阅读说明：本技术 成形用树脂组合物 (Resin composition for molding ) 是由 谷口宽 望月弘章 于 2018-09-26 设计创作，主要内容包括：本发明提供一种成形用树脂组合物和使用了成形用树脂组合物的成形体和管,所述成形用树脂组合物能够制造具有优异的耐热性、机械性能且表面平滑性高的成形体。本发明是一种成形用树脂组合物,其含有氯化氯乙烯系树脂、热稳定剂和耐冲击改性剂。此外,上述氯化氯乙烯系树脂的氯含量为63～72质量％,上述热稳定剂包含含钙的化合物和含锌的化合物,相对于上述氯化氯乙烯系树脂100质量份,含有0.4～10.0质量份的上述热稳定剂、1.0～10.0质量份的上述耐冲击改性剂。(The invention provides a resin composition for molding, and a molded article and a pipe using the resin composition for molding, wherein the resin composition for molding can be used for manufacturing a molded article with excellent heat resistance, mechanical performance and high surface smoothness. The present invention is a molding resin composition containing a chlorinated vinyl chloride resin, a heat stabilizer and an impact modifier. The chlorinated vinyl chloride resin has a chlorine content of 63 to 72% by mass, the heat stabilizer includes a calcium-containing compound and a zinc-containing compound, and the heat stabilizer and the impact modifier are contained in an amount of 0.4 to 10.0 parts by mass and 1.0 to 10.0 parts by mass, respectively, per 100 parts by mass of the chlorinated vinyl chloride resin.)

1. A molding resin composition comprising a chlorinated vinyl chloride resin, a heat stabilizer and an impact modifier, wherein,

the chlorinated vinyl chloride resin has a chlorine content of 63 to 72 mass%,

the heat stabilizer comprises a calcium-containing compound and a zinc-containing compound,

the heat stabilizer is contained in an amount of 0.4 to 10.0 parts by mass and the impact modifier is contained in an amount of 1.0 to 10.0 parts by mass based on 100 parts by mass of the chlorinated vinyl chloride resin.

2. The resin composition for molding according to claim 1, wherein the chlorinated vinyl chloride-based resin has structural units (a) to (c) represented by the following formulae (a) to (c), and the proportion of the structural unit (a) is 17.5 mol% or less, the proportion of the structural unit (b) is 46.0 mol% or more, and the proportion of the structural unit (c) is 37.0 mol% or less, based on the total mole number of the structural units (a), (b), and (c),

-CCl₂- (a)

-CHCl- (b)

-CH₂- (c)。

3. the molding resin composition according to claim 1 or 2, which contains 70% by mass or more of a chlorinated vinyl chloride-based resin.

4. The molding resin composition according to claim 1, 2 or 3, wherein the impact modifier is a methyl methacrylate-butadiene-styrene copolymer and/or an acrylonitrile-butadiene-styrene copolymer.

5. The molding resin composition according to claim 1, 2, 3 or 4, which is free of a β -diketone.

6. The molding resin composition according to claim 1, 2, 3, 4 or 5, wherein the heat distortion temperature HDT measured according to ASTM D648 is 110 ℃ or higher.

7. The molding resin composition according to claim 1, 2, 3, 4, 5 or 6, wherein the unit classification specified by ASTM D1784 is at least 2-4-4-4-8.

8. The molding resin composition according to claim 1, 2, 3, 4, 5, 6 or 7, wherein the IZOD notched impact strength at the notched portion is 266.9J/m or more.

9. A molded article obtained by molding the resin composition for molding according to claim 1, 2, 3, 4, 5, 6, 7 or 8.

10. A pipe molded from the molding resin composition according to claim 1, 2, 3, 4, 5, 6, 7 or 8.

11. The pipe according to claim 10, characterized in that it is used for hot and cold water applications.

Technical Field

The present invention relates to a molding resin composition capable of producing a molded article having excellent heat resistance and mechanical properties and high surface smoothness, and a molded article and a pipe using the molding resin composition.

Background

Conventionally, vinyl chloride resins (hereinafter referred to as PVC) have been used in a variety of fields as materials having excellent mechanical strength, weather resistance, and chemical resistance. However, the following developments have been made because of poor heat resistance: chlorinated vinyl chloride-based resins (hereinafter referred to as CPVC) having improved heat resistance are obtained by chlorinating PVC. PVC has a low heat distortion temperature and a usable upper limit temperature of about 60 to 70 ℃ and is therefore unusable for hot water, while CPVC has a heat distortion temperature 20 to 40 ℃ higher than that of PVC and is therefore usable for hot water, and is suitable for heat-resistant pipes, heat-resistant joints, heat-resistant valves, heat-resistant plates, and the like.

On the other hand, heat-resistant pipes using CPVC are often used for hot water supply pipes, and if the heat resistance is insufficient, the pipe is deformed to a large extent when hot water is supplied, and the pipe is damaged or leaks water, and therefore, higher heat resistance is required.

On the other hand, for example, patent document 1 proposes a heat-resistant vinyl chloride resin pipe having heat resistance and hygienic properties, as well as easy workability and adhesion, using a chlorinated vinyl chloride resin having a chlorine content of 67.5 wt% or more and a specific compounding agent.

However, CPVC has a problem that the heat resistance of the molded article is improved as the degree of chlorination is higher, but the molded article has a higher viscosity and a longer stress relaxation time than general PVC, and therefore the smoothness of the molded article is deteriorated and the unevenness of the inner surface is large. Such problems are not only poor appearance but also propagation of bacteria due to retention of water or the like easily caused by the influence of irregularities on the surface, and therefore it is difficult to use the molded product of CPVC as a pipe for supplying hot water or a pipe for ultrapure water for plant equipment.

On the other hand, patent document 2 describes a method for improving heat resistance by adding a specific amount of an organotin stabilizer, a lubricant, and the like to CPVC containing chlorine at a high concentration.

However, this method also requires the use of CPVC having a high chlorine content, and therefore, the problem of poor moldability associated with the reduction in flowability still remains unsolved.

Disclosure of Invention

Problems to be solved by the invention

The purpose of the present invention is to provide a molding resin composition that can produce a molded article having excellent heat resistance and mechanical properties and high surface smoothness, and to provide a molded article and a pipe that use the molding resin composition.

Means for solving the problems

The present invention is a molding resin composition containing a chlorinated vinyl chloride resin, a heat stabilizer and an impact modifier, wherein the chlorinated vinyl chloride resin has a chlorine content of 63 to 72% by mass, the heat stabilizer contains a calcium-containing compound and a zinc-containing compound, and the heat stabilizer and the impact modifier are contained in an amount of 0.4 to 10.0 parts by mass and 1.0 to 10.0 parts by mass, respectively, per 100 parts by mass of the chlorinated vinyl chloride resin.

