JP2024001620A - Carboxyl group-containing polymer and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel cross-linked carboxyl group-containing polymer that is excellent in solubility in water and further excellent in transparency of a composition obtained by dissolving in water, compared with a so far proposed cross-linked carboxyl group-containing polymer.

SOLUTION: A method for producing a carboxyl group-containing polymer by copolymerizing an α,β-unsaturated carboxylic acid (a1) and a compound (a2) having two or more ethylenically unsaturated groups, the method comprising: copolymerizing (a1) and (a2) in the presence of an inert solvent containing an emulsifier, the emulsifier includes a fatty acid alkylene oxide adduct and a modified polyoxyalkylene, and an amount of the fatty acid alkylene oxide adduct is 3.5 to 4.5 pts.mass per 100 pts.mass of (a1), and the amount of the polyoxyalkylene modified substance is 1 pt.mass or more per 100 pts.mass of (a1).

SELECTED DRAWING: None

COPYRIGHT: (C)2024,JPO&INPIT

Description

The present disclosure relates to a carboxyl group-containing polymer, a method for producing the same, and the like.

Conventionally, crosslinked carboxyl group-containing polymers have been widely used as thickeners for cosmetics, moisturizing agents for poultices, emulsifiers, suspension stabilizers for suspensions, gel bases for batteries, etc. There is. Examples of such crosslinked carboxyl group-containing polymers include copolymers of α,β-unsaturated carboxylic acids such as acrylic acid and polyallyl ether (Patent Document 1), α,β-unsaturated carboxylic acids, etc. and hexaallyl trimethylene trisulfone (Patent Document 2), a copolymer of α,β-unsaturated carboxylic acid and triallyl phosphate (Patent Document 3), α,β-unsaturated carboxylic acid and Copolymers with glycidyl methacrylate and the like (Patent Document 4) are known.

These crosslinked carboxyl group-containing polymers are dissolved in water and then neutralized with a neutralizing agent such as an alkaline compound to form a neutralized viscous liquid that is used for the above purposes.

In order to use the crosslinked carboxyl group-containing polymer for these purposes, it is necessary to prepare a homogeneous aqueous solution thereof. However, the crosslinked carboxyl group-containing polymer is usually produced as a powder, and when the crosslinked carboxyl group-containing polymer powder is dissolved in water, lumps are likely to be formed. Once mako is formed, a gel-like layer is formed on its surface, which slows down the rate at which water permeates into the inside, making it difficult to obtain a uniform solution. Therefore, when using a cross-linked carboxyl group-containing polymer, in order to prevent the formation of mako, it is necessary to gradually add the cross-linked carboxyl group-containing polymer to water under high-speed stirring, which is an inefficient operation. In some cases, special dissolving equipment may be required to prevent the formation of mako.

For example, Patent Document 5 describes a crosslinked carboxyl group-containing polymer in which the formation of mamako as described above is suppressed, when a carboxyl group-containing polymer is produced by polymerizing α,β-unsaturated carboxylic acid, etc. A technique has been proposed in which a specific amount of at least one compound selected from polyhydric alcohol fatty acid ester and polyhydric alcohol fatty acid ester alkylene oxide adduct is added. Further, Patent Document 6 describes that a copolymer containing a specific olefinically unsaturated carboxylic acid or anhydride and a specific steric stabilizer has excellent water dispersibility. Furthermore, Patent Document 7 discloses that, in addition to a specific carboxyl group-containing polymer, a composition containing a specific polyhydric alcohol fatty acid ester alkylene oxide adduct and a specific polyoxyalkylene modified product has a high solubility in water and a specific polyoxyalkylene modified product. It is described that it has excellent thickening properties, and that the composition obtained when dissolved in water and neutralized has high transparency.

US Patent No. 2,923,692 US Patent No. 2958679 US Patent No. 3,426,004 Japanese Patent Application Publication No. 58-84819 Japanese Patent Application Publication No. 2000-355614 US Patent No. 5,468,797 International Publication No. 2016/056591

The present inventors have discovered that the solubility in water is even better than that of the crosslinked carboxyl group-containing polymers that have been proposed in the past, and the transparency of the composition obtained by dissolving and neutralizing in water is also even higher. In order to obtain an excellent new crosslinked carboxyl group-containing polymer, we conducted studies.

The present inventors have proposed a method of copolymerizing an α,β-unsaturated carboxylic acid and a compound having two or more ethylenically unsaturated groups in the presence of an inert solvent containing an emulsifier. By using specific amounts of the oxide adduct and polyoxyalkylene modified product, the carboxyl group has excellent solubility in water and excellent transparency of the composition obtained by dissolving in water and neutralizing it. We discovered the possibility of preparing a polymer composition containing the same, and made further improvements.

