Chlorinated vinyl chloride resin composition, method for producing same, and molded body using same

Abstract

The present invention relates to a chlorinated vinyl chloride resin composition which contains a chlorinated vinyl chloride resin and a plasticizer, the plasticizer comprising one or more ether plasticizers Z that are selected from the group consisting of fatty acid ester-based ether plasticizers and formal-based ether plasticizers. As a result, the present invention provides: a chlorinated vinyl chloride resin composition which is softened and has high powder fluidity; a method for producing the same; and a molded body using the same.

Description

Chlorinated vinyl chloride resin composition, its production method, and molded article using the same

[0001] The present invention relates to a chlorinated vinyl chloride resin composition containing a chlorinated vinyl chloride resin and a plasticizer, a method for producing the same, and a molded article using the same.

[0002] Chlorinated vinyl chloride resins are resins that have been chlorinated to improve heat resistance and flame retardancy while retaining the excellent weather resistance and mechanical properties of vinyl chloride resins. Like vinyl chloride resins, chlorinated vinyl chloride resins are widely used in various fields, such as automobiles, machinery, electricity, medicine, and construction. Chlorinated vinyl chloride resins are typically used in combination with stabilizers, stabilization aids, processing aids, lubricants, and inorganic fillers, but plasticizers may also be used. For example, Patent Document 1 describes a molding resin composition containing a chlorinated vinyl chloride resin, a heat stabilizer, and a polyhydric alcohol and / or a partial ester of a polyhydric alcohol. Patent Document 2 describes an agricultural vinyl chloride resin film containing a chlorinated vinyl chloride resin, chlorinated polyethylene, and a plasticizer. Patent Document 3 describes expandable vinyl chloride resin particles containing a chlorinated vinyl chloride resin, a plasticizer, and a blowing agent.

[0003] International Publication No. 2015 / 046456 Japanese Patent Application Laid-Open No. 2001-224258 Japanese Patent Application Laid-Open No. 2022-55452

[0004] On the other hand, compositions in which a plasticizer is blended with a chlorinated polyvinyl chloride resin to soften it are required to have powder fluidity for later processing, but when a plasticizer normally used in polyvinyl chloride resins is used, there is a problem that the powder fluidity decreases.

[0005] In order to solve the above problems, the present invention provides a chlorinated vinyl chloride resin composition that is softened and has high powder flowability, a method for producing the same, and a molded article made from the same.

[0006] The present invention relates to a chlorinated vinyl chloride resin composition comprising a chlorinated vinyl chloride resin and a plasticizer, wherein the plasticizer comprises one or more ether plasticizers Z selected from the group consisting of fatty acid ester-based ether plasticizers and formal-based ether plasticizers.

[0007] The present invention also relates to a method for producing the chlorinated vinyl chloride resin composition, comprising a step of mixing a chlorinated vinyl chloride resin and the ether plasticizer Z, wherein, in the mixing step, where Te is the expansion initiation temperature of a mixture containing the chlorinated vinyl chloride resin and the ether plasticizer Z and Tg is the gelation temperature of the mixture, [Tg - Te] is 20°C or higher, the mixing is performed with heating at an initial temperature of room temperature to 80°C and an end temperature of [Te + 10°C] to [Tg - 2°C].

[0008] The present invention also relates to a molded article obtained by molding the chlorinated vinyl chloride resin composition.

[0009] According to the present invention, it is possible to provide a softened chlorinated vinyl chloride resin composition having high powder flowability and a molded article obtained by molding the same. Furthermore, according to the production method of the present invention, it is possible to obtain a softened chlorinated vinyl chloride resin composition having high powder flowability.

[0010] The present inventors discovered that when a plasticizer is blended with a chlorinated vinyl chloride resin to soften it, the use of a conventional plasticizer used in vinyl chloride resins results in reduced powder flowability. They conducted extensive research to solve this problem. One possible solution would be to use a chlorinated vinyl chloride resin in combination with a vinyl chloride resin, but this results in reduced flame retardancy compared to when the vinyl chloride resin is not used. The present inventors surprisingly discovered that, in a chlorinated vinyl chloride resin composition containing a chlorinated vinyl chloride resin and a plasticizer, the use of one or more ether plasticizers Z selected from the group consisting of fatty acid ester-based ether plasticizers and formal-based ether plasticizers as the plasticizer improves dry-up properties and improves the powder flowability of the chlorinated vinyl chloride resin composition even without the use of a vinyl chloride resin. In particular, they found that the use of one or more ether plasticizers Z selected from the group consisting of fatty acid ester-based ether plasticizers and formal-based ether plasticizers improves the powder flowability of a chlorinated vinyl chloride resin composition with a high plasticizer content.

[0011] In this specification, when a numerical range is indicated with "to", the numerical range includes both end values ​​(upper and lower limits). For example, a numerical range of "A to B" includes both end values ​​A and B, and is the same range as "A or more and B or less". Any number within that range and any range included within that range are specifically disclosed. In addition, when multiple numerical ranges are described in this specification, they are intended to include numerical ranges obtained by appropriately combining the upper and lower limits of different numerical ranges. In addition, when multiple upper and lower limits are described separately for a numerical range, they are intended to include numerical ranges obtained by appropriately combining each of the upper and lower limits.

