JPWO2020158414A1 - Surface protective film - Google Patents

Abstract

It has high adhesive strength and high light peelability, and after being attached to an adherend (preferably an adherend having a water contact angle of the surface of a certain level or higher), it is subjected to high temperature and high pressure treatment by an autoclave or the like, and then at room temperature. Provided is a surface protective film capable of suppressing the generation of air bubbles even when the pressure is returned. The surface protection film of the present invention is a surface protection film including a pressure-sensitive adhesive layer and a base material layer, and a free induction decay signal obtained by pulse NMR measurement of the pressure-sensitive adhesive layer is separated into two components by a nonlinear minimum square method. When this is done, the component with a short relaxation time is defined as the hard component (S), the component with a long relaxation time is defined as the soft component (L), and the spin-spin relaxation time T2 (L) of the proton of the soft component (L) measured at 30 ° C. The ratio T2 (L) 60 / T2 (L) 30 of L) 30 to the spin-spin relaxation time T2 (L) 60 of the proton of the soft component (L) measured at 60 ° C. is 2.15-3. It is 05, the shear adhesive force is 10 N / cm2 or more, and the high-speed peeling force is 0.8 N / 25 mm or less.

Description

The present invention relates to a surface protective film.

In the manufacturing process of optical members and electronic members, a surface protective film is generally attached to an exposed surface in order to prevent scratches on the surface during processing, assembly, inspection, transportation, and the like. Such a surface protective film is peeled off from an optical member or an electronic member when the need for surface protection is eliminated (Patent Document 1).

The surface protective film may be subjected to high temperature and high pressure treatment by an autoclave or the like in order to be crimped after being attached to the adherend. After performing such high temperature and high pressure treatment, it is necessary to return to normal temperature and pressure.

However, the conventional surface protective film has a problem that bubbles are likely to be generated when the surface protective film is attached to an adherend and then subjected to high temperature and high pressure treatment and then returned to normal temperature and pressure. In particular, the surface protective film designed to harden the adhesive in consideration of application to applications where light peelability is required is fine bubbles (typically) caused by foreign matter and processed edge roughness (burrs). Has a problem that bubbles with a diameter of about several millimeters are likely to be generated.

Therefore, surface protective films capable of solving such problems have been proposed so far (Patent Documents 2 and 3).

The surface protective film described in Patent Document 2 has a problem that it is heavy to peel off and cannot be applied to applications requiring light peelability.

The surface protective film for a polarizing plate described in Patent Document 3 has an object of preventing tunnel-like floating, and the level of light peelability is not sufficient.

In particular, when the surface protective film is applied to an adherend having a water contact angle of the surface of a certain level or more, the above-mentioned problem of bubble generation is remarkably observed.

Japanese Unexamined Patent Publication No. 2016-17109 Japanese Unexamined Patent Publication No. 11-961 JP-A-2007-304317

The subject of the present invention is that it has high adhesive strength and high light peelability, and is subjected to high-temperature and high-pressure treatment by an autoclave or the like after being attached to an adherend (preferably, an adherend having a water contact angle of a surface having a water contact angle of a certain level or more). It is an object of the present invention to provide a surface protective film capable of suppressing the generation of bubbles even when the pressure is returned to normal temperature and pressure thereafter.

The surface protective film of the present invention is
A surface protective film containing an adhesive layer and a base material layer.
When the free induction decay signal obtained by pulse NMR measurement of the pressure-sensitive adhesive layer is separated into two components by the non-linear least square method, the component with a short relaxation time is the hard component (S) and the component with a long relaxation time is the soft component (the component with a long relaxation time). _{L), the spin-spin relaxation time T2 (L) 30} of the proton of the soft component (L) measured at 30 ° C. and the spin-spin relaxation time T2 of the proton of the soft component (L) measured at 60 ° C. The ratio of (L) ₆₀ to T2 (L) ₆₀ / T2 (L) ₃₀ is 2.15 to 3.05.
Shear adhesive strength is 10 N / cm ² or more,
The high-speed peeling force is 0.8 N / 25 mm or less.

In one embodiment, the thickness of the pressure-sensitive adhesive layer is 1 μm to 500 μm.

In one embodiment, the thickness of the base material layer is 1 μm to 500 μm.

In one embodiment, the pressure-sensitive adhesive layer is composed of a pressure-sensitive adhesive formed from the pressure-sensitive adhesive composition, and the pressure-sensitive adhesive composition comprises a (meth) acrylic copolymer (A) and a polyfunctional alcohol (C). ) And the cross-linking agent (D).

In one embodiment, the (meth) acrylic copolymer (A) is a (meth) acrylic acid alkyl ester, (a2), wherein the alkyl group of the (a1 component) alkyl ester moiety has 4 to 12 carbon atoms. It is formed by polymerization from the composition (a) containing (component) an (meth) acrylic acid ester having an OH group.

In one embodiment, the composition (a) comprises (meth) acrylic acid.

In one embodiment, the polyfunctional alcohol (C) has 3 to 6 functional groups.

In one embodiment, the polyfunctional alcohol (C) has a number average molecular weight of 50 to 10,000.

In one embodiment, the pressure-sensitive adhesive composition is polymerized from the composition (b) containing a (meth) acrylic acid alkyl ester in which the alkyl group of the (b1 component) alkyl ester moiety is an alicyclic hydrocarbon group. Contains the (meth) acrylic copolymer (B) to be formed.

In one embodiment, the composition (b) comprises a (meth) acrylic acid alkyl ester in which the alkyl group of the (b2 component) alkyl ester moiety has 1-3 carbon atoms.

In one embodiment, the composition (b) comprises a mercaptan.

In one embodiment, the Tg of the (meth) acrylic copolymer (B) is 50 ° C to 250 ° C.

In one embodiment, the weight average molecular weight of the (meth) acrylic copolymer (B) is 1000 to 30,000.

In one embodiment, the pressure-sensitive adhesive composition comprises an ionic liquid.

In one embodiment, the surface protective film of the present invention has 10 or less bubbles generated after high temperature and high pressure treatment.

In one embodiment, the surface protective film of the present invention is used to protect the surface of an adherend having a water contact angle of 60 degrees or more on the surface.

According to the present invention, it has high adhesive strength and high light peelability, and is subjected to high-temperature and high-pressure treatment by an autoclave or the like after being attached to an adherend (preferably, an adherend having a water contact angle of a surface having a water contact angle of a certain level or more). It is possible to provide a surface protective film capable of suppressing the generation of bubbles even when the pressure is returned to normal temperature and pressure thereafter.

It is a schematic sectional drawing of one Embodiment of the surface protection film of this invention. It is a schematic sectional drawing which shows the manufacturing method of the polarizing plate (A) used for the adherend (A). It is a schematic sectional drawing which shows the manufacturing method of the polarizing element used for the adherend (C).

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

In the present specification, the expression "(meth) acrylic" means "acrylic and / or methacrolein", and the expression "(meth) acrylate" means "acrylate and / or methacrylate". When the expression "(meth) allyl" is used, it means "allyl and / or methacrolein", and when the expression "(meth) acrolein" is used, "acrolein and / or methacrolein" is used. It means "rain".

≪≪Surface protection film≫≫
The surface protective film of the present invention includes an adhesive layer and a base material layer.

The surface protective film of the present invention may be provided with any suitable other member as long as it has the pressure-sensitive adhesive layer and the base material layer, as long as the effects of the present invention are not impaired. Typically, the surface protective film of the present invention comprises a base material layer and an adhesive layer.

FIG. 1 is a schematic cross-sectional view of a surface protective film according to an embodiment of the present invention. In FIG. 1, the surface protective film 10 includes a base material layer 1 and an adhesive layer 2. In FIG. 1, the base material layer 1 and the pressure-sensitive adhesive layer 2 are directly laminated.

In FIG. 1, the surface of the pressure-sensitive adhesive layer 2 on the opposite side of the base material layer 1 may be provided with an arbitrary suitable release liner for protection until use or the like (not shown). As the release liner, for example, the surface of the base material (liner base material) such as paper or plastic film is treated with silicone, and the surface of the base material (liner base material) such as paper or plastic film is made of polyolefin resin. Examples include a laminated release liner. Examples of the plastic film as the liner base material include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, and polybutylene terephthalate film. Examples thereof include a polyurethane film and an ethylene-vinyl acetate copolymer film. The plastic film as the liner base material is preferably a polyethylene film.

The thickness of the release liner is preferably 1 μm to 500 μm, more preferably 3 μm to 450 μm, still more preferably 5 μm to 400 μm, and particularly preferably 10 μm to 300 μm.

The thickness of the surface protective film of the present invention is preferably 10 μm to 500 μm, more preferably 15 μm to 400 μm, further preferably 20 μm to 350 μm, particularly preferably 25 μm to 300 μm, and most preferably 30 μm to 30 μm. It is 250 μm.

The surface protective film of the present invention is cut into a size of 10 mm in width and 100 mm in length, and after the separator is peeled off, the water contact angle of the surface is set so that ^{the adhesive (adhesive) area of the exposed adhesive layer is 1 cm 2.} It is bonded to an adherend of 60 degrees or more (for example, an unsheared TAC polarizing plate obtained in Production Example 5 described later (width 70 mm, length 100 mm, water contact angle = 69.9 degrees)) and attached to 23 ° C × 50. After standing for 30 minutes in an environment of% RH, the film is peeled in the shearing direction at a peeling speed of 0.06 mm / min, and the maximum load (N / cm ² ) at that time is used as the shear adhesive force, and the shear adhesive is measured under the above conditions. force, preferably 10 N / cm ² or more, more preferably ^{10N / cm 2 ~80N / cm 2} , more preferably from ^{10N / cm 2 ~50N / cm 2} , particularly preferably 15N / cm ² a ~45N / cm ^2, and most preferably ^{20N / cm 2 ~40N / cm 2} . When the shear adhesive force is within the above range, the surface protective film of the present invention can exhibit high adhesive force.

The surface protective film of the present invention is an adherend having a water contact angle of 60 degrees or more after cutting the surface protective film into a size of 25 mm in width and 100 mm in length and peeling off the separator (for example, in Production Example 5 described later). After crimping to the surface of the obtained unkenken TAC polarizing plate (width 70 mm, length 100 mm, water contact angle = 69.9 degrees) with a hand roller, under crimping conditions of 0.25 MPa and 0.3 m / min. Laminate to prepare an evaluation sample, peel off the separator on the polarizing plate side of the evaluation sample, and press it onto a slide glass with a thickness of 1.3 mm, a width of 65 mm, and a length of 165 mm with a hand roller to create an environment of 23 ° C x 50% RH. After leaving it underneath for 30 minutes, one end of the surface protective film was peeled off at a tensile speed of 30 m / min and a peeling angle of 180 ° with a universal tensile tester in an environment of 23 ° C. × 50% RH. The adhesive force at this time is defined as a high-speed peeling force, and the high-speed peeling force measured under the above conditions is preferably 10 N / 25 mm or less, more preferably 0.01 N / 25 mm to 10 N / 25 mm, and further preferably 0.01 N. It is / 25 mm to 5 N / 25 mm, particularly preferably 0.05 N / 25 mm to 3 N / 25 mm, and most preferably 0.05 N / 25 mm to 2 N / 25 mm. If the high-speed peeling force is within the above range, the surface protective film of the present invention can exhibit high light peeling property.

The surface protective film of the present invention is an adherend having a water contact angle of 60 degrees or more on the surface after cutting the surface protective film into a size of 65 mm in width and 90 mm in length and peeling off the separator (for example, a production example described later). After crimping to the surface of the unkenken TAC polarizing plate (width 70 mm, length 100 mm, water contact angle = 69.9 degrees) obtained in step 5 with a hand roller, crimping at 0.25 MPa and 0.3 m / min. Laminate under the conditions, cut four sides from the surface protection film side with a cutting machine so that the width is 50 mm and the length is 80 mm, use it as an evaluation sample, peel off the separator on the polarizing plate side, and remove the separator on the polarizing plate side to have a thickness of 1.3 mm and a width of 65 mm. , Crimped to a slide glass with a length of 165 mm with a hand roller, left in an environment of 23 ° C × 50% RH for 30 minutes, then autoclaved in an environment of 50 ° C and 5 atm for 40 minutes, and then at room temperature. After returning to the pressure, the number of bubbles generated at the end of the polarizing plate immediately after is counted to obtain the number of bubbles generated (the number of bubbles generated after high-temperature and high-pressure treatment), and the number of bubbles generated is preferably 10 or less, more preferably. The number is 8 or less, more preferably 5 or less, particularly preferably 3 or less, and most preferably 0. As described above, the surface protective film of the present invention can suppress the generation of air bubbles even if it is attached to an adherend and then subjected to high temperature and high pressure treatment by an autoclave or the like and then returned to normal temperature and pressure.

The surface protective film of the present invention can be produced by any suitable method. As such a manufacturing method, for example,
(1) A method of applying a solution of a material for forming an adhesive layer or a thermal melt solution onto a base material layer,
(2) A method of transferring a pressure-sensitive adhesive layer formed by applying a solution of a material for forming a pressure-sensitive adhesive layer or a heat-melting liquid on a separator onto a base material layer.
(3) A method of extruding a material for forming an adhesive layer onto a base material layer to form and apply the adhesive layer.
(4) A method of extruding a base material layer and an adhesive layer in two or multiple layers,
(5) A method of laminating a single layer of an adhesive layer on a base material layer or a method of laminating two layers of an adhesive layer together with a laminating layer.
(6) A method of laminating a pressure-sensitive adhesive layer and a base material layer forming material such as a film or a laminate layer in two or multiple layers.
It can be carried out according to any suitable manufacturing method such as.

As the coating method, for example, a roll coater method, a comma coater method, a die coater method, a reverse coater method, a silk screen method, a gravure coater method and the like can be used.

≪Adhesive layer≫
The pressure-sensitive adhesive layer is composed of a pressure-sensitive adhesive formed from the pressure-sensitive adhesive composition. As a method for producing the pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer may be produced by any suitable production method. Examples of such a manufacturing method include a method in which a pressure-sensitive adhesive composition is applied onto a base material layer and, if necessary, heated or dried to form a pressure-sensitive adhesive layer on the base material layer. Examples of the method for applying the pressure-sensitive adhesive composition of the present invention onto the substrate layer include roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating method, and extrusion coating using a die coater. Be done.

The thickness of the pressure-sensitive adhesive layer is preferably 1 μm to 500 μm, more preferably 2 μm to 300 μm, further preferably 3 μm to 200 μm, particularly preferably 4 μm to 150 μm, and most preferably 5 μm to 100 μm. ..

