WO2022114072A1 - ポリオレフィン系樹脂用結晶化抑制剤、ポリオレフィン系樹脂組成物、成形品、ポリオレフィン系樹脂組成物の製造方法およびポリオレフィン系樹脂の結晶化抑制方法 - Google Patents
ポリオレフィン系樹脂用結晶化抑制剤、ポリオレフィン系樹脂組成物、成形品、ポリオレフィン系樹脂組成物の製造方法およびポリオレフィン系樹脂の結晶化抑制方法 Download PDFInfo
- Publication number
- WO2022114072A1 WO2022114072A1 PCT/JP2021/043251 JP2021043251W WO2022114072A1 WO 2022114072 A1 WO2022114072 A1 WO 2022114072A1 JP 2021043251 W JP2021043251 W JP 2021043251W WO 2022114072 A1 WO2022114072 A1 WO 2022114072A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- polyolefin
- polyolefin resin
- fatty acid
- nucleating agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/203—Solid polymers with solid and/or liquid additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/156—Heterocyclic compounds having oxygen in the ring having two oxygen atoms in the ring
- C08K5/1575—Six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
Definitions
- the present invention relates to a crystallization inhibitor for a polyolefin resin, a polyolefin resin composition, a molded product, a method for producing a polyolefin resin composition, and a method for suppressing crystallization of a polyolefin resin.
- the present invention relates to a crystallization inhibitor for a polyolefin resin, a polyolefin resin composition, a molded product, a method for producing the polyolefin resin composition, and a method for suppressing crystallization of the polyolefin resin.
- Patent Document 1 proposes a method of adding silicone oil.
- Patent Document 1 may not sufficiently suppress the crystallization of the polyolefin-based resin.
- an object of the present invention is a crystallization inhibitor for a polyolefin resin that can sufficiently suppress the crystallization of a polyolefin resin, a polyolefin resin composition, a molded product, a method for producing a polyolefin resin composition, and a polyolefin. It is an object of the present invention to provide a method for suppressing crystallization of a system resin.
- the present inventors unexpectedly solve the above problems with the crystallization inhibitor for polyolefin resins including the nucleating agent for polyolefin resins and the lubricant. We found that and came to complete the present invention.
- the crystallization inhibitor for a polyolefin resin of the present invention is a crystallization inhibitor for a polyolefin resin, which comprises (A) a nucleating agent for a polyolefin resin and (B) a lubricant.
- the (A) nucleating agent for a polyolefin resin contains (A-1) an acetal compound represented by the following general formula (1), and the above (B).
- the lubricant preferably comprises at least one selected from the group consisting of (B-1) fatty acid esters and (B-2) fatty acid amides.
- R 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
- R 2 , R 3 , R 4 and R 5 independently represent a hydrogen atom, a halogen atom, and a cyano group.
- It represents an alkylene dioxy group of the number 1 to 4
- X represents a single bond, -CH (OH) -group or -CH (OH) CH (OH) -group.
- the (B-1) fatty acid ester preferably contains a glycerol fatty acid monoester
- the (B-2) fatty acid amide is a fatty acid monoamide and an alkylene. It preferably contains at least one selected from the group consisting of bis fatty acid amides.
- the present invention contains a polyolefin-based resin, (A) a nucleating agent for a polyolefin-based resin, and (B) a lubricant, and contains (A) a nucleating agent for a polyolefin-based resin with respect to 100 parts by mass of the polyolefin-based resin.
- the polyolefin-based resin composition is characterized in that the amount is 0.005 part by mass or more and 0.1 part by mass or less.
- the nucleating agent for (A) polyolefin-based resin contains (A-1) an acetal compound represented by the following general formula (1), and the (B) lubricant is: It preferably contains at least one selected from the group consisting of (B-1) fatty acid ester and (B-2) fatty acid amide.
- R 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
- R 2 , R 3 , R 4 and R 5 independently represent a hydrogen atom, a halogen atom, and a cyano group.
- It represents an alkylene dioxy group of the number 1 to 4
- X represents a single bond, -CH (OH) -group or -CH (OH) CH (OH) -group.
- the present invention is a molded product characterized by being obtained by molding the above-mentioned polyolefin resin composition.
- the present invention includes a blending step of blending (A) a nucleating agent for a polyolefin-based resin and (B) a lubricant with a polyolefin-based resin, and in the blending step, 100 parts by mass of the polyolefin-based resin.
- the present invention is a method for suppressing crystallization of a polyolefin-based resin, which comprises blending (A) a nucleating agent for a polyolefin-based resin and (B) a lubricant with a polyolefin-based resin.
- a crystallization inhibitor for a polyolefin resin that can sufficiently suppress the crystallization of a polyolefin resin, a polyolefin resin composition, a molded product, a method for producing a polyolefin resin composition, and a polyolefin resin.
- the crystallization inhibitor for a polyolefin resin of the present embodiment includes (A) a nucleating agent for a polyolefin resin and (B) a lubricant.
- the crystallization inhibitor for the polyolefin resin of the present embodiment the crystallization of the polyolefin resin can be sufficiently suppressed.
- the nucleating agent for (A) polyolefin resin may be, for example, a melt diffusion type nucleating agent.
- the melt-diffusion type nucleating agent is melted or dissolved in the polyolefin-based resin at the molding processing temperature of the polyolefin-based resin, dispersed in the resin matrix, and before the start of crystallization of the resin matrix in the cooling process of the molding process. It is a nucleating agent that crystallizes into a fine solid and acts as a fine solid.
- melt-diffusion type nucleating agent examples include (A-1) an acetal compound represented by the following general formula (1), (A-2) an amide compound represented by the following general formula (2), and the like.
- R 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms
- R 2 , R 3 , R 4 and R 5 are independent hydrogen atoms and halogens, respectively.
- X is a single bond, -CH (OH) -group or -CH.
- R 6 and R 7 each independently represent an alkyl group having 1 to 6 carbon atoms
- R 8 to R 15 independently represent a hydrogen atom, a halogen atom, a cyano group, and 1 carbon atom. It represents an alkyl group of up to 6 or an alkoxy group having 1 to 6 carbon atoms
- Y represents a single bond or an arcandyl group having 1 to 4 carbon atoms.
- the alkyl groups having 1 to 6 carbon atoms in R 1 to R 5 include a methyl group, an ethyl group, an n-propyl group and an isopropyl group.
- examples thereof include an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, an n-hexyl group and an isohexyl group.
- the alkoxy group having 1 to 6 carbon atoms in R2 to R5 includes a methoxy group, an ethoxy group, an n-propoxy group and an isopropoxy group. , N-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n-pentyloxy group, isopentyloxy group, n-hexyloxy group, isohexyloxy group and the like.
- alkylene group having 3 to 6 carbon atoms when R 2 and R 3 or R 4 and R 5 are linked to each other is, for example, , Propylene group, butylene group, pentylene group, hexylene group and the like.
- (A-1) In the acetal compound represented by the general formula (1), the alkylenedioxy group having 1 to 6 carbon atoms when R 2 and R 3 or R 4 and R 5 are linked to each other is used.
- a methylenedioxy group, an ethylenedioxy group, a propylenedioxy group, a butylenedioxy group, a pentylenedioxy group, a hexylenedioxy group and the like can be mentioned.
- examples of the halogen atom in R2 to R5 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
- R 1 , R 2 , R 3 , R 4 and R 5 are independently hydrogen atoms or carbon atoms 1 to 6, which are preferable. Is 1 to 4 alkyl groups, and X is preferably an —CH (OH) — group.
