JPH0966570A - Fluororesin-based molded product, roll and manufacturing method thereof - Google Patents

Abstract

(57) Abstract: A heat-meltable fluororesin and a fluororubber elastomer are contained, and the fluororubber elastomer is 100% by weight in total of the heat-meltable fluororesin and the fluororubber elastomer. And a fluororesin-based composition present in an amount of 1 to 60% by weight, formed bodies such as fluororesin-based films, sheets and tubes. A rubber layer and a fluororesin-based surface layer are laminated on the outer peripheral surface of the core material in this order in a concentric cross-section, and the fluororesin-based surface layer is formed by the fluororesin-based tube. . [Effect] This fluororesin tube has excellent friction characteristics while retaining the original characteristics of fluororesin such as non-adhesiveness, heat resistance, and abrasion resistance, especially non-adhesiveness.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a fluororesin film,
Regarding fluororesin-based molded products such as sheets and tubes, and rolls, in more detail, while retaining the original properties of fluororesin, such as non-adhesiveness, heat resistance and abrasion resistance, especially non-adhesiveness, excellent friction properties And a molded product such as a fluororesin film, a sheet, a tube, and a roll.

The present invention also relates to a method for manufacturing the above fluororesin-based molded product and roll.

[0003]

2. Description of the Related Art Conventionally, heat resistance, toner releasability, and abrasion resistance to paper have been required for transport rolls, particularly heating rolls used in copying machines (PPC).

In particular, electrophotographic PPC, LBP, F
In the image fixing device in AX or the like, the toner transferred onto the copy paper is heated and fixed in the fixing portion. In the heat fixing of the toner, the copy paper is passed between the heating roll and the pressure fixing roll. It is done by

In the heating roll, the temperature of the heating roll and the pressure fixing roll must withstand the high temperature because the temperature of the heating roll rises to 150 to 200 ° C. when the toner is melted. It is necessary to have releasability so that the melted toner does not adhere, and for this purpose, a roll coated with a fluororesin has been used.

As such a heating roll, for example,
As disclosed in Japanese Examined Patent Publication No. 1-24311 (Japanese Patent Laid-Open No. 57-89785), an elastic layer made of fluororubber or silicone rubber is provided on the outer surface of a metal roller, and fluorine is further provided on the elastic layer. A fixing roller (heating roll) for melting and fixing a toner image, which is characterized by coating a fluororesin to a thickness of 0.1 to 50 μm by applying and baking a resin dispersion liquid, can be mentioned. In this publication, tetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkoxyethylene copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer is used as the fluororesin constituting the fixing roller surface. Resin (FEP)
Are listed.

However, since the surface of this fixing roller (or heating roll) is formed of a fluororesin such as PFA, the releasing characteristics are excellent, but in terms of the feeding characteristics of copy paper, PFA or the like is used. However, there is a problem in that the fluororesin of (3) is slippery and is inferior in the biteability of copy paper or the like between rolls.

Therefore, it has been strongly desired to improve not only the releasing property of the melted toner but also the frictional property of the roll, in particular, the paper feeding property is improved. The inventors of the present invention have conducted extensive studies to solve such problems and found that the surface of a heating roll or the like contains a heat-meltable fluororesin and a fluororubber elastomer, and the fluororubber elastomer is specified. In the fluororesin roll coated with the fluororesin tube made of the fluororesin composition contained in the amount of Property, especially non-stickiness is retained,
Furthermore, they have found that they also have excellent frictional characteristics, and have completed the present invention.

[0009]

SUMMARY OF THE INVENTION The present invention is intended to solve the problems associated with the prior art as described above, and has the inherent characteristics of heat-melting fluororesin such as non-adhesiveness, heat resistance and abrasion resistance.
Especially, while maintaining non-adhesiveness, it also has excellent friction characteristics,
It is an object of the present invention to provide a molded product such as a fluororesin film, a sheet or a tube which is preferably used as a surface material of a roll and has excellent transportability.

It is another object of the present invention to provide a fluororesin roll which is coated on the surface with the above-mentioned fluororesin film, sheet, tube or the like and has excellent transportability.

[0011]

SUMMARY OF THE INVENTION A fluororesin-based molded article according to the present invention contains a heat-meltable fluororesin, preferably PFA, and a fluororubber-based elastomer, preferably a fluororubber-based thermoplastic elastomer. 10 in total of heat-meltable fluororesin and fluororubber elastomer
It is characterized in that the fluororesin composition is present in an amount of 1 to 60% by weight in 0% by weight. Examples of such a molded product include a film, a sheet, a tube and the like.

