Chlorinated polyolefin composition

Abstract

To provide a chlorinated polyolefin composition, or more specifically, a chlorinated polyolefin composition that has great values of tensile elongation at break and fracture strength, small taber abrasion, and excellent durability such as acid resistance, alkali resistance, and heat resistance.SOLUTION: A chlorinated polyolefin composition contains chlorinated polyolefin and an acid acceptor, the acid acceptor including epoxidized polybutadiene and epoxidized oil.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a chlorinated polyolefin composition. [Background technology]

[0002] Chlorinated polyolefins are chlorine-containing polymers that do not have unsaturated bonds in their main chains. They have excellent resistance to heat aging, oil, weather, chemicals, ozone, and flame retardancy, and are therefore used in a variety of applications, including hoses, electrical wire coatings, rollers, and packing.

[0003] On the other hand, because chlorinated polyolefins contain chloro groups in the polymer, excessive thermal degradation can liberate acid components derived from the chloro groups. For this reason, it is generally known that compounding agents such as acid acceptors must be added to prevent the liberation of acid components from the polymer. Compounding agents that are known to be added include lead monoxide, magnesium oxide, and synthetic hydrotalcite.

[0004] However, as is well known, chlorinated polyolefin compositions that generally use lead monoxide as an acid acceptor have an environmental impact when used, and chlorinated polyolefin compositions that use magnesium oxide or synthetic hydrotalcite have poor acid resistance, alkali resistance, and water resistance, making them difficult to use in applications where they come into contact with acidic or alkaline chemicals or water. Therefore, there has been a demand for chlorinated polyolefin compositions that have good acid resistance, alkali resistance, water resistance, and heat resistance.

[0005] Chlorinated polyolefins also include chlorosulfonated polyolefins containing sulfonic acid (see, 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, an epoxidized polybutadiene, or an epoxidized oil, based on 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 ethylene homopolymers or copolymers of ethylene and an α-olefin and having a density of 0.90 or higher, and 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 crystalline fusion measured by a DSC method of 20 to 60 J / g; 1 to 15 parts by mass of an epoxy derivative selected from epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, epichlorohydrin derivatives, and epoxycyclohexane derivatives; and 0.05 to 3 parts by mass of a stabilizer selected from the hydrotalcite group. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Publication No. 2017-88872 [Patent Document 2] Japanese Patent Application Laid-Open No. 2006-342343 Summary of the Invention [Problem to be solved by the invention]

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

[0009] In various applications such as hoses, electric wire coating materials, rollers, and packing, molded articles are often exposed to conditions such as acidic conditions, alkaline conditions, and high-temperature conditions. However, molded articles made of conventional chlorinated polyolefin compositions do not necessarily satisfy these requirements. In addition, acid acceptors such as epoxidized polybutadiene are expensive, making cost reduction an issue.

[0010] Therefore, an object of the present invention is to provide a chlorinated polyolefin composition which is inexpensive, has a large tensile elongation at break, and is excellent in durability such as acid resistance, alkali resistance, heat resistance, and water resistance. [Means for solving the problem]

[0011] As a result of extensive research, the present inventors have found that The inventors have found that the above problems can be solved by combining a chlorinated polyolefin with a specific acid acceptor, and have thus completed the present invention.

[0012] That is, 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, A chlorinated polyolefin composition, characterized in that the acid acceptor comprises an epoxidized polybutadiene and an epoxidized oil. [2] The chlorinated polyolefin composition according to [1], wherein the chlorinated polyolefin is a chlorinated polyethylene. [3] The chlorinated polyolefin composition according to [1] or [2], wherein the acid acceptor has an epoxy equivalent of 100 or more and 400 or less. [4] The chlorinated polyolefin composition according to any one of [1] to [3], wherein the epoxidized oil has a molecular weight of 200 or more and 2,000 or less. [5] The chlorinated polyolefin composition according to any one of [1] to [4], wherein the epoxidized oil is an epoxidized fatty acid alkyl ester having an alkyl group with 1 to 8 carbon atoms. [6] The chlorinated polyolefin composition according to any one of [1] to [5], wherein the acid acceptor is present in an amount of 1 part by mass or more and 50 parts by mass or less per 100 parts by mass of the chlorinated polyolefin. [7] The chlorinated polyolefin composition according to any one of [1] to [6], wherein the chlorinated polyolefin has a Mooney viscosity of 30 or more and 140 or less. [8] The chlorinated polyolefin composition according to any one of [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 any one of [1] to [8], which is for use in roller rubber.

