JPS59220349A - Fixing roll made of addition type liquid silicone rubber - Google Patents

Abstract

PURPOSE:To provide the title fixing roll generating no peeling-off and having high durability, formed by containing a plurality of specific siloxane compounds, an organotitanate compound and a small amount of a platinum group metal compound as the components of a primer. CONSTITUTION:In a fixing roll wherein an addition type liquid silicone rubber is adhered to a core metal through a primer, as the components of the primer, vinyl group-containing organopolysiloxane, an organopolysiloxane resin, organoalkoxysilane, organohydrogenpolysiloxane, a platinum group metal catalyst and organotitanate are contained. On the basis of 100pts.wt. vinyl group-containing organopolysiloxane, 1X10<-6>-1X10<-4>pts.wt. of platinum in the platinum group metal catalyst is contained. By containig the above mentioned components, the heat resistance and oil resistance of the primer itself can be enhanced and, further, by adjusting the platinum group metal catalyst to a predetermined amount, the primer can be well bonded to the core metal and silicone rubber and durability is enhanced.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a fixing roll for use in electrophotographic copying machines, printers, etc., which fuses images transferred to paper. The present invention relates to an additive-type liquid silicone rubber fuser roll bonded through a bonding layer.

Conventional primers for fuser rolls include those containing organic peroxide as a curing agent, but although these primers are effective against organic peroxide-vulcanized silicone rubber, When used in the above-mentioned addition-type liquid silicone rubber, the adhesion between the core and the primer or between the primer and the silicone rubber is poor, and the heat resistance of the primer itself is low, and as the silicone rubber is used, the core deteriorates. It has the disadvantage that it peels off from gold and causes poor heat transfer from the heater to the outer surface of the silicone rubber, resulting in poor fixing.Also, the oil resistance of the primer is low, and silicone is used during fixing to improve mold releasability. In the case of applying oil, there is a drawback that peeling occurs earlier and durability is significantly reduced.

In view of the above points, and based on various considerations, the present invention provides a primer that has good adhesion to both core metal and silicone rubber, and has excellent heat resistance and oil resistance. An object of the present invention is to provide a highly durable fixing roll that does not cause peeling.

In order to achieve the above object, the present invention provides an addition-type liquid silicone rubber fixing roller as described above, in which vinyl group-containing organopolysiloxane, organopolysiloxane resin, organoalkoxysiloxane, etc. are used as primer components. , containing a platinum-based catalyst and an organic titanate ester I, containing 1 x platinum in the platinum-based catalyst for 100 parts by weight of the vinyl group-containing organopolysiloxane. 1o-L
It is characterized by containing 1xlcr" parts by weight.

That is, as a result of various considerations, it was discovered that the heat resistance and oil resistance of the primer itself could be improved by incorporating the above-mentioned components while using a platinum-based catalyst in a primer for adhering addition-type liquid silicone rubber. Depending on the content of platinum-based catalyst, the core metal, primer,
They have also discovered that it has a significant effect on the adhesion between the primer and silicone rubber.

Specifically, in manufacturing the fuser roll, a primer is applied to the core metal, and then silicone rubber is bonded by injection molding, and the primer sometimes flows out due to the pressure during injection molding. In order to make sure that the primer is in contact with the core metal and solidified, a so-called pre-bake process is applied, in which the primer is applied to the core metal, dried, and then preheated at about 100 to 180°C for about 15 to 60 minutes. is interposed. However, when the content of platinum-based catalyst is low, the adhesion of the primer to the core metal is poor.
Because the film strength is weak, the primer has the disadvantage of easily flowing out during injection as mentioned above.On the other hand, if the platinum-based catalyst content is high, the reaction of the primer itself will proceed during the pre-baking process, resulting in poor adhesion with silicone rubber. Based on these considerations, in the present invention, platinum-based Since the content of the catalyst is adjusted to a predetermined amount, while the primer adheres well to the core metal, it also prevents the functional groups necessary for adhesion to the silicone rubber from decreasing due to the pre-baking process. Maintaining a high level of activity allows for good adhesion of injection-injected silicone rubber, which not only improves the heat resistance and oil resistance of the brimer itself, but also improves the adhesion between the core metal and the primer, as well as between the primer and the silicone rubber. This improves the durability of not only types that do not apply silicone oil to the fixing roll during fixing, but also types that apply silicone oil, and allows for long-term fixing without peeling. We are now able to provide something that works well.