The pressure-sensitive adhesive composition is preferably preferred.
(1) A pressure-sensitive adhesive composition containing a (meth) acrylic copolymer (A), a polyfunctional alcohol (C), and a cross-linking agent (D).
(2) Adhesive composition containing a polyol and a polyfunctional isocyanate,
At least one selected from.

An acrylic pressure-sensitive adhesive can be obtained from the above (1), and a urethane-based pressure-sensitive adhesive can be obtained from the above (2).

The pressure-sensitive adhesive composition more preferably contains a (meth) acrylic copolymer (A), a polyfunctional alcohol (C), and a cross-linking agent (D).

The pressure-sensitive adhesive layer is preferably formed by causing the pressure-sensitive adhesive composition to undergo a characteristic cross-linking reaction. Specifically, from the results of various studies, the polyfunctional alcohol (C) is contained in the pressure-sensitive adhesive composition, so that the polyfunctional alcohol (C) and the cross-linking agent (D) are combined to form a specific type. It is presumed that the (meth) acrylic copolymer (A) obtained from the composition requiring the monomer component of the above is imparted with a characteristic viaduct structure. As a result, the pressure-sensitive adhesive layer has high adhesive strength and high light peelability, and the surface protective film of the present invention having the pressure-sensitive adhesive layer is subjected to high-temperature and high-pressure treatment by an autoclave or the like after being attached to an adherend. It is presumed that the generation of air bubbles can be suppressed even if the pressure is returned to normal temperature and pressure thereafter.

Further, in designing the pressure-sensitive adhesive layer (or the pressure-sensitive adhesive constituting the pressure-sensitive adhesive) of the surface protective film of the present invention to have the characteristic viaduct structure as described above, the pressure-sensitive adhesive composition will be described later. It has been found that when a characteristic (meth) acrylic copolymer (B) is contained, an increase in adhesive strength over time can be effectively suppressed, and more excellent light peelability can be exhibited.

It is observed from several viewpoints that the pressure-sensitive adhesive layer has a viaduct structure. These viewpoints include, for example, the relaxation time observed by pulse NMR.

Since the reciprocal of the spin-spin relaxation time and the cross-linking density of the polymer (degree of constraint of molecular motion) show a positive linear correlation, the spin-spin relaxation time T2 is an index of the cross-linking density of the polymer components constituting the pressure-sensitive adhesive layer. Can be. Specifically, when the pulse NMR of the polymer is measured, one or more components (for example, 2 or 3) spin-spin relaxation time T2 can be obtained, and the magnitude of the spin-spin relaxation time T2 constitutes the pressure-sensitive adhesive layer. Corresponds to the high and low crosslink density of polymer components. The method of separating the components according to the magnitude of the spin-spin relaxation time is divided by the nonlinear square method, and if the analysis residue (offset) is less than 10%, it can be judged that the resolution is appropriate. Assuming that the component having a high cross-linking density when separated into two components is the S component and the component having a low cross-linking density is the L component and the spin-spin relaxation times are T2 (S) and T2 (L), the cross-linking is constrained by molecular motion. The spin-spin relaxation time T2 (S) of the dense polymer component S can be small, and the pin-spin relaxation time T2 (L) of the low crosslink polymer component L can be large.

When the free induction decay signal obtained by pulse NMR measurement of the pressure-sensitive adhesive layer is separated into two components by the nonlinear minimum square method, the component with a short relaxation time is the hard component (S) and the component with a long relaxation time is the soft component (L). _{), The spin-spin relaxation time T2 (L) 30} of the proton of the soft component (L) measured at 30 ° C. and the spin-spin relaxation time T2 (L) of the proton of the soft component (L) measured at 60 ° C. L) _{The ratio of 60} to T2 (L) ₆₀ / T2 (L) ₃₀ is preferably 1 or more, more preferably 1 to 5, still more preferably 1.5 to 4, and particularly preferably 2 to 2. It is 3.5, most preferably 2.15 to 3.

The T2 (L) ₃₀ is preferably 500 μsec to 5000 μsec, more preferably 700 μsec to 4000 μsec, still more preferably 800 μsec to 3000 μsec, and particularly preferably 900 μsec to 2500 μsec. Most preferably, it is 1000 μsec to 2300 μsec.

The T2 (L) ₆₀ is preferably 500 μsec to 9000 μsec, more preferably 1000 μsec to 8000 μsec, still more preferably 1500 μsec to 7000 μsec, and particularly preferably 2000 μsec to 6500 μsec. Most preferably, it is 2500 μsec to 6000 μsec.

The fact that the pressure-sensitive adhesive layer has a viaduct structure may be reflected in the degree of swelling. When the pressure-sensitive adhesive layer has a viaduct structure, the degree of swelling of the pressure-sensitive adhesive layer is preferably 250% or less, more preferably 80% to 250%, still more preferably 85% to 240%, and particularly. It is preferably 90% to 235%, and most preferably 95% to 230%.

The degree of swelling can be measured by, for example, the following method. That is, about 0.1 g of the polymer after the cross-linking reaction was collected, wrapped in a porous tetrafluoroethylene sheet (trade name "NTF1122", manufactured by Nitto Denko Co., Ltd.) with an average pore size of 0.2 μm, and then tied with octopus thread. The weight at that time was measured, and the weight was taken as the weight before immersion (the total weight of the polymer, the tetrafluoroethylene sheet and the octopus yarn), while the total weight of the tetrafluoroethylene sheet and the octopus yarn was also measured. Let the weight be the package weight. Next, the above polymer wrapped in a tetrafluoroethylene sheet and bound with octopus thread (referred to as "sample") was placed in a 50 ml container filled with ethyl acetate, allowed to stand at 23 ° C. for 7 days, and then the container. The sample after soaking in ethyl acetate is taken out from the sample, and the ethyl acetate adhering to the sample is sufficiently wiped off with a waste cloth to measure the weight. After drying in a time dryer to remove ethyl acetate, the weight is measured, and the weight is taken as the weight after drying, and the degree of swelling can be calculated from the following formula.
Swelling degree (%) = (ab) / (c-b) × 100 (1)
In the formula (1), a is the weight after immersion, b is the weight of the bag, and c is the weight after drying.
Further, when collecting the polymer after cross-linking, it may be collected from the pressure-sensitive adhesive layer surface of the surface protective film, or the same pressure-sensitive adhesive layer as that separately provided on the surface protection film is applied to a silicone separator or the like and dried. It may be collected from.

≪Adhesive composition≫
The pressure-sensitive adhesive composition contains a (meth) acrylic copolymer (A). The (meth) acrylic copolymer (A) may be of only one type or of two or more types.

The content ratio of the (meth) acrylic copolymer (A) in the pressure-sensitive adhesive composition is preferably 50% by weight to 99.9% by weight, more preferably, in that the effect of the present invention can be more exhibited. Is 60% by weight to 99.5% by weight, more preferably 70% by weight to 99% by weight, particularly preferably 80% by weight to 99% by weight, and most preferably 85% by weight to 99% by weight. be.

The pressure-sensitive adhesive composition comprises a polyfunctional alcohol (C). The polyfunctional alcohol (C) may be only one kind or two or more kinds.

As the content of the polyfunctional alcohol (C) in the pressure-sensitive adhesive composition, any appropriate content may be adopted as long as the effect of the present invention is not impaired. Such a content is preferably 0.01 part by weight with respect to the solid content (100 parts by weight) of the (meth) acrylic copolymer (A) in that the effect of the present invention can be more exhibited. It is 10 parts by weight, more preferably 0.05 parts by weight to 7 parts by weight, further preferably 0.1 parts by weight to 5 parts by weight, and particularly preferably 0.2 parts by weight to 3 parts by weight. be.

The pressure-sensitive adhesive composition contains a cross-linking agent (D). The cross-linking agent (D) may be only one kind or two or more kinds.

As the content of the cross-linking agent (D) in the pressure-sensitive adhesive composition, any appropriate content can be adopted as long as the effect of the present invention is not impaired. Such a content is preferably 0.01 part by weight with respect to the solid content (100 parts by weight) of the (meth) acrylic copolymer (A) in that the effect of the present invention can be more exhibited. It is ~ 50 parts by weight, more preferably 0.01 part by weight to 30 parts by weight, further preferably 0.01 part by weight to 20 parts by weight, and particularly preferably 0.01 part by weight to 10 parts by weight. be.

The pressure-sensitive adhesive composition contains a (meth) acrylic copolymer (A), a polyfunctional alcohol (C), and a cross-linking agent (D), and any other suitable component is used as long as the effect of the present invention is not impaired. May include. Such other components may be only one kind or two or more kinds.

The pressure-sensitive adhesive composition may be prepared by blending its constituents by any suitable method.

<(Meta) acrylic copolymer (A)>
As the (meth) acrylic copolymer (A), any suitable (meth) acrylic copolymer may be adopted as long as the effects of the present invention are not impaired.

The weight average molecular weight of the (meth) acrylic copolymer (A) is preferably 100,000 to 5 million, more preferably 200,000 to 4 million, in that the effects of the present invention can be more exhibited. It is more preferably 250,000 to 3.5 million, and particularly preferably 300,000 to 3 million.

The (meth) acrylic copolymer (A) preferably has 4 to 12 carbon atoms in the alkyl group of the (a1 component) alkyl ester moiety in that the effects of the present invention can be further exhibited (meth). ) A (meth) acrylic copolymer formed by polymerization from the composition (a) containing an acrylic acid alkyl ester and a (meth) acrylic acid ester having an OH group (component a2).

(A1 component) may be only one kind or two or more kinds. (A2 component) may be only one kind or two or more kinds.

Examples of the (meth) acrylic acid alkyl ester (a1 component) in which the alkyl group of the alkyl ester moiety has 4 to 12 carbon atoms include n-butyl (meth) acrylic acid, isobutyl (meth) acrylic acid, and (meth). S-butyl acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2--octyl (meth) acrylate Ethylhexyl, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate And so on. Among these, 2-ethylhexyl (meth) acrylate is preferable, and 2-ethylhexyl acrylate (2EHA) is more preferable, because the effects of the present invention can be more exhibited.

(Meta) Acrylic acid alkyl ester (a1 component) in which the number of carbon atoms of the alkyl group of the alkyl ester moiety is 4 to 12 with respect to the total amount (100% by weight) of the monomer components constituting the (meth) acrylic copolymer (A). The content of the above is preferably 50% by weight to 99.9% by weight, more preferably 60% by weight to 99.9% by weight, still more preferably 70, in that the effect of the present invention can be more exhibited. It is from% to 99.9% by weight, particularly preferably 80% by weight to 99.9% by weight, and most preferably 85% by weight to 99.9% by weight.

Examples of the (meth) acrylic acid ester (a2 component) having an OH group include (meth) hydroxyethyl acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate. ) Acrylic acid ester and the like. Among these, 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are preferable, and 2-hydroxy acrylate is more preferable, because the effects of the present invention can be more exhibited. Ethyl (HEA), 4-hydroxybutyl acrylate (4HBA), and particularly preferably 4-hydroxybutyl acrylate (4HBA).

The content ratio of the (meth) acrylic acid ester (a2 component) having an OH group to the total amount (100% by weight) of the monomer components constituting the (meth) acrylic copolymer (A) further expresses the effect of the present invention. In terms of possible, it is preferably 0.1% by weight to 50% by weight, more preferably 0.1% by weight to 40% by weight, still more preferably 0.2% by weight to 30% by weight, and particularly. It is preferably 0.5% by weight to 20% by weight, and most preferably 1% by weight to 10% by weight.

The composition (a) may contain a copolymerizable monomer other than (a1 component) and (a2 component). The copolymerizable monomer may be only one kind or two or more kinds.

The composition (a) may contain (meth) acrylic acid as a copolymerizable monomer. Examples of the (meth) acrylic acid include at least one selected from the group consisting of acrylic acid and methacrylic acid, and acrylic acid is preferable in that the effects of the present invention can be further exhibited.

The content ratio of (meth) acrylic acid with respect to the total amount (100% by weight) of the monomer components constituting the (meth) acrylic copolymer (A) is preferably 0 weight in that the effect of the present invention can be more exhibited. % To 10% by weight, more preferably 0% by weight to 8% by weight, still more preferably 0% by weight to 5% by weight, particularly preferably 0% by weight to 2% by weight, and most preferably. It is 0% by weight to 1% by weight.

Examples of the copolymerizable monomer other than (meth) acrylic acid include itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid, and acid anhydrides thereof (for example, maleic anhydride, itaconic anhydride and the like). Monomer containing a carboxyl group (excluding (meth) acrylic acid); (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl Amido group-containing monomers such as (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide; aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, (meth) acrylic Amino group-containing monomers such as t-butylaminoethyl acid; glycidyl (meth) acrylate, epoxy group-containing monomers such as (meth) methyl glycidyl acrylate; cyano group-containing monomers such as acrylonitrile and methacrylonitrile; N-vinyl- Heterocyclic-containing vinyl monomers such as 2-pyrrolidone, (meth) acryloylmorpholine, N-vinylpiperidone, N-vinylpiperazine, N-vinylpyrrole, N-vinylimidazole, vinylpyridine, vinylpyrimidine, vinyloxazole; sodium vinylsulfonate. Sulphonic acid group-containing monomers such as 2-hydroxyethylacryloyl phosphate and other phosphate group-containing monomers; imide group-containing monomers such as cyclohexylmaleimide and isopropylmaleimide; isocyanate group-containing monomers such as 2-methacryloyloxyethyl isocyanate; cyclopentyl ( (Meta) acrylic acid ester having an alicyclic hydrocarbon group such as meta) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentadienyl (meth) acrylate; phenyl (meth) acrylate, phenoxyethyl (Meta) acrylic acid ester having an aromatic hydrocarbon group such as (meth) acrylate and benzyl (meth) acrylate; Vinyl ester such as vinyl acetate and vinyl propionate; Aromatic vinyl compound such as styrene and vinyl toluene; Ethylene, Examples thereof include olefins and dienes such as butadiene, isoprene and isobutylene; vinyl ethers such as vinyl alkyl ether; vinyl chloride; and the like.

As the copolymerizable monomer, a polyfunctional monomer may also be adopted. The polyfunctional monomer means a monomer having two or more ethylenically unsaturated groups in one molecule. As the ethylenically unsaturated group, any suitable ethylenically unsaturated group can be adopted as long as the effect of the present invention is not impaired. Examples of such an ethylenically unsaturated group include radically polymerizable functional groups such as a vinyl group, a propenyl group, an isopropenyl group, a vinyl ether group (vinyloxy group) and an allyl ether group (allyloxy group). Examples of the polyfunctional monomer include hexanediol di (meth) acrylate, butanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, and neopentyl glycol. Di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethyl propanthry (meth) acrylate, tetramethylol methanetri (meth) acrylate, allyl. Examples thereof include (meth) acrylate, vinyl (meth) acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, and urethane acrylate. Such a polyfunctional monomer may be only one kind, or may be two or more kinds.

