WO2022215632A1 - Composition d'additif de résine, composition de résine et article moulé - Google Patents

Composition d'additif de résine, composition de résine et article moulé Download PDF

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Publication number
WO2022215632A1
WO2022215632A1 PCT/JP2022/016159 JP2022016159W WO2022215632A1 WO 2022215632 A1 WO2022215632 A1 WO 2022215632A1 JP 2022016159 W JP2022016159 W JP 2022016159W WO 2022215632 A1 WO2022215632 A1 WO 2022215632A1
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Prior art keywords
resin
aromatic phosphate
aromatic
ion
content
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PCT/JP2022/016159
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English (en)
Japanese (ja)
Inventor
悠里 横田
優 山口
直子 丹治
晶群 佐藤
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株式会社Adeka
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Publication of WO2022215632A1 publication Critical patent/WO2022215632A1/fr

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    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • 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

Definitions

  • the present invention relates to resin additive compositions, resin compositions, and molded articles.
  • Patent Document 1 describes the addition of a nucleating agent (a nucleating agent, a crystallization accelerator, a clarifying agent, and the like are hereinafter collectively referred to as a "nucleating agent") to a polyolefin resin. (Claim 1 of Patent Document 1, etc.).
  • nucleating agent from the group consisting of an organic compound A having at least two amide functional groups, and metal salts of organic acids, metal salts of organic phosphoric acids, and metal salts of polyols, and their precursor systems Combination systems of compound B that can be selected are exemplified (Claim 1, Examples, etc. of Patent Document 1).
  • R 1 to R 5 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • R 6 to R 8 each independently represent an alkyl group having 1 to 6 carbon atoms
  • Z 1 to Z 3 each independently represent a *—C(O)—NH— group or * represents a -NH-C(O)- group, where * represents a bond that bonds to a benzene ring.
  • aromatic amide compound (B) A resin additive composition comprising The aromatic phosphate metal salt (AS) comprises an aromatic phosphate alkali metal salt composed of the aromatic phosphate ion (A) and the alkali metal ion (C), The content ratio Y/W in terms of mass of the content Y of the aromatic amide compound (B) to the content W of the metal salt of aromatic phosphate (AS) is 0.01 or more and 0.15 or less. is A resin additive composition is provided.
  • polyolefin resin P
  • an aromatic phosphate ester metal salt AS
  • an aromatic phosphate ester metal salt AS
  • a resin composition comprising The aromatic phosphate metal salt (AS) comprises an aromatic phosphate alkali metal salt composed of the aromatic phosphate ion (A) and the alkali metal ion (C),
  • the content ratio Y/W in terms of mass of the content Y of the aromatic amide compound (B) to the content W of the metal salt of aromatic phosphate (AS) is 0.01 or more and 0.15 or less.
  • a resin additive composition a resin composition, and a molded product with excellent transparency are provided.
  • the resin additive composition of the present embodiment comprises an aromatic phosphate ion (A) represented by the following general formula (1), an aromatic amide compound (B) represented by the following general formula (2), and alkali metal ion (C), and the content ratio Y/X in terms of mass of the content Y of the aromatic amide compound (B) to the content X of the aromatic phosphate ester ion (A) is 0 0.01 or more and 0.15 or less.
  • the resin additive composition in another embodiment is an aromatic phosphate ester metal salt ( AS), and an aromatic amide compound (B) represented by the following general formula (2), wherein the aromatic phosphate metal salt (AS) is an aromatic phosphate ion (A) and an alkali metal ion Content in terms of mass of the content Y of the aromatic amide compound (B) with respect to the content W of the aromatic phosphate metal salt (AS), including the aromatic phosphate alkali metal salt consisting of (C)
  • the ratio Y/W is configured to be 0.01 or more and 0.15 or less.
  • the resin additive composition of the present embodiment functions as a nucleating agent/clarifying agent added during the molding process of a resin such as a polyolefin resin, and can achieve a modification effect such as an improvement in transparency.
  • the transparency of the resin can be significantly improved.
  • the resin additive composition of the present embodiment can also improve transparency performance when a resin such as a polyolefin resin is thickened.
  • the method for producing the resin additive composition of the present embodiment includes, for example, an aromatic phosphate metal salt (AS) and an aromatic amide compound (B), and, if necessary, a fatty acid metal salt (DS) or the like. and mixing the ingredients of A known means such as a mixer can be adopted as the mixing means.
  • the mixing temperature is not particularly limited, but may be room temperature.
  • the timing of addition of each component is arbitrary, and all components may be mixed together, or one component may be added to the other component all at once or sequentially during mixing.
  • the content of the aromatic phosphate ion (A) in the resin additive composition can be quantified by high performance liquid chromatography. Specifically, using a mixed solvent of methanol/water/acetic acid (volume ratio 70/25/5), the aromatic phosphate ester ion (A) is extracted from the resin additive composition to obtain an extract. . Here, all of the aromatic phosphate ions (A) extracted in the extract are protonated by the acetic acid contained in the mixed solvent to form aromatic phosphates. Then, the amount of aromatic phosphate ester contained in the extract is quantified by high-performance liquid chromatography, and the content of aromatic phosphate ion (A) in the resin additive composition is calculated based on the quantified value. do.
  • the content of the aromatic phosphate ion (A) in the resin additive composition is quantified by the following procedure.
