WO2019159643A1 - Composé contenant du polyalkylène glycol - Google Patents

Composé contenant du polyalkylène glycol Download PDF

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Publication number
WO2019159643A1
WO2019159643A1 PCT/JP2019/002321 JP2019002321W WO2019159643A1 WO 2019159643 A1 WO2019159643 A1 WO 2019159643A1 JP 2019002321 W JP2019002321 W JP 2019002321W WO 2019159643 A1 WO2019159643 A1 WO 2019159643A1
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Prior art keywords
group
carbon atoms
polyalkylene glycol
containing compound
compound
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PCT/JP2019/002321
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English (en)
Japanese (ja)
Inventor
大祐 道尭
西川　毅
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Nippon Shokubai Co Ltd
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Nippon Shokubai Co Ltd
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Priority claimed from JP2018228092A external-priority patent/JP2019137833A/ja
Application filed by Nippon Shokubai Co Ltd filed Critical Nippon Shokubai Co Ltd
Priority to US16/969,103 priority Critical patent/US20210032568A1/en
Priority to EP19755163.3A priority patent/EP3753968A1/fr
Publication of WO2019159643A1 publication Critical patent/WO2019159643A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • the present invention relates to a polyalkylene glycol-containing compound. More specifically, the present invention relates to a polyalkylene glycol-containing compound useful for a detergent or the like.
  • the compound having a polyalkylene glycol chain is imparted with properties such as hydrophilicity, hydrophobicity, flexibility and steric repulsion by appropriately adjusting the chain length and the constituent alkylene oxide, and is a detergent builder, detergent and water treatment agent. It is used in various applications such as scale inhibitors and dispersants.
  • Patent Document 1 discloses a polyalkylene glycol represented by a specific structure used as a scale inhibitor, a detergent composition, and a pigment dispersant.
  • Patent Document 1 discloses a polyalkylene glycol represented by a specific structure used as a detergent composition, but conventional polyalkylene glycol-containing compounds have room for improvement in detergency. there were.
  • This invention is made
  • the present inventor has conducted various studies on the polyalkylene glycol-containing compound, and the polyalkylene glycol-containing compound having a specific structure having a hydrophobic group at the end of the polyalkylene glycol chain is superior in detergency to conventional polyalkylene glycol-containing compounds. As a result, the inventors have arrived at the present invention by conceiving that the above problems can be solved brilliantly.
  • the first aspect of the present invention is the following formula (1-1);
  • R 0 is .R 1 representing a divalent organic group having 1 to 20 carbon atoms are the same or different
  • .R a representative of the alkylene group having 2 to 20 carbon atoms is a C1- An alkyl group having 20 substituents, an aryl group having 6 to 20 carbon atoms, an aryl group optionally having substituents, or a substituent having 1 to 20 carbon atoms
  • N represents an average added mole number of an oxyalkylene group and represents a number of 1 to 300).
  • R a is an alkyl group having 1 to 20 carbon atoms, or formula (1-2); —CH 2 CH (OR a2 ) CH 2 —OR a1 (1-2) (Wherein R a1 represents an alkyl group or heterocyclic group having 1 to 17 carbon atoms, or an aryl group having 6 to 17 carbon atoms. R a2 represents a hydrogen atom or a substituent having 1 to 16 carbon atoms. An optionally substituted alkyl group having 6 to 16 carbon atoms, an optionally substituted aryl group, or an optionally substituted heterocyclic group having 1 to 16 carbon atoms It is preferable that it is group represented by this.
  • R 0 represents an alkylene group having 1 to 20 carbon atoms, the following formula (1-4); — (CH 2 ) p —O—CH 2 CH (OR 01 ) CH 2 — (1-4) (Wherein R 01 represents a hydrogen atom or an organic group having 1 to 17 carbon atoms, p represents a number of 0 to 10), the following formula (1-7); — (CH 2 ) p ′ —CH (OH) CH 2 — (1-7) (Wherein p ′ represents a number of 0 to 5), or the following formula (1-8); —R 03 —S—R 04 — (1-8) (Wherein R 03 and R 04 are the same or different and each represents an optionally substituted alkylene group having 1 to 10 carbon atoms).
  • the second aspect of the present invention is a compound represented by the formula (2-1);
  • R 0 represents a divalent organic group having 1 to 20 carbon atoms.
  • R 1 is the same or different and represents an alkylene group having 2 to 20 carbon atoms.
  • R b represents 21 to 21 carbon atoms.
  • n is an average added mole number of an oxyalkylene group, and represents a number of 1 to 300.
  • R b represents the following formula (2-2); —CH 2 CH (OR b2 ) CH 2 OR b1 (2-2) (Wherein R b1 represents an organic group having 1 to 47 carbon atoms, and R b2 represents a hydrogen atom or an organic group having 1 to 46 carbon atoms).
  • R b is preferably an alkyl group having 21 to 30 carbon atoms which may have a substituent, or an aryl group having 21 to 30 carbon atoms which may have a substituent.
  • R 0 represents an alkylene group having 1 to 20 carbon atoms, the following formula (1-4); — (CH 2 ) p —O—CH 2 CH (OR 01 ) CH 2 — (1-4) (Wherein R 01 represents a hydrogen atom or an organic group having 1 to 17 carbon atoms, p represents a number of 0 to 10), the following formula (1-7); — (CH 2 ) p ′ —CH (OH) CH 2 — (1-7) (Wherein p ′ represents a number of 0 to 5), or the following formula (1-8); —R 03 —S—R 04 — (1-8) (Wherein R 03 and R 04 are the same or different and each represents an optionally substituted alkylene group having 1 to 10 carbon atoms).
  • R 2 represents a divalent organic group having 21 to 100 carbon atoms.
  • R 1 is the same or different and represents an alkylene group having 2 to 20 carbon atoms.
  • R c represents 1 to 1 carbon atoms. 50, an alkyl group which may have a substituent, an aryl group having 6 to 50 carbon atoms, an optionally substituted aryl group, or a substituent having 1 to 50 carbon atoms.
  • N is an average added mole number of the oxyalkylene group, and represents a number of 1 to 300.
  • R 2 represents the following formula (3-5); —CH 2 CH 2 OCH 2 CH (OR 22 ) CH 2 — (3-5) (Wherein R 22 represents an organic group having 16 to 95 carbon atoms).
  • the present invention also includes a composition comprising the polyalkylene glycol-containing compound and other components other than the compound, wherein the content of the polyalkylene glycol-containing compound is 1 to 99% by mass with respect to 100% by mass of the composition. It is also a thing.
  • the present invention is also a detergent composition comprising the polyalkylene glycol-containing compound and a detergent additive other than the compound.
  • polyalkylene glycol-containing compound of the present invention has the above-described configuration and is superior in detergency to conventional polyalkylene glycol-containing compounds, it can be suitably used for detergents and the like.
  • the polyalkylene glycol-containing compound of the first invention (hereinafter also referred to as the PAG compound of the first invention) is represented by the above formula (1-1).
  • R a in the above formula (1-1) is an alkyl group having 1 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, Alternatively, it is a heterocyclic group having 1 to 20 carbon atoms, which may have a substituent.
  • the PAG compound of the first invention comprises a pyrrolidone skeleton that interacts with carboxyl groups and ester groups contained in dirt such as sebum, and a hydrophobic group having a specific structure represented by Ra at the polyalkylene glycol chain end. Since the interaction with dirt (especially oil dirt) is strengthened and the interfacial tension between water and oil can be reduced, the detergency is improved. In addition, since the PAG compound of the first invention has the above structure, it has an excellent balance between hydrophobicity and hydrophilicity. Also excellent.
  • the number of carbon atoms of the alkyl group is preferably 2-19. More preferably, it is 3-18, still more preferably 4-17, still more preferably 6-16, still more preferably 8-15, and particularly preferably 12-14.
  • the carbon number of the alkyl group includes the carbon number of the substituent. In the following, the carbon number of a hydrocarbon group that may have a substituent also includes the carbon number of the substituent.
  • alkyl group examples include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group (amyl group), n-hexyl group, n-heptyl group, n-octyl group, n- Nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n- Nonadecyl group, n-eicosanyl group, i-propyl group, sec-butyl group, i-butyl group, t-butyl group, 1-methylbutyl group, 1-ethylpropyl group, 2-methylbutyl group, i-a
  • the aryl group preferably has 6 to 19 carbon atoms. More preferably, it is 6 to 16, more preferably 6 to 10, and particularly preferably 6 to 8.
  • Examples of the aryl group include phenyl, benzyl, phenethyl, o-, m- or p-tolyl, 2,3- or 2,4-xylyl, mesityl, naphthyl, anthryl, phenanthryl.
  • a phenyl group and a benzyl group are preferable.
  • the number of carbon atoms of the heterocyclic group is preferably 1-19. More preferably, it is 2 to 16, more preferably 2 to 10, and particularly preferably 2 to 8.
  • the heterocyclic group is preferably an aromatic heterocyclic group having aromaticity, for example, a pyrrole group, a furan group, a thiophene group, an imidazole group, a pyrazole group, an oxazole group, an isoxazole group, a thiazole group, an isothiazole group.
