Chlorinated polyolefin composition

Abstract

To provide a chlorinated polyolefin composition, or more specifically, a chlorinated polyolefin composition that has great tensile elongation at break and also has excellent durability such as acid resistance, alkali resistance, and heat resistance.SOLUTION: A chlorinated polyolefin composition contains chlorinated polyolefin, an acid acceptor, a triazine compound, and a sulfur-containing vulcanization accelerator, the acid acceptor being at least one selected from epoxidized oil and epoxidized polybutadiene.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to chlorinated polyolefin compositions. [Background technology]

[0002] Chlorinated polyolefins are chlorine-containing polymers that do not have unsaturated bonds in their main chain. Because they have excellent heat aging resistance, oil resistance, weather resistance, chemical resistance, ozone resistance, and flame retardancy, they are used in a variety of applications such as hoses, wire coatings, rollers, and gaskets.

[0003] On the other hand, because chlorinated polyolefins contain chloro groups in the polymer, excessive thermal degradation can cause acidic components derived from these chloro groups to be released. Therefore, it is generally known that compounding agents such as acid acceptors are necessary to prevent the release of acidic components from the polymer. Lead monoxide, magnesium oxide, and synthetic hydrotalcite are known to be used as acid acceptors.

[0004] However, as is well known, chlorinated polyolefin compositions using lead monoxide as an acid acceptor have environmental burdens. Chlorinated polyolefin compositions using magnesium oxide or synthetic hydrotalcite have poor acid, alkali, and water resistance, making them unsuitable for applications involving contact with acids, alkalis, or water. Therefore, there has been a demand for chlorinated polyolefin compositions with good acid, alkali, water, and heat resistance.

[0005] Furthermore, chlorinated polyolefins include chlorosulfonated polyolefins that contain sulfonic acid (for example, Patent Document 1). Patent Document 1 discloses a chlorosulfonated polyolefin composition characterized by containing 3 to 50 parts by weight of an aliphatic glycidyl ether, epoxidized polybutadiene, or epoxidized oil per 100 parts by weight of a chlorosulfonated polyolefin.

[0006] Patent Document 2 discloses a chlorinated polyolefin composition containing: 100 parts by mass of a chlorinated polyolefin obtained by chlorinating a polyolefin selected from an ethylene homopolymer or a copolymer of ethylene and α-olefin, having a density of 0.90 or higher, having a chlorine content of 25 to 45% by mass, a melt flow rate of 0.1 to 300 g / 10 min, and a heat of fusion of crystals by DSC of 20 to 60 J / g; 1 to 15 parts by mass of an epoxy derivative selected from epoxidized unsaturated oils and fats, epoxidized unsaturated fatty acid esters, epichlorohydrin derivatives, and epoxycyclohexane derivatives; and 0.05 to 3 parts by mass of a stabilizer selected from hydrotalcite. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Publication No. 2017-88872 [Patent Document 2] Japanese Patent Publication No. 2006-342343 [Overview of the project] [Problems that the invention aims to solve]

[0008] However, although the composition described in Patent Document 1 is said to have excellent water resistance and acid resistance, further improvements were needed. Patent Document 2 only focuses on the transparency, mechanical strength, permanent elongation, and whitening resistance of products such as tubes.

[0009] Furthermore, in various applications such as hoses, wire insulation, rollers, and gaskets, these materials are often exposed to conditions such as acidic, alkaline, and high-temperature environments. However, conventional molded products made from chlorinated polyolefin compositions have not always satisfied these requirements. Therefore, the present invention aims to provide a chlorinated polyolefin composition that exhibits high tensile elongation at break and excellent durability, including resistance to acids, alkalis, heat, and water. [Means for solving the problem]

[0010] As a result of diligent research, the inventors discovered that the above problems could be solved by combining chlorinated polyolefin with a specific acid acceptor, and thus completed the present invention.