[0012] (Chlorinated vinyl chloride resin composition) The chlorinated vinyl chloride resin composition (hereinafter also simply referred to as resin composition) of one or more embodiments of the present invention contains a chlorinated vinyl chloride resin and a plasticizer.

[0013] The chlorinated vinyl chloride resin is not particularly limited, and a chlorinated vinyl chloride resin can be used as appropriate. Chlorination of vinyl chloride resin can be carried out, for example, by dispersing vinyl chloride resin in water and irradiating with ultraviolet light while blowing chlorine gas into the resin, or by dispersing vinyl chloride resin in water and heating and adding an oxidizing agent while blowing chlorine gas into the resin. Alternatively, chlorination can be carried out by flowing vinyl chloride resin in chlorine gas and irradiating with ultraviolet light.

[0014] The chlorine content of the chlorinated vinyl chloride resin is not particularly limited, but may be, for example, 60 to 75% by weight, 62 to 72% by weight, or 63 to 69% by weight. The average degree of polymerization of the chlorinated vinyl chloride resin is not particularly limited, but may be, for example, 400 to 1500, or 500 to 1200. In this specification, the chlorine content and average degree of polymerization of the chlorinated vinyl chloride resin can be measured, for example, as described in the Examples.

[0015] The average particle size of the chlorinated vinyl chloride resin is not particularly limited and may be 0.1 to 350 μm, 5 to 250 μm, 10 to 230 μm, or 50 to 200 μm. In this specification, the average particle size of the chlorinated vinyl chloride resin can be measured, for example, as described in the Examples.

[0016] The vinyl chloride resin is not particularly limited, and may be, for example, a vinyl chloride homopolymer or a vinyl chloride copolymer of vinyl chloride (monomer) and another monomer copolymerizable therewith.

[0017] The other monomers are not particularly limited and include, for example, olefins such as ethylene, propylene, and butene; vinyl esters such as vinyl acetate, vinyl propionate, and vinyl stearate; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, octyl vinyl ether, and lauryl vinyl ether; vinylidenes such as vinylidene chloride; unsaturated carboxylic acids and their anhydrides such as acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, maleic anhydride, and itaconic anhydride; unsaturated carboxylic acid esters such as methyl acrylate, ethyl acrylate, monomethyl maleate, dimethyl maleate, and butylbenzyl maleate; aromatic vinyl compounds such as styrene, α-methylstyrene, and divinylbenzene; unsaturated nitriles such as acrylonitrile; and crosslinkable monomers such as diallyl phthalate. The amount of these monomers used is preferably less than 50% by weight in the mixture with vinyl chloride (monomer). The vinyl chloride copolymer may contain more than 50% by weight of units derived from vinyl chloride, may contain 55 to 95% by weight of units derived from vinyl chloride and 5 to 45% by weight of units derived from other monomers, may contain 60 to 90% by weight of units derived from vinyl chloride and 10 to 40% by weight of units derived from other monomers, may contain 65 to 85% by weight of units derived from vinyl chloride and 15 to 35% by weight of units derived from other monomers, or may contain 70 to 85% by weight of units derived from vinyl chloride and 15 to 30% by weight of units derived from other monomers.

[0018] The vinyl chloride resin may be produced by any of known polymerization methods, such as suspension polymerization, microsuspension polymerization, emulsion polymerization, and bulk polymerization.

[0019] The plasticizer includes one or more ether plasticizers Z selected from the group consisting of fatty acid ester-based ether plasticizers and formal-based ether plasticizers. Hereinafter, unless otherwise specified, the ether plasticizer Z means one or more selected from the group consisting of fatty acid ester-based ether plasticizers and formal-based ether plasticizers.

[0020] From the viewpoint of further improving softening and powder flowability, the fatty acid ester-based ether plasticizer preferably contains a compound represented by the following general formula (1):

[0021]

[0022] In the general formula (1), X is a linear or branched alkylene group having 1 to 9 carbon atoms, and A 1 and A 2 are the same or different and each is an alkylene group having 2 to 4 carbon atoms; R 1 and R 2 are the same or different and each is a linear or branched alkyl group having 1 to 9 carbon atoms; n1 and n2 are the same or different and each is an integer of 1 to 7; and n1+n2 is an integer of 3 or more.

[0023] More specifically, examples of the fatty acid ester-based ether plasticizer represented by the general formula (1) include adipate ester-based ether plasticizers in which X represents an alkylene group having 4 carbon atoms, and azelaate ester-based ether plasticizers in which X represents an alkylene group having 7 carbon atoms in the general formula (1). From the viewpoints of availability and versatility, adipate ester-based ether plasticizers may also be used.

[0024] The adipic acid ester-based ether plasticizer can be, for example, an esterified compound of adipic acid and two molecules of ether alcohol. The ether alcohol may be one type of ether alcohol or two types of ether alcohol. Examples of ether alcohols that can be used as raw materials for the adipic acid ester-based ether plasticizer include ethylene oxide adducts and propylene oxide adducts of linear or branched aliphatic alcohols having 1 to 9 carbon atoms. More specific examples include ethylene oxide adducts such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and triethylene glycol monobutyl ether; and propylene oxide adducts such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, and tripropylene glycol monobutyl ether.

