pigments, and colorants.
• a base such as aqueous ammonia
• additives commonly used in adhesives such as tackifier resins, thickeners, surfactants, antioxidants, fillers, pigments, and colorants.
• tackifier resin for example, one or more types selected from various tackifier resins such as rosin-based resins, rosin derivative resins, petroleum-based resins, terpene-based resins, phenol-based resins, and ketone-based resins can be used.
• the content of the tackifier resin is preferably 60 parts by mass or less, more preferably 50 parts by mass or less, even more preferably 40 parts by mass or less, and even more preferably 30 parts by mass or less, per 100 parts by mass of the base polymer.
• Thickeners include, for example, polyacrylic acid-based thickeners, urethane-based thickeners, polyvinyl alcohol-based thickeners, etc. Among these, polyacrylic acid-based thickeners and urethane-based thickeners are preferred.
• the content of the thickener is preferably 10 parts by mass or less, and more preferably 5 parts by mass or less, per 100 parts by mass of the base polymer.
• the amount of adhesive (mass of adhesive per unit length) is preferably 2 mg/m or more, more preferably 5 mg/m or more, and even more preferably 8 mg/m or more.
• the amount of adhesive is preferably 200 mg/m or less, more preferably 180 mg/m or less, and even more preferably 160 mg/m or less. In this specification, the amount of adhesive applied is sometimes referred to as "adhesive amount.”
• the elastic modulus of the adhesive in the thread-like adhesive body at 23°C is preferably 1.0 x 10 3 to 1.0 x 10 7 Pa, more preferably 5.0 x 10 3 to 5.0 x 10 6 Pa, and even more preferably 1.0 x 10 4 to 1.0 x 10 6 Pa.
• the elastic modulus of the adhesive at 23°C can be measured, for example, using an elastic modulus measuring device or a dynamic viscoelasticity measuring device.
• the area ratio of the cross section of the thread-like adhesive body calculated by the following formula (1) is 0.2 to 1.0, preferably 0.25 to 0.95, more preferably 0.3 to 0.9, and even more preferably 0.4 to 0.8.
• (Area ratio) (Area of adhesive)/(Area of core material) (1)
• the adhesive present on the outer periphery of the thread-like adhesive body will be insufficient, which is undesirable because it will weaken the adhesive strength. In such cases, the thickness of the adhesive layer formed on the outer periphery of the thread-like adhesive body will be very thin, or there will be parts on the outer periphery where the adhesive layer is absent, resulting in weak adhesive strength.
• the area ratio exceeds 1.0, the amount of adhesive present on the outer periphery of the thread-like adhesive body becomes excessive, which is undesirable because it causes problems with self-adhesion.
• a thick layer of adhesive is formed on the outer periphery of the thread-like adhesive body, so that when the thread-like adhesive body is wound, the adjacent thread-like adhesive bodies adhere strongly to each other, resulting in problems with self-adhesion.
• the area ratio can be determined from the image obtained by observing the cross section of the dyed thread-like adhesive with a scanning electron microscope (SEM). Heavy metals, for example, can be used to dye the thread-like adhesive.
• SEM scanning electron microscope
• the image obtained from the SEM observation is binarized using analysis software, the area of the adhesive and the area of the core material corresponding to each color portion are determined, and the area ratio is determined from the ratio of these.
• the image obtained from the SEM observation is ternarized using analysis software, the area of the adhesive, the area of the core material, and the area of the voids corresponding to each color portion are determined, and the area ratio is determined from the ratio of the area of the adhesive, the area of the core material, and the area of the voids.
• the area ratio can be adjusted in various ways.
• the area ratio can be adjusted by changing the amount of adhesive and core material used, by changing the viscosity of the coating liquid when applying the adhesive to the core material, or by the coating speed when applying the adhesive to the core material.
• the thread-like adhesive body of this embodiment has a cross-sectional void ratio of preferably 20% by area or less, more preferably 19% by area or less, and even more preferably 18% by area or less.
• the cross-sectional void ratio of the thread-like adhesive body is 20% by area or less, the amount of adhesive impregnated into the core material is not too small, and a certain degree of adhesion is maintained between the adhesive and the core material. This is preferable because it can prevent the thread-like adhesive body from being broken and the adhesive from being separated from the core material, thereby preventing the adhesive from being broken and the adhesive from being reduced.
• the lower limit of the void ratio in the cross section of the thread-like adhesive body is preferably 1 area % or more, more preferably 2 area % or more, and even more preferably 3 area % or more.
