JP6205081B1 - Adhesive sheet - Google Patents

Abstract

The present invention provides a pressure-sensitive adhesive sheet having good metal corrosion prevention and excellent member holding performance. A pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer formed from a pressure-sensitive adhesive composition comprising a base polymer, two or more types of cross-linking agents having different types of cross-linkable functional groups, and an azole anticorrosive agent. Provided. Here, one of the two or more crosslinking agents is an isocyanate crosslinking agent. The monomer component constituting the base polymer includes a carboxy group-containing monomer. The content of the azole rust inhibitor in the pressure-sensitive adhesive layer is less than 8 parts by weight with respect to 100 parts by weight of the base polymer. [Selection] Figure 1

Description

  The present invention relates to an adhesive sheet.

  In general, a pressure-sensitive adhesive (also referred to as a pressure-sensitive adhesive; the same shall apply hereinafter) is in the form of a soft solid (viscoelastic body) in a temperature range near room temperature and has a property of easily adhering to an adherend by pressure. Taking advantage of such properties, the pressure-sensitive adhesive is typically in the form of a pressure-sensitive adhesive sheet including a layer of the pressure-sensitive adhesive in various industrial fields such as home appliances, automobiles, various machines, electrical equipment, and electronic equipment. It is widely used as a joining means with good workability and high adhesion reliability. The pressure-sensitive adhesive sheet is preferably used for fixing members in portable electronic devices such as mobile phones, smartphones, and tablet computers. Patent documents 1-4 are mentioned as technical literature about an adhesive sheet.

International Publication No. 2015/145767 JP 2011-154700 A JP 2006-045315 A JP-A-7-242863

  By the way, it is desirable that the pressure-sensitive adhesive sheet used for fixing a member having a metal surface has a property of preventing the metal surface from being corroded (metal corrosion preventing property). Conventionally, the representative method for preventing metal corrosion in the field of pressure-sensitive adhesive sheets employs a pressure-sensitive adhesive based on a monomer composition that does not contain a carboxy group-containing monomer as the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet. It was to do. In order to prevent metal corrosion, it has also been proposed to add a rust inhibitor such as benzotriazole to the adhesive.

  However, for example, in fixing a member in a portable electronic device, the demand for the holding performance of the member (that is, the ability to keep the member fixed) is increasing year by year from the viewpoint of durability, long life, safety, and the like. The conventional pressure-sensitive adhesive sheet designed with the intention of preventing metal corrosion cannot sufficiently respond to such an increase in demand.

  The present invention has been made in view of such circumstances, and an object thereof is to provide a pressure-sensitive adhesive sheet having good metal corrosion prevention properties and excellent member holding performance.

  According to this specification, a pressure-sensitive adhesive comprising a pressure-sensitive adhesive layer formed from a pressure-sensitive adhesive composition comprising a base polymer, two or more types of crosslinking agents having different types of crosslinkable functional groups, and an azole anticorrosive. A sheet is provided. One of the two or more crosslinking agents is an isocyanate crosslinking agent. The monomer component constituting the base polymer includes a carboxy group-containing monomer. The content of the azole rust inhibitor in the pressure-sensitive adhesive layer is less than 8 parts by weight with respect to 100 parts by weight of the acrylic polymer.

  The pressure-sensitive adhesive sheet having such a structure includes a carboxy group-containing monomer in the composition of the monomer component constituting the base polymer, thereby having good durability against the impact in the shear direction (shear impact resistance; for example, described later) It can be evaluated by impact adhesive strength). Moreover, cohesive force (for example, heat-resistant cohesive force) and metal corrosion resistance can be suitably achieved by using a combination of an isocyanate-based cross-linking agent and another cross-linking agent in a composition containing an azole anti-corrosive agent. . As a result, a pressure-sensitive adhesive sheet having good metal corrosion prevention and excellent member holding performance can be realized.

  The technique disclosed here can be preferably implemented in an embodiment where the pressure-sensitive adhesive layer has a relative dielectric constant at 300 kHz of 3 or more. Such a pressure-sensitive adhesive layer exhibiting a relative dielectric constant can be preferably used for, for example, an application for fixing a dielectric pressure sensor.

  In one embodiment, the monomer component contains 50% by weight or more of (meth) acrylate having a hydrocarbon group having 4 or less carbon atoms at the ester end. Thus, in the structure which uses as a base polymer the acrylic polymer of the monomer composition containing many monomers with a short alkyl chain, an adhesive layer with a high dielectric constant is easy to be obtained. This can be advantageous in applications where, for example, a capacitive pressure sensor is fixed.

  In one embodiment, the content of the carboxy group-containing monomer in the monomer component is more than 3% by weight. According to the monomer component having such a composition, a pressure-sensitive adhesive layer showing higher shear impact resistance tends to be realized.

  The content of the azole rust inhibitor may be, for example, 0.2 parts by weight or more and 15 parts by weight or less per 10 parts by weight of the carboxy group-containing monomer. In such a configuration, good shear impact resistance and heat-resistant cohesive strength due to the use of the carboxy group-containing monomer and metal corrosion prevention property due to the use of the azole rust preventive can be suitably achieved.

  The pressure-sensitive adhesive layer in the technology disclosed herein may contain a tackifier resin. By including a tackifying resin in the pressure-sensitive adhesive layer, it is possible to improve the adhesion to the adherend and improve the holding performance of the member.

  In the pressure-sensitive adhesive sheet according to one aspect, the tackifier resin contained in the pressure-sensitive adhesive layer contains a tackifier resin having a hydroxyl value of 30 mgKOH / g or more. By including a tackifier resin having a relatively high hydroxyl value in the pressure-sensitive adhesive layer as described above, the adhesion to the adherend can be improved and the holding performance of the member can be effectively improved. As the tackifying resin having a hydroxyl value of 30 mgKOH / g or more, for example, a phenolic tackifying resin such as a terpene phenol resin can be preferably used.

  The pressure-sensitive adhesive sheet disclosed herein preferably has a room temperature peel strength with respect to polyethylene terephthalate (PET) of 15 N / 25 mm or more. Such a pressure-sensitive adhesive sheet can exhibit better component holding performance.

  The azole rust inhibitor is at least one selected from the group consisting of 1,2,3-benzotriazole, 5-methylbenzotriazole, 4-methylbenzotriazole, and carboxybenzotriazole from the viewpoint of rust prevention effect. These benzotriazole compounds can be preferably employed.

  The pressure-sensitive adhesive sheet disclosed herein has good metal corrosion prevention properties and excellent member holding performance (for example, shear impact resistance), and thus can be suitably used for fixing members in portable electronic devices. For example, it can be preferably used in such a manner that the pressure-sensitive sensor is fixed to another member constituting the portable electronic device.

It is sectional drawing which shows one structural example of an adhesive sheet typically. It is sectional drawing which shows the other structural example of an adhesive sheet typically.

  Hereinafter, preferred embodiments of the present invention will be described. Note that matters other than the matters specifically mentioned in the present specification and necessary for the implementation of the present invention are based on the teachings on the implementation of the invention described in the present specification and the common general technical knowledge at the time of filing. Can be understood by those skilled in the art. The present invention can be carried out based on the contents disclosed in this specification and common technical knowledge in the field. Further, in the following drawings, members / parts having the same action may be described with the same reference numerals, and overlapping descriptions may be omitted or simplified. In addition, the embodiment described in the drawings is schematically illustrated for clearly explaining the present invention, and does not necessarily accurately represent the size and scale of the pressure-sensitive adhesive sheet of the present invention that is actually provided as a product. .

In the present specification, the “pressure-sensitive adhesive” refers to a material that exhibits a soft solid (viscoelastic body) state in a temperature range near room temperature and has a property of easily adhering to an adherend by pressure as described above. . The adhesive here is generally complex tensile elastic modulus E ^* (1 Hz) as defined in “CA Dahlquist,“ Adhesion: Fundamental and Practice ”, McLaren & Sons, (1966) P. 143”. It may be a material having a property satisfying <10 ⁷ dyne / cm ² (typically, a material having the above property at 25 ° C.).

  In this specification, “(meth) acryloyl” means acryloyl and methacryloyl comprehensively. Similarly, “(meth) acrylate” means acrylate and methacrylate, and “(meth) acryl” generically means acrylic and methacryl.

  In this specification, the “acrylic polymer” refers to a polymer containing monomer units derived from a monomer having at least one (meth) acryloyl group in one molecule as monomer units constituting the polymer. Hereinafter, a monomer having at least one (meth) acryloyl group in one molecule is also referred to as an “acrylic monomer”. Accordingly, the acrylic polymer in this specification is defined as a polymer including monomer units derived from an acrylic monomer. A typical example of the acrylic polymer is a polymer of a monomer component containing more than 50% by weight of an acrylic monomer. In a preferred embodiment, the proportion of the acrylic monomer in the monomer component may be about 70% by weight or more (eg, about 90% by weight or more).

  The pressure-sensitive adhesive sheet disclosed herein includes a pressure-sensitive adhesive layer formed from a pressure-sensitive adhesive composition containing a base polymer, a crosslinking agent, and a rust inhibitor. Here, the base polymer refers to a main component of a rubber-like polymer (a polymer exhibiting rubber elasticity in a temperature range near room temperature) included in the pressure-sensitive adhesive layer. Further, in this specification, “main component” refers to a component contained in an amount exceeding 50% by weight unless otherwise specified.

  The pressure-sensitive adhesive sheet disclosed herein may be a pressure-sensitive adhesive sheet with a base material in a form having the pressure-sensitive adhesive layer on one or both sides of a non-peelable base material (support base material), and the pressure-sensitive adhesive layer is peeled off. It may be a base material-less pressure-sensitive adhesive sheet (that is, a pressure-sensitive adhesive sheet not having a non-peelable base material) such as a form held by a liner. The concept of the pressure-sensitive adhesive sheet herein may include what are called pressure-sensitive adhesive tapes, pressure-sensitive adhesive labels, pressure-sensitive adhesive films and the like. The pressure-sensitive adhesive sheet disclosed herein may be in the form of a roll or a single sheet. Or the adhesive sheet of the form processed into various shapes may be sufficient.

  An example of the structure of a double-sided pressure-sensitive adhesive baseless pressure-sensitive adhesive sheet (baseless double-sided pressure-sensitive adhesive sheet) is shown in FIGS. The pressure-sensitive adhesive sheet 1 shown in FIG. 1 has a configuration in which both surfaces 21A and 21B of a base material-less pressure-sensitive adhesive layer 21 are protected by release liners 31 and 32 having at least a pressure-sensitive adhesive layer side, respectively. The pressure-sensitive adhesive sheet 2 shown in FIG. 2 has a configuration in which one surface (adhesive surface) 21A of the base material-less pressure-sensitive adhesive layer 21 is protected by a release liner 31 having both surfaces as release surfaces. When wound, the other surface (adhesive surface) 21B of the pressure-sensitive adhesive layer 21 is brought into contact with the back surface of the release liner 31 so that the other surface 21B is also protected by the release liner 31. The technique disclosed here can be preferably implemented in such a substrate-less form from the viewpoint of reducing the thickness of the pressure-sensitive adhesive sheet. Alternatively, the pressure-sensitive adhesive sheet disclosed herein may be in the form of a double-sided pressure-sensitive adhesive sheet with a base material having a pressure-sensitive adhesive layer on both surfaces of a non-peelable base material (support base material), although not particularly illustrated.

<Adhesive layer>
In the technology disclosed herein, the type of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is not particularly limited. For example, acrylic adhesives, rubber adhesives (natural rubbers, synthetic rubbers, mixed systems thereof), silicone adhesives, polyester adhesives, urethane adhesives, polyether adhesives, polyamide adhesives It may be a pressure-sensitive adhesive layer comprising one or more pressure-sensitive adhesives selected from various known pressure-sensitive adhesives such as pressure-sensitive adhesives and fluorine-based pressure-sensitive adhesives. Here, the acrylic pressure-sensitive adhesive refers to a pressure-sensitive adhesive having an acrylic polymer as a base polymer (a main component of the polymer component, that is, a component contained in excess of 50% by weight). The same applies to rubber-based adhesives and other adhesives.

  The technology disclosed herein is in the form of a pressure-sensitive adhesive sheet including a pressure-sensitive adhesive layer containing an acrylic pressure-sensitive adhesive as a main component (that is, a component contained in excess of 50% by weight) from the viewpoints of transparency and weather resistance. It can be preferably implemented. The content of the acrylic pressure-sensitive adhesive in the pressure-sensitive adhesive layer is preferably 70% by weight or more, more preferably 90% by weight or more, and may be more than 98% by weight, and is substantially composed of an acrylic pressure-sensitive adhesive. It may be an adhesive layer. Hereinafter, the pressure-sensitive adhesive sheet having an acrylic polymer as a base polymer and the pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive will be mainly described, but the pressure-sensitive adhesive sheet disclosed herein is not limited thereto.

(Acrylic polymer)
The acrylic polymer in the technology disclosed herein preferably contains an alkyl (meth) acrylate as a main monomer and a carboxy group-containing monomer, and if necessary, a submonomer copolymerizable with the main monomer. Furthermore, it is a polymer of monomer components that may be included. Here, the main monomer means a main component in the monomer component constituting the acrylic polymer, that is, a component contained in the monomer component in an amount exceeding 50% by weight.

