Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
• • 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
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
  • C08G69/10—Alpha-amino-carboxylic acids
• • 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
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/48—Polymers modified by chemical after-treatment
• • 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
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere

Definitions

• the present invention relates to a crosslinked product of modified polyaspartic acid or a salt thereof, and a thickening composition.
• Carbomer is the most commonly used cosmetic thickener on the market. Characteristics of carbomer that are not found in other thickeners include its extremely high thickening properties and its refreshing feel when applied to the skin. Carbomer is a polyacrylic acid-based polymer. Polyaspartic acid has a chemical structure similar to polyacrylic acid, can exhibit similar functions, and is biodegradable, so it is expected to be an alternative material with a low environmental impact. Furthermore, polyaspartic acid (salt) whose chains are partially crosslinked with a polyvalent amine compound has been reported (Patent Document 1).
• the present invention was made to solve the above problems, and by using a crosslinked product of modified polyaspartic acid or a salt thereof to which a compound having an amino group and a carboxyl group such as an amino acid is added, it is possible to maintain a constant temperature for a longer period of time. It is an object of the present invention to provide a thickening composition that can maintain a viscosity higher than the above. Another object of the present invention is to provide a crosslinked product of modified polyaspartic acid or a salt thereof contained in the thickening composition.
• the content of the present disclosure includes the following embodiments [1] to [15].
• [1] A crosslinked product of modified polyaspartic acid or a salt thereof, A crosslinked product of modified polyaspartic acid or a salt thereof, wherein the modified polyaspartic acid is obtained by adding a compound having an amino group and a carboxy group to polyaspartic acid.
• [2] The modified polyaspartic acid or its modified polyaspartic acid according to [1], wherein the compound having an amino group and a carboxy group is one or more selected from the group consisting of amino acids, amino acid carboxylates, and amino acid esters.
• Cross-linked salt is one or more selected from the group consisting of amino acids, amino acid carboxylates, and amino acid esters.
• PSI polysuccinimide
• Cross-linked salt [4] The crosslinked product of modified polyaspartic acid or its salt according to [3], which is obtained by crosslinking the modified polyaspartic acid or its salt using a polyfunctional amine as a crosslinking agent.
• modified polyaspartic acid is Polysuccinimide (PSI) and The compound having the amino group and carboxy group; A compound (A:a1-A1-a2) having a first functional group (a1) and a second functional group (a2), The crosslinked product of modified polyaspartic acid or a salt thereof according to [1] or [2], which is a reaction product of [1] or [2].
• PSI Polysuccinimide
• the first functional group (a1) is an amino group (NH 2 -)
• the modified compound according to [6] has lower reactivity with polysuccinimide (PSI) than the first functional group (a1).
• PSI polysuccinimide
• the first functional group (a1) is an amino group (NH 2 -)
• the second functional group (a2) is an amino group (NH 2 ⁇ )
• the modified polyaspartic acid according to [6] or [7] wherein the amino group of the second functional group (a2) is an amino group in the structure represented by the following formula (1). or a cross-linked product of its salt.
• G represents a carboxylic acid group or a salt thereof.
• a thickening composition that can maintain a viscosity above a certain level for a longer period of time, and a crosslinked product of modified polyaspartic acid or a salt thereof contained in the thickening composition.
• ⁇ means a value greater than or equal to the value before the description " ⁇ ” and less than or equal to the value after the description " ⁇ ".
• the modified polyaspartic acid is added to the polyaspartic acid with an amino acid.
• This is an addition of a compound having a group and a carboxy group.
• the modified polyaspartic acid according to this embodiment is preferably a reaction product of polysuccinimide (PSI) and the compound having an amino group and a carboxy group.
• PSI polysuccinimide
• the modified polyaspartic acid according to this embodiment is preferably obtained by ring-opening polysuccinimide (PSI) using a compound having an amino group and a carboxy group.
• PSI ring-opening polysuccinimide
• the polysuccinimide (PSI) according to this embodiment is a polymer represented by the following formula (2).
• the method for producing polysuccinimide (PSI) is not particularly limited, but for example, it is produced by heating and dehydrating aspartic acid at 170 to 190° C. in vacuum in the presence of phosphoric acid.
• the polysuccinimide (PSI) obtained as described above may be treated with a condensing agent such as dicyclohexylcarbodiimide.
• the molecular weight of polysuccinimide (PSI) is not particularly limited.
• the weight average molecular weight is preferably 20,000 or more, more preferably 50,000 or more, and even more preferably 70,000 or more.
• the molecular weight of polysuccinimide (PSI) is preferably 500,000 or less, more preferably 200,000 or less.
• the weight average molecular weight in this case is a value calculated by GPC using polystyrene as a standard substance.
• the compound having an amino group and a carboxy group is preferably one or more selected from the group consisting of amino acids, amino acid carboxylates, and amino acid esters. Further, a compound having an amino group and a carboxy group, or an acid salt thereof may be used as the raw material.
• the acidic salt of the compound having an amino group and a carboxyl group include hydrochlorides such as lysine hydrochloride, ornithine hydrochloride, and arginine hydrochloride, and similar sulfates.
• amino acids include aliphatic amino acids such as glycine, alanine, valine, leucine, and isoleucine; oxyamino acids such as serine and threonine; sulfur-containing amino acids such as methionine, cysteine, and cystine; and aspartic acid and glutamic acid.
• Acidic amino acids Basic amino acids such as lysine, ornithine, and arginine; Aromatic amino acids such as phenylalanine and tyrosine; Heterocyclic amino acids such as tryptophan, histidine, proline, and oxyproline; Amino acids with amide groups such as asparagine and glutamine, etc. It will be done. These can be used regardless of whether they are L-form, D-form, or DL-form.
• the above amino acid is preferably a compound represented by the following formula (3).
• R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.
• the alkoxy groups of 1 to 5 may be further substituted with other organic groups. Examples of the organic groups include amino groups, carboxy groups, etc. It is preferable that n is an integer of 1 to 3.
• R is preferably a hydrogen atom, a methyl group, or an ethyl group, and more preferably a hydrogen atom.
• carboxylic acid salts of amino acids examples include alkali metal salts, alkaline earth metal salts, and the like.
