JP6500379B2 - Surface protective film - Google Patents

Description

  The present invention relates to a surface protective film.

  Conventionally, in various fields, a surface protective film is provided on the surface from the viewpoint of suppressing scratching on the surface.

  Here, in Patent Document 1, the release layer provided on the outermost surface of the heat fixing member is formed of a mixture of a fluororubber and a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, and the release layer is A fixing device is disclosed in which the contact angle to water is adjusted within the range of 80 ° to 103 °.

  Further, Patent Document 2 describes a fixing member for an electrophotographic image forming apparatus, wherein a toner releasing layer is provided on the surface of the fixing member, and the toner releasing layer is mainly contained in the molecule as a main component. A fixing member is disclosed which contains a fluororubber having an ether bond and further contains a polysiloxane surfactant having a polyether structure.

  Further, according to Patent Document 3, in the fixing roller formed by forming a fluorocarbon resin layer on the outer surface of a roller-like substrate via a rubber layer, the fluorocarbon resin layer has (A) a tetramer having an average particle diameter of 1 to 15 μm. It is formed by a fluorocarbon resin mixture containing 20 to 97% by weight of fluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA) and 3 to 80% by weight of (B) polytetrafluoroethylene (PTFE) having an average particle diameter of 1 μm or less A fuser roller is disclosed.

  Further, Patent Document 4 discloses a fixing roll comprising a base material and a fluororubber surface layer obtained by crosslinking a crosslinkable composition containing a fluororubber (A) and a fluorocarbon resin (B). It is done.

  Further, according to Patent Document 5, in a fixing device having a heat fixing member and a pressure fixing member pressed against the heat fixing member, the heat fixing member is a fluoroelastomer in which carbon black subjected to surface oxidation treatment is dispersed. A fixing device is disclosed that includes an oil supply unit that includes at least a surface layer and applies dimethyl silicone oil having a unsaturated bond to the surface of the heat fixing member.

Japanese Patent Application Laid-Open No. 10-26896 JP 2007-58197 A Japanese Patent Application Laid-Open No. 10-142990 JP, 2013-20025, A JP, 2005-157173, A

  An object of the present invention is to provide a surface protection film having excellent releasability.

The above object is achieved by the present invention described below.
That is, the invention according to < 1 > is
A structure in which a fluorine resin having a perfluoroalkylene ether structure in its main chain is crosslinked and polymerized,
At least one structure selected from the group consisting of a silicone structure represented by the following general formula (S) and an alkylene structure having 5 to 20 carbon atoms,
And a surface protection film containing a crosslinked polymer.

(In the general formula (S), R ^S1 and R ^S2 each independently represent -CH ₃ , -CF ₃ or a hydrogen atom.)

The invention pertaining to < 2 > is
It is a surface protective film as described in < 1 > which has at least 1 type of structure in which the said perfluoro alkylene ether structure is selected from the structure represented by the following general formula (F).

(In the general formula ^(F), representing the ^{R F1} and ^{R F2} fluorine atom or -CF ₃ each independently. ^However, .N1 never both ^{R F1} and ^{R F2} is a fluorine atom 1 to 5 N2 represents an integer of 0 or more and 2 or less, and the total number of n1 and n2 is 5 or less.)

The invention relating to < 3 > is
The crosslinked polymer is in a position corresponding to the ends of the main chain of the fluorine resin, acryloyl group _{(CH 2 = CH-CO-)} , methacryloyl group _{(CH 2 = C (CH 3} ) -CO-), an epoxy group , a hydroxyl group, an amino group, an ester group, a carboxyl group, a thiol group, and is selected from the functional groups consisting of trialkoxysilyl group having a modified structure modifying group containing at least one functional group <1> or < It is a surface protective film as described in 2 > .

The invention pertaining to < 4 > is
It is a surface protection film as described in < 3 > in which the said crosslinked polymer has at least 1 type of structure selected from the group which consists of said silicone structure and said alkylene structure in the position corresponding to the said modification group.

The invention pertaining to < 5 > is
The cross-linked polymer has at least one structure selected from the group consisting of the silicone structure and the alkylene structure at a position corresponding to the modifying group, and is selected from the functional group group included in the modifying group It is a surface protection film as described in < 3 > which has a structure which the compound which has a group which can react to at least one functional group, and this functional group.

According to the invention relating to < 1 > , < 2 > , < 3 > , < 4 > and < 5 > , a cross-linked polymer of only a fluorocarbon resin having a perfluoroalkylene ether structure in its main chain or the fluorocarbon resin and silicone structure And the surface protective film provided with the outstanding releasability compared with the case of being a surface protective film by a crosslinked polymer with a polyfunctional which does not have any of C5 or more and 20 or less alkylene structure is provided.

It is a perspective view showing a schematic structure of an endless belt concerning this embodiment. It is a sectional view of an endless belt concerning this embodiment. It is a schematic block diagram which shows the image forming apparatus using the endless belt which concerns on this embodiment. FIG. 1 is a schematic configuration view showing an image fixing device using an endless belt according to the present embodiment.

  Hereinafter, embodiments of the surface protective film will be described in detail.

  The surface protective film according to the present embodiment has a structure in which a fluorine resin having a perfluoroalkylene ether structure in its main chain is crosslinked and polymerized, a silicone structure represented by the following general formula (S), and an alkylene having 5 to 20 carbon atoms. And a crosslinked polymer having at least one structure selected from the group consisting of structures.

(In the general formula (S), R ^S1 and R ^S2 each independently represent -CH ₃ , -CF ₃ or a hydrogen atom.)

In recent years, providing a surface protective film has been performed in various fields from the viewpoint of suppressing scratching on the surface. In the surface protective film, in addition to scratch resistance, surface slippage may be required from the viewpoint of surface antifouling properties.
On the other hand, the surface protective film according to the present embodiment is excellent in that it further has at least one of a silicone structure and an alkylene structure in addition to a structure in which a fluorine resin having a perfluoroalkylene ether structure in its main chain is crosslinked and polymerized. It has scratch resistance and surface slip resistance.

[Composition of surface protective film]
Next, the crosslinked polymer contained in the surface protective film according to the present embodiment will be described.
The crosslinked polymer in the present embodiment has a structure in which a fluororesin having a perfluoroalkylene ether structure in its main chain is crosslinked and polymerized. The method for introducing the silicone structure represented by the general formula (S) and the crosslinked polymer having an alkylene structure having 5 to 20 carbon atoms is not particularly limited. For example, the following methods may be mentioned. Be

  (I) A method of reacting with a crosslinking group at the time of crosslinking polymerization: namely, carrying out a crosslinking polymerization using a fluorine resin having a perfluoroalkylene ether structure in the main chain and having a reactive group (reactive crosslinking group) at the end In this case, there is mentioned a method of adding at least one of a silicone compound and an alkylene compound having one or two or more groups capable of binding to the reactive group to introduce at least one of the silicone structure and the alkylene structure. In addition, when the said silicone compound and an alkylene compound have 2 or more groups which can couple | bond with the said reactive group, it also functions as a crosslinking agent which carries out the crosslinking of fluorocarbons.

  By synthesizing a crosslinked polymer by the method of (I) above, it has at least one of the silicone structure and the alkylene structure at the end of the fluorocarbon resin (position corresponding to the position modified by the modifying group) A crosslinked polymer having a structure in which the compound having a group capable of reacting with the functional group contained in the modifying group and the functional group are obtained.

  (II) A method in which crosslinking polymerization is carried out after being introduced into a fluorine resin in advance: That is, the above-mentioned fluorine resin having a perfluoroalkylene ether structure in the main chain is reacted with at least one of a silicone compound and an alkylene compound in advance. The method of introduce | transducing at least one of a silicone structure and the said alkylene structure, and carrying out the crosslinking polymerization of fluorocarbons on it is mentioned.

  A crosslinked polymer having at least one of the silicone structure and the alkylene structure at an end of the fluorocarbon resin (a position corresponding to a position modified by a modifying group) by synthesizing the crosslinked polymer by the method of (II). Is obtained.

  Hereinafter, the methods (I) and (II) will be described.

(I) A method of reacting with a crosslinking group at the time of crosslinking polymerization: At least one of the silicone structure and the alkylene structure is contained at the terminal of the fluorocarbon resin (position corresponding to the position modified by the modifying group) and contained in the modifying group. A crosslinked polymer having a structure in which a compound having a group capable of reacting with a functional group, and the functional group react with each other, and a method of obtaining the crosslinked polymer (the method of the above (I)) will be described.

(Fluororesin)
In the present embodiment, examples of the perfluoroalkylene ether structure in the crosslinked polymer include a structure represented by the following general formula (F).

(In the general formula ^(F), representing the ^{R F1} and ^{R F2} fluorine atom or -CF ₃ each independently. ^However, .N1 never both ^{R F1} and ^{R F2} is a fluorine atom 1 to 5 N2 represents an integer of 0 or more and 2 or less, and the total number of n1 and n2 is 5 or less.)

  In addition, a fluorine resin having a perfluoroalkylene ether structure in its main chain and having a reactive group (reactive crosslinking group) at its terminal (hereinafter simply referred to as “perfluoroalkylene ether-containing compound”) to be subjected to the above-mentioned crosslinking polymerization is also used. Examples of the compound) include compounds represented by the following general formula (1).

