KR20190143387A - Surface protection film - Google Patents

Abstract

The present invention relates to a surface protective film having sufficiently low contamination of a surface of an object to be attached. The surface protective film of the present invention comprises an adhesive formed by an adhesive composition, wherein the adhesive composition includes an adhesive layer including a base polymer and a silicon-based additive and/or a fluorine-based additive.

Description

Surface protection film {SURFACE PROTECTION FILM}

The present invention relates to a surface protective film.

In the manufacturing process of an optical member or an electronic member, in order to prevent the surface of the said optical member or the said electronic member from being damaged at the time of processing, assembly, inspection, transport, etc., exposure of the said optical member or the said electronic member is generally carried out. A surface protective film is attached to the surface. Such a surface protection film is peeled from an optical member or an electronic member at the time when surface protection is no longer needed (patent document 1).

In the optical member or the electronic member with such a surface protection film, it is important that the surface protection film can be peeled smoothly only at the interface between the surface protection film and the optical member or the electronic member when the surface protection film is to be peeled off as described above. Do.

However, when the optical member or the electronic member is provided with a fragile member such as a thin glass or a barrier film, if the surface protective film is to be peeled off, even when a conventional surface protective film with light peelability is used, The fragile member may be broken by the peeling force.

For this reason, the surface protection film provided with lighter peelability, ie, superhard peeling property, compared with the conventional surface protection film provided with light peelability (patent document 2) is reported.

However, in the prior art, for example, when stored for a long time in a harsh environment, there is a problem that the adhesive force rises with time and becomes heavy.

In order to suppress heavy peeling, the method of adding the additive as reported in Japanese Patent Document 2 in excess amount is also mentioned. However, if such a method is adopted, the degree of contamination of the surface of the adherend after peeling off of the surface protection film is large, and if the surface protection film is to be adhered again, the surface protection film becomes difficult to adhere due to contamination of the surface of the adherend. There is.

As mentioned above, in the manufacturing process of an optical member or an electronic member, in the surface protection film adhere | attached on an exposed surface in order to prevent the damage of the surface at the time of processing, assembly, inspection, transport, etc., especially in severe environment Even when it is stored for a long time, it is required to be able to sufficiently suppress heavy desquamation over time and to sufficiently reduce the contamination on the surface of the adherend.

Japanese Patent Application Laid-Open No. 2016-17109 Japanese Patent Publication No. 2017-160422

The subject of this invention does not peel easily from a to-be-adhered body, and even when it is stored for a long time in a severe environment, heavy peeling at time can fully be suppressed, and the surface of the said to-be-adhered body by adhering to a to-be-adhered body is attached. It is to provide the surface protection film with low enough contamination.

The surface protection film of this invention,

As a surface protection film which has an adhesive layer,

After bonding the said adhesive layer of the said surface protection film to a glass plate, and leaving it to stand at the temperature of 23 degreeC for 30 minutes, when peeling the said surface protection film from the said glass plate at 180 degree of peeling angles, and the peeling rate of 300 mm / min at the temperature of 23 degreeC, When the peeling force is referred to as peeling force A, the peeling force A is 0.005 N / 25 mm to 0.50 N / 25 mm,

After bonding the said adhesive layer of the said surface protection film to a glass plate, and leaving it at the temperature of 100 degreeC for 2 days, when peeling the said surface protection film from the said glass plate at 180 degree of peeling angles and peeling rate 300mm / min at the temperature of 23 degreeC, When the peeling force is referred to as peeling force B, the peeling force elongation rate P calculated by (peeling force B / peeling force A) × 100 is 400% or less,

The storage modulus at -70 ° C of the pressure-sensitive adhesive layer is 5.0 × 10 ⁸ Pa to 1.0 × 10 ¹⁰ Pa,

The storage elastic modulus at 23 degrees C of the said adhesive layer is 7.0 * 10 < ⁵ > Pa ^~ 1.0 * 10 <^7> Pa,

The storage modulus at 100 ° C. of the pressure-sensitive adhesive layer is 7.0 × 10 ⁵ Pa to 5.0 × 10 ⁶ Pa.

In one embodiment, after bonding the said adhesive layer of the said surface protection film to a glass plate, and leaving it to stand at 23 degreeC for 7 days, the said surface protection film is 180 degree from the said glass plate at a temperature of 23 degreeC, and peeling rate is 300 mm / When the peeling force at the time of peeling in minutes is made into peeling force C, the peeling force time rise rate Q computed by (peeling force C / peeling force A) x100 is 160% or less.

In one embodiment, the surface protection film of this invention is 50% or more of residual adhesiveness with respect to the glass plate in 23 degreeC.

In one embodiment, the adhesive which comprises the said adhesive layer is formed from an adhesive composition, and the said adhesive composition contains a base polymer, a silicone type additive, and / or a fluorine-type additive.

In one embodiment, the said adhesive composition contains a fatty acid ester.

In one embodiment, the said silicone type additive is at least 1 sort (s) chosen from a siloxane bond containing compound, a hydroxyl group containing silicone type compound, and a crosslinkable functional group containing silicone type compound.

In one embodiment, the said fluorine-type additive is at least 1 sort (s) chosen from a fluorine-containing compound, a hydroxyl-containing fluorine-type compound, and a crosslinkable functional group-containing fluorine-type compound.

In one embodiment, the said base polymer is at least 1 sort (s) chosen from a urethane prepolymer, a polyol, acrylic resin, rubber resin, and silicone resin.

The optical member of the present invention is to which the surface protection film of the present invention is bonded.

The electronic member of the present invention is to which the surface protection film of the present invention is bonded.

According to the present invention, it is not easy to peel off from the adherend, and even if the initial peeling force after adhering to the adherend is large, heavy peeling in time can be sufficiently suppressed, and the adherend by attaching to the adherend It is possible to provide a surface protective film with sufficiently low contamination of the surface.

1 is a schematic cross-sectional view of a surface protection film according to one embodiment of the present invention.

≪≪A. Surface protection film≫≫

The surface protection film of this invention has an adhesive layer. As long as the surface protection film of this invention has an adhesive layer, you may be equipped with arbitrary other suitable members in the range which does not impair the effect of this invention. Typically, the surface protection film of this invention has a base material layer and an adhesive layer.

1 is a schematic cross-sectional view of a surface protection film according to one embodiment of the present invention. In FIG. 1, the surface protection film 10 is equipped with the base material layer 1 and the adhesive layer 2. FIG. In FIG. 1, the base material layer 1 and the adhesive layer 2 are laminated | stacked directly.

In FIG. 1, the surface on the opposite side of the base material layer 1 of the adhesive layer 2 may be equipped with arbitrary appropriate peeling liners (sometimes called a peeling sheet, a separator) for protection until use. (Not shown). As the release liner, for example, a release liner in which a surface of a base material (liner base material) such as paper or plastic film is siliconized, or a surface of a base material (liner base material) such as paper or plastic film is laminated with polyolefin resin Etc. can be mentioned. As a plastic film as a liner base material, a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethyl pentene film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyethylene terephthalate film, a polybutylene tere Phthalate film, polyurethane film, ethylene-vinyl acetate copolymer film, etc. are mentioned. As a plastic film as a liner base material, Preferably it is 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 is preferably 5 µm to 500 µm, more preferably 10 µm to 450 µm, still more preferably 15 µm to 400 µm, and particularly preferably 20 µm to 300 µm.

In the surface protection film of this invention, after bonding the adhesive layer of a surface protection film to a glass plate and leaving it for 30 minutes at the temperature of 23 degreeC, the said surface protection film is 180 degree from the said glass plate at a temperature of 23 degreeC, and peeling rate is 300 mm / min. When the peeling force at the time of peeling with the peeling force A, peeling force A becomes like this. Preferably it is 0.005N / 25mm-0.50N / 25mm, More preferably, it is 0.007N / 25mm-0.40N / 25mm, More preferably Preferably it is 0.010N / 25mm-0.30N / 25mm, More preferably, it is 0.012N / 25mm-0.20N / 25mm, More preferably, it is 0.015N / 25mm-0.10N / 25mm, Especially preferably 0.017N / 25 mm-0.075 N / 25 mm, Most preferably, they are 0.020 N / 25 mm-0.050 N / 25 mm. If the peeling force A is in the said range, the surface protection film of this invention may become difficult to peel easily from a to-be-adhered body, and typically, in the manufacturing process of an optical member or an electronic member, Peeling of the surface protection film of this invention adhering to the exposed surface may become difficult to occur. In addition, the detail of the measurement of peeling force A is mentioned later.

In the surface protection film of this invention, after bonding the adhesive layer of a surface protection film to a glass plate and leaving it for 2 days at the temperature of 100 degreeC, the said surface protection film is 180 degree from the said glass plate at a temperature of 23 degreeC, and peeling rate is 300 mm / min. When the peeling force at the time of peeling with the peeling force B, peeling force B becomes like this. Preferably it is 0.010N / 25mm-1.0N / 25mm, More preferably, it is 0.015N / 25mm-0.75N / 25mm, More preferably Preferably it is 0.020N / 25mm-0.50N / 25mm, Especially preferably, it is 0.025N / 25mm-0.255N / 25mm, Most preferably, it is 0.030N / 25mm-0.20N / 25mm. When peeling force B exists in the said range, even if it is stored for a long term in severe environment, the surface protection film of this invention can fully suppress the heavy peeling at time. In addition, the detail of the measurement of peeling force B is mentioned later.

As for the surface protection film of this invention, with respect to peeling force A and the peeling force B, the peeling force temporal increase rate P computed by (peeling force B / peeling force A) * 100 becomes like this. Preferably it is 400% or less, More preferably, It is 375% or less, More preferably, it is 350% or less, Especially preferably, it is 325% or less, Most preferably, it is 300% or less. Although it is so preferable that it is small, it is more preferable about the lower limit of peeling force lapse rate P over time, Preferably it is 80% or more. When the peeling force elongation rate P is in the said range, the surface protection film of this invention does not peel easily from a to-be-adhered body, and even when it is stored for a long time in a severe environment, heavy peeling at time can fully be suppressed. .

In the surface protection film of this invention, after bonding the adhesive layer of a surface protection film to a glass plate and leaving it to stand at 23 degreeC for 7 days, the said surface protection film is peeled off from the said glass plate at the temperature of 23 degreeC with peeling angle of 180 degree, and peeling rate 300mm / min. When the peeling force at the time of peeling is called peeling force C, peeling force C becomes like this. Preferably it is 0.005N / 25mm-0.50N / 25mm, More preferably, it is 0.007N / 25mm-0.40N / 25mm, More preferably, Is 0.010 N / 25 mm to 0.30 N / 25 mm, more preferably 0.012 N / 25 mm to 0.20 N / 25 mm, more preferably 0.015 N / 25 mm to 0.10 N / 25 mm, particularly preferably 0.017 N / 25 mm It is -0.075N / 25mm, Most preferably, it is 0.020N / 25mm-0.060N / 25mm. When peeling force C exists in the said range, the surface protection film of this invention can fully suppress the heavy peeling in time, even when stored for a long time in severe environment. In addition, the detail of the measurement of the said peeling force C is mentioned later.

As for the surface protection film of this invention, with respect to peeling force A and the peeling force C, the peeling force temporal increase rate Q computed by (peeling force C / peeling force A) * 100 becomes like this. Preferably it is 160% or less, More preferably, It is 155% or less, More preferably, it is 150% or less, Especially preferably, it is 145% or less, Most preferably, it is 140% or less. Although it is so preferable that it is small, it is more preferable that it is small about the minimum of peeling time lapse | temporal rise rate Q, Preferably it is 80% or more. When the peeling force elongation rate Q is in the said range, the surface protection film of this invention will not peel easily from a to-be-adhered body, and even if it is stored for a long time in a severe environment, it will be able to fully suppress the heavy peeling at time. Can be.

In the surface protection film of this invention, the storage elastic modulus at -70 degreeC of an adhesive layer becomes like this. Preferably it is 5.0 * 10 < ⁸ > Pa ~ 1.0 * 10 <^10> Pa, More preferably, it is 7.0 * 10 < ⁸ > Pa ~ 8.0 * 10 <^9>. and Pa, more preferably from ^{9.0 × 10 8 Pa~6.0 × 10 9} Pa , and particularly preferably from ^{1.0 × 10 9 Pa~4.0 × 10 9} Pa , and most preferably 1.5 × 10 ⁹ Pa~3.0 × 10 ⁹ Pa. If the storage elastic modulus at -70 degreeC of an adhesive layer exists in the said range, the surface protection film of this invention does not peel easily from a to-be-adhered body, Even if the initial peeling force after adhering to a to-be-adhered body is large, Heavy peeling can be fully suppressed, and the effect that the contamination of the surface of the said adherend by adhering to a to-be-adhered body is sufficiently low can be expressed more. In addition, the detail of the measurement of the storage elastic modulus at -70 degreeC of an adhesive layer is mentioned later.

In the surface protection film of this invention, the storage elastic modulus at 23 degrees C of an adhesive layer becomes like this. Preferably it is 7.0 * 10 < ⁵ > Pa ^~ 1.0 * 10 <^7> Pa, More preferably, it is 7.0 * 10 < ⁵ > Pa ^~ 8.0 * 10 <^6> Pa More preferably 7.0 × 10 ⁵ Pa to 6.0 × 10 ⁶ Pa, particularly preferably 7.0 × 10 ⁵ Pa to 4.0 × 10 ⁶ Pa, most preferably 7.0 × 10 ⁵ Pa to 2.0 × 10 ⁶ Pa. If the storage elastic modulus at 23 degrees C of an adhesive layer exists in the said range, the surface protection film of this invention does not peel easily from a to-be-adhered body, Even if the initial peeling force after adhering to a to-be-adhered body is large, it is heavy at time. Lysification can be sufficiently suppressed, and the effect that the contamination of the surface of the adherend by adhering to the adherend is sufficiently low can be more expressed. In addition, the detail of the measurement of the storage elastic modulus at 23 degreeC of an adhesive layer is mentioned later.