The present invention is described in detail below.

The inventors of the present invention have conducted extensive studies and found that: the present inventors have found that a molded article having excellent thermal stability and high impact resistance and surface smoothness can be produced by adding specific amounts of a thermal stabilizer and an impact modifier containing a calcium-containing compound and a zinc-containing compound to a molding resin composition containing a chlorinated vinyl chloride resin, and completed the present invention.

In particular, in the present invention, since excellent heat resistance can be achieved even when a chlorinated vinyl chloride-based resin having a low chlorine content is used, when the chlorinated vinyl chloride-based resin is used for a heat-resistant pipe, damage due to deformation when hot water is supplied can be suppressed.

The molding resin composition of the present invention contains a chlorinated vinyl chloride resin (hereinafter also referred to as "CPVC").

The CPVC has a chlorine content of 63 to 72 mass%.

The heat resistance of the molded article is sufficient by setting the chlorine content to 63 mass% or more, and the moldability is improved by setting the chlorine content to 72 mass% or less. The chlorine content is preferably 66 mass% or more, and more preferably 69 mass% or less.

The chlorine content in the CPVC can be measured by the method described in JIS K7229.

The gelling time of the CPVC is preferably 100 to 200 seconds. More preferably 110 to 190 seconds.

When the gelation time is within the above range, the resin is appropriately dispersed and fused, and the appearance and physical properties can be improved during molding.

The gelation time is: the sample in which the thermal stabilizer, lubricant, and impact modifier were added to CPVC was subjected to rotor rotation by LABO plastics or the like, and the motor torque was the most increased time.

The UV absorbance of the CPVC at a wavelength of 216nm is preferably 8.0 or less, more preferably 0.1 or more and 0.8 or less.

In addition, in the ultraviolet absorption spectrum, the wavelength of 216nm is a wavelength at which — CH ═ CH — C (═ O) -and-CH ═ CH — CH ═ CH-in the CPVC, which are heterogeneous structures, show absorption.

The value of the UV absorbance of CPVC can be used as an index for thermal stability by quantifying the amount of a different structure in the molecular chain during the chlorination reaction. In the molecular structure of CPVC, chlorine atoms carried by carbons adjacent to the carbon forming a double bond are unstable. Therefore, the chlorine atom is used as the starting point to generate HCl removal. That is, as the value of UV absorbance at a wavelength of 216nm is larger, HCl elimination is more likely to occur, and thermal stability is lowered.

In particular, when the chlorine content of the CPVC is 63 mass% or more and less than 69 mass%, the value of UV absorbance is preferably 0.8 or less. When the value of UV absorbance exceeds 0.8, the influence of the heterogeneous structure in the molecular chain becomes large, and as a result, the thermal stability may be lowered.

When the chlorine content of the CPVC is 69 mass% or more and 72 mass% or less, the value of UV absorbance is preferably 8.0 or less. When the value of the UV absorbance exceeds 8.0, the influence of the heterogeneous structure in the molecular chain becomes large, and the thermal stability is lowered.

The time required for HCl removal at 190 ℃ of the CPVC to reach 7000ppm is preferably 60 seconds or longer, and more preferably 100 seconds or longer.

The CPVC generates HCl gas when thermally decomposed at a high temperature. In general, as the chlorination degree of CPVC becomes higher, the VC unit decreases, and therefore, the HCl desorption amount tends to decrease. However, as the degree of chlorination increases, the heterogeneous chlorinated state and heterogeneous structure increase, and the thermal stability decreases. Therefore, by measuring the amount of HCl removal, it is possible to analyze the uneven chlorination state and the increase in the heterogeneous structure. For example, the time required for the HCl elimination amount at 190 ℃ to become 7000ppm can be used as an index of thermal stability, and the shorter the time, the lower the thermal stability.

In particular, when the chlorine content of the CPVC is 63 mass% or more and less than 69 mass%, the time required for the HCl removal amount at 190 ℃ to reach 7000ppm is preferably 60 seconds or more. If the time is less than 60 seconds, thermal stability is greatly impaired. Therefore, the time is preferably 60 seconds or longer, more preferably 70 seconds or longer, and further preferably 80 seconds or longer.

When the chlorine content of the CPVC is 69 mass% or more and 72 mass% or less, the time is preferably 100 seconds or more. If the time is less than 100 seconds, the thermal stability is greatly lowered, and therefore, it is preferably 100 seconds or more, more preferably 120 seconds or more, and further preferably 140 seconds or more.

The time required for the HCl desorption at 190 ℃ to reach 7000ppm can be determined as follows. First, 1g of chlorinated vinyl chloride resin was put into a test tube, heated at 190 ℃ using an oil bath, and the generated HCl gas was recovered. The recovered HCl gas was dissolved in 100ml of ion-exchanged water, and the pH was measured. The HCl concentration (ppm) was calculated based on the pH (i.e., several g of HCl was generated per 100 ten thousand g of chlorinated vinyl chloride-based resin). The time until the HCl concentration reached 7000ppm was measured.

The CPVC has structural units (a) to (c) represented by the following formulae (a) to (c), and the proportion of the structural unit (a) is preferably 17.5 mol% or less, the proportion of the structural unit (b) is preferably 46.0 mol% or more, and the proportion of the structural unit (c) is preferably 37.0 mol% or less, based on the total mole number of the structural units (a), (b), and (c). This CPVC has high thermal stability and good moldability.

[ solution 1]

-CCl₂- (a)

-CHCl- (b)

-CH₂- (c)

The molar ratio of the constituent units (a), (b) and (c) of the CPVC reflects the site where chlorine is introduced when the vinyl chloride resin (PVC) is chlorinated. Ideally, PVC before chlorination is in a state where the structural unit (a), the structural unit (b), and the structural unit (c) are substantially 0 mol%, 50.0 mol%, and 50.0 mol%, respectively, but the structural unit (c) decreases with chlorination, and the structural unit (b) and the structural unit (a) increase. In this case, when the number of structural units (a) which are unstable due to large steric hindrance is excessively increased or chlorinated sites and non-chlorinated sites are present in the same particle of CPVC, the unevenness in the chlorinated state becomes large. If this inhomogeneity becomes large, the thermal stability of the CPVC is significantly impaired.

On the other hand, in the present invention, by setting the molar ratio of the constituent units (a), (b), and (c) of the CPVC to be within the above range, the CPVC becomes highly uniform and has good thermal stability.

In the present invention, the proportion of the structural unit (a) is 17.5 mol% or less based on the total mole number of the structural units (a), (b) and (c), but the proportion of the structural unit (a) is preferably 16.0 mol% or less. Further, it is preferably 2.0 mol% or more.