(In the above general formula (1), R ¹ and R ² each independently represent a fluorine atom or —CF ₃ (trifluoromethyl group), provided that both of R ¹ and R ² are a fluorine atom Absent.
n1 represents an integer of 1 or more and 5 or less, n2 represents an integer of 0 or more and 2 or less, and the total number of n1 and n2 is 5 or less. m represents an integer of 1 or more.
A ¹ and A ² each independently represent a divalent group represented by the following general formula (2).
B ¹ and ^{B 2} represents a divalent radical selected from the group consisting of a single bond and the following (B-1) to (B-3) independently.
X ¹ and X ² each independently represent a monovalent group having at least one reactive crosslinking group selected from the group consisting of (X-1) to (X-8) below. )

(In the above general formula (2), R ³ and R ⁴ each independently represent a fluorine atom or a trifluoromethyl group. However, neither R ³ nor R ⁴ is a fluorine atom.
n3 represents an integer of 0 to 5, n4 represents an integer of 0 to 2, n5 represents an integer of 0 or more, n6 represents 0 or 1, and n7 represents an integer of 0 or more. However, n3, n4, n5 and n6 can not all be zero.
Incidentally, the divalent group represented by the general formula (2) bonded to perfluoroalkylene ether structure (* 1) portion, (* 2) part ^(-O-B 1 -X ¹⁾ or ( ^{-O-B 2} -X 2) to bind. )

((B-1) to (B-3) respectively bind to X ¹ or X ² in the (# 2) portion, and (-O-A ¹ ...) Or (-O in the (# 1) portion -A ² ...) combined with the side))

(R ^X1 in (X-1) represents a hydrogen atom, a methyl group or a trifluoromethyl group. R ^X2 in (X-6) represents a hydrogen atom or an alkyl group. (X-8) R ^X3 in represents an alkyl group)

Perfluoroalkylene Ether Structure Part First, the general formula (1) has a perfluoroalkylene ether structure part surrounded by [] _m . In this perfluoroalkylene ether structural moiety, R ¹ and R ² each independently represent a fluorine atom or a trifluoromethyl group. However, neither R ¹ nor R ² is a fluorine atom.
n1 represents an integer of 1 or more and 5 or less, n2 represents an integer of 0 or more and 2 or less, and the total number of n1 and n2 is 5 or less. n1 is more preferably 1 or more and 3 or less, n2 is more preferably 0 or more and 1 or less, and the total of n1 and n2 is preferably 1 or more and 3 or less.

M, which is the number of [] surrounding the perfluoroalkylene ether structural moiety, represents an integer of 1 or more. The plurality of perfluoroalkylene ether structures (-(CF ₂ ) _n ^1- (C (R ¹ ) (R ² )) _{n 2} -O-) in the case where m is 2 or more are different even though they have the same structure It may be a structure. m is further preferably 2 or more and 100 or less, and more preferably 5 or more and 50 or less.

Specific examples of the perfluoroalkylene ether structural moiety ([-(CF ₂ ) _n ^1- (C (R ¹ ) (R ² )) _{n 2} -O-] _m ) include, for example, the following (m-1) to (m-) The structure of 8) is mentioned. In addition, m1 and m2 shown by (m-2), (m-3), and (m-4) each independently represent an integer of 1 or more, and the total number of m1 and m2 is m.

  Among the structures of (m-1) to (m-8), the structures of (m-2), (m-6), (m-7) and (m-8) are preferable, and (m-) The structure of 2) is more preferable.

・ A ¹ and A ²
In Formula (1), A ¹ and A ² each independently represent a divalent group represented by Formula (2).

In the above general formula (2), R ³ and R ⁴ each independently represent a fluorine atom or a trifluoromethyl group. However, neither R ³ nor R ⁴ is a fluorine atom.
n3 represents an integer of 0 to 5, n4 represents an integer of 0 to 2, n5 represents an integer of 0 or more, n6 represents 0 or 1, and n7 represents an integer of 0 or more. However, n3, n4, n5 and n6 can not all be zero.
Incidentally, the divalent group represented by the general formula (2) bonded to perfluoroalkylene ether structure (* 1) portion, (* 2) part ^(-O-B 1 -X ¹⁾ or ( ^{-O-B 2} -X 2) to bind.

  In the general formula (2), the total number of n5 and n6 is preferably 2 or less, and more preferably 1 or less.

  The preferred structure of the divalent group represented by the above general formula (2) is shown below.

In the above (A-6), o represents an integer of 1 or more, preferably 1 or more and 50 or less, and more preferably 1 or more and 20 or less.

  Among the structures of (A-1) to (A-12), particularly, (A-1), (A-2), (A-3), (A-6), (A-8), The structures of (A-11) and (A-12) are more preferable.

・ B ¹ and B ²
In General Formula (1), B ¹ and B ² each independently represent a single bond and a divalent group selected from the group consisting of (B-1) to (B-3) below.

The (B-1) to (B-3) respectively bind to X ¹ or X ² in the (# 2) portion, and (-O-A ¹ ...) Or (-O-) in the (# 1) portion A ² ...) It joins with the side.

As the ^{B 1} and ^{B 2} Among the groups, more preferably the structure of the particular (B-1).

・ X ¹ and X ²
In the general formula (1), X ¹ and X ^{2 each} represent a monovalent group having at least one reactive crosslinking group selected from the group consisting of (X-1) to (X-8) below: Represent.

In addition, when said B ¹ (or B ² ) is said (B-2) or (B-3), X ¹ (or X ² ) is a crosslinking group in which B ¹ (or B ² ) is reactive. In the case of having at least one reactive crosslinking group selected from the group consisting of (X-1) to (X-8), it is preferable to have one or more.
On the other hand, when said B ¹ (or B ² ) is a single bond or said (B-1), that is, when B ¹ (or B ² ) does not have a reactive crosslinking group, said (X-1) It is preferable to have 2 or more of at least 1 sort of reactive crosslinking group selected from the group which consists of) to (X-8).
That is, in the general formula (1), each of ^-B 1 -X ¹ portion and ^-B 2 -X ² moiety, the reactivity of the crosslinking group it is preferred to have two or more. When X ¹ , X ² and B ¹ , B ² satisfy this configuration, a crosslinked product obtained by cross-linking polymerizing this compound, starting from -B ¹ -X ¹ , -B ² -X ² , in general A structure is obtained in which at least three of the groups of the structure excluding X ¹ (or X ² ) from the formula (1) are cross-linked and polymerized.

R ^X1 in the above (X-1) represents a hydrogen atom (that is, a crosslinking group = an acryloyl group), a methyl group (that is, a crosslinking group = a methacryloyl group), or a trifluoromethyl group.
Among the above, a hydrogen atom and a trifluoromethyl group are more preferable as R ^X1 .

  The crosslinking group represented by (X-3) represents an epoxy group, the crosslinking group represented by (X-4) represents a hydroxyl group, and the crosslinking group represented by (X-5) represents an amino group.

R ^X2 in the above (X-6) represents a hydrogen atom (that is, a crosslinking group = carboxy group), or an alkyl group (that is, a crosslinking group = an ester group).
The alkyl group represented by R ^X2 in (X-6) is preferably one having 1 to 18 carbon atoms, and more preferably one having 1 to 4 carbon atoms.
The alkyl group represented by R ^X2 may be linear, molecular chain or cyclic, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and n- And pentyl, cyclopentyl, n-hexyl, cycloexyl, 2-ethylhexyl, lauryl, stearyl and the like.
Among the above, methyl, ethyl, n-propyl, isopropyl, n-butyl and isobutyl are more preferable as R ^X2 .

  The crosslinking group represented by the above (X-7) represents a thiol group.

R ^X3 in the above (X-8) represents an alkyl group (that is, a crosslinking group = trialkoxysilyl group).
The alkyl group represented by R ^X3 in (X-8) is preferably one having 1 to 10 carbon atoms, and more preferably one having 1 to 4 carbon atoms.
The alkyl group represented by R ^X3 may be linear, molecular or cyclic, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and n- And pentyl, cyclopentyl, n-hexyl, cyclohexyl, 2-ethylhexyl, lauryl, stearyl and the like.
Among the above, methyl, ethyl, n-propyl, isopropyl, n-butyl and isobutyl are more preferable as R ^X3 .

Among the structures of (X-1) to (X-8) above, the reactive crosslinking group possessed by X ¹ and X ² is, in particular, (X-1), (X-2), (X-3) , (X-5) and (X-6) (X-8) are preferable, and further (X-1), (X-2), (X-3) and (X-8) are more preferable. .

The number of reactive crosslinking groups that X ¹ and X ² have is preferably 1 or more and 20 or less, and more preferably 2 or more and 10 or less.

In X ¹ and X ² , another linking group may be present between one or more reactive crosslinking groups and a point of bonding to B ¹ (or B ² ). That is, X ¹ and X ² may be composed of one or more reactive crosslinking groups and another divalent or higher linking group.

The linking group possessed by X ¹ and X ² is a divalent or higher valent organic group, such as an alkyl chain, an aromatic chain, an ether group (—O—), a carbonyl group (—CO—), an ester group (—CO—O) The organic group of 2 or more valences which consists of the structure which combined 1 type of chain | strands or 2 or more types of chain | strands selected from-) is mentioned.

As a specific example of the said coupling group, the organic group of the following (1) thru | or (7) is mentioned, for example. In the following specific examples of the linking group, the * part binds to B ¹ or B ² and the # part binds to the reactive crosslinking group.

Here, specific examples of X ¹ and X ² are shown below.
First, the following (X-1a) to (X-1f) may be mentioned as examples having the crosslinking group (X-1) as the reactive crosslinking group. Incidentally, ^{R X1} in the following (X-1a) to (X-1f) has the same meaning as ^{R X1} in the (X1).

  Moreover, following (X-2a) thru | or (X-2 f) are mentioned as an example which has a crosslinking group of said (X-2) as a reactive crosslinking group.

  Similarly, as an example having the crosslinking group of (X-3) to (X-8) as the reactive crosslinking group, in the "#" part of the linking group represented by the above (1) to (7) The monovalent group which the bridge | crosslinking group of said (X-3) thru | or (X-8) couple | bonded is mentioned.

-Specific example of fluorine resin Here, the specific example of the fluorine resin (perfluoro alkylene ether containing compound) represented by the said General formula (1) is shown. However, the fluorine resin (perfluoro alkylene ether containing compound) in this embodiment is not limited to the following example.

Method of Synthesizing Fluorine Resin Next, an example of a method of synthesizing the fluorine resin (perfluoroalkylene ether-containing compound) represented by the general formula (1) will be described. In addition, the method of synthesize | combining the fluorine resin (perfluoro alkylene ether containing compound) used for the method of said (I) is not limited to the following method.