In the surface protection film of this invention, the storage elastic modulus at 100 degrees C of an adhesive layer becomes like this. Preferably it is 7.0 * 10 < ⁵ > Pa ^~ 5.0 * 10 <^6> Pa, More preferably, it is 7.0 * 10 < ⁵ > Pa <3.0 * 10 <^6> Pa More preferably 7.0 × 10 ⁵ Pa to 2.0 × 10 ⁶ Pa, particularly preferably 7.0 × 10 ⁵ Pa to 1.0 × 10 ⁶ Pa, most preferably 7.0 × 10 ⁵ Pa to 9.9 × 10 ⁵ Pa. If the storage elastic modulus at 100 degrees C of an adhesive layer exists in the said range, the surface protection film of this invention does not peel easily from a to-be-adhered body, Even if the initial peeling force after adhering to a to-be-adhered body is large, it is heavy at time. Lysification can be sufficiently suppressed, and the effect that the contamination of the surface of the adherend by adhering to the adherend is sufficiently low can be more expressed. In addition, the detail of the measurement of the storage elastic modulus at 100 degreeC of an adhesive layer is mentioned later.

The surface protection film of the present invention preferably has a residual adhesion rate of 50% or more, more preferably 60% to 100%, still more preferably 70% to 100%, and particularly preferably 80% to 100%. Most preferably, it is 85%-100%. When the residual adhesion rate is in the above range, the surface protective film of the present invention can exhibit an effect that the contamination on the surface of the adherend by adhering to the adherend is sufficiently low. In addition, the detail of the measurement of residual adhesion rate is mentioned later.

The surface protection film of this invention can be manufactured 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 hot melt on a base material layer,

(2) Method of depositing the adhesive layer formed by apply | coating the solution and the heat melt of the formation material of the adhesive layer on a separator,

(3) a method of extruding and applying the forming material of the pressure-sensitive adhesive layer onto a base material layer;

(4) a method of extruding the base material layer and the pressure-sensitive adhesive layer into two or multiple layers,

(5) a method of single layer laminating an adhesive layer on a base material layer or a method of laminating an adhesive layer in two layers together with a laminate layer,

(6) It can carry out according to arbitrary appropriate manufacturing methods, such as the method of laminating | stacking two layers or multilayers of base material layer forming materials, such as an adhesive layer and a film and a laminate layer.

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, or the like can be used.

≪A-1. Base layer≫

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

The thickness of the base material layer is preferably 4 µm to 450 µm, more preferably 8 µm to 400 µm, still more preferably 12 µm to 350 µm, and particularly preferably 16 µm to 250 µm.

About the surface which does not lay the adhesive layer of a base material layer, a mold release process is performed by adding fatty acid amide, polyethyleneimine, a long chain alkyl type additive, etc. to a base material layer for the purpose of formation of the winding body which is easy to rewind, etc. Alternatively, a coat layer made of any suitable release agent such as silicone, long chain alkyl or fluorine may be provided.

As a material of a base material layer, arbitrary appropriate materials can be employ | adopted according to a use. For example, plastics, paper, a metal film, a nonwoven fabric etc. are mentioned. Preferably plastic. That is, the base material layer is preferably a plastic film. The base material layer may be comprised by 1 type of material, and may be comprised by 2 or more types of material. For example, you may be comprised from 2 or more types of plastics.

Examples of the plastics include polyester resins, polyamide resins, polyolefin resins, and the like. As polyester-based resin, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc. are mentioned, for example. As polyolefin resin, the homopolymer of an olefin monomer, the copolymer of an olefin monomer, etc. are mentioned, for example. Specifically as polyolefin resin, it is a homo polypropylene, for example; Propylene copolymers such as block-based, random-based and graft-based copolymers having an ethylene component as a copolymerization component; Reactor TPO; Ethylene polymers such as low density, high density, linear low density and ultra low density; Ethylene propylene copolymer, ethylene vinyl acetate copolymer, ethylene methyl acrylate copolymer, ethylene ethyl acrylate copolymer, ethylene butyl acrylate copolymer, ethylene methacrylic acid copolymer, ethylene methyl methacrylate copolymer Ethylenic copolymers such as these; Etc. can be mentioned.

The base material layer may contain arbitrary appropriate additives as needed. As an additive which may be contained in a base material layer, antioxidant, a ultraviolet absorber, a light stabilizer, an antistatic agent, a filler, a pigment, etc. are mentioned, for example. The kind, the number, and the amount of the additive which may be contained in the substrate layer may be appropriately set according to the purpose. In particular, when the material of the base material layer is plastic, it is preferable to contain several of the above additives for the purpose of preventing degradation. From the viewpoint of improving weather resistance and the like, the additives are particularly preferably antioxidants, ultraviolet absorbers, light stabilizers and fillers.

Arbitrary suitable antioxidant can be employ | adopted as antioxidant. Examples of such antioxidants include phenolic antioxidants, phosphorus-based heat stabilizers, lactone-based heat stabilizers, sulfur-based heat stabilizers, phenol-phosphorus antioxidants and the like. The content ratio of the antioxidant is preferably 1% by weight or less, more preferably 0.5% by weight or less, relative to the base resin of the substrate layer (if the substrate layer is a blended material, the blended material is a base resin). Preferably it is 0.01 weight%-0.2 weight%.

Arbitrary appropriate ultraviolet absorbers can be employ | adopted as a ultraviolet absorber. As such a ultraviolet absorber, a benzotriazole type ultraviolet absorber, a triazine type ultraviolet absorber, a benzophenone type ultraviolet absorber etc. are mentioned, for example. The content ratio of the ultraviolet absorber is preferably 2% by weight or less, more preferably 1% by weight or less with respect to the base resin forming the substrate layer (when the substrate layer is a blended material, the blended material is a base resin). More preferably, they are 0.01 weight%-0.5 weight%.

Arbitrary suitable light stabilizers can be employ | adopted as a light stabilizer. As such a light stabilizer, a hindered amine light stabilizer, a benzoate light stabilizer, etc. are mentioned, for example. The content ratio of the light stabilizer is preferably 2% by weight or less, more preferably 1% by weight or less, relative to the base resin that forms the substrate layer (if the substrate layer is a blended material, the blended material is a base resin). More preferably, they are 0.01 weight%-0.5 weight%.

Arbitrary appropriate fillers can be employ | adopted as a filler. As such a filler, an inorganic filler etc. are mentioned, for example. Specifically as an inorganic filler, carbon black, titanium oxide, zinc oxide, etc. are mentioned, for example. The content ratio of the filler is preferably 20% by weight or less, more preferably 10% by weight or less, with respect to the base resin that forms the substrate layer (if the substrate layer is a blended material, the blended material is a base resin), More preferably, they are 0.01 weight%-10 weight%.

Moreover, as an additive, inorganic, low molecular weight, and high molecular weight antistatic agents, such as surfactant, an inorganic salt, polyhydric alcohol, a metal compound, carbon, are mentioned suitably for the purpose of providing antistatic property. In particular, a high molecular weight antistatic agent or carbon is preferable from the viewpoint of contamination and stickiness.

≪A-2. Adhesive Layer≫

The pressure-sensitive adhesive layer may be composed of an adhesive. The pressure-sensitive adhesive may be formed of a pressure-sensitive adhesive composition.

The pressure-sensitive adhesive layer can be formed by any suitable method. As such a method, the method of apply | coating an adhesive composition on a base material layer, and forming an adhesive layer on a base material layer is mentioned, for example. As such a coating method, the extrusion coat by a roll coat, a gravure coat, a reverse coat, a roll brush, a spray coat, an air knife coat method, a die coater, etc. are mentioned, for example.

Preferably the thickness of an adhesive layer is 1 micrometer-150 micrometers, More preferably, it is 2 micrometers-140 micrometers, More preferably, it is 3 micrometers-130 micrometers, More preferably, it is 4 micrometers-120 micrometers, More preferably Preferably it is 5 micrometers-100 micrometers, More preferably, it is 10 micrometers-90 micrometers, Especially preferably, it is 20 micrometers-85 micrometers, Most preferably, it is 30 micrometers-80 micrometers.

The pressure-sensitive adhesive composition preferably comprises a base polymer, a low molecular weight polyol, a silicone additive and / or a fluorine additive. When the pressure-sensitive adhesive composition contains a base polymer, a low molecular weight polyol, a silicone-based additive and / or a fluorine-based additive, the surface protective film of the present invention does not easily peel off from the adherend, and the initial peeling force after adhering to the adherend. Even if this is large, the heavy peeling at time can fully be suppressed, and the effect that the contamination of the surface of the said to-be-adhered body by adhering to a to-be-adhered body is sufficiently low can be expressed more. In a preferred embodiment of the present invention, it is possible to adhere to the adherend without being easily peeled off from the adherend, by adopting a technical idea that is not particularly used in combination with a low molecular weight polyol and a silicone-based additive and / or a fluorine-based additive. Even if the initial peeling force after this is large, the heavy peeling at time can fully be suppressed, and the surface protection film which can express more the effect that the contamination of the surface of the said adherend by adhering to a to-be-adhered body is low enough can be expressed more. Can be.

The content ratio of the total amount of the base polymer, the low molecular weight polyol, the silicone additive and the fluorine additive in the pressure-sensitive adhesive composition is preferably 50% by weight to 100% by weight, more preferably 60% by weight to 100% by weight, still more preferably It is 70 to 100 weight%, Especially preferably, it is 75 to 100 weight%, Most preferably, it is 80 to 100 weight%. When the content ratio of the total amount of the base polymer, the silicone-based additive, and the fluorine-based additive in the pressure-sensitive adhesive composition is in the above range, the surface protective film of the present invention does not easily peel off from the adherend, and the initial peeling force after adherence to the adherend is Even if it is large, heavy peeling at time can fully be suppressed, and the effect that the contamination of the surface of the said adherend by adhering to a to-be-adhered body is sufficiently low can be expressed more.

Content of the low molecular weight polyol in an adhesive composition becomes like this. Preferably it is 0.01 weight part-50 weight part, More preferably, it is 0.05 weight part-25 weight part, More preferably, it is 0.07 weight part-with respect to 100 weight part of base polymers. It is 30 weight part, More preferably, it is 0.1 weight part-20 weight part, More preferably, it is 0.3 weight part-15 weight part, Especially preferably, it is 0.5 weight part-10 weight part, Most preferably, 0.7 weight part It is 7.0 weight part. When content of the low molecular weight polyol in an adhesive composition exists in the said range, the surface protection film of this invention does not peel easily from a to-be-adhered body, Even if the initial peeling force after adhering to a to-be-adhered body is large, the delamination in time will be performed. It can fully suppress and the effect that the contamination of the surface of the said to-be-adhered body by adhering to a to-be-adhered body is sufficiently low can be expressed more.

The content of the silicone-based additive and / or the fluorine-based additive in the pressure-sensitive adhesive composition is a total amount of the silicone-based additive and the fluorine-based additive relative to 100 parts by weight of the base polymer, preferably 0.001 part by weight to 50 parts by weight, and more preferably 0.005 part by weight to 25 parts by weight. It is a weight part, More preferably, it is 0.01 weight part-10 weight part, More preferably, it is 0.01 weight part-1 weight part, More preferably, it is 0.01 weight part-0.50 weight part, Especially preferably, it is 0.01 weight part. It is -0.30 weight part, Most preferably, it is 0.01 weight part-0.10 weight part. When content of the silicone type additive and / or fluorine additive in an adhesive composition exists in the said range, the surface protection film of this invention does not peel easily from a to-be-adhered body, Even if the initial peeling force after adhering to a to-be-adhered body is large over time Can be sufficiently suppressed, and the effect that the contamination on the surface of the adherend by adhering to the adherend is sufficiently low can be more expressed.

That is, when a silicone additive is included in an adhesive composition but does not contain a fluorine additive, the content ratio of a silicone additive with respect to 100 weight part of base polymers becomes like this. Preferably it is 0.001 weight part-50 weight part, More preferably, it is 0.005 weight part It is 25-25 weight part, More preferably, it is 0.01 weight part-10 weight part, More preferably, it is 0.01 weight part-1 weight part, More preferably, it is 0.01 weight part-0.50 weight part, Especially preferably, it is 0.01 weight part-0.30 weight part, Most preferably, they are 0.01 weight part-0.10 weight part. When content of the silicone additive in an adhesive composition exists in the said range, the surface protection film of this invention does not peel easily from a to-be-adhered body, Even if the initial peeling force after adhering to a to-be-adhered body is large, heavy peeling at time is sufficient. It can suppress, and the effect that the contamination of the said to-be-adhered body surface by adhering to a to-be-adhered body is sufficiently low can be expressed more.

In addition, when a silicone additive is not contained in an adhesive composition but a fluorine additive is included, the content rate of a fluorine additive with respect to 100 weight part of base polymers becomes like this. Preferably it is 0.001 weight part-50 weight part, More preferably, it is 0.005 weight part It is 25-25 weight part, More preferably, it is 0.01 weight part-10 weight part, More preferably, it is 0.01 weight part-1 weight part, More preferably, it is 0.01 weight part-0.50 weight part, Especially preferably, it is 0.01 weight part-0.30 weight part, Most preferably, they are 0.01 weight part-0.10 weight part. When content of the fluorine-type additive in an adhesive composition exists in the said range, the surface protection film of this invention does not peel easily from a to-be-adhered body, Even if the initial peeling force after adhering to a to-be-adhered body is large, sufficient delamination in time is sufficient. It can suppress, and the effect that the contamination of the said to-be-adhered body surface by adhering to a to-be-adhered body is sufficiently low can be expressed more.

In addition, when both a silicone type additive and a fluorine additive are included in an adhesive composition, the content rate of the sum total of a silicone additive and a fluorine additive with respect to 100 weight part of base polymers becomes like this. Preferably it is 0.001 weight part-50 weight part, More preferably, Preferably it is 0.005 weight part-25 weight part, More preferably, it is 0.01 weight part-10 weight part, More preferably, it is 0.01 weight part-1 weight part, More preferably, it is 0.01 weight part-0.50 weight part, Especially preferably, they are 0.01 weight part-0.30 weight part, Most preferably, they are 0.01 weight part-0.10 weight part. When content of the sum total of the silicone type additive and fluorine-type additive in an adhesive composition exists in the said range, the surface protection film of this invention does not peel easily from a to-be-adhered body, Even if the initial peeling force after adhering to a to-be-adhered body is large over time. Can be sufficiently suppressed, and the effect that the contamination on the surface of the adherend by adhering to the adherend is sufficiently low can be more expressed.

