TW202200739A - Film with adhesive layer - Google Patents

Abstract

Provided is a separatorless film with an adhesive layer in which a polyethylene-based film is not used as a substrate layer, wherein winding and unwinding are possible without a separatorless and contamination of a surface of an adherent can be suppressed. The film with an adhesive layer according to an embodiment of the present invention comprises a release layer, a substrate layer, and an adhesive layer, in that order, wherein there is no separator on the side of the adhesive layer opposite the substrate layer, the release layer is a layer formed from a release layer forming material that includes a polyvinyl alcohol-based resin and an isocyanate that includes a long-chain alkyl group, the substrate layer includes a polyester-based resin, and the thickness of the adhesive layer is 0.5 [mu]m-5.0 [mu]m.

Description

Adhesive layer film

The present invention relates to a film with an adhesive layer.

In the manufacturing steps of optical components or electronic components, in order to prevent damage to the component surfaces during processing, assembly, inspection, transportation, etc., a surface protection film (SPV) is attached.

As the surface protection film, various types of surface protection films having a substrate layer, an adhesive layer, and a release film in this order have been typically reported. For example, a surface protection film with a release film is reported, which does not contaminate the surface of the adherend and is not easily deformed by external force when the total thickness is reduced (Patent Document 1).

On the other hand, in order to reduce the cost of the separator, etc., as a surface protective film used in the production steps of optical members or electronic members, a surface protective film without a separator (no separator) on the surface side of the adhesive layer has recently been pursued. . As such a surface protective film without a separator, a surface protective film in which a polyethylene-based film and an adhesive layer are laminated is reported (Patent Document 2). The surface protective film is produced by extrusion molding, and by embossing the back surface of the polyethylene film, it can be wound and unrolled without a separator, and can be provided as a roll.

However, the polyethylene-based film has a problem that lumps (fish eyes) in which the resin is not completely melted are likely to be contained. Moreover, since an embossing process was given to the back surface of a polyethylene-type film, there existed a problem, such as a dent in an optical member or an electronic member at the time of bonding. prior art literature Patent Literature

Patent Document 1: Japanese Patent Laid-Open No. 2017-31278 Patent Document 2: Japanese Patent Laid-Open No. 06-033022

[Problems to be Solved by Invention]

The subject of the present invention is to provide a film with an adhesive layer without a separator, which does not use a polyethylene-based film as a film with an adhesive layer on a substrate layer, and which can be rolled without a separator Take out and roll out, can prevent the surface of the adhered body from being polluted. [Technical means to solve problems]

The inventors of the present invention focused on the use of a polyester-based film that can suppress the problem of fish-eyes and dents as a film with an adhesive layer without a release film as a base layer, and conducted intensive research to make the thickness of the adhesive layer very thin. , and the release layer formed by a specific treatment agent is arranged on the opposite side of the base material layer and the adhesive layer to solve the above problems.

The film with the adhesive layer according to the embodiment of the present invention has a release layer, a substrate layer, and an adhesive layer in sequence, and There is no release film on the side of the adhesive layer opposite to the base material layer, The release layer is a layer formed of a release layer-forming material comprising a long-chain alkyl group-containing isocyanate and a polyvinyl alcohol-based resin, The base material layer contains polyester resin, The thickness of the adhesive layer is 0.5 μm˜5.0 μm.

In one embodiment, the film with the above-mentioned adhesive layer is measured at a temperature of 23° C. and a humidity of 50% RH, with a peeling speed of 0.3 m/min and a peeling angle of 180 degrees. The peel force is 0.01 N/25 mm or more.

In one embodiment, the film with the above-mentioned adhesive layer is measured at a temperature of 23° C. and a humidity of 50% RH with a peeling speed of 10 m/min and a peeling angle of 180 degrees. The peel force is 0.20 N/25 mm or less.

In one embodiment, the thickness of the release layer is 1 nm˜200 nm.

In one embodiment, the above-mentioned long-chain alkyl group-containing isocyanate is a monofunctional isocyanate.

In one embodiment, the long-chain alkyl group contained in the long-chain alkyl group-containing isocyanate is an alkyl group having 6 or more carbon atoms.

In one Embodiment, the said polyvinyl alcohol-type resin has an acetal group, an acetyl group, and a hydroxyl group.

In one embodiment, the above-mentioned adhesive layer is formed of an adhesive composition, and the adhesive composition is an acrylic adhesive composition, and the acrylic adhesive composition includes an acrylic polymer and a crosslinking agent.

In one embodiment, the above-mentioned acrylic polymer is formed from the composition (A), and the composition (A) comprises: (a component) (a component) the carbon number of the alkyl group of the alkyl ester moiety is 4-12 (methyl) at least one selected from the group consisting of (meth)acrylate and (meth)acrylic acid having an OH group. [Effect of invention]

According to the present invention, it is possible to provide a film with an adhesive layer without a separator, which does not use a polyethylene-based film as a film with an adhesive layer on a base layer, and can be rolled without a separator. Take out and roll out, can prevent the surface of the adhered body from being polluted.

In this specification, the expression "weight" may be replaced by "mass", which is conventionally used as a unit of the SI system to express weight.

In this specification, the expression "(meth)acrylic acid" means "acrylic acid and/or methacrylic acid", and the expression "(meth)acrylate" means "acrylate and/or methacrylate ester". ", the expression "(meth)allyl" means "allyl and/or methallyl", and the expression "(meth)acrolein" means "acrolein and/or meth acrolein".

≪≪1. Film with adhesive layer≫≫ The adhesive layer-attached film of the embodiment of the present invention has a release layer, a substrate layer, and an adhesive layer in sequence, and does not have a release film on the side of the adhesive layer opposite to the substrate layer.

If the film to which the adhesive layer is attached has a release layer, a substrate layer, and an adhesive layer in sequence, and there is no release film on the side of the adhesive layer opposite to the substrate layer, the effect of the present invention may not be impaired. There are any suitable other layers within the range.

As shown in FIG. 1 , one embodiment of the film with an adhesive layer is a form in which the film 100 with an adhesive layer of the present invention is directly laminated in this order with a release layer 10 , a substrate layer 20 , and an adhesive layer 30 film.

As shown in FIG. 2, another embodiment of the film with an adhesive layer is the following form, that is, the film 100 with an adhesive layer of the present invention is directly laminated in sequence with the release layer 10, the substrate layer 20, the antistatic layer The film formed by the layer 40 and the adhesive layer 30 .

As shown in FIG. 3 , another embodiment of the film with an adhesive layer is as follows, that is, the film 100 with an adhesive layer of the present invention is directly laminated in sequence with the release layer 10 , the antistatic layer 40 , and the substrate. A film formed by layer 20 and adhesive layer 30 .

The film to which the adhesive layer of the embodiment of the present invention is attached can be used for various purposes. Representatively, there can be exemplified surface protection films or slides, etc., which are used in optical components or electronic components (such as glass, polarizers, wavelength plates, retardation plates, optical compensation films, etc. used in liquid crystal displays, etc.). In the manufacturing steps of reflector, brightness enhancement film, transparent conductive film, etc.), the surface is protected in order to prevent damage to the surface of the component during processing, assembly, inspection, transportation, etc.

As the form of the film to which the pressure-sensitive adhesive layer according to the embodiment of the present invention is attached, any appropriate form can be adopted within a range that does not impair the effects of the present invention. As such a form, a winding body (it is also called a roll body), a single-piece body, etc. are mentioned, for example.

The film with the adhesive layer is measured at a temperature of 23°C and a humidity of 50% RH, with a peeling speed of 0.3 m/min and a peeling angle of 180 degrees. The low-speed peeling force of the adhesive layer to the release layer is preferably 0.01 N/25 mm or more, more preferably 0.01 N/25 mm to 0.15 N/25 mm, further preferably 0.01 N/25 mm to 0.10 N/25 mm, particularly preferably 0.01 N/25 mm to 0.05 N/25 mm. In the case where the above-mentioned low-speed peeling force does not reach 0.01 N/25 mm, for example, there is a relationship between the adhesive layer and the release layer during winding to make a wound body or in the state of the wound body that has been wound. Adhesion becomes low, and there exists a possibility that it may not be able to wind up smoothly, or there exists a possibility that the shape of a winding body cannot be maintained. When the said low-speed peeling force exists in the said range, the windability without a separator can be made favorable. The details of the measurement method of the above-mentioned low-speed peel force are described below.

The film with the adhesive layer is measured at a temperature of 23°C and a humidity of 50% RH, with a peeling speed of 10 m/min and a peeling angle of 180 degrees. The high-speed peeling force of the adhesive layer to the release layer is preferably 0.20 N/25 mm or less, more preferably 0.01 N/25 mm to 0.15 N/25 mm, further preferably 0.01 N/25 mm to 0.10 N/25 mm, particularly preferably 0.01 N/25 mm to 0.05 N/25 mm. If the above-mentioned high-speed peeling force exceeds 0.20 N/25 mm, for example, when the film with the adhesive layer is rolled out from the wound body, heavy peeling occurs, and there is a possibility that it cannot be rolled out smoothly. When the said high-speed peeling force exists in the said range, the unwinding property without a separator can be made favorable. The details of the measurement method of the above-mentioned high-speed peel force are described below.

It is preferable that the film with the adhesive layer is such that the above-mentioned low-speed peeling force and the above-mentioned high-speed peeling force are in the relationship of low-speed peeling force≦high-speed peeling force. If it exists in such a relationship, in the case where a separator does not exist, it can express more excellent winding property and more excellent unwinding property.

For the film with the adhesive layer, at a temperature of 23°C and a humidity of 50% RH, in a non-clean environment (specifically, different from the clean room that is classified according to the definition in ISO146441-1:2015 and the management standard is set space), the adhesive layer and the optical film (specifically, the "transparent protective film 1A" described in the examples of Japanese Patent Laid-Open No. 2017-26939) are pasted with a size of 10 cm ² × 10 cm ² When attaching, mark the foreign matter that bites in during lamination, confirm the size of the foreign matter with an optical microscope, calculate the foreign matter larger than 100 μm, calculate the foreign matter remaining in the optical film after peeling off the film with the adhesive layer, and measure the foreign matter removal rate. The removal rate is preferably 50% or more, more preferably 60% or more, still more preferably 70% or more, particularly preferably 80% or more. If the said foreign material removal rate is low, since it becomes a bright spot for an optical film, there exists a possibility that a yield may fall. The details of the measurement method of the foreign matter removal rate are described below.

The total thickness of the film with the adhesive layer is preferably 25 μm to 100 μm, more preferably 25 μm to 75 μm, further preferably 30 μm to 50 μm, particularly preferably 35 μm to 45 μm. If the total thickness of the film with the adhesive layer is within the above range, the effect of the present invention can be further exhibited.

The total light transmittance of the film with the adhesive layer is preferably 60% or more, more preferably 70% to 100%, further preferably 80% to 100%, particularly preferably 83% to 100%, and most preferably 85% %～100%.

The haze of the film with the adhesive layer is preferably 15% or less, more preferably 0% to 10%, further preferably 0% to 8%, particularly preferably 0% to 7%, and most preferably 0% to 10%. 6%.

≪1-1. Release layer≫ The release layer is a layer formed of a release layer-forming material containing a long-chain alkyl group-containing isocyanate and a polyvinyl alcohol-based resin.

The release layer can be defined as one formed of the above-described release layer forming material. It is impossible and impractical to directly identify the release layer by its structure (“impossible/impractical”) Therefore, the release layer is appropriately specified as an "object" by defining it as "formed by a release layer forming material".

The release layer forming material includes a long-chain alkyl group-containing isocyanate and a polyvinyl alcohol-based resin. In the release layer forming material, the content ratio of the long-chain alkyl group-containing isocyanate is preferably 100 to 1000 parts by weight, more preferably 100 to 900 parts by weight, relative to 100 parts by weight of the polyvinyl alcohol-based resin. , more preferably 150-850 parts by weight, still more preferably 200-800 parts by weight, particularly preferably 250-700 parts by weight, and most preferably 300-600 parts by weight.

The effect of the present invention can be exhibited by the release layer forming material containing the long-chain alkyl group-containing isocyanate and the polyvinyl alcohol-based resin, the film having the adhesive layer of the release layer formed by the reaction thereof.

Only one type of long-chain alkyl group-containing isocyanate may be used, or two or more types may be used.

Only one type of polyvinyl alcohol-based resin may be used, or two or more types may be used.

As the long-chain alkyl group-containing isocyanate, any appropriate long-chain alkyl group-containing isocyanate can be used within a range that does not impair the effects of the present invention.

The long-chain alkyl group-containing isocyanate is preferably a monofunctional isocyanate in order to further exhibit the effects of the present invention. If a polyfunctional isocyanate is used as the long-chain alkyl group-containing isocyanate, unreacted isocyanate groups may react with hydroxyl groups that may be included in the adhesive layer, and the risk of poor peeling increases. Moreover, there exists a possibility that the risk of gelatinization by crosslinking at the time of reaction of the release layer forming material may become high, for example, there exists a possibility that thin-layer coating cannot be performed by the following coating method.

The long-chain alkyl group of the long-chain alkyl group-containing isocyanate is preferably an alkyl group having 6 or more carbon atoms, more preferably an alkyl group having 8 or more carbon atoms, in order to further exhibit the effects of the present invention. An alkyl group having 10 or more carbon atoms is preferable, and an alkyl group having 12 or more carbon atoms is particularly preferable. In order to further express the effect of the present invention, the upper limit of the carbon number of the long-chain alkyl group contained in the long-chain alkyl group-containing isocyanate is preferably 24 or less. As such a long-chain alkyl group, an octyl group, a decyl group, a lauryl group, an octadecyl group, a behenyl group, etc. are mentioned, for example.

Specific examples of the long-chain alkyl group-containing isocyanate include octyl isocyanate, decyl isocyanate, lauryl isocyanate, octadecyl isocyanate, and behenyl isocyanate. etc., preferably octadecyl isocyanate.

As the polyvinyl alcohol-based resin, any appropriate polyvinyl alcohol-based resin can be used within a range that does not impair the effects of the present invention.

As the polyvinyl alcohol-based resin, for example, polyvinyl alcohol; vinyl alcohol-α-olefin copolymer; , Acetyl and hydroxyl polyvinyl alcohol resins. As a polyvinyl alcohol-type resin which has such an acetal group, an acetyl group, and a hydroxyl group, butyral resin is mentioned typically.

The release layer forming material preferably contains a solvent. Only one solvent may be used, or two or more types may be used.

As a solvent, in order to further express the effect of this invention, it is preferable to contain the solvent which does not have a hydroxyl group as a main solvent. Polyvinyl alcohol-based resins are generally easy to dissolve in alcohol-based solvents such as ethanol, so alcohol-based solvents may be selected as solvents. However, in the present invention, the hydroxyl group of a solvent having a hydroxyl group reacts with an isocyanate containing a long-chain alkyl group In view of this situation, it was found that, in order to further express the effects of the present invention, it is preferable to include a solvent not having a hydroxyl group as a main solvent.

The content ratio of the solvent having no hydroxyl group in the total amount of the solvent is preferably more than 50% by weight and 100% by weight or less, more preferably 70% by weight to 100% by weight, and still more preferably 90% by weight to 100% by weight , preferably 95% by weight to 100% by weight, and most preferably 98% by weight to 100% by weight. If the content ratio of the solvent without a hydroxyl group in the total amount of the solvent is 50% by weight or less, the hydroxyl group of the solvent having a hydroxyl group may react with the long-chain alkyl group-containing isocyanate, and the desired release layer may not be obtained. Yu.

As the solvent having no hydroxyl group, any appropriate solvent having no hydroxyl group can be used within a range not impairing the effects of the present invention. As a solvent which does not have such a hydroxyl group, the aromatic hydrocarbon solvent which does not have a hydroxyl group, such as toluene, toluene, etc. are mentioned, for example.

