CN117377734A

CN117377734A - Pressure-sensitive adhesive sheet, display device, and laminate

Info

Publication number: CN117377734A
Application number: CN202280036018.XA
Authority: CN
Inventors: 西胁匡崇; 伊神俊辉; 山元健一
Original assignee: Nitto Denko Corp
Current assignee: Nitto Denko Corp
Priority date: 2021-05-28
Filing date: 2022-03-28
Publication date: 2024-01-09
Also published as: WO2022249726A1; JP2022182495A

Abstract

The invention provides an adhesive sheet with a structure in which the thickness is limited, and which can maintain sufficient adhesive force as a structural material even when exposed to an acidic liquid and an alkaline liquid. The invention provides an adhesive sheet with a thickness of 100 μm or less. The adhesive sheet has an adhesive layer containing an acrylic polymer. The acrylic polymer is a polymer containing 60% by weight or more of a monomer component of an alkyl (meth) acrylate having an alkyl group having 5 or more carbon atoms at the ester end. In addition, the monomer component contains a monomer having a nitrogen atom-containing ring and a carboxyl group-containing monomer.

Description

Pressure-sensitive adhesive sheet, display device, and laminate

Technical Field

The invention relates to an adhesive sheet, a display device and a laminate.

The present application claims priority based on japanese patent application No. 2021-090083 filed 5/28 of 2021, the entire contents of which are incorporated herein by reference.

Background

In general, an adhesive (also referred to as a pressure-sensitive adhesive; hereinafter, the same applies) exhibits a soft solid (viscoelastic body) state in a temperature range around room temperature, and has a property of being easily adhered to an adherend by pressure. By utilizing such properties, adhesives are widely used for the purpose of joining components, surface protection, and the like in various industrial fields such as home electric products, automobiles, OA equipment, and the like, in the form of a base-material-attached adhesive sheet having an adhesive layer on a supporting base material, or in the form of a base-material-free adhesive sheet having no supporting base material. Patent documents 1 to 3 are cited as technical documents related to the pressure-sensitive adhesive sheet. Patent document 1 discloses an adhesive sheet for use in the interior of a touch panel. Patent document 2 discloses an adhesive sheet having a viscoelastic layer with a thickness of 200 μm or more as a support layer. Patent document 3 discloses a back surface grinding tape for fixing and protecting a semiconductor wafer in a back surface grinding process of semiconductor wafer processing.

Prior art literature

Patent literature

Patent document 1: japanese patent application laid-open No. 2014-34655

Patent document 2: japanese patent application laid-open No. 2015-147870

Patent document 3: japanese patent application laid-open No. 2017-212441

Disclosure of Invention

Problems to be solved by the invention

An adhesive sheet is widely used as a so-called structural material (for example, patent document 1) in which members are joined or fixed and assembled together with the members into an article; or as a so-called process material (for example, patent document 3) which is temporarily stuck to an adherend during the production, processing, and transportation of various articles as the adherend, and which is removed from the adherend after achieving the object. The pressure-sensitive adhesive sheet used as a structural material is different from the use of a process material requiring removability from an adherend, and generally requires long-term adhesive reliability so as not to peel from the adherend until the end of the life of the product in which the pressure-sensitive adhesive sheet is incorporated. For example, an adhesive sheet used for fixing members of a portable electronic device tends to be light in weight, small in size, and thin in thickness, and has a small adhesive area and a limited thickness. In general, when the thickness of the adhesive sheet becomes smaller, the adhesive force decreases, and thus improvement in adhesive reliability has an inverse relationship with thickness reduction of the adhesive sheet. In such a limitation, it is necessary to maintain a good adhesive state for a long period of time.

Further, various members of the portable electronic device may be perforated or the like. For example, an organic EL (electro luminescence) panel or a metal member used in a portable electronic device may be provided with an opening for various sensors such as a fingerprint sensor or a camera lens. The processing of the above-described member is usually performed before the adhesive sheet is attached, but if the processing can be performed in a state where the adhesive sheet is attached (for example, in a state where the member is bonded by the adhesive sheet), it can be advantageous in terms of production efficiency and the like. In such a processing step, the pressure-sensitive adhesive sheet needs to be adhered to a member as an adherend, and to maintain a good adhesion state to the adherend even after the processing step of the member. For example, the processing such as forming the opening of the metal member may include a chemical treatment step such as etching treatment in which a non-processed portion of the metal member is masked or the like and immersed in an acidic etching solution. Further, after immersing in the etching solution, the metal member may be cleaned with an alkaline cleaning solution or the like. Therefore, the pressure-sensitive adhesive sheet to be used in the processing step of the metal member in a state of being adhered to the metal member can be exposed to an acidic etching solution and an alkaline cleaning solution together with the metal member as an adherend, and therefore, even when the pressure-sensitive adhesive sheet is exposed to an acidic and alkaline liquid, the pressure-sensitive adhesive sheet can maintain a good adhesive state, and is required to have characteristics (acid resistance and alkali resistance) that are not liable to swell and do not cause swelling and peeling. If such an adhesive sheet for a structural material having excellent acid resistance and alkali resistance can be realized, it is practically useful to be able to cope with the processing of an adherend in a state of being adhered to the adherend.

The present invention has been made in view of the above circumstances, and an object thereof is to provide an adhesive sheet having a limited thickness and capable of maintaining a sufficient adhesive force as a structural material even when exposed to an acidic liquid and an alkaline liquid. Another related object is to provide a display device and a laminate having the above adhesive sheet.

Means for solving the problems

According to the present specification, an adhesive sheet having a thickness of 100 μm or less is provided. The adhesive sheet has an adhesive layer containing an acrylic polymer. The acrylic polymer is a polymer containing 60% by weight or more of a monomer component of an alkyl (meth) acrylate having an alkyl group having 5 or more carbon atoms at the ester end. In addition, the monomer component contains a monomer having a nitrogen atom-containing ring and a carboxyl group-containing monomer. According to the above constitution, even in the case of exposure to an acidic liquid and an alkaline liquid, a sufficient adhesive force can be maintained as a structural material, although having a limited thickness of 100 μm or less.

The action by the above-described constitution is not particularly limited, and the following can be considered. That is, by using a monomer having a nitrogen atom-containing ring and a carboxyl group-containing monomer in combination as the monomer component of the acrylic polymer contained in the adhesive layer, an adhesive suitable for preventing permeation of an acidic liquid and a basic liquid into the adhesive can be formed. By using the monomer having a nitrogen atom-containing ring and the carboxyl group-containing monomer in combination, the cohesive force of the adhesive is improved, and by using one or more of alkyl (meth) acrylates having an alkyl group having 5 or more carbon atoms at the ester end as the main monomer, the adhesive strength can be easily obtained, and the wettability of the adhesive surface is improved, whereby penetration of an acidic liquid or an alkaline liquid from the adhesive sheet end face to the adhesive interface can be prevented or suppressed, as compared with the case of using n-Butyl Acrylate (BA) having an alkyl group having 4 carbon atoms at the ester end. By such an action, it is considered that, although the thickness of the entire adhesive sheet is limited to 100 μm or less, sufficient adhesive force can be maintained as a structural material even when exposed to acidic and basic liquids. The above-described examination was an examination by the inventors based on the experimental results of the examples described later, and the technique disclosed herein is not limited to the above explanation.

In some preferred embodiments, the total ratio of the monomer having a nitrogen atom-containing ring and the carboxyl group-containing monomer in the monomer component is 6.5% by weight or more and 40% by weight or less. In the synthesis of the acrylic polymer, by appropriately setting the total amount of the monomer having a nitrogen atom-containing ring and the carboxyl group-containing monomer used in the above range, a binder having sufficient adhesive force and capable of preventing or suppressing permeation of an acidic liquid and a basic liquid can be satisfactorily obtained.

In some preferred embodiments, the content (A) of the monomer having a nitrogen atom-containing ring _N ) Relative to the content (A) of the carboxyl group-containing monomer _C ) Ratio (A) _N /A _C ) In the range of 1 to 40. In the synthesis of the acrylic polymer, by appropriately setting the use ratio of the monomer having a nitrogen atom-containing ring and the carboxyl group-containing monomer within the above-described range, an adhesive agent having sufficient adhesive force and capable of preventing or suppressing permeation of an acidic liquid and a basic liquid can be satisfactorily obtained.

In some preferred embodiments, the monomer component comprises a hydroxyl group-containing monomer in a proportion of 10% by weight or less. The effect produced by the technique disclosed herein can be preferably achieved by using an acrylic polymer containing a hydroxyl group-containing monomer as a monomer component in a proportion of 10% by weight or less.

Some embodiments of the adhesive sheet are substrate-free double-sided adhesive sheets composed of the adhesive layer. The substrate-less double-sided adhesive sheet can be thinned to the extent that it does not have a substrate, and can contribute to downsizing and space saving of a product to which the double-sided adhesive sheet is applied. In addition, according to the base-material-free adhesive sheet, the adhesive layer such as adhesive force and impact resistance can be maximally used. According to the technology disclosed herein, an adhesive sheet capable of maintaining sufficient adhesive force as a structural material even in the case of exposure to an acidic liquid or an alkaline liquid, independent of a base material, based on the chemical structure of an acrylic polymer contained in an adhesive layer, is now being developed.

Another embodiment of the pressure-sensitive adhesive sheet is a double-sided pressure-sensitive adhesive sheet with a substrate, which further has a substrate layer and the pressure-sensitive adhesive layer is provided on each side of the substrate layer. For example, a pressure-sensitive adhesive sheet with a base material such as a resin film base material is excellent in handleability and workability, and therefore can be processed into various shapes and the like for use in various applications.

The adhesive sheet disclosed herein is suitable for use in fixing members constituting a portable electronic device. Specifically, the pressure-sensitive adhesive sheet is suitable for use in portable electronic devices, in which miniaturization and thickness reduction are strongly demanded, because the pressure-sensitive adhesive sheet can be bonded and fixed with high reliability in a configuration having a thickness of 100 μm or less. In addition, various members such as metal members constituting the portable electronic device can be subjected to processing such as opening formation for various sensors and camera lenses after the adhesive sheet is attached thereto. The processing step may include a step of using an acidic liquid or an alkaline liquid, such as immersing in an acidic etching liquid or cleaning with an alkaline cleaning liquid. The adhesive sheet disclosed herein can maintain a sufficient adhesive force as a structural material even when used in such a manner that it is exposed to an acidic liquid and an alkaline liquid in a state where a member is fixed.

Further, according to the present specification, there is provided a display device including a display portion including a cover member and an organic EL unit, and a support portion. In the display device, an adhesive sheet having a thickness of 100 μm or less is adhered to the support portion. In addition, the adhesive sheet has an adhesive layer containing an acrylic polymer. The acrylic polymer is a polymer containing 60% by weight or more of a monomer component of an alkyl (meth) acrylate having an alkyl group having 5 or more carbon atoms at the ester end. Further, the monomer component contains a monomer having a nitrogen atom-containing ring and a carboxyl group-containing monomer. The pressure-sensitive adhesive sheet disclosed herein can be preferably used as a constituent element (structural material, specifically, member joining means) of the display device described above.

Further, according to the present specification, a laminate is provided which has a metal member and an adhesive sheet attached to a surface of the metal member. In the laminate, the thickness of the adhesive sheet is 100 μm or less. In addition, the adhesive sheet has an adhesive layer containing an acrylic polymer. The acrylic polymer is a polymer containing 60% by weight or more of a monomer component of an alkyl (meth) acrylate having an alkyl group having 5 or more carbon atoms at the ester end. Further, the monomer component contains a monomer having a nitrogen atom-containing ring and a carboxyl group-containing monomer. The pressure-sensitive adhesive sheet disclosed herein can be preferably used in the form of a laminate to be adhered to a metal member that can be exposed to an acidic liquid or an alkaline liquid. According to the laminate, even when exposed to an acidic liquid and an alkaline liquid for processing of a metal member or the like, the adhesive sheet can maintain a good adhesion state to the metal member with a structure in which the thickness is limited.

Drawings

Fig. 1 is a cross-sectional view schematically showing one configuration example of an adhesive sheet.

Fig. 2 is a cross-sectional view schematically showing another configuration example of the pressure-sensitive adhesive sheet.

Fig. 3 is a cross-sectional view schematically showing an exemplary configuration of the laminate.

Fig. 4 is an exploded perspective view schematically showing a configuration example of the display device.

Detailed Description

Hereinafter, preferred embodiments of the present invention will be described. It is to be noted that matters necessary for carrying out the present invention other than those specifically mentioned in the present specification may be understood by those skilled in the art based on the teachings of the present invention and technical knowledge at the time of application. The present invention may be implemented based on the disclosure in the present specification and technical knowledge in the art. In the drawings, members and portions that serve the same function may be denoted by the same reference numerals, and repeated description may be omitted or simplified. In order to clearly illustrate the present invention, the embodiments described in the drawings are schematically illustrated, and do not necessarily accurately represent the dimensions and scale of the adhesive sheet of the present invention actually provided as a product.

In the present specification, the term "adhesive" refers to a material which is in a soft solid (viscoelastic body) state in a temperature range around room temperature as described above and has a property of being easily adhered to an adherend by pressure. The so-called adhesives here are, for example, "c.a. dahlquist," Adhesion: fundamental and Practice ", mcLaren&Sons, (1966) P.143", may be generally defined as having a modulus E that satisfies the complex tensile elastic modulus ^* (1Hz)＜10 ⁷ dyne/cm ² Is a material having the above properties (typically, a material having the above properties at 25 ℃).

< Structure of adhesive sheet >)

The pressure-sensitive adhesive sheet disclosed herein may be a pressure-sensitive adhesive sheet with a base material having the pressure-sensitive adhesive layer on one side or both sides of a non-releasable base material (supporting base material), or may be a non-base material pressure-sensitive adhesive sheet having the pressure-sensitive adhesive layer held on a release liner or the like (i.e., a pressure-sensitive adhesive sheet having no non-releasable base material). In some preferred embodiments, the adhesive sheet is in the form of a double-sided adhesive sheet. The double-sided adhesive sheet can be bonded to an adherend by adhering the respective sides to the adherend, and therefore can be preferably used as a structural material for bonding or fixing members. The term "adhesive sheet" as used herein may include articles called an adhesive tape, an adhesive label, an adhesive film, and the like. The pressure-sensitive adhesive sheet disclosed herein may be in the form of a roll or a sheet. Alternatively, the pressure-sensitive adhesive sheet may be further processed into various shapes.

Fig. 1 shows an example of a structure of a double-sided adhesive type base-less adhesive sheet (base-less double-sided adhesive sheet). The pressure-sensitive adhesive sheet 1 shown in fig. 1 has a structure in which both sides 21A and 21B of a pressure-sensitive adhesive layer 21 without a base material are protected by release liners 31 and 32, respectively, at least on the pressure-sensitive adhesive layer side of which is a release surface. Alternatively, the pressure-sensitive adhesive sheet may have a structure in which one surface (the pressure-sensitive adhesive surface, the first pressure-sensitive adhesive surface) of the pressure-sensitive adhesive layer without a base material is protected by a release liner having both surfaces as release surfaces, and when the pressure-sensitive adhesive sheet is wound, the other surface (the pressure-sensitive adhesive surface, the second pressure-sensitive adhesive surface) of the pressure-sensitive adhesive layer is brought into contact with the back surface of the release liner, whereby the second pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer is also protected by the release liner. The technology disclosed herein can be preferably implemented in such a substrate-free form from the viewpoint of reducing the thickness of the adhesive sheet. The pressure-sensitive adhesive sheet without a base material is easily thinned, and is advantageous in that the pressure-sensitive adhesive sheet can exhibit adhesive properties such as adhesive strength and impact resistance to the maximum extent.

