JPH11100417A - Rubber composition and rubber roll using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a rubber composition giving rubber rolls improved in adhesivity between rubber-rubber and excellent in durability by compounding a specified rubber with a specific amount of an organic peroxide, a specific amount of a specified compound and a specific amount of sulfur. SOLUTION: This rubber composition comprises (A) 100 pts.wt. of a hydrogenated acrylonitrile-butadiene copolymer rubber, (B) 0.005-0.020 mole of an organic peroxide [e.g. 1,3-bis(t-butylperoxyisopropyl)benzene], (C) 5-50 pts.wt., preferably 5-30 pts.wt., of a methacrylic acid polyhydric alcohol ester (e.g. trimethylolpropane methacrylate), and (D) <3 pts.wt., preferably 0.5-2.5 pts.wt., of sulfur, so as to satisfy the equation: y/x=1/30 to 4/30 [(x) is the amount (pts.wt.) of the compounded component C; (y) is the amount (pts.wt.) of the compounded component D]. A rubber sheet comprising the vulcanized rubber composition is spirally wound on a metal core and subsequently vulcanized to produce a rubber roll.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rubber composition having improved adhesion between rubber and rubber, and a rubber roll having improved roll durability by using this rubber composition.

[0002]

2. Description of the Related Art 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, iron making, and printing. Conventionally, a hydrogenated acrylonitrile-butadiene copolymer rubber excellent in heat resistance and chemical resistance has been used as a rubber material for the rubber roll. In this case, hydrogenated acrylonitrile-
In order to increase the heat resistance of butadiene copolymer rubber, an organic peroxide is used as a vulcanizing agent.

[0003] In recent years, in the industry using rubber rolls, higher speed and higher load of production lines have been attempted in order to improve productivity, and therefore, the durability of rubber rolls used has been further improved. It has been requested.
However, in the hydrogenated acrylonitrile-butadiene copolymer rubber-organic peroxide vulcanization system, the adhesion between rubber and rubber was not sufficient, and it was difficult to further improve the roll durability. Note that the roll durability refers to the load durability of the rubber roll.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a rubber composition having improved adhesion between rubber and rubber, and a rubber roll having improved roll durability by using this rubber composition. And Here, the rubber-rubber adhesiveness refers to the adhesiveness between one rubber composition and the other rubber composition having the same composition.

[0005]

Means for Solving the Problems The rubber composition of the present invention comprises:
Hydrogenated acrylonitrile-butadiene copolymer rubber 10
0.005 mol to 0.020 mol of organic peroxide, 5 to 50 parts by weight of methacrylic acid polyhydric alcohol ester and less than 3 parts by weight of sulfur per 0 parts by weight, and the compounding amount of methacrylic acid polyhydric alcohol ester Is x parts by weight and the amount of sulfur is y parts by weight, y / x = 1 /
It is characterized by satisfying the ratio of 30 to 4/30.

The rubber roll of the present invention comprises 0.005 mol to 0.020 mol of an organic peroxide, 5 to 50 parts by weight of a polyhydric alcohol ester of methacrylic acid, and 100 parts by weight of a hydrogenated acrylonitrile-butadiene copolymer rubber. When less than 3 parts by weight is blended, and when the blending amount of methacrylic acid polyhydric alcohol ester is x part by weight and the blending amount of sulfur is y part by weight, the ratio of y / x = 1/30 to 4/30. Characterized by comprising a rubber composition satisfying the following.

As described above, in the present invention, the adhesion between rubber and rubber is improved because the methacrylic acid polyhydric alcohol ester and sulfur are added to the hydrogenated acrylonitrile-butadiene copolymer rubber-organic peroxide vulcanization system. However, this makes it possible to improve the durability of the roll.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hydrogenated acrylonitrile-butadiene copolymer rubber An acrylonitrile-butadiene copolymer rubber having a double bond hydrogenated by hydrogenation (hereinafter referred to as HNBR)
). As the HNBR, a commercially available product may be used, for example, Zetpol 2030L (HN manufactured by Zeon Corporation).
BR (acrylonitrile content 36%, hydrogenation rate 90%, diene content 6.4%) can be used.