[0011] In other words, the present invention relates to the following chlorinated polyolefin compositions [1] to

[12] . [1] A chlorinated polyolefin composition comprising a chlorinated polyolefin, an acid acceptor, a triazine compound, and a sulfur-containing vulcanization accelerator, The acid acceptor is characterized by being at least one selected from epoxidized oil and epoxidized polybutadiene. A chlorinated polyolefin composition. [2] The chlorinated polyolefin composition according to [1], wherein the chlorinated polyolefin is chlorinated polyethylene. [3] The chlorinated polyolefin composition according to [1] or [2], wherein the triazine compound has two or three mercapto groups in the molecule. [4] The chlorinated polyolefin composition according to any one of [1] to [3], wherein the epoxy equivalent of the acid acceptor is 100 or more and 400 or less. [5] The chlorinated polyolefin composition according to any one of [1] to [4], wherein the acid acceptor is an epoxidized oil and the molecular weight of the acid acceptor is 200 or more and 2000 or less. [6] The chlorinated polyolefin composition according to [5], wherein the epoxidized oil is an epoxidized fatty acid alkyl ester having 1 to 8 carbon atoms in the alkyl group. [7] The chlorinated polyolefin composition according to any one of [1] to [4], wherein the acid acceptor is epoxidized polybutadiene and the molecular weight of the acid acceptor is 1100 or more and 10000 or less. [8] The acid acceptor is 1 to 50 parts by mass with respect to 100 parts by mass of the chlorinated polyolefin, and the chlorinated polyolefin composition according to any one of [1] to [7]. [9] The Mooney viscosity of the chlorinated polyolefin is 30 or more and 140 or less, and the chlorinated polyolefin composition according to any one of [1] to [8].

[10] The chlorine content of the chlorinated polyolefin is 25% by mass or more and 50% by mass or less, and the chlorinated polyolefin composition according to any one of [1] to [9].

[11] The chlorinated polyolefin composition is for roller rubber, and the chlorinated polyolefin composition according to any one of [1] to

[10] .

[12] A molded body obtained by molding the chlorinated polyolefin composition according to any one of [1] to

[11] .

Advantages of the Invention

[0012] The chlorinated polyolefin composition of the present embodiment has a larger tensile elongation at break than conventionally known chlorinated polyolefin compositions, and has good acid resistance, alkali resistance, and water resistance, and also has better acid resistance than chlorosulfonated polyolefin compositions. Therefore, resin products using the chlorinated polyolefin composition of the present invention have unprecedented high durability in applications where acid compounds, alkali compounds, and water are likely to come into contact.

Modes for Carrying Out the Invention

[0013] The chlorinated polyolefin composition of the present embodiment contains (A) chlorinated polyolefin, (B) acid acceptor, (E) triazine compound, and (F) sulfur-containing vulcanization accelerator. Further, it may contain (C) reinforcing material and (D) plasticizer.

[0014] (A) Chlorinated Polyolefin (A) Chlorinated polyolefin is obtained by chlorinating polyolefin. Examples of polyolefin include homopolymers of α-olefins having 2 to 10 carbon atoms such as polyethylene and polypropylene (hereinafter sometimes abbreviated as PP), or copolymers of two or more α-olefins, for example, block copolymer PP, random PP, and the like. Among these, polyolefins that are not sulfonated are more preferable in terms of productivity, mechanical strength, flexibility, and crosslinkability during chlorination, and polyethylene is particularly preferable.

[0015] The chlorination of the above polyolefin can be carried out, for example, by introducing chlorine gas into an aqueous suspension of the polyolefin. The lower limit of the chlorine content of the chlorinated polyolefin is preferably 25% by mass or more, more preferably 30% by mass or more, and even more preferably 35% by mass or more. Also, the upper limit of the chlorine content is preferably 50% by mass or less, more preferably 45% by mass or less, and even more preferably 43% by mass or less. When the chlorine content is 25% by mass or more, flexibility can be obtained, which is preferable. When the chlorine content is 50% by mass or less, good flexibility, chemical resistance, and heat resistance can be obtained, which is preferable.

[0016] The Mooney viscosity ML of the chlorinated polyolefin at 121 °C

[0015] has a lower limit that is preferably 30 or more, more preferably 50 or more, and even more preferably 55 or more. If the Mooney viscosity ML (1+4) is 30 or more, the kneading processability is good, and the mechanical strength, chemical resistance, and abrasion resistance are excellent, which is preferable. The upper limit of the Mooney viscosity ML of the chlorinated polyolefin at 121 °C (1+4) is preferably 140 or less, more preferably 130 or less, and even more preferably 120 or less. If the Mooney viscosity ML (1+4) is 140 or less, the kneading processability is excellent and the mechanical strength is excellent, which is preferable.

