WO2019065886A1

WO2019065886A1 - Adhesive article

Info

Publication number: WO2019065886A1
Application number: PCT/JP2018/036051
Authority: WO
Inventors: 淳 ▲高▼嶋; 陽介巻幡; 銀次水原
Original assignee: 日東電工株式会社
Priority date: 2017-09-29
Filing date: 2018-09-27
Publication date: 2019-04-04
Also published as: TW201920551A

Abstract

The present invention relates to an adhesive article that includes a linear adhesive body and a non-adhesive layer covering a longitudinal-direction surface of the adhesive body, wherein the adhesive article exhibits adhesiveness when the non-adhesive body is broken by stretching the adhesive article.

Description

Adhesive articles

TECHNICAL FIELD The present invention relates to a pressure-sensitive adhesive article, and more particularly to a pressure-sensitive adhesive article that exhibits tackiness by stretching.

Pressure-sensitive adhesive sheets and pressure-sensitive adhesive tapes are used for bonding various adherends such as metal, glass, wood, paper, cardboard, and plastic materials. In such a pressure-sensitive adhesive sheet, the pressure-sensitive adhesive surface is usually protected by a separator (release sheet) in order to protect the pressure-sensitive adhesive surface until the pressure-sensitive adhesive sheet is attached to an adherend. In addition, in the case of a wound form such as a roll-shaped pressure-sensitive adhesive tape, in order to facilitate unwinding, a base material subjected to a peeling treatment on the back surface with which the pressure-sensitive adhesive surface comes in contact is used.

However, in the pressure-sensitive adhesive sheet using a separator, since the separator to be peeled off at the time of use is discarded after peeling, its use is not desirable from the viewpoint of resource saving and cost reduction. In addition, when the user uses them while wearing gloves or when the size of the adhesive sheet or adhesive tape used is small, the workability when peeling the separator from the adhesive sheet or when rewinding the adhesive tape is improved. There is a problem of being bad. Therefore, it would be useful if a pressure-sensitive adhesive sheet or pressure-sensitive adhesive tape which does not require peeling treatment of the separator or the back surface of the substrate can be provided.

In relation to this, in Patent Document 1, a non-adhesive substance is fixed on the adhesive surface of adhesive sheets by interfacial contact reaction to form a non-adhesive thin layer, and the non-adhesive thin layer is formed, and when attached to an adherend A tackiness reappearance method is described that breaks tacky laminae to recapacitate.

Japanese Patent No. 4380837

However, when the surface shape of the adherend is a curved surface or a complicated shape such as a concavo-convex shape, when a sheet-like (film-like) pressure-sensitive adhesive sheet is attached to the adherend, the pressure-sensitive adhesive sheet Myself may occur, and an overlap may occur on a part of the adhesive sheet, which may make application difficult.

Further, for example, when application to a narrow area is desired, it may be considered to use an adhesive sheet with a thin cut, but there is a limit to the cuttable width. In such a case, although it is conceivable to use a liquid adhesive, there is a possibility that a drip of the adhesive may occur or the thickness of the adhesive layer may become uneven.

In view of the problems as described above, the present invention, while being substantially non-adhesive in the initial state, can exhibit adhesiveness by a simple operation at the time of use, and the surface of an applicable adherend An object of the present invention is to provide a tacky article having various shapes and areas.

One aspect of the present invention is a pressure-sensitive adhesive article comprising a linear pressure-sensitive adhesive body and a non-adhesive layer covering the surface in the longitudinal direction of the pressure-sensitive adhesive body, the non-adhesive layer being broken by stretching of the adhesive article The present invention relates to an adhesive article which is adhesively developed.

In one aspect of the present invention, the pressure-sensitive adhesive body may include a linear core material and a pressure-sensitive adhesive layer covering the surface in the longitudinal direction of the core material.

In one aspect of the present invention, the adhesive article is preferably in the form of threads.

In one aspect of the present invention, the non-adhesive layer preferably contains a polymeric material.

In one aspect of the present invention, the non-adhesive layer preferably contains an aggregate of a plurality of emulsion particles.

In one aspect of the present invention, the tack value after 2 times stretching in the lengthwise direction of the adhesive article measured by the following probe tack test 2 is from the tack value before stretching measured by the following probe tack test 1 It is preferable to be larger than 1 gf.
(Probe tack test 1)
A load of 2 mm in diameter made of stainless steel (SUS304) with a contact load of 50 gf is applied to the surface of the adhesive article at a measurement temperature of 23 ° C., and then the load applied to the probe when pulled apart by 1 mm at a speed of 30 mm / min. Is measured over time, and the maximum load required for peeling is determined.
(Probe tack test 2)
After the adhesive article is stretched in the length direction under an environment of measurement temperature 23 ° C., a stainless steel probe (SUS 304) with a diameter of 2 mm is brought into contact with the surface of the adhesive article with a contact load of 50 gf, and 30 mm The load applied to the probe is measured with time when pulling 1 mm apart at a speed of 1 / min, and the maximum load required for peeling is determined.

The adhesive article according to one aspect of the present invention is substantially non-adhesive in the initial state, and thus does not require a separator or peeling treatment. Moreover, adhesiveness can be expressed by simple operation, and it is excellent in workability. Furthermore, the surface shape and area of the applicable adherend are various.

FIG. 1 is a schematic cross-sectional view of one structural example of the adhesive article. FIG. 2 is a schematic cross-sectional view of one structural example of the adhesive article.

Hereinafter, embodiments of the present invention will be described in detail.
In the following drawings, the same reference numerals may be given to members / parts having the same function, and overlapping descriptions may be omitted or simplified. In addition, the embodiments described in the drawings are schematically illustrated in order to clearly explain the present invention, and do not necessarily accurately represent the actual product size and scale.
Moreover, in the present specification, the proportion (percentage, part, etc.) based on mass is the same as the proportion (percentage, part, etc.) based on weight.

A pressure-sensitive adhesive article according to an embodiment of the present invention is a pressure-sensitive adhesive article including a linear pressure-sensitive adhesive body and a non-adhesive layer covering the surface in the longitudinal direction of the pressure-sensitive adhesive body. The non-adhesive layer is broken to develop adhesiveness.

The pressure-sensitive adhesive article of the present embodiment is a pressure-sensitive adhesive article that exhibits tackiness by stretching, and in the initial state before stretching, has substantially no tackiness, that is, is substantially non-tacky. And since the non-adhesive layer is fractured by stretching, the adhesiveness by the adhesive is expressed. That is, the non-adhesive layer is broken in the drawing process, and fragments of the non-adhesive layer broken by the drawing typically adhere to the surface of the adhesive article (adhesive body). On the other hand, since the surface area of the adhesive article is increased by the stretching of the adhesive article, in the adhesive article after stretching, the surface to which the fragments of the non-adhesive layer are not attached is in the state where the adhesive is exposed. Adhesiveness will be developed.