As the copolymerizable monomer, (meth) acrylic acid alkoxyalkyl ester may also be adopted. Examples of the (meth) acrylate alkoxyalkyl ester include (meth) acrylate 2-methoxyethyl, (meth) acrylate 2-ethoxyethyl, (meth) acrylate methoxytriethylene glycol, and (meth) acrylate 3-. Examples thereof include methoxypropyl, 3-ethoxypropyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, and 4-ethoxybutyl (meth) acrylate. The (meth) acrylic acid alkoxyalkyl ester may be only one kind or two or more kinds.

The composition (a) may contain any suitable other ingredients as long as the effects of the present invention are not impaired. Examples of such other components include polymerization initiators, chain transfer agents, solvents and the like. As the content of these other components, any appropriate content may be adopted as long as the effect of the present invention is not impaired.

As the polymerization initiator, a thermal polymerization initiator, a photopolymerization initiator (photoinitiator), or the like can be adopted depending on the type of the polymerization reaction. The polymerization initiator may be only one kind or two or more kinds.

The thermal polymerization initiator can be preferably adopted when the acrylic polymer is obtained by solution polymerization. Examples of such a thermal polymerization initiator include an azo-based polymerization initiator, a peroxide-based polymerization initiator (for example, dibenzoyl peroxide, tert-butyl permalate, etc.), a redox-based polymerization initiator, and the like. .. Among these thermal polymerization initiators, the azo-based polymerization initiator disclosed in JP-A-2002-69411 is particularly preferable. Such an azo-based polymerization initiator is preferable in that the decomposition product of the polymerization initiator does not easily remain in the acrylic polymer as a portion that causes the generation of heat-generating gas (out gas). Examples of the azo-based polymerization initiator include 2,2'-azobisisobutyronitrile (hereinafter, may be referred to as AIBN) and 2,2'-azobis-2-methylbutyronitrile (hereinafter, referred to as AMBN). , 2,2'-azobis (2-methylpropionic acid) dimethyl, 4,4'-azobis-4-cyanovalerian acid and the like. The amount of the azo-based polymerization initiator used is preferably 0.001 part by weight to 1 part by weight with respect to the total amount (100 parts by weight) of the monomer components constituting the (meth) acrylic copolymer (A). It is more preferably 0.005 part by weight to 1 part by weight, further preferably 0.005 part by weight to 0.8 part by weight, and particularly preferably 0.01 part by weight to 0.8 part by weight, most preferably. It is preferably 0.01 parts by weight to 0.7 parts by weight.

The photopolymerization initiator can be preferably adopted when the (meth) acrylic copolymer (A) is obtained by active energy ray polymerization. Examples of the photopolymerization initiator include a benzoin ether-based photopolymerization initiator, an acetophenone-based photopolymerization initiator, an α-ketol-based photopolymerization initiator, an aromatic sulfonyl chloride-based photopolymerization initiator, and a photoactive oxime-based photopolymerization initiator. Examples thereof include agents, benzoin-based photopolymerization initiators, benzyl-based photopolymerization initiators, benzophenone-based photopolymerization initiators, ketal-based photopolymerization initiators, thioxanthone-based photopolymerization initiators, and the like.

Examples of the benzoin ether-based photopolymerization initiator include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethan-1-one, and anisole. Examples include methyl ether. Examples of the acetophenone-based photopolymerization initiator include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenylketone, 4-phenoxydichloroacetophenone, and 4- (t-butyl). Examples include dichloroacetophenone. Examples of the α-ketol-based photopolymerization initiator include 2-methyl-2-hydroxypropiophenone, 1- [4- (2-hydroxyethyl) phenyl] -2-methylpropan-1-one, and the like. .. Examples of the aromatic sulfonyl chloride-based photopolymerization initiator include 2-naphthalene sulfonyl chloride and the like. Examples of the photoactive oxime-based photopolymerization initiator include 1-phenyl-1,1-propanedione-2- (o-ethoxycarbonyl) -oxime. Examples of the benzoin-based photopolymerization initiator include benzoin and the like. Examples of the benzyl-based photopolymerization initiator include benzyl and the like. Examples of the benzophenone-based photopolymerization initiator include benzophenone, benzoylbenzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, α-hydroxycyclohexylphenylketone and the like. Examples of the ketal-based photopolymerization initiator include benzyldimethyl ketal and the like. Examples of the thioxanthone-based photopolymerization initiator include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, and dodecylthioxanthone.

The amount of the photopolymerization initiator used is preferably 0.001 part by weight to 10 parts by weight, based on the total amount (100 parts by weight) of the monomer components constituting the (meth) acrylic copolymer (A). It is preferably 0.005 parts by weight to 8 parts by weight, more preferably 0.01 parts by weight to 5 parts by weight, particularly preferably 0.02 parts by weight to 5 parts by weight, and most preferably 0.05 parts by weight. It is 3 parts by weight by weight.

As a method for obtaining the (meth) acrylic copolymer (A), for example, as a method for synthesizing the (meth) acrylic copolymer, such as a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, and a suspension polymerization method. Various known polymerization methods can be appropriately adopted.

<Polyfunctional alcohol (C)>
As the polyfunctional alcohol (C), any suitable polyfunctional alcohol can be adopted as long as the effect of the present invention is not impaired.

The number of functional groups of the polyfunctional alcohol (C) is preferably 2 or more, more preferably 3 to 6, still more preferably 3 to 5, and particularly preferably 2 or more in that the effect of the present invention can be more exhibited. It is preferably 3 to 4, and most preferably 3.

Examples of the polyfunctional alcohol (C) include polyether polyols and polyester polyols.

Examples of the polyether polyol include polypropylene glycol (bifunctional), diol (bifunctional) in which propylene oxide is added to bisphenol A, triol (trifunctional) in which propylene oxide is added to glycerin, and propylene oxide to trimethylolpropane. Triol (trifunctional) with propylene oxide added, tetraol (tetrafunctional) with propylene oxide added to active hydrogen of ethylenediamine, polyol (polyfunctional) with propylene oxide added to sorbitol or shoecrose, propylene oxide with glycerin. Triol with ethylene oxide added and the end blocked with ethylene oxide (trifunctional), tetraol with propylene oxide and ethylene oxide added to the active hydrogen of ethylenediamine, and the end is blocked with ethylene oxide. All (4-functional), polypropylene polyethylene glycol whose ends are blocked with ethylene oxide (bifunctional), diols obtained by adding propylene oxide and ethylene oxide to bisphenol A, whose ends are blocked by ethylene oxide. Diol (bifunctional), triol (trifunctional) with ethylene oxide added to trimethylolpropane, polypropylene polyethylene glycol (bifunctional) with ethylene oxide and propylene oxide randomly added to polypropylene polyethylene glycol, and propylene oxide to glycerin. Examples of the triol to which ethylene oxide is added include triol (trifunctional) to which ethylene oxide and propylene oxide are randomly added, and a flame-retardant polyol (bifunctional).

Commercially available products of polyether polyols include, for example, ADEKA CORPORATION (for example, P series, BPX series, G series, T series, EDP series, SP series, SC series, R series, RD series, AM series, etc. BM series, CM series, EM series, GM series, PR series, GR series, flame-retardant polyols, etc., Sanyo Kasei Kogyo Co., Ltd. polyols (for example, Sanniks GP series, Sanniks PP series, Sanniks TP-400 series) , Sanniks SP-750 series, Sanniks PL-2100 / PP series, Sun Esther series, Prime pole series, New pole series, Melpole series, PEG series, Macrogol series, etc.).

As the polyether polyol, triol (trifunctional) obtained by adding propylene oxide to glycerin and triol (trifunctional) obtained by adding propylene oxide to trimethylolpropane are preferable because the effects of the present invention can be more exhibited. , Triol with propylene oxide and ethylene oxide added to glycerin and whose ends are blocked with ethylene oxide (trifunctional), Triol with ethylene oxide added to trimethylolpropane (trifunctional), propylene oxide and ethylene oxide with glycerin Is a triol to which ethylene oxide and propylene oxide are randomly added (triol), more preferably triol (trifunctional) to which propylene oxide is added to glycerin, and propylene oxide and ethylene oxide to glycerin. Triol added with ethylene oxide whose ends are blocked (trifunctional), triol with propylene oxide and ethylene oxide added to glycerin, and triol with ethylene oxide and propylene oxide randomly added (trifunctional). Yes, more preferably triol (trifunctional) with propylene oxide added to glycerin.

Examples of the polyester polyol include a polyester polyol obtained by reacting an acid component with a glycol component. Examples of the acid component include terephthalic acid, adipic acid, azelaic acid, sebatic acid, phthalic anhydride, isophthalic acid, trimellitic acid and the like. Examples of the glycol component include ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, 1,6-hexaneglycol, 3-methyl-1,5-pentanediol, 3,3'-dimethylolheptan, and polyoxyethylene glycol. Examples thereof include polyoxypropylene glycol, 1,4-butanediol, neopentyl glycol, butylethylpentanediol, and polyol components such as glycerin, trimethylolpropane, and pentaerythritol. Examples of the polyester polyol (a1) also include a polyester polyol obtained by ring-opening polymerization of lactones such as polycaprolactone, poly (β-methyl-γ-valerolactone) and polyvalerolactone.

Examples of commercially available polyester polyols include ADEKA CORPORATION (eg, F18-62, F7-67, Y9-10, Y4-5, Y52-13, Y52-21, V14-90, YG-). 108, F1212-29, # 50, Y65-55, YT-101, YT-651, NS-2400, etc.) and the like.

The number average molecular weight of the polyfunctional alcohol (C) is preferably 50 to 10000, more preferably 60 to 5000, still more preferably 70 to 2500, in that the effects of the present invention can be more exhibited. It is particularly preferably 75 to 2000, and most preferably 80 to 1000.

<Crosslinking agent (D)>
As the cross-linking agent (D), any suitable cross-linking agent can be adopted as long as the effect of the present invention is not impaired.

Examples of the cross-linking agent (D) include a polyfunctional isocyanate-based cross-linking agent, an epoxy-based cross-linking agent, a melamine-based cross-linking agent, a peroxide-based cross-linking agent, a urea-based cross-linking agent, a metal alkoxide-based cross-linking agent, and a metal chelate-based cross-linking agent. , Metal salt-based cross-linking agent, carbodiimide-based cross-linking agent, oxazoline-based cross-linking agent, aziridine-based cross-linking agent, amine-based cross-linking agent and the like. Among these, at least one selected from the group consisting of a polyfunctional isocyanate-based cross-linking agent and an epoxy-based cross-linking agent is preferable in that the effects of the present invention can be further exhibited.

Examples of the polyfunctional isocyanate-based cross-linking agent include lower aliphatic polyisocyanates such as 1,2-ethylene diisocyanate, 1,4-butylene diisocyanate, and 1,6-hexamethylene diisocyanate; cyclopentylene diisocyanate, cyclohexylene diisocyanate, and the like. Alicyclic polyisocyanates such as isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate; 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, etc. Aromatic polyisocyanates and the like. Examples of the polyfunctional isocyanate-based cross-linking agent include trimethylolpropane / tolylene diisocyanate adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name “Coronate L”) and trimethylolpropane / hexamethylene diisocyanate adduct (Japan Polyurethane Industry Co., Ltd.). Company, product name "Coronate HL"), product name "Coronate HX" (manufactured by Nippon Polyurethane Industry Co., Ltd.), trimethylolpropane / xylylene diisocyanate adduct (manufactured by Mitsui Chemicals Co., Ltd., product name "Takenate 110N"), Commercial products such as the product name "Takenate 600" (manufactured by Mitsui Chemicals Co., Ltd.) can also be mentioned.

Examples of the epoxy-based cross-linking agent (polyfunctional epoxy compound) include N, N, N', N'-tetraglycidyl-m-xylenediamine, diglycidylaniline, and 1,3-bis (N, N-diglycidylamino). Methyl) cyclohexane, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether, Glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitan polyglycidyl ether, trimethylolpropane polyglycidyl ether, adipic acid diglycidyl ester, o-phthalic acid diglycidyl ester, triglycidyl-tris (2- In addition to hydroxyethyl) isocyanurate, resorcin diglycidyl ether, and bisphenol-S-diglycidyl ether, epoxy-based resins having two or more epoxy groups in the molecule can be mentioned. Examples of the epoxy-based cross-linking agent include commercially available products such as the trade name "Tetrad C" (manufactured by Mitsubishi Gas Chemical Company, Inc.).

<(Meta) acrylic copolymer (B)>
The pressure-sensitive adhesive composition is a composition (b) containing a (meth) acrylic acid alkyl ester in which the alkyl group of the (b1 component) alkyl ester moiety is an alicyclic hydrocarbon group, in that the effect of the present invention can be further exhibited. ) May contain a (meth) acrylic copolymer (B) formed by polymerization. The (meth) acrylic copolymer (B) may be of only one type or of two or more types.

As the content of the (meth) acrylic copolymer (B) in the pressure-sensitive adhesive composition, any appropriate content can be adopted as long as the effect of the present invention is not impaired. Such a content is preferably 0.01 part by weight with respect to the solid content (100 parts by weight) of the (meth) acrylic copolymer (A) in that the effect of the present invention can be more exhibited. ~ 30 parts by weight, more preferably 0.01 parts by weight to 20 parts by weight, further preferably 0.01 parts by weight to 10 parts by weight, and particularly preferably 0.01 parts by weight to 5 parts by weight. be.

The (meth) acrylic copolymer (B) is formed by polymerization from the composition (b) containing a (meth) acrylic acid alkyl ester in which the alkyl group of the (b1 component) alkyl ester moiety is an alicyclic hydrocarbon group. Will be done.

(B1 component) may be only one kind or two or more kinds.

Examples of the (meth) acrylic acid alkyl ester (b1 component) in which the alkyl group of the alkyl ester moiety is an alicyclic hydrocarbon group include cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and di. Cyclopentadienyl (meth) acrylate and the like can be mentioned, and dicyclopentadienyl (meth) acrylate is preferable, and dicyclopentadienyl methacrylate is more preferable, in that the effect of the present invention can be more exhibited. Is.

