TW202235573A - Surface protective film - Google Patents

Abstract

Provided is a surface protective film capable of exhibiting light peelability, and suppressing the occurrence of black spots. Also provided are an optical member and an electronic member to which such a surface protective film is attached. A surface protective film according to an embodiment of the present invention includes an adhesive layer, wherein the adhesive layer is composed of a urethane-based adhesive formed from a urethane-based adhesive composition, and the urethane-based adhesive composition contains a base polymer and a fluorine-based compound. The base polymer includes a urethane prepolymer, and the percentage of a hydroxyl group contained in the urethane-based adhesive composition is less than 30 mmol with respect to 100 g of the base polymer.

Description

surface protection film

The present invention relates to a surface protection film.

Optical components or electronic components are attached with a surface protection film to prevent damage to the surface during processing, assembly, inspection, transportation, and the like. Such a surface protection film peels off from an optical member or an electronic member when surface protection is unnecessary (patent document 1).

For an optical member or an electronic member to which such a surface protection film is bonded, it is important that when the surface protection film is to be peeled off as described above, it is only possible to smoothly peel off.

As an adhesive agent layer with which a surface protection film is equipped, the adhesive agent layer containing a urethane type adhesive agent is known. In addition, as the production method of the urethane-based adhesive, the following two production methods are known: a one-step method, which directly reacts a polyol and a polyfunctional isocyanate without using a urethane prepolymer. Manufacture of urethane adhesives; prepolymer method, which reacts urethane prepolymers with polyfunctional isocyanates to produce urethane adhesives.

It is known to contain a fluorine-based compound in an adhesive composition for forming a urethane-based adhesive for the purpose of expressing light peelability, etc., of a surface protection film having an adhesive layer containing a urethane-based adhesive. technology (Patent Document 2).

However, when observing the previous surface protection film, it was found that the occurrence of black spots presumably caused by smudges was found. The adhesive layer of the agent. If a large number of such black spots appear, not only the quality of the surface protection film may be reduced, but also the inspection property of the surface protection film bonded to, for example, an optical member or an electronic member may be reduced. [Prior Art Literature] [Patent Document]

Patent Document 1: Japanese Patent Laid-Open No. 2016-17109 Patent Document 2: Japanese Patent No. 6896927

[Problem to be solved by the invention]

The subject of this invention is to provide the surface protection film which can express light peelability, and can suppress generation|occurrence|production of black spots. Moreover, the optical member or electronic member which bonded such a surface protection film is provided. [Technical means to solve the problem]

The surface protection film system of the embodiment of the present invention Those containing an adhesive layer, The adhesive layer includes a urethane-based adhesive formed from a urethane-based adhesive composition, The urethane-based adhesive composition includes a base polymer and a fluorine-based compound, The base polymer comprises a urethane prepolymer, The ratio of the hydroxyl groups contained in the urethane-based adhesive composition is less than 30 mmol with respect to 100 g of the base polymer.

(通式(1)中，R ¹表示選自由氫原子、碳數1～4之烷基、及碳數1～6之羥烷基所組成之群中之1種。複數個R ¹相互可相同亦可不同。n表示1～4之整數。m表示1～200之整數) In one embodiment, the above-mentioned base polymer includes a polyoxyalkylene structure represented by general formula (1). [chemical 1]

(In general formula (1), R ¹ represents one species selected from the group consisting of a hydrogen atom, an alkyl group with 1 to 4 carbons, and a hydroxyalkyl group with 1 to 6 carbons. A plurality of R ^1s may mutually be The same or different. n represents an integer from 1 to 4. m represents an integer from 1 to 200)

In one embodiment, the above-mentioned urethane prepolymer includes a polyoxyalkylene structure represented by the above-mentioned general formula (1).

In one embodiment, the above-mentioned base polymer comprises a polyol which is not a urethane prepolymer.

(通式(1)中，R ¹表示選自由氫原子、碳數1～4之烷基、及碳數1～6之羥烷基所組成之群中之1種。複數個R ¹相互可相同亦可不同。n表示1～4之整數。m表示1～200之整數) In one embodiment, the above-mentioned polyol includes a polyoxyalkylene structure represented by general formula (1). [Chem 2]

(In general formula (1), R ¹ represents one species selected from the group consisting of a hydrogen atom, an alkyl group with 1 to 4 carbons, and a hydroxyalkyl group with 1 to 6 carbons. A plurality of R ^1s may mutually be The same or different. n represents an integer from 1 to 4. m represents an integer from 1 to 200)

In one embodiment, the content ratio of the above-mentioned urethane prepolymer to the above-mentioned polyol in the above-mentioned urethane-based adhesive composition is calculated by weight ratio, and the urethane prepolymer: Polyol=70:30～100:0.

In one embodiment, the haze of the adhesive layer is 3.5% or less.

In one embodiment, the surface tension of the above-mentioned fluorine-based compound when prepared as a 0.1% propylene glycol monomethyl ether solution is 23 mN/m or more.

In one embodiment, the said urethane adhesive composition contains 0.05 weight part or more of ionic compounds with respect to 100 weight part of said base polymers.

The optical member of embodiment of this invention has the surface protection film of embodiment of this invention bonded.

The electronic component according to the embodiment of the present invention is bonded with the surface protection film according to the embodiment of the present invention. [Effect of Invention]

According to the present invention, it is possible to provide a surface protection film capable of expressing light peelability and suppressing generation of black spots. Moreover, the optical member and electronic member which bonded such a surface protection film can be provided.

""1. Surface Protection Film"" The surface protection film of embodiment of this invention contains an adhesive agent layer. The surface protection film according to the embodiment of the present invention preferably includes a base material layer and an adhesive layer.

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

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

Any appropriate release liner may also be bonded to the adhesive side (sometimes called the adhesive side) side of the adhesive layer within the range that does not impair the effects of the present invention.

As the release liner, for example, a release liner obtained by treating the surface of a base material such as paper or plastic film (liner base material) with silicone; a base material such as paper or plastic film (liner base material) The surface is laminated with a release liner made of polyolefin resin.

Regarding the plastic film as the base material included in the release liner, for example, any appropriate plastic film can be employed within the range that does not impair the effect of the present invention. As such plastic films, for example, polyethylene films, polypropylene films, polybutene films, polybutadiene films, polymethylpentene films, polyvinyl chloride films, vinyl chloride copolymer films, polyethylene Ethylene phthalate film, polybutylene terephthalate film, polyurethane film, ethylene-vinyl acetate copolymer film.

The thickness of the release liner is preferably from 1 μm to 500 μm, more preferably from 3 μm to 450 μm, further preferably from 5 μm to 400 μm, especially preferably from 10 μm to 300 μm.

When the surface protection film according to the embodiment of the present invention includes a base material layer and an adhesive layer, the surface of the base layer opposite to the adhesive layer is for the purpose of forming a wound body that is easy to unwind, for example Add aliphatic amide, polyethyleneimine, long-chain alkyl additives, etc. to the substrate layer for release treatment, or set any appropriate release agent including silicone-based, long-chain alkyl-based, fluorine-based, etc. agent coating.

The surface protection film of embodiment of this invention may have arbitrary other appropriate layers in the range which does not impair the effect of this invention.

Fig. 1 is a schematic sectional view of a surface protection film according to a preferred embodiment of the present invention. As shown in FIG. 1 , a surface protection film 10 according to a preferred embodiment of the present invention has a substrate layer 1 and an adhesive layer 2 , and is formed by directly laminating the substrate layer 1 and the adhesive layer 2 .

The thickness of the surface protective film according to the embodiment of the present invention can be set to any appropriate thickness depending on the application. Typically, it is preferably 10 μm to 300 μm, more preferably 15 μm to 250 μm, still more preferably 20 μm to 200 μm, and particularly preferably 25 μm to 170 μm.

It is preferable that the surface protection film of embodiment of this invention can express light peelability. After the surface protection film of the present invention is bonded to a glass plate and held at 23°C for 30 minutes, the peeling force when peeled off from the glass plate at a peeling angle of 180 degrees and a peeling speed of 300 mm/min is relatively high. Preferably 0.5 gf/25 mm to 5.0 gf/25 mm, more preferably 0.5 gf/25 mm to 4.0 gf/25 mm, more preferably 0.5 gf/25 mm to 3.0 gf/25 mm, most preferably 0.5 gf /25 mm to 2.5 gf/25 mm, preferably 0.5 gf/25 mm to 2.0 gf/25 mm. If the said peeling force exists in the said range, the surface protection film which concerns on embodiment of this invention can express the outstanding light peelability. In addition, the measuring method of the said peeling force is demonstrated in detail.

It is preferable that the surface protection film of embodiment of this invention can realize low haze. The haze of the adhesive layer included in the surface protection film of the present invention is preferably 4.0% or less, more preferably 3.0% or less, further preferably 2.0% or less, especially preferably 1.5% or less, most preferably 1.0% the following. If the said haze is in the said range, the surface protection film which concerns on embodiment of this invention can realize the outstanding low haze, for example, can express the outstanding inspectionability. Furthermore, the measurement method of the said haze is demonstrated in detail.

In the surface protection film according to the embodiment of the present invention, after the adhesive layer contained therein is attached to a glass plate and placed in an environment of 23° C. and 50% RH for 1 day, it is peeled from the glass plate at a peeling angle of 150 degrees and a peeling speed of The peeling static voltage when peeling at 30 m/min is preferably 15 kV or less, more preferably 10 kV or less, further preferably 5 kV or less, especially preferably 2 kV or less, most preferably 1 kV or less. If the said peeling electrostatic voltage exists in the said range, the surface protection film which concerns on embodiment of this invention can prevent the static electricity at the time of peeling effectively. Furthermore, the method of measuring the above-mentioned peeling electrostatic voltage will be described in detail.

"1-1. Adhesive Layer" The adhesive layer contains a urethane adhesive. The urethane-based adhesive is formed from a urethane-based adhesive composition. That is, the urethane-based adhesive formed from the urethane-based adhesive composition becomes an adhesive layer by constituting a layer shape.

The thickness of the adhesive layer can be set to any appropriate thickness depending on the application. Typically, it is preferably 1 μm to 150 μm, more preferably 5 μm to 130 μm, further preferably 10 μm to 110 μm, and particularly preferably 20 μm to 100 μm.

The urethane-based adhesive composition includes a base polymer and a fluorine-based compound. Only 1 type may be sufficient as a base polymer, and 2 or more types may be sufficient as it. A fluorine-type compound may be only 1 type, and may be 2 or more types.

The base polymer comprises a urethane prepolymer. The urethane prepolymer is described in detail.

The base polymer may also contain polyols. Polyols are described in detail. Furthermore, as described below, the polyols of the present invention are not urethane prepolymers.

A preferred embodiment of the base polymer of the present invention is (A) Embodiments comprising urethane prepolymers but no polyols; or (B) An embodiment including both a urethane prepolymer and a polyol.

An embodiment of the base polymer of the present invention is more preferably (a) Embodiments comprising urethane prepolymers; or (b) An embodiment comprising a urethane prepolymer and a polyol.

The content ratio of the base polymer in the urethane-based adhesive composition is preferably 50% by weight to 99.99% by weight, more preferably 70% by weight, based on the viewpoint that the effects of the present invention can be further exhibited ~99.99% by weight, more preferably 90% by weight to 99.99% by weight, especially preferably 95% by weight to 99.99% by weight. The surface protection film of this invention can express the effect of this invention further by adjusting the content ratio of the base polymer in a urethane-type adhesive composition to the said range.

The ratio of hydroxyl groups contained in the urethane-based adhesive composition is less than 30 mmol, preferably 5 mmol to 28 mmol, more preferably 5 mmol to 25 mmol, relative to 100 g of the base polymer, Further preferably, it is 5 mmol to 22 mmol, and especially preferably 5 mmol to 20 mmol. The effect of this invention can be expressed by making the ratio of the hydroxyl group contained in a urethane-type adhesive composition into the said range with respect to 100 g of base polymers.

When the present invention was completed, the present inventors conducted various studies on the suppression of generation of black spots which is a subject. As a result, it is considered that the cause of the black spots may be as follows: the fluorine-based compound around the air bubbles generated during the formation of the adhesive acts as a surfactant to form stable micelles, which eventually leads to the formation of the adhesive layer. The air bubbles produce glue marks. Therefore, the present inventors thought that if the formation of the above-mentioned micelles could be suppressed, or the generation of black spots could be suppressed, and further studies were conducted. As a result, they focused on the base polymer in the urethane-based adhesive composition (typically, , is the compatibility of urethane prepolymer and polyol as an optional component) with fluorine-based compounds. Furthermore, as a result of repeated studies from the viewpoint of adjusting the compatibility between the base polymer and the fluorine-based compound, it was found that by combining the urethane-based adhesive with respect to 100 g of the base polymer If the ratio of the hydroxyl groups contained in the compound is set within the above range, the generation of black spots can be effectively suppressed.

The urethane-based adhesive can be defined as being formed from a urethane-based adhesive composition. The reason for this is that, for urethane-based adhesives, since the urethane-based adhesive composition undergoes a cross-linking reaction due to heating or ultraviolet radiation, etc., it becomes a urethane-based adhesive. Therefore, it is impossible to directly specify the urethane-based adhesive based on its structure, and there is a completely impractical situation ("impossible/impractical situation"), so by " Urethane-based adhesives are safely specified as "things" by the provisions of "formers of urethane-based adhesive compositions".

As a method of forming the urethane-based adhesive from the urethane-based adhesive composition, any appropriate formation method can be adopted within the range that does not impair the effect of the present invention. As such a forming method, for example, direct coating of the urethane-based adhesive composition on any appropriate base film (for example, the base layer in the surface protection film according to the embodiment of the present invention) A method of drying or hardening (direct method); coating a urethane-based adhesive composition on the surface (release surface) of a release liner and drying or hardening it, thereby forming a A urethane-based adhesive layer, the urethane-based adhesive layer is bonded to a substrate film (for example, the substrate layer in the surface protective film according to the embodiment of the present invention) and the amine is transferred. The method of the urethane-based adhesive layer (transfer method).

As a coating method of the urethane-based adhesive composition, any appropriate coating method can be adopted within the range that does not impair the effect of the present invention. Examples of such coating methods include roll coating, gravure roll coating, reverse roll coating, touch roll coating, dip roll coating, and bar coating. , Roller brushing method, spraying method, blade coating method, air knife coating method, chipped wheel coating method, direct coating method, die coating, roller brush coating method.

Drying of the urethane-based adhesive composition may be performed under heating (for example, by heating to about 60° C. to 150° C.) if necessary.

As a method of curing the urethane-based adhesive composition, any appropriate curing method can be adopted within the range not impairing the effect of the present invention. Examples of such curing methods include ultraviolet irradiation, laser irradiation, α-ray irradiation, β-ray irradiation, γ-ray irradiation, X-ray irradiation, and electron beam irradiation.

The base polymer (typically, at least one selected from the following urethane prepolymers and polyols) preferably includes a polyoxyalkylene structure represented by general formula (1) . By making the base polymer contain the polyoxyalkylene structure represented by the general formula (1), it is possible to further express light peelability. Furthermore, it can be confirmed by any appropriate method that the base polymer contains the polyoxyalkylene structure represented by the general formula (1). As such a method, NMR measurement, IR measurement, etc. are mentioned, for example. [Chem 3]

In the general formula (1), R ¹ represents one species selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 4 carbons, and a hydroxyalkyl group having 1 to 6 carbons. Furthermore, a plurality of R ¹ may be the same as or different from each other.

In the general formula (1), when R ¹ is an alkyl group having 1 to 4 carbon atoms, the alkyl group may, for example, be linear alkyl such as methyl, ethyl, or n-propyl; isopropyl branched chain alkyl such as isobutyl, 2-ethylhexyl, etc.

In the general formula (1), when R ¹ is a hydroxyalkyl group having 1 to 6 carbon atoms, examples of the hydroxyalkyl group include: hydroxymethyl group, 2-hydroxyethyl group, 2-methyl-1 ,4-Hydroxybutyl.

As R ¹ in the general formula (1), preferably, one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbons, more preferably, one selected from the group consisting of hydrogen One of the group consisting of an atom and a methyl group, more preferably a hydrogen atom.

In the general formula (1), n represents the repeating number of the structural unit and represents an integer of 1-4. n is preferably an integer of 1-3, more preferably 1 or 2, and still more preferably 2, from the viewpoint that the effects of the present invention can be further exhibited.

In general formula (1), m is the repeating number of a structural unit, and represents the integer of 1-200. From the viewpoint that the effect of the present invention can be further expressed, m is preferably from 10 to 100, more preferably from 15 to 75, and still more preferably from 20 to 50.

The base polymer (typically, at least one selected from the following urethane prepolymers and polyols) preferably includes a polyoxyalkylene structure represented by general formula (2) . By making the base polymer contain the polyoxyalkylene structure represented by the general formula (2), it is possible to further express light peelability. Furthermore, it can be confirmed by any appropriate method that the base polymer contains the polyoxyalkylene structure represented by the general formula (2). As such a method, NMR measurement, IR measurement, etc. are mentioned, for example. [chemical 4]

In the general formula (2), R ² represents one species selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms. Furthermore, a plurality of R ² may be the same as or different from each other.

In the general formula ( ² ), when R2 is an alkyl group having 1 to 4 carbon atoms, the alkyl group may, for example, be linear alkyl such as methyl, ethyl, or n-propyl; isopropyl branched chain alkyl such as isobutyl and isobutyl.

R ² in the general formula (2) preferably includes one selected from the group consisting of a hydrogen atom and a methyl group, more preferably a hydrogen atom.

In general formula (2), p is the repeating number of a structural unit, and represents the integer of 1-300. Considering that the effect of the present invention can be further exhibited, p is preferably an integer of 10-250, more preferably an integer of 20-200, and still more preferably an integer of 30-150.

《1-1-1. Urethane Prepolymer》 The base polymer comprises a urethane prepolymer.

The urethane prepolymer may be only 1 type, or may be 2 or more types.

It is preferable that the number average molecular weight Mn of a urethane prepolymer is 1,000-100,000 from the point which can express the effect of this invention further.

The base polymer may also contain a polyhydric alcohol as described later. However, the polyols of the present invention are not urethane prepolymers. That is, the urethane-based adhesive composition may contain polyols that are not urethane prepolymers. As mentioned above, the reason why the polyol in this specification is not defined as a urethane prepolymer is as follows. That is, the reason is that the urethane prepolymers in this specification are generally called "urethane prepolymers" in the manufacturing process of urethane resins (prepolymer method). The urethane prepolymer used) is different from the "polyol" (polyol used in the one-step process), but since the urethane prepolymer also has multiple hydroxyl groups, it is used in In this specification, a urethane prepolymer is clearly distinguished from a polyol.

Considering that the effect of the present invention can be further expressed, the content ratio of the urethane prepolymer and the polyol in the base polymer is in weight ratio, preferably the urethane prepolymer: polyol = 50:50～100:0, more preferably urethane prepolymer:polyol=55:45～100:0, more preferably urethane prepolymer:polyol=60:40 ~100:0, especially urethane prepolymer: polyol = 70:30 ~ 100:0, the best is urethane prepolymer: polyol = 80:20 ~ 100:0 .

