JP2016183299A - Surface protective film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a surface protective film which has surface stain resistance and which has excellent heat resistance.SOLUTION: A surface protective film includes a crosslinked polymer of: a perfluoroalkylene ether-containing compound with a specified structure, having one to five difluoromethylene linking groups and a methylene linking group including a trifluoromethyl group or a fluorine group, and further having a trialkoxysilane group in the molecule; and an organometallic compound represented by general formula (2) (M is an organometal selected from titanium, zirconium, silicon, aluminum or zinc; R21 and R22 are each independently an alkyl group, a cycloalkyl group, an alkenyl group, or an acetyl group; o+p+q is equal to a valence of the organometal represented by M; o is an integer of 0 or more and not more than the valence; p is an integer of 0 or more and not more than (the valence-2); q is an integer of 0 or more and not more than the valence; and o+q is 2 or more).SELECTED DRAWING: None

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 antifouling property on the surface and the like.

  Here, in Patent Document 1, in a fixing roller in which a fluororesin layer is formed on the outer surface of a roller-shaped substrate via a rubber layer, the fluororesin layer has (A) an average particle diameter of 1 to 15 μm. Formed from a fluororesin mixture containing 20 to 97% by weight of tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA) and 3 to 80% by weight of polytetrafluoroethylene (PTFE) having an average particle diameter of 1 μm or less. A fixing roller is disclosed.

  Further, in Patent Document 2, in a roll in which a fluororesin coating layer is provided directly on the shaft body or via another coating layer, the fluororesin coating layer is made of an uncrosslinked fluororesin on the inner peripheral surface side, And the roll which coat | covered the surface which the outer peripheral surface side consists of bridge | crosslinking fluororesin with bridge | crosslinking fluororesin is disclosed.

  Patent Document 3 discloses an active energy ray-curable resin composition for a film protective layer containing an active energy ray-curable resin composition and a reactive fluorine antifouling agent, the reactive fluorine antifouling agent A film which is a reactive fluorine antifouling agent containing a perfluoropolyether having a turbidity of less than 20% and having one active hydrogen and a monomer having an active hydrogen and a carbon-carbon double bond Active energy ray-curable resin composition for protective layer, optical sheet made of cured product of active energy ray-curable resin composition for film protective layer, active energy ray-curable resin composition for film protective layer on film A protective adhesive film is disclosed in which a protective layer that is a cured product is formed, and an adhesive surface is provided on the back surface of the film.

Patent Document 4 discloses a silicate compound represented by Si (OR) ₄ (R is an organic group or inorganic group or H which may contain O, N, F, and Cl), and (X ¹ ) _n Al. (OR ¹ ) _m and / or (X ² ) _p Zr (OR ² ) _q (X ¹ , X ² are organic silicate groups optionally containing O, N, F, Cl, R ¹ , R ² are O And an anti-fouling agent comprising a co-oligomer of an organoaluminum and / or zirconium compound represented by H), which may contain N, F, and Cl, and the inhibitor and a coating resin. For example, a coating composition comprising a curing agent and / or a curing catalyst is disclosed.

  Patent Document 5 discloses component 1): 1. a) a (per) fluoropolyether (PFPE) diol having a partially fluorinated prepolymer having free NCO groups and an average molecular weight Mn in the range of 800 to 1,500, and isophorone diisocyanate A prepolymer obtained by reaction of a nate (IPDI) with a cyclic trimer; b) Mixture comprising hexamethylene diisocyanate acyclic isocyanate trimer, component 2): (per) fluoropolyether (PFPE) diol having an average molecular weight Mn in the range of 350 to 700, component 3): crosslinking reaction A composition comprising an inert organic solvent under conditions is disclosed.

  Patent Document 6 discloses that at least the titanium compound oligomer (a1) having a condensed structure of component (A) is a silicon compound (a2) having one or more alkoxy groups in the molecule, and 1 in the molecule. There is disclosed a surface treatment composition containing a composite compound having a structure in which a resin (a3) having at least one epoxy group is reacted or a mixed composition, and a component (B) solvent.

Japanese Patent Laid-Open No. 10-142990 JP 2003-36002 A JP 2010-222524 A JP-A-10-259327 JP 2001-226629 A JP 2010-150490 A

  The object of the present invention is to provide surface protection with superior heat resistance as compared to the case where the methacrylate portion of the perfluoroalkylene ether-containing compound modified at both ends with urethane-containing methacrylate contains only a crosslinked polymer obtained by crosslinking polymerization. It is to provide a membrane.

The above-mentioned subject is achieved by the following present invention.
That is, the invention according to claim 1
A surface protective film comprising a crosslinked polymer of a perfluoroalkylene ether-containing compound represented by the following general formula (1) and an organometallic compound represented by the following general formula (2).

(In the general formula (1), Z represents a divalent group selected from the group consisting of the above (Z-1) to (Z-2) or two or more and five or less groups selected from the group. And Z represents a divalent group represented by (Z-1) and includes a divalent group represented by (Z-1) in the range of 1 to 5 and the divalent group represented by (Z-2). And a group containing 0 or more and 2. In the above (Z-2), R ^Z1 and R ^Z2 each independently represent a fluorine atom or a trifluoromethyl group, provided that at least one of R ^Z1 and R ^Z2 represents a trifluoromethyl group. In the case where Z contains two divalent groups represented by the above (Z-2), a plurality of R ^Z1 and R ^Z2 may be the same or different.
m represents an integer of 1 or more. However, when m is 2 or more, a plurality of Z may be the same or different.
A ¹ and A ² each independently represent a divalent organic group. na1 and na2 each independently represents 0 or 1.
X ¹ and X ² each independently represent a reactive crosslinking group selected from the group consisting of (X-1) to (X-2). R ^X1 in the above (X-1) represents a hydrogen atom or an alkyl group having 10 or less carbon atoms which may have a substituent. R ^X21 , R ^X22 and R ^X23 in (X-2) each independently represent a hydrogen atom or an alkyl group having 10 or less carbon atoms which may have a substituent. )

(In the general formula (2), M represents an organic metal selected from the group consisting of titanium, zirconium, silicon, aluminum, and zinc.
R ²¹ represents an alkyl group, a cycloalkyl group, an alkenyl group, or an acetyl group. The group represented by R ²¹ may have a substituent.
R ²² represents an alkyl group, a cycloalkyl group, an alkenyl group, or an acetyl group. The group represented by R ²² may have a substituent.
R ²³ represents a saturated or unsaturated divalent hydrocarbon group that forms a chelate ring by binding to the organic metal represented by M via the two O atoms represented by the general formula (2). The hydrocarbon group represented by R ²³ may have a substituent or may have a hetero atom.
o + p + q is equal to the valence of the organic metal represented by M, o is an integer from 0 to the valence, p is an integer from 0 to (the valence-2), q is 0 The above represents an integer less than the valence, and o + q is 2 or more.
However, when o is 2 or more, a plurality of R ^{21 s} are present, when p is 2 or more, a plurality of R ^{22 s} are present, and when q is 2 or more, a plurality of R ^{23 s} are the same, May be different. )

The invention according to claim 2
2. The device according to claim 1, wherein at least one of the na1 and na2 in the general formula (1) is 1, and the A ¹ and A ² represent a divalent group represented by the following general formula (A-1). Surface protective film.