<A-2-1. Base Polymer>

The base polymer is preferably at least one selected from urethane prepolymers, polyols, acrylic resins, rubber resins, and silicone resins. If the base polymer is at least one selected from urethane prepolymers, polyols, acrylic resins, rubber resins, and silicone resins, the surface protective film of the present invention does not easily peel off from the adherend, and is initially peeled off after adhering to the adherend. Even if the force is large, heavy peeling at time can be sufficiently suppressed, and the effect that the contamination on the surface of the adherend by adhering to the adherend is sufficiently low can be more expressed.

[A-2-1-a. Urethane Prepolymer]

The urethane prepolymer is preferably a polyurethane polyol, more preferably a polyester polyol (a1) or a polyether polyol (a2) alone or in a mixture of (a1) and (a2), in the presence of a catalyst or without a catalyst It is made to react with an organic polyisocyanate compound (a3) under the following.

Arbitrary suitable polyester polyol can be used as polyester polyol (a1). As such polyester polyol (a1), the polyester polyol obtained by making an acid component and a glycol component react is mentioned, for example. Examples of the acid component include terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid, trimellitic acid and the like. As the glycol component, for example, ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, 1,6-hexane glycol, 3-methyl-1,5-pentanediol, 3,3'-dimethylolheptane, polyoxy Ethylene glycol, polyoxypropylene glycol, 1, 4- butanediol, neopentyl glycol, butyl ethyl pentanediol, glycerin, trimethylol propane, pentaerythritol etc. are mentioned as a polyol component. Examples of the polyester polyol (a1) include polyester polyols obtained by ring-opening polymerization of lactones such as polycaprolactone, poly (β-methyl-γ-valerolactone) and polyvalerolactone.

As a molecular weight of polyester polyol (a1), it can use from low molecular weight to high molecular weight. As molecular weight of polyester polyol (a1), a number average molecular weight becomes like this. Preferably it is 100-100000. When number average molecular weight is less than 100, there exists a possibility that it may become easy to gelatinize because reactivity becomes high. When the number average molecular weight exceeds 100000, the reactivity becomes low, and furthermore, there is a fear that the cohesive force of the polyurethane polyol itself becomes small. The amount of the polyester polyol (a1) used is preferably 0 mol% to 90 mol% among the polyols constituting the polyurethane polyol.

Arbitrary suitable polyether polyol can be used as a polyether polyol (a2). As such a polyether polyol (a2), low molecular weight polyols, such as water, propylene glycol, ethylene glycol, glycerin, trimethylol propane, are used as an initiator, for example, ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, etc. The polyether polyol obtained by superposing | polymerizing the oxirane compound of is mentioned. Specific examples of such polyether polyol (a2) include polyether polyols having two or more functional groups such as polypropylene glycol, polyethylene glycol, and polytetramethylene glycol.

As a molecular weight of a polyether polyol (a2), it can use from low molecular weight to high molecular weight. As molecular weight of a polyether polyol (a2), a number average molecular weight becomes like this. Preferably it is 100-100000. When number average molecular weight is less than 100, there exists a possibility that it may become easy to gelatinize because reactivity becomes high. When the number average molecular weight exceeds 100000, the reactivity becomes low, and furthermore, there is a fear that the cohesive force of the polyurethane polyol itself becomes small. The amount of the polyether polyol (a2) used is preferably 0 mol% to 90 mol% among the polyols constituting the polyurethane polyol.

Polyether polyol (a2) is partially ethylene glycol, 1,4-butanediol, neopentylglycol, butylethylpentanediol, glycols such as glycerin, trimethylolpropane, pentaerythritol, ethylenediamine and N-amino as necessary. It can substitute and use together polyhydric amines, such as ethyl ethanolamine, isophorone diamine, and xylene diamine, and can use together.

As the polyether polyol (a2), only a bifunctional polyether polyol may be used, the number average molecular weight is 100 to 100000, and some or all of the polyether polyols having at least three or more hydroxyl groups in one molecule may be used. When the polyether polyol (a2) has a number average molecular weight of 100 to 100,000 and a polyether polyol having at least three or more hydroxyl groups in one molecule, part or all of the polyether polyol (a2) may have a good balance of adhesion and re-peelability. In such a polyether polyol, when the number average molecular weight is less than 100, there is a fear that the reactivity becomes high and the gelation becomes easy. Moreover, in such a polyether polyol, when a number average molecular weight exceeds 100000, there exists a possibility that reactivity may become low and also the cohesion force of polyurethane polyol itself may become small. The number average molecular weight of such polyether polyol becomes like this. More preferably, it is 100-10000.

Arbitrary suitable organic polyisocyanate compounds can be used as an organic polyisocyanate compound (a3). As such an organic polyisocyanate compound (a3), aromatic polyisocyanate, aliphatic polyisocyanate, aromatic aliphatic polyisocyanate, alicyclic polyisocyanate, etc. are mentioned, for example.

As aromatic polyisocyanate, it is 1, 3- phenylene diisocyanate, 4, 4'- diphenyl diisocyanate, 1, 4- phenylene diisocyanate, 4, 4'- diphenylmethane diisocyanate, 2, 4, for example. -Tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanatebenzene, dianisidine diisocyanate , 4,4'-diphenyl ether diisocyanate, 4,4 ', 4 "-triphenylmethane triisocyanate, etc. are mentioned.

Examples of the aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butyl Lene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, etc. are mentioned.

As an aromatic aliphatic polyisocyanate, for example, ω, ω'- diisocyanate-1,3-dimethylbenzene, ω, ω'-diisocyanate-1,4-dimethylbenzene, ω, ω'-diisocyanate-1,4 -Diethyl benzene, 1, 4- tetramethyl xylylene diisocyanate, 1, 3- tetramethyl xylylene diisocyanate, etc. are mentioned.

As the alicyclic polyisocyanate, for example, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate Isocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanatemethyl) cyclohexane, 1 And 4-bis (isocyanate methyl) cyclohexane.

As an organic polyisocyanate compound (a3), the trimethylolpropane adduct body, the burette body reacted with water, the trimer which has an isocyanurate ring, etc. can be used together.

Arbitrary suitable catalysts can be used as a catalyst which can be used when obtaining a polyurethane polyol. As such a catalyst, a tertiary amine compound, an organometallic compound, etc. are mentioned, for example.

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

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

Examples of the tin compound include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, and dibutyl. Tin sulfide, tributyl tin sulfide, tributyl tin oxide, tributyl tin acetate, triethyl tin ethoxide, tributyl tin ethoxide, dioctyl tin oxide, tributyl tin chloride, tributyl tin trichloro acetate And 2-ethylhexanoic acid tin are mentioned.

As a non-tin compound, For example, Titanium compounds, such as a dibutyl titanium dichloride, tetrabutyl titanate, butoxy titanium trichloride; Lead-based compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, and naphthenate; Iron-based compounds such as iron 2-ethylhexanoate and iron acetyl acetate; Cobalt compounds such as cobalt benzoate and cobalt 2-ethylhexanoate; Zinc-based compounds such as zinc naphthenate and zinc 2-ethylhexanoate; Zirconium compounds such as zirconium naphthenate; Etc. can be mentioned.

When a catalyst is used to obtain a polyurethane polyol, there is a problem of gelation or turbidity of the reaction solution in a system of a single catalyst because of the difference in reactivity in a system in which two kinds of polyols, a polyester polyol and a polyether polyol exist. It is easy to occur. Therefore, by using two kinds of catalysts when obtaining a polyurethane polyol, it becomes easy to control reaction rate, selectivity of a catalyst, etc., and can solve these problems. As a combination of these two types of catalysts, tertiary amine / organic metal type, tin type / non-tin type, tin type / tin type are mentioned, Preferably they are tin type / tin type, More preferably, It is a combination of butyltin dilaurate and tin 2-ethylhexanoic acid. The compounding ratio of tin 2-ethylhexanoate / dibutyltin dilaurate is preferably less than 1, more preferably 0.2 to 0.6 by weight. If the blending ratio is 1 or more, there is a risk of gelation easily due to the balance of the catalyst activity.

When using a catalyst when obtaining a polyurethane polyol, the amount of the catalyst used is preferably 0.01% by weight to 1.0% by weight based on the total amount of the polyester polyol (a1), the polyether polyol (a2), and the organic polyisocyanate compound (a3). %to be.

When using a catalyst when obtaining a polyurethane polyol, reaction temperature becomes like this. Preferably it is less than 100 degreeC, More preferably, it is 85 degreeC-95 degreeC. If it is 100 degreeC or more, there exists a possibility that control of reaction rate and a crosslinked structure may become difficult, and it may become difficult to obtain the polyurethane polyol which has a predetermined molecular weight.

When obtaining a polyurethane polyol, it is not necessary to use a catalyst. In that case, reaction temperature becomes like this. Preferably it is 100 degreeC or more, More preferably, it is 110 degreeC or more. Moreover, when obtaining a polyurethane polyol under a catalyst, it is preferable to make it react for 3 hours or more.

As a method of obtaining a polyurethane polyol, for example, 1) a polyester polyol, a polyether polyol, a catalyst and an organic polyisocyanate are added to the flask in its entirety, and 2) a polyester polyol, a polyether polyol and a catalyst are added to the flask. The method of dripping and adding organic polyisocyanate is mentioned. As a method of obtaining a polyurethane polyol, the method of 2) is preferable at the point of controlling reaction.

Any suitable solvent can be used when obtaining a polyurethane polyol. As such a solvent, methyl ethyl ketone, ethyl acetate, toluene, xylene, acetone, etc. are mentioned, for example. Among these solvents, Toluene is preferable.

[A-2-1-b. Polyol]

As a polyol, Preferably, polyester polyol, polyether polyol, polycaprolactone polyol, polycarbonate polyol, castor oil type polyol is mentioned, for example. As a polyol, More preferably, it is a polyether polyol.

As polyester polyol, it can obtain by esterification reaction of a polyol component and an acid component, for example.

Examples of the polyol component include ethylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, neopentylglycol, 3-methyl-1,5-pentanediol, and 2-butyl-2-ethyl-1 , 3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2- Methyl-1,8-octanediol, 1,8-decanediol, octadecanediol, glycerin, trimethylolpropane, pentaerythritol, hexanetriol, polypropylene glycol and the like. As the acid component, for example, succinic acid, methyl succinic acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, 1,12-dodecanoic acid, 1,14-tetradecanoic acid, dimer acid, 2-methyl-1, 4-cyclohexanedicarboxylic acid, 2-ethyl-1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 4,4 ' -Biphenyl dicarboxylic acid, these acid anhydrides, etc. are mentioned.

Examples of the polyether polyols include water, low molecular weight polyols (propylene glycol, ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, etc.), bisphenols (such as bisphenol A), dihydroxybenzenes (catechol, resorcin, hydro). The polyether polyol obtained by addition-polymerizing alkylene oxides, such as ethylene oxide, a propylene oxide, butylene oxide, using quinone etc.) etc. as an initiator is mentioned. Specifically, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc. are mentioned, for example.

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

As a polycarbonate polyol, For example, Polycarbonate polyol obtained by making a polycondensation reaction of the said polyol component and phosgene; Ester of the polyol component and carbonic acid diesters such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, ethyl butyl carbonate, ethylene carbonate, propylene carbonate, diphenyl carbonate and dibenzyl carbonate Polycarbonate polyols obtained by exchange condensation; Copolymerized polycarbonate polyol obtained by using 2 or more types of said polyol components together; Polycarbonate polyol obtained by esterifying the said various polycarbonate polyol and carboxyl group-containing compound; Polycarbonate polyols obtained by etherification of the various polycarbonate polyols and hydroxyl group-containing compounds; Polycarbonate polyol obtained by transesterifying the said various polycarbonate polyol and ester compound; Polycarbonate polyol obtained by transesterifying the said various polycarbonate polyol and hydroxyl group containing compound; Polyester type polycarbonate polyol obtained by making polycondensation reaction of the said various polycarbonate polyol and a dicarboxylic acid compound; Copolymerized polyether polycarbonate polyols obtained by copolymerizing various polycarbonate polyols with alkylene oxides; Etc. can be mentioned.

As a castor oil type polyol, the castor oil type polyol obtained by making a castor oil fatty acid and the said polyol component react is mentioned, for example. Specifically, the castor oil type polyol obtained by making a castor oil fatty acid and polypropylene glycol react is mentioned, for example.

The number average molecular weight (Mn) of the polyol is preferably 300 to 100000, more preferably 400 to 7500, still more preferably 450 to 50000, and particularly preferably 500 to 30000. If the number average molecular weight (Mn) of a polyol exists in the said range, the surface protection film of this invention does not peel easily from a to-be-adhered body, and even if the initial peeling force after adhering to a to-be-adhered body is large, it becomes heavy peeling at time. It can fully suppress and the effect that the contamination of the surface of the said to-be-adhered body by adhering to a to-be-adhered body is sufficiently low can be expressed more.

As a polyol, Preferably, the number average molecular weight (Mn) which has three OH groups contains 300-100000 polyols (A1). 1 type of polyols (A1) may be sufficient and 2 or more types may be sufficient as it.

The content rate of polyol (A1) in a polyol becomes like this. Preferably it is 5 weight% or more, More preferably, it is 25 weight%-100 weight%, More preferably, it is 50 weight%-100 weight%. If the content rate of polyol (A1) in a polyol exists in the said range, the surface protection film of this invention does not peel easily from a to-be-adhered body, Even if the initial peeling force after adhering to a to-be-adhered body is large, it peels in time. Can be sufficiently suppressed, and the effect that the contamination on the surface of the adherend by adhering to the adherend is sufficiently low can be more expressed.

Preferably the number average molecular weight (Mn) of a polyol (A1) is 1000-100000, More preferably, it is more than 1000 and is 80000 or less, More preferably, it is 1100-70000, More preferably, it is 1200-60000, More preferably, it is 1300-50000, More preferably, it is 1400-30000, More preferably, it is 1500-35000, Especially preferably, it is 1700-32000, Most preferably, it is 2000-30000. If the number average molecular weight (Mn) of a polyol (A1) exists in the said range, the surface protection film of this invention does not peel easily from a to-be-adhered body, Even if the initial peeling force after adhering to a to-be-adhered body is large over time Heavy peeling can be fully suppressed, and the effect that the contamination of the surface of the said adherend by adhering to a to-be-adhered body is sufficiently low can be expressed more.