The release layer forming material may contain other additives. As such other additives, any appropriate other additives may be employed within the range not impairing the effects of the present invention. Examples of such other additives include powders such as antistatic agents, colorants, and pigments; surfactants; plasticizers; adhesion imparting agents; low-molecular-weight polymers; surface lubricants; leveling agents; antioxidants ; Corrosion inhibitor; Light stabilizer; Ultraviolet absorber; Polymerization inhibitor; Silane coupling agent; Inorganic filler; Organic filler; Metal powder; Organic particles; Inorganic particles, etc.

As long as it is a method of forming the release layer from the release layer forming material, the release layer can be formed by any appropriate method within the range that does not impair the effects of the present invention. As such a method, the method of forming a release layer on a base material layer by apply|coating a release layer forming material on a base material layer, drying and removing a solvent etc. is mentioned, for example. After the release layer is formed on the base material layer, it can be cured for the purpose of adjusting the transfer of the components of the release layer. In addition, when the release layer forming material is coated on the base layer to form the release layer, one or more solvents other than the solvent originally contained in the release layer forming material may be re-added to the release layer forming material , so that it can be evenly coated on the substrate layer.

As a method of coating the release layer forming material on the base material layer, any appropriate coating method can be adopted within the range not impairing the effects of the present invention. As such a method, a roll coating method, a gravure coating method, a reverse coating method, a roll brush coating method, a spray coating method, an air knife coating method, and a die coater method may be mentioned. Such as extrusion coating method and so on.

The thickness of the release layer is preferably 1 nm to 200 nm, more preferably 5 nm to 100 nm, and more preferably 10 nm to 50 nm. If the thickness of the release layer is within the above range, the effect of the present invention can be further exhibited.

≪1-2. Substrate layer≫ In order to express the effects of the present invention, the base material layer contains a polyester-based resin.

The content ratio of the polyester resin in the base material layer is preferably more than 50% by weight and not more than 100% by weight, more preferably 70% by weight to 100% by weight, further preferably 90% by weight to 100% by weight, especially It is preferably 95% by weight to 100% by weight, and most preferably 98% by weight to 100% by weight. If the content ratio of the polyester-based resin in the base material layer is within the above-mentioned range, the effect of the present invention can be further exhibited.

As the polyester-based resin, any appropriate polyester-based resin can be used within a range that does not impair the effects of the present invention. As such a polyester-based resin, in order to further express the effect of the present invention, it is preferably selected from polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethylene terephthalate At least one of the group consisting of butylene formate (PBT), more preferably polyethylene terephthalate (PET).

The thickness of the base material layer is preferably 1 μm to 300 μm, more preferably 5 μm to 200 μm, further preferably 10 μm to 150 μm, particularly preferably 20 μm in order to further exhibit the effects of the present invention. ~100 μm, the best is 30 μm ~ 80 μm.

The base material layer may be only one layer, or may be two or more layers.

The substrate layer can be extended.

The substrate layer may be subjected to surface treatment. As surface treatment, corona treatment, plasma treatment, chromic acid treatment, ozone exposure, flame exposure, high voltage electric shock exposure, ionizing radiation treatment, coating treatment with a primer, etc. are mentioned, for example.

In the base material layer, any appropriate additive may be contained within a range not impairing the effects of the present invention. Examples of such additives include powders such as antistatic agents, colorants, and pigments; surfactants; plasticizers; adhesion imparting agents; low-molecular-weight polymers; surface lubricants; leveling agents; antioxidants; Corrosion inhibitor; light stabilizer; ultraviolet absorber; polymerization inhibitor; silane coupling agent; inorganic filler; organic filler; metal powder; organic particles; inorganic particles, etc.

≪1-3. Adhesive layer≫ As the adhesive layer, any appropriate adhesive layer can be used within a range that does not impair the effects of the present invention. The adhesive layer may be only one layer, or may be two or more layers.

In order to be able to exhibit the effects of the present invention, the thickness of the adhesive layer is 0.5 μm to 5.0 μm, preferably 0.5 μm to 4.0 μm, more preferably 0.5 μm to 3.0 μm, further preferably 0.6 μm to 2.5 μm, especially Preferably, it is 0.7 μm to 2.0 μm, and most preferably, it is 0.8 μm to 1.5 μm. By making the thickness of the adhesive layer within the above-mentioned range, it is possible to provide an adhesive layer-free film without a separator, which does not use a polyethylene-based film as a film for the adhesive layer of the substrate layer, and can be used in Winding and unwinding without the presence of a separator can prevent the surface of the adherend from being contaminated. In particular, by making the thickness of the adhesive layer within the above-mentioned range, the obtained adhesive layer-attached film has excellent windability and excellent unwinding properties in the absence of a separator and is compatible with the adherend. The contamination reduction of the surface can show a good balance.

Furthermore, when the main purpose is to contaminate the surface of the adherend, the thickness of the adhesive layer of the obtained film with the adhesive layer is preferably 0.5 μm to 5.0 μm, more preferably 0.6 μm to 0.6 μm. 5.0 μm, more preferably 0.8 μm to 5.0 μm.

The adhesive layer preferably contains at least one selected from the group consisting of acrylic adhesives, urethane-based adhesives, and polysiloxane-based adhesives.

The adhesive layer can be formed by any suitable method. As such a method, for example, a method of mixing an adhesive composition (preferably selected from an acrylic adhesive composition, a urethane adhesive composition, and a silicone adhesive composition) can be exemplified. At least one of the group consisting of) is coated on any appropriate substrate (eg, a substrate layer), heated and dried as necessary, and cured as necessary to form an adhesive layer on the substrate. As such a coating method, for example, a method of coating with a coater such as a gravure roll coater, a reverse roll coater, a touch roll coater, or a dip roll can be exemplified. Type coater, rod coater, blade coater, air knife coater, spray coater, notch wheel coater, direct coater, roll brush coater, etc.

The adhesive layer may contain conductive components. Only one type of conductive component may be used, or two or more types may be used.

<1-3-1. Acrylic adhesive> The acrylic adhesive is formed from an acrylic adhesive composition.

In order to further express the effect of the present invention, the acrylic adhesive composition preferably contains an acrylic polymer and a crosslinking agent.

Acrylic polymers may be referred to as so-called base polymers in the field of acrylic adhesives. Only one type of acrylic polymer may be used, or two or more types may be used.

The content ratio of the acrylic polymer in the acrylic adhesive composition is preferably 60% by weight to 99.9% by weight, more preferably 65% by weight to 99.9% by weight, and more preferably 70% by weight in terms of solid content ~ 99.9 wt %, particularly preferably 75 wt % to 99.9 wt %, and most preferably 80 wt % to 99.9 wt %.

As the acrylic polymer, any appropriate acrylic polymer can be used within a range not impairing the effects of the present invention.

In order to further exhibit the effects of the present invention, the weight-average molecular weight of the acrylic polymer is preferably 300,000 to 2.5 million, more preferably 350,000 to 2,000,000, further preferably 400,000 to 1.8 million, and particularly preferably 45,000 to 2,000,000. 10,000 to 1.5 million.

As an acrylic polymer, in order to further express the effect of the present invention, an acrylic polymer formed by polymerizing a composition (A) comprising the following components, which are (a component) alkyl esters, is preferred At least one selected from the group consisting of (meth)acrylic acid alkyl ester having 4 to 12 carbon atoms in the alkyl group, and (b component) of (meth)acrylic acid ester having an OH group and (meth)acrylic acid 1 type.

(a component) and (b component) each independently may be only 1 type, and may be 2 or more types.

Alkyl (meth)acrylate (component a) having 4 to 12 carbon atoms in the alkyl ester moiety, for example, n-butyl (meth)acrylate and isobutyl (meth)acrylate. ester, 2-butyl (meth)acrylate, 3-butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, (meth)acrylate Octyl acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, Isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, and the like. Among them, in order to further express the effect of the present invention, n-butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate are preferred, and n-butyl acrylate and 2-ethylhexyl acrylate are more preferred. ester.

As at least one (b component) selected from the group consisting of (meth)acrylate having an OH group and (meth)acrylic acid, for example, 2-hydroxyethyl (meth)acrylate, ( (meth)acrylates having OH groups such as 3-hydroxypropyl meth)acrylate and 4-hydroxybutyl (meth)acrylate; (meth)acrylic acid. Among them, in order to further express the effect of the present invention, 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and (meth)acrylic acid are preferred, and 4-hydroxy acrylate is more preferred. Butyl ester, acrylic acid.

The composition (A) may contain comonomers other than (a) component and (b) component. Only one type of copolymerizable monomer may be used, or two or more types may be used. Examples of such comonomers include itonic acid, maleic acid, fumaric acid, crotonic acid, methacrylic acid, and acid anhydrides of these (for example, maleic anhydride, iconic acid, etc.) Acid anhydride and other acid anhydride group-containing monomers) and other carboxyl group-containing monomers (however, (meth)acrylic acid is excluded); (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N-hydroxyl Methyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-hydroxyethyl (meth) propylene Amino group-containing monomers such as amide; Monomers; epoxy group-containing monomers such as glycidyl (meth)acrylate and methyl glycidyl (meth)acrylate; cyano group-containing monomers such as acrylonitrile or methacrylonitrile; N-vinyl-2 -pyrrolidone, (meth)acrylomorpholine, N-vinylpiperidone, N-vinylpiperidone, N-vinylpyrrole, N-vinylimidazole, vinylpyridine, vinylpyrimidine, Heterocycle-containing vinyl monomers such as vinyloxazole; sulfonic acid group-containing monomers such as sodium vinylsulfonate; phosphoric acid group-containing monomers such as 2-hydroxyethyl acryloyl phosphate; cyclohexyl maleic Imide group-containing monomers such as imide and isopropylmaleimide; isocyanate group-containing monomers such as 2-methacryloyloxyethyl isocyanate; (meth)acrylic acid (Meth)acrylates with alicyclic hydrocarbon groups such as cyclopentyl ester, cyclohexyl (meth)acrylate, iso(meth)acrylate, etc.; phenyl (meth)acrylate, benzene (meth)acrylate (meth)acrylates with aromatic hydrocarbon groups such as oxyethyl ester and benzyl (meth)acrylate; vinyl esters such as vinyl acetate and vinyl propionate; aromatic vinyl compounds such as styrene and vinyltoluene; Olefins or dienes such as ethylene, butadiene, isoprene, isobutylene; vinyl ethers such as vinyl alkyl ether; vinyl chloride, etc.

As a copolymerizable monomer, a polyfunctional monomer can also be used. The polyfunctional monomer system refers to a monomer having two or more ethylenically unsaturated groups in one molecule. As the ethylenically unsaturated group, any appropriate ethylenically unsaturated group can be used within a range not impairing the effects of the present invention. Examples of such ethylenically unsaturated groups include radically polymerizable functional groups such as vinyl, propenyl, isopropenyl, vinyl ether (vinyloxy), and allyl ether (allyloxy). . As a polyfunctional monomer, for example, hexanediol di(meth)acrylate, butanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, ) propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, Trimethylolpropane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, allyl(meth)acrylate, vinyl(meth)acrylate, divinylbenzene, epoxy Acrylates, acrylic polyesters, acrylic urethanes, etc. Only one type of such a polyfunctional monomer may be sufficient as it, and two or more types may be sufficient as it.

As a comonomer, (meth)acrylic-acid alkoxyalkyl ester can also be used. As alkoxyalkyl (meth)acrylate, for example, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, methyl (meth)acrylate may be mentioned. Oxytriethylene glycol, 3-methoxypropyl (meth)acrylate, 3-ethoxypropyl (meth)acrylate, 4-methoxybutyl (meth)acrylate, (methyl) ) 4-ethoxybutyl acrylate, etc. Only one type of alkoxyalkyl (meth)acrylate may be used, or two or more types may be used.

In order to further express the effects of the present invention, an alkyl (meth)acrylate having 4 to 12 carbon atoms in the alkyl group of the alkyl ester moiety is required relative to the total amount (100% by weight) of the monomer components constituting the acrylic polymer. The content of the base ester (component a) is preferably 30% by weight or more, more preferably 35% by weight to 99% by weight, still more preferably 40% by weight to 98% by weight, and particularly preferably 50% by weight to 95% by weight.

In order to further express the effect of the present invention, the group consisting of (meth)acrylate and (meth)acrylic acid having an OH group is selected from the total amount (100% by weight) of the monomer components constituting the acrylic polymer. The content of at least one of the group (component b) is preferably 1% by weight or more, more preferably 1% by weight to 30% by weight, still more preferably 2% by weight to 20% by weight, particularly preferably 3% by weight to 15% by weight.

In the case of using both (meth)acrylate and (meth)acrylic acid having an OH group as the (b component), in order to further express the effects of the present invention, the monomer components constituting the acrylic polymer are In the total amount (100% by weight), the content of the (meth)acrylate having an OH group is preferably 2% by weight or more, more preferably 3% by weight to 30% by weight, and still more preferably 4% by weight to 20% by weight , particularly preferably 5% by weight to 15% by weight.

In the case of using both (meth)acrylate and (meth)acrylic acid having an OH group as the (b component), in order to further express the effects of the present invention, the monomer components constituting the acrylic polymer are The total amount (100% by weight), the content of (meth)acrylic acid is preferably 0.001% by weight or more, more preferably 0.001% by weight to 10% by weight, more preferably 0.005% by weight to 5% by weight, and particularly preferably 0.01% by weight % by weight to 1% by weight.

The composition (A) may contain any appropriate other components within a range not impairing the effects of the present invention. As such other components, a polymerization initiator, a chain transfer agent, a solvent, etc. are mentioned, for example. As the content of these other components, any appropriate content can be adopted within a range not impairing the effects of the present invention.

As the polymerization initiator, a thermal polymerization initiator, a photopolymerization initiator (photoinitiator), or the like can be used depending on the kind of the polymerization reaction. Only one type of polymerization initiator may be used, or two or more types may be used.

The thermal polymerization initiator is preferably used when obtaining an acrylic polymer by solution polymerization. As such thermal polymerization initiators, for example, azo-based polymerization initiators, peroxide-based polymerization initiators (for example, dibenzyl peroxide, 3-butyl peroxide maleate) may be mentioned. etc.), redox-based polymerization initiators, etc. Among these thermal polymerization initiators, the azo-based initiators disclosed in Japanese Patent Laid-Open No. 2002-69411 are particularly preferred. Such an azo-based polymerization initiator is preferable in that the decomposition product of the polymerization initiator is less likely to remain in the acrylic polymer as a part that generates heat-generated gas (outgassing). As the azo-based polymerization initiator, 2,2'-azobisisobutyronitrile (hereinafter, sometimes referred to as AIBN), 2,2'-azobis-2-methylbutyronitrile ( Hereinafter, it may be referred to as AMBN), 2,2'-azobis(2-methylpropionic acid) dimethyl ester, 4,4'-azobis-4-cyanovaleric acid, and the like.

系光聚合起始劑等。The photopolymerization initiator is preferably used when obtaining an acrylic polymer by active energy ray polymerization. As a photopolymerization initiator, for example, a benzoin ether-based photopolymerization initiator, an acetophenone-based photopolymerization initiator, an α-keto alcohol-based photopolymerization initiator, an aromatic sulfonyl chloride-based photopolymerization initiator may, for example, be mentioned. Initiator, photoactive oxime-based photopolymerization initiator, benzoin-based photopolymerization initiator, benzoin-based photopolymerization initiator, benzophenone-based photopolymerization initiator, ketal-based photopolymerization initiator agent, 9-oxysulfur 𠮿

It is a photopolymerization initiator, etc.

