CN106256865B - Surface protective film - Google Patents

Abstract

The invention provides a surface protection film which can easily obtain a starting point of peeling from an adherend, can be easily peeled, and has high detection rate of damage and foreign matter mixing. And an optical component and an electronic component to which the surface protective film is attached. The surface protection film of the present invention is a surface protection film having a base material layer containing a polyester resin as a main component and a pressure-sensitive adhesive layer, wherein the base material layer is a colored base material layer containing a black pigment, the total light transmittance of the surface protection film is 5% or less, the initial peel force of the surface protection film at a peel speed of 0.3 m/min and a peel angle of 90 degrees with respect to glass is 1N/25mm or less, the peel force of the surface protection film at a peel speed of 0.3 m/min and a peel angle of 180 degrees with respect to glass is 0.1N/25mm or less, and the wetting speed of the surface protection film with respect to glass is 0.05cm²More than one second.

Description

Surface protective film

Technical Field

The present invention relates to a surface protective film. The present invention also relates to an optical component and an electronic component to which such a surface protective film is attached.

Background

In general, a surface protective film is attached to an exposed surface of an LCD, an organic EL, a touch panel using them, a lens portion of a camera, an optical component of an electronic device, and an electronic component in order to prevent surface damage during processing, assembly, inspection, transportation, and the like.

Such a surface protective film generally has a base material layer and an adhesive layer, and a separator is provided to protect the surface of the adhesive layer. Such a surface protection film is attached to an adherend such as an optical component or an electronic component after the separator is peeled off to expose the pressure-sensitive adhesive layer, and then peeled off from the adherend such as an optical component or an electronic component at a time when surface protection is no longer required (for example, patent documents 1 and 2). Therefore, it is required that a starting point of peeling from an adherend can be easily obtained and peeling can be easily performed.

In the manufacturing process of optical components and electronic components, in order to detect defective products, it is required to detect damage to the optical components and the electronic components and the mixing of foreign substances.

However, since optical components and electronic components to which conventional surface protective films are attached have high transparency as a whole, there is a problem that the detection rate of damage and contamination of foreign substances in the production process is low.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2005-306996

Patent document 2: japanese patent laid-open publication No. 2005-309071

Disclosure of Invention

Problems to be solved by the invention

The invention provides a surface protection film which can easily obtain a starting point of peeling from an adherend, can be easily peeled, and has high detection rate of damage and foreign matter mixing. The present invention also provides an optical component and an electronic component to which such a surface protective film is attached.

Means for solving the problems

The surface protection film of the present invention is a surface protection film having a base layer mainly composed of a polyester resin and a pressure-sensitive adhesive layer,

the substrate layer is a colored substrate layer containing a black pigment,

the total light transmittance of the surface protective film is 5% or less,

the surface protective film has an initial peel force at a peel speed of 0.3 m/min and a peel angle of 90 degrees of 1N/25mm or less with respect to glass,

the surface protective film has a peeling force at a peeling speed of 0.3 m/min and a peeling angle of 180 degrees of 0.1N/25mm or less with respect to glass,

the surface protective film had a wetting speed of 0.05cm with respect to glass²More than one second.

In1 embodiment, the pressure-sensitive adhesive layer contains at least 1 pressure-sensitive adhesive selected from the group consisting of polyurethane pressure-sensitive adhesives and acrylic pressure-sensitive adhesives.

The surface-protecting film of the present invention is bonded to the optical member of the present invention.

The surface protective film of the present invention is attached to an electronic component of the present invention.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, it is possible to provide a surface protection film which can easily obtain a starting point for peeling from an adherend, can be easily peeled, and has a high detection rate of damage and foreign matter contamination. Further, according to the present invention, an optical component and an electronic component to which such a surface protective film is attached can be provided.

Drawings

Fig. 1 is a schematic sectional view of a surface protection film according to a preferred embodiment of the present invention.

Description of the reference numerals

1 base material layer

2 adhesive layer

3 diaphragm

10 surface protective film

Detailed Description

Surface protective film

The surface protection film of the present invention has a base layer mainly composed of a polyester resin and a pressure-sensitive adhesive layer.

Fig. 1 is a schematic sectional view of a surface protection film according to 1 embodiment of the present invention. The surface protection film 10 includes a base material layer 1 and a pressure-sensitive adhesive layer 2 in this order. The surface protective film of the present invention may further have any suitable other layer as necessary. For example, as shown in fig. 1, the pressure-sensitive adhesive layer 2 has a separator 3 on the side opposite to the base material layer 1.

The separator may be formed of a single layer or a plurality of layers.

The thickness of the separator may be set to any suitable thickness according to the application. From the viewpoint of sufficiently exhibiting the effects of the present invention, it is preferably 20 μm to 100. mu.m, more preferably 25 μm to 90 μm, still more preferably 30 μm to 80 μm, and particularly preferably 35 μm to 70 μm.

As the material of the separator, any suitable material may be used within a range not impairing the effects of the present invention. Examples of such a material include plastic, paper, a metal film, and nonwoven fabric. Of these materials, plastics are preferred. The separator may be made of 1 kind of material, or may be made of 2 or more kinds of materials.

For example, a fatty acid amide, polyethyleneimine, or a long-chain alkyl additive may be added to the surface of the base material layer 1 on which the pressure-sensitive adhesive layer 2 is not provided, and a release treatment may be performed, or a coating layer formed of an optional suitable release agent such as silicone, long-chain alkyl, or fluorine may be provided, in order to form a roll-up body or the like that is easily unwound.

The thickness of the surface protection film of the present invention may be set to any suitable thickness depending on the application. From the viewpoint of sufficiently exhibiting the effects of the present invention, it is preferably 25 μm to 135 μm, more preferably 30 μm to 120 μm, still more preferably 35 μm to 100 μm, and particularly preferably 35 μm to 75 μm.

The surface protection film of the present invention has a total light transmittance of 5% or less, preferably 4.5% or less, more preferably 4% or less, further preferably 3.5% or less, and particularly preferably 3% or less. The lower limit value of the total light transmittance is preferably 0%. By adjusting the total light transmittance of the surface protection film of the present invention to be within the above range, a surface protection film having a high detection rate of damage or contamination of foreign substances can be provided. The details of the method for measuring the total light transmittance are described later.

The surface protection film of the present invention has an initial peel force at a peel speed of 0.3 m/min and a peel angle of 90 degrees of 1N/25mm or less, preferably 0.8N/25mm or less, more preferably 0.5N/25mm or less, still more preferably 0.3N/25mm or less, particularly preferably 0.1N/25mm or less, and most preferably 0.08N/25mm or less, with respect to glass. The lower limit of the initial peeling force is preferably 0.01N/25 mm. By adjusting the initial peel force of the surface protective film of the present invention at a peeling speed of 0.3 m/min and a peeling angle of 90 degrees with respect to glass to the above range, the starting point of peeling of the surface protective film of the present invention adhered to an adherend can be easily obtained. The details of the method for measuring the initial peel force are described later.

The surface protection film of the present invention has a peeling force at a peeling angle of 180 degrees of 0.1N/25mm or less, preferably 0.08N/25mm or less, more preferably 0.06N/25mm or less, further preferably 0.05N/25mm or less, particularly preferably 0.04N/25mm or less, and most preferably 0.03N/25mm or less, with respect to glass at a peeling speed of 0.3 m/min. The lower limit of the peeling force is preferably 0.005N/25 mm. By adjusting the peeling force of the surface protective film of the present invention at a peeling speed of 0.3 m/min and a peeling angle of 180 degrees with respect to glass to the above range, the surface protective film of the present invention adhered to an adherend can be peeled off easily. The details of the method for measuring the peeling force will be described later.

The wetting speed of the surface protective film of the present invention with respect to glass was 0.05cm²A second or more, preferably 0.08cm²At least one second, more preferably 0.1cm²At least one second, more preferably 1cm²At least one second, particularly preferably 5cm²More than one second, most preferably 10cm²More than one second. The upper limit value of the wetting speed is preferably 1000cm²Second, more preferably 100cm²Second, more preferably 50cm²Second, particularly preferably 20cm²In seconds. By adjusting the wetting rate of the surface protection film of the present invention with respect to glass to the above range, inclusion of air bubbles or foreign matter can be suppressed, and a surface protection film with a high detection rate of damage or foreign matter inclusion can be provided. The details of the method for measuring the wetting rate will be described later.

The surface protection film of the present invention is obtained by satisfying all of the following conditions as described above:

(a) the total light transmittance is less than 5 percent,

(b) the initial peel force at a peel speed of 0.3 m/min and a peel angle of 90 degrees with respect to the glass is 1N/25mm or less,

(c) a peeling force at a peeling speed of 0.3 m/min and a peeling angle of 180 degrees with respect to the glass of 0.1N/25mm or less,

(d) the wetting speed with respect to the glass was 0.05cm²More than one second of the reaction time,

the starting point of peeling from the adherend can be easily obtained, and peeling can be easily performed, and the detection rate of damage or foreign matter mixing is improved.

< substrate layer >

The base material layer contains a polyester resin as a main component. Specifically, the content ratio of the polyester resin in the base material layer is preferably 50 to 99.99% by weight, more preferably 70 to 99.95% by weight, even more preferably 90 to 99.9% by weight, particularly preferably 92 to 99.7% by weight, and most preferably 95 to 99.5% by weight. By adjusting the content ratio of the polyester resin in the base material layer to be within the above range, it is possible to provide a surface protective film which can easily obtain a starting point for peeling from an adherend and can be easily peeled, and which has a higher detection rate of scratches and foreign matter inclusion.

Examples of the polyester resin include: polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and the like. The number of the polyester resins in the base material layer may be only 1, or may be 2 or more.

The substrate layer may be formed of a single layer or a plurality of layers. The substrate layer may be unstretched or stretched.

The thickness of the base material layer may be set to any suitable thickness according to the application. From the viewpoint of sufficiently exhibiting the effects of the present invention, it is preferably 20 μm to 150 μm, more preferably 25 μm to 125 μm, still more preferably 30 μm to 100 μm, and particularly preferably 35 μm to 75 μm.

The base material layer is a colored base material layer containing a black pigment. By providing the base material layer as a colored base material layer containing a black pigment, a surface protective film having a high detection rate of scratches and contamination of foreign matter can be provided. Further, by adopting a means using a black pigment as a means for making the base layer a colored base layer, the problem of a decrease in coloring effect due to the falling-off of the colored layer or the like and the problem of contamination of the production line due to the falling-off of the colored layer or the like are reduced as compared with the case where the base layer is made a colored base layer by a means for providing a colored layer (for example, a printed layer). In addition, the substrate layer is a colored substrate layer containing a black pigment, and the black pigment is uniformly dispersed, whereby a uniformly colored substrate layer can be produced.

As the black pigment, any suitable black pigment may be used within a range not impairing the effects of the present invention. Examples of such black pigments include: carbon black, titanium black, black chromium oxide, black iron oxide, carbon nanotubes, aniline black, perylene pigments, c.i. solvent black 123, and the like. As the black pigment, carbon black is preferable.

The content ratio of the black pigment in the base material layer is preferably 0.01 to 30% by weight, more preferably 0.05 to 20% by weight, even more preferably 0.1 to 10% by weight, particularly preferably 0.3 to 5% by weight, and most preferably 0.5 to 1% by weight. By adjusting the content ratio of the black pigment in the base material layer to be within the above range, a surface protection film having a higher detection rate of damage or contamination of foreign matter can be provided. In addition, by adjusting the content ratio of the black pigment in the base material layer to be within the above range, a uniformly colored base material layer can be produced by uniform dispersion of the black pigment, and from this point of view, a surface protection film having a higher detection rate of damage or contamination of foreign substances can also be provided.

The black pigment may be added to the base material layer at any time before, during, or after the polymerization for producing the polyester resin. Examples of such a method include: a composite pellet method in which the black pigment is directly melted and dispersed in the polyester resin in an extruder and added.

The substrate layer may contain any suitable additive as needed. Examples of additives that can be contained in the base material layer include: antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, fillers, pigments, and the like. The kind, number, and amount of the additives that can be contained in the base material layer can be appropriately set according to the purpose.

As the antioxidant, any suitable antioxidant can be used. Examples of such antioxidants include: phenol antioxidants, phosphorus processing heat stabilizers, lactone processing heat stabilizers, sulfur heat stabilizers, phenol-phosphorus antioxidants, and the like. The content ratio of the antioxidant to the polyester resin in the base layer is preferably 1 wt% or less, more preferably 0.5 wt% or less, and further preferably 0.01 wt% to 0.2 wt%.

As the ultraviolet absorber, any suitable ultraviolet absorber can be used. Examples of such ultraviolet absorbers include: benzotriazole-based ultraviolet absorbers, triazine-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, and the like. The content ratio of the ultraviolet absorber to the polyester resin in the base material layer is preferably 2 wt% or less, more preferably 1 wt% or less, and further preferably 0.01 wt% to 0.5 wt%.

As the light stabilizer, any suitable light stabilizer can be used. Examples of such light stabilizers include: hindered amine light stabilizers, benzoate light stabilizers, and the like. The content ratio of the light stabilizer is preferably 2% by weight or less, more preferably 1% by weight or less, and still more preferably 0.01 to 0.5% by weight, based on the polyester resin in the base layer.

As the filler, any suitable filler can be used. Examples of such fillers include inorganic fillers other than black pigments. The content ratio of the filler to the polyester resin in the base layer is preferably 20% by weight or less, more preferably 10% by weight or less, and still more preferably 0.01% by weight to 10% by weight.

Further, as additives, for imparting antistatic properties, there can be mentioned: surfactants, inorganic salts, polyols, metal compounds, carbon and other inorganic antistatic agents, low molecular weight antistatic agents, high molecular weight antistatic agents.

The substrate layer may be produced by any suitable method within a range not impairing the effects of the present invention. In order to sufficiently exhibit the effects of the present invention, for example, in a film forming apparatus having an extruder, a mixture of chips of a dry polyester resin, main chips of a dry black pigment, and other additives as required is supplied to an extruder heated to 260 to 300 ℃, melted, introduced into a T-die opening, and subjected to extrusion molding. The molten sheet is electrostatically bonded and cooled and solidified on a drum cooled to a surface temperature of 10 to 60 ℃ to produce an unstretched film. The unstretched film thus obtained may be used as it is, or may be biaxially stretched mainly in the longitudinal direction and the width direction to be formed into a sheet having a desired optimum thickness. The stretching may be carried out in-line biaxial stretching or simultaneous biaxial stretching in both directions. Further, the redrawing may be further performed in the length and/or width direction. In an example of the sequential biaxial stretching, an unstretched film is guided to a roll set heated to 70 to 120 ℃, stretched 2 to 5 times in the longitudinal direction (longitudinal direction, i.e., the film traveling direction), and cooled by a roll set at 20 to 30 ℃. Then, the film stretched in the longitudinal direction is guided to a tenter while being sandwiched between both ends thereof, and stretched 2 to 5 times in the direction (width direction) perpendicular to the longitudinal direction in an atmosphere heated at 90 to 150 ℃. The area ratio of stretching (longitudinal stretching ratio multiplied by transverse stretching ratio) is preferably 6 to 20 times. If the area ratio is less than 6 times, the strength of the resulting film tends to be insufficient, whereas if it exceeds 20 times, the film tends to be easily broken during stretching. The biaxially stretched film thus obtained is subjected to a heat treatment step at 150 to 238 ℃ for 1 to 30 seconds in a tenter for the purpose of imparting flatness and dimensional stability by crystal orientation, and is uniformly and slowly cooled, and then cooled to room temperature, and after the winding step is completed, the film is cut into an appropriate size to obtain a base material layer. In the heat treatment step, the relaxation treatment may be performed by 3 to 12% in the width direction or the longitudinal direction, as necessary. In addition, in the case of simultaneously biaxially stretching an unstretched sheet prepared similarly to this method, the area magnification of stretching is also preferably 6 to 20 times. Further, after biaxial stretching, re-stretching may be performed in either or both of the longitudinal direction and the transverse direction. Further, the stretching temperature and the ratio are preferably appropriately selected according to the amounts of the black pigment and other additives added to the polyester resin.

