JP7132371B2 - Film with adhesive layer - Google Patents

Description

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

In the manufacturing process of optical members and electronic members, a surface protective film (SPV) is attached to prevent the surface of the member from being damaged during processing, assembly, inspection, transportation, and the like.

As the surface protective film, conventionally, many typical surface protective films having a substrate layer, an adhesive layer and a separator in this order have been reported. For example, there has been reported a separator-attached surface protective film that does not contaminate the surface of an adherend and is resistant to deformation by external force even when the total thickness is reduced (Patent Document 1).

On the other hand, as a surface protection film used in the manufacturing process of optical members and electronic members, recently, for reasons such as reducing the cost of the separator, a surface protection film that does not have a separator on the adhesive layer surface side (separatorless) Film is required. As such a separatorless surface protective film, a surface protective film in which a polyethylene film and an adhesive layer are laminated has been reported (Patent Document 2). This surface protection film is manufactured by extrusion molding, and by embossing the back surface of the polyethylene film, it can be wound up and unwound without a separator, and can be provided as a wound body.

However, the polyethylene film has a problem that it tends to contain lumps (fisheyes) in which the resin has not completely melted. Moreover, since the back surface of the polyethylene film is embossed, there is a problem that dents or the like are generated on the optical member or the electronic member at the time of lamination.

In addition, the separatorless surface protective film has conventionally been provided with a release layer on the outermost surface of the substrate layer opposite to the pressure-sensitive adhesive layer for the purpose of facilitating separatorless winding and unwinding. There are many things. Therefore, various components contained in the release layer migrate to the pressure-sensitive adhesive layer, and when the surface protective film is attached to an adherend, the surface of the adherend is contaminated.

In addition, conventional surface protective films have problems such as the generation of adhesive scum during processing and the problem of low print adhesion to the surface protective film.

JP 2017-31278 A JP-A-06-033022

An object of the present invention is to provide a pressure-sensitive adhesive layer-attached film that does not use a polyethylene film as a substrate layer, can be wound and unwound without a separator, can suppress contamination of the surface of the adherend, To provide a separator-less adhesive layer-attached film which hardly generates adhesive scum during processing and has excellent print adhesion.

The pressure-sensitive adhesive layer-attached film according to the embodiment of the present invention is
An adhesive layer-attached film having a substrate layer and an adhesive layer,
The pressure-sensitive adhesive layer does not have a separator on the side opposite to the base layer,
does not have a release layer on the side opposite to the pressure-sensitive adhesive layer of the base layer,
The base material layer contains a polyester-based resin,
The pressure-sensitive adhesive layer is a urethane-based pressure-sensitive adhesive layer composed of a urethane-based pressure-sensitive adhesive,
The adhesive layer has a thickness of 1.0 μm to 6.0 μm.

In one embodiment, at a temperature of 23° C. and a humidity of 50% RH, the pressure-sensitive adhesive layer is peeled off from the surface of the base layer opposite to the pressure-sensitive adhesive layer at a peel speed of 0.3 m/min and a peel angle of 180. The low speed peel force measured in degrees is 0.01 N/25 mm or more.

In one embodiment, at a temperature of 23° C. and a humidity of 50% RH, the pressure-sensitive adhesive layer is peeled off from the surface of the substrate layer opposite to the pressure-sensitive adhesive layer at a peel speed of 10 m/min and a peel angle of 180 degrees. The measured high-speed peel force is 0.10 N/25 mm or less.

In one embodiment, the urethane-based pressure-sensitive adhesive is formed from a urethane-based pressure-sensitive adhesive composition, and the urethane-based pressure-sensitive adhesive composition contains a polyol (A1) and a polyfunctional isocyanate compound (B).

In one embodiment, the polyol (A1) contains a polyol having a number average molecular weight Mn of 400-20,000.

In one embodiment, the content ratio of the polyfunctional isocyanate compound (B) to the polyol (A1) is 5% by weight to 60% by weight.

According to the present invention, a film with an adhesive layer that does not use a polyethylene film as a base layer, can be wound and unwound without a separator, can suppress contamination of the surface of the adherend, It is possible to provide a separator-less pressure-sensitive adhesive layer-attached film that is less likely to generate adhesive scum during processing and has excellent print adhesion.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic sectional drawing of one embodiment of the film with an adhesive layer of this invention.

In the present specification, the expression "weight" may be read as "mass" which is commonly used as an SI unit indicating weight.

When the expression "(meth) acrylic" is used in this specification, it means "acrylic and/or methacrylic", and when the expression "(meth) acrylate" is used, "acrylate and/or methacrylate ", and the expression "(meth)allyl" means "allyl and/or methallyl", and the expression "(meth)acrolein" means "acrolein and/or methacrolein". means rain.

<<<1. Film with adhesive layer>>>>
A pressure-sensitive adhesive layer-attached film according to an embodiment of the present invention is a pressure-sensitive adhesive layer-attached film having a base layer and a pressure-sensitive adhesive layer, wherein the pressure-sensitive adhesive layer has a separator on the side opposite to the base layer. and does not have a release layer on the opposite side of the base layer to the pressure-sensitive adhesive layer. The pressure-sensitive adhesive layer-attached film according to the embodiment of the present invention is typically a pressure-sensitive adhesive layer-attached film having a base layer and a pressure-sensitive adhesive layer, wherein the base layer and the pressure-sensitive adhesive layer are the outermost layers. be.

The pressure-sensitive adhesive layer-attached film according to the embodiment of the present invention does not have a separator on the side of the pressure-sensitive adhesive layer opposite to the base layer, so the cost of the separator can be reduced and the separator peeling process can be omitted.

Since the adhesive layer-attached film according to the embodiment of the present invention does not have a release layer on the opposite side of the adhesive layer of the base layer, the transfer of various components contained in the release layer to the adhesive layer is avoided. It is possible to suppress the problem of contamination of the surface of the adherend when the surface protection film is attached to the adherend.

The pressure-sensitive adhesive layer-attached film according to the embodiment of the present invention has any appropriate other layer as long as it has a substrate layer and an adhesive layer, as long as the pressure-sensitive adhesive layer-attached film does not impair the effects of the present invention. You may have

As shown in FIG. 1, one embodiment of the pressure-sensitive adhesive layer-attached film 100 of the present invention is a film in which a substrate layer 10 and a pressure-sensitive adhesive layer 20 are directly laminated.

The pressure-sensitive adhesive layer-attached film according to the embodiment of the present invention can be used for various purposes. Typically, manufacturing of optical members and electronic members (for example, glass used in liquid crystal displays, polarizing plates, wave plates, retardation plates, optical compensation films, reflective sheets, brightness enhancement films, transparent conductive films, etc.) Examples include a surface protection film and a carrier sheet for protecting the surface of a member to prevent the surface from being damaged during processing, assembly, inspection, transportation, and the like.

As the form of the pressure-sensitive adhesive layer-attached film according to the embodiment of the present invention, any appropriate form can be adopted as long as the effects of the present invention are not impaired. Such a form includes, for example, a wound body (also referred to as a roll body), a sheet body, and the like.

In the pressure-sensitive adhesive layer-attached film according to the embodiment of the present invention, the substrate layer contains a polyester-based resin. By including the polyester resin in the base material layer, the effects of the present invention can be exhibited more effectively, and in particular, the conventional problems in the case of using a polyethylene film as the base material layer can be resolved.

In the pressure-sensitive adhesive layer-attached film according to the embodiment of the present invention, the pressure-sensitive adhesive layer is a urethane-based pressure-sensitive adhesive layer composed of a urethane-based pressure-sensitive adhesive. By using a urethane-based pressure-sensitive adhesive layer composed of a urethane-based pressure-sensitive adhesive, the effects of the present invention can be exhibited more effectively, and in particular, the problem of the occurrence of adhesive scum during processing can be suppressed.

In the adhesive layer-attached film according to the embodiment of the present invention, the thickness of the adhesive layer is adjusted within the range of 1.0 μm to 6.0 μm. The thickness of the adhesive layer is preferably 1.0 μm to 5.5 μm, more preferably 1.0 μm to 5.0 μm, still more preferably 1.0 μm to 4.5 μm, and particularly preferably 1.0 μm to 5.0 μm. 5 μm to 4.0 μm, most preferably 1.5 μm to 3.5 μm. By adjusting the thickness of the pressure-sensitive adhesive layer within the above range, the effect of the present invention can be further exhibited. If the thickness of the pressure-sensitive adhesive layer is too large outside the above range, the low-speed peel strength and the high-speed peel strength may become too high. There is a possibility that a problem such as peeling occurring at a location may occur.

The pressure-sensitive adhesive layer-attached film according to the embodiment of the present invention has a peel rate of 0.3 m/min for the pressure-sensitive adhesive layer on the opposite side of the pressure-sensitive adhesive layer of the base layer at a temperature of 23° C. and a humidity of 50% RH. , The low-speed peel force measured at a peel angle of 180 degrees is preferably 0.01 N/25 mm or more, more preferably 0.01 N/25 mm to 0.15 N/25 mm, and still more 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. When the low-speed peel force is less than 0.01 N/25 mm, for example, when winding to form a wound body or in the state of a wound body that has been wound, the pressure-sensitive adhesive layer against the base layer. There is a risk that the adhesiveness will be lowered, and that winding will not be smooth, and that the shape of the wound body will not be maintained. When the low-speed peeling force is within the above range, separatorless winding property can be improved. The details of the method for measuring the low-speed peel force will be described later.

The pressure-sensitive adhesive layer-attached film according to the embodiment of the present invention is peeled at a temperature of 23° C. and a humidity of 50% RH at a peel rate of 10 m / min of the pressure-sensitive adhesive layer from the surface of the base layer opposite to the pressure-sensitive adhesive layer. The high-speed peel strength measured at an angle of 180 degrees is preferably 0.10 N/25 mm or less, more preferably 0.01 N/25 mm to 0.10 N/25 mm, still more preferably 0.02 N/25 mm to 0.02 N/25 mm. 10 N/25 mm, particularly preferably 0.03 N/25 mm to 0.10 N/25 mm. If the high-speed peel force exceeds 0.10 N/25 mm, for example, when the pressure-sensitive adhesive layer-attached film is unwound from a roll, heavy peeling may occur, and unwinding may not be smooth. If the high-speed peeling force is within the above range, the separator-less unwinding property can be good. The details of the method for measuring the high-speed peel force will be described later.

In the pressure-sensitive adhesive layer-attached film according to the embodiment of the present invention, it is preferable that the low-speed peel strength and the high-speed peel strength have a relationship of low-speed peel strength≦high-speed peel strength. With such a relationship, it is possible to develop excellent separatorless winding and unwinding properties.

The total thickness of the pressure-sensitive adhesive layer-attached film according to the embodiment of the invention is preferably 20 μm to 100 μm, more preferably 25 μm to 80 μm, still more preferably 30 μm to 60 μm. If the total thickness of the pressure-sensitive adhesive layer-attached film according to the embodiment of the present invention is within the above range, the effects of the present invention can be exhibited more effectively.

The pressure-sensitive adhesive layer-attached film according to the embodiment of the present invention preferably has a total light transmittance of 60% or more, more preferably 70% to 100%, still more preferably 80% to 100%, especially Preferably 83% to 100%, most preferably 85% to 100%.

The pressure-sensitive adhesive layer-attached film according to the embodiment of the present invention preferably has a haze of 15% or less, more preferably 0% to 10%, still more preferably 0% to 8%, and particularly preferably 0%. % to 7%, most preferably 0% to 6%.

<<1-1. Base layer≫
The base material layer contains a polyester-based resin in that it can exhibit the effects of the present invention.

The content of the polyester resin in the substrate layer 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. %, particularly preferably 95% to 100% by weight, most preferably 98% to 100% by weight. If the content of the polyester-based resin in the substrate layer is within the above range, the effects of the present invention can be exhibited more effectively.

As the polyester-based resin, any appropriate polyester-based resin can be adopted as long as the effects of the present invention are not impaired. Such a polyester-based resin is preferably at least selected from the group consisting of polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate (PBT), in order to further express the effects of the present invention. One of them, 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, still more preferably 10 μm to 150 μm, and particularly preferably 20 μm, in terms of allowing the effect of the present invention to be more expressed. ~100 μm, most preferably between 30 μm and 80 μm.

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

The substrate layer may be stretched.

The substrate layer may be surface-treated. Examples of surface treatment include corona treatment, plasma treatment, chromic acid treatment, ozone exposure, flame exposure, high voltage shock exposure, ionizing radiation treatment, and coating treatment with a primer.

The base material layer may contain any suitable additive as long as the effects of the present invention are not impaired. Such additives include, for example, antistatic agents, colorants, powders such as pigments, surfactants, plasticizers, tackifiers, low molecular weight polymers, surface lubricants, leveling agents, antioxidants, corrosion Examples include inhibitors, light stabilizers, ultraviolet absorbers, polymerization inhibitors, silane coupling agents, inorganic fillers, organic fillers, metal powders, organic particles, and inorganic particles.

<<1-2. Adhesive layer≫
The pressure-sensitive adhesive layer may consist of only one layer, or may consist of two or more layers.

The thickness of the adhesive layer is adjusted within the range of 1.0 μm to 6.0 μm, as described above. The thickness of the adhesive layer is preferably 1.0 μm to 5.5 μm, more preferably 1.0 μm to 5.0 μm, still more preferably 1.0 μm to 4.5 μm, and particularly preferably 1.0 μm to 5.0 μm. 5 μm to 4.0 μm, most preferably 1.5 μm to 3.5 μm. By adjusting the thickness of the pressure-sensitive adhesive layer within the above range, the effect of the present invention can be further exhibited. As described above, if the thickness of the pressure-sensitive adhesive layer is too large outside the above range, the low-speed peel force and the high-speed peel force may become too high. In actual use, problems such as peeling at unintended locations may occur.