In the fluororesin roll according to the present invention, a rubber layer and a fluororesin surface layer are laminated in this order on the outer peripheral surface of a core material in a concentric cross section, and the fluororesin surface layer is formed of A fusible fluororesin, preferably PFA, and a fluororubber elastomer, preferably a fluororubber thermoplastic elastomer, are contained, and the fluororubber elastomer is
It is characterized by comprising a fluororesin composition present in an amount of 1 to 60% by weight in a total of 100% by weight of a heat-meltable fluororesin and a fluororubber elastomer.

In the fluororesin roll of the present invention, it is preferable that the rubber layer is made of fluororubber or silicone rubber. In the first method for producing a fluororesin roll according to the present invention, in producing a fluororesin roll in which a rubber layer and a fluororesin surface layer are laminated in a concentric cross section in this order on the outer peripheral surface of a core material. After forming a rubber layer on the outer peripheral surface of the core material, providing an adhesive layer on the surface of this rubber layer, and then coating the surface of this adhesive layer with a fluororesin tube as described below. It has a feature.

This fluororesin tube contains a hot-melt fluororesin, preferably PFA, and a fluororubber elastomer, preferably a fluororubber thermoplastic elastomer, and the fluororubber elastomer is a hot-melt fluororesin. 100% by weight with fluoroelastomer
Of the fluororesin-based composition present in an amount of 1 to 60% by weight, and the inner peripheral surface of the tube is preferably surface-treated. The surface treatment means is preferably N
H ₃ -Na solution (A), 1 or complex compounds of metallic sodium can be added to the tetrahydrofuran solution of naphthalene solution
(B), corona discharge, plasma, or ultraviolet (UV) irradiation is used.

In the second method for producing a fluororesin roll according to the present invention, a fluororesin roll in which a rubber layer and a fluororesin surface layer are laminated concentrically in cross section in this order on the outer peripheral surface of a core material is used. When manufacturing, a mold having a cylindrical space, a tube having a diameter slightly smaller than the inner diameter of the mold, the tube inner surface has been subjected to a surface adhesion treatment,
The tube is made of a heat-meltable fluororesin, preferably PFA.
And a fluororubber elastomer, preferably a fluororubber thermoplastic elastomer, wherein the fluororubber elastomer is 1 to 60% by weight in a total of 100% by weight of the heat-meltable fluororesin and the fluororubber elastomer. The fluororesin-based tube made of the fluororesin-based composition that is present in the amount of is inserted into the tube and the roll core is inserted into the tube, and then rubber is injected and filled between the tube and the roll core, followed by curing. It is characterized by that. Also in this second method, the tube inner peripheral surface treating means similar to the above is preferably adopted.

The fluororesin tube according to the present invention is characterized by non-adhesiveness, heat resistance, which are inherent properties of a heat-meltable fluororesin,
While maintaining abrasion resistance, especially non-adhesiveness, it is also excellent in friction characteristics, and is suitable for use as a roll surface material and has excellent transportability.

The fluororesin roll according to the present invention is
The surface is coated with the fluororesin tube as described above, and it has excellent transportability. Especially, it is a fixing roller for copying machines, a roller used in the food industry (eg, a roller for rolling and transporting bread dough), and a plastic roller. It is preferably used for rolling, forming, and conveying rollers.

[0018]

DETAILED DESCRIPTION OF THE INVENTION The fluororesin-based molded product, roll and method for producing the same according to the present invention will be specifically described below.

[Fluororesin-Based Molded Body and Roll] The fluororesin-based molded body according to the present invention contains a heat-meltable fluororesin and a fluororubber elastomer, and the fluororubber-based elastomer is a heat-meltable fluorine resin. The fluororesin composition is present in an amount of 1 to 60% by weight in the total 100% by weight of the resin and the fluororubber elastomer. Examples of such a molded product include various shapes such as a film, a sheet, and a tube, and the shape thereof is not particularly limited.

In the fluororesin roll according to the present invention, a rubber layer and a surface layer made of the fluororesin tube (fluororesin surface layer) are laminated in this order on the outer peripheral surface of the core material in a concentric cross section. ing.