The content ratio of the urethane prepolymer in the urethane-based adhesive composition is preferably 80% by weight to 99.99% by weight, more preferably when the base polymer does not contain a polyol It is 85% by weight to 99.99% by weight, more preferably 90% by weight to 99.99% by weight, particularly preferably 95% by weight to 99.99% by weight. When the base polymer does not contain a polyol, by adjusting the content ratio of the urethane prepolymer in the urethane adhesive composition to the above range, the surface protection film of the present invention The effects of the present invention can be further exhibited.

The content ratio of the urethane prepolymer in the urethane-based adhesive composition is preferably 40% by weight to 99.98% by weight, more preferably 42% by weight to 99.98% by weight, more preferably 44% by weight to 99.98% by weight, particularly preferably 46% by weight to 99.98% by weight. When the base polymer contains a polyol, by adjusting the content ratio of the urethane prepolymer in the urethane adhesive composition to the above range, the surface protection film of the present invention can be Further exhibit the effect of the present invention.

The urethane prepolymer preferably includes a polyoxyalkylene structure represented by the above general formula (1). By making the urethane prepolymer contain the polyoxyalkylene structure represented by the said general formula (1), light release property can be expressed.

The urethane prepolymer preferably includes a polyoxyalkylene structure represented by the above general formula (2). By making the urethane prepolymer contain the polyoxyalkylene structure represented by the said general formula (2), light release property can be expressed further.

As a specific preferred embodiment of the urethane prepolymer, for example: <Embodiment a> A urethane prepolymer (U1 ); <Embodiment b> A urethane prepolymer including both the polyoxyalkylene structure represented by the above general formula (1) and the polyoxyalkylene structure represented by the above general formula (2) ( U2); <Embodiment c> Urethane prepolymer (U3 ).

The content ratio of the polyoxyalkylene structure represented by the above-mentioned general formula (1) to the polyoxyalkylene structure represented by the above-mentioned general formula (2) in the urethane prepolymer (U2) does not impair the present invention. Any appropriate content ratio can be adopted within the range of the effect. As such a content ratio, the polyoxyalkylene structure represented by the above general formula (1) is relative to the polyoxyalkylene structure represented by the above general formula (1) and the polyoxyalkylene structure represented by the above general formula (2). The content ratio of the total amount of oxyalkylene structures is preferably 50% by weight to 99.9% by weight, more preferably 60% by weight to 99% by weight, further preferably 65% by weight to 98% by weight, and most preferably 70% by weight to 95% by weight. By comparing the polyoxyalkylene structure represented by the above general formula (1) with respect to the polyoxyalkylene structure represented by the above general formula (1) and the polyoxyalkylene group represented by the above general formula (2) When the content ratio of the total amount of the structure is adjusted within the above-mentioned range, the surface protection film of the present invention can further express the effect of the present invention.

Typically, the urethane prepolymer is a polyurethane polyol, preferably at least one selected from polyether polyol and polyester polyol in the presence of a catalyst or It is obtained by reacting with polyfunctional isocyanate compound (A) without catalyst.

Only 1 type may be sufficient as a polyether polyol, and 2 or more types may be sufficient as it.

Only 1 type may be sufficient as polyester polyol, and 2 or more types may be sufficient as it.

As the urethane prepolymer, a commercially available urethane prepolymer can also be used.

(oxirane)化合物聚合而獲得之聚醚多元醇。作為此種聚醚多元醇，例如可例舉：聚丙二醇(亦稱為聚氧丙二醇)、聚乙二醇(亦稱為聚氧乙二醇)、聚1,4-丁二醇(亦稱為聚氧四亞甲基二醇)、聚氧伸丙基三醇等官能基數為2以上之聚醚多元醇、其等之改性物。Any appropriate polyether polyol can be used as the polyether polyol within the range that does not impair the effect of the present invention. As such polyether polyols, for example, ethylene oxide, propylene oxide, etc. , butylene oxide, tetrahydrofuran and other oxygen

Polyether polyol obtained by polymerizing (oxirane) compound. As such polyether polyols, for example, polypropylene glycol (also known as polyoxypropylene glycol), polyethylene glycol (also known as polyoxyethylene glycol), poly-1,4-butylene glycol (also known as Polyoxytetramethylene glycol), polyoxypropylene triol and other polyether polyols with 2 or more functional groups, and their modified products.

As for polyether polyol, it may be partially replaced with, for example, ethylene glycol, 1,4-butanediol, neopentyl glycol, butylethylpentanediol, glycerin, trimethylolpropane, pentaerythritol, etc. Diols, or polyamines such as ethylenediamine, N-aminoethylethanolamine, isophoronediamine, and xylylenediamine are used in combination.

The number average molecular weight Mn of the polyether polyol is preferably from 500 to 5,000, more preferably from 1,000 to 4,500, and still more preferably from 1,000 to 4,000. When the number average molecular weight is less than 500, there is a possibility that the reactivity becomes high and gelation becomes easy. When the number average molecular weight exceeds 5,000, the reactivity may decrease, and furthermore, the cohesion force of the polyurethane polyol itself may decrease.

As the polyether polyol, only a bifunctional polyether polyol may be used, or a polyether polyol having a number average molecular weight of 500 to 5000 and having at least 3 or more hydroxyl groups in one molecule may be used partly or entirely. When some or all of the polyether polyols are used with an average molecular weight of 500-5000 and having at least 3 or more hydroxyl groups in one molecule, the balance between adhesive force and re-peelability can be improved. In such a polyether polyol, when the number average molecular weight is less than 500, reactivity may become high and gelation may become easy. Moreover, in such a polyether polyol, when the number average molecular weight exceeds 5000, reactivity may become low, and the cohesive force of the urethane prepolymer itself may become small.

Any appropriate polyester polyol can be used as the polyester polyol within the range that does not impair the effect of the present invention. As such a polyester polyol, the polyester polyol obtained by making an acid component and a diol component react, for example is mentioned. As the acid component, for example, terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid, and trimellitic acid may, for example, be mentioned. As the diol component, for example, ethylene glycol, propylene glycol, diethylene glycol, butanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3'- Dimethylol heptane, polyoxyethylene glycol, polyoxypropylene glycol, 1,4-butanediol, neopentyl glycol, butylethylpentanediol, as the polyhydric alcohol component, for example: glycerin, tris Methylolpropane, Pentaerythritol. As the polyester polyol, in addition to the above-mentioned polyols obtained by ring-opening polymerization of lactones such as polycaprolactone, poly(β-methyl-γ-valerolactone), polyvalerolactone, etc. Ester polyols, etc.

The number average molecular weight Mn of the polyester polyol is preferably 500-5000. When the number average molecular weight is less than 500, there is a possibility that the reactivity becomes high and gelation becomes easy. When the number average molecular weight exceeds 5,000, the reactivity may decrease, and furthermore, the cohesion force of the polyurethane polyol itself may decrease. Furthermore, regarding the amount of polyester polyol used, based on the aspect that can further express the effect of the present invention, in the total amount of polyether polyol and polyester polyol which are raw materials of urethane prepolymer , preferably 1 mol% to 90 mol%, more preferably 3 mol% to 70 mol%, more preferably 5 mol% to 50 mol%, especially preferably 7 mol% to 30 mol% mole %.

When the urethane prepolymer is used as the urethane prepolymer (U1), the polyol (selected from polyether polyol and polyester polyol) as the raw material of the urethane prepolymer At least one of the alcohols) is preferably a polyether polyol (PO1) containing a polyoxyalkylene structure represented by the above-mentioned general formula (1), and does not contain a polyoxyethylene polyol (PO1) represented by the above-mentioned general formula (2). Polyether polyol (PO2) with oxyalkylene structure. In this case, based on the aspect that can further express the effect of the present invention, polyether polyol (PO1) is used as a polyol (selected from polyether polyol and polyester polyol) as a raw material of urethane prepolymer. The content ratio of at least one type of alcohol) in the total amount is preferably 50% by weight to 100% by weight, more preferably 70% by weight to 100% by weight, still more preferably 90% by weight to 100% by weight, most preferably 95% by weight to 100% by weight.

When the urethane prepolymer adopts the urethane prepolymer (U2), the polyol (selected from polyether polyol and polyester polyol) as the raw material of the urethane prepolymer At least one of the alcohols) is preferably a polyether polyol (PO1) containing a polyoxyalkylene structure represented by the above general formula (1) and a polyoxyalkylene compound represented by the above general formula (2) The polyether polyol (PO2) of the base structure. In this case, based on the aspect that can further express the effect of the present invention, the use ratio of polyether polyol (PO1) and polyether polyol (PO2) is expressed as polyether polyol (PO1) relative to polyether polyol ( The usage amount of the total amount of PO1) and polyether polyol (PO2) is preferably 50% by weight to 99% by weight, more preferably 60% by weight to 95% by weight, further preferably 70% by weight to 90% by weight %, preferably 75% to 85% by weight.

When the urethane prepolymer adopts the urethane prepolymer (U3), the polyol (selected from polyether polyol and polyester polyol) as the raw material of the urethane prepolymer At least one of the alcohols) is preferably a polyether polyol (PO2) containing a polyoxyalkylene structure represented by the above-mentioned general formula (2), and does not contain a polyoxyethylene polyol (PO2) represented by the above-mentioned general formula (1). Polyether polyol (PO1) with oxyalkylene structure. In this case, based on the aspect that can further express the effect of the present invention, polyether polyol (PO2) is used in the polyol (selected from polyether polyol and polyester polyol) as the raw material of urethane prepolymer. The content ratio of at least one type of alcohol) in the total amount is preferably 50% by weight to 100% by weight, more preferably 60% by weight to 100% by weight, still more preferably 70% by weight to 100% by weight, most preferably 80% by weight to 100% by weight.

As polyether polyol (PO1), poly 1, 4- butanediol (it is also called polyoxytetramethylene glycol) and its modified|denatured thing are mentioned, for example.

Considering that the effect of the present invention can be further expressed, the number average molecular weight Mn of the polyether polyol (PO1) is preferably 1000-5000, more preferably 1500-4500, further preferably 2000-4000, especially 2200 ~3800, preferably 2500~3500.

Examples of the polyether polyol (PO2) include polypropylene glycol (also called polyoxypropylene glycol), polyethylene glycol (also called polyoxyethylene glycol), polyoxypropylene triol, and the like. of modified products.

Based on the aspect that can further express the effect of the present invention, the number average molecular weight Mn of polyether polyol (PO2) is preferably 500-4500, more preferably 600-4000, further preferably 700-3500, especially preferably 800 ~3000, preferably 900~2500.

In the case of using polyether polyol (PO2) as the raw material of the urethane prepolymer (U3), it is preferable to use polyether polyol (PO2) with a number average molecular weight Mn of 1500 or more in consideration of the further performance of the effect of the present invention. Polyether polyol (PO2) and polyether polyol (PO2) whose number average molecular weight Mn is less than 1500. In this case, the content ratio of the polyether polyol (PO2) with a number average molecular weight Mn of 1500 or more in the total amount of polyether polyol (PO2) used as a raw material for the urethane prepolymer (U3) It is preferably 10% by weight to 90% by weight, more preferably 20% by weight to 80% by weight, further preferably 30% by weight to 70% by weight, most preferably 40% by weight to 60% by weight.

Any appropriate polyfunctional isocyanate compound can be used as the polyfunctional isocyanate compound (A) within the range that does not impair the effects of the present invention. As such a polyfunctional isocyanate compound (A), aromatic polyisocyanate, aliphatic polyisocyanate, araliphatic polyisocyanate, and alicyclic polyisocyanate are mentioned, for example.

As the aromatic polyisocyanate, for example, 1,3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-benzene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2 ,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-toluene diisocyanate, 2,4,6-toluene triisocyanate, 1,3, 5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4',4''-triphenylmethane triisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate base diisocyanate.

As the aliphatic polyisocyanate, for example, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylidene diisocyanate, 2, 3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate.

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

Examples of alicyclic polyisocyanates include: 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, 1,3-cyclopentene diisocyanate, 1,3 -Cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylene Bis(cyclohexyl isocyanate), 1,4-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, isophorone diisocyanate, hydrogenated Diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated toluene diisocyanate, hydrogenated tetramethyl xylylene diisocyanate.

Examples of the polyfunctional isocyanate compound (A) include: trimethylolpropane adducts of the various polyfunctional isocyanate compounds mentioned above, biurets formed by reacting with water, and polyfunctional isocyanurate ring-containing The terpolymer. Also, they may be used in combination.

Any appropriate catalyst can be used as the catalyst that can be used in the production of the urethane prepolymer within the range that does not impair the effect of the present invention. Such a catalyst may, for example, be a tertiary amine compound or an organometallic compound. A catalyst may be only 1 type, and may be 2 or more types.

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

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

Examples of tin-based compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin maleate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dibutyltin sulfide, Tributyltin Sulfide, Tributyltin Oxide, Tributyltin Acetate, Triethyltin Ethoxide, Tributyltin Ethoxide, Dioctyltin Oxide, Tributyltin Chloride, Tributyltin Trichloroacetate, Tin 2-Ethylhexanoate.

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

As the catalyst, tin-based compounds are preferably used from the viewpoint of further expressing the effects of the present invention, while non-tin-based compounds are preferably used from the viewpoint of environmental measures.

When a catalyst is used in the manufacture of urethane prepolymer, the amount of catalyst used is relative to the polyol (selected from polyether polyol and polyester polyol) as the raw material of urethane prepolymer The total amount of at least one type of alcohol) and the polyfunctional isocyanate compound (A) is preferably 0.01% by weight to 1.0% by weight.

When a catalyst is used for the production of a urethane prepolymer, the reaction temperature is preferably less than 100°C, more preferably 85°C to 95°C. If it is 100° C. or higher, it may be difficult to control the reaction rate and the crosslinked structure, and it may be difficult to obtain a urethane prepolymer having a specific molecular weight.

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

As a method for producing a urethane prepolymer, for example, the following method can be mentioned: 1) polyol (at least one selected from polyether polyol and polyester polyol), catalyst, A method of adding all polyfunctional isocyanate compounds (A) to the reactor; 2) Adding polyol (at least one selected from polyether polyol and polyester polyol) and catalyst as raw materials to the reactor Afterwards, the method of adding the polyfunctional isocyanate compound (A) dropwise. In view of controlling the reaction, the method for producing the urethane prepolymer is preferably the method of 2).

When producing a urethane prepolymer, any appropriate solvent can be used within the range which does not impair the effect of this invention. Such a solvent may, for example, be methyl ethyl ketone, ethyl acetate, toluene, xylene or acetone. Among these solvents, ethyl acetate and toluene are preferred.

《1-1-2. Polyols》 The base polymer may also contain polyols. However, as mentioned above, the polyols in the present invention are not urethane prepolymers.

When the base polymer contains a polyol, the content ratio of the polyol in the urethane-based adhesive composition is preferably 0.02% by weight to 80% by weight, more preferably 0.02% by weight to 70% by weight, More preferably, it is 0.02 weight% - 60 weight%, Especially preferably, it is 0.02 weight% - 55 weight%. When the base polymer contains a polyol, by adjusting the content ratio of the polyol in the urethane-based adhesive composition to the above-mentioned range, the surface protection film of the present invention can further express the characteristics of the present invention. Effect.

As polyols, polyester polyols, polyether polyols, polycaprolactone polyols, polycarbonate polyols, and castor oil-based polyols may be mentioned, for example. As the polyol, polyester polyol and polyether polyol are more preferable.

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

Examples of polyhydric alcohol components include ethylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, and 3-methyl-1,5-pentane Diol, 2-butyl-2-ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol , 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,8-decanediol, octadecanediol, glycerin, trimethylol Propane, pentaerythritol, hexanetriol, polypropylene glycol.

As the acid component, for example, succinic acid, methylsuccinic acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid, 1,14-tetradecane Diacid, dimer acid, 2-methyl-1,4-cyclohexanedicarboxylic acid, 2-ethyl-1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, ortho Anhydrides of phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalene dicarboxylic acid, 4,4'-biphenyl dicarboxylic acid, etc.

As polyether polyols, for example, the following polyether polyols can be exemplified, which are obtained by mixing water, low molecular polyols (propylene glycol, ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, etc.), bisphenols ( Bisphenol A, etc.), dihydroxybenzene (catechol, resorcinol, hydroquinone, etc.) Obtained by addition polymerization. Specifically, polyethylene glycol, polypropylene glycol, poly-1,4-butylene glycol, etc. are mentioned, for example.

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

As the polycarbonate polyol, for example, the following polycarbonate polyol, etc. may be exemplified: a polycarbonate polyol obtained by polycondensing the above-mentioned polyol component with phosgene; Carbonic diesters such as diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, ethylbutyl carbonate, ethylene carbonate, propylene carbonate, diphenyl carbonate, dibenzyl carbonate, etc. Polycarbonate polyols obtained by transesterification condensation; copolycarbonate polyols obtained by using two or more of the above polyol components; obtained by esterifying the above polycarbonate polyols with carboxyl-containing compounds polycarbonate polyols; polycarbonate polyols obtained by etherification of the above-mentioned polycarbonate polyols with hydroxyl-containing compounds; transesterification of the above-mentioned polycarbonate polyols with ester compounds Polycarbonate polyols; polycarbonate polyols obtained by transesterification of the above-mentioned polycarbonate polyols with hydroxyl-containing compounds; polycondensation reactions of the above-mentioned polycarbonate polyols with dicarboxylic acid compounds Polyester-based polycarbonate polyol; Copolyether-based polycarbonate polyol obtained by copolymerizing the above-mentioned various polycarbonate polyols with alkylene oxide.

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

As the polyol, polyether polyol (PO1) including a polyoxyalkylene structure represented by the above general formula (1) can also be used.

As polyether polyol (PO1), similarly to the above, poly 1, 4- butanediol (it is also called polyoxytetramethylene glycol) and its modified|denatured thing are mentioned, for example.

The polyol preferably includes a first polyol having a number average molecular weight Mn of 5,000 to 20,000 and a second polyol having a number average molecular weight Mn of 300 to 4,999 in view of further expressing the effects of the present invention.

The 1st polyol A1 may be only 1 type, and may be 2 or more types.

The 2nd polyhydric alcohol A2 may be only 1 type, and may be 2 or more types.

Considering that the effect of the present invention can be further expressed, the content ratio of the total amount of the first polyol and the second polyol in the polyol is preferably 80% by weight to 100% by weight, more preferably 90% by weight to 100% by weight. % by weight, more preferably 95% by weight to 100% by weight, particularly preferably 98% by weight to 100% by weight, most preferably substantially 100% by weight.

The number average molecular weight Mn of the first polyol is 5000-20000, preferably 6000-18000, more preferably 7000-16000, still more preferably 8000-15000, especially preferably 9000-14000. If the number average molecular weight Mn of the first polyhydric alcohol is within the above range, the effects of the present invention can be further exhibited.

The number average molecular weight Mn of the second polyol is 300-4999, preferably 500-4500, more preferably 1000-4000, still more preferably 1500-3800, especially preferably 2000-3500. If the number average molecular weight Mn of the second polyol is within the above range, the effect of the present invention can be further exhibited.