As the alkyl (meth) acrylate, for example, a compound represented by the following formula (1) can be preferably used.
CH ₂ = C (R ¹¹ ) COOR ¹² (1)
Here, R ¹¹ in the above formula (1) is a hydrogen atom or a methyl group. R ¹² is a chain alkyl group having 1 to 20 carbon atoms (hereinafter, such a range of the number of carbon atoms may be represented as “C _1-20 ”). From the viewpoint of the storage elastic modulus of the pressure-sensitive adhesive, an alkyl (meth) acrylate in which R ¹² is a C _1-14 chain alkyl group is preferable, and R ¹² is an alkyl (meta) that is a C _1-10 chain alkyl group. ) Acrylate is more preferred.

Specific examples of the alkyl (meth) acrylate in which R ¹² is a C _1-20 chain alkyl group are not particularly limited, but for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (Meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (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) a Relate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, Examples include octadecyl (meth) acrylate, nonadecyl (meth) acrylate, and eicosyl (meth) acrylate. These alkyl (meth) acrylates can be used alone or in combination of two or more. Preferable examples of the alkyl (meth) acrylate include n-butyl acrylate (BA) and 2-ethylhexyl acrylate (2EHA).

  The proportion of the alkyl (meth) acrylate in the monomer component constituting the acrylic polymer is typically more than 50% by weight, for example, 70% by weight or more, and may be 85% by weight or more. It is good also as weight% or more. The proportion of the alkyl (meth) acrylate in the monomer component is typically less than 100% by weight, and is usually suitably 99.5% by weight or less, and 98% by weight or less (eg, 97% by weight). %)). According to the monomer component having such a composition, a pressure-sensitive adhesive sheet excellent in member holding performance is easily obtained.

The technique disclosed here can be preferably carried out in an embodiment in which the monomer component contains 50% by weight or more of C _1-4 alkyl (meth) acrylate. According to the acrylic polymer having such a monomer composition, the pressure-sensitive adhesive layer has a higher relative dielectric constant than an acrylic polymer having a main monomer of (meth) acrylate having an alkyl group having 5 or more carbon atoms at the ester end. Tend to be formed. The high dielectric constant of the pressure-sensitive adhesive layer means that the pressure-sensitive sensor is improved in sensitivity in a pressure-sensitive adhesive sheet that is assumed to be attached to a pressure-sensitive sensor (for example, a capacitive pressure-sensitive sensor). From the viewpoint of Such a pressure-sensitive adhesive sheet is typically in the form of a double-sided pressure-sensitive adhesive sheet, and can be preferably used, for example, for fixing a capacitive pressure sensor. From the viewpoint of further increasing the relative dielectric constant, the proportion of the C _1-4 alkyl (meth) acrylate in the monomer component may be 70% by weight or more, or 85% by weight or more (for example, 90% by weight or more). On the other hand, from the viewpoint of obtaining good member retention performance, the proportion of C _1-4 alkyl (meth) acrylate in the monomer component is usually suitably 99.5% by weight or less, and 98% by weight or less ( For example, it may be less than 97% by weight).

The technique disclosed here can be preferably implemented in an embodiment in which the monomer component contains 50% by weight or more (eg, 70% by weight or more, or 85% by weight or more, or 90% by weight or more) of C _2-4 alkyl acrylate. Specific examples of the C _2-4 alkyl acrylate include ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate (BA), isobutyl acrylate, s-butyl acrylate, and t-butyl acrylate. _C2-4 alkyl acrylate can be used individually by 1 type or in combination of 2 or more types. According to such an embodiment, it is easy to realize a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer having a high relative dielectric constant and having good adhesion to a member (adhered body). Among these, a preferred embodiment includes an embodiment in which the monomer component contains more than 50% by weight of BA (for example, 70% by weight or more, or 85% by weight or more, or 90% by weight or more). On the other hand, from the viewpoint of obtaining good member retention performance, the proportion of C _1-4 alkyl (meth) acrylate in the monomer component is usually suitably 99.5% by weight or less, and 98% by weight or less ( For example, it may be less than 97% by weight).

The technique disclosed herein may also include an embodiment in which the monomer component contains 50% by weight or more (eg, 70% by weight or more, 85% by weight or more, or 90% by weight or more) of C _5-20 alkyl (meth) acrylate. Can be implemented. According to the acrylic polymer having such a monomer composition, a pressure-sensitive adhesive layer having a lower relative dielectric constant tends to be formed as compared with an acrylic polymer having a monomer composition containing _C1-4 alkyl (meth) acrylate as a main monomer. . The low dielectric constant of the pressure-sensitive adhesive layer makes it difficult to impair the signal of the pressure-sensitive sensor in a pressure-sensitive adhesive sheet that is assumed to be attached to a pressure-sensitive sensor (for example, a resistance-type pressure-sensitive sensor) ( For example, it can be advantageous from the viewpoint of reducing signal strength. Such a pressure-sensitive adhesive sheet is typically in the form of a double-sided pressure-sensitive adhesive sheet and can be preferably used, for example, for fixing a resistance-type pressure-sensitive sensor. As _C5-20 alkyl (meth) acrylate, _C6-14 alkyl (meth) acrylate is preferable. In one embodiment, C _6-10 alkyl acrylate (eg, C _8-10 alkyl acrylate) may be preferably employed.

  In the base polymer in the technology disclosed herein, a monomer component constituting the base polymer (for example, an acrylic polymer) includes a carboxy group-containing monomer. When the monomer component contains a carboxy group-containing monomer, it is easy to obtain a pressure-sensitive adhesive sheet exhibiting good durability (shear impact resistance) against impact in the shear direction. Moreover, it may be advantageous for improving the adhesion between the pressure-sensitive adhesive layer and the adherend (such as a member to be fixed). Examples of the carboxy group-containing monomer include ethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, crotonic acid, and isocrotonic acid; maleic acid, itaconic acid, citracone Examples thereof include ethylenically unsaturated dicarboxylic acids such as acids and anhydrides thereof (maleic anhydride, itaconic anhydride, etc.); Any of these may be used alone or in combinations of two. Among these, preferable carboxy group-containing monomers include acrylic acid (AA) and methacrylic acid (MAA). AA is particularly preferred.

  The content of the carboxy group-containing monomer in the monomer component constituting the base polymer can be, for example, 0.2% by weight or more (typically 0.5% by weight or more) of the monomer component. It is suitable to set it as weight% or more, and it is good also as 2 weight% or more, and good also as 3 weight% or more. By setting the content of the carboxy group-containing monomer to more than 3% by weight, a higher effect (for example, an effect of improving impact adhesive strength) can be exhibited, and a pressure-sensitive adhesive sheet with more excellent member holding performance can be realized. . From such a viewpoint, in one embodiment, the content of the carboxy group-containing monomer can be 3.2% by weight or more of the monomer component, may be 3.5% by weight or more, or may be 4% by weight or more. It is good also as 4.5 weight% or more. The upper limit of the content of the carboxy group-containing monomer is not particularly limited, but can be, for example, 15% by weight or less, or 12% by weight or less, from the viewpoint of easily reducing the amount of the rust inhibitor used, and may be 10% by weight. % Or less. The technique disclosed here is such that the content of the carboxy group-containing monomer is 7% by weight or less (typically less than 7% by weight, for example, 6.8% by weight or 6.0% by weight or less). Certain embodiments can also be preferably implemented.

A submonomer having copolymerizability with the main monomer, alkyl (meth) acrylate, can be useful for introducing a crosslinking point into the acrylic polymer or increasing the cohesive strength of the acrylic polymer. The submonomer can also help to adjust the dielectric constant of the adhesive layer. As a submonomer, the following functional group containing monomers can be used individually by 1 type or in combination of 2 or more types, for example.
Hydroxyl group-containing monomers: For example, hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; Unsaturated alcohols such as vinyl alcohol and allyl alcohol; polypropylene glycol mono (meth) acrylate.
Amide group-containing monomer: For example, (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methylolpropane (meth) acrylamide, N-methoxymethyl (Meth) acrylamide, N-butoxymethyl (meth) acrylamide.
Amino group-containing monomer: for example, aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate.
Monomers having an epoxy group: for example, glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, allyl glycidyl ether.
Cyano group-containing monomer: for example, acrylonitrile, methacrylonitrile.
Keto group-containing monomers: for example, diacetone (meth) acrylamide, diacetone (meth) acrylate, vinyl methyl ketone, vinyl ethyl ketone, allyl acetoacetate, vinyl acetoacetate.
Monomers having a nitrogen atom-containing ring: for example, N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrazine, N-vinyl Pyrrole, N-vinylimidazole, N-vinyloxazole, N-vinylmorpholine, N-vinylcaprolactam, N- (meth) acryloylmorpholine.
Alkoxysilyl group-containing monomer: For example, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxy Propylmethyldiethoxysilane.

  When the monomer component constituting the acrylic polymer includes the functional group-containing monomer as described above, the content of the functional group-containing monomer in the monomer component is not particularly limited. From the viewpoint of appropriately exhibiting the effect of the use of the functional group-containing monomer, the content of the functional group-containing monomer in the monomer component can be, for example, 0.1% by weight or more, and usually 0.5% by weight or more. It is appropriate to make it 1% by weight or more. Moreover, from the viewpoint of easily balancing the adhesion performance in relation to the main monomer and the carboxy group-containing monomer, the content of the functional group-containing monomer in the monomer component is usually suitably 40% by weight or less, It is preferably 20% by weight or less, and may be 10% by weight or less (for example, 5% by weight or less). The technology disclosed herein is also preferably implemented in an embodiment in which the monomer component does not substantially contain a functional group-containing monomer (for example, an embodiment in which the monomer component is substantially composed only of an alkyl (meth) acrylate and a carboxy group-containing monomer). obtain. Here, that the monomer component does not substantially contain a functional group-containing monomer means that at least intentionally the functional group-containing monomer is not used, for example, 0.05% by weight or less (typically 0.01% It is acceptable that unintentional inclusion of functional group-containing monomers in the order of (% by weight or less).

  The monomer component constituting the acrylic polymer may contain a copolymer component other than the above-mentioned submonomer for the purpose of improving cohesive force. Examples of other copolymerization components include vinyl ester monomers such as vinyl acetate, vinyl propionate and vinyl laurate; aromatic vinyl compounds such as styrene, substituted styrene (α-methylstyrene, etc.), vinyl toluene; cyclohexyl ( Cycloalkyl (meth) acrylates such as meth) acrylate, cyclopentyl (meth) acrylate, isobornyl (meth) acrylate; aryl (meth) acrylate (eg phenyl (meth) acrylate), aryloxyalkyl (meth) acrylate (eg phenoxyethyl ( (Meth) acrylates), arylalkyl (meth) acrylates (eg benzyl (meth) acrylates) and other aromatic ring-containing (meth) acrylates; ethylene, propylene, isoprene, butadiene, isobutylene Olefin-based monomers; chlorine-containing monomers such as vinyl chloride and vinylidene chloride; isocyanate group-containing monomers such as 2- (meth) acryloyloxyethyl isocyanate; alkoxy groups such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate Monomer; Vinyl ether monomers such as methyl vinyl ether and ethyl vinyl ether; Polymerization of 2 or more (for example, 3 or more) per molecule such as 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, etc. And a polyfunctional monomer having a functional group (for example, a (meth) acryloyl group).

  The amount of such other copolymerization component is not particularly limited as long as it is appropriately selected depending on the purpose and application, but it is usually appropriate to be 0.05% by weight or more from the viewpoint of appropriately exhibiting the effect of use. It is good also as 0.5 weight% or more. Further, from the viewpoint of easily balancing the adhesive performance, the content of the other copolymer component in the monomer component is usually suitably 20% by weight or less, and 10% by weight or less (eg, 5% by weight or less). ). The technique disclosed here can also be preferably implemented in an embodiment in which the monomer component does not substantially contain other copolymerization components. Here, that the monomer component does not substantially contain other copolymer component means that at least intentionally the other copolymer component is not used, and the other copolymer component is, for example, 0.01% by weight or less. To some extent, unintentional inclusion is acceptable.

The copolymer composition of the acrylic polymer is suitably designed so that the glass transition temperature (Tg) of the polymer is about −15 ° C. or lower (for example, about −70 ° C. or higher and −15 ° C. or lower). Here, the Tg of the acrylic polymer refers to a Tg determined by the Fox formula based on the composition of the monomer component used for the synthesis of the polymer. The formula of Fox is a relational expression between Tg of a copolymer and glass transition temperature Tgi of a homopolymer obtained by homopolymerizing each of the monomers constituting the copolymer, as shown below.
1 / Tg = Σ (Wi / Tgi)
In the above Fox equation, Tg is the glass transition temperature (unit: K) of the copolymer, Wi is the weight fraction of monomer i in the copolymer (copolymerization ratio on a weight basis), and Tgi is the monomer i. Represents the glass transition temperature (unit: K) of the homopolymer.

As the glass transition temperature of the homopolymer used for the calculation of Tg, the values described in known materials are used. For example, for the monomers listed below, the following values are used as the glass transition temperature of the homopolymer of the monomer.
2-Ethylhexyl acrylate -70 ° C
Isononyl acrylate -60 ° C
n-Butyl acrylate -55 ° C
Ethyl acrylate -22 ° C
Methyl acrylate 8 ℃
Methyl methacrylate 105 ° C
2-hydroxyethyl acrylate -15 ° C
4-hydroxybutyl acrylate -40 ° C
Vinyl acetate 32 ° C
Acrylic acid 106 ℃
Methacrylic acid 228 ° C

  Regarding the glass transition temperature of homopolymers of monomers other than those exemplified above, the values described in the “Polymer Handbook” (3rd edition, John Wiley & Sons, Inc., 1989) are used. The highest value is adopted for the monomer whose values are described in this document. When not described in the above Polymer Handbook, values obtained by the measuring method described in JP-A-2007-51271 are used.