< adhesive layer >

The adhesive layer preferably contains at least 1 adhesive selected from a polyurethane-based adhesive and an acrylic adhesive. The pressure-sensitive adhesive layer contains at least 1 pressure-sensitive adhesive selected from the group consisting of urethane pressure-sensitive adhesives and acrylic pressure-sensitive adhesives, and thus can be a pressure-sensitive adhesive layer having a low initial peel force, a low 180-degree peel force, and a high wetting speed.

The adhesive layer may be formed of a single layer or may be formed of a plurality of layers.

The thickness of the adhesive layer may be set to any suitable thickness according to the application. From the viewpoint of sufficiently exhibiting the effects of the present invention, it is preferably 5 μm to 50 μm, more preferably 6 μm to 40 μm, still more preferably 7 μm to 30 μm, and particularly preferably 8 μm to 20 μm.

The content ratio of the binder in the binder layer is preferably 96 to 100% by weight, more preferably 97 to 100% by weight, still more preferably 98 to 100% by weight, and particularly preferably 99 to 100% by weight. By adjusting the content ratio of the pressure-sensitive adhesive in the pressure-sensitive adhesive layer within the above range, a pressure-sensitive adhesive layer having a light initial peel force, a light 180-degree peel force, and a high wetting speed can be produced, and by combining with the specific base material layer employed in the present invention, a surface protective film which can easily obtain a starting point for peeling from an adherend, and can be easily peeled off, and further has a higher detection rate of scratches and foreign matter inclusion can be provided.

[ polyurethane-based adhesive ]

The polyurethane adhesive contains a polyurethane resin.

The content ratio of the polyurethane resin in the polyurethane adhesive is preferably 40% by weight or more, more preferably 50% by weight or more, further preferably 55% by weight or more, further preferably 60% by weight or more, particularly preferably 65% by weight or more, and most preferably 70% by weight or more, as a lower limit, and is preferably 99.999% by weight or less, more preferably 99.99% by weight or less, further preferably 99.9% by weight or less, further preferably 99% by weight or less, particularly preferably 95% by weight or less, and most preferably 90% by weight or less, as an upper limit. By adjusting the content ratio of the polyurethane resin in the polyurethane adhesive to the above range, a pressure-sensitive adhesive layer having a lighter initial peel force, a lighter 180-degree peel force, and a faster wetting speed can be obtained, and by combining with the specific base material layer used in the present invention, a surface protective film which can easily obtain a starting point for peeling from an adherend and has a higher detection rate of easy peeling, further damage, and inclusion of foreign substances can be provided.

The number of the polyurethane resin may be only 1, or may be 2 or more.

The polyurethane resin is obtained by curing a composition containing a polyol (a) and a polyfunctional isocyanate compound (B).

The polyol (a) may be only 1 type, or may be 2 or more types.

As the polyol (a), any suitable polyol can be used as long as it is a polyol having 2 or more OH groups. Examples of such a polyol (a) include: a polyol (diol) having 2 OH groups, a polyol (triol) having 3 OH groups, a polyol (tetraol) having 4 OH groups, a polyol (pentaol) having 5 OH groups, a polyol (hexaol) having 6 OH groups, and the like.

In the present invention, as the polyol (a), a polyol (triol) having 3 OH groups is preferably used as an essential component. When a polyol (triol) having 3 OH groups is used as the polyol (a) as described above as an essential component, for example, a pressure-sensitive adhesive layer having a light initial peel force, a light 180-degree peel force, and a high wetting rate can be obtained, and a surface protection film having a higher detection rate of scratches and foreign matter inclusion can be provided by combining the pressure-sensitive adhesive layer with the specific base material layer used in the present invention. The content ratio of the polyol (triol) having 3 OH groups in the polyol (a) is preferably 50 to 100% by weight, more preferably 70 to 100% by weight, even more preferably 80 to 100% by weight, even more preferably 90 to 100% by weight, particularly preferably 95 to 100% by weight, and most preferably substantially 100% by weight.

The polyol (A) preferably contains a polyol having a number average molecular weight Mn of 400 to 20000. The content ratio of the polyol having a number average molecular weight Mn of 400 to 20000 in the polyol (a) is preferably 50 to 100% by weight, more preferably 70 to 100% by weight, even more preferably 90 to 100% by weight, particularly preferably 95 to 100% by weight, and most preferably substantially 100% by weight. By adjusting the content ratio of the polyol having a number average molecular weight Mn of 400 to 20000 in the polyol (a) within the above range, a pressure-sensitive adhesive layer having a lighter initial peel force, a lighter 180-degree peel force and a faster wetting rate can be produced.

In the present invention, when a polyol (triol) having 3 OH groups is used as the essential component as the polyol (A), it is preferable to use a triol having a number average molecular weight Mn of 7000 to 20000, a triol having a number average molecular weight Mn of 2000 to 6000 and a triol having a number average molecular weight Mn of 400 to 1900 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 triol having a number average molecular weight Mn of 500 to 1800 in combination, still 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 in combination. When these 3 types of trihydric alcohols are used in combination, a pressure-sensitive adhesive layer having a lighter initial peel force, a lighter 180-degree peel force and a faster wetting rate can be obtained, and by combining with the specific base material layer used in the present invention, a surface protective film which can easily obtain a starting point for peeling from an adherend and can be easily peeled off and has a higher detection rate of scratches and foreign matter inclusion can be provided.

Examples of the polyol (a) include: polyester polyols, polyether polyols, polycaprolactone polyols, polycarbonate polyols, castor oil polyols, and the like.

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

Examples of the polyol component include: 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, glycerol, trimethylolpropane, pentaerythritol, Hexanetriol (Hexanetriol), polypropylene glycol, and the like.

Examples of the acid component 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' -biphenyldicarboxylic acid, anhydrides thereof, and the like.

Examples of polyether polyols include: and polyether polyols obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide using water, low-molecular-weight polyols (propylene glycol, ethylene glycol, glycerin, trimethylolpropane, pentaerythritol and the like), bisphenols (bisphenol a and the like), dihydroxybenzenes (catechol, resorcinol, hydroquinone and the like) and the like as initiators. Specifically, examples thereof include: polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like.

Examples of the polycaprolactone polyol include caprolactone polyesterdiol obtained by ring-opening polymerization of a cyclic ester monomer such as e-caprolactone or e-valerolactone.

Examples of the polycarbonate polyol include: a polycarbonate polyol obtained by subjecting the polyol component and phosgene to a polycondensation reaction; polycarbonate polyols obtained by subjecting the above polyol component to ester exchange condensation with a carbonic acid diester such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, ethylbutyl carbonate, ethylene carbonate, propylene carbonate, diphenyl carbonate, or dibenzyl carbonate; a copolymerized polycarbonate polyol obtained by using 2 or more of the above polyol components in combination; polycarbonate polyols obtained by subjecting the above-mentioned various polycarbonate polyols and a carboxyl-group-containing compound to an esterification reaction; polycarbonate polyols obtained by etherification of the above-mentioned various polycarbonate polyols with a hydroxyl group-containing compound; polycarbonate polyols obtained by subjecting the above-mentioned various polycarbonate polyols and an ester compound to an ester exchange reaction; polycarbonate polyols obtained by subjecting the above-mentioned various polycarbonate polyols and a hydroxyl group-containing compound to an ester exchange reaction; polyester polycarbonate polyols obtained by polycondensation of the above polycarbonate polyols with dicarboxylic acid compounds; a copolymerized polyether polycarbonate polyol obtained by copolymerizing the above-mentioned various polycarbonate polyols with an alkylene oxide; and so on.

Examples of the castor oil polyol include castor oil polyols obtained by reacting castor oil fatty acid with the above polyol component. Specifically, for example, castor oil-based polyols obtained by reacting castor oil fatty acids with polypropylene glycol can be cited.

The number of the polyfunctional isocyanate compounds (B) may be only 1, or may be 2 or more.

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

Examples of the polyfunctional aliphatic isocyanate compound include: trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1, 2-propylene diisocyanate, 1, 3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4, 4-trimethylhexamethylene diisocyanate, and the like.

Examples of the polyfunctional alicyclic isocyanate compound include: 1, 3-cyclopentene diisocyanate, 1, 3-cyclohexane diisocyanate, 1, 4-cyclohexane diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated tetramethylxylylene diisocyanate, and the like.

Examples of the polyfunctional aromatic diisocyanate compound include: phenylene diisocyanate, 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, 2 '-diphenylmethane diisocyanate, 4' -toluidine diisocyanate, 4 '-diphenyl ether diisocyanate, 4' -diphenyl diisocyanate, 1, 5-naphthalene diisocyanate, xylylene diisocyanate, and the like.

Examples of the polyfunctional isocyanate compound (B) include: trimethylolpropane adducts of various polyfunctional isocyanate compounds as described above, biuret products obtained by reaction with water, trimers having an isocyanurate ring, and the like. Further, they may be used in combination.

The content ratio of the polyfunctional isocyanate compound (B) is preferably 5 to 60% by weight, more preferably 8 to 60% by weight, and still more preferably 10 to 60% by weight, based on the polyol (a). By adjusting the content ratio of the polyfunctional isocyanate compound (B) within the above range, a pressure-sensitive adhesive layer having a lighter initial peel force, a lighter 180-degree peel force, and a faster wetting speed can be obtained, and by combining with the specific base material layer used in the present invention, a surface protective film which can easily obtain a starting point for peeling from an adherend and has a higher detection rate of easy peeling, further damage, and inclusion of foreign substances can be provided.

The equivalent ratio of NCO groups to OH groups in the polyol (A) and the polyfunctional isocyanate compound (B) is more than 1.0 and 5.0 or less, preferably 1.1 to 5.0, more preferably 1.2 to 4.0, further preferably 1.5 to 3.5, and particularly preferably 1.8 to 3.0 in terms of NCO groups/OH groups. By adjusting the equivalent ratio of NCO groups/OH groups within the above range, a pressure-sensitive adhesive layer having a lighter initial peel force, a lighter peel force at 180 degrees peel and a faster wetting rate can be produced, and by combining with a specific base material layer used in the present invention, a surface protective film which can easily obtain a starting point for peeling from an adherend and can be easily peeled off and has a higher detection rate of scratches and foreign matter inclusion can be provided.

The polyurethane resin is obtained by curing a composition containing a polyol (a) and a polyfunctional isocyanate compound (B). In such a composition, any suitable other component other than the polyol (a) and the polyfunctional isocyanate compound (B) may be contained within a range not impairing the effects of the present invention. Examples of such other components include: a catalyst, a resin component other than the polyurethane resin, an adhesion promoter, an inorganic filler, an organic filler, metal powder, a pigment, a foil, a softening agent, a plasticizer, an anti-aging agent, a conductive agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a surface lubricant, a leveling agent, an anticorrosive agent, a heat stabilizer, a polymerization inhibitor, a lubricant, a solvent, and the like.

The polyurethane resin preferably contains an antioxidant, an ultraviolet absorber, a light stabilizer, and other deterioration preventing agents. Since the urethane resin contains the deterioration inhibitor, adhesive residue and the like are not easily generated on the adherend even when the urethane resin is stored in a heated state after being attached to the adherend, and the adhesive residue prevention property can be improved. The deterioration prevention agent may be only 1 type, or 2 or more types. As the deterioration preventing agent, an antioxidant is particularly preferable.

The content ratio of the deterioration preventing agent is preferably 0.01 to 20% by weight, more preferably 0.02 to 15% by weight, even more preferably 0.03 to 10% by weight, even more preferably 0.05 to 7% by weight, even more preferably 0.1 to 5% by weight, particularly preferably 0.1 to 3% by weight, and most preferably 0.1 to 1% by weight, based on the polyol (a). By adjusting the content ratio of the deterioration preventing agent within the above range, adhesive residue and the like are not easily generated on the adherend even when stored in a heated state after being attached to the adherend, and the adhesive residue preventing property can be further improved. If the content ratio of the deterioration inhibitor is too small, the residual gum preventive property may not be sufficiently exhibited. If the content ratio of the deterioration preventing agent is too large, there is a concern that: there are problems that the cost becomes unfavorable, the adhesive property cannot be maintained, or the adherend is contaminated.

Examples of the antioxidant include: radical chain inhibitors, peroxide decomposers, and the like.

Examples of the radical chain inhibitor include: phenolic antioxidants, aminic antioxidants, and the like.

Examples of the peroxide decomposer include: sulfur-based antioxidants, phosphorus-based antioxidants, and the like.

Examples of the phenolic antioxidant include: monophenol antioxidants, bisphenol antioxidants, high-molecular phenol antioxidants, and the like.

Examples of the monophenol-based antioxidant include: 2, 6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2, 6-di-t-butyl-4-ethylphenol, stearic acid-beta- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, and the like.

Examples of the bisphenol-based antioxidant include: 2,2 '-methylenebis (4-methyl-6-tert-butylphenol), 2' -methylenebis (4-ethyl-6-tert-butylphenol), 4 '-thiobis (3-methyl-6-tert-butylphenol), 4' -butylidenebis (3-methyl-6-tert-butylphenol), 3, 9-bis [1, 1-dimethyl-2- [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ] ethyl ]2,4,8, 10-tetraoxaspiro [5,5] undecane and the like.

Examples of the polymeric phenol antioxidant 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) butanoic acid ] diol ester, 1,3, 5-tris (3 ', 5 ' -di-t-butyl-4 ' -hydroxybenzyl) s-triazine-2, 4,6- (1H,3H,5H) trione, tocopherol, and the like.

Examples of the sulfur-based antioxidant include: dilauryl 3,3 ' -thiodipropionate, dimyristyl 3,3 ' -thiodipropionate, distearyl 3,3 ' -thiodipropionate, and the like.

Examples of the phosphorus-based antioxidant include: triphenyl phosphite, diphenylisodecyl phosphite, phenyldiisodecyl phosphite, and the like.

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

Examples of the benzophenone-based ultraviolet absorber include: 2, 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2 ' -dihydroxy-4-dimethoxybenzophenone, 2 ' -dihydroxy-4, 4 ' -dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, bis (2-methoxy-4-hydroxy-5-benzoylphenyl) methane and the like.

Examples of the benzotriazole-based ultraviolet absorber include: 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' -octyloxyphenyl) benzotriazole, 2- [2 '-hydroxy-3' - (3 ", 4 ', 5 ', 6 ', -tetrahydrophthalimidomethyl) -5 ' -methylphenyl ] benzotriazole, 2 ' methylenebis [4- (1,1,3, 3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol ], 2- (2 ' -hydroxy-5 ' -methacryloxyphenyl) -2H-benzotriazole and the like.