FIG. 1 is a schematic cross-sectional view in a direction perpendicular to the longitudinal direction of the adhesive article, regarding one structural example of the adhesive article according to the present embodiment. In the adhesive article 1 shown in FIG. 1, the non-adhesive layer 31 covers the surface (the surface in the longitudinal direction) of the linear adhesive body 21. The term “linear” as used herein is a concept including, in addition to straight lines, curved lines, broken lines, etc., a state capable of being bent in various directions and angles like yarn (hereinafter also referred to as thread). It is.

The adhesive article of this configuration example is a support-less adhesive article comprising a linear adhesive body and a non-adhesive layer. In addition, although the shape of the cross section of the adhesive article of this structural example is circular, this embodiment is not limited to this, As a shape of the cross section, rectangles, such as an ellipse and a square besides a circle, etc. Can take In the present embodiment, when the cross-sectional shape of the adhesive article is circular, the diameter of the cross section is not particularly limited, but if the diameter is too small, the adhesive article may break at the time of stretching. Is preferably, and more preferably 30 μm or more. Further, if the diameter is too large, a large stress may be required at the time of stretching, so for example, it is preferably 2000 μm or less, and more preferably 1000 μm or less.

In this case, the diameter of the cross section of the pressure-sensitive adhesive body is not particularly limited, but it is preferably, for example, 9.8 μm or more, since the adhesive article may break when stretched if the diameter is too small. It is more preferable that In addition, if the diameter is too large, a large stress may be required at the time of stretching, so for example, it is preferably 1999 μm or less, and more preferably 999 μm or less.

The thickness of the non-adhesive layer covering the adhesive body is preferably, for example, 0.1 μm or more, and preferably 1 μm or more, from the viewpoint of securing the substantially non-adhesiveness before stretching and protecting the adhesive layer. It is more preferable that In addition, for example, the thickness is preferably 60 μm or less, and more preferably 20 μm or less from the viewpoint of developing the adhesive strength.

The end face of the pressure-sensitive adhesive body may or may not be covered with a non-pressure-sensitive adhesive layer. For example, if the adhesive article is cut during the manufacturing process or in use, the end face of the adhesive body may not be covered by the non-adhesive layer.

In the adhesive article of the present embodiment, the non-adhesive layer covers the adhesive body in the initial state before stretching, but the non-adhesive layer is broken by stretching the adhesive article, and the adhesiveness of the adhesive article is expressed Do.

In order that the non-adhesive layer appropriately has substantial non-adhesiveness, the storage elastic modulus at 23 ° C. of the non-adhesive layer is preferably 1 × 10 ⁷ Pa or more, and 5 × 10 ⁷ Pa or more. It is more preferable that Also, from the viewpoint of flexibility, the elastic modulus at 23 ° C. of the non-adhesive layer is, for example, preferably 1 × 10 ¹⁰ Pa or less, and more preferably 5 × 10 ⁹ Pa or less. The elastic modulus at 23 ° C. of the non-adhesive layer is measured by a dynamic visco-elastic device (product name: RSA-III, manufactured by TA Instruments), and the measurement method described in the column of the example is described in detail. Measured by

Moreover, in the adhesive article of this embodiment, in order to assist the fracture | rupture of the non-adhesive layer at the time of extending | stretching, you may put a stripe (cut) in a non-adhesive layer. There are no particular limitations on the direction of the streaks when the streaks are inserted into the non-sticky layer, but breakage due to stretching of the non-sticky layer may tend to occur relatively in the direction perpendicular to the stretching direction. In such a case, in order to finely break the non-adhesive layer by stretching, it is preferable to put a streak in the stretching direction. In addition, the direction in which the streaks are formed is not limited to one direction, and may be in any plural directions, for example, two directions of the stretching direction and a direction perpendicular to the stretching direction. By forming a line (cut) in the non-adhesive layer, the non-adhesive layer can be broken into smaller pieces by breakage due to stretching.

As the material of the non-adhesive layer, it can be used by appropriately selecting from materials which can itself be coated with an adhesive without substantially having adhesiveness, and can be broken by stretching, for example, polymeric materials, Metal materials, inorganic materials and the like can be mentioned. Among them, a polymer material is preferably used from the viewpoint of the ease of breaking by stretching. Examples of the polymer material include resins (polyolefin, polyester, polystyrene, acrylic resin, vinyl chloride, phenol resin, polyurethane, nylon etc.), elastomers, rubber, natural polymers (fiber cellulose, protein etc.), starch etc. Among them, acrylic resins are preferable because self-fusion does not easily occur (hard to prevent blocking). In addition, these materials can be used individually by 1 type or in combination of 2 or more types.

Below, the case where a non-adhesion layer consists of resin is demonstrated. When the non-adhesive layer is made of a resin, the composition containing a polymer used to form the non-adhesive layer (hereinafter, also referred to as a polymer-containing composition for forming a non-adhesive layer) is It may be a polymer-containing composition for forming an adhesive layer, or it may be a polymer-containing composition for forming a non-adhesive layer of a solvent type.
In the present specification, a non-adhesive layer formed of a water-dispersed non-adhesive layer-forming polymer-containing composition may be referred to as an emulsion-based non-adhesive layer, and a solvent-type polymer for non-adhesive layer formation The non-adhesion layer formed by the containing composition may be referred to as a solvent-based non-adhesion layer. Moreover, a "polymer" is the concept also including a copolymer.

The non-adhesive layer formed by the water-dispersed non-adhesive layer forming polymer-containing composition is formed as a layer containing an aggregate of a plurality of emulsion particles. Here, as the non-adhesive layer, a layer (an emulsion-based non-adhesive layer) containing an aggregate of a plurality of emulsion particles (emulsion polymer particles) can be expressed because better adhesiveness is developed after stretching. preferable.

In the case where the non-adhesive layer is a layer containing aggregates of a plurality of emulsion particles (emulsion-based non-adhesive layer), the reason why better adhesiveness is developed after stretching is not necessarily clear, but It is guessed. That is, in the case where the non-adhesive layer is an emulsion-based non-adhesive layer, when the adhesive article is stretched, the non-adhesive layer is broken in various directions from the interface between the aggregated emulsion particles to form fine scaly fragments Typically, it is in a state of being attached to the surface of the adhesive article (adhesive body). On the other hand, since the surface area of the adhesive article is increased by the stretching of the adhesive article, in the adhesive article after stretching, the surface to which the fragments of the non-adhesive layer are not attached is in the state where the adhesive is exposed. Adhesiveness will be developed. In addition, when the adhesive article is attached to the adherend in a state where the non-adhesive layer thus formed into fine scaly fragments adheres to the surface of the adhesive, non-adhesive by pressure upon attachment. Since scaly fragments of the layer penetrate into the adhesive and the exposed area of the adhesive increases, it is considered that the adhesiveness by the adhesive is better expressed.