- R 1 to R 5 are the same as those in the general formula (1).
- R 2 and R 4 are independently alkyl groups having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms are preferable, and R 1 and R 4 are preferable.
- 3 and R 5 are independently hydrogen atoms or alkyl groups having 1 to 6 carbon atoms, preferably 1 to 4, respectively, and R 2 and R 4 are independently having 1 to 6 carbon atoms, preferably 1 It is more preferably an alkyl group of -4, wherein X is a —CH (OH) — group.
- (A-1) As a specific example of the acetal compound represented by the general formula (1), for example, the following compound No. 1 to No. 4 etc. can be mentioned. From the viewpoint of further sufficiently suppressing the crystallization of the polyolefin-based resin, (A-1) the acetal compound represented by the following general formula (1) is the compound No. 1. Compound No. 2. Compound No. 3 and compound No. It is preferable to contain at least one selected from the group consisting of 4, and the compound No. 1. Compound No. 2 and compound No. It is more preferable to contain at least one selected from the group consisting of 3, and the compound No. 1 and compound No. It is more preferable to contain at least one selected from the group consisting of 2, and the compound No. It is even more preferable to include 2.
- Examples of the method for producing an acetal compound represented by the general formula (1) include a method of dehydrating and condensing an algitol compound such as sorbitol and arylaldehyde in the presence of an acid catalyst.
- examples of the alkyl group having 1 to 6 carbon atoms in R 6 to R 15 include a methyl group, an ethyl group, an n-propyl group and an isopropyl group. , N-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, n-hexyl group, isohexyl group and the like.
- examples of the halogen atom in R8 to R15 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
- examples of the alkoxy group having 1 to 6 carbon atoms in R8 to R15 include a methoxy group, an ethoxy group, an n-propoxy group and an isopropoxy.
- examples thereof include a group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, a tert-butyloxy group, an n-pentyloxy group, an isopentyloxy group, an n-hexyloxy group and an isohexyloxy group.
- the alkanediyl group having 1 to 4 carbon atoms in Y includes a methylene group, an ethane-1,2-diyl group, and a propane-1,3.
- -Examples include an alkylene group such as a diyl group and a butane-1,4-diyl group, an ethane-1,1-diyl group, and a propane-2,2-diyl group.
- R 6 and R 7 are independently alkyl groups having 1 to 6 carbon atoms, and R 8 to R 15 are independent. It is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Y is an alkanediyl group having 1 to 4 carbon atoms.
- (A-2) As a specific example of the amide compound represented by the general formula (2), for example, the following compound No. 5 to No. 8 etc. can be mentioned. Among these, compound No. 5. Compound No. 6. Compound No. 8 is preferable, and compound No. 8 is preferable. 5. Compound No. 8 is more preferable.
- Examples of the method for producing the amide compound represented by the general formula (2) include a method of reacting a diamine compound with a carboxylated product in the presence of a base such as triethylamine.
- the nucleating agent for (A) polyolefin resin may be a dispersed nucleating agent.
- the dispersed nucleating agent is a nucleating agent that is solid at the molding processing temperature of the polyolefin-based resin, does not dissolve in the polyolefin-based resin, and disperses and acts in the resin matrix as a fine solid during melt-kneading. Is.
- Examples of the dispersed nucleating agent include (A-3) an aromatic phosphate ester metal salt represented by the following general formula (3).
- R 16 to R 21 independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, n represents 1 or 2, and when n is 1, M is an alkali metal or dihydroxy. It represents aluminum, where when n is 2, M represents an alkaline earth metal, zinc or hydroxyaluminum.
- R 18 and R 21 may be linked to each other to form a methylene group or an ethylene group.
- examples of the alkyl group having 1 to 6 carbon atoms in R 16 to R 21 include a methyl group, an ethyl group and n-.
- examples thereof include a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, an n-hexyl group and an isohexyl group.
- examples of the alkali metal in M include lithium, sodium and potassium. Further, examples of the alkaline earth metal in M include magnesium, calcium, barium and the like.
- R 16 to R 21 are independently hydrogen atoms or alkyl groups having 1 to 6 carbon atoms, respectively, and n Is 1, and M is preferably sodium.
- (A-3) As a specific example of the aromatic phosphate ester metal salt represented by the general formula (3), for example, the following compound No. 9-No. 12 is mentioned. Among these, compound No. 11. Compound No. 12 is preferable, and compound No. 12 is preferable. 11 is more preferable.
- A-3 As a method for producing an aromatic phosphate ester metal salt represented by the general formula (3), for example, phosphorus chloride is reacted with a phenol compound, and then a metal hydroxide such as sodium hydroxide is reacted. There is a method to make it.
- the nucleating agent for the (A) polyolefin resin is the general formula (A-1) (1). ), The amide compound represented by (A-2) general formula (2), and the aromatic phosphate ester metal salt represented by (A-3) general formula (3). It is preferable to contain at least one selected, and at least selected from the group consisting of (A-1) an acetal compound represented by the general formula (1) and (A-2) an amide compound represented by the general formula (2). It is more preferable to include one. Further, the nucleating agent for the polyolefin resin (A) may contain an aromatic phosphoric acid ester metal salt represented by the general formula (3) (A-3).
- examples of the (B) lubricant include (B-1) fatty acid ester, (B-2) fatty acid amide, fatty acid such as stearic acid, higher alcohol such as stearyl alcohol, mannitol, and hardened castor oil.
- the (B) lubricant is the (B-1) fatty acid ester and the (B-2) fatty acid. It preferably contains at least one selected from the group consisting of amides.
- the lubricant (B) may contain (B-1) fatty acid ester and (B-2) fatty acid amide.
- the lubricant (B) may contain (B-2) fatty acid amide and may not contain (B-1) fatty acid ester. Further, the (B) lubricant may contain (B-1) fatty acid ester and (B-2) fatty acid amide.
- fatty acid ester examples include fatty acid alkyl esters such as fatty acid methyl and fatty acid ethyl, alkylene glycol fatty acid monoesters such as ethylene glycol fatty acid monoester and propylene glycol fatty acid monoester, ethylene glycol fatty acid diester, and propylene glycol fatty acid diester.
- alkylene glycol fatty acid diester glycerol fatty acid monoester, glycerol fatty acid diester, glycerol fatty acid triester and the like
- pentaerythritol fatty acid monoester pentaerythritol fatty acid diester, pentaerythritol fatty acid triester, pentaerythritol fatty acid tetraester and the like.
- pentaerythritol fatty acid ester examples thereof include pentaerythritol fatty acid ester.
- the fatty acid residue constituting the (B-1) fatty acid ester may be, for example, one having 7 to 29 carbon atoms.
- the fatty acid residue refers to a group obtained by removing a carboxyl group from a fatty acid.
- the number of carbon atoms of the fatty acid residue is preferably 11 to 23, more preferably 13 to 21.
- Examples of the fatty acid residue include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, arachidic acid, arachidonic acid, behenic acid, lignoseric acid, cellotic acid, montanic acid, and melicic acid.
- -A group obtained by removing a carboxyl group from a fatty acid such as hydroxystearic acid or ricinoleic acid can be mentioned.
- a group obtained by removing a carboxyl group from lauric acid, myristic acid, palmitic acid, and stearic acid is preferable, and a group obtained by removing a carboxyl group from stearic acid is particularly preferable.
- the (B-1) fatty acid ester contains a glycerol fatty acid monoester.