系光聚合起始劑，例如可例舉：9-氧硫𠮿

、2-氯9-氧硫𠮿

、2-甲基9-氧硫𠮿

、2,4-二甲基9-氧硫𠮿

、異丙基9-氧硫𠮿

、2,4-二異丙基9-氧硫𠮿

、十二烷基9-氧硫𠮿

等。As a benzoin ether-based photopolymerization initiator, for example, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-di Phenylethane-1-one, anisole, etc. As the acetophenone-based photopolymerization initiator, for example, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl Phenyl ketone, 4-phenoxydichloroacetophenone, 4-(tert-butyl)dichloroacetophenone, etc. As an α-ketoalcohol-based photopolymerization initiator, for example, 2-methyl-2-hydroxypropiophenone, 1-[4-(2-hydroxyethyl)phenyl]-2-methylpropane- 1-keto, etc. As an aromatic sulfonyl chloride-based photopolymerization initiator, 2-naphthalenesulfonyl chloride etc. are mentioned, for example. As a photoactive oxime-based photopolymerization initiator, 1-phenyl-1,1-propanedione-2-(o-ethoxycarbonyl)-oxime etc. are mentioned, for example. As a benzoin type photopolymerization initiator, benzoin etc. are mentioned, for example. As a benzil-type photopolymerization initiator, benzil etc. are mentioned, for example. Examples of the benzophenone-based photopolymerization initiator include benzophenone, benzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, polyvinyl Benzophenone, α-hydroxycyclohexyl phenyl ketone, etc. As a ketal type photopolymerization initiator, benzil dimethyl ketal etc. are mentioned, for example. as 9-oxysulfur 𠮿

It is a photopolymerization initiator, for example, 9-oxysulfur 𠮿

, 2-chloro-9-oxysulfur

, 2-methyl 9-oxothio

, 2,4-dimethyl 9-oxothio

, isopropyl 9-oxothioate

, 2,4-diisopropyl 9-oxothio

, dodecyl 9-oxysulfur

Wait.

As described above, in order to further express the effects of the present invention, the acrylic pressure-sensitive adhesive composition preferably contains a crosslinking agent. By using the crosslinking agent, the cohesive force of the acrylic adhesive can be improved, and the effect of the present invention can be further exhibited.

Only one type of crosslinking agent may be used, or two or more types may be used.

As the crosslinking agent, a polyfunctional isocyanate-based crosslinking agent, an epoxy-based crosslinking agent, a melamine-based crosslinking agent, a peroxide-based crosslinking agent, a urea-based crosslinking agent, and a metal alkoxide-based crosslinking agent may, for example, be mentioned. Cross-linking agent, metal chelate-based cross-linking agent, metal salt-based cross-linking agent, carbodiimide-based cross-linking agent, oxazoline-based cross-linking agent, aziridine-based cross-linking agent, amine-based cross-linking agent agent, etc. Among them, in order to further express the effect of the present invention, at least one (component c) selected from the group consisting of a polyfunctional isocyanate-based crosslinking agent and an epoxy-based crosslinking agent is preferred.

Examples of polyfunctional isocyanate-based crosslinking agents include lower aliphatic polyisocyanates such as 1,2-ethylene diisocyanate, 1,4-butylene diisocyanate, and 1,6-hexamethylene diisocyanate. cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylene diisocyanate and other cycloaliphatic polyisocyanates; 2,4-toluene diisocyanate, 2, Aromatic polyisocyanates such as 6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, and xylylene diisocyanate, and the like. As the polyfunctional isocyanate-based crosslinking agent, for example, trimethylolpropane/toluene diisocyanate adduct (manufactured by Japan Polyurethane Industry Co., Ltd., trade name "Coronate L"), trimethylolpropane/ Hexamethylene diisocyanate adduct (manufactured by Japan Polyurethane Industry Co., Ltd., trade name "Coronate HL"), trade name "Coronate HX" (Japan Polyurethane Industry Co., Ltd.), trimethylolpropane/xylylene A base diisocyanate adduct (manufactured by Mitsui Chemicals Co., Ltd., trade name "Takenate 110N") is commercially available.

As an epoxy-based crosslinking agent (polyfunctional epoxy compound), for example, N,N,N',N'-tetraglycidyl-m-xylylenediamine, diglycidylaniline, 1,3- Bis(N,N-diglycidylaminomethyl)cyclohexane, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether Glycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitan polyglycidyl ether Glycidyl ether, trimethylolpropane polyglycidyl ether, diglycidyl adipate, diglycidyl phthalate, triglycidyl tris(2-hydroxyethyl) isocyanurate, isophthalic acid Phenol diglycidyl ether, bisphenol S diglycidyl ether, epoxy resins having two or more epoxy groups in the molecule, and the like. As an epoxy-type crosslinking agent, a commercial item, such as a brand name "Tetrad C" (made by Mitsubishi Gas Chemical Co., Ltd.), can also be mentioned.

As the content of the crosslinking agent in the acrylic pressure-sensitive adhesive composition, any appropriate content can be adopted within a range that does not impair the effects of the present invention. As such a content, for example, in order to further express the effect of the present invention, it is preferably 0.05 to 20 parts by weight, more preferably 0.1 part by weight, relative to the solid content (100 parts by weight) of the acrylic polymer. ~18 parts by weight, more preferably 0.5 parts by weight to 15 parts by weight, particularly preferably 0.5 parts by weight to 10 parts by weight.

The acrylic pressure-sensitive adhesive composition may contain any appropriate other components within a range that does not impair the effects of the present invention. Examples of such other components include polymer components other than acrylic polymers, cross-linking accelerators, cross-linking catalysts, silane coupling agents, adhesion-imparting resins (rosin derivatives, polyterpene resins, petroleum resins) , oil-soluble phenol, etc.), antioxidants, inorganic fillers, organic fillers, metal powders, colorants (pigments or dyes, etc.), foils, UV absorbers, antioxidants, light stabilizers, chain transfer agents, Plasticizer, softener, surfactant, antistatic agent, conductive agent, stabilizer, surface lubricant, leveling agent, anti-corrosion agent, heat-resistant stabilizer, polymerization inhibitor, lubricant, solvent, catalyst, etc.

<1-3-2. Urethane-based adhesive> As the urethane-based adhesive, any appropriate urethane-based adhesive can be used within a range that does not impair the effects of the present invention, such as known ones described in Japanese Patent Laid-Open No. 2017-039859 and the like Urethane based adhesives, etc. As such a urethane-based adhesive, for example, there is a urethane-based adhesive formed from a urethane-based adhesive composition, and the urethane-based adhesive combined The product includes at least one selected from the group consisting of a urethane prepolymer and a polyol, and a crosslinking agent. Only one type of urethane-based adhesive may be used, or two or more types may be used. The urethane-based adhesive may contain any appropriate components within a range that does not impair the effects of the present invention.

Typical examples of such urethane-based adhesives include: urethane-based adhesives formed from a composition containing a urethane prepolymer and a polyfunctional isocyanate compound; A urethane-based adhesive formed from a composition containing a polyol and a polyfunctional isocyanate compound.

[urethane prepolymer] The urethane prepolymer is preferably a polyurethane polyol, more preferably a polyester polyol (a1) or a polyether polyol (a2) in the presence or absence of a catalyst. ), respectively, alone or by reacting a mixture of (a1) and (a2) with an organic polyisocyanate compound (a3).

As the polyester polyol (a1), any appropriate polyester polyol can be used. As such a polyester polyol (a1), the polyester polyol obtained by making an acid component and a diol component react, for example is mentioned. As an acid component, terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid, trimellitic acid, etc. are mentioned, for example. As a glycol component, for example, ethylene glycol, propylene glycol, diethylene glycol, butanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3' -Dimethylolheptane, polyoxyethylene glycol, polyoxypropylene glycol, 1,4-butanediol, neopentyl glycol, butylethylpentanediol, glycerol as a polyol component, trimethylol Propane, pentaerythritol, etc. As the polyester polyol (a1), a polymer obtained by ring-opening polymerization of lactones such as polycaprolactone, poly(β-methyl-γ-valerolactone), and polyvalerolactone can also be mentioned. Ester polyols, etc.

As the molecular weight of the polyester polyol (a1), a low molecular weight to a high molecular weight can be used. Regarding the molecular weight of the polyester polyol (a1), the number average molecular weight is preferably 100 to 100,000. If the number average molecular weight is less than 100, the reactivity may become high, and there is a possibility that gelation is likely to occur. When the number average molecular weight exceeds 100,000, there is a possibility that the reactivity will become low and the cohesive force of the polyurethane polyol itself will become small. Among the polyols constituting the polyurethane polyol, the amount of the polyester polyol (a1) used is preferably 0 mol % to 90 mol %.

As the polyether polyol (a2), any appropriate polyether polyol can be used. As such a polyether polyol (a2), for example, a polyether polyol obtained by using a low molecular weight polyol such as water, propylene glycol, ethylene glycol, glycerin, and trimethylolpropane as the The initiator polymerizes ethylene oxide compounds such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran. As such a polyether polyol (a2), specifically, the polyether polyol with a functional group number of 2 or more, such as polypropylene glycol, polyethylene glycol, polytetramethylene glycol, etc. can be mentioned, for example.

As the molecular weight of the polyether polyol (a2), a low molecular weight to a high molecular weight can be used. Regarding the molecular weight of the polyether polyol (a2), the number average molecular weight is preferably 100 to 100,000. If the number average molecular weight is less than 100, the reactivity may become high, and there is a possibility that gelation is likely to occur. When the number average molecular weight exceeds 100,000, there is a possibility that the reactivity will become low and the cohesive force of the polyurethane polyol itself will become small. Among the polyols constituting the polyurethane polyol, the polyether polyol (a2) is preferably used in an amount of 0 mol % to 90 mol %.

Part of the polyether polyol (a2) may be replaced by diethylene glycol, 1,4-butanediol, neopentyl glycol, butyl ethyl pentanediol, glycerol, trimethylolpropane, pentaerythritol, etc. Alcohols, or polyamines such as ethylenediamine, N-aminoethylethanolamine, isophoronediamine, and xylylenediamine are used in combination.

As the polyether polyol (a2), only a bifunctional polyether polyol may be used, or a part or all of a polyether polyol having a number average molecular weight of 100 to 100,000 and having at least three or more hydroxyl groups in one molecule may be used. . As the polyether polyol (a2), a part or all of a polyether polyol having a number-average molecular weight of 100 to 100,000 and having at least three or more hydroxyl groups in one molecule can be used to balance the adhesive force and the releasability. Sex is good. In such a polyether polyol, if the number-average molecular weight is less than 100, the reactivity becomes high and there is a possibility that it becomes easy to gel. Moreover, in such a polyether polyol, when the number average molecular weight exceeds 100,000, there is a possibility that the reactivity will become low and the cohesive force of the polyurethane polyol itself will become small. The number average molecular weight of such a polyether polyol is more preferably 100-10,000.

As the organic polyisocyanate compound (a3), any appropriate organic polyisocyanate compound can be used. As such an organic polyisocyanate compound (a3), an aromatic polyisocyanate, an aliphatic polyisocyanate, an aromatic aliphatic polyisocyanate, an alicyclic polyisocyanate etc. are mentioned, for example.

As the aromatic polyisocyanate, for example, 1,3-benzenediisocyanate, 4,4'-diphenyldiisocyanate, 1,4-benzenediisocyanate, 4,4'-diphenylmethanediisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-toluene diisocyanate, 2,4,6-toluene triisocyanate, 1,3,5-benzene triisocyanate, dimethoxyaniline Diisocyanate, 4,4'-diphenylether diisocyanate, 4,4',4''-triphenylmethane triisocyanate, etc.

As aliphatic polyisocyanates, for example, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2, 3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, etc.

As araliphatic polyisocyanate, for example, ω,ω'-diisocyanato-1,3-dimethylbenzene, ω,ω'-diisocyanato-1,4-dimethylbenzene, Benzene, ω,ω'-diisocyanato-1,4-diethylbenzene, 1,4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, etc. .

As alicyclic polyisocyanate, for example, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexyl isocyanate, Alkane diisocyanate, 1,4-cyclohexanediisocyanate, methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate, 4,4'-methylenebis( cyclohexyl isocyanate), 1,4-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, and the like.

As the organic polyisocyanate compound (a3), a trimethylolpropane adduct, a biuret body formed by reacting with water, a trimer having an isocyanurate ring, and the like can be used in combination.

Any appropriate catalyst can be used as a catalyst that can be used when obtaining a polyurethane polyol. As such a catalyst, a tertiary amine compound, an organometallic compound, etc. are mentioned, for example.

As a tertiary amine-type compound, triethylamine, triethylenediamine, 1,8-diazabicyclo(5,4,0)-undecene-7(DBU) etc. are mentioned, for example.

As an organometallic compound, a tin type compound, a non-tin type compound, etc. are mentioned, for example.

Examples of tin-based compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), Dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, Tributyltin trichloroacetate, stannous 2-ethylhexanoate, etc.

Examples of non-tin-based compounds include titanium-based compounds such as dibutyltitanium dichloride, tetrabutyl titanate, and butoxytitanium trichloride; lead oleate, lead 2-ethylhexanoate, benzene Lead compounds such as lead formate and lead naphthenate; iron compounds such as iron 2-ethylhexanoate and iron acetylacetonate; cobalt compounds such as cobalt benzoate and cobalt 2-ethylhexanoate; zinc naphthenate , zinc-based compounds such as zinc 2-ethylhexanoate; zirconium-based compounds such as zirconium naphthenate, etc.

In the case of using a catalyst to obtain polyurethane polyol, in a system with two types of polyols, polyester polyol and polyether polyol, their reactivity is different, so in a separate catalyst system, Problems such as gelation or turbidity of the reaction solution are likely to occur. Therefore, by using two kinds of catalysts when obtaining the polyurethane polyol, it becomes easy to control the reaction rate, the selectivity of the catalysts, and the like, and these problems can be solved. As a combination of such two catalysts, for example, tertiary amine/organometallic, tin/non-tin, tin/tin, preferably tin/tin, more preferably dilaurel A combination of dibutyltin acid and stannous 2-ethylhexanoate. Regarding the blending ratio, the ratio by weight of stannous 2-ethylhexanoate/dibutyltin dilaurate is preferably less than 1, and more preferably 0.2 to 0.6. When the compounding ratio is 1 or more, there is a possibility that gelation is likely to occur due to the balance of catalyst activity.

When a catalyst is used to obtain a polyurethane polyol, the amount of the catalyst relative to the total amount of the polyester polyol (a1), the polyether polyol (a2) and the organic polyisocyanate compound (a3) is The usage amount is preferably 0.01% by weight to 1.0% by weight.

When a catalyst is used to obtain a polyurethane polyol, the reaction temperature is preferably less than 100°C, more preferably 85°C to 95°C. If the reaction temperature is 100° C. or higher, it may be difficult to control the reaction rate and the crosslinked structure, and there may be a possibility that it may be difficult to obtain a polyurethane polyol having a specific molecular weight.

When obtaining a polyurethane polyol, a catalyst may not be used. In this case, the reaction temperature is preferably 100°C or higher, more preferably 110°C or higher. Moreover, when obtaining a polyurethane polyol without a catalyst, it is preferable to react for 3 hours or more.

As a method of obtaining a polyurethane polyol, for example, 1) a method of adding the total amount of polyester polyol, polyether polyol, catalyst, and organic polyisocyanate to a flask; 2) polyester polyol, polyether polyol, catalyst, and organic polyisocyanate are added in full The method of adding polyol, polyether polyol and catalyst to the flask and dropping organic polyisocyanate. As a method of obtaining a polyurethane polyol, in order to control the reaction, the method of 2) is preferable.

In obtaining the polyurethane polyol, any suitable solvent can be used. As such a solvent, methyl ethyl ketone, ethyl acetate, toluene, xylene, acetone, etc. are mentioned, for example. Among these solvents, toluene is preferred.