The (meth) acrylic acid alkyl ester (b1 component) in which the alkyl group of the alkyl ester moiety is an alicyclic hydrocarbon group with respect to the total amount (100% by weight) of the monomer components constituting the (meth) acrylic copolymer (B). The content of the ester is preferably 5% by weight or more, more preferably 10% by weight or more, still more preferably 20% by weight or more, and particularly preferably 30% in terms of allowing the effects of the present invention to be more exhibited. By weight or more, most preferably from 30% by weight to 99.9% by weight.

The composition (b) contains a copolymerizable monomer other than (b1 component). The copolymerizable monomer may be only one kind or two or more kinds.

The composition (b) is an alkyl (meth) acrylate having 1 to 3 carbon atoms in the alkyl group of the (b2 component) alkyl ester moiety as a copolymerizable monomer in that the effect of the present invention can be further exhibited. It preferably contains an ester.

Examples of the (meth) acrylic acid alkyl ester (b2 component) in which the alkyl group of the alkyl ester moiety has 1 to 3 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, and (meth) acrylic acid. Examples include propyl. The (meth) acrylic acid alkyl ester in which the alkyl group of the alkyl ester moiety has 1 to 3 carbon atoms is preferably methyl (meth) acrylate, and more. Methyl methacrylate is preferred.

The (meth) acrylic acid alkyl ester (b2 component) in which the number of carbon atoms of the alkyl group of the alkyl ester moiety is 1 to 3 with respect to the total amount (100% by weight) of the monomer components constituting the (meth) acrylic copolymer (B). The content of the above is preferably 10% by weight to 90% by weight, more preferably 15% by weight to 85% by weight, still more preferably 20% by weight to 80% by weight in that the effects of the present invention can be more exhibited. It is% by weight, particularly preferably 25% by weight to 75% by weight, and most preferably 30% by weight to 70% by weight.

Examples of the copolymerizable monomer other than the (meth) acrylic acid alkyl ester (b2 component) in which the alkyl group of the alkyl ester moiety has 1 to 3 carbon atoms include (meth) acrylic acid, itaconic acid, maleic acid, and fumal. Carboxyl group-containing monomers such as acids, crotonic acids, isocrotonic acids, these acid anhydrides (eg, acid anhydride group-containing monomers such as maleic anhydride, itaconic anhydride); hydroxyethyl (meth) acrylate, (meth). (Meta) acrylates having OH groups such as hydroxypropyl acrylate, hydroxybutyl (meth) acrylate; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, N- Amido group-containing monomers such as methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide; aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, (meth). ) Amino group-containing monomers such as t-butylaminoethyl acrylate; epoxy group-containing monomers such as (meth) glycidyl acrylate and methyl glycidyl (meth) acrylate; cyano group-containing monomers such as acrylonitrile and methacrylonitrile; N- Monomer containing a heterocycle such as vinyl-2-pyrrolidone, (meth) acryloylmorpholine, N-vinylpiperidone, N-vinylpiperazine, N-vinylpyrrole, N-vinylimidazole, vinylpyridine, vinylpyrimidine, vinyloxazole; vinylsulfone. Sulphonic acid group-containing monomer such as sodium acid; Phosphoric acid group-containing monomer such as 2-hydroxyethylacryloyl phosphate; Iimide group-containing monomer such as cyclohexylmaleimide and isopropylmaleimide; isocyanate group-containing monomer such as 2-methacryloyloxyethyl isocyanate; (Meta) acrylic acid ester having an alicyclic hydrocarbon group such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentadienyl (meth) acrylate; phenyl (meth) acrylate, (Meta) acrylic acid ester having an aromatic hydrocarbon group such as phenoxyethyl (meth) acrylate and benzyl (meth) acrylate; vinyl ester such as vinyl acetate and vinyl propionate; styrene and vinyl Examples include aromatic vinyl compounds such as toluene; olefins and dienes such as ethylene, butadiene, isoprene and isobutylene; vinyl ethers such as vinyl alkyl ethers; vinyl chloride; and the like.

As the copolymerizable monomer, a polyfunctional monomer may also be adopted. The polyfunctional monomer means a monomer having two or more ethylenically unsaturated groups in one molecule. As the ethylenically unsaturated group, any suitable ethylenically unsaturated group can be adopted as long as the effect of the present invention is not impaired. Examples of such an ethylenically unsaturated group include radically polymerizable functional groups such as a vinyl group, a propenyl group, an isopropenyl group, a vinyl ether group (vinyloxy group) and an allyl ether group (allyloxy group). Examples of the polyfunctional monomer include hexanediol di (meth) acrylate, butanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, and neopentyl glycol. Di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethyl propanthry (meth) acrylate, tetramethylol methanetri (meth) acrylate, allyl. Examples thereof include (meth) acrylate, vinyl (meth) acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, and urethane acrylate. Such a polyfunctional monomer may be only one kind, or may be two or more kinds.

As the copolymerizable monomer, (meth) acrylic acid alkoxyalkyl ester may also be adopted. Examples of the (meth) acrylate alkoxyalkyl ester include (meth) acrylate 2-methoxyethyl, (meth) acrylate 2-ethoxyethyl, (meth) acrylate methoxytriethylene glycol, and (meth) acrylate 3-. Examples thereof include methoxypropyl, 3-ethoxypropyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, and 4-ethoxybutyl (meth) acrylate. The (meth) acrylic acid alkoxyalkyl ester may be only one kind or two or more kinds.

The composition (b) preferably contains a mercaptan as a chain transfer agent in that the effects of the present invention can be more exhibited. Examples of the mercaptan include thioglycolic acid alkyl esters, and specific examples thereof include methyl thioglycolate and ethyl thioglycolate.

As the content of the chain transfer agent in the composition (b), any appropriate content may be adopted as long as the effect of the present invention is not impaired. Such a content is preferably 0, with respect to the total amount (100 parts by weight) of the monomer components constituting the (meth) acrylic copolymer (B), in that the effect of the present invention can be more exhibited. It is 01 parts by weight to 25 parts by weight, more preferably 0.02 parts by weight to 20 parts by weight, further preferably 0.05 parts by weight to 15 parts by weight, and particularly preferably 0.1 parts by weight to 15 parts by weight. It is a part by weight.

The Tg of the (meth) acrylic copolymer (B) is preferably 50 ° C. to 250 ° C., more preferably 70 ° C. to 230 ° C., and even more preferably, in that the effects of the present invention can be more exhibited. Is 80 ° C. to 220 ° C., particularly preferably 90 ° C. to 210 ° C., and most preferably 100 ° C. to 200 ° C.

The Tg of the (meth) acrylic copolymer (B) is the Tg of the homopolymer of each monomer constituting the (meth) acrylic copolymer (B) and the weight fraction of the monomer (meth). A value obtained from the Fox equation based on the weight-based copolymerization ratio). As shown below, the Fox formula is a relational formula between the Tg of the copolymer and the glass transition temperature Tgi of the homopolymer obtained by homopolymerizing each of the monomers constituting the copolymer.
1 / Tg = Σ (Wi / Tgi)

In the Fox formula, Tg is the glass transition temperature (unit: K) of the copolymer, Wi is the weight fraction of the monomer i in the copolymer (copolymerization ratio based on the weight), and Tgi is the homopolymer of the monomer i. Represents the glass transition temperature (unit: K) of. As the Tg of the homopolymer, the value described in the publicly known material shall be adopted.

As the Tg of the homopolymer, for example, the following values can be specifically used.
Dicyclopentadienyl methacrylate 175 ° C
Methyl methacrylate 105 ° C

For Tg of homopolymers other than those exemplified above, the numerical values described in "Polymer Handbook" (3rd edition, John Wiley & Sons, Inc., 1989) can be used. When a plurality of numerical values are described in the above "Polymer Handbook", the value of conventional is adopted. For the monomers not described in the above "Polymer Handbook", the catalog values of the monomer manufacturing companies are adopted. As the Tg of the homopolymer of the monomer which is not described in the above "Polymer Handbook" and the catalog value of the monomer manufacturing company is not provided, the value obtained by the measuring method described in JP-A-2007-51271 is used. do.

The weight average molecular weight of the (meth) acrylic copolymer (B) is preferably 1000 to 30,000, more preferably 1250 to 25,000, and further preferably 1500 in that the effects of the present invention can be more exhibited. It is ~ 20000, particularly preferably 2000-15000, and most preferably 2000-10000.

The composition (b) may contain any suitable other ingredients as long as the effects of the present invention are not impaired. Examples of such other components include polymerization initiators, chain transfer agents, solvents and the like. As the content of these other components, any appropriate content may be adopted as long as the effect of the present invention is not impaired. For these details, the description in the section <(meth) acrylic copolymer (A)> can be incorporated.

As a method for obtaining the (meth) acrylic copolymer (B), for example, as a method for synthesizing the (meth) acrylic copolymer, such as a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, and a suspension polymerization method. Various known polymerization methods can be appropriately adopted.

<Ionic liquid>
The pressure-sensitive adhesive composition may contain an ionic liquid. Since the pressure-sensitive adhesive composition contains an ionic liquid, it is possible to provide a pressure-sensitive adhesive composition having excellent antistatic properties. Such an ionic liquid may be only one kind or two or more kinds.

In the present invention, the ionic liquid means a molten salt (ionic compound) that exhibits a liquid at 25 ° C.

The ionic liquid is preferably an ionic liquid containing a fluoroorganic anion. The ionic liquid containing a fluoroorganic anion is preferably an ionic liquid composed of a fluoroorganic anion and an onium cation. By adopting an ionic liquid composed of a fluoroorganic anion and an onium cation as the ionic liquid, it is possible to provide a pressure-sensitive adhesive composition having extremely excellent antistatic properties.

As the onium cation that can form an ionic liquid, any suitable onium cation can be adopted as long as the effect of the present invention is not impaired. The onium cation is preferably at least one selected from a nitrogen-containing onium cation, a sulfur-containing onium cation, and a phosphorus-containing onium cation. By selecting these onium cations, it is possible to provide a pressure-sensitive adhesive composition having extremely excellent antistatic properties.

The onium cation that can form an ionic liquid is preferably at least one selected from cations having structures represented by the general formulas (1) to (5).

In the general formula (1), Ra represents a hydrocarbon group having 4 to 20 carbon atoms and may contain a heteroatom, and Rb and Rc are the same or different, hydrogen or a hydrocarbon having 1 to 16 carbon atoms. It represents a hydrogen group and may contain a heteroatom. However, when the nitrogen atom contains a double bond, there is no Rc.

In the general formula (2), Rd represents a hydrocarbon group having 2 to 20 carbon atoms and may contain a heteroatom, and Re, Rf, and Rg are the same or different from hydrogen or 1 carbon atom. It represents 16 hydrocarbon groups and may contain heteroatoms.

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

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

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 a pyridinium cation, a pyrrolidinium cation, a piperidinium cation, a cation having a pyrroline skeleton, and a cation having a pyrrole skeleton.

Specific examples of the cation represented by the general formula (1) include, for example, 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-ethyl-3-methylpyridinium cation, 1-butyl. -3-Methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1-octyl-4-methylpyridinium cation, 1-butyl-3,4-dimethylpyridinium cation, Pyridinium cations such as 1,1-dimethylpyrrolidinium cations; 1-ethyl-1-methylpyrrolidinium cations, 1-methyl-1-propylpyrrolidinium cations, 1-methyl-1-butylpyrrolidinium cations, 1-Methyl-1-pentylpyrrolidinium cation, 1-methyl-1-hexylpyrrolidinium cation, 1-methyl-1-heptylpyrridinium cation, 1-ethyl-1-propylpyrrolidinium cation, 1 -Ethyl-1-butylpyrridinium cation, 1-ethyl-1-pentylpyrrolidinium cation, 1-ethyl-1-hexylpyrrolidinium cation, 1-ethyl-1-heptylpyrrolidinium cation, 1 , 1-Dipropylpyrridinium cation, 1-propyl-1-butylpyrridinium cation, 1,1-dibutylpyrridinium cation and other pyrrolidinium cations; 1-propylpiperidinium cation, 1-pentylpi Pyridinium cation, 1-methyl-1-ethylpiperidinium cation, 1-methyl-1-propylpiperidinium cation, 1-methyl-1-butylpiperidinium cation, 1-methyl-1-pentylpiperidinium Cations, 1-methyl-1-hexylpiperidinium cations, 1-methyl-1-heptylpiperidinium cations, 1-ethyl-1-propylpiperidinium cations, 1-ethyl-1-butylpiperidinium cations , 1-ethyl-1-pentylpiperidinium cation, 1-ethyl-1-hexylpiperidinium cation, 1-ethyl-1-heptylpiperidinium cation, 1-propyl-1-butylpiperidinium cation, Piperidinium cations such as 1,1-dimethylpyridinium cation, 1,1-dipropylpiperidinium cation, 1,1-dibutylpiperidinium cation; 2-methyl-1-pyrrolinate cation; 1-d. Chill-2-phenylindole cations; 1,2-dimethylindole cations; 1-ethylcarbazole cations; and the like.

Among these, 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-ethyl-3-methylpyridinium cation, 1-ethylpyridinium cation are preferable in that the effect of the present invention can be further exhibited. -Pyridinium cations such as butyl-3-methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1-octyl-4-methylpyridinium cation; 1-ethyl-1- Methylpyrridinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-butylpyrrolidinium cation, 1-methyl-1-pentylpyrrolidinium cation, 1-methyl-1-hexyl Pyridinium cation, 1-methyl-1-heptylpyrrolidinium cation, 1-ethyl-1-propylpyrrolidinium cation, 1-ethyl-1-butylpyrrolidinium cation, 1-ethyl-1-pentylpyrrolidinium Pyridinium cations such as nium cations, 1-ethyl-1-hexylpyrrolidinium cations, 1-ethyl-1-heptylpyrrolidinium cations; 1-methyl-1-ethylpiperidinium cations, 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 cations, 1-ethyl-1-heptylpyridinium cations, piperidinium cations such as 1-propyl-1-butylpiperidinium cations; and the like; more preferably 1-hexyl. Pyridinium cation, 1-ethyl-3-methylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-octyl-4-methylpyridinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1 -A propylpyridinium cation.

