JPH1160955A - Fluororesin or fluorine latex coated silicone rubber fixing roll - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fluororesin coating having a low hardness silicone rubber layer, which has a long service life, hardly changes the rubber hardness of the silicone rubber layer even when exposed to a high temperature state in a coating process. Provide a silicone rubber fixing roll. SOLUTION: In a fixing roll in which a silicone rubber layer is formed on the outer peripheral surface of a roll shaft and the surface thereof is coated with a fluororesin, the silicone rubber layer (A) is bonded to silicon atoms only in a side chain in one molecule. Organopolysiloxane (B) containing two or more aliphatic unsaturated hydrocarbon groups, and having a content of the same group-containing siloxane unit of 0.05 to 5 mol%, in at least two silicon atoms in one molecule. Organohydrogenpolysiloxane (C) having a directly bonded hydrogen atom, platinum or platinum-based compound
Catalytic amount (D) Filler (E) Contains a heat resistance improver selected from carbon black, cerium oxide, cerium hydroxide and iron oxide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fixing roll used for a copying machine, a laser beam printer, a facsimile, etc., wherein a silicone rubber layer is formed on the outer peripheral surface of a roll shaft, and The present invention relates to a fluorine resin or fluorine latex-coated silicone rubber fixing roll coated with a resin or fluorine latex.

[0002]

2. Description of the Related Art
Silicone rubber is used for fixing rolls used in copiers, laser beam printers, faxes, and the like.
This is because silicone rubber has superior releasability to toner, heat resistance, compression set and the like as compared with other rubber materials.

[0003] Furthermore, with the recent increase in the speed of this type of equipment,
An oil fuse that supplies silicone oil to the roll surface is used to improve the toner releasability, and a fixing width (nip width) between the rolls is secured to increase the fixing time when the speed is increased. For the purpose, rubber materials have been reduced in hardness.

However, since silicone rubber is originally composed of the same siloxane unit as silicone oil and has good affinity, there is a problem that if the hardness is further reduced, the silicone rubber swells due to the fused silicone oil. I have.

Therefore, as a method of solving these problems, a roll surface made of low-hardness silicone rubber or silicone rubber foam is covered with a film formed by coating a fluorine resin or a fluorine latex. I have.

However, this method can significantly improve the service life of the fixing roll. For example, a fluororesin tube prepared by curing silicone rubber in a fluororesin tube previously formed into a cylindrical shape is used. Unlike the case of silicone rubber rolls coated with, the process of coating the fluorocarbon resin at the melting temperature or higher when coating the surface of the silicone rubber roll with the fluorocarbon resin, or the process of coating the surface of the silicone rubber roll with the fluorine latex and firing at high temperature 300 ~
It is necessary to set the temperature to a high temperature of 350 ° C. for 15 minutes to 1 hour.
There is a drawback that the yield of roll production becomes poor. This change in hardness is more remarkable as the hardness of the roll becomes lower. Therefore, with the recent decrease in hardness, improvement of the roll material has been urgently required.

[0007] The silicone rubber roll coated with a fluororesin or fluorine latex to form a coating forms a thinner fluororesin layer or a fluorine latex layer than a silicone rubber roll coated with a fluororesin tube. To obtain a more flexible and highly durable roll in which the fluororesin / latex layer and the silicone rubber layer are more firmly adhered and the fluororesin / latex layer and the silicone rubber layer have good followability. This is advantageous in that it can be performed.

The present invention has been made in view of the above circumstances, has a long life as a fixing roll, can secure a nip width, and has a rubber hardness of a silicone rubber layer even when exposed to a high temperature in a coating process. It is an object of the present invention to provide a fluororesin or fluorine latex-coated silicone rubber fixing roll having a silicone rubber layer of low hardness, which hardly changes.

[0009]

Means for Solving the Problems and Embodiments of the Invention The present inventors have conducted intensive studies to achieve the above object, and as a result, a silicone rubber layer has been formed on the outer peripheral surface of the roll shaft. In a fluorine resin or fluorine latex-coated silicone rubber fixing roll in which a layer surface is coated with a fluorine resin or a fluorine latex, the silicone rubber layer is formed by (A) aliphatic unsaturation in which only a side chain in one molecule is bonded to a silicon atom. 2 hydrocarbon groups
And (B) at least two silicon atoms in one molecule in one molecule, and an organopolysiloxane containing 0.05 to 5 mol% of the aliphatic unsaturated hydrocarbon group-containing siloxane unit. A hydrogen atom-containing organohydrogenpolysiloxane, (C) platinum or a platinum-based compound, (D) a filler, and (E) a heat resistance improver selected from carbon black, cerium oxide, cerium hydroxide and iron oxide. And the rubber hardness after curing (JIS
When formed from a cured product of a silicone rubber composition having a JIS-A hardness of 15 or less (K6301), the life as a fixing roll is extremely long, and the nip width can be sufficiently secured. In the process of coating the fluorocarbon resin at the melting temperature or higher when coating the surface of the silicone rubber roll, or in the process of coating the surface of the silicone rubber roll with the fluorine latex at a high temperature and then firing at a high temperature of 300 to 350 ° C. for 15 minutes to 1 hour In addition, the present inventors have found that a rubber roll hardly changes before and after this high temperature state, has a low hardness silicone rubber layer, and has a good yield at the time of production.