[10] A molded article obtained by molding the chlorinated polyolefin composition according to any one of [1] to [9]. [Effects of the Invention]

[0013] The chlorinated polyolefin composition of the present embodiment is less expensive than conventionally known chlorinated polyolefin compositions, has high tensile elongation at break and strength at break, low Taber abrasion, and good acid resistance, alkali resistance, and water resistance, and also has good acid resistance compared to chlorosulfonated polyolefin compositions.

[0014] Therefore, resin products using the chlorinated polyolefin composition of the present invention have unprecedented high durability in applications where they are likely to come into contact with acid compounds, alkaline compounds, or water. DETAILED DESCRIPTION OF THE INVENTION

[0015] The chlorinated polyolefin composition of the present embodiment contains (A) a chlorinated polyolefin, (B) an acid acceptor, and may also contain (C) a reinforcing material, (D) a plasticizer, and (E) an organic peroxide.

[0016] (A) Chlorinated polyolefin (A) Chlorinated polyolefins are obtained by chlorinating polyolefins. Examples of polyolefins include homopolymers of α-olefins having 2 to 10 carbon atoms, such as polyethylene and polypropylene (hereinafter sometimes abbreviated as PP), and copolymers of two or more α-olefins, such as block copolymer PP and random PP. Among these, non-sulfonated polyolefins are more preferred in terms of productivity during chlorination, mechanical strength, flexibility, and crosslinkability, and polyethylene is particularly preferred.

[0017] The chlorination of the 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. 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. A chlorine content of 25% by mass or more is preferred because flexibility can be obtained. A chlorine content of 50% by mass or less is preferred because good flexibility, chemical resistance, and heat resistance can be obtained.

[0018] Chlorinated polyolefins have a Mooney viscosity of ML at 121°C. (1+4) The lower limit of the Mooney viscosity ML is preferably 30 or more, more preferably 50 or more, and even more preferably 55 or more. (1+4) If the Mooney viscosity ML of the chlorinated polyolefin at 121°C is 30 or more, the kneading processability is good, and the mechanical strength, chemical resistance, and abrasion resistance are excellent, which is preferable. (1+4) The upper limit of the Mooney viscosity ML is preferably 140 or less, more preferably 130 or less, and even more preferably 120 or less. (1+4) If the value is 140 or less, the kneading processability and mechanical strength are excellent, which is preferable.

[0019] The mass average molecular weight Mw of the chlorinated polyolefin is preferably 100,000 or more, more preferably 150,000 or more. The upper limit of Mw is 300,000 or less, more preferably 250,000 or less. Within this range, the Mooney viscosity can be adjusted to the above-mentioned range, and the desired properties can be fully exhibited.

[0020] The chlorinated polyolefin in this embodiment is preferably amorphous. Here, amorphous means that the heat of crystalline fusion measured by using a differential scanning calorimeter to raise the temperature of a measurement sample from 30°C at a rate of 10°C per minute is 2.0 J / g or less. Amorphous chlorinated polyolefins can provide greater flexibility.

[0021] (B) Acid acceptor The acid acceptor (B) contains an epoxidized polybutadiene and an epoxidized oil. These two components may be used alone or in combination. By using two acid acceptors in this manner, the absolute value of the tensile elongation at break is large, and an inexpensive composition can be obtained.

[0022] The epoxidized polybutadiene is not particularly limited, but examples thereof include epoxy-modified polybutadiene, etc. In particular, compounds in which epoxy groups are introduced by oxidation of vinyl groups are more preferred.

