KR20200125657A - Thermoplastic adhesive sheet and its use - Google Patents

Abstract

A thermoplastic adhesive sheet capable of exhibiting a temporary adhesiveness and deformation recovery property and excellent adhesive function is provided. The thermoplastic adhesive sheet provided by the present invention has a thermoplastic adhesive layer. The thermoplastic adhesive sheet has the following characteristics:
(A) The peel strength of the polyester-based urethane foam is 2N/10 mm or more; And
(B) After 50% elongation at 23°C at a rate of 300 mm/min and hold for 3 seconds, and then shrinking at a rate of 300 mm/min, the elongation strength at 30% elongation F _E30% shrinkage strength the hysteresis _S30 obtained from the _F% ratio _{[F S30% / F E30%} ] of not less than 35%; Satisfies

Description

Thermoplastic adhesive sheet and its use

The present invention relates to a thermoplastic adhesive sheet and a fabric bonded by the thermoplastic adhesive sheet. This application claims priority based on Japanese Patent Application No. 2018-33435 for which it applied on February 27, 2018, and the entire contents of the application are incorporated by reference in this specification.

Various adhesives formed in a sheet form are widely used in various industrial fields such as home appliances, automobiles, and OA equipment. In addition to having well-known advantages such as bonding efficiency and stable quality when compared to other bonding means, this kind of sheet-like adhesive may have unique advantages in each application. For example, when compared to the sewing of the clothing, the clothing after bonding may have an excellent fit. Specifically, while the sewing thread of the stitched portion in the undergarment has skin irritation, the adhesive can bond fabrics to each other while keeping the fabric surface smooth, so that the skin irritation of the sewn clothing does not occur. Patent document 1 is mentioned as a document which discloses a conventional technique used for such a purpose. In Patent Document 1, in order to obtain temporary adhesiveness, a tape for fabric bonding in which an adhesive layer is disposed on the surface of a hot melt adhesive is proposed. Patent Documents 2 and 3 show a state of a flexible solid (viscoelastic body) in a temperature range near room temperature, and a pressure-sensitive adhesive adhesive having a property of being easily adhered to an adherend by pressure (hereinafter also referred to as ``pressure sensitive adhesive''). ), and discloses a pressure-sensitive adhesive containing a styrenic block copolymer.

Japanese Patent Application Publication No. 2008-81724 Japanese Patent Application Publication No. 2015-28130 Japanese Patent Application Publication No. 2017-88702

As the adhesive used for bonding the fabric, the thermoplastic adhesive described in Patent Document 1 may be mentioned. After the thermoplastic adhesive is positioned at the bonding point of the cloth, it is impregnated into the cloth by hot pressing to bond the cloth to each other. However, such a thermoplastic adhesive is usually not viscous, and does not adhere to a rough surface such as a cloth at room temperature. Therefore, other means such as the surface pressure-sensitive adhesive layer used in Patent Document 1 are required for temporary bonding for alignment or the like. Further, for example, an adhesive impregnated with a stretchable material such as cloth by hot pressing is difficult to follow the stretch of an adherend material because of its hardness at room temperature. Therefore, it is possible to reduce the elasticity of the adherend material at the bonding site with the adhesive. Such a change causes a sense of incongruity in the fit in the garment using cloth.

An object of the present invention is to provide a thermoplastic adhesive sheet that has been created in view of the above circumstances, has temporary adhesiveness and deformation recovery, and is capable of exhibiting a good adhesive function. Another object of the present invention is to provide a fabric bonded by a thermoplastic adhesive sheet.

According to the present specification, a thermoplastic adhesive sheet (hereinafter, also simply referred to as "adhesive sheet") having a layer of a thermoplastic adhesive (hereinafter, also simply referred to as "adhesive agent") is provided. This thermoplastic adhesive sheet has the following characteristics:

(A) A thermoplastic adhesive sheet was bonded to a polyester-based urethane foam having a thickness of 10 mm in an environment of 23°C and 50% RH by reciprocating a roller of 2 kg, and leaving it in the same environment for 30 minutes, and then a tensile speed of 300 The peel strength measured under the conditions of mm/min and a peel angle of 180 degrees is 2N/10 mm or more; And

(B) A measurement sample of a thermoplastic adhesive sheet having a measurement length of 100 mm was prepared, and the measurement sample was elongated by 50% at 23°C at a rate of 300 mm/min and held for 3 seconds, and then at a rate of 300 mm/min. When contracted, the hysteresis determined from the ratio of the shrinkage strength F _S30% to the stretch strength F _E30% at 30% elongation length [F _S30% /F _E30% ] is 35% or more;

Satisfies

According to the above configuration, by satisfying the characteristic (A), the adhesive sheet has viscosity at room temperature (about 23°C), and, for example, good temporary adhesiveness is achieved by applying it to a rough surface such as cloth by hand at room temperature. Show. The adhesive sheet bonded to the adherend material by temporary bonding is bonded to the adherend with good positional accuracy by subsequent bonding by a hot press or the like (also referred to as “main bonding”). In the main bonding, good adhesion and fixation are realized by utilizing the thermoplastic properties of the thermoplastic adhesive sheet. Particularly, when the surface of the adherend is a rough surface or the adherend is a material to be impregnated, the adhesive sheet is spread widely by heating or penetrates into the adherend, thereby exhibiting good adhesion performance. Here, the material to be impregnated refers to a material having a property that allows impregnation of a fluid (typically a liquid body). In addition, by satisfying the characteristic (B), for example, in the aspect of affixing to a material having deformation recovery properties, such as an elastic material or a rubber elastic material, bonding with the deformation (for example, stretching) of the material. After the sheet is deformed, it can be restored to its original shape together with the adherend material. That is, the adhesive sheet does not impede the shape recovery (eg, elasticity) of the adherend material. The strain recovery that can follow the strain recovery (eg, elasticity) of the adherend may be one that does not impair the fit of, for example, clothing (especially underwear). In short, the thermoplastic adhesive sheet satisfying the above properties can exhibit a good adhesive function while having both temporary adhesiveness and deformation recovery properties.

The thermoplastic adhesive sheet according to a preferred aspect has the following characteristics:

(C) For the thermoplastic adhesive sheet measurement sample having a measurement length of 100 mm, the 30% modulus measured at a rate of 300 mm/min at 23° C. is 0.6 MPa or less;

More satisfying.

Since the adhesive sheet satisfying the above characteristic (C) is excellent in flexibility, it does not impair the flexibility of the material when it is used for bonding a flexible material such as, for example, cloth. For example, in the case where the adhesive sheet is used in a manner in which the adherend material is impregnated, it is advantageous to be able to ensure flexibility in the material. As an example of the effect of this configuration, there is a reduction in the hardness (hardness) of the conventional adhesive applied to the fabric.

The thermoplastic adhesive sheet according to a preferred aspect has the following characteristics:

(D) After pressing the thermoplastic adhesive sheet to a stainless steel sheet under the conditions of 120°C, 0.2 MPa, and 10 seconds, and allowed to stand at 23°C for 30 minutes, the peel strength measured under the conditions of a tensile speed of 300 mm/min and a peel angle of 180° , 15N/10mm or more;

More satisfying.

The thermoplastic adhesive sheet that satisfies the above characteristic (D) can be firmly bonded to an adherend having a rough surface such as cloth by thermocompression bonding, and thus has excellent bonding reliability.

In a preferred aspect, the thermoplastic adhesive layer is a rubber adhesive layer containing a rubber polymer as a base polymer. Further, it is more preferable that the thermoplastic adhesive layer contains, as a base polymer, a block copolymer of a monovinyl substituted aromatic compound and a conjugated diene compound. By employing the above-described rubber-based adhesive, the properties and effects disclosed herein can be preferably realized.

In a preferred embodiment, the thermoplastic adhesive layer contains, as a tackifying resin, a tackifying resin T _LOH having a hydroxyl value of 30 mgKOH/g or less. Deterioration of the adhesive sheet is preferably suppressed by using a tackifying resin having a hydroxyl value equal to or less than a predetermined value.

In a preferred aspect, the thermoplastic adhesive layer is a non-crosslinkable adhesive layer. The non-crosslinkable adhesive is liable to obtain good adhesive strength by thermocompression.

In a preferred aspect, the thickness of the thermoplastic adhesive sheet is 0.03 mm to 1 mm. By setting the thickness of the adhesive sheet to a predetermined value or more, there is a tendency that the temporary adhesiveness and the main adhesiveness are improved. Further, by making the thickness less than or equal to a predetermined value, the deformation recovery property of the adherend material is easily maintained.

The thermoplastic adhesive sheet according to a preferred aspect is configured as a base-free adhesive sheet composed of only an adhesive layer. By constituting in this way, each of the above characteristics can be preferably satisfied, and the effect of the technology disclosed herein can be preferably exhibited. In addition, bonding of the adherend can be completed only with a thermoplastic adhesive without using a substrate. This is meaningful in terms of productivity, bonding efficiency, and weight reduction of the adhesive sheet.

Since the thermoplastic adhesive sheet disclosed herein has temporary adhesiveness and can exhibit a good adhesive function, it is preferably used for bonding of fabrics requiring alignment by temporary bonding. In addition, the adhesive sheet is also excellent in deformation recovery. Therefore, it is preferable for the use of bonding elastic fabrics (suitably undergarments). By applying the technology disclosed here to the bonding of the fabric, the adhesive sheet is positioned at the bonding portion of the fabric with high precision using its temporary adhesiveness, and then the adhesive sheet is impregnated with the fabric by main bonding by heating, resulting in good adhesion. And also well follows the elasticity of the fabric. This leads, for example, to not impair the fit of a garment made using the fabric. Therefore, according to the technique disclosed herein, a fabric bonded by any thermoplastic adhesive sheet disclosed herein is provided.

In addition, in the present specification, the bonding of fabrics may be a bonding of one piece of cloth and another piece of cloth, or may be bonding of a portion of one piece of cloth to another piece of cloth.