The polyol may contain the polyol (A2) whose number average molecular weight (Mn) which has three or more OH groups is 20000 or less. 1 type of polyols (A2) may be sufficient and 2 or more types may be sufficient as it. The number average molecular weight (Mn) of the polyol (A2) is preferably 100 to 20,000, more preferably 150 to 10000, still more preferably 200 to 7500, particularly preferably 300 to 6000, most preferably Is 300 to 5000. When the number average molecular weight (Mn) of a polyol (A2) deviates from the said range, there exists a possibility that especially the synchronism of the peeling force of the surface protection film of this invention may increase over time. The polyol (A2) is preferably a polyol having three OH groups (triol), a polyol having four OH groups (tetraol), a polyol having five OH groups (pentaol), and a polyol having six OH groups (hexaol) ).

The total amount of polyol (tetraol) having four OH groups as polyol (A2), polyol (pentaol) having five OH groups, and polyol (hexaol) having six OH groups is a content ratio in the polyol, preferably 70 It is weight% or less, More preferably, it is 60 weight% or less, More preferably, it is 40 weight% or less, Especially preferably, it is 30 weight% or less. The content ratio in the polyol of the total amount of the polyol (tetraol) which has four OH groups as a polyol (A2), the polyol (pentaol) which has five OH groups, and the polyol (hexaol) which has six OH groups in a polyol is the said range. If it exists in, the adhesive layer excellent in transparency can be provided, and the surface protection film of this invention does not peel easily from a to-be-adhered body, and it is heavy peeling at time even if the initial peeling force after adhering to a to-be-adhered body is large. Can be sufficiently suppressed, and the effect that the contamination on the surface of the adherend by adhering to the adherend is sufficiently low can be more expressed.

The content rate of polyol (A2) in a polyol becomes like this. Preferably it is 95 weight% or less, More preferably, it is 0 to 75 weight%. When the content rate of polyol (A2) in a polyol is in the said range, the surface protection film of this invention does not peel easily from a to-be-adhered body, and even if the initial peeling force after adhering to a to-be-adhered body is large, it peels off in time. Can be sufficiently suppressed, and the effect that the contamination on the surface of the adherend by adhering to the adherend is sufficiently low can be more expressed.

The content ratio of the polyol having a number average molecular weight (Mn) having 4 or more of OH groups as the polyol (A2) of 20000 or less is preferably less than 70% by weight, more preferably 60% by weight or less, based on the entire polyol. Preferably it is 50 weight% or less, Especially preferably, it is 40 weight% or less, Most preferably, it is 30 weight% or less. When the content ratio of the polyol having a number average molecular weight (Mn) having 4 or more of OH groups as the polyol (A2) of 20,000 or less is in the above range with respect to the entire polyol, the pressure-sensitive adhesive layer excellent in transparency can be provided, and the surface of the present invention The protective film does not easily peel off from the adherend, and even if the initial peeling force after adhering to the adherend is large, heavy peeling in time can be sufficiently suppressed, and the adhesion of the adherend surface by adhering to the adherend The effect that contamination is low enough can be expressed more.

[A-2-1-c. Acrylic resin]

As acrylic resin, arbitrary appropriate acrylic adhesives, such as a well-known acrylic adhesive described in Unexamined-Japanese-Patent No. 2013-241606, etc. can be employ | adopted in the range which does not impair the effect of this invention.

Acrylic resin may contain arbitrary appropriate components in the range which does not impair the effect of this invention. Examples of such components include resin components other than acrylic resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foil-like substances, softeners, antioxidants, conductive agents, ultraviolet absorbers, antioxidants, light stabilizers, and surface lubricants. , Leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts, and the like.

[A-2-1-d. Rubber-based resin]

Arbitrary suitable rubber adhesives, such as a well-known rubber adhesive described in Unexamined-Japanese-Patent No. 2015-074771, etc. can be employ | adopted as rubber-based resin, for example in the range which does not impair the effect of this invention. 1 type may be sufficient as these and 2 or more types may be sufficient as them.

The rubber-based resin may contain any suitable component in a range that does not impair the effects of the present invention. Examples of such a component include resin components other than rubber resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foil-like substances, softeners, antioxidants, conductive agents, ultraviolet absorbers, antioxidants, light stabilizers, and surface lubricants. , Leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts, and the like.

[A-2-1-e. Silicone resin]

As a silicone pressure sensitive adhesive, arbitrary appropriate silicone pressure sensitive adhesives, such as a well-known silicone pressure sensitive adhesive described in Unexamined-Japanese-Patent No. 2014-047280, etc. can be employ | adopted in the range which does not impair the effect of this invention. 1 type may be sufficient as these and 2 or more types may be sufficient as them.

The silicone resin may contain any suitable component within a range that does not impair the effects of the present invention. Examples of such components include resin components other than silicone resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, antioxidants, conductive agents, ultraviolet absorbers, antioxidants, light stabilizers, and surface lubricants. , Leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts, and the like.

<A-2-2. Low Molecular Weight Polyols>

1 type of low molecular weight polyols may be sufficient, and 2 or more types may be sufficient as it.

The low molecular weight polyol may employ any suitable low molecular weight polyol within a range that does not impair the effects of the present invention. As such a low molecular weight polyol, Preferably, the polyol whose number average molecular weight (Mn) is 1500 or less is mentioned.

The number average molecular weight (Mn) of the low molecular weight polyol is preferably 1400 or less, more preferably 1300 or less, still more preferably 1200 or less, particularly preferably 1100 or less, and most preferably 1000 or less. The lower limit of the number average molecular weight (Mn) of the low molecular weight polyol is preferably 50 or more, more preferably 100 or more, still more preferably 150 or more, particularly preferably 200 or more, most preferably 250 or more to be. When the number average molecular weight (Mn) of the low molecular weight polyol is in the above range, the surface protective film of the present invention does not easily peel off from the adherend, and even if the initial peeling force after adhering to the adherend is large Lysification can be sufficiently suppressed, and the effect that the contamination of the surface of the adherend by adhering to the adherend is sufficiently low can be more expressed.

As low molecular weight polyol, Preferably, polyester polyol, polyether polyol, polycaprolactone polyol, polycarbonate polyol, castor oil type polyol is mentioned, for example. As low molecular weight polyol, More preferably, it is polyether polyol.

Examples of the polyether polyols include water, low molecular weight polyols (propylene glycol, ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, etc.), bisphenols (such as bisphenol A), dihydroxybenzenes (catechol, resorcin, hydro). And polyether polyols obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide and the like as quinone). Specifically, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyoxypropylene glyceryl ether, etc. are mentioned, for example.

The number of OH groups in the low molecular weight polyol is preferably 2 to 6, more preferably 3 to 5, still more preferably 3 to 4, particularly preferably 3. When the number of OH groups in the low molecular weight polyol is within the above range, the surface protective film of the present invention does not easily peel off from the adherend, and even after the adhesion to the adherend has a large initial peel force, It can fully suppress and the effect that the contamination of the surface of the said to-be-adhered body by adhering to a to-be-adhered body is sufficiently low can be expressed more.

<A-2-3. Silicone Additives>

The silicone-based additive may employ any suitable silicone-based additive within the scope of not impairing the effects of the present invention. As such a silicone type additive, Preferably, at least 1 sort (s) chosen from a siloxane bond containing compound, a hydroxyl group containing silicone type compound, and a crosslinkable functional group containing silicone type compound is mentioned.

1 type of silicone type additives may be sufficient, and 2 or more types may be sufficient as it.

Examples of the siloxane bond-containing compound include a polyether-modified polyorganosiloxane having a polyether group introduced into the main chain or side chain of the polyorganosiloxane skeleton (polydimethylsiloxane, etc.) or the main chain or side chain of the polyorganosiloxane skeleton. Group-modified polyorganosiloxane, polyorganosiloxane organic compound introduced organic compound introduced into the main chain or side chain of the polyorganosiloxane, (meth) acrylic-based silicone modified polyorganosiloxane introduced polyorganosiloxane ( The silicone modified organic compound which introduce | transduced the polyorganosiloxane into the meta) acrylic resin, the organic compound, the silicone containing organic compound which copolymerized the organic compound and a silicone compound, etc. are mentioned. As such a siloxane bond containing polymer, it is a commercial item, for example, brand name "LE-302" (made by Kyoeisha Chemical Co., Ltd.), BYK Japan KK made by BYK series leveling agent ("BYK-300", "BYK-301) / 302 "," BYK-306 "," BYK-307 "," BYK-310 "," BYK-315 "," BYK-313 "," BYK-320 "," BYK-322 "," BYK-323 " "BYK-325", "BYK-330", "BYK-331", "BYK-333", "BYK-337", "BYK-341", "BYK-344", "BYK-345 / 346" "BYK-347", "BYK-348", "BYK-349", "BYK-370", "BYK-375", "BYK-377", "BYK-378", "BYK-UV 3500" , `` BYK-UV 3510 '', `` BYK-UV 3570 '', `` BYK-3550 '', `` BYK-SILCLEAN 3700 '', `` BYK-SILCLEAN 3720 '', etc., leveling agent of AC series made in Algin-Chemie (`` AC FS180 "," AC FS360 "," AC S20 ", etc., leveling agent of POLYFLOW series (" POLYFLOW KL-400X "," POLYFLOW KL-400HF "," POLYFLOW KL-401 ") made by Kyoeisha Chemical Co., Ltd. , `` POLYFLOW KL-402 '', `` POLYFLOW KL-403 '', `` POLYF LOW KL-404 '', etc., KP series leveling agent ("KP-323", "KP-326", "KP-341", "KP-104", " KP-110 "," KP-112 ", etc., X22 series by Shin-Etsu Chemical Co., Ltd., KF series, etc., Leveling agent (" LP-7001 ", by Dow Corning Toray Co., Ltd., "LP-7002", "8032 ADDITIVE", "57 ADDITIVE", "L-7604", "FZ-2110", "FZ-2105", "67 ADDITIVE", "8618 ADDITIVE", "3 ADDITIVE", " 56 ADDITIVE ”and the like.

As a hydroxyl-containing silicone type compound, For example, polyester in the main chain or side chain of polyether modified polyorganosiloxane and polyorganosiloxane skeleton which introduce | transduced the polyether group into the main chain or side chain of polyorganosiloxane skeleton (polydimethylsiloxane etc.) Group-modified polyorganosiloxane, polyorganosiloxane organic compound introduced organic compound introduced into the main chain or side chain of the polyorganosiloxane, (meth) acrylic-based silicone modified polyorganosiloxane introduced polyorganosiloxane ( The silicone modified organic compound which introduce | transduced the polyorganosiloxane into the meta) acrylic resin, the organic compound, the silicone containing organic compound which copolymerized the organic compound and a silicone compound, etc. are mentioned. In these, a hydroxyl group may have a polyorganosiloxane skeleton, and a polyether group, a polyester group, a (meth) acryloyl group, and an organic compound may have. As such a hydroxyl-containing silicone, it is a commercial item, for example, brand names "X-22-4015", "X-22-4039", "KF6000", "KF6001", "KF6002", "KF6003", "X-22-170BX" `` X-22-170DX '', `` X-22-176DX '', `` X-22-176F '' (manufactured by Shin-Etsu Chemical Co., Ltd.), `` BYK-370 '' made by BYK Japan KK, `` BYK-SILCLEAN 3700 "," BYK-SILCLEAN 3720 ", etc. are mentioned.

As a crosslinkable functional group containing silicone type compound, For example, in the main chain or side chain of the polyether modified polyorganosiloxane and polyorganosiloxane skeleton which introduce | transduced the polyether group into the main chain or side chain of polyorganosiloxane skeleton (polydimethylsiloxane etc.), Polyester-modified polyorganosiloxane incorporating polyester group, organic compound incorporation incorporating organic compound in main chain or side chain of polyorganosiloxane backbone, silicone incorporating polyorganosiloxane in (meth) acrylic resin The silicone modified organic compound which introduce | transduced the polyorganosiloxane into modified (meth) acrylic-type resin, an organic compound, the silicone containing organic compound which copolymerized the organic compound and a silicone compound, etc. are mentioned. In these, a crosslinkable functional group may have a polyorganosiloxane skeleton, and a polyether group, a polyester group, a (meth) acryloyl group, and an organic compound may have. As a crosslinkable functional group, an amino group, an epoxy group, a mercapto group, a carboxyl group, an isocyanate group, a methacrylate group, etc. are mentioned. As such isocyanate group-containing silicone, as a commercial item, for example, "BY16-855", "SF8413", "BY16-839", "SF8421", "BY16-750", "BY16" manufactured by Dow Corning Toray Co., Ltd. -880 "," BY16-152C "," KF-868 "," KF-865 "," KF-864 "," KF-859 "," KF-393 "made by Shin-Etsu Chemical Co., Ltd. , `` KF-860 '', `` KF-880 '', `` KF-8004 '', `` KF-8002 '', `` KF-8005 '', `` KF-867 '', `` KF-8021 '', `` KF-869 '', `` "KF-861", "X-22-343", "KF-101", "X-22-2000", "X-22-4741", "KF-1002", "KF-2001", "X- 22-3701E "," X-22-164 "," X-22-164A "," X-22-164B "," X-22-164AS ", and" X-22-2445 ".

<A-2-4. Fluorinated Additives>

The fluorine-based additive may employ any suitable fluorine-based additive within a range that does not impair the effects of the present invention. As such a fluorine-type additive, Preferably, at least 1 sort (s) chosen from a fluorine-containing compound, a hydroxyl-containing fluorine-type compound, and a crosslinkable functional group containing fluorine-type compound is mentioned.

1 type may be sufficient as a fluorine additive, and 2 or more types may be sufficient as it.