• the amino acid carboxylate is a sodium salt, potassium salt, calcium salt, or the like.
• amino acid esters examples include alkyl esters, cycloalkyl esters, benzyl esters, etc. of the above amino acids.
• the carboxylate of the amino acid or the amino acid ester is preferably a compound represented by the following formula (4).
• X represents an alkyl group, a cycloalkyl group, a benzyl group, an alkali metal, or an alkaline earth metal; R and n are the same as in the general formula (3) above.
• X is a methyl group, Alkyl group such as ethyl group; preferably an alkali metal.
• n is preferably an integer of 1 to 3.
• "-CO-O-X" means carboxylate.
• Method for producing amino acid ester The method for producing amino acid esters according to this embodiment is not particularly limited.
• the amino acid ester according to the present embodiment is generally produced by heating an amino acid in excess alcohol in the presence of a mineral acid catalyst such as sulfuric acid or hydrochloric acid.
• Examples of the method for producing modified polyaspartic acid or its salt according to the present embodiment include a ring-opening reaction method of polysuccinimide (PSI) by reaction with a compound having an amino group and a carboxy group. By reacting polysuccinimide (PSI) with the compound having an amino group and a carboxy group, the imide ring of polysuccinimide (PSI) is opened. When carrying out the ring-opening reaction by using the compound having an amino group and a carboxy group in an amount less than 1 times the equivalent of the monomer unit of polysuccinimide (PSI), generally , unreacted imide rings remain.
• PSI polysuccinimide
• the compound having an amino group and a carboxy group is an amino acid ester.
• the modified polyaspartic acid or its salt according to the present embodiment is an amino acid ester-modified polyaspartic acid or its salt (sometimes referred to as "amino acid ester modified product").
• the imide ring of polysuccinimide (PSI) is opened by reacting polysuccinimide (PSI) with the amino acid ester.
• the unreacted imide ring may remain, or a ring-opening reaction may be performed using another compound having an amino group and a carboxy group. Furthermore, if desired, the unreacted imide ring may be ring-opened with a substituted amine such as ethanolamine, cysteamine, dibutylamine, or the like.
• a substituted amine such as ethanolamine, cysteamine, dibutylamine, or the like.
• the organic solvent may be one that substantially dissolves polysuccinimide (PSI) and a compound having an amino group and a carboxy group, and/or There is no particular restriction as long as it does not substantially inhibit the progress of the reaction.
• PSI polysuccinimide
• organic solvent examples include aprotic solvents such as dimethylformamide (DMF), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), dimethylimidazolidinone (DMI), dimethylsulfoxide (DMSO), and sulfolane.
• aprotic solvents such as dimethylformamide (DMF), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), dimethylimidazolidinone (DMI), dimethylsulfoxide (DMSO), and sulfolane.
• polar organic solvents examples include polar organic solvents. These can be used alone or in combination.
• Amount of compound containing amino group and carboxy group used The amount of the compound having an amino group and a carboxy group according to the present embodiment to be used is not particularly limited as long as it is substantially dissolved in the organic solvent and/or does not substantially inhibit the progress of the reaction.
• the amount used is generally 0.1 to 10 times the equivalent of the monomer unit of polysuccinimide (PSI), preferably 0.1 to 1.0 times the equivalent.
• the optionally used basic catalyst is not particularly limited as long as it substantially accelerates the reaction rate.
• the basic catalyst include aliphatic tertiary amines such as trimethylamine, triethylamine, tripropylamine, tributylamine, diisopropylethylamine (DIEA), triethanolamine, and triethylenediamine (DABCO); N-methylmorpholine alicyclic tertiary amines such as; aromatic tertiary amines such as dimethylaniline and diethylaniline; and tetramethylguanidine. These can be used alone or in combination.
• the amount of the basic catalyst used is not particularly limited as long as it substantially accelerates the reaction rate.
• the amount of the basic catalyst used is generally 0 to 2 times the equivalent of the compound having an amino group and a carboxy group.
• the amino acid ester is a mineral acid salt, a base equivalent to neutralization is further added.
• reaction temperature In the method for producing modified polyaspartic acid or a salt thereof according to the present embodiment, the reaction temperature is not particularly limited as long as the progress of the reaction can be substantially maintained.
• the reaction temperature is generally selected from a temperature range of 5 to 150°C, and usually room temperature.
• the above reaction temperature can be selected from a temperature range of 5 to 150°C, which is optimal for the compound having an amino group and a carboxy group to be used.
• concentration of the reaction system employed in the method for producing modified polyaspartic acid or its salt according to the present embodiment is not particularly limited as long as the progress of the reaction can be substantially maintained.
• concentration of the reaction system is selected based on the concentration of polysuccinimide (PSI), and generally, the concentration of polysuccinimide (PSI) is selected from a concentration range of 1 to 50% by weight.
• concentration of polysuccinimide (PSI) in the above reaction system can be selected from the range of 1 to 50% by weight, and the optimum concentration for the compound having an amino group and a carboxy group to be used.
• the method of isolating the produced polymer from the reaction solution after the completion of the reaction which is adopted in the method for producing modified polyaspartic acid or its salt according to the present embodiment, can substantially isolate the reaction product with the desired purity. There are no particular restrictions as long as it is.
• the above isolation method may be any known or publicly used method. Generally, known and commonly used isolation operations such as concentration, recrystallization, or reprecipitation are employed.
• Step A1 After the completion of the reaction, an excess of a poor solvent (e.g., methyl alcohol, ethyl alcohol, isopropyl alcohol, etc.) is added to the reaction solution in which the reaction product is dissolved at an appropriate temperature to crystallize the reaction product. Precipitate.
• Step A2 The crystals of the reaction product precipitated in Step 1 are isolated by decantation, filtration, suction filtration, or the like.
• Step A3 After sufficient washing with a poor solvent that does not dissolve the crystals isolated in Step 2, the crystals are dried.
• Other specific examples include, for example, a method including the following steps B1 to B3.
• Step B1 After the completion of the reaction, the reaction solution in which the reaction product is dissolved is added to the same excess poor solvent as above at an appropriate temperature to precipitate crystals of the reaction product.
• Step B2 The crystals of the reaction product precipitated in Step 1 are isolated in the same manner as in Step A2.