The adhesive sheet disclosed herein may have, for example, a cross-sectional structure schematically shown in fig. 2. The adhesive sheet 2 shown in fig. 2 has the following constitution: on each surface (non-release property) of the base material (base material layer) 10, pressure-sensitive adhesive layers 21, 22 (also referred to as a first pressure-sensitive adhesive layer 21 and a second pressure-sensitive adhesive layer 22, respectively) are provided, and these pressure-sensitive adhesive layers are protected by release liners 31, 32, at least on the pressure-sensitive adhesive layer side of which is a release surface. Alternatively, the pressure-sensitive adhesive sheet may have the following constitution: each side of the substrate (non-releasable) is provided with an adhesive layer (first adhesive layer, second adhesive layer), and one of the adhesive layers (first adhesive layer) is protected by a release liner having both sides as release surfaces. The adhesive sheet may be constituted as follows: the other adhesive layer (second adhesive layer) is also protected by the release liner by bringing the other adhesive layer (second adhesive layer) into contact with the back surface of the release liner by winding the adhesive sheet.

< adhesive layer >)

(acrylic Polymer)

The adhesive layer constituting the adhesive sheet disclosed herein contains an acrylic polymer. The pressure-sensitive adhesive layer is typically an adhesive layer containing an acrylic polymer as a base polymer (a main component in a polymer component, that is, a component constituting 50% by weight or more). Such an adhesive layer is also referred to as an acrylic adhesive layer. The base polymer is a main component of a rubbery polymer (a polymer exhibiting rubber elasticity in a temperature range around room temperature) contained in the adhesive layer. In the present specification, unless otherwise specified, "main component" means a component having a content of more than 50% by weight.

In the present specification, the "acrylic polymer" refers to a polymer containing a monomer unit derived from a monomer having at least one (meth) acryloyl group in one molecule as a monomer unit constituting the polymer, and is also referred to as an acrylic polymer. Hereinafter, a monomer having at least one (meth) acryloyl group in one molecule is also referred to as an "acrylic monomer". In addition, "(meth) acryl" refers to both acryl and methacryl in general. Similarly, "(meth) acrylate" refers collectively to acrylates and methacrylates, and "(meth) acrylic" refers collectively to acrylic and methacrylic.

The acrylic polymer disclosed herein is a polymer containing a monomer component of an alkyl (meth) acrylate having an alkyl group having 5 or more carbon atoms at the ester end (hereinafter also referred to as a C5 or more alkyl (meth) acrylate). The alkyl (meth) acrylate having 5 or more carbon atoms may be represented by the following formula (1).

CH ₂ ＝C(R ¹ )COOR ² (1)

Here, R in the above formula (1) ¹ Is a hydrogen atom or a methyl group. In addition, R ² Is a chain alkyl group having 5 or more carbon atoms. By using an acrylic polymer containing an alkyl (meth) acrylate of 5 or more as a main monomer component, sufficient adhesive strength can be easily obtained, and the wettability of the adhesive surface can be improved, whereby penetration of an acidic liquid and an alkaline liquid from the adhesive sheet end face to the adhesive interface can be suppressed. The number of carbon atoms of the alkyl group of the C5 or more alkyl (meth) acrylate is typically 5 or more and 20 or less (hereinafter, such a range of the number of carbon atoms is sometimes referred to as "C5-20"). The alkyl group of the alkyl (meth) acrylate may have, for example, 18 or less carbon atoms, and may have an alkyl group of the alkyl (meth) acrylate from the viewpoint of the storage modulus of the adhesive, etcThe number of carbon atoms is preferably 14 or less, more preferably 12 or less, and still more preferably 10 or less (for example, 9 or less). The number of carbon atoms may be 6 or more, or 7 or more, typically 8.

Specific examples of the alkyl (meth) acrylate of C5 or more include, but are not particularly limited to: amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate, and the like. The above alkyl (meth) acrylate may be used singly or in combination of two or more. As a preferable example of the above alkyl (meth) acrylate, 2-ethylhexyl acrylate (2 EHA) may be mentioned.

The proportion of the alkyl (meth) acrylate of at least 5 to the monomer component constituting the acrylic polymer is at least 60% by weight. This can exert the effect of using the alkyl (meth) acrylate having 5 or more carbon atoms. The proportion of the alkyl (meth) acrylate C5 or more is preferably 65% by weight or more, more preferably 70% by weight or more (for example, more than 70% by weight), and may be 75% by weight or more. The upper limit of the proportion of the alkyl (meth) acrylate of C5 or more is suitably set, for example, to 95% by weight or less in view of the characteristics (for example, cohesive force) of the copolymerization of the monomer having a nitrogen atom ring and the carboxyl group-containing monomer described later, and may be 93.5% by weight or less, preferably 90% by weight or less, more preferably 85% by weight or less, for example, 80% by weight or less from the viewpoints of the adhesive force, cohesive force and the like.

The acrylic polymer disclosed herein may contain, as a monomer component, one or two or more of alkyl (meth) acrylates having an alkyl group having 4 or less carbon atoms at the ester end (C1-4 alkyl (meth) acrylates). Specific examples of the C1-4 alkyl (meth) acrylate include: methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and the like.

The proportion of the alkyl (meth) acrylate having a chain alkyl group at the ester end (hereinafter, also simply referred to as "alkyl (meth) acrylate") contained as the monomer component of the acrylic polymer is, for example, more than 70% by weight, and from the viewpoint of effectively exhibiting the effect of using the C5 or higher alkyl (meth) acrylate, it is preferably 80% by weight or more, more preferably 90% by weight or more, and still more preferably 95% by weight or more (for example, 99% by weight or more). The upper limit of the proportion of the alkyl (meth) acrylate of at least 5 carbon atoms in the whole alkyl (meth) acrylate is 100% by weight, and may be, for example, 95% by weight or less or 90% by weight or less.

The monomer component constituting the acrylic polymer contains a monomer having a nitrogen atom-containing ring (hereinafter also referred to as "N-ring-containing monomer") and a carboxyl group-containing monomer. By using the N-ring-containing monomer and the carboxyl-containing monomer in combination as the monomer components, the cohesive force of the adhesive is improved, and by combining the actions of both monomers, an adhesive that prevents or inhibits penetration of an acidic liquid and a basic liquid into the adhesive can be obtained.

The N-ring-containing monomer refers to a monomer having a polymerizable group and a ring containing a nitrogen atom. Examples of the polymerizable group include a (meth) acryl group and a vinyl group. The nitrogen atom-containing ring means a cyclic structure containing a nitrogen atom (N) as an atom constituting the ring. The nitrogen atom-containing ring generally preferably has a heterocyclic structure containing a nitrogen atom (N) and a carbon atom (C) as atoms constituting the ring, and further contains an oxygen atom (O) as atoms constituting the ring. Examples of the nitrogen atom-containing ring include: lactam structures such as pyrrolidinoneMorpholine ring, piperidine ring, pyrrolidine ring, piperazine ring, pyridine ring, piperidone ring, pyrimidine ring, pyrazine ring, pyrrole ring, imidazole ring,Azole ring, etc., of which lactam structure and morpholine ring are preferable, and morpholine ring is particularly preferable. The N-ring-containing monomer may be used singly or in combination of two or more.

Examples of the N-ring-containing monomer include: lactam vinyl monomers such as N-vinyl-2-pyrrolidone, N-methyl vinyl pyrrolidone, N-vinyl-epsilon-caprolactam, etc.; vinyl pyridine; vinyl piperidone; vinyl pyrimidine; vinyl piperazine; vinyl pyrazine; vinyl pyrrole; vinyl imidazole; vinyl groupAn azole; vinyl morpholine; n- (meth) acryloylmorpholine; n- (meth) acryloylpiperidine; n- (meth) acryloylpyrrolidine; etc. Among them, preferred are lactam vinyl monomers and N- (meth) acryloylmorpholine, and more preferred are N-vinyl-2-pyrrolidone (NVP) and N-Acryloylmorpholine (ACMO). When NVP is used, there is a tendency that higher adhesion is easily obtained, and when ACMO is used, adhesion and cohesion are easily balanced.

The amount of the N-ring-containing monomer to be used is set within a range that exerts the effect of the combination with the carboxyl-containing monomer. The content of the N-ring-containing monomer is set to, for example, 5 wt% or more, preferably 10 wt% or more, more preferably 16 wt% or more, still more preferably 20 wt% or more, particularly preferably 22 wt% or more, and may be 28 wt% or more (for example, 32 wt% or more) of the entire monomer component. The more the N-ring-containing monomer is used, the more the cohesive force increases, and the more the penetration of the acidic liquid and the basic liquid into the adhesive can be satisfactorily prevented. The content of the N-ring-containing monomer is suitably set to, for example, 40% by weight or less of the entire monomer component, and may be 35% by weight or less or 30% by weight or less. By limiting the amount of the N-ring-containing monomer to an appropriate range, it is easy to achieve both adhesion and cohesion.

In addition, by using a carboxyl group-containing monomer as a monomer component, an adhesive sheet exhibiting good adhesive properties (cohesive force, etc.) can be easily obtained, and the adhesion between the adhesive layer and the adherend can be advantageously improved. In addition, the acid resistance of the adhesive tends to be improved. In addition, for example, in the case of adding a black colorant such as carbon black to the adhesive, the appropriate amount of the carboxyl group-containing monomer is copolymerized, so that the colorant can be easily dispersed in the layer, and the adhesive property can be satisfactorily maintained.

As carboxyl group-containing monomers, it is possible to use: acrylic Acid (AA), methacrylic acid (MAA), carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid, and the like. Among them, AA and MAA are preferable. The carboxyl group-containing monomer may be used singly or in combination of two or more.

The content of the carboxyl group-containing monomer in the monomer component is set within a range that exerts the effect of being used in combination with the N-ring-containing monomer. The carboxyl group-containing monomer may be set to, for example, 0.2% by weight or more (typically 0.5% by weight or more) of the monomer component, and is suitably set to 1% by weight or more, preferably 1.5% by weight or more, more preferably 2.0% by weight or more, and still more preferably 2.5% by weight or more. By increasing the content of the carboxyl group-containing monomer, a higher effect can be exerted. The upper limit of the content of the carboxyl group-containing monomer is not particularly limited, and may be set to, for example, 10% by weight or less, preferably 7% by weight or less, more preferably 5% by weight or less, still more preferably 4.5% by weight or less, still more preferably 4.0% by weight or less, and may be, for example, 3.5% by weight or less.

In some embodiments, the total ratio of the N-ring-containing monomer and the carboxyl-containing monomer in the monomer component is, for example, in the range of 5% by weight to 40% by weight, and preferably 6.5% by weight to 40% by weight. By appropriately setting the total amount of the N-ring-containing monomer and the carboxyl-containing monomer, an adhesive agent having sufficient adhesive force and improved cohesive force and suitable for preventing permeation of an acidic liquid and a basic liquid can be satisfactorily obtained. In some preferred embodiments, the total ratio of the N-ring-containing monomer and the carboxyl-containing monomer in the monomer component is 8 wt% or more, more preferably 12 wt% or more, still more preferably 15 wt% or more, particularly preferably 18 wt% or more, and may be 21 wt% or more, 23 wt% or more, or 26 wt% or more. The total ratio of the N-ring-containing monomer and the carboxyl-containing monomer in the monomer component is preferably 36% by weight or less, more preferably 32% by weight or less, and may be 30% by weight or less. By limiting the total amount of the N-ring-containing monomer and the carboxyl-containing monomer to an appropriate range, both the adhesive force and the cohesive force can be better achieved.

The use ratio of the N-ring-containing monomer to the carboxyl-containing monomer is set within a range that exerts the effects produced by the techniques disclosed herein. In some embodiments, the content (A) of the N-ring-containing monomer used as the monomer component _N ) Content (A) relative to carboxyl group-containing monomer _C ) Ratio (A) _N /A _C ) Can be set in the range of 1 to 40 on a weight basis. By appropriately setting the use ratio of the N-ring-containing monomer and the carboxyl-containing monomer within the above range, an adhesive agent which has sufficient adhesive force and is suitable for preventing permeation of an acidic liquid and a basic liquid can be satisfactorily obtained. From the viewpoint of effectively exhibiting the effect of using the N-ring-containing monomer, the ratio (A) _N /A _C ) Preferably 3 or more, more preferably 5 or more, still more preferably 7 or more, and also 8 or more. In addition, from the viewpoint of effectively exhibiting the effect of using the carboxyl group-containing monomer, the ratio (A) _N /A _C ) Preferably 30 or less, more preferably 25 or less, further preferably 20 or less, particularly preferably 15 or less, and also 10 or less.

In some embodiments, the monomer component may comprise a hydroxyl-containing monomer. By using the hydroxyl group-containing monomer, the cohesive force and the crosslinking density of the adhesive can be adjusted, and the adhesive force and the cohesive force can be adjusted within preferable ranges. Examples of the hydroxyl group-containing monomer include: hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate; polypropylene glycol mono (meth) acrylate; n-hydroxyethyl (meth) acrylamide, and the like. Among them, preferred hydroxyl group-containing monomers include hydroxyalkyl (meth) acrylates in which the alkyl group is a linear alkyl group having 2 to 4 carbon atoms. The hydroxyl group-containing monomer may be used singly or in combination of two or more.

The monomer component may or may not contain a hydroxyl group-containing monomer. In some embodiments, the content of the hydroxyl group-containing monomer is, for example, less than 15% by weight of the entire monomer component, and is suitably set to 10% by weight or less, and may be 8% by weight or less, may be 5% by weight or less, or may be 3% by weight or less. According to the techniques disclosed herein, the desired effect may be achieved by using a small amount of hydroxyl-containing monomers or by not using hydroxyl-containing monomers. In some preferred embodiments, the amount of hydroxyl-containing monomer is less than 2 wt.% of the monomer component as a whole, may be less than 1.0 wt.%, may be less than 0.5 wt.%, and may be less than 0.3 wt.%. The amount of the hydroxyl group-containing monomer used is not particularly limited, and the content of the hydroxyl group-containing monomer may be, for example, 0.01% by weight or more, 0.03% by weight or more, 0.05% by weight or more, or 0.1% by weight or more of the entire monomer component.

Other copolymerizable monomers (monomers other than chain alkyl (meth) acrylate, N-ring-containing monomers, carboxyl-containing monomers, and hydroxyl-containing monomers) may be copolymerized in the acrylic polymer in the technology disclosed herein within a range that does not impair the effects of the invention. As other copolymerizable monomers which may be used, there may be mentioned: an acid anhydride group-containing monomer, an amide group-containing monomer, an amino group-containing monomer, an epoxy group-containing monomer, a cyano group-containing monomer, a ketone group-containing monomer, an alkoxysilyl group-containing monomer, an imide group-containing monomer, and the like. The above functional group-containing monomers may be used singly or in combination of two or more.