As a fluorine-containing compound, the compound which has a fluoroaliphatic hydrocarbon backbone, the fluorine-containing organic compound which copolymerized the organic compound and a fluorine compound, the fluorine-containing compound containing an organic compound, etc. are mentioned, for example. Examples of fluoroaliphatic hydrocarbon backbones include fluoromethane, fluoroethane, fluoropropane, fluoroisopropane, fluorobutane, fluoroisobutane, fluorot-butane, fluoropentane, fluorohexane and the like. Fluoro C1-C10 alkanes; and the like. As such a fluorine-containing compound, it is a commercial item, for example, the leveling agent of the SURFLON series ("S-242", "S-243", "S-420", "S-611" made from AGC SEIMI CHEMICAL CO., LTD.). , `` S-651 '', `` S-386 ''), BYK Japan KK leveling agent (`` BYK-340 ''), Algin-Chemie AC series leveling agent (`` AC 110a '', `` AC 100a '', etc., leveling agent (`` Megafac F-114 '', `` Megafac F-410 '', `` Megafac F-444 '', `` Megafac EXP TP-2066 '', `` Megafac F- '' made by DIC Corporation) 430 "," Megafac F-472SF "," Megafac F-477 "," Megafac F-552 "," Megafac F-553 "," Megafac F-554 "," Megafac F-555 "," Megafac R-94 " "Megafac RS-72-K", "Megafac RS-75", "Megafac F-556", "Megafac EXP TF-1367", "Megafac EXP TF-1437", "Megafac F-558", "Megafac" EXP TF-1537 '', etc.), leveling agent of FC series made of Sumitomo 3M Ltd. (`` FC-4430 '', `` FC-4432 '', etc.), of FTERGENT series made of NEOS Co., Ltd. Leveling agent (FTERGENT 100 '', FTERGENT 100C '', FTERGENT 110 '', FTERGENT 150 '', FTERGENT 150CH '', FTERGENT AK '', FTERGENT 501 '', FTERGENT 250 '', FTERGENT 251 '', FTERGENT 222F '', FTERGENT 208G '', FTERGENT 300 '' , FTERGENT 310 ", FTERGENT 400SW", etc., PF series leveling agent ("PF-136A", "PF-156A", "PF-151N", "PF-636", manufactured by Kitamura Chemicals Co., Ltd., "PF-6320", "PF-656", "PF-6520", "PF-651", "PF-652", "PF-3320", etc.) are mentioned.

As the hydroxyl group-containing fluorine-based compound, conventionally known resins can be used, for example, International Publication No. 94/06870, Japanese Patent Application Laid-Open No. 8-12921, Japanese Patent Application Laid-Open No. 10-72569, And hydroxyl group-containing fluorine resins described in Japanese Patent Application Laid-Open No. 4-275379, International Publication No. 97/11130, and International Publication No. 96/26254. As other hydroxyl-containing fluororesin, for example, Japanese Patent Application Laid-Open No. 8-231919, Japanese Patent Application Laid-Open No. 10-265731, Japanese Patent Application Laid-Open No. 10-204374, Japanese Patent Application Laid-Open No. 8-12922 The fluoroolefin copolymer etc. which were described in these etc. are mentioned. In addition, the copolymer of the compound which has a fluorinated alkyl group in a hydroxyl group containing compound, the fluorine-containing organic compound which copolymerized the fluorine-containing compound in the hydroxyl group containing compound, the fluorine-containing compound containing a hydroxyl group containing organic compound, etc. are mentioned. As such a hydroxyl-containing fluorine-based compound, commercially available products include, for example, trade name "LUMIFLON" (manufactured by Asahi Glass Co., Ltd.), trade name "CEFRAL COAT" (manufactured by Central Glass Co., Ltd.), and trade name "SURFRON" (Toagosei Co.). , Ltd.), a brand name "ZEFFLE" (made by Daikin Industries, Ltd.), a brand name "Megafac F-571", "FLUONATE" (made by DIC Corporation), and the like.

Examples of the crosslinkable functional group-containing fluorine-based compound include carboxylic acid compounds having fluorinated alkyl groups such as perfluorooctanoic acid, copolymers of compounds having fluorinated alkyl groups in the crosslinkable functional group-containing compound, and crosslinkable functional group-containing compounds. The fluorine-containing compound etc. which contain the fluorine-containing organic compound which copolymerized the fluorine-containing compound, the crosslinkable functional group containing compound, etc. are mentioned. As such a crosslinkable functional group containing fluorine-type compound, as a commercial item, for example, brand name "Megafac F-570", "Megafac RS-55", "Megafac RS-56", "Megafac RS-72-K", "Megafac RS-75" "," Megafac RS-76-E "," Megafac RS-76-NS "," Megafac RS-78 "," Megafac RS-90 "(made by DIC Corporation), etc. are mentioned.

By using a low molecular weight polyol, a silicone type additive, and / or a fluorine type additive together, it does not peel easily from a to-be-adhered body, and even when it is stored for a long time in a severe environment, heavy peeling at time can be suppressed more fully, It is possible to provide a surface protection film having a sufficiently low contamination property on the surface of the adherend by adhering to the adherend.

When using a low molecular weight polyol, a silicone type additive, and / or a fluorine additive together, content of the low molecular weight polyol in an adhesive composition becomes like this. Preferably it is 0.01 weight part-50 weight part with respect to 100 weight part of base polymer, More preferably, it is 0.05 It is weight part-25 weight part, More preferably, it is 0.07 weight part-30 weight part, More preferably, it is 0.1 weight part-20 weight part, More preferably, it is 0.3 weight part-15 weight part, Especially preferably, Is 0.5 to 10 parts by weight, most preferably 0.7 to 7.0 parts by weight. When using a low molecular weight polyol, a silicone type additive, and / or a fluorine additive together, if content of the low molecular weight polyol in an adhesive composition exists in the said range, the surface protection film of this invention will not peel easily from a to-be-adhered body, Even if the initial peeling force after adhering to a complex is large, heavy peeling at time can be suppressed more fully, and the effect that the contamination of the surface of the said to-be-adhered body by adhering to a to-be-adhered body is more sufficiently low can be expressed more.

In the case of using a low molecular weight polyol and a silicone additive and / or a fluorine additive together, the content of the silicone additive and / or the fluorine additive in the pressure-sensitive adhesive composition is a total amount of the silicone additive and the fluorine additive with respect to 100 parts by weight of the base polymer, preferably 0.001 weight It is part-50 weight part, More preferably, it is 0.005 weight part-25 weight part, More preferably, it is 0.01 weight part-10 weight part, More preferably, it is 0.01 weight part-1 weight part, More preferably, it is It is 0.01 weight part-0.50 weight part, Especially preferably, it is 0.01 weight part-0.30 weight part, Most preferably, it is 0.01 weight part-0.10 weight part. When using a low molecular weight polyol, a silicone type additive, and / or a fluorine additive in combination, when the content of the silicone additive and / or the fluorine additive in the pressure-sensitive adhesive composition is within the above range, the surface protective film of the present invention is more easily peeled from the adherend. And, even if the initial peeling force after adhering to the adherend is large, heavy peeling over time can be more sufficiently suppressed, and the effect that the contamination on the surface of the adherend by adhering to the adherend is more sufficiently low is expressed more. can do. Specifically, it is as follows.

When the low molecular weight polyol and the silicone-based additive are used in combination but the fluorine-based additive is not used in combination, the content of the silicone-based additive in the pressure-sensitive adhesive composition is preferably 0.001 part by weight to 50 parts by weight, more preferably 0.005 part by weight based on 100 parts by weight of the base polymer. It is 25-25 weight part, More preferably, it is 0.01 weight part-10 weight part, More preferably, it is 0.01 weight part-1 weight part, More preferably, it is 0.01 weight part-0.50 weight part, Especially preferably, it is 0.01 weight part-0.30 weight part, Most preferably, they are 0.01 weight part-0.10 weight part. When the low molecular weight polyol and the silicone additive are used in combination but the fluorine additive is not used in combination, when the content of the silicone additive in the pressure-sensitive adhesive composition is within the above range, the surface protective film of the present invention does not easily peel off from the adherend, Even if the initial peeling force after adhering to a complex is large, heavy peeling at time can be suppressed more fully, and the effect that the contamination of the surface of the said to-be-adhered body by adhering to a to-be-adhered body is more sufficiently low can be expressed more.

When the low molecular weight polyol and the fluorine-based additive are used in combination but the silicone-based additive is not used in combination, the content of the fluorine-based additive in the pressure-sensitive adhesive composition is preferably 0.001 part by weight to 50 parts by weight, more preferably 0.005 part by weight based on 100 parts by weight of the base polymer. It is 25-25 weight part, More preferably, it is 0.01 weight part-10 weight part, More preferably, it is 0.01 weight part-1 weight part, More preferably, it is 0.01 weight part-0.50 weight part, Especially preferably, it is 0.01 weight part-0.30 weight part, Most preferably, they are 0.01 weight part-0.10 weight part. When the low molecular weight polyol and the fluorine-based additive are used in combination but the silicone-based additive is not used in combination, when the content of the fluorine-based additive in the pressure-sensitive adhesive composition is within the above range, the surface protective film of the present invention does not easily peel off from the adherend, Even if the initial peeling force after adhering to a complex is large, heavy peeling at time can be suppressed more fully, and the effect that the contamination of the surface of the said to-be-adhered body by adhering to a to-be-adhered body is more sufficiently low can be expressed more.

When using a low molecular weight polyol, a silicone additive, and a fluorine additive together, the content rate of the sum total of a silicone additive and a fluorine additive with respect to 100 weight part of base polymers becomes like this. Preferably it is 0.001 weight part-50 weight part, More preferably, it is 0.005 weight part It is 25-25 weight part, More preferably, it is 0.01 weight part-10 weight part, More preferably, it is 0.01 weight part-1 weight part, More preferably, it is 0.01 weight part-0.50 weight part, Especially preferably, it is 0.01 weight part-0.30 weight part, Most preferably, they are 0.01 weight part-0.10 weight part. When using a low molecular weight polyol, a silicone type additive, and a fluorine additive together, if the content rate of the sum total of a silicone type additive and a fluorine additive in an adhesive composition exists in the said range, the surface protection film of this invention may peel more easily from a to-be-adhered body. And even if the initial peeling force after adhering to a to-be-adhered body is large, the heavy peeling at time can be suppressed more fully, and the effect that the contamination of the surface of the to-be-adhered body by adhering to a to-be-adhered body is more sufficiently low can be expressed more. Can be.

<A-2-5. Urethane Resin>

The urethane prepolymer and the polyol as the base polymer may each be a component of a composition for forming a urethane resin in combination with a polyfunctional isocyanate compound (B). By employ | adopting the above as a component of a composition for forming a urethane type resin, the surface protection film of this invention does not peel easily from a to-be-adhered body, Even if the initial peeling force after adhering to a to-be-adhered body is large over time Heavy peeling can be fully suppressed, and the effect that the contamination of the surface of the said adherend by adhering to a to-be-adhered body is sufficiently low can be expressed more.

The composition for forming the urethane-based resin may contain any suitable other components within a range that does not impair the effects of the present invention. Such components include, for example, resin components other than urethane resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foil shapes, softeners, antioxidants, conductive agents, ultraviolet absorbers, antioxidants, light stabilizers, and surface lubricants. , Leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts, and the like.

The composition for forming the urethane-based resin preferably contains a deterioration inhibitor such as an antioxidant, an ultraviolet absorber, and a light stabilizer. When the composition for forming a urethane resin contains a deterioration inhibitor, even if it preserve | stores in the warm state after attaching the adhesive layer formed to a to-be-adhered body, it can become excellent in adhesive residue prevention property, such that an adhesive residue is hard to produce on a to-be-adhered body. . 1 type may be sufficient as a deterioration inhibitor, and 2 or more types may be sufficient as it. As the deterioration inhibitor, particularly preferably, it is an antioxidant.

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

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

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

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

As monophenolic antioxidant, a 2, 6- di- t- butyl- p- cresol, a butylated hydroxyanisole, 2, 6- di- t- butyl- 4-ethyl phenol, stearin- (beta)- (3,5-di-t-butyl-4-hydroxyphenyl) propionate etc. are mentioned.

As a bisphenol-type antioxidant, 2,2'- methylene bis (4-methyl-6-t-butylphenol), 2,2'- methylene bis (4-ethyl-6-t-butylphenol), 4, for example , 4'-thiobis (3-methyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 3,9-bis [1,1 -Dimethyl-2- [β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane and the like Can be mentioned.

As the polymer type phenolic antioxidant, for example, 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,6 -Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) prop Cypionate] methane, bis [3,3'-bis- (4'-hydroxy-3'-t-butylphenyl) butyric acid] glycol ester, 1,3,5-tris (3 ', 5'-di- t-butyl-4'-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, a tocophenol, etc. are mentioned.

Examples of sulfur-based antioxidants include dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, and the like. Can be mentioned.

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

As a ultraviolet absorber, a benzophenone type ultraviolet absorber, a benzotriazole type ultraviolet absorber, a salicylic acid type ultraviolet absorber, an oxalic acid anilide type ultraviolet absorber, a cyanoacrylate type ultraviolet absorber, a triazine type ultraviolet absorber, etc. are mentioned, for example.

As a benzophenone type ultraviolet absorber, 2, 4- dihydroxy benzophenone, 2-hydroxy-4- methoxy benzophenone, 2-hydroxy-4- octoxy benzophenone, 2-hydroxy-4, for example. Dodecyloxy benzophenone, 2,2'-dihydroxy-4-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy benzophenone, 2-hydroxy-4-meth Methoxy-5-sulfobenzophenone, bis (2-methoxy-4-hydroxy-5-benzoylphenyl) methane, etc. are mentioned.

As a benzotriazole type ultraviolet absorber, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-tert- butylphenyl) benzotriazole, 2, for example -(2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chloro Benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) 5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di- tert-amylphenyl) benzotriazole, 2- (2'-hydroxy-4'-octoxyphenyl) benzotriazole, 2- [2'-hydroxy-3 '-(3' ', 4' ', 5 '', 6 '', tetrahydrophthalimidemethyl) -5'-methylphenyl] benzotriazole, 2,2'methylenebis [4- (1,1,3,3-tetramethylbutyl) -6 -(2H-benzotriazol-2-yl) phenol], 2- (2'-hydroxy-5'-methacryloxyphenyl) -2H-benzotriazole, etc. are mentioned.

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

As a cyanoacrylate type ultraviolet absorber, 2-ethylhexyl-2-cyano-3,3'- diphenyl acrylate, ethyl-2-cyano-3,3'- diphenyl acrylate, etc. are mentioned, for example. Can be mentioned.

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

Examples of the hindered amine light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (1,2,2,6,6-pentamethyl-4- Piperidyl) sebacate, methyl-1,2,2,6,6-pentamethyl-4-piperidyl sebacate, and the like.