• Step B3 The crystals isolated in Step 2 are washed and dried in the same manner as in Step A3.
• the obtained modified polyaspartic acid or its salt is not isolated, and the mixed solution after the reaction is used as it is to participate in the crosslinking reaction described below. Good too. Further, if necessary, only some unreacted raw materials other than the solvent may be removed to participate in the crosslinking reaction described below. Further, the concentration may be adjusted by increasing or decreasing the amount of solvent in the mixed solution.
• a crosslinked product of modified polyaspartic acid or a salt thereof according to this embodiment (sometimes referred to as a crosslinked product of this embodiment) is a polyaspartic acid or a salt thereof crosslinked using a polyfunctional amine as a crosslinking agent.
• the crosslinked product according to this embodiment has a polyaspartic acid skeleton, and has a structure in which polyaspartic acid chains are connected to each other by polyfunctionality.
• the degree of crosslinking of the crosslinked product is preferably 1.0 to 5.0 mol%.
• the modified polyaspartic acid according to this embodiment is a polymer formed by peptide bonds of aspartic acid.
• the amide bond in the main chain of polyaspartic acid may be an ⁇ bond or a ⁇ bond. Further, these bonding modes may be the same or different for each structural unit. Note that the bond between the amino group of modified aspartic acid and the carboxy group at the ⁇ -position of the modified aspartic acid is an ⁇ bond, and the bond between the amino group of the modified aspartic acid and the carboxy group at the ⁇ -position is a ⁇ bond.
• the side chain of modified polyaspartic acid is represented by -CH 2 -COOH (in the case of ⁇ bond) or -COOH (in the case of ⁇ bond).
• the polyfunctional amine is a diamine
• the carboxy group present in the side chain on one modified polyaspartic acid chain and the carboxy group present in the side chain on another polyaspartic acid chain are crosslinked by the carboxyl group forming an amide bond with the amino group of the diamine.
• the polyfunctional amine is a diamine
• the carboxy group derived from the compound having the amino group and the carboxyl group (“ (referred to as "addition-derived carboxy groups”) are also present in side chains on the chain.
• the addition-derived carboxy group and the carboxy group present in the side chain on another polyaspartic acid chain form an amide bond with the amino group of the diamine, so that the polyasparagine Acid chains may be crosslinked.
• addition-derived carboxy group and the addition-derived carboxy group present in the side chain on another polyaspartic acid chain form an amide bond with the amino group of the diamine, so that the polyaspartic acid chains are cross-linked. may be done.
• a portion of the carboxy groups on the side chains of modified polyaspartic acid form such a crosslink.
• Another part (or even the entire remainder) of the carboxy groups on the side chains of polyaspartic acid may be a free carboxylic acid or may form a salt.
• the salt is not particularly limited, and examples include alkali metal salts such as sodium salt and potassium salt, and salts consisting of organic bases such as triethylamine, N-methylmorpholine, triethanolamine, and diisopropylethylamine.
• a specific example of the salt of polyaspartic acid includes, for example, the sodium salt of polyaspartic acid.
• the carboxy group of the unmodified polyaspartic acid side chain can bond with -NH- in the amide bond of the main chain to form an imide ring. Therefore, an imide ring may be present in a part of the main chain. That is, the main chain portion in some of the structural units in the crosslinked product of this embodiment may form a part of the imide ring formed as described above.
• "partially crosslinked” refers to a portion of the carboxy groups on the side chains of polyaspartic acid forming a crosslink.
• the weight average molecular weight of the individual modified polyaspartic acid chains connected to each other by crosslinking in the crosslinked product of this embodiment is preferably 40,000 or more, more preferably 80,000 or more, and 100,000 or more. It is more preferable that The greater the weight average molecular weight of the modified polyaspartic acid chains, the greater the thickening effect.
• PSI polysuccinimide
• these weight average molecular weights are calculated by hydrolyzing the polysuccinimide (PSI) used as the raw material. By measuring the obtained polyaspartic acid salt by GPC, it can be determined as a value in terms of pullulan, which is a standard substance.
• the method for producing a crosslinked product of modified polyaspartic acid or a salt thereof according to this embodiment is not particularly limited, but for example, the modified polyaspartic acid of this embodiment It can be obtained by reacting an acid or a salt thereof with a polyfunctional amine compound and then performing a hydrolysis reaction of the reaction product while adjusting the pH in an aqueous solution. Alternatively, it can be obtained by reacting and hydrolyzing the modified polyaspartic acid of this embodiment or its salt with a polyfunctional amine in an aqueous solution. At this time, imide rings may remain in some of the structural units.
• the polyfunctional amine according to this embodiment is preferably an amine having at least two primary and/or secondary amino groups.
• diamine compounds include aliphatic diamines such as ethylene diamine and hexamethylene diamine; aliphatic diamines containing aromatic rings such as xylene diamine; alicyclic diamines such as norbornene diamine; 1,2-bis(2-aminoethoxy) Ether diamines such as ethane, diethylene glycol bis(3-aminopropyl) ether, polyoxyethylene diamine, and polyoxypropylene diamine; Amino acids and their derivatives with amino groups in their side chains, such as lysine and ornithine; cystine, Examples include monoamino compounds connected by disulfide bonds, such as cystamine, and derivatives thereof.
• lysine, ornithine, cystine, cystamine, and derivatives thereof which are highly safe polymer decomposition products.
• derivatives include diketopiperazines, which are cyclic dimers of lysine and ornithine, and esters of lysine, ornithine, and cystine.
• polyfunctional amine compounds other than diamine examples include tris(2-aminoethyl)amine, tris(3-aminopropyl)amine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine.
• a method for reacting the modified polyaspartic acid or its salt with the polyfunctional amine of the present embodiment there is, for example, a method in which the reaction is carried out in an organic solvent.
• An example in which the polyfunctional amine according to this embodiment is a diamine will be explained.
• a solution of the diamine in the organic solvent is added dropwise.
• aprotic polar organic solvent examples include dimethylformamide (DMF), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), dimethylimidazolidinone (DMI), dimethylsulfoxide (DMSO), and sulfolane.