  Although not particularly limited, from the viewpoint of adhesion to an adherend (for example, a member to be fixed), the Tg of the acrylic polymer is advantageously about −25 ° C. or less, preferably about − 35 ° C. or lower, more preferably about −40 ° C. or lower. In one embodiment, from the viewpoint of cohesive strength, the Tg of the acrylic polymer may be, for example, about −65 ° C. or more, about −60 ° C. or more, or about −55 ° C. or more. The technique disclosed herein can be preferably implemented in an embodiment where the Tg of the acrylic polymer is about −65 ° C. or more and −35 ° C. or less (for example, about −55 ° C. or more and −40 ° C. or less). The Tg of the acrylic polymer can be adjusted by appropriately changing the monomer composition (that is, the type and amount ratio of monomers used for the synthesis of the polymer).

  The method for obtaining the acrylic polymer is not particularly limited, and various polymerization methods known as synthetic methods for acrylic polymers, such as solution polymerization method, emulsion polymerization method, bulk polymerization method, suspension polymerization method, photopolymerization method, etc. Can be adopted as appropriate. For example, a solution polymerization method can be preferably employed. The polymerization temperature at the time of performing the solution polymerization can be appropriately selected according to the type of monomer and solvent to be used, the type of polymerization initiator, and the like, for example, about 20 ° C to 170 ° C (typically 40 ° C to 140 ° C). C.).

  The solvent (polymerization solvent) used for the solution polymerization can be appropriately selected from conventionally known organic solvents. For example, aromatic compounds such as toluene (typically aromatic hydrocarbons); acetates such as ethyl acetate; aliphatic or alicyclic hydrocarbons such as hexane and cyclohexane; 1,2-dichloroethane, etc. Halogenated alkanes; lower alcohols such as isopropyl alcohol (for example, monohydric alcohols having 1 to 4 carbon atoms); ethers such as tert-butyl methyl ether; ketones such as methyl ethyl ketone; Any one kind of solvent or two or more kinds of mixed solvents can be used.

  The initiator used for the polymerization can be appropriately selected from conventionally known polymerization initiators according to the type of the polymerization method. For example, one or more azo polymerization initiators such as 2,2'-azobisisobutyronitrile (AIBN) can be preferably used. Other examples of the polymerization initiator include persulfates such as potassium persulfate; peroxide initiators such as benzoyl peroxide and hydrogen peroxide; substituted ethane initiators such as phenyl-substituted ethane; aromatic carbonyl compounds And the like. Still another example of the polymerization initiator includes a redox initiator based on a combination of a peroxide and a reducing agent. Such a polymerization initiator can be used individually by 1 type or in combination of 2 or more types. The amount of the polymerization initiator used may be a normal amount, for example, about 0.005 to 1 part by weight (typically about 0.01 to 1 part by weight with respect to 100 parts by weight of the monomer component. ) Can be selected from the range.

  According to the solution polymerization, a polymerization reaction liquid in a form in which an acrylic polymer is dissolved in an organic solvent is obtained. The pressure-sensitive adhesive layer in the technology disclosed herein may be formed from a pressure-sensitive adhesive composition containing the above-mentioned polymerization reaction liquid or an acrylic polymer solution obtained by subjecting the reaction liquid to an appropriate post-treatment. As said acrylic polymer solution, what prepared the said polymerization reaction liquid to the appropriate viscosity (concentration) as needed can be used. Alternatively, an acrylic polymer solution prepared by synthesizing an acrylic polymer by a polymerization method other than solution polymerization (for example, emulsion polymerization, photopolymerization, bulk polymerization, etc.) and dissolving the acrylic polymer in an organic solvent may be used. Good.

The weight average molecular weight (Mw) of the base polymer (preferably an acrylic polymer) in the technique disclosed herein is not particularly limited, and may be, for example, in the range of about 10 × 10 ^{4 to} 500 × 10 ⁴ . From the viewpoint of adhesive performance, the Mw of the base polymer is about 30 × 10 ⁴ to 200 × 10 ⁴ (more preferably about 45 × 10 ^{4 to} 150 × 10 ⁴ , typically about 65 × 10 ^{4 to} 130 × 10 ^4. It is preferable that it exists in the range of ⁴ ). Here, Mw refers to a value in terms of standard polystyrene obtained by GPC (gel permeation chromatography). As the GPC apparatus, for example, a model name “HLC-8320GPC” (column: TSKgelGMH-H (S), manufactured by Tosoh Corporation) can be used.

(Rust inhibitor)
The pressure-sensitive adhesive layer in the technology disclosed herein contains an azole rust inhibitor. As the azole rust preventive agent, a 5-membered aromatic compound containing two or more heteroatoms, and an azole compound containing at least one of the heteroatoms as a nitrogen atom is preferably used. Can be. As the azole compound, an azole compound that has been conventionally used as a rust preventive for metals such as copper can be appropriately employed.

  Examples of such azole compounds include imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, selenazole, 1,2,3-triazole, 1,2,4-triazole, 1,2,5-oxa. Diazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,3,4-thiadiazole, tetrazole, 1,2,3,4-thiatriazole, etc. Azoles thereof; derivatives thereof; amine salts thereof; metal salts thereof; and the like. Examples of azole derivatives include compounds having a structure containing a condensed ring of an azole ring and another ring, for example, a benzene ring. Specific examples include indazole, benzimidazole, benzotriazole (that is, 1,2,3-benzotriazole having a structure in which an azole ring and a benzene ring of 1,2,3-triazole are condensed), benzothiazole, and the like. Furthermore, these derivatives are alkylbenzotriazoles (for example, 5-methylbenzotriazole, 5-ethylbenzotriazole, 5-n-propylbenzotriazole, 5-isobutylbenzotriazole, 4-methylbenzotriazole), alkoxybenzotriazole (for example, 5-methoxybenzotriazole), alkylaminobenzotriazole, alkylaminosulfonylbenzotriazole, mercaptobenzotriazole, hydroxybenzotriazole, nitrobenzotriazole ( 4-nitrobenzotriazole), halobenzotriazole (eg 5-chlorobenzotriazole), hydroxyalkylbenzotriazole, hydrobenzotriazole, aminobenzotriazole, (substituted aminomethyl) -tolyltriazole, carboxybenzotriazole, N-alkylbenzo Examples thereof include triazole, bisbenzotriazole, naphthotriazole, mercaptobenzothiazole, aminobenzothiazole, amine salts thereof, metal salts thereof, and the like. Other examples of azole derivatives include non-fused ring structure azole derivatives such as 3-amino-1,2,4-triazole and 5-phenyl-1H-tetrazole on non-fused azole rings. Examples thereof include compounds having a structure having a substituent. An azole type compound can be used individually by 1 type or in combination of 2 or more types.

  A preferred example of a compound that can be used as an azole rust inhibitor is a benzotriazole rust inhibitor containing a benzotriazole compound as an active ingredient. The technique disclosed here can be preferably implemented, for example, in an embodiment in which the base polymer is an acrylic polymer and the rust inhibitor is a benzotriazole rust inhibitor. In such an embodiment, a pressure-sensitive adhesive sheet having good metal corrosion prevention properties and excellent member holding performance can be suitably realized.

  The benzotriazole-based compound is not particularly limited as long as it is a compound having a benzotriazole skeleton, but having a structure represented by the following formula (2) provides a more excellent corrosion prevention effect. preferable.

Here, in the above formula (2), R ¹ is a substituent on the benzene ring, for example, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or 6 to 14 carbon atoms. Aryl group, carboxy group, carboxyalkyl group having 2 to 6 carbon atoms, amino group, mono- or di-C _1-10 alkylamino group, amino-C _1-6 alkyl group, mono- or di-C _1-10 It may be selected from substituents such as alkylamino-C _1-6 alkyl groups, mercapto groups, alkoxycarbonyl groups having 1 to 6 carbon atoms, and the like. N in the formula (2) is an integer of 0 to 4, and when n is 2 or more, the n R ¹ contained in the formula (2) may be the same or different from each other. Also good. R ² in the above formula (2) is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 14 carbon atoms, an amino group, mono or di -C _1-10 alkylamino group, amino-C _1-6 alkyl group, mono- or di-C _1-10 alkylamino-C _1-6 alkyl group, mercapto group, alkoxycarbonyl group having 1 to 12 carbon atoms, And so on. R ¹ and R ² may be the same or different. Preferable examples of the benzotriazole compound represented by the formula (2) include 1,2,3-benzotriazole, 5-methylbenzotriazole, 4-methylbenzotriazole, carboxybenzotriazole and the like.

  The content of the azole rust preventive agent (for example, benzotriazole rust preventive agent) is not particularly limited, and for example, 0.01 parts by weight or more (typically 0.05 parts by weight with respect to 100 parts by weight of the base polymer). Or more). From the viewpoint of obtaining a better metal corrosion prevention effect, the content may be 0.1 parts by weight or more, 0.3 parts by weight or more, or 0.5 parts by weight or more. On the other hand, from the viewpoint of increasing the cohesive force of the pressure-sensitive adhesive (for example, heat-resistant cohesive force), the content of the azole rust preventive is usually suitably less than 8 parts by weight relative to 100 parts by weight of the base polymer. It may be 6 parts by weight or less, or 5 parts by weight or less.

  Although it does not specifically limit, in one aspect | mode, content of the azole type | system | group antirust agent in an adhesive layer is 0.2 weight part per 10 weight part of carboxy group containing monomers contained in the monomer component which comprises a base polymer. The amount corresponding to the above can be used. The content of the azole rust inhibitor per 10 parts by weight of the carboxy group-containing monomer may be 0.5 parts by weight or more, 1 part by weight or more, or 1.5 parts by weight or more. The increase in the content of the azole rust inhibitor per 10 parts by weight of the carboxy group-containing monomer tends to improve the metal corrosion prevention effect. In some embodiments, the content of the azole rust inhibitor per 10 parts by weight of the carboxy group-containing monomer may be, for example, 4 parts by weight or more, and may be 6 parts by weight or more. Further, from the viewpoint of suitably achieving both the metal corrosion prevention effect and the member holding performance, the content of the azole rust inhibitor per 10 parts by weight of the carboxy group-containing monomer may be, for example, 30 parts by weight or less. It may be up to 15 parts by weight, down to 10 parts by weight, up to 5 parts by weight (eg up to 3 parts by weight).

  The pressure-sensitive adhesive layer disclosed herein may further contain a rust inhibitor other than the azole-based rust preventive, if necessary, as long as the effects of the present invention are not significantly impaired. Examples of such rust preventives are not particularly limited, but include, for example, amine compounds, nitrites, ammonium benzoate, ammonium phthalate, ammonium stearate, ammonium palmitate, ammonium oleate, ammonium carbonate, dicyclohexylamine. Examples include benzoate, urea, urotropin, thiourea, phenyl carbamate, cyclohexylammonium-N-cyclohexylcarbamate (CHC), and the like. These rust preventives other than azoles (non-azole rust preventives) can be used singly or in combination of two or more. The technology disclosed herein can be preferably implemented even in an embodiment in which a non-azole-based rust preventive is not substantially used.

  Examples of the amine compound include 2-amino-2-methyl-1-propanol, monoethanolamine, monoisopropanolamine, diethylethanolamine, hydroxy group-containing amine compounds such as ammonia and aqueous ammonia; cyclic amines such as morpholine; cyclohexyl And cyclic alkylamine compounds such as amines; and linear alkylamines such as 3-methoxypropylamine. Examples of nitrites include dicyclohexylammonium nitrite (DICHAN), diisopropylammonium nitrite (DIPAN), sodium nitrite, potassium nitrite, and calcium nitrite.

(Crosslinking agent)
As the crosslinking agent in the technique disclosed herein, an isocyanate-based crosslinking agent and at least one crosslinking agent having a different type of crosslinkable functional group are used in combination with the isocyanate-based crosslinking agent. The present inventor can effectively improve the heat cohesion force by using a combination of a base polymer (typically an acrylic polymer) copolymerized with a carboxy group-containing monomer and an isocyanate crosslinking agent. I found. However, in the above configuration, it has been found that the effect of improving the heat-resistant cohesive strength is impaired when an azole rust inhibitor is contained in order to prevent metal corrosion which is a concern due to the use of a carboxy group-containing monomer. According to the technique disclosed herein, a crosslinking agent other than an isocyanate-based crosslinking agent (that is, a crosslinking agent having a different type of crosslinkable reactive group from an isocyanate-based crosslinking agent; hereinafter also referred to as “non-isocyanate-based crosslinking agent”). By using in combination with an isocyanate-based crosslinking agent, it is possible to suitably achieve both high heat cohesion and excellent metal corrosion resistance in a configuration including an azole-based rust inhibitor. Note that the pressure-sensitive adhesive layer in the technology disclosed herein comprises the above-mentioned crosslinking agent in a form after the crosslinking reaction, a form before the crosslinking reaction, a partially crosslinked reaction, an intermediate or composite form thereof, and the like. May be contained. The crosslinking agent is typically contained in the pressure-sensitive adhesive layer exclusively in the form after the crosslinking reaction.

