JP2011012150A - Method for producing polymer builder for detergent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for stably producing a polymer builder capable of being stably blended even with a liquid detergent containing a high concentration of a surfactant and excellent in color and odor.SOLUTION: This method for producing the polymer builder for a detergent by performing the polymerization reaction of a specific unsaturated carboxylic acid-based monomer (I) such as acrylic acid, and a specific allyl ether-based monomer (II) such as a polyethylene glycol monoallyl ether, by using a liquid reaction medium in a reaction vessel uses a liquid containing a lower alcohol as the liquid reaction medium, and includes putting-in the monomers (I) and (II) of predetermined amounts in the reaction vessel in advance before the initiation of the polymerization, and then adding the remaining monomers (I) and (II) after the initiation of the polymerization to the reaction vessel.

Description

  The present invention relates to a method for producing a polymer builder for a cleaning agent.

  In recent years, environmental awareness has increased, and there is a strong demand for the appearance of cleaning agents that have a low environmental impact. So-called concentrated type cleaning agents with higher cleaning component concentrations than conventional cleaning agents reduce the size of the cleaning agent itself, reduce the amount of container resin, reduce transportation costs, reduce waste after use, etc. It is thought that it is very effective for reducing.

  However, such a surfactant-rich liquid detergent composition has a problem that the builder component is difficult to be stably blended in addition to the storage stability of the composition itself. For example, polyacrylic acid-based polymers are known to have excellent mud dispersibility and re-contamination prevention properties. In some cases, the substrate may be separated as a solid in the solution.

  Further, in the production of a builder, a method using a chain transfer agent at the time of polymerization is known in order to adjust the molecular weight range suitable as a builder, but a compound containing a sulfur element often used as a chain transfer agent Has a problem of deteriorating the scent of the detergent blended with it because it remains in the polymer solution after polymerization and emits a unique odor.

  Patent Document 1 discloses a step of adding at least one low-reactive monomer to a reaction vessel while reducing the addition rate in producing a copolymer composed of monomers having different reactivities, and at least one kind. And a step of adding less than 1% by weight of the highly reactive monomer to the reaction vessel. Although differences in monomer reactivity are taken into account, depending on the type and combination of monomers actually used, this disclosure condition is not always sufficient, and more detailed conditions are required for polymer builders for detergents. The design of was requested.

  Patent Documents 2 to 4 disclose that a polymer obtained by copolymerizing a (meth) acrylic acid monomer and a polyalkylene glycol monoallyl ether monomer is used as a builder for a detergent. ing. However, in these documents, detailed examination is not made about the addition method of the monomer at the time of manufacturing a polymer.

  In addition, as a method for producing a polymer suitable as a cement additive, Patent Document 5 describes the polymerization of an unsaturated polyalkylene glycol monomer and an unsaturated carboxylic acid monomer in a reactor during polymerization. It is disclosed that the concentration of water is 50% by weight or less, at least a part of the monomer to be polymerized is initially charged in the reactor in advance, and the remaining monomer is charged into the reactor after the start of polymerization. ing. However, although there is disclosure that a part of a mixture of two or more monomers is initially charged, it is not assumed that the monomers having different reactivities are copolymerized with each other. It is not set for each body.

JP 2007-231276 A JP 2004-75977 A Japanese Patent Laid-Open No. 58-5398 JP 58-47099 A JP 2001-2734 A

  The object of the present invention is to stably produce a polymer builder which can be stably blended in a liquid detergent, particularly a liquid detergent containing a high concentration of a surfactant, and excellent in the color and odor of the solution. It is to provide a method and to provide a polymer builder thus obtained.

The present invention provides a liquid reaction between a monomer represented by the following general formula (I) [hereinafter referred to as monomer (I)] and a monomer represented by the following general formula (II) [hereinafter referred to as monomer (II)]. In producing a polymer builder for a detergent by polymerizing in a reaction vessel using a medium,
Using a liquid containing a lower alcohol as a liquid reaction medium,
Monomer (I) in an amount corresponding to 1 to 20% by weight of the total monomer (I) used, and monomer (II) in an amount corresponding to 30 to 80% by weight of the total monomer (II) used are monomer ( Before the polymerization is started, the reaction vessel is preliminarily set so that the ratio of I) to monomer (II) is monomer (I): monomer (II) = 0.4: 99.6 to 15:85 (weight ratio). Preparation,
Adding the remainder of monomer (I) and monomer (II) to the reaction vessel after the start of polymerization,
The present invention relates to a method for producing a polymer builder for cleaning agents.

[Wherein, R ¹ represents a hydrogen atom or —COOM, R ² represents a hydrogen atom or a methyl group, and each M independently represents a hydrogen atom, a monovalent metal, or a divalent metal (1/2 atom). Represents an ammonium group or a substituted ammonium group. ]

[Wherein, R ³ represents a hydrogen atom or a methyl group, A represents one or more alkylene groups having 2 to 3 carbon atoms, X represents a hydrogen atom, a methyl group, a phenyl group or a benzyl group, and n represents It is the average number of moles added and represents a number between 10 and 100. ]

  The present invention also relates to a polymer builder for cleaning agents obtained by the production method of the present invention.