[0017] The mass-average molecular weight Mw of the chlorinated polyolefin is preferably 100,000 or more, and more preferably 150,000 or more. Furthermore, the upper limit of Mw is 300,000 or less, and more preferably 250,000 or less. Within this range, the viscosity can be adjusted to the Mooney viscosity described above, and the desired properties can be fully exhibited.

[0018] In this embodiment, the chlorinated polyolefin is preferably amorphous. Here, amorphous means that the heat of fusion of the crystals, measured using a differential scanning calorimeter by raising the temperature of the sample from 30°C at a rate of 10°C per minute, is 2.0 J / g or less. Amorphous polyolefins are more flexible.

[0019] (B) Acid absorber (B) The acid acceptor is selected from at least one of epoxidized oil and epoxidized polybutadiene, and two or more of these may be mixed together. Epoxy oil refers to epoxidized fatty acid esters, and is not particularly limited whether the alkyl chain of the fatty acid or the alkyl chain of the ester is epoxidized. However, it is usually an epoxidized fatty acid ester, and examples include epoxidized fatty acid alkyl esters (alkyl with 1 to 30 carbon atoms), epoxidized linseed oil, and epoxidized aliphatic esters, with epoxidized fatty acid alkyl esters (alkyl with 1 to 8 carbon atoms) being preferred.

[0020] The molecular weight of the epoxidized oil is preferably 200 or more, more preferably 300 or more, and even more preferably 350 or more. The upper limit of the molecular weight is preferably 2000 or less, more preferably 1500 or less, and even more preferably 1000 or less. By using an acid acceptor with such a molecular weight, a chlorinated polyolefin composition with excellent acid resistance, alkali resistance, and water resistance can be obtained.

[0021] The epoxidized polybutadiene is not particularly limited, but examples include epoxy-modified polybutadienes. Compounds in which epoxy groups are introduced by oxidation of vinyl groups are particularly preferred.

[0022] For example, commercially available products include NISSO-PB® JP-100 and JP-200 (both manufactured by Nippon Soda Co., Ltd.), Epolide® PB3600 and 4700 (both manufactured by Daicel Corporation), Adekasizer® BF-1000 (manufactured by ADEKA Corporation), and Ricon® 657 (manufactured by Clay Valley Corporation), which can be used individually or in combination of two or more types.

[0023] The number-average molecular weight of epoxidized polybutadiene is preferably 1100 or more, more preferably 1150 or more, and even more preferably 1200 or more. The number-average molecular weight of epoxidized polybutadiene is preferably 10000 or less, more preferably 8000 or less, and even more preferably 6000 or less. By using epoxidized polybutadiene having such a number-average molecular weight, a chlorinated polyolefin composition with particularly excellent alkali resistance and water resistance can be obtained.

[0024] The epoxy equivalent of the acid acceptor is preferably 400 or less, more preferably 300 or less, with a lower limit of 100 or more, and even more preferably 140 or more. By using an acid acceptor having an epoxy equivalent within this range, a chlorinated polyolefin composition with excellent water resistance and acid resistance can be obtained.

[0025] (B) The amount of acid acceptor added is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and even more preferably 5 parts by mass or more, per 100 parts by mass of (A) chlorinated polyolefin. (B) The amount of acid acceptor added is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 20 parts by mass or less, per 100 parts by mass of (A) chlorinated polyolefin.

[0026] By using such an acid acceptor, it is possible to provide a chlorinated polyolefin composition that exhibits high tensile elongation at break and excellent durability, including resistance to acids, alkalis, heat, and water. The chlorinated polyolefin composition of this embodiment may contain the following additives depending on the purpose.

[0027] (C) Reinforcement material The chlorinated polyolefin composition of this embodiment may contain (C) a reinforcing material. The (C) reinforcing material is not particularly limited, but specific examples include carbon black, silica, calcium carbonate, talc, clay, aluminum hydroxide, magnesium hydroxide, magnesia, etc. Carbon black and silica are more preferred due to their excellent abrasion resistance. These (C) reinforcing materials may be surface-treated for purposes such as antistatic properties.