1 is a schematic cross-sectional view showing a configuration of a thermoplastic adhesive sheet (double-sided adhesive sheet without a base) according to an embodiment.
2 is a schematic cross-sectional view showing a configuration of a thermoplastic adhesive sheet (double-sided adhesive sheet having a base material) according to another embodiment.
3 is a schematic cross-sectional view showing a configuration of a thermoplastic adhesive sheet (a single-sided adhesive sheet having a base material) according to another embodiment.

Hereinafter, preferred embodiments of the present invention will be described. In addition, matters necessary for carrying out the present invention as matters other than matters specifically mentioned in the present specification can be grasped as design matters by those skilled in the art based on the prior art in the relevant field. The present invention can be implemented based on the content disclosed in this specification and the common technical knowledge in the field.

In the following drawings, members and portions exhibiting the same action are denoted by the same reference numerals, and overlapping descriptions may be omitted or simplified. In addition, the embodiment described in the drawings is schematically designed to clearly explain the present invention, and does not accurately represent the size or scale of the adhesive sheet of the present invention actually provided as a product.

In this specification, the "thermoplastic adhesive" refers to an adhesive that is softened and plastically deformed by heating at a predetermined temperature or higher. In addition, the thermoplastic adhesive is a material having a property of curing again when cooled to a melting temperature or lower, and repeats softening and curing reversibly by heat. The thermoplastic adhesive disclosed herein may be one that exhibits fluidity at a temperature of about 80° C. or higher (eg, about 100° C. or higher, typically about 120° C. or higher). Thermoplastic properties are usually controlled by appropriately setting conditions (temperature, pressure, time, etc.) during main bonding. Further, in a typical embodiment, the thermoplastic adhesive has a weight fraction (gel fraction) of an organic solvent insoluble component measured by immersion in an organic solvent such as toluene for 1 week is about 3% or less (eg, 0 to 1%). The gel fraction is measured using a porous polytetrafluoroethylene membrane (for example, a brand name "Nitoplon NTF1122" manufactured by Nitto Denko Corporation, an average pore diameter of 0.2 µm, and a porosity of 75%).

In this specification, the "pressure-sensitive adhesive" refers to a material having a property of being easily bonded to an adherend by pressure, which represents the state of a flexible solid (viscoelastic body) in a temperature range near room temperature, as described above. The pressure-sensitive adhesive referred to herein is, as defined in "CA Dahlquist, "Adhesion: Fundamental and Practice", McLaren & Sons, (1966) P. 143", in general, the complex tensile modulus E ^* (1Hz) <10 ⁷ dyne It is a material having a property satisfying /cm2 (typically, a material having the above property at 25°C). The pressure-sensitive adhesive in the technique disclosed herein can also be grasped as a solid content of an adhesive composition or a constituent component of an adhesive layer. In the technique disclosed herein, the adhesive and adhesive layer satisfying the characteristics (A) described later are typical examples of the pressure-sensitive adhesive and pressure-sensitive adhesive layer.

In addition, in this specification, the "block copolymer of a monovinyl substituted aromatic compound and a conjugated diene compound" is a segment (referring to a copolymerization component exceeding 50 weight%, the same hereafter) containing a monovinyl substituted aromatic compound as a main monomer (the same applies hereinafter). Hereinafter, also referred to as "A segment") and a segment containing a conjugated diene compound as a main monomer (hereinafter, referred to as "B segment"), respectively, refers to a polymer having at least one. In general, the glass transition temperature of segment A is higher than that of segment B. As a typical structure of such a polymer, a triblock-structured copolymer having A segment (hard segment) at both ends of a B segment (soft segment) (a triblock structure of an ABA structure), one A segment and one B segment. Diblock structure copolymer (AB structure diblock product) etc. are mentioned.

In addition, in this specification, a "styrene-type block copolymer" means a polymer which has at least one styrene block. The styrene block refers to a segment containing styrene as a main monomer. The segment containing substantially only styrene is a typical example of the styrene block mentioned here. In addition, the "styrene isoprene block copolymer" refers to a polymer having at least one styrene block and at least one isoprene block (a segment containing isoprene as a main monomer). As a representative example of a styrene isoprene block copolymer, a triblock-structured copolymer (triblock body) having a styrene block (hard segment) at both ends of an isoprene block (soft segment), one isoprene block and one styrene block The copolymer (diblock body) etc. of the diblock structure to be included are mentioned. "Styrene butadiene block copolymer" refers to a polymer having at least one styrene block and at least one butadiene block (a segment containing butadiene as a main monomer).

In addition, in this specification, the "styrene content" of a styrene-type block copolymer means the weight ratio of a styrene component to the total weight of the said block copolymer. The styrene content can be measured by NMR (nuclear magnetic resonance spectroscopy).

In addition, the ratio of the diblock body occupied in the styrene-based block copolymer (hereinafter sometimes referred to as "diblock body ratio" or "diblock ratio") is determined by the following method. That is, a styrenic block copolymer was dissolved in tetrahydrofuran (THF), and a total of 4 columns were connected in series with 2 columns for liquid chromatography of GS5000H and G4000H manufactured by Tosoh Corporation, respectively, and THF was added to the mobile phase. Using, high-performance liquid chromatography is performed under the conditions of a temperature of 40°C and a flow rate of 1 mL/min. From the obtained chart, the peak area corresponding to the diblock body is measured. And by calculating the percentage of the peak area corresponding to the diblock body with respect to the total peak area, the ratio of the diblock body is obtained.

<Structure Example of Thermoplastic Adhesive Sheet>

The adhesive sheet disclosed herein (which may be in the form of a long shape such as a tape) may be in the form of a double-sided adhesive sheet 1 without a base (ie, without a base) as shown in FIG. 1, for example. have. This adhesive sheet 1 is a base-free adhesive sheet comprising a thermoplastic adhesive layer 11. The adhesive layer 11 typically has a single layer structure. In the double-sided adhesive sheet 1 before use (before affixing to an adherend), the first adhesive surface 11A and the second adhesive surface 11B of the adhesive layer 11 are at least the surface of the adhesive layer side (front The side) may be in a form protected by release liners 21 and 22, respectively, which are release surfaces. Alternatively, the release liner 22 is omitted, and the second adhesive surface 11B is peeled off by overlapping the release liner 21 with both sides of the release liner and winding the adhesive layer 11 in a spiral shape. It may be a form protected by contacting the rear surface of the liner 21.

The technique disclosed here is preferably applied to a double-sided adhesive sheet without a substrate as shown in Fig. 1, and can also be applied to a double-sided adhesive sheet 2 having a substrate as shown in Fig. 2. This double-sided adhesive sheet 2 includes a substrate (for example, a polyurethane film) 15 and a first adhesive layer 11 and a second adhesive layer 12 supported on both surfaces of the substrate 15, respectively. Equipped. More specifically, the first adhesive layer 11 and the second adhesive layer 12 are provided on the first surface 15A and the second surface 15B (both are non-peelable) of the substrate 15. The double-sided adhesive sheet 2 before use (before affixing to an adherend) is the surface (adhesive surface) 11A of the first adhesive layer 11 and the surface (adhesive surface) 12A of the second adhesive layer 12 ) May be in a form in which at least the surface (front surface) on the side of the adhesive layer is each protected by a release liner having a release surface. Alternatively, for example, as shown in FIG. 2, by using a release liner 21 having both sides as release surfaces, the first adhesive layer 11 is overlapped and wound in a vortex shape. The surface 11A of) may be in contact with the rear surface of the release liner 21 to be protected.

The technology disclosed herein further includes a substrate of a single-sided adhesive type comprising a substrate 15 and an adhesive layer 11 supported on the first side (non-removable side) 15A of the substrate, as shown in FIG. 3. It can also be applied to the adhesive sheet 3 having. As for the adhesive sheet 3 before use, as shown in FIG. 3, for example, the surface (adhesive surface) 11A of the adhesive layer 11 is at least the surface (front surface) on the side of the adhesive layer as a peeling surface. It may be in the form of protection with the release liner 21 that has been made. Alternatively, the first adhesive surface 11A is formed by winding the adhesive sheet 3 having the base material by omitting the release liner 21 and using the base material 15 having the second surface 15B as the release surface. It may be in a form protected by contacting the second surface 15B of the substrate 15.

The total thickness of the adhesive sheet disclosed herein is not particularly limited, and from the viewpoint of thinning, miniaturization, weight reduction, resource saving, etc., it is appropriate to be about 3 mm or less, preferably about 1 mm or less, more preferably Preferably, it is about 0.7 mm or less, more preferably about 0.5 mm or less (eg, about 0.4 mm or less). The adhesive layer with a limited thickness tends to have a small influence on the deformation recovery (e.g., elasticity) of the adherend due to the impregnation because the amount of impregnation into the adherend such as cloth is also limited during thermal compression. . In addition, from the viewpoint of securing good adhesive properties, the total thickness is suitably about 0.01 mm or more, preferably about 0.03 mm or more, more preferably about 0.05 mm or more, even more preferably about It is 0.1mm or more. In addition, the thickness of the adhesive layer and the base material is included in the total thickness of the adhesive sheet, but the thickness of the release liner is not included.

<The characteristics of the thermoplastic adhesive sheet>

(Characteristic (A))

The adhesive sheet disclosed herein is characterized by having an adhesive force to a foam (large foam adhesive force) of about 2 N/10 mm or more. Since the foam surface is a rough surface, an adhesive sheet that satisfies the above characteristics exhibits good temporary adhesiveness by applying it to a rough surface such as cloth by hand at room temperature, for example. This enables high-precision positional alignment with respect to the surface of the adherend. The adhesive force of the large foam is preferably about 3N/10mm or more, more preferably about 4N/10mm or more. The adhesive strength of the large foam may be about 5 N/10 mm or more, but from the viewpoint of reattachability and the like, it is appropriate to be about 10 N/10 mm or less, and preferably about 8 N/10 mm or less (for example, about 6 N/ 10 mm or less).