This disclosure encompasses, for example, the subject matter described in the following sections.
Item 1.
A method for producing a carboxyl group-containing polymer by copolymerizing an α,β-unsaturated carboxylic acid (a1) and a compound (a2) having two or more ethylenically unsaturated groups, the method comprising:
(a1) and (a2) are copolymerized in the presence of an inert solvent containing an emulsifier,
The emulsifier includes a fatty acid alkylene oxide adduct and a polyoxyalkylene modified product,
The amount of fatty acid alkylene oxide adduct is 3.5 to 4.5 parts by mass based on 100 parts by mass of (a1),
The amount of the polyoxyalkylene modified substance is 1 part by mass or more per 100 parts by mass of (a1),
Production method.
Item 2.
Item 2. The production method according to item 1, wherein the inert solvent contains an aliphatic hydrocarbon having 2 to 8 carbon atoms and an acetic acid alkyl ester.
Item 3.
The following (A) to (C):
(A) Polymer obtained by copolymerizing α,β-unsaturated carboxylic acid (a1) and compound (a2) having two or more ethylenically unsaturated groups (B) Fatty acid alkylene oxide adduct (C) Polymer Contains oxyalkylene modified products,
A carboxyl group-containing polymer composition, which has a non-stirring swelling time of less than 10 minutes as measured under the following measurement conditions, and has a transmittance of 90% or more as measured under the following measurement conditions.
[No-stirring swelling time measurement conditions]
Add 3 g of the carboxyl group-containing polymer composition to 100 g of water at 25° C., leave to stand, and visually measure the time required for the composition to completely wet.
[Permeability measurement conditions]
Add 5 g of the carboxyl group-containing polymer composition to 495 g of water at 25°C, disperse it, and neutralize it by adding an aqueous sodium hydroxide solution. The transmittance (ratio when the transmittance of ion-exchanged water is taken as 100%) is measured.
Item 4.
The content of (B) is 3.5 parts by mass to 4.5 parts by mass per 100 parts by mass of (a1),
The content of (C) is 1 part by mass or more per 100 parts by mass of (a1),
Item 3. The carboxyl group-containing polymer composition according to item 3.

A new cross-linked type polymer that has better solubility in water than conventionally proposed cross-linked carboxyl group-containing polymers, and has even better transparency of the composition obtained by dissolving it in water and neutralizing it. A carboxyl group-containing polymer composition is provided.

Each embodiment included in the present disclosure will be described in further detail below. The present disclosure preferably includes specific carboxyl group-containing polymers, methods for producing the same, etc., but is not limited thereto, and the present disclosure includes everything that is disclosed herein and can be recognized by those skilled in the art.

A method for producing a carboxyl group-containing polymer included in the present disclosure comprises copolymerizing an α,β-unsaturated carboxylic acid (a1) and a compound (a2) having two or more ethylenically unsaturated groups ( A) A method for producing a carboxyl group-containing polymer, which comprises copolymerizing (a1) and (a2) in the presence of an inert solvent containing an emulsifier. The emulsifier includes (B) a fatty acid alkylene oxide adduct and (C) a modified polyoxyalkylene product. Hereinafter, the manufacturing method included in the present disclosure may be referred to as the "manufacturing method of the present disclosure." In addition, according to the manufacturing method of the present disclosure, in addition to the (A) carboxyl group-containing polymer, (B) fatty acid alkylene oxide adduct and (C) polyoxyalkylene Carboxyl group-containing polymer compositions containing modified products can be prepared.

In the production method of the present disclosure, as described above, an α,β-unsaturated carboxylic acid (a1) and a compound (a2) having two or more ethylenically unsaturated groups are copolymerized to produce (A) a carboxyl group-containing compound. Produce a polymer.

The α,β-unsaturated carboxylic acid (a1) is not particularly limited as long as it can form the (A) carboxyl group-containing polymer, and examples include acrylic acid, methacrylic acid, crotonic acid, maleic acid, and itaconic acid. and olefinically unsaturated carboxylic acids having 3 to 5 carbon atoms such as fumaric acid. Among these α,β-unsaturated carboxylic acids (a1), acrylic acid, methacrylic acid is preferably used. One type of α,β-unsaturated carboxylic acid (a1) may be used alone, or two or more types may be used in combination.

The compound (a2) having at least two ethylenically unsaturated groups in its molecule is copolymerized with the α,β-unsaturated carboxylic acid (a1) to form the carboxyl group-containing polymer (A). In the present invention, the compound (a2) having at least two ethylenically unsaturated groups in its molecule functions as a crosslinking agent for the carboxyl group-containing polymer (A).

In addition, regarding the production method of the present disclosure, as described above, (a1) and (a2) are copolymerized to produce (A) carboxyl group-containing polymer, but in this specification, (A) ) The carboxyl group-containing polymer is a concept that includes a compound in which (a1) and (a2) are polymerized (in other words, a compound in which (a2) is crosslinked). That is, the carboxyl group-containing polymer (A) includes a compound in which the (a1) polymer is crosslinked with (a2).

The compound (a2) having at least two ethylenically unsaturated groups in its molecule is one that can be copolymerized with α,β-unsaturated carboxylic acid (a1) to form (A) a carboxyl group-containing polymer. There are no particular restrictions, but examples include acrylic esters of polyols with two or more substitutions; methacrylic esters of polyols with two or more substitutions; allyl ethers of polyols with two or more substitutions; diallyl phthalate, triallyl phosphate, methacryl Examples include allyl acid, tetraallyloxyethane, triallyl cyanurate, divinyl adipate, vinyl crotonate, 1,5-hexadiene, divinylbenzene, and the like. The polyols include ethylene glycol, propylene glycol, polyoxyethylene glycol, polyoxypropylene glycol, glycerin, polyglycerin, trimethylolpropane, pentaerythritol, saccharose, sorbitol, and the like. Among these, pentaerythritol tetraallyl ether, pentaerythritol triallyl ether, pentaerythritol diallyl ether, Tetraallyloxyethane, triallyl phosphate, and polyallyl sucrose are preferably used. The compound (a2) having at least two or more ethylenically unsaturated groups in the molecule may be used singly or in combination of two or more.