[0028] (D) Plasticizer The chlorinated polyolefin composition of this embodiment may contain (D) a plasticizer. As (D) the plasticizer, plasticizers commonly used in polyvinyl chloride can be used. Specifically, alkylsulfonic acid phenyl ester (trade name Mesamoll®); dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, di-n-octyl phthalate, 2-ethylhexyl phthalate (hereinafter sometimes abbreviated as DOP), isononyl phthalate, octyldecyl phthalate, butylbenzyl phthalate, dicyclohexyl phthalate, n-octyl tetrahydrophthalate, di-2-ethylhexyl tetrahydrophthalate, tetrahydrophthalate Phthalate ester plasticizers such as diisodecyl trahydrofurate; aliphatic monobasic acid ester plasticizers such as butyl oleate and glycerin monooleate; dibutyl adipate, di-n-hexyl adipate, di-2-ethylhexyl adipate, diisononyl adipate, diisodecyl adipate, dialkyl 610 adipate, dibutyl diglycol adipate, di-2-ethylhexyl azelaate, di-n-hexyl azelaate, dibutyl sebacate, sebacate Aliphatic dibase ester plasticizers such as di-2-ethylhexyl phosphate; trimellitic acid ester plasticizers such as trialkyl (C4-11) trimellitic acid, cyclohexenecarboxylic acid ester, trioctyl trimellitic acid, and isononyl trimellitic acid ester; polyester plasticizers such as propylene glycol adipate and 1,3-butylene glycol adipate, which consist of polymers of dibasic acids such as adipic acid, azelaic acid, sebacic acid, and phthalic acid with glycols, glycerins, and monobasic acids; phosphate ester plasticizers such as triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, triphenyl phosphate, tricresyl phosphate, trichloroethyl phosphate, trisdichloropropyl phosphate, tributoxyethyl phosphate, tris(β-chloropropyl) phosphate, octyldiphenyl phosphate, tris(isopropylphenyl) phosphate, and cresyldiphenyl phosphate; and chlorinated paraffinic plasticizers can be used.

[0029] (D) The amount of plasticizer added is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less, per 100 parts by mass of (A) chlorinated polyolefin. The amount of plasticizer added is preferably 0.1 parts by mass or more, more preferably 1.0 part by mass or more, and even more preferably 5.0 parts by mass or more, per 100 parts by mass of (A) chlorinated polyolefin. If the blending ratio of (D) plasticizer to 100 parts by mass of (A) chlorinated polyolefin is 30 parts by mass or less, a molded article with appropriate hardness can be obtained.

[0030] (E) Triazine compound The triazine compound used in the present invention is preferably a compound represented by general formula (I), preferably having two or three mercapto groups in its molecule, and is used as a vulcanizing agent or vulcanizing accelerator.

[0031] [ka] (In the formula, R1 is selected from the group consisting of mercapto groups and amino groups. In formula (I) above, the amino group of R1 may also be a hydrocarbon group having 1 to 20 carbon atoms.)

[0032] Examples of triazine compounds include 1,3,5-trithiocyanuric acid, 1-hexylamino-3,5-dimethylcaptotriazine, 1-diethylamino-3,5-dimethylcaptotriazine, 1-cyclohexylamino-3,5-dimethylcaptotriazine, and 2,4,6-mercaptotriazine, with 2,4,6-mercaptotriazine being preferred.

[0033] Using triazine compounds makes it easier to vulcanize chlorinated polyolefins, similar to the sulfur vulcanization of common rubber. Specifically, they are preferable because they offer good processability during crosslinking and, unlike peroxides, allow for proper surface crosslinking even in an oxygen atmosphere.

[0034] The amount of triazine compound blended is 0.1 to 5 parts by weight per 100 parts by weight of (A) chlorinated polyolefin, preferably 0.5 to 3 parts by weight, and particularly preferably 1 to 2 parts by weight. When the blending amount is within the above range, vulcanization is carried out sufficiently, and the mechanical properties of the resulting crosslinked product are excellent.

[0035] (F) Sulfur-containing vulcanization accelerator The sulfur-containing vulcanization accelerator functions as a vulcanization accelerator for triazine compounds and is not particularly limited as long as it has a sulfur atom and can be used in rubber compositions. The sulfur-containing vulcanization accelerator may also be a salt. (F) The sulfur-containing vulcanization accelerator does not contain (E) a triazine compound.