Accordingly, the present invention provides a fluororesin or fluorolatex-coated silicone rubber fixing roll in which a silicone rubber layer is formed on the outer peripheral surface of a roll shaft and the surface of the silicone rubber layer is coated with a fluororesin or fluorolatex. The silicone rubber layer contains (A) two or more aliphatic unsaturated hydrocarbon groups bonded to a silicon atom only in a side chain in one molecule, and the content of the aliphatic unsaturated hydrocarbon group-containing siloxane unit is 100 parts by weight of an organopolysiloxane having a content of 0.05 to 5 mol% (B) An organohydrogenpolysiloxane having at least two hydrogen atoms directly bonded to a silicon atom in one molecule In the organopolysiloxane of the component (A) Component (B) organohydrogenpolysiloxane relative to the aliphatic unsaturated hydrocarbon group of (C) Platinum or platinum-based compound Catalyst amount (D) Filler 5-300 parts by weight (E) Carbon black, cerium oxide, water It contains 0.1 to 30 parts by weight of a heat resistance improver selected from cerium oxide and iron oxide, and has a rubber hardness after curing (JIS K6).
The present invention provides a fluorine resin or fluorine latex-coated silicone rubber fixing roll, which is formed of a cured product of a silicone rubber composition having a JIS-A hardness of 301 or less (15 or less).

Hereinafter, the present invention will be described in more detail. The fluororesin or fluorolatex-coated silicone rubber fixing roll of the present invention has a silicone rubber layer formed on the outer peripheral surface of a roll shaft, and the fluororesin is coated on the surface of the silicone rubber layer. Alternatively, a film of fluorine latex is coated by means such as melting or baking, and the silicone rubber layer is formed of a cured product of the silicone rubber composition containing the above components (A) to (E). It is a thing.

The component (A) used in the present invention comprises, in one molecule, an aliphatic unsaturated hydrocarbon group bonded to a silicon atom only in a side chain of the molecule (that is, bonded to a silicon atom of a diorganosiloxane unit). Only as a substituent)
Basically, it is a linear diorganopolysiloxane, which is the main component of the present invention.

Here, as the organopolysiloxane, those represented by the following average molecular formula (I) can be suitably used.

[0014]

Embedded image (However, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group other than an aliphatic unsaturated hydrocarbon group, R ² is a monovalent aliphatic unsaturated hydrocarbon group, and m and n are each m ≧ 38, n ≧
2, 40 ≦ m + n ≦ 20,000, preferably 100 ≦
m + n ≦ 10,000, 0.05 ≦ [n / (m + n)]
× 100 ≦ 5, preferably 0.1 ≦ [n / (m + n)]
It is an integer satisfying × 100 ≦ 3. )

In the above formula (I), R ¹ preferably has 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, Alkyl groups such as isobutyl group, tert-butyl group, hexyl group, cyclohexyl group, octyl group and decyl group, aryl groups such as phenyl group and tolyl group, aralkyl groups such as benzyl group and phenylethyl group, and hydrogen of these groups Chloromethyl, bromoethyl, 3,3,3-trifluoropropyl, cyanoethyl and the like, in which some or all of the atoms have been substituted with a halogen atom such as chlorine, bromine or fluorine, or a cyano group, and the like. Groups, phenyl groups and 3,3,3-trifluoropropyl groups are preferred. R ² is an aliphatic unsaturated hydrocarbon group such as a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a hexenyl group or the like having 2 to 6 carbon atoms, particularly an alkenyl group having 2 to 4 carbon atoms. Particularly, a vinyl group is preferable.

In the above formula (I), each substituent is different
Or the same, but the component (A) of the present invention
The organopolysiloxane has only side chains in the molecule (ie,
R¹ R^Two SiO_2/2A diorganosiloxane unit represented by
Substituent R bonded to the silicon atom of^Two Only)
Containing the above aliphatically unsaturated hydrocarbon groups and
The amount of the siloxane unit containing a sum hydrocarbon group is 0.05
To 5 mol%, preferably 0.1 to 3 mol%.
is necessary. In the present invention, the aliphatic unsaturated hydrocarbon
The amount (mol%) of the siloxane unit containing an elemental group is
(A) Diorganosiloxane unit constituting the main chain of component
(Ie, R¹ _TwoSiO_2/2Unit and R¹ R^Two SiO_2/2Units
Siloxane unit containing aliphatic unsaturated group (total)
Chi, R¹ _TwoSiO_2/2Unit)
You. When the content of the aliphatic unsaturated hydrocarbon group is 0.05
If the ratio is less than 100%, physical properties of rubber such as mechanical strength
It is difficult to maintain, and if it exceeds 5 mol%, low hardness
It is very difficult to obtain a cured product of