Examples of the ultraviolet stabilizer include nickel bis (octylphenyl) sulfide, [2,2'-thiobis (4-tert-octylphenolate)]-n-butylamine nickel, nickel complex-3,5-di-tert -Butyl-4-hydroxybenzyl-phosphate monoethylate, nickel-dibutyl dithiocarbamate, a benzoate type quencher, nickel-dibutyl dithiocarbamate, and the like.

[A-2-5-a. Urethane resin formed from the composition containing a urethane prepolymer and a polyfunctional isocyanate compound (B)]

The urethane resin formed from the composition containing a urethane prepolymer and a polyfunctional isocyanate compound (B) is a urethane resin formed from the composition containing a polyurethane polyol and a polyfunctional isocyanate compound (B) as a urethane prepolymer, for example. have.

1 type of urethane prepolymers may be sufficient, and 2 or more types may be sufficient as it.

1 type of polyfunctional isocyanate compounds (B) may be sufficient, and 2 or more types may be sufficient as it.

As a polyfunctional isocyanate compound (B), arbitrary appropriate polyfunctional isocyanate compounds which can be used for a urethanation reaction can be employ | adopted. As such a polyfunctional isocyanate compound (B), a polyfunctional aliphatic isocyanate compound, a polyfunctional alicyclic isocyanate, a polyfunctional aromatic isocyanate compound, etc. are mentioned, for example.

Examples of the polyfunctional aliphatic isocyanate compound include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,3-butylene diisocyanate and dodeca. Methylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, etc. are mentioned.

As a polyfunctional alicyclic isocyanate compound, it is 1, 3- cyclopentene diisocyanate, 1, 3- cyclohexane diisocyanate, 1, 4- cyclohexane diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, for example. And hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated tetramethylxylylene diisocyanate and the like.

Examples of the polyfunctional aromatic diisocyanate compound include phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4 ' -Diphenylmethane diisocyanate, 4,4'-toluidine diisocyanate, 4,4'-diphenylether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate Etc. can be mentioned.

Examples of the polyfunctional isocyanate compound (B) include trimethylolpropane adducts of various polyfunctional isocyanate compounds as described above, a biuret reacted with water, and a trimer having an isocyanurate ring. Moreover, you may use together.

The composition containing the urethane prepolymer and the polyfunctional isocyanate compound (B) may contain any suitable other components within a range that does not impair the effects of the present invention. As such other components, for example, resin components other than polyurethane-based resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foil-like materials, softeners, antioxidants, conductive agents, ultraviolet absorbers, antioxidants, light stabilizers, Surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts and the like.

As a method of forming a polyurethane resin with the composition containing a urethane prepolymer and a polyfunctional isocyanate compound (B), if it is a method of manufacturing a polyurethane resin using what is called a "urethane prepolymer" as a raw material, arbitrary appropriate manufacturing methods are employ | adopted. can do.

The number average molecular weight (Mn) of the urethane prepolymer is preferably 3000 to 1000000.

The equivalent ratio of the NCO group and the OH group in the urethane prepolymer and the polyfunctional isocyanate compound (B) is preferably an NCO group / OH group, preferably 5.0 or less, more preferably 0.01 to 4.75, still more preferably 0.02 to 4.5 It is especially preferably 0.03 to 4.25, most preferably 0.05 to 4.0. When the equivalence ratio of NCO group / OH group exists in the said range, the surface protection film of this invention does not peel easily from a to-be-adhered body, Even if the initial peeling force after adhering to a to-be-adhered body is large, sufficient delamination in time is sufficient. It can suppress, and the effect that the contamination of the said to-be-adhered body surface by adhering to a to-be-adhered body is sufficiently low can be expressed more.

The content ratio of the polyfunctional isocyanate compound (B) is preferably 0.01% by weight to 30% by weight, more preferably 0.05% by weight to 25% by weight with respect to the urethane prepolymer. Preferably it is 0.1 to 20 weight%, Especially preferably, it is 0.5 to 17.5 weight%, Most preferably, it is 1 to 15 weight%. When the content ratio of the polyfunctional isocyanate compound (B) is within the above range, the surface protective film of the present invention does not easily peel off from the adherend, and even if the initial peeling force after attaching to the adherend is large, Lysification can be sufficiently suppressed, and the effect that the contamination of the surface of the adherend by adhering to the adherend is sufficiently low can be more expressed.

[A-2-5-b. Urethane resin formed from the composition containing a polyol and a polyfunctional isocyanate compound (B)]

The urethane resin formed from the composition containing a polyol and a polyfunctional isocyanate compound (B), Specifically, Preferably it is a urethane resin obtained by hardening | curing the composition containing a polyol and a polyfunctional isocyanate compound (B).

1 type of polyols may be sufficient and 2 or more types may be sufficient as it.

1 type of polyfunctional isocyanate compounds (B) may be sufficient, and 2 or more types may be sufficient as it.

The above-mentioned thing can be used as a polyfunctional isocyanate compound (B).

The equivalent ratio of the NCO group and the OH group in the polyol (A) and the polyfunctional isocyanate compound (B) is preferably an NCO group / OH group, preferably 5.0 or less, more preferably 0.1 to 3.0, still more preferably 0.2 It is -2.5, Especially preferably, it is 0.3-2.25, Most preferably, it is 0.5-2.0. When the equivalence ratio of NCO group / OH group exists in the said range, the surface protection film of this invention does not peel easily from a to-be-adhered body, Even if the initial peeling force after adhering to a to-be-adhered body is large, sufficient delamination in time is sufficient. It can suppress, and the effect that the contamination of the said to-be-adhered body surface by adhering to a to-be-adhered body is sufficiently low can be expressed more.

The content ratio of the polyfunctional isocyanate compound (B) is preferably 1.0% by weight to 30% by weight, more preferably 1.5% by weight to 27% by weight with respect to the polyol, and more preferably Is 2.0 wt% to 25 wt%, particularly preferably 2.3 wt% to 23 wt%, and most preferably 2.5 wt% to 20 wt%. When the content ratio of the polyfunctional isocyanate compound (B) is within the above range, the surface protective film of the present invention does not easily peel off from the adherend, and even if the initial peeling force after attaching to the adherend is large, Lysification can be sufficiently suppressed, and the effect that the contamination of the surface of the adherend by adhering to the adherend is sufficiently low can be more expressed.

Polyurethane-based resin is specifically preferably formed by curing a composition containing a polyol and a polyfunctional isocyanate compound (B). As a method of hardening the composition containing a polyol and a polyfunctional isocyanate compound (B), and forming a urethane-type resin, arbitrary appropriate in the range which does not impair the effect of this invention, such as the urethanation reaction method using block polymerization or solution polymerization, etc. Method may be employed.

In order to cure the composition containing a polyol and a polyfunctional isocyanate compound (B), a catalyst is used preferably. As such a catalyst, an organometallic compound, a tertiary amine compound, etc. are mentioned, for example.

As an organometallic compound, an iron type compound, a tin type compound, a titanium type compound, a zirconium type compound, a lead type compound, a cobalt type compound, a zinc type compound etc. are mentioned, for example. Among these, an iron compound and a tin compound are preferable at the point of reaction speed and the pot life of an adhesive layer.

As an iron type compound, iron acetyl acetate, iron 2-ethylhexanoate, etc. are mentioned, for example.

Examples of the tin compound include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin maleate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin sulfide, Tributyltin methoxide, tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, dioctyltin dilaurate, tributyltin chloride, tributyltin trichloroacetate, 2 -Ethyl hexanoate, etc. are mentioned.

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

As a zirconium type compound, zirconium naphthenate, a zirconium acetyl acetate, etc. are mentioned, for example.

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

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

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

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

1 type of catalysts may be sufficient and 2 or more types may be sufficient as it. Moreover, you may use together a catalyst, a crosslinking retarder, etc. The amount of the catalyst is preferably 0.005% by weight to 1.00% by weight with respect to the polyol, more preferably 0.01% by weight to 0.75% by weight, still more preferably 0.01% by weight to 0.50% by weight, particularly preferably 0.01 % By weight to 0.20% by weight. When the amount of the catalyst is within the above range, the surface protective film of the present invention does not easily peel off from the adherend, and even if the initial peeling force after adhering to the adherend is large, heavy peeling in time can be sufficiently suppressed. , The effect that the contamination on the surface of the adherend by adhering to the adherend is sufficiently low can be more expressed.

The composition containing the polyol and the polyfunctional isocyanate compound (B) may contain any suitable other components within a range that does not impair the effects of the present invention. As such other components, for example, resin components other than polyurethane-based resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foil-like materials, softeners, antioxidants, conductive agents, ultraviolet absorbers, antioxidants, light stabilizers, Surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts and the like.

<A-2-6. Fatty Acid Ester>

The pressure-sensitive adhesive composition preferably comprises a fatty acid ester. 1 type of fatty acid esters may be sufficient, and 2 or more types may be sufficient as it. When the pressure-sensitive adhesive composition contains a fatty acid ester, the surface protective film of the present invention does not easily peel off from the adherend, and even if the initial peeling force after adhering to the adherend is large, heavy peeling in time can be sufficiently suppressed. , The effect that the contamination on the surface of the adherend by adhering to the adherend is sufficiently low can be more expressed.

The number average molecular weight (Mn) of the fatty acid ester is preferably 100 to 800, more preferably 150 to 750, still more preferably 200 to 700, particularly preferably 200 to 650, most preferably 200 It is -600. If the number average molecular weight (Mn) of a fatty acid ester exists in the said range, the surface protection film of this invention does not peel easily from a to-be-adhered body, and even if the initial peeling force after adhering to a to-be-adhered body is large, it is heavy peeling at time. Can be sufficiently suppressed, and the effect that the contamination on the surface of the adherend by adhering to the adherend is sufficiently low can be more expressed.

As fatty acid ester, arbitrary appropriate fatty acid ester can be employ | adopted in the range which does not impair the effect of this invention. As such fatty acid ester, for example, polyoxyethylene bisphenol A lauric acid ester, butyl stearate, 2-ethylhexyl palmitic acid, 2-ethylhexyl stearate, behenic acid monoglyceride, 2-ethylhexanoic acid cetyl, Myristic acid isopropyl, isopropyl palmitic acid, isostearic acid cholesteryl, methacrylate lauryl, palm fatty acid methyl, methyl laurate, methyl oleate, methyl stearate, myristic acid myristyl, myristic acid Octyldodecyl, pentaerythritol monooleate, pentaerythritol monostearate, pentaerythritol tetrapalmitate, stearyl stearate, isotridecyl stearate, 2-ethylhexanoic acid triglyceride, butyl laurate, octyl oleate, etc. Can be mentioned.

When the pressure-sensitive adhesive composition contains a fatty acid ester, the content ratio of the fatty acid ester is preferably 0.01 part by weight to 50 parts by weight, more preferably 0.05 part by weight to 45 parts by weight, and more preferably 100 parts by weight of the base polymer. Preferably it is 0.1 weight part-40 weight part, More preferably, it is 0.3 weight part-35 weight part, More preferably, it is 0.5 weight part-30 weight part, Especially preferably, it is 0.5 weight part-25 weight part Most preferably, they are 0.5 weight part-20 weight part. If the content ratio of fatty acid ester is in the said range with respect to 100 weight part of base polymers, the surface protection film of this invention does not peel easily from a to-be-adhered body, Even if the initial peeling force after adhering to a to-be-adhered body is large over time. Can be sufficiently suppressed, and the effect that the contamination on the surface of the adherend by adhering to the adherend is sufficiently low can be more expressed.

<A-2-7. Other Ingredients>

The pressure-sensitive adhesive composition may contain any suitable other components within a range that does not impair the effects of the present invention. As such other components, for example, other resin components, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foil shapes, softeners, antioxidants, conductive agents, ultraviolet absorbers, antioxidants, light stabilizers, surface lubricants, leveling Agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts, and the like.

The pressure-sensitive adhesive composition may contain an ionic liquid containing a fluoro organic anion. By the pressure-sensitive adhesive composition comprising an ionic liquid containing a fluoro organic anion, it is possible to provide the pressure-sensitive adhesive composition excellent in antistatic properties. 1 type of these ionic liquids may be sufficient, and 2 or more types may be sufficient as them.

In this invention, an ionic liquid means the dissolved salt (ionic compound) which shows a liquid state at 25 degreeC.

As the ionic liquid, any suitable ionic liquid can be employed as long as it is an ionic liquid containing a fluoro organic anion, so long as the effects of the present invention are not impaired. The ionic liquid is preferably an ionic liquid composed of a fluoro organic anion and an onium cation. As an ionic liquid, by employing an ionic liquid composed of a fluoro organic anion and an onium cation, a pressure-sensitive adhesive composition excellent in antistatic property can be provided.

As the onium cation which can constitute an ionic liquid, any suitable onium cation can be adopted within a range that does not impair the effects of the present invention. 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, the pressure-sensitive adhesive composition having excellent antistatic property can be provided.

As a fluoro organic anion which can comprise an ionic liquid, arbitrary appropriate fluoro organic anions can be employ | adopted in the range which does not impair the effect of this invention. Such a fluoro organic anion may be completely fluorinated (perfluorinated) or partially fluorinated.

As such a fluoro organic anion, for example, fluorinated arylsulfonate, perfluoroalkanesulfonate, bis (fluorosulfonyl) imide, bis (perfluoroalkanesulfonyl) imide, cyanoperfluoro Alkanesulfonamides, Bis (cyano) perfluoroalkanesulfonylmethates, Cyano-bis- (perfluoroalkanesulfonyl) methides, Tris (perfluoroalkanesulfonyl) methides, trifluoroacetates , Perfluoroalkylate, tris (perfluoroalkanesulfonyl) methide, (perfluoroalkanesulfonyl) trifluoroacetamide, and the like.

Although an ionic liquid may use a commercially available thing, it is also possible to synthesize | combine as follows. The method for synthesizing the ionic liquid is not particularly limited as long as the target ionic liquid is obtained, but is generally described in the document "Ionic Liquid-Forefront and Future of Development" (published by CMC). The same halide method, hydroxide method, acid ester method, complexing method, and neutralization method are used.

