WO2024101424A1 - 粘着体 - Google Patents
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- WO2024101424A1 WO2024101424A1 PCT/JP2023/040415 JP2023040415W WO2024101424A1 WO 2024101424 A1 WO2024101424 A1 WO 2024101424A1 JP 2023040415 W JP2023040415 W JP 2023040415W WO 2024101424 A1 WO2024101424 A1 WO 2024101424A1
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- adhesive
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- core material
- mass
- adhesive body
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- 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
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
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- 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
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- 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
- C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C09J201/10—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08L61/14—Modified phenol-aldehyde condensates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L93/00—Compositions of natural resins; Compositions of derivatives thereof
- C08L93/04—Rosin
-
- 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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
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- 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
- C09J2433/00—Presence of (meth)acrylic polymer
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- 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
- C09J2499/00—Presence of natural macromolecular compounds or on derivatives thereof, not provided for in groups C09J2489/00 - C09J2497/00
Definitions
- the present invention relates to an 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.
- Patent Document 1 discloses a linear adhesive body with a small change in gel fraction after aging.
- Patent Document 2 discloses a thread-like adhesive body with strong adhesive strength that uses four or more multifilaments as a core material.
- the adhesive body does not have a release liner, which causes a problem of a decrease in adhesive strength when the adhesive body is stored or transported.
- Patent Documents 1 and 2 sufficient consideration is not given to the problem of maintaining adhesive strength.
- the present invention has been made in consideration of the above-mentioned conventional situation, and aims to provide an adhesive body that does not lose adhesive strength after storage and transportation, even if the adhesive body does not have a release liner.
- the inventors discovered that the above problems can be solved by providing an adhesive body with an adhesive in which the adhesive composition that forms the adhesive contains a base polymer and a tackifier resin with a weight-average molecular weight of 1,500 or less, thereby solving the present invention.
- An adhesive body having an adhesive The adhesive composition forming the adhesive comprises a base polymer and a tackifier resin having a weight average molecular weight of 1,500 or less.
- the adhesive body according to [1] wherein the weight average molecular weight of the tackifier resin is 1,000 or less.
- the adhesive body according to [3], wherein the core material is composed of four or more filaments.
- the adhesive body according to [1] or [2], wherein the content of the tackifier resin in the adhesive composition is 5 to 100 parts by mass per 100 parts by mass of the base polymer.
- the present invention provides an adhesive that suppresses the decrease in adhesive strength after storage and transportation, even when the adhesive does not have a release liner.
- FIG. 1 is a schematic cross-sectional view of an example of a configuration of a roll of an adhesive body.
- FIG. 2 is a schematic cross-sectional view of one configuration example of an adhesive body.
- FIG. 3 is a schematic cross-sectional view of one configuration example of the adhesive body.
- FIG. 4 is a schematic diagram of an example of a configuration of a roll of an adhesive body.
- the adhesive body 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 adhesive body includes an adhesive,
- the pressure-sensitive adhesive composition that forms the pressure-sensitive adhesive contains a base polymer and a tackifier resin having a weight-average molecular weight of 1,500 or less.
- the adhesive body according to an embodiment of the present invention by setting the weight average molecular weight (Mw) of the tackifier resin contained in the adhesive composition to 1,500 or less (preferably 1,000 or less), the compatibility between the tackifier resin and the base polymer is excellent and the tackifier resin is uniformly dispersed in the adhesive, so that a decrease in adhesive strength after storage and transportation can be prevented. Furthermore, in the adhesive body according to an embodiment of the present invention, even if the surfaces of the adhesives come into contact with each other, the contacting adhesives can be adhered to each other and then peeled off at the interface, eliminating the need for a release liner.
- Mw weight average molecular weight
- the adhesive may be wound in a roll or may be a laminate of multiple adhesives. It may also be a laminate of adhesives processed into various shapes.
- the adhesive body according to the embodiment of the present invention may be in the form of a sheet or a line.
- the adhesive body may further include a substrate, but may be an adhesive body consisting of only an adhesive without including a substrate.
- the pressure-sensitive adhesive is in the form of a sheet, it may further include a substrate, in which case the pressure-sensitive adhesive is provided on one or both sides of the sheet-like substrate.
- the concept of a sheet here may include what are called tapes, labels, films, etc.
- FIG. 1 shows an example of the structure of an adhesive body in an embodiment of the present invention.
- the adhesive body may be in the form of a sheet-shaped adhesive body 2 spirally wound around a core as an axis, as in the roll 100 shown in FIG. 1, or may be in the form of a roll without a core.
- the adhesive body 2 may be, for example, a double-sided adhesive sheet having a cross-sectional structure shown in FIG. 1.
- the adhesive body 2 is configured to include a substrate 20, and a first adhesive layer 11 and a second adhesive layer 12 provided on a first surface and a second surface of the substrate 20, respectively. In the roll 100 of the adhesive body having such a form, the surface of the second adhesive layer 12 is in contact with the surface of the first adhesive layer 11.
- the adhesive when it is linear, it may be a support-less (core material) adhesive consisting of a linear adhesive layer, or it may further include a core material.
- Figure 2 shows a schematic cross-sectional view of an example of the adhesive body 3 in an embodiment of the present invention, taken in a direction perpendicular to the longitudinal direction of the adhesive body 3.
- the adhesive body 3 in this example is a support-less adhesive body made of a linear adhesive layer 13.
- the term "linear” as used here is a concept that includes not only straight lines, curved lines, and broken lines, but also a state in which the adhesive body can be bent in various directions and at various angles like a thread (hereinafter sometimes referred to as "thread-like").
- the adhesive layer in this specification also includes linear adhesive bodies.
- the adhesive body according to the embodiment of the present invention may be a thread-like adhesive body.
- thread-like refers to a shape in which the longitudinal length is sufficiently longer than the width direction length, the ratio of the long axis length to the short axis length in the cross-sectional shape (long axis/short axis) is, for example, 200 or less, and the shape can be bent in various directions and at various angles like a thread.
- the thread-like adhesive can be bent in a variety of directions and angles, so it can be bent to match the shape of the bonding area, making it possible to accommodate a variety of shapes of bonding areas.
- cross-sectional shape of the adhesive body in this configuration example is circular, this embodiment is not limited to this, and the cross-sectional shape can be circular, elliptical, rectangular, or other shapes.
- Figure 3 shows a schematic cross-sectional view of an example of the configuration of an adhesive body according to an embodiment of the present invention, taken in a direction perpendicular to the longitudinal direction of the adhesive body.
- the adhesive body 4 shown in Figure 3 comprises a linear core material 14 and an adhesive layer 13 that covers the longitudinal surface of the core material 14.
- the cross-sectional shape of the adhesive body 4 in this configuration example is circular, this embodiment is not limited to this, and the cross-sectional shape can be an ellipse, a rectangle such as a square, etc., in addition to a circle.
- Another configuration example of the adhesive body in the embodiment of the present invention is shown in Fig. 4.
- the adhesive body may be a wound body 200 in which the adhesive body 4 is wound around a winding core.
- the material of the core can be any suitable material of the core, but for example, paper, plastic, etc. can be used.