[0023] For example, commercially available products include NISSO-PB (registered trademark) JP-100 and JP-200 (both manufactured by Nippon Soda Co., Ltd.), Epolead (registered trademark) PB3600 and 4700 (both manufactured by Daicel Corporation), Adeka Cizer (registered trademark) BF-1000 (manufactured by ADEKA Corporation), and Ricon (registered trademark) 657 (manufactured by Cray Valley Chemical Industries, Ltd.), and these may be used alone or in combination of two or more types.

[0024] The number average molecular weight of the 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 the epoxidized polybutadiene is preferably 10000 or less, more preferably 8000 or less, and even more preferably 6000 or less. By using an epoxidized polybutadiene having such a number average molecular weight, a chlorinated polyolefin composition can be obtained that is particularly excellent in epoxidized polybutadiene, and has excellent alkali resistance and water resistance.

[0025] The epoxy equivalent of the epoxidized polybutadiene is preferably 400 or less, more preferably 300 or less, with the lower limit being 100 or more, and even more preferably 140 or more. By using an epoxidized polybutadiene having an epoxy equivalent within this range, a chlorinated polyolefin composition having excellent water resistance and acid resistance can be obtained.

[0026] The amount of epoxidized polybutadiene blended 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 chlorinated polyolefin. The amount of epoxidized polybutadiene blended 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 chlorinated polyolefin.

[0027] The epoxidized oil refers to an epoxidized fatty acid ester, and is not particularly limited as to whether the alkyl chain of the fatty acid or the alkyl chain of the ester is epoxidized. However, the oil is usually an ester of an epoxidized fatty acid, and examples thereof include epoxidized fatty acid alkyl esters (alkyl having 1 to 30 carbon atoms), epoxidized linseed oil, and epoxidized aliphatic esters, with epoxidized fatty acid alkyl esters (alkyl having 1 to 8 carbon atoms) being preferred.

[0028] 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 having such a molecular weight, a chlorinated polyolefin composition having excellent acid resistance, alkali resistance, and water resistance can be obtained.

[0029] The epoxy equivalent of the epoxidized oil is preferably not more than 400, more preferably not more than 300, with the lower limit being not less than 100, even more preferably not less than 140. By using an acid acceptor having an epoxy equivalent within this range, a chlorinated polyolefin composition having excellent water resistance and acid resistance can be obtained.

[0030] The amount of the epoxidized oil 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 the (A) chlorinated polyolefin. The amount of the epoxidized oil 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 the (A) chlorinated polyolefin.

[0031] The amount of the acid acceptor is the sum of the epoxidized polybutadiene and the epoxidized oil. The amount of the acid acceptor is preferably 2 parts by mass or more, more preferably 6 parts by mass or more, and even more preferably 10 parts by mass or more, per 100 parts by mass of the (A) chlorinated polyolefin. The amount of the acid acceptor is preferably 100 parts by mass or less, more preferably 60 parts by mass or less, and even more preferably 40 parts by mass or less, per 100 parts by mass of the (A) chlorinated polyolefin.

[0032] By combining an acid acceptor in this manner, it is possible to provide a chlorinated polyolefin composition which has a large tensile elongation at break and excellent durability in terms of acid resistance, alkali resistance, heat resistance, water resistance, etc. The chlorinated polyolefin composition of the present embodiment may contain the following additives depending on the purpose.

[0033] (C) Reinforcement The chlorinated polyolefin composition of this embodiment may contain a (C) 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., with carbon black and silica being more preferred due to their excellent abrasion resistance. These (C) reinforcing materials may be surface-treated for purposes such as antistatic properties.