Incidentally, this organopolysiloxane is
Generally, the main chain is basically a diorganosiloxane unit
(Ie, R¹ _TwoSiO_2/2Unit and R¹ R^Two SiO_2/2unit)
, And both ends of the molecular chain are triorganosiro
A xy group (ie, R¹ _ThreeSiO_{1 / Two}Unit)
Diorganopolysiloxane in the form of¹
SiO_3/2Unit, R^Two SiO_3/2Unit or SiO_4/2Units
It may be a branched shape or a ring shape.

The degree of polymerization (or the number of silicon atoms in the molecule) of the organopolysiloxane of the above formula (I) is 50.
20,000, especially 100-15,000, especially about 500-10,000 are suitable.

The organohydrogenpolysiloxane of the component (B) used in the present invention reacts with the component (A) and acts as a crosslinking agent. The molecular structure of the organohydrogenpolysiloxane is not particularly limited, and is conventionally produced. For example, various types such as linear, cyclic, branched, and three-dimensional network (resin-like) structures can be used, but hydrogen bonded to at least two, preferably three or more silicon atoms in one molecule is available. Atoms (ie,
(SiH group).

A hydrogen atom (SiH) bonded to this silicon atom
Group) may be bonded to either the silicon atom at the terminal of the molecular chain or the silicon atom in the middle of the molecular chain, or may be bonded to both. The number of silicon atoms in the molecule is 200 or less, usually 2 to 150, and particularly 4 to
The number is preferably about 50.

As the substituent other than the hydrogen atom bonded to the silicon atom of the organohydrogenpolysiloxane, the substituent R ¹ of the organopolysiloxane of the component (A) is used.
Specific examples include the same as those exemplified above, particularly, unsubstituted or substituted monovalent hydrocarbon groups other than a methyl group, a phenyl group, a 3,3,3-trifluoropropyl group, and an aliphatic unsaturated group.

The above-mentioned organohydrogenpolysiloxane can be produced by a known production method.
Very common production methods include hexamethyldisiloxane and / or 1,1'-dihydro-2,2 ', 3,3' which can be an end group with octamethylcyclotetrasiloxane and / or tetramethylcyclotetrasiloxane.
A compound containing a tetramethyldisiloxane unit can be easily obtained by equilibrating at a temperature of about −10 to + 40 ° C. in the presence of a catalyst such as sulfuric acid, trifluoromethanesulfonic acid or methanesulfonic acid.

The amount of the organohydrogenpolysiloxane of the component (B) is such that the amount of the organohydrogenpolysiloxane of the component (B) is based on one aliphatic unsaturated hydrocarbon group contained in the organopolysiloxane of the component (A). The amount of the silicon-bonded hydrogen atoms (SiH groups) contained in the siloxane is in the range of 0.1 to 3 in molar ratio, preferably in the range of 0.5 to 2, and if this ratio is less than 0.1, If the crosslinking density becomes too low, the heat resistance of the cured silicone rubber is adversely affected. If it is more than 3, foaming problems due to the dehydrogenation reaction may occur, and the heat resistance may also be adversely affected.

The platinum (P) or platinum compound as the component (C) used in the present invention is used as a catalyst for accelerating the above-mentioned curing addition reaction (hydrosilation) of the components (A) and (B). Things.

As the platinum or platinum-based compound, known compounds can be used, and specifically, platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, chloroplatinic acid and olefin, aldehyde, vinylsiloxane Or, complexes with acetylene alcohols and the like are exemplified.

The amount of platinum or platinum-based compound to be added may be appropriately increased or decreased according to the desired curing speed. Usually, the amount of platinum or platinum-based compound is 0.1 to 0.1% of the total weight of components (A) and (B). The range is preferably from 1 to 1,000 ppm, particularly preferably from 1 to 200 ppm.

The component (D) filler used in the present invention imparts physical strength such as predetermined hardness and tensile strength to the liquid addition-curable silicone rubber composition. As the filler, those conventionally used in conventional silicone rubber compositions can be used, and examples thereof include fumed silica, crystalline silica (quartz powder), precipitated silica, and silica subjected to hydrophobic treatment. May be used alone or in combination of two or more.