As other examples of other copolymerizable monomers, there may be mentioned: vinyl ester monomers such as vinyl acetate, vinyl propionate and vinyl laurate; aromatic vinyl compounds such as styrene, substituted styrene (α -methylstyrene, etc.), and vinyl toluene; cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, isobornyl (meth) acrylate, and the like; aromatic ring-containing (meth) acrylates such as aryl (meth) acrylates (e.g., phenyl (meth) acrylate), aryloxyalkyl (meth) acrylates (e.g., phenoxyethyl (meth) acrylate), and aralkyl (meth) acrylates (e.g., benzyl (meth) acrylate); olefin monomers such as ethylene, propylene, isoprene, butadiene, and isobutylene; chlorine-containing monomers such as vinyl chloride and vinylidene chloride; isocyanate group-containing monomers such as 2- (meth) acryloyloxyethyl isocyanate; alkoxy-containing monomers such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate; vinyl ether monomers such as methyl vinyl ether and ethyl vinyl ether; a polyfunctional monomer having two or more (for example, 3 or more (meth) acryl groups) polymerizable functional groups (for example, a (meth) acryl group) in one molecule, such as 1, 6-hexanediol di (meth) acrylate and trimethylolpropane tri (meth) acrylate; etc.

The monomer component constituting the acrylic polymer may or may not contain the other copolymerizable monomer described above. The amount of the other copolymerizable monomer is not particularly limited as long as it is appropriately selected according to the purpose and use. The content of the other copolymerizable monomer in the above monomer component is suitably set to, for example, less than 30% by weight, preferably less than 10% by weight, more preferably less than 5% by weight, and may be set to less than 3% by weight (for example, less than 1% by weight). The techniques disclosed herein can also be satisfactorily practiced in a manner such that the monomer components contain substantially no other copolymerizable monomers. Here, the monomer component substantially not containing other copolymerizable monomer means that at least other copolymerizable monomer is not intentionally used, and it is permissible to unintentionally contain, for example, about 0.01% by weight or less of other copolymerizable monomer.

The method for obtaining the acrylic polymer is not particularly limited, and various polymerization methods known as a synthetic method of an acrylic polymer, such as a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, a suspension polymerization method, and a photopolymerization method, can be suitably employed. For example, a solution polymerization method can be preferably employed. The polymerization temperature in the solution polymerization can be appropriately selected depending on the types of monomers and solvents used, the types of polymerization initiators, and the like, and may be set to, for example, about 20℃to about 170℃and typically about 40℃to about 140 ℃.

The solvent (polymerization solvent) used for the solution polymerization may be appropriately selected from conventionally known organic solvents (toluene, ethyl acetate, etc.). The initiator used for the polymerization may be appropriately selected from conventionally known polymerization initiators (for example, azo-based polymerization initiators such as 2,2' -Azobisisobutyronitrile (AIBN) and peroxide-based initiators) depending on the kind of polymerization method. The amount of the polymerization initiator to be used may be a usual amount, and for example, may be selected from the range of about 0.005 to about 1 part by weight (typically about 0.01 to about 1 part by weight) based on 100 parts by weight of the monomer component.

The molecular weight of the acrylic polymer obtained by appropriately using the above-mentioned various polymerization methods is not particularly limited, and may be set in an appropriate range according to the desired properties and the like. In some embodiments, the weight average molecular weight (Mw) of the above-described polymers may be in the range of about 10X 10 ⁴ About 500X 10 ⁴ Within a range of (2). From the viewpoint of combining the adhesive force and the cohesive force in a balanced manner, the Mw is about 30X 10 ⁴ The above is suitable, and the Mw is preferably about 50X 10 from the viewpoint of adhesion reliability ⁴ The above, more preferably about 70X 10 ⁴ The above is more preferably about 90×10 ⁴ Above, may be more than 100×10 ⁴ . The upper limit of Mw of the above polymer may be about 300X 10 ⁴ Hereinafter, it may be about 200X 10 ⁴ The following (for example, about 150×10) ⁴ The following are described below). For example, as the Mw of the polymer obtained by solution polymerization, the Mw in the above range can be preferably used. Here, mw refers to a value in terms of standard polystyrene obtained by GPC (gel permeation chromatography). As a GPC apparatus, for example, model name "HLC-8320GPC" (column: TSKgelGMH-H (S), manufactured by Tosoh Co., ltd.) may be used. In the following descriptionThe same applies to the examples.

(tackifying resin)

The adhesive layer may contain a tackifying resin. This can improve the adhesive force of the adhesive sheet. As the tackifying resin, one or two or more of known various tackifying resins selected from rosin-based tackifying resins, phenol-based tackifying resins, terpene-based tackifying resins, modified terpene-based tackifying resins, hydrocarbon-based tackifying resins, epoxy-based tackifying resins, polyamide-based tackifying resins, elastomer-based tackifying resins, ketone-based tackifying resins and the like can be used. For example, rosin-based tackifying resins, phenol-based tackifying resins, terpene-based tackifying resins, modified terpene-based tackifying resins, hydrocarbon-based tackifying resins are preferable, and rosin-based tackifying resins are more preferable.

Specific examples of the rosin-based tackifying resin include: unmodified rosins (raw rosins) such as gum rosin, wood rosin, tall oil rosin, and the like; modified rosins (hydrogenated rosins, disproportionated rosins, polymerized rosins, other chemically modified rosins, etc.. The same applies to the following) obtained by modifying these unmodified rosins by hydrogenation, disproportionation, polymerization, etc.; other various rosin derivatives; etc. Examples of the rosin derivatives include: rosin esters such as rosin derivatives obtained by esterifying unmodified rosin with alcohols (i.e., esters of rosin), rosin derivatives obtained by esterifying modified rosin with alcohols (i.e., esters of modified rosin); unsaturated fatty acid-modified rosins obtained by modifying an unmodified rosin and a modified rosin with an unsaturated fatty acid; unsaturated fatty acid-modified rosin esters obtained by modifying rosin esters with unsaturated fatty acids; rosin alcohols obtained by reducing carboxyl groups in unmodified rosin, modified rosin, unsaturated fatty acid modified rosin or unsaturated fatty acid modified rosin esters; metal salts of rosins (particularly rosin esters) such as unmodified rosin, modified rosin, and various rosin derivatives; rosin phenol resins obtained by adding phenol to rosin (unmodified rosin, modified rosin, various rosin derivatives, etc.) in the presence of an acid catalyst and thermally polymerizing the resultant; etc. Specific examples of rosin esters include, but are not particularly limited to: esters of unmodified or modified rosins (hydrogenated, disproportionated, polymerized, etc.), such as methyl esters, triethylene glycol esters, glycerol esters, pentaerythritol esters, etc., of unmodified or modified rosins (hydrogenated, disproportionated, polymerized, etc.). Among them, rosin esters are preferable. The rosin-based tackifying resin may be used singly or in combination of two or more.

Examples of the phenolic tackifying resins include terpene phenol resins, hydrogenated terpene phenol resins, and alkyl phenol resins.

Terpene phenol resin is a polymer containing terpene residues and phenol residues, and is a concept including both a copolymer of terpenes and a phenolic compound (terpene-phenol copolymer resin) and a resin obtained by phenol-modifying a terpene homopolymer or copolymer (phenol-modified terpene resin). Preferred examples of terpenes constituting such terpene phenol resins include: monoterpenes such as alpha-pinene, beta-pinene, limonene (including d-bodies, l-bodies, and d/l-bodies (terpineol)). The hydrogenated terpene phenol resin is a hydrogenated terpene phenol resin having a structure obtained by hydrogenating such a terpene phenol resin. Sometimes also referred to as hydrogenated terpene phenol resins.

The alkylphenol resin is a resin (oleophenol resin) obtained from alkylphenol and formaldehyde. Examples of the alkylphenol resin include novolac type and resol type.

Examples of terpene-based tackifying resins include polymers of terpenes (typically monoterpenes) such as α -pinene, β -pinene, d-limonene, l-limonene, terpineol, and the like. The terpene may be a homopolymer or a copolymer of two or more terpenes. Examples of the terpene homopolymer include α -pinene polymer, β -pinene polymer, and terpineol polymer. Examples of the modified terpene resin include resins obtained by modifying the terpene resin. Specifically, styrene-modified terpene resins, hydrogenated terpene resins, and the like can be exemplified.

Examples of hydrocarbon tackifying resins include: various hydrocarbon resins such as aliphatic hydrocarbon resins, aromatic hydrocarbon resins, aliphatic cyclic hydrocarbon resins, aliphatic/aromatic petroleum resins (styrene-olefin copolymers and the like), aliphatic/alicyclic petroleum resins, hydrogenated hydrocarbon resins, coumarone-indene resins and the like.

Preferable examples of the tackifying resin include rosin-based tackifying resins. Among them, rosin esters can be preferably used. The proportion of the rosin-based tackifying resin in the entire tackifying resin contained in the adhesive layer may be set to, for example, about 50% by weight or more, about 70% by weight or more, or about 80% by weight or more. The techniques disclosed herein can be preferably practiced with substantially all (e.g., about 97 wt% or more or 99 wt% or more, or 100 wt%) of the tackifying resin being a rosin-based tackifying resin.

The softening point of the tackifying resin is not particularly limited. The softening point of the tackifying resin may be, for example, about 50 ℃ or higher, preferably about 60 ℃ or higher, and may be about 70 ℃ or higher, from the viewpoint of exhibiting a proper cohesive force. The upper limit of the softening point of the tackifying resin is not particularly limited. From the viewpoint of improving the adhesion to an adherend, in some embodiments, a tackifying resin having a softening point of about 200 ℃ or less (more preferably about 150 ℃ or less, for example, less than 130 ℃) may be preferably used.

In some preferred embodiments, the tackifying resin comprises a tackifying resin T having a softening point of 110 ℃ or less _L . By using tackifying resin T _L The adhesion to an adherend (initial adhesion, etc.) is improved, good adhesion is easily obtained, and penetration of an acidic liquid or an alkaline liquid into an adhesive interface is easily prevented. Tackifying resin T _L The softening point of (a) is suitably less than 110 ℃, preferably about 105 ℃ or less, more preferably about 100 ℃ or less, even more preferably about 95 ℃ or less (e.g., less than 95 ℃), particularly preferably about 90 ℃ or less (e.g., about 85 ℃ or less). For tackifying resin T _L The lower limit of the softening point of (b) is not particularly limited, and in some embodiments, the tackifying resin T is from the viewpoint of exhibiting an appropriate cohesive force _L The softening point of (a) may be, for example, about 50℃or higher, may be about 60℃or higher, may be about 65℃or higher,or may be at about 70℃or higher.

Although not particularly limited, as the tackifying resin T _L Examples of rosin-based tackifying resins that are preferably used include rosin esters such as unmodified rosin esters and modified rosin esters. As a preferable example of the modified rosin ester, hydrogenated rosin esters can be cited. For example, esters of unmodified rosin or modified rosin (e.g., hydrogenated rosin), such as rosin esters such as methyl ester, glycerol ester of unmodified rosin or modified rosin (e.g., hydrogenated rosin), can be used as the tackifying resin T _L . In some preferred embodiments of the adhesive layer, tackifying resin T _L Comprising hydrogenated rosin esters. Tackifying resin T _L Only one or two or more hydrogenated rosin esters may be contained as the rosin esters.

Tackifying resin T _L In addition to the rosin-based tackifying resin, other tackifying resins are included. As the other tackifying resin, one type of tackifying resin having a softening point of 110 ℃ or lower may be appropriately selected from the above exemplified tackifying resins, and two or more types may be used singly or in combination.

In some embodiments, the rosin-based tackifying resin is present in tackifying resin T _L The proportion of the total amount may be set to, for example, about 50% by weight or more, about 65% by weight or more, or about 75% by weight or more. The technology disclosed herein can be preferably used as tackifying resin T _L Substantially all (for example, about 97 wt% or more, 99 wt% or more, 100 wt%) of the resin is a rosin-based tackifying resin.

The adhesive layer may contain a tackifying resin T _L The tackifying resin T may not be contained _L . In addition, tackifying resin T _L The amount of the tackifying resin used (in the case of containing two or more tackifying resins, the total amount thereof) is set so as to exert the effect produced by the technique disclosed herein. Tackifying resin T in adhesive layer _L The content of (2) may be appropriately set within a range of about 60 parts by weight or less based on 100 parts by weight of the acrylic polymer, and is appropriately set to 50 parts by weight or less, preferably 45 parts by weight or less, more preferably from the viewpoint of the cohesive force or the likeThe amount is 40 parts by weight or less and may be 35 parts by weight or less. Containing tackifying resin T in the adhesive layer _L In the mode (a), tackifying resin T _L The amount of the tackifying resin T is set to about 1 part by weight or more based on 100 parts by weight of the acrylic polymer _L In some preferred embodiments, the effect of (2) is suitably set to 5 parts by weight or more, from the viewpoint of improving the adhesive force, and the like, and may be 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, or 25 parts by weight or more. In other embodiments, the adhesive layer is substantially free of tackifying resin T _L . In this manner, the adhesive layer may be allowed to contain about 0.3 wt% or less (e.g., about 0.1 wt% or less, typically about 0.01 wt% or less) of tackifying resin T _L 。

In some embodiments, the adhesive layer may contain a tackifier resin T having a softening point of 110 ℃ or less _L And a tackifying resin T having a softening point greater than 110 ℃ (typically greater than 110 ℃ and less than or equal to 200 ℃) _H . By combining tackifying resin T _L And tackifying resin T _H Higher adhesion is easily achieved. As tackifying resin T _H One or a combination of two or more of the above exemplified tackifying resins having a softening point of more than 110 ℃ may be used alone. Tackifying resin T _H Preferably, the resin composition contains one or more kinds selected from rosin-based tackifying resins. More preferably tackifying resin T _L And tackifying resin T _H All comprising rosin-based tackifying resins.

From the viewpoint of improving the cohesive force, the tackifying resin T _H The softening point of (2) may be about 115 ℃ or higher, may be about 120 ℃ or higher, may be about 130 ℃ or higher, or may be about 140 ℃ or higher. For tackifying resin T _H The upper limit of the softening point of (a) is not particularly limited, and from the viewpoint of adhesion to an adherend, a tackifying resin having a softening point of about 200 ℃ or less (more preferably about 160 ℃ or less, still more preferably 145 ℃ or less, for example about 130 ℃ or less) can be preferably used.

The adhesive layer may contain a tackifying resin T _H Or does not need toComprises tackifying resin T _H . In addition, tackifying resin T _H The amount of the tackifying resin used (in the case of containing two or more tackifying resins, the total amount thereof) is set so as to exert the effect produced by the technique disclosed herein. Tackifying resin T in adhesive layer _H The content of (2) is suitably set to less than 30 parts by weight, preferably less than 20 parts by weight, and may be 18 parts by weight or less, for example, relative to 100 parts by weight of the acrylic polymer. Containing tackifying resin T in the adhesive layer _H In the mode (a), tackifying resin T _H The amount of the tackifying resin T is set to about 1 part by weight or more based on 100 parts by weight of the acrylic polymer _H In some embodiments, the effect of (2) is suitably set to 5 parts by weight or more, and may be 10 parts by weight or more, or may be 12 parts by weight or more, from the viewpoint of improving the adhesive force. The technology disclosed herein uses an adhesive layer that is substantially free of tackifying resin T _H In a manner that is satisfactory.