For example, in the case of synthesizing a compound having a divalent group represented by (B-1) as B ¹ and B ² in the general formula (1), as shown in the following synthesis scheme, the terminal of X ^* A compound having an OH group (where X ^* represents X ¹ or X ² in the general formula (1)) and a succinic anhydride to synthesize an intermediate, and this intermediate and the general formula (1) by reacting a compound having an OH group on the outside of the a ¹ and a ^2, perfluoroalkylene ether-containing compound represented by the general formula (1) is synthesized in the.

When a compound having a divalent group represented by (B-2) and (B-3) as B ¹ and B ² is synthesized, the succinic anhydride in the above synthesis scheme is itaconic anhydride. Or synthetic by replacing with maleic anhydride.

In addition, in the case of synthesizing a compound in which B ¹ and B ² have a single bond, the step of obtaining the intermediate by reacting the compound represented by X ^* -OH with succinic anhydride is not carried out, and X ^* The compound can be synthesized by directly reacting —OH with a compound having an OH group outside of A ¹ and A ² in General Formula (1).

Polyfunctional Compound The perfluoroalkylene ether structure in the crosslinked polymer has a perfluoroalkylene ether structure represented by the general formula (1) in its main chain and has a reactive crosslinking group at its terminal. You may form by carrying out the cross-linking polymerization of fluorine resin (perfluoro alkylene ether containing compound), and also in the case of this cross-linking polymerization, you may add the other reactive polyfunctional compound more than bifunctional.
Specific examples of the reactive polyfunctional compound include polyfunctional acrylates having the following structures.
· Tris (2-acryloxyethyl) Isocyanate of the following structure: ethoxylated isocyanuric acid triacrylate (AEICN)
-Pentaerythritol Triacrylate of the following structure: pentaerythritol triacrylate (A-TMM)
-Tetramethylol Methane Tetraacrylate of the following structure: pentaerythritol tetraacrylate (PETA)

(Silicone compounds and alkylene compounds)
In the method of reacting with a crosslinking group at the time of (I) crosslinking polymerization described above, a fluorocarbon resin (perfluoroalkylene ether-containing compound) having a perfluoroalkylene ether structure in the main chain and having a reactive group (reactive crosslinking group) at the end In the crosslinking polymerization using the compound), at least one of a silicone compound and an alkylene compound having one or more groups capable of binding to the reactive group is added, and at least one of the silicone structure and the alkylene structure Introduce one.
In addition, when the said silicone compound and an alkylene compound have 2 or more groups which can couple | bond with the said reactive group, it also functions as a crosslinking agent which carries out the crosslinking of fluorocarbons.

-Silicone compound Specifically, the silicone compound used for the method of said (I) has a structure of following General formula (S), and the said reactive group which the said fluororesin (perfluoro alkylene ether containing compound) has. It is a compound having a group capable of binding to (reactive crosslinking group).

(In the general formula (S), R ^S1 and R ^S2 each independently represent -CH ₃ , -CF ₃ or a hydrogen atom.)

  As a silicone compound used for the method of said (I), the compound represented by the following general formula (Sk1) which has the group which can couple | bond with a reactive group only in one terminal, and the group which can couple | bond with a reactive group The compound represented by the following general formula (Sk2) having at both ends is preferable.

(In the general formula (Sk1) and ^{(Sk2), R S1} and ^{R S2} each has the same meaning as ^{R S1} and ^{R S2} in the general formula (S) ^{.R S3} is a single _bond, C _{X H 2X (X} is 1 or more R ^S4 represents -CH ₃ , -CF ₃ , or a hydrogen atom, ns represents an integer of 1 or more (more preferably an integer of 1 to 500, still more preferably an integer of 1 to 200) X ³ represents a group capable of binding to a reactive group (reactive crosslinking group) of the fluorocarbon resin (perfluoroalkylene ether-containing compound).

When the fluorocarbon resin (perfluoroalkylene ether-containing compound) has at least one of the (X-1) (acryloyl group, methacryloyl group, etc.) and (X-2) as a reactive group, the reactive group which the silicone compound has the group (X ³⁾ capable of binding to, include a group having a carbon = carbon double bonds, and specific examples thereof include the same groups as the (X-1) and (X-2). That is, compounds represented by the following formulas (Sk1-1), (Sk2-1), (Sk1-2) and (Sk2-2) can be mentioned.

(In general formulas (Sk1-1), (Sk2-1), (Sk1-2) and (Sk2-2), R ^S1 , R ^S2 , R ^S3 , R ^S4 and ns are general formulas (Sk1) and (Sk2) And R ^X1 has the same ^{meaning as} that of the general formula (X-1).

When the fluorine resin (perfluoroalkylene ether-containing compound) has the (X-3) (epoxy group) as a reactive group, a group (X ³ ) which can be bonded to the reactive group of the silicone compound is a hydroxyl group And carboxyl group, trialkoxysilyl group, epoxy group, amino group, thiol group and vinyl group.

When the fluorine resin (perfluoroalkylene ether-containing compound) has the (X-4) (hydroxyl group) as a reactive group, the group (X ³ ) which can be bonded to the reactive group of the silicone compound is a hydroxyl group Examples thereof include a carboxyl group, a trialkoxysilyl group, an epoxy group, an amino group, a thiol group and a vinyl group.

When the fluorine resin (perfluoroalkylene ether-containing compound) has the (X-5) (amino group) as a reactive group, the group (X ³ ) which can be bonded to the reactive group of the silicone compound is a hydroxyl group And carboxyl group, trialkoxysilyl group, epoxy group, amino group, thiol group and vinyl group.

When the fluorine resin (perfluoroalkylene ether-containing compound) has the (X-6) (carboxy group, ester group, etc.) as a reactive group, a group (X ³ ) capable of binding to the reactive group of the silicone compound Examples thereof include a hydroxyl group, a carboxyl group, a trialkoxysilyl group, an epoxy group, an amino group, a thiol group and a vinyl group.

When the fluorine resin (perfluoroalkylene ether-containing compound) has the (X-7) (thiol group) as a reactive group, a group (X ³ ) capable of binding to the reactive group of the silicone compound is a hydroxyl group And carboxyl group, trialkoxysilyl group, epoxy group, amino group, thiol group and vinyl group.

When the fluorine resin (perfluoroalkylene ether-containing compound) has the (X-8) (trialkoxysilyl group) as a reactive group, the group (X ³ ) which can be bonded to the reactive group of the silicone compound is And a hydroxyl group, a carboxyl group, a trialkoxysilyl group, an epoxy group, an amino group, a thiol group and a vinyl group.

  Among the silicone compounds listed above, as the silicone compound used in the method (I), those represented by the general formulas (Sk1-1), (Sk2-1), (Sk1-2) and (Sk2-2) can be used. The compound represented is preferable, the compound represented by said general formula (Sk2-1) and (Sk2-2) is more preferable, and the compound represented by said general formula (Sk2-1) is still more preferable.

  The number average molecular weight of the silicone compound is preferably in the range of 100 or more and 1,000,000 or less, and more preferably in the range of 1000 or more and 100,000 or less.

  The number average molecular weight of the silicone compound in the crosslinked polymer after polymerization can be determined by dissolving the silicone compound in toluene or THF and using exclusion chromatography (SEC) using a standard sample.

  The amount of the silicone compound added to the fluorine resin (perfluoroalkylene ether-containing compound) (that is, the content of the silicone structure in the crosslinked polymer in the present embodiment) is preferably in the range of 5% by mass to 50% by mass, The range of mass% or more and 40 mass% or less is more preferable, and the range of 10 mass% or more and 30 mass% or less is more preferable.

· Alkylene Compound The alkylene compound used in the method of the above (I) specifically has an alkylene structure having 5 to 20 carbon atoms, and the above-mentioned reactivity of the fluorine resin (perfluoroalkylene ether-containing compound) It is a compound having a group capable of binding to a group (reactive crosslinking group).

The carbon number in the alkylene structure is more preferably 10 or more and 20 or less, still more preferably 15 or more and 20 or less.
As the carbon number of the alkylene structure increases, the cohesion between the molecules increases and the crystallinity increases, so that it becomes difficult to be compatible with other materials.

  Examples of the alkylene compound used in the method (I) include a compound represented by the following general formula (Ak1) having a group capable of binding to a reactive group at only one end, and a group capable of binding to a reactive group The compound represented by the following general formula (Ak2) having at both ends is preferable.

(In the general formulas (Ak1) and (Ak2), R ^A1 represents an alkyl group having 5 or more and 20 or less carbon atoms, and X ³ represents a reactive group (reactive crosslinking) possessed by the fluorocarbon resin (perfluoroalkylene ether-containing compound) Represents a group capable of binding to a group))

When the fluorocarbon resin (perfluoroalkylene ether-containing compound) has at least one of the (X-1) (acryloyl group, methacryloyl group, etc.) and (X-2) as a reactive group, the reactive group which the alkylene compound has the group (X ³⁾ capable of binding to, include a group having a carbon = carbon double bonds, and specific examples thereof include the same groups as the (X-1) and (X-2). That is, compounds represented by the following general formulas (Ak1-1), (Ak2-1), (Ak1-2) and (Ak2-2) can be mentioned.

(Formula (Ak1-1), (Ak2-1), it is synonymous with (Ak1-2) and ^{R A1} is the formula in (Ak2-2) (Ak1) and (Ak2). ^{Further, R X1} is generally It is synonymous with a formula (X-1).)

When a fluorine resin (perfluoroalkylene ether-containing compound) has the (X-3) (epoxy group) as a reactive group, a group (X ³ ) which can be bonded to the reactive group of the alkylene compound is a hydroxyl group And carboxyl group, trialkoxysilyl group, epoxy group, amino group, thiol group and vinyl group.

When the fluorine resin (perfluoroalkylene ether-containing compound) has the (X-4) (hydroxyl group) as a reactive group, the group (X ³ ) capable of binding to the reactive group of the alkylene compound is a hydroxyl group, Examples thereof include a carboxyl group, a trialkoxysilyl group, an epoxy group, an amino group, a thiol group and a vinyl group.

When the fluorine resin (perfluoroalkylene ether-containing compound) has the (X-5) (amino group) as a reactive group, a group (X ³ ) which can be bonded to the reactive group of the alkylene compound is a hydroxyl group And carboxyl group, trialkoxysilyl group, epoxy group, amino group, thiol group and vinyl group.