As the compounding amount of the ionic liquid, the amount of the ionic liquid varies depending on the compatibility between the polymer to be used and the ionic liquid. However, the amount of the ionic liquid can not be defined uniformly, but is generally 0.001 to 50 parts by weight based on 100 parts by weight of the base polymer. More preferably, it is 0.01 weight part-40 weight part, More preferably, it is 0.01 weight part-30 weight part, Especially preferably, it is 0.01 weight part-20 weight part, Most preferably, 0.01 weight part-10 weight part to be. By adjusting the compounding quantity of an ionic liquid in the said range, the adhesive composition excellent in the antistatic property can be provided. If the said compounding quantity of an ionic liquid is less than 0.01 weight part, there exists a possibility that sufficient antistatic property may not be obtained. When the compounding amount of the ionic liquid exceeds 50 parts by weight, contamination to the adherend tends to increase.

The pressure-sensitive adhesive composition may contain a modified silicone oil within a range that does not impair the effects of the present invention. When an adhesive composition contains a modified silicone oil, the effect of antistatic property can be expressed. In particular, by using together with an ionic liquid, the effect of an antistatic characteristic can be expressed more effectively.

When the pressure-sensitive adhesive composition contains a modified silicone oil, the content ratio thereof is preferably 0.001 part by weight to 50 parts by weight, more preferably 0.005 part by weight to 40 parts by weight, further preferably 100 parts by weight of the base polymer. Preferably it is 0.007 weight part-30 weight part, Especially preferably, it is 0.008 weight part-20 weight part, Most preferably, it is 0.01 weight part-10 weight part. By adjusting the content rate of modified silicone oil in the said range, the effect of an antistatic characteristic can be expressed more effectively.

Arbitrary suitable modified silicone oil can be employ | adopted in the range which does not impair the effect of this invention as modified silicone oil. 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 employing a polyether modified silicone oil, the effect of the antistatic property can be more effectively expressed.

Examples of the polyether-modified silicone oil include polyether-modified silicone oil of side chain type, polyether-modified silicone oil of sock end, and the like. Among these, the sock end type polyether modified silicone oil is preferable at the point which can fully express the effect of antistatic characteristic more effectively.

≪≪B. Use≫≫

The surface protection film of this invention does not peel easily from a to-be-adhered body, Even if the initial peeling force after adhering to a to-be-adhered body is large, heavy peeling in time can fully be suppressed, and the said by adhering to a to-be-adhered body The effect that contamination on the surface of an adherend is sufficiently low can be exhibited. For this reason, it can use suitably for the surface protection of an optical member or an electronic member. The optical member of the present invention is to which the surface protection film of the present invention is bonded. The electronic member of the present invention is to which the surface protection film of the present invention is bonded.

Example

Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples at all. In addition, the test and evaluation method in an Example etc. are as follows. In addition, when it describes as "part", it means "weight part" unless there is a special matter, and when it describes as "%", it means "weight%" unless there is a special matter.

Peeling force A from the glass plate (after leaving at 23 ° C. for 30 minutes)

The pressure-sensitive adhesive layer side of the surface protection film (width 25mm X length 140mm) which separated the separator was bonded to a glass plate (soda lime glass, Matsunami Glass Ind., Ltd.) by 2 kg hand roller 1 reciprocation, and it is 30 under the environment temperature of 23 degreeC I left for a minute.

The sample for evaluation obtained as mentioned above was measured with the tensile tester. As a tensile tester, the brand name "Autograph AG-Xplus HS 6000mm / min high speed model (AG-50NX plus)" by Shimadzu Corporation was used. The sample for evaluation was set to the tension tester, and the tension test was started. Specifically, the load at the time of peeling a surface protection film from the said glass plate was measured, and the average load at that time was made into the peeling force A from the glass plate of a surface protection film. The conditions of the tensile test were test environment temperature: 23 degreeC, peeling angle: 180 degree | times, and peeling speed (tensile speed): 300 mm / min.

<Heeling force B from glass plate (after standing at temperature 100 degreeC for 2 days)>

The pressure-sensitive adhesive layer side of the surface protection film (25 mm in width X 140 mm in length) which separated the separator was bonded to a glass plate (soda lime glass, Matsunami Glass Ind., Ltd.) with 2 kg hand roller 1 reciprocating, I left for a day.

The sample for evaluation obtained as mentioned above was measured with the tensile tester. As a tensile tester, the brand name "Autograph AG-Xplus HS 6000mm / min high speed model (AG-50NX plus)" by Shimadzu Corporation was used. The sample for evaluation was set to the tension tester, and the tension test was started. Specifically, the load at the time of peeling a surface protection film from the said glass plate was measured, and the average load at that time was made into the peeling force B from the glass plate of a surface protection film. The conditions of the tensile test were test environment temperature: 23 degreeC, peeling angle: 180 degree | times, and peeling speed (tensile speed): 300 mm / min.

<Peel force C from the glass plate (after leaving for 7 days at a temperature of 23 ° C.)>

The adhesive layer side of the surface protection film (25 mm in width X 140 mm in length) which separated the separator was bonded to a glass plate (soda lime glass, Matsunami Glass Ind., Ltd.) by 2 kg hand roller 1 reciprocating, I left for a day.

The sample for evaluation obtained as mentioned above was measured with the tensile tester. As a tensile tester, the brand name "Autograph AG-Xplus HS 6000mm / min high speed model (AG-50NX plus)" by Shimadzu Corporation was used. The sample for evaluation was set to the tension tester, and the tension test was started. Specifically, the load at the time of peeling a surface protection film from the said glass plate was measured, and the average load at that time was made into the peeling force C from the glass plate of a surface protection film. The conditions of the tensile test were test environment temperature: 23 degreeC, peeling angle: 180 degree | times, and peeling speed (tensile speed): 300 mm / min.

<Residual Adhesion Rate to Glass Plate at 23 ° C>

The adhesive layer side of the surface protection film which peeled a separator to the glass plate (made by Matsunami Glass Ind., Ltd., 1.35 mm x 10 cm x 10 cm) is bonded to the whole surface with 1 kg of 2 kg hand rollers, and temperature 23 degreeC, humidity 55% RH After storing for 24 hours in the atmosphere of, the surface protective film was peeled off at a rate of 0.3 m / min to prepare a finished glass plate.

Subsequently, No. of 19 mm width cut | disconnected by 150 mm in length to the surface which the surface protection film of the said processed glass plate peeled. A 31B tape (Nitto Denko Co., Ltd. make, substrate thickness: 25 micrometers) was affixed by 1 kg of 2 kg hand rollers in the atmosphere of the temperature of 23 degreeC, and 55% RH of humidity. After curing for 30 minutes in an atmosphere of a temperature of 23 ° C. and a humidity of 55% RH, the peeling angle was obtained using a tensile tester (trade name `` Autograph AG-Xplus HS 6000mm / min high speed model (AG-50NX plus) manufactured by Shimadzu Corporation) ''. : It peeled at 180 degree | times and peeling rate: 300 mm / min, and measured the adhesive force a.

Separately, the glass plate (1.35 mm x 10 cm x 10 cm, which was manufactured by Matsunami Glass Ind., Ltd.) that was not subjected to the above-mentioned surface protection film bonding and peeling treatment was also subjected to No. 19 mm width. The adhesion force b of the 31B tape was measured.

The residual adhesion rate was calculated by the following formula.

Residual Adhesion (%) = (Adhesion a / Adhesion b) × 100

This residual adhesion rate is an index of how much the components of the pressure-sensitive adhesive layer of the surface protective film are transferred to and contaminated on the surface of the adherend with respect to the adherend. The higher the value of the residual adhesion rate, the more the surface protective film is less likely to contaminate the surface of the adherend with the components of the pressure-sensitive adhesive layer. The lower the value of the residual adhesion rate is the surface protection film that is more susceptible to contamination of the surface of the adherend with the components of the pressure-sensitive adhesive layer. to be.

<Elastic modulus of storage>

(How to make a sample)

The pressure-sensitive adhesive composition was applied to a peeling treatment surface of a 38-micrometer-thick polyester film (trade name: MRF, manufactured by Mitsubishi Chemical Corporation) having a single side peeled with silicone, so that the thickness after drying was 50 μm with a fountain roll, and the drying temperature was 130 ° C. It cured and dried on the conditions of 3 minutes of drying time. In this way, the adhesive layer was produced on the base material. Subsequently, a 38-micrometer-thick polyester film (brand name: MRF, Mitsubishi Chemical Corporation) which peeled one side | surface with silicone was coat | covered on the surface of an adhesive layer so that the peeling process surface of the said film might be an adhesive layer side. In this way, an adhesive sheet was produced.

(How to measure)

Only the adhesive layer was taken out and laminated | stacked from the obtained adhesive sheet, it was made into thickness of about 2 mm, it punched at phi 7.9 mm, the columnar pellet was produced, and it was set as the sample for a measurement. The measurement sample was fixed to the jig of a φ7.9 mm parallel plate, and the storage modulus (G ') was calculated by a dynamic viscoelasticity measuring device (manufactured by Rheometrics Co., ARES). Measurement conditions are as follows. In addition, "a. E + b '' generally means "a x 10 ^b ", as is well known.

Measurement: Shear Mode

Temperature range: -70 ℃ to 150 ℃

Temperature rise rate: 5 ℃ / min

Frequency: 1 Hz

[Production example 1]

Polypropylene glycol (product name `` SANNIX PP-2000 '') for 1L round bottom separable flask, separable cover, liquid separation lot, thermometer, nitrogen introduction tube, Liebig chiller, battery seal, stirring rod, polymerization apparatus equipped with stirring blade , Sanyo Chemical Industries, Ltd.): 150 g, polyester polyol (product name "Kuraray Polyol P-2010", manufactured by Kuraray Co., Ltd.): 150 g, toluene (manufactured by Tosoh Corporation): 110 g, as a solvent Dibutyl laurate diIV (IV) (made by Wako Pure Chemical Industries, Ltd.): 0.041g was added and stirred, and nitrogen substitution was performed at normal temperature for 1 hour. Thereafter, while stirring under nitrogen inflow, hexamethylene diisocyanate (product name "HDI", manufactured by Tosoh Corporation): 33.5 g was added thereto, and maintained for 4 hours while controlling the solution temperature in the experimental apparatus to 90 ± 2 ° C in a water bath. After that, polypropylene glycol (product name "GP1000", manufactured by Sanyo Chemical Industries, Ltd.): 74.9 g was added thereto, and maintained for 2 hours while controlling the solution temperature in the experimental apparatus to 90 ± 2 ° C in a water bath, Hexamethylene diisocyanate (product name "HDI", manufactured by Tosoh Corporation): 25.4 g was added thereto and maintained for 2 hours while controlling the solution temperature in the experimental apparatus to be 90 ± 2 ° C. in a water bath to obtain a urethane prepolymer solution A. In addition, toluene was appropriately added dropwise for the purpose of temperature control during polymerization and prevention of agitation deterioration due to viscosity increase during polymerization. The total amount of toluene dropped was 320 g. Solid content concentration of urethane prepolymer solution A was 50 weight%.

EXAMPLE 1

As shown in Table 1, 100 parts by weight of the urethane prepolymer solution A obtained in Production Example 1 in terms of polymer solid content, and an isocyanate crosslinking agent (trade name "CORONATE HL", manufactured by Nippon Polyurethane Industry Co., Ltd.) in terms of solid content 14.6 parts by weight, 0.5 parts by weight of a heat stabilizer (trade name "Irganox 1010", manufactured by BASF) in terms of solid content, a low molecular weight polyol (trade name "SANNIX GP250", number average molecular weight (Mn) = 250, Sanyo Chemical Industries, Ltd.) to 1.0 parts by weight in terms of solids, 0.05 parts by weight of fluorine-containing polymer (trade name "F-571", manufactured by DIC Corporation) in terms of solids, and a fatty acid ester (trade name "Salacos 816", Nisshin Oillio Group Ltd. .1) was mixed with 1 part by weight in terms of solid content, and diluted with ethyl acetate so that the total solid content was 45% by weight to obtain an adhesive composition (1).

The obtained adhesive composition (1) was apply | coated to the base material (brand name "T100-75S", thickness 75 micrometers, Mitsubishi Chemical Corporation make) which consists of polyester resins so that thickness after drying might be 75 micrometers, and drying temperature 130 degreeC, drying time 3 Cured and dried under conditions of minutes. In this way, the adhesive layer 1 formed of the adhesive composition 1 on the base material was produced.

Subsequently, the siliconization surface of the separator (brand name "MRF25", thickness 25micrometer, the product made by Mitsubishi Chemical Corporation) which consists of a polyester resin with a thickness of 25 micrometers which gave one surface the siliconization on the surface of the obtained adhesive layer 1 was carried out. It bonded together and obtained the surface protection film (1).

The obtained surface protection film (1) performed aging at normal temperature for 7 days, and evaluated. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 2.

EXAMPLE 2

As shown in Table 1, the compounding quantity of an isocyanate type crosslinking agent (brand name "CORONATE HL", the product made by Nippon Polyurethane Industry Co., Ltd.) is 16.0 weight part in terms of solid content, and low molecular weight polyol (brand name "SANNIX GP250", number average) Except having changed the compounding quantity of molecular weight (Mn) = 250 by Sanyo Chemical Industries, Ltd. to 1.5 weight part in conversion of solid content, it carried out similarly to Example 1, and carried out the adhesive layer 2 formed from the adhesive composition 2 by It produced and obtained the surface protection film (2). The results are shown in Table 2.

EXAMPLE 3

As shown in Table 1, the compounding quantity of an isocyanate type crosslinking agent (brand name "CORONATE HL", the product made by Nippon Polyurethane Industry Co., Ltd.) was 16.6 weight part in terms of solid content, and low molecular weight polyol (brand name "SANNIX GP250", number average) Except having changed the compounding quantity of molecular weight (Mn) = 250 by Sanyo Chemical Industries, Ltd. into 2.0 weight part in conversion of solid content, it carried out similarly to Example 1, and carried out the adhesive layer 3 formed from the adhesive composition 3 by It produced and obtained the surface protection film (3). The results are shown in Table 2.

EXAMPLE 4

As shown in Table 1, the compounding quantity of an isocyanate type crosslinking agent (brand name "CORONATE HL" and Nippon Polyurethane Industry Co., Ltd.) was changed to 6.5 weight part in conversion of solid content, and fatty acid ester (brand name "Salacos 816", Nisshin) Except not using Oillio Group Ltd.), it carried out similarly to Example 1, the adhesive layer 4 formed from the adhesive composition 4 was produced, and the surface protection film 4 was obtained. The results are shown in Table 2.