The pressure-sensitive adhesive layer is a urethane-based pressure-sensitive adhesive layer composed of a urethane-based pressure-sensitive adhesive, as described above. By using a urethane-based pressure-sensitive adhesive layer composed of a urethane-based pressure-sensitive adhesive, the effects of the present invention can be exhibited more effectively, and in particular, the problem of the occurrence of adhesive scum during processing can be suppressed.

A urethane-based pressure-sensitive adhesive is formed from a urethane-based pressure-sensitive adhesive composition. That is, the urethane-based pressure-sensitive adhesive formed from the urethane-based pressure-sensitive adhesive composition forms a layer shape to form the pressure-sensitive adhesive layer.

A urethane-based pressure-sensitive adhesive may be defined as being formed from a urethane-based pressure-sensitive adhesive composition. This is because the urethane-based pressure-sensitive adhesive becomes a urethane-based pressure-sensitive adhesive when the urethane-based pressure-sensitive adhesive composition undergoes a cross-linking reaction by heating, ultraviolet irradiation, or the like. However, due to the fact that it is impossible and almost impractical (“impossible/impractical circumstances”), urethane It is a valid specification of the system adhesive as a "thing".

A urethane-based pressure-sensitive adhesive is formed from a urethane-based pressure-sensitive adhesive composition. As such a forming method, any appropriate forming method can be adopted as long as the effects of the present invention are not impaired. As such a forming method, for example, a method for forming a urethane-based pressure-sensitive adhesive generally known in the past can be adopted. Specifically, such a forming method includes, for example, directly applying a urethane pressure-sensitive adhesive composition to any appropriate base film (for example, the base layer in the surface protection film according to the embodiment of the present invention). A method of drying or curing with a heat source (direct method), or applying a urethane-based pressure-sensitive adhesive composition to the surface (release surface) of a release liner and drying or curing it to form a urethane-based pressure-sensitive adhesive layer on the surface. A method (transfer method) of transferring the urethane-based pressure-sensitive adhesive layer to a film (for example, the base layer of the surface protection film according to the embodiment of the present invention) may be used. From the viewpoint of the anchoring property of the pressure-sensitive adhesive layer, typically, a direct method can be preferably employed. As for the various conditions in these forming methods, various conditions in conventionally known methods for forming urethane pressure-sensitive adhesives can be adopted.

Examples of methods for applying (typically coating) such a urethane pressure-sensitive adhesive layer include roll coating, gravure coating, reverse coating, kiss coating, dip roll coating, bar coating, and roll brushing. Various conventionally known methods such as coating method, spray coating method, knife coating method, air knife coating method, spray coating method, comma coating method, direct coating method, and coating method using a die coater can be appropriately employed.

Drying of the urethane pressure-sensitive adhesive composition can be performed under heating (for example, by heating to about 60° C. to 150° C.), if necessary. As means for curing the urethane pressure-sensitive adhesive composition, for example, ultraviolet rays, laser rays, α rays, β rays, γ rays, X rays, and electron beams can be appropriately employed.

As a method for producing urethane-based adhesives, there are two methods of manufacturing urethane-based adhesives: the one-shot method, in which a polyol and a polyfunctional isocyanate compound are directly reacted without using a urethane prepolymer, and the urethane prepolymer and a polyfunctional isocyanate compound. There are two types of production methods: a prepolymer method in which a urethane-based pressure-sensitive adhesive is produced by reacting . Here, since the "urethane prepolymer" can have a plurality of hydroxyl groups, in order to clarify the distinction from the "polyol", the "polyol (A1)" in the description of the present invention is replaced with " Urethane prepolymer (A2)” shall not be included.

<1-2-1. Urethane adhesive manufactured by one-shot method>
One embodiment of the polyurethane-based pressure-sensitive adhesive is a polyurethane-based pressure-sensitive adhesive obtained by curing a urethane-based pressure-sensitive adhesive composition containing a polyol (A1) and a polyfunctional isocyanate compound (B). That is, the urethane-based pressure-sensitive adhesive composition in this form contains a polyol (A1) and a polyfunctional isocyanate compound (B).

The content of the total amount of the polyol (A1) and the polyfunctional isocyanate compound (B) in the urethane-based pressure-sensitive adhesive composition in this form is preferably 50% by weight to 100% by weight, more preferably excluding the solvent. is 55% to 95% by weight, more preferably 60% to 90% by weight, particularly preferably 65% to 85% by weight, most preferably 70% to 80% by weight.

[1-2-1-a. Polyol (A1)]
Only one kind of polyol (A1) may be used, or two or more kinds thereof may be used.

Any appropriate polyol can be adopted as the polyol (A1) as long as it has two or more OH groups. Examples of such a polyol (A1) include a polyol having two OH groups (diol), a polyol having three OH groups (triol), a polyol having four OH groups (tetraol), and a polyol having five OH groups. polyols (pentaol) having one OH group, and polyols (hexaol) having six OH groups.

In the present invention, as the polyol (A1), a polyol (triol) having three OH groups is preferably employed as an essential component. When a polyol (triol) having three OH groups is employed as the polyol (A1) as an essential component, the effect of the present invention can be further exhibited.

The content of the polyol (triol) having three OH groups in the polyol (A1) is preferably 50% to 100% by weight, more preferably 70% to 100% by weight, and still more preferably 80% to 100% by weight, more preferably 90% to 100% by weight, particularly preferably 95% to 100% by weight, most preferably substantially 100% by weight.

The polyol (A1) preferably contains a polyol having a number average molecular weight Mn of 400 to 20,000. The content of the polyol having a number average molecular weight Mn of 400 to 20000 in the polyol (A1) is preferably 50% to 100% by weight, more preferably 70% to 100% by weight, and still more preferably 90% to 100% by weight, particularly preferably 95% to 100% by weight, most preferably substantially 100% by weight. By adjusting the content of the polyol having a number average molecular weight Mn of 400 to 20,000 in the polyol (A1) within the above range, the effect of the present invention can be further expressed.

In the present invention, when a polyol (triol) having three OH groups is employed as an essential component as the polyol (A1), preferably a triol having a number average molecular weight Mn of 7000 to 20000 and a number average molecular weight Mn of 2000 to 6000 and a triol having a number average molecular weight Mn of 400 to 1900 are used in combination, more preferably a triol having a number average molecular weight Mn of 8000 to 15000, a triol having a number average molecular weight Mn of 2000 to 5000, and a number average A triol having a molecular weight Mn of 500 to 1800 is used in combination, more preferably a triol having a number average molecular weight Mn of 8000 to 12000, a triol having a number average molecular weight Mn of 2000 to 4000, and a triol having a number average molecular weight Mn of 500 to 1500. Used in combination with a triol. The effect of the present invention can be further exhibited by using such three types of triols in combination.

Examples of polyols (A1) include polyester polyols, polyether polyols, polycaprolactone polyols, polycarbonate polyols, and castor oil-based polyols.

A polyester polyol can be obtained, for example, by an esterification reaction between a polyol component and an acid component.

Polyol components include, for example, ethylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 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, trimethylolpropane, pentaerythritol, hexanetriol, polypropylene glycol.

Examples of acid components include succinic acid, methylsuccinic acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid, 1,14-tetradecanedioic acid, dimer acid, 2-methyl-1, 4-cyclohexanedicarboxylic acid, 2-ethyl-1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid , and acid anhydrides thereof.

Examples of polyether polyols include water, low-molecular-weight polyols (propylene glycol, ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, etc.), bisphenols (bisphenol A, etc.), dihydroxybenzenes (catechol, resorcinol, hydroquinone, etc.). is used as an initiator, polyether polyols obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide. Specific examples of polyether polyols include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

Examples of polycaprolactone polyols include caprolactone-based polyester diols obtained by ring-opening polymerization of cyclic ester monomers such as ε-caprolactone and σ-valerolactone.

Polycarbonate polyols include, for example, polycarbonate polyols obtained by subjecting the above polyol component and phosgene to a polycondensation reaction; Polycarbonate polyols obtained by subjecting carbonic acid diesters such as propylene carbonate, diphenyl carbonate and dibenzyl carbonate to transesterification condensation; copolymerized polycarbonate polyols obtained by combining two or more of the above polyol components; various polycarbonate polyols and carboxyl groups above. Polycarbonate polyol obtained by esterification reaction with the containing compound; Polycarbonate polyol obtained by etherification reaction of the above various polycarbonate polyols and hydroxyl group-containing compounds; Obtained by transesterifying the above various polycarbonate polyols and ester compounds. Polycarbonate polyols obtained by transesterification of various polycarbonate polyols and hydroxyl group-containing compounds; Polyester-based polycarbonate polyols obtained by polycondensation reaction of various polycarbonate polyols and dicarboxylic acid compounds; Various polycarbonates above a copolymerized polyether-based polycarbonate polyol obtained by copolymerizing a polyol and an alkylene oxide;

Examples of castor oil-based polyols include castor oil-based polyols obtained by reacting castor oil fatty acids with the above polyol components. Specific examples of castor oil-based polyols include castor oil-based polyols obtained by reacting castor oil fatty acids with polypropylene glycol.

[1-2-1-b. Polyfunctional isocyanate compound (B) used in one-shot method]
The number of polyfunctional isocyanate compounds (B) used in the one-shot method may be one, or two or more.

As the polyfunctional isocyanate compound (B), any suitable polyfunctional isocyanate compound that can be used in the urethanization reaction can be adopted. Examples of such polyfunctional isocyanate compounds (B) include polyfunctional aliphatic isocyanate compounds, polyfunctional alicyclic isocyanates, and polyfunctional aromatic isocyanate compounds.

Polyfunctional aliphatic isocyanate compounds include, for example, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4, 4-trimethylhexamethylene diisocyanate may be mentioned.

Examples of polyfunctional alicyclic isocyanate compounds include 1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, Hydrogenated tolylene diisocyanate and hydrogenated tetramethylxylylene diisocyanate can be mentioned.

Polyfunctional aromatic diisocyanate compounds include, for example, phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene 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 and xylylene diisocyanate.

Examples of the polyfunctional isocyanate compound (B) include trimethylolpropane adducts, water-reacted biuret forms, and isocyanurate ring-containing trimethylolpropane adducts of various polyfunctional isocyanate compounds as described above. Moreover, you may use these together.

The content of the polyfunctional isocyanate compound (B) is preferably 5% to 60% by weight, more preferably 8% to 60% by weight, relative to the polyol (A1). %, more preferably 10 wt % to 60 wt %. By adjusting the content of the polyfunctional isocyanate compound (B) within the above range, the effects of the present invention can be exhibited more.

The equivalent ratio of the NCO group to the OH group in the polyol (A1) and the polyfunctional isocyanate compound (B) is more than 1.0 and 5 as the NCO group/OH group in that the effects of the present invention can be more expressed. .0 or less, preferably 1.1 to 5.0, more preferably 1.2 to 4.0, still more preferably 1.5 to 3.5, particularly preferably 1.8 ~3.0.

[1-2-1-c. Other ingredients]
The urethane-based pressure-sensitive adhesive composition may contain any appropriate other component within a range that does not impair the effects of the present invention. Such other components include, for example, other resin components, cross-linking agents other than the polyfunctional isocyanate compound (B), cross-linking retarders, ionic compounds, fluorine-based additives, silicone-based additives, fatty acid esters, adhesives Granting agents, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, anti-aging agents, conductive agents, UV absorbers, antioxidants, light stabilizers, surface lubricants, leveling agents, corrosion Examples include inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, and catalysts.

(Ionic compound)
When an ionic compound is included as another component, the antistatic performance of the pressure-sensitive adhesive layer-attached film according to the embodiment of the present invention can be improved.

As the content of the ionic compound, any appropriate content can be adopted as long as the effects of the present invention are not impaired. The content of the ionic compound with respect to the total amount of the polyol (A1) is preferably 0.05% by weight or more, and more preferably, from the viewpoint that the antistatic performance of the pressure-sensitive adhesive layer-attached film according to the embodiment of the present invention can be further improved. is 0.10% to 50% by weight, more preferably 0.20% to 30% by weight, particularly preferably 0.30% to 10% by weight, most preferably 0.50% by weight % to 1% by weight.

As the ionic compound, any suitable ionic compound can be adopted as long as the effects of the present invention are not impaired. Only one kind of ionic compound may be used, or two or more kinds thereof may be used.

The ionic compound is preferably an ionic compound containing at least one selected from onium cations and metal cations and a fluoroorganic anion, and an ionic group-containing silicone oligomer, in that the effects of the present invention can be further exhibited. An ionic compound containing at least one selected from onium cations and metal cations and a fluoroorganic anion is more preferable in that the appearance of the pressure-sensitive adhesive layer can be improved.

The ionic compound may be an ionic liquid. An ionic liquid means a molten salt (ionic compound) that exhibits a liquid state at 25°C.

As the ionic group-containing silicone oligomer, any suitable ionic group-containing silicone oligomer can be employed as long as the effects of the present invention are not impaired. Examples of ionic group-containing silicone oligomers include the trade name “X-40-2450” manufactured by Shin-Etsu Chemical Co., Ltd.