  • Method for quantifying content of aromatic phosphate ion (A) 1. Accurately weigh the resin additive composition in an eggplant flask, add a mixed solvent of methanol / water / acetic acid (volume ratio 70/25/5), and irradiate with ultrasonic waves at 25 ° C. for 15 minutes to obtain an aromatic phosphate. An extract is obtained by extracting the ion (A) in the form of an aromatic phosphate. 2.
  • the resulting extract is transferred to a volumetric flask and diluted with a mixed solvent of methanol/water/acetic acid (volume ratio 70/25/5) to obtain a sample solution.
  • a mixed solvent of methanol/water/acetic acid volume ratio 70/25/5
  • the extract is filtered to remove the insoluble matter, and the filtrate is transferred to a volumetric flask.
  • a reversed-phase column (manufactured by JASCO Corporation: trade name FINEPAK SIL C18-10 250 mm ⁇ 4.6 mm) and a photodiode array detector (manufactured by Shimadzu Corporation: SPD-M20A equipped with a high-performance liquid chromatograph device (Shimadzu Corporation) Manufactured by: High Speed Chromatography (manufactured by Shimadzu Corporation), the mobile phase is a mixed solvent of methanol / water / acetic acid (volume ratio 70/25/5), column temperature 40 ° C., flow rate 1 mL / min, detection A sample solution is measured at an instrument wavelength of 275 nm, and the amount of aromatic phosphate contained in the sample solution is quantified by a calibration curve method. 4. The content of the aromatic phosphate ester ion (A) in the resin additive composition is calculated based on the obtained quantitative value, weight of the weighed resin additive composition, and dilution ratio.
  • the amount of the resin additive composition to be weighed, the amount of the mixed solvent used for extraction, and the amount of dilution of the extract are determined by the amount of the aromatic phosphate ester ion (A) contained in the resin additive composition. The amount is adjusted accordingly.
  • the content of the aromatic amide compound (B) in the resin additive composition can be quantified by gas chromatography. Specifically, using chloroform as a solvent, the aromatic amide compound (B) is extracted from the resin additive composition to obtain an extract. Then, the amount of the aromatic amide compound (B) contained in the extract is quantified by gas chromatography, and the content of the aromatic amide compound (B) in the resin additive composition is calculated based on the quantified value. .
  • the content of the aromatic amide compound (B) in the resin additive composition is quantified by the following procedure.
  • Method for quantifying content of aromatic amide compound (B) 1.
  • the resin additive composition is precisely weighed in an eggplant flask, chloroform is added, and ultrasonic waves are applied at 25° C. for 15 minutes to extract the aromatic amide compound (B) to obtain an extract.
  • the resulting extract is transferred to a volumetric flask and diluted with chloroform to obtain a sample solution.
  • the extract is filtered to remove the insoluble matter, and the filtrate is transferred to a volumetric flask. 3.
  • a gas chromatograph (GC-2010, manufactured by Shimadzu Corporation) equipped with a capillary column (manufactured by Shimadzu GLC Co., Ltd.: BPX-5) and a hydrogen flame ionization detector Photoda was used, the carrier gas was helium, and the inlet temperature was 100°C. , column flow rate of 10 mL/min, oven temperature of 100 to 360° C., and heating rate of 15° C./min. do. 4.
  • the content of the aromatic amide compound (B) in the resin additive composition is calculated based on the obtained quantitative value, the weight of the weighed resin additive composition, and the dilution ratio.
  • the amount of the resin additive composition to be weighed, the amount of the mixed solvent used for extraction, and the amount of dilution of the extract are determined according to the content of the aromatic amide compound (B) in the resin additive composition. adjusted accordingly.
  • X is the content in terms of mass of the aromatic phosphate ion (A) in the resin additive composition quantified by the high performance liquid chromatography method, and the content is quantified by the gas chromatography method.
  • the content of the aromatic amide compound (B) in the resin additive composition in terms of mass is defined as Y, and the content ratio of Y to X is defined as Y/X.
  • Y/X is 0.01 or more and 0.15 or less, preferably 0.02 or more and 0.13 or less, more preferably 0.04 or more and 0.12 or less, still more preferably 0.05 or more and 0.10 or less, and still more It is preferably 0.06 or more and 0.09 or less.
  • Y/X is 0.01 or more and 0.15 or less, preferably 0.02 or more and 0.13 or less, more preferably 0.04 or more and 0.12 or less. , more preferably 0.05 or more and 0.10 or less, still more preferably 0.06 or more and 0.09 or less.
  • Y/X is 0.01 or more and 0.15 or less, preferably 0.02 or more and 0.13 or less, more preferably 0.04 or more and 0.12 or less, and further It is preferably 0.05 or more and 0.10 or less, and more preferably 0.06 or more and 0.09 or less.
  • the content X in terms of mass of (A) in the resin additive composition is, for example, 2.5% by mass or more, preferably 5% by mass or more, more preferably 10% by mass of the total resin additive composition. above, more preferably 40% by mass or more. This can improve transparency. On the other hand, X may be, for example, 99% by mass or less of the entire resin additive composition.
  • the content Y in terms of mass of the aromatic amide compound (B) in the resin additive composition is, for example, 0.1% by mass or more, preferably 0.5% by mass or more, based on the total resin additive composition. , more preferably 1% by mass or more. Thereby, transparency can be improved. On the other hand, Y may be, for example, 35% by mass or less.