The weight ratio of the first polyol to the second polyol is preferably 0.7≦(the first polyol/the second polyol)≦3.5, more preferably 1.0≦(the first polyol/the second polyol)≦3.0, Furthermore, it is more preferably 1.1≦(first polyol/second polyol)≦2.5, and more preferably 1.2≦(first polyol/second polyol)≦2.0. If the weight ratio of the first polyol to the second polyol is within the above range, the surface protection film according to the embodiment of the present invention can achieve excellent low haze, for example, can exhibit excellent inspection properties.

Considering that the effect of the present invention can be further expressed, the number of OH groups in the first polyol is preferably 3 to 6, more preferably 3 to 5, and even more preferably 3 to 4 1, preferably 3.

Considering that the effect of the present invention can be further expressed, in the first polyol, the triol having 3 OH groups is preferably contained in 50% by weight to 100% by weight, more preferably in 70% by weight to 100% by weight %, more preferably 90% by weight to 100% by weight, particularly preferably 95% by weight to 100% by weight, most preferably substantially 100% by weight.

Considering that the effect of the present invention can be further expressed, the number of OH groups in the second polyol is preferably 3-6, more preferably 3-5, and more preferably 3-4. 1, preferably 3.

Considering that the effect of the present invention can be further expressed, in the second polyol, the triol having 3 OH groups is preferably contained in 50% by weight to 100% by weight, more preferably in 70% by weight to 100% by weight %, more preferably from 90% by weight to 100% by weight, especially preferably from 95% by weight to 100% by weight, most preferably substantially 100% by weight.

《1-1-3. Polyfunctional isocyanate compound (B)》 The urethane-based adhesive composition preferably contains a polyfunctional isocyanate compound (B). By making the urethane adhesive composition contain the polyfunctional isocyanate compound (B), the urethane prepolymer contained in the urethane adhesive composition and the The cross-linking reaction of polyols can form urethane-based adhesives.

The polyfunctional isocyanate compound (B) may be only 1 type, and may be 2 or more types.

As the polyfunctional isocyanate compound (B), any appropriate polyfunctional isocyanate compound that can be used in a urethanization reaction can be used. As such a polyfunctional isocyanate compound (B), aromatic polyisocyanate, aliphatic polyisocyanate, araliphatic polyisocyanate, and alicyclic polyisocyanate are mentioned, for example.

As the aromatic polyisocyanate, for example, 1,3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-benzene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2 ,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-toluene diisocyanate, 2,4,6-toluene triisocyanate, 1,3, 5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4',4''-triphenylmethane triisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate base diisocyanate.

As the aliphatic polyisocyanate, for example, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylidene diisocyanate, 2, 3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecyl diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate.

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

Examples of alicyclic polyisocyanates include: 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, 1,3-cyclopentene diisocyanate, 1,3 -Cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylene Bis(cyclohexyl isocyanate), 1,4-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, isophorone diisocyanate, hydrogenated Diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated toluene diisocyanate, hydrogenated tetramethyl xylylene diisocyanate.

Examples of the polyfunctional isocyanate compound (B) include trimethylolpropane adducts of the above-mentioned various polyfunctional isocyanate compounds, biurets formed by reacting with water, and polyfunctional isocyanate ring-containing The terpolymer. Also, they can be used in combination.

Considering that the effects of the present invention can be further expressed, the content ratio of the polyfunctional isocyanate compound (B) in the urethane adhesive composition is preferably 2.0 parts by weight relative to 100 parts by weight of the base polymer ~40 parts by weight, more preferably 2.3 parts by weight~30 parts by weight, still more preferably 2.5 parts by weight~20 parts by weight, especially preferably 3.0 parts by weight~15 parts by weight.

Considering that the effects of the present invention can be further expressed, the equivalent ratio of NCO groups and OH groups in the urethane-based adhesive composition is calculated as NCO groups/OH groups, preferably 1.0 to 2.0, more preferably 1.1 ~1.9, more preferably 1.2~1.8, especially preferably 1.2~1.7.

《1-1-4. Fluorine Compounds》 The urethane-based adhesive composition contains a fluorine-based compound. By making the urethane-based adhesive composition contain a fluorine-based compound, the effects of the present invention can be further expressed.

A fluorine-type compound may be only 1 type, and may be 2 or more types.

The content ratio of the fluorine-based compound in the urethane-based adhesive composition is preferably 0.01 parts by weight or more with respect to 100 parts by weight of the base polymer, more preferably from the viewpoint that the effect of the present invention can be further expressed Preferably, it is 0.03 weight part - 30 weight part, More preferably, it is 0.05 weight part - 10 weight part, Most preferably, it is 0.05 weight part - 1 weight part.

The surface tension of fluorine compounds when made into 0.1% propylene glycol monomethyl ether solution is preferably above 23 mN/m, more preferably 23 mN/m～26 mN/m (the surface tension of propylene glycol monomethyl ether is 27.1 mN/m m). If the surface tension of the fluorine-based compound when prepared as a 0.1% propylene glycol monomethyl ether solution is within the above-mentioned range, the effect of the present invention can be further exhibited. In particular, if the surface tension of the fluorine-based compound when prepared as a 0.1% propylene glycol monomethyl ether solution is within the above-mentioned range, the occurrence of black spots can be further effectively suppressed.

As the fluorine-based compound, for example, at least one selected from the group consisting of fluorine-containing compounds, hydroxyl-containing fluorine-based compounds, and crosslinkable functional group-containing fluorine-based compounds may be mentioned.

Examples of the fluorine-containing compound include a compound having a fluoroaliphatic hydrocarbon skeleton, a fluorine-containing organic compound obtained by copolymerizing an organic compound and a fluorine-based compound, and a fluorine-containing compound containing an organic compound. Examples of the fluoroaliphatic hydrocarbon skeleton include fluoromethane, fluoroethane, fluoropropane, fluoroisopropane, fluorobutane, fluoroisobutane, fluorobutane, fluoropentane, and fluorohexane. C1～C10 alkanes. Here, the notation of "C1-C10" means 1-10 carbon atoms.

A preferred embodiment of the fluorine-containing compound is an oligomer having a fluorine-containing group, and a hydrophilic group and/or an lipophilic group (“specific fluorine-containing compound”).

Typical examples of the fluorine-containing group include fluorine-containing alkyl groups (eg, CF ₃ -, etc.) and/or fluorine-containing alkylene groups (eg, -CF ₂ -CF ₂ -, etc.).

Hydrophilic base is a base with hydrophilicity. Hydrophilic is translated as "hydrophilic" in English, meaning "has affinity with water", which is a characteristic generally known by the industry (for example, refer to the Mcgraw-Hill Dictionary of Scientific and Technical Terms (revised) 3rd edition, Nikkan Kogyo Shimbun) etc.). Lipophilic base is a base with lipophilicity. Lipophilic English is translated as "lipophilic", which means "having affinity with oil", which is a characteristic generally known by the industry (for example, refer to the Mcgraw-Hill Dictionary of Scientific and Technical Terms (revised) 3rd edition, Nikkan Kogyo Shimbun) etc.).

By using such a "specific fluorine compound" as a fluorine compound, the effect of this invention can be expressed further. In particular, the surface protection film according to the embodiment of the present invention can exhibit excellent light peelability by employing the "specific fluorine compound" as the fluorine compound.

If such a "specific fluorine compound" is used together with an ionic compound described later, the antistatic performance of the surface protection film according to the embodiment of the present invention can be further improved. The reason for this is presumed to be that the ionic compound is concentrated on the surface side of the urethane-based adhesive layer (the side to be bonded to the adherend) due to the specific fluorine-based compound.

As a fluorine-containing compound, the following are mentioned as a commercial item, for example.

MEGAFAC series manufactured by DIC: Representative examples include: "MEGAFAC F-114", "MEGAFAC F-253", "MEGAFAC F-281", "MEGAFAC F-410", "MEGAFAC F-430", "MEGAFAC F-444 ", "MEGAFAC F-477", "MEGAFAC F-510", "MEGAFAC F-551", "MEGAFAC F-553", "MEGAFAC F-554", "MEGAFAC F-556", "MEGAFAC F-557" , "MEGAFAC F-559", "MEGAFAC F-561", "MEGAFAC F-562", "MEGAFAC F-565", "MEGAFAC F-568", "MEGAFAC F-570", "MEGAFAC F-571", "MEGAFAC F-576", "MEGAFAC R-01", "MEGAFAC R-40", "MEGAFAC R-40-LM", "MEGAFAC R-41", "MEGAFAC R-41-LM", "MEGAFAC R- 94", "MEGAFAC RS-56", "MEGAFAC RS-72-K", "MEGAFAC RS-75-A", "MEGAFAC RS-75-NS", etc.

Surflon series manufactured by AGC Qingmei Chemical Co., Ltd.: Typical examples include "S-242", "S-243", and "S-386".

FC series manufactured by Sumitomo 3M: Typical examples include "FC-4430", "FC-4432" and the like.

FTERGENT series manufactured by NEOS: Typical examples include "FTERGENT100", "FTERGENT100C", "FTERGENT110", "FTERGENT150", "FTERGENT150CH", "FTERGENT250", and "FTERGENT400SW".

PF series manufactured by Kitamura Chemical Co., Ltd.: Representative examples include: "PF-136A", "PF-156A", "PF-151N", "PF-636", "PF-6320", "PF-656", "PF-6520 ", "PF-651", "PF-652", "PF-3320", etc.

As the hydroxyl group-containing fluorine-based compound, for example, previously known resins can be used, for example: International Publication No. 94/06870 Specification, Japanese Patent Laid-Open No. 8-12921, Japanese Patent Laid-Open No. 10-72569, Hydroxyl-containing fluororesins described in Japanese Patent Laid-Open No. 4-275379, International Publication No. 97/11130, International Publication No. 96/26254, etc. Other hydroxyl-containing fluororesins include, for example, Japanese Patent Laid-Open No. 8-231919, Japanese Patent Laid-Open No. 10-265731, Japanese Patent Laid-Open No. 10-204374, and Japanese Patent Laid-Open No. 8-12922. Fluoroolefin copolymers and the like described in Publication No. In addition, a copolymer of a compound having a fluorinated alkyl group among hydroxyl-containing compounds, a fluorine-containing organic compound obtained by copolymerizing a hydroxyl-containing compound and a fluorine-containing compound, and a fluorine-containing compound containing a hydroxyl-containing organic compound Wait. Commercially available products of such hydroxyl-containing fluorine compounds include, for example, the trade name "Lumiflon" (manufactured by Asahi Glass Co., Ltd.), the trade name "CEFRAL COAT" (manufactured by Central Glass Co., Ltd.), the trade name " ZAFLON" (manufactured by Toagosei Co., Ltd.), trade name "ZEFFLE" (manufactured by Daikin Industries Co., Ltd.), etc.

Examples of the crosslinkable functional group-containing fluorine-based compound include, for example, copolymers of carboxylic acid compounds having a fluorinated alkyl group such as perfluorooctanoic acid, and compounds having a fluorinated alkyl group among crosslinkable functional group-containing compounds. Compounds, fluorine-containing organic compounds copolymerized with crosslinkable functional group-containing compounds and fluorine-containing compounds, fluorine-containing compounds containing crosslinkable functional group-containing compounds, etc. Commercially available products of such crosslinkable functional group-containing fluorine compounds include, for example, trade names "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" (manufactured by DIC Co., Ltd.) Wait.

Among the commercially available fluorine-containing compounds, those belonging to the above-mentioned "oligomer having a fluorine-containing group and a hydrophilic group and/or lipophilic group" typically include: DIC (Share) Manufacturing "MEGAFAC F-251" (an oligomer containing fluorine-containing groups, hydrophilic groups, and lipophilic groups, the surface tension of 0.1% propylene glycol monomethyl ether solution = 22.7 mN/m), "MEGAFAC F-477" (an oligomer containing fluorine-containing groups, hydrophilic groups, and lipophilic groups, the surface tension of 0.1% propylene glycol monomethyl ether solution = 25.4 mN/m), "MEGAFAC F-551" (an oligomer containing fluorine-containing groups and lipophilic groups, the surface tension of 0.1% propylene glycol monomethyl ether solution = 25.9 mN/m), "MEGAFAC F-553" (an oligomer containing fluorine-containing groups, hydrophilic groups, and lipophilic groups, the surface tension of 0.1% propylene glycol monomethyl ether solution = 25.4 mN/m), "MEGAFAC F-554" (an oligomer containing fluorine-containing groups and lipophilic groups, the surface tension of 0.1% propylene glycol monomethyl ether solution = 25.0 mN/m), "MEGAFAC F-555" (an oligomer containing fluorine-containing groups, hydrophilic groups, and lipophilic groups, the surface tension of 0.1% propylene glycol monomethyl ether solution = 20.5 mN/m), "MEGAFAC F-557" (an oligomer containing fluorine-containing groups, hydrophilic groups, and lipophilic groups, the surface tension of 0.1% propylene glycol monomethyl ether solution = 25.6 mN/m), "MEGAFAC F-559" (an oligomer containing fluorine-containing groups, hydrophilic groups, and lipophilic groups, the surface tension of 0.1% propylene glycol monomethyl ether solution = 24.3 mN/m), "MEGAFAC F-563" (an oligomer containing fluorine-containing groups and lipophilic groups, the surface tension of 0.1% propylene glycol monomethyl ether solution = 21.4 mN/m), "MEGAFAC F-569" (an oligomer containing fluorine groups and hydrophilic groups, the surface tension of 0.1% propylene glycol monomethyl ether solution = 19.7 mN/m), "MEGAFAC F-571" (an oligomer containing a fluorine group and a hydrophilic group, the surface tension when prepared as a 0.1% propylene glycol monomethyl ether solution = 24.2 mN/m), etc.

《1-1-5. Ionic compounds》 The urethane-based adhesive composition may also contain an ionic compound. If the urethane-based adhesive composition contains an ionic compound, the antistatic performance of the surface protection film according to the embodiment of the present invention can be improved.

As the content ratio of the ionic compound, any appropriate content ratio can be adopted within the range that does not impair the effect of the present invention. Considering that the antistatic performance of the surface protection film of the present invention can be further improved, the content ratio of the ionic compound in the urethane-based adhesive composition is preferably 0.05 weight with respect to 100 parts by weight of the base polymer Part or more, more preferably 0.10 to 50 parts by weight, more preferably 0.20 to 30 parts by weight, particularly preferably 0.30 to 10 parts by weight, most preferably 0.40 to 1 part by weight. When the content ratio of the ionic compound in the urethane-based adhesive composition is too less than the above-mentioned range, sufficient antistatic performance may not be imparted to the surface protection film of the present invention. When the content ratio of the ionic compound in the urethane-based adhesive composition exceeds the above-mentioned range too much, the contamination to the adherend may increase.

As the ionic compound, any appropriate ionic compound can be employed within the range not impairing the effects of the present invention.

Only 1 type may be sufficient as an ionic compound, and 2 or more types may be sufficient as it.

Considering that the effect of the present invention can be further expressed, the ionic compound is preferably an ionic compound containing at least one selected from onium cations and metal cations and a fluoroorganic anion, or an ionic group-containing silicone oligomer , is more preferably an ionic compound containing at least one selected from onium cations and metal cations and a fluoroorganic anion from the viewpoint of further improving the appearance of the adhesive layer.

The ionic compound may also be an ionic liquid. The ionic liquid means a molten salt (ionic compound) that is liquid at 25°C.

As the ionic group-containing silicone oligomer, any appropriate ionic group-containing silicone oligomer can be used within the range that does not impair the effects of the present invention. As an ionic group-containing silicone oligomer, for example, the product name "X-40-2450" by Shin-Etsu Chemical Co., Ltd. is mentioned.

Any appropriate onium cation can be used as the onium cation within the range that does not impair the effect of the present invention. Based on the aspect that can further show the effects of the present invention, as such onium cations, it is preferably selected from ammonium cations (nitrogen-containing onium cations), perium cations (sulfur-containing onium cations), phosphonium-containing onium cations (phosphonium cations). ), more preferably ammonium cation.

As the metal cation, any appropriate metal cation can be used within the range that does not impair the effect of the present invention. Such metal cations are preferably alkali metal cations such as Li cations, Na cations, and K cations because they can further express the effects of the present invention.

As the fluorine organic anion, any appropriate fluorine organic anion can be used within the range that does not impair the effects of the present invention. Fluoroorganic anions can be fully fluorinated (perfluorinated) or partially fluorinated.

Such fluorine organic anions include, for example, fluorinated arylsulfonates, perfluoroalkanesulfonates, bis(fluorosulfonyl)imides, bis(perfluoroalkanesulfonyl)acyl imine, cyanoperfluoroalkanesulfonylamide, bis(cyano)perfluoroalkanesulfonylmethylate, cyano-bis-(perfluoroalkanesulfonyl)methylate, tris(perfluoroalkanesulfonyl)methide Alkanesulfonyl)methyl compounds, trifluoroacetates, perfluoroalkyl compounds, tris(perfluoroalkanesulfonyl)methyl compounds, (perfluoroalkanesulfonyl)trifluoroacetamides, and the like.

Among these fluoroorganic anions, based on the consideration that the effect of the present invention can be further exhibited, perfluoroalkanesulfonate, bis(fluorosulfonyl)imide, bis(perfluoroalkanesulfonyl) Amides, more specifically, for example, trifluoromethanesulfonate, pentafluoroethanesulfonate, heptafluoropropanesulfonate, nonafluorobutanesulfonate, bis(fluorosulfonyl)imide, Bis(trifluoromethanesulfonyl)imide, preferably bis(fluorosulfonyl)imide and bis(trifluoromethanesulfonyl)imide.

The ionic compound is more preferably an ionic compound composed of an onium cation and a fluoroorganic anion because it can further express the effects of the present invention.

As an onium cation, it is preferable to have at least 1 sort(s) chosen from the structure represented by General formula (3)-(6). [chemical 5]

In general formula (3), Ra represents a hydrocarbon group having 4 to 20 carbons and may contain heteroatoms, Rb and Rc are the same or different, represent hydrogen or a hydrocarbon group having 1 to 16 carbons and may contain heteroatoms. However, when the nitrogen atom contains a double bond, there is no Rc.

In the general formula (4), Rd represents a hydrocarbon group with 2 to 20 carbons, and may contain heteroatoms, Re, Rf, and Rg are the same or different, represent hydrogen or a hydrocarbon group with 1 to 16 carbons, and may contain heteroatoms.

In the general formula (5), Rh represents a hydrocarbon group with 2 to 20 carbons, and may contain heteroatoms, and Ri, Rj, and Rk are the same or different, represent hydrogen or a hydrocarbon group with 1 to 16 carbons, and may contain heteroatoms.

In the general formula (6), Z represents a nitrogen atom, a sulfur atom, or a phosphorus atom, and R1, Rm, Rn, and Ro are the same or different, represent a hydrocarbon group with 1 to 20 carbon atoms, and may contain heteroatoms. However, when Z is a sulfur atom, there is no Ro.

Examples of the cationic structure represented by the general formula (3) include pyridinium cationic structures, pyrrolidinium cationic structures, piperidinium cationic structures, cationic structures having a pyrroline skeleton, and cationic structures having a pyrrole skeleton.