• the amount of organic solvent used to dissolve the modified polyaspartic acid or its salt of the present embodiment is not particularly limited, but it is usually used at a polymer concentration of 1 to 50% by mass.
• the temperature at which the modified polyaspartic acid or its salt of the present embodiment is reacted with the diamine is not particularly limited, but is, for example, room temperature to 80°C.
• reaction temperature reaction temperature, reaction time, reaction concentration, amount of diamine used, etc.
• reaction temperature reaction temperature, reaction time, reaction concentration, amount of diamine used, etc.
• the generated precursor of the crosslinked product of this embodiment is isolated, a hydrolysis reaction of the imide ring of the precursor of the isolated crosslinked product is performed.
• the compound having an amino group and a carboxyl group used is preferably an amino acid ester.
• the obtained modified polyaspartic acid or its salt has an ester moiety derived from the amino acid ester.
• the ester moiety derived from the amino acid ester is also subjected to a hydrolysis reaction in the hydrolysis reaction.
• reaction conditions are not particularly limited as long as the following can be achieved. ⁇ Substantially, the stirring of the reaction system can be maintained, the efficiency of hydrolysis of the imide ring and the ester moiety is sufficient, the degree of hydrolysis of the amide bond in the main chain is small, and the pH can be controlled. .
• the reaction system for hydrolyzing the precursor of the crosslinked product of this embodiment is usually carried out by suspending the precursor of the crosslinked product of this embodiment in an aqueous solution, but it may contain various organic solvents that are miscible with water. It's okay. Specific examples of various organic solvents that are miscible with water include alcohols such as methyl alcohol and ethyl alcohol, acetone, and tetrahydrofuran.
• the pH during hydrolysis of crosslinked polysuccinimide (PSI) is usually preferably 8.0 to 11.5, more preferably 9.0 to 11.0. The higher this value is, the higher the efficiency of hydrolysis of the imide ring is, and the lower this value is, the lower the degree of hydrolysis of the undesirable amide bond in the main chain.
• the alkali used for hydrolyzing the precursor of the crosslinked product of this embodiment is usually used in the form of an aqueous solution.
• the concentration is not particularly limited as long as it is the following concentration, but is preferably 5 to 48%, more preferably 10 to 30%.
• the crosslinked product of this embodiment which is produced by the hydrolysis reaction of the precursor of the crosslinked product of this embodiment, can be isolated by conventional isolation operations such as recrystallization, reprecipitation, filtration, and concentration. Manipulation can be used.
• the modified polyaspartic acid or its salt is produced, and then the modified polyaspartic acid or its salt is reacted with a polyfunctional amine to produce a crosslinked product.
• the reaction for producing modified polyaspartic acid or its salt and the crosslinking reaction may be performed simultaneously.
• polysuccinimide (PSI) polysuccinimide
• the compound having an amino group and a carboxy group examples thereof include the following three production methods.
• (I) A step of reacting polysuccinimide (PSI) with the compound having an amino group and a carboxy group to obtain the polyaspartic acid or its salt (P1), and the reaction product (P1) obtained in the above step. and a polyfunctional amine (hereinafter referred to as method (I)).
• (II) A manufacturing method in which polysuccinimide (PSI) and the compound having an amino group and a carboxyl group are first mixed and reacted, and then a polyfunctional amine is added at a constant rate (hereinafter referred to as method). (II)).
• (III) A manufacturing method (hereinafter referred to as method (III)) in which polysuccinimide (PSI), the compound having an amino group and a carboxy group, and a polyfunctional amine are mixed and then reacted. Method (I) or method (II) is preferred, and method (I) is more preferred.
• the size (average particle size) of the crosslinked body of this embodiment is not particularly limited, but is preferably 150 ⁇ m or less, more preferably 100 ⁇ m or less, and even more preferably 80 ⁇ m or less.
• the average particle size is preferably 150 ⁇ m or less, more preferably 100 ⁇ m or less, and even more preferably 80 ⁇ m or less.
• the amount of the polyfunctional amine used in this embodiment may be appropriately selected depending on the desired degree of crosslinking.
• the amount of diamine used is determined based on the molar equivalent of polysuccinimide (PSI).
• PSI polysuccinimide
• the amount is 0.5 to 25 moles, preferably 1.0 to 20 moles, more preferably 1.5 to 15 moles, and even more preferably 2.0 to 10 moles.
• the amount of diamine used is 3 moles per 100 moles of polysuccinimide (PSI), it is simply defined as "the amount of diamine used is 3 mol %.”
• the thickening composition of this embodiment can maintain a viscosity above a certain level for a longer period of time.
• the equivalent number of moles of polysuccinimide (PSI) means the number of moles of aspartic acid, which is the raw material used, in the case of the above-mentioned method for synthesizing polysuccinimide (PSI).
• the amount (mol %) of polyfunctional amine used relative to polysuccinimide (PSI) refers to the "degree of crosslinking" in the present invention.
• “mol%” is used.
• the degree of crosslinking of the crosslinked product according to this embodiment is the same as that of the crosslinked polysuccinimide (PSI) before hydrolysis. Obtained from the degree of crosslinking.
• the degree of crosslinking of the crosslinked product according to this embodiment is 0.5 to 25 mol%, preferably 1.0 to 20 mol%, more preferably 1.5 to 15 mol%, even more preferably 2 .0 to 10 mol%.
• the modified polyaspartic acid is a polysuccinimide (PSI), a compound having an amino group and a carboxyl group, and a compound having a first functional group (a1) and a second functional group (a2). (A:a1-A1-a2).
• the modified polyaspartic acid or its salt according to the present embodiment is obtained by ring-opening polysuccinimide (PSI) using a compound having an amino group and a carboxyl group and a compound (A: a1-A1-a2).
• PSI ring-opening polysuccinimide
• the compound (A:a1-A1-a2) has a first functional group (a1) and a second functional group (a2).
• Polysuccinimide (PSI) As the polysuccinimide (PSI) according to this embodiment, a polysuccinimide (PSI) similar to the "polysuccinimide (PSI)" described in the first embodiment can be used.
• Compound having an amino group and a carboxy group As the compound having an amino group and a carboxyl group according to the present embodiment, a compound having an amino group and a carboxyl group similar to the "compound having an amino group and a carboxyl group" described in the first embodiment can be used. When this compound has a carboxyl group, the thickening properties of a crosslinked product of modified polyaspartic acid or its salt are improved.