The vinyl group-containing organodisiloxane used in the present invention has an average compositional formula R"a"SiO,-1 (!l is one
- a positive number from 1.9 to 2.8) - The viscosity at 125°C is 5000 centistokes or more. This is a cell material that gives flexibility to the brimer film and improves adhesion with silicone rubber. In addition, the substituted or unsubstituted monovalent hydrocarbon group represented by R1 in the formula includes alkylcycloalkyl groups such as methyl group, ethyl group, and propyl group, alkenyl group, cycloalkenyl group, aryl group, Examples include hydrogen groups, and at least 0.15 moles of R1 must be alkenyl groups, particularly vinyl groups.

In addition, organopolysiloxane resin has an average composition of
The substituted or unsubstituted monovalent hydrocarbon group represented by R in the formula is methyl group, ethyl group,
Examples include furoyl group, vinyl group, and phenyl group.

This resin is obtained by co-hydrolyzing various chlorosilanes, and should be in the range of 5 to 200 parts by weight, preferably 5 to 100 parts by weight, per 100 parts by weight of the vinyl group-containing organopolysiloxane. Good. This is F
If it is less than 5 parts by weight, the strength of the primer counter-alignment will be insufficient,
On the other hand, if it exceeds 200 parts by weight, the film becomes brittle and lacks durability.

In addition, organoalkoxysilane has the average compositional formula 'e''=
R”a”(ORυesiO, -c-d-e (c tr
i O≦C≦8, d is 0≦d≦82≦e≦4, but 2≦
c+d+e≦4] and has at least two alkoxy groups bonded to silicon atoms in one molecule. In the formula, the substituted or unsubstituted monovalent hydrocarbon group represented by R'' is exemplified by a methyl group, an ethyl group, a vinyl group, a phenyl group, etc. The condensation anticentric monovalent hydrocarbon group includes addition-reactive, condensation centrality functional groups such as methacryloxy group, vinyl group, allyl group, amino group, and mercapto group. R'H, methyl group, ethyl group. group, propyl group, butyl group, or a partially hydrolyzed condensate thereof.
It is used in a range of 500 parts by weight. If the amount is less than 5 parts by weight, the adhesion will decrease, and if 500 parts by weight is used, it will result in poor curing and a decrease in the strength of the skin pattern.

In addition, Si is contained in the organohydrodiene polysiloxane.
Any polymer having at least two H groups may be used, and the degree of polymerization is at least 2. In the formula, R4 is exemplified by an alkyl group such as a methyl group, an alknyl group such as a vinyl group, an aryl group such as a phenyl group, and the like. This organohydrodiene polysiloxane is used in an amount of 1 to 500 parts by weight based on 100 parts by weight of the vinyl group-containing organopolysiloxane.
Used in the area of heavy scenery. This means that if the amount is less than 1 part by weight, the adhesiveness will decrease, while if it exceeds 500 parts by weight,
9 Skin contact with unstable adhesion also becomes weak.

Examples of the platinum-based medium include chloroplatinic acid and composites of platinum chloride and ethylene, propylene, getadiene, cyclohexane, or similar substances, and the amount of platinum based on 100 parts by weight of the vinyl group-containing organopolysiloxane is exemplified. , I Xl0-' to 1 x 10-' parts by weight. Less than 1 xio' parts by weight, the alknyl groups in the vinyl group-containing organopolysiloxane, organopolysiloxane resin, and organoalkoxysilane, respectively. , the vinyl group does not react with the SiH group of organohydrodiene polysiloxane, the strength of the primer itself is low, and there is a risk of it flowing or coming out during injection molding of silicone rubber. This is because the reaction of the primer itself progresses too much in the pre-paking process, reducing the number of functional groups necessary for contact with the silicone rubber, resulting in poor adhesion with the silicone rubber, resulting in the above-mentioned peeling. .

In addition, organic titanium esters cure the primer composition, impart air-drying properties, and improve adhesion to the core metal. Examples of such compounds include tetrapropyl titanate, tetra-n-butyl titanate, and butyl titanate. Examples include titanate dimer and partially hydrolyzed condensates thereof, which are used in an amount of 0.5 to 50 parts by weight based on 100 parts by weight of the vinyl group-containing organopolysiloxane. If the amount is less than 0.5 parts by weight, both the air drying properties and the adhesion between the core metal and the primer will be poor, and if it exceeds 50 parts by weight, the storage stability of this composition will be poor. As a result, the film becomes brittle.