Specific examples of the cation represented by the general formula (3) include: 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-ethyl-3-methano Basepyridinium cation, 1-butyl-3-methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1-octyl-4- Pyridinium cation, 1-butyl-3,4-dimethylpyridinium cation, 1,1-dimethylpyrrolidinium cation and other pyridinium cations; 1-ethyl-1-methylpyrrolidinium Cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-butylpyrrolidinium cation, 1-methyl-1-pentylpyrrolidinium cation, 1-methyl-1 -hexylpyrrolidinium cation, 1-methyl-1-heptylpyrrolidinium cation, 1-ethyl-1-propylpyrrolidinium cation, 1-ethyl-1-butylpyrrolidinium cation, 1 -Ethyl-1-pentylpyrrolidinium cation, 1-ethyl-1-hexylpyrrolidinium cation, 1-ethyl-1-heptylpyrrolidinium cation, 1,1-dipropylpyrrolidinium Pyrrolidinium cations such as cations, 1-propyl-1-butylpyrrolidinium cations, 1,1-dibutylpyrrolidinium cations; 1-propylpiperidinium cations, 1-pentylpiperidinium cations , 1-methyl-1-ethylpiperidinium cation, 1-methyl-1-propylpiperidinium cation, 1-methyl-1-butylpiperidinium cation, 1-methyl-1- Pentylpiperidinium cation, 1-methyl-1-hexylpiperidinium cation, 1-methyl-1-heptylpiperidinium cation, 1-ethyl-1-propylpiperidinium cation, 1- Ethyl-1-butylpiperidinium cation, 1-ethyl-1-pentylpiperidinium cation, 1-ethyl-1-hexylpiperidinium cation, 1-ethyl-1-heptylpiperidinium Onium cation, 1-propyl-1-butylpiperidinium cation, 1,1-dimethylpiperidinium cation, 1,1-dipropylpiperidinium cation, 1,1-dibutylpiperidinium Onium cations such as piperidinium cations; 2-methyl-1-pyrroline cations; 1-ethyl-2-phenylindole cations; 1,2-dimethylindole cations; 1-ethylcarbazole cations ; These cations further have at least one cation selected from vinyl (CH ₂ =CH-group) and allyl (CH ₂ =CH-CH ₂ -group).

Among them, based on the consideration that the effects of the present invention can be further expressed, preferred examples include: 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-ethyl- 3-methylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1-octyl -Pyridinium cations such as 4-methylpyridinium cation; 1-ethyl-1-methylpyrrolidinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-butyl Pyrrolidinium cation, 1-methyl-1-pentylpyrrolidinium cation, 1-methyl-1-hexylpyrrolidinium cation, 1-methyl-1-heptylpyrrolidinium cation, 1-ethyl -1-propylpyrrolidinium cation, 1-ethyl-1-butylpyrrolidinium cation, 1-ethyl-1-pentylpyrrolidinium cation, 1-ethyl-1-hexylpyrrolidinium cation , 1-ethyl-1-heptylpyrrolidinium cation and other pyrrolidinium cations; 1-methyl-1-ethylpiperidinium cation, 1-methyl-1-propylpiperidinium cation, 1- Methyl-1-butylpiperidinium cation, 1-methyl-1-pentylpiperidinium cation, 1-methyl-1-hexylpiperidinium cation, 1-methyl-1-heptylpiperidinium Onium cation, 1-ethyl-1-propylpiperidinium cation, 1-ethyl-1-butylpiperidinium cation, 1-ethyl-1-pentylpiperidinium cation, 1-ethyl- Piperidinium cations such as 1-hexylpiperidinium cation, 1-ethyl-1-heptylpiperidinium cation, 1-propyl-1-butylpiperidinium cation, etc.; A cation of at least one of (CH ₂ =CH-group) and allyl group (CH ₂ =CH-CH ₂ -yl), more preferably 1-hexylpyridinium cation, 1-ethyl-3-methyl Pyridinium cation, 1-butyl-3-methylpyridinium cation, 1-octyl-4-methylpyridinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1 -Propylpiperidinium cation, these cations further have at least one cation selected from the group consisting of vinyl (CH ₂ =CH- group) and allyl (CH ₂ =CH-CH ₂ - group).

Examples of the cation structure represented by the general formula (4) include an imidazolium cation structure, a tetrahydropyrimidinium cation structure, and a dihydropyrimidinium cation structure.

Specific examples of the cation represented by the general formula (4) include, for example, 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3-methyl Imidazolium cation, 1-butyl-3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-decyl-3-methyl 1-dodecyl-3-methylimidazolium cation, 1-dodecyl-3-methylimidazolium cation, 1-tetradecyl-3-methylimidazolium cation, 1,2-dimethyl-3-propylimidazolium cation , 1-ethyl-2,3-dimethylimidazolium cation, 1-butyl-2,3-dimethylimidazolium cation, 1-hexyl-2,3-dimethylimidazolium cation and other imidazolium Cation; 1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium cation, 1, 2,3,4-tetramethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,2,3,5-tetramethyl-1,4,5,6-tetrahydropyrimidinium cation, etc. Tetrahydropyrimidinium cation; 1,3-dimethyl-1,4-dihydropyrimidinium cation, 1,3-dimethyl-1,6-dihydropyrimidinium cation, 1,2,3-trimethyl Base-1,4-dihydropyrimidinium cation, 1,2,3-trimethyl-1,6-dihydropyrimidinium cation, 1,2,3,4-tetramethyl-1,4-dihydro Dihydropyrimidinium cations such as pyrimidinium cations, 1,2,3,4-tetramethyl-1,6-dihydropyrimidinium cations; these cations in turn have a group selected from vinyl (CH ₂ =CH-group) and A cation of at least one kind of allyl group (CH ₂ =CH-CH ₂ -group).

Among them, 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, and Onium cation, 1-butyl-3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-decyl-3-methyl Imidazolium cations, 1-dodecyl-3-methylimidazolium cations, ₁ -tetradecyl-3-methylimidazolium cations, and these cations further have ) and allyl (CH ₂ =CH-CH ₂ -yl) cations such as at least one imidazolium cation, more preferably 1-ethyl-3-methylimidazolium cation, 1-hexyl-3- The methylimidazolium cation and these cations further have at least one cation selected from the group consisting of vinyl (CH ₂ =CH- group) and allyl group (CH ₂ =CH-CH ₂ - group).

As a cation structure represented by General formula (5), a pyrazolium cation structure and a pyrazolinium cation structure are mentioned, for example.

Specific examples of the cation represented by the general formula (5) include: 1-methylpyrazolium cation, 3-methylpyrazolium cation, 1-ethyl-2-methylpyrazolinium Cation, 1-ethyl-2,3,5-trimethylpyrazolium cation, 1-propyl-2,3,5-trimethylpyrazolium cation, 1-butyl-2,3,5 -Pyrazolium cations such as trimethylpyrazolium cation; 1-ethyl-2,3,5-trimethylpyrazolinium cation, 1-propyl-2,3,5-trimethylpyrazole Pyrazolinium cations such as olinium cations, ₁ -butyl-2,3,5-trimethylpyrazolinium cations; these cations in turn have A cation of at least one of the groups (CH ₂ =CH-CH ₂ -group).

As the cation structure represented by the general formula (6), for example, a tetraalkylammonium cation structure, a trialkylconium cation structure, a tetraalkylphosphonium cation structure, or a part of the above-mentioned alkyl group substituted with an alkenyl group or Alkoxy or epoxy groups.

Specific examples of the cation represented by the general formula (6) include, for example, tetramethylammonium cation, tetraethylammonium cation, tetrabutylammonium cation, tetrapentylammonium cation, tetrahexylammonium cation, tetraheptylammonium cation, Trimethylammonium cation, triethylmethylammonium cation, tributylethylammonium cation, trimethylpropylammonium cation, trimethyldecylammonium cation, N,N-diethyl-N-methyl-N -(2-methoxyethyl)ammonium cation, glycidyltrimethylammonium cation, diallyldimethylammonium cation, N,N-dimethyl-N-ethyl-N-propylammonium Cation, N,N-Dimethyl-N-ethyl-N-butylammonium cation, N,N-Dimethyl-N-ethyl-N-pentylammonium cation, N,N-Dimethyl- N-ethyl-N-hexylammonium cation, N,N-dimethyl-N-ethyl-N-heptylammonium cation, N,N-dimethyl-N-ethyl-N-nonylammonium cation , N,N-dimethyl-N,N-dipropylammonium cation, N,N-diethyl-N-propyl-N-butylammonium cation, N,N-dimethyl-N-propane -N-pentylammonium cation, N,N-dimethyl-N-propyl-N-hexylammonium cation, N,N-dimethyl-N-propyl-N-heptylammonium cation, N, N-Dimethyl-N-butyl-N-hexylammonium cation, N,N-diethyl-N-butyl-N-heptyl ammonium cation, N,N-dimethyl-N-pentyl- N-hexylammonium cation, N,N-dimethyl-N,N-dihexylammonium cation, trimethylheptylammonium cation, N,N-diethyl-N-methyl-N-propylammonium cation , N,N-diethyl-N-methyl-N-pentyl ammonium cation, N,N-diethyl-N-methyl-N-heptyl ammonium cation, N,N-diethyl-N -Propyl-N-pentylammonium cation, triethylpropylammonium cation, triethylpentylammonium cation, triethylheptylammonium cation, N,N-dipropyl-N-methyl-N- Ethylammonium cation, N,N-dipropyl-N-methyl-N-pentylammonium cation, N,N-dipropyl-N-butyl-N-hexylammonium cation, N,N-dipropylammonium cation Base-N,N-dihexylammonium cation, N,N-dibutyl-N-methyl-N-pentylammonium cation, N,N-dibutyl-N-methyl-N-hexylammonium cation, Tetraalkylammonium cations such as trioctylmethylammonium cation, N-methyl-N-ethyl-N-propyl-N-pentylammonium cation; trialkylconium cation, trihexylconium cation, diethylmethylconium cation, dibutylethylconium cation, dimethyldecylconium cation, and other trialkylconium cations; tetramethylphosphonium cation, tetraethylphosphonium cation , tetrabutylphosphonium cation, tetrahexylphosphonium cation, tetraoctylphosphonium cation, triethylmethylphosphonium cation, tributylethylphosphonium cation, trimethyldecylphosphonium cation and other tetraalkylphosphonium cations; The cation further has at least one cation selected from vinyl group (CH ₂ =CH- group) and allyl group (CH ₂ =CH-CH ₂ - group).

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

Considering that the effect of the present invention can be further expressed, it is an ionic compound, specifically, 1-hexylpyridinium bis(fluorosulfonyl)imide, 1-ethyl-3-picoline Onium triflate, 1-ethyl-3-methylpyridinium pentafluoroethanesulfonate, 1-ethyl-3-methylpyridinium heptafluoropropanesulfonic acid, 1-ethyl-3- Pyridinium nonafluorobutanesulfonate, 1-butyl-3-methylpyridinium triflate, 1-butyl-3-methylpyridinium bis(trifluoromethanesulfonyl)acyl imine, 1-octyl-4-methylpyridinium bis(fluorosulfonyl)imide, 1-methyl-1-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-methyl-1-propylpyrrolidinium bis(fluorosulfonyl)imide, 1-methyl-1-propylpiperidinium bis(trifluoromethanesulfonyl)imide, 1- Methyl-1-propylpiperidinium bis(fluorosulfonyl)imide, 1-ethyl-3-methylimidazolium triflate, 1-ethyl-3-methylimidazolium Heptafluoropropanesulfonic acid, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide Amine, 1-hexyl-3-methylimidazolium bis(fluorosulfonyl)imide, 1-allyl-3-methyl-imidazolium triflate, 1-allyl-3 -Methyl-imidazolium heptafluoropropanesulfonic acid, 1-allyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide, 1-allyl-3-methyl-imidazole Onium bis(fluorosulfonyl)imide, methyltrioctylammonium bis(trifluoromethanesulfonyl)imide, trimethylpropylammonium bis(trifluoromethanesulfonyl)imide, Lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, more preferably, 1-butyl-3-methylpyridinium bis(trifluoromethanesulfonyl) ) imide, 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide, 1-allyl-3-methyl-imidazolium bis(trifluoromethanesulfonyl)imide Imine, methyltrioctylammonium bis(trifluoromethanesulfonyl)imide, trimethylpropylammonium bis(trifluoromethanesulfonyl)imide, bis(trifluoromethanesulfonyl)imide Lithium imide, especially 1-butyl-3-methylpyridinium bis(trifluoromethanesulfonyl)imide, 1-ethyl-3-methylimidazolium bis(fluorosulfonyl) Imide, 1-allyl-3-methyl-imidazolium bis(trifluoromethanesulfonyl)imide, methyltrioctylammonium bis(trifluoromethanesulfonyl)imide, tris Methylpropylammonium bis(trifluoromethanesulfonyl)imide.

As the ionic compound, commercially available ones may be used, or those synthesized by any appropriate method may be used. For example, ionic liquids can also be obtained by the halide method, hydroxide method, ester method, complex method, and neutralization method, etc. to synthesize.

《1-1-6. Other ingredients》 The urethane-based adhesive composition may contain any appropriate other components within the range that does not impair the effect of the present invention. Such other components include, for example, resin components other than the base polymer, crosslinking agents other than the polyfunctional isocyanate compound (B), crosslinking retarders, silicone-based additives, fatty acid esters, tackifiers, etc. additives, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, anti-aging agents, conductive agents, UV absorbers, antioxidants, light stabilizers, surface lubricants, leveling agents, preservatives , heat-resistant stabilizer, polymerization inhibitor, lubricant, catalyst, solvent. Representative other components are described below.

[Silicone-based additives] It is a preferred embodiment that the urethane-based adhesive composition includes a silicone-based additive. When a silicone-based additive is included as another component, the light peelability of the surface protection film according to the embodiment of the present invention can be further improved.

Considering that the effect of the present invention can be further expressed, the content ratio of the silicone-based additive in the urethane-based adhesive composition is preferably 0.01 parts by weight or more with respect to 100 parts by weight of the base polymer, more preferably It is 0.03 weight part - 30 weight part, More preferably, it is 0.05 weight part - 10 weight part, Most preferably, it is 0.05 weight part - 1 weight part.

As the silicone-based additive, any appropriate silicone-based additive can be used within the range that does not impair the effects of the present invention.

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

Considering that the effect of the present invention can be further expressed, the content ratio of the total amount of the silicone-based additive and the above-mentioned fluorine-based additive is preferably at least 0.01 part by weight, more preferably 0.03 part by weight, based on 100 parts by weight of the base polymer. ~30 parts by weight, more preferably 0.05 parts by weight~10 parts by weight, especially preferably 0.05 parts by weight~1 part by weight.

Silicone-based additives Any appropriate silicone-based additives can be used within the range that does not impair the effects of the present invention. Examples of such silicone-based additives include reactive silicone oil and non-reactive silicone oil.

As the reactive silicone oil, for example, a side chain type reactive silicone oil in which an organic group as a side chain is bonded to a Si atom providing a siloxane bond, and a Si atom located at both ends of the structure Two-terminal reactive silicone oil with an organic group bonded to the atom, a single-terminal reactive silicone oil with an organic group bonded to only one Si atom located at the two ends of the structure, used for siloxane A side chain two-terminal type reactive silicone oil in which an organic group as a side chain is bonded to the Si atom of the bond and an organic group is bonded to the Si atoms located at both ends of the structure.

[Antioxidants] The urethane-based adhesive composition may contain an antioxidant as another component from the viewpoint of deterioration suppression of the urethane-based adhesive layer. Antioxidant may be only 1 type, and may be 2 or more types.

The content rate of the antioxidant in a urethane type adhesive composition can adopt arbitrary appropriate content rate within the range which does not impair the effect of this invention. The content ratio of the antioxidant in the urethane-based adhesive composition is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, and even more preferably 0.05 to 5 parts by weight relative to 100 parts by weight of the base polymer. Preferably, it is 0.1 weight part - 3 weight part, and it is especially preferable that it is 0.2 weight part - 1 weight part.

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

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

As a peroxide decomposing agent, a sulfur type antioxidant and a phosphorus type antioxidant are mentioned, for example.

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

Examples of monophenolic antioxidants include: 2,6-di-tert-butyl-p-cresol, butylated hydroxymethoxybenzene, 2,6-di-tert-butyl-4-ethyl Phenol, stearyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate.

Examples of bisphenol-based antioxidants include 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl -6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 4,4'-butylenebis(3-methyl-6-th Tributylphenol), 3,9-bis[1,1-dimethyl-2-[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl base] 2,4,8,10-tetraoxaspiro[5,5]undecane.

Examples of polymeric phenolic antioxidants include 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-tris Methyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tetrakis-[methylene-3-(3',5'-di-tertiary Butyl-4'-hydroxyphenyl)propionate]methane, bis[3,3'-bis-(4'-hydroxy-3'-tert-butylphenyl)butyrate]diol, 1, 3,5-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)-symmetrical tris-2,4,6-(1H,3H,5H)trione, tocopherol.

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

As a phosphorus antioxidant, triphenyl phosphite, diphenylisodecyl phosphite, and phenyl diisodecyl phosphite are mentioned, for example.

[ultraviolet absorber] The urethane-based adhesive composition may contain an ultraviolet absorber as another component from the viewpoint of deterioration suppression of the urethane-based adhesive layer. The ultraviolet absorber may be only 1 type, and may be 2 or more types.

The content rate of the ultraviolet absorber in a urethane type adhesive composition can employ|adopt arbitrary appropriate content rate within the range which does not impair the effect of this invention. The content ratio of the ultraviolet absorber in the urethane-based adhesive composition is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the base polymer. More preferably, it is 0.1 weight part - 3 weight part, and it is especially preferable that it is 0.2 weight part - 1 weight part.

Examples of the ultraviolet absorber include: benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, salicylic acid-based ultraviolet absorbers, oxalylaniline-based ultraviolet absorbers, cyanoacrylate-based ultraviolet rays Absorbent, three 𠯤 series ultraviolet absorber.

Examples of benzophenone-based ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxydiphenone, Benzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-dimethoxybenzophenone, 2,2'-dihydroxy-4,4 '-Dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, bis(2-methoxy-4-hydroxy-5-benzoylphenyl ) methane.

Examples of benzotriazole-based ultraviolet absorbers include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-butyl phenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3'-third Butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)5-chlorobenzotriazole , 2-(2'-hydroxy-3',5'-di-tert-pentylphenyl)benzotriazole, 2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole , 2-[2'-Hydroxy-3'-(3'',4'',5'',6'',-tetrahydrophthalimidomethyl)-5'-methylphenyl ]benzotriazole, 2,2'methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], [2(2'-Hydroxy-5'-methacryloxyphenyl)-2H-benzotriazole.

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

Examples of cyanoacrylate UV absorbers include 2-ethylhexyl 2-cyano-3,3'-diphenylacrylate, 2-cyano-3,3'-diphenylacrylate ethyl ester.

[Light stabilizer] The urethane-based adhesive composition may contain a light stabilizer as another component from the viewpoint of deterioration suppression of the urethane-based adhesive layer. The light stabilizer may be only 1 type, and may be 2 or more types.

The content rate of the light stabilizer in a urethane type adhesive composition can employ|adopt arbitrary appropriate content rate within the range which does not impair the effect of this invention. The content ratio of the light stabilizer in the urethane-based adhesive composition is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the base polymer. More preferably, it is 0.1 weight part - 3 weight part, and it is especially preferable that it is 0.2 weight part - 1 weight part.