The heat-meltable fluororesin and fluororubber elastomer used for forming the surface layer of the fluororesin molding such as the fluororesin tube or the fluororesin roll will be described below. As the heat-fusible fluororesin , conventionally known ones can be used. Specifically, for example, FEP (tetrafluoroethylene-hexafluoropropylene copolymer resin), PFA
(Tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin), ETFE (tetrafluoroethylene-ethylene copolymer resin), PVDF (vinylidene fluoride resin), E-CTFE (trifluorochloroethylene-ethylene copolymer resin) ), CTFE, PVF (polyvinyl fluoride) and the like, and PFA is preferably used.

As this PFA, tetrafluoroethylene is used.
The copolymerization ratio ((i) / (ii) molar ratio) of (i) and perfluoroalkyl vinyl ether (ii) is 99.6-96.0 /
0.4 to 4.0 and its molecular weight is 1 × 10 ⁵ to 1 ×
About 10 ⁶ is preferably used, and examples thereof include those sold under the trade name of Teflon (350-J) by Mitsui DuPont Fluorochemicals.

[Fluororubber- based Elastomer] Examples of the fluororubber-based elastomer include non-thermoplastic elastomers and thermoplastic elastomers (including those that can be crosslinked), and fluororubber-based thermoplastic elastomers are preferably used.

Examples of the non-thermoplastic type elastomer (fluorine rubber) include vinylidene fluoride rubber, fluorosilicone rubber, tetrafluoroethylene-propylene rubber, fluorophosphazene rubber, tetrafluoroethylene-perfluorovinyl ether rubber. Examples include rubber.

The fluororubber thermoplastic elastomer is vulcanized at room temperature to exhibit rubber elasticity, and exhibits plastic flow upon heating, and contains an elastomeric polymer chain segment and a non-elastomeric polymer chain segment.
At least one of these is a fluoropolymer chain segment.

Among such fluororubber thermoplastic elastomers, elastomeric polymer chain segments are included.
The ratio of (i) to the non-elastomeric polymer chain segment (ii) is 40 to 95/60 by weight ratio ((i) / (ii)).
5, preferably 70-90 / 30-10 (however, (i) +
(ii) = 100 parts by weight) is preferable.

The specific structure of this fluororubber thermoplastic elastomer is as follows: the elastomeric polymer chain segment (i) and the non-elastomeric polymer chain segment (ii).
And an iodine atom present at one end of the chain, and a residue obtained by removing at least one iodine atom from the iodide compound present at the other end of the chain.

Elastomeric polymer chain segment (i)
Is (1): a copolymer of vinylidene fluoride / hexafluoropropylene or pentafluoropropylene / tetrafluoroethylene (molar ratio 40 to 90/5 to 50/0 to 35), or (2): perfluoroalkyl vinyl ether. / Tetrafluoroethylene / vinylidene fluoride (molar ratio 15-75 / 0-85 / 0-85), having a molecular weight of 30,000 (30,000) -1,2.
It is 100,000 (1.2 million).

The non-elastomeric polymer chain segment (ii) is a copolymer of (3): vinylidene fluoride / tetrafluoroethylene (molar ratio 0-100 / 0-100), or (4): ethylene / tetra Fluoroethylene / [hexafluoropropylene, 3,3,3-trifluoropropylene-1,2-trifluoromethyl-3,3
3,3-trifluoropropylene-1 or perfluoroalkyl vinyl ether] (molar ratio 40 to 60/60
To 40/0 to 30) with a molecular weight of 3,
It is 000 to 400,000 (400,000). However, the total number of moles of each component in each copolymer is 100 moles. Among such fluororubber thermoplastic elastomers, those comprising the elastomeric polymer chain segment (1) and the non-elastomeric polymer chain segment (4) are preferably used.

Details of such a fluororubber thermoplastic elastomer are described in JP-A-53-3495 and JP-B-6-53823. Examples of such an elastomer include Daikin Industries ( stock)
Some are sold under the product name of DAIEL.

In the present invention, the fluororubber-based non-thermoplastic elastomer is disclosed in JP-A-56-16625.
It is possible to use those described in Japanese Patent No. 1, specifically, any one or two of tetrafluoroethylene and perfluoromethyl perfluorovinyl ether, and perfluoro (4-cyanobutyl vinyl ether), Perfluoro (4-carbomethoxybutyl vinyl ether), perfluoro (2-phenoxypropyl vinyl ether), perfluoro (3-phenoxypropyl vinyl ether), perfluoro (6-cyano-5-methyl-3,6-dioxa-1- Octene), and any one or two or more of them can be used.

Among the fluororubber-based non-thermoplastic elastomers, preferably, a part composed of tetrafluoroethylene and perfluoromethylperfluorovinyl ether and a part composed of perfluoro (2-phenoxypropyl vinyl ether) (cured part). , Or a cross-linking site).