- the outer diameter of the core can be, for example, 4 cm or more and 20 cm or less.
- the inner diameter of the core can be, for example, 3 cm or more and 19 cm or less.
- the width of the core can be, for example, 1 cm or more and 100 cm or less.
- the adhesive body according to the embodiment of the present invention may further include a core material, and the adhesive may cover the surface of the core material in the longitudinal direction.
- the pressure-sensitive adhesive body according to the embodiment of the present invention preferably contains a pressure-sensitive adhesive as the outermost layer.
- the adhesive when the adhesive according to the embodiment of the present invention further includes a core material, it is preferable that the adhesive coats 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 peripheral surface 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.
- an adhesive with excellent strength is obtained. This is thought to be because the core material is not exposed on the surface, preventing stress from concentrating on one part of the core material and causing it to break.
- 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 obtain an adhesive body with excellent strength.
- the adhesive may be impregnated into the core material.
- the adhesive is impregnated into the core material means that the adhesive is present between multiple filaments in the core material. When the adhesive is impregnated into the core material, the adhesive and the core material maintain adhesion, making them less likely to peel off, and improving the strength of the adhesive body.
- the adhesive that makes up the adhesive body is explained below.
- the pressure-sensitive adhesive body includes a pressure-sensitive adhesive composition that forms the pressure-sensitive adhesive, the pressure-sensitive adhesive composition including a base polymer and a tackifier resin having a weight-average molecular weight of 1,500 or less. That is, in an embodiment of the present invention, the pressure-sensitive adhesive can be formed from a pressure-sensitive adhesive composition.
- the type of adhesive is not particularly limited, and examples that can be used include acrylic adhesives, rubber adhesives, vinyl alkyl ether adhesives, silicone adhesives, polyester adhesives, polyamide adhesives, urethane adhesives, fluorine adhesives, and epoxy adhesives.
- acrylic adhesives urethane adhesives, silicone adhesives, rubber adhesives, or polyester adhesives are preferred, with acrylic adhesives being particularly preferred because adhesiveness is easy to control.
- acrylic adhesives being particularly preferred because adhesiveness is easy to control.
- only one type of adhesive may be used alone, or two or more types may be used in combination.
- the adhesive in the embodiment of the present invention is preferably a pressure-sensitive adhesive that has adhesiveness at room temperature and can attach an adherend to its surface by the pressure generated when the surface of the adhesive comes into contact with the surface of the adherend. Pressure-sensitive adhesives do not require heating and can be applied to adherends that are sensitive to heat.
- acrylic adhesive refers to an adhesive that uses an acrylic polymer as the base polymer (the main component of the polymer component, i.e., a component that accounts for 50% or more by weight).
- 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 weight 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 as a 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.
- alkyl (meth)acrylate for example, a compound represented by the following formula (1) can be suitably used.
- CH2 C( R1 ) COOR2 (1) (wherein R 1 represents a hydrogen atom or a methyl group, and R 2 represents an alkyl group having 2 to 14 carbon atoms).
- 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% by weight or more (for example, about 80 to 99.8% by weight), preferably 85% by weight or more (for example, about 85 to 99.5% by weight), and more preferably 90% by weight or more (for example, about 90 to 99% by weight).
- 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, 0.5 to 12 parts by weight, and preferably about 1 to 8 parts by weight, per 100 parts by weight 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 adhesive article.
- the amount of crosslinking agent per 100 parts by weight of the monomer raw material (excluding the crosslinking agent) is preferably 0.005 to 5 parts by weight, and more preferably in the range of 0.01 to 3 parts by weight.
- 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 thereof 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 adhesive composition may be either a solvent-based adhesive or a water-dispersed adhesive.
- Water-dispersed adhesive compositions are preferred because they can be applied at high speed, are environmentally friendly, and have little effect on the core material (swelling, dissolution) due to the solvent.
- 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 weight per 100 parts by weight 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 weight, and preferably about 0.5 to 5 parts by weight, per 100 parts by weight 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 thickeners, surfactants, antioxidants, fillers, pigments, and colorants.
- a base such as aqueous ammonia
- an acid to adjust the pH
- additives commonly used in adhesives such as thickeners, surfactants, antioxidants, fillers, pigments, and colorants.
- the adhesive may also contain various additives, such as crosslinking agents, viscosity adjusters (thickeners, etc.), leveling agents, release adjusters, plasticizers, softeners, fillers, colorants (pigments, dyes, etc.), surfactants, antistatic agents, preservatives, antioxidants, UV absorbers, antioxidants, and light stabilizers.
- additives such as crosslinking agents, viscosity adjusters (thickeners, etc.), leveling agents, release adjusters, plasticizers, softeners, fillers, colorants (pigments, dyes, etc.), surfactants, antistatic agents, preservatives, antioxidants, UV absorbers, antioxidants, and light stabilizers.
- 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 weight or less, and more preferably 5 parts by weight or less, per 100 parts by weight of the base polymer.
- the pressure-sensitive adhesive composition (which may be a pressure-sensitive adhesive) according to an embodiment of the present invention contains a tackifier resin having a weight average molecular weight of 1,500 or less.
- the tackifier resin is not particularly limited as long as it has a weight average molecular weight of 1,500 or less, and any appropriate tackifier resin can be used.
- the weight average molecular weight of the tackifier resin is preferably 1,000 or less, more preferably 100 to 1,000, even more preferably 300 to 990, and particularly preferably 500 to 980.
- a tackifier resin with a weight average molecular weight of 1,500 or less By using a tackifier resin with a weight average molecular weight of 1,500 or less, the base polymer and the tackifier resin become more compatible with each other, and segregation of the tackifier resin on the surface layer of the adhesive is suppressed. Therefore, even if the adhesive is stored without being protected by a release liner, a decrease in the adhesive strength of the adhesive after storage is suppressed. Furthermore, even if a tackifier resin having a weight average molecular weight of 1500 or less (preferably 1000 or less) segregates on the surface layer of the adhesive depending on storage conditions, it can maintain its compatibility and therefore maintain its adhesiveness. Tackifying resins having a weight average molecular weight of more than 1,500 are incompatible and cannot maintain adhesion.
- tackifying resins include rosin-based tackifying resins (e.g., unmodified rosin, modified rosin, rosin phenolic resins, rosin ester resins, etc.), terpene-based tackifying resins (e.g., terpene resins, terpene phenolic resins, styrene-modified terpene resins, aromatic modified terpene resins, hydrogenated terpene resins), hydrocarbon-based tackifying resins (e.g., aliphatic hydrocarbon resins, aliphatic cyclic hydrocarbon resins, aromatic hydrocarbon resins (e.g., styrene-based resins, xylene-based resins, etc.), aliphatic and aromatic petroleum resins, aliphatic and alicyclic petroleum resins, hydrogenated hydrocarbon resins, coumarone resins, coumarone indene resins, etc.), phenol-based tackifying
- Tackifying resins may be used alone or in combination of two or more.