The softening point of the tackifying resin described herein is defined as a value measured based on the softening point test method (the ring and ball method) specified in JIS K5902 and JIS K2207. Specifically, the sample was melted rapidly at a temperature as low as possible, and carefully filled into a ring placed on a flat metal plate in such a manner that no bubbles were formed. After cooling, the raised portion is cut off from the plane containing the upper end of the ring with a slightly heated knife. Next, the support (ring table) was placed in a glass container (heating bath) having a diameter of 85mm or more and a height of 127mm or more, and glycerin was injected to a depth of 90mm or more. Next, a steel ball (9.5 mm in diameter, 3.5g in weight) and a ring filled with a sample were immersed in glycerin so as not to contact each other, and the temperature of glycerin was maintained at 20.+ -. 5 ℃ for 15 minutes. Then, the steel ball is placed in the center of the surface of the sample in the ring, and is placed in a fixed position on the support. Then, the distance from the upper end of the ring to the glycerin surface was kept at 50mm, and a thermometer was placed so that the center of the bulb of water of the thermometer was at the same height as the center of the ring, and the container was heated. The flame of the bunsen burner used for heating is brought into contact with the center of the bottom of the container and the middle of the rim to uniformly heat. The rate of rise in bath temperature after reaching 40℃from the start of heating must be 5.0deg.C.+ -. 0.5℃per minute. The temperature at which the sample gradually softens and flows down the ring and eventually contacts the bottom plate was read as the softening point. At the same time, the softening points were measured for 2 or more pieces, and the average value was used.

The technology disclosed herein may be implemented in either a manner in which the adhesive layer contains a tackifying resin or a manner in which the adhesive layer does not contain a tackifying resin. The amount of the tackifier resin used (the total amount (total amount) in the case of containing two or more kinds of tackifier resins)) is set so as to exert the effect produced by the technology disclosed herein. The content of the tackifier resin in the pressure-sensitive adhesive layer may be appropriately set in a range of, for example, about 100 parts by weight or less relative to 100 parts by weight of the acrylic polymer, and is appropriately set to 60 parts by weight or less, preferably 50 parts by weight or less (for example, 40 parts by weight or less) from the viewpoint of the cohesive force or the like. In the case where the pressure-sensitive adhesive layer contains a tackifying resin, the content of the tackifying resin is set to about 1 part by weight or more based on 100 parts by weight of the acrylic polymer so as to exert the effect of containing the tackifying resin, and in some preferred embodiments, it is set to 5 parts by weight or more, preferably 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, or 25 parts by weight or more, from the viewpoint of improving the adhesive force. In other embodiments, the adhesive layer is substantially free of tackifying resin. In this manner, the adhesive layer may be allowed to contain about 0.3 wt% or less (e.g., about 0.1 wt% or less, typically about 0.01 wt% or less) of tackifying resin.

(crosslinking agent)

In the technology disclosed herein, the adhesive composition used in the formation of the adhesive layer may contain a crosslinking agent as needed. By using a proper kind and amount of the crosslinking agent for other components (acrylic polymer, tackifying resin, etc.) in the adhesive layer, the characteristics of the adhesive can be adjusted, so that an adhesive having desired characteristics can be satisfactorily realized. No special kind of cross-linking agentThe crosslinking agent may be appropriately selected from conventionally known crosslinking agents. Examples of such a crosslinking agent include: isocyanate-based crosslinking agent, epoxy-based crosslinking agent,Oxazoline-based crosslinking agents, aziridine-based crosslinking agents, melamine-based crosslinking agents, peroxide-based crosslinking agents, urea-based crosslinking agents, metal alkoxide-based crosslinking agents, metal chelate-based crosslinking agents, metal salt-based crosslinking agents, carbodiimide-based crosslinking agents, hydrazine-based crosslinking agents, amine-based crosslinking agents, silane-based coupling agents, and the like. Among them, isocyanate-based crosslinking agent, epoxy-based crosslinking agent and +_ are preferable>The oxazoline-based crosslinking agent, the aziridine-based crosslinking agent, and the melamine-based crosslinking agent, and the isocyanate-based crosslinking agent and the epoxy-based crosslinking agent are more preferable. The crosslinking agent may be used singly or in combination of two or more. The crosslinking agent is contained in the adhesive layer in a form after the crosslinking reaction, a form before the crosslinking reaction, a form after the partial crosslinking reaction, an intermediate or composite form thereof, or the like. The above-mentioned crosslinking agent is typically contained in the adhesive layer only in a form after the crosslinking reaction.

In some preferred embodiments, as the crosslinking agent, an isocyanate-based crosslinking agent may be used. As the isocyanate-based crosslinking agent, polyfunctional isocyanates (refer to compounds having an average of two or more isocyanate groups per molecule, including substances having an isocyanurate structure) can be preferably used. The isocyanate-based crosslinking agent may be used singly or in combination of two or more.

Examples of the polyfunctional isocyanate include: aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and the like.

Specific examples of the aliphatic polyisocyanate include: 1, 2-ethylene diisocyanate; butylene diisocyanate such as 1, 2-butylene diisocyanate, 1, 3-butylene diisocyanate, and 1, 4-butylene diisocyanate; hexamethylene diisocyanate such as 1, 2-hexamethylene diisocyanate, 1, 3-hexamethylene diisocyanate, 1, 4-hexamethylene diisocyanate, 1, 5-hexamethylene diisocyanate, 1, 6-hexamethylene diisocyanate and 2, 5-hexamethylene diisocyanate; 2-methyl-1, 5-pentane diisocyanate, 3-methyl-1, 5-pentane diisocyanate, lysine diisocyanate, and the like.

Specific examples of the alicyclic polyisocyanate include: isophorone diisocyanate; cyclohexyl diisocyanate such as 1, 2-cyclohexyl diisocyanate, 1, 3-cyclohexyl diisocyanate, and 1, 4-cyclohexyl diisocyanate; cyclopentyl diisocyanate such as 1, 2-cyclopentyl diisocyanate and 1, 3-cyclopentyl diisocyanate; hydrogenated xylylene diisocyanate, hydrogenated toluene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tetramethylxylylene diisocyanate, 4' -dicyclohexylmethane diisocyanate, and the like.

Specific examples of the aromatic polyisocyanate include: 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, 4' -diphenylmethane diisocyanate, 2' -diphenylmethane diisocyanate, 4' -diphenyl ether diisocyanate, 2-nitrodiphenyl-4, 4' -diisocyanate, 2' -diphenylpropane-4, 4' -diisocyanate 3,3' -dimethyldiphenylmethane-4, 4' -diisocyanate, 4' -diphenylpropane diisocyanate, isophthalate diisocyanate, p-phenylene diisocyanate, naphthylene 1, 4-diisocyanate, naphthylene 1, 5-diisocyanate, 3' -dimethoxydiphenyl-4, 4' -diisocyanate, xylylene-1, 4-diisocyanate, xylylene-1, 3-diisocyanate, and the like.

As the preferable polyfunctional isocyanate, polyfunctional isocyanates having three or more isocyanate groups on average per molecule can be exemplified. The trifunctional or higher isocyanate may be a polymer (typically a dimer or trimer) of a difunctional or higher isocyanate, a derivative (e.g., an addition reaction product of a polyol and two or more polyfunctional isocyanates), a polymer, or the like. Examples include: dimers of diphenylmethane diisocyanate or trimers of diphenylmethane diisocyanate, isocyanurate bodies of hexamethylene diisocyanate (isocyanurate structure trimer adducts), reaction products of trimethylolpropane and toluene diisocyanate, reaction products of trimethylolpropane and hexamethylene diisocyanate, polymethylene polyphenyl isocyanate, polyether polyisocyanate, polyester polyisocyanate and other polyfunctional isocyanates. Examples of the commercial products of the polyfunctional isocyanate include: trade names "Duranate TPA-100" manufactured by Asahi chemical Co., ltd., trade name "CORONATE L" manufactured by Tosoh Co., ltd., and "CORONATE HL" manufactured by Tosoh Co., ltd., and "CORONATE HK" manufactured by Tosoh Co., ltd., and "CORONATE 2096" manufactured by Tosoh Co., ltd., and the like.

The amount of the isocyanate-based crosslinking agent used is not particularly limited. For example, the amount of the acrylic polymer may be set to about 0.5 parts by weight or more based on 100 parts by weight of the acrylic polymer. The amount of the isocyanate-based crosslinking agent used may be, for example, 1.0 part by weight or more, or 1.5 parts by weight or more (for example, 2.0 parts by weight or more) based on 100 parts by weight of the acrylic polymer, from the viewpoint of both the cohesive force and the adhesion, impact resistance, and the like. On the other hand, from the viewpoint of improving the adhesion to an adherend, the amount of the isocyanate-based crosslinking agent used is suitably 10 parts by weight or less, and may be 8 parts by weight or less, or 5 parts by weight or less, or 3 parts by weight or less (for example, less than 3 parts by weight) based on 100 parts by weight of the acrylic polymer.

As other preferable examples of the crosslinking agent, epoxy-based crosslinking agents can be cited. As the epoxy-based crosslinking agent, a compound having two or more epoxy groups in one molecule can be used without particular limitation. Epoxy-based crosslinking agents having three to five epoxy groups in one molecule are preferred. The epoxy-based crosslinking agent may be used singly or in combination of two or more.

Specific examples of the epoxy-based crosslinking agent include, but are not particularly limited to: n, N, N ', N' -tetraglycidyl m-xylylenediamine, 1, 3-bis (N, N-diglycidyl aminomethyl) cyclohexane, 1, 6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polyglycidyl ether, and the like. Examples of the commercial products of the epoxy-based crosslinking agent include: trade names "TETRAD-C" and "TETRAD-X" manufactured by Mitsubishi gas chemical corporation, trade name "EPICLON CR-5L" manufactured by DIC corporation, trade name "Denacol EX-512" manufactured by Nagase Chemte X corporation, trade name "TEPIC-G" manufactured by Nissan chemical industry corporation, and the like.

The amount of the epoxy-based crosslinking agent used is not particularly limited. The amount of the epoxy-based crosslinking agent to be used may be set to be, for example, greater than 0 parts by weight and equal to or less than about 1 part by weight (typically, about 0.001 parts by weight to about 0.5 parts by weight) based on 100 parts by weight of the acrylic polymer. The amount of the epoxy-based crosslinking agent to be used is preferably about 0.005 parts by weight or more, more preferably about 0.01 parts by weight or more, still more preferably about 0.02 parts by weight or more, and still more preferably about 0.03 parts by weight or more, based on 100 parts by weight of the acrylic polymer, from the viewpoint of properly exhibiting the effect of improving the cohesive force. In addition, the amount of the epoxy-based crosslinking agent to be used is suitably set to about 0.5 parts by weight or less, preferably about 0.2 parts by weight or less, more preferably less than 0.1 parts by weight, still more preferably 0.07 parts by weight or less (for example, about 0.05 parts by weight or less) based on 100 parts by weight of the acrylic polymer, from the viewpoint of improving the adhesion to an adherend. By reducing the amount of the epoxy-based crosslinking agent, impact resistance tends to be improved.

In some preferred embodiments, as the crosslinking agent, an isocyanate-based crosslinking agent and at least one crosslinking agent having a different kind of crosslinkable functional group from the isocyanate-based crosslinking agent may be used in combination. According to the technology disclosed herein, excellent cohesive force can be exerted by using a combination of a crosslinking agent other than an isocyanate-based crosslinking agent (that is, a crosslinking agent having a different kind of crosslinkable reactive group from the isocyanate-based crosslinking agent; hereinafter also referred to as "non-isocyanate-based crosslinking agent").

The type of the non-isocyanate-based crosslinking agent that can be used in combination with the isocyanate-based crosslinking agent is not particularly limited, and may be appropriately selected from the above-mentioned crosslinking agents. The non-isocyanate crosslinking agent may be used singly or in combination of two or more. In some preferred embodiments, an epoxy-based crosslinking agent may be used as the non-isocyanate-based crosslinking agent. For example, the combination of an isocyanate-based crosslinking agent and an epoxy-based crosslinking agent facilitates both of the cohesiveness and impact resistance.

In the technology disclosed herein, there is no particular limitation on the relationship between the content of the isocyanate-based crosslinking agent and the content of the non-isocyanate-based crosslinking agent (e.g., epoxy-based crosslinking agent). The content of the non-isocyanate-based crosslinking agent may be set to, for example, about 1/10 or less of the content of the isocyanate-based crosslinking agent. The content of the non-isocyanate-based crosslinking agent is preferably set to about 1/20 or less, more preferably about 1/30 or less (e.g., 1/40 or less) of the content of the isocyanate-based crosslinking agent on a weight basis, from the viewpoint of more suitably satisfying both the adhesion to an adherend and the cohesive strength. In addition, from the viewpoint of appropriately exhibiting the effect of using the isocyanate-based crosslinking agent and the non-isocyanate-based crosslinking agent (for example, the epoxy-based crosslinking agent) in combination, the content of the non-isocyanate-based crosslinking agent is set to about 1/1000 or more, for example, about 1/500 or more, and may be about 1/300 or more, may be about 1/100 or more, or may be about 1/60 or more.

The total amount (total amount) of the crosslinking agent used is not particularly limited. For example, the amount of the acrylic polymer may be set to about 10 parts by weight or less, and may be selected from the range of preferably about 0.005 to about 10 parts by weight, more preferably about 0.01 to about 5 parts by weight, relative to 100 parts by weight of the acrylic polymer.

(colorant)

The adhesive layer may or may not contain a colorant. By containing the colorant, the light transmittance (light blocking property) of the adhesive layer can be adjusted. Adjusting the light transmittance of the adhesive layer may also help to adjust the light transmittance of the adhesive sheet containing the adhesive layer. As the above-mentioned colorant, various materials capable of attenuating light traveling in the adhesive layer by reflection and/or absorption can be used. The color of the colorant is not particularly limited, and may be, for example, black, gray, white, red, blue, yellow, green, yellowish green, orange, purple, gold, silver, pearl, or the like. The above-mentioned colorant may be typically contained in the adhesive layer in a state dispersed in the constituent material of the adhesive layer (may be in a dissolved state).

As the colorant, various pigments and dyes can be used. Examples of pigments include: inorganic pigments such as zinc carbonate, zinc oxide, zinc sulfide, talc, kaolin, calcium carbonate, titanium oxide, silica, lithium fluoride, calcium fluoride, barium sulfate, aluminum oxide, zirconium oxide, iron oxides, iron hydroxides, chromium oxides, spinel firing, chromic acid, chromium Zhu Gonglei, prussian blue, aluminum powder, bronze powder, silver powder, and calcium phosphate; phthalocyanines, azo compounds, condensed azo compounds, azo lakes, anthraquinone compounds, perylene-violet ketones, indigo compounds, thioindigo compounds, isoindolinones, methylimines, di-amines Organic pigments such as oxazine, quinacridone, nigrosine, triphenylmethane, and carbon black. Examples of the dye include: azo dyes, anthraquinone, quinophthalone, styryl, diphenylmethane, triphenylmethane,/->Oxazine, triazine, xanthan gum, methane, azomethine, acridine, and diazine. The colorant may be used singly or in combination of two or more.