In such a fluororubber-based non-thermoplastic elastomer, the above-mentioned tetrafluoroethylene (a), perfluoromethyl perfluorovinyl ether (b) and curing site (c) have a molar ratio ((a) / ( b) / (c)), 53-7
It is preferably 9.8 / 20 to 45 / 0.2 to 2 (however, the total is 100 mol).

When forming the fluororesin tube according to the present invention, the fluororubber elastomer is used as the fluororesin composition in a total amount of 100% by weight of the heat-meltable fluororesin and the fluororubber elastomer. It is desirable to use those present in an amount of 1 to 60% by weight, preferably 5 to 30% by weight.

In the present specification, the distinction between the heat-meltable fluororesin and the fluororubber thermoplastic elastomer can be made, for example, according to the definition of ASTM D883 (1985).

Next, among the fluororesin-based molded products according to the present invention as described above, in particular, a tubular product will be described in detail. Molded products of other shapes, for example, films,
A molded product such as a sheet can also be manufactured according to this. [Production of Fluororesin Tube ] A fluororesin tube may be produced from a fluororesin composition containing such a heat-meltable fluororesin and a fluororubber elastomer according to a conventional method. This heat-meltable fluororesin (eg: PFA) and fluororubber elastomer (eg: fluororubber thermoplastic elastomer [elastomer polymer chain segment (i) is (i) vinylidene fluoride / (b) hexafluoropropylene / (C) Consisting of tetrafluoroethylene and the molar ratio ((B) / (B) / (C)) is 40 to 90.
/ 5 to 50/0 to 35 (total 100 mol), and the molecular weight is 30,000 (30,000) to 1,200,000 (12
0,000) and a non-elastomeric polymer chain segment
(ii) is (h) ethylene / (ri) tetrafluoroethylene /
(Nu) Hexafluoropropylene, whose molar ratio ((chi) / (ri) / (nu)) is 40-60 / 60-40 / 0-30
(Total 100 mol), and the molecular weight is 3,000 to 40.
And the weight ratio of both segments ((i) / (ii)) is 40 to 95/60 to 5 (total 100 parts by weight)]} Temperature above the melting point of the water-soluble fluororesin and fluororubber elastomer) to below the decomposition temperature, for example 320-390 ° C., preferably 36
Knead at a temperature of 0 to 390 ° C. for about 10 to 30 minutes,
It may be extruded into a tube having an inner diameter of 1.0 to 10.0 cmφ and a wall thickness of about 30 to 200 μm. At this time, an extruder or the like can be used.

The fluororesin-based tube thus obtained can be used as it is for a roll coating material or the like, but if necessary, the tube may be treated with ionizing radiation. For example, as disclosed in Japanese Examined Patent Publication No. 6-53823, 1 to 50 in an atmosphere in which oxygen, ozone, or a mixed gas thereof is, for example, 1.5% by volume or less.
A method of irradiating the tube with Mrad ionizing radiation (eg, X-ray, γ-ray, electron beam, proton beam, deuteron beam, α-ray, β-ray) to crosslink and cure the fluororubber elastomer is used. Further, in the fluororesin composition, in addition to the heat-meltable fluororesin and the fluororubber elastomer (fluororubber thermoplastic elastomer or fluororubber non-thermoplastic elastomer), if necessary, a crosslinking agent (eg, sulfur, polyol , Vulcanizing agents such as peroxides), fillers, crosslinking aids,
Reinforcing agents, plasticizers, processing aids, anti-aging agents, anti-scorch agents, and other rubber chemicals or fillers may be contained. Such fluororesin-based compositions may be vulcanized (fluorinated by a conventional method). Vulcanization (crosslinking) of the rubber elastomer may be performed. In the present invention, such as rubber chemicals, the fluororesin-based composition, as described above, if necessary, a crosslinking agent, a co-crosslinking agent, a crosslinking aid, a reinforcing agent,
Rubber chemicals such as processing aids, anti-aging agents, anti-scorch agents,
Fillers and the like are contained.

The above crosslinking agent used in the present invention includes:
Examples thereof include sulfur-based crosslinking agents, peroxide-based crosslinking agents, co-crosslinking agents, and other crosslinking agents usually used for rubber. These can be used alone or in combination.