[Polyol] As a polyol, for example, a polyester polyol, a polyether polyol, a polycaprolactone polyol, a polycarbonate polyol, and a castor oil type polyol can be mentioned preferably, for example. As a polyol, polyether polyol is more preferable.

The polyester polyol can be obtained, for example, by esterification of a polyol component and an acid component.

As the polyol component, for example, ethylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, and 3-methyl-1,5-pentane may be mentioned. Diol, 2-butyl-2-ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol , 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,8-decanediol, octadecanediol, glycerin, trimethylol Propane, pentaerythritol, hexanetriol, polypropylene glycol, etc. As the acid component, for example, succinic acid, methylsuccinic acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid, 1,14-decanedioic acid may be mentioned. Tetraalkanedioic acid, dimer acid, 2-methyl-1,4-cyclohexanedicarboxylic acid, 2-ethyl-1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid , phthalic acid, 1,4-naphthalenedicarboxylic acid, 4,4'-biphenyl dicarboxylic acid, anhydrides of these, etc.

Examples of polyether polyols include polyether polyols obtained by using water, low-molecular-weight polyols (propylene glycol, ethylene glycol, glycerol, trimethylolpropane, pentaerythritol, etc.), di Phenols (bisphenol A, etc.), dihydroxybenzenes (catechol, resorcinol, hydroquinone, etc.), etc., are used as starting agents to make ethylene oxide, propylene oxide, butylene oxide, etc. Alkylene oxide addition polymerization. Specifically, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc. are mentioned, for example.

As the polycaprolactone polyol, for example, caprolactone-based polyester diols obtained by ring-opening polymerization of cyclic ester monomers such as ε-caprolactone and σ-valerolactone can be mentioned.

Examples of polycarbonate polyols include polycarbonate polyols obtained by polycondensing the above-mentioned polyol components and phosgene; Obtained by transesterification condensation of carbonic acid diesters such as propyl ester, diisopropyl carbonate, dibutyl carbonate, ethylbutyl carbonate, ethylene carbonate, propylene carbonate, diphenyl carbonate, and dibenzyl carbonate Polycarbonate polyols; Copolycarbonate polyols obtained by using two or more of the above-mentioned polyol components; Polycarbonate polyols obtained by esterification of the above-mentioned various polycarbonate polyols with carboxyl-containing compounds ; Polycarbonate polyols obtained by etherifying the above-mentioned various polycarbonate polyols with hydroxyl-containing compounds; Polycarbonate polyols obtained by carrying out transesterification reactions between the above-mentioned various polycarbonate polyols and ester compounds; Polycarbonate polyols obtained by subjecting the above-mentioned various polycarbonate polyols and hydroxyl-containing compounds to a transesterification reaction; polyester-based polycarbonates obtained by subjecting the above-mentioned various polycarbonate polyols and dicarboxylic acid compounds to a polycondensation reaction Polyols; copolyether-based polycarbonate polyols obtained by copolymerizing the above-mentioned various polycarbonate polyols and alkylene oxides, etc.

As a castor oil type polyol, the castor oil type polyol obtained by making a castor oil fatty acid react with the said polyol component is mentioned, for example. Specifically, for example, castor oil-based polyols obtained by reacting castor oil fatty acid and polypropylene glycol can be mentioned.

The number average molecular weight Mn of the polyol is preferably 300-100,000, more preferably 400-75,000, still more preferably 450-50,000, particularly preferably 500-30,000.

The polyol (A1) having three OH groups and having a number average molecular weight Mn of 300 to 100,000 is preferred as the polyol. Only one type of polyol (A1) may be used, or two or more types may be used.

The content ratio of the polyol (A1) in the polyol is preferably 5% by weight or more, more preferably 25% by weight to 100% by weight, and still more preferably 50% by weight to 100% by weight.

The number-average molecular weight Mn of the polyol (A1) is preferably 1,000-100,000, more preferably 1,200-80,000, more preferably 1,500-70,000, still more preferably 1,750-50,000, particularly preferably 1,500-40,000, and most preferably 2000～30000.

The polyol may contain a polyol (A2) having three or more OH groups and a number average molecular weight Mn of 20,000 or less. Only one type of polyol (A2) may be used, or two or more types may be used. The number average molecular weight Mn of the polyol (A2) is preferably 100-20,000, more preferably 150-10,000, further preferably 200-7,500, particularly preferably 300-6,000, and most preferably 300-5,000. As the polyol (A2), preferable examples include: a polyol (triol) having 3 OH groups, a polyol (tetraol) having 4 OH groups, and a polyol (5) having 5 OH groups. alcohol), a polyol (hexaol) having 6 OH groups.

In terms of the content ratio in the polyol, as the polyol (A2), a polyol (tetraol) having 4 OH groups, a polyol (pentaol) having 5 OH groups, and a polyol having 6 OH groups The total amount of (hexaol) is preferably 70% by weight or less, more preferably 60% by weight or less, still more preferably 40% by weight or less, and particularly preferably 30% by weight or less.

The content ratio of the polyol (A2) in the polyol is preferably 95% by weight or less, more preferably 0% by weight to 75% by weight.

The content ratio of a polyol having 4 or more OH groups and a number-average molecular weight Mn of 20,000 or less as the polyol (A2) is preferably less than 70 wt %, more preferably 60 wt % or less, relative to the entire polyol, Furthermore, it is preferably 50% by weight or less, more preferably 40% by weight or less, and most preferably 30% by weight or less.

[Polyfunctional isocyanate compound] Only one type of polyfunctional isocyanate compound may be used, or two or more types may be used.

As the polyfunctional isocyanate compound, any appropriate polyfunctional isocyanate compound that can be used for the urethane reaction can be used. As such a polyfunctional isocyanate compound, a polyfunctional aliphatic isocyanate compound, a polyfunctional alicyclic isocyanate, a polyfunctional aromatic isocyanate compound etc. are mentioned, for example.

As the polyfunctional aliphatic isocyanate compound, for example, trimethylene diisocyanate, tetramethylene diisocyanate, 1,2-ethylidene diisocyanate, 1,6-hexamethylene diisocyanate, pentamethylene diisocyanate, Methyl diisocyanate, 1,2-propylidene diisocyanate, 1,3-butylene diisocyanate, 1,4-butylene diisocyanate, dodecylene diisocyanate, 2,4,4-triisocyanate Methylhexamethylene diisocyanate, etc.

As a polyfunctional alicyclic isocyanate compound, 1, 3- cyclopentene diisocyanate, 1, 3- cyclohexane diisocyanate, 1, 4- cyclohexane diisocyanate, isophorone diisocyanate, for example Isocyanates, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated toluene diisocyanate, hydrogenated tetramethyl xylylene diisocyanate, and the like.

As the polyfunctional aromatic diisocyanate compound, for example, phenylenediisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4 '-diphenylmethane diisocyanate, 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, benzene Dimethyl diisocyanate, etc.

Examples of the polyfunctional isocyanate compound include trimethylolpropane adducts of various polyfunctional isocyanate compounds as described above, biuret bodies obtained by reacting with water, and the third type having an isocyanurate ring. polymer etc. In addition, these can be used together.

As the polyfunctional isocyanate compound, for example, trimethylolpropane/toluene diisocyanate adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "Coronate L"), trimethylolpropane/hexamethylene can also be mentioned. Trimethylolpropane/xylylene diisocyanate Adducts (manufactured by Mitsui Chemicals Co., Ltd., trade name "Takenate 110N") are commercially available.

[Ingredients of a composition for forming a urethane-based adhesive] The urethane prepolymer and the polyol can each be combined with a polyfunctional isocyanate compound to form a composition of a urethane-based adhesive.

As a composition for forming a urethane-based adhesive, for example, a resin component other than a urethane-based resin, an adhesion imparting agent, a fatty acid ester, an inorganic filler, an organic filler, a metal powder, Pigments, foils, softeners, antiaging agents, conductive agents, UV absorbers, antioxidants, light stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat-resistant stabilizers, polymerization inhibitors, lubricants, solvents , catalyst and other ingredients. Only one type of such other components may be used, or two or more types may be used.

The composition for forming a urethane-based adhesive may also contain deterioration inhibitors such as antioxidants, ultraviolet absorbers, and light stabilizers. Only one type of deterioration inhibitor may be used, or two or more types may be used. As a deterioration inhibitor, an antioxidant is especially preferable.

As an antioxidant, a radical chain inhibitor, a peroxide decomposer, etc. are mentioned, for example.

As a radical chain inhibitor, a phenolic antioxidant, an amine antioxidant, etc. are mentioned, for example.

As a peroxide decomposer, a sulfur-based antioxidant, a phosphorus-based antioxidant, etc. are mentioned, for example.

As a phenolic antioxidant, a monophenolic antioxidant, a bisphenolic antioxidant, a polymer type phenolic antioxidant, etc. are mentioned, for example.

As monophenolic antioxidants, for example, 2,6-di-tert-butyl-p-cresol, butylhydroxyanisole, 2,6-di-tert-butyl-4-ethylphenol, β-(3,5-di-tert-butyl-4-hydroxyphenyl) stearyl propionate, etc.

As a bisphenol-based antioxidant, for example, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl -6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 4,4'-butylene bis(3-methyl-6-tert-butylphenol) tributylphenol), 3,9-bis[1,1-dimethyl-2-[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl base] 2,4,8,10-tetraoxaspiro[5,5]undecane, etc.

As a polymer type phenolic antioxidant, for example, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-tris Methyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tetra-[methylene-3-(3',5'-di-tertiary) Butyl-4'-hydroxyphenyl)propionate]methane, bis[3,3'-bis-(4'-hydroxy-3'-tert-butylphenyl)butyric acid]diol, 1, 3,5-Tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)-S-tris-2,4,6-(1H,3H,5H)trione, vitamin E Wait.

Examples of sulfur-based antioxidants include dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, and 3,3'-thiodipropionic acid. Distearate, etc.

As a phosphorus antioxidant, triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, etc. are mentioned, for example.

Examples of the ultraviolet absorber include: benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, salicylic acid-based ultraviolet absorbers, oxaniline-based ultraviolet absorbers, and cyanoacrylate-based ultraviolet absorbers Ultraviolet absorber, three 𠯤 series ultraviolet absorber, etc.

As a benzophenone type ultraviolet absorber, for example, 2, 4- dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxydi Benzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-dimethoxybenzophenone, 2,2'-dihydroxy-4,4 '-Dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, bis(2-methoxy-4-hydroxy-5-benzylphenyl) ) methane, etc.

As a benzotriazole type ultraviolet absorber, for example, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tertiary butyl) phenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3'-tertiary Butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)5-chlorobenzotriazole , 2-(2'-hydroxy-3',5'-di-tert-pentylphenyl)benzotriazole, 2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole , 2-[2'-hydroxy-3'-(3'',4'',5'',6'',-tetrahydrophthalimidomethyl)-5'-methylphenyl ] benzotriazole, 2,2'methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], 2-(2'-hydroxy-5'-methacryloyloxyphenyl)-2H-benzotriazole, etc.

As a salicylic acid type ultraviolet absorber, phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate, etc. are mentioned, for example.

As a cyanoacrylate type ultraviolet absorber, for example, 2-ethylhexyl acrylate-2-cyano-3,3'-diphenyl, acrylate ethyl-2-cyano-3,3'- Diphenyl ester, etc.

As a light stabilizer, a hindered amine light stabilizer, an ultraviolet-ray stabilizer, etc. are mentioned, for example.

Examples of hindered amine-based light stabilizers include bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate, bis(1,2,2,6,6- Pentamethyl-4-piperidinyl) sebacate, methyl-1,2,2,6,6-pentamethyl-4-piperidinyl sebacate, etc.

As the ultraviolet stabilizer, for example, bis(octylphenyl)nickel sulfide, [2,2'-thiobis(4-tert-octylphenol)]-n-butylamine nickel, 3,5 -Di-tert-butyl-4-hydroxybenzyl-nickel monoethoxide phosphate complex, nickel dibutyldithiocarbamate, benzoate type quencher, dibutyldithioamine Nickel formate etc.

The composition used to form the urethane-based adhesive may contain fatty acid esters. Only one type of fatty acid ester may be used, or two or more types may be used. By including the fatty acid ester in the composition used to form the urethane-based adhesive, the wetting speed of the urethane-based adhesive can be increased.

The content ratio of the fatty acid ester is preferably 5% by weight to 50% by weight, more preferably 7% by weight to 40% by weight, further preferably 8% by weight to 35% by weight, and particularly preferably 8% by weight to 35% by weight relative to the polyol (A). 9% by weight to 30% by weight, preferably 10% by weight to 20% by weight. Wetting speed can be further improved by adjusting the content rate of fatty acid ester in the said range. If the content ratio of the fatty acid ester is too small, there is a possibility that the wetting speed cannot be sufficiently improved. If the content ratio of the fatty acid ester is too large, there is a problem that the cost is disadvantageous, a problem that the adhesive property cannot be maintained, or a problem that the adherend is polluted.

The number average molecular weight Mn of the fatty acid ester is preferably 200-400, more preferably 210-395, further preferably 230-380, particularly preferably 240-360, and most preferably 270-340. By adjusting the number average molecular weight Mn of the fatty acid ester within the above range, the wetting speed can be further improved. If the number-average molecular weight Mn of the fatty acid ester is too small, there is a possibility that the wetting speed will not be improved even if the number of additions is large. If the number-average molecular weight Mn of the fatty acid ester is too large, the sclerosing properties of the adhesive at the time of drying may deteriorate, which may adversely affect not only the wetting properties but also other adhesion properties.

As the fatty acid ester, any appropriate fatty acid ester can be used within a range that does not impair the effects of the present invention. Examples of such fatty acid esters include polyoxyethylene bisphenol A laurate, butyl stearate, 2-ethylhexyl palmitate, 2-ethylhexyl stearate, and behenic acid. Monoglyceride, Cetyl 2-Ethylhexanoate, Isopropyl Myristate, Isopropyl Palmitate, Cholesteryl Isostearate, Lauryl Methacrylate, Methyl Coconut Fatty Acid, Methyl Laurate , Methyl Oleate, Methyl Stearate, Myristyl Myristate, Octyldodecyl Myristate, Pentaerythritol Monooleate, Pentaerythritol Monostearate, Pentaerythritol Tetrapalmitate, Stearyl Acid stearyl ester, isotridecyl stearate, 2-ethylhexanoic acid triglyceride, butyl laurate, octyl oleate, etc.

The composition used to form the urethane-based adhesive may contain a leveling agent. Only one type of leveling agent may be used, or two or more types may be used. By including a leveling agent in the composition used to form the urethane-based adhesive, uneven appearance caused by orange peel can be prevented.

The content ratio of the leveling agent is preferably 0.001% by weight to 1% by weight, more preferably 0.002% by weight to 0.5% by weight, still more preferably 0.003% by weight to 0.1% by weight, particularly preferably 0.003% by weight to 0.1% by weight relative to the polyol (A). It is 0.004 to 0.05% by weight, preferably 0.005 to 0.01% by weight. By adjusting the content ratio of the leveling agent within the above-mentioned range, the appearance unevenness caused by orange peel can be further prevented. If the content rate of the leveling agent is too small, there is a possibility that the appearance unevenness caused by the orange peel cannot be prevented. If the content ratio of the leveling agent is too large, there is a problem of being disadvantageous in cost, a problem of not being able to maintain the adhesive properties, or a problem of contamination of the adherend.

