Chlorinated polyolefin composition

Abstract

This invention provides a chlorinated polyolefin composition with excellent durability, including resistance to acids, alkalis, and heat. [Solution] A chlorinated polyolefin composition comprising (A) a chlorinated polyolefin, (B) an acid acceptor, (C) a reinforcing agent, (D) a plasticizer, (E) an organic peroxide, and a crosslinking aid, wherein the acid acceptor is at least one selected from aliphatic glycidyl ethers and epoxidized oils, the molecular weight of the acid acceptor is 200 or more, and the composition is for use in roller rubber.

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, and 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.

[0005] Therefore, there was a need for a chlorinated polyolefin composition that had good acid and heat resistance, while maintaining a certain level of alkali and water resistance. Furthermore, chlorinated polyolefins include chlorosulfonated polyolefins that contain sulfonic acid (for example, Patent Document 1).

[0006] 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.

[0007] 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]

[0008] [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]

[0009] 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. Although the composition described in Patent Document 1 is said to have excellent water resistance and acid resistance, further improvements are needed. Furthermore, Patent Document 2 only focuses on the transparency, mechanical strength, permanent elongation, and whitening resistance of products such as tubes.

[0010] Conventional molded articles made from chlorinated polyolefin compositions did not always satisfy these requirements. Therefore, the present invention aims to provide a chlorinated polyolefin composition that exhibits excellent durability, such as acid resistance and heat resistance. [Means for solving the problem]

[0011] And, after diligently conducting research, the inventors found that We discovered that the above problems could be solved by combining chlorinated polyolefin with a specific acid acceptor, and thus completed the present invention.

[0012] In other words, the present invention relates to the following chlorinated polyolefin compositions [1] to

[10] . [1] A chlorinated polyolefin composition comprising a chlorinated polyolefin and an acid acceptor, The acid acceptor is at least one selected from aliphatic glycidyl ethers and epoxidized oils. A chlorinated polyolefin composition characterized in that the molecular weight of the acid acceptor is 200 or more. [2] The chlorinated polyolefin composition of [1], wherein the chlorinated polyolefin is chlorinated polyethylene. [3] A chlorinated polyolefin composition according to [1] or [2], wherein the epoxy equivalent of the acid acceptor is 100 or more and 400 or less. [4] The chlorinated polyolefin composition according to [1] to [3], wherein the molecular weight of the acid acceptor is 2000 or less. [5] The chlorinated polyolefin composition according to [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] The chlorinated polyolefin composition according to [1] to [5], wherein the epoxidized oil is an epoxidized aliphatic alkyl ester having 1 to 8 carbon atoms in the alkyl group. [7] The chlorinated polyolefin composition according to [1] to [6], wherein the Mooney viscosity of the chlorinated polyolefin is 30 or more and 140 or less. [8] The chlorinated polyolefin composition according to [1] to [7], wherein the chlorine content of the chlorinated polyolefin is 25% by mass or more and 50% by mass or less. [9] The chlorinated polyolefin composition according to [1] to [8], wherein the chlorinated polyolefin composition is for roller rubber. A molded article formed by molding a chlorinated polyolefin composition of

[10] [1] to [9].

Advantages of the Invention

[0013] The chlorinated polyolefin composition has better acid resistance than conventionally known chlorinated polyolefin compositions, and has equivalent alkali resistance and water resistance. Also, it has better acid resistance than chlorosulfonated polyolefin compositions.

[0014] 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.

Embodiments for Carrying Out the Invention

[0015] The chlorinated polyolefin composition of the present embodiment contains (A) a chlorinated polyolefin and (B) an acid acceptor. It may also contain (C) a reinforcing material, (D) a plasticizer, and (E) an organic peroxide. (A) Chlorinated polyolefin (A) The chlorinated polyolefin is obtained by chlorinating a polyolefin. Examples of polyolefins 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, etc. 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.