  According to the present invention, a polymer builder that can be stably blended into a liquid detergent, particularly a liquid detergent containing a high concentration (for example, 50% by weight or more) of a surfactant and excellent in the color and odor of the solution. Can be manufactured stably.

  According to the production method of the present invention, a polymer builder that can be stably blended in a liquid detergent containing a surfactant at a high concentration (for example, 50% by weight or more) can be obtained by monomer (I): monomer (II This is presumably because the copolymerization ratio of) did not change and a polymer with a weight ratio as designed was produced. In addition, since a predetermined amount of monomer (I) and monomer (II) are previously charged in a reaction vessel together with a liquid reaction medium containing a lower alcohol, polymerization is started, so that no chain transfer agent causing sulfur odor is required. It is considered that the color and odor of the polymer solution are excellent because the molecular weight range can be controlled to be optimal. Furthermore, since the lower alcohol stably dissolves the polymer obtained by polymerization, the polymerization reaction can proceed stably.

In the monomer (I), R ¹ represents a hydrogen atom or —COOM, and R ² represents a hydrogen atom or a methyl group. Each M independently represents a hydrogen atom, a monovalent metal, a divalent metal (1/2 atom), an ammonium group or a substituted ammonium group, preferably a hydrogen atom, a monovalent metal or a substituted ammonium group.

  Specific examples of the monomer (I) include acrylic acid, methacrylic acid and maleic acid when used in an unneutralized acid form (that is, M in the formula (I) is a hydrogen atom), preferably Acrylic acid, methacrylic acid, more preferably acrylic acid. A salt of a monovalent or divalent metal, an ammonium group, or an organic amine group can also be used. Examples of the salt to be neutralized include lithium, potassium, sodium, calcium, magnesium, ammonium, monoethanolamine, diethanolamine, and triethanolamine, and sodium, ammonium, monoethanolamine, diethanolamine, and triethanolamine are preferable. In addition, as for the range of the neutralization degree of the monomer used for superposition | polymerization, 0-0.5 are preferable, 0-0.2 are more preferable, 0-0.1 are still more preferable, 0 is especially preferable.

In the monomer (II), R ³ represents a hydrogen atom or a methyl group. A represents one or more alkylene groups having 2 to 3 carbon atoms, and preferably an alkylene group having 2 carbon atoms. X represents a hydrogen atom, a methyl group, a phenyl group or a benzyl group, preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom. n is the average number of moles added, and represents a number of 10 to 100. From the viewpoint of blending stability into the liquid detergent, the number of 15 to 80 is preferable, and the number of 19 to 35 is more preferable.

  Specific examples of the monomer (II) include polyethylene glycol allyl ether, methoxy polyethylene glycol allyl ether, poly (ethylene glycol / propylene glycol) allyl ether, and methoxy poly (ethylene glycol / propylene glycol) allyl ether, preferably Polyethylene glycol allyl ether, methoxy polyethylene glycol allyl ether, more preferably polyethylene glycol allyl ether.

  The arrangement of the structural unit (I) derived from the monomer (I) and the structural unit (II) derived from the monomer (II) may be random, block, or alternating, but is preferably random or alternating.

  In the present invention, a liquid reaction medium containing a lower alcohol is charged into a reaction vessel in advance before the start of polymerization. The liquid reaction medium is a liquid solvent, a dispersion medium, or a dispersion solvent. By using a liquid reaction medium containing a lower alcohol, it is possible to prevent the polymer produced during the polymerization from becoming insoluble or, in some cases, gelling, and to carry out the polymerization smoothly even at a high polymerization concentration. As the lower alcohol to be used, monohydric alcohols such as methanol, ethanol, propanol and 2-propanol (preferably monohydric alcohol having 2 to 3 carbon atoms); ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin and sorbitol Polyhydric alcohols such as Among them, since the polyhydric alcohol has a high boiling point, it can be used for polymerization at a high temperature, and the solvent odor of the obtained polymer solution is preferable from the viewpoint of low. Further preferred polyhydric alcohols are C 2-6 polyhydric alcohols, and 2-6 valent alcohols. More preferred is one or more selected from ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol, and particularly preferred is propylene glycol.

  The proportion of the lower alcohol in the liquid reaction medium is preferably 20 to 80% by weight, more preferably 30 to 70% by weight, and particularly preferably 40 to 60% by weight. As a component other than the lower alcohol in the liquid reaction medium, water is preferable.

  In the present invention, the monomer (I) in an amount corresponding to 1 to 20% by weight of the total monomer (I) to be used is charged into the reaction vessel in advance before the start of polymerization. From the viewpoint of productivity and stability in blending with a liquid detergent, it is preferable to add an amount corresponding to 3 to 18% by weight, more preferably 5 to 15% by weight of the total monomer (I) used.

  In the present invention, the amount of the monomer (I) added to the reaction vessel after the initiation of polymerization is preferably an amount corresponding to 80% by weight or more of the total monomers (I) used, more preferably 82% by weight or more, and 85% by weight. The above is more preferable.