As the onium cation, any suitable onium cation can be adopted as long as the effects of the present invention are not impaired. From the viewpoint that the effects of the present invention can be more expressed, such onium cations are preferably ammonium cations (nitrogen-containing onium cations), sulfonium cations (sulfur-containing onium cations), and phosphorus-containing onium cations (phosphonium cations). At least one selected, more preferably an ammonium cation.

Any appropriate metal cation can be employed as the metal cation as long as the effects of the present invention are not impaired. Such metal cations are preferably alkali metal cations such as Li cations, Na cations, and K cations, in that the effects of the present invention can be expressed more effectively.

As the fluoroorganic anion, any suitable fluoroorganic anion can be employed as long as the effects of the present invention are not impaired. The fluoroorganic anions may be fully fluorinated (perfluorinated) or partially fluorinated.

Such fluoroorganic anions include, for example, fluorinated arylsulfonates, perfluoroalkanesulfonates, bis(fluorosulfonyl)imides, bis(perfluoroalkanesulfonyl)imides, cyanoperfluoroalkanesulfonylamides, bis(cyano) perfluoroalkanesulfonylmethide, cyano-bis-(perfluoroalkanesulfonyl)methide, tris(perfluoroalkanesulfonyl)methide, trifluoroacetate, perfluoroalkylate, tris(perfluoroalkanesulfonyl)methide, (perfluoroalkane sulfonyl)trifluoroacetamides.

Among these fluoroorganic anions, perfluoroalkylsulfonates, bis(fluorosulfonyl)imides, and bis(perfluoroalkanesulfonyl)imides are preferred from the viewpoint that the effects of the present invention can be more expressed. More specifically, is for example trifluoromethanesulfonate, pentafluoroethanesulfonate, heptafluoropropanesulfonate, nonafluorobutanesulfonate, bis(fluorosulfonyl)imide, bis(trifluoromethanesulfonyl)imide, preferably bis(fluorosulfonyl)imide, Bis(trifluoromethanesulfonyl)imide.

As the ionic compound, an ionic compound composed of an onium cation and a fluoroorganic anion is more preferable in that the effects of the present invention can be exhibited more effectively.

The onium cation preferably has at least one selected from structures represented by general formulas (1) to (4).

In general formula (1), Ra represents a hydrocarbon group having 4 to 20 carbon atoms and may contain a heteroatom; It represents a hydrogen group and may contain a heteroatom. However, when the nitrogen atom contains a double bond, there is no Rc.

In general formula (2), Rd represents a hydrocarbon group having 2 to 20 carbon atoms and may contain a heteroatom, and Re, Rf, and Rg are the same or different and are hydrogen or It represents 16 hydrocarbon groups and may contain heteroatoms.

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

In general formula (4), Z represents a nitrogen atom, a sulfur atom, or a phosphorus atom; Rl, Rm, Rn, and Ro are the same or different and represent a hydrocarbon group having 1 to 20 carbon atoms; It may contain atoms. However, when Z is a sulfur atom, there is no Ro.

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

Specific examples of the cation represented by formula (1) include 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-ethyl-3-methylpyridinium cation, 1-butyl -3-methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1-octyl-4-methylpyridinium cation, 1-butyl-3,4-dimethylpyridinium cation, pyridinium cations such as 1,1-dimethylpyrrolidinium cation; 1-ethyl-1-methylpyrrolidinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-butylpyrrolidinium 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-ethyl-1-heptylpyrrolidinium cation, 1 , 1-dipropylpyrrolidinium cation, 1-propyl-1-butylpyrrolidinium cation, 1,1-dibutylpyrrolidinium cation and other pyrrolidinium cations; 1-propylpiperidinium cation, 1-pentylpi peridinium cation, 1-methyl-1-ethylpiperidinium cation, 1-methyl-1-propylpiperidinium cation, 1-methyl-1-butylpiperidinium cation, 1-methyl-1-pentylpiperidinium Cation, 1-methyl-1-hexylpiperidinium cation, 1-methyl-1-heptylpiperidinium cation, 1-ethyl-1-propylpiperidinium cation, 1-ethyl-1-butylpiperidinium cation , 1-ethyl-1-pentylpiperidinium cation, 1-ethyl-1-hexylpiperidinium cation, 1-ethyl-1-heptylpiperidinium cation, 1-propyl-1-butylpiperidinium cation, Piperidinium cations such as 1,1-dimethylpiperidinium cation, 1,1-dipropylpiperidinium cation, 1,1-dibutylpiperidinium cation; 2-methyl-1-pyrroline cation; 1,2-dimethylindole cation; 1-ethylcarbazole cation; these cations further form vinyl groups (CH ₂ =CH-groups) and allyl groups (CH ₂ =CH-CH ₂ -groups). ) a cation having at least one selected from;

Among these, 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-ethyl-3-methylpyridinium cation, 1 -pyridinium cations such as butyl-3-methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1-octyl-4-methylpyridinium cation; 1-ethyl-1- methylpyrrolidinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-butylpyrrolidinium cation, 1-methyl-1-pentylpyrrolidinium cation, 1-methyl-1-hexyl pyrrolidinium cation, 1-methyl-1-heptylpyrrolidinium cation, 1-ethyl-1-propylpyrrolidinium cation, 1-ethyl-1-butylpyrrolidinium cation, 1-ethyl-1-pentylpyrrolidinium cation cation, 1-ethyl-1-hexylpyrrolidinium cation, 1-ethyl-1-heptylpyrrolidinium cation; 1-methyl-1-ethylpiperidinium cation, 1-methyl -1-propylpiperidinium cation, 1-methyl-1-butylpiperidinium cation, 1-methyl-1-pentylpiperidinium cation, 1-methyl-1-hexylpiperidinium cation, 1-methyl-1 -heptylpiperidinium cation, 1-ethyl-1-propylpiperidinium cation, 1-ethyl-1-butylpiperidinium cation, 1-ethyl-1-pentylpiperidinium cation, 1-ethyl-1- piperidinium cations such as hexylpiperidinium cation, 1-ethyl-1-heptylpiperidinium cation, 1-propyl- ₁ -butylpiperidinium cation; group) and an allyl group (CH ₂ ═CH—CH ₂ — group); more preferably, 1-hexylpyridinium cation and 1-ethyl-3-methylpyridinium cation , 1-butyl-3-methylpyridinium cation, 1-octyl-4-methylpyridinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-propylpiperidinium cation, These cations are cations further having at least one selected from a vinyl group (CH ₂ =CH- group) and an allyl group (CH ₂ =CH--CH ₂ -- group).

Examples of the cation structure represented by general formula (2) include an imidazolium cation structure, a tetrahydropyrimidinium cation structure, and a dihydropyrimidinium cation structure.

Specific examples of the cation represented by the general formula (2) include, for example, 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 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, 1-dodecyl-3-methylimidazolium cation lithium cation, 1-tetradecyl-3-methylimidazolium cation, 1,2-dimethyl-3-propylimidazolium cation, 1-ethyl-2,3-dimethylimidazolium cation, 1-butyl-2,3-dimethylimidazolium cation imidazolium cations such as lithium cations, 1-hexyl-2,3-dimethylimidazolium cations; 1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium cations, 1,2,3-trimethyl- 1,4,5,6-tetrahydropyrimidinium cation, 1,2,3,4-tetramethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,2,3,5-tetramethyl- Tetrahydropyrimidinium cations such as 1,4,5,6-tetrahydropyrimidinium cations; 1,3-dimethyl-1,4-dihydropyrimidinium cations, 1,3-dimethyl-1,6-dihydropyrimidinium cations cation, 1,2,3-trimethyl-1,4-dihydropyrimidinium cation, 1,2,3-trimethyl-1,6-dihydropyrimidinium cation, 1,2,3,4-tetramethyl- Dihydropyrimidinium cations such as 1,4-dihydropyrimidinium cation, 1,2,3,4 _- tetramethyl-1,6-dihydropyrimidinium cation; - group) and a cation having at least one selected from an allyl group (CH ₂ =CH-CH ₂ - group);

Among these, 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 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, 1-dodecyl-3- methylimidazolium cation, 1-tetradecyl-3-methylimidazolium cation, and at least one of these cations further selected from a vinyl group (CH ₂ =CH- group) and an allyl group (CH ₂ =CH-CH _2- group) imidazolium cations such as cations having a seed, more preferably 1-ethyl-3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, these cations further having a vinyl group (CH ₂ = CH— group) and an allyl group (CH ₂ ═CH—CH ₂ — group).

Examples of the cation structure represented by general formula (3) include a pyrazolium cation structure and a pyrazolinium cation structure.

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- pyrazolium cations such as 2,3,5-trimethylpyrazolium cation, 1-propyl-2,3,5-trimethylpyrazolium cation, 1-butyl-2,3,5-trimethylpyrazolium cation; pyrazolinium cation such as 1-ethyl-2,3,5-trimethylpyrazolinium cation, 1-propyl-2,3,5-trimethylpyrazolinium cation, 1-butyl-2,3,5-trimethylpyrazolinium cation Zolinium cations; cations further having at least one selected from a vinyl group (CH ₂ =CH- group) and an allyl group (CH ₂ =CH-CH ₂ - group);

Examples of the cation structure represented by the general formula (4) include, for example, a tetraalkylammonium cation structure, a trialkylsulfonium cation structure, a tetraalkylphosphonium cation structure, and a part of the above alkyl group being an alkenyl group, an alkoxyl group, or an epoxy group. Those substituted with are mentioned.

Specific examples of the cation represented by formula (4) include tetramethylammonium cation, tetraethylammonium cation, tetrabutylammonium cation, tetrapentylammonium cation, tetrahexylammonium cation, tetraheptylammonium cation, and triethylmethylammonium. cations, tributylethylammonium cation, trimethylpropylammonium cation, trimethyldecylammonium cation, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium cation, glycidyltrimethylammonium cation, diallyldimethylammonium cation, N, N-dimethyl-N-ethyl-N-propylammonium cation, N,N-dimethyl-N-ethyl-N-butylammonium cation, N,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-diethyl-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-diethyl-N-butyl-N -heptylammonium cation, N,N-dimethyl-N-pentyl-N-hexylammonium cation, N,N-dimethyl-N,N-dihexylammonium cation, trimethylheptylammonium 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, triethylpentylammonium 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-pentylammonium cation, N,N-dibutyl-N-methyl-N-hexylammonium cation, trioctylmethylammonium cation, N-methyl-N-ethyl-N-propyl-N- tetraalkylammonium cations such as pentylammonium cation; trialkylsulfonium cations such as trimethylsulfonium cation, triethylsulfonium cation, tributylsulfonium cation, trihexylsulfonium cation, diethylmethylsulfonium cation, dibutylethylsulfonium cation, dimethyldecylsulfonium cation; tetramethyl tetraalkylphosphonium cations such as phosphonium cations, tetraethylphosphonium cations, tetrabutylphosphonium cations, tetrahexylphosphonium cations, tetraoctylphosphonium cations, triethylmethylphosphonium cations, tributylethylphosphonium cations, trimethyldecylphosphonium cations; cations having at least one selected from (CH ₂ =CH- group) and allyl groups (CH ₂ =CH-CH ₂ - group);

The ionic compound is preferably an ionic compound containing at least one selected from the above onium cations and the above metal cations and the above fluoroorganic anion, or an ionic group-containing silicone oligomer, more preferably the above and at least one selected from the above metal cations and the above fluoroorganic anion, and more preferably an ionic compound containing the above onium cation and the above fluoroorganic anion.

Specifically, the ionic compound is preferably 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-methylpyridinium bis(fluorosulfonyl)imide, 1-methyl-1-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1 -methyl-1-propylpyrrolidinium 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-methylimidazolium bis(fluorosulfonyl)imide, 1-allyl-3-methyl-imidazolium trifluoromethanesulfonate, 1-allyl-3-methyl-imidazo Lithium Heptafluoropropanesulfonate, 1-allyl-3-methyl-imidazolium bis(trifluoromethanesulfonyl)imide, 1-allyl-3-methyl-imidazolium bis(fluorosulfonyl)imide, methyltrioctylammonium bis(trifluoromethanesulfonyl) ) imide, trimethylpropylammonium bis(trifluoromethanesulfonyl)imide, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, more preferably 1-butyl-3-methylpyridinium bis(trifluoromethanesulfonyl ) imide, 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imido imide, 1-allyl-3-methyl-imidazolium bis(trifluoromethanesulfonyl)imide, methyltrioctylammonium bis(trifluoromethanesulfonyl)imide, trimethylpropylammonium bis(trifluoromethanesulfonyl)imide, lithium bis(trifluoromethanesulfonyl)imide imide, more preferably 1-butyl-3-methylpyridinium bis(trifluoromethanesulfonyl)imide, 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide, 1-allyl-3-methyl-imidazolium bis(trifluoromethanesulfonyl)imide, methyltrioctylammonium bis(trifluoromethanesulfonyl)imide, and trimethylpropylammonium bis(trifluoromethanesulfonyl)imide.

Commercially available ionic compounds may be used, or those synthesized by any appropriate method may be used. For example, ionic liquids can be obtained by the halide method, hydroxide method, acid ester method, complex formation method, as described in "Ionic liquids - the front line of development and the future" (published by CMC Publishing). and may be synthesized by a neutralization method or the like.

(Fluorine-based additive)
When a fluorine-based additive is included as another component, it is possible to further improve the separatorless winding and unwinding properties of the pressure-sensitive adhesive layer-attached film according to the embodiment of the present invention, as well as the antistatic performance.

As the fluorine-based additive, any suitable fluorine-based additive can be employed as long as the effects of the present invention are not impaired.