[0036] The sulfur-containing vulcanization accelerator is preferably a dithiocarbamate-based accelerator or a thiazole-based accelerator. Examples of dithiocarbamate-based accelerators include pentamethylenedithiocarbamate, dimethyldithiocarbamate, and dithiocarbamate, with dithiocarbamate being more preferred.

[0037] Examples of thiazole-based promoters include mercaptobenzothiazole and dibenzothiadyl disulfide, with mercaptobenzothiazole being more preferred. Examples of salts that constitute part of the sulfur-containing vulcanization accelerator include amine salts, sodium salts, and potassium salts, with amine salts being preferred due to the faster vulcanization rate of the triazine compound.

[0038] Of these, amine salts of mercaptobenzothiazole or amine salts of dithiocarbamic acid are more preferred. Amine salts of mercaptobenzothiazole are salts of mercaptobenzothiazole represented by general formula (II) with a primary, secondary, or tertiary amine.

[0039] [ka] (In the formula, R2, R3, and R4 may be the same or different, and are hydrogen or hydrocarbon groups with at most 18 carbon atoms, but they may be groups without substituents including heteroatoms, or R2, R3, and R4 may be bonded to each other to form a hydrocarbon ring, or they may be bonded via heteroatoms to form a heterocyclic ring, but they may not all be hydrogen at the same time.)

[0040] The hydrocarbon group in the sulfur-containing vulcanization accelerator can be selected from alkyl groups, cycloalkyl groups, allyl groups, and aralkyl groups. Preferred examples include methyl groups, ethyl groups, propyl groups, butyl groups, cyclohexyl groups, and benzyl groups.

[0041] Furthermore, specific examples of amines constituting the sulfur-containing vulcanization accelerator include ethylamine, propylamine, hexylamine, octylamine, laurylamine, cyclohexylamine, diethylamine, dipropylamine, dibutylamine, dihexylamine, dioctylamine, dilaurylamine, dicyclohexylamine, piperidine, pipecorine, morpholine, and piperazine, with dicyclohexylamine being preferred. Specific examples of sulfur-containing vulcanization accelerators used in the present invention include cyclohexylamine salt of 2-mercaptobenzothiazole, dicyclohexylamine salt of 2-mercaptobenzothiazole, and tricyclohexylamine salt of 2-mercaptobenzothiazole.

[0042] The sulfur-containing vulcanization accelerator is generally used in combination with a triazine compound, and the amount added is 0.1 to 10 parts by weight, preferably 0.5 to 7.5 parts by weight, and particularly preferably 1 to 5 parts by weight, per 100 parts by weight of (A) chlorinated polyolefin. When the amount added is within the above range, it exhibits a sufficient vulcanization-accelerating effect, and a crosslinked product with excellent mechanical properties can be obtained.

[0043] Acid acceptors other than (G)(B) The chlorinated polyolefin composition of this embodiment may contain acid acceptors other than (G) and (B).

[0044] The amount of acid acceptors other than (G) and (B) is preferably 0 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 1 part by mass or more, per 100 parts by mass of (A) chlorinated polyolefin. The amount of acid acceptors other than (G) and (B) is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 3 parts by mass or less, per 100 parts by mass of (A) chlorinated polyolefin.

[0045] The chlorinated polyolefin composition of this embodiment may contain various additives in the art, such as crosslinking aids, stabilizers, antioxidants, processing aids, viscosity modifiers, flame retardants, pigments, etc., to the extent that they do not impair the properties of the present invention.

[0046] The chlorinated polyolefin composition of this embodiment can be molded into a molded article by various molding methods, such as compression molding, injection molding, transfer molding, and extrusion molding. If it contains organic peroxides, crosslinking may be performed, and various methods such as hot air crosslinking, microwave crosslinking, and electron beam crosslinking can be used as crosslinking methods.

[0047] The crosslinking temperature of the molded article in this embodiment depends on the thermal decomposition temperature of the organic peroxide used, but its lower limit is preferably 130°C or higher, more preferably 140°C or higher. The upper limit of the crosslinking temperature of the molded article in this embodiment is preferably 200°C or lower, more preferably 190°C or lower, and even more preferably 180°C or lower. If the temperature is 140°C or higher, crosslinking can be performed appropriately. If the temperature is 190°C or lower, the generation of acid can be trapped by the acid acceptor, and crosslinking can be performed appropriately.