  • Tetrazole group Tetrazole group, pyridinyl group, pyrimidinyl group, pyridazinyl group, pyrazinyl group, 1,2,3-triazinyl group, quinolinyl group, isoquinolinyl group, quinazolinyl group, phthalazinyl group, buteridinyl group, coumarinyl group, chromonyl group, 1,4- Examples include benzodiazepinyl group, indole group, benzimidazole group, benzofuranyl group, purinyl group, acridinyl group, phenoxazinyl group, phenothiazinyl group, and those having the above alkyl group in the aromatic heterocycle. . Among these, a tetrazole group and an imidazole group are preferable.
  • alkyl group, aryl group, and heterocyclic group may have include a hydroxyl group, an alkoxy group, a carboxyl group, an acyl group, a sulfonic acid group, an amino group, a phosphoric acid group, an ether group, and a thioether.
  • R a has a substituent, the following formula (1-2); —CH 2 CH (OR a2 ) CH 2 —OR a1 (1-2) (Wherein R a1 represents an alkyl group or heterocyclic group having 1 to 17 carbon atoms, or an aryl group having 6 to 17 carbon atoms. R a2 represents a hydrogen atom or a substituent having 1 to 16 carbon atoms. An optionally substituted alkyl group having 6 to 16 carbon atoms, an optionally substituted aryl group, or an optionally substituted heterocyclic group having 1 to 16 carbon atoms It is preferable that it is group represented by this.
  • the reaction product obtained in the first step is reacted with a hydrophobic group-containing compound having a glycidyl ether group.
  • a PAG compound having R a having a group represented by the above formula (1-2) can be obtained.
  • the carbon number of the alkyl group for R a1 is preferably 8 to 14, more preferably 12 to 14.
  • the number of carbon atoms in the aryl group of R a1 is preferably 6 to 14, more preferably 6 to 12, still more preferably 6 to 10, and particularly preferably 6 to 8.
  • the number of carbon atoms of the heterocyclic group for R a1 is preferably 2 to 14, more preferably 2 to 12, and still more preferably 2 to 8.
  • R a2 is an alkyl group having 1 to 16 carbon atoms which may have a substituent, an aryl group having 6 to 16 carbon atoms which may have a substituent, or 1 to 16 carbon atoms.
  • a heterocyclic group which may have a substituent the following formula (1-3); — [CH 2 CH (CH 2 —O—R a3 ) —O] m —H (1-3) (Wherein R a3 are the same or different and each represents an alkyl group having 1 to 13 carbon atoms, an aryl group having 6 to 13 carbon atoms, or a heterocyclic group having 1 to 13 carbon atoms. It is preferably a group represented by 4).
  • the reaction product obtained in the first step was reacted with a hydrophobic group-containing compound having a glycidyl ether group.
  • a hydrophobic group-containing compound having a glycidyl ether group when one molecule of a hydrophobic group-containing compound having a glycidyl ether group further reacts with the hydroxyl group in the generated —CH 2 CH (OH) CH 2 —OR a1 , m in the above formula (1-3) A PAG compound of 1 is produced.
  • a PAG compound having m of 2 is produced.
  • the alkyl group, aryl group, and heterocyclic group in R a3 are included in the above description.
  • the number of carbon atoms of the alkyl group for R a3 is preferably 4 to 13, and more preferably 8 to 12.
  • the number of carbon atoms of the aryl group of R a3 is preferably 6 to 13, and more preferably 6 to 10.
  • the number of carbon atoms in the heterocyclic group for R a3 is preferably 1 to 13, and more preferably 2 to 10.
  • R a3 is preferably an alkyl group having 1 to 13 carbon atoms. Further, R a3 is preferably the same group as R a1 .
  • the m is preferably 1.
  • R a in the above formula (1-1) is an alkyl group having 1 to 20 carbon atoms, or R a is a group represented by the above formula (1-2), and R a2 is a hydrogen atom.
  • R 1 in the above formula (1-1) represents an alkylene group having 2 to 20 carbon atoms “same or different”, and this is because all the alkylene groups of R 1 existing in n in the polyalkylene glycol are all present. It means that they may be the same or different.
  • the oxyalkylene group represented by R 1 O is an alkylene oxide adduct. Examples of such alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, 1-butene. Examples thereof include alkylene oxides having 2 to 8 carbon atoms such as oxide, 2-butene oxide and styrene oxide.
  • alkylene oxides having 2 to 4 carbon atoms such as ethylene oxide, propylene oxide, butylene oxide, and still more preferred are ethylene oxide and propylene oxide.
  • the polyalkylene glycol is any two or more alkylene oxide adducts selected from ethylene oxide, propylene oxide, butylene oxide, styrene oxide, etc., any of random addition, block addition, alternating addition, etc. Form may be sufficient.
  • the oxyalkylene group in the polyalkylene glycol preferably has an oxyethylene group as an essential component, and more preferably 50 mol% or more is an oxyethylene group. More preferably, 90 mol% or more is an oxyethylene group.
  • n is the average added mole number of the oxyalkylene group and represents a number of 1 to 300.
  • n is preferably 2 to 200, more preferably 3 to 100, still more preferably 5 to 50, and particularly preferably 7 to 30.
  • R 0 in the above formula (1-1) represents a divalent organic group having 1 to 20 carbon atoms.
  • the carbon number of the divalent organic group is preferably 2-15. More preferably, it is 2 to 10, still more preferably 2 to 8, and particularly preferably 2 to 5. Although it does not restrict
  • the divalent hydrocarbon group may have are as described above, and preferably a hydroxyl group, an alkoxy group, an ether group, a thioether group, and a carbonyl group.
  • groups represented by the following formulas (1-4), (1-7) and (1-8) are preferable.
  • the divalent hydrocarbon group is preferably an alkylene group obtained by extracting one hydrogen atom from an aliphatic alkyl group or an alicyclic alkyl group. That is, R 0 is preferably an alkylene group having 1 to 20 carbon atoms. Examples of the alkylene group include methylene group, methylmethylene group, ethylene group, n-propylene group, isopropylene group, n-butylene group, isobutylene group, sec-butylene group, tert-butylene group, n-pentylene group, and isopentylene group.
  • Neopentylene group hexylene group, heptylene group, octylene group, nonylene group, decylene group, undecylene group, dodecylene group, tridecylene group, tetradecylene group, pentadecylene group, hexadecylene group, heptadecylene group, octadecylene group and the like.
  • R 0 represents the following formula (1-4); — (CH 2 ) p —O—CH 2 CH (OR 01 ) CH 2 — (1-4)
  • R 01 represents a hydrogen atom or an organic group having 1 to 17 carbon atoms.
  • P represents a number of 0 to 10).
  • the p is preferably 1 to 8, and more preferably 2 to 5.
  • Examples of the organic group in R 01 include a hydrocarbon group which may have a substituent.
  • a hydrocarbon group which may have a substituent.
  • the above-mentioned aliphatic or alicyclic alkyl group, an aryl group, etc. are mentioned.
  • Specific examples of the substituent that the hydrocarbon group may have are as described above.
  • the organic group having 1 to 17 carbon atoms is preferably the following formula (1-5);
  • R 02 is the same or different and represents an alkyl group having 1 to 12 carbon atoms.
  • Q is a number of 1 to 2.
  • R 1 is the same or different and has 2 to 20 carbon atoms.
  • R 1 in the formula (1-5) is the same as R 1 in the formula (1).
  • Specific examples of the alkyl group having 1 to 12 carbon atoms in R 02 of the above formula (1-5) are included in the description of R a .
  • the number of carbon atoms of the alkyl group represented by R 02 is preferably 4 to 12, and more preferably 8 to 12.
  • R 02 is preferably the same group as R a .
  • the q is preferably 1.
  • R 01 is preferably a hydrogen atom.
  • Examples of the group represented by the formula (1-4) include the following formula (1-6); —CH 2 CH 2 OCH 2 CH (OH) CH 2 — (1-6) It is preferable that it is group represented by these.
  • R 0 is preferably a group represented by the above formula (1-6) or an alkylene group having 1 to 20 carbon atoms.
  • the alkylene group preferably has 1 to 15 carbon atoms, more preferably 2 to 10 carbon atoms, still more preferably 2 to 8 carbon atoms, and particularly preferably 2 to 5 carbon atoms.
  • R 0 represents the following formula (1-7); — (CH 2 ) p ′ —CH (OH) CH 2 — (1-7) (Wherein p ′ represents a number of 0 to 5) is also a preferred embodiment of the present invention.
  • the p ′ is preferably 1 to 4, more preferably 1 to 3, and most preferably 1.
  • R 0 represents the following formula (1-8); —R 03 —S—R 04 — (1-8) (Wherein R 03 and R 04 are the same or different and each represents an optionally substituted alkylene group having 1 to 10 carbon atoms).
  • R 03 and R 04 are the same or different and each represents an optionally substituted alkylene group having 1 to 10 carbon atoms.