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

As the hindered amine light stabilizer, for example, [bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate], bis(1,2,2,6, 6-pentamethyl-4-piperidinyl) sebacate, methyl 1,2,2,6,6-pentamethyl-4-piperidinyl sebacate.

As the ultraviolet stabilizer, for example, bis(octylphenyl)sulfide nickel, [2,2'-thiobis(4-tertiary octylphenol)]-n-butylamine nickel, nickel aluminum Compound-3,5-di-tert-butyl-4-hydroxybenzyl-phosphate monoethanolate, nickel dibutyldithiocarbamate, benzoate-type inhibitors, dibutyldithiocarbamate Nickel urethane.

[Fatty acid ester] In consideration of improving the wettability of the urethane-based adhesive layer, etc., the urethane-based adhesive composition may also contain fatty acid esters as other components. Only 1 type may be sufficient as fatty acid ester, and 2 or more types may be sufficient as it.

The content ratio of the fatty acid ester in the urethane-based adhesive composition can be any appropriate content ratio within the range that does not impair the effect of the present invention. The content ratio of the fatty acid ester in the urethane-based adhesive composition is preferably 0.01 to 50 parts by weight, more preferably 0.05 to 45 parts by weight, with respect to 100 parts by weight of the base polymer, and further Preferably it is 0.1 weight part - 40 weight part, especially preferably it is 0.5 weight part - 25 weight part.

The number average molecular weight Mn of the fatty acid ester is preferably 200-400, more preferably 210-395, further preferably 230-380, especially preferably 240-360, most preferably 250-350. By adjusting the number average molecular weight Mn of the fatty acid ester within the above range, the wetting speed can be further improved. If the number average molecular weight Mn of the fatty acid ester is too small, there is a possibility that the wetting speed may not be improved even if the number of parts added is large. If the number average molecular weight Mn of the fatty acid ester is too large, the curability of the adhesive during drying may deteriorate, which may adversely affect not only the wettability but also other adhesive properties.

Any appropriate fatty acid ester can be used as the fatty acid ester within the range not impairing the effect of the present invention. Examples of such fatty acid esters include: polyoxyethylene bisphenol A laurate, butyl stearate, 2-ethylhexyl palmitate, 2-ethylhexyl stearate, behenic acid Monoglycerides, Cetyl 2-Ethylhexanoate, Isopropyl Myristate, Isopropyl Palmitate, Cholesterol Isostearate, Lauryl Methacrylate, Methyl Coco Fatty Acid, Methyl Laurate, Methyl Oleate, Methyl Stearate, Myristyl Myristate, Octyldodecyl Myristate, Pentaerythritol Monooleate, Pentaerythritol Monostearate, Pentaerythritol Tetrapalmitate, Stearic Acid Stearyl, Isotridecyl Stearate, Glyceryl Tris-2-Ethylhexanoate, Butyl Laurate, Octyl Oleate.

[catalyst] As the catalyst that can be contained in the urethane-based adhesive composition, any appropriate catalyst can be used within the range that does not impair the effect of the present invention. As such a catalyst, a tertiary amine compound and an organometallic compound are mentioned, for example. A catalyst may be only 1 type, and may be 2 or more types.

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

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

Examples of tin-based compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin maleate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dibutyltin sulfide, Tributyltin Sulfide, Tributyltin Oxide, Tributyltin Acetate, Triethyltin Ethoxide, Tributyltin Ethoxide, Dioctyltin Oxide, Tributyltin Chloride, Tributyltin Trichloroacetate, Tin 2-Ethylhexanoate.

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

Considering that the effect of the present invention can be further exhibited, the catalyst that can be included in the urethane adhesive composition is preferably a non-tin compound, more preferably iron 2-ethylhexanoate, Iron-based compounds such as iron acetylpyruvate.

The usage-amount of the catalyst which may be contained in a urethane-type adhesive composition is preferably 0.001 weight% - 1.0 weight% with respect to the base polymer whole quantity.

[solvent] Any appropriate solvent can be used as the solvent that may be contained in the urethane-based adhesive composition within the range that does not impair the effects of the present invention. As such a solvent, methyl ethyl ketone, ethyl acetate, toluene, xylene, acetone are mentioned, for example. Among these solvents, ethyl acetate and toluene are preferred.

""1-2. Substrate layer"" As the thickness of the base material layer, any appropriate thickness can be adopted depending on the application. The thickness of the substrate layer is preferably from 5 μm to 300 μm, more preferably from 10 μm to 250 μm, further preferably from 15 μm to 200 μm, especially preferably from 20 μm to 150 μm.

The substrate layer may be a single layer or a laminate of two or more layers. The substrate layer may also be extended.

As the material of the base layer, any appropriate material can be used depending on the application. For example, plastic, paper, metal film, nonwoven fabric, etc. are mentioned. Preferably it is plastic. The base material layer may be composed of one kind of material, or may be composed of two or more kinds of materials. For example, it may be composed of two or more types of plastics.

Examples of the aforementioned plastics include polyester-based resins, polyamide-based resins, and polyolefin-based resins. It is preferably a polyester-based resin, and examples thereof include polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate.

The base material layer may contain arbitrary appropriate additives as needed. Examples of additives that may be contained in the substrate layer include antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, fillers, and pigments. The type, number, and amount of additives that may be contained in the substrate layer can be appropriately set depending on the purpose. Especially when the material of the substrate layer is plastic, it is preferable to contain some of the above-mentioned additives for the purpose of anti-deterioration and the like. From the standpoint of improving weather resistance, etc., particularly preferable examples of additives include antioxidants, ultraviolet absorbers, photostabilizers, and fillers.

《《2. Manufacturing method of surface protection film》》 The surface protection film of embodiment of this invention can be manufactured by any appropriate method. As such a manufacturing method, for example, it can be carried out according to any appropriate manufacturing method as follows: (1) A method of applying a solution or a hot-melt solution of an adhesive layer forming material on a substrate layer, (2) A method of transferring and adhering the adhesive layer thus coated and formed on the release liner to the substrate layer, (3) A method of extruding a material for forming an adhesive layer onto a substrate layer to form a coating, (4) The method of extruding the substrate layer and the adhesive layer in two or more layers, (5) A method of laminating an adhesive layer on a substrate layer as a single layer or a method of laminating an adhesive layer and a laminated layer together in two layers, (6) A method of laminating two or more layers of an adhesive layer and a substrate layer forming material such as a film or a laminate layer.

Examples of coating methods include roll coating, gravure roll coating, reverse roll coating, touch roll coating, dip roll coating, rod coating, and brush roll coating. , Spray coating method, blade coating method, air knife coating method, chipping wheel coating method, direct coating method, die coating, roller brush coating method.

""3. Use of Surface Protection Film"" The surface protective film according to the embodiment of the present invention can be used for any appropriate purpose. It is preferable that the surface protection film of the present invention has very little contamination to the adherend, and it is preferably excellent in wettability or secondary processability, so it can be preferably used for surface protection of optical components or electronic components, for example. As an optical member, LCD (liquid crystal display, liquid crystal display device), the touch panel using LCD etc., the color filter used for LCD, a polarizing plate, etc. are mentioned, for example.

A member to which the surface protection film according to the embodiment of the present invention is bonded, such as an optical member or an electronic member, can be bonded and peeled off the bonded surface protection film multiple times manually.

That is, the optical member of embodiment of this invention is what bonded the surface protection film of this invention. Moreover, the electronic component of embodiment of this invention is what bonded the surface protection film of this invention. [Example]

Hereinafter, the present invention will be specifically described with examples, but the present invention is not limited by these examples. In addition, the test and evaluation method in an Example etc. are as follows. In addition, "parts" means "parts by weight" unless otherwise specified, and "%" means "% by weight" unless otherwise specified.

＜Adhesion to glass＞ The surface protection film (width 25 mm x length 140 mm) from which the release liner had been peeled was bonded to glass (soda lime glass, manufactured by Songnami Glass Co., Ltd.) by reciprocating once with a 2 kg hand pressure roller. Thereafter, it was left for 30 minutes at an ambient temperature of 23°C. The obtained sample for evaluation was measured using a tensile tester. As a tensile testing machine, a product name "Automatic Stereograph AG-Xplus HS 6000 mm/min High Speed Model (AG-50NX plus)" manufactured by Shimadzu Corporation was used. After setting the sample for evaluation in the tensile testing machine, the tensile test was started. The conditions of the tensile test were peeling angle = 180 degrees, peeling speed (tensile speed) = 300 mm/min. The load when peeling off the surface protection film from glass was measured, and the average load at this time was made into the adhesive force (peeling force) of the surface protection film with respect to glass.

<Peel-off static voltage for glass> Cut the surface protective film peeled off the release liner into a size of 70 mm in width and 100 mm in length, and press it on the surface of glass (soda lime glass, manufactured by Songnang Glass Industry Co., Ltd.) with a hand pressure roller to protect the surface. One end of the film protrudes 30 mm from the end of the adherend. After leaving the sample in an environment of 23° C.×50% RH for 1 day, it was set at a specific position on a sample fixing table with a height of 20 mm. The end of the surface protection film protruding 30 mm from the adherend was fixed to an automatic winder (not shown), and peeled at a peeling angle of 150° and a peeling speed of 30 m/min. Using a potentiometer (manufactured by SHISHIDO ELECTROSTATIC Co., Ltd., model "STATIRON DZ-4") fixed at a position 30 mm from the center of the adherend, the potential of the surface of the adherend generated at this time was measured. As "peeling static voltage". The measurement is carried out under the environment of 23°C and 50%RH.

＜Haze＞ Put the urethane-based adhesive composition on the release-treated surface of a polyester film with a thickness of 75 μm (trade name: DIAFOIL MRF75, manufactured by Mitsubishi Chemical Co., Ltd.) that has undergone silicone release treatment on one side. Under the conditions of the comparative example, coating and drying were performed to prepare a urethane-based adhesive layer. Next, a polyester film with a thickness of 75 μm (trade name: DIAFOIL MRE75, manufactured by Mitsubishi Chemical Co., Ltd.) that has been treated with silicone release on one side is used as a urethane-based adhesive on the release-treated side of the polyester film. The layer side is coated on the surface of the urethane-based adhesive layer, and aged at room temperature for 5 days. Prepare two pieces of 50 mm x 50 mm thick paper with a hole of 20 mm x 20 mm in the center, use a hand roller to go back and forth once on one of the pieces to stick the sample alone, and then stick the other piece. The haze of the evaluation sample obtained in the above manner was measured using "HM-150N" manufactured by Murakami Color Technology Laboratory Co., Ltd.

＜Smudge Evaluation＞ The blade of the cutter was inserted at 30 degrees to the center of the adhesive side of the surface protection film (width 25 mm x length 140 mm) from which the release liner had been peeled off, and 1 cm was cut. The case where the smear was confirmed visually was made into x, and the case where the smear was not confirmed was made into (circle).

＜Black dot evaluation＞ The amount of generation of black spots (glue marks) per 10 cm square of the surface protective film from which the release liner was peeled was confirmed visually.

<The ratio of hydroxyl groups contained in the urethane-based adhesive composition> Based on the total of 100 g of the hydroxyl value (OHV) of the base polymer contained in the urethane-based adhesive composition and the molecular weight (56.1) of KOH, it was calculated by the following formula. OHV[mgKOH/g]/56.1[mg/mmol]=OH[mmol/g]

[Manufacturing example 1]: Manufacture of a solution of urethane prepolymer A Put poly-1,4- Butanediol (product name "PTMG3000", manufactured by Mitsubishi Chemical Co.) 333 g, polypropylene glycol (product name "SANNIX GP-1500", manufactured by Sanyo Chemical Co., Ltd.) 83 g, ethyl acetate as a solvent (manufactured by Tosoh Co.) 110 g g, while stirring, 0.041 g of dibutyltin(IV) dilaurate (manufactured by Wako Pure Chemical Industries, Ltd.) was added as a catalyst, and nitrogen replacement was performed at room temperature for 1 hour. Thereafter, under nitrogen flow, 13.0 g of hexamethylene diisocyanate (product name "HDI", manufactured by Tosoh Co.) was added while stirring, and the temperature of the solution in the experimental device was controlled by a water bath to reach 90±2°C, and kept for 4 hours , to obtain a solution of urethane prepolymer A. Furthermore, in the middle of the polymerization, add ethyl acetate dropwise appropriately to control the temperature during the polymerization and prevent the decrease in agitation caused by the increase in viscosity. The total amount of ethyl acetate added dropwise was 320 g. The solid content concentration of the solution of the urethane prepolymer A was 50 weight%.

[Manufacturing Example 2]: Manufacture of a solution of urethane prepolymer B Put polypropylene glycol (product name "SANNIX PP-2000", manufactured by Sanyo Chemical Industry Co., Ltd.) 197 g, polyester polyol (product name "KURARAY POLYOL P-2010", manufactured by Kuraray Co., Ltd.) 197 g, toluene as a solvent (manufactured by Tosoh Corporation) 110 g . 0.041 g of dibutyltin (IV) dilaurate (manufactured by Wako Pure Chemical Industries, Ltd.) as a catalyst, nitrogen substitution was carried out at room temperature for 1 hour while stirring. Then, under nitrogen flow, 33.5 g of hexamethylene diisocyanate (product name "HDI", manufactured by Tosoh Co.) was added while stirring, and the temperature of the solution in the experimental device was controlled by a water bath to reach 90±2°C, and kept for 4 hours Finally, 44 g of polypropylene glycol (product name "GP1000", manufactured by Sanyo Chemical Industry Co., Ltd.) was added, and the temperature of the solution in the experimental device was controlled by a water bath to reach 90 ± 2 °C, and after keeping for 2 hours, hexamethylene diisocyanate (product Name "HDI", manufactured by Tosoh Company) 25.4 g, use a water bath to control the solution temperature in the experimental device to 90±2°C, and keep it for 2 hours to obtain a solution of urethane prepolymer B. Furthermore, in the middle of the polymerization, toluene is added dropwise appropriately to control the temperature during the polymerization and prevent the decrease in agitation caused by the increase in viscosity. The total amount of toluene added dropwise was 380 g. The solid content concentration of the solution of the urethane prepolymer B was 50 weight%.

[Example 1] 100 parts by weight of urethane prepolymer A; 3.2 parts by weight of isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent; MEGAFAC F-571 (DIC 0.5 parts by weight; Irganox 1010 (manufactured by BASF) as an antioxidant 0.5 parts by weight; 0.03 parts by weight of iron triacetylacetonate (manufactured by Nippon Chemical Industry Co., Ltd.) as a catalyst to achieve 50% by weight of the overall solid content The method was diluted with ethyl acetate to obtain a urethane-based adhesive solution. Then, the urethane-based adhesive solution was applied to a polyester resin base material (trade name "T100-75S", thickness 75 μm, Mitsubishi Chemical Co., Ltd. production), cured and dried at a drying temperature of 130° C. and a drying time of 3 minutes to produce an adhesive layer containing an adhesive composition. Next, a release liner made of a polyester resin (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Co., Ltd.) with one side treated with silicone and a thickness of 25 μm was attached to the surface of the obtained adhesive layer. Silicone treated surface to obtain a surface protective film (1). Aging was performed at normal temperature for 5 days, and evaluation was performed.

[Example 2] 100 parts by weight of urethane prepolymer B; 2.9 parts by weight of isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent; MEGAFAC F-571 (DIC 0.5 parts by weight; Irganox 1010 (manufactured by BASF) as an antioxidant 0.5 parts by weight; 0.03 parts by weight of iron triacetylacetonate (manufactured by Nippon Chemical Industry Co., Ltd.) as a catalyst to achieve 50% by weight of the overall solid content The method was diluted with ethyl acetate to obtain a urethane-based adhesive solution. Then, the urethane-based adhesive solution was applied to a polyester resin base material (trade name "T100-75S", thickness 75 μm, Mitsubishi Chemical Co., Ltd. production), cured and dried at a drying temperature of 130° C. and a drying time of 3 minutes to produce an adhesive layer containing an adhesive composition. Next, a release liner made of a polyester resin (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Co., Ltd.) with one side treated with silicone and a thickness of 25 μm was attached to the surface of the obtained adhesive layer. Silicone treated surface to obtain a surface protection film (2). Aging was performed at normal temperature for 5 days, and evaluation was performed.

[Example 3] 95 parts by weight of urethane prepolymer B; as a polyol, 3 parts by weight of a polyol with 3 hydroxyl groups, namely PREMINOL S3011 (manufactured by Asahi Glass Co., Mn=10000), and 3 parts by weight of a polyol with 3 hydroxyl groups, namely PTGL3000 (manufactured by Hodogaya Chemical Industry Co., Ltd., Mn=3000) 2 parts by weight; 3.7 parts by weight of an isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent, MEGAFAC F-571 of a fluorine-based oligomer (manufactured by DIC Corporation) 0.5 parts by weight; 0.5 parts by weight of Irganox 1010 (manufactured by BASF Corporation) as an antioxidant; 0.03 parts by weight of iron triacetylacetonate (manufactured by Nippon Chemical Industry Co., Ltd.) as a catalyst reaches 50 parts by weight as a whole % by weight was diluted with ethyl acetate to obtain a urethane-based adhesive solution. Then, the urethane-based adhesive solution was applied to a polyester resin base material (trade name "T100-75S", thickness 75 μm, Mitsubishi Chemical Co., Ltd. production), cured and dried at a drying temperature of 130° C. and a drying time of 3 minutes to produce an adhesive layer containing an adhesive composition. Next, a release liner made of a polyester resin (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Co., Ltd.) with one side treated with silicone and a thickness of 25 μm was attached to the surface of the obtained adhesive layer. Silicone treated surface to obtain a surface protective film (3). Aging was performed at normal temperature for 5 days, and evaluation was performed.

[Example 4] 95 parts by weight of urethane prepolymer A; 3.5 parts by weight of a polyol with 3 hydroxyl groups, that is, PREMINOL S3011 (manufactured by Asahi Glass Co., Ltd., Mn=10000), and a polyol with 3 hydroxyl groups, that is, SANNIX GP3000 (manufactured by Sanyo Chemical, Mn=3000) 1.5 parts by weight; 3.8 parts by weight of an isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Company) as a crosslinking agent, MEGAFAC F-571 of a fluorine-based oligomer ( DIC company manufacture) 0.5 weight part; Irganox1010 (BASF company manufacture) as antioxidant 0.5 weight part; As catalyst iron triacetyl acetonate (Nippon Chemical Industry Co., Ltd. manufacture) 0.03 weight part reaches 50 weight parts with the whole solid content % was diluted with ethyl acetate to obtain a urethane-based adhesive solution. Then, the urethane-based adhesive solution was applied to a polyester resin base material (trade name "T100-75S", thickness 75 μm, Mitsubishi Chemical Co., Ltd. production), cured and dried at a drying temperature of 130° C. and a drying time of 3 minutes to produce an adhesive layer containing an adhesive composition. Next, a release liner made of a polyester resin (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Co., Ltd.) with one side treated with silicone and a thickness of 25 μm was attached to the surface of the obtained adhesive layer. Silicone treated surface to obtain a surface protective film (4). Aging was performed at normal temperature for 5 days, and evaluation was performed.