[0048] The crosslinking time conditions for the molded article in this embodiment depend on the thermal decomposition temperature of the organic peroxide used, but the lower limit is preferably 10 minutes or more, more preferably 15 minutes or more, and even more preferably 20 minutes or more. The upper limit of the crosslinking time conditions for the molded article in this embodiment is preferably 300 minutes or less, more preferably 200 minutes or less, and even more preferably 150 minutes or less. If the crosslinking time is 10 minutes or more, appropriate crosslinking can be achieved. Also, if the crosslinking time is 300 minutes or less, appropriate crosslinking can be achieved.

[0049] Molded products manufactured using this method exhibit excellent durability, including resistance to acids, alkalis, water, and heat, and can be used in various applications such as wire insulation, mono pump stator materials, industrial rubber rollers, automotive dust boots, and automotive hoses.

[0050] In particular, the molded body of this embodiment is preferably used for rubber rollers. The rubber roller consists of a cylindrical base material, as described in Japanese Patent Application Publication No. 2006-207660, and the base material is made of the chlorinated polyolefin composition according to this embodiment. The base material is provided on the outer circumferential surface of a shaft, and the shaft is made of metal and is formed in a cylindrical shape. [Examples]

[0051] The present invention will be described in detail below with reference to examples, but the present invention is not limited in any way to these examples. The test methods used in the examples and comparative examples are as follows:

[0052] • Molecular weight of acid acceptor (B) The molecular weight is measured using an Agilent Technologies 7200B model by ionization (electron shock spectrometry), with the mass separation tube consisting of a quadrupole type in the front stage and a time-of-flight type in the rear stage, and is determined by mass spectrometry.

[0053] • Epoxy equivalent of the acid acceptor In this application, the epoxy equivalent is a value measured in accordance with JIS K7236(2001).

[0054] - Mooney viscosity of chlorinated polyolefin and chlorinated polyolefin composition Using a Mooney viscometer (SMV-300RT manufactured by Shimadzu Corporation) as the measuring device, in accordance with the method specified in JIS K6300-2:2001, using an L rotor, the Mooney viscosity ML (at 121 °C (after preheating for 1 minute and rotating for 4 minutes)) was measured. 1+4 (at 121 °C) was measured.

[0055] - Chlorine content of chlorinated polyolefin The chlorine content was determined by heating and burning the sample in a glass tube with the flame of a gas burner, decomposing it by dehydrochlorination, absorbing the generated hydrochloric acid gas in distilled water, and neutral titrating and quantifying it with 0.1 mol / 1 sodium hydroxide standard solution.

[0056] [Examples 1 to 2, Comparative Examples 1 to 42] Preparation of composition The following materials were used in the examples and comparative examples. (A) Chlorinated polyolefin, etc. - Chlorinated polyethylene (1); Elaslen 402NA-X5 manufactured by Showa Denko K.K., chlorine content 40% by mass, Mooney viscosity ML at 121 °C (1+4) 70 - Chlorinated polyethylene (2); Elaslen 401A manufactured by Showa Denko K.K., chlorine content 40% by mass, Mooney viscosity ML at 121 °C (1+4) 115 - Chlorinated polyethylene (3); Elaslen 301A manufactured by Showa Denko K.K., chlorine content 30% by mass, Mooney viscosity ML at 121 °C (1+4) 85 - Chlorosulfonated polyethylene; TOSO-CSM TS-530 manufactured by Tosoh Corporation, chlorine content 35% by mass, sulfur content 1.0% by mass, Mooney viscosity ML at 100 °C (1+4) 56

[0057] (B) Acid acceptor - Epoxidized polybutadiene (1); NISSO-PB-JP-100 manufactured by Nippon Soda Co., Ltd., molecular weight 1300, epoxy equivalent 190 - 210 • Epoxy-modified polybutadiene (2); manufactured by Nippon Soda Co., Ltd. NISSO-PB-JP-200 Molecular weight 2200 Epoxy equivalent 210-240 • Epoxy-modified polybutadiene (3); manufactured by Daicel Corporation, Epolide PB3600, molecular weight 5900, epoxy equivalent 185-210 • Epoxylated polybutadiene (4); manufactured by Daicel Corporation, Epolid PB4700, molecular weight 2000-3500, epoxy equivalent 152-178 • Epoxy soybean oil: ADEKA Corporation, ADEKA Sizer O-130P, Molecular weight 1000, Epoxy equivalent 239 • Epoxy linseed oil: ADEKA Corporation, ADEKA Sizer O-180A, Molecular weight 1000, Epoxy equivalent 145 • Epoxy resin; manufactured by Mitsubishi Chemical Corporation, JER828, molecular weight 370, epoxy equivalent weight 184-194 • Epoxylated fatty acid octyl ester; ADEKA Corporation, ADEKA Sizer D-32, Molecular weight 409, Epoxy equivalent 372 • Epoxylated fatty acid alkyl ester; ADEKA Corporation, ADEKA Sizer D-55, Molecular weight 356, Epoxy equivalent 333