[0034] (D) Plasticizer The chlorinated polyolefin composition of this embodiment may contain (D) a plasticizer. As the (D) plasticizer, plasticizers commonly used for polyvinyl chloride can be used. Specific examples of the plasticizer include alkylsulfonic acid phenyl ester (trade name Mesamoll (registered trademark)); dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, di-n-octyl phthalate, 2-ethylhexyl phthalate (hereinafter sometimes abbreviated as DOP), isononyl phthalate, octyldecyl phthalate, butyl benzyl phthalate, dicyclohexyl phthalate, n-octyl tetrahydrophthalate, di-2-ethylhexyl tetrahydrophthalate, tetramethyl ... Phthalate ester plasticizers such as diisodecyl tetrahydrofuranate; 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 adipate 610, dibutyl diglycol adipate, di-2-ethylhexyl azelaate, di-n-hexyl azelaate, dibutyl sebacate, sebacic acid Examples of plasticizers that can be used include aliphatic dibasic ester plasticizers such as di-2-ethylhexyl phosphate; trimellitic ester plasticizers such as trialkyl (C4-11) trimellitate, cyclohexene carboxylic acid ester, trioctyl trimellitate, and isononyl trimellitate; polyester plasticizers such as propylene glycol adipate and 1,3-butylene glycol adipate, which are formed by 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, octyl diphenyl phosphate, tris(isopropylphenyl) phosphate, and cresyl diphenyl phosphate; and chlorinated paraffin plasticizers.

[0035] The blending amount of (D) plasticizer 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 blending amount of plasticizer is preferably 0.1 part 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. When the blending ratio of (D) plasticizer per 100 parts by mass of (A) chlorinated polyolefin is 30 parts by mass or less, a molded product with appropriate hardness can be obtained.

[0036] (E)Organic peroxide The type of organic peroxide (E) blended in the chlorinated polyolefin composition of 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-hexylperoxyisopropyl monocarbonate, t-butyl ... Examples of organic peroxides 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 (registered trademark) P), dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxyl)hexyne-3 (trade name: Perhexyne (registered trademark) 25B-40), and 2,5-di(t-butylperoxy)-2,5-dimethyl-hexane (trade name: Perhexa (registered trademark) 25B). These organic peroxides (E) may be used alone or in combination of two or more.

[0037] Among these (E) organic peroxides, those having a one-minute half-life temperature of 130° C. or higher are preferred. If the one-minute half-life temperature is 130° C. or higher, a crosslinked molded article can be easily obtained.

[0038] Here, the one-minute half-life temperature of (E) organic peroxide is the temperature at which the (E) organic peroxide decomposes and the initial amount of active oxygen is reduced to half in one minute. The measurement method is not particularly limited, but it can be determined, for example, by determining the half-life of the organic peroxide at a peroxide concentration of 0.10 mol / L in a solvent relatively inert to radicals (such as benzene) at multiple temperatures and plotting the data.

[0039] The amount of (E) organic peroxide, calculated as 100% purity, based on 100 parts by mass of chlorinated polyolefin, is preferably 0.4 parts by mass or more, more preferably 0.8 parts by mass or more, and even more preferably 1.0 parts by mass or more, and 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 (E) organic peroxide, calculated as 100% purity, is 0.4 parts by mass or more, the crosslinking reaction of the composition proceeds rapidly, making it easier to obtain molded articles with excellent mechanical strength and abrasion resistance, which is preferable. On the other hand, if the amount of (E) organic peroxide, calculated as 100% purity, is 8.0 parts by mass or less, molded articles can be easily obtained from the composition.

[0040] To the chlorinated polyolefin composition of the present embodiment, various additives known in the art, such as crosslinking aids, stabilizers, antioxidants, processing aids, viscosity imparting agents, flame retardants, pigments, etc., can be added within a range that does not impair the properties of the present invention.

[0041] The chlorinated polyolefin composition of the present embodiment can be molded into a molded article by various molding methods, such as compression molding, injection molding, transfer molding, extrusion molding, etc. When an organic peroxide is contained, crosslinking may be carried out, and various crosslinking methods such as hot air crosslinking, microwave crosslinking, and electron beam crosslinking can be used.