Although the case where the non-adhesive layer contains the aggregate of the emulsion particle (acrylic polymer emulsion particle) which consists of an acrylic polymer below is explained, the present invention is not limited to this.

The non-adhesive layer containing the aggregate of acrylic polymer emulsion particles can be formed using a composition containing a water-dispersed acrylic polymer as the non-adhesive layer-forming polymer-containing composition. The water-dispersible acrylic polymer is a composition in the form of an emulsion in which the acrylic polymer is dispersed in water. The acrylic polymer is preferably an acrylic polymer whose main monomer unit is, for example, methyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, isobornyl (meth) acrylate, cyclohexyl acrylate or the like. There may be mentioned co-polymers. Among them, an acrylic copolymer (1) in which the main monomer unit is n-butyl methacrylate is preferable, and specifically, an acrylic copolymer containing n-butyl methacrylate and a carboxy group-containing monomer as the monomer unit (1-1) an acrylic copolymer containing n-butyl methacrylate, a carboxy group-containing monomer, and a (meth) acrylic acid C _1-14 alkyl ester other than n-butyl methacrylate as a monomer unit (1-2 Etc.).

The carboxy group-containing monomer is not particularly limited, and examples thereof include (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid and the like. . Among them, acrylic acid and / or methacrylic acid is preferred, and more preferably acrylic acid and methacrylic acid in combination. When acrylic acid and methacrylic acid are used in combination, the amount ratio is not particularly limited, but it is preferable that they be approximately the same amount. The carboxy group-containing monomer can be used alone or in combination of two or more.

In (meth) acrylic acid C _1-14 alkyl esters other than n-butyl methacrylate, the alkyl group having 1 to 14 carbon atoms may be linear or branched, for example, Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate T-Butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, (meth) acrylate Cyclohexyl, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, (meth And the like.) Include isononyl acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate and tetradecyl (meth) acrylate. Such (meth) acrylic acid C _1-14 alkyl ester is preferably acrylic acid C _2-12 alkyl ester, more preferably acrylic acid C _4-8 alkyl ester.

The acrylic copolymer (1) preferably contains 50 to 99% by weight, more preferably 60 to 90% by weight, and preferably 60 to 70% by weight of n-butyl methacrylate in all monomer units. It is particularly preferred to

The composition of the acrylic copolymer (1-1) containing n-butyl methacrylate and a carboxy group-containing monomer as monomer units is 80 to 99:20 of n-butyl methacrylate: carboxy group-containing monomer (weight ratio) 1 is preferable, 80 to 95: 20 to 5 is more preferable, and 85 to 95: 15 to 5 is particularly preferable. In addition, the composition of an acrylic copolymer (1-2) containing, as monomer units, n-butyl methacrylate, a carboxy group-containing monomer, and a (meth) acrylic acid C _1-14 alkyl ester other than n-butyl methacrylate as a monomer unit is And n-butyl methacrylate: carboxy group-containing monomer: (meth) acrylic acid C _1-14 alkyl ester (weight ratio) other than n-butyl methacrylate is 50 to 98: 1 to 20: 1 to 30 (however, The total weight of the three components is preferably 100), and more preferably 60 to 90: 5 to 20: 5 to 20 (provided that the total weight of the three components is 100).

The acrylic copolymers (1) and (1-1) may each be, in the range of 10% by weight or less of the total monomer units, methacrylic acid C _1-18 alkyl esters other than n-butyl methacrylate or A hydroxy group-containing monomer can be contained as a monomer unit. In addition, the acrylic copolymer (1-2) can contain, as a monomer unit, a C _15-18 alkyl ester of methacrylic acid or a hydroxy group-containing monomer within a range of 10% by weight or less in all the monomer units. .

Examples of the hydroxy group-containing monomer include hydroxyethyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxyoctyl (meth) acrylate, hydroxydecyl (meth) acrylate ( Examples include hydroxylauryl methacrylate, (4-hydroxymethylcyclohexyl) methyl methacrylate and the like.

The glass transition temperature of the acrylic polymer forming the non-adhesive layer containing the aggregates of the acrylic polymer emulsion particles is not particularly limited, but in order to exhibit good non-adhesiveness, it is 5 ° C or higher. Is preferably, and more preferably 10 ° C. or more. Also, the upper limit value is not particularly limited, but it is, for example, 150 ° C. or less from the viewpoint of film forming property.

In the present specification, the glass transition temperature (° C.) of the acrylic polymer is the theoretical glass transition temperature (K) calculated by the following formula of FOX from the monomer units constituting the acrylic polymer and the ratio thereof: It is converted to Celsius (° C).

Formula of FOX: 1 / Tg = W ₁ / Tg ₁ + W ₂ / Tg ₂ +... + W _n / Tg _n
(Tg: glass transition temperature of the polymer _{_{(K), Tg 1, Tg}} 2, ···, Tg n: glass transition temperature of the homopolymer of each monomer _{_{(K), W 1, W}} 2, ···, W _n : weight fraction of each monomer)

The theoretical glass transition temperature (converted to degree Celsius (° C.)) determined from the equation of FOX matches well with the actual glass transition temperature determined by differential scanning calorimetry (DSC), dynamic viscoelasticity, or the like.

As a method of polymerizing such a monomer to obtain a water-dispersible acrylic polymer, known or conventional polymerization methods can be employed, and an emulsion polymerization method can be preferably used. As a monomer supply method at the time of performing emulsion polymerization, a batch preparation method of supplying all the monomer components at one time, a continuous supply (dropping) method, a divided supply (dropping) method, and the like can be appropriately adopted. A part or all (typically all) of the monomers is emulsified beforehand by mixing with water (typically, an appropriate amount of emulsifier is used together with water), and the emulsion (monomer emulsion) is reacted It may be supplied all at once, continuously or in portions in the container. The polymerization temperature can be appropriately selected according to the type of monomer to be used, the type of polymerization initiator, etc., and can be, for example, about 20 ° C. to 100 ° C. (typically, 40 ° C. to 80 ° C.).

As a polymerization initiator used at the time of superposition | polymerization, it can select suitably from well-known thru | or a usual polymerization initiator according to the kind of polymerization method. For example, in the emulsion polymerization method, an azo polymerization initiator can be preferably used. Specific examples of the azo polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylpropionamidine) disulfate, and 2,2′-azobis (2-amidino Propane) dihydrochloride, 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis (N, N′-dimethylene isobutylamidine), 2,2'-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'- Azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonyl) Le), 2,2'-azobis (2,4,4-trimethylpentane), dimethyl-2,2'-azobis (2-methyl propionate), and the like.