As the leveling agent, any appropriate leveling agent can be used within a range not impairing the effects of the present invention. As such a leveling agent, an acrylic leveling agent, a fluorine-type leveling agent, a polysiloxane-type leveling agent, etc. are mentioned, for example. As an acrylic leveling agent, Polyflow No. 36, Polyflow No. 56, Polyflow No. 85HF, Polyflow No. 99C (all are manufactured by Kyoeisha Chemical Co., Ltd.) etc. are mentioned. As a fluorine-type leveling agent, MEGAFAC F470N, MEGAFAC F556 (all are manufactured by DIC Corporation), etc. are mentioned. As a polysiloxane-type leveling agent, Grandic PC4100 (made by DIC Corporation) etc. are mentioned.

[Urethane-based adhesive formed from a composition containing a urethane prepolymer and a polyfunctional isocyanate compound] Examples of the urethane-based adhesive formed from a composition containing a urethane prepolymer and a polyfunctional isocyanate compound include, for example, a urethane prepolymer containing a urethane prepolymer. A urethane-based adhesive formed from a combination of an ester polyol and a polyfunctional isocyanate compound.

Only one type of urethane prepolymer may be used, or two or more types may be used.

Only one type of polyfunctional isocyanate compound may be used, or two or more types may be used.

As a method of forming a polyurethane-based adhesive from a composition containing a urethane prepolymer and a polyfunctional isocyanate compound, it is only necessary to use a so-called "urethane prepolymer" as a raw material to produce a polymer The method of the urethane-based adhesive may be sufficient, and any appropriate production method can be adopted.

The number-average molecular weight Mn of the urethane prepolymer is preferably 3,000 to 1,000,000.

In terms of NCO group/OH group, the equivalent ratio of NCO group and OH group in the urethane prepolymer and the polyfunctional isocyanate compound is preferably 5.0 or less, more preferably 0.01 to 4.75, and still more preferably 0.02 to 4.5 , preferably 0.03 to 4.25, and most preferably 0.05 to 4.0.

The content ratio of the polyfunctional isocyanate compound is preferably 0.01% by weight to 30% by weight, more preferably 0.05% by weight to 25% by weight, and still more preferably 0.01% by weight to 25% by weight relative to the urethane prepolymer. 0.1% by weight to 20% by weight, particularly preferably 0.5% by weight to 17.5% by weight, and most preferably 1% by weight to 15% by weight.

[Urethane-based adhesive formed from a composition containing a polyol and a polyfunctional isocyanate compound] As a urethane-based adhesive formed from a composition containing a polyol and a polyfunctional isocyanate compound, specifically, a urethane obtained by curing a composition containing a polyol and a polyfunctional isocyanate compound is preferable Ester based adhesive.

Only one type of polyol may be used, or two or more types may be used.

Only one type of polyfunctional isocyanate compound may be used, or two or more types may be used.

As the polyfunctional isocyanate compound, the above-mentioned compounds can be cited.

In terms of NCO group/OH group, the equivalent ratio of NCO group and OH group in the polyol and the polyfunctional isocyanate compound is preferably 5.0 or less, more preferably 0.1-3.0, further preferably 0.2-2.5, particularly preferably 0.3- 2.25, the best is 0.5 to 2.0.

The content ratio of the polyfunctional isocyanate compound is preferably 1.0% by weight to 30% by weight, more preferably 1.5% by weight to 27% by weight, and still more preferably 2.0% by weight to 25% by weight relative to the polyol. %, preferably 2.3 to 23% by weight, and most preferably 2.5 to 20% by weight.

Specifically, the polyurethane-based adhesive is preferably formed by curing a composition containing a polyol and a polyfunctional isocyanate compound. As a method of hardening a composition containing a polyol and a polyfunctional isocyanate compound to form a urethane-based adhesive, any appropriate method can be adopted within a range that does not impair the effects of the present invention, such as using block polymerization or Urethane reaction method of solution polymerization, etc., etc.

In order to harden the composition containing a polyol and a polyfunctional isocyanate compound, it is preferable to use a catalyst. As such a catalyst, an organometallic compound, a tertiary amine compound, etc. are mentioned, for example.

Examples of the organometallic compound include iron-based compounds, tin-based compounds, titanium-based compounds, zirconium-based compounds, lead-based compounds, cobalt-based compounds, zinc-based compounds, and the like. Among them, an iron-based compound and a tin-based compound are preferred in terms of the reaction rate and the pot life of the adhesive layer.

As the iron-based compound, for example, iron acetylacetonate, iron 2-ethylhexanoate, etc. may be mentioned.

As the tin-based compound, for example, dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin maleate, dibutyltin dilaurate, and dibutyltin diacetate may be mentioned. , dibutyl tin sulfide, tributyl tin methoxide, tributyl tin acetate, triethyl tin ethoxide, tributyl tin ethoxide, dioctyl tin oxide, dioctyl tin dilaurate, tributyl tin chloride, tributyl tin Tributyltin chloroacetate, stannous 2-ethylhexanoate, etc.

As a titanium type compound, dibutyl titanium dichloride, tetrabutyl titanate, butoxy titanium trichloride etc. are mentioned, for example.

As a zirconium-type compound, zirconium naphthenate, zirconium acetopyruvate, etc. are mentioned, for example.

As a lead type compound, lead oleate, lead 2-ethylhexanoate, lead benzoate, lead naphthenate, etc. are mentioned, for example.

As a cobalt-type compound, cobalt 2-ethylhexanoate, cobalt benzoate, etc. are mentioned, for example.

As a zinc-based compound, zinc naphthenate, zinc 2-ethylhexanoate, etc. are mentioned, for example.

As a tertiary amine compound, triethylamine, triethylenediamine, 1,8-diazabicyclo-(5,4,0)-undecene-7 etc. are mentioned, for example.

Only one type of catalyst may be used, or two or more types may be used. Moreover, a catalyst, a crosslinking retarder, etc. may be used together. The amount of the catalyst is preferably 0.005% by weight to 1.00% by weight, more preferably 0.01% by weight to 0.75% by weight, still more preferably 0.01% by weight to 0.50% by weight, and particularly preferably 0.01% by weight to 0.00% by weight relative to the polyol. 0.20% by weight.

<1-3-3. Polysiloxane-based adhesive> As the polysiloxane-based adhesive, any appropriate polysiloxane-based adhesive can be used within the range that does not impair the effects of the present invention, such as the known polysiloxane-based adhesives described in Japanese Patent Laid-Open No. 2014-047280 and the like. Adhesives etc. These may be only 1 type, or 2 or more types may be sufficient as them. The polysiloxane-based adhesive may contain any appropriate components within a range that does not impair the effects of the present invention.

<1-3-4. Conductive components> The adhesive layer may contain conductive components. Typically, the adhesive composition (preferably selected from the group consisting of an acrylic adhesive composition, a urethane adhesive composition, and a polysiloxane adhesive composition) that becomes the material of the adhesive layer at least one of the group) may contain a conductive component.

As the conductive component, any appropriate conductive component can be used within a range that does not impair the effects of the present invention. As such a conductive component, at least one compound selected from the group consisting of ionic liquids, ion-conductive polymers, ion-conductive fillers, and conductive polymers is preferred.

When the adhesive composition includes a conductive component, the ratio of the base polymer (eg, acrylic polymer, polyol, urethane prepolymer, polysiloxane polymer) to the conductive component is relative to 100 parts by weight of the base polymer, the conductive component is preferably 0.01 parts by weight to 10 parts by weight, more preferably 0.05 parts by weight to 9.0 parts by weight, more preferably 0.075 parts by weight to 8.0 parts by weight, and particularly preferably 0.1 parts by weight to 0.1 parts by weight. 7.0 parts by weight.

As the ionic liquid, any appropriate ionic liquid can be used within a range that does not impair the effects of the present invention. Here, the ionic liquid means a molten salt (ionic compound) in a liquid state at 25°C. Only one type of ionic liquid may be used, or two or more types may be used.

As such an ionic liquid, an ionic liquid containing a fluoroorganic anion and an onium cation is preferable.

As the onium cation that can constitute the ionic liquid, any appropriate onium cation can be used within a range that does not impair the effects of the present invention. Such an onium cation is preferably at least one selected from the group consisting of nitrogen-containing onium cations, sulfur-containing onium cations, and phosphorus-containing onium cations.

The onium cation that can constitute the ionic liquid is preferably at least one selected from the group consisting of cations having structures represented by general formulae (1) to (5) in order to further exhibit the effects of the present invention. [hua 1]

In the general formula (1), Ra represents a hydrocarbon group with 4 to 20 carbon atoms, which may contain a heteroatom, and Rb and Rc are the same or different, and represent hydrogen or a hydrocarbon group with 1 to 16 carbon atoms, and may contain a heteroatom. However, in the case where the nitrogen atom contains a double bond, Rc does not exist.

In the general formula (2), Rd represents a hydrocarbon group with 2 to 20 carbon atoms, which may contain a heteroatom, and Re, Rf and Rg are the same or different, and represent hydrogen or a hydrocarbon group with 1 to 16 carbon atoms, which may contain a heteroatom.

In the general formula (3), Rh represents a hydrocarbon group with 2 to 20 carbon atoms and may contain a heteroatom, and Ri, Rj and Rk are the same or different, and represent hydrogen or a hydrocarbon group with 1 to 16 carbon atoms, and may contain a heteroatom.

In the general formula (4), Z represents a nitrogen atom, a sulfur atom or a phosphorus atom, and R ₁ , Rm, Rn and Ro are the same or different, represent a hydrocarbon group having 1 to 20 carbon atoms, and may contain a hetero atom. However, when Z is a sulfur atom, Ro does not exist.

In the general formula (5), X represents a Li atom, a Na atom or a K atom.

Examples of the cation represented by the general formula (1) include pyridinium cations, pyrrolidinium cations, piperidinium cations, cations having a pyrroline skeleton, and cations having a pyrrole skeleton.

Specific examples of the cation represented by the general formula (1) include, for example, 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-ethyl-3-methyl cation pyridinium cation, 1-butyl-3-methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1-octyl-4- Pyridinium cations such as methylpyridinium cation; 1-ethyl-1-methylpyrrolidinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-butylpyrrolidinium cation Cation, 1-methyl-1-pentylpyrrolidinium cation, 1-methyl-1-hexylpyrrolidinium cation, 1-methyl-1-heptylpyrrolidinium cation, 1-ethyl-1- Propylpyrrolidinium cation, 1-ethyl-1-butylpyrrolidinium cation, 1-ethyl-1-pentylpyrrolidinium cation, 1-ethyl-1-hexylpyrrolidinium cation, 1- Pyrrolidinium cations such as ethyl-1-heptylpyrrolidinium cation; 1-methyl-1-ethylpiperidinium cation, 1-methyl-1-propylpiperidinium cation, 1-methyl- 1-butylpiperidinium cation, 1-methyl-1-pentyl piperidinium cation, 1-methyl-1-hexyl piperidinium cation, 1-methyl-1-heptyl piperidinium cation, 1-Ethyl-1-propylpiperidinium cation, 1-ethyl-1-butylpiperidinium cation, 1-ethyl-1-pentylpiperidinium cation, 1-ethyl-1-hexyl Piperidinium cations such as piperidinium cations, 1-ethyl-1-heptylpiperidinium cations, 1-propyl-1-butylpiperidinium cations, etc., more preferably 1-hexylpyridinium cations, 1-hexylpyridinium cations, and the like -Ethyl-3-methylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-octyl-4-methylpyridinium cation, 1-methyl-1-propylpyrrolidinium cation cation, 1-methyl-1-propylpiperidinium cation.

As a cation represented by general formula (2), an imidazolium cation, an tetrahydropyrimidinium cation, a dihydropyrimidinium cation, etc. are mentioned, for example.

Specific examples of the cation represented by the general formula (2) include, for example, 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, and 1-ethyl-3-methylimidazolium cation , 1-butyl-3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-decyl-3-methylimidazolium cation cations, imidazolium cations such as 1-dodecyl-3-methylimidazolium cation, 1-tetradecyl-3-methylimidazolium cation, etc., more preferably 1-ethyl-3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation.

As a cation represented by general formula (3), a pyrazolium cation, a pyrazolinium cation, etc. are mentioned, for example.

Specific examples of the cation represented by the general formula (3) include, for example, 1-methylpyrazolium cation, 3-methylpyrazolium cation, 1-ethyl-2-methylpyrazolinium Cation, 1-ethyl-2,3,5-trimethylpyrazolium cation, 1-propyl-2,3,5-trimethylpyrazolium cation, 1-butyl-2,3,5 - Pyrazolonium cations such as trimethylpyrazolium cation; 1-ethyl-2,3,5-trimethylpyrazolinium cation, 1-propyl-2,3,5-trimethylpyrazole Pyrazolinium cations such as phosphonium cations, 1-butyl-2,3,5-trimethylpyrazolinium cations, and the like.

As the cation represented by the general formula (4), for example, a tetraalkylammonium cation, a trialkyl perionium cation, a tetraalkylphosphonium cation, or a part of the above-mentioned alkyl group is substituted with an alkenyl group or an alkoxy group, and further Substituted by epoxy group, etc.

Specific examples of the cation represented by the general formula (4) include triethylmethylammonium cation, tributylethylammonium cation, trimethyldecylammonium cation, and diethylmethyl ammonium cation. , asymmetric tetraalkylammonium cations such as dibutyl ethyl phosphonium cation, dimethyl decyl saccharide cation, triethyl methyl phosphonium cation, tributyl ethyl phosphonium cation, trimethyl decyl phosphonium cation, trimethyl phosphonium cation, etc. Alkyl perionium cation, tetraalkylphosphonium cation, or N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium cation, glycidyltrimethylammonium cation, diene Propyldimethylammonium cation, N,N-dimethyl-N-ethyl-N-propylammonium cation, N,N-dimethyl-N-ethyl-N-butylammonium cation, N,N-dimethyl-N-ethyl-N-butylammonium cation N-dimethyl-N-ethyl-N-pentylammonium cation, N,N-dimethyl-N-ethyl-N-hexylammonium cation, N,N-dimethyl-N-ethyl- N-heptylammonium cation, N,N-dimethyl-N-ethyl-N-nonylammonium cation, N,N-dimethyl-N,N-dipropylammonium cation, N,N-dipropylammonium cation Ethyl-N-propyl-N-butylammonium cation, N,N-dimethyl-N-propyl-N-pentylammonium cation, N,N-dimethyl-N-propyl-N- Hexylammonium cation, N,N-dimethyl-N-propyl-N-heptylammonium cation, N,N-dimethyl-N-butyl-N-hexylammonium cation, N,N-diethylammonium -N-butyl-N-heptylammonium cation, N,N-dimethyl-N-pentyl-N-hexylammonium cation, N,N-dimethyl-N,N-dihexylammonium cation, trihexylammonium cation Methylheptylammonium cation, N,N-diethyl-N-methyl-N-propylammonium cation, N,N-diethyl-N-methyl-N-pentylammonium cation, N,N -Diethyl-N-methyl-N-heptylammonium cation, N,N-diethyl-N-propyl-N-pentylammonium cation, triethylpropylammonium cation, triethylpentyl cation Ammonium cation, triethylheptylammonium cation, N,N-dipropyl-N-methyl-N-ethylammonium cation, N,N-dipropyl-N-methyl-N-pentylammonium cation , N,N-dipropyl-N-butyl-N-hexylammonium cation, N,N-dipropyl-N,N-dihexylammonium cation, N,N-dibutyl-N-methyl- N-amylammonium cation, N,N-dibutyl-N-methyl-N-hexylammonium cation, trioctylmethylammonium cation, N-methyl-N-ethyl-N-propyl-N -Amylammonium cation, etc., more preferably trimethylpropylammonium cation.

As the fluoroorganic anion that can constitute the ionic liquid, any appropriate fluoroorganic anion can be used within a range that does not impair the effects of the present invention. Such fluoroorganic anions can be fully fluorinated (perfluorination) or partially fluorinated.