  In the present invention, the monomer (II) in an amount corresponding to 30 to 80% by weight of the total monomer (II) to be used is charged into the reaction vessel in advance before the polymerization is started. From the viewpoint of productivity and stability of incorporation into a liquid detergent, it is more preferable to charge the reaction vessel in advance in an amount corresponding to 35 to 70% by weight, and further 40 to 60% by weight of the total monomer (II) to be used.

  In the present invention, polymerization is initiated so that the ratio of monomer (I) to monomer (II) is monomer (I): monomer (II) = 0.4: 99.6 to 15:85 (weight ratio). Charge the reaction vessel in advance. From the viewpoint of easily and stably obtaining a polymer having an intended copolymerization ratio, the weight ratio is preferably 0.6: 99.4 to 10:90, and more preferably 1:99 to 7:93.

  In the present invention, the ratio of the monomer (I) and the monomer (II) in the reaction vessel after the start of polymerization is such that monomer (I): monomer (II) = 0.4: 99.6 to 15:85 (weight ratio) It is preferable to have a step of adding the remainder of monomer (I) and monomer (II) to the reaction vessel. That is, the ratio of the monomer (I) and the monomer (II) in the reaction vessel after the start of polymerization was such that the monomer (I): monomer (II) = 0.4: 99.6 to 15:85 (weight ratio). As such, it is preferred that there is a period during which the remainder of monomer (I) and monomer (II) is added to the reaction vessel.

  Also, during the period from the start of polymerization until 80% by weight or more of all monomers (II) to be used is added (from 0 minutes after the start of polymerization, a specific time point n at which 80% by weight or more of all monomers (II) to be used have been added) The difference between the maximum value and the minimum value of the ratio (%) of the weight of monomer (I) to the total weight of monomer (I) and monomer (II) in the reaction solution is within 10% Within 5 points, more preferably within 5% (within 5 points), particularly preferably within 3% (within 3 points). Thus, by reducing the range of fluctuation of the monomer (I) concentration in the reaction solution, a polymer having a designed copolymerization ratio can be obtained more easily and stably. As a method for determining the monomer ratio in more detail in order to reduce the range of fluctuation of the monomer (I) concentration in this way, for example, Seisho ("Essential Polymer Science" (written by Nakahama Kiyoichi et al., Kodansha) 1992, p. 209), by using the curve fitting method, the intersection method, the Fineman-Ross method, the method using the Mayo-Lewis relational equation, etc. The monomer reactivity ratio established during II) can be obtained, and from the obtained monomer reactivity ratio value, it can be calculated as the optimum monomer concentration ratio in the reaction solution for obtaining the desired copolymerization ratio. In the present invention, the reaction liquid containing the monomer (I) and the monomer (II) reaches a predetermined polymerization temperature (preferably 50 to 150 ° C. as described later), and the reaction liquid is opened. The time at which the initiator is added can be determined as the start of polymerization.

The weight ratio of the monomers in the reaction solution after the polymerization initiation (I) and monomer (II) is, for example, a small amount of the reaction solution was collected, unreacted monomers (I) and as measured by ¹ H-NMR and liquid chromatography It can be calculated based on the amount of monomer (II). The timing and frequency at which this calculation is performed are as follows: immediately after the start of polymerization, once at a specific time point when 80% by weight or more of the total monomer (II) to be used has been added, and at least once in the meantime, preferably It is preferable to carry out it twice or more after a fixed time.

  In order to control the monomer ratio in the reaction solution within the above range, the amount of monomer (I) and monomer (II) in the reaction solution is taken into consideration in consideration of the amount of monomer in the reaction solution that is successively consumed as the polymerization proceeds. It is preferable to adjust the addition amount (speed).

  It is preferable that there is a period in which the monomer (I) and the monomer (II) are added to the reaction vessel at a weight ratio of monomer (I): monomer (II) = 10: 90 to 60:40 after the start of polymerization, Furthermore, it is preferred that there is a period of addition at a weight ratio of 12:88 to 50:50, especially 15:85 to 40:60.

  The method of adding the monomer (I) and the remainder of the monomer (II) to the reaction vessel after the start of polymerization is preferably dropwise. Moreover, you may perform the multistep dripping from which the weight ratio and dripping speed of monomer (I): monomer (II) differ.

  It is preferable that the monomer (I) and the monomer (II) to be added after the start of the polymerization are continuously dropped into the reaction vessel at a constant rate together with the initiator (and optionally a liquid reaction medium).

  Preferably, the monomer (I) is added until an amount corresponding to 80% by weight or more, more preferably 90% by weight or more, further preferably 95% by weight or more, particularly preferably 100% by weight of the total monomer (II) used is added. ) And the remainder of monomer (II) are added to the reaction vessel at a weight ratio of monomer (I): monomer (II) = 10: 90 to 60:40.

  Moreover, in this invention, after adding monomer (II) of the quantity equivalent to 80 weight% or more of all the monomers (II) to be used, monomer (I): monomer (II) = 10: 90-60: 40 It is preferable that there is a period in which the monomer (I) and / or the monomer (II), preferably the monomer (I) is added at a slower rate than the addition rate employed in the case of addition at a weight ratio of.