[Example 5] 95 parts by weight of urethane prepolymer A; 3 parts by weight of a polyol with 3 hydroxyl groups, namely PREMINOL S3011 (manufactured by Asahi Glass Co., Ltd., Mn=10000), as a polyol, and a polyol with 3 hydroxyl groups, namely SANNIX 2 parts by weight of GP3000 (manufactured by Sanyo Chemicals, Mn=3000); 3.9 parts by weight of isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Company) as a crosslinking agent, MEGAFAC F-571 ( DIC company manufacture) 0.5 weight part; Irganox1010 (BASF company manufacture) as antioxidant 0.5 weight part; As catalyst iron triacetyl acetonate (Nippon Chemical Industry Co., Ltd. manufacture) 0.03 weight part reaches 50 weight parts with the whole solid content % was diluted with ethyl acetate to obtain a urethane-based adhesive solution. Then, the urethane-based adhesive solution was applied to a polyester resin base material (trade name "T100-75S", thickness 75 μm, Mitsubishi Chemical Co., Ltd. production), cured and dried at a drying temperature of 130° C. and a drying time of 3 minutes to produce an adhesive layer containing an adhesive composition. Next, a release liner made of a polyester resin (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Co., Ltd.) with one side treated with silicone and a thickness of 25 μm was attached to the surface of the obtained adhesive layer. Silicone treated surface to obtain a surface protective film (5). Aging was performed at normal temperature for 5 days, and evaluation was performed.

[Example 6] 80 parts by weight of urethane prepolymer A; 12 parts by weight of a polyol with 3 hydroxyl groups, namely PREMINOL S3011 (manufactured by Asahi Glass Co., Ltd., Mn=10000), as a polyol, and SANNIX as a polyol with 3 hydroxyl groups GP3000 (manufactured by Sanyo Chemical, Mn=3000) 8 parts by weight; 6.0 parts by weight of isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Company) as a crosslinking agent, MEGAFAC F-571 ( DIC company manufacture) 0.5 weight part; Irganox1010 (BASF company manufacture) as antioxidant 0.5 weight part; As catalyst iron triacetyl acetonate (Nippon Chemical Industry Co., Ltd. manufacture) 0.03 weight part reaches 50 weight parts with the whole solid content % was diluted with ethyl acetate to obtain a urethane-based adhesive solution. Then, the urethane-based adhesive solution was applied to a polyester resin base material (trade name "T100-75S", thickness 75 μm, Mitsubishi Chemical Co., Ltd. production), cured and dried at a drying temperature of 130° C. and a drying time of 3 minutes to produce an adhesive layer containing an adhesive composition. Next, a release liner made of a polyester resin (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Co., Ltd.) with one side treated with silicone and a thickness of 25 μm was attached to the surface of the obtained adhesive layer. Silicone treated surface to obtain a surface protective film (6). Aging was performed at normal temperature for 5 days, and evaluation was performed.

[Example 7] 60 parts by weight of urethane prepolymer A; 28 parts by weight of a polyol with 3 hydroxyl groups, that is, PREMINOL S3011 (manufactured by Asahi Glass Co., Ltd., Mn=10000), and a polyol with 3 hydroxyl groups, namely SANNIX 12 parts by weight of GP3000 (manufactured by Sanyo Chemical Industry Co., Ltd., Mn=3000); 8.0 parts by weight of isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Company) as a crosslinking agent; MEGAFAC F-571 ( DIC company manufacture) 0.5 weight part; Irganox1010 (BASF company manufacture) as antioxidant 0.5 weight part; As catalyst iron triacetyl acetonate (Nippon Chemical Industry Co., Ltd. manufacture) 0.03 weight part reaches 50 weight parts with the whole solid content % was diluted with ethyl acetate to obtain a urethane-based adhesive solution. Then, the urethane-based adhesive solution was applied to a polyester resin base material (trade name "T100-75S", thickness 75 μm, Mitsubishi Chemical Co., Ltd. production), cured and dried at a drying temperature of 130° C. and a drying time of 3 minutes to produce an adhesive layer containing an adhesive composition. Next, a release liner made of a polyester resin (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Co., Ltd.) with one side treated with silicone and a thickness of 25 μm was attached to the surface of the obtained adhesive layer. Silicone treated surface to obtain a surface protective film (7). Aging was performed at normal temperature for 5 days, and evaluation was performed.

[Example 8] 60 parts by weight of urethane prepolymer A; 25 parts by weight of a polyol having 3 hydroxyl groups, namely PREMINOL S3011 (manufactured by Asahi Glass Co., Ltd., Mn=10000), and 25 parts by weight of a polyol having 3 hydroxyl groups, namely SANNIX 15 parts by weight of GP3000 (manufactured by Sanyo Chemicals, Mn=3000); 8.6 parts by weight of isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Company) as a crosslinking agent; MEGAFAC F-571 ( DIC company manufacture) 0.5 weight part; Irganox1010 (BASF company manufacture) as antioxidant 0.5 weight part; As catalyst iron triacetyl acetonate (Nippon Chemical Industry Co., Ltd. manufacture) 0.03 weight part reaches 50 weight parts with the whole solid content % was diluted with ethyl acetate to obtain a urethane-based adhesive solution. Then, the urethane-based adhesive solution was applied to a polyester resin base material (trade name "T100-75S", thickness 75 μm, Mitsubishi Chemical Co., Ltd. production), cured and dried at a drying temperature of 130° C. and a drying time of 3 minutes to produce an adhesive layer containing an adhesive composition. Next, a release liner made of a polyester resin (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Co., Ltd.) with one side treated with silicone and a thickness of 25 μm was attached to the surface of the obtained adhesive layer. Silicone treated surface to obtain a surface protective film (8). Aging was performed at normal temperature for 5 days, and evaluation was performed.

[Example 9] 50 parts by weight of urethane prepolymer A; 30 parts by weight of a polyol having 3 hydroxyl groups, namely PREMINOL S3011 (manufactured by Asahi Glass Co., Ltd., Mn=10000), and 30 parts by weight of a polyol having 3 hydroxyl groups, namely SANNIX 20 parts by weight of GP4000 (manufactured by Sanyo Chemicals, Mn=4000); 8.7 parts by weight of an isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Company) as a crosslinking agent, MEGAFAC F-571 of a fluorine-based oligomer ( DIC company manufacture) 0.5 weight part; Irganox1010 (BASF company manufacture) 0.5 weight part as anti-oxidant; 0.03 weight part of iron triacetyl acetonate (Nippon Chemical Industry Co., Ltd. manufacture) as catalyst reaches 50 weight parts with the whole solid content % was diluted with ethyl acetate to obtain a urethane-based adhesive solution. Then, the urethane-based adhesive solution was applied to a polyester resin base material (trade name "T100-75S", thickness 75 μm, Mitsubishi Chemical Co., Ltd. production), cured and dried at a drying temperature of 130° C. and a drying time of 3 minutes to produce an adhesive layer containing an adhesive composition. Next, a release liner made of a polyester resin (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Co., Ltd.) with one side treated with silicone and a thickness of 25 μm was attached to the surface of the obtained adhesive layer. Silicone treated surface to obtain a surface protective film (9). Aging was performed at normal temperature for 5 days, and evaluation was performed.

[Example 10] 100 parts by weight of urethane prepolymer A; 3.2 parts by weight of isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent; MEGAFAC F-563 (DIC 0.5 parts by weight; Irganox 1010 (manufactured by BASF) as an antioxidant 0.5 parts by weight; 0.03 parts by weight of iron triacetylacetonate (manufactured by Nippon Chemical Industry Co., Ltd.) as a catalyst to achieve 50% by weight of the overall solid content The method was diluted with ethyl acetate to obtain a urethane-based adhesive solution. Then, the urethane-based adhesive solution was applied to a polyester resin base material (trade name "T100-75S", thickness 75 μm, Mitsubishi Chemical Co., Ltd. production), cured and dried at a drying temperature of 130° C. and a drying time of 3 minutes to produce an adhesive layer containing an adhesive composition. Next, a release liner made of a polyester resin (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Co., Ltd.) with one side treated with silicone and a thickness of 25 μm was attached to the surface of the obtained adhesive layer. Silicone treated surface to obtain a surface protective film (10). Aging was performed at normal temperature for 5 days, and evaluation was performed.

[Example 11] 100 parts by weight of urethane prepolymer B; 2.9 parts by weight of isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent; MEGAFAC F-563 (DIC 0.5 parts by weight; Irganox 1010 (manufactured by BASF) as an antioxidant 0.5 parts by weight; 0.03 parts by weight of iron triacetylacetonate (manufactured by Nippon Chemical Industry Co., Ltd.) as a catalyst to achieve 50% by weight of the overall solid content The method was diluted with ethyl acetate to obtain a urethane-based adhesive solution. Then, the urethane-based adhesive solution was applied to a polyester resin base material (trade name "T100-75S", thickness 75 μm, Mitsubishi Chemical Co., Ltd. production), cured and dried at a drying temperature of 130° C. and a drying time of 3 minutes to produce an adhesive layer containing an adhesive composition. Next, a release liner made of a polyester resin (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Co., Ltd.) with one side treated with silicone and a thickness of 25 μm was attached to the surface of the obtained adhesive layer. Silicone treated surface to obtain a surface protective film (11). Aging was performed at normal temperature for 5 days, and evaluation was performed.

[Example 12] 95 parts by weight of urethane prepolymer B; as a polyol, 3 parts by weight of a polyol with 3 hydroxyl groups, namely PREMINOL S3011 (manufactured by Asahi Glass Co., Mn=10000), and 3 parts by weight of a polyol with 3 hydroxyl groups, namely PTGL3000 (manufactured by Hodogaya Chemical Industry Co., Ltd., Mn=3000) 2 parts by weight; 3.7 parts by weight of an isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent, MEGAFAC F-563 of a fluorine-based oligomer (manufactured by DIC Corporation) 0.5 parts by weight; 0.5 parts by weight of Irganox 1010 (manufactured by BASF Corporation) as an antioxidant; 0.03 parts by weight of iron triacetylacetonate (manufactured by Nippon Chemical Industry Co., Ltd.) as a catalyst reaches 50 parts by weight as a whole % by weight was diluted with ethyl acetate to obtain a urethane-based adhesive solution. Then, the urethane-based adhesive solution was applied to a polyester resin base material (trade name "T100-75S", thickness 75 μm, Mitsubishi Chemical Co., Ltd. production), cured and dried at a drying temperature of 130° C. and a drying time of 3 minutes to produce an adhesive layer containing an adhesive composition. Next, a release liner made of a polyester resin (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Co., Ltd.) with one side treated with silicone and a thickness of 25 μm was attached to the surface of the obtained adhesive layer. Silicone treated surface to obtain a surface protective film (12). Aging was performed at normal temperature for 5 days, and evaluation was performed.

[Example 13] 95 parts by weight of urethane prepolymer A; 3.5 parts by weight of a polyol with 3 hydroxyl groups, that is, PREMINOL S3011 (manufactured by Asahi Glass Co., Ltd., Mn=10000), and a polyol with 3 hydroxyl groups, that is, SANNIX GP3000 (manufactured by Sanyo Chemical, Mn=3000) 1.5 parts by weight; 3.8 parts by weight of isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Company) as a crosslinking agent, MEGAFAC F-563 ( DIC company manufacture) 0.5 weight part; Irganox1010 (BASF company manufacture) as antioxidant 0.5 weight part; As catalyst iron triacetyl acetonate (Nippon Chemical Industry Co., Ltd. manufacture) 0.03 weight part reaches 50 weight parts with the whole solid content % was diluted with ethyl acetate to obtain a urethane-based adhesive solution. Then, the urethane-based adhesive solution was applied to a polyester resin base material (trade name "T100-75S", thickness 75 μm, Mitsubishi Chemical Co., Ltd. production), cured and dried at a drying temperature of 130° C. and a drying time of 3 minutes to produce an adhesive layer containing an adhesive composition. Next, a release liner made of a polyester resin (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Co., Ltd.) with one side treated with silicone and a thickness of 25 μm was attached to the surface of the obtained adhesive layer. Silicone treated surface to obtain a surface protective film (13). Aging was performed at normal temperature for 5 days, and evaluation was performed.

[Example 14] 95 parts by weight of urethane prepolymer A; 3 parts by weight of a polyol with 3 hydroxyl groups, namely PREMINOL S3011 (manufactured by Asahi Glass Co., Ltd., Mn=10000), as a polyol, and a polyol with 3 hydroxyl groups, namely SANNIX 2 parts by weight of GP3000 (manufactured by Sanyo Chemicals, Mn=3000); 3.9 parts by weight of isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Company) as a crosslinking agent, MEGAFAC F-563 ( DIC company manufacture) 0.5 weight part; Irganox1010 (BASF company manufacture) as antioxidant 0.5 weight part; As catalyst iron triacetyl acetonate (Nippon Chemical Industry Co., Ltd. manufacture) 0.03 weight part reaches 50 weight parts with the whole solid content % was diluted with ethyl acetate to obtain a urethane-based adhesive solution. Then, the urethane-based adhesive solution was applied to a polyester resin base material (trade name "T100-75S", thickness 75 μm, Mitsubishi Chemical Co., Ltd. production), cured and dried at a drying temperature of 130° C. and a drying time of 3 minutes to produce an adhesive layer containing an adhesive composition. Next, a release liner made of a polyester resin (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Co., Ltd.) with one side treated with silicone and a thickness of 25 μm was attached to the surface of the obtained adhesive layer. Silicone treated surface to obtain a surface protective film (14). Aging was performed at normal temperature for 5 days, and evaluation was performed.

[Example 15] 80 parts by weight of urethane prepolymer A; 12 parts by weight of a polyol with 3 hydroxyl groups, namely PREMINOL S3011 (manufactured by Asahi Glass Co., Ltd., Mn=10000), as a polyol, and SANNIX as a polyol with 3 hydroxyl groups GP3000 (manufactured by Sanyo Chemical, Mn=3000) 8 parts by weight; 6.0 parts by weight of isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Company) as a crosslinking agent, MEGAFAC F-563 ( DIC company manufacture) 0.5 weight part; Irganox1010 (BASF company manufacture) as antioxidant 0.5 weight part; As catalyst iron triacetyl acetonate (Nippon Chemical Industry Co., Ltd. manufacture) 0.03 weight part reaches 50 weight parts with the whole solid content % was diluted with ethyl acetate to obtain a urethane-based adhesive solution. Then, the urethane-based adhesive solution was applied to a polyester resin base material (trade name "T100-75S", thickness 75 μm, Mitsubishi Chemical Co., Ltd. production), cured and dried at a drying temperature of 130° C. and a drying time of 3 minutes to produce an adhesive layer containing an adhesive composition. Next, a release liner made of a polyester resin (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Co., Ltd.) with one side treated with silicone and a thickness of 25 μm was attached to the surface of the obtained adhesive layer. Silicone treated surface to obtain a surface protective film (15). Aging was performed at normal temperature for 5 days, and evaluation was performed.

[Example 16] 60 parts by weight of urethane prepolymer A; 28 parts by weight of a polyol with 3 hydroxyl groups, that is, PREMINOL S3011 (manufactured by Asahi Glass Co., Ltd., Mn=10000), and a polyol with 3 hydroxyl groups, namely SANNIX 12 parts by weight of GP3000 (manufactured by Sanyo Chemicals, Mn=3000); 8.0 parts by weight of isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Company) as a crosslinking agent; MEGAFAC F-563 ( DIC company manufacture) 0.5 weight part; Irganox1010 (BASF company manufacture) as antioxidant 0.5 weight part; As catalyst iron triacetyl acetonate (Nippon Chemical Industry Co., Ltd. manufacture) 0.03 weight part reaches 50 weight parts with the whole solid content % was diluted with ethyl acetate to obtain a urethane-based adhesive solution. Then, the urethane-based adhesive solution was applied to a polyester resin base material (trade name "T100-75S", thickness 75 μm, Mitsubishi Chemical Co., Ltd. production), cured and dried at a drying temperature of 130° C. and a drying time of 3 minutes to produce an adhesive layer containing an adhesive composition. Next, a release liner made of a polyester resin (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Co., Ltd.) with one side treated with silicone and a thickness of 25 μm was attached to the surface of the obtained adhesive layer. Silicone treated surface to obtain a surface protective film (16). Aging was performed at normal temperature for 5 days, and evaluation was performed.

[Example 17] 60 parts by weight of urethane prepolymer A; 25 parts by weight of a polyol having 3 hydroxyl groups, namely PREMINOL S3011 (manufactured by Asahi Glass Co., Ltd., Mn=10000), and 25 parts by weight of a polyol having 3 hydroxyl groups, namely SANNIX 15 parts by weight of GP3000 (manufactured by Sanyo Chemical Industry Co., Ltd., Mn=3000); 8.6 parts by weight of isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Company) as a crosslinking agent; MEGAFAC F-563 ( DIC company manufacture) 0.5 weight part; Irganox1010 (BASF company manufacture) as antioxidant 0.5 weight part; As catalyst iron triacetyl acetonate (Nippon Chemical Industry Co., Ltd. manufacture) 0.03 weight part reaches 50 weight parts with the whole solid content % was diluted with ethyl acetate to obtain a urethane-based adhesive solution. Then, the urethane-based adhesive solution was applied to a polyester resin base material (trade name "T100-75S", thickness 75 μm, Mitsubishi Chemical Co., Ltd. production), cured and dried at a drying temperature of 130° C. and a drying time of 3 minutes to produce an adhesive layer containing an adhesive composition. Next, a release liner made of a polyester resin (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Co., Ltd.) with one side treated with silicone and a thickness of 25 μm was attached to the surface of the obtained adhesive layer. Silicone treated surface to obtain a surface protective film (17). Aging was performed at normal temperature for 5 days, and evaluation was performed.

[Example 18] 50 parts by weight of urethane prepolymer A; 30 parts by weight of a polyol with 3 hydroxyl groups, namely PREMINOL S3011 (manufactured by Asahi Glass Co., Mn=10000), as a polyol, and a polyol with 3 hydroxyl groups, namely SANNIX 20 parts by weight of GP4000 (manufactured by Sanyo Chemicals, Mn=4000); 8.7 parts by weight of isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Company) as a crosslinking agent, MEGAFAC F-563 ( DIC company manufacture) 0.5 weight part; Irganox1010 (BASF company manufacture) as antioxidant 0.5 weight part; As catalyst iron triacetyl acetonate (Nippon Chemical Industry Co., Ltd. manufacture) 0.03 weight part reaches 50 weight parts with the whole solid content % was diluted with ethyl acetate to obtain a urethane-based adhesive solution. Then, the urethane-based adhesive solution was applied to a polyester resin base material (trade name "T100-75S", thickness 75 μm, Mitsubishi Chemical Co., Ltd. production), cured and dried at a drying temperature of 130° C. and a drying time of 3 minutes to produce an adhesive layer containing an adhesive composition. Next, a release liner made of a polyester resin (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Co., Ltd.) with one side treated with silicone and a thickness of 25 μm was attached to the surface of the obtained adhesive layer. Silicone treated surface to obtain a surface protective film (18). Aging was performed at normal temperature for 5 days, and evaluation was performed.