  As the isocyanate-based crosslinking agent, a polyfunctional isocyanate (refers to a compound having an average of two or more isocyanate groups per molecule, including those having an isocyanurate structure) can be preferably used. An isocyanate type crosslinking agent can be used individually by 1 type or in combination of 2 or more types.

Examples of the polyfunctional isocyanate include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates and the like.
Specific examples of the aliphatic polyisocyanates include 1,2-ethylene diisocyanate; tetramethylene diisocyanate such as 1,2-tetramethylene diisocyanate, 1,3-tetramethylene diisocyanate, 1,4-tetramethylene diisocyanate; -Hexamethylene diisocyanate such as hexamethylene diisocyanate, 1,3-hexamethylene diisocyanate, 1,4-hexamethylene diisocyanate, 1,5-hexamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,5-hexamethylene diisocyanate; Examples include 2-methyl-1,5-pentane diisocyanate, 3-methyl-1,5-pentane diisocyanate, and lysine diisocyanate.

  Specific examples of alicyclic polyisocyanates include isophorone diisocyanate; cyclohexyl diisocyanates such as 1,2-cyclohexyl diisocyanate, 1,3-cyclohexyl diisocyanate, 1,4-cyclohexyl diisocyanate; 1,2-cyclopentyl diisocyanate, 1,3 -Cyclopentyl diisocyanate such as cyclopentyl diisocyanate; hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tetramethylxylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and the like.

  Specific examples of the aromatic polyisocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, and 2,2′-diphenylmethane diisocyanate. 4,4′-diphenyl ether diisocyanate, 2-nitrodiphenyl-4,4′-diisocyanate, 2,2′-diphenylpropane-4,4′-diisocyanate, 3,3′-dimethyldiphenylmethane-4,4′-diisocyanate 4,4'-diphenylpropane diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, naphthylene-1,4-diisocyanate, naphthylene-1,5-diisocyanate, 3,3'-dimethoxy Diphenyl-4,4'-diisocyanate, xylylene-1,4-diisocyanate, xylylene-1,3-diisocyanate.

  Preferable polyfunctional isocyanates include polyfunctional isocyanates having an average of 3 or more isocyanate groups per molecule. Such a trifunctional or higher functional isocyanate is a difunctional or trifunctional or higher polymer (typically a dimer or trimer), a derivative (for example, a polyhydric alcohol and two or more polyfunctional isocyanates). Addition reaction product), polymer and the like. For example, diphenylmethane diisocyanate dimer or trimer, hexamethylene diisocyanate isocyanurate (trimer adduct of isocyanurate structure), reaction product of trimethylolpropane and tolylene diisocyanate, trimethylolpropane and hexamer Examples of the reaction product with methylene diisocyanate include polyfunctional isocyanates such as polymethylene polyphenyl isocyanate, polyether polyisocyanate, and polyester polyisocyanate. As commercial products of such polyfunctional isocyanates, trade names “Duranate TPA-100” manufactured by Asahi Kasei Chemicals Corporation, trade names “Coronate L”, “Coronate HL”, “Coronate HK”, “Coronate HK” manufactured by Tosoh Corporation HX ”,“ Coronate 2096 ”and the like.

  The amount of the isocyanate crosslinking agent used is not particularly limited. For example, it can be about 0.5 parts by weight or more with respect to 100 parts by weight of the base polymer. From the viewpoint of obtaining higher cohesive strength (particularly heat-resistant cohesive strength), the amount of the isocyanate crosslinking agent used relative to 100 parts by weight of the base polymer can be, for example, 1.0 part by weight or more, and 1.5 parts by weight or more. Also good. On the other hand, from the viewpoint of improving the adhesion to the adherend, the amount of the isocyanate-based crosslinking agent used is usually suitably 10 parts by weight or less with respect to 100 parts by weight of the base polymer, and 8 parts by weight or less. Alternatively, it may be 5 parts by weight or less (for example, 3 parts by weight or less). In one embodiment, the amount of the isocyanate crosslinking agent used relative to 100 parts by weight of the base polymer can be about 1 part by weight or more and about 7 parts by weight or less (eg, about 1.5 parts by weight or more and about 5 parts by weight or less).

  The kind of the non-isocyanate-based crosslinking agent used in combination with the isocyanate-based crosslinking agent is not particularly limited, and can be appropriately selected from conventionally known crosslinking agents. Examples of such crosslinking agents include epoxy crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, melamine crosslinking agents, carbodiimide crosslinking agents, hydrazine crosslinking agents, amine crosslinking agents, and peroxide crosslinking agents. Agents, metal chelate crosslinking agents, metal alkoxide crosslinking agents, metal salt crosslinking agents, silane coupling agents and the like. A non-isocyanate type crosslinking agent can be used individually by 1 type or in combination of 2 or more types.

  In a preferred embodiment, an epoxy crosslinking agent can be employed as the non-isocyanate crosslinking agent. As the epoxy-based crosslinking agent, a compound having two or more epoxy groups in one molecule can be used without particular limitation. An epoxy-based crosslinking agent having 3 to 5 epoxy groups in one molecule is preferable. An epoxy type crosslinking agent can be used individually by 1 type or in combination of 2 or more types.

  Although it does not specifically limit, As a specific example of an epoxy-type crosslinking agent, for example, N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) ) Cyclohexane, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polyglycerol polyglycidyl ether, and the like. Commercially available epoxy crosslinking agents include trade names “TETRAD-C” and “TETRAD-X” manufactured by Mitsubishi Gas Chemical Company, “Epicron CR-5L” manufactured by DIC, and Nagase ChemteX Corp. Product name “Denacol EX-512”, product name “TEPIC-G” manufactured by Nissan Chemical Industries, Ltd., and the like.

  The amount of the epoxy crosslinking agent used is not particularly limited. The amount of the epoxy crosslinking agent used is, for example, more than 0 parts by weight and about 1 part by weight or less (typically about 0.001 to 0.5 parts by weight) with respect to 100 parts by weight of the base polymer. Can do. From the viewpoint of suitably exhibiting the effect of improving the cohesive force, it is usually appropriate that the amount of the epoxy crosslinking agent used is about 0.002 parts by weight or more with respect to 100 parts by weight of the base polymer. 005 parts by weight or more is preferable, and about 0.008 parts by weight or more is more preferable. From the viewpoint of improving the adhesion to the adherend, it is usually appropriate that the amount of the epoxy crosslinking agent used is about 0.2 parts by weight or less with respect to 100 parts by weight of the base polymer. The amount is preferably 1 part by weight or less, more preferably less than about 0.05 part by weight, and further preferably less than about 0.03 part by weight (for example, about 0.025 part by weight or less).

  In the technique disclosed here, the relationship between the content of the isocyanate-based crosslinking agent and the content of the non-isocyanate-based crosslinking agent (for example, epoxy-based crosslinking agent) is not particularly limited. The content of the non-isocyanate crosslinking agent can be, for example, about 1/50 or less of the content of the isocyanate crosslinking agent. The content of the non-isocyanate crosslinking agent is preferably about 1/75 or less of the content of the isocyanate crosslinking agent on a weight basis from the viewpoint of more suitably achieving both adhesion to the adherend and cohesion. It is suitable and is preferably about 1/100 or less (for example, 1/150 or less). In addition, from the viewpoint of suitably exhibiting the effect of using a combination of an isocyanate crosslinking agent and a non-isocyanate crosslinking agent (for example, an epoxy crosslinking agent), the content of the non-isocyanate crosslinking agent is usually isocyanate crosslinking. It is appropriate that the content of the agent is about 1/1000 or more, for example, about 1/500 or more.

(Tackifying resin)
The pressure-sensitive adhesive layer in the technology disclosed herein can contain a tackifier resin. Thereby, the peeling strength of an adhesive sheet can be improved and the holding | maintenance performance of a member can be improved. As tackifying resins, phenolic tackifying resins, terpene tackifying resins, modified terpene tackifying resins, rosin tackifying resins, hydrocarbon tackifying resins, epoxy tackifying resins, polyamide tackifying resins, 1 type (s) or 2 or more types selected from well-known various tackifying resin, such as an elastomer type tackifying resin and a ketone type tackifying resin, can be used.

Examples of the phenolic tackifier resin include terpene phenol resin, hydrogenated terpene phenol resin, alkylphenol resin, and rosin phenol resin.
The terpene phenol resin refers to a polymer containing a terpene residue and a phenol residue. A copolymer of a terpene and a phenol compound (terpene-phenol copolymer resin) and a terpene homopolymer or copolymer This is a concept that includes both phenol-modified products (phenol-modified terpene resins). Preferable examples of terpenes constituting such a terpene phenol resin include monoterpenes such as α-pinene, β-pinene and limonene (including d-form, l-form and d / l-form (dipentene)). Is mentioned. The hydrogenated terpene phenol resin refers to a hydrogenated terpene phenol resin having a structure obtained by hydrogenating such a terpene phenol resin. Sometimes referred to as hydrogenated terpene phenol resin.
The alkylphenol resin is a resin (oil-based phenol resin) obtained from alkylphenol and formaldehyde. Examples of the alkylphenol resin include those of novolak type and resol type.
The rosin phenolic resin is typically a phenol-modified product of rosins or the above-mentioned various rosin derivatives (including rosin esters, unsaturated fatty acid-modified rosins and unsaturated fatty acid-modified rosin esters). Examples of the rosin phenol resin include a rosin phenol resin obtained by a method in which phenol is added to a rosin or the above-mentioned various rosin derivatives with an acid catalyst and thermally polymerized.

  Examples of terpene-based tackifier resins include polymers of terpenes (typically monoterpenes) such as α-pinene, β-pinene, d-limonene, l-limonene, and dipentene. It may be a homopolymer of one terpene or a copolymer of two or more terpenes. Examples of the homopolymer of one kind of terpene include an α-pinene polymer, a β-pinene polymer, a dipentene polymer, and the like. Examples of the modified terpene resin include those obtained by modifying the terpene resin. Specific examples include styrene-modified terpene resins and hydrogenated terpene resins.

  The concept of rosin-based tackifying resin here includes both rosins and rosin derivative resins. Examples of rosins include unmodified rosins such as gum rosin, wood rosin, tall oil rosin (raw rosin); modified rosins modified with hydrogenation, disproportionation, polymerization, etc. Averaged rosin, polymerized rosin, other chemically modified rosins, etc.).

  The rosin derivative resin is typically a derivative of rosins as described above. The concept of the rosin resin here includes derivatives of unmodified rosin and derivatives of modified rosin (including hydrogenated rosin, disproportionated rosin and polymerized rosin). For example, rosin esters such as an unmodified rosin ester that is an ester of an unmodified rosin and an alcohol, and a modified rosin ester that is an ester of a modified rosin and an alcohol; for example, an rosin modified with an unsaturated fatty acid. Saturated fatty acid-modified rosins; for example, unsaturated fatty acid-modified rosin esters obtained by modifying rosin esters with unsaturated fatty acids; for example, rosins or various rosin derivatives described above (rosin esters, unsaturated fatty acid-modified rosins and unsaturated Rosin alcohols obtained by reducing the carboxy group of fatty acid-modified rosin esters); for example, rosins or metal salts of the various rosin derivatives described above. Specific examples of rosin esters include unmodified rosin or modified rosin (hydrogenated rosin, disproportionated rosin, polymerized rosin, etc.) methyl ester, triethylene glycol ester, glycerin ester, pentaerythritol ester and the like.

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

  The softening point of the tackifier resin is not particularly limited. From the viewpoint of improving the cohesive force, in one embodiment, a tackifier resin having a softening point (softening temperature) of about 80 ° C. or higher (preferably about 100 ° C. or higher) can be preferably used. In the technique disclosed herein, the total amount of tackifying resin contained in the pressure-sensitive adhesive layer is 100% by weight, and more than 50% by weight (more preferably more than 70% by weight, for example, more than 90% by weight) has the above softening point. It can preferably be implemented in an embodiment that is a tackifying resin. For example, a phenolic tackifier resin (terpene phenol resin or the like) having such a softening point can be preferably used. The tackifying resin may contain, for example, a terpene phenol resin having a softening point of about 135 ° C. or higher (and further about 140 ° C. or higher). The upper limit of the softening point of the tackifier resin is not particularly limited. From the viewpoint of improving the adhesion to the adherend, in one embodiment, a tackifying resin having a softening point of about 200 ° C. or lower (more preferably about 180 ° C. or lower) can be preferably used. In addition, the softening point of tackifying resin can be measured based on the softening point test method (ring ball method) prescribed | regulated to JISK2207.

  In the case where the pressure-sensitive adhesive layer contains a tackifying resin, the amount of the tackifying resin used is not particularly limited, and can be appropriately set within a range of, for example, about 1 to 100 parts by weight with respect to 100 parts by weight of the base polymer. From the viewpoint of suitably exhibiting the effect of improving the peel strength, the amount of the tackifying resin used is usually 5 parts by weight or more with respect to 100 parts by weight of the base polymer (for example, acrylic polymer). Part or more, preferably 15 parts by weight or more. From the viewpoint of heat-resistant cohesive strength, the amount of tackifying resin used is usually 50 parts by weight or less, and may be 40 parts by weight or less, based on 100 parts by weight of the base polymer (for example, acrylic polymer). 30 parts by weight or less.