When the fluorine resin (perfluoroalkylene ether-containing compound) has the (X-6) (carboxy group, ester group, etc.) as a reactive group, a group (X ³ ) which can be bonded to the reactive group of the alkylene compound Examples thereof include a hydroxyl group, a carboxyl group, a trialkoxysilyl group, an epoxy group, an amino group, a thiol group and a vinyl group.

When the fluorine resin (perfluoroalkylene ether-containing compound) has the (X-7) (thiol group) as a reactive group, a group (X ³ ) capable of binding to the reactive group of the alkylene compound is a hydroxyl group And carboxyl group, trialkoxysilyl group, epoxy group, amino group, thiol group and vinyl group.

When the fluorine resin (perfluoroalkylene ether-containing compound) has the (X-8) (trialkoxysilyl group) as a reactive group, a group (X ³ ) which can be bonded to the reactive group of the alkylene compound is And a hydroxyl group, a carboxyl group, a trialkoxysilyl group, an epoxy group, an amino group, a thiol group and a vinyl group.

  Among the alkylene compounds listed above, as the alkylene compound used in the method (I), those represented by the general formulas (Ak1-1), (Ak2-1), (Ak1-2) and (Ak2-2) can be used. The compound represented is preferable, the compound represented by said general formula (Ak2-1) and (Ak2-2) is more preferable, and the compound represented by said general formula (Ak2-1) is still more preferable.

  The addition amount of the above-mentioned alkylene compound to the fluorocarbon resin (perfluoroalkylene ether-containing compound) (that is, the content of the alkylene structure in the crosslinked polymer in the present embodiment) is preferably 5% by mass or more and 50% by mass or less. The range of mass% or more and 40 mass% or less is more preferable, and the range of 10 mass% or more and 30 mass% or less is more preferable.

.Method of forming surface protective film (method of crosslinking polymerization)
In the method of reacting the crosslinking group at the time of (I) crosslinking polymerization described above, the surface protective film according to the present embodiment comprises at least the above-mentioned fluororesin (perfluoroalkylene ether-containing compound) and at least the above silicone compound and alkylene compound. It forms by apply | coating the coating liquid containing one and, on a base material, and cross-linking-polymerizing.

  The crosslinking polymerization may be performed via a crosslinking agent.

Here, for example, as a fluorine resin (perfluoroalkylene ether-containing compound), a crosslinking group (acryloyl group or the like) represented by the above (X-1) or (X-2) as a reactive crosslinking group in X ¹ and X ² In the case of using one having one, it is possible to carry out crosslinking polymerization without using a crosslinking agent.
On the other hand, as a fluorine resin (perfluoroalkylene ether-containing compound), the crosslinking groups represented by (X-3) to (X-8) above as reactive crosslinking groups in X ¹ and X ² (that is, epoxy group, hydroxyl group When using those having an amino group, a carboxyl group, etc.), a method using a crosslinking agent as a curing agent, or a combination in which reactive crosslinking groups react with each other (for example, X ¹ and X ² with an epoxy group) The cross-linking polymerization can be carried out by the method of using a compound having the compound and a compound having an amino group, a hydroxyl group or a carboxyl group at X ¹ and X ² ).

Crosslinking agent As a crosslinking agent which can be used for a compound having a group (epoxy group) represented by (X-3) as a reactive crosslinking group, pentaerythritol, dipentaerythritol, tripentaerythritol, polycarbonate diol, poly Ether diol, tris (2-hydroxyethyl) isocyanurate, etc. are mentioned.

  As a crosslinking agent which can be used for a compound having a group (a hydroxyl group, an amino group, a carboxyl group, etc.) represented by (X-4) (X-5) or (X-6) as a reactive crosslinking group, 2 Crosslinkers containing one or more epoxy groups are preferred. For example, 1,5-hexadiene diepoxide, 1,7-octadiene diepoxide, neopentyl glycol diglycidyl ether, 1,2-cyclohexanedicarboxylic acid diglycidyl, 2,2-bis (4-glycidyloxyphenyl) propane, tri Glycidyl isocyanurate, 1, 6-bis (2, 3- epoxy propoxy) naphthalene, etc. are mentioned.

  Moreover, as a crosslinking agent that can be used for a compound having a group (such as an acryloyl group) represented by (X-1) or (X-2) as a reactive crosslinking group, a crosslink containing two or more acryloyl groups Agents are preferred. For example, 2-hydroxy-3-acryloyloxypropyl methacrylate, polyethylene glycol diacrylate, tricyclodecane dimethanol diacrylate, 1,10-decanediol diacrylate, 1,6-hexanediol diacrylate, tripropylene glycol diacrylate, Ethoxylated isocyanuric acid triacrylate, ε-caprolactone modified tris- (2-acryloxyethyl) isocyanurate, pentaerythritol triacrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, pentaerythritol tetraacrylate Acrylate, dipentaerythritol polyacrylate, dipentaerythritol hex Acrylate, and the like.

  In the case of using a crosslinking agent, the addition amount to the fluorocarbon resin (perfluoroalkylene ether-containing compound) is preferably adjusted to 1% to 500% with respect to the mass of the fluorocarbon resin, and further 5% to It is more preferable to make it 200%.

Moreover, when using a liquid thing as a fluororesin (perfluoro alkylene ether containing compound), you may use it as said coating liquid as it is.
When using a fluorine resin (perfluoroalkylene ether-containing compound) which can be dissolved in a solvent regardless of solid or liquid, at least one of a fluorine resin, a silicone compound and an alkylene compound, and a curing agent (crosslinking agent) are required If it is the case, the coating solution is prepared by further dissolving the curing agent (crosslinking agent), other additives and the like in a solvent, and the coating solution is coated on a substrate and crosslinked and formed.
In addition, in the case of using a solid which does not dissolve in the solvent as the fluorocarbon resin (perfluoroalkylene ether-containing compound), at least one of the fluorocarbon resin, the silicone compound and the alkylene compound needs a curing agent (crosslinking agent) For example, the curing agent (crosslinking agent), other additives, etc. are formed by heating to a temperature at which they can be dissolved and performing crosslinking polymerization.
However, from the viewpoint of manufacturability, it is preferable to form the surface protective film using a compound that is soluble in a solvent or a compound that is liquid at normal temperature (25 ° C.).

  Examples of the solvent used for the coating solution include acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, butyl acetate, isobutyl acetate, amyl acetate, toluene, Xylene, hexane, heptane, 1,4-dioxane, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, methanol, ethanol, 1-propanol, 2-propanol, 1 -Butanol, tetrahydrofuran, 2H, 3H-decafluoropentane, 1-methoxyheptafluoropropane, 1-methoxynonaful Robutan, 1-ethoxy-nonafluorobutane, and the like.

  When the crosslinking polymerization is performed, energy may be supplied from the outside, and examples thereof include energy supply by means of irradiating ultraviolet light, means of irradiating an electron beam, means of heating, and the like.

  Moreover, you may add the polymerization initiator for performing the said crosslinking polymerization. Specific examples of the polymerization initiator include, for example, IRGACURE 184, IRGACURE 651, IRGACURE 123, IRGACURE 819, DAROCURE 1173, IRGACURE 784, IRGACURE OXE 01, IRGACURE OXE 02 as a radical type, IRGACURE 250 as a cation type, IRGACURE 270 (all manufactured by BASF Co., etc.) .

(II) Method of Cross-Linking Polymerization after Introduction into Fluoro Resin In the next place, a method of cross-linking polymerization after introduction into fluoro resin in advance will be described. In the method (II), at least one of the silicone structure and the alkylene structure is introduced by reacting at least one of a silicone compound and an alkylene compound with a fluorine resin having a perfluoroalkylene ether structure in the main chain in advance. Then, the cross-linking polymerization of the fluororesins is performed.
A crosslinked polymer having at least one of the silicone structure and the alkylene structure at an end of the fluorocarbon resin (a position corresponding to a position modified by a modifying group) by synthesizing the crosslinked polymer by the method of (II). Is obtained.

(Silicone structure and alkylene structure)
-Silicone structure As a silicone structure previously introduce | transduced into a fluorine resin, the range whose number average molecular weight is 100-1 million is preferable, and the range which is 1000-100000 is more preferable.

  The number average molecular weight of the silicone structure in the crosslinked polymer after polymerization can be measured by the method described in the method of (I) above.

  The range of 5 mass% or more and 50 mass% or less is preferable, as for content of the silicone structure in the crosslinked polymer of this embodiment, the range of 5 mass% or more and 40 mass% or less is more preferable, and 10 mass% or more and 30 mass% or less Is more preferable.

-Alkylene structure The alkylene structure has 5 to 20 carbon atoms, and the carbon number in the alkylene structure is more preferably 10 to 20, and still more preferably 15 to 20. As the carbon number of the alkylene structure increases, the cohesion between the molecules increases and the crystallinity increases, so that it becomes difficult to be compatible with other materials.

  The range of 5 mass% or more and 50 mass% or less is preferable, as for content of the alkylene structure in the crosslinked polymer of this embodiment, the range of 5 mass% or more and 40 mass% or less is more preferable, and 10 mass% or more and 30 mass% or less Is more preferable.

(Fluororesin introduced with at least one of silicone structure and alkylene structure)
The fluorine resin introduced with at least one of the silicone structure and the alkylene structure (hereinafter simply referred to as "silicone-alkylene-incorporated fluorine resin") used in the method (II) has a perfluoroalkylene ether structure in the main chain And it has at least 1 type of structure selected from the group which consists of a silicone structure shown by said general formula (S), and a C5-C20 alkylene structure.
In addition, as a perfluoro alkylene ether structure, the structure represented by the following general formula (F) is mentioned.

(In the general formula ^(F), representing the ^{R F1} and ^{R F2} fluorine atom or -CF ₃ each independently. ^However, .N1 never both ^{R F1} and ^{R F2} is a fluorine atom 1 to 5 N2 represents an integer of 0 or more and 2 or less, and the total number of n1 and n2 is 5 or less.)