The proportion of the structural unit (b) is 46.0 mol% or more based on the total mole number of the structural units (a), (b), and (c), but the proportion of the structural unit (b) is preferably 53.5 mol% or more. Further, it is preferably 70.0 mol% or less.

Further, the proportion of the structural unit (c) is 37.0 mol% or less with respect to the total mole number of the structural units (a), (b), and (c), but the proportion of the structural unit (c) is preferably 30.5 mol% or less. Further, it is preferably 1.0 mol% or more.

In the present invention, it is particularly preferable that the proportion of the structural unit (b) is 58.0 mol% or more and the proportion of the structural unit (c) is 35.8 mol% or less. With such a configuration, higher thermal stability can be obtained.

The molar ratio of the structural units (a), (b), and (c) of CPVC can be measured by molecular structure analysis using NMR. NMR analysis can be carried out according to the methods described in R.A. Komoroski, R.G.Parker, J.P.shocker, Macromolecules, 1985, 18, 1257-1265.

The PVC moiety of the CPVC, which is not chlorinated, in the molecular structure thereof can be represented by a structural unit (d) represented by the following formula (d), and is referred to as a VC unit in the present specification.

The content of VC units in the molecular structure of the CPVC used in the present invention, which are not less than the quadruplex region, is preferably not more than 30.0 mol%. Here, VC units above the quadruplex region refer to a portion to which 4 or more VC units are continuously bonded.

[ solution 2]

-CH₂-CHCl- (d)

When the VC units present in the CPVC become starting points of HCl elimination and the VC units are continuous, a continuous HCl elimination reaction called a zipper reaction easily occurs. That is, as the amount of VC units in the four-chain region or more increases, HCl desorption is more likely to occur, and thermal stability in CPVC decreases. Therefore, the VC unit in the four-chain region or more is preferably 30.0 mol% or less, and more preferably 28.0 mol% or less. When the chlorine content in the CPVC is 69 mass% or more and less than 72 mass%, the VC unit in the quadruplex region or more is preferably 18.0 mol% or less, and more preferably 16.0 mol% or less.

The content of vinyl chloride units in the four-chain region or more contained in the molecular structure can be measured by molecular structure analysis using NMR.

The CPVC is a chlorinated vinyl chloride resin (PVC).

As the PVC, a vinyl chloride homopolymer, a copolymer of a monomer having an unsaturated bond copolymerizable with a vinyl chloride monomer and a vinyl chloride monomer, a graft copolymer obtained by graft-copolymerizing a vinyl chloride monomer to a polymer, and the like can be used. These polymers may be used alone, or 2 or more of them may be used in combination.

Examples of the monomer having an unsaturated bond copolymerizable with the vinyl chloride monomer include α -olefins, vinyl esters, vinyl ethers, (meth) acrylates, aromatic ethylenes, halogenated ethylenes, and N-substituted maleimides, and 1 or 2 or more of them can be used.

Examples of the α -olefins include ethylene, propylene, and butene.

Examples of the vinyl esters include vinyl acetate and vinyl propionate.

Examples of the vinyl ethers include butyl vinyl ether and cetyl vinyl ether.

Examples of the (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, butyl acrylate, and phenyl methacrylate.

Examples of the aromatic vinyl include styrene and α -methylstyrene.

Examples of the halogenated ethylenes include vinylidene chloride and vinylidene fluoride.

Examples of the N-substituted maleimide include N-phenylmaleimide and N-cyclohexylmaleimide.

The polymer to be graft-copolymerized with vinyl chloride is not particularly limited as long as vinyl chloride is graft-polymerized. Examples thereof include ethylene copolymers, acrylonitrile-butadiene copolymers, polyurethanes, chlorinated polyethylenes, and chlorinated polypropylenes. These may be used alone, or 2 or more of them may be used in combination.

Examples of the ethylene copolymer include an ethylene-vinyl acetate copolymer, an ethylene-vinyl acetate-carbon monoxide copolymer, an ethylene-ethyl acrylate copolymer, an ethylene-butyl acrylate-carbon monoxide copolymer, an ethylene-methyl methacrylate copolymer, and an ethylene-propylene copolymer.

The average polymerization degree of the PVC is not particularly limited, but is preferably 400 to 3000, more preferably 600 to 1500, which is generally used. The average polymerization degree can be determined by JIS K6720-2: 1999, the measurement was carried out by the method described in.

The polymerization method of the PVC is not particularly limited, and conventionally known aqueous suspension polymerization, bulk polymerization, solution polymerization, emulsion polymerization, and the like can be used.

In the molding resin composition of the present invention, the content of the CPVC is preferably 70 to 95% by mass. By containing CPVC in this range, a molded article having both heat resistance and impact resistance and excellent surface smoothness can be obtained.

The molding resin composition of the present invention contains a heat stabilizer comprising a calcium-containing compound and a zinc-containing compound. Since the heat stabilizer does not contain a heavy metal, a molding resin composition containing no heavy metal can be obtained.

In addition, when such a thermal stabilizer is used, hydrochloric acid generated by thermal decomposition of the chlorinated vinyl chloride-based resin immediately reacts with a zinc compound to form zinc chloride. Further, the growth of polyene produced by the desalting of chlorinated vinyl chloride resin is stopped by the binding thereof with calcium alkylcarboxylate, thereby suppressing color development.

On the other hand, the zinc chloride produced has a property of promoting thermal decomposition of the chlorinated vinyl chloride resin, but in the present invention, the zinc chloride reacts with calcium alkylcarboxylate to produce calcium chloride and zinc alkylcarboxylate. As a result, the above-mentioned thermal stabilizer has a remarkable synergistic effect because the action of the zinc compound to rapidly capture hydrochloric acid is utilized and the action of zinc chloride to promote thermal decomposition is suppressed.

The calcium-containing compound is preferably calcium alkylcarboxylate.

Examples of the calcium alkylcarboxylate include calcium salts of valeric acid, caproic acid, heptanoic acid, caprylic acid, cyclohexylpropionic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, 12-hydroxystearic acid, arachidic acid, behenic acid, lignoceric acid, montanic acid, and the like.

Among them, calcium alkylcarboxylates having 8 to 28 carbon atoms are preferably used.

Examples of the zinc-containing compound include an inorganic zinc compound and an organic zinc compound.

Examples of the inorganic zinc compound include compounds derived from a system including a carbonate, a chloride, a sulfate, an oxide, a hydroxide, a basic oxide, and a mixed oxide of zinc.

Examples of the above-mentioned organozinc compound include an alkylzinc compound such as dialkylzinc and/or monoalkylzinc, an organoaliphatic zinc carboxylate, an unsubstituted or substituted organoaromatic zinc carboxylate, an organozinc phosphite, a substituted or unsubstituted zinc phenoxide, a zinc amino acid or its derivative, and a zinc organothiolate.