The fluorine-based additive may be used alone or in combination of two or more.

As the content of the fluorine-based additive, any appropriate content can be adopted as long as the effects of the present invention are not impaired. From the point of view of further improving the separatorless winding and unwinding properties and antistatic performance of the pressure-sensitive adhesive layer-attached film according to the embodiment of the present invention, the content of the fluorine-based additive with respect to the total amount of the polyol (A1) is It is preferably 0.01% by weight or more, more preferably 0.03% by weight to 30% by weight, still more preferably 0.05% by weight to 10% by weight, and particularly preferably 0.05% by weight to 1 part by weight.

From the point of view that the effect of the present invention can be more expressed, the content ratio of the total amount of the fluorine-based additive and the silicone-based additive described later with respect to the total amount of the polyol (A1) is preferably 0.01% by weight or more, and more preferably. is 0.03 to 30 parts by weight, more preferably 0.05 to 10 parts by weight, particularly preferably 0.05 to 1 part by weight.

Examples of fluorine-based additives include at least one selected from fluorine-containing compounds, hydroxyl group-containing fluorine-based compounds, and crosslinkable functional group-containing fluorine-based compounds.

The fluorine-containing compound includes, for example, a compound having a fluoroaliphatic hydrocarbon skeleton, a fluorine-containing organic compound obtained by copolymerizing an organic compound and a fluorine compound, and a fluorine-containing compound containing an organic compound. Fluoroaliphatic hydrocarbon backbones include, for example, fluoroC1-C10 alkanes such as fluoromethane, fluoroethane, fluoropropane, fluoroisopropane, fluorobutane, fluoroisobutane, fluoro-t-butane, fluoropentane, and fluorohexane. . Here, the notation "C1-C10" means 1-10 carbon atoms.

A preferred embodiment of the fluorine-containing compound is an oligomer (“specific fluorine compound”) having a fluorine-containing group and a hydrophilic group and/or a lipophilic group. By adopting such a "specific fluorine-based compound", separatorless winding and unwinding properties and antistatic performance of the pressure-sensitive adhesive layer-attached film according to the embodiment of the present invention can be further improved. Typical fluorine-containing groups include fluorine-containing alkyl groups (eg, CF ₃ —) and/or fluorine-containing alkylene groups (eg, —CF ₂ —CF ₂ —). A hydrophilic group is a group having hydrophilicity, and hydrophilicity is translated into English as "hydrophilic" and is a property generally known to those skilled in the art as "having an affinity for water". (See, for example, McGraw-Hill Encyclopedia of Science and Technology Terms (revised 3rd edition, Nikkan Kogyo Shimbun, Ltd.), etc.). A lipophilic group is a group having lipophilic properties, and lipophilicity is translated in English as "lipophilic" and is a property generally known to those skilled in the art as "having an affinity for oils". (See, for example, McGraw-Hill Encyclopedia of Science and Technology Terms (revised 3rd edition, Nikkan Kogyo Shimbun, Ltd.), etc.).

As the fluorine-containing compound, a 0.1% toluene solution is used from the viewpoint that the film with a pressure-sensitive adhesive layer according to the embodiment of the present invention can be further improved in separatorless winding and unwinding properties and antistatic performance. preferably has a surface tension of 19.0 mN/m to 26.0 mN/m (the surface tension of toluene is 27.9 mN/m).

As the fluorine-containing compound, a 0.1% toluene solution is used from the viewpoint that the film with a pressure-sensitive adhesive layer according to the embodiment of the present invention can be further improved in separatorless winding and unwinding properties and antistatic performance. is preferably 26.0 mN/m to 28.0 mN/m (the surface tension of toluene is 27.9 mN/m).

Commercially available fluorine-containing compounds include, for example, the following.

Megafuck series manufactured by DIC Corporation:
Typically, "Megafuck F-114", "Megafuck F-251", "Megafuck F-253", "Megafuck F-281", "Megafuck F-410", "Megafuck F- 430", "Megafuck F-444", "Megafuck F-477", "Megafuck F-510", "Megafuck F-551-A", "Megafuck F-553", "Megafuck F- 554", "Megafuck F-555-A", "Megafuck F-556", "Megafuck F-557", "Megafuck F-558", "Megafuck F-559", "Megafuck F- 560", "Megafuck F-561", "Megafuck F-562", "Megafuck F-563", "Megafuck F-565", "Megafuck F-568", "Megafuck F-569" , “Megafuck F-570”, “Megafuck F-576”, “Megafuck R-01”, “Megafuck R-40”, “Megafuck R-40-LM”, “Megafuck R-41” , "Megafuck R-41-LM", "Megafuck R-94", "Megafuck RS-56", "Megafuck RS-72-K", "Megafuck RS-75-A", "Megafuck RS-75-NS", "Megafac RS-78", "Megafac RS-90", etc.

Surflon series manufactured by AGC Seimi Chemical Co., Ltd.:
Typical examples are "S-242", "S-243", "S-386" and the like.

FC series manufactured by Sumitomo 3M:
Typical examples are "FC-4430" and "FC-4432".

Futergent series manufactured by Neos Co., Ltd.:
Representative examples are "Ftergent 100", "Ftergent 100C", "Ftergent 110", "Ftergent 150", "Ftergent 150CH", "Ftergent 250", "Ftergent 400SW" and the like.

PF series manufactured by Kitamura Chemical Industry Co., Ltd.:
Typically, "PF-136A", "PF-156A", "PF-151N", "PF-636", "PF-6320", "PF-656", "PF-6520", "PF- 651”, “PF-652”, “PF-3320”, etc.

As the hydroxyl group-containing fluorine-based compound, for example, conventionally known resins can be used. No. 97/11130 pamphlet, and International Publication No. 96/26254 pamphlet. Other hydroxyl group-containing fluororesins include, for example, JP-A-8-231919, JP-A-10-265731, JP-A-10-204374, JP-A-8-12922, and the like. A polymer etc. are mentioned. In addition, a copolymer of a compound having a fluorinated alkyl group in a hydroxyl group-containing compound, a fluorine-containing organic compound obtained by copolymerizing a fluorine-containing compound in a hydroxyl group-containing compound, and a fluorine-containing compound containing a hydroxyl group-containing organic compound. Examples of such hydroxyl group-containing fluorine-based compounds include commercially available products such as "Lumiflon" (manufactured by Asahi Glass Co., Ltd.), "Cefral Coat" (manufactured by Central Glass Co., Ltd.), and "Zaflon" (trade name). (manufactured by Toagosei Co., Ltd.) and trade name "Zeffle" (manufactured by Daikin Industries, Ltd.).

Examples of crosslinkable functional group-containing fluorine-based compounds include carboxylic acid compounds having a fluorinated alkyl group such as perfluorooctanoic acid, and compounds having a crosslinkable functional group-containing compound having a fluorinated alkyl group. Polymers, fluorine-containing organic compounds obtained by copolymerizing fluorine-containing compounds with crosslinkable functional group-containing compounds, and fluorine-containing compounds containing crosslinkable functional group-containing compounds can be mentioned. Examples of such crosslinkable functional group-containing fluorine-based compounds include commercially available products such as "Megafac F-570", "Megafac RS-55", "Megafac RS-56", and "Megafac RS-72-K", "Megafac RS-75", "Megafac RS-76-E", "Megafac RS-76-NS", "Megafac RS-78", "Megafac RS-90" (manufactured by DIC Corporation).

Among commercially available fluorine-containing compounds, those corresponding to the above-mentioned "oligomer having a fluorine-containing group and a hydrophilic group and/or a lipophilic group" are typically available from DIC Corporation. made of
"Megafac F-477" (fluorine-containing group-hydrophilic group-lipophilic group-containing oligomer, surface tension = 26.4 mN/m when used as a 0.1% toluene solution),
"Megafac F-551-A" (fluorinated group/lipophilic group-containing oligomer, surface tension = 25.6 mN/m when used as a 0.1% toluene solution),
"Megafac F-553" (fluorine-containing group/hydrophilic group/lipophilic group-containing oligomer, surface tension = 26.4 mN/m when used as a 0.1% toluene solution),
"Megafac F-554" (fluorinated group/lipophilic group-containing oligomer, surface tension = 25.0 mN/m when used as a 0.1% toluene solution),
"Megafac F-555-A" (fluorine-containing group-hydrophilic group-lipophilic group-containing oligomer, surface tension = 20.4 mN / m when used as a 0.1% toluene solution),
"Megafac F-557" (fluorine-containing group-hydrophilic group-lipophilic group-containing oligomer, surface tension = 26.3 mN/m when used as a 0.1% toluene solution),
"Megafac F-559" (fluorine-containing group-hydrophilic group-lipophilic group-containing oligomer, surface tension = 26.1 mN/m when used as a 0.1% toluene solution),
"Megafac F-563" (fluorinated group/lipophilic group-containing oligomer, surface tension = 20.2 mN/m when used as a 0.1% toluene solution),
"Megafac F-569" (fluorinated group/hydrophilic group-containing oligomer, surface tension = 19.7 mN/m when used as a 0.1% toluene solution),
etc.

(Silicone additive)
When a silicone-based additive is included as another component, it is possible to further improve the separatorless winding and unwinding properties of the pressure-sensitive adhesive layer-attached film according to the embodiment of the present invention.

As the silicone additive, any appropriate silicone additive can be employed as long as the effects of the present invention are not impaired.

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

As the content of the silicone-based additive, any appropriate content can be adopted as long as the effects of the present invention are not impaired. The content of the silicone-based additive relative to the total amount of the polyol (A1) is preferably 0.00%, in order to further improve the separatorless winding and unwinding properties of the pressure-sensitive adhesive layer-attached film according to the embodiment of the present invention. 01% by weight or more, more preferably 0.015% by weight to 30% by weight, still more preferably 0.02% by weight to 10% by weight, and particularly preferably 0.025% by weight to 1% by weight. be.

From the point of view that the effect of the present invention can be more expressed, the content ratio of the total amount of the fluorine-based additive and the silicone-based additive to the total amount of the polyol (A1) is preferably 0.01% by weight or more, and more preferably. is 0.03 to 30 parts by weight, more preferably 0.05 to 10 parts by weight, particularly preferably 0.05 to 1 part by weight.

Any appropriate silicone-based additive can be adopted as the silicone-based additive as long as it does not impair the effects of the present invention. Examples of such silicone additives include reactive silicone oils and non-reactive silicone oils.

Reactive silicone oils include, for example, side chain type reactive silicone oils in which organic groups are bonded as side chains to Si atoms that provide siloxane bonds, and double-end type in which organic groups are bonded to Si atoms located at both ends of the structure. Reactive silicone oil, single-end reactive silicone oil in which an organic group is bonded to only one of the Si atoms located at both ends of the structure, organic groups are bonded as side chains to the Si atoms used for siloxane bonding, and both ends of the structure Side chain double-ended reactive silicone oils in which an organic group is bonded to the Si atom located at the end are exemplified.

Examples of side-chain reactive silicone oils include amino-modified side-chain reactive silicone oils, epoxy-modified side-chain reactive silicone oils, carbinol-modified side-chain reactive silicone oils, mercapto Modified side-chain reactive silicone oils, carboxyl-modified side-chain reactive silicone oils, and methylhydrogensilicone oil-type side-chain reactive silicone oils can be used. Examples of these commercial products include various silicone oils marketed as side-chain reactive silicone oils manufactured by Shin-Etsu Chemical Co., Ltd.

Examples of the double-end reactive silicone oil include amino-modified double-end reactive silicone oil, epoxy-modified double-end reactive silicone oil, carbinol-modified double-end reactive silicone oil, methacryl Modified type reactive silicone oil at both ends, polyether-modified reactive silicone oil at both ends, mercapto-modified reactive silicone oil at both ends, carboxyl-modified reactive silicone oil at both ends, phenol-modified type reactive silicone oil, silanol-terminated reactive silicone oil, acrylic-modified reactive silicone oil, and carboxylic acid anhydride-modified reactive silicone oil. be done. Examples of these commercial products include various silicone oils marketed as double-ended reactive silicone oils manufactured by Shin-Etsu Chemical Co., Ltd. In particular, carbinol-modified double-ended reactivity such as "KF-6000", "KF-6001", "KF-6002", "KF-6003", and "KF-6028" manufactured by Shin-Etsu Chemical Co., Ltd. Silicone oil can be preferably employed.

The single-end reactive silicone oil includes, for example, a single-end reactive modified type single-end reactive silicone oil and an average single-end carboxyl-modified single-end reactive silicone oil. Examples of these commercial products include various silicone oils marketed as single-ended reactive silicone oils manufactured by Shin-Etsu Chemical Co., Ltd. In particular, carbinol-modified single-ended reactive silicone oils such as "X-22-170BX", "X-22-170DX" and "X-22-4015" manufactured by Shin-Etsu Chemical Co., Ltd. can be preferably employed. .

Examples of the side-chain both-terminal reactive silicone oil include side-chain amino/both-terminal methoxy-modified side-chain both-terminal reactive silicone oil and epoxy-modified side-chain both-terminal reactive silicone oil. . Examples of these commercial products include various silicone oils marketed as reactive silicone oils with both side chain ends manufactured by Shin-Etsu Chemical Co., Ltd.

Non-reactive silicone oils include, for example, side-chain non-reactive silicone oils in which organic groups are bonded as side chains to Si atoms that provide siloxane bonds, and organic groups in which organic groups are bonded to Si atoms located at both ends of the structure. A terminal type non-reactive silicone oil may be mentioned.

