JP3377534B2 - Silicone rubber roller for heat fixing - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silicone rubber roller used in a heat fixing section using a primer composition having excellent adhesion between silicone rubber and a fluororesin.

[0002]

TECHNICAL BACKGROUND AND PROBLEMS OF THE INVENTION As a method for fixing a toner powder image transferred from a transfer drum onto a support such as paper in a dry electrophotographic method onto the support, the support is heated with a heating roller. A method is used in which the toner powder image is fixed on the support by heating and pressurizing the support through a pressure roller.

In this method, since unfixed toner powder easily adheres to the pressure roller, a pressure roller having a good releasability from the toner powder is required. Silicone rubber is used as the rubber layer.

However, although this silicone rubber roll is relatively excellent in non-adhesiveness (releasing property), as the number of times of paper feeding increases, the surface of the roll becomes soiled and the image quality becomes worse. Also had the drawback of having an adverse effect.

In order to eliminate such drawbacks, a method of coating the surface of the silicone rubber with a fluororesin has been adopted. In this type of roll, the silicone rubber and the fluororesin are increased as the number of paper feeds increases. There was a fatal defect that the flakes peeled off.

[0006]

An object of the present invention is to solve the above problems and to provide an inner layer made of silicone rubber provided on the outer periphery of a roller core shaft,
A silicone rubber roller for heat fixing, which comprises an outer layer made of a fluororesin tube covering the outer circumference of the inner layer, improves the adhesiveness between the inner layer and the outer layer, and provides a silicone rubber roller for heat fixing having excellent durability. As a result of intensive studies aimed at that, it was found that it is extremely effective to apply a specific primer composition for the inner layer and the outer layer, and the present invention has been completed.

[0007]

That is, the present invention is provided on the outer circumference of a roller core shaft.
The inner layer made of silicone rubber and the outer periphery of the inner layer.
Consists of an outer layer consisting of a fluororesin tube that covers
In the heat fixing silicone rubber roller, the outer layer
At least the following (A) to the inner surface of the fluororesin tube
Apply the primer composition consisting of (E), then apply
Injection reaction type silicone rubber is injected between the lathe shaft and the outer layer.
Silicone rubber is used for the inner layer centered around the core shaft
Heat, characterized in that the layers consist of fluoroplastic tubes
A fixing silicone rubber roller.

(A) General formula

[0009]

[Chemical 3]

(Wherein R ¹ represents a substituted or unsubstituted monovalent hydrocarbon group, a represents 0, 1 or 2 and b represents 1 or 2, provided that a + b is 1 to 3). 100 parts by weight of a polyorganohydrogensiloxane having at least two hydrogen atoms bonded to silicon atoms in the molecule (B)

[0011]

[Chemical 4]

Wherein R ² represents a substituted or unsubstituted monovalent hydrocarbon group, R ³ represents a substituted or unsubstituted monovalent hydrocarbon group, and c is 0 or 1. Alkoxysilane and / or its partial hydrolysis-condensation product 200 to 250 parts by weight (C) Organic titanate ester 100 to 133 parts by weight (D) Platinum compound (A) + (B) + (C) + (E) The amount (E) of the organic solvent 233 to 4550 parts by weight, which is 10 to 30 ppm as platinum atom based on the components, the primer composition used in the present invention and the heat fixing silicone rubber roller using the primer composition will be described.

The polyorganohydrogensiloxane of the component (A) used in the present invention comprises the constitutional unit represented by the above general formula (I) and has at least two hydrogen atoms bonded to silicon atoms in the molecule. Is. In the formula,
R ¹ represents a substituted or unsubstituted monovalent hydrocarbon group, for example, an alkyl group such as methyl, ethyl, propyl, butyl, hexyl and dodecyl; an aryl group such as phenyl; β-phenylethyl, β-phenylpropenyl Aralkyl groups such as phenyl; further chloromethyl, 3,3,3
-Substituted hydrocarbon groups such as trifluoropropyl may be mentioned. Of these groups, the methyl group is most preferable from the viewpoint of ease of synthesis. Further, this polyorganohydrogensiloxane preferably has a viscosity of 1 to 10,000 cP at 25 ° C. for ease of synthesis and handling. As such a polyorganohydrogensiloxane, a linear, branched or cyclic polymer or a mixture thereof can be used.