Specific examples of the sulfur-based crosslinking agent include powdered sulfur, precipitated sulfur, colloidal sulfur, surface-treated sulfur, insoluble sulfur and sulfur chloride. Specific examples of the peroxide crosslinking agent include 1,3-bis (tert-butylperoxyisopropyl) benzene, tert-butylhydroperoxide, 1,4-bis (tert-butylperoxyisopropyl) benzene, 2,5-Dimethylhexane-2,5-dihydroperoxide, dicumyl peroxide, 2,5-dimethyl
-2,5-bis (tert-butylperoxy) hexane, tert-
Butyl cumyl peroxide, 2,5-dimethyl-2,5-tert--
Butylperoxyhexyne-3,1,1-bis (tert-butylperoxy) cyclododecane, 2,2-bis (tert-butylperoxy) octane, 1,1-bis (tert-butylperoxy)- 3,3,5-trimethylcyclohexane, n-butyl-4,
4-bis (tert-butylperoxy) valerate, tert-butylperoxybenzoate, tert-butylperoxyisopropyl carbonate, zinc peroxide and the like can be mentioned.

Specific examples of the co-crosslinking agent include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 3chloro 2 hydroxypropyl methacrylate, zinc methacrylate, triallyl cyanurate, triallyl isocyanurate, dimer 2,
4 Toluene diisocyanate, triallyl trimellitate, diallyl phthalate, diallyl chlorendate and the like can be mentioned.

Such a cross-linking agent is usually used in an amount of 0.1 to 10 parts by weight, preferably 0.3 to 8 parts by weight, based on 100 parts by weight of the fluororesin composition. Upon kneading, the following rubber chemicals may be added together with the cross-linking agent within a range not impairing the object of the present invention.

Examples of such a rubber chemical include a crosslinking aid, a reinforcing agent, a plasticizer, a processing aid, an antioxidant and an anti-scorch agent, in addition to the above-mentioned crosslinking agent. As the cross-linking aid, guanidine compounds, sulfenamide compounds, thiuram compounds, dithiocarbamate compounds, aldehyde amine compounds, thiourea compounds,
Examples thereof include xanthate compounds.

Such a cross-linking aid can be usually used in an amount of 0.5 to 10 parts by weight with respect to 100 parts by weight of the fluororesin composition. Further, these crosslinking aids can also be used as a crosslinking agent.

The rubber reinforcing agent also functions as a filler, and examples of such a rubber reinforcing agent (filler) include carbon black, silica, clay, silicate, alumina, aluminum hydroxide, calcium carbonate, and silica. An acid etc. can be mentioned.

The rubber reinforcing agent (filler) can be usually used in an amount of 5 to 150 parts by weight based on 100 parts by weight of the fluororesin composition. Examples of the plasticizer include process oil, DOP (dioctyl phthalate), DOS (dioctyl sebacate), vegetable oil, factice and the like.

Such a plasticizer can be used usually in an amount of 5 to 50 parts by weight with respect to 100 parts by weight of the fluororesin composition. Examples of processing aids include zinc oxide, stearic acid, polyethylene glycol and the like.

The processing aid can be usually used in an amount of 0.5 to 6 parts by weight with respect to 100 parts by weight of the fluororesin composition. As an anti-aging agent, 2,6-di-tert-butyl
-4-methylphenol, N-isopropyl-N'-phenyl-p-
Phenylenediamine, poly (2,2,4-trimethyl-1,2-dihydroquinoline), 2 mercaptobenzimidazole,
Specific wax can be used.

The antiaging agent is a fluororesin composition 100.
Usually, it can be used in an amount of 0.5 to 3 parts by weight based on parts by weight. The fluororesin composition used in the present invention may contain molybdenum disulfide and conductive carbon, if necessary, in addition to the above components. [ Production of Fluororesin Roll ] Further, in the present invention in which a rubber layer and a fluororesin surface layer are laminated in this order in a concentric cross section on the outer peripheral surface of a core material using such a fluororesin tube. To produce such a fluororesin roll, after forming a rubber layer made of silicone rubber, fluororubber or the like on the surface of the core material, providing an adhesive layer on the surface of this rubber layer,
Next, the surface of the adhesive layer may be covered with the fluororesin tube.

More specifically, first, for example, in order to form a silicone rubber layer on the surface of a core material made of metal or the like, an aluminum core metal (core material) is set in the center of the mold and the core is formed. A vulcanized silicone rubber layer is formed on the outer peripheral surface of the core metal by arranging a silicon-based raw rubber containing a vulcanizing agent, a filler, etc. around the core metal so as to cover the outer peripheral surface of the gold and heating and pressing. Then, an adhesive layer is formed on the outer peripheral surface of the silicone rubber layer. Next, the surface of the adhesive layer is covered with a fluororesin tube to obtain a desired fluororesin roll.
The inner peripheral surface of the fluororesin tube used at this time is N
It is preferable that the surface treatment is performed using a H ₃ —Na solution or the like.