  • the aromatic phosphate ion (A) is represented by the following general formula (1). These may be used alone or in combination of two or more.
  • R 1 to R 5 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • the alkyl group having 1 to 6 carbon atoms includes, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, isobutyl group, amyl group, isoamyl group, tert-amyl group, hexyl group and cyclohexyl group.
  • R 1 , R 2 , R 3 and R 4 are preferably one group selected from the group consisting of methyl group, ethyl group, sec-butyl group and tert-butyl group. A group selected from the group consisting of groups is more preferred, and a tert-butyl group is even more preferred.
  • R5 is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.
  • alkyl group includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups).
  • substituents include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, a cyano group, an amino group, a nitro group, a hydroxy group, a carboxy group, an alkoxy group having 1 to 20 carbon atoms, and a number of carbon atoms. 6 to 20 aryl groups, 6 to 20 aryloxy groups, and the like.
  • the ion represented by the above general formula (1) more preferably contains at least one of the following chemical formulas (A1) to (A4), and more preferably contains the following chemical formula (A2).
  • Alkali metal ions (C) include, for example, one or more selected from the group consisting of sodium ions, potassium ions, and lithium ions.
  • the alkali metal ion (C) may contain either a sodium ion or a lithium ion, and preferably contains a lithium ion from the viewpoint of improving transparency. It may also contain sodium ions.
  • the content of the alkali metal ion (C) in the resin additive composition of the present embodiment may be, for example, 0.3 to 5.0 molar times the aromatic phosphate ester ion. It is preferably up to 2.0 mol times, more preferably 0.7 to 1.5 mol times. This can improve transparency.
  • the content of alkali metal ions in the resin additive composition can be quantified by ICP emission spectrometry. Specifically, after adding 61 wt% nitric acid to the resin additive composition, the resin additive composition was subjected to acid decomposition treatment using a microwave sample decomposition device (manufactured by Analytik Jena, trade name: TOPwave), and the sample to obtain a solution. Then, the sample solution is measured using an ICP emission spectrometer (SPS3500 manufactured by Seiko Instruments Inc.), the amount of alkali metal ions contained in the sample solution is quantified by the calibration curve method, and based on the obtained quantitative value The content of alkali metal ions in the resin additive composition is calculated.
  • a microwave sample decomposition device manufactured by Analytik Jena, trade name: TOPwave
  • the aromatic amide compound (B) is represented by the following general formula (2). These may be used alone or in combination of two or more.
  • R 6 to R 8 each independently represent an alkyl group having 1 to 6 carbon atoms
  • Z 1 to Z 3 each independently represent a *—C(O)—NH— group or * —NH—C(O)— represents a group.
  • * represents a bond that bonds to the benzene ring.
  • the alkyl group having 1 to 6 carbon atoms includes, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, isobutyl group, amyl group, isoamyl group, tert-amyl group, hexyl group and cyclohexyl group.
  • R 6 to R 8 are preferably a group selected from the group consisting of methyl group, ethyl group, propyl group, isopropyl group, sec-butyl group, tert-butyl group and tert-amyl group, and isopropyl group, sec-butyl group, tert-butyl group and tert-amyl group, more preferably one group selected from the group consisting of isopropyl group and tert-butyl group. .
  • Z 1 to Z 3 are preferably *—NH—C(O)— groups from the viewpoint of transparency.
  • the compound represented by the general formula (2) preferably contains any one of the following chemical formulas (B1) to (B3), and among these, from the viewpoint of transparency, the following chemical formula (B1) is included. is particularly preferred.
  • the resin additive composition of the present embodiment may be composed of only the above components (A) to (C) as components to be detected by a predetermined quantitative method for each component.
  • Components other than components (A) to (C) may be contained within the range of achieving
  • fatty acid ions (D) examples include fatty acid ions (D), nucleating agents that do not contain components (A) and (B), silicic acid-based inorganic additives, and hydrotalcites.
  • other additives added to the resin composition described later may be used as other components. These may be used alone or in combination of two or more.
  • the resin additive composition of the present embodiment preferably contains fatty acid ions (D).
  • the dispersibility of the resin additive composition in the polyolefin resin can be improved.
  • the content of the fatty acid ions (D) may be, for example, 0.1 to 3.0 mol times the alkali metal ions (C). From the viewpoint of further improving the dispersibility of the resin additive composition in the system resin, it is preferably 0.25 to 2.0 times the molar amount of the alkali metal ion (C), and 0.5 to 1.0 A molar ratio is more preferable.
  • the content of fatty acid ions (D) in the resin additive composition can be quantified by gas chromatography. Specifically, after adding 6 mol/L hydrochloric acid to the resin additive composition to protonate the fatty acid ion (D) in the resin additive composition to form a fatty acid, hexane was used as a solvent to obtain the resin additive composition. Fatty acids are extracted from a mixture of the substance and 6 mol/L hydrochloric acid to obtain an extract. Then, the amount of fatty acid contained in the extract is quantified by gas chromatography in accordance with JIS K 3331, and the content of fatty acid ions (D) in the resin additive composition is calculated based on the quantified value. Here, by adding 6 mol/L hydrochloric acid, all of the fatty acid ions (D) in the resin additive composition are protonated into fatty acids.