(In the general formula (A-1), A ³ represents a divalent group selected from the group consisting of (A3-1) to (A3-4) or two or more groups selected from the group. A ³ represents a combined divalent group, and A ³ includes a divalent group represented by (A3-1) of 0 to 5 inclusive, and the divalent group represented by (A3-2). The group contains 0 or more and 2 or less, the divalent group represented by (A3-3) contains 0 or more, and the divalent group represented by (A3-4) contains 0 or 1. R ^A1 and R ^A2 in A3-2) each independently represent a fluorine atom or a trifluoromethyl group, provided that at least one of R ^A1 and R ^A2 represents a trifluoromethyl group, and A ³ represents the above (A3-2). each of R ^A1 and R ^A2 there are multiple same when) containing two divalent groups represented by It may be different even.
Y represents —O— or —NH—. na3 represents an integer of 0 or more, and na4 represents an integer of 1 to 3. However, when na3 is 2 or more, a plurality of [ _—Y— (CH ₂ ) _na4 —] groups may be the same or different.
The divalent group represented by the general formula (A-1) is bonded to the perfluoroalkylene ether structure at the (* 1) portion, and (—X ¹ ) or (—X ² ) at the (* 2) portion. ). )

The invention according to claim 3
The surface protective film according to claim 1, wherein the p in the general formula (2) is 1 or more.

The invention according to claim 4
The surface protection film according to claim 1, wherein the q in the general formula (2) is 1 or more.

The invention according to claim 5
The surface protective film according to claim 1, wherein the organic metal represented by M in the general formula (2) is titanium or silicon.

The invention according to claim 6
The surface protective film according to any one of claims 2 to 5, wherein the na3 in the general formula (A-1) is 1 or more.

  According to the invention according to claim 1 and claim 2, it is superior to the case where the methacrylate portion of the perfluoroalkylene ether-containing compound modified at both ends with urethane-containing methacrylate contains only a crosslinked polymer obtained by crosslinking polymerization. A surface protective film having high heat resistance is provided.

  According to the third aspect of the present invention, a surface protective film excellent in film forming performance is provided as compared with the case where p in the general formula (2) is 0.

  According to the invention which concerns on Claim 4, compared with the case where said q in General formula (2) is 0, the surface protective film excellent in the film-forming performance is provided.

  According to the invention which concerns on Claim 5, compared with the case where said M in General formula (2) is a zirconium, the surface protective film excellent in the film-forming performance is provided.

  According to the invention which concerns on Claim 6, compared with the case where said na3 in general formula (A-1) is 0, the surface protective film excellent in the film-forming performance is provided.

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

  Hereinafter, embodiments of the present invention will be described in detail.

<Surface protective film>
The surface protective film according to the present embodiment comprises a crosslinked polymer of a perfluoroalkylene ether-containing compound represented by the general formula (1) described later and an organometallic compound represented by the general formula (2) described later. Including.

  In recent years, a surface protective film has been provided in various fields from the viewpoint of suppressing surface contamination (antifouling property), and for example, a cross-linked fluororesin material has been used. However, the cross-linked fluororesin material has low heat stability, and the heat resistance sometimes causes poor resin durability.

  On the other hand, in the surface protective film according to the present embodiment, the perfluoroalkylene ether-containing compound represented by the following general formula (1) and the organometallic compound represented by the following general formula (2) are crosslinked. Since the cross-linked polymer having the structure is included, excellent heat resistance can be realized. Furthermore, it is possible to obtain a surface protective film that exhibits excellent antifouling properties and is excellent in water repellency, oil repellency, and wear resistance.

Here, the crosslinked polymer contained in the surface protective film according to the present embodiment will be described.
The crosslinked polymer is obtained by crosslinking polymerization of the following perfluoroalkylene ether-containing compound and the following organometallic compound.

(Perfluoroalkylene ether-containing compound)
The perfluoroalkylene ether-containing compound used in the present embodiment has a structure represented by the following general formula (1).

(In the general formula (1), Z represents a divalent group selected from the group consisting of the above (Z-1) to (Z-2) or two or more and five or less groups selected from the group. And Z represents a divalent group represented by (Z-1) and includes a divalent group represented by (Z-1) in the range of 1 to 5 and the divalent group represented by (Z-2). And a group containing 0 or more and 2. In the above (Z-2), R ^Z1 and R ^Z2 each independently represent a fluorine atom or a trifluoromethyl group, provided that at least one of R ^Z1 and R ^Z2 represents a trifluoromethyl group. In the case where Z contains two divalent groups represented by the above (Z-2), a plurality of R ^Z1 and R ^Z2 may be the same or different.
m represents an integer of 1 or more. However, when m is 2 or more, a plurality of Z may be the same or different.
A ¹ and A ² each independently represent a divalent organic group. na1 and na2 each independently represents 0 or 1.
X ¹ and X ² each independently represent a reactive crosslinking group selected from the group consisting of (X-1) to (X-2). R ^X1 in the above (X-1) represents a hydrogen atom or an alkyl group having 10 or less carbon atoms which may have a substituent. R ^X21 , R ^X22 and R ^X23 in (X-2) each independently represent a hydrogen atom or an alkyl group having 10 or less carbon atoms which may have a substituent. )

-Perfluoroalkylene ether structure part First, the said General formula (1) has the perfluoroalkylene ether structure part enclosed by [] _m . In this perfluoroalkylene ether structure portion, Z is a divalent group selected from the group consisting of (Z-1) to (Z-2) or (Z-1) to (Z-2). It represents a divalent group formed by combining 2 or more and 5 or less groups selected from the group.

Z includes a divalent group (—CF ₂ —) represented by (Z-1) in the range of 1 to 5, and a divalent group (—CR ^Z1 ) represented by (Z-2). R ^Z2 —) is 0 or more and 2 or less.
In Z, the number of divalent groups represented by (Z-1) is preferably 1 or more and 3 or less, and the number of divalent groups represented by (Z-2) is further 0 or more and 1 or less. The total number of the divalent group represented by (Z-1) and the divalent group represented by (Z-2) is more preferably 1 or more and 3 or less.

R ^Z1 and R ^Z2 in (Z-2) each independently represent a fluorine atom or a trifluoromethyl group. However, at least one of R ^Z1 and R ^Z2 represents a trifluoromethyl group. When Z contains two divalent groups (—CR ^Z1 R ^Z2 —) represented by the above (Z-2), a plurality of R ^Z1 and R ^Z2 may be the same or different. .