Specific examples of such a material include Aerosil 130, 200, 30 as hydrophilic silica.
0 (Nippon Aerosil, Degussa), Cab
osil MS-5, MS-7 (Cabot), R
Herosil QS-102, 103 (manufactured by Tokuyama Soda Co., Ltd.), Nipsil LP (manufactured by Nippon Silica Co., Ltd.), etc., are Aerosil R-812, R- as hydrophobic silica.
812S, R-972, R-974 (manufactured by Degussa), Rheosil MT-10 (manufactured by Tokuyama Soda), Nipsil SS series (manufactured by Nippon Silica)
Are crystalline silica, Minus, Minus
il, Imisil and the like.

The amount of the filler is 100 parts (A).
5 to 300 parts by weight, preferably 20 to 2 parts by weight per part by weight
00 parts by weight.

As the heat resistance improver of the component (E), those selected from carbon black, cerium oxide, cerium hydroxide and iron oxide (silver) are used alone or in combination of two or more. This heat resistance improver is 300 to 35
It is an essential component for obtaining a cured product that does not change its rubber hardness even at a high temperature of 0 ° C. for 15 minutes to 1 hour and has excellent adhesion durability to a fluororesin / fluorine latex coating layer.

Here, carbon black can be generally classified into furnace black, channel black, acetylene black, thermal black and the like depending on the production method. However, if the content of sulfur and amine is large, the composition is cured by an addition curing reaction of the composition. Acetylene black is particularly preferably used because of inhibition.

The amount of carbon black used is 0.2 to 15 parts by weight, especially 2 to 1 part by weight, per 100 parts by weight of component (A).
0 parts by weight is suitable. If the amount is less than 0.2 parts by weight, there may be no effect on the change in hardness and the adhesion durability to the fluororesin / latex layer. May be impaired.

Cerium oxide and cerium hydroxide may be used alone. In particular, when they are added together with the above-mentioned carbon and / or iron oxide, they act synergistically to suppress a change in hardness and to reduce fluorine. Adhesion durability with the resin / latex layer can be improved. The amount of cerium oxide and cerium hydroxide used is 0.1 to 5 parts by weight, especially 0.2 to 100 parts by weight of component (A).
When the amount is less than 0.2 part by weight, there is a case where there is no effect on the change in hardness and adhesion durability, and when the amount is more than 5 parts by weight, the curing reaction of the composition becomes abnormal and the curing is inhibited. May be done.

Black iron oxide (Fe ₃ O ₄ ) and red iron oxide (Fe ₂ O ₃ ) are preferably used as iron oxide or red iron oxide. The amount of bengara used is (A) component 100
0.2 to 30 parts by weight, especially 2 to 20 parts by weight, based on parts by weight is suitable. If the amount is less than 0.2 parts by weight, there may be no effect on hardness change and adhesion durability, and 30 parts by weight. If the amount exceeds the above range, the fluidity of the material may be impaired.

The total amount of the heat resistance improver used is 0.1 to 30 parts by weight, preferably 1 to 10 parts by weight, and less than 0.1 part by weight, per 100 parts by weight of the component (A). It has no effect on the change in hardness resistance and adhesion durability, and when it exceeds 30 parts by weight, the curing reaction of the composition becomes abnormal and the curing is inhibited.

Further, in order to put these materials into practical use,
When it is necessary to adjust the curing time, a vinyl group-containing organopolysiloxane such as tetravinyltetramethylcyclotetrasiloxane, triallyl isocyanurate, alkyl maleate, acetylene alcohols and their silanes, siloxanes as control agents Modified product, hydroperoxide, teramethylethylenediamine,
A compound selected from the group consisting of benzotriazole and a mixture thereof can be used.

The silicone rubber composition according to the present invention comprises:
It contains the above components, and the rubber hardness after curing is JIS
JIS-A hardness of 1 when measured according to K6301
It is necessary to be 5 or less, preferably 0 to 10, particularly 0 to 6. If the hardness of the cured product exceeds 15, the fixing width (nip width) between the rolls is not sufficient, resulting in poor fixing.

[0038] The fluororesin or fluorine latex coating fixing roll of the present invention is provided with a fluororesin or fluorine latex through a silicone rubber layer formed of a cured product of the silicone rubber composition on the outer peripheral surface of the roll shaft. A layer is provided.

As a method of preparing the fixing roll, for example, a metal roll shaft made of iron or aluminum is placed inside a roll forming die, and then the silicone rubber composition is press-fitted into a cavity. To cure. Thereafter, the silicone rubber roll is taken out of the mold, and the surface of the rubber roll is subjected to a primer treatment.
Or a method of coating the surface of a rubber roll with a fluororesin heated to a melting temperature or higher, or spraying fluorine latex on the surface of the rubber roll and baking at 300 to 350 ° C. at a high temperature.

In this case, the thickness of the silicone rubber layer is
It is preferably from 0.1 to 30 mm, particularly preferably from 1 to 10 mm.