The characteristic (A) (large foam adhesion) is specifically measured by the following method. That is, the thermoplastic adhesive sheet is cut to a size of 100 mm x 10 mm to prepare a measurement sample. When the measurement object is a double-sided adhesive sheet, a single surface (non-measured adhesive surface) is affixed to a 25 µm-thick polyethylene terephthalate (PET) film and backed. Subsequently, under an environment of 23°C and 50% RH, the surface of the thermoplastic adhesive layer to be measured is exposed, and the exposed adhesive surface is rounded off a 2 kg roller to the surface of a polyester urethane foam having a thickness of 10 mm as an adherend. To join (compression). After allowing this to stand for 30 minutes in the same environment, the peel strength (large foam adhesion) [N/10 mm] is measured under conditions of a tensile speed of 300 mm/min and a peel angle of 180 degrees using a universal tensile compression tester. As the adherend, a polyester-based soft urethane foam (trade name "SC" (grey) manufactured by Innoac Corporation, density 31 kg/m 3) is used. In addition, as the universal tensile compression testing machine, a commercially available device (for example, the device name "tensile compression testing machine, TG-1kN" manufactured by Minevea Corporation) can be used. Also in Examples described later, it is measured by the same method.

(Property (B))

In addition, the adhesive sheet disclosed herein is characterized by having a hysteresis (30% hysteresis at 50% elongation) of about 35% or more measured by the following method. By satisfying this property, for example, in an aspect in which the adhesive sheet is deformed due to deformation (e.g., expansion and contraction) of the material, in an aspect in which it is attached to a deformation recovery material such as an elastic material, the adherend material With it, it can be restored to its original shape. That is, the adhesive sheet does not impede the shape recovery (eg, elasticity) of the adherend material. The 30% hysteresis at the time of 50% elongation is preferably about 40% or more, more preferably about 50% or more (eg, 55% or more). The hysteresis is ideally 100%, but from the viewpoint of compatibility with other properties such as temporary adhesiveness, it may be about 80% or less, and for example, about 70% or less.

The characteristic (B) (30% hysteresis at 50% elongation) is specifically measured by the following method. That is, the thermoplastic adhesive sheet is cut into a width of 50 mm so as to have a measurement length of 100 mm, and is wound in the width direction to prepare a measurement sample in a cylindrical shape. In addition, since this measurement depends on the length of the measurement sample, but does not depend on the cross-sectional area (ie, thickness and width), a width other than 50 mm may be adopted within a range that does not interfere with the measurement. For the same reason, it is not necessary to take a winding or a cylinder shape as long as the measurement is not hindered. The prepared measurement sample was set so that the interchuck distance (measurement length) was 100 mm in a tensile compression tester, stretched 50% at a rate of 300 mm/min at 23°C (and thus stretched to 150 mm), and stretched 50%. After holding in the state for 3 seconds, a contraction operation is performed at a rate of 300 mm/min this time, and the elongation is returned to 0% (distance between chuck 100 mm). In this measurement, the elongation strength F _E30% [N] at 30% elongation length (130 mm) and the shrinkage strength F _S30% [N] at 30% elongation length are recorded, and elongation strength F _E30% From the ratio of the shrinkage strength F _S30% to [N] [F _S30% /F _E30% ], the hysteresis value (%) is obtained from the following equation.

Hysteresis value (%) = F _S30% /F _E30% ×100

As the universal tensile compression testing machine, a commercially available device (for example, the device name "tensile compression testing machine, TG-1kN" manufactured by Minevea Corporation) can be used. Also in Examples described later, it is measured by the same method.

(Characteristic (C))

The adhesive sheet according to a preferred aspect has a 30% modulus of 0.6 MPa or less. When the object to be adhered to the adhesive sheet is a flexible material such as fabric, by using an adhesive sheet that satisfies the above properties, adhesion without disturbing the deformation of the material and not impairing the flexibility is realized. The 30% modulus is more preferably about 0.5 MPa or less, and still more preferably about 0.45 MPa or less (eg, 0.4 MPa or less). The 30% modulus is usually appropriately about 0.1 MPa or more, preferably about 0.2 MPa or more, more preferably about 0.3 MPa or more (e.g., 0.35 MPa or more) from the viewpoint of being compatible with other properties such as strain recovery. ㎫ or more).

The characteristic (C) (30% modulus) is measured at a rate of 300 mm/min at 23°C for a measurement sample of a thermoplastic adhesive sheet having a measurement length of 100 mm. Specifically, in the measurement of the characteristic (B), 30% modulus [MPa] is obtained by dividing the elongation strength F _E30% [N] at 30% elongation length (130 mm) by the cross-sectional area [mm 2] of the adhesive sheet. You can get it. Since the 30% modulus does not depend on the length of the measurement sample, at the time of measurement, the interchuck distance of the tensile compression tester may be appropriately changed. In addition, since the cross-sectional area is divided, the width and thickness can be changed within a range that does not interfere with measurement. For the same reason, there is no need to be wound or cylindrical in a range that does not interfere with measurement. Other measurement conditions are basically the same as those of the characteristic (B). Also in Examples described later, it is measured by the same method.

(Property (D))

The adhesive sheet according to a preferred embodiment has a thermocompression bonding force (relative to SUS thermocompression bonding) of about 15N/10mm or more to stainless steel measured under a thermocompression bonding condition of 120°C, 0.2 MPa, and 10 seconds. The thermocompression bonding strength of SUS is different from the thermocompression bonding bonding strength to a rough surface such as a cloth, but exhibits a high correlation. Since the thermoplastic adhesive sheet satisfying this characteristic tends to exhibit a predetermined or higher thermocompression bonding strength even on a rough surface such as a cloth, it can be firmly adhered to the adherend having the rough surface in the main bonding after temporary fixing. The adhesive force of the SUS thermocompression bonding is more preferably about 18N/10mm or more, more preferably about 20N/10mm or more, particularly preferably about 22N/10mm or more, for example about 25N/10mm It may be more than, about 28N/10mm or more, and about 30N/10mm or more may be sufficient. The upper limit of the SUS thermocompression bonding strength is not particularly limited, and may be, for example, about 50N/10mm or less.

The characteristic (D) (to SUS thermocompression bonding force) is specifically measured by the following method. That is, the thermoplastic adhesive sheet is cut to a size of 100 mm x 10 mm to prepare a measurement sample. When the measurement object is a double-sided adhesive sheet, a single surface (non-measurement adhesive surface) is affixed to a 50 µm-thick PET film and backed. Then, in an environment of 23°C and 50% RH, the surface of the thermoplastic adhesive layer to be measured is exposed, and the exposed adhesive surface is exposed to the surface of a stainless steel plate (SUS304 plate) as an adherend under conditions of 120°C, 0.2 MPa, and 10 seconds. Thermocompression bonding. After allowing this to stand for 30 minutes in the same environment, the peel strength (relative to SUS thermocompression bonding) [N/10 mm] is measured under conditions of a tensile speed of 300 mm/min and a peel angle of 180 degrees using a universal tensile compression tester. . As the universal tensile compression testing machine, a commercially available device (for example, the device name "tensile compression testing machine, TG-1kN" manufactured by Minevea Corporation) can be used. Also in Examples described later, it is measured by the same method.

<Thermoplastic adhesive layer>

The type of adhesive constituting the thermoplastic adhesive layer disclosed herein is not particularly limited. The adhesive layer is, for example, acrylic, polyester, urethane, polyether, olefin, rubber, silicone, polyamide, fluorine, vinyl acetate, vinyl chloride, vinyl alcohol, vinyl acetal, vinyl It may be an adhesive layer formed of an adhesive composition comprising one or two or more selected from various polymers (adhesive polymers) such as butyral as a base polymer (a main component in the polymer component, that is, a component occupying 50% by weight or more). The technology disclosed herein may be preferably implemented in the form of an adhesive sheet having an adhesive layer comprising an acrylic polymer, a polyester polymer, a urethane polymer, or a rubber polymer as a base polymer. Among them, it can be carried out particularly preferably in the form of an adhesive sheet having a rubber-based adhesive layer comprising a rubber-based polymer as a base polymer.

Examples of the base polymer contained in the rubber-based adhesive layer include natural rubber; Styrene butadiene rubber; Polyisoprene; Acrylonitrile butadiene rubber; Chloroprene rubber; Butene (referring to 1-butene, and cis- or trans-2-butene) and/or 2-methylpropene (isobutylene) as a main monomer; AB-type or ABA-type block copolymer rubber and its hydrides, such as styrene-butadiene-styrene block copolymer rubber (SBS), styrene-isoprene-styrene block copolymer rubber (SIS), styrene that is a hydride of SBS -Ethylene-butylene-styrene block copolymer rubber, styrene-ethylene-propylene-styrene block copolymer rubber which is a hydride of SIS; And various rubber-based polymers. These rubber-based polymers can be used alone or in combination of two or more.

<Base polymer>

The adhesive layer according to a preferred embodiment contains, as a base polymer, a block copolymer of a monovinyl substituted aromatic compound and a conjugated diene compound. The monovinyl substituted aromatic compound refers to a compound in which one functional group having a vinyl group is bonded to an aromatic ring. As a representative example of the aromatic ring, a benzene ring (which may be a benzene ring substituted with a functional group not having a vinyl group (eg, an alkyl group)) is mentioned. Specific examples of the monovinyl substituted aromatic compound include styrene, α-methylstyrene, vinyl toluene, and vinyl xylene. As a specific example of the said conjugated diene compound, 1,3-butadiene, isoprene, etc. are mentioned. These block copolymers can be used as a base polymer alone or in combination of two or more.

The A segment (hard segment) in the block copolymer has a copolymerization ratio of about 70% by weight or more (more preferably about 90% by weight or more) of the monovinyl substituted aromatic compound (two or more types can be used in combination). , It may be substantially 100% by weight). The B segment (soft segment) in the block copolymer has a copolymerization ratio of the conjugated diene compound (two or more can be used in combination) of about 70% by weight or more (more preferably about 90% by weight or more, and substantially It is preferably 100% by weight). According to such a block copolymer, a higher performance adhesive sheet can be realized.