With respect to the fluorine resin, the introduction position of the silicone structure and the alkylene structure previously introduced before the crosslinking polymerization may be introduced into the main chain of the fluorine resin or into the side chain,
It is preferred from the viewpoint of ease of introduction to introduce into the side chain.

  Although it does not specifically limit as a fluorine resin (silicone alkylene introduction fluorine resin) which introduce | transduced at least one of a silicone structure and an alkylene structure, For example, the compound represented by following General formula (3) is mentioned.

(In the above general formula (3), R ¹ , R ² , n ¹ , n 2, m, A ¹ , A ² , B ¹ , B ² , X ¹ and X ² are R ¹ and R ² in the general formula (1) ^{, n1, n2, m, a} 1, a 2, B 1, B 2, X 1, X 2 synonymous .Y ¹ and ^{Y 2} are silicone structure and 5 carbon atoms represented by the general formula (S) Represents a group having at least one kind of structure selected from the group consisting of an alkylene structure of not less than 20.

Incidentally, (a portion surrounded by _{[] m)} perfluoroalkylene ether structure part in the general formula (3), as a preferred structure of ^{A 1} and ^A 2, ^{B 1} and ^B 2, ^{X 1} and ^{X 2,} the aforementioned The same structure as the structure enumerated in General formula (1) is mentioned.

・ Y ¹ and Y ²
Y ¹ and Y ² each represent a group having at least one of a silicone structure represented by the general formula (S) and an alkylene structure having 5 to 20 carbon atoms. In addition, it is preferable to have the said silicone structure and alkylene structure in the position corresponded to the side chain in the compound (fluororesin) represented by the said General formula (3).

The structure of Y ¹ and Y ^2, the general formula (3) and main chain groups linking the "O" sandwiching the front and rear of Y ¹ and Y ² in the in the side chain of the main chain group formula (S) And a structure having at least one of a silicone structure represented by and a C 5 or more and 20 or less carbon alkylene structure.
The main chain group is a trivalent or higher organic group, and is selected, for example, from an alkyl chain, an aromatic chain, an ether group (-O-), a carbonyl group (-CO-), an ester group (-CO-O-) And trivalent or higher organic groups having a structure in which one kind of chain or a combination of two or more kinds of chains is combined.

  As a specific example of the said principal chain group, the organic group of the following (a) is mentioned, for example. In the following specific examples of the linking group, the * part bonds to “O”, and the # part bonds to the silicone structure or the alkylene structure.

-Specific example of silicone-alkylene introduction fluorine resin Here, the specific example of the fluorine resin (silicone-alkylene introduction fluorine resin) represented by the said General formula (3) is shown. However, the silicone-alkylene-introducing fluororesin in the present embodiment is not limited to the following example.

· Synthesis method of silicone · alkylene introduced fluoro resin Then, an example of a synthesis method of the fluorine resin (silicone · alkylene introduced fluoro resin) in which at least one of the silicone structure and the alkylene structure represented by the general formula (3) is introduced is explained. Do. The method of synthesizing the silicone-alkylene-introduced fluorocarbon resin used in the method (II) is not limited to the following method.

For example, it has a main chain group represented by the above (a) as Y ¹ and Y ² in the general formula (3), and a divalent group represented by the above (B-1) as B ¹ and B ² The case of synthesizing a compound having the compound is described.
The OH group of the compound having an OH group on the outside of A ¹ and A ² in the general formula (3) is modified with epoxy and then ring-opening polymerization of the epoxy group is carried out to at least one of the silicone structure and the alkylene structure ( Intermediate 1 is synthesized by reacting a group having R ⁴ ).
On the other hand, intermediate 2 is synthesized by reacting a compound having an OH group at the end of X ^* (where X ^* represents X ¹ or X ² in the general formula (1)) with succinic anhydride. By reacting the intermediate 2 with the intermediate 1, the silicone-alkylene-introduced fluororesin represented by the general formula (3) is synthesized.

When a compound having a divalent group represented by (B-2) and (B-3) as B ¹ and B ² is synthesized, the succinic anhydride in the above synthesis scheme is itaconic anhydride. Or synthetic by replacing with maleic anhydride.

When a compound in which B ¹ and B ² have a single bond is synthesized, the step of reacting the compound represented by X ^* -OH with succinic anhydride to obtain the intermediate 2 is not carried out. It can be synthesized by directly reacting ^* -OH with Intermediate 1.

-Physical property of surface protective film The surface protective film containing the crosslinked polymer in this embodiment becomes a material excellent in surface slip property in addition to scratch resistance as mentioned above.

Therefore, the contact angle of water at 25 ° C. is preferably 90 ° or more, and more preferably 100 ° or more.
The contact angle of hexadecane at 25 ° C. is preferably 80 ° or less, more preferably 70 ° or less.

  The measurement of the contact angle is carried out by the θ / 2 method at 25 ° C. using a contact angle meter using water and using a surface protective film sample coated on a film. Also, the contact angle with respect to hexadecane is measured by changing the water to hexadecane.

  The thickness of the surface protective film is not particularly limited, but is preferably 1 μm to 500 μm, and more preferably 10 μm to 50 μm.

[Use]
The surface protective film according to the present embodiment, which is obtained as described above, can be used without particular limitation as long as it is a substance that may cause scratches on the surface due to contact with foreign matter. Examples of objects that may be contacted by foreign matter on the surface and scratched by contact with the foreign matter include, for example, the body or screen of a smartphone, mobile phone, portable terminal such as a portable game, car body or window glass, case of a personal computer Image formation used for body, lens of glasses, recording surface of optical disc such as CD, DVD, BD, etc., solar cell panel, panel for reflecting sunlight, fixing member in image forming apparatus, intermediate transfer member, recording medium conveying member etc. Equipment includes endless belts and rolls, floors, mirrors, window glass, etc.

In portable terminals such as smartphones, mobile phones, and portable game machines, there are cases where an abrasion may occur because the tip of a finger (nail) or the tip of a stick for operation contacts and rubs on the body or screen.
In addition, window glass, car window glass and the body are scratched by various factors such as contact with sand, leaves, tree branches, etc. carried by wind because they are exposed to the outdoor environment, contact with insects, etc. There were times when
In addition, fine particles (dirt) may be attached to the surface of the lens of the glasses, etc., and the surface may be scratched by drying.
In addition, the recording surface of an optical disc such as a CD, DVD, BD, etc., contacts the corner of the case at the time of loading and unloading from the case, or at the corner of the device when loading and unloading from a reproducing apparatus, recording apparatus, etc They may come in contact with each other or the tips of the fingers (nails) may come in contact, and rubbing with these may cause scratching.
In addition, solar panels and panels that reflect sunlight are scratched by various factors such as contact with sand, leaves, tree branches, etc. carried by wind because they are exposed to the outdoor environment, contact with insects, etc. There were times when
Further, an endless belt or a roll for an image forming apparatus used for a fixing member, an intermediate transfer member, a recording medium conveyance member, etc. in an image forming apparatus contacts a recording medium such as paper in the image forming apparatus, and other members Because of the contact, abrasion with these may cause scratching.
Moreover, if it is a thing which a foreign material contacts not only the said aspect but the surface, abrasion with this foreign material might cause a scratch on the surface.

  By providing the surface protective film according to the present embodiment on the surface of an object in contact with the foreign matter, a flaw caused by the contact with the foreign matter is efficiently repaired.

[Endless belt]
The endless belt for an image forming apparatus according to the present embodiment has a belt-like base, and the surface protection film according to the above-described present embodiment provided on the belt-like base.

FIG. 1 is a perspective view (partly shown in section) of an endless belt according to the present embodiment, and FIG. 2 is an end view of the endless belt as viewed in the direction of arrow A in FIG. .
As shown to FIG. 1 and FIG. 2, the endless belt 1 of this embodiment is an endless belt which has the base material 2 and the surface layer 3 laminated | stacked on the surface of the base material 2. As shown in FIG.
As the surface layer 3, the surface protective film according to the above-described embodiment is applied.

  Examples of applications of the endless belt 1 include a fixing belt in an image forming apparatus, an intermediate transfer belt, a recording medium conveyance belt, and the like.

Hereinafter, the case where the endless belt 1 is used as a fixing belt will be described.
As a material used for the base material 2, a heat-resistant material is preferable, and specifically, it is used by being selected from various known plastic materials and metal materials.

  Among plastic materials, those generally referred to as engineering plastics are suitable, such as fluoroplastics, polyimides (PI), polyamidoimides (PAI), polybenzimidazoles (PBI), polyetheretherketones (PEEK), polysulfones (PSU). Polyether sulfone (PES), polyphenylene sulfide (PPS), polyether imide (PEI), wholly aromatic polyester (liquid crystal polymer) and the like are preferable. Among these, thermosetting polyimides, thermoplastic polyimides, polyamide imides, polyether imides, fluoro resins and the like which are excellent in mechanical strength, heat resistance, abrasion resistance, chemical resistance and the like are preferable.

  Moreover, there is no restriction | limiting in particular as a metal material used for the base material 2, Various metals and alloy materials are used, For example, SUS, nickel, copper, aluminum, iron etc. are used suitably. Further, a plurality of the heat resistant resin or the metal material may be laminated.

  Hereinafter, the case where the endless belt 1 is used as an intermediate transfer belt or a recording medium conveyance belt will be described.

  Examples of materials used for the substrate 2 include polyimide resins, polyamideimide resins, polyester resins, polyamide resins, fluorine resins, etc. Among these, it is more preferable to use polyimide resins and polyamideimide resins. preferable. The base material may or may not have a joint as long as it is annular (endless), and the thickness of the base material 2 is preferably 0.02 to 0.2 mm in general.