The fluororesin forming the fluororesin layer is, for example, polytetrafluoroethylene resin (P
TFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin (PFA), fluorinated ethylene polypropylene copolymer (FEP), polyvinylidene fluoride resin (PVDF), polyvinyl fluoride resin (PVF), and the like.

Examples of the fluorine latex forming the fluorine latex layer include PTFE latex and Daiel latex (fluorine latex manufactured by Daikin Industries, Ltd.).

The thickness of the fluorine resin or fluorine latex layer is preferably 0.1 mm or less, particularly preferably in the range of 0.1 to 30 μm.

[0044]

The fluororesin or fluorine latex-coated silicone rubber fixing roll of the present invention has a very long life as a fixing roll and is coated with the fluororesin at a melting temperature or higher when the fluororesin is coated on the silicone rubber roll surface. And the process of coating the surface of the silicone rubber roll with fluorine latex, and then baking at a high temperature of 300 to 350 ° C. for 15 minutes to 1 hour, the rubber hardness hardly changes before and after this high temperature state. The silicone rubber layer has low hardness,
Good production yield.

[0045]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Preparation Examples, Examples and Comparative Examples, but the present invention is not limited to the following Examples. In the following examples, all parts are parts by weight.

[Preparation Example 1] A linear dimethylsiloxane polymer having both ends of a molecular chain blocked with a trimethylsilyl group and having an average of about 5 side-chain vinyl groups as methylvinylsiloxane units (degree of polymerization: about 700; hereinafter, both ends) 100 parts of trimethylsiloxy group-blocked dimethylsiloxane methylvinylsiloxane copolymer), specific surface area of 300
40 parts of fumed silica having m ² / g, 8 parts of hexamethyldisilazane, and 1 part of water were charged into a kneader, and the mixture was stirred and mixed at room temperature for 1 hour, and then heated to 150 ° C. and kept mixed for 2 hours. went. Thereafter, the mixture is cooled to room temperature, and 20 parts of a dimethylsiloxane polymer having a molecular weight of 10,000 centipoise at 25 ° C. and both ends of which are blocked with a dimethylvinylsilyl group is further represented by the following formula (1). 3 parts of methyl hydrogen polysiloxane viscosity at room temperature of about 10 centipoise, vinyl group directly attached to a silicon atom _{[-Si (CH 3) (CH =} CH 2) O- units)
Of vinylmethylpolysiloxane having a viscosity of 1,000 centipoise at room temperature and containing 5 mol% of the same, and 50 ppm of a platinum-vinylsiloxane complex as a platinum atom were added thereto, and mixed well until the mixture became uniform. Obtained.

[0047]

Embedded image

[Preparation Example 2] 100 parts of a dimethylsiloxane methylvinylsiloxane copolymer capped with trimethylsiloxy groups at both ends used in Preparation Example 1, 35 parts of crystalline silica (average particle size: 5 μm), represented by the following formula (2) 3.1 parts of methyl hydrogen polysiloxane, 0.2 parts of a platinum catalyst (Pt concentration 1%), 1-ethynyl-1 as a reaction control agent
Liquid composition 2 by mixing 0.1 part of cyclohexanol
I got

[0049]

Embedded image

[Preparation Example 3] 100 parts of a dimethylsiloxane methylvinylsiloxane copolymer capped with trimethylsiloxy groups at both ends used in Preparation Example 1, 20 parts of crystalline silica (average particle size: 20 μm), represented by the above formula (1) 2 parts of methyl hydrogen polysiloxane, 5 parts of methyl hydrogen polysiloxane represented by the following formula (3), 0.2 part of a platinum catalyst (Pt concentration 1%), 1-ethynyl-1-cyclohexanol as a reaction control agent The liquid composition 3 was obtained by mixing 0.1 part.

[0051]

Embedded image

Example 1 147 parts of the liquid composition 1 was mixed with 3 parts of iron oxide Fe ₂ O ₃ , heated and cured at 150 ° C. for 30 minutes, and further post-cured at 200 ° C. for 4 hours. The hardness of the cured product was measured using a rubber hardness meter A (JIS K6301) and found to be 5.

The surface of the cured product is uniformly coated with Daiel latex and primer GLP-103SR for silicone rubber (manufactured by Daikin Co., Ltd.), heated at 80 ° C. for 10 minutes, and spray-coated with Daiel latex GLS-213 evenly. Then, it was heated and baked at 300 ° C. for 1 hour. The hardness of the coated rubber is measured using a rubber hardness meter A (JIS K630).
It was 6 when measured in 1).