The amount of the compound (a2) having at least two ethylenically unsaturated groups in the molecule is preferably 0.01 to 10 parts by mass per 100 parts by mass of α,β-unsaturated carboxylic acid (a1). parts, more preferably 0.05 to 10 parts by weight, and still more preferably 0.05 to 3 parts by weight. By using the amount of the compound (a2) having at least two or more ethylenically unsaturated groups in the molecule within this range, the viscosity of the neutralized viscous liquid using the resulting carboxyl group-containing polymer composition can be increased. The adjustment effect can be expressed more suitably, and it can be suitably dissolved in water.

(A) The carboxyl group-containing polymer further contains other monomers in addition to the α,β-unsaturated carboxylic acid (a1) and the compound (a2) having at least two ethylenically unsaturated groups in the molecule. It may also be a polymerized one. Other monomers include α,β-unsaturated compounds (compounds having α,β-unsaturated bonds) different from the above (a1) or (a2).

The α,β-unsaturated compound is not particularly limited as long as it is different from (a1) or (a2) above, and examples thereof include methyl acrylate, ethyl acrylate, isopropyl acrylate, butyl acrylate, octyl acrylate, - Acrylic esters such as ethylhexyl acrylate, decyl acrylate, lauroyl acrylate, stearyl acrylate, eicosanyl acrylate, behenyl acrylate, tetracosanyl acrylate, glycidyl acrylate; methacrylic esters corresponding to the above acrylic esters Glycidyl ethers such as vinyl glycidyl ether, isopropenyl glycidyl ether, allyl glycidyl ether, butenyl glycidyl ether; Acrylamides such as acrylamide, N-methylacrylamide, N-ethylacrylamide, N-t-butylacrylamide; Examples include methacrylamides corresponding to the above; vinyl esters such as vinyl acetate, vinyl propionate, and vinyl benzoate. Among these α,β-unsaturated compounds, acrylic esters and methacrylic esters are preferably used, and stearyl methacrylate, eicosanyl methacrylate, behenyl methacrylate, and tetracosanyl methacrylate are particularly preferably used. Note that the α,β-unsaturated compounds may be used alone or in combination of two or more types. As the acrylic esters and methacrylic esters, for example, commercially available products such as Bremmer VMA70 (trade name, manufactured by NOF Corporation) can be used.

The amount of the α,β-unsaturated compound to be used is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, based on 100 parts by mass of α,β-unsaturated carboxylic acid (a1). Department. By using the α,β-unsaturated compound in such a range, the effect of adjusting the viscosity of the neutralized viscous liquid using the obtained carboxyl group-containing polymer composition can be more preferably expressed. can.

(B) Fatty acid alkylene oxide adduct The fatty acid alkylene oxide adduct is preferably a copolymer of fatty acid and alkylene oxide. The copolymer is preferably a random copolymer or a block copolymer, and particularly preferably a block copolymer.

The number of fatty acid units in the copolymer is 2 or more, preferably about 2 to 30. The upper or lower limits of the range are, for example, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23. , 24, 25, 26, 27, 28, or 29. For example, the range may be 1-25 or 2-25.

The fatty acid is preferably a straight-chain or branched-chain fatty acid having 8 to 20 carbon atoms, which may be substituted with a hydroxy group. The upper or lower limit of the number of carbon atoms may be 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, or 19; for example, the number may be 10 to 18. Moreover, straight chain fatty acids are more preferable. Furthermore, as mentioned above, the fatty acid may be substituted with a hydroxy group, and when it is substituted, it is preferably substituted with 1, 2, or 3 hydroxy groups, and 1 hydroxy group. More preferably, it is substituted with.

Further, the number of alkylene oxide units in the copolymer is preferably about 1 to 100. The upper or lower limits of the range are, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22 , 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47 , 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72 , 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97 , 98, or 99. For example, the range may be 2-80 or 2-40.

In addition, the alkylene oxide unit in the copolymer has the formula:
-( _CH2 - ^CHR1 -O)-
(In the formula, R ¹ represents a hydrogen atom, a methyl group, or an ethyl group.) Preferred examples include units represented by the following formula. As mentioned above, about 1 to 100 of the units are preferably present in the copolymer, and when a plurality of the units are present, R ¹ in the above formula in each unit is independently a hydrogen atom, It represents a methyl group or an ethyl group, and especially preferably, R ¹ of the above formula in each unit is the same and represents a hydrogen atom, a methyl group, or an ethyl group. Particularly preferably, R 1 of the above formula in each unit All ¹ 's are the same and represent a hydrogen atom.