[0016] (A) The chlorinated polyolefin of the present invention does not include those in which hydrogen atoms are substituted by other than halogen atoms. 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 still more preferably 35% by mass or more. The upper limit of the chlorine content is preferably 50% by mass or less, more preferably 45% by mass or less, and still more preferably 43% by mass or less. A chlorine content of 25% by mass or more is preferable to obtain flexibility. A chlorine content of 50% by mass or less is preferable to obtain good flexibility, chemical resistance, and heat resistance.

[0017] The Mooney viscosity ML of the chlorinated polyolefin at 121 °C (1+4) is preferably at least 30, more preferably at least 50, and still more preferably at least 55. 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 at most 140, more preferably at most 130, and still more preferably at most 120. 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.

[0018] The mass average molecular weight Mw of the chlorinated polyolefin is preferably 100,000 or more, and more preferably 150,000 or more. The upper limit of Mw is preferably 300,000 or less, and more preferably 250,000 or less. Within this range, the above-mentioned Mooney viscosity can be adjusted, and the desired properties can be fully exhibited.

[0019] The chlorinated polyolefin in this embodiment is preferably amorphous. Here, amorphous means that the heat of crystal melting measured by using a differential scanning calorimeter with a temperature increase rate of 10 °C per minute from 30 °C for the measurement sample is 2.0 J / g or less. If it is amorphous, a more flexible one can be obtained. (B) Acid acceptor (B) The acid acceptor is an aliphatic glycidyl ether or an epoxidized oil with a molecular weight of 200 or more, and these may be used alone or in a mixture of two or more types.

[0020] Aliphatic glycidyl ethers are not limited to those in which a glycidyl group is linked to an aliphatic main chain via an ether bond, but examples include glycerin-epichlorohydrin adducts, ethylene glycol-epichlorohydrin adducts, polyethylene glycol #400 diglycidyl ether epoxidized soybean oil, etc. Aliphatic glycidyl ether compounds having a glycidyl group at any of the terminals are particularly preferred.

[0021] 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.

[0022] Among these, epoxidized aliphatic glycidyl ethers are preferred in terms of their excellent water resistance, and aliphatic glycidyl ether compounds having glycidyl groups at both ends are more preferred.

[0023] (B) The molecular weight of the acid acceptor is 200 or more, preferably 300 or more, and 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 can be obtained.

[0024] (B) 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] The chlorinated polyolefin composition of this embodiment may contain the following additives depending on the purpose. (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.

[0027] (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.

[0028] (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.

[0029] (E)Organic peroxide The type of (E) organic peroxide incorporated into the chlorinated polyolefin composition in this embodiment is not particularly limited as long as it can crosslink the chlorinated polyolefin. For example, stearoyl peroxide, lauroyl peroxide, benzoyl peroxide, 4-methylbenzoyl peroxide, 1,1-bis(t-butylperoxy)2-methylcyclohexane, 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxylaurate, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t- Examples include xyl peroxybenzoate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butyl peroxybenzoate, n-butyl-4,4-bis(t-butylperoxy)valerate, di-t-butylperoxyisophthalate, α,α'-bis(t-butylperoxy)diisopropylbenzene (trade name: Perbutyl® P), dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxyl)hexyn-3 (trade name: Perhexyn® 25B-40), and 2,5-di(t-butylperoxy)-2,5-dimethyl-hexane (trade name: Perhexa® 25B). These (E) organic peroxides may be used individually or in combination of two or more.

[0030] Among these (E) organic peroxides, those with a 1-minute half-life temperature of 130°C or higher are preferred. If the 1-minute half-life temperature is 130°C or higher, a cross-linked molded article can be easily obtained.

[0031] Here, the 1-minute half-life temperature of (E) organic peroxide is the temperature at which (E) organic peroxide decomposes and the initial amount of reactive oxygen species is halved in 1 minute. The measurement method is not particularly limited, but for example, it can be determined by calculating the half-life of the organic peroxide at a peroxide concentration of 0.10 mol / L at multiple temperatures in a solvent that is relatively inactive to radicals (such as benzene) and plotting these data.