From the viewpoint of being able to effectively adjust the light blocking property by a small amount of the colorant, a black colorant can be preferably used. Specific examples of the black colorant include: carbon black (furnace black, channel black, acetylene black, thermal black, lamp black, pine, etc.), graphite, copper oxide, manganese dioxide, aniline black, perylene black, titanium black, cyanine black, hematite, activated carbon, ferrite (nonmagnetic ferrite, magnetic ferrite, etc.), magnetite, chromium oxide, iron oxide, molybdenum disulfide, chromium complexes, anthraquinone-based colorants, etc. These may be used singly or in combination of two or more. Among them, carbon black is preferable. As the carbon black particles, surface-modified carbon black particles having a functional group such as a carboxyl group, an amino group, a sulfonic acid group, a silicon-containing group (for example, an alkoxysilyl group or an alkylsilyl group) can be used. Such surface-modified carbon black particles are also called self-dispersing carbon black, and the addition amount of the dispersing agent is not required or can be reduced. The above carbon black particles may be used singly or in combination of two or more.

From the viewpoint that the light blocking property of the adhesive layer can be effectively adjusted by a small amount of the colorant, a particulate colorant (pigment) can be preferably used. In some preferred embodiments, colorants having an average particle size of about 10nm or greater (e.g., about 30nm or greater) may be used (e.g., particulate black colorants such as carbon black). The average particle diameter is, for example, about 50nm or more, may be about 100nm or more, or may be about 150nm or more. The upper limit of the average particle diameter of the colorant is not particularly limited, and may be, for example, about 3000nm or less and about 1000nm or less. The average particle diameter of the colorant is preferably about 500nm or less from the viewpoint of improving the light blocking property.

The average particle diameter of the colorant in the present specification means a volume average particle diameter, specifically a particle diameter at which the cumulative value in the particle size distribution measured by a particle size distribution measuring apparatus based on a laser scattering/diffraction method is 50% (50% volume average particle diameter; hereinafter, may be simply referred to as "D") ₅₀ . ). As the measuring device, for example, the product name "microtrack MT3000II" manufactured by Microtrac Bell corporation or an equivalent thereof can be used.

The content of the colorant is not limited to a specific range. The content of the colorant in the pressure-sensitive adhesive layer may be set to about 0.1 wt% or more, preferably about 0.5 wt% or more, from the viewpoint of obtaining the effect of adding the colorant, and from the viewpoint of light blocking property, it is preferably about 1 wt% or more, more preferably about 2 wt% or more, and still more preferably about 3 wt% or more (for example, about 5 wt% or more). The upper limit of the content of the colorant in the adhesive layer may be set to, for example, less than 15% by weight, preferably less than 10% by weight, more preferably less than 8% by weight, and even more preferably less than 7% by weight. From the viewpoint of suppressing the decrease in the adhesive property and maintaining the target performance, it is preferable to limit the amount of the colorant contained in the adhesive layer.

(antirust agent)

Some preferred adhesive layers may include rust inhibitors. The rust inhibitor is not particularly limited, and examples thereof include: azole rust inhibitors, amine compounds, nitrites, ammonium benzoate, ammonium phthalate, ammonium stearate, ammonium palmitate, ammonium oleate, ammonium carbonate, dicyclohexylamine benzoate, urea, urotropine, thiourea, phenyl carbamate, N-cyclohexylammonium carbamate (CHC), and the like. The rust inhibitor may be used singly or in combination of two or more.

As the rust inhibitor, an azole rust inhibitor can be preferably used. As the azole rust inhibitor, an azole rust inhibitor containing an azole compound containing two or more hetero atoms as an active ingredient and at least one of the hetero atoms being a nitrogen atom is preferably used. As preferable examples of the compound which can be used as the azole rust inhibitor, benzotriazole rust inhibitors containing benzotriazole compounds as an active ingredient can be cited. Preferable examples of the benzotriazole compounds include: 1,2, 3-benzotriazole, 5-methylbenzotriazole, 4-methylbenzotriazole, carboxybenzotriazole and the like.

The content of the rust inhibitor is not particularly limited, and may be set to 0.01 parts by weight or more (typically 0.05 parts by weight or more) with respect to 100 parts by weight of the acrylic polymer, for example. The content may be 0.1 part by weight or more, 0.3 parts by weight or more, or 0.5 parts by weight or more from the viewpoint of obtaining a more excellent effect of preventing metal corrosion. On the other hand, from the viewpoint of improving the cohesive force of the adhesive, the content of the rust inhibitor is suitably set to less than 8 parts by weight relative to 100 parts by weight of the acrylic polymer, and may be set to 5 parts by weight or less, or may be set to 2 parts by weight or less.

(other additives)

The adhesive composition may contain various additives commonly used in the adhesive field, such as leveling agents, crosslinking aids, plasticizers, softeners, antistatic agents, anti-aging agents, ultraviolet absorbers, antioxidants, and light stabilizers, as required. The adhesive composition may optionally contain a polymer other than the acrylic polymer (such as a rubber polymer) or an oligomer (for example, an acrylic oligomer having a Mw of about 1000 or more and less than about 30000) within a range that does not impair the effects of the present invention. As such various additives, conventionally known ones can be used by a conventional method, and are not characteristic of the present invention, and therefore, detailed description thereof is omitted.

(adhesive composition)

The adhesive layer (layer composed of an adhesive) disclosed herein may be an adhesive layer formed of an aqueous adhesive composition, a solvent-based adhesive composition, a hot-melt adhesive composition, an active energy ray-curable adhesive composition cured by irradiation of active energy rays such as ultraviolet rays or electron rays. The aqueous adhesive composition is an adhesive composition in the form of an adhesive (adhesive layer forming component) contained in a solvent (aqueous solvent) containing water as a main component, and typically includes a composition in the form of a so-called water-dispersible adhesive composition (a composition in which at least a part of the adhesive is dispersed in water), and the like. The solvent-type adhesive composition is an adhesive composition in a form containing an adhesive in an organic solvent. As the organic solvent contained in the solvent-type adhesive composition, one or two or more kinds of organic solvents (toluene, ethyl acetate, etc.) exemplified as the organic solvents usable in the above-mentioned solution polymerization can be used without particular limitation. The technology disclosed herein can be preferably implemented in such a manner as to have an adhesive layer formed of a solvent-type adhesive composition from the viewpoint of adhesive properties and the like. In the case of the method having the solvent-based adhesive layer formed of the solvent-based adhesive composition, the refractive index improving effect by the technique disclosed herein can be satisfactorily achieved.

(formation of adhesive layer)

The adhesive layer disclosed herein can be formed by a conventionally known method. For example, a method of forming an adhesive layer by applying an adhesive composition to a surface (release surface) having releasability and drying it can be employed. For the pressure-sensitive adhesive sheet having a structure of a substrate, for example, a method (direct method) of forming a pressure-sensitive adhesive layer by directly applying (typically coating) a pressure-sensitive adhesive composition to the substrate and drying the composition can be used. In addition, a method (transfer method) of forming an adhesive layer on a surface (release surface) having releasability by applying an adhesive composition to the surface and drying the composition, and transferring the adhesive layer to a substrate may be employed. As the release surface, for example, a surface of a release liner described later can be preferably used. The adhesive layer disclosed herein is typically formed continuously, but is not limited to this, and may be formed in a regular or irregular pattern such as dots, stripes, or the like, for example.

The adhesive composition may be applied using a conventionally known coater such as a gravure roll coater, a die coater, or a bar coater. Alternatively, the adhesive composition may be applied by dipping, curtain coating, or the like.

Drying of the adhesive composition is preferably performed under heating from the viewpoints of promoting the crosslinking reaction, improving the production efficiency, and the like. The drying temperature may be set, for example, at about 40 to about 150 ℃, preferably at about 60 to about 130 ℃. After drying the adhesive composition, further curing may be performed for the purpose of adjusting the transfer of components in the adhesive layer, proceeding of the crosslinking reaction, relaxation of strain that may exist in the adhesive layer, and the like.

The pressure-sensitive adhesive layer disclosed herein may have a single-layer structure or a multilayer structure having two or more layers. The pressure-sensitive adhesive layer is preferably a single-layer structure from the viewpoint of productivity and the like.

The thickness of the adhesive layer is set in a range where the total thickness of the adhesive sheet is 100 μm or less. For example, the thickness of the adhesive layer is suitably about 100 μm or less, preferably about 70 μm or less, more preferably about 50 μm or less. The thickness of the adhesive layer may be set to about 35 μm or less. The pressure-sensitive adhesive layer having a limited thickness can suitably meet the demand for thickness reduction and weight reduction. In addition, according to the technology disclosed herein, by the constitution in which the thickness is limited as described above, an adhesive having acid resistance and alkali resistance and having sufficient adhesive force can be obtained. The lower limit of the thickness of the pressure-sensitive adhesive layer is not particularly limited, and is set to be favorably about 1 μm or more, preferably about 3 μm or more, more preferably about 10 μm or more, still more preferably about 15 μm or more, still more preferably about 20 μm or more, and may be about 30 μm or more, and may be about 35 μm or more, and may be about 40 μm or more, from the viewpoint of adhesion to an adherend. By increasing the thickness of the adhesive layer, more excellent adhesive properties are easily obtained. In addition, when the thickness of the pressure-sensitive adhesive layer increases, the permeability in the thickness direction of the acidic liquid and the alkaline liquid tends to be excellent. In the pressure-sensitive adhesive sheet having pressure-sensitive adhesive layers (first pressure-sensitive adhesive layer and second pressure-sensitive adhesive layer) on each side of the substrate, the thickness of each pressure-sensitive adhesive layer may be the same or different.

Substrate (substrate layer) >, substrate layer

In the embodiment in which the adhesive sheet disclosed herein is in the form of a single-sided adhesive or double-sided adhesive base-material-carrying adhesive sheet, a resin film, paper, cloth, a rubber sheet, a foam sheet, a metal foil, a composite thereof, or the like can be used as a base material for supporting (backing) the adhesive layer. As examples of the paper, there may be mentioned: japanese paper, kraft paper, cellophane, quality paper, synthetic paper, surface-coated paper, and the like. Examples of the cloth include woven fabrics and nonwoven fabrics obtained by blending various fibrous materials alone or in combination. Examples of the fibrous material include: cotton, staple fibers, abaca, pulp, rayon, acetate, polyester, polyvinyl alcohol, polyamide, polyolefin, and the like. Examples of the rubber sheet include: natural rubber sheets, butyl rubber sheets, and the like. Examples of the foam sheet include: foamed polyurethane sheets, foamed neoprene sheets, and the like. Examples of the metal foil include aluminum foil and copper foil.

The term "nonwoven fabric" as used herein mainly refers to a concept of nonwoven fabric for an adhesive sheet used in the field of an adhesive tape and other adhesive sheets, and typically refers to a nonwoven fabric (sometimes referred to as "paper") produced by using a general paper machine. The term "resin film" as used herein means typically a non-porous resin sheet, and means a resin film substantially free of bubbles (void-free). Therefore, the resin film is a concept different from (i.e., excluding) a foam film, a nonwoven fabric, and a woven fabric. The resin film may be any of a non-stretched film, a uniaxially stretched film, and a biaxially stretched film.

As the base material constituting the adhesive sheet with a base material, a base material containing a resin film as a base film can be preferably used. The base film is typically a (independent) member that can independently maintain shape. The substrate in the technology disclosed herein may consist essentially of such a base film. Alternatively, the base material may include an auxiliary layer in addition to the base film. Examples of the auxiliary layer include a colored layer, a reflective layer, an undercoat layer, and an antistatic layer provided on the surface of the base film.

The resin film is a film containing a resin material as a main component (for example, a component having a content of more than 50% by weight in the resin film). Examples of the resin film include: polyolefin resin films such as Polyethylene (PE), polypropylene (PP), and ethylene-propylene copolymers; polyester resin films such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN); a vinyl chloride resin film; vinyl acetate resin film; a polyimide resin film; a polyamide resin film; a fluorine-containing resin film; glass paper; etc. The resin film may be a rubber film such as a natural rubber film or a butyl rubber film. Among them, from the viewpoint of handleability and workability, a polyester film is preferable, and among them, a PET film is particularly preferable.

The substrate may have transparency, light blocking property, or light reducing property. In some embodiments, a colorant may be contained in the substrate (e.g., resin film). This can adjust the light transmittance (light blocking property) of the base material. Adjusting the light transmittance (e.g., vertical light transmittance) of the substrate helps to adjust the light transmittance of the substrate, and thus the light transmittance of the adhesive sheet containing the substrate.

As the colorant, pigments and dyes known in the prior art can be used, as can the colorant that can be contained in the adhesive layer. The colorant is not particularly limited, and may be, for example, black, gray, white, red, blue, yellow, green, yellow-green, orange, violet, gold, silver, pearl, or the like.

The base material (for example, a resin film) may be blended with various additives such as a filler (inorganic filler, organic filler, etc.), a dispersant (surfactant, etc.), an anti-aging agent, an antioxidant, an ultraviolet absorber, an antistatic agent, a lubricant, a plasticizer, etc., as required. The blend ratio of the various additives may be less than about 30 wt% (e.g., less than about 20 wt%, typically less than about 10 wt%).

The substrate (for example, a resin film) may have a single-layer structure, or may have a multilayer structure of two layers, three layers, or more than three layers. From the viewpoint of shape stability, the substrate is preferably a single-layer structure. In the case of a multilayer structure, at least one layer (preferably all layers) is preferably a layer having a continuous structure of the above-mentioned resin (for example, polyester-based resin). The method for producing the base material (typically, a resin film) is not particularly limited, and conventionally known methods can be suitably employed. For example, conventionally known usual film molding methods such as extrusion molding, inflation molding, T-die casting molding, and calender roll molding can be suitably employed.

The base material may be colored by a coloring layer disposed on the surface of the base film (preferably, a resin film). In the base material having such a structure including the base film and the coloring layer, the base film may or may not contain a coloring agent. The colored layer may be disposed on any one surface of the base film or may be disposed on both surfaces. In the constitution in which the coloring layers are disposed on both surfaces of the base film, the constitution of these coloring layers may be the same or different.

The surface of the substrate may be subjected to conventionally known surface treatments such as corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, acid treatment, alkali treatment, and primer coating. Such a surface treatment may be a treatment for improving the adhesion between the substrate and the adhesive layer, in other words, the anchoring property of the adhesive layer to the substrate.

In the case where the technology disclosed herein is implemented in the form of a single-sided pressure-sensitive adhesive sheet with a base material, the back surface of the base material may be subjected to a peeling treatment as needed. The release treatment may be, for example, a treatment of applying a release treatment agent such as a general silicone, long-chain alkyl, fluorine, etc., typically in the form of a film of about 0.01 μm to about 1 μm (for example, 0.01 μm to 0.1 μm). By performing the peeling treatment, the effect of easily unwinding the roll of the adhesive sheet into a roll can be obtained.

The thickness of the base material is set in a range of 100 μm or less in total thickness of the adhesive sheet. In some embodiments, the thickness of the base material may be about 70 μm or less, about 30 μm or less, or about 15 μm or less (e.g., about 8 μm or less) depending on the purpose of use or the mode of use of the adhesive sheet. The substrate with limited thickness can well meet the requirements of thickness reduction and light weight. In addition, according to the pressure-sensitive adhesive sheet having a substrate with a limited thickness, the pressure-sensitive adhesive layer tends to function better. The lower limit of the thickness of the substrate is not particularly limited. The thickness of the base material is preferably about 2 μm or more, more preferably about 5 μm or more, for example about 10 μm or more, from the viewpoint of handleability (handleability), workability, and the like of the adhesive sheet.