The alkoxysilane and / or its partial hydrolysis-condensation product which is the component (B) of the composition of the present invention is
Alkoxysilane is a compound of the general formula, which is required for the composition to cure to a good elastic body.

[0015]

[Chemical 5]

(Wherein R ² , R ³ and c are as described above).

In the general formula, R ² may be an alkyl group such as a methyl group, an ethyl group or a propyl group, a phenyl group, a vinyl group and OR ¹ , and R ³ may be a hydrolyzable group of OR ³ . Can generally include methyl and ethyl groups.

Examples of the component (B) include alkyl orthosilicates such as ethyl silicate and propyl silicate, and polyalkyl silicates which are partial hydrolysates thereof, methyltriethoxysilane, phenyltriethoxysilane, phenyltrimethoxy. Examples thereof include silanes, alkoxysilanes such as vinyltriethoxysilane, and partially hydrolyzed siloxanes thereof. In addition to these, a group of alkoxysilanes well known as carbon functional silanes represented by the following molecular formula and their partially hydrolyzed siloxanes can also be effectively used in the present invention. In the following description, Me represents a methyl group and Et represents an ethyl group.

[0019]

[Chemical 6]

The amount of component (B) compounded is in the range of 200 to 250 parts by weight per 100 parts by weight of component (A).

The organic titanic acid esters used as the component (C) in the present invention include not only organic titanic acid esters but also partially alkoxylated and partially chelated compounds of titanium, chelated compounds of titanium, silicic acid of titanium. A chelate compound with an ester and a partially hydrolyzed condensate thereof are included.

Specifically, tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate, diethoxytitanium acetylacetonate, titanium diacetylacetonate, titanium octylglycatotitanium lactate, titanium lactate. Examples thereof include ethyl ester, titanium triethanolaminate, and partial hydrolysis-condensation products thereof, which may be used alone or 2
It is also possible to use two or more species together.

The amount of component (C) compounded is in the range of 100 to 133 parts by weight per 100 parts by weight of component (A).

Examples of the platinum compound of the component (D) used in the present invention include platinum coordination compounds, chloroplatinic acid, platinum coordination compounds such as platinum-olefin complex or platinum-alcohol complex.

The blending amount of the component (D) is the same as the component (A) +
10 to 30 as platinum atom for (B) + (C) + (E)
ppm.

The organic solvent of component (E) used in the present invention includes benzene, toluene, xylene, heptane,
Hexane, trichlorethylene, perchlorethylene,
Methylene chloride, ethyl acetate, ethanol, isopropanol, butanol and the like can be mentioned, and these can be used alone or as a mixed solvent of two or more thereof.

The compounding amount of the component (E) is 233 to 4550 parts by weight based on 100 parts by weight of the component (A).

Of the components (A) to (E) above, (A)
In items (D) to (D), the addition reaction type silicone rubber and the fluororesin tube are essential components necessary for imparting a strong and time-degraded adhesion, and even if any one component is omitted, No effect is achieved, in other words, it is achieved only with the composition according to the invention.

The metal cored bar of the roll used in the present invention may be made of any material such as iron, aluminum and stainless steel as long as it has sufficient mechanical strength, and may be a primer-treated one.

Examples of the fluororesin used in the present invention include tetrafluoroethylene resin, tetrafluoroethylene-perfluorovinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer and tetrafluoroethylene. -Ethylene copolymers, polyvinylidene fluoride and the like can be mentioned, and they are available in the form of heat-shrinkable tubes, films and the like. Among fluororesin tubes, those whose inner surface has been treated by the sodium / naphthalene method, sputter etching method, corona discharge treatment method, etc. strengthen the adhesion with silicone rubber and are useful. The thing consisting of a perfluoro vinyl ether copolymer is excellent in adhesiveness and heat resistance, and is useful.

The roller of the present invention is manufactured by the following steps. First, a method of forming a coating layer with an addition reaction type silicone rubber on the outer periphery of a metal core after applying a primer composition comprising the above components (A) to (E) on the inner surface of a fluororesin tube, There is a method of injecting and forming an addition reaction type silicone rubber in a fluororesin tube treated with the above-mentioned primer.

According to the present invention, since the specific primer composition is used, the fluororesin and the addition reaction type silicone rubber are firmly adhered, and the adhesion durability is excellent, and the heat fixing roller has a long life. Can be obtained.