Examples of side-chain non-reactive silicone oils include polyether-modified side-chain non-reactive silicone oils, aralkyl-modified side-chain non-reactive silicone oils, and batho alkyl-modified side-chain non-reactive silicone oils. Reactive silicone oil, long-chain alkyl-modified side-chain non-reactive silicone oil, higher fatty acid ester-modified side-chain non-reactive silicone oil, higher fatty acid-containing side-chain non-reactive silicone oil, phenyl Modified side chain type non-reactive silicone oils are included. Examples of these commercial products include various silicone oils marketed as side-chain non-reactive silicone oils manufactured by Shin-Etsu Chemical Co., Ltd. In particular, "KF-351A", "KF-352A", "KF-353", "KF-354L", "KF-355A", "KF-615A", "KF-945" manufactured by Shin-Etsu Chemical Co., Ltd., Polyether modified type such as "KF-640", "KF-642", "KF-643", "KF-644", "KF-6020", "KF-6204", "X-22-4515" side chain type non-reactive silicone oil can be preferably employed.

Among these polyether-modified side-chain non-reactive silicone oils, the HLB value is preferably 8 or more, more preferably 9 or more, and still more preferably 10 or more in terms of further reducing adhesive residue. Polyether-modified side-chain non-reactive silicone oils are preferred. Examples of such polyether-modified side chain non-reactive silicone oils include "KF-351A" (HLB = 12), "KF-353" (HLB = 10), "KF-354L" (HLB = 16), “KF-355A” (HLB = 12), “KF-615A” (HLB = 10), “KF-640” (HLB = 14), “KF-642” (HLB = 12), “KF -643” (HLB=14), “KF-644” (HLB=11), and “KF-6204” (HLB=10).

Examples of the double-ended non-reactive silicone oil include polyether-modified double-ended non-reactive silicone oil. Examples of these commercial products include various silicone oils marketed as double-ended non-reactive silicone oils manufactured by Shin-Etsu Chemical Co., Ltd. In particular, a polyether-modified double-ended non-reactive silicone oil such as "KF-6004" manufactured by Shin-Etsu Chemical Co., Ltd. can be preferably used.

As the silicone-based additive, in addition to the above, any suitable silicone-based additive conventionally known can be employed. Examples of such silicone additives include siloxane bond-containing polymers other than those described above, hydroxyl group-containing silicone compounds other than those described above, and silicone compounds containing crosslinkable functional groups other than those described above.

Examples of commercial products of siloxane bond-containing polymers other than those described above include, for example, the product name "LE-302" (manufactured by Kyoeisha Chemical Co., Ltd.), BYK series leveling agent manufactured by BYK Chemie Japan Co., Ltd. ("BYK-300 , BYK-301/302, BYK-306, BYK-307, BYK-310, BYK-315, BYK-313, BYK-320, BYK-322 ”, “BYK-323”, “BYK-325”, “BYK-330”, “BYK-331”, “BYK-333”, “BYK-337”, “BYK-341”, “BYK-344”, "BYK-345/346", "BYK-347", "BYK-348", "BYK-349", "BYK-370", "BYK-375", "BYK-377", "BYK-378", "BYK-UV3500", "BYK-UV3510", "BYK-UV3570", "BYK-3550", "BYK-SILCLEAN3700", "BYK-SILCLEAN3720", etc.), AC series leveling agents manufactured by Algin Chemie (" AC FS180", "AC FS360", "AC S20", etc.), Polyflow series leveling agents manufactured by Kyoeisha Chemical Co., Ltd. ("Polyflow KL-400X", "Polyflow KL-400HF", "Polyflow KL-401") , "Polyflow KL-402", "Polyflow KL-403", "Polyflow KL-404", etc.), KP series leveling agents manufactured by Shin-Etsu Chemical Co., Ltd. ("KP-323", "KP-326", "KP-341", "KP-104", "KP-110", "KP-112", etc.), leveling agents manufactured by Dow Corning Toray Co., Ltd. ("LP-7001", "LP-7002", "8032ADDITIVE", "57ADDITIVE", "L-7604", "FZ-2110", "FZ-2105", "67ADDITIVE", "8618ADDITIVE", "3ADDITIVE", "56ADDITIVE", etc.).

Examples of commercially available hydroxyl group-containing silicones other than those mentioned above include "BYK-370", "BYK-SILCLEAN3700" and "BYK-SILCLEAN3720" manufactured by BYK-Chemie Japan.

Examples of commercially available crosslinkable functional group-containing silicone compounds other than those described above include "BY16-855", "SF8413", "BY16-839", and "SF8421" manufactured by Dow Corning Toray Co., Ltd. "BY16-750", "BY16-880", and "BY16-152C".

(degradation inhibitor)
The urethane-based pressure-sensitive adhesive composition may contain a deterioration inhibitor as another component from the viewpoint of suppressing deterioration of the urethane-based pressure-sensitive adhesive. Only one kind of anti-degradation agent may be used, or two or more kinds thereof may be used.

Anti-deterioration agents include, for example, antioxidants, ultraviolet absorbers, and light stabilizers.

Only one kind of antioxidant may be used, or two or more kinds thereof may be used.

Any appropriate content can be adopted as the content of the antioxidant in the urethane-based pressure-sensitive adhesive composition as long as the effects of the present invention are not impaired. Such a content ratio is preferably 0.01% by weight to 10% by weight or more, more preferably 0.05% by weight to 5% by weight, as the content ratio of the antioxidant with respect to the total amount of polyol (A1). , more preferably 0.1 wt% to 3 wt%, particularly preferably 0.2 wt% to 1 wt%.

Antioxidants include, for example, radical chain inhibitors and peroxide decomposers.

Examples of radical chain inhibitors include phenol antioxidants and amine antioxidants.

Examples of peroxide decomposers include sulfur-based antioxidants and phosphorus-based antioxidants.

Examples of phenolic antioxidants include monophenolic antioxidants, bisphenolic antioxidants, and polymeric phenolic antioxidants.

Examples of monophenol antioxidants include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, stearin-β-( 3,5-di-t-butyl-4-hydroxyphenyl)propionate.

Examples of bisphenol antioxidants include 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 4,4' -thiobis(3-methyl-6-t-butylphenol), 4,4′-butylidenebis(3-methyl-6-t-butylphenol), 3,9-bis[1,1-dimethyl-2-[β-( 3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]2,4,8,10-tetraoxaspiro[5,5]undecane.

Examples of polymeric phenolic antioxidants include 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-trimethyl-2,4, 6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tetrakis-[methylene-3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionate]methane , bis[3,3′-bis-(4′-hydroxy-3′-t-butylphenyl)butyric acid]glycol ester, 1,3,5-tris(3′,5′-di-t-butyl -4′-hydroxybenzyl)-S-triazine-2,4,6-(1H,3H,5H)trione, tocopherol.

Examples of sulfur-based antioxidants include dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, and distearyl 3,3'-thiodipropionate.

Phosphorus-based antioxidants include, for example, triphenylphosphite, diphenylisodecylphosphite, and phenyldiisodecylphosphite.

Only one ultraviolet absorber may be used, or two or more ultraviolet absorbers may be used.

Any appropriate content can be adopted as the content of the ultraviolet absorber in the urethane-based pressure-sensitive adhesive composition as long as the effects of the present invention are not impaired. Such a content ratio is preferably 0.01% by weight to 10% by weight or more, more preferably 0.05% by weight to 5% by weight, as the content ratio of the ultraviolet absorber with respect to the total amount of polyol (A1). , more preferably 0.1 wt% to 3 wt%, particularly preferably 0.2 wt% to 1 wt%.

Examples of the ultraviolet absorber include benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, salicylic acid-based ultraviolet absorbers, oxalic acid anilide-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, and triazine-based ultraviolet absorbers. .

Benzophenone-based UV absorbers include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 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-benzoylphenyl ) methane.

Benzotriazole-based UV absorbers include, for example, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-butylphenyl)benzotriazole, 2-( 2′-hydroxy-3′,5′-di-tert-butylphenyl)benzotriazole, 2-(2′-hydroxy-3′-tert-butyl-5′-methylphenyl)-5-chlorobenzotriazole, 2 -(2'-hydroxy-3',5'-di-tert-butylphenyl)5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-amylphenyl)benzotriazole, 2-(2'-hydroxy-4'-octoxyphenyl)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'-methacryloxyphenyl)-2H-benzotriazole.

Examples of salicylic acid-based ultraviolet absorbers include phenyl salicylate, p-tert-butylphenyl salicylate, and p-octylphenyl salicylate.

Examples of cyanoacrylate ultraviolet absorbers include 2-ethylhexyl-2-cyano-3,3'-diphenyl acrylate and ethyl-2-cyano-3,3'-diphenyl acrylate.

Only one kind of light stabilizer may be used, or two or more kinds thereof may be used.

Any appropriate content can be adopted as the content of the light stabilizer in the urethane-based pressure-sensitive adhesive composition as long as the effects of the present invention are not impaired. Such a content ratio is preferably 0.01% by weight to 10% by weight or more, more preferably 0.05% by weight to 5% by weight, as the content ratio of the light stabilizer with respect to the total amount of the polyol (A1). , more preferably 0.1 wt% to 3 wt%, particularly preferably 0.2 wt% to 1 wt%.

Light stabilizers include, for example, hindered amine light stabilizers and ultraviolet stabilizers.

Examples of hindered amine light stabilizers include [bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate] and bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate. , methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate.

UV stabilizers include, for example, nickel bis(octylphenyl) sulfide, [2,2′-thiobis(4-tert-octylphenolate)]-n-butylamine nickel, nickel complex-3,5-di-tert- Butyl-4-hydroxybenzyl-phosphate monoethylate, nickel-dibutyldithiocarbamate, benzoate-type quenchers, nickel-dibutyldithiocarbamate.

The deterioration inhibitor is preferably a deterioration inhibitor having a hindered phenol structure. When an anti-degradation agent having a hindered phenol structure is included as an anti-degradation agent, the content is preferably 0.01% by weight to 10% by weight, more preferably 0.05%, relative to the polyol (A). % to 10% by weight, more preferably 0.1% to 10% by weight. By adjusting the content of the anti-degradation agent having a hindered phenol structure within the above range, the effect of the present invention can be more manifested.

As a deterioration inhibitor having a hindered phenol structure, for example, a group having a large steric hindrance such as a tertiary butyl group is bonded to at least one of the carbon atoms adjacent to the carbon atoms on the aromatic ring to which the OH group of the phenol is bonded. A deterioration inhibitor having a hindered phenol structure is mentioned.

Specific examples of anti-degradation agents having a hindered phenol structure include, for example, dibutylhydroxytoluene (BHT); trade name "IRGANOX1010" (manufactured by BASF), trade name "IRGANOX1010FF" (manufactured by BASF), trade name "IRGANOX1035" ” (manufactured by BASF), trade name “IRGANOX1035FF” (manufactured by BASF), trade name “IRGANOX1076” (manufactured by BASF), trade name “IRGANOX1076FD” (manufactured by BASF), trade name “IRGANOX1076DWJ” (manufactured by BASF), trade name “IRGANOX1098 ” (manufactured by BASF), trade name “IRGANOX1135” (manufactured by BASF), trade name “IRGANOX1330” (manufactured by BASF), trade name “IRGANOX1726” (manufactured by BASF), trade name “IRGANOX1425WL” (manufactured by BASF), trade name “IRGANOX1520L ” (manufactured by BASF), trade name “IRGANOX245” (manufactured by BASF), trade name “IRGANOX245FF” (manufactured by BASF), trade name “IRGANOX259” (manufactured by BASF), trade name “IRGANOX3114” (manufactured by BASF), trade name “IRGANOX565 ” (manufactured by BASF), trade name “IRGANOX295” (manufactured by BASF), etc.; trade name “TINUVIN P” (manufactured by BASF), trade name “TINUVIN P FL” (manufactured by BASF), trade name "TINUVIN234" (manufactured by BASF), trade name "TINUVIN326" (manufactured by BASF), trade name "TINUVIN326FL" (manufactured by BASF), trade name "TINUVIN328" (manufactured by BASF), trade name "TINUVIN329" (manufactured by BASF), trade name Benzotriazole-based ultraviolet absorbers such as "TINUVIN329FL" (manufactured by BASF); liquid ultraviolet absorbers such as the trade name "TINUVIN213" (manufactured by BASF) and the trade name "TINUVIN571" (manufactured by BASF); the trade name "TINUVIN1577ED" (manufactured by BASF) ); benzoate UV absorbers such as the trade name “TINUVIN120” (manufactured by BASF); and hindered amine light stabilizers such as the trade name “TINUVIN144” (manufactured by BASF).

(fatty acid ester)
The urethane-based pressure-sensitive adhesive composition may contain a fatty acid ester as another component from the viewpoint of improving the wettability of the urethane-based pressure-sensitive adhesive. Only one kind of fatty acid ester may be used, or two or more kinds thereof may be used.

Any appropriate content ratio can be adopted as the content ratio of the fatty acid ester in the urethane-based pressure-sensitive adhesive composition as long as the effects of the present invention are not impaired. Such a content ratio is preferably 1 wt% to 60 wt%, more preferably 5 wt% to 55 wt%, still more preferably 10 wt% to 50 wt%, relative to the total amount of polyol (A). %, particularly preferably 15% to 45% by weight, most preferably 20% to 40% by weight.

The number average molecular weight Mn of the fatty acid ester is preferably 200 to 400, more preferably 210 to 395, still more preferably 230 to 380, particularly preferably 240 to 360, most preferably 250 to 350. is. 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, the wetting speed may not improve even if the number of parts added is large. If the number average molecular weight Mn of the fatty acid ester is too large, the curability of the pressure-sensitive adhesive during drying may deteriorate, which may adversely affect not only wettability but also other pressure-sensitive adhesive properties.