In the present invention, the remainder of monomer (I) and monomer (II) are added to the reaction vessel after the start of polymerization so as to satisfy the following (1) and (2), and further (1), (2) and (3) It is preferable to do. In this embodiment, after a part of the remaining monomer (I) and the entire remaining monomer (II) are added to the reaction vessel at a predetermined weight ratio, the remainder of the remaining monomer (I) is further added to the reaction vessel. Is.
(1) Monomer (I) until an amount of monomer (II) corresponding to 80% by weight or more, further 90% by weight or more, further 95% by weight or more, and further 100% by weight of the total monomer (II) used is added. And monomer (II) is added to the reaction vessel at a weight ratio of monomer (I): monomer (II) = 10: 90 to 60:40.
(2) When the monomer (II) is added in an amount corresponding to 100% by weight of the total monomer (II) used, the added amount of the monomer (I) is less than 100% by weight of the total monomer (I) used ( The amount is preferably 15 to 75% by weight, more preferably 25 to 70% by weight, and still more preferably 35 to 65% by weight.
(3) After the addition of monomer (II) in an amount corresponding to 100% by weight of the total monomer (II) used, the monomer (I) is slower than the addition rate of monomer (I) in (2) above Add to reaction vessel at rate.

  The weight ratio of the total monomer (I) used in the present invention to the total monomer (II) used is: monomer (I): monomer (II) = 10: 90 to 60:40. From the viewpoint of blending stability into an agent and detergency, it is more preferably 12:88 to 50:50, and further preferably 15:85 to 40:60. It is preferable to adjust the amounts of the monomers (I) and (II) added to the reaction vessel before and after the start of polymerization so as to be within this range.

  By controlling the reaction as described above, in the present invention, the weight ratio of all monomers (I) and all monomers (II) used, and the structural unit (I) and monomers derived from monomer (I) in the polymer ( II) A polymer in which the weight ratio of the structural unit (II) derived from the polymer is almost equal, that is, the residual monomer is small and the component of the designed copolymerization ratio is large (copolymerization distribution is narrow) is obtained.

  In the present invention, in addition to the monomer (I) and the monomer (II), other copolymerizable monomers may be copolymerized. Specifically, carboxylic acids such as fumaric acid and itaconic acid; vinyl compounds such as styrenesulfonic acid (salt), styrene and vinyl acetate; alkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, (meth) acrylic (Meth) acrylic acid esters such as dimethylaminoethyl acid (salt); (meth) acrylamides such as (meth) acrylamide, N-alkyl- (meth) acrylamide, 2-acrylamido-2-methylpropanesulfonic acid (salt) Derivatives: Allyl compounds such as diallyldimethylammonium salt, diallylmethylamine (salt), diallylamine (salt), and allylamine (salt).

  The amount (% by weight) of these other copolymerizable monomers based on the total weight of all the monomers (I) and (II) used is preferably 10% by weight or less, more preferably 5% by weight or less. 0% by weight is more preferable. In the present invention, the ratio of the monomer (I) to the monomer (II) is 10:90 to 60: 40% by weight, further 12:88 to 50: 50% by weight, and even more, in all monomers used for the production of the polymer builder. It is preferable that it is 15: 85-40: 60 weight%.

  In the present invention, the polymerization reaction method may be any method such as solution polymerization, suspension polymerization, emulsion polymerization, precipitation polymerization, and dispersion polymerization, but solution polymerization is preferred. In solution polymerization, a solvent containing a lower alcohol is used as a liquid reaction medium.

  Moreover, it is preferable to perform a polymerization reaction using an initiator. A well-known thing can be used as an initiator. For example, persulfates such as sodium persulfate (sodium peroxodisulfate), potassium persulfate (potassium peroxodisulfate), ammonium persulfate (ammonium peroxodisulfate); hydrogen peroxide; 2,2′-azobis (2-amidinopropane) ) Azo compounds such as dihydrochloride, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, cumene hydro And peroxides such as peroxides. Furthermore, reducing agents such as sodium hydrogen sulfite, sodium sulfite, sodium pyrobisulfite, and ascorbic acid, and amine compounds such as ethylenediamine, sodium ethylenediaminetetraacetate, and glycine may be used in combination. It may be used alone or in combination of two or more. Of these, sodium persulfate, potassium persulfate, ammonium persulfate, hydrogen peroxide, 2,2′-azobis (2-amidinopropane) dihydrochloride, and 2,2′-azobis (2,4-dimethylvaleronitrile) are preferable. More preferred are sodium persulfate, potassium persulfate, ammonium persulfate and hydrogen peroxide.

  The addition amount of the initiator is preferably 1 to 10 mol%, more preferably 2 to 9 mol%, as a ratio of the total number of moles of the initiator to the total number of moles of the monomer (I) and the monomer (II). ˜8 mol% is particularly preferred.