Examples of such fluoroorganic anions include perfluoroalkylsulfonate, bis(fluorosulfonyl)imide, and bis(perfluoroalkanesulfonyl)imide, and more specifically, trifluoro Mesylate, pentafluoroethanesulfonate, heptafluoropropanesulfonate, nonafluorobutanesulfonate, bis(fluorosulfonyl)imide, bis(trifluoromethanesulfonyl)imide.

As a specific example of an ionic liquid, it can select and use suitably from the combination of the said cation component and the said anionic component. Specific examples of such ionic liquids include 1-hexylpyridinium bis(fluorosulfonyl)imide, 1-ethyl-3-methylpyridinium trifluoromethanesulfonate, 1-ethyl -3-methylpyridinium pentafluoroethanesulfonate, 1-ethyl-3-methylpyridinium heptafluoropropanesulfonate, 1-ethyl-3-methylpyridinium nonafluorobutanesulfonate, 1-Butyl-3-methylpyridinium trifluoromethanesulfonate, 1-butyl-3-methylpyridinium bis(trifluoromethanesulfonyl)imide, 1-octyl-4-methyl pyridinium bis(fluorosulfonyl)imide, 1-methyl-1-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-methyl-1-propylpyrrolidine Onium bis(fluorosulfonyl)imide, 1-methyl-1-propylpiperidinium bis(trifluoromethanesulfonyl)imide, 1-methyl-1-propylpiperidinium bis (fluorosulfonyl)imide, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium heptafluoropropanesulfonate, 1-ethyl -3-Methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide, 1-hexyl-3-methyl Imidazolium bis(fluorosulfonyl)imide, bis(trifluoromethanesulfonyl)imide trimethylpropylammonium, lithium bis(trifluoromethanesulfonyl)imide, bis(fluorosulfonyl)imide acyl) lithium imide.

A commercially available ionic liquid can be used, or it can be synthesized as follows. The method for synthesizing the ionic liquid is not particularly limited, as long as the target ionic liquid can be obtained. Generally, as described in the document "Ionic Liquids - Frontiers and Futures of Development-" (published by CMC Corporation) The halide method, hydroxide method, acid ester method, complex method and neutralization method, etc.

In the following, for the halide method, hydroxide method, ester method, complex method and neutralization method, the synthesis method of nitrogen-containing onium salt is shown as an example, and other ionic liquids such as other sulfur-containing onium salts and phosphorus-containing onium salts are shown below. It can also be obtained by the same method.

The halide method is a method carried out by the reactions shown in the reaction formulae (1) to (3). First, a halide is obtained by reacting a tertiary amine with a halogenated alkyl group (reaction formula (1), using chlorine, bromine, and iodine as the halogen).

Obtained by reacting the obtained halide with an acid (HA ⁾ or a salt (MA, M are cations that form salts with target anions such as ammonium, lithium, sodium, potassium, etc.) Target ionic liquid (R ₄ NA).

[hua 2]

The hydroxide method is a method performed by the reactions shown in the reaction formulae (4) to (8). First, for halide (R ₄ NX), electrolysis by ion exchange membrane method (reaction formula (4)), OH type ion exchange resin method (reaction formula (5)) or reaction with silver oxide (Ag ₂ O) (Reaction formula (6)) to obtain hydroxide (R ₄ NOH) (using chlorine, bromine, and iodine as halogen).

The target ionic liquid (R ₄ NA) is obtained by using the reaction of the reaction formulas (7) to (8) in the same manner as the above-mentioned halogenation method for the obtained hydroxide.

[hua 3]

The acid ester method is a method carried out by the reactions shown in the reaction formulae (9) to (11). First, a tertiary amine (R ₃ N) is reacted with an acid ester to obtain an acid ester (reaction formula (9), and as the acid ester, an ester of a mineral acid such as sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, and carbonic acid, or methyl ester is used esters of organic acids such as sulfonic acid, methylphosphonic acid, formic acid, etc.).

The target ionic liquid (R ₄ NA) was obtained by using the reaction of the reaction formulas (10) to (11) in the same manner as the above-mentioned halogenation method for the obtained acid ester. Moreover, by using methyl trifluoromethanesulfonate, methyl trifluoroacetate, etc. as an acid ester, an ionic liquid can also be obtained directly.

[hua 4]

The neutralization method is a method carried out by the reaction shown in the reaction formula (12). Tertiary amines can be reacted with organic acids such as CF ₃ COOH, CF ₃ SO ₃ H, (CF ₃ SO ₂ ) ₂ NH, (CF ₃ SO ₂ ) ₃ CH, (C ₂ F ₅ SO ₂ ) ₂ NH, etc. and obtained.

[hua 5]

R in the above reaction formulae (1) to (12) represents hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, and may contain a hetero atom.

As the ion-conducting polymer, any appropriate ion-conducting polymer can be employed within a range not impairing the effects of the present invention. Examples of such ion-conductive polymers include: ion-conductive polymers obtained by polymerizing or copolymerizing a monomer having a quaternary ammonium salt group); polythiophene, polyaniline, polypyrrole, polyethylidene Conductive polymers such as amines and allylamine-based polymers, etc. Only one type of the ion conductive polymer may be used, or two or more types may be used.

As the ion-conducting filler, any appropriate ion-conducting filler can be used within a range not impairing the effects of the present invention. Examples of such ion conductive fillers include tin oxide, antimony oxide, indium oxide, cadmium oxide, titanium oxide, zinc oxide, indium, tin, antimony, gold, silver, copper, aluminum, nickel, chromium, titanium, Iron, cobalt, copper iodide, ITO (indium oxide/tin oxide), ATO (antimony oxide/tin oxide), etc. Only one type of the ion conductive filler may be used, or two or more types may be used.

As the conductive polymer, any appropriate conductive polymer can be used within a range not impairing the effects of the present invention. As such a conductive polymer, (3, 4- ethylenedioxythiophene)-poly (styrenesulfonic acid) etc. are mentioned, for example.

<1-3-5. Other ingredients> An adhesive composition (preferably at least one selected from the group consisting of acrylic adhesive composition, urethane adhesive composition, and polysiloxane adhesive composition) to be the material of the adhesive layer 1) Any appropriate other components may be contained within the range that does not impair the effects of the present invention. Examples of such other components include other polymer components, catalysts, cross-linking accelerators, cross-linking retarders, silane coupling agents, adhesion-imparting resins (rosin derivatives, polyterpene resins, petroleum resins, oil soluble phenol, etc.), antioxidants, inorganic fillers, organic fillers, metal powders, colorants (pigments or dyes, etc.), foils, UV absorbers, antioxidants, light stabilizers, chain transfer agents, plasticizers Agents, softeners, surfactants, antistatic agents, conductive agents, stabilizers, surface lubricants, leveling agents, anticorrosion agents, heat-resistant stabilizers, polymerization inhibitors, lubricants, solvents, etc.

Among other components, at least one selected from catalysts, cross-linking retarders, and surfactants is preferably used, and at least one selected from catalysts and cross-linking retarders is more preferably used.

(catalyst) Examples of the catalyst include tin-based catalysts such as dibutyltin dilaurate and dioctyltin dilaurate; tris(acetylpyruvate)iron, Tris(2,4-heptanedionate)iron, tris(3,5-heptanedionate)iron, tris(5-methyl-2,4-hexanedione acid)iron, tris(2,4- Suberic acid) iron, tris(6-methyl-2,4-heptanedionate) iron, tris(2,6-dimethyl-3,5-heptanedionate) iron, tris(2,5-heptanedionate) iron 4-Nanedione acid) iron, tris (4,6- nonanedione acid) iron, tris (2,2,6,6-tetramethyl-3,5-heptanedionate) iron, tris (6 , 8-tridecanedione acid) iron, tris (1-phenyl-1,3-butanedione acid) iron, tris (hexafluoroacetone acetone) iron, tris (ethylacetate) iron, Tris(acetate-n-propyl)iron, tris(acetoacetate-isopropyl)iron, tris(acetoacetate-n-butyl)iron, tris(acetoacetate-2-butyl)iron, tris(acetoacetate)iron tert-butyl)iron, tris(propyl methyl acetate) iron, tris(propyl ethyl acetate) iron, tris(propyl propyl acetate n-propyl acetate) iron, tris(propyl propyl acetate isopropyl acetate) iron, tris(propyl propyl acetate) iron (n-butyl propylacetate)iron, tris(dibutyl propylacetate)iron, tris(tertiary butyl propylacetate)iron, tris(benzylacetate)iron, tris(dimalonate)iron methyl) iron, tris(diethylmalonate) iron, trimethoxy iron, triethoxy iron, triisopropoxy iron, iron chloride and other iron-based catalysts.

Only one type of catalyst may be used, or two or more types may be used.

Relative to 100 parts by weight of the base polymer (such as acrylic polymer, polyol, urethane prepolymer, polysiloxane polymer), the content of the catalyst is preferably 0.002 to 0.5 part by weight, More preferably, it is 0.005 weight part - 0.3 weight part, More preferably, it is 0.01 weight part - 0.1 weight part. Within this range, the speed of the cross-linking reaction when the adhesive layer is formed is faster, and the pot life of the adhesive composition is also longer, which is a preferable aspect.

(Crosslinking retarder) Typical examples of the crosslinking retarder include compounds that generate keto-enol tautomerism. If a compound that produces keto-enol tautomerism is used as the crosslinking retarder, for example, excessive increase in viscosity or gelation of the adhesive composition can be suppressed, and the effect of prolonging the pot life of the adhesive composition can be exhibited. This technique is preferably applied when the adhesive composition is in the form of an organic solvent solution or a solvent-free form.

As a keto-enol tautomerization compound, various β-dicarbonyl compounds can be used, for example. Specific examples include acetone acetone, 2,4-hexanedione, 3,5-heptanedione, 2-methyl-3,5-hexanedione, 6-methyl-2,4 - β-diketones such as heptanedione, 2,6-dimethyl-3,5-heptanedione; methyl acetoacetate, ethyl acetate, isopropyl acetoacetate, acetoacetate Acetyl acetates such as tributyl; propyl acetates such as ethyl acetate, ethyl acetate, isopropyl acetate, tert-butyl acetate; ethyl acetate, Isobutylacetate such as ethyl isobutylacetate, isopropyl isobutylacetate, tert-butyl isobutylacetate, etc.; malonate esters such as methyl malonate, ethyl malonate, etc. Among them, at least one selected from the group consisting of acetylacetone and acetylacetate is preferred.

There may be only one compound that produces keto-enol tautomerism, or two or more compounds.

With respect to 100 parts by weight of the base polymer (eg, acrylic polymer, polyol, urethane prepolymer, polysiloxane polymer), the content of the compound that produces keto-enol tautomerism is preferably 100 parts by weight. 0.1 to 20 parts by weight, more preferably 0.5 to 15 parts by weight, still more preferably 1 to 10 parts by weight. If the content of the compound that produces keto-enol tautomerism is too small, there is a possibility that a sufficient use effect may not be exhibited. If the compound which produces a keto-enol tautomerism is used too much, it may remain in the adhesive layer and there exists a possibility that a cohesion force may fall.

(surfactant) In order to improve the releasability and the wettability of the adhesive composition to the adherend, the adhesive composition (preferably selected from the group consisting of acrylic adhesive composition, urethane adhesive At least one of the group consisting of the adhesive composition and the polysiloxane-based adhesive composition) may contain a surfactant.

As a surfactant, a well-known anionic surfactant, a well-known nonionic surfactant, a well-known cationic surfactant, a well-known amphoteric surfactant, etc. are mentioned.

Only one type of surfactant may be used, or two or more types may be used.

The content of the surfactant is preferably 0.01 to 10 parts by weight relative to 100 parts by weight of the base polymer (such as acrylic polymer, polyol, urethane prepolymer, polysiloxane polymer) , more preferably 0.1 part by weight to 1 part by weight.

≪1-4. Antistatic layer≫ The film adhering to the adhesive layer according to the embodiment of the present invention may have an antistatic layer between the substrate layer and the adhesive layer, and may also have an antistatic layer between the release layer and the substrate layer.

As the thickness of the antistatic layer, any appropriate thickness can be adopted within a range that does not impair the effects of the present invention. Such a thickness is preferably 1 nm to 1000 nm, more preferably 5 nm to 900 nm, further preferably 7.5 nm to 800 nm, particularly preferably 10 nm to 700 nm.

The antistatic layer may be only one layer, or may be two or more layers.

As the antistatic layer, any appropriate antistatic layer may be used within a range that does not impair the effect of the present invention as long as it can exhibit an antistatic effect. As such an antistatic layer, an antistatic layer formed by coating a conductive coating liquid containing a conductive polymer on any appropriate substrate layer is preferred. Specifically, for example, it is an antistatic layer formed by coating a conductive coating liquid containing a conductive polymer on a substrate (eg, a substrate layer). As a specific coating method, a roll coating method, a gravure coating method, a reverse coating method, a roll brush coating method, a spray coating method, an air knife coating method, a die coating method, Extrusion coating method by cloth machine, etc.

As the conductive coating liquid containing the conductive polymer, any appropriate conductive coating liquid can be employed within a range not impairing the effects of the present invention. Such a conductive coating liquid preferably contains a conductive polymer, a binder, a cross-linking agent and a solvent. In the process of forming the antistatic layer, the solvent is volatilized or evaporated due to heating, etc., and substantially disappears. Therefore, the antistatic layer preferably includes a conductive polymer, a binder and a crosslinking agent.

As the conductive polymer, any appropriate conductive polymer can be used within a range not impairing the effects of the present invention. As such a conductive polymer, the conductive polymer etc. which are doped with a polyanion in a π-conjugated conductive polymer are mentioned, for example. Examples of the π-conjugated conductive polymer include chain conductive polymers such as polythiophene, polypyrrole, polyaniline, and polyacetylene. As the polyanion, polystyrene sulfonic acid, polyisoprene sulfonic acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, polyethyl acrylate sulfonic acid, polymethacryloyl carboxylic acid may, for example, be mentioned. Wait. Only one type of conductive polymer may be used, or two or more types may be used.

The content ratio of the conductive polymer in the antistatic layer is preferably 3% by weight to 80% by weight, more preferably 5% by weight to 60% by weight.

As a solvent, an organic solvent, water, or these mixed solvents are mentioned, for example. Examples of the organic solvent include: esters such as ethyl acetate; ketones such as methyl ethyl ketone, acetone, and cyclohexanone; cyclic ethers such as tetrahydrofuran (THF) and diethylene; n-hexane, cyclohexane and the like Aliphatic or alicyclic hydrocarbons such as alkane; aromatic hydrocarbons such as toluene and xylene; aliphatic or alicyclic alcohols such as methanol, ethanol, n-propanol, isopropanol, cyclohexanol; Alcohol monoalkyl ethers (for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether), and glycol ethers such as dialkylene glycol monoalkyl ethers, and the like. The solvent is preferably water or a mixed solvent containing water as a main component (for example, a mixed solvent of water and ethanol).

The content ratio of the binder in the antistatic layer is preferably 50% by weight to 95% by weight, more preferably 60% by weight to 90% by weight.

As the binder that can be contained in the conductive coating liquid, any appropriate binder can be used within a range that does not impair the effects of the present invention. Only one type of binder may be used, or two or more types may be used. As such a binder, resin is preferable, and polyester resin is more preferable. The ratio of the polyester resin to the binder is preferably 90% by weight to 100% by weight, more preferably 98% by weight to 100% by weight.

The polyester resin preferably contains polyester as a main component (preferably more than 50 wt %, more preferably 75 wt % or more, further preferably 90 wt % or more, particularly preferably a component accounting for substantially 100 wt %) .

As the polyester, any appropriate polyester can be used within a range not impairing the effects of the present invention. Such a polyester preferably has a structure selected from polycarboxylic acids having two or more carboxyl groups in one molecule (such as dicarboxylic acid compounds) and derivatives thereof (such as anhydrides of polycarboxylic acids, One or more compounds (polycarboxylic acid components) of esters, halides, etc.), and one or more selected from polyols (such as diols) having two or more hydroxyl groups in one molecule The compound (polyol component) is condensed.