[0032] (E) The amount of organic peroxide added is preferably 0.4 parts by mass or more, more preferably 0.8 parts by mass or more, even more preferably 1.0 part by mass or more, based on 100 parts by mass of chlorinated polyolefin, with a lower limit of 0.4 parts by mass or more, more preferably 0.8 parts by mass or more, even more preferably 1.0 part by mass or more, with an upper limit of preferably 8.0 parts by mass or less, more preferably 5.0 parts by mass or less, and even more preferably 4.0 parts by mass or less. If the amount of organic peroxide added is 0.4 parts by mass or more, based on 100% purity, the crosslinking reaction of the composition proceeds quickly, making it easier to obtain a molded article with excellent mechanical strength and wear resistance, which is preferable. On the other hand, if the amount of organic peroxide added is 8.0 parts by mass or less, based on 100% purity, a molded article can be easily obtained from the composition.

[0033] (F) Other acid acceptors The chlorinated polyolefin composition of this embodiment may contain (F) other acid acceptors. (F) Other acid acceptors are acid acceptors other than those described in (B). (F) Examples of other acid acceptors include epoxidized polybutadiene.

[0034] (F) The amount of other acid acceptors added 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. (F) The amount of other acid acceptors added 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.

[0035] 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.

[0036] 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.

[0037] 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.

[0038] 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.

[0039] 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.

[0040] In particular, the composition 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 surface of a shaft, and the shaft is made of metal and is formed in a cylindrical shape. [Examples]

[0041] 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: • 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.

[0042] • Epoxy equivalent of the acid acceptor In this application, the epoxy equivalent is a value measured in accordance with JIS K7236(2001). • Mooney viscosity of chlorinated polyolefins and chlorinated polyolefin compositions A Mooney viscometer (SMV-300RT, manufactured by Shimadzu Corporation) was used as the measuring device, and the Mooney viscosity ML was measured at 121°C (after preheating for 1 minute and rotating for 4 minutes) using the L rotor, according to the method specified in JIS K6300-2:2001. 1+4 (121℃) was measured.

[0043] • Chlorine content of chlorinated polyolefins The chlorine content was determined by heating and burning the sample in a glass tube with a gas burner flame to dehydrogenate it, absorbing the resulting hydrochloric acid gas into distilled water, and then titrating it with 0.1 mol / 1 caustic soda normal solution.

[0044] [Examples 1-6, Comparative Examples 1-19] Preparation of composition The following materials were used in the examples and comparative examples. (A) Chlorinated polyolefins and the like · Chlorinated polyethylene (1); manufactured by Showa Denko K.K., Elaslen 402NA-X5, chlorine content 40% by mass, Mooney viscosity ML at 121 °C (1+4) 70 · Chlorinated polyethylene (2); manufactured by Showa Denko K.K., Elaslen 401A, chlorine content 40% by mass, Mooney viscosity ML at 121 °C (1+4) 115 · Chlorinated polyethylene (3); manufactured by Showa Denko K.K., Elaslen 301A, chlorine content 40% by mass, Mooney viscosity ML at 121 °C (1+4) 85 · Chlorosulfonated polyethylene; manufactured by Tosoh Corporation, TOSO-CSM TS-530, chlorine content 35%, sulfur content 1.0% by mass, Mooney viscosity ML at 100 °C (1+4) 56

[0045] (B) Acid acceptors · Epoxidized fatty acid octyl ester; manufactured by ADEKA, Adekasizer D-32, molecular weight 409, epoxy equivalent 372 · Epoxidized fatty acid alkyl ester; manufactured by ADEKA, Adekasizer D-55, molecular weight 356, epoxy equivalent 333 · Glycerol-epichlorohydrin-0 to 1 mol adduct - polyglycidyl ether; manufactured by NOF Corporation, Epicol (registered trademark) G-100, molecular weight 204-352, epoxy equivalent 160 · Ethylene glycol-epichlorohydrin-0 to 2 mol adduct - polyglycidyl ether; manufactured by NOF Corporation, Epicol 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

[0046] (F) Other acid acceptors · Epoxidized polybutadiene (1); manufactured by Nippon Soda Co., Ltd., NISSO-PB-JP-100, 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 resin; manufactured by Mitsubishi Chemical Corporation, JER828, molecular weight 370, epoxy equivalent weight 184-194 • 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 Corporation, JER828, molecular weight 370, epoxy equivalent weight 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