[0033]

The primer composition of the present invention has a remarkable effect in improving the adhesiveness between silicone rubber and fluororesin, and a silicone rubber roller for heat fixing using the primer composition has an inner layer and an outer layer. It is useful because it has improved adhesiveness and excellent durability.

[0034]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

In the examples, "part" means "part by weight", and the viscosity means a value at 25 ° C. Example 1 2 parts of linear polymethylhydrogensiloxane having both ends blocked with trimethylsilyl groups, containing 0.92% by weight of hydrogen atoms bonded to silicon atoms, and having a viscosity of 30 cP, 5 parts of phenyltriethoxysilane, tetraisopropyl A primer composition 1 was prepared by mixing 2 parts of titanate, 91 parts of ethyl acetate and 10 ppm of chloroplatinic acid in isopropyl alcohol as platinum atoms and uniformly dispersing them.

Next, width 25 mm x length 150 mm x thickness 50 μm
The primer composition 1 is applied to the surface of the fluororesin of the tetrafluoroethylene-hexafluoropropylene copolymer, and is set in the mold, and the addition reaction liquid silicone rubber TSE3402
(Trade name, manufactured by Toshiba Silicone Co., Ltd.)
It was heated for 30 minutes to prepare a test piece as shown in FIG.
For this, 500 in the initial and 200 ° C ovens
The peeling force after time aging was measured according to JIS K 6301. The results are shown in Table 1. Example 2 (CH ₃ ) ₂ HSiO _1/2 units and SiO ₂ units, containing 1.03% by weight of hydrogen atoms bonded to silicon atoms, and having a viscosity of 23 cP, 15 parts of polymethylhydrogensiloxane, tetraethoxysilane 30 Parts, diethoxytitanium acetylacetonate
A primer composition 2 was prepared by mixing 20 parts by weight, 35 parts by weight of n-hexane, and 30 ppm of chloroplatinic acid in isopropyl alcohol as platinum atoms and uniformly dispersing them.

Then, a test piece was prepared in the same manner as in Example 1 except that the primer composition 2 was used, and the peel strength was measured. The results are shown in Table 1. Comparative Example 1 A primer composition 3 (comparative product) was prepared in the same manner as in Example 1 except that the isopropyl alcohol solution of chloroplatinic acid was not added.

Then, a test piece was prepared in the same manner as in Example 1 except that the primer composition 3 was used, and the peeling force was measured. The results are shown in Table 1. Comparative Example 2 In Example 2, instead of the isopropyl alcohol solution of chloroplatinic acid, 97 mol% of dimethylsiloxane units and 3 mol% of methylvinylsiloxane units were used, and the viscosity was 1
Primer composition 4 was prepared in the same manner except that 100 parts by weight of methylvinylpolysiloxane of 000 cP was mixed.
(Comparative product) was prepared.

Then, a test piece was prepared in the same manner as in Example 1 except that the primer composition 4 was used, and the peeling force was measured. The results are shown in Table 1. Comparative Example 3 In Example 2, instead of the isopropyl alcohol solution of chloroplatinic acid, 30 mol% of methylsiloxane units, 35 mol% of phenylsiloxane units, and dimethylsiloxane units were used.
35 mol%, silanol content 0.1 mol% / 10
Other than mixing 50 parts by weight of silicone resin, which is 0 g,
A primer composition 5 (comparative product) was prepared in the same manner.

Then, a test piece was prepared in the same manner as in Example 1 except that the primer composition 5 was used, and the peel strength was measured. The results are shown in Table 1.

[0041]

[Table 1]

Next, using the primer compositions 1 to 5 prepared as described above, a heat fixing silicone rubber roller was prepared and tested and evaluated. Example 3 A primer ME151 (trade name, manufactured by Toshiba Silicone Co., Ltd.) for addition reaction type liquid silicone rubber was coated on an aluminum shaft having a diameter of 8 mm and a length of 300 mm, and the inner surface was coated with the primer composition 1 as the outermost layer. After setting a heat-shrinkable tube of tetrafluoroethylene-propylene hexafluoride copolymer, addition reaction type liquid silicone rubber TSE34
Inject 53 (trade name, manufactured by Toshiba Silicone Co., Ltd.), 1
A roll having an outer diameter of 28 mm and a length of 250 mm was produced by heating at 50 ° C for 30 minutes.