Among the fatty acid alkylene oxide adducts, ethylene oxide adducts of linear or branched chain fatty acids having 8 to 20 carbon atoms which may be substituted with hydroxy groups are particularly preferred; Ethylene oxide adducts of straight chain fatty acids of ~18 are more preferred. More specific examples include 12-hydroxystearic acid/PEG (12-hydroxystearic acid/ethylene glycol block copolymer), distearic acid/PEG, dilauric acid/PEG, and more specifically, for example, Distearic acid/PEG-12, dilauric acid/PEG-8, etc., and 12-hydroxystearic acid/PEG block copolymers with 8 to 10 12-hydroxystearic acid units and 27 to 33 ethylene oxide units, etc. Can be mentioned. Such a copolymer of fatty acid and alkylene oxide can also be purchased and used commercially.

One kind of fatty acid alkylene oxide adduct can be used alone or two or more kinds can be used in combination.

(B) The fatty acid alkylene oxide adduct preferably includes a fatty acid alkylene oxide adduct with an HLB value of less than 9, and a fatty acid with an HLB value of 3 to 8, 3 to 7, or 3 to 6. More preferably, it contains an alkylene oxide adduct. In addition, (B) fatty acid alkylene oxide adducts may contain fatty acid alkylene oxide adducts that do not have these HLB values, as long as the effect is not impaired. May contain. (B) The HLB value of the fatty acid alkylene oxide adduct (if multiple types of fatty acid alkylene oxide adducts are included, the HLB value of the whole (B) fatty acid alkylene oxide adduct) becomes the above-mentioned HLB value. This is particularly preferred.

(C) Modified polyoxyalkylene product The modified polyoxyalkylene product is a modified product of polyoxyalkylene, and is at least one of an ether (c1) consisting of an aliphatic alcohol and a polyoxyalkylene and a polyoxyalkylene fatty acid ester (c2). Yes, and (c1) is preferably used.

In (c1) and (c2), preferable examples of the aliphatic group of the aliphatic alcohol and the aliphatic group of the fatty acid ester include a linear or branched alkyl group or alkenyl group having 8 to 20 carbon atoms, respectively. Examples include groups. Each type of aliphatic group may be used alone or in combination of two or more types.

Preferred specific examples of the aliphatic alcohol of the ether (c1) consisting of an aliphatic alcohol and polyoxyalkylene are monohydric higher alcohols having 8 or more carbon atoms, with lauryl alcohol, stearyl alcohol, and isostearyl alcohol being particularly preferred. A specific example is given.

Preferred specific examples of the fatty acid of the polyoxyalkylene fatty acid ester (c2) include monocarboxylic acids having 8 or more carbon atoms, with particularly preferred specific examples of lauric acid, oleic acid, and isostearic acid.

Suitable examples of the polyoxyalkylene chain of the ether (c1) consisting of an aliphatic alcohol and polyoxyalkylene and the polyoxyalkylene fatty acid ester (c2) include the following formula:
-(CH ₂ -CHR ^c2 -O) _n -
(In the formula, n R ^c2 each independently represent a hydrogen atom, a methyl group, or an ethyl group, and n represents an integer of 1 to 100.) More preferably, all R ^c2 are the same.

Specific examples of the ether (c1) consisting of an aliphatic alcohol and polyoxyalkylene include polyoxyethylene (2) lauryl ether, polyoxyethylene (3) lauryl ether, polyoxyethylene (4) lauryl ether, polyoxyethylene ( 6) Lauryl ether, polyoxyethylene (5) stearyl ether, polyoxyethylene (5) isostearyl ether, and the like.

Specific examples of the polyoxyalkylene fatty acid ester (c2) include polyethylene glycol laurate 4-adduct, polyethylene glycol laurate 8-adduct, polyethylene glycol oleate 8-adduct, and polyethylene glycol isostearate 6-adduct.

(C) The polyoxyalkylene modified product preferably includes a polyoxyalkylene modified product having an HLB value in the range of 9 to 15. Note that (C) polyoxyalkylene modified products may include polyoxyalkylene modified products that do not have these HLB values, as long as the effects are not impaired. May contain. (C) The HLB value of the polyoxyalkylene modified product (if multiple types of polyoxyalkylene modified products are included, the HLB value of the entire (C) polyoxyalkylene modified product) becomes the above-mentioned HLB value. It is particularly preferable.

(C) The polyoxyalkylene modified product preferably includes a polyoxyalkylene modified product that is liquid at 25° C. under atmospheric pressure. Note that (C) polyoxyalkylene modified product includes a polyoxyalkylene modified product that is liquid at 25°C under atmospheric pressure, but also includes a polyoxyalkylene modified product that is not liquid at 25°C under atmospheric pressure. You can stay there. The (C) polyoxyalkylene modified product (in the case where multiple types of polyoxyalkylene modified products are included, the entire (C) polyoxyalkylene modified product) contained in the carboxyl group-containing polymer composition of the present invention is Particularly preferred is a liquid at 25° C. under atmospheric pressure.

In the production method of the present disclosure, the fatty acid alkylene oxide adduct (B) is used in an amount of 3.5 to 4.5 parts by mass per 100 parts by mass of α,β-unsaturated carboxylic acid (a1). The upper or lower limit of the range may be, for example, 3.6, 3.7, 3.8, 3.9, 4, 4.1, 4.2, 4.3, or 4.4 parts by weight.