[Example 5]

As shown in Table 1, the compounding quantity of an isocyanate type crosslinking agent (brand name "CORONATE HL", Nippon Polyurethane Industry Co., Ltd.) is 13.2 weight part in terms of solid content, and low molecular weight polyol (brand name "SANNIX GP250", number average) The pressure-sensitive adhesive layer 5 formed of the pressure-sensitive adhesive composition 5 was formed in the same manner as in Example 4 except that the compounding amount of the molecular weight (Mn) = 250, manufactured by Sanyo Chemical Industries, Ltd. was changed to 3.0 parts by weight in terms of solid content. It produced and obtained the surface protection film (5). The results are shown in Table 2.

EXAMPLE 6

As shown in Table 1, the compounding quantity of an isocyanate type crosslinking agent (brand name "CORONATE HL", Nippon Polyurethane Industry Co., Ltd.) was made into 20.0 weight part in conversion of solid content, and low molecular weight polyol (brand name "SANNIX GP250", number average) The pressure-sensitive adhesive layer 6 formed of the pressure-sensitive adhesive composition 6 was formed in the same manner as in Example 4 except that the compounding amount of the molecular weight (Mn) = 250, manufactured by Sanyo Chemical Industries, Ltd. was changed to 5.0 parts by weight in terms of solid content. It produced and obtained the surface protection film (6). The results are shown in Table 2.

EXAMPLE 7

As shown in Table 1, the compounding quantity of an isocyanate type crosslinking agent (brand name "CORONATE HL", Nippon Polyurethane Industry Co., Ltd.) was changed to 4.5 weight part in conversion of solid content, and low molecular weight polyol (brand name "SANNIX GP250", Instead of number average molecular weight (Mn) = 250, manufactured by Sanyo Chemical Industries, Ltd., a low molecular weight polyol (brand name "SANNIX GP600", number average molecular weight (Mn) = 600, manufactured by Sanyo Chemical Industries, Ltd.) in terms of solid content Except having used 1.0 weight part, it carried out similarly to Example 4, the adhesive layer 7 formed from the adhesive composition 7 was produced, and the surface protection film 7 was obtained. The results are shown in Table 2.

EXAMPLE 8

As shown in Table 1, the compounding quantity of an isocyanate type crosslinking agent (brand name "CORONATE HL", the product made by Nippon Polyurethane Industry Co., Ltd.) is 7.3 weight part in terms of solid content, and low molecular weight polyol (brand name "SANNIX GP600", number average) Except having changed the compounding quantity of molecular weight (Mn) = 600, Sanyo Chemical Industries, Ltd.) into 3.0 weight part in conversion of solid content, it carried out similarly to Example 7, and carried out the adhesive layer 8 formed from the adhesive composition 8 by It produced and obtained the surface protection film (8). The results are shown in Table 2.

EXAMPLE 9

As shown in Table 1, the compounding quantity of an isocyanate type crosslinking agent (brand name "CORONATE HL", the product made by Nippon Polyurethane Industry Co., Ltd.) is 10.0 weight part in terms of solid content, and low molecular weight polyol (brand name "SANNIX GP600", number average) Except having changed the compounding quantity of molecular weight (Mn) = 600, Sanyo Chemical Industries, Ltd.) into 5.0 weight part in conversion of solid content, it carried out similarly to Example 7, and performs the adhesive layer 9 formed from the adhesive composition 9 by It produced and obtained the surface protection film (9). The results are shown in Table 2.

EXAMPLE 10

As shown in Table 1, the compounding quantity of an isocyanate type crosslinking agent (brand name "CORONATE HL", a Nippon Polyurethane Industry Co., Ltd. product) was changed to 4.0 weight part in conversion of solid content, and the low molecular weight polyol (brand name "SANNIX GP250", Instead of number average molecular weight (Mn) = 250, manufactured by Sanyo Chemical Industries, Ltd., a low molecular weight polyol (trade name "SANNIX GP1000", number average molecular weight (Mn) = 1000, manufactured by Sanyo Chemical Industries, Ltd.) in terms of solid content Except having used 1.0 weight part, it carried out similarly to Example 4, the adhesive layer 10 formed from the adhesive composition 10 was produced, and the surface protection film 10 was obtained. The results are shown in Table 2.

EXAMPLE 11

As shown in Table 1, the compounding quantity of an isocyanate type crosslinking agent (brand name "CORONATE HL", Nippon Polyurethane Industry Co., Ltd.) is 5.6 weight part in terms of solid content, and low molecular weight polyol (brand name "SANNIX GP1000", number average) The pressure-sensitive adhesive layer 11 formed of the pressure-sensitive adhesive composition 11 was formed in the same manner as in Example 10 except that the compounding amount of the molecular weight (Mn) = 1000, manufactured by Sanyo Chemical Industries, Ltd. was changed to 3.0 parts by weight in terms of solid content. It produced and obtained the surface protection film (11). The results are shown in Table 2.

EXAMPLE 12

As shown in Table 1, the compounding quantity of an isocyanate type crosslinking agent (brand name "CORONATE HL", Nippon Polyurethane Industry Co., Ltd.) is 7.3 weight part in terms of solid content, and low molecular weight polyol (brand name "SANNIX GP1000", number average) Except having changed the compounding quantity of molecular weight (Mn) = 1000 by Sanyo Chemical Industries, Ltd. into 5.0 weight part in conversion of solid content, it carried out similarly to Example 10, and carried out the adhesive layer 12 formed from the adhesive composition 12 by It produced and obtained the surface protection film (12). The results are shown in Table 2.

EXAMPLE 13

As shown in Table 1, the compounding quantity of an isocyanate type crosslinking agent (brand name "CORONATE HL", the product made by Nippon Polyurethane Industry Co., Ltd.) is 16.0 weight part in terms of solid content, and low molecular weight polyol (brand name "SANNIX GP250", number average) Molecular weight (Mn) = 250, manufactured by Sanyo Chemical Industries, Ltd. was changed to 1.5 parts by weight in terms of solid content, and instead of fluorine-containing polymer (trade name "F-571", manufactured by DIC Corporation), hydroxyl group-containing silicone (brand name " X-22-4015, manufactured by Shin-Etsu Chemical Co., Ltd.), was used in the same manner as in Example 4 except that 0.05 parts by weight of the pressure-sensitive adhesive layer 13 formed of the pressure-sensitive adhesive composition 13 was used. It produced and obtained the surface protection film (13). The results are shown in Table 2.

[Comparative Example 1]

As shown in Table 1, the compounding quantity of an isocyanate type crosslinking agent (brand name "CORONATE HL", Nippon Polyurethane Industry Co., Ltd.) was changed to 3.2 weight part in conversion of solid content, and the low molecular weight polyol (brand name "SANNIX GP250", Except for using the number average molecular weight (Mn) = 250, manufactured by Sanyo Chemical Industries, Ltd., and not using a fluorine-containing polymer (trade name "F-571", manufactured by DIC Corporation), as in Example 4. It carried out and produced the adhesive layer (C1) formed from an adhesive composition (C1), and obtained the surface protection film (C1). The results are shown in Table 2.

[Comparative Example 2]

As shown in Table 1, it carried out similarly to the comparative example 1 except having changed the compounding quantity of the isocyanate type crosslinking agent (brand name "CORONATE HL", Nippon Polyurethane Industry Co., Ltd.) into 4.6 weight part in solid content conversion. The adhesive layer (C2) formed from the composition (C2) was produced, and the surface protection film (C2) was obtained. The results are shown in Table 2.

(Comparative Example 3)

As shown in Table 1, except having mix | blended 0.05 weight part of fluorine-containing polymer (brand name "F-571", product made by DIC Corporation) in conversion of solid content, it carried out similarly to the comparative example 2, and is formed in adhesive composition (C3). The adhesive layer (C3) used was produced and the surface protection film (C3) was obtained. The results are shown in Table 2.

(Comparative Example 4)

As shown in Table 1, it carried out similarly to the comparative example 2 except having mix | blended 5 weight part of fatty acid esters (brand name "Salacos 816", Nisshin Oillio Group Ltd.) in solid content conversion, and carried out as the adhesive composition (C4) The adhesive layer (C4) formed was produced and surface protection film (C4) was obtained. The results are shown in Table 2.

(Comparative Example 5)

As shown in Table 1, the compounding quantity of an isocyanate type crosslinking agent (brand name "CORONATE HL", Nippon Polyurethane Industry Co., Ltd. product) was changed to 9.3 weight part in conversion of solid content, and a fluorine-containing polymer (brand name "F-571" And 0.01 parts by weight of DIC Corporation) in terms of solids content, and 1 part by weight of a fatty acid ester (trade name "Salacos 816", manufactured by Nisshin Oillio Group Ltd.) in terms of solids content, was the same as in Comparative Example 1. The adhesive layer (C5) formed by the adhesive composition (C5) was produced, and the surface protection film (C5) was obtained. The results are shown in Table 2.

(Comparative Example 6)

As shown in Table 1, it carried out similarly to the comparative example 5 except having changed the compounding quantity of the isocyanate type crosslinking agent (brand name "CORONATE HL", Nippon Polyurethane Industry Co., Ltd.) to 12.4 weight part in conversion of solid content. The adhesive layer (C6) formed from the composition (C6) was produced, and the surface protection film (C6) was obtained. The results are shown in Table 2.

(Comparative Example 7)

As shown in Table 1, 100 parts by weight of a commercially available urethane prepolymer solution (trade name "CYABINE SH-109", manufactured by Toyochem Co., Ltd.) in terms of polymer solids was used instead of the urethane prepolymer solution A obtained in Production Example 1. Instead of isocyanate-based crosslinking agent (brand name "CORONATE HL", product made by Nippon Polyurethane Industry Co., Ltd.), 3.6 wt.% Of isocyanate-based crosslinking agent (product name "CORONATE HX", product made by Nippon Polyurethane Industry Co., Ltd.) Pressure-sensitive adhesive layer formed in the pressure-sensitive adhesive composition (C7) in the same manner as in Comparative Example 1, except that 1.0 part by weight of a fluorine-containing polymer (trade name "F-571", manufactured by DIC Corporation) was further added in a solid content conversion manner. C7) was produced and the surface protection film (C7) was obtained. The results are shown in Table 2.

[Examples 14 to 26]

About each of the surface protection films (1)-(13) obtained in Examples 1-13, a separator is peeled off and the adhesive layer side is made into the polarizing plate (Nitto Denko Co., Ltd. make, brand name "TEG1465DUHC") which is an optical member. It bonded, and the optical member to which the surface protection film was bonded was obtained.

[Examples 27-39]

About each of the surface protection films (1)-(13) obtained in Examples 1-13, a separator is peeled off and the adhesive layer side is an electroconductive film (Nitto Denko Co., Ltd. make, brand name "ELECRYSTA V270L-) which is an electronic member. TFMP ”) to obtain an electronic member having a surface protective film bonded thereto.

(Industrial availability)

The surface protection film of this invention can be used for arbitrary suitable uses. Preferably, the surface protection film of this invention is used suitably in the field of an optical member or an electronic member.

1: substrate layer
2: adhesive layer
10: surface protection film

Claims (10)

As a surface protection film which has an adhesive layer,
After bonding the said adhesive layer of the said surface protection film to a glass plate, and leaving it to stand at the temperature of 23 degreeC for 30 minutes, when peeling the said surface protection film from the said glass plate at 180 degree of peeling angles, and the peeling rate of 300 mm / min at the temperature of 23 degreeC, When the peeling force is referred to as peeling force A, the peeling force A is 0.005 N / 25 mm to 0.50 N / 25 mm,
After bonding the said adhesive layer of the said surface protection film to a glass plate, and leaving it at the temperature of 100 degreeC for 2 days, when peeling the said surface protection film from the said glass plate at 180 degree of peeling angles and peeling rate 300mm / min at the temperature of 23 degreeC, When the peeling force is referred to as peeling force B, the peeling force elongation rate P calculated by (peeling force B / peeling force A) × 100 is 400% or less,
The storage modulus at -70 ° C of the pressure-sensitive adhesive layer is 5.0 × 10 ⁸ Pa to 1.0 × 10 ¹⁰ Pa,
The storage elastic modulus at 23 degrees C of the said adhesive layer is 7.0 * 10 < ⁵ > Pa ^~ 1.0 * 10 <^7> Pa,
The surface protection film whose storage elastic modulus at 100 degrees C of the said adhesive layer is 7.0 * 10 < ⁵ > Pa ^~ 5.0 * 10 <^6> Pa. The method of claim 1,
After bonding the said adhesive layer of the said surface protection film to a glass plate, and leaving it to stand at 23 degreeC for 7 days, peeling when peeling the said surface protection film from the said glass plate at 180 degree of peel angles and peeling rate 300mm / min at the temperature of 23 degreeC. When the force is referred to as peel force C, the surface protective film having a peel force with time increase rate Q calculated by (peel force C / peel force A) × 100 is 160% or less. The method according to claim 1 or 2,
The surface protection film whose residual adhesiveness with respect to the glass plate in 23 degreeC is 50% or more. The method according to any one of claims 1 to 3,
The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is formed of a pressure-sensitive adhesive composition, the pressure-sensitive adhesive composition comprises a base polymer, a silicone-based additive and / or a fluorine-based additive. The method of claim 4, wherein
Surface protective film wherein the pressure-sensitive adhesive composition comprises a fatty acid ester. The method according to claim 4 or 5,
The said silicone type additive is a surface protection film which is at least 1 sort (s) chosen from a siloxane bond containing compound, a hydroxyl group containing silicone type compound, and a crosslinkable functional group containing silicone type compound. The method according to any one of claims 4 to 6,
Surface protection film whose said fluorine-type additive is at least 1 sort (s) chosen from a fluorine-containing compound, a hydroxyl-containing fluorine-type compound, and a crosslinkable functional group-containing fluorine-type compound. The method according to any one of claims 4 to 7,
The surface protection film whose said base polymer is at least 1 sort (s) chosen from a urethane prepolymer, a polyol, acrylic resin, rubber resin, and silicone resin. The optical member to which the surface protection film as described in any one of Claims 1-8 was adhere | attached. The electronic member with which the surface protection film in any one of Claims 1-8 was adhere | attached.

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