[0025] Among these, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, etc. are preferred, and diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, etc. are more preferred.

[0026] More specifically, the adipic acid ester ether plasticizer can be suitably exemplified by bis[2-(2-butoxyethoxy)ethyl] adipate (also referred to as bisbutylcarbitol adipate), which is an ester compound of adipic acid and two molecules of diethylene glycol monobutyl ether. Bisbutylcarbitol adipate is represented by the general formula (1), where X is an alkylene group having 4 carbon atoms, A 1 and A 2 Each of n1 and n2 is an ethylene group, each of n1 and n2 is 2, R 1 and R 2 are compounds each showing an n-butyl group.

[0027] From the viewpoint of further improving softening and powder flowability, the formal ether plasticizer preferably contains a compound represented by the following general formula (2).

[0028]

[0029] In the general formula (2), R 3 is hydrogen or an alkyl group having 1 to 3 carbon atoms, and B 1 and B 2 are the same or different and each is an alkylene group having 2 to 4 carbon atoms; R 4 and R 5 are the same or different and each is a linear or branched alkyl group having 1 to 9 carbon atoms; m1 and m2 are the same or different and each is an integer of 1 to 7;

[0030] The formal ether plasticizer represented by the general formula (2) can be, for example, a compound obtained by reacting an aldehyde compound such as formaldehyde and acetaldehyde with two molecules of an ether alcohol. The ether alcohol may be one type of ether alcohol or two types of ether alcohol. As the ether alcohol raw material for the formal ether plasticizer, the ether alcohols exemplified as raw materials for the adipate ester ether plasticizer can be appropriately used.

[0031] More specifically, the formal ether plasticizer represented by the general formula (2) is preferably bis(butyldiethylglycol) formal (also referred to as butylcarbitol formal), which is obtained by reacting formaldehyde with two molecules of diethylene glycol monobutyl ether. Butylcarbitol formal is a compound represented by the general formula (2), R 3 is hydrogen, B 1 and B 2 Each of m1 and m2 is an ethylene group, each of m1 and m2 is 2, R 4 and R 5 are compounds each showing an n-butyl group.

[0032] The molecular weight of the ether plasticizer Z is not particularly limited, but may be, for example, 200 to 1500 or 250 to 1000 from the viewpoint of further improving the softening effect and powder fluidity and suppressing bleed-out onto the surface of the molded body.

[0033] The ether plasticizer Z may be used alone or in combination of two or more. From the viewpoints of availability, softening, and powder flowability, the ether plasticizer Z preferably contains one or more selected from the group consisting of bisbutylcarbitol adipate and butylcarbitol formal, and more preferably contains bisbutylcarbitol adipate.

[0034] The content of the ether plasticizer Z in the resin composition is not particularly limited, but for example, from the viewpoint of softening effect, the resin composition may contain 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more of the ether plasticizer Z per 100 parts by weight of the chlorinated vinyl chloride resin. Furthermore, from the viewpoint of powder flowability and suppression of bleed-out on the surface of a molded article, the resin composition may contain 60 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, or 30 parts by weight or less of the ether plasticizer Z per 100 parts by weight of the chlorinated vinyl chloride resin. More specifically, the resin composition may contain 10 to 60 parts by weight, 10 to 50 parts by weight, 10 to 40 parts by weight, 10 to 30 parts by weight, 15 to 40 parts by weight, or 15 to 30 parts by weight of the ether plasticizer Z per 100 parts by weight of the chlorinated vinyl chloride resin.

[0035] The resin composition may further contain other additives such as a stabilizer, a stabilizing aid, a processing aid, a lubricant, and an inorganic filler (also called a bulking agent), as needed.

[0036] The stabilizer is not particularly limited, but examples thereof include epoxy-based stabilizers, barium-based stabilizers, calcium-based stabilizers, tin-based stabilizers, zinc-based stabilizers, hindered amine-based light stabilizers, calcium-zinc (Ca-Zn) stabilizers, and barium-zinc (Ba-Zn) stabilizers. One type of stabilizer may be used alone, or two or more types may be used in combination. The amount of the stabilizer may be 8 parts by weight or less, 5 parts by weight or less, or 0.01 to 3 parts by weight, per 100 parts by weight of the chlorinated vinyl chloride resin.

[0037] The stabilizing aid is not particularly limited, but examples thereof include zeolites and hydrotalcites. These may be used alone or in combination of two or more. The amount of the stabilizing aid may be 5 parts by weight or less, 3 parts by weight or less, or 0.01 to 3 parts by weight per 100 parts by weight of the chlorinated vinyl chloride resin.

[0038] The processing aid (also referred to as a modifier) ​​is not particularly limited, but examples thereof include acrylic processing aids. Examples of the acrylic processing aid include (meth)acrylate polymers and styrene-acrylonitrile copolymers. Examples of the (meth)acrylate polymer include copolymers of (meth)acrylate with one or more copolymerization components selected from the group consisting of butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, styrene, vinyl acetate, and acrylonitrile. Furthermore, commercially available (meth)acrylate polymers, such as Kane Ace (registered trademark) PA-20, Kane Ace (registered trademark) PA-40, and Kane Ace (registered trademark) PA-60 manufactured by Kaneka, can be used. The amount of the processing aid may be 7 parts by weight or less, 5 parts by weight or less, 3 parts by weight or less, or 0.01 to 3 parts by weight, per 100 parts by weight of the chlorinated vinyl chloride resin.