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

Specific examples of the cation represented by the general formula (2) include, for example, 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, and 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 Rium cation, 1-tetradecyl-3-methylimidazolium cation, 1,2-dimethyl-3-propylimidazolium cation, 1-ethyl-2,3-dimethylimidazolium cation, 1-butyl-2,3-dimethylimidazolium cation Imidazolium cations such as lithium cations, 1-hexyl-2,3-dimethylimidazolium cations; 1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium cations, 1,2,3-trimethyl- 1,4,5,6-Tetrahydropyrimidinium cation, 1,2,3,4-tetramethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,2,3,5-tetramethyl- Tetrahydropyrimidinium cations such as 1,4,5,6-tetrahydropyrimidinium cations; 1,3-dimethyl-1,4-dihydropyrimidinium cations, 1,3-dimethyl-1,6-dihydropyrimidi Nium cation, 1,2,3-trimethyl-1,4-dihydropyrimidinium cation, 1,2,3-trimethyl-1,6-dihydropyrimidinium cation, 1,2,3,4-tetramethyl- Dihydropyrimidinium cations such as 1,4-dihydropyrimidinium cation, 1,2,3,4-tetramethyl-1,6-dihydropyrimidinium cation; and the like.

Among these, 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1 are preferable in that the effect of the present invention can be further exhibited. -Butyl-3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-decyl-3-methylimidazolium cation, 1-dodecyl-3- Methylimidazolium cations, 1-tetradecyl-3-methylimidazolium cations and other imidazolium cations, more preferably 1-ethyl-3-methylimidazolium cations, 1-hexyl-3-methylimidazolium cations. be.

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

Specific examples of the cation represented by the general formula (3) include 1-methylpyrazolium cation, 3-methylpyrazolium cation, 1-ethyl-2-methylpyrazolinium cation, and 1-ethyl-. Pyrazolium cations such as 2,3,5-trimethylpyrazolium cation, 1-propyl-2,3,5-trimethylpyrazolium cation, 1-butyl-2,3,5-trimethylpyrazolium cation; Pila such as 1-ethyl-2,3,5-trimethylpyrazolinium cation, 1-propyl-2,3,5-trimethylpyrazolinium cation, 1-butyl-2,3,5-trimethylpyrazolinium cation Zolinium cation; and the like.

Examples of the cation represented by the general formula (4) include a tetraalkylammonium cation, a trialkylsulfonium cation, a tetraalkylphosphonium cation, and a part of the above alkyl group is replaced with an alkenyl group, an alkoxyl group, or an epoxy group. The ones that have been done are mentioned.

Specific examples of the cation represented by the general formula (4) include, for example, tetramethylammonium cation, tetraethylammonium cation, tetrabutylammonium cation, tetrapentylammonium cation, tetrahexylammonium cation, tetraheptylammonium cation, and triethylmethylammonium. Cations, tributylethylammonium cations, trimethylpropylammonium cations, trimethyldecylammonium cations, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium cations, glycidyltrimethylammonium cations, trimethylsulfonium cations, triethylsulfonium cations , Tributyl sulfonium cation, trihexyl sulfonium cation, diethyl methyl sulfonium cation, dibutyl ethyl sulfonium cation, dimethyl decyl sulfonium cation, tetramethyl phosphonium cation, tetraethyl phosphonium cation, tetra butyl phosphonium cation, tetrahexyl phosphonium cation, tetraoctyl phosphonium cation, triethyl Examples thereof include a methylphosphonium cation, a tributylethylphosphonium cation, a trimethyldecylphosphonium cation, and a diallyldimethylammonium cation.

Among these, triethylmethylammonium cation, tributylethylammonium cation, trimethyldecylammonium cation, diethylmethylsulfonium cation, dibutylethylsulfonium cation, dimethyldecylsulfonium cation, are preferable in that the effect of the present invention can be further exhibited. Asymmetric tetraalkylammonary cations such as triethylmethylphosphonium cations, tributylethylphosphonium cations, trimethyldecylphosphonium cations, trialkylsulfonium cations, tetraalkylphosphonium cations, and N, N-diethyl-N-methyl-N- (2-methoxy). Ethyl) ammonium cation, glycidyltrimethylammonium cation, diallyldimethylammonium cation, N, N-dimethyl-N-ethyl-N-propylammonium cation, N, N-dimethyl-N-ethyl-N-butylammonium cation, N, N -Dimethyl-N-ethyl-N-pentylammonium cations, N, N-dimethyl-N-ethyl-N-hexylammonary cations, N, N-dimethyl-N-ethyl-N-heptylammonium cations, N, N-dimethyl -N-ethyl-N-nonylammonium cation, N, N-dimethyl-N, N-dipropylammonium cation, N, N-diethyl-N-propyl-N-butylammonary cation, N, N-dimethyl-N- Propyl-N-pentylammonium cation, N, N-dimethyl-N-propyl-N-hexylammonium cation, N, N-dimethyl-N-propyl-N-heptylammonium cation, N, N-dimethyl-N-butyl- N-hexylammonium cations, N, N-diethyl-N-butyl-N-heptylammonium cations, N, N-dimethyl-N-pentyl-N-hexylammonium cations, N, N-dimethyl-N, N-dihexylammonium Cations, trimethylheptylammonium cations, N, N-diethyl-N-methyl-N-propylammonary cations, N, N-diethyl-N-methyl-N-pentylammonium cations, N, N-diethyl-N-methyl-N -Heptylammonium cation, N, N-diethyl-N-propyl-N-pentylammonium cation, triethylpropylammonium cation, triethylpentylammonium Cations, triethylheptylammonium cations, N, N-dipropyl-N-methyl-N-ethylammonary cations, N, N-dipropyl-N-methyl-N-pentylammonium cations, N, N-dipropyl-N-butyl-N -Hexylammonium cations, N, N-dipropyl-N, N-dihexylammonium cations, N, N-dibutyl-N-methyl-N-pentylammonium cations, N, N-dibutyl-N-methyl-N-hexylammonium cations , Trioctylmethylammonium cations, N-methyl-N-ethyl-N-propyl-N-pentylammonium cations and the like, more preferably trimethylpropylammonium cations.

As the fluoroorganic anion that can constitute an ionic liquid, any suitable fluoroorganic anion can be adopted as long as the effects of the present invention are not impaired. Such fluoroorganic anions may be completely fluorinated (perfluoro) or partially fluorinated.

Examples of such fluoroorganic anions include fluorinated arylsulfonates, perfluoroalkanesulfonates, bis (fluorosulfonyl) imides, bis (perfluoroalkanesulfonyl) imides, cyanoperfluoroalkanesulfonylamides, and bis (cyano). Perfluoroalkanesulfonyl methide, cyano-bis- (perfluoroalkanesulfonyl) methide, tris (perfluoroalkanesulfonyl) methide, trifluoroacetate, perfluoroalkanelate, tris (perfluoroalkanesulfonyl) methide, (perfluoroalkane sulfonyl) Sulfonyl) Trifluoroacetamide and the like.

Among these fluoroorganic anions, perfluoroalkyl sulfonate, bis (fluorosulfonyl) imide, and bis (perfluoroalkanesulfonyl) imide are more preferable, and more specifically, for example, trifluoromethanesulfonate and pentafluoroethane. They are sulfonate, heptafluoropropane sulfonate, nonafluorobutane sulfonate, bis (fluorosulfonyl) imide, and bis (trifluoromethanesulfonyl) imide.

As a specific example of the ionic liquid, it can be appropriately selected from the combination of the above-mentioned cationic component and the above-mentioned anionic component and used. Specific examples of such an ionic liquid include 1-hexylpyridinium bis (fluorosulfonyl) imide, 1-ethyl-3-methylpyridinium trifluoromethanesulfonate, 1-ethyl-3-methylpyridinium pentafluoroethanesulfonate, and the like. 1-Ethyl-3-methylpyridinium heptafluoropropanesulfonate, 1-ethyl-3-methylpyridinium nonafluorobutane sulfonate, 1-butyl-3-methylpyridinium trifluoromethanesulfonate, 1-butyl-3-methylpyridinium bis (trifluoromethane) Sulfonyl) imide, 1-butyl-3-methylpyridinium bis (pentafluoroethanesulfonyl) imide, 1-octyl-4-methylpyridinium bis (fluorosulfonyl) imide, 1,1-dimethylpyrrolidinium bis (trifluoromethanesulfonyl) Imide, 1-methyl-1-ethylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpyrrolidinium bis (1-methyl-1-propylpyrrolidinium bis) Fluorosulfonyl) imide, 1-methyl-1-butylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-pentylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-hexylpyrroli Diniumbis (trifluoromethanesulfonyl) imide, 1-methyl-1-heptylpyrrolidiniumbis (trifluoromethanesulfonyl) imide, 1-ethyl-1-propylpyrrolidiniumbis (trifluoromethanesulfonyl) imide, 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, 1,1-dipropylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-propyl-1-butylpyrrolidinium bis (1-propyl-1-butylpyrrolidinium bis) Trifluoromethanesulfonyl) imide, 1,1-dibutylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-propylpiperidinium bis (trifluoromethanesul) Honyl) imide, 1-pentylpiperidinium bis (trifluoromethanesulfonyl) imide, 1,1-dimethylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-ethylpiperidinium bis (trifluoromethanesulfonyl) Imide, 1-methyl-1-propylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpiperidinium bis (fluorosulfonyl) imide, 1-methyl-1-butylpiperidinium bis (trifluo) Lomethanesulfonyl) imide, 1-methyl-1-pentylpiperidiniumbis (trifluoromethanesulfonyl) imide, 1-methyl-1-hexylpiperidiniumbis (trifluoromethanesulfonyl) imide, 1-methyl-1-hepti Lupiperidinium 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, 1,1-dipropyl piperidinium bis (trifluoromethanesulfonyl) imide, 1-propyl-1-butyl piperidinium bis (trifluoromethanesulfonyl) imide, 1,1-dibutyl piperidinium bis (trifluoromethane) Sulfonyl) imide, 1,1-dimethylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-ethylpyrrolidinium 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 (penta) Fluoroetan Sulfonyl) imide, 1-ethyl-1-butylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-pentylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-hexyl Pyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-heptylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1,1-dipropylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-propyl-1-butylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1,1-dibutylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-propylpiperidinium bis (pentafluoroethanesulfonyl) imide , 1-pentylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1,1-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-heptylpiperidiniumbis (pentafluoroethanesulfonyl) imide, 1 -Ethyl-1-propylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-butylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-pentylpiperidinium bis (penta) Fluoroethanesulfonyl) imide, 1-ethyl-1-hexylpiperidiniumbis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-heptylpiperidiniumbis (pentafluoroethanesulfonyl) imide, 1,1- Dipropylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-propyl-1-butylpiperidiniumbis (pentafluoroethanesulfonyl) imide, 1,1-dibutylpiperidiniumbis (pentafluoroethanesulfonyl) imide, 1-Ethyl-3-methylimidazole Umtrifluoroacetate, 1-ethyl-3-methylimidazolium heptafluorobutyrate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium heptafluoropropanesulfonate, 1-ethyl- 3-Methyl imidazolium nonafluorobutane sulfonate, 1-ethyl-3-methyl imidazolium bis (trifluoromethanesulfonyl) imide, 1-ethyl-3-methyl imidazolium bis (fluorosulfonyl) imide, 1-ethyl-3-methyl Imidazolium 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-trimethylpyrazo Riumbis (pentafluoroethanesulfonyl) imide, 1-butyl-2,3,5-trimethylpyrazolium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-2,3,5-trimethylpyrazolium (trifluoromethane) Sulfonyl) trifluoroacetamide, 1-propyl-2,3,5-trimethylpyrazolium (trifluoromethanesulfonyl) trifluoroacetamide, 1-butyl-2,3,5-trimethylpyrazolium (trifluoro) Methansulfonyl) trifluoroacetamide, trimethylpropylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-propylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl- N-butylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-hexylammonium bis ( Trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-nonylammonyl bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N, N-dipropylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-propyl-N-butylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N -Propyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-propyl-N-hexyl ammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-propyl-N-heptyl Ammonyl bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-butyl-N-hexyl ammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-butyl-N-heptyl ammonium bis (trifluoromethanesulfonyl) ) Imide, N, N-dimethyl-N-pentyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N, N-dihexylammonium bis (trifluoromethanesulfonyl) imide, trimethylheptylammonium bis (trifluoromethanesulfonyl) Trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl-N-propylammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl-N, N-heptylammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-propyl-N-pentyluan Monium bis (trifluoromethanesulfonyl) imide, triethylpropylammonium bis (trifluoromethanesulfonyl) imide, triethylpentylammonium bis (trifluoromethanesulfonyl) imide, triethylheptylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N-methyl -N-Ethylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N-butyl-N-hexylammonium bis (Trifluoromethanesulfonyl) imide, N, N-dipropyl-N, N-dihexylammonium bis (trifluoromethanesulfonyl) imide, N, N-dibutyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, 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, N- Diethyl-N-methyl-N- (2-methoxyethyl) ammonium trifluoromethanesulfonate, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (trifluoromethanesulfonyl) imide, N, N- Diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (pentafluoroethanesulfonyl) imide, glycidyltrimethylammonium trifluoromethanesulfonate, glycidyltrimethylammo Niumbis (trifluoromethanesulfonyl) imide, glycidyltrimethylammonium bis (pentafluoroethanesulfonyl) imide, diallyldimethylammonium bis (trifluoromethanesulfonyl) imide, diallyldimethylbis (pentafluoroethanesulfonyl) imide, lithium bis (trifluoromethanesulfonyl) Examples thereof include imide and lithium bis (fluorosulfonyl) imide.

Among these ionic liquids, 1-hexylpyridinium bis (fluorosulfonyl) imide, 1-ethyl-3-methylpyridinium trifluoromethanesulfonate, 1-ethyl-3-methylpyridinium pentafluoroethanesulfonate, 1- Ethyl-3-methylpyridinium heptafluoropropanesulfonate, 1-ethyl-3-methylpyridinium nonafluorobutane sulfonate, 1-butyl-3-methylpyridinium trifluoromethanesulfonate, 1-butyl-3-methylpyridinium bis (trifluoromethanesulfonyl) Imide, 1-octyl-4-methylpyridinium bis (fluorosulfonyl) imide, 1-methyl-1-propylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpyrrolidinium bis (fluorosulfonyl) Imide, 1-methyl-1-propylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpiperidinium bis (fluorosulfonyl) imide, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-Ethyl-3-methylimidazolium heptafluoropropanesulfonate, 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-ethyl-3-methylimidazolium bis (fluorosulfonyl) imide, 1-hexyl -3-Methylimidazolium bis (fluorosulfonyl) imide, trimethylpropylammonium bis (trifluoromethanesulfonyl) imide, lithium bis (trifluoromethanesulfonyl) imide, lithium bis (fluorosulfonyl) imide.