Other examples of polymerization initiators include persulfates such as potassium persulfate and ammonium persulfate; benzoyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, t-butyl peroxybenzoate, and dicumyl benzoate Peroxide systems such as peroxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, hydrogen peroxide Initiators; substituted ethane initiators such as phenyl-substituted ethane; aromatic carbonyl compounds; and the like. Still another example of the polymerization initiator includes a redox initiator based on a combination of a peroxide and a reducing agent. Examples of such redox initiators include combinations of peroxides and ascorbic acid (combinations of hydrogen peroxide water and ascorbic acid, etc.), combinations of peroxides and iron (II) salts (hydrogen peroxide water Combinations of iron and iron (II) salts, etc., combinations of persulfates and sodium bisulfite, etc.

Such polymerization initiators can be used alone or in combination of two or more. The amount of the polymerization initiator used may be a usual amount, for example, about 0.005 to 1 part by weight (typically 0.01 to 1 part by weight) with respect to 100 parts by weight of all the monomer components. It can be selected from the range.

An emulsifier can be used as needed in preparation of a water dispersion type acrylic polymer. As an emulsifier, any of an anionic type, a nonionic type, and a cationic type can be used. Usually, the use of an anionic or nonionic emulsifier is preferred. Such an emulsifier can be preferably used, for example, when emulsion polymerizing a monomer component, or when dispersing an acrylic polymer obtained by another method in water.

As an anionic emulsifier, for example, an alkyl sulfate type anionic emulsifier such as sodium lauryl sulfate, ammonium lauryl sulfate, potassium lauryl sulfate and the like; a polyoxyethylene alkyl ether sulfate type anionic emulsifier such as polyoxyethylene lauryl ether sodium sulfate etc Polyoxyethylene alkylphenyl ether sulfate type anionic emulsifier such as polyoxyethylene lauryl phenyl ether ammonium sulfate, sodium polyoxyethylene lauryl phenyl ether sulfate; sulfonate type anionic emulsifier such as sodium dodecylbenzene sulfonate; Sulfosuccinic acid type anionic emulsifiers such as disodium lauryl acid and disodium lauryl polyoxyethylene sulfosuccinate;

Moreover, as nonionic emulsifiers, for example, polyoxyethylene alkyl ether nonionic emulsifiers such as polyoxyethylene lauryl ether; polyoxyethylene alkyl phenyl ether nonionic emulsifiers such as polyoxyethylene lauryl phenyl ether; polyoxyethylene fatty acid Esters; polyoxyethylene polyoxypropylene block polymers; and the like. A radically polymerizable emulsifier (reactive emulsifier) having a structure in which a radically polymerizable group (propenyl group or the like) is introduced to the above-mentioned anionic or nonionic emulsifier may be used.

One such emulsifier may be used alone, or two or more may be used in combination. The amount of the emulsifier used is not particularly limited as long as it can be used to prepare the acrylic polymer in the form of an emulsion. For example, it is suitable to select in the range of, for example, about 0.2 to 10 parts by weight (preferably, about 0.5 to 5 parts by weight) on the basis of solid content per 100 parts by weight of the acrylic polymer. If the amount of the emulsifier used is too small, it may be difficult to obtain desired dispersion stability (polymerization stability, mechanical stability, etc.). If the amount of emulsifier used is too high, it may contaminate the adherend.

In the above description, although the non-adhesive layer mainly includes an aggregate of emulsion particles (acrylic polymer emulsion particles) consisting of an acrylic polymer, the present invention is not limited to this. For example, also in the case where the non-adhesive layer contains an aggregate of emulsion particles composed of a polymer other than an acrylic polymer, the above can be appropriately applied.

When a solvent-type composition is used as the non-adhesive layer-forming polymer-containing composition for forming the non-adhesive layer, the polymer forming the non-adhesive layer may be toluene, ethyl acetate, ethanol or the like. A solution dissolved in an appropriate solvent can be used.

In addition, the polymer-containing composition for forming a non-adhesive layer may contain an acid or a base (such as aqueous ammonia) used for the purpose of pH adjustment, if necessary. Also, crosslinking agents, viscosity modifiers (thickeners, etc.), leveling agents, release modifiers, plasticizers, softeners, fillers, colorants (pigments, dyes, etc.), surfactants, antistatic agents, preservatives You may contain various additives, such as an antiaging agent, an ultraviolet absorber, antioxidant, and a light stabilizer. However, since the non-adhesive layer becomes too hard, it may be difficult to break the non-adhesive layer, or the pressure-sensitive adhesive layer (pressure-sensitive adhesive layer) may also be broken by an impact at the time of breakage of the non-adhesive layer. Preferably, the composition for forming a non-adhesive layer contains no crosslinking agent.

In the pressure-sensitive adhesive article of the present embodiment, the pressure-sensitive adhesive constituting the pressure-sensitive adhesive body is not particularly limited, and a known pressure-sensitive adhesive can be used. For example, acrylic pressure sensitive adhesive, rubber pressure sensitive adhesive, vinyl alkyl ether pressure sensitive adhesive, silicone pressure sensitive adhesive, polyester pressure sensitive adhesive, polyamide pressure sensitive adhesive, urethane pressure sensitive adhesive, fluorine based pressure sensitive adhesive, epoxy pressure sensitive adhesive, etc. It can be mentioned. Among them, from the viewpoint of adhesiveness, rubber-based pressure-sensitive adhesives and acrylic pressure-sensitive adhesives are preferable, and acrylic pressure-sensitive adhesives are particularly preferable. In addition, an adhesive may be used individually by 1 type, and may be used combining 2 or more types. Further, the pressure-sensitive adhesive according to the present embodiment is a pressure-sensitive adhesive that has adhesiveness at normal temperature and can adhere the adherend to the surface by the pressure generated when the surface of the pressure-sensitive adhesive contacts the surface of the adherend. Is preferred. If it is a pressure sensitive adhesive, it does not require heating and can be applied to adherends that are weak to heat.

The acrylic pressure-sensitive adhesive is mainly composed of (meth) acrylic acid alkyl ester such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, isononyl acrylate, and, if necessary, acrylonitrile, vinyl acetate, Main component is a polymer of a monomer formed by adding a modifying monomer such as styrene, methyl methacrylate, acrylic acid, maleic anhydride, vinyl pyrrolidone, glycidyl methacrylate, dimethylaminoethyl methacrylate, hydroxyethyl acrylate, acrylamide and the like It is

Rubber-based pressure-sensitive adhesives include natural rubber, styrene-isoprene-styrene block copolymer, styrene-butadiene-styrene block copolymer, styrene-ethylene / butylene-styrene block copolymer, styrene butadiene rubber, polybutadiene, polyisoprene, Rubber-based polymers such as polyisobutylene, butyl rubber, chloroprene rubber and silicone rubber are the main ingredients.