Further, in the production method of the present disclosure, the polyoxyalkylene modified product (C) is used in an amount of 1 part by mass or more, and 1 to 10 parts by mass, based on 100 parts by mass of the α,β-unsaturated carboxylic acid (a1). It is preferable to use 1 to 8, 1 to 6, or 1 to 5 parts by mass.

In addition, in the production method of the present disclosure, while the above range of the amount of (B) or (C) used alone is maintained, the total amount of (B) and (C) used is More preferably, the amount is 4.5 to 10 parts by weight per 100 parts by weight of acid (a1).

Reaction Solvent The reaction solvent used in the production method of the present disclosure is not particularly limited as long as it is an inert solvent (inert solvent) with respect to the above polymerization reaction, but α,β-unsaturated carboxylic acid (a1) It is preferable to use a solvent that dissolves a monomer mainly composed of, but does not easily dissolve the resulting carboxyl group-containing polymer composition, such as normal pentane, normal hexane, isohexane, normal heptane, normal octane, isooctane, etc. Aliphatic hydrocarbons having 2 to 8 carbon atoms; Alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, and methylcyclohexane; Aromatic hydrocarbons such as benzene, toluene, and xylene; Halogen compounds such as chlorobenzene and ethylene dichloride ; acetic acid alkyl esters such as ethyl acetate and isopropyl acetate; and ketone compounds such as methyl ethyl ketone and methyl isobutyl ketone. Among these reaction solvents, aliphatic hydrocarbons having 2 to 8 carbon atoms and acetic acid C _{1 to 4} alkyl esters are preferred from the viewpoint of stable quality and easy availability. Hexane, cyclohexane, normal heptane, ethylene dichloride, and ethyl acetate are preferably used. One type of reaction solvent may be used alone, or two or more types may be used in combination.

The amount of reaction solvent used is preferably 200 to 10,000 parts by mass, more preferably 300 to 2,000 parts by mass, per 100 parts by mass of α,β-unsaturated carboxylic acid (a1). When the amount of the reaction solvent used is within this range, the reaction system can be uniformly stirred, and the reaction can be easily controlled. Furthermore, it is possible to suppress a decrease in the amount of carboxyl group-containing polymer composition produced per batch of polymerization, and improve economic efficiency.

The production method of the present disclosure includes (A) a carboxyl group-containing copolymer of an α,β-unsaturated carboxylic acid (a1) and a compound (a2) having at least two ethylenically unsaturated groups in the molecule; There are no particular limitations as long as a composition containing a polymer, (B) a fatty acid alkylene oxide adduct, and (C) a modified polyoxyalkylene product can be obtained. For example, the manufacturing method of the present disclosure includes, for example, the following methods (1) to (4), and can be preferably carried out by these methods.

Method (1)
When polymerizing the α,β-unsaturated carboxylic acid (a1) and the compound (a2) having at least two ethylenically unsaturated groups in the molecule, a predetermined amount of (B) fatty acid alkylene oxide adduct, and ( C) Method of coexisting polyoxyalkylene modified product from the initial stage of polymerization

Method (2)
After mixing the α,β-unsaturated carboxylic acid (a1) and the compound (a2) having at least two ethylenically unsaturated groups in the molecule, a predetermined amount of (B) fatty acid alkylene oxide adduct, and (C ) A method of polymerizing α,β-unsaturated carboxylic acid (a1) and a compound (a2) having at least two ethylenically unsaturated groups in the molecule while adding a polyoxyalkylene modified product.

Method (3)
The α,β-unsaturated carboxylic acid (a1) and the compound (a2) having at least two ethylenically unsaturated groups in the molecule are first polymerized, and after the polymerization is completed, the resulting slurry (B ) Method of adding fatty acid alkylene oxide adduct and (C) polyoxyalkylene modified product

Method (4)
After mixing α,β-unsaturated carboxylic acid (a1), (B) fatty acid alkylene oxide adduct, and (C) polyoxyalkylene modified product, an ethylenically unsaturated group is added to the resulting mixture. A method of polymerizing while adding at least two or more compounds (a2)

The manufacturing method of the present disclosure will be described in more detail below using the above method (1) as an example. Note that the above methods (2) to (4) and other methods can also be implemented with reference to the details of method (1). First, in a reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas blowing tube, and a cooling tube, a desired amount of α,β-unsaturated carboxylic acid (a1), which has an ethylenically unsaturated group in the molecule, was prepared. Compound (a2) having at least two or more of the above, (B) a fatty acid alkylene oxide adduct, (C) a polyoxyalkylene modified product, a reaction solvent (inert solvent), and a radical polymerization initiator if necessary. . Next, the contents in the reaction vessel are stirred and mixed to have a uniform composition, and then the oxygen gas contained in the upper space of the reaction vessel and the dissolved oxygen dissolved in the contents are removed. To do this, blow nitrogen gas into the contents. The polymerization reaction can be carried out by heating to 20 to 120°C, preferably 30 to 90°C using a hot bath or the like. The polymerization reaction is usually completed in 2 to 10 hours. After the polymerization reaction is completed, the reaction solvent (inert solvent) is distilled off from the reaction solution by heating under reduced pressure or normal pressure, whereby a carboxyl group-containing polymer composition can be obtained as a white fine powder.