• the void ratio in the cross section of the thread-like adhesive can be determined, like the area ratio, by observing the cross section of the dyed thread-like adhesive with a scanning electron microscope (SEM) and looking at the image obtained.
• SEM scanning electron microscope
• the image obtained from the SEM observation is converted into a ternary value using analysis software, and the void ratio in the cross section of the thread-like adhesive can be determined from the ratio of the area of the void to the sum of the area of the adhesive, the area of the core material, and the area of the void obtained as the area of each color.
• the porosity in the cross section of the thread-like adhesive can be adjusted by various methods.
• the porosity can be adjusted by changing the amount of adhesive and core material used, by changing the viscosity of the coating liquid when applying the adhesive to the core material, or by the coating speed when applying the adhesive to the core material.
• the thickness of the thread-like adhesive is preferably 50 to 2000 ⁇ m, more preferably 100 to 1000 ⁇ m, from the viewpoints of strength and ease of handling.
• the thread-like adhesive body of this embodiment can be produced by known methods, for example, a method including a coating step of applying a coating liquid containing an adhesive to a core material.
• the coating liquid may be applied to the core material by, for example, dipping, immersion, coating or the like, and may be dried by heating as necessary.
• the heat drying may be carried out, for example, at a temperature of 80 to 120° C., preferably 90 to 110° C., for example, 20 seconds to 3 minutes, preferably 30 seconds to 2 minutes.
• the coating liquid can be applied using a conventional coater such as a gravure roll coater, reverse roll coater, kiss roll coater, dip roll coater, bar coater, knife coater, or spray coater.
• a conventional coater such as a gravure roll coater, reverse roll coater, kiss roll coater, dip roll coater, bar coater, knife coater, or spray coater.
• the method for producing a thread-like adhesive body of the present embodiment may or may not include a fiber-spreading step.
• the core material is spread by being moved along a non-rotating roller when the adhesive is applied to the core material.
• the porosity in the filamentous adhesive body can be adjusted to be high, whereas when the filamentous adhesive body of this embodiment is produced with a fiber-spreading step, the porosity in the filamentous adhesive body can be adjusted to be low.
• the method for producing the thread-like adhesive of this embodiment includes a coating step
• a roller is used in the coating step, and the rotation speed of the roller is 0.3 to 5.0 times the payout speed of the core material.
• the rotation speed of the roller is preferably 0.4 to 4.0 times the core material unwinding speed, more preferably 0.5 to 3.0 times, and most preferably 0.8 to 1.5 times.
• a tension of 6.0 mN/dtex or less it is preferable to apply a tension of 6.0 mN/dtex or less to the core material during the coating process.
• a tension of 6.0 mN/dtex or less it is possible to prevent the core material from opening up, and to make it easier to keep the void ratio of the thread-like adhesive body of this embodiment within the above-mentioned range.
• the tension applied to the core material is preferably 0.2 to 6.0 mN/dtex, and more preferably 0.4 to 5.0 mN/dtex.
• the thread-like adhesive body of the present embodiment can be attached to narrow members or narrow areas while suppressing overflow, can be easily applied to complex shapes such as curves, curved surfaces, and uneven surfaces, and can be easily disassembled (reworked).Furthermore, since it has excellent adhesive strength, it can be used to adhere various items.
• the thread-like adhesive of this embodiment can be suitably used for fixing items in the manufacture of electronic devices and for fixing vehicle-mounted components, and can be applied to fixing the narrow bezels of mobile terminals such as mobile phones and smartphones, and for fixing batteries, motors, etc.
• the thread-like adhesive body of this embodiment can be firmly applied without causing wrinkles or overlaps even when applied to a portion having a complex shape such as a curve, a curved surface, or an uneven surface. Furthermore, since the thread-like adhesive body can be applied to the desired portion at once, i.e., in one process, it is also excellent in workability and can be applied to an automated line. Specifically, the thread-like adhesive of this embodiment can be suitably used for applications in which various wires (linear members) such as electric wires and optical fibers, LED fiber lights, optical fiber sensors such as FBGs (Fiber Bragg Gratings), threads, strings, wires, and other such wire materials (linear members), and thin members are fixed in a desired shape.
• various wires such as electric wires and optical fibers, LED fiber lights, optical fiber sensors such as FBGs (Fiber Bragg Gratings), threads, strings, wires, and other such wire materials (linear members), and thin members are fixed in a desired shape.