In order to perform the surface treatment only on the inner peripheral surface of the fluororesin tube in this manner, a conventionally known method can be appropriately adopted. For example, in the fluororesin tube whose outer surface is masked in advance. To the surface treatment solution, or a method of immersing the fluororesin tube whose outer surface is masked in the surface treatment solution in the above, Japanese Patent Application Laid-Open No. 5-5
The method described in Japanese Patent Application No. 9195 (Japanese Patent Application No. 3-172041) may be used.

In the method described in Japanese Patent Laid-Open No. 5-59195, a fluororesin-based tube having a closed portion by sandwiching it with a pair of pinch rolls, pinch boards, etc.
A fluororesin tube is obtained by injecting the surface treatment liquid from the open end of the tube to store the surface treatment liquid at a position above the closed portion and moving the relative position of the closed portion with respect to the longitudinal direction of the tube. Only the inner peripheral surface of the fluororesin tube can be treated by moving the contact portion between the inner peripheral surface and the surface treatment liquid. In order to move the relative position of the closed portion with respect to the longitudinal direction of the tube as described above, for example, the tube is fixed and the closed portion is moved vertically along the tube, or the closed portion is moved. The part may be fixed and the tube may be moved in the vertical direction.

Examples of the surface treatment liquid include a liquid ammonia solution (a) of an alkali metal such as sodium used in the “sodium / liquid ammonia solution method” and an electron donation of an alkali metal used in the “tetraetch method”. Type complex (eg: sodium dispersion of sodium having a relatively high melting point in which naphthalene is dispersed as a medium), solution (b), etc. can be mentioned, and it is preferable for uniform and efficient surface treatment (adhesion treatment) effect. An excellent alkali metal liquid ammonia solution (a) is used. The surface treatment (inner peripheral surface) of the tube can be performed by irradiation with energy rays such as ultraviolet rays (UV), laser, and plasma, in addition to the chemical treatment method as described above.

In the present invention, the following method is used for producing a fluororesin roll in which a rubber layer and a fluororesin surface layer are laminated in this order on the outer peripheral surface of a core material in a concentric cross section. May be adopted.

That is, a die having a cylindrical space is a tube having a diameter slightly smaller than the inner diameter of the die, and the inner surface of the tube is subjected to surface adhesion treatment. A tube made of a material may be inserted, a roll core may be inserted into the tube, and then rubber may be injected and filled between the tube and the roll core, followed by curing (simultaneous vulcanization adhesion). Also in this method, the tube inner peripheral surface treating means similar to the above is preferably adopted. Further, the adhesive layer as described above may be formed on either or both of the inner peripheral surface of the tube and the outer peripheral surface of the roll core.

The surface of the fluororesin roll thus obtained contains the heat-meltable fluororesin and the fluororubber-based elastomer in the above amounts, and therefore the heat-meltable fluororesin is used. It retains the original properties of non-adhesiveness, heat resistance, and abrasion resistance, especially non-adhesiveness, and also has excellent frictional properties, and is suitably used as a roll for transporting paper and the like. Such a fluororesin-based roll according to the present invention is used as a fixing roller of a copying machine, a food industry (eg, bread making industry).
It can be used for various purposes such as rollers for rolling / forming / conveying of raw materials or processed products used in, as well as rollers for rolling / forming / conveying of plastics.

[0056]

EFFECTS OF THE INVENTION The molded article such as the fluororesin tube according to the present invention contains the heat-meltable fluororesin and the fluororubber elastomer in the above-mentioned amounts, and therefore the heat-meltable fluororesin is essentially While maintaining the non-adhesiveness, heat resistance, and abrasion resistance, especially non-adhesiveness, which are the characteristics of 1.

Since the surface layer of the fluororesin roll according to the present invention is made of the fluororesin composition containing the above-mentioned amounts of the heat-fusible fluororesin and the fluororubber elastomer, the heat-meltability is improved. It retains the original properties of fluororesin such as non-adhesiveness, heat resistance and abrasion resistance, especially non-adhesiveness, and also has excellent frictional properties, and is suitably used as a roll for transporting paper and the like.