- the glycerol fatty acid monoester include glycerol lauric acid monoester, glycerol myristic acid monoester, glycerol palmitic acid monoester, glycerol stearate monoester, glycerol oleic acid monoester, glycerol linoleic acid monoester, and glycerol linolene.
- Acid monoester glycerol arachidic acid monoester, glycerol arachidonic acid monoester, glycerol behenic acid monoester, glycerol lignoseric acid monoester, glycerol cellotic acid monoester, glycerol montanic acid monoester, glycerol melicinic acid monoester, Examples thereof include glycerol 12-hydroxystearic acid monoester and glycerol lysinol acid monoester.
- glycerol lauric acid monoester glycerol myristic acid monoester, glycerol palmitic acid monoester, and glycerol stearic acid monoester are preferable, and glycerol stearic acid monoester is particularly preferable.
- fatty acid amide examples include alkylene bis fatty acid amides such as fatty acid monoamide, methylene bis fatty acid amide and ethylene bis fatty acid amide, alkylol fatty acid amides such as methylol fatty acid amide and ethylol fatty acid amide, and N-alkyl fatty acid amides. Be done.
- Examples of the fatty acid residue constituting the (B-2) fatty acid amide include the same as those exemplified as the fatty acid residue constituting the (B-1) fatty acid ester.
- the (B-2) fatty acid amide contains at least one selected from the group consisting of fatty acid monoamides and alkylene bis fatty acid amides.
- the fatty acid amide may contain a fatty acid monoamide and may not contain an alkylene bis fatty acid amide.
- the (B-2) fatty acid amide may contain an alkylene bis fatty acid amide and may not contain a fatty acid monoamide.
- the (B-2) fatty acid amide may contain a fatty acid monoamide and an alkylene bis fatty acid amide.
- fatty acid monoamide examples include lauric acid amide, myristic acid amide, palmitic acid amide, stearate amide, oleic acid amide, linoleic acid amide, linolenic acid amide, erucic acid amide, arachidic acid amide, and arachidonic acid amide.
- examples thereof include behenic acid amide, lignoseric acid amide, cellotic acid amide, montanic acid amide, melisic acid amide, 12-hydroxystearic acid amide, ricinoleic acid amide and the like.
- lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, oleic acid amide and erucic acid amide are preferable, stearic acid amide, oleic acid amide and erucic acid amide are more preferable, and oleic acid amide, Elcaic acid amides are even more preferred, and oleic acid amides are even more preferred.
- alkylene bis fatty acid amide examples include methylene bislauric acid amide, methylene bismilistic acid amide, methylene bispalmitic acid amide, methylene bisstearic acid amide, methylene bisoleic acid amide, and methylene bislinol acid amide.
- methylene bislauric acid amide methylene bismilistic acid amide, methylene bispalmitic acid amide, methylene bisstearic acid amide, ethylene bislauric acid amide, ethylene bismilistic acid amide, ethylene bispalmitic acid amide, ethylene bisstearic acid amide.
- Acid amides are preferred, methylene bisstearic acid amides and ethylene bisstearic acid amides are more preferred, and ethylene bisstearic acid amides are particularly preferred.
- the content of the lubricant (B) may be, for example, 10 to 1000 parts by mass with respect to 100 parts by mass of the nucleating agent for the polyolefin resin (A).
- the content of the lubricant (B) is preferably 15 to 600 parts by mass, more preferably 25 to 400 parts by mass, and 30 to 30 parts by mass with respect to 100 parts by mass of the nucleating agent compound for (A) polyolefin resin. It is even more preferably 300 parts by mass, and even more preferably 50 to 300 parts by mass.
- the nucleating agent for a polyolefin resin contains (A-1) an acetal compound represented by the general formula (1), and (B).
- the lubricant may contain at least one selected from the group consisting of (B-1) fatty acid esters and (B-2) fatty acid amides.
- the crystallization inhibitor for a polyolefin resin of the present embodiment further includes a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, other antioxidants, a hindered amine compound, an ultraviolet absorber, a fatty acid metal salt, and the like.
- additives such as flame retardants, flame retardant aids, fillers, hydrotalcites, antistatic agents, fluorescent whitening agents, pigments, dyes, etc. (hereinafter referred to as "other additives"). It may include the above.
- phenolic antioxidant examples include 2,6-di-tert-butyl-4-ethylphenol, 2-tert-butyl-4,6-dimethylphenol, styrated phenol, and 2,2'-methylenebis (4).
- -Ethyl-6-tert-butylphenol 2,2'-thiobis- (6-tert-butyl-4-methylphenol)
- 2,2'-thiodiethylenebis [3- (3,5-di-tert-) Butyl-4-hydroxyphenyl) propionate]
- 2-methyl-4,6-bis (octylsulfanylmethyl) phenol, 2,2'-isobutylidenebis (4,6-dimethylphenol) isooctyl-3- (3) , 5-Di-tert-butyl-4-hydroxyphenyl) propionate, N, N'-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-
- Examples of the phosphorus antioxidant include triphenylphosphite, diisooctylphosphite, heptaxis (dipropylene glycol) triphosphite, triisodecylphosphite, diphenylisooctylphosphite, diisooctylphenylphosphite, and diphenyl.
- Tridecylphosphite triisooctylphosphite, trilaurylphosphite, diphenylphosphite, tris (dipropylene glycol) phosphite, dioleylhydrogenphosphite, trilauryltrithiophosphite, bis (tridecyl) phosphite, tris (Isodecyl) phosphite, tris (tridecyl) phosphite, diphenyldecylphosphite, dinonylphenylbis (nonylphenyl) phosphite, poly (dipropylene glycol) phenylphosphite, tetraphenyldipropylene glycol diphosphite, trisnonyl Phenyl Phenyl Phenyl Phenyl, Tris (2,4-di-tert-butylpheny
- sulfur-based antioxidant examples include tetrakis [methylene-3- (laurylthio) propionate] methane and bis (methyl-4- [3-n-alkyl (C12 / C14) thiopropionyloxy] 5-tert-butylphenyl.
- antioxidants include N-benzyl- ⁇ -phenylnitrone, N-ethyl- ⁇ -methylnitrone, N-octyl- ⁇ -heptylnitrone, N-lauryl- ⁇ -undecylnitrone, N-tetradecyl- ⁇ .
- hindered amine compound examples include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-. Tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3 , 4-Butan Tetracarboxylate, Tetrakiss (1,2,2,6,6-Pentamethyl-4-piperidyl) -1,2,3,4-Butane Tetracarboxylate, Bis (2,2,6,6- Tetramethyl-4-piperidyl) di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -di (tridecyl)- 1,2,3,4-butanetetracar
- Examples of the ultraviolet absorber include 2-hydroxybenzophenones such as 2,4-dihydroxybenzophenone and 5,5'-methylenebis (2-hydroxy-4-methoxybenzophenone); 2- (2-hydroxy-5-methylphenyl).
- 2-hydroxybenzophenones such as 2,4-dihydroxybenzophenone and 5,5'-methylenebis (2-hydroxy-4-methoxybenzophenone); 2- (2-hydroxy-5-methylphenyl).
- Benzotriazole 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2) -Hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-dicumylphenyl) benzotriazole, 2,2'-methylenebis (4-tert- Octyl-6-benzotri
- Examples of the fatty acid metal salt include linear or branched metal salts of fatty acids having 12 to 30 carbon atoms.
- Examples of the metal ion constituting the fatty acid metal salt include sodium ion, potassium ion, lithium ion, dihydroxyaluminum ion, calcium ion, zinc ion, barium ion, magnesium ion, hydroxyaluminum ion and the like.