In addition to the above-mentioned components, the primer of the present invention may also contain various inorganic fillers (humid silica, etc., heat-resistant agents such as red iron, agglomerated Yaricum, titanium oxide, carbon black, etc.) and various other materials to improve film strength. An organic solvent may be included. The solvent is selected in consideration of primer inspection work and compatibility with various components.

Embodiments of the present invention will be described below with reference to the drawings.

First, the manufacturing process of the fixing roll will be explained.

fil First cleaning step (see Figure 1) Using a cleaning machine (4) equipped with wet temperature (1), ultrasonic melting (2) and steam melting (3), core metal (5) made of aluminum or the like is cleaned. Attach the transport tool (6) K and wash it in order to remove cutting oil etc. adhering to the surface of the core metal (5). In the figure, (8a) shows a cooling pipe.

(2) Core metal surface 6 processing process (see Figure 2) After cleaning, the core metal (5) is attached to the rotary table (7), and the chemical solution is supplied through the nozzle (8) to remove the core metal (5). Activate the surface of the
The surface of the core metal (5) is roughened using a blasting machine (not shown).

(3) Second cleaning process (see Figure 8) The cleaning machine (4
), ultrasonic melting (2) and steam melting (3) are used to remove contaminants that have adhered during the above-mentioned surface treatment.

(4) Brimer application process (see Figure 4) Core metal (5)
is supported by a rotary offshore tool +911 +91, and the rotating core bar (5) is coated with a brimer of an example described below to a thickness of 0.5 to 20 μm using a spray device (10).

(6) Air drying process (see Figure 5) The core metal [5a] coated with the primer is attached to the support stand σD in an upright position, and is dried at room temperature by blowing air in the drying room f121 for 15 to 60 minutes.

, and apply hot air at 100 to 180℃ for 15 to 60 minutes.
Heat the braimer to harden it.

(7) Injection molding process (see Figure 7) The core metal (5a) with hardened primer is
Fixed mold heated to 00℃ (fixed and supported by 141,
Attach the moving mold (151) to it, and
Inject liquid silicone rubber through nozzle ue,
30 seconds to l until the silicone rubber hardens due to addition curing.
Leave it as it is for 0 minutes.

(8) After leaving the aging process (see Figure 8), the obtained roll (5b) was placed in a constant temperature oven (171) and heated at 100~
Aging is performed by heating at 250°C for 60 to 800 minutes to further improve the hardness of the rubber material that has completed the primary hardening caused by leaving it during injection molding as described above, and to improve physical properties such as permanent compression strain. let

(9) Polishing process (see Figure 9) After aging, use a polishing machine (for
5b)" Finish the outer periphery of the silicone rubber layer to a cut IJL, an outer diameter close to the final outer diameter. In addition, the outer diameter force of the roll (5b) after aging; if it is close to the final outer diameter,
This polishing step is omitted and the roll (5b) is transported (6a).
) and put it in the oil tank tll, and put it in the same silicone oil that is applied when installing it in a copying machine and fixing it.
It is immersed while flowing with a stirrer f, and when copying,
As the silicone oil is applied, the silicone coat A di swells due to the impregnation of the silicone oil, and the roll (5
In order to prevent the outer diameter of the roll (5b) from changing, the roll (5b) is allowed to swell in equilibrium in advance.

(Ill Polishing Step (See FIG. 9)) Finally, the outer surface of the roll (5b) is cut using the same polishing machine (l mark) as in the polishing step described above to obtain a fixing roll as a product with predetermined dimensions.

Note that if the final outer diameter is guaranteed even after the oil dipping step, this step may be omitted.

〔Example〕

It consists of 97 moles of dimethylsiloxane units and 8 moles of methylvinylsiloxane units, and has a tenacity of 5,000,0
00 centistokes (25°C) 100 p parts of methylvinylpolysiloxane, 85 methylsiloxane units
molti, 20 parts by weight of a silicone resin consisting of 80 mols of dimethyldisiloxane units and 85 mols of phenylsiloxane units and having a silanol content of 0.12 mols/10oz, 10 parts by weight of γ-tacryloxypropyltrimethoxydisilane, Ethyl polysilicate 100mt
am, Viscosity K 15 centistokes 100 parts by weight of methylhydrogen polysiloxane (dimethylsiloxane unit 80 mol, methylhydrogen siloxane unit 70 mol%), 1 weight of isopropanol solution of chloroplatinic acid (Pt concentration 10-'' concentration) Primer Σ was prepared by adding 500 parts by weight of toluene and 1000 parts by weight of ethyl acetate to 5 parts by weight of tetrapropyl titanate and stirring well.