  • R 03 and R 04 are the same or different and each represents an optionally substituted alkylene group having 1 to 10 carbon atoms.
  • R 03 and R 04 are the same or different and each represents an optionally substituted alkylene group having 1 to 10 carbon atoms.
  • R 03 and R 04 are the same or different and each represents an optionally substituted alkylene group having 1 to 10 carbon atoms.
  • Specific examples of the alkylene group having 1 to 10 carbon atoms are as described above.
  • the number of carbon atoms of the alkylene group in R 03 is preferably 1 to 8, more preferably 1 to 6, still more preferably 1 to 4, and most
  • R 03 is preferably an alkylene group having no substituent. More preferably, methylene group, methylmethylene group, ethylene group, n-propylene group, isopropylene group, n-butylene group, isobutylene group, sec-butylene group, tert-butylene group, n-pentylene group, isopentylene group, neopentylene group More preferred are a methylene group, a methylmethylene group, an ethylene group and an n-propylene group, and particularly preferred is an ethylene group.
  • R 04 is preferably an alkylene group having 1 to 5 carbon atoms having a substituent such as a carbonyl group, a hydroxyl group, a carboxyl group, or a sulfonic acid group. More preferably, it is a C 1-5 alkylene group having a carbonyl group.
  • the alkylene group having a carbonyl group is preferably in a form in which the carbonyl carbon of R 04 is bonded to an oxygen atom derived from polyalkylene glycol.
  • the preferred form of the alkylene group for R 04 is the same as that for R 03 .
  • the group represented by the above formula (1-8) is preferably the following formula (1-9); —R 05 —S—R 06 CO— (1-9) (Wherein R 05 represents an alkylene group having 1 to 10 carbon atoms; R 06 represents an alkylene group having 1 to 9 carbon atoms), and more preferably the following formula ( 1-10); —CH 2 CH 2 —S—CH 2 CH 2 —CO— (1-10) It is group represented by these.
  • the PAG compound of the first invention preferably has a number average molecular weight of 500 to 100,000. More preferably, it is 600 to 50,000, still more preferably 650 to 10,000, and particularly preferably 700 to 5,000.
  • the number average molecular weight of the PAG compound can be calculated based on the molecular weight of each structural unit constituting the PAG compound and the number of each structural unit.
  • the content ratio of the group represented by Ra in the formula (1-1) is preferably 2.5 to 60% by mass with respect to 100% by mass of the PAG compound. .
  • the hydrophobicity of a PAG compound becomes a more suitable range, the interaction with respect to dirt, such as sebum, improves more. More preferably, it is 3 to 50% by mass, and still more preferably 4 to 40% by mass.
  • the polyalkylene glycol-containing compound of the second invention (hereinafter also referred to as the PAG compound of the second invention) is a compound represented by the above formula (2-1).
  • R 0, R 1 and n in the formula (2-1) is the same as R 0, R 1 and n in the above formula (1-1).
  • R b in the above formula (2-1) is an organic group having 21 to 50 carbon atoms.
  • the PAG compound of the second invention also has a pyrrolidone skeleton that interacts with carboxyl groups and ester groups contained in dirt such as sebum, and a carbon number represented by R b at the end of the polyalkylene glycol chain.
  • Examples of the organic group include a hydrocarbon group which may have a substituent and a hydrocarbon group which may have a hetero atom.
  • Examples of the hydrocarbon group include an aliphatic alkyl group, an alicyclic alkyl group, an alkenyl group, an alkynyl group, and an aryl group.
  • Examples of the hydrocarbon group having a hetero atom include the above-described heterocyclic groups.
  • Examples of the aliphatic alkyl group having 21 to 50 carbon atoms include heicosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group, octacosyl group, nonacosyl group, triacontyl group, pentatriacontyl group , Tetracontyl group, pentatetracontyl group, pentacontyl group and the like.
  • Examples of the alicyclic alkyl group having 21 to 50 carbon atoms include cyclopropyloctadecyl group, cyclobutylheptadecyl group, cyclopentylhexadecyl group, cyclohexylpentadecyl group, cycloheptyltetradecyl group, cyclooctyltridecyl group and the like.
  • An alicyclic alkyl group is mentioned.
  • alkenyl group having 21 to 50 carbon atoms examples include, for example, eicosenyl group, henycocenyl group, dococenyl group, tricocenyl group, tetracocenyl group, pentacocenyl group, hexacocenyl group, heptacocenyl group, octacocenyl group, nonacosenyl group, triaconenyl group, pentatria Examples thereof include a contenyl group, a tetracontenyl group, a pentatetracontenyl group, and a pentacontenyl group.
  • alkynyl group having 21 to 50 carbon atoms examples include eicosinyl group, henocosinyl group, docosinyl group, tricosinyl group, tetracosinyl group, pentacosinyl group, hexacosinyl group, heptacosinyl group, octacosinyl group, nonacosynyl group, triacontinyl group, pentatria Continyl group, tetracontinyl group, pentatetracontinyl group, pentacontinyl group and the like can be mentioned.
  • Examples of the aryl group having 21 to 50 carbon atoms include a quarterphenyl group, a kinkphenyl group, and the like, and these groups, phenyl group, naphthyl group, fluorenyl group, anthracenyl group, phenanthryl group, biphenyl group, terphenyl group, Examples include groups in which an alkyl group or the like is bonded to an aromatic ring such as a distyrenated phenyl group.
  • the carbon number of the organic group having 21 to 50 carbon atoms is preferably 21 to 40, more preferably 21 to 35, still more preferably 21 to 30, even more preferably 21 to 28, The preferred range is 21-25.
  • R b is an alkyl group having 21 to 30 carbon atoms which may have a substituent or an aryl group having 21 to 30 carbon atoms which may have a substituent is the form of the present invention. This is one of the preferred embodiments.
  • R b When R b has a substituent, R b is represented by the following formula (2-2); —CH 2 CH (OR b2 ) CH 2 OR b1 (2-2) (Wherein R b1 represents an organic group having 1 to 47 carbon atoms, and R b2 represents a hydrogen atom or an organic group having 1 to 46 carbon atoms).
  • R b1 represents an organic group having 1 to 47 carbon atoms
  • R b2 represents a hydrogen atom or an organic group having 1 to 46 carbon atoms.
  • R b1 is an organic group having 1 to 47 carbon atoms
  • R b2 is a hydrogen atom or an organic group having 1 to 46 carbon atoms.
  • R b1 is an organic group having 18 to 47 carbon atoms.
  • the organic group include hydrocarbon groups such as aliphatic or alicyclic alkyl groups, aryl groups, and heterocyclic groups. Specific examples of the aliphatic or alicyclic alkyl group having 1 to 46 carbon atoms, the aryl group, and the heterocyclic group are included in the above description. Specific examples of the substituent that the hydrocarbon group may have are as described above.
  • R b2 is an organic group having 1 to 46 carbon atoms
  • the following formula (2-3) — [CH 2 CH (CH 2 —O—R b3 ) —O] k —H (2-3) (Wherein R b3 are the same or different and each represents an alkyl group having 1 to 43 carbon atoms, k is a number of 1 to 11).
  • R b3 are the same or different and each represents an alkyl group having 1 to 43 carbon atoms, k is a number of 1 to 11).
  • R b3 Specific examples of the alkyl group having 1 to 43 carbon atoms in R b3 are included in the above.
  • the number of carbon atoms of the alkyl group for R b3 is preferably 1 to 40, and more preferably 8 to 30.
  • R b3 is preferably the same group as R b1 .
  • the k is preferably 1.
  • R b in the above formula (2-1) is an alkyl group having 21 to 50 carbon atoms, or R b is a group represented by the above formula (2-2), and R b2 is a hydrogen atom. Groups are preferred.
  • the PAG compound of the second invention preferably has a number average molecular weight of 500 to 100,000. More preferably, it is 600 to 50,000, still more preferably 650 to 10,000, and particularly preferably 700 to 5,000.
  • the content ratio of the group represented by R b in the formula (2-1) is preferably 2.5 to 60% by mass with respect to 100% by mass of the PAG compound. .
  • the hydrophobicity of a PAG compound becomes a more suitable range, the interaction with respect to dirt, such as sebum, improves more. More preferably, it is 3 to 50% by mass, and still more preferably 4 to 40% by mass.
  • the polyalkylene glycol-containing compound of the third invention (hereinafter also referred to as the PAG compound of the third invention) is represented by the above formula (3-1).
  • R 1 and n in the formula (3-1) is the same as R 1 and n in the above formula (1-1).
  • R 2 is a divalent organic group having 21 to 100 carbon atoms.
  • R c is an alkyl group having 1 to 50 carbon atoms which may have a substituent, an aryl group having 6 to 50 carbon atoms, which may have a substituent, or 1 to 50 carbon atoms, It is a heterocyclic group which may have a substituent.
  • the PAG compound of the third aspect of the present invention has a pyrrolidone skeleton that interacts with a carboxyl group or an ester group contained in dirt such as sebum, and a carbon number represented by R 2 between the pyrrolidone skeleton and the polyalkylene glycol chain.