When the endless belt 1 is used as an intermediate transfer belt or a recording medium conveyance belt of an image forming apparatus, the surface resistivity is in the range of 1 × 10 ⁹ Ω / □ to 1 × 10 ¹⁴ Ω / □, and 1 × 10 ⁸ to 1 × It is preferable to control the volume resistivity in the range of 10 ¹³ Ωcm. Therefore, as described above, carbon black such as ketjen black and acetylene black as a conductive agent, metal or alloy such as graphite, aluminum, nickel and copper alloy as a conductive agent, tin oxide, zinc oxide, titanium It is preferable to add metal oxides such as potassium oxide, tin oxide-indium oxide or tin oxide-antimony oxide composite oxide, and conductive polymers such as polyaniline, polypyrrole, polysulfone, polyacetylene, etc. “Conductive” means that the volume resistivity is less than 10 ⁷ Ω · cm). These conductive agents may be used alone or in combination of two or more.

  Here, the above-mentioned surface resistivity and volume resistivity are measured according to JIS-K6911 under an environment of 22 ° C. and 55% RH using Hiresta UPMCP-450 type UR probe manufactured by Dia Instruments Co., Ltd. .

  In the case of fixing applications, endless belt 1 may comprise an elastic layer between substrate 2 and surface layer 3. As a material of an elastic layer, various rubber materials are used, for example. As various rubber materials, for example, urethane rubber, ethylene / propylene rubber (EPM), silicone rubber, fluororubber (FKM) and the like can be mentioned, and in particular, silicone rubber excellent in heat resistance and processability is preferable. Examples of the silicone rubber include RTV silicone rubber, HTV silicone rubber, etc. Specifically, polydimethyl silicone rubber (MQ), methyl vinyl silicone rubber (VMQ), methyl phenyl silicone rubber (PMQ), fluorocarbon Silicone rubber (FVMQ) etc. are mentioned.

When the endless belt 1 is used as the fixing belt in the electromagnetic induction type fixing device, a heat generating layer may be provided between the base 2 and the surface layer 3.
Examples of materials used for the heat generating layer include nonmagnetic metals, and specific examples thereof include gold, silver, copper, aluminum, zinc, tin, lead, bismuth, beryllium, antimony, and alloys thereof (these And metal materials such as alloys).
The thickness of the heat generating layer is preferably in the range of 5 to 20 μm, more preferably in the range of 7 to 15 μm, and particularly preferably in the range of 8 to 12 μm.

[roll]
The image forming apparatus roll according to the present embodiment has a cylindrical base, and the surface protection film according to the above-described present embodiment provided on the cylindrical base.

Next, the roll according to the present embodiment will be described. The roll of the present embodiment is a cylindrical roll having a substrate and a surface layer laminated on the surface of the substrate.
In addition, the surface protection film which concerns on above-mentioned this embodiment is applied as said surface layer.

  Examples of applications of the cylindrical roll include a fixing roll in an image forming apparatus, an intermediate transfer roll, a recording medium conveyance roll, and the like.

Hereinafter, the case where a cylindrical roll is used as a fixing roll will be described.
The fixing roll 610 as the fixing member shown in FIG. 4 is not particularly limited in its shape, structure, size and the like, and the surface layer 613 is provided on the cylindrical core 611. Further, as shown in FIG. 4, an elastic layer 612 may be provided between the core 611 and the surface layer 613.

  Examples of the material of the cylindrical core 611 include aluminum (for example, A-5052 material), a metal such as SUS, iron and copper, an alloy, a ceramic, and an FRM. The fixing device 72 of the present embodiment is formed of a cylindrical body having an outer diameter of 25 mm, a thickness of 0.5 mm, and a length of 360 mm.

  The material of the elastic layer 612 is selected from known materials, but any material may be used as long as it is an elastic body having high heat resistance. In particular, it is preferable to use an elastic body such as rubber or elastomer having a rubber hardness of about 15 to 45 (JIS-A), and examples thereof include silicone rubber and fluororubber.

  In the present embodiment, among these materials, silicone rubber is preferred in view of its small surface tension and excellent elasticity. Examples of the silicone rubber include RTV silicone rubber, HTV silicone rubber, etc. Specifically, polydimethyl silicone rubber (MQ), methyl vinyl silicone rubber (VMQ), methyl phenyl silicone rubber (PMQ), fluorocarbon Silicone rubber (FVMQ) etc. are mentioned.

  The thickness of the elastic layer 612 is preferably 3 mm or less, and more preferably in the range of 0.5 to 1.5 mm. In the fixing device 72, the core is coated with HTV silicone rubber having a rubber hardness of 35 ° (JIS-A) at a thickness of 72 μm.

  As thickness of the surface layer 613, 5 micrometers or more and 50 micrometers or less are mentioned, for example, 10 micrometers or more and 30 micrometers or less may be sufficient.

  For example, a halogen lamp 660 is used as a heating source for heating the fixing roll 610, and it is not particularly limited as long as it has a shape and a structure to be accommodated inside the core 611, and is selected according to the purpose. The surface temperature of the fixing roll 610 heated by the halogen lamp 660 is measured by a temperature-sensitive element 690 provided on the fixing roll 610, and the temperature is controlled by the control means. There is no restriction | limiting in particular as the thermo sensor 690, For example, a thermistor, a temperature sensor, etc. are mentioned.

[Image forming apparatus]
Next, an image forming apparatus of the present embodiment using the endless belt of the present embodiment and the roll of the present embodiment will be described. FIG. 3 includes the endless belt according to the present embodiment as a pressure belt of the fixing device, the endless belt according to the present embodiment as an intermediate transfer belt, and the roll according to the present embodiment as a fixing roll of the fixing device. FIG. 12 is a schematic view for explaining the main part of the tandem type image forming apparatus.

  Specifically, the image forming apparatus 101 includes a photosensitive member 79 (electrostatic latent image holding member), a charging roll 83 for charging the surface of the photosensitive member 79, and the surface of the photosensitive member 79 to expose an electrostatic latent image. A laser generator 78 (electrostatic latent image forming means) to be formed, and a developing device 85 (developing means) for developing a latent image formed on the surface of the photosensitive member 79 using a developer to form a toner image; An intermediate transfer belt 86 (intermediate transfer body) on which the toner image formed by the developing device 85 is transferred from the photosensitive member 79 (intermediate transfer body); and a primary transfer roll 80 (primary transfer means) for transferring the toner image to the intermediate transfer belt 86; A photoreceptor cleaning member 84 for removing toner, dust, etc. adhering to the photoreceptor 79, a secondary transfer roll 75 (secondary transfer means) for transferring the toner image on the intermediate transfer belt 86 to the recording medium, and Fixing device 72 (for fixing a toner image of And Chakushudan), is configured to include a. The photosensitive member 79 and the primary transfer roll 80 may be disposed immediately above the photosensitive member 79 as shown in FIG. 3 or may be disposed at a position deviated from immediately above the photosensitive member 79.

Further, the configuration of the image forming apparatus 101 shown in FIG. 3 will be described in detail.
In the image forming apparatus 101, around the photosensitive member 79, the charging roller 83, the developing device 85, and the primary transfer roller 80 disposed with the intermediate transfer belt 86 in a counterclockwise direction, and the photosensitive member cleaning member 84 are disposed. These one set of members form a developing unit corresponding to one color. Further, a toner cartridge 71 for replenishing the developer to the developing device 85 is provided for each developing unit, and the charging roller 83 (rotational direction of the photosensitive member 79) with respect to the photosensitive member 79 of each developing unit. A laser generator 78 is provided which irradiates a laser beam corresponding to image information on the surface of the photosensitive member 79 on the downstream side and on the upstream side of the developing device 85.

  Four developing units corresponding to four colors (for example, cyan, magenta, yellow, black) are disposed in series in the horizontal direction in the image forming apparatus 101, and the photosensitive members 79 of the four developing units and the primary are provided. An intermediate transfer belt 86 is provided so as to pass through the transfer region with the transfer roll 80. The intermediate transfer belt 86 is supported by a support roll 73, a support roll 74, and a drive roll 81 provided counterclockwise on the inner surface side in the following order, and forms a belt support device 90. The four primary transfer rolls are located downstream of the support roll 73 (in the rotational direction of the intermediate transfer belt 86) and upstream of the support roll 74. A transfer cleaning member 82 for cleaning the outer peripheral surface of the intermediate transfer belt 86 is provided on the opposite side of the drive roll 81 via the intermediate transfer belt 86 so as to be in contact with the drive roll 81.

  Further, the toner formed on the outer peripheral surface of the intermediate transfer belt 86 on the surface of the recording sheet conveyed from the sheet supply unit 77 via the sheet path 76 on the opposite side of the support roll 73 via the intermediate transfer belt 86 A secondary transfer roll 75 for transferring an image is provided in contact with the support roll 73.

  Further, a sheet supply unit 77 for storing a recording medium is provided at the bottom of the image forming apparatus 101, and a support roll 73 and a secondary transfer roll that constitute a secondary transfer unit from the sheet supply unit 77 via the sheet path 76 A recording medium is supplied to pass through the contact portion with 75. The recording medium having passed through the contact portion is further transported by a transport unit (not shown) so as to pass through the contact portion of the fixing device 72, and is finally discharged out of the image forming apparatus 101.

  Next, an image forming method using the image forming apparatus 101 shown in FIG. 3 will be described. The formation of a toner image is performed for each developing unit, and after charging the surface of the photosensitive member 79 rotated counterclockwise by the charging roll 83, the latent image is latently formed on the surface of the photosensitive member 79 charged by the laser generator 78 (exposure device). An image (electrostatic latent image) is formed, and then the latent image is developed by a developer supplied from a developing device 85 to form a toner image, and a contact portion between the primary transfer roll 80 and the photosensitive member 79. The toner image carried on the transfer belt 86 is transferred onto the outer peripheral surface of the intermediate transfer belt 86 rotating in the direction of arrow C. After the toner image is transferred, the toner, dust, and the like attached to the surface of the photosensitive member 79 are cleaned by the photosensitive member cleaning member 84 to prepare for the formation of the next toner image.

  The toner image developed for each developing unit of each color is conveyed to the secondary transfer portion in the state of being sequentially superimposed on the outer peripheral surface of the intermediate transfer belt 86 so as to correspond to the image information, and is carried by the secondary transfer roll 75. The sheet is transferred from the sheet supply unit 77 to the surface of the recording sheet conveyed through the sheet path 76. The recording sheet to which the toner image has been transferred is further fixed by being pressurized and heated when passing through the contact portion of the fixing device 72, and after an image is formed on the surface of the recording medium, the recording sheet is discharged out of the image forming apparatus. Be done.