Radical Polymerization Initiator When using a radical polymerization initiator in the production method of the present disclosure, examples of the radical polymerization initiator include, but are not particularly limited to, α,α'-azobisisobutyronitonyl, 2,2'-azobis -2,4-dimethylvaleronitrile, 2,2'-azobismethylisobutyrate, benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, tertiary butyl hydroperoxide and the like. These radical polymerization initiators may be used alone or in combination of two or more.

The amount of the radical polymerization initiator used is preferably 0.01 to 0.45 parts by mass, more preferably 0.01 to 0 parts by mass, per 100 parts by mass of α,β-unsaturated carboxylic acid (a1). .35 parts by mass. By using the amount of the radical polymerization initiator within such a range, it becomes possible to suppress a decrease in the polymerization reaction rate and to economically produce the desired carboxyl group-containing polymer composition. Moreover, it is possible to suppress the polymerization reaction rate from becoming too high and to appropriately control the reaction.

Inert Gas In the production method of the present disclosure, the atmosphere of the polymerization reaction system is usually preferably an inert gas atmosphere such as nitrogen gas or argon gas. In addition, the reaction temperature during polymerization is 50 to 90°C from the viewpoint of facilitating reaction control by suppressing the increase in viscosity of the reaction solution and from the viewpoint of controlling the bulk density of the obtained carboxyl group-containing polymer composition. The temperature is preferably set to 55 to 80°C, more preferably 55 to 80°C. The reaction time for polymerization cannot be determined unconditionally since it varies depending on the reaction temperature, but is usually 0.5 to 10 hours. The desired carboxyl group-containing polymer composition can be isolated as a fine white powder by performing a drying step to dry the solvent after the reaction is completed, and heating the reaction solution to 80 to 120°C to remove the solvent. I can do it.

The carboxyl group-containing polymer composition obtained by the production method of the present disclosure has excellent solubility in water even when dissolved in water at a high concentration, and furthermore, it has a neutralized viscous liquid obtained by mixing with water. It is characterized by high transparency. The carboxyl group-containing polymer composition obtained by the production method of the present disclosure may be referred to as the polymer composition of the present disclosure.

The polymer composition of the present disclosure comprises (A) a polymer obtained by copolymerizing an α,β-unsaturated carboxylic acid (a1) and a compound (a2) having two or more ethylenically unsaturated groups; ) a fatty acid alkylene oxide adduct, and (C) a modified polyoxyalkylene product. Regarding these (A) to (C), the above-mentioned contents apply as is.

Further, in the polymer composition of the present disclosure, the content of (B) is 3.5 parts by mass to 4.5 parts by mass based on 100 parts by mass of α,β-unsaturated carboxylic acid (a1) constituting (A). Preferably, it is 5 parts by mass. The upper or lower limit of the range may be, for example, 3.6, 3.7, 3.8, 3.9, 4, 4.1, 4.2, 4.3, or 4.4 parts by weight.

Furthermore, in the polymer composition of the present disclosure, the content of (C) is 1 part by mass or more based on 100 parts by mass of α,β-unsaturated carboxylic acid (a1) constituting (A). It is preferably 1 to 10 parts by weight, more preferably 1 to 8, 1 to 6, or 1 to 5 parts by weight.

In addition, while the above content range of (B) or (C) is maintained, the total content of (B) and (C) is 4 parts by mass based on 100 parts by mass of α,β-unsaturated carboxylic acid (a1). More preferably, the amount is .5 to 10 parts by mass.

In addition, since (A) is a polymer formed by copolymerizing (a1) and (a2), (a1) constituting (A) more precisely refers to (a1) constituting (A). (a1)-derived moiety (α,β-unsaturated carboxylic acid unit); however, in this specification, in the description of the polymer composition of the present disclosure, α,β-unsaturated carboxylic acid unit is referred to as α,β-unsaturated carboxylic acid unit. , β-unsaturated carboxylic acid (a1).

The polymer composition of the present disclosure has a non-stirring swelling time of less than 10 minutes when measured under the following measurement conditions, and a transmittance of 90% or more when measured under the following measurement conditions.
[No-stirring swelling time measurement conditions]
Add 3 g of the carboxyl group-containing polymer composition to 100 g of water at 25° C., leave to stand, and visually measure the time required for the composition to completely wet.
[Permeability measurement conditions]
Add 5 g of the carboxyl group-containing polymer composition to 495 g of water at 25°C, disperse it, and neutralize it by adding an aqueous sodium hydroxide solution. The transmittance (ratio when the transmittance of ion-exchanged water is taken as 100%) is measured.

The non-stirring swelling time is preferably 9.5 minutes or less, more preferably 9 minutes or less. Further, the transmittance is more preferably 91% or more or 92% or more.

Although not particularly limited, the polymer composition of the present disclosure has (B) and (C) attached to the surface of the particles of (A) by being prepared by the production method of the present disclosure described above. More specifically, it is preferable that the surface of the particles of (A) be coated with (B) and (C). In this case, components other than (B) and (C) may be attached (coated) to the surface of the particles of (A).