The block copolymer may be in the form of a diblock body, a triblock body, a radial body, or a mixture thereof. In a triblock body or a radial body, it is preferable that an A segment (for example, a styrene block) is arrange|positioned at the terminal of a polymer chain. This is because the A segment disposed at the end of the polymer chain tends to gather together to form a domain, thereby forming a pseudo-crosslinked structure to improve cohesiveness of the adhesive.

As the block copolymer in the technology disclosed herein, from the viewpoint of adhesion (peel strength) to an adherend, it is appropriate to use one having a diblock body ratio of about 30% by weight or more, and the diblock body ratio is, It is preferably at least about 40% by weight, more preferably at least about 50% by weight, still more preferably at least about 60% by weight, particularly preferably at least about 65% by weight. From the viewpoint of peel strength, a block copolymer having a diblock body ratio of about 70% by weight or more is most preferred. Further, from the viewpoint of cohesiveness and the like, a block copolymer having a diblock body ratio of about 90% by weight or less (more preferably about 85% by weight or less, for example, about 80% by weight or less) can be preferably used.

<Styrene block copolymer>

In a preferred aspect of the technology disclosed herein, the base polymer is a styrenic block copolymer. For example, it is preferable that the base polymer includes at least one of a styrene isoprene block copolymer and a styrene butadiene block copolymer. Among the styrenic block copolymers contained in the adhesive, the ratio of the styrene isoprene block copolymer is about 70% by weight or more, the ratio of the styrene butadiene block copolymer is 70% by weight or more, or the styrene isoprene block copolymer and the styrene butadiene block It is preferred that the total proportion of the copolymer is about 70% by weight or more. In one preferred embodiment, substantially all (eg, about 95 to 100% by weight) of the styrenic block copolymer is a styrene isoprene block copolymer.

The styrene content of the styrenic block copolymer may be, for example, about 5 to 40% by weight. From the viewpoint of cohesiveness, usually, a styrene-based block copolymer having a styrene content of about 10% by weight or more (more preferably more than 10% by weight, for example, 12% by weight or more) is preferable. In addition, from the viewpoint of peel strength, the styrene content is preferably about 35% by weight or less (typically about 30% by weight or less, more preferably about 25% by weight or less), and 20% by weight or less (typically about 20% by weight or less). Less than 18% by weight, for example up to 18% by weight) is particularly preferred. From the viewpoint of better exerting the effect of applying the technique disclosed herein (for example, the effect of improving temporary adhesion), a styrene-based block copolymer having a styrene content of 12% by weight or more and less than 20% by weight is preferably used. Can be adopted.

In the technology disclosed herein, when using a block copolymer of a monovinyl substituted aromatic compound and a conjugated diene compound (for example, a styrene block copolymer) as the base polymer, a rubber-like polymer other than the block copolymer is used. It can contain 1 type or 2 or more types. Such rubber-like polymers are known in the field of adhesives: acrylic, polyester, urethane, polyether, olefin, rubber, silicone, polyamide, fluorine, vinyl acetate, vinyl chloride, vinyl alcohol, It may be various polymers such as vinyl acetal-based and vinyl butyral-based. Examples of the rubber-based rubber polymer include natural rubber, acrylonitrile butadiene rubber, isoprene rubber, chloroprene rubber, polyisobutylene, butyl rubber, and recycled rubber. In the case where the adhesive layer contains a rubber-like polymer other than the block copolymer, the amount of the rubber-like polymer is usually suitably set to about 50 parts by weight or less per 100 parts by weight of the block copolymer, preferably. Is about 30 parts by weight or less, more preferably about 10 parts by weight or less (eg, about 5 parts by weight or less). The technology disclosed herein is a mode in which the adhesive layer substantially does not contain a rubber-like polymer other than the block copolymer (for example, the content per 100 parts by weight of the block copolymer is 0 to 1 part by weight). It can be carried out preferably.

<Adhesion imparting resin>

It is preferable that the adhesive layer disclosed here contains tackifying resin in addition to the said base polymer. As the tackifying resin, one type selected from various known tackifying resins such as petroleum resin, styrene resin, coumarone indene resin, terpene resin, modified terpene resin, rosin resin, rosin derivative resin, and ketone resin, or Two or more types can be used.

Examples of petroleum resins include aliphatic (C5) petroleum resins, aromatic (C9) petroleum resins, aliphatic/aromatic copolymers (C5/C9) petroleum resins, and hydrogenated substances thereof (e.g., aromatic petroleum resins And alicyclic petroleum resins obtained by hydrogenation).

Examples of styrenic resins include those containing a single polymer of styrene as a main component, those containing a single polymer of α-methylstyrene as a main component, those containing a single polymer of vinyltoluene as a main component, among styrene, α-methylstyrene, and vinyltoluene. A copolymer containing two or more types in the monomer composition as a main component (for example, α-methylstyrene/styrene copolymer resin containing an α-methylstyrene/styrene copolymer as a main component), etc. are mentioned.

As the coumarone indene resin, a resin containing coumarone and indene as a monomer component constituting the skeleton (main chain) of the resin can be used. Examples of monomer components that can be included in the skeleton of the resin other than coumarone and indene include styrene, α-methylstyrene, methylindene, and vinyltoluene.

Examples of the terpene resin include α-pinene polymer, β-pinene polymer, dipentene polymer, and the like. Examples of the modified terpene resin include those obtained by modifying the terpene resin (phenol modification, styrene modification, hydrogenation modification, hydrocarbon modification, etc.). Specifically, a terpene phenol resin, a styrene-modified terpene resin, a hydrogenated terpene resin, etc. are illustrated.

The ``terpene phenol resin'' refers to a polymer containing a terpene residue and a phenol residue, and a copolymer of a terpene and a phenol compound (terpene-phenol copolymer resin), and a homopolymer or copolymer of a terpene (terpene resin, typically Is a concept including both the unmodified terpene resin) phenol-modified (phenol-modified terpene resin). Suitable examples of the terpenes constituting the terpene phenol resin include monoterpenes such as α-pinene, β-pinene, and limonene (including d-form, l-form and d/l-form (dipentene)).

Specific examples of the rosin-based resin include unmodified rosin (raw rosin) such as gum rosin, wood rosin and tall oil rosin; Modified rosin (hydrogenated rosin, disproportionated rosin, polymerized rosin, other chemically modified rosin, etc.) obtained by modifying these unmodified rosin by hydrogenation, disproportionation, polymerization, or the like; And the like. In addition, examples of rosin derivative resins are those obtained by esterifying unmodified rosin with alcohols (i.e., esterified products of rosin), and modified rosin (hydrogenated rosin, disproportionate rosin, polymerized rosin, etc.) with alcohols. Rosin esters such as modified rosin (i.e. esterified products of modified rosin), unsaturated fatty acid modified rosin, rosin in which unmodified rosin or modified rosin (hydrogenated rosin, disproportionated rosin, polymerized rosin, etc.) is modified with unsaturated fatty acid In unsaturated fatty acid-modified rosin esters, unmodified rosin, modified rosin (hydrogenated rosin, disproportionated rosin, polymerized rosin, etc.), unsaturated fatty acid-modified rosin, or unsaturated fatty acid-modified rosin esters Phenol in metal salts of rosin (especially rosin esters) such as rosin alcohols, unmodified rosin, modified rosin, and various rosin derivatives, and rosin (unmodified rosin, modified rosin, various rosin derivatives, etc.) Rosin phenol resin obtained by thermal polymerization by adding an acid catalyst.

<Adhesion imparting resin T _LOH >

In a preferred aspect of the technique disclosed herein, the adhesive layer may contain a tackifying resin T _LOH having a hydroxyl value of about 30 mgKOH/g or less. Deterioration of the adhesive sheet is preferably suppressed by using a tackifying resin having a hydroxyl value equal to or less than a predetermined value. _Tackifying resin T _LOH can be used individually by 1 type or in combination of 2 or more types. The hydroxyl value of the tackifying resin T _LOH is preferably less than about 20 mgKOH/g, more preferably less than about 15 mgKOH/g, more preferably less than about 10 mgKOH/g, and particularly preferably about Less than 5 mgKOH/g (eg less than 3 mgKOH/g). For example, a tackifying resin T _LOH having a hydroxyl value of less than 1 mgKOH/g or in which no hydroxyl group is detected can be preferably used.

Here, as the value of the hydroxyl value, a value measured by the potentiometric titration method specified in JIS K0070:1992 can be adopted. The specific measurement method is as shown below.

[Measurement method of hydroxyl value]

1. Reagent

(1) As an acetylation reagent, about 12.5 g (about 11.8 mL) of acetic anhydride is taken, pyridine is added to this, and the total amount is 50 mL, and sufficiently stirred. Alternatively, about 25 g (about 23.5 mL) of acetic anhydride is taken, pyridine is added thereto, the total amount is made 100 mL, and sufficiently stirred is used.

(2) As a measurement reagent, a 0.5 mol/L potassium hydroxide ethanol solution is used.

(3) In addition, toluene, pyridine, ethanol and distilled water are prepared.

2. Operation

(1) Approximately 2 g of a sample is regularly collected in a flat bottom flask, 5 mL of an acetylation reagent and 10 mL of pyridine are added, and an air cooling tube is attached.

(2) The flask was heated in a 100°C bath for 70 minutes, allowed to cool, and then 35 mL of toluene was added and stirred as a solvent from the top of the cooling tube, and then 1 mL of distilled water was added and stirred to decompose acetic anhydride. In order to complete the decomposition, it is heated again in a bath for 10 minutes and allowed to cool.

(3) Wash the cooling tube with 5 mL of ethanol and remove. Next, 50 mL of pyridine is added as a solvent and stirred.