- the content of the tackifier resin in the pressure-sensitive adhesive composition is preferably 1 part by mass or more, more preferably 5 parts by mass or more, even more preferably 10 parts by mass or more, even more preferably 20 parts by mass or more, and particularly preferably 30 parts by mass or more, relative to 100 parts by mass of the base polymer, from the viewpoint of improving the adhesive strength. Also, from the viewpoint of suppressing a decrease in the adhesive strength of the pressure-sensitive adhesive, the content is preferably 100 parts by mass or less, more preferably 90 parts by mass or less.
- the pressure-sensitive adhesive composition contains a base polymer and a tackifier resin, and preferably contains 1 to 100 parts by mass of the tackifier resin relative to 100 parts by mass of the base polymer, more preferably contains 5 to 100 parts by mass, even more preferably contains 10 to 100 parts by mass, even more preferably contains 10 to 90 parts by mass, particularly preferably contains 20 to 90 parts by mass, and most preferably contains 30 to 90 parts by mass.
- the method for forming the adhesive body is not particularly limited, but for example, when forming an adhesive layer, a method in which an adhesive composition is directly applied to a peelable or non-peeling substrate and then dried or cured (direct method); a method in which an adhesive composition is applied to a peelable surface and then dried or cured to form an adhesive layer on the surface, and then the adhesive layer is transferred by laminating it to a substrate (transfer method); etc. can be used.
- the sheet-shaped pressure-sensitive adhesive (pressure-sensitive adhesive sheet) can be obtained, for example, by applying the pressure-sensitive adhesive composition onto a substrate and thermally crosslinking the composition to form a pressure-sensitive adhesive layer.
- the pressure-sensitive adhesive layer can be formed on a release liner, and the release liner can be removed to obtain a pressure-sensitive adhesive sheet without a substrate.
- the pressure-sensitive adhesive sheet may be a pressure-sensitive adhesive tape, and from the viewpoints of strength and handling, the width of the pressure-sensitive adhesive tape is preferably 0.01 mm or more, more preferably 0.02 mm or more, and is preferably 40 mm or less, more preferably 20 mm or less, since the pressure-sensitive adhesive can be applied to a variety of adherends having different surface shapes and regions.
- the thickness is not particularly limited, but if the thickness is too small, handling may be impaired, so for example, it is preferably 1 ⁇ m or more, and more preferably 5 ⁇ m or more. Also, if the thickness is too large, flexibility may be lacking, so for example, it is preferably 100 ⁇ m or less, and more preferably 50 ⁇ m or less.
- the substrate has a higher adhesive strength between the adhesive layer and the substrate than between the adhesive layers themselves, from the viewpoint of maintaining the shape of the adhesive.
- plastic films such as polypropylene film, ethylene-propylene copolymer film, polyester film, and polyvinyl chloride; paper such as kraft paper; and metal foil can be used.
- the plastic film may be either a non-stretched film or a stretched (uniaxially stretched or biaxially stretched) film.
- the surface of the substrate to which the adhesive composition is applied may be subjected to a surface treatment such as a commonly used primer or a corona discharge method.
- the thickness of the substrate can be appropriately selected depending on the purpose, but is generally about 10 to 500 ⁇ m.
- the thickness of the adhesive layer is not particularly limited and can be selected appropriately depending on the purpose. Generally, the thickness of the adhesive layer is appropriately set to about 1 ⁇ m to 200 ⁇ m, and preferably to about 3 ⁇ m to 150 ⁇ m.
- the adhesive composition 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, spray coater, etc.
- the adhesive composition is applied so that the thickness of the adhesive layer after drying is, for example, about 10 to 100 ⁇ m.
- the drying temperature can be appropriately selected, but is preferably 40°C to 200°C, more preferably 50°C to 180°C, and particularly preferably 70°C to 120°C.
- An appropriate drying time can be selected as appropriate.
- the drying time is preferably 5 seconds to 20 minutes, more preferably 5 seconds to 10 minutes, and particularly preferably 10 seconds to 5 minutes.
- Thermal crosslinking is carried out by a conventional method, for example, by heating to a temperature at which the crosslinking reaction proceeds depending on the type of crosslinking agent.
- the solvent-insoluble portion of the crosslinked adhesive is, for example, about 5 to 70% by weight.
- the molecular weight (weight average molecular weight; standard polystyrene equivalent) of the solvent-soluble portion of the crosslinked adhesive is, for example, about 100,000 to 600,000, preferably about 200,000 to 450,000.
- the molecular weight of the solvent-insoluble portion and solvent-soluble portion of the crosslinked adhesive can be set as desired, for example, by appropriately adjusting the ratio of the crosslinking agent or functional group-containing monomer to the total amount of monomers, the type and amount of the chain transfer agent, and particularly the amounts of the crosslinking agent and chain transfer agent.
- the linear adhesive body can be obtained, for example, by the following method.
- the method of forming the linear adhesive body is not particularly limited, but for example, a method of preparing an adhesive composition constituting the adhesive body, applying the adhesive composition in a line on a release liner using a dispenser to form an adhesive body once, and then removing the release liner can be mentioned.
- the adhesive body is an adhesive body having a core material and an adhesive
- the adhesive composition can be applied to the surface of the core material by dipping, immersion, coating, etc., and then heated and dried to form the adhesive on the surface of the core material.
- the application of the adhesive composition can be performed using a conventional coater such as a gravure roll coater, reverse roll coater, kiss roll coater, dip roll coater, bar coater, knife coater, spray coater, etc.
- the drying temperature can be appropriately adopted, but is preferably 40°C to 200°C, more preferably 50°C to 180°C, and particularly preferably 70°C to 120°C.
- the drying time can be appropriately adopted. The drying time is preferably 5 seconds to 20 minutes, more preferably 5 seconds to 10 minutes, and particularly preferably 10 seconds to 5 minutes.
- the diameter of the cross-section of the adhesive body is not particularly limited, but since a diameter that is too small may cause the adhesive body to break easily, it is preferable that the diameter is, for example, 20 ⁇ m or more, and more preferably 50 ⁇ m or more. Furthermore, since a diameter that is too large may cause the adhesive body to lack flexibility, it is preferable that the diameter is, for example, 1000 ⁇ m or less, and more preferably 500 ⁇ m or less.
- the adhesive when the adhesive is a linear adhesive having a core material, the adhesive may cover the entire surface of the core material (surface in the longitudinal direction), or may cover only a portion of the surface of the core material.
- the adhesive is typically formed continuously, but is not limited to such a form, and may be formed in a regular or random pattern such as dots or stripes.
- the end faces of the core material may or may not be covered with the adhesive. For example, in cases where the adhesive article is cut during the manufacturing process or during use, the end faces of the core material may not be covered with the adhesive.
- the core material used in the adhesive is not particularly limited, but may be, for example, a resin, rubber, foam, inorganic fiber, or a composite of these. From the viewpoint of maintaining the shape of the adhesive, it is preferable that the adhesive strength between the adhesive layer and the core material is higher than the self-adhesive strength between the adhesive layers.
- resins include polyolefins such as polyethylene (PE), polypropylene (PP), ethylene-propylene copolymer, and ethylene-vinyl acetate copolymer; polyesters such as polyethylene terephthalate (PET); vinyl chloride resins; vinyl acetate resins; polyimide resins; polyamide resins; fluorine-based resins; and the like.