  • alkyl group, aryl group, and heterocyclic group in R c are included in the specific examples of the alkyl group, aryl group, and heterocyclic group described above.
  • the number of carbon atoms of the alkyl group which may have a substituent in R c is preferably 2 to 40, more preferably 4 to 30, still more preferably 8 to 20, and particularly preferably. 10 to 18, most preferably 12 to 14.
  • the number of carbon atoms of the aryl group which may have a substituent for R c is preferably 6 to 40, more preferably 6 to 30, and still more preferably 6 to 25.
  • the number of carbon atoms of the heterocyclic group which may have a substituent in R c is preferably 1 to 40, more preferably 2 to 30, and still more preferably 2 to 20.
  • Specific examples of the substituent that the alkyl group, aryl group, and heterocyclic group may have are as described above, preferably a hydroxyl group, an alkoxy group, and an ether group.
  • R c represents the following formula (3-2); —CH 2 CH (OR c2 ) CH 2 OR c1 (3-2) (Wherein R c1 represents an alkyl group or heterocyclic group having 1 to 47 carbon atoms or an aryl group having 6 to 47 carbon atoms. R c2 represents a hydrogen atom or a substituent having 1 to 46 carbon atoms.
  • the reaction product obtained in the first step is reacted with a hydrophobic group-containing compound having a glycidyl ether group.
  • a PAG compound having R c having a group represented by the above formula (3-2) can be obtained.
  • the alkyl group of R c1 preferably has 4 to 30 carbon atoms, more preferably 8 to 20 carbon atoms.
  • the number of carbon atoms of the aryl group represented by R c1 is preferably 6-30, more preferably 6-25.
  • the number of carbon atoms in the heterocyclic group of R c1 is preferably 1-30, more preferably 2-20.
  • R c2 is an alkyl group having 1 to 46 carbon atoms which may have a substituent, an aryl group having 6 to 46 carbon atoms, which may have a substituent, or 1 to 46 carbon atoms.
  • a heterocyclic group which may have a substituent the following formula (3-3); — [CH 2 CH (CH 2 —O—R c3 ) —O] j —H (3-3) (Wherein R c3 are the same or different and each represents an alkyl group having 1 to 43 carbon atoms, an aryl group having 6 to 43 carbon atoms, or a heterocyclic group having 1 to 43 carbon atoms.
  • the reaction product obtained in the first step was reacted with a hydrophobic group-containing compound having a glycidyl ether group.
  • a hydrophobic group-containing compound having a glycidyl ether group when one molecule of a hydrophobic group-containing compound having a glycidyl ether group further reacts with the hydroxyl group in the —CH 2 CH (OH) CH 2 —OR c1 to be generated, j in the above formula (3-3) A PAG compound of 1 is produced.
  • a PAG compound having j of 2 is produced.
  • the alkyl group, aryl group, and heterocyclic group in R c3 are included in the above description.
  • the number of carbon atoms of the alkyl group represented by R c3 is preferably 4 to 30, and more preferably 8 to 20.
  • the number of carbon atoms of the aryl group of R c3 is preferably 6 to 30, and more preferably 6 to 25.
  • the number of carbon atoms in the heterocyclic group represented by R c3 is preferably 1-30 , more preferably 2-20.
  • R c3 is preferably an alkyl group having 12 to 14 carbon atoms.
  • R c3 is preferably the same group as R c1 .
  • J is preferably 1 to 5. More preferably, it is 1-2.
  • R c in the above formula (3-1) is preferably an alkyl group which may have a substituent having 1 to 50 carbon atoms, more preferably a linear or branched aliphatic alkyl having no substituent. It is a group.
  • R 2 in the above formula (3-1) represents a divalent organic group having 21 to 100 carbon atoms.
  • divalent organic group which may have a substituent.
  • divalent hydrocarbon group examples include groups obtained by extracting one hydrogen atom from a monovalent hydrocarbon group such as an aliphatic alkyl group, an alicyclic alkyl group, and an aryl group. Specific examples of the aliphatic or alicyclic alkyl group having 21 to 100 carbon atoms are included in the above.
  • R 2 is preferably an aliphatic or alicyclic alkylene group which may have a substituent.
  • the following formula (3-4) — (CH 2 ) s —O—CH 2 CH (OR 21 ) CH 2 — (3-4) (Wherein R 21 represents an organic group having 8 to 97 carbon atoms, and s represents a number of 0 to 10). The above s is preferably 1 to 8, and more preferably 2 to 5.
  • R 2 is more preferably the following formula (3-5); —CH 2 CH 2 —O—CH 2 CH (OR 22 ) CH 2 — (3-5) (Wherein R 22 represents an organic group having 16 to 95 carbon atoms).
  • the following formula (3-6) is preferable. );
  • R 23 is the same or different and represents an alkyl group having 1 to 92 carbon atoms.
  • T is a number of 1 to 16.
  • R 1 is the same or different and has 2 to 20 carbon atoms. Represents an alkylene group, and u is an average addition mole number of the oxyalkylene group, which is a number of 1 to 46).
  • R 1 is the same as R 1 in the above formula (1-1).
  • the number of carbon atoms of the alkyl group in R 23 is preferably 3 to 18, more preferably 4 to 14, and still more preferably 8 to 12.
  • R 23 is preferably the same group as R c .
  • the t is preferably 1 to 10, more preferably 1 to 5, and still more preferably 1 to 3.
  • U is preferably 1 to 30, more preferably 1 to 20, and still more preferably 8 to 18.
  • the PAG compound of the third invention preferably has a number average molecular weight of 500 to 100,000. More preferably, it is 600 to 50,000, still more preferably 650 to 10,000, and particularly preferably 700 to 5,000.
  • the content ratio of the group represented by R c in the formula (3-1) is preferably 2.5 to 60% by mass with respect to 100% by mass of the PAG compound. .
  • the hydrophobicity of a PAG compound becomes a more suitable range, the interaction with respect to dirt, such as sebum, improves more. More preferably, it is 3 to 50% by mass, and still more preferably 4 to 40% by mass.
  • the method for producing the PAG compound of the present invention is not particularly limited. For example, (i) a first step of reacting a compound having a pyrrolidone skeleton with an alkylene oxide, and a compound having a hydrophobic group in the resulting reaction product (hydrophobic group) And (ii) a compound having a pyrrolidone skeleton and a compound having a hydrophobic group at one end of the polyalkylene glycol (hydrophobic group-containing polyalkylene glycol).
  • the method of manufacturing by performing the process made to react is mentioned.
  • the compound having the pyrrolidone skeleton (hereinafter also referred to as pyrrolidone skeleton-containing compound) is represented by the following formula (4);
  • R 3 represents a hydrogen atom or an organic group having 1 to 20 carbon atoms.
  • R 0 represents a divalent organic group having 1 to 20 carbon atoms.
  • R 1 is the same or different and represents an alkylene group having 2 to 20 carbon atoms.
  • N represents an average of oxyalkylene groups.
  • R 4 -X 1 (6) (Wherein R 4 is an alkyl group having 1 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms and optionally having a substituent, or a carbon number) Represents a heterocyclic group which may have a substituent of 1 to 20.
  • X 1 represents a functional group having reactivity with a hydroxyl group) and is reacted with a hydrophobic group-containing compound represented by It is preferable to manufacture by performing two steps.
  • R 3 is a hydrogen atom or an organic group having 1 to 20 carbon atoms.
  • the organic group having 1 to 20 carbon atoms is reactive with alkylene oxide. It is preferable to have a functional group having In the method (ii), the organic group having 1 to 20 carbon atoms preferably has a functional group having reactivity with a compound represented by the formula (7) described later.
  • the organic group having 1 to 20 carbon atoms preferably has a functional group having reactivity with a compound represented by the formula (7) described later.
  • limit especially as said functional group Polymerizable unsaturated groups, such as a hydroxyl group, a carboxyl group, an epoxy group, a glycidyl group, an amino group, a sulfonic acid group, a phosphoric acid group, a vinyl group, etc. are mentioned.
  • a hydroxyl group, an epoxy group, and a glycidyl group are preferable.
  • the organic group having 1 to 20 carbon atoms is preferably a group in which the functional group is bonded to a hydrocarbon group such as an aliphatic alkyl group, an alicyclic alkyl group, or an aryl group.
  • a hydrocarbon group such as an aliphatic alkyl group, an alicyclic alkyl group, or an aryl group.
  • Specific examples of the aliphatic alkyl group, the alicyclic alkyl group, and the aryl group and the preferable range of the carbon number thereof are as described in R 0 of the above formula (1-1).
  • Specific examples of the compound having a pyrrolidone skeleton represented by the above formula (4) include N-hydroxyethyl pyrrolidone, N-hydroxypropyl pyrrolidone, N-hydroxybutyl pyrrolidone, N-hydroxypentyl pyrrolidone, N-hydroxyhexyl pyrrolidone. Examples thereof include compounds having a hydroxyalkyl group having 1 to 20 carbon atoms on the nitrogen atom of 2-pyrrolidone.