• the first functional group (a1) of the compound (A) according to this embodiment is preferably an amino group (NH 2 -). More preferably, the amino group of the first functional group (a1) is an NH 2 --CH 2 -- amino group.
• the present invention may be the polyfunctional amine according to the first embodiment described above.
• the compound (A) according to this embodiment is a polyfunctional amine, it is preferably a diamine compound.
• the specific example of the diamine compound according to this embodiment may also be the same as the specific example described in the first embodiment.
• the first functional group (a1) of the compound (A) according to the present embodiment is an amino group (NH 2 -) and the second functional group (a2) is also an amino group (NH 2 -), It is more preferable that the amino group of the second functional group (a2) is an amino group in the structure represented by the following formula (1).
• G represents a carboxylic acid group or a salt thereof.
• the salt includes alkali metal salts such as sodium salts and potassium salts; alkaline earth metal salts such as calcium salts and magnesium salts; organic base salts such as amine salts, lysine salts, Examples include basic amino acid salts such as arginine salts.
• alkali metal salts such as sodium salts and potassium salts
• alkaline earth metal salts such as calcium salts and magnesium salts
• organic base salts such as amine salts, lysine salts
• Examples include basic amino acid salts such as arginine salts.
• preferred salts are alkali metal salts, and more preferred salts include sodium salts and potassium salts.
• the first functional group (a1) of the compound (A) according to this embodiment is an amino group (NH 2 -), and the second functional group (a2) of the compound (A) according to this embodiment is also an amino group (NH 2 -).
• the amino group of the second functional group of the compound (A) has lower reactivity with polysuccinimide (PSI) than the amino group of the first functional group.
• examples of the compound (A) include diamines having different terminal structures containing each amino group. Examples include asymmetric diamines.
• the first functional group (a1) of the compound (A) according to the present embodiment is an NH 2 -CH 2 - amino group
• the second functional group (a2) has a structure represented by the above formula (1).
• An example of the amino group in the group includes a compound represented by the following formula (5).
• n 1 to 10, preferably 2 to 8, more preferably 3 to 5)
• the compound (A) according to this embodiment may be a salt of the carboxylic acid group of the compound represented by the above formula (5).
• the salts include alkali metal salts such as sodium salts and potassium salts; alkaline earth metal salts such as calcium salts and magnesium salts; organic base salts such as amine salts; basic amino acid salts such as lysine salts and arginine salts. Examples include salt.
• preferred salts are alkali metal salts, and more preferred salts include sodium salts and potassium salts.
• the first functional group (a1) of the compound (A) according to this embodiment is an amino group and the second functional group (a2) is also an amino group
• the first functional group (a1) is NH 2 -CH
• Examples of compounds (A) in which the amino group of the second functional group (a2) is an amino group in the structure represented by the above formula (1) include the following formula (6). The following compounds are mentioned.
• n is Represents an integer of 1 to 10, preferably 2 to 8, more preferably 3 to 5.
• the compound (A) according to the present embodiment may be a salt of the carboxylic acid group of the compound represented by the above formula (6), and in that case, the salt includes an alkali metal salt such as a sodium salt or a potassium salt; Salts, alkaline earth metal salts such as magnesium salts; organic base salts such as amine salts; basic amino acid salts such as lysine salts and arginine salts.
• alkali metal salt such as a sodium salt or a potassium salt
• Salts alkaline earth metal salts such as magnesium salts
• organic base salts such as amine salts
• basic amino acid salts such as lysine salts and arginine salts.
• preferred salts are alkali metal salts, and more preferred salts include sodium salts and potassium salts.
• the first functional group (a1) of the compound (A) according to this embodiment is an amino group
• a compound represented by the following formula (7) may be mentioned.
• n represents an integer of 1 to 10, preferably 2 to 8, more preferably 3 to 5.
• the compound (A) according to the present embodiment may be a salt of the phosphonooxy group of the compound represented by the above formula (7).
• the salts include alkali metal salts such as sodium salts and potassium salts; alkaline earth metal salts such as calcium salts and magnesium salts; organic base salts such as amine salts; basic amino acid salts such as lysine salts and arginine salts. Examples include salt.
• preferred salts are alkali metal salts, and more preferred salts include sodium salts and potassium salts.
• Examples of the compound (A) according to this embodiment include lysine, ornithine, and arginine. Furthermore, when the compound (A) according to the present embodiment contains an amino group, an acid salt of the compound (A) may be used as a raw material. Examples of the acidic salt of the compound (A) include hydrochlorides such as lysine hydrochloride, ornithine hydrochloride, and arginine hydrochloride, and similar sulfates.
• a dipeptide can be used as the compound (A) according to this embodiment.
• the dipeptides mentioned above include basic amino acids at the C-terminus, such as glycine-lysine (isopeptide bond), alanine-lysine (isopeptide bond), glycine-ornithine (isopeptide bond), and alanine-ornithine (isopeptide bond).
• Dipeptides having a basic amino acid residue at the N-terminus such as lysine-glycine, lysine-alanine, ornithine-glycine, ornithine-alanine, and the like.
• glycine-lysine is a dipeptide represented by the following formula (8)
• lysine-glycine is a dipeptide represented by the following formula (9).
• the method for producing modified polyaspartic acid or its salt includes the production of polysuccinimide (PSI) by reacting the compound having an amino group and a carboxy group with the compound (A: a1-A1-a2).
• PSI polysuccinimide
• a ring-opening reaction method is mentioned.
• the compound having an amino group and a carboxy group is an amino acid ester.
• the modified polyaspartic acid or its salt according to the present embodiment is an amino acid ester-modified polyaspartic acid or its salt (sometimes referred to as "amino acid ester modified product").
• the method for producing the modified amino acid ester according to the present embodiment includes a ring-opening reaction method of polysuccinimide (PSI) by reacting the amino acid ester with the compound (A) (a1-A1-a2). By reacting polysuccinimide (PSI) with the amino acid ester and compound (A) (a1-A1-a2), the imide ring of polysuccinimide (PSI) is opened.