(4) Add 25 mL of 0.5 mol/L potassium hydroxide ethanol solution using a hole pipette.

(5) Potentiometric titration is performed with a 0.5 mol/L potassium hydroxide ethanol solution. The inflection point of the obtained titration curve is taken as the end point.

(6) In the blank test, the above (1) to (5) are performed without adding a sample.

3. Calculation

The hydroxyl value is calculated by the following formula.

Hydroxyl value (mgKOH/g)=[(B-C)×f×28.05]/S+D

here,

B: Amount of 0.5 mol/L potassium hydroxide ethanol solution used in the blank test (mL)

C: Amount of 0.5 mol/L potassium hydroxide ethanol solution used in the sample (mL)

f: Factor of 0.5 mol/L potassium hydroxide ethanol solution

S: weight of the sample (g)

D: acid value

28.05: 1/2 of the molecular weight of potassium hydroxide 56.11

to be.

The adhesive layer according to a preferred embodiment contains, as the tackifying resin T _LOH , a tackifying resin T _LOH1 having a softening point of 120°C or higher. From the viewpoint of high temperature cohesiveness and adhesion reliability (adhesive reliability after main adhesion by hot pressing, etc.), the softening point of the tackifying resin T _LOH1 is more preferably about 130°C or more, more preferably about 140°C or more, particularly preferably Is about 145°C or higher (for example, 150°C or higher). From the viewpoint of peeling strength to the adherend, etc., the softening point of the tackifying resin T _LOH1 is usually appropriately about 200°C or less, preferably about 180°C or less, more preferably about 170°C or less (for example 160°C or less).

The softening point of the tackifying resin here is defined as a value measured based on the softening point test method (ring ball method) specified in JIS K5902 and JIS K2207. Specifically, the sample is melted as quickly as possible at a low temperature, and it is carefully filled in a ring placed on a flat metal plate so that no air bubbles are generated. After cooling, cut off the raised part from the plane including the top of the ring with a small, slightly heated blade. Next, a holder (circle) is put in a glass container (heating bath) having a diameter of 85 mm or more and a height of 127 mm or more, and glycerin is injected until the depth becomes 90 mm or more. Next, the steel balls (diameter 9.5 mm, weight 3.5 g) and the ring filled with the sample are immersed in glycerin so that they do not come into contact with each other, and the temperature of glycerin is maintained at 20°C±5°C for 15 minutes. Next, a steel ball is placed in the center of the surface of the sample in the ring, and it is placed in the correct position on the support. Next, the distance from the top of the ring to the glycerin surface is kept at 50 mm, a thermometer is placed, and the position of the center of the mercury sphere of the thermometer is the same height as the center of the ring, and the container is heated. The flame of the Bunsen burner used for heating reaches the center of the bottom of the container and the middle of the edge, so that the heating is equalized. In addition, the rate at which the bath temperature rises after reaching 40°C after starting heating should be 5.0±0.5°C per minute. The sample gradually softens and flows down from the ring, and the temperature when it comes into contact with the bottom plate is read, and this is taken as the softening point. Two or more measurements of the softening point are performed at the same time, and the average value is employed.

As the tackifying resin T _LOH , one having an aromatic ring is preferably used. Examples of the tackifying resin T _LOH having an aromatic ring include the aromatic petroleum resin, aliphatic/aromatic copolymerized petroleum resin, styrene resin, coumarone indene resin, styrene-modified terpene resin, phenol-modified terpene resin, rosin phenol resin, etc. Can be mentioned. Among them, as the tackifying resin T _LOH having an aromatic ring, it is more preferable to use a _tackifying resin T _LOH1 having a softening point of 120°C or higher. The tackifying resin T _LOH1 having an aromatic ring is particularly preferably used for an adhesive layer containing a base polymer containing a monovinyl substituted aromatic compound such as styrene as a main monomer. _Tackifying resin T _LOH1 generally has a high softening point, which tends to decrease compatibility with the base polymer, and has a hydroxyl value of 30 mgKOH/g or less. Therefore, the monovinyl substituted aromatic compound unit of the base polymer It is easy to be compatible with the hard domain composed of, and the heat resistance of the pseudo-crosslinking by the hard domain can be improved.

As suitable examples of materials that can be used as tackifying resin T _LOH1 having a hydroxyl value of 30 mgKOH/g or less, a softening point of 120° C. or more, and an aromatic ring, aromatic petroleum resins, aliphatic/aromatic copolymerized petroleum resins , A styrene resin and a coumarone indene resin. As the aliphatic/aromatic copolymerized petroleum resin, it is preferable that the copolymerization ratio of the C5 fraction is less than 15% by weight (more preferably less than 10% by weight, more preferably less than 5% by weight, for example less than 3% by weight). . Further, it is preferable that the copolymerization ratio of the C9 fraction is 55% by weight or more (more preferably 60% by weight or more, and still more preferably 65% by weight or more). Among them, preferred tackifying resin T _LOH1 includes aromatic petroleum resins and styrene resins (eg, α-methylstyrene/styrene copolymer resins).

The amount of tackifying resin T _LOH1 is not particularly limited. From the viewpoint of deterioration suppression, high temperature cohesiveness, etc., the amount of tackifying resin T _LOH1 to 100 parts by weight of the base polymer is suitably set to about 5 parts by weight or more, preferably about 10 parts by weight or more, more preferably It is about 15 parts by weight or more, more preferably about 20 parts by weight or more, particularly preferably about 25 parts by weight or more. In addition, from the viewpoint of _achieving high level of adhesion reliability and temporary adhesion in main adhesion, the amount of tackifying resin T _LOH1 to 100 parts by weight of the base polymer may be, for example, about 100 parts by weight or less, Usually about 80 parts by weight or less (for example, about 60 parts by weight or less) is preferred. In consideration of the adhesion performance at low temperature (for example, temporary adhesion), the amount of tackifying resin T _LOH1 to 100 parts by weight of the base polymer is preferably about 40 parts by weight or less, and about 35 parts by weight or less.

The adhesive layer according to a preferred embodiment contains, as the tackifying resin T _LOH , a tackifying resin T _LOH2 having a softening point of less than 120°C. By using the tackifying resin T _LOH2 , an adhesive sheet having more excellent temporary adhesiveness can be realized. The lower limit of the softening point of the tackifying resin T _LOH2 is not particularly limited. Usually, those having a softening point of about 40°C or higher (typically about 60°C or higher) can be preferably used. From the viewpoint of achieving high level of adhesion reliability and temporary adhesion in the main adhesion, a tackifying resin T _LOH2 having a softening point of about 80°C or higher (more preferably about 100°C or higher) less than 120°C can be preferably employed. have. Among them, the use of _tackifying resin T _{LOH2 having} a softening point of 110°C or more and less than 120°C is preferable.

The tackifying resin T _LOH2 is not particularly limited, except that the hydroxyl value is 30 mgKOH/g or less, and the softening point is less than 120°C, and its structure (for example, the presence or absence of an aromatic ring, the presence or absence of an isoprene unit, a terpene skeleton The presence or absence of, the presence or absence of a rosin skeleton, etc.) is not particularly limited. It can be suitably selected and used from among the various tackifying resins described above (petroleum resin, styrene resin, coumarone indene resin, terpene resin, modified terpene resin, rosin resin, rosin derivative resin, ketone resin, etc.).

The technique _disclosed herein can be preferably implemented in an aspect in which the adhesive layer includes at least one of a petroleum resin and a terpene resin as the tackifying resin T _LOH2 . For example, a _{composition in which} the main component of the tackifying resin T _LOH2 (that is, a component that accounts for more than 50% by weight in the tackifying resin T _LOH2 ) is a petroleum resin, a composition that is a terpene resin, a composition that is a combination of a petroleum resin and a terpene resin, etc. Can be preferably employed. From the viewpoint of adhesion and compatibility, an aspect in which the main component of the tackifying resin T _LOH2 is a terpene resin (for example, an α-pinene polymer or a β-pinene polymer) is preferable. Substantially all (for example, 95% by weight or more) of the tackifying resin T _LOH2 may be a terpene resin.

The amount of tackifying resin T _LOH2 used is not particularly limited. From the standpoint of deterioration suppression, temporary adhesiveness, etc., the amount of tackifying resin T _LOH2 to 100 parts by weight of the base polymer is suitably set to about 10 parts by weight or more, preferably about 20 parts by weight or more, more preferably. Preferably, it is about 30 parts by weight or more, more preferably about 40 parts by weight or more (for example, 45 parts by weight or more). In addition, from the viewpoint of _achieving a high level of adhesion reliability and temporary adhesion in main adhesion, the amount of tackifying resin T _LOH2 to 100 parts by weight of the base polymer may be, for example, about 120 parts by weight or less, Usually about 90 parts by weight or less is preferable, and about 70 parts by weight or less (for example, about 60 parts by weight or less) is more preferable.

In a preferred embodiment, as the tackifying resin T _LOH having a hydroxyl value of 30 mgKOH/g or less, a tackifying resin T _LOH1 having a softening point of 120°C or higher and a tackifying resin T _LOH2 having a softening point of less than 120°C are _used in combination. The content ratio is not particularly limited, and the ratio of the content of the tackifying resin T _{LOH2 to} the content of the tackifying resin T _LOH1 (T _LOH2 /T _LOH1 ) is suitably about 0.5 or more, preferably about 0.8 or more, more preferably about 1.2 or more, and even more preferably about 1.5 or more. In addition, the ratio (T _LOH2 /T _LOH1 ) is suitably about 3 or less, preferably about 2.5 or less, more preferably about 2 or less, and even more preferably about 1.8 or less.