  • Preferred compounds having a pyrrolidone skeleton represented by the formula (4) are N-hydroxyethyl pyrrolidone, N-hydroxypropyl pyrrolidone and N-hydroxybutyl pyrrolidone.
  • R 0 is a divalent organic group having 1 to 20 carbon atoms
  • R 3 in the above formula (4) is a divalent organic group formed by reaction with alkylene oxide.
  • R 4 represents an alkyl group having 1 to 20 carbon atoms, which may have a substituent, an aryl group having 6 to 20 carbon atoms, which may have a substituent, or And a heterocyclic group having 1 to 20 carbon atoms which may have a substituent. Specific examples and preferred examples of these groups are as described for R a in the above formula (1-1).
  • X 1 in the above formula (6) is not particularly limited as long as it is a functional group having reactivity with the hydroxyl group at the polyalkylene glycol terminal of the compound represented by formula (5).
  • X 1 is preferably a halogen atom or a glycidyl group.
  • the halogen atom include fluorine, chlorine, bromine, iodine and the like, preferably chlorine.
  • hydrophobic group-containing compound represented by the above formula (6) examples include a hydrophobic group-containing compound having a halogen atom such as an alkyl halide having 1 to 20 carbon atoms; an alkyl glycidyl having 1 to 20 carbon atoms.
  • hydrophobic group-containing compounds having a glycidyl ether group such as ether.
  • alkyl halide having 1 to 20 carbon atoms examples include methyl chloride, ethyl chloride, propyl chloride, butyl chloride, pentyl chloride, hexyl chloride, heptyl chloride, octyl chloride, nonyl chloride, decyl chloride, undecyl chloride, dodecyl chloride (lauryl). Chloride), tridecyl chloride, tetradecyl chloride, pentadecyl chloride, hexadecyl chloride, heptadecyl chloride, octadecyl chloride, nonadesil chloride, eicosanyl chloride and the like.
  • alkyl halides having 4 to 18 carbon atoms more preferred are 8 to 16 carbon atoms, and still more preferred are 12 to 14 carbon atoms.
  • alkyl glycidyl ether having 1 to 20 carbon atoms examples include methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether
  • Examples include ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, and heptadec
  • R a is —CH 2 CH (OH) CH 2 —.
  • a compound that is OR a1 is produced.
  • the compound represented by the formula (1-1) has a hydroxyl group, and when a hydrophobic group-containing compound having a glycidyl ether group further reacts with the hydroxyl group, Ra is represented by the formula (1-2).
  • R a2 is a structure represented by the formula (1-3).
  • R 1 is the same or different and represents an alkylene group having 2 to 20 carbon atoms, n represents an average addition mole of an oxyalkylene group And represents a number from 1 to 300.
  • X 2 is preferably a hydrogen atom or a reactive functional group).
  • R 1, R a and n in the above formula (7) is the same as R 1, R a and n in the above formula (1-1).
  • X 2 in the above formula (7) is a hydrogen atom or a reactive functional group, and as long as it can react with the organic group represented by R 3 in the compound having a pyrrolidone skeleton represented by the formula (4),
  • the reactive functional group include a halogen atom, a glycidyl group, a hydroxyl group, a carboxyl group, an amino group, and an organic group having 1 to 10 carbon atoms having a thiol group at the terminal.
  • X 2 is preferably a hydrogen atom, a halogen atom, a glycidyl group, or an organic group having 1 to 10 carbon atoms having a thiol group at the terminal, more preferably a hydrogen atom, a glycidyl group, or a carbon number having 1 to 10 carbon atoms having a thiol group at the terminal. 10 organic groups.
  • Specific examples of the compound represented by the formula (7) and having a glycidyl group include alkoxy polyalkylene glycol glycidyl ether having an alkoxy group having 1 to 20 carbon atoms.
  • alkoxy group in the above alkoxy polyalkylene glycol glycidyl ether include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, undecyloxy group.
  • dodecyloxy group (lauryloxy group), tridecyloxy group, tetradecyloxy group, pentadecyloxy group, hexadecyloxy group, heptadecyloxy group, octadecyloxy group, nonadecyloxy group, eicosanyloxy group, etc. Can be mentioned.
  • R 0 is represented by formula (1).
  • a compound which is a group represented by -6) is formed.
  • the compound represented by the formula (1-1) has a hydroxyl group, and when the alkoxypolyalkylene glycol glycidyl ether further reacts with this hydroxyl group, R 0 is represented by the above formula (1-4).
  • R 01 is a structure represented by the formula (1-5).
  • the organic group having 1 to 10 carbon atoms having a thiol group at the terminal in X 2 is preferably the following formula (7-1): -R 04 -SH (7-1) (Wherein R 04 represents an alkylene group having 1 to 10 carbon atoms which may have a substituent).
  • R 04 represents an alkylene group having 1 to 10 carbon atoms which may have a substituent.
  • a carbonyl group, a hydroxyl group, a carboxyl group, a sulfonic acid group and the like are preferable, and a carbonyl group is more preferable.
  • the group represented by the above formula (7-1) is more preferably the following formula (7-2); -CO-R 06 -SH (7-2) (Wherein R 06 represents an alkylene group having 1 to 9 carbon atoms), more preferably the following formula (7-3); —CO—CH 2 CH 2 —SH (7-3) It is group represented by these.
  • R 04 and R 06 are the same as R 04 in formula (1-8) and R 06 in formula (1-9).
  • the compound in which X 2 in the formula (7) is a group represented by the formula (7-2) can be obtained by reacting a mercaptocarboxylic acid with a compound in which X 2 in the formula (7) is a hydrogen atom.
  • a mercaptocarboxylic acid include thioglycolic acid (mercaptoacetic acid), 3-mercaptopropionic acid, 2-mercaptopropionic acid (thiolactic acid), 4-mercaptobutanoic acid, thiomalic acid, and the like. 3-mercaptopropionic acid is preferred.
  • the compound having a pyrrolidone skeleton represented by the formula (4) is a compound represented by the formula (7). It is sufficient if it has a functional group reactive with the hydroxyl group at the terminal of the polyalkylene glycol, but those having an epoxy group are preferred.
  • the pyrrolidone skeleton-containing compound having an epoxy group is preferably the following formula (4-1);
  • ⁇ in the formula (4-1) is preferably 0 to 3, more preferably 0 to 2, and still more preferably 0 or 1.
  • Examples of the compound represented by the above formula (4-1) include N-hydroxyethylpyrrolidone, N-hydroxypropylpyrrolidone, N-hydroxybutylpyrrolidone, N-hydroxypentylpyrrolidone, N-hydroxyhexylpyrrolidone and 2-pyrrolidone.
  • This pyrrolidone skeleton-containing compound can be obtained by reacting a compound having a functional group having reactivity with a nitrogen atom or a hydrogen atom in the pyrrolidone skeleton-containing compound and an epoxy group.
  • Examples of the functional group having reactivity with a nitrogen atom or a hydrogen atom include an epoxy group, a halogen atom, a hydroxyl group, a carboxyl group, and an amino group, and a halogen atom is preferable.
  • the compound having an epoxy group and a halogen atom is preferably epihalohydrin, more preferably epichlorohydrin.
  • the compound when a compound in which X 2 in the formula (7) is an organic group having 1 to 10 carbon atoms having a thiol group at the terminal is used, the compound has a pyrrolidone skeleton represented by the formula (4).
  • the compound preferably has a polymerizable unsaturated group such as a vinyl group, more preferably a pyrrolidone skeleton-containing compound having a vinyl group.
  • Specific examples include N-vinylpyrrolidone and 1- (2-propenyl) -2-pyrrolidone. N-vinylpyrrolidone is preferred.
  • the PAG compound of the second present invention can also be produced by the above method (i) or the method (ii). Of these, the method (i) is preferred.
  • the first step is carried out in the same manner as in the method for producing the PAG compound of the first invention described above, and in the second step, the compound represented by the above formula (5) and the following (8);
  • R b4 represents an organic group having 18 to 47 carbon atoms
  • R b4 in the above formula (8) is the same as R b1 in the case where R b2 in the formula (2-2) is a hydrogen atom.
  • R b is a group represented by the formula (2-2).
  • R b2 is a hydrogen atom
  • the compound represented by the formula (2-1) has a hydroxyl group
  • R b2 in the above formula (2-2) represents The structure is represented by Formula (2-3).
  • the PAG compound of the third present invention can also be produced by the above method (i) or (ii).
  • the method (i) in the first step, the following formula (9) ;
  • R 5 represents an organic group having 21 to 100 carbon atoms
  • R 5 in the above formula (9) is an organic group having 21 to 100 carbon atoms, and preferably has a functional group reactive with alkylene oxide.
  • the functional group include the same groups as the functional group in R 3 of the formula (4). Preferably it is a hydroxyl group.
  • the organic group having 21 to 100 carbon atoms is preferably a group in which the functional group is bonded to a hydrocarbon group such as an aliphatic alkyl group, an alicyclic alkyl group, or an aryl group.