Next, a primer NO. For addition-curable liquid silicone rubber was placed on an aluminum shaft having a diameter of 24 mm and a length of 300 mm. 101A / B (Shin-Etsu Chemical Co., Ltd.)
Was applied. Further, the aluminum shaft was filled with a liquid composition obtained by mixing 147 parts of liquid composition 1 and 3 parts of iron oxide Fe ₂ O ₃ , and was heated and cured at 150 ° C. for 30 minutes, and further post-cured at 200 ° C. for 4 hours. did. Daiel latex and primer GLP-103SR for silicone rubber (manufactured by Daikin) are uniformly applied to the surface of the cured product,
Heat at 80 ° C for 10 minutes.
-213 was uniformly applied by spraying and baked at 300 ° C. for 1 hour. A low-hardness silicone rubber roll having a diameter of 26 mm and a length of 250 mm was obtained.

Next, a latex coating of polytetrafluoroethylene was applied to the surface of an aluminum shaft having a diameter of 50 mm and a length of 300 mm.
Heated and baked for minutes. The fluorine latex-coated roll was brought into contact with the roll, a load of 2 kgf was applied thereto, and the nip width was measured to be 20 mm.

Further, the above-mentioned low-hardness silicone rubber roll coated with DAIEL latex was incorporated as a fixing roll of a PPC copying machine, and 100,000 copies were made. Good copies were obtained. In addition, the silicone rubber layer and the Daiel latex coating layer are firmly bonded,
No peeling was observed.

[Comparative Example 1] Liquid composition 1 was heated at 150 ° C for 3 hours.
The mixture was cured by heating for 0 minute and further post-cured at 200 ° C. for 4 hours. The hardness of this cured product is measured using a rubber hardness meter A (JIS K
6301), and was 5.

On the surface of the cured product, a Daiel latex and a primer GLP-103SR for silicone rubber (manufactured by Daikin Co., Ltd.) are uniformly applied, heated at 80 ° C. for 10 minutes, and further spray-coated with a Daiel latex GLS-213 evenly. Then, it was heated and baked at 300 ° C. for 1 hour. The hardness of the coated rubber is measured using a rubber hardness meter A (JIS K630).
It was 17 when measured in 1), and there was a hardness change of 12 points.

Next, a primer No. 1 for addition-curable liquid silicone rubber was placed on an aluminum shaft having a diameter of 24 mm and a length of 300 mm. 101A / B (Shin-Etsu Chemical Co., Ltd.)
Was applied. Further, 147 parts of the liquid composition 1 was filled on this aluminum shaft, and in the same manner as in Example 1,
A silicone rubber roll having an outer diameter of 26 mm and a length of 250 mm was obtained. The nip width measured in the same manner as in Example 1 was 8 mm.

Further, the above-mentioned silicone rubber roll coated with the latex latex was incorporated as a fixing roll of a PPC copier, and 10,000 copies were made. As a result, a copy having uneven color was obtained. Partial peeling was observed between the silicone rubber layer and the DIE latex coating layer.

[Examples 2 and 3]
The mixture was mixed with 3 parts of iron oxide Fe ₂ O ₃ and 1 part of cerium oxide, heated and cured at 150 ° C. for 30 minutes, and further post-cured at 200 ° C. for 4 hours. The hardness of this cured product was measured with a rubber hardness meter type A (JIS K6301) and found to be 2.

The cured product surface is uniformly coated with a DIAL latex and a primer GLP-103SR for silicone rubber (manufactured by Daikin), heated at 80 ° C. for 10 minutes, and further spray-coated uniformly with a DIAL latex GLS-213. Then, it was baked at 350 ° C. for 1 hour. The hardness of the coated rubber is measured using a rubber hardness meter A (JIS K630).
It was 3 when measured in 1).

138 parts of the liquid composition 2 was mixed with 2 parts of acetylene black carbon and 1 part of cerium oxide.
The film was cured by heating at 150 ° C. for 30 minutes, and further post-cured at 200 ° C. for 4 hours. The hardness of the cured product was 1 when measured with a rubber hardness meter type A (JIS K6301).

On the surface of the cured product, in the same manner as described above, Dye latex and primer GLP-1 for silicone rubber were used.
03SR, and further, Diel latex GLS-213 was applied and heated and baked. The hardness of the coated rubber was measured with a rubber hardness meter A (JIS K6301), and was 2.

Next, a primer NO. For addition-curable liquid silicone rubber was placed on two aluminum shafts having a diameter of 24 mm and a length of 300 mm. 101A / B (Shin-Etsu Chemical Co., Ltd.) was applied. Further, 138 parts of the liquid composition 2 and 3 parts of iron oxide Fe ₂ O ₃ and 1 part of cerium oxide were mixed on the two aluminum shafts (Example 2).
And 138 parts of liquid composition 2 and each of the liquid compositions (Example 3) obtained by mixing 2 parts of acetylene black carbon and 1 part of cerium oxide, and heat-cured at 150 ° C. for 30 minutes, and further heated at 200 ° C. Post-cured for 4 hours. The cured product surface is uniformly coated with DAILY latex and a primer GLP-103SR for silicone rubber (manufactured by Daikin), heated at 80 ° C. for 10 minutes, and further spray-coated with DAILY latex GLS-213 evenly. 35
Baking for 1 hour at 0 ° C, outer diameter 26mm x length 250
2 mm low-hardness silicone rubber rolls were obtained.