• the thread-like adhesive of this embodiment can be used to firmly fix the wire or thin member with excellent workability while suppressing protrusion, wrinkles, and overlaps in accordance with the complex shape that the wire or thin member should have.
• the thread-like adhesive of this embodiment can be attached in advance to the surface of the other member in accordance with the shape in which the wire or thin member should be fixed, and then the wire or thin member can be attached to the thread-like adhesive attached to the surface of the other member to fix it.
• the thread-like adhesive of this embodiment can be attached to the wire or thin member, and then the wire or thin member can be fixed to the other member in the desired shape.
• the thread-like adhesive material of the present embodiment can also be suitably used for the purpose of temporarily fixing (temporarily fastening) an article, for example, for the purpose of temporarily fixing (temporarily fastening) an article to the surface of another article. More specifically, the thread-like adhesive material of the present embodiment can be used for the purpose of temporarily fixing (temporarily fastening) an article when manufacturing textile products such as clothes, shoes, bags, hats, and leather products. However, the purpose is not limited thereto, and the thread-like adhesive material can be suitably used for various purposes in which temporary fixing (temporarily fastening) is desired.
• the first article is provisionally fixed to the surface of the other article using a thread-like adhesive to position it, and then the two articles are fixed (mainly fixed) by a fixing method such as thermocompression bonding or sewing.
• a fixing method such as thermocompression bonding or sewing.
• the thread-like adhesive of this embodiment it is easy to provisionally fix the two articles while avoiding the fixing part provided between them.
• sewing textile products or leather products if provisional fixing is performed using a thread-like adhesive, it is easy to provisionally fix the articles while avoiding the sewing part, and it is easy to prevent the adhesive from adhering to the needle.
• the thread-like adhesive of this embodiment can be used to effectively attach both articles while minimizing overflow, wrinkles, and overlaps, even if the articles have complex shapes such as curves, curved surfaces, or uneven shapes, and can be attached in a single process, making it easy to work with. Furthermore, even in the case of materials that are easily deformed, such as fabric, cloth, leather, etc. that make up textile products or leather products, by temporarily fixing them using the thread-like adhesive of this embodiment, deformation of the materials due to tension can be suppressed or prevented, resulting in good design after fixing (full fixation).
• the thread-like adhesive of this embodiment after the two articles are fixed (mainly fixed), it is easy to remove the thread-like adhesive of this embodiment from between the two fixed (mainly fixed) articles as necessary. In this way, it is possible to prevent the adhesive from spilling out, and to effectively prevent deterioration of the design caused by discoloration of the remaining adhesive over time.
• the thread-like adhesive of this embodiment can be twisted together with threads made of other materials to form combined threads, or woven with threads or fabrics (including nonwoven fabrics and sheets) made of other materials to achieve multiple functions.
• the thread-like adhesive of this embodiment can be used as a dam material to prevent the adhesive or pressure-sensitive adhesive from spilling out when the adhesive or pressure-sensitive adhesive is applied to an object to be bonded (adherend).
• the dam material can be used, for example, to prevent the sealing resin used to bond optical panels from spilling out.
• the thread-like adhesive can be peeled off after the adhesive or pressure-sensitive adhesive has hardened, or it can be left in place.
• ⁇ 1> A thread-like adhesive body having a core material and an adhesive
• the cross section of the thread-like adhesive body has an area ratio calculated by the following formula (1) of 0.2 to 1.0.
• (Area ratio) (Area of adhesive)/(Area of core material) (1)
• ⁇ 2> The thread-like adhesive body described in ⁇ 1>, wherein the number of filaments contained in the core material is four or more.
• ⁇ 3> A thread-like adhesive body described in ⁇ 1> or ⁇ 2>, wherein the porosity in the cross section of the thread-like adhesive body is 20 area % or less.
• ⁇ 4> The thread-like adhesive body according to any one of ⁇ 1> to ⁇ 3>, wherein the number of twists of the core material is 1 to 500 times/m.
• ⁇ 5> The thread-like adhesive material according to any one of ⁇ 1> to ⁇ 4>, wherein the adhesive has an elastic modulus of 1.0 ⁇ 10 3 to 1.0 ⁇ 10 7 Pa at 23° C.