[0058]

EXAMPLES The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the table, the amount of each component is
It is a "weight part" display. The physical properties and the like of the samples used in the following examples and comparative examples are as follows. (1) Physical property value of PFA : Copolymerization ratio of tetrafluoroethylene (i) and perfluoroalkyl vinyl ether (ii) in PFA ((i) / (ii) molar ratio) = 99.6-96.0 / 0.4 ~
4.0, molecular weight 1 × 10 ⁵ to 1 × 10 ⁶ , manufactured by Mitsui DuPont Fluorochemicals, trade name: Teflon 350-J. (2) Physical properties of fluororubber elastomer: Elastomer polymer chain segment (i) is (a) vinylidene fluoride /
(B) Hexafluoropropylene / (c) Tetrafluoroethylene, and the molar ratio ((b) / (b) / (c)) is 40-9.
0/5 to 50/0 to 35 (total 100 mol), the molecular weight is 30,000 to 1.2 million, and the non-elastomeric polymer chain segment (ii) is (h) ethylene / (ri) tetrafluoroethylene / (Nu) consisting of hexafluoropropylene,
The molar ratio ((chi) / (ri) / (nu)) is 40-60 / 60-40
/ 0 to 30 (total 100 mol) and molecular weight of 30,000 to
400,000, and the weight ratio of both segments ((i) / (ii)) is 4
0 to 95/60 to 5 (total 100 parts by weight), manufactured by Daikin Industries, Ltd., product name: Daier Thermoplastic T
530.

[0059]

[Examples 1 to 3 and Comparative Example 1] (a) Production of fluororesin tube PFA ( manufactured by Mitsui DuPont Fluorochemical Co., Teflon 3)
50-J) and fluoroelastomer thermoplastic elastomer (Daikin Thermoplastic T530 manufactured by Daikin Industries, Ltd.)
And, as shown in Table 1, the amount of the fluororubber thermoplastic elastomer in the obtained composition was 5% by weight, respectively.
(Example 1), 10 wt% (Example 2), 20 wt%
(Example 3), blended in an amount of 0% by weight (Comparative Example 1), kneaded with a ball mill type stirrer or rocking mixer for 30 minutes to uniformly mix, and then charged into an extruder. At a molding temperature of 380 ° C, the wall thickness is 50 μm
Extruded a thin wall tube.

Then, on the inner peripheral surface of this thin-walled tube, N
Surface treatment was performed with a H ₃ -Na solution. That is, a surface treatment liquid (NH ₃ -Na liquid: a solution in which 0.3 to 20.0 g of sodium is dissolved in 1 liter of liquid ammonia) is placed in a tube provided with a closed portion by being sandwiched by a pair of pinch rolls. ) Was injected to store the surface treatment solution above the closed part, and the closed part was moved downward at a speed of 20 m / min relative to the tube, whereby only the inner peripheral surface of the tube was processed.

The physical properties are shown in Table 1. (B) Production of fluororesin roll A fluororesin roll using this thin tube as a cover for a fixing roll was produced as follows.

That is, the outer peripheral surface of the roll having the silicone rubber layer formed on the outer peripheral surface of the cored bar was integrally covered with the above-mentioned thin-walled tube via an adhesive to manufacture a fluororesin fixing roll. In detail, an aluminum cored bar (carbon steel, diameter 10 mmφ x length 25 cm) is set in the center of the mold, and a vulcanizing agent is applied around the cored bar so as to cover the outer peripheral surface of the cored bar. Place a silicone-based rubber compounded with a filler or the like, and heat (170 ° C x 30 minutes) / pressurize (100
kgf / cm ² ) to form a concentric (equal thickness) vulcanized silicone rubber layer on the outer peripheral surface of the cored bar.

Next, a silicone-based primer was applied to the outer peripheral surface of this silicone rubber layer to form an adhesive layer.
Next, the surface of the adhesive layer was covered with the thin-walled tube having the inner peripheral surface treated to manufacture a fluororesin roll.

The measuring methods in the table below are as follows. (* 1) Contact angle (θ °): Kyowa Interface Science Co., Ltd., using contact angle meter CA-A type, droplet method ,: pure water, 25 ° C.

(* 2) Friction coefficient: According to JIS K 7125. However, friction speed 600mm / min, friction force 1600g
f (44 gf / cm ² ).

(* 3) Breaking strength (kgf / mm ² ), elongation (%): According to JIS K 6897. Uses micro dumbbells, pulling speed: 200 mm / min, chuck distance:
20 mm.