  • aliphatic alkyl group aliphatic alkyl group, alicyclic alkyl group and aryl group are the same as the aliphatic alkyl group, alicyclic alkyl group and aryl group described in R 2 of the above formula (3-1). is there.
  • Specific examples of the compound represented by the above formula (9) include 2 such as N-hydroxyhenicosylpyrrolidone, N-hydroxydocosylpyrrolidone, N-hydroxypentacosylpyrrolidone, N-hydroxytriacontylpyrrolidone and the like.
  • the PAG compound of the third invention is preferably produced by the method (ii) above.
  • R 1 is the same or different and represents an alkylene group having 2 to 20 carbon atoms.
  • R c is an alkyl group having 1 to 50 carbon atoms which may have a substituent;
  • R 2 is A compound that is (CH 2 ) s —O—CH 2 CH (OH) CH 2 — will be produced.
  • the compound represented by the formula (3-1) has a hydroxyl group, and when the compound represented by the formula (11) further reacts with this hydroxyl group, R 2 in the formula (3-1) is represented by the formula In the group represented by (3-5), R 22 has a structure represented by the above formula (3-6).
  • the amount of the hydrophobic group-containing compound used in the second step of the production method (i) of the PAG compound of the present invention is not particularly limited, but it is 90 to 500 mol with respect to 100 mol% of the reaction product obtained in the first step. % Is preferred. More preferably, it is 100 to 300 mol%.
  • the amount of the hydrophobic group-containing polyalkylene glycol used in the production methods (ii) of the first and second PAG compounds of the present invention is 90 to 500 mol% with respect to 100 mol% of the compound having a pyrrolidone skeleton. Is preferred. More preferably, it is 100 to 300 mol%.
  • the amount of the hydrophobic group-containing polyalkylene glycol used in the production method (ii) of the third PAG compound of the present invention is 90 to 1000 mol% with respect to 100 mol% of the compound having a pyrrolidone skeleton. preferable. More preferably, it is 100 to 500 mol%.
  • reaction catalysts include mineral acids such as sulfuric acid and phosphoric acid, acid catalysts such as Lewis acids such as tin tetrachloride and boron trifluoride; basics such as alkali metal hydroxides such as sodium hydroxide and potassium hydroxide Catalyst; polymerization catalyst.
  • a basic catalyst and a polymerization catalyst are preferred.
  • polymerization catalyst examples include persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate; hydrogen peroxide; azoamidine compounds such as 2,2′-azobis-2-methylpropionamidine hydrochloride, 2,2′-azobis And water-soluble azo initiators such as cyclic azoamidine compounds such as -2- (2-imidazolin-2-yl) propane hydrochloride, and azonitrile compounds such as 2-carbamoylazoisobutyronitrile.
  • persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate
  • hydrogen peroxide hydrogen peroxide
  • azoamidine compounds such as 2,2′-azobis-2-methylpropionamidine hydrochloride, 2,2′-azobis And water-soluble azo initiators
  • cyclic azoamidine compounds such as -2- (2-imidazolin-2-yl) propane hydrochloride
  • the (poly) alkylene glycol compound when a compound having a polyalkylene glycol terminal is a hydroxyl group or a compound having a glycidyl group, or in the first step and the second step of the method (i) It is preferable to use a basic catalyst. Sodium hydroxide is more preferable as the basic catalyst.
  • a water-soluble azo initiator when a (poly) alkylene glycol compound having a thiol group at the terminal is used, it is preferable to use a water-soluble azo initiator. An azoamidine compound is more preferable as the water-soluble azo initiator.
  • the reaction temperature in the first step, the second step of the method (i) and the reaction step of the method (ii) is not particularly limited, but is preferably 20 to 180 ° C, more preferably 30 to 160 ° C. It is.
  • As the reaction pressure is preferably not more than 20 Kg / cm 2 G from atmospheric pressure, and more preferably 1 ⁇ 10Kg / cm 2 G.
  • the first and second steps of the method (i) and the reaction step of the method (ii) are preferably performed in an atmosphere of an inert gas such as nitrogen gas. Moreover, you may preserve
  • a solvent may be used, but the reaction is preferably performed without a solvent.
  • a purification step is optionally performed after or during the first step, the second step of the method (i), and the reaction step of the method (ii). It may be provided.
  • the purification step include a step of removing residual raw materials, by-products, moisture, catalyst residues, and the like, a step of neutralizing the catalyst, and the like.
  • a step of neutralizing the catalyst for example, when the reaction is carried out in the presence of sodium hydroxide and / or potassium hydroxide, a solid acid such as sulfuric acid, acetic acid or activated clay is used as the neutralizing agent at that time. Can do.
  • composition containing the PAG compound of the present invention contains the PAG compound of the present invention as an essential component.
  • the composition may contain other components such as unreacted raw materials, by-products, catalyst residues, and solvents.
  • the content of the PAG compound of the present invention in the composition is preferably 1 to 99.9% by mass with respect to 100% by mass of the composition. More preferably, it is 1 to 99% by mass. That is, the composition containing the polyalkylene glycol-containing compound of the present invention includes the polyalkylene glycol-containing compound and other components other than the compound, and the content of the polyalkylene glycol-containing compound is 100% by mass of the composition. 1 to 99.9% by mass.
  • the content of the polyalkylene glycol-containing compound is preferably 30 to 99.9% by mass, and more preferably 50 to 99.9% by mass.
  • the polyalkylene glycol-containing compound of the present invention is used in various applications such as detergent builders, detergents, water treatment agents, scale inhibitors, dispersants, etc., but preferably used in detergent builders, detergents and the like. .
  • a method of using the polyalkylene glycol-containing compound as a detergent builder, detergent additive, water treatment agent, scale inhibitor or dispersant is also one aspect of the present invention.
  • the present invention is also a detergent composition
  • a detergent composition comprising the polyalkylene glycol-containing compound of the present invention and a detergent additive other than the compound.
  • the detergent additive other than the polyalkylene glycol-containing compound of the present invention is not particularly limited as long as it is an additive used for a surfactant or a normal detergent, and conventionally known knowledge can be appropriately referred to in the detergent field.
  • the detergent composition may be a powder detergent composition or a liquid detergent composition.
  • the surfactant is preferably one or more selected from the group consisting of an anionic surfactant, a nonionic surfactant, a cationic surfactant and an amphoteric surfactant.
  • anionic surfactants include alkylbenzene sulfonate, alkyl ether sulfate, alkenyl ether sulfate, alkyl sulfate, alkenyl sulfate, ⁇ -olefin sulfonate, ⁇ -sulfo fatty acid or ester salt, alkane sulfonate , Saturated fatty acid salt, unsaturated fatty acid salt, alkyl ether carboxylate, alkenyl ether carboxylate, amino acid type surfactant, N-acyl amino acid type surfactant, alkyl phosphate ester or salt thereof, alkenyl phosphate ester or Its salts are preferred.
  • An alkyl group such as a methyl group may be branched from the alkyl group or alkenyl group in these anionic surfactants.
  • Nonionic surfactants include polyoxyalkylene alkyl ethers, polyoxyalkylene alkenyl ethers, polyoxyethylene alkyl phenyl ethers, higher fatty acid alkanolamides or alkylene oxide adducts thereof, sucrose fatty acid esters, alkyl glycoxides, fatty acid glycerin mono Esters, alkylamine oxides and the like are preferred.
  • An alkyl group such as a methyl group may be branched from the alkyl group or alkenyl group in these nonionic surfactants.
  • cationic surfactant a quaternary ammonium salt or the like is suitable.
  • amphoteric surfactant a carboxyl type amphoteric surfactant, a sulfobetaine type amphoteric surfactant, and the like are suitable.
  • the alkyl group and alkenyl group in these cationic surfactants and amphoteric surfactants may be branched from an alkyl group such as a methyl group.
  • the blending ratio of the surfactant is usually 10 to 60% by mass, preferably 15 to 50% by mass, more preferably 20 to 45% by mass, particularly preferably based on the total amount of the detergent composition. Is 25 to 40% by mass. If the surfactant content is too small, sufficient detergency may not be achieved, and if the surfactant content is too high, the economy may be reduced.
  • washing rate (%) ((whiteness of contaminated cloth before washing) ⁇ (whiteness of contaminated cloth after washing)) / ((whiteness of contaminated cloth before washing) ⁇ (whiteness of white cloth)) ⁇ 100 The larger the value of the cleaning rate, the better the cleaning power.
  • a targot meter is set at 25 ° C., 1 L of hard water (2), 5.0 g of a sample aqueous solution (3), 5.0 g of a surfactant aqueous solution (4), carbon black (foundation) 0.25 g of Washing Science Association) and 0.50 g of clay (1-11 kinds of powder for JIS test (Kanto loam baked product)) were placed in a pot and stirred at 100 rpm for 1 minute. Then, 5 cotton cloths were put and stirred at 100 rpm for 10 minutes.