• monomer emulsion A 85 parts by mass of 2-ethylhexyl acrylate, 13 parts by mass of methyl acrylate, 1.25 parts by mass of acrylic acid, 0.75 parts by mass of methacrylic acid, 0.05 parts by mass of lauryl mercaptan (chain transfer agent), 0.02 parts by mass of ⁇ -methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name "KBM-503”), and 2 parts by mass of sodium polyoxyethylene lauryl sulfate (emulsifier) were added to 30 parts by mass of ion-exchanged water and emulsified.
• a tackifier resin emulsion (manufactured by Arakawa Chemical Industries, Ltd., product name "Super Ester E-865NT”) was added so that the tackifier resin was 32 parts by mass per 100 parts by mass of the acrylic polymer contained in the acrylic polymer emulsion 1. Furthermore, ion-exchanged water was added to adjust the solid concentration to 50% by mass, and coating liquid 1 was obtained.
• the storage modulus of the pressure-sensitive adhesive was determined by the following method using a dynamic viscoelasticity measuring device ("ARES-G2 Rheometer" manufactured by TA Instruments).
• the above obtained coating solution 1 was applied onto a release liner and dried to prepare a 20 ⁇ m thick adhesive layer on the release liner.
• This adhesive layer was laminated to a thickness of about 1 mm, which was punched out to ⁇ 7.9 mm to prepare a cylindrical pellet to be used as a viscoelasticity measurement sample.
• the measurement sample was fixed to a ⁇ 7.9 mm parallel plate fixture, and the storage modulus G' was measured under the following conditions using the dynamic viscoelasticity measurement device.
• the storage modulus G' at 23° C. was read from the result.
• Coating Solution 2 Preparation of acrylic adhesive (Coating Solution 2) Coating Solution 2 was obtained in the same manner as in Production Example 1, except that the amount of tackifier resin emulsion (manufactured by Arakawa Chemical Industries, Ltd., product name "SUPER ESTER E-865NT") added was adjusted so that the tackifier resin was 10 parts by mass per 100 parts by mass of the acrylic polymer contained in the acrylic polymer emulsion.
• tackifier resin emulsion manufactured by Arakawa Chemical Industries, Ltd., product name "SUPER ESTER E-865NT
• Coating Solution 3 Preparation of acrylic adhesive (Coating Solution 3) Coating Solution 3 was obtained in the same manner as in Production Example 1, except that the tackifier resin emulsion was changed to Arakawa Chemical Industries, Ltd. (product name: "Tamanol E200NT”) and further, the tackifier resin was adjusted to 35 parts by mass per 100 parts by mass of the acrylic polymer contained in the acrylic polymer emulsion.
• a tackifier resin emulsion (manufactured by Arakawa Chemical Industries, Ltd., product name "Tamanol E200NT”) was added so that the tackifier resin was 35 parts by mass per 100 parts by mass of the acrylic polymer contained in the acrylic polymer emulsion 2. Furthermore, ion-exchanged water was added to adjust the solid content concentration to 50% by mass, and coating liquid 4 was obtained.
• a multifilament yarn was prepared by twisting 70 times per meter of seven polyethylene terephthalate (PET) fibers (manufactured by Teijin Frontier Co., Ltd.) (fineness: 167 dtex, number of filaments: 48) (fineness: 1169 dtex, number of filaments: 336).
• PET polyethylene terephthalate
• the coating solution 1 was diluted to adjust the solid content concentration, and then coated onto the core material by dipping using a coating roller. It was then dried at 100°C for 1 minute to obtain a thread-like adhesive with a glue amount of 50 mg/m.
• the obtained thread-like adhesive body was wound up to a length of 30 m with a winding width of 50 mm on a bobbin having an outer diameter of 48 mm, an inner diameter of 38 mm (1.5 inches), and a width of 70 mm to obtain a wound body.
• the amount of glue was calculated using the following formula (2) from the mass per unit length W1 [mg/m] of the polyethylene terephthalate (PET) fiber used as the core material and the mass per unit length W2 [mg/m] of the thread-like adhesive body after coating and drying.
• Amount of glue [mg/m] W2 [mg/m] - W1 [mg/m] (2)
• the obtained thread-like adhesive was cut, and a cross section without crushing or distortion in the cross section shape was extracted.
• the thread-like adhesive was stained by immersing it in a ruthenium solution, and an image of the cross section was obtained by SEM.
• the obtained image was processed by ternary software [ImageJ, AVIZO (manufactured by Thermo Fisher Scientific) (Rasband, WS, ImageJ, U.S. National Institutes of Health, Bethesda, Maryland, USA, http://imagej.nih.gov/ij/, 1997-2012; Schneider, CA, Rasband, WS, Eliceiri, KW "NIH Image to ImageJ: 25 years of image analysis”.