[Example 19] 100 parts by weight of urethane prepolymer A; 3.2 parts by weight of isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent; MEGAFAC F-477 (DIC 0.5 parts by weight; Irganox 1010 (manufactured by BASF) as an antioxidant 0.5 parts by weight; 0.03 parts by weight of iron triacetylacetonate (manufactured by Nippon Chemical Industry Co., Ltd.) as a catalyst to achieve 50% by weight of the overall solid content The method was diluted with ethyl acetate to obtain a urethane-based adhesive solution. Then, the urethane-based adhesive solution was applied to a polyester resin base material (trade name "T100-75S", thickness 75 μm, Mitsubishi Chemical Co., Ltd. production), cured and dried at a drying temperature of 130° C. and a drying time of 3 minutes to produce an adhesive layer containing an adhesive composition. Next, a release liner made of a polyester resin (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Co., Ltd.) with one side treated with silicone and a thickness of 25 μm was attached to the surface of the obtained adhesive layer. Silicone treated surface to obtain a surface protective film (19). Aging was performed at normal temperature for 5 days, and evaluation was performed.

[Example 20] 100 parts by weight of urethane prepolymer B; 2.9 parts by weight of isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent; MEGAFAC F-477 (DIC 0.5 parts by weight; Irganox 1010 (manufactured by BASF) as an antioxidant 0.5 parts by weight; 0.03 parts by weight of iron triacetylacetonate (manufactured by Nippon Chemical Industry Co., Ltd.) as a catalyst to achieve 50% by weight of the overall solid content The method was diluted with ethyl acetate to obtain a urethane-based adhesive solution. Then, the urethane-based adhesive solution was applied to a polyester resin base material (trade name "T100-75S", thickness 75 μm, Mitsubishi Chemical Co., Ltd. production), cured and dried at a drying temperature of 130° C. and a drying time of 3 minutes to produce an adhesive layer containing an adhesive composition. Next, a release liner made of a polyester resin (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Co., Ltd.) with one side treated with silicone and a thickness of 25 μm was attached to the surface of the obtained adhesive layer. Silicone treated surface to obtain a surface protective film (20). Aging was performed at normal temperature for 5 days, and evaluation was performed.

[Example 21] 100 parts by weight of urethane prepolymer A; 3.2 parts by weight of isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent; MEGAFAC F-556 (DIC 0.5 parts by weight; Irganox 1010 (manufactured by BASF) as an antioxidant 0.5 parts by weight; 0.03 parts by weight of iron triacetylacetonate (manufactured by Nippon Chemical Industry Co., Ltd.) as a catalyst to achieve 50% by weight of the overall solid content The method was diluted with ethyl acetate to obtain a urethane-based adhesive solution. Then, the urethane-based adhesive solution was applied to a polyester resin base material (trade name "T100-75S", thickness 75 μm, Mitsubishi Chemical Co., Ltd. production), cured and dried at a drying temperature of 130° C. and a drying time of 3 minutes to produce an adhesive layer containing an adhesive composition. Next, a release liner made of a polyester resin (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Co., Ltd.) with one side treated with silicone and a thickness of 25 μm was attached to the surface of the obtained adhesive layer. Silicone treated surface to obtain a surface protective film (21). Aging was performed at normal temperature for 5 days, and evaluation was performed.

[Example 22] 100 parts by weight of urethane prepolymer B; 2.9 parts by weight of isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent; MEGAFAC F-556 (DIC 0.5 parts by weight; Irganox 1010 (manufactured by BASF) as an antioxidant 0.5 parts by weight; 0.03 parts by weight of iron triacetylacetonate (manufactured by Nippon Chemical Industry Co., Ltd.) as a catalyst to achieve 50% by weight of the overall solid content The method was diluted with ethyl acetate to obtain a urethane-based adhesive solution. Then, the urethane-based adhesive solution was applied to a polyester resin base material (trade name "T100-75S", thickness 75 μm, Mitsubishi Chemical Co., Ltd. production), cured and dried at a drying temperature of 130° C. and a drying time of 3 minutes to produce an adhesive layer containing an adhesive composition. Next, a release liner made of a polyester resin (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Co., Ltd.) with one side treated with silicone and a thickness of 25 μm was attached to the surface of the obtained adhesive layer. Silicone treated surface to obtain a surface protective film (22). Aging was performed at normal temperature for 5 days, and evaluation was performed.

[Example 23] 100 parts by weight of urethane prepolymer A; 3.2 parts by weight of isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent; MEGAFAC F-571 (DIC 0.5 parts by weight; 0.5 parts by weight of 1-ethyl-3-methylimidazolium tris(fluoromethylsulfonyl)imide (AS110, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) as an ionic compound; 0.5 parts by weight of Irganox 1010 (manufactured by BASF Corporation) of the oxidizing agent; 0.03 parts by weight of iron triacetylacetonate (manufactured by Nippon Chemical Industry Co., Ltd.) as a catalyst is diluted with ethyl acetate so that the overall solid content reaches 50% by weight, Thus, a urethane-based adhesive solution was obtained. Then, the urethane-based adhesive solution was applied to a polyester resin base material (trade name "T100-75S", thickness 75 μm, Mitsubishi Chemical Co., Ltd. production), cured and dried at a drying temperature of 130° C. and a drying time of 3 minutes to produce an adhesive layer containing an adhesive composition. Next, a release liner made of a polyester resin (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Co., Ltd.) with one side treated with silicone and a thickness of 25 μm was attached to the surface of the obtained adhesive layer. Silicone treated surface to obtain a surface protective film (23). Aging was performed at normal temperature for 5 days, and evaluation was performed.

[Example 24] 100 parts by weight of urethane prepolymer A; 3.2 parts by weight of isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent; MEGAFAC F-571 (DIC Company manufacture) 0.5 parts by weight; 1-ethyl-3-methylimidazolium tris(fluoromethylsulfonyl)imide (AS110, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) as an ionic compound 0.10 parts by weight; 0.5 parts by weight of Irganox 1010 (manufactured by BASF Corporation) of the oxidizing agent; 0.03 parts by weight of iron triacetylacetonate (manufactured by Nippon Chemical Industry Co., Ltd.) as a catalyst is diluted with ethyl acetate so that the overall solid content reaches 50% by weight, Thus, a urethane-based adhesive solution was obtained. Then, the urethane-based adhesive solution was applied to a polyester resin base material (trade name "T100-75S", thickness 75 μm, Mitsubishi Chemical Co., Ltd. production), cured and dried at a drying temperature of 130° C. and a drying time of 3 minutes to produce an adhesive layer containing an adhesive composition. Next, a release liner made of a polyester resin (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Co., Ltd.) with one side treated with silicone and a thickness of 25 μm was attached to the surface of the obtained adhesive layer. Silicone treated surface to obtain a surface protective film (24). Aging was performed at normal temperature for 5 days, and evaluation was performed.

[Example 25] 100 parts by weight of urethane prepolymer A; 3.2 parts by weight of isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent; MEGAFAC F-571 (DIC 0.5 parts by weight; 0.5 parts by weight of 1-ethyl-3-methylimidazolium tris(fluoromethylsulfonyl)imide (AS110, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) as an ionic compound; 0.5 parts by weight of Irganox 1010 (manufactured by BASF Corporation) of the oxidizing agent; 0.03 parts by weight of iron triacetylacetonate (manufactured by Nippon Chemical Industry Co., Ltd.) as a catalyst is diluted with ethyl acetate so that the overall solid content reaches 50% by weight, Thus, a urethane-based adhesive solution was obtained. Then, the urethane-based adhesive solution was applied to a polyester resin base material (trade name "T100-75S", thickness 75 μm, Mitsubishi Chemical Co., Ltd. production), cured and dried at a drying temperature of 130° C. and a drying time of 3 minutes to produce an adhesive layer containing an adhesive composition. Next, a release liner made of a polyester resin (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Co., Ltd.) with one side treated with silicone and a thickness of 25 μm was attached to the surface of the obtained adhesive layer. Silicone treated surface to obtain a surface protective film (25). Aging was performed at normal temperature for 5 days, and evaluation was performed.

[Example 26] 100 parts by weight of urethane prepolymer A; 3.2 parts by weight of isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent; MEGAFAC F-571 (DIC company) 0.5 parts by weight; 1-ethyl-3-methylimidazolium tris(fluoromethylsulfonyl)imide (AS110, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) as an ionic compound 1.00 parts by weight; 0.5 parts by weight of Irganox 1010 (manufactured by BASF Corporation) of the oxidizing agent; 0.03 parts by weight of iron triacetylacetonate (manufactured by Nippon Chemical Industry Co., Ltd.) as a catalyst is diluted with ethyl acetate so that the overall solid content reaches 50% by weight, Thus, a urethane-based adhesive solution was obtained. Then, the urethane-based adhesive solution was applied to a polyester resin base material (trade name "T100-75S", thickness 75 μm, Mitsubishi Chemical Co., Ltd. production), cured and dried at a drying temperature of 130° C. and a drying time of 3 minutes to produce an adhesive layer containing an adhesive composition. Next, a release liner made of a polyester resin (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Co., Ltd.) with one side treated with silicone and a thickness of 25 μm was attached to the surface of the obtained adhesive layer. Silicone treated surface to obtain a surface protective film (26). Aging was performed at normal temperature for 5 days, and evaluation was performed.

[Example 27] 100 parts by weight of urethane prepolymer A; 3.2 parts by weight of isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent; MEGAFAC F-563 (DIC 0.5 parts by weight; 0.5 parts by weight of 1-ethyl-3-methylimidazolium tris(fluoromethylsulfonyl)imide (AS110, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) as an ionic compound; 0.5 parts by weight of Irganox 1010 (manufactured by BASF Corporation) of the oxidizing agent; 0.03 parts by weight of iron triacetylacetonate (manufactured by Nippon Chemical Industry Co., Ltd.) as a catalyst is diluted with ethyl acetate so that the overall solid content reaches 50% by weight, Thus, a urethane-based adhesive solution was obtained. Then, the urethane-based adhesive solution was applied to a polyester resin base material (trade name "T100-75S", thickness 75 μm, Mitsubishi Chemical Co., Ltd. production), cured and dried at a drying temperature of 130° C. and a drying time of 3 minutes to produce an adhesive layer containing an adhesive composition. Next, a release liner made of a polyester resin (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Co., Ltd.) with one side treated with silicone and a thickness of 25 μm was attached to the surface of the obtained adhesive layer. Silicone treated surface to obtain a surface protective film (27). Aging was performed at normal temperature for 5 days, and evaluation was performed.

[Example 28] 100 parts by weight of urethane prepolymer A; 3.2 parts by weight of isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent; MEGAFAC F-477 (DIC 0.5 parts by weight; 0.5 parts by weight of 1-ethyl-3-methylimidazolium tris(fluoromethylsulfonyl)imide (AS110, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) as an ionic compound; 0.5 parts by weight of Irganox 1010 (manufactured by BASF Corporation) of the oxidizing agent; 0.03 parts by weight of iron triacetylacetonate (manufactured by Nippon Chemical Industry Co., Ltd.) as a catalyst is diluted with ethyl acetate so that the overall solid content reaches 50% by weight, Thus, a urethane-based adhesive solution was obtained. Then, the urethane-based adhesive solution was applied to a polyester resin base material (trade name "T100-75S", thickness 75 μm, Mitsubishi Chemical Co., Ltd. production), cured and dried at a drying temperature of 130° C. and a drying time of 3 minutes to produce an adhesive layer containing an adhesive composition. Next, a release liner made of a polyester resin (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Co., Ltd.) with one side treated with silicone and a thickness of 25 μm was attached to the surface of the obtained adhesive layer. Silicone treated surface to obtain a surface protective film (28). Aging was performed at normal temperature for 5 days, and evaluation was performed.

[Example 29] 100 parts by weight of urethane prepolymer A; 3.2 parts by weight of isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent; MEGAFAC F-556 (DIC 0.5 parts by weight; 0.5 parts by weight of 1-ethyl-3-methylimidazolium tris(fluoromethylsulfonyl)imide (AS110, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) as an ionic compound; 0.5 parts by weight of Irganox 1010 (manufactured by BASF Corporation) of the oxidizing agent; 0.03 parts by weight of iron triacetylacetonate (manufactured by Nippon Chemical Industry Co., Ltd.) as a catalyst is diluted with ethyl acetate so that the overall solid content reaches 50% by weight, Thus, a urethane-based adhesive solution was obtained. Then, the urethane-based adhesive solution was applied to a polyester resin base material (trade name "T100-75S", thickness 75 μm, Mitsubishi Chemical Co., Ltd. production), cured and dried at a drying temperature of 130° C. and a drying time of 3 minutes to produce an adhesive layer containing an adhesive composition. Next, a release liner made of a polyester resin (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Co., Ltd.) with one side treated with silicone and a thickness of 25 μm was attached to the surface of the obtained adhesive layer. Silicone treated surface to obtain a surface protective film (29). Aging was performed at normal temperature for 5 days, and evaluation was performed.

[Example 30] 95 parts by weight of urethane prepolymer A; 3.5 parts by weight of a polyol with 3 hydroxyl groups, that is, PREMINOL S3011 (manufactured by Asahi Glass Co., Ltd., Mn=10000), and a polyol with 3 hydroxyl groups, that is, SANNIX GP3000 (manufactured by Sanyo Chemical, Mn=3000) 1.5 parts by weight; 3.8 parts by weight of an isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Company) as a crosslinking agent, MEGAFAC F-571 of a fluorine-based oligomer ( DIC Corporation) 0.5 parts by weight; 0.50 parts by weight of 1-ethyl-3-methylimidazolium tris(fluoromethylsulfonyl)imide (AS110, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) as an ionic compound; 0.5 parts by weight of Irganox 1010 (manufactured by BASF) as an antioxidant; 0.03 parts by weight of iron triacetylacetonate (manufactured by Nippon Chemical Industry Co., Ltd.) as a catalyst was diluted with ethyl acetate so that the overall solid content reached 50% by weight , to obtain a urethane-based adhesive solution. Then, the urethane-based adhesive solution was applied to a polyester resin base material (trade name "T100-75S", thickness 75 μm, Mitsubishi Chemical Co., Ltd. production), cured and dried at a drying temperature of 130° C. and a drying time of 3 minutes to produce an adhesive layer containing an adhesive composition. Next, a release liner made of a polyester resin (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Co., Ltd.) with one side treated with silicone and a thickness of 25 μm was attached to the surface of the obtained adhesive layer. Silicone treated surface to obtain a surface protection film (30). Aging was performed at normal temperature for 5 days, and evaluation was performed.

[Example 31] 95 parts by weight of urethane prepolymer A; 3 parts by weight of a polyol with 3 hydroxyl groups, namely PREMINOL S3011 (manufactured by Asahi Glass Co., Ltd., Mn=10000), as a polyol, and a polyol with 3 hydroxyl groups, namely SANNIX 2 parts by weight of GP3000 (manufactured by Sanyo Chemicals, Mn=3000); 3.9 parts by weight of isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Company) as a crosslinking agent, MEGAFAC F-571 ( DIC Corporation) 0.5 parts by weight; 0.50 parts by weight of 1-ethyl-3-methylimidazolium tris(fluoromethylsulfonyl)imide (AS110, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) as an ionic compound; 0.5 parts by weight of Irganox 1010 (manufactured by BASF) as an antioxidant; 0.03 parts by weight of iron triacetylacetonate (manufactured by Nippon Chemical Industry Co., Ltd.) as a catalyst was diluted with ethyl acetate so that the overall solid content reached 50% by weight , to obtain a urethane-based adhesive solution. Then, the urethane-based adhesive solution was applied to a polyester resin base material (trade name "T100-75S", thickness 75 μm, Mitsubishi Chemical Co., Ltd. production), cured and dried at a drying temperature of 130° C. and a drying time of 3 minutes to produce an adhesive layer containing an adhesive composition. Next, a release liner made of a polyester resin (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Co., Ltd.) with one side treated with silicone and a thickness of 25 μm was attached to the surface of the obtained adhesive layer. Silicone treated surface to obtain a surface protective film (31). Aging was performed at normal temperature for 5 days, and evaluation was performed.

[Example 32] 80 parts by weight of urethane prepolymer A; 12 parts by weight of a polyol with 3 hydroxyl groups, namely PREMINOL S3011 (manufactured by Asahi Glass Co., Ltd., Mn=10000), as a polyol, and SANNIX as a polyol with 3 hydroxyl groups GP3000 (manufactured by Sanyo Chemical, Mn=3000) 8 parts by weight; 6.0 parts by weight of isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Company) as a crosslinking agent, MEGAFAC F-571 ( DIC Corporation) 0.5 parts by weight; 0.50 parts by weight of 1-ethyl-3-methylimidazolium tris(fluoromethylsulfonyl)imide (AS110, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) as an ionic compound; 0.5 parts by weight of Irganox 1010 (manufactured by BASF) as an antioxidant; 0.03 parts by weight of iron triacetylacetonate (manufactured by Nippon Chemical Industry Co., Ltd.) as a catalyst was diluted with ethyl acetate so that the overall solid content reached 50% by weight , to obtain a urethane-based adhesive solution. Then, the urethane-based adhesive solution was applied to a polyester resin base material (trade name "T100-75S", thickness 75 μm, Mitsubishi Chemical Co., Ltd. production), cured and dried at a drying temperature of 130° C. and a drying time of 3 minutes to produce an adhesive layer containing an adhesive composition. Next, a release liner made of a polyester resin (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Co., Ltd.) with one side treated with silicone and a thickness of 25 μm was attached to the surface of the obtained adhesive layer. Silicone treated surface to obtain a surface protective film (32). Aging was performed at normal temperature for 5 days, and evaluation was performed.

[Example 33] 60 parts by weight of urethane prepolymer A; 28 parts by weight of a polyol with 3 hydroxyl groups, that is, PREMINOL S3011 (manufactured by Asahi Glass Co., Ltd., Mn=10000), and a polyol with 3 hydroxyl groups, namely SANNIX 12 parts by weight of GP3000 (manufactured by Sanyo Chemical Industry Co., Ltd., Mn=3000); 8.0 parts by weight of isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Company) as a crosslinking agent; MEGAFAC F-571 ( DIC Corporation) 0.5 parts by weight; 0.50 parts by weight of 1-ethyl-3-methylimidazolium tris(fluoromethylsulfonyl)imide (AS110, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) as an ionic compound; 0.5 parts by weight of Irganox 1010 (manufactured by BASF) as an antioxidant; 0.03 parts by weight of iron triacetylacetonate (manufactured by Nippon Chemical Industry Co., Ltd.) as a catalyst was diluted with ethyl acetate so that the overall solid content reached 50% by weight , to obtain a urethane-based adhesive solution. Then, the urethane-based adhesive solution was applied to a polyester resin base material (trade name "T100-75S", thickness 75 μm, Mitsubishi Chemical Co., Ltd. production), cured and dried at a drying temperature of 130° C. and a drying time of 3 minutes to produce an adhesive layer containing an adhesive composition. Next, a release liner made of a polyester resin (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Co., Ltd.) with one side treated with silicone and a thickness of 25 μm was attached to the surface of the obtained adhesive layer. Silicone treated surface to obtain a surface protective film (33). Aging was performed at normal temperature for 5 days, and evaluation was performed.