  • a fatty acid ion (D) is represented, for example, by the following general formula (3). These may be used alone or in combination of two or more.
  • R 8 represents an aliphatic group having 9 to 30 carbon atoms.
  • Aliphatic groups having 9 to 30 carbon atoms include alkyl groups and alkenyl groups having 9 to 30 carbon atoms, which may be substituted with hydroxyl groups.
  • the aliphatic group having 9 to 30 carbon atoms preferably has 11 to 21 carbon atoms, more preferably 13 to 21 carbon atoms, and more preferably 13 to 19 carbon atoms. More preferred are those having 13 to 17 carbon atoms.
  • fatty acid ions (D) include capric acid, 2-ethylhexanoic acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, nonadecylic acid, and arachidic acid.
  • heicosylic acid behenic acid, tricosylic acid, lignoceric acid, cerotic acid, montanic acid, ions of saturated fatty acids such as melissic acid, 4-decenoic acid, 4-dodecenoic acid, palmitoleic acid, ⁇ -linolenic acid, linoleic acid, ⁇ -Ions of linear unsaturated fatty acids such as linolenic acid, stearidonic acid, petroselinic acid, oleic acid, elaidic acid, vaccenic acid, eicosapentaenoic acid, docosapentaenoic acid, docosahexaenoic acid, ricinoleic acid, 12-hydroxystearic acid, etc.
  • saturated fatty acids such as melissic acid, 4-decenoic acid, 4-dodecenoic acid, palmitoleic acid, ⁇ -linolenic acid, linole
  • the fatty acid ion (D) is preferably laurate ion, myristate ion, palmitate ion, stearate ion, behenate ion, oleate ion, 12-hydroxystearate ion, myristate ion, palmitate ion.
  • stearate, behenate and 12-hydroxystearate are more preferred, and myristate, palmitate, stearate and 12-hydroxystearate are more preferred.
  • nucleating agents that do not contain component (A) and component (B) include sodium benzoate, 4-tert-butylbenzoic acid aluminum salt, sodium adipate and disodium bicyclo[2.2.1]heptane-2. ,3-dicarboxylate, carboxylic acid metal salts such as calcium cyclohexane 1,2-dicarboxylate, dibenzylidene sorbitol, bis(methylbenzylidene) sorbitol, bis(3,4-dimethylbenzylidene) sorbitol, bis(p-ethyl benzylidene) sorbitol, and bis(dimethylbenzylidene) sorbitol, polyol derivatives such as 1,2,3-trideoxy-4,6:5,7-o-bis(4-propylbenzylidene)nonitol, N,N',N' amide compounds such as '-tris[2-methylcyclohexyl]-1,2,3
  • silicic acid-based inorganic additives examples include fumed silica, fine particle silica, silica, diatomaceous earths, clay, kaolin, silica gel, calcium silicate, sericite, kaolinite, flint, feldspar, vermiculite, attapulgite, and talc. , mica, minnesotite, pyrophyllite, etc. Among them, those having a layered grain structure and those having a silicon content of 15% by mass or more are preferable.
  • Preferred inorganic additives include sericite, kaolinite, talc, mica, minnesotite and pyrophyllite, with talc and mica being more preferred, and talc being particularly preferred.
  • hydrotalcites may be complex salt compounds containing magnesium, aluminum, hydroxyl groups, carbonate groups, and any water of crystallization, and may be natural or synthetic.
  • hydrotalcites may be those in which at least part of magnesium or aluminum is substituted with other metals such as alkali metals and zinc, and at least part of hydroxyl groups and carbonate groups are substituted with other anion groups. can be anything.
  • Hydrotalcites may be those obtained by dehydrating water of crystallization, and include higher fatty acids such as stearic acid, higher fatty acid metal salts such as alkali metal oleate, and organic metal sulfonates such as alkali metal dodecylbenzenesulfonate. It may be coated with a salt, higher fatty acid amide, higher fatty acid ester, wax, or the like.
  • the resin additive composition of the present embodiment include, for example, an aromatic phosphate metal salt (AS) containing an aromatic phosphate ion (A) and a metal ion (M) and an aromatic amide compound
  • AS aromatic phosphate metal salt
  • M metal ion
  • an aromatic amide compound examples include resin additive compositions containing (B).
  • the aromatic phosphate metal salt (AS) includes an aromatic phosphate alkali metal salt composed of an aromatic phosphate ion (A) and an alkali metal ion (C).
  • the resin additive composition is a fatty acid metal salt (DS) containing fatty acid ions (D) and metal ions (M) in addition to the aromatic phosphate metal salt (AS) and the aromatic amide compound (B).
  • the component (DS) may further contain hydroxide ions.
  • the content ratio Y of the content Y of the aromatic amide compound (B) to the content W of the aromatic phosphate metal salt (AS) as the denominator /W may be configured to be 0.01 or more and 0.15 or less in terms of mass.
  • the content ratio Y/W of the content Y of the aromatic amide compound (B) to the content W of the metal salt of aromatic phosphate (AS) as the denominator is preferably 0.02 in terms of mass. 0.13 or less, more preferably 0.04 or more and 0.12 or less, still more preferably 0.05 or more and 0.1 or less, and even more preferably 0.06 or more and 0.09 or less. Thereby, transparency can be improved.