Moreover, tackifier resins such as rosins, terpenes, styrenes, aliphatic petroleum, aromatic petroleum, xylene, phenol, coumarone indene, their hydrogenated substances, and crosslinkers can be used as these adhesives. Agents, viscosity modifiers (thickeners etc), leveling agents, release modifiers, plasticizers, softeners, fillers, colorants (pigments, dyes etc), surfactants, antistatic agents, preservatives, antiaging Various additives, such as an agent, an ultraviolet absorber, an antioxidant, and a light stabilizer, can be suitably blended.

In addition, as an adhesive, any type of a solvent type adhesive and a water dispersion type adhesive can be used. Here, a water-dispersed pressure-sensitive adhesive is preferable from the viewpoint of being capable of high-speed coating, being environmentally friendly, and having little influence (swelling, dissolution) on the core material by the solvent.

Further, the linear pressure-sensitive adhesive body may include a core material and a pressure-sensitive adhesive layer covering the core material.
FIG. 2 is a schematic cross-sectional view in a direction perpendicular to the longitudinal direction of the adhesive article, regarding one structural example of the adhesive article according to the present embodiment. The adhesive article 2 shown in FIG. 2 is provided with a linear adhesive body 21 composed of a linear core material 22 and an adhesive layer 23 covering the surface of the core material 22 in the longitudinal direction. The non-adhesive layer 31 covers the surface (the surface in the longitudinal direction) of the adhesive layer 23 in the adhesive body 21.

In addition, although the shape of the cross section of the adhesive article of this structural example is circular, this embodiment is not limited to this, As a shape of the cross section, rectangles, such as an ellipse and a square besides a circle, etc. Can take

Here, in the pressure-sensitive adhesive body having a core, the pressure-sensitive adhesive layer may cover the entire surface of the core (surface in the longitudinal direction), but may cover only a part of the surface of the core. The pressure-sensitive adhesive layer is typically formed continuously, but is not limited to such a form, and may be formed, for example, in a regular or random pattern such as dot-like or stripe-like. The end face of the core material may or may not be covered with the pressure-sensitive adhesive layer. For example, if the adhesive article is cut during the manufacturing process or in use, the end face of the core may not be covered by the adhesive layer. Moreover, in any case, the surface (surface in the longitudinal direction) of the pressure-sensitive adhesive layer is covered with the non-adhesive layer.

The core material used for the adhesive article is not particularly limited as long as it does not prevent the stretching of the adhesive article, but it is preferably made of a material that can be stretched by itself, for example, resin, rubber, foam, inorganic Fibers, composites of these, etc. can be used. Examples of the resin include polyolefins such as polyethylene (PE), polypropylene (PP), ethylene / propylene copolymer, ethylene / vinyl acetate copolymer, etc .; polyesters such as polyethylene terephthalate (PET); vinyl chloride resin; vinyl acetate resin Polyimide resin; polyamide resin; fluorine resin etc. may be mentioned. Examples of the rubber include natural rubber, synthetic rubber such as urethane rubber, and the like. Examples of the foam include foamed polyurethane, foamed polychloroprene rubber and the like. Examples of fibers include glass fibers, carbon fibers, metal fibers and the like. Although the cross-sectional shape of the core material is not particularly limited, it usually has a cross-sectional shape corresponding to the cross-sectional shape of the adhesive article.

Moreover, as a material of the threadlike core material which can be used for threadlike adhesive articles, rayon, cupra, acetate, promix, nylon, aramid, vinylon, vinylidene, polyvinyl chloride, polyester, acrylic, polyethylene, polypropylene, polyurethane Various polymeric materials such as polychlore and polylactic acid, various rubbers such as glass, carbon fiber, synthetic rubber such as natural rubber and polyurethane, natural materials such as cotton and wool, metals and the like can be used. In addition, as the form of the thread core, for example, other than monofilament, multifilament, spun yarn, processed yarn generally referred to as textured yarn, bulky yarn, and stretch yarn subjected to crimp processing, bulking processing, etc. Or, a yarn combined by twisting these or the like can be used. In addition, the cross-sectional shape may be not only circular, but may be a rectangular or star-shaped short thread, an elliptical shape, a hollow, or the like.

In the core material, if necessary, a filler (inorganic filler, organic filler, etc.), an antioxidant, an antioxidant, an ultraviolet absorber, an antistatic agent, a lubricant, a plasticizer, a colorant (pigment (pigment) , Dyes, etc.) may be blended. The surface of the core material may be subjected to known or conventional surface treatment such as corona discharge treatment, plasma treatment, application of a primer and the like.

The size of the cross section of the core material is not particularly limited and can be appropriately selected according to the purpose, but in the case of, for example, a circular cross sectional shape, the diameter in terms of handling properties (ease of drawing, difficulty in cutting) Is preferably 1 μm to 2000 μm, more preferably 10 μm to 1000 μm.

As an adhesive which comprises an adhesive layer, the thing similar to the adhesive which can comprise the adhesive body mentioned above can be used.

In the case of a pressure-sensitive adhesive article having a core as shown in FIG. 2, the thickness of the pressure-sensitive adhesive layer is not particularly limited, but from the viewpoint of adhesion, for example, preferably 1 μm or more, and more preferably 3 μm or more. preferable. Further, from the viewpoint of drying property, for example, the particle diameter is preferably 200 μm or less, and more preferably 150 μm or less.

The thickness of the non-adhesive layer is not particularly limited, but from the viewpoint of securing the substantially non-adhesiveness before stretching and protecting the pressure-sensitive adhesive layer, for example, 0.1 μm or more is preferable, and 1 μm or more. It is more preferable that Further, from the viewpoint of expression of adhesive strength, for example, the particle diameter is preferably 60 μm or less, and more preferably 20 μm or less.

In this specification, the adhesive article in the initial state (before stretching) is "substantially free of tackiness (substantially non-tacky)" means the following probe tack on the surface of the tacky article: It represents that the tack value measured by test 1 is 2 gf or less. In addition, the adhesive article in the initial state (before stretching) "having tackiness" means that the tack value measured by the following probe tack test 1 on the surface of the adhesive article is more than 2 gf. More specifically, the tack value is measured in accordance with the probe tack measurement method described in the column of Examples described later.