  • the oil-water interface tension was measured using a DY-500 system (hereinafter also referred to as DY-500) manufactured by Kyowa Interface Science Co., Ltd. according to the following procedure. (1) Pure water was added to 0.4 g of sodium laurylbenzenesulfonate to make 1000 g, and an aqueous sodium laurylbenzenesulfonate solution (400 ppm) was prepared.
  • the interaction strength between each sample and the soil component is measured by using the CalCalITC200 system (hereinafter also referred to as ITC) manufactured by Malvern, and the absolute value of the calorific value change that occurs when the aqueous solution of each sample is dropped onto the aqueous solution of the soil component is measured. It was evaluated by. (1) 10 g of an aqueous solution with a solid content of 800 ppm for each evaluation sample was prepared in a 20 mL screw tube. (2) Separately, 5 g of a 1% solid content aqueous solution of each soil component was prepared in a 10 mL screw tube.
  • model soil component methyl acetate, acetic acid, alkyl fatty acid or the like was selected. (3) Each evaluation sample adjusted in (1) was charged in an ITC sample cell, and the dirt component adjusted in (2) was charged in a syringe, and titration was started.
  • the number of titrations was 19 times, the cell temperature was 25 ° C., the power applied to the reference cell during measurement was 5 ⁇ cal, the time from the start of data acquisition to the first titration was 60 seconds, the stirring speed was 750 rpm, per time
  • the titration amount was 0.4 ⁇ L for the first time, 2 ⁇ L for the second to 19th times, the titration time per time was 4 seconds, the sensory time for titration was 150 seconds, and the data averaging time was 5 seconds.
  • a sample charged with pure water was also measured instead of the sample solution of (1).
  • the sum of the maximum absolute value of the calorific value change that occurred in the 2nd to 19th times was defined as the strength of interaction. In other words, the larger the sum obtained above, the stronger the interaction.
  • Example 1 In a SUS autoclave reaction vessel equipped with a thermometer, a stirrer, a raw material introducing tube and a nitrogen introducing tube, 374.6 g (2.9 mol) of N-hydroxyethylpyrrolidone (hereinafter sometimes referred to as HEP) was used as a reaction catalyst. 0.33 g of sodium hydroxide was charged, the inside of the reaction vessel was purged with nitrogen with stirring, and the mixture was heated to 120 ° C. in a nitrogen atmosphere. Then, 1281.8 g (29.0 mole) of ethylene oxide was introduced into the reactor over 3.5 hours while maintaining 120 ⁇ 5 ° C. under safe pressure, and the temperature was maintained for another 2 hours after the introduction.
  • HEP N-hydroxyethylpyrrolidone
  • Example 2 A SUS autoclave reaction vessel equipped with a thermometer, a stirrer, a raw material introduction tube and a nitrogen introduction tube was charged with 600 g (1.1 mol) of the polyalkylene glycol-containing compound (1), and the inside of the reaction vessel was purged with nitrogen under stirring. And heated to 120 ° C. under a nitrogen atmosphere. Then, 195.1 g (4.4 mol) of ethylene oxide was introduced into the reactor over 2.5 hours while maintaining 120 ⁇ 5 ° C. under safe pressure, and the temperature was maintained for another 1.5 hours after the introduction. Finally, the inside of the reaction vessel was purged with nitrogen under stirring and cooled to room temperature.
  • a polyalkylene glycol-containing compound (2) in which 14.2 moles of ethylene oxide was added to HEP on average was obtained. Furthermore, in a SUS autoclave reaction vessel equipped with a thermometer, a stirrer, a raw material introducing tube and a nitrogen introducing tube, 780.7 g (1.1 mol) of the polyalkylene glycol-containing compound (2) produced above was charged and stirred. The reaction vessel was purged with nitrogen and heated to 120 ° C. in a nitrogen atmosphere. Then, 284.2 g (6.5 mol) of ethylene oxide was introduced into the reactor over 5.3 hours while maintaining 120 ⁇ 5 ° C. under safe pressure, and the temperature was maintained for another 4.2 hours after the introduction.
  • Example 3-1 In a glass four-necked eggplant flask reaction vessel equipped with a thermometer, a stirrer, a reflux tube, and a nitrogen introduction tube, 2.91 g (5.1 mmol) of the polyalkylene glycol-containing compound (1) and sodium hydroxide of 0. 30 g (7.5 mmol) was charged, and the inside of the reaction vessel was purged with nitrogen under stirring, and heated to 60 ° C. in a nitrogen atmosphere. After adding 1.23 g (5.1 mmol) of lauryl glycidyl ether to the reaction vessel all at once while maintaining 60 ° C. under normal pressure, the temperature was further maintained for 10 hours under a nitrogen atmosphere. Thereafter, the reaction solution was allowed to cool to room temperature to obtain a polyalkylene glycol-containing compound (6-1) having an organic group at the terminal.
  • Example 4-1 In a glass four-necked eggplant flask reaction vessel equipped with a thermometer, a stirrer, a reflux tube, and a nitrogen introduction tube, 2.91 g (5.1 mmol) of the polyalkylene glycol-containing compound (1) and sodium hydroxide of 0. 30 g (7.5 mmol) was charged, and the inside of the reaction vessel was purged with nitrogen under stirring, and heated to 60 ° C. in a nitrogen atmosphere. While maintaining 60 ° C. under normal pressure, 0.95 g (5.1 mmol) of 2-ethylhexyl glycidyl ether was added all at once to the reaction vessel, and the temperature was further maintained for 10 hours under a nitrogen atmosphere. Thereafter, the reaction solution was allowed to cool to room temperature to obtain a polyalkylene glycol-containing compound (7-1) having an organic group at the terminal.
  • Example 5-1 In a glass four-necked eggplant flask reaction vessel equipped with a thermometer, a stirrer, a reflux tube, and a nitrogen introduction tube, 2.91 g (5.1 mmol) of the polyalkylene glycol-containing compound (1) and sodium hydroxide of 0. 30 g (7.5 mmol) was charged, and the inside of the reaction vessel was purged with nitrogen under stirring, and heated to 60 ° C. in a nitrogen atmosphere. 1.67 g (5.1 mmol) of stearyl glycidyl ether was added all at once to the reaction vessel while maintaining 60 ° C. under normal pressure, and the temperature was further maintained for 12 hours under a nitrogen atmosphere. Thereafter, the reaction solution was allowed to cool to room temperature to obtain a polyalkylene glycol-containing compound (8-1) having an organic group at the terminal.
  • Example 6-1 In a glass four-necked eggplant flask reaction vessel equipped with a thermometer, a stirrer, a reflux tube, and a nitrogen introduction tube, 5.15 g (5.1 mmol) of the polyalkylene glycol-containing compound (3) and sodium hydroxide as a reaction catalyst were added in an amount of 0.1%. 30 g (7.5 mmol) was charged, and the inside of the reaction vessel was purged with nitrogen under stirring, and heated to 60 ° C. in a nitrogen atmosphere. After adding 1.23 g (5.1 mmol) of lauryl glycidyl ether to the reaction vessel all at once while maintaining 60 ° C. under normal pressure, the temperature was further maintained for 12 hours under a nitrogen atmosphere. Thereafter, the reaction solution was allowed to cool to room temperature to obtain a polyalkylene glycol-containing compound (9-1) having an organic group at the terminal.
  • Example 7-1 In a glass four-necked eggplant flask reaction vessel equipped with a thermometer, a stirrer, a reflux tube and a nitrogen introduction tube, 0.66 g (5.1 mmol) of N-hydroxyethylpyrrolidone (hereinafter sometimes referred to as HEP), reaction As a catalyst, 0.30 g (7.5 mmol) of sodium hydroxide was charged, and the reaction vessel was purged with nitrogen under stirring, and heated to 60 ° C. in a nitrogen atmosphere. While maintaining 60 ° C.
  • HEP N-hydroxyethylpyrrolidone
  • Example 8-1 In a glass four-necked eggplant flask reaction vessel equipped with a thermometer, a stirrer, a reflux tube and a nitrogen introduction tube, 0.66 g (5.1 mmol) of N-hydroxyethylpyrrolidone (hereinafter sometimes referred to as HEP), reaction As a catalyst, 0.30 g (7.5 mmol) of sodium hydroxide was charged, and the reaction vessel was purged with nitrogen under stirring, and heated to 60 ° C. in a nitrogen atmosphere. While maintaining 60 ° C.
  • HEP N-hydroxyethylpyrrolidone
  • Example 3-2> A glass four-necked eggplant flask reaction vessel equipped with a thermometer, a stirrer and a nitrogen introducing tube was charged with 11.38 g (20 mmol) of the polyalkylene glycol-containing compound (1) and 0.52 g of sodium hydroxide as a catalyst, with stirring. The inside of the reaction vessel was purged with nitrogen, heated to 120 ° C. in a nitrogen atmosphere, and the temperature was maintained for 1 hour under normal pressure. Thereafter, the temperature was lowered to 80 ° C. and 5.12 g (20 mmol) of lauryl glycidyl ether was added all at once to the reaction vessel, and the temperature was further maintained for 7 hours under a nitrogen atmosphere. Thereafter, the reaction solution was allowed to cool to room temperature to obtain a polyalkylene glycol-containing compound (6-2) having an organic group at the terminal.