Examples of the organic aliphatic carboxylic acid constituting the organic aliphatic carboxylic acid zinc include montanic acid, rice bran fatty acid, behenic acid, erucic acid, stearic acid, oleic acid, linoleic acid, rice fatty acid, ricinoleic acid, myristic acid, palmitic acid, lauric acid, lower fatty acid, caprylic acid, isostearic acid, dimer acid, naphthenic acid, and acetic acid.

The organic aliphatic carboxylic acid includes dicarboxylic acids such as azelaic acid, sebacic acid, adipic acid, succinic acid, malonic acid, maleic acid, crotonic acid, malic acid, and tartaric acid, and monoesters thereof.

Further, examples of the organic aliphatic carboxylic acid include citric acid and its monoester or diester, lactic acid, glycolic acid, thiodipropionic acid and its monoester, and the like.

Examples of the unsubstituted or substituted aromatic carboxylic acid constituting the unsubstituted or substituted organic aromatic carboxylic acid zinc include benzoic acid, o-toluic acid, m-toluic acid, p-tert-butylbenzoic acid, p-hydroxybenzoic acid, salicylic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, and monoesters or diesters thereof.

Examples of the organic phosphorous acid constituting the organic zinc phosphite include acid phosphites which are reaction products of aliphatic alcohols and phosphorus pentoxide. Specific examples thereof include butyl acid phosphite, octyl acid phosphite, stearyl acid phosphite, and behenyl acid phosphite.

Examples of the substituted or unsubstituted phenol constituting the above-mentioned substituted or unsubstituted zinc phenol include phenol, cresol, mixed xylene, octylphenol, nonylphenol, dinonylphenol, cyclohexylphenol and phenylphenol. Examples of the substituted or unsubstituted phenol include bisphenol a, bisphenol S, bisphenol F, esters of p-hydroxybenzoic acid, and esters of salicylic acid.

Examples of the amino acid and its derivative include calcined glutamic acid, glycine, alanine, and the like.

Examples of the organic thiol constituting the zinc organosulfurol include lauryl thiol, thioglycolic acid and esters thereof, mercaptopropionic acid and esters thereof, and thiomalic acid and monoesters or diesters thereof.

The heat stabilizer includes a calcium-containing compound and a zinc-containing compound, but is preferably a mixture of the calcium-containing compound and the zinc-containing compound.

Examples of the form of the heat stabilizer include powder and granular form. By forming the heat stabilizer in this form, the heat stabilizer can be used as a one pack (one pack).

When the heat stabilizer is a powder or granule, the particle size thereof can be arbitrarily adjusted according to the purpose, and generally, the average particle size is preferably 50 μm to 5mm, particularly preferably 70 μm to 2 mm.

As a method for producing the heat stabilizer for the granular material, for example, a known granulation method itself, such as an extrusion granulation method, a spray granulation method, a rotary disk granulation method, a rotary granulation method, or a compression granulation method, can be used.

The heat stabilizer preferably has a heat loss rate of less than 5% by mass at 230 ℃.

When the heat loss rate at 230 ℃ is 5% by mass or more, the strength of the molded article may be insufficient due to the inclusion of air bubbles therein, or a striped pattern may be formed in the vicinity of the surface of the molded article, resulting in appearance defects.

The heat loss rate at 230 ℃ is more preferably less than 3% by mass.

The lower limit is not particularly limited, but is preferably 0.1% by mass.

The heat loss rate at 230 ℃ can be measured by a Thermogravimetry (TG) apparatus.

The heat stabilizer comprises a calcium-containing compound and a zinc-containing compound, and the mixing ratio of the calcium-containing compound to the zinc-containing compound (calcium-containing compound: zinc-containing compound) is preferably 9: 1 to 4: 6. Further, the mixing ratio is more preferably 8: 2 to 5: 5.

In the molding resin composition of the present invention, the content of the heat stabilizer is 0.4 to 10.0 parts by mass with respect to 100 parts by mass of the chlorinated vinyl chloride-based resin. When the heat stabilizer is contained in this range, the heat stability can be further improved and the good appearance of the molded article can be maintained. The content of the heat stabilizer is more preferably in the range of 0.4 to 6.0 parts by mass per 100 parts by mass of the chlorinated vinyl chloride resin. More preferably 0.5 to 3.0 parts by mass.

In the molding resin composition of the present invention, the content of calcium derived from the heat stabilizer is preferably 0.01 to 0.35% by mass, more preferably 0.02 to 0.30% by mass, based on the entire molding resin composition. The above numerical range can be calculated from the content of calcium contained in the heat stabilizer.

According to the present invention, a molding resin composition containing no heavy metal can be obtained.

In the present specification, heavy metal refers to a metal having a high density, and generally refers to a metal having a density of 4 to 5g/cm³The above metals. The term "free of heavy metals" means that the content of heavy metals is 1000ppm or less. The content of the heavy metal is preferably 100ppm or less.

Examples of the heavy metal include transition metals other than scandium, and examples thereof include Mn, Ni, Fe, Cr, Co, Cu, and Au. Further, metals (for example, Sn, Pb, Bi), Cd, Hg, and the like of p-block elements in the fourth period or less are also included.

The molding resin composition of the present invention preferably further contains a stabilizing assistant. By including the above-mentioned stabilizing assistant, thermal stability can be further improved.

As the above-mentioned stabilizing assistant, a stabilizing assistant not containing heavy metals can be used. Examples thereof include organic acid salts, epoxy compounds, phosphoric acid compounds, metal hydroxides, sodium adipate, glycidyl (meth) acrylate copolymers, oxetane compounds, vinyl ether compounds and zeolite compounds.

Examples of the epoxy compound include epoxidized soybean oil, epoxidized linseed oil, epoxidized tetrahydrophthalate, epoxidized polybutadiene, bisphenol a type epoxy compounds, and the like.

Examples of the phosphoric acid compound include organic phosphorus compounds, phosphites, phosphates, and the like.

Examples of the metal hydroxide include calcium hydroxide and sodium hydroxide.

These may be used alone, or 2 or more of them may be used in combination. The above-mentioned stabilizing assistant is different from calcium alkylcarboxylate and zinc compound.

Further, the heating decrement of the above-mentioned stabilizing assistant at 200 ℃ is preferably less than 5% by mass.

The molding resin composition of the present invention contains an impact modifier.

The impact modifier is used for the purpose of improving the impact resistance of the molded article obtained, and contains a rubber component.

Examples of the impact modifier include a copolymer of a (meth) acrylate monomer component and a rubber component, and a silicone acrylic rubber containing a (meth) acrylate monomer component and an organosiloxane monomer component.