[0039] The lubricant is not particularly limited, but examples thereof include higher fatty acid metal salts such as calcium stearate, higher alcohols, polyethylene waxes, and ester waxes. These may be used alone or in combination of two or more. The amount of the lubricant may be 7 parts by weight or less, 5 parts by weight or less, 3 parts by weight or less, or 0.01 to 3 parts by weight per 100 parts by weight of the chlorinated vinyl chloride resin.

[0040] The inorganic filler is not particularly limited, but examples thereof include calcium carbonate, magnesium carbonate, calcium sulfate, magnesium sulfate, and talc. These may be used alone or in combination of two or more. The amount of the filler to be added may be 50 parts by weight or less, 30 parts by weight or less, or 0.01 to 30 parts by weight per 100 parts by weight of the chlorinated vinyl chloride resin.

[0041] The resin composition may contain other additives, such as crosslinking agents, foaming agents, antioxidants, reinforcing agents, ultraviolet absorbers, antistatic agents, colorants, surface treatment agents, thixotropic agents, mildew inhibitors, flame retardants, and detergents, as needed, within the scope of the present invention. The other additives may be used singly or in combination of two or more. The amount of the other additives may be 0 to 10 parts by weight, 0 to 8 parts by weight, 0 to 5 parts by weight, or 0 to 3 parts by weight, per 100 parts by weight of the chlorinated vinyl chloride resin.

[0042] More specifically, from the viewpoint of flame retardancy, the resin composition preferably contains 40 wt % or more of chlorinated vinyl chloride resin, more preferably 40 to 80 wt %, even more preferably 50 to 75 wt %, and even more preferably 55 to 70 wt %. From the viewpoint of enhancing flame retardancy, the resin composition preferably contains only chlorinated vinyl chloride resin as the halogen-containing resin, and does not contain vinyl chloride resin.

[0043] From the viewpoint of softness, the resin composition may have a hardness of 75 or less, 70 or less, or 65 or less as measured with a Type A durometer in accordance with JIS K 6253-3. The lower limit of the hardness is not particularly limited, but may be, for example, 35 or more from the viewpoint of normal heat resistance temperature. The hardness can be measured using a molded article obtained by molding the resin composition.

[0044] From the viewpoint of excellent powder flowability, the resin composition preferably has an angle of repose of 50° or less, more preferably 45° or less, and even more preferably 40° or less. In this specification, the angle of repose can be measured as described in the examples.

[0045] (Method for Producing Chlorinated Polyvinyl Chloride Resin Composition) The resin composition can be produced while maintaining a powder form by, for example, mixing (compounding) a chlorinated polyvinyl chloride resin and an ether plasticizer Z. For the mixing, a stirrer such as a ribbon blender, a Hemmel mixer, a planetary mixer, or a super mixer can be used.

[0046] In the mixing step, when the expansion initiation temperature Te of the mixture containing the chlorinated vinyl chloride resin and the ether plasticizer Z is taken as the temperature, and the gelation temperature Tg of the mixture is taken as the temperature, [Tg - Te] is preferably 20°C or higher, more preferably 21°C or higher, and even more preferably 25°C or higher, from the viewpoint of powder fluidity of the resulting resin composition.

[0047] The mixture may contain 10 to 60 parts by weight, 10 to 50 parts by weight, 10 to 40 parts by weight, 10 to 30 parts by weight, 15 to 40 parts by weight, or 15 to 30 parts by weight of ether plasticizer Z relative to 100 parts by weight of chlorinated vinyl chloride resin.

[0048] The mixture may contain a stabilizer, a stabilizing aid, a processing aid, a lubricant, and an inorganic filler. The stabilizers, processing aids, lubricants, and inorganic fillers described above can be used as appropriate. The mixture may contain, per 100 parts by weight of chlorinated vinyl chloride resin, 8 parts by weight or less, 5 parts by weight or less, or 0.01 to 3 parts by weight of the stabilizer; 5 parts by weight or less, 3 parts by weight or less, or 0.01 to 3 parts by weight of the stabilizing aid; 7 parts by weight or less, 5 parts by weight or less, or 0.01 to 3 parts by weight of the processing aid; 5 parts by weight or less, 3 parts by weight or less, or 0.01 to 3 parts by weight of the lubricant; and 50 parts by weight or less, 30 parts by weight or less, or 0.1 to 30 parts by weight of the inorganic filler.

[0049] The mixture may contain other additives, such as a crosslinking agent, a foaming agent, an antioxidant, a reinforcing agent, an ultraviolet absorber, an antistatic agent, a colorant, a surface treatment agent, a thixotropic agent, an antifungal agent, a flame retardant, and a detergent, as needed, within the range that does not impair the effects of the present invention. The mixture may contain 0 to 10 parts by weight, 0 to 8 parts by weight, 0 to 5 parts by weight, or 0 to 3 parts by weight of the other additives per 100 parts by weight of the chlorinated vinyl chloride resin.