This brimer was applied to an aluminum core metal (outer diameter: 40 ttm) to a film thickness of 10 μm by spray coating, and then air-dried and subjected to a pre-baking process at 150° C. for 40 minutes.

Next, as an addition-curing liquid silicone rubber, dimethylpolysiloxane *f:/10 with a viscosity of 5QOO centistokes at 25°C and both terminals blocked with dimethylvinylsilyl groups was used.
0 parts by weight, 3 parts by weight of methylhydrodiene polysiloxane having a viscosity of 80 centistokes at 25°C, 0.2 parts by weight of an ethanol solution of chloroplatinic acid (Pt concentration 1%),
And, 20 parts by weight of dry fine powder silica and 15 parts by weight of wet fine powder silica.
After adding parts by weight and mixing well, the mixture was subjected to the following steps at the temperature and for 6 hours to finally obtain an addition-type liquid silicone rubber fixing roll with a silicone rubber thickness of 0.5 rrrm.

0 Injection molding process mold temperature 150℃ Standing time 5 minutes O Aging process temperature BOO℃ Time 4 hours 0 Oil dipping process temperature 180℃ Time 24 hours I/'i as silicone oil, viscosity at 25℃ is 10
0 centistoke was used.

[Comparative Example 1] In the primer recombination product of the example, only the white chloride acid-containing isopropanol solution (Pt concentration 10"1 concentration) was omitted, and the fixing roll was the same in all seven examples except for Obtained.

[Comparative Example 2] In the brimer composition of the example, the content of the chloroplatinic acid impropatul solution (Pt concentration tO - concentration) was adjusted to 50 parts by weight, that is, the platinum content in the platinum-based catalyst was adjusted to 50 parts by weight.
A fixing roll was obtained in the same manner as in Example except that j'l was expressed as parts by weight of XlO-'.

The fixing rolls obtained in the above Examples, Comparative Example 1 and Comparative Example 2 were installed in a silicone oil coating type copying machine, the heating temperature for the fixing roll was controlled to 160°C, and copies were made using A4 paper passing horizontally. As a result, the following results were obtained.

Example: No abnormality was observed even after 500,000 copies were made.

Comparative Example 1: Peeling occurred between the core metal and the brimer after 50,000 sheets.

Comparative Example 2 = 30,000 sheets, and peeling occurred between the brimer and the silicone rubber.

Furthermore, when copying was carried out in the same manner as described above with the heating temperature controlled at 180°C, there was no problem even with 500,000 copies in Example 1, whereas the number of copies was reduced in both Comparative g7Il 1 and Comparative Example 2. did.

That is, from the above results, it can be seen that the fixed roll of the present invention has good adhesion between the core metal and the brimer, and between the brimer and the silicone rubber, and is also excellent in both heat resistance and oil resistance. It was obvious.

[Brief explanation of the drawing]

The drawings are explanatory diagrams showing each process for manufacturing the fixing roll of the present invention, and FIG. 1 shows the first cleaning process, FIG. 2 shows the core metal surface treatment process, and FIG. 3 shows the second cleaning process. The process, Figure 4 shows the brimer coating process, Figure 5 shows the air drying process, Figure 6 shows the pre-baking process, Figure 7 shows the injection molding process, Figure 8 shows the aging process, Figure 9 shows the polishing process, and The figures show the oil dipping process, respectively. Figure 1 Figure 5-M6

Claims (1)

[Claims] In a fixing roll in which an addition-type liquid silicone rubber is adhered to a core metal via a primer, the components of the primer include a vinyl group-containing organopolyxane, an organopolysiloxane resin, an organoalkoxysilane, an organohydrodiene polysiloxane, and a platinum-based It contains a catalyst and an organic titanate ester, and contains 5 parts of platinum in the platinum-based catalyst based on 100 parts by weight of the vinyl group-containing organopolysiloxane. Additive liquid silicone rubber fuser roll.