• PSI polysuccinimide
• Organic solvent In the method for producing modified polyaspartic acid or its salt according to the present embodiment, the organic solvent can be used as long as it substantially dissolves the following compounds and as long as it does not substantially inhibit the progress of the reaction. , not particularly limited.
• the above compounds include polysuccinimide (PSI), a compound having an amino group and a carboxy group, and the compound (A).
• organic solvent examples include aprotic solvents such as dimethylformamide (DMF), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), dimethylimidazolidinone (DMI), dimethylsulfoxide (DMSO), and sulfolane.
• aprotic solvents such as dimethylformamide (DMF), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), dimethylimidazolidinone (DMI), dimethylsulfoxide (DMSO), and sulfolane.
• polar organic solvents examples include polar organic solvents, which can be used alone or in combination.
• Amount of compound containing amino group and carboxy group used The amount of the compound having an amino group and a carboxy group according to the present embodiment to be used is not particularly limited as long as it is substantially dissolved in the organic solvent and/or does not substantially inhibit the progress of the reaction.
• the amount used is generally 0.1 to 10 times the equivalent of the monomer unit of polysuccinimide (PSI), preferably 0.1 to 1.0 times the equivalent.
• Base catalyst In the method for producing a modified polyaspartic acid or a salt thereof according to the present embodiment, the optionally used basic catalyst may be the same as that described in the method for producing a modified polyaspartic acid or a salt thereof according to the first embodiment. good.
• the amount of the basic catalyst used is the same as that described in the method for producing a modified polyaspartic acid or a salt thereof according to the first embodiment.
• reaction temperature In the method for producing a modified polyaspartic acid or a salt thereof according to the present embodiment, the reaction temperature may be the same as that described in the method for producing a modified polyaspartic acid or a salt thereof according to the first embodiment.
• the concentration of the reaction system employed in the method for producing modified polyaspartic acid or its salt according to the present embodiment is not particularly limited as long as the progress of the reaction can be substantially maintained.
• the concentration of the reaction system is selected based on the concentration of polysuccinimide (PSI), and generally, the concentration of polysuccinimide (PSI) is selected from a concentration range of 1 to 50% by weight.
• the concentration of polysuccinimide (PSI) in the above reaction system can be selected from the range of 1 to 50% by weight, and the optimum concentration for the compound having an amino group and a carboxy group to be used.
• the concentration of the compound (A) used can be appropriately selected depending on the degree of crosslinking described below.
• the method for isolating the produced polymer from the reaction solution after the completion of the reaction adopted in the method for producing modified polyaspartic acid or its salt according to the present embodiment is the method for producing modified polyaspartic acid or its salt according to the first embodiment. It may be the same as that described in .
• the obtained modified polyaspartic acid or its salt is not isolated, and the mixed solution after the reaction is used as it is to participate in the crosslinking reaction described below. Good too. Further, if necessary, only some unreacted raw materials other than the solvent may be removed to participate in the crosslinking reaction described below. Further, the concentration may be adjusted by increasing or decreasing the amount of solvent in the mixed solution.
• the crosslinked product of the modified polyaspartic acid or its salt of the present embodiment (sometimes referred to as the crosslinked product of the present embodiment) is composed of the modified polyaspartic acid or its salt according to the present embodiment, and the polyfunctional epoxy (B). It is a reactant of and.
• the modified polyaspartic acid or its salt contains a PSI-a1 (A) bond formed by an addition reaction between the first functional group (a1) and polysuccinimide (PSI).
• the crosslinked product of this embodiment includes a Ba2 (A) bond formed by reacting the second functional group (a2) with the polyfunctional epoxy (B).
• the crosslinked body includes a crosslinked structure (PABAP) represented by PSI-a1-A1-a2-B-a2-A1-a1-PSI.
• the polyvalent epoxy compounds according to this embodiment include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, diglycerol polyglycidyl ether, and polyglycerol polyglycidyl ether.
• the method for producing a cross-linked product of modified polyaspartic acid or a salt thereof starts with the modified polyaspartic acid according to the present embodiment.
• a step of subjecting aspartic acid or a salt thereof to a hydrolysis reaction to obtain a hydrolyzed modified polyaspartic acid or a salt thereof (sometimes referred to as a "hydrolyzed modified product"), the hydrolyzed modified product, and a polyfunctional epoxy (B) and a step of reacting with water or a water-containing solvent to produce a crosslinked product.
• the modified polyaspartic acid or its salt and the polyfunctional epoxy (B) are the same as those described in the crosslinked product of this embodiment, and their preferred examples are also the same.
• the modified polyaspartic acid or its salt according to this embodiment when an amino acid ester is used as the compound having an amino group and a carboxy group, the modified polyaspartic acid or its salt according to this embodiment is an amino acid ester.
• Modified polyaspartic acid or its salt (sometimes referred to as "amino acid ester modified product").
• the method for producing a crosslinked product of modified polyaspartic acid or a salt thereof according to the present embodiment preferably uses the modified amino acid ester.
• the method for producing the crosslinked product of the present embodiment includes first hydrolyzing the modified amino acid ester.
• the method includes a step of reacting to obtain a modified amino acid, and a step of reacting the modified amino acid and polyfunctional epoxy (B) in water or a water-containing solvent to produce a crosslinked product.
• the method for producing a crosslinked product of modified polyaspartic acid or a salt thereof is a method for producing a crosslinked product of modified polyaspartic acid or a salt thereof according to the present embodiment.
• the method may also include a step of reacting the salt and the polyfunctional epoxy (B) in water or a water-containing solvent to produce a crosslinked product.
• the modified polyaspartic acid or its salt is produced, and then the modified polyaspartic acid or its salt is reacted with a polyfunctional epoxy (B) to form a crosslinked product. May be generated.
• the reaction for producing modified polyaspartic acid or its salt and the crosslinking reaction may be performed simultaneously. Examples include the following methods (i) to (iii).
• method (i) a step of reacting polysuccinimide (PSI) with the compound having an amino group and a carboxy group and compound (A) to obtain the modified polyaspartic acid or its salt (P1);
• a manufacturing method comprising a step of reacting the obtained reactant (P1) with a polyfunctional epoxy compound.