[0050] The mixing step is preferably carried out under heating, with the starting temperature being preferably room temperature to 80°C and the ending temperature being more preferably [Te + 10°C] to [Tg - 2°C], and even more preferably the starting temperature being room temperature to 60°C and the ending temperature being [Te + 12°C] to [Tg - 4°C]. This allows the ether plasticizer Z to be easily absorbed into the chlorinated vinyl chloride resin, resulting in a resin composition with improved powder fluidity. In this specification, room temperature means 5 to 45°C.

[0051] After the mixing step, the mixture is cooled to room temperature, whereby a resin composition having excellent powder flowability can be obtained.

[0052] (Molded Article) The resin composition can be appropriately molded into a molded article, which can be used as a film, sheet, electric wire, cord, packaging material, vehicle part, building material, etc. The molding method is not particularly limited, and various molding methods such as roll molding, press molding, powder slush molding, extrusion molding, injection molding, and calendar molding can be used appropriately depending on the application and shape of the molded article. The resin composition exhibits good dry-up properties of the ether plasticizer Z against chlorinated vinyl chloride resin, and the molded article obtained by molding exhibits low bleed-out of the ether plasticizer Z.

[0053] The present invention will be described in more detail below using examples, but the present invention is not limited to the following examples.

[0054] The compounds used in the examples and comparative examples will be explained below. Vinyl chloride resin: vinyl chloride homopolymer, average degree of polymerization 1000, average particle size 120 μm, manufactured by Kaneka Corporation, grade name "S1001N" Chlorinated vinyl chloride resin 1: chlorinated vinyl chloride resin obtained by chlorinating vinyl chloride homopolymer, chlorine content 67.6 wt%, average degree of polymerization 600, average particle size 130 μm, manufactured by Kaneka Corporation, grade name "H716S" Chlorinated vinyl chloride resin 2: chlorinated vinyl chloride resin obtained by chlorinating vinyl chloride homopolymer, chlorine content 64 wt%, average degree of polymerization 800, average particle size 150 μm, manufactured by Kaneka Corporation, grade name "H438" Plasticizer 1: butyl carbitol formal, molecular weight 336, manufactured by Emery Oleochemicals, grade name "EDENOL (registered trademark) 123" Plasticizer 2: bisbutyl carbitol adipate, molecular weight 463, manufactured by Emery Oleochemicals Oleochemicals, Grade "EDENOL (registered trademark) 111" Plasticizer 3: dioctyl phthalate, molecular weight 391, J-Plus Corporation, Grade "DOP" Plasticizer 4: diisononyl phthalate, molecular weight 419, J-Plus Corporation, Grade "DINP" Plasticizer 5: acetyl tributyl citrate, molecular weight 402, J-Plus Corporation, Grade "ATBC" Plasticizer 6: trimellitic acid C 8-10Plasticizer 7: dioctyl sebacate, molecular weight 427, manufactured by Emery Oleochemicals, grade "EDENOL (registered trademark) T810" Plasticizer 8: fatty acid ester, molecular weight 426, manufactured by Emery Oleochemicals, grade "EDENOL (registered trademark) 102" Plasticizer 9: benzoic acid ester represented by the following chemical formula (3), manufactured by ADEKA Corporation, grade "ADEKA CIZER PN-6122" Plasticizer 10: adipic acid polyester, molecular weight approximately 2000, manufactured by ADEKA Corporation, grade "ADEKA CIZER P-200" Plasticizer 11: Adipic acid polyester, molecular weight approximately 3000, manufactured by Emery Oleochemicals, grade name "EDENOL (registered trademark) E1233SP"

[0055]

[0056] Example 1 Using a mixer (50 ml capacity; manufactured by Brabender, Germany, model number "Mixer Type 50") attached to a Plastograph EC, 20 g of chlorinated vinyl chloride resin 1 was added from the hopper, and mixing was initiated at a rotation speed of 20 rpm. After 1 minute and 30 seconds, plasticizer 1 was added to the hopper in the amount shown in Table 1 below, and mixing was continued. After adding plasticizer 1, the hopper of the mixer was observed, and the change in torque was measured using a torque measuring device attached to the mixer. The heating conditions for the mixer were set as follows: the temperature was raised to 100°C in 5 minutes, held for 1 minute, then raised to 120°C in 5 minutes, held for 1 minute, and then raised to 140°C in 5 minutes. The hopper of the mixer was visually observed, and the temperature at which the volume of the mixture expanded and overflowed from the hopper outlet, making the kneader no longer visible from the top of the hopper, was defined as the "expansion onset temperature." The temperature at which the torque detected by the torque measuring device installed in the mixer began to clearly increase was defined as the "gelation temperature." In Example 1, the expansion starting temperature Te of the compound (mixture) was 90°C, and the gelation temperature Tg was 119°C. The mixture overflowing from the hopper was collected and left to cool at room temperature on a medicine wrapping paper to obtain a resin composition.

[0057] (Example 2) A resin composition was obtained by mixing in the same manner as in Example 1, except that the plasticizer shown in Table 1 below was used as the plasticizer. In Example 2, the expansion starting temperature Te and gelation temperature Tg of the compound (mixture) were as shown in Table 1 below.

[0058] (Example 3) Mixing was carried out in the same manner as in Example 1 to obtain a resin composition, except that the blend amount of the plasticizer was changed as shown in the following Table 1. In Example 3, the expansion starting temperature Te and gelation temperature Tg of the blend (mixture) were as shown in the following Table 1.