  The polymerization temperature is preferably 50 to 150 ° C, more preferably 60 to 120 ° C, still more preferably 70 to 100 ° C, and particularly preferably 80 to 90 ° C. The polymerization temperature is appropriately adjusted depending on the decomposition temperature of the initiator used. In the present invention, it is preferable that the reaction solution is brought to a temperature within the above-mentioned range from the time when the liquid reaction medium containing monomer (I), monomer (II) and lower alcohol is previously charged in the reaction vessel until the polymerization reaction is completed.

  As the chain transfer agent, a known one can be used if necessary, but it is preferable not to use it in terms of the color and smell of the solution.

As a preferable example of the production method of the present invention,
(A) an amount of monomer (I) corresponding to 1 to 20% by weight of the total monomer (I) used, an amount of monomer (II) corresponding to 30 to 80% by weight of the total monomer (II) used, and A step in which a liquid reaction medium containing a lower alcohol is charged into a reaction vessel in advance before the start of polymerization, and the ratio of the monomer (I) and the monomer (II) charged in the reaction vessel in advance before the start of polymerization is a monomer ( I): monomer (II) = 0.4: 99.6 to 15:85 (weight ratio),
(B) A step of adding (preferably dropping) the monomer (I), the monomer (II), and the initiator (preferably an amount corresponding to 30 to 70% by weight of the total initiator used) to the reaction vessel. Adding a portion of the remaining monomer (I) and the entire remaining monomer (II);
(C) What has the process of adding the whole quantity of the remaining monomer (I) which was not added by said (b), and an initiator (preferably whole quantity of a remaining initiator) to reaction container is mentioned. In the steps (a) to (c), the temperature of the reaction solution containing the monomer (I), the monomer (II) and the liquid reaction medium is preferably 70 to 100 ° C., respectively. Moreover, after performing the process of (c) at 70-100 degreeC and adding all the monomers (I) and all the monomers (II) to be used, a reaction liquid is continuously hold | maintained at 70-100 degreeC for 1 to 5 hours. It is preferable. In the step (b), the weight ratio of the monomer (I) and the monomer (II) added to the reaction vessel is preferably monomer (I): monomer (II) = 10: 90 to 60:40. .

<Polymer builder for cleaning agent>
The polymer builder for a detergent obtained by the production method of the present invention preferably contains the structural unit (I) derived from the monomer (I) and the structural unit (II) derived from the monomer (II). ) And the structural unit (II) in the structural unit (I): structural unit (II) is preferably 10:90 to 60:40, more preferably 12:88 to 50:50, still more preferably 15: It is a high molecular compound of 85-30: 70.

  If necessary, the polymer compound obtained by the production method of the present invention comprises alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; hydroxides of alkaline earth metals such as calcium hydroxide and magnesium hydroxide. The product may be neutralized with an alkali carbonate such as sodium carbonate or sodium hydrogen carbonate; an organic amine such as monoethanolamine, diethanolamine, or triethanolamine, and the polymer builder for a cleaning agent of the present invention.

  The weight average molecular weight of the polymer compound according to the present invention is preferably in the range of 5,000 to 100,000, more preferably 10,000 to 70,000, and still more preferably 15,000 to 50,000, from the viewpoint of improving detergency against mud dirt at high hardness. It is. This weight average molecular weight was determined by gel permeation chromatography (GPC) using TSKgel α-M (two-linked) manufactured by Tosoh Corporation as a column, a differential refractometer as a detector, and an eluent of 60 mmol / L phosphorus. It is a weight average molecular weight when measured under the conditions of dimethylformamide added with an acid, 50 mmol / L lithium bromide, and polyethylene glycol as a sample.

  The polymer builder for a cleaning agent obtained by the production method of the present invention is not particularly limited to the form of the cleaning agent, and can be blended in, for example, a powder cleaning agent or a liquid cleaning agent. In particular, the polymer builder for garment detergents of the present invention is excellent in compatibility with surfactants, especially nonionic surfactants, and is excellent for liquid detergents. By being excellent in compatibility with the surfactant, when blended with a liquid detergent, the composition has good transparency and can be a highly concentrated liquid detergent composition.

  The polymer builder for a detergent obtained by the production method of the present invention is excellent in hydrolysis resistance. It is difficult to hydrolyze even when stored at high temperatures, and has excellent performance and stability of formulation. Moreover, it is excellent in the color and smell of the solution.

  The polymer builder for detergent obtained by the production method of the present invention is blended in a clothes detergent, preferably a liquid detergent for clothes. As an example of a clothing detergent containing the polymer builder for detergent, 0.1-10 wt% of the polymer builder for detergent of the present invention, 20-70 wt% of nonionic surfactant, an anionic surfactant A liquid detergent for clothes containing 5 to 20 wt%, 1 to 30 wt% of solvent, and 5 to 50 wt% of water (preferably a total of 50 wt% or more of nonionic surfactant and anionic surfactant) Can be mentioned.

[Example 1: Synthesis of synthetic polymer (1)]
Acrylic acid / polyethylene glycol (average number of moles of ethylene oxide added 21) allyl ether = 28/72 (weight ratio) copolymer [synthetic polymer (1)] was synthesized as follows.