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

Examples of the cyanoacrylate-based ultraviolet absorber include: 2-ethylhexyl 2-cyano-3, 3 '-diphenylacrylate, ethyl 2-cyano-3, 3' -diphenylacrylate, and the like.

Examples of the light stabilizer include: hindered amine light stabilizers, ultraviolet light stabilizers, and the like.

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

Examples of the ultraviolet stabilizer include: nickel bis (octylphenyl) sulfide, [2, 2' -thiobis (4-tert-octylphenol) ] -n-butylamine nickel, 3, 5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid monoethanol nickel complex, nickel dibutyldithiocarbamate, a benzoate-type quencher, nickel dibutyldithiocarbamate and the like.

As the deterioration preventing agent, a deterioration preventing agent having a hindered phenol structure is preferable. When the deterioration inhibitor having a hindered phenol structure is contained as the deterioration inhibitor, the content ratio thereof is preferably 0.01 to 10% by weight, more preferably 0.05 to 10% by weight, and still more preferably 0.1 to 10% by weight, based on the polyol (a). By adjusting the content ratio of the deterioration preventing agent having a hindered phenol structure within the above range, the adhesive residue and the like are less likely to occur on the adherend when stored in a heated state after the adherend is attached to the adherend, and the adhesive residue preventing property can be further excellent. If the content of the deterioration inhibitor having a hindered phenol structure is too small, the residual gum preventing property may not be sufficiently exhibited. If the content ratio of the deterioration preventing agent having a hindered phenol structure is too large, there is a concern that: there are problems that the cost becomes unfavorable, the adhesive property cannot be maintained, or the adherend is contaminated.

As the deterioration prevention agent having a hindered phenol structure, for example, any suitable deterioration prevention agent may be used as long as it has a hindered phenol structure in which a bulky group such as a tert-butyl group is bonded to at least one of adjacent carbon atoms of an aromatic ring carbon atom to which an OH group of phenol is bonded. It is considered that by using a specific deterioration inhibitor such as one having such a hindered phenol structure, the effect of suppressing the lowering of the molecular weight of the polyol becomes extremely large as compared with the conventional one, and therefore, the effect of preventing the gum residue can be remarkably excellent as compared with the conventional one.

Specific examples of such a deterioration preventing agent having a hindered phenol structure include: dibutylhydroxytoluene (BHT); trade name "IRGANOX 1010" (manufactured by BASF), trade name "IRGANOX 1010 FF" (manufactured by BASF), trade name "IRGANOX 1035 FF" (manufactured by BASF), trade name "IRGANOX 1076 FD" (manufactured by BASF), trade name "IRGANOX 1076 DWJ" (manufactured by BASF), trade name "IRGANOX 1098" (manufactured by BASF), trade name "IRGANOX 1135" (manufactured by BASF), trade name "IRGANOX 1330" (manufactured by BASF), trade name "IRGANOX 1726" (manufactured by BASF), trade name "IRGANOX 142nox 5 1425 WL" (manufactured by BASF), trade name "IRGANOX 1520L" (manufactured by BASF), trade name "IRGANOX 245 FF" (manufactured by BASF 259 "(manufactured by BASF), trade name" IRGANOX3114 "(manufactured by BASF), trade name" IRGANOX565 "(manufactured by BASF) and hindered antioxidants (manufactured by BASF 295); benzotriazole-based ultraviolet absorbers such as a trade name "TINUVIN P" (manufactured by BASF), a trade name "TINUVIN P FL" (manufactured by BASF), a trade name "TINUVIN 234" (manufactured by BASF), a trade name "TINUVIN 326 FL" (manufactured by BASF), a trade name "TINUVIN 328" (manufactured by BASF), a trade name "TINUVIN 329" (manufactured by BASF), and a trade name "TINUVIN 329 FL" (manufactured by BASF); liquid ultraviolet absorbers such as the trade name "TINUVIN 213" (manufactured by BASF) and the trade name "TINUVIN 571" (manufactured by BASF); triazine ultraviolet absorbers under the trade name "TINUVIN 1577 ED" (manufactured by BASF); benzoic acid ester ultraviolet absorbers under the trade name "TINUVIN 120" (manufactured by BASF); hindered amine light stabilizers such as "TINUVIN 144" (manufactured by BASF); and so on.

The polyurethane resin preferably contains a fatty acid ester. The polyurethane resin contains a fatty acid ester, and thus the wetting rate can be increased. The fatty acid ester may be only 1 kind or 2 or more kinds.

The content ratio of the fatty acid ester is preferably 5 to 50% by weight, more preferably 7 to 40% by weight, still more preferably 8 to 35% by weight, particularly preferably 9 to 30% by weight, and most preferably 10 to 20% by weight, based on the polyol (a). By adjusting the content ratio of the fatty acid ester to be within the above range, the wetting rate can be further increased. If the content of the fatty acid ester is too small, the wetting rate may not be sufficiently increased. If the content ratio of the fatty acid ester is too high, there is a fear that: there are problems that the cost becomes unfavorable, the adhesive property cannot be maintained, or the adherend is contaminated.

The number average molecular weight Mn of the fatty acid ester is preferably 200 to 400, more preferably 210 to 395, further preferably 230 to 380, particularly preferably 240 to 360, and most preferably 270 to 340. By adjusting the number average molecular weight Mn of the fatty acid ester to be within the above range, the wetting rate can be further increased. If the number average molecular weight Mn of the fatty acid ester is too small, the wetting rate may not be increased even if the number of added components is increased. If the number average molecular weight Mn of the fatty acid ester is too large, curability of the adhesive during drying may be deteriorated, and not only the wet property but also other adhesive properties may be adversely affected.

As the fatty acid ester, any suitable fatty acid ester may be used within a range not impairing 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, isopropyl myristate, isopropyl palmitate, cholesterol isostearate, lauryl methacrylate, methyl coconut fatty acid, methyl laurate, methyl oleate, methyl stearate, myristyl myristate, octyldodecyl myristate, pentaerythritol monooleate, pentaerythritol monostearate, pentaerythritol tetrapalmitate, stearyl stearate, isotridecyl stearate, triglyceryl 2-ethylhexanoate, butyl laurate, octyl oleate, and the like.

The urethane resin preferably contains a leveling agent. By containing the leveling agent in the urethane resin, unevenness in appearance due to orange peel can be prevented. The number of the leveling agents may be only 1, or may be 2 or more.

The content ratio of the leveling agent is preferably 0.001 to 1% by weight, more preferably 0.002 to 0.5% by weight, even more preferably 0.003 to 0.1% by weight, particularly preferably 0.004 to 0.05% by weight, and most preferably 0.005 to 0.01% by weight, based on the polyol (a). By adjusting the content ratio of the leveling agent to be within the above range, unevenness in appearance due to orange peel can be further prevented. If the content of the leveling agent is too small, the unevenness in appearance due to the orange peel may not be prevented. If the content ratio of the leveling agent is too large, there is a concern that: there are problems that the cost becomes unfavorable, the adhesive property cannot be maintained, or the adherend is contaminated.

As the leveling agent, any suitable leveling agent may be used within a range not impairing the effects of the present invention. Examples of such leveling agents include: acrylic leveling agents, fluorine leveling agents, silicon leveling agents, and the like. Examples of the acrylic leveling agent include: POLYFLOW No.36, POLYFLOW No.56, POLYFLOW No.85HF, POLYFLOW No.99C (all manufactured by Kyoeisha chemical Co., Ltd.), and the like. Examples of the fluorine-based leveling agent include: megafac F470N and Megafac F556 (both produced by DIC corporation), and the like. Examples of the silicon leveling agent include: GRANDIC PC4100(DIC corporation).

As a method for obtaining a polyurethane resin by curing a composition containing the polyol (a) and the polyfunctional isocyanate compound (B), any suitable method using a urethanization reaction method such as bulk polymerization or solution polymerization can be employed within the range not impairing the effect of the present invention. However, since the conventional polyurethane resin obtained via a so-called urethane prepolymer may not exhibit the effects of the present invention, a method other than the method for obtaining a polyurethane resin via a urethane prepolymer is preferable as a method for obtaining a polyurethane resin by curing a composition containing a polyol (a) and a polyfunctional isocyanate compound (B).

In order to cure the composition containing the polyol (a) and the polyfunctional isocyanate compound (B), a catalyst is preferably used. Examples of such a catalyst include: organometallic compounds, tertiary amine compounds, and the like.

Examples of the organometallic compound include: iron-based compounds, tin-based compounds, titanium-based compounds, zirconium-based compounds, lead-based compounds, cobalt-based compounds, zinc-based compounds, and the like. Among these, iron-based compounds and tin-based compounds are preferable from the viewpoint of reaction rate and the lifetime of the adhesive layer.

Examples of the iron-based compound include: ferric acetylacetonate, iron 2-ethylhexanoate, and the like.

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

Examples of the titanium-based compound include: dibutyltitanium dichloride, tetrabutyltitanate, butoxytitanium trichloride, and the like.

Examples of the zirconium-based compound include: zirconium naphthenate, zirconium acetylacetonate, and the like.

Examples of the lead-based compound include: lead oleate, lead 2-ethylhexoate, lead benzoate, lead naphthenate, and the like.

Examples of the cobalt compound include: cobalt 2-ethylhexanoate, cobalt benzoate, and the like.

Examples of the zinc-based compound include: zinc naphthenate, zinc 2-ethylhexanoate, and the like.

Examples of the tertiary amine compound include: triethylamine, triethylenediamine, 1, 8-diazabicyclo- (5,4,0) -undecene-7, and the like.

The number of the catalyst may be only 1 or 2 or more. Further, a catalyst, a crosslinking retarder, and the like may be used in combination. The amount of the catalyst is preferably 0.02 to 0.10% by weight, more preferably 0.02 to 0.08% by weight, much more preferably 0.02 to 0.06% by weight, particularly preferably 0.02 to 0.05% by weight, based on the polyol (A). By adjusting the amount of the catalyst within the above range, a pressure-sensitive adhesive layer having a light initial peel force, a light 180-degree peel force, and a high wetting rate can be obtained, and by combining with the specific base material layer used in the present invention, a surface protective film which can easily obtain a starting point for peeling from an adherend, and can be easily peeled off, and further has a high detection rate of scratches and foreign matter inclusion can be provided.

The polyurethane-based adhesive may comprise an ionic liquid containing a fluoro organic anion. The polyurethane adhesive containing the ionic liquid containing the fluorine organic anion can provide a polyurethane adhesive having very excellent antistatic properties. The number of ionic liquids that may be contained in the polyurethane adhesive may be only 1, or may be 2 or more.

In the present invention, the ionic liquid refers to a molten salt (ionic compound) that is in a liquid state at 25 ℃.

As long as the ionic liquid is an ionic liquid containing a fluorine organic anion, any suitable ionic liquid can be used within a range not impairing the effects of the present invention. As such an ionic liquid, an ionic liquid composed of a fluorine organic anion and an onium cation is preferable. By using an ionic liquid composed of a fluorine organic anion and an onium cation as the ionic liquid, a polyurethane adhesive having extremely excellent antistatic properties can be provided.

As the onium cation capable of constituting the ionic liquid, any suitable onium cation may be used within a range not impairing the effects of the present invention. Such onium cations are preferably at least 1 kind selected from nitrogen-containing onium cations, sulfur-containing onium cations, and phosphorus-containing onium cations. By selecting these onium cations, a polyurethane adhesive having extremely excellent antistatic properties can be provided.

The onium cation capable of constituting the ionic liquid is preferably at least 1 kind selected from cations having structures represented by general formulae (1) to (5).

[ chemical formula 1]

In the general formula (1), R_aRepresents a C4-20 hydrocarbon group, which may contain a hetero atom, R_bAnd R_cThe same or different, represent hydrogen or C1-C16 hydrocarbon group, and may contain hetero atom. Wherein, when the nitrogen atom contains a double bond, R is absent_c。

In the general formula (2), R_dRepresents a C2-20 hydrocarbon group, which may contain a hetero atom, R_e、R_fAnd R_gThe same or different, represent hydrogen or C1-C16 hydrocarbon group, and may contain hetero atom.

In the general formula (3), R_hRepresents a C2-20 hydrocarbon group, which may contain a hetero atom, R_i、R_jAnd R_kThe same or different, represent hydrogen or C1-C16 hydrocarbon group, and may contain hetero atom.

In the general formula (4), Z represents a nitrogen atom, a sulfur atom or a phosphorus atom, R_l、R_m、R_nAnd R_oThe same or different alkyl groups represent C1-20 alkyl groups, and may contain hetero atoms. Wherein, when Z is a sulfur atom, R is absent_o。

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

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

Specific examples of the cation represented by the general formula (1) include: pyridinium cations such as 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, and 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-dipropylpyrrolidinium cation, 1-propylpyrrolidinium cation, 1-ethylpyrrolidinium cation, 1-propylpyrrolidinium cation, and mixtures thereof, Pyrrolidinium cations such as 1-propyl-1-butylpyrrolidinium cation and 1, 1-dibutylpyrrolidinium cation; 1-propylpiperidinium cation, 1-pentylpiperidinium 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-ethyl-1-pentylpiperidinium cation, 1-ethyl-1-hexylpiperidinium cation, 1-ethyl, Piperidinium cations such as 1-propyl-1-butylpiperidinium cation, 1-dimethylpiperidinium cation, 1-dipropylpiperidinium cation and 1, 1-dibutylpiperidinium cation; 2-methyl-1-pyrroline cation; 1-ethyl-2-phenylindole cation; 1, 2-dimethylindole cation; a 1-ethyl carbazole cation; and so on.

Among these, from the viewpoint of further exhibiting the effects of the present invention, preferred examples include: pyridinium cations such as 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, and 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-hexylpyrrolidinium cation, 1-methyl-1-heptylpyrrolidinium cation, pyrrolidinium cations such as 1-ethyl-1-propylpyrrolidinium cation, 1-ethyl-1-butylpyrrolidinium cation, 1-ethyl-1-pentylpyrrolidinium cation, 1-ethyl-1-hexylpyrrolidinium cation, and 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, piperidinium cations such as 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, and 1-propyl-1-butylpiperidinium cation; and the like, more preferably 1-hexylpyridinium cation, 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.

Examples of the cation represented by the general formula (2) include: imidazolium cations, tetrahydropyrimidinium cations, dihydropyrimidinium cations, and the like.

Specific examples of the cation represented by the general formula (2) include: 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, 1, 2-dimethyl-3-propylimidazolium cation, 1-ethyl-2, 3-dimethylimidazolium cation, 1-butyl-3-dimethylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-decyl-3-methylimidazoliu, Imidazolium cations such as 1-hexyl-2, 3-dimethylimidazolium cation; tetrahydropyrimidinium cations such as1, 3-dimethyl-1, 4,5, 6-tetrahydropyrimidinium cation, 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-1, 4,5, 6-tetrahydropyrimidinium cation; dihydropyrimidinium cations such as1, 3-dimethyl-1, 4-dihydropyrimidinium cation, 1, 3-dimethyl-1, 6-dihydropyrimidinium cation, 1,2, 3-trimethyl-1, 4-dihydropyrimidinium cation, 1,2, 3-trimethyl-1, 6-dihydropyrimidinium cation, 1,2,3, 4-tetramethyl-1, 4-dihydropyrimidinium cation, and 1,2,3, 4-tetramethyl-1, 6-dihydropyrimidinium cation; and so on.