The amount of tackifying resin T _LOH (the total amount when using the tackifying resin T _LOH1 and the tackifying resin T _LOH2 together) is not particularly limited. From the viewpoint of desirably exerting the effect of the technology disclosed herein, the amount of tackifying resin T _LOH to 100 parts by weight of the base polymer is appropriately set to about 15 parts by weight or more, and preferably about 35 parts by weight. Or more, more preferably about 50 parts by weight or more, even more preferably about 65 parts by weight or more (for example, about 70 parts by weight or more). In addition, the amount of tackifying resin T _LOH to 100 parts by weight of the base polymer may be, for example, about 220 parts by weight or less, and usually, about 170 parts by weight or less is preferable, and about 120 parts by weight or less (for example, For example, about 100 parts by weight or less) is more preferable.

<Adhesion imparting resin T _HOH >

In one aspect of the technology disclosed herein, in place of the tackifying resin T _LOH having a hydroxyl value of 30 mgKOH/g or less, or in combination with the tackifying resin T _LOH , a hydroxyl value exceeding 30 mgKOH/g An imparting resin T _HOH can be used. The hydroxyl value of the tackifying resin T _HOH may be, for example, about 40 mgKOH/g or more, or about 50 mgKOH/g or more. As the tackifying resin T _HOH , even in an aspect including a tackifying resin having a hydroxyl value of about 80 mgKOH/g or more (eg, 90 mgKOH/g or more), the technique disclosed herein can be implemented. The hydroxyl value of the tackifying resin T _LOH is typically about 200 mgKOH/g or less, and preferably about 150 mgKOH/g or less (eg, 120 mgKOH/g or less).

The tackifying resin T _HOH is not particularly limited, and a tackifying resin having a hydroxyl value of more than 30 mgKOH/g can be used as the various tackifying resins described above. For example, terpene phenol resin, rosin phenol resin, polymerized rosin, esterified product of polymerized rosin, etc. can be used. As a typical example, a phenolic resin (including terpene phenol resin and rosin phenol resin) having a phenol structure in the molecule can be mentioned. These tackifying resins T _HOH can be used alone or in combination of two or more.

The amount of tackifying resin T _HOH used is not particularly limited, and can be appropriately set according to the purpose or use of the adhesive composition. From the viewpoint of suppression of deterioration, etc., the amount of tackifying resin T _HOH to 100 parts by weight of the base polymer may be, for example, about 100 parts by weight or less, and it is appropriate to be about 60 parts by weight or less, preferably It is about 30 parts by weight or less, more preferably 10 parts by weight or less. For example, by limiting the amount of the phenolic resin used as the tackifying resin T _HOH , deterioration of the adhesive tends to be preferably suppressed. The technology disclosed herein can be implemented even in an embodiment in which the amount of tackifying resin T _HOH is used in an amount of about 5 parts by weight or less (for example, about 1 part by weight or less) with respect to 100 parts by weight of the base polymer, and the adhesive layer is tackified. Even in an aspect which does not contain resin T _HOH substantially, it can implement preferably. In addition, that the adhesive layer does not contain the tackifying resin T _HOH substantially means that the amount of the tackifying resin T _HOH relative to 100 parts by weight of the base polymer is less than 0.1 parts by weight.

<crosslinking agent>

The technology disclosed herein can be preferably implemented in an embodiment in which the base polymer includes an adhesive layer made of a non-crosslinkable adhesive (non-crosslinkable adhesive). Here, the term "adhesive layer made of a non-crosslinkable adhesive" refers to an intentional treatment (i.e., crosslinking treatment, for example, blending of a crosslinking agent) for forming a chemical bond between the base polymers when forming the adhesive layer. It refers to the adhesive layer that has not been applied. Such an adhesive layer and the adhesive composition used to form the adhesive layer may be those that do not contain substantially a crosslinking agent such as an isocyanate compound. That the adhesive composition does not contain a crosslinking agent substantially means that the content of the crosslinking agent contained in the adhesive composition is less than 0.1% by weight (eg, 0 to 0.05% by weight).

<Other ingredients>

The adhesive composition disclosed herein is, if necessary, a leveling agent, a crosslinking aid, a plasticizer, a softener, a filler (typically inorganic particles), a colorant (pigment, dye, etc.), an antistatic agent, an anti-aging agent, an ultraviolet absorber, an antioxidant. , Light stabilizers, etc., may contain various additives common in the field of adhesives. For these various additives, conventionally known additives can be used by a conventional method. The adhesive composition disclosed herein is about 0.1 to 10 parts by weight (preferably about 1 to 7 parts by weight, for example, 1.5 to 5 parts by weight, based on 100 parts by weight of the base polymer) from the viewpoint of preventing deterioration, aging, etc. Degree) of an anti-aging agent. In addition, the adhesive disclosed herein does not substantially contain liquid rubber such as polybutene (for example, the content per 100 parts by weight of the base polymer is 1 part by weight or less, and may be 0 parts by weight). Can be implemented. With such an adhesive, an adhesive sheet having excellent adhesion reliability at the time of main adhesion can be realized.

In a preferred embodiment, the adhesive composition may be a composition comprising 90% by weight or more of the total weight of the adhesive (ie, the weight of the adhesive layer constituted by the adhesive), the total amount of the base polymer and the tackifying resin. . For example, an aspect in which the total amount of the base polymer and the tackifying resin is 90 to 99.8% by weight (typically, 95 to 99.5% by weight) of the total weight of the adhesive can be preferably adopted.

In another preferred aspect, the adhesive composition may be a composition that does not substantially contain a chelate compound. Here, the chelate compound refers to a chelate compound of an oxide of an alkaline earth metal and a resin (such as an alkylphenol resin) having a functional group (hydroxyl group, methylol group, etc.) capable of coordinating the oxide. The technique disclosed herein can be preferably implemented in an embodiment in which the adhesive composition does not contain such a chelate compound at all, or the content ratio of the chelate compound is 1% by weight or less. According to this aspect, an adhesive sheet having more excellent adhesive strength can be realized.

The form of the adhesive composition disclosed herein is not particularly limited, for example, an adhesive composition in a form (solvent type) containing an adhesive (adhesive component) of the above-described composition in an organic solvent, wherein the adhesive is dispersed in an aqueous solvent. It may be an adhesive composition in a form (water dispersion type, typically an aqueous emulsion type), a hot melt adhesive composition, and the like. From the viewpoint of realizing higher adhesive performance, a solvent-type adhesive composition is particularly preferred. Such a solvent-type adhesive composition is typically prepared in the form of a solution containing each of the above-described components in an organic solvent. The organic solvent can be appropriately selected from known to common organic solvents. For example, aromatic compounds such as toluene and xylene (typically aromatic hydrocarbons); Acetic acid esters such as ethyl acetate and butyl acetate; Aliphatic or alicyclic hydrocarbons such as hexane, cyclohexane, and methylcyclohexane; Halogenated alkanes such as 1,2-dichloroethane; Ketones such as methyl ethyl ketone and acetyl acetone; Any one type of solvent selected from, or a mixed solvent of two or more types can be used. Although it does not specifically limit, Usually, it is suitable to adjust the said solvent-type adhesive composition to 30-65 weight% (for example, 40-55 weight%) of solid content (NV). If the NV is too low, the manufacturing cost tends to increase, and if the NV is too high, the handling properties such as coating properties may be deteriorated.

As a method of obtaining the adhesive sheet from the adhesive composition, various conventionally known methods can be applied. For example, a method of forming an adhesive layer by directly applying (typically applying) the adhesive composition to a substrate and drying it (direct method) can be preferably employed. In addition, the method of forming an adhesive layer on the surface by applying the adhesive composition to a surface having good releasability (for example, the surface of a release liner, the back of a support substrate subjected to release treatment, etc.) and drying it is a substrateless adhesive sheet It is preferably employed in the manufacture of. After the adhesive layer is formed, a method of transferring the adhesive layer to the substrate (transfer method) may be employed.

Application of the adhesive composition can be performed using known or commonly used coaters such as gravure roll coaters, reverse roll coaters, kiss roll coaters, dip roll coaters, bar coaters, knife coaters, and spray coaters. From the viewpoint of improving production efficiency, it is preferable to dry the adhesive composition under heating. Usually, for example, a drying temperature of about 40°C to 150°C (typically 40°C to 120°C, for example 50°C to 120°C, further 70°C to 100°C) can be preferably employed. The drying time is not particularly limited, but may be about several tens of seconds to several minutes (for example, within about 5 minutes, preferably about 30 seconds to 2 minutes). After that, you may provide an additional drying process as needed. The adhesive layer is typically formed continuously, but may be formed in a regular or random pattern such as a dot shape or a stripe shape, depending on the purpose and use.

Although not particularly limited, the thickness of the adhesive layer is appropriately set to be about 3 mm or less, preferably about 1 mm or less, more preferably about 0.7 from the viewpoint of thinning, miniaturization, weight reduction, and resource saving. Mm or less, more preferably about 0.5 mm or less (eg about 0.4 mm or less). Since the adhesive layer having a limited thickness also limits the amount of impregnation into an adherend such as cloth, the influence of the impregnation on deformation recovery (eg, elasticity) of the adherend is also reduced. In addition, from the viewpoint of securing good adhesive properties, the thickness is suitably about 0.01 mm or more, preferably about 0.03 mm or more, more preferably about 0.05 mm or more, even more preferably about 0.1 It is more than mm. In the case of a double-sided adhesive sheet having a substrate, an adhesive layer having the above thickness may be provided on each of both surfaces of the substrate.

<material>

When the technology disclosed herein is applied to a double-sided adhesive sheet having a substrate or a single-sided adhesive sheet having a substrate, examples of the substrate include polypropylene film, ethylene-propylene copolymer film, polyester film, polyurethane film, poly Plastic films such as vinyl chloride films; Foam sheets made of foams such as polyurethane foam, polyethylene foam, and polychloroprene foam; Various fibrous materials (natural fibers such as hemp, cotton, synthetic fibers such as polyester, vinylon, polyurethane, semi-synthetic fibers such as acetate, etc.) It means to include tributaries.); Metal foils such as aluminum foil and copper foil; Etc. can be appropriately selected and used according to the application of the adhesive sheet. As the plastic film (typically refers to a non-porous plastic film, which is a concept distinct from woven or non-woven fabric), both non-stretched films and stretched (uniaxially stretched or biaxially stretched) films can be used. Further, the surface of the substrate on which the adhesive layer is provided may be subjected to surface treatment such as application of a primer or corona discharge treatment. The thickness of the substrate can be appropriately selected depending on the purpose, but is generally about 2 μm to 500 μm (typically 10 μm to 200 μm).