  A preferable embodiment includes an embodiment in which the tackifying resin contains one or more phenolic tackifying resins (typically terpene phenol resins). The technique disclosed herein can be preferably implemented in an embodiment in which, for example, the total amount of the tackifying resin is 100% by weight, and about 25% by weight or more (more preferably about 30% by weight or more) is a terpene phenol resin. About 50% by weight or more of the total amount of the tackifying resin may be terpene phenol resin, and about 80% by weight or more (for example, about 90% by weight or more) may be terpene phenol resin. Substantially all of the tackifying resin (eg, about 95-100% by weight, or even about 99-100% by weight) may be a terpene phenol resin.

  Although not particularly limited, in one embodiment of the technology disclosed herein, the tackifier resin may include a tackifier resin having a hydroxyl value higher than 20 mgKOH / g. Among these, a tackifier resin having a hydroxyl value of 30 mgKOH / g or more is preferable. Hereinafter, a tackifier resin having a hydroxyl value of 30 mgKOH / g or more may be referred to as a “high hydroxyl value resin”. According to the tackifier resin containing such a high hydroxyl value resin, an adhesive layer having excellent adhesion to the adherend and high cohesion can be realized. In one embodiment, the tackifying resin may contain a high hydroxyl value resin having a hydroxyl value of 50 mgKOH / g or more (more preferably 70 mgKOH / g or more).

As the value of the hydroxyl value, a value measured by a potentiometric titration method defined in JIS K0070: 1992 can be adopted. The specific measurement method is as follows.
[Measurement method of hydroxyl value]
1. Reagent (1) As an acetylating reagent, about 12.5 g (about 11.8 mL) of acetic anhydride is taken, and pyridine is added thereto to make a total volume of 50 mL, and the mixture is sufficiently stirred. Alternatively, about 25 g (about 23.5 mL) of acetic anhydride is taken, and pyridine is added thereto to make a total volume of 100 mL, and the mixture is sufficiently stirred.
(2) As a measuring reagent, a 0.5 mol / L potassium hydroxide ethanol solution is used.
(3) Prepare toluene, pyridine, ethanol and distilled water.
2. Operation (1) About 2 g of a sample is accurately weighed in a flat bottom flask, 5 mL of an acetylating reagent and 10 mL of pyridine are added, and an air cooling tube is attached.
(2) The flask was heated in a bath at 100 ° C. for 70 minutes, allowed to cool, and 35 mL of toluene was added as a solvent from the top of the condenser and stirred, and then 1 mL of distilled water was added and stirred to acetic anhydride. Disassemble. Heat again in the bath for 10 minutes to complete decomposition and allow to cool.
(3) Wash the cooling tube with 5 mL of ethanol and remove it. Next, 50 mL of pyridine is added as a solvent and stirred.
(4) Add 25 mL of 0.5 mol / L potassium hydroxide ethanol solution using a whole pipette.
(5) Potentiometric titration with 0.5 mol / L potassium hydroxide ethanol solution. The inflection point of the obtained titration curve is the end point.
(6) In the blank test, the above (1) to (5) are performed without putting a sample.
3. Calculation The hydroxyl value is calculated by the following formula.
Hydroxyl value (mgKOH / g) = [(BC) × f × 28.05] / S + D
here,
B: Amount of 0.5 mol / L potassium hydroxide ethanol solution used for the blank test (mL),
C: The amount of 0.5 mol / L potassium hydroxide ethanol solution used for the sample (mL),
f: factor of 0.5 mol / L potassium hydroxide ethanol solution,
S: weight of the sample (g),
D: Acid value,
28.05: 1/2 of the molecular weight of potassium hydroxide 56.11,
It is.

  As high hydroxyl value resin, what has the hydroxyl value more than predetermined value among the various tackifying resin mentioned above can be used. High hydroxyl value resin can be used individually by 1 type or in combination of 2 or more types. For example, a phenolic tackifier resin having a hydroxyl value of 30 mgKOH / g or more can be preferably employed as the high hydroxyl value resin. In a preferable embodiment, a terpene phenol resin having a hydroxyl value of 30 mgKOH / g or more is used as the tackifier resin. The terpene phenol resin is advantageous because the hydroxyl value can be arbitrarily controlled by the copolymerization ratio of phenol.

  The upper limit of the hydroxyl value of the high hydroxyl value resin is not particularly limited. From the viewpoint of compatibility with the base polymer, the hydroxyl value of the high hydroxyl value resin is usually appropriately about 200 mgKOH / g or less, preferably about 180 mgKOH / g or less, more preferably about 160 mgKOH / g or less, Preferably, it is about 140 mgKOH / g or less. The technology disclosed herein can be preferably implemented in an embodiment in which the tackifying resin contains a high hydroxyl value resin (for example, a phenolic tackifying resin, preferably a terpene phenol resin) having a hydroxyl value of 30 to 160 mgKOH / g. In one embodiment, a high hydroxyl value resin having a hydroxyl value of 30 to 80 mgKOH / g (for example, 30 to 65 mgKOH / g) can be preferably used. In another embodiment, a high hydroxyl value resin having a hydroxyl value of 70 to 140 mgKOH / g can be preferably used.

  Although not particularly limited, when a high hydroxyl value resin is used, the proportion of the high hydroxyl value resin (for example, terpene phenol resin) in the entire tackifying resin contained in the pressure-sensitive adhesive layer is, for example, about 25% by weight or more. About 30% by weight or more is preferable, and about 50% by weight or more (eg, about 80% by weight or more, typically about 90% by weight or more) is more preferable. Substantially all of the tackifying resin (for example, about 95 to 100% by weight, and further about 99 to 100% by weight) may be a high hydroxyl value resin.

(Coloring agent)
The pressure-sensitive adhesive layer can contain a colorant. Thereby, the light transmittance (light-shielding property) of an adhesive layer can be adjusted. For example, the light transmittance of the pressure-sensitive adhesive layer can be adjusted. Adjusting the light transmittance of the pressure-sensitive adhesive layer can also help to adjust the light transmittance of a pressure-sensitive adhesive sheet including the pressure-sensitive adhesive layer. A colorant can also be used to adjust the relative dielectric constant.

  As the colorant, conventionally known pigments and dyes can be used. Examples of the pigment include zinc carbonate, zinc oxide, zinc sulfide, talc, kaolin, calcium carbonate, titanium oxide, silica, lithium fluoride, calcium fluoride, barium sulfate, alumina, zirconia, iron oxide series, and iron hydroxide series. , Chromium oxide, spinel firing, chromic acid, chromium vermilion, bituminous, aluminum powder, bronze powder, silver powder, calcium phosphate, and other inorganic pigments, phthalocyanine, azo, and condensed azo Organic pigments such as azo lake, anthraquinone, perylene / perinone, indigo, thioindigo, isoindolinone, azomethine, dioxazine, quinacridone, aniline black, triphenylmethane, carbon black It is done. Examples of the dye include azo dyes, anthraquinone, quinone phthalone, styryl, diphenylmethane, triphenylmethane, oxazine, triazine, xanthan, methane, azomethine, acridine, and diazine. A coloring agent can be used individually by 1 type or in combination of 2 or more types as appropriate.

  A black colorant can be preferably used because the light-shielding property can be efficiently adjusted with a small amount of the colorant. Specific examples of black colorants include carbon black (furnace black, channel black, acetylene black, thermal black, lamp black, pine smoke, etc.), graphite, copper oxide, manganese dioxide, aniline black, perylene black, titanium black, cyanine. Examples thereof include black, activated carbon, ferrite (nonmagnetic ferrite, magnetic ferrite, etc.), magnetite, chromium oxide, iron oxide, molybdenum disulfide, chromium complex, anthraquinone colorant and the like. Of these, carbon black is preferred.

The blending amount of the colorant can be set so that an adhesive layer satisfying a desired light transmittance is formed, and is not particularly limited. Usually, it is suitable that it is 0.5 parts by weight or more with respect to 100 parts by weight of the base polymer, preferably 1.0 part by weight or more, and more preferably 1.5 parts by weight or more. Moreover, the compounding quantity of a coloring agent can be 15 weight part or less with respect to 100 weight part of base polymers, for example. From the viewpoint of suppressing a decrease in adhesive properties that may occur due to the blending of the colorant, the blending amount of the colorant is usually suitably 12 parts by weight or less with respect to 100 parts by weight of the base polymer, and 10 parts by weight or less. Preferably, the amount is 8 parts by weight or less. In a preferred embodiment, the blending amount of the colorant with respect to 100 parts by weight of the base polymer can be 7 parts by weight or less.
The content of the colorant in the pressure-sensitive adhesive layer is usually suitably 0.3% by weight or more of the pressure-sensitive adhesive layer, preferably 0.5% by weight or more, and more preferably 1.0% by weight or more. preferable. The content of the colorant can be, for example, less than 13% by weight, preferably less than 10% by weight, more preferably less than 9% by weight, and still more preferably less than 7% by weight. In a preferred embodiment, the colorant content of the pressure-sensitive adhesive layer can be less than 6% by weight.

(Other additives)
In addition to the above-described components, the pressure-sensitive adhesive composition includes a leveling agent, a crosslinking aid, a plasticizer, a softener, an antistatic agent, an anti-aging agent, an ultraviolet absorber, an antioxidant, and a light stabilizer as necessary. Various additives that are common in the field of pressure-sensitive adhesives may be included. About such various additives, conventionally well-known things can be used by a conventional method, and since it does not characterize this invention in particular, detailed description is abbreviate | omitted.

  The pressure-sensitive adhesive layer (layer made of a pressure-sensitive adhesive) disclosed herein is an aqueous energy-sensitive adhesive composition, a solvent-type pressure-sensitive adhesive composition, a hot-melt-type pressure-sensitive adhesive composition, or an active energy ray such as an ultraviolet ray or an electron beam. It can be an adhesive layer formed from an active energy ray-curable adhesive composition that is effective by irradiation. The water-based pressure-sensitive adhesive composition refers to a pressure-sensitive adhesive composition in a form containing a pressure-sensitive adhesive (pressure-sensitive adhesive layer forming component) in a water-based solvent (water-based solvent), and is typically dispersed in water. What is called a type pressure-sensitive adhesive composition (a composition in which at least a part of the pressure-sensitive adhesive is dispersed in water) and the like are included. Moreover, a solvent-type adhesive composition means the adhesive composition of the form which contains an adhesive in an organic solvent. The technique disclosed here can be preferably implemented in an aspect including a pressure-sensitive adhesive layer formed from a solvent-type pressure-sensitive adhesive composition from the viewpoint of pressure-sensitive adhesive properties and the like.

(Formation of adhesive layer)
The pressure-sensitive adhesive layer disclosed herein can be formed by a conventionally known method. For example, a method of forming a pressure-sensitive adhesive layer by applying a pressure-sensitive adhesive composition to a peelable surface (peeling surface) and drying it can be employed. In the pressure-sensitive adhesive sheet having a support base material, for example, a method (direct method) for forming a pressure-sensitive adhesive layer by directly applying (typically coating) the pressure-sensitive adhesive composition to the support base material and drying it is used. Can be adopted. Also, a method (transfer method) in which a pressure-sensitive adhesive composition is applied to a peelable surface (peeling surface) and dried to form a pressure-sensitive adhesive layer on the surface, and the pressure-sensitive adhesive layer is transferred to a supporting substrate. ) May be adopted. As the release surface, for example, the surface of a release liner described later can be preferably used. The pressure-sensitive adhesive layer disclosed herein is typically formed continuously, but is not limited to such a form, for example, a regular or random pattern such as a dot or stripe. The formed adhesive layer may be sufficient.

The pressure-sensitive adhesive composition can be applied using a conventionally known coater such as a gravure roll coater, a die coater, or a bar coater. Alternatively, the pressure-sensitive adhesive composition may be applied by impregnation or curtain coating.
From the viewpoint of promoting the crosslinking reaction and improving the production efficiency, the pressure-sensitive adhesive composition is preferably dried under heating. A drying temperature can be about 40-150 degreeC, for example, and it is preferable to usually be about 60-130 degreeC. After the pressure-sensitive adhesive composition is dried, aging may be further performed for the purpose of adjusting the component transfer in the pressure-sensitive adhesive layer, progressing the crosslinking reaction, alleviating strain that may be present in the pressure-sensitive adhesive layer, and the like.

  The thickness of the pressure-sensitive adhesive layer is not particularly limited. From the viewpoint of avoiding an excessively thick adhesive sheet, the thickness of the adhesive layer is usually about 100 μm or less, preferably about 70 μm or less, more preferably about 50 μm or less (for example, about 30 μm or less). is there. The lower limit of the thickness of the pressure-sensitive adhesive layer is not particularly limited, but from the viewpoint of adhesion to the adherend, it is advantageous to be about 4 μm or more, preferably about 6 μm or more, more preferably about 10 μm or more (for example, About 15 μm or more).

(Relative permittivity of adhesive layer)
The pressure-sensitive adhesive sheet disclosed herein may include a pressure-sensitive adhesive layer having a relative dielectric constant at 300 kHz of 3 or more (for example, 3.1 or more). Here, the relative dielectric constant means a dielectric constant defined in JIS K6911. The relative dielectric constant at 300 kHz of the pressure-sensitive adhesive layer can be measured according to JIS K6911. The same applies to the embodiments described later. Hereinafter, unless otherwise specified, the relative permittivity in this specification refers to the relative permittivity at 300 kHz.
The high dielectric constant of the pressure-sensitive adhesive layer means that the pressure-sensitive sensor is improved in sensitivity in a pressure-sensitive adhesive sheet that is assumed to be attached to a pressure-sensitive sensor (for example, a capacitive pressure-sensitive sensor). From the viewpoint of A pressure-sensitive adhesive sheet including a pressure-sensitive adhesive layer having a high relative dielectric constant is typically in the form of a double-sided pressure-sensitive adhesive sheet (preferably, a double-sided pressure-sensitive adhesive sheet without a substrate), for example, for fixing a capacitive pressure sensor. It can be preferably used. The upper limit of the relative dielectric constant of the pressure-sensitive adhesive layer is not particularly limited. However, since it is easy to obtain a pressure-sensitive adhesive sheet that achieves both high levels of metal corrosion prevention and member holding performance, it is usually 6 or less. It may be 5 or less.
The relative dielectric constant of the pressure-sensitive adhesive layer is, for example, the composition of monomer components constituting the base polymer (for example, the type of main monomer, the amount of carboxy group-containing monomer used, the presence or absence of a functional group-containing monomer and the amount used), It can be adjusted by the amount of the crosslinking agent used.