In order to carry out a mounting test of this roll, this roll was incorporated as a fixing roll of a PPC copying machine, and 50,000 copies were made at a pressure between rolls of 3 kgf / cm ² , and no abnormality was found on the roll itself. And a good copy was obtained. Example 4 A roll was prepared in the same manner as in Example 3 except that the primer composition 2 was used instead of the primer composition 1 and a mounting test was conducted. The roll itself showed an abnormality even after copying 50,000 sheets. It was not seen, and a good copy was obtained. Comparative Example 4 A roll was prepared in the same manner as in Example 1 except that the primer composition 3 was used in place of the primer composition 1 and a mounting test was conducted. Occurred, and a paper jam occurred. A part of the fluorine tube on the surface of the roll itself was peeled off. Comparative Example 5 When a roll was prepared in the same manner as in Example 4 except that the primer composition 4 was used instead of the primer composition 2 and a mounting test was conducted, an abnormal sound was generated at the 8,000th sheet. , A paper jam occurred. A part of the fluorine tube on the surface of the roll itself was peeled off. Comparative Example 6 When a roll was prepared in the same manner as in Example 4 except that the primer composition 5 was used instead of the primer composition 2 and a mounting test was performed, an abnormal sound was generated at the 7,000th sheet. , A paper jam occurred. A part of the fluorine tube on the surface of the roll itself was peeled off.

[Brief description of drawings]

FIG. 1 is a diagram showing a peeling force measuring test piece used in Examples, (a) is a top view, (b) is a front view, and (c) is a diagram showing a state at the time of peeling force measurement. Is.

[Explanation of symbols]

1 ... Fluorine resin 2 ... Primer layer 3 ... Silicone rubber

─────────────────────────────────────────────────── ─── Continued Front Page (51) Int.Cl. ⁷ Identification FI C09J 183/04 C09J 183/04 // (C09D 183/04 C09D 183: 05 183: 05 185: 00 185: 00) C09J 183: 05 (C09J 183/04 185: 00 183: 05 185: 00) (56) Reference JP-A-3-274145 (JP, A) JP-A-60-115661 (JP, A) JP-A-60-233153 ( JP, A-118587 (JP, A) JP, 64-70783 (JP, A) JP, 1-236282 (JP, A) JP, 5-86352 (JP, A), JP2610748 (JP, B2) Patent 2922712 (JP, B2) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03G 15/20 B29D 31/00 C09D 5/00 C09D 183/04-183/08 C09D 185 / 00 C09J 5/02 C09J 183/04-183/08 C09J 185/00

Claims (2)

(57) [Claims] 1. A silicone provided on the outer periphery of a roller core shaft.
An inner layer made of rubber and a fluorine resin covering the outer periphery of the inner layer
A heat fixing sheet composed of an outer layer made of an oil tube.
In the silicone rubber roller, the outer layer of fluorocarbon resin
On the inner surface of the probe, at least the following (A) to (E)
After applying the lymer composition, the roller core and the outer layer
A core made by injecting and curing an addition reaction type silicone rubber in between
Inner layer is silicone rubber and outer layer is fluororesin
Silicone for heat fixing characterized by consisting of a tube
Rubber roller. (A) General formula: (In the formula, R ¹ represents a substituted or unsubstituted monovalent hydrocarbon group, a represents 0, 1 or 2, and b represents 1 or 2. However, a + b is 1 to 3.) 100 parts by weight of a polyorganohydrogensiloxane having at least two hydrogen atoms bonded to silicon atoms in the molecule consisting of the constituent units shown by the formula (B) (In the formula, R ² is a substituted or unsubstituted monovalent hydrocarbon group, R ³
Represents a substituted or unsubstituted monovalent hydrocarbon group, and c is 0
Alkoxysilane and / or its partial hydrolysis-condensation product 200 to 250 parts by weight (C) Organic titanate esters 100 to 133 parts by weight (D) Platinum compound (A) + (B) + (C) + (E) component 10 to 30 ppm as platinum atom (E) Organic solvent 233 to 4550 parts by weight 2. A fluororesin tube is tetrafluoroethylene
-Perfluoro vinyl ether copolymer
1. The heat-fixing silicone rubber roller according to 1.