JP3529204B2 - Rubber roll - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rubber roll having improved roll durability by improving adhesion between rubber and rubber. [0002] A rubber roll is a roll in which a metal core such as an iron core is adhered and covered with rubber, and is generally manufactured by spirally winding a rubber sheet around a metal core. This rubber roll is used for various uses such as papermaking, ironmaking, and printing. Conventionally, as a rubber material of the rubber roll, an ethylenically unsaturated nitrile-conjugated diene-based highly saturated copolymer rubber represented by a hydrogenated acrylonitrile-butadiene copolymer rubber excellent in heat resistance and chemical resistance has been used. ing. In this case, an organic peroxide is used as a vulcanizing agent in order to increase the heat resistance of the ethylenically unsaturated nitrile-conjugated diene-based highly saturated copolymer rubber. [0003] In recent years, in the industry where rubber rolls are used, higher speeds and higher loads on production lines have been attempted in order to improve productivity, and therefore, the durability of the rubber rolls used has been further improved. It has been requested.
However, in the case of the ethylenically unsaturated nitrile-conjugated diene-based highly saturated copolymer rubber-organic peroxide vulcanized system, the adhesion between the rubber and the rubber is not sufficient, so that it is difficult to further improve the roll durability. Met. In addition, the roll durability is
Refers to the load durability of the rubber roll. [0004] It is an object of the present invention to provide a rubber roll having improved roll durability by improving the adhesion between rubber and rubber. Here, the rubber-rubber adhesiveness refers to the adhesiveness between one rubber composition constituting the rubber roll and the other rubber composition having the same composition as the rubber composition. [0005] The rubber roll of the present invention comprises:
A rubber comprising 100 parts by weight of an ethylenically unsaturated nitrile-conjugated diene-based highly saturated copolymer rubber mixed with an organic peroxide and 1 to 15 parts by weight of maleic anhydride-modified 1,2-polybutadiene. It is characterized by comprising a composition. Thus, ethylenically unsaturated nitrile-
The addition of maleic anhydride-modified 1,2-polybutadiene to the conjugated diene-based highly saturated copolymer rubber-organic peroxide vulcanized system improves the rubber-rubber adhesion, thereby improving roll durability. It becomes possible. Further, since the ethylenically unsaturated nitrile-conjugated diene-based highly saturated copolymer rubber is used, the heat resistance and the chemical resistance of the rubber roll can be favorably maintained. BEST MODE FOR CARRYING OUT THE INVENTION Ethylenically unsaturated nitrile-conjugated diene-based highly saturated copolymer rubber In the present invention, ethylenically unsaturated nitrile-conjugated diene-based highly saturated copolymer rubber includes acrylonitrile, methacrylonitrile From 10 to 60% by weight of an ethylenically unsaturated nitrile such as α-chloroacrylonitrile and butadiene,
40 to 90% by weight of a conjugated diene such as isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and other monomers copolymerizable therewith, for example, acrylic acid, methacrylic acid, maleic acid Α, β-unsaturated carboxylic acids such as acid and crotonic acid, carboxylic acid esters of methyl acrylate, ethyl acrylate, butyl acrylate, etc.
% By weight of a copolymer obtained by hydrogenating a conjugated diene unit in a copolymer having a Mooney viscosity of 30 to 150 and an iodine value of 60 or less. In the present invention, such an ethylenically unsaturated nitrile-conjugated diene-based highly saturated copolymer rubber is
In particular, a rubber obtained by hydrogenating butadiene units in an acrylonitrile-butadiene copolymer, that is, a hydrogenated nitrile rubber (hereinafter referred to as HNBR), is a highly hydrogenated nitrile rubber in which 80 to 98% of the butadiene units are hydrogenated. It is preferably used. Such a hydrogenated nitrile rubber can be obtained, for example, from Zeon Corporation as Zetpol. A commercially available HNBR may be used.