- Examples of rubbers include synthetic rubbers such as natural rubber and urethane rubber; examples of foams include polyurethane foam and polychloroprene rubber foam; examples of fibers include glass fiber, carbon fiber, metal fiber, and the like.
- the cross-sectional shape of the core material is not particularly limited, but it usually has a cross-sectional shape corresponding to the cross-sectional shape of the adhesive article.
- the material of the thread-like core material that can be used for the thread-like adhesive body is not particularly limited, and may be chemical fiber or natural fiber.
- chemical fibers include various polymer materials such as rayon, cupra, acetate, promix, nylon, aramid, vinylon, vinylidene, polyvinyl chloride, polyester, acrylic, polyethylene, polypropylene, polyurethane, polychlar, polylactic acid, glass, carbon fiber, synthetic rubber such as polyurethane, metal, etc.
- natural fibers include silk, natural rubber, cotton, wool, etc.
- polyester is preferred as the material of the core material because it is easy to control the physical properties such as diameter and tensile strength, and polyethylene terephthalate (PET) is more preferred.
- the thread-like core material for example, in addition to monofilament, multifilament, spun yarn, textured yarn generally called textured yarn, bulky yarn, stretch yarn, etc., which has been subjected to crimping or bulking processing, or yarns which are combined by twisting these together, etc.
- the cross-sectional shape may be not only circular, but also short shaped yarn such as a square or star, elliptical, hollow, etc.
- the core material preferably has multiple filaments and is a multifilament yarn made by doubling or twisting multiple filaments. If the core material is a multifilament yarn, sufficient strength and stable physical properties can be obtained.
- 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 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 known or conventional surface treatments, such as corona discharge treatment, plasma treatment, application of a primer, etc.
- the cross-sectional size of the core material is not particularly limited and can be selected appropriately depending on the purpose, but for example, if the cross-sectional shape is circular, from the viewpoint of handleability (resistance to cutting), the diameter is preferably 1 ⁇ m to 2000 ⁇ m, and more preferably 10 ⁇ m to 1000 ⁇ m.
- the thickness of the adhesive layer is not particularly limited, but from the viewpoint of adhesiveness, it is preferably, for example, 1 ⁇ m or more, and more preferably 3 ⁇ m or more. Also, from the viewpoint of drying property, it is preferably, for example, 200 ⁇ m or less, and more preferably 150 ⁇ m or less.
- the diameter of the adhesive body is not particularly limited, but for example, when the cross-sectional shape is circular, from the viewpoint of processability, it is preferably 50 ⁇ m to 1000 ⁇ m, more preferably 100 ⁇ m to 800 ⁇ m, and even more preferably 200 ⁇ m to 600 ⁇ m.
- the linear adhesive body in the embodiment of the present invention is preferable in that it can be attached to a narrow member or a narrow area while suppressing overflow, and can be easily disassembled (reworked).
- the linear adhesive body is also referred to as a linear adhesive body.
- the linear adhesive body in the embodiment of the present invention can be suitably used for fixing an article in the manufacture of an electronic device and for fixing an in-vehicle component, and can also be applied to fixing a narrow frame of a mobile terminal such as a mobile phone or a smartphone, and fixing a battery, a motor, etc.
- the adhesive body in the embodiment of the present invention is linear, it can be inserted into a narrow gap to adhere to the surface of the gap or fill the gap.
- the adhesive body in the embodiment of the present invention is preferably bendable, and is particularly preferably a thread-like adhesive body that can be bent in various directions and angles like a thread.
- a bendable adhesive body particularly a thread-like adhesive body, has the advantage of being easily applicable to complex shapes such as curves, curved surfaces, and unevenness.
- a thread-like adhesive body is also referred to as a thread-like adhesive body.
- the adhesive body in the embodiment of the present invention is preferably a thread-like adhesive body.
- the adhesive body has bendability, particularly the filamentous adhesive body, it 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.
- the filamentous adhesive body can be applied to the desired portion at once, i.e., in one process, so that it is excellent in workability and can be applied to an automated line.
- the thread-like adhesive can be used to fix cables such as electric wires and optical fibers, LED fiber lights, optical fiber sensors such as FBG (Fiber Bragg Gratings), various wires (linear members) such as threads, strings, and wires, and thin members in a desired shape.
- cables such as electric wires and optical fibers, LED fiber lights, optical fiber sensors such as FBG (Fiber Bragg Gratings), various wires (linear members) such as threads, strings, and wires, and thin members in a desired shape.
- FBG Fiber Bragg Gratings
- various wires linear members
- the thread-like adhesive 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 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 adhesive attached to the surface of the other member to fix it.
- the thread-like adhesive may be attached to a wire or narrow member, and then the wire or narrow member may be fixed to another member in the desired configuration.
- the thread-like adhesive can also be suitably used for the purpose of temporarily fixing (temporarily fastening) an article to the surface of another article. More specifically, the thread-like adhesive is particularly suitably 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 use is not limited thereto, and the thread-like adhesive can be suitably used for various purposes where temporary fixing (temporarily fastening) is desired. For example, when fixing one article to the surface of another article, 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 it is easy to provisionally fix the two articles while avoiding the fixing part provided between the two articles.
- the two articles can be attached well while minimizing overflow, wrinkles, and overlaps, even if they have complex shapes such as curves, curved surfaces, or unevenness, and furthermore, they can be attached in a single process, making the process easy to work with.
- the adhesive is a thread-like adhesive, it is easy to remove the thread-like adhesive from between the two fixed (full-fixed) articles after the two articles are fixed (full-fixed) together, if necessary. In this way, the adhesive can be prevented from spilling out, and the deterioration of the design caused by the discoloration of the remaining adhesive over time can be effectively prevented.
- the thread-like adhesive according to the embodiment of the present invention can be used as a dam material for preventing the adhesive or pressure-sensitive adhesive from protruding 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 protrusion of a sealing resin used in bonding optical panels.
- the thread-like adhesive may be peeled off after the adhesive or pressure-sensitive adhesive has hardened, or may be left in place.
- the thread-like adhesive material according to the embodiment of the present invention can be twisted 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 can be produced by known methods, for example, a method including a coating step in which a coating liquid containing an adhesive is applied 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 may or may not include a fiber-spreading step.
- the core material is spread by running the core material along a non-rotating roller when the adhesive is applied to the core material.
- the method for producing a thread-like adhesive body 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 more preferably 0.4 to 4.0 times the core material payout speed, further preferably 0.5 to 3.0 times, and particularly preferably 0.8 to 1.5 times.
- the coating step it is preferable to apply a tension of 6.0 mN/dtex or less to the core material.
- 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.
- An adhesive body having an adhesive The adhesive composition forming the adhesive comprises a base polymer and a tackifier resin having a weight average molecular weight of 1,500 or less.
- the adhesive body according to any one of [1] to [5], wherein the content of the tackifier resin in the adhesive composition is 5 to 100 parts by mass per 100 parts by mass of the base polymer.
- Preparation of Acrylic Polymer Emulsion 1 40 parts by mass of ion-exchanged water was placed in a reaction vessel equipped with a cooling tube, a nitrogen inlet tube, a thermometer, and a stirrer, and nitrogen substitution was performed by stirring at 60°C for 1 hour or more while introducing nitrogen gas. 0.1 parts by mass of 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] n-hydrate (polymerization initiator) was added to this reaction vessel. While maintaining the reaction liquid at 60°C, the following Monomer Emulsion A was gradually added dropwise over 4 hours to allow the emulsion polymerization reaction to proceed.