(Probe tack test 1)
After contacting a 2 mm diameter stainless steel probe (SUS 304) with a contact load of 50 gf to the surface of the adhesive article at a measurement temperature of 23 ° C., the load applied to the probe is 1 mm apart at a speed of 30 mm / min. Measure over time and find the maximum load required for peeling.

Moreover, in the present specification, the term "substantially free of tackiness (substantially non-tacky)" means that the stretched adhesive article has the following probe tack test 2 of the surface of the adhesive article. Represents that the tack value measured by the above is 2 gf or less. Moreover, the adhesive article after extending | stretching "adhesivity" represents that the tack value measured by the following probe tack test 2 of the surface of this adhesive article is more than 2 gf. More specifically, the tack value is measured in accordance with the probe tack measurement method described in the column of Examples described later.

(Probe tack test 2)
After stretching the adhesive article in the length direction under an environment of measurement temperature 23 ° C., after contacting the surface of the adhesive article with a stainless steel probe (SUS 304) with a diameter of 2 mm with a contact load of 50 gf, 30 mm / min The load applied to the probe is measured over time when it is separated by 1 mm at a speed of 1 to determine the maximum load required for peeling.

In addition, the term "the adhesive exhibits tackiness by stretching" means that the tacky article is substantially non-tacky in the initial state before stretching, and has tackiness after stretching.

Here, in order for the development of the adhesiveness by stretching to be exhibited better, the tack value after 2 times stretching in the lengthwise direction of the adhesive article is 1 gf or more larger than the tack value before stretching. It is preferably 1.5 gf or more, more preferably 2 gf or more.

From the same point of view, the tack value after 2-fold stretching in the longitudinal direction of the adhesive article is preferably 1 gf or more, more preferably 1.5 gf or more, and still more preferably 2 gf or more. The upper limit value of the tack value after 2 times stretching in the length direction of the adhesive article is not particularly limited, but is, for example, 100 gf or less from the viewpoint of balance with the shear force.

From the same viewpoint, the tack value after 4 times stretching in the lengthwise direction of the adhesive article is preferably 2 gf or more, more preferably 3 gf or more, and more preferably 4 gf or more larger than the tack value before stretching. Is more preferred.

From the same viewpoint, the tack value after 4-fold stretching in the longitudinal direction of the adhesive article is preferably 2 gf or more, more preferably 3 gf or more, and still more preferably 4 gf or more. The upper limit of the tack value after 4 times stretching in the longitudinal direction of the adhesive article is not particularly limited, but is, for example, 100 gf or less from the viewpoint of balance with the shear force.

Although the method to form the adhesive article of this embodiment is not specifically limited, For example, an example of the formation method at the time of using the polymer containing composition for non-adhesion layer formation is shown below.
First, a pressure-sensitive adhesive constituting the pressure-sensitive adhesive body is prepared, and is applied linearly on a separator using a dispenser to form the pressure-sensitive adhesive body. In the case where the pressure-sensitive adhesive body is a pressure-sensitive adhesive body having a core and a pressure-sensitive adhesive layer, the surface of the core is coated with the pressure-sensitive adhesive by dipping, dipping, coating, etc. The pressure-sensitive adhesive layer can be formed. The application of the pressure-sensitive adhesive can be performed using, for example, a conventional coater such as a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, or a spray coater. 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. As the drying time, any appropriate time may be employed. The above-mentioned drying time is preferably 5 seconds to 20 minutes, more preferably 5 seconds to 10 minutes, and particularly preferably 10 seconds to 5 minutes.

In forming the non-adhesive layer on the pressure-sensitive adhesive layer, for example, when using a resin, each method for forming the above-mentioned adhesive body using a polymer-containing composition for non-adhesive layer formation is appropriately adopted. Just do it. Moreover, drying conditions can also be suitably employ | adopted and can also be conformed to the drying conditions of the adhesive body mentioned above. In the case of using a polymer material other than resin, the same method may be adopted appropriately using the solution.

In addition, when forming a non-adhesive layer of an emulsion system as a non-adhesive layer, drying of the polymer containing composition for non-adhesive layer formation of water dispersion type is carried out so that fusion (film formation) of emulsion particles is suppressed. It is preferable to adjust the conditions. Although such drying conditions depend on the polymer constituting the emulsion particles, for example, as the drying temperature, the glass transition temperature of the polymer is preferably Tg to Tg, preferably Tg to Tg + 50 ° C, more preferably Tg + 5 to Tg + 30 ° C. The drying time is preferably 5 seconds to 20 minutes, more preferably 5 seconds to 10 minutes. The non-adhesive layer in which the fusion between the emulsion particles is suppressed is considered to break easily in various directions from the interface between the aggregated emulsion particles when the adhesive article is stretched, and it becomes easy to become fine scaly fragments Be

When a metal material is used as the non-adhesive layer, vapor deposition, sputtering or the like can be applied, and when an inorganic material is used, a preparation method using a sol-gel reaction or the like can be applied.

Since the adhesive article of the present embodiment is linear, it can be attached to narrow members and narrow regions while suppressing the protrusion, and is preferable in that it can be easily reworked (rework). For example, it is applicable also to fixation of the narrow frame of portable terminals, such as a mobile phone and a smart phone.
In addition, since the adhesive article of the present embodiment is linear, it can be adhered to the surface of the gap or can be filled by filling the narrow gap and then stretching to develop adhesiveness. Can be

Furthermore, the adhesive article of the present embodiment is preferably bendable, and is particularly preferably a thread-like thread that can be bent in various directions and angles. In addition to the effects described above, the adhesive article having bendability, in particular a filamentous adhesive article, has the advantage of being easily applied to complicated shapes such as curves, curved surfaces, and irregularities.
For example, when an adhesive tape is attached to an adherend having a complex shape such as a curve, a curved surface, or an unevenness, the adhesive tape may be wrinkled or overlapped in such a portion, and the protrusion may be suppressed to prevent sticking. It is difficult to apply, and wrinkles and overlapping portions may also be a factor that reduces adhesion. Further, in order to stick the adhesive tape while preventing the occurrence of wrinkles and overlapping, it may be considered to stick the adhesive tape while cutting it finely, but the workability will be greatly deteriorated. On the other hand, in the case of an adhesive article having bendability, in particular a filamentous adhesive article, it is firmly adhered without being wrinkled or overlapping even when it is attached to a part having a complicated shape such as a curve, curved surface or unevenness. It can be pasted. Furthermore, since such an adhesive article can be attached to a portion to be attached at one time, that is, in one step, it has excellent workability and can be applied to an automation line.