In a glass reactor equipped with a thermometer, stirrer, nitrogen inlet tube, and reflux condenser, 206 g of propylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 126 g of ion-exchanged water, 80% acrylic acid aqueous solution (Toagosei Chemical) Co., Ltd.) 5.2 g (5% based on the total weight of acrylic acid), polyethylene glycol (21 average number of moles of ethylene oxide added) 100.8 g of allyl ether (50% based on the total weight of polyethylene glycol allyl ether), nitrogen The mixture was mixed under an atmosphere and the temperature was raised to 85 ° C. A solution prepared by mixing 49 g of an 80% aqueous solution of acrylic acid, 25 g of ion-exchanged water and 100.8 g of polyethylene glycol (ethylene oxide average addition mole number 21) allyl ether (acrylic acid: polyethylene glycol allyl ether = 28: 72 (weight ratio)). And 3.7 g of sodium persulfate (manufactured by Wako Pure Chemical Industries, Ltd.) and 18.6 g of ion-exchanged water were separately added dropwise over 84 minutes. After completion of the dropwise addition, 43.9 g of an 80% aqueous acrylic acid solution and a liquid obtained by mixing 3.3 g of sodium persulfate and 16.7 g of ion-exchanged water were separately added dropwise over 153 minutes. After completion of the dropping, stirring was continued at 85 ° C. for 3 hours. The temperature was returned to room temperature, and 700 g (polymer concentration: 40% by weight) of a solution containing the synthetic polymer (1) was obtained. As a result of GPC measurement of the obtained synthetic polymer (1), the weight average molecular weight was 21,000 (in terms of polyethylene glycol). Further, as a result of ¹ H-NMR measurement, the acrylic acid remaining in the obtained solution was less than the detection limit as the concentration in the solution, and similarly polyethylene glycol allyl ether was 1.2% by weight. The monomer addition amount, weight ratio, etc. are as shown in Table 1. In this example, the weight of the monomer (I) with respect to the weight of the total monomer in the reaction solution from the start of polymerization (0 minute) to the addition of 86% by weight of the total monomer (II) used (60 minutes). The difference between the maximum value and the minimum value of the percentage (%) was 0% (0 points). In the table, the weight ratio of monomer (I) / monomer (II), the weight ratio in the reaction solution is based on the charged amount for 0 minutes, and the weight ratio after that is calculated from the measured values. (The same applies hereinafter). In addition, in the table | surface, it means that addition of the monomer is complete | finished when the ratio (weight% / cumulative amount basis) with respect to the total usage amount reaches 100% (the same applies hereinafter).

  The color of the solution of the synthetic polymer (1) was colorless and transparent and had a light solvent odor but no specific odor derived from the thio compound.

[Example 2: Synthesis of synthetic polymer (2)]
Acrylic acid / polyethylene glycol (ethylene oxide average addition mole number 25) allyl ether = 25/75 (weight ratio) copolymer [synthetic polymer (2)] was synthesized as follows.

In a glass reactor equipped with a thermometer, stirrer, nitrogen inlet tube, and reflux condenser, 295 g of propylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 192 g of ion-exchanged water, 80% aqueous acrylic acid (Toagosei Chemical) 6.3 g (5% based on the total weight of acrylic acid), polyethylene glycol (average number of moles of added ethylene oxide 25) 150 g of allyl ether (50% based on the total weight of polyethylene glycol allyl ether), put under nitrogen atmosphere And heated up to 85 ° C. A solution (acrylic acid: polyethylene glycol allyl ether = 25: 75 (weight) of 62.5 g of 80% acrylic acid aqueous solution, 37.5 g of ion exchange water and 150 g of polyethylene glycol (ethylene oxide average addition mole number 25) allyl ether was mixed there. Ratio)) and a solution in which 5.3 g of sodium persulfate (manufactured by Wako Pure Chemical Industries, Ltd.) and 21.2 g of ion-exchanged water were separately added dropwise over 75 minutes. After completion of the dropwise addition, a solution prepared by mixing 56.3 g of an 80% aqueous acrylic acid solution, 4.8 g of sodium persulfate and 19.1 g of ion-exchanged water was separately added dropwise over 135 minutes. After completion of the dropping, stirring was continued at 85 ° C. for 3 hours. It returned to room temperature and obtained 1000g (polymer concentration: 40 weight%) of solutions containing a synthetic polymer (2). As a result of GPC measurement of the obtained synthetic polymer (2), the weight average molecular weight was 21,000 (in terms of polyethylene glycol). As a result of ¹ H-NMR measurement, the acrylic acid remaining in the obtained solution was not more than the detection limit as the concentration in the solution, and similarly polyethylene glycol allyl ether was 1.6% by weight. The monomer addition amount, weight ratio, etc. are as shown in Table 2. In this example, the weight of monomer (I) with respect to the weight of all monomers in the reaction solution from the start of polymerization (0 minutes) until 90% by weight of all monomers (II) used is added (60 minutes). The difference between the maximum value and the minimum value of the percentage (%) was 0% (0 points).

  The color of the solution of the synthetic polymer (2) was colorless and transparent and had a light solvent odor but no specific odor derived from the thio compound.