- Sodium ion, potassium ion, lithium ion and calcium ion are preferable.
- fatty acids constituting the fatty acid metal salt include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, arachidic acid, arachidonic acid, behenic acid, lignoseric acid, serotinic acid, montanic acid and melicin. Acids, 12-hydroxystearic acid, ricinoleic acid and the like can be mentioned, and among these, myristic acid and stearic acid are preferable.
- Examples of the flame retardant include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyldiphenyl phosphate, cresyl-2,6-dixylenyl phosphate, resorcinolbis (diphenyl phosphate), (1-methylethylidene).
- FP-800 ”aromatic phosphate ester divinyl phenylphosphonate, diallyl phenylphosphonate, phosphonic acid ester such as phenylphosphonic acid (1-butenyl), phenyl diphenylphosphinate, methyl diphenylphosphinate, 9,10-dihydro Phenylic acid esters such as -9-oxa-10-phosphaphenanthrene-10-oxide derivative, phosphazene compounds such as bis (2-allylphenoxy) phosphazene, dicredylphosphazene, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, Melum polyphosphate, ammonium polyphosphate, piperazine phosphate, piperazine pyrophosphate, piperazine polyphosphate, phosphorus-containing vinylbenzyl compound and phosphorus-based flame retardants such as red phosphorus, metal hydroxides such as magnesium hydroxide and aluminum hydroxide,
- Bisphenol A type epoxy resin brominated phenol novolac type epoxy resin, hexabromobenzene, pentabromotoluene, ethylenebis (pentabromophenyl), ethylenebistetrabromophthalimide, 1,2-dibromo-4- (1,2-) Dibromoethyl) cyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis (tribromophenoxy) ethane, brominated polyphenylene ether, brominated polystyrene and 2,4,6-tris (tribromophenoxy) -1,3,5 -Examples include triazine, tribromophenylmaleimide, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromobisphenol A-type dimethacrylate, pentabromobenzyl acrylate, and bro
- the filler examples include talc, mica, calcium carbonate, calcium oxide, calcium hydroxide, magnesium carbonate, magnesium hydroxide, magnesium oxide, magnesium sulfate, aluminum hydroxide, barium sulfate, glass powder, glass fiber, clay, and dolomite.
- Silica, Alumina, Potassium Titanium Whisker, Wallastenite, Fibrous Magnesium Oxysulfate and the like, and the particle size (fiber diameter, fiber length and aspect ratio in the fibrous form) can be appropriately selected and used. ..
- talc is particularly preferably used because it has an excellent effect of imparting rigidity and is easily available.
- a surface-treated filler can be used if necessary.
- the hydrotalcites may be any complex salt compound containing magnesium, aluminum, hydroxyl group, carbonate group and arbitrary water of crystallization, and may be a natural product or a synthetic product. Further, the crystal structure, particle shape and particle size of hydrotalcites are not particularly limited. Further, the hydrotalcites may be those in which at least a part of magnesium or aluminum is replaced with another metal such as an alkali metal or zinc, and at least a part of a hydroxyl group or a carbonic acid group is a other anionic group. It may be replaced.
- the hydrotalcites may be those obtained by dehydrating crystalline water, and the surface thereof may be a fatty acid such as stearic acid, a fatty acid metal salt such as an alkali metal oleic acid salt, an alkali metal salt of dodecylbenzene sulfonic acid, or the like. It may be coated with an organic sulfonic acid metal salt, wax or the like.
- the antistatic agent examples include a low molecular weight antistatic agent using a nonionic, anionic, cationic or amphoteric surfactant, and a high molecular weight antistatic agent using a polymer compound.
- the nonionic surfactant include polyethylene glycol-type nonionic surfactants such as higher alcohol ethylene oxide adduct, higher alkylamine ethylene oxide adduct, and polyolefin glycol ethylene oxide adduct; polyethylene oxide, alkyl ether of polyhydric alcohol, and alkanolamine. Examples thereof include polyhydric alcohol-type nonionic surfactants such as fatty acid amides.
- anionic surfactant examples include carboxylates such as alkali metal salts of higher fatty acids; sulfate esters such as higher alcohol sulfates and higher alkyl ether sulfates, alkylbenzene sulfonates and alkyl sulfonates. Sulfates such as paraffin sulfonates; phosphate ester salts such as higher alcohol phosphates and the like can be mentioned.
- examples of the cationic surfactant include quaternary ammonium salts such as alkyltrimethylammonium salts.
- amphoteric tenside examples include amino acid-type amphoteric tenside agents such as higher alkylaminopropionate, and betaine-type amphoteric tenside agents such as higher alkyldimethylbetaine and higher alkyldihydroxyethylbetaine.
- amino acid-type amphoteric tenside agents such as higher alkylaminopropionate
- betaine-type amphoteric tenside agents such as higher alkyldimethylbetaine and higher alkyldihydroxyethylbetaine.
- anionic surfactants are preferable, and sulfonates such as alkylbenzene sulfonates, alkyl sulfonates, and paraffin sulfonates are particularly preferable.
- Examples of the polymer-type antistatic agent include ionomers and block polymers having polyethylene glycol as a hydrophilic portion.
- Examples of the ionomer include the ionomer described in JP-A-2010-132927.
- Examples of the polymer having polyethylene glycol as a hydrophilic portion include a polyether ester amide described in JP-A-7-10989, a polymer composed of polyolefin and polyethylene glycol described in US Pat. No. 6,552,131, and JP-A-2016-023254. Examples thereof include the polymer composed of polyester and polyethylene glycol described in the publication.
- Fluorescent whitening agent is a compound that absorbs ultraviolet rays of sunlight or artificial light, converts it into purple to blue visible light and radiates it, and promotes the whiteness and bluish tint of the molded product.
- fluorescent whitening agent include benzoxazole compounds C.I. I. Fluorescent Fluorescenter 184; Coumarin-based compound C.I. I. Fluorescent Fluorescent 52; diaminostilbene dissulphonic acid-based compound C.I. I. Fluorescent Fluorescenter 24, 85, 71 and the like can be mentioned.
- the pigment is not particularly limited, and a commercially available pigment can also be used.
- Specific examples of the pigment include, for example, Pigment Red 1, 2, 3, 9, 10, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123. , 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228.
- Pigment Green 7, 10, 36 Pigment Blue 15, 15 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 22, 24, 29, 56, 60, 61, 62, 64; Pigment Violet 1, 15, 19, 23, 27 , 29, 30, 32, 37, 40, 50 and the like.
- Dyes include azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridin dyes, stillben dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxadin dyes, and phthalocyanine dyes. , Cyanine dyes and the like.
- the method for producing the crystallization inhibitor for the polyolefin resin of the present embodiment is not particularly limited, and for example, (A) a nucleating agent for a polyolefin resin, (B) a lubricant and other additives as needed. After blending, a method of mixing using a mixing device such as an FM mixer, a mill roll, a Banbury mixer, and a super mixer can be mentioned.
- the crystallization inhibitor for the polyolefin resin of the present embodiment may be a one-pack composite additive further blended with a granulation aid such as a binder, a wax, a solvent, and silica, and granulated. Further, the crystallization inhibitor for the polyolefin resin of the present embodiment may be a masterbatch further containing a thermoplastic resin.
- thermoplastic resin contained in the master batch examples include polyolefin resins, polyamide resins, polyester resins, acrylic resins, urethane resins, styrene resins, polycarbonate resins, polyacetal resins and the like.