Among these, from the viewpoint of further exhibiting the effect of the present invention, 1, 3-dimethylimidazolium cation, 1, 3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1-butyl-3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation are preferable, imidazolium cations such as 1-octyl-3-methylimidazolium cation, 1-decyl-3-methylimidazolium cation, 1-dodecyl-3-methylimidazolium cation, and 1-tetradecyl-3-methylimidazolium cation, and more preferably 1-ethyl-3-methylimidazolium cation and 1-hexyl-3-methylimidazolium cation.

Examples of the cation represented by the general formula (3) include: pyrazolium cations, pyrazolinium cations, and the like.

Specific examples of the cation represented by the general formula (3) include: pyrazolium cations such as 1-methylpyrazolium cation, 3-methylpyrazolium cation, 1-ethyl-2, 3, 5-trimethylpyrazolium cation, 1-propyl-2, 3, 5-trimethylpyrazolium cation, and 1-butyl-2, 3, 5-trimethylpyrazolium cation; pyrazolinium cations such as 1-ethyl-2, 3, 5-trimethylpyrazolinium cation, 1-propyl-2, 3, 5-trimethylpyrazolinium cation, and 1-butyl-2, 3, 5-trimethylpyrazolinium cation; and so on.

Examples of the cation represented by the general formula (4) include: tetraalkylammonium cations, trialkylsulfonium cations, tetraalkylphosphonium cations, cations in which a part of the alkyl groups is substituted with alkenyl groups, alkoxy groups, and epoxy groups, and the like.

Specific examples of the cation represented by the general formula (4) include: tetramethylammonium cation, tetraethylammonium cation, tetrabutylammonium cation, tetrapentylammonium cation, tetrahexylammonium cation, tetraheptylammonium cation, triethylmethylammonium cation, tributylethylammonium cation, trimethylpropylammonium cation, trimethyldecylammonium cation, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium cation, glycidyltrimethylammonium cation, trimethylsulfonium cation, triethylsulfonium cation, tributylsulfonium cation, trihexylsulfonium cation, diethylmethylsulfinium cation, dibutylethylsulfonium cation, dimethyldecylsulfonium cation, tetramethylphosphonium cation, tetraethylphosphonium cation, tetrabutylphosphonium cation, tetrahexylphosphonium cation, tetraoctylphosphonium cation, triethylmethylphosphonium cation, tributylethylphosphonium cation, tetrabutylphosphonium cation, tetramethylphosphonium cation, trimethyldecylphosphonium cation, diallyldimethylammonium cation, and the like.

Among these, from the viewpoint of further exhibiting the effects of the present invention, preferred examples include: asymmetric tetraalkylammonium cations such as triethylmethylammonium cation, tributylethylammonium cation, trimethyldecylammonium cation, diethylmethylsulfinium cation, dibutylethylsulfonium cation, dimethyldecylsulfinium cation, triethylmethylphosphonium cation, tributylethylammonium cation, trimethyldecylphosphonium cation, trialkylsulfinium cation, tetraalkylphosphonium cation, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium cation, glycidyltrimethylammonium cation, diallyldimethylammonium cation, N-dimethyl-N-ethyl-N-propylammonium cation, N-dimethyl-N-ethyl-N-butylammonium cation, N-dimethyl-N-ethyl-N-pentylammonium cation, N, N-dimethyl-N-ethyl-N-hexylammonium cation, N-dimethyl-N-ethyl-N-heptylammonium cation, N-dimethyl-N-ethyl-N-nonylammonium cation, N-dimethyl-N, N-dipropylammonium cation, N-diethyl-N-propyl-N-butylammonium cation, N-dimethyl-N-propyl-N-pentylammonium cation, N-dimethyl-N-propyl-N-hexylammonium cation, N-dimethyl-N-propyl-N-heptylammonium cation, N-dimethyl-N-butyl-N-hexylammonium cation, N-dimethyl-N-hexyl ammonium cation, N, N, N-diethyl-N-butyl-N-heptylammonium cation, N-dimethyl-N-pentyl-N-hexylammonium cation, N-dimethyl-N, N-dihexylammonium cation, trimethylheptylammonium cation, N-diethyl-N-methyl-N-propylammonium cation, N-diethyl-N-methyl-N-pentylammonium cation, N-diethyl-N-methyl-N-heptylammonium cation, N-diethyl-N-propyl-N-pentylammonium cation, triethylpropylammonium cation, triethylpentylammonium cation, triethylheptylammonium cation, N-diethyl-N-butyl-N-heptylammonium cation, N-diethyl-N-propyl-N-pentylammonium cation, N-diethyl-N-, N, N-dipropyl-N-methyl-N-ethylammonium cation, N-dipropyl-N-methyl-N-pentylammonium cation, N-dipropyl-N-butyl-N-hexylammonium cation, N-dipropyl-N, N-dihexylammonium cation, N-dibutyl-N-methyl-N-pentylammonium cation, N-dibutyl-N-methyl-N-hexylammonium cation, trioctylmethylammonium cation, N-methyl-N-ethyl-N-propyl-N-pentylammonium cation, etc., and the like, more preferably trimethylpropylammonium cation.

As the fluoroorganic anion capable of constituting the ionic liquid, any suitable fluoroorganic anion may be used within a range not impairing the effects of the present invention. Such fluoroorganic anions may be fully fluorinated (perfluorinated) or partially fluorinated.

Examples of such a fluoroorganic anion include: fluorinated arylsulfonate, perfluoroalkanesulfonate, bis (fluorosulfonyl) imide, bis (perfluoroalkanesulfonyl) imide, cyanoperfluoroalkanesulfonylamide, bis (cyano) perfluoroalkanesulfonylmethide, cyano-bis- (perfluoroalkanesulfonyl) methide, tris (perfluoroalkanesulfonyl) methide, trifluoroacetate, perfluoroalkylide, tris (perfluoroalkanesulfonyl) methide, (perfluoroalkanesulfonyl) trifluoroacetamide, and the like.

Among these fluoro organic anions, perfluoroalkyl sulfonate, bis (fluorosulfonyl) imide and bis (perfluoroalkanesulfonyl) imide are more preferable, and more specifically, trifluoromethanesulfonate, pentafluoroethanesulfonate, heptafluoropropanesulfonate, nonafluorobutanesulfonate, bis (fluorosulfonyl) imide and bis (trifluoromethanesulfonyl) imide are more preferable.

As a specific example of the ionic liquid that can be contained in the polyurethane-based adhesive, it can be appropriately selected and used from the combination of the above-mentioned cationic component and the above-mentioned anionic component. Specific examples of such an ionic liquid include: 1-hexylpyridinium bis (fluorosulfonyl) imide, 1-ethyl-3-methylpyridinium trifluoromethanesulfonate, 1-ethyl-3-methylpyridinium pentafluoroethanesulfonate, 1-ethyl-3-methylpyridinium heptafluoropropanesulfonate, 1-ethyl-3-methylpyridinium nonafluorobutanesulfonate, 1-butyl-3-methylpyridinium trifluoromethanesulfonate, 1-butyl-3-methylpyridinium bis (trifluoromethanesulfonyl) imide, 1-butyl-3-methylpyridinium bis (pentafluoroethanesulfonyl) imide, 1-octyl-4-methylpyridinium bis (fluorosulfonyl) imide, 1-dimethylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-3-methylpyridinium trifluoromethanesulfonyl-ate, 1-ethyl-3-methylpyridinium, 1-methyl-1-ethylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpyrrolidinium bis (fluorosulfonyl) imide, 1-methyl-1-butylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-pentylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-hexylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-heptylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-propylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpyrrolidinium bis (trifluoromethanesulfonyl) imide, and mixtures thereof, 1-Ethyl-1-butylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-Ethyl-1-pentylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-Ethyl-1-hexylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-Ethyl-1-heptylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-dipropylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-propyl-1-butylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-dibutylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-propylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-pentylpiperidinium bis (trifluoromethanesulfonyl) imide, 1, 1-dimethylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-ethylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpiperidinium bis (fluorosulfonyl) imide, 1-methyl-1-butylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-pentylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-hexylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-heptylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-propylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-Ethyl-1-butylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-Ethyl-1-pentylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-Ethyl-1-hexylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-Ethyl-1-heptylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-dipropylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-propyl-1-butylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-dibutylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-dimethylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-ethylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-Ethyl-1-pyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-propylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-butylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-pentylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-hexylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-heptylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-propylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-butylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-pentylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-hexylpyrrolidinium bis (pentafluoro, 1-Ethyl-1-hexylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-Ethyl-1-heptylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-dipropylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-propyl-1-butylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-dibutylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-propylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-pentylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-dimethylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-ethylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-propylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-butylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-pentylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-hexylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-heptylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-propylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-butylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-pentylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-hexylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-Ethyl-1-heptylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-dipropylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-propyl-1-butylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-dibutylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-3-methylimidazolium trifluoroacetate, 1-ethyl-3-methylimidazolium heptafluorobutyrate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium heptafluoropropanesulfonate, 1-ethyl-3-methylimidazolium nonafluorobutanesulfonate, 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-ethyl-3-methylimidazolium bis (fluorosulfonyl) imide, 1-ethyl-3-methylimidazolium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-3-methylimidazolium tris (trifluoromethanesulfonyl) methide, 1-butyl-3-methylimidazolium trifluoroacetate, 1-butyl-3-methylimidazolium heptafluorobutyrate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium perfluorobutanesulfonate, 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-hexyl-3-methylimidazolium trifluoromethanesulfonate, 1-hexyl-3-methylimidazolium bis (fluorosulfonyl) imide, 1, 2-dimethyl-3-propylimidazolium bis (trifluoromethanesulfonyl) imide, 1-ethyl-2, 3, 5-trimethylpyrazolium bis (trifluoromethanesulfonyl) imide, 1-propyl-2, 3, 5-trimethylpyrazolium bis (trifluoromethanesulfonyl) imide, 1-butyl-2, 3, 5-trimethylpyrazolium bis (trifluoromethanesulfonyl) imide, 1-ethyl-2, 3, 5-trimethylpyrazolium bis (pentafluoroethanesulfonyl) imide, 1-propyl-2, 3, 5-trimethylpyrazolium bis (pentafluoroethanesulfonyl) imide, 1-butyl-2, 3, 5-trimethylpyrazolium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-2, 3, 5-trimethylpyrazolium (trifluoromethanesulfonyl) trifluoroacetamide, 1-propyl-2, 3, 5-trimethylpyrazolium (trifluoromethanesulfonyl) trifluoroacetamide, 1-butyl-2, 3, 5-trimethylpyrazolium (trifluoromethanesulfonyl) trifluoroacetamide, trimethylpropylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-ethyl-N-propylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-ethyl-N-butylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-ethyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N-trimethyl-N-propylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-propylammonium bis (trifluoromethanesulfonyl, N, N-dimethyl-N-ethyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-ethyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-ethyl-N-nonylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N, N-dipropylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-propyl-N-butylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-propyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-propyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-hexyl-ammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-propyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-butyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-butyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-pentyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N, N-dihexylammonium bis (trifluoromethanesulfonyl) imide, trimethylheptylammonium bis (trifluoromethanesulfonyl) imide, N-diethyl-N-methyl-N-propylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-propyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-hexyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-propylammonium, N, N-diethyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N-diethyl-N-methyl-N, N-heptylammonium bis (trifluoromethanesulfonyl) imide, N-diethyl-N-propyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, triethylpropylammonium bis (trifluoromethanesulfonyl) imide, triethylpentylammonium bis (trifluoromethanesulfonyl) imide, triethylheptylammonium bis (trifluoromethanesulfonyl) imide, N-dipropyl-N-methyl-N-ethylammonium bis (trifluoromethanesulfonyl) imide, N-dipropyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N-butyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N-dipropyl-N, N-dihexylammonium bis (trifluoromethanesulfonyl) imide, N-dibutyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N-dibutyl-N-methyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, trioctylmethylammonium bis (trifluoromethanesulfonyl) imide, N-methyl-N-ethyl-N-propyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, 1-butylpyridinium (trifluoromethanesulfonyl) trifluoroacetamide, 1-butyl-3-methylpyridinium (trifluoromethanesulfonyl) trifluoroacetamide, 1-ethyl-3-methylimidazolium (trifluoromethanesulfonyl) trifluoroacetamide, tetrahexylammonium bis (trifluoromethanesulfonyl) imide, diallyldimethylammonium trifluoromethanesulfonate, diallyldimethylammonium bis (trifluoromethanesulfonyl) imide, diallyldimethylammonium bis (pentafluoroethanesulfonyl) imide, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium trifluoromethanesulfonate, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (trifluoromethanesulfonyl) imide, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (pentafluoroethanesulfonyl) imide, N-diethyl, Glycidyl trimethylammonium triflate, glycidyl trimethylammonium bis (trifluoromethanesulfonyl) imide, glycidyl trimethylammonium bis (pentafluoroethanesulfonyl) imide, diallyldimethylammonium bis (trifluoromethanesulfonyl) imide, diallyldimethyl bis (pentafluoroethanesulfonyl) imide, lithium bis (trifluoromethanesulfonyl) imide, lithium bis (fluorosulfonyl) imide, and the like.

Of these ionic liquids, more preferred are 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-ethyl-3-methylpyridinium heptafluoropropanesulfonate, 1-ethyl-3-methylpyridinium nonafluorobutanesulfonate, 1-butyl-3-methylpyridinium trifluoromethanesulfon, 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, trimethylpropylammonium bis (trifluoromethanesulfonyl) imide, lithium bis (fluorosulfonyl) imide.

The ionic liquid may be commercially available, or may be synthesized as described below. As a method for synthesizing an ionic liquid, there is no particular limitation as long as the target ionic liquid is used, and generally, there can be used a halide method, a hydroxide method, an acid ester method, a complex formation method, an neutralization method, and the like, which are described in the literature "ionic liquid-developed first and future" (イオン liquid-open future) laid open (と future-open CMC published).

The following synthesis method is given for the halide method, hydroxide method, acid ester method, complex formation method and neutralization method using a nitrogen-containing onium salt as an example, and other ionic liquids such as sulfur-containing onium salts and phosphonium-containing onium salts can be obtained by the same method.

The halide method is a method in which reactions represented by the reaction formulas (1) to (3) are performed. First, a tertiary amine is reacted with an alkyl halide to obtain a halide (reaction formula (1), and chlorine, bromine, and iodine are used as a halogen).

The obtained halide and the catalystAnion structure of targeted ionic liquid (A)^－) The acid (HA) or salt (MA, M are cations forming a salt with an objective anion such as ammonium, lithium, sodium, potassium) to obtain an objective ionic liquid (R)₄NA)。

[ chemical formula 2]

(1)R₃N+RX→R₄NX(X：Cl，Br，I)

(2)R₄NX+HA→R₄NA+HX

(3)R₄NX+MA→R₄NA+MX(M:NH₄Li, Na, K, Ag, etc.)