• the hollow part of the bobbin was passed through a horizontally extending shaft, and the resulting wound body was set.
• a tensile tester Shimadzu Corporation
• the thread-like adhesive body was pulled up from the wound body to a vertical displacement of 175 mm at 23°C and a tensile speed of 1000 mm/min. From the obtained displacement-stress value graph, the top 10 stress values between 0 and 175 mm displacement were selected, and the average value was taken as the self-adhesive strength (N).
• the adhesive strength of the thread-like adhesive body was evaluated by the following cleavage peel strength.
• the obtained bonded body for evaluation was set in a tensile testing machine (Shimadzu Autograph AG-100M2 manufactured by Shimadzu Corporation), and the ABS resin plate and the SUS plate were peeled off in a direction perpendicular to the plane of the plates under conditions of 23°C and a tensile speed of 300 mm/min, and the obtained stress value was defined as the cleavage peel force (N).
• Example 2 and 4 The coating liquid 1 was diluted to adjust the solid content concentration, and a fiber-opening process was included before the dipping process using a coating roller, so that the amount of glue, area ratio, and void ratio were as shown in Table 1.
• the thread-like adhesive bodies of Examples 2 and 4 were obtained in the same manner as in Example 1, except that the coating liquid 1 was diluted to adjust the solid content concentration, and a fiber-opening process was included before the dipping process using a coating roller, so that the amount of glue, area ratio, and void ratio were as shown in Table 1.
• the evaluation results are shown in Table 1.
• Example 3 The thread-like adhesive body of Example 3 was obtained in the same manner as Example 1, except that the coating liquid 1 was diluted to adjust the solid content concentration so that the amount of glue, area ratio, and porosity were as shown in Table 1. The evaluation results are shown in Table 1.
• Example 5 The thread-like adhesive body of Example 5 was obtained in the same manner as Example 1, except that the coating liquid 2 was diluted to adjust the solid content concentration so that the amount of glue, area ratio, and porosity were as shown in Table 1. The evaluation results are shown in Table 1.
• Example 6 to 10 The filamentous adhesive bodies of Examples 6 to 10 were obtained in the same manner as in Example 1, except that the coating liquid 1 was diluted to adjust the solid content concentration so that the amount of glue, area ratio, and porosity were as shown in Table 2. The evaluation results are shown in Table 2.
• Example 11 The thread-like adhesive body of Example 11 was obtained in the same manner as Example 1, except that the coating liquid 3 was diluted to adjust the solid content concentration so that the amount of glue, area ratio and void ratio were as shown in Table 3. The evaluation results are shown in Table 3.
• Example 12 The thread-like adhesive body of Example 12 was obtained in the same manner as Example 1, except that the coating liquid 4 was diluted to adjust the solid content concentration so that the amount of glue, area ratio and void ratio were as shown in Table 3. The evaluation results are shown in Table 3.
• Comparative Example 1 A thread-like adhesive body of Comparative Example 1 was obtained in the same manner as in Example 1, except that the coating liquid 1 was diluted to adjust the solid content concentration so that the amount of glue, area ratio, and porosity were as shown in Table 3. The evaluation results are shown in Table 3. Note that, since the thread-like adhesive body of Comparative Example 1 could not be used to bond an ABS resin plate and a SUS plate, it was not possible to evaluate the cleavage peel strength.
• Comparative Example 2 A thread-like adhesive body of Comparative Example 2 was obtained in the same manner as in Example 1, except that coating liquid 1 was used without dilution, and the amount of glue, area ratio, and void ratio were as shown in Table 3. The evaluation results are shown in Table 3.
• the thread-like adhesive of the present invention maintains excellent adhesive strength and inhibits self-adhesion even when wound into a roll, so that the thread-like adhesive can be stored and transported in a roll and can be used, for example, to fasten objects in the manufacture of electronic devices.

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• 2023
  • 2023-11-09 JP JP2024557847A patent/JPWO2024101422A1/ja active Pending
  • 2023-11-09 WO PCT/JP2023/040410 patent/WO2024101422A1/ja not_active Ceased
  • 2023-11-09 CN CN202380078337.1A patent/CN120187815A/zh active Pending
  • 2023-11-10 TW TW112143429A patent/TW202436544A/zh unknown

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