[0059] Example 4 A resin composition was obtained by mixing in the same manner as in Example 1, except that chlorinated vinyl chloride resin 2 was used as the chlorinated vinyl chloride resin. In Example 4, the expansion onset temperature Te and gelation temperature Tg of the blend (mixture) were as shown in Table 1 below.

[0060] Example 5 A resin composition was obtained by mixing in the same manner as in Example 2, except that chlorinated vinyl chloride resin 2 was used as the chlorinated vinyl chloride resin. In Example 5, the expansion onset temperature Te and gelation temperature Tg of the blend (mixture) were as shown in Table 1 below.

[0061] Example 6 A resin composition was obtained by mixing in the same manner as in Example 3, except that chlorinated vinyl chloride resin 2 was used as the chlorinated vinyl chloride resin. In Example 6, the expansion onset temperature Te and gelation temperature Tg of the blend (mixture) were as shown in Table 1 below.

[0062] Comparative Examples 1 to 9 Resin compositions were obtained by mixing in the same manner as in Example 1, except that the plasticizers shown in Table 1 below were used. In Comparative Examples 1 to 9, the expansion onset temperature Te and gelation temperature Tg of the blends (mixtures) were as shown in Table 1 below.

[0063] (Comparative Example 10) A resin composition was obtained by mixing in the same manner as in Example 4, except that the plasticizer shown in Table 1 below was used. In Comparative Example 10, the expansion onset temperature Te and gelation temperature Tg of the compound (mixture) were as shown in Table 1 below.

[0064] Reference Example 1 A resin composition was obtained by mixing in the same manner as in Example 1, except that a vinyl chloride resin was used instead of a chlorinated vinyl chloride resin and that the plasticizers shown in Table 1 below were used. In Reference Example 1, the expansion onset temperature Te and gelation temperature Tg of the compound (mixture) were as shown in Table 1 below.

[0065] The powder flowability of the resin compositions obtained in Examples 1 to 6, Comparative Examples 1 to 10, and Reference Example 1 was evaluated as follows. The results are shown in Table 1 below. In Table 1 below, the amount of plasticizer blended is the amount blended per 100 parts by weight of chlorinated vinyl chloride resin or vinyl chloride resin. The chlorine content, average degree of polymerization, and average particle size of the chlorinated vinyl chloride resins used in the examples and comparative examples were measured as follows.

[0066] (Chlorine Content) The chlorine content of the chlorinated polyvinyl chloride resin was measured in accordance with JIS K 7229.

[0067] (Average Degree of Polymerization) The average degree of polymerization of the raw vinyl chloride resin was used as the average degree of polymerization of the chlorinated vinyl chloride resin. The average degree of polymerization of the vinyl chloride resin was measured in accordance with the method described in JIS K 6720-2 Appendix / Test Method for Vinyl Chloride Resins.

[0068] (Average Particle Diameter) The average particle diameter of the chlorinated polyvinyl chloride resin was measured in accordance with JIS K 7369.

[0069] (Powder fluidity) The resin composition was visually observed and subjected to a sensory evaluation according to the following two-stage scale. A rating indicates good powder fluidity, and B rating indicates poor powder fluidity. A: Powder state that is smooth B: Powder state that is wet

[0070]

[0071] As can be seen from the data in Table 1, the resin compositions of Examples 1 to 6, which contained a chlorinated vinyl chloride resin and a fatty acid ester ether plasticizer or a formal ether plasticizer, had a difference between the gelation temperature Tg and the expansion onset temperature Te of 21°C or more, and exhibited good powder fluidity. On the other hand, the chlorinated vinyl chloride resin compositions of Comparative Examples 1 to 10, which used a phthalate ester plasticizer, acetyl tributyl citrate, trimellitate ester plasticizer, fatty acid ester plasticizer, or adipic acid polyester, which are commonly used in vinyl chloride resins, had a difference between the gelation temperature Tg and the expansion onset temperature Te of 17°C or less, and exhibited poor powder fluidity.

[0072] Example 7 Using a planetary mixer (manufactured by Toyo Seiki Seisakusho, model number "P600") attached to a Labo Plastomill, the mixture was preheated to 60°C, and 150 g of chlorinated vinyl chloride resin 1 was added. Mixing was initiated at a rotation speed of 60 rpm. After 2 minutes, plasticizer 1 was added in the amount shown in Table 2 below, and mixing was continued. After 1 minute, the temperature was raised at a rate of approximately 2.1°C / min. When the temperature rose to 80°C, 21.5 g of another additive set (consisting of 21 wt% barium-zinc stabilizer, 49 wt% acrylic processing aid, 2 wt% lubricant, and 28 wt% inorganic filler) was added, and mixing was continued. After the temperature rose to 110°C, mixing was terminated. The mixture was then transferred to a stainless steel bowl and allowed to cool at 24±5°C to obtain a resin composition (compound).

[0073] Example 8 A resin composition was obtained in the same manner as in Example 7, except that the plasticizer shown in Table 2 below was used.

[0074] Example 9 A resin composition was obtained in the same manner as in Example 7, except that the amount of butyl carbitol formal was changed as shown in Table 2 below.