[Example 3: Synthesis of synthetic polymer (3)]
Acrylic acid / polyethylene glycol (ethylene oxide average addition mole number 25) allyl ether = 25/75 (weight ratio) copolymer [synthetic polymer (3)] was synthesized as follows.

In a glass reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser, 880.4 g of propylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 551.2 g of ion-exchanged water, 80% acrylic acid aqueous solution (Made by Toagosei Chemical Co., Ltd.) 18.8 g (5% based on the total weight of acrylic acid), polyethylene glycol (average number of moles of added ethylene oxide 25) 450.1 g of allyl ether (50% based on the total weight of polyethylene glycol allyl ether) Were mixed in a nitrogen atmosphere and heated to 85 ° C. A solution prepared by mixing 187.5 g of an 80% acrylic acid aqueous solution, 450.0 g of polyethylene glycol (ethylene oxide average addition mole number 25) allyl ether and 112.5 g of ion-exchanged water, and sodium persulfate (Wako Pure Chemical Industries, Ltd.) )) 15.9 g, ion-exchanged water 63.6 g and 30% hydrogen peroxide solution (manufactured by Sigma-Aldrich) 15.6 g were separately added dropwise over 75 minutes. After completion of dropping, 168.8 g of 80% acrylic acid aqueous solution and 14.3 g of sodium persulfate, 57.3 g of ion-exchanged water, and 14.1 g of 30% hydrogen peroxide solution were separately added over 135 minutes. It was dripped. After completion of the dropping, stirring was continued at 85 ° C. for 3 hours. The temperature was returned to room temperature, and 3000 g (polymer concentration: 40% by weight) of the solution containing the synthetic polymer (3) was obtained. As a result of GPC measurement of the resulting synthetic polymer (3), the weight average molecular weight was 22,000 (in terms of polyethylene glycol). Moreover, as a result of ¹ H-NMR measurement, the acrylic acid remaining in the obtained solution was not more than the detection limit as the concentration in the solution, and similarly polyethylene glycol allyl ether was 2.2% by weight. The monomer addition amount, weight ratio, etc. are as shown in Table 3. In this example, the weight of monomer (I) with respect to the weight of all monomers in the reaction solution from the start of polymerization (0 minutes) until 90% by weight of all monomers (II) used is added (60 minutes). The difference between the maximum value and the minimum value of the percentage (%) was 1% (1 point).

Moreover, the color of the solution of the synthetic polymer (3) was colorless and transparent, and the smell was light, but there was no specific odor derived from the thio compound.

[Comparative Example 1: Synthesis of comparative synthetic polymer (1)]
Acrylic acid / polyethylene glycol (average number of added moles of ethylene oxide 25) allyl ether = 25/75 (weight ratio) copolymer [comparative synthetic polymer (1)] And synthesized.

In a glass reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser, 295.0 g of propylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 154.6 g of ion-exchanged water, 80% polyethylene glycol ( Ethylene oxide average addition mole number: 25) 375.0 g of allyl ether aqueous solution (100% based on the total weight of polyethylene glycol allyl ether) was added, mixed in a nitrogen atmosphere, and heated to 85 ° C. There, 125.0 g of 80% aqueous acrylic acid solution (manufactured by Toagosei Co., Ltd.) (100% based on the total weight of acrylic acid), 10.1 g of sodium persulfate (manufactured by Wako Pure Chemical Industries, Ltd.) and ions The liquid mixed with 40.3 g of exchange water was separately added dropwise over 60 minutes. After completion of the dropping, stirring was continued at 85 ° C. for 3 hours. It returned to room temperature and obtained 1000g (polymer concentration: 40 weight%) of solutions containing a comparative synthetic polymer (1). As a result of GPC measurement of the obtained comparative synthetic polymer (1), the weight average molecular weight was 29,000 (in terms of polyethylene glycol). Further, as a result of ¹ H-NMR measurement, the acrylic acid remaining in the obtained solution was not more than the detection limit as the concentration in the solution, and similarly polyethylene glycol allyl ether was 2.0%. The monomer addition amount, weight ratio, etc. are as shown in Table 4.

Moreover, the color of the solution of the comparative synthetic polymer (1) was colorless and transparent, and the smell was light, but there was no specific odor derived from the thio compound.

[Comparative Example 2]
Acrylic acid / polyethylene glycol (ethylene oxide average addition mole number 25) allyl ether = 25/75 (weight ratio) copolymer was tried using only water as a liquid reaction medium as follows, but the reaction was continued. The target copolymer could not be obtained.