• method (ii) While polysuccinimide (PSI), the compound having an amino group and a carboxy group, and compound (A) are first mixed and reacted, the polyfunctional epoxy compound is then added at a constant rate.
• a manufacturing method hereinafter referred to as method (ii)).
• method (iii) A manufacturing method in which polysuccinimide (PSI), the compound having an amino group and a carboxy group, compound (A), and a polyfunctional epoxy compound are mixed and then reacted (hereinafter referred to as method (iii)) . From the viewpoint that it is easy to control the structure of the obtained modified polyaspartic acid crosslinked product, method (i) or method (ii) is preferred, and method (i) is more preferred.
• the manufacturing method of this embodiment will be described in detail by taking the method (i) above as an example.
• the modified polyaspartic acid or its salt obtained in the above-described method for producing modified polyaspartic acid or its salt of the present embodiment is hydrolyzed to produce hydrated polyaspartic acid or its salt. It is preferable to include a step of obtaining a decomposed modified polyaspartic acid or a salt thereof.
• the modified polyaspartic acid or its salt after hydrolysis can be converted into a polyfunctional epoxy compound as a reactant (P1) in a later step.
• the modified polyaspartic acid or its salt obtained by the method for producing modified polyaspartic acid or its salt of the present embodiment described above is the amino acid ester modified product
• the step of obtaining the reactant (P1) it is preferable to include a step of hydrolyzing the modified amino acid ester to obtain the modified amino acid.
• the amino acid modified product is preferably converted into a polyfunctional epoxy compound as a reactant (P1) in a later step.
• the following method may be used in the step of obtaining reactant (P1). It is preferable that the compound having an amino group and a carboxy group and the compound (A) are first dissolved in water.
• a compound having 0.2 to 2.0 parts by weight of the above amino group and a carboxy group is preferable, and 0.5 to 1.5 parts by weight of the above amino group and Compounds having a carboxy group are more preferred.
• 5 to 50 parts by weight of water is preferably used, more preferably 7 to 15 parts by weight, per 1 part by weight of compound (A).
• PSI Polysuccinimide
• the compounding ratio is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, of compound (A) to 10 parts by mass of polysuccinimide (PSI). , more preferably 1.5 to 10 parts by mass.
• the amount of the compound having an amino group and a carboxy group is preferably 0.5 to 20 parts by weight, more preferably 1 to 15 parts by weight, relative to 10 parts by weight of polysuccinimide (PSI).
• the amount is preferably 1.5 to 10 parts by mass, and more preferably 1.5 to 10 parts by mass.
• the proportion of units to which compound (A) is added is preferably 2 to 50%, more preferably 5 to 35%, and 8 to 25% of the total units. It is even more preferable that there be.
• the proportion of units to which compound (A) is added is determined by the integral value Ia of the peak derived from protons of -CH 2 - in the polyaspartic acid main chain skeleton and -CH 2 - in compound (A) in proton NMR.
• the ratio of units to which the compound having an amino group and a carboxy group is added is preferably 50 to 99, more preferably 60 to 95, and more preferably 70 to 99 to the total units. More preferably, it is 90.
• the proportion of units to which the compound having an amino group and a carboxyl group is added is determined by the integral value Ia of the peak derived from the proton of -CH 2 - in the main chain skeleton of polyaspartic acid in proton NMR and the ratio of the unit to which the compound having an amino group and a carboxyl group is added. It is determined from the ratio Ic/(Ia+Ib+Ic) of the integral value Ib of the peak derived from the proton of --CH 2 -- in the compound having an amino group and a carboxy group and the integral value Ic of the peak derived from the proton of --CH 2 -- in the compound having an amino group and a carboxy group.
• the amount of the polyfunctional epoxy compound blended is 0.5 to 10 parts by mass with respect to 100 parts by mass of the reactant (P1).
• the amount is preferably 1.0 to 5.0 parts by mass, and more preferably 1.0 to 5.0 parts by mass.
• the reactant (P1) a solid reactant (P1) obtained by isolating the reactant (P1) from the reaction solution obtained in the step of producing the reactant (P1) can be used. In that case, it is preferable to first prepare an aqueous solution of the reactant (P1) before blending the polyfunctional epoxy compound.
• a polyfunctional epoxy compound can be blended as it is in a solution state from the reaction solution obtained in the reactant (P1) production step without isolating the reactant (P1).
• the reaction temperature between the reactant (P1) and the polyfunctional epoxy compound can be 30°C to 100°C.
• the temperature is preferably 40 to 80°C, more preferably 50 to 70°C.
• the reaction time can be, for example, 10 minutes to 600 minutes at 60°C. More preferably, the time is 20 to 300 minutes.
• the size (average particle size) of the crosslinked product of this embodiment is not particularly limited, but for example, for use in thickening compositions, it is preferably 150 ⁇ m or less, more preferably 100 ⁇ m or less, and even more preferably It is 80 ⁇ m or less.
• the average particle size is preferably 150 ⁇ m or less, more preferably 100 ⁇ m or less, and even more preferably It is 80 ⁇ m or less.
• [Crosslinking degree] The amounts of the compound having an amino group and a carboxy group, the compound (A), and the polyfunctional epoxy (B) to be used in the polysuccinimide (PSI) according to this embodiment are appropriately selected depending on the desired degree of crosslinking. do it. For example, in the case of the production method using the above method (i), the blending ratio of polysuccinimide (PSI), the compound having an amino group and a carboxyl group, and the compound (A) is adjusted within the above range, Furthermore, the degree of crosslinking can be controlled by adjusting the polyfunctional epoxy (B).
• the proportion of units to which compound (A) is added is preferably 1 to 30%, more preferably 2 to 25%, even more preferably 3 to 20%, based on the total unit.
• the addition rate can be measured by NMR.
• the thickening composition of one embodiment of the present invention includes at least one type selected from the group consisting of the crosslinked product of the first embodiment and the crosslinked product of the second embodiment (this embodiment). (sometimes referred to as a crosslinked body depending on the form).
• the thickening composition of this embodiment does not need to contain water.
• the thickening composition of the present embodiment obtained by the method described below may be further subjected to a drying treatment to obtain a powdery thickening composition.