- monomer emulsion B 68 parts by mass of butyl acrylate (BA), 29.1 parts by mass of 2-ethylhexyl acrylate, 2.9 parts by mass of acrylic acid, 0.05 parts by mass of lauryl mercaptan (chain transfer agent), 0.03 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 25 parts by mass of ion-exchanged water and emulsified.
- BA butyl acrylate
- 2-ethylhexyl acrylate 2.9 parts by mass of acrylic acid
- lauryl mercaptan chain transfer agent
- ⁇ -methacryloxypropyltrimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd., product name "KBM-503
- Adhesive composition Preparation of Adhesive Liquid 1
- a tackifier resin emulsion manufactured by Arakawa Chemical Industries, Ltd., product name "Tamanol E200NT" was added 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 1. Further, ion-exchanged water was added to adjust the solid content concentration to 45% by mass, and adhesive liquid 1 was obtained.
- the weight average molecular weight of the tackifier resin can be measured by gel permeation chromatography (GPC) and calculated as a standard polystyrene equivalent value. Specifically, the weight average molecular weight can be measured under the following conditions using a GPC measuring device with the trade name "HLC-8220GPC" (manufactured by Tosoh Corporation). The same applies to the examples described later.
- GPC measurement conditions Sample concentration: 0.2% by weight (tetrahydrofuran solution) Sample injection volume: 10 ⁇ L Eluent: tetrahydrofuran (THF) Flow rate (flow rate): 0.6 mL/min Column temperature (measurement temperature): 40° C.
- Adhesive Solutions 2 to 4 The adhesive liquids were prepared in the same manner as Adhesive Liquid 1, except that the amount of tackifier resin emulsion added was changed to 20 parts by mass, 30 parts by mass, or 35 parts by mass of the tackifier resin per 100 parts by mass of the acrylic polymer.
- Adhesive Liquid 5 (Preparation of Adhesive Liquid 5) 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. Further, ion-exchanged water was added to adjust the solid content concentration to 45% by mass, and thus an adhesive liquid 5 was obtained.
- Adhesive Liquid 6 (Preparation of Adhesive Liquid 6) 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 3. Further, ion-exchanged water was added to adjust the solid content concentration to 45% by mass, and thus a pressure-sensitive adhesive liquid 6 was obtained.
- Adhesive Liquid 7 (Preparation of Adhesive Liquid 7) A tackifier resin emulsion (manufactured by Arakawa Chemical Industries, Ltd., product name "Super Ester NS100H") was added 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 1. Further, ion-exchanged water was added to adjust the solid content concentration to 45% by mass, and thus an adhesive liquid 7 was obtained.
- Adhesive Liquid 8 (Preparation of Adhesive Liquid 8) A tackifier resin emulsion (manufactured by Arakawa Chemical Industries, Ltd., product name "Super Ester E865NT”) 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. Further, ion-exchanged water was added to adjust the solid content concentration to 45% by mass, thereby obtaining a pressure-sensitive adhesive liquid 8.
- Example 1 The adhesive liquid 1 was applied to a 25 ⁇ m thick PET film (Lumirror #25) so that the thickness when dried would be 20 ⁇ m, and dried for 2 minutes at 100° C. After drying, a release liner (DIAFOIL MRF #38) was placed over the film to obtain an adhesive tape.
- DIAFOIL MRF #38 a release liner
- Adhesive tapes were prepared in the same manner as in Example 1, except that adhesive liquids 2 to 8 were used instead of adhesive liquid 1 to produce the adhesive tapes.
- the adhesive strength refers to the 180 degree peel strength (180 degree peel adhesive strength) against an acrylonitrile butadiene styrene copolymer resin plate (ABS plate).
- ABS plate acrylonitrile butadiene styrene copolymer resin plate
- the sample was allowed to stand for 30 minutes in an environment of 23°C and 50% humidity, and then pulled at a peel rate of 300 mm/min using a tensile tester (Shimadzu Autograph AG-100M2, manufactured by Shimadzu Corporation) to measure the initial adhesive strength (N/10 mm).
- a tensile tester Shimadzu Autograph AG-100M2, manufactured by Shimadzu Corporation
- the adhesive tapes of the examples and comparative examples were each cut to a width of 10 mm and a length of 70 mm, the release liner was peeled off, and the tape was left to stand in a thermostatic chamber at 60°C for 7 days. After 7 days, the adhesive tape was removed from the thermostatic chamber and left to stand in a 23°C, 50% humidity environment for 1 hour. The adhesive tape was then pressed against an ABS plate with a 2 kg roller in one reciprocating motion to prepare a sample.
- the sample was left to stand for 30 minutes in a 23°C, 50% humidity environment without being protected by a release liner, and then pulled at a peeling speed of 300 mm/min with a tensile tester (Shimadzu Autograph AG-100M2 manufactured by Shimadzu Corporation) in the same manner as in the initial adhesive strength test, and the adhesive strength (N/10 mm) after storage was measured.
- a tensile tester Shimadzu Autograph AG-100M2 manufactured by Shimadzu Corporation
- Adhesive strength retention rate Adhesive strength after storage ⁇ 100 / Initial adhesive strength (2)
- the polymer column indicates the monomer type and amount (parts by mass) of each monomer that constitutes the polymer.
- “acrylic liquid” and “acrylic liquid polymer” in the table refer to the acrylic polymer emulsion described above.
- the adhesive of the present invention it is possible to provide an adhesive that suppresses the decrease in adhesive strength after storage and transportation, even if the adhesive does not have a release liner.