<Support base material>
In the embodiment in which the pressure-sensitive adhesive sheet disclosed herein is in the form of a single-sided pressure-sensitive adhesive type or double-sided pressure-sensitive adhesive sheet with a base material, the base material for supporting (lining) the pressure-sensitive adhesive layer is a resin film, paper, cloth, rubber Sheets, foam sheets, metal foils, composites of these, and the like can be used. Examples of resin films include polyolefin films such as polyethylene (PE), polypropylene (PP), and ethylene / propylene copolymers; polyester films such as polyethylene terephthalate (PET); vinyl chloride resin films; vinyl acetate resin films; Resin film; polyamide resin film; fluororesin film; cellophane and the like. Examples of paper include Japanese paper, kraft paper, glassine paper, high quality paper, synthetic paper, top coat paper, and the like. Examples of the fabric include woven fabrics and non-woven fabrics made of various fibrous substances alone or by blending. Examples of the fibrous material include cotton, suf, manila hemp, pulp, rayon, acetate fiber, polyester fiber, polyvinyl alcohol fiber, polyamide fiber, polyolefin fiber and the like. Examples of rubber sheets include natural rubber sheets and butyl rubber sheets. Examples of the foam sheet include a foamed polyurethane sheet and a foamed polychloroprene rubber sheet. Examples of the metal foil include aluminum foil and copper foil.

  The term “nonwoven fabric” as used herein refers to a non-woven fabric for pressure-sensitive adhesive sheets mainly used in the field of pressure-sensitive adhesive tapes and other pressure-sensitive adhesive sheets, and is typically a non-woven fabric produced using a general paper machine. (Sometimes called "paper"). Moreover, the resin film here is typically a non-porous resin sheet, and is a concept that is distinguished from, for example, a nonwoven fabric (that is, does not include a nonwoven fabric). The resin film may be an unstretched film, a uniaxially stretched film, or a biaxially stretched film.

  The thickness of the support substrate is not particularly limited. From the viewpoint of avoiding an excessively thick adhesive sheet, the thickness of the support substrate can be set to, for example, approximately 200 μm or less (for example, approximately 100 μm or less). Depending on the purpose and mode of use of the adhesive sheet, the thickness of the support substrate may be about 70 μm or less, about 30 μm or less, or about 10 μm or less (for example, about 5 μm or less). The lower limit of the thickness of the supporting substrate is not particularly limited. From the viewpoint of handling property (handling property) and processability of the pressure-sensitive adhesive sheet, the thickness of the supporting substrate is usually suitably about 2 μm or more, preferably about 5 μm or more, for example, about 10 μm or more.

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

<Release liner>
In the technology disclosed herein, a release liner can be used in forming the pressure-sensitive adhesive layer, preparing the pressure-sensitive adhesive sheet, storing the pressure-sensitive adhesive sheet before use, distributing it, and processing the shape. The release liner is not particularly limited. 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 fluoropolymer (polytetrafluoroethylene, etc.), a polyolefin resin (polyethylene, A release liner made of a low adhesion material such as polypropylene can be used. The release treatment layer may be formed, for example, by surface-treating the liner base material with a release treatment agent such as silicone-based, long-chain alkyl-based, fluorine-based, or molybdenum sulfide.

<Adhesive sheet>
The total thickness of the pressure-sensitive adhesive sheet disclosed herein (including the pressure-sensitive adhesive layer and further including the support base material but not including the release liner in the configuration having the support base material) is not particularly limited. The total thickness of the pressure-sensitive adhesive sheet can be, for example, about 300 μm or less, and is usually about 200 μm or less from the viewpoint of thinning, and may be about 100 μm or less (for example, about 70 μm or less). The lower limit of the thickness of the pressure-sensitive adhesive sheet is not particularly limited, but is usually suitably about 4 μm or more, preferably about 6 μm or more, more preferably about 10 μm or more (for example, about 15 μm or more). In the base material-less pressure-sensitive adhesive sheet, the thickness of the pressure-sensitive adhesive layer is the thickness of the pressure-sensitive adhesive sheet.

The pressure-sensitive adhesive sheet disclosed herein may exhibit an impact adhesive strength of 0.25 mJ / cm ² or more in an impact adhesive strength test performed by a method described in Examples described later. Such a pressure-sensitive adhesive sheet can be a joining means having excellent durability against an impact in the shear direction. Therefore, for example, it can be preferably used as a member fixing means in a portable electronic device that is assumed to be exposed to an impact caused by a drop or a collision. According to the technique disclosed herein, there is provided a pressure-sensitive adhesive sheet exhibiting a shear impact resistance having an impact adhesive strength of 0.30 mJ / cm ² or more (more preferably 0.35 mJ / cm ² or more, for example, 0.40 mJ / cm ² or more). Can be provided. The upper limit of impact adhesive strength is not particularly limited, and may be, for example, 1.00 mJ / cm ² or less. From the viewpoint of easily achieving compatibility with other characteristics (for example, heat resistance holding force) at a higher level, the impact adhesive strength may be, for example, 0.70 mJ / cm ² or less, and 0.60 mJ / cm ² or less. It may be 0.50 mJ / cm ² or less.
The impact adhesive strength is adjusted by, for example, the composition of the monomer component constituting the base polymer (for example, the amount of the carboxy group-containing monomer used, the presence or absence of the functional group-containing monomer and the amount used), the amount of the crosslinking agent used, be able to.

  The pressure-sensitive adhesive sheet disclosed herein preferably exhibits a heat-resistant cohesive strength at a level that is maintained for 1 hour or more in a high-temperature holding force test performed by a method described in Examples described later. Such an adhesive sheet is used for fixing a member, and can maintain the fixing position of the member with high accuracy. For example, even if the member is used in a mode in which the member is fixed in a product that can be placed in a high temperature environment or a product in which stress in the shearing direction can be applied for a long time, the displacement of the member can be highly suppressed. Therefore, it is suitable for an application for fixing a member (for example, sensors) in a portable electronic device in which improvement in assembly accuracy and position accuracy is desired from the viewpoint of miniaturization and high integration. An example of a preferred application of the pressure-sensitive adhesive sheet disclosed herein is fixing a pressure-sensitive sensor for a touch panel that requires high positional accuracy. According to a preferred aspect of the technology disclosed herein, in the high temperature holding force test, the positional deviation after 1 hour is a level that remains at 1 mm or less (more preferably 0.70 mm or less, more preferably 0.50 mm or less). A pressure-sensitive adhesive sheet exhibiting heat-resistant cohesive strength can be provided.

  The pressure-sensitive adhesive sheet disclosed herein has a time until the discoloration of the copper plate is visually recognized under the conditions of 65 ° C. and 90% RH in the corrosivity test performed by the method described in the examples described later. It is preferable that it is more than time, and it is more preferable that it is more than 500 hours. Such a pressure-sensitive adhesive sheet having a metal corrosion preventing property is a member of an electronic device (for example, a substrate on which a conductive circuit pattern made of copper or the like is printed on the surface, a pressure sensor that includes at least a portion of the substrate, etc. This is suitable for use in fixing electronic components).

  The pressure-sensitive adhesive sheet disclosed herein is a room temperature peel strength with respect to polyethylene terephthalate (PET), that is, a 180 ° peel strength measured at room temperature (23 ° C.) using PET as an adherend (hereinafter also referred to as “vs PET room temperature peel strength”). ) Is preferably 15 N / 25 mm or more (more preferably 17 N / 25 mm or more, for example, 19 N / 25 mm or more). Such an adhesive sheet is suitable for fixing a member having at least a part of a surface made of a resin material such as PET or polyimide. The upper limit of the room temperature peel strength with respect to PET is not particularly limited, but may be, for example, 40 N / 25 mm or less, or 30 N / 25 mm or less from the viewpoint of facilitating coexistence with good heat cohesion.

  The room temperature peel strength against PET can be measured as follows. Specifically, a 50 μm thick PET film (trade name “Lumirror S10”, manufactured by Toray Industries, Inc.) fixed to a stainless steel plate with a double-sided adhesive tape is used as the adherend. A measurement sample is prepared by cutting the pressure-sensitive adhesive sheet into a size of 25 mm in width and 100 mm in length, and the pressure-sensitive adhesive surface of the measurement sample is the surface of the adherend (PET film surface) in an environment of 23 ° C. and 50% RH. Then, a 2 kg roller is reciprocated once to be pressure-bonded. After leaving this in the same environment for 30 minutes, using a universal tensile compression tester, in accordance with JIS Z0237: 2009, at a tensile speed of 300 mm / min and a peel angle of 180 degrees, the peel strength (N / 25 mm ). As a universal tensile and compression tester, for example, “Tensile and compression tester, TG-1kN” manufactured by Minebea can be used. In a double-sided adhesive sheet without a base material, an appropriate resin film is attached to one adhesive surface of the adhesive sheet (the surface opposite to the adhesive surface to be measured), and then the adhesive sheet is backed. A measurement sample may be prepared by cutting into the above size. As the backing film, for example, a trade name “Lumirror S10” manufactured by Toray Industries, Inc. may be used. The same applies to the embodiments described later.

<Application>
The pressure-sensitive adhesive sheet disclosed herein is typically in the form of a double-sided pressure-sensitive adhesive sheet and can be preferably used for the purpose of fixing a member. The double-sided pressure-sensitive adhesive sheet may be baseless or may be provided with a base material. From the viewpoint of thinning, in one embodiment, the form of a double-sided pressure-sensitive adhesive sheet without a substrate can be preferably adopted.
The pressure-sensitive adhesive sheet disclosed herein is suitable for, for example, a member fixing application in a portable electronic device. Non-limiting examples of the above-mentioned portable electronic devices include mobile phones, smartphones, tablet computers, notebook computers, various wearable devices (for example, wrist wear devices that are worn on the wrist like watches, clips, straps, etc. Modular type, eyeglass type (monocular type or binocular type, including head mount type), clothing type that attaches to shirts, socks, hats, etc. in the form of accessories, earphones, etc. Earphone type that attaches to the ear, etc.), digital camera, digital video camera, audio equipment (portable music player, IC recorder, etc.), calculator (calculator, etc.), portable game device, electronic dictionary, electronic notebook, electronic book, in-vehicle Information equipment, portable radio, portable television, portable printer, portable scanner, portable modem, and the like. The pressure-sensitive adhesive sheet disclosed herein can be preferably used for the purpose of fixing the pressure-sensitive sensor and other members in, for example, a portable electronic device including a pressure-sensitive sensor among such portable electronic devices. In a preferred embodiment, the pressure-sensitive adhesive sheet is composed of a device (typically a pen-type or mouse-type device) for indicating a position on the screen and a device for detecting the position (typically a plate (typically). It is used to fix a pressure-sensitive sensor and other members in an electronic device (typically a portable electronic device) having a function that allows an absolute position to be specified on a touch panel). obtain. In this specification, “carrying” means that it is not sufficient to be able to carry it alone, but that it has a level of portability that allows an individual (standard adult) to carry it relatively easily. Shall mean.

  The pressure-sensitive adhesive sheet disclosed herein can be preferably used for fixing a pressure-sensitive sensor in a portable electronic device, for example. That is, it can be preferably used in a mode in which one pressure-sensitive adhesive surface of the pressure-sensitive adhesive sheet is attached to the pressure-sensitive sensor. As a suitable example of the pressure sensor to be affixed (adhered body), a pressure sensor for a touch panel can be mentioned. For example, the pressure-sensitive adhesive sheet disclosed herein can be preferably used for fixing a pressure-sensitive sensor for a touch panel capable of identifying and responding to strength such as finger pressing. Such a pressure-sensitive sensor includes, for example, one or a plurality of capacitor plates, and simply uses the fact that the distance between the touch panel and the capacitor plate is reduced when a display surface (for example, a glass surface) of the touch panel is pressed with a finger. It may be configured to distinguish between touch (touch) and depression. Such a pressure-sensitive sensor is preferably arranged on the back side of the display module (for example, in a portable electronic device including a liquid crystal panel, typically on the back side of the backlight). Can be placed on the side. The pressure-sensitive sensor to be attached typically includes a flexible printed circuit board (FPC) at least in part. The FPC includes a layer (insulating layer) made of an electrical insulator, and a circuit pattern is formed on the surface of the insulating layer with a conductive material (typically copper or a copper alloy). The FPC may be further provided with a conductive or insulating layer depending on required performance and function. Such an FPC may have a multilayer structure in which a plurality of circuit boards are stacked. The pressure-sensitive adhesive sheet disclosed here is typically affixed to the back surface (the surface opposite to the circuit pattern forming surface) of the FPC constituting the pressure-sensitive sensor. More specifically, the pressure-sensitive adhesive sheet is attached to an insulating layer that constitutes the back surface of the pressure sensor.