< Release liner >)

In the technology disclosed herein, a release liner may be used in the formation of an adhesive layer, the production of an adhesive sheet, the preservation of an adhesive sheet before use, circulation, shape processing, and the like. The release liner is not particularly limited, and for example, a release liner having a release treatment layer on the surface of a liner substrate such as a resin film or paper; a release liner comprising a low-tackiness material such as a fluoropolymer (polytetrafluoroethylene or the like) or a polyolefin resin (polyethylene, polypropylene or the like). The release treatment layer may be formed by surface-treating the gasket base material with a release treatment agent such as silicone, long-chain alkyl, fluorine, or molybdenum sulfide.

< Properties of adhesive sheet etc. >)

(Normal adhesion F0)

The 180-degree peel strength (normal adhesion) F0 of the adhesive sheet disclosed herein to a stainless steel plate may vary depending on the purpose of use and the application site. The normal adhesive force F0 of the adhesive sheet used as the structural material is set to, for example, about 2.0N/5mm or more, preferably about 3.0N/5mm or more, more preferably about 3.5N/5mm or more, still more preferably 4.0N/5mm or more, particularly preferably 4.5N/5mm or more, and may be about 5.0N/5mm or more, from the viewpoint of obtaining good adhesive reliability to an adherend. The adhesive sheet having the above adhesive force has an adhesive force suitable for bonding fixation, and is suitable for use in portable electronic devices, for example, where the adhesive area and thickness are limited and high adhesive reliability is required. The upper limit of the adhesive force F0 is not particularly limited, and may be about 10N/5mm or less (for example, 8N/5mm or less). The adhesive force F0 is the peel strength to a stainless steel sheet measured under the conditions of a tensile speed of 300 mm/min and a peel angle of 180 degrees based on JIS Z0237, and more specifically, is measured by the method described in examples described later. In the case of a double-sided pressure-sensitive adhesive sheet having pressure-sensitive adhesive surfaces on both sides, the pressure-sensitive adhesive force F0 of each pressure-sensitive adhesive surface may be the same or different.

(adhesive force F1 after immersion in an acidic solution)

The adhesive force F1 of the adhesive sheet disclosed herein after immersion in an acidic solution is maintained at a predetermined value or more. The adhesive force F1 after immersion in an acidic solution is, for example, about 2.0N/5mm or more, preferably about 2.4N/5mm or more, more preferably about 3.0N/5mm or more, still more preferably about 3.5N/5mm or more, and particularly preferably 4.0N/5mm or more. According to the adhesive sheet exhibiting the adhesive force F1 after immersion in an acidic solution as described above, even when used in such a manner as to be exposed to an acidic liquid such as an acidic etching solution, it is possible to maintain a good adhesive state to an adherend. In accordance with the techniques disclosed herein, there is providedIs excellent in acid resistance. The upper limit of the adhesive force F1 after the immersion in an acidic solution is not particularly limited, and may be about 10N/5mm or less (for example, 8N/5mm or less). The adhesive force F1 after immersion in an acidic solution is obtained by adhering an adhesive sheet having a width of 5mm to a stainless steel plate as an adherend in an aqueous ferrous chloride solution (5% FeCl) at 50 ℃ ₂ Aqueous solution) for 30 minutes, and then measured for peel strength [ N/5mm ] under conditions of a tensile speed of 300 mm/min and a peel angle of 180 degrees ]More specifically, the measurement was performed by the method described in examples described below. In the case of a double-sided pressure-sensitive adhesive sheet having pressure-sensitive adhesive surfaces on both sides, the pressure-sensitive adhesive force F1 after immersion in an acidic solution may be the same or different.

(adhesive force F2 after immersion in an alkaline solution)

The adhesive force F2 of the adhesive sheet disclosed herein after immersion in an alkaline solution is maintained at a predetermined value or more. The adhesive force F2 after immersion in an alkaline solution is, for example, about 2.0N/5mm or more, preferably about 2.4N/5mm or more, more preferably about 3.0N/5mm or more, still more preferably about 3.5N/5mm or more, and particularly preferably 4.0N/5mm or more. According to the adhesive sheet exhibiting the adhesive force F2 after immersion in an alkaline solution as described above, for example, even when used in such a manner as to be exposed to an alkaline liquid such as an alkaline cleaning liquid, it is possible to maintain a good adhesive state to an adherend. According to the technology disclosed herein, an adhesive sheet excellent in such alkali resistance is provided. The upper limit of the adhesive force F2 after the immersion in the alkaline solution is not particularly limited, and may be about 10N/5mm or less (for example, 8N/5mm or less). The adhesive force F2 after immersion in an alkaline solution is a peel strength [ N/5mm ] measured under conditions of a tensile speed of 300 mm/min and a peel angle of 180 degrees by immersing an adhesive sheet having a width of 5mm, which is adhered to a stainless steel sheet as an adherend, in an aqueous sodium hydroxide solution (50% aqueous naoh solution) at 50 ℃ for 30 minutes, and more specifically, by a method described in examples described later. In the case of a double-sided pressure-sensitive adhesive sheet having pressure-sensitive adhesive surfaces on both sides, the pressure-sensitive adhesive force F2 after immersion in an alkaline solution may be the same or different.

(adhesive force retention after immersion in an acidic solution/after immersion in an alkaline solution)

Typically, the adhesive sheet disclosed herein has an adhesive force retention rate after immersion in an acidic solution and an adhesive force retention rate after immersion in an alkaline solution of 80% or more. The retention of adhesion after immersion in an acidic solution [% ] is obtained from the ratio (F1/F0×100) of the adhesion F1[ N/5mm ] after immersion in an acidic solution to the normal adhesion F0[ N/5mm ], and the retention of adhesion after immersion in an alkaline solution [% ] is obtained from the ratio (F2/F0×100) of the adhesion F2[ N/5mm ] after immersion in an alkaline solution to the normal adhesion F0[ N/5mm ]. An adhesive sheet satisfying the above characteristics is an adhesive sheet which maintains a sufficient adhesive force as a structural material, and can be an adhesive sheet which is less susceptible to swelling and peeling even when exposed to acidic and alkaline liquids, and which has excellent adhesive reliability. At least one (preferably both) of the adhesive force retention rate after immersion in an acidic solution and the adhesive force retention rate after immersion in an alkaline solution is preferably 85% or more, more preferably 90% or more, further preferably 95% or more, and particularly preferably 100% or more. The upper limit of the adhesive force retention rate after immersion in an acidic solution and the adhesive force retention rate after immersion in an alkaline solution is not particularly limited, and may be 300% or less, 200% or less, or 150% or less, for example. In the case of a double-sided adhesive sheet having adhesive surfaces on both sides, the adhesive force retention rate after immersion in an acidic solution and the adhesive force retention rate after immersion in an alkaline solution may be the same or different for each adhesive surface.

(total thickness of adhesive sheet)

The pressure-sensitive adhesive sheet disclosed herein (which includes a base layer in a composition including a pressure-sensitive adhesive layer and a base layer, but does not include a release liner) has a thickness (total thickness) of 100 μm or less. As described above, the pressure-sensitive adhesive sheet having a limited thickness is suitable for applications in portable electronic devices, in which miniaturization and thickness reduction are strongly demanded, in response to the demands for thickness reduction and weight reduction. In addition, according to the technology disclosed herein, by the constitution in which the thickness is limited as described above, an adhesive sheet having acid resistance and alkali resistance and capable of maintaining sufficient adhesive force can be obtained. The thickness of the pressure-sensitive adhesive sheet is preferably about 70 μm or less, more preferably about 50 μm or less, and may be about 35 μm or less, for example. The lower limit of the thickness of the pressure-sensitive adhesive sheet is not particularly limited, and may be set to about 1 μm or more, for example, about 3 μm or more, preferably about 6 μm or more, more preferably about 10 μm or more (for example, about 15 μm or more), and still more preferably about 20 μm or more. The pressure-sensitive adhesive sheet having a thickness of a predetermined value or more has good handleability and tends to be excellent in adhesive force and permeation resistance in the thickness direction of an acidic liquid and an alkaline liquid. In the substrate-less adhesive sheet, the thickness of the adhesive layer is the total thickness of the adhesive sheet.

< usage >

The pressure-sensitive adhesive sheet disclosed herein can achieve highly reliable bonding and fixing with a thickness of 100 μm or less, and is suitable for use as a structural material for various applications requiring acid resistance and alkali resistance, for example. The pressure-sensitive adhesive sheet used as a structural material is usually not intended to be peeled off from an adherend and is kept in a state of being semi-permanently adhered to the adherend. The pressure-sensitive adhesive sheet disclosed herein is suitable for use in portable electronic devices, where miniaturization and thickness reduction are strongly demanded, because it can achieve highly reliable bonding and fixing with a thickness of 100 μm or less. In addition, various members such as metal members constituting the portable electronic device may be subjected to processing such as formation of openings for various sensors such as fingerprint sensors and camera lenses. Such a processing step may include a step of immersing an acidic etching solution, washing with an alkaline washing solution, or the like, using an acidic liquid or an alkaline liquid, and therefore, by applying the adhesive sheet disclosed herein to perform bonding fixation excellent in acid resistance and alkali resistance, it is possible to process a member in a state where the adhesive sheet is attached. The adhesive sheet is particularly suitable for fixing members for portable electronic devices to which such processing is applied.

Non-limiting examples of such portable electronic devices include: a mobile phone, a smart phone, a tablet personal computer, a notebook personal computer, various wearable devices (for example, wrist wearing type worn on a wrist such as a wristwatch, modularized type worn on a part of a body with a clip, a band, or the like, eye wearing (eye wearing) type including glasses type (monocular type, binocular type, helmet type is also included), clothing type worn on a shirt, socks, hat, or the like in the form of, for example, ornaments, ear wearing type worn on an ear such as an earphone, or the like), a digital camera, a digital video camera, an acoustic device (portable music player, recording pen, or the like), a calculator (desktop calculator, or the like), a portable game device, an electronic dictionary, an electronic notepad, an electronic book, a vehicle-mounted information device, a portable radio, a portable television, a portable printer, a portable scanner, a portable modem, or the like. It should be noted that "portable" in this specification is interpreted as being insufficient to be portable only, and it is actually portable at a level that an individual (standard adult) can relatively easily carry.

The adhesive sheet disclosed herein may be used, for example, for the purpose of fixing a pressure-sensitive sensor and other members in a portable electronic device having the pressure-sensitive sensor in such a portable electronic device. In some modes, the adhesive sheet may be used for fixing the pressure-sensitive sensor and other members in an electronic apparatus (typically a portable electronic apparatus) having a function capable of specifying an absolute position on a board (typically a touch panel) corresponding to a screen by means of a means for indicating a position on the screen (typically a pen-type, mouse-type means) and a means for detecting a position.

In addition, the adhesive sheet disclosed herein is also suitable for the following uses: a back surface of a display screen (display unit) such as a touch panel display disposed in a portable electronic device. For example, in an electronic device such as a portable electronic device, there is an electronic device including a light emitting element for the purpose of image display or the like, and therefore, in order to prevent light leakage or the like, the adhesive sheet may be required to have a limited light transmittance (for example, light blocking property). For such an electronic device, an adhesive sheet having a predetermined light blocking property can be used. For example, the adhesive sheet can be used in an electronic device including various light sources such as LEDs (light emitting diodes) and light emitting elements such as self-emitting organic ELs. The electronic device may be an electronic device (typically, a portable electronic device) having an organic EL display device or a liquid crystal display device. For example, the pressure-sensitive adhesive sheet disclosed herein is suitable for use on the back surface of a display screen (display unit) such as a touch panel display disposed in a portable electronic device.

The adhesive sheet disclosed herein is suitable for portable electronic devices incorporating various sensors such as fingerprint sensors and cameras. The pressure-sensitive adhesive sheet disclosed herein is suitable for use in joining and fixing members forming openings for sensors and camera lenses of portable electronic devices, because it is possible to process (open) an adherend such as a metal member while the pressure-sensitive adhesive sheet is adhered to the adherend. Examples of the sensor (optical sensor) include an acceleration sensor, a proximity sensor, and a luminance sensor (ambient light sensor). Such a sensor may have a light receiving element for receiving light rays such as ultraviolet rays, visible rays, and infrared rays, and may have a light emitting element for emitting specific light rays such as infrared rays.

The material (adherend material) to which the pressure-sensitive adhesive sheet disclosed herein is attached is not particularly limited, and examples thereof include: examples of the metal material include metal materials such as copper, silver, gold, iron, tin, palladium, aluminum, nickel, titanium, chromium, zinc, and an alloy containing two or more of them, and examples include various resin materials (typically, plastic materials) such as polyimide resins, acrylic resins, polyether nitrile resins, polyether sulfone resins, polyester resins (PET resins, PEN resins, and the like), polyvinyl chloride resins, polyphenylene sulfide resins, polyether ether ketone resins, polyamide resins (so-called aramid resins, and the like), polyarylate resins, polycarbonate resins, and liquid crystal polymers, and inorganic materials such as alumina, zirconia, soda lime glass, quartz glass, and carbon. Among them, metallic materials such as copper, aluminum, and stainless steel, resin materials (typically plastic materials) such as polyester resins such as PET, polyimide resins, aramid resins, and polyphenylene sulfide resins are widely used. The adhesive sheet disclosed herein can be used by being stuck to a member made of the above-mentioned material. The adhesive sheet (specifically, the double-sided adhesive sheet) used as the structural material is an adhesive sheet in which each adhesive surface (first adhesive surface and second adhesive surface) adheres favorably to an adherend composed of a different material, and can be satisfactorily used for joining two or more different materials of the various adherend materials.

The material may be a material constituting a member of a product such as an electronic device. The material may be a material constituting a fixed object (for example, a back surface member such as an electromagnetic wave shield or a reinforcing plate) such as the pressure-sensitive sensor or the display unit. The fixed object is an object to which the adhesive sheet is attached, that is, an adherend. The back surface member is a member disposed on the opposite side of the front surface (visual recognition side) of the pressure-sensitive sensor and the display portion in the portable electronic device, and may be a member constituting a support portion 240 disposed on the back surface of the display device 200 shown in fig. 4 described later. The fixing object may have a single-layer structure or a multi-layer structure, or may be formed by subjecting the surface (the adhesive surface) of the adhesive sheet to various surface treatments. Although not particularly limited, as an example of the object to be fixed, there is a back surface member having a thickness of about 1 μm or more (typically about 5 μm or more, for example about 60 μm or more, further about 120 μm or more) and about 1500 μm or less (for example about 800 μm or less).

The adhesive sheet disclosed herein is suitable for use in, for example, a member having a surface (adhesive sheet adhering surface) made of a metal material. Examples of such an adherend include a member having various metal materials (for example, aluminum, stainless steel, etc.) exemplified as the above-mentioned adherend material on the surface, and examples of the preferable material include a metal member such as a stainless steel member and an aluminum member. In the form of a laminate having an adhesive sheet attached thereto, the metal member may be exposed to an acidic liquid or an alkaline liquid for opening processing or the like, and an adhesive sheet having acid resistance and alkali resistance is preferably used as a constituent of such a laminate. According to the laminate, even when exposed to an acidic liquid and an alkaline liquid due to processing of a metal member or the like, the adhesive sheet can maintain a good adhesion state to the metal member. The metal member may be, for example, a member constituting a support portion 240 of the display device 200 shown in fig. 4 described later. In the case where the pressure-sensitive adhesive sheet is a double-sided pressure-sensitive adhesive sheet and different adherends (members or articles) are adhered to the respective sides, one side of the adherend is preferably a metal member. The pressure-sensitive adhesive sheet used in the above-mentioned application may be one in which holes are formed in advance by punching or the like at positions corresponding to the processed portions (opening forming portions or the like) of the metal member.