As the fatty acid ester, any suitable fatty acid ester can be adopted as long as it 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, monoglyceride behenate, cetyl 2-ethylhexanoate, and myristic acid. Isopropyl, isopropyl palmitate, cholesteryl isostearate, lauryl methacrylate, methyl cocoate, methyl laurate, methyl oleate, methyl stearate, myristyl myristate, octyldodecyl myristate, pentaerythritol monooleate, pentaerythritol monostearate , pentaerythritol tetrapalmitate, stearyl stearate, isotridecyl stearate, 2-ethylhexanoic acid triglyceride, butyl laurate, and octyl oleate.

(catalyst)
Other components may include catalysts. Examples of catalysts include organometallic compounds and tertiary amine compounds. Only one kind of catalyst may be used, or two or more kinds thereof may be used.

Examples of organometallic compounds include iron-based compounds, tin-based compounds, titanium-based compounds, zirconium-based compounds, lead-based compounds, cobalt-based compounds, and zinc-based compounds. Among these, iron-based compounds and tin-based compounds are preferable in terms of reaction speed and pot life of the pressure-sensitive adhesive layer.

Examples of iron-based compounds include iron acetylacetonate and iron 2-ethylhexanoate.

Examples of tin compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin maleate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin sulfide, tributyltin methoxide, tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, dioctyltin dilaurate, tributyltin chloride, tributyltin trichloroacetate, and tin 2-ethylhexanoate.

Titanium-based compounds include, for example, dibutyl titanium dichloride, tetrabutyl titanate, and butoxy titanium trichloride.

Zirconium-based compounds include, for example, zirconium naphthenate and zirconium acetylacetonate.

Examples of lead-based compounds include lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate.

Cobalt-based compounds include, for example, cobalt 2-ethylhexanoate and cobalt benzoate.

Examples of zinc-based compounds include zinc naphthenate and zinc 2-ethylhexanoate.

Examples of tertiary amine compounds include triethylamine, triethylenediamine, and 1,8-diazabisic-(5,4,0)-undecene-7.

The amount of the catalyst is preferably 0.02% to 0.50% by weight, more preferably 0.05% to 0.40% by weight, more preferably 0% by weight, relative to the polyol (A). 0.07 wt % to 0.30 wt %, particularly preferably 0.10 wt % to 0.20 wt %.

(Crosslinking retarder)
Crosslinking retarders typically include compounds that undergo keto-enol tautomerism. When a compound that produces keto-enol tautomerism is employed as a cross-linking retarder, for example, excessive viscosity increase and gelation of the urethane-based pressure-sensitive adhesive composition can be suppressed, and the pot life of the urethane-based pressure-sensitive adhesive composition can be shortened. can be expressed. This technique can be preferably applied when the urethane pressure-sensitive adhesive composition is in the form of an organic solvent solution or solvent-free.

As compounds that cause keto-enol tautomerism, for example, various β-dicarbonyl compounds can be used. Specific examples include acetylacetone, 2,4-hexanedione, 3,5-heptanedione, 2-methylhexane-3,5-dione, 6-methylheptane-2,4-dione, 2,6-dimethyl β-diketones such as heptane-3,5-dione; acetoacetates such as methyl acetoacetate, ethyl acetoacetate, isopropyl acetoacetate and tert-butyl acetoacetate; ethyl propionyl acetate, ethyl propionyl acetate, isopropyl propionyl acetate, propionyl acetate esters such as tert-butyl propionyl acetate; isobutyryl acetate esters such as ethyl isobutyryl acetate, ethyl isobutyryl acetate, isopropyl isobutyryl acetate, tert-butyl isobutyryl acetate; malonic esters such as methyl malonate and ethyl malonate; etc. Among these, at least one selected from acetylacetone and acetoacetate is preferred.

Only one kind of compound that causes keto-enol tautomerism may be used, or two or more kinds thereof may be used.

The content of the compound that causes keto-enol tautomerism is preferably from 0.1 part by weight to 100 parts by weight of the base polymer (eg, acrylic polymer, polyol, urethane prepolymer, silicone polymer). 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 causes keto-enol tautomerism is too low, it may become difficult to exhibit sufficient effects. If the compound that causes keto-enol tautomerism is used more than necessary, it may remain in the pressure-sensitive adhesive layer and reduce the cohesive strength.

(Surfactant)
The urethane-based pressure-sensitive adhesive composition, which is the material for the pressure-sensitive adhesive layer, may contain a surfactant from the viewpoint of improving removability and wettability of the pressure-sensitive adhesive composition to the adherend.

Surfactants include known anionic surfactants, known nonionic surfactants, known cationic surfactants, known amphoteric surfactants, and the like.

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, more preferably 100 parts by weight, based on 100 parts by weight of the base polymer (eg, acrylic polymer, polyol, urethane prepolymer, silicone polymer). is 0.1 to 1 part by weight.

<1-2-2. Urethane adhesive manufactured by prepolymer method>
One embodiment of the polyurethane-based pressure-sensitive adhesive is a polyurethane-based pressure-sensitive adhesive obtained by curing a urethane-based pressure-sensitive adhesive composition containing a urethane prepolymer (A2) and a polyfunctional isocyanate compound (B). That is, the urethane-based pressure-sensitive adhesive composition in this form contains the urethane prepolymer (A2) and the polyfunctional isocyanate compound (B).

The content ratio of the total amount of the urethane prepolymer (A2) and the polyfunctional isocyanate compound (B) in the urethane-based pressure-sensitive adhesive composition in this form, excluding the solvent, is preferably 50% to 100% by weight, More preferably 55% to 95% by weight, still more preferably 60% to 90% by weight, particularly preferably 65% to 85% by weight, most preferably 70% to 80% by weight. be.

[1-2-2-a. Urethane prepolymer (A2)]
The urethane prepolymer (A2) may be of only one type, or may be of two or more types.

The number average molecular weight Mn of the urethane prepolymer (A2) is preferably 3,000 to 1,000,000.

The urethane prepolymer (A2) is preferably a polyurethane polyol, more preferably polyester polyol (a21) or polyether polyol (a22), either alone or as a mixture of (a21) and (a22). , in the presence or absence of a catalyst, with an organic polyisocyanate compound (a23).

Any appropriate polyester polyol can be used as the polyester polyol (a21). Examples of such polyester polyols (a21) include polyester polyols obtained by reacting an acid component and a glycol component. Examples of acid components include terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid, and trimellitic acid. Examples of glycol components include ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, 1,6-hexane glycol, 3-methyl-1,5-pentanediol, 3,3′-dimethylolheptane, polyoxyethylene glycol, Examples include polyoxypropylene glycol, 1,4-butanediol, neopentyl glycol, butylethylpentanediol, and polyol components such as glycerin, trimethylolpropane, and pentaerythritol. Polyester polyols (a1) also include polyester polyols obtained by ring-opening polymerization of lactones such as polycaprolactone, poly(β-methyl-γ-valerolactone) and polyvalerolactone.

As the molecular weight of the polyester polyol (a21), a low molecular weight to a high molecular weight can be used. As for the molecular weight of the polyester polyol (a21), the number average molecular weight Mn is preferably 100 to 100,000. If the number average molecular weight Mn is less than 100, the reactivity becomes high and gelation may easily occur. If the number-average molecular weight Mn exceeds 100,000, the reactivity may be lowered and the cohesive strength of the polyurethane polyol itself may be lowered. The amount of the polyester polyol (a21) used is preferably 0 mol % to 90 mol % of the polyol constituting the polyurethane polyol.

Any appropriate polyether polyol can be used as the polyether polyol (a22). Examples of such polyether polyols (a22) include water, propylene glycol, ethylene glycol, glycerin, trimethylolpropane, and other low-molecular-weight polyols as initiators, and ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, and the like. Examples include polyether polyols obtained by polymerizing oxirane compounds. Specific examples of such polyether polyols (a22) include polyether polyols having two or more functional groups, such as polypropylene glycol, polyethylene glycol, and polytetramethylene glycol.

As the molecular weight of the polyether polyol (a22), it is possible to use from low molecular weight to high molecular weight. As for the molecular weight of the polyether polyol (a22), the number average molecular weight Mn is preferably 100 to 100,000. If the number average molecular weight Mn is less than 100, the reactivity becomes high and gelation may easily occur. If the number-average molecular weight Mn exceeds 100,000, the reactivity may be lowered and the cohesive strength of the polyurethane polyol itself may be lowered. The amount of the polyether polyol (a22) used is preferably 0 mol % to 90 mol % of the polyol constituting the polyurethane polyol.

Part of the polyether polyol (a22), if necessary, glycols such as ethylene glycol, 1,4-butanediol, neopentyl glycol, butylethylpentanediol, glycerin, trimethylolpropane, pentaerythritol, It can be used in combination with polyvalent amines such as ethylenediamine, N-aminoethylethanolamine, isophoronediamine, xylylenediamine, and the like.

As the polyether polyol (a22), only a bifunctional polyether polyol may be used, or a polyether having a number average molecular weight Mn of 100 to 100,000 and at least 3 or more hydroxyl groups in one molecule. Part or all of the ether polyol may be used. As the polyether polyol (a22), a polyether polyol having a number average molecular weight Mn of 100 to 100,000 and having at least 3 or more hydroxyl groups in one molecule is used partially or wholly. can be well balanced. In such a polyether polyol, if the number average molecular weight Mn is less than 100, the reactivity becomes high and there is a possibility that gelation is likely to occur. Moreover, in such a polyether polyol, if the number average molecular weight Mn exceeds 100,000, the reactivity may be lowered, and the cohesive strength of the polyurethane polyol itself may be lowered. The number average molecular weight Mn of such polyether polyols is more preferably 100-10,000.

Any appropriate organic polyisocyanate compound can be used as the organic polyisocyanate compound (a23). Examples of such organic polyisocyanate compounds (a23) include aromatic polyisocyanates, aliphatic polyisocyanates, araliphatic polyisocyanates, and alicyclic polyisocyanates.

Examples of aromatic polyisocyanates include 1,3-phenylene diisocyanate, 4,4'-diphenyldiisocyanate, 1,4-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6 - tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanatotoluene, 1,3,5-triisocyanatobenzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4', 4″-triphenylmethane triisocyanate may be mentioned.

Examples of aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate may be mentioned.

Examples of araliphatic polyisocyanates include ω,ω'-diisocyanate-1,3-dimethylbenzene, ω,ω'-diisocyanate-1,4-dimethylbenzene, ω,ω'-diisocyanate-1,4-diethylbenzene , 1,4-tetramethylxylylene diisocyanate, and 1,3-tetramethylxylylene diisocyanate.

Examples of alicyclic polyisocyanates include 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2 ,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebis(cyclohexyl isocyanate), 1,4-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane. .

As the organic polyisocyanate compound (a23), a trimethylolpropane adduct, a water-reacted biuret compound, a trimer having an isocyanurate ring, and the like can be used in combination.

Any appropriate catalyst can be used as the catalyst that can be used when obtaining the polyurethane polyol. Examples of such catalysts include tertiary amine compounds and organometallic compounds.

Examples of tertiary amine compounds include triethylamine, triethylenediamine, and 1,8-diazabicyclo(5,4,0)-undecene-7 (DBU).

Examples of organometallic compounds include tin-based compounds and non-tin-based compounds.

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

Examples of non-tin compounds include titanium compounds such as dibutyl titanium dichloride, tetrabutyl titanate, and butoxy titanium trichloride; lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate. iron-based compounds such as iron 2-ethylhexanoate and iron acetylacetonate; cobalt-based compounds such as cobalt benzoate and cobalt 2-ethylhexanoate; zinc-based compounds such as zinc naphthenate and zinc 2-ethylhexanoate; zirconium-based compounds such as zirconium naphthenate;

When a catalyst is used to obtain a polyurethane polyol, in a system in which two types of polyols, a polyester polyol (a21) and a polyether polyol (a22), are present, due to the difference in reactivity, in a single catalyst system, Problems such as gelation and turbidity of the reaction solution tend to occur. Therefore, by using two kinds of catalysts when obtaining a polyurethane polyol, the reaction rate, the selectivity of the catalyst, etc. can be easily controlled, and these problems can be solved. Combinations of such two types of catalysts include, for example, tertiary amine/organometallic, tin/non-tin, and tin/tin, preferably tin/tin, and more preferably. is a combination of dibutyltin dilaurate and tin 2-ethylhexanoate. The weight ratio of tin 2-ethylhexanoate/dibutyltin dilaurate is preferably less than 1, more preferably 0.2 to 0.6. If the compounding ratio is 1 or more, gelation may tend to occur due to the balance of catalytic activity.

When a catalyst is used in obtaining the polyurethane polyol, the amount of the catalyst used is preferably 0.01 with respect to the total amount of the polyester polyol (a21), the polyether polyol (a22) and the organic polyisocyanate compound (a23). % to 1.0% by weight.

If a catalyst is used in obtaining the polyurethane polyol, the reaction temperature is preferably below 100°C, more preferably between 85°C and 95°C. If the temperature is 100° C. or higher, it may become difficult to control the reaction rate and the crosslinked structure, and it may become difficult to obtain a polyurethane polyol having a predetermined molecular weight.

When obtaining a polyurethane polyol, it is not necessary to use a catalyst. In that case, the reaction temperature is preferably 100° C. or higher, more preferably 110° C. or higher. Moreover, when obtaining a polyurethane polyol under no catalyst, it is preferable to carry out reaction for 3 hours or more.