[0058] • Glycerin-epichlorohydrin-0~1 molar adduct-polyglycidyl ether; manufactured by NOF Corporation. Epiol (registered trademark) G-100 Molecular weight 204-352 Epoxy equivalent 160 • Polyglycidyl ether of ethylene glycol-epichlorohydrin-0-2 molar adduct; manufactured by NOF Corporation. Epiol E-100LC Molecular weight 174-350 Epoxy equivalent 145 Ethylene glycol diglycidyl ether; manufactured by Kyoeisha Chemical Co., Ltd. Epolite 40E Molecular weight 174 Epoxy equivalent 125-140 • Lead oxide; Reinchemie Renogran PbO-80 Magnesium oxide; manufactured by Kyowa Chemical Industry Co., Ltd. Kyowa Mag 150 Synthetic hydrotalcite; manufactured by Kyowa Chemical Industry Co., Ltd., DHT-4A • Synthetic hydrocalmite; manufactured by Katsuta Chemical Co., Ltd. E-1300 • Epoxy resin; manufactured by Mitsubishi Chemical, JER828, molecular weight 370, epoxy equivalent 184 -194 • Calcium silicate; manufactured by Shiraishi Kogyo Co., Ltd., Silmos C Magnesium hydroxide; manufactured by Kyowa Chemical Industry Co., Ltd., Kisma 5J • Calcium hydroxide; manufactured by Katsuta Chemical Co., Ltd. CA-100T • Calcium-substituted zeolite; manufactured by Katsuta Chemical Co., Ltd., CS100K • Perchloric acid-treated hydrotalcite; manufactured by Katsuta Chemical Co., Ltd., KA-100 Sodium type A zeolite; manufactured by Katsuta Chemical Co., Ltd., NA-100

[0059] (C) Reinforcement material Carbon Black; Furnace Process Carbon Black, manufactured by Cabot Japan, Shoblack N550G

[0060] (D) Plasticizer Isononyl trimellitic acid (manufactured by ADEKA Corporation, ADEKA Sizer C-9N)

[0061] (E) Triazine compound 2,4,6-Trimercapto-s-triazine: Sankyo Chemical Co., Ltd., JISNET F, Molecular weight: 177

[0062] (F) Sulfur-containing vulcanization accelerator 2-Mercaptobenzothiazole-dicyclohexylamine salt: Sanshin Chemical Industry Co., Ltd. Sunceller MA Molecular weight: 352

[0063] (Other) Organic peroxides α,α'-di(t-butylperoxy)diisopropylbenzene, manufactured by NOF Corporation, Perbutyl P

[0064] (Other) Crosslinking agents Triallyl isocyanurate, manufactured by Nippon Kasei Co., Ltd.

[0065] The mixture was weighed to achieve the composition shown in Table 1, kneaded under water cooling using a 1.8L Banbury® mixer at 60 rpm for 3 minutes, and after being discharged as composition A, it was rolled out into a sheet using a 10-inch (25.4 cm) roller.

[0066] [Table 1]

[0067] Next, the obtained A-component was mixed with a triazine compound, a sulfur-containing vulcanization accelerator, and an organic peroxide in the amounts shown in Table 2. The mixture was kneaded for 5 minutes under water cooling using a 10-inch (25.4 cm) roll, and the resulting B-component was transferred to a sheet.

[0068] [Table 2]

[0069] Next, each acid acceptor shown in Table 3 was mixed with the B paste composition in the amounts shown in Table 3 to obtain a chlorinated polyolefin composition. The chlorinated polyolefin composition was cooled with water, and each acid acceptor was added to the B paste composition using a 10-inch (25.4 cm) roll. The mixture was kneaded for 5 minutes, and then transferred to a 2.3 mm thick sheet to obtain a molded body. The amount of acid acceptor was determined relative to 100 parts by mass of (A) chlorinated polyolefin.