The member or material to be adhered to the pressure-sensitive adhesive sheet (at least one adherend in the double-sided pressure-sensitive adhesive sheet) may be a member or material having light transmittance. The light transmittance of the adherend may be, for example, greater than 50% and may be 70% or more. In some preferred embodiments, the light transmittance of the adherend is 80% or more, more preferably 90% or more, and may be 95% or more (e.g., 95% to 100%). Such a material may be a resin film (for example, a polyester resin film such as a PET film) disposed on the back surface of an image display portion of various devices such as a portable electronic device. The pressure-sensitive adhesive sheet disclosed herein can be preferably used as being attached to an adherend (e.g., a member) having a light transmittance of a predetermined value or more as described above. The light transmittance is in accordance with JIS K7136:2000, the measurement was performed using a commercially available transmittance meter.

As described above, according to the technology disclosed herein, a laminate having an adhesive sheet and a member to which the adhesive sheet is attached is provided. In some embodiments, the laminate including the adhesive sheet is a laminate including the adhesive sheet and a metal member (first member). In some embodiments, an adherend having the light transmittance is adhered to the side of the adhesive sheet opposite to the metal member adhering surface. In this embodiment, the laminate including the adhesive sheet is a laminate including the adhesive sheet and a member (second member) having light transmittance. In some preferred embodiments, the laminate is a laminate having a metal member (first member), an adhesive sheet, and a member having light transmittance (second member) in this order. The pressure-sensitive adhesive sheet is also referred to as a pressure-sensitive adhesive layer in the laminate.

In some embodiments, the laminate including the adhesive sheet is a laminate including the adhesive sheet and a member (second member) having light transmittance. In such a structure, the adhesive sheet is typically a double-sided adhesive sheet. In this aspect, one adhesive surface of the adhesive sheet is adhered to the light-transmitting member. Such a laminate is also called an adhesive sheet with a light-transmitting member. The other adhesive surface of the adhesive sheet may be adhered to the metal member.

Fig. 3 illustrates the structure of the laminate. The laminate 50 shown in fig. 3 has a first member 41, a base-material-free adhesive sheet 1, and a second member 42 in this order. Specifically, in the laminate 50, one adhesive surface (first adhesive surface) 1A of the base-material-free adhesive sheet 1 is adhered to the first member 41, and the other adhesive surface (second adhesive surface) 1B of the adhesive sheet 1 is adhered to the second member 42. In this embodiment, each of the first member 41 and the second member 42 has a sheet-like or plate-like shape, and the laminated body 50 has a multilayer structure. Details of members constituting the laminate are as described above for the members, materials, and adherends, and thus, the description thereof will not be repeated.

In some preferred embodiments, the first member 41 is a metal member, and a metal material or a metal member exemplified as the adherend material is used. Such a metal member may be, for example, a member constituting a support portion 240 of the display device 200 shown in fig. 4 described later. In some preferred embodiments, the second member 42 is a light-transmitting member having the light transmittance of the light-transmitting adherend. The second member 42 is preferably a member including a resin film, more preferably a polyester-based resin film (more specifically, a PET-based resin film). The second member 42 may be, for example, a member disposed on the back surface side of the display unit in the display device. The laminate 50 described above may be typically a component such as an organic EL display device or a liquid crystal display device. The laminate 50 is suitable for use, for example, in a back surface of an image display unit (which may be a display unit such as a touch panel display) of various devices such as a portable electronic device.

The adhesive sheet disclosed herein is satisfactorily used in electronic devices including various light sources such as LEDs and light emitting elements such as self-emitting organic ELs. For example, the present invention can be satisfactorily used in electronic devices (typically portable electronic devices) having an organic EL display device and a liquid crystal display device, which require predetermined optical characteristics.

Fig. 4 is an exploded perspective view schematically showing a configuration example of the display device. As shown in fig. 4, the display device 200 included in the portable electronic device 100 includes a display unit 220 and a support unit 240, and the display unit 220 is configured by a cover member, an organic EL unit, and the like. The display device 200 further includes an adhesive sheet 230. In this configuration example, the pressure-sensitive adhesive sheet 230 is a double-sided pressure-sensitive adhesive sheet (double-sided pressure-sensitive adhesive sheet) for fixing members constituting the display unit 220 and the support unit 240. The support portion 240 is configured to include a substrate (a metal plate such as a stainless steel plate or an aluminum plate) or the like. The pressure-sensitive adhesive sheet disclosed herein is preferably used as a constituent element of the display device described above.

Among the matters disclosed by the present specification, the following are included.

[1] A display device includes a display portion including a cover member and an organic EL unit, and a support portion, wherein,

an adhesive sheet is adhered to the supporting portion,

the thickness of the adhesive sheet is 100 μm or less,

the adhesive sheet has an adhesive layer containing an acrylic polymer,

the acrylic polymer is a polymer containing 60% by weight or more of a monomer component of an alkyl (meth) acrylate having an alkyl group having 5 or more carbon atoms at the ester end,

The monomer component includes a monomer having a nitrogen atom-containing ring and a carboxyl group-containing monomer.

[2] The display device according to the above [1], wherein a total ratio of the monomer having a nitrogen atom-containing ring and the carboxyl group-containing monomer in the monomer component is 6.5% by weight or more and 40% by weight or less.

[3]As described above [1]]Or [2]]The display device, wherein the content (A) of the monomer having a nitrogen atom-containing ring _N ) Relative to the content (A) of the carboxyl group-containing monomer _C ) Ratio (A) _N /A _C ) In the range of 1 to 40.

[4] The display device according to any one of [1] to [3], wherein the monomer component contains a hydroxyl group-containing monomer at a ratio of 10% by weight or less.

[5] The display device according to any one of [1] to [4], wherein the pressure-sensitive adhesive sheet is a substrate-free double-sided pressure-sensitive adhesive sheet composed of the pressure-sensitive adhesive layer.

[6] The display device according to any one of [1] to [4], wherein the pressure-sensitive adhesive sheet further has a substrate layer, and the pressure-sensitive adhesive sheet is a double-sided pressure-sensitive adhesive sheet with a substrate having the pressure-sensitive adhesive layer on each side of the substrate layer.

[7] The display device according to any one of [1] to [6], wherein the adhesive sheet has a 180-degree peel strength F0 to a stainless steel plate of 3.0N/5mm or more.

[8] The display device according to any one of [1] to [7], wherein the adhesive force retention rate of the adhesive sheet after immersion in an acidic solution and the adhesive force retention rate after immersion in an alkaline solution are each 80% or more.

[11] An adhesive sheet having a thickness of 100 μm or less, wherein,

the adhesive sheet has an adhesive layer containing an acrylic polymer,

[12] The adhesive sheet according to the above [11], wherein the total ratio of the monomer having a nitrogen atom-containing ring and the carboxyl group-containing monomer in the monomer component is 6.5% by weight or more and 40% by weight or less.

[13]As described above [11]]Or [12]]The adhesive sheet, wherein the content (A) of the monomer having a nitrogen atom-containing ring _N ) Relative toThe content (A) of the carboxyl group-containing monomer _C ) Ratio (A) _N /A _C ) In the range of 1 to 40.

[14] The adhesive sheet according to any one of [11] to [13], wherein the monomer component comprises a hydroxyl group-containing monomer in a proportion of 10% by weight or less.

[15] The adhesive sheet according to any one of [11] to [14], wherein the adhesive sheet is a substrate-free double-sided adhesive sheet composed of the adhesive layer.

[16] The pressure-sensitive adhesive sheet according to any one of the above [11] to [14], wherein the pressure-sensitive adhesive sheet further comprises a base layer, and the pressure-sensitive adhesive sheet is a double-sided pressure-sensitive adhesive sheet with a base having the pressure-sensitive adhesive layer on each side of the base layer.

[17] The adhesive sheet according to any one of [11] to [16], wherein the adhesive sheet has a 180-degree peel strength F0 to a stainless steel plate of 3.0N/5mm or more.

[18] The adhesive sheet according to any one of [11] to [17], wherein the adhesive force retention rate of the adhesive sheet after immersion in an acidic solution and the adhesive force retention rate after immersion in an alkaline solution are each 80% or more.

[19] The adhesive sheet according to any one of [11] to [18], wherein the adhesive sheet is used for fixing a member of a portable electronic device.

[21] A laminate having a metal member (first member) and an adhesive sheet adhered to a surface of the metal member, wherein,

the thickness of the adhesive sheet is 100 μm or less,

the adhesive sheet has an adhesive layer containing an acrylic polymer,

[22] A laminate (also referred to as an adhesive sheet with a light-transmitting member) comprising: a light-transmitting member (second member) and a double-sided adhesive pressure-sensitive adhesive sheet,

the thickness of the adhesive sheet is 100 μm or less,

the adhesive sheet has an adhesive layer containing an acrylic polymer,

[23] A laminate comprising, in order, a metal member (first member), an adhesive sheet, and a member (second member) having light transmittance,

the thickness of the adhesive sheet is 100 μm or less,

the adhesive sheet has an adhesive layer containing an acrylic polymer,

[24] The laminate according to any one of [21] to [23], wherein the metal member is an aluminum member or a stainless steel member.

[25] The laminate according to [22] or [23], wherein the light transmittance of the light-transmissive member is more than 50%.

[26] The laminate according to [22], [23] or [25], wherein the light-transmitting member comprises a resin film.

[27] The laminate according to any one of [21] to [26], wherein the total ratio of the monomer having a nitrogen atom-containing ring and the carboxyl group-containing monomer in the monomer component is 6.5% by weight or more and 40% by weight or less.

[28]As described above [21]]～[27]The laminate according to any one of the preceding claimsWherein the content (A) of the monomer having a nitrogen atom-containing ring _N ) Relative to the content (A) of the carboxyl group-containing monomer _C ) Ratio (A) _N /A _C ) In the range of 1 to 40.

[29] The laminate according to any one of [21] to [28], wherein the monomer component comprises a hydroxyl group-containing monomer in an amount of 10% by weight or less.

[30] The laminate according to any one of [21] to [29], wherein the pressure-sensitive adhesive sheet is a substrate-free double-sided pressure-sensitive adhesive sheet comprising the pressure-sensitive adhesive layer.

[31] The laminate according to any one of [21] to [29], wherein the pressure-sensitive adhesive sheet further comprises a substrate layer, and the pressure-sensitive adhesive sheet is a double-sided pressure-sensitive adhesive sheet with a substrate having the pressure-sensitive adhesive layer on each side of the substrate layer.

[32] The laminate according to any one of [21] to [31], wherein the adhesive sheet has a 180-degree peel strength to a stainless steel plate of 3.0N/5mm or more.

[33] The laminate according to any one of [21] to [32], wherein the adhesive force retention rate of the adhesive sheet after immersion in an acidic solution and the adhesive force retention rate after immersion in an alkaline solution are each 80% or more.

[34] The laminate according to any one of [21] to [33], wherein the laminate is used for a portable electronic device.

Examples

Hereinafter, some embodiments of the present invention are described, but the present invention is not intended to be limited to what is shown in these embodiments. Unless otherwise specified, "parts" in the following description are weight basis.

< evaluation method >)

[ Normal adhesion F0]

A PET film having a thickness of 50 μm was stuck to one adhesive surface of a double-sided adhesive sheet at 23℃under 50% RH, and the sheet was backed, and the sheet was cut into dimensions of 5mm in width and 50mm in length to prepare a measurement sample. In this environment, a 2kg roller was reciprocated 1 time, and the adhesive surface (surface to be measured) of the measurement sample thus prepared was pressed against the surface of a stainless steel plate (SUS 304BA plate, size 10 cm. Times.10 cm). It was placed in a constant temperature bath at 50℃for 30 minutes. Then, a tensile tester was used at 23℃under 50% RH, according to JIS Z0237: 2000, peel strength (normal adhesion F0) [ N/5mm ] was measured under conditions of a tensile speed of 300 mm/min and a peel angle of 180 degrees. As the tensile testing machine, for example, the device name "tensilon" manufactured by shimadzu corporation or an equivalent thereof may be used. In the case of the single-sided pressure-sensitive adhesive sheet, the backing of the PET film is not required.

[ adhesion force F1 after immersion in an acidic solution ]

In the same manner as in the measurement of the normal adhesive force F0, a measurement sample (adhesive sheet) having a PET film backing with a width of 5mm and a length of 50mm was produced, and the adhesive surface (measurement target surface) of the measurement sample was pressed against the surface of a stainless steel plate (size 10 cm. Times.10 cm). The sample was placed horizontally so that the stainless steel plate faced the lower surface, and an aqueous ferrous chloride solution (5% FeCl) was added dropwise to the entire end surface (four sides) of the sample to be measured adhered to the stainless steel plate ₂ Aqueous solution) until the end face of the measurement sample is not exposed, immersing the end face of the measurement sample in the aqueous solution of the ferrous chloride. The whole of the above measurement sample on the stainless steel plate was covered with a PET film so that the moisture was not volatilized, and then placed in a constant temperature bath at 50 ℃ for 30 minutes. Then, the above-mentioned measurement sample adhered to the stainless steel plate was taken out from the constant temperature bath, the PET film was removed, and then the aqueous ferrous chloride solution was rinsed with tap water, and the water adhered to the measurement sample and the stainless steel plate was wiped with a waste cloth. Then, the adhesive force F1[ N/5mm after immersion in an acidic solution was measured using a tensile tester under the same conditions as those for the normal adhesive force F0 ]. The time from the impregnation of 30 minutes of the aqueous solution of the ferrous chloride to the measurement of the adhesive force is 10 minutes or less.

[ adhesion force F2 after immersion in alkaline solution ]

In the same manner as in the measurement of the normal adhesive force F0, a measurement sample (adhesive sheet) having a PET film backing with a width of 5mm and a length of 50mm was produced, and the adhesive surface (measurement target surface) of the measurement sample was pressed against the surface of a stainless steel plate (size 10 cm. Times.10 cm). The end face of the measurement sample is immersed in the aqueous sodium hydroxide solution (50% aqueous naoh solution) by placing the stainless steel plate horizontally so that the stainless steel plate faces the lower surface, and dropping the aqueous sodium hydroxide solution (50% aqueous naoh solution) onto the entire end face (four sides) of the measurement sample adhered to the stainless steel plate until the end face of the measurement sample is not exposed. The whole of the above measurement sample on the stainless steel plate was covered with a PET film so that the moisture was not volatilized, and then placed in a constant temperature bath at 50 ℃ for 30 minutes. Then, the above-mentioned measurement sample adhered to the stainless steel plate was taken out from the constant temperature bath, the PET film was removed, and then the aqueous sodium hydroxide solution was rinsed with tap water, and the water adhered to the measurement sample and the stainless steel plate was wiped with a waste cloth. Then, the adhesive force F2[ N/5mm ] after immersion in an alkaline solution was measured using a tensile tester under the same conditions as those for the normal adhesive force F0. The time from the immersion in 30 minutes of the aqueous sodium hydroxide solution to the measurement of the adhesive force was 10 minutes or less.