  • examples of metal atoms constituting the metal ion (M) include alkali metal atoms, alkaline earth metal atoms, aluminum, titanium, manganese, iron, zinc, silicon, zirconium, yttrium, and hafnium.
  • an alkali metal atom, an alkaline earth metal atom, and aluminum are preferred, and an alkali metal atom and aluminum are more preferred.
  • the alkali metal atom sodium or lithium is more preferable, and lithium is particularly preferable.
  • magnesium or calcium is preferred as the alkaline earth metal atom.
  • the aromatic phosphate metal salt (AS) includes an aromatic phosphate alkali metal salt composed of an aromatic phosphate ion (A) and an alkali metal ion (C).
  • the aromatic phosphate alkali metal salt include aromatic phosphate sodium salt, aromatic phosphate potassium salt, and aromatic phosphate lithium salt.
  • the aromatic phosphate metal salt (AS) may contain either an aromatic phosphate sodium salt or an aromatic phosphate lithium salt, and from the viewpoint of improving transparency, an aromatic phosphate lithium salt is preferably included. It may also contain an aromatic phosphate sodium salt.
  • Y/W is 0.01 or more and 0.15 or less, preferably 0.02 or more and 0.13 or less, more preferably 0 0.04 or more and 0.12 or less, more preferably 0.05 or more and 0.10 or less, and still more preferably 0.06 or more and 0.09 or less.
  • the aromatic phosphate metal salt (AS) contains an aromatic phosphate sodium salt
  • Y/W is 0.01 or more and 0.15 or less, preferably 0.02 or more and 0.13 or less, more preferably 0 0.04 or more and 0.12 or less, more preferably 0.05 or more and 0.10 or less, and still more preferably 0.06 or more and 0.09 or less.
  • the fatty acid metal salt (DS) contains a fatty acid alkali metal salt.
  • the fatty acid alkali metal salt comprises a fatty acid lithium salt.
  • the resin composition of the present embodiment comprises a polyolefin resin (P), an aromatic phosphate ester ion (A) represented by the above general formula (1), and an aromatic amide compound represented by the above general formula (2). (B), and an alkali metal ion (C), and the content ratio Y/ X is configured to be 0.01 or more and 0.15 or less.
  • Y/X in the resin composition can adopt the same numerical range as Y/X shown in the description of the resin additive composition.
  • component (A), component (B), component (C) and component (D) in the resin composition can be determined by solvent extraction of each component from the resin composition by a known method to obtain an extract. After that, the content of each component in the obtained extract can be quantified by the same method as the quantification method shown in the description of the resin additive composition.
  • the content of the aromatic phosphate ion (A) with respect to 100 parts by mass of the polyolefin resin (P) is, for example, 0.001 part by mass or more and 10 parts by mass or less, preferably 0.001 part by mass or more and 10 parts by mass or less. 005 mass parts or more and 8 mass parts or less, more preferably 0.01 mass parts or more and 5 mass parts or less.
  • the content of the aromatic amide compound (B) with respect to 100 parts by mass of the polyolefin resin (P) is, for example, 0.001 parts by mass or more and 10 parts by mass or less, preferably 0.001 part by mass or more and 10 parts by mass or less. 005 mass parts or more and 8 mass parts or less, more preferably 0.01 mass parts or more and 5 mass parts or less.
  • the content of the alkali metal ion (C) in the resin composition of the present embodiment may be, for example, 0.3 to 5.0 times the molar amount of the aromatic phosphate ester ion. It is preferably up to 2.0 mol times, more preferably 0.7 to 1.5 mol times. This can improve the transparency of the resin composition.
  • the resin composition of the present embodiment preferably contains fatty acid ions (D).
  • the content of the fatty acid ions (D) may be, for example, 0.0.1 to 3.0 mol times the alkali metal ions (C). It is preferably 0.25 to 2.0 mol times, more preferably 0.5 to 1.0 mol times the metal ion (C).
  • a specific example of the resin composition of the present embodiment includes a resin composition containing a polyolefin resin (P), an aromatic phosphate metal salt (AS) and an aromatic amide compound (B).
  • the aromatic phosphate metal salt (AS) includes an aromatic phosphate alkali metal salt composed of an aromatic phosphate ion (A) and an alkali metal ion (C).
  • the resin composition may further contain a fatty acid metal salt (DS) in addition to the polyolefin resin (P), the aromatic phosphate metal salt (AS) and the aromatic amide compound (B).
  • the content ratio Y/W of the content Y of the aromatic amide compound (B) is , in terms of mass, 0.01 or more and 0.15 or less.
  • Y/W in the resin composition can adopt the same numerical range as Y/W shown in the description of the resin additive composition.
  • the resin composition of the present embodiment contains a polyolefin resin (P) and the above resin additive composition
  • the aromatic amide compound (B ) may be configured such that the content ratio Y/X in terms of mass of the content Y is within the numerical range described above.
  • the resin composition of the present embodiment contains the polyolefin resin (P) and the above resin additive composition, and when the content W of the aromatic phosphate metal salt (AS) is used as the denominator, It may be configured such that the content ratio Y/W of the content Y of the aromatic amide compound (B) in terms of mass falls within the numerical range described above.