[0075] Example 10 A resin composition was obtained in the same manner as in Example 7, except that chlorinated vinyl chloride resin 2 was used as the chlorinated vinyl chloride resin.

[0076] Example 11 A resin composition was obtained in the same manner as in Example 8, except that chlorinated vinyl chloride resin 2 was used as the chlorinated vinyl chloride resin.

[0077] Example 12 A resin composition was obtained in the same manner as in Example 9, except that chlorinated vinyl chloride resin 2 was used as the chlorinated vinyl chloride resin.

[0078] Comparative Examples 11 to 19 Resin compositions were obtained in the same manner as in Example 7, except that the plasticizers shown in Table 2 below were used.

[0079] Comparative Example 20 A resin composition was obtained in the same manner as in Example 10, except that the plasticizer shown in Table 2 below was used.

[0080] Reference Example 2 A resin composition was obtained in the same manner as in Example 7, except that a vinyl chloride resin was used instead of the chlorinated vinyl chloride resin, and the plasticizers shown in Table 1 below were used.

[0081] The powder flowability and angle of repose of the resin compositions obtained in Examples 7 to 12, Comparative Examples 11 to 20, and Reference Example 2 were measured as follows. The results are shown in Table 2 below.

[0082] (Powder fluidity) The resin composition was visually observed and subjected to a sensory evaluation according to the following four-level scale. A rating indicates good powder fluidity, while B to D ratings indicate poor powder fluidity. A: Powder in a smooth state B: Powder in a moist state C: Moist with a small amount of granular lumps D: Moist with mostly granular lumps

[0083] (Angle of repose) A container for measuring bulk specific gravity (cylindrical, 42 mm in diameter, 81 mm in height) specified in JIS K 6721:1977 was placed upside down, and 20 g of a weighed resin composition was dropped onto the top of the container from the funnel of the bulk specific gravity measuring device (inner diameter of the narrowest part: 8 mm). The angle of repose of the resin composition deposited on the top of the container was measured.

[0084]

[0085] As can be seen from the data in Table 2, the chlorinated vinyl chloride resin compositions of Examples 7 to 12, which used a fatty acid ester ether plasticizer or a formal ether plasticizer, had good powder fluidity, even when containing other additives such as a stabilizer in addition to a plasticizer. On the other hand, the chlorinated vinyl chloride resin compositions of Comparative Examples 11 to 20, which used a phthalate ester plasticizer, acetyl tributyl citrate, trimellitate ester plasticizer, fatty acid ester plasticizer, or adipic acid polyester commonly used in vinyl chloride resins, had poor powder fluidity, even when containing other additives such as a stabilizer in addition to a plasticizer.

[0086] (Test Example 1) A mixture of 100 parts by weight of chlorinated vinyl chloride resin 1, 50 parts by weight of butyl carbitol formal as a plasticizer, 2.5 parts by weight of a barium-zinc stabilizer, 3.0 parts by weight of an acrylic processing aid, 0.9 parts by weight of a lubricant, and 1.0 part by weight of an inorganic filler was mixed and kneaded with a heated roll (two rolls) at 165 to 170°C for 5 minutes or more to prepare a roll sheet (thickness 0.6 mm). The obtained roll sheet was very soft.

[0087] Test Example 2 A roll sheet (thickness: 0.6 mm) was produced in the same manner as in Test Example 1, except that bisbutylcarbitol adipate was used as the plasticizer. The obtained roll sheet was soft.

[0088] The hardness and migration properties of the roll sheets obtained in Test Examples 1 and 2 were measured and evaluated as follows. The results are shown in Table 3 below.

[0089] (Hardness) The hardness was measured using an Asker hardness tester Type A (Type A durometer) in accordance with JIS K 6253-3. A test piece was prepared by laminating roll sheets and pressing them in a press (manufactured by Shoji Iron Works Co., Ltd.) at 160°C and 3 MPa for 3 minutes to obtain a molded body with a thickness of 6 mm.

[0090] (Migration) Two roll sheets were stacked, and the stack was left at room temperature for 12 days with a pressure of 9.8 N applied to one surface of the stack. Thereafter, the degree of adhesion between the two roll sheets was checked.

[0091]

[0092] As can be seen from the results in Table 3, the sheets obtained in Test Examples 1 and 2 had low hardness. In addition, migration of the plasticizer from the sheets obtained in Test Examples 1 and 2 was suppressed.

[0093] The present invention is not particularly limited, but may include, for example, the following embodiments.