-Fixing device (image fixing device)-
FIG. 4 is a schematic configuration diagram of the fixing device 72 provided in the image forming apparatus 101 according to the present embodiment. The fixing device 72 shown in FIG. 4 includes a pressure roller 640, which is a pressure member for pressing the fixing roller 610 via the endless belt 620 (pressure belt) and the endless belt 620 (pressure belt), as a rotating body that is rotationally driven. And is configured. The pressure pad 640 may be such that the endless belt 620 and the fixing roll 610 are relatively pressurized. Therefore, the endless belt 620 may be pressed against the fixing roll 610, and the fixing roll 610 may be pressed against the endless belt 620.

  Inside the fixing roll 610, a halogen lamp 660 is disposed as an example of a heating unit that heats the unfixed toner image in the nipping area. The heating means is not limited to the halogen lamp, and another heat generating member that generates heat may be used.

  On the other hand, a temperature sensitive element 690 is disposed in contact with the surface of the fixing roll 610. The lighting of the halogen lamp 660 is controlled based on the temperature measurement value by the temperature sensing element 690, and the surface temperature of the fixing roll 610 is maintained at the set temperature (for example, 150 ° C.).

  The endless belt 620 is rotatably supported by a pressure pad 640 and a belt travel guide 630 disposed inside and an edge guide (not shown). The fixing roller 610 is disposed in contact with the fixing roller 610 in a state where the fixing roller 610 is pressed.

  The pressure pad 640 is disposed on the inner side of the endless belt 620 so as to be pressed against the fixing roller 610 via the endless belt 620, and forms a pinching area N with the fixing roller 610. The pressure pad 640 has a pre-sandwiring member 641 for securing a wide pinching region N at the inlet side of the pinching region N, and holds the peeling pinching member 642 for applying a distortion to the fixing roll 610. It is arranged at the exit side of the loading area N.

  Furthermore, in order to reduce the sliding resistance between the inner circumferential surface of endless belt 620 and pressure pad 640, low friction sheet 680 is provided on the surface in contact with endless belt 620 of pre-clamping member 641 and peeling sandwiching member 642. ing. The pressure pad 640 and the low friction sheet 680 are held by a metal holder 650.

  Further, a belt travel guide 630 is attached to the holder 650, and the endless belt 620 is configured to rotate smoothly. That is, the belt travel guide 630 is formed of a material having a small coefficient of static friction in order to rub against the inner circumferential surface of the endless belt 620. Further, the belt travel guide 630 is formed of a material having a low thermal conductivity so that it is difficult to take heat from the endless belt 620.

  The fixing roll 610 is rotated in the direction of arrow C by a drive motor (not shown), and the endless belt 620 rotates in the direction opposite to the rotation direction of the fixing roll 610 following the rotation. That is, while the fixing roll 610 rotates clockwise in FIG. 4, the endless belt 620 rotates counterclockwise.

  The sheet K having the unfixed toner image is guided by the fixing inlet guide 560 and conveyed to the nipping area N. Then, when the sheet K passes through the nipping area N, the toner image on the sheet K is fixed by the pressure acting on the nipping area N and the heat supplied from the fixing roll 610.

  In the fixing device 72, the nipping area N is secured by the concave pre-nipping member 641 following the outer peripheral surface of the fixing roll 610.

  Further, in the fixing device 72 according to the present embodiment, the distortion of the fixing roll 610 in the exit area of the pinching area N is localized by disposing the peeling sandwiching member 642 so as to protrude with respect to the outer peripheral surface of the fixing roll 610. It is configured to be large. With this configuration, the sheet K after fixing is separated from the fixing roll 610.

  In addition, a peeling member 700 is disposed on the downstream side of the sandwiching area N of the fixing roll 610 as an auxiliary means for peeling. The peeling member 700 is held by the holder 720 in a state in which the peeling baffle 710 approaches the fixing roll 610 in the direction (counter direction) opposite to the rotation direction of the fixing roll 610.

<Portable device>
The surface protective film according to the present embodiment can be used as a protective film on a screen or the like for displaying an image in a portable terminal (portable device).
When the tip of a finger (nail) touches the screen (for example, a liquid crystal screen) in a mobile terminal (portable device) such as a smartphone, a mobile phone, or a portable game machine, or there is a stick for operation In some cases, the tip of the stick contacts and rubs to cause abrasion. On the other hand, by having the surface protective film according to the present embodiment as a protective film, the scratch is repaired even if the scratch occurs, so that the scratch (permanent scratch) permanently remaining on the surface is generated. Is effectively suppressed.

<Window glass, car body>
The surface protective film which concerns on this embodiment can be used as a protective film of window glass in a building, a car, etc. Moreover, the surface protective film which concerns on this embodiment can be used as a protective film of the body of a car.
The window glass of a building, the window glass of a car, the body, etc. are scratched due to various factors such as contact with sand, leaves, tree branches, etc. carried by the wind because they are exposed to the outdoor environment, contact with insects, etc. There were times when On the other hand, by having the surface protective film according to the present embodiment as a protective film, the scratch is repaired even if the scratch occurs, so that the scratch (permanent scratch) permanently remaining on the surface is generated. Is effectively suppressed.

<Lens of glasses>
The surface protective film which concerns on this embodiment can be used as a protective film of the lens of spectacles.
In the lens of the glasses, fine particles (dirt) may be attached to the surface, and there may be a case where the surface is scratched by drying from above. On the other hand, by having the surface protective film according to the present embodiment, the scratch is repaired even if the scratch occurs, so that the generation of the scratch (permanent scratch) permanently remaining on the surface is efficient. Suppressed.

<Optical disc>
The surface protective film according to the present embodiment can be used as a protective film of the recording surface of the optical disc.
The recording surface of an optical disc such as a CD, DVD, BD, etc. contacts the corner of the case at the time of loading and unloading from the case, or contacts the corner of the device at loading and unloading from the reproducing device, recording device, etc. Also, the tips of the fingers (nails) may come in contact, and rubbing with these may cause scratching. As a result, a reading error may occur due to a scratch on the recording surface. On the other hand, by having the surface protective film according to the present embodiment as a protective film, the scratch is repaired even if the scratch occurs, so that the scratch (permanent scratch) permanently remaining on the surface is generated. Is effectively suppressed. As a result, the occurrence of read errors is also effectively suppressed.

<Solar panel>
The surface protective film which concerns on this embodiment can be used as a protective film of the reflective surface of a solar panel.
Photovoltaic panels and panels that reflect sunlight are scratched by various factors such as contact with sand, leaves, tree branches, etc. carried by wind because they are exposed to the outdoor environment, contact with insects, etc. There was a thing. On the other hand, by having the surface protective film according to the present embodiment as a protective film, the scratch is repaired even if the scratch occurs, so that the scratch (permanent scratch) permanently remaining on the surface is generated. Is effectively suppressed.

  Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited to the examples shown below. In the following, "parts" and "%" are based on mass unless otherwise noted.

〔Example〕
<Surface protective film introduced with a silicone structure during crosslinking polymerization>
The following composition was mixed by the composition of following Table 1, and the coating liquid was prepared.
A fluorine resin having a perfluoroalkylene ether structure in the main chain (manufactured by Solvay, trade name: MT70 (concentration 82%), structure / main chain: a unit in which n1 is 1 and n2 is 0 in General Formula (F), Copolymerization with n1 = 2, n2 = 0 unit, 100 mol% of the structural unit represented by the general formula (F) with respect to all the structural units, terminal: modified at both terminals with methacrylate, functional group number 4, number average molecular weight 2000 )
Polyfunctional: ethoxylated isocyanuric acid triacrylate (AEICN) silicone compound (Shin-Etsu Chemical Co., Ltd., trade name: X-22-164, structure: structure shown in the following X-22-164 (= R ^S3 is C _X H _{2 X} ), reactive group weight 190 g / mol)

The above coating solution is applied (casted) to a polyimide film of 90 μm thickness, dried at 80 ° C. for 5 minutes to evaporate the solvent, and irradiated with ultraviolet light with an ultraviolet curing device to obtain a cured film, resin layer sample Obtained. The irradiation conditions of ultraviolet light irradiated the light quantity of 1000 mmJ / cm < ² > using the high pressure mercury lamp under nitrogen atmosphere (oxygen concentration 1% or less).

[Evaluation]
-Measurement of Contact Angle The contact angle of the resin layer sample obtained above was measured using water or hexadecane. In addition, the measurement of the said contact angle was performed by the (theta) / 2 method at 25 degreeC using the contact angle meter (Kyowa Interface Science Co., Ltd. make, model number: CA-S- Rugata). The results are shown in the table.

Scratch resistance The resin layer sample obtained above was subjected to a scratch test at a normal temperature (25 ° C.) with a load of 2 N using a scratch-type hardness tester (manufactured by ERICHSEN, tip diameter 0.75 mm) at 80 ° C. After heating for 30 seconds, the scratched area was observed to evaluate the presence or absence of a scratch.
B: Scratch on protective film sample A: No scratch on protective film sample

Toner Releasability The resin sample obtained above was attached to the surface of a fixing roll of a fixing device, and a black unfixed solid image was passed to confirm the fixing property. In addition, brand name: DocuCentre C2101 made by Fuji Xerox Co., Ltd. was used as the fixing device. Evaluation criteria are as follows, and A evaluation is accepted. The results are shown in the table.
C: Toner adheres to the entire surface of the protective film sample B: Toner adheres to about half of the protective film sample A: No toner adheres to the protective film sample

  In addition, the "addition amount" in Table 1 represents the quantity with respect to a fluororesin (MT70). The same applies to Table 2.