  • the method of adding the above resin additive composition to the polyolefin resin (P) is not particularly limited, and generally used methods can be applied as they are. For example, a method of dry-blending the powder or pellets of the polyolefin resin (P) and the powder of the resin additive composition can be used.
  • the above resin composition can be used in various forms, and may be in the form of pellets, granules, or powder, for example. Pellets are preferred from the viewpoint of handling.
  • polystyrene resin (P) examples include polypropylene, high-density polyethylene, low-density polyethylene, linear low-density polyethylene, polybutene-1, poly-3-methylpentene, poly-4-methylpentene, ethylene/propylene block or random copolymer.
  • polypropylene high-density polyethylene
  • low-density polyethylene linear low-density polyethylene
  • polybutene-1 poly-3-methylpentene
  • poly-4-methylpentene examples include ethylene/propylene block or random copolymer.
  • ⁇ -olefin polymers such as coalescence.
  • the polyolefin-based resin (P) may contain a polypropylene-based resin.
  • polypropylene-based resins include polyethylene-based resins such as low-density polyethylene, linear low-density polyethylene, high-density polyethylene, crosslinked polyethylene, and ultra-high molecular weight polyethylene, homopolypropylene, random copolymer polypropylene, block copolymer polypropylene, impact copolymer polypropylene, High impact copolymer polypropylene, polypropylene resins such as maleic anhydride-modified polypropylene, polybutene-1, cycloolefin polymer, poly-3-methyl-1-butene, poly-3-methyl-1-pentene, poly-4-methyl- Examples include ⁇ -olefin polymers such as 1-pentene, ⁇ -olefin copolymers such as ethylene-methyl methacrylate copolymer and ethylene-vinyl acetate copolymer.
  • polyolefin-based resins may be used alone or in combination of two or more. Moreover, the polyolefin resin may be alloyed. Molecular weight of polyolefin resin, degree of polymerization, density, softening point, ratio of insoluble matter in solvent, degree of stereoregularity, presence or absence of catalyst residue, type and blending ratio of raw material monomers, catalyst used for polymerization The type (for example, Ziegler catalyst, metallocene catalyst, etc.) is not particularly limited and can be selected as appropriate.
  • the polyolefin-based resin (P) preferably contains a polypropylene-based resin from the viewpoint of obtaining a resin composition having excellent mechanical properties. Moreover, the polyolefin-based resin (P) may contain a thermoplastic elastomer.
  • the resin composition may contain rubber components such as isoprene rubber, butadiene rubber, and thermoplastic elastomer.
  • the resin composition may optionally contain antioxidants, light stabilizers, ultraviolet absorbers, pigments, fillers, plasticizers, epoxy compounds, foaming agents, antistatic agents, flame retardants, lubricants, and heavy metal deactivators. , hydrotalcites, organic carboxylic acids, coloring agents, silicic acid additives, processing aids, and the like. These may be used alone or in combination of two or more. Other components described in the resin additive composition may also be used. Examples of the antioxidants include phosphorus antioxidants, phenolic antioxidants, thioether antioxidants, and the like.
  • antistatic agent examples include cationic surfactants, anionic surfactants, nonionic surfactants, low-molecular-weight antistatic agents including amphoteric surfactants, ionomers, block polymers having polyethylene glycol as a hydrophilic portion, and the like.
  • the flame retardant include halogen-based compounds, phosphoric acid ester-based compounds, phosphoramide-based compounds, melamine-based compounds, melamine salt compounds of polyphosphoric acid, fluororesins, metal oxides, and the like.
  • the lubricant include hydrocarbon-based, fatty acid-based, aliphatic alcohol-based, aliphatic ester-based, aliphatic amide-based, and metallic soap-based lubricants.
  • the content of the additive in the resin composition is preferably, for example, 0.001 to 10 parts by weight with respect to 100 parts by weight of the polyolefin resin. By setting it as such a numerical range, the improvement of the effect of an additive is obtained.
  • the resin composition includes injection molded articles, fibers, flat yarns, biaxially stretched films, uniaxially stretched films, non-stretched films, sheets, thermoformed articles, extrusion blow molded articles, injection blow molded articles, injection stretch blow molded articles, It can be used for moldings such as profile extrusion moldings and rotational moldings. Among these, injection molded articles, films, sheets, and thermoformed articles are preferable as molded articles.
  • the method for producing a molded product of the present embodiment includes a step of molding the resin composition based on various molding methods, thereby obtaining the above-described molded product.
  • the molding method is not particularly limited, and may be injection molding, extrusion molding, blow molding, rotational molding, vacuum molding, inflation molding, calendar molding, slush molding, dip molding, foam molding. law, etc. Among these, the injection molding method, the extrusion molding method, and the blow molding method are preferable.
  • the above resin composition can be used in various applications such as building materials, agricultural materials, vehicle parts such as automobiles, trains, ships, and aircraft, packaging materials, miscellaneous goods, toys, home appliances, and medical products.
  • automotive parts such as bumpers, dashboards, instrument panels, battery cases, luggage cases, door panels, door trims, and fender liners; resin parts for household appliances such as refrigerators, washing machines, and vacuum cleaners; dishes and bottles.