The hydroxide method is a method in which reactions represented by reaction formulas (4) to (8) are performed. First of all, the halide (R)₄NX) is electrolyzed by an ion exchange membrane method (reaction formula (4)), an OH-type ion exchange resin method (reaction formula (5)), or with silver oxide (Ag)₂O) (reaction formula (6)) to obtain a hydroxide (R)₄NOH) (as halogen, chlorine, bromine, iodine were used).

The obtained hydroxide was subjected to the reactions of the reaction formulae (7) to (8) to obtain the desired ionic liquid (R) in the same manner as in the halogenation method described above₄NA)。

[ chemical formula 3]

(4)R₄NX+H₂O→R₄NOH+1/2H₂+1/2X₂(X：Cl，Br，I)

(5)R₄NX+P-OH→R₄NOH + P-X (P-OH: OH type ion exchange resin)

(6)R₄NX+1/2Ag₂O+1/2H₂O→R₄NOH+AgX

(7)R₄NOH+HA→R₄NA+H₂O

(8)R₄NOH+MA→R₄NA+MOH(M:NH₄Li, Na, K, Ag, etc.)

The acid ester method is a method in which the reaction is performed by the reactions represented by the reaction formulae (9) to (11). First, a tertiary amine (R)₃N) with an acid ester to obtain an acid ester (reaction formula (9), and examples of the acid ester include esters of inorganic acids such as sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid and carbonic acid, and esters of organic acids such as methanesulfonic acid, methylphosphonic acid and formic acid)。

The acid ester obtained can be reacted by the reaction formulae (10) to (11) to obtain the desired ionic liquid (R) in the same manner as in the halogenation method described above₄NA). Further, by using methyl trifluoromethanesulfonate, methyl trifluoroacetate or the like as the acid ester, an ionic liquid can be obtained as it is.

[ chemical formula 4]

(9)R₃N+ROY→R₄NOY

(OY

Etc.)

(10)R₄NOY+HA→R₄NA+HOY

(OY:

In the case of,

)

(11)R₄NOY+MA→R₄NA+MOY(M:NH₄Li, Na, K, Ag, etc.)

The neutralization method is a method carried out by a reaction shown in the reaction formula (12). Can be prepared by reacting a tertiary amine with CF₃COOH、CF₃SO₃H、(CF₃SO₂)₂NH、(CF₃SO₂)₃CH、(C₂F₅SO₂)₂NH, etc.

[ chemical formula 5]

(12)R₃N+HZ→R₃NN⁺Z^-

[HZ:CF₃COOH,CF₃SO₃H,(CF₃SO₂)₂NH,(CF₃SO₂)₃CH,(C₂F₅SO₂)₂Organic acids such as NH]

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

The amount of the ionic liquid to be blended varies depending on the compatibility between the polymer to be used and the ionic liquid, and cannot be generally defined, and is generally preferably 0.001 to 50 parts by weight, more preferably 0.01 to 40 parts by weight, further preferably 0.01 to 30 parts by weight, particularly preferably 0.01 to 20 parts by weight, and most preferably 0.01 to 10 parts by weight, based on 100 parts by weight of the polyurethane resin. By adjusting the amount of the ionic liquid to be blended within the above range, a polyurethane-based adhesive having very excellent antistatic properties can be provided. If the amount of the ionic liquid added is less than 0.01 parts by weight, sufficient antistatic properties may not be obtained. When the amount of the ionic liquid added exceeds 50 parts by weight, the adherend tends to be contaminated more.

The polyurethane adhesive may contain any suitable other component in addition to the above polyurethane resin and ionic liquid within a range not impairing the effects of the present invention. Examples of such other components include: other resin components than the polyurethane resin, an adhesion promoter, an inorganic filler, an organic filler, metal powder, a pigment, a foil, a softening agent, a plasticizer, an anti-aging agent, a conductive agent, an ultraviolet absorber, an antioxidant, a light stabilizer, a surface lubricant, a leveling agent, an anti-corrosion agent, a heat stabilizer, a polymerization inhibitor, a lubricant, a solvent, and the like.

The polyurethane-based adhesive may contain a modified silicone oil. The polyurethane adhesive containing the modified silicone oil can further effectively exhibit the effects of the present invention.

When the polyurethane adhesive contains the modified silicone oil, the content ratio thereof is preferably 0.001 to 50 parts by weight, more preferably 0.01 to 40 parts by weight, still more preferably 0.01 to 30 parts by weight, particularly preferably 0.01 to 20 parts by weight, and most preferably 0.01 to 10 parts by weight, based on 100 parts by weight of the polyurethane resin. By adjusting the content ratio of the modified silicone oil within the above range, the effects of the present invention can be more effectively exhibited.

As the modified silicone oil, any suitable modified silicone oil may be used within a range not impairing the effects of the present invention. Examples of such modified silicone oils include those commercially available from shin-Etsu chemical Co.

The modified silicone oil is preferably a polyether-modified silicone oil. By using the polyether-modified silicone oil, the effects of the present invention can be further effectively exhibited.

Examples of the polyether-modified silicone oil include: side chain type polyether modified silicone oil, both terminal type polyether modified silicone oil, and the like. Of these, both-end type polyether-modified silicone oils are preferable from the viewpoint that the effects of the present invention can be more sufficiently exhibited.

[ acrylic adhesive ]

The acrylic adhesive contains an acrylic polymer.

The lower limit of the content of the acrylic polymer in the acrylic pressure-sensitive adhesive is preferably 40% by weight or more, more preferably 50% by weight or more, further preferably 55% by weight or more, further preferably 60% by weight, particularly preferably 65% by weight, and most preferably 70% by weight, and the upper limit thereof is preferably 99.999% by weight or less, more preferably 99.99% by weight or less, further preferably 99.9% by weight or less, further preferably 99% by weight or less, particularly preferably 95% by weight or less, and most preferably 90% by weight or less. By adjusting the content ratio of the acrylic polymer in the acrylic pressure-sensitive adhesive within the above range, a pressure-sensitive adhesive layer having a lighter initial peel force, a lighter 180-degree peel force, and a faster wetting rate can be obtained, and by combining with the specific base material layer used in the present invention, a surface protective film which can easily obtain a starting point for peeling from an adherend and has a higher detection rate of easy peeling, and further damage and foreign matter inclusion can be provided.

The acrylic polymer is a polymer containing an acrylic monomer (a monomer having a (meth) acryloyl group in a molecule) as a constituent monomer component.

The number of the acrylic polymer may be only 1, or may be 2 or more. The number of the acrylic monomer may be only 1, or may be 2 or more.

The acrylic polymer preferably contains an alkyl (meth) acrylate as a monomer component constituting the polymer. Examples of the alkyl (meth) acrylate include: alkyl (meth) acrylates having an alkyl group having 6 to 14 carbon atoms such as hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tridecyl (meth) acrylate, and n-tetradecyl (meth) acrylate. Among these, alkyl (meth) acrylates having an alkyl group having 7 to 13 carbon atoms are preferable, and 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, and n-tridecyl (meth) acrylate are more preferable. The number of the alkyl (meth) acrylates may be only 1, or may be 2 or more.

The content ratio of the alkyl (meth) acrylate to the total monomer components (100 wt%) constituting the acrylic polymer is preferably 70 wt% to 98 wt%, more preferably 80 wt% to 98 wt%, still more preferably 85 wt% to 98 wt%, and particularly preferably 90 wt% to 98 wt%. By adjusting the content ratio of the alkyl (meth) acrylate to the total monomer components (100 wt%) constituting the acrylic polymer within the above range, a pressure-sensitive adhesive layer having a lighter initial peel force, a lighter 180-degree peel force, and a faster wetting speed can be obtained.

The monomer component constituting the acrylic polymer preferably further contains a hydroxyl group-containing monomer. Examples of the hydroxyl group-containing monomer include: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, 4-hydroxymethylcyclohexyl methacrylate, N-methylol (meth) acrylamide, vinyl alcohol, allyl alcohol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, and the like. The hydroxyl group-containing monomer may be only 1 kind or 2 or more kinds.

The content ratio of the hydroxyl group-containing monomer to the entire monomer components (100 wt%) constituting the acrylic polymer is preferably 0.1 to 15 wt%, more preferably 0.5 to 13 wt%, still more preferably 2 to 10 wt%, and particularly preferably 3 to 8 wt%. By adjusting the content ratio of the hydroxyl group-containing monomer to the total monomer components (100 wt%) constituting the acrylic polymer to the above range, the cohesive force is obtained by forming the crosslinking points, and therefore, a pressure-sensitive adhesive layer having a lighter initial peel force, a lighter 180-degree peel force, and a faster wetting rate can be obtained.

The acrylic polymer may contain, for example, a polyfunctional monomer in the monomer component thereof from the viewpoint of introducing a crosslinked structure into the acrylic polymer and obtaining a suitable cohesive force.

Examples of the polyfunctional monomer include: ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6 hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, divinylbenzene, N' -methylenebisacrylamide, and the like. The number of the polyfunctional monomers may be only 1, or may be 2 or more.

The content ratio of the polyfunctional monomer to the entire monomer components (100% by weight) constituting the acrylic polymer is preferably 0.1% by weight to 30% by weight, and more preferably 0.1% by weight to 10% by weight. By adjusting the content ratio of the polyfunctional monomer to the total monomer components (100% by weight) constituting the acrylic polymer to the above range, the cohesive force is obtained by forming the crosslinking points, and therefore, a pressure-sensitive adhesive layer having a lighter initial peel force, a lighter peel force at 180 degrees peel and a faster wetting rate can be obtained.

The monomer component constituting the acrylic polymer may contain an alkylene oxide group-containing reactive monomer. The number of the epoxy alkyl group-containing reactive monomers may be only 1, or may be 2 or more.

The average number of moles of oxyalkylene units added as the alkylene oxide group-containing reactive monomer is preferably 3 to 40, more preferably 4 to 35, and further preferably 5 to 30, from the viewpoint of compatibility with a surfactant when the surfactant is used. By adjusting the average molar number of addition of the oxyalkylene units of the alkylene oxide group-containing reactive monomer to the above range, the effect of reducing contamination of the object to be protected by the use of the surfactant can be obtained efficiently. The terminal of the oxyalkylene chain may be a hydroxyl group as it is, or may be substituted with another functional group or the like.

The content ratio of the epoxy alkyl group-containing reactive monomer to the entire monomer components (100% by weight) constituting the acrylic polymer is preferably 10% by weight or less, more preferably 7% by weight or less, still more preferably 5% by weight or less, particularly preferably 3% by weight or less, and most preferably 1% by weight or less. By adjusting the content ratio of the alkylene oxide group-containing reactive monomer to the total monomer components (100% by weight) constituting the acrylic polymer within the above range, the effect of reducing contamination of the protected object by the use of the surfactant can be obtained efficiently.

The oxyalkylene unit of the alkylene oxide group-containing reactive monomer is preferably an oxyalkylene unit having an alkylene group having 1 to 6 carbon atoms, and examples thereof include: oxymethylene, oxyethylene, oxypropylene, oxybutylene and the like. The hydrocarbon group of the oxyalkylene chain may be a straight chain or a branched chain.

The alkylene oxide group-containing reactive monomer is preferably a reactive monomer having, for example, an ethylene oxide group. By using an acrylic polymer containing a reactive monomer having an ethylene oxide group as a constituent component, the compatibility of the acrylic polymer with a surfactant is improved, bleeding out of an adherend is suitably suppressed, and an acrylic pressure-sensitive adhesive with low staining can be obtained.

Examples of the alkylene oxide group-containing reactive monomer include: alkylene oxide (meth) acrylate adducts; a reactive surfactant having a reactive substituent such as an acryloyl group, a methacryloyl group, or an allyl group in the molecule; and so on.

Examples of the (meth) acrylic acid alkylene oxide adduct include: polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, polyethylene glycol-polybutylene glycol (meth) acrylate, polypropylene glycol-polybutylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, butoxypolyethylene glycol (meth) acrylate, octoxypolyethylene glycol (meth) acrylate, dodecyloxypolyethylene glycol (meth) acrylate, octadecyloxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, octoxypolyethylene glycol-polypropylene glycol (meth) acrylate, and the like.

Examples of the reactive surfactant as the alkylene oxide group-containing reactive monomer include: an anionic reactive surfactant having a (meth) acryloyl group or allyl group, a nonionic reactive surfactant, a cationic reactive surfactant, and the like.

Examples of the anionic reactive surfactant include those represented by the formulae (a1) to (a 10).

[ chemical formula 6]

R in the formula (A1)¹Represents hydrogen or methyl, R²Represents a C1-30 hydrocarbon group or acyl group, X represents an anionic hydrophilic group, R³And R⁴The same or different, and represents C1-C6 alkylene, and the average addition mole number m and n is 0-40, wherein (m + n) represents 3-40.

[ chemical formula 7]

R in the formula (A2)¹Represents hydrogen or methyl, R²And R⁷The same or different, represent C1-C6 alkylene, R³And R⁵Identical or different, represents hydrogen or alkyl, R⁴And R⁶The same or different, represents hydrogen, alkyl, benzyl or styryl, X represents an anionic hydrophilic group, and the average addition mole number m and n is 0 to 40, wherein (m + n) represents a number of 3 to 40.

[ chemical formula 8]

R in the formula (A3)¹Represents hydrogen or methyl, R²Represents an alkylene group having 1 to 6 carbon atoms, X represents an anionic hydrophilic group, and the average addition mole number n represents a number of 3 to 40.

[ chemical formula 9]

R in the formula (A4)¹Represents hydrogen or methyl, R²R represents a C1-30 hydrocarbon group or an acyl group³And R⁴The same or different, represent alkylene of carbon number 1-6, X represents anionic hydrophilic group, average addition mole number m and n is 0-40, wherein (m + n) represents number of 3-40.

[ chemical formula 10]

R in the formula (A5)¹Represents a hydrocarbon group, an amino group, a carboxylic acid residue, R²Represents an alkylene group having 1 to 6 carbon atoms, X represents an anionic hydrophilic group, and the average addition mole number n represents a number of 3 to 40.

[ chemical formula 11]

R in the formula (A6)¹R represents a C1-30 hydrocarbon group²Represents hydrogen or a C1-30 hydrocarbon group, R³Represents hydrogen or propenyl, R⁴Represents an alkylene group having 1 to 6 carbon atoms, X represents an anionic hydrophilic group, and the average addition mole number n represents a number of 3 to 40.

[ chemical formula 12]

R in the formula (A7)¹Represents hydrogen or methyl, R²And R⁴The same or different, represent C1-C6 alkylene, R³Represents a hydrocarbon group having 1 to 30 carbon atoms, M represents hydrogen, an alkali metal, an ammonium group or an alkanol ammonium group, and the average addition mole number M and n is 0 to 40, wherein (M + n) represents a number of 3 to 40.

[ chemical formula 13]

R in the formula (A8)¹And R⁵Identical or different, represents hydrogen or methyl, R²And R⁴The same or different, represent C1-C6 alkylene, R³Represents a hydrocarbon group having 1 to 30 carbon atoms, M represents hydrogen, an alkali metal, an ammonium group or an alkanol ammonium group, and the average addition mole number M and n is 0 to 40, wherein (M + n) represents a number of 3 to 40.