<Surface Protective Film Introduced Alkylene Structure in Cross-Linking Polymerization>
The following composition was mixed by the composition of following Table 2, and the coating liquid was prepared.
A fluorine resin having a perfluoroalkylene ether structure in the main chain (manufactured by Solvay, trade name: MT70 (concentration 82%), structure / main chain: a unit in which n1 is 1 and n2 is 0 in General Formula (F), Copolymerization with n1 = 2, n2 = 0 unit, 100 mol% of the structural unit represented by the general formula (F) with respect to all the structural units, terminal: modified at both terminals with methacrylate, functional group number 4, number average molecular weight 2000 )
・ Alkylene compound C12 Ac (structure: structure shown in the following C12 Ac)
・ Alkylene compound C10diAc (structure: structure shown in the following C10diAc)
・ Alkylene compound C18 Ac (structure: structure shown in the following C18 Ac)

The coating solution is applied (casted) to a polyimide film of 90 μm thickness and dried at 100 ° C. for 5 minutes to volatilize the solvent, and ultraviolet irradiation is performed with an ultraviolet curing device to obtain a cured film, and a resin layer sample is obtained. Obtained. The irradiation conditions of ultraviolet light irradiated the light quantity of 1000 mmJ / cm < ² > using the high pressure mercury lamp under nitrogen atmosphere (oxygen concentration 1% or less).

[Evaluation]
Evaluation was performed in the same manner as described above.

<Surface protective film introduced with silicone structure or alkylene structure during crosslink polymerization>
The following composition was mixed by the composition of following Table 3, and the coating liquid was prepared.
・ Fluororesin having a perfluoroalkylene ether structure in the main chain (manufactured by DIC, trade name: Megafuck® RS-76 (concentration 40%), terminal: both ends modified with acrylate)
Silicone compound (Shin-Etsu Chemical Co., Ltd. trade name: X-22-164, structure: structure shown in the above X-22-164 (= R ^S3 represents C _X H _{2 X} ), reactive group weight 190 g / mol )
・ Alkylene compound C10diAc (structure: structure shown in the above C10diAc)
・ Silicone compound (manufactured by JNC, trade name: Silaplain FM-0711, structure: structure (n = 10) shown in the following FM-0711, molecular weight; 1000, monofunctional silicone system having a methyl methacrylate group at one molecular terminal end Macromonomer)

The coating solution is applied (casted) to a polyimide film of 90 μm thickness and dried at 100 ° C. for 5 minutes to volatilize the solvent, and ultraviolet irradiation is performed with an ultraviolet curing device to obtain a cured film, and a resin layer sample is obtained. Obtained. The irradiation conditions of ultraviolet light irradiated the light quantity of 1000 mmJ / cm < ² > using the high pressure mercury lamp under nitrogen atmosphere (oxygen concentration 1% or less).

[Evaluation]
Evaluation was performed in the same manner as described above.

<Surface protective film cross-linked and polymerized using a fluorine resin having an alkylene structure introduced in advance>
According to the scheme shown below, the fluorine resin which introduce | transduced the alkylene structure was synthesize | combined, and the coating liquid containing the fluorine resin which introduce | transduced this alkylene structure was prepared. In addition, the number average molecular weight of the perfluoro alkylene ether structure part was 1600.

Further, in the above scheme, the alkylene chain portion (C ₁₁ H ₂₃ portion) in the synthesis of the intermediate C ₁₁ is replaced with “C ₁₃ H ₂₇ ” and “C ₁₅ H ₃₁ ”, and the alkylene chain portion is C ₁₃ H ₂₇ The fluorocarbon resin C13 and the fluorocarbon resin C15 were synthesized.

The coating solution is applied (casted) to a polyimide film of 90 μm thickness and dried at 100 ° C. for 5 minutes to volatilize the solvent, and ultraviolet irradiation is performed with an ultraviolet curing device to obtain a cured film, and a resin layer sample is obtained. Obtained. The irradiation conditions of ultraviolet light irradiated the light quantity of 1000 mmJ / cm < ² > using the high pressure mercury lamp under nitrogen atmosphere (oxygen concentration 1% or less).

[Evaluation]
Evaluation was performed in the same manner as described above.

DESCRIPTION OF SYMBOLS 1 endless belt 2 base material 3 surface layer 72 fixing device 75 secondary transfer roll 78 laser generator 79 photosensitive member 80 primary transfer roll 83 charging roll 85 developing device 86 intermediate transfer belt 101 image forming apparatus 610 fixing roll 620 endless belt K Paper

Claims (3)

A structure in which a fluorine resin having a perfluoroalkylene ether structure in its main chain is crosslinked and polymerized,
At least one structure selected from the group consisting of a silicone structure represented by the following general formula (S) and an alkylene structure having 5 to 20 carbon atoms,
Have a following i) or ii) a surface protective film comprising a cross-linked polymer.


(In the general formula (S), R ^S1 and R ^S2 each independently represent -CH ₃ , -CF ₃ or a hydrogen atom.)

i) a compound represented by the following general formula (1) and a silicone compound represented by the following general formula (Sk1-1), (Sk2-1), (Sk1-2) or (Sk2-2), or Crosslinked polymer obtained by crosslinking and polymerizing a silicone compound represented by general formula (Ak1-1), (Ak2-1), (Ak1-2) or (Ak2-2)

(In the above general formula (1), R ¹ and R ² each independently represent a fluorine atom or —CF ₃ (trifluoromethyl group), provided that both of R ¹ and R ² are a fluorine atom Absent.
n1 represents an integer of 1 or more and 5 or less, n2 represents an integer of 0 or more and 2 or less, and the total number of n1 and n2 is 5 or less. m represents an integer of 1 or more.
A ¹ and A ² each independently represent a divalent group represented by the following general formula (2).
B ¹ and ^{B 2} represents a divalent radical selected from the group consisting of a single bond and the following (B-1) to (B-3) independently.
Each of X ¹ and X ² independently represents a monovalent group having at least one reactive crosslinking group selected from the following (X-1). )

(In the above general formula (2), R ³ and R ⁴ each independently represent a fluorine atom or a trifluoromethyl group. However, neither R ³ nor R ⁴ is a fluorine atom.
n3 represents an integer of 0 to 5, n4 represents an integer of 0 to 2, n5 represents an integer of 0 or more, n6 represents 0 or 1, and n7 represents an integer of 0 or more. However, n3, n4, n5 and n6 can not all be zero.
Incidentally, the divalent group represented by the general formula (2) bonded to perfluoroalkylene ether structure (* 1) portion, (* 2) part ^(-O-B 1 -X ¹⁾ or ( ^{-O-B 2} -X 2) to bind. )

((B-1) to (B-3) respectively bind to X ¹ or X ² in the (# 2) portion, and (-O-A ¹ ...) Or (-O in the (# 1) portion -A ² ...) combined with the side))

(R ^X1 in the above (X-1) represents a hydrogen atom, a methyl group, or a trifluoromethyl group.)

(In the above general formulas (Sk1-1), (Sk2-1), (Sk1-2) and (Sk2-2), R ^S1 and R ^S2 are each independently —CH ₃ , —CF ₃ or a hydrogen atom R ^S3 represents a single bond, C _X H _{2 X} (X represents an integer of 1 or more) R ^S4 represents -CH ₃ , -CF ₃ or a hydrogen atom, and ns represents an integer of 1 or more R ^X1 represents a hydrogen atom, a methyl group or a trifluoromethyl group.)

(In the above general formulas (Ak1-1), (Ak2-1), (Ak1-2) and (Ak2-2), R ^A1 represents an alkyl group having 5 to 20 carbon atoms, R ^X1 represents a hydrogen atom, Represents a methyl group or a trifluoromethyl group)
ii) Crosslinked polymer of fluorine resin represented by the following general formula (3)

(In the above general formula (3), R ¹ and R ² each independently represent a fluorine atom or —CF ₃ (trifluoromethyl group), provided that both of R ¹ and R ² are a fluorine atom Absent.
n1 represents an integer of 1 or more and 5 or less, n2 represents an integer of 0 or more and 2 or less, and the total number of n1 and n2 is 5 or less. m represents an integer of 1 or more.
A ¹ and A ² each independently represent a divalent group represented by the following general formula (2).
Y ¹ and Y ² each represent a group having at least one structure selected from the group consisting of a silicone structure represented by the above general formula (S) and an alkylene structure having 5 to 20 carbon atoms.
B ¹ and ^{B 2} represents a divalent radical selected from the group consisting of a single bond and the following (B-1) to (B-3) independently.
X ¹ and X ² each independently represent a monovalent group having at least one reactive crosslinking group selected from the group consisting of (X-1) below. )

(In the above general formula (2), R ³ and R ⁴ each independently represent a fluorine atom or a trifluoromethyl group. However, neither R ³ nor R ⁴ is a fluorine atom.
n3 represents an integer of 0 to 5, n4 represents an integer of 0 to 2, n5 represents an integer of 0 or more, n6 represents 0 or 1, and n7 represents an integer of 0 or more. However, n3, n4, n5 and n6 can not all be zero.
Incidentally, the divalent group represented by the general formula (2) (* 1) part combined with perfluoroalkylene ether structure, (* 2) portions ^{(-O-Y 1 -O-B} 1 - X ¹⁾ or binding to ^{(-O-Y 2 -O-B} 2 -X 2). )

((B-1) to (B-3) respectively bind to X ¹ or X ² in the (# 2) portion, and (-O-Y ¹ -O-A ¹ ... In the (# 1) portion ) or ^(binds to ^{-O-Y 2 -O-a 2} ···) side.)

(R ^X1 in the above (X-1) represents a hydrogen atom, a methyl group, or a trifluoromethyl group.) The surface protective film according to claim 1, wherein the perfluoroalkylene ether structure has at least one structure selected from the structures represented by the following general formula (F).


(In the general formula ^(F), representing the ^{R F1} and ^{R F2} fluorine atom or -CF ₃ each independently. ^However, .N1 never both ^{R F1} and ^{R F2} is a fluorine atom 1 to 5 N2 represents an integer of 0 or more and 2 or less, and the total number of n1 and n2 is 5 or less.) X in the general formula (1) or (3) ¹ And X ² The surface protective film according to claim 1 or 2, wherein R is a group represented by the following (X-1a) to (X-1f).

(R in (X-1a) to (X-1f) ^X1 Represents a hydrogen atom, a methyl group or a trifluoromethyl group. )