[0042] The crosslinking temperature of the molded article of this embodiment depends on the thermal decomposition temperature of the organic peroxide used, and the 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 of 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, appropriate crosslinking can be achieved. If the temperature is 190°C or lower, the generated acid can be trapped by the acid acceptor, allowing appropriate crosslinking.

[0043] The crosslinking time conditions for the molded article of 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 of 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. Furthermore, if the crosslinking time is 300 minutes or less, appropriate crosslinking can be achieved.

[0044] The molded articles produced by this method have excellent durability, such as acid resistance, alkali resistance, water resistance, and heat resistance, and can be used for a variety of purposes, such as electrical wire coating materials, mono pump stator materials, industrial rubber rollers, automotive dust boots, and automotive hoses.

[0045] The molded article of this embodiment is particularly preferably used for a rubber roller. As described in JP 2006-207660 A, the rubber roller is made of a cylindrical substrate, and the substrate is made of the chlorinated polyolefin composition of this embodiment. The substrate is provided on the outer circumferential surface of a shaft, and the shaft is made of metal and formed into a cylindrical shape. [Example]

[0046] The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples in any way. The test methods used in the examples and comparative examples are as follows.

[0047] Molecular weight of acid acceptor (B) The molecular weight is measured by mass spectrometry using an Agilent Technologies 7200B model, with an ionization method of EI (electron impact method), and a mass separation tube of quadrupole type in the front stage and time-of-flight type in the rear stage.

[0048] Epoxy equivalent of acid acceptor In the present application, the epoxy equivalent is a value measured in accordance with JIS K7236 (2001).

[0049] Mooney viscosity of chlorinated polyolefins and chlorinated polyolefin compositions The Mooney viscosity (ML) at 121°C (after 1 minute of preheating and 4 minutes of rotation) was measured using a Mooney viscometer (Shimadzu Corporation, SMV-300RT) according to the method specified in JIS K6300-2:2001, using an L rotor. 1+4 (121°C) was measured.

[0050] 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 to remove hydrochloric acid, absorbing the generated hydrochloric acid gas into distilled water, and neutralizing and titrating it with a 0.1 mol / 1 normal solution of caustic soda.

[0051] [Examples 1 to 2, Comparative Examples 1 to 41] Preparation of the composition The following materials were used in the examples and comparative examples. (A) Chlorinated polyolefin, etc. Chlorinated polyethylene (1): Showa Denko Co., Ltd. Elaslen 402NA-X5, chlorine content 40% by mass, Mooney viscosity 121°C ML (1+4) 70 Chlorinated polyethylene (2): Showa Denko Co., Ltd., Elaslen 401A, chlorine content 40% by mass, Mooney viscosity 121°C ML (1+4) 115 Chlorinated polyethylene (3): Showa Denko Co., Ltd., Elaslen 301A, chlorine content 30% by mass, Mooney viscosity 121℃ ML (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 100°C ML (1+4) 56