[0047] (C) Reinforcement material • Carbon black; Furnace process carbon black, manufactured by Cabot Japan, Shoblack N550G (D) Plasticizer Isononyl trimellitic acid (manufactured by ADEKA Corporation, ADEKA Sizer C-9N) (E)Organic peroxide α,α'-di(t-butylperoxy)diisopropylbenzene, manufactured by NOF Corporation, Perbutyl P

[0048] (Other) Crosslinking agents Triallyl isocyanurate, manufactured by Nippon Kasei Co., Ltd. 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.

[0049] [Table 1] Next, the obtained A-component and organic peroxide were kneaded together for 5 minutes under water cooling using a 10-inch (25.4 cm) roll to the proportions shown in Table 2, and the resulting B-component was transferred to a sheet.

[0050] [Table 2] Next, each acid acceptor shown in Table 3 was blended in the amounts shown in Table 3 to obtain a chlorinated polyolefin composition. The chlorinated polyolefin composition was added to the B-compound mixture using a 10-inch (25.4 cm) roll under water cooling and kneaded for 5 minutes. The chlorinated polyolefin composition was then transferred to a 2.3 mm thick sheet to obtain a molded body.

[0051] 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.

[0052] Test method Measurements were performed using sheets prepared according to the specimen preparation method described above. Durometer hardness (H) was measured according to JIS-K6253-3:2012 Type A, and the modulus (M100) at 100% elongation at 23°C at 500 mm / min, fracture strength (TB), and tensile elongation at break (EB) were measured according to JIS-K6251-2017. The results are shown in Table 3.

[0053] Furthermore, Table 3 also shows the results of measuring the volume change (ΔV), durometer hardness change (ΔHS), fracture strength change (ΔTB), and tensile elongation change at break (ΔEB) after immersing the test specimens prepared after the crosslinking treatment in the following chemicals, maintaining the temperature at 80°C for 168 hours, and then removing them. • 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, 97% by mass, diluted to 10% by mass with pure water. Pure water; factory pure water

[0054] [Table 3-1]

[0055] [Table 3-2]

[0056] [Table 3-3] The chlorinated polyolefin composition of the example did not exhibit bleeding after durability testing with chemical solutions other than 20% by mass nitric acid. On the other hand, the chlorinated polyolefin compositions of Comparative Examples 17 to 19, which used organic substances as acid acceptors, exhibited bleeding after durability testing with any of the chemical solutions other than 20% by mass nitric acid. Furthermore, the Δ volume of the chlorinated polyolefin composition of the example was within 12% after durability testing with 10% by mass nitric acid, which is smaller than that of Comparative Examples 1 to 16. From the above, it can be concluded that only the chlorinated polyolefin composition of the example did not exhibit either Δ volume or bleeding after durability testing with 10% by mass nitric acid. The chlorinated polyolefin composition of the example shows no changes in volume, hardness, etc., within a certain range after immersion in any chemical, and can be suitably used in hoses, wire coatings, rollers, packings, etc., which may be immersed in chemicals.

Claims

1. A composition comprising (A) chlorinated polyolefin, (B) acid acceptor, (C) reinforcing agent, (D) plasticizer, (E) organic peroxide, and crosslinking aid, The acid acceptor is at least one selected from aliphatic glycidyl ethers and epoxidized oils, and the molecular weight of the acid acceptor is 200 or more. A chlorinated polyolefin composition characterized in that the composition is for use in roller rubber.

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

3. The chlorinated polyolefin composition according to claim 1 or 2, wherein the epoxy equivalent of the acid acceptor is 100 or more and 400 or less.

4. The chlorinated polyolefin composition according to any one of claims 1 to 3, wherein the molecular weight of the acid acceptor is 2000 or less.

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

8. The chlorinated polyolefin composition according to any one of claims 1 to 7, wherein the chlorine content of the chlorinated polyolefin is 25% by mass or more and 50% by mass or less.

9. A molded article obtained by molding a chlorinated polyolefin composition according to any one of claims 1 to 8.

Images