Methods for obtaining polyurethane polyol include, for example, 1) a method of charging a polyester polyol, a polyether polyol, a catalyst, and an organic polyisocyanate into a volumetric flask, and 2) a method of charging a polyester polyol, a polyether polyol, and a catalyst into a flask to produce an organic polyisocyanate. can be added dropwise. As a method for obtaining a polyurethane polyol, the method 2) is preferable from the viewpoint of controlling the reaction.

Any suitable solvent may be used in obtaining the polyurethane polyol. Examples of such solvents include methyl ethyl ketone, ethyl acetate, toluene, xylene and acetone. Among these solvents, toluene is preferred.

[1-2-1-b. Polyfunctional isocyanate compound (B) used in prepolymer method]
The number of polyfunctional isocyanate compounds (B) used in the prepolymer method may be one, or two or more.

As the polyfunctional isocyanate compound (B) used in the prepolymer method, the aforementioned polyfunctional isocyanate compound (B) used in the one-shot method can be used.

The equivalent ratio of NCO groups to OH groups in the urethane prepolymer (A2) and the polyfunctional isocyanate compound (B) is preferably 5.0 or less, more preferably 0.01 to 4, as NCO groups/OH groups. .75, more preferably 0.02 to 4.5, particularly preferably 0.03 to 4.25, most preferably 0.05 to 4.0. If the equivalent ratio of NCO group/OH group is within the above range, the effects of the present invention can be exhibited more effectively.

The content of the polyfunctional isocyanate compound (B) is preferably 0.01% by weight to 30% by weight, more preferably 0.01% by weight to 30% by weight, based on the urethane prepolymer (A2). 05 wt % to 25 wt %, more preferably 0.1 wt % to 20 wt %, particularly preferably 0.5 wt % to 17.5 wt %, most preferably 1 wt % to 15 wt %. % by weight. If the content of the polyfunctional isocyanate compound (B) is within the above range, the effects of the present invention can be exhibited more effectively.

As a method for forming a urethane-based pressure-sensitive adhesive from a urethane-based pressure-sensitive adhesive composition containing a urethane prepolymer (A2) and a polyfunctional isocyanate compound (B), a so-called "urethane prepolymer" is used as a raw material to produce a polyurethane-based resin. Any appropriate manufacturing method can be adopted as long as it is a manufacturing method.

<<1-3. Antistatic layer≫
The pressure-sensitive adhesive layer-attached film according to the embodiment of the present invention may have an antistatic layer between the substrate layer and the pressure-sensitive adhesive layer.

Any appropriate thickness can be adopted as the thickness of the antistatic layer as long as the effects of the present invention are not impaired. Such a thickness is preferably 1 nm to 1000 nm, more preferably 5 nm to 900 nm, even more preferably 7.5 nm to 800 nm, and particularly preferably 10 nm to 700 nm.

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

As the antistatic layer, any appropriate antistatic layer can be employed as long as it is a layer capable of exhibiting an antistatic effect, as long as it does not impair the effects of the present invention. Such an antistatic layer is preferably an antistatic layer formed by coating a conductive coating liquid containing a conductive polymer on any suitable base material layer. Specifically, for example, it is an antistatic layer formed by coating a substrate (for example, a substrate layer) with a conductive coating liquid containing a conductive polymer. Specific coating methods include roll coat method, gravure coat method, reverse coat method, roll brush method, spray coat method, and air knife coat method. , an extrusion coating method using a die coater or the like.

As the conductive coating liquid containing the conductive polymer, any appropriate conductive coating liquid can be adopted as long as the effects of the present invention are not impaired. Such a conductive coating liquid preferably contains a conductive polymer, a binder, a cross-linking agent and a solvent. Since this solvent is substantially lost by volatilization or evaporation due to heating or the like during the process of forming the antistatic layer, the antistatic layer preferably contains a conductive polymer, a binder and a cross-linking agent.

As the conductive polymer, any appropriate conductive polymer can be adopted as long as the effects of the present invention are not impaired. Examples of such a conductive polymer include a conductive polymer obtained by doping a π-conjugated conductive polymer with a polyanion. Examples of π-conjugated conductive polymers include linear conductive polymers such as polythiophene, polypyrrole, polyaniline and polyacetylene. Polyanions include polystyrene sulfonic acid, polyisoprene sulfonic acid, polyvinyl sulfonic acid, polyallylsulfonic acid, polyethyl acrylate sulfonic acid, polymethacrylic carboxylic acid, and the like. Only one type of conductive polymer may be used, or two or more types may be used.

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

Examples of solvents include organic solvents, water, and mixed solvents thereof. Examples of organic solvents include esters such as ethyl acetate; ketones such as methyl ethyl ketone, acetone and cyclohexanone; cyclic ethers such as tetrahydrofuran (THF) and dioxane; aromatic hydrocarbons such as toluene and xylene; aliphatic or alicyclic alcohols such as methanol, ethanol, n-propanol, isopropanol and cyclohexanol ; glycol ethers such as alkylene glycol monoalkyl ether (eg, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether), dialkylene glycol monoalkyl ether; 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 of the binder in the antistatic layer is preferably 50% to 95% by weight, more preferably 60% to 90% by weight.

As the binder that can be contained in the conductive coating liquid, any suitable binder can be adopted as long as the effects of the present invention are not impaired. Only one binder may be used, or two or more binders may be used. Such a binder is preferably a resin, more preferably a polyester resin. The proportion of the polyester resin in the binder is preferably 90 wt % to 100 wt %, more preferably 98 wt % to 100 wt %.

The polyester resin is mainly composed of polyester (preferably more than 50% by weight, more preferably 75% by weight or more, still more preferably 90% by weight or more, and particularly preferably substantially 100% by weight). It is preferable to include as

As the polyester, any appropriate polyester can be adopted as long as the effects of the present invention are not impaired. Such polyesters preferably include polycarboxylic acids having two or more carboxyl groups in one molecule (e.g., dicarboxylic acid compounds) and derivatives thereof (e.g., polycarboxylic anhydrides, esters, halides, etc.) selected from one or more compounds (polycarboxylic acid components) and polyhydric alcohols having two or more hydroxyl groups in one molecule (e.g., diols) It preferably has a condensed structure with one or more compounds (polyhydric alcohol components).

Any appropriate polyvalent carboxylic acid may be employed as the polyvalent carboxylic acid component as long as the effects of the present invention are not impaired. Examples of such polyvalent carboxylic acid components include oxalic acid, malonic acid, difluoromalonic acid, alkylmalonic acid, succinic acid, tetrafluorosuccinic acid, alkylsuccinic acid, (±)-malic acid, meso-tartaric acid, itaconic acid, maleic acid, methylmaleic acid, fumaric acid, methylfumaric acid, acetylenedicarboxylic acid, glutaric acid, hexafluoroglutaric acid, methylglutaric acid, glutaconic 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, perfluorosebacine acids, brassylic acid, dodecyldicarboxylic acid, tridecyldicarboxylic acid, tetradecyldicarboxylic acid and other aliphatic dicarboxylic acids; cycloalkyldicarboxylic acids (eg, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid), 1 alicyclic dicarboxylic acids such as ,4-(2-norbornene)dicarboxylic acid, 5-norbornene-2,3-dicarboxylic acid (himic acid), adamantanedicarboxylic acid, spiroheptanedicarboxylic acid; phthalic acid, isophthalic acid, dithioisophthalic acid acid, methylisophthalic acid, dimethylisophthalic acid, chloroisophthalic acid, dichloroisophthalic acid, terephthalic acid, methylterephthalic acid, dimethylterephthalic acid, chloroterephthalic acid, bromoterephthalic acid, naphthalenedicarboxylic acid, oxofluorenedicarboxylic acid, anthracenedicarboxylic acid, biphenyldicarboxylic acid, biphenylenedicarboxylic acid, dimethylbiphenylenedicarboxylic acid, 4,4″-p-terephenylenedicarboxylic acid, 4,4″-p-qualylphenyldicarboxylic acid, bibenzyldicarboxylic acid, azobenzenedicarboxylic acid, homophthalic acid, phenylenediacetic acid, phenylenedipropionic acid, naphthalenedicarboxylic acid, naphthalenedipropionic acid, biphenyldiacetic acid, biphenyldipropionic acid, 3,3′-[4,4′-(methylenedi-p-biphenylene)dipropionic acid, 4 ,4'-bibenzyldiacetic acid, 3,3'(4,4'-bibenzyl)dipropionic acid, oxydi-p-phenylenediacetic acid and other aromatic dicarboxylic acids; acid anhydrides of any of the above polyvalent carboxylic acids esters of any of the above polycarboxylic acids (e.g., lucyl ester. monoesters, diesters, etc.); acid halides corresponding to any of the above polyvalent carboxylic acids (eg, dicarboxylic acid chlorides); and the like.

Polyvalent carboxylic acid components preferably include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid and their acid anhydrides; adipic acid, sebacic acid, azelaic acid, succinic acid, fumaric acid, maleic acid, Himic acids, aliphatic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid and their acid anhydrides; lower alkyl esters of these dicarboxylic acids (for example, esters with monoalcohols having 1 to 3 carbon atoms); mentioned.

As the polyhydric alcohol component, any suitable polyhydric alcohol can be used as long as the effects of the present invention are not impaired. Examples of such polyhydric alcohol components include ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 3-methylpentanediol, diethylene glycol, 1,4-cyclohexanedimethanol 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl- 1,3-propanediol, xylylene glycol, hydrogenated bisphenol A, diols such as bisphenol A; alkylene oxide adducts of these diols (e.g., ethylene oxide addition products, propylene oxide adducts, etc.);

The molecular weight of the polyester resin is preferably 5×10 ³ to 1.5×10 ⁵ and more preferably 5×10 3 to 1.5×10 5 as a weight average molecular weight (Mw) in terms of standard polystyrene measured by gel permeation chromatography (GPC). is between 1×10 ⁴ and 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, a commercially available product such as "Vylonal" manufactured by Toyobo Co., Ltd. can be used.

In the conductive coating liquid, resins other than polyester resins (for example, acrylic resins, acrylic retane resins, acrylic styrene resins, acrylic silicone resins, silicone resins, at least one resin selected from polysilazane resins, polyurethane resins, fluororesins, and polyolefin resins).

As the cross-linking agent that can be contained in the conductive coating solution, any suitable cross-linking agent can be employed as long as the effects of the present invention are not impaired. The number of cross-linking agents may be one, or two or more. Such cross-linking agents preferably include isocyanate-based cross-linking agents, epoxy-based cross-linking agents, melamine-based cross-linking agents, peroxide-based cross-linking agents, urea-based cross-linking agents, metal alkoxide-based cross-linking agents, and metal oxide cross-linking agents. Examples include a triglyceride-based cross-linking agent, a metal salt-based cross-linking agent, a carbodiimide-based cross-linking agent, an oxazoline-based cross-linking agent, an aziridine-based cross-linking agent, and an amine-based cross-linking agent. Among them, a melamine-based cross-linking agent is preferred.

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

Any appropriate other component may be contained in the antistatic layer as long as the effects of the present invention are not impaired.

<<1-4. Conductive layer≫
The pressure-sensitive adhesive layer-attached film according to the embodiment of the present invention may have a conductive layer between the substrate layer and the pressure-sensitive adhesive layer.

The number of conductive layers may be one, or two or more.

The conductive layer can be provided by forming it on any suitable substrate (eg, substrate layer).

The conductive layer may be formed by any suitable thin film forming method such as, for example, vacuum deposition, sputtering, ion plating, spray pyrolysis, chemical plating, electroplating, or combinations thereof. A conductive film is formed on a suitable substrate (eg, substrate layer). Among these thin film forming methods, the vacuum vapor deposition method and the sputtering method are preferable from the viewpoints of the forming speed of the conductive film, the formability of the large-area film, the productivity, and the like.

Materials for forming the conductive film include, for example, gold, silver, platinum, palladium, copper, aluminum, nickel, chromium, titanium, iron, cobalt, tin, metal-based materials such as alloys thereof; indium oxide; Metal oxide materials such as tin oxide, titanium oxide, cadmium oxide, and mixtures thereof; other metal compounds such as copper iodide; and the like are used.

As the thickness of the conductive layer, any appropriate thickness can be adopted according to the purpose as long as the effects of the present invention are not impaired. Such a thickness is, for example, preferably 30 Å to 600 Å when formed from a metal-based material, and preferably 80 Å to 5000 Å when formed from a metal oxide-based material.

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

When forming a conductive film on any suitable base material (e.g., base material layer), the surface of the base material (e.g., base material layer) may be subjected to corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, sputtering. Any appropriate pretreatment such as etching treatment, undercoating treatment, or the like can be applied to enhance adhesion between the conductive film and the substrate (eg, substrate layer).

<<<2. Method for producing a film with an adhesive layer>>>>
The pressure-sensitive adhesive layer-attached film according to the embodiment of the present invention can be produced by any appropriate method as long as the effects of the present invention are not impaired.

As a representative example of the method for producing a pressure-sensitive adhesive layer-attached film, as shown in FIG. A case will be described.

When the pressure-sensitive adhesive layer-attached film is a film in which a substrate layer and a pressure-sensitive adhesive layer are directly laminated, representative production methods include the following methods (1) and (2). .
(1) Prepare an adhesive composition for forming an adhesive layer.
(2) A pressure-sensitive adhesive composition is applied to the surface of the substrate layer, heated and dried as necessary, and cured as necessary to form a pressure-sensitive adhesive layer on the substrate layer.