Examples of specific applications of threadlike adhesive articles include cables such as electric wires and optical fibers, LED fiber lights, optical fiber sensors such as FBG (Fiber Bragg Gratings), yarns, cords, wires, etc. The application which fixes the various wire (linear member) of these, and a narrow member in a desired form is mentioned. For example, even in the case where a wire or a narrow member is fixed to another member in a complicated shape, in the case of a threadlike adhesive article, according to the complicated shape that the wire or the narrow member should have It can be firmly fixed with excellent workability while suppressing protrusion, wrinkles and overlaps. In addition, when fixing a wire and a narrow member to another member, a threadlike adhesive article is attached in advance according to the form to which the wire and the narrow member on the surface of the other member should be fixed. Later, according to the adhesive article stuck to the other member surface, a wire and a narrow member can be stuck and fixed. Alternatively, after attaching a threadlike adhesive article to a wire or a narrow member, the wire or the narrow member may be fixed to another member in a desired form.

In addition, a threadlike adhesive article can be suitably used for temporarily fixing (temporarily fixing) an article for temporarily fixing (temporarily fixing) one article to the surface of another article. More specifically, threadlike adhesive articles are particularly suitably used, for example, for temporary fixing (temporary fixing) when producing textile products such as clothes, shoes, bags, hats, and leather products. However, the application is not limited to this, and it is suitably used for various applications where temporary fixing (temporary fixing) is desired.
For example, when one article is fixed to the surface of another article, the one article is temporarily fixed to the surface of the other article using a threadlike adhesive article and then positioned, and then both articles are heated. Fix (finally fix) by a fixing method such as crimping or sewing. In this case, if it is a thread-like adhesive article, it is easy to temporarily fix by avoiding the fixing portion provided between the two articles. For example, when sewing textile products or leather products, if temporary fixing is performed using a threadlike adhesive article, it is easy to temporarily fix by avoiding the sewing part, and adhesion of the adhesive to the needle is easily prevented. it can.
In addition, if it is a filamentous adhesive article, as described above, even if the shape of both articles is a complex shape such as a curve, a curved surface, or an unevenness, it can be favorably affixed while suppressing the oversue, the wrinkles, and the overlap. Moreover, it can be attached in one step, and the workability is good.
For example, even if it is a member which is easy to be deformed, such as cloth, cloth, leather, etc. which constitutes textile products or leather products, temporary fixation with a threadlike adhesive article suppresses or prevents deformation of the members due to tension. The designability after fixation (final fixation) is good.
Furthermore, in the case of a filamentous adhesive article, it is also easy to extract and remove the filamentous adhesive article from between the two articles fixed as needed (this fixation) after fixing (this fixation) of both articles. is there. In this way, it is possible to prevent the protrusion of the pressure-sensitive adhesive and well prevent the deterioration of the design due to the temporal discoloration of the remaining pressure-sensitive adhesive.

Moreover, if it is a thread-like adhesive article, it functions as a yarn obtained by twisting and combining with yarns made of other materials, or by knitting with yarns and cloths (including non-woven fabrics and sheets) made of other materials. Can also be combined.

EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples.

Example 1
(Preparation of Water-Dispersed Acrylic Pressure-Sensitive Adhesive Composition for Forming Pressure-Sensitive Adhesive Layer)
In a reaction vessel equipped with a cooling pipe, a nitrogen introducing pipe, a thermometer and a stirrer, 40 parts by weight of ion-exchanged water was added, and stirring was carried out at 60 ° C. for 1 hour or more while introducing nitrogen gas to perform nitrogen substitution. To this reaction vessel, 0.1 parts by weight of 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] n-hydrate (polymerization initiator) was added. While maintaining the system at 60 ° C., a monomer emulsion A was gradually added dropwise over 4 hours to advance the emulsion polymerization reaction. As monomer emulsion A, 98 parts by weight of 2-ethylhexyl acrylate, 1.25 parts by weight of acrylic acid, 0.75 parts by weight of methacrylic acid, 0.05 parts by weight of lauryl mercaptan (chain transfer agent), γ-methacryloxypropyltrimethoxy An emulsion obtained by adding 0.02 parts by weight of silane (Shin-Etsu Chemical Co., Ltd., trade name "KBM-503") and 2 parts by weight of sodium polyoxyethylene lauryl sulfate (emulsifier) to 30 parts by weight of ion exchanged water used. After completion of dropping of the monomer emulsion A, the temperature is kept at 60 ° C. for 3 hours, and after cooling the system to room temperature, the pH is adjusted to 7 by addition of 10% ammonia water, and acrylic polymer emulsion (water dispersion type acrylic Based polymer) A was obtained.

20 parts by weight of a tackifying resin emulsion (trade name "E-865 NT" manufactured by Arakawa Chemical Industries, Ltd.) was added based on solid content per 100 parts by weight of the acrylic polymer contained in the above acrylic polymer emulsion A. . Furthermore, a pH of 7.2 and a viscosity of 10 Pa are obtained using 10% by weight aqueous ammonia as a pH adjuster and polyacrylic acid as a thickener (trade name "Aron B-500" manufactured by Toagosei Co., Ltd.).・ We adjusted to s. Thus, a water-dispersible acrylic pressure-sensitive adhesive composition A for a pressure-sensitive adhesive layer was obtained.

(Preparation of acrylic polymer emulsion for forming non-adhesive layer)
In a reaction vessel equipped with a cooling pipe, a nitrogen introducing pipe, a thermometer and a stirrer, 40 parts by weight of ion-exchanged water was added, and stirring was carried out at 60 ° C. for 1 hour or more while introducing nitrogen gas to perform nitrogen substitution. To this reaction vessel, 0.1 parts by weight of 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] n-hydrate (polymerization initiator) was added. While maintaining the system at 60 ° C., a monomer emulsion B was gradually added dropwise over 4 hours to advance the emulsion polymerization reaction. As the monomer emulsion B, one obtained by emulsifying 95 parts by weight of butyl methacrylate, 5 parts by weight of acrylic acid and 2 parts by weight of sodium polyoxyethylene lauryl sulfate (emulsifier) in 30 parts by weight of ion exchanged water was used. After the dropping of the monomer emulsion B was completed, the temperature was kept at 60 ° C. for 3 hours. The pH was adjusted to 7 by the addition of 10% by weight aqueous ammonia, and then the solid content was adjusted to 35% with ion-exchanged water to obtain an acrylic polymer emulsion (water-dispersed acrylic polymer) B.

(Production of adhesive article)
The water-dispersible acrylic pressure-sensitive adhesive composition A was applied to a polyurethane elastic fiber (multifilament, 310 dtex) by dipping, followed by drying at 80 ° C. for 5 minutes to form a pressure-sensitive adhesive layer. The thickness of the formed pressure-sensitive adhesive layer was 65 μm. Next, after applying acrylic polymer emulsion B by dipping on the adhesive layer, it was dried at 70 ° C. for 5 minutes to form a non-adhesive layer. The thickness of the non-adhesive layer formed was 8 μm. Thus, a sample of the threadlike adhesive article according to Example 1 was produced.