  M, which is the number of [] surrounding the perfluoroalkylene ether structure portion, represents an integer of 1 or more. When m is 2 or more, a plurality of Z may be the same or different. 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 structure portion ([—Z—O—] _m ) include, for example, the following structures (m-1) to (m-8). Note that m1 and m2 shown in (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 (m-1) to (m-8), the structure (m-2), (m-6), (m-7) or (m-8) is preferable, and (m- The structure 2) is more preferable.

A ¹ and A ²
In the general formula (1), A ¹ and A ² each independently represent a divalent organic group.
Incidentally, na1 and na2 each independently represent 0 or 1, i.e. perfluoroalkylene ether-containing compound represented by the general formula (1) may not have have a A ¹ and A ² . However, it is preferable that at least one of na1 and na2 is 1, and it is more preferable that both na1 and na2 are 1.

Examples of the divalent organic group represented by A ¹ and A ² include an alkylene group, a fluorinated alkylene group, a divalent group such as —C (═O) —, —O—, —NH—, or the like. And a divalent group formed by combining two or more groups selected from the group consisting of:

The divalent organic group represented by A ¹ and A ² is preferably a divalent group represented by the following general formula (A-1).

(In the general formula (A-1), A ³ represents a divalent group selected from the group consisting of (A3-1) to (A3-4) or two or more groups selected from the group. A ³ represents a combined divalent group, and A ³ includes a divalent group represented by (A3-1) of 0 to 5 inclusive, and the divalent group represented by (A3-2). The group contains 0 or more and 2 or less, the divalent group represented by (A3-3) contains 0 or more, and the divalent group represented by (A3-4) contains 0 or 1. R ^A1 and R ^A2 in A3-2) each independently represent a fluorine atom or a trifluoromethyl group, provided that at least one of R ^A1 and R ^A2 represents a trifluoromethyl group, and A ³ represents the above (A3-2). each of R ^A1 and R ^A2 there are multiple same when) containing two divalent groups represented by It may be different even.
Y represents —O— or —NH—. na3 represents an integer of 0 or more, and na4 represents an integer of 1 to 3. However, when na3 is 2 or more, a plurality of [ _—Y— (CH ₂ ) _na4 —] groups may be the same or different.
The divalent group represented by the general formula (A-1) is bonded to the perfluoroalkylene ether structure at the (* 1) portion, and (—X ¹ ) or (—X ² ) at the (* 2) portion. ). )

A ³ is a divalent group selected from the group consisting of (A3-1) to (A3-4), or two or more selected from the group consisting of (A3-1) to (A3-4) Represents a divalent group formed by combining these groups.

A ³ includes a divalent group (—CF ₂ —) represented by (A3-1) of 0 to 5 inclusive, and a divalent group (—CR ^A1 ) represented by (A3-2). R ^A2 —) is 0 or more and 2 or less, the divalent group (—CH ₂ —) represented by (A3-3) is 0 or more, and the divalent group represented by (A3-4) Contains 0 or 1 group (—CO—).
The number of divalent groups represented by (A3-1) in A ³ is preferably 1 or more and 3 or less, and the number of divalent groups represented by (A3-2) is further 0 or 1. Preferably, the number of divalent groups represented by (A3-3) is more preferably 0 or more and 2 or less. The total number of the divalent group (—CH ₂ —) represented by (A3-3) and the divalent group (—CO—) represented by (A3-4) is 2 or less. It is more preferable that it is 1 or less.

R ^A1 and R ^A2 in (A3-2) each independently represent a fluorine atom or a trifluoromethyl group. However, at least one of R ^A1 and R ^A2 represents a trifluoromethyl group. R ^A1 is preferably a fluorine atom, and R ^A2 is preferably a trifluoromethyl group. When A ³ contains two divalent groups (—CR ^A1 R ^A2 —) represented by the above (A3-2), a plurality of R ^A1 and R ^A2 may be the same or different from each other. Good.

Y represents —O— or —NH—.
na3 represents an integer of 0 or more.
na4 represents an integer of 1 to 3, and preferably 2 to 3.
However, when na3 is 2 or more, a plurality of [ _—Y— (CH ₂ ) _na4 —] groups may be the same or different.

Here, na3 is preferably 1 or more, that is, at least one of X ¹ and X ² in the general formula (1) is a perfluoroalkylene ether structure via a group ( _—Y— (CH ₂ ) _na4 —). It is preferable that it is couple | bonded with. The structure represented by the general formula (1) is a structure having a group ( _—Y— (CH ₂ ) _{na 4} —) between at least one of X ¹ and X ² and the perfluoroalkylene ether structure. The speed of crosslinking between the fluoroalkylene ether-containing compound and the organometallic compound represented by the general formula (2) described later is appropriately adjusted. Therefore, the gelation reaction before coating in the coating liquid for forming the surface protective film according to this embodiment can be suppressed, and a surface protective film having excellent coating properties and excellent film forming performance can be obtained as a result. .
na3 is further preferably 1 or more and 50 or less, and more preferably 1 or more and 20 or less.
Further, na3 when Y is —NH— is more preferably 1, and na3 when na4 is 3 is more preferably 1.

  Preferred structures of the divalent group represented by the general formula (A-1) are shown below.

Na30 in (A-6) above 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.
Na40 in the above (A-13) represents an integer of 1 to 3, and 3 is preferable.
Na41 in the above (A-14) represents an integer of 1 to 3, and 3 is preferable.

  Of the structures (A-1) to (A-14), (A-1), (A-2), (A-3), (A-6), (A-8), The structures (A-9), (A-10), (A-13), and (A-14) are more preferable.

X ¹ and X ²
In the general formula (1), X ¹ and X ² each independently represent a reactive crosslinking group selected from the group consisting of (X-1) to (X-2).

R ^X1 in (X-1) represents a hydrogen atom or an optionally substituted alkyl group having 10 or less carbon atoms, that is, X ¹ and X ² represent a hydroxyl group or an alkoxy group having 10 or less carbon atoms.
The alkyl group represented by R ^X1 has more preferably 8 or less carbon atoms, and still more preferably 4 or less carbon atoms. The alkyl group may be linear, branched or cyclic.
Specific examples of the alkyl group represented by R ^X1 include methyl, ethyl, n-propyl, i-propyl, cyclopropyl, n-butyl, i-butyl, sec-butyl, tert-butyl, cyclobutyl, and n-pentyl. , Cyclopentyl, n-hexyl, cyclohexyl, 2-ethylhexyl and the like.
Among these, as R ^X1 , hydrogen atom, methyl group, ethyl group, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, n-pentyl, cyclopentyl, n-hexyl Cyclohexyl and 2-ethylhexyl are preferable, and further a hydrogen atom, a methyl group, an ethyl group, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, n-pentyl, n-hexyl, 2- More preferred is ethylhexyl.