<Peeling liner>

As the release liner, a common release paper or the like can be used, and it is not particularly limited. For example, a release liner having a release treatment layer on the surface of a substrate such as a plastic film or paper, and a low-adhesion material such as fluorine-based polymer (polytetrafluoroethylene, etc.) or polyolefin-based resin (polyethylene, polypropylene, etc.) are included. A release liner or the like can be used. The release treatment layer may be formed by surface-treating the substrate with a release treatment agent such as silicon-based, long-chain alkyl-based, fluorine-based, or molybdenum sulfide.

<use>

The adhesive sheet disclosed herein is suitable for bonding between members in various OA devices, home appliances, automobiles, clothes, household goods, home goods, leisure goods, etc. (for example, for fixing various parts in such products). useful. The adhesive sheet disclosed herein can be used for bonding hard members such as resin parts, but taking advantage of its temporary adhesiveness, deformation recovery, flexibility and adhesion reliability of a preferred aspect, fabric, leather, paper, rubber It is suitably used for bonding applications of flexible materials such as sheets and resin sheets. Among them, fabrics are mentioned as preferred targets for application of the technology disclosed herein. The fabric includes natural fibers, synthetic fibers, semi-synthetic fibers, woven fabrics formed from these composite fibers, and knitted fabrics, and includes all of what is referred to as fabric. Leather includes artificial leather, synthetic leather, and semi-synthetic leather.

Suitable examples of products containing the above flexible material include clothing such as coats, jackets, shirts, pants, underwear, daily necessities such as shoes, bags, towels, housewares such as curtains and carpets, sofas, and bedding, and wetsuits. Sporting goods, etc. As a means for sewing replacement bonding (seamless bonding) in the above applications, the adhesive sheet disclosed herein is preferably used. Bonding (typically seamless bonding) of stretchable fabrics such as undergarments is a particularly preferred application use of the technique disclosed herein. Such an elastic material may be formed of natural fibers such as cotton, various synthetic fibers such as acrylic, polyester, urethane, and natural/synthetic composite fibers thereof. The bonding mode of fabric, etc. using an adhesive sheet is not particularly limited, for example, a mode in which ends of an adherend such as fabric are butted to each other, and an adhesive sheet is disposed at the abutted portion, and an adherend such as fabric is bonded The mode of partially overlapping and joining through through may be appropriately employed. The technique disclosed herein can be preferably implemented in the form of partially overlapping and bonding an adherend via an adhesive sheet.

<Fabric bonded with thermoplastic adhesive>

As described above, the adhesive sheet disclosed herein can be preferably used for bonding of fabrics (typically seamless bonding). Therefore, according to the technique disclosed herein, a cloth (adhesive bonding cloth) bonded by a thermoplastic adhesive is provided. Such an adhesive bonded fabric is produced by, for example, placing a thermoplastic adhesive sheet between one fabric and another fabric for temporary bonding, followed by heat pressing. By adopting this method, fabric bonding (typically seamless bonding) can be carried out with high precision without the need for sewing, and products such as clothing including fabrics bonded with an adhesive can be manufactured with high productivity. I can. In the product such as clothing manufactured in this way, the bonding point by the adhesive closely follows the flexibility and elasticity of the clothing or the like, and an excellent fit can be provided.

The matters disclosed by this specification include the following.

(1) a thermoplastic adhesive sheet having a thermoplastic adhesive layer,

The following characteristics:

(A) A thermoplastic adhesive sheet was bonded to a polyester-based urethane foam having a thickness of 10 mm in an environment of 23°C and 50% RH by reciprocating a roller of 2 kg, and leaving it in the same environment for 30 minutes, and then a tensile speed of 300 The peel strength measured under the conditions of mm/min and a peel angle of 180 degrees is 2N/10 mm or more; And

(B) A measurement sample of a thermoplastic adhesive sheet having a measurement length of 100 mm was prepared, and the measurement sample was elongated by 50% at 23°C at a rate of 300 mm/min and held for 3 seconds, and then at a rate of 300 mm/min. When contracted, the hysteresis determined from the ratio of the shrinkage strength F _S30% to the stretch strength F _E30% at 30% elongation length [F _S30% /F _E30% ] is 35% or more;

Satisfying, thermoplastic adhesive sheet.

(2) the following characteristics:

(C) For the thermoplastic adhesive sheet measurement sample having a measurement length of 100 mm, the 30% modulus measured at a rate of 300 mm/min at 23° C. is 0.6 MPa or less;

The thermoplastic adhesive sheet according to (1), further satisfying.

(3) the following characteristics:

(D) After pressing the thermoplastic adhesive sheet to a stainless steel sheet under the conditions of 120°C, 0.2 MPa, and 10 seconds, and allowed to stand at 23°C for 30 minutes, the peel strength measured under the conditions of a tensile speed of 300 mm/min and a peel angle of 180° , 15N/10mm or more;

The thermoplastic adhesive sheet according to (1) or (2), further satisfying.

(4) The thermoplastic adhesive sheet according to any one of (1) to (3), wherein the thermoplastic adhesive layer is a rubber adhesive layer containing a rubber polymer as a base polymer.

(5) The thermoplastic adhesive sheet according to (4), wherein the thermoplastic adhesive layer contains, as a base polymer, a block copolymer of a monovinyl substituted aromatic compound and a conjugated diene compound.

(6) The thermoplastic adhesive sheet according to (5), wherein the base polymer is a styrenic block copolymer.

(7) The thermoplastic adhesive sheet according to (5) or (6), wherein the ratio of the diblock body of the base polymer is 65% or more.

(8) The thermoplastic adhesive sheet according to any one of (1) to (7), wherein the thermoplastic adhesive layer contains a tackifying resin T _LOH having a hydroxyl value of 30 mgKOH/g or less as a tackifying resin.

(9) The thermoplastic adhesive sheet according to (8), wherein the tackifying resin T _LOH contains a tackifying resin T _LOH1 having a softening point of 120°C or higher.

(10) The thermoplastic adhesive sheet according to (9), wherein the tackifying resin T _LOH1 contains a tackifying resin having an aromatic ring.

(11) The thermoplastic adhesive sheet according to any one of (8) to (10), wherein the tackifying resin T _LOH contains a tackifying resin T _LOH2 having a softening point of less than 120°C.

(12) Any of the above (8) to (11), wherein the content of the tackifying resin T _{LOH in} the thermoplastic adhesive layer is 15 to 220 parts by weight based on 100 parts by weight of the base polymer contained in the thermoplastic adhesive layer. The thermoplastic adhesive sheet according to one.

(13) The thermoplastic adhesive sheet according to any one of (1) to (12), wherein the thermoplastic adhesive layer does not contain tackifying resin T _HOH having a hydroxyl value exceeding 30 mgKOH/g.

(14) The thermoplastic adhesive sheet according to any one of (1) to (13), wherein the thermoplastic adhesive layer is a non-crosslinkable adhesive layer.

(15) The thermoplastic adhesive sheet according to any one of (1) to (14), wherein the thermoplastic adhesive sheet has a thickness of 0.03 mm to 1 mm.

(16) The thermoplastic adhesive sheet according to any one of (1) to (15), configured as a base-free adhesive sheet comprising only the thermoplastic adhesive layer.

(17) The thermoplastic adhesive sheet according to any one of (1) to (16), which is used to bond fabrics together.

(18) A thermoplastic adhesive sheet having a release liner comprising the thermoplastic adhesive sheet according to any one of the above (1) to (17), and a release liner that protects the adhesive surface of the thermoplastic adhesive sheet.

(19) Fabric bonded with the thermoplastic adhesive sheet according to any one of (1) to (18) above.

Hereinafter, some examples of the present invention will be described, but it is not intended to limit the present invention to those shown in these examples. In addition, in the following description, "part" and "%" are based on weight unless otherwise specified.

<Example 1>

[Preparation of Thermoplastic Adhesive Composition]

100 parts of styrene isoprene block copolymer as a base polymer (manufactured by Nippon Xeon, product name ``Quintac 3520'', 15% styrene content, 78% diblock body ratio), and 50 parts of terpene resin (manufactured by Yasuhara Chemical, Inc., Product name "YS resin PX1150N", softening point 115°C, hydroxyl value less than 1 mgKOH/g), aromatic petroleum resin (JX Nikko Nisseki Energi), product name "Nisseki Neo Polymer 150", softening point 155°C, hydroxyl value 30 parts of 1 mgKOH/g), 3 parts of an anti-aging agent (product name "IRGANOX 1010" manufactured by BASF), and toluene as a solvent were stirred and mixed to prepare an NV 50% thermoplastic adhesive composition.

[Production of Thermoplastic Adhesive Sheet]

The thermoplastic adhesive composition prepared above was applied to the peeling-treated surface of the peeling liner A subjected to peeling with a silicone-based peeling agent, and dried at 120° C. for 3 minutes to form a thermoplastic adhesive layer having a thickness of 0.2 mm. A release liner B subjected to a release treatment with a silicone release agent was bonded to the thermoplastic adhesive layer. In this way, a substrate-free thermoplastic adhesive sheet comprising a thermoplastic adhesive layer was produced.

<Examples 2 to 3>

A thermoplastic adhesive sheet according to each example was produced in the same manner as in Example 1 except that the thermoplastic adhesive layer was changed to the thickness shown in Table 1.

<Example 4>

The product name "No. 501K" manufactured by Nitto Denko Corporation was used as the adhesive sheet according to this example. "No.501K" is a double-sided adhesive tape having a substrate having a thickness of 0.17 mm in which an acrylic pressure-sensitive adhesive layer is formed on both surfaces of a nonwoven fabric substrate.