- polyolefin-based resin examples include polyethylene-based resins such as low-density polyethylene, linear low-density polyethylene, high-density polyethylene, crosslinked polyethylene, and ultrahigh-molecular-weight polyethylene, homopolypolypoly, random copolymer polypropylene, block copolymer polypropylene, and impact.
- Polypropylene-based resins such as copolymer polypropylene, high-impact copolymer polypropylene, maleic anhydride-modified polypropylene, polybutene-1, cycloolefin polymer, poly-3-methyl-1-butene, poly-3-methyl-1-pentene, poly-4.
- Examples thereof include ⁇ -olefin polymers such as -methyl-1-pentene, ethylene-methylmethacrylate copolymers, and ⁇ -olefin copolymers such as ethylene-vinyl acetate copolymers.
- One of these polyolefin resins may be used alone, or two or more thereof may be used in combination. Further, the polyolefin-based resin may be alloyed.
- the type for example, a Cheegler catalyst, a metallocene catalyst, etc.
- the type are not particularly limited and may be appropriately selected.
- the content of the thermoplastic resin in the masterbatch may be, for example, 90% by mass or less, preferably 80% by mass or less, and more preferably 60% by mass or less.
- the content of the thermoplastic resin in the masterbatch may be, for example, 10% by mass or more.
- the polyolefin-based resin composition of the present embodiment contains a polyolefin-based resin, (A) a nucleating agent for a polyolefin-based resin, and (B) a lubricant.
- the content of the nucleating agent for the (A) polyolefin resin with respect to 100 parts by mass of the polyolefin resin is 0.005 parts by mass or more and 0.1 parts by mass or less.
- the polyolefin-based resin composition of the present embodiment is such that the crystallization of the polyolefin-based resin is sufficiently suppressed.
- polyolefin-based resin examples include the same ones exemplified as the polyolefin-based resin that may be contained in the above-mentioned masterbatch. From the viewpoint of improving the heat resistance, it is particularly preferable that the polyolefin-based resin contains a polypropylene-based resin in the polyolefin-based resin composition of the present embodiment.
- the polyolefin-based resin may contain a polyolefin-based thermoplastic elastomer.
- the molded product made of the polyolefin-based resin composition has excellent impact resistance.
- the polyolefin-based resin composition of the present embodiment may further contain an elastomer other than the polyolefin-based thermoplastic elastomer.
- the molded product made of the polyolefin-based resin composition has even better impact resistance.
- the elastomer other than the polyolefin-based thermoplastic elastomer include thermoplastic elastomers such as polystyrene-based thermoplastic elastomers, polyvinyl chloride-based thermoplastic elastomers, polyurethane-based thermoplastic elastomers, polyester-based thermoplastic elastomers, and polyamide-based thermoplastic elastomers.
- thermoplastic elastomers are preferable from the viewpoint of improving the processability of the polyolefin-based resin composition and further reducing the weight of the molded product made of the polyolefin-based resin composition.
- the total content of the polyolefin-based thermoplastic elastomer and the content of the elastomer other than the polyolefin-based thermoplastic elastomer may be 50% by mass or less of the total resin component. It is preferably 1% by mass or less, and more preferably 25% by mass or less.
- the total content of the polyolefin-based thermoplastic elastomer and the content of the elastomer other than the polyolefin-based thermoplastic elastomer may be, for example, 5% by mass or more of the total resin component.
- Examples of (A) the nucleating agent for the polyolefin-based resin contained in the polyolefin-based resin composition of the present embodiment include the same as those contained in the above-mentioned crystallization inhibitor for the polyolefin-based resin.
- the content of the nucleating agent for the (A) polyolefin resin with respect to 100 parts by mass of the polyolefin resin is 0.005 parts by mass or more and 0.1 parts by mass or less.
- the content of the nucleating agent is more preferably 0.01 parts by mass or more and 0.08 parts by mass or less, and further preferably 0.02 parts by mass or more and 0.075 parts by mass or less.
- examples of the (B) lubricant contained in the polyolefin-based resin composition of the present embodiment include the same lubricants contained in the above-mentioned crystallization inhibitor for polyolefin-based resins.
- the content of the lubricant (B) with respect to 100 parts by mass of the polyolefin resin may be, for example, 0.001 part by mass or more and 10 parts by mass or less, preferably 0.005 part by mass or more and 1 part by mass or less. It is more preferably 01 parts by mass or more and 0.5 parts by mass or less, further preferably 0.01 parts by mass or more and 0.2 parts by mass or less, and 0.025 parts by mass or more and 0.15 parts by mass or less. Is even more preferable.
- the content of the lubricant (B) may be, for example, 10 to 1000 parts by mass, preferably 15 to 600 parts by mass, and 25 by mass with respect to 100 parts by mass of the nucleating agent for the polyolefin resin (A). It is more preferably to 400 parts by mass, further preferably 30 to 300 parts by mass, and even more preferably 50 to 300 parts by mass.
- the nucleating agent for the polyolefin-based resin contains (A-1) the acetal compound represented by the general formula (1), and (B) the lubricant contains. It may contain at least one selected from the group consisting of (B-1) fatty acid ester and (B-2) fatty acid amide.
- the polyolefin-based resin composition of the present embodiment may further contain other additives exemplified as the additives contained in the above-mentioned crystallization inhibitor for polyolefin-based resins.
- the method for producing a polyolefin-based resin composition of the present embodiment includes a compounding step of blending (A) a nucleating agent for a polyolefin-based resin and (B) a lubricant with the polyolefin-based resin. Then, in the compounding step, the compounding amount of the nucleating agent for the polyolefin resin (A) is 0.005 part by mass or more and 0.1 part by mass or less with respect to 100 parts by mass of the polyolefin resin.
- the method for producing the polyolefin-based resin composition of the present embodiment may include steps other than the compounding step. Examples of other steps include a preparation step and a melt-kneading step.
- a polyolefin-based resin (A) a nucleating agent for a polyolefin-based resin, and (B) a lubricant are prepared.
- (A) a nucleating agent for a polyolefin resin and (B) a lubricant are added to the polyolefin resin.
- the blending method is not particularly limited. For example, after adding a crystallization inhibitor for a polyolefin resin and other additives as necessary to the polyolefin resin, an FM mixer, a mill roll, a Banbury mixer, and a super mixer. Examples thereof include a method of mixing using a mixing device such as.
- (A) the nucleating agent for the polyolefin resin and (B) the lubricant may be blended as the above-mentioned crystallization inhibitor for the polyolefin resin.
- the method of blending is such that at least one component of (A) a nucleating agent for a polyolefin resin, (B) a lubricant and, if necessary, other additives is added to the polyolefin resin monomer or the polyolefin resin oligomer before polymerization.
- a method may be used in which the polymer is added during polymerization to carry out a polymerization reaction, and the remaining components are added to the obtained polymer.
- the method for producing the polyolefin-based resin composition may be a method including a melt-kneading step in which the mixture obtained in the blending step is further melt-kneaded using a melt-kneading device such as a single-screw extruder or a twin-screw extruder. ..
- the temperature of the melt-kneading may be, for example, 180 to 280 ° C.
- the method for producing the polyolefin-based resin composition may be a method including a granulation step of granulating the kneaded product obtained in the melt-kneading step.
- the granulation method is not particularly limited, and examples thereof include a method using a granulation device such as a granulator.
- the shape of the polyolefin-based resin composition obtained by granulation is not particularly limited, and may be, for example, pellet-shaped.
- the molded product of this embodiment is obtained by molding the above-mentioned polyolefin resin composition.