R ^X21 , R ^X22 and R ^X23 in (X-2) each independently represent a hydrogen atom or an alkyl group having 10 or less carbon atoms which may have a substituent.
Specific examples of R ^{X21 to} R ^X23 include the same specific examples as those of R ^X1, and preferred ranges thereof are the same as those of R ^X1 .

  Here, specific examples of the perfluoroalkylene ether-containing compound represented by the general formula (1) are shown. However, the perfluoroalkylene ether-containing compound according to the present embodiment is not limited to the following examples.

(Organic metal compound)
The organometallic compound used in the present embodiment has a structure represented by the following general formula (2).

(In the general formula (2), M represents an organic metal selected from the group consisting of titanium, zirconium, silicon, aluminum, and zinc.
R ²¹ represents an alkyl group, a cycloalkyl group, an alkenyl group, or an acetyl group. The group represented by R ²¹ may have a substituent.
R ²² represents an alkyl group, a cycloalkyl group, an alkenyl group, or an acetyl group. The group represented by R ²² may have a substituent.
R ²³ represents a saturated or unsaturated divalent hydrocarbon group that forms a chelate ring by binding to the organic metal represented by M via the two O atoms represented by the general formula (2). The hydrocarbon group represented by R ²³ may have a substituent or may have a hetero atom.
o + p + q is equal to the valence of the organic metal represented by M, o is an integer from 0 to the valence, p is an integer from 0 to (the valence-2), q is 0 The above represents an integer less than the valence, and o + q is 2 or more.
However, when o is 2 or more, a plurality of R ^{21 s} are present, when p is 2 or more, a plurality of R ^{22 s} are present, and when q is 2 or more, a plurality of R ^{23 s} are the same, May be different. )

-Organic metal M represents the organic metal shown above, and among these, titanium, zirconium, silicon, and aluminum are preferable.
M is preferably titanium or silicon. By using titanium or silicon, the speed of crosslinking between the perfluoroalkylene ether-containing compound represented by the general formula (1) and the organometallic compound represented by the general formula (2) described later is appropriately adjusted. Therefore, the gelation reaction before coating in the coating liquid for forming the surface protective film according to this embodiment can be suppressed, and a surface protective film having excellent coating properties and excellent film forming performance can be obtained as a result. .

However, in the case of applying silicon as M, it is preferable to consider the suppression of hydrolysis. From this viewpoint, as the perfluoroalkylene ether-containing compound to be subjected to crosslinking polymerization, X ¹ and X ² in the general formula (1) are the above ( X-2) It is more preferable to employ a compound having ( ^-Si- (OR ^X21 ) (OR ^X22 ) (OR ^X23 )).

In the organometallic compound represented by the general formula (2), (a)-[OR ²¹ ], (b)-[R ²² ], and (c)-[O. One or more groups selected from R ²³ ... O] → are bonded. The groups (a) and (c) are crosslinking groups having reactivity with the perfluoroalkylene ether-containing compound represented by the general formula (1).
Here, o + p + q is equal to the valence of the organic metal represented by M.
o + q is 2 or more, that is, the organometallic compound represented by the general formula (2) has at least two crosslinking groups having the reactivity.
o represents an integer of 0 or more and the valence or less, preferably 2 or more.
p represents an integer of 0 or more and (the valence −2) or less, preferably 0 or 1.
q represents an integer of 0 or more and the valence or less, preferably 1 or more.
In addition, when o is 2 or more, p is 2 or more, and q is 2 or more, there are a plurality of R ²¹ , R ²² , and R ²³ , respectively. ²¹ , R ²² , and R ²³ may be the same or different.

In addition, it is preferable that said p is 1 or more from a viewpoint of improving the applicability | paintability in the coating liquid for forming the surface protective film which concerns on this embodiment, and obtaining the surface protective film excellent in the film-forming performance as a result. . When p is 1 or more, that is, (b)-[R ²² ] is bonded, the number of reactive crosslinking groups is reduced and gelation is suppressed, and gelation before coating of the coating solution is performed. It is considered that the reaction can be suppressed.

In addition, q is preferably 1 or more from the viewpoint of improving the coating property in the coating liquid for forming the surface protective film according to the present embodiment and, as a result, obtaining a surface protective film having excellent film forming performance. . When q is 1 or more, that is, having a chelate ring represented by (c)-[O ... R ²³ ... O] →, the perfluoroalkylene ether-containing compound represented by the general formula (1) and the general formula It is considered that the speed of crosslinking with the organometallic compound represented by (2) is appropriately adjusted, and the gelation reaction before application of the coating solution can be suppressed.

^{· (A) - [OR 21} ]
R ²¹ represents the group shown above, and among them, an alkyl group is preferable.
The alkyl group represented by R ²¹ preferably has 1 to 15 carbon atoms, more preferably 1 to 8 carbon atoms. The alkyl group may be linear, branched or cyclic (that is, a cycloalkyl group), and may have a substituent.
Further, the carbon number in the alkenyl group and the carbon number in the acetyl group (—C (═O) —R ^AC (R ^AC represents an alkyl group)) are also preferably in the same range as described above.

Specific examples of —OR ²¹ include —OMe, —OEt, —OnPr, —OiPr, —OnBu, —OiBu, —OtBu, —OC ₅ H ₁₁ , —OC ₆ H ₁₃ , —OC ₇ H ₁₅ , —OC. _{8 H 17, -OC 10 H 21} , -OC 3 H 5, -OC 4 H 7, -OC 5 H 9, -OC 6 H 11 and the like.
-OMe Among these, -OEt, -OnPr, -OiPr, -OnBu , -OiBu, -OC 5 H 9, -OC 6 H 11 is more preferred.

  In the above specific examples, Me represents a methyl group, Et represents an ethyl group, iPr represents an isopropyl group, and Bu represents a normal butyl group.

^{· (B) - [R 22} ]
R ²² represents a group shown above, and an alkyl group is particularly preferable.
The alkyl group represented by R ²² preferably has 1 to 15 carbon atoms, and more preferably 1 to 8 carbon atoms. The alkyl group may be linear, branched, or cyclic (that is, a cycloalkyl group), and may have a substituent. The carbon number in the alkenyl group, an acetyl group (—C ( The number of carbon atoms in = O) -R ^AC (R ^AC represents an alkyl group)) is also preferably in the same range as described above.

Specific examples of ^{-R 22, -Me, -Et, -nPr} , -iPr, -nBu, -iBu, -tBu, -C 5 H 11, -C 6 H 13, -C 7 H 15, -C _{8 H 17, -C 10 H 21} , -C 3 H 5, -C 4 H 7, -C 5 H 9, -C 6 H 11 and the like.
-Me Among these, -Et, -nPr, -iPr, -nBu , -iBu, -C 5 H 11, -C 6 H 13, -C 5 H 9, -C 6 H 11 is more preferred.