  • Household goods such as caps, buckets, and bathing goods; connecting resin parts such as connectors; miscellaneous goods such as toys, storage containers, and synthetic paper; medical packs, syringes, catheters, medical tubes, syringes, infusion bags, and reagents Molded products for medical use, such as containers, drug containers, individual drug packages; Building materials such as wall materials, floor materials, window frames, wallpapers, and windows; Wire covering materials; Agricultural materials such as houses, tunnels, flat yarn mesh bags, etc. ;Industrial materials such as pallets, pails, back grind tapes, LCD protection tapes, pipes, and modified silicone polymers for sealing materials;Food packaging materials such as wraps, trays, cups, films, bottles, caps, and storage containers, etc.
  • Examples include 3D printer materials, battery separator films, and the like.
  • various post-treatments such as medical applications, food packaging applications and other applications that are sterilized by radiation, or for improving surface properties such as paintability
  • low-temperature plasma is used after molding. It can be used for applications such as treatment. Among these, it is preferable to use it for automobile parts, household goods, and food packaging materials.
  • the raw materials shown in Table 1 are as follows.
  • AS1 Aromatic phosphate ester sodium salt represented by the following chemical formula AS1 obtained by the following synthesis procedure 2,2'-methylenebis[4,6-bis(1,1- dimethylethyl)] 42.5 g of phenol, 16.1 g of phosphorus oxychloride and 2.4 g of triethylamine were charged and stirred at
  • Aromatic phosphate ester metal salt AS2 Aromatic phosphate ester lithium salt represented by the following chemical formula AS2 obtained by the following synthesis procedure White obtained by synthesizing the above aromatic phosphate ester metal salt AS1 25.4 g (50 mmol) of powder was dissolved in methanol, an aqueous solution of 1.2 g (50 mmol) of lithium hydroxide was added, and the mixture was stirred at room temperature for 1 hour to obtain a slurry. After filtering the resulting slurry, the filter residue was washed with water until the pH reached 8 to obtain a white solid. The obtained white solid was dried under reduced pressure and then pulverized in a dry medium stirring mill to obtain 20.5 g of an aromatic phosphate metal salt AS2 represented by the following chemical formula AS2 as a white granular product.
  • Aromatic amide compound B1 0.5 g (4 mmol) of aromatic amide compound 3,5-diaminoaniline represented by the following chemical formula B1 obtained by the following synthesis procedure and 30 mL of n-butyl acetate were added to a 100 ml Schlenk flask. and stirred at 25° C. under a nitrogen atmosphere to form a uniform solution. 2.3 g (12 mmol) of pivalic anhydride was added to this solution with a syringe, and the mixture was stirred at 25° C. for 12 hours.
  • Fatty acid metal salt (DS) Fatty acid metal salt DS1: Lithium 12-hydroxystearate
  • the content of the aromatic phosphate ion (A) in the obtained resin additive composition was quantified by the following method. 1. About 20 mg of the resin additive composition was precisely weighed in a 100 mL eggplant flask, 30 mL of a mixed solvent of methanol/water/acetic acid (volume ratio 70/25/5) was added, and ultrasonic irradiation was performed at 25 ° C. for 15 minutes to give an aroma. An extract was obtained by extracting the group phosphate ion (A) in the form of an aromatic phosphate. 2.
  • the resulting extract was transferred to a 50 mL volumetric flask and diluted with a mixed solvent of methanol/water/acetic acid (volume ratio 70/25/5) to obtain a sample solution.
  • a reversed-phase column (manufactured by JASCO Corporation: trade name FINEPAK SIL C18-10 250 mm ⁇ 4.6 mm) and a photodiode array detector (manufactured by Shimadzu Corporation: SPD-M20A equipped with a high-performance liquid chromatograph device (Shimadzu Corporation)
  • the mobile phase is a mixed solvent of methanol / water / acetic acid (volume ratio 70/25/5), column temperature 40 ° C., flow rate 1 mL / min, detection
  • a sample solution was measured under the condition of an instrument wavelength of 275 nm, and the amount of aromatic phosphate contained in the sample solution was quantified by a calibration curve method.
  • the content X (% by mass) of the aromatic phosphate ion (A) in 100% by mass of the resin additive composition was calculated. Calculated. As a result, it was found that the resin additive composition of each example contained an aromatic phosphate ion (A).
  • the content of the aromatic amide compound (B) in the obtained resin additive composition was quantified by the following method. 1. About 20 mg of the resin additive composition was precisely weighed in a 300 mL eggplant flask, 80 ml of chloroform was added, and ultrasonic waves were applied at 25° C. for 15 minutes to extract the aromatic amide compound (B) to obtain an extract. 2. The resulting extract was transferred to a 100 mL volumetric flask and diluted with chloroform to obtain a sample solution. 3.
  • a gas chromatograph (GC-2010, manufactured by Shimadzu Corporation) equipped with a capillary column (manufactured by Shimadzu GLC Co., Ltd.: BPX-5) and a hydrogen flame ionization detector Photoda was used, the carrier gas was helium, and the inlet temperature was 100°C. , column flow rate of 10 mL/min, oven temperature of 100 to 360° C., and heating rate of 15° C./min. did. 4.
  • the content Y (% by mass) of the aromatic amide compound (B) in 100% by mass of the resin additive composition was calculated based on the obtained quantitative value, the weight of the weighed resin additive composition, and the dilution ratio. . As a result, it was found that the resin additive composition of each example contained the aromatic amide compound (B).