As a polyhydric carboxylic acid component, any appropriate polyhydric carboxylic acid can be used in the range which does not impair the effect of this invention. As such a polyvalent carboxylic acid component, for example, oxalic acid, malonic acid, difluoromalonic acid, alkylmalonic acid, succinic acid, tetrafluorosuccinic acid, alkylsuccinic acid, (±) - Malic acid, mesotartaric acid, itaconic acid, maleic acid, methyl maleic acid, fumaric acid, methyl fumaric acid, acetylene dicarboxylic acid, glutaric acid, Hexafluoroglutaric acid, methylglutaric acid, glutaric acid, adipic acid, dithioadipic acid, methyladipic acid, dimethyladipic acid, tetramethyladipic acid, methylene Adipic acid, muconic acid, galactaric acid, pimelic acid, suberic acid, perfluorosuberic acid, 3,3,6,6-tetramethylsuberic acid, azelaic acid, sebacic acid , Perfluorosebacic acid, tridecanedioic acid, dodecyl dicarboxylic acid, tridecyl dicarboxylic acid, tetradecyl dicarboxylic acid and other aliphatic dicarboxylic acids; cycloalkyl dicarboxylic acids ( For example, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid), 1,4-(2-noralkene)dicarboxylic acid, 5-noralkene-2,3-dicarboxylic acid Alicyclic dicarboxylic acids such as carboxylic acid (bicycloheptenedicarboxylic acid), adamantane dicarboxylic acid, spiroheptane dicarboxylic acid; phthalic acid, isophthalic acid, dithioisophthalic acid, methyl isophthalic acid, dimethyl isophthalic acid, chloroisophthalic acid, dichloroisophthalic acid, terephthalic acid, methyl terephthalic acid, dimethyl terephthalic acid, chloroterephthalic acid Formic acid, bromoterephthalic acid, naphthalenedicarboxylic acid, oxodicarboxylic acid, anthracene dicarboxylic acid, biphenyl dicarboxylic acid, biphenylenedicarboxylic acid, dimethyl biphenylenedicarboxylic acid, 4,4 ''-p-triphenylenedicarboxylic acid, 4,4''-p-tetraphenylenedicarboxylic acid, bibenzyl dicarboxylic acid, azobenzene dicarboxylic acid, homophthalic acid, benzene diacetic acid, benzene dicarboxylic acid Propionic acid, naphthalenedicarboxylic acid, naphthalenedipropionic acid, biphenyl diacetic acid, biphenyl dipropionic acid, 3,3'-[4,4'-(methylene di-p-biphenyl)dipropionic acid, 4,4 Aromatic dicarboxylic acids such as '-bibenzyldiacetic acid, 3,3'(4,4'-bibenzyl)dipropionic acid, oxydi-p-phenylenediacetic acid; the acid anhydride of any of the above-mentioned polycarboxylic acids; the above-mentioned Esters of any polycarboxylic acid (such as alkyl esters, monoesters, diesters, etc.); acyl halides corresponding to any of the above polycarboxylic acids (such as dicarboxylate chloride), etc.

As the polyvalent carboxylic acid component, preferable examples include: aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalene dicarboxylic acid, and their acid anhydrides; adipic acid, sebacic acid, azelaic acid, succinic acid, etc. Aliphatic dicarboxylic acids such as acid, fumaric acid, maleic acid, bicycloheptenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and their anhydrides; lower alkyl esters of these dicarboxylic acids (For example, an ester with a monoalcohol having 1 to 3 carbon atoms) and the like.

As the polyol component, any appropriate polyol can be used within a range not to impair the effects of the present invention. As such a polyol component, for example, ethylene glycol, propylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, and neopentyl glycol may be mentioned. , 1,5-pentanediol, 1,6-hexanediol, 3-methylpentanediol, diethylene glycol, 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol Diol, 2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, xylylenediol , Hydrogenated bisphenol A, bisphenol A and other glycols; the alkylene oxide adducts of these glycols (such as ethylene oxide adducts, propylene oxide adducts, etc.) and the like.

The molecular weight of the polyester resin is preferably 5×10 ³ to 1.5×10 ⁵ in terms of the weight average molecular weight (Mw) in terms of standard polystyrene measured by gel permeation chromatography (GPC), more preferably 1 ×10 ⁴ to 6×10 ⁴ .

The glass transition temperature (Tg) of the polyester resin is preferably 0°C to 120°C, more preferably 10°C to 80°C.

As the polyester resin, for example, commercially available trade names "VYLONAL" manufactured by Toyobo Co., Ltd., etc. can be used.

The conductive coating liquid may further contain resins other than polyester resins (for example, selected from acrylic resins, acrylic urethane resins, acrylic styrene resins, acrylic polysiloxanes, At least one of polysiloxane resin, polysilazane resin, polyurethane resin, fluororesin, and polyolefin resin) as a binder.

As the cross-linking agent that can be contained in the conductive coating liquid, any appropriate cross-linking agent can be used within a range that does not impair the effects of the present invention. Only one type of crosslinking agent may be used, or two or more types may be used. As such a cross-linking agent, preferable examples include: isocyanate-based cross-linking agent, epoxy-based cross-linking agent, melamine-based cross-linking agent, peroxide-based cross-linking agent, urea-based cross-linking agent, metal alkane Oxide-based cross-linking agent, metal chelate-based cross-linking agent, metal salt-based cross-linking agent, carbodiimide-based cross-linking agent, oxazoline-based cross-linking agent, aziridine-based cross-linking agent, amine Department of cross-linking agents, etc. Among them, a melamine-based crosslinking agent is preferred.

The content ratio of the crosslinking agent in the antistatic layer is preferably 1% by weight to 30% by weight, more preferably 2% by weight to 20% by weight.

In the antistatic layer, any appropriate other components may be contained within a range not impairing the effects of the present invention.

≪1-5. Conductive layer≫ The film adhering to the adhesive layer according to the embodiment of the present invention may have a conductive layer between the substrate layer and the adhesive layer, and may also have a conductive layer between the release layer and the substrate layer.

The conductive layer may be only one layer, or may be two or more layers.

The conductive layer can be provided by being formed on any suitable substrate (eg, a substrate layer).

The conductive layer is formed on any suitable base by any suitable thin-film formation method, such as vacuum evaporation, sputtering, ion plating, spray thermal decomposition, electroless plating, electroplating, or a combination thereof. A conductive film is formed on a material (eg, a substrate layer). Among these thin film forming methods, the vacuum deposition method or the sputtering method is preferable in terms of the formation speed of the conductive film, the formability of a large-area film, and the productivity.

As a material for forming the conductive film, for example, metal-based materials including gold, silver, platinum, palladium, copper, aluminum, nickel, chromium, titanium, iron, cobalt, tin, alloys of these, etc.; including indium oxide can be used , tin oxide, titanium oxide, cadmium oxide, metal oxide materials such as mixtures of these; other metal compounds including copper iodide, etc.

As the thickness of the conductive layer, any appropriate thickness can be adopted according to the purpose within the range that does not impair the effects of the present invention. As such a thickness, for example, when it is formed of a metal-based material, it is preferably 30 Å to 600 Å, and when it is formed of a metal oxide-based material, it is preferably 80 Å to 5000 Å.

The surface resistance value of the conductive layer is preferably 1.0×10 ¹⁰ Ω/□ or less, more preferably 1.0×10 ⁹ Ω/□ or less, further preferably 1.0×10 ⁸ Ω/□ or less, particularly preferably 1.0×10 ⁷ . Ω/□ or less.

When forming a conductive film on any appropriate substrate (eg, substrate layer), the surface of the substrate (eg, substrate layer) can also be subjected to corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, sputter etching Any appropriate pretreatment such as treatment and primer treatment can improve the adhesion between the conductive film and the substrate (eg, the substrate layer).

≪≪2. Manufacturing method of film with adhesive layer≫≫ The film to which the adhesive layer of the embodiment of the present invention is attached can be produced by any appropriate method within the range not impairing the effects of the present invention.

As a representative example of the production method of the film with the adhesive layer, as shown in FIG. 1 , the film 100 with the adhesive layer is formed by directly laminating the release layer 10 , the base layer 20 , and the adhesive layer 30 in this order. The case of the form of a film is demonstrated.

When the film to which the adhesive layer is attached is a film formed by directly laminating a release layer, a substrate layer, and an adhesive layer in this order, the following (1) to (4) can be exemplified as a representative production method. Methods (the order of (3) and (4) can be reversed). (1) Preparation of a release layer forming material for forming a release layer. (2) Preparation of an adhesive composition for forming an adhesive layer. (3) Coating a release layer forming material on one surface of the base material layer, drying the solvent and the like to remove it, and forming a release layer on the base material layer. (4) Coating the adhesive composition on the other surface of the base material layer, heating and drying as needed, and curing it as needed, to form an adhesive layer on the base material layer. [Example]

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited by these examples at all. In addition, the test and evaluation method in an Example etc. are as follows. Furthermore, when it is described as "parts", unless there is any special description, it means "weight parts", and when it is described as "%", unless there is no special description, it means "weight parts". %".

<Determination of thickness> The thickness of the adhesive layer of the examples and comparative examples was measured using an interference film thickness meter (manufactured by Otsuka Electronics Co., Ltd., product name "MCPD-3700". The thickness of the release layer was measured after heavy metal dyeing treatment. Resin-embedded, by ultra-thin sectioning, a TEM "H-7650" manufactured by Hitachi Co., Ltd. was used, and a cross-sectional image was obtained under the conditions of accelerating voltage: 100 kV and magnification: 60,000 times. The cross-sectional image was binarized. After the chemical treatment, divide the cross-sectional area of the top coat by the length of the sample in the field of view, thereby actually measuring the thickness of the top coat (average thickness in the field of view), and the result is 10 nm to 50 nm.

<Measurement of Tg> Regarding the glass transition temperature (Tg) (°C), the glass transition temperature of the homopolymer obtained from each monomer was defined as Tgn (°C), and was determined from the following formula using the following literature values. Formula: 1/(Tg+273)=Σ[Wn/(Tgn+273)] (wherein, Tg (°C) represents the glass transition temperature of the copolymer, Wn represents the weight fraction of each monomer, Tgn (°C) represents the glass transition temperature of the homopolymer obtained from each monomer, and n represents each monomer type) Glass transition temperature of homopolymer of 2-ethylhexyl acrylate (2EHA): -70°C Glass transition temperature of homopolymer of hydroxyethyl acrylate (HEA): -15℃ Glass transition temperature of homopolymer of 4-hydroxybutyl acrylate (HBA): -32°C Glass transition temperature of homopolymer of acrylic acid (AA): 106℃ Furthermore, regarding the literature value, refer to "Synthesis, Design and Development of New Uses of Acrylic Resin" (published by the Publishing Department of the Central Business Development Center).

<Measurement of weight average molecular weight> The weight average molecular weight is measured by gel permeation chromatography (GPC). Specifically, using the trade name "HLC-8120GPC" (manufactured by Tosoh Corporation) as a GPC measuring device, the measurement was performed under the following conditions, and it was calculated from the standard polystyrene conversion value. (Molecular weight measurement conditions) ・Sample concentration: 0.2% by weight (tetrahydrofuran solution) ・Sample injection volume: 10 μL ・Column: Trade name "TSKguardcolumn SuperHZ-H (1 piece) + TSKgel SuperHZM-H (2 pieces)" (manufactured by Tosoh Corporation) ・Reference column: Trade name "TSKgel SuperH-RC (1 piece)" (manufactured by Tosoh Corporation) ・Eluent: Tetrahydrofuran (THF) ・Flow rate: 0.6 mL/min ・Detector: Differential Refractometer (RI) ・Column temperature (measurement temperature): 40°C

<Measurement of the low-speed peeling force of the adhesive layer to the release layer at a peeling speed of 0.3 m/min and a peeling angle of 180 degrees> For the produced film with an adhesive layer, the adhesive was laminated to the release layer with a hand pressing roller, and then laminated under the pressure of 0.25 MPa and 0.3 m/min. 20 minutes under 50% environment. Thereafter, the film was cut to a width of 25 mm, and the adhesive layer on the opposite side of the release layer was attached to a SUS plate (SUS304BA) and fixed. Using a universal tensile tester (manufactured by Minebea Co., Ltd., product name: TCM-1kNB), the adhesive layer was peeled off from the release layer at a peeling speed of 0.3 m/min and a peeling angle of 180 degrees, and the peeling force at this time was set to for low-speed peel force.

<Measurement of the high-speed peeling force of the adhesive layer to the release layer at a peeling speed of 10 m/min and a peeling angle of 180 degrees> For the produced film with an adhesive layer, the adhesive was laminated to the release layer with a hand pressing roller, and then laminated under the pressure of 0.25 MPa and 0.3 m/min. 20 minutes under 50% environment. Thereafter, the film was cut to a width of 25 mm, and the adhesive layer on the opposite side of the release layer was attached to a SUS plate (SUS304BA) and fixed. Using a universal tensile tester (manufactured by Minebea Co., Ltd., product name: TCM-1kNB), the adhesive layer was peeled off from the release layer at a peeling speed of 10 m/min and a peeling angle of 180 degrees. For high-speed peel force.

<Determination of Foreign Matter Removal Rate> For the produced film with an adhesive layer, at a temperature of 23°C and a humidity of 50% RH, in a non-clean environment (specifically, different from the definition in ISO146441-1:2015) The space of the clean room that is classified and set the management standard), the adhesive layer and the optical film (specifically, the “transparent protective film 1A” described in the examples of Japanese Patent Laid-Open No. 2017-26939) are separated into The size of 10 cm ² × 10 cm ² is attached, and the foreign objects that are bitten during the lamination are marked, and the size of the foreign objects is confirmed with an optical microscope. Calculate the foreign matter of 100 μm or more, calculate the foreign matter remaining on the optical film after peeling off the film with the adhesive layer, and check the foreign matter removal rate.

[Production Example 1]: Preparation of Acrylic Polymer (1) In a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen introduction tube, and a cooler, 2-ethylhexyl acrylate (2EHA): 100 parts by weight, 4-hydroxybutyl acrylate (4HBA): 10 parts by weight, acrylic acid were added (AA): 0.02 parts by weight, 2,2'-azobisisobutyronitrile (AIBN) (manufactured by Wako Pure Chemical Industries, Ltd.) as a polymerization initiator: 0.2 parts by weight, ethyl acetate: 157 parts by weight, while stirring slowly While introducing nitrogen gas, the liquid temperature in the flask was kept around 65° C., and a polymerization reaction was performed for about 6 hours to prepare a solution of the acrylic polymer (1) (solid content concentration=40% by weight). The weight average molecular weight (Mw) of the obtained acrylic polymer (1) was 540,000, and Tg was -67 degreeC.

[Production Example 2]: Preparation of Acrylic Adhesive Composition (1) The solution (solid content concentration = 40% by weight) of the acrylic polymer (1) obtained in Production Example 1 was diluted with ethyl acetate to 5% by weight with respect to the acrylic polymer (1) in the solution. : 100 parts by weight (solid content), added with isocyanurate of hexamethylene diisocyanate (Coronate HX, manufactured by Nippon Polyurethane Industry Co., Ltd.): 6 parts by weight, dioctyl dilaurate as a tin-based catalyst Base tin (manufactured by Tokyo Fine Chemical, Enbilizer OL-1): 0.03 parts by weight, acetoacetone as a crosslinking retarder: 10 parts by weight, kept at around 25°C, and mixed and stirred for about 1 minute to prepare an acrylic adhesive Composition (1).