- Examples of the molded product of this embodiment include an injection molded product, a fiber, a flat yarn, a biaxially stretched film, a uniaxially stretched film, a non-stretched film, a sheet, a thermoforming molded product, an extrusion blow molded product, and an injection blow molded product. Examples thereof include injection stretch blow molded products, deformed extrusion molded products, and rotary molded products.
- a molded product that is required to sufficiently suppress the crystallization of the polyolefin-based resin during production is particularly suitable. Specific examples of such a molded product include a laminate obtained by laminating synthetic fibers, films, and resins on a base material made of wood or fibrous material.
- the method for producing the molded product of the present embodiment is not particularly limited, and for example, an injection molding method, an extrusion molding method, a blow molding method, a rotary molding method, a vacuum molding method, an inflation molding method, a calendar molding method, and the like. Molding methods such as a slush molding method, a dip molding method, and a foam molding method can be mentioned. Of these, the extrusion molding method and the calendar molding method are particularly preferable as the molding method.
- the method for suppressing crystallization of the polyolefin-based resin of the present embodiment is a method of blending (A) a nucleating agent for a polyolefin-based resin and (B) a lubricant with the polyolefin-based resin.
- the crystallization of the polyolefin-based resin can be sufficiently suppressed.
- a test piece is placed on a rotary leometer (DHR2 manufactured by TA Instruments) equipped with a parallel plate with a diameter of 25 mm, and the test piece is heated at 230 ° C. for 1 minute in a nitrogen atmosphere, and then the distance between the plates is determined. It was set to 0.9 mm and excess resin was removed. Subsequently, after heating the test piece at 230 ° C. for another 15 minutes, the reometer was set under the conditions of strain amount 1%, angular velocity 1 rad / s, starting temperature 230 ° C., and cooling temperature 5 ° C./min, and 10 from the start of measurement. Dynamic viscoelasticity measurements were performed every second.
- the measurement points in the region where the sample temperature is 140 ° C or lower and the ⁇ * is 10 3 to 10 6 Pa s in the graph plotting ⁇ * (Pa s) and sample temperature (° C) are A 1 , A 2 in chronological order from the start of measurement. , A 3 ..., and when the straight line passing through A i and A i + 1 is a straight line Li, the straight line L 1 is defined as the straight line L 1 and the straight line L 2 ...
- a straight line L2 passes through a measurement point 18 minutes after the start of measurement (corresponding to the set temperature of the leometer at 140 ° C.) and a measurement point 20 minutes after the start of measurement (corresponding to the set temperature of the leometer at 130 ° C.).
- the temperature corresponding to the intersection P of the straight line L1 and the straight line L2 was defined as the crystallization temperature (° C.).
- the crystallization temperature (° C.) determined by the above method was determined. The results are shown in Tables 1 and 2.
- the crystallization inhibitor for the polyolefin resin of the present invention can sufficiently suppress the crystallization of the polyolefin resin.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本実施形態のポリオレフィン系樹脂用結晶化抑制剤は、(A)ポリオレフィン系樹脂用核剤と、(B)滑剤と、を含む。
<ポリオレフィン系樹脂組成物>
本実施形態のポリオレフィン系樹脂組成物は、ポリオレフィン系樹脂と、(A)ポリオレフィン系樹脂用核剤と、(B)滑剤と、を含むものである。そして、ポリオレフィン系樹脂100質量部に対する(A)ポリオレフィン系樹脂用核剤の含有量が0.005質量部以上0.1質量部以下である。
<ポリオレフィン系樹脂組成物の製造方法>
本実施形態のポリオレフィン系樹脂組成物の製造方法は、ポリオレフィン系樹脂に対して、(A)ポリオレフィン系樹脂用核剤と、(B)滑剤と、を配合する配合工程を含む。そして、配合工程において、ポリオレフィン系樹脂100質量部に対する(A)ポリオレフィン系樹脂用核剤の配合量が0.005質量部以上0.1質量部以下である。
まず、ポリオレフィン系樹脂と、(A)ポリオレフィン系樹脂用核剤と、(B)滑剤と、を準備する。
次に、ポリオレフィン系樹脂に(A)ポリオレフィン系樹脂用核剤および(B)滑剤を配合する。配合の方法としては特に限定されるものではなく、例えばポリオレフィン系樹脂にポリオレフィン系樹脂用結晶化抑制剤および必要に応じてその他の添加剤を添加した後、FMミキサー、ミルロール、バンバリーミキサー、スーパーミキサー等の混合装置を用いて混合する方法等が挙げられる。ここで、(A)ポリオレフィン系樹脂用核剤および(B)滑剤は、上述したポリオレフィン系樹脂用結晶化抑制剤として配合してもよい。また、配合の方法は、(A)ポリオレフィン系樹脂用核剤、(B)滑剤および必要に応じてその他の添加剤のうち少なくとも一つの成分を、ポリオレフィン系樹脂モノマーまたはポリオレフィン系樹脂オリゴマーの重合前または重合中に添加して重合反応を行い、得られた重合体に残りの成分を添加する方法であってもよい。
<成形品>
本実施形態の成形品は、上述したポリオレフィン系樹脂組成物を成形して得られるものである。
<ポリオレフィン系樹脂の結晶化抑制方法>
本実施形態のポリオレフィン系樹脂の結晶化抑制方法は、ポリオレフィン系樹脂に対して(A)ポリオレフィン系樹脂用核剤と、(B)滑剤と、を配合する方法である。
(実施例1~13、比較例1)
ポリオレフィン系樹脂(シリンダー温度230℃、荷重2.16kgにおけるメルトフローレート7.7g/10minのホモポリプロピレン)100質量部に対し、フェノール系酸化防止剤としてテトラキス[メチレン-3-(3’,5’-ジ-tert-ブチル-4’-ヒドロキシフェニル)プロピオネート]メタンを0.05質量部、リン系酸化防止剤としてトリス(2,4-ジ-tert-ブチルフェニル)ホスファイトを0.1質量部、脂肪酸金属塩としてステアリン酸カルシウムを0.05質量部、並びに、表1および2に示す(A)ポリオレフィン系樹脂用核剤および(B)滑剤を表1および2に示す配合量配合し、ヘンシェルミキサーを用いて混合した後、二軸押出機(東洋精機製作所製 ラボプラストミルマイクロ)を用いて230℃の押出温度で溶融混練し、造粒することにより、実施例1~13および比較例1の樹脂組成物ペレットを得た。表1および2において各成分の配合量の単位は質量部である。なお、表1および2に記載の(A)ポリオレフィン系樹脂用核剤および(B)滑剤は以下の通りである。