· (C) - [O ... R 23 ... O] →
In the general formula (2), the group surrounded by [] _q , that is, the group (c)-[O... R ²³ ... O] → is bonded to the organic metal represented by M to form a chelate ring. It is a group to do.
R ²³ represents a saturated or unsaturated divalent hydrocarbon group, which may have a substituent, or may have a hetero atom.
The saturated or unsaturated divalent hydrocarbon group represented by R ²³ preferably has 1 to 20 carbon atoms, and more preferably has 2 to 10 carbon atoms. The hydrocarbon group may be linear or branched, and may further have a ring.
Examples of the substituent that the divalent hydrocarbon group represented by R ²³ may have include —OH, —O ^—— NH ₄ ^{+, and the} like.
Examples of the hetero atom that the divalent hydrocarbon group represented by R ²³ may have include a nitrogen atom, an oxygen atom, and a sulfur atom.

Specific examples of (c)-[O... R ²³ ... O] → are acetylacetone chelate rings by groups represented by the following (R23-1), and ethyl acetoacetates by groups represented by the following (R23-2). Chelate ring, octylene glycol chelate ring by the group represented by the following (R23-3), triethanolamine chelate ring by the group represented by the following (R23-4), group represented by the following (R23-5) And a lactic acid chelate ring by the group represented by the following (R23-6).
Among these, an acetylacetone chelate ring is more preferable.

Here, the relative organometallic represented by M (c) - shows the ^{[O ... R 23 ... O]} → combine to examples Aspects forming a chelate ring. For example, the structure of an organometallic compound having Zr as M and having an acetylacetone chelate ring formed by four groups represented by the above (R23-1) with respect to Zr is the structure shown below.

Specific examples of the organometallic compound represented by the general formula (2) are shown. However, the organometallic compound according to the present embodiment is not limited to the following example.
-((2) -1) Ti- (O-iPr) ₄
-((2) -2) Ti- (O-iPr) ₂ (AcAc) ₂
・ ((2) -3) Ti- (AcAc) ₄
・ ((2) -4) Zr- (O-Bu) ₄
・ ((2) -5) Zr- (O-Bu) ₃ (AcAc)
・ ((2) -6) Zr- (AcAc) ₄
・ ((2) -7) Si- (O-Me) ₄
・ ((2) -8) Si- (O-Et) ₄
・ ((2) -9) Si- (Me) (O-Me) ₃
・ ((2) -10) Si- (Me) (O-Ee) ₃
・ ((2) -11) Si- (Et) (O-Me) ₃
・ ((2) -12) Si- (Et) (O-Ee) ₃
・ ((2) -13) Al- (O-iPr) ₃
In the above specific examples, AcAc represents a chelate ring by acetylacetone.

(Crosslinked polymer)
The crosslinked polymer contained in the surface protective film according to the present embodiment includes a perfluoroalkylene ether-containing compound represented by the general formula (1) and an organometallic compound represented by the general formula (2). Cross-linked and polymerized.
Examples of preferred combinations of the perfluoroalkylene ether-containing compound represented by the general formula (1) and the organometallic compound represented by the general formula (2) include the following combinations.

(Method for forming surface protective film (crosslinking polymerization method))
The surface protective film according to this embodiment is a coating liquid (surface) containing a perfluoroalkylene ether-containing compound represented by the general formula (1) and an organometallic compound represented by the general formula (2). It is formed by applying a coating solution for forming a protective film) onto a substrate and crosslinking polymerization.

  Ratio of addition amount of organometallic compound represented by general formula (2) added as crosslinking agent to amount of perfluoroalkylene ether-containing compound represented by general formula (1) (amount of general formula (2) / Amount of the general formula (1) × 100 [% by mass]) is preferably 2% by mass to 100% by mass, more preferably 5% by mass to 80% by mass, and more preferably 10% by mass to 60% by mass. Further preferred.

When the mixture of the perfluoroalkylene ether-containing compound and the organometallic compound is a liquid, it may be used as it is as the coating liquid for forming the surface protective film.
When using a mixture of the perfluoroalkylene ether-containing compound and the organometallic compound that can be dissolved in a solvent regardless of whether it is solid or liquid, the compound and other additives are dissolved in the solvent and the coating solution Is prepared, applied onto a substrate, and subjected to cross-linking polymerization.
Further, when using a mixture of the perfluoroalkylene ether-containing compound and the organometallic compound that is solid and insoluble in a solvent, the mixture is heated to a temperature at which these compounds and other additives can be dissolved, It is formed by polymerization.
However, from the viewpoint of manufacturability, it is preferable to form the surface protective film using a compound that can be dissolved in a solvent or a compound that is liquid at room temperature (25 ° C.).

  Examples of the solvent used in the coating solution include acetone, methyl ethyl ketone (2-butanone), methyl butyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, ethyl acetate, propyl acetate, isopropyl 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- Toki Shino Na perfluorobutane, 1-ethoxy-nonafluorobutane, and the like.

When performing the cross-linking polymerization, energy may be supplied from the outside, and examples thereof include supply of energy by means of irradiating ultraviolet rays, means of irradiating electron beams, and means of heating. Further, a catalyst may be added to perform the crosslinking polymerization.
Especially, it is preferable to heat, and as the temperature, 140 to 250 degreeC is preferable, and 160 to 230 degreeC is more preferable. By applying heat, cross-linking polymerization can be promoted, and by-products (for example, isopropanol, butanol, etc.) due to the cross-linking reaction can be efficiently removed.

(Physical properties of surface protective film)
The surface protective film according to this embodiment is a material having excellent heat resistance as described above. Note that the excellent heat resistance means specifically exhibiting excellent scratch resistance even in a high temperature environment.
Here, the heat-resistant temperature (usable temperature range) in the surface protective film according to this embodiment is preferably 60 ° C. or higher and 200 ° C. or lower, and more preferably 80 ° C. or higher and 160 ° C. or lower.

  In the surface protective film according to this embodiment, the contact angle of water at 25 ° C. is preferably 90 ° or more, and more preferably 100 ° or more.

  The contact angle is measured by the θ / 2 method at 25 ° C. using a contact angle meter using water on the surface protective film sample applied on the film. Moreover, the contact angle with respect to the hexadecane mentioned later is measured by changing the water to hexadecane.

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

[Usage]
The surface protective film according to the present embodiment is assumed to be used in an environment in which the use environment is higher than normal temperature (25 ° C.) and the surface can be scratched by contact with foreign matter. It can use without being specifically limited.
For example, an endless belt or roll for an image forming apparatus used for a fixing member, an intermediate transfer member, a recording medium conveying member, etc. in an image forming apparatus, a car body or window glass, a solar cell panel, a panel that reflects sunlight, etc. Can be mentioned.