  The insulating material constituting the insulating layer is not particularly limited. For example, polyimide resin, acrylic resin, polyether nitrile resin, polyether sulfone resin, polyester resin (polyethylene terephthalate) Resin, polyethylene naphthalate resin, etc.), polyvinyl chloride resin, polyphenylene sulfide resin, polyether ether ketone resin, polyamide resin (so-called aramid resin, etc.), polyarylate resin, polycarbonate resin, liquid crystal polymer A resin material such as a plastic material (typically a plastic material) can be preferably used. Especially, the polyimide resin excellent in heat resistance is preferably used as an insulating layer constituting material for a pressure-sensitive sensor, and the pressure-sensitive adhesive sheet used for this application may exhibit good adhesion to the polyimide resin. desirable. The surface of the insulating layer can be subjected to various surface treatments (for example, corona discharge treatment, plasma treatment, roughening treatment, hydrolysis treatment, etc.) in order to ensure adhesion with the adhesive sheet. The thickness of the insulating layer as a component of the pressure sensor is not particularly limited, but is appropriately about 2 μm or more, and is usually 4 μm or more (typically 8 μm or more, for example, 15 μm or more). The upper limit of the insulating layer is not particularly limited, and is approximately 120 μm or less (typically 40 μm or less, for example, 25 μm or less). In addition, formation of a circuit pattern (typically a metal pattern such as copper) on the surface of the insulating layer can be performed by appropriately adopting and modifying a known method, and does not particularly characterize the present invention. Detailed description is omitted.

  Moreover, the other adhesive surface (adhesive surface located on the opposite side to the adhesive surface which fixes a pressure sensor) of an adhesive sheet is affixed on various objects (for example, member). Typically, it is affixed to the structural member of various electronic devices. Although it is not particularly limited, it can be applied to a case of a mobile electronic device such as a mobile phone, a smartphone, a tablet-type personal computer, a back member such as a motor, a substrate, a cover, or an electromagnetic wave shield or a reinforcing plate disposed on the back surface of an FPC. The other pressure-sensitive adhesive surface of the pressure-sensitive adhesive sheet disclosed herein can be attached. Since the pressure-sensitive adhesive sheet disclosed herein can exhibit a good adhesive function even if it is thin, it can be preferably used in portable electronic device applications where there is a significant demand for downsizing and space saving.

  The material constituting the fixed object of the pressure sensor (for example, a back member such as an electromagnetic wave shield or a reinforcing plate) is not particularly limited. For example, copper, silver, gold, iron, tin, palladium, Metal materials such as aluminum, nickel, titanium, chromium, zinc, etc., or alloys containing two or more of these, various resin materials exemplified as the insulating layer constituent material, alumina, zirconia, soda glass, quartz glass, carbon, etc. Inorganic materials and the like. Among these, metal materials such as copper, aluminum, and stainless steel, and resin materials (typically plastic materials) such as polyimide resins, aramid resins, and polyphenylene sulfide resins are widely used. Moreover, the fixed object may be in any form of a single layer structure or a multilayer structure, and various surface treatments may be applied to the surface (attachment surface) to which the adhesive sheet is attached. Although not particularly limited, as an example of the fixed object, a back member having a thickness of about 1 μm or more (typically 5 μm or more, for example, 60 μm or more, further 120 μm or more), about 1500 μm or less (for example, 800 μm or less). Can be mentioned.

  The pressure-sensitive adhesive sheet disclosed herein is preferably used in a mode in which one pressure-sensitive adhesive surface is bonded to a pressure-sensitive sensor and then the other pressure-sensitive adhesive surface is bonded to an object (for example, another member constituting a portable electronic device). It is done. In this aspect, the pressure-sensitive adhesive sheet attached to the pressure-sensitive sensor functions as a pressure-sensitive adhesive layer in the laminated structure with the pressure-sensitive sensor. Such a pressure-sensitive sensor with an adhesive layer may be in a state where the other adhesive surface located on the side opposite to the pressure-sensitive sensor side is protected by a release liner. The release liner is removed from the other pressure-sensitive adhesive surface when affixed to an object to be fixed to the pressure sensor. Alternatively, in another aspect, the pressure-sensitive adhesive sheet is used by sticking the other pressure-sensitive adhesive surface to an object (an object to be fixed to the pressure-sensitive sensor, such as a member), and then sticking one pressure-sensitive adhesive surface to the pressure-sensitive sensor. It is done. In that case, one pressure-sensitive adhesive surface of the pressure-sensitive adhesive sheet (also referred to as a pressure-sensitive adhesive layer) attached to the object may be in a state protected by a release liner before being attached to the pressure-sensitive sensor. After fixing the pressure-sensitive sensor to the object using the adhesive sheet, it has a laminated structure including an object (for example, a member), a pressure-sensitive sensor, and an adhesive layer that joins the object and the pressure-sensitive sensor. An electronic device (typically a portable electronic device) is obtained.

The matters disclosed by this specification include the following.
(1) An adhesive sheet including an adhesive layer,
The pressure-sensitive adhesive layer is a pressure-sensitive adhesive layer formed from a pressure-sensitive adhesive composition containing a base polymer, two or more types of cross-linking agents having different types of cross-linkable functional groups, and an azole-based antirust agent.
One of the two or more crosslinking agents is an isocyanate crosslinking agent,
The monomer component constituting the base polymer includes a carboxy group-containing monomer,
Content of the said azole type | system | group antirust agent in the said adhesive layer is an adhesive sheet which is less than 8 weight part with respect to 100 weight part of said base polymers.
(2) The pressure-sensitive adhesive sheet according to (1), wherein the pressure-sensitive adhesive layer has a relative dielectric constant at 300 kHz of about 3 or more (for example, about 3 or more and about 6 or less).
(3) The monomer component that constitutes the base polymer contains C _1-4 alkyl (meth) acrylate in an amount of about 50% by weight or more (eg, about 70% by weight or more, or about 90% by weight or more, typically Is approximately 99% by weight or less). The pressure-sensitive adhesive sheet according to the above (1) or (2).
(4) The content of the carboxy group-containing monomer in the monomer component is more than about 3 wt% (for example, about 3.5 wt% or more, or about 4 wt% or more, typically about 15 wt% or less, for example, The pressure-sensitive adhesive sheet according to any one of (1) to (3), wherein the pressure-sensitive adhesive sheet is less than 7% by weight.
(5) The content of the azole rust inhibitor is about 0.2 parts by weight (for example, about 0.5 parts by weight or more) and about 15 parts by weight or less (for example, 10 parts by weight) per 10 parts by weight of the carboxy group-containing monomer. The pressure-sensitive adhesive sheet according to any one of the above (1) to (4), which is at most 5 parts by weight or less.
(6) The azole rust inhibitor is at least one benzotriazole compound selected from the group consisting of 1,2,3-benzotriazole, 5-methylbenzotriazole, 4-methylbenzotriazole and carboxybenzotriazole. The pressure-sensitive adhesive sheet according to any one of (1) to (5), comprising:
(7) The pressure-sensitive adhesive sheet according to any one of (1) to (6), wherein the pressure-sensitive adhesive layer contains a tackifier resin.
(8) The pressure-sensitive adhesive sheet according to (7), wherein the content of the tackifying resin is about 10 parts by weight or more and about 50 parts by weight or less with respect to 100 parts by weight of the base polymer.
(9) The pressure-sensitive adhesive sheet according to (7) or (8) above, which contains a tackifier resin having a hydroxyl value of about 30 mgKOH / g or more as the tackifier resin.
(10) The pressure-sensitive adhesive sheet according to any one of the above (7) to (9), comprising a tackifier resin having a hydroxyl value of about 70 mgKOH / g or more as the tackifier resin.
(11) The pressure-sensitive adhesive sheet according to any one of (7) to (10), which contains a terpene phenol-based resin as the tackifier resin.
(12) The pressure-sensitive adhesive sheet according to (7), wherein the pressure-sensitive adhesive layer contains about 10 to 50 parts by weight of a terpene phenol resin having a hydroxyl value of about 30 to 65 mgKOH / g with respect to 100 parts by weight of the base polymer. .
(13) The pressure-sensitive adhesive sheet according to (7), wherein the pressure-sensitive adhesive layer contains about 10 to 50 parts by weight of a terpene phenol resin having a hydroxyl value of about 70 to 150 mgKOH / g with respect to 100 parts by weight of the base polymer. .
(14) The above-mentioned (1) to (13), wherein the room temperature peel strength with respect to PET is about 15 N / 25 mm or more (for example, about 17 N / 25 mm or more, typically about 40 N / 25 mm or less, for example, about 30 N / 25 mm or less). The pressure-sensitive adhesive sheet according to any one of the above.
(15) The above-mentioned (1) to (14), wherein the room temperature peel strength for aluminum is about 15 N / 25 mm or more (for example, about 17 N / 25 mm or more, typically about 40 N / 25 mm or less, for example, about 30 N / 25 mm or less). The pressure-sensitive adhesive sheet according to any one of the above.
(16) The pressure-sensitive adhesive sheet according to any one of the above (1) to (15), which has a heat-resistant peel strength against PET of about 7 N / 25 mm or more (for example, about 9 N / 25 mm or more, typically about 30 N / 25 mm or less). .
(17) The above-mentioned (1) to (16), wherein the heat-resistant peel strength against aluminum is about 5 N / 25 mm or more (for example, about 10 N / 25 mm or more, typically about 30 N / 25 mm or less, for example, about 20 N / 25 mm or less). The pressure-sensitive adhesive sheet according to any one of the above.
(18) Impact bond strength is about 0.30 mJ / cm ² or more (for example, about 0.40 mJ / cm ² or more, typically about 1.00 mJ / cm ² or less, for example, about 0.70 mJ / cm ² or less). The pressure-sensitive adhesive sheet according to any one of the above (1) to (17).
(19) The pressure-sensitive adhesive sheet according to any one of (1) to (18), wherein a deviation distance in the high-temperature holding force test described in the examples is about 1 mm or less (for example, about 0.5 mm or less).
(20) The content of the isocyanate-based crosslinking agent in the pressure-sensitive adhesive composition is about 0.5 parts by weight or more and about 10 parts by weight or less with respect to 100 parts by weight of the base polymer. ) The pressure-sensitive adhesive sheet according to any one of the above.
(21) Among the above two or more types of crosslinking agents, one type other than the above-mentioned isocyanate crosslinking agent is an epoxy crosslinking agent, an oxazoline crosslinking agent, an aziridine crosslinking agent, a melamine crosslinking agent, a carbodiimide crosslinking agent, or a hydrazine crosslinking agent. At least one non-isocyanate type crosslinking agent selected from the group consisting of an agent, an amine crosslinking agent, a peroxide crosslinking agent, a metal chelate crosslinking agent, a metal alkoxide crosslinking agent, a metal salt crosslinking agent and a silane coupling agent The pressure-sensitive adhesive sheet according to any one of (1) to (20), which is an agent.
(22) The pressure-sensitive adhesive sheet according to (21), wherein the non-isocyanate-based crosslinking agent includes an epoxy-based crosslinking agent.
(23) The content of the non-isocyanate crosslinking agent (for example, epoxy crosslinking agent) in the pressure-sensitive adhesive composition is about 1/1000 or more and about 1/50 or less of the content of the isocyanate crosslinking agent on a weight basis. The pressure-sensitive adhesive sheet according to the above (21) or (22).
(24) The pressure-sensitive adhesive sheet according to any one of (1) to (23), wherein the pressure-sensitive adhesive layer has a thickness of about 10 μm or more and about 50 μm or less.
(25) The pressure-sensitive adhesive sheet according to any one of (1) to (24), wherein the pressure-sensitive adhesive sheet is configured as a baseless double-sided pressure-sensitive adhesive sheet.
(26) A pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer,
The pressure-sensitive adhesive layer is a pressure-sensitive adhesive formed from a pressure-sensitive adhesive composition comprising a base polymer, two or more types of cross-linking agents having different types of cross-linkable functional groups, an azole rust inhibitor, and a tackifier resin. Agent layer,
The monomer component constituting the base polymer contains C _1-4 alkyl (meth) acrylate in an amount of 70% by weight or more of the monomer component,
The monomer component constituting the base polymer includes a carboxy group-containing monomer of 3.5% by weight to 10% by weight of the monomer component,
The content of the azole rust inhibitor in the pressure-sensitive adhesive layer is 0.5 parts by weight or more and 6 parts by weight or less with respect to 100 parts by weight of the base polymer,
The two or more crosslinking agents include an isocyanate crosslinking agent and an epoxy crosslinking agent,
Content of the said isocyanate type crosslinking agent in the said adhesive composition is 0.5 weight part or more and 10 weight part or less with respect to 100 weight part of the said base polymer,
The content of the epoxy crosslinking agent in the pressure-sensitive adhesive composition is 1/1000 or more and 1/100 or less of the content of the isocyanate crosslinking agent,
Content of the said tackifying resin is an adhesive sheet which is 10 to 50 weight part with respect to 100 weight part of said base polymers.
(27) The pressure-sensitive adhesive sheet according to any one of (1) to (26), which is used for fixing a member in a portable electronic device.
(28) The pressure-sensitive adhesive sheet according to (27), wherein the member is a pressure-sensitive sensor (for example, a capacitance-type pressure-sensitive sensor or a resistance-type pressure-sensitive sensor).
(29) a pressure-sensitive sensor (for example, a capacitance-type or resistance-type pressure-sensitive sensor), another member constituting the portable electronic device, and an adhesive sheet that joins the pressure-sensitive sensor and the other member A portable electronic device having a laminated structure comprising:
The said adhesive sheet is a portable electronic device which is an adhesive sheet in any one of said (1)-(26).