Examples of the (meth) acrylate monomer component include alkyl (meth) acrylates having 1 to 12 carbon atoms, such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethyl (meth) acrylate, and 2-ethylhexyl methacrylate. These monomer components may be used alone, or 2 or more (for example, 3) monomers may be used in combination.

The content of the (meth) acrylate monomer component in the polymer constituting the impact modifier is not particularly limited, and is preferably 20 to 40% by mass.

The rubber component may be any of a diene component and a non-diene component, and may be a homopolymer or a copolymer (including a binary copolymer and a ternary copolymer). As the copolymer, random copolymerization, alternating copolymerization, block copolymerization and graft copolymerization may be mentioned.

Examples of the diene component include butadiene, isoprene, and chloroprene. Further, a copolymer containing a monomer component selected from the group consisting of a diene, an unsaturated nitrile, an α -olefin and an aromatic vinyl may be mentioned. More specifically, there may be mentioned a copolymer of an unsaturated nitrile and a diene (for example, an acrylonitrile-butadiene copolymer), a copolymer of an aromatic vinyl and a diene (for example, a butadiene-styrene copolymer, a styrene-isoprene copolymer), a copolymer of an olefin and a diene (for example, an ethylene-propylene-diene copolymer), and the like.

The content of the diene component in the polymer constituting the impact modifier is preferably 40 to 65% by mass.

Examples of the non-diene component include polymers containing 1 or 2 or more monomer components selected from alkyl (meth) acrylates having a second-order transition temperature of a homopolymer of less than-20 ℃, olefins, and organosiloxanes. More specifically, acrylic rubbers, olefin rubbers (e.g., ethylene-propylene rubbers, etc.), and silicone acrylic rubbers may be cited.

Examples of the alkyl (meth) acrylate having a second-order transition temperature of the homopolymer of less than-20 ℃ include alkyl (meth) acrylates and polar group-containing acrylates.

Examples of the alkyl (meth) acrylate include ethyl methacrylate, n-propyl methacrylate, isopropyl (meth) acrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl (meth) acrylate, and n-hexyl methacrylate. In addition, cyclohexyl (meth) acrylate and the like can also be used.

Examples of the polar group-containing acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-acryloyloxyethylphthalic acid.

More specifically, methyl methacrylate-butadiene-styrene copolymer (MBS), acrylonitrile-butadiene-styrene copolymer (ABS), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS), methyl methacrylate-butadiene copolymer (MB), and the like are preferably used as the impact modifier.

Further, as the impact modifier, methyl methacrylate-acrylic butadiene rubber copolymers, methyl methacrylate-acrylic butadiene rubber-styrene copolymers, methyl methacrylate-acrylic rubber copolymers, and methyl methacrylate- (acrylic silicone composite) copolymers are preferably used. Among them, methyl methacrylate-butadiene-styrene copolymer and/or acrylonitrile-butadiene-styrene copolymer are preferable.

In the molding resin composition of the present invention, the content of the impact modifier is 1.0 to 10.0 parts by mass per 100 parts by mass of the chlorinated vinyl chloride-based resin. When the impact modifier is contained in this range, the impact resistance of the molded article obtained can be further improved.

The lower limit of the content of the impact modifier is preferably 3.0 parts by mass, and the upper limit is preferably 8.0 parts by mass.

In the molding resin composition of the present invention, the ratio of the heat stabilizer to the impact resistance improver (impact resistance modifier/heat stabilizer) is preferably 10.0 or less. More preferably 0.6 to 10.0. By setting the amount within this range, a molded body having both heat resistance and impact resistance and excellent surface smoothness can be obtained. More preferably 1.0 to 8.5.

The impact modifier is preferably in the form of particles, and the average particle diameter is preferably small. The average particle diameter of the impact modifier particles is preferably 0.1 to 200 μm.

The molding resin composition of the present invention preferably further contains an antioxidant.

As the antioxidant, for example, a phenol-based antioxidant, a phosphate-based antioxidant, a sulfur-based antioxidant, an amine-based antioxidant, and the like can be used. These may be used alone or in combination of two or more. Among these, phenol antioxidants are preferable, and hindered phenol antioxidants are particularly preferable.

Examples of the hindered phenol-based antioxidant include 2, 6-di-t-butyl-p-cresol, 2, 6-diphenyl-4-octadecyloxyphenol, stearyl (3, 5-t-butyl-4-hydroxyphenyl) propionate, distearyl (3, 5-t-butyl-4-hydroxybenzyl) phosphonate, 2 '-methylenebis (4-methyl-6-t-butylphenol), 2' -methylenebis (4-ethyl-6-t-butylphenol), bis [3, 3-bis (4-hydroxy-3-t-butylphenyl) butyrate ] diol, 4 '-butylidenebis (6-t-butyl-m-cresol), 2' -ethylidenebis (4, 6-di-t-butylphenol), 2, 2' -ethylidenebis (4-sec-butyl-6-tert-butylphenol), 1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [ 2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl ] terephthalate, 1, 3, 5-tris (2, 6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1, 3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) -2, 4, 6-trimethylbenzene, 1, 3, 5-tris [ (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl ] isocyanurate, pentaerythritol-tetrakis [ methylene-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 2-tert-butyl-4-methyl-6- (2 '-acryloyloxy-3' -tert-butyl-5 '-methylbenzyl) phenol, 3, 9-bis (1', 1 '-dimethyl-2' -hydroxyethyl) -2, 4, 8, 10-tetraoxaspiro [ 5, 5 ] undecane, bis [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ], and the like. Among these, 1, 3, 5-tris (3, 5-di-t-butyl-4-hydroxybenzyl) isocyanurate, pentaerythritol-tetrakis [ methylene-3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], and the like are preferable. These may be used alone, or 2 or more of them may be used in combination.

The heat loss rate of the antioxidant at 200 ℃ is preferably 0.1 mass% or more and less than 5 mass%.

When the heating loss rate at 200 ℃ is 5% by mass or more, bubbles are contained in the molded article and the strength becomes insufficient, or a striped pattern is generated in the vicinity of the surface and appearance defects are generated in some cases.

The heat loss rate at 200 ℃ is more preferably 0.1 mass% or more and less than 3 mass%.

In the molding resin composition of the present invention, the content of the antioxidant is preferably in the range of 0.1 to 3 parts by mass, more preferably 0.2 to 2.5 parts by mass, per 100 parts by mass of the chlorinated vinyl chloride-based resin. By including the antioxidant in this range, a molded article with less coloration due to yellowing can be obtained.

The molding resin composition of the present invention may be mixed with additives such as a lubricant, a processing aid, a heat resistance improver, an ultraviolet absorber, a light stabilizer, a filler, a thermoplastic elastomer, and a pigment, if necessary.