[ adhesive force retention ]

The adhesive force retention after immersion in an acidic solution and the adhesive force retention after immersion in an alkaline solution of each adhesive sheet were calculated as the ratio [% ] of the adhesive force F1[ N/5mm ] after immersion in an acidic solution to the normal adhesive force F0[ N/5mm ] and the ratio [% ] of the adhesive force F2[ N/5mm ] after immersion in an alkaline solution to the normal adhesive force F0[ N/5mm ], respectively. If the retention of adhesive force after immersion in an acidic solution and the retention of adhesive force after immersion in an alkaline solution were both 80% or more, the test was judged to be acceptable.

[ evaluation of end-portion swelling after immersion in an acidic solution and after immersion in an alkaline solution ]

In the above measurement of the adhesive force F1 after immersion in an acidic solution, after immersion in an aqueous ferrous chloride solution, washing with tap water was performed to visually confirm whether or not there was an end bulge on the adhesive surface between the stainless steel plate and the measurement sample after wiping the water with a waste cloth (end bulge evaluation after immersion in an acidic solution).

In the above measurement of the adhesive force F2 after immersion in an alkaline solution, after immersion in an aqueous sodium hydroxide solution, washing with tap water was performed to visually confirm whether or not there was an end bulge on the adhesive surface between the stainless steel plate and the measurement sample after wiping the water with a waste cloth (end bulge evaluation after immersion in an alkaline solution).

The resin composition was judged to be "good" (acceptable) when no edge ridge was found after the impregnation in the acidic solution and after the impregnation in the alkaline solution, and was judged to be "x" when an edge ridge was found.

< example 1 >

(preparation of acrylic Polymer)

To a reaction vessel having a stirrer, a thermometer, a nitrogen inlet pipe, a reflux condenser and a dropping funnel, 75 parts of 2-ethylhexyl acrylate (2 EHA), 3 parts of Acrylic Acid (AA), 0.1 part of 2-hydroxyethyl acrylate (HEA) and 25 parts of N-Acryloylmorpholine (ACMO) as monomer components and ethyl acetate as a polymerization solvent were charged, and stirred for 2 hours while introducing nitrogen. The oxygen in the polymerization system was thus removed, and then 0.2 part of 2,2' -Azobisisobutyronitrile (AIBN) was added as a polymerization initiator, and solution polymerization was performed at 60 ℃ for 8 hours, thereby obtaining a solution of the acrylic polymer (A1). The Mw of the acrylic polymer (A1) was about 110X 10 ⁴ 。

(preparation of adhesive composition)

To 100 parts of the acrylic polymer (A1) contained in the above-mentioned acrylic polymer (A1) solution, 0.03 parts of an epoxy-based crosslinking agent (trade name "tetra d-C", manufactured by mitsubishi gas chemical company, 1, 3-bis (N, -diglycidyl aminomethyl) cyclohexane) was added as a crosslinking agent, and stirred and mixed, thereby preparing an adhesive composition.

(production of adhesive sheet)

The adhesive composition was applied to a release surface of a release liner made of polyester (trade name "DIAFOIL MRF", manufactured by Mitsubishi polyester Co., ltd.) having a thickness of 38. Mu.m, and dried at 100℃for 2 minutes, thereby forming an adhesive layer having a thickness of 35. Mu.m. A release liner made of polyester (trade name "DIAFOIL MRF", manufactured by Mitsubishi polyester Co., ltd.) having a thickness of 25 μm was laminated on the adhesive layer. Thus, a substrate-free double-sided pressure-sensitive adhesive sheet having a thickness of 35 μm and double-sided protected by the two polyester release liners was obtained.

< example 2 >

To 100 parts of the acrylic polymer (A1) contained in the solution of the acrylic polymer (A1) prepared in example 1, 30 parts of a tackifying resin (B1) (product name "Haritak SE10", manufactured by Ha Lima chemical company, hydrogenated rosin glyceride, softening point 75 to 85 ℃), 2 parts of an isocyanate-based crosslinking agent (trade name "cornate L", manufactured by eastern co., 75% ethyl acetate solution of trimethylolpropane/toluene diisocyanate trimer adduct) and 0.04 parts of an epoxy-based crosslinking agent (trade name "tetra d-C", manufactured by mitsubishi gas chemical company, 1, 3-bis (N, N' -diglycidyl aminomethyl) cyclohexane) were added, and stirred and mixed, thereby preparing an adhesive composition. A base material-free double-sided adhesive sheet of this example was produced in the same manner as in example 1, except that the obtained adhesive composition was used.

< example 3 >

To the acrylic polymer (A1) solution prepared in example 1, 30 parts of the tackifying resin (B1), 2 parts of the isocyanate-based crosslinking agent as a crosslinking agent, and 0.05 part of the epoxy-based crosslinking agent were added to 100 parts of the acrylic polymer (A1) contained in the solution, and carbon black particles (trade name "Multi rack a903", manufactured by eastern color corporation, average particle diameter 400 nm) were added to the adhesive layer so as to be 6.58%, and the mixture was stirred and mixed, thereby preparing an adhesive composition. A substrate-free double-sided adhesive sheet of this example was produced in the same manner as in example 1, except that the obtained adhesive composition was used.

< example 4 >

To 100 parts of the acrylic polymer (A1) contained in the solution of the acrylic polymer (A1) prepared in example 1, 10 parts of the above-mentioned tackifying resin (B1) and 15 parts of the tackifying resin (B2) (product name "Haritak PCJ", manufactured by Ha Lima chemical company, polymerized rosin ester, softening point of about 118 ℃ to 128 ℃), 2 parts of the above-mentioned isocyanate-based crosslinking agent as a crosslinking agent and 0.07 part of the above-mentioned epoxy-based crosslinking agent were added and mixed with stirring, thereby preparing an adhesive composition. A substrate-free double-sided adhesive sheet of this example was produced in the same manner as in example 1, except that the obtained adhesive composition was used.

< example 5 >

The same procedure as for the preparation of the acrylic polymer (A1) was conducted except that the monomer components were changed to 80 parts of 2EHA, 3 parts of AA, 0.1 part of HEA and 20 parts of ACMO, to obtain a solution of the acrylic polymer (A2). An adhesive composition of this example was prepared in the same manner as in example 2 except that the obtained acrylic polymer (A2) solution was used, and a base-free double-sided adhesive sheet of this example was produced in the same manner as in example 1 using the adhesive composition.

< example 6 >

The same procedure as for the preparation of the acrylic polymer (A1) was conducted except that the monomer components were changed to 65 parts of 2EHA, 3 parts of AA, 0.1 part of HEA and 35 parts of ACMO, to obtain a solution of the acrylic polymer (A3). An adhesive composition of this example was prepared in the same manner as in example 2 except that the obtained acrylic polymer (A3) solution was used, and a base-free double-sided adhesive sheet of this example was produced in the same manner as in example 1 using the adhesive composition.

< example 7 >

The same procedure as for the preparation of the acrylic polymer (A1) was conducted except that the monomer components were changed to 90 parts of 2EHA, 3 parts of AA, 0.1 part of HEA and 10 parts of ACMO, to obtain a solution of the acrylic polymer (A4). An adhesive composition of this example was prepared in the same manner as in example 2 except that the obtained acrylic polymer (A4) solution was used, and a base-free double-sided adhesive sheet of this example was produced in the same manner as in example 1 using the adhesive composition.

< example 8 >

The same procedure as for the preparation of the acrylic polymer (A1) was conducted except that the monomer components were changed to 75 parts of 2EHA, 3 parts of AA, 0.1 part of HEA and 25 parts of N-vinyl-2-pyrrolidone (NVP), to obtain a solution of the acrylic polymer (A5). An adhesive composition of this example was prepared in the same manner as in example 2 except that the obtained acrylic polymer (A5) solution was used, and a base-free double-sided adhesive sheet of this example was produced in the same manner as in example 1 using the adhesive composition.

< example 9 >

The same procedure as for the production of the acrylic polymer (A1) was conducted except that the monomer components were changed to 95 parts of 2EHA and 5 parts of AA, to obtain a solution of the acrylic polymer (A6). To the resulting acrylic polymer (A6) solution, 20 parts of a tackifying resin (B3) (trade name "YS Polyster T-115", manufactured by Anyuan chemical Co., ltd., terpene phenol resin, softening point about 115 ℃) and 0.03 part of the above-mentioned epoxy-based crosslinking agent as a crosslinking agent were added with stirring and mixing, relative to 100 parts of the acrylic polymer (A6) contained in the solution, to prepare an adhesive composition. A substrate-free double-sided adhesive sheet of this example was produced in the same manner as in example 1, except that the obtained adhesive composition was used.

< example 10 >

The same procedure as for the preparation of the acrylic polymer (A1) was conducted except that the monomer components were changed to 63 parts of 2EHA, 13 parts of HEA, 15 parts of NVP and 9 parts of Methyl Methacrylate (MMA), to obtain a solution of the acrylic polymer (A7). To the obtained acrylic polymer (A7) solution, 20 parts of the tackifying resin (B1) and 1 part of the isocyanate-based crosslinking agent as a crosslinking agent were added to 100 parts of the acrylic polymer (A7) contained in the solution, and the mixture was stirred and mixed to prepare an adhesive composition. A substrate-free double-sided adhesive sheet of this example was produced in the same manner as in example 1, except that the obtained adhesive composition was used.

< example 11 >

The same procedure as for the preparation of the acrylic polymer (A1) was conducted except that the monomer components were changed to 75 parts of n-Butyl Acrylate (BA), 3 parts of AA, 0.1 part of HEA and 25 parts of ACMO, to obtain a solution of the acrylic polymer (A8). An adhesive composition of this example was prepared in the same manner as in example 2 except that the obtained acrylic polymer (A8) solution was used, and a base-free double-sided adhesive sheet of this example was produced in the same manner as in example 1 using the adhesive composition.

< example 12 >

The same procedure as for the production of the acrylic polymer (A1) was conducted except that the monomer components were changed to 95 parts of BA and 5 parts of AA, to obtain a solution of the acrylic polymer (A9). To the resulting acrylic polymer (A9) solution, 20 parts of the tackifying resin (B3), 3 parts of the isocyanate-based crosslinking agent as a crosslinking agent, and 0.01 part of the epoxy-based crosslinking agent were added to 100 parts of the acrylic polymer (A9) contained in the solution, and the mixture was stirred and mixed to prepare an adhesive composition. A substrate-free double-sided adhesive sheet of this example was produced in the same manner as in example 1, except that the obtained adhesive composition was used.

The summary and evaluation results of the adhesive sheets of each example are shown in table 1.

As shown in Table 1, in the adhesive sheets of examples 1 to 12 having a thickness of 100 μm or less, in examples 1 to 8 using as the adhesive component an acrylic polymer containing 60% by weight or more of an alkyl (meth) acrylate having an alkyl group having 5 or more carbon atoms at the ester end (C5 or more alkyl (meth) acrylate), a monomer having a nitrogen atom-containing ring (N-ring-containing monomer) and a carboxyl group-containing monomer as the monomer components, the normal adhesive force F0 was 3.0N/5mm or more, and the adhesive force retention rates after immersion in an acidic solution and after immersion in an alkaline solution were 80% or more. On the other hand, in examples 9 to 12, in which an acrylic polymer containing no one of a C5 or more alkyl (meth) acrylate, an N-ring-containing monomer, and a carboxyl-containing monomer as a monomer component was used in the adhesive, the normal adhesive force F0 was less than 3.0N/5mm, or the adhesive force retention after immersion in an acidic solution or after immersion in an alkaline solution was less than 80%.

More specifically, in example 9 using an acrylic polymer composed of a monomer containing no N-ring monomer, the adhesive force retention rate after immersion in an alkaline solution was lowered, and in example 10 using an acrylic polymer composed of a monomer containing no carboxyl group monomer, the adhesive force retention rate after immersion in an acidic solution was lowered. In example 9, the cohesive force was reduced because the N-ring-containing monomer and the carboxyl group-containing monomer were not used, and in example 10, the penetration of the acidic liquid into the adhesive was considered to be insufficient because the carboxyl group-containing monomer was not used. In addition, example 11, which does not contain a monomer composition of an alkyl (meth) acrylate of C5 or more, does not have sufficient normal adhesion F0. It is considered that the wettability of the adhesive surface is insufficient and sufficient adhesion is not exhibited. In example 12 in which the main monomer was changed to BA from example 9, the adhesive force retention rate after immersion in an acidic solution and after immersion in an alkaline solution was further decreased. According to the comparison of example 9 and example 12, it is considered that, according to the acrylic polymer containing the alkyl (meth) acrylate of C5 or more as the monomer component, the wettability of the adhesive surface is improved compared with the case of using BA in which the number of carbon atoms of the alkyl group is 4, and the penetration of the acidic solution and the alkaline solution from the adhesive sheet end face to the adhesive interface is suppressed.

From the above results, it is found that by using an adhesive agent comprising 60% by weight or more of an alkyl (meth) acrylate having an alkyl group having 5 or more carbon atoms at the ester end as a monomer component and comprising an acrylic polymer of a monomer having a nitrogen atom-containing ring and a carboxyl group-containing monomer, even if the thickness of the adhesive sheet is limited to a constitution of 100 μm or less, sufficient adhesive force can be maintained as a structural material after exposure to an acidic liquid and an alkaline liquid.

Specific examples of the present invention have been described in detail hereinabove, but these examples are merely illustrative and do not limit the claims. The technology described in the claims includes what is obtained by variously modifying or changing the specific examples illustrated above.

Description of the reference numerals

1 adhesive sheet

1A first adhesive surface

1B second adhesive face

10. Substrate (substrate layer)

21. Adhesive layer (first adhesive layer)

21A adhesive side, first adhesive side

21B adhesive side, second adhesive side

22 adhesive layer (second adhesive layer)

31. 32 release liner

41. First component

42. Second component

50. Laminate body

100 portable electronic device

200 display device

220 display unit

240 support part

Claims

1. An adhesive sheet having a thickness of 100 μm or less, wherein,

The adhesive sheet has an adhesive layer containing an acrylic polymer,

2. The adhesive sheet according to claim 1, wherein the total ratio of the monomer having a nitrogen atom-containing ring and the carboxyl group-containing monomer in the monomer component is 6.5% by weight or more and 40% by weight or less.

3. The adhesive sheet according to claim 1 or 2, wherein the content (a _N ) Relative to the content (A) of the carboxyl group-containing monomer _C ) Ratio (A) _N /A _C ) In the range of 1 to 40.

4. The adhesive sheet according to any one of claims 1 to 3, wherein the monomer component comprises a hydroxyl group-containing monomer in a proportion of 10% by weight or less.

5. The adhesive sheet according to any one of claims 1 to 4, wherein the adhesive sheet is a substrate-free double-sided adhesive sheet composed of the adhesive layer.

6. The adhesive sheet according to any one of claims 1 to 4, wherein the adhesive sheet further has a substrate layer, and the adhesive sheet is a double-sided adhesive sheet with a substrate having the adhesive layer on each side of the substrate layer.

7. The adhesive sheet according to any one of claims 1 to 6, wherein the adhesive sheet is used for fixing a member of a portable electronic device.

8. A display device includes a display portion including a cover member and an organic EL unit, and a support portion, wherein,

an adhesive sheet having a thickness of 100 μm or less is adhered to the support portion,

the adhesive sheet has an adhesive layer containing an acrylic polymer,

9. A laminate having a metal member and an adhesive sheet adhered to a surface of the metal member, wherein,

the thickness of the adhesive sheet is 100 μm or less,

the adhesive sheet has an adhesive layer containing an acrylic polymer,