[ chemical formula 14]

R in the formula (A9)¹Represents C1-C6 alkylene, R²Represents a hydrocarbon group having 1 to 30 carbon atoms, M represents hydrogen, an alkali metal, an ammonium group or an alkylolammonium group, and the average addition mole number n represents a number of 3 to 40.

[ chemical formula 15]

R in the formula (A10)¹、R²And R³Identical or different, represents hydrogen or methyl, R⁴Represents a C0-30 hydrocarbon group (C0 represents no R)⁴)，R⁵And R⁶The same or different, represent alkylene of carbon number 1-6, X represents anionic hydrophilic group, average addition mole number m and n is 0-40, wherein (m + n) represents number of 3-40.

X in formulae (a1) to (a6) and formulae (a10) to (a10) represents an anionic hydrophilic group. Examples of the anionic hydrophilic group include groups represented by formulae (a1) to (a 2).

[ chemical formula 16]

-SO₃M¹ (a1)

M in the formula (a1)¹Represents hydrogen, an alkali metal, an ammonium group or an alkylolammonium group.

[ chemical formula 17]

M in the formula (a2)²And M³The same or different, represents hydrogen, an alkali metal, an ammonium group or an alkanolammonium group.

Examples of the nonionic reactive surfactant include those represented by the formulae (N1) to (N6).

[ chemical formula 18]

R in the formula (N1)¹Represents hydrogen or methyl, R²R represents a C1-30 hydrocarbon group or an acyl group³And R⁴The same or different, and represents C1-C6 alkylene, and the average addition mole number m and n is 0-40, wherein (m + n) represents 3-40.

[ chemical formula 19]

R in the formula (N2)¹Represents hydrogen or methyl, R²、R³And R⁴The same or different alkylene groups having 1 to 6 carbon atoms, and the average molar number n, m and l of addition is 0 to 40, and (n + m + l) represents a number of 3 to 40.

[ chemical formula 20]

R in the formula (N3)¹Represents hydrogen or methyl, R²And R³The same or different, represent C1-C6 alkylene, R⁴Represents a C1-30 hydrocarbon group or acyl group, and the average addition mole number m and n is 0-40, wherein (m + n) represents a number of 3-40.

[ chemical formula 21]

R in the formula (N4)¹And R²The same or different, each represents a C1-30 hydrocarbon group, R³Represents hydrogen or propenyl, R⁴Represents an alkylene group having 1 to 6 carbon atoms, and the average molar number n of addition represents a number of 3 to 40.

[ chemical formula 22]

R in the formula (N5)¹And R³The same or different, represent C1-C6 alkylene, R²And R⁴The same or different, represent hydrogen, alkyl with 1-30 carbon atoms, or acyl, and the average addition mole number m and n is 0-40, wherein (m + n) represents 3-40.

[ chemical formula 23]

R in the formula (N6)¹、R²And R³Identical or different, represents hydrogen or methyl, R⁴Represents a C0-30 hydrocarbon group (C0 represents no R)⁴)，R⁵And R⁶The same or different, and represents C1-C6 alkylene, and the average addition mole number m and n is 0-40, wherein (m + n) represents 3-40.

As the alkylene oxide group-containing reactive monomer, commercially available products such as BLEMER PME-400, BLEMER PME-1000, BLEMER 50POEP-800B (all of which are manufactured by NOF corporation), LATEMUL PD-420, LATEMUL PD-430 (all of which are manufactured by Kao corporation), ADEKA REASOAP ER-10, and ADEKA REASOAP-10 (all of which are manufactured by Asahi Denka Co., Ltd.) can be used.

The monomer component constituting the acrylic polymer may contain a monomer (other monomer) other than the alkyl (meth) acrylate, the hydroxyl group-containing monomer, the polyfunctional monomer, and the alkylene oxide group-containing reactive monomer. Examples of the other monomers include: cyano group-containing monomers, vinyl ester monomers, aromatic vinyl monomers, amide group-containing monomers, imide group-containing monomers, amino group-containing monomers, epoxy group-containing monomers, vinyl ether monomers, N-acryloyl morpholine and the like. Among these, cyano group-containing monomers, vinyl ester monomers, and aromatic vinyl monomers are preferable from the viewpoint of improving the cohesive force and the heat resistance. In addition, from the viewpoint of improving the adhesive strength and having a functional group which functions as a crosslinking point, an amide group-containing monomer, an imide group-containing monomer, an amino group-containing monomer, an epoxy group-containing monomer, a vinyl ether monomer, and N-acryloylmorpholine are preferable. The number of the other monomers may be only 1, or may be 2 or more.

Examples of the cyano group-containing monomer include: acrylonitrile, methacrylonitrile, and the like.

Examples of the vinyl ester monomer include: vinyl esters such as vinyl acetate, vinyl propionate, and vinyl laurate.

Examples of the aromatic vinyl monomer include: styrene, chlorostyrene, chloromethylstyrene, alpha-methylstyrene, other substituted styrenes, and the like.

Examples of the amide group-containing monomer include: acrylamide, methacrylamide, diethylacrylamide, N-vinylpyrrolidone, N-dimethylacrylamide, N-dimethylmethacrylamide, N-diethylacrylamide, N-diethylmethacrylamide, N' -methylenebisacrylamide, N-dimethylaminopropylacrylamide, N-dimethylaminopropylmethacrylamide, diacetoneacrylamide and the like.

Examples of the imide group-containing monomer include: cyclohexylmaleimide, isopropylmaleimide, N-cyclohexylmaleimide, itaconimide, and the like.

Examples of the amino group-containing monomer include: aminoethyl (meth) acrylate, N-dimethylaminoethyl (meth) acrylate, N-dimethylaminopropyl (meth) acrylate, and the like.

Examples of the epoxy group-containing monomer include: glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, allyl glycidyl ether, and the like.

Examples of the vinyl ether monomer include: methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, and the like.

The content ratio of the other monomer to the total monomer components (100 wt%) constituting the acrylic polymer is preferably 0 to 40 wt%, more preferably more than 0 wt% and 40 wt% or less, further preferably more than 0 wt% and 35 wt% or less, and particularly preferably more than 0 wt% and 30 wt% or less.

From the viewpoint of suppressing the increase of the adhesive force to the adherend, the monomer component constituting the acrylic polymer is preferably free of a carboxyl group-containing monomer, a sulfonic group-containing monomer, a phosphoric group-containing monomer, and an acid anhydride group-containing monomer. That is, the other monomers preferably do not include a carboxyl group-containing monomer, a sulfonic group-containing monomer, a phosphoric acid group-containing monomer, and an acid anhydride group-containing monomer.

The acrylic polymer can be obtained by polymerizing monomer components constituting the acrylic polymer. Examples of the polymerization method include: solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, photopolymerization (active energy ray polymerization), and the like. Among these, solution polymerization is preferable from the viewpoint of cost and productivity. The acrylic polymer obtained may be any of a random copolymer, a block copolymer, an alternating copolymer, a graft copolymer, and the like.

Examples of the method of solution polymerization include: a method of dissolving monomer components, a polymerization initiator, and the like in a solvent, and heating the solution to polymerize the monomer components and the polymerization initiator to obtain an acrylic polymer solution containing an acrylic polymer.

As the solvent used in the solution polymerization, various conventional solvents can be used. Examples of such solvents include: aromatic hydrocarbons such as toluene, benzene, and xylene; esters such as ethyl acetate and n-butyl acetate; aliphatic hydrocarbons such as n-hexane and n-heptane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; ketones such as methyl ethyl ketone and methyl isobutyl ketone; and the like. The number of the solvents may be only 1, or 2 or more.

For example, the blending ratio of the solvent is preferably 10 to 1000 parts by weight, more preferably 50 to 500 parts by weight, based on the total amount (100 parts by weight) of the monomer components constituting the acrylic polymer.

Examples of the polymerization initiator used in the solution polymerization include: peroxide polymerization initiators, azo polymerization initiators, and the like. Examples of the peroxide-based polymerization initiator include: peroxycarbonates, ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, and the like, and more specifically, there may be mentioned: benzoyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, t-butyl peroxybenzoate, dicumyl peroxide, 1-bis (t-butylperoxy) -3,3, 5-trimethylcyclohexane, 1-bis (t-butylperoxy) cyclododecane, and the like. Examples of the azo polymerization initiator include: 2,2 '-azobisisobutyronitrile, 2' -azobis-2-methylbutyronitrile, 2 '-azobis (2, 4-dimethylvaleronitrile), dimethyl 2, 2' -azobis (2-methylpropionate), 2 '-azobis (4-methoxy-2, 4-dimethylvaleronitrile), 1' -azobis (cyclohexane-1-carbonitrile), 2 '-azobis (2,4, 4-trimethylpentane), 4, 4' -azobis-4-cyanopentanoic acid, 2 '-azobis (2-amidinopropane) dihydrochloride, 2' -azobis [2- (5-methyl-2-imidazolin-2-yl) propane ] dihydrochloride, 2,2 '-azobis (2-methylpropionamidine) disulfate, 2' -azobis (N, N '-dimethyleneisobutylamidine) hydrochloride, 2' -azobis [ N- (2-carboxyethyl) -2-methylpropionamidine ] hydrate, and the like. The number of polymerization initiators may be only 1, or may be 2 or more.

For example, the compounding ratio of the polymerization initiator is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, based on the total amount (100 parts by weight) of the monomer components constituting the acrylic polymer.

The heating temperature in the case of heating for polymerization in the solution polymerization is, for example, 50 to 80 ℃. Examples of the heating time include 1 hour to 24 hours.

The weight average molecular weight of the acrylic polymer is preferably 10 to 500 ten thousand, more preferably 20 to 400 ten thousand, and further preferably 30 to 300 ten thousand. By adjusting the weight average molecular weight of the acrylic polymer within the above range, a pressure-sensitive adhesive layer having a lighter initial peel force, a lighter 180-degree peel force, and a faster wetting rate can be produced, and by combining with the specific base material layer used in the present invention, a surface protective film which can easily obtain a starting point for peeling from an adherend, can be easily peeled, and has a higher detection rate of scratches and foreign matter inclusion can be provided. When the weight average molecular weight is less than 10 ten thousand, the cohesive force may be reduced, and the adhesive residue may occur on the surface of the adherend from which the surface protective film of the present invention is peeled off, and the effects of uniform wettability and adhesiveness on the surface of the adherend after peeling off may not be obtained. If the weight average molecular weight exceeds 500 ten thousand, the wettability of the adherend surface after peeling the surface protective film of the present invention may become insufficient.

The glass transition temperature (Tg) of the acrylic polymer is preferably 0 ℃ or lower, more preferably-10 ℃ or lower. By adjusting the glass transition temperature of the acrylic polymer within the above range, a pressure-sensitive adhesive layer having a lighter initial peel force, a lighter 180-degree peel force, and a faster wetting rate can be obtained, and by combining with the specific base material layer used in the present invention, a surface protective film which can easily obtain a starting point for peeling from an adherend, and can be easily peeled, and further has a higher detection rate of damage and foreign matter inclusion can be provided. When the glass transition temperature is higher than 0 ℃, the wettability of the adherend surface after peeling the surface protective film of the present invention may become insufficient. The glass transition temperature of the acrylic polymer can be adjusted by changing the composition ratio of the monomer components constituting the acrylic polymer.

When the glass transition temperature of the homopolymer obtained from each monomer is Tgn (c), the glass transition temperature (Tg) can be determined by the following formula.

1/(Tg+273)＝Σ[Wn/(Tgn+273)]

Wherein Tg (. degree.C.) represents the glass transition temperature of the copolymer, Wn (-) represents the mass fraction of each monomer, Tgn (. degree.C.) represents the glass transition temperature of a homopolymer obtained from each monomer, and n represents the kind of each monomer.

The acid value of the acrylic polymer is preferably 15 or less. The acid value can be measured using an automatic titrator (COM-550, manufactured by Pouzolk industries, Ltd.) and calculated by the following formula.

A＝{(Y-X)×f×5.611}/M

A: acid value

Y: titration amount (ml) of sample solution

X: titration amount (ml) of solution of mixed solvent of only 50g

f: coefficient of titration solution

M: weight of Polymer sample (g)

The measurement conditions are as follows.

Sample solution: about 0.5g of the polymer sample was dissolved in 50g of a mixed solvent (toluene/2-propanol/distilled water: 50/49.5/0.5 by weight) as a sample solution.

Titration solution: 0.1N, 2-Propanolamine potassium hydroxide solution (for neutralization test of petroleum products, manufactured by Wako pure chemical industries, Ltd.)

An electrode: a glass electrode; GE-101, a reference electrode; RE-201

Measurement mode: petroleum product neutralization test 1

From the viewpoint of further improving the wettability of the surface protection film of the present invention, the acrylic adhesive may contain a surfactant.

Examples of the surfactant include: nonionic surfactants such as polyoxyalkylene fatty acid esters, polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene sorbitol fatty acid esters, polyoxyalkylene alkyl ethers, polyoxyalkylene alkyl allyl ethers, polyoxyalkylene alkyl phenyl ethers, polyoxyalkylene derivatives, polyoxyalkylene alkyl amines, polyoxyalkylene alkylamine fatty acid esters, sulfonates such as sodium alkylbenzenesulfonate, alkylsulfates such as sodium lauryl sulfate, dialkylarylsulfonates such as dialkylsulfosuccinates, higher fatty acid alkali salts, polyoxyalkylene alkyl ether sulfate salts, polyoxyalkylene alkyl ether phosphate salts, polyoxyalkylene alkyl phenyl ether sulfate salts, polyoxyalkylene alkyl phenyl ether phosphate salts, and anionic surfactants such as polyoxyalkylene alkyl ether phosphate salts, cationic surfactants having an alkylene oxide group, nonionic surfactants such as polyoxyalkylene alkyl ethers, polyoxyalkylene alkyl allyl ethers, polyoxyalkylene alkyl ether phosphate salts, and the like, cationic surfactants having an alkylene oxide group, nonionic surfactants such as alkyl group, polyoxyalkylene alkyl ether alkyl sulfonates, polyoxyalkylene alkyl allyl alkyl ether sulfonate salts, and, And a zwitterionic surfactant. The molecule may have a reactive substituent such as a (meth) acryloyl group or an allyl group. The number of the surfactants may be only 1, or may be 2 or more.

As the surfactant, an anionic surfactant is preferable from the viewpoint that the effects of the present invention can be sufficiently exhibited. Examples of anionic surfactants that can provide particularly excellent effects include: polyoxyalkylene alkyl phenyl ether sulfate (especially polyoxyethylene nonyl propenyl phenyl ether ammonium sulfate), dialkyl sulfosuccinic acid alkali metal salt (especially dioctyl sodium sulfosuccinate). Further, as the surfactant which can obtain excellent effects, compounds given by the formulae (1) and (2) can be mentioned.

[ chemical formula 24]

In the formula (1), R represents a C1-12 hydrocarbon group (particularly a C10 hydrocarbon group or a C12 hydrocarbon group), X represents an anionic hydrophilic group, and the average addition mole number n represents a number of 3-40.

[ chemical formula 25]

X in the formula (2) represents an anionic hydrophilic group.