  In a glass reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser, 147 g of ion-exchanged water, 6.3 g of 80% acrylic acid aqueous solution (manufactured by Toagosei Chemical Co., Ltd.) (based on the total weight of acrylic acid) 5%), 80% polyethylene glycol (average number of moles of ethylene oxide added 25) 188 g of allyl ether aqueous solution (50% based on the total weight of polyethylene glycol allyl ether) was added, mixed in a nitrogen atmosphere, and heated to 85 ° C. Thereto, 62.5 g of 80% acrylic acid aqueous solution and 188 g of 80% polyethylene glycol (ethylene oxide average addition mole number 25) allyl ether aqueous solution and 2.7 g of sodium persulfate (manufactured by Wako Pure Chemical Industries, Ltd.) Then, 21.2 g of ion-exchanged water and 2.6 g of 30% hydrogen peroxide solution (manufactured by Sigma-Aldrich) were separately added dropwise over 75 minutes. After completion of dropping, 56.3 g of 80% acrylic acid aqueous solution, 2.4 g of sodium persulfate, 19.1 g of ion-exchanged water, and 2.3 g of 30% hydrogen peroxide solution were separately added over 135 minutes. Although an attempt was made to drop the solution, when 95 minutes passed, the viscosity of the reaction solution increased and gelation of the produced polymer was observed, making it difficult to continue the polymerization.

<Reference Examples 1-2, Comparative Reference Example 1>
Using the synthetic polymers (2) and (3) obtained above and the comparative synthetic polymer (1), the solubility in the liquid detergent composition was evaluated as follows.

[I] Evaluation of solubility (I-1)
2-aminoethanol (manufactured by Wako Pure Chemical Industries, Ltd.) is added to the solutions of the synthetic polymers (2) and (3) and the comparative synthetic polymer (1) to completely neutralize the solution so that the polymer concentration becomes 20% by weight. Adjust with ion exchange water.

(I-2)
A liquid detergent composition was prepared using the 20 wt% solution of the neutralized polymer prepared in (I-1) above and the components shown in Table 5. The components in Table 5 were mixed, degassed, and allowed to stand at 25 ° C. for 1 hour to obtain a liquid detergent composition, and then with a UV measurement device (Shimadzu Corporation UV-2550, 1 cm cell, wavelength 660 nm). The transmittance was measured. The evaluation results are shown in Table *, and it can be determined that a transmittance of 95% or more is transparent dissolution, and less than 95% is turbid. In addition, the numerical value of the addition amount in a table | surface is weight% of solid content or an active ingredient conversion.

* 1: Polyoxyethylene polyoxypropylene alkyl ether (Emulgen LS-110, manufactured by Kao Corporation)
* 2: Linear alkyl (C12-14) benzenesulfonic acid * 3: Wako Pure Chemical Industries, Ltd. * 4: Wako Pure Chemical Industries, Ltd.

Claims (6)

Using a liquid reaction medium, a monomer represented by the following general formula (I) [hereinafter referred to as monomer (I)] and a monomer represented by the following general formula (II) [hereinafter referred to as monomer (II)] In producing a polymer builder for a detergent by polymerizing in a reaction vessel,
Using a liquid containing a lower alcohol as a liquid reaction medium,
Monomer (I) in an amount corresponding to 1 to 20% by weight of the total monomer (I) used, and monomer (II) in an amount corresponding to 30 to 80% by weight of the total monomer (II) used are monomer ( Before the polymerization is started, the reaction vessel is preliminarily set so that the ratio of I) to monomer (II) is monomer (I): monomer (II) = 0.4: 99.6 to 15:85 (weight ratio). Preparation,
Adding the remainder of monomer (I) and monomer (II) to the reaction vessel after the start of polymerization,
Manufacturing method of polymer builder for cleaning agent.

[Wherein, R ¹ represents a hydrogen atom or —COOM, R ² represents a hydrogen atom or a methyl group, and each M independently represents a hydrogen atom, a monovalent metal, or a divalent metal (1/2 atom). Represents an ammonium group or a substituted ammonium group. ]

[Wherein, R ³ represents a hydrogen atom or a methyl group, A represents one or more alkylene groups having 2 to 3 carbon atoms, X represents a hydrogen atom, a methyl group, a phenyl group or a benzyl group, and n represents It is the average number of moles added and represents a number between 10 and 100. ]   The polymer builder for the detergent comprises the structural unit (I) derived from the monomer (I) and the structural unit (II) derived from the monomer (II) as structural unit (I): structural unit (II) = 10: 90-60. The method for producing a polymer builder for a cleaning agent according to claim 1, wherein the polymer builder is a polymer compound contained in a weight ratio of 40.   The ratio of monomer (I) and monomer (II) in the reaction solution after the start of polymerization is such that monomer (I): monomer (II) = 0.4: 99.6 to 15:85 (weight ratio) The method for producing a polymer builder for cleaning agent according to claim 1 or 2, further comprising a step of adding the monomer (I) and the remainder of the monomer (II) to a reaction vessel.   The monomer (I) is adjusted so that the ratio of the total monomer (I) to be used and the total monomer (II) to be used is monomer (I): monomer (II) = 10: 90 to 60:40 (weight ratio). ) And the remainder of the monomer (II) are added to the reaction vessel. The method for producing a polymer builder for a cleaning agent according to any one of claims 1 to 3.   Until the amount corresponding to 80% by weight or more of the total monomer (II) used is added, the monomer (I) and the remainder of the monomer (II) are replaced with monomer (I): monomer (II) = 10: 90-60: The manufacturing method of the polymer builder for detergents of any one of Claims 1-4 added to reaction container by the weight ratio of 40.   A polymer builder for a detergent obtained by the production method according to claim 1.