[0052] (B) Acid acceptor Epoxidized fatty acid octyl ester: ADEKA Corporation, Adeka Cizer D-32, molecular weight 409, epoxy equivalent weight 372 Epoxidized fatty acid alkyl ester: ADEKA Corporation, Adeka Cizer D-55, molecular weight 356, epoxy equivalent weight 333 Polyglycidyl ether of glycerin-epichlorohydrin 0-1 mole adduct; NOF Corporation, Epiol (registered trademark) G-100, molecular weight 204-352, epoxy equivalent 160 Polyglycidyl ether of ethylene glycol-epichlorohydrin 0-2 mole adduct; NOF Corporation, Epiol E-100LC, molecular weight 174-350, epoxy equivalent 145 Ethylene glycol diglycidyl ether; Kyoeisha Chemical Co., Ltd., Epolite 40E, molecular weight 174, epoxy equivalent weight 125-140 Epoxidized polybutadiene (1); NISSO-PB-JP-100 manufactured by Nippon Soda Co., Ltd. Molecular weight: 1300 Epoxy equivalent: 190-210 Epoxidized polybutadiene (2); NISSO-PB-JP-200 manufactured by Nippon Soda Co., Ltd., molecular weight 2200, epoxy equivalent weight 210-240 Epoxidized polybutadiene (3): Epolead PB3600 manufactured by Daicel Corporation, molecular weight 5900, epoxy equivalent weight 185-210 Epoxidized polybutadiene (4): Epolead PB4700 manufactured by Daicel Corporation, molecular weight 2000-3500, epoxy equivalent weight 152-178 Lead oxide: Rhenogran PbO-80 manufactured by Rhein Chemie Magnesium oxide: Kyowamag 150 manufactured by Kyowa Chemical Industry Co., Ltd. Synthetic hydrotalcite: DHT-4A manufactured by Kyowa Chemical Industry Co., Ltd. Synthetic hydrocalumite; E-1300 manufactured by Katsuta Chemical Industry Co., Ltd. Epoxy resin: Mitsubishi Chemical Corporation JER828, molecular weight 370, epoxy equivalent weight 184-194 Calcium silicate: Silmos C manufactured by Shiraishi Kogyo Co., Ltd. Magnesium hydroxide: Kisma 5J manufactured by Kyowa Chemical Industry Co., Ltd. Calcium hydroxide: CA-100T manufactured by Katsuta Chemical Co., Ltd. Calcium-substituted zeolite: CS100K manufactured by Katsuta Chemical Industry Co., Ltd. Perchloric acid treated hydrotalcite; KA-100 manufactured by Katsuta Chemical Industry Co., Ltd. Sodium A-type zeolite; NA-100 manufactured by Katsuta Chemical Industry Co., Ltd. Epoxidized soybean oil: ADEKA Corporation, Adeka Cizer O-130P, molecular weight 1000, epoxy equivalent weight 239 Epoxidized linseed oil: ADEKA Corporation, Adeka Cizer O-180A, molecular weight 1000, epoxy equivalent weight 145

[0053] (C) Reinforcement Carbon black: Furnace carbon black, manufactured by Cabot Japan, Shoblack N550G

[0054] (D) Plasticizer Trimellitic acid isononyl ester (ADEKA Corporation) Adeka Cizer C-9N

[0055] (E)Organic peroxide α,α'-Di(t-butylperoxy)diisopropylbenzene NOF Corporation Perbutyl P In Comparative Examples 13 and 35, the following triazine compounds and sulfur-containing vulcanization accelerators were used instead of the above organic peroxides. Triazine compounds 2,4,6-trimercapto-s-triazine: Jisnet F, manufactured by Sankyo Kasei Co., Ltd., molecular weight: 177 ·Sulfur-containing vulcanization accelerator 2-Mercaptobenzothiazole-dicyclohexylamine salt: Sansera MA, Sanshin Chemical Industry Co., Ltd. Molecular weight: 352

[0056] (Other) Crosslinking aids Triallyl isocyanurate (Taikyu, manufactured by Nippon Kasei Co., Ltd.)

[0057] The ingredients were weighed out in the amounts required to obtain the composition shown in Table 1, and mixed for 3 minutes at 60 rpm using a 1.8 L Banbury (registered trademark) mixer under water cooling. The mixture was discharged as kneaded composition A and then rolled out into a sheet using a 10-inch (25.4 cm) roll.

[0058] [Table 1]

[0059] Next, the obtained kneaded composition A was mixed with a triazine compound, a sulfur-containing vulcanization accelerator, and an organic peroxide crosslinking agent in the amounts shown in Table 2. Under water cooling, the crosslinking agent was added to the kneaded composition A using a 10-inch (25.4 cm) roll, and the mixture was kneaded for 5 minutes, and then taken out into a sheet as kneaded composition B.

[0060] [Table 2]

[0061] Next, each acid acceptor shown in Table 3 was blended with the B-kneaded composition in the amounts shown in Table 3 to prepare a chlorinated polyolefin composition. Each acid acceptor was added to the B-kneaded composition using a 10-inch (25.4 cm) roll under water cooling, and the mixture was kneaded for 5 minutes. The resulting mixture was taken out into a 2.3 mm thick sheet as the chlorinated polyolefin composition, and a molded product was obtained.