[0067]

[Table 1]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08J 7/00 304 C08J 7/00 304 C08L 27/12 LGB C08L 27/12 LGB 27/18 LGB 27 / 18 LGB // B29K 27:12 83:00 B29L 31:32 (72) Inventor Shinji Takahashi 232-1 Tanasawa, Atsugi City, Kanagawa Prefecture Japan Balcar Industry Co., Ltd. (72) Inventor Yoshitaka Samura Osaka 5-5, Annaka-cho, Yao-shi, Japan Inside Japan Bulker Industry Co., Ltd.

Claims (18)

[Claims] 1. A heat-meltable fluororesin and a fluororubber elastomer, the fluororubber elastomer comprising:
A fluororesin-based molded article comprising a fluororesin-based composition present in an amount of 1 to 60% by weight in a total of 100% by weight of a heat-meltable fluororesin and a fluororubber-based elastomer. 2. The fluororesin-based molded product according to claim 1, wherein the heat-meltable fluororesin is PFA. 3. The fluororesin-based molded product according to claim 1, wherein the fluororubber-based elastomer is thermoplastic. 4. The fluororesin-based molded article according to any one of claims 1 to 3, wherein the shape of the fluororesin-based molded article is any one of a film, a sheet and a tube. 5. A rubber layer and a fluororesin-based surface layer are laminated on the outer peripheral surface of a core material in this order in a concentric cross-section, and the fluororesin-based surface layer comprises a heat-meltable fluororesin and a fluororubber-based surface layer. From a fluororesin-based composition containing an elastomer, the fluororubber-based elastomer being present in an amount of 1 to 60% by weight in a total of 100% by weight of the heat-meltable fluororesin and the fluororubber-based elastomer. A fluororesin-based roll characterized by 6. The fluororesin roll according to claim 5, wherein the heat-meltable fluororesin is PFA. 7. The fluororesin roll according to claim 5, wherein the fluororubber elastomer is thermoplastic. 8. The fluororesin roll according to claim 5, wherein the rubber layer is formed of silicone rubber. 9. A rubber layer is formed on the surface of a core material when manufacturing a fluororesin roll in which a rubber layer and a fluororesin surface layer are laminated in this order in a concentric cross section on the outer peripheral surface of the core material. Then, an adhesive layer is provided on the surface of the rubber layer, and then the surface of the adhesive layer contains a heat-meltable fluororesin and a fluororubber elastomer, and the fluororubber elastomer is 100% by weight of resin and fluororubber elastomer
Of a fluororesin composition present in an amount of 1 to 60% by weight, the inner peripheral surface of which is covered with a fluororesin tube whose surface is treated. Method. 10. The method according to claim 9, wherein the heat fusible fluororesin is PFA. 11. The method according to claim 9, wherein the fluororubber elastomer is thermoplastic. 12. The inner peripheral surface of the fluororesin tube is NH
_3- Na solution (A) or complex compound solution (B) prepared by adding sodium metal to tetrahydrofuran solution of naphthalene
The method according to any one of claims 9 to 11, wherein the method is surface-treated with. 13. The method according to claim 9, wherein the inner peripheral surface of the fluororesin tube is subjected to ultraviolet (UV) treatment. 14. When manufacturing a fluororesin roll in which a rubber layer and a fluororesin surface layer are laminated in this order in a concentric circular cross section on the outer peripheral surface of a core material, a die having a cylindrical space is provided with a die. A tube having a diameter slightly smaller than the mold inner diameter,
The inner surface of the tube is subjected to surface adhesion treatment, the tube contains a heat-meltable fluororesin and a fluororubber elastomer, and the fluororubber elastomer is
A fluororesin tube made of a fluororesin composition present in an amount of 1 to 60% by weight is inserted into a total of 100% by weight of a heat-meltable fluororesin and a fluororubber elastomer, and a roll is placed in the tube. A method for producing a fluororesin roll, comprising: inserting a core, and then injecting and filling rubber between the tube and the roll core, followed by curing. 15. The method according to claim 14, wherein the heat-meltable fluororesin is PFA. 16. The method according to claim 14 or 15, wherein the fluororubber elastomer is thermoplastic. 17. The inner peripheral surface of the fluororesin tube is NH
_3- Na solution (A) or complex compound solution (B) prepared by adding sodium metal to tetrahydrofuran solution of naphthalene
The method according to any one of claims 14 to 16, wherein the method is surface treatment with. 18. The method according to claim 14, wherein the inner peripheral surface of the fluororesin tube is subjected to ultraviolet (UV) treatment.