Commercially available ionic liquids may be used, but they can also be synthesized as described below. The method for synthesizing an ionic liquid is not particularly limited as long as the desired ionic liquid can be obtained, but in general, the document "Ionic Liquid-Forefront and Future of Development-" (CMC Publishing Co., Ltd.) The halide method, hydroxide method, acid ester method, complex formation method, neutralization method and the like as described in (Issued) are used.

The halide method, hydroxide method, acid ester method, complex formation method, and neutralization method are shown below by taking a nitrogen-containing onium salt as an example, but other sulfur-containing onium salts and phosphorus-containing onium salts are shown below. Other ionic liquids such as, can also be obtained by the same method.

The halide method is a method performed by a reaction as shown in the reaction formulas (1) to (3). First, a halide is obtained by reacting a tertiary amine with an alkyl halide (reaction formula (1), chlorine, bromine, or iodine is used as the halogen).

An acid (HA) or salt (MA, M is ammonium, lithium, sodium, potassium, etc.) having ^{an anion structure (A −} ) of an ionic liquid intended for the obtained halide and a cation forming a salt with the desired anion. ) is reacted with an objective ionic liquid (R 4 _NA) is obtained.

The hydroxide method is a method performed by a reaction as shown in the reaction formulas (4) to (8). First halide _(R 4 NX) ion-exchange membrane method electrolysis (reaction equation (4)), OH-type ion exchange resin method (reaction equation (5)) or silver oxide _(Ag 2 O) and of the reaction (reaction formula ( obtain a hydroxide _(R 4 NOH) 6)) (as a halogen, chlorine, bromine or iodine is used).

By using the reaction of reaction formula as above halogenation process (7) - (8) The obtained hydroxide, the ionic liquid (R 4 _NA) to obtain the objective.

The acid ester method is a method performed by a reaction as shown in the reaction formulas (9) to (11). First tertiary amine (R 3 _N) to obtain the ester was reacted with ester (Scheme (9), as acid ester, sulfuric, sulfurous, phosphoric acid, phosphorous acid, an inorganic acid such as carbonic acid Esters, esters of organic acids such as methanesulfonic acid, methylphosphonic acid, and formic acid are used).

By using the reaction of as above halogenation process reaction formulas (10) to (11) The obtained ester product, the ionic liquid (R 4 _NA) to obtain the objective. Further, by using methyltrifluoromethanesulfonate, methyltrifluoroacetate or the like as the acid ester, a directly ionic liquid can also be obtained.

The neutralization method is a method performed by a reaction as shown in the reaction formula (12). Reacts tertiary amines with organic acids such as _{CF 3} COOH, CF ₃ SO ₃ H, (CF ₃ SO ₂ ) ₂ NH, (CF ₃ SO ₂ ) ₃ CH, (C ₂ F ₅ SO ₂ ) _{2 NH.} Can be obtained by

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

As the content of the ionic liquid in the pressure-sensitive adhesive composition, any appropriate content may be adopted as long as the effect of the present invention is not impaired. Such a content is preferably 0.001 part by weight with respect to the solid content (100 parts by weight) of the (meth) acrylic copolymer (A) in that the effect of the present invention can be more exhibited. ~ 50 parts by weight, more preferably 0.01 parts by weight to 40 parts by weight, further preferably 0.01 parts by weight to 30 parts by weight, and particularly preferably 0.01 parts by weight to 20 parts by weight. Most preferably, it is 0.01 parts by weight to 10 parts by weight. By adjusting the blending amount of the ionic liquid within the above range, it is possible to provide a pressure-sensitive adhesive composition having excellent antistatic properties. If the blending amount of the ionic liquid is less than 0.01 parts by weight, sufficient antistatic properties may not be obtained. If the blending amount of the ionic liquid exceeds 50 parts by weight, contamination of the adherend may increase.

<Modified silicone oil>
The pressure-sensitive adhesive composition may contain a modified silicone oil. By including the modified silicone oil in the pressure-sensitive adhesive composition, the effect of antistatic properties can be more exhibited. In particular, when used in combination with an ionic liquid, the effect of antistatic properties can be exhibited even more effectively.

As the content of the modified silicone oil in the pressure-sensitive adhesive composition, any appropriate content may be adopted as long as the effect of the present invention is not impaired. Such a content is preferably 0.001 part by weight with respect to the solid content (100 parts by weight) of the (meth) acrylic copolymer (A) in that the effect of the present invention can be more exhibited. It is ~ 50 parts by weight, more preferably 0.005 parts by weight to 40 parts by weight, further preferably 0.007 parts by weight to 30 parts by weight, and particularly preferably 0.008 parts by weight to 20 parts by weight. Most preferably, it is 0.01 parts by weight to 10 parts by weight. By adjusting the content ratio of the modified silicone oil within the above range, the effect of the antistatic property can be more effectively exhibited.

As the modified silicone oil, any suitable modified silicone oil may be adopted as long as the effects of the present invention are not impaired. Examples of such modified silicone oils include modified silicone oils available from Shin-Etsu Chemical Co., Ltd.

The modified silicone oil is preferably a polyether-modified silicone oil. By adopting a polyether-modified silicone oil, the effect of antistatic properties can be exhibited even more effectively.

Examples of the polyether-modified silicone oil include side-chain type polyether-modified silicone oil and both-terminal type polyether-modified silicone oil. Among these, the double-ended type polyether-modified silicone oil is preferable in that the effect of the antistatic property can be sufficiently and more effectively exhibited.

<Other components that may be contained in the pressure-sensitive adhesive composition>
The pressure-sensitive adhesive composition may contain any suitable other ingredients as long as the effects of the present invention are not impaired. Examples of such other components include other polymer components, cross-linking accelerators, cross-linking catalysts, silane coupling agents, tackifier resins (rosin derivatives, polyterpene resins, petroleum resins, oil-soluble phenols, etc.), and antiaging agents. , Inorganic fillers, organic fillers, metal powders, colorants (pigments, dyes, etc.), foils, UV absorbers, antioxidants, light stabilizers, chain transfer agents, plasticizers, softeners, surfactants , Antistatic agents, conductive agents, stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts and the like.

≪Base material layer≫
The base material layer may be only one layer or two or more layers. The base material layer may be a stretched one.

The thickness of the base material layer is preferably 1 μm to 500 μm, more preferably 5 μm to 400 μm, still more preferably 10 μm to 300 μm, and particularly preferably 15 μm to 200 μm.

For the surface of the base material layer to which the pressure-sensitive adhesive layer is not attached, for the purpose of forming a wound body that can be easily rewound, for example, fatty acid amide, polyethyleneimine, and a long-chain alkyl-based additive are added to the base material layer. Etc. may be added to perform mold release treatment, or a coat layer made of any suitable release agent such as silicone-based, long-chain alkyl-based, and fluorine-based may be provided.

As the material of the base material layer, any suitable material may be adopted depending on the intended use. For example, plastic, paper, metal film, non-woven fabric and the like can be mentioned. It is preferably plastic. That is, the base material layer is preferably a plastic film. The base material layer may be composed of one kind of material or may be made of two or more kinds of materials. For example, it may be composed of two or more kinds of plastics.

Examples of the plastic include polyester-based resin, polyamide-based resin, and polyolefin-based resin. Examples of the polyester-based resin include polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate. Examples of the polyolefin-based resin include homopolymers of olefin monomers and copolymers of olefin monomers. Specific examples of the polyolefin-based resin include homopolypoly; a block-based, random-based, and graft-based propylene-based copolymer having an ethylene component as a copolymer; reactor TPO; low density, high density, and linear. Low-density, ultra-low-density, etc. ethylene-based copolymers; ethylene / propylene copolymer, ethylene / vinyl acetate copolymer, ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer, ethylene / acrylic acid Examples thereof include a butyl copolymer, an ethylene / methacrylic acid copolymer, an ethylene-based copolymer such as an ethylene / methyl methacrylate copolymer; and the like.

The substrate layer may contain any suitable additives, if desired. Examples of the additive that can be contained in the base material layer include antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, fillers, pigments and the like. The type, number, and amount of additives that can be contained in the base material layer can be appropriately set according to the purpose. In particular, when the material of the base material layer is plastic, it is preferable to contain some of the above additives for the purpose of preventing deterioration and the like. From the viewpoint of improving weather resistance and the like, particularly preferable additives include antioxidants, ultraviolet absorbers, light stabilizers and fillers.

As the antioxidant, any suitable antioxidant may be employed. Examples of such antioxidants include phenol-based antioxidants, phosphorus-based processing heat stabilizers, lactone-based processing heat stabilizers, sulfur-based heat-resistant stabilizers, phenol-phosphorus-based antioxidants, and the like. The content ratio of the antioxidant is preferably 1% by weight or less, more preferably 1% by weight or less, based on the base resin of the base material layer (when the base material layer is a blend product, the blend product is the base resin). It is 0.5% by weight or less, more preferably 0.01% by weight to 0.2% by weight.

As the ultraviolet absorber, any suitable ultraviolet absorber may be adopted. Examples of such an ultraviolet absorber include a benzotriazole-based ultraviolet absorber, a triazine-based ultraviolet absorber, and a benzophenone-based ultraviolet absorber. The content ratio of the ultraviolet absorber is preferably 2% by weight or less with respect to the base resin forming the base material layer (when the base material layer is a blend product, the blend product is the base resin), and more. It is preferably 1% by weight or less, and more preferably 0.01% by weight to 0.5% by weight.

As the light stabilizer, any suitable light stabilizer may be adopted. Examples of such a light stabilizer include a hindered amine-based light stabilizer and a benzoate-based light stabilizer. The content ratio of the light stabilizer is preferably 2% by weight or less with respect to the base resin forming the base material layer (when the base material layer is a blend product, the blend product is the base resin), and more. It is preferably 1% by weight or less, and more preferably 0.01% by weight to 0.5% by weight.

As the filler, any suitable filler may be adopted. Examples of such a filler include an inorganic filler and the like. Specific examples of the inorganic filler include carbon black, titanium oxide, zinc oxide and the like. The content ratio of the filler is preferably 20% by weight or less, more preferably 20% by weight or less, based on the base resin forming the base material layer (when the base material layer is a blend product, the blend product is the base resin). Is 10% by weight or less, more preferably 0.01% by weight to 10% by weight.

Further, as the additive, an inorganic type such as a surfactant, an inorganic salt, a polyhydric alcohol, a metal compound, and carbon, a low molecular weight type, and a high molecular weight type antistatic agent are also preferably mentioned for the purpose of imparting antistatic properties. In particular, from the viewpoint of contamination and maintenance of adhesiveness, high molecular weight antistatic agents and carbon are preferable.

≪≪Use≫≫
The surface protective film of the present invention has high adhesive strength and high light peelability, and even if it is subjected to high temperature and high pressure treatment by an autoclave or the like after being attached to an adherend and then returned to normal temperature and pressure, bubbles are generated. Can be suppressed. Therefore, it can be suitably used for surface protection of an adherend, which is required to have the above performance with respect to the surface protection film.

As such an adherend, preferably, an adherend having a water contact angle of 60 degrees or more on the surface thereof can be mentioned. The water contact angle on the surface of such an adherend is preferably 65 degrees or more, more preferably 70 degrees or more, still more preferably 75 degrees or more, and particularly preferably 80 degrees or more. If the adherend whose surface has a water contact angle within the above range is subjected to high-temperature and high-pressure treatment by an autoclave or the like after attaching a conventional surface protective film, and then returned to normal temperature and pressure, bubbles are generated. It is easy to occur. When the surface protective film of the present invention is used, even if it is attached to an adherend whose surface has a water contact angle within the above range, then subjected to high temperature and high pressure treatment by an autoclave or the like and then returned to normal temperature and pressure. The generation of bubbles can be suppressed.

Examples of such an adherend include an unsaponified TAC (triacetyl cellulose) film, an organic EL display, a barrier film that can be used for a device such as an OLED, and the like.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. The tests and evaluation methods in the examples and the like are as follows. In addition, when it is described as "part", it means "part by weight" unless there is a special note, and when it is described as "%", it means "% by weight" unless there is a special note.

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

<Measurement of pulse NMR of adhesive layer>
The measurement of pulse NMR was measured by the CPMG method. Specifically, as a pulse NMR measuring device, a trade name "TD-NMR the minispec mq20" (manufactured by Brukar) was used, and measurement was performed under the following conditions.
(Relaxation time measurement conditions)
-Measurement method: CPMG method-90 ° pulse width: 2.1 μs
・ Repeat time: 1 second ・ Number of integrations: 64 times ・ Measurement temperature: 30 ° C, 60 ° C
・ Analysis method: Non-linear least squares method

<Measurement of shear adhesive force>
After cutting the surface protective film into a size of 10 mm in width and 100 mm in length and peeling off the separator, the unsheared force obtained in Production Example 5 described later is obtained so that ^{the adhesive (adhesive) area of the exposed adhesive layer becomes 1 cm 2.} It was attached to a TAC polarizing plate (width 70 mm, length 100 mm, water contact angle = 69.9 degrees), left to stand for 30 minutes in an environment of 23 ° C × 50% RH, and then peeled at a peeling speed of 0.06 mm / min. The film was peeled off in the shear direction, and the maximum load (N / cm ² ) at that time was taken as the shear adhesive force.

<Measurement of high-speed peeling force>
The surface protective film was cut into a size of 25 mm in width and 100 mm in length, and after the separator was peeled off, the unkeratinized TAC polarizing plate obtained in Production Example 5 described later (width 70 mm, length 100 mm, water contact angle = 69. After crimping to the surface of 9 degrees) with a hand roller, it was laminated under crimping conditions of 0.25 MPa and 0.3 m / min to prepare an evaluation sample. Next, the separator on the polarizing plate side of the evaluation sample was peeled off, crimped onto a slide glass having a thickness of 1.3 mm, a width of 65 mm, and a length of 165 mm with a hand roller, and left in an environment of 23 ° C. × 50% RH for 30 minutes. The adhesive strength when one end of the surface protective film was peeled off at a tensile speed of 30 m / min and a peeling angle of 180 ° was measured with a universal tensile tester. The measurement was performed in an environment of 23 ° C. × 50% RH.