[0062] Test specimen preparation The material was crosslinked for 120 minutes using a press molding machine with a mold temperature of 150°C to obtain a crosslinked sheet with a thickness of 2 mm. In accordance with JIS-K6251-2017, test pieces for tensile tests were punched out using a No. 3 dumbbell. In addition, 20 mm square test pieces were punched out to measure the volume change rate in immersion tests in various chemicals.

[0063] Test Method Measurements were carried out using sheets prepared according to the above test specimen preparation method. Durometer hardness (HS) was measured in accordance with JIS-K6253-3:2012 Type A, and modulus at 100% elongation (M100), breaking strength (TB), and tensile elongation at break (EB) were measured at 500 mm / min at 23°C in accordance with JIS-K6251-2017. The results are shown in Table 3.

[0064] Furthermore, the test pieces prepared after the crosslinking treatment were immersed in the following chemicals, kept at 80°C for 168 hours, and then removed. The volume change rate (ΔV), durometer hardness (ΔHS), breaking strength (ΔTB), and tensile elongation at break (ΔEB) were measured, and the results are also shown in Table 3.

[0065] Each chemical to be immersed 10% hydrochloric acid: Kanto Chemical Co., Ltd., special grade hydrochloric acid, 35% by mass diluted with pure water to 10% by mass 10% sulfuric acid: Kanto Chemical Co., Ltd. sulfuric acid, special grade, 96% by mass diluted with pure water to 10% by mass 10% nitric acid: Kanto Chemical Co., Ltd., special grade nitric acid, 70% by mass diluted with pure water to 10% by mass 20% nitric acid: Kanto Chemical Co., Ltd., special grade nitric acid, 70% by mass diluted with pure water to 20% by mass 10% sodium hydroxide: Kanto Chemical Co., Ltd., special grade sodium hydroxide, 97% by mass diluted with pure water to 10% by mass Pure water; Factory pure water

[0066] [Table 3-1]

[0067] [Table 3-2]

[0068] [Table 3-3]

[0069] [Table 3-4]

[0070] The chlorinated polyolefin compositions of the Examples, even when used in combination with an epoxidized oil such as an epoxidized fatty acid alkyl ester that is less expensive than epoxidized polybutadiene rather than epoxidized polybutadiene alone, maintained constant values, such as an absolute value of tensile elongation at break of 290 MPa or more, a breaking strength of 17.5 MPa or more, and a taper abrasion of 0.038 cc / 1000 times or less, and changes in volume, hardness, etc. after immersion in any chemical remained within certain ranges, and no bleeding was observed, making them suitable for use in hoses, wire coating materials, rollers, packing, etc. that may be immersed in chemicals.

Claims

1. A chlorinated polyolefin composition comprising a chlorinated polyolefin and an acid acceptor, the acid acceptor comprises an epoxidized polybutadiene and an epoxidized oil; A chlorinated polyolefin composition, characterized in that the acid acceptor is contained in an amount of 1 part by mass or more and 50 parts by mass or less per 100 parts by mass of the chlorinated polyolefin.

2. 2. The chlorinated polyolefin composition of claim 1, wherein the chlorinated polyolefin is a chlorinated polyethylene.

3. 3. The chlorinated polyolefin composition according to claim 1, wherein the acid acceptor has an epoxy equivalent of 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 epoxidized oil is 200 or more and 2,000 or less.

5. 5. The chlorinated polyolefin composition according to claim 1, wherein the epoxidized oil is an epoxidized fatty acid alkyl ester having an alkyl group having 1 to 8 carbon atoms.

6. The chlorinated polyolefin composition according to any one of claims 1 to 5, wherein the chlorinated polyolefin has a Mooney viscosity at 121°C of 30 or more and 140 or less.

7. The chlorinated polyolefin composition 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. The chlorinated polyolefin composition according to any one of claims 1 to 7, which is used for roller rubber.

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

Images