Examples of the anionic hydrophilic group in the compound represented by formula (1) and the compound represented by formula (2) include groups represented by formulae (a1) to (a 2).

As the compound represented by the formula (1), for example, there can be mentioned: ammonium polyoxyethylene-1- (allyloxymethyl) alkylether sulfate, and the like. As the compound represented by the formula (2), for example, there can be mentioned: polyoxyethylene styrenated phenyl ether ammonium sulfate and the like.

As the anionic surfactant, general commercial products can be used, and examples thereof include: the trade name "Aquaron HS-10" (manufactured by first Industrial pharmaceutical Co., Ltd.), the trade name "NEOCOL P" (manufactured by first Industrial pharmaceutical Co., Ltd.), the trade name "HITENOL N-08" (manufactured by first Industrial pharmaceutical Co., Ltd.), and the like. Further, there may be mentioned: the trade name "HITENOL NF-13" (manufactured by first Industrial pharmaceutical Co., Ltd.), the trade name "HITENOL NF-17" (manufactured by first Industrial pharmaceutical Co., Ltd.), the trade name "Aquaron KH-10" (manufactured by first Industrial pharmaceutical Co., Ltd.), and the like.

The compounding amount of the surfactant is preferably 0.1 to 4% by weight, more preferably 0.15 to 3% by weight, relative to the total weight (100% by weight) of the adhesive layer.

The amount of the surfactant to be blended is preferably 0.2 to 4 parts by weight, more preferably 0.2 to 3 parts by weight, and still more preferably 0.3 to 3 parts by weight, based on 100 parts by weight of the acrylic polymer. By adjusting the amount of the surfactant to be blended with 100 parts by weight of the acrylic polymer within the above range, a pressure-sensitive adhesive layer having a lighter initial peel force, a lighter 180-degree peel force, and a faster wetting rate can be produced, and by combining with the specific base material layer used in the present invention, a surface protective film which can easily obtain a starting point for peeling from an adherend and can be easily peeled off, and further has a higher detection rate of scratches and foreign matter incorporation can be provided.

From the viewpoint of obtaining a moderate cohesive force, the acrylic adhesive may contain a crosslinking agent. Examples of the crosslinking agent include: isocyanate crosslinking agents, epoxy crosslinking agents, melamine crosslinking agents, aziridine crosslinking agents, metal chelate crosslinking agents, and the like. Among these, isocyanate-based crosslinking agents and epoxy-based crosslinking agents are preferable from the viewpoint of sufficiently exhibiting the effects of the present invention. The number of the crosslinking agents may be only 1, or may be 2 or more.

Examples of the isocyanate-based crosslinking agent include: lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate, alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate, aromatic isocyanates such as 2, 4-tolylene diisocyanate, 4' -diphenylmethane diisocyanate and xylylene diisocyanate, and isocyanate adducts such as trimethylolpropane/tolylene diisocyanate trimer adduct (trade name "CORONATE L", manufactured by Nippon polyurethane industries Co., Ltd.), trimethylolpropane/hexamethylene diisocyanate trimer adduct (trade name "CORONATE HL", manufactured by Nippon polyurethane industries Co., Ltd.), and isocyanurate of hexamethylene diisocyanate (trade name "CORONATE HX", manufactured by Nippon polyurethane industries Co., Ltd.).

Examples of the epoxy crosslinking agent include: bisphenol A, epichlorohydrin-based epoxy resins, ethylene glycidyl ether, polyethylene glycol diglycidyl ether, glycerol triglycidyl ether, 1, 6-hexanediol glycidyl ether, trimethylolpropane triglycidyl ether, diglycidylaniline, diamine glycidyl amine, N, N, N ', N' -tetraglycidyl m-xylylenediamine (product name "TETRAD-X" manufactured by Mitsubishi gas chemical Co., Ltd.), 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane (product name "TETRAD-C" manufactured by Mitsubishi gas chemical Co., Ltd.), and the like.

The compounding amount of the crosslinking agent is preferably 0.01 to 15% by weight, more preferably 0.5 to 10% by weight, relative to the total weight (100% by weight) of the adhesive layer.

The amount of the crosslinking agent blended is preferably 0.01 to 15 parts by weight, more preferably 0.5 to 10 parts by weight, still more preferably 2 to 9 parts by weight, and particularly preferably 6 to 8 parts by weight, based on 100 parts by weight of the acrylic polymer. By adjusting the amount of the crosslinking agent to be blended with 100 parts by weight of the acrylic polymer within the above range, a pressure-sensitive adhesive layer having a lighter initial peel force, a lighter 180-degree peel force, and a faster wetting rate can be obtained, and by combining with the specific base material layer used in the present invention, a surface protective film which can easily obtain a starting point of peeling from an adherend and can be easily peeled off and has a higher detection rate of scratches and foreign matter inclusion can be provided.

The acrylic adhesive may contain a crosslinking catalyst. Examples of the crosslinking catalyst include: metal crosslinking catalysts (particularly tin crosslinking catalysts) such as tetra-n-butyl titanate, tetra-isopropyl titanate, iron acetylacetonate, butyltin oxide, and dioctyltin dilaurate. The crosslinking catalyst may be only 1 kind or 2 or more kinds.

The compounding amount of the crosslinking catalyst is preferably 0.004 to 0.05% by weight, more preferably 0.004 to 0.03% by weight, relative to the total weight (100% by weight) of the adhesive layer.

The amount of the crosslinking catalyst to be blended is preferably 0.001 to 0.05 parts by weight, more preferably 0.003 to 0.04 parts by weight, and still more preferably 0.005 to 0.03 parts by weight, based on 100 parts by weight of the acrylic polymer. By adjusting the amount of the crosslinking catalyst to be blended with 100 parts by weight of the acrylic polymer within the above range, a pressure-sensitive adhesive layer having a lighter initial peel force, a lighter 180-degree peel force, and a faster wetting rate can be obtained, and by combining with the specific base material layer used in the present invention, a surface protective film which can easily obtain a starting point of peeling from an adherend and can be easily peeled off and has a higher detection rate of scratches and foreign matter inclusion can be provided. Further, by adjusting the compounding amount of the crosslinking catalyst to be within the above range with respect to 100 parts by weight of the acrylic polymer, crosslinking proceeds rapidly, and therefore productivity can be improved.

The acrylic adhesive may contain a crosslinking retarder. Examples of the crosslinking retarder include: beta-keto esters such as methyl acetoacetate, ethyl acetoacetate, octyl acetoacetate, oleyl acetoacetate, lauryl acetoacetate, and stearyl acetoacetate, and beta-diketones such as acetylacetone, 2, 4-hexanedione, and benzoylacetone. Of these, acetylacetone is preferable from the viewpoint that the effects of the present invention can be sufficiently exhibited. The number of crosslinking retarders may be only 1, or may be 2 or more.

The compounding amount of the crosslinking retarder is preferably 0.1 to 10% by weight, more preferably 0.1 to 3% by weight, relative to the total weight (100% by weight) of the adhesive layer.

The amount of the crosslinking retarder blended is preferably 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, and still more preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the acrylic polymer. By adjusting the amount of the crosslinking retarder to be blended with 100 parts by weight of the acrylic polymer within the above range, a pressure-sensitive adhesive layer having a lighter initial peel force, a lighter 180-degree peel force, and a faster wetting rate can be produced, and by combining with the specific base material layer used in the present invention, a surface protective film which can easily obtain a starting point for peeling from an adherend and can be easily peeled off, and further has a higher detection rate of scratches and foreign matter inclusion can be provided. Further, by adjusting the compounding amount of the crosslinking retarder with respect to 100 parts by weight of the acrylic polymer within the above range, the usable time of the acrylic adhesive can be extended.

The acrylic adhesive may contain a solvent. Examples of the solvent include: the solvent used in the above solution polymerization method.

The acrylic pressure-sensitive adhesive may contain additives such as a plasticizer, an antioxidant, a colorant (pigment, dye, etc.), an antistatic agent, and an tackifier resin within a range not to impair the effects of the present invention.

The acrylic adhesive can be prepared by mixing, for example, an acrylic polymer, a crosslinking agent, a crosslinking catalyst, a crosslinking retarder, other additives, and the like.

Method for producing surface protective film

The surface protective film of the present invention can be produced by any suitable method.

The surface protection film of the present invention can be preferably obtained by producing a laminate of a base layer and an adhesive layer.

The laminate of the base layer and the pressure-sensitive adhesive layer can be prepared by any suitable method such as the following method:

(1) a method of coating a solution or hot melt of a material for forming an adhesive layer on a base material layer,

(2) the method of transferring the adhesive layer coated and formed on the separator according to (1) onto the base material layer,

(3) a method of forming a coating by extruding a material for forming an adhesive layer onto a base material layer,

(4) a method of extruding the substrate layer and the adhesive layer in two or more layers,

(5) a method of single-layer laminating an adhesive layer on a substrate layer or a method of two-layer laminating an adhesive layer together with a lamination layer,

(6) a method of laminating two or more layers of an adhesive layer and a base material layer-forming material such as a film or a laminate layer.

Application

The surface protection film of the present invention can be easily obtained as a starting point for peeling from an adherend, and can be easily peeled off, and further, has a high detection rate of damage and contamination of foreign substances, and therefore, can be suitably used for surface protection of optical components and electronic components. That is, the optical member of the present invention is to which the surface protection film of the present invention is attached. The electronic component of the present invention is one to which the surface protection film of the present invention is attached.

Examples

The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples at all. The test and evaluation methods in examples and the like are as follows. In the case where "part" is described, the term "part by weight" is used unless otherwise specified, and in the case where "%" is described, the term "wt%" is used unless otherwise specified.

< weight average molecular weight >

The weight average molecular weight is a parameter measured by a Gel Permeation Chromatography (GPC) method. More specifically, the measurement can be carried out under the following conditions using a GPC measurement apparatus having the trade name "HLC-8220 GPC" (manufactured by Tosoh corporation), and the value can be calculated from the standard polystyrene conversion value.

(conditions for measuring molecular weight)

Sample concentration: 0.2 wt% (tetrahydrofuran solution)

Sample injection amount: 10 μ L

Sample chromatography column: TSKguardcolumn SuperHZ-H (1 root) + TSKgel SuperHZM-H (2 roots)

A reference chromatography column; TSKgel SuperH-RC (1 root)

Eluent: tetrahydrofuran (THF)

Flow rate: 0.6mL/min

The detector: differential Refractometer (RI)

Column temperature (measurement temperature): 40 deg.C

< Total light transmittance >

The total light transmittance was measured by using a haze meter (HM-150, manufactured by color technology research on village) according to the method prescribed in JIS K7361 "test method for total light transmittance of plastic-transparent Material".

< initial peeling force at a peeling speed of 0.3 m/min and a peeling angle of 90 degrees with respect to glass >

The pressure-sensitive adhesive layer side of the surface protection film cut into a width of 25mm and having the separator peeled therefrom was bonded to the surface of a glass plate (product name: microscope slide glass S, manufactured by Sonlang Nitri K.K.) using a 2kg roller, and then left at 23 ℃ and 50% RH for 20 minutes, and peeled under conditions of a peeling angle of 90 degrees and a peeling speed of 0.3 m/min, and the maximum force at the time when the surface protection film started to be peeled was read as an initial peeling force.

< peeling force at a peeling speed of 0.3 m/min and a peeling angle of 180 degrees with respect to glass >

The pressure-sensitive adhesive layer side of the surface protection film cut into a width of 25mm and from which the separator was peeled was bonded to the surface of a glass plate (product name: microscope slide glass S, manufactured by Sonlang Nitri K.K.) using a 2kg roller, and then left at 23 ℃ and 50% RH for 20 minutes, and peeled at a peeling angle of 180 ℃ and a peeling speed of 0.3 m/min, and the peel force of the surface protection film was measured.

< speed of wetting with respect to glass >

(1) A test piece (a surface protective film cut to 2.5 cm. times.15.0 cm) was held by hand so that the angle was 20 to 30 degrees in a state where a part of the pressure-sensitive adhesive layer surface of the test piece was in contact with an adherend (a glass plate (trade name: microscope slide S, manufactured by Song-Rao Seisaku Kogyo Co., Ltd.)).

(2) Next, the test piece was released from the hand, and the camera recorded the state in which the adhesive layer side of the test piece was in contact with the glass plate and was wetted in one direction from the contact portion. In the above (1), measurement and recording were not performed in a state where the test piece was wetted from a portion other than the portion where a part of the pressure-sensitive adhesive layer surface of the test piece was brought into contact with the glass plate of the adherend.

(3) The time until the test piece was completely wetted out was recorded in terms of wetting speed (cm)²Measured area (25 cm) in seconds²) The number of seconds recorded (seconds) was calculated as the wetting speed (cm)²In seconds).

(4) The measurement was performed 3 times independently, and the average value was used. In addition, the measurement was performed in a class 10000 clean room (temperature 23 ℃ C., humidity 50% RH).

< ease of inspection >

A flaw having a length of about 2mm was formed on a glass plate (trade name: microscope slide S, manufactured by Songlanza Kogyo Co., Ltd.) with a glass cutter, a surface protective film was attached to the surface opposite to the flaw-forming surface, and the flaw was evaluated as O if the flaw could be easily recognized by visual observation by reflection, and was evaluated as X if the flaw was difficult to be recognized.

< detachment of colored layer >

The surface of the surface protective film opposite to the pressure-sensitive adhesive layer was wiped 3 times with waste cotton ends dipped in ethyl acetate, and the case where no color transfer was observed to the waste cotton ends was evaluated as "o" and the case where no color transfer was observed was evaluated as "x".

[ production example 1 ]: production of colored substrate (A)

A polyethylene terephthalate film (manufactured by tokyo co., ltd., lumiror X30, thickness 50 μm) in which carbon black was kneaded in an amount of less than 1% was used as the colored substrate (a).

[ production example 2 ]: production of transparent substrate (B)

A transparent polyethylene terephthalate film (manufactured by tokyo corporation, lumiror S10, thickness 38 μm) was used as the transparent substrate (B).

[ production example 3 ]: production of colored substrate (C)

A transparent polyethylene terephthalate film (manufactured by tokyo corporation, lumiror S10, thickness 38 μm) was coated with black ink 5 times or more on one surface thereof by a gravure printing method to obtain a colored substrate (C).

[ example 1]

As the polyol, primiol S3011 (manufactured by asahi glass co., ltd., Mn 10000): 85 parts by weight of SANNIX GP3000 (Mn 3000, manufactured by sanyo chemical industries co., ltd): 13 parts by weight, 2 parts by weight of sannarix GP1000 (Mn 1000, manufactured by sanyo chemical industries co., ltd.) and, as the polyfunctional isocyanate compound, CORONATE HX (japan polyurethane industries co., ltd.): 18 parts by weight of a catalyst (trade name: iron acetylacetonate, manufactured by Nippon chemical industries Co., Ltd.): 0.08 parts by weight of Irganox1010 (manufactured by BASF) as a deterioration inhibitor: 0.5 part by weight of isopropyl myristate (trade name: EXCEPARL IPM, manufactured by Kao corporation) as a wettability additive: 30 parts by weight of ethyl acetate as a diluting solvent: 210 parts by weight, was stirred with a disperser, to obtain a polyurethane adhesive composition.