Note that in this specification, the term "comprising" includes "consisting essentially of" and "consisting of." Additionally, the present disclosure encompasses any and all combinations of the features described herein.

Further, the various characteristics (properties, structures, functions, etc.) described for each embodiment of the present disclosure described above may be combined in any manner in order to specify the subject matter covered by the present disclosure. That is, the present disclosure encompasses all subject matter consisting of any and all combinations of the combinable features described herein.

Hereinafter, embodiments of the present disclosure will be described in more detail by showing examples, but the embodiments of the present disclosure are not limited to the following examples.

Example 1
In a 500 mL (milliliter) four-necked flask equipped with a stirrer, a thermometer, a nitrogen blowing tube, and a cooling tube, 40 g of acrylic acid and α,β-unsaturated carboxylic acid were added as α,β-unsaturated carboxylic acid (a1). 0.4 g of stearyl methacrylate (Blenmar SMA, manufactured by NOF Corporation) as (a1), 0.27 g of pentaerythritol allyl ether as the compound (a2) having at least two ethylenically unsaturated groups in the molecule, radical polymerization 0.096 g of 2,2'-azobis(methyl isobutyrate) was charged as an initiator, and 198.6 g of n-heptane and 49.6 g of ethyl acetate were charged as reaction solvents. Subsequently, after stirring and mixing the solution uniformly, nitrogen gas was blown into the solution in order to remove oxygen present in the upper space of the reaction vessel (four-necked flask), the raw materials, and the reaction solvent. Next, under a nitrogen atmosphere, the mixture was heated to 70°C, and a block copolymer of 12-hydroxystearic acid and polyoxyethylene (Claudia A solution of 1.6 g of Cithrol DPHS (manufactured by Kao Co., Ltd., Cithrol DPHS) and 0.4 g of polyoxyethylene (4) lauryl ether (manufactured by Kao Co., Ltd., Emulgen 104P) as the polyoxyalkylene modified product (C) was charged into a reaction vessel and It was kept at ℃ for 3 hours. Thereafter, the resulting slurry was heated to 105°C to distill off n-heptane and ethyl acetate, and further dried under reduced pressure at 117°C and 20 mmHg for 9 hours to obtain a carboxyl group-containing polymer composition as a white fine powder. 38g of product was obtained.

Example 2
38 g of a carboxyl group-containing polymer composition in the form of white fine powder was obtained in the same manner as in Example 1, except that the amount of polyoxyethylene (4) lauryl ether added was changed to 0.8 g.

Example 3
39 g of a carboxyl group-containing polymer composition in the form of white fine powder was obtained in the same manner as in Example 1, except that the amount of polyoxyethylene (4) lauryl ether added was changed to 1.2 g.

Example 4
Example 1 was repeated except that polyoxyethylene (4) lauryl ether was replaced with polyoxyethylene (6) lauryl ether (manufactured by Kao, Emulgen 108) and the amount added was changed to 1.6 g. In the same manner, 39 g of a carboxyl group-containing polymer composition in the form of a white fine powder was obtained.

Comparative example 1
37 g of a carboxyl group-containing polymer composition in the form of a white fine powder was obtained in the same manner as in Example 1, except that polyoxyethylene (4) lauryl ether was not added. Comparative Example 1 is a carboxyl group-containing polymer composition that does not contain (C) a polyoxyalkylene modified product.

Comparative example 2
In Example 4, a block copolymer of 12-hydroxystearic acid and polyoxyethylene (manufactured by Croda, Cithrol DPHS) was not added, and polyoxyethylene (6) lauryl ether (manufactured by Kao, Emulgen 108) was mixed with polyoxyethylene. (4) 37 g of a carboxyl group-containing polymer composition in the form of a white fine powder was obtained in the same manner as in Example 4, except that lauryl ether (Emulgen 104P, manufactured by Kao Corporation) was used. Comparative Example 2 is a carboxyl group-containing polymer composition that does not contain (B) a fatty acid alkylene oxide adduct.

Comparative example 3
In Example 4, a white fine powder containing a carboxyl group-containing polymer was prepared in the same manner as in Example 4, except that the block copolymer of 12-hydroxystearic acid and polyoxyethylene (manufactured by Croda, Cithrol DPHS) was not added. 38 g of combined composition was obtained.

Comparative example 4
In Example 2, the block copolymer of 12-hydroxystearic acid and polyoxyethylene (manufactured by Croda, Cithrol DPHS) was changed to polyoxyethylene triisostearate hydrogenated castor oil (manufactured by Nippon Emulsion, Emarex RWIS-350). Except for this, 38 g of a carboxyl group-containing polymer composition in the form of white fine powder was obtained in the same manner as in Example 2.

Comparative example 5
In Comparative Example 4, a white fine powder containing carboxyl groups was prepared in the same manner as in Comparative Example 4, except that polyoxyethylene (6) lauryl ether (manufactured by Kao, Emulgen 108) was used instead of polyoxyethylene (4) lauryl ether. 38 g of combined composition was obtained.

Comparative example 6
38 g of a carboxyl group-containing polymer composition in the form of white fine powder was obtained in the same manner as in Example 1, except that the amount of polyoxyethylene (4) lauryl ether added was changed to 0.2 g.