[Manufacturing example 3]: Preparation of release layer forming material (1) Resin obtained by drying butyraldehyde resin (manufactured by Sekisui Chemical Industry Co., Ltd., S-LEC KW-10): 100 parts by weight was dissolved in xylene (manufactured by Sun Chemical Co., Ltd., Xylol): 900 parts by weight, followed by adding isocyanate ten Octaalkyl ester (manufactured by Ohara Paragium Chemical Co., Ltd., R-NCO): 480 parts by weight. Further, the solution was diluted with toluene (manufactured by Idemitsu Petrochemical Co., Ltd.) so that the solid content was 0.2% by weight to prepare a release layer forming material (1).

[Manufacture example 4]: Preparation of release layer forming material (2) Except having changed the usage amount of octadecyl isocyanate (manufactured by Ohara Paragium Chemical Co., Ltd., R-NCO) to 200 parts by weight, it was carried out in the same manner as in Production Example 3 to prepare a release layer forming Materials (2).

[Manufacture example 5]: Preparation of release layer forming material (3) Except having changed the usage amount of octadecyl isocyanate (manufactured by Ohara Paragium Chemical Co., Ltd., R-NCO) to 100 parts by weight, it was carried out in the same manner as in Production Example 3 to prepare a release layer forming Materials (3).

[Manufacture example 6]: Preparation of release layer forming material (4) Dispersion A (manufactured by Toyobo Co., Ltd., trade name "Vinaroll MD-1480" (aqueous dispersion of saturated copolyester resin) containing 25% by weight of polyester resin as a binder was prepared, hereinafter referred to as "adhesion". Agent Dispersion A"). Furthermore, an aqueous dispersion of carnauba wax (hereinafter referred to as "slippery agent dispersion B") as a slip agent was prepared. Furthermore, a conductive polymer containing poly(3,4-ethylenedioxythiophene) (PEDT): 0.5 wt % and polystyrene sulfonate (number average molecular weight: 150,000) (PSS): 0.8 wt % was prepared (product of HCStark company, trade name "Baytron P", hereinafter referred to as "conductive polymer aqueous solution C"). In a mixed solvent of water and ethanol, add 100 parts by weight of the above-mentioned binder dispersion liquid A in terms of the solid content, 30 parts by weight of the above-mentioned lubricant dispersion B in terms of the solid content, and 30 parts by weight of the solid content. The above-mentioned conductive polymer aqueous solution C and the melamine-based crosslinking agent in an amount of 50 parts by weight were stirred and mixed well for 20 minutes. In this way, a release layer forming material (4) having a solid content of 0.15% by weight was produced.

[Production Example 7]: Preparation of Urethane-Based Adhesive Composition (2) As the polyol (A), PREMINOL S3011 (manufactured by Asahi Glass Co., Ltd., Mn=10000) which is a polyol having three OH groups: 85 parts by weight, SANNIX GP-3000 which is a polyol having three OH groups is used (manufactured by Sanyo Chemical Co., Ltd., Mn=3000): 13 parts by weight, SANNIX GP-1000 (manufactured by Sanyo Chemical Co., Ltd., Mn=1000) as a polyol having 3 OH groups: 2 parts by weight, prepared as The polyfunctional alicyclic isocyanate compound of the polyfunctional isocyanate compound (B) is Coronate HX (Japan Polyurethane Industry Co., Ltd.): 18 parts by weight, catalyst (manufactured by Nippon Chemical Industry Co., Ltd., trade name: triethylacetone) Iron): 0.15 parts by weight, Irganox 1010 (manufactured by BASF) as a deterioration inhibitor: 0.50 parts by weight, fatty acid ester (isopropyl palmitate, manufactured by Kao, trade name: EXCEPARL IPP, Mn=299): 30 parts by weight, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (manufactured by Daiichi Industrial Pharmaceutical Co., Ltd., IL210): 0.01 parts by weight, ethyl acetate as a diluting solvent: 241 parts by weight, It stirred with a disperser, and obtained the urethane type adhesive composition (2).

[Example 1] The release layer forming material (1) obtained in Production Example 3 was coated on a PET film (manufactured by Mitsubishi Chemical, DIAFOIL T100C38) with a thickness of 38 μm as the base layer (1), and dried at 130° C. for 60 seconds , to produce a layered body (A1) of the release layer (1) and the base material layer (1). The thickness of the release layer after drying is 20 nm. Furthermore, the acrylic adhesive composition (1) obtained in Production Example 2 was applied on the opposite side of the release layer (1) of the above-mentioned laminate (A1), and heated at 130° C. for 60 seconds to form a thickness of 0.5 The adhesive layer ( 1 ) of μm is used to manufacture a film ( 1 ) with an adhesive layer without a separator. The results are shown in Table 1.

[Example 2] Except having set the thickness of the adhesive layer (1) to 0.7 μm, it was carried out in the same manner as in Example 1 to produce a film (2) with an adhesive layer without a separator. The results are shown in Table 1.

[Example 3] Except having made the thickness of the adhesive layer (1) 1.0 μm, it was carried out in the same manner as in Example 1 to produce a film (3) with an adhesive layer without a separator. The results are shown in Table 1.

[Example 4] Except having made the thickness of the adhesive layer (1) 2.0 micrometers, it carried out similarly to Example 1, and produced the film (4) of the adhesive layer with no separator. The results are shown in Table 1.

[Example 5] Except having made the thickness of the adhesive layer (1) 3.0 micrometers, it carried out similarly to Example 1, and produced the film (5) with an adhesive layer without a separator. The results are shown in Table 1.

[Example 6] Except having made the thickness of the adhesive layer (1) 4.0 micrometers, it carried out similarly to Example 1, and produced the film (6) of the adhesive layer without a separator. The results are shown in Table 1.

[Example 7] Except having made the thickness of the adhesive layer (1) 5.0 micrometers, it carried out similarly to Example 1, and produced the film (7) of the adhesive layer without a separator. The results are shown in Table 1.

[Example 8] Except having made the thickness of the adhesive layer (1) 1.5 micrometers, it carried out similarly to Example 1, and produced the film (8) of the adhesive layer without a separator. The results are shown in Table 1.

[Example 9] Except having set the thickness of the adhesive layer (1) to 0.9 μm, it was carried out in the same manner as in Example 1 to produce a film (9) with an adhesive layer without a separator. The results are shown in Table 1.

[Example 10] Except having made the thickness of the adhesive layer (1) 1.2 micrometers, it carried out similarly to Example 1, and produced the film (10) with an adhesive layer without a separator. The results are shown in Table 1.

[Example 11] Except having changed the release layer formation material (1) to the release layer formation material (2), it carried out in the same manner as Example 3, and produced the film (11) of the adhesive layer without a separator. The results are shown in Table 1.

[Example 12] Except having changed the release layer formation material (1) to the release layer formation material (3), it carried out in the same manner as Example 3, and produced the film (12) of the adhesive layer without a separator. The results are shown in Table 1.

[Comparative Example 1] Except not providing a release layer, it carried out in the same manner as Example 3, and produced the film (C1) of the adhesive layer which does not have a separator. The results are shown in Table 1.

[Comparative Example 2] Except having made the thickness of the adhesive layer (1) 0.3 micrometer, it carried out similarly to Example 1, and produced the film (C2) of the adhesive layer without a separator. The results are shown in Table 1.

[Comparative Example 3] Except having changed the release layer formation material (1) to the release layer formation material (4), it carried out similarly to Example 3, and produced the film (C3) of the adhesive layer without a separator. The results are shown in Table 1.

[Comparative Example 4] Except having made the thickness of the adhesive layer (1) 5.5 micrometers, it carried out similarly to Example 1, and produced the film (C4) with which the adhesive layer without a separator was attached. The results are shown in Table 1.

[Comparative Example 5] Except having made the thickness of the adhesive layer (1) 6.0 micrometers, it carried out similarly to Example 1, and produced the film (C5) of the adhesive layer without a separator. The results are shown in Table 1.

[Comparative Example 6] A production was carried out in the same manner as in Example 1, except that SK Dyne 2563NS (manufactured by Soken Chemical Co., Ltd.) as a rubber-based adhesive was used instead of the acrylic adhesive composition (1) to form an adhesive layer with a thickness of 0.3 μm. Film (C6) with adhesive layer without release film. The results are shown in Table 1.

[Comparative Example 7] A production was carried out in the same manner as in Example 1, except that SK Dyne 2563NS (manufactured by Soken Chemical Co., Ltd.) as a rubber-based adhesive was used instead of the acrylic adhesive composition (1) to form an adhesive layer with a thickness of 0.5 μm. Film (C7) with adhesive layer without release film. The results are shown in Table 1.

[Comparative Example 8] A production was carried out in the same manner as in Example 1, except that SK Dyne 2563PS (manufactured by Soken Chemical Co., Ltd.) as a rubber-based adhesive was used instead of the acrylic adhesive composition (1) to form an adhesive layer with a thickness of 0.5 μm. Film (C8) with adhesive layer without release film. The results are shown in Table 1.

[Comparative Example 9] A production was carried out in the same manner as in Example 1, except that SK Dyne 2563PS (manufactured by Soken Chemical Co., Ltd.) as a rubber-based adhesive was used instead of the acrylic adhesive composition (1) to form an adhesive layer with a thickness of 1.0 μm. Film with adhesive layer without release film (C9). The results are shown in Table 1.

[Table 1] adhesive layer Adhesive layer thickness (μm) release layer Peeling force from backside Removal rate of foreign matter removal Low speed peel force 0.3 m/min (N/25 mm) High-speed peel force 10 m/min (N/25 mm) Example 1 Adhesive Layer(1) 0.5 Release layer(1) 0.01 0.01 57% 2 Adhesive Layer(1) 0.7 Release layer(1) 0.01 0.02 67% 3 Adhesive Layer(1) 1.0 Release layer(1) 0.02 0.04 81% 4 Adhesive Layer(1) 2.0 Release layer(1) 0.05 0.07 85% 5 Adhesive Layer(1) 3.0 Release layer(1) 0.06 0.12 86% 6 Adhesive Layer(1) 4.0 Release layer(1) 0.07 0.14 93% 7 Adhesive Layer(1) 5.0 Release layer(1) 0.07 0.17 93% 8 Adhesive Layer(1) 1.5 Release layer(1) 0.03 0.05 83% 9 Adhesive Layer(1) 0.9 Release layer(1) 0.02 0.03 76% 10 Adhesive Layer(1) 1.2 Release layer(1) 0.02 0.04 81% 11 Adhesive Layer(1) 1.0 Release layer(2) 0.02 0.08 80% 12 Adhesive Layer(1) 1.0 Release layer(3) 0.01 0.03 81% Comparative example 1 Adhesive Layer(1) 1.0 No release layer 0.12 0.35 82% 2 Adhesive Layer(1) 0.3 Release layer(1) can't close can't close 46% 3 Adhesive Layer(1) 1.0 Release layer(4) 0.11 0.28 81% 4 Adhesive Layer(1) 5.5 Release layer(1) 0.10 0.21 93% 5 Adhesive Layer(1) 6.0 Release layer(1) 0.13 0.23 94% 6 Sk Dyne 2563NS 0.3 Release layer(1) can't close can't close Unable to measure 7 Sk Dyne 2563NS 0.5 Release layer(1) can't close can't close Unable to measure 8 Sk Dyne 2563PS 0.5 Release layer(1) can't close can't close Unable to measure 9 Sk Dyne 2563PS 1.0 Release layer(1) can't close can't close Unable to measure

[Example 13] The release layer forming material (1) obtained in Production Example 3 was coated on a PET film (manufactured by Mitsubishi Chemical, DIAFOIL T100C38) with a thickness of 38 μm as the base layer (1), and dried at 130° C. for 60 seconds , to produce a layered body (A1) of the release layer (1) and the base material layer (1). The thickness of the release layer after drying is 20 nm. Furthermore, the urethane-based adhesive composition (2) obtained in Production Example 7 was applied on the opposite side of the release layer (1) of the above-mentioned laminate (A1), and heated at 130° C. for 2 minutes , forming an adhesive layer (2) with a thickness of 1.0 μm, and producing a film (13) with an adhesive layer without a separator. The results are shown in Table 2.

[Example 14] Except having made the thickness of the adhesive layer (2) 2.0 micrometers, it carried out similarly to Example 13, and produced the film (14) of the adhesive layer without a separator. The results are shown in Table 2.

[Example 15] Except having made the thickness of the adhesive layer (2) 3.0 micrometers, it carried out similarly to Example 13, and produced the film (15) of the adhesive layer with no separator. The results are shown in Table 2.

[Table 2] adhesive layer Adhesive layer thickness (μm) release layer Peeling force from backside Removal rate of foreign matter removal Low speed peel force 0.3 m/min (N/25 mm) High-speed peel force 10 m/min (N/25 mm) Example 13 Adhesive layer (2) 1.0 Release layer(1) 0.01 0.03 83% 14 Adhesive layer (2) 2.0 Release layer(1) 0.01 0.04 85% 15 Adhesive layer (2) 3.0 Release layer(1) 0.02 0.05 88% [Industrial Availability]

The film to which the adhesive layer of the present invention is attached is suitable for use in the production steps of optical members or electronic members, and the like.

10: Release layer 20: Substrate layer 30: Adhesive layer 40: Antistatic layer 100: film with adhesive layer

FIG. 1 is a schematic cross-sectional view of one embodiment of the adhesive layer-adhering film of the present invention. FIG. 2 is a schematic cross-sectional view of another embodiment of the adhesive layer-adhering film of the present invention.

10: Release layer

20: Substrate layer

30: Adhesive layer

100: film with adhesive layer

Claims (9)

A film with an adhesive layer, which has a release layer, a substrate layer, and an adhesive layer in sequence, and There is no release film on the side of the adhesive layer opposite to the base material layer, The release layer is a layer formed of a release layer-forming material comprising a long-chain alkyl group-containing isocyanate and a polyvinyl alcohol-based resin, The base material layer contains polyester resin, The thickness of the adhesive layer is 0.5 μm˜5.0 μm. The film with the adhesive layer as claimed in claim 1, wherein at a temperature of 23°C and a humidity of 50% RH, the low speed of the adhesive layer to the release layer measured at a peeling speed of 0.3 m/min and a peeling angle of 180 degrees The peel force is 0.01 N/25 mm or more. The film with the adhesive layer as claimed in claim 1 or 2, wherein at a temperature of 23°C and a humidity of 50% RH, the adhesive layer is measured at a peeling speed of 10 m/min and a peeling angle of 180 degrees to the release layer. The high-speed peel force is below 0.20 N/25 mm. The film with an adhesive layer according to any one of claims 1 to 3, wherein the thickness of the release layer is 1 nm to 200 nm. The adhesive layer-attached film according to any one of claims 1 to 4, wherein the long-chain alkyl group-containing isocyanate is a monofunctional isocyanate. The adhesive layer-attached film according to any one of claims 1 to 5, wherein the long-chain alkyl group contained in the long-chain alkyl group-containing isocyanate is an alkyl group having 6 or more carbon atoms. The adhesive layer-attached film according to any one of claims 1 to 6, wherein the polyvinyl alcohol-based resin has an acetal group, an acetyl group, and a hydroxyl group. The adhesive layer-attached film according to any one of claims 1 to 7, wherein the adhesive layer is formed of an adhesive composition, the adhesive composition is an acrylic adhesive composition, and the acrylic adhesive composition Contains acrylic polymer and crosslinking agent. The film for an adhesive layer according to claim 8, wherein the above-mentioned acrylic polymer is formed from a composition (A) comprising: (a component) the carbon number of the alkyl group of the alkyl ester moiety It is at least 1 sort(s) chosen from the group which consists of 4-12 (meth)acrylic acid alkyl esters and (b component) which have an OH group (meth)acrylic acid ester and (meth)acrylic acid.

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