  Several examples relating to the present invention will be described below, but the present invention is not intended to be limited to those shown in the examples. In the following description, “part” is based on weight unless otherwise specified.

<Production of adhesive sheet>
(Example 1)
A reactor equipped with a stirrer, thermometer, nitrogen gas inlet tube, reflux condenser and dropping funnel was charged with 95 parts of BA and 5 parts of AA as monomer components and 233 parts of ethyl acetate as a polymerization solvent, and nitrogen gas was introduced. The mixture was stirred for 2 hours. After removing oxygen in the polymerization system in this way, 0.2 part of 2,2′-azobisisobutyronitrile was added as a polymerization initiator, and solution polymerization was performed at 60 ° C. for 8 hours to obtain an acrylic polymer. A solution was obtained. The acrylic polymer had an Mw of about 70 × 10 ⁴ .
To 100 parts of the acrylic polymer contained in the acrylic polymer solution, 0.8 part of 1,2,3-benzotriazole (trade name “BT-120”, manufactured by Johoku Chemical Co., Ltd.), 20 parts of terpene phenol resin (trade name “YS Polystar T-115”, softening point of about 115 ° C., hydroxyl value of 30 to 60 mg KOH / g, manufactured by Yasuhara Chemical Co .; hereinafter referred to as “tackifying resin A”) as a tackifying resin; As a crosslinking agent, 2 parts of an isocyanate crosslinking agent (trade name “Coronate L”, 75% ethyl acetate solution of trimethylolpropane / tolylene diisocyanate trimer adduct, manufactured by Tosoh Corporation) and an epoxy crosslinking agent (trade name “TETRAD”) -C ", 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, manufactured by Mitsubishi Gas Chemical Co., Ltd.) 0.01 parts It was added thereto to prepare a pressure-sensitive adhesive composition was stirred and mixed.
The pressure-sensitive adhesive composition was applied to the release surface of a 38 μm-thick polyester release liner (trade name “Diafoil MRF”, manufactured by Mitsubishi Polyester), dried at 100 ° C. for 2 minutes, and a pressure-sensitive adhesive with a thickness of 25 μm. A layer was formed. A release surface of a 25 μm thick polyester release liner (trade name “Diafoil MRF”, 25 μm thick, manufactured by Mitsubishi Polyester) was bonded to this pressure-sensitive adhesive layer. In this way, a base-less double-sided pressure-sensitive adhesive sheet having a thickness of 25 μm and having both surfaces protected by the two polyester release liners was obtained.

(Examples 2 to 8)
In the preparation of the pressure-sensitive adhesive composition according to Example 1, the types and amounts used of the monomer component, tackifying resin, rust inhibitor and cross-linking agent were set as shown in Table 1. About the other point, it carried out similarly to Example 1, each prepared the adhesive composition which concerns on Examples 2-8, and produced the base-material-free double-sided adhesive sheet using this adhesive composition.
“Tackifier resin B” in Table 1 is a trade name “YS Polystar S-145” (terpene phenol resin, softening point of about 145 ° C., hydroxyl value of 70 to 110 mg KOH / g) manufactured by Yasuhara Chemical Co., Ltd.

(Example 9)
To a monomer mixture composed of 66 parts of 2EHA, 15 parts of N-vinyl-2-pyrrolidone (NVP) and 18 parts of 2-hydroxyethyl acrylate (HEA), 0.07 part of photopolymerization initiator (trade name “Irgacure made by BASF” 184 "and trade name" Irgacure 651 "in a weight ratio of 1: 1), and a prepolymer in which a part of the monomer component is polymerized by irradiating with ultraviolet rays until the viscosity becomes about 20 Pa · s. A composition was obtained. Next, 10 parts of dicyclopentanyl methacrylate (DCPMA) and methyl methacrylate (MMA), a low polymer (copolymerization composition: DCPMA / MMA = 60/40), 0.25 parts of acrylate (HDDA), 0.3 parts of silane coupling agent (trade name “KBM-403”, manufactured by Shin-Etsu Chemical Co., Ltd.) and 1,2,3-benzotriazole (trade name “BT-120”) 0.2 parts of Johoku Chemical Industry Co., Ltd.) was added and mixed to obtain an adhesive composition (composition before curing).
The pressure-sensitive adhesive composition was applied on a polyethylene terephthalate (PET) release liner (trade name “MRF50”, manufactured by Mitsubishi Plastics Co., Ltd.) so that the final thickness (thickness of the pressure-sensitive adhesive layer) was 25 μm. The coated layer was covered with a PET release liner (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd.) to block oxygen, and then cured by irradiating with ultraviolet rays having an illuminance of 5 mW / cm ² for 300 seconds. A baseless double-sided pressure-sensitive adhesive sheet having a thickness of 25 μm protected with a release liner was obtained.

(Examples 10 and 11)
In the preparation of the pressure-sensitive adhesive composition according to Example 1, the types and amounts of use of the rust inhibitor and the cross-linking agent were set as shown in Table 1. Kogyo Co., Ltd. product name “ATDN101 Black”) was used. About the other point, it carried out similarly to Example 1, and prepared the adhesive composition which concerns on Examples 10 and 11, respectively, and produced the base-material-free double-sided adhesive sheet using this adhesive composition.

  After the obtained double-sided PSA sheet was cured for 1 day in an environment of 23 ° C. and 50% RH, the following evaluation test was performed on the double-sided PSA sheet.

<Evaluation test>
[Measurement of peel strength for PET]
In a measurement environment of 23 ° C. and 50% RH, a PET film having a thickness of 50 μm is attached to one adhesive surface of a double-sided adhesive sheet and backed, and cut into a size of 25 mm in width and 100 mm in length to produce a measurement sample. did. About the other adhesion surface of the measurement sample, the PET room temperature peeling strength (N / 25mm) was measured by the method mentioned above.
Moreover, after pasting the measurement sample on the adherend (the surface of the PET film) in the same manner as the measurement of the above-mentioned PET room temperature peel strength in an environment of 23 ° C. and 50% RH, The heat resistant peel strength against PET (N / 25 mm) was measured under the conditions of a tensile speed of 300 mm / min and a peel angle of 180 degrees. The results are shown in Table 1.

[Measurement of peel strength against aluminum]
The room temperature peel strength against aluminum and the heat resistant peel strength against aluminum were measured in the same manner as the measurement of peel strength for PET except that a 3 mm thick aluminum plate was used as the adherend. The results are shown in Table 1.

[Measurement of impact bond strength]
The impact adhesive strength was measured using a pendulum type adhesive shear impact tester based on JIS K6855 (corresponding to international standard ISO 9653). As a test piece, a 10 mm square, 5 mm thick stainless steel (SUS304) plate is used as another stainless steel (SUS304) plate by using a pressure sensitive adhesive sheet piece obtained by cutting the substrate-less double-sided adhesive sheet according to each example into a 10 mm square. After pressure bonding with a load of 35 N on the top for 10 seconds, a material cured at room temperature for 48 hours was used. The measurement was performed under the conditions of a hammer energy of 2.75 J and a hammer speed (impact speed) of 3.5 m / sec.

[High temperature holding power]
According to JIS Z0237: 2009, the heat-resistant cohesive strength was evaluated by conducting a high temperature holding power test at a temperature of 80 ° C. That is, in an environment of 23 ° C. and 50% RH, a PET film having a thickness of 50 μm was attached to one adhesive surface of the double-sided pressure-sensitive adhesive sheet, lined, and cut into a width of 10 mm to prepare a measurement sample. The other adhesive surface of the measurement sample was attached to a bakelite plate as an adherend by reciprocating a 2 kg roller once with a bonding area of 10 mm in width and 20 mm in length. The measurement sample attached to the adherend in this manner was dropped in an environment of 80 ° C. and left for 30 minutes, and then a 1 kg load was applied to the free end of the measurement sample. With respect to the measurement sample after being left for 1 hour in an environment at 80 ° C. with the load applied, the displacement distance (mm) from the first application position was measured. The test was performed using three measurement samples for the pressure-sensitive adhesive sheet according to each example (that is, n = 3), and the arithmetic average value of the shift distances is shown in Table 1. When one of the three measurement samples was peeled off from the adherend within 1 hour and dropped, “falling” was displayed in the column of the heat resistant cohesive force in Table 1.

[Corrosion test]
A transparent PET film with a thickness of 200 μm is attached to one adhesive surface of a double-sided adhesive sheet, and this is laminated on both sides of a copper foil with a thickness of 25 μm, and then cut into a 10 mm square shape. Thus, a laminate sample having a structure of PET film / double-sided PSA sheet / copper foil / double-sided PSA sheet / PET film was prepared. This sample was stored under high temperature and high humidity conditions of 85 ° C. and 85% RH. In 200 hours and 500 hours after the start of the preservation, and observation watch foil visually the PET film over, the presence or absence of appearance change was evaluated by the following three steps. The results are shown in Table 1.
E: No discoloration was observed in the observation after 500 hours (excellent corrosion resistance).
G: Slight discoloration was observed at the corners of the sample in the observation after 500 hours, but no discoloration was observed in the observation after 200 hours (good corrosion resistance).
P: A clear discoloration was observed in observation after 200 hours (poor corrosion resistance).

[Specific permittivity measurement]
The pressure-sensitive adhesive layer (baseless double-sided pressure-sensitive adhesive sheet) according to each example was sandwiched between a copper foil and an electrode, and the relative dielectric constant at a frequency of 300 kHz was measured with the following apparatus. Three samples were prepared for measurement, and the average of the measured values of these three samples was taken as the dielectric constant. The relative dielectric constant of the pressure-sensitive adhesive layer at a frequency of 300 kHz was measured under the following conditions according to JIS K6911. The results are shown in Table 1.
Measuring method: Capacity method (apparatus: using Agilent Technologies E4980A Precision LCR Meter)
Electrode configuration: 12.1 mmφ, 0.5 mm thick aluminum plate Counter electrode: 3 oz copper plate Measurement environment: 23 ° C., 55% RH

  As shown in Table 1, the base polymer of the pressure-sensitive adhesive layer has a monomer composition containing a carboxy group-containing monomer, and in the composition containing an azole anticorrosive agent, an isocyanate crosslinking agent and another crosslinking agent are combined. The pressure-sensitive adhesive sheets of Examples 1 to 6, 10, and 11 used have superior shear impact resistance compared to the pressure-sensitive adhesive sheet according to Example 9 in which the base polymer of the pressure-sensitive adhesive layer does not contain a carboxy group-containing monomer. Compared to the pressure-sensitive adhesive sheet, it has higher heat cohesion and good metal corrosion prevention. Particularly good results were obtained with the pressure-sensitive adhesive sheets according to Examples 1, 2, 4, 5, 10, and 11.

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

1, 2 Adhesive sheet 21 Adhesive layer 21A, 21B Adhesive surface 31, 32 Release liner

Claims (10)

An adhesive sheet including an adhesive layer,
The pressure-sensitive adhesive layer, an acrylic polymer as a base polymer, a cross-linking agent, and azole corrosion inhibitor, a PSA layer formed from a PSA composition containing a
The crosslinking agent includes an isocyanate crosslinking agent and an epoxy crosslinking agent ,
The monomer component constituting the base polymer includes a carboxy group-containing monomer,
Content of the said azole type | system | group antirust agent in the said adhesive layer is an adhesive sheet which is less than 8 weight part with respect to 100 weight part of said base polymers.   The pressure-sensitive adhesive sheet according to claim 1, wherein the pressure-sensitive adhesive layer has a relative dielectric constant of 3 or more at 300 kHz.   The pressure-sensitive adhesive sheet according to claim 1 or 2, wherein the monomer component constituting the base polymer includes (meth) acrylate having an alkyl group having 4 or less carbon atoms at the ester terminal at 50% by weight or more of the monomer component.   The pressure-sensitive adhesive sheet according to any one of claims 1 to 3, wherein the content of the carboxy group-containing monomer in the monomer component is more than 3% by weight.   The content of the azole rust inhibitor in the pressure-sensitive adhesive layer is 0.2 parts by weight or more and 15 parts by weight or less per 10 parts by weight of the carboxy group-containing monomer contained in the monomer component constituting the base polymer. Item 5. The pressure-sensitive adhesive sheet according to any one of items 1 to 4.   The pressure-sensitive adhesive sheet according to any one of claims 1 to 5, wherein the pressure-sensitive adhesive layer contains a tackifier resin.   The pressure-sensitive adhesive sheet according to claim 6, comprising a tackifier resin having a hydroxyl value of 30 mgKOH / g or more as the tackifier resin.   The pressure-sensitive adhesive sheet according to any one of claims 1 to 7, wherein the room temperature peel strength with respect to polyethylene terephthalate is 15 N / 25 mm or more.   As the azole rust inhibitor, including at least one benzotriazole compound selected from the group consisting of 1,2,3-benzotriazole, 5-methylbenzotriazole, 4-methylbenzotriazole and carboxybenzotriazole, The pressure-sensitive adhesive sheet according to any one of claims 1 to 8.   The pressure-sensitive adhesive sheet according to any one of claims 1 to 9, which is used for fixing a member in a portable electronic device.

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