<Measurement of the number of bubbles generated after high temperature and high pressure treatment>
The surface protective film was cut into a size of 65 mm in width and 90 mm in length, the separator was peeled off, and then the surface of the adherend (70 mm in width and 100 mm in length) was pressure-bonded with a hand roller. Laminating was performed under crimping conditions of 3 m / min, and four sides were cut from the surface protective film side with a cutting machine so as to have a width of 50 mm and a length of 80 mm, and used as an evaluation sample. The separator on the polarizing plate side is peeled off, crimped onto a slide glass having a thickness of 1.3 mm, a width of 65 mm, and a length of 165 mm with a hand roller, left in an environment of 23 ° C × 50% RH for 30 minutes, and then at 50 ° C, 5 atm. After performing the autoclave treatment for 40 minutes in the above environment, the pressure was returned to normal temperature and pressure, and the bubbles generated at the end of the polarizing plate immediately after that were counted and used as the number of bubbles generated.
As the adherend, the following substances prepared in the production example described later were used.
Adhesion (A): Unsaponified TAC polarizing plate with adhesive layer (water contact angle = 69.9 degrees)
Adhesive body (B): Antiglare-treated polarizing plate with adhesive layer (water contact angle = 88.4 degrees)
Adhesive body (C): Saponified TAC polarizing plate with adhesive layer (water contact angle = 53.1 degrees)

<Measurement of water contact angle>
Using DM-501 manufactured by Kyowa Surface Chemistry Co., Ltd., ion-exchanged water was prepared by dropping 2 μL of the prepared liquid with a syringe, and the waiting time until the measurement after dropping was measured as 1000 ms. Further, the water contact angle was measured at 5 points in the width direction at any plurality of points of the adherend, and the average value was taken as the water contact angle of the adherend.

<Measurement of swelling degree>
The degree of swelling was measured by the following method. That is, about 0.1 g of the polymer after the cross-linking reaction was collected, wrapped in a porous tetrafluoroethylene sheet (trade name "NTF1122", manufactured by Nitto Denko Co., Ltd.) with an average pore size of 0.2 μm, and then tied with octopus thread. The weight at that time was measured, and the weight was taken as the weight before immersion (the total weight of the polymer, the tetrafluoroethylene sheet and the octopus yarn), while the total weight of the tetrafluoroethylene sheet and the octopus yarn was also measured. The weight was taken as the package weight. Next, the above polymer wrapped in a tetrafluoroethylene sheet and bound with octopus thread (referred to as "sample") was placed in a 50 ml container filled with ethyl acetate, allowed to stand at 23 ° C. for 7 days, and then the container. The sample after soaking in ethyl acetate is taken out from the sample, and the ethyl acetate adhering to the sample is sufficiently wiped off with a waste cloth to measure the weight. After drying in an hour dryer to remove ethyl acetate, the weight was measured, and the weight was taken as the weight after drying, and the degree of swelling was calculated from the following formula.
Swelling degree (%) = (ab) / (c-b) × 100 (1)
In the formula (1), a is the weight after immersion, b is the weight of the bag, and c is the weight after drying.
Further, when collecting the polymer after cross-linking, it may be collected from the pressure-sensitive adhesive layer surface of the surface protective film, or the same pressure-sensitive adhesive layer as that separately provided on the surface protection film is applied to a silicone separator or the like and dried. It may be collected from.

[Production Example 1]: Production of acrylic copolymer (1) 2-ethylhexyl acrylate (2EHA) (manufactured by Nihon Kasei Co., Ltd.) in a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, and a cooler. ): 100 parts by weight, 4-hydroxybutyl acrylate (4HBA) (manufactured by Nihon Kasei Co., Ltd.): 10 parts by weight, acrylic acid (AA) (manufactured by Nihon Kasei Co., Ltd.): 0.02 parts by weight, 2,2 as a polymerization initiator '-Azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd.): 0.02 parts by weight, ethyl acetate: 180 parts by weight are charged, nitrogen gas is introduced while gently stirring, and the liquid temperature in the flask is 65. The polymerization reaction was carried out for 6 hours while keeping the temperature at around ° C. to prepare a solution (solid content: 35% by weight) of the acrylic copolymer (1) having a weight average molecular weight of 540,000.

[Production Example 2]: Production of acrylic copolymer (2) 2-ethylhexyl acrylate (2EHA) (manufactured by Nippon Catalyst Co., Ltd.) in a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, and a cooler. ): 100 parts by weight, 2-hydroxyethyl acrylate (HEA) (manufactured by Toa Synthetic Co., Ltd.): 4 parts by weight, 2,2'-azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd.) as a polymerization initiator: 0 .02 parts by weight, ethyl acetate: 180 parts by weight were charged, nitrogen gas was introduced while gently stirring, and the polymerization reaction was carried out for 6 hours while keeping the liquid temperature in the flask at around 65 ° C., and the weight average molecular weight was 560,000. A solution (solid content: 35% by weight) of the acrylic copolymer (2) was prepared.

[Production Example 3]: Production of methacrylic copolymer (3) In a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, and a cooler, 100 parts by weight of toluene and dicyclopentadienyl methacrylate (dicyclopentadienyl methacrylate) ( DCPMA) (trade name: FA-513M, manufactured by Hitachi Kasei Kogyo Co., Ltd.): 60 parts by weight, methyl methacrylate (MMA) (manufactured by Mitsubishi Gas Chemical Company, Inc.): 40 parts by weight, and methyl thioglycolate as a chain transfer agent: 3.5. The heavy part was put in. Then, after stirring at 70 ° C. under a nitrogen atmosphere for 1 hour, 2,2'-azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd.): 0.2 parts by weight was added as a polymerization initiator, and 70 was added. A methacrylic copolymer having a weight average molecular weight of 4400 and Tg = 144 ° C. (calculated from Fox's formula) was reacted at ° C. for 2 hours, then at 80 ° C. for 4 hours, and then at 90 ° C. for 1 hour. The solution of 3) (solid content: 60% by weight) was prepared.

[Production Example 4]: Production of an acrylic pressure-sensitive adhesive composition (P1) for forming a pressure-sensitive adhesive for a polarizing plate (production of a solution of an acrylic polymer (A1)).
Butyl acrylate (BA): 94.9 parts by weight, acrylic acid (AA): 5 parts by weight, hydroxyethyl acrylate (HEA) in a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, and a cooler. : A monomer mixture containing 0.1 parts by weight was charged. Further, with respect to 100 parts by weight of the monomer mixture, 2,2'-azobisisobutyronitrile (AIBN): 0.1 part by weight was charged together with ethyl acetate as a polymerization initiator, and nitrogen gas was added while gently stirring. After the introduction and substitution with nitrogen, the liquid temperature in the flask was maintained at around 55 ° C. and the polymerization reaction was carried out for 7 hours. Then, ethyl acetate was added to the obtained reaction solution to prepare a solution of an acrylic polymer (A1) having a weight average molecular weight of 2 million adjusted to a solid content concentration of 20%.
(Acrylic Adhesive Composition (P1))
Isocyanate-based cross-linking agent (trade name: Coronate L, trimethylolpropane / tolylene isocyanate, manufactured by Nippon Polyurethane Industry Co., Ltd.): 0.6 with respect to 100 parts by weight of the solid content of the obtained acrylic polymer (A1) solution. By weight, silane coupling agent (trade name "KBM-403", manufactured by Shin-Etsu Chemical Co., Ltd.): 0.1 part by weight was blended to prepare an acrylic pressure-sensitive adhesive composition (P1).

[Manufacturing Example 5]: Manufacture of the adherend (A) (manufacture of a stator)
Using a polyvinyl alcohol film having a thickness of 75 μm (manufactured by Kuraray Co., Ltd .: VF-PS7500, width 1000 mm), the mixture was immersed in pure water at 30 ° C. for 60 seconds and stretched to a draw ratio of 2.5 times to reach 30 ° C. Staining in an aqueous iodine solution (weight ratio: pure water / iodine (I) / potassium iodide (KI) = 100/0.01/1) for 45 seconds and a draw ratio of 5.8 in a 4 wt% boric acid aqueous solution. It was stretched to double and immersed in pure water for 10 seconds, and then dried at 60 ° C. for 5 minutes while maintaining the tension of the film to obtain a substituent. The thickness of this polarizing element was 25 μm, and the water content was 15% by weight.
(Making a transparent protective film with an adhesive layer)
PVA resin (manufactured by Nippon Synthetic Chemical Industry Co., Ltd .: Gosenol): 100 parts by weight and cross-linking agent (manufactured by Dainippon Ink and Chemicals Co., Ltd .: water sol): 35 parts by weight are dissolved in pure water: 3760 parts by weight. Adjusted the adhesive. This adhesive is applied to one side of a 60 μm-thick triacetyl cellulose (TAC) film (manufactured by Fujifilm: TD-60UL) with a slot die and then dried at 85 ° C. for 1 minute to adhere to a thickness of 0.1 μm. A TAC film with an adhesive layer having an agent layer was obtained.
(Preparation of polarizing plate (A))
A polarizing plate (A) was produced by the method shown in FIG. The above-mentioned polarizing element was used as the polarizing element, and the unsaponified TAC film with the above-mentioned adhesive layer was used as the first transparent protective film B1. An acrylic film with an adhesive layer was used for the second transparent protective film B2, and the acrylic film with an adhesive layer had the above-mentioned adhesive layer except that an acrylic film having a thickness of 40 μm was used instead of the TAC film. It was made in the same manner as the TAC film of. As shown in FIG. 2, the TAC film with the adhesive layer (first transparent protective film B1) is from the side of the first roll R1, and the acrylic film with the adhesive layer (second transparent protective film B2) is from the second roll. It was conveyed from the side of R2. As the first roll R1 and the second roll R2, iron rolls having a diameter of 200 mm were used. The transport speed of each film was 20 m / min. The obtained polarizing plate (A) was dried at 80 ° C. for 2 minutes after bonding.
(Manufacturing of adherend (A))
The acrylic pressure-sensitive adhesive composition (P1) obtained in Production Example 4 was uniformly coated on the surface of a polyethylene terephthalate film (separator) having a thickness of 38 μm treated with a silicone-based release agent with a fountain coater at 155 ° C. A pressure-sensitive adhesive layer having a thickness of 20 μm was prepared by drying in an air-circulating constant temperature oven for 2 minutes. Next, the surface of the second transparent protective film of the above-mentioned polarizing plate (A) is corona-treated, and a separator having an adhesive layer formed is bonded to the corona-treated surface to form an adhesive as an adherend (A). An unkeratinized TAC polarizing plate with a layer was prepared. The water contact angle of the prepared unsaponified TAC polarizing plate with an adhesive layer was 69.9 degrees.

[Production Example 6]: Production of the adherend (B) (adjustment of the adhesive aqueous solution)
Polyvinyl alcohol-based resin containing an acetoacetyl group (average degree of polymerization: 1200, saponification degree: 98.5 mol%, acetoacetyl group modification degree: 5 mol%): 100 parts by weight, methylol melamine: 50 parts by weight, An aqueous solution prepared by dissolving in pure water at 30 ° C. and adjusting the solid content concentration to 3.7% by weight was prepared. An alumina colloidal aqueous solution (average particle size: 15 nm, solid content concentration: 10% by weight, positive charge): 18 parts by weight was added to 100 parts by weight of this aqueous solution to prepare an adhesive aqueous solution. The viscosity of the aqueous adhesive solution was 9.6 mPa · s, and the pH was in the range of 4 to 4.5.
(Manufacturing of polarizing plate with surface treatment)
UV-curable urethane acrylate monomer: 100 parts by weight and benzophenone-based photopolymerization initiator: A UV-curable resin composition consisting of 3 parts by weight, silica particles having an average particle diameter of 0.5 μm: 15 parts by weight and an average particle diameter of 1. .4 μm silica particles: 10 parts by weight were added to obtain a resin mixture. A viscosity adjusting solvent was further added to the obtained resin mixture to bring the solid content concentration to 50% by weight, and then the mixture was mixed with a high-speed stirrer. The obtained mixed solution is coated on the first transparent protective film B1 (TAC film) side of the polarizing plate (A) produced in Production Example 5 with a bar coater, and after the solvent is volatilized, it is irradiated with ultraviolet rays to cure it. An antiglare-treated polarizing plate (B) having a fine surface uneven structure and a thickness of 7 μm made of an ultraviolet curable resin film was obtained.
(Manufacturing of adherend (B))
The same procedure as in Production Example 5 was carried out except that the antiglare-treated polarizing plate (B) was used instead of the polarizing plate (A) to obtain an antiglare-treated polarizing plate with an adhesive layer as an adherend (B). .. The water contact angle of the prepared antiglare-treated polarizing plate with an adhesive layer was 88.4 degrees.

[Production Example 7]: Production of the adherend (C) A polyvinyl alcohol film having a thickness of 60 μm (average polymerization degree 2400, Kuraray VF-PE-A # 6000) was used as the raw film. The polyvinyl alcohol film was subjected to the following steps in the following order.
(Swelling process)
The swelling step was performed by two swelling baths of the embodiment shown in FIG. Pure water was used as the treatment liquid for each swelling bath. An expander roll having a radius of curvature of 2000 mm was used as the guide roll 13 installed in the first-stage swelling bath in FIG. The expander roll was placed at a position of 80% of the length of the polyvinyl alcohol film immersed in the treatment liquid (the length of the broken lines of p1 and p2 in FIG. 3). A flat roll was used as the other guide roll.
<1st stage>
The polyvinyl alcohol film was conveyed to a swelling bath having a one-step surface, immersed in pure water adjusted to 40 ° for 60 seconds, and uniaxially stretched to a draw ratio of 1.80 times while swelling.
<Second stage>
Subsequently, the polyvinyl alcohol film subjected to the first-step swelling step was transferred to the second-step swelling bath, immersed in pure water adjusted to 30 ° C. for 60 seconds, and stretched at a stretching ratio of 1. It was uniaxially stretched to 10 (total stretching ratio 1.98 times).
(Dyeing process)
As the treatment liquid for the dyeing bath, an iodine dyeing solution having a concentration of iodine: potassium iodide (weight ratio = 0.5: 8) of 0.3% by weight was used. The swelled polyvinyl alcohol film was transferred to a dyeing bath, immersed in the iodine dyeing solution adjusted to 30 ° C. for 60 seconds, and dyed while being uniaxially stretched to a total draw ratio of 3 times the original length. ..
(Crosslinking process)
As the treatment liquid for the cross-linking bath, an aqueous boric acid solution containing 3% by weight of boric acid and 3% by weight of potassium iodide was used. The treated polyvinyl alcohol film was transported to a cross-linked bath and uniaxially stretched to a total extension factor of 4 times with respect to the original length while being immersed in the boric acid aqueous solution adjusted to 30 ° C. for 19 seconds.
(Stretching process)
As the treatment liquid for the stretching bath, an aqueous boric acid solution containing 4% by weight of boric acid and 5% by weight of potassium iodide was used. The treated polyvinyl alcohol film was transported to a stretching bath and uniaxially stretched to a total stretching ratio of 6 times the original length while being immersed in a boric acid aqueous solution adjusted to 60 ° C. for 13 seconds.
(Washing process)
As the treatment liquid for the washing bath, an aqueous solution containing 3% by weight of potassium iodide was used. The treated polyvinyl alcohol film was transferred to a washing bath and immersed in the aqueous solution adjusted to 30 ° C. for 10 seconds.
(Drying process)
Then, the treated polyvinyl alcohol-based film was dried in an oven at 60 ° C. for 4 minutes to obtain a polarizing element.
(Manufacturing of adherend (C))
A triacetyl cellulose film having been saponified to a thickness of 80 μm was laminated on both sides of the above-mentioned polarizing element via an adhesive consisting of a 5% by weight fully saponified polyvinyl alcohol aqueous solution, and rolled. After close contact with, it was dried at 70 ° C. for 4 minutes. After that, the same procedure as in Production Example 5 was carried out except that the saponified TAC polarizing plate (C) was used instead of the polarizing plate (A), and the saponified TAC polarizing plate with an adhesive layer as the adherend (C) was obtained. Obtained. The water contact angle of the produced saponified TAC polarizing plate with an adhesive layer was 53.1 degrees.