Comparative example 7
A carboxyl group-containing polymer composition of white fine powder was prepared in the same manner as in Example 1, except that the amount of the block copolymer of 12-hydroxystearic acid and polyoxyethylene was changed to 1.2 g. 37g of product was obtained.

Comparative example 8
In Example 1, except that the amount of the block copolymer of 12-hydroxystearic acid and polyoxyethylene was changed to 2.0 g, and the amount of polyoxyethylene (4) lauryl ether added was changed to 0.8 g. In the same manner as in Example 1, 39 g of a carboxyl group-containing polymer composition in the form of white fine powder was obtained.

<Evaluation method>
(1) Evaluation of solubility in water (swelling time without stirring)
100 g of ion exchange water was placed in a 200 mL beaker, and the temperature of the ion exchange water was adjusted to 25°C. Into this beaker, 3.0 g of the carboxyl group-containing polymer composition was added at once under non-stirring conditions, and the swelling state of the carboxyl group-containing polymer composition was visually observed. The time (minutes) required for the material to completely get wet without any dry parts was measured. If the time required for swelling was less than 10 minutes, it was judged that the swelling property was excellent, it was difficult to form lumps, and the water dispersibility at high concentrations was excellent. In addition, if the swelling was not completed even after 60 minutes and some dry parts remained, the swelling time was evaluated as "60<".

(2) Transparency evaluation of neutralized viscous liquid (2-1) Preparation of neutralized viscous liquid 495 g of ion-exchanged water was placed in a 500 mL beaker, and the temperature of the ion-exchanged water was adjusted to 25°C. While stirring this beaker at a rotation speed of 200 r/min using a stirrer equipped with a four-blade paddle (blade diameter: 50 mm), 5 g of the carboxyl group-containing polymer composition was charged and dispersed. The obtained aqueous dispersion was neutralized (that is, adjusted to pH=7) using a 18% by mass aqueous sodium hydroxide solution to obtain a neutralized viscous liquid for evaluation.

(2-2) Measurement of light transmittance The transmittance of the neutralized viscous liquid for evaluation was measured using a spectrophotometer (model number: UV-1850) manufactured by Shimadzu Corporation. Specifically, the neutralized viscous liquid for evaluation was placed in a cell for UV measurement (light path 1 cm), and degassed in a centrifuge at 2,000 revolutions per minute for 5 minutes (defoaming was completed). (If not, perform the same operation in a centrifuge to make sure that the bubbles are completely removed from the top of the sample), then set the neutralized viscous liquid in a spectrophotometer and set the measurement wavelength to 425 nm and transmit it. The rate was measured. If the light transmittance of the neutralized viscous liquid was 90% or more when the light transmittance of ion-exchanged water was taken as 100%, it was evaluated as having high transparency.

The measurement results are shown in Table 1 below.

The carboxyl group-containing polymer composition obtained by the method described in the examples has (1) a non-stirring swelling time of less than 10 minutes, and (2) a neutralized viscous liquid with a transparency of 90% or more. Therefore, it was a polymer with excellent properties.

Claims (4)

A method for producing a carboxyl group-containing polymer by copolymerizing an α,β-unsaturated carboxylic acid (a1) and a compound (a2) having two or more ethylenically unsaturated groups, the method comprising:
(a1) and (a2) are copolymerized in the presence of an inert solvent containing an emulsifier,
The emulsifier includes a fatty acid alkylene oxide adduct and a polyoxyalkylene modified product,
The amount of fatty acid alkylene oxide adduct is 3.5 to 4.5 parts by mass based on 100 parts by mass of (a1),
The amount of the polyoxyalkylene modified substance is 1 part by mass or more per 100 parts by mass of (a1),
Production method. The manufacturing method according to claim 1, wherein the inert solvent contains an aliphatic hydrocarbon having 2 to 8 carbon atoms and an acetic acid alkyl ester. The following (A) to (C):
(A) Polymer obtained by copolymerizing α,β-unsaturated carboxylic acid (a1) and compound (a2) having two or more ethylenically unsaturated groups (B) Fatty acid alkylene oxide adduct (C) Polymer Contains oxyalkylene modified products,
A carboxyl group-containing polymer composition, which has a non-stirring swelling time of less than 10 minutes as measured under the following measurement conditions, and has a transmittance of 90% or more as measured under the following measurement conditions.
[No-stirring swelling time measurement conditions]
Add 3 g of the carboxyl group-containing polymer composition to 100 g of water at 25° C., leave to stand, and visually measure the time required for the composition to completely wet.
[Permeability measurement conditions]
5 g of the carboxyl group-containing polymer composition was added to 495 g of water at 25° C. and dispersed, and neutralized by adding an aqueous sodium hydroxide solution to obtain a neutralized viscous liquid. The transmittance (ratio when the transmittance of ion-exchanged water is taken as 100%) is measured. The content of (B) is 3.5 parts by mass to 4.5 parts by mass per 100 parts by mass of (a1),
The content of (C) is 1 part by mass or more per 100 parts by mass of (a1),
The carboxyl group-containing polymer composition according to claim 3.