The obtained polyurethane adhesive composition was applied to the colored substrate (a) obtained in production example 1 with a coater so that the thickness after drying was 10 μm, and cured and dried under conditions of a drying temperature of 130 ℃ and a drying time of 2 minutes. In this manner, a pressure-sensitive adhesive layer composed of the polyurethane pressure-sensitive adhesive (a) was obtained on the colored substrate (a). Then, a surface-protecting film (1) was obtained on the silicone-treated surface of the polyester resin substrate having a thickness of 25 μm, which was silicone-treated on the surface of the pressure-sensitive adhesive layer to be bonded.

The results are shown in Table 1.

[ example 2]

As the polyol, primiol S3011 (manufactured by asahi glass co., ltd., Mn 10000): 85 parts by weight of SANNIX GP3000 (Mn 3000, manufactured by sanyo chemical industries co., ltd): 13 parts by weight, 2 parts by weight of sannarix GP1000 (Mn 1000, manufactured by sanyo chemical industries co., ltd.) and, as the polyfunctional isocyanate compound, CORONATE HX (japan polyurethane industries co., ltd.): 18 parts by weight of a catalyst (trade name: iron acetylacetonate, manufactured by Nippon chemical industries Co., Ltd.): 0.08 parts by weight of Irganox1010 (manufactured by BASF) as a deterioration inhibitor: 0.5 part by weight of isopropyl myristate (trade name: EXCEPARL IPM, manufactured by Kao corporation) as a wettability additive: 30 parts by weight of 1-ethyl-3-methylimidazolium bis (fluorosulfonyl) imide (trade name: ELEXCEL AS110, manufactured by first Industrial pharmaceutical Co., Ltd.) AS an antistatic agent: 1.25 parts by weight of a modified silicone (trade name: KF-6004, manufactured by shin-Etsu chemical Co., Ltd.): 0.01 parts by weight of ethyl acetate as a diluting solvent: 210 parts by weight, was stirred with a disperser, to obtain a polyurethane adhesive composition.

The obtained polyurethane adhesive composition was applied to the colored substrate (a) obtained in production example 1 with a coater so that the thickness after drying was 10 μm, and cured and dried under conditions of a drying temperature of 130 ℃ and a drying time of 2 minutes. In this manner, a pressure-sensitive adhesive layer composed of the polyurethane pressure-sensitive adhesive (B) was obtained on the colored substrate (a). Then, a surface-protecting film (2) was obtained on the silicone-treated surface of the polyester resin substrate having a thickness of 25 μm, which was silicone-treated on the surface of the pressure-sensitive adhesive layer to be bonded.

The results are shown in Table 1.

[ example 3]

Into a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube and a cooler, 200 parts by weight of 2-ethylhexyl acrylate, 8 parts by weight of 2-hydroxyethyl acrylate, 0.4 part by weight of 2, 2' -azobisisobutyronitrile as a polymerization initiator and 312 parts by weight of ethyl acetate as a solvent were charged, nitrogen gas was introduced while slowly stirring, and polymerization was carried out for 6 hours while maintaining the liquid temperature in the flask at about 65 ℃ to obtain an acrylic polymer solution (40% by weight). The weight average molecular weight of the acrylic polymer was 54 ten thousand, the glass transition temperature (Tg) was-68 ℃ and the acid value was 0.0.

The acrylic polymer solution (40 wt%) was diluted with ethyl acetate to 20 wt%, and isocyanurate of hexamethylene diisocyanate (trade name: CORONATE HX, manufactured by Nippon polyurethane industries, Ltd.) was added as a crosslinking agent to 100 parts by weight of the solid content in the solution: 4 parts by weight of dibutyltin dilaurate (manufactured by Tokyo Fine Chemical Co., Ltd., trade name: EMBILIZER OL-1, 0.5% by weight ethyl acetate solution) as a crosslinking catalyst: 0.015 part by weight of acetylacetone as a crosslinking retarder in an amount of 3 parts by weight based on the total solvent amount were mixed and stirred to obtain an acrylic pressure-sensitive adhesive composition.

The obtained acrylic pressure-sensitive adhesive composition was applied to the colored substrate (a) obtained in production example 1 with a coater so that the thickness after drying was 10 μm, cured at a drying temperature of 130 ℃ for a drying time of 2 minutes, and dried. Thus, a pressure-sensitive adhesive layer composed of the acrylic pressure-sensitive adhesive (A) was obtained on the colored substrate (A). Then, a surface-protecting film (3) was obtained on the silicone-treated surface of the polyester resin substrate having a thickness of 25 μm, which was silicone-treated on the surface of the pressure-sensitive adhesive layer to be bonded.

The results are shown in Table 1.

[ example 4]

Into a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube and a cooler, 200 parts by weight of 2-ethylhexyl acrylate, 8 parts by weight of 2-hydroxyethyl acrylate, 0.4 part by weight of 2, 2' -azobisisobutyronitrile as a polymerization initiator and 312 parts by weight of ethyl acetate as a solvent were charged, nitrogen gas was introduced while slowly stirring, and polymerization was carried out for 6 hours while maintaining the liquid temperature in the flask at about 65 ℃ to obtain an acrylic polymer solution (40% by weight). The weight average molecular weight of the acrylic polymer was 54 ten thousand, the glass transition temperature (Tg) was-68 ℃ and the acid value was 0.0.

The acrylic polymer solution (40 wt%) was diluted with ethyl acetate to 20 wt%, and isocyanurate of hexamethylene diisocyanate (trade name: CORONATE HX, manufactured by Nippon polyurethane industries, Ltd.) was added as a crosslinking agent to 100 parts by weight of the solid content in the solution: 5 parts by weight of ammonium polyoxyethylene nonylphenyl ether sulfate (trade name: Aquaron HS-10, manufactured by first Industrial pharmaceutical Co., Ltd.) as an anionic surfactant: 0.3 part by weight of dibutyltin dilaurate (manufactured by Tokyo Fine Chemical Co., Ltd., trade name: EMBILIZER OL-1, 0.5% by weight ethyl acetate solution) as a crosslinking catalyst: 0.015 part by weight of acetylacetone as a crosslinking retarder in an amount of 3 parts by weight based on the total solvent amount were mixed and stirred to obtain an acrylic pressure-sensitive adhesive composition.

The obtained acrylic pressure-sensitive adhesive composition was applied to the colored substrate (a) obtained in production example 1 with a coater so that the thickness after drying was 10 μm, cured at a drying temperature of 130 ℃ for a drying time of 2 minutes, and dried. Thus, a pressure-sensitive adhesive layer composed of the acrylic pressure-sensitive adhesive (B) was obtained on the colored substrate (A). Then, a surface-protecting film (4) was obtained on the silicone-treated surface of the polyester resin substrate having a thickness of 25 μm, which was silicone-treated on the surface of the pressure-sensitive adhesive layer to be bonded.

The results are shown in Table 1.

Comparative example 1

As the polyol, primiol S3011 (manufactured by asahi glass co., ltd., Mn 10000): 85 parts by weight of SANNIX GP3000 (Mn 3000, manufactured by sanyo chemical industries co., ltd): 13 parts by weight, 2 parts by weight of sannarix GP1000 (Mn 1000, manufactured by sanyo chemical industries co., ltd.) and, as the polyfunctional isocyanate compound, CORONATE HX (japan polyurethane industries co., ltd.): 18 parts by weight of a catalyst (trade name: iron acetylacetonate, manufactured by Nippon chemical industries Co., Ltd.): 0.08 parts by weight of Irganox1010 (manufactured by BASF) as a deterioration inhibitor: 0.5 part by weight of isopropyl myristate (trade name: EXCEPARL IPM, manufactured by Kao corporation) as a wettability additive: 30 parts by weight of ethyl acetate as a diluting solvent: 210 parts by weight, was stirred with a disperser, to obtain a polyurethane adhesive composition.

The obtained polyurethane adhesive composition was applied to the transparent substrate (B) obtained in production example 2 with a coater so that the thickness after drying was 10 μm, and cured and dried under conditions of a drying temperature of 130 ℃ and a drying time of 2 minutes. Thus, an adhesive layer comprising the polyurethane adhesive (a) was formed on the transparent substrate (B). Then, a surface-protecting film (C1) was obtained on the silicone-treated surface of the polyester resin substrate having a thickness of 25 μm, which was silicone-treated on the surface of the pressure-sensitive adhesive layer to be bonded.

The results are shown in Table 1.

Comparative example 2

A four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet tube and a cooler was charged with 190 parts by weight of butyl acrylate, 5 parts by weight of acrylic acid, 0.4 part by weight of 2, 2' -azobisisobutyronitrile as a polymerization initiator and 312 parts by weight of ethyl acetate as a solvent, and nitrogen was introduced while slowly stirring, and the polymerization reaction was carried out for 6 hours while keeping the liquid temperature in the flask at about 65 ℃ to obtain an acrylic polymer solution (40% by weight). The weight average molecular weight of the acrylic polymer was 54 ten thousand, the glass transition temperature (Tg) was-68 ℃ and the acid value was 0.0.

The acrylic polymer solution (40 wt%) was diluted with ethyl acetate to 20 wt%, and 1, 3-bis (N, N-glycidylaminomethyl) cyclohexane (trade name: TETRAD-C, manufactured by Mitsubishi gas chemical) as a crosslinking agent was added to 100 parts by weight of the solid content in the solution: 6 parts by weight, followed by mixing and stirring to obtain an acrylic pressure-sensitive adhesive composition.

The obtained acrylic pressure-sensitive adhesive composition was applied to the colored substrate (a) obtained in production example 1 with a coater so that the thickness after drying was 10 μm, cured at a drying temperature of 130 ℃ for a drying time of 2 minutes, and dried. Thus, a pressure-sensitive adhesive layer composed of the acrylic pressure-sensitive adhesive (C) was obtained on the colored substrate (A). Then, a surface-protecting film (C2) was obtained on the silicone-treated surface of the polyester resin substrate having a thickness of 25 μm, which was silicone-treated on the surface of the pressure-sensitive adhesive layer to be bonded.

The results are shown in Table 1.

Comparative example 3

As the polyol, primiol S3011 (manufactured by asahi glass co., ltd., Mn 10000): 85 parts by weight of SANNIX GP3000 (Mn 3000, manufactured by sanyo chemical industries co., ltd): 13 parts by weight, 2 parts by weight of sannarix GP1000 (Mn 1000, manufactured by sanyo chemical industries co., ltd.) and, as the polyfunctional isocyanate compound, CORONATE HX (japan polyurethane industries co., ltd.): 18 parts by weight of a catalyst (trade name: iron acetylacetonate, manufactured by Nippon chemical industries Co., Ltd.): 0.08 parts by weight of Irganox1010 (manufactured by BASF) as a deterioration inhibitor: 0.5 part by weight of isopropyl myristate (trade name: EXCEPARL IPM, manufactured by Kao corporation) as a wettability additive: 30 parts by weight of ethyl acetate as a diluting solvent: 210 parts by weight, was stirred with a disperser, to obtain a polyurethane adhesive composition.

The obtained polyurethane adhesive composition was applied to the colored substrate (C) obtained in production example 3 with a coater so that the thickness after drying was 10 μm, and cured and dried under conditions of a drying temperature of 130 ℃ and a drying time of 2 minutes. In this manner, a pressure-sensitive adhesive layer composed of the polyurethane pressure-sensitive adhesive (a) was obtained on the colored substrate (C). Then, a surface-protecting film (C3) was obtained on the silicone-treated surface of the polyester resin substrate having a thickness of 25 μm, which was silicone-treated on the surface of the pressure-sensitive adhesive layer to be bonded.

The results are shown in Table 1.

[ Table 1]

[ example 5]

The separator of the surface protection film (1) obtained in example 1 was peeled off, and the pressure-sensitive adhesive layer side was attached to a polarizing plate (product name "TEG 1465 DUHC" manufactured by hitto electrical corporation) as an optical member, to obtain an optical member to which a surface protection film was attached.

[ example 6]

The separator of the surface protection film (2) obtained in example 2 was peeled off, and the pressure-sensitive adhesive layer side was attached to a polarizing plate (product name "TEG 1465 DUHC" manufactured by hitto electrical corporation) as an optical member, to obtain an optical member to which a surface protection film was attached.

[ example 7]

The separator of the surface protection film (3) obtained in example 3 was peeled off, and the pressure-sensitive adhesive layer side was attached to a polarizing plate (product name "TEG 1465 DUHC" manufactured by hitto electrical corporation) as an optical member, to obtain an optical member to which a surface protection film was attached.

[ example 8]

The separator of the surface protection film (4) obtained in example 4 was peeled off, and the pressure-sensitive adhesive layer side was attached to a polarizing plate (product name "TEG 1465 DUHC" manufactured by hitto electrical corporation) as an optical member, to obtain an optical member to which a surface protection film was attached.

[ example 9]

The separator of the surface protection film (1) obtained in example 1 was peeled off, and the pressure-sensitive adhesive layer side was attached to a conductive film (product name "ELECRYSTA V270L-TFMP" manufactured by ritong electrical corporation) as an electronic component, to obtain an electronic component to which the surface protection film was attached.

[ example 10]

The separator of the surface protection film (2) obtained in example 2 was peeled off, and the pressure-sensitive adhesive layer side was attached to a conductive film (product name "ELECRYSTA V270L-TFMP" manufactured by ritong electrical corporation) as an electronic component, to obtain an electronic component to which the surface protection film was attached.

[ example 11]

The separator of the surface protection film (3) obtained in example 3 was peeled off, and the pressure-sensitive adhesive layer side was attached to a conductive film (product name "ELECRYSTA V270L-TFMP" manufactured by ritong electrical corporation) as an electronic component, to obtain an electronic component to which the surface protection film was attached.

[ example 12]

The separator of the surface protection film (4) obtained in example 4 was peeled off, and the pressure-sensitive adhesive layer side was attached to a conductive film (product name "ELECRYSTA V270L-TFMP" manufactured by ritong electrical corporation) as an electronic component, to obtain an electronic component to which the surface protection film was attached.

Industrial applicability

The surface protection film of the present invention can be suitably used for surface protection of optical parts and electronic parts.

Claims (4)

1. A surface-protecting film comprising a base layer mainly composed of a polyester resin and a pressure-sensitive adhesive layer,

the substrate layer is a colored substrate layer containing a black pigment,

the content ratio of the black pigment in the substrate layer is 0.01 to 20% by weight,

the black pigment comprises carbon black, titanium black, black chromium oxide, black iron oxide, carbon nano tubes, aniline black, perylene pigment or C.I. solvent black 123,

the total light transmittance of the surface protective film is 5% or less,

the surface protective film has an initial peel force at a peel speed of 0.3 m/min and a peel angle of 90 degrees of 1N/25mm or less with respect to glass,

the surface protective film has a peeling force at a peeling speed of 0.3 m/min and a peeling angle of 180 degrees of 0.1N/25mm or less with respect to glass,

the surface protective film had a wetting speed of 0.05cm with respect to glass²More than one second.

2. The surface protection film according to claim 1, wherein the adhesive layer contains at least 1 adhesive selected from a urethane-based adhesive and an acrylic adhesive.

3. An optical member to which the surface protective film according to claim 1 or 2 is attached.

4. An electronic component to which the surface protective film according to claim 1 or 2 is attached.

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