[Example 1]: Production of the pressure-sensitive adhesive composition (1) and the surface protective film (1) The solution of the acrylic copolymer (1) obtained in Production Example 1 with respect to 100 parts by weight of the solid content thereof. , Organosiloxane (KF-353, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) having an oxyalkylene chain as a silicone component diluted to 10% by weight with ethyl acetate: 2 parts by weight (0.2 parts by weight in solid content), charged. As an alkali metal salt (ionic compound) as an inhibitor, lithium bis (trifluoromethanesulfonyl) imide (LiN (CF ₃ SO ₂ ) ₂ : LiTFSI, manufactured by Tokyo Kasei Kogyo Co., Ltd.): 0.15 parts by weight, isocyanate-based cross-linking Agent (trade name "Coronate HX", manufactured by Toso Co., Ltd.): 3.4 parts by weight, Narsem ferric iron as a cross-linking catalyst: 0.006 parts, Envirizer OL-1 (manufactured by Tokyo Fine Chemicals Co., Ltd.): 0.01 Add 0.2 parts by weight of the solution of the methacrylic copolymer (2) obtained in Production Example 2 as a solid content, and further add a polyoxyalkylene glycol compound (Sannicks GP-250, Sanyo Kasei Kogyo Co., Ltd.). (Manufactured by the same company) was added so as to be 1 part by weight with respect to 100 parts by weight of the solid content of the solution of the acrylic copolymer (1) obtained in Production Example 1, and the total solid content was 20% by weight. It was diluted with toluene so as to be, and stirred with a disper to obtain a pressure-sensitive adhesive composition (1).
The obtained pressure-sensitive adhesive composition (1) is applied to a base material "Lumilar S10" (thickness 38 μm, manufactured by Toray Industries, Inc.) made of a polyester resin with a fountain roll so that the thickness after drying is 10 μm, and the drying temperature is 130. It was cured and dried under the conditions of ° C. and a drying time of 20 seconds. In this way, the pressure-sensitive adhesive layer was produced on the substrate. Next, a silicone-treated surface of a base material made of a polyester resin having a thickness of 19 μm, one of which was treated with silicone, was attached to the surface of the pressure-sensitive adhesive layer to obtain a surface protective film (1).
The results are shown in Table 1.

[Example 2]: Production of the pressure-sensitive adhesive composition (2) and the surface protective film (2) The amount of coronate HX was changed to 8.1 parts by weight in terms of solid content, and the amount of GP250 was changed to 3 parts by weight. Except for the above, the same procedure as in Example 1 was carried out to obtain a pressure-sensitive adhesive composition (2) and a surface protective film (2).
The results are shown in Table 1.

[Example 3]: Production of adhesive composition (3) and surface protective film (3) The amount of coronate HX was changed to 12.8 parts by weight in terms of solid content, and the amount of GP250 was changed to 5 parts by weight. Except for the above, the same procedure as in Example 1 was carried out to obtain a pressure-sensitive adhesive composition (3) and a surface protective film (3).
The results are shown in Table 1.

[Example 4]: Production of adhesive composition (4) and surface protective film (4) The amount of coronate HX was changed to 1.7 parts by weight in terms of solid content, and GP250 was changed to GP600 (manufactured by Sanyo Chemical Industries, Ltd.). Polyoxypropylene glyceryl ether, Mn = 600): The same procedure as in Example 1 was carried out except that the content was changed to 1 part by weight to obtain a pressure-sensitive adhesive composition (4) and a surface protective film (4).
The results are shown in Table 1.

[Example 5]: Production of adhesive composition (5) and surface protective film (5) The amount of coronate HX was changed to 1.6 parts by weight in terms of solid content, and GP250 was changed to GP1000 (manufactured by Sanyo Chemical Industries, Ltd.). Polyoxypropylene glyceryl ether, Mn = 1000): The same procedure as in Example 1 was carried out except that the content was changed to 1 part by weight to obtain a pressure-sensitive adhesive composition (5) and a surface protective film (5).
The results are shown in Table 1.

[Example 6]: Production of adhesive composition (6) and surface protective film (6) The amount of coronate HX was changed to 3.6 parts by weight in terms of solid content, and GP250 was changed to ADEKApolyether EDP-300 (stock). Manufactured by ADEKA Corporation, N, N, N', N', -tetrakis (2-hydroxypropyl) ethylenediamine, Mn = 300): changed to 1 part by weight, and Nasem zinc instead of Envirizer OL-1 as a cross-linking catalyst. (Acetylacetone zinc monohydrate manufactured by Nippon Kagaku Sangyo Co., Ltd.) The same procedure as in Example 1 was carried out except that the content was changed to 0.01 parts by weight, and the pressure-sensitive adhesive composition (6) and the surface protective film (6) were applied. Obtained.
The results are shown in Table 1.

[Example 7]: Production of the pressure-sensitive adhesive composition (7) and the surface protective film (7) As the polyol (A), Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having three OH groups: Sanniks GP-3000 (manufactured by Sanyo Kasei Co., Ltd., Mn = 3000), which is a polyol having 85 parts by weight and three OH groups: Sanniks GP-1000 (Sanyo), which is a polyol having 13 parts by weight and three OH groups. Kasei Co., Ltd., Mn = 1000): 2 parts by weight is used, and as the polyfunctional isocyanate compound (B), coronate HX (Nippon Polyol Industry Co., Ltd.), which is a polyfunctional alicyclic isocyanate compound,: 13.5 parts by weight. A catalyst (manufactured by Nippon Kagaku Sangyo Co., Ltd., trade name: Nasem ferrous iron): 0.04 part by weight, ethyl acetate: 210 parts by weight as a diluting solvent, and agitated with a disper to make a pressure-sensitive adhesive composition ( 7) was obtained.
The obtained pressure-sensitive adhesive composition (7) was applied to a base material "Lumilar S10" (thickness 38 μm, manufactured by Toray Industries, Inc.) made of a polyester resin with a fountain roll so that the thickness after drying was 10 μm, and the drying temperature was 130 ° C. The mixture was cured and dried under the condition of a drying time of 2 minutes. In this way, the pressure-sensitive adhesive layer was produced on the substrate. Next, a silicone-treated surface of a base material made of a polyester resin having a thickness of 19 μm, one of which was treated with silicone, was attached to the surface of the pressure-sensitive adhesive layer to obtain a surface protective film (7). The results are shown in Table 1. Indicated.

[Comparative Example 1]: Production of Adhesive Composition (C1) and Surface Protective Film (C1) The solution of the acrylic copolymer (1) obtained in Production Example 1 was diluted with ethyl acetate to 20% by weight. A solution obtained by diluting an organosiloxane (KF-353, manufactured by Shinetsu Chemical Industry Co., Ltd.) having an oxyalkylene chain as a silicone component in 500 parts by weight (100 parts by weight in solid content) of this solution with ethyl acetate to 10% by weight: 2 parts by weight. Part (0.2 parts by weight in solid content), as an alkali metal salt (ionic compound) that is an antistatic agent, lithium bis (trifluoromethanesulfonyl) imide (LiN (CF ₃ SO ₂ ) ₂ : LiTFSI, Tokyo Kasei Kogyo (Manufactured by): 0.15 parts by weight, isocyanate-based cross-linking agent (trade name "Coronate HX", manufactured by Toso Co., Ltd.) by 3.5 parts by weight, Envirizer OL-1 (manufactured by Tokyo Fine Chemical Co., Ltd.) as a cross-linking catalyst Add 0.5 part by weight of 0.02 part by weight and 0.5 part by weight of the solution of the methacrylic copolymer (2) obtained in Production Example 2 as a solid content, and dilute with toluene so that the total solid content becomes 20% by weight. Then, the mixture was stirred with a disper to obtain a pressure-sensitive adhesive composition (C1).
The obtained pressure-sensitive adhesive composition (C1) was applied to a base material "Lumilar S10" (thickness 38 μm, manufactured by Toray Industries, Inc.) made of a polyester resin with a fountain roll so that the thickness after drying was 15 μm, and the drying temperature was 130. It was cured and dried under the conditions of ° C. and a drying time of 20 seconds. In this way, the pressure-sensitive adhesive layer was produced on the substrate. Next, a silicone-treated surface of a base material made of a polyester resin having a thickness of 19 μm, one of which was treated with silicone, was attached to the surface of the pressure-sensitive adhesive layer to obtain a surface protective film (C1).
The results are shown in Table 1.

[Comparative Example 2]: Production of Adhesive Composition (C2) and Surface Protective Film (C2) The solution of the acrylic copolymer (2) obtained in Production Example 2 was diluted with ethyl acetate to 20% by weight. In 100 parts by weight of this solution, an organosiloxane having a polyoxyalkylene chain in the main chain (trade name: KF6004, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) diluted to 10% by weight with ethyl acetate: 0.8 parts by weight, bis ( Trifluoromethanesulfonyl) imidelithium (manufactured by Tokyo Kasei Kogyo Co., Ltd.) diluted to 10% by weight with ethyl acetate: 0.2 parts by weight, isocyanate-based cross-linking agent (trade name: Coronate L, manufactured by Toso Co., Ltd., 75% by weight) : 0.8 parts by weight, Envirizer OL-1 (manufactured by Tokyo Fine Chemicals Co., Ltd.) as a cross-linking catalyst: Add 0.02 parts by weight, dilute with toluene so that the total solid content is 20% by weight, and disperse. To obtain the pressure-sensitive adhesive composition (C2).
The obtained pressure-sensitive adhesive composition (C2) was applied to a base material "Lumilar S10" (thickness 38 μm, manufactured by Toray Industries, Inc.) made of a polyester resin with a fountain roll so that the thickness after drying was 10 μm, and the drying temperature was 130. It was cured and dried under the conditions of ° C. and a drying time of 20 seconds. In this way, the pressure-sensitive adhesive layer was produced on the substrate. Next, a silicone-treated surface of a base material made of a polyester resin having a thickness of 19 μm, one of which was treated with silicone, was attached to the surface of the pressure-sensitive adhesive layer to obtain a surface protective film (C2).
The results are shown in Table 1.

The surface protective film of the present invention can be used for any suitable application. Preferably, the surface protective film of the present invention is preferably used in the field of optical members and electronic members.

1 Base material layer 2 Adhesive layer 10 Surface protective film A Polarizer B1 First transparent protective film B2 Second transparent protective film R1 First roll R2 Second roll M Angle changing means

Claims (16)

A surface protective film containing an adhesive layer and a base material layer.
When the free induction decay signal obtained by pulse NMR measurement of the pressure-sensitive adhesive layer is separated into two components by the non-linear least square method, the component with a short relaxation time is the hard component (S) and the component with a long relaxation time is the soft component (the component with a long relaxation time). _{L), the spin-spin relaxation time T2 (L) 30} of the proton of the soft component (L) measured at 30 ° C. and the spin-spin relaxation time T2 of the proton of the soft component (L) measured at 60 ° C. The ratio of (L) ₆₀ to T2 (L) ₆₀ / T2 (L) ₃₀ is 2.15 to 3.05.
Shear adhesive strength is 10 N / cm ² or more,
High-speed peeling force is 0.8 N / 25 mm or less,
Surface protective film. The surface protective film according to claim 1, wherein the pressure-sensitive adhesive layer has a thickness of 1 μm to 500 μm. The surface protective film according to claim 1 or 2, wherein the base material layer has a thickness of 1 μm to 500 μm. The pressure-sensitive adhesive layer is composed of a pressure-sensitive adhesive formed from the pressure-sensitive adhesive composition, and the pressure-sensitive adhesive composition comprises a (meth) acrylic copolymer (A), a polyfunctional alcohol (C), and a cross-linking agent (D). The surface protective film according to any one of claims 1 to 3, which comprises. The (meth) acrylic copolymer (A) has a (meth) acrylic acid alkyl ester having 4 to 12 carbon atoms in the alkyl group of the (a1 component) alkyl ester moiety, and a (a2 component) OH group (. The surface protective film according to claim 4, which is formed by polymerization from the composition (a) containing a meta) acrylic acid ester. The surface protective film according to claim 5, wherein the composition (a) contains (meth) acrylic acid. The surface protective film according to any one of claims 4 to 6, wherein the polyfunctional alcohol (C) has 3 to 6 functional groups. The surface protective film according to any one of claims 4 to 7, wherein the polyfunctional alcohol (C) has a number average molecular weight of 50 to 10000. The pressure-sensitive adhesive composition is formed by polymerization from the composition (b) containing a (meth) acrylic acid alkyl ester in which the alkyl group of the (b1 component) alkyl ester moiety is an alicyclic hydrocarbon group. The surface protective film according to any one of claims 4 to 8, which comprises the system copolymer (B). The surface protective film according to claim 9, wherein the composition (b) contains a (meth) acrylic acid alkyl ester in which the alkyl group of the (b2 component) alkyl ester moiety has 1 to 3 carbon atoms. The surface protective film according to claim 9 or 10, wherein the composition (b) contains a mercaptan. The surface protective film according to any one of claims 9 to 11, wherein the (meth) acrylic copolymer (B) has a Tg of 50 ° C to 250 ° C. The surface protective film according to any one of claims 9 to 12, wherein the (meth) acrylic copolymer (B) has a weight average molecular weight of 1000 to 30,000. The surface protective film according to any one of claims 4 to 13, wherein the pressure-sensitive adhesive composition contains an ionic liquid. The surface protective film according to any one of claims 1 to 14, wherein the number of bubbles generated after the high-temperature and high-pressure treatment is 10 or less. The surface protective film according to claim 15, which is used to protect the surface of an adherend having a water contact angle of 60 degrees or more on the surface.

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