(A-1a)化合物No.1
(A-1b)化合物No.2
(A-2a)化合物No.5
(A-2b)化合物No.8
(A-3a)化合物No.11
(B)滑剤
(B-1)グリセロールステアリン酸モノエステル
(B-2a)オレイン酸アミド
(B-2b)エチレンビスステアリン酸アミド
得られた実施例1~13および比較例1の樹脂組成物ペレットを、50tプレス機を用いて230℃、15MPa、3minの条件で溶融圧縮し、一辺の長さ10cm、厚み1.0mmの正方形シートを得た。得られたシートから直径25mmの円盤状の試験片を切り出し、この試片について、結晶化温度を以下の手順で測定した。
Claims (9)
- (A)ポリオレフィン系樹脂用核剤と、
(B)滑剤と、
を含むことを特徴とするポリオレフィン系樹脂用結晶化抑制剤。 - 前記(A)ポリオレフィン系樹脂用核剤が、(A-1)下記一般式(1)で表されるアセタール化合物を含み、
前記(B)滑剤が、(B-1)脂肪酸エステルおよび(B-2)脂肪酸アミドからなる群より選ばれる少なくとも一種を含む、
請求項1記載のポリオレフィン系樹脂用結晶化抑制剤。
(一般式(1)中、R1は水素原子または炭素原子数1~4のアルキル基を表し、R2、R3、R4およびR5はそれぞれ独立に水素原子、ハロゲン原子、シアノ基、炭素原子数1~4のアルキル基または炭素原子数1~4のアルコキシ基を表し、あるいはR2およびR3またはR4およびR5が互いに連結した炭素原子数3~6のアルキレン基または炭素原子数1~4のアルキレンジオキシ基を表し、Xは単結合、-CH(OH)-基または-CH(OH)CH(OH)-基を表す。) - 前記(B-1)脂肪酸エステルが、グリセロール脂肪酸モノエステルを含む請求項2記載のポリオレフィン系樹脂用結晶化抑制剤。
- 前記(B-2)脂肪酸アミドが、脂肪酸モノアミドおよびアルキレンビス脂肪酸アミドからなる群より選ばれる少なくとも一種を含む請求項2または3記載のポリオレフィン系樹脂用結晶化抑制剤。
- ポリオレフィン系樹脂と、
(A)ポリオレフィン系樹脂用核剤と、
(B)滑剤と、
を含み、
前記ポリオレフィン系樹脂100質量部に対する(A)ポリオレフィン系樹脂用核剤の含有量が、0.005質量部以上0.1質量部以下であることを特徴とするポリオレフィン系樹脂組成物。 - 前記(A)ポリオレフィン系樹脂用核剤が、(A-1)下記一般式(1)で表されるアセタール化合物を含み、
前記(B)滑剤が、(B-1)脂肪酸エステルおよび(B-2)脂肪酸アミドからなる群より選ばれる少なくとも一種を含む、
請求項5記載のポリオレフィン系樹脂組成物。
(一般式(1)中、R1は水素原子または炭素原子数1~4のアルキル基を表し、R2、R3、R4およびR5はそれぞれ独立に水素原子、ハロゲン原子、シアノ基、炭素原子数1~4のアルキル基または炭素原子数1~4のアルコキシ基を表し、あるいはR2およびR3またはR4およびR5が互いに連結した炭素原子数3~6のアルキレン基または炭素原子数1~4のアルキレンジオキシ基を表し、Xは単結合、-CH(OH)-基または-CH(OH)CH(OH)-基を表す。) - 請求項5または6記載のポリオレフィン系樹脂組成物を成形して得られることを特徴とする成形品。
- ポリオレフィン系樹脂に対して、
(A)ポリオレフィン系樹脂用核剤と、
(B)滑剤と、
を配合する配合工程を含み、
前記配合工程において、前記ポリオレフィン系樹脂100質量部に対する(A)ポリオレフィン系樹脂用核剤の配合量が、0.005質量部以上0.1質量部以下であることを特徴とするポリオレフィン系樹脂組成物の製造方法。 - ポリオレフィン系樹脂に対して、
(A)ポリオレフィン系樹脂用核剤と、
(B)滑剤と、
を配合することを特徴とするポリオレフィン系樹脂の結晶化抑制方法。
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020237020250A KR20230111609A (ko) | 2020-11-25 | 2021-11-25 | 폴리올레핀계 수지용 결정화 억제제, 폴리올레핀계 수지 조성물, 성형품, 폴리올레핀계 수지 조성물의 제조 방법 및 폴리올레핀계 수지의 결정화 억제 방법 |
| JP2022565414A JPWO2022114072A1 (ja) | 2020-11-25 | 2021-11-25 | |
| US18/038,491 US20240010815A1 (en) | 2020-11-25 | 2021-11-25 | Crystallization inhibitor for polyolefin resin, polyolefin resin composition, molded article, method for producing polyolefin resin composition, and method for inhibiting crystallization of polyolefin resin |
| EP21898044.9A EP4253470A4 (en) | 2020-11-25 | 2021-11-25 | Crystallization inhibitor for polyolefin resin, polyolefin resin composition, molded article, method for producing polyolefin resin composition, and method for inhibiting crystallization of polyolefin resin |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020195480 | 2020-11-25 | ||
| JP2020-195480 | 2020-11-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2022114072A1 true WO2022114072A1 (ja) | 2022-06-02 |
Family
ID=81754315
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2021/043251 Ceased WO2022114072A1 (ja) | 2020-11-25 | 2021-11-25 | ポリオレフィン系樹脂用結晶化抑制剤、ポリオレフィン系樹脂組成物、成形品、ポリオレフィン系樹脂組成物の製造方法およびポリオレフィン系樹脂の結晶化抑制方法 |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20240010815A1 (ja) |
| EP (1) | EP4253470A4 (ja) |
| JP (1) | JPWO2022114072A1 (ja) |
| KR (1) | KR20230111609A (ja) |
| WO (1) | WO2022114072A1 (ja) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116444892A (zh) * | 2023-03-10 | 2023-07-18 | 金发科技股份有限公司 | 一种聚丙烯材料及其制备方法和应用 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US12435205B2 (en) * | 2019-05-24 | 2025-10-07 | Adeka Corporation | Resin composition and molded article thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0710989A (ja) | 1993-04-16 | 1995-01-13 | Sanyo Chem Ind Ltd | ポリエーテルエステルアミドおよび樹脂組成物 |
| JPH09176407A (ja) | 1995-12-25 | 1997-07-08 | Nippon Poriorefuin Kk | ポリプロピレン系樹脂組成物及びその延伸フィルム |
| JP2001081206A (ja) * | 1999-09-14 | 2001-03-27 | Heisei Polymer Co Ltd | 透明シート |
| US6552131B1 (en) | 1999-02-10 | 2003-04-22 | Sanyo Chemical Industries, Ltd. | Block polymer and antistatic agent comprising the same |
| JP2010132927A (ja) | 2007-12-07 | 2010-06-17 | Du Pont Mitsui Polychem Co Ltd | カリウムアイオノマーからなる高分子型帯電防止剤 |
| JP2012246366A (ja) * | 2011-05-26 | 2012-12-13 | Suzuki Motor Corp | ポリプロピレン系樹脂組成物 |
| JP2016023254A (ja) | 2014-07-22 | 2016-02-08 | 株式会社Adeka | 帯電防止剤、帯電防止剤組成物、帯電防止性樹脂組成物および成形体 |
| WO2019082930A1 (ja) * | 2017-10-25 | 2019-05-02 | 株式会社Adeka | 結晶化遅延剤、これを含有する組成物、オレフィン系樹脂組成物、その成形品、およびオレフィン樹脂の結晶化の遅延方法 |
| JP2019137017A (ja) * | 2018-02-15 | 2019-08-22 | 東洋紡株式会社 | ポリプロピレン系樹脂シート、これを用いた積層体、包装容器 |
| JP2020037668A (ja) * | 2018-08-30 | 2020-03-12 | 株式会社Adeka | 組成物、これを含有する熱可塑性樹脂組成物およびその成形品 |
| WO2020241503A1 (ja) * | 2019-05-24 | 2020-12-03 | 株式会社Adeka | 樹脂組成物およびその成形品 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3514201B1 (en) * | 2016-09-16 | 2026-01-28 | New Japan Chemical Co., Ltd. | Crystal nucleator for polyolefin resins |