Further, the two silicone rubber rolls each having a low hardness coated with the DAIEL latex were each subjected to PPC.
When it was incorporated as a fixing roll of a copying machine and 100,000 copies were made, good copies were obtained in each case. Also,
In each of the two rolls, the silicone rubber layer and the DIE latex coating layer were firmly adhered, and no peeling was observed.

[Comparative Example 2] Evaluation was made in the same manner as in Examples 2 and 3 except that only the liquid composition 2 was used without the addition of a heat resistance improver.
It was 1 in the type (JIS K6301). Also, 350
Heated and baked at ℃ for 1 hour, the hardness of the coated rubber is
It was 10 and there was a change in hardness of 9 points. A silicone rubber roll was prepared in the same manner as in Examples 2 and 3 except that only the liquid composition 2 was used without the addition of a heat resistance improver. As a result of copying, a copy having uneven color was obtained. Partial peeling was observed between the silicone rubber layer and the DIE latex coating layer.

Example 4 132 parts of the liquid composition 3 and 2 parts of acetylene black carbon were mixed,
The mixture was cured by heating for 0 minute and further post-cured at 200 ° C. for 4 hours. The hardness of this cured product is measured using a rubber hardness meter A (JIS K
6301) was 0, but the rubber hardness (Asker C) was 10.

On the surface of the cured product, a Dye latex and a primer GLP-103SR for silicone rubber (manufactured by Daikin) are uniformly applied, heated at 80 ° C. for 10 minutes, and further spray-coated with a Dye latex GLS-213 uniformly. Then, it was heated and baked at 300 ° C. for 1 hour. The hardness of the coated rubber is measured using a rubber hardness meter A (JIS K630).
It was 0 when measured in 1), but was 13 when measured with a rubber hardness tester (Asker C).

Next, a primer NO. For addition-curable liquid silicone rubber was placed on an aluminum shaft having a diameter of 24 mm and a length of 300 mm. 101A / B (Shin-Etsu Chemical Co., Ltd.)
Was applied. Further, the aluminum shaft was filled with a liquid composition obtained by mixing 132 parts of liquid composition 3 and 2 parts of acetylene black, and was heated and cured at 150 ° C. for 30 minutes, and further post-cured at 200 ° C. for 4 hours. The surface of the cured product is uniformly coated with a DIAL latex and a primer GLP-103SR for silicone rubber (manufactured by Daikin), heated at 80 ° C. for 10 minutes, and further spray-coated uniformly with a DIAL latex GLS-213. 1 in ° C
It was heated and baked for hours. A low-hardness silicone rubber roll having a diameter of 26 mm and a length of 250 mm was obtained.

Next, a polytetrafluoroethylene latex coating was applied to the surface of an aluminum shaft having a diameter of 50 mm and a length of 300 mm.
Heated and baked for minutes. This fluorine latex-coated roll was brought into contact with the roll, a load of 2 kgf was applied thereto, and the nip width was measured to be 25 mm.

Furthermore, the above-mentioned low-hardness silicone rubber roll coated with DAIEL latex was incorporated as a fixing roll of a PPC copying machine, and when 100,000 copies were made, a good copy was obtained. In addition, the silicone rubber layer and the Daiel latex coating layer are firmly bonded,
No peeling was observed.

Comparative Example 3 132 parts of liquid composition 3
The film was cured by heating at 50 ° C. for 30 minutes, and further post-cured at 200 ° C. for 4 hours. The hardness of the cured product was 0 when measured with a rubber hardness meter A (JIS K6301), but was 10 when measured with a rubber hardness meter (Asker C).
Met.

The surface of the cured product is uniformly coated with a DIAL latex and a primer GLP-103SR for silicone rubber (manufactured by Daikin), heated at 80 ° C. for 10 minutes, and further spray-coated with a DIAL latex GLS-213 uniformly. Then, it was heated and baked at 300 ° C. for 1 hour. The hardness of the coated rubber is measured using a rubber hardness meter A (JIS K630).
It was 7 when measured in 1) and 30 when measured with a rubber hardness tester (Asker C) (that is, JIS).
-There was a change in hardness of 7 points in A hardness and 20 points in Asker C hardness).

Next, a primer NO. For addition-curable liquid silicone rubber was placed on an aluminum shaft having a diameter of 24 mm and a length of 300 mm. 101A / B (Shin-Etsu Chemical Co., Ltd.)
Was applied. Further, 132 parts of the liquid composition 3 was filled on this aluminum shaft, and a low-hardness silicone rubber roll coated with a Djyl latex having an outer diameter of 26 mm and a length of 250 mm was obtained in the same manner as in Example 3. When the nip width was measured in the same manner as in Example 4,
5 mm.