[Example 34] 60 parts by weight of urethane prepolymer A; 25 parts by weight of a polyol having 3 hydroxyl groups, namely PREMINOL S3011 (manufactured by Asahi Glass Co., Ltd., Mn=10000), and 25 parts by weight of a polyol having 3 hydroxyl groups, namely SANNIX 15 parts by weight of GP3000 (manufactured by Sanyo Chemicals, Mn=3000); 8.6 parts by weight of isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Company) as a crosslinking agent; MEGAFAC F-571 ( DIC Corporation) 0.5 parts by weight; 0.50 parts by weight of 1-ethyl-3-methylimidazolium tris(fluoromethylsulfonyl)imide (AS110, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) as an ionic compound; 0.5 parts by weight of Irganox 1010 (manufactured by BASF) as an antioxidant; 0.03 parts by weight of iron triacetylacetonate (manufactured by Nippon Chemical Industry Co., Ltd.) as a catalyst was diluted with ethyl acetate so that the overall solid content reached 50% by weight , to obtain a urethane-based adhesive solution. Then, the urethane-based adhesive solution was applied to a polyester resin base material (trade name "T100-75S", thickness 75 μm, Mitsubishi Chemical Co., Ltd. production), cured and dried at a drying temperature of 130° C. and a drying time of 3 minutes to produce an adhesive layer containing an adhesive composition. Next, a release liner made of a polyester resin (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Co., Ltd.) with one side treated with silicone and a thickness of 25 μm was attached to the surface of the obtained adhesive layer. Silicone treated surface to obtain a surface protective film (34). Aging was performed at normal temperature for 5 days, and evaluation was performed.

[Example 35] 50 parts by weight of urethane prepolymer A; 30 parts by weight of a polyol with 3 hydroxyl groups, namely PREMINOL S3011 (manufactured by Asahi Glass Co., Mn=10000), as a polyol, and a polyol with 3 hydroxyl groups, namely SANNIX 20 parts by weight of GP4000 (manufactured by Sanyo Chemicals, Mn=4000); 8.7 parts by weight of an isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Company) as a crosslinking agent, MEGAFAC F-571 of a fluorine-based oligomer ( DIC Corporation) 0.5 parts by weight; 0.50 parts by weight of 1-ethyl-3-methylimidazolium tris(fluoromethylsulfonyl)imide (AS110, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) as an ionic compound; 0.5 parts by weight of Irganox 1010 (manufactured by BASF) as an antioxidant; 0.03 parts by weight of iron triacetylacetonate (manufactured by Nippon Chemical Industry Co., Ltd.) as a catalyst was diluted with ethyl acetate so that the overall solid content reached 50% by weight , to obtain a urethane-based adhesive solution. Then, the urethane-based adhesive solution was applied to a polyester resin base material (trade name "T100-75S", thickness 75 μm, Mitsubishi Chemical Co., Ltd. production), cured and dried at a drying temperature of 130° C. and a drying time of 3 minutes to produce an adhesive layer containing an adhesive composition. Next, a release liner made of a polyester resin (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Co., Ltd.) with one side treated with silicone and a thickness of 25 μm was attached to the surface of the obtained adhesive layer. Silicone treated surface to obtain a surface protective film (35). Aging was performed at normal temperature for 5 days, and evaluation was performed.

[Comparative example 1] 100 parts by weight of urethane prepolymer A; 3.2 parts by weight of isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Company) as a crosslinking agent; 0.5 parts by weight of Irganox 1010 (manufactured by BASF Corporation) as an antioxidant parts; 0.03 parts by weight of iron triacetylacetonate (manufactured by Nippon Chemical Industry Co., Ltd.) as a catalyst is diluted with ethyl acetate so that the overall solid content reaches 50% by weight to obtain a urethane-based adhesive solution. Then, the urethane-based adhesive solution was applied to a polyester resin base material (trade name "T100-75S", thickness 75 μm, Mitsubishi Chemical Co., Ltd. production), cured and dried at a drying temperature of 130° C. and a drying time of 3 minutes to produce an adhesive layer containing an adhesive composition. Next, a release liner made of a polyester resin (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Co., Ltd.) with one side treated with silicone and a thickness of 25 μm was attached to the surface of the obtained adhesive layer. Silicone treated surface to obtain a surface protective film (C1). Aging was performed at normal temperature for 5 days, and evaluation was performed.

[Comparative example 2] 100 parts by weight of urethane prepolymer B; 2.9 parts by weight of isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Company) as a crosslinking agent; 0.5 parts by weight of Irganox 1010 (manufactured by BASF Company) as an antioxidant parts; 0.03 parts by weight of iron triacetylacetonate (manufactured by Nippon Chemical Industry Co., Ltd.) as a catalyst is diluted with ethyl acetate so that the overall solid content reaches 50% by weight to obtain a urethane-based adhesive solution. Then, the urethane-based adhesive solution was applied to a polyester resin base material (trade name "T100-75S", thickness 75 μm, Mitsubishi Chemical Co., Ltd. production), cured and dried at a drying temperature of 130° C. and a drying time of 3 minutes to produce an adhesive layer containing an adhesive composition. Next, a release liner made of a polyester resin (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Co., Ltd.) with one side treated with silicone and a thickness of 25 μm was attached to the surface of the obtained adhesive layer. Silicone treated surface to obtain a surface protection film (C2). Aging was performed at normal temperature for 5 days, and evaluation was performed.

[Comparative example 3] 50 parts by weight of urethane prepolymer A; 35 parts by weight of a polyol having 3 hydroxyl groups, that is, PREMINOL S3011 (manufactured by Asahi Glass Co., Ltd., Mn=10000), and 35 parts by weight of a polyol having 3 hydroxyl groups, namely SANNIX 15 parts by weight of GP3000 (manufactured by Sanyo Chemicals, Mn=3000); 9.2 parts by weight of isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Company) as a crosslinking agent, MEGAFAC F-571 of fluorine-based oligomers ( DIC company manufacture) 0.5 weight part; Irganox1010 (BASF company manufacture) as antioxidant 0.5 weight part; As catalyst iron triacetyl acetonate (Nippon Chemical Industry Co., Ltd. manufacture) 0.03 weight part reaches 50 weight parts with the whole solid content % was diluted with ethyl acetate to obtain a urethane-based adhesive solution. Then, the urethane-based adhesive solution was applied to a polyester resin base material (trade name "T100-75S", thickness 75 μm, Mitsubishi Chemical Co., Ltd. production), cured and dried at a drying temperature of 130° C. and a drying time of 3 minutes to produce an adhesive layer containing an adhesive composition. Next, a release liner made of a polyester resin (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Co., Ltd.) with one side treated with silicone and a thickness of 25 μm was attached to the surface of the obtained adhesive layer. Silicone treated surface to obtain a surface protection film (C3). Aging was performed at normal temperature for 5 days, and evaluation was performed.

[Comparative example 4] 50 parts by weight of urethane prepolymer A; 30 parts by weight of a polyol with 3 hydroxyl groups, namely PREMINOL S3011 (manufactured by Asahi Glass Co., Mn=10000), as a polyol, and a polyol with 3 hydroxyl groups, namely SANNIX 20 parts by weight of GP3000 (manufactured by Sanyo Chemicals, Mn=3000); 10.1 parts by weight of isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Company) as a crosslinking agent; MEGAFAC F-571 ( DIC company manufacture) 0.5 weight part; Irganox1010 (BASF company manufacture) as antioxidant 0.5 weight part; As catalyst iron triacetyl acetonate (Nippon Chemical Industry Co., Ltd. manufacture) 0.03 weight part reaches 50 weight parts with the whole solid content % was diluted with ethyl acetate to obtain a urethane-based adhesive solution. Then, the urethane-based adhesive solution was applied to a polyester resin base material (trade name "T100-75S", thickness 75 μm, Mitsubishi Chemical Co., Ltd. production), cured and dried at a drying temperature of 130° C. and a drying time of 3 minutes to produce an adhesive layer containing an adhesive composition. Next, a release liner made of a polyester resin (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Co., Ltd.) with one side treated with silicone and a thickness of 25 μm was attached to the surface of the obtained adhesive layer. Silicone treated surface to obtain a surface protection film (C4). Aging was performed at normal temperature for 5 days, and evaluation was performed.

[Example 36-70] For each of the surface protection films obtained in Examples 1 to 35, the release liner was peeled off and attached to a polarizing plate (manufactured by Nitto Denko Co., Ltd., trade name "TEG1465DUHC") as an optical member to obtain a bonded product. Optical components of surface protection film.

[Example 71-105] For each of the surface protection films obtained in Examples 1 to 35, the release liner was peeled off and attached to a conductive film (manufactured by Nitto Denko Co., Ltd., trade name "ELECRYSTA V270L-TFMP") as an electronic component, An electronic component bonded with a surface protective film is obtained.

[Table 1] base polymer Urethane prepolymer Polyol Urethane prepolymer A [weight parts] Urethane prepolymer B [parts by weight] The first polyol (Mn=5,000~20,000) [parts by weight] Second polyol (Mn=300~4,999) [parts by weight] PTMG3000 (Mn=3,000) SANNIX GP-1500 (Mn=1,500) SANNIX PP-2000 (Mn=2,000) SANNIX GP-1000 (Mn=1,000) KURARAY POLYOL P-2010 PREMINOL S 3011 (Mn=10,000) SANNIX GP-4000 (Mn=4,000) SANNIX GP-3000 (Mn=3,000) PTGL3000 (Mn=3,000) 80% by weight 20% by weight 45% by weight 45% by weight 10% by weight - - - - Example 1 100 - - - - - Example 2 - 100 - - - - Example 3 - 95 3 - - 2 Example 4 95 - 3.5 - 1.5 - Example 5 95 - 3 - 2 - Example 6 80 - 12 - 8 - Example 7 60 - 28 - 12 - Example 8 60 - 25 - 15 - Example 9 50 - 30 20 - - Example 10 100 - - - - - Example 11 - 100 - - - - Example 12 - 95 3 - - 2 Example 13 95 - 3.5 - 1.5 - Example 14 95 - 3 - 2 - Example 15 80 - 12 - 8 - Example 16 60 - 28 - 12 - Example 17 60 - 25 - 15 - Example 18 50 - 30 20 - - Example 19 100 - - - - - Example 20 - 100 - - - - Example 21 100 - - - - - Example 22 - 100 - - - - Example 23 100 - - - - - Example 24 100 - - - - - Example 25 100 - - - - - Example 26 100 - - - - - Example 27 100 - - - - - Example 28 100 - - - - - Example 29 100 - - - - - Example 30 95 - 3.5 - 1.5 - Example 31 95 - 3 - 2 - Example 32 80 - 12 - 8 - Example 33 60 - 28 - 12 - Example 34 60 - 25 - 15 - Example 35 50 - 30 20 - - Comparative example 1 100 - - - - - Comparative example 2 - 100 - - - - Comparative example 3 50 - 35 - 15 - Comparative example 4 50 - 30 - 20 - [Table 2] Urethane polymer: polyol (weight ratio) Weight ratio of 1st polyol to 2nd polyol (1st polyol/2nd polyol) Crosslinking agent [weight part] Ratio of hydroxyl group to 100 g of base polymer [mmol] [NCO] /[OH] ionic compound Fluorine compounds type Blending amount [parts by weight] type Blending amount [parts by weight] C/HX Example 1 100:0 - 3.2 11 1.5 - - F-571 0.5 Example 2 100:0 - 2.9 10 1.5 - - F-571 0.5 Example 3 95:5 1.5 3.7 12 1.5 - - F-571 0.5 Example 4 95:5 2.3 3.8 13 1.5 - - F-571 0.5 Example 5 95:5 1.5 3.9 13 1.5 - - F-571 0.5 Example 6 80:20 1.5 6.0 20 1.5 - - F-571 0.5 Example 7 60:40 2.3 8.0 27 1.5 - - F-571 0.5 Example 8 60:40 1.7 8.6 29 1.5 - - F-571 0.5 Example 9 50:50 1.5 8.7 29 1.5 - - F-571 0.5 Example 10 100:0 - 3.2 11 1.5 - - F-563 0.5 Example 11 100:0 - 2.9 10 1.5 - - F-563 0.5 Example 12 95:5 1.5 3.7 12 1.5 - - F-563 0.5 Example 13 95:5 2.3 3.8 13 1.5 - - F-563 0.5 Example 14 95:5 1.5 3.9 13 1.5 - - F-563 0.5 Example 15 80:20 1.5 6.0 20 1.5 - - F-563 0.5 Example 16 60:40 2.3 8.0 27 1.5 - - F-563 0.5 Example 17 60:40 1.7 8.6 29 1.5 - - F-563 0.5 Example 18 50:50 1.5 8.7 29 1.5 - - F-563 0.5 Example 19 100:0 - 3.2 11 1.5 - - F-477 0.5 Example 20 100:0 - 2.9 10 1.5 - - F-477 0.5 Example 21 100:0 - 3.2 11 1.5 - - F-251 0.5 Example 22 100:0 - 2.9 10 1.5 - - F-251 0.5 Example 23 100:0 - 3.2 11 1.5 AS110 0.05 F-571 0.5 Example 24 100:0 - 3.2 11 1.5 AS110 0.10 F-571 0.5 Example 25 100:0 - 3.2 11 1.5 AS110 0.50 F-571 0.5 Example 26 100:0 - 3.2 11 1.5 AS110 1.00 F-571 0.5 Example 27 100:0 - 3.2 11 1.5 AS110 0.50 F-251 0.5 Example 28 100:0 - 3.2 11 1.5 AS110 0.50 F-477 0.5 Example 29 100:0 - 3.2 11 1.5 AS110 0.50 F-251 0.5 Example 30 95:5 2.3 3.8 13 1.5 AS110 0.50 F-571 0.5 Example 31 95:5 1.5 3.9 13 1.5 AS110 0.50 F-571 0.5 Example 32 80:20 1.5 6.0 20 1.5 AS110 0.50 F-571 0.5 Example 33 60:40 2.3 8.0 27 1.5 AS110 0.50 F-571 0.5 Example 34 60:40 1.7 8.6 29 1.5 AS110 0.50 F-571 0.5 Example 35 50:50 1.5 8.7 29 1.5 AS110 0.50 F-571 0.5 Comparative example 1 100:0 - 3.2 11 1.5 - - - - Comparative example 2 100:0 - 2.9 10 1.5 - - - - Comparative example 3 50:50 2.3 9.2 31 1.5 - - F-571 0.5 Comparative example 4 50:50 1.5 10.1 34 1.5 - - F-571 0.5 [table 3] Evaluation of black dots [piece/100 cm ² ] Adhesion to glass [gf/25 mm] Peeling static voltage for glass [kV] (absolute value) Haze[%] Smudge evaluation Example 1 0 2.3 10.5 0.4 ○ Example 2 0 3.1 10.2 0.6 ○ Example 3 0 2.8 10.2 0.6 ○ Example 4 0 2.2 11.7 3.8 ○ Example 5 0 2.2 12.5 2.2 ○ Example 6 0 2.1 12.4 2.2 ○ Example 7 0 2.2 12.0 4.0 x Example 8 0 2.1 11.4 2.0 x Example 9 0 2.1 12.0 1.6 x Example 10 2 2.5 10.1 0.4 ○ Example 11 2 3.4 9.9 0.6 ○ Example 12 2 2.9 9.9 0.6 ○ Example 13 2 2.4 11.3 3.8 ○ Example 14 2 2.4 12.1 2.2 ○ Example 15 3 2.3 11.9 2.2 ○ Example 16 4 2.4 11.5 4.0 x Example 17 4 2.3 11.0 2.0 x Example 18 4 2.2 11.6 1.6 x Example 19 0 2.9 10.2 0.4 ○ Example 20 0 3.8 9.9 0.6 ○ Example 21 3 2.9 10.7 0.4 ○ Example 22 3 4.0 10.5 0.6 ○ Example 23 0 2.2 1.3 0.4 ○ Example 24 0 2.1 1.0 0.4 ○ Example 25 0 2.0 0.6 0.4 ○ Example 26 0 1.9 0.5 0.4 ○ Example 27 2 2.3 0.7 0.4 ○ Example 28 0 2.6 0.4 0.4 ○ Example 29 3 2.7 0.8 0.4 ○ Example 30 0 1.9 0.4 3.8 ○ Example 31 0 1.9 0.5 2.2 ○ Example 32 0 1.8 0.3 2.2 ○ Example 33 0 1.8 0.4 4.0 x Example 34 0 1.7 0.5 2.0 x Example 35 0 1.7 0.5 1.6 x Comparative example 1 0 6.1 10.1 0.4 ○ Comparative example 2 0 6.4 9.8 0.6 ○ Comparative example 3 5 1.2 11.4 3.6 x Comparative example 4 6 1.1 11.6 1.6 x [Industrial availability]

The surface protection film of the present invention can be used for any appropriate purpose. Preferably, the surface protection film of the present invention can be preferably used for surface protection of optical members or electronic members.

1: Substrate layer 2: Adhesive layer 10: Surface protection film

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

1: Substrate layer

2: Adhesive layer

10: Surface protection film

Claims (11)

A surface protection film comprising an adhesive layer, The adhesive layer includes a urethane-based adhesive formed from a urethane-based adhesive composition, The urethane-based adhesive composition includes a base polymer and a fluorine-based compound, The base polymer comprises a urethane prepolymer, The ratio of the hydroxyl groups contained in the urethane-based adhesive composition is less than 30 mmol with respect to 100 g of the base polymer. The surface protection film as claimed in claim 1, wherein the above-mentioned base polymer comprises a polyoxyalkylene structure represented by general formula (1), [Chem. 1]

(In general formula (1), R ¹ represents one species selected from the group consisting of a hydrogen atom, an alkyl group with 1 to 4 carbons, and a hydroxyalkyl group with 1 to 6 carbons; a plurality of R ^1s may mutually be The same or different; n represents an integer of 1 to 4; m represents an integer of 1 to 200). The surface protection film according to claim 2, wherein the above-mentioned urethane prepolymer comprises a polyoxyalkylene structure represented by the above-mentioned general formula (1). The surface protection film according to any one of claims 1 to 3, wherein the above-mentioned base polymer comprises polyol, which is not a urethane prepolymer. The surface protection film as claimed in item 4, wherein the above-mentioned polyhydric alcohol comprises a polyoxyalkylene structure represented by general formula (1), [Chemical 2]

(In general formula (1), R ¹ represents one species selected from the group consisting of a hydrogen atom, an alkyl group with 1 to 4 carbons, and a hydroxyalkyl group with 1 to 6 carbons; a plurality of R ^1s may mutually be The same or different; n represents an integer of 1 to 4; m represents an integer of 1 to 200). The surface protection film according to claim 4 or 5, wherein the content ratio of the above-mentioned urethane prepolymer to the above-mentioned polyol in the above-mentioned urethane-based adhesive composition is calculated by weight ratio, urethane Ester prepolymer:polyol=70:30～100:0. The surface protection film according to any one of claims 1 to 6, wherein the haze of the adhesive layer is 3.5% or less. The surface protection film according to any one of claims 1 to 7, wherein the surface tension of the above-mentioned fluorine-based compound when prepared as a 0.1% propylene glycol monomethyl ether solution is 23 mN/m or more. The surface protection film according to any one of claims 1 to 8, wherein the urethane-based adhesive composition contains 0.05 parts by weight or more of an ionic compound relative to 100 parts by weight of the base polymer. An optical member bonded with the surface protection film according to any one of claims 1 to 9. An electronic component, which is bonded with the surface protection film according to any one of claims 1 to 9.

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