EXAMPLES The present invention will be specifically described below with reference to Examples, but the present invention is not limited to these Examples. The tests and evaluation methods used in Examples and the like are as follows. "Parts" means "parts by weight" unless otherwise specified, and "%" means "% by weight" unless otherwise specified.

<Measurement of thickness>
The thickness of the pressure-sensitive adhesive layer in Examples and Comparative Examples was measured using an interference film thickness meter (manufactured by Otsuka Electronics Co., Ltd., product name "MCPD-3700").

<Measurement of Tg>
The glass transition temperature (Tg) (°C) was determined by the following formula using the following literature value as Tgn (°C), which is the glass transition temperature of the homopolymer of each monomer.
Formula: 1/(Tg+273)=Σ[Wn/(Tgn+273)]
(In the formula, Tg (°C) is the glass transition temperature of the copolymer, Wn is the weight fraction of each monomer, Tgn (°C) is the glass transition temperature of the homopolymer of each monomer, and n is the type of each monomer. )
Glass transition temperature of homopolymer of 2-ethylhexyl acrylate (2EHA): -70°C
Glass transition temperature of homopolymer of hydroxyethyl acrylate (HEA): -15°C
Glass transition temperature of homopolymer of 4-hydroxybutyl acrylate (HBA): -32°C
Glass transition temperature of homopolymer of acrylic acid (AA): 106°C
Reference was made to "Synthesis, Design and Development of New Applications of Acrylic Resins" (published by Central Management Development Center Publishing Department) as literature values.

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

<Measurement of low-speed peel force measured at a peel speed of 0.3 m/min and a peel angle of 180 degrees>
For the produced adhesive layer-attached film, the adhesive layer was pressed against the base material layer with a hand roller, and then laminated under the pressing conditions of 0.25 MPa and 0.3 m / min, 23 ° C., humidity 50% RH. It was left in the environment for 20 minutes. After that, the film was cut into a width of 25 mm, and the side of the pressure-sensitive adhesive layer opposite to the base layer was adhered and fixed to a SUS plate (SUS304BA). Using a universal tensile tester (manufactured by Minebea Co., Ltd., product name: TCM-1kNB), the adhesive layer was peeled from the base layer at a peel speed of 0.3 m / min and a peel angle of 180 degrees. The peel force at which the sample was applied was taken as the low-speed peel force.

<Measurement of high-speed peel force measured at a peel speed of 10 m/min and a peel angle of 180 degrees>
For the produced film with an adhesive layer, the adhesive layer was pressure-bonded to the base material layer with a hand roller, and then laminated under pressure conditions of 0.25 MPa and 0.3 m / min, 23 ° C., relative humidity 50% RH. was left for 20 minutes under the environment of After that, the film was cut into a width of 25 mm, and the side of the pressure-sensitive adhesive layer opposite to the base layer was adhered and fixed to a SUS plate (SUS304BA). Using a universal tensile tester (manufactured by Minebea Co., Ltd., product name: TCM-1kNB), the adhesive layer is peeled from the base layer at a peel speed of 10 m / min and a peel angle of 180 degrees. The force was taken as the high speed peel force.

<Contaminant removal rate>
For the produced film with an adhesive layer, under a temperature of 23 ° C. and a humidity of 50% RH, under a non-clean environment (specifically, ISO 146441-1: 2015 Classification and management criteria are established. The pressure-sensitive adhesive layer and the optical film (specifically, the “transparent protective film 1A” described in the examples of JP-A-2017-26939) are placed in a space different from a clean room such as a 10 cm ² × 10 cm ² The size of the foreign matter was marked, and the size of the foreign matter was confirmed with an optical microscope. Foreign matter of 100 μm or more was counted, and foreign matter remaining on the optical film after peeling off the pressure-sensitive adhesive layer-attached film was counted to confirm the foreign matter removal rate.

<Print Adhesion>
Under the measurement environment of 23 ° C. × 50% RH, using Shachihata's X stamper, after printing on the back of the adhesive layer-attached film (that is, the base layer), Nichiban Co., Ltd. A cellotape (registered trademark) manufactured by the manufacturer was affixed, and then peeled off under the conditions of a peeling speed of 30 m/min and a peeling angle of 180 degrees. After that, the surface of the substrate layer after peeling was visually observed, and when 50% or more of the printed area was peeled off, x (poor printability), and when 50% or more of the printed area remained without being peeled off, ○ ( good printability).

<Adhesive scum evaluation>
The surface of the pressure-sensitive adhesive layer was rubbed with the tip of a pen, and whether or not the pressure-sensitive adhesive layer was destroyed was visually judged.
Visual observation was performed under a fluorescent lamp. It was assumed that if the adhesive layer was not destroyed, no adhesive scum was generated, and if the adhesive layer was ruptured, adhesive scum was generated. Evaluation was performed according to the following criteria.
◯: No adhesive scum was observed.
x: Adhesive scum was observed.

[Production Example 1]
As the polyol (A1), Preminol S3011 (manufactured by Asahi Glass Co., Ltd., Mn = 10000), which is a polyol having three OH groups: 85 parts by weight, Sannics GP-3000 (Sanyo Kasei Co., Ltd.), which is a polyol having three OH groups Sannics GP-1000 (manufactured by Sanyo Chemical Co., Ltd., Mn = 3000): 13 parts by weight, a polyol having three OH groups (Mn = 1000): Using 2 parts by weight, a polyfunctional isocyanate compound (B ) is a polyfunctional alicyclic isocyanate compound Coronate HX (Nippon Polyurethane Industry Co., Ltd.): 18 parts by weight, catalyst (manufactured by Nippon Kagaku Sangyo Co., Ltd., trade name: Nasem ferric): 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: Excepar IPP, Mn = 299): 30 parts by weight, ethyl acetate as a dilution solvent: 241 parts by weight was blended and stirred with a disper to obtain a urethane-based adhesive composition (1).

[Production Example 2]
2-ethylhexyl acrylate (2EHA): 100 parts by weight, 4-hydroxybutyl acrylate (4HBA): 10 parts by weight, acrylic acid (AA ): 0.02 parts by weight, 2,2'-azobisisobutyronitrile (AIBN) (manufactured by Wako Pure Chemical Industries) as a polymerization initiator: 0.2 parts by weight, ethyl acetate: 157 parts by weight, slowly Nitrogen gas was introduced while stirring, and the liquid temperature in the flask was maintained at about 65° C., and the polymerization reaction was carried out for about 6 hours to prepare a solution of acrylic polymer (1) (solid content concentration=40% by weight). The obtained acrylic polymer (1) had a weight average molecular weight (Mw) of 540,000 and a Tg of -67°C. The obtained acrylic polymer (1) solution (solid content concentration = 40% by weight) was diluted with ethyl acetate to 5% by weight, and acrylic polymer (1) in this solution: 100 parts by weight (solid content) On the other hand, an isocyanurate form of hexamethylene diisocyanate (Coronate HX, manufactured by Nippon Polyurethane Industry Co., Ltd.): 6 parts by weight, dioctyltin dilaurate as a tin-based catalyst (Envilizer OL-1, manufactured by Tokyo Fine Chemicals): 0.03 parts by weight, Acetylacetone: 10 parts by weight was added as a cross-linking retarder, and mixed and stirred for about 1 minute while maintaining the temperature at around 25°C to prepare an acrylic pressure-sensitive adhesive composition (1).

[Production Example 3]: Preparation of release layer forming material (1) Resin obtained by drying butyral resin (manufactured by Sekisui Chemical Co., Ltd., S-lec KW-10): 100 parts by weight, xylene (manufactured by Taiyo Kagaku, Xylol ): 900 parts by weight, and then octadecyl isocyanate (manufactured by Ohara Palladium Chemical Co., Ltd., R-NCO): 480 parts by weight was added. Further, this solution was diluted with toluene (manufactured by Idemitsu Petrochemical Co., Ltd.) so that the solid content was 0.2% by weight, to prepare release layer forming material (1).

[Example 1]
The urethane-based pressure-sensitive adhesive composition (1) obtained in Production Example 1 was applied to a PET film (Diafoil T100C38, manufactured by Mitsubishi Chemical) having a thickness of 38 μm as a base layer, and dried at 130° C. for 30 seconds. A 1.0 μm-thick urethane-based adhesive layer was formed to produce a separator-less pressure-sensitive adhesive layer-attached film (1) having a structure of a substrate layer (thickness: 38 μm)/urethane-based adhesive layer (thickness: 1.0 μm). Table 1 shows the results.

[Example 2]
In the same manner as in Example 1 except that the thickness of the adhesive layer was 2.0 μm, a separatorless adhesive layer having a structure of a base layer (thickness of 38 μm) / urethane-based adhesive layer (thickness of 2.0 μm) was prepared. Attached film (2) was produced. Table 1 shows the results.

[Example 3]
In the same manner as in Example 1 except that the thickness of the adhesive layer was 3.0 μm, a separatorless adhesive layer having a structure of a base layer (thickness of 38 μm) / urethane-based adhesive layer (thickness of 3.0 μm) was prepared. Attached film (3) was produced. Table 1 shows the results.

[Example 4]
In the same manner as in Example 1 except that the thickness of the adhesive layer was 6.0 μm, a separatorless adhesive layer having a structure of a base layer (thickness of 38 μm) / urethane-based adhesive layer (thickness of 6.0 μm) was prepared. Attached film (4) was produced. Table 1 shows the results.

[Comparative Example 1]
The release layer-forming material (1) obtained in Production Example 3 is applied to a 38 μm-thick PET film (Diafoil T100C38, manufactured by Mitsubishi Chemical) as a base layer, dried at 130° C. for 60 seconds, and released. A laminate of the layer and the substrate layer was produced. The thickness of the release layer after drying was 20 nm. Furthermore, the acrylic pressure-sensitive adhesive composition (1) obtained in Production Example 2 was applied to the opposite side of the base layer of the laminate from the release layer, and heated at 130° C. for 60 seconds to give a thickness of 1.5. Forming an acrylic pressure-sensitive adhesive layer of 5 μm, a separator-less pressure-sensitive adhesive layer-attached film ( C1) was produced. Table 1 shows the results.

[Comparative Example 2]
The acrylic pressure-sensitive adhesive composition (1) obtained in Production Example 2 was applied to a 38 μm thick PET film (manufactured by Mitsubishi Chemical, Diafoil T100C38) as a base layer, dried at 130° C. for 60 seconds, and the thickness An acrylic pressure-sensitive adhesive layer having a thickness of 1.0 μm was formed to produce a separatorless pressure-sensitive adhesive layer-attached film (C2) having a structure of base layer (thickness: 38 μm)/acrylic pressure-sensitive adhesive layer (thickness: 1.0 μm). Table 1 shows the results.

[Comparative Example 3]
In the same manner as in Example 1 except that the thickness of the adhesive layer was 0.5 μm, a separatorless adhesive layer having a structure of a base layer (38 μm thick) / urethane adhesive layer (0.5 μm thick) was prepared. An attached film (C3) was produced. Table 1 shows the results.

[Comparative Example 4]
In the same manner as in Example 1 except that the thickness of the adhesive layer was 9.0 μm, a separatorless adhesive layer having a structure of a base layer (thickness 38 μm) / urethane adhesive layer (thickness 9.0 μm) was prepared. An attached film (C4) was produced. Table 1 shows the results.

The pressure-sensitive adhesive layer-attached film of the present invention can be suitably used for manufacturing processes of optical members and electronic members.

base material layer 10
Adhesive layer 20
Film with adhesive layer 100

Claims (6)

An adhesive layer-attached film having a substrate layer and an adhesive layer,
The pressure-sensitive adhesive layer does not have a separator on the side opposite to the base layer,
does not have a release layer on the side opposite to the pressure-sensitive adhesive layer of the base layer,
The base material layer contains a polyester-based resin,
The pressure-sensitive adhesive layer is a urethane-based pressure-sensitive adhesive layer composed of a urethane-based pressure-sensitive adhesive,
The pressure-sensitive adhesive layer has a thickness of 1.0 μm to 6.0 μm,
Film with adhesive layer. Low-speed peel force measured at a peel speed of 0.3 m/min and a peel angle of 180 degrees for the pressure-sensitive adhesive layer against the surface of the base layer opposite to the pressure-sensitive adhesive layer at a temperature of 23° C. and a humidity of 50% RH. is 0.01 N/25 mm or more, the pressure-sensitive adhesive layer-attached film according to claim 1. At a temperature of 23° C. and a humidity of 50% RH, the high-speed peel strength of the pressure-sensitive adhesive layer against the surface of the base layer opposite to the pressure-sensitive adhesive layer measured at a peel speed of 10 m/min and a peel angle of 180 degrees is The pressure-sensitive adhesive layer-attached film according to claim 1 or 2, which is 0.10 N/25 mm or less. Any one of claims 1 to 3, wherein the urethane-based pressure-sensitive adhesive is formed from a urethane-based pressure-sensitive adhesive composition, and the urethane-based pressure-sensitive adhesive composition contains a polyol (A1) and a polyfunctional isocyanate compound (B). The pressure-sensitive adhesive layer-attached film described above. 5. The pressure-sensitive adhesive layer-attached film according to claim 4, wherein the polyol (A1) contains a polyol having a number average molecular weight Mn of 400 to 20,000. 6. The pressure-sensitive adhesive layer-attached film according to claim 4, wherein the content of said polyfunctional isocyanate compound (B) relative to said polyol (A1) is 5% by weight to 60% by weight.

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