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Abstract
Description
〔1〕
粘着剤を備えた粘着体であって、
前記粘着剤を形成する粘着剤組成物がベースポリマーと、重量平均分子量1500以下の粘着付与樹脂とを含む、粘着体。
〔2〕
前記粘着付与樹脂の重量平均分子量が1000以下である、〔1〕に記載の粘着体。
〔3〕
更に芯材を備え、前記粘着剤が前記芯材の長手方向の表面を被覆する、〔1〕に記載の粘着体。
〔4〕
糸状粘着体である、〔1〕又は〔2〕に記載の粘着体。
〔5〕
前記芯材がフィラメント数4本以上で構成された〔3〕に記載の粘着体。
〔6〕
前記粘着剤組成物における前記粘着付与樹脂の含有量は、前記ベースポリマー100質量部に対して、5~100質量部である、〔1〕又は〔2〕に記載の粘着体。
なお、本発明は、以下に説明する実施形態に限定されるものではない。また、本明細書において「~」という表現を用いる場合は、その前後の数値又は物性値を含む表現として用いる。
また、本明細書において、「重量」と「質量」、「重量%」と「質量%」、および「重量部」と「質量部」は、それぞれ同義語として扱う。
粘着体は、粘着剤を備え、
前記粘着剤を形成する粘着剤組成物がベースポリマーと、重量平均分子量1500以下の粘着付与樹脂とを含む。
また、本発明の実施形態に係る粘着体は、粘着剤の表面が互いに接触した場合であっても、接触した粘着剤が互いに接着した後に界面で剥離することが可能であるため、はく離ライナーが不要である。
粘着体がシート状である場合、基材を更に含んでいてもよく、この場合にはシート状の基材の片面又は両面に粘着剤が設けられる。ここでいうシートの概念には、テープ、ラベル、フィルム等と称されるものが包含され得る。
図1に、本発明の実施形態における粘着体の一構成例について示す。粘着体は、図1に示す巻回体100のように、巻芯を軸としてシート状の粘着体2が渦巻き状に巻回された形態であってもよく、巻芯なしで巻回された形態であってもよい。粘着体2は、例えば、図1に示す断面構造を有する形態の両面粘着シートであってもよい。粘着体2は、基材20と、その基材20の第一面および第二面にそれぞれ設けられた第一粘着剤層11および第二粘着剤層12とを含んで構成されている。かかる形態の粘着体の巻回体100は、第二粘着剤層12の表面が、第一粘着剤層11の表面に接触している。
ここで、糸状とは、長手方向の長さが幅方向の長さに対して十分に長く、断面形状における短軸の長さに対する長軸の長さの割合(長軸/短軸)が、例えば200以下であり、また、糸のように多様な方向、多様な角度に曲げられうる状態の形状を意味する。
図4に、本発明の実施形態における粘着体の他の構成例について示す。粘着体は、図4に示すように、粘着体4を巻芯に巻回させた巻回体200としてもよい。
また、巻芯の寸法にも特に制限がない。巻芯の外径は、例えば、4cm以上、20cm以下とすることができる。巻芯の内径は、例えば、3cm以上、19cm以下とすることができる。巻芯の幅は、例えば、1cm以上、100cm以下とすることができる。
また、本発明の実施形態に係る粘着体は、粘着剤を最外層として含むことが好ましい。
本発明の実施形態に係る粘着体は、粘着剤を備える。粘着剤を形成する粘着剤組成物がベースポリマーと、重量平均分子量1500以下の粘着付与樹脂とを含む。
すなわち、本発明の実施形態において、粘着剤は、粘着剤組成物により形成することができる。
(式中、R1は水素原子又はメチル基、R2は炭素数2~14のアルキル基を示す)で表される化合物が挙げられる。
水分散型粘着剤組成物は、例えば、前記(メタ)アクリル酸アルキルエステルを主成分とし且つシラン系単量体を含む単量体混合物を慣用の乳化重合に付して、(メタ)アクリル酸エステル共重合体の水分散液を得、これに必要に応じて前記他の架橋剤を添加することにより調製できる。
上記粘着付与樹脂としては、重量平均分子量が1500以下のものであれば特に制限は無く、任意の適切な粘着付与樹脂が用いられる。
粘着付与樹脂の重量平均分子量は1000以下が好ましく、100~1000がより好ましく、300~990がさらに好ましく、500~980が特に好ましい。
重量平均分子量が1500以下の粘着付与樹脂を用いることにより、ベースポリマーと粘着付与樹脂が相溶し易くなり、粘着付与樹脂が粘着剤表層に偏析することが抑えられるため、はく離ライナーにより粘着剤を保護せずに保管した場合であっても、保管後の粘着剤の粘着力低下を抑制する。
また、重量平均分子量が1500以下(好ましくは1000以下)の粘着付与樹脂が、保管条件によって粘着剤表層に偏析しても相溶状態を維持することで粘着性を維持することができる。
重量平均分子量が1500超の粘着付与樹脂では非相溶となり、粘着性を維持できない。
粘着剤組成物は、ベースポリマーと粘着付与樹脂とを含み、ベースポリマー100質量部に対して、粘着付与樹脂を1~100質量部含むことが好ましく、5~100質量部含むことがより好ましく、10~100質量部含むことがさらに好ましく、10~90質量部含むことがよりさらに好ましく、20~90質量部含むことが特に好ましく、30~90質量部含むことが最も好ましい。
粘着シートは、粘着テープであってもよく、強度及びハンドリングの観点から粘着テープの幅は0.01mm以上であることが好ましく、0.02mm以上であることがより好ましい。また、適用可能な被着体の表面形状や領域が多様な粘着体とし得ることから、40mm以下であることが好ましく、20mm以下であることがより好ましい。
本実施形態において線状粘着体を形成する方法は特に限定されないが、例えば、粘着体を構成する粘着剤組成物を用意し、はく離ライナー上にディスペンサを用いて線状に塗布して粘着体をいったん形成し、はく離ライナーを除去する方法が挙げられる。なお、粘着体が芯材及び粘着剤を有する粘着体である場合には、芯材の表面に粘着剤組成物をディッピング、浸漬、塗布等により塗工した後に加熱乾燥させることにより、芯材の表面に粘着剤を形成させることができる。上記粘着剤組成物の塗布は、例えば、グラビアロールコーター、リバースロールコーター、キスロールコーター、ディップロールコーター、バーコーター、ナイフコーター、スプレーコーター等の慣用のコーターを用いて行うことができる。乾燥温度は、適宜採用可能であるが、好ましくは40℃~200℃であり、さらに好ましくは、50℃~180℃であり、特に好ましくは70℃~120℃である。乾燥時間は、適宜、適切な時間が採用され得る。上記乾燥時間は、好ましくは5秒~20分、さらに好ましくは5秒~10分、特に好ましくは、10秒~5分である。
また、糸状の芯材の形態としては、例えば、モノフィラメントの他、マルチフィラメント、スパンヤーン、捲縮加工や嵩高加工等を施した一般的にテクスチャードヤーン、バルキーヤーン、ストレッチヤーンと称される加工糸、あるいはこれらを撚り合わせる等して組み合わせた糸が使用できる。また、断面形状も、円形だけでなく、四角形状や星型等の短形状の糸や楕円形状、中空等でありうる。
加えて、本発明の実施形態における粘着体が線状であると、狭い隙間に入り込ませることで、隙間の表面に接着したり、隙間を埋めたりすることができる。
例えば、曲線や曲面、凹凸などの複雑な形状の部分を有する被着体に粘着テープを貼り付けようとすると、かかる部分において粘着テープにしわや重なりが生じてしまい、はみ出しを抑えて綺麗に貼り付けることは困難であり、また、しわや重なりの生じた部分は粘着力が低下する要因ともなるおそれがある。また、しわや重なりを生じないようにしながら粘着テープを貼り付けるには、粘着テープを細かく切断しながら貼り付けることも考えられるが、作業性が大幅に悪化することとなる。一方、可曲性を有する粘着体、特に糸状粘着体であれば、曲線や曲面、凹凸などの複雑な形状の部分に貼り付ける際にも、しわや重なりを生じることなく強固に貼り付けることができる。さらに、糸状粘着体は、貼り付けたい部分に、一度に、すなわち一工程で貼り付け可能であることから、作業性にも優れ、自動化ラインにも適用可能である。