[0094] [1] A chlorinated vinyl chloride resin composition comprising a chlorinated vinyl chloride resin and a plasticizer, wherein the plasticizer comprises one or more ether plasticizers Z selected from the group consisting of fatty acid ester ether plasticizers and formal ether plasticizers. [2] The chlorinated vinyl chloride resin composition according to [1], wherein the fatty acid ester ether plasticizer comprises a compound represented by the following general formula (1): (In the general formula (1), X is a linear or branched alkylene group having 1 to 9 carbon atoms, and A 1 and A 2 are the same or different and each is an alkylene group having 2 to 4 carbon atoms; R 1 and R 2 are the same or different and each is a linear or branched alkyl group having 1 to 9 carbon atoms, n1 and n2 are the same or different and are an integer of 1 to 7, and n1 + n2 is an integer of 3 or greater.) [3] The chlorinated vinyl chloride resin composition according to [1] or [2], wherein the formal ether plasticizer contains a compound represented by the following general formula (2): (However, in the general formula (2), R 3 is hydrogen or an alkyl group having 1 to 3 carbon atoms, and B 1 and B 2 are the same or different and each is an alkylene group having 2 to 4 carbon atoms; R 4 and R 5are the same or different and each represents a linear or branched alkyl group having 1 to 9 carbon atoms, and m1 and m2 are the same or different and each represents an integer of 1 to 7.) [4] The chlorinated vinyl chloride resin composition according to any one of [1] to [3], wherein the ether plasticizer Z comprises one or more selected from the group consisting of bis[2-(2-butoxyethoxy)ethyl] adipate and bis(butyldiethyl glycol) formal. [5] The chlorinated vinyl chloride resin composition according to any one of [1] to [4], wherein the ether plasticizer Z comprises 10 to 60 parts by weight per 100 parts by weight of the chlorinated vinyl chloride resin. [6] The chlorinated vinyl chloride resin composition according to any one of [1] to [5], wherein the chlorinated vinyl chloride resin composition comprises 40 to 80% by weight of the chlorinated vinyl chloride resin. [7] The chlorinated vinyl chloride resin composition according to any one of [1] to [6], wherein the chlorinated vinyl chloride resin composition does not contain a vinyl chloride resin. [8] A method for producing a chlorinated vinyl chloride resin composition according to any one of [1] to [7], comprising a step of mixing a mixture containing chlorinated vinyl chloride resin and the ether plasticizer Z, wherein in the mixing step, where Te is the expansion initiation temperature of the mixture containing the chlorinated vinyl chloride resin and the ether plasticizer Z and Tg is the gelation temperature of the mixture, [Tg - Te] is 20°C or higher, and the mixing is carried out while heating, with the starting temperature being room temperature to 80°C and the ending temperature being [Te + 10°C] to [Tg - 2°C]. [9] A molded article produced by molding the chlorinated vinyl chloride resin composition according to any one of [1] to [7].

[10] The molded article according to [9], wherein the molded article has a hardness of 75 or less as measured with a Type A durometer in accordance with JIS K 6253-3.

Claims

1. A chlorinated vinyl chloride resin composition comprising a chlorinated vinyl chloride resin and a plasticizer, wherein the plasticizer comprises one or more ether plasticizers Z selected from the group consisting of fatty acid ester-based ether plasticizers and formal-based ether plasticizers.

2. The chlorinated vinyl chloride resin composition according to claim 1, wherein the fatty acid ester ether plasticizer comprises a compound represented by the following general formula (1): (In the general formula (1), X is a linear or branched alkylene group having 1 to 9 carbon atoms, and A 1 and A 2 are the same or different and each is an alkylene group having 2 to 4 carbon atoms; R 1 and R 2 are the same or different and each represents a linear or branched alkyl group having 1 to 9 carbon atoms, n1 and n2 are the same or different and each represents an integer of 1 to 7, and n1+n2 is an integer of 3 or more.

3. The chlorinated vinyl chloride resin composition according to claim 1, wherein the formal ether plasticizer comprises a compound represented by the following general formula (2): (However, in the general formula (2), R 3 is hydrogen or an alkyl group having 1 to 3 carbon atoms, and B 1 and B 2 are the same or different and each is an alkylene group having 2 to 4 carbon atoms; R 4 and R 5 are the same or different and each represents a linear or branched alkyl group having 1 to 9 carbon atoms, and m1 and m2 are the same or different and each represents an integer of 1 to 7.

4. The chlorinated vinyl chloride resin composition according to claim 1, wherein the ether plasticizer Z comprises at least one selected from the group consisting of bis[2-(2-butoxyethoxy)ethyl] adipate and bis(butyldiethylglycol) formal.

5. The chlorinated vinyl chloride resin composition according to claim 1, wherein the ether plasticizer Z is contained in an amount of 10 to 60 parts by weight per 100 parts by weight of the chlorinated vinyl chloride resin.

6. The chlorinated vinyl chloride resin composition according to claim 1, wherein the chlorinated vinyl chloride resin composition contains 40 to 80% by weight of chlorinated vinyl chloride resin.

7. The chlorinated vinyl chloride resin composition according to claim 1, wherein the chlorinated vinyl chloride resin composition does not contain a vinyl chloride resin.

8. A method for producing a chlorinated vinyl chloride resin composition according to any one of claims 1 to 7, comprising the step of mixing chlorinated vinyl chloride resin and said ether plasticizer Z, wherein in said mixing step, where Te is the expansion initiation temperature of a mixture containing chlorinated vinyl chloride resin and said ether plasticizer Z and Tg is the gelling temperature of said mixture, [Tg - Te] is 20°C or higher, and said mixing is carried out while heating, with the starting temperature being room temperature to 80°C and the ending temperature being [Te + 10°C] to [Tg - 2°C].

9. A molded article obtained by molding the chlorinated vinyl chloride resin composition according to any one of claims 1 to 7.

10. The molded article according to claim 9, wherein the molded article has a hardness of 75 or less as measured with a type A durometer in accordance with JIS K 6253-3.

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