• the thickening composition of this embodiment may consist only of the crosslinked product according to this embodiment. That is, it is not necessary to substantially contain other components other than the crosslinked body according to the present embodiment. "Substantially free of other components" means, for example, that the content of the crosslinked material in the thickening composition is 95.0 to 100% by mass, and preferably 98.0 to 100% by mass. It is preferably 99.0 to 100% by mass, more preferably 100%.
• the thickening composition of this embodiment may contain water.
• the thickening composition of this embodiment obtained by the method described above may be used as it is without being subjected to dehydration treatment.
• the water in this embodiment include ion exchange water.
• the "thickening composition containing water” is sometimes referred to as a "thickening solution.” It is preferable that the content of the crosslinked material is 0.05 to 10% by mass, and 0.1 to 7.0% by mass with respect to a total of 100% by mass of the thickening composition (thickening solution) containing water. The content is more preferably 0.3 to 5.0% by mass, even more preferably 0.5 to 3.0% by mass.
• the thickening composition contains water
• its pH value is preferably in the range of 4.5 to 10.0, more preferably in the range of 5.0 to 9.0.
• the method for adjusting the pH value is not particularly limited, and examples thereof include methods using acidic substances and basic substances.
• Specific examples of acids include organic acids such as citric acid.
• Specific examples of the base include organic basic compounds such as ammonia and inorganic basic compounds such as sodium hydroxide.
• the thickening composition of this embodiment may further contain other components.
• examples include cosmetic active ingredients. Also included are additives often used in cosmetics, such as surface forming agents, stabilizers, and humectants.
• ⁇ Method for preparing thickening composition for example, the crosslinked product according to the present embodiment described above is weighed in a predetermined amount, and if necessary, water or other components are added in a predetermined amount. Examples include a method of adding and stirring.
• an aqueous dispersion of the crosslinked product according to this embodiment is first prepared, and if necessary, it may be mixed with other components.
• a predetermined amount of the solid crosslinked product may be weighed and, if necessary, mixed with other solid components.
• a dispersion containing the crosslinked body and water may be prepared first, and if necessary, mixed with other components to prepare a mixed liquid, followed by drying.
• the cosmetic composition according to this embodiment includes the above-mentioned thickening composition and a cosmetic active ingredient.
• Cosmetic active ingredients include, for example, higher alcohols, lower alcohols, polyhydric alcohols, pH adjusters, surfactants, sequestering agents, antioxidants, physical and chemical sunscreens, vitamins, and skin protection agents. agents, oils and fats, hydrocarbon oils, humectants, antiperspirants, detergents, fragrances, cosmetic colorants, antibacterial agents, bactericidal agents, feel improvers and foam stabilizers, other thickeners, etc.
• the cosmetic composition according to this embodiment may further contain water.
• the content of the crosslinked product according to the present embodiment may be 0.05 to 10% by mass based on the total 100% by mass of the cosmetic composition. It is preferably 0.1 to 7.0% by weight, more preferably 0.3 to 5.0% by weight, and particularly preferably 0.5 to 3.0% by weight.
• One or more types selected from the group consisting of the crosslinked product of the first embodiment and the crosslinked product of the second embodiment can be used for absorbing diapers, sanitary products, etc. It can be used as a water-absorbing composition constituting an absorbent body for sexual articles.
• the size (average particle size) is preferably 1 to 5000 ⁇ m, more preferably 10 to 1000 ⁇ m, and even more preferably 100 to 1000 ⁇ m. It is 800 ⁇ m.
• the crosslinked product according to this embodiment can be used as a thickening composition.
• the size (average particle size) is preferably 150 ⁇ m or less, more preferably 100 ⁇ m or less, and still more preferably 80 ⁇ m or less. .
• the weight average molecular weight of polysuccinimide (PSI) was determined as a polystyrene equivalent value using a GPC method (differential refractometer).
• a G1000HHR column, a G4000HHR column, and a GMHHR-H column (TSKgel (registered trademark), Tosoh Corporation) were used for the measurement.
• Dimethylformamide containing 10 mM lithium bromide was used as the eluent.
• Synthesis example 2 ⁇ Synthesis of ⁇ -alanine ethyl ester/L-lysine methyl ester modified product> 10 parts of polysuccinimide (PSI) obtained in Synthesis Example 1 was mixed with 40 parts of dimethylformamide, and the mixture was stirred at 60° C. for 5 hours to dissolve. While heating the solution to 40°C, 12.7 parts of ⁇ -alanine ethyl ester hydrochloride and 10 parts of triethylamine were added, and the mixture was reacted for 8 hours while being maintained at 40°C.
• PSI polysuccinimide
• Example 1 ⁇ Synthesis of ⁇ -alanine ethyl ester modified diamine crosslinked product> 5.0 parts of polysuccinimide (PSI) obtained in Synthesis Example 1 was mixed with 20 parts of dimethylformamide and dissolved by stirring at 60° C. for 5 hours. While heating the solution to 40°C, 7.1 parts of ⁇ -alanine ethyl ester hydrochloride and 5.6 parts of triethylamine were added, and the mixture was reacted for 8 hours while being maintained at 40°C. After triethylamine hydrochloride in the reaction solution was filtered off, the reaction solution was heated to 40°C again.
• PSI polysuccinimide
• a mixed solution of 0.78 parts of hexamethylene diamine and 0.78 parts of dimethylformamide was added dropwise, and the mixture was reacted for 6 hours while being kept at 40°C. After the obtained gel was finely ground, it was added to 350 parts of ethyl acetate and washed for 1 hour. After filtering, the mixture was further washed with 350 parts of ethyl acetate for 1 hour and vacuum-dried at 60°C to obtain 8.6 parts of a ⁇ -alanine ethyl ester modified diamine crosslinked product.
• Example 2 ⁇ Synthesis of ⁇ -alanine/L-lysine modified epoxy crosslinked product> 2.0 parts of the ⁇ -alanine sodium/L-lysine sodium modified product obtained in Synthesis Example 3 was dissolved in 3.0 parts of ion-exchanged water. 0.16 part of a 20% aqueous solution of polyfunctional epoxy compound EX-810 (manufactured by Nagase ChemteX) was mixed and reacted at 60° C. for 2 hours. The obtained gel composition was vacuum dried at 60°C.

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