  • a polyalkylene glycol-containing compound (6-2) having an organic group at the terminal.
  • Example 4-2 A glass four-necked eggplant flask reaction vessel equipped with a thermometer, a stirrer and a nitrogen introducing tube was charged with 11.38 g (20 mmol) of the polyalkylene glycol-containing compound (1) and 0.52 g of sodium hydroxide as a catalyst, with stirring.
  • the inside of the reaction vessel was purged with nitrogen, heated to 120 ° C. in a nitrogen atmosphere, and the temperature was maintained for 1 hour under normal pressure. Thereafter, the temperature was lowered to 80 ° C., and 3.73 g (20 mmol) of 2-ethylhexyl glycidyl ether was added all at once to the reaction vessel, and the temperature was maintained for 7 hours under a nitrogen atmosphere. Thereafter, the reaction solution was allowed to cool to room temperature to obtain a polyalkylene glycol-containing compound (7-2) having an organic group at the terminal.
  • Example 5-2> A glass four-necked eggplant flask reaction vessel equipped with a thermometer, a stirrer and a nitrogen introducing tube was charged with 11.38 g (20 mmol) of the polyalkylene glycol-containing compound (1) and 0.52 g of sodium hydroxide as a catalyst, with stirring. The inside of the reaction vessel was purged with nitrogen, heated to 120 ° C. in a nitrogen atmosphere, and the temperature was maintained for 1 hour under normal pressure. Thereafter, the temperature was lowered to 80 ° C. and 6.53 g (20 mmol) of stearyl glycidyl ether was added all at once to the reaction vessel, and the temperature was further maintained for 7 hours under a nitrogen atmosphere. Thereafter, the reaction solution was allowed to cool to room temperature to obtain a polyalkylene glycol-containing compound (8-2) having an organic group at the terminal.
  • Example 6-2 A glass four-necked eggplant flask reaction vessel equipped with a thermometer, a stirrer and a nitrogen inlet tube was charged with 20.18 g (20 mmol) of a polyalkylene glycol-containing compound (3) and 0.52 g of sodium hydroxide as a catalyst, and stirred.
  • the inside of the reaction vessel was purged with nitrogen, heated to 120 ° C. in a nitrogen atmosphere, and the temperature was maintained for 1 hour under normal pressure. Thereafter, the temperature was lowered to 80 ° C. and 5.12 g (20 mmol) of lauryl glycidyl ether was added all at once to the reaction vessel, and the temperature was further maintained for 7 hours under a nitrogen atmosphere. Thereafter, the reaction solution was allowed to cool to room temperature to obtain a polyalkylene glycol-containing compound (9-2) having an organic group at the terminal.
  • Example 7-2> In a glass four-necked eggplant flask reaction vessel equipped with a thermometer, stirrer and nitrogen introduction tube, 12.92 g (100 mmol) of 1- (2-hydroxyethyl) -2-pyrrolidone (HEP) and 2 g of sodium hydroxide as a catalyst The reaction vessel was purged with nitrogen under stirring, heated to 120 ° C. in a nitrogen atmosphere, and the temperature was maintained under normal pressure for 1 hour.
  • HEP 1- (2-hydroxyethyl) -2-pyrrolidone
  • Example 8-2> In a glass four-necked eggplant flask reaction vessel equipped with a thermometer, stirrer and nitrogen introduction tube, 12.92 g (100 mmol) of 1- (2-hydroxyethyl) -2-pyrrolidone (HEP) and 2 g of sodium hydroxide as a catalyst The reaction vessel was purged with nitrogen under stirring, heated to 120 ° C. in a nitrogen atmosphere, and the temperature was maintained under normal pressure for 1 hour.
  • HEP 1- (2-hydroxyethyl) -2-pyrrolidone
  • Example 10 To a glass four-necked eggplant flask reaction vessel equipped with a thermometer, a stirrer, and a nitrogen introduction tube, Nippon Shokubai Co., Ltd. Softanol 90 (compound having an average of 9 mol of ethylene oxide added to a secondary alcohol having 12 to 14 carbon atoms) And hereinafter also referred to as SFT90.) 19.07 g (32 mmol) and 0.18 g (0.32 mmol) of potassium hydroxide as a catalyst were charged, and the reaction vessel was purged with nitrogen under stirring. Until the temperature was maintained under normal pressure for 1 hour.
  • Example 12 In a glass reactor equipped with a moisture meter with a Dimroth condenser, a stirrer with a stirring blade and a stirring seal, and a temperature sensor with a glass protective tube, 20.75 g of azeotropic solvent cyclohexane and EO10 to lauryl alcohol Mole adduct 200 g (0.32 mol), mercaptopropionic acid 33.9 g (0.32 mol), paratoluenesulfonic acid monohydrate 4.68 g (24.6 mmol), phenothiazine 0.12 g (0.59 mmol) Prepared. After filling the moisture meter with cyclohexane, the reaction system was heated to reflux while stirring.
  • the temperature in the reaction system was adjusted to 110 ⁇ 5 ° C. by adding cyclohexane and stirred for 10 hours. Thereafter, the reaction solution was allowed to cool to about 70 ° C. with stirring so as not to solidify, and 3.12 g (23.4 mmol) of a 30% aqueous sodium hydroxide solution was quickly charged into the reactor. Next, 220 g of ion-exchanged water was added, and the reaction system was heated to reflux while stirring. The cyclohexane accumulated in the moisture determination receiver was completely removed from the reaction system while draining. Thus, a polyalkylene glycol-containing compound (15) having a thiol group at the terminal was obtained.
  • NVP N-vinylpyrrolidone
  • V-50 2,2′-azobis (2-methylpropioamidine) dihydrochloride
  • the dropping time was 160 minutes for NVP, 190 minutes for V-50, and 160 minutes for the polyalkylene glycol-containing compound (15).
  • the temperature was maintained at 80 ° C. until the end of dropping. Furthermore, the same temperature was maintained for 60 minutes after completion of the dropping, and aging was performed to complete the polymerization. After completion of the polymerization, the reaction solution was allowed to cool to room temperature to obtain a polyalkylene glycol-containing compound (16) having an organic group at the terminal.
  • the structures of the polyalkylene glycol-containing compounds (graft polymers) obtained in Examples 1 to 12 and Comparative Examples 1 and 2 are represented by the above formula (1-1), (2-1), or (3-1).
  • Tables 1 and 2 show R 0 , R 1 , R 2 , R a , R b , R c and n in the compounds to be prepared.
  • the said evaluation test was done and the result was shown in Table 3.

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Abstract

L'invention concerne un composé contenant du polyalkylène glycol qui présente un pouvoir détergent plus excellent que les composés contenant du polyalkylène glycol classiques. Ce composé contenant du polyalkylène glycol est caractérisé en ce qu'il est représenté par la formule (1-1).
PCT/JP2019/002321 2018-02-14 2019-01-24 Composé contenant du polyalkylène glycol Ceased WO2019159643A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01502435A (ja) * 1987-03-02 1989-08-24 ジーエイエフ・コーポレーション エポキシ　ピロリドンからなる非イオン界面活性剤
JP2012149186A (ja) 2011-01-20 2012-08-09 Nippon Shokubai Co Ltd ポリアルキレングリコールおよびその製造方法およびその用途
JP2014091754A (ja) * 2012-11-01 2014-05-19 Nippon Shokubai Co Ltd 重合体、その製造方法、およびその用途
JP2015209534A (ja) * 2014-04-30 2015-11-24 株式会社日本触媒 （ポリ）アルキレングリコール化合物及び（ポリ）アルキレングリコール系重合体
US20150344461A1 (en) * 2013-01-22 2015-12-03 Isp Investments Inc. Hemi-aminal ethers and thioethers of n-alkenyl cyclic compounds
JP2018177918A (ja) * 2017-04-10 2018-11-15 信越化学工業株式会社 ポリシロキサンモノマー及びその製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01502435A (ja) * 1987-03-02 1989-08-24 ジーエイエフ・コーポレーション エポキシ　ピロリドンからなる非イオン界面活性剤
JP2012149186A (ja) 2011-01-20 2012-08-09 Nippon Shokubai Co Ltd ポリアルキレングリコールおよびその製造方法およびその用途
JP2014091754A (ja) * 2012-11-01 2014-05-19 Nippon Shokubai Co Ltd 重合体、その製造方法、およびその用途
US20150344461A1 (en) * 2013-01-22 2015-12-03 Isp Investments Inc. Hemi-aminal ethers and thioethers of n-alkenyl cyclic compounds
JP2015209534A (ja) * 2014-04-30 2015-11-24 株式会社日本触媒 （ポリ）アルキレングリコール化合物及び（ポリ）アルキレングリコール系重合体
JP2018177918A (ja) * 2017-04-10 2018-11-15 信越化学工業株式会社 ポリシロキサンモノマー及びその製造方法

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