例えば、一の物品を他の物品の表面に固定する際に、該一の物品を該他の物品の表面に糸状粘着体を用いて予め仮固定させて位置決めした後に、両物品を熱圧着や縫製等の固定方法により固定(本固定)する。この場合において、糸状粘着体であれば、両物品間に設けられる固定部を避けて仮固定することが容易である。例えば、繊維製品や皮革製品を縫製する場合において、糸状粘着体により仮固定を行えば、縫製部分を避けて仮固定することが容易であり、粘着剤の針への付着を容易に防止できる。
また、糸状粘着体であれば、上述したように、両物品の形状が曲線や曲面、凹凸などの複雑な形状であっても、はみ出しやしわ、重なりを抑えながら良好に貼り付けでき、しかも一工程で貼り付け可能であり、作業性が良好である。
また、例えば、繊維製品ないし皮革製品を構成する生地、布、皮革等といった変形しやすい部材であっても、糸状粘着体による仮固定を行うことにより、引張による部材の変形が抑制ないし防止でき、固定(本固定)後の意匠性が良好となる。
さらには、糸状粘着体であれば、両物品の固定(本固定)後に、必要に応じて固定(本固定)された両物品間から糸状粘着体を抜き取り除去することも容易である。このようにすれば、粘着剤のはみ出しが防止でき、残存する粘着剤の経時的な変色に由来する意匠性の劣化を良好に防止できる。
また、本発明の実施形態に係る糸状粘着体は、接着対象物(被着体)に接着剤や粘着剤を塗布する際に、接着剤や粘着剤のはみ出し防止のためのダム材として使用することができる。ダム材は、例えば、光学用パネルの貼り合わせに用いる封止樹脂のはみ出し防止のために使用することができる。糸状粘着体をダム材として使用する場合は、接着剤や粘着剤が硬化した後に糸状粘着体を剥がしてもよいし、残してもよい。
加熱乾燥は、例えば80~120℃、好ましくは90~110℃の条件下で、例えば20秒間~3分間、好ましくは30秒間~2分間行えばよい。
ローラーの回転速度は、芯材の繰り出し速度の0.4~4.0倍であることがより好ましく、0.5~3.0倍であることがさらに好ましく、0.8~1.5倍であることが特に好ましい。
芯材にかけるテンションは、0.2~6.0mN/dtexが好ましく、0.4~5.0mN/dtexがより好ましい。
〔1〕
粘着剤を備えた粘着体であって、
前記粘着剤を形成する粘着剤組成物がベースポリマーと、重量平均分子量1500以下の粘着付与樹脂とを含む、粘着体。
〔2〕
前記粘着付与樹脂の重量平均分子量が1000以下である、〔1〕に記載の粘着体。
〔3〕
更に芯材を備え、前記粘着剤が前記芯材の長手方向の表面を被覆する、〔1〕又は〔2〕に記載の粘着体。
〔4〕
糸状粘着体である、〔1〕~〔3〕のいずれかに記載の粘着体。
〔5〕
前記芯材がフィラメント数4本以上で構成された〔3〕に記載の粘着体。
〔6〕
前記粘着剤組成物における前記粘着付与樹脂の含有量は、前記ベースポリマー100質量部に対して、5~100質量部である、〔1〕~〔5〕のいずれかに記載の粘着体。
(アクリル系重合体エマルション1の調製)
冷却管、窒素導入管、温度計及び攪拌機を備えた反応容器に、イオン交換水40質量部を入れ、窒素ガスを導入しながら60℃で1時間以上攪拌して窒素置換を行った。この反応容器に、2,2’-アゾビス[N-(2-カルボキシエチル)-2-メチルプロピオンアミジン]n水和物(重合開始剤)0.1質量部を加えた。反応液を60℃に保ちつつ、ここに下記のモノマーエマルションAを4時間かけて徐々に滴下して乳化重合反応を進行させた。
冷却管、窒素導入管、温度計及び攪拌機を備えた反応容器に、イオン交換水40質量部を入れ、窒素ガスを導入しながら60℃で1時間以上攪拌して窒素置換を行った。この反応容器に、2,2’-アゾビス[N-(2-カルボキシエチル)-2-メチルプロピオンアミジン]n水和物(重合開始剤)0.1質量部を加えた。反応液を60℃に保ちつつ、ここに下記のモノマーエマルションBを4時間かけて徐々に滴下して乳化重合反応を進行させた。
冷却管、窒素導入管、温度計及び攪拌機を備えた反応容器に、イオン交換水40質量部を入れ、窒素ガスを導入しながら60℃で1時間以上攪拌して窒素置換を行った。この反応容器に、2,2’-アゾビス[N-(2-カルボキシエチル)-2-メチルプロピオンアミジン]n水和物(重合開始剤)0.1質量部を加えた。反応液を60℃に保ちつつ、ここに下記のモノマーエマルションCを4時間かけて徐々に滴下して乳化重合反応を進行させた。
(粘着液1の調製)
アクリル系重合体エマルション1に含まれるアクリル系重合体100質量部当たり、粘着付与樹脂が10質量部となるように粘着付与樹脂エマルション(荒川化学工業株式会社製、商品名「タマノルE200NT」)を加えた。さらに、イオン交換水を加えて固形分濃度を45質量%に調整して、粘着液1を得た。
[GPCの測定条件]
サンプル濃度:0.2重量%(テトラヒドロフラン溶液)
サンプル注入量:10μL
溶離液:テトラヒドロフラン(THF)
流量(流速):0.6mL/分
カラム温度(測定温度):40℃
カラム:
サンプルカラム:商品名「TSKguardcolumn SuperHZ-H」1本+商品名「TSKgel SuperHZM-H」2本」(東ソー社製)
リファレンスカラム:商品名「TSKgel SuperH-RC」1本(東ソー社製)
検出器:示差屈折計(RI)
標準試料:ポリスチレン
粘着付与樹脂エマルションの添加量を、アクリル系重合体100質量部当たり、粘着付与樹脂が20質量部、30質量部、35質量部となるようにそれぞれ変更したこと以外は粘着液1と同様に作製した。
アクリル系重合体エマルション2に含まれるアクリル系重合体100質量部当たり、粘着付与樹脂が35質量部となるように粘着付与樹脂エマルション(荒川化学工業株式会社製、商品名「タマノルE200NT」)を加えた。さらに、イオン交換水を加えて固形分濃度を45質量%に調整して、粘着液5を得た。
アクリル系重合体エマルション3に含まれるアクリル系重合体100質量部当たり粘着付与樹脂が35質量部となるように粘着付与樹脂エマルション(荒川化学工業株式会社製、商品名「タマノルE200NT」)を加えた。さらに、イオン交換水を加えて固形分濃度を45質量%に調整して、粘着液6を得た。
アクリル系重合体エマルション1に含まれるアクリル系重合体100質量部当たり粘着付与樹脂が10質量部となるように粘着付与樹脂エマルション(荒川化学工業株式会社製、商品名「スーパーエステルNS100H」)を加えた。さらに、イオン交換水を加えて固形分濃度を45質量%に調整して、粘着液7を得た。
アクリル系重合体エマルション1に含まれるアクリル系重合体100質量部当たり、粘着付与樹脂が32質量部となるように粘着付与樹脂エマルション(荒川化学工業株式会社製、商品名「スーパーエステルE865NT」)を加えた。さらに、イオン交換水を加えて固形分濃度を45質量%に調整して、粘着液8を得た。
(実施例1)
厚み25μmのPETフィルム(ルミラー#25)に乾燥時の厚みが20μmになるよう粘着液1を塗工して、100℃2分間乾燥した。乾燥後、はく離ライナー(DIAFOIL MRF#38)を被せて粘着テープを得た。
粘着液1に替えて粘着液2~8を用いて粘着テープを製造したこと以外は実施例1と同様にして粘着テープを作製した。
粘着力は、アクリロニトリルブタジエンスチレン共重合体樹脂板(ABS板)に対する180度剥離強度(180度引き剥がし粘着力)を指す。
(初期粘着力試験)
実施例及び比較例の粘着テープをそれぞれ幅10mm長さ70mmにカットした。カットした粘着テープからはく離ライナーを剥がし、ABS板に2kgローラー1往復で圧着してサンプルを作製した。
サンプルを23℃50%環境下に30分間静置した後に、引張試験機(株式会社島津製作所製「シマズオートグラフAG-100M2」)にて剥離速度300mm/minで引っ張り、初期粘着力(N/10mm)を測定した。