<Example 5>

Styrene butadiene block copolymer as a base polymer (Asahi Kasei Chemicals' product name ``Surprene T-432'', styrene content 30%) 100 parts and alicyclic hydrocarbon resin 120 parts (Arakawa Chemical Co., Ltd. make, product name ``Alcon M -115", softening point 115 degreeC) and toluene as a solvent were stirred and mixed, and the thermoplastic adhesive composition of NV 50% was prepared.

The thermoplastic adhesive composition prepared above was applied to the peeling-treated surface of a peeling liner A subjected to a peeling treatment with a silicone-based release agent, and dried at 120° C. for 3 minutes to form a 0.05 mm-thick thermoplastic adhesive layer. A release liner B subjected to a release treatment with a silicone release agent was bonded to the thermoplastic adhesive layer. In this way, a substrate-free thermoplastic adhesive sheet comprising a thermoplastic adhesive layer was produced.

[Temporary adhesion to fabric]

The adhesive sheet for each example was cut into a rectangle having a width of 10 mm. Two commercially available underwear fabrics cut into strips having a width of 20 mm were prepared, and in an environment of 23°C and 50% RH, each of the two fabrics was applied to each adhesive surface of the adhesive sheet piece with a 2 kg roller. A measurement sample was prepared by reciprocating and pressing. The obtained measurement sample was left to stand for 30 minutes in the same environment, and then the measurement sample was removed into a T-shape using a universal tensile compression tester. Specifically, one end in the longitudinal direction of the two fabrics bonded by the adhesive sheet piece in the measurement sample is held by the two chucks of the tester, respectively, one chuck upwards and the other chuck downward, respectively. By stretching at a speed of 100 mm/min, the two fabrics bonded by the adhesive sheet piece were torn off in a T-shape. This T-type peeling is peeling off so as to form a T-shape when the plane of the measurement sample (the plane of the fabric bonded by the adhesive sheet) is set to 0°, one transition is +90° and the other is −90°. The force required for this T-shaped peeling was measured with the tester, and this was taken as a temporary adhesive force to the fabric (Daecheon provisional adhesive force) [N/10 mm].

As the universal tensile compression testing machine, the device name "tensile compression testing machine, TG-1kN" manufactured by Minevea was used, but an equivalent product thereof or a commercially available device can be used.

[Main adhesion to fabric]

The temporary adhesiveness described above except for performing T-type peeling after the pressure bonding condition of the adhesive sheet according to each example to the fabric was 150°C, 0.5 MPa, and 15 seconds, and after being pressed, left at room temperature (23°C) for 1 hour. By the same method as the evaluation, the main adhesive force to the fabric (large cloth main adhesive force) [N/10 mm] was measured.

[30% elongation strength and 50% elongation residual strain]

The adhesive sheet for each example was cut into a rectangle having a width of 10 mm so as to have a measurement length of 100 mm. In addition, two commercially available underwear fabrics cut into strips having a width of 20 mm so as to have a measurement length of 100 mm were prepared, and each of the two fabrics was bonded to each of the adhesive sheet pieces under an environment of 23°C and 50% RH. A measurement sample was prepared by pressing the cotton under the conditions of 150°C, 0.5 MPa, and 15 seconds. After allowing the obtained measurement sample to stand at room temperature (23°C) for 1 hour, set the chuck distance (measurement length) to 100 mm (L0) in a tensile compression tester, and elongate 50% at a rate of 100 mm/min at 23°C. (Therefore, it was stretched to 150 mm), maintained for 3 seconds in a 50% stretched state, released and allowed to stand for 30 minutes, and the measurement length L1 [mm] was recorded. From the above operation, the strength (30% elongation strength) [N] when the measurement sample was elongated by 30% and the residual strain (50% elongation residual strain) [%] after standing for 30 minutes were determined. The residual strain [%] is the formula:

Residual strain [%] = (L1-L0)/L0×100

Obtained from

Schematic configuration of the adhesive sheet for each example, 30% modulus [MPa], 30% hysteresis at 50% elongation [%], adhesion to large foams [N/10 mm], adhesion to SUS thermal compression [N/10 mm], Daecheon Table 1 shows the evaluation results of the temporary adhesive force [N/10 mm], the main adhesive force [N/10 mm], the 30% elongation strength [N] and 50% elongation residual strain [%] of the adhesive bonded fabric.

As shown in Table 1, the thermoplastic adhesive sheet according to Examples 1 to 3, wherein the large foam adhesion (property (A)) is 2N/10 mm or more, and 30% hysteresis (property (B)) at 50% elongation is 35% or more. Represents a temporary adhesive force of 0.1 N/10 mm or more (specifically, 0.4 to 0.6 N/10 mm) to the fabric, and the residual strain of the fabric bonded with the adhesive sheet was 5% or less. In contrast, the double-sided pressure-sensitive adhesive sheet having the nonwoven fabric base material according to Example 4 in which the hysteresis was not measurable due to fracture had a residual strain of more than 5%. In addition, the adhesive sheet according to Example 5 in which the large foam adhesive force was less than 2N/10 mm had a remarkably small temporary adhesive force to the fabric, and did not have sufficient temporary adhesiveness. Further, from the above evaluation results, although the absolute values of the measured values were different between the large foam adhesive force and the Daecheon temporary adhesive force, a constant correlation was shown in that both adherend surfaces were rough. In addition, of Examples 1 to 3 in which 30% modulus is 0.6 MPa or less, the fabric bonded with the adhesive sheet according to Example 1 having a thickness of 0.06 mm was the adhesive bonding fabric according to Example 5 (30% modulus of the adhesive sheet exceeding 0.6 MPa, Thickness 0.05 mm), the 30% elongation strength was suppressed low, and the original flexibility of the fabric was maintained. In addition, in Examples 1 to 3, where the adhesive strength of the SUS thermocompression bonding is relatively high, the tendency of the original bonding strength of Daecheon to increase was confirmed. Confirmed.

From the above results, according to a thermoplastic adhesive sheet that satisfies the properties (A) and (B), the thermoplastic adhesive sheet having a large foam adhesion of 2N/10 mm or more and 30% hysteresis at 50% elongation is 35% or more, that is, It can be seen that it has temporary adhesiveness and strain recovery, and can exhibit a good adhesive function. Further, it can be seen that a thermoplastic adhesive sheet having a 30% modulus of 0.6 MPa or less, that is, satisfying the characteristic (C), does not impair the flexibility of the adherend material. In addition, it can be seen that a thermoplastic adhesive sheet having a thermocompression bonding force of SUS of 15 N/10 mm or more, that is, satisfying the characteristic (D), has excellent adhesion reliability based on its strong adhesion.

As mentioned above, specific examples of the present invention have been described in detail, but these are only examples and do not limit the scope of the claims. The technology described in the claims includes various modifications and changes of the specific examples illustrated above.

1, 2, 3: Thermoplastic adhesive sheet
11: adhesive layer (first adhesive layer)
12: second adhesive layer
15: description
21, 22: release liner

Claims (11)

It is a thermoplastic adhesive sheet having a thermoplastic adhesive layer,
The following characteristics:
(A) A thermoplastic adhesive sheet was bonded to a polyester-based urethane foam having a thickness of 10 mm in an environment of 23°C and 50% RH by reciprocating a roller of 2 kg, and leaving it in the same environment for 30 minutes, and then a tensile speed of 300 The peel strength measured under the conditions of mm/min and a peel angle of 180 degrees is 2N/10 mm or more; And
(B) A measurement sample of a thermoplastic adhesive sheet having a measurement length of 100 mm was prepared, and the measurement sample was elongated by 50% at 23°C at a rate of 300 mm/min and held for 3 seconds, and then at a rate of 300 mm/min. When contracted, the hysteresis determined from the ratio of the shrinkage strength F _S30% to the stretch strength F _E30% at 30% elongation length [F _S30% /F _E30% ] is 35% or more;
Satisfying, thermoplastic adhesive sheet. The method of claim 1,
The following characteristics:
(C) For the thermoplastic adhesive sheet measurement sample having a measurement length of 100 mm, the 30% modulus measured at a rate of 300 mm/min at 23° C. is 0.6 MPa or less;
To further satisfy, the thermoplastic adhesive sheet. The method according to claim 1 or 2,
The following characteristics:
(D) After pressing the thermoplastic adhesive sheet to a stainless steel sheet under the conditions of 120°C, 0.2 MPa, and 10 seconds, and allowed to stand at 23°C for 30 minutes, the peel strength measured under the conditions of a tensile speed of 300 mm/min and a peel angle of 180° , 15N/10mm or more;
To further satisfy, the thermoplastic adhesive sheet. The method according to any one of claims 1 to 3,
The thermoplastic adhesive layer is a rubber-based adhesive layer containing a rubber-based polymer as a base polymer, a thermoplastic adhesive sheet. The method of claim 4,
The thermoplastic adhesive layer, as a base polymer, contains a block copolymer of a monovinyl substituted aromatic compound and a conjugated diene compound. The method according to any one of claims 1 to 5,
The thermoplastic adhesive layer, as a tackifying resin, contains a tackifying resin T _LOH having a hydroxyl value of 30 mgKOH/g or less. The method according to any one of claims 1 to 6,
The thermoplastic adhesive layer is a non-crosslinkable adhesive layer, a thermoplastic adhesive sheet. The method according to any one of claims 1 to 7,
The thermoplastic adhesive sheet has a thickness of 0.03 mm to 1 mm. The method according to any one of claims 1 to 8,
A thermoplastic adhesive sheet configured as a base-free adhesive sheet comprising only the thermoplastic adhesive layer. The method according to any one of claims 1 to 9,
A thermoplastic adhesive sheet used to bond fabrics together. The fabric bonded with the thermoplastic adhesive sheet according to any one of claims 1 to 9.

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