Any organic peroxide may be used as long as it is generally used for peroxide vulcanization of rubber. For example, dicumyl peroxide, di-t-butyl peroxide, t-butyl cumyl peroxide, benzoyl peroxide, 1,3-bis (t-butylperoxyisopropyl) benzene, and the like.

[0010] Methacrylic acid polyhydric alcohol ester is not particularly limited. For example, trimethylolpropane methacrylate (TMMPA), triallyl isocyanurate (TAIC), diallyl phthalate (D
AP). What is generally used for vulcanization of sulfur rubber may be used. For example, powdered sulfur, precipitated sulfur, colloidal sulfur and the like.

[0011] The rubber composition of the present invention comprises the above-mentioned HNBR
0.005 mol to 0.02 mol of the organic peroxide per 100 parts by weight.
0 moles of the methacrylic acid polyhydric alcohol ester 5
50 parts by weight, preferably 5 to 30 parts by weight, and less than 3 parts by weight of the sulfur, preferably 0.5 to 2.5 parts by weight. The compounding amount of the organic peroxide of 0.005 mol to 0.020 mol is a general compounding amount for rubber.

The reason why the amount of the methacrylic acid polyhydric alcohol ester is set to 5 to 50 parts by weight is that if the amount is less than 5 parts by weight, the adhesion between rubber and rubber is inferior. This is because the vulcanized rubber mixing processability is remarkably deteriorated, and the vulcanization properties are also decreased in tensile strength, rubber-rubber adhesive strength, and roll durability. Reduce the amount of sulfur to 3
Less than 3 parts by weight is more than 3 parts by weight, tensile strength,
This is because 100% tensile stress is reduced and roll durability is reduced.

Further, methacrylic acid polyhydric alcohol ester
The amount of sulfur is x part by weight and the amount of sulfur is y part by weight.
Then, the ratio y / x = 1/30 to 4/30 is satisfied. this
Is the compounding amount x of TMPMMA and the compounding amount of sulfur shown in FIG.
It is clear from the relationship with y. That is, FIG.
The amount x of MPMA and the amount y of sulfur are variously changed.
To make a test rubber roll (HNBR content and
The amount of organic peroxide is constant), and the following steps
Measure the value of the load that can withstand the load by applying the
The values are listed. In FIG. 1, "x" indicates 50 kgf / cm.^TwoLess than
If the load can withstand, "▲" indicates 50-70kgf / cm^TwoLess than
“●” indicates 70kgf / cm when the load can be withheld. ^TwoMore than load
In each case. Roll durability is one
Generally, 50kgf / cm^TwoIt is good to be able to withstand the above load
It is. Therefore, in the present invention, 50 kgf / cm^TwoOver load
If it can withstand heavy weight, it is said that the roll durability is good. This
Looking at Fig. 1 from the viewpoint of "?", "▲" and "●" exist.
Is less than 3 parts by weight of sulfur and 5 of TMPMA
5050 parts by weight, and y = 1 / 30x to y = 4 / 30x
It is. Therefore, in the present invention, y / x = 1/30 to 4/30
doing. The rubber composition of the present invention comprises these components
In addition, various compounding agents such as carbon black
Can be contained.

Step method : A test rubber roll is pressed against a cylindrical iron roll while applying a load, and while rotating these rolls at a speed of 300 rpm, the load (linear pressure = initial 10 kgf / cm)
² ) The durability test is performed while increasing by 10 kgf / cm ² every 12 hours. The load and time required for cracks, rubber-rubber layer peeling, material destruction, and the like to occur on the roll surface of the test rubber roll are recorded.

[0015] The rubber roll of the present invention comprises the above rubber composition. In order to produce this rubber roll, a rubber sheet made of an unvulcanized rubber composition may be spirally wound around a metal core, and then vulcanized by a conventional method.

[0016]

EXAMPLES Rubber compositions were prepared according to the contents (parts by weight) shown in Tables 1 and 2 (Examples 1 to 10, Comparative Examples 1 to 1).
0). The rubber-rubber adhesiveness of this rubber composition was evaluated as follows. Further, a rubber roll was prepared from this rubber composition, and a small roll durability test was performed by the above-described step method to evaluate roll durability. The results are shown in Tables 1 and 2.