実施例及び比較例の粘着テープをそれぞれ幅10mm長さ70mmにカットして、はく離ライナーを剥がし、恒温槽にて60℃下に7日間静置した。7日後、粘着テープを恒温槽から取り出して、23℃50%環境下に1時間静置させた。その後、粘着テープをABS板に2kgローラー1往復で圧着してサンプルを作製した。サンプルをはく離ライナーにより保護せずに23℃50%環境下に30分間静置して保管した後に、初期粘着力試験と同様にして引張試験機(株式会社島津製作所製「シマズオートグラフAG-100M2」)にて剥離速度300mm/minで引っ張り、保管後の粘着力(N/10mm)を測定した。
上記で得られた初期粘着力及び保管後の粘着力から、下式(2)により粘着力維持率を算出した。
粘着力維持率 [%] = 保管後粘着力×100/初期粘着力 (2)
これに対して、粘着剤組成物が含む粘着付与樹脂の分子量が所定の範囲から外れる比較例1の粘着体は、保管後の粘着力が著しく低下することが分かった。
本出願は、2022年11月11日出願の日本特許出願(特願2022-181324)に基づくものであり、その内容はここに参照として取り込まれる。
2、3、4 粘着体
11 第一粘着剤層
12 第二粘着剤層
13 粘着剤層
14 芯材
20 基材
Claims (6)
- 粘着剤を備えた粘着体であって、
前記粘着剤を形成する粘着剤組成物がベースポリマーと、重量平均分子量1500以下の粘着付与樹脂とを含む、粘着体。 - 前記粘着付与樹脂の重量平均分子量が1000以下である、請求項1に記載の粘着体。
- 更に芯材を備え、前記粘着剤が前記芯材の長手方向の表面を被覆する、請求項1又は2に記載の粘着体。
- 糸状粘着体である、請求項1又は2に記載の粘着体。
- 前記芯材がフィラメント数4本以上で構成された請求項3に記載の粘着体。
- 前記粘着剤組成物における前記粘着付与樹脂の含有量は、前記ベースポリマー100質量部に対して、5~100質量部である、請求項1又は2に記載の粘着体。
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| EP23888769.9A EP4617340A1 (en) | 2022-11-11 | 2023-11-09 | Adhesive body |
| CN202380078335.2A CN120265724A (zh) | 2022-11-11 | 2023-11-09 | 粘合体 |
| KR1020257015259A KR20250103644A (ko) | 2022-11-11 | 2023-11-09 | 점착체 |
| JP2024557849A JPWO2024101424A1 (ja) | 2022-11-11 | 2023-11-09 |
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| CN (1) | CN120265724A (ja) |
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|---|---|---|---|---|
| JPH03231980A (ja) * | 1990-02-07 | 1991-10-15 | Ishizaki Shizai Kk | 糸状接着具及びその製造方法 |
| JP2014080598A (ja) * | 2012-09-28 | 2014-05-08 | Arakawa Chem Ind Co Ltd | 水系粘・接着剤用の粘着付与剤、粘着付与樹脂エマルジョン及び水系粘・接着剤組成物 |
| US20170335145A1 (en) * | 2016-05-17 | 2017-11-23 | Nitto Denko Materials (Malaysia) Sdn. Bhd. | Double-sided pressure-sensitive adhesive tape |
| JP2020019923A (ja) | 2018-02-21 | 2020-02-06 | 日東電工株式会社 | 粘着性物品 |
| WO2020071508A1 (ja) * | 2018-10-05 | 2020-04-09 | 日東電工株式会社 | 粘着性物品 |
| JP2020076066A (ja) | 2018-10-05 | 2020-05-21 | 日東電工株式会社 | 粘着性物品 |
| JP2021195401A (ja) * | 2020-06-10 | 2021-12-27 | 東洋インキScホールディングス株式会社 | 水性粘着剤および粘着シート |
| JP2022181324A (ja) | 2021-05-26 | 2022-12-08 | 株式会社東芝 | 回転電機の異常検知装置、方法及びプログラム |
-
2023
- 2023-11-09 KR KR1020257015259A patent/KR20250103644A/ko active Pending
- 2023-11-09 EP EP23888769.9A patent/EP4617340A1/en active Pending
- 2023-11-09 JP JP2024557849A patent/JPWO2024101424A1/ja active Pending
- 2023-11-09 WO PCT/JP2023/040415 patent/WO2024101424A1/ja not_active Ceased
- 2023-11-09 CN CN202380078335.2A patent/CN120265724A/zh active Pending
- 2023-11-10 TW TW112143431A patent/TW202436562A/zh unknown
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| JPH03231980A (ja) * | 1990-02-07 | 1991-10-15 | Ishizaki Shizai Kk | 糸状接着具及びその製造方法 |
| JP2014080598A (ja) * | 2012-09-28 | 2014-05-08 | Arakawa Chem Ind Co Ltd | 水系粘・接着剤用の粘着付与剤、粘着付与樹脂エマルジョン及び水系粘・接着剤組成物 |
| US20170335145A1 (en) * | 2016-05-17 | 2017-11-23 | Nitto Denko Materials (Malaysia) Sdn. Bhd. | Double-sided pressure-sensitive adhesive tape |
| JP2020019923A (ja) | 2018-02-21 | 2020-02-06 | 日東電工株式会社 | 粘着性物品 |
| WO2020071508A1 (ja) * | 2018-10-05 | 2020-04-09 | 日東電工株式会社 | 粘着性物品 |
| JP2020076066A (ja) | 2018-10-05 | 2020-05-21 | 日東電工株式会社 | 粘着性物品 |
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| JP2022181324A (ja) | 2021-05-26 | 2022-12-08 | 株式会社東芝 | 回転電機の異常検知装置、方法及びプログラム |
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| JPWO2024101424A1 (ja) | 2024-05-16 |
| EP4617340A1 (en) | 2025-09-17 |
| CN120265724A (zh) | 2025-07-04 |
| KR20250103644A (ko) | 2025-07-07 |
| TW202436562A (zh) | 2024-09-16 |
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