(Example 2)
(Pressure-sensitive adhesive composition for forming pressure-sensitive adhesive layer)
As a pressure-sensitive adhesive composition for the pressure-sensitive adhesive layer, the water-dispersible acrylic pressure-sensitive adhesive composition A prepared in Example 1 was used.

(Preparation of acrylic polymer solution for forming non-adhesive layer)
150 parts by weight of toluene, 90 parts by weight of butyl methacrylate and 10 parts by weight of acrylic acid are put into a reaction vessel equipped with a cooling pipe, a nitrogen introducing pipe, a thermometer and a stirrer, and stirred at room temperature for 1 hour or more while introducing nitrogen gas Then, nitrogen substitution was performed. 0.6 parts by weight of benzoyl peroxide was added to this reaction vessel, and the temperature was raised to 70 ° C., and reaction was carried out for 8 hours, and then toluene was added to make the solid content 20%, to obtain an acrylic polymer solution C.

(Production of adhesive article)
In the same manner as in Example 1 except that acrylic polymer solution C was used instead of acrylic polymer emulsion B as a material for forming the non-adhesive layer, a sample of a threadlike adhesive article according to Example 2 was produced. .

[Measurement of tack value in initial state (before stretching)]
A sample of the adhesive article according to each example is bonded to a slide glass manufactured by Matsunami Glass Industry Co., Ltd. using a double-sided adhesive tape "No. 5000 N" (thickness: 0.16 mm) manufactured by Nitto Denko Corporation. , Test pieces were made.

The prepared sample was subjected to a probe tack test using a probe tack tester (TACKINESS TESTER Model TAC-II manufactured by RHESCA).
Specifically, a stainless steel probe (SUS 304) with a diameter of 2 mm is contacted with a contact load of 50 gf to the surface of the sample side of the test piece under an environment of measurement temperature 23 ° C., and then 1 mm at a speed of 30 mm / min. The load applied to the probe at the time of separation was measured over time, the maximum load required at the time of separation was determined, and the tack value (gf) in the initial state (before stretching) was determined.

If the tack value measured by the probe tack test is 2 gf or less, it is evaluated as "substantially free of tackiness (substantially non-tacky)".

[Measurement of tack value after stretching]
The sample of the adhesive article according to each example is stretched twice or four times in the length direction, and then using a double-sided adhesive tape "No. 5000 N" (thickness: 0.16 mm) manufactured by Nitto Denko Corporation. It bonded to the slide glass made from Matsunami Glass Industry Co., Ltd. product, and produced the test piece.

About the produced test piece, the probe tack test was done by the test method and test conditions similar to the tack value of an initial state (before extending | stretching), and the tack value (gf) after 2 times extending | stretching and 4 times extending | stretching was measured.

(Elastic modulus at 23 ° C of non-adhesive layer)
The elastic modulus at 23 ° C. of the non-adhesive layer was measured by the following measurement method.
For Example 1, using acrylic polymer emulsion B for forming non-adhesive layer, and using acrylic polymer solution C for forming non-adhesive layer for Example 2, each at 70 ° C. for 5 minutes A sheet-like test piece of width 3 mm × length 30 mm × thickness 0.04 mm was produced under the drying conditions of For each of these test pieces, the vibration frequency of the test piece: 1 Hz, temperature range: -40 to 200 ° C., using a dynamic viscoelasticity measuring device (product name: RSA-III, manufactured by TA Instruments). Temperature rate: The storage elastic modulus at 5 ° C./min was measured.

Table 1 shows the measurement results of the tack value in the initial state (before stretching), the tack value after stretching by 2 times, and the tack value after stretching by 4 times for the samples according to each example. Moreover, the measurement result of the storage elastic modulus of a non-adhesion layer is shown collectively.

The adhesive articles of any of Examples 1 and 2 were substantially non-tacky in the initial state, but developed tackiness by stretching. The adhesive article of Example 1 using an emulsion-based non-adhesive layer as the non-adhesive layer has a higher tack value after stretching than Example 2 using a solvent-based non-adhesive layer as the non-adhesive layer. Indicated.

Although various embodiments have been described above with reference to the drawings, it goes without saying that the present invention is not limited to such examples. It will be apparent to those skilled in the art that various changes and modifications can be made within the scope of the appended claims, and of course these also fall within the technical scope of the present invention. It is understood. In addition, the components in the above-described embodiment may be arbitrarily combined without departing from the scope of the invention.

The present application is the Japanese patent application filed on September 29, 2017 (Japanese Patent Application No. 2017-192139), the Japanese patent application filed on June 29, 2018 (Japanese Patent Application No. 2018-124925) and the Japanese patent application filed on July 23, 2018. The present invention is based on Japanese Patent Application No. 2018-13775 of the application, the contents of which are incorporated by reference into the present application.

1, 2 adhesive article 21 adhesive body 22 core material 23 adhesive layer 31 non-adhesive layer

Claims

An adhesive article comprising: a linear adhesive; and a non-adhesive layer covering a longitudinal surface of the adhesive;
An adhesive article, wherein the non-adhesive layer is broken by stretching of the adhesive article to develop adhesiveness.
The pressure-sensitive adhesive article according to claim 1, wherein the pressure-sensitive adhesive body includes a linear core material and a pressure-sensitive adhesive layer covering a surface in a longitudinal direction of the core material.
The adhesive article according to claim 1, wherein the adhesive article is in the form of threads.
The adhesive article according to any one of claims 1 to 3, wherein the non-adhesive layer comprises a polymeric material.
The adhesive article according to claim 4, wherein the non-adhesive layer comprises an aggregate of a plurality of emulsion particles.
The tack value after 2 times stretching in the length direction of the adhesive article measured by the following probe tack test 2 is 1 gf or more larger than the tack value before stretching measured by the following probe tack test 1 The adhesive article according to any one of 5.
(Probe tack test 1)
A load of 2 mm in diameter made of stainless steel (SUS304) with a contact load of 50 gf is applied to the surface of the adhesive article at a measurement temperature of 23 ° C., and then the load applied to the probe when pulled apart by 1 mm at a speed of 30 mm / min. Is measured over time, and the maximum load required for peeling is determined.
(Probe tack test 2)
After the adhesive article is stretched in the length direction under an environment of measurement temperature 23 ° C., a stainless steel probe (SUS 304) with a diameter of 2 mm is brought into contact with the surface of the adhesive article with a contact load of 50 gf, and 30 mm The load applied to the probe is measured with time when pulling 1 mm apart at a speed of 1 / min, and the maximum load required for peeling is determined.