[0070] Specimen preparation A 2mm thick crosslinked sheet was obtained by crosslinking for 120 minutes in a press molding machine at a mold temperature of 150°C. Test specimens for punching tensile tests were obtained using a No. 3 dumbbell in accordance with JIS-K6251-2017. For volume change rate measurement in immersion tests with various chemicals, 20mm square test specimens were used.

[0071] Test method Measurements were performed using sheets prepared according to the specimen preparation method described above. Durometer hardness (HS) was measured according to Type A of JIS-K6253-3:2012, and the modulus (M100), breaking strength (TB), and tensile elongation at break (EB) were measured according to JIS-K6251-2017 at 500 mm / min and 23°C. The results are shown in Table 3.

[0072] Furthermore, Table 3 also shows the results of measuring the volume change rate (ΔV), durometer hardness (ΔHS), breaking strength (ΔTB), and tensile elongation at break (ΔEB) of the test specimens prepared after the crosslinking treatment, after immersion in the following chemicals and maintaining a temperature of 80°C for 168 hours.

[0073] • Each chemical to be immersed 10% Hydrochloric Acid; Kanto Chemical Co., Ltd. Hydrochloric Acid, Special Grade, 35% by mass, diluted to 10% by mass with pure water. 10% Sulfuric Acid; Kanto Chemical Co., Ltd. Sulfuric acid, special grade, 96% by mass, diluted to 10% by mass with pure water. 10% Nitric Acid; Kanto Chemical Co., Ltd. Nitric Acid, Special Grade, 70% by mass, diluted to 10% by mass with pure water. 20% Nitric Acid; Kanto Chemical Co., Ltd. Nitric Acid, Special Grade, 70% by mass, diluted to 20% by mass with pure water. 10% Sodium Hydroxide; Kanto Chemical Co., Ltd. Sodium Hydroxide, Special Grade, Concentration 97% by Mass Dilute with pure water to 10% by mass. Pure water; factory pure water

[0074] [Table 3-1]

[0075] [Table 3-2]

[0076] [Table 3-3]

[0077] [Table 3-4]

[0078] [Table 3-5]

[0079] The chlorinated polyolefin composition of the example exhibits an absolute value of over 400% tensile elongation at break, which is greater than that of any of the comparative examples, making it suitable for use in hoses, wire coatings, rollers, gaskets, etc. Furthermore, changes in volume, hardness, etc., remain within a certain range even after all durability tests (chemical immersion), making it suitable for use in hoses, wire coatings, rollers, gaskets, etc., which may be immersed in chemicals.

Claims

1. A chlorinated polyolefin composition comprising a chlorinated polyolefin, an acid acceptor, a triazine compound, and a sulfur-containing vulcanization accelerator, A chlorinated polyolefin composition for roller rubber, characterized in that the acid acceptor is epoxidized polybutadiene and the molecular weight of the acid acceptor is 1100 or more and 10000 or less.

2. The chlorinated polyolefin composition for roller rubber according to claim 1, wherein the chlorinated polyolefin is chlorinated polyethylene.

3. The chlorinated polyolefin composition for roller rubber according to claim 1 or 2, wherein the triazine compound has two or three mercapto groups in the molecule.

4. A chlorinated polyolefin composition for roller rubber according to any one of claims 1 to 3, wherein the epoxy equivalent of the acid acceptor is 100 or more and 400 or less.

5. A chlorinated polyolefin composition for roller rubber according to any one of claims 1 to 4, wherein the acid acceptor is present in an amount of 1 to 50 parts by mass per 100 parts by mass of the chlorinated polyolefin.

6. A chlorinated polyolefin composition for roller rubber according to any one of claims 1 to 5, wherein the Mooney viscosity of the chlorinated polyolefin is 30 or more and 140 or less.

7. A chlorinated polyolefin composition for roller rubber according to any one of claims 1 to 6, wherein the chlorine content of the chlorinated polyolefin is 25% by mass or more and 50% by mass or less.

8. A molded article obtained by molding a chlorinated polyolefin composition for roller rubber according to any one of claims 1 to 7.

Images