For example, Zetpol 2030L (HNBR manufactured by Zeon Corporation)
(An acrylonitrile content of 36% and an iodine value of 57%) can be used. Any material that is generally used for peroxide vulcanization of an organic peroxide rubber may be used. For example, dicumyl peroxide, di-t-butyl peroxide, t-butyl cumyl peroxide, benzoyl peroxide, 1,3-bis (t-butylperoxyisopropyl) benzene, and the like. [0010] Maleic anhydride-modified 1,2-polybutadiene is not particularly limited, and a general commercial product may be used. The number average molecular weight is from 500 to 5,000, and the 1,2-vinyl bond content is preferably at least 50%, preferably at least 70%, and is liquid at room temperature. For example, there may be mentioned Lycobond 1756 manufactured by Advanced Resins. The rubber roll according to the present invention is characterized in that the organic peroxide is blended with 100 parts by weight of the ethylenically unsaturated nitrile-conjugated diene-based highly saturated copolymer rubber and the maleic anhydride-modified 1,2- It is composed of a rubber composition containing 1 to 15 parts by weight, preferably 2 to 12 parts by weight of polybutadiene. In addition, trimethylolpropane trimethacrylate, tri (2-ethylhexyl) trimethacrylate, etc. as a co-crosslinking agent used in combination with the organic peroxide may be used as a rubber 1
It can be used in an amount of 1 to 30 parts by weight based on 00 parts by weight. The organic peroxide is preferably blended in an amount of 1 to 15 parts by weight, more preferably 2 to 10 parts by weight, per 100 parts by weight of the ethylenically unsaturated nitrile-conjugated diene-based highly saturated copolymer rubber. When the amount is less than 1 part by weight, the number of crosslinking points is small and physical properties are hardly exhibited. When the amount is more than 15 parts by weight, the organic peroxide residue undesirably affects thermal aging. The modification rate of maleic anhydride in polybutadiene is 1 to 40% by weight, specifically, 10% by weight, 17% by weight, and 23% by weight.
It is preferable that the content be not less than% by weight in view of the effect of providing adhesion. The blending amount of the maleic anhydride-modified 1,2-polybutadiene is 1 to 15 parts by weight, because it is less than 1 part by weight or 15 parts by weight.
If the amount is more than the weight part, the adhesiveness between rubber and rubber becomes insufficient, and the roll durability decreases. In addition, the said rubber composition can contain various compounding agents, such as carbon black and an antioxidant, as needed in addition to these components. In order to produce the rubber roll of the present invention, a rubber sheet made of the unvulcanized rubber composition is spirally wound around a metal core, or extruded into a mold and subsequently vulcanized by a vulcanizing apparatus. According to. EXAMPLES Rubber compositions were prepared according to the content (parts by weight) shown in Table 1 (Examples 1 to 3 and Comparative Examples 1 to 5). This rubber composition was evaluated for rubber-rubber adhesion as follows. Further, a rubber roll was prepared from this rubber composition, and a small roll durability test was performed by the following step method to evaluate the roll durability. Table 1 shows the results. Rubber-Rubber Adhesion : Evaluated by adhesion (kgf / inch) and rubber adhesion. What is excellent in both of these is that the adhesion between rubber and rubber is good. In Table 1, ΔRT means room temperature. Adhesive strength (kgf / inch) was measured using a kneading roll.
A non-vulcanized rubber sheet having a thickness of mm is stuck using a stitcher roll, and vulcanized at 160 ° C for 45 minutes with a press to obtain a co-rubber bonded sample, which is then cut into a 25 mm width tank-like shape, and In the graph, the measurement was performed by peeling by a 180 ° peel method. The higher the value, the better. Evaluation of the presence of rubber was made by visually observing the peeled state of the peeled surface of the peeled sample. “X” indicates poor, “Δ” indicates good, and “○” indicates the best. Step method : A test rubber roll (outer diameter 175 mm, width 180 mm) is pressed against a cylindrical iron roll by applying a load, and while rotating these rolls at a speed of 300 rpm, the load (linear pressure = initial 10 kgf / cm) is applied. The durability test is performed while increasing by 10 kgf / cm every 12 hours. Cracks on the roll surface of the test rubber roll,
The load and time required for rubber-rubber layer peeling, material destruction, and the like, are recorded. [Table 1] As is clear from Table 1, it can be seen that the rubber rolls of the present invention (Examples 1 to 3) have excellent roll durability because the constituent rubber composition has excellent rubber-rubber adhesion. Further, when zinc methacrylate was blended, the heat generation of the roll was increased in a small roll durability test, and the roll durability was lowered, which was not good. Therefore, liquid 1,2-polybutadiene and metal carboxylate must not be mixed together. In addition, since the liquid 1,2-polybutadiene and the metal carboxylate react during the mixing to form the metal salt of 1,2-polybutadiene carboxylic acid, the metal salt of 1,2-polybutadiene carboxylic acid must not be similarly mixed. . As described above, according to the present invention, maleic anhydride-modified 1,2 is added to an ethylenically unsaturated nitrile-conjugated diene-based highly saturated copolymer rubber-organic peroxide vulcanized system. -Because the polybutadiene is blended, the rubber-rubber adhesiveness is improved, so that the roll durability can be improved. Further, since the ethylenically unsaturated nitrile-conjugated diene-based highly saturated copolymer rubber is used, the heat resistance and the chemical resistance of the rubber roll can be favorably maintained.

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Claims (1)

(57) [Claim 1] An organic peroxide is compounded with 100 parts by weight of an ethylenically unsaturated nitrile-conjugated diene-based highly saturated copolymer rubber, and at the same time, maleic anhydride-modified 1, A rubber roll composed of a rubber composition containing 1 to 15 parts by weight of 2-polybutadiene.