| WO2019045015A1 (ja) * | 2017-08-31 | 2019-03-07 | 株式会社Adeka | 組成物、これを用いたオレフィン系樹脂組成物、およびその成形品 |
| EP3916039A4 (en) * | 2019-01-21 | 2022-09-28 | Adeka Corporation | NUCLATING AGENT COMPOSITION, OLEFIN-BASED RESIN COMPOSITION, MOLDING THEREOF AND METHOD OF MAKING AN OLEFIN-BASED RESIN COMPOSITION |
-
2021
- 2021-11-25 KR KR1020237020250A patent/KR20230111609A/ko active Pending
- 2021-11-25 US US18/038,491 patent/US20240010815A1/en active Pending
- 2021-11-25 JP JP2022565414A patent/JPWO2022114072A1/ja active Pending
- 2021-11-25 WO PCT/JP2021/043251 patent/WO2022114072A1/ja not_active Ceased
- 2021-11-25 EP EP21898044.9A patent/EP4253470A4/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0710989A (ja) | 1993-04-16 | 1995-01-13 | Sanyo Chem Ind Ltd | ポリエーテルエステルアミドおよび樹脂組成物 |
| JPH09176407A (ja) | 1995-12-25 | 1997-07-08 | Nippon Poriorefuin Kk | ポリプロピレン系樹脂組成物及びその延伸フィルム |
| US6552131B1 (en) | 1999-02-10 | 2003-04-22 | Sanyo Chemical Industries, Ltd. | Block polymer and antistatic agent comprising the same |
| JP2001081206A (ja) * | 1999-09-14 | 2001-03-27 | Heisei Polymer Co Ltd | 透明シート |
| JP2010132927A (ja) | 2007-12-07 | 2010-06-17 | Du Pont Mitsui Polychem Co Ltd | カリウムアイオノマーからなる高分子型帯電防止剤 |
| JP2012246366A (ja) * | 2011-05-26 | 2012-12-13 | Suzuki Motor Corp | ポリプロピレン系樹脂組成物 |
| JP2016023254A (ja) | 2014-07-22 | 2016-02-08 | 株式会社Adeka | 帯電防止剤、帯電防止剤組成物、帯電防止性樹脂組成物および成形体 |
| WO2019082930A1 (ja) * | 2017-10-25 | 2019-05-02 | 株式会社Adeka | 結晶化遅延剤、これを含有する組成物、オレフィン系樹脂組成物、その成形品、およびオレフィン樹脂の結晶化の遅延方法 |
| JP2019137017A (ja) * | 2018-02-15 | 2019-08-22 | 東洋紡株式会社 | ポリプロピレン系樹脂シート、これを用いた積層体、包装容器 |
| JP2020037668A (ja) * | 2018-08-30 | 2020-03-12 | 株式会社Adeka | 組成物、これを含有する熱可塑性樹脂組成物およびその成形品 |
| WO2020241503A1 (ja) * | 2019-05-24 | 2020-12-03 | 株式会社Adeka | 樹脂組成物およびその成形品 |
Non-Patent Citations (1)
| Title |
|---|
| See also references of EP4253470A4 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116444892A (zh) * | 2023-03-10 | 2023-07-18 | 金发科技股份有限公司 | 一种聚丙烯材料及其制备方法和应用 |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20230111609A (ko) | 2023-07-25 |
| EP4253470A4 (en) | 2024-10-23 |
| JPWO2022114072A1 (ja) | 2022-06-02 |
| US20240010815A1 (en) | 2024-01-11 |
| EP4253470A1 (en) | 2023-10-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2287246B1 (en) | Polyolefin resin composition | |
| US9701812B2 (en) | Clarifying agent composition, and polyolefin resin composition containing same | |
| JP7717214B2 (ja) | 核剤組成物、オレフィン系樹脂組成物、その成形品およびオレフィン系樹脂組成物の製造方法 | |
| WO2022114072A1 (ja) | ポリオレフィン系樹脂用結晶化抑制剤、ポリオレフィン系樹脂組成物、成形品、ポリオレフィン系樹脂組成物の製造方法およびポリオレフィン系樹脂の結晶化抑制方法 | |
| KR20200046062A (ko) | 조성물, 이것을 사용한 열가소성 수지 조성물, 및 그의 성형체 | |
| JP2022011537A (ja) | 発泡成形品および発泡成形品の製造方法 | |
| CN115335447B (zh) | 成核剂、树脂组合物、树脂组合物的制造方法和成形品 | |
| TWI856224B (zh) | 樹脂組成物、其成形品及該樹脂組成物的製造方法 | |
| JP7431734B2 (ja) | 添加剤組成物、これを含有するポリオレフィン系樹脂組成物、ポリオレフィン系樹脂組成物の製造方法、およびその成形品 | |
| WO2022039244A1 (ja) | 化合物、合成樹脂用添加剤、合成樹脂用添加剤組成物、樹脂組成物およびその成形品 | |
| WO2021200842A1 (ja) | 添加剤組成物、これを含む樹脂組成物、その製造方法および成形品 | |
| JP2019044063A (ja) | 結晶化遅延剤、これを含むポリオレフィン系樹脂組成物およびその成形品 | |
| WO2023127938A1 (ja) | 樹脂組成物、成形品および樹脂組成物の製造方法 | |
| JPH06299014A (ja) | シンジオタクチックポリプロピレン組成物 | |
| EP4357405A1 (en) | Nucleating agent composition, resin composition, molded article thereof, and method for manufacturing resin composition | |
| WO2019045015A1 (ja) | 組成物、これを用いたオレフィン系樹脂組成物、およびその成形品 | |
| WO2018150755A1 (ja) | 新規化合物、核剤、樹脂組成物、及び成形体 | |
| JP2024117817A (ja) | 樹脂組成物、成形品、樹脂組成物の製造方法、合成樹脂の結晶化促進方法および合成樹脂の透明性向上方法 | |
| JP2025170794A (ja) | 樹脂組成物、成形品、樹脂組成物の製造方法、樹脂添加剤組成物および樹脂の結晶性向上方法 | |
| WO2025013891A1 (ja) | 樹脂組成物、成形品、樹脂添加剤組成物、樹脂組成物の製造方法、結晶性樹脂の結晶性向上方法および樹脂添加剤組成物用材料 | |
| WO2022025187A1 (ja) | 添加剤組成物、樹脂組成物、樹脂組成物の製造方法および成形品 | |
| JP2025160482A (ja) | トリアジン誘導体、核剤組成物、樹脂組成物、成形品、樹脂組成物の製造方法および結晶性樹脂の結晶性向上方法 | |
| WO2025192736A1 (ja) | 延伸フィルムの製造方法、延伸フィルム、包装体、延伸フィルムの生産性向上方法およびβ晶核剤 | |
| JP2024051849A (ja) | 熱可塑性樹脂用核剤、樹脂組成物、成形品および熱可塑性樹脂の結晶化の促進方法 | |
| JP2019127496A (ja) | 核剤、これを含有するオレフィン系樹脂組成物およびその成形品 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 21898044 Country of ref document: EP Kind code of ref document: A1 |
|
| ENP | Entry into the national phase |
Ref document number: 2022565414 Country of ref document: JP Kind code of ref document: A |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 18038491 Country of ref document: US |
|
| ENP | Entry into the national phase |
Ref document number: 20237020250 Country of ref document: KR Kind code of ref document: A |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| ENP | Entry into the national phase |
Ref document number: 2021898044 Country of ref document: EP Effective date: 20230626 |