[Endless belt]
Here, an endless belt for an image forming apparatus, which is an example of a use application of the surface protective film according to the present embodiment, will be described.
The endless belt for an image forming apparatus according to the present embodiment includes a belt-shaped base material and the surface protective film according to the above-described present embodiment provided on the belt-shaped base material.

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

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

Hereinafter, the case where the endless belt 1 is used as a fixing belt will be described.
The material used for the substrate 2 is preferably a heat-resistant material, and specifically selected from various known plastic materials and metal materials.

  Among plastic materials, what are generally called engineering plastics are suitable, for example, fluorine resin, polyimide (PI), polyamideimide (PAI), polybenzimidazole (PBI), polyetheretherketone (PEEK), polysulfone (PSU). Polyethersulfone (PES), polyphenylene sulfide (PPS), polyetherimide (PEI), wholly aromatic polyester (liquid crystal polymer) and the like are preferable. Of these, thermosetting polyimides, thermoplastic polyimides, polyamide imides, polyether imides, fluororesins, and the like that are excellent in mechanical strength, heat resistance, wear 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, For example, 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 resins and the metal materials may be laminated.

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

  Examples of the material used for the substrate 2 include a polyimide resin, a polyamideimide resin, a polyester resin, a polyamide resin, a fluorine resin, and the like. Among these, it is more preferable to use a polyimide resin and a polyamideimide resin. preferable. In addition, if a base material is cyclic | annular (endless shape), it may or may not have a joint, and the thickness of the base material 2 is usually preferably 0.02 to 0.2 mm.

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 within a range of 10 ¹³ Ωcm. Therefore, as described above, the base material 2 and the surface layer 3 are coated with carbon black such as ketjen black and acetylene black, metals or alloys such as graphite, aluminum, nickel and copper alloys, tin oxide, zinc oxide and titanium as a conductive agent. It is preferable to add a metal oxide such as potassium oxide, tin oxide-indium oxide or tin oxide-antimony oxide composite oxide, a conductive polymer such as polyaniline, polypyrrole, polysulfone, polyacetylene, etc. “Conductivity” means that the volume resistivity is less than 10 ⁷ Ω · cm). These conductive agents are used alone or in combination of two or more.

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

  In the case of fixing applications, the endless belt 1 may include an elastic layer between the base material 2 and the surface layer 3. As a material for the elastic layer, for example, various rubber materials are used. Examples of the various rubber materials include urethane rubber, ethylene / propylene rubber (EPM), silicone rubber, and fluorine rubber (FKM). Silicone rubber having excellent heat resistance and workability is particularly preferable. Examples of the silicone rubber include RTV silicone rubber and HTV silicone rubber. Specifically, polydimethyl silicone rubber (MQ), methyl vinyl silicone rubber (VMQ), methyl phenyl silicone rubber (PMQ), fluoro Examples include silicone rubber (FVMQ).

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 substrate 2 and the surface layer 3.
Examples of the material used for the heat generating layer include non-magnetic metals. Specifically, for example, gold, silver, copper, aluminum, zinc, tin, lead, bismuth, beryllium, antimony, and alloys thereof (these A metal material such as an alloy containing
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 roll for an image forming apparatus according to the present embodiment includes a cylindrical base material and the surface protective film according to the above-described present embodiment provided on the cylindrical base material.

Next, the roll according to this embodiment will be described. The roll of this embodiment is a cylindrical roll having a base material and a surface layer laminated on the surface of the base material.
As the surface layer, the surface protective film according to the above-described embodiment is applied.

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

Hereinafter, a 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 includes a surface layer 613 on a cylindrical core 611. Further, as illustrated 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), metals such as SUS, iron, and copper, alloys, ceramics, and FRM. The fixing device 72 of the present embodiment is configured by 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 with high heat resistance. In particular, an elastic body such as rubber or elastomer having a rubber hardness of about 15 to 45 ° (JIS-A) is preferably used, and examples thereof include silicone rubber and fluororubber.

  In the present embodiment, among these materials, silicone rubber is preferable because it has low surface tension and excellent elasticity. Examples of the silicone rubber include RTV silicone rubber and HTV silicone rubber. Specifically, polydimethyl silicone rubber (MQ), methyl vinyl silicone rubber (VMQ), methyl phenyl silicone rubber (PMQ), fluoro Examples include silicone rubber (FVMQ).

  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 an HTV silicone rubber having a rubber hardness of 35 ° (JIS-A) with a thickness of 72 μm.

  The thickness of the surface layer 613 is, for example, 5 μm or more and 50 μm or less, and may be 10 μm or more and 30 μm or less.

  As a heat source for heating the fixing roll 610, for example, a halogen lamp 660 is used, and there is no particular limitation as long as it has a shape and structure accommodated in 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 temperature sensing element 690, For example, a thermistor, a temperature sensor, etc. are mentioned.

[Image forming apparatus]
Next, the image forming apparatus of this embodiment using the endless belt of this embodiment and the roll of this 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. 3 is a schematic diagram for explaining a main part of an image forming apparatus of a tandem type.

  Specifically, the image forming apparatus 101 exposes the surface of the photosensitive member 79 by exposing the surface of the photosensitive member 79 to the photosensitive member 79 (electrostatic latent image holding member), a charging roll 83 that charges the surface of the photosensitive member 79, and forming an electrostatic latent image. A laser generator 78 (electrostatic latent image forming means) to be formed, a developing device 85 (developing means) for developing a latent image formed on the surface of the photoreceptor 79 using a developer, and forming a toner image; An intermediate transfer belt 86 (intermediate transfer body) to which the toner image formed by the developing device 85 is transferred from the photosensitive member 79; a primary transfer roll 80 (primary transfer means) for transferring the toner image to the intermediate transfer belt 86; A photoreceptor cleaning member 84 that removes toner, dust, and the like attached to the photoreceptor 79, a secondary transfer roll 75 (secondary transfer unit) that transfers the toner image on the intermediate transfer belt 86 to the recording medium, and a recording medium Fixing device 72 for fixing the toner image ( And Chakushudan), is configured to include a. The photoconductor 79 and the primary transfer roll 80 may be arranged immediately above the photoconductor 79 as shown in FIG. 3, or may be arranged at a position shifted from just above the photoconductor 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, a primary transfer roll 80 and a photosensitive member cleaning member 84 are arranged around the photosensitive member 79 counterclockwise via a charging roll 83, a developing device 85, and an intermediate transfer belt 86. These one set of members form a developing unit corresponding to one color. Each developing unit is provided with a toner cartridge 71 for replenishing the developer in the developing unit 85, and a charging roll 83 (rotating direction of the photosensitive member 79) is provided with respect to the photosensitive member 79 of each developing unit. A laser generator 78 that irradiates the surface of the photoreceptor 79 downstream and upstream of the developing device 85 with laser light corresponding to image information is provided.