  • the sample solution is measured using an ICP emission spectrometer (SPS3500 manufactured by Seiko Instruments Inc.), the amounts of lithium ions and sodium ions contained in the sample solution are quantified by the calibration curve method, and the obtained quantitative value is Based on this, the respective contents (% by mass) of lithium ions and sodium ions in 100% by mass of the resin additive composition were calculated. As a result, it was found that the resin additive compositions of Examples 1, 3, 4 and 5 contained lithium ions, and Example 2 contained sodium ions.
  • the aqueous layer was further extracted twice with 5 mL of n-hexane, and the hexane layer was transferred to a 25 mL volumetric flask and then diluted with n-hexane to obtain an extract. Then, the amount of fatty acid contained in the extract is quantified by a gas chromatography method in accordance with JIS K 3331, and the content of fatty acid ions (D) in 100% by mass of the resin additive composition ( % by mass) was calculated. As a result, it was found that the resin additive composition of each example contained fatty acid ions (D).
  • the obtained resin additive composition was evaluated as follows. In the table, "-" indicates that no raw material component is included or evaluation has not been carried out.
  • the resulting mixture was melt-kneaded using a twin-screw extruder (TEX28V manufactured by Japan Steel Works, Ltd.) at an extrusion temperature of 240°C, a screw rotation speed of 150 rpm, and a feed speed of 15 kg/h to produce a resin composition in the form of pellets. .
  • TEX28V twin-screw extruder
  • no resin additive composition was used in the production of the resin composition of Reference Example.
  • the haze change rate of Example 1, 3, 4 or 5 relative to Comparative Example 1 [(Haze of Example 1, 3, 4 or 5 - Haze of Comparative Example 1) / Haze of Comparative Example 1 x 100] (%)
  • Haze change rate of Comparative Example 3 to Comparative Example 1 [(Haze of Comparative Example 3 ⁇ Haze of Comparative Example 1)/Haze of Comparative Example 1 ⁇ 100] (%)
  • Haze of Example 2 to Comparative Example 2 The rate of change [(haze of Example 2 ⁇ haze of Comparative Example 2)/haze of Comparative Example 2 ⁇ 100] (%) was calculated and shown in Table 1.
  • the resin additive composition of each example showed results of improving the transparency of the resin composition compared to each corresponding comparative example.
  • Examples 1 to 5 when the corresponding Comparative Examples 1 and 2, which do not contain the aromatic amide compound (B), are used as a standard, compared with Comparative Example 3, the absolute value of the negative value of the haze change rate Since the value increases, it was confirmed that the transparency of the resin composition can be improved.
  • Examples 1, 3, 4 and 5 have smaller haze than corresponding Comparative Examples 1 and 3 containing the same aromatic phosphate metal salt (AS2), transparency can be improved.
  • Example 2 has a smaller haze than the corresponding Comparative Example 2 containing the same aromatic phosphate metal salt (AS1), confirming that the transparency of the resin composition can be improved.

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  • 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

Cette composition d'additif de résine comprend des ions (A) d'un ester d'acide phosphorique aromatique donné, un composé amide aromatique donné (B) et des ions de métaux alcalins (C) et a été conçue de sorte que le rapport de masse de la teneur Y du composé amide aromatique (B) à la teneur X des ions (A) d'un ester d'acide phosphorique aromatique, Y/X, est de 0,01 à 0,15.
PCT/JP2022/016159 2021-04-05 2022-03-30 Composition d'additif de résine, composition de résine et article moulé WO2022215632A1 (fr)

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WO2024031013A1 (fr) * 2022-08-04 2024-02-08 Fina Technology, Inc. Compositions de polypropylène présentant une clarté améliorée

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WO2020056034A1 (fr) * 2018-09-12 2020-03-19 Fina Technology, Inc. Mélanges d'agents clarifiants pour une performance optimale

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JP2013505309A (ja) * 2009-09-18 2013-02-14 ビーエーエスエフ ソシエタス・ヨーロピア 引っかき抵抗性、機械的安定性、およびヘイズの向上したポリマー組成物
JP2012152933A (ja) * 2011-01-24 2012-08-16 Japan Polypropylene Corp プロピレン系樹脂射出成形品
JP2016089176A (ja) * 2014-10-31 2016-05-23 サンアロマー株式会社 ポリプロピレン系樹脂組成物及び成形品
JP2016121219A (ja) * 2014-12-24 2016-07-07 日本ポリプロ株式会社 医療用プロピレン系樹脂組成物およびその成形品
WO2016158258A1 (fr) * 2015-03-31 2016-10-06 株式会社Adeka Composition d'additif pour résine et composition de résine thermoplastique antistatique
JP2017036356A (ja) * 2015-08-06 2017-02-16 サンアロマー株式会社 ポリプロピレン系樹脂組成物及び射出成形品
JP2018104673A (ja) * 2016-12-26 2018-07-05 サンアロマー株式会社 ポリプロピレン系樹脂組成物及び射出圧縮成形体
WO2020056034A1 (fr) * 2018-09-12 2020-03-19 Fina Technology, Inc. Mélanges d'agents clarifiants pour une performance optimale

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Publication number Priority date Publication date Assignee Title
WO2024031013A1 (fr) * 2022-08-04 2024-02-08 Fina Technology, Inc. Compositions de polypropylène présentant une clarté améliorée

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