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 Tables 1 and 2,

RT means room temperature. Adhesive strength (kgf / inch) was measured using a kneading roll. A 3mm thick unvulcanized rubber sheet was stuck together using a stitcher roll and vulcanized at 160 ° C for 45 minutes using a press. Was obtained, cut into a 25 mm wide tank shape, and peeled off using an autograph by a 180 ° peel method to measure. The higher the value, the better.

Evaluation of the presence of the 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.

[0020]

[Table 1]

[0021]

[Table 2] Note) * 1 Hydrogenated NBR (HNBR), Zeon Corporation
Made. * 2 Antioxidant, 4,4-bis-dimethylbenzyldiphenylamine, manufactured by Uniroyal.

* 3 Tri (2-methylhexyl) trimellitate, Adekasizer C-8, manufactured by Asahi Denka Kogyo KK * 4 Peroxide, 1,3-bis (t-butylperoxyisopropyl) benzene, Peroximon F-40, NOF Corporation
Made. * 5 Trimethylolpropane methacrylate.

As is clear from Tables 1 and 2, the rubber compositions of the present invention (Examples 1 to 10) are excellent in rubber-rubber adhesion, and the rubber rolls made with the rubber compositions are rolls. It turns out that it is excellent in durability.

[0024]

As described above, according to the present invention, H
Since the methacrylic acid polyhydric alcohol ester and the sulfur are blended in the NBR-organic peroxide vulcanization system, the adhesion between rubber and rubber is improved, thereby enabling the roll durability to be improved. Incidentally, the rubber composition of the present invention is excellent in rubber-rubber adhesiveness, so that a mold,
It is also applicable to lining and the like.

[Brief description of the drawings]

BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a relational diagram between a blending amount x part by weight of TMPMA (trimethylolpropane methacrylate) and a blending amount y of sulfur.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁶ Identification code FI C08L 51/04 C08L 51/04 // B29K 55:00 (72) Inventor Hiroshi Sakakida 1-2, Yamitsu, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture. 1 Zeon Corporation General Development Center (72) Inventor Koichi Nishimura 1-2-1 Yakko, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture Zeon Corporation General Development Center

Claims (6)

[Claims] 1. An organic peroxide in an amount of 0.005 mol to 0.020 mol, 5 to 50 parts by weight of a polyhydric alcohol ester of methacrylic acid, and less than 3 parts by weight of sulfur, based on 100 parts by weight of a hydrogenated acrylonitrile-butadiene copolymer rubber. When the blending amount of methacrylic acid polyhydric alcohol ester is x part by weight and the blending amount of sulfur is y part by weight, y
A rubber composition satisfying a ratio of / x = 1/30 to 4/30. 2. The organic peroxide is dicumyl peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, benzoyl peroxide, and 1,2.
The rubber composition according to claim 1, which is one kind selected from the group consisting of 3-bis (t-butylperoxyisopropyl) benzene. 3. The rubber composition according to claim 1, wherein the polyhydric alcohol ester of methacrylic acid is one selected from the group consisting of trimethylolpropane methacrylate, triallyl isocyanurate, and diallyl phthalate. 4. An amount of 0.005 mol to 0.020 mol of an organic peroxide, 5 to 50 parts by weight of a polyhydric alcohol ester of methacrylic acid, and less than 3 parts by weight of sulfur based on 100 parts by weight of a hydrogenated acrylonitrile-butadiene copolymer rubber. When the blending amount of methacrylic acid polyhydric alcohol ester is x part by weight and the blending amount of sulfur is y part by weight, y
A rubber roll composed of a rubber composition satisfying a ratio of / x = 1/30 to 4/30. 5. The organic peroxide comprises dicumyl peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, benzoyl peroxide, and 1,
The rubber roll according to claim 4, which is one kind selected from the group consisting of 3-bis (t-butylperoxyisopropyl) benzene. 6. The rubber roll according to claim 4, wherein the methacrylic acid polyhydric alcohol ester is one selected from the group consisting of trimethylolpropane methacrylate, triallyl isocyanurate, and diallyl phthalate.