  Four developing units corresponding to four colors (for example, cyan, magenta, yellow, and black) are arranged in series in the horizontal direction in the image forming apparatus 101, and the photosensitive member 79 of the four developing units and the primary are arranged. An intermediate transfer belt 86 is provided so as to pass through a 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 on the inner surface side in the following order in the counterclockwise direction, thereby forming 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 with the intermediate transfer belt 86 in contact with the drive roll 81.

  The toner formed on the outer peripheral surface of the intermediate transfer belt 86 on the surface of the recording paper conveyed from the paper supply unit 77 via the paper path 76 to 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 so as to contact the support roll 73.

  In addition, a paper supply unit 77 that accommodates 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 paper supply unit 77 via a paper path 76. The recording medium is supplied so as to pass through the contact portion with 75. The recording medium that has passed through the contact portion is further transported by a transport means (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 toner image is formed for each developing unit. After charging the surface of the photoreceptor 79 rotating counterclockwise by the charging roll 83, the toner image is latently formed on the surface of the photoreceptor 79 charged by the laser generator 78 (exposure device). An image (electrostatic latent image) is formed, and then the latent image is developed with 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 photoreceptor 79 is formed. Is transferred to the outer peripheral surface of the intermediate transfer belt 86 rotating in the direction of arrow C. The photosensitive member 79 after the toner image is transferred is cleaned by the photosensitive member cleaning member 84 for toner, dust, etc. attached to the surface of the photosensitive member 79 in preparation for the next toner image formation.

  The toner images developed for each color development unit are sequentially superimposed on the outer peripheral surface of the intermediate transfer belt 86 so as to correspond to the image information, and are conveyed to the secondary transfer unit by the secondary transfer roll 75. The image is transferred from the paper supply unit 77 to the surface of the recording paper conveyed via the paper path 76. The recording paper on which the toner image has been transferred is further fixed by being heated by pressure when passing through the contact portion of the fixing device 72. After an image is formed on the surface of the recording medium, the recording paper is discharged out of the image forming device. Is 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. A fixing device 72 shown in FIG. 4 includes a fixing roll 610 as a rotating body that is driven to rotate, an endless belt 620 (pressure belt), and a pressure pad 640 that is a pressure member that pressurizes the fixing roll 610 via the endless belt 620. And is configured. Note that the endless belt 620 and the fixing roll 610 need only be relatively pressed on the pressure pad 640. Accordingly, the endless belt 620 side may be pressed against the fixing roll 610, and the fixing roll 610 side may be pressed against the endless belt 620.

  Inside the fixing roll 610, a halogen lamp 660 as an example of a heating unit for heating the unfixed toner image in the sandwiching area is disposed. The heating means is not limited to the halogen lamp, and other heat generating members that generate 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 a set temperature (for example, 150 ° C.).

  The endless belt 620 is rotatably supported by a pressure pad 640 disposed therein, a belt travel guide 630, and an edge guide (not shown). In the sandwiching area N, the fixing roll 610 is placed in contact with the pressurized roll 610 in a pressurized state.

  The pressure pad 640 is disposed inside the endless belt 620 in a state of being pressed against the fixing roll 610 via the endless belt 620, and forms a sandwiching region N between the pressure pad 640 and the fixing roll 610. In the pressure pad 640, a pre-nip member 641 for securing a wide pinching area N is disposed on the entrance side of the pinching area N, and a peeling pinch member 642 for distorting the fixing roll 610 is pinched. It is arranged on the exit side of the insertion area N.

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

  Further, a belt traveling guide 630 is attached to the holder 650, and the endless belt 620 is configured to rotate smoothly. That is, the belt running guide 630 is made of a material having a small static friction coefficient in order to rub against the inner peripheral surface of the endless belt 620. Further, the belt traveling guide 630 is formed of a material having low thermal conductivity so that it is difficult to remove 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 is rotated in a direction opposite to the rotation direction of the fixing roll 610 following the rotation. That is, the fixing roll 610 rotates in the clockwise direction in FIG. 4, whereas the endless belt 620 rotates in the counterclockwise direction.

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

  In the fixing device 72, the pinching region N is secured by the concave pre-pinching member 641 that follows the outer peripheral surface of the fixing roll 610.

  Further, in the fixing device 72 according to the present embodiment, the separation of the fixing roll 610 is disposed so as to protrude from the outer peripheral surface of the fixing roll 610, so that the distortion of the fixing roll 610 is locally localized in the exit area of the clamping area N. It is comprised so that it may become large. With this configuration, the fixed sheet K is peeled off from the fixing roll 610.

  Further, 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 where the peeling baffle 710 is close to the fixing roll 610 in a direction (counter direction) opposite to the rotation direction of the fixing roll 610.

  Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited only to the following examples. In the following, “part” is based on mass unless otherwise specified.

〔Example〕
<Preparation of coating solution for forming surface protective film>
The following composition was mixed to prepare a coating solution.

In addition, the fluororesins (A) to (B) shown in Table 1 are perfluoroalkylene ether-containing compounds having the following structures.
Fluorine resin (A): manufactured by Solvay, number average molecular weight 1600
-Fluororesin (B): manufactured by Solvay, number average molecular weight 2000, R ^{B1 to} R ^B6 each independently represent an ethyl group or a methyl group.

<Formation of surface protective film (crosslinking polymerization)>
The coating solution was applied (cast) to a 90 μm-thick polyimide film, dried at 80 ° C. for 5 minutes to volatilize the solvent, and further heated at 200 ° C. for 1 hour to obtain a surface protective film.

[Comparative Example 1]
50 parts perfluoroalkylene ether compound having hydroxyl groups at both ends (Solvay, D4000, structure / a compound in which the number of m1 and m2 in the fluororesin (A) is different and the number average molecular weight is 4000) 14 parts of-(bisacryloyloxymethyl) ethyl isocyanate and 0.01 part of dibutyltin dilaurate were added and stirred at 60 ° C. for 6 hours. A perfluoroalkylene ether having both ends modified with urethane-containing methacrylate was obtained.
Add 0.5 parts DAROCUR1173 (BASF), apply (cast) to 90μm-thick polyimide film, and evaporate the solvent by drying at 80 ° C for 5 minutes. The surface protective film was obtained. Irradiation conditions of ultraviolet rays were as follows: under a nitrogen atmosphere (oxygen concentration of 1% or less), a high-pressure mercury lamp was used and a light amount of 1000 mmJ / cm ² was irradiated.