Further, the low-hardness silicone rubber roll coated with the above-mentioned Daiel latex was incorporated as a fixing roll of a PPC copying machine, and 5,000 copies were made. As a result, a copy having uneven color was obtained. Partial peeling was observed between the silicone rubber layer and the DIE latex coating layer.

[Examples 5 and 6] The liquid composition 2 was treated with 138
The mixture was mixed with 3 parts of iron oxide Fe ₂ O ₃ and 1 part of cerium oxide, heated and cured at 150 ° C. for 30 minutes, and further post-cured at 200 ° C. for 4 hours. The hardness of this cured product was measured with a rubber hardness meter type A (JIS K6301) and found to be 2.

A primer for silicone rubber (X-33-156-1, manufactured by Shin-Etsu Chemical Co., Ltd.) was evenly applied to the surface of the cured product, air-dried at 25 ° C. for 30 minutes, and further melted and heated to 320 ° C. The hardness of a rubber obtained by coating the surface of a rubber layer with an ethylene-perfluoroalkylvinyl ether copolymer resin (PFA) is measured using a rubber hardness meter A (J
It was 3 as measured by IS K6301).

Further, 138 parts of the liquid composition 2 was mixed with 2 parts of acetylene black carbon and 1 part of cerium oxide,
The film was cured by heating at 150 ° C. for 30 minutes, and further post-cured at 200 ° C. for 4 hours. The hardness of the cured product was 1 when measured with a rubber hardness meter type A (JIS K6301).

The surface of the cured product was uniformly coated with a DIE latex and a primer GLP-103SR for silicone rubber, and the surface of the rubber layer was coated with PTFE melted and heated at 350 ° C. The hardness of the rubber was measured using a rubber hardness meter A ( It was 2 when measured according to JIS K6301).

Next, a primer NO. For addition-curable liquid silicone rubber was placed on two aluminum shafts having a diameter of 24 mm and a length of 300 mm. 101A / B (Shin-Etsu Chemical Co., Ltd.) was applied. Further, 138 parts of the liquid composition 2 and 3 parts of iron oxide Fe ₂ O ₃ and 1 part of cerium oxide were mixed on the two aluminum shafts (Example 5).
And 138 parts of the liquid composition 2 were charged with each of the liquid compositions (Example 6) obtained by mixing 2 parts of acetylene black carbon and 1 part of cerium oxide, and were cured by heating at 150 ° C. for 30 minutes and further at 200 ° C. Post-cured for 4 hours. A primer for silicone rubber (X-
33-156-1, manufactured by Shin-Etsu Chemical Co., Ltd.), air-dried at 25 ° C. for 30 minutes, and further coated with PFA melt-heated to 320 ° C. on the rubber layer surface, outer diameter 26 mm
X Two PFA-coated low-hardness silicone rubber rolls having a length of 250 mm were obtained.

Further, each of the two PFA-coated low-hardness silicone rubber rolls was incorporated as a fixing roll of a PPC copying machine, and 100,000 copies were made.
In each case, good copies were obtained. The silicone rubber layer and the PFA coating layer were firmly adhered to each of the two rolls, and no peeling was observed.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Nobumasa Tomizawa 1-10 Hitomi, Matsuida-cho, Usui-gun, Gunma Prefecture Within Silicone Electronic Materials Technology Laboratory, Shin-Etsu Chemical Co., Ltd.

Claims (1)

[Claims] 1. A fluorine resin or fluorine latex coated silicone rubber fixing roll in which a silicone rubber layer is formed on the outer peripheral surface of a roll shaft and the surface of the silicone rubber layer is coated with a fluorine resin or fluorine latex, wherein the silicone rubber layer Contains (A) two or more aliphatic unsaturated hydrocarbon groups bonded to a silicon atom only in a side chain in one molecule, and the content of the aliphatic unsaturated hydrocarbon group-containing siloxane unit is 0.05 to 100 parts by weight of an organopolysiloxane which is 5 mol% (B) an organohydrogenpolysiloxane having at least two hydrogen atoms directly bonded to a silicon atom in one molecule, and an aliphatic polysiloxane in the organopolysiloxane of the component (A). With respect to the saturated hydrocarbon group, the silicon atom in the organohydrogenpolysiloxane of the component (B) is directly (C) platinum or platinum-based compound catalytic amount (D) filler 5 to 300 parts by weight (E) from carbon black, cerium oxide, cerium hydroxide and iron oxide The rubber composition contains 0.1 to 30 parts by weight of the selected heat resistance improver and has a rubber hardness after curing (JIS K6
Fluororesin or fluorine latex-coated silicone rubber fixing roll formed of a cured product of a silicone rubber composition having a JIS-A hardness of 301 or less (15 or less).