Examples of the lubricant include an internal lubricant and an external lubricant. The internal lubricant is used for the purpose of reducing the flow viscosity of the molten resin during molding and preventing frictional heat generation. The internal lubricant is not particularly limited, and examples thereof include butyl stearate, lauryl alcohol, stearyl alcohol, glycerol monostearate, stearic acid, and bisamide. These may be used alone, or 2 or more of them may be used in combination.

The heating loss rate of the lubricant at 200 ℃ is preferably 0.1 mass% to less than 5 mass%.

The external lubricant can be used for the purpose of improving the sliding effect between the molten resin and the metal surface during the molding process. The external lubricant is not particularly limited, and examples thereof include polyolefin waxes such as paraffin wax and polyethylene-based lubricant, ester waxes such as fatty acid ester-based lubricant, and montanic acid wax. These may be used alone, or 2 or more of them may be used in combination.

The heat resistance improver is not particularly limited, and examples thereof include an α -methylstyrene type resin, an N-phenylmaleimide type resin, and the like.

The light stabilizer is not particularly limited, and examples thereof include hindered amine light stabilizers and the like.

In the molding resin composition of the present invention, the content of the lubricant is preferably 0.3 to 5.0 parts by mass with respect to 100 parts by mass of the chlorinated vinyl chloride-based resin. By including the lubricant in this range, a molded article having excellent surface smoothness and free from occurrence of gray spots or foaming during molding can be produced.

The processing aid preferably contains an acrylic resin having a weight average molecular weight of 90 to 500 ten thousand.

Examples of the acrylic resin include homopolymers of acrylic acid, methacrylic acid, and (meth) acrylic acid esters, and (meth) acrylic copolymers containing these.

Examples of the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and the like. Examples of the (meth) acrylic acid esters include n-pentyl (meth) acrylate, isopentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and n-octyl (meth) acrylate. Wherein the (meth) acrylic acid represents acrylic acid or methacrylic acid. In the present invention, as the processing aid, a polymer of methyl (meth) acrylate (MMA) is preferably used.

The ultraviolet absorber is not particularly limited, and examples thereof include salicylic acid ester-based, benzophenone-based, benzotriazole-based, cyanoacrylate-based, and the like.

The pigment is not particularly limited, and examples thereof include organic pigments such as azo-based, phthalocyanine-based, selenium-based, and dye lake-based pigments; oxide-based pigments such as titanium dioxide, sulfide-selenide-based inorganic pigments such as ferricyanide-based inorganic pigments, and the like.

The molding resin composition of the present invention may contain a plasticizer for the purpose of improving processability during molding, and the use of a large amount of the plasticizer is not preferred because the thermal stability of a molded article may be lowered. The plasticizer is not particularly limited, and examples thereof include dibutyl phthalate, di-2-ethylhexyl adipate and the like.

The molding resin composition of the present invention may contain a thermoplastic elastomer for the purpose of improving workability. Examples of the thermoplastic elastomer include nitrile thermoplastic elastomers, olefin thermoplastic elastomers, vinyl chloride thermoplastic elastomers, styrene thermoplastic elastomers, urethane thermoplastic elastomers, polyester thermoplastic elastomers, and polyamide thermoplastic elastomers.

Examples of the nitrile thermoplastic elastomer include acrylonitrile-butadiene copolymer (NBR).

Examples of the olefinic thermoplastic elastomer include ethylene thermoplastic elastomers such as ethylene-vinyl acetate copolymer (EVA) and ethylene-vinyl acetate-carbon monoxide copolymer (EVACO).

Examples of the vinyl chloride-based thermoplastic elastomer include a vinyl chloride-vinyl acetate copolymer, a vinyl chloride-vinylidene chloride copolymer, and the like.

These thermoplastic elastomers may be used alone, or two or more of them may be used in combination.

The molding resin composition of the present invention preferably contains no β -diketone. The β -diketone is a component added to a conventional heat stabilizer for the purpose of improving heat stability. However, when a heat stabilizer containing a β -diketone is used, the appearance of a molded article is easily impaired when the resin composition is molded by extrusion molding or injection molding to produce the molded article. For example, yellow to reddish brown stripes having a thickness of about 0.1 to 1mm are formed on the surface of the molded article in parallel with the flow direction of the resin. In this way, the molded body with the damaged appearance becomes a defective product. In particular, when a mold used for a long time is used, such a defective product is likely to occur. However, according to the present invention, a molding resin composition having excellent thermal stability can be provided without using a heat stabilizer containing a β -diketone.

The Heat Distortion Temperature (HDT) of the molding resin composition of the present invention measured according to ASTM D648 is preferably 110 ℃ or higher and 120 ℃ or lower. Thereby enabling thermal expansion and contraction to be reduced.

The IZOD notched impact strength of the molding resin composition of the present invention at the notched part is preferably 266.9J/m or more and 800.7J/m or less. This makes it possible to obtain a molded article having excellent impact resistance.

The molding resin composition of the present invention preferably has a unit classification of at least 2-4-4-4-8 as defined in ASTM D1784. This enables to obtain a molded article having excellent heat resistance and impact resistance.

As a method for producing the molding resin composition of the present invention, the following method can be used, for example. The following method may be used, which performs the following steps: preparing a chlorinated vinyl chloride-based resin by suspending a vinyl chloride-based resin in an aqueous medium in a reaction vessel to prepare a suspension, introducing chlorine into the reaction vessel, and chlorinating the vinyl chloride-based resin by any conventionally known method; then the following steps are carried out: specific amounts of the heat stabilizer and the impact modifier are added to and mixed with the chlorinated vinyl chloride resin.

As the reaction vessel used in the step of producing the chlorinated vinyl chloride-based resin, for example, a generally used vessel such as an enameled stainless steel reaction vessel or a titanium reaction vessel can be used.

The method for preparing a suspension by suspending the vinyl chloride-based resin in an aqueous medium is not particularly limited, and a cake-like PVC obtained by subjecting PVC after polymerization to a monomer removal treatment may be used, or a dried product may be resuspended in an aqueous medium. Further, a suspension obtained by removing substances unsuitable for chlorination reaction from the polymerization system may be used, but a cake-like resin obtained by subjecting PVC after polymerization to a demonomerization treatment is preferably used.

As the aqueous medium, for example, ion-exchange-treated pure water can be used. The amount of the aqueous medium is not particularly limited, and is preferably 150 to 400 parts by mass per 100 parts by mass of PVC.

The chlorine introduced into the reaction vessel may be either liquid chlorine or gaseous chlorine. In order to inject a large amount of chlorine in a short time, it is effective to use liquid chlorine. Chlorine may be added during the reaction to adjust the pressure or to replenish chlorine. In this case, gaseous chlorine may be appropriately blown in addition to liquid chlorine. Preferably, chlorine obtained by purifying 5 to 10 mass% of chlorine in the liquefied gas cylinder is used.

The gauge pressure in the reaction vessel is not particularly limited, and is preferably in the range of 0.3 to 2MPa since the higher the chlorine pressure is, the more likely chlorine permeates into the PVC particles.

The method for chlorinating PVC in the suspended state is not particularly limited, and examples thereof include: a method of promoting chlorination by exciting PVC bonds and chlorine by thermal energy (hereinafter referred to as thermal chlorination); and a method of promoting chlorination by photoreactivity upon irradiation with light energy such as ultraviolet light (hereinafter referred to as photochlorination). The heating method in the case of chlorination by thermal energy is not particularly limited, and for example, heating from the reactor wall by an external jacket method is effective. In addition, when light energy such as ultraviolet light is used, a device capable of performing irradiation of light energy such as ultraviolet irradiation under conditions of high temperature and high pressure is required. The chlorination reaction temperature during the photochlorination is preferably 40-80 ℃.

Among the above-mentioned chlorination methods, a thermal chlorination method in which ultraviolet irradiation is not performed is preferable, and a method in which a chlorination reaction is promoted by exciting a bond or chlorine of a vinyl chloride resin with heat alone or heat and hydrogen peroxide is preferable.

In the case of the above-described chlorination reaction based on light energy, the amount of light energy required for chlorination of PVC is significantly affected by the distance between the PVC and the light source. Therefore, the surface and the inside of the PVC particles are subjected to different energies, and chlorination does not occur uniformly. As a result, CPVC with low uniformity was obtained. On the other hand, in the method of chlorination by heat without ultraviolet irradiation, a more uniform chlorination reaction can be achieved, and CPVC with high uniformity can be obtained.

When the chlorination is carried out by heating only, the temperature is preferably in the range of 70 to 140 ℃. If the temperature is too low, the chlorination rate decreases. If the temperature is too high, the HCl removal reaction occurs concurrently with the chlorination reaction, and the resulting CPVC is colored. The heating temperature is more preferably in the range of 100 to 135 ℃. The heating method is not particularly limited, and heating can be performed from the reaction vessel wall by, for example, an external jacket method.

In the chlorination, it is preferable to further add hydrogen peroxide to the suspension. The rate of chlorination can be increased by adding hydrogen peroxide. For hydrogen peroxide, it is preferable to add PVC in an amount of 5 to 500ppm per 1 hour of reaction time. If the amount of addition is too small, the effect of increasing the rate of chlorination cannot be obtained. If the amount is too large, the thermal stability of CPVC decreases.

When the hydrogen peroxide is added, the chlorination rate is increased, and thus the heating temperature can be lowered. For example, the temperature may be in the range of 65 to 110 ℃.

In the case of the chlorination, it is preferable to perform chlorination after the time when the final chlorine content reaches 5 mass% at a chlorine consumption rate of 0.010 to 0.015 Kg/PVC-Kg.5 min, and further perform chlorination after the time when the final chlorine content reaches 3 mass% at a chlorine consumption rate of 0.005 to 0.010 Kg/PVC-Kg.5 min. Here, the chlorine consumption rate means the chlorine consumption amount per 1kg of raw material PVC for 5 minutes.

By performing chlorination by the above-described method, CPVC having less unevenness in the chlorinated state and excellent thermal stability can be obtained.

The method for producing the molding resin composition of the present invention comprises the following steps: specific amounts of a specific heat stabilizer and an impact modifier are added to and mixed with the chlorinated vinyl chloride resin, and an antioxidant is added as needed.

The method of mixing the antioxidants is not particularly limited, and examples thereof include a method by hot blending and a method by cold blending.

According to the configuration of the present invention as described above, a molding resin composition having excellent thermal stability and containing no heavy metal such as lead, cadmium, or tin can be provided.

Further, according to another aspect of the present invention, there is provided a molded article molded from the molding resin composition of the present invention. Such a shaped body is also one of the present invention.

The molding method may be any conventionally known molding method, and examples thereof include extrusion molding and injection molding.

The molded article of the present invention does not contain heavy metals as in the molding resin composition of the present invention, and therefore has the excellent advantage of not adversely affecting the environment, and has excellent thermal stability and a good appearance, and therefore, can be suitably used for applications such as building parts, plumbing equipment, and housing materials.

The pipe molded from the molding resin composition of the present invention can be suitably used for hot water and cold water applications. Such a tube is also one of the present inventions.

The surface roughness (Rmax) of the surface of the molded article of the present invention is preferably 0.1 μm or more and 2 μm or less.

The average (WcA) of the filter waviness center line of the surface of the molded article of the present invention is preferably 0.1 μm or more and 2 μm or less. The filter waviness unevenness (Wct) is preferably 1.0 μm or more and 10 μm or less.

The surface roughness (Rmax) can be measured by a method in accordance with JIS B0601, and the filter waviness center line average (WcA) and the filter waviness unevenness (Wct) can be measured by a method in accordance with JIS B0610.

ADVANTAGEOUS EFFECTS OF INVENTION

The present invention provides a molding resin composition capable of producing a molded article having excellent heat resistance and mechanical properties and high surface smoothness, and a molded article and a pipe using the molding resin composition.

Detailed Description

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[ example 1]

(preparation of chlorinated vinyl chloride resin)

200kg of ion-exchanged water and 56kg of vinyl chloride resin having a polymerization degree of 1000 were put into an enameled reaction vessel having an inner volume of 300L. The mixture was stirred and further water was added to the reaction vessel to disperse the mixture in water. Then, the pressure was reduced to remove oxygen in the reaction vessel, and the temperature was raised to 90 ℃.

Then, chlorine was supplied into the reaction vessel so that the chlorine partial pressure became 0.4MPa, and a chlorination reaction was carried out while adding 0.2 mass% hydrogen peroxide at a rate of 1 part by mass per 1 hour (320 ppm/hour). The reaction was continued until the chlorine content of the chlorinated vinyl chloride resin reached 61 mass%. When the chlorine content of the chlorinated vinyl chloride resin reached 61 mass% (5 mass% before), the chlorination was performed by adjusting the average chlorine consumption rate to 0.012 kg/PVC-kg.5 min by reducing the amount of 0.2 mass% hydrogen peroxide added to 0.1 part by mass (200 ppm/hr) per 1 hour. When the chlorine content reached 63 mass% (3 mass%) the amount of 0.2 mass% hydrogen peroxide added was adjusted to 150 ppm/hr per 1 hour, and the chlorination was performed so that the average chlorine consumption rate reached 0.008 kg/PVC-kg.5 min. Thus, a chlorinated vinyl chloride-based resin having a chlorine content of 67.3 mass% was obtained. The chlorine content of the chlorinated vinyl chloride-based resin was measured in accordance with JIS K7229.

The gelation time of the chlorinated vinyl chloride-based resin was measured by the following method.

(measurement of gelation time)

A mixture sample was prepared by adding and mixing 1.2 parts by mass of a heat stabilizer, 1.0 part by mass of a polyethylene lubricant, 0.5 part by mass of an oxidized polyethylene lubricant, and 5.5 parts by mass of an impact modifier to 100 parts by mass of a chlorinated vinyl chloride resin. The following were used as a heat stabilizer, a polyethylene lubricant, an oxidized polyethylene lubricant, and an impact modifier.

Heat stabilizer (TVS #1380 manufactured by Nindong chemical industry Co., Ltd.)

Polyethylene lubricant (Hiwax 220MP, Mitsui chemical Co., Ltd.)

Oxidized polyethylene type lubricant (A-C316A, product of Honeywell Co., Ltd.)

Impact modifier (Kaneka KaNEACE M-511)

Next, 59g of the mixture sample was put into LABO PLASTOMIL (4C 150, manufactured by Toyo Seiki Seisaku-Sho Ltd.) at a temperature of 180 ℃ and preheated for 80 seconds, and then the rotor was rotated at a rotational speed of 30rpm, and the time when the motor torque was most increased was defined as the gelation time.

(preparation of chlorinated vinyl chloride resin composition)

To 100 parts by mass of the obtained chlorinated vinyl chloride-based resin (polymerization degree: 1000), 1.5 parts by mass of calcium stearate and 1.0 part by mass of zinc stearate as heat stabilizers and 6.0 parts by mass of MBS-1 resin as an impact modifier were added and mixed. As the MBS-1 resin, the following resins were used.

MBS-1 (methyl methacrylate-butadiene-styrene copolymer) resin: the content of the methyl methacrylate component was 28% by mass, the content of the diene component was 52% by mass, and the average particle diameter was 0.1 μm

Further, 0.3 part by mass of pentaerythritol tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ] (hindered phenol antioxidant, Irganox 1010, manufactured by BASF) was added and mixed as an antioxidant.

Further, 1.0 part by mass of a polyethylene lubricant (Hiwax 220MP, manufactured by Mitsui chemical Co., Ltd.), 0.5 part by mass of an ester lubricant (LOXIOL G-15, manufactured by Emery Oleo Chemicals Japan Co., Ltd.), and 3.0 parts by mass of titanium dioxide (TIPAQUE CR-90, manufactured by Stone Production Co., Ltd.) were added and mixed uniformly by a super mixer to obtain a chlorinated vinyl chloride resin composition.

(production of extrusion molded article)

The chlorinated vinyl chloride-based resin composition thus obtained was fed to a twin-screw counter-rotating conical extruder (manufactured by Yangtze Fayowa, Ltd., "SLM-50") having a diameter of 50mm, and the resin temperature and back pressure were 209.0 ℃ and 280.0kg/cm²And an extrusion amount of 25.0kg/hr, to prepare a tubular extrusion-molded article having an inner diameter of 20mm and a thickness of 3 mm.

Examples 2 to 21 and comparative examples 2 to 7

A chlorinated vinyl chloride-based resin composition and an extrusion-molded article were produced in the same manner as in example 1, except that the chlorinated vinyl chloride-based resin, the heat stabilizer, the impact modifier, and the lubricant were used in the kinds and amounts shown in table 1.

In examples 7 and 8, an ABS resin (acrylic component content: 34% by mass, diene component content: 53% by mass) was used in place of the MBS-1 resin.

In examples 20 and 21, MBS-2 resin (25 mass% of methyl methacrylate component, 60 mass% of diene component, and 0.1 μm of average particle diameter) and MBS-3 resin (25 mass% of methyl methacrylate component, 40 mass% of diene component, and 0.3 μm of average particle diameter) were used in place of MBS-1 resin.

Further, an acrylic modifier (methyl methacrylate-acrylic rubber copolymer, available from Mitsubishi chemical corporation, METABLEN W-450) was used in example 15, and a silicon modifier (silicone acrylic rubber, available from Mitsubishi chemical corporation, METABLEN S-2001) was used in example 16.

Comparative example 1

A chlorinated vinyl chloride resin composition and an extrusion molded article were produced in the same manner as in example 1, except that 2.5 parts by mass of a tin-based heat stabilizer (mercaptobutyltin, Mark292, manufactured by Garata chemicals) was used instead of 1.5 parts by mass of calcium stearate and 1.0 part by mass of zinc stearate as the heat stabilizer.

< evaluation >

The following evaluations were made with respect to the chlorinated vinyl chloride-based resin compositions and extrusion molded articles obtained in examples and comparative examples. The results are shown in Table 1.

[ evaluation of chlorinated vinyl chloride resin composition ]

< mechanical Properties (IZOD impact Strength, tensile elastic modulus, Heat distortion temperature) >

The chlorinated vinyl chloride-based resin composition thus obtained was fed to two 8-inch rolls, and kneaded at 205 ℃ for 3 minutes to prepare a sheet having a thickness of 1.0 mm. The obtained sheets were superposed, preheated for 3 minutes by pressing at 205 ℃ and then pressed for 4 minutes to obtain a pressed sheet having a thickness of 3 mm. Test pieces were cut out of the resulting pressboards by machining. Using the test piece, IZOD impact strength was measured in accordance with ASTM D256, and tensile strength and tensile modulus of elasticity were measured in accordance with ASTM D638. Further, according to ASTM D648 at 186N/cm²The heat distortion temperature was measured. The heat distortion temperature was measured after annealing the obtained pressed plate for 24 hours in a gill oven at 100 ℃.

< cell Classification >

The unit classification specified in ASTM D1784 was determined.

[ evaluation of molded article ]

< surface roughness >

The surface roughness (Rmax) was measured by a method in accordance with JIS B0601 using a surface roughness measuring apparatus (SURFCOM 480A, manufactured by tokyo precision corporation). The measurement conditions were: the evaluation length was 0.3mm, the measurement speed was 0.3mm/sec, and the cut-off value was 0.08 mm.

< degree of filter waviness >

The average center line of the filter waviness (filter center waviness, WcA) and the unevenness of the filter waviness (Wct) of the outer surface were measured by a method in accordance with JIS B0610 using a surface roughness measuring apparatus (SURFCOM 480A, manufactured by tokyo precision corporation). The measurement conditions were: the evaluation length is 30mm, the measurement speed is 3mm/sec, and the cut-off value is 0.25-8 mm.

[ Table 1]

Industrial applicability

The present invention provides a molding resin composition capable of producing a molded article having excellent heat resistance and mechanical properties and high surface smoothness, and a molded article and a pipe using the molding resin composition.