[Comparative Example 2]
Addition of 20 parts of tetrahydrofuran (THF) to 50 parts of a perfluoroalkylene ether compound having hydroxyl groups at both ends (Solvay, D1600, structure / perfluoroalkylene ether-containing compound having the structure shown in the fluororesin (A)) Then, 5 parts of 1,1- (bisacryloyloxymethyl) ethyl isocyanate and 0.01 part of dibutyltin dilaurate were added under stirring. After stirring at 60 ° C. for 5 hours, the reaction solution was concentrated to obtain 55 parts of perfluoroalkylene ether having both ends modified with urethane-containing methacrylate.
Add 0.5 parts DAROCUR1173 (BASF), apply (cast) to 90μm-thick polyimide film, and evaporate the solvent by drying at 80 ° C for 5 minutes. The surface protective film was obtained. Irradiation conditions of ultraviolet rays were as follows: under a nitrogen atmosphere (oxygen concentration of 1% or less), a high-pressure mercury lamp was used and a light amount of 1000 mmJ / cm ² was irradiated.

[Evaluation]
Scratch resistance evaluation The surface protective film samples obtained in the above examples and comparative examples were scratched at a normal temperature (25 ° C) with a load of 2 N using a scratch hardness meter (manufactured by ERICHSEN, tip diameter: 0.75 mm). After scratching at 80 ° C. for 30 seconds, the scratched portion was observed to evaluate the presence or absence of scratches.
B (x): Protective film sample is scratched A (○): Protective film sample is not damaged

Toner peelability The surface protective film samples obtained in the above Examples and Comparative Examples, and the samples heated at 180 ° C. for 20 hours are attached to the fixing roll surface of the fixing machine, and the black unfixed solid image is passed through. Paper was used to confirm the fixability.
As the fixing device, a product name: DocuCentre C2101 manufactured by Fuji Xerox Co., Ltd. was used. The evaluation criteria are as follows.
C (x): Toner adheres to the entire surface of the protective film sample B (△): Adhers toner to half of the protective film sample A (◯): No toner adheres to the protective film sample

-Contact angle evaluation About the surface protective film sample obtained by the said Example and comparative example, the contact angle 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 (the Kyowa Interface Science company make, model number: CA-S-Rugata).

-Surface change with time The surface protective film samples obtained in the above Examples and Comparative Examples were heated at 140 ° C. under a load of ² kg / cm ² . The contact angle of hexadecane after heating at 140 ° C. for 10 hours and after heating at 140 ° C. for 20 hours was measured to evaluate surface degradation.
The results are shown in Table 2 below.

DESCRIPTION OF SYMBOLS 1 Endless belt, 2 Substrate, 3 Surface layer, 72 Fixing device, 75 Secondary transfer roll, 78 Laser generator, 79 Photoreceptor, 80 Primary transfer roll, 83 Charging roll, 85 Developer, 86 Intermediate transfer belt, 101 Image forming apparatus, 610 fixing roll, 620 endless belt, K paper

Claims (6)

A surface protective film comprising a crosslinked polymer of a perfluoroalkylene ether-containing compound represented by the following general formula (1) and an organometallic compound represented by the following general formula (2).


(In the general formula (1), Z represents a divalent group selected from the group consisting of the above (Z-1) to (Z-2) or two or more and five or less groups selected from the group. And Z represents a divalent group represented by (Z-1) and includes a divalent group represented by (Z-1) in the range of 1 to 5 and the divalent group represented by (Z-2). And a group containing 0 or more and 2. In the above (Z-2), R ^Z1 and R ^Z2 each independently represent a fluorine atom or a trifluoromethyl group, provided that at least one of R ^Z1 and R ^Z2 represents a trifluoromethyl group. In the case where Z contains two divalent groups represented by the above (Z-2), a plurality of R ^Z1 and R ^Z2 may be the same or different.
m represents an integer of 1 or more. However, when m is 2 or more, a plurality of Z may be the same or different.
A ¹ and A ² each independently represent a divalent organic group. na1 and na2 each independently represents 0 or 1.
X ¹ and X ² each independently represent a reactive crosslinking group selected from the group consisting of (X-1) to (X-2). R ^X1 in the above (X-1) represents a hydrogen atom or an alkyl group having 10 or less carbon atoms which may have a substituent. R ^X21 , R ^X22 and R ^X23 in (X-2) each independently represent a hydrogen atom or an alkyl group having 10 or less carbon atoms which may have a substituent. )


(In the general formula (2), M represents an organic metal selected from the group consisting of titanium, zirconium, silicon, aluminum, and zinc.
R ²¹ represents an alkyl group, a cycloalkyl group, an alkenyl group, or an acetyl group. The group represented by R ²¹ may have a substituent.
R ²² represents an alkyl group, a cycloalkyl group, an alkenyl group, or an acetyl group. The group represented by R ²² may have a substituent.
R ²³ represents a saturated or unsaturated divalent hydrocarbon group that forms a chelate ring by binding to the organic metal represented by M via the two O atoms represented by the general formula (2). The hydrocarbon group represented by R ²³ may have a substituent or may have a hetero atom.
o + p + q is equal to the valence of the organic metal represented by M, o is an integer from 0 to the valence, p is an integer from 0 to (the valence-2), q is 0 The above represents an integer less than the valence, and o + q is 2 or more.
However, when o is 2 or more, a plurality of R ^{21 s} are present, when p is 2 or more, a plurality of R ^{22 s} are present, and when q is 2 or more, a plurality of R ^{23 s} are the same, May be different. ) 2. The device according to claim 1, wherein at least one of the na1 and na2 in the general formula (1) is 1, and the A ¹ and A ² represent a divalent group represented by the following general formula (A-1). Surface protective film.


(In the general formula (A-1), A ³ represents a divalent group selected from the group consisting of (A3-1) to (A3-4) or two or more groups selected from the group. A ³ represents a combined divalent group, and A ³ includes a divalent group represented by (A3-1) of 0 to 5 inclusive, and the divalent group represented by (A3-2). The group contains 0 or more and 2 or less, the divalent group represented by (A3-3) contains 0 or more, and the divalent group represented by (A3-4) contains 0 or 1. R ^A1 and R ^A2 in A3-2) each independently represent a fluorine atom or a trifluoromethyl group, provided that at least one of R ^A1 and R ^A2 represents a trifluoromethyl group, and A ³ represents the above (A3-2). each of R ^A1 and R ^A2 there are multiple same when) containing two divalent groups represented by It may be different even.
Y represents —O— or —NH—. na3 represents an integer of 0 or more, and na4 represents an integer of 1 to 3. However, when na3 is 2 or more, a plurality of [ _—Y— (CH ₂ ) _na4 —] groups may be the same or different.
The divalent group represented by the general formula (A-1) is bonded to the perfluoroalkylene ether structure at the (* 1) portion, and (—X ¹ ) or (—X ² ) at the (* 2) portion. ). )   The surface protective film according to claim 1, wherein the p in the general formula (2) is 1 or more.   The surface protection film according to claim 1, wherein the q in the general formula (2) is 1 or more.   The surface protective film according to claim 1, wherein the organic metal represented by M in the general formula (2) is titanium or silicon.   The surface protective film according to any one of claims 2